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WO2008052993A2 - Procédé de fabrication d'acroléine et autres composés oxygénés à partir de glycérol dans un réacteur à lit transporté - Google Patents

Procédé de fabrication d'acroléine et autres composés oxygénés à partir de glycérol dans un réacteur à lit transporté Download PDF

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Publication number
WO2008052993A2
WO2008052993A2 PCT/EP2007/061695 EP2007061695W WO2008052993A2 WO 2008052993 A2 WO2008052993 A2 WO 2008052993A2 EP 2007061695 W EP2007061695 W EP 2007061695W WO 2008052993 A2 WO2008052993 A2 WO 2008052993A2
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WIPO (PCT)
Prior art keywords
glycerol
process according
catalyst
acrolein
acid
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Ceased
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PCT/EP2007/061695
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English (en)
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WO2008052993A3 (fr
Inventor
Paul O'connor
Avelino Corma Camos
George Huber
Louis Andre Savanaud
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Bioecon International Holding NV
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Bioecon International Holding NV
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Publication of WO2008052993A3 publication Critical patent/WO2008052993A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/52—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition by dehydration and rearrangement involving two hydroxy groups in the same molecule

Definitions

  • This invention relates to a process for production of acrolein and other oxygenates from glycerol with acidic solid materials in a transported bed reactor.
  • Biodiesel production is increasing worldwide as our society looks to overcome problems caused by our dependence on fossil fuels (Bendz 2005; Knothe, Krahl et al . 2005; Huber, Iborra et al . In Press).
  • Biodiesel also called fatty acid methyl esters or FAME, is produced by transesterification of vegetable oils (triglycerides) and methanol with glycerol produced as a byproduct with a molar ratio of 1:1 glycerol to triglyceride (Bendz 2005; Knothe, Krahl et al . 2005; Huber, Iborra and Corma 2006). It is estimated that approximately 80 % of the biofuels in Europe are biodiesel (Bendz 2005) .
  • Glycerol is currently a valuable by-product of biodiesel production. As biodiesel production increases the price of glycerol is projected to significantly drop, and the price of glycerol has already dropped by almost half over the last few years (McCoy 2005) . Therefore it is desirable to develop inexpensive processes for the conversion of glycerol into valuable chemicals.
  • the glycerol by-product from a biodiesel plant contains a number of impurities including water, soaps, bases, and salts. The concentration and level of these impurities will depend on the type of process that is used for biodiesel production.
  • Acrolein is a valuable chemical and is used to produce a wide range of chemicals, including acrylic acid, acrylic acid esters, superabsorber polymers, and detergents.
  • Sabatier and Gaudion produced acrolein from glycerol by dehydration in the gas-phase with both AI2O3 and UO2 catalysts at 360 and 350 0 C, respectively (Sabatier and Gaudion 1918) .
  • a 10 % acrolein yield was observed, with other products being ethanol, water and allyl alcohol.
  • Freund patented a process for producing unsaturated organic compounds by dehydration with siliceous clays or other aluminum magnesium hydrosilicates (Freund 1928) .
  • Freund observed that pure acrolein could be produced from glycerol at 180 0 C using diatomaceous silica (Freund 1928), with no indications on the by-products formed.
  • Hoyt and Manninen patented a method for production of acrolein from glycerol water mixtures (Hoyt and Manninen 1951).
  • the glycerol-water solution was treated with a solid phosphoric acid catalyst.
  • the solid acid catalyst was prepared by impregnating 100 parts of a solid catalytic support with 3-25 parts of orthophosphoric acid, meta-phosphoric acid, pyrophosphoric acid or phosphorus pentoxide (Hoyt and Manninen 1951). According to Fougret et al .
  • phosphoric acid supported on Ti ⁇ 2, Si ⁇ 2 and Si ⁇ 2-Ti ⁇ 2 have H 0 (Hammett acidity function) from -3.0 to -8.2 depending on the proportion of the different forms of phosphoric acid supports (Fougret, Atkins et al . 1999).
  • Pure AI2O3 has a H 0 around +1 (Jansen, Palmieri et al . 1996) . Therefore, it is likely that phosphoric acid support on AI2O3 would have Ho from +1 to -8.2, depending on the proportion of the different forms of phosphoric acid relative to the support.
  • Solid phosophoric acid catalysts are well known acid catalysts, and have been used industrially since 1930(Eglorr 1936; Fougret, Atkins et al . 1999; Coetzee, Mashapa et al . 2006).
