0.0950. 0.0101. 0.0105. 0.0742. 0.0089. 0.0090. 26. 1/m [Ln (1/(1-x))]. NO. NOx. 185. ) ...... (20) ml NaCl 3N solution for 24 hours at room temperature . The ion.
CH
NOx
CH, NOx, NO
NO – NOx – CH
NO – NOx – CH
1
I CH NO, NOx [4-1] 1 I 1 1 I
CH NO, NOx
CH
NO, NOx
2 1 I
NO, NOx, CH 2
CH
1
NO, NOx 71 2 1
3 1 I 1
1 2
2
2
3 4
4 (B)
5 (A)
6 7 8 9 10 11 12 13 14 15 16 17 4 1 I
CH, NOx, NO [7-5] dm
1
n 1
vg
vg dm
PA
2 atm-1
n (1) 3
KA
[8]
KA
vA (2)
(3)
(sec-1) k
3
(4)
4 (5)
4
dn/n 5
n (6)
t
X 1
(t) (7)
4
F
4
m 6
7
t
5
(8)
2
8
KA
VA = vA m
6
8
5
9
F
5 1 I (SIGMA – ALDRICH)
1
(Alumina Oxide 90, Merck)
2
(Z)
3
(ZJ)
4 (B)
5 6 1 I
(Seouential ARL 8410) X.R.F.
1
(P W 1830 PHILIS X. R. X.R.D.
2 D)
(DTG-60H SHIMADZU) D.T.A.
3
(Micromeritics Gemini 3) BET (Kane)
4 5 6
(Carbolite)
7 8 7 1 I 1 2
6
3 3 2 1 0.3 0.2
4
5 3
5 7 6
6 5
6
°550
7 8 1 I
100
10
8
2
1
1
2 3
4
3
(A)
3
(B)
11
(A)
10
4
9
8
12 13 5
(B)
(A)
(B)
5
9 7 (A)
(B)
(A)
10
9
6 8 13
12 5
7
7
9 1 I 1
ZB-Ag2O, Al2O3-Ag2O
1
88.33
46.91
50
166.78 4 5
400 400 111
110
9 1 I 9 1 I
1 2 3
550
4
(B)
400
1
(B)
0.075 400 0.075
2
333
3
(Z) 0.6
1 2 3
5 2 5
550
3
8
4 5 6
2 1 2
9 1 I
2 2
9 1 I
1 2 2
9 1 I
2 2 2
9 1 I
3 2 2
9 1 I
IR
3 2
Adsorption of Nitrogen 1
9 1 I 2
9 1 I
1 2
9 1 I
BET BET
II
9 1 I
4
1
5 4
[9]
(ZB-Ag2O, Al2O3-Ag2O)
2 2
9 1 I
1 2 2
9 1 I
NO, NOx 200
2
NO, NOx 9
NO, NOx (ZB-Ag2O, Al2O3-Ag2O) 196.3688
211.1097 238.5045 203.1487
6
6 200
h-1
3
150 250
272.17
283.0085
7
7 200
298.1306
200 -
274.5508
h-1
4
150 250 200 [14-10] 2 2 2
9 1 I [5]
1/m [Ln (1/(1-X))] = 1/F0 KA
F0
5
Ln
X
150 10
m k 8
5 NO, NOx 10 NO KAk 22.4
KAk = / 22.4 KAk = 0.081 / 22.4 = 0.00361 (m mol)/ gr. sec atm NOx KAk 22.4 KAk = / 22.4 KAk = 0.082 / 22.4 = 0.00366 (m mol)/ gr. sec atm 10
(KAk) 1
2
[15] 1 9 1 I
3 2 2
Log {1/m [Ln (1/(1-x))]} = (1/T)
R
R x 2.3 x 10
ZB-Ag2O, Al2O3-Ag2O
IR IR
3 2
9 1 I
1 3 2
9 1 I 9
IR
2 3 2
10
9 1 I
10 6
ZB-Ag2O, Al2O3-Ag2O
IR 10 1 I ZB-Ag2O, Al2O3-MoO3- Ag2O
1
88.33
6.66
1
46.91
2 3
50
4
166.78
4 5
110 550 11
10 1 I
5 6 7
400
(B)
393.34
(B)
400 0.075
1
393.34
2
0.075 111
(Z)
333
3
0.6 1 2 5
3 2 5
4 5
550
3
6 2 1 2 :2 2
IR
12
10 1 I
10 1 I 10 1
:1-2 2
10 1 I
:2-2 2
10 1 I
:3-2 2
10 1 I
:3 2
I
10 1 I
Adsorption of Nitrogen 7
2
10 1 I
1 2
10 1 I
BET BET
11
12 11 II [9]
II
10 1 I
:2 2
:1-2 2
(ZB-Ag2O,
10 1 I
NO, NOx, CH 150
Al2O3-MoO3 - Ag2O)
NO, NOx, CH 8 NO, NOx, CH (ZB-Ag2O, Al2O3-MoO3 - Ag2O) h-1 222.2170 - 217.5772 - 249.9523 13 9 h-1 270.2766 – 287.1702 – 268.8831 14 13 14 10 185
13
:2-2 2
10 1 I
[5] 1/m [Ln (1/(1-X))] = 1/F0 KA
F0
11
Ln
150 16
X
m k
12
185
15
10
12
(KAK)
11 NO, NOx
13
185 150 [15]
10
:3-2 2
10 1 I
Log {1/m [Ln (1/(1-x))]} = (1/T)
R
R x 2.3 x 185
3
150
6.5156 7.2247 7.3288 17 19.4129 18.8347
3
135
7.9247
14
NOx NO
8.4201 7.8839 18 22.8972
21.8060
15
NOx NO [16] IR IR
:3 2
10 1 I
1 3 2
10 1 I
19
14
IR
2 3 2
10 1 I
20
16 (ZB-Ag2O, Al2O3-MoO3 - Ag2O) IR 11 1 I ZJB-Ag2O, Al2O3-Ag2O
88.33 50
1
46.91 166.78
4 5
11 1 I
1 2
110 550
3 4
400
(B)
400 0.075
1
400
(B)
400 0.075 333 0.6
2
111
(ZJ)
3
1
15
2 3
5 2 5
4 5 6
550
3
IR
:2
11 1 I
1 2
11 1 I
:2 2
11 1 I
:1-2 2
11 1 I
:2-2 2
11 1 I
:3-2 2
11 1 I
:3 2
11 1 I :2
Adsorption of Nitrogen 17
1 2
11 1 11 1 I
BET BET
21
22 21 II [9] :2 2
16
11 1 I
:1-2 2
(ZJB-Ag2O, Al2O3-
11 1 I
NO, NOx 150
18
Ag2O)
NO, NOx NO, NOx
23
23 200 150
h-1 347.1557
19
351.8485
24
(ZJB-Ag2O, Al2O3-Ag2O)
359.1284
355.0448
24
20
200
150 250
185 :2-2 2
11 1 I
[5] 1/m [Ln (1/(1-X))] = 1/F0 KA 185
F0 150
Ln
25
X
21
m k
150
10
21 NO, NOx
26
22
185
10
22
(KAK)
NO, NOx 23
185
150
10 [15] :3-2 2
Log {1/m [Ln (1/(1-x))]} = (1/T) 17
11 1 I
24
R
R x 2.3 x IR IR
:3 2
11 1 I
:1-3 2
11 1 I 27
IR
:2-3 2
11 1 I
28 25 ZJB-Ag2O, Al2O3-Ag2O
IR 12 1 I ZB-Cr2O3, Al2O3- Cr2O3
88.33
1
110.48 166.78
4 5
400
12 1 I
1 2 3 4 5
110 550
(B)
400
1
400
2
0.075 400
(B) 0.075
18
111
(Z)
333
3
0.6
1 2 5
3 2 5
4 5
550
3
6
IR
BET
BET
19
12 1 I
1 2
12 1 I
:2 2
12 1 I
:1-2 2
12 1 I
:2-2 2
12 1 I
:3-2 2
12 1 I
:3 2
Adsorption of Nitrogen 26
:2
12 1 I :2
12 1 I
1 2
12 1 I
30 29 II
29 [9] :2 2
:1-2 2
(ZB-Cr2O3, Al2O3-
12 1 I
12 1 I
CH 310
27
Cr2O3)
CH CH (ZB-Cr2O3, Al2O3- Cr2O3)
214.5841
211.1097
31
198.2497
31 400
249.9523
h-1
28
310
248.7588
32
216.3712
32
247.1841
249.9523 h-1
29
400 [17-19] :2-2 2
12 1 I
[5] 1/m [Ln (1/(1-X))] = 1/F0 KA
F0
30
Ln
X
310 10
30
m k 33
CH CH 20
(KAk)
KAk 22.4 KAk = / 22.4 KAk = 0.068 / 22.4 = 0.00303 (m mol)/ gr. sec atm [15]
:3-2 2
12 1 I
Log {1/m [Ln (1/(1-x))]} = (1/T)
R
R x 2.3 x 400
6 2919
6 1899
5 8128
7. 2476
260 3
31
9.5514 7.2938
310
6 3442 34
7.3288
355
CH
7.3288 35
3
32
21.6145
CH IR IR
:3 2
12 1 I
:1-3 2
12 1 I 36
IR
:2-3 2
37
37 33
ZB-Cr2O3, Al2O3- Cr2O3
IR
21
12 1 I
13 1 I 1-13
ZB-Cr2O3, Al2O3-Cr2O3-MoO3
88.33
6.66
1
110.4 166.78
2 3
4
4 5
5
400
1 I
110 550
6
(B)
400
1
393.3
2
333
3
0.075 393.3
(B) 0.075
111
(Z) 0.6
1 2 3
5 2 5
550
3 22
4 5 6
2 1 2
13 1 I
:2 2
13 1 I
:1-2 2
13 1 I
:2-2 2
13 1 I
:3-2 2
13 1 I
IR
:3 2
Adsorption of Nitrogen 34
13 1 I
13 1 I 2
13 1 I
1 2
13 1 I
:2 2
13 1 I
BET
BET
39 38 II [9]
38
:1-2 2
(ZB-Cr2O3,Al2O3-
CH 310
13 1 I
Cr2O3-MoO3)
CH 35 23
CH (ZB-Cr2O3, Al2O3-Cr2O3-MoO3) 204.7453
209.4101
40
40 400
344.8561
41 400
h-1
36
310
352.6421
41
208.2946 209.1289
347.1557
347.1557 h-1
37
355 [19-17] 260 :2-2 2
13 1 I
[5] 1/m [Ln (1/(1-X))] = 1/F0 KA
F0
38
Ln
X
m k 42
310 10
38 CH CH
(KAk) KAk 22.4
KAk = / 22.4 KAk = 0.078 / 22.4 = 0.00348 (m mol)/ gr. sec atm [15] :3-2 2
13 1 I
Log {1/m [Ln (1/(1-x))]} = (1/T)
R
R x 2.3 x 400
24
355
310
260
6 0033
6 1401
6 1318
6 1318 43 14.2840
10.3397
10.1789
3
39 CH
10.1789 44
3
40
31.9910
10.1115
CH IR
:3 2
:1-3
IR
2
13 1 I 13 1 I 45
IR 41
:2-3
2
13 1 I
46
ZBCr2O3, Al2O3-Cr2O3-MoO3
IR
CH NO
CH
NO – NOx
43 42
25
II
1
26
1
2
27
3
ZB-Ag2O, Al2O3-Ag2O
Z
B
BET
1 ZB
ZB-Ag2O, Al2O3-Ag2O ZB-Ag2O, Al2O3Ag2O
ZB
27.1070
Z
B
52.6014
49.3041
51.7946
42.5744
81.9353
76.2058
82.1938
2.8837
9.5036
13.3858
0.4878
24.2233
43.0978
35.9183
51.3067
0.0013
0.0047
0.0069
0.0001
0.0425
0.0631
0.0515
0.0620
62.6644
48.0197
41.7892
47.8927
28
2
BET
2
2 2 3
3
P/P0
4
ZB-Ag2O, Al2O3-Ag2O
5
ZB-Ag2O, Al2O3Ag2O
29
NO, NOx 200
2 (ZB-Ag2O, Al2O3-Ag2O)
h-1 211.1097 200 NOx
NO
0
0
0
78.0822
77.1429
60
78.0822
77.1429
120
80.8219
80.0000
180
h-1 283.0085 200 NOx
0 82.9060 84.6154 84.6154 86.3248 86.3248
30
NO
0 84.0708 84.0708 84.0708 85.8407 85.8407
0 60 120 180 240 300
h-1 367.5768 200 NOx
NO
0 74.5763 77.9661 77.9661
0 73.6842 77.1930 77.1930
0 60 120 180
h-1 519.0041 200 NOx
NO
0 69.9531 70.8920 71.8310 72.7700 74.6479 74.6479 75.5869 h-1 589.5094
0 69.6078 70.5882 71.5686 72.5490 74.5098 74.5098 75.4902
0 60 120 180 240 300 360 420
200 NOx
NO
0
0
0
62.3932
62.8319
60
62.3932
62.8319
120
62.3932
62.8319
180
31
3 (ZB-Ag2O, Al2O3-Ag2O) h-1
% NOx
% NO
203.1487
72.9730
72.9730
°150
238.5045
57.8947
57.8947
°175
211.1097
80.8219
80.0000
°200
196.3688
47.8261
48.3146
°250
6 NO, NOx
(ZB-Ag2O, Al2O3-Ag2O) 4
(ZB-Ag2O, Al2O3-Ag2O) h-1
% NOx
% NO
274.5508
69.2308
68.2540
°150
298.1306
56.3636
54.7170
°175
283.0085
86.3248
85.8407
°200
272.17
37.0787
36.4706
°250
32
7 NO, NOx NO –
(ZB-Ag2O, Al2O3-Ag2O)
10
5
(ZB-Ag2O, Al2O3-Ag2O)
150
NOx
NOx 1/m [Ln (1/(1-x))]
NO 1/m [Ln (1/(1-x))]
1/ F0
0.0121 0.0115 0.0095 0.0061 0.0046 0.0026
0.0121 0.0111 0.0093 0.0060 0.0045 0.0027
0.1679 0.1242 0.1013 0.0738 0.0567 0.0295
1/m [Ln (1/(1-x))]
8
(ZB-Ag2O, Al2O3-Ag2O)
150
33
NOx NO
IR
9
IR
34
10
6 ZB-Ag2O, Al2O3-Ag2O
OH
AL-OH Si-OH
cm-1
cm-1
cm-1
1051.01
1456.96
3445.21
1045.23
1426.10
3450.03
Z
B
7
BET ZB
ZB-Ag2O, Al2O3-MoO3-Ag2O ZB-Ag2O, Al2O3MoO3Ag2O
ZB
Z
B
2
34.4682
52.6014
49.3041
51.7946
54.4739
81.9353
76.2058
82.1938
1.3130
9.5036
13.3858
0.4878
33.1553
43.0978
35.9183
51
0.00046
0.0047
0.0069
0.000017
0.0489
0.0631
0.0515
0.0620
56.7551
48.0197
41.7892
47.8927
35
BET
2 2 2 3
3
P/P0
11
ZB-Ag2O, Al2O3-MoO3Ag2O
12
ZB-Ag2O, Al2O3-MoO3Ag2O
36
(ZB-
NO, NOx
8
150
Ag2O, Al2O3-MoO3 - Ag2O)
246.4030 h-1
217.5772h-1
°150
°150
Removal of NOx %
Removal of NO %
Removal of CH %
Time
Removal of NO %
Removal of CH %
Time
Sec
Removal of NOx %
0.0000 62.1622 64.8649 67.5676 67.5676 67.5676
0.0000 61.1111 63.8889 66.6667 66.6667 66.6667
0.0000 31.8841 33.3333 34.0580 32.6087 32.6087
0.0000 40 71 132 188 248
0.0000 69.2308 73.0769 73.0769 75.0000 75.0000
0.0000 68.0000 72.0000 72.0000 74.0000 74.0000
0.0000 47.0968 52.2581 56.1290 53.5484 56.1290
0.0000 60 120 180 240 300
328.8841 h-1
287.1702 h-1
°150
°150
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0 37.8378 48.6486 51.3514 51.3514
0 38.8889 47.2222 50.0000 50.0000
0.0000 18.6567 22.3881 23.8806 26.1194
0 60 120 180 240
Sec
Sec
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0.0000 48.0000 61.3333 66.6667 66.6667 68.0000 69.3333
0.0000 47.2222 61.1111 66.6667 66.6667 68.0556 69.4444
0.0000 25.0000 35.5263 37.5000 37.5000 38.8158 38.8158
0.0000 60 120 180 240 300 360
37
Sec
929.8820h-1
491.2594 h-1
°150
°150
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0.0000 22.7273 22.7273 20.4545
0.0000 21.4286 21.4286 19.0476
0.0000 -
0.0000 60 120 180
Sec
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0.0000 34.2105 34.2105 31.5789 31.5789
0.0000 35.1351 35.1351 32.4324 32.4324
0.0000 18.5714 14.2857 14.2857 8.5714
0.0000 71 131 191 251
38
Sec
9 (ZB-Ag2O, Al2O3-MoO3 - Ag2O)
% CH
h-1
% NOx
NO
249.9523
48
61.111
61.111
°135
217.5772
56.1290
75.0000
74.0000
°150
222.2170
78.8890
82.6920
82.0000
°185
13 NO, NOx, CH
(ZB-Ag2O, Al2O3-MoO3 - Ag2O) 10
(ZB-Ag2O, Al2O3-MoO3 - Ag2O) NO h-1
% CH
% NOx
268.8831
7.6923
50.0000
50.0000
°135
287.1702
38.8158
69.3333
69.4444
°150
270.2766
45.0549
78.5714
77.5000
°185
39
14 NO, NOx, CH NO –
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
10
11
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
150
NOx 1/m [Ln (1/(1-x))]
NO 1/m [Ln (1/(1-x))]
0.0138 0.0112 0.0118 0.0072 0.0038 0.0023
0.0134 0.0120 0.0118 0.0069 0.0039 0.0021
1/m [Ln (1/(1-x))]
NOx
1/ F0 0.1568 0.1384 0.1188 0.1037 0.0694 0.0367
15
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
150
40
NOx NO
NO –
10
12
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
185
NOx 1/m [Ln (1/(1-x))]
NO 1/m [Ln (1/(1-x))]
0.0175 0.0154 0.0107 0.0107 0.0044 0.0016
0.0171 0.0149 0.0103 0.0103 0.0043 0.0017
NOx
1/ F0 0.1535 0.1262 0.1044 0.0845 0.0443 0.0186
1/m [Ln (1/(1-x))]
16
(ZB-Ag2O, Al2O3-MoO3 - Ag2O) 10
185
KAk
NOx NO
13
de-NO
de-NOx
KAk
KAk
m mol/ gr. sec atm
m mol/ gr. sec atm
0.00361
0.0037
150°
0.00495
0.00513
185°
41
C
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
14
Log {1/m [Ln (1/(1-x))]}
F0 K-1
3
NOx
NO
-2.0259
-2.0259
0.0025
7.3288
-1.9496
-1.9603
0.0024
7.2247
-1.7571
-1.7669
0.0022
6.5156
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
17
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
15
Log {1/m [Ln (1/(1-x))]}
F0 K-1
3
NOx
NO
-2.1603
-2.1603
0.0025
7.8839
-1.9285
-1.9272
0.0024
8.4201
-1.8135
-1.8275
0.0022
7.9247
42
(ZB-Ag2O, Al2O3-MoO3 - Ag2O)
18
IR
43
19
IR
20
16 (ZB-Ag2O, Al2O3-MoO3 - Ag2O) OH
AL-OH Si-OH
cm-1
cm-1
cm-1 1424.17
1043.30
3451.96 1639.20 1468.53
1033.66
3373.85 1508.06
44
ZJ
B
BET
17 ZJB
ZJB-Ag2O, Al2O3-Ag2O ZJB-Ag2O, Al2O3Ag2O
ZJB
23.2847
59.5029
ZJ
B
51.4587
51 7946 2
36.5823
92.7012
78.6582
82.1938
2.7801
10.5466
20.0431
0.4878
20.5046
48.9563
31.4156
51.3067
0.001265
0.005249 0.010510
0.000017
0.036630
0.067492 0.045336
0.0620
62.9256
45.3706
47.8927
35.2406
2 2 2 3
3
P/P0
21
ZJB-Ag2O, Al2O3-Ag2O 45
BET
22
ZJB-Ag2O, Al2O3Ag2O
NO, NOx 150
18 (ZJB-Ag2O, Al2O3-Ag2O)
h-1 211.6815 150 NOx
0 90.9091 90.9091 90.9091
46
NO
0 90.4762 90.4762 90.4762
0 60 120 180
h-1 241.4539 150 NOx
NO
0 87.7551 87.7551 87.7551
0 87.2340 87.2340 87.2340
0 60 120 180
h-1 282.4961 150 NOx
NO
0 85.7143 85.7143 85.7143
0 85.1852 85.1852 85.1852
0 60 120 180
h-1 355.0448 150 NOx
0 82.3529 82.3529 82.3529
47
NO
0 81.8182 81.8182 81.8182
0 60 120 180
h-1 437.5915 150 NOx
NO
0 80.6452 78.4946 76.3441 76.3441
0 79.7753 77.5281 75.2809 75.2809
0 60 120 180 240
19 (ZJB-Ag2O, Al2O3-Ag2O) h-1
% NOx
NO
211.6815
90.9091
90.4762
°150
211.1097
84.9057
84.3137
°185
243.2448
84.6154
84.6154
°200
205.014
46.1538
46.1538
°250
23 NO, NOx
(ZJB-Ag2O-Al2O3-Ag2O)
48
20 (ZJB-Ag2O, Al2O3-Ag2O) h-1
% NOx
% NO
355.0448
82.3529
81.8182
°150
359.1284
64.1509
62.7451
°185
351.8485
68.8889
67.4419
°200
347.1557
48.2759
464286
°250
24 NO, Nox
NO –
(ZJB-Ag2O, Al2O3-Ag2O)
10
21
(ZJB-Ag2O, Al2O3-Ag2O)
150
NOx 1/m [Ln (1/(1-x))]
NO 1/m [Ln (1/(1-x))]
0.0238 0.0208 0.0193 0.0172 0.0150
0.0233 0.0204 0.0189 0.0169 0.0146
49
NOx
1/F0 0.1611 0.1413 0.1207 0.0961 0.0779
1/m [Ln (1/(1-x))]
25
(ZJB-Ag2O, Al2O3-Ag2O)
150
NOx NO
10
22
(ZJB-Ag2O, Al2O3-Ag2O) 185
NO – NOx
NOx 1/m [Ln (1/(1-x))]
NO 1/m [Ln (1/(1-x))]
0.0187 0.0157 0.0133 0.0105 0.0090
0.0184 0.0154 0.0130 0.0101 0.0089
1/m [Ln (1/(1-x))]
1/F0 0.1616 0.1375 0.1175 0.0950 0.0742
26
(ZJB-Ag2O, Al2O3-Ag2O)
185
50
NOx NO
10
KAk
23
de-NO
de-NOx
KAk
KAk
m mol/ gr. sec atm
m mol/ gr. sec atm
0.006875
0.00701
150°
0.005
0.00509
185°
(T)
C
NO – NOx
24
(ZJB-Ag2O, Al2O3-Ag2O) de-NOx
de-NO
KAk
KAk
T
m mol/ gr. sec atm
m mol/ gr. sec atm
0.00701
0.006875
423
0.00509
0.005
458
0.0054
0.00537
473
0.00209
0.00205
523
IR 51
27
IR
28
25 (ZJB-Ag2O, Al2O3-Ag2O) OH
AL-OH Si-OH
cm-1
cm-1
cm-1
1063.55
1458.89
3447.13
1049.09
1422.24
3446.17
52
Z
B
BET
26
(ZB-Cr2O3, Al2O3- Cr2O3) ZB-Cr2O3, Al2O3Cr2O3
ZB
ZB
Z
B
43.8431
52.7564
50.3678
51.7946
69.1211
82.1931
77.6223
82.1938
3.1516
9.3874
14.2969
0.4878
40.6915
43.3690
36.0710
51.3067
0.001308
0.004654 0.007487
0.000017
0.062081
0.063976 0.047057
0.0620
56.6395
48.5065
47.8927
37.3709
53
2
BET
2
2
2
3
3
P/P0
29
ZB-Cr2O3, Al2O3- Cr2O3
30
ZB-Cr2O3, Al2O3- Cr2O3
54
CH
27
310 h-1 198.2497
(ZB-Cr2O3, Al2O3- Cr2O3) h-1 186.8550
310
310
CH
CH
0 76.7123 78.0822 79.4521
0 76.6667 75.0000 70.0000
0 60 120 180
h-1 308.7349
h-1 247.1841
310
310
CH
CH
0 33.3333 40.6250 43.7500
0 60 120 180
0 60 120 180
0 37.3333 65.3333 69.3333
55
0 60 120 180
h-1 347.1557 310 CH
0 19.5767 32.2751 37.5661 34.3915
0 60 120 180 240
28 (ZB-Cr2O3, Al2O3- Cr2O3) h-1 216.3712 198.2497 211.1097 214.5841
% CH 63.2911 79.4521 76.4706 79.5455
56
°260 °310 °355 °400
31 CH
(ZB-Cr2O3, Al2O3- Cr2O3)
29 (ZB-Cr2O3, Al2O3- Cr2O3) h-1
% CH
249.9523 247.1841 248.7588 249.9523
52.9412 69.3333 85.1351 84.9057
°260 °310 °355 °400
32 CH
(ZB-Cr2O3, Al2O3- Cr2O3)
57
CH
10
30
(ZB-Cr2O3, Al2O3- Cr2O3)
CH
310
CH 1/m [Ln (1/(1-x))]
1/F0
0.0133
0.1825
0.0151
0.1720
0.0085
0.1380
0.0049
0.1105
0.0037
0.0982
1/m [Ln (1/(1-x))]
33
(ZB-Cr2O3, Al2O3- Cr2O3)
58
310
31
ZB-Cr2O3, Al2O3- Cr2O3
Log {1/m [Ln (1/(1-x))]}
F0 K-1
3
-2.0024
0.0019
6.3442
-1.8221
0.0017
5.8128
-1.8261
0.0016
6.1899
-1.8028
0.0015
6.2919
CH
ZB-Cr2O3, Al2O3- Cr2O3
34
ZB-Cr2O3, Al2O3- Cr2O3
32
Log {1/m [Ln (1/(1-x))]}
F0 K-1
3
-2.1570
0.0019
7.3288
-2.0731
0.0017
7.2476
-1.7501
0.0016
7.2938
-1.7546
0.0015
7.3288
CH
59
35
ZB-Cr2O3, Al2O3- Cr2O3
IR
60
36
IR
37
33 ZB-Cr2O3, Al2O3- Cr2O3
OH
AL-OH Si-OH
cm-1
cm-1
cm-1
3448.10 1049.09
1422.24 2365.26 3448.10
1049.09
1457.92 2517.61
61
Z
B
BET
34
(ZB-Cr2O3, Al2O3-Cr2O3-MoO3) ZB-Cr2O3, Al2O3Cr2O3MoO3
33.6362
ZB
52.7564
ZB
Z
B
50.3678
51.7946 2
52.9426
82.1931
77.6223
BET
82.1938 2
3.1309
9.3874
14.2969
0.4878
30.5053
43.3690
36.0710
51.3067
0.001368
0.004654 0.007487
0.000017
0.047712
0.063976 0.047057
0.0620
2
2 3
3
56.7393
48.5065
37.3709
P/P0
47.8927
38
ZB-Cr2O3, Al2O3-Cr2O3-MoO3
62
39
ZB-Cr2O3, Al2O3-Cr2O3MoO3
CH 310
35 (ZB-Cr2O3, Al2O3-Cr2O3-MoO3)
h-1 208.2946
h-1 188.4453
310
310
CH
CH
0 79.7872 81.9149 79.7872
0 80.1105 82.3204 80.1105
0 60 120 180
63
0 60 120 180
h-1 278.9655
h-1 233.8616
310
310
CH
CH
0 43.2990 47.4227 47.4227
0 57.0681 60.2094 66.4921
0 60 120 180
0 60 120 180
h-1 347.1557 310 CH 0 41.2371 39.1753 41.2371 43.2990
64
0 60 120 180 240
36 (ZB-Cr2O3, Al2O3-Cr2O3-MoO3) h-1 209.1289 208.2946 209.4101 204.7453
CH 58.8235 79.7872 81.4433 79.6296
°260 °310 °355 °400
40 CH
(ZB-Cr2O3, Al2O3-Cr2O3-MoO3) 37
(ZB-Cr2O3, Al2O3-Cr2O3-MoO3) h-1
% CH
347.1557
25.9740
°260
347.1557
43.2990
°310
352.6421
73.2143
°355
344.8561
74.6032
°400
65
41 CH CH
(ZB-Cr2O3, Al2O3-Cr2O3-MoO3)
10
38
(ZB-Cr2O3, Al2O3-Cr2O3-MoO3)
CH
310
CH 1/m [Ln (1/(1-x))]
1/F0
0.0164 0.0162 0.0094 0.0061 0.0053
0.1810 0.1637 0.1458 0.1223 0.0982
1/m [Ln (1/(1-x))]
42
(ZB-Cr2O3, Al2O3-Cr2O3-MoO3)
66
310
39 F0
Log {1/m [Ln (1/(1-x))]} CH
K-1
3
-2.0560 -1.7907 -1.7681 -1.7685
0.0019 0.0017 0.0016 0.0015
6.1318 6.1318 6.1401 6.0033
43
ZB-Cr2O3, Al2O3-Cr2O3-MoO3
40 Log {1/m [Ln (1/(1-x))]} K-1
CH -2.4772
0.0019
-2.2785
0.0017
-1.8844
0.0016
-1.8672
0.0015
67
3
10.1789 10.1789 10.3397 10.1115
44
ZB-Cr2O3, Al2O3-Cr2O3-MoO3
IR
68
45
IR
46
41 ZB-Cr2O3, Al2O3-Cr2O3-MoO3
AL-OH
OH
Si-OH cm-1
cm-1
cm-1
1060.66
1513.85
2371.05
1634.38 3450.99 1052.94
1472.38 2344.05 1426.10
69
NO - NOx
42
ZJB-Ag2O, Al2O3-Ag2O 1
ZJB-Ag2O, Al2O3-Ag2O
NOx
NO
NOx
NO 3
-
-
% 76.3441
% 75.2809
437.5915
150
% 80
% 80
-
-
421.0787
175
CH
43
ZB-Cr2O3,Al2O3-Cr2O3-MoO3 2
CH %
ZB-Cr2O3,Al2O3-Cr2O3-MoO3
3
CH %
3
347.1557
°250
% 25.9740
347.1557
°260
%43.8914
301.002
°350
% 73.7705
287.1702
355
%46.9320
339.6102
400
%74.6032
344.8561
400
70
71
1 NO, NOx, CH 1
3 1 I 2 2 4 1
I 3
CH NO, NOx 71 1
9 1 I
4
ZB-Ag2O, Al2O3-Ag2O
11 8 I
ZB-Ag2O, Al2O3-MoO3- Ag2O
15 11 1
11 1 I
1
10 1
ZJB-Ag2O, Al2O3-Ag2O
18 15 1
12 1 I
ZB-Cr2O3, Al2O3- Cr2O3
21 18 1 I
ZB-Cr2O3, Al2O3-Cr2O3-MoO3
25 22
72
1-13
NO – NOx – CH
NO – NOx – CH
73
[1] Coq, B., Mauvezin, M., Delahay, G., Butet and J. B., Kieger, S., 2000, The simultaneous catalytic reduction of NO and N2O by NH3 using an Fe-zeolite-beta catalyst. Appl. Catal., B Vol. 27 pp. 193-198. [2] Burch, R., Breen, J. P., and Meunier, F. C., 2002, A review of the selective reduction of NOx with hydrocarbons under lean-burn conditions with non-zeolitic oxide and Platinum group metal catalysts. Appl. Catal. B, Vol. 39 pp. 283-303. [3] Subbiah, A., Cho, B. K., Blint, R. J., Gujar, A., Price, G. L. and Yie, J. E., 2003, NOx reduction over metal-ion exchanged novel zeolite under lean conditions: activity and hydrothermal stability. Appl. Catal. B, Vol. 42 pp. 155-178 [4] Pieterse, J. A. Z., Brink, R. W., Booneveld, S. and Bruijn, F. A., 2003, Influence of Zeolite structure on the activity and durability of Co-Pd-Zeolite catalyst in the reduction of NOx with methane. Appl. Catal. B, Vol. 46 pp. 239-250. [5] Bassed, D. W. and Habgood, H. W., 1959, A gas chromatographic study of the catalytic isomerization of cyclopropane. Jour. Phys. Chem., Vol. 64 pp. 769-773. [6] K. V. Topchieva, B. V. Romanovskii, L. I. Thoang, Y. W. Bizreh, Procc. 4th Inter. Cong. Catal. 2 (1971) 135. [7] Bizreh, Y. W. and Gates, B. C., 1984, Butane cracking catalyzed by the zeolite HZSM-5. Jour. Catal., Vol. 88 pp. 240-243. [8] Ya. Girasimov and others, Phys. Chem. 1 (1974) 534. [9] H. A. De Boer, Proc. X Symp. Colston Research Sco. Unvi. Bristol, (Eds. Everttd, N., Stone, F. S. and Butterw Orths), Sci. Bull. London (1958) 68-94. [10] Kooten, W. E. J., Krijsen, H. C., Bleek, C. M. and Calis, H. P. A., 2000, Deactivation of zeolite catalysts used for NOx removal. Appl. Catal. B, Vol. 25 pp. 125-135. [11] Ohtsuka, H. and Tabata, T., 2001, Roles of palladium and platinum in the selective catalytic reduction of nitrogen oxides by methane on palladium-platinum-loaded sulfated zirconia. Appl. Catal. B, Vol. 29 pp. 177-183. [12] Shi, C., Cheng, M., Qu, Z., Yang, X. and Bao, X., 2002, On the selectively catalytic reduction of NOx with methane over Ag-ZSM-5 catalysts. Appl. Catal. B, Vol. 36 pp. 173182. [13] Zhu, Z., Liu, Z., Liu, S., Niu, H., Hu, T., Liu, T. and Xie, Y., 2000, NO reduction with NH3 over an activated carbon-supported cooper oxide catalysts at low temperatures. Appl. Catal. B, Vol. 26 pp. 25-35. [14] Moreno-Tost, R., Castellon, E. R. and Jimenez-Lopez, A., 2006, Cobalt-iridium impregnated zirconium-doped mesoporous silica as catalysts for the selective catalytic reduction of NO with ammonia. Jour. Molec. Catal. A Chem., Vol. 248 pp. 126-134.
74
[15] Serra, R., Vecchietti, M. J., Miro, E. and Boix, A., 2008, In, Fe-zeolites: Active and stable catalysts for SCR of NOx-Kinetics, characterization and deactivation studies. Catal. Today Vol. 133-135 pp. 480-486. [16] Richter, M., Bentrup, U., Eckelt, R., Schneider, M., Pohl, M. M. and Fricke, R., 2004, The effect of hydrogen on the selective catalytic reduction of NO in excess Oxygen over Ag/Al2O3. Appl. Catal. B, Vol. 51 pp. 261-274. [17] Mccabe, R. W. and Mitchell, P. J., 1986, Exhaust catalyst development for methanolfueled vehicles: 1. A comparative study of methanol oxidation over alumina-supported catalysts containing group 9, 10, and 11 metals. Appl. Catal. B, Vol. 27 NO. 1 pp. 83-98. [18] Xanthopoulou, G. and Vekinis, G., 1998, Investigation of catalytic oxidation of carbon monoxide over a Cu–Cr-oxide catalyst made by self-propagating high-temperature synthesis. Appl. Catal. B, Vol. 19 NO.1 pp. 37-44. [19] Mescia, D., Cauda, E., Russo, N., Fino , D., Saracco, G. and Specchia,V., 2006, Towards practical application of lanthanum chromite catalysts for diesel particulate combustion. Catal. Today, Vol. 117 NO.1-3 pp. 369-375.
75
1 2
I
2 2
1 I
2
1 1 I
2
2 1 I
2
3 1 I
3
4 1 I
6
5 1 I
6
6 1 I
6
7 1 I
7
8 1 I
8
9 1 I
8 8
1
ZB-Ag2O, Al2O3-Ag2O
1
9 1 I 9 1 I
9
2
9 1 I
9
1 2
9 1 I
9
2 2
9 1 I
76
9
1 2 2
9 1 I
10
2 2 2
9 1 I
11
3 2 2
9 1 I
3 2
9 1 I
1 3 2
9 1 I
11
IR
11
IR
11
IR
11
11
2 3 2
1
ZB-Ag2O,
1
9 1 I
10 1 I
10 1 I
Al2O3-MoO3- Ag2O
13
2
10 1 I
13
1 2
10 1 I
13
2 2
10 1 I
13
1 2 2
10 1 I
14
2 2 2
10 1 I
77
14 14
IR
14
IR
15
IR
3 2 2
10 1 I
3 2
10 1 I
1 3 2
10 1 I
2 3 2
15 15
10 1 I
11 1 I ZJB-Ag2O, Al2O3-
1
11 1 I Ag2O
16
2
11 1 I
16
1 2
11 1 I
16
2 2
11 1 I
17
1 2 2
11 1 I
17
2 2 2
11 1 I
17
3 2 2
11 1 I
3 2
11 1 I
18
IR
78
18
IR
18
IR
1 3 2
2 3 2
18 18
11 1 I
11 1 I
12 1 I ZB-Cr2O3, Al2O3- Cr2O3
1
12 1 I
19
2
12 1 I
19
1 2
12 1 I
20
2 2
12 1 I
20
1 2 2
12 1 I
20
2 2 2
12 1 I
21
3 2 2
12 1 I
3 2
12 1 I
1 3 2
12 1 I
21
IR
21
IR
21
IR
79
2 3 2
12 1 I
22 22
13 1 I ZB-Cr2O3, Al2O3-
1
13 1 I
Cr2O3-MoO3
23
2
13 1 I
23
1 2
13 1 I
23
2 2
13 1 I
23
1 2 2
13 1 I
24
2 2 2
13 1 I
24
3 2 2
13 1 I
3 2
13 1 I
1 3 2
13 1 I
25
IR
25
IR
25
IR
25
2 3 2
CH NO
26
80
13 1 I
II
71 72 73 73 74
81
A New Developed Flow Micropulse- Like Catalytic Pilot Plant For Testing And Determination The Catalytic Activity And Kinetics For de-NOx or de-CH From Car Exhaust Gas Emissions By Use Of Catalysts From Metal Oxides Supported By Matrixs From –Syrian Natural Zeolite And Bentonite-And Alumina Theoretical Of The Innovated Developed Pilot Plant For Kinetics Of Catalytic Removal Of NO, NOx, And CH Pollutants From Gases Emitted From Car Exhausts
Prof. YAHYA WALID AL BIZREH LUBNA AL HAMOUD Prof. MALAK AL JOUBEH Key Words: Matrixes of Syrian and Jordanian zeolites and Syrian bentonite for catalytic removal of NO – NOx and CH emitted with car exhaust gases. Flow micro pulse- like device for testing and measuring catalytic activity and kinetics for removal of NO – NOx and CH emitted with exhaust gases.
