WO2008113927A1 - Procede de synthese d'acrylonitrile a partir de glycerol - Google Patents
Procede de synthese d'acrylonitrile a partir de glycerol Download PDFInfo
- Publication number
- WO2008113927A1 WO2008113927A1 PCT/FR2008/050261 FR2008050261W WO2008113927A1 WO 2008113927 A1 WO2008113927 A1 WO 2008113927A1 FR 2008050261 W FR2008050261 W FR 2008050261W WO 2008113927 A1 WO2008113927 A1 WO 2008113927A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- glycerol
- acrylonitrile
- reaction
- ammoxidation
- acrolein
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/08—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds
- C07C253/10—Preparation of carboxylic acid nitriles by addition of hydrogen cyanide or salts thereof to unsaturated compounds to compounds containing carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
- C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Definitions
- the present invention relates to a new synthetic route for acrylonitrile from a renewable raw material and more particularly relates to a process for synthesizing acrylonitrile from glycerol.
- the reaction is carried out in a fluidized bed reactor, at a temperature generally of between 400 ° C. and 500 ° C., and preferably from 420 ° C. to 450 ° C. for the most modern catalysts, under a pressure that may range from 20 kPa to 300 kPa, and more often from 150 kPa to 300 kPa.
- Different catalysts are used, such as bismuth-based complexes, or bismuth molybdate, or mixed molybdates of iron and bismuth, or iron antimonate, or phosphomolybdate, or antimony-uranium combinations.
- Acrylonitrile obtained by ammoxidation of propylene contains impurities and by-products which must be separated and which are not always valued.
- the main by-products include hydrogen cyanide (HCN), acetonitrile (CH 3 CN) and carbon oxides. They result from the disruption of the propylene CC bond during the ammoxidation reaction carried out at high temperature and in the presence of very active catalysts.
- the hydrocyanic acid after extraction and purification, can be used in methyl methacrylate synthesis processes for example.
- acetonitrile given its limited applications, is usually destroyed. It therefore appears particularly interesting to use a different raw material, which by nature will lead to the desired product by a different reaction mechanism, and generating fewer byproducts.
- the ammoxidation reaction of propylene is highly exothermic and therefore requires reactor technologies to effectively remove the heat of reaction, such as for example multitubular reactors or fluidized beds. Because of the significant runaway risks related to the exothermicity of the reaction, dilute streams are used, in particular, a propylene / air / ammonia mixture is generally used, in which propylene only represents a few%. In this configuration, the reactor is sized according to the total amount of gas in the installation, and therefore oversized with respect to the amount of the propylene reactant, which leads to an additional cost for the reactor.
- Distillers obtains acrylonitrile yields greater than 70% compared to acrolein, using as catalysts compounds based on antimony, tin and oxygen.
- the reaction can be carried out in the presence of an inert gas, such as nitrogen, water vapor, carbon dioxide or propane, butane or isobutane.
- BE 628 287 discloses a process for the ammoxidation of acrolein to produce acrylonitrile in yields greater than 87% with an arsenic catalyst and a significant proportion of water vapor as a diluent.
- Patent EP 558 424 describes a process for the ammoxidation of propane in the presence of a catalyst comprising vanadium, antimony and at least one metal chosen from iron, gallium or indium. Acrylonitrile selectivities of up to 70% are obtained.
- US Pat. No. 4,138,430 describes the ammoxidation of n-propanol.
- the reaction is carried out in the presence of oxygen and ammonia by passing the gas stream successively on two catalyst beds: a first bed of catalyst consisting of boron phosphate, silica-alumina co-precipitated or co-precipitated alumina-tungsten oxide, on which the dehydration reaction of propanol to olefin and a second catalyst bed, carrying out the olefin ammoxidation reaction, consisting of mixed oxides of Fe, Co, Ni, Bi, P, Mo and K, mixed oxides of Fe, Co, W, Bi, Mo and Mg, mixed oxides of Sb and U, bismuth molybdate or bismuth phosphomolybdate, or a mixture of these compounds.
- ammoxidation reaction of propylene, of aldehydes such as acrolein, ketones or alcohols such as propanol or isopropanol has been the subject of numerous fundamental studies to determine the reaction mechanisms involved, or to study the effect of various parameters, such as the nature of the catalyst or the presence of water vapor as a diluent.
- Glycerol is derived from the methanolysis of vegetable oils at the same time as the methyl esters which are used in particular as fuels or fuels in diesel and domestic fuel (D. Ballerini and G. Hillion, L' may chimique - nov. Dec. 2002 - pages 64-69). It is a natural product that has a "green" aura, is available in large quantities and can be stored and transported without difficulty.