  • Hoyt and Manninen's patent they claim that finely divided carbon, activated carbon, coke, asbestos, silica gel and activated alumina can all be used as catalyst supports for phosphoric acid.
  • Overall yields of 72 % of acrolein from a 95 wt% glycerol solution (5 % water) at 286 0 C were observed.
  • H 0 varies from +1 (the value for Al 2 O 3 ) to -24 (value for zeolite catalysts) (Jansen, Palmieri et al . 1996; Haw 2002) . Heinemann et al . observed acrolein yields of up to 42 % from glycerol using Bauxite catalysts by gas-phase reactions at 430 0 C (Heinemann, Wert et al . 1949). In 1993, Degussa patented a process to produce acrolein by dehydration of glycerol in the liquid or gaseous phase with solid acidic catalysts (Neher, Haas et al . 1995).
  • aqueous solutions from 10-40 wt% glycerol can be converted to acrolein at 180-340 0 C in the liquid phase or 250-340 0 C in the gaseous phase.
  • phosphoric acid supported on AI2O3 as a catalyst.
  • phosphoric acid on alumina was already shown by Hoyt et al to be an effective catalyst for acrolein production (Hoyt and
  • Acrolein can also be prepared from glycerol using sub- and supercritical water (Ramayya, Brittain et al . 1987; Buhler, Dinjus et al . 2002; Ott, Bicker et al . 2006) or with homogenous catalysts (Drent and Jager 2000).
  • the maximum acrolein yield with sub-and supercritical water was reported to be 37.5 % at 360 0 C, 25 MPa, and 470 ppm (g g "1 ) of zinc sulfate by Ott et al . (Ott, Bicker et al . 2006).
  • the method of the present invention has a number of advantages over prior art processes.
  • Our process can process glycerol solution in whatever concentration, with only small changes in selectivity and activity of the catalyst; it does not need any co-solvent to carry out the reaction; and continuously regenerates the catalyst so that catalyst activity can be maintained over large periods of time, even with contaminated feeds.
  • the less valuable heavy by-products of the reaction can be burned inside the process, thus generating the heat that is necessary to carry out the process, as water vaporization requires large heat input.
  • This invention relates to a process for the production of acrolein and other oxygenates by dehydration of glycerol.
  • the glycerol feed may be in the form of pure glycerol, a glycerol-water mixture, or glycerol-containing solutions produced in the transesterification of vegetable oils.
  • the process is carried out in a transported bed reactor.
  • the transported bed reactor preferably is part of a continuous process whereby, in a first step, salts present in the feed are removed from this by adsorption ion exchange or by evaporating the feed.
  • the resulting feed is mixed with a catalyst and passed through a heated zone.
  • the catalyst and reaction products are separated, and the catalyst is continuously regenerated.
  • the catalyst used is a solid acid catalyst (either Br ⁇ nsted or Lewis acid) .
  • ZSM-5 zeolite is preferably included as the main catalyst component.
  • One of the requirements is the use of a transported bed at high space velocities, with continuous regeneration of the catalysts a desired embodiment.
  • Fig. 1 is a schematic representation of the production of acrolein from glycerol.
  • the glycerol is first purified to remove any bases, salts or other impurities that may poison the catalyst.
  • the catalyst is circulated from the regenerator (Reactor 1) to the glycerol dehydration transported reactor (Transported bed reactor 21), followed by the stripper (Reactor 3) , which separates the reaction products from the catalyst.
  • the catalyst is returned to the regenerator in order to burn coke on the catalyst surface to provide process heat and regenerate the catalyst.
  • a part of the catalyst may be recycled from the stripper to the reactor without regeneration.
  • the present invention relates to a process for the production of dehydrated oxygenated compounds comprising contacting a glycerol-water solution containing from 10-100 wt% glycerol with an acidic solid catalyst in a moving bed reactor at 200-650 0 C.
  • the glycerol may be in an aqueous solution (from 10 to 100 wt% glycerol) , which definition includes pure glycerol.
  • the glycerol solution may be a byproduct of biodiesel production from transesterification of vegetable oils.
  • a glycerol solution from a biodiesel process is first neutralized to remove bases and salts that may poison the catalyst. To improve downstream processing,
  • (additional) water may be added to the glycerol feed.
  • the glycerol solution is contacted with a catalyst react in a moving bed reactor, typically transported by a vapor lift, as shown in Figure 1.
  • the temperature of the moving bed reactor may range from 200-650 0 C, more specifically from 290 to 400 0 C.
  • Contact time is in the range of 0.005 to 5 seconds.
  • Catalyst-to-glycerol weight ratios are in the range of from 2 to 100, preferentially from 5 to 20.
  • the glycerol feed is contacted with the catalyst by convenient means, such as a multiple spray nozzles that ensure a good distribution of the feed through the reactor.
  • Such injection devices are well known to those trained in the art of the fluid catalytic cracking processes.
  • Gas products and catalyst are then transported through the reactor 21 to the stripper 3, where the catalyst and the gas products are separated. Separation means are the same as those used in fluid catalytic cracking.
  • the catalyst is then passed to a regenerator where the coke is burned off the catalyst, which provides process heat for evaporating the feed (to remove salts) , as well as for carrying out the reaction, which is endothermic.
  • the heat necessary to carry out the reaction depends on the thermal properties of the glycerol solution, in particular the water/glycerol ratio, as water and glycerol have rather different properties.
  • reaction products preferably are separated from the catalyst in a separate reactor.
  • Coke removal preferably includes burning the coke in an oxygen-containing gas, such as air, whereby the required heat is produced.
  • an oxygen-containing gas such as air
  • coke may be burned off in flowing air at a temperature in the range of from 400 to 700 0 C.
  • Suitable solid acid catalysts for this process include: (1) amorphous or crystalline alumina-silicates, as for instance amorphous silica-alumina or zeolites, (2) fluid catalytic cracking catalysts, such as Y-zeolite in a silica-alumina matrix, or commercial equilibrium FCC catalysts, (3) oxidic catalysts such as AI2O3, Zr ⁇ 2, ZrSO 4 , Ti ⁇ 2, Si ⁇ 2, Si ⁇ 2-Al 2 ⁇ 3, and mixtures thereof; (4) supported phosphoric acid or heteropolyacid materials.
  • suitable zeolites include ZSM-5, in particular H-ZSM-5, mordenite, montmorillonite, zeolite beta, Y-zeolite, and mixtures thereof.
  • supported catalysts include catalysts comprising a carrier, for example an oxidic or siliceous carrier, coated with a mono-, di-, or polybasic inorganic acid or with an acid salt of an inorganic acid.
  • a carrier for example an oxidic or siliceous carrier
  • the glycerol solution (50/50 wt% glycerol/water) was dehydrated at 350 0 C and a gas residece time of 0.5 s as shown as Experiment Number 1 in Table 2.
  • a commercial FCC additive based on ZSM-5 zeolite (ZSM-5) was used as a catalyst. It contained around 15 % zeolite and had a BET area around 70 m 2 /g.
  • a clay binder was used to shape the catalyst as 60-100 ⁇ m microspheres. At these conditions an acrolein selectivity of 57 % was observed.
  • the other major oxygenates produced were acetaldehyde, acetone, 2- hydroxypropenal (first dehydration product from glycerol) , with metacrolein, dioxanes, furans and polyols also being produced in trace amounts.
  • the total yield of oxygenated products was 82 %.
  • fOther oxygenates involve a wide spectrum of oxygenates including furans and dioxans with 0 to 3 methyl substituents .
  • Example 2 fOther oxygenates involve a wide spectrum of oxygenates including furans and dioxans with 0 to 3 methyl substituents .
  • the ZSM-5 based catalyst of Example 1 was used
  • Example 5 A 20% glycerol solution was dehydrated at 350 0 C, CTO 12, and residence time around 0.8 second.
  • the ZSM-5 catalyst of example 1 was used.
  • the carbon selectivity to acrolein among the products that exited the reactor was 73%.
  • Example 5 Example 5:
  • a 85% glycerol solution was dehydrated at similar conditions to those in example 4 (350 0 C, CTO 10, residence time 0.8 second) and with the same catalyst as in example 1. This concentration is typical of the glycerol solutions that are obtained from a biodiesel plant. Acrolein selectivity was 56%, ethanal selectivity was 5 % and total oxygenates yield was 74%. These tests show that it is possible to process a glycerol/water stream with a broad range of concentrations while the selectivity towards acrolein is maintained between 56 and 61%.
  • a catalyst based on beta zeolite was used. It contained 20 % beta zeolite embedded in a silica/alumina matrix, and had a BET area of 190 m2/g. A 50% glycerol solution was processed on this catalyst with the following operating conditions: 350 0 C, CTO 12, and residence time around 0.8 second. This sample gave a 38 % selectivity to acrolein, a 9% selectivity to ethanal and a 35% selectivity to coke. This last selectivity may be due to the high surface area of the catalyst sample.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé pour la fabrication d'acroléine et autres composés oxygénés à partir du glycérol. Utilisation est faite d'un catalyseur acide dans un réacteur à lit mobile à 200 - 650°C.
PCT/EP2007/061695 2006-11-01 2007-10-30 Procédé de fabrication d'acroléine et autres composés oxygénés à partir de glycérol dans un réacteur à lit transporté Ceased WO2008052993A2 (fr)

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US85574606P 2006-11-01 2006-11-01
US60/855,746 2006-11-01

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WO2008052993A3 WO2008052993A3 (fr) 2008-07-17

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009029540A3 (fr) * 2007-08-24 2009-09-17 Battelle Memorial Institute Procédés, systèmes de production chimique et compositions catalytiques
WO2010006402A1 (fr) * 2008-07-16 2010-01-21 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada Conversion du glycérol en composés oxygénés de type naphta
US7872158B2 (en) 2007-08-24 2011-01-18 Battelle Memorial Institute Chemical production processes, systems, and catalyst compositions
US7872159B2 (en) 2007-08-24 2011-01-18 Battelle Memorial Institute Chemical production processes, systems, and catalyst compositions
EP2281797A1 (fr) * 2009-07-29 2011-02-09 Lonza Ltd. Procédé de fabrication sélective d'acétaldéhyde à partir d'acroléine et d'un ou plusieurs sels d'ammonium dissouts dans l'eau
CN102000597A (zh) * 2010-10-27 2011-04-06 南开大学 一种复合型固体超强酸的制备方法
FR2952057A1 (fr) * 2009-11-04 2011-05-06 Arkema France Procede de synthese de pyridine et picolines bioressourcees
US20110213174A1 (en) * 2008-10-24 2011-09-01 Arkema France Process for manufactguring acrolein from glycerol
WO2012056166A1 (fr) 2010-10-26 2012-05-03 Adisseo France S.A.S. Procédé d'obtention d'acroléine par déshydratation catalytique de glycérol ou de glycérine
US8530703B2 (en) 2009-12-18 2013-09-10 Battelle Memorial Institute Multihydric compound dehydration systems, catalyst compositions, and methods
WO2013156706A1 (fr) 2012-04-18 2013-10-24 Arkema France Procede de fabrication d'acroleine et/ou d'acide acrylique a partir de glycerol
CN104056656A (zh) * 2014-06-26 2014-09-24 沈阳理工大学 一种具有光催化净化功能的分子筛及其制备方法
CN104475147A (zh) * 2014-12-01 2015-04-01 复旦大学 一种用于甘油脱水制丙烯醛的纳米ZSM-5/γ-Al2O3复合催化剂及其制备方法和应用
US9017428B2 (en) 2010-11-16 2015-04-28 Kior, Inc. Two-stage reactor and process for conversion of solid biomass material
US9944837B2 (en) 2008-06-30 2018-04-17 Inaeris Technologies, Llc Co-processing solid biomass in a conventional petroleum refining process unit
US10934491B2 (en) 2012-01-06 2021-03-02 Mard, Inc. Two-stage process for conversion of solid biomass material

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5157181A (en) * 1990-12-03 1992-10-20 Uop Moving bed hydrocarbon conversion process
DE4238493C1 (de) * 1992-11-14 1994-04-21 Degussa Verfahren zur Herstellung von Acrolein und dessen Verwendung
FR2882052B1 (fr) * 2005-02-15 2007-03-23 Arkema Sa Procede de deshydratation du glycerol en acroleine
FR2882053B1 (fr) * 2005-02-15 2007-03-23 Arkema Sa Procede de deshydratation du glycerol en acrolene

