US20110288323A1 - Method for preparing acrolein from glycerol or glycerine - Google Patents

Method for preparing acrolein from glycerol or glycerine Download PDF

Info

Publication number
US20110288323A1
US20110288323A1 US13/140,109 US200913140109A US2011288323A1 US 20110288323 A1 US20110288323 A1 US 20110288323A1 US 200913140109 A US200913140109 A US 200913140109A US 2011288323 A1 US2011288323 A1 US 2011288323A1
Authority
US
United States
Prior art keywords
metal
catalyst
glycerol
oxide
zirconium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US13/140,109
Other languages
English (en)
Inventor
Virginie Belliere-Baca
Stephane Loridant
Jean-Marc Millet
Pascaline Lauriol-Garbey
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre National de la Recherche Scientifique CNRS
Adisseo France SAS
Original Assignee
Centre National de la Recherche Scientifique CNRS
Adisseo France SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre National de la Recherche Scientifique CNRS, Adisseo France SAS filed Critical Centre National de la Recherche Scientifique CNRS
Assigned to CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, ADISSEO FRANCE S.A.S reassignment CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BELLIERE-BACA, VIRGINIE, MILLET, JEAN-MARC, LAURIOL-GARBEY, PASCALINE, LORIDANT, STEPHANE
Publication of US20110288323A1 publication Critical patent/US20110288323A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/90—Regeneration or reactivation
    • B01J23/92—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/12—Treating with free oxygen-containing gas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a catalytic method for making acrolein by dehydration of glycerol or glycerine and to the application of such a method.
  • glycerol is meant a glycerol either purified or not, preferably stemming from biomass and notably a highly purified or partly purified glycerol.
  • a purified glycerol has a purity greater than or equal to 98%, obtained by distillation of glycerine.
  • a non-purified or only partly purified glycerol may be in solution in methanol when it for example stems from transesterification of triglycerides, as described hereafter.
  • glycerine is notably meant glycerine of natural origin, stemming from hydrolysis of vegetable oils and/or animal fats, or more or less purified or refined or else raw glycerine of synthetic origin stemming from petroleum.
  • raw glycerine has a titer comprised between 80 and 85%.
  • a glycerol or a glycerine stemming from biomass but the invention of course is not limited thereto and its benefit extends to all glycerols and glycerines, regardless of their origins and their degrees of purity.
  • biodiesel is a fuel produced from vegetable or animal oil.
  • Diester® (or MEVOs, Methyl Esters of Vegetable Oils) is a biodiesel made by transesterification of triglycerides present in oleaginous liquids, notably palm, rapeseed and sunflower vegetable oils, by methanol. This transesterification co-produces approximately and according to the contemplated methods, 100 kg of glycerol per metric ton of Diester®. The non-lipid portion of the raw material used, the cakes, is mainly exploited in animal feed.
  • Acrolein and acrylic acid are traditionally used by controlled oxidation in the gas phase of propylene by oxygen from air in the presence of catalysts based on molybdenum and/or bismuth oxides.
  • the thereby obtained acrolein may either be directly integrated into a two-step method for producing acrylic acid, or be used as a synthesis intermediate.
  • the production of both of these monomers is therefore closely related to propylene which in substance is produced by steam cracking or catalytic cracking of petroleum cuts.
  • acrolein a highly reactive compound because of its structure, finds many applications, notably as a synthesis intermediate. It is most particularly used as a key intermediate entering the synthesis of D,L-methionine and of its hydroxyl-analog derivative, 2-hydroxy-4-methylthiobutanoic acid (HMTBA).
  • HMTBA 2-hydroxy-4-methylthiobutanoic acid
  • These food additives are massively used since they enter the composition of food supplements indispensable to the growth of animals (poultry, pigs, ruminants, fish, . . . ). In a certain number of cases, it may be profitable to be able to increase, or even ensure production capacities of existing industrial units by diversifying the engaged raw material. It therefore appears to be most particularly of interest to be able to increase acrolein productivity, while reducing the dependency towards this resource stemming from petroleum which is propylene.