- 12 C is stable, that is to say that the number of atoms of 12 C in a given sample is constant over time.
- the 14 C it is radioactive (each gram of carbon of a living being contains enough isotope
- n no exp (-at) in which: - no is the number of 14 C at the origin (at the death of the creature, animal or plant),
- n is the number of 14 C atoms remaining at the end of time t
- Acrylonitrile obtained from glycerol consists of 100% organic carbon derived from a renewable resource, i.e. it contains of the order of 10 ⁇ 10% by weight of 14 C to the total mass of carbon, which could be certified by determination of the 14 C content according to one of the methods described in ASTM D6866-06 or ASTM D 7026-04, in particular by mass spectrometry methods or by liquid scintillation spectrometry described in ASTM D8866-06. These methods measure the ratio 14 CV 12 C of a sample and compare it with the ratio 14 CV 12 C of a reference sample of 100% renewable origin, to give a relative percentage of C of renewable origin in the sample .
- An object of the present invention is therefore to respond to sustainable development concerns while overcoming the disadvantages of current processes.
- Glycerol is used pure, or as a concentrated or dilute aqueous solution.
- an aqueous glycerol solution with a concentration ranging from 10% to 100% by weight. The concentration should not be too high to avoid side reactions such as the formation of glycerol ethers or reactions between acrylonitrile produced and glycerol.
- the glycerol solution should not be diluted too much because of the energy cost induced by the evaporation of the aqueous glycerol solution.
- the water vapor resulting from the aqueous glycerol solution can vary within wide limits, but for a good implementation of the process according to the invention, the content of reaction gas, defined as the glycerol-ammonia-oxygen sum. is preferably at least 2%, more preferably at least 4% in the mixture including water vapor and inert gases including nitrogen air when it is used as oxidant.
- Inert diluent gases can be used under reaction conditions such as helium, nitrogen or argon.
- the ammonia / glycerol molar ratio can vary between 1 and 1.5, and preferably between 1 and 1, 2 and the oxygen / glycerol molar ratio can vary between 0.5 and 10 and preferably between 0.5 and 7.
- the catalyst used in the glycerol ammoxidation process is an acid catalyst which is not saturated with ammonia at the reaction temperature.
- the catalyst may comprise one or more mixed oxides chosen, for example, from molybdenum, bismuth, iron, antimony, tin, vanadium, tungsten, antimony, zirconium, titanium, chromium, nickel, aluminum, phosphorus, gallium.
- the reaction is carried out in a single reactor, that is to say according to a direct ammoxidation of glycerol where all the elementary steps take place in the same reactor.
- Any device suitable for ammoxidation or vapor phase oxidation reactions may be used.
- the process can be carried out continuously or batchwise, using a fixed bed, a fluidized bed, a circulating bed, a plate heat exchanger with a modular catalyst arrangement, a micro-structured reactor or a milli-structured reactor.
- the acrolein produced is naturally diluted in water vapor, and all the more so that the glycerol is diluted in water.
- the reaction can be carried out in concentrated reagent medium while remaining outside the flammability limits. Under these conditions of highly concentrated medium, it is possible to economically recycle reagents that have not reacted or have been insufficiently converted.
- the two steps of the process are carried out at the same temperature, preferably between 400 ° C. and 500 ° C.
- the dehydration step of glycerol is carried out in the gas phase in the presence of a catalyst, at a temperature ranging from 150 ° C. to 500 ° C., preferably between 250 ° C. and 350 ° C., and a pressure of between 1 ° C. and 5 bars.
- the preferred catalysts are sulphated zirconias, zirconium phosphates, tungsten zirconias, silicified zirconias, sulphated titanium or tin oxides, phosphated aluminas or silicas.
- the ammonia is introduced only at the second stage.
- the step of ammoxidation of the acrolein acrylonitrile is then carried out on an ammoxidation catalyst at a temperature generally between 300 0 C and 550 0 C and, preferably, between 400 ° C and 500 0 C. and at a pressure generally between 1 and 5 bar and preferably between 1 and 4 bar.
- the composition of the reaction mixture can vary within wide limits and inert diluent gases can be used under the reaction conditions such as helium, nitrogen or argon, or nitrogen. air when it is used as an oxidizer.
- Ammonia / acrolein and oxygen / acrolein molar ratios can vary widely.
