WO2007058221A1 - Procede de deshydratation des polyols - Google Patents

Procede de deshydratation des polyols Download PDF

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Publication number
WO2007058221A1
WO2007058221A1 PCT/JP2006/322777 JP2006322777W WO2007058221A1 WO 2007058221 A1 WO2007058221 A1 WO 2007058221A1 JP 2006322777 W JP2006322777 W JP 2006322777W WO 2007058221 A1 WO2007058221 A1 WO 2007058221A1
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WIPO (PCT)
Prior art keywords
catalyst
acrolein
producing
glycerin
reaction
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PCT/JP2006/322777
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English (en)
Japanese (ja)
Inventor
Bo-Qing Xu
Song-Hai Chai
Tsukasa Takahashi
Masahide Shima
Satoshi Sato
Ryouji Takahashi
Original Assignee
Nippon Shokubai Co., Ltd.
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Priority claimed from JP2005330481A external-priority patent/JP2007137785A/ja
Application filed by Nippon Shokubai Co., Ltd. filed Critical Nippon Shokubai Co., Ltd.
Publication of WO2007058221A1 publication Critical patent/WO2007058221A1/fr

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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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • B01J23/16—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
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively

Definitions

  • the present invention relates to a method for producing a dehydration product using a compound having three or more hydroxyl groups as a raw material, and a catalyst for gas phase dehydration. More specifically, the present invention relates to a method for producing a dehydrated product suitable for producing acrolein or an acrolein aqueous solution by contacting glycerol with a catalyst in the gas phase to dehydrate, and a gas phase dehydrating catalyst used therefor.
  • the present invention also relates to a catalyst for producing acrolein and a method for producing acrolein using the same, and is suitable for a method for producing acrolein using glycerin not derived from petroleum as a raw material. More specifically, the present invention relates to an acrolein production catalyst suitable for producing acrolein or an acrolein aqueous solution by dehydrating glycerin using a catalyst, and an acrolein production method using the same.
  • a method for producing a dehydrated product using a compound having three or more hydroxyl groups as a raw material is useful as a method for producing industrial raw materials such as glycerin-acrolein, and various methods have been studied.
  • the production of acrolein by dehydration of glycerin has the following advantages.
  • acrolein is usually produced by propylene gas-phase acid, but the raw material propylene is a fossil resource, and there are concerns about future resource depletion and increased carbon dioxide in the atmosphere. is there.
  • glycerin used as a raw material can be obtained from vegetable oil.
  • Non-Patent Document 1 “Industrial Science”, 1934, 37th (Suppl, binding), p. See 538;).
  • the catalyst include iron phosphate, activated clay, KHSO K S
  • Non-Patent Document 5 “Preblind'Ob'Paper's American'Chemical'Society 1, Tyhi, Chillon '”
  • “Fuenore” Chemistry (Preprints of Papers-American Chemical Society, Division of Fuel Chemistry;) (USA), 1985, No. 30, No. 3, pp. 78-87
  • Non-Patent Document 6 "Energy from Biomass and Wastes;” (USA), 1987, No. 10, p. 865-877, and Non-Patent Document 7; "Fuel", (United Kingdom), 1987, 66, No. 10, pp. 13 64–1371 etc.).
  • the method of using supercritical water is an industrial practice. ⁇ It is difficult to say that it is economically advantageous.
  • Patent Document 3 United Kingdom
  • Patent Document 4 Chinese Patent No. 1272495
  • Patent Document 4 Chinese Patent No. 1272495
  • the glycerin used as a raw material can be obtained from vegetable oil, and it can also be used as a biodiesel fuel by transesterification of plant oil and as a by-product in the production of sarcophagus. Obtainable. Therefore, in the method in which glycerin can be used as a raw material, it can be regenerated because glycerin is derived from a plant, and the carbon source for which there is no concern about resource depletion is that it is carbon dioxide in the atmosphere. Therefore, it has the advantage that it does not contribute to the increase of carbon dioxide in the atmosphere.
  • Patent Document 2 Japanese Patent Laid-Open No. 6-211724
  • Patent Document 4 Chinese Patent No. 1272495
  • Non-Patent Document 3 Koichi ISHIKAWA et al., “Analytical Chemistry (BUN SEKI KAGAKU)”, 1983, No. 32, No. 10, pp. E321—E325
  • Non-Patent Document 4 Lee H. Dao et al., “Reactions' Ob 'Model Compound' Ob 'Biomass Pyrolysis Inenoles' Over ⁇ ⁇ ZSM-5 Zeolite Catalysts (Reactions of Model and ompounas of Biomass- PyrolysisOiis over ZSM-5 z-eolite Catalysts) —American Chemical Society Symposium Series (USA), 1988, No. 376 (Pyrolysis Oils Biomass), pp. 328—341
  • Non-Patent Document 5 "Preprints of Papers-American Chemical Society, Division of FudChemistry” (USA), 1985, 30th, No. 3, pp. 78—87
  • Non-Patent Document 7 “Fuel” (UK), 1987, 66th, No. 10, PP. 136 4-1371
  • the present inventors As a result of searching for a catalyst for obtaining a dehydrated product and various methods for producing the dehydrated product, the present inventors, for example, when acrolein is obtained by glycerin force dehydration reaction, the raw material is contacted with the catalyst. Focusing on the fact that the gas phase dehydration reaction to be carried out is advantageous in terms of resources and the environment, if a catalyst using a group 6 element is essential, the desired dehydration product can be obtained with high selectivity. I found it advantageous. It was also found that such a catalyst has high stability over time, and it is difficult for the catalyst activity to decrease even in a reaction using a high-concentration glycerin solution. Thus, the inventors have arrived at the present invention by conceiving that the above-mentioned problems can be solved by specifying the essential elements contained in the catalyst in the gas phase dehydration reaction.
  • acrolein obtained by dehydrating glycerin is a highly reactive substance, and so many reactions are known.