  • the invention lies in the application of robust, active, selective and regenerable catalysts, with which acrolein may be directly produced from glycerol or glycerine, notably stemming from the biomass, according to the reaction:
  • the invention further relates to an application of this reaction to the synthesis of 3-(methylthio)propionic aldehyde (MMP), 2-hydroxy-4-methylthiobutyronitrile (HMTBN), methionine and its analogs such as 2-hydroxy-4-methylthiobutanoic acid (HMTBA), esters of HMTBA such as the isopropyl ester, 2-oxo-4-methylthiobutanoic acid, from acrolein.
  • MMP 3-(methylthio)propionic aldehyde
  • HMTBN 2-hydroxy-4-methylthiobutyronitrile
  • methionine and its analogs
  • 2-hydroxy-4-methylthiobutanoic acid HMTBA
  • esters of HMTBA such as the isopropyl ester, 2-oxo-4-methylthiobutanoic acid, from acrolein.
  • acrolein is generally obtained by oxidation of propylene and/or of propane. Oxidation of propylene into acrolein by air in the presence of water is partial, and the resulting raw product, based on acrolein, also contains unreacted propylene and propane, water and by-products of the oxidation reaction, notably acids, aldehydes and alcohols.
  • Glycerol also called glycerine
  • glycerine has been known for a long time as a source of acrolein (thermal transformation), it is a product which is widely found in nature, in the form of esters (triglycerides), in particular in all animal or vegetable oils and fats, which makes it a starting reagent available in sufficient quantity and in this respect may be used in industry.
  • esters triglycerides
  • esters triglycerides
  • glycerol decomposes and gives acrolein when it is brought to temperatures above 280° C. This weakly selective reaction is accompanied by the formation of many by-products including acetaldehyde, hydroxyacetone, in addition to total oxidation products, CO, CO 2 .
  • documents WO-A-2006087083 and WO-A-2006087084 describe a method for catalytic dehydration of glycerol into acrolein in the gas phase, in the presence of molecular oxygen and of a strongly acid catalyst selected from zeolites, Nafion®, oxides of metals selected from aluminium, zirconium, titanium, niobium, tantalum, silicon, impregnated with acid functions in the form of sulfate, borate, tungstate, silicate and phosphate groups.
  • zeolites Nafion®
  • oxides of metals selected from aluminium, zirconium, titanium, niobium, tantalum, silicon
  • WO-A-2007132926 discloses a method for converting glycerol into acrolein in the presence of a catalyst selected from acid crystalline metallosilicates such as zeolites of the MFI or BEA structural type, comprising silicon and an element preferably selected from Al, Fe and Ga.
  • a catalyst selected from acid crystalline metallosilicates such as zeolites of the MFI or BEA structural type, comprising silicon and an element preferably selected from Al, Fe and Ga.
  • this catalyst was based on zirconium oxide and comprised at least:
  • a silicon oxide and a mixed oxide of zirconium and of at least one metal M said metal being selected from tungsten, cerium, manganese, niobium, titanium, vanadium and silicon,
  • a silicon oxide and a mixed oxide of zirconium and of at least one metal M said metal being selected from tungsten, cerium, manganese, niobium, tantalum, vanadium and titanium,
  • a titanium oxide and a mixed oxide of zirconium and of at least one metal M said metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon.
  • a titanium oxide and a mixed oxide of zirconium and of at least one metal M said metal being selected from tungsten, cerium, manganese, niobium, tantalum, titanium, vanadium and silicon.
  • the invention relates to a method for obtaining acrolein from glycerol or glycerine, in the presence of a catalyst as defined above, and to the use of this catalyst for converting glycerol or glycerine into acrolein.
  • a catalyst of the invention allows controlled conversion of glycerol or glycerine into acrolein, i.e. not promoting conversion as far as acrylic acid.
  • a preferred catalyst of the invention does not comprise, or does not comprise in a majority weight proportion relatively to each of the other oxides making it up, of molybdenum oxide and/or copper oxide.
