CN114728272A - Catalyst, method for producing same, and method for producing unsaturated hydrocarbon - Google Patents
Catalyst, method for producing same, and method for producing unsaturated hydrocarbon Download PDFInfo
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- CN114728272A CN114728272A CN202080079057.9A CN202080079057A CN114728272A CN 114728272 A CN114728272 A CN 114728272A CN 202080079057 A CN202080079057 A CN 202080079057A CN 114728272 A CN114728272 A CN 114728272A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 55
- 229930195735 unsaturated hydrocarbon Natural products 0.000 title claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 148
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 148
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 85
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 55
- 150000003624 transition metals Chemical class 0.000 claims abstract description 55
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 23
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 19
- 239000012018 catalyst precursor Substances 0.000 claims description 58
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000001282 iso-butane Substances 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
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- 239000007787 solid Substances 0.000 claims description 10
- 150000003623 transition metal compounds Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
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- 230000008569 process Effects 0.000 claims description 6
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- 239000007789 gas Substances 0.000 description 53
- 238000006243 chemical reaction Methods 0.000 description 50
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- 150000001336 alkenes Chemical class 0.000 description 12
- 239000012495 reaction gas Substances 0.000 description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
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- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 239000002923 metal particle Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
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- 229910018106 Ni—C Inorganic materials 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
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- 239000001307 helium Substances 0.000 description 6
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910000314 transition metal oxide Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
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- 239000001294 propane Substances 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- GFJUOMJGSXRJJY-UHFFFAOYSA-N 2-methylprop-1-ene Chemical compound CC(C)=C.CC(C)=C GFJUOMJGSXRJJY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 2
- 229910017541 Cu-K Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
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- 239000000945 filler Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 230000003100 immobilizing effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
Classifications
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- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/58—
-
- 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
-
- 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
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C11/00—Aliphatic unsaturated hydrocarbons
- C07C11/02—Alkenes
- C07C11/08—Alkenes with four carbon atoms
- C07C11/09—Isobutene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/42—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with a hydrogen acceptor
Abstract
The present invention provides a catalyst capable of producing an unsaturated hydrocarbon with high selectivity in dehydrogenation of an alkane, a method for producing the same, and a method for producing an unsaturated hydrocarbon. The catalyst is characterized in that a transition metal and carbon are supported on a carrier, and the carbon contains fibrous carbon. The catalyst is brought into contact with a mixed gas containing an alkane and carbon dioxide to produce an unsaturated hydrocarbon from the alkane.
Description
Technical Field
The present invention relates to a catalyst and a method for producing the same, and a method for producing unsaturated hydrocarbons.
Background
Generally, a method for producing an olefin by dehydrogenating an alkane is known, and various catalysts used for the dehydrogenation have been studied.
For example, patent document 1 describes a dehydrogenation catalyst in which nickel and tin are supported on a composite carrier in which a specific amount of zinc oxide is supported on a specific γ -alumina carrier. Further, an example of producing isobutene (isobutene) by dehydrogenating isobutane by using the dehydrogenation catalyst is described.
Patent document 2 describes a catalyst obtained by supporting zinc and a metal of group VIIIA of the periodic table on a specific zeolite support. Also described is a process for producing an unsaturated hydrocarbon by dehydrogenating a hydrocarbon in the presence of the catalyst. Examples of producing butenes (1-butene, 2-butene, isobutene) by dehydrogenating n-butane using the catalyst are described as examples.
Further, patent document 3 describes a method for producing an oxidative dehydrogenation catalyst, which includes the steps of: a step (a) of dispersing a silicate in water, a step (b) of adding a chromium element, a step (c) of adding a surfactant after the step (a) or the step (b) and performing a heat treatment at a temperature of 50 to 150 ℃ for 1 to 20 hours, and a step (d) of performing a heat treatment at a temperature of 200 to 700 ℃ for 1 to 10 hours. Also disclosed is a method for producing an olefin from an alkane by bringing the obtained catalyst into contact with a mixed gas containing an alkane and oxygen at a specific mixing ratio. Examples of the production of isobutene (isobutene) from isobutane by using this catalyst are described as examples.
Patent document 4 describes that a catalyst in which a transition metal is supported on a carrier is pretreated in a hydrocarbon conversion step, but since the pretreatment is carried out for a short period of time, 30 minutes to 90 minutes, the aggregation of the transition metal cannot be suppressed, and a high selectivity cannot be achieved.
Documents of the prior art
Patent document
Patent document 1 Japanese patent application laid-open No. 9-75732
Patent document 2 Japanese patent laid-open publication No. 2013-163647
Patent document 3 Japanese patent laid-open No. 2014-140827
Patent document 4 Japanese patent publication No. 2018-520858
Disclosure of Invention
In a method for producing an unsaturated hydrocarbon by dehydrogenation of an alkane, high productivity is expected, and therefore, it is required to obtain an unsaturated hydrocarbon with a higher selectivity.
Accordingly, an object of the present invention is to solve the above-described problems, and to provide a catalyst capable of producing an unsaturated hydrocarbon with high selectivity in dehydrogenation of an alkane, a method for producing the same, and a method for producing an unsaturated hydrocarbon.
According to one embodiment of the present invention, there is provided a catalyst wherein a transition metal and carbon are supported on a carrier, and the carbon contains fibrous carbon.