- the molar ratio ammonia / acrolein may vary between 1 and 1.5, and preferably between 1 and 1, 2 and the oxygen / acrolein molar ratio may vary between 0.5 and 10 and preferably between 0.5 and 7.
- a catalyst for the ammoxidation of acrolein an acid catalyst which is not saturated with ammonia at the reaction temperature will be used.
- An advantage of this embodiment is a better choice of the catalyst pair. Indeed, the dehydration reaction requires acid catalysts that can be inhibited by the presence of ammonia if they are too acidic. The separation of the two stages makes it possible to individually optimize the operating conditions of each of the two dehydration and ammoxidation reactions.
- a prior step of dehydration of glycerol implemented in the form of aqueous solution has the disadvantage of leading to a flow containing not only acrolein produced and by-products, but also a significant amount of water on the one hand, from the glycerol solution, on the other hand from the water produced by the dehydration reaction.
- the purpose of the partial condensation step is to condense a portion of the water and products having a higher boiling point than acrolein.
- the partial condensation unit may be an absorption column coupled or not to a stripper, a heat exchanger, a condenser, a dephlegmator, as well as any apparatus well known to those skilled in the art, making it possible to perform a partial condensation of an aqueous stream.
- This unit can also be used to heat the aqueous solution of glycerol, thus optimizing the energy cost of the installation.
- the acrolein-rich stream is sent to the ammoxidation catalyst, adding the ammonia necessary for the reaction and adjusting the partial pressures of acrolein and oxygen reactants and optionally diluting the reaction gas. with an inert gas.
- the glycerol is introduced in (1) in the form of an aqueous solution, into a first dehydration reactor (10).
- Molecular oxygen (2) is also introduced, for example in the form of air or in the form of enriched or depleted air with molecular oxygen.
- the dehydration reaction is carried out in the gas phase in the reactor (10) in the presence of a dehydration catalyst, at a temperature of between 250 ° C. and 350 ° C. and at a pressure of between 1 and 5 bars.
- the gaseous flow at the outlet of the reactor (10) consists of a mixture comprising acrolein, water, unprocessed glycerol and by-products.
- By-products include hydroxypropanone, propanaldehyde, acetaldehyde, acetone, phenol, adducts acrolein on glycerol, polycondensation products of glycerol, cyclic glycerol ethers or not.
- This flow is sent to a condensing unit (11), which separates, on the one hand, a mixture (3) rich in water containing the heavy by-products, on the other hand a stream (4) rich in acrolein containing the sub-products.
- -Light products such as acetaldehyde, propanaldehyde, acetone and possibly inert gases, CO and CO 2 .
- the stream (3) is sent wholly or partly, either to a rectification column in order to recover the light fraction that could be absorbed in this stream, or to a wastewater treatment station. It can also be sent to a thermal oxidizer, or a portion of this stream is recycled to dilute the glycerol to the desired concentration.
- the flow (4), rich in acrolein and freed of heavy by-products and most of the water is sent to the ammoxidation reactor (12) comprising a fixed bed of acrolein ammoxidation catalyst.
- the ammoxidation reaction is carried out at a temperature of between 400 ° C. and 500 ° C. and at a pressure of between 1 and 5 bars.
- the effluent (7) from the ammoxidation stage, rich in acrylonitrile, is then purified on a separation unit (13) to separate, on the one hand, the light products (8) and the unconverted acrolein, and on the other hand acrylonitrile (9) may still contain traces of heavy byproducts.
- the ammoxidation reaction of glycerol is carried out in the presence of a gas containing propylene.
- the propylene-containing gas can be co-fed with glycerol, or it can be fed after the glycerol dehydration reaction.
- the ammoxidation reaction of glycerol is carried out in the presence of a thermal ballast, such as for example propane or a gas containing propane, methane, ethane or CO2.
- Thermal ballast is a heat transfer fluid, which can be used to bring calories necessary for the dehydration reaction, but also to bring calories produced during the ammoxidation reaction.
- the thermal ballast can be introduced together with glycerol, or when the dehydration and ammoxidation steps are disjointed, it can be introduced between these steps. Thermal ballast such as propane is eventually recovered and recycled.
- acrylonitrile of high purity, with good productivity, while reducing the dependence on a fossil resource such as propylene.
- the acrylonitrile obtainable by this process contains 14 C, advantageously acrylonitrile contains 14 C at a content greater than 10-11 % relative to the total carbon, which could be certified by measurement according to one of the methods described in ASTM D6866-06.
- a gaseous flow at 331 ° C. at 2.0 bar (188 kmol / h glycerol, 963 kmol / h water, 426 kmol / h nitrogen, 113 kmol / h oxygen) is sent to a fixed-bed multitubular reactor (10) containing a heterogeneous dehydration catalyst coupled to a molten salt bath. From this reactor a gas stream (14) leaves at 320 ° C.
- the mixture is heated to 300 ° C. and then injected into a second multitubular reactor (12) comprising an ammoxidation catalyst.
- a gaseous stream (7) is obtained at 1.4 bar (2030 kmol / h nitrogen, 830 kmol / h water, 118 kmol / h acrylonitrile, 52 kmol / h oxygen, 155 kmol / h carbon, 85 kmol / h carbon monoxide).
- This stream is cooled to 157 ° C and then injected at the bottom of the absorption column (13).
- the process makes it possible to remove certain impurities produced in the dehydration reactor (10) from the aqueous phase (22): for example, the flow rates of hydroxypropanone and acetic acid in the gaseous flow at the outlet of the dehydration reactor. (10) are respectively 1 and 4 kmol / h. They are respectively 0.02 and 0.3 kmol / h at the inlet of the oxidation reactor (12).
- Yield of acrolein (%) number of moles of acrolein produced / number of moles of glycerol introduced.
- a tubular reactor consisting of a 35 cm long tube and an internal diameter of 22 mm was used to carry out the dehydration reaction of glycerol in the gas phase at atmospheric pressure.
- This reactor is placed in a heated enclosure maintained at the reaction temperature of 300 ° C., unless otherwise indicated.
- the catalyst used is milled and / or pelletized to obtain particles of 0.5 to 1.0 mm. 10 ml of catalyst are loaded into the reactor to form a catalytic bed of length 5 cm. This is brought to the reaction temperature for 5 to 10 minutes before the introduction of the reagents.
- the reactor is fed with an aqueous solution containing 20% by weight of glycerol with an average feed rate of 12 ml / h, and with a flow rate of 0.8 l / h of molecular oxygen for the examples according to the invention. .
- the relative proportion O 2 / vaporized glycerol / water vapor is 6 / 4.5 / 89.5.
- the aqueous glycerol solution is vaporized in the heated chamber and then passes over the catalyst.
- the calculated contact time is of the order of 2.9 s. After reaction, the products are condensed in a trap refrigerated with crushed ice.
- the total mass of input and output products is measured, which makes it possible to perform a mass balance.
- the products formed are analyzed by chromatography.
- the products thus quantified are unreacted glycerol, acrolein formed, and by-products such as hydroxypropanone, acetaldehyde, propanaldehyde, acetone and phenol.
- the catalyst (10 ml) tested is a tungsten zirconia (90.7% ZrO 2 - 9.3% WO 3) from Daiichi Kigenso (supplier reference H1417).
- the catalyst is characterized by a loss on ignition at 1000 ° C. of 1.75% and a specific surface area of 47.4 m 2 / g (BET, 1 point).
- the results are shown in the following table:
- the acrolein produced does not contain hydroxypropanone or phenol.
- the reactor is then connected to the test facility.
- the temperature of the catalyst is regulated at 420 ° C. and the WH is adjusted to 1200 h -1
- the reactor is fed with a gaseous mixture of 4.5% acrolein / 8.7
- % oxygen / 5.4% ammonia / (rest) helium-krypton / 15% water % oxygen / 5.4% ammonia / (rest) helium-krypton / 15% water.
- the helium-Krypton gas mixture contains 4.92% krypton which serves as internal standard.
- the water-acrolein mixture from Example 2 vaporized upstream of the reactor, is used after concentration.
- the effluents are collected at the outlet of the reactor by a cold ice trap and the acrylonitrile produced is assayed by chromatographic analysis.
- the yield of acrylonitrile is 60%.
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Abstract
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Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
UAA200909494A UA104992C2 (uk) | 2007-02-16 | 2008-02-18 | Спосіб синтезу акрилонітрилу з гліцерину |
MX2009008746A MX2009008746A (es) | 2007-02-16 | 2008-02-18 | Procedimiento de sintesis de acrilonitrilo a partir de glicerol. |
EP08762109A EP2118053A1 (fr) | 2007-02-16 | 2008-02-18 | Procede de synthese d'acrylonitrile a partir de glycerol |
BRPI0807736-3A2A BRPI0807736A2 (pt) | 2007-02-16 | 2008-02-18 | Processo para síntese de acrilonitrila a partir de glicerol |
CA2676669A CA2676669C (fr) | 2007-02-16 | 2008-02-18 | Procede de synthese d'acrylonitrile a partir de glycerol |
CN200880005292.0A CN101636381B (zh) | 2007-02-16 | 2008-02-18 | 从甘油合成丙烯腈的方法 |
US12/527,352 US8829223B2 (en) | 2007-02-16 | 2008-02-18 | Method for the synthesis of acrylonitrile from glycerol |
RU2009134501/04A RU2471774C2 (ru) | 2007-02-16 | 2008-02-18 | Способ синтеза акрилонитрила из глицерина |
JP2009549463A JP5579447B2 (ja) | 2007-02-16 | 2008-02-18 | グリセロールからのアクリロニトリルの合成方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0753293A FR2912742B1 (fr) | 2007-02-16 | 2007-02-16 | Procede de synthese d'acrylonitrile a partir de glycerol |
FR0753293 | 2007-02-16 |
Publications (1)
Publication Number | Publication Date |
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WO2008113927A1 true WO2008113927A1 (fr) | 2008-09-25 |
Family
ID=38474295
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/FR2008/050261 WO2008113927A1 (fr) | 2007-02-16 | 2008-02-18 | Procede de synthese d'acrylonitrile a partir de glycerol |
Country Status (11)
Country | Link |
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US (1) | US8829223B2 (fr) |
EP (1) | EP2118053A1 (fr) |
JP (1) | JP5579447B2 (fr) |
CN (1) | CN101636381B (fr) |
BR (1) | BRPI0807736A2 (fr) |
CA (1) | CA2676669C (fr) |
FR (1) | FR2912742B1 (fr) |
MX (1) | MX2009008746A (fr) |
RU (1) | RU2471774C2 (fr) |
UA (1) | UA104992C2 (fr) |
WO (1) | WO2008113927A1 (fr) |
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ES2319949A1 (es) * | 2007-11-13 | 2009-05-14 | Consejo Superior De Investigaciones Cientificas | Proceso catalitico de produccion de nitrilos a partir de alcoholes. |
KR20110077007A (ko) * | 2008-10-24 | 2011-07-06 | 아르끄마 프랑스 | 글리세롤로부터의 아크롤레인의 제조방법 |
WO2012010923A1 (fr) | 2010-07-19 | 2012-01-26 | Arkema France | Procédé de fabrication d'acroléine à partir de glycérol |
JP2012514590A (ja) * | 2009-01-06 | 2012-06-28 | アルケマ フランス | バイオマス由来のメチルメタクリレートの製造方法 |
WO2013008279A1 (fr) | 2011-07-14 | 2013-01-17 | Nippon Kayaku Kabushiki Kaisha | Procédé de préparation d'un catalyseur utilisé dans la production de l'acroléine et/ou de l'acide acrylique et procédé de préparation d'acroléine et/ou d'acide acrylique par une réaction de déshydratation de la glycérine |
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EP2695672A2 (fr) | 2009-09-18 | 2014-02-12 | Nippon Kayaku Kabushiki Kaisha | Production d'acroleine par deshydrogenation de glycerine en presence d'un catalyseur |
JP2015134826A (ja) * | 2008-11-27 | 2015-07-27 | アルケマ フランス | バイオマス由来のメチルメタクリレートの製造方法 |
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FR2920767B1 (fr) | 2007-09-06 | 2009-12-18 | Arkema France | Procede de vaporisation reactive de glycerol |
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JP5761940B2 (ja) * | 2010-08-02 | 2015-08-12 | 旭化成ケミカルズ株式会社 | アクリロニトリルの製造方法 |
WO2012101471A1 (fr) * | 2011-01-28 | 2012-08-02 | Arkema France | Procédé amélioré pour fabriquer de l'acroléine/acide acrylique |
CN103804224B (zh) * | 2014-02-20 | 2015-04-08 | 河北工业大学 | 一种催化甘油氨化制备腈类化合物的方法 |
