CN117642227A - Catalyst for synthesis of liquefied petroleum gas and method for producing liquefied petroleum gas - Google Patents
Catalyst for synthesis of liquefied petroleum gas and method for producing liquefied petroleum gas Download PDFInfo
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- CN117642227A CN117642227A CN202280047374.1A CN202280047374A CN117642227A CN 117642227 A CN117642227 A CN 117642227A CN 202280047374 A CN202280047374 A CN 202280047374A CN 117642227 A CN117642227 A CN 117642227A
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- catalyst material
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- liquefied petroleum
- petroleum gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 452
- 239000003915 liquefied petroleum gas Substances 0.000 title claims abstract description 222
- 230000015572 biosynthetic process Effects 0.000 title claims description 139
- 238000003786 synthesis reaction Methods 0.000 title claims description 138
- 238000004519 manufacturing process Methods 0.000 title claims description 55
- 239000000463 material Substances 0.000 claims abstract description 280
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 193
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 191
- 239000010457 zeolite Substances 0.000 claims abstract description 191
- 229910017518 Cu Zn Inorganic materials 0.000 claims abstract description 65
- 229910017752 Cu-Zn Inorganic materials 0.000 claims abstract description 65
- 229910017943 Cu—Zn Inorganic materials 0.000 claims abstract description 65
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 65
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 61
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 61
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 40
- 239000007789 gas Substances 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 8
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 164
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 119
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 117
- 239000001294 propane Substances 0.000 description 82
- 239000001273 butane Substances 0.000 description 46
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 46
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 46
- 229910052763 palladium Inorganic materials 0.000 description 36
- 229910052697 platinum Inorganic materials 0.000 description 36
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 28
- 239000002245 particle Substances 0.000 description 25
- 239000000203 mixture Substances 0.000 description 24
- 239000000243 solution Substances 0.000 description 24
- 239000002253 acid Substances 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 18
- 239000007864 aqueous solution Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005470 impregnation Methods 0.000 description 14
- 229910000510 noble metal Inorganic materials 0.000 description 14
- 235000011007 phosphoric acid Nutrition 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- 239000004570 mortar (masonry) Substances 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 11
- 150000004687 hexahydrates Chemical class 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910004298 SiO 2 Inorganic materials 0.000 description 9
- 238000011049 filling Methods 0.000 description 9
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000005751 Copper oxide Substances 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 8
- 229910000431 copper oxide Inorganic materials 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 238000001354 calcination Methods 0.000 description 7
- 230000006866 deterioration Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 230000007774 longterm Effects 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000011973 solid acid Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007937 lozenge Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000003826 tablet Substances 0.000 description 2
- 210000002268 wool Anatomy 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000016936 Dendrocalamus strictus Nutrition 0.000 description 1
- FTVZOQPUAHMAIA-UHFFFAOYSA-N O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FTVZOQPUAHMAIA-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052903 pyrophyllite Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The catalyst for synthesizing liquefied petroleum gas comprises: a Cu-Zn-based catalyst material; an MFI type zeolite catalyst material carrying Pt; the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass (M2) of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is 0.30 to 0.95.
Description
Technical Field
The present invention relates to a catalyst for synthesis of liquefied petroleum gas and a method for manufacturing the liquefied petroleum gas.
Background
Liquefied Petroleum Gas (LPG) containing propane and butane as main components is present in oil fields and natural gas fields in a state of being mixed with impurity gases such as methane and ethane. After such gas is transferred to an above-ground facility, propane and butane are separated and recovered from the gas, and impurities such as sulfur and mercury are further removed to obtain liquefied petroleum gas.
And, liquefied petroleum gas is also contained in crude oil. Therefore, propane and butane can be separated and extracted in the refining step of the oil production station to obtain liquefied petroleum gas.
In addition, a method for producing liquefied petroleum gas from synthesis gas of carbon monoxide and hydrogen is also being studied. For example: patent documents 1 to 4 describe a method for producing a liquefied petroleum gas, the main component of which is butane.
Further, non-patent documents 1 to 2 disclose a method for producing hydrocarbons mainly comprising isobutane from a synthesis gas of carbon monoxide and hydrogen.
In the above patent documents, the production of liquefied petroleum gas and gasoline is mainly performed using a mixed catalyst of a methanol synthesis catalyst and a palladium-supported zeolite.
In the case of synthesizing liquefied petroleum gas using a conventional mixed catalyst such as the above patent document, when synthesizing at a high temperature in order to increase the yield of liquefied petroleum gas such as propane and butane, the mixed catalyst may deteriorate, and the yield of liquefied petroleum gas may decrease with time, making it difficult to stably synthesize liquefied petroleum gas for a long period of time. In particular, when a cu—zn-based catalyst having good catalyst activity is used, deterioration due to high temperature is remarkable.
On the other hand, if the synthesis of liquefied petroleum gas is performed at a low temperature using a conventional mixed catalyst such as the above patent document in order to suppress the deterioration of the catalyst due to such a high temperature, there is a problem that the yield of liquefied petroleum gas such as propane is very low.
Further, since propane is easily vaporized and is easily used as a fuel even in, for example, cold areas, the yield of propane is expected to be particularly high in liquefied petroleum gas.
[ Prior Art literature ]
(patent literature)
Patent document 1: japanese patent No. 5405103
Patent document 2: japanese patent No. 4965258
Patent document 3: japanese patent No. 4558751
Patent document 4: japanese patent laid-open publication No. 2019-37939
Non-patent document 1: congming Li, kaoru Fujimoto, inc. "Synthesis gas conversion to iso-bunane-rich hydrocarbons over a hybrid catalyst containing Beta zeolite-role of doped palladium and influence of the SiO 2 /Al 2 O 3 ratio”、Catalysis Science&Technology、2015、5、4501-4510
Non-patent document 2: congming Li, hongyan Bans, weijie Cai, yu Zhang, zhongLi, kaoru Fujimoto "Direct synthesis of iso-butane from synthesis gas or CO2over CuZnZrAl/Pd-beta hybrid catalyst", journal of Saudi Chemical Society (2017) 21, 974-982
Disclosure of Invention
[ problem to be solved by the invention ]
The purpose of the present invention is to provide a catalyst for synthesis of liquefied petroleum gas and a method for producing liquefied petroleum gas, which can produce propane with high yield even when the synthesis temperature of liquefied petroleum gas is low.
[ means of solving the problems ]
[1] A catalyst for synthesis of liquefied petroleum gas, comprising: a Cu-Zn-based catalyst material; an MFI type zeolite catalyst material carrying Pt; the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass (M2) of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is 0.30 to 0.95.
[2] The catalyst for synthesis of liquefied petroleum gas according to the above [1], wherein the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is 0.30 or more and less than 0.70.
[3] The catalyst for synthesis of liquefied petroleum gas as described in the above [1], wherein a ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is 0.50 to 0.95.
[4] The catalyst for synthesis of liquefied petroleum gas according to any one of the above [1] to [3], wherein the MFI-type zeolite catalyst material carries Pt alone.
[5] The catalyst for synthesis of liquefied petroleum gas according to any one of the above [1] to [3], wherein the MFI-type zeolite catalyst material further supports Pd.
[6]As described above [5]]In the catalyst for synthesis of liquefied petroleum gas, the mass (M) of Pd supported on the MFI-type zeolite catalyst material Pd ) Mass relative to Pt (M Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) Ratio (M) Pd /(M Pt +M Pd ) 0.70 or less.
[7]As described above [5]]Or [6 ]]In the catalyst for synthesis of liquefied petroleum gas, the mass (M2) of Pt in the MFI-type zeolite catalyst material is calculated based on the mass of the MFI-type zeolite catalyst material (M Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) Is 0.1 mass% or more and 1.0 mass% or less.
[8] The catalyst for synthesis of liquefied petroleum gas according to any one of the above [1] to [7], wherein the Cu-Zn catalyst material and the MFI-type zeolite catalyst material are present independently of each other, and the Cu-Zn catalyst material and the MFI-type zeolite catalyst material are both in the form of a powder or a molded body.
[9] A method for producing liquefied petroleum gas, comprising: a reduction treatment step of subjecting the catalyst for synthesis of liquefied petroleum gas described in any one of [1] to [8] to a reduction treatment; a supply step of supplying carbon monoxide and hydrogen to the catalyst for synthesizing liquefied petroleum gas after the reduction treatment in the reduction treatment step; and a synthesis step of synthesizing liquefied petroleum gas by reacting carbon monoxide and hydrogen supplied in the supply step with the catalyst for synthesizing liquefied petroleum gas after the reduction treatment.