1
I- Technical Description of the invention A- Former technical condition: Removal of NO, NOx and CH from car exhaust gases have been the main issue among numerous researches on air pollutants. The current work is a mere contribution to the global efforts in this field of scientific investigations [1-4]. B- I-1- Technical Description of the invention: The detailed explanation of the invention: I – 1 – 1 Innovation: a) We have constructed a micro pulse flow catalytic pilot plant for researches and tests on catalytic activity and determination of kinetic parameters concerning the de-NOx, de-NO and de-CH catalysts. b) Preparation of matrixes of Syrian and Jordanian zeolites and Syrian bentonite for use as supports of metal oxides catalyzing the deNOx, de-NO and de-CH processes. I – 1 – 2 Innovation step and industrial capability : a) Development of anew catalytic micro pulse –like flow pilot plant for use as a device for measuring the interaction between the car exhaust pollutants such as NO, NOx and CH and the catalyst to be used for the first time in the field of car exhaust between catalysis (Figs. 1, 2). b) Use of the car exhaust gas as a substitute for a carrier gas. c) Use of the catalyst in its industrial form with in relatively large size and quantities. d) Preparation of matrixes of Syrian and Jordanian zeolites and Syrian bentonite for use as supports of metal oxides catalyzing the deNOx, de-NO and de-CH processes (p. 70 ) I – 1 – 3 Technical description of the pilot plant: The invention is a pilot plant constuents of which are represented in the scheme of Figs. 1, 2: 1- A motor car with internal combustion engine. 2- Gases emitted from car exhaust passing through a condensate of water vapors. 2
3- Car exhaust gas compressor attached with a gas regulator. 4- Three way gas velocity controlling valve. 5- Pass by flow gas tube through the heating system with a valve B. 6- Flow gas tube with valve A for the reacting gas in the catalytic reactor. 7- A glass cylinder for the passing by gas analysis. 8- Catalytic pilot plant reactor. 9- Electric heater. 10-
The catalyst layer on a bed.
11-
Three way valve.
12-
Velocity foam bubble gas meter.
13-
A glass cylinder for the out coming gas from the reactor.
14-
Barometer.
15-
Thermo couple connected with a thermostat.
16-
Thermometer for relatively high temperatures.
17- Gas Analyzer (detector) I – 1 – 4: Theoretical of the innovated development pilot plant for kinetics of catalytic removal of NO, NOx and CH pollutants from gases emitted from car exhausts Dependence of conversion rate on flow rate for car exhaust gas at different temperatures was determined by means of micro pulse flow method that already was used for isomerization and cracking of light hydrocarbons [5-7] and it has been modified and suggested for the first time in our work and reviewed to fit the current innovation. The rate constant equation is derived as following: 1- When a volume of gas with the reacting material passes through the catalytic reactor containing dm gr. of the catalyst at an instant, m moles of the reactant will be distributed between the gas phase of the volume vg dm where vg is the volume of the gas space at the sector of the catalytic reactor that contains 1 gr. catalyst, and the adsorbed phase where the reaction takes place. 3
2- Assuming that PA is the partial pressure of the reactant, and KA is the adsorption equilibrium constant for 1 gr. of the catalyst, then we may write the total mole number n as the following: (1) 3- The adsorption equilibrium constant KA is related with the adsorbed volume of the reactant gas by one gram of the catalyst vA with the equation [8]: (2) and the value of n will be (3) 4- Since the surface reaction controls the reaction rate and k (sec-1) is the first order real rate constant of the surface reaction, the rate of reaction of the adsorbed reactant in the related section of catalyst is:
(4) Rearranging (4) we get the following equation: (5) and the conversion rate is independent on the pressure. 5- If n in equation (4) is replaced with the whole reacting moles in the space of reaction, then the integration of equation (5) will lead to: (6) Where X is the conversion rate and t is the time of stayment of the reacting moles on the surface of the catalyst
4
6- When F (ml sec-1) is the flow rate of the gases mixture in the reacting molecules at the reactor temperature and the mean pressure. The time of stayment (t) of the reactant in the reacting space is: (7) where m is the whole mass of the catalyst 7- Substituting (7) in the equation (6) is
(8) Replacing KA in equation (8) with its value from equation (2) we receive:
where the VA is the adsorbed volume of the reactant on the surface of the catalyst (VA = vA m) 8- The flow rate (F) in an experiment is measured at room temperature and mean pressure and the then corrected to zero C° to become:
If (9) is taken into account, the equation (8) will have the form
5
The apparent activation energy of the considered reaction can be determined from
I – 1 – 5: The invented catalysts components are: 1- Metal nitrates (SIGMA – ALDRICH). 2- Aluminum oxide (Alumina Oxide 90, Merck). 3- Syrian zeolite (Z). 4- Jordanian zeolite (ZJ). 5- Syrian bentonite (B). I – 1 – 6: Equipments used in the work: 1- X-Ray Fluorescence X.R.F. (Seouential ARL 8410). 2- X-Ray diffraction (P W 1830 PHILIS). 3- Differential Thermal Analysis D.T.A. (DTG-60H SHIMADZU). 4- The Surface Area device (Micromeritics Gemini 3). 5- GAS Analyzer (Kane). 6- Compressor 7- Furnace (Carbolite). 8- The new developed micro pulse -like flow catalytic pilot plant. I – 1 – 7: General Method: 1- Impregnation of the metal nitrate on alumina. 2- Impregnation of the metal nitrate on the Syrian or Jordanian zeolite. 3- Impregnation of the metal nitrate on the bentonite. 4- Finishing the matrix by mixing the peats resulting in the above mentioned 1-2 and 3 steps until being homogenized. 5- Formation of cylindrical tablets of 3-5 cm and internal diameter of 0.2 – 0.3 cm. 6
6- Leaving in shade to dry within 6-7 days. 7- Heating at 550°C for 5-6 hours. I – 1 – 8: Method of Experiment: 1- Inserting 100 g. of the catalyst (10) into the reactor (8). 2- Transmitting the car exhaust gas from the vehicle (1) via rubber tubes (2) and water vapor condenser (2) to gas compressor (3). 3- The reacting gas passes from the compressor (3) to a three way gas velocity controlling valve (4). 4- In order to start the measurements valve (B) is closed simultaneously with valve (A) opened to make the car exhaust gas pass through to the catalytic reactor (8) heated by the heater (9). The reacted with the contact mass (10) moves through the three way valve (11) to the bubble gas velocity meter (12) for the out put gas. 5- Valve (A) is closed and valve (B) is opened to make the gas flow from valve (B) through the tube (5) via heater (9) passing by the catalyst to be analyzed after being catalyzed in a glass cylinder (7), the result of analyses provide the structure of the passby gas exhaust heated to the same temperature of the heated catalyst in the reactor 6- The next step is to open valve (A) and shut the valve (B) at the same moment in order to make three minutes gas pulse pass through in the reactor (8) and get reacted in the catalyst layer (10). The resulting gas and products of the catalytic reaction pass to the three way valve (11) to be collected in the glass cylinder (13) and analyzed by means of the KANE GAS ANALZER. 7- Step (5) is to be repeated to make sure that the structure of the initial reacting car exhaust gas before the catalytic measurements is identical to the structure of the initial gas after measuring the catalytic activity at the same temperature and mean pressure.
7
I – 1 – 9: Preparation and the experiments of the catalysts: I – 1 – 9: Preparation and the experiments of the Syrian Silver catalysts I – 1 –9-1: Preparation of The catalyst ZB-Ag2O, Al2O3-Ag2O: was prepared in the following stages: Stage A: Preparation of the alumina supported metal oxide: 1A- 46.91 gr. of silver nitrate were dissolved in 88.3 ml of hot distillated water (solution I). 2A- Solution I was impregnated with 166.78 gr. of alumina to form a paste, more than 50 ml of distillated water were added and mixed with the paste, the paste was put to dry in the shade. 3A- The dried product was heated at 110°C for 4 hours. 4A- The resulting mass was heated at 550°C in the oven for 5 hours. Stage B: impregnation of Syrian bentonite (B) and Syrian zeolite (Z) with silver nitrate solution: 1B- 400 gr. of Syrian bentonite (B) were impregnated with 400 ml of 0.075 N silver nitrate solution. 2B- 400 gr. of Syrian bentonite (B) were impregnated with 400 ml of 0.075 N silver nitrate solution. 3B- 333 gr. of natural Syrian zeolite (Z) from (Sis) deposit was mixed with 111 ml of 0.6 N silver nitrate solution. Stage C: 1C- The produced powder of stage A was divided into three parts, each of them was added to each one of the masses 1B, 2B, 3B of stage B respectively. 2C- The paste was formed in cylinder of 5 cm. length and internal diameter of 2 mm. 3C- The received tubes were dried at room temperature in shade for 7 days. 4C- The dried tubes were heated in the Carbolite oven at 550°C for 5 hours.
8
5C- The prepared catalyst was used after cooling in the same oven till the next day (Fig. 3). I – 1 – 9-2: Experimental Results: I – 1 – 9-2-1:N2 adsorption – desorption measurements I – 1 – 9-2-2:Results of the catalytic study: I – 1 – 9-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates. I – 1 – 9-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction I – 1 – 9-2-2-3: Calculation of the kinetic parameters. I – 1 – 9-2-3: IR characteristics diagrams. I – 1 – 9-2: Experimental Results: I – 1 – 9-2-1:N2 adsorption – desorption measurements: surface area of the catalyst was measured by means of Micromeritics Gemini 3 device data of which are listed in table (1). The Table (1) indicates a sharp decrease of surface area in the direction bentonite-zeolite-ZB-Ag2O, Al2O3-Ag2O, whereas the pore diameter average increased in the same direction. Plots for N2 adsorption the ZB-Ag2O, Al2O3-Ag2O catalyst and pore distribution are shown in Figs (4-5). The adsorption desorption isotherm may be classified as type II of De Bore's classification of capillary condensation hysteresis loops [9] . I – 1 – 9-2-2:Results of the catalytic study: I – 1 – 9-2-2-1: Dependence of conversion rate on time at different temperatures and flow rates: Dependence of the de-NO, de-NOx conversion on time and different flow rate at 200°C are shown in the flowing tables and curves. These results and curves show increasing conversion rates at first, to reach a stationary state and consequently a constant conversion rate later (Table 2). -Dependence of the de-NO, de-NOx reaction on temperature at close flow rates for the Syrian sliver catalyst ZB-Ag2O, Al2O3-Ag2O at the flowing space velocities: - Result for the space velocities: 203.1487- 238.5045-211.1097196.3688h-1 (Table 3 and Fig. 6). The Fig. 6 indicates maximum for 9
de-NO and de-NOx at 150°C and 200°C, whereas decrease of the deNO and de-NOx catalytic activity is observed over 200°C till 250°C. - Results for the space velocities: 274.5508 - 298.1306 - 283.0085 272.17h-1 (Table 4 and Fig. 7). The Fig. 7 indicates maximum for de-NO and de-NOx at 150°C and 200°C, whereas decrease of the de-NO and de-NOx catalytic activity is observed over 200°C till 250°C [10-14]. I – 1 – 9-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction: The related kinetic equation used in [5] is: 1/m [Ln (1/(1-X))] = 1/F0 Where: m: is the mass of the catalyst, X: conversion rate for the de-NO, de- NOx reaction, KA: the adsorption equilibrium constant, k: the real rate constant as for the NO and NOx reagents. The results for 150°C are represented in the Table 5 and Fig. 8. The Results in table 5 show good agreement with the equation (10) indicating a pseudo first order reaction as for de-NO, de-NOx conversion in conditions of our experiments. Values of KAk by means of the equation (10):
1- For NO: Slope = KAk 22.4 KAk = Slope / 22.4 KAk = 0.081 / 22.4 = 0.00361 (m mol)/ gr. sec atm
2- For NOx: Slope = KAk 22.4 KAk = Slope / 22.4 KAk = 0.082 / 22.4 = 0.00366 (m mol)/ gr. sec atm Those results are generally in accord with the results obtained by [15] using another method, where a fractional order for de-NO, as observed for a catalyst different from our catalysts. The satisfaction of first order equation, however depends on the nature of used catalyst, the contents of the car exhaust gases, and reaction temperature .
10
I – 1 – 9-2-2-3: Calculation activation energy: The activation energy were calculated by means of equation: Log {1/m [Ln (1/(1-x))]} =
(1/T) Activation energy = slope 2.303 R constant.
where
R
is
universal
gases
The data received was not in accord with equation (10) . I – 1 – 9-2-3:IR characteristics diagrams: The characteristic IR diagrams of the catalyst before and after the catalytic reaction are shown in Figs. 9 and 10, respectively. The distinguished wave numbers are listed in Table (6) the resulting wave numbers may be attributed to Valence vibrations' listed in that table. Heat treatment and chemical structure of the catalyst have the mean impact on the resulting IR diagrams. I – 1 – 10: Preparation and the experiments of the Syrian sliver and molybdenum ZB-Ag2O, Al2O3-MoO3 - Ag2O: I – 1 –10-1 Preparation of the catalyst ZB-Ag2O, Al2O3-MoO3 - Ag2O it was prepared as the following stages: Stage A: Preparation of the alumina supported metal oxide: 1A- 6.66 gr. of ammonium molibdate were dissolved in 88.3 ml of hot distillated water, 46.92gr. of silver nitrate were added and dissolved to the solution (solution I). 2A- Solution (I) was impregnated with 166.78 gr. of alumina to form a paste, more than 50 ml of distillated water were added and mixed with the paste, the paste was put to dry in the shade. 3A- The dried product was heated at 110°C for 4 hours. 4A- The outcomming mass was heated at 550°C in the oven for 5 hours. Stage B: impregnation of Syrian bentonite (B) and Syrian zeolite (Z) with silver nitrate solution: 1B- 400 gr. of Syrian bentonite (B) were impregnated with 400 ml of 0.075 N silver nitrate solution. 2B- 393 gr. of Syrian bentonite (B) were impregnated with 393 ml of 0.075 N silver nitrate solution. 3B- 333 gr. of natural Syrian zeolite (Z) from Sis deposit was mixed with 111 ml of 0.6 N silver nitrate solution. 11
Stage C: 1C- The produced powder of stage A was divided into three parts, each of them was added to each one of the masses 1B, 2B, 3B of stage B respectively. 2C- The paste was formed in cylinder of 5 cm. length and internal diameter of 2 mm. 3C- The received tubes were dried at room temperature in shade for 7 days. 4C- The dried tubes were heated in the Carbolite oven at 550°C for 5 hours. 5C- The prepared catalyst was used after cooling in the very oven till the next day (Fig. 3). I – 1 – 10-2: Experimental Results: I – 1 – 10-2-1:N2 adsorption – desorption measurements I – 1 – 10-2-2:Results of the catalytic study: I – 1 –10-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates. I – 1 – 10-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction I – 1 – 10-2-2-3: Calculation of the kinetic parameters I – 1 – 10-2-3:IR characteristics diagrams. I – 1 – 10-2: Experimental Results: I – 1 – 10-2-1:N2 adsorption – desorption measurements: surface area of the catalyst was measured by means of Micromeritics Gemini 3 device data of which are listed in table (7). The Table (7) indicates a sharp decrease of surface area in the direction bentonite-zeolite-ZBAg2O,Al2O3-MoO3-Ag2O, whereas the pore diameter average increased in the same direction. Plots for N2 adsorption the ZB-Ag2O, Al2O3-MoO3Ag2O catalyst and pore distribution are shown in Figs. (11-12). The adsorption desorption isotherm may be classified as type II of De Bore's classification of capillary condensation hysteresis loops [9]. I – 1 – 10-2-2:Results of the catalytic study: 12
I – 1 – 10-2-2-1: Dependence of conversion rate on time at different temperatures and flow rates: Dependence of the de-NO, de-NOx conversion on time and different flow rate at 150°C are shown in the flowing tables and curves. These results and curves show increasing conversion rates at first, to reach a stationary state and consequently a constant conversion rate later (Table 8). - Dependence of the de-NO, de-NOx, de-CH reaction on temperature at close flow rates for the Syrian sliver catalyst ZB-Ag2O, Al2O3-MoO3Ag2O at the flowing space velocities: -
Result for the space velocities: 249.9523- 217.5772- 222.2170h-1 (Table 9 and Fig. 13). The Fig. 13 indicates maximum for de-NO, de-NOx and de-CH at 185°C, whereas decrease of the de-NO, deNOx and de-CH catalytic activity is observed at 135°C.
-
Result for the space velocities: 268.8831- 287.1702 - 270.2766 h1 (Table 10 and Fig. 14). The Fig. 14 indicates maximum for deNO, de-NOx and de-CH at 185°C, whereas decrease of the de-NO, de-NOx and de-CH catalytic activity is observed at 135°C.
I – 1 – 10-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction: The related kinetic equation used in [5] is: 1/m [Ln (1/(1-X))] = 1/F0 Where: m: is the mass of the catalyst, X: conversion rate for the de-NO, de- NOx reaction, KA: the adsorption equilibrium constant, k: the real rate constant as for the NO and NOx reagents. The result for 150°C (Table 11 and Fig. 15) and 185°C (Table 12 and Fig. 16). Results in Tables 11 and 12 show good agreement with the equation (10) indicating a pseudo first order reaction as for de-NO, de-NOx conversion in conditions of our experiments. Values of KAk by means of the equation (10) are listed in table 13. Those results are generally in accord with the results obtained by [15] where a fractional order for de-NO , as observed for a catalyst different from our catalysts. I– 1– 10-2-2-3: Calculation activation energy: The activation energy were calculated by means of equation: Log {1/m [Ln (1/(1-x))]}= (1/T) Activation energy = slope 2.303 R constant
where
R
is
universal
gases
The activation energy was calculated with data of 135°C – 150°C - 185°C 13
- Group A: The activation energy at flow rates of 7.3288- 7.22476.5156 cm3/sec (Table 14 and Fig. 17). The calculated apparent activation energy for group A is 18.8347 and 19.4129 K Jol/mol for NO and NOx respectively. - Group B: The activation energy at flow rates of 7.8839- 8.42017.9247 cm3/sec (Table 15 and Fig. 18). The calculated apparent activation energy for group B is 21.8060 and 22.8972K Jol/mol for NO and NOx respectively. The received values of activation energy are in accordance with those obtained in [16] I – 1 – 10-2-3:IR characteristics diagrams: The characteristic IR diagrams of the catalyst before and after the catalytic reaction are shown in Figs. 19 and 20 respectively. The distinguished wave numbers are listed in Table (16) the resulting wave numbers may be attributed to Valence vibrations' listed in that table. Heat treatment and chemical structure of the catalyst have the mean impact on the resulting IR diagrams.
I – 1 – 11: Preparation and the experiments of the Jordanian silver catalyst: I – 1 –11-1:The catalyst ZJB-Ag2O, Al2O3-Ag2O: was prepared in the following stages: Stage A: Preparation of the alumina supported metal oxide: 1A- 46.91 gr. of silver nitrate were dissolved in 88.3 ml of hot distillated water (solution I). 2A- Solution I was impregnated with 166.78 gr. of alumina to form a paste, more than 50 ml of distillated water were added and mixed with the paste, the paste was put to dry in the shade. 3A- The dried product was heated at 110°C for 4 hours. 4A- The resulting mass was heated at 550°C in the oven for 5 hours. Stage B: impregnation of Syrian bentonite (B) and Syrian zeolite (Z) with silver nitrate solution:
14
1B- 400 gr. of Syrian bentonite (B) were impregnated with 400 ml of 0.075 N silver nitrate solution. 2B- 400 gr. of Syrian bentonite (B) were impregnated with 400 ml of 0.075 N silver nitrate solution. 3B- 333 gr. of natural Jordanian zeolite (ZJ) was mixed with 111 ml of 0.6 N silver nitrate solution. Stage C: 1C- The produced powder of stage A was divided into three parts, each of them was added to each one of the masses 1B, 2B, 3B of stage B respectively. 2C- The paste was formed in cylinder of 5 cm. length and internal diameter of 2 mm. 3C- The received tubes were dried at room temperature in shade for 7 days. 4C- The dried tubes were heated in the Carbolite oven at 550°C for 5 hours. 5C- The prepared catalyst was used after cooling in the same oven till the next day (Fig. 3). I – 1 – 11-2: Experimental Results: I – 1 – 11-2-1:N2 adsorption – desorption measurements I – 1 – 11-2-2:Results of the catalytic study: I – 1 –11-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates. I – 1 – 11-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction I – 1 – 11-2-2-3: Calculation of the kinetic parameters I – 1 – 11-2-3:IR characteristics diagrams. I – 1 – 11-2: Experimental Results: I – 1 – 11-2-1:N2 adsorption – desorption measurements: surface area of the catalyst was measured by means of Micromeritics Gemini 3 device data of which are listed in table (17). The Table (17) indicates a sharp 15
decrease of surface area in the direction bentonite-zeolite-ZJB-Ag2O, Al2O3-Ag2O, whereas the pore diameter average increased in the same direction. Plots for N2 adsorption the ZJB-Ag2O, Al2O3-Ag2O catalyst and pore distribution are shown in Figs (21-22). The adsorption desorption isotherm may be classified as type II of De Bore's classification of capillary condensation hysteresis loops [9]. I – 1 – 11-2-2:Results of the catalytic study: I – 1 – 11-2-2-1: Dependence of conversion rate on time at different temperatures and flow rates: Dependence of the de-NO, de-NOx conversion on time and different flow rate at 150°C are shown in the flowing tables and curves. These results and curves show increasing conversion rates at first, to reach a stationary state and consequently a constant conversion rate later (Table 18). -Dependence of the de-NO, de-NOx reaction on temperature at close flow rates for the Jordanian sliver catalyst ZJB-Ag2O, Al2O3-Ag2O at the flowing space velocities: - Result for the space velocities: 211.6815- 211.1097 - 243.2448 205.014 h-1 (Table 19 and Fig. 23). The Fig. 23 indicates approximately constant de-NO and de-NOx at (150-200)°C flow by decreasing conversion with increasingly higher temperatures. -
Result for the space velocities: 355.0448- 359.1284 - 351.8485347.1557 h-1 (Table 20 and Fig. 24). The Fig. 24 indicates maximum de-NO and de-NOx at 150°C and 200°C, respectively, accompanied with decreasing de-NO and de-NOx catalytic conversion is 185°C and 250°C, respectively.
I – 1 – 11-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction: The related kinetic equation used in [5] is: 1/m [Ln (1/(1-X))] = 1/F0 Where: m: is the mass of the catalyst, X: conversion rate for the de-NO, de- NOx reaction, KA: the adsorption equilibrium constant, k: the real rate constant as for the NO and NOx reagents. The result for 150°C (Table 21 and Fig. 25) and 185°C (Table 22 and Fig. 26). The results in tables 21 and 22 show good agreement with the equation (10) indicating a pseudo first order reaction as for de-NO, de-NOx conversion in conditions of our experiments. Values of KAk by means of the equation (10) are listed in Table 23. The results in Table 23 are generally in accord with the results 16
obtained by [15] where a fractional order for de-NO , as observed for a catalyst different from our catalysts. I – 1 – 11-2-2-3: Calculation activation energy: The activation energy were calculated by means of equation: Log {1/m [Ln (1/(1-x))]} = (1/T) Activation energy = slope 2.303 R where R is universal gases constant (Table 24). The results listed in Table 24 indicate a decrease in the value of apparent rate calculated for the de-NO, de-NOx reactions with increasing temperature that may be attributed to the NO and NOx adsorption decrease with increasing temperature, leading to conclusion that the rate limiting step in the de-NO,de-NOx catalyst should be the adsorption of NO and NOx. I – 1 – 11-2-3:IR characteristics diagrams: The characteristic IR diagrams of the catalyst before and after the catalytic reaction are shown in Figs. 27 and 28. The distinguished wave numbers are listed in Table (25) the resulting wave numbers may be attributed to Valence vibrations' listed in that table. Heat treatment and chemical structure of the catalyst have the mean impact on the resulting IR diagrams. I – 1 – 12: Preparation and the experiments of the Syrian chromium catalyst: I – 1 –12-1: The catalyst ZB-Cr2O3, Al2O3-Cr2O3: it was prepared as the following stages: Stage A: Preparation of the alumina supported metal oxide: 1A- 110.48 gr. of hydrous Cr3+ nitrate were dissolved in 188.78 ml of hot distillated water (solution I). 2A- Solution I was impregnated with 166.78 gr. of alumina to form a paste, the paste was put to dry in the shade. 3A- The dried product was heated at 110°C for 4 hours. 4A- The outcomming mass was heated at 550°C in the oven for 5 hours. Stage B: impregnation of Syrian bentonite (B) and Syrian zeolite (Z) with hydrous chromium solution: 1B- 400 gr. of Syrian bentonite were impregnated (B) with 400 ml of 0.075 N hydrous chromium nitrate solution. 2B- 400 gr. of Syrian bentonite were impregnated (B) with 400 ml of 0.075 N hydrous chromium nitrate solution. 17
3B- 333 gr. of natural Syrian zeolite (Z) from Sis deposit was mixed with 111 ml of 0.6 N hydrous chromium nitrate solution. Stage C: 1C- The produced powder of stage A was divided into three parts, each of them was added to each one of the masses 1B, 2B, 3B of stage B respectively. 2C- The paste was formed in cylinder of 5 cm. length and internal diameter of 2 mm. 3C- The received tubes were dried at room temperature in shade for 7 days. 4C- The dried tubes were heated in the Carbolite oven at 550°C for 5 hours. 5C- The prepared catalyst was used after cooling in the very oven till the next day (Fig. 3). I – 1 – 12-2: Experimental Results: I – 1 – 12-2-1:N2 adsorption – desorption measurements I – 1 – 12-2-2:Results of the catalytic study: I – 1 – 12-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates. I – 1 – 12-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction I – 1 – 12-2-2-3: Calculation of the kinetic parameters. I – 1 – 12-2-3:IR characteristics diagrams. I – 1 – 12-2: Experimental Results: I – 1 – 12-2-1:N2 adsorption – desorption measurements: surface area of the catalyst was measured by means of Micromeritics Gemini 3 device data of which are listed in Table (26). The Table (26) indicates a decrease as for the catalyst area and slight differences in the direction bentonitezeolite-ZB-Cr2O3,Al2O3-Cr2O3, whereas the pore diameter average increased slightly after the addition Cr2O3. Plots for N2 adsorption the ZB-Cr2O3, Al2O3- Cr2O3 catalyst and pore distribution are shown in Figs (29-30). The adsorption desorption isotherm may be classified as type II of De Bore's classification of capillary condensation hysteresis loops [9]. 18
I – 1 – 12-2-2:Results of the catalytic study: I – 1 – 12-2-2-1: Dependence of conversion rate on time at different temperatures and flow rates: Dependence of the de-CH conversion on time and different flow rate at 310°C are shown in the flowing tables and curves. These results and curves show increasing conversion rates at first, to reach stationary state and consequently a constant conversion rate later Table 27). - Dependence of the de- CH reaction on temperature at close flow rates for the catalyst ZB-Cr2O3, Al2O3- Cr2O3 at the flowing space velocities: -Result for the space velocities: 216.3712- 198.2497-211.1097214.5841 h-1 (Table 28 and Fig. 31). The Fig. 30 indicates maximum deCH at 310°C and 400°C. -Result for the space velocities: 249.9523- 247.1841-248.7588249.9523 h-1 (Table 29 and Fig. 32). The Fig. 32 indicates maximum deCH at 355°C and 400°C [17-19]. I – 1 – 12-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction: As in Habgood and Basset work equation [5] 1/m [Ln (1/(1-X))] = 1/F0 Where: m: is the mass of the catalyst, X: conversion rate for the de-CH, reaction, KA: the adsorption equilibrium constant, k: the real rate constant as for the CH reagent. The result for 310°C (Table 30 and Fig. 33). The results in Table 30 show good agreement with the equation (10) indicating a tendency to a pseudo first order reaction as for de-CH conversion in conditions of our experiments. Values of KAk by means of the equation (10) for CH: Slope = KAk 22.4 KAk = Slope / 22.4 KAk = 0.068 / 22.4 = 0.00303 (m mol)/ gr. sec atm Those results are generally in accord with the results obtained by [15] where a fractional order for de-NO as observed on a different catalyst from ours. I – 1 – 12-2-2-3: Calculation activation energy: The activation energy were calculated by means of equation: Log {1/m [Ln (1/(1-x))]} = (1/T) 19
Activation energy = slope 2.303 R constant
where
R
is
universal
gases
The activation energy was calculated with data of 260°C – 310°C - 355°C - 400°C and flow rates of at tow groups (A & B) - Group A: Flow rates of at 6.3442 - 5.8128 - 6.1899 - 6.2919 cm3/sec (Table 31 and Fig. 34). The calculated apparent activation energy for group A is 9.5514 K Jol/mol. - Group B: Flow rates of at 7.3288 - 7.2476 - 7.2938 - 7.3288 cm3/sec (Table 32 and Fig. 35). The calculated apparent activation energy for group B is 21.6145 K Jol/mol. I – 1 – 12-2-3:IR characteristics diagrams: The characteristic IR diagrams of the catalyst before and after the catalytic reaction are shown in Figs. 36 and 37 respectively. The distinguished wave numbers are listed in Table (33) the resulting wave numbers may be attributed to Valence vibrations' listed in that table. Heat treatment and chemical structure of the catalyst have the mean impact on the resulting IR diagrams. I – 1 – 13: Preparation and the experiments of the Syrian chromium and molybdenum catalyst: I – 1 –13-1: The catalyst ZB-Cr2O3, Al2O3-Cr2O3-MoO3: it was prepared as the following stages: Stage A: Preparation of the alumina supported metal oxide: 1A- 6.66 gr. of ammonium molybdenum were dissolved in 88.3 ml of hot distillated water, 110.48 gr. of hydrous chromium nitrate were added and dissolved to the solution (solution I). 2A- Solution (I) was impregnated with 166.78 gr. of alumina to form a paste, the paste was put to dry in the shade. 3A- The dried product was heated at 110°C for 4 hours. 4A- The outcomming mass was heated at 550°C in the oven for 5 hours. Stage B: impregnation of Syrian bentonite (B) and Syrian zeolite (Z) with silver nitrate solution: 1B- 400 gr. of Syrian bentonite (B) were impregnated with 400 ml of 0.075 N hydrous chromium nitrate solution.
20
2B- 393 gr. of Syrian bentonite (B) were impregnated with 393 ml of 0.075 N hydrous chromium nitrate solution. 3B- 333 gr. of natural Syrian zeolite (Z) from Sis deposit was mixed with 111 ml of 0.6 N hydrous chromium nitrate solution. Stage C: 1C- The produced powder of stage A was divided into three parts, each of them was added to each one of the masses 1B, 2B, 3B of stage B respectively. 2C- The paste was formed in cylinder of 5 cm. length and internal diameter of 2 mm. 3C- The received tubes were dried at room temperature in shade for 7 days. 4C- The dried tubes were heated in the Carbolite oven at 550°C for 5 hours. 5C- The prepared catalyst was used after cooling in the very oven till the next day (Fig. 3). I – 1 – 13-2: Experimental Results: I – 1 – 13-2-1:N2 adsorption – desorption measurements I – 1 – 13-2-2:Results of the catalytic study: I – 1 – 13-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates. I – 1 – 13-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction I – 1 – 13-2-2-3: Calculation of the kinetic parameters. I – 1 – 13-2-3:IR characteristics diagrams. I – 1 – 13-2: Experimental Results: I – 1 – 13-2-1:N2 adsorption – desorption measurements: surface area of the catalyst was measured by means of Micromeritics Gemini 3 device data of which are listed in Table (34). The Table (34) indicates a sharp decrease of surface area in the direction bentonite-zeolite-ZB-Cr2O3, Al2O3-Cr2O3-MoO3, whereas the pore diameter average increased in the same direction. Plots for N2 adsorption the ZB-Cr2O3, Al2O3-Cr2O3-MoO3 21
catalyst and pore distribution are shown in Figs (38-39). The adsorption desorption isotherm may be classified as type II of De Bore's classification of capillary condensation hysteresis loops [9]. I – 1 – 13-2-2:Results of the catalytic study: I – 1 – 13-2-2-1: Dependence of conversion rate on time at different temperatures and flow rates: Dependence of the de-CH conversion on time and different flow rate at 310°C are shown in the flowing tables and curves. These results and curves show increasing conversion rates at first, to reach stationary state and consequently a constant conversion rate later (Table 35). -Dependence of the de- CH reaction on temperature at close flow rates for the catalyst ZB-Cr2O3, Al2O3-Cr2O3-MoO3 at the flowing space velocities: -Result for the space velocities: 209.1289 - 208.2946 - 209.4101204.7453h-1 (Table 36 and Fig. 40). The Fig. 40 indicates maximum deCH at 310°C till 400°C. -Result for the space velocities: 347.1557 - 347.1557 - 352.6421 344.8561 h-1 (Table 37 and Fig. 41). The Fig. 41 indicates maximum deCH at 355°C and 400°C decrease at 260°C [17-19]. I – 1 – 13-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures on the parameters of equation for micro pulse-like flow reaction: As in Habgood and Basset work equation [5] 1/m [Ln (1/(1-X))] = 1/F0 Where: m: is the mass of the catalyst, X: conversion rate for the de-CH, reaction, KA: the adsorption equilibrium constant, k: the real rate constant as for the CH reagent. The result for 310°C (Table 38 and Fig. 42). The results in Table 38 show good agreement with the equation (10) indicating a tendency to a pseudo first order reaction as for de-CH conversion in conditions of our experiments. Values of KAk by means of the equation (10) for CH: Slope = KAk 22.4 KAk = Slope / 22.4 KAk = 0.078 / 22.4 = 0.00348 (m mol)/ gr. sec atm
22
Those results are generally in accord with the results obtained by [15] where a fractional order for de-NO as observed on a different catalyst from ours. I – 1 – 13-2-2-3: Calculation activation energy: The activation energy were calculated by means of equation: Log {1/m [Ln (1/(1-x))]} = (1/T) Activation energy = slope 2.303 R where R is universal gases constant The activation energy was calculated with data of 260°C – 310°C - 355°C - 400°C and flow rates of at two groups (A & B) -Group A: Flow rates of at 6.1318 - 6.1318 - 6.1401 - 6.0033 cm3/sec (Table 39 and Fig. 43). The calculated apparent activation energy for group A is 14. 2840 K Jol/mol. - Group B: Flow rates of at 10.1789 - 10.1789 - 10.3397 - 10.1115 cm3/sec (Table 40 and Fig. 44). The calculated apparent activation energy for group B is 31.9910 K Jol/mol. I – 1 – 13-2-3:IR characteristics diagrams: The characteristic IR diagrams of the catalyst before and after the catalytic reaction are shown in Figs. 45 and 46, respectively. The distinguished wave numbers are listed in Table (41) the resulting wave numbers may be attributed to Valence vibrations' listed in that table. Heat treatment and chemical structure of the catalyst have the mean impact on the resulting IR diagrams. II- A comparative study was conducted between our catalyst ZJBAg2O, Al2O3-Ag2O and a commercial catalyst manufactured for use in gasoline vehicles: The experimental measurement were carried out with our developed rig in almost close conditions. Results of NO, NOx and CH removal catalyzed by our catalysts ZJB-Ag2O, Al2O3-Ag2O and ZB-Cr2O3, Al2O3-Cr2O3-MoO3 are in close agreement with those received when the commercial catalyst was applied in the same rig (Tables 42 and 43).
23
Figures, Tables and Plots:
Fig. 1: scheme of the gas measurement unit
24
Fig. 2: A photo graph of the related developed to Fig. (1) rig.
25
Fig. 3: Fractions of silver catalyst ZB-Ag2O, Al2O3-Ag2O Table (1): Data surface properties for bentonite (B), zeolite (Z), the combined bentonite and zeolite (ZB) and the catalyst ZB-Ag2O, Al2O3-Ag2O ZB-Ag2O, Al2O3Ag2O
Combined ZB
Zeolite
Bentonite
(Z)
(B)
Sample of sliver Syrian catalyst Surface area
27.1070
52.6014
49.3041
51.7946
42.5744
81.9353
76.2058
82.1938
2.8837
9.5036
13.3858
0.4878
Micropore area m2/gr.
24.2233
43.0978
35.9183
51.3067
External surface area m2/gr.
0.0013
0.0047
0.0069
0.000017
Micropore value cm3/gr.
0.0425
0.0631
0.0515
0.0620
Overall micropore area a certain value P/P0 cm3/gr.