  • Japanese Patent Laid-Open No. 4 266884 describes a method of obtaining acrolein glycerin acetal by reacting glycerin as a raw material of the present application with acrolein as a product.
  • various reactions such as Michael addition and Diels-Alder reaction may occur.
  • the method for producing a dehydrated product by vapor-phase dehydration using a compound having 3 or more hydroxyl groups that can generate acrolein as a raw material is a regioselectivity of a reaction that is not limited to simple dehydration power. Suitable catalysts are difficult to predict because sequential reactions have a major impact.
  • the present inventor studied the production of acrolein using glycerin that can be easily obtained from naturally derived oils and fats as a raw material.
  • the inventors have found that acrolein can be obtained more efficiently by the method for producing acrolein in which glycerin is reacted in the presence of a heteropolyacid catalyst, and the present invention has been completed.
  • the present invention is also a method for producing a dehydrated product by dehydrating a compound having 3 or more hydroxyl groups, wherein the production method comprises reacting glycerin in the presence of a heteropolyacid catalyst to produce acrolein. It is also a method for producing a dehydrated product.
  • the method for producing a dehydrated product is preferably a method for producing a dehydrated product, which is a method for producing acrolein by dehydrating glycerin.
  • the catalyst is preferably a method for producing a dehydrated product in which the Group 6 element is at least one element selected from the group consisting of tungsten, chromium, and molybdenum.
  • the catalyst is preferably a method for producing a dehydrated product in which the Group 6 element is tungsten.
  • the heteropolyacid catalyst is preferably a method for producing a dehydrated product having a Keggin structure.
  • the catalyst is preferably a method for producing a dehydrated product supported on an inorganic carrier.
  • the inorganic carrier is preferably a method for producing a dehydrated product having at least one element selected from the group consisting of silicon, aluminum, titanium, and zirconium.
  • a method for producing a dehydrated product by dehydrating a compound having three or more hydroxyl groups wherein the production method comprises a step of contacting with a catalyst containing at least one group 6 element
  • this method is also referred to as a method for producing a dehydrated product using a catalyst containing at least one group 6 element.
  • the production method comprises dehydration by reacting glycerin in the presence of a heteropolyacid catalyst to produce acrolein.
  • the production method of the product is also referred to as acrolein production method.
  • the content of the Group 6 element is preferably 1 or more, more preferably 20 or more, and still more preferably 60, out of all 1000 atoms excluding oxygen and hydrogen from the catalyst constituents including the support. More than one.
  • the upper limit of the content of the Group 6 element is not particularly limited, but even if it contains 80% or more of the catalyst weight, no effect can be expected.
  • elements other than Group 6 elements are not particularly limited, but vanadium increases by-products and decreases the acrolein yield, so that the amount of vanadium atoms exceeds the number of tungsten atoms. Saddle is not preferred.
  • the catalyst having the Group 6 element only needs to contain at least one group 6 element, and its form is not specified.
  • an amorphous compound, a single oxide, or a complex oxide may be used. included.
  • the source of addition of elements in Group 6 is not specified, but inorganic salts such as nitrates, sulfates, hydrochlorides, phosphates and carbonates, and organic acid salts such as oxalates, citrates and tartrates, Complex salts or acid compounds can be used.
  • Heteropolyacids such as phosphotungstic acid can also be suitably used. Of these, heteropolyacids are particularly preferred.
  • the gas phase dehydration catalyst may be one in which a Group 6 element is supported on an inorganic carrier.
  • a supported catalyst By using a supported catalyst, the active substance can be used effectively and the shape of the catalyst can be easily provided.
  • the shape of the catalyst may be an indefinite shape such as a crushed product, but preferably a spherical shape, ring shape, cylindrical shape, saddle shape, half ring shape or the like generally used for a gas phase reaction is preferably used.
  • the inorganic carrier includes at least one element selected from the group consisting of zirconium, aluminum, and silicon, such oxides, hydrated oxides, nitrides, carbides, and the like. Available. Further, it is particularly preferable to contain zirconium.
  • zirconium for example, as such an inorganic carrier, industrially used oxides such as zirconium, alumina and silica, and powders and molding carriers made of complex oxides or mixtures thereof can be used.
  • these precursors such as hydroxides, hydrated oxides and salts can be used.
  • a solution containing at least one group 6 element is supported by impregnating a solution containing at least one group 6 element using a composition carrier made of an inorganic oxide containing one or more of zirconium, aluminum, and silicon as a constituent element. Also good.
  • a salt solution containing any one of zirconium, aluminum, and silicon may be used. Even if it is a method of adding at least one group 6 element, precipitating by neutralization method, etc., then drying and firing, the form in which group 6 element finally exists on the surface of these inorganic oxides If the method becomes! /, The method of deviation can also be used.
  • Hammett's acidity function is defined by the degree of discoloration of an indicator using a specific indicator group of neutral base (B) and the tendency of an oxide to transfer protons to these indicators. is there. If the dissociation constant of the acid form BH + of the indicator is K,
  • the degree function H is defined by the following equation.
  • the method for producing a dehydrated product of the present invention is a method for producing a dehydrated product by dehydrating a compound having 3 or more hydroxyl groups.
  • the compound having 3 or more hydroxyl groups as a raw material for production may be a compound such as a polyhydric alcohol having at least 3 hydroxyl groups in one molecule.
  • a compound having 3 hydroxyl groups is used. It is preferable to use some glycerin.
  • glycerin In the dehydration reaction using glycerin as a raw material, acrolein is obtained as a dehydrated product.
  • the reaction pressure is not particularly specified but is preferably 1 atm or less.
  • the temperature in the gas phase dehydration is preferably 200 to 500 ° C. If the temperature is lower than 200 ° C, the reaction rate may extremely decrease, and if it exceeds 500 ° C, the degradation of dariselin or the sequential reaction of the generated acrolein may increase, leading to a decrease in selectivity. There is. More preferably, it is 200-450 degreeC.