[10] The method for producing liquefied petroleum gas according to the above [9], wherein in the supplying step, a gas space velocity (GHSV) of supplying carbon monoxide and hydrogen is 300/h or more and 20000/h or less.
[11] The method for producing liquefied petroleum gas according to [9] or [10], wherein in the synthesis step, carbon monoxide and hydrogen are reacted at a temperature of 260℃to 360 ℃.
[12] The method for producing a liquefied petroleum gas according to any one of [9] to [11] above, wherein in the synthesis step, carbon monoxide and hydrogen are reacted at a pressure of 2.0MPa to 6.0 MPa.
[ efficacy ]
According to the present invention, a catalyst for synthesis of liquefied petroleum gas and a method for producing liquefied petroleum gas capable of producing propane with high yield even when the synthesis temperature of liquefied petroleum gas is low can be provided.
Drawings
FIG. 1 is a graph showing the results of examples 1 to 3 and comparative example 1.
FIG. 2 is a graph showing the results of examples 3 to 5.
FIG. 3 is a graph showing the results of comparative examples 2 to 5.
Fig. 4 is a graph showing the results of the middle-stage performance test of example 10.
FIG. 5 is a graph showing the results of the long-term performance test of example 8.
Detailed Description
The following is a detailed description of embodiments.
As a result of the repeated efforts of the present inventors, the following facts have been found and the present invention has been completed in accordance with such technical ideas: in a catalyst for synthesis of liquefied petroleum gas containing a Cu-Zn catalyst material and a zeolite catalyst material, propane can be produced in high yield even when the synthesis temperature of liquefied petroleum gas is low, by setting the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass (M1) of the mass (M2) of the Cu-Zn catalyst material and the mass (M2) of the zeolite catalyst material to a specific range, and setting the constitution and supporting material of the zeolite catalyst material to a specific one.
The catalyst for synthesis of liquefied petroleum gas according to the present embodiment comprises: a Cu-Zn-based catalyst material; and an MFI-type zeolite catalyst material (hereinafter also simply referred to as zeolite catalyst material) supporting Pt; the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is 0.30 to 0.95.
As described above, the catalyst for synthesis of liquefied petroleum gas according to the embodiment includes: a Cu-Zn-based catalyst material; an MFI-type zeolite catalyst material. The catalyst for synthesis of liquefied petroleum gas can synthesize liquefied petroleum gas from carbon monoxide and hydrogen. The liquefied petroleum gas synthesized by the catalyst for synthesis of liquefied petroleum gas of the present embodiment contains propane and butane as main components, and contains more propane than butane. The ratio of the sum of propane and butane of the liquefied petroleum gas synthesized by the catalyst for synthesis of liquefied petroleum gas according to the present embodiment to the liquefied petroleum gas is, for example, 20cmol% or more. The ratio of propane to the total of propane and butane in the liquefied petroleum gas synthesized by the catalyst for synthesis of liquefied petroleum gas according to the present embodiment is, for example, 55vol% or more.
The cu—zn catalyst material constituting the catalyst for synthesis of liquefied petroleum gas has a function of a catalyst for synthesis of a liquefied petroleum gas precursor such as methanol and dimethyl ether from carbon monoxide and hydrogen.
The cu—zn catalyst material constituting the catalyst for synthesis of liquefied petroleum gas is a catalyst containing copper oxide and zinc oxide, and is excellent in the performance of the synthesized liquefied petroleum gas precursor among the catalysts for synthesis of the liquefied petroleum gas precursor. The cu—zn-based catalyst material may further contain, in addition to copper oxide and zinc oxide: alumina, gallium oxide, zirconia, indium oxide, and the like. By including aluminum oxide, gallium oxide, zirconium oxide, indium oxide, and the like, dispersibility of copper oxide and zinc oxide can be improved. The cu—zn-based catalyst material is preferably a ternary oxide of copper oxide and zinc oxide and aluminum oxide from the viewpoint of efficiently forming the number of interfaces of copper and zinc estimated as active sites.
The zeolite catalyst material constituting the catalyst for synthesis of liquefied petroleum gas synthesizes liquefied petroleum gas from a liquefied petroleum gas precursor produced from a cu—zn based catalyst material. In the present embodiment, the synthesized liquefied petroleum gas contains propane and butane as main components and contains more propane than butane.
Regarding zeolite catalyst materials used to constitute a catalyst for synthesis of liquefied petroleum gas, the zeolite is of MFI type. We speculate that: since the MFI-type zeolite catalyst material has a smaller pore diameter than the β -type zeolite, the components constituting the liquefied petroleum gas can synthesize propane more efficiently than butane or the like, and the yield of propane can be improved.
Further, the MFI-type zeolite catalyst material carries Pt (platinum). Preferably, the method comprises the following steps: the MFI-type zeolite catalyst material carries only Pt (platinum). We speculate that: the MFI zeolite catalyst material carrying Pt can efficiently react the liquefied petroleum gas precursor, and thus can improve the yield of propane.
In the present embodiment, the ratio (M1/(m1+m2)) of the mass (M1) of the cu—zn catalyst material to the total mass (M1) of the cu—zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material (hereinafter also referred to as simply the mass ratio of the cu—zn catalyst material) is 0.30 or more and 0.95 or less. When the mass ratio of the cu—zn catalyst material is within the above range, liquefied petroleum gas can be efficiently synthesized from carbon monoxide and hydrogen.
If the ratio (M1/(m1+m2)) is 0.30 or more and less than 0.70 in the above range, the initial catalyst activity in the catalyst for synthesis of liquefied petroleum gas is high. The lower limit is preferably 0.35 or more, more preferably 0.40 or more, and the upper limit is preferably 0.65 or less, more preferably 0.60 or less.
In the above range, the ratio (M1/(m1+m2)) is not less than 0.50 and not more than 0.95, and the catalyst activity in the catalyst for synthesis of liquefied petroleum gas is excellent in long-term stability. Regarding the above ratio, the lower limit is preferably 0.50 or more, more preferably 0.60 or more, still more preferably 0.70 or more, and the upper limit is preferably 0.95 or less, still more preferably 0.90 or less, still more preferably 0.85 or less.
CO and H on catalyst for synthesis of liquefied petroleum gas 2 The liquefied petroleum gas production reaction is performed by the following reaction mechanism. First, CO and H 2 In the presence of Cu-Zn catalyst materials (e.g. CuZnOZrO 2 Al 2 O 3 ) Up-conversion to liquefied petroleum gas precursorIs methanol. The methanol produced is then dehydrated by acid sites on an MFI zeolite catalyst (e.g., pt/P-ZSM-5) to convert to dimethyl ether. Dimethyl ether is dehydrated by acid sites on the MFI zeolite catalyst, and the carburetion reaction and the decomposition reaction are repeated to change into olefin. The produced olefin is hydrogenated on a noble metal such as Pt on an MFI zeolite catalyst to produce liquefied petroleum gas or the like.
Here, when the synthesis temperature is increased in the synthesis of the liquefied petroleum gas, the yield of the liquefied petroleum gas such as propane can be increased. However, when a cu—zn catalyst having excellent performance of a synthetic liquefied petroleum gas precursor is used, the cu—zn catalyst is aggregated at high temperature, and thus the cu—zn catalyst is significantly degraded with time, and it is difficult to stably synthesize the liquefied petroleum gas for a long period of time. On the other hand, if the synthesis temperature is lowered (for example, 330 ℃ or lower) in order to suppress the deterioration of the cu—zn catalyst due to such a high temperature, the deterioration of the cu—zn catalyst can be suppressed, but the yield of liquefied petroleum gas such as propane is low.
However, by using the catalyst for synthesis of liquefied petroleum gas of the present embodiment, propane can be produced with high yield even if the synthesis temperature of liquefied petroleum gas is low (for example, 330 ℃ or less). Therefore, by using the catalyst for synthesis of liquefied petroleum gas according to the present embodiment and synthesizing at a low temperature (for example, 330 ℃ or lower), propane can be produced with high yield, and deterioration of the catalyst due to high temperature can be suppressed. The synthesis temperature refers to the temperature of the catalyst for synthesis of liquefied petroleum gas.
In the present embodiment, the yield of propane in the produced liquefied petroleum gas is, for example, low even at a synthesis temperature (for example, 330 ℃ or lower): it may be 10Cmol% or more, 15Cmol% or more, and 17Cmol% or more.