62.6644
48.0197
41.7892
47.8927
Average pore diameter A0
(m2/gr. BET) Surface area
26
(m2/gr. Langmure)
Fig. 4: N2 adsorption – desorption isotherms for the catalyst ZB-Ag2O, Al2O3-Ag2O
Fig. 5: Pore volume distribution as a function of diameters in case of adsorption for the catalyst ZB-Ag2O, Al2O3-Ag2O
27
Table (2): Results and curves for conversion rate of the de-NO and de-NOx, reactions at 150°C and different space velocities for ZBAg2O, Al2O3-Ag2O
211.1097 h-1
Space Velocity
°200
Temperature
Removal of NOx %
Removal of NO %
0
0
Sec 0
78.0822
77.1429
60
78.0822
77.1429
120
80.8219
80.0000
180
283.0085 h-1
Space Velocity
°200
Temperature
Syrian sliver catalyst
Removal of NOx %
Removal of NO %
0
0
Sec 0
82.9060
84.0708
60
84.6154
84.0708
120
84.6154
84.0708
180
86.3248
85.8407
240
86.3248
85.8407
300
28
Syrian sliver catalyst Time
Time
367.5768 h-1
Space Velocity
°200
Temperature
Removal of NOx %
Syrian sliver catalyst
Removal of NO %
Time
0 74.5763 77.9661 77.9661
0 73.6842 77.1930 77.1930
0 60 120 180
519.0041 h-1
Space Velocity
°200
Temperature
Syrian sliver catalyst
Removal of NOx %
Removal of NO %
Time
0 69.9531 70.8920 71.8310 72.7700 74.6479 74.6479 75.5869
0 69.6078 70.5882 71.5686 72.5490 74.5098 74.5098 75.4902
0 60 120 180 240 300 360 420
29
Sec
Sec
589.5094 h-1
Space Velocity
°200
Temperature
Removal of NOx %
Syrian sliver catalyst
Removal of NO %
Time
0
0
0
62.3932
62.8319
60
62.3932
62.8319
120
62.3932
62.8319
180
Sec
Table (3): Dependence of de-NO, de-NOx Conversion at different temperatures at close space velocities for ZB-Ag2O, Al2O3-Ag2O
Space Velocity h-1
de-NOx (%)
de-NO (%)
Temperature C°
203.1487
72.9730
72.9730
°150
238.5045
57.8947
57.8947
°175
211.1097
80.8219
80.0000
°200
196.3688
47.8261
48.3146
°250
30
Fig. 6: Curves of de-NO, de-NOx as a function of temperatures for ZB-Ag2O, Al2O3-Ag2O
Table (4): Dependence of de-NO, de-NOx Conversion at different temperatures at close space velocities for ZB-Ag2O, Al2O3-Ag2O
Space Velocity h-1
de-NOx (%)
de-NO (%)
Temperature C°
274.5508
69.2308
68.2540
°150
298.1306
56.3636
54.7170
°175
283.0085
86.3248
85.8407
°200
272.17
37.0787
36.4706
°250
Fig. 7: Curves of de-NO, de-NOx as a function of temperatures for ZB-Ag2O, Al2O3-Ag2O 31
Table (5): Dependence of 1/m [ln (1/(1-X))] on 1/F0 for de-NO, deNOx at 150°C for ZB-Ag2O, Al2O3-Ag2O
NOx
NO
1/m [Ln (1/(1-X))]
1/m [Ln (1/(1-X))]
0.0121
0.0121
0.1679
0.0115
0.0111
0.1242
0.0095
0.0093
0.1013
0.0061
0.0060
0.0738
0.0046
0.0045
0.0567
0.0026
0.0027
0.0295
1/F0
Fig. 8: 1/m [ln (1/(1-X))] as a function of 1/F0 for de-NO, de-NOx catalytic reaction for ZB-Ag2O, Al2O3-Ag2O
32
Fig. 9: IR Characteristic diagram of the catalyst before catalytic reaction
Fig. 10: IR characteristic diagram of the catalyst after catalytic reaction
33
Table (6): The observed Valence vibrations' wave numbers characteristic for ZB-Ag2O, Al2O3-Ag2O before and after the catalytic reaction Bonds
AL-OH
O-Me…OAds
OH Hydrogen bonds with metal oxide
Valence vibrations' Wave Number
cm-1
cm-1
cm-1
1051.01
1456.96
3445.21
Valence vibrations' Wave Number Before Catalytic Reaction
1045.23
1426.10
3450.03
Valence vibrations' Wave Number After Catalytic Reaction
Si-OH
Catalyst
Table (7): Data surface properties for bentonite (B), zeolite (Z), the combined bentonite and zeolite (ZB) and the catalyst ZB-Ag2O, Al2O3-MoO3 - Ag2O ZB-Ag2O, Al2O3MoO3Ag2O
Combined ZB
Zeolite
Bentonite
(Z)
(B)
34.4682
52.6014
49.3041
51.7946
Sample of Molybdenum and Silver Syrian catalyst
Surface area (m2/gr. BET) Surface area 54.4739
81.9353
76.2058
82.1938
1.3130
9.5036
13.3858
0.4878
Micropore area m2/gr.
33.1553
43.0978
35.9183
51.3067
External surface area m2/gr.
0.00046
0.0047
0.0069
0.000017
Micropore value cm3/gr.
0.0489
0.0631
0.0515
0.0620
Overall micropore area a certain value P/P0 cm3/gr.
56.7551
48.0197
41.7892
47.8927
Average pore diameter A0
34
(m2/gr. Langmure)
Fig. 11: N2 adsorption – desorption isotherms for the catalyst ZB-Ag2O, Al2O3-MoO3- Ag2O
Fig. 12: Pore volume distribution as a function of diameters in case of adsorption for the catalyst ZB-Ag2O, Al2O3-MoO3- Ag2O
35
Table (8): Results and curves for conversion rate of the de-NO, deNOx and de-CH reactions at 150°C and different space velocities for ZB-Ag2O, Al2O3-MoO3- Ag2O 246.4030 h-1
Space Velocity
°150
Temperature
Syrian Molybdenum and Silver catalyst
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0.0000 62.1622 64.8649 67.5676 67.5676 67.5676
0.0000 61.1111 63.8889 66.6667 66.6667 66.6667
217.5772h-1
Space Velocity
°150
Temperature
Syrian Molybdenum and Silver catalyst
Removal of NO %
Removal of CH %
Time
Sec
Removal of NOx %
0.0000 31.8841 33.3333 34.0580 32.6087 32.6087
0.0000 40 71 132 188 248
0.0000 69.2308 73.0769 73.0769 75.0000 75.0000
0.0000 68.0000 72.0000 72.0000 74.0000 74.0000
0.0000 47.0968 52.2581 56.1290 53.5484 56.1290
0.0000 60 120 180 240 300
328.8841 h-1
Space Velocity
287.1702 h-1
Space Velocity
°150
Temperature
Syrian Molybdenum and Silver catalyst
°150
Temperature
Syrian Molybdenum and Silver catalyst
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0 37.8378 48.6486 51.3514 51.3514
0 38.8889 47.2222 50.0000 50.0000
0.0000 18.6567 22.3881 23.8806 26.1194
0 60 120 180 240
Sec
Sec
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0.0000 48.0000 61.3333 66.6667 66.6667 68.0000 69.3333
0.0000 47.2222 61.1111 66.6667 66.6667 68.0556 69.4444
0.0000 25.0000 35.5263 37.5000 37.5000 38.8158 38.8158
0.0000 60 120 180 240 300 360
36
Sec
929.8820h-1
Space Velocity
°150
Temperature
Syrian Molybdenum and Silver catalyst
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0.0000 22.7273 22.7273 20.4545
0.0000 21.4286 21.4286 19.0476
0.0000 2.3256 -
0.0000 60 120 180
Sec
491.2594 h-1
Space Velocity
°150
Temperature
Syrian Molybdenum and Silver catalyst
Removal of NOx %
Removal of NO %
Removal of CH %
Time
0.0000 34.2105 34.2105 31.5789 31.5789
0.0000 35.1351 35.1351 32.4324 32.4324
0.0000 18.5714 14.2857 14.2857 8.5714
0.0000 71 131 191 251
37
Sec
Table 9: Dependence of de-NO, de-NOx, de-CH Conversion at different temperatures at close space velocities for ZB-Ag2O, Al2O3-MoO3- Ag2O Space Velocity h-1
de-NOx (%)
de-NO (%)
249.9523
61.111
61.111
48.5714
°135
217.5772
75.0000
74.0000
56.1290
°150
222.2170
82.6920
82.0000
78.8890
°185
de-CH (%)
Temperature C°
Fig. 13: Curves of de-NO, de-NOx, de-CH as a function of temperatures for ZB-Ag2O, Al2O3-MoO3 - Ag2O Table 10: Dependence of de-NO, de-NOx, de-CH Conversion at different temperatures at close space velocities for ZB-Ag2O, Al2O3-MoO3- Ag2O Space Velocity h-1
de-NOx (%)
de-NO (%)
de-CH (%)
Temperature C°
268.8831
50.0000
50.0000
7.6923
°135
287.1702
69.3333
69.4444
38.8158
°150
270.2766
78.5714
77.5000
45.0549
°185
38
Fig. 14: Curves of de-NO, de-NOx, de-CH as a function of temperatures for ZB-Ag2O, Al2O3-MoO3- Ag2O Table 11: Dependence of 1/m [ln (1/(1-X))] on 1/F0 for de-NO, deNOx at 150°C for ZB-Ag2O, Al2O3-MoO3- Ag2O
NOx
NO
1/m [Ln (1/(1-X))]
1/m [Ln (1/(1-X))]
0.0138
0.0134
0.1568
0.0112
0.0120
0.1384
0.0118
0.0118
0.1188
0.0072
0.0069
0.1037
0.0038
0.0039
0.0694
0.0023
0.0021
0.0367
1/F0
Fig. 15: 1/m [ln (1/(1-X))] as a function of 1/F0 for de-NO, de-NOx catalytic reaction at 150°C for ZB-Ag2O, Al2O3-MoO3 - Ag2O 39
Table 12: Dependence of 1/m [ln (1/(1-X))] on 1/F0 for de-NO, deNOx at 185°C for ZB-Ag2O, Al2O3-MoO3- Ag2O NOx
NO
1/m [Ln (1/(1-X))]
1/m [Ln (1/(1-X))]
0.0175 0.0154 0.0107 0.0107 0.0044 0.0016
0.0171 0.0149 0.0103 0.0103 0.0043 0.0017
1/F0
0.1535 0.1262 0.1044 0.0845 0.0443 0.0186
Fig. 16: 1/m [ln (1/(1-X))] as a function of 1/F0 for de-NO, de-NOx catalytic reaction at 185°C for ZB-Ag2O, Al2O3-MoO3- Ag2O
Table 13: Values of KAk by means of the equation (10) de-NO
de-NOx Temperatures
KAk
KAk
m mol/ gr. sec atm
m mol/ gr. sec atm
0.00361
0.0037
150°
0.00495
0.00513
185°
40
C
Table 14: The kinetic parameters for group A for the activation energy for ZB-Ag2O, Al2O3-MoO3- Ag2O
NOx
NO
K-1
F0 Flow Rate cm3/sec
-2.0259
-2.0259
0.0025
7.3288
-1.9496
-1.9603
0.0024
7.2247
-1.7571
-1.7669
0.0022
6.5156
Log {1/m [Ln (1/(1-X))]}
1/T
Fig. 17: Diagrams for Log {1/m [Ln (1/(1-X))]} = (1/T) for group A for ZB-Ag2O, Al2O3-MoO3- Ag2O
Table 15: The kinetic parameters for group B for the activation energy for ZB-Ag2O, Al2O3-MoO3- Ag2O F0
Log {1/m [Ln (1/(1-X))]}
1/T -1
K
Flow Rate cm3/sec
NOx
NO
-2.1603
-2.1603
0.0025
7.8839
-1.9285
-1.9272
0.0024
8.4201
-1.8135
-1.8275
0.0022
7.9247
41
Fig. 18: Diagrams for Log {1/m [Ln (1/(1-X))]} = (1/T) for group B for ZB-Ag2O, Al2O3-MoO3- Ag2O
Fig. 19: IR characteristic diagram of the catalyst before catalytic reaction
42
Fig. 20: IR characteristic diagram of the catalyst after catalytic reaction Table 16: The observed Valence vibrations' wave numbers characteristic for ZB-Ag2O, Al2O3-MoO3- Ag2O before and after the catalytic reaction Bonds
AL-OH
O-Me…OAds
OH Hydrogen bonds with metal oxide
cm-1
cm-1
cm-1
Si-OH
Catalyst
3451.96
Valence vibrations' Wave Number Before Catalytic Reaction
3373.85
Valence vibrations' Wave Number After Catalytic Reaction
1424.17 1043.30
Valence vibrations' Wave Number
1639.20 1468.53 1033.66 1508.06
43
Table 17: Data surface properties for bentonite (B), zeolite (ZJ), the combined bentonite and zeolite (ZJB) and the catalyst ZJB-Ag2O, Al2O3Ag2O
ZJB-Ag2O, Combined Al2O3ZJB Ag2O
Zeolite
Bentonite
Sample of Silver
(ZJ)
(B)
Jordanian catalyst Surface area
23.2847
59.5029
51.4587
51.7946
36.5823
92.7012
78.6582
82.1938
2.7801
10.5466
20.0431
0.4878
Micropore area m2/gr.
20.5046
48.9563
31.4156
51.3067
External surface area m2/gr.
0.001265
0.005249
0.010510
0.000017
Micropore value cm3/gr.
0.036630
0.067492
0.045336
0.0620
Overall micropore area a certain value P/P0 cm3/gr.
62.9256
45.3706
35.2406
47.8927
Average pore diameter A0
(m2/gr. BET) Surface area (m2/gr. Langmure)
Fig. 21: N2 adsorption – desorption isotherms for the catalyst ZJB-Ag2O, Al2O3Ag2O
44
Fig. 22: Pore volume distribution as a function of diameters in case of adsorption for the catalyst ZJB-Ag2O, Al2O3-Ag2O
Table 18: Results and curves for conversion rate of the de-NO and de-NOx, reactions at 150°C and different space velocities for ZJBAg2O, Al2O3-Ag2O
211.6815 h-1
Space Velocity
°150
Temperature
Removal of NOx %
Removal of NO %
0
0
Sec 0
90.9091
90.4762
60
90.9091
90.4762
120
90.9091
90.4762
180
45
Jordanian sliver catalyst Time
241.4539 h-1
Space Velocity
°150
Temperature
Removal of NOx %
Removal of NO %
0
0
Sec 0
87.7551
87.2340
60
87.7551
87.2340
120
87.7551
87.2340
180
282.4961 h-1
Space Velocity
°150
Temperature
Jordanian sliver catalyst
Removal of NOx %
Removal of NO %
0
0
Sec 0
85.7143
85.1852
60
85.7143
85.1852
120
85.7143
85.1852
180
46
Jordanian sliver catalyst Time
Time
355.0448 h-1
Space Velocity
°150
Temperature
Removal of NOx %
Removal of NO %
0
0
Sec 0
82.3529
81.8182
60
82.3529
81.8182
120
82.3529
81.8182
180
437.5915 h-1
Space Velocity
°150
Temperature
Jordanian sliver catalyst
Removal of NOx %
Removal of NO %
0
0
Sec 0
80.6452
79.7753
60
78.4946
77.5281
120
76.3441
75.2809
180
76.3441
75.2809
240
Jordanian sliver catalyst Time
Time
Table 19: Dependence of de-NO, de-NOx Conversion at different temperatures at close space velocities for ZJB-Ag2O, Al2O3-Ag2O Space Velocity h-1
de-NOx (%)
de-NO (%)
Temperature C°
211.6815
90.9091
90.4762
°150
211.1097
84.9057
84.3137
°185
243.2448
84.6154
84.6154
°200
205.014
46.1538
46.1538
°250
47
Fig. 23: Curves of de-NO, de-NOx as a function of temperatures for ZJB-Ag2O, Al2O3-Ag2O Table 20: Dependence of de-NO, de-NOx Conversion at different temperatures at close space velocities for ZJB-Ag2O, Al2O3-Ag2O Space Velocity h-1
de-NOx (%)
de-NO (%)
Temperature C°
355.0448
82.3529
81.8182
°150
359.1284
64.1509
62.7451
°185
351.8485
68.8889
67.4419
°200
347.1557
48.2759
46.4286
°250
Fig. 24: Curves of de-NO, de-NOx as a function of temperatures for ZJB-Ag2O, Al2O3-Ag2O
48
Table 21: Dependence of 1/m [ln (1/(1-X))] on 1/F0 for de-NO, deNOx at 150°C for ZJB-Ag2O, Al2O3-Ag2O NOx
NO
1/m [Ln (1/(1-X))]
1/m [Ln (1/(1-X))]
0.0238
0.0233
0.1611
0.0208
0.0204
0.1413
0.0193
0.0189
0.1207
0.0172
0.0169
0.0961
0.0150
0.0146
0.0779
1/F0
Fig. 25: 1/m [ln (1/(1-X))] as a function of 1/F0 for de-NO, de-NOx catalytic reaction at 150°C for ZJB-Ag2O, Al2O3-Ag2O Table 22: Dependence of 1/m [ln (1/(1-X))] on 1/F0 for de-NO, deNOx at 185°C for ZJB-Ag2O, Al2O3-Ag2O NOx
NO
1/m [Ln (1/(1-X))]
1/m [Ln (1/(1-X))]
0.0187
0.0184
0.1616
0.0157
0.0154
0.1375
0.0133
0.0130
0.1175
0.0105
0.0101
0.0950
0.0090
0.0089
0.0742
49
1/F0
Fig. 26: 1/m [ln (1/(1-X))] as a function of 1/F0 for de-NO, de-NOx catalytic reaction at 185°C for ZJB-Ag2O, Al2O3-Ag2O Table 23: Values of KAk by means of the equation (10) de-NO
de-NOx Temperatures
KAk
KAk
m mol/ gr. sec atm
m mol/ gr. sec atm
0.006875
0.00701
150°
0.005
0.00509
185°
C
Table 24: Dependence of KAk on Temperature (T) for NO, NOx de-NOx
de-NO Temperature
KAk
KA k
m mol/ gr. sec atm
m mol/ gr. sec atm
0.00701
0.006875
423
0.00509
0.005
458
0.0054
0.00537
473
0.00209
0.00205
523
50
T
Fig. 27: IR Characteristic diagram of the catalyst before catalytic reaction
Fig. 28: IR Characteristic diagram of the catalyst after catalytic reaction
51
Table 25: The observed Valence vibrations' wave numbers characteristic for ZJB-Ag2O, Al2O3-Ag2O before and after the catalytic reaction Bonds
AL-OH
O-Me…OAds
OH Hydrogen bonds with metal oxide
Valence vibrations' Wave Number
cm-1
cm-1
cm-1
1063.55
1458.89
3447.13
Valence vibrations' Wave Before Catalytic Reaction
1049.09
1422.24
3446.17
Valence vibrations' Wave Number After Catalytic Reaction
Si-OH
Catalyst Number
Table 26: Data surface properties for bentonite (B), zeolite (Z), the combined bentonite and zeolite (ZB) and the catalyst ZB-Cr2O3, Al2O3- Cr2O3 ZB-Cr2O3, Combined Al2O3ZB Cr2O3
Zeolite
Bentonite
(Z)
(B)
Sample of chromium Syrian catalyst Surface area
43.8431
52.7564
50.3678
51.7946
69.1211
82.1931
77.6223
82.1938
3.1516
9.3874
14.2969
0.4878
Micropore area m2/gr.
40.6915
43.3690
36.0710
51.3067
External surface area m2/gr.
0.001308
0.004654
0.007487
0.000017
Micropore value cm3/gr.
0.062081
0.063976
0.047057
0.0620
Overall micropore area a certain value P/P0 cm3/gr.
56.6395
48.5065
37.3709
47.8927
Average pore diameter A0
(m2/gr. BET) Surface area
52
(m2/gr. Langmure)
Fig. 29: N2 adsorption – desorption isotherms for the catalyst ZB-Cr2O3, Al2O3- Cr2O3
Fig. 30: Pore volume distribution as a function of diameters in case of adsorption for the catalyst ZB-Cr2O3, Al2O3- Cr2O3
53
Table 27: Results and curves for conversion rate of the de-NO and de-NOx, reactions at 310°C and different space velocities for ZBAg2O, Al2O3-Ag2O Space Velocity 198.2497 h-1
Syrian chromium catalyst
Temperature 310°
Space Velocity 186.8550 h-1
Syrian chromium catalyst
Temperature 310°
Removal of CH
Time
Removal of CH
Time
% 0
Sec 0
% 0
Sec 0
76.7123
60
76.6667
60
78.0822
120
75.0000
120
79.4521
180
70.0000
180
Space Velocity 308.7349 h-1
Syrian chromium catalyst
Temperature 310°
Space Velocity 247.1841 h-1
Syrian chromium catalyst
Temperature 310°
Removal of CH
Time
Removal of CH
Time
% 0
Sec 0
% 0
Sec 0
33.3333
60
37.3333
60
40.6250
120
65.3333
120
43.7500
180
69.3333
180
54
Space Velocity 347.1557 h-1
Syrian chromium catalyst
Temperature 310° Removal of CH
Time
% 0
Sec 0
19.5767
60
32.2751
120
37.5661
180
34.3915
240
Table 28: Dependence of de-CH Conversion at different temperatures at close space velocities for ZB-Cr2O3, Al2O3- Cr2O3 Space Velocity h-1
de-CH (%)
Temperature C°
216.3712
63.2911
°260
198.2497
79.4521
°310
211.1097
76.4706
°355
214.5841
79.5455
°400
55
Fig. 31: Curves of de-CH as a function of temperatures for ZB-Cr2O3, Al2O3- Cr2O3 Table 29: Dependence of de-CH Conversion at different temperatures at close space velocities for ZB-Cr2O3, Al2O3- Cr2O3 Space Velocity h-1
de-CH (%)
Temperature C°
249.9523
52.9412
°260
247.1841
69.3333
°310
248.7588
85.1351
°355
249.9523
84.9057
°400
Fig. 32: Curves of de-CH as a function of temperatures for ZB-Cr2O3, Al2O3- Cr2O3
56
Table 30: Dependence of 1/m [ln (1/(1-X))] on 1/F0 for de-CH at 310°C for ZB-Cr2O3, Al2O3- Cr2O3 CH 1/F0
1/m [Ln (1/(1-X))] 0.0133
0.1825
0.0151
0.1720
0.0085
0.1380
0.0049
0.1105
0.0037
0.0982
Fig. 33: 1/m [ln (1/(1-X))] as a function of 1/F0 for de-CH catalytic reaction at 310° for ZB-Cr2O3, Al2O3- Cr2O3
Table 31: The kinetic parameters for the activation energy for Group A for ZB-Cr2O3, Al2O3- Cr2O3 F0
Log {1/m [Ln (1/(1-X))]}
1/T -1
K
CH
Flow Rate cm3/sec
-2.0024
0.0019
6.3442
-1.8221
0.0017
5.8128
-1.8261
0.0016
6.1899
-1.8028
0.0015
6.2919
57
Fig. 34: Diagrams for Log {1/m [Ln (1/(1-X))]} = (1/T) for group A for ZB-Cr2O3, Al2O3- Cr2O3 Table 32: The kinetic parameters for the activation energy for Group B for ZB-Cr2O3, Al2O3- Cr2O3 Log {1/m [Ln (1/(1-X))]}
1/T
CH
K-1
-2.1570 -2.0731 -1.7501 -1.7546
0.0019 0.0017 0.0016 0.0015
F0 Flow Rate cm3/sec
7.3288 7.2476 7.2938 7.3288
Fig. 35: Diagrams for Log {1/m [Ln (1/(1-X))]} = (1/T) for group B for ZB-Cr2O3, Al2O3- Cr2O3
58
Fig. 36: IR characteristic diagram of the catalyst before catalytic reaction
Fig. 37: IR characteristic diagram of the catalyst after catalytic reaction
59
Table 33: The observed Valence vibrations' wave numbers characteristic for ZB-Cr2O3, Al2O3- Cr2O3 before and after the catalytic reaction Bonds O-Me…OAds cm-1
OH AL-OH Valence vibrations' Wave Number Hydrogen Si-OH bonds with metal oxide cm-1 Catalyst -1 cm
1049.09
1422.24
1049.09
1457.92
3448.10 Valence vibrations' Wave Number Before Catalytic Reaction 2365.26 3448.10 2517.61
Valence vibrations' Wave Number After Catalytic Reaction
Table 34: Data surface properties for bentonite (B), zeolite (Z), the combined bentonite and zeolite (ZB) and the catalyst ZB-Cr2O3, Al2O3-Cr2O3-MoO3 ZB-Cr2O3, Al2O3Combined Cr2O3ZB MoO3
33.6362
52.7564
Zeolite
Bentonite
(Z)
(B)
50.3678
51.7946
Sample of chromium and molidium Syrian catalyst
Surface area (m2/gr. BET)
52.9426
82.1931
77.6223
82.1938
Surface area (m2/gr. Langmure)
3.1309
9.3874
14.2969
0.4878
Micropore area m2/gr.
30.5053
43.3690
36.0710
51.3067
External surface area m2/gr.
0.001368
0.004654 0.007487 0.000017
Micropore value cm3/gr.
0.047712
0.063976 0.047057
0.0620
Overall micropore area a certain value P/P0 cm3/gr.
56.7393
48.5065
47.8927
Average pore diameter A0
37.3709
60
Fig. 38: N2 adsorption – desorption isotherms for the catalyst ZB-Cr2O3, Al2O3-Cr2O3-MoO3
Fig. 39: Pore volume distribution as a function of diameters in case of adsorption for the catalyst ZB-Cr2O3, Al2O3-Cr2O3-MoO3
61
Table 35: Results and curves for conversion rate of the de-NO and de-NOx, reactions at 310°C and different space velocities for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Space Velocity 208.294 h-1
Space Velocity 188.4453 h-1
Temperature 310°
Syrian chromium & molbidium catalyst
Temperature 310°
Syrian chromium & molbidium catalyst
Removal of CH
Time
Removal of CH
Time
% 0
Sec 0
% 0
Sec 0
79.7872
60
80.1105
60
81.9149
120
82.3204
120
79.7872
180
80.1105
180
Space Velocity 278.9655 h-1
Space Velocity 233.8616 h-1
Temperature 310°
Syrian chromium & molbidium catalyst
Temperature 310°
Syrian chromium & molbidium catalyst
Removal of CH
Time
Removal of CH
Time
% 0
Sec 0
% 0
Sec 0
43.2990
60
57.0681
60
47.4227
120
60.2094
120
47.4227
180
66.4921
180
62
Space Velocity 347.1557 h-1 Temperature 310°
Syrian chromium & molbidium catalyst
Removal of CH
Time
% 0
Sec 0
41.2371
60
39.1753
120
41.2371
180
43.2990
240
Table 36: Dependence of de-CH Conversion at different temperatures at close space velocities for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Space Velocity h-1
de-CH (%)
Temperature C°
209.1289
58.8235
°260
208.2946
79.7872
°310
209.4101
81.4433
°355
204.7453
79.6296
°400
63
Fig. 40: Curves of de-CH as a function of temperatures for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Table 37: Dependence of de-CH Conversion at different temperatures at close space velocities for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Space Velocity h-1
de-CH (%)
Temperature C°
347.1557
25.9740
°260
347.1557
43.2990
°310
352.6421
73.2143
°355
344.8561
74.6032
°400
Fig. 41: Curves of de-CH as a function of temperatures for ZB-Cr2O3, Al2O3-Cr2O3-MoO3
64
Table 38: Dependence of 1/m [ln (1/(1-X))] on 1/F0 for de-CH at 310°C for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 CH 1/F0
1/m [Ln (1/(1-X))] 0.0164
0.1810
0.0162
0.1637
0.0094
0.1458
0.0061
0.1223
0.0053
0.0982
Fig. 42: 1/m [ln (1/(1-X))] as a function of 1/F0 for de-CH catalytic reaction at 310° for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Table 39: The kinetic parameters for the activation energy for Group A for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Log {1/m [Ln (1/(1-X))]}
1/T
CH
K-1
-2.0560 -1.7907 -1.7681 -1.7685
0.0019 0.0017 0.0016 0.0015
F0 Flow Rate cm3/sec
65
6.1318 6.1318 6.1401 6.0033
Fig. 43: Diagrams for Log {1/m [Ln (1/(1-X))]} = (1/T) for group A for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Table 40: The kinetic parameters for the activation energy for Group B for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 Log {1/m [Ln (1/(1-X))]}
1/T
CH
K-1
-2.4772 -2.2785 -1.8844 -1.8672
0.0019 0.0017 0.0016 0.0015
F0 Flow Rate cm3/sec
10.1789 10.1789 10.3397 10.1115
Fig. 44: Diagrams for Log {1/m [Ln (1/(1-X))]} = (1/T) for group B for ZB-Cr2O3, Al2O3-Cr2O3-MoO3
66
Fig. 45: IR characteristic diagram of the catalyst before catalytic reaction
Fig. 46: IR characteristic diagram of the catalyst after catalytic reaction
67
Table 41: The observed Valence vibrations' wave numbers characteristic for ZB-Cr2O3, Al2O3-Cr2O3-MoO3 before and after the catalytic reaction Bonds O-Me…OAds cm-1
1060.66
OH Hydrogen bonds with metal oxide cm-1
AL-OH
1513.85
2371.05
Valence vibrations' Wave Number Before Catalytic Reaction
3450.99
Valence vibrations' Wave Number After Catalytic Reaction
Si-OH cm-1
1634.38 1052.94
Valence vibrations' Wave Number
1472.38
Catalyst
2344.05 1426.10
Table 42: de-No, de-NOx rates of commercial catalyst compared with those of our catalyst Commercial Catalyst (1)
ZJB-Ag2O, Al2O3-Ag2O
Space Temperature Velocity C cm3/sec
de-NOx
de-NO
de-NOx
de-NO
%
%
%
%
-
-
% 76.3441
% 75.2809
437.5915
150
% 80
% 80
-
-
421.0787
175
68
Table 43: de-CH rates of commercial catalyst compared with those of our catalyst Commercial Catalyst (2) de-CH %
ZB-Cr2O3,Al2O3-Cr2O3-MoO3 de-CH
Space Temperature Velocity C cm3/sec
%
Space Temperature Velocity C cm3/sec
347.1557
°250
% 25.9740 347.1557
°260
301.002
°350
% 73.7705 287.1702
355
%46.9320 339.6102
400
%74.6032 344.8561
400
%43.8914
69
Industrial Chart:
70
What is claimed to: 1- Development of anew catalytic micro pulse –like flow pilot plant for use as a device for measuring the interaction between the car exhaust pollutants such as NO, NOx and CH and the catalyst to be used for the first time in the field of car exhaust between catalysis.[ section I – 1 – 3 and fig (1) (2) in the manuscript ]. 2- Modification of the theoretical basis for determination of the catalytic activity and parameters by means of the above rig in a way that fits the subject of the suggested patent. .[ section I – 1 – 4 in the manuscript]. 3- Preparation of matrixes of Syrian and Jordanian zeolites and Syrian bentonite for use as supports of metal oxides catalyzing the deNOx, de-NO and de-CH processes. 4- Synthesis of novel catalysis and described in the items (Industrial Chart p. 70): A- The catalyst ZB-Ag2O, Al2O3-Ag2O item (I – 1 –9-1) and related pp. 8-11. B- The catalyst ZB-Ag2O, Al2O3-MoO3 - Ag2O item (I – 1 –10-1) and related pp. 11-14. C- The catalyst ZJB-Ag2O, Al2O3-Ag2O item (I – 1 –11-1) and related pp. 14-17. D- The catalyst ZB-Cr2O3, Al2O3-Cr2O3 item (I – 1 –12-1) and related pp. 17-20. E- The catalyst ZB-Cr2O3, Al2O3-Cr2O3-MoO3 item (I – 1 –13-1) and related pp. 20-23.
71
ABSTRACT Researches on car exhaust gas pollutants require accurate informations particularly those of kinetics of catalytic reactions concerning de-NO, de-NOx and de-CH, that take place in the catalytic converters connected directly with the engine of the motor car. Unstable velocity of out coming flow gas from car exhaust is the main impediment to be overcome in order to determine the desired kinetic parameters. Therefore, we have constructed a laboratory pilot plant ,data obtained by means of which have been proved to be in accord with the kinetic equation for the pulse flow catalytic reactions. This pilot plant has been repeatedly used to determine the kinetic parameters and catalytic activity for new catalysts prepared by us from metal oxides supported by matrix of Syrian natural zeolite and bentonite.
Key Words: Matrixes of Syrian and Jordanian zeolites and Syrian bentonite for catalytic removal of NO – NOx and CH emitted with car exhaust gases. Flow micro pulse- like device for testing and measuring catalytic activity and kinetics for removal of NO – NOx and CH emitted with exhaust gases.
72
References: [1] Coq, B., Mauvezin, M., Delahay, G., Butet and J. B., Kieger, S., 2000, The simultaneous catalytic reduction of NO and N2O by NH3 using an Fe-zeolite-beta catalyst. Appl. Catal., B Vol. 27 pp. 193-198. [2] Burch, R., Breen, J. P., and Meunier, F. C., 2002, A review of the selective reduction of NOx with hydrocarbons under lean-burn conditions with non-zeolitic oxide and Platinum group metal catalysts. Appl. Catal. B, Vol. 39 pp. 283-303. [3] Subbiah, A., Cho, B. K., Blint, R. J., Gujar, A., Price, G. L. and Yie, J. E., 2003, NOx reduction over metal-ion exchanged novel zeolite under lean conditions: activity and hydrothermal stability. Appl. Catal. B, Vol. 42 pp. 155-178 [4] Pieterse, J. A. Z., Brink, R. W., Booneveld, S. and Bruijn, F. A., 2003, Influence of Zeolite structure on the activity and durability of Co-PdZeolite catalyst in the reduction of NOx with methane. Appl. Catal. B, Vol. 46 pp. 239-250. [5] Bassed, D. W. and Habgood, H. W., 1959, A gas chromatographic study of the catalytic isomerization of cyclopropane. Jour. Phys. Chem., Vol. 64 pp. 769-773. [6] K. V. Topchieva, B. V. Romanovskii, L. I. Thoang, Y. W. Bizreh, Procc. 4th Inter. Cong. Catal. 2 (1971) 135. [7] Bizreh, Y. W. and Gates, B. C., 1984, Butane cracking catalyzed by the zeolite H-ZSM-5. Jour. Catal., Vol. 88 pp. 240-243. [8] Ya. Girasimov and others, Phys. Chem. 1 (1974) 534. [9] H. A. De Boer, Proc. X Symp. Colston Research Sco. Unvi. Bristol, (Eds. Everttd, N., Stone, F. S. and Butterw Orths), Sci. Bull. London (1958) 68-94. [10] Kooten, W. E. J., Krijsen, H. C., Bleek, C. M. and Calis, H. P. A., 2000, Deactivation of zeolite catalysts used for NOx removal. Appl. Catal. B, Vol. 25 pp. 125-135. [11] Ohtsuka, H. and Tabata, T., 2001, Roles of palladium and platinum in the selective catalytic reduction of nitrogen oxides by methane on palladium-platinum-loaded sulfated zirconia. Appl. Catal. B, Vol. 29 pp. 177-183.
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[12] Shi, C., Cheng, M., Qu, Z., Yang, X. and Bao, X., 2002, On the selectively catalytic reduction of NOx with methane over Ag-ZSM-5 catalysts. Appl. Catal. B, Vol. 36 pp. 173-182. [13] Zhu, Z., Liu, Z., Liu, S., Niu, H., Hu, T., Liu, T. and Xie, Y., 2000, NO reduction with NH3 over an activated carbon-supported cooper oxide catalysts at low temperatures. Appl. Catal. B, Vol. 26 pp. 25-35. [14] Moreno-Tost, R., Castellon, E. R. and Jimenez-Lopez, A., 2006, Cobalt-iridium impregnated zirconium-doped mesoporous silica as catalysts for the selective catalytic reduction of NO with ammonia. Jour. Molec. Catal. A Chem., Vol. 248 pp. 126-134. [15] Serra, R., Vecchietti, M. J., Miro, E. and Boix, A., 2008, In, Fezeolites: Active and stable catalysts for SCR of NOx-Kinetics, characterization and deactivation studies. Catal. Today Vol. 133-135 pp. 480-486. [16] Richter, M., Bentrup, U., Eckelt, R., Schneider, M., Pohl, M. M. and Fricke, R., 2004, The effect of hydrogen on the selective catalytic reduction of NO in excess Oxygen over Ag/Al2O3. Appl. Catal. B, Vol. 51 pp. 261-274. [17] Mccabe, R. W. and Mitchell, P. J., 1986, Exhaust catalyst development for methanol-fueled vehicles: 1. A comparative study of methanol oxidation over alumina-supported catalysts containing group 9, 10, and 11 metals. Appl. Catal. B, Vol. 27 NO. 1 pp. 83-98. [18] Xanthopoulou, G. and Vekinis, G., 1998, Investigation of catalytic oxidation of carbon monoxide over a Cu–Cr-oxide catalyst made by selfpropagating high-temperature synthesis. Appl. Catal. B, Vol. 19 NO.1 pp. 37-44. [19] Mescia, D., Cauda, E., Russo, N., Fino , D., Saracco, G. and Specchia,V., 2006, Towards practical application of lanthanum chromite catalysts for diesel particulate combustion. Catal. Today, Vol. 117 NO.1-3 pp. 369-375.
74
CONTENS Page No. Title of Invention
1
I-Technical Description of the invention
2
A- Former technical condition
2
B- I-1- Technical Description of the invention
2
I – 1 – 1 Innovation
2
I – 1 – 2 Innovation step and industrial capability
2
I – 1 – 3 Technical description of the pilot plant
2
I – 1 – 4: Theoretical of the innovated development pilot plant
3
I – 1 – 5: The invented catalysts components are
6
I – 1 – 6: Equipments used in the work
6
I – 1 – 7: General Method
6
I – 1 – 8: Method of Experiment
7
I – 1 – 9: Preparation and the experiments of the catalyst
8
I – 1 – 9: Preparation and the experiments of the Syrian sliver catalyst
8
I – 1 –9-1: Preparation of The Syrian sliver catalyst ZB-Ag2O, Al2O3-Ag2O
8
I – 1 – 9-2: Experimental Results
9
I – 1 – 9-2-1: N2 adsorption – desorption measurements
9
I – 1 – 9-2-2:Results of the catalytic study
9
I – 1 – 9-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates
9
75
I – 1 – 9-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures
10
I – 1 – 9-2-2-3: Calculation of the kinetic parameters
11
I – 1 – 9-2-3: IR characteristics diagrams
11
I – 1 – 10: Preparation and the experiments of the Syrian sliver and molybdenum catalyst
11
I – 1 –10-1: Preparation the catalyst ZB-Ag2O, Al2O3-MoO3 Ag2O
11
I – 1 – 10-2: Experimental Results
12
I – 1 – 10-2-1: N2 adsorption–desorption measurements
12
I – 1 – 10-2-2: Results of the catalytic study
12
I – 1 – 10-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates
13
I – 1 – 10-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures
13
I – 1 – 10-2-2-3: Calculation of the kinetic parameters
13
I – 1 – 10-2-3: IR characteristics diagrams
14
I – 1 – 11: Preparation and the experiments of the Jordanian silver catalyst
14
I – 1 –11-1: Preparation the catalyst ZJB-Ag2O, Al2O3-Ag2O
14
I – 1 – 11-2: Experimental Results
15
I – 1 – 11-2-1: N2 adsorption–desorption measurements
15
I – 1 – 11-2-2: Results of the catalytic study
16
I – 1 – 11-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates
16
I – 1 – 11-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures
16
76
I – 1 – 11-2-2-3: Calculation of the kinetic parameters
17
I – 1 – 11-2-3: IR characteristics diagrams
17
I – 1 – 12: Preparation and the experiments of the Syrian chromium catalyst
17
I – 1 –12-1: Preparation the catalyst ZB-Cr2O3, Al2O3-Cr2O3
17
I – 1 – 12-2: Experimental Results
18
I – 1 – 12-2-1: N2 adsorption–desorption measurements
18
I – 1 – 12-2-2: Results of the catalytic study
19
I – 1 – 12-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates
19
I – 1 – 12-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures
19
I – 1 – 12-2-2-3: Calculation of the kinetic parameters
19
I – 1 – 12-2-3: IR characteristics diagrams
20
I – 1 – 13: Preparation and the experiments of the Syrian chromium and molybdenum catalyst
20
I – 1 –13-1: Preparation the catalyst ZB-Cr2O3, Al2O3-Cr2O3MoO3
20
I – 1 – 13-2: Experimental Results
21
I – 1 – 13-2-1: N2 adsorption–desorption measurements
21
I – 1 – 13-2-2: Results of the catalytic study
22
I – 1 – 13-2-2-1: Dependence of conversion rate and time on different temperatures and flow rates
22
I – 1 – 13-2-2-2: Dependence of conversion rate on flow rate of car exhaust gas at different temperatures
22
I – 1 – 13-2-2-3: Calculation of the kinetic parameters
23
77
I – 1 – 13-2-3: IR characteristics diagrams
23
II- Comparative study was conductive between our catalyst ZJB-Ag2O, Al2O3-Ag2O and a commercial catalyst manufactory for use in gasoline vehicles
23
Figures, Tables and Plots
24
Industrial Chart
70
What is claimed to
71
Abstract
72
Key Words
72
References
73
78
1-Title of the invention Removal Of OMWW By Turning Its Condensate Into NO3- Ions Adsorbents Carried On Syrian Pumice And Foam Improving Additive In Hard Soap Industry
Additional patent to 5654 patent
Prof.Dr.Y.Walid Al- Bizreh and Wareef Al-Yazjy
1
2- Technical description of the invention A- Previous technical condition: A-1 Technical description the invention
Details explanation of the invention A-1 -1- Novelty: innovative multifunctional co-ion exchangers have been synthesized from OMWW, Syrian Beyloone, and Omanii Zeolite A.