  • the invention also relates to the use of at least any one of the catalysts a), b), c), d), e) and f), as defined earlier for converting glycerol or glycerine into acrolein.
  • the catalyst may be prepared in various ways (co-precipitation, hydrothermal synthesis . . . ).
  • An effective procedure was described by Kantcheva et. al., Catalysis Communications (2008), 9(5), p 874-879, in patents FR 2907444 and FR 2907445.
  • the catalyst of the invention has the benefit of being able to be easily regenerated, and this without affecting the yield of the dehydration or the acrolein selectivity.
  • the reaction according to the invention may be applied in a gas phase or in a liquid phase, preferably in a gas phase.
  • different process technologies may be used, i.e. a fixed bed process, a fluidized bed process or a process with a circulating fluidized bed.
  • the regeneration of the catalyst may be separated from the catalytic reaction.
  • it may be accomplished ex situ with conventional regeneration methods, such as combustion in air or with a gas mixture containing molecular oxygen.
  • the regeneration may be accomplished in situ since the temperatures and pressures at which regeneration is accomplished are close to the reaction conditions of the process.
  • the reaction may be achieved in a conventional reactor for reaction in a liquid phase on a solid catalyst, but also in a reactor of the catalytic distillation type considering the significant difference between the boiling points of glycerol (290° C.) and of acrolein (53° C.).
  • a process in a liquid phase may also reasonably be contemplated at a relatively low temperature which allows continuous distillation of the produced acrolein, thereby limiting the consecutive reactions of acrolein degradation.
  • the experimental conditions of the reaction in the gas phase are preferably a temperature comprised between 250 and 400° C., at a pressure comprised between 1 and 10 bars. In the liquid phase, the reaction operates between 150 and 350° C. and at a pressure which may range from 3 to 70 bars.
  • Another advantage of the method of the invention lies in the form of the starting glycerol or glycerine which may be in pure or partly purified form or in solution, notably an aqueous solution.
  • an aqueous solution of glycerol is used.
  • the concentration of the glycerol is preferably of at least 1%, at best it varies from 10 to 50% by weight and preferably between 15 and 30% by weight in the reactor.
  • the glycerol concentration should not be too high for the purpose of avoiding parasitic reactions which burden the acrolein yield, like the formation of glycerol ethers or acetalization reactions between the produced acrolein and the non-converted glycerol.
  • the glycerol solution should not be too diluted, because of a redhibitory energy cost induced by the evaporation of the glycerol.
  • the invention further provides a method for making 3-(methylthio)propionic aldehyde (MMP), 2-hydroxy-4-methylthiobutyronitrile (HMTBN), methionine, 2-hydroxy-4-methylthiobutanoic acid (HMTBA), esters of the latter, notably the isopropyl ester, and 2-oxo-4-methylthiobutanoic acid (KMB) from acrolein, according to which the acrolein is obtained by a method described above.
  • MMP 3-(methylthio)propionic aldehyde
  • HMTBN 2-hydroxy-4-methylthiobutyronitrile
  • HMTBA 2-hydroxy-4-methylthiobutanoic acid
  • KMB 2-oxo-4-methylthiobutanoic acid
  • the acrolein produced according to the aforementioned method may contain impurities different from those of the traditional method, both under the angle of their amount and of their nature. According to the contemplated use, synthesis of acrylic acid or of me
  • the acrolein is directly obtained according to the invention or after purification, it is set to react with methylmercaptan (MSH) in order to produce 3-(methylthio)propionic aldehyde (or MMP).
  • MMP is put into contact with hydrocyanic acid in order to produce 2-hydroxy-4-(methylthio) butryronitrile (HMTBN).
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-(methylthio) butryronitrile
  • HMTBN 2-hydroxy-4-
  • FIG. 1 shows the development of the conversion into glycerol and of the corresponding acrolein selectivity over time, on each of the catalysts A, B, C and D described in the examples 1, 7, 8 and 9 respectively; the catalysts A and B are catalysts of the invention, the catalysts C and D are catalysts of the prior art.
  • the time indicated for each point is that of the end of sampling corresponding to trapping for one hour.