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NL2030511B1 (en) | 2022-01-12 | 2023-07-17 | Trillium Renewable Chemicals Inc | Integrated process for the conversion of glycerol to acrylonitrile |
WO2023105430A1 (fr) | 2021-12-08 | 2023-06-15 | Trillium Renewable Chemicals, Inc. | Procédé intégré pour la conversion de glycérol en acrylonitrile |
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2008
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- 2008-02-18 JP JP2009549463A patent/JP5579447B2/ja not_active Expired - Fee Related
- 2008-02-18 MX MX2009008746A patent/MX2009008746A/es active IP Right Grant
- 2008-02-18 US US12/527,352 patent/US8829223B2/en not_active Expired - Fee Related
- 2008-02-18 BR BRPI0807736-3A2A patent/BRPI0807736A2/pt not_active IP Right Cessation
- 2008-02-18 RU RU2009134501/04A patent/RU2471774C2/ru not_active IP Right Cessation
- 2008-02-18 WO PCT/FR2008/050261 patent/WO2008113927A1/fr active Application Filing
- 2008-02-18 CN CN200880005292.0A patent/CN101636381B/zh not_active Expired - Fee Related
- 2008-02-18 EP EP08762109A patent/EP2118053A1/fr not_active Withdrawn
- 2008-02-18 CA CA2676669A patent/CA2676669C/fr not_active Expired - Fee Related
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WO2009063120A1 (fr) * | 2007-11-13 | 2009-05-22 | Consejo Superior De Investigaciones Científicas | Procédé catalytique de production de nitriles à partir d'alcools |
ES2319949A1 (es) * | 2007-11-13 | 2009-05-14 | Consejo Superior De Investigaciones Cientificas | Proceso catalitico de produccion de nitrilos a partir de alcoholes. |
KR20110077007A (ko) * | 2008-10-24 | 2011-07-06 | 아르끄마 프랑스 | 글리세롤로부터의 아크롤레인의 제조방법 |
JP2012506398A (ja) * | 2008-10-24 | 2012-03-15 | アルケマ フランス | グリセロールからアクロレインを製造する方法 |
KR101711220B1 (ko) * | 2008-10-24 | 2017-02-28 | 아르끄마 프랑스 | 글리세롤로부터의 아크롤레인의 제조방법 |
JP2017066149A (ja) * | 2008-11-27 | 2017-04-06 | アルケマ フランス | バイオマス由来のメチルメタクリレートの製造方法 |
JP2015134826A (ja) * | 2008-11-27 | 2015-07-27 | アルケマ フランス | バイオマス由来のメチルメタクリレートの製造方法 |
JP2015180637A (ja) * | 2009-01-06 | 2015-10-15 | アルケマ フランス | バイオマス由来のメチルメタクリレートの製造方法 |
JP2012514590A (ja) * | 2009-01-06 | 2012-06-28 | アルケマ フランス | バイオマス由来のメチルメタクリレートの製造方法 |
US9162954B2 (en) | 2009-09-18 | 2015-10-20 | Arkema France | Catalyst and process for preparing acrolein and/or acrylic acid by dehydration reaction of glycerin |
EP2695672A2 (fr) | 2009-09-18 | 2014-02-12 | Nippon Kayaku Kabushiki Kaisha | Production d'acroleine par deshydrogenation de glycerine en presence d'un catalyseur |
WO2012010923A1 (fr) | 2010-07-19 | 2012-01-26 | Arkema France | Procédé de fabrication d'acroléine à partir de glycérol |
WO2013008279A1 (fr) | 2011-07-14 | 2013-01-17 | Nippon Kayaku Kabushiki Kaisha | Procédé de préparation d'un catalyseur utilisé dans la production de l'acroléine et/ou de l'acide acrylique et procédé de préparation d'acroléine et/ou d'acide acrylique par une réaction de déshydratation de la glycérine |
WO2013018915A2 (fr) | 2011-07-29 | 2013-02-07 | Arkema France | Procédé amélioré concernant les réactions de déshydratation |
WO2013017942A2 (fr) | 2011-07-29 | 2013-02-07 | Arkema France | Procédé perfectionné de mise en œuvre de réactions de déshydratation |
Also Published As
Publication number | Publication date |
---|---|
CA2676669A1 (fr) | 2008-09-25 |
RU2009134501A (ru) | 2011-03-27 |
MX2009008746A (es) | 2009-08-27 |
US8829223B2 (en) | 2014-09-09 |
BRPI0807736A2 (pt) | 2014-06-03 |
RU2471774C2 (ru) | 2013-01-10 |
EP2118053A1 (fr) | 2009-11-18 |
JP2010519191A (ja) | 2010-06-03 |
CA2676669C (fr) | 2015-06-16 |
JP5579447B2 (ja) | 2014-08-27 |
CN101636381A (zh) | 2010-01-27 |
CN101636381B (zh) | 2014-10-15 |
US20100048850A1 (en) | 2010-02-25 |
UA104992C2 (uk) | 2014-04-10 |
FR2912742B1 (fr) | 2010-03-05 |
FR2912742A1 (fr) | 2008-08-22 |
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