A-1 -2- Inventive step: Removal of OMWW being a main component in a novel co-ion exchangers mentioned above making a considerable contribution to the exchange activity.
A-1 -3- The industrial capability is schematically explained in (page 16 ) and the text concerning the current patent. A-1 -4-Non of research centers concerned in OMWW happened to remove the OMWW by converting it into ion exchangers along with Syrian Beyloone of 55% montmorilloite content, and Omanii Zeolite A. The results of chemical analysis of the above mentioned components are listed in tables (1,2,3 ) formula of some phenols compound in shap (1) A sample of each of the innovated co-ion exchangers can be given if required. Table (1)Chemical Structure of Raw Syrian Bentonite )Component( W% )Component( W%
AL2O3 12.18 Mn2O3 0.150
CaO 8.22 Na2O >0.06
CL>0.002
Cr2O3 0.044
P2O5 0.082
F0.020
SO3 >0.002
Fe2O3 8.52 SiO2 46.38
Table ( 2 )Chemical Structure of Oman Zeolite A
2
K2O 0.438 TiO2 1.12
MgO 8.34 L.O.I 14.18
)Component( W%
AL2O3 29.24
Na2O 17.38
SiO2 32.88
H2O 20.63
Table( 3 ) composition of OMWW which produce by press and centrifugation technologies Parameter pH Dry material Density Oil Reduction sugar Polyphenols O-Di phenol Hydroxy Tyrosol Ash COD Organic nitrogen Total phosphorous Sodium Potassium Calcium Magnesium Iron Copper Zink Manganese Nicl Cobalt Lead
Unit pH g/l g/l g/l g/l g/l mg/l g/l g/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l
Traditional process 5.73-4.73 266.00-15.50 1.09-1.02 11.50-0.12 67.10-9.70 14.30-1.40 13.30-0.90 937-71 42.60-4.00 389.50-42.00 1106-154 915-157 285-38 5000-1500 408-58 337-90 86.40-16.40 4.75-1.10 6.50-1.60 8.90-2.16 1.58-0.44 0.96-0.18 1.85-0.40
3
Modern process 4.55-5.89 161.20-9.50 1.046-1.007 29.80-0.41 34.70-1.60 7.10-0.40 6.00-0.30 426-43 12.5-0.40 199.20-15.20 966-140 485-42 124-18 2500-630 200-47 180-60 31.50-8.80 3.42-1.16 4.48-1.42 5.20-0.87 1.44-0.29 48.00-0.12 0.72-0.35
O
HO
OH
HO
O
O
OH
OH
OH OH
OH
OH
p-hydroxybenzoic acid (p-HBA)
Gallic acid (GA)
O
CH3
O
OH
O
3,4-Dihydroxybenzoic acid Di-HBA
O
OH
CH3
O
OH
OH
Syringic acid (SA)
Vanillic acid (VA)
CH3
OH
HO tyrosol (Ty)
O
OH
OH
O
O
OH
OH
OH cinnamic acid CA
p-hydroxycinnamic acid p-HCA
o-hydroxycinnamic acid o-HCA
OH
HO O H3C
OH
OH
OH O O
3,4-Dihydroxycinnamic acid Di-HCA
ferulic acid (FA)
Shape (1) Formula of some phenol compounds in OMWW
4
A-1 -5- Preparation A-1 -5-1- The ion exchanger OMWWBZ-CP 100 g of Syrian Beyloon were added to 100 g of Zeolite in a thermo plastic Beaker and mixed with 100 g of OMWW until a homogenous past is formed. The past was left to the next day. In order to carry out the poly condensation procces of the phenols content 2 ml of Formaldehyde and 4 ml of Ammonia hydroxide were added to the past and well mixed. An increase in temperature of the past from 31.3 Cْ to 34.4C ْwas observed. The past became more elastic (the observed rise in temperature indicated an exothermic chemical reaction, condensation of phenols contained in a water bath at 50-60 C ْfor 40 minuets. The resulting past was left to the next day to undergo the granulation , drying and calcination at 400 Cْ. Loss of weight was 10% . In order to obtain the Na-ion exchanger, (2) g of granules were immersed in (20) ml NaCl 3N solution for 24 hours at room temperature . The ion exchanger OMWWBZ-PC was filtered, washed, and dried to be used in next step. A-1 -5-2 -The ion exchanger OMWWBZ Neither formaldehyde nor Ammonia hydroxide were used in the preparation of this ion exchanger. Zeolite, Syrian Beyloone and OMWW were mixed, being let to rest to the next day, granulated, dried at room temperature, and calcinated at 400 C ْfor 4 hours. Granules of product were immersed in 3N solution of NaCl for 24 hours, washed, dried, and prepared for conducting experiments. A-1 -5-3- The ion exchanger BZ This form was made to compare our ion exchangers with. All the above mentioned steps were implicated with one difference: we did not add OMWW to form the past, distilled water 100g was used instead. The resulting past was granulated, dried at room temperature and cacinated at 400 C ْfor 4 hours. The ion exchanger was produced in its form Na-form as mentioned above as for the other received ion exchangers. A-1 -6- Measurements (explanation) Hard water for testing the performance of the studied ion exchanger was prepared from chemical pure {(2) g CaCl2.xH2O (M=110.99) + (2)g MgSO4.7H2O} solved, and diluted to 1 liter with distilled water. 5
The ion exchanger{ (1) g} was set on a glass wool bed in ion exchanger column (section area=1cm3) . Hard water was dropped into the column by means of a Burette . (Ca+2,Mg+2) contents were Determined as the following : 5 ml of the desired water were taken with a measuring tube, along with (1) ml of buffer solution {from (440)ml ammonia solution + (54)g NH 4Cl in 1 liter distilled water} adding 0.05-0.1 gr of the indicator Irocrom Black T and titrated with 0.01M EDTA. Ca+2 was determined in a similar way with one difference that Murexide was used instead of Irocrom Black-T and NaOH 0.1N to produce a pH of 12 to 13 instead of buffer solution. Tests were conducted at room temperature with the flow rate (1ml/75 sec). Ca+2,Mg+2 ions were measured after hard water being dropped through the ion exchanger until the hardness of the out- coming water is equal with that of the incoming hard water. At this moment the absorbance capacity is determined. The ion exchangers were regenerated by immersing the used (1) g in (20) ml of 3N Sodium chloride solution for 24 hours. A-1 -7- Results : Results for the prepared ion exchangers as for dynamic method are listed in tables (4 , 5 , 6 ). Table (4 ) The ion exchange capacity of ion exchanger prepared for removing Ca+2 and Mg+2 ions( mgr.eq/100g ) Ion exchanger type Numbered of regenerated Base 1 2 3 4 5 6 7 8 9 10 Mean Sum
OMWBZ
OMWBZ-PC
BZ
238.39 180.36 180.18 171.43 198.57 162.50 207.54 196.16 206.29 169.64 165.00 188.73
234.54 193.50 161.04 177.71 150.89 220.71 202.61 194.64 183.92 187.20 160.08 187.89
210.57 150.00 165.91 162.83 163.57 182.24 171.60 162.00 167.80 136.00 136.00 164.41
6
Table (5 ) The ion exchange capacity of ion exchanger prepared for removing Ca+2 ions ( mgr.eq/100g ) Ion exchanger type Numbered of regenerated Base 1 2 3 4 5 6 7 8 9 10 Mean Sum
OMWBZ
OMWBZ-PC
BZ
201.79 135.71 155.89 139.29 154.82 141.07 162.46 153.89 160.36 130.64 147.60 153.05
184.29 167.86 126.86 142.29 125.00 171.07 155.21 152.86 143.52 150.80 132.00 150.16
206.85 133.93 134.98 123.36 125.00 141.36 150.80 129.20 120.80 109.00 110.00 135.03
Table (6 ) The ion exchange capacity of ion exchanger prepared for removing Mg+2 ions ( mgr.eq/100g ) Ion exchanger type Numbered of regenerated
Base 1 2 3 4 5 6 7 8 9 10 Mean Sum
OMWBZ
OMWBZ-PC
BZ
36.61 44.64 24.29 32.14 43.75 21.43 45.07 42.27 45.93 39.00 17.40 35.68
50.25 25.64 34.18 35.43 25.89 49.64 47.39 41.78 40.40 36.40 28.08 37.74
3.72 16.07 30.93 39.47 38.57 40.88 20.80 32.80 47.00 27.00 26.00 29.39
7
A-1 -8-Estimation of chemical equilibrium Constant KT maximum absorption capacity Sm of the prepared ion exchangers: The ion exchange reaction between the Na+ ions and (Ca+2,Mg+2) in aqueous medium occurs to the following equation 2[Na+]s + [Ca+2]w = [Ca+2]s + 2 [Na+]w According to the low of mass action the chemical equilibrium constant KT KT
[Ca 2 ] s [ Na ] 2w [ Na ] 2s [Ca 2 ] w
Where: [Ca+2]w=C1 is the equilibrium concentration of Calcium ion [Ca+2]s=S1, is the initial concentration of [Ca+2] before using the ion[Ca+2]. [Na+]w= C2 is the equilibrium concentration of the Na+ ions whereas 2 [Ca+2]s= [Na+]w [Na+]s=S2 is the [allover exchangeable Na+ ions- [Na+]w] . The equilibrium constants were determind statically as mentioned above at (30-40-50)C ْ. Results for the prepared ion exchangers [OMWBZ,OMWBZ-PC, BZ]are listed in tables (7,8,9,10,11,12,13,14,15) respectively Table (7) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[OMWBZ] at 30 Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca+2]w for mmole/liter
11.1 19.8 37.25 42.5 51
22.2 39.6 74.5 85 102
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.1 0.3 5.05 8.9 14.35
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-
C1S2/C22
0.200 0.600 10.100 17.800 28.700
22.000 39.000 64.400 67.200 73.300
44.000 78.000 128.800 134.400 146.600
239.360 205.360 154.560 148.960 136.760
9.680 10.140 1.643 1.015 0.749
2.604 1.081 0.371 0.330 0.255
0.0042 0.0049 0.0065 0.0067 0.0073
0.0247 0.0203 0.0941 0.1468 0.1826
1
Table (8) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[OMWBZ] at 40 Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca+2]w for mmole/liter
9.100 19.150 36.200 42.500 51.000
18.200 38.300 72.400 85.000 102.000
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.050 0.650 6.050 12.550 17.4
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-
C1S2/C22
0.100 1.300 12.100 25.100 34.800
18.100 37.000 60.300 59.900 67.200
36.200 74.000 120.600 119.800 134.400
247.160 209.360 162.760 163.560 148.960
13.104 4.212 1.202 0.572 0.519
3.375 1.185 0.439 0.447 0.330
0.00405 0.00478 0.00614 0.00611 0.00671
0.0189 0.0497 0.1354 0.2860 0.2870
8
1
Table (9) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[OMWBZ] at 50 Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca+2]w for mmole/liter
9.100 19.150 36.200 42.500 51.000
18.200 38.300 72.400 85.000 102.000
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.100 0.600 5.300 11.400 16.65
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-1
C1S2/C22
0.200 1.200 10.600 22.800 33.300
18.000 37.100 61.800 62.200 68.700
36.000 74.200 123.600 124.400 137.400
247.360 209.160 159.760 158.960 145.960
6.480 4.588 1.441 0.679 0.567
3.399 1.179 0.413 0.406 0.310
0.0040 0.0048 0.0063 0.0063 0.0069
0.0382 0.0456 0.1109 0.2342 0.2575
Table (10) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[OMWBZ-PC] at 30Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca+2]w for mmole/liter
11.100 19.800 37.250 42.500 51.000
22.200 39.600 74.500 85.000 102.000
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.100 0.500 4.700 10.300 15.600
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-1
C1S2/C22
0.200 1.000 9.400 20.600 31.200
22.000 38.600 65.100 64.400 70.800
44.000 77.200 130.200 128.800 141.600
230.560 197.360 144.360 145.760 132.960
9.680 5.960 1.803 0.805 0.643
2.416 1.009 0.320 0.330 0.250
0.0043 0.0051 0.0069 0.0069 0.0075
0.0238 0.0331 0.0800 0.1810 0.2069
Table (11) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[OMWBZ-PC] at 40Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca+2]w for mmole/liter
9.100 19.150 36.200 42.500 51.000
18.200 38.300 72.400 85.000 102.000
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.050 0.700 7.900 13.400 19.550
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-1
C1S2/C22
0.100 1.400 15.800 26.800 39.100
18.100 36.900 56.600 58.200 62.900
36.200 73.800 113.200 116.400 125.800
238.360 200.760 161.360 158.160 148.760
13.104 3.890 0.811 0.506 0.405
3.139 1.092 0.460 0.430 0.352
0.0042 0.0050 0.0062 0.0063 0.0067
0.0182 0.0516 0.1990 0.3128 0.3675
9
Table (12) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[OMWBZ-PC] at 50 Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca+2]w for mmole/liter
9.100 19.150 36.200 42.500 51.000
18.200 38.300 72.400 85.000 102.000
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.050 0.700 7.450 12.600 18.200
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-1
C1S2/C22
0.100 1.400 14.900 25.200 36.400
18.100 36.900 57.500 59.800 65.600
36.200 73.800 115.000 119.600 131.200
238.360 200.760 159.560 154.960 143.360
13.104 3.890 0.888 0.568 0.473
3.139 1.092 0.443 0.402 0.313
0.00420 0.00498 0.00627 0.00645 0.00698
0.0182 0.0516 0.1798 0.2730 0.3032
Table (13 ) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[BZ] at 30 Cْ
Volume of EDTA solution for 5 ml the initial solutions
11.100 19.800 37.250 42.500 51.000
[Ca+2]w for mmole/liter
Volume of EDTA solution used for 5 ml after use of ion exchanger
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-1
C1S2/C22
22.200 39.600 74.500 85.000 102.000
0.050 0.500 6.100 9.600 14.300
0.100 1.000 12.200 19.200 28.600
22.100 38.600 62.300 65.800 73.400
44.200 77.200 124.600 131.600 146.800
191.320 158.320 110.920 103.920 88.720
19.536 5.960 1.273 0.902 0.754
1.656 0.649 0.197 0.164 0.107
0.00523 0.00632 0.00902 0.00962 0.01127
0.0098 0.0266 0.0872 0.1152 0.1177
Table (14) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[BZ] at 40 Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca+2]w for mmole/liter
9.100 19.150 36.200 42.500 51.000
18.200 38.300 72.400 85.000 102.000
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.050 0.500 7.700 13.583 18.750
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-1
C1S2/C22
0.100 1.000 15.400 27.166 37.500
18.100 37.300 57.000 57.834 64.500
36.200 74.600 114.000 115.668 129.000
199.320 160.920 121.520 119.852 106.520
13.104 5.565 0.844 0.492 0.444
2.195 0.694 0.259 0.248 0.176
0.00502 0.00621 0.00823 0.00834 0.00939
0.0152 0.0289 0.1440 0.2434 0.2400
10
Table (15) results for equilibrium concentrations of [Na+],[Ca+2,Mg+2] ions for the ion exchanger[BZ] at 50 Cْ Volume of EDTA solution for 5 ml the initial solutions
[Ca ]w for m mole/liter
9.100 19.150 36.200 42.500 51.000
18.200 38.300 72.400 85.000 102.000
+2
Volume of EDTA solution used for 5 ml after use of ion exchanger 0.050 0.600 6.100 12.100 17.550
C1=[Ca+2]w mmole/liter
[Ca+2]s mmole/liter
C2=[Na+]w mmole/liter
S2=[Na+]s mmole/liter
[Na+]2w [Ca+2]w mole/liter
[Na+]2s [Ca+2]s mole/liter
1/S2 (mmole/l)-1
C1S2/C22
0.100 1.200 12.200 24.200 35.100
18.100 37.100 60.200 60.800 66.900
36.200 74.200 120.400 121.600 133.800
199.320 161.320 115.120 113.920 101.720
13.104 4.588 1.188 0.611 0.510
2.195 0.701 0.220 0.213 0.155
0.00502 0.00620 0.00869 0.00878 0.00983
0.0152 0.0352 0.0969 0.1864 0.1994
A-1 -8-1- Determination of chemical equilibrium constant and the maximal absorption capacities for the prepared ion exchangers. The maximal absorption capacity of ion exchanger is the sum of the concentrations of [Na+] =S2 and [(Ca+2,Mg+2)]=S1 ions on the surface of the ion-exchanger: *S1+2S2=Sm 2 S C 1 2 K 2 S C 2 1 Substituting S2 from the expression 2 K S C 2 1 S 1 2 K C S 2 1 1 T 1 2 C 2 in equations * we receive: S S S C2 2 m m 2 C1C 2 1 1 can be used to determine Plots in coordinates from the ƒ 2 Sm S2 C2 1 intercept value of , and the slope of the resulting line (f.g. 2,3,4) S2
Results for the studied ion exchangers are listed in table (16) and ( 17 ) Table (16 ) values for K and Sm at room temperature Co-ion exchanger OMWBZ OMWBZ-PC BZ
K 1.94475 1.736262 4.056406
11
Sm mgr.eq/100g 222.22 219.78 188.67
Table ( 17 ) values for K,Sm,and ∆Sm=Sm-(Sm)BZ at room temperatures Co-Ion exchanger K BZ 4.056 OMWBZ-PC 1.736 OMWBZ 1.944
Sm (mgr.eq/100gr) 188.00 219.78 222.20
∆Sm=Sm-(Sm BZ) (mgr.eq /100gr)
0 31.78 34.2
A-1 -8-1-1-Data of tables (16 ) and (17 )show a firm evidence that the component OMWW has made a contribution of 29% and 31% to the ion exchanger efficiency of the exchangers OMWBZ-PC and OMWBZ respectively. Despite the small differences between the values of Sm for both OMWW exchangers, OMWBZ-PC was observed to be more stable in terms of multi regeneration. A-1 -8-1-2- When 500 gr of OMWW were dried at room temperature a 27.66 gr elastic mass remained. Heating 1/5 of this mass for 4 hours at 120 Cْ reduced the mass from 5.293 to 4.4068 gr of elastic character, calcination of this mass in the atmosphere of N2 produced 1.606 gr of solid mass which gave rise to the added value of ion exchanger to be ∆Sm = 34.2 (mgr.eq/100gr) A-1 -8-1-3- Poly -condensation of the poly phenols took place at 50-70 Cْ when 50 ml of Ammonia solution and 20 ml of Formaldehyde were added as described above to 500gr of OMWW. Evaporation of the resulting solution at room temperature left 25.75 gr as elastic mass with more adhesive property. Heating 1/5 of this mass for 4 hours at 120 Cْ reduced the mass from 4.393 gr to 3.146 gr, and a persisting bubble of the mass was observed during the heating. Calcination of this mass in the atmosphere of N2 for 4 hours produced 1.034 gr of solid mass value of which gave rise to the added value of ion exchanger to be ∆Sm= 31.78 (mgr.eq/100gr) and comprises 29% of the ion exchanger,. The lower value of the elastic mass for OMWBZ-PC may be attributed to water formed as a product of polycondensation of the phenols content A-1 -9-Thermo dynamical parameters at 30Cْ for the invented ion exchangers listed in table ( 18 ) and were determined from equations
1 LnK ƒ and F RTLnK T
12
(f.g 5,6,7).
Table ( 18) Thermo dynamical parameter of the invented Co-ion exchangers at 30Cْ Co-ion exchanger
OMWBZ-PC OMWBZ BZ
∆F cal/mol -332.207 -400.385 -843.138
∆H cal/mol -11923.045 -15102.526 -10730.76
∆S e.u -38.254 -48.522 -32.632
A-1 -10- Removal NO3- and NH4+ ions at room temperature A-1 -10-1- NO3- onions were completely exchanged in solutions of less than 100 ppm NO3- ions and after regeneration in NaCl 3N solution at room temperature table( 19 ). Table (19 ) Removal of NO3- and NH4+ ions from the solution contain less than 100 ppm at room temperature. Co-ion exchanger OMWBZ OMWBZ-PC BZ
Removal NH4+ ions % Before After regeneration regeneration 84.38 70.97 85.31 72.75 83.87 73.86
Removal NO3- ions % Before After regeneration regeneration 100 100 100 100 100 100
A-1 -10-2 -NH4+ cations were exchanged with Na+ ions in similar conditions as well table ( 19 ). A-1 -10-3- Unfortunately ,in contrast with Ca+2,Mg+2, neither data for NH4+ ions nor data for NO3- ions was confirming to the formula for ion exchange law. A-1 -10-4- This conclusion may be attributed to less electric charges and larger diameter of NO3- ( d= 1.89 Aْ) and NH4 + ( d= 1.43 Aْ) than Mg +2 ( d= 0.77 Aْ) and Ca+2 (d= 0.98Aْ) and to the pore structure of the ion exchangers. A-1 -10-5- NO3- anions were removed from industrial polluted “waters in water treatment planet of Damascus” table ( 20 ) . Table (20 ) Removal of NO3- and NH4+ ions from the treatment water plant of Damascus at room temperature *. Ion exchanger OMWBZ OMWBZ-PC BZ
Removal NH4+ ions % Before After regeneration regeneration 81.79 98.91 79.35 98.91 78.26 98.91 13
Removal NO3- ions % Before After regeneration regeneration 90.18 32.14 90.18 39.29 91.52 23.21
*Apparatus: Colorimeter Dr/890 Results for NO3- remopval may be atrebuted to its large diameter (1.89 A)high content of NO3- and to the serounding ions or impurities in this water that may have narrowered the pores in the ion exchanger. A-1 -11- When the innovated ion exchangers were tested in KMnO4 solutions, data were proved to suit molecular adsorption rules, rather than ion exchange regulation. A-1 -11-1- The BZ product shows a typical Langmure curve
KC 1 KC
with sharp slope in the field of small concentrations of KMnO4 with poor mono molecular layer ( am). A-1 -11-2- As for OMWBZ, adsorption of KMnO4 shows good appliance with Frendicsh formula (a/m=KC1/n) with a relatively high value of (am). A-1 -11-3- Adsorption of KMnO4 on OMWBZ-PC happened to be directly proportional with small concentrations of KMnO4 ( a=amKC) with a value of (am) near to that of OMWBZ. Results of KMnO4 adsorption are show in table (21 ). Table ( 21 )values of (am ) and ( Δam ) of KMnO4 adsorption for BZ, OMWBZ, and OMWBZ-PC at room temperature.
Ion exchanger adsorbent
am mmol/100gr
Δam mmole/100gr
BZ
2.920
0
OMWBZ 10.282 7.362 OMWBZ-PC 10.268 7.348 Apparatus: Colorimeter Dr/890 , = 400 nm
formula
KC 1 KC
(a/m=KC1/n) ( a=amKC)
A-1 -11-4 Data of table (21) reflect the big contribution of the OMWW to the adsorption efficiency of OMWBZ and OMWBZ-PC in comparison with BZ. A-1 -12- Molecular separation of the invented products in polar-nonpolar liquid system was tested for CH3OH-CCl4 liquid system. Results in the coordinates of Gibss equation: G1
m 2 ( K 1) X 1 (1 X 1 ) are listed in table 1 ( K1, 2 1) X 1
(22) (f.g.8,9,10) . 14
Table ( 22 ) Values of Kβ and m for CCl4, and CH3OH adsorption on BZ, OMWBZ-PC, OMWBZ at room temperature. Ion exchanger
OMWBZ OMWBZ-PC BZ
CCL4 Kß 20.753 37.735 20.753
m
0.107 0.148 0.127
CH3OH Kß 37.735 53.778 81.000
m
0.0826 0.156 0.100
Results in table (22 ) indicate more tendency to unpolar adsorption with decrease in polar adsorption as for OMWBZ-PC if compared with the molecular separation property of BZ. A-1 -13- Syrian Beyloone is deposited near Aleppo (Syria) in as thick as 216 meters layers. Syrian Beyloone differs from other Bentonites: In addition to 50-55 % contents of montmorillonite, quarts, Ca, Mg carbonates and other compounds, results of the chemical analysis of Syrian Bentonite is shown in table ( 1 ). The detailed information about Syrian Beyloon are published in reference (4-7 ). A-1 -14- The DTA curves show indo thermal process at 94-97Cْ for all studied samples are simillar before and after regeneration with NaCl (f.g.11,12) A-1 -15- No substantial differences were observed between the diagrams of X ray diffraction for OMWBZ,OMWBZ-PC and BZ in which the Zeolite and Bentonite picks are well distinguished, and the generation with NaCl didn’t affect the diagrams (f.g.13,14). A-1 -16 - No hazardous compounds( heavy metals) in the suggested ion exchangers according to analysis with atomic absorption (Appendex 1).
15
A-2 Chart,Diegrams, Curves and Appendix lairtsudnIIndustrial chart for removing OMWW OMWW Syrian Bentonite
zeolite
Mixer
Digester
Ammonia hydroxide
PolycondensationVan 60-50Cْ
Granulator
Drier
Calcination
Cooling
Packing
16
Formaldehyde
0.008 0.007 0.006 1/S2
0.005 0.004 0.003 0.002 0.010 0.030 0.050 0.070 0.090 0.110 0.130 0.150 0.170 0.190 2
C1S2/C2
2 (F.g 2) for 30و ْ نهمبادل OMWBZ اندرجة COMWBZفي انشكم ( S2/1 )1بدالنة 1S2/C 2
0.008 0.007 0.006
1/S2
0.005 0.004 0.003
0.250
0.200
0.150
0.050
0.100
0.002 0.000
C1S 2/C22
(F.g.3) for OMWBZ-PC 2
انشكم ( S2/1 ) 4بدالنة C1S2/C2في اندرجة 30وْ نهمبادل OMWBZ-PC
0.012 0.011 0.010 0.009 1/S2
0.008 0.007 0.006 0.005 0.140
0.120
0.100
0.080
0.060
0.040
0.020
C1S2/C22 2 )(F.g.4 for BZ اندرجة 30وْ نهمبادل BZ C1Sفي انشكم ( S2/1 ) 7بدالنة 2/C2
17
0.004 0.000 1/S2
1.600 1.400
Ln K
1.200 1.000 0.800 0.600 0.400 0.200 0.000 0.003
0.0031
0.0032 1/T (Kْ)-1
0.0033
(Fig 5) for BZ 1.400 1.000 0.600
LnK
0.200
-0.200 0.0030
0.0031
0.0032
0.0033
-0.600 -1.000 -1.400
1/T (Kْ)-1
(Fig .6) for OMWBZ
1.400 1.000
Ln K
0.600 0.200
-0.200 0.003 -0.600
0.0031
0.0032
-1.000 -1.400
-1 1/T (Kْ)
(Fig. 7) for OMWBZ-PC
18
0.0033
0.1
0.08
0.06
0.04
0.02
0 0.2
0.4
0.6
0.8
mol/g1
G
0
-0.02
-0.04
-0.06
-0.08
-0.1
-0.12
X
(Fig.8)Adsorption in binary liquid system CH3OH,CC4 for OMWBZ
19
1.2
mol/g 0.1000
0.0800
0.0600
0.0400
0.0200
0.2000
0.4000
0.6000
0.8000
1.0000
G
0.0000 0.0000
-0.0200
-0.0400
-0.0600
-0.0800
-0.1000
-0.1200
X
(F.g.9)Adsorption in binary liquid system CH3OH,CC4 for OMWBZPC
20
1.2000
mol/g 0.1
0.08
0.06
0.04
0.02
0 G
0
0.2
0.4
0.6
0.8
1
-0.02
-0.04
-0.06
-0.08
-0.1
-0.12 X1
(F.g.10) Adsorption in binary liquid system CH3OH,CC4 for BZ
21
1.2
( F.g. 11) DTA for Na-form of the ion exchanger OMWBZ-PC
22
(F.g. 12) DTA for OMWBZ-PC
23
(F.g. 13) X.R.D Na-form of the ion exchanger OMWBZ-PC
24
(F.g.14) X.R.D for OMWBZ-PC
25
Appendix (1) Results for Heavy ions detection Ion exchanger before regeneration wastewater OMWBZ+wastewater OMWBZ-PC+wastewater BZ+wastewater
Heavy Metals concentration (μ g/l) Cd Cu Zn Pb Mn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Ion exchanger after regeneration
Heavy Metals concentration (μ g/l) Cd Cu Zn Pb Mn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
wastewater OMWBZ+wastewater OMWBZ-PC+wastewater BZ+wastewater
26
A-3 What is claimed to : A-3-1-Method for Removal of the pollutant Olive Mill Wastewater (OMWW) by turning it into new multifunctional co-ion exchangers.
A-3-2- Preparation of new ion exchanger (OMWBZ-PC) from (Omani Zeolite A+Beyloone+OMWW) with surface polycondensation of the phenols components.
A-3-3- Preparation of new ion exchanger (OMWBZ) from (Omani Zeolite A+Beyloone+OMWW) without polycondensation.
A-3-4- Preparation of ion exchanger (BZ) from (Omani Zeolite A+Beyloone).
A-3-5- Hard water treatment with the ion (OMWBZ, OMWBZ-PC, BZ), determination of chemical equilibrium constant and the maximal absorption capacities and thermal dynamical parameters for (OMWBZ, OMWBZ-PC, BZ).
A-3-6- Removal of NO3- and NH4+ ions from polluted with them waters. A-3-7- Adsorption KMnO4 on (OMWBZ, OMWBZ-PC, BZ). A-3-8- Molecular separation in polar-unpolar binary liquid system CH3OHCCl4 by use of (OMWBZ, OMWBZ-PC, BZ).
A-3-9- Introducing DTA curves and XRD diagrams of (OMWBZ, OMWBZ-PC, BZ).
A-3-10- The mentioned above claims may go with all kinds of Zeolites and Bentonites along with OMWW
27
A-4- Abstract A new method for removing the pollutant OMWW has been developed to turn it into multi functional co-ion exchanger along with Syrian Beyloone and Omani zeolite A. The presence of less than 1% w of the calcinated material resulting from OMWW and polycondensed phenols of it , gave rise to about 31% increase in the ion exchange efficiency in terms of small diameter ions (Ca+2 , Mg+2 ( , and to 200% excess in case of KMnO4 adsorption on the innovated products. Moreover the resulting ion exchangers were proved to be good enough to act in terms of relatively large diameter ions (NO3-, NH4+) for concentrations less than 100 ppm, in addition to their competency to molecular separation in polar- nonpolar liquid systems.
Key words: Olive Mill Wastewater (OMWW), Ion exchanger from (OMWW, Beyloone, Zeolite), Removal of OMWW, Ion exchangers.
28
A-5-References References on Zeolite 1 Breck D.W. 1974Zeolite Molecular Sieves-Structure,Chemistry and Use. Wiley Interscience, New York. 2 Breck, Zeolite Molecular Sieves, New York: Wiley(1979); cited in Rompp, Chemie Lexikon, Band 6,9. Auflage (1992), Georg Thieme Verlag, Stuttgart. 3 Allen, H.E.,Cho S.H. Neubecker T. A. 1983. Ion exchange and hydrolysis of type A Zeolite in natural water. Water Res. 17, 1871, 1879. References on Syrian Bentonite 4 Y. W. Bizreh, Damascus University Journal Vol (18) N ْ= 5, part (2) page 7-38, (1989) 5 Hamwee, N. master degree dissertation P.29-39 Supervisered by Prof. Y. W. Bizreh, Damascus University (1996). 6 Shaheen Abeer, master degree dissertation P.47-52 Supervised by Prof. Y. W. Bizreh, Damascus University. 7 Abudullah, Suzan master degree dissertation P.39-74 Supervised by Prof. Y. W. Bizreh, Damascus University, Faculty of sciences (2003). Reference for OMWW 9 Isabel P. Marques. Anaerobic digestion treatment of olive mill wastewater for effluent re-use in irrigation. Departamento de Energias Renováveis, Instituto Nacional de Engenharia e Tecnologia Industria, 21 August 2000. 10 Basheer Sobhi,* Sabbah Isam, Yazbek Ahmad, Haj Jacob, Saleeba. Ahlam REDUCING THE ENVIRONMENTAL IMPACT OF OLIVE MILL WASTEWATER IN JORDAN, PALESTINE. 10 The treatment of olive oil milling wastewater. Objective and results of the CAT-MED. 5TH FRAMEWORK PROGRAMME -INCO-MED PROGRAMMECONFIRMING THE INTERNATIONAL ROLE OF COMMUNITY RESEARCH Shared Cost Actionsww2.unime.it/catalysis/cat-med. 11 ANONYMOUS: Food and agriculture organization of the United Nations, Online under URL: www.fao.org [last Access on 23.03.2005]. 12 ANONYMOUS: International Olive Oil Council, Online under URL: www.internationaloliveoil.org [last Access on 23.03.2005]
29
13 MULINACCI, N., et al. (2001): Polyphenolic Content in Olive Oil Waste Waters and Related Olive Samples, Journal of Agricultural and Food Chemistry (2001) 49: 1005 – 1009. 14 MULINACCI, N., et al. (2001): Polyphenolic Content in Olive Oil Waste Waters and Related Olive Samples, Journal of Agricultural and Food Chemistry (2001) 49: Page: 1005 – 1009. 15 FIORENTINO, A., et al. (2003): Environmental effects caused by olive oil mill wastewaters: Toxicity comparison of low-molecularweight phenol components, Journal of Agricultural and Food Chemistry (2003) 51: Page: 1005 – 1009. 16 Igor Kobek," Waste Treatment- TDC-OLIVE project" Framework Programme of the European Union http://www.tdcolive.net/documents/booklet/D14k_Waste_Treatment_ V1.0.pdf 17 ANONYMOUS (2004): Project INASOOP - Integrated Approach to Sustainable Olive Oil and Table Olive Production (COLL-CT-2003500467) - Report on Relevant Olive Oil and Table Olives Production Techniques and Technologies, Pages: 20. " .. أ حمٍ عبهش. فشاًسىا, لشٍ بُج.م.د.أ. هحوذ,ٍد الوٌجذ عل. أ. هحوذ,د هبشن شهُش. أ18 هعبلجت الوُبٍ الصٌبعُت الٌبحجت عي هعبصش الضَخىى ببسخخذام حمبًبث األكسذة الوخمذهت . جبهعت دهشك, كلُت العلىم, الوحفضة ضىئًُب و بىجىد أًصبف الٌىالل" سسبلت هبجسخُش .2004 االحجبهبث الحذَثت فٍ إداسة. الوؤحوش العشبٍ الثبلث لإلداسة البُئُت. حبفظ شبهُي. د19 الوُخلفبث الولىثت للبُئت هفهىم وأًىاع الوُخلفبث الولىثت للبُئت وأسبلُب هعبلجخهب Management of Olive Mills Wastes in the Palestinian جبهعت، كلُت الهٌذست,هخلفبث الضَخىى وإداسحهب فٍ الوٌبطك الفلسطٌُُتTerritories .فلسطُي-ًببلس,الٌجبح الىطٌُت دساست وححذَذ أًىاع وًسب الوشكببث الفٌُىلُت الطبُعُت فٍ صَج.د هحوذ دَب ًذاف. أ20 الضَخىى البكش السىسٌ وهذي حأثُش طشَمت اسخخالص الضَج علً هحخىاٍ هي هزٍ الوشآببث - سىسَت, جبهعت حششَي- آلُت الضساعت- لسن علىم األغزَت." بهذف ححسُي الجىدة الالرلُت جبهعت." " طشق هعبلجت هبء الجفج الٌبحج عي عصش الضَخىى, الٌصبس أحوذ هحوذ21 سىسَب, كلُت الهٌذست الضساعُت,دهشك Reference of ion exchangers 22 -Andrei A , Zagordni” Ion exchange Materials properties and Applications “ Elsvier, 2007.
30
B- Details explanation of the invention
B1-1 Novelty: innovative adsorbents have been synthesized from the following components 1- OMWW,2- crushed granular pumice (0.1-0.5 mm) 3- granular pumice 4Basaltic or pumice wool . B-1-2 Inventing a new form of solid soap by employing the condensed OMWW in natural soap industry .
B -2 Inventing step: B-2-1 Removal of OMWW being a main component along with Syrian Shahba pumice novel NO3- adsorbents from polluted with NO3- ions waters. B- 2-2 : Use of the condensed OMWW in natural solid soap industry as a foam improving ingredient and antioxidant.
B-3 The industrial appliance capability: is schematically explained in (45,46) and in the text concerning this patent
31
B-4 Technical description the invention B-4-1: Non of the research centers concerned in OMWW happened to carry OMWW on pumice (Syria , Shahba) or basaltic wool to obtain adsorbents for NO3- ions removal from waters. The chemical structure of the pumice is shown in table (1) and the OMWW is listed in table (2). The formula for some phenol compounds are shown in fig (1) Table( 2 ) composition of OMWW which produce by press and centrifugation technologies Parameter pH Dry material Density Oil Reduction sugar Polyphenols O-Di phenol Hydroxy Tyrosol Ash COD Organic nitrogen Total phosphorous Sodium Potassium Calcium Magnesium Iron Copper Zink Manganese Nicl Cobalt Lead
Unit pH g/l g/l g/l g/l g/l mg/l g/l g/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l
Traditional process 5.73-4.73 266.00-15.50 1.09-1.02 11.50-0.12 67.10-9.70 14.30-1.40 13.30-0.90 937-71 42.60-4.00 389.50-42.00 1106-154 915-157 285-38 5000-1500 408-58 337-90 86.40-16.40 4.75-1.10 6.50-1.60 8.90-2.16 1.58-0.44 0.96-0.18 1.85-0.40
32
Modern process 4.55-5.89 161.20-9.50 1.046-1.007 29.80-0.41 34.70-1.60 7.10-0.40 6.00-0.30 426-43 12.5-0.40 199.20-15.20 966-140 485-42 124-18 2500-630 200-47 180-60 31.50-8.80 3.42-1.16 4.48-1.42 5.20-0.87 1.44-0.29 48.00-0.12 0.72-0.35
O
HO
OH
HO
O
O
OH
OH
OH OH
OH
OH
p-hydroxybenzoic acid (p-HBA)
Gallic acid (GA)
O
3,4-Dihydroxybenzoic acid Di-HBA
O
OH
O
O
OH
CH3
O
OH
OH
Syringic acid (SA)
Vanillic acid (VA)
CH3
CH3
OH
HO tyrosol (Ty)
O
OH
OH
O
O
OH
OH
OH cinnamic acid CA
p-hydroxycinnamic acid p-HCA
o-hydroxycinnamic acid o-HCA
OH
HO O H3C
OH
OH
OH O O
3,4-Dihydroxycinnamic acid Di-HCA
ferulic acid (FA)
Fig (1) formula of some phenol compounds in OMWW.
