(12) United States Patent

US009546102B2

(12) United States Patent

(10) Patent No.:

Rytwo

( 45 )

(54)

METHOD FOR PRETREATMENT OF WASTEWATER AND RECREATIONAL WATER WITH NANOCOMPOSITES

(71)

Applicant: Gavish-Galilee Bio Applications, Ltd., Kiryat Shmona (IL)

(72)

Inventor:

(73)

Assignee: GAVISH-GALILEE BIO APPLICATIONS LTD., Kiryat Shmona (IL)

(* )

Notice:

(58)

Giora Rytwo, Kiryat Shmona (IL)

(56)

Appl. No.: 13/967,644

(22)

Filed:

(51)

EP

Feb. 13, 2014

(52)

Continuation-in-part of application PCT/IL2012/000245, filed on Jun. 21, 2012. (Continued) Int. Cl. B 0ID 21/01 C 0 2 F 1/52 C 0 2 F 1/56 B03D 3/00 C 0 2 F 1/00 C 0 2 F 101/10 C 0 2 F 101/16 C 0 2 F 101/34

References Cited

FOREIGN PATENT DOCUMENTS 1870380 A1 * 12/2007

............... C02F 1/52

OTHER PUBLICATIONS

Related U.S. Application Data (63)

(2013.01) ; C02F 2101/105 (2013.01); C02F 2101/163 (2013.01); C02F 2101/345 (2013.01) ; C02F 2103/007 (2013.01); C02F 2103/20 (2013.01); C02F 2103/22 (2013.01); C02F 2103/26 (2013.01); C02F 2103/322 (2013.01) ; C02F 2103/325 (2013.01); C02F 2305/08 (2013.01) Field of Classification Search None See application file for complete search history.

(Continued)

Prior Publication Data US 2014/0042100 A1

Jan. 17, 2017

3,066,095 A 11/1962 Hronas 5,433,865 A * 7/1995 Laurent ........................ 210/727

Aug. 15, 2013

(65)

Date of Patent:

U.S. PATENT DOCUMENTS

Subject to any disclaimer, the term o f this patent is extended or adjusted under 35 U.S.C. 154(b) by 233 days.

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US 9,546,102 B2

No.

(2006.01) (2006.01) (2006.01) (2006.01) (2006.01) (2006.01) (2006.01) (2006.01) (Continued)

U.S. Cl. CPC ............. C02F 1/5236 (2013.01); B 0ID 21/01 (2013.01); C02F 1/56 (2013.01); C02F 1/5272

G. Jock Churchman: “Formation of complexes between bentonite and different cationic polyelectrolytes and their use as sorbents for non-ionic and anionic pollutants”; Applied Clay Science 21; pp. 177-189. (2002).

(Continued) Primary Examiner — Nam Nguyen Assistant Examiner — Clare Perrin (74) Attorney, Agent, or Firm — Browdy and Neimark, PLLC (57)

ABSTRACT

A single step pretreatment of wastewater or recreational water is provided comprising treatment with nanocomposites consisting of an anchoring particle such as a clay mineral and one or more polymers. 23 Claims, 24 Drawing Sheets (19 of 24 Drawing Sheet(s) Filed in Color)

US 9,546,102 B2 Page 2 Related U.S. Application Data (60)

Provisional application No. 61/500,296, filed on Jun. 23, 2011.

(51)

Int. Cl. C 0 2 F 103/00 C 0 2 F 103/20 C 0 2 F 103/22 C 0 2 F 103/26 C 0 2 F 103/32

(56)

(2006.01) (2006.01) (2006.01) (2006.01) (2006.01) References Cited

Rytwo et al: “Organo-sepiolite particles for efficient pretreatment of organic wastewater: Application to winery effluents”; Applied Clay Science 51; pp. 390-394. (2011). Rytwo et al: “Very fast sorbent for organic dyes and pollutants”; Colloid Polyrn Sci 284; pp. 817-820 (2006). Zadaka et al: Atrazine removal from water by polycation-clay composites: Effect of dissolved organic matter and comparison to activated carbon; Water Research 43; pp. 677-683. (2009). Total Organic Carbon, On line Analysis of organic in water, pp. 1-6, Teledyne Analytical Instruments (2015). Zimmels et al., Removal of high organic loads from winery wastewater by aquatic plants, Water Environ Res., 80 (9):806-22 (2008). Masi et al., Winery high organic content wastewater treated by constructed wetlands in Mediterranean climate, Conference Proceedings of the IWA 8thInternational Conference on Wetland Systerns for Water Pollution Control, Arusha (TZ), vol. 1, 274-282 ( 2002 ) .

U.S. PATENT DOCUMENTS 2005/0258103 Al * 2007/0172913 Al * 2009/0206040 A l*

11/2005 Cort ............................. 210/695 7/2007 Hughes et al.................... 435/41 8/2009 Berg et al...................... 210/728

OTHER PUBLICATIONS Ganigar et al: “Polymer-clay nanocomposites for the removal of trichlorophenol and trinitrophenol from water”; Applied Clay Science 49; pp. 311-316. (2010). S. M. Mousavi et al:“Use of Modified Bentonite for Phenolic Adsorption in Treatment of Olive Oil Mill Wastewater”; Iranian Journal of Science & Technology, Transaction B, Engineering, vol. 30, No. B5: pp. 613-619 (2006). Giora Rytwo; “The Use of Clay-Polymer Nanocomposites in Wastewater Pretreatment”; The ScientificWorld Journal vol. 2012; pp. 1-7. (2011). Rytwo et al: “Use of CV- and TPP-montmorillonite for the removal of priority pollutants from water”; Applied Clay Science 36 ; pp. 182-190. (2007).

Rytwo and Malka, “A pilot plant for the treatment of cowshed effluents” Water & Irrigation, 530:6-9 (Sep.-Oct. 2013). Dharmappa et al., Wastewater characteristics, management and reuse in mining & mineral processing industries, Encyclopedia of Life Support Systems (EOLSS), vol. I, pp. 1-10 (2002-2011). Rytwo, et al., “Three unusual techniques for the analysis of surface modification of clays and nanocomposites” in: Beall, G., Powell, C.. (Eds.), Clays Minerals Society Workshop Series vol. 20 “Surface Modification of Clays and Nanocomposites.” Clay Mineral Society, Boulder, CO, pp. 1-16 (2016). Rytwo, et al., “Direct Relationship Between Electrokinetic Surfacecharge Measurement of Effluents and Coagulant Type and Dose” Colloids Interface Sci. Commun. 1:27-30 (2014). Rytwo, et al., “Clarification of olive mill and winery wastewater by means of clay-polymer nanocomposites” Sci. Total Environ. 442:134-142 (2013). Von Homeyer et al., “Optimization of the polyelectrolyte dosage for dewatering sewage sludge suspensions by means of a new centrifiigation analyser with an optoelectronic sensor” Colloid Polym. Sci. 277, 637-645 (1999).

* cited by examiner

U.S. Patent

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Sheet 1 of 24

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Fig, 2 A

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Sheet 2 of 24

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Sheet 3 of 24

Charge (mmoi/Kg)

F is . 3

Added PD (mg polymer/g day)

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Sheet 4 of 24

(m m /s)

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harmonic m ean velocity (m m /s)

harmonic mean velocity

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Polymer-clay ratio (mg/g)

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Sheet 5 of 24

relative attenuation

Fig. 6

time (hours)

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Sheet 6 of 24

Fig. 7A

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Sheet 7 of 24

Fig. 7B

c‫־‬spacing [A]

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Fig. 8

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Sheet 9 of 24

Fig. 9

m

8

E 0

‫נד‬

2

3

cy cle

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Sheet 10 of 24

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Fig. 10.4

.........100 ‫״■״״ ״‬200 — < 320 « . ‫■״‬490 — ?0

relative light intensity [%]

60 50 40 30 20

10 0

650 —

800 — ‫ ״‬970 — ‫ י‬- OMW

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Sheet 11 of 24

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Fig. 10B

100 —

1 60•

200

‫ ״‬320 ‫ ״‬- ‫ ״ ״‬490

relative light intensity [%]

70 60 50

40 30 20 10

0 lime [minj

•650

970------GMW

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Fi

11A

Fig, 11B

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Fig. 11C

Fig. 11D

P#§itlnn in

mm

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Fig, H E

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Sheet 15 of 24

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Fig. 12A.

Light intensity [%!

100

90 80 70 80 50 40 30 20 10 0

PDAD MAC-S9 (mg polymer per gram clay)

Lig h t Intensity [%J

Fig. 12B

chitosan‫״‬S 9 (mg polymer per gram clay)

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Sheet 16 of 24

Fig. 12C

Fig. 13

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Sheet 17 of 24

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Fig. 14

Fig. 15 BO

NH21

NCI 9

NC26

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Sheet 18 of 24

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Fig. 16

c O

£

c few

NG2S NCSQ NCI 00 PD40 PD80 PD 160 AL2.30 AL460 AL910 OUW

Fig. 17

-500 15 -1000 Ui

I

0

1 -1500 ©

OS

I 2000‫־‬ o

-2500 polymer/clay ratio (mg/g)

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Sheet 19 of 24

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Fig. 18 80

70 £ 60 I

#3

50

m

I

40

1 30

£ ^

20 1Q

0

20

30

40

60 80 100 160 240 320 400 500 DE NMV / clay ratio [mg/g]

Fig. 19

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Fig. 20

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Fig. 21

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0

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Fig. 24

Transmission [%]

Fig. 25 80 70 60 50 40 30

‫־‬1 H ‫־‬

1

20

10 0 CN

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CM CD

O

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