WO2015037580A1 - ブタジエンの製造方法 - Google Patents
ブタジエンの製造方法 Download PDFInfo
- Publication number
- WO2015037580A1 WO2015037580A1 PCT/JP2014/073800 JP2014073800W WO2015037580A1 WO 2015037580 A1 WO2015037580 A1 WO 2015037580A1 JP 2014073800 W JP2014073800 W JP 2014073800W WO 2015037580 A1 WO2015037580 A1 WO 2015037580A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- alkali metal
- catalyst
- silica
- butanediol
- butadiene
- Prior art date
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 151
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 69
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 68
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims abstract description 64
- -1 alkali metal salt Chemical class 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 44
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 38
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 10
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 238000006297 dehydration reaction Methods 0.000 claims description 27
- 230000018044 dehydration Effects 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 4
- 238000010304 firing Methods 0.000 abstract description 8
- 239000000941 radioactive substance Substances 0.000 abstract description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 39
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 27
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- 239000000126 substance Substances 0.000 description 20
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- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical group [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 9
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- 239000012159 carrier gas Substances 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
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- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
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- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
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- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
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- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010907 stover Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- 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
- B01J27/18—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 with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/14—Phosphorus; Compounds thereof
- C07C2527/16—Phosphorus; Compounds thereof containing oxygen
- C07C2527/167—Phosphates or other compounds comprising the anion (PnO3n+1)(n+2)-
- C07C2527/173—Phosphoric acid or other acids with the formula Hn+2PnO3n+1
Definitions
- the present invention relates to a method for producing butadiene from 2,3-butanediol.
- Butadiene is a raw material for butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ABS resin, etc., and is one of the most important organic compounds in the chemical industry.
- Butadiene can be converted into adiponitrile, which is an intermediate for the synthesis of nylon 66, chloroprene, which is a raw material for chloroprene rubber, and 1,4-butanediol, which is a raw material for polybutylene terephthalate.
- adiponitrile which is an intermediate for the synthesis of nylon 66
- chloroprene which is a raw material for chloroprene rubber
- 1,4-butanediol which is a raw material for polybutylene terephthalate.
- These butadiene-based polymer compounds are widely used not only for industrial products such as automobile tires, electric wire coatings, and engineering plastics, but also for daily use such as clothing, and
- Butadiene is produced mainly by extraction and separation from the C4 fraction during ethylene production by naphtha crackers.
- 2,3-butanediol is a kind of polyol used as a raw material for inks, perfumes, liquid crystals, insecticides, softening reagents, explosives, plasticizers, etc., and industrially 2-butene oxide is dissolved in perchloric acid aqueous solution. It is manufactured by the method of hydrolyzing.
- 2,3-butanediol can be produced by a microbial fermentation method using monosaccharides such as glucose and xylose as raw materials (Patent Document 1), and is a substance that can be derived from biomass resources. Therefore, if butadiene can be produced by dehydration of 2,3-butanediol, butadiene, and further, existing synthetic resins using these as raw materials can be replaced with biomass resource-derived substances.
- 2,3-butanediol can be dehydrated using an acid catalyst.
- a method of dehydrating by contacting 2,3-butanediol with acid clay has been disclosed (Non-patent Document 1).
- a method for dehydrating by treating 2,3-butanediol in an aqueous sulfuric acid solution is disclosed (Non-patent Document 2).
- a method of dehydrating 2,3-butanediol by contacting with zeolite (Non-patent Document 3).
- the main product in these processes is methyl ethyl ketone rather than butadiene.
- Non-Patent Document 4 a method using a thorium oxide (ThO 2 ) catalyst, a method using a cesium oxide-supported silica catalyst in Patent Document 2, and a method using a composite catalyst of hydroxyapatite and alumina in Patent Document 3, respectively. It is disclosed.
- butadiene can also be produced by dehydration of 1,3-butanediol.
- sodium dihydrogen phosphate NaH 2 PO 4
- calcium monohydrogen phosphate CaHPO 4
- phosphoric acid H 3 PO 4
- butylamine phosphate BuNH 2 ⁇ H 3 PO 4
- Non-Patent Document 1 when 2,3-butanediol is dehydrated using an acid catalyst, the main product is methyl ethyl ketone and hardly produces butadiene.
- Non-Patent Document 2 methyl ethyl ketone is produced with a selectivity of 66 mol%, 96 mol%, or 90 mol% or more, respectively.
- Non-Patent Document 4 a method for selectively producing butadiene from 2,3-butanediol has been reported.
- selection of butadiene is performed.
- the rate is 62.1 mol%.
- thorium oxide is a radioactive substance and is difficult to use in industrial applications.
- butadiene can also be selectively produced by dehydration of 1,3-butanediol (Patent Document 4).