  • the lower limit of the reaction temperature is also limited by the vapor pressure of glycerin, and it is preferable that all of the supplied glycerin be at or above the temperature at which it can exist in a gaseous state.
  • the feed rate of the raw material gas to the catalyst is preferably about 100 to 5000 Zhr as the space velocity. If it is less than lOOZhr, the yield may decrease due to the sequential reaction, and if it exceeds 5000 Zhr, the reaction does not proceed sufficiently. The conversion rate may be reduced.
  • a catalyst layer can be formed by filling a catalyst in a reaction tube.
  • the ratio of glycerin to an inert condensable substance such as water is preferably 0 to 12 mol of inert condensable substance with respect to 1 mol of glycerin, for example. . That is, the glycerin concentration is preferably 7.7 to: LOOmol%. More preferably, the glycerin concentration is 23 to: LOOmol%, and still more preferably the glycerin concentration is 31 to: LOOmol%.
  • acrolein can be obtained in a high yield even when such a high-concentration glycerin solution is used, and thus a high-concentration acrolein solution can be obtained directly.
  • the reaction product gas can be cooled and condensed to be acrolein or an acrolein solution, used as a raw material for producing acrylic acid or methionine, and acrolein obtained by condensation can be used.
  • Acrylic acid can be obtained by vaporizing again and mixing with a suitable amount of air or water vapor using a known method of gas phase oxidation to oxidize. Also, omitting the condensation step, for example, tandem, which is currently used in the production of acrylic acid by propylene two-stage gas phase acid, is directly acrylic acid using a method using a single reactor. Can also be obtained.
  • the two-stage gas phase acid is a reaction site that mainly generates acrolein by oxidizing propylene and a reaction site force that generates acrylic acid by oxidizing the generated acrolein.
  • the above-described production method is an example of a method for producing a dehydrated product, and can be applied to other methods for producing a dehydrated product.
  • the catalyst of the present invention is preferably applied to a gas phase dehydration reaction for dehydrating a compound having 3 or more hydroxyl groups in the gas phase to obtain a dehydrated product.
  • the preferred form of the catalyst for vapor phase dehydration of the present invention is as described above, and is suitably applied to a method for producing acrolein by vapor phase dehydration of glycerin.
  • the group 6 element is preferably at least one element selected from the group consisting of tungsten, chromium, and molybdenum, and more preferably the group 6 element is tungsten.
  • the Group 6 element is supported on an inorganic carrier.
  • the inorganic carrier preferably has at least one element selected from the group consisting of zirconium, aluminum, and silicon. Better ,.
  • both the conversion rate and the selectivity are high, but it is more important that the selectivity is high.
  • the reason is that the selectivity is largely related to the quality of the product. If the conversion rate is low but the selectivity is high, the final yield can be improved by recovering and reusing unreacted raw materials. It is also the power that can bring the selection rate close.
  • the present invention is also a method for producing acrolein in which glycerin is reacted in the presence of a heteropolyacid catalyst.
  • the method for producing a product is a method for producing acrolein in which the glycerin is reacted in the presence of a heteropolyacid catalyst.
  • the catalyst support that the heteropolyacid preferably contains at least one of silicon, phosphorus, tungsten, and molybdenum is at least silica, alumina, titanium, and zircoure. Although it is desirable to contain any of the acids, it is not limited to these.
  • glycerin is used for producing glycerin acrolein which is desired to be subjected to the reaction as glycerin water having a water content of 95% by weight or less.
  • a second means is a method for producing acrolein in which glycerin is reacted in the presence of a catalyst having a heteropolyacid and a catalyst carrier.
  • the catalyst for producing acrolein according to the present embodiment preferably has a heteropolyacid and a catalyst carrier.
  • the raw material glycerin can be dehydrated to produce acrolein.
  • the dehydration reaction of glycerin is a reaction in which glycerin is converted to acrolein, and the raw material (glycerin or glycerin water) is vaporized into gaseous form, and this gaseous raw material is brought into gas phase contact with the catalyst to be reacted. This is preferred.
  • the present invention provides a further excellent effect by using a catalyst having a heteropolyacid and a catalyst carrier as in the first means, but is not limited to a form having a catalyst carrier, and a single catalyst A sufficiently high effect can be obtained even if it is used.
  • the raw material can be used as a catalyst by adhering and supporting the raw material on a catalyst carrier.
  • SiO, Al 2 O, TiO, or ZrO can be used as the catalyst carrier. These are usually
  • the reaction apparatus used in the production of acrolein is not particularly limited.
  • the reaction temperature in the process for producing acrolein using this catalyst is preferably in the temperature range of 150 ° C or higher and 450 ° C or lower.
  • a temperature of 150 ° C or higher is a preferred by-product This is because 450 ° C. or lower is preferable in order to suppress the formation of the product and improve the selectivity of acrolein as the target product.
  • the reaction temperature in the above acrolein production method means the reaction temperature in the dehydration reaction step of producing acrolein by dehydrating glycerin.
  • the temperature is 0 ° C to 400 ° C.
  • the supply rate of the raw material gas to the catalyst is preferably about 100 to 5000 Zhr as the space velocity. If it is less than lOOZhr, the yield may decrease due to the sequential reaction, and if it is 5000 Zhr or more, the reaction is sufficient. There is a possibility that the conversion does not proceed and the conversion rate decreases.
  • a catalyst layer can be formed by filling a catalyst in a reaction tube.
  • the glycerin solution used is water-soluble A liquid can be used suitably.
  • an organic solvent may be used if it is a substance that dissolves glycerin and does not inhibit the reaction.
  • a glycerin solution in which glycerin is dissolved in an organic solvent can also be used.
  • concentration of the glycerin solution is not particularly limited, and may be 100% by mass of glycerin.