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7872158B2 (en) 2007-08-24 2011-01-18 Battelle Memorial Institute Chemical production processes, systems, and catalyst compositions
US7872159B2 (en) 2007-08-24 2011-01-18 Battelle Memorial Institute Chemical production processes, systems, and catalyst compositions
WO2009029540A3 (fr) * 2007-08-24 2009-09-17 Battelle Memorial Institute Procédés, systèmes de production chimique et compositions catalytiques
US9944837B2 (en) 2008-06-30 2018-04-17 Inaeris Technologies, Llc Co-processing solid biomass in a conventional petroleum refining process unit
WO2010006402A1 (fr) * 2008-07-16 2010-01-21 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Natural Resources Canada Conversion du glycérol en composés oxygénés de type naphta
US20110213174A1 (en) * 2008-10-24 2011-09-01 Arkema France Process for manufactguring acrolein from glycerol
US8378136B2 (en) * 2008-10-24 2013-02-19 Arkema France Process for manufacturing acrolein from glycerol
EP2281797A1 (fr) * 2009-07-29 2011-02-09 Lonza Ltd. Procédé de fabrication sélective d'acétaldéhyde à partir d'acroléine et d'un ou plusieurs sels d'ammonium dissouts dans l'eau
WO2011012253A3 (fr) * 2009-07-29 2011-06-30 Lonza Ltd Procédé de préparation sélective d'acétaldéhyde à partir d'acroléine et d'au moins un sel d'ammonium dissous dans l'eau
JP2013510130A (ja) * 2009-11-04 2013-03-21 アルケマ フランス バイオベースのピリジンおよびピコリンの合成方法
WO2011055057A1 (fr) * 2009-11-04 2011-05-12 Arkema France Procede de synthese de pyridine et picolines bioressourcees
FR2952057A1 (fr) * 2009-11-04 2011-05-06 Arkema France Procede de synthese de pyridine et picolines bioressourcees
US8785645B2 (en) 2009-11-04 2014-07-22 Arkema France Method for synthesizing bio-based pyridine and picolines
US8907135B2 (en) 2009-12-18 2014-12-09 Battelle Memorial Institute Multihydric compound dehydration systems, catalyst compositions, and methods
US8530703B2 (en) 2009-12-18 2013-09-10 Battelle Memorial Institute Multihydric compound dehydration systems, catalyst compositions, and methods
WO2012056166A1 (fr) 2010-10-26 2012-05-03 Adisseo France S.A.S. Procédé d'obtention d'acroléine par déshydratation catalytique de glycérol ou de glycérine
CN102000597A (zh) * 2010-10-27 2011-04-06 南开大学 一种复合型固体超强酸的制备方法
US9017428B2 (en) 2010-11-16 2015-04-28 Kior, Inc. Two-stage reactor and process for conversion of solid biomass material
US10934491B2 (en) 2012-01-06 2021-03-02 Mard, Inc. Two-stage process for conversion of solid biomass material
US9527791B2 (en) 2012-04-18 2016-12-27 Arkema France Method for producing acrolein and/or acrylic acid from glycerol
WO2013156706A1 (fr) 2012-04-18 2013-10-24 Arkema France Procede de fabrication d'acroleine et/ou d'acide acrylique a partir de glycerol
US10407371B2 (en) 2012-04-18 2019-09-10 Arkema France Method for producing acrolein and/or acrylic acid from glycerol
CN104056656A (zh) * 2014-06-26 2014-09-24 沈阳理工大学 一种具有光催化净化功能的分子筛及其制备方法
CN104475147A (zh) * 2014-12-01 2015-04-01 复旦大学 一种用于甘油脱水制丙烯醛的纳米ZSM-5/γ-Al2O3复合催化剂及其制备方法和应用
CN104475147B (zh) * 2014-12-01 2017-01-25 复旦大学 一种用于甘油脱水制丙烯醛的纳米ZSM‑5/γ‑Al2O3复合催化剂及其制备方法和应用

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