- 1,3-butanediol is easily dehydrated to give butadiene, but when 2,3-butanediol is dehydrated using acid clay, the selectivity of butadiene is It has been reported that the selectivity to methyl ethyl ketone is 66%, staying at 4%. That is, although 1,3-butanediol and 2,3-butanediol have similar chemical structures, the reactivity with respect to dehydration is greatly different. Under these conditions, dehydration of 2,3-butanediol involves methyl ethyl ketone. It is clearly shown that the selective production of butadiene is not easy due to the preferential progress of dehydration in the route of formation.
- An object of the present invention is to provide a method for producing butadiene with a high selectivity from 2,3-butanediol without using a radioactive substance.
- the present inventors have produced butadiene by dehydrating 2,3-butanediol in the presence of a catalyst in which an alkali metal salt of phosphoric acid is supported on silica.
- the present inventors have found a method to do this and have completed the present invention.
- the present invention provides a method for producing butadiene, which includes a step of dehydrating 2,3-butanediol in the presence of a catalyst in which an alkali metal salt of phosphoric acid is supported on silica.
- the alkali metal salt of phosphoric acid is an alkali metal dihydrogen phosphate.
- the alkali metal salt of phosphoric acid is an alkali metal dihydrogen phosphate
- the weight ratio of the alkali metal dihydrogen phosphate to the total weight of the silica and the alkali metal dihydrogen phosphate is phosphorous.
- a catalyst having a content of 5 wt% or more and 40 wt% or less before preparation for supporting the alkali metal dihydrogen acid on silica is used.
- the alkali metal of the alkali metal salt of phosphoric acid in the catalyst used is one or more selected from the group consisting of K, Rb, and Cs.
- the catalyst is prepared by calcining silica to which an alkali metal phosphate is attached in the step of supporting an alkali metal phosphate of silica on silica.
- the reaction temperature in the dehydration step of 2,3-butanediol is 380 ° C. or more and 520 ° C. or less.
- the sum of the contents of titanium and aluminum per unit surface area of the silica support is 750 ng / m 2 or less.
- the dehydration step for producing butadiene from 2,3-butanediol of the present invention can be described by the following reaction formula.
- butadiene can be produced from 2,3-butanediol with high selectivity without using a radioactive substance.
- the biomass resource means an organic resource derived from a renewable organism, and refers to a resource made of organic matter generated by fixing a carbon dioxide by a plant using solar energy.
- a renewable organism e.g., corn, sugarcane, potatoes, wheat, rice, soybeans, pulp, kenaf, rice straw, straw, bagasse, corn stover, switchgrass, weeds, waste paper, wood, charcoal, natural rubber, cotton, soybean oil , Palm oil, safflower oil, castor oil and the like.
- a biomass resource-derived substance means a substance derived from a biomass resource by fermentation, chemical conversion or the like, a substance that can be induced, or a derived substance.
- 2,3-butanediol derived from biomass resources and 2,3-butanediol derived from fossil resources such as petroleum can be used as raw materials.
- 2,3-butanediol has three optical isomers: (2R, 3R) -2,3-butanediol, (2S, 3S) -2,3-butanediol, and meso-2,3-butanediol.
- the 2,3-butanediol of the present invention may be any isomer or a mixture of a plurality of isomers.
- 2,3-butanediol derived from biomass resources can be produced by microbial fermentation of sugars obtained from biomass resources, as disclosed in Patent Document 1.
- microorganisms that ferment sugars as a carbon source Klebsiella pneumoniae, Klebsiella oxymora, and Paenibacillus polymyxa are naturally present and produce (2R, 3R) -2,3-butanediol and meso-2,3-butanediol. Can do.
- (2S, 3S) -2,3-butanediol is selectively produced in the genus Ochribactrum as shown in International Publication No. 2007/094178.
- Clostridium autoethanogenum is also known as a microorganism that ferments using carbon monoxide as a carbon source, and 2,3-butanediol produced from such a microorganism is also present. Can be the subject of the invention.
- a method using a microorganism imparted with 2,3-butanediol-producing ability by gene recombination may be used. Specific examples include “Applied Microbiology and Biotechnology, Vol. 87, No. 6, p. 2001-2009 ( 2010) ”.
- the carbon source of the fermentation raw material examples include sugars such as glucose, fructose, sucrose, xylose, arabinose, galactose, mannose, and starch.
- the saccharide may be a commercial product, but it may be a decomposed product such as recycled resources or biomass derived from plants, and a cellulose, hemicellulose, or lignin raw material decomposed by chemical or biological treatment is also used. be able to.
- carbon monoxide is a carbon source, which is obtained from incomplete combustion of coal, oil and biomass resources, as well as hydrogen and methane generated during the production of coke used for iron making It is also possible to use a mixed gas of
- 2,3-butanediol derived from fossil resources is available on the market and can be easily obtained.
- the catalyst used in the present invention will be described.
- the “alkali metal salt of phosphoric acid” means the following (A), (B) or (C).
- M represents an alkali metal, that is, Li (lithium), Na (sodium), K (potassium), Rb (rubidium) or Cs (cesium).