B 4-2 In addition , we believe that we are the first to produce a new form of natural solid soap by adding the OMWW condensate to the hot liquid phase of soap with stirring before hardening . B-5 Preparations B-5-1 The adsorbent BW-PC 300 ml of OMWW were added to 18 gr of basaltic wool. The resulting mass was left to dry at the room temperature to result 37±1 grs of the product. 33
Once 12 ml of (36%) Ammonia and 6 ml of formaldehyde were added and mixed together, temperature rasid from 34C ْ to 38 C ْ indicating to an exothermal process. The produced mass that waited 37.8 gr after drying at room temperature was calcinated at 400 C ْ for four hours the final product was the adsorbent that waited 25.7 gr B-5-2 the adsorbanent BG-PC : 18 gr granular pumice were mixed with 27 gr of OMWW condensate resulting from drying 500 ml OMWW at room temperature ,20 ml of Ammonia (36%) and 10 ml of formaldehyde were added , and mixed along together with the whole mass the temperature of which increased from 31.2 to 33.8 C ْ . After drying at room temperature , the product was calcinated for 4 hours at 400 C ْ , the resulting mass 21.77gr. B-5-3 The adsorbent BG 18 grs of the granual pumice were mixed with 27 gr of the OMWW condensate , 38 grs of mixture was inserted in a cylinder and calcinated for 4 hours at 400 C B-5-4 The adsorbent BS: 18 grs of the rushed pumice ( ф= 0.1-0.5mm) were mixed with 27 gr of the OMWW condensate mentioned above fourteen grs of the adsorbent BS were received from calcinating 30 gr of the mixture in a closed cylinder for 4 hours at 400 C . B-5-5 Soap with the OMWW condensate. 500 ml of OMWW were dried at room temperature , 27 gr of the condensate were received, 10 grs of this condensate were well mixed with 990 gr of the hot liquid phase of the soap . the liquid new form of soap was powered out into a frame to harden in the desired form.
34
B-6 Measurements B-6-1 Removal of NO3- ions of the adsorbents BW-PC, BG-PC, BG, and BS was tested statically as for water pumped from Dooma (Al-Rehan) region as far as 10 Km from the city of Damascus . One gram of each sorbent was put in 50 ml of water for 48 hours , then the concentrations of Alkaline P , Alkaline M, Total Alkaline and NO3- ions were determined in addition to pH at room temperature. B-7 Results of experiments: Table ( 3 ) Performance of the prepared adsorbents for NO3- ions removal from a sample of Dooma ( Rehan) well water at 30 C ْ Sample ID pH Alkaline P (CaCO3)mg/l Alkaline M (CaCO3)mg/l Total Alkaline mg/l NO3 - concentration mg/l Percentage of NO3 – removal%
Sample BG-PC
BW-PC
BG
BS
8.13
9.96
10.27
10.02
10.53
40
600
400
400
660
340
700
840
580
900
380
1300
1240
980
1560
338.12
233.26
126.26
173.34
111.28
31.01
62.66
48.73
67.09
The results listed in table (3 ) show that the performance of the adsorbents in terms of the percentage of NO3- ions follow the order: BS>BW-PC>BG-PC>BG. B-8 Kinetics The kinetical study was focused on the adsorbent BS due to its good performance and low coast if it was compared with the other prepared adsorbents. One gram of the BS adsorbent was submerged in 50 ml of the
35
polluted with NO3- water for 48 hours at room temperature for different time periods . Results are listed in table ( 4 ) and represented by the kinetical curve fig( 2) Table (4 ) kinetic study of the adsorbent BS Time (hour) 0.00 24.00 30.00 36.00 42.00 48.00
Concentration mg/l 308.57 120.00 105.00 96.43 92.14 77.14
Removed NO3mg/l 0.00 188.57 203.57 212.14 216.43 231.43
Percentage of NO3 – removal % 0.00 61.11 65.97 68.75 70.14 75.00
Fig (2) Shows that, the efficiency of the BS adsorbent reached 61.11% in 24 h, and increased to 75 % after 48 hour, that is the time period required for decreasing the NO3- ions concentration to the needed levels can be known once the initial NO3- concentration is known ; This information helps minimize the coast of treatment. B-9 Determination of the adsorption parameters Study on NO3- ions adsorption in waters was conducted on the adsorbent BS . One gr of the BS adsorbent was submerged in 50 ml for each sample for 48 h at room temperature. The concentration of NO3- for each sample are shown in table (5 )
36
Table ( 5 ) Adsorption of NO3- ions on the adsorbent BS at different concentrations of NO3- in water Initial concentra tion of NO3mg/l
Concentrati on of NO3after adsorption mg/l
Initial concentrat ion (mmol/ l)
321.429 312.857 295.714 231.429 190.714 162.857 130.714 105.000
106.071 90.000 85.714 32.143 26.786 21.429 18.214 19.286
5.184 5.046 4.770 3.733 3.076 2.627 2.108 1.694
Equilibri -um concentr ation (mmol/ l) 1.711 1.452 1.382 0.518 0.432 0.346 0.294 0.311
Adsorbed 1/C 1/ α NO3- on 1 gr (mmol/l (mmol -1 /gr) (mmol/g) )-1 0.174 0.180 0.169 0.161 0.132 0.114 0.091 0.069
0.585 0.689 0.723 1.929 2.315 2.893 3.404 3.215
α/αm
5.758 5.564 5.905 6.222 7.564 8.768 11.022 14.467
0.660 0.683 0.644 0.611 0.502 0.433 0.345 0.263
We have found out that these data satisfy well the langmiur equation in adsorption:
θ
a KC a 1 KC m
- the fraction coverage - quantity of adsorbate on 1 gr BS a
a - the monolayer capacity on 1 gr BS m K C
- the equilibrium constant of adsorption - the equilibrium concentration of the adsorbate
1 Fig (3) represents as a function of of
1 The section cut off on the axis C
ordinate and the slope enabled us to determine amto be equal to 1/3.6= 0.277 (mmol/g) , whereas the slope made it possible to calculate the equilibrium constant of adsorption. Therefore, the calculated value of K is (1.547) (mmol)-1 .
37
Otherwise, in order to determine K, the equilibrium constant of adsorption in the region of low concentration Henry,s equation is applied and K is calculated from the slope of the straight like curve as shown in fig (4) to be equal to (1.4) (mmol)-1, that is the value of K is in the range (1.4-1.547) (mmol)-1 . B-10 The surface studies Studies on N2 adsorption at -196 C ْ to determine the surface properties of the studied adsorpents and research on the NO3- ions adsorption from waters were conducted as well . B-10-1 the good accordance with Langmiure equation indicates to the homogeneity of the surface of the BS adsorbent. B-11 The IR studies: The IR studies were conducted by mean of the device Jascon FT /IR-300 E. A sample of the studied adsorbent is pressed enough to form a transparent cyclic sample to be installed in special holder . the sample was moved to the IR spectroscopy apparatus to be exposed to the IR rays . B-11-1 The efficiency of prepared andsorbents as for NO3- removal from water follows the order BS>BW-PC>BG-PC>BG . Differences of adsorption activity of those products may be explained by comparing one IR specter of one adsorbent before and after the adsorption process and the IR spectrum of the carrier (Pumice) and by determination of the adsorption equilibrium constant K. Obvious absorption bands were observed as a result of the product of the OMWW calcinations being deposited on the carrier ( pumice) as for the absorbents BS and BW-PC fig(6,9) whereas most of those bands ; whereas most of those bands disappeared as for those two adsorbent as a result of the adsorption fig(7,10 ) this may be attributed to strong bonding between the 38
active centers of the adsorbent and the NO3- that resulted the change in the adsorption bands of the adsorbent observed before adsorption . As a result the adsorption activity has increased. This conclusion is in accord with the value of K the adsorption equilibrium constant (K>1). The value of K involves the quantity of the adsorption potential , that is , the interaction between the molecules of adsorbate and the active centers on the surface of the adsorbent due to the principles of statical thermodynamics of the surface layer. B-11-2 In order to remove the OMWW ultimately in an economically profitable and benifitable way one weight part from OMWW condensate has been added to 99 weight parts of the hot liquid phase of soap and stirred in the bulk until homogeneity is reached. The phenolic content of OMWW played the role of antioxidant. No microps or bacterias have been observed in the resulting hard soap at pH=7-9 for 6 months . The other components of the condensed OMWW have improved the quality of the foam of the soap if compared with the untreated with the OMWW condensate. The foam structure turned softer as for its appearance or for hair wash. B-11-3 Due to our suggested method no residual OMWW remain by use OMWW condensate in this sort of solid soaps as an additive. B-11-4 Due to our experiments : OMWW could not be used satisfactorily on large scale as an additive or component to shampoo . It can be used in its ordinary condition in very small rats about (0.09-0.18)% or (0.9-1.8)Kg of ordinary (unconensated OMWW) for one ton VS 200Kg /ton of OMWW that can be removed if compared with our suggested method for soap mentioned B-112,B-11-3. 39
5- Spectrum and Chart Percentag removal of NO3- %
80
y = -0.038x2 + 3.3211x + 0.5225
70
2
R = 0.9932
60 50
Fig ( 2) kinetical study on the adsorbent BS
40 30 20 10 0 0
6
12
18
24
30
36
42
48
54
Time (hour) fig (
2 1
)
Kinetical study on adsorbent BS
16.00 14.00 y = 2.2546x + 3.7193 R2 = 0.7035
12.00
1/a (mmol/g)-1
10.00
1/α
(mmol/g)_1
8.00 6.00 4.00 2.00 0.00 0.000
0.500
1.000
1 Fig (3)
1.500
ƒ
2.000
1 C
2.500
3.000
3.500
4.000
1.600
1.800
1/C (mmol/l)-1
for the adsorbent
a/am mmol/g
0.800 m 0.700 0.600 0.500 0.400 0.300 0.200 0.100 0.000 0.000
0.200
0.400
0.600
0.800
1.000
1.200
1.400
C mmol/l
C انتوازني a/am تابعية انشكم fig (4) α/ αmنهتركيس = ƒ( C ) for the )3( adsorbent 40
BS
Fig ( 5) IR Spectrum for crushed pumice
Fig (6 ) IR Spectrum for BS before adsorption
Fig (7 ) IR Spectrum for BS after adsorption NO3 -
41
Fig ( 8 ) IR Spectrum of pumice wool
Fig (9) Spectrum of BW-PC before adsorption
Fig( 10) IR Spectrum of BW-PC after adsorption NO3 -
42
Fig ( 11) Spectrum of the crushed pumice
Fig( 12 ) IR Spectrum of BG-PC before adsorption
Fig( 13 ) IR Spectrum of BG-PC after adsorption NO3 43
Fig ( 14) Spectrum of the crushed pumice
Fig ( 15) IR Spectrum of BG before adsorption
Fig ( 16) IR Spectrum of BG after adsorption NO3 44
Industrial chart for removing OMWW by carrying of its condensate on Syrian pumice industry Pumice in its different forms
OMWW Condensate
Solar Energy or another
OMWW
Mixing
Drying
Calcination at 400 Cْ
Cooling
Granular separating Storage
45
Industrial chart for removing OMWW by employing its condensate in Soap Industry OMWW
Solar Energy or any other energy OMWW Condensate
Storage 0f OMWW Condensate Hot Liquid Phase of soap
≈ 1% ≈99%
Stirring
OMWW Soap Hardening on frame surface
One ton of the soap with OMWW “ removes” { 200 Kg of ordinary OMWW ≈10 Kg condensate}
Notices: A sample of the new soap with OMWW can be presented if required
Soap Formation
Soap Packing
Storage
46
4- What claimed to: 4-1 Removal of OMWW and OMWW condensate by carrying it on Syria pumice to Produce adsorbents for removing NO3- ions from polluted water . 4-2 Use of Syria Pumice and Wool Pumice as a carrier in adsorbents industry . 4-3 Recirculation of pumice for use as a carrier of OMWW.
4-4 Use of mixtures of pumice and bentonite as carrier of OMWW.
4-5 Use of OMWW condensate in solid soap industry as a valuable material.
4-6 Removal of OMWW on large scale by condensing it by means of solar energy or any other energy and employing it as an additive of antioxidant and foam softening properties in novel solid soap production
47
5- Abstract Removal of OMWW and OMWW condensate has been carried out on Syrian pumice and wool pumice to Produce adsorbents for removing NO3ions from polluted water .We have used the OMWW condensate on large scale by [condensing the ordinary OMWW by means of solar energy] as an additive of antioxidant and foam softening properties in a novel solid soap production .
Key words: Olive Mill Wastewater (OMWW), Adsorbent, Nitrate ion, Pumice, Basaltic wool, Bentonite, Solid soap.
48
6- References 1- P.K.GOEL, Water Pollution-Causes, Effects and control, P(197-198). New Delhi.1997. 2- Yazjy, Wareef, M.Sc. Thesis P(10-11) Damascus University, Faculty of sciences, (2004). 3- T.M. Addiscott, NITRATE, AGRICULTURE AND THE ENVIRONMENT, UK, P (27-28,30-40) , 2005 ٔصاسح,45 سلى. يٍبِ انششة انًشاجؼخ األٔنى, ٍْئخ انًٕاصفبد ٔانًمبٌٍس انؼشثٍخ انسٕسي- 4 .1994 ,انصُبػخ يٍبِ انصشف انصحً انًؼبنجخ ألغشاض, ٍْئخ انًٕاصفبد ٔانًمبٌٍس انؼشثٍخ انسٕسٌخ- 5 .2003 , ٔصاسح انصُبػخ.2752 سلى,انشي كهٍخ, لسى ػهى األحٍبء انُجبتٍخ, انجضء انُظشي-ِ يٍكشٔثٍٕنٕجٍب انًٍب,ٌ ػذَب, ػهً َظبو. د- 6 .2004-2003 , جبيؼخ ديشك, انؼهٕو 7- M. Matosic, I. Mijatouic, and E. Hodzic , Nitrate Removal from Drinking Water Using Ion Exchange – Comparison of Chloride and Bicarbonate Form of the Resins, Chem.Biochem. Eng, P(141-146) ,2000. 8- Manal F. Abou Taleba, , Ghada A. Mahmouda, Samia M. Elsigenyb, El-Sayed A. Hegazya. , Adsorption and desorption of phosphate and nitrate ions using quaternary (polypropylene-g-N,N-dimethylamino ethylmethacrylate) graft copolymer, Journal of Hazardous Materials , P(372–379) ,2008.www.elsevier.com/locate/jhazmat 9- Stephany burge,Rolf Halden, Nitrat and Perchlorate Removal from Ground water by Ion exchange , University of Idaho Moscow,1999.
49
10- Aušra Mažeikienė1, Marina Valentukevičienė, Mindaugas Rimeika, Algirdas Bronislovas Matuzevičius, Regimantas Dauknys, Removal Of Nitrates and Ammonium Ions from water using natural sorbent Zeolite (Clinoptilolite), Dept of Water Management, Vilnius Gediminas Technical University, P(38–44) ,2008. اَفبق االلتصبدٌخ نُٕاتج انجشكُخ فً سٕسٌب,ػجذ انسالو.ًَ انتشكًب,فبسٔق.انؼًبدي
- 11
تمشٌش يُشٕس داخم انًؤسسخ, ) انصخٕس انجبصنتٍخ سكٕسٌب ٔ انطف-(انصخٕس انتشاكٍتٍخ .2004 , ديشك,انؼبيخ نهجٍٕنٕجٍب ٔ انثشٔح انًؼذٍَخ ( ( ٌٕ انتخهص يٍ يٍبِ ػصش انضٌت,ً ٔسٌف انٍبصج, ػذَبٌ دٌت. د,ٌحٍى ٔنٍذ انجضسح.د. أ- 12 ثتحٌٕهّ ( يغ تكبثف انًكَٕبد انفٍُٕنٍخ ػهى انسطح ٔ ثذَّٔ ) إنى يجبدلOMWW ٔ االصطُبع-І
شبسدي يشتشن يتؼذد انٕظبئف نًؼبنجخ انًٍبِ انًستخذيخ فً انصُبػخ
يجهخ جبيؼخ ديشك نهؼهٕو,يؼبنجخ انًٍبِ انحبٌٔخ ػهى األٌَٕبد راد األلطبس انصغٍشح .2009 , انؼذد األٔل25 األسبسٍخ –انًجهذ 13-
Francis Rouessac, Annich Rouessac, Chemical Analysis-
Second Edition, University of Lemans, France. 2007. 14-
Standard Methods for the Examination of Water and
Wastewater 20 th Edition, American Public Health Association, American Water Works association, Water Environment Federation,1999. ٔصاسح اإلسكبٌ ٔ انًشافك, دنٍم طشائك انتحبنٍم انًخجشٌخ نًشالجخ جٕدح يٍبِ انششة- 15 .2001 , ديشك,ثبنتؼبٌٔ يغ يُظًخ األيى انًتحذح نهطفٕنخ ٌٍَٕسف لسى,ً انمسى انؼًه- يؼبنجخ انًٍبِ ٔ َفبٌبد انًصبَغ,ً يحًذ ػه, انشؼبس.د.أ
- 16
.2008-2007. جبيؼخ ديشك, كهٍخ انُٓذسخ انكًٍٍبئٍخ ٔ انجتشٔنٍخ,انُٓذسخ انغزائٍخ 17 - LEO M. L. NOLLET , Handbook of water analysis- Second edition ,Boca Raton London New York, P(201-217) , 2007. 18- YA. GIRASIMOV and others, Physical Chemistry, Vol 1, P(487), Mir Publishers, Mosco,1974. 50
19- Syrian patent number 5654, 2008/2009, examined by WIPO ( IC/09/2843/SY-BG )
51
ػُٕاٌ االخزشاع: -1انزخهض يٍ OMWWثزسٕٚم يكثلّ إنٗ يبدح يبصح أل ٌٕٚانُزشاد ٔ إنٗ يبدح يضبكخ يسغُخ نهشؿبء ٔ يضبدح نألكغذح ك ٙطُبػخ انظبثٌٕ انظهت ثشاءح إضبكٛخ نهجشاءح سهى 5654
أ.د ٚسٔ ٗٛنٛذ انجضسح ٔ ٔسٚق انٛبصخٙ
1
2
أ -انسبنخ انزوُٛخ انغبثوخ
أ -1-انٕطق انلُ ٙنالخزشاع انششذ انًلظم نالخزشاع
ال ٓشزشًًب ٓزؼذد اُٞظبئق عذ٣ذا ًػِ ٠شٌَ أ -1-1-يٍ زٛث اندذّح :اطـ٘ؼ٘ب ٓجبد ً ؽج٤جبد ثو٤بط ≈ ٖٓ ِْٓ 0.5صالصخ ٌٓٗٞبد : ٢ٛ ٓ - 1بء اُغلذ ) -2 (OMWWاُج ِٕٞ٤اُغٞس ٖٓ) ١رَ ؽغبس ؽِت) -3اُض٤ُٞ٣ذ اُؼٔبٗA٢ أ -2--1-يٍ زٛث انخطٕح اإلثزكبسٚخ :رْ ألٓ ٍٝشح اُزخِض ٖٓ ٓبء اُغلذ OMWWثادخبُٚ ًٌٓٗٞب ٛبًٓب كٓ ٢جبدٍ أ ٢ٗٞ٣رشبسًٓ ٢جزٌش ٓزؼذد اُٞظبئق ٣ ٝغ ْٜك ٢كؼبُ٤خ أُجبدٍ ئعٜبًٓب ع٤ذاً. أ -3--1-هبثهٛخ انزطجٛن انظُبػٗ : ٙش ٟرُي ك ٢أُخـؾ اُظ٘بػ ٢أُشكن ( طلؾخ ٝ ) 14ك٢ ٗض اُجشاءح أُوزشؽخ.
2
أ -4-1-ك ٢أٓ ٖٓ ١شاًض اُجؾش ك ٢اُذ ٍٝأُٜزٔخ ثٔبء اُغلذ ٣ ُْ OMWWزْ اُزخِض ؽز٠ آُ ٖٓ ّٞ٤بء اُغلذ أُِِٞس ثزؾ ِٚ٣ٞئُٓ ٠جبدالد أ٤ٗٞ٣خ ثبالشزشاى ٓغ اُج ِٕٞ٤اُغٞس ١اُؾب١ٝ ٗٞٓ55%زٔٞس٤ِِٗٞ٣ذ ٝاُض٤ُٞ٣ذ اُؼٔبٗ. A ٢ ٞٗ ٝسد كٔ٤ب ٗ ٢ِ٣زبئظ اُزؾِ َ٤اٌُ٤ٔ٤بئ ٖٓ ٌَُ ٢اُج٘ز٤ٗٞذ ٝاُض٤ُٞ٣ذ ٓ ٝبء اُغلذ OMWWك٢ اُغذا٣ ٝ )3,2,1( ٍٝج ٖ٤اُشٌَ ( )1اُظ٤ؾ اٌُ٤ٔ٤بئ٤خ ُجؼغ األشٌبٍ أُٞعٞدح ك.OMWW ٢ ٌٖٔ٣روذ ْ٣ػ٘٤خ ٖٓ ًَ ٖٓ ٛز ٙأُ٘زغبد ػ٘ذ اُـِت. اندذٔل ) (1انزشكٛت انكًٛٛبئ ٙنهجٛهٌٕ انغٕس٘ انًكٌٕ W%
AL2O3 12.18
CaO 8.22
CL>0.002
Cr2O3 0.044
F0.020
انًكٌٕ W%
Mn2O3 0.150
Na2O >0.06
P2O5 0.082
SO3 >0.002
SiO2 46.38
K 2O 0.438
Fe2O3 8.52 TiO2 1.12
MgO 8.34 L.O.I 14.18
اندذٔل ) (2انزشكٛت انكًٛٛبئ ٙنهضٕٚنٛذ انؼًبَA ٙ انًكٌٕ W%
Na2O 17.38
AL2O3 29.24
SiO2 32.88
H 2O 20.63
اندذٔل ( ) 3يٕاطلبد ًَٕرج ػٍ يٛبِ اندلذ انُبردخ ػٍ طشٚوز ٙانضـط ٔ انطشد انًشكض٘ انًبدح األط انٓٛذسٔخُٙٛ انًٕاد اندبكخ انكثبكخ انضٚذ انغكبكش انًشخؼخ انلُٕٛالد انًزؼذدح أٔسرٕ د٘ كُٕٛل ْٛذسٔكغ ٙرٛشٔصٔل سيبد COD َزشٔخ ٍٛػضٕ٘ كٕعلٕس كهٙ طٕدٕٚو ثٕربعٕٛو كبنغٕٛو
انطشٚوخ انزوهٛذٚخ 5.73-4.73 266.00-15.50 1.09-1.02 11.50-0.12 67.10-9.70 14.30-1.40 13.30-0.90 937-71 42.60-4.00 389.50-42.00 1106-154 915-157 285-38 5000-1500 408-58
انٕزذح pH g/l g/l g/l g/l g/l mg/l g/l g/l mg/l mg/l mg/l mg/l mg/l
3
انطشٚوخ انسذٚثخ 4.55-5.89 161.20-9.50 1.046-1.007 29.80-0.41 34.70-1.60 7.10-0.40 6.00-0.30 426-43 12.5-0.40 199.20-15.20 966-140 485-42 124-18 2500-630 200-47
180-60 31.50-8.80 3.42-1.16 4.48-1.42 5.20-0.87 1.44-0.29 48.00-0.12 0.72-0.35
337-90 86.40-16.40 4.75-1.10 6.50-1.60 8.90-2.16 1.58-0.44 0.96-0.18 1.85-0.40 O
HO
OH
HO
ٕوٚيـُض ذٚزذ َسبط صَك ضُٛيُـ كمَٛ كٕثبنذ سطبص
mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l O
O
OH
OH
OH OH
OH
OH
p-hydroxybenzoic acid (p-HBA)
Gallic acid (GA)
O
CH3
O
OH
O
3,4-Dihydroxybenzoic acid Di-HBA
O
OH
CH3
O
OH
OH
Syringic acid (SA)
Vanillic acid (VA)
CH3
OH
HO tyrosol (Ty)
O
OH
OH
O
O
OH
OH
OH cinnamic acid CA
p-hydroxycinnamic acid p-HCA
o-hydroxycinnamic acid o-HCA
OH
HO O H3C
OH
OH O O
3,4-Dihydroxycinnamic acid Di-HCA
ferulic acid (FA)
4
OH
انشكم ) (1انظٛؾ انكًٛٛبئٛخ نجؼض انًشكجبد انلُٕٛنٛخ ٔ انًٕخٕدح ك ٙيٛبِ يؼبطش انضٚزٌٕ
أ -5-1-طشٚوخ انزسضٛش: أ 1-5-1-انًجبدل األٔل OMWBZ-PC ٓضط 100ؽ ٖٓ اُج ِٕٞ٤اُؾِج ٢ك ٢ث٤شش ٖٓ اُجالعز٤ي اُؾشاسٓ ١غ 100ؽ ٖٓ اُض٤ُٞ٣ذ ٓضعًب ع٤ذًا صْ أػ٤ق ئُٜ٤ب 100ؽ ٖٓ ٓ ٝOMWWضط ٓغٔٞع ٛز ٙأُٞاد ٓضعًب ع٤ذًا ؽز ٠اُؾظ ٍٞػِ٠ ,ه٤غذ دسعخ ػغ٘٤خ .رشًذ ٛز ٙاُؼغ٘٤خ ئُ ٠اُ ّٞ٤اُزبُ ٢ؽ٤ش ُٞؽظ أٜٗب أطجؾذ أًضش رٔبعٌبً ؽشاسح اُؼغ٘٤خ كٌبٗذ ٝ ّْ 31.3ثٜذف ئؽذاس اُزٌبصق أُزؼذد اُلٞ٘٤الد ك OMWW ٢أػ٤ق ثؼذ رُي( ٓ ٖٓ َٓ4ؾِٓ ٍٞبءاد االٓ36% ّٞ٤ٗٞثذ ٕٝرٔذ٣ذ ٖٓ َٓ2 ٝاٍكٞسّ أُذ٤ٛذ ) ٝرْ ٓضط أُغٔٞػخ اُ٘برغخ ؽز ٠اُزغبٗظ ؽ٤ش ُٞؽظ أٜٗب ارخزد هٞآًب هش٣جًب ٖٓ اُِذٗٝخ ٓ ٝغ اعزٔشاس ػِٔ٤خ أُضط ُٞؽظ اسرلبع ك ٢دسعخ ؽشاسح اُؼغ٘٤خ ؽزٜٗ ٠ب٣خ ػظٔٔٓ ّْ(34.4) ٠ب ٣ذٍ ػِ ٠ؽظٍٞ رلبػَ ٗبشش ُِؾشاسح داخَ اُؼغ٘٤خ ٞٛرلبػَ اُزٌبصق أُزؼذد ,عش ٟثؼذ رُي رغخّٖ اُؼغ٘٤خ اُ٘برغخ ك ٢ؽٔبّ ٓبئ ٢دسعخ ؽشاسر ٚثُٔ ّْ 60-50 ٖ٤ذح 40ده٤وخ ٓغ اُؼغٖ ًَ ػششح دهبئن ,رشًذ ٝ ,ِْٓ1-0.5رشى اُ٘برظ اُؼغ٘٤خ ؽز ٠اُ ّٞ٤اُزبُ ٢ؽ٤ش عشد ػِٔ٤خ اُزؾض٤ش ئُ ٠ؽج٤جبد ثو٤بط ٝ ,صٗذ 100ؽ ٖٓ اُؾج٤جبد اُغبكخ أُؾضش ُ٤غق ثجؾء ك ٢اُٜٞاء ٝك ٢دسعخ ؽشاسح اُـشكخ ٝٝػؼذ ك ٢اُلشٕ ك ٢دسعخ اُؾشاسح )ُٔ ّْ(400ذح 4عبػبد ,صْ ٝصٗذ اُؾج٤جبد اُجبسدح ك ٢اُّٞ٤ اُزبُ ٢كٌبٕ ٝصٜٗب )(90ؽ ,صْ ٝػغ 2ؽ ٖٓ أُجبدٍ ك20 cm3 ٢كٓ ٢ؾُِٔ 3N NaCl ٍٞذح 24عبػخ ك ٢دسعخ ؽشاسح اُـشكخ ؽ٤ش ؽظِ٘ب ػِ ٠أُجبدٍ اُظٞد ٢ٓٞ٣اُز ١ؿغَ ثبُٔبء أُوـش ٝعلق صْ ؽلظ الخزجبس كؼبُ٤ز ٚك ٢ئصاُخ ػغشح أُ٤ب.ٙ أ - 2-5-1-انًجبدل انثبَOMWBZ ٙ ٓضط 100ؽ ٖٓ اُج ِٕٞ٤اُؾِجٓ ٢غ 100ؽ ٖٓ اُض٤ُٞ٣ذ ٓضعًب ع٤ذًا ك ٢ث٤شش ٖٓ اُجالعز٤ي اُؾشاس ٝ ١أػ٤ق ئُ100 ٚ٤ؽ ٖٓ ٓبء اُغلذ ٝ ,OMWWثؼذ أُضط اُغ٤ذ رشًذ اُغِٔخ اُ٘برغخ ئُ ٠اُ ّٞ٤اُزبُ٣ ُْ ٝ ٢زْ ئػبكخ اُلٞسّ أُذ٤ٛذ أٓ ٝبءاد األٓ ّٞ٤ٗٞئُ ٠أُض٣ظ ُْ ٝرغش ػِ ٚ٤ا ػِٔ٤خ اُزٌبسف ,صْ اٗزوِ٘ب ٓجبششح ئُ ٠ػِٔ٤خ اُزؾض٤ش ٝرغل٤ق اُؾج٤جبد اُ٘برغخ . أخز 100ؽ ٖٓ اُؾج٤جبد اُ٘برغخ ٝٝػؼذ داخَ أعـٞاٗخ ٓـِوخ ك ٢اُلشٕ ثذسعخ ؽشاسح ْ ّ400 ُٔذح 4عبػبد ً ٝبٕ ٝصٕ اُ٘برظ 83ؽ ٝ.رْ اُؾظ ٍٞػِ ٠اُشٌَ اُظٞدًٔ ٢ٓٞ٣ب رًشٗب ك٢ اُلوشح.1-a- І أ -3-5-1-انًجبدل انثبنث BZ رْ ٓضط 100ؽ ٖٓ اُج ِٕٞ٤اُؾِج100 ٝ ٢ؽ ٖٓ اُض٤ُٞ٣ذ ٓغ 100ؽ ٖٓ أُبء أُوـش ك ٢ث٤شش ثالعز ٢ٌ٤ؽشاس ١ؽ٤ش ػغ٘ذ أٌُٗٞبد ع٤ذًا ٝرشًذ ئُ ٠اُ ّٞ٤اُضبٗ ٢صْ اعش ١ػِ٤ب ػِٔ٤خ اُزؾض٤ش ٝاُزغل٤ق٣ ُْٝ .ؼق OMWWثٜذف أُوبسٗخ ٓغ أُجبدٍ اُضبٗ ٝ ٢اُضبُش.
5
أخز 90ؽ ٖٓ اُؾج٤جبد ٝٝػؼذ داخَ أعـٞاٗخ ٓـِوخ ك ٢كشٕ دسعخ ؽشاسرُٔ ّْ 400 ٚذح أسثغ عبػبد ٝثؼذ اُزجش٣ذ ًبٕ اُٞصٕ 86ؽ ٝ ,رْ اُؾظ ٍٞػِ ٠أُجبدٍ اُظٞد ٢ٓٞ٣ث٘وغ 10ؽ ٖٓ اُؾج٤جبد اُ٘برغخ كٓ ٢ؾًِِٞ ٍٞس اُظٞدُٔ 3N NaCl ّٞ٣ذح 24عبػخ صْ اُـغَ ٝاُزغل٤ق.