  • Condensable substance, CO in order to adjust the gas concentration and the space velocity with respect to the catalyst, Condensable substance, CO
  • the two-stage gas-phase acid has a reaction site that mainly generates acrolein by oxidizing propylene and a reaction site that generates acrylic acid by oxidizing the generated acrolein.
  • the catalyst of the present application By installing the catalyst of the present application at the site where acidification occurs, the raw material is converted into propylene power and glycerin, so that acrolein that also generates glycerin power Acrylic acid can also be produced directly by feeding it to the reaction site to obtain acrylic acid by acidification.
  • air or oxygen which is the oxidant necessary for the oxidation reaction, may be supplied from the first-stage dewatering reaction inlet force, or supplied to the second-stage oxidation reaction inlet!
  • the acrolein production method described above is an example of a dehydrated product production method, and can be applied to other dehydrated product production methods.
  • a structure with 12 coordinate elements is sometimes referred to as A-type.
  • X represents a hetero element and is not particularly limited as long as it is an element capable of forming a heteropolyacid.
  • M represents a coordination element and is not particularly limited as long as it is an element capable of forming heteropolyacid as a coordination element, and examples thereof include molybdenum, tungsten, niobium, and vanadium.
  • O represents an oxygen atom.
  • the hetero element is phosphorus, silicon, gel Manium and arsenic are preferred.
  • the hetero element is preferably cerium or thorium.
  • the hetero element is preferably phosphorus, arsenic, or germanium.
  • the heteropolyacid has a Dawson structure, the hetero element is preferably phosphorus or arsenic.
  • the heteropolyacid has an Anderson structure, it is preferable that the hetero element is tellurium, iodine, connort, aluminum, or chromium.
  • the heteropolyacid catalyst has a Keggin structure. Since the heteropolyacid catalyst has a Keggin structure, thermal stability is increased.
  • the heteropolyacid catalyst having a Keggin structure preferably has a structure represented by the above general formula (1).
  • the yield and selectivity of acrolein can be improved.
  • the method for producing acrolein having the above embodiment is, in other words, a method for producing a dehydrated product by dehydrating a compound having 3 or more hydroxyl groups, wherein the production method comprises converting glycerol to a heteropolyacid catalyst.
  • the heteropolyacid catalyst has the above form, the yield and selectivity of acrolein can be improved. More preferably, the coordination element is tungsten.
  • the active ingredient heteropolyacid is uniformly highly dispersed, which makes it more suitable for the production of acrolein and improves the yield and selectivity of acrolein.
  • the inorganic carrier has at least one element selected from the group consisting of zirconium, aluminum and silicon, or these oxides, hydrated oxides, nitrides, carbides and the like can be used. In particular, it is preferable to contain silicon.
  • industrially used powders such as silica, alumina, titer, and zirconium oxide, and composite powders and mixtures of these oxides and mixtures are used. be able to.
  • These precursors such as hydroxides, hydrates and salts can also be used.
  • the inorganic carrier contains silicon oxide as a main component. It is.
  • the inorganic carrier is one prepared using tetraethoxysilane as a raw material, and is also one preferred embodiment of the present invention.
  • tetraethoxysilane which is substantially free of sodium element
  • the inorganic carrier preferably includes a portion prepared using tetraethoxysilane as a raw material.
  • the inorganic carrier preferably has a weight ratio of 50% by weight or more occupied by a portion prepared using tetraethoxysilane in 100% by weight of the inorganic carrier. The weight ratio is more preferably 80% by weight or more. More preferably, it is 90% by weight or more, and particularly preferably 95% by weight or more.
  • the inorganic carrier has a specific surface area of 30 to 1500 m 2 / g.
  • the specific surface area is preferably 50 to: L000m 2 / g. More preferably, it is 100 to 800 m 2 Zg.
  • the specific surface area is more preferably 200 to 700 m 2 / g. Particularly preferred is 250 to 600 m 2 Zg. Most preferably, it is 300 to 500 m 2 Zg.
  • the inorganic carrier has binary pores.
  • the binary pore is an inorganic porous material having both macropores having a pore size in the micrometer region and nanopores having a pore size in the nanometer region.
  • the inorganic carrier having binary pores as described above is a macropore having excellent mass transporting ability, and In addition, it has both nanopores with a high specific surface area, has sufficient mechanical strength, and has little pressure loss. Therefore, it is suitable as a catalyst support used in the above production method, and further, acrolein selectivity and yield are obtained. The rate can be improved.
  • the macropores preferably have a pore diameter of 0.5 to 200 m. More preferably, 1 to: LOO / z m.
  • the nanopore is preferably 1 to 50 nm, and preferably has a structure in which the through holes are entangled in a three-dimensional network.
  • the macropores can be measured by mercury porosimetry or direct observation with an electron microscope. The nanopores can be confirmed by mercury porosimetry or nitrogen adsorption.
  • the inorganic carrier having binary pores is preferably in the form of particles having an average particle diameter of 5 to 10 mm.
  • the pore volume of the inorganic carrier is preferably 0.3 to 4 cm 3 per lg of carrier. In consideration of the ease of production, it is preferably 1 to 3 cm 3 .
  • the method for producing the inorganic carrier having the binary pores is not particularly limited.
  • the inorganic carrier having the binary pores includes a structure having through holes entangled in a three-dimensional network.
  • the inorganic carrier having the above-mentioned binary pores is an inorganic carrier having binary pores indispensable for macropores and nanopores. It is one of the preferred embodiments of the present invention that the pore diameter is 0.5 to 200 / ⁇ ⁇ and the pore diameter of the nanopore is 1 to 50 nm.
  • the inorganic carrier having the above-mentioned binary pores has a specific surface area of 300 to L000m 2 Zg.
  • the specific surface area of the inorganic carrier having binary pores is preferably 400 to 900 m 2 Zg, more preferably 500 to 850 m 2 / g. More preferably, it is 550 to 800 m 2 / g. Particularly preferred is 650 to 800 m 2 Zg.