  • the reaction conditions and the calculation methods used by the acrolein conversion and selectivity are described later on.
  • FIG. 2 illustrates the conversion to glycerol and the acrolein selectivity obtained on the catalyst A according to the invention before and after regeneration under an air flow.
  • FIG. 3 illustrates a comparison of the conversion into glycerol and of the acrolein selectivity of this conversion over time, with each of the catalysts A′, C and D described in Examples 2, 8 and 9 respectively;
  • catalyst A′ is a catalyst of the invention, catalysts C and D are catalysts of the prior art.
  • FIG. 4 illustrates the conversion into glycerol and the acrolein selectivity obtained with the catalyst A′ according to the invention before and after regeneration under air flow.
  • the reaction for dehydration of the glycerol is conducted on the indicated catalysts, at atmospheric pressure, in a straight reactor with a fixed bed of diameter 18 mm.
  • the reactor is placed in an oven which allows the catalyst to be maintained at the reaction temperature which is 300° C.
  • the volume of catalyst loaded into the reactor is 4.5 mL, which gives a bed height of about 1.8 cm.
  • the reactor is fed with a flow rate of 3.77 g/h of aqueous solution with 20% by weight of glycerol.
  • the aqueous solution is vaporized by means of a C.E.M (Controlled Evaporator Mixer) Bronkhorst® evaporator in the presence of a nitrogen flow rate of 75 mL/min.
  • C.E.M Controlled Evaporator Mixer
  • the glycerol/water/nitrogen molar relative portion is 2.3/46.3/51.4.
  • the calculated contact time is of the order of 1.9 s i.e. a GHSV of 1930 h ⁇ 1 .
  • the contact time is defined as follows:
  • Examples 10, 11, 12, 16, 17 and 18 were obtained with a system of three traps mounted in series.
  • the first trap contains a known mass of water and is cooled by crushed ice.
  • the two other traps contain ethanol and are cooled by a cryostat to ⁇ 25° C.
  • Examples 13, 14 and 15 were obtained with a simple trap containing a known mass of water and cooled by crushed ice.
  • the trapping period is one hour and the feed rate is not interrupted during the changes of traps.
  • the formed products are analyzed by chromatography, two analyses are conducted for each sample:
  • the glycerol conversion, the acrolein selectivity and the yield of different products are defined as follows:
  • Glycerol conversion (%) 100 ⁇ (1 ⁇ number of remaining glycerol moles/number of introduced glycerol moles)
  • Acrolein selectivity (%) 100 ⁇ (number of produced acrolein moles/number of unreacted glycerol moles)
  • a catalyst according to the invention of the zirconium and niobium oxide type prepared from zirconium oxide hydrate and ammonium oxalate-niobiate, (NH 4 )(C 2 O 4 ) 2 NbO.xH 2 O (Aldrich, 99.99%).
  • the ammonium oxalate-niobiate is dissolved in permuted water acidified with concentrated HNO 3 at pH ⁇ 0.5 and heated to 45° C. After returning to room temperature, the zirconium hydroxide hydrate is added in a ZrO 2 /Nb 2 O 5 molar ratio of 3:1, the hydration degree of the zirconium oxide hydrate is determined beforehand by thermogravimetric analysis (TGA). After 24 h with stirring, the mixture is filtered and the solid is calcined under air flow at 600° C. The specific surface area of this catalyst is 40 m 2 /g. The specific surface areas of the solids were measured with the BET (Brunauer Emmet and Teller) method at ⁇ 196° C.
  • BET Brunauer Emmet and Teller
  • the solids are desorbed beforehand at 300° C. for 3 h in a vacuum of 5 ⁇ 10 ⁇ 5 mbars.
  • the niobium and zirconia contents of the different prepared solids were determined by ICP-OES (Inductively Coupled Plasma Optical Emission Spectrometry).
  • the Zr/Nb molar ratio of the catalyst A calculated from these analyses is 9.3.
  • a catalyst according to the invention of the zirconium and niobium oxide type is prepared according to the procedure described by Kantcheva. et. Al, Catalysis Communications (2009), 9(5), p 874-879, by impregnation of zirconium oxide hydrate.
  • the zirconium oxide hydrate was prepared by co-precipitation of a solution of zirconium oxonitrate ZrO(NO 3 ) 2 .xH 2 O (Aldrich, 99%) and of a 28% ammonia solution.
  • the precursor of Nb(V), (NH 4 )(C 2 O 4 ) 2 NbO.xH 2 O (Aldrich, 99.99%) is added with stirring to a 35% hydrogen peroxide solution (Sigma Aldrich) acidified to pH ⁇ 0.5 with concentrated HNO 3 and heated to 50° C.