أ -6-1-انوٛبعبد رْ رؾؼ٤ش أُبء اُوبع ٢أُغزخذّ ك ٢اخزجبس أداء أُجبدالد اُشبسد٣خ ثؾَ ( (2ؽ CaCl2.xH2O )(M=110.99ؽ 2+ؽ ٖٓ MgSO4.7H2Oك ٢أُبء أُوـش ٝئرٔبّ اُؾغْ ئُُ1 ٠زش . ٝػغ) (1ؽ ٖٓ أُجبدٍ اُشبسد ١ػِ ٠عش٣ش ٖٓ اُظٞف اُضعبع ٢ك ٢ػٔٞد اُزجبدٍ اُزٓ ١غبؽخ ٓوـؼ ٝ , cm2 1 ٚرْ رؼٓ ٖ٤٤ؾز ٟٞأُبء ٖٓ أٗٞ٣بد اٌُبُغ ٝ ّٞ٤أُـ٘ض ّٞ٣ػِ ٠اُشٌَ اُزبُ: ٢ ه٤غذ اُوغبٝح االثزذائ٤خ اٌُِ٤خ ٝ,اٌُبُغ٤ٓٞ٤خ ٝأُـ٘ض٤ٓٞ٣خ ,صْ ٓشسد هـلبد ٖٓ ٛز ٙأُ٤ب ٙاُوبع٤خ ػِ ٠أُجبدٍ ؽغْ ًَ هـلخ ٝ َٓ50ه٤غذ اُوغبٝح اٌُِ٤خ ثٔؼب٣شح ًَ ٖٓ َٓ5هـلخ ثٔؾٍِ ٞ M 0.01 EDTAثؼذ ئػبكخ ٖٓ َٓ1أُؾِ ٍٞأُٞه ٢أُؾؼش ٖٓ ( 54ؽ ٖٓ ًِٞس األّٓٞ٤ٗٞ اُجِٞس ١ك٤ٛ َٓ440 ٢ذسًٝغ٤ذ األًٓ ّٞ٤ٗٞضبكز 0.91 ٚصْ ٔ٣ذد أُؾِ ٍٞئُُ1 ٠زش ثبُٔبء أُوـش ( ٓغ 0.5-0.1ؽ ٖٓ ٓشؼش أعٞد األسًٞ٣ش T ّٝئُ ٠اُؼ٘٤خ أُلؾٞطخ. رْ رؼٓ ٖ٤٤ؾز ٟٞأٗٞ٣بد Ca+2ثبُـش٣وخ رارٜب ثبعزجذاٍ أُشؼش اُغبثن ثٔشؼش أُ٤شًٝغ٤ذ ٝ ,ئػبكخ ٓؾِ NaOH ٍٞػٞػًب ػٖ أُؾِ ٍٞأُٞهُِٞ ٢ط ٍٞئُ. (13-12) pH ٠ /75 َٓ1صب ,ثؾ٤ش ٘٣وؾ أُبء عشد اُو٤بعبد ثذسعخ ؽشاسح اُـشكخ ٝػ٘ذ عشػخ رذكن هذسٛب اُؼغش ػِ ٠أُجبدٍ ٝروبط هغبٝح أُبء اُؼغش اُخبسط ٖٓ ػٔٞد اُزجبدٍ ئُ ٠إٔ ٣زغب ٟٝرشً٤ض أٗٞ٣بد Mg+2 ٝCa+2كٓ ٚ٤غ ٓضِٜٔ٤ب ك ٢أُبء اُذاخَ ئُ ٠ػٔٞد اُزجبدٍ ٝ ,ػ٘ذ رُي رؾغت عؼخ آزظبص أُجبدٍ. 3 ثؼذ ًَ ه٤بط ٣ؼبد ر٘ش٤ؾ أُجبدٍ أُذسٝط ثـٔش ٙأ(1 ( ١ؽ كٓcm (20) ٢ؾًِِٞ ٍٞس اُظٞدّٞ٣ ُٔ3Nذح 24عبػخ ك ٢دسعخ ؽشاسح اُـشكخ. أ -7-1-انُزبئح: ٗذسط ك ٢اُغذاٗ ) 6 , 5 , 4( ٍٝزبئظ اُغؼبد اُزجبدُ٤خ ُِٔجبدالد أُذسٝعخ اُغذ٣ذح ثبُـش٣وخ اُذ٘٣بٓ٤ٌ٤خ ٝثؼذ االعزخذاّ ػشش ٓشاد. +2 +2 اندذٔل ) (4انغؼبد انزجبدنٛخ نهًجبدالد انًذسٔعخ اندذٚذح يغ إَٔٚبد Mg ٔ Caثؼذ كم رُشٛط ( يٛه ٙيكبكئ ؿشاي 100/ٙؿشاو) OMWBZ رٕطٛق انًجبدل BZ OMWBZ-PC سهى انزُشٛط أعبعٙ يُشط نهًشح )(1 يُشط نهًشح )(2 يُشط نهًشح )(3 يُشط نهًشح )(4 يُشط نهًشح )(5
234.54 193.50 161.04 177.71 150.89 220.71
238.39 180.36 180.18 171.43 198.57 162.50
6
210.57 150.00 165.91 162.83 163.57 182.24
يُشط نهًشح )(6 يُشط نهًشح )(7 يُشط نهًشح )(8 يُشط نهًشح )(9 يُشط نهًشح)(10
انًزٕعط انسغبثٙ
202.61 194.64 183.92 187.20 160.08 187.89
207.54 196.16 206.29 169.64 165.00 188.73
171.60 162.00 167.80 136.00 136.00 164.41
اندذٔل ) (5انغؼبد انزجبدنٛخ نهًجبدالد انًذسٔعخ اندذٚذح يغ إَٔٚبد Ca+2ثؼذ كم رُشٛط )يٛه ٙيكبكئ ؿشاي 100/ٙؿشاو( رٕطٛق انًجبدل سهى انزُشٛط أعبعٙ يُشط نهًشح )(1 يُشط نهًشح )(2 يُشط نهًشح )(3 يُشط نهًشح )(4 يُشط نهًشح )(5 يُشط نهًشح )(6 يُشط نهًشح )(7 يُشط نهًشح )(8 يُشط نهًشح )(9 يُشط نهًشح)(10
انًزٕعط انسغبثٙ
OMWBZ
OMWBZ-PC
BZ
201.79 135.71 155.89 139.29 154.82 141.07 162.46 153.89 160.36 130.64 147.60 153.05
184.29 167.86 126.86 142.29 125.00 171.07 155.21 152.86 143.52 150.80 132.00 150.16
206.85 133.93 134.98 123.36 125.00 141.36 150.80 129.20 120.80 109.00 110.00 135.03
اندذٔل ) (6انغؼبد انزجبدنٛخ نهًجبدالد انًذسٔعخ اندذٚذح يغ إَٔٚبد Mg+2ثؼذ كم رُشٛط )يٛه ٙيكبكئ ؿشاي 100/ٙؿشاو( OMWBZ رٕطٛق انًجبدل BZ OMWBZ-PC سهى انزُشٛط أعبعٙ يُشط نهًشح )(1 يُشط نهًشح )(2 يُشط نهًشح )(3 يُشط نهًشح )(4 يُشط نهًشح )(5 يُشط نهًشح )(6 يُشط نهًشح )(7 يُشط نهًشح )(8 يُشط نهًشح )(9 يُشط نهًشح)(10
36.61 44.64 24.29 32.14 43.75 21.43 45.07 42.27 45.93 39.00 17.40
50.25 25.64 34.18 35.43 25.89 49.64 47.39 41.78 40.40 36.40 28.08
3.72 16.07 30.93 39.47 38.57 40.88 20.80 32.80 47.00 27.00 26.00
انًزٕعط انسغبثٙ
35.68
37.74
29.39
7
أ -8-1-زغبة ثبثذ رٕاصٌ رلبػم انزجبدل األ ٔ َٕٙٚعؼخ االيزظبص انؼظًٗ انًجبدالد انًسضشح: ٣غش ١رلبػَ اُزجبدٍ ث ٖ٤أٗٞ٣بد اُظٞد ّٞ٣أُٞعٞدح ػِ ٠عـؼ أُجبدٍ ٝأٗٞ٣بد اٌُبُغٝ ّٞ٤ أُـ٘ض ّٞ٣أُٞعٞدح ك ٢أُؾِ ٍٞؽغت أُؼبدُخ ثشٌِٜب أُجغؾ: + 2[Na ]s + [Ca+2]w = [Ca+2]s + 2 [Na+]w طهت يسهٕل طهت يسهٕل ٝثبُزبُ ٢رٌ ٕٞػجبسح صبثذ اُزٞاصٕ ًٔب:٢ِ٣
ػهٗ عطٕذ
[Ca 2 ] s [ Na ] 2w KT [ Na ] 2s [Ca 2 ] w
ؽ٤ش: :C1=[Ca+2]wرشً٤ض اٌُبُغ ّٞ٤أُٞعٞدح ك ٢أُؾِ ٍٞػ٘ذ ؽظ ٍٞاُزٞاصٕ. :S1= [Ca+2]sرشً٤ض أٗٞ٣بد اٌُبُغ ٝ ّٞ٤أُـ٘ض ّٞ٣أُزٞػؼخ ػِ ٠عـؼ أُجبدٍ أُٞعٞد ك٢ ُ1زش ػ٘ذ اُزٞاصٕ (رشً٤ض Ca+2هجَ ٝػغ أُجبدٍ كٗ ٚ٤بهظًب .(C1=[Ca+2]w : S2= [Na+]sرشً٤ض أٗٞ٣بد اُظٞد ّٞ٣اُوبثِخ ُِزجبدٍ ٝأُزجو٤خ ػِ ٠عـؼ أُجبدٍ أُٞعٞد ك٢ ُ1زش ٖٓ أُؾِ ٍٞػ٘ذ اُزٞاصٕ . :C2= [Na+]wرشً٤ض أٗٞ٣بد اُظٞد ّٞ٣أُٞعٞدح ك ٢أُؾِ ٍٞػ٘ذ اُزٞاصٕ ثؾ٤ش ٌٕٞ٣ .2[Ca+2]s= [Na+]w ٝهذ رْ رؼ ٖ٤٤اُزشاً٤ض اُزٞاصٗ٤خ ثبُـش٣وخ اُشاًذح ًٔب ٝطق أػالٝ , ٙرج ٖ٤اُغذا ٍٝاُزبُ٤خ (-9-8-7 ٗ )15-14-13-12-11-10زبئظ اُو٤بعبد ك ٢دسعبد اُؾشاسح أُخزِلخ (ٖٓ ٌَُ ْ ّ ( 50-40-30 أُجبدالد أُذسٝعخ ػِ ٠اُزٞاُ:٢ انًجبدل )(OMWBZ +2 اندذٔل )(7انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(OMWBZك ٙانذسخخ ْ 30و زدى EDTA انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبعٛخ
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ يٕل/نزش
11.1 19.8 37.25 42.5 51
22.2 39.6 74.5 85 102
زدى EDTA انالصو نًؼبٚش 5 يم يٍ انًسبنٛم ثؼذ انًؼبندخ 0.1 0.3 5.05 8.9 14.35
+2
+
C1=[Ca+2]w يٛه ٙيٕل/نزش
[Ca ]s يٛهٙ يٕل/نزش
C2=[Na+]w يٛه ٙيٕل/نزش
S2=[Na ]s يٛهٙ يٕل/نزش
[Na+]2w [Ca+2]w يٕل/نزش
[Na+]2s [Ca+2]s يٕل/نزش
0.200 0.600 10.100 17.800 28.700
22.000 39.000 64.400 67.200 73.300
44.000 78.000 128.800 134.400 146.600
239.360 205.360 154.560 148.960 136.760
9.680 10.140 1.643 1.015 0.749
2.604 1.081 0.371 0.330 0.255
1/S2 1
C1S2/C22
0.0247 0.0203 0.0941 0.1468 0.1826
0.0042 0.0049 0.0065 0.0067 0.0073
اندذٔل )(8انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(OMWBZك ٙانذسخخ ْ 40و زدى EDT A
][Ca+2 نهًسبنٛم األعبعٛخ
زدى EDT A
]C1=[Ca+2 wيٛهٙ يٕل/نزش
][Ca+2 sيٛهٙ يٕل/نزش
]C2=[Na+ wيٛهٙ يٕل/نزش
8
]S2=[Na+ sيٛهٙ يٕل/نزش
[Na+]2
[Na+]2
w
s
][Ca+2
][Ca+2
1/S2
C1S2/C2 2
انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبعٙ ح
يٛهٙ يٕل/نزش
انالصو نًؼبٚش 5 يم يٍ انًسبنٛم ثؼذ انًؼبندخ
9.100
18.200
0.050
0.100
19.150
38.300
0.650
1.300
37.000
36.200
72.400
6.050
12.100
60.300
120.600
42.500
85.000
12.55 0
25.100
59.900
119.800
163.560
51.000
102.00 0
17.4
34.800
67.200
134.400
148.960
w
s
يٕل/نزش
يٕل/نزش
18.100
36.200
247.160
13.104
3.375
74.000
209.360
4.212
1.185
162.760
1.202
0.439
0.572
0.447
0.519
0.330
1
0.004 0 0.004 8 0.006 1 0.006 1 0.006 7
0.0189 0.0497 0.1354 0.2860 0.2870
اندذٔل )(9انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(OMWBZك ٙانذسخخ ْ 50و زدى EDTA انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبعٛخ
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ يٕل/نزش
9.100
18.200
زدى EDTA انالصو نًؼبٚش 5 يم يٍ انًسبنٛم ثؼذ انًؼبندخ 0.100
0.200
19.15 0 36.20 0 42.50 0 51.00 0
38.300
0.600
1.200
72.400
5.300
10.600
85.000
11.40 0 16.65
22.800
102.00 0
]C1=[Ca+2 wيٛهٙ يٕل/نزش
[Ca+2]s يٛهٙ يٕل/نزش
]C2=[Na+ wيٛهٙ يٕل/نزش
]S2=[Na+ sيٛهٙ يٕل/نزش
18.00 0 37.10 0 61.80 0 62.20 0 68.70 0
[Na+]2 w +2
1/S2 [Na+]2
] [Ca
s
يٕل/نزش
s
36.000
247.360
6.480
3.399
74.200
209.160
4.588
1.179
123.600
159.760
1.441
0.413
124.400
158.960
0.679
0.406
137.400
145.960
0.567
0.310
1
][Ca+2
w
C1S2/C2 2
يٕل/نزش
33.300
0.004 0 0.004 8 0.006 3 0.006 3 0.006 9
0.0382 0.0456 0.1109 0.2342 0.2575
خذٔل )(10انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(OMWBZ-CPك ٙانذسخخ ْ 30و زدى EDT A انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبعٙ ح 11.100
22.200
19.800
39.600
0.500
37.250
74.500
4.700
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ يٕل/نزش
زدى EDT A انالصو نًؼبٚش 5 يم يٍ انًسبنٛم ثؼذ انًؼبندخ 0.100
يٕل/نزش
يٕل/نزش
0.200
22.000
44.000
230.560
9.680
2.416
1.000
38.600
77.200
197.360
5.960
1.009
9.400
65.100
130.200
144.360
1.803
0.320
[Na+]2 +2
+2
+
+
] C1=[Ca wيٛهٙ يٕل/نزش
] [Ca sيٛهٙ يٕل/نزش
] C2=[Na wيٛهٙ يٕل/نزش
] S2=[Na sيٛهٙ يٕل/نزش
9
[Na+]2
w
][Ca+2 w
1/S2
s
C1S2/C2
][Ca+2 s
2
1
0.004 3 0.005 1 0.006
0.0238 0.0331 0.0800
42.500
85.000
51.000
102.00 0
10.30 0 15.60 0
20.600
64.400
128.800
145.760
0.805
0.330
31.200
70.800
141.600
132.960
0.643
0.250
9 0.006 9 0.007 5
0.1810 0.2069
اندذٔل )(11انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(OMWBZ-PCك ٙانذسخخ ْ 40و زدى EDT A انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبعٙ ح 9.100
18.200
19.150
38.300
0.700
36.200
72.400
7.900
15.800
42.500
85.000
51.000
102.00 0
13.40 0 19.55 0
26.800
58.200
39.100
62.900
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ يٕل/نزش
زدى EDT A انالصو نًؼبٚش 5 يم يٍ انًسبنٛم ثؼذ انًؼبندخ 0.050
يٕل/نزش
يٕل/نزش
0.100
18.100
36.200
238.360
13.104
3.139
1.400
36.900
73.800
200.760
3.890
1.092
56.600
113.200
161.360
0.811
0.460
116.400
158.160
0.506
0.430
125.800
148.760
0.405
0.352
[Na+]2 ]C1=[Ca+2 wيٛهٙ يٕل/نزش
][Ca+2 sيٛهٙ يٕل/نزش
]C2=[Na+ wيٛهٙ يٕل/نزش
]S2=[Na+ sيٛهٙ يٕل/نزش
w
][Ca+2 w
[Na+]2
1/S2
s
C1S2/C2
][Ca+2 s
2
1
0.004 2 0.005 0 0.006 2 0.006 3 0.006 7
0.0182 0.0516 0.1990 0.3128 0.3675
اندذٔل ( )12انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(OMWBZ-PCك ٙانذسخخ ْ 50و زدى EDT A انالصو نًؼبٚش 5يم يٍ انًسبنٛم ثؼذ انًؼبندخ 0.050
]C1=[Ca+2 wيٛهٙ يٕل/نزش
][Ca+2 sيٛهٙ يٕل/نزش
]C2=[Na+ wيٛهٙ يٕل/نزش
]S2=[Na+ sيٛهٙ يٕل/نزش
0.100 1.400
18.10 0 36.90 0 57.50 0 59.80 0 65.60 0
زدى EDT A انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبط ٚخ
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ يٕل/نزش
9.100
18.200
19.15 0 36.20 0 42.50 0 51.00 0
38.300
0.700
72.400
7.450
14.900
85.000
12.60 0 18.20 0
25.200
102.00 0
[Na+]2
36.400
w
][Ca+2 w
[Na+]2 s
C1S2/C2
][Ca+2 s
يٕل/نزش
يٕل/نزش
36.200
238.360
13.104
3.139
73.800
200.760
3.890
1.092
115.000
159.560
0.888
0.443
119.600
154.960
0.568
0.402
131.200
143.360
0.473
0.313
10
1/S2
2
1
0.0042 0 0.0049 8 0.0062 7 0.0064 5 0.0069 8
0.0182 0.0516 0.1798 0.2730 0.3032
اندذٔل ( ) 13انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(BZك ٙانذسخخ ْ 30و زدى EDT A انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبط ٚخ 11.10 0 19.80 0 37.25 0 42.50 0 51.00 0
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ يٕل/نزش
زدى EDT A انالصو نًؼبٚش 5يم يٍ انًسبنٛم ثؼذ انًؼبندخ
] C1=[Ca wيٛهٙ يٕل/نزش
22.200
0.050
0.100
39.600
0.500
1.000
74.500
6.100
12.200
85.000
9.600
19.200
102.00 0
14.30 0
28.600
+2
][Ca+2
]C2=[Na+
]S2=[Na+
s
w
s
يٛهٙ يٕل/نزش
22.10 0 38.60 0 62.30 0 65.80 0 73.40 0
يٛهٙ يٕل/نزش
يٛهٙ يٕل/نزش
[Na+]2 w
[Na+]2 s
][Ca+2
][Ca+2
w
s
يٕل/نزش
يٕل/نزش
44.200
191.320
19.536
1.656
77.200
158.320
5.960
0.649
124.600
110.920
1.273
0.197
131.600
103.920
0.902
0.164
146.800
88.720
0.754
0.107
C1S2/C2
1/S2
2
0.0052 3 0.0063 2 0.0090 2 0.0096 2 0.0112 7
0.0098 0.0266 0.0872 0.1152 0.1177
اندذٔل) ( 14انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(BZ ك ٙانذسخخ ْ 40و زدى EDT A انالصو نًؼبٚش 5يم يٍ انًسبنٛم ثؼذ انًؼبندخ 0.050
] C1=[Ca wيٛهٙ يٕل/نزش
] [Ca sيٛهٙ يٕل/نزش
] C2=[Na wيٛهٙ يٕل/نزش
] S2=[Na sيٛهٙ يٕل/نزش
0.100
38.300
0.500
1.000
72.400
7.700
15.400
85.000
13.58 3 18.75 0
27.166
18.10 0 37.30 0 57.00 0 57.83 4 64.50 0
زدى EDT A انالصو نًؼبٚش 5 يم يٍ انًسبنٛم األعبط ٚخ
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ يٕل/نزش
9.100
18.200
19.15 0 36.20 0 42.50 0 51.00 0
102.00 0
[Na+]2 +2
37.500
+2
+
[Na+]2
+
w
][Ca+2 w
s
1/S2
C1S2/C2
][Ca+2
2
1
s
يٕل/نزش
يٕل/نزش
36.200
199.320
13.104
2.195
74.600
160.920
5.565
0.694
114.000
121.520
0.844
0.259
115.668
119.852
0.492
0.248
129.000
106.520
0.444
0.176
0.0050 2 0.0062 1 0.0082 3 0.0083 4 0.0093 9
0.0152 0.0289 0.1440 0.2434 0.2400
اندذٔل ( )15انزشاكٛض انزٕاصَٛخ ألَٕٚبد Ca+2 (Mg+2) ٔNa+ك ٙانًسهٕل ػهٗ انًجبدل )(BZ ك ٙانذسخخ ْ 50و زدى EDT A انالصو
][Ca+2 نهًسبنٛم األعبعٛخ يٛهٙ
زدى EDT A انالصو
]C1=[Ca+2 wيٛهٙ يٕل/نزش
][Ca+2 sيٛهٙ يٕل/نزش
]C2=[Na+ wيٛهٙ يٕل/نزش
11
]S2=[Na+ sيٛهٙ يٕل/نزش
[Na+]2 w +2
[Na+]2
1/S2
C1S2/C2
s
] [Ca
][Ca+2
w
s
2
1
نًؼبٚش 5 يم يٍ انًسبنٛم األعبط ٚخ
يٕل/نزش
9.100
18.200
نًؼبٚش 5يم يٍ انًسبنٛم ثؼذ انًؼبندخ 0.050
0.100
19.15 0 36.20 0 42.50 0 51.00 0
38.300
0.600
1.200
72.400
6.100
12.200
85.000
12.10 0 17.55 0
24.200
102.00 0
35.100
18.10 0 37.10 0 60.20 0 60.80 0 66.90 0
يٕل/نزش
يٕل/نزش
36.200
199.320
13.104
2.195
74.200
161.320
4.588
0.701
120.400
115.120
1.188
0.220
121.600
113.920
0.611
0.213
133.800
101.720
0.510
0.155
أ- 1-8-1-رؼ ٍٛٛثبثذ انزٕاصٌ انكًٛٛبئ ٔ ٙعؼخ االيزظبص األػظًٛخ: رؼ ٖ٤عؼخ االٓزظبص األػظٔ٤خ ٖٓ ٓغٔٞع رشً٤ض أٗٞ٣بد اُظٞد[Na ]S ّٞ٣ ٝأٗٞ٣بد اٌُبُغ ٝ ّٞ٤أُـ٘٤ض S1= [Ca+2]s ّٞ٣ػ٘ذ اُزٞاصٕ أ ١إٔ : * Sm=2S1+S2 ٝثبُؼٞدح ئُ ٠ه ْ٤صبثذ اُزٞاصٕ ٗغز٘زظ إٔ : +
0.0050 2 0.0062 0 0.0086 9 0.0087 8 0.0098 3
0.0152 0.0352 0.0969 0.1864 0.1994
=S2ػِ ٠عـؼ أُجبدٍ
2 S C 1 2 K 2 S C 2 1
K S2 C ٗ ٚ٘ٓ ٝغز٘زظ هٔ٤خ 2 1 S اُز٘٣ ٢زظ ٖٓ رؼ٣ٞؼٜب ك* ٢إٔ 1 C2 2 2K C S 1 1 S S 2 m
T 1 2 S C2 m 2 C1S2 1 2K ٖٓ ٝروبؿؼٓ ٚغ ٗؾظَ ػِ ٠خؾ ٓغزوِٚ٤ٓ ْ٤ ٝ ٝثشعْ اُخؾ اُج٤بٗ ٢ثٖ٤ S2 Sm C 22 1 ٓؾٞس اُؼ٘٤بد ٗؾظَ ػِ٣ ٚ٘ٓٝ S . ٠ؾغت صبثذ اُزٞاصٕ ٝ Kعؼخ االٓزظبص اُؼظٔSm ٠ m
ك ٢دسعخ اُؾشاسح أُؼـبح ًٔب ك ٢األشٌبٍ ( .)4,3,2 ٗٝج ٖ٤ك ٢اُغذا )17,16( ٍٝه ٖٓ ٌَُSm ٝK ْ٤أُجبدالد أُذسٝعخ
اندذٔل ) (16هٛى Sm ٔ Kك ٙدسخخ انسشاسح االػزٛبدٚخ انًجبدل OMWBZ OMWBZ-CP BZ
K 1.94475 1.736262 4.056406
12
( Smيٛه ٙيكبكئ ؿشاي100/ٙؽ) 222.22 219.78 188.67
اندذٔل ) (17هٛى ٔ Sm ٔ Kانلشم Sm=Sm-∆ (Sm)BZك ٙدسخخ انسشاسح االػزٛبدٚخ انًجبدل
K
( S mيٛه ٙيكبكئ ؿشاي100/ٙؽ)
BZ OMWBZ OMWBZ-CP
4.056 1.736 1.944
188.00 219.78 222.2
Sm=Sm-∆ (Sm)BZ
(يٛه ٙيكبكئ ؿشاي100/ٙؽ) 0 31.78 34.20
أ٣-1-1-8-1-الؽظ ٖٓ اُغذ( 17 ) ٝ(16 ) ٖ٤ُٝئٕ أٌُ OMWW ٕٞهذ أػبف ٓوذاسًا ٓؾغٞع ًب ٖٓ اُلؼبُ٤خ اُزجبدُ٤خ ٓوذاس %29 ٝ % 31 ٙثبُ٘غجخ ُِٔجبدُOMWBZ-PC ,OMWBZ ٖ٤ ػِ ٠اُزشر٤ت ٝ .ثبُشؿْ ٖٓ روبسة كؼبُ٤خ أُجبدُ ٖ٤األخ٤ش ٖ٣ئال إٔ كؼبُ٤خ OMWBZ-PCأًضش صجبرًب ثوِ ٖٓ َ٤ؽبُخ . OMWBZ أُ -2-1- 8-1-ذ ٟرجخ٤ش 500ؽ ٖٓ ٗ OMWWزغذ ًزِخ ُضعخ عٌٔ٤خ ٓوذاسٛب 27.66ؽ ٝ 1 4.407ؽ ٝ , ثزغخ 5 ٖ٤اٌُزِخ ك ٢اُذسعخ ّْ 120ؽز ٠صجب د اُٞصٕ أطجؼ ٝصٕ اُ٘برظ ثبُزٌِ٤ظ ثٔؼضٍ ػٖ اُٜٞاء أطجؾذ اٌُزِخ 1.606ؽ ٢ٛ ٝأٌُ٤خ أُٞعٞدح ك100 ٢ؽ ٓجبدٍ ٝ ٢ٛاُز ٢عججذ اُض٣بدح ٓ ٝ∆ Smوذاسٛب ٌٓ ٢ِ٤ٓ(34.2بكئ ؿشآ100/٢ؽ) أ ١أٜٗب شٌِذ ٖٓ % 31 كؼبُ٤خ أُجبدٍ اٌُِ٤خ. 500ؽ ٖٓ َٓ20كٞسّ أُذ٤ٛذ ئُ٠ أ - 3-1-8-1-ثؼذ ئػبكخ ٓ َٓ50بءاد األٓٝ ّٞ٤ٗٞ ٝ OMWWئعشاء ػِٔ٤خ اُزٌبصق ( (PCػِٜ٤ب صْ اُزغل٤ق ؽظِ٘ب ػًِ ٠زِخ ٓوذاسٛب 25.75ؽ, ُٝذ ٟرغخ ٖ٤اٌُزِخ اُؼبئذح ُ ٛ1/5ز ٙأٌُ٤خ ك ٢اُذسعخ ّْ 120ؽز ٠صجبد اُٞصٕ ُٞؽظ اٗزلبؿ صبثذ ٝ ًبٕ ٝصٕ اُ٘برظ 3.146ؽ ٝ.ثزٌِ٤ظ ٛز ٙاٌُزِخ ك ٢اُذسعخ ُٔ ّْ400ذح 4عبػبد ؽظِ٘ب ػًِ ٠زِخ ∆Sm ٓوذاسٛب 1.034ؽ ٛ ٝ,ز ٙاٌُزِخ ٢ٛأُغإُٝخ ػٖ اُض٣بدح ك ٢اُلؼبُ٤خ اُزجبدُ٤خ ٝهذسٛب =ٌٓ ٢ِ٤ٓ 31.78بكئ ؿشآ 100/ ٢ؿشاّ. أ ١أٜٗب شٌِذ ٖٓ % 29اُلؼبُ٤خ اُزجبدُ٤خ اٌُِ٤خ ٗ ٝؼزوذ ثإٔ اُزٌبصق اُؾبطَ ٞٛاُز ١أػـ٠ اُضجبد ٝاالعزوشاس اُ٘غج OMWBZ-PCُ ٢ثبُٔوبسٗخ ٓغ MOWBZئر عجت ٓض٣ذًا ٖٓ أُغبٓ٤خ ك ٢ث٘٤خ أُجبدٍ ثبُشؿْ ٖٓ روبسة ُِٔ ∆Smجبدُ ٌٖٔ٣ٝ. ٖ٤إٔ ٣ؼض ٟاٗخلبع ه ْ٤اٌُزِخ أُزخِلخ ػٖ رجخ٤ش ٖٓ َٓ500أُبدح كٛ ٢ز ٙاُؾبُخ ئُ ٠أُبء أُزشٌَ ٗز٤غخ ػِٔ٤خ اُزٌبصق صْ رجخش ٙكٔ٤ب ثؼذ.
أ -9-1-ؽغجذ ه ْ٤األثؼبد اُزشٓٞد٘٣بٓ٤ٌ٤خ ُِٔجبدالد أُجزٌشح ٖٓ اُؼالهزƒ 1 ٖ٤ ٝ F RTLnK ٝهذ أدسعذ ك ٢اُغذ ,(18 ) ٍٝاألشٌبٍ (.)7,6,5
T
LnK
اندذٔل ) (18األثؼبد انزشيٕدُٚبيٛكٛخ نهًجبدالد انًجزكشح ك ٙانذسخخ 30و ْ انًجبدل OMWBZ-PC OMWBZ BZ
∆H cal/mol -11923.045 -15102.526 -10730.76
∆F cal/mol -332.207 -400.385 -843.138
13
∆S e.u -38.254 -48.522 -32.632
أ -10-1-انزخهض يٍ إَٔٚبد انُزشاد ٔ NO3-األيَٕٕٛو NH4+ثذسخخ انسشاسح االػزٛبدٚخ رْ ه٤بط رشً٤ض األٗٞ٣بد اُغبثوخ ك ٢أُ٤ب ٙهجَ ٝثؼذ ر٘ش٤ؾ أُجبدٍ ثبعزخذاّ عٜبص Colorimeter Dr/890ػ٘ذ ؿٞٓ ٍٞعخ 400nmثبُ٘غجخ ُِ٘زشاد ٝؿٞٓ ٍٞعخ 425 nm ثبُ٘غجخ ُألٓ ّٞ٤ٗٞاُغذ)19( ٍٝ اندذٔل ) (19إصانخ إَٔٚبد انُزشاد ٔ األيَٕٕٛو يٍ و ٚبِ يسطخ انًؼبندخ ثذيشن ثذسخخ انسشاسح االػزٛبدٚخ انًجبدل OMWBZ OMWBZ-PC BZ
انُغجخ انًئٕٚخ إلصانخ NO3-ج 1ؽ يجبدل %ثؼذ انزُشٛط %هجم انزُشٛط 32.14 90.18 39.29 90.18 23.21 91.52
انُغجخ انًئٕٚخ إلصانخ NH4+ج 1ؽ يجبدل %هجم انزُشٛط %ثؼذ انزُشٛط 98.91 81.79 98.91 79.35 98.91 78.26
أٗ -1-10-1-ش ٟكٛ ٢زا اُغذ ٍٝأدا ًء ع٤ذًا ُِٔجبدالد كٔ٤ب ٣زؼِن ثأ ٕٞ٣األٓ ّٞ٤ٗٞهجَ ٝثؼذ اُز٘ش٤ؾ, ك ٢ؽ ٖ٤إٔ ٛزا األداء ع٤ذ ثبُ٘غجخ ُِ٘زشاد هجَ اُز٘ش٤ؾ ٣ ٝز٘بهض ئُ ٠اُضِش ثؼذ اُز٘ش٤ؾ ٌٖٔ٣ٝ ,إٔ ٣ؼض ٟرُي ئًُ ٠جش هـش أ ٕٞ٣اُ٘زشاد ٝ ,اٗخلبع شؾ٘ز ٝ ٚئُ ٠ص٣بدح رشً٤ض اُ٘زشاد ك٤ٓ ٢بٙ أُؾـخ ٝئُ ٠اإلؽبؿخ األ٤ٗٞ٣خ ٝاُغض٣ئ٤خ اُز ٌٖٔ٣ ٢إٔ رؼ٤ن أُغبٓبد ك ٢أُجبدالد. أ٣ ُْ -2-10-1-زجغ اُزجبدٍ ث ٝ NH4+ ٝ NO3- ٖ٤أٗٞ٣بد Na+ػِ ٠اُغـؼ هبٗ ٕٞاُزجبدٍ األ٢ٗٞ٣ ًٔب ك ٢ؽبُخ .Mg+2 ٝCa+2 أ ٌٖٔ٣ -3-10-1-رلغ٤ش االعز٘زبط ثبُشؾ٘خ اٌُٜشثبئ٤خ األطـش ٝثبُوـش األًجش أل ٕٞ٣اُ٘زشاد ( ٝ )d=1.89 Aأ ٕٞ٣األٓ ( d= 1.43A) ّٞ٤ٗٞئػبكخ ئُ ٠اُج٘٤خ أُغبٓ٤خ ُِٔجبدالد أُجزٌشح . أ -4-10-1-رْ رخل٤غ رشً٤ض ًَ ٖٓ أٗٞ٣بد اُ٘زشاد ٝاألٓ ّٞ٤ٗٞك ٢أُ٤ب ٙاُظ٘بػ٤خ أُِٞصخ اُ٘برغخ ػٖ ٓؾـخ ٓؼبُغخ أُ٤ب ٙك ٢دٓشن اُغذ. )19( ٍٝ أ - 5-10-1-ػ٘ذٓب عش ٟاخزجبس أُجبدالد ػِٓ ٠ؾبُ َ٤اُ٘زشاد أُخجش٣خ اُز ٢روَ رشاً٤ضٛب ػًٖ 100 ppmبٕ األداء ػبًُ٤ب عٞاء هجَ اُز٘ش٤ؾ أ ٝثؼذًٔ ٙب ك ٢اُغذ.)20( ٍٝ
14
اندذٔل ) ( 20إصانخ إَٔٚبد انُزشاد ٔ األيَٕٕٛو يٍ انًسبنٛم انزٚ ٙوم يسزٕاْب ػٍ 100ppm ك ٙدسخخ انسشاسح االػزٛبدٚخ. انًجبدل OMWBZ OMWBZ-PC BZ
انُغجخ انًئٕٚخ إلصانخ NO3-ج 1ؽ يجبدل %ثؼذ انزُشٛط %هجم انزُشٛط 100 100 100 100 100 100
انُغجخ انًئٕٚخ إلصانخ NH4+ج 1ؽ يجبدل %هجم انزُشٛط %ثؼذ انزُشٛط 70.97 84.38 72.75 85.31 73.86 83.87
أ -11-1-نذٖ اخزجبس كؼبنٛخ انًجبدالد األَٕٛٚخ انًجزكشح ك ٙانًسبنٛم انًبئٛخ ن KMnO4رج ٍٛيٍ انجٛبَبد انُبردخ أَٓب رزجغ هٕاَ ٍٛااليزضاص اندضٚئ ٔ ٙنٛظ أَظًخ انزجبدل األ.َٕٙٚ أ -1-11-1-أػـ ٠أُ٘زظ ٘ٓ BZؾً٘٤ب ٗٔٞرعً٤ب ٓشبثٜب ُٔ٘ؾ٘ ٢ال ٗـٔٞ٤س
KC 1 KC
ٓ غ َٓ٤
ؽبد كٓ ٢غبٍ اُزشاً٤ض اُظـ٤شح ُ ٓ , KMnO4غ ه ْ٤طـ٤شح ُِـجوخ األؽبد٣خ اُغض٣ئخ .am أ - 2- 11-1-أٓب ثبُ٘غجخ ُ OMWBZكوذ أظٜشد ٗزبئظ آزضاص KMnO4رٞاكوًب ع٤ذًا ٓغ ٓؼبدُخ كش٘٣ذُ٤ش )ٓ (a/m=KC1/nغ هٔ٤خ ػبُ٤خ ٗغجً٤ب ﻟ .am أ ٝ -3-11-1-أٓب آزضاص KMnO4ػِ OMWBZ-PC ٠كوذ أٗزظ ر٘بعجبً ؿشدً٣ب ٓغ اُزشاً٤ض اُظـ٤شح )ٓ ( a=amKCغ هٔ٤خ رغش٣ج٤خ ُ amروزشة ٖٓ هٔ٤زٜب ثبُ٘غجخ ﻟ ِٗ ٝ .OMWBZخض ٗزبئظ آزضاص KMnO4ػِ ٠أُ٘زغبد أُجزٌشح اُغذ.)21( ٍٝ اندذٔل ) ( 21هٛى Δam ٔ amن ايزضاص KMnO4ػهٗ BZ, OMWBZ, OMWBZ-PC ك ٙدسخخ زشاسح انـشكخ. انًجبدل األ َٕٙٚانًبص
amيٛه ٙيٕل/100ؽ Δamيٛه ٙيٕل /100ؽ
BZ
2.920
0
OMWBZ OMWBZ-PC
10.282 10.268
7.362 7.348
انًؼبدنخ KC 1 KC
)(a/m=KC1/n )( a=amKC
أ1-ة٣ -4-11-ؼٌظ اُغذ ( 21 ) ٍٝئعٜبٓب ًج٤شاً ُ OMWWك ٢اُلؼبُ٤خ االٓزضاص٣خ ٌَُ ٖٓ OMWBZ-PC ٝOMWBZثبُٔوبسٗخ ٓغ كؼبُ٤خ .BZ أ -12-1-عش ٟاخزجبس اُلظَ اُغض٣ئ ٢ك ٢اُغَٔ اُض٘بئ٤خ اُغبئِخ اُوـج٤خ ٝاُالهـج٤خ ػِ ٠عـٞػ أُ٘زغبد أُجزٌشح ُِغِٔخ اُغبئِخ ٣ ٝ CCL4 -CH3OHج ٖ٤اُغذ ٍٝاُ٘زبئظ ؽغت ٓؼبدُخ ع٤جظ 15
) m, 2 ( K 1) X 1 (1 X 1 1 ( K1, 2 1) X 1
G1
ٝرج ٖ٤األشٌبٍ (٘ٓ ) 10,9,8ؾ٘٤بد ع٤جظ اُزغش٣ج٤خ,
ِٗ ٝخض ك ٢اُغذٗ )22( ٍٝزبئظ ٛز ٙاُذساعخ. اندذٔل ) (22هٛى αٔ KBثبنُغجخ اليزضاص CH3OHٔ CCl4ػهٗ انًُزدبد BZ,OMWBZ-PC,OMWBZثذسخخ زشاسح انـشكخ انًجبدل OMWBZ OMWBZ-PC BZ
CCl4 Kß 20.753 37.735 20.753
CH3OH αm 0.107 0.148 0.127
Kß 37.735 53.778 81.000
αm 0.0826 0.156 0.100
رجٗ ٖ٤زبئظ اُغذ٤ٓ ٍٝالً أًجش ٗؾ ٞاالٓزضاص اُالهـج ٢ػ٘ذ ٓ OMWBZ-PCغ ر٘بهض ك ٢االٓزضاص اُوـج ٢ثبُ٘غجخ ٍ OMWBZ ٝOMWBZ-PCثبُٔوبسٗخ ٓغ خٞاص اُلظَ اُغض٣ئBZ ُ٢ ٓ2-16زشاً ٝ. أ٣ -13-1-زٞػغ اُج ِٕٞ٤اُغٞس ١اُخبّ هشة ؽِت ثـجوبد عٔبًزٜب رزشاٝػ ثٖ٤ ٣خزِق ػٖ ثو٤خ اُـؼبس٣بد ك ٢أٗ٣ ٚؾز ١ٞػِٗٞٓ50-55 % ٠زٔٞس٤ِٗٞ٣ذ ئػبكخ ئُ ٠ثبُ٤لٞسعِ٤ذ ٝاٌُبؤ٤٘٤ُٝذ ٝاُ٤ٜذسٌ٤ٓٝب ٝاٌُٞاسرض ٝاٌُشثٗٞبد اٌُِغ٤خ ٝأُـ٘ض٤ٓٞ٣خ ٝؿ٤شٛب ٗ ٝش ٟرشً٤جٚ اٌُ٤ٔ٤بئ ٢ك ٢اُغذ ٝ(1 ) ٍٝهذ ٗششٗب ك ٢أُشعغ ][ 7-4دساعخ ٓلظِخ ػٖ اُج ِٕٞ٤اُغٞس.١ أ٣- -14-1-الؽظ ك ٢عٔ٤غ ٓخــبد اُ ٝ DTAعٞد كؼَ ٓبص ُِؾشاسح ًج٤ش كٛ ٢ز ٙأُجبدالد ك ٢دسعبد اُؾشاسح أُ٘خلؼخ هجَ ٝثؼذ اُز٘ش٤ؾ ج ٔٓ NaClب ٣ذٍ ػِٝ ٠عٞد صٓش ٤ٛذسًٝغ٤ِ٤خ , ٛٝز ٙاُضٓش رِؼت دٝسٛب ك ٢ػِٔ٤خ االٓزضاص أُِؾن (.)12,11 أ٣ ُْ --15-1-الؽظ أ ١اخزالف كٓ ٢خــبدُِٔ X.R.Dجبدالد( ,OMWBZ,OMWBZ-PC ٖٓ)BZؽ٤ش هْٔ اُج٘ز٤ٗٞذ ٝاُض٤ُٞ٣ذ أُٔ٤ضح ٣ ُْٝ ,إصش اُز٘ش٤ؾ ث NaClأُِؾن (.)14,13 أ -16-1-ال ٞ٣عذ ٓؼبدٕ صوِ٤خ ٗبرغخ ػٖ أُجبدالد أُؾؼشح ًٔب ٓ ٞٛجٗ ٖٓ ٖ٤زبئظ رؾِ َ٤اُؼ٘٤بد أُبئ٤خ أُؼبُغخ ثٜز ٙأُجبدالد ثٞاعـخ عٜبص االٓزظبص اُزس GBC 932 AA١أُِؾن (. )1
16
أ -2-انشعٕو ٔ انًخططبد ٔ انًالزن انًخطط انظُبػ ٙإلصانخ يبء اندلذ OMWW ٓبء اُغلذ ص٤ُٞ٣ذ ػٔبٗA ٢
ث ِٕٞ٤ؽِج٢
ٓضط
رٜؼْ٤
كٞسّ أُذ٤ٛذ
ٓبءاد األّٓٞ٤ٗٞ رٌض٤ق ك ٢اُذسعخ ْ ّ 60-50
رؾض٤ش
رغل٤ق
رٌِ٤ظ
رجش٣ذ
رخضٖ٣
17
0.008 0.007 0.006
1/S2
0.005 0.004 0.003 0.002 0.010 0.030 0.050 0.070 0.090 0.110 0.130 0.150 0.170 0.190 2
C 1S2/C 2
( S2/1 )1بدالنة C 1S2/C 22في اندرجة 30و ْ نهمبادل OMWBZ انشكم 2
0.008 0.007 0.006
1/S2
0.005 0.004 0.003
0.250
0.150
0.200
0.050
0.100
0.002 0.000
C1S 2/C22
3
2
انشكم ( S2/1 ) 4بدالنت C1S2/C2في اندرجت 30وْ نهمببدل OMWBZ-PC
0.012 0.011 0.010 0.009
0.007 0.006 0.005 0.140
0.120
0.100
0.080
0.060
0.040
0.020
C1S2/C22 S2/1 ) 7بدالنت C1S2/C22في اندرجت 30وْ نهمببدل BZ انشكم ( 4
18
0.004 0.000
1/S2
0.008
1.600 1.400 1.200 0.800
Ln K
1.000 0.600 0.400 0.200 0.0033
0.0032 -1
)ْ(K
0.0031
0.000 0.003
1/T
انشكم ( LnK )5ثذالنخ 1/Tنهًجبدل BZ 1.400 1.000 0.600
0.0033
0.0031
0.0032
LnK
0.200
-0.200 0.0030 -0.600 -1.000
(Kْ)-1
-1.400
1/T
انشكم ( LnK )6ثذالنخ 1/Tنهًجبدل OMWBZ 1.400 1.000 0.600
0.0033
0.0031
0.0032
Ln K
0.200
-0.200 0.003 -0.600 -1.000
(Kْ)-1
-1.400 1/T
انشكم ( LnK )7ثذالنخ 1/Tنهًجبدل OMWBZ-PC
19
0.1
0.08
0.06
0.04
0.02
0 1.2
1
0.8
0.6
0.4
0.2
0
G -0.02
ٓ/ٍٞؽ -0.04
-0.06
-0.08
-0.1
-0.12
X
انشكم ( )8االيزضاص ك ٙاندًهخ انثُبئٛخ CCL4-CH3OHن OMWBZ
20
0.1000
0.0800
0.0600
0.0400
0.0200
1.2000
1.0000
0.8000
0.6000
0.4000
0.2000
0.0000 0.0000
G -0.0200
ٓ/ٍٞؽ -0.0400
-0.0600
-0.0800
-0.1000
X
انشكم ( )9االيزضاص ك ٙاندًهخ انثُبئٛخ CCL4-CH3OHن OMWBZ-PC
21
-0.1200
0.1
0.08
0.06
0.04
0.02
0 0.8
G
1.2
1
0.6
0.4
0.2
0 -0.02
ٓ/ٍٞؽ -0.04
-0.06
-0.08
-0.1
-0.12 X1
انشكم ( )10االيزضاص ك ٙاندًهخ انثُبئٛخ CCL4-CH3OHﻟ BZ
22
OMWBZ-PC ٕٙيٚانظٕد
11
23
OMWBZ-PC
12
24
OMWBZ-PC
X.R.D
13
25
OMWBZ-PC ٕٙيٚانظٕد
X.R.D
26
14
انًهسن ()1 َزبئح رسهٛم انًؼبدٌ انثوٛهخ
انًجبدل هجم انزُشٛط انًٛبِ انًهٕثخ يٛبِ يهٕثخOMWBZ+ يٛبِ يهٕثخOMWBZ-PC+ يٛبِ يهٕثخBZ+
رشكٛض انًؼبدٌ ثوٛهخ ( يٛكشٔؿشاو/نزش) Mn Pb Zn Cu Cd 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 رشكٛض انًؼبدٌ ثوٛهخ (يٛكشٔؿشاو/نزش) Mn Pb Zn Cu Cd 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
انًجبدل ثؼذ انزُشٛط يٛبِ يهٕثخ يٛبِ يهٕثخOMWBZ+ يٛبِ يهٕثخOMWBZ-PC+ يٛبِ يهٕثخBZ+
27
أ -3-االدػبءاد انًطهٕة زًبٚزٓب أ – 1-3-ؿش٣وخ ُِزخِض ٖٓ ٓ٤ب ٙاُغلذ أُِّٞصخ ) (OMWWثزؾِٜ٣ٞب آُ ٠جبدالد أ٤ٗٞ٣خ رشبسً٤خ ٓزؼذدح األؿشاع ٓإُلخ ٖٓ أٌُٗٞبد ( + OMWWث ِٕٞ٤عٞس + ١ص٤ُٞ٣ذ ػٔبٗ.)A ٢ أ -2-3-رؾؼ٤ش ٓجبدٍ عذ٣ذ ٖٓ OMWBZ-PCأٌُٗٞبد ( + OMWWث ِٕٞ٤عٞس+ ١ ص٤ُٞ٣ذ ػٔبٗٓ )A ٢غ رٌبصق ػِ ٠اُغـؼ ٌُِٔٗٞبد اُل٤ُٞ٘٤خ ُ .OMWW أ -3-3-رؾؼ٤ش ٓجبدٍ OMWBZثذ ٕٝثِٔشح ٌٓٗٞبد .OMWW أ -4-3-رؾؼ٤ش ٓجبدٍ ٖٓ اُض٤ُٞ٣ذ اُؼٔبٗ ٝ A ٢اُج ِٕٞ٤اُؾِج٘ٓ ٢لشد.BZ ٖ٣ أٓ -5-3-ؼبُغخ أُ٤ب ٙاُوبع٤خ ثٜز ٙأُجبدالد (ٝ ,)OMWBZ, OMWBZ-PC, BZؽغبة صبثذ اُزٞاصٕ ٝعؼخ االٓزظبص اُؼظُِٔٔ ٠جبدالد ٝؽغبة األثؼبد اُزشٓٞد٘٣بٓ٤ٌ٤خ ُٜز ٙأُجبدالد. أ -6-3-اُزخِض ٖٓ أٗٞ٣بد اُ٘زشاد ٝاألٓ ّٞ٤ٗٞك ٢أُ٤ب ٙأُِٞصخ ثٜب ثبُٔجبدالد ( OMWBZ, .)OMWBZ-PC, BZ أ -7-3-آزضاص ثشٓ٘ـ٘بد اُجٞربع ٖٓ ّٞ٤أُؾبُ َ٤أُبئ٤خ ػِٛ ٠ز ٙأُ٘زغبد( OMWBZ, .)OMWBZ-PC, BZ أ -8-3-اُلظَ اُغض٣ئ ٢ك ٢اُغَٔ اُغبئِخ اُوـج٤خ ٝاُالهـج٤خ ٝػِ ٠عـٞػ أُ٘زغبد أُجزٌشح ُِغِٔخ اُغبئِخ . CH3OH- CCl4 أ -9-3-رؼٓ ٖ٤٤خــبد ُٜ DTA, XRDز ٙأُجبدالد (.)OMWBZ, OMWBZ-PC, BZ أ- -10-3-عٔ٤غ األكٌبس اُز ٢رًشد ر٘ـجن ػِ ًَ ٠أٗٞاع اُض٤ُٞ٣ذ ٝ Aاُج٘ز٤ٗٞذ ٓغ ٓ٤ب ٙاُغلذ.