  • the present invention is also a heteropolyacid catalyst used in the above production method. That is, the heteropolyacid catalyst of the present invention is applied to a gas phase dehydration reaction for dehydrating glycerol in the gas phase to obtain acrolein.
  • a preferred form of the heteropolyacid catalyst is as described in the above production method.
  • the heteropolyacid catalyst of the present invention is useful from the viewpoint of activity, selectivity, and productivity in the production of industrial dehydration products, and its operational effects can be sufficiently enhanced by the above preferred embodiments. Is.
  • the method for producing the dehydrated product and the method for producing acrolein are common in the means and effects of dehydrating a compound having 3 or more hydroxyl groups to obtain the desired dehydrated product with high selectivity.
  • preferred embodiments and reaction conditions in the acrolein production method are preferred embodiments for the dehydration product production method, and can be appropriately applied to the dehydration product production method.
  • preferred embodiments, reaction conditions, and the like in the method for producing the dehydrated product are also preferred embodiments for the method for producing acrolein, and can be appropriately applied to the method for producing acrolein. .
  • the activity is higher than when a conventional acidic oxide catalyst is used. It exhibits excellent characteristics in both selectivity and suppresses the decrease in activity and selectivity over time, which is economically advantageous in industrial implementation. Moreover, it is economically advantageous in industrial implementation in that acrolein can be obtained without being derived from petroleum. In particular, glycerin can also be obtained with high selectivity by gas phase dehydration reaction.
  • acrolein can be obtained in a high yield, whereby a high-concentration acrolein solution can be obtained directly, and further, there is little deterioration of the catalyst over time.
  • the form can be provided.
  • a catalyst suitable for acrolein production can be provided, and acrolein can be obtained using V and raw materials not derived from petroleum. Compared to the case of using a conventional catalyst, it shows excellent characteristics in both activity (conversion rate, yield) and selectivity, and suppresses the decrease in activity and selectivity over time, making it economical in industrial implementation. Is advantageous.
  • gas phase dehydration By the reaction glycerin can also obtain acrolein with high selectivity. In this case, even when a high-concentration glycerin solution is used, acrolein can be obtained in a high yield, whereby a high-concentration acrolein solution can be obtained directly, and the catalyst deterioration over time can be reduced. Less form can be provided.
  • acrylic acid can be produced by reacting acrolein obtained by the production method of the present invention with an acid reaction.
  • the present invention is also a method for producing acrylic acid by an industrially advantageous method starting from glycerin.
  • the selectivity of acrolein is 60 mol% or more.
  • the acrolein selectivity is preferably 65 mol% or more. More preferably, it is 70 mol% or more, still more preferably 75 mol% or more, particularly preferably 80 mol% or more, and most preferably 85 mol% or more.
  • the selectivity is high Rukoto of Akurorein production method of the above-mentioned Akurorein is still becomes good industrially more efficient, and the selectivity of Akurorein is 60 mole 0/0 above, i.e., the Akurorein It means that the yield (mole) is 60 mol% or more with respect to the amount (mole) of glycerin converted in the above production method.
  • the acrolein selectivity is preferably obtained, for example, as follows.
  • acrolein and the amount of glycerin using a gas chromatography analyzer, for example, using a Shimadzu GC-8A, TC-WAX capillary column, can do.
  • the method for producing the Akurorein, it Akurorein yield is 40 mol 0/0 above is one preferred embodiment of the present invention.
  • the yield of acrolein is preferably 70 mol% or more. More preferably, it is 74% or more, more preferably 77% by mole or more, particularly preferably 80% or more, most preferably 83% by mole or more, and most preferably 85% or more. More than mol% It is.
  • the yield of acrolein is preferably determined, for example, as follows.
  • the conversion rate and selectivity in industrial production, it is preferable that both the conversion rate and the selectivity are high, but it is more important that the selectivity is high. The reason is that the selectivity is largely related to the quality of the product. If the conversion rate is low but the selectivity is high, the final yield can be improved by recovering and reusing unreacted raw materials. It is also the power that can bring the selection rate close.
  • the ability to recover and reuse unreacted glycerin means that the conversion of glycerin to a byproduct that is not acrolein requires that glycerin be recovered and reused. Means you can no longer do.
  • the amount of glycerin transferred to a by-product that is not acrolein is an amount of waste of glycerin. Therefore, from the viewpoint of reducing costs by reducing the amount of wasted glycerin, it is preferable to reduce as much as possible the amount of glycerin transferred to a byproduct that is not acrolein.
  • the yield of by-products produced by glycerin force is 55 mol% or less.
  • the yield of by-products produced by converting the glycerin power is preferably 45 mol% or less. More preferably, it is 35 mol% or less, more preferably 25 mol% or less, particularly preferably 20 mol% or less, and most preferably 15 to 10 mol%.
  • the by-product generated by the conversion of the glycerin force is, in other words, a compound formed by the conversion of glycerin, and is a compound that is not acrolein.
  • the yield of the by-product produced by the above glycerin force conversion is preferably obtained, for example, as follows.
  • acrylic acid can be produced by reacting acrolein obtained by the above acrolein production method with an acid reaction. That is, the present invention is also a method for producing acrylic acid comprising a step of acidifying acrolein obtained by the above production method and converting it to acrylic acid.
  • a catalyst for gas phase dehydration When producing a dehydrated product using the catalyst of the present invention (particularly preferably, a catalyst for gas phase dehydration), activity (conversion rate, yield) and selectivity are compared with the case of using a conventional acidic oxide catalyst. Both exhibit excellent properties and suppress the decrease in activity and selectivity over time, which is economically advantageous in industrial implementation. Moreover, it is economically advantageous in industrial implementation in that acrolein can be obtained without being derived from petroleum. In particular, glycerin can also be obtained with high selectivity by gas phase dehydration reaction.
  • acrolein can be obtained in a high yield, whereby a high-concentration acrolein solution can be obtained directly, and further, there is little deterioration of the catalyst over time.
  • the form can be provided.