  • the H 2 O 2 /oxalate molar ratio is 13/1.
  • the solution is heated for 1 h at 50° C. before being cooled down to room temperature.
  • the zirconium oxide hydrate is again added while ensuring a ZrO 2 :Nb 2 O 5 ratio of 6:1, the hydration degree of the zirconium oxide hydrate being determined by thermogravimetric analysis (TGA).
  • TGA thermogravimetric analysis
  • the specific surface area of this catalyst is 51 m 2 /g.
  • the specific surface areas of the solids were measured by the BET (Brunauer Emmet and Teller) a ⁇ 196° C. on a Micromeritics ASAP 2020 apparatus.
  • the solids are desorbed beforehand at 300° C. for 3 hours in a vacuum of 5 ⁇ 10 ⁇ 5 mbars.
  • the niobium and zirconium contents of the obtained solids were determined by ICP-OES.
  • the Zr/Nb molar ratio of this solid is 3.3.
  • a catalyst according to the invention of the zirconium and niobium oxide type is prepared according to the procedure described by Kantcheva. et. Al, (Catalysis Communications 9(5), (2008) p 874-879), by impregnation of zirconium oxide hydrate with a solution containing a mixed ammonium and niobium oxalate.
  • Nb(V), (NH 4 )(C 2 O 4 ) 2 NbO.xH 2 O (Aldrich, 99.99%) is added with stirring to a 35% hydrogen peroxide solution (Sigma Aldrich) acidified to pH ⁇ 0.5 with concentrated HNO 3 and heated to 50° C.
  • the H 2 O 2 /oxalate molar ratio is 13/1.
  • the solution is heated for 1 h at 50° C. before being cooled down to room temperature.
  • the zirconium oxide hydrate prepared beforehand by co-precipitation of a solution of zirconium oxonitrate (ZrO(NO 3 ) s .xH 2 O (Aldrich, 99%) and of a 28% ammonia solution, is added while ensuring a ZrO 2 :Nb 2 O 5 ratio of 6:1.
  • the mixture is maintained with stirring at room temperature for 24 hrs and the liquid phase is then evaporated in vacuo at T ⁇ 70° C.
  • the obtained solid is calcined under an air flow at 600° C.
  • the specific surface area of this catalyst determined in a similar way to that of catalyst A is 39 m 2 /g.
  • the niobium and zirconium contents of the obtained solid were determined by ICP-OES.
  • the molar ratio Zr/Nb of this solid is 3.7.
  • a catalyst according to the invention of the zirconium, niobium and vanadium oxide type is prepared.
  • the vanadium precursor was prepared from NH 4 VO 3 (Sigma, ACS Reagent 99.7%) according to the following method:
  • Ammonium metavanadate is dissolved in a 9% hydrogen peroxide solution containing oxalic acid (Aldrich, 99%).
  • the oxalic acid/introduced NH 4 VO 3 molar ratio is 1.3. After 1 hr with stirring at room temperature, the solution is evaporated in vacuo; a blue solid is obtained.
  • the vanadium oxide content of this compound is determined by thermogravimetric analysis.
  • the vanadium precursor, the mixed niobium and ammonium oxylate (NH 4 )C 2 O 4 ) 2 NbO.xH 2 O (Aldrich, 99.99%), and the zirconium oxide hydrate prepared as described in Example 1 are introduced into an aqueous solution acidified with concentrated HNO 3 (pH ⁇ 0.5) with a Zr/Nb/V molar ratio of 72/22/3.2. After 24 hrs with stirring, the reaction medium is filtered and the solid is calcined under air flow at 600° C. The specific surface area of this catalyst determined in a similar way to that of catalyst A is 48 m 2 /g. The niobium, vanadium and zirconium contents of the obtained solid were determined by ICP-OES. The Zr/Nb/V molar composition of this catalyst is 90.4/8.4/1.2.
  • a catalyst according to the invention of the tungstated zirconia type doped with silica is prepared.
  • the preparation of this solid includes three steps.
  • the second step comprises stabilizing the zirconium hydroxide hydrate with silicic species according to the procedure described by Nahas et. al (Journal of Catalysis 247 (2007), p 51-60).
  • the zirconium hydroxide hydrate is placed in a glass flask containing an ammoniacal solution, the pH of which is adjusted to 11. The mixture is refluxed for 72 hrs and then filtered and washed with permuted water. The last step is the exchange between tungstic acid H 2 WO 4 (Aldrich 99%) dissolved in hydrogen peroxide and zirconium hydroxide. The tungstic acid is dissolved in a 35% hydrogen peroxide solution at 60° C. The tungstic acid concentration of the solution is 0.04M. The tungstic acid solution is then cooled down to room temperature, and the zirconium hydroxide doped with silica is slowly added. The obtained solid is filtered and then calcined in air at 650° C.