28
أ -4-انًهخــــض
رى ألٔل يشح انزخهض يٍ يٛبِ اندلذ انًهٕثخ نهجٛئخ OMWWثزسٕٚهٓب إنٗ يجبدالد إَٔٛٚخ رشبسكٛخ ػذٚذح انٕظبئق يغ انضٕٚنٛذ انؼًبَ ٔ A ٙانجٛهٌٕ انغٕس٘. أدد َغجخ أهم يٍ % 1يٍ انًبدح اندبكخ انًكهغخ انُبردخ ػٍ اَزشبس OMWWكٙ انًجبدل أٔ ػٍ ركبثق يزؼذد انلُٕٛالد انذاخهخ ك ٙرشكٛجٓب ػهٗ انغطر انلؼبنٛخ انزجبدنٛخ ثًب ٚوبسة
إنٗ صٚبدح كٙ
% 31يٍ أخم األَٕٚبد راد األهطبس انظـٛشح
) ٔ (Ca+2,Mg+2صٚبدح هذسْب % 200روشٚج ًب ك ٙزبنخ االيزضاص اندضٚئ ٙنجشيُـُبد انجٕربعٕٛو. إضبكخ إنٗ طالزٛخ انًجبدالد انُبردخ ك ٙإصانخ األَٕٚبد راد األهطبس انكجٛشح َغجً ٛب يثم ٔ, NH4+ ٔ NO3هذسرٓب ػهٗ انلظم ك ٙاندًم انثُبئٛخ انوطجٛخ ٔ انالهطجٛخ ٔ نىٚؼشف يُزح كٓزا ك ٙأ٘ يشكض ثسث ٙك ٙانؼبنى ززٗ ا.ٌٜ
انكهًبد انًلزبزٛخ ٓ:بء اُغلذ ,OMWWأُجبدٍ األ ٢ٗٞ٣أُظ٘غ ٖٓ ص٤ُٞ٣ذ) ,ئصاُخ ٓبء اُغلذٓ ,جبدالد أ٤ٗٞ٣خ.
29
(ٓبء اُغلذ ,ث,ِٕٞ٤
انًشاخغ-5-أ ذٕٛنٚيشاخغ انض 1 Breck D.W. 1974Zeolite Molecular Sieves-Structure,Chemistry and Use. Wiley Interscience, New York. 2 Breck, Zeolite Molecular Sieves, New York: Wiley(1979); cited in Rompp, Chemie Lexikon, Band 6,9. Auflage (1992), Georg Thieme Verlag, Stuttgart. 3 Allen, H.E.,Cho S.H. Neubecker T. A. 1983. Ion exchange and hydrolysis of type A Zeolite in natural water. Water Res. 17, 1871, 1879. ٘ذ انغٕسَٕٛيشاخغ انجُز 4 Y. W. Bizreh, Damascus University Journal Vol (18) N ْ= 5, part (2) page 7-38, (1989) 5 Hamwee, N. master degree dissertation P.29-39 Supervisered by Prof. Y. W. Bizreh, Damascus University (1996). 6 Shaheen Abeer, master degree dissertation P.47-52 Supervised by Prof. Y. W. Bizreh, Damascus University. 7 Abudullah, Suzan master degree dissertation P.39-74 Supervised by Prof. Y. W. Bizreh, Damascus University, Faculty of sciences (2003). يشاخغ يبء اندلذ 8 Isabel P. Marques. Anaerobic digestion treatment of olive mill wastewater for effluent re-use in irrigation. Departamento de Energias Renováveis, Instituto Nacional de Engenharia e Tecnologia Industria, 21 August 2000. 9 Basheer Sobhi,* Sabbah Isam, Yazbek Ahmad, Haj Jacob, Saleeba. Ahlam REDUCING THE ENVIRONMENTAL IMPACT OF OLIVE MILL WASTEWATER IN JORDAN, PALESTINE . 10 The treatment of olive oil milling wastewater. Objective and results of the CAT-MED. 5TH FRAMEWORK PROGRAMME -INCO-MED PROGRAMMECONFIRMING THE INTERNATIONAL ROLE OF COMMUNITY RESEARCH Shared Cost Actionsww2.unime.it/catalysis/cat-med. 11 MOUS: Food and agriculture organization of the United Nations, Online under URL: www.fao.org [last Access on 23.03.2005]. 12 MULINACCI, N., et al. (2001): Polyphenolic Content in Olive Oil Waste Waters and Related Olive Samples, Journal of Agricultural and Food Chemistry (2001) 49: Page: 1005 – 1009.
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13 FIORENTINO, A., et al. (2003): Environmental effects caused by olive oil mill wastewaters: Toxicity comparison of low-molecularweight phenol components, Journal of Agricultural and Food Chemistry (2003) 51: Page: 1005 – 1009. 14 Igor Kobek," Waste Treatment- TDC-OLIVE project" Framework Programme of the European Union http://www.tdcolive.net/documents/booklet/D14k_Waste_Treatment_ V1.0.pdf 15 ANONYMOUS: Food and agriculture organization of the United Nations, Online under URL: www.fao.org [last Access on 23.03.2005]. 16 ANONYMOUS: International Olive Oil Council, Online under URL: www.internationaloliveoil.org [last Access on 23.03.2005] 17 ANONYMOUS (2004): Project INASOOP - Integrated Approach to Sustainable Olive Oil and Table Olive Production (COLL-CT-2003500467) - Report on Relevant Olive Oil and Table Olives Production Techniques and Technologies, Pages: 20. ئداسح٢ضخ ك٣بد اُؾذٛ االرغب. خ٤ئ٤ اُضبُش ُإلداسح اُج٢ أُإرٔش اُؼشث. ٖ٤ٛ ؽبكظ شب18 بٜت ٓؼبُغز٤ُأعبٝ ئخ٤صخ ُِجُِٞٔاع أُُخِلبد اٞٗأٝ ّٜٞئخ ٓل٤صخ ُِجُِٞٔأُُخِلبد ا Management of Olive Mills Wastes in the Palestinian عبٓؼخ،٘ذعخُٜخ ا٤ًِ , خ٤٘٤ أُ٘بؿن اُلِغـ٢ب كٜئداسرٝ ٕٞز٣ٓخِلبد اُضTerritories .ٖ٤كِغـ-ٗبثِظ,خ٤٘ؿُٞاُ٘غبػ ا ٕٞز٣ذ اُض٣ ص٢خ ك٤ؼ٤خ اُـج٤ُٞ٘٤ٗغت أُشًجبد اُلٝ اعٞٗذ أ٣رؾذٝ دساعخ.ت ٗذاف٣ ٓؾٔذ د19 ذفٜ أُشآثبد ثٙزٛ ٖٓ ٙاٞ ٓؾز٠ِذ ػ٣وخ اعزخالص اُض٣ش ؿش٤ رأصٟٓذٝ ١سٞاُجٌش اُغ خ٤اُالره-خ٣سٞ ع,ٖ٣ عبٓؼخ رشش- خ اُضساػخ٤ُ آ-خ٣ّ األؿزِٞ هغْ ػ." دحٖٞ اُغ٤رؾغ عبٓؼخ دٓشن. ٕٞز٣ اُ٘ظبس أؽٔذ ٓؾٔذ"ؿش ٓؼبُغخ ٓبء اُغلذ اُ٘برظ ػٖ ػظش اُض20 .ب٣سٞخ ع٤٘ذعخ اُضساػُٜخ ا٤ًِ " .. ػبٓش٢ أ ؽو.اٞ كشاٗغ,ذ٤ ثٙ هش.ّ.د.أ. ٓؾٔذ,٢ِد أُ٘غذ ػ. أ. ٓؾٔذ,ش٤ٜبشْ شٛ د. أ21 ٕ ثبعزخذاّ روبٗبد األًغذح أُزوذٓخٞز٣خ اُ٘برغخ ػٖ ٓؼبطش اُض٤ اُظ٘بػٙب٤ُٔٓؼبُغخ ا . عبٓؼخ دٓشن,ِّٞخ اُؼ٤ًِ , ش٤اهَ" سعبُخ ٓبعغزُٞ٘د أٗظبف اٞعٞ ثٝ ًب٤ئٞأُؾلضح ػ .2004 خٚيشاخغ انًجبدالد انشبسد 22-Andrei A , Zagordni” Ion exchange Materials properties and Applications “ Elsvier, 2007.
31
ة – ششذ يلظم نالخزشاع ة -1-يٍ زٛث اندذح ة 1-1-اطـ٘ؼ٘ب ػذح ٓٞاد ٓبصح ٖٓ أٌُٗٞبد اُزبُ٤خ: ٓ -1بء اُغلذ ٓ -2غؾٞم اُخلبٕ اُجبصُز ٢هـش ؽج٤جبر -3 ِْٓ)0.5-0.1 ( ٚاُظٞف اُجبصُز-4 ٢ اُخلبٕ اُجبصُذ اُؾج٤ج٣ ٝ ٢زٔ٤ض ثزغبٗظ عـؼ اُؾج٤جخ ػِ ٠شٌَ ًش.١ٝ ة 2-1-رظ٘٤غ ٗٞع عذ٣ذ ٖٓ اُظبث ٕٞثبعزخذاّ ٌٓضق .OMWW ة 2-يٍ زٛث انخطٕح االثزكبسٚخ ة 1-2-رْ ألٓ ٍٝشح اُزخِض ٖٓ ٓبء اُغلذ OMWWثادخبًٌُٗٞٓ ٚب ٛبٓبً ٓغ اُخلبٕ اُجبصُز ٢ك٢ رظ٘٤غ ٓبدح ٓبصح إلصاُخ أٗٞ٣بد اُ٘زشاد ٖٓ أُ٤ب. ٙ ة 2-2-ئدخبٍ ٌٓضق OMWWك ٢ط٘بػخ اُظبثًٔ ٕٞبدح ٓؾغ٘خ ُِشؿٞح ٓ ٝؼبدح ُِزأًغذ. ة -3 -هبثهٛخ انزطجٛن انظُبػخ ٗ :ش ٟرُي ك ٢أُخـؾ اُظ٘بػ ٢أُشكن ( اُجشاءح أُوزشؽخ .
32
ٝ ) 46,45كٗ ٢ض
ة 4-انسبنخ انزوُٛخ نالخزشاع ة 1-4-ك ٢أٓ ٖٓ ١شاًض اُجؾش ك ٢اُذ ٍٝأُٜزٔخ ثٔبء اُغلذ
٣ ُْ OMWWزْ اُزخِض ؽز٠
آُ ٖٓ ّٞ٤بء اُغلذ أُِِٞس ثزؾ ِٚ٣ٞئُٓ ٠جبدالد أ٤ٗٞ٣خ ثبالشزشاى ٓغ اُج ِٕٞ٤اُغٞس ١اُؾب١ٝ ٗٞٓ55%زٔٞس٤ِِٗٞ٣ذ ٝاُض٤ُٞ٣ذ اُؼٔبٗ ٝ A ٢رؾ ِٚ٣ٞأ٣ؼًب ئُٓ ٠بدح ٓبصح ثبالشزشاى ٓغ ٓغؾٞم اُخلبٕ اُجبصُز ٝ ٢اُظٞف اُجبصُز ٢ر ٝاُزشً٤ت اٌُ٤ٔ٤بئ ٢أُج ٖ٤ك ٢اُغذ. ) 1 ( ٍٝ اندذٔل ( )1انزشكٛت انكًٛٛبئ ٙنهخلبٌ انجبصنزٙ انزشكٛت انكًٛٛبئٙ MgO
(4.50-8.99)%
SiO2
(41.82-47.09)%
Na2O
(2.05-4.83)%
Al2O3
(12.42-18.8)%
K2O
(0.88-1.90)%
TiO2
(1.050-3.37)%
CaO
(8.41-11.93)%
Fe2O3
(4.03-15.35)%
FeO
(3.40-10.34)%
ال عذ٣ذًا ٖٓ اُظبث ٕٞاُـج٤ؼ ٢ثاػبكخ ٌٓضق OMWW ةًٔ 2-4-ب ٗؼزوذ أٗ٘ب أٗزغ٘ب ألٓ ٍٝشح شٌ ً ئُ ٠اُـٞس اُغبئَ اُغبخٖ ٖٓ اُظبثٓ ٝ ٕٞضعٜٔب ٓؼبً هجَ اُزظِت. ٣ ٝج ٖ٤اُغذ )2 ( ٍٝاُزشً٤ت اٌُ٤ٔ٤بئًٔOMWW ِ ٢ب ٣ج ٖ٤اُشٌَ ( )1ط٤ؾ ٝأشٌبٍ اُلٞ٘٤الد أُزؼذدح أُٞعٞدح كOMWW ٢ اندذٔل ( ) 2يٕاطلبد ًَٕرج ػٍ يٛبِ اندلذ انُبردخ ػٍ طشٚوز ٙانضـط ٔ انطشد انًشكض٘ انًبدح األط انٓٛذسٔخُٙٛ انًٕاد اندبكخ انكثبكخ انضٚذ انغكبكش انًشخؼخ انلُٕٛالد انًزؼذدح أٔسرٕ د٘ كُٕٛل ْٛذسٔكغ ٙرٛشٔصٔل سيبد
انٕزذح pH g/l g/l g/l g/l g/l
انطشٚوخ انزوهٛذٚخ 5.73-4.73 266.00-15.50 1.09-1.02 11.50-0.12 67.10-9.70 14.30-1.40 13.30-0.90
انطشٚوخ انسذٚثخ 4.55-5.89 161.20-9.50 1.046-1.007 29.80-0.41 34.70-1.60 7.10-0.40 6.00-0.30
mg/l
937-71
426-43
g/l
42.60-4.00
12.5-0.40
33
199.20-15.20 966-140 485-42 124-18 2500-630 200-47 180-60 31.50-8.80 3.42-1.16 4.48-1.42 5.20-0.87 1.44-0.29 48.00-0.12 0.72-0.35
389.50-42.00 1106-154 915-157 285-38 5000-1500 408-58 337-90 86.40-16.40 4.75-1.10 6.50-1.60 8.90-2.16 1.58-0.44 0.96-0.18 1.85-0.40 O
g/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l mg/l HO
OH
HO
COD ٍٕ٘ ػضَٛزشٔخ ٙكٕعلٕس كه ٕوٚطٕد ٕوٛثٕربع ٕوٛكبنغ ٕوٚيـُض ذٚزذ َسبط صَك ضُٛيُـ كمَٛ كٕثبنذ سطبص O
O
OH
OH
OH OH
OH
OH
p-hydroxybenzoic acid (p-HBA)
Gallic acid (GA)
O
O
OH
O
O
CH3
3,4-Dihydroxybenzoic acid Di-HBA
OH
CH3
O
OH
OH
Syringic acid (SA)
Vanillic acid (VA)
CH3
OH
HO O
tyrosol (Ty)
OH
OH
O
O
OH
OH
OH cinnamic acid CA
p-hydroxycinnamic acid p-HCA
o-hydroxycinnamic acid o-HCA
OH
HO O H3C
OH
OH
OH O O ferulic acid (FA)
3,4-Dihydroxycinnamic acid Di-HCA
ٌٕزٚبِ يؼبطش انضٛ يٙخ ٔ انًٕخٕدح كُٕٛنٛخ نجؼض انًشكجبد انلٛبئًٛٛؾ انكٛ(انظ1 ) انشكم 34
ة -5-طشٚوخ انزسضٛش ة 1-5-رسضٛش انًبدح انًبصح BW-PC أػ٤ق OMWW َٓ 300ئُ 18 ٠ؽ طٞف ثبصُز ٝ ٢رشًذ اٌُزِخ ُزغق كٌبٕ ٝصٕ اُ٘برظ 37ؽ .ه٤غذ دسعخ ؽشاسح اٌُزِخ اُغبكخ كٌبٗذ , ّْ 34أػ٤ق ُٜب ٖٓ َٓ 12األٓ٤ٗٞب أُشًضح ( ٝ )%36 ٖٓ َٓ 6اُلٞسّ أُذ٤ٛذ ٝرْ ٓضط أُغٔٞػخ اُ٘برغخ ؽز ٠اُزغبٗظ ؽ٤ش ُٞؽظ اسرلبع ك ٢دسعخ اُؾشاسح اٌُزِخ ؽزٔٓ ّْ38 ٠ب ٣ذٍ ػِ ٠ؽظ ٍٞرلبػَ ٗبشش ُِؾشاسح ,صْ عش ٟثؼذ رُي رغل٤ق اٌُزِخ ك ٢اُٜٞاء اُؼبد ١كٌبٕ ٝصٜٗب 37.8ؽ ٝٝ ,ػؼذ ك ٢اُلشٕ ك ٢دسعخ اُؾشاسح
ُٔ ّْ 400ذح 4
عبػبد ,كٌبٕ ٝصٕ اُ٘برظ ثؼذ اُزجش٣ذ 25.6ؽ . ة 2-5-رسضٛش انًبدح انًبصح BG-PC ٓضط 18ؽ خلبٕ ثبصُز ٢ؽج٤جٓ ٢غ
27ؽ ٓبدح ٌٓضلخ ٗبرغخ ػٖ رٌض٤ق
OMWWك ٢دسعخ
اُؾشاسح اُؼبد٣خ ,صْ أػ٤ق َٓ 20أٓ٤ٗٞب ٓشًضح ( َٓ 10 ٝ )%36كٞسّ أُذ٤ٛذ ئُ ٠أُض٣ظ اُغبثن اُزً ١بٗذ دسعخ ؽشاسر ّْ 31.2 ٚكبسرلؼذ ئُ ّْ 33.8 ٠ثؼذ اإلػبكخ اُغبثوخ ٝأُضط اُغ٤ذ .عشٟ ثؼذ رُي رغل٤ق أُض٣ظ ك ٢اُٜٞاء اُؼبد ١كؾظِ٘ب ػًِ ٠زِخ ٝصٜٗب 44.26ؽ ,رْ ٝػؼٜب ك ٢كشٕ دسعخ ؽشاسرُٔ ّْ 400 ٚذح 4عبػبد كٌبٕ ٝصٕ اُ٘برظ ثؼذ اُزجش٣ذ 21.77ؽ. ة 3-5-رسضٛش انًبدح انًبصح BG ٓضط 18ؽ ثبصُذ ؽج٤جٓ ٢غ 27ؽ ٖٓ أُبدح أٌُضلخ ِ . OMWWأخز 35ؽ ٖٓ أُض٣ظ اُغبثن ٝٝػغ ك ٢أعـٞاٗخ ٓـِوخ ك ٢كشٕ دسعخ ؽشاسرُٔ ّْ 400 ٚذح 4عبػبد كٌبٕ ٝصٕ اُ٘برظ 19.9ؽ. ة 4-5-رسضٛش انًبدح انًبصح BS أػ٤ق ئُ 18 ٠ؽ خلبٕ ثبصُزٓ ٢ـؾٗ ٕٞظق هـش ؽج٤جبر 27 ِْٓ)0.5-0.1 ( ٚؽ ٖٓ أُبدح أٌُضلخ اُ٘برغخ ػٖ رغل٤ق OMWWك ٢اُٜٞاء اُؼبدٝ .١ػغ 30ؽ ٖٓ أُض٣ظ اُغبثن ك ٢أعـٞاٗخ ٓـِوخ ك ٢كشٕ دسعخ ؽشاسرُٔ ّْ400 ٚذح 4عبػبد ,كٌبٕ ٝصٕ اُ٘برظ ثؼذ رجش٣ذ 14 ٙؽ. ة -5-5-رسضٛش انظبثٌٕ انسبٔ٘ OMWW عش ٟرٌض٤ق OMWWكٝ ٢ػبء ٝاعغ اُغـؼ ك ٢أُخزجش ثٞاعـخ أشؼخ اُشٔظ .ؽظِ٘ب ػِ27 ٠ 1 ±ؽ ٖٓ أٌُضق ٖٓ OMWW َٓ500أُبئغ .أػ٤لذ 10ؽ ٖٓ ٛزا أٌُضق ئُ 490 ٠ؽ ٖٓ اُظبث ٕٞاُغبخٖ اُ٘برظ ر َٞآًٖ ٝػبء اُزظ٘٤غ ٓغ أُضط اُغ٤ذ ,عش ٟثؼذ رُي ٝػغ اُ٘برظ أُزغبٗظ اُغبئَ ك ٢اُوبُت أُشؿٞة ؽز ٠اُزظِت ٓغ ئػـبء اُشٌَ أُشؿٞة.
35
ة -6-انوٛبعبد ة 1-6-اخزجش أداء أُٞاد أُؾؼشح BW-PC,BG-PC,BG,BSك ٢ئصاُخ اُ٘زشاد ٖٓ ٓ٤ب ٙثئش ٓؼذح ُِششة ك٘ٓ ٢ـوخ اُش٣ؾبٕ ثذٓٝب ثبعزخذاّ اُـش٣وخ اُشاًذح ؽ٤ش ٝػغ
1ؽ ٖٓ ًَ ٖٓ
أُغزؾؼشاد ك ٖٓ َٓ 50 ٢أُ٤بُٔ ٙذح 48عبػخ ٝه٤غذ ثؼذٛب رشً٤ض ًَ ٖٓ أٗٞ٣بد اُ٘زشاد ٝ اُوِ٣ٞخ ٝ Mاُوِ٣ٞخ ٝ Pاُوِ٣ٞخ اٌُِ٤خ ئػبكخ ُزؾذ٣ذ اِ pH ة 7-انُزبئح اندذٔل ()3يوبسَخ أداء انًٕاد انًبصح انًسضشح ك ٙإصانخ انُزشاد يٍ ػُٛخ يٛبِ يُطوخ دٔيب ثٕخٕد األَٕٚبد انغبنجخ األخشٖ ػُذ دسخخ زشاسح ْ 29.7و اعى انؼُٛخ
ػُٛخ انًٛبِ BW-PC BG-PC
BG
BS
pH
8.13
9.96
10.27
10.02
10.53
انوهٕٚخ Pػهٗ أعبط كشثَٕبد انكبنغٕٛو يهؾ/ل
40
600
400
400
660
انوهٕٚخ Mػهٗ أعبط كشثَٕبد انكبنغٕٛو يهؾ/ل
340
700
840
580
900
انوهٕٚخ انكهٛخ Tيهؾ/ل
380
1300
1240
980
1560
رشكٛض أNO3 - ٌٕٚ
338.12
233.26
126.26
173.34
111.28
أظٜشد اُ٘زبئظ اُٞاسدح ك ٢اُغذ )3 (ٍٝإٔ أداء اأُٞاد أُبصح ٝكوًب ُِ٘غجخ أُئ٣ٞخ إلصاُخ أ ٕٞ٣اُ٘زشاد ٓشرجخ ػِ ٠اُشٌَ اُزبُ. BG< BG-PC < BW-PC < BS ٢ ة 8-انذساعخ انسشكٛخ -أعش٣ذ اُذساعخ اُؾشً٤خ ػِ ٠أُؾؼش
ٗ BSظشًا ألدائ ٚاُغ٤ذ ك ٢ئصاُخ اُ٘زشاد ٝرٌِلزٚ
االهزظبد٣خ أُ٘خلؼخ ٓوبسٗخ ثجو٤خ أُؾؼشاد ؽ٤ش ٝػغ 1ؽ ٖٓ BSك ٖٓ َٓ 50 ٢ػ٘٤خ أُ٤بٙ أُخزجشح ٝرْ ه٤بط رشً٤ض أ NO3 - ٕٞ٣ك ٢أصٓ٘خ ٓخزِلخًٝ ،بٗذ اُ٘زبئظ ًٔب ٝ ٢ٛاسدح ك ٢اُغذٍٝ ( ٝ )4اُز٣ ١ؼجش ػ٘ ٚاُشٌَ ( . )2
36
اندذٔل ()4انذساعخ انسشكٛخ نهًبدح انًبصح BS انضيٍ (عبػخ) 0.00 24.00 30.00 36.00 42.00 48.00
انزشكٛض يهؾ/ل 308.57 120.00 105.00 96.43 92.14 77.14
انُغجخ انًئٕٚخ نإلصانخ% 0.00 61.11 65.97 68.75 70.14 75.00
انكًٛخ انًضانخ يهؾ/ل 0.00 188.57 203.57 212.14 216.43 231.43
٣ج ٖ٤اُغذ ٝ)4( ٍٝاُشٌَ ( )2إٔ كؼبُ٤خ أُبدح أُبصح ثِـذ %61.11ثؼذ 24عبػخ ٖٓ ٝصْ اسرلؼذ ئُ %75 ٠ثؼذ 48عبػخٛ ٝ ,زا ٣ؼـ٘٤ب كٌشح ػٖ اُضٖٓ اُالصّ ُزخل٤غ رشً٤ض أ ٕٞ٣اُ٘زشاد ئُ٠ أُغز٣ٞبد أُـِٞثخ ٝرُي ثؼذ ٓؼشكخ اُزشً٤ض االثزذائ ٢أل ٕٞ٣اُ٘زشاد ٓٔب ٣غب ْٛك ٢رٞك٤ش عبػبد اُؼَٔ اُز٣ ١إصش ػِ ٠اُ٘بؽ٤خ االهزظبد٣خ اُخبطخ ثظشٝف اُزشـ.َ٤ ة – 9-زغبة األثؼبد االيزضاصٚخ أعش٣ذ اُذسعخ االٓزضاص٣خ ػِ ٠أُبدح أُبصح BSاألًجش كؼبُ٤خ ٝرُي ثزؾؼ٤ش عِغِخ ٖٓ اُزشاً٤ض ٓأخٞرح ٖٓ اُؼ٘٤خ األطِ٤خ ٝرْ ٝػغ 1ؽ ٖٓ BSك ٖٓ َٓ 50 ٢اُؼ٘٤بد أُبئ٤خ أُخزِلخ اُزشً٤ض ٝؽغجذ اُ٘زبئظ ٝكن اُغذ.)5( ٍٝ اندذٔل ()5انؼالهخ ث ٍٛايزضاص أ ٌٕٚانُزشاد ثبخزالف رشكٛض انًسهٕل ػهٗ انًبدح انًبصح BS انزشكٛض االثزذائٙ ألٌٕٚ انُزشاد يهؾ/ل 321.429 312.857 295.714 231.429 190.714 162.857 130.714 105.000
رشكٛض إٌٔٚ انُزشاد ثؼذ االيزضاص ( يهؾ/ل) 106.071 90.000 85.714 32.143 26.786 21.429 18.214 19.286
انزشكٛض الثزذائٙ (يٛهٙ يٕل/ل) 5.184 5.046 4.770 3.733 3.076 2.627 2.108 1.694
Cانزشكٛض انزٕاصَٙ (يٛه ٙيٕل /ل ) 1.711 1.452 1.382 0.518 0.432 0.346 0.294 0.311
كًٛخα انًبدحانًًزضح ػهٗ 1ؽ ( يٛه ٙيٕل/ؽ) 0.174 0.180 0.169 0.161 0.132 0.114 0.091 0.069
37
1/C (1/ αيٛهٙ (يٛهٙ 1 1يٕل/ؽ)يٕل/ل) 0.585 0.689 0.723 1.929 2.315 2.893 3.404 3.215
5.758 5.564 5.905 6.222 7.564 8.768 11.022 14.467
α/αm
0.660 0.683 0.644 0.611 0.502 0.433 0.345 0.263
a KC a 1 KC m
ٝهذ رج ٖ٤إٔ ٛز ٙاُ٘زبئظ رزجغ ٓؼبدُخ الٗـٔٞ٤س ك ٢االٓزضاص
ؽ٤ش :θدسعخ آزالء اُغـؼ أُبص ثبُٔبدح أُٔزضح ٤ًٔ = aخ أُبدح أُٔزضح ػِ 1 ٠ؽ ٖٓ أُبدح أُبصح ٤ًٔ = aخ أُبدح أُٔزضح ك ٢اُـجوخ أُٔزضح أؽبد٣خ اُغض١ء ػِ 1 ٠ؽ ٖٓ أُبدح أُبصح
m
=Kصبثذ اُزٞاصٕ االٓزضاص١ = Cاُزشً٤ض اُزٞاصُِٗٔ ٢بدح أُٔزضح
1
1 ٝرْ اعز٘زبط هٔ٤خ ٖٓ aسعْ ربثؼ٤خ ) ( ƒ m C
ٝثزؾذ٣ذ ٓوِٞة ٗوـخ روبؿغ اُخؾ اُج٤بٗ٢
ٓغ ٓؾٞس اُؼ٘٤بد )a = 1/3.6= 0.277 (mmol/g m
ُ ٝؾغبة صبثذ اُزٞاصٕ االٓزضاصٗ ١ؾغت ٓ َ٤أُغزو ْ٤اُوبؿغ ُٔؾٞس اُؼ٘٤بد ك ٢اُشٌَ ( )3 1 mK
ٚ٘ٓ ٝ tng
1 m .tng
K
6.4 3.6 1 2.33 K 1.547 1.2 0 2.33 * 0.277
tng
ٝػ٘ذ رؼ ٖ٤٤صبثذ اُزٞاصٕ كٓ ٢غبٍ اُزشاً٤ض اُظـ٤شح ( ٓغبٍ ٘ٛش ( )١أ ١ػ٘ذٓب رٌ1 >> KC ٕٞ را ٣ؼـ:٢ ك ٢ػالهخ الٗـٔٞ٤س) ؽ٤ش ٗ θ =KCؾغت ٓ َ٤أُٔبط ُِٔ٘ؾ٘ ٢ك ٢اُشٌَ( )4ف 0.28 0 ) 1.4(mmol 1 0 0.20
K tng
أ ١إٔ ه K ْ٤رشاٝؽذ ث(mmol) -1 1.4 ٝ1.547 ٖ٤ ة 10-انذساعخ انغطسٛخ ٔ انطٛلٛخ IRيب ث ٍٛإَٔٚبد انُزشاد ٔ انًبدح انًبصح دسط آزضاص اُ٘زشٝع ٖ٤ك ٢اُذسعخ ّْ 196 -ثغٜبص ( )Micromeritics – Geminiئػبكخ ئُ٠ ٓزضاص اُ٘زشاد ٖٓ أُ٤ب ٙأُِٞصخ ثٜب. ة٣ 1-10-الؽظ ٖٓ اُشٌِ )4ٝ3 ( ٖ٤اٗـجبهًب ٓوجٞالً ُِٔؼـ٤بد ػِٓ ٠ؼبدُخ الٗـٔٞ٤س ٓٔب ٣ذٍ ػِ٠ رغبٗظ عـؼ أُغزؾؼش ٞٛ ٝ BSاألًجش كؼبُ٤خ ثبُ٘غجخ الٓزضاص اُ٘زشاد ٝػِ ٠ػذّ ؽظٍٞ رشاًْ ُِغض٣ئبد أُٔزضح. 38
ةٗ ُْ 2-10-ؾظَ ػِ ٠ا٣ضٝرشّ ُِٔٞاد أُبصح اُغذ٣ذح ثغجت عؼخ االٓزضاص ٝؿج٤ؼخ اُغـؼ اُؾبَٓ. ة 11-رٔذ اُو٤بعبد اُـ٤ل٤خ ػِ ٠عٜبص )Jascom FT/IR-300E ( IRاألشٌبٍ( ٝ )16-5رُي ثـؾٖ ِٓ 0.3-0.2ؾ ٖٓ أُشًت أُذسٝط ٓغ 0.1ؽ ٖٓ ثش٤ٓٝذ اُجٞربع ّٞ٤اُغبف ,صْ ٝػؼذ ًٔ٤خ ٖٓ أُض٣ظ أُـؾ ٕٞث ٖ٤هشطٓ ٖ٤ؼذٗٗ ٝ ٖ٤٤ز٤غخ اُؼـؾ رؾُٞذ أُبدح ئُ ٠هشص شلبف ٓزٔبعي ػٖٔ ٓبعي خبص ٝٝػغ ثؼذ رُي كٓ ٢ـ٤بف األشؼخ رؾذ اُؾٔشاء . ة 1-11-رزغِغَ أُٞاد أُبصح أُذسٝعخ ٝكوًب ُلؼبُ٤زٜب ك ٢اُزخِض ٖٓ أ ٕٞ٣اُ٘زشاد ػِ ٠اُشٌَ اُزبُ٣ٝ , BG< BG-PC < BW-PC < BS ٢لغش رـ٤ش ٛز ٙاُلؼبُ٤خ ٖٓ خالٍ دساعخ ٓخــبد ُِٞٔ IRاد أُبصح أُذسٝعخ ( ٝاُز ٢رؼزجش ٓٔ٤ضح ُغـؼ ًَ ٓبدح ) صْ ٓوبسٗزٜب ٓغ ؿ٤ق األشؼخ ُِؾبَٓ األعبع( ٢اُخلبٕ اُجبصُزُِٔ ٝ )٢بدح أُبصح هجَ ٝثؼذ االٓزضاص األشٌبٍ( ًٝ , )16-5زُي ٖٓ ؽغبة صبثذ اُزٞاصٕ االٓزضاص:K ١ كوذ ُٞؽظ رشٌَ ػظبثبد آزظبص ٝاػؾخ ٝعذ٣ذح ثؼذ رٞػغ ٗٞارظ رٌِ٤ظ أُبدح OMWWػِ ٠اُؾبَٓ ( خلبٕ ثبصُزٓ ٢ـؾ -ٕٞطٞف ثبصُز ) ٢ثبُ٘غجخ ُِٔبدر ٖ٤أُبصرٝ BS ٖ٤ BW-PCاُشٌَ ( ٝ )9,6ؿ٤بة ٓؼظْ ٛز ٙاُؼظبثبد ثؼذ ؽذٝس االٓزضاص ػِٛ ٠بر ٖ٤أُبدرٖ٤ اُشٌَ (٣ٝ ,)10,7لغَش رُي ثؾذٝس اسرجبؽ ه ١ٞث ٖ٤أُشاًض اُلؼبُخ ك ٢أُبدح أُٔزضح أُُؾذصخ ٝثٖ٤ أ ٕٞ٣اُ٘زشاد أد ٟئُ ٠رـ٤ش ػظبثبد االٓزظبص ثبُ٘غجخ ُِٔبدح أُبصح هجَ االٓزضاص ٝثبُزبُ ٢صادد اُلؼبُ٤خ االٓزضاص٣خ٣ٝ ,زٞاكن رُي ٓغ ه ْ٤صبثذ اُزٞاصٕ االٓزضاص ١ثبُ٘غجخ ُِٔبدح أُبصح اُز ٢أػـذ أكؼَ اُ٘زبئظ كِٞؽظ إٔ K>1ؽ٤ش رذٍ Kػِ ٠ه ْ٤أٌُ ٕٞاالٓزضاص ١أ ١ػِ ٠اُلؼَ أُزجبدٍ ثٖ٤ عض٣ئبد أُبدح أُٔزضح ٝأُشاًض اُلؼبُخ ػِ ٠اُغـؼ اعز٘بداً ئُ ٠هٞاٗ ٖ٤اُزشٓٞد٘٣بٓ٤ي اإلؽظبئ٢ ُِـجوخ اُغـؾ٤خ. ة 2 - 11-أدخِ٘ب ٌٓضق ( OMWWثٔؼذٍ عضء ٝصٗ ٖٓ ٢أٌُضق ئُ 99 ٠عضء ٝصٗ ٖٓ ٢ؿٞس اُغبئَ اُظبث ٢ٗٞاُغبخٖ اُٜ٘بئ ٢اُ٘برظ ٖٓ أُظ٘غ) ك ٢ط٘بػخ اُظبث ٕٞاُظ٘بػ ٢ؿ٤ش اُزشً٤ج٢ ٝاعزلذٗب ٖٓ اُلٞ٘٤الد أُزؼذدح ك ٢أٌُضق ٌُٜٗٞب ٓؼبدح ُِزأًغذ ٝثزُي أٌٖٓ اُزخِض ًِ٤بً ٝثذٕٝ كؼالد ٖٓ OMWWثـش٣وخ ٓل٤ذح ٓ ٝشثؾخ ٣ ُْٝ ,الؽظ ُِٗٔ ٞلـش٣بد أ ٝاُغشاص٘ٓ ْ٤ز إٔ رْ ط٘بػخ اُظبث ٕٞئُ ٠ا ٕ٥أُٔ ١ذح رزغبٝص عزخ أشٜش .
39
٣ ٝؼبدٍ ٝصٕ ٌٓضق OMWWأُؼبف ئُ 99 ٠عضء ٝصٗ ٖٓ ٢اُظبث ٖٓ ٕٞاُـٞس اُغبئَ اُغبخٖ ٖٓ اُظبث ٕٞاُخبسط ٖٓ ٝػبء اُزلبػَ ً 200ؾ ٖٓ OMWWاُغبئِخ اُؼبد٣خ هجَ اُزٌض٤ق ٌَُ ؿٖ ٖٓ اُظبث ٕٞاُ٘برظ . ةٛٝ 3-11-ز ٙاُـش٣وخ ٌٖٔ٣اعزخذآٜب ػِٗ ٠ـبم ٝاعغ ٝال ٞ٣عذ كٜ٤ب أٓ ١خِلبد ٗبرغخ ػٖ اعزؼٔبٍ . OMWW ةٝ 4-11-اعز٘بداً ئُٓ ٠ؼـ٤بر٘ب كإ اعزؼٔبٍ OMWWك ٢ؽبُز ٚاالػز٤بد٣خ ؿ٤ش أٌُضلخ ٓؾذٝد ثبؽزٞاء اُشبٓج ٞػِٗ ٠غجخ OMWW ٖٓ %0.09 - %0.18ؿ٤ش أٌُضق ,أ ١أٗ ٌٖٔ٣ ٚاُزخِض ٖٓ (ً)1.8-0.9ؾ كوؾ ٖٓ OMWWاُؼبد ١ؿ٤ش أٌُضق ثبؽزٞائ ٚك 1 ٢ؿٖ روش٣جًب ٖٓ اُشبٓج,ٞ ثٔ٘٤ب ٌٖٔ٣اُزخِض ٖٓ ً 200ؾ OMWWثؼذ رٌض٤لٜب ٝئػبكخ أٌُضق ئُ ٠ؿٖ ٖٓ اُظبثٕٞ أُٞطٞف ك ٢اُؼَٔ ؽغت ؿش٣وز٘ب أُوزشؽخ ك ٢اُج٘ذ ة ٝ 2-11-ة.3-11-
40
-3انشعٕيبد ٔ انًخططبد 80
60 50 40 30 20 10
اننسبت انمئويت إلزانت اننتراث% NO3 -
y = -0.038x2 + 3.3211x + 0.5225 R2 = 0.9932
70
0 54
48
36
42
24
30
12
18
0
6
انسمن (سبعت) ان شكم ( )12اندراست انحركيت نهمبدة ان مبزة BS
16.00 14.00 y = 2.2546x + 3.7193
1/α
(mmol/g)_ 12.00 1 10.00
2
R = 0.7035
6.00 4.00
1/a (mmol/g)-1
8.00
2.00 4.000
3.500
3.000
2.500
2.000
1.500
1.000
0.500
0.00 0.000
1/C (mmol/l)-1
1/Cنهًغزسضش BS 1/αa\1 اثؼٛخ () 3)1 انشكم ( بدالنةه C\1 تابعية انشكم 0.800 m 0.700 0.500 0.400 0.300 0.200 0.100 1.800
1.600
1.400
1.200
1.000
0.800
0.600
0.400
0.200
C mmol/l
a/amنهتركيس انتوازني Cنهًغزسضش BS α/αm ( )3تببعيت انشكم)(4 41
0.000 0.000
a/am mmol/g
0.600
IR
BS IR
NO3-
BS IR
42
5
6
7
IR
8
BW-PC IR
NO3 -
BW-PC
43
9
IR
10
IR
BG-PC
NO3 -
IR
BG-PC IR 44
11
12
13
IR
BG
NO3 -
IR
BG IR 45
14
15
16
انًخطط انظُبػ ٙنهزخهض يٍ OMWWثزسًٛهّ ػهٗ انخلبٌ انجبصنز ٙانغٕس٘ نظُبػخ انًٕاد انًبصح ألَٕٚبد انُزشاد يٍ انًٛبِ
OMWW
ٌٓضق OMWW
ٓضط
رغل٤ق
رٌِ٤ظ ثبُذسعخ ْ ّ 400
رجش٣ذ
رخضٖ٣
46
خلبٕ ثبصُز٢ ثبألشٌبٍ أُخزلِخ
انًخطط انظُبػ ٙلنزخهض يٍ OMWWثزكثٛلّ ٔ اعزخذاو يكثلّ ك ٙطُبػخ انظبثٌٕ انظهت انطجٛؼٙ ًَ 1ؿٖ ٖٓ اُظبث ٕٞاُؾب ١ٝػِ OMWW ٠اُ٘برظ ٣غزِٜي ً 10ؾ ٖٓ ٌٓضق ٝ OMWWاُز٢ ر٘زظ ػٖ رٌض٤ق ً 200ؾ ٖٓ ٛٝ , OMWWز ٙاُـش٣وخ ٓشثؾخ ُِزخِض ٖٓ OMWWثذٕٝ ٓخِلبد. رٌض٤ق ثبُـبهخ اُشٔغ٤خ أ ٝؿ٤شٛب OMWW
اُ٘برظ أٌُضق ِ OMWW
رخض ٖ٣أٌُضق OMWW
≈ %1 خالؽ
روغ٤خ اُظبثٕٞ ػِ ٠عـؼ ٓؾظٞس
رشٌ َ٤هـغ اُظبثٕٞ
يالزظخ ٌٖٔ٣ :روذ ْ٣ػ٘٤خ ٖٓ اُظبث ٕٞأُشبس ئُ ٚ٤ك٢ اُجشاءح ػ٘ذ اُـِت.
اُزؼجئخ
اُزخضٖ٣
47
≈ W%99
ٓظذس اُـٞس اُغبئَ اُغبخٖ اُٜ٘بئُِ ٢ظبثٕٞ
-4االدػبءاد انًطهٕة زًبٚزٓب 1-4اُزخِض ٖٓ ٓبء اُغلذ ٝ OMWWاعزخذاّ ٌٓضل ٚثبُزؾٔ َ٤ػِ ٠اُخلبٕ اُجبصُز ٢اُغٞس١ ُِؾظ ٍٞػِٞٓ ٠اد ٓبصح ُِزخِض ٖٓ أٗٞ٣بد اُ٘زشاد ك ٢أُ٤ب ٙأُِٞصخ ثٜب. 2-4اعزخذاّ اُخلبٕ اُجبصُز ٝ ٢اُظٞف اُجبصُز ٢اُغٞسً ١ؾبَٓ ك ٢ط٘بػخ أُٞاد أُبصح . 3-4ئػبدح اعزؼٔبٍ اُخلبٕ اُجبصُز ٢ك ٢ط٘بػخ أُبدح أُبصح. 4-4اعزخذاّ ٓضائظ ث٘غت ٓخزِلخ ٖٓ اُخلبٕ اُجبصُز ٝ ٢اُج٘ز٤ٗٞذ ك ٢ط٘بػخ أُبدح أُبصح ُِ٘زشاد 5-4اعزخذاّ ٌٓضق OMWWك ٢ط٘بػخ اُظبث ٕٞاُظِت. 6-4اُزخِض ٖٓ OMWWػِٗ ٠ـبم ٝاعغ ثزٌض٤ل ٚثٞاعـخ اُـبهخ اُشٔغ٤خ ٝاعزخذآًٔ ٚبدح ٓؼبكخ راد خٞاص ٓؼبدح ُِزأًغذ ٘ٓ ٝؼٔخ ك ٢ط٘بػخ ٗٞع عذ٣ذ ٖٓ اُظبث.ٕٞ
48
- 5انًهخض عش ٟاُزخِض ٖٓ ٓبء اُغلذ ٝ OMWWاعزخذاّ ٌٓضل ٚثبُزؾٔ َ٤ػِ ٠اُخلبٕ اُجبصُز ٝ ٢اُظٞف اُجبصُذ اُغٞسُِ ١ؾظ ٍٞػِٞٓ ٠اد ٓبصح ُِزخِض ٖٓ أٗٞ٣بد اُ٘زشاد ك ٢أُ٤ب ٙأُِٞصخ ثٜبًٔ .ب اعزخذاّ ٌٓضق OMWWثٞاعـخ اُـبهخ اُشٔغ٤خ ًٔبدح ٓؼبكخ راد خٞاص ٓؼبدح ُِزأًغذ ٘ٓٝؼٔخ ك ٢ط٘بػخ ٗٞع عذ٣ذ ٖٓ اُظبث ٕٞاُظِت.
OMWW ,
49
انًشاخغ- 6 1- P.K.GOEL, Water Pollution-Causes, Effects and control, P(197-198). New Delhi.1997. 2- Yazjy, Wareef, M.Sc. Thesis P(10-11) Damascus University, Faculty of sciences, (2004). 3- T.M. Addiscott, NITRATE, AGRICULTURE AND THE ENVIRONMENT, UK, P (27-28,30-40) , 2005 صاسحٝ ,45 ْ سه.٠ُٝ اُششة أُشاعؼخ األٙب٤ٓ ,١سٞخ اُغ٤ظ اُؼشث٤٣أُوبٝ اطلبدُٞٔئخ ا٤ٛ - 4 .1994 ,اُظ٘بػخ أُؼبُغخ ألؿشاع٢ اُظشف اُظؾٙب٤ٓ ,خ٣سٞخ اُغ٤ظ اُؼشث٤٣أُوبٝ اطلبدُٞٔئخ ا٤ٛ - 5 .2003 ,صاسح اُظ٘بػخٝ .2752 ْ سه,١اُش خ٤ًِ ,خ٤بء اُ٘جبر٤ هغْ ػِْ األؽ, ١ اُغضء اُ٘ظش-ٙب٤ُٔب ا٤عُٞٞ٤ثٌٝش٤ٓ ,ٕ ػذٗب, ّ ٗظب٢ِ ػ. د- 6 .2004-2003 , عبٓؼخ دٓشن, ِّٞاُؼ 7- M. Matosic, I. Mijatouic, and E. Hodzic , Nitrate Removal from Drinking Water Using Ion Exchange – Comparison of Chloride and Bicarbonate Form of the Resins, Chem.Biochem. Eng, P(141-146) ,2000. 8- Manal F. Abou Taleba, , Ghada A. Mahmouda, Samia M. Elsigenyb, El-Sayed A. Hegazya. , Adsorption and desorption of phosphate and nitrate ions using quaternary (polypropylene-g-N,N-dimethylamino ethylmethacrylate) graft copolymer, Journal of Hazardous Materials , P(372–379) ,2008.www.elsevier.com/locate/jhazmat 50
9- Stephany burge,Rolf Halden, Nitrat and Perchlorate Removal from Ground water by Ion exchange , University of Idaho Moscow,1999. 10- Aušra Mažeikienė1, Marina Valentukevičienė, Mindaugas Rimeika, Algirdas Bronislovas Matuzevičius, Regimantas Dauknys, Removal Of Nitrates and Ammonium Ions from water using natural sorbent Zeolite (Clinoptilolite), Dept of Water Management, Vilnius Gediminas Technical University, P(38–44) ,2008. ب٣سٞ ع٢ارظ اُجشً٘خ كُٞ٘ خ٣كبم االهزظبد٥ ا,ّػجذ اُغال.٢ٗ اُزشًٔب,مٝكبس.١اُؼٔبد
- 11
س داخَ أُإعغخٞش ٓ٘ش٣روش, ) اُـقٝ ب٣سٌٞخ ع٤س اُجبصُزٞ اُظخ-خ٤ز٤ًس اُزشاٞ(اُظخ .2004 , دٓشن,خ٤ٗح أُؼذٝ اُضشٝ ب٤عُٞٞ٤اُؼبٓخ ُِغ ( ( ٕٞز٣ ػظش اُضٙب٤ٓ ٖٓ اُزخِض,٢بصع٤ُق ا٣سٝ ,ت٣ ػذٗبٕ د. د,ذ اُجضسح٤ُٝ ٠٤ؾ٣.د. أ- 12 ٍ ٓجبد٠ُ ) ئٚٗٝ ثذٝ اُغـؼ٠ِخ ػ٤ُٞ٘٤ٗبد اُلٌُٞٔ ( ٓغ رٌبصق اِٚ٣ٞ ثزؾOMWW ٝ االطـ٘بع-І
اُظ٘بػخ٢ أُغزخذٓخ كٙب٤ُٔظبئق ُٔؼبُغخ اُٞ ٓشزشى ٓزؼذد ا١شبسد
ِّٞ ٓغِخ عبٓؼخ دٓشن ُِؼ,شح٤ٗبد راد األهـبس اُظـٞ٣ األ٠ِخ ػ٣ٝ اُؾبٙب٤ُٔٓؼبُغخ ا .2009 ,ٍٝ اُؼذد األ25 خ –أُغِذ٤األعبع 13-
Francis Rouessac, Annich Rouessac, Chemical Analysis-
Second Edition, University of Lemans, France. 2007. 14-
Standard Methods for the Examination of Water and
Wastewater 20 th Edition, American Public Health Association, American Water Works association, Water Environment Federation,1999. أُشاكنٝ ٕصاسح اإلعٌبٝ , اُششةٙب٤ٓ دحٞخ ُٔشاهجخ ع٣َ أُخجش٤َُ ؿشائن اُزؾب٤ُ د- 15 .2001 , دٓشن,غق٤ٗٞ٣ ُخٕٞ ٓغ ٓ٘ظٔخ األْٓ أُزؾذح ُِـلٝثبُزؼب ْ هغ,٢ِٔ اُوغْ اُؼ-بد أُظبٗغ٣ ٗلبٝ ٙب٤ُٔ ٓؼبُغخ ا,٢ِ ٓؾٔذ ػ, اُشؼبس.د.أ
- 16
.2008-2007. عبٓؼخ دٓشن,خ٤ُٝ اُجزشٝ خ٤بئ٤ٔ٤ٌُ٘ذعخ اُٜخ ا٤ًِ ,خ٤٘ذعخ اُـزائُٜا 17 - LEO M. L. NOLLET , Handbook of water analysis- Second edition ,Boca Raton London New York, P(201-217) , 2007. 51
18- YA. GIRASIMOV and others, Physical Chemistry, Vol 1, P(487), Mir Publishers, Mosco,1974. 2009 /2008 , 5654 ْخ سه٣سٞ اُجشاءح اُغ,-19 examined by WIPO ( IC/09/2843/SY-BG )
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Patent No.5627
جسئٍ ًب فً الكٍروسٍن السبئل منC10-C14 صنبعت مصفبة جسٌئٍت هجٍنت جذٌذة لفصل البرافٍنبث السلسلٍت ) Vegobond A حذىٌر السٌىلٍج االصطنبعً ( األلىمٍنى سٍلٍكبث البلّىرٌت
Hybrid Molecular Sieve Produced From The Modification Of Crystalline Sodium Aluminum Silicate (Vegobond A) For Partial Separation C10 – C14 Linear Paraffin's From Liquid Kerosene
ٌذٍى ولٍذ البسرة. د.أ Prof. Yahya Walid Al-Bizreh
خٍٛ انخبو انغبئم ػٍ ثقٛشٔعٛب يٍ انكٛ خضئC10-C14 خُٛبد انخغٛخ نفصم انجشافٛئٚرىّ ألٔل يشّح اثزكبس يصفبح خض ُبدٛ نهجشافٙشاٌ يٍ خٓخ ; ٔيصفبح يقزشزخ نهفصم انكهٍٛ انغٛشٔعٛانًكَِٕبد نهسصٕل ػهٗ قغفخ رصهر نك ذٕٛنٚشانضٕٚ ٔرنك ثزس.ٖ صُبػخ انًُظفبد يٍ خٓخ أخشٙ انًؼقذح العزؼًبنٓب فUOP ضادٛٓ ردٙانًزكٕسح ف ؼًمٚ ٘ش خٓبص يخجشٕٚ يغ رغٙذ انغٕس٘ انًسغٍّ نالعزخذاو انصُبػَٕٛغ ثبنجُزُٛ انزصَٙ انؼًبVegobon A . خٛئٚخ انًصفبح اندضٛرسذ انضغظ ٔانخالء ٔ دسخبد انسشاسح انًخزهفخ نهكشف ػٍ فؼبن
A new hybrid molecular sieve for partial separating of linear C10-C14 paraffin's from liquid kerosene's has been invented from modified zeolite Vegobond A of Oman Chemicals with improved Syrian Bentonite for industrial use. This molecular sieve makes it possible to receive a fraction of avia –kerosene in terms of this work .On the other hand; it may be considered for full deparaffinization in terms of UOP plant in conditions of use in detergent industry. In addition, a new device has been developed to detect the efficiency of molecular sieves under different temperatures,vacuums, and pressures.
page الصفذت 1
2-3
5
4
6
Contents Technical condition of the invention
الذبلت الخقنٍت لالخخراع-1
Technical Description of the invention
الىصف الفنً لالخخراع-2
Manufacturing scheme
Claims to be protected
References
Appendix (1) Chemical structure of Zeolite and Bentonite
7
8
10- 11
12
13-14
15
16
المذخىٌبث
ً المخطط الصنبع- -3 اإلدعبءاث المطلىة دمبٌخهب-4 المراجع-5 )1( ملذق-6 الخركٍت الكٍمٍبئً للسٌىلٍج والبنخىنٍج
Appendix (2) Syrian Kerosene Analyses
)2( ملذق-7 الخذلٍل الكٍمٍبئً للكٍروسٍن السىري
The surface parameters Table (1), Fig (1)
الذراست السطذٍت-8
Explanation to Table (1) and Fig (1)
DTA results
XRD image
Experimental results
17-18
The pilot plant image
19
The G.C image
حىضٍخ للذراست السطذٍت-9 ً– نخبئج الخذلٍل الذراري الخفبضل10 – نخبئج انعراج األشعت السٍنٍت11 – النخبئج الخجرٌبٍت12 – صىرة الجهبز المقخرح13 G.C – صىرة14
الذبلت الخقنٍت لالخخراع شٕٚ( ٔ نزنك خشٖ رسOman Chemicals) Vegobond A ف جًٛكٍ انزكٚ خ ٔنىٛئٚذ يُفشداً كًصفبح خضَٕٛؼًم انجُزٚ نى شْب يغٛ رأثٙخ رزًبثم فٛئٚ صُبػخ انًُظفبد نهٕصٕل إنٗ يصفبح خضٙ ٔ يبدح ثُبء فَٕٙٚ انًغزخذو كًجبدل أٙذ االصغُبػٕٛنٚانض ٍ يC10 –C14 خُٛبد انخغّٛخ نفصم انجشافًٛ انصُبػخ انؼبنٙ انًغزخذيخ فUOP خ انًصُؼّخ انخبصخ جٛئٚانًصفبح اندض ˚ و180 خٕ ٔ دسخخ انسشاسح30 ششٔط يزًبثهخ رسذ انضغظٙظ فٍٛ إنٗ ػًٕد اإليزضاص ثبنزُقٛشٔعٛٔ قذ أدخم انك.ٍٛشٔعٛانك خ يٍ ْزا انُٕعٛئٚ صُبػخ يصفبح خضٙذ فٕٛنٚغزخذو ْزا انُٕع يٍ انضٚ خٓبص صًى نٓزا انغشض ٔ نىٍٙ فٛ خٕ يٍ انُزشٔخٙف . ٌٜززٗ ا ػًٕدٙش انًًزض ثئَقبص انضغظ فٍٛ غٛشٔعٛ ٔقذ رى أخز انك. ٘ذ انغٕسَٕٛ انجُزٙٓش فٕٚ انزسٙخ فٛغٛأيب انًبدح انشئ (2) ٔ (1) خ فقذ رى أخزْب ػهٗ دفؼبدٛئٚ انًصفبح اندضٙ رى ايزضاصْب فٙخ انزُٛبد انخغٛاإليزضاصززٗ انضغظ اندٕ٘ أيب انجبساف . فٛخ نهزكثٍَٛ ٔ زهضَٔبد يؼذّٛخ ٔ ثٕخٕد انُزشٔخٛثٕاعغخ يخه (2) ٔ (1) ٍٛ انًهسقٍٙ انغٕس٘ فٛشٔعٛذ ٔ انكَٕٛذ انًذسٔط ٔ انجُزٕٛنٚ نكم يٍ انضٙبئًٛٛم انكٛٔ قذ أٔسدَب َزبئح انزسه
Technical Condition Of The Invention
The synthetic crystalline zeolite Vegobnd A (Oman chemical) used in the detergent industry as co-builder has been modified to manage to receive a molecular sieve similar to that used by UOP in the world-wide industry for separating linear C10-C14 paraffin's from kerosene's under similar conditions: pressure 30 atm, t = 180 C˚ in a special developed device filled with nitrogen, and molecular sieve , kerosene was dropped into the adcorption column. Syrian bentonite has been one of the main materials used for the modification of the of mentioned zeolite in this work .Unadsorbed liquid fraction of kerosene was removed when pressur was decreased in the adsorption column to normal. Desorption of adsorbed linear paraffin's took place under vacuum by means of a vacuum pump and spiral metallic tubes for condensation . Chemical structures of Vegobond A (Oman chemical) Syrian bentonite and kerosene are given in Appendix 1, 2
(1)
الىصف الفنً لالخخراع زجٛجبد ثٛضبء ضبسثخ إنٗ انصفشح قغشِ ا 1-0.5يهى صهجخ نذسخخ كبفٛخ أخشٚذ ػهٓٛب انذساعبد انزبنٛخ: –1دساعخ انًغبزخ انغغسٛخ ثبيزضاص انُزشٔخ ٍٛف ٙانذسخخ 196-و˚ زٛث ثُٛذ ْزِ انذساعخ أٌ أقغبس انًغبيبد أصغش يٍ قغش خض٘ء انُزشٔخ ٍٛثًُٛب ثُٛذ ردبسة انفصم ٔخٕد يغبيبد ايزألد ثبنجبسافُٛبد انخغٛخ ] انشكم ٔ 1اندذٔل. [ 1 – 2دساعخ انزسهٛم انسشاس٘ انزفبضه :ٙرج ٍٛدساعخ يُسُٛبد انزسهٛم انسشاس٘ انزفبضه ٙنهضٕٚنٛذ انصبف(Vegobond A) ٙ (انشكم ٔ )2نهضٕٚنٛذ َفغّ انًسٕس (انشكم )3ظٕٓس قًخ َبششح نهسشاسح ف ٙيدبل 308و˚ ] ركٕ ٍٚيشكت خذٚذ يغ انجُزَٕٛذ انًسغٍّ [ ٔ رشكٛم ثٛكبد صغٛشح يبصخ نهسشاسح ػُذ دسخبد انسشاسح األػهٗ يًبٚذل ػهٗ ٔخٕد صيش OH انًشرجغخ كًٛٛبئًٛب ف ٙانًصفبح اندضٚئٛخ انُبردخ ٔ .الَدذ ْزِ انجٛكبد ف ٙانضٕٚنٛذ Vegobond Aانًغخٍ إنٗ 400و˚ ٔ انز٘ ٚزًٛض ثبززٕائّ ػهٗ قًخ ٔاضسخ خذًا ف ٙدسخخ انسشاسح 889و˚ ,يقبثم فؼه ٍٛضؼٛف( ٍٛانشكم )3ف ٙانًشكت اندذٚذ يًب ٚذل ػهٗ ٔخٕد رفبػالد كًٛٛبئٛخ ث ٍٛانًكَِٕبد ف ٙانسبنز. ٍٛ – 3دساعخ اَؼشاج األشؼخ انغُٛٛخ :رجذ٘ يُسُٛبد اَؼشاج أشؼخ سَٔزدٍ (انشكم )4نهًصفبح اندضٚئٛخ انُبردخ صٕسح ًَٕرخٛخ نهضٕٚنٛذ انًجهٕس ٔ انًسٕس ثبنجُزَٕٛذ رًٛض انًصفبح اندضٚئٛخ اندذٚذح . َ – 4زبئح دساعخ انفصمَ :شٖ َزبئح فصم اندضٚئبد انخغٛخ C10-C14يٍ انكٛشٔع ٍٛانخبو انغبئم ف ٙانششعٍٛ ] 30خٕ 180 +و˚[ يٍ اندذٔل ( )2زٛث َؼجش ج I/Nػٍ َغجخ األٚضٔ ثبسا ف I ٌٙإنٗ انجبساف ٍٛانخغN ٙ نكم يٍ انكٛشٔع ٍٛانخبو ٔ انكٛشٔع ٍٛانًكشس نكم يٍ انًصفبح اندضٚئٛخ ٔ VBP ٔ UOPثئخشاء انًقبسَخ يٍ أخم انقغفخ انُٓبئٛخ ثى يٍ أخم انقغفخ قجم انُٓبئٛخ ث ٍٛانًصفبر ٍٛاندضٚئٛز ٍٛانًزكٕسر ٍٛفغٕف َشٖ ثٕضٕذ أٌ كهزب انًصفبرٍٛ اندضٚئٛز ٍٛيزقبسثزبٌ يٍ زٛث قذسرًٓب ػهٗ فصم خضٚئبد انجبساف ٍٛانخغٛخ يٍ انكٛشٔع ٍٛف ٙانششٔط انًزكٕسح أػالِ – 5صٕسح اندٓبص انًغزخذو ٔ ششزٓب ٔ اإلشبسح إنٗ أخضائّا( انشكم .) 5 – 6أخشٚذ رسبنٛم انجشافُٛبد ف ٙانكٛشٔع ٍٛػهٗ خٓبص CARLO ERBA GCخبص ثًؼًم إَزبج انكٛم انخغLAB ٙ ْٕٔ يدٓض ثكًجٕٛرش ٔيكبيم ٔ ػًٕد خبص ثزسهٛم انجبسافُٛبد انًٕخٕدح ف ٙانكٛشٔع ٍٛػهٗ إَٔاػٓب( انشكم . ) 6 ًٚ – 7كٍ إػغبء ػُٛخ يٍ انًُزح إرا عُهجذ . يالزظخ :رؼزجش عشٚقخ انقٛبط َصف انصُبػٛخ انًجغغخ انز ٙعٕسَب يؤششًا خٛذًا ػهٗ أداء انًُزح ٔ ٚؼٕد رنك إنٗ ضخبيخ انًُشأح انصُبػٛخ ٔ ثبنزبن ٙانًُٕرج َصف انصُبػٔ ٙانزؼقٛذ انؼبن ٙنٓب.
)(2
Technical Description Of The Invention Solid White – yellow granulated material (Ф=0.5-1mm) underwent tests results of which are summarized in the followings 1- Nitrogen adsorption at -196C˚resulted poor adsorption of nitrogen [table (1), fig (1)] which can be attributed to smaller diameters of the zeolite pores than the diameter of Nitrogen molecule. The observed ability of the new adsorbent to separate C10-C14 linear paraffin's molecules from liquid kerosene is a good evidence of the existence of pores fitting those molecules. 2- A Comparison between the DTA diagrams of the preheated at 400C˚for 4 hours Vegobond A [Fig ( 2 )] and the modified Vegobond A [fig ( 3 )] shows the appearance of small exothermal pick at about308 C˚ [formation of anew compound with the improved bentonite] and new Endothermic picks at higher temperatures indicating the presence of chemically bonded OH groups in the new molecular sieve where as those picks do not exist in the simple preheated at 400C˚Vegobond A [fig ( 2)] which is characterized with a substantial exothermic pick at 889C˚. Instead, two small picks appear at this temperature in the molecular sieve [fig (3)] which, in both cases, may be attributed to chemical reaction between the components of the zeolite and improved bentonite. 3- The X ray Diffraction [fig 4] shows a very typical zeolite and bentonite crystalline structures Of the new molecular sieveVBP. 4- Results of separating C10-C14 molecules from liquid kerosene are listed in Table [2]. In which the content of leaner paraffin's is expressed with the ratio of Isoparafines (I) to the normal (linear) paraffin's (N) for raw and refined by means of UOP and VBP molecular sieves. When the comparison is conducted between the final and the pre-final fractions in table (2) It would be obvious that both molecular sieves are functioning nearly close to each other under the same mentioned above conditions. 5- Due to the complexity of both UOP refinery and its pilot plant, we believe that our suggested relatively simple device is a good indicator for such molecular sieve performance[ fig5]. 6- Analysis of paraffin's in kerosene were conducted by means of CARLA ERBA GC equipped with integrator and a column special for LAB plants to detect different molecules of paraffin's in kerosene's[fig6]. 7-Asample of the produced molecular sieve is available if required. (3)
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اإلدعبءاث المطلىة دمبٌخهب .خُٛبد انخغٛخ نفصم انجبسافٛئٚش يصفبح خضٕٚنزغVegobond A ذٕٛنٚاعزخذاو انض-1 .شٕٚ ْزا انزغٙ فA ذٕٛنٚذ انغٕس٘ يغ انضَٕٛاعزخذاو انجُز-2 .غجق صُؼٓب يٍ قجم يٍ انًكَٕبد انًزكٕسحٚ ذح نىُٚخ خذٛخ ْدٛئٚم يصفبح خضٛ رشك-3 اإليزضاصٙزٛ ػًهٙ) ٔ اعزخذايّ فٙش خٓبص انفصم (يخجش٘ َصف صُبػٕٚ يالزظخ رغ-4 . خٛئٚخ انًصفبح اندضٛٔ ػكظ اإليزضاص كًؤشش ػهٗ فؼبن
Claims To Be Protected 1- Use of the crystalline zeoletite A already implemented in detergent industry, to developed a molecular sieve for linear C10-C14 separation from kerosin 2- Use of Syrian Bentonite for this perpose. 3- A hybrid new molecular sieve formed from the above mentioned compounds. 4- Development of a laboratory pilotplant for this purpose is to be observed.
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المراجع References References on Zeolite 1- Breck D.W.1974 Zeolite Molecular Sieves-Structure, Chemistry and Use. Wiley Interscience, New York 2- Breck, Zeolite Molecular Sieves, New York: Wiley (1979); cited in: Römpp, Chemie Lexikon, Band 6, 9.Auflage (1992), Georg Thieme Verlag, Stuttgart 3- Allen, H.E., Cho S.H. Neubecker T.A.1983. Ion exchange and hydrolysis of type A Zeolite in natural waters. Water Res. 17, 1871-1879
References on Syrian Bentonite 4- Y.W.Bizreh, Damascus University journal Vol (18) N˚‗5, part (2) page7-38 (1989) 5- Hamwee, N. master degree dissertation P.29-39 Supervisered by Prof .Y.W.Bizreh, Damascus University (1996) 6- Shaheen Abeer, master degree dissertation Supervised by Prof .Y.W.Bizreh, P.47-52 7- Abdullah, Suzan master degree dissertation Supervised by Prof.Y.W.Bizreh P.39-74 Damascus University, Faculty of sciences (2003)
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Patent No.5333
ﺍﻟﺒﺮﺍءﺓ ﺭﻗﻢ 5224
Patent No.5190 New perborate activator for bleaching powders ﺍﺻﻄﻨﺎﻉ ﻣﺎﺩﺓ ﻣﻨﺸﻄﺔ ﺟﺪﻳﺪﺓ ﻟﺘﻔﺎﻋﻞ ﺗﻔﻜﻴﻚ ﺍﻟﺒﺮﺑﻮﺭﺍﺕ ﻓﻲ ﻣﺴﺎﺣﻴﻖ ﺍﻟﺘﻨﻈﻴﻒ
Patent No.5044
ﺍﻟﺒﺮﺍءﺓ ﺭﻗﻢ 4532
ﺍﻟﺒﺮﺍءﺓ ﺭﻗﻢ 4216 ﺗﻄﻮﻳﺮ ﻃﺮﻳﻘﺔ ﻻﺳﺘﺜﻤﺎﺭ ﻓﺤﻢ ﺍﻟﻜﻮﻙ ﺍﻟﺒﺘﺮﻭﻟﻲ ﺍﻟﻤﺸﻮﺏ ﺑﻨﺴﺐ ﻣﺮﺗﻔﻌﺔ ﻣﻦ ﺍﻟﻜﺒﺮﻳﺖ ﻓﻲ ﻣﺠﺎﻝ ﺗﻮﻟﻴﺪ ﺍﻟﻄﺎﻗﺔ
ﺍﻟﺒﺮﺍءﺓ ﺭﻗﻢ 4153
Fe3+, Co2+, Ni2+, Cr3+, Hg2+
5729 5654
2
2
16400
11400
0.56 7 1
100
2 3 ppm 1000 1
1 25
1000
1000
1000
1000
1000
ppm
8.79
19.1
8.670
0.472
17
ppm
99.12
98.09
99.13
99.95
98.3
2
0.27
25
1000
1000
1000
1000
1000
ppm
1.384
5.6
0
0.397
5
ppm
99.86
99.44
100
99.96
99.5
100 99
2010
5729
1
2009
5654
2
5729
6564
Removal And Recirculation of Heavy Metal Cations Fe3+, Co2+, Ni2+, Cr3+, Hg2+ From Their Water Solution By Adsorbents Made Of Olive Mill Waste Water
Appendix To Patents 5654 & 5729
Prof. YAHYA WALID AL BIZREH Prof. MALAK AL JAUB'E Ass. Prof. ADNAN DEAB Ass. LUBNA AL-HAMOUD
ABSTRACT Heavy metal cations have been removed from their water solution by means of adsorbents prepared from olive mill waste water. Removal of these cations has reached a value of 99 – 100 %.
Technical description of the invention: A- Condition: black powder may be carried on aluminsilicate carriers Density: 0.56 cm3/gr Surface area: 16400 cm2/gr Average diameter: 7 A° B- As for the invention: 1- No body has removed heavy metal cations from their water solutions by means of adsorbents prepared from olive mill waste water and recirculated those cations 2- As for the innovating step: A 99% - 100% removal of heavy metal cations from water solutions and recirculating those cations by our adsorbents in un preceded step. 3- Industrial application ability: this point is explained in the industrial scheme. C- Experiential results: 1- Water solutions of 1000 ppm concentration were prepared for each of Fe3+, Co2+, Ni2+, Cr3+, Hg2+ cations starting from their nitrate salts. 2- One gram of the adsorbent produced from carrying the OMWW coal on aluminosilicate was immersed in 25 ml of
each the above mentioned solutions for 3 days in a statical state. The resulting filtered solutions were almost free of the polluting cations. Results for the purifying efficiency of the suggested adsorbent are listed in the following table: Hg2+
Fe3+
Cr3+
Ni2+
Before Adsorption ppm
1000
1000
1000
1000 1000
After Adsorption ppm
17
0.472
8.670
19.1
98.3
99.95
99.13 99.09 99.12
Cation
Removal %
Co2+
8.79
When 25 ml of the polluted waters was treated with 0.27 gr. of the invented material, in the same way mentioned above, similar results listed in the following table were received: Hg2+
Fe3+
Cr3+
Ni2+
Before Adsorption ppm
1000
1000
1000
1000 1000
After Adsorption ppm
5
0.397
0
99.5
99.96
100
Cation
Removal %
5.6
Co2+
1.384
99.44 99.86
What is claimed to: Adsorption of Hg2+, Fe3+, Cr3+, Ni2+, Co2+, on active carbon produced from olive mill waste water and their recirculation.
Industrial Chart
Original References: 1- Syrian Patent 5654/ 2009 2- Syrian Patent 5729 / 2010