  • a catalyst suitable for acrolein production can be provided, and acrolein can be obtained using V and raw materials not derived from petroleum. Compared to the case of using a conventional catalyst, it shows excellent characteristics in both activity (conversion rate, yield) and selectivity, and suppresses the decrease in activity and selectivity over time, making it economical in industrial implementation. Is advantageous.
  • glycerin can also be obtained with high selectivity by gas phase dehydration reaction. In this case, even when a high-concentration glycerin solution is used, acrolein can be obtained in a high yield, whereby a high-concentration acrolein solution can be obtained directly, and the catalyst deterioration over time can be reduced. Less form can be provided.
  • acrylic acid can be produced by reacting acrolein obtained by the production method of the present invention with an acid reaction.
  • the present invention is also a method for producing acrylic acid by an industrially advantageous method starting from glycerin.
  • the catalyst dehydrated by heating was kept in dry benzene, the Hammett indicators of +6.8, -3.0, -8.2 were added in order, the maximum acid strength was measured, and then each indicator was added.
  • the dehydrated catalyst was added to dry benzene, and titration was performed with an n-butylamine benzene solution with a known concentration until the color disappeared, and the acid amount in each acid strength range was also measured.
  • the finished catalyst A has a Hammett acidity of ⁇ 8.2 ⁇ H and ⁇ 3, and 0.099m per lg of catalyst.
  • the Hammett acidity was measured by the same method.
  • the ⁇ -alumina powder was added and kneaded, dried in air at 110 ° C for 1 hour, and further dried in vacuum at 150 ° C for 4 hours. After lightly crushing, it was adjusted to 20-40 mesh (mesh) using a sieve.
  • the finished catalyst B has a Hammett acidity of ⁇ 8.2 ⁇ H and ⁇ 3 and 0.008 m per lg of catalyst.
  • the resulting catalyst C has a Met acidity of ⁇ 8.2 ⁇ H and ⁇ 3 and a catalyst of 0.007 m per lg.
  • a quartz reaction tube with an inner diameter of 10.4 mm was installed in an electrothermal annular furnace with a total length of 400 mm installed vertically and controlled at 315 ° C. Nitrogen was circulated at a standard state of 8.5 mlZ, and 0.63 ml of catalyst A was charged in the isothermal part obtained by measuring the temperature distribution in the reaction tube. Both ends of the catalyst layer were filled with 5 mm quartz wool and the top was filled with 30 mm quartz sand. A 36 mass% glycerin aqueous solution was introduced from the upper part of the reaction tube at a rate of 0.58 gZ time (hr).
  • the reaction was performed in the same manner as in Example 1 except that the catalyst C was used as the catalyst.
  • the conversion of glycerin was 70 mol%
  • the yield of acrolein was 41 mol%
  • the selectivity was 59 mol%.
  • the product gas collected 3 to 5 hours after the start of glycerin introduction and analyzed by gas chromatography showed that the conversion rate of glycerin was 88 mol%, the yield of acrolein was 51 mol%, and the selectivity Was 58 mol%, and both the activity and selectivity decreased with time. Further, 14 mol% of hydroxyacetone was produced.
  • Example 2 Comparative Examples 2 to 6
  • the reaction was conducted in the same manner as in Example 1 except that Catalyst B and Catalysts D and F to H were used as catalysts, and the produced gas was collected for 8 to 10 hours after the introduction of glycerin and analyzed by gas chromatography. . Since the yield of catalyst E was too low, the reaction was stopped in 4 hours, and the product gas was collected for 3 to 4 hours and analyzed by gas chromatography. The result was 3 ⁇ 4kl.
  • the reaction was conducted in the same manner as in Example 1 except that Catalyst I was used as a catalyst and a 36 mass% glycerin aqueous solution was used as a raw material at an introduction rate of 2.9 g Z time (hr).
  • the conversion rate of glycerin was 100 mol% and the selectivity of acrolein was 70 mol%.
  • the conversion rate of glycerin was 70 mol% and the selectivity of acrolein was 72 mol%.
  • a catalyst having a tungsten composition which is zircoure and a group 6 element, showed a conversion rate of 100 mol%, a selectivity of 63 mol%, and a yield of 63 mol% even after 10 hours, indicating that the activity and the selection were high. It showed excellent characteristics in terms of sex, and there was no decrease in activity or selectivity over time.
  • the selectivity after time was 70 mol%, and the selectivity with time was not decreased.
  • Other acid oxides SO / ZrO, B 2 O 3 / ZrO, Nb 2 O, H-type ZSM-5 (SiO 2 / Al
  • the conversion rate is 100 mol% and the selectivity is 38 mol%.
  • the conversion rate is 25 mol% and the selectivity is 53 mol%, and the selectivity of the catalyst containing the Group 6 element is high. It has been shown.
  • the fixed bed atmospheric pressure gas flow reactor used in the examples and comparative examples is mainly composed of a reactor having an inner diameter of 18 mm and a total length of 300 mm.
  • the reactor has a reaction gas collection vessel with a carrier gas inlet and a raw material inlet at the upper end and a gas outlet at the lower end.
  • the reactor has a vaporization layer between the raw material inlet and the reaction layer.
  • the crude reaction liquid collected in a collection container at 78 ° C was measured with gas chromatography (Shimadzu GC-8A, TC—WAX Kiri-Kiri Ichiram), and after calibration curve correction, The yield and the remaining amount of raw materials were determined, and the conversion rate (%; molar basis) and the selectivity (%; molar basis) were determined from these values.
  • the conversion rate is (the amount of raw material minus the remaining amount of raw material) the amount of Z raw material
  • the selectivity is the target product yield Z (the amount of raw material equal to the remaining amount of raw material).
  • the average value for the first 5 hours. A conversion of 100% means that the catalytic activity did not decrease during the reaction for 5 hours.