- N represents a positive real number of 3 or less. That is, the salt of “phosphoric acid” includes dihydrogen phosphate (H 2 PO 4 ⁇ ), monohydrogen phosphate (HPO 4 2 ⁇ ), and phosphate (PO 4 3 ⁇ ).
- the catalyst used in the present invention can be prepared by supporting an alkali metal salt of phosphoric acid on a carrier.
- the alkali metal salt of phosphoric acid can be supported by a general impregnation method described in, for example, “Catalyst Handbook (Kodansha Co., Ltd., issued on Dec. 10, 2008) pages 284 to 285”.
- the impregnation method includes an evaporation to dryness method or an equilibrium adsorption method. In the evaporation to dryness method, an impregnating liquid containing a supported component is impregnated with a carrier, the impregnating solution is removed by distillation, and then the catalyst is dried and / or calcined to immobilize the supported component on the carrier. Is the method.
- the equilibrium adsorption method is a method in which an impregnating liquid containing a supported component is impregnated with a carrier, the impregnating liquid is removed by filtration, and then the catalyst is dried and / or calcined to immobilize the supported component on the carrier.
- the supported component is an alkali metal salt of phosphoric acid
- the catalyst used in the present invention is impregnated with an aqueous solution containing an alkali metal salt of phosphoric acid to remove moisture, and then dried. And / or by baking.
- the impregnation liquid can be easily prepared by dissolving an alkali metal salt of phosphoric acid in water.
- an alkali metal salt of phosphoric acid ammonium dihydrogen phosphate ((NH 4 ) H 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) or the like is used as a phosphoric acid source.
- alkali metal source alkali metal nitrate (MNO 3 ), alkali metal carbonate (MCO 3 ), alkali metal hydrogen carbonate (MHCO 2 ), or the like can also be used.
- Unnecessary salts other than the alkali metal salt of phosphoric acid generated in this case can be liberated from the catalyst as nitrogen oxide gas or carbon oxide gas when the catalyst is calcined.
- the temperature at the time of impregnating the carrier is not particularly limited as long as it is 100 ° C. or less, but it is convenient and preferable to carry out at room temperature that does not require a device or operation for reducing or heating.
- the removal of the impregnating liquid can be performed by distillation or filtration.
- the silica impregnated with the alkali metal salt solution of phosphoric acid and adhered with the alkali metal of phosphoric acid as described above can be dried, for example, by circulating air at a temperature of about 80 to 100 ° C. it can. By drying under such temperature conditions, it is possible to prepare a catalyst in which the above-mentioned (A) or (B) non-dehydrated “alkali metal phosphate” or a mixture thereof is supported on silica.
- These firings can be performed at a firing temperature of 300 ° C. or higher and 600 ° C. or lower, preferably 450 ° C. or higher and 550 ° C. or lower.
- the atmosphere at the time of firing is not particularly limited as long as oxygen is contained, but it is easy to carry out under air circulation.
- a catalyst in which a dehydration condensate of an alkali metal phosphate mainly supported on silica is produced by firing in the step of supporting the alkali metal salt of phosphoric acid on silica is used. It is preferable.
- the catalyst used in the present invention can be appropriately formed into an arbitrary shape and used.
- the molding method is, for example, the extrusion molding method, compression molding method, rolling granulation method, spray drying granulation method described in “Catalyst Handbook (Kodansha Co., Ltd., issued December 10, 2008) pages 290 to 301”. Etc.
- a molding additive may be used.
- the organic component can be removed by firing in an air stream after molding of the catalyst.
- the firing temperature at this time is preferably 450 ° C. or higher and 600 ° C. or lower.
- the alkali metal salt of phosphoric acid supported on the carrier is preferably an alkali metal dihydrogen phosphate.
- one type selected from the group consisting of NaH 2 PO 4 , KH 2 PO 4 , RbH 2 PO 4 and CsH 2 PO 4 or a mixture of two or more types thereof can be preferably used.
- Carrier supporting the alkali metal salt of phosphoric acid if silica (SiO 2), the kind thereof is not particularly limited, can be produced with high selectivity to butadiene.
- silica examples include CARiACT [Q, G, P] (Fuji Silysia Chemical); N601, N602 (JGC Catalysts &Chemicals); Silica gel [40, 60, 100] (Merck); Silica gel [60, 60N] (Kanto) Chemistry); sunsphere [H, L], M.M. S.
- GEL [DF, DM, D], Sun Outdoor [C, TZ, LFS] (AGC S-Itech); Wakogel [C, DX, FC, G, LP, Q, S], Wakosil [C, 25SIL, 25C18, 40SIL] 40C18] (Wako Pure Chemical Industries); JRC-SIO-1, JRC-SIO-3, JRC-SIO-4, JRC-SIO-5, JRC-SIO-6, JRC-SIO-7, JRC-SIO- 8, JRC-SIO-9 (Catalyst Society Reference Catalyst); Leolosil [QS, MT, DM, KS, HM, PM] (Tokuyama); Mizukasil [P, SK] (Mizusawa Chemical Industry); Fumed silica, silica gel [ Grade 3, 12, 22, 40, 62, 922, 923], Silica, mesustructured [MSU-F, MCM-41, H S] (Sigma Aldrich); Davisil [Grade
- the silica may contain a metal such as titanium or aluminum.
- a metal such as titanium or aluminum.
- any generally available silica as described above can be used as it is.
- butadiene can be produced with high selectivity by using silica having a total content of titanium and aluminum per unit surface area of 1100 ng / m 2 or less as a support.
- the catalyst used in the method of the present invention preferably has a performance capable of maintaining a high butadiene selectivity for a long time in a gas phase flow reaction described later.
- silica having a small content of metal such as titanium or aluminum specifically, a silica having a total content of titanium and aluminum per unit surface area of the silica support of 750 ng / m 2 or less is used as the support. preferable.
- the carrier is magnesia (MgO), titania (TiO 2 ), alumina (Al 2 O 3 ), zirconia (ZrO 2 ) or the like instead of the silica of the present invention, sufficient butadiene selectivity can be obtained. I can't.
- the alkali metal salt of phosphoric acid supported on silica it is important to use the alkali metal salt of phosphoric acid supported on silica.
- an alkali metal salt of phosphoric acid not supported on silica is used as a catalyst, the conversion rate of 2,3-butanediol is reduced, and a large amount of 3-buten-2-ol is produced, and the selectivity of butadiene is reduced. (Refer to Comparative Example 5). Further, even when silica not supporting an alkali metal salt of phosphoric acid is used as a catalyst, sufficient butadiene selectivity cannot be obtained (see Comparative Example 6).
- the weight ratio of the alkali metal dihydrogen phosphate to the total weight of the silica and the alkali metal dihydrogen phosphate is preferably 5% by weight or more and 40% by weight or less. Furthermore, it is preferably 10% by weight or more and 40% by weight or less.
- the weight ratio of the alkali metal dihydrogen phosphate is the weight ratio before the alkali metal dihydrogen phosphate is supported on the silica.
- it is the weight ratio of the alkali metal dihydrogen phosphate to the total weight of the silica and the alkali metal dihydrogen phosphate when the impregnation liquid containing the alkali metal dihydrogen phosphate is impregnated with silica.
- the alkali metal contained in the catalyst used in the present invention is more preferably one or more selected from the group consisting of K, Rb and Cs.
- the selectivity of methyl ethyl ketone produced by dehydration of 2,3-butanediol tends to be low, and the selectivity of butadiene tends to be high.
- a catalyst in which one or more selected from the group consisting of KH 2 PO 4 , RbH 2 PO 4 and CsH 2 PO 4 is supported on silica is used.
- the amount of the above catalyst in which an alkali metal salt of phosphoric acid is supported on silica is not particularly limited and can be set as appropriate, but is usually 0.1 g or more per 1 g / hour of 2,3-butanediol supply rate. Preferably it is 0.3 g or more.
- the upper limit of the amount of the catalyst used is not particularly limited, but is usually 10 g or less per 1 g / hour of 2,3-butanediol supply rate from the viewpoint of cost.
- the dehydration step of 2,3-butanediol in the present invention can be performed by a gas phase flow reaction.
- the gas phase flow reaction is a reaction format in which a tubular reactor is filled with a solid catalyst and the vaporized raw material is allowed to flow through a catalyst layer for reaction.
- Specific examples include a fixed bed flow type in which the catalyst is allowed to stand, a moving bed flow type in which the catalyst is moved, and a fluidized bed flow type in which the catalyst is fluidized. Applicable.
- the vaporized raw material can be circulated through the catalyst layer together with the carrier gas.
- carrier gas Inert gas, such as nitrogen, helium, argon, or hydrogen, or these mixed gas is used preferably.
- the carrier gas may contain water vapor, air, oxygen and the like.
- the apparatus illustrated in FIG. 1 can be used as the fixed bed flow type reaction apparatus.
- the apparatus shown in FIG. 1 includes a reaction tube 1 having a raw material introduction port 4 and a carrier gas introduction port 3, a reaction crude liquid collection vessel (cooler) 5, and a tubular furnace 2. It can be fixed inside the tube 1.
- the tube 1 can heat the reaction tube 1 to a desired temperature.
- the gas phase flow reaction using the apparatus of FIG. 1 can be carried out by supplying a carrier gas and a raw material from the carrier gas inlet 3 and the raw material inlet 4 respectively and introducing them into the reaction tube 1.
- the condensing liquid compound can be collected in the reaction crude liquid collecting container 5, and the non-condensing gas component can be recovered from the gas outlet 7.
- the reaction temperature in the 2,3-butanediol dehydration step is preferably 380 ° C. or more and 520 ° C. or less. If the reaction temperature is less than the above range, a sufficient conversion of 2,3-butanediol may not be obtained. If the reaction temperature exceeds the above range, hydrocarbons having 1 to 4 carbon atoms are by-produced. However, there is a possibility that sufficient selectivity of the target product, butadiene, cannot be obtained.
- the weight hourly space velocity of the raw material gas supplied to the reactor is not particularly limited but is preferably 0.1 h -1 or 10h -1 or less, more preferably 0.5h -1 or more and 3h -1 or less.
- WHSV indicates the weight of 2,3-butanediol supplied per unit time per unit weight of the catalyst.
- the reaction pressure is not particularly limited, but is preferably 0.01 MPa or more and 0.5 MPa or less, and is preferably performed under an atmospheric pressure that does not require an apparatus or operation for pressure reduction or pressurization. Convenient.
- Patent Document 2 discloses a method for producing butadiene by a dehydration reaction of 2,3-butanediol.
- a cesium oxide-supported silica catalyst is used at a reaction temperature of 400 ° C. According to the inventors' further examination, it was found that the catalyst of this document has a low selectivity for butadiene (see Comparative Example 7).
- the method using a catalyst comprising an alkali metal salt of phosphoric acid and silica of the present invention butadiene can be produced with good selectivity.
- Butadiene generated in the dehydration process of 2,3-butanediol is a known technique, for example, Japanese Patent Publication No. 45-17407, Japanese Patent Publication No. 60-126235, Japanese Patent Publication No. 3-48891, and International Publication No. 2012/157495. It can be separated and purified by the method described in the above.
- Catalyst Preparation An example of a method for preparing silica carrying an alkali metal dihydrogen phosphate is shown.
- silica sica gel 60 (Merck), 70-230 mesh, BET specific surface area 500 m 2 / g, hereinafter referred to as “SiO 2 (A)”) .
- SiO 2 (A) BET specific surface area 500 m 2 / g
- the catalyst obtained here is hereinafter referred to as “10% NaH 2 PO 4 / SiO 2 (A)”.
- silica carrier instead of SiO 2 (A), SiO 2 (B) (CA RiACT Q-6 (Fuji Silysia Chemical), BET specific surface area 536 m 2 / g), SiO 2 (C) (CARPLEX BS303 (DSL) Japan), BET specific surface area 562 m 2 / g), SiO 2 (D) (MS GEL D70 120A (AGC S-Tech), BET specific surface area 450 m 2 / g), SiO 2 (E) (silica gel 60 (Kanto) Chemical), BET specific surface area 700 m 2 / g), SiO 2 (F) (Aerolyst 3041 (Evonik Industries AG), BET specific surface area 160 m 2 / g), SiO 2 (G) (Aerolyst 3045 (Evonik Industries AG), BET with a specific surface area of 160 m 2 / g), respectively, 10% CsH 2 PO 4 / SiO 2 (B) ","
- magnesia (MgO: Reference Catalyst JRC-MGO3), titania (TiO 2 : Wako Pure Chemical Industries), alumina (Al 2 O 3 : Reference Catalyst JRC-ALO-6), Zirconia (ZrO 2 : Reference Catalyst JRC-ZRO-3) is used in place of the above silica (SiO 2 (A), Merck, Silica Gel 60, 70-230 mesh), and “10% CsH 2 PO 4 / “MgO”, “10% CsH 2 PO 4 / TiO 2 ”, “10% CsH 2 PO 4 / Al 2 O 3 ”, “10% CsH 2 PO 4 / ZrO 2 ” were prepared.
- the dehydration reaction of 2,3-butanediol was carried out by using a quartz Y-shaped reaction tube 1 having an inner diameter of 15 mm and a total length of 350 mm shown in FIG. This was carried out using a fixed bed flow type reactor comprising a tubular furnace 2 (Asahi Rika Seisakusho ARF-20KC). A carrier gas inlet 3 and a raw material inlet 4 are provided in the upper part of the reaction tube, and a reaction crude liquid collecting container 5 having a gas outlet is connected under the reaction tube. The catalyst was filled in the central part of the reaction tube and fixed by sandwiching with quartz wool (6).
- the crude liquid recovered in the ice bathed collection container is diluted with methanol to 20 ml (same as in Examples 1 to 10 and Comparative Examples 1 to 7) or 10 ml (same as in Examples 11 to 17) and gas. Quantified by chromatographic measurement. In addition, gas products that did not aggregate in the ice bathed collection container were analyzed by gas chromatography directly connected to the gas outlet 7. The raw materials and products were quantified using an absolute calibration curve prepared using a standard. The conversion rate (mol%) of 2,3-butanediol and the selectivity (mol%) of each product were calculated by the following calculation formulas (Formula 1) and (Formula 2), respectively.
- the metal content per unit surface area of the silica support (ng / m 2 ) was calculated by dividing the metal impurity concentration determined by the above measurement by the BET specific surface area of silica. Table 2 shows the calculated values.
- Example 1 10% NaH 2 PO 4 / SiO 2 (A) (1.0 g) was charged into the reaction tube, and nitrogen was supplied from the top of the reaction tube at 30 ml / min. The temperature of the tubular furnace was raised to 500 ° C. and maintained at that temperature for 1 hour, and then 2,3-butanediol (Tokyo Kasei, meso-2,3-butanediol: 63%, (2R, 3R) -2, 3-butanediol: 29%, (2S, 3S) -2,3-butanediol: 8%) at 2 ml / h (WHSV: 1.97 h ⁇ 1 ) from the top of the reaction tube to the catalyst layer together with a nitrogen stream Supplied. The reaction was carried out for 5 hours, and the conversion of 2,3-butanediol and the selectivity of the product were calculated. The results are shown in Table 1.
- Example 2 The reaction was performed in the same manner as in Example 1 except that 10% KH 2 PO 4 / SiO 2 (A) was used as the catalyst. The results are shown in Table 1.
- Example 3 The reaction was performed in the same manner as in Example 1 except that 10% RbH 2 PO 4 / SiO 2 (A) was used as the catalyst. The results are shown in Table 1.
- Example 4 The reaction was performed in the same manner as in Example 1 except that 10% CsH 2 PO 4 / SiO 2 (A) was used as the catalyst. The results are shown in Table 1.
- Example 5 The reaction was carried out in the same manner as in Example 1 except that 5% CsH 2 PO 4 / SiO 2 (A) was used as the catalyst. The results are shown in Table 1.
- Example 6 The reaction was carried out in the same manner as in Example 1 except that 20% CsH 2 PO 4 / SiO 2 (A) was used as the catalyst. The results are shown in Table 1.
- Example 7 The reaction was performed in the same manner as in Example 1 except that 30% CsH 2 PO 4 / SiO 2 (A) was used as the catalyst. The results are shown in Table 1.
- Example 8 The reaction was carried out in the same manner as in Example 1 except that 40% CsH 2 PO 4 / SiO 2 (A) was used as the catalyst. The results are shown in Table 1.
- Example 9 The reaction was conducted in the same manner as in Example 4 except that the reaction temperature was 400 ° C. The results are shown in Table 1.
- Example 10 The reaction was carried out in the same manner as in Example 4 except that the reaction temperature was 450 ° C. The results are shown in Table 1.
- Comparative Example 1 The reaction was carried out in the same manner as in Example 1 except that 10% CsH 2 PO 4 / MgO was used as the catalyst. The results are shown in Table 1.
- Comparative Example 2 The reaction was carried out in the same manner as in Example 1 except that 10% CsH 2 PO 4 / TiO 2 was used as the catalyst. The results are shown in Table 1.
- Comparative Example 3 The reaction was performed in the same manner as in Example 1 except that 10% CsH 2 PO 4 / Al 2 O 3 was used as the catalyst. The results are shown in Table 1.
- Comparative Example 4 The reaction was carried out in the same manner as in Example 1 except that 10% CsH 2 PO 4 / ZrO 2 was used as the catalyst. The results are shown in Table 1.
- Comparative Example 5 White crystals (6.4 g) were obtained by heating CsH 2 PO 4 (Mitsuwa Chemical Industry: 6.9 g) at 500 ° C. using an electric furnace (Denken KDF-S70G) under air flow. The crystals were lightly crushed in a mortar to obtain a dehydrated condensate of CsH 2 PO 4 .
- the catalyst obtained here is expressed as CsH 2 PO 4 -500 (alkali metal salt of phosphoric acid as raw material—heating temperature (° C.)).
- Comparative Example 6 The reaction was performed in the same manner as in Example 1 except that SiO 2 (A) calcined at 500 ° C. under air flow was used as the catalyst. The results are shown in Table 1.
- Example 11 10% CsH 2 PO 4 / SiO 2 (A) (1.0 g) was charged into the reaction tube, and nitrogen was supplied from the top of the reaction tube at 30 ml / min. The temperature of the tubular furnace was raised to 405 ° C.
- Example 12 The reaction was performed in the same manner as in Example 11 except that 10% CsH 2 PO 4 / SiO 2 (B) was used as the catalyst. The results are shown in Table 2.
- Example 13 The reaction was performed in the same manner as in Example 11 except that 10% CsH 2 PO 4 / SiO 2 (C) was used as the catalyst. The results are shown in Table 2.
- Example 14 The reaction was performed in the same manner as in Example 11 except that 10% CsH 2 PO 4 / SiO 2 (D) was used as the catalyst. The results are shown in Table 2.
- Example 15 The reaction was performed in the same manner as in Example 11 except that 10% CsH 2 PO 4 / SiO 2 (E) was used as the catalyst. The results are shown in Table 2.
- Example 16 The reaction was performed in the same manner as in Example 11 except that 10% CsH 2 PO 4 / SiO 2 (F) was used as the catalyst. The results are shown in Table 2.
- Example 17 The reaction was performed in the same manner as in Example 11 except that 10% CsH 2 PO 4 / SiO 2 (G) was used as the catalyst. The results are shown in Table 2.
- Examples 4, 9, and 10 showed that the reaction temperature was 400 ° C. to 500 ° C., and butadiene could be produced with high selectivity.
- butadiene can be produced with a high selectivity in a catalyst using a silica support in which the sum of the contents of titanium and aluminum per unit surface area is 1100 ng / m 2 or less.
- butadiene can be produced with high selectivity from 2,3-butanediol, which can be derived from biomass resources, without using a radioactive substance.
- the raw material of butadiene can be replaced from fossil resources to biomass resources. Since butadiene is a raw material for industrial chemicals such as synthetic rubbers and plastics, the present invention is extremely useful industrially.
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Abstract
Description
(A):一般式(I)「MnH3-nPO4」で表される「リン酸アルカリ金属」(脱水縮合されていない単量体を意味する。)、
(B):(A)のアルカリ金属が異なる「リン酸アルカリ金属」の混合物、又は
(C):(A)又は(B)の全部若しくは一部のリン酸基が脱水縮合した「リン酸アルカリ金属の脱水縮合物」。
リン酸二水素アルカリ金属を担持したシリカの調製方法の1例を示す。
以下の実施例、比較例において、2,3-ブタンジオールの脱水反応は、図1に示す内径15mm、全長350mmの石英製Y字型反応管1とセラミックス電気管状炉2(アサヒ理化製作所ARF-20KC)からなる固定床流通式反応装置を用いて行った。反応管の上部には、キャリアガス導入口3と原料導入口4があり、反応管の下には、ガス抜け口を有する反応粗液捕集容器5がつながっている。触媒は反応管の中央部に充填し、石英ウールで挟み込み固定した(6)。氷浴した捕集容器内に回収した粗液は、メタノールで20ml(実施例1から10、比較例1から7で同じ。)または10ml(実施例11から17で同じ。)に希釈し、ガスクロマトグラフィ測定により定量した。また氷浴した捕集容器で凝集しないガス生成物はガス抜け口7に直結したガスクロマトグラフィにより分析した。原料、生成物の定量は標品を用いて作成した絶対検量線により行った。なお、2,3-ブタンジオールの転化率(モル%)および各生成物の選択率(モル%)は下記の計算式(式1)および(式2)によってそれぞれ算出した。
(式1) 転化率(モル%)=(原料の量-原料の残量)/原料の量×100
(式2) 選択率(モル%)=(生成物の収量)/(原料の量-原料の残量)×100。
硫酸存在下、フッ化水素酸を添加して分析対象のシリカ担体を溶解し、加熱することによりフッ化水素酸を除去してシリカを揮散させた後、希硝酸を添加した。この溶液について、原子吸光法及びICP発光分析法により、金属不純物濃度を定量した。なお、これらの分析には、原子吸光装置(島津製作所:AA-6200)及びICP発酵分析装置(パーキンエルマー:Optima 4300DV)を用いた。
10%NaH2PO4/SiO2(A)(1.0g)を反応管に充填し、反応管の上部から窒素を30ml/minで供給した。管状炉を500℃まで昇温し、該温度でそのまま1時間保持したのち、2,3-ブタンジオール(東京化成、meso-2,3-ブタンジオール:63%、(2R,3R)-2,3-ブタンジオール:29%、(2S,3S)-2,3-ブタンジオール:8%)を2ml/h(WHSV:1.97h-1)にて窒素気流と共に反応管の上部から触媒層に供給した。5時間反応を行い、2,3-ブタンジオールの転化率、生成物の選択率を算出した。結果を表1に示す。
触媒に10%KH2PO4/SiO2(A)を用いたことを除いては、実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に10%RbH2PO4/SiO2(A)を用いたことを除いては、実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に10%CsH2PO4/SiO2(A)を用いたことを除いては、実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に5%CsH2PO4/SiO2(A)を用いたことを除いては、実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に20%CsH2PO4/SiO2(A)を用いたことを除いては、実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に30%CsH2PO4/SiO2(A)を用いたことを除いては、実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に40%CsH2PO4/SiO2(A)を用いたことを除いては、実施例1と同様な方法で反応を行った。結果を表1に示す。
反応温度を400℃にしたことを除いては、実施例4と同様な方法で反応を行った。結果を表1に示す。
反応温度を450℃にしたことを除いては、実施例4と同様な方法で反応を行った。結果を表1に示す。
触媒に10%CsH2PO4/MgOを用いたことを除いては実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に10%CsH2PO4/TiO2を用いたことを除いては実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に10%CsH2PO4/Al2O3を用いたことを除いては実施例1と同様な方法で反応を行った。結果を表1に示す。
触媒に10%CsH2PO4/ZrO2を用いたことを除いては実施例1と同様な方法で反応を行った。結果を表1に示す。
CsH2PO4(三津和化学工業:6.9g)を空気流通下、電気炉(デンケンKDF-S70G)を用いて、500℃で加熱することにより白色結晶(6.4g)を得た。この結晶を乳鉢中で軽く砕くことによりCsH2PO4の脱水縮合物を得た。ここで得られた触媒を、CsH2PO4-500(原料のリン酸のアルカリ金属塩-加熱温度(℃))と表記する。
触媒に空気流通下500℃で焼成したSiO2(A)を用いたことを除いては実施例1と同様な方法で反応を行った。結果を表1に示す。
特許文献2にしたがいセシウム酸化物-シリカ複合体を調製した。Cs2CO3(4.65g:和光純薬)を水(50ml)に溶解させ、シリカゲル(Davisil(登録商標)、35-60mesh、シグマ-アルドリッチ、10g)を含浸させた。該溶液を撹拌しながら80℃で24時間加熱して水を蒸発させて乾燥し、生成した粉末を空気流通下、600℃で焼成し、セシウム酸化物-シリカ複合体(13.1g)を得た。
10%CsH2PO4/SiO2(A)(1.0g)を反応管に充填し、反応管の上部から窒素を30ml/minで供給した。管状炉を405℃まで昇温し、該温度でそのまま1時間保持したのち、2,3-ブタンジオール(東京化成、meso-2,3-ブタンジオール:63%、(2R,3R)-2,3-ブタンジオール:29%、(2S,3S)-2,3-ブタンジオール:8%)を1ml/h(WHSV:0.98h-1)にて窒素気流と共に反応管の上部から触媒層に供給した。2,3-ブタンジオール供給後1時間を反応開始時間(0時間)として、8時間反応を行い、0-1時間目及び7-8時間目のブタジエン選択率を算出した。また、選択率低下の指標として、ブタジエン選択率の変化を式3によって算出した。結果を表2に示す。
(式3) ブタジエン選択率の変化=(7-8時間目のブタジエン選択率)-(0-1時間目のブタジエン選択率)
触媒に10%CsH2PO4/SiO2(B)を用いたことを除いては実施例11と同様な方法で反応を行った。結果を表2に示す。
触媒に10%CsH2PO4/SiO2(C)を用いたことを除いては実施例11と同様な方法で反応を行った。結果を表2に示す。
触媒に10%CsH2PO4/SiO2(D)を用いたことを除いては実施例11と同様な方法で反応を行った。結果を表2に示す。
触媒に10%CsH2PO4/SiO2(E)を用いたことを除いては実施例11と同様な方法で反応を行った。結果を表2に示す。
触媒に10%CsH2PO4/SiO2(F)を用いたことを除いては実施例11と同様な方法で反応を行った。結果を表2に示す。
触媒に10%CsH2PO4/SiO2(G)を用いたことを除いては実施例11と同様な方法で反応を行った。結果を表2に示す。
2 電気管状炉
3 キャリアガス導入口
4 原料導入口
5 反応粗液捕集容器(冷却器)
6 触媒層
7 ガス抜け口
Claims (6)
- リン酸のアルカリ金属塩をシリカに担持した触媒の存在下、2,3-ブタンジオールを脱水する工程を含む、ブタジエンの製造方法。
- リン酸のアルカリ金属塩が、リン酸二水素アルカリ金属である、請求項1に記載の製造方法。
- 前記触媒におけるシリカ及びリン酸二水素アルカリ金属の合計重量に対するリン酸二水素アルカリ金属の重量比が、リン酸二水素アルカリ金属をシリカに担持する工程の前において5重量%以上40重量%以下である、請求項2に記載の製造方法。
- リン酸のアルカリ金属塩のアルカリ金属が、K、Rb及びCsからなる群より選ばれる1種又は2種以上である、請求項1~3のいずれか1項に記載の製造方法。
- 前記触媒が、リン酸のアルカリ金属塩をシリカに担持する工程において、リン酸のアルカリ金属を付着させたシリカを焼成して調製したものである、請求項1~4のいずれか1項に記載の製造方法。
- 2,3-ブタンジオールの脱水工程の反応温度が380℃以上520℃以下である、請求項1~5のいずれか1項に記載の製造方法。
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EP3045437A1 (en) | 2016-07-20 |
JPWO2015037580A1 (ja) | 2017-03-02 |
US20160229765A1 (en) | 2016-08-11 |
BR112016004986A8 (pt) | 2020-02-11 |
CN105452204B (zh) | 2018-09-28 |
TW201518255A (zh) | 2015-05-16 |
US9790140B2 (en) | 2017-10-17 |
EP3045437B1 (en) | 2018-04-18 |
MY177848A (en) | 2020-09-23 |
CN105452204A (zh) | 2016-03-30 |
TWI630190B (zh) | 2018-07-21 |
BR112016004986B1 (pt) | 2021-02-23 |
JP6229721B2 (ja) | 2017-11-15 |
EP3045437A4 (en) | 2017-04-19 |
SG11201601958WA (en) | 2016-04-28 |
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