According to another aspect of the present invention, there is provided a method for producing a catalyst, including the steps of:
a step of mixing a solution containing a transition metal compound with a carrier, heating the mixture to remove the solvent and obtain a catalyst precursor,
a step of bringing a carbon-containing gas into contact with the catalyst precursor to form a catalyst on which a transition metal and carbon are supported,
in the step of forming the catalyst, a carbon-containing gas is brought into contact with the catalyst precursor to form and support fibrous carbon.
According to another aspect of the present invention, there is provided a method for producing an unsaturated hydrocarbon from an alkane by bringing the catalyst into contact with a mixed gas containing the alkane and carbon dioxide.
According to another aspect of the present invention, there is provided a method for producing unsaturated hydrocarbons, wherein a catalyst is produced by the above-described method for producing a catalyst, and then a mixed gas containing an alkane and carbon dioxide is brought into contact with the obtained catalyst, thereby producing unsaturated hydrocarbons from the alkane.
According to another aspect of the present invention, there is provided a method for producing unsaturated hydrocarbons, comprising the steps of:
a step of bringing a carbon-containing gas into contact with a catalyst precursor in which a transition metal compound is supported on a carrier to thereby support carbon containing fibrous carbon on the catalyst precursor and form a catalyst in which a transition metal and carbon are supported,
the mixed gas containing alkane and carbon dioxide is brought into contact with the obtained catalyst, and unsaturated hydrocarbons are produced from the alkane.
According to the present invention, a catalyst capable of producing an unsaturated hydrocarbon with high selectivity in dehydrogenation of an alkane, a method for producing the same, and a method for producing an unsaturated hydrocarbon can be provided.
Drawings
Fig. 1 is an SEM image of the catalyst of example 2 of the present invention.
Fig. 2 is an SEM image showing grid-like dividing lines on the SEM image of fig. 1.
Detailed Description
The catalyst and the method for producing the same according to the embodiment of the present invention, and the method for producing an unsaturated hydrocarbon (preferably an olefin) from an alkane will be described in detail below.
(catalyst)
The catalyst according to the embodiment of the present invention is a catalyst in which carbon is supported on a carrier on which a transition metal is supported.
The catalyst is a solid catalyst having catalytic activity in the formation of unsaturated hydrocarbons by dehydrogenation of alkanes. In the method for producing an unsaturated hydrocarbon from an alkane described later, the catalyst is preferably used as a catalyst for a reaction of forming an unsaturated hydrocarbon (preferably an olefin) by dehydrogenation of an alkane.
In this catalyst, the carrier supporting the transition metal and carbon is not particularly limited, and for example, at least 1 kind selected from silica, alumina, zirconia, and titania can be used. One kind of these may be used alone or 2 or more kinds may be used in combination. Of these, alumina is preferred, and γ -alumina is particularly preferred.
The particle size of the carrier may be appropriately selected, and is preferably adjusted so that the pressure loss in the catalyst layer of a reactor (for example, a reaction tube) filled with the obtained catalyst does not become excessive. From the viewpoint of suppressing the pressure loss in the catalyst layer and securing the surface area of the catalyst, the particle size of the carrier is preferably as small as possible, and when a sieve based on Japanese Industrial Standards (JIS) is used, it is preferably 3.5 mesh (mesh 5.6mm) or more, and particularly preferably 8.6 mesh (mesh 2.0mm) or more. On the other hand, from the viewpoint of difficulty in handling the fine particle components and influence of increase in pressure loss when filling the reactor on reactivity, the mesh size is preferably 635 mesh (mesh size 20 μm) or less, and particularly preferably 280 mesh (mesh size 53 μm) or less.
The catalyst according to the embodiment of the present invention may be filled in a powder state into a reactor (for example, a reaction tube). In this case, the particle size is preferably adjusted so that the pressure loss in the catalyst layer does not become excessive. From the viewpoint of suppressing the pressure loss in the catalyst layer and securing the surface area of the catalyst, the particle size of the catalyst is preferably as small as possible. In addition, from the viewpoint of suppressing the pressure loss in the catalyst layer, the catalyst may be mixed with other materials and may be filled after molding. As the other material, a filler (silica spheres, alumina spheres) which is inactive to the catalyst and does not deteriorate the catalyst performance can be used. In addition, the molding may be carried out by adding a binder to the obtained catalyst without deteriorating the performance of the catalyst, kneading the resulting mixture, and heating the kneaded mixture to sinter the kneaded mixture. Examples of the binder (sintering agent) include silica-based, alumina-based, zirconia-based, and diatomaceous earth-based binders. Examples of the shape after molding include a sheet, a pellet, a sphere, and an extrusion. By molding, strength and workability can be improved.
As the transition metal to be supported on the carrier, at least one selected from molybdenum, tungsten, chromium, nickel, iron, noble metals (Au, Ag, Pt, Pd, Rh, Ir, Ru, Os), vanadium, manganese, and zinc may be used, and a plurality of them may be used. Of these, nickel (Ni) is preferable from the viewpoint of cost and catalyst performance.
The amount of the transition metal supported on the carrier is preferably 1.0 to 30.0% by mass based on the carrier from the viewpoint of exhibiting good activity as a catalyst. By setting the amount of the transition metal supported on the carrier to 1.0 mass% or more, the transition metal particles present as active sites are easily held on the surface of the carrier, and thus the conversion rate of alkane can be improved. Further, by setting the amount of the transition metal supported on the carrier to 30.0 mass% or less, aggregation of the transition metal particles supported on the carrier can be further suppressed, the surface area of the active sites can be maintained large, and the conversion rate of alkane and the selectivity of alkene corresponding to the alkane can be improved. Among the above, the amount of the transition metal supported on the carrier is more preferably 3.0% by mass or more, further preferably 5.0% by mass or more, particularly preferably 10.0% by mass or more, and most preferably 15.0% by mass or more, and on the other hand, is more preferably 28.0% by mass or less, further preferably 25.0% by mass or less, and particularly preferably 23.0% by mass or less. In the present invention, the amount of the transition metal supported on the carrier can be measured by an X-ray fluorescence analyzer.
The catalyst of the present embodiment further supports carbon containing fibrous carbon on the transition metal as described above. The catalyst can increase the conversion rate of alkane and the selectivity of olefin corresponding to the alkane in the dehydrogenation reaction of alkane by supporting carbon containing fibrous carbon. The reason is not clear, but is considered to be the following reason.
In a general metal-supported catalyst, metal particles on a carrier aggregate into coarse particles as the reaction proceeds, and the surface area of active sites is reduced to cause a reduction in reactivity, and the structure of the active sites is changed to cause a reduction in selectivity. However, it is considered that since carbon containing a specific amount of fibrous carbon is supported in advance on the transition metal, aggregation of the transition metals due to heat or vibration in the reaction can be suppressed by the presence of the carbon containing the fibrous carbon, and thus a good active site can be maintained, and the selectivity of alkane, the selectivity of alkene corresponding to the alkane, and the selectivity of unsaturated hydrocarbon can be improved. In the present invention, carbon stretched into a fibrous shape (carbon present in a so-called elongated shape) is referred to as fibrous carbon when observed by a Scanning Electron Microscope (SEM). The cross-sectional shape (the shape of the cross-section perpendicular to the longitudinal direction) of the carbon drawn into a fiber shape may be any of a circle, an ellipse, a triangle, a quadrangle, a polygon, and the like, or may be an amorphous shape, and may be a thin plate shape. The ratio of the length of the fibrous carbon to the average diameter of the cross section is not particularly limited. The fibrous carbon may be bent, linearly stretched, or branched.
The amount of carbon containing fibrous carbon supported on the carrier is preferably 510 mass% or more, and preferably 2500 mass% or less, with respect to the supported transition metal. If the amount of carbon containing fibrous carbon supported on the carrier is 550 mass% or more relative to the supported transition metal, the effect of immobilizing the transition metal particles is easily obtained, and therefore aggregation of the transition metal particles during the reaction is easily suppressed. As a result, the conversion rate of alkane and the selectivity of olefin corresponding to the alkane can be improved. The carbon supported on the carrier may contain fibrous carbon, and if the amount of carbon containing fibrous carbon is in such a range, the above-described effects can be more sufficiently obtained. The point that the carbon supported on the carrier contains fibrous carbon (the fibrous carbon supported on the carrier is present) can be confirmed by Scanning Electron Microscopy (SEM). The observation image obtained by SEM is divided into 12 equal lattices, and preferably fibrous carbon is formed on the support to such an extent that the presence of the fibrous carbon can be confirmed in each lattice.
On the other hand, if the amount of carbon containing fibrous carbon supported on the carrier is 2500 mass% or less with respect to the supported transition metal, it is possible to further prevent the transition metal particles from being coated with excessive carbon to impair the catalytic activity, and to improve the conversion of alkane and the selectivity of alkene corresponding to the alkane.
Among the above, the amount of carbon containing fibrous carbon supported on the carrier is more preferably 700 mass% or more, particularly preferably 1000 mass% or more, and on the other hand more preferably 2300 mass% or less, particularly preferably 2000 mass% or less, with respect to the supported transition metal.
In the present invention, the amount of carbon containing fibrous carbon supported on the carrier can be measured by raising the temperature to 1000 ℃ using thermogravimetric-differential thermal analysis (TG-DTA), starting from the weight loss at that time. In the examples described later, the weight loss at the time of heating to 200 ℃ is caused by desorption of adsorbed water, and therefore the weight loss in the temperature raising process from 200 ℃ to 1000 ℃ is calculated as the amount of carbon supported and containing fibrous carbon.
The fibrous carbon supported on the transition metal-supporting carrier preferably has an average diameter of 20nm to 100 nm. If the average diameter of the fibrous carbon is 20nm or more, aggregation of the transition metal particles can be further prevented during the reaction, and the conversion rate of alkane and the selectivity of olefin corresponding to the alkane can be further improved. On the other hand, if the average diameter of the fibrous carbon is 100nm or less, the coating of the transition metal particles by the fibrous carbon can be further suppressed, and the decrease in the catalytic activity tends to be easily prevented. Among them, the average diameter of the fibrous carbon is more preferably 25nm or more, particularly preferably 30nm or more, and on the other hand, more preferably 95nm or less, particularly preferably 90nm or less.
In the present invention, the average diameter of the fibrous carbon means: an observation image obtained by a Scanning Electron Microscope (SEM) is divided into 12 equal grids, and a position where the diameter of the fibrous carbon is the largest and a position where the diameter of the fibrous carbon is the smallest are selected from the grids as diameter representative values, and an average value of the diameter representative values of the fibrous carbon is defined as an average diameter of the fibrous carbon.
(method for producing catalyst)
The method for producing a catalyst according to an embodiment of the present invention includes the steps of: mixing a solution containing a transition metal compound with a carrier, and heating the mixture to remove the solvent to obtain a catalyst precursor; and a step of bringing a carbon-containing gas into contact with the catalyst precursor to form a catalyst on which a transition metal and carbon are supported. By bringing a carbon-containing gas into contact with the above catalyst precursor, fibrous carbon can be formed and supported.
The step of obtaining the catalyst precursor may include: mixing a solution in which a transition metal compound is dissolved with a carrier, and heating the mixture to evaporate the solvent to obtain a solid; and a step of pulverizing the solid to obtain a powdery catalyst precursor.
In the step of obtaining the catalyst precursor, a solution may be prepared by dissolving a transition metal compound containing a supported transition metal in a solvent, and a carrier may be added to the solution to obtain a mixed solution containing the transition metal compound and the carrier. In the present invention, the addition is 1 type of the mixture, but this means that the mixture may be further mixed after the addition.
As the carrier used in the step of obtaining the catalyst precursor, at least 1 selected from the group consisting of silica, alumina, zirconia and titania described above can be used. Of these, alumina is preferred, and γ -alumina is particularly preferred.
Next, the mixed solution containing the transition metal compound and the carrier is heated to evaporate the solvent, thereby obtaining a catalyst precursor in which the transition metal is supported on the carrier as a solid. The powdery catalyst precursor can be obtained by pulverizing the obtained catalyst precursor (solid).
The obtained catalyst precursor may be dried at, for example, 20 to 200 ℃ for, for example, 1 to 20 hours. The temperature of the drying treatment is more preferably 60 ℃ or higher, still more preferably 100 ℃ or higher, and still more preferably 120 ℃ or lower. The time of the drying treatment is more preferably 5 hours or more, and is more preferably 15 hours or less.
The obtained catalyst precursor may be subjected to a heat treatment (calcination) at a high temperature of, for example, 300 to 1000 ℃ for, for example, 2 to 30 hours. The temperature of the heat treatment (calcination) is more preferably 400 ℃ or higher, and is more preferably 800 ℃ or lower. The time for this heat treatment (calcination) is more preferably 3 hours or longer, and is more preferably 12 hours or shorter.
The obtained powdery catalyst precursor may be filled into a reactor (e.g., a reaction tube) in a powdery state. In this case, it is preferable to adjust the particle size so that the pressure loss in the catalyst precursor phase does not become excessive. From the viewpoint of suppressing the pressure loss in the catalyst precursor phase and securing the surface area of the catalyst precursor, the particle diameter of the catalyst precursor is preferably as small as possible.
In addition, from the viewpoint of suppressing the pressure loss in the catalyst precursor phase, the catalyst precursor may be mixed with other materials or may be filled after molding. As another material, a filler (silica spheres, alumina spheres) which is inactive to the catalyst and does not deteriorate the catalyst performance can be used. In addition, the molding may be performed by adding a binder to the catalyst precursor without deteriorating the performance of the finally obtained catalyst, and kneading and heating the mixture to sinter the mixture. Examples of the binder (sintering agent) include silica-based, alumina-based, zirconia-based, and diatomaceous earth-based binders. Examples of the shape after molding include a sheet, a pellet, a sphere, and an extrusion. By molding, strength and workability can be improved.
Next, a carbon-containing gas is brought into contact with the resulting catalyst precursor. Thereby, the carbon-containing gas is carbonized by the oxidation reaction thereof. At the same time, the transition metal (transition metal oxide) existing in an oxidized state is reduced on the catalyst precursor, whereby carbon is supported simultaneously with the reduction of the transition metal oxide, thereby forming a catalyst (catalyst for alkane dehydrogenation) in which the transition metal and carbon are supported. In this case, since the reduction of the transition metal oxide and the support of carbon can be performed simultaneously, carbon is generated between the transition metal oxides during the reduction of the transition metal oxide, and the aggregation of the transition metal crystallites can be suppressed.
The diameter of the transition metal crystallites supported on (the carrier of) the catalyst is preferably 0.80 or less, more preferably more than 0.00 and 0.60 or less, and even more preferably 0.20 to 0.50, in terms of the ratio of the diameter of the transition metal crystallites after contact with the carbon-containing gas to the diameter of the crystallites when the carbon supported on the carrier contains the fibrous carbon, or in terms of the ratio of the diameter of the transition metal crystallites supported on the carrier when the carbon supported on the carrier does not contain the fibrous carbon. The conditions shown below may be appropriately adjusted in such a manner as to fall within this range.
In the measurement of the diameter of the transition metal crystallites supported on the carrier, the catalyst can be subjected to powder X-ray analysis measurement, and the obtained results can be calculated from the scherrer equation using the peaks ascribed to the transition metal crystallites. In the present invention, SmartLab/R/INP/DX (Rigaku corporation) was used for powder X-ray analysis. The measurement conditions were carried out under a tube voltage of 45kV and a tube current of 150mA, using Cu-K.alpha.rays as an X-ray source. For example, when nickel is used as the transition metal, the peak belonging to the (112) plane at 44 ° 2 θ can be used for calculation.
The reference of the ratio of the crystallite diameter of the transition metal supported on (the carrier for) the catalyst may be, as described above, the crystallite diameter of the transition metal when the catalyst precursor is not contacted with the carbon-containing gas, or the crystallite diameter of the transition metal supported on the carrier when the supported carbon does not contain fibrous carbon. The crystallite diameter as such a reference is preferably the crystallite diameter of the transition metal when the catalyst precursor is subjected to hydrogen reduction treatment (contact with a pretreatment gas containing hydrogen but not a carbon-containing gas). In particular, it is preferable that the crystallite diameter of the transition metal supported on the carrier after the hydrogen reduction treatment (contact with a pretreatment gas containing hydrogen but not a carbon-containing gas) is performed on the catalyst precursor under the conditions of comparative example 3 described later is used as a reference.
The carbon-containing gas preferably contains a hydrocarbon as a source of carbon (carbon source) supported on the catalyst precursor. The hydrocarbon is preferably an alkane having 2 to 5 carbon atoms. Examples of the alkane having 2 to 5 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, and isopentane. These can be used alone in 1 kind, or mixed with 2 or more kinds.
In the case where the step of producing the catalyst and the step of dehydrogenating an alkane to produce an unsaturated hydrocarbon using the obtained catalyst are continuously performed, the carbon source for carbon support and the alkane feedstock for dehydrogenation may be different hydrocarbons or the same hydrocarbon, but from the viewpoint of simplification of the process, the same hydrocarbon is preferable. In this case, the carbon source and the alkane raw material are preferably alkanes having 2 to 5 carbon atoms (e.g., ethane, propane, n-butane, isobutane, n-pentane, and isopentane), and more preferably isobutane.
The carbon-containing gas may contain an inert gas such as helium or nitrogen in addition to the carbon source.
The concentration of the carbon source (preferably hydrocarbon) contained in the carbon-containing gas (volume ratio of the carbon source to the carbon-containing gas) is preferably 1 to 30% by volume, particularly preferably 5% by volume or more, and particularly preferably 20% by volume or less. By setting the concentration of the carbon source to 1% by volume or more, a sufficient amount of carbon can be supported more favorably, and the selectivity of the unsaturated hydrocarbon can be further improved. Further, by setting the concentration of the carbon source to 30% by volume or less, the excessive carbon load can be controlled more easily, and the decrease in the conversion rate of the alkane and the selectivity of the unsaturated hydrocarbon can be suppressed more sufficiently.
The temperature in the step of supporting carbon on the catalyst precursor (the temperature when the carbon-containing gas is brought into contact with the catalyst precursor) is preferably 300 to 1000 ℃, particularly preferably 400 ℃ or higher, more preferably 700 ℃ or lower, and particularly preferably 600 ℃ or lower. By setting the temperature in the carbon supporting step to 300 ℃ or higher, a more sufficient carbon supporting amount can be obtained. In addition, by setting the temperature in the carbon supporting step to 1000 ℃ or lower, the decrease in the amount of carbon supported and the decrease in the catalyst activity due to the thermal decomposition reaction of the alkane as the carbon source can be more sufficiently suppressed.
The pressure in the step of supporting carbon on the catalyst precursor (the pressure when the carbon-containing gas is brought into contact with the catalyst precursor) may be appropriately selected depending on the type of the carbon-containing gas used, and is preferably 0.01 to 1 MPa. When the pressure is 0.01MPa or more, the components on the carrier under reduced pressure can be easily inhibited from being released. Further, by setting the pressure to 1MPa or less, it is possible to more sufficiently prevent an increase in reactivity due to pressurization, and to prevent an excessive amount of the supported carbon from being carried on the carrier. Among the above, 0.8MPa or less is more preferable, 0.5MPa or less is particularly preferable, and 0.05MPa or more is further preferable. The pressure may be atmospheric pressure (0.101 MPa).
As a method of bringing the carbon-containing gas into contact with the catalyst precursor, a fixed-bed flow reaction system in which the carbon-containing gas is caused to flow through a reactor (e.g., a reaction tube) filled with the catalyst precursor can be employed.
The W/F ratio when the catalyst precursor is brought into contact with the carbon-containing gas is preferably 0.03 g/min/ml to 0.5 g/min/ml.
W is the mass (g) of the catalyst precursor filled in the reaction tube, and F is the flow rate (ml/min) of the carbon-containing gas flowing in the reaction tube filled with the catalyst precursor. That is, W/F is the mass of the catalyst precursor filled in the reaction tube with respect to the flow velocity of the carbon-containing gas flowing in the reactor, and is represented by the following formula.
W/F (amount of catalyst precursor [ g ] charged into reaction tube)/(flow rate of carbon-containing gas flowing through reaction tube [ ml/min ])
By setting the W/F to 0.03 g/min/ml or more, the amount of carbon supported can be prevented from becoming insufficient. Further, by setting the W/F to 0.5 g/min/ml or less, the carbon supporting amount can be prevented from becoming excessive. Among the above, W/F is particularly preferably 0.05 g/min/ml or more, and particularly preferably 0.2 g/min/ml or less.
(method for producing unsaturated hydrocarbons from alkanes)
In the method for producing unsaturated hydrocarbons according to the embodiment of the present invention, the catalyst according to the present invention is brought into contact with a mixed gas containing alkanes and carbon dioxide (hereinafter, also referred to as "reaction gas" as appropriate), and unsaturated hydrocarbons are produced from alkanes.
The alkane raw material used for the dehydrogenation reaction of alkane is not particularly limited, but alkane having 2 to 5 carbon atoms is preferable. By setting the number of carbon atoms to 5 or less, the generation of a by-product having a lower carbon number due to the decomposition reaction can be suppressed. Examples of the alkane having 2 to 5 carbon atoms include ethane, propane, n-butane, isobutane, n-pentane, and isopentane. These can be used alone in 1 kind, or mixed with 2 or more kinds. By dehydrogenation, ethylene is produced mainly from ethane, propylene is produced mainly from propane, butadiene is produced mainly from n-butane, isobutene is produced mainly from isobutane, pentene is produced mainly from n-pentane and isoprene is produced mainly from isopentane.
In the production method according to the embodiment of the present invention, the dehydrogenation reaction of the alkane is performed to produce the corresponding unsaturated hydrocarbon. The dehydrogenation reaction is carried out by bringing a mixed gas (reaction gas) containing an alkane and carbon dioxide into contact with the catalyst of the present invention. The molar ratio of carbon dioxide to alkane contained in the mixed gas (reaction gas) is preferably 0.1 to 1.9, more preferably 0.25 or more, and still more preferably 1.6 or less. When the molar ratio is less than 0.1, the concentration of carbon dioxide is low, and thus the reactivity tends to decrease. On the other hand, if the molar ratio is more than 1.9, the concentration of carbon dioxide is high, and thus the selectivity tends to decrease.
The mixed gas (reaction gas) may contain inert gases such as helium and nitrogen, water vapor (water), methane, hydrogen, and the like, in addition to the alkane and the carbon dioxide, within a range not to impair the effects of the present invention.
The concentration of the alkane in the mixed gas (reaction gas) is preferably 1% by volume to 30% by volume, more preferably 1% by volume or more, further preferably 5% by volume or more, and further preferably 20% by volume or less. By setting the alkane concentration to 1% by volume or more, the decrease in the selectivity of unsaturated hydrocarbons due to the increase in the conversion of alkanes can be further suppressed. In addition, by setting the alkane concentration to 30% by volume or less, the decrease in the alkane conversion rate can be further suppressed.
The temperature of the dehydrogenation reaction of the alkane (the temperature at the time of contacting the mixed gas with the catalyst) is preferably 300 to 1000 ℃, more preferably 400 ℃ or higher, and on the other hand, more preferably 700 ℃ or lower, and still more preferably 600 ℃ or lower. By setting the temperature of the dehydrogenation reaction to 300 ℃ or higher, more sufficient catalyst activity can be obtained. Further, when the temperature of the dehydrogenation reaction is 1000 ℃ or lower, the decrease in the selectivity of the unsaturated hydrocarbon and the decrease in the catalyst activity due to the thermal decomposition reaction of the alkane can be further suppressed.
The pressure in the dehydrogenation reaction of the alkane may be appropriately selected depending on the kind of the alkane used in the reaction, and may be usually 1MPa or less, preferably 0.01MPa to 1 MPa. The pressure is more preferably 0.8MPa or less, still more preferably 0.5MPa or less, and on the other hand, more preferably 0.05MPa or more, still more preferably 0.1MPa or more. The pressure may be atmospheric pressure (0.101 MPa). By setting the pressure to 0.01MPa or more, the active sites on the catalyst can be more appropriately brought into contact with the alkane during the reaction, and the selectivity of the alkane can be easily increased. Further, by setting the pressure to 1MPa or less, it is possible to further suppress runaway reaction caused by excessive contact between the alkane in the reaction gas and the produced unsaturated hydrocarbon and the active site on the catalyst, and to improve the selectivity of the corresponding olefin.
The reaction form used in the method for producing unsaturated hydrocarbons according to the embodiment of the present invention is not particularly limited, and a general form used in catalytic reactions may be used. For example, a fixed bed, a moving bed, a fluidized bed and other reaction forms can be mentioned. Among these, the fixed bed system is preferably used from the viewpoint of the simplicity of the apparatus and the ease of process design. That is, in the method for producing unsaturated hydrocarbons according to the embodiment of the present invention, the dehydrogenation reaction of alkanes can be performed by a fixed-bed flow reaction system in which a mixed gas (reaction gas) containing alkanes as raw materials, carbon dioxide, and the like is passed through a reactor (for example, a reaction tube) filled with the catalyst according to the present invention.
The W/F ratio in the dehydrogenation reaction of alkane is preferably 0.001 g/min/ml to 1000 g/min/ml. The W/F is more preferably 0.01 g/min/ml or more, and still more preferably 100 g/min/ml or less.
W is the mass (g) of the catalyst filled in the reaction tube, and F is the flow rate (ml/min) of the mixed gas (reaction gas) containing alkane and carbon dioxide flowing through the reaction tube filled with the catalyst. That is, W/F is the mass of the catalyst filled in the reaction tube with respect to the flow rate of the mixed gas (reaction gas) flowing through the reaction tube, and is represented by the following formula.
W/F (amount of catalyst [ g ] charged into reaction tube)/(flow rate of mixed gas flowing through reaction tube [ ml/min ])
When the W/F is 0.001 g/min/ml or more, the reaction time of alkane with respect to the catalyst can be further secured, and the conversion rate of alkane can be improved. Further, by setting the W/F to 1000g · min/ml or less, it is possible to further prevent the alkane from reacting over the catalyst for an excessive time, and to further prevent the produced olefin from reacting on the catalyst to become carbon dioxide, which leads to a decrease in selectivity.
Examples
The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.
(example 1)
First, a catalyst (Ni-C/γ -Al) was prepared as follows2O3A catalyst).
With Ni relative to gamma-Al2O3To make the amount of (1) to be charged to 20 mass%, 3.89 parts by mass of nickel nitrate hexahydrate (Wako pure chemical industries, Ltd.) was added to 15 parts by mass of water and dissolved to obtain an aqueous solution.
Thereafter, 4 parts by mass of γ -Al was added to the aqueous solution2O3(light metals of Japan) was mixed. Next, the mixture was heated to evaporate water to obtain a solid. The resulting solid was pulverized and dried under vacuum at 110 ℃ for 12 hours.
The pulverized solid was further calcined at 550 ℃ for 1 hour (rate of temperature rise 1 ℃/min). The obtained solid was pulverized again to obtain a powdery catalyst precursor 1 (nickel-supported γ -Al)2O3)。
The obtained catalyst precursor 1 was charged into a quartz reaction tube having a diameter of 9mm and a length of 35mm, which was installed in a fixed bed flow-through reaction apparatus, and heated to 550 ℃ while circulating helium. Thereafter, the pretreatment gas containing 85.8 vol% of helium and 14.2 vol% of isobutane was set to have a W/F ratio of 0.12 g/min/ml under each condition. So that the pretreatment gas flows in the reaction tubeThe reaction lasts for 3 hours to obtain Ni-C/gamma-Al of which the carbon is loaded on the catalyst precursor 12O3A catalyst.
In addition, the catalyst obtained (Ni-C/. gamma. -Al) was carried out2O3Catalyst) by powder X-ray analysis. SmartLab/R/INP/DX (manufactured by Rigaku corporation) was used for the X-ray analysis. The measurement conditions were carried out under a tube voltage of 45kV and a tube current of 150mA, using Cu-K.alpha.rays as an X-ray source. The crystallite diameter of Ni was calculated using the peak assigned to the (112) plane at 2 θ ═ 44 °.
Next, using this catalyst, isobutene was produced from isobutane as follows.
In a state where the catalyst obtained as described above was directly filled in the reaction tube, a reaction gas adjusted to 73.7% by volume of helium, 14.2% by volume of isobutane, and 12.1% by volume of carbon dioxide was circulated. At this time, the respective conditions were set so that W/F became 0.017g · min/ml.
The reaction tube outlet gas after 6 hours from the start of the flow of the reaction gas was measured by a gas chromatograph, and the isobutane conversion rate, the isobutene selectivity and the isobutene yield were obtained. The results are shown in Table 1.
The "W/F" is represented by the following formula.
W/F (amount of catalyst precursor or catalyst filled in the reaction tube) (g)/rate of supply of carbon-containing gas or reaction gas into the reaction tube (ml/min)
In addition, the isobutane conversion, isobutene selectivity and isobutene yield are represented by the following formulas.
Isobutane conversion (%) - (moles of isobutane reacted)/(moles of isobutane supplied)
Isobutylene selectivity (%) (number of moles of isobutylene produced)/(number of moles of isobutane reacted)
Yield (%) of isobutylene (moles of isobutylene produced)/(moles of isobutane supplied)
(example 2)
A catalyst (Ni-C/. gamma. -Al) was prepared in the same manner as in example 1, except that the flow time of the pretreatment gas was changed to 5 hours2O3Catalyst), followed by production of isobutylene by the same method as in example 1.
In addition, the obtained catalyst (Ni-C/gamma-Al)2O3Catalyst) was heated to 1000 ℃ by thermogravimetry-differential thermal analysis (TG-DTA), and the amount of carbon supported was measured from the weight loss at that time. In this case, the weight loss at the time of heating to 200 ℃ is caused by the desorption of adsorbed water, and therefore the weight loss in the temperature raising process from 200 ℃ to 1000 ℃ is calculated as the amount of carbon supported. Next, it was confirmed by a Scanning Electron Microscope (SEM) that the carbon of the catalyst was fibrous carbon (SEM images are shown in fig. 1 and 2). The average diameter of the fibrous carbon was 41.9 nm. The results are shown in Table 1.
(example 3)
A catalyst (Ni-C/. gamma. -Al) was prepared in the same manner as in example 1, except that the flow time of the pretreatment gas was changed to 7 hours2O3Catalyst), followed by production of isobutylene by the same method as in example 1. The results are shown in Table 1.
Comparative example 1
Ni/γ -Al was produced in the same manner as in example 1, except that the pretreatment gas was not circulated2O3The catalyst was then used to produce isobutylene in the same manner as in example 1. The results are shown in Table 1.
Comparative example 2
Ni/γ -Al was produced in the same manner as in example 1 except that the pretreatment gas was changed to a gas containing 80.0 vol% of helium and 20.0 vol% of hydrogen, and the conditions were changed such that the W/F ratio was 0.0042 g/min/ml and the flow time of the pretreatment gas was 1 hour2O3The catalyst was then used to produce isobutylene in the same manner as in example 1. The results are shown in Table 1.
Comparative example 3
Ni/γ -Al was produced in the same manner as in comparative example 2, except that the flow time of the pretreatment gas was changed to 5 hours2O3Catalyst, followed by and carried outIsobutylene was produced in the same manner as in example 1.
The results are shown in Table 1.
Comparative example 4
Ni/γ -Al was produced in the same manner as in example 1, except that the flow time of the pretreatment gas was changed to 1 hour2O3The catalyst was then used to produce isobutylene in the same manner as in example 1.
The results are shown in Table 1.
Claims (28)
1. A catalyst characterized in that a transition metal and carbon are supported on a carrier, the carbon comprising fibrous carbon.
2. The catalyst according to claim 1, wherein a ratio of a crystallite diameter of the transition metal when the carbon supported by the carrier contains the fibrous carbon to a crystallite diameter of the transition metal when the carbon supported by the carrier does not contain the fibrous carbon is 0.80 or less.
3. The catalyst according to claim 1 or 2, wherein the amount of the carbon relative to the transition metal is 510 to 2500 mass%.
4. A catalyst as claimed in any one of claims 1 to 3, wherein the catalyst is a catalyst for the dehydrogenation of alkanes.
5. A catalyst as claimed in any one of claims 1 to 4 wherein the transition metal is nickel.
6. The catalyst according to any one of claims 1 to 5, wherein the carrier is at least 1 selected from silica, alumina, zirconia and titania.
7. The catalyst of any one of claims 1 to 5, wherein the support is gamma alumina.
8. A method for producing a catalyst, comprising the steps of:
a step of mixing a solution containing a transition metal compound with a carrier, heating the mixture to remove the solvent and obtain a catalyst precursor, an
A step of bringing a carbon-containing gas into contact with the catalyst precursor to form a catalyst on which a transition metal and carbon are supported,
in the step of forming the catalyst, a carbon-containing gas is brought into contact with the catalyst precursor, thereby forming and supporting fibrous carbon.
9. The method for producing a catalyst according to claim 8, wherein the step of obtaining the catalyst precursor comprises: mixing a solution in which a transition metal compound is dissolved with a carrier, and heating the mixture to evaporate the solvent to obtain a solid; and a step of pulverizing the solid to obtain a powdery catalyst precursor.
10. The method for producing a catalyst according to claim 8 or 9, wherein the carbon-containing gas contains a hydrocarbon.
11. The method for producing a catalyst according to claim 10, wherein the hydrocarbon is an alkane having 2 to 5 carbon atoms.
12. The method for producing a catalyst according to claim 10, wherein the hydrocarbon is isobutane.
13. The method for producing a catalyst according to any one of claims 10 to 12, wherein a volume ratio of the hydrocarbon to the carbon-containing gas is 1 to 30% by volume.
14. The method for producing a catalyst according to any one of claims 8 to 13, wherein the temperature at which the carbon-containing gas is contacted with the catalyst precursor is 300 ℃ to 1000 ℃.
15. The method for producing a catalyst according to any one of claims 8 to 14, wherein a ratio W/F of an amount of the catalyst precursor to a supply rate of the carbon-containing gas when the carbon-containing gas is brought into contact with the catalyst precursor is 0.03 g/min/ml to 0.5 g/min/ml.
16. The method for producing a catalyst according to any one of claims 8 to 15, wherein the transition metal is nickel.
17. The method for producing a catalyst according to any one of claims 8 to 16, wherein the carrier is at least 1 selected from the group consisting of silica, alumina, zirconia and titania.
18. The method for producing a catalyst according to any one of claims 8 to 16, wherein the carrier is γ -alumina.
19. The method for producing a catalyst according to any one of claims 8 to 18, wherein a ratio of a crystallite diameter of the transition metal supported by the catalyst to a crystallite diameter of the transition metal on the catalyst precursor when the catalyst precursor is not in contact with the carbon-containing gas is 0.80 or less.
20. A process for producing an unsaturated hydrocarbon, which comprises contacting the catalyst according to any one of claims 1 to 8 with a mixed gas containing an alkane and carbon dioxide to produce an unsaturated hydrocarbon from the alkane.
21. The unsaturated hydrocarbon production method according to claim 20, wherein a molar ratio of the carbon dioxide to the alkane in the mixed gas is 0.1 to 1.9.
22. A method for producing unsaturated hydrocarbons according to claim 20 or 21, wherein the alkane is an alkane having 2 to 5 carbon atoms.
23. The unsaturated hydrocarbon production method according to claim 20 or 21, wherein the alkane is isobutane.
24. A method for producing unsaturated hydrocarbons according to any of claims 20 to 23, wherein the temperature at which the mixed gas is brought into contact with the catalyst is 300 ℃ to 1000 ℃.
25. A method for producing unsaturated hydrocarbons according to any of claims 20 to 24, wherein a ratio W/F of an amount of the catalyst to a supply rate of the mixed gas when the mixed gas is brought into contact with the catalyst is 0.001 g-min/ml to 1000 g-min/ml.
26. A method for producing an unsaturated hydrocarbon, which comprises producing a catalyst by the production method according to any one of claims 8 to 19, and then bringing a mixed gas containing an alkane and carbon dioxide into contact with the obtained catalyst to produce an unsaturated hydrocarbon from the alkane.
27. A method for producing an unsaturated hydrocarbon, comprising the steps of:
a step of bringing a carbon-containing gas into contact with a catalyst precursor in which a transition metal compound is supported on a carrier to thereby support carbon containing fibrous carbon on the catalyst precursor and form a catalyst in which the transition metal and the carbon containing fibrous carbon are supported,
a mixed gas containing an alkane and carbon dioxide is brought into contact with the obtained catalyst, and an unsaturated hydrocarbon is produced from the alkane.
28. A method for producing unsaturated hydrocarbons according to claim 26 or 27, wherein the molar ratio of the carbon dioxide to the alkane in the mixed gas is 0.1 to 1.9.
Applications Claiming Priority (5)
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| PCT/JP2020/042127 WO2021095782A1 (en) | 2019-11-14 | 2020-11-11 | Catalyst and method for manufacturing same, and method for manufacturing unsaturated hydrocarbon |
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