  • Dodecatungstokeic acid H SiW 2 O, purity 99.0% or more
  • 14 g of support consisting mainly of silica (Fujishirishi CARiACT Q-6 specific surface area 466 m 2 Zg) 6. 100 ml of Og
  • dodecamolybdophosphoric acid H PMo O purity 99.0% or more
  • the reaction was carried out in the same manner as in Example 6 except that the charge amount of the Q6-SiW-30 catalyst prepared in Example 5 was 0.3 g and the reaction temperature was changed.
  • the reaction temperature is 225 except 325 ° C. C, 250. C, 275. C, 300. C, and 350.
  • Table 3 shows the glycerin conversion, acrolein selectivity and hydroxyacetone selectivity depending on the reaction temperature.
  • the Q6—SiW-30 catalyst prepared in Example 5 above was packed into a fixed bed gas phase flow reactor.
  • the upper force of the fixed bed atmospheric pressure gas flow reactor with the catalyst layer Nitrogen gas was flowed at a flow rate of 1.8 lZh as the carrier gas.
  • glycerin manufactured by Wako Pure Chemical Co., Ltd., 10% by weight
  • 1.67 ml Zh was vaporized in the vaporization layer and supplied.
  • the reaction was performed at 275 ° C.
  • the catalyst loading was 0.6 g and 0.9 g in addition to 0.3 g.
  • Table 4 shows the glycerin conversion, acrolein selectivity, and hydroxyacetone selectivity according to the difference in catalyst loading.
  • CARIACT Q-3 (specific surface area of 733m 2 Zg) manufactured by Fujishiriya as the catalyst support silica Except that it was used, the same procedure as in Example 6 was carried out with 30% by weight of dodecatan dust key acid.
  • the catalyst was dried in a dryer at 110 ° C. to obtain a catalyst (B6—SiW-30) having a dodecatan dust key acid loading ratio of 30% by weight.
  • the reaction was carried out in the same manner as in Example 6 except that the amount of B6-SiW-30 catalyst prepared in Example 11 was changed to 0.3 g and the reaction temperature was changed. In addition to 325 ° C, the reaction temperatures were 225 ° C, 250 ° C, 275 ° C and 300 ° C. Table 7 shows the glycerin conversion, acrolein selectivity, and hydroxyacetone selectivity for different reaction temperatures.
  • Example 1 with the exception of using silica (B10) having a dual pore structure with a specific surface area of 698 m 2 Zg
  • the reaction was carried out with 30% by weight of dodecatan dust caustic acid (BIO—SiW-30).
  • the macropores and mesopores of the catalyst (BIO—SiW-30) used in Example 14 were 2 / zm in macropores and 10 nm in mesopores.
  • Catalyst (Type of support) (Element symbol of heteroelement ⁇ Element symbol of coordination element) (Catalyst loading (wt%))
  • TEOS tetraethoxysilane
  • Q3 means a CARiACT Q-3 (specific surface area of 733 m 2 Zg) carrier manufactured by Fujishirishia.
  • Q6 means a carrier (Fujishirishi CARiACT Q-6 specific surface area 466 m 2 / g).
  • Q10 means a CARiACT Q10 (specific surface area 310 m 2 Zg) carrier manufactured by Fujishirishia.
  • B3 means a silica (specific surface area 548 m 2 Zg) support having binary pores.
  • B6 means a silica (specific surface area 780 m 2 Zg) support having binary pores.
  • B10 means a silica (specific surface area 698 m 2 / g) support having binary pores.
  • B6-SiW-30 means a catalyst prepared as in Example 7 above.

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Abstract

La présente invention concerne un procédé de production de déshydrates par déshydratation en phase gazeuse, lequel est excellent en termes de rendement et de sélectivité et avantageux sur le plan économique dans la pratique industrielle et un catalyseur de déshydratation en phase gazeuse à utiliser dans le procédé. La présente invention concerne également, en tant que modes de réalisation préférables, un mode de réalisation dans lequel l’acroléine peut être obtenue à partir du glycérol par l’intermédiaire d’une déshydratation en phase gazeuse avec une sélectivité élevée, en particulier, un mode de réalisation dans lequel l’acroléine peut être produite avec un rendement élevé même lorsqu'une solution à concentration élevée en glycérol est utilisée de façon à obtenir directement de ce fait une solution à concentration élevée en acroléine, et un mode de réalisation dans lequel le catalyseur est peu détérioré même après un certain lapse de temps. La présente invention concerne en outre un nouveau catalyseur approprié pour produire l’acroléine à partir du glycérol ne provenant pas du pétrole et un procédé de production d’acroléine de manière efficace à partir d'un tel glycérol. La présente invention concerne un procédé de production de déshydrates par déshydratation en phase gazeuse d’un composé ayant trois ou plusieurs groupes hydroxyle comprenant l'étape de mise en contact du composé avec un catalyseur en phase gazeuse de déshydratation contenant au moins un élément du Groupe 6.
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JP2009057305A (ja) * 2007-08-30 2009-03-19 Nippon Shokubai Co Ltd グリセリンからのアクロレインの製造方法
WO2009136537A1 (fr) 2008-04-16 2009-11-12 日本化薬株式会社 Catalyseur pour produire de l'acroléine et de l'acide acrylique par déshydratation de glycérine et procédé de production de ce catalyseur
WO2009029536A3 (fr) * 2007-08-24 2009-12-10 Battelle Memorial Institute Processus de production chimique, systèmes et compositions de catalyseur
WO2010047405A1 (fr) 2008-10-24 2010-04-29 日本化薬株式会社 Catalyseur pour la fabrication d’acroléine et d’acide acrylique par une réaction de déshydratation de glycérine, et son procédé de fabrication
US7872158B2 (en) 2007-08-24 2011-01-18 Battelle Memorial Institute Chemical production processes, systems, and catalyst compositions
US7951978B2 (en) 2006-12-01 2011-05-31 Nippon Shokubai Co., Ltd. Process for producing acrolein and glycerin-containing composition
JP2011518111A (ja) * 2008-04-16 2011-06-23 アルケマ フランス グリセリンからアクロレインを製造する方法
WO2011083254A1 (fr) 2009-12-21 2011-07-14 Adisseo France S.A.S. Procede de preparation d'acroleine a partir de glycerol ou de glycerine
JP2011522015A (ja) * 2008-06-03 2011-07-28 アルケマ フランス グリセロールを脱水してアクロレインを製造する方法
WO2012005348A1 (fr) 2010-07-09 2012-01-12 日本化薬株式会社 Nouveau catalyseur de déshydratation du glycérol et procédé de production associé
WO2012010923A1 (fr) 2010-07-19 2012-01-26 Arkema France Procédé de fabrication d'acroléine à partir de glycérol
WO2012035540A1 (fr) 2010-09-16 2012-03-22 Ganapati Dadasaheb Yadav Procédé de production d'acroléïne et d'un catalyseur réutilisable
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
JP2012512236A (ja) * 2008-12-16 2012-05-31 アディッソ・フランス・エス．エー．エス． グリセロールまたはグリセリンからアクロレインを調製する方法
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
WO2013017904A1 (fr) * 2011-07-29 2013-02-07 Arkema France Procédé amélioré pour les réactions de déshydratation
WO2013018752A2 (fr) 2011-07-29 2013-02-07 日本化薬株式会社 Catalyseur pour la fabrication d'acroléine et de l'acide acrylique par la déshydratation de glycérine, et son procédé de fabrication
CN102989515A (zh) * 2012-12-17 2013-03-27 江南大学 一种二氧化钛/杂多酸复合光催化剂的制备方法
CN103242149A (zh) * 2013-05-15 2013-08-14 常州工学院 一种选择性制备丙烯醛和羟基丙酮的方法
US8530703B2 (en) 2009-12-18 2013-09-10 Battelle Memorial Institute Multihydric compound dehydration systems, catalyst compositions, and methods
EP2695672A2 (fr) 2009-09-18 2014-02-12 Nippon Kayaku Kabushiki Kaisha Production d'acroleine par deshydrogenation de glycerine en presence d'un catalyseur
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US7951978B2 (en) 2006-12-01 2011-05-31 Nippon Shokubai Co., Ltd. Process for producing acrolein and glycerin-containing composition
US7872158B2 (en) 2007-08-24 2011-01-18 Battelle Memorial Institute Chemical production processes, systems, and catalyst compositions
WO2009029536A3 (fr) * 2007-08-24 2009-12-10 Battelle Memorial Institute Processus de production chimique, systèmes et compositions de catalyseur
US7872159B2 (en) 2007-08-24 2011-01-18 Battelle Memorial Institute Chemical production processes, systems, and catalyst compositions
JP2009057305A (ja) * 2007-08-30 2009-03-19 Nippon Shokubai Co Ltd グリセリンからのアクロレインの製造方法
WO2009136537A1 (fr) 2008-04-16 2009-11-12 日本化薬株式会社 Catalyseur pour produire de l'acroléine et de l'acide acrylique par déshydratation de glycérine et procédé de production de ce catalyseur
JP2011518111A (ja) * 2008-04-16 2011-06-23 アルケマ フランス グリセリンからアクロレインを製造する方法
US8252960B2 (en) 2008-04-16 2012-08-28 Arkema France Process for manufacturing acrolein or acrylic acid from glycerin
JP5297450B2 (ja) * 2008-04-16 2013-09-25 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、その製造法
JP2011522015A (ja) * 2008-06-03 2011-07-28 アルケマ フランス グリセロールを脱水してアクロレインを製造する方法
WO2010047405A1 (fr) 2008-10-24 2010-04-29 日本化薬株式会社 Catalyseur pour la fabrication d’acroléine et d’acide acrylique par une réaction de déshydratation de glycérine, et son procédé de fabrication
US9447009B2 (en) 2008-12-16 2016-09-20 Adisseo France S.A.S. Method for preparing acrolein from glycerol or glycerine
JP2012512236A (ja) * 2008-12-16 2012-05-31 アディッソ・フランス・エス．エー．エス． グリセロールまたはグリセリンからアクロレインを調製する方法
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
US8530703B2 (en) 2009-12-18 2013-09-10 Battelle Memorial Institute Multihydric compound dehydration systems, catalyst compositions, and methods
US8907135B2 (en) 2009-12-18 2014-12-09 Battelle Memorial Institute Multihydric compound dehydration systems, catalyst compositions, and methods
WO2011083254A1 (fr) 2009-12-21 2011-07-14 Adisseo France S.A.S. Procede de preparation d'acroleine a partir de glycerol ou de glycerine
US8604234B2 (en) 2009-12-21 2013-12-10 Adisseo France S.A.S. Method for preparing acrolein from glycerol by catalytic dehydration of glycerol using a heteropolyacid catalyst
US9079841B2 (en) 2010-06-17 2015-07-14 Adisseo France S.A.S. Process for preparing acrolein from glycerol or glycerin
WO2012005348A1 (fr) 2010-07-09 2012-01-12 日本化薬株式会社 Nouveau catalyseur de déshydratation du glycérol et procédé de production associé
WO2012010923A1 (fr) 2010-07-19 2012-01-26 Arkema France Procédé de fabrication d'acroléine à partir de glycérol
WO2012035540A1 (fr) 2010-09-16 2012-03-22 Ganapati Dadasaheb Yadav Procédé de production d'acroléïne et d'un catalyseur réutilisable
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
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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CN102989515A (zh) * 2012-12-17 2013-03-27 江南大学 一种二氧化钛/杂多酸复合光催化剂的制备方法
CN103242149A (zh) * 2013-05-15 2013-08-14 常州工学院 一种选择性制备丙烯醛和羟基丙酮的方法
CN103242149B (zh) * 2013-05-15 2015-07-15 常州工学院 一种选择性制备丙烯醛和羟基丙酮的方法

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