  • the catalyst H is prepared according to the synthesis method described in Example 1.
  • the pH of the nitric acid solution is slightly more acid (pH ⁇ 0.1) in the case of the catalyst H.
  • the obtained solid has a specific surface area of 57 m 2 /g and a Zr/Nb molar ratio of 11.8.
  • the ZrTiSiW catalyst according to the invention was prepared by Rhodia according to the method described in patent FR2907445A.
  • the specific surface area of this catalyst, determined in a similar way to that of catalyst A, is 105 m 2 /g.
  • the weight composition of oxides of this catalyst is 54% of ZrO 2 , 35% of TiO 2 , 7.5% of SiO 2 and 3.5% of WO 3 .
  • the catalyst C is a tungstated zirconia (89.5% ZrO 2 — 10.5% WO 3 ) synthesised by Daiichi Kigenso (supplier reference: Z-1104).
  • the specific surface area of this catalyst determined in a similar way to that of catalyst A is 77 m 2 /g.
  • Catalyst D is an H-ZSM-5 zeolite provided by Zeochem (ZEOcat PZ-2/5OH).
  • the specific surface area of this catalyst determined in a similar way to that of catalyst A is 406 m 2 /g.
  • Table 1 gives the performances obtained with the catalysts A, B, C and D at 6 hrs of reaction.
  • the catalysts A and B are therefore more active and more selective than the catalysts of the prior art.
  • the catalysts A and B maintain constant acrolein selectivity and high glycerol conversion over several days unlike the catalysts C and D of the prior art which are strongly deactivated within less than 24 hrs.
  • the catalysts A and B of the invention are therefore more active, more acrolein-selective but also more stable over time than the best catalysts claimed in the prior art.
  • the catalyst A according to the invention is regenerated under an air flow of 450° C. for 2 hrs (air flow rate: 51 mL/min). After regeneration, the catalyst is tested under the same operating conditions as before regeneration.
  • the obtained results are shown in FIG. 2 .
  • the regeneration in air at 450° C. allowed the catalyst A to recover its activity and its initial yield.
  • the catalyst A according to the invention is therefore regenerable over a short time and without any loss of activity and selectivity. Not only the catalyst A is active and selective but it is also entirely and easily regenerable.
  • Table 2 gives the performances obtained at 300° C. with the catalysts A′, B and C at 5 hrs of reaction.
  • the catalyst A′ (invention) maintains quasi-constant acrolein selectivity and high glycerol conversion over one week in a reaction flow unlike the catalysts D and C of the prior art which are strongly deactivated within less than 24 hrs.
  • the catalyst A′ of the invention is therefore more active, more acrolein selective and more stable over time than the best catalysts claimed in the prior art.
  • the catalyst A′ according to the invention is regenerated under air flow at 450° C. for 1 hr (air flow rate: 51 mL/min). After regeneration, the catalyst is tested under the same operating conditions as before the regeneration.
  • the catalyst A′ Regeneration in air at 450° C. allowed the catalyst A′ to recover its activity and its initial yield.
  • the catalyst A′ according to the invention is therefore regenerable over a short time and without any loss of activity and selectivity. Not only the catalyst A′ is active and selective but it is also entirely and easily regenerable.
  • Table 4 gives the performances of the catalyst.
  • the performances of catalyst H were evaluated with a solution of raw industrial glycerine with a titer of 82% by weight.
  • This glycerine is characterized in that it contains more than 15% by weight of methanol.
  • the catalyst volume in the reactor is 4.5 mL
  • the nitrogen flow rate is 74.5 mL/min
  • the reaction temperature is 300° C.
  • the flow rate of the aqueous solution with 20% by weight of glycerine is 3.77 g/h.
  • the glycerol/water/nitrogen molar relative proportion is 1.9/46.5/51.6. The obtained results are given in table 5.
US13/140,109 2008-12-16 2009-12-16 Method for preparing acrolein from glycerol or glycerine Abandoned US20110288323A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0858624A FR2939791B1 (fr) 2008-12-16 2008-12-16 Procede de preparation d'acroleine a partir de glycerol ou de glycerine brute
FR0858624 2008-12-16
PCT/FR2009/052577 WO2010076510A2 (fr) 2008-12-16 2009-12-16 Procede de preparation d'acroleine a partir de glycerol ou de glycerine

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/FR2009/052577 A-371-Of-International WO2010076510A2 (fr) 2008-12-16 2009-12-16 Procede de preparation d'acroleine a partir de glycerol ou de glycerine

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/010,724 Continuation US9447009B2 (en) 2008-12-16 2013-08-27 Method for preparing acrolein from glycerol or glycerine

Publications (1)

Publication Number Publication Date
US20110288323A1 true US20110288323A1 (en) 2011-11-24

Family

ID=40791517

Family Applications (2)

Application Number Title Priority Date Filing Date
US13/140,109 Abandoned US20110288323A1 (en) 2008-12-16 2009-12-16 Method for preparing acrolein from glycerol or glycerine
US14/010,724 Active US9447009B2 (en) 2008-12-16 2013-08-27 Method for preparing acrolein from glycerol or glycerine

Family Applications After (1)

Application Number Title Priority Date Filing Date
US14/010,724 Active US9447009B2 (en) 2008-12-16 2013-08-27 Method for preparing acrolein from glycerol or glycerine

Country Status (10)

Country Link
US (2) US20110288323A1 (es)
EP (1) EP2365954B1 (es)
JP (1) JP6116799B2 (es)
KR (1) KR101778103B1 (es)
CN (2) CN102245552A (es)
ES (1) ES2709479T3 (es)
FR (1) FR2939791B1 (es)
RU (1) RU2531277C2 (es)
SG (1) SG171721A1 (es)
WO (1) WO2010076510A2 (es)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130197258A1 (en) * 2010-06-17 2013-08-01 Centre National De La Recherche Scientifique Process for preparing acrolein from glycerol or glycerin
US9187395B2 (en) 2012-10-30 2015-11-17 Adisseo France S.A.S. Method for preparing acrolein from glycerol
US9447009B2 (en) 2008-12-16 2016-09-20 Adisseo France S.A.S. Method for preparing acrolein from glycerol or glycerine
US10435347B2 (en) 2015-12-23 2019-10-08 Lg Chem, Ltd. Method for preparing acrylic acid from glycerin
US10569259B2 (en) 2015-12-22 2020-02-25 Lg Chem, Ltd. Catalyst for dehydration of glycerin, preparation method thereof, and production method of acrolein using the catalyst

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2966456B1 (fr) * 2010-10-26 2013-03-15 Adisseo France Sas Procede d'obtention d'acroleine par deshydratation catalytique de glycerol ou de glycerine
FR3001728B1 (fr) * 2013-02-04 2015-11-13 Adisseo France Sas Procede de preparation d’une olefine par conversion catalytique d’au moins un alcool
KR101616528B1 (ko) 2013-07-16 2016-04-28 주식회사 엘지화학 글리세린 탈수반응용 촉매, 이의 제조 방법 및 아크롤레인의 제조 방법
WO2015168683A1 (en) 2014-05-02 2015-11-05 University Of Tennessee Research Foundation Novel glycerol dehydration methods and products thereof
CN104892382B (zh) * 2015-05-28 2017-08-11 珠海凯美科技有限公司 甘油液相氧化制备丙烯醛的方法
KR102210508B1 (ko) * 2015-12-23 2021-02-01 주식회사 엘지화학 글리세린 탈수 반응용 촉매의 제조 방법 및 아크롤레인의 제조 방법
CN109305899B (zh) * 2017-07-28 2021-09-03 中国石油化工股份有限公司 甘油脱水生产丙烯醛的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7846861B2 (en) * 2007-01-29 2010-12-07 Evonik Degussa Gmbh Process for regenerating a catalyst

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU52208A1 (ru) * 1936-04-22 1936-11-30 Ю.Н. Вольнов Способ получени акролеина из глицерина
US4524077A (en) * 1983-11-14 1985-06-18 Monsanto Company Liquid 2-hydroxy-4-methylthiobutyric acid and process for the preparation thereof
DE102005003990A1 (de) * 2005-01-28 2006-08-03 Degussa Ag Herstellung von 3-(Alkylthio)propanal
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
FR2884818B1 (fr) * 2005-04-25 2007-07-13 Arkema Sa Procede de preparation d'acide acrylique a partir de glycerol
WO2007058221A1 (ja) * 2005-11-15 2007-05-24 Nippon Shokubai Co., Ltd. 多価アルコールの脱水方法
JP4041512B2 (ja) * 2006-03-30 2008-01-30 株式会社日本触媒 グリセリン脱水用触媒、グリセリン脱水用触媒の製造方法、アクロレインの製造方法、およびアクロレイン誘導体の製造方法
WO2007132926A1 (en) 2006-05-12 2007-11-22 Nippon Shokubai Co., Ltd. Production method of acrolein
TW200811086A (en) 2006-07-11 2008-03-01 Adisseo Ireland Ltd Process for preparing 2-hydroxy-4-(methylthio)butyronitrile and methionine
FR2907444B1 (fr) 2006-10-20 2008-12-19 Rhodia Recherches & Tech Composition a acidite elevee a base d'oxydes de zirconium,de silicium et d'au moins un autre element choisi parmi le titane,l'aluminium,le tungstene,le molybdene,le cerium,le fer et le manganese
FR2907445B1 (fr) 2006-10-20 2010-09-03 Rhodia Recherches & Tech Composition a acidite elevee a base d'oxyde de zirconium, d'oxyde de titane et d'oxyde de tungstene,procede de preparation et utilisation dans le traitement des gaz d'echappement
US8076509B2 (en) 2006-12-01 2011-12-13 Nippon Shokubai Co., Ltd. Process for producing acrylic acid
DE102007004351A1 (de) 2007-01-29 2008-07-31 Evonik Degussa Gmbh Neue Katalysatoren und Verfahren zur Dehydratisierung von Glycerin
JP2008266165A (ja) * 2007-04-17 2008-11-06 Nippon Shokubai Co Ltd アクロレインの製造方法
FR2920767B1 (fr) 2007-09-06 2009-12-18 Arkema France Procede de vaporisation reactive de glycerol
WO2009136537A1 (ja) 2008-04-16 2009-11-12 日本化薬株式会社 グリセリンの脱水反応によるアクロレイン及びアクリル酸の製造用触媒と、その製造方法
WO2009127889A1 (en) 2008-04-16 2009-10-22 Arkema France Process for manufacturing acrolein from glycerol
FR2938535B1 (fr) 2008-11-20 2012-08-17 Arkema France Procede de fabrication de methylmercaptopropionaldehyde et de methionine a partir de matieres renouvelables
FR2939791B1 (fr) 2008-12-16 2011-01-14 Adisseo France Sas Procede de preparation d'acroleine a partir de glycerol ou de glycerine brute
FR2954312B1 (fr) 2009-12-21 2012-02-10 Adisseo France Sas Procede de preparation d'acroleine par deshydratation catalytique de glycerol ou glycerine
FR2961507B1 (fr) 2010-06-17 2016-03-04 Adisseo France Sas Procede de preparation d'acroleine a partir de glycerol ou de glycerine

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7846861B2 (en) * 2007-01-29 2010-12-07 Evonik Degussa Gmbh Process for regenerating a catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9447009B2 (en) 2008-12-16 2016-09-20 Adisseo France S.A.S. Method for preparing acrolein from glycerol or glycerine
US20130197258A1 (en) * 2010-06-17 2013-08-01 Centre National De La Recherche Scientifique Process for preparing acrolein from glycerol or glycerin
US9079841B2 (en) * 2010-06-17 2015-07-14 Adisseo France S.A.S. Process for preparing acrolein from glycerol or glycerin
US9187395B2 (en) 2012-10-30 2015-11-17 Adisseo France S.A.S. Method for preparing acrolein from glycerol
US10569259B2 (en) 2015-12-22 2020-02-25 Lg Chem, Ltd. Catalyst for dehydration of glycerin, preparation method thereof, and production method of acrolein using the catalyst
US10435347B2 (en) 2015-12-23 2019-10-08 Lg Chem, Ltd. Method for preparing acrylic acid from glycerin

Also Published As

Publication number Publication date
FR2939791A1 (fr) 2010-06-18
US20140171676A1 (en) 2014-06-19
RU2011123484A (ru) 2013-01-27
CN105837420A (zh) 2016-08-10
JP6116799B2 (ja) 2017-04-19
FR2939791B1 (fr) 2011-01-14
KR101778103B1 (ko) 2017-09-13
EP2365954B1 (fr) 2018-11-07
US9447009B2 (en) 2016-09-20
WO2010076510A3 (fr) 2010-10-14
CN105837420B (zh) 2019-09-13
EP2365954A2 (fr) 2011-09-21
JP2012512236A (ja) 2012-05-31
SG171721A1 (en) 2011-07-28
KR20110094198A (ko) 2011-08-22
ES2709479T3 (es) 2019-04-16
CN102245552A (zh) 2011-11-16
RU2531277C2 (ru) 2014-10-20
WO2010076510A2 (fr) 2010-07-08

Similar Documents

Publication Publication Date Title
US9447009B2 (en) Method for preparing acrolein from glycerol or glycerine
US9079841B2 (en) Process for preparing acrolein from glycerol or glycerin
CN102159521B (zh) 利用双反应区方法由乙酸生产乙烯
JP6021878B2 (ja) グリセロールの脱水によるアクロレインの製造方法
US8604234B2 (en) Method for preparing acrolein from glycerol by catalytic dehydration of glycerol using a heteropolyacid catalyst
US8686195B2 (en) Method for synthesizing acrolein from glycerol
US8785645B2 (en) Method for synthesizing bio-based pyridine and picolines
US9187395B2 (en) Method for preparing acrolein from glycerol
WO2014108417A1 (en) Production of acrylic acid
MX2008010086A (es) Metodo de preparacion de acido acrilico

Legal Events

Date Code Title Description
AS Assignment

Owner name: ADISSEO FRANCE S.A.S, FRANCE

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BELLIERE-BACA, VIRGINIE;LORIDANT, STEPHANE;MILLET, JEAN-MARC;AND OTHERS;SIGNING DATES FROM 20110517 TO 20110629;REEL/FRAME:026718/0922

Owner name: CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE, FRAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BELLIERE-BACA, VIRGINIE;LORIDANT, STEPHANE;MILLET, JEAN-MARC;AND OTHERS;SIGNING DATES FROM 20110517 TO 20110629;REEL/FRAME:026718/0922

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION