WO2014196517A1 - オレフィンの製造方法、およびこれに用いられる脱水触媒 - Google Patents
オレフィンの製造方法、およびこれに用いられる脱水触媒 Download PDFInfo
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- WO2014196517A1 WO2014196517A1 PCT/JP2014/064708 JP2014064708W WO2014196517A1 WO 2014196517 A1 WO2014196517 A1 WO 2014196517A1 JP 2014064708 W JP2014064708 W JP 2014064708W WO 2014196517 A1 WO2014196517 A1 WO 2014196517A1
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- WIPO (PCT)
- Prior art keywords
- silica gel
- alcohol
- olefin
- general formula
- weight
- Prior art date
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- 238000006297 dehydration reaction Methods 0.000 title claims abstract description 99
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 53
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 38
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims description 83
- 230000018044 dehydration Effects 0.000 title claims description 61
- 238000006772 olefination reaction Methods 0.000 title 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 239000000741 silica gel Substances 0.000 claims abstract description 102
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 100
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 90
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 55
- -1 propylene Chemical class 0.000 claims abstract description 44
- 239000011148 porous material Substances 0.000 claims abstract description 36
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 230000000694 effects Effects 0.000 abstract description 12
- 208000005156 Dehydration Diseases 0.000 description 57
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 38
- 238000000034 method Methods 0.000 description 38
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000002994 raw material Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 16
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000002576 ketones Chemical class 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 4
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000006384 oligomerization reaction Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910002026 crystalline silica Inorganic materials 0.000 description 2
- 150000001908 cumenes Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 0 CC(*)(C(*)N)N Chemical compound CC(*)(C(*)N)N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ZRGUXTGDSGGHLR-UHFFFAOYSA-K aluminum;triperchlorate Chemical compound [Al+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZRGUXTGDSGGHLR-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UFRQQBZAYHXOKS-UHFFFAOYSA-N cumene;phenol Chemical compound OC1=CC=CC=C1.CC(C)C1=CC=CC=C1 UFRQQBZAYHXOKS-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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
- 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
- B01J21/04—Alumina
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J21/12—Silica and alumina
-
- 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
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07C2521/12—Silica and alumina
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a method for producing olefin with high efficiency by dehydration reaction of alcohol, and a dehydration catalyst used in this method.
- it relates to a method for producing propylene by intramolecular dehydration reaction of isopropyl alcohol, and a dehydration catalyst used in this method.
- a method for producing cumene by reacting benzene and propylene, a method for producing cumene hydroperoxide by oxidizing cumene, and a method for producing phenol and acetone by acid decomposition of cumene hydroperoxide are already known.
- a method combining these reactions is a phenol production method generally called a cumene method, and is currently the mainstream of the phenol production method.
- This cumene method is characterized by the fact that acetone is co-produced, and it is an advantage if you want acetone at the same time, but if the co-produced acetone exceeds its demand, the price difference from propylene, which is the raw material, is disadvantageous. May work in the wrong direction and worsen the economics of cumene phenol.
- a method has been proposed in which co-produced acetone is converted to propylene by various methods and reused as a raw material for the cumene method.
- Acetone is easily converted to isopropyl alcohol by hydrogenation, and propylene obtained by the dehydration reaction of isopropyl alcohol is further reacted with benzene to obtain cumene, that is, acetone is converted to propylene by a two-stage reaction, and cumene is obtained.
- Processes that are reused as raw materials for the law have been proposed (Patent Documents 1 and 2).
- LHSV liquid space velocity
- a phenomenon in which reaction activity and propylene selectivity rapidly deteriorate may occur.
- the development of dehydration reaction technology with higher productivity has been demanded by the industry.
- impurities may be produced as a by-product due to simultaneous occurrence of oligomerization reaction of produced propylene, which causes a problem in that the selectivity is lowered.
- An object of the present invention is to provide a dehydration catalyst in which a dehydration reaction of alcohol proceeds with high efficiency.
- An object is to provide a method for producing propylene with high activity and high selectivity.
- the present inventors have found that the above problems can be solved by using a dehydration catalyst satisfying specific properties, and have reached the present invention. That is, the gist of the present invention is as follows.
- R 1 is selected from an alkyl group having 1 to 5 carbon atoms
- R 2 is selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.
- the silica gel (A) has an average pore diameter of 20 to 50 nm, and The method for producing an olefin according to [1], wherein the supported amount of the aluminum compound is more than 1,000 ppm by weight and not more than 10,000 ppm by weight as an aluminum element.
- the alcohol represented by the general formula (I) is subjected to a dehydration reaction in the presence of the dehydration catalyst in the form of a hydrous alcohol, as described in [1] or [2] Production method.
- the chemically treated silica gel (X) is a silica gel obtained by bringing silica gel (A) into contact with a water-soluble aluminum compound and then baking it, [1] to [4] The manufacturing method of the olefin in any one.
- olefin can be produced with high efficiency, that is, with high alcohol conversion and high olefin selectivity even in a high LHSV region in the dehydration reaction of alcohol.
- the present invention dehydrates chemically treated silica gel (X) in which 1,000 to 1000 ppm by weight of an aluminum compound as an aluminum element is supported on silica gel (A) having an average pore diameter of 10 to 50 nm. It is a method for producing an olefin represented by the following general formula (II) from an alcohol represented by the following general formula (I), characterized by being used as a catalyst.
- this manufacturing method is Including a step of performing a dehydration reaction of an alcohol represented by the following general formula (I) in the presence of a dehydration catalyst composed of chemically treated silica gel (X),
- the chemically treated silica gel (X) is obtained by supporting an aluminum compound on silica gel (A) having an average pore diameter of 10 to 50 nm,
- the method for producing an olefin represented by the following general formula (II) in which the supported amount of the aluminum compound in the chemically treated silica gel (X) is in the range of 1,000 ppm to 10,000 ppm by weight as an aluminum element Can also be seen.
- R 1 is selected from an alkyl group having 1 to 5 carbon atoms
- R 2 is selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.
- “dehydration” is defined as a reaction in which hydrogen atoms and hydroxyl groups on adjacent carbon atoms in the same molecule are removed as water molecules, and the same applies to all terms prefixed or suffixed with this term. Defined as having meaning. In the present invention, “dehydration” may be referred to as “intramolecular dehydration”.
- the dehydration reaction of this alcohol is carried out using “chemically treated silica gel (X)” as a dehydration catalyst.
- the dehydration reaction of the alcohol represented by the following general formula (I) is specifically a mode in which a hydroxyl atom and a hydrogen atom at the adjacent position ( ⁇ position) of carbon bonded to the hydroxyl group are eliminated. Is carried out to give an olefin represented by the following general formula (II).
- R 1 is selected from an alkyl group having 1 to 5 carbon atoms
- R 2 is selected from a hydrogen atom and an alkyl group having 1 to 5 carbon atoms.
- examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, and n-amyl group. be able to.
- R 1 is preferably a methyl group and R 2 is preferably a hydrogen atom.
- a preferred example of the alcohol represented by the general formula (I) used in the present invention is an alcohol in which R 1 is a methyl group and R 2 is a hydrogen atom, that is, isopropyl alcohol. In this case, it is converted into the corresponding olefin represented by the general formula (II), that is, propylene, by the dehydration reaction of isopropyl alcohol.
- ⁇ Silica gel (X)> chemically treated silica gel (X) is used as a dehydration catalyst.
- the dehydration catalyst used in the present invention is a dehydration catalyst composed of “chemically treated silica gel (X)”.
- silica gel (X) is silica gel (A) having an average pore diameter of 10 to 50 nm, and aluminum compound is 1,000 to 10,000 ppm by weight, preferably 1,000 to 5,000 ppm by weight as an aluminum element. More preferably, it is a chemically treated silica gel loaded with 1,500 to 5,000 ppm by weight.
- the silica gel (X) used in the present invention is a silica gel (A) having an average pore diameter of 10 to 50 nm, and from the viewpoint of high activity and high selectivity, an aluminum compound is used as an aluminum element.
- the loading amount of the aluminum compound on the silica gel (A) is expressed in terms of aluminum element.
- the supported amount of the aluminum compound is represented not by the amount of the aluminum compound in the silica gel (X) but by the content of the aluminum element contained in the aluminum compound subjected to the support. And when it says "weight ppm" about an aluminum compound, the ratio of content of the aluminum element contained in the aluminum compound with which it was supported with respect to the weight of the whole silica gel (X) is said.
- Silica gel (A) Silica gel (A) having an average pore diameter of 10 to 50 nm is not particularly limited as long as it is generally used as an adsorbent.
- the average pore size is 10-50 nm, preferably more than 10 nm and less than 50 nm Can be mentioned.
- silica gel having an average pore diameter of 20 to 50 nm is preferable from the viewpoint of reducing oligomerized impurities, for example, silica gel having an average pore diameter of 30 to 50 nm is preferable.
- silica gel (A) used in the present invention silica gel having a specific surface area of 50 to 900 m 2 / g and a pore volume of 0.3 to 1.8 ml / g is preferable.
- Silica gel having a volume of 200 m 2 / g and a pore volume of 0.7 to 1.8 ml / g is more preferable.
- Such silica gel can be prepared by a known method [for example, Japanese Patent Application Laid-Open No. 9-30809 and Akasaki et al., Tosoh Research and Technical Report Vol. 45, 65-69 (2001)]. It can also be used.
- An example of such a commercial product is Cariact (CARiACT), which is a silica for a catalyst carrier manufactured by Fuji Silysia Co., Ltd., which is used in the following examples.
- the type of silica gel used as the silica gel (A) may be crystalline silica gel or amorphous silica gel.
- the acid strength of the resulting dehydration catalyst may become too strong.
- oligomerization of olefins such as propylene obtained by the dehydration reaction easily proceeds, and as a result, selectivity to olefins tends to decrease.
- the silica gel is preferably amorphous.
- the chemically treated silica gel (X) used as a dehydration catalyst used in the present invention is one in which the aluminum compound is supported on the silica gel (A) as described above as an aluminum element.
- the aluminum compound supported on the silica gel (A) contains aluminum as a constituent metal element.
- silica gel (A) itself may further contain an impurity-derived metal element contained in a very small amount in commercially available silica as another metal element.
- an impurity-derived metal element contained in a very small amount in commercially available silica as another metal element.
- Ca, Fe, Mg, Na, Ti, Zr may be included.
- the aluminum compound may be water-soluble, and examples thereof include aluminum nitrate, aluminum sulfate, aluminum phosphate, and aluminum perchlorate.
- “chemical treatment” is defined as bringing a raw material silica gel into contact with a water-soluble aluminum compound.
- the water-soluble aluminum compound is usually used as an aqueous solution containing an aluminum compound.
- the contact is usually performed by solid-liquid contact.
- the silica gel (X) according to the present invention is prepared by subjecting the silica gel (A) to a solid-liquid contact treatment with the aqueous solution.
- the aluminum compound may be the same as or different from the aluminum compound used for supporting.
- the silica gel (X) when the silica gel (X) is obtained by bringing the silica gel (A) into contact with the water-soluble aluminum compound and then baking it, in the course of baking or the like, a part of the water-soluble aluminum compound or The whole may be decomposed and changed to a second aluminum compound different from the water-soluble aluminum compound.
- the silica gel (X) may contain the said 2nd aluminum compound finally as an aluminum compound, in the manufacturing method of this invention, it does not interfere.
- the chemically treated silica gel (X) is a silica gel obtained by “chemical treatment” of the silica gel (A) with an aluminum compound, and more specifically, Silica gel obtained by bringing silica gel (A) into contact with a water-soluble aluminum compound and then baking is preferred.
- silica gel (X) for example, a method in which silica gel (A) is brought into contact with an aqueous solution of a water-soluble aluminum compound, and then water is distilled off, dried and fired, or water-soluble for the pore volume of silica gel. It is prepared by a known method in which an aqueous solution of an aluminum compound is impregnated in silica gel and dried and fired. More specifically, the former method uses aluminum nitrate as a water-soluble aluminum compound, contacts and mixes with the silica gel (A) in the form of a low-concentration aqueous solution, and then removes water under reduced pressure, at 120 ° C. This is a method of carrying out drying and baking at 500 ° C.
- the latter method is a method in which an aqueous solution of aluminum nitrate corresponding to the pore volume of silica gel (A) is mixed with silica gel (A) and impregnated in pores, and then 120 ° C.
- This is a method of performing lower drying and firing at 500 ° C.
- the latter method is preferably employed because the process is simplified to the extent that no water distillation operation is required. In the embodiments of the present invention, the latter method is adopted.
- baking at a high temperature of 500 ° C. is preferable because it often changes the surface state and leads to suppression of side reactions.
- the shape of the chemically treated silica gel (X) as the dehydration catalyst according to the present invention is not particularly limited, and may be any of a spherical shape, a cylindrical shape, an extruded shape, and a crushed shape, and the particle size is 0.01 mm to What is necessary is just to select suitably according to the magnitude
- the alcohol represented by the general formula (I) is subjected to a dehydration reaction in the presence of the dehydration catalyst in the form of pure alcohol or in the form of a crude alcohol containing impurities.
- the alcohol represented by the general formula (I) that can contain impurities in a form actually used for the dehydration reaction in the presence of the dehydration catalyst is referred to as “raw alcohol”.
- raw alcohol the alcohol represented by the general formula (I) that can contain impurities in a form actually used for the dehydration reaction in the presence of the dehydration catalyst.
- impurities that may be contained in such raw material alcohol unreacted raw materials used in the production of the alcohol represented by the general formula (I), and by-products in the production process of the alcohol represented by the general formula (I) By-products and the like.
- an alcohol containing water may be used as a “raw alcohol”.
- an alcohol containing such water is used as an alcohol. It may be called “hydrated alcohol” regardless of the presence or absence of other impurities such as unreacted raw materials and by-products.
- pure alcohol when the alcohol represented by the general formula (I) is referred to as “pure alcohol”, it refers to an alcohol composed only of the alcohol represented by the general formula (I).
- the reaction temperature is not particularly limited, but is preferably in the range of 50 to 500 ° C, more preferably 60 to 400 ° C.
- the preferred operating pressure range is 0.1 to 500 atmospheres, more preferably 0.5 to 100 atmospheres.
- the raw material alcohol used as a raw material for the dehydration reaction in the present invention will be described in a little more detail.
- the “raw alcohol” actually used for the dehydration reaction in the presence of the dehydration catalyst is not necessarily limited to the form of pure alcohol, and may contain impurities.
- an alcohol represented by the above general formula (I) obtained by hydrogenating a corresponding ketone may be used as a raw material alcohol.
- the production method of the present invention may be used.
- the corresponding unreacted ketone may be contained in the raw material alcohol used in the above.
- isopropyl alcohol is used as the alcohol represented by the general formula (I)
- isopropyl alcohol obtained by hydrogenating acetone may be used as the raw material alcohol.
- unreacted acetone may be contained.
- 0.01 to 1 part by weight of the corresponding ketone before hydrogenation of the alcohol is 1 part by weight of the alcohol represented by the general formula (I).
- the alcohol represented by the general formula (I) Even in the coexisting system, that is, when a mixture containing 1 part by weight of the alcohol represented by the above general formula (I) and 0.01 to 1 part by weight of the corresponding ketone is used as the raw alcohol.
- the raw alcohol used as a raw material for the dehydration reaction in the present invention may contain moisture. This is also true when an alcohol obtained by hydrogenating the corresponding ketone is used as the raw alcohol, for example, when isopropyl alcohol obtained by hydrogenating acetone is used as the raw alcohol.
- the dehydration reaction can proceed efficiently even if water is mixed in the reaction system, especially even if water is mixed in the raw alcohol. It is.
- the moisture concentration in the system typically the moisture concentration in the raw alcohol, is usually 1 to 10% by weight, preferably 1 to 8% by weight, more preferably 1 to 6% by weight. Even if water coexists in the raw material alcohol, when the produced olefin is a gas under normal pressure, such as propylene, water can be easily separated, so that no special load is imposed on the purification step after the reaction.
- the dehydration catalyst is converted into hydrated alcohol in the form of isopropyl alcohol. It can be used for dehydration reaction in the presence.
- the dehydration catalyst comprising the silica gel (X) can be used for producing propylene by a dehydration reaction of hydrous isopropyl alcohol.
- the method can be carried out in any of batch, semi-batch and continuous flow methods. It can be carried out in any form of a liquid phase, a gas phase, and a gas-liquid mixed phase.
- a catalyst filling method various methods such as a fixed bed, a fluidized bed, a suspension bed, and a shelf fixed bed are adopted, and any method may be used.
- the catalyst of the present invention that is, only the dehydration catalyst composed of the silica gel (X) may be filled, or a general-purpose catalyst may be used in part May be included.
- a general-purpose catalyst may be used in part May be included.
- the activity of the dehydration catalyst can be recovered by performing regeneration by a known method.
- a merry-go-round system in which two or three reactors are arranged in parallel and the remaining one or two reactors carry out the reaction while one reactor is being regenerated. You can take it.
- a method may be used in which the other two reactors are connected in series to reduce fluctuations in production.
- LHSV Liquid Space Velocity
- LHSV Liquid Space Velocity
- the application of the olefin production method according to the present invention described above is not particularly limited, but as a typical application destination, regeneration of propylene from acetone by-produced during the synthesis of phenol by the cumene method is possible. Can be mentioned.
- benzene and propylene are subjected to an addition reaction to form cumene, and this cumene is oxidized to cumene hydroperoxide, and further, this cumene hydroperoxide is decomposed to obtain phenol and acetone.
- the regeneration of propylene from acetone can be carried out by hydrogenating the acetone to lead to isopropyl alcohol, and further dehydrating the isopropyl alcohol. Can be reused for phenol synthesis.
- the above-described method for producing an olefin according to the present invention can be advantageously applied to the regeneration of propylene from isopropyl alcohol obtained by hydrogenation reaction of acetone. This is because even if the raw material alcohol used for the dehydration reaction of isopropyl alcohol includes acetone or the like, conversion from isopropyl alcohol to propylene can be performed efficiently.
- one of the applications of the present invention is a method of producing cumene using propylene obtained by the above-described olefin production method.
- cumene can be obtained by addition reaction of benzene and propylene by a conventional method such as Friedel-Crafts reaction.
- the cumene obtained in this way can be used as an intermediate raw material in phenol synthesis by the cumene method.
- An SUS316 reactor with an inner diameter of 1 cm was charged with 1 ml of a dehydration catalyst classified to 250 to 500 ⁇ m, pressurized to 2.0 MPa with nitrogen, and then isopropylated at 300 ° C. under a nitrogen stream of 10 ml / min from the reactor inlet side. Alcohol was distributed. The reaction was performed while introducing 200 ml / min of nitrogen by a high-pressure nitrogen mass flow between the reactor outlet and the back pressure valve.
- the raw material isopropyl alcohol was obtained by a hydrogenation reaction of acetone, and one containing 0.4% by weight of acetone and 4.7% by weight of water was used.
- the activity of the catalyst was evaluated by comprehensively comparing reaction results when LHSV was changed.
- Example 1 In a 50 ml beaker, 10.0 g of silica gel CARiACT (Q-10) manufactured by Fuji Silysia Chemical Co., Ltd. and 25 g of a 1.39 wt% aluminum nitrate aqueous solution were charged and allowed to stand at room temperature for 1 hour, and then an aluminum nitrate aqueous solution not impregnated with silica gel ( Approximately 15 g) was removed by filtration, dried at 120 ° C. for 3 hours, and calcined at 500 ° C. for 6 hours to obtain silica gel (X) carrying 1,000 ppm by weight of aluminum as a dehydration catalyst according to the present invention. . Table 1 shows the results of the dehydration catalyst performance of this catalyst according to the dehydration catalyst evaluation method.
- Example 2 In Example 1, Q-15 was used instead of silica gel Q-10, and the same procedure was performed except that 2.78 wt% aluminum nitrate aqueous solution was used instead of 1.39 wt% aluminum nitrate aqueous solution. Silica gel (X) carrying aluminum was obtained. Table 1 shows the results of the dehydration catalyst performance of this catalyst according to the dehydration catalyst evaluation method.
- Example 3 Example 2 was carried out in the same manner as in Example 2 except that Q-20 was used instead of silica gel Q-15 to obtain silica gel (X) supporting 2,000 ppm by weight of aluminum. Table 1 shows the results of the dehydration catalyst performance of this catalyst according to the dehydration catalyst evaluation method.
- Example 4 Example 2 was carried out in the same manner as in Example 2 except that Q-30 was used instead of silica gel Q-15 to obtain silica gel (X) carrying 2,000 ppm by weight of aluminum. Table 1 shows the results of the dehydration catalyst performance of this catalyst according to the dehydration catalyst evaluation method.
- Example 5 Example 2 was carried out in the same manner as in Example 2 except that Q-50 was used instead of silica gel Q-15 to obtain silica gel (X) carrying 2,000 ppm by weight of aluminum. Table 1 shows the results of the dehydration catalyst performance of this catalyst according to the dehydration catalyst evaluation method.
- Table 1 shows the results of the dehydration catalyst performance of ⁇ -alumina (N612N) manufactured by JGC Catalysts & Chemicals, Inc., which is industrially used as a dehydration catalyst for alcohol, according to the dehydration catalyst evaluation method.
- the numerical value following Q of CARiACT manufactured by Fuji Silysia Chemical Ltd. indicates the average pore diameter (nm) of silica gel, and the larger the value, the larger the pore diameter.
- Example 6 In Example 4, it carried out similarly except using 2.09 weight% aluminum nitrate aqueous solution instead of 2.78 weight% aluminum nitrate aqueous solution, and obtained silica gel (X) which carry
- Table 2 shows the results of the dehydration catalyst performance of this catalyst in accordance with the dehydration catalyst evaluation method.
- Example 7 In Example 5, it carried out similarly except using 4.17 weight% aluminum nitrate aqueous solution instead of 2.78 weight% aluminum nitrate aqueous solution, and obtained silica gel (X) which supported 3,000 weightppm aluminum. Table 2 shows the results of the dehydration catalyst performance of this catalyst in accordance with the dehydration catalyst evaluation method.
- Example 8 In Example 5, it carried out similarly except having used 6.95 weight% aluminum nitrate aqueous solution instead of 2.78 weight% aluminum nitrate aqueous solution, and obtained silica gel (X) which carry
- an optimal silica gel and an optimal aluminum loading can be selected according to operating conditions.
- an alcohol such as propylene has high efficiency and high selectivity even in a high LHSV region by an intramolecular dehydration reaction of an alcohol such as isopropyl alcohol.
- a method of manufacturing is provided.
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Abstract
Description
すなわち、本発明の骨子は以下の通りである。
〔2〕前記シリカゲル(A)の平均細孔径が20~50nmであり、且つ、
前記アルミニウム化合物の担持量が、アルミニウム元素として1,000重量ppmを超え、かつ10,000重量ppm以下である
〔1〕に記載のオレフィンの製造方法。
〔4〕前記含水アルコール中の、水の含有量が1~10重量%であることを特徴とする〔3〕に記載の製造方法。
〔5〕前記化学処理されたシリカゲル(X)が、シリカゲル(A)と水溶性アルミニウム化合物とを接触し、次いで焼成して得られるシリカゲルであることを特徴とする〔1〕~〔4〕のいずれかに記載のオレフィンの製造方法。
〔8〕平均細孔径が20~50nmであるシリカゲル(A)にアルミニウム化合物がアルミニウム元素として1,000重量ppmを超えて10,000重量ppm以下が担持された、化学処理されたシリカゲル(X)からなり、
含水イソプロピルアルコールの脱水反応によるプロピレン製造に用いられることを特徴とするプロピレン製造用脱水触媒。
[オレフィンの製造方法]
本発明は、平均細孔径が10~50nmであるシリカゲル(A)にアルミニウム化合物がアルミニウム元素として1,000重量ppm~10,000重量ppmが担持された、化学処理されたシリカゲル(X)を脱水触媒として用いることを特徴とする、下記一般式(I)で表されるアルコールから下記一般式(II)で表されるオレフィンを製造する方法である。言い換えると、この製造方法は、
化学処理されたシリカゲル(X)からなる脱水触媒の存在下で、下記一般式(I)で表されるアルコールの脱水反応を行う工程を含み、
前記化学処理されたシリカゲル(X)が、平均細孔径が10~50nmであるシリカゲル(A)にアルミニウム化合物が担持されてなるものであり、
前記化学処理されたシリカゲル(X)における前記アルミニウム化合物の担持量が、アルミニウム元素として1,000重量ppm~10,000重量ppmの範囲にある
下記一般式(II)で表されるオレフィンの製造方法と見ることもできる。
なお本発明における「脱水」とは、同一分子における互いに隣接する炭素原子上の水素原子と水酸基が水分子として取り除かれる反応として定義され、この用語を接頭または接尾にもつ全ての用語についても同様な意味を持つものとして定義される。なお、本発明では「脱水」を「分子内脱水」と呼称する場合もある。
本発明に係るオレフィンの製造方法では、『化学処理されたシリカゲル(X)』を脱水触媒として用いて、このアルコールの脱水反応を行う。ここで、下記一般式(I)で表されるアルコールの脱水反応は、具体的には、水酸基と、当該水酸基に結合する炭素の隣接位(β位)にある水素原子が脱離する態様で行われ、下記一般式(II)で表されるオレフィンを与えるのである。
ここで、炭素数1~5のアルキル基としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、s-ブチル基、t-ブチル基、n-アミル基を例示することができる。後述するように、クメン法において併産されるアセトンの水添反応によって得られるイソプロピルアルコールの脱水によってクメン法原料であるプロピレンを再生産できるプロセスに直ちに適用できるという視点からは、上記一般式(I)及び(II)においてR1がメチル基でありR2が水素原子であることが好ましい。言い換えると、本発明で用いられる一般式(I)で表されるアルコールの好適な例として、R1がメチル基でありR2が水素原子であるアルコール、すなわちイソプロピルアルコールが挙げられる。この場合、イソプロピルアルコールの脱水反応により、対応する一般式(II)で表されるオレフィン、すなわち、プロピレンに変換されることになる。
本発明に係るオレフィンの製造方法においては、脱水触媒として、化学処理されたシリカゲル(X)が用いられる。別の見方をすると、本発明で用いられる脱水触媒は、「化学処理されたシリカゲル(X)」からなる脱水触媒であるともいえる。
平均細孔径が10~50nmであるシリカゲル(A)としては、吸着剤として一般的に用いられているものであれば特に限定されるものではなく、例えば、実験化学講座9,無機化合物の合成と精製(昭和33年12月20日発行,丸善株式会社)513ページに記載された6つの方法で製造された全てのシリカゲルのうち、平均細孔径が10~50nm、好ましくは、10nmを越え50nm以下のものを挙げることができる。ただ、このようなシリカゲル(A)として、オリゴメリ化した不純物を低減する観点から、平均細孔径20~50nmであるシリカゲルが好ましく、例えば、平均細孔径30~50nmであるシリカゲルが好ましい。また、本発明で用いられるシリカゲル(A)として、比表面積が50~900m2/gであり、且つ細孔容積が0.3~1.8ml/gであるシリカゲルが好ましく、中でも比表面積50~200m2/gであり、且つ細孔容積0.7~1.8ml/gであるシリカゲルがより好ましい。平均細孔径を適正なサイズにすることで、細孔活性点での生成オレフィンの拡散が容易となり、これにより細孔活性点にて不純物となるオリゴマーの副生を抑制できるものと推測する。このようなシリカゲルは公知の方法によって調製することもできるが〔例えば、特開平9-30809号公報、および赤崎ら,東ソー研究・技術報告 第45巻,65-69(2001)〕、市販品を用いることもできる。このような市販品としては後掲する本実施例において用いた、富士シリシア株式会社製の触媒担体用シリカであるキャリアクト(CARiACT)を例示することができる。
本発明で用いられる脱水触媒として用いられる化学処理されたシリカゲル(X)は、上記のようなシリカゲル(A)に、アルミニウム化合物がアルミニウム元素として上述した割合で担持されたものである。
本発明において、「化学処理」とは、原料シリカゲルと水溶性アルミニウム化合物とを接触させることとして定義される。ここで、前記水溶性アルミニウム化合物は、通常はアルミニウム化合物含有水溶液として用いられる。また、前記接触は通常固液接触により行われる。具体的には本発明に係わるシリカゲル(X)は、シリカゲル(A)を前記水溶液と固液接触処理することによって調製される。
本発明において、化学処理されたシリカゲル(X)は、上記シリカゲル(A)をアルミニウム化合物により「化学処理」して得られるシリカゲルであり、より具体的には、上記シリカゲル(A)と水溶性アルミニウム化合物とを接触し、次いで焼成して得られるシリカゲルであることが好ましい。
本発明に係るオレフィンの製造方法では、上記脱水触媒の存在下で、上記一般式(I)で表されるアルコールの脱水反応が行われる。
上述したように、上記脱水触媒の存在下での脱水反応に実際に供される「原料アルコール」は、必ずしも、純アルコールの形のものに限られず、不純物を含む場合もある。本発明における典型的な態様においては、原料アルコールとして、対応するケトンを水添して得られる上記一般式(I)で表されるアルコールが用いられることがあり、この場合、本発明の製造方法に用いられる原料アルコール中に、上記一般式(I)で表されるアルコールのほか未反応の当該対応するケトンが含まれることがある。例えば、上記一般式(I)で表されるアルコールとしてイソプロピルアルコールが用いられる場合、原料アルコールとしてアセトンを水添して得られるイソプロピルアルコールが用いられることがあり、このとき、原料アルコールには、イソプロピルアルコールのほかに、未反応のアセトンなどが含まれることがある。
発明を実施するに際して、その方法はバッチ式、セミバッチ式、または連続流通式のいずれの方法においても実施することが可能である。液相、気相、気-液混合相の、いずれの形態においても実施することが可能である。触媒の充填方式としては、固定床、流動床、懸濁床、棚段固定床等種々の方式が採用され、いずれの方式で実施しても差し支えない。
オレフィンの生産量を維持するために、反応器を2つまたは3つ並列に並べ、一つの反応器が再生している間に、残った1つまたは2つの反応器で反応を実施するメリーゴーランド方式をとっても構わない。さらに反応器が3つある場合、他の反応器2つを直列につなぎ、生産量の変動を少なくする方法をとっても良い。また流動床流通反応方式や移動床反応方式で実施する場合には、反応器から連続的または断続的に、一部またはすべての触媒を抜き出し、相当する分を補充することにより一定の活性を維持することが可能である。
上述した本発明に係るオレフィンの製造方法の応用については、特に限定されるわけではないが、典型的な応用先として、クメン法によるフェノール合成の際に副生するアセトンからの、プロピレンの再生が挙げられる。
〔実施例で用いた脱水触媒〕
シリカゲル(X)の原料となるシリカゲル、すなわち、シリカゲル(A)として、富士シリシア化学社から販売されている次のシリカを使用した。なお各性状値はカタログ記載値である。
・CARiACT Q-15;平均細孔径15nm、細孔容積1.0ml/g、比表面積200m2/g
・CARiACT Q-20;平均細孔径20nm、細孔容積1.0ml/g、比表面積150m2/g
・CARiACT Q-30;平均細孔径30nm、細孔容積1.0ml/g、比表面積100m2/g
・CARiACT Q-50;平均細孔径50nm、細孔容積1.0ml/g、比表面積80m2/g
〔脱水触媒の評価方法〕
(1)アルミニウムの担持量
下記実施例で得られたシリカゲル(X)中のアルミニウムの担持量は、各シリカゲル(X)を誘導結合プラズマ(ICP)分析によって金属分析することによって求めた。
脱水触媒によるイソプロピルアルコール(以下の説明では、IPAと略称する場合がある)の脱水反応性能を評価するため、高圧用フィードポンプ、高圧用窒素マスフロー、電気炉、触媒充填部分を有する反応器、背圧弁を設置した固定床反応装置を用い、ダウンフローによる加圧気相流通反応を行った。
50mlビーカーに、富士シリシア化学社製シリカゲルCARiACT(Q-10)10.0gと1.39重量%硝酸アルミニウム水溶液25gを仕込み室温で1時間静置した後、シリカゲルに含浸されなかった硝酸アルミニウム水溶液(およそ15g)はろ過操作により除去し、120℃で3時間乾燥、500℃で6時間焼成を行い本発明に係る脱水触媒としての1,000重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表1に示す。
実施例1において、シリカゲルQ-10の代わりにQ-15を用い、1.39重量%硝酸アルミニウム水溶液の代わりに2.78重量%硝酸アルミニウム水溶液を用いる以外同様に行い、2,000重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表1に示す。
実施例2において、シリカゲルQ-15の代わりにQ-20を用いる以外実施例2と同様に行い、2,000重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表1に示す。
実施例2において、シリカゲルQ-15の代わりにQ-30を用いる以外実施例2と同様に行い、2,000重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表1に示す。
実施例2において、シリカゲルQ-15の代わりにQ-50を用いる以外実施例2と同様に行い、2,000重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表1に示す。
アルコールの脱水触媒として工業的に使用されている、日揮触媒化成(株)製γ-アルミナ(N612N)の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表1に示す。
実施例4において、2.78重量%硝酸アルミニウム水溶液の代わりに2.09重量%硝酸アルミニウム水溶液を用いる以外同様に行い、1,500重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表2に示す。
実施例5において、2.78重量%硝酸アルミニウム水溶液の代わりに4.17重量%硝酸アルミニウム水溶液を用いる以外同様に行い、3,000重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表2に示す。
実施例5において、2.78重量%硝酸アルミニウム水溶液の代わりに6.95重量%硝酸アルミニウム水溶液を用いる以外同様に行い、5,000重量ppmのアルミニウムを担持したシリカゲル(X)を得た。本触媒の脱水触媒性能を脱水触媒評価方法に順じて行った結果を表2に示す。
本触媒系では、運転条件に応じて、最適なシリカゲルと最適なアルミニウム担持量を選択することができる。
Claims (8)
- 前記シリカゲル(A)の平均細孔径が20~50nmであり、且つ、
前記アルミニウム化合物の担持量が、アルミニウム元素として1,000重量ppmを超え、かつ10,000重量ppm以下である
請求項1に記載のオレフィンの製造方法。 - 前記一般式(I)で表されるアルコールが、含水アルコールの形で、前記脱水触媒存在下での脱水反応に供されることを特徴とする請求項1または2に記載の製造方法。
- 前記含水アルコール中の、水の含有量が1~10重量%であることを特徴とする請求項3に記載の製造方法。
- 前記化学処理されたシリカゲル(X)が、シリカゲル(A)と水溶性アルミニウム化合物とを接触し、次いで焼成して得られるシリカゲルであることを特徴とする請求項1~4のいずれか1項に記載のオレフィンの製造方法。
- 前記一般式(I)で表されるアルコールがイソプロピルアルコールであり、前記一般式(II)で表されるオレフィンがプロピレンであることを特徴とする請求項1~5のいずれか1項に記載のオレフィンの製造方法。
- 脱水反応温度が、50~500℃であることを特徴とする請求項1~6のいずれか1項に記載のオレフィンの製造方法。
- 平均細孔径が20~50nmであるシリカゲル(A)にアルミニウム化合物がアルミニウム元素として1,000重量ppmを超えて10,000重量ppm以下が担持された、化学処理されたシリカゲル(X)からなり、
含水イソプロピルアルコールの脱水反応によるプロピレン製造に用いられることを特徴とするプロピレン製造に用いられる脱水触媒。
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JPH0341035A (ja) * | 1989-07-10 | 1991-02-21 | Mitsui Toatsu Chem Inc | プロピレンの製造方法 |
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