In addition, by using the catalyst for synthesis of liquefied petroleum gas of the present embodiment, a high butane yield can be obtained. For example: the yield of butane is, for example, even if the synthesis temperature is low (e.g., 330 ℃ or lower): the concentration is 8Cmol% or more, and may be 10Cmol% or more, and further 12Cmol% or more.
In the present embodiment, the yields of propane and butane (total of the yields of propane and butane) produced are, for example: it is 25Cmol% or more, preferably 30Cmol% or more.
Further, by using the catalyst for synthesis of liquefied petroleum gas according to the present embodiment, a high ratio of propane to the total of propane and butane can be obtained. In this embodiment, the ratio of propane to the sum of propane and butane (mol number of propane/(mol number of propane+mol number of butane)) ×100 of the produced liquefied petroleum gas is, for example: more preferably, it is 55vol% or more, still more preferably 60vol% or more, still more preferably 65vol% or more, still more preferably 70vol% or more.
The zeolite catalyst material may further support platinum group elements such as Pd (palladium), rhodium (Rh), and ruthenium (Ru) in addition to Pt. The noble metal may be 1 or 2 or more. When the noble metal is 2 or more, the state of the noble metal supported on the zeolite catalyst material is not particularly limited, and examples thereof include: the noble metals may be mixed with each other in the form of a metal single body, may be alloyed, or may be mixed with an alloy.
Among them, the zeolite catalyst material is preferably supported with Pd (palladium) in addition to Pt. By supporting Pd in addition to Pt, the butane yield can be improved while maintaining a high propane yield when Pt alone is supported.
The state of Pt and Pd supported on the zeolite catalyst material may be such that Pt of a metal monomer and Pd of a metal monomer are mixed, or Pt and Pd may be alloyed, or at least one of Pt and Pd may be mixed with an alloy of Pt and Pd.
When Pt and Pd are supported on the zeolite catalyst material, the mass (M Pd ) Mass relative to Pt (M Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) Ratio (M) Pd /(M Pt +M Pd ) (hereinafter also referred to as mass ratio (M) Pd /(M Pt +M Pd ) A) the upper limit value is preferably 0.70 or less, more preferably 0.60 or less, and still more preferably 0.50 or less. In addition, the mass ratio (M Pd /(M Pt +M Pd ) Lower limit value such as: it is preferably 0.01 or more, more preferably 0.15 or more, still more preferably 0.20 or more, and still more preferably 0.25 or more. If the mass ratio (M Pd /(M Pt +M Pd ) If the butane yield is 0.70 or less, the butane yield can be further improved.
Further, the mass (M2) of Pt in the zeolite catalyst material relative to the mass (M2) of the zeolite catalyst material Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) The lower limit of (2) is preferably not less than 0.1 mass%, more preferably not less than 0.2 mass%, still more preferably not less than 0.3 mass%, and the upper limit is preferably not more than 1.0 mass%, still more preferably not more than 0.8 mass%, still more preferably not more than 0.7 mass%. When the zeolite catalyst material does not support Pd, the Pd content ratio in the total content ratio is 0 (zero), that is, the total content ratio is the Pt content ratio.
The mass (M2) of Pt relative to the mass (M2) of the zeolite catalyst material Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) When the amount is 0.1 mass% or more, liquefied petroleum gas can be efficiently synthesized. In addition, the mass (M) of Pt relative to the mass (M2) of the zeolite catalyst material Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) When the mass ratio is 1.0% or less, the cost increase of Pt and Pd can be suppressed while maintaining efficient synthesis of liquefied petroleum gas.
Pd and Pt supported on the zeolite catalyst material or not, and the mass ratio (M Pd /(M Pt +M Pd ) Mass (M) of Pt as described above Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) The mass (M2) of the zeolite catalyst material can be measured by ICP-OES (inductively coupled plasma optical emission spectroscopy).
In addition, siO contained in the zeolite catalyst material 2 Relative to Al 2 O 3 Ratio of mol number (SiO) 2 mol/Al of (2) 2 O 3 The mol number of (2) (hereinafter also referred to as simply the mol ratio (SiO) 2 /Al 2 O 3 ) More preferably 20 to 60. The zeolite catalyst material is an aluminosilicate. Since a part of silicon atoms in silicate constituting zeolite skeleton of the zeolite catalyst material is replaced with aluminum atoms, the aluminum atoms become acid points, and the zeolite catalyst material exhibits the function of solid acid.
If the above molar ratio (SiO 2 /Al 2 O 3 ) If the acid point of the zeolite catalyst material is 60 or less, the acid point increases, and therefore the amount of liquefied petroleum gas produced can be increased, and propane can be efficiently synthesized, and therefore the amount of propane contained in the liquefied petroleum gas can be increased. In addition, if the above molar ratio (SiO 2 /Al 2 O 3 ) When the amount is 20 or more, the zeolite catalyst material supporting Pt can be easily produced while maintaining the high liquefied petroleum gas production capability and the high propane synthesis capability.
From the viewpoint of easiness in production of the zeolite catalyst material, the molar ratio (SiO 2 /Al 2 O 3 ) Preferably 20 or more, more preferably 25 or more, and still more preferably 30 or more. In addition, from the viewpoint of the high catalyst performance, the above molar ratio (SiO 2 /Al 2 O 3 ) Preferably 60 or less, more preferably 50 or less, and even more preferably 40 or less.
The above molar ratio (SiO 2 /Al 2 O 3 ) The measurement can be performed by ICP-OES (inductively coupled plasma optical emission spectroscopy).
In addition, the solid acid amount of the zeolite catalyst material is, for example: it is preferably at least 0.6mmol/g, more preferably at least 0.8 mmol/g. When the solid acid amount is 0.6mmol/g or more, the zeolite catalyst material supporting the noble metal can be easily produced while maintaining the high liquefied petroleum gas production capability and the high propane synthesis capability.
The solid acid amount can be NH 3 TPD (ammonia temperature desorption method) for measurement.
Preferably, the method comprises the following steps: the Cu-Zn catalyst material and the MFI-type zeolite catalyst material are independent of each other, and the Cu-Zn catalyst material and the MFI-type zeolite catalyst material are both a powder or a molded body. Catalyst for synthesis of liquefied petroleum gasPreferably, it is: the cu—zn catalyst material and the MFI-type zeolite catalyst material are not integrated (integrated). The Cu-Zn catalyst material and the zeolite catalyst material may be in the form of powder (powder, for example, having a particle diameter of 10 -9 ～10 -4 m), and may be particles having a larger particle diameter than the powder particles, and if the cu—zn catalyst material is a molded body containing the cu—zn catalyst material and the zeolite catalyst material is a molded body containing the zeolite catalyst material, the yields of propane and butane can be further improved. In other words, the catalyst for liquefied petroleum gas synthesis is preferably a mixture of a molded body containing a cu—zn catalyst material and a molded body containing a zeolite catalyst material.
The molded article containing the Cu-Zn catalyst material preferably contains the Cu-Zn catalyst material in an amount of 80 mass% or more, more preferably 90 mass% or more, and still more preferably 95 mass% or more. When the content ratio is 80 mass% or more, a liquefied petroleum gas precursor can be efficiently synthesized from carbon monoxide and hydrogen. The cu—zn catalyst material contained in the molded article may be contained in an amount of 100 mass%. The content is preferably 98% by mass or less, more preferably 96% by mass or less, and still more preferably 94% by mass or less. When the content is 98 mass% or less, the formability and mechanical strength of the molded article can be improved while maintaining efficient synthesis of the liquefied petroleum gas precursor.
The molded article containing the Cu-Zn catalyst material may contain various additives for improving moldability and mechanical strength in addition to the Cu-Zn catalyst material. Examples of the various additive materials include: graphite, carbon black, and the like.
The molded article containing the zeolite catalyst material preferably contains the zeolite catalyst material in an amount of 70 mass% or more, more preferably 80 mass% or more, and still more preferably 90 mass% or more. When the content ratio is 70 mass% or more, liquefied petroleum gas can be efficiently synthesized from the liquefied petroleum gas precursor. The content of the molded body containing the zeolite catalyst material in the molded body may be 100 mass%. The content is preferably 98% by mass or less, more preferably 96% by mass or less, and still more preferably 94% by mass or less. When the content is 98 mass% or less, the formability and mechanical strength of the molded article can be improved while maintaining efficient synthesis of the liquefied petroleum gas.
The molded article containing the zeolite catalyst material may contain various additives for improving moldability and mechanical strength in addition to the zeolite catalyst material, similarly to the molded article containing the cu—zn-based catalyst material. Examples of the various additive materials include: various clay binders, alumina-based binders, silica-based binders, and the like. Examples of the clay binders include: kaolin, bentonite, talc, pyrophyllite, ferric salt (molysite), vercullite, montmorillonite, chlorite, cereal Le Dan (halloysite) and the like. In order to efficiently increase the catalyst activity and to suppress the formation of catalyst poisoning substances such as coke, a silica-based binder is preferable as the molding binder.
The shapes of the cu—zn-based catalyst material and the zeolite catalyst material are not particularly limited. When the cu—zn-based catalyst material and the zeolite catalyst material are molded bodies, for example, it is possible to select: cylindrical, clover-like, annular, spherical, porous, etc. In the case of a cylindrical and clover-shaped molded article, the extruded article is preferable.
The particle diameter of the molded body containing the Cu-Zn catalyst material and the molded body containing the zeolite catalyst material is preferably 200 μm or more, more preferably 300 μm or more, and preferably 10mm or less, more preferably 5mm or less, and even more preferably 3mm or less. If the particle diameter is 200 μm or more, the pressure loss in the reactor can be prevented. In addition, if the diameter is 10mm or less, the contact efficiency between the reactant and the catalyst in the reactor can be improved. Particle size can be determined by a dry screening test method.
Further, the bulk density of the molded body containing the Cu-Zn catalyst material and the molded body containing the zeolite catalyst material was set to a lower limit of 0.5g/cm 3 The upper limit is preferably 1.5g/cm 3 The following is preferable, 1.0g/cm 3 The following is preferred. Bulk density can be determined by a SOCK-packed bulk density measurement method using a measuring cylinder.
In addition, the zeolite catalyst material preferably contains P (phosphorus). If the zeolite catalyst material contains P, the acid sites (solid acid sites) of the zeolite catalyst material are increased and changed to weak acid sites, so that the ratio of propane to the total of propane and butane can be increased. We speculate that: when the zeolite catalyst material contains P, P is bonded to Si-bonded O (oxygen) and Al-bonded O existing on the surface of the zeolite catalyst material as represented by the following formula (1).
Regarding the content ratio of P contained in the zeolite catalyst material, the mass (M) of P in the zeolite catalyst material relative to the mass (M2) of the zeolite catalyst material P ) The lower limit of (2) is preferably more than 0 mass%, more preferably more than 0.5 mass%, still more preferably more than 1.0 mass%, particularly preferably less than 5.0 mass%, particularly preferably less than 4.0 mass%, still more preferably less than 3.0 mass%, particularly preferably less than 2.5 mass%.
If the mass (M2) of the above P relative to the mass (M of the zeolite catalyst material P ) If the amount exceeds 0 mass%, the ratio of propane to the total of propane and butane can be increased. In addition, the mass (M) of P is calculated from the mass (M2) of the zeolite catalyst material P ) If the content is less than 5.0 mass%, a decrease in the ratio of propane to the total of propane and butane due to the excessive content of P and a decrease in the yields of propane and butane can be suppressed.
The presence or absence of P in the zeolite catalyst material and the content ratio of P can be measured by ICP-OES (inductively coupled plasma optical emission spectroscopy).
Examples of the element that generates the same function as P include: B. mg, ca, la, zr. These elements, like P, are capable of changing the acid nature of the zeolite catalyst material from strong to weak acids. Therefore, when B, mg, ca, la, zr, which is the same amount as P, is contained in the zeolite catalyst material, the ratio of propane to the total of propane and butane increases.
Next, a method for producing liquefied petroleum gas according to an embodiment will be described.
The method for producing a liquefied petroleum gas according to an embodiment comprises: a reduction treatment step, a supply step, and a synthesis step.
In the reduction treatment step, the catalyst for synthesizing liquefied petroleum gas is subjected to reduction treatment. The catalyst for synthesis of liquefied petroleum gas is preferably subjected to a reduction treatment with hydrogen gas.
In the supplying step performed after the reducing step, carbon monoxide (CO) and hydrogen (H) are supplied to the catalyst for synthesis of liquefied petroleum gas after the reducing step 2 ). Carbon monoxide and hydrogen are gases. As for the supply method, carbon monoxide and hydrogen may be supplied individually, and a mixed gas containing carbon monoxide and hydrogen such as synthesis gas may be supplied.
In the synthesis step performed after the supply step, the liquefied petroleum gas is synthesized by reacting the carbon monoxide and hydrogen supplied in the supply step with the catalyst for synthesis of liquefied petroleum gas after the reduction treatment. By using the catalyst for synthesis of liquefied petroleum gas as described above to react carbon monoxide with hydrogen, the yield of propane can be improved even when the synthesis temperature (the temperature of the catalyst in the synthesis step) is low, for example, 330 ℃ or less. The catalyst for synthesis of liquefied petroleum gas according to the present embodiment is not easily degraded and has excellent long-term stability, and can exhibit excellent catalyst performance for a long period of time (for example, 70 hours or more when the synthesis temperature is 330 ℃ or less).
In the supplying step, the gas space velocity (GHSV) of the supplied carbon monoxide and hydrogen is preferably 300/h or more, more preferably 500/h or more, still more preferably 1000/h or more, and the upper limit is preferably 20000/h or less, more preferably 10000/h or less, still more preferably 5000/h or less.
When the gas space velocity (GHSV) is 300/h or more, liquefied petroleum gas can be efficiently produced from carbon monoxide and hydrogen. Further, when the gas space velocity (GHSV) is 20000/h or less, the content of unreacted substances such as carbon monoxide and hydrogen can be suppressed from increasing in the liquefied petroleum gas-containing gas obtained after synthesis.
In addition, the lower limit of the temperature (synthesis temperature) of the catalyst in the synthesis step is preferably 260℃or more, more preferably 270℃or more, still more preferably 280℃or more, and the upper limit is preferably 360℃or less, more preferably 340℃or less, still more preferably 330℃or less, particularly preferably 320℃or less.
In the synthesis step, when carbon monoxide and hydrogen are reacted at a temperature of 260 ℃ or higher, liquefied petroleum gas can be efficiently produced from carbon monoxide and hydrogen. In addition, if carbon monoxide and hydrogen are reacted at a temperature of 360 ℃ or less in the synthesis step, deterioration of the catalyst performance of the catalyst for liquefied petroleum gas synthesis with respect to temperature can be suppressed. In addition, if carbon monoxide and hydrogen are reacted at a temperature of 360 ℃ or lower in the synthesis step, the yield of the produced liquefied petroleum gas can be suppressed from decreasing due to excessive decomposition (decomposition of propane into ethane and decomposition of ethane into methane).
Further, regarding the pressure in the synthesis step, carbon monoxide is reacted with hydrogen at a lower limit value of preferably 2.0MPa or more, more preferably 3.0MPa or more, still more preferably 3.5MPa or more, and an upper limit value of preferably 6.0MPa or less, more preferably 5.5MPa or less, still more preferably 5.0MPa or less.
In the synthesis step, when carbon monoxide and hydrogen are reacted at a pressure of 2.0MPa or more, liquefied petroleum gas can be efficiently produced from carbon monoxide and hydrogen. In the synthesis step, when carbon monoxide and hydrogen are reacted at a pressure of 6.0MPa or less, deterioration of the pressure due to the catalyst performance of the catalyst for liquefied petroleum gas synthesis can be suppressed.
The catalyst for synthesis of liquefied petroleum gas can be produced, for example, by: the Cu-Zn catalyst material is mixed with the zeolite catalyst material. The composition, proportion, state, etc. of the cu—zn catalyst material and the zeolite catalyst material can be appropriately set in accordance with the desired liquefied petroleum gas.
In addition, the above-mentioned mol ratio (SiO 2 /Al 2 O 3 ) Can be controlled by, for example, the following: the amount of aluminum source added in the synthesis of the zeolite catalyst material.
In addition, the amount of solid acid of the zeolite catalyst material can be controlled by, for example, the following: synthesis conditions (pH, etc.) at the time of synthesizing the zeolite catalyst substance.
The method for supporting the noble metal such as platinum and palladium on the zeolite catalyst material is not particularly limited, and examples thereof include: impregnation, and ion exchange.
When platinum and palladium are supported on the zeolite catalyst material, it is preferable to use an immersion liquid containing platinum and palladium and an immersion liquid to support platinum and palladium simultaneously, as compared with supporting each metal by successive impregnation or successive impregnation.
The starting materials of platinum and palladium supported on a zeolite catalyst material may be exemplified by compounds containing platinum and palladium. The starting material for platinum can be: chloroplatinic acid hexahydrate, dinitrodiamine platinum, dichlorotetramine platinum, platinum oxide, platinum chloride, and the like. Palladium starting materials can be used: palladium chloride, palladium nitrate, dinitrodiamine palladium, palladium sulfate, palladium oxide, and the like.
When a solution containing a compound of platinum and palladium such as a chloroplatinic acid solution or a palladium chloride solution is impregnated into a zeolite catalyst material or a zeolite catalyst material is impregnated into a solution containing a compound of platinum and palladium and then the impregnated or impregnated zeolite catalyst material is calcined, pt and Pd can be efficiently dispersed in the zeolite catalyst material, and the amount of Pt and Pd supported on the zeolite catalyst material can be easily controlled.
The concentration of the platinum and palladium-containing compound in the solution of the platinum and palladium-containing compound is set in accordance with the amount of platinum and palladium to be carried. For example: the concentration of the chloroplatinic acid hexahydrate solution is preferably 0.15% by mass or more and 3.50% by mass or less. The concentration of the palladium chloride solution is preferably 0.1 mass% or more and 2.5 mass% or less. The loading of Pt and Pd can be controlled by the concentration of the solution.
In order to allow platinum and palladium to sufficiently permeate the zeolite catalyst material, the impregnation time and the impregnation time of the solution are preferably 10 minutes or more and 5 hours or less.
The calcination temperature of the zeolite catalyst material is preferably 300 ℃ to 600 ℃, and the calcination time of the zeolite catalyst material is preferably 30 minutes to 300 minutes.
The method for supporting phosphorus on the zeolite catalyst material is not particularly limited, and examples thereof include: impregnation, and impregnation.
The starting material of phosphorus when phosphorus is supported on a zeolite catalyst material can be used: orthophosphoric acid, and phosphoric acid esters, and the like. For example: aqueous solutions of orthophosphoric acid and phosphoric acid esters can be used as impregnation liquids or impregnating liquids.
In the impregnation method or the impregnation method in which phosphorus is carried, when a solution of orthophosphoric acid and phosphoric acid ester (hereinafter also referred to as "phosphoric acid solution") is impregnated into a zeolite catalyst material, or when the zeolite catalyst material is impregnated into a phosphoric acid solution and then the impregnated or impregnated zeolite catalyst material is calcined, P can be contained in the zeolite catalyst material efficiently, and the amount of P contained in the zeolite catalyst material can be easily controlled.
The concentration of the phosphoric acid solution is preferably 2% by mass or more and 20% by mass or less.
In order to allow the phosphoric acid solution to sufficiently permeate the zeolite catalyst material, the impregnation time and the impregnation time of the phosphoric acid solution are preferably 10 minutes or more and 5 hours or less.
The calcination temperature of the zeolite catalyst material is preferably 300 ℃ to 600 ℃, and the calcination time of the zeolite catalyst material is preferably 30 minutes to 300 minutes.
The content ratio of P can be controlled by the concentration of the phosphoric acid solution and by the impregnation time or impregnation time of the phosphoric acid solution.
Further, it is preferable that a noble metal such as platinum or palladium is supported on the zeolite catalyst material after the zeolite catalyst material is made to contain P. Specifically, it is preferable that, for example: the zeolite catalyst material is impregnated or impregnated with a phosphoric acid solution, and then calcined, and the zeolite catalyst material impregnated or impregnated with a solution containing noble metals such as platinum and palladium is impregnated or impregnated with a solution containing noble metals such as platinum and palladium, and then calcined.
Since the liquefied petroleum gas obtained using the catalyst for synthesis of liquefied petroleum gas contains a large amount of propane as a component, the liquefied petroleum gas can be suitably used as a fuel that can be stably used even in cold regions.
The present invention is not limited to the above-described embodiments, but can be variously modified within the scope of the present invention including all aspects included in the concepts and claims.
Examples (example)
Next, examples and comparative examples are described, but the present invention is not limited to these examples.
Example 1 ]
(Cu-Zn catalyst substance)
The Cu-Zn catalyst material was a ternary oxide of copper oxide, zinc oxide and aluminum oxide (product name: manufactured by 45776Copper based methanol synthesis catalyst,Alfa Aesar Co.). The Cu-Zn catalyst material was formed into particles (pellet) having a diameter of 20mm and a thickness of about 1mm under a pressure of 5MPa by using a tablet forming machine, and the particles were pulverized in a mortar, and then 300 μm mesh was overlapped with 500 μm mesh to screen a pulverized sample. Thereby, a molded article comprising a Cu-Zn catalyst material having a particle diameter of 300 to 500 μm, a granular shape and a bulk density of 0.9g/cm is obtained 3 。
(MFI type zeolite catalyst substance)
MFI type zeolite (ZSM-5, siO) 2 mol/Al of (2) 2 O 3 Mol=40) 10g was put into an agate mortar, and 0.1334g of chloroplatinic acid hexahydrate was dropped into 7.5758g of 10% hydrochloric acid by a dropper The resulting aqueous solution was mixed with a pestle to homogeneity and impregnated with the aqueous solution for about 1 hour. Then, the mixture was dried at 100℃for 10 hours, and the temperature was raised from room temperature to 500℃in an air atmosphere for 50 minutes, and calcination was carried out at the same temperature for 120 minutes, to obtain a Pt-supported MFI-type zeolite. Then, this sample was set to particles of 20mm diameter and about 1mm thickness using a lozenge shaper, and after pulverizing the particles with a mortar, 300 μm mesh was used overlapping with 500 μm mesh to screen the pulverized sample. Thereby, a molded article comprising a Pt-supported MFI-type zeolite catalyst material having a particle diameter of 300 to 500 μm, a granular shape and a bulk density of 0.8g/cm is obtained 3 。
(production of liquefied Petroleum gas)
The catalyst for synthesis of liquefied petroleum gas is a mixture of the molded body composed of the cu—zn catalyst material obtained in the above and the molded body composed of the MFI-type zeolite catalyst material obtained in the above. The ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the mixed Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is shown in Table 1. M2 is the sum of the mass of the noble metal supported (Pt, pd) and the mass of the MFI-type zeolite catalyst material supporting the noble metal and the mass of P contained when P is contained. Then, a catalyst for synthesis of liquefied petroleum gas was used to produce liquefied petroleum gas under the following conditions.
First, a catalyst for synthesis of liquefied petroleum gas is subjected to a reduction treatment with hydrogen gas. Then, the gas space velocity (GHSV) was set to 2000/h to supply carbon monoxide and hydrogen to the catalyst for synthesizing liquefied petroleum gas. Liquefied petroleum gas is synthesized from carbon monoxide and hydrogen by supplying carbon monoxide and hydrogen to a catalyst for synthesis of liquefied petroleum gas while controlling the temperature (synthesis temperature) to 320 ℃ and the pressure to 5.0 MPa.
In a mixed gas (CO: H) of carbon monoxide and hydrogen 2 =1: 2 (mol ratio)) in the synthesis of liquefied petroleum gas, a fixed bed high pressure flow-through reactor was used. ReactionThe device was made of stainless steel (inner diameter 6.2mm, total length 60 cm). The catalyst was packed in the center of the reactor in a form of being sandwiched in glass wool. The reactor was placed in an electric furnace, and the temperature of the electric furnace was measured by a thermocouple inserted into the center of the furnace and controlled by PID (proportional-integral-derivative). The temperature of the catalyst was measured by a thermocouple inserted into the center of the catalyst layer in the reactor. The catalyst temperature is the synthesis temperature. The reduction treatment of the catalyst for synthesis of liquefied petroleum gas is performed in the following manner: h was introduced into the reactor at 380℃with a flow rate of 40mL/min for the catalyst in the reactor 2 The feed was for 2 hours.
(with respect to filling of the reactor with catalyst)
The catalyst for synthesis of liquefied petroleum gas filled in the reactor may be obtained by physically mixing a cu—zn catalyst material and an MFI zeolite catalyst material in a ratio. Alternatively, only the MFI-type zeolite catalyst material may be filled in the outlet side of the reactor, and a catalyst in which a cu—zn-based catalyst material and the MFI-type zeolite catalyst material are physically mixed may be filled in the inlet side of the reactor. Alternatively, a catalyst in which a cu—zn based catalyst material and an MFI type zeolite catalyst material are physically mixed in a specific ratio may be packed in the outlet side of the reactor, and a catalyst in which a cu—zn based catalyst material and an MFI type zeolite catalyst material are physically mixed in a specific ratio may be packed in the inlet side of the reactor. Alternatively, the MFI-type zeolite catalyst material and the cu—zn-based catalyst material may be filled in a reactor in a multistage manner as follows: the catalyst is produced by filling only the MFI-type zeolite catalyst material on the outlet side of the reactor, then filling a catalyst in which a Cu-Zn-based catalyst material and the MFI-type zeolite catalyst material are physically mixed in a specific ratio, then filling only the MFI-type zeolite catalyst material, and then filling a catalyst in which a Cu-Zn-based catalyst material and the MFI-type zeolite catalyst material are physically mixed in another ratio. Alternatively, a catalyst having a specific ratio of the MFI-type zeolite catalyst material to the cu—zn-based catalyst material and a catalyst having another ratio of the MFI-type zeolite catalyst material to the cu—zn-based catalyst material may be filled in a reactor in a multistage manner as follows: the catalyst is prepared by filling a catalyst in which a Cu-Zn catalyst material and an MFI-type zeolite catalyst material are physically mixed in a specific ratio on the outlet side of a reactor, then filling a catalyst in which a Cu-Zn catalyst material and an MFI-type zeolite catalyst material are physically mixed in another ratio, then filling a catalyst in which a Cu-Zn catalyst material and an MFI-type zeolite catalyst material are physically mixed in a specific ratio, and then filling a catalyst in which a Cu-Zn catalyst material and an MFI-type zeolite catalyst material are physically mixed in another ratio.
(analysis of gas composition)
At a given time point after the start of the reaction (after 6 hours), analysis of the gas was performed using an online connected gas chromatograph. The gas chromatograph used was GC-2014 (Shimadzu corporation). The analysis object and the analysis conditions are described below.
< analysis conditions >
And (3) pipe column: RT-Q-BOND
Heating program: (i) 45 ℃ (hold for 30 min)
(ii) The temperature was raised at 2℃per minute until 175 ℃.
(iii) 175 ℃ (keep 40 min)
Analysis time 135min
[ measurement and evaluation ]
The catalyst for synthesis of liquefied petroleum gas used in examples and comparative examples, and liquefied petroleum gas obtained in the examples and comparative examples were measured and evaluated as follows. The results are shown in tables 1 to 4 and FIGS. 1 to 3. With respect to the drawings, the results of examples 1 to 3 and comparative example 1 are shown in FIG. 1, the results of examples 3 to 5 are shown in FIG. 2, and the results of comparative examples 2 to 5 are shown in FIG. 3. The liquefied petroleum gas is a result measured after 6 hours from the start of the reaction between carbon monoxide and hydrogen.
[1]mol ratio (SiO) 2 mol/Al of (2) 2 O 3 Mol number of (2)
SiO 2 /Al 2 O 3 Ratio (SiO) 2 mol/Al of (2) 2 O 3 Mol) is measured by ICP-OES (inductively coupled plasma optical emission spectroscopy).
[2]With or without Pd and Pt, mass of Pt (M Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) The ratio of the mass (M2) relative to the MFI-type zeolite catalyst material (((M) Pt +M Pd ) /M2). Times.100), and the mass of Pd (M) Pd ) Mass relative to Pt (M Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) Ratio (M) Pd /(M Pt +M Pd ))
Pd and Pt are supported on the MFI-type zeolite catalyst material or not, and the ratio ((M) Pt +M Pd ) (M2). Times.100), and the ratio (M) Pd /(M Pt +M Pd ) Measurement is performed by ICP-OES (inductively coupled plasma optical emission spectroscopy).
[3]With or without P and the content ratio of P (mass (M) of P in MFI-type zeolite catalyst material P ) The ratio ((M) of the mass (M2) relative to the MFI-type zeolite catalyst material P /M2)×100))
The presence or absence of P in the MFI-type zeolite catalyst material and the content ratio of P to the MFI-type zeolite catalyst material were measured by ICP-OES (inductively coupled plasma optical emission spectroscopy).
[4] CO conversion (CO conversion in the figure)
CO conversion [% ] = [ (CO flow at inlet (. Mu.mol/min) -CO flow at outlet (. Mu.mol/min))/CO flow at inlet (. Mu.mol/min) ]. Times.100
The CO conversion represents the ratio of carbon monoxide (CO) in the reaction raw material gas to hydrocarbons and the like.
[5] Yield of propane (C3 yield in the figure)
Yield of propane (Cmol%) = [ (C3 production rate×3) (CO flow rate at inlet) ×106/22400] ×100
C3 production rate is expressed in terms of C. Mu. Mol/min and CO flow at the inlet is expressed in terms of mL (Normal)/min. C3 is propane.
[6] Yield of butane (C4 yield in the figure)
Yield of butane (Cmol%) = [ (C4 production rate×4) (CO flow rate at inlet) ×106/22400] ×100
The unit of the rate of C4 production was C. Mu. Mol/min, and the unit of the CO flow rate at the inlet was mL (Normal)/min. C4 is butane.
[7] Ratio of propane to total of propane and butane (ratio of C3/(C3+C4) in the figure)
The ratio of propane to the sum of propane and butane= [ mol number of propane/(mol number of propane+mol number of butane) ]100
[8] Initial catalyst Activity (initial Performance) of catalyst for liquefied Petroleum gas Synthesis
Ranking of initial performances of the catalyst for liquefied petroleum gas synthesis was performed. Specifically, the LPG yield of the initial performance and the propane yield of the initial performance are ranked on the basis of the following criteria, and the ranking lower of the LPG yield of the initial performance and the propane yield of the initial performance is set as the ranking of the comprehensive judgment of the initial performance. Regarding the comprehensive determination of the initial performance, the class a, the class B, and the class C are qualified, and the class D is unqualified.
< LPG yield of initial Performance (LPG (propane+butane) yield Cmol%) >
A: the yield of liquefied petroleum gas (propane+butane) after 6 hours from the start of the production of liquefied petroleum gas is 30.0Cmol% or more.
B: the yield of liquefied petroleum gas (propane+butane) after 6 hours from the start of the production of liquefied petroleum gas is 25.0Cmol% or more and less than 30.0Cmol%.
C: the yield of liquefied petroleum gas (propane+butane) after 6 hours from the start of the production of liquefied petroleum gas is 20.0Cmol% or more and less than 25.0Cmol%.
D: the yield of liquefied petroleum gas (propane+butane) after 6 hours from the start of the production of liquefied petroleum gas was less than 20.0Cmol%.
< propane yield of initial Performance (propane yield Cmol%) >
A: the propane yield after 6 hours from the start of the production of liquefied petroleum gas was 20.0Cmol% or more.
B: the propane yield after 6 hours from the start of the production of liquefied petroleum gas was 15.0Cmol% or more and less than 20.0Cmol%.
C: the propane yield after 6 hours from the start of the production of liquefied petroleum gas was 10.0Cmol% or more and less than 15.0Cmol%.
D: the propane yield after 6 hours from the start of the production of liquefied petroleum gas was less than 10.0Cmol%.
[9] Catalyst Activity (mid-term Performance) of catalyst for liquefied Petroleum gas Synthesis after 1 week
Ranking of middle-term performance of the catalyst for liquefied petroleum gas synthesis was performed. Grade A, grade B and grade C are qualified, grade D is unqualified.
A: the ratio of the yield of the liquefied petroleum gas after 1 week from the start of the production of the liquefied petroleum gas to the yield (Cmol%) of the liquefied petroleum gas (propane+butane) after 6 hours from the start of the production of the liquefied petroleum gas is 90.0% or more.
B: the ratio of the yield of liquefied petroleum gas after 1 week from the start of production of liquefied petroleum gas to the yield (Cmol%) of liquefied petroleum gas (propane+butane) after 6 hours from the start of production of liquefied petroleum gas is 80.0% or more and less than 90.0%.
C: the ratio of the yield of liquefied petroleum gas after 1 week from the start of production of liquefied petroleum gas to the yield (Cmol%) of liquefied petroleum gas (propane+butane) after 6 hours from the start of production of liquefied petroleum gas is 60.0% or more and less than 80.0%.
D: the ratio of the yield of liquefied petroleum gas after 1 week from the start of production of liquefied petroleum gas to the yield (Cmol%) of liquefied petroleum gas (propane+butane) after 6 hours from the start of production of liquefied petroleum gas was less than 60.0%.
[10] Catalyst Activity (Long term Performance) of catalyst for liquefied Petroleum gas Synthesis after 1 month
Ranking of long-term performance of catalyst for liquefied petroleum gas synthesis was performed. Grade A, grade B and grade C are qualified, grade D is unqualified.
A: the ratio of the yield of the liquefied petroleum gas after 1 month from the start of the production of the liquefied petroleum gas to the yield of the liquefied petroleum gas (Cmol%) after 6 hours from the start of the production of the liquefied petroleum gas is 90.0% or more.
B: the ratio of the yield of the liquefied petroleum gas after 1 month of starting the production of the liquefied petroleum gas to the yield of the liquefied petroleum gas (Cmol%) after 6 hours of starting the production of the liquefied petroleum gas is 80.0% or more and less than 90.0%.
C: the ratio of the yield of the liquefied petroleum gas after 1 month of starting the production of the liquefied petroleum gas to the yield of the liquefied petroleum gas (Cmol%) after 6 hours of starting the production of the liquefied petroleum gas is 60.0% or more and less than 80.0%.
D: the ratio of the yield of liquefied petroleum gas after 1 month of starting the production of liquefied petroleum gas to the yield of liquefied petroleum gas (Cmol%) after 6 hours of starting the production of liquefied petroleum gas is less than 60.0%.
Example 2 ]
The same operations as in example 1 were performed except that an aqueous solution obtained by dissolving 0.0667g of chloroplatinic acid hexahydrate and 0.0419g of palladium chloride in 7.5758g of 10% hydrochloric acid was used instead of an aqueous solution obtained by dissolving 0.1334g of chloroplatinic acid hexahydrate in 7.5758g of 10% hydrochloric acid.
Example 3 ]
The same operations as in example 1 were performed except that an aqueous solution obtained by dissolving 0.0419g of chloroplatinic acid hexahydrate and 0.0574g of palladium chloride in 7.5758g of 10% hydrochloric acid was used instead of an aqueous solution obtained by dissolving 0.1334g of chloroplatinic acid hexahydrate in 7.5758g of 10% hydrochloric acid.
Comparative example 1]
The same operations as in example 1 were carried out except that an aqueous solution in which 0.0837g of palladium chloride was dissolved in 7.5758g of 10% hydrochloric acid was used instead of an aqueous solution in which 0.1334g of chloroplatinic acid hexahydrate was dissolved in 7.5758g of 10% hydrochloric acid.
< example 4 and 5>
The same operations as in example 3 were performed except that the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material was set to the values in Table 1.
Comparative examples 2 to 5 ]
Except for the use of beta zeolite (SiO 2 mol/Al of (2) 2 O 3 Molar number=40) substituted MFI zeoliteThe same operations as in examples 1 to 3 and comparative example 1 were performed in the rest.
TABLE 1
/>
As shown in tables 1 and 1 to 3, examples 1 to 6 contained a cu—zn catalyst material and an MFI-type zeolite catalyst material supporting Pt, and the ratio (M1/(m1+m2)) of the mass (M1) of the cu—zn catalyst material to the total mass (M2) of the mass (M1) of the cu—zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material was in the range of 0.30 to 0.95 inclusive, while the yield of propane was high even though the synthesis temperature was 320 ℃. In comparative examples 2 to 5, zeolite beta was used, and the ratio of propane to the total of propane and butane in examples 1 to 6 was higher than in comparative examples 2 to 5. Further, regarding the mass ratio M shown in FIG. 1 Pd /(M Pt +M Pd ) In examples 2 to 3, the butane yield of examples 2 to 3 was higher than that of example 1, while the butane yield of examples 2 to 3 was outside the range of 0.15 to 0.70. On the other hand, comparative example 1, in which Pd was supported and Pt was not supported, used zeolite beta in comparative examples 2 to 5, and propane yield was low. Furthermore, the CO conversion rates of the examples and comparative examples were 80% or more, and the CO was sufficiently reacted.
Example 6 ]
Except that MFI type zeolite (ZSM-5, siO) 2 mol/Al of (2) 2 O 3 Mol number=40) of the mixture was put into an agate mortar, and an aqueous solution in which 0.6456g of orthophosphoric acid was dissolved in 6.000g of pure water was added dropwise thereto with a dropper, and the mixture was mixed uniformly with a pestle and impregnated with the aqueous solution for about 1 hour, and then dried at 100 ℃ for 10 hours, and heated from room temperature to 500 ℃ in an air atmosphere for 50 minutes, and calcined at the same temperature for 120 minutes, and then an aqueous solution in which 0.0419g of chloroplatinic acid hexahydrate and 0.0574g of palladium chloride were dissolved in 7.5758g of 10% hydrochloric acid were added dropwise thereto with a dropper, and the other steps were performed in the same manner as in example 3.
Example 7 ]
(Cu-Zn catalyst substance)
Solution A was prepared by dissolving 95.13g of copper nitrate trihydrate, 49.73g of zinc nitrate hexahydrate, 19.33g of aluminum nitrate nonahydrate, and 5.31g of zirconium nitrate dihydrate in 584g of distilled water. In addition, 148g of anhydrous sodium carbonate was dissolved in 2000g of distilled water to prepare solution B.
500g of distilled water was put into 5000mL of a separate flask equipped with a stirrer, and heated in a hot water bath so that the water temperature became 65 ℃. After that, the speed of the liquid feeding pump was set so that the addition was completed within 70 minutes, and then the total amount of liquid a and 900mL of liquid B were added dropwise to the above-described separate flask. The mixture was stirred vigorously with a stirrer during the dropwise addition. The temperature of the precipitation slurry was adjusted by a hot water bath at any time so that the temperature became 65 ℃. The pH after the completion of the dropwise addition of the solutions A and B was about 5.6. Then, the remaining solution B was slowly dropped so that the pH became 6.5. After the pH was 6.5, the precipitate slurry was vigorously stirred at 65℃for 2 hours. The pH after 2 hours was about 7.2.
The precipitated slurry is then transferred to a suction filtration device for filtration to obtain a precipitated cake. The resulting precipitated filter cake was rinsed 20 times with 250mL of distilled water, and Na ions were removed from the precipitated filter cake.
After rinsing, the precipitated filter cake was transferred to an evaporation dish and dried in a drying oven at 120 ℃ for 12 hours. Then, the temperature was raised to 350℃at a rate of 10℃per minute in a calciner, and the resultant calcined product was calcined at 350℃for 2 hours, and then sufficiently pulverized in an agate mortar to obtain a powder. The powder was formed into particles having a diameter of 20mm and a thickness of about 1mm under a pressure of 5MPa using a tablet forming machine, and the particles were pulverized in a mortar, and then 300 μm mesh was overlapped with 500 μm mesh to screen a pulverized sample. Thereby, a molded article comprising a Cu-Zn catalyst material having a particle diameter of 300 to 500 μm, a granular shape and a bulk density of 0.9g/cm is obtained 3 。
The Cu-Zn catalyst material is composed of copper oxide (CuO), zinc oxide (ZnO), zirconium oxide (ZrO 3) and oxygenAluminum (Al) 2 O 3 ) The chemical composition was 62.7 mass% of copper oxide, 27.3 mass% of zinc oxide, 5.0 mass% of zirconium oxide, and 5.3 mass% of aluminum oxide.
(MFI type zeolite catalyst substance)
MFI type zeolite (ZSM-5, siO) 2 mol/Al of (2) 2 O 3 Mol=40) 36g was put into an agate mortar, and an aqueous solution of 2.3241g of orthophosphoric acid dissolved in 21.6g of pure water was added dropwise thereto with a dropper, and mixed uniformly with a pestle, and it took about 1 hour to impregnate. Then, it was dried at 100℃for 10 hours, and heated from ordinary temperature up to 500℃in an air atmosphere for 50 minutes, and calcined at the same temperature for 120 minutes.
30g of the calcined P-containing MFI zeolite was charged into an agate mortar, and an aqueous solution prepared by dissolving 0.4002g of chloroplatinic acid hexahydrate in 22.7274g of 10% hydrochloric acid was added dropwise thereto with a dropper, and the mixture was mixed uniformly with a pestle and impregnated for about 1 hour. Then, the mixture was dried at 100℃for 10 hours, and the temperature was raised from room temperature to 500℃in an air atmosphere for 50 minutes, and calcination was carried out at the same temperature for 120 minutes, to obtain a Pt-supporting MFI-type zeolite containing P. Then, this sample was set to particles of 20mm diameter and about 1mm thickness using a lozenge shaper, and after pulverizing the particles with a mortar, 300 μm mesh was used overlapping with 500 μm mesh to screen the pulverized sample. Thereby, a molded article comprising a P-containing and Pt-supporting MFI-type zeolite catalyst material having a particle diameter of 300 to 500 μm, a granular shape and a bulk density of 0.8g/cm is obtained 3 。
The chemical composition of the MFI type zeolite catalyst material is as follows: platinum 0.5% by mass (M Pt 0.50 mass% of/M2). Times.100, 2.0 mass% of phosphorus (M) P 2.0 mass% of/M2). Times.100, the remainder being ZSM-5.
(production of liquefied Petroleum gas)
The catalyst for synthesis of liquefied petroleum gas is a mixture of the molded body composed of the cu—zn catalyst material obtained in the above and the molded body composed of the MFI-type zeolite catalyst material obtained in the above. The catalyst is mixed such that the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the mixed Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material is 0.80. M2 is the sum of the mass of the supported noble metal (Pt) and the mass of the MFI-type zeolite catalyst material supporting the noble metal (Pt) and the mass of P. Then, a catalyst for synthesis of liquefied petroleum gas was used to produce liquefied petroleum gas under the following conditions.
First, a catalyst for synthesis of liquefied petroleum gas is subjected to a reduction treatment with hydrogen gas. Then, the gas space velocity (GHSV) was set to 750/h to supply carbon monoxide and hydrogen to the catalyst for liquefied petroleum gas synthesis. Liquefied petroleum gas is synthesized from carbon monoxide and hydrogen by supplying carbon monoxide and hydrogen to a catalyst for synthesis of liquefied petroleum gas while controlling the temperature (synthesis temperature) to 320 ℃ and the pressure to 5.0 MPa.
In a mixed gas (CO: H) of carbon monoxide and hydrogen 2 =1: 2 (mol ratio)) in the synthesis of liquefied petroleum gas, a fixed bed high pressure flow-through reactor was used. The reactor was made of stainless steel (inner diameter 6.2mm, total length 60 cm). The catalyst was packed in the center of the reactor in a form of being sandwiched in glass wool. The reactor was placed in an electric furnace, and the temperature of the electric furnace was measured by a thermocouple inserted into the center of the furnace and controlled by PID (proportional-integral-derivative). The temperature of the catalyst was measured by a thermocouple inserted into the center of the catalyst layer in the reactor. The catalyst temperature is the synthesis temperature. The reduction treatment of the catalyst for synthesis of liquefied petroleum gas is performed in the following manner: h was introduced into the reactor at 380℃with a flow rate of 40mL/min for the catalyst in the reactor 2 The feed was for 2 hours.
(analysis of gas composition)
At a given time point (after 6 hours, after 1 week, after 1 month) after the start of the reaction, analysis of the gas was performed using an online connected gas chromatograph. The gas chromatograph used was GC-2014 (Shimadzu corporation). The analysis object and the analysis conditions are described below.
< analysis conditions >
And (3) pipe column: RT-Q-BOND
Heating program: (i) 45 ℃ (hold for 30 min)
(ii) The temperature was raised at 2℃per minute until 175 ℃.
(iii) 175 ℃ (keep 40 min)
Analysis time 135min
[ measurement and evaluation ]
The catalyst for synthesis of liquefied petroleum gas and the liquefied petroleum gas obtained in the examples and comparative examples were evaluated for performance in the same manner as described above.
Example 8 ]
The same operations as in example 7 were carried out, except that a specific catalyst was used and the temperature (synthesis temperature) was set to 310 ℃, which was: a catalyst was used in which a mixture of a molded body composed of a cu—zn catalyst material and a molded body composed of an MFI-type zeolite catalyst material was used in the same manner as in example 7, and the catalyst was mixed so that the ratio (M1/(m1+m2)) of the mass (M1) of the cu—zn catalyst material to the total mass of the mass (M1) of the mixed cu—zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material was 0.78.
Example 9 ]
The same operations as in example 7 were carried out except that a specific catalyst was used, a catalyst of MFI type zeolite catalyst material alone was filled in the lower stage of the reactor and a mixed catalyst was filled in the upper stage after silica wool (silica wool) was inserted, and the temperature (synthesis temperature) was set to 300 c, and the specific catalyst was: a mixture of a molded body composed of a cu—zn catalyst material and a molded body composed of an MFI-type zeolite catalyst material was used as in example 7, and a catalyst (mixed catalyst) and an MFI-type zeolite catalyst material were mixed so that the ratio (M1/(m1+m2)) of the mass (M1) of the cu—zn catalyst material to the total mass (M2) of the mass (M1) of the mixed cu—zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material became 0.72.
Example 10 ]
The same operations as in example 7 were carried out except that a specific catalyst was used, a catalyst of MFI-type zeolite catalyst material alone was filled in the lower stage of the reactor and quartz wool was inserted, a mixed catalyst was filled in the upper stage, and the temperature (synthesis temperature) was set to 300 ℃. A mixture of a molded body composed of a cu—zn catalyst material and a molded body composed of an MFI-type zeolite catalyst material was used as in example 7, and a catalyst (mixed catalyst) and an MFI-type zeolite catalyst material were mixed so that the ratio (M1/(m1+m2)) of the mass (M1) of the cu—zn catalyst material to the total mass (M2) of the mass (M1) of the mixed cu—zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material became 0.64, and a catalyst of the MFI-type zeolite catalyst material alone.
Example 11 ]
Except that a specific catalyst was used and the temperature (synthesis temperature) was set at 280℃and GHSV was set at 1000h -1 The same operations as in example 7 were carried out except that the specific catalyst was as follows: a catalyst was used in which a mixture of a molded body composed of a cu—zn catalyst material and a molded body composed of an MFI-type zeolite catalyst material was used in the same manner as in example 7, and the catalyst was mixed so that the ratio (M1/(m1+m2)) of the mass (M1) of the cu—zn catalyst material to the total mass of the mass (M1) of the mixed cu—zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material was 0.50.
Example 12 ]
(Cu-Zn catalyst substance)
The Cu-Zn catalyst material was a ternary oxide of copper oxide, zinc oxide and aluminum oxide (product name: manufactured by 45776Copper based methanol synthesis catalyst,Alfa Aesar Co.). The Cu-Zn catalyst material was formed into particles having a diameter of 20mm and a thickness of about 1mm under a pressure of 5MPa by using a tablet-forming machine, and the particles were pulverized in a mortar, and then 300 μm mesh was overlapped with 500 μm mesh to screen the pulverized sample. Thereby, a molded article comprising the Cu-Zn catalyst material is obtained,the molded article has a particle diameter of 300 to 500 μm, a granular shape and a bulk density of 0.9g/cm 3 。
The Cu-Zn catalyst material is composed of copper oxide (CuO), zinc oxide (ZnO), magnesium oxide (MgO) and aluminum oxide (Al) 2 O 3 ) The chemical composition was 63.5 mass% of copper oxide, 25.0 mass% of zinc oxide, 1.5 mass% of magnesium oxide, and 10.0 mass% of aluminum oxide.
(MFI type zeolite catalyst substance)
MFI type zeolite (ZSM-5, siO) 2 mol/Al of (2) 2 O 3 Mol=40) 12g was put into an agate mortar, and an aqueous solution of 0.3834g of orthophosphoric acid dissolved in 7.2000g of pure water was added dropwise thereto with a dropper, and mixed uniformly with a pestle and impregnated with the aqueous solution for about 1 hour, and then dried at 100 ℃ for 10 hours, and heated from normal temperature to 500 ℃ in 50 minutes in an air atmosphere, and calcined at the same temperature for 120 minutes.
10g of the calcined P-containing MFI-type zeolite was charged into an agate mortar, and an aqueous solution prepared by dissolving 0.0419g of chloroplatinic acid hexahydrate and 7.5758g of palladium chloride in 10% hydrochloric acid was added dropwise thereto with a dropper, and the mixture was mixed uniformly with a pestle and impregnated for about 1 hour. Then, the mixture was dried at 100℃for 10 hours, and the temperature was raised from room temperature to 500℃in an air atmosphere for 50 minutes, and calcination was carried out at the same temperature for 120 minutes, to obtain an MFI-type zeolite containing P and supported with Pt and Pd. Then, this sample was set to particles of 20mm diameter and about 1mm thickness using a lozenge shaper, and after pulverizing the particles with a mortar, 300 μm mesh was used overlapping with 500 μm mesh to screen the pulverized sample. Thereby, a molded article comprising an MFI-type zeolite catalyst material containing P and supporting Pt and Pd, having a particle diameter of 300 to 500 μm, a granular shape and a bulk density of 0.8g/cm 3 。
The chemical composition of the MFI type zeolite catalyst material is as follows: