JL DUBOIS - Glycerol

Sustainable Glycerine Dehydration to Acrolein and Acrylic Acid

Jean-Luc DUBOIS Scientific Director

Arkema’s Plant-Based factories 4 Vegetable Oil-based 1 Wood-based 11 % of Turnover (~ 700 M€ / 1 G$) Coating Solutions

Feuchy (since 1928)

Hengshui (since 2008)

Fatty Nitriles & Amines

Castor Oil-Based PA Monomers Sebacic Acid

Vegetable Oil based

Blooming Prairie (since 1970)

Epoxidized Linseed & soybean Oils, Terpenes

Parentis (since 1941)

Wood-based Activated Carbons

Marseille St Menet (since 1955)

Castor Oil based Polyamide Monomer

Arkema’s Renewable Products have technical advantages

3

Jean-Luc DUBOIS, Arkema France, AOCS, 4-7th May 2014

Malaysia

BioMethionine Under construction

New Biobased Products and R&D Projects Corporate

Coating Solutions

Target for Biobased products in Arkema: 15 % of Turnover in 2016 XX

Carling/Pierre Bénite

Carbon Nanotubes

Vegetable Oil based Biobased Acrylic Acid

Corporate

Vegetable Oil-Based Monomers Biobased Acrolein

PMMA RNew

Improved Performance

CECA

CRRA, Pierre-Benite

Feuchy

New Lignocellulosics Activated Carbons

Metathesis based Specialty Monomer

Fatty Nitriles & Amines

Arkema’s Renewable Products have technical advantages

4


Patent Applications including Glycerol, Dehydration, and Acrolein in Title, Abstract or Claims

Selective elimination of Propanal in acrolein (Priority 28 Jan 2011)

Arkema’s Acrylonitrile patent (Priority: 16 Feb 2007)

Arkema’s 1st patents – Co-feeding of O2 – Catalysts include W/ZrO2, W/TiO2, PW/TiO2… acid catalysts (Priority: 15 Feb 2005) 1 step to Acrylic Acid (Priority 25 Apr 2005)

5


Catalyst Pore size distribution (Priority 29 July 2011)

Top 10 Assignees (by patent Family)

6


European and US production of Glycerine. Sources: HBI, EBB, US Bureau of Census, EPA

European and USA production of Glycerine 1200

Production (throusand tons)

1000

Europe USA

800

600

400

200

0 1994

1996

1998

2000

2002

2004 Year

7


2006

2008

2010

2012

2014

Glycerine prices on European and US markets (Sources: HBI, EBB)

Glycerine Kosher 99.7 % and Crude 80 % prices 2000

120

100

1600

Prices (€/ton)

1400

80

1200 1000

60

800 40

600 400 200 0 j-93

USA Kosher quality, €/ton Europe Kosher quality, €/ton Euroepe Crude 80 %, €/ton USA Kosher quality, cents/lb

o-95

j-98

a-01

20

j-04

o-06 Date

8


j-09

a-12

d-14

0 s-17

Average SU Spot prices delivered in Bulk (Kosher Refined) cents/lb

1800

Acrolein/ Acrylic Acid: ARKEMA’s Project Acrolein and Acrylic acid are currently produced from propylene (Petroleum). Double internal dehydration of Glycerol leads to Acrolein which is further oxidized to Acrylic acid Crude Glycerol Tank

Acrolein/Acrylic Acid Unit

Methionine

Fine Chemicals/ Fragrances

Separation

Tank

Acrolein or Acrylic acid

Ubiquitous O

OH HO OH

Thermal Oxidizer

H2C

+

2H2O

H2C

Polyacrylate= dispersing agents for minerals

O

Wastes: salts…

OH

Superabsorbants

Classical Acrolein and Acrylic acid processes Standard Acrolein plant: Methionine: 30 kt/yr Pyridine: few kt/tr Glutaraldehyde: few kt/yr Fine chemicals: few 100t/yr

Standard Acrylic Acid plant: Superabsorbants, Esters: 80 - 160 kt/yr

Techniques de l’ingénieur, 1995, J6055 and J6100 11


Glycerol – a new raw material for Chemical Industry

12


Environmentally Friendly Process: Avoid scenarios of past accidents Target: develop a new process for on-site Acrolein production (PROXI-plants) to avoid storage and transportation of a highly toxic Chemical. Pierre Bénite, France. July 10, 1976. Taft, USA/ December 10, 1982.

Major contamination of the Rhône River, during clean-up of a train tank 367 Tons dead fish

12


Explosion of a Storage facility 17000 people evacuated

Cradle to gate analysis CO2

Acrolein ex propylene: 3190 kg CO2/t

Plant growth = consumption of atmospheric CO2

Acrol. ex glycerol: Target 980 kg/t Acrylic acid ex Propylene: 950 kg CO2 /t Acrylic Ac. ex glycerol: target 0 kg/t

Methanol Transesterification

Diesel Blend Biodiesel

Vegetable Oil

Glycerine Acrolein/ Acrylic Acid Done within the Glyvalacr Project sponsored by Ademe 13


Reaction mechanism O

HO

HO HO

- H2O

OH

OH

- H2O

OH

H 1,3-dihydroxy-propene

OH HO

Ethenol

formaldehyde

-H2O

O

OH

O

OH

Acrolein

glycerol

O

Heavies

Hydrogen transfer

H HO

H

2,3-dihydroxy-propene

H O

HO hydroxyacetone (acetol)

14

O H

- H2O

O H

OH

O

+

3-hydroxy-propanal

H O

O

O

vinyl alcohol acetaldehyde

O

O

- H2O


+

Propanal

OH

+H*

O

OH Prop-2-en-1-ol

O O

O

OH

Acetals

H3C

CH3

acetone

Glycerin – Basic data. Boiling Point Temperature °C

OH HO

Pressure Hg

290

760

274

500

222

100

165

10

OH Heating Value

GLYCERINE

15


Compound

kcal/kg

Glycerin

4 076

Natural Gas

12 000

Fuel N°2

10 000

mm

Fluid properties: Concentrations range of pumpable material

16


Vapor-Liquid

Temperature need to be high enough to avoid Glycerine condensation 17


Energy Intensive process (energy consumption for water evaporation only partly recovered)

300 260 220 180 140 100 0

20

40

80

60

Boiling point at 760 mmHg, °C

Boiling points of Aqueous Glycerol Solutions

100

Glycerol weight % Ref: Industrial Solvents Handbook (5th Ed)

18


Winter Storage conditions

Melting Point: 18 °C Freezing Point (eutectic): -46.5 °C (66.7 % glycerol solution)

It is preferable to use Crude Glycerine, or aqueous Glycerine solutions to avoid heated tanks All properties combined point to a 30 to 90 %, and preferably about 50 wt % concentration

Vapor Pressure of Glycerine

Vapor Pressure, mm Hg

0.01

1

0.001

0.1

0.00 60 80

100 120 140

180

220

Temperature, °F 20


260

300

0.01 340

Vapor Pressure of Glycerine 260

300

340

380

420

Vapor Pressure, mm Hg

100

10

1000

280 °C

300 °C

1

100 Temperature, °F

21

420


460

500

540

580

Effect of Glycerol – water weight ratio

Molar selectivities (mol C / mol converted gly)

DL090209_2 DL090209_3 DL090209_4 Date 09-feb-09 17-feb-09 23-feb-09 Reaction time 23 h 23 h 23 h O2 / Glycerol mol ratio 0.62 0.62 0.60 Glycerol / H 20 mass ratio 20% 20% 30% Glycerol 4.1% 4.1% 6.4% Inlet gas composition (%) H20 84.1% 84.1% 75.9% N2 9.2% 9.2% 13.9% O2 2.5% 2.5% 3.8% SBT : Salt bath temperature (°C) 320°C 320°C 320°C PT : Peak temperature (°C) 335°C 335°C 341°C ∆Τ (PT - SBT) 14.7°C 14.6°C 21.1°C SV0 (glycerol) (h-1) 91 92 94 SV total (h-1) 2224 2225 1477 Glycerol conversion 100.0% 100.0% 100.0% Acrolein Yield 74.8% 74.1% 71.6% Acrolein 74.8% 74.1% 71.6% Formaldehyde 1.36% 1.50% 1.62% Methylglyoxal 3.25% 2.77% 3.02% Propionaldehyde 0.47% 0.43% 0.53% Propionic acid 0.10% 0.11% 0.15% Acetaldehyde 6.85% 6.25% 7.58% Acetone 0.00% 0.00% 0.00% Hydroxyacetone 0.17% 0.17% 0.14% Allylic alcohol 0.00% 0.00% 0.00% Acrylic acid 2.22% 2.16% 3.38% Acetic acid 1.57% 1.59% 2.12% CO + CO2 5.21% 5.41% 6.98% Hydroxypropionaldehyde 0.31% 0.27% 0.17% Acetals (as ACO + Glycerol) 0.16% 0.17% 0.20% Heavies (mass) 1.74% 1.08% 1.03% Carbon balance 98.3% 96.0% 98.5%

Raw material : ● Glycerol : Refined glycerol ● Catalyst ref. Z1044 : 10%WO3ZrO2, from DAI ICHI (cylinders, bulk catalyst)

Reference conditions : ● GHSV= 2250 h-1 ● Catalyst weight: 511 g ● Flow rate: 878 Nl/h

Reaction temperature ●

320 °C

Regeneration step after each run Run duration : 24hr

Glycerol dehydration to acrolein

Initial catalyst screening (high throughput screening): 250 catalysts Catalyst optimization: 250 catalysts tested Scale up in 1 m fixed bed: 15 catalysts tested

Glycerol intramolecular dehydration 1m fixed bed reactor results W/ZrO2 1st generation Acrolein Yield (%) Run duration (h) Number of regenerations tested Water/glycerol weight Ratio

Propionaldehyde yield (%)

A

B

C

70

65

75

78

75

24-36

18-24

24-48

72

72

51

10

2

2

(1200 hrs)

(264 hrs) 2.3

2.3

1

2.3

0.3

0.5

0.5

0.4

2.3

1

(30 wt % glycerol)

(50 wt % glycerol)

0.7

0.7

80

As of Jan 2013: completed 1700 hrs of operation and 70 regeneration cycles 24


Glycerol to Acrolein- Operating conditions (Typical) Operating Conditions. ● Temperature: 300-320°C ● Pressure: 2 bara ● GHSV: 2 250 Hr-1

WO33/ZrO /ZrO22(here), Catalyst: WO (solid HPA/TiO acid) 2, W/TiO2, and other solid acids Ratio Glycerol/Water: 30/70 (w./w.) Ratio O2/Glycerol: 0.42 (mole/mole) ● Glycerol: 6.7 % vol. ● Water: 79.9 % vol. ● O2: 2.8 % vol. ● N2: 10.6 % vol.

Acrolein purification Example of product qualities

Reference Batch A

Reference Batch B

Reference Batch B-purified

wt % 3.24

wt % 4.16

wt % 3.00

0.22%

0.34%

0.11%

0.08%

1.18%

0.75%

0.55%

0.05%

0.00%

0.00%

Formaldehyde

0.065%

0.154%

0.049%

Acetaldehyde

10.5%

12.2%

0.74%

2-oxopropanal

0.0496%

0.0201%

Crotonaldehyde

0.0998%

0.0240%

Acrolein dimer

0.0019%

0.0011%

0.1879%

0.1325%

H2O Acetone 2,3-butanedione Propionaldehyde Hydroxypropionaldehyde

HydroQuinone (stabilizer) 26


0.2165%

Improvement of product quality

27


Improvement of Acrolein Quality: Reduction of Propanaldehyde content

Besides the main reaction (Glycerol to Acrolein) there is formation of coke accompanied by Hydrogen transfer reactions. A possible propanaldehyde formation mechanism is Acrolein hydrogenation. Propanaldehyde cannot be separated from Acrolein through distillation. Propanaldehyde will generate impurities in most Acrolein applications. A new Catalytic process has been develop to selectively react propanal (tentatively through oxydehydrogenation) without affecting significantly the Acrolein yield.

Selective propanaldehyde elimination Catalyst GHSV (h-1)

FeMoOx 10 000

FeMoOx 20 000

FeMoOx 20 000

BiMoFeOx 5 800

TiO2 3 700

TiO2 15 000

Vaporizer and Reactor temperature (°C)

305

330

305

325

300

270

Aco/Pal/O2/N2/H2O

a

a

b

a

a

a

Propanal conversion (%)

98

99

99

96

16

99 76

Catalyst PW/TiO2 (1st layer) and CsPMoO (2nd layer) Glycerin aqueous solution (50 wit %) Evaporation rate 12.4 g/hr, Nitrogen 14.4 Nl/hr, Oxygen 0.95 Nl/hr (composition: glycerol/water/O2/N2=6.2/31.5/3.5/58.5) GHSV=2500 h-1 (1st layer), 10000 hr-1 (2nd layer); 280 °C, 1.7 Bars Gauge

Reaction mechanism and impact of coke formation Coke formation on catalyst ● Generate diffusion limitations

required to operate at high linear gas velocities

● Without O2 in the feed, fast deactivation ● With O2 in the feed slow deactivation. Coke formation still observed. ●

a low T coke is continuously burned, and a high T coke continues to build-up.

Regeneration is limited by mass/heat transfer ●

Small Catalyst Particle size (fluid bed process)

●

Large Catalyst Particles: Bimodal pore size distribution (fixed bed process) –

Facilitate catalyst regeneration and improves reactivity

Very small pores are quickly blocked by capillary condensation, unless one operates in diluted conditions (energy intensive, low productivity…)

Temperature – Pore size relation for Capillary condensation at 1 Bar, 16 mol % Glycerine eq to 50 wt % glycerine aqueous solution) Sources: surface tension (www.surface-tension.de), Vm (molar volume), r radius

To avoid capillary condensation: use highly diluted glycerol, high temperature, or large pore catalyst 310

Catalyst working temperature

290

Temperature, °C

CAPILLARY CONDENSATION

250

230

Zeolite A

Alumina

ZSM 5 Zeolite Y MCM-41,SBA-15

210

190 0.1 32

Kelvin equation: Ln(P/Po)=-2γVm/rRT

270


Zirconia Silica

1

Titania

10 Pore size (nm)

(Diameter)

100

Deactivation by Coke formation: Impact of catalyst pore structure see for example Arkema patent applications WO 2013/017942 & W0 2013/018915

Total Pore Volume (ml/g)

Ratio PV Macro/ meso pores

Mesopore diam. at peak max (nm)

Macropore diam. at peak max (nm)

Surface Area (m²/g)

Glycerol conv. at 19 hrs (%)

Acrolein Yield at 19 hrs (%)

Glycerol conv. at 43 hrs (%)

Acrolein Yield at 43 hrs (%)

1

0.36

1.4

18.5

130

48.2

99.6

77.0

95.6

73.6

4

0.36

1.3

19.9

160

39.9

99.5

77.4

93.2

70.9

5

0.36

1.4

18.4

159

45.6

99.7

76.9

94.8

72.1

8

0.40

0.9

20.5

134

53.0

99.4

74.5

94.7

69.4

COMP1

0.40

0.4

16.6

452

75.0

99.3

73.5

88.2

64.8

COMP2

0.32

0.3

18.9

140

52.0

96.8

70.4

78.0

56.2

Catalyst

Operating conditions: 20 mm internal diameter reactor, 30 ml catalyst, furnace temperature: 290 °C. 50 wt % Glycerol aqueous solution, cofeeding with air. Glycerol/O2/N2/H2O: 4.7 / 2.8 / 68.5 / 24 (mol %); GHSV: 2020 h-1. 33


Acid and Basic sites involved in the reaction selectivity Selectivity to acrolein increases as number of Basic sites decreases Basic sites catalyze side products formation.

D Stosic, S Bennici, JL Couturier, JL Dubois, A Auroux, Catalysis Communications 17 (2012) 23-28 34


Acrolein Uses

35


Acrolein: a platform molecule, for Bio-based products CH3

R1

O

R1

R1

R2

R2

O

R2

O

H3C

H3C

R3

R4

R4

O

O

O

H3C

O

O

R3

R3

O

O O

O

R4

O

O

H3C

O

O O

CH3

CH2

R

Mg Cl

HO

R

R1

R1

O

R

O

R

O

O

R2

O

R2

O

R O

R

R

R

O

O

O

O O

R

R

O

H2C

NH2

CH2

n

CH2

N

O

O

N H

O O

R

O

O

O

O

N

NH

Br Br

O

O

O

O

CH3

CH3 O

Cl

O

CH3

Cl

H3C

O

O

O

O O

O

O

O

CH3

O

O CH3

N

N N

36

CH3


CH3 N

Some products made out of Acrolein Cl

O O

Cloquintocet-M Ciba Geigy’s herbicide

Quinfamide Winthrop antiprotozoan

N

O

O CH3

N Cl O

O

O

O

O

CH3

Cl

CH3 OH

HN

Pentabromopseulidin H N

Br

Br

F

Br Br

O

Intermediate to ATORVASTATIN

O

Br

R

H3C O

O

Cyclopentenone (used in Jasmone industry)

Cl OH

O

NH2

O

S R

+

NH

O

O

CH3

CH3

O


N

O

Cl

Chlothenoxazine (analgesic) 37

H N

O

Dopaminergic

Some other products made from Acrolein O S

Chloroquin H2C

S NH

N

CH3

O

S

Cl

O

Letosteine

HN

H3C

N

Methional

O

Methionine

CH3 CH3

H2C

OH

O

H3C

O

H3C O

H3C

SH

S

S H2N

Meticran (diuretic)

CH3

S O

O

O H3C

NH

N

O

O

O

Melatonin

H3C

S

H3C

N H

N

CH3

O NH H3C

N

Sumatriptan 38

N


N H

Rizatriptan

N

N H

CH3

CH3

12 Principles of Green Chemistry 1.

Prevent waste

2.

Design safer Chemicals and Products

3.

Design less hasardous chemical synthesis

4.

Use Renewable feedstocks

5.

Use catalysts not stoichiometric reagents

6.

Avoid Chemical derivatives

7.

Maximize atom economy

8.

Use safer solvents and reaction conditions

9.

Increase Energy effciency

10.

We use a waste Same products offer market access Process for on-site production

Glycerol Heterogeneous Catalyst

Direct route C3 to C3 no solvent, safer process

Translated into CO2 balance

Design Chemicals and products to degrade after use to the atmosphere

11.

Analyse in Real time to prevent pollution

12.

Minimize the potential for accidents

return plant-based CO2

Target = on-time consumption

Avoid transportation and storage

Thank you for your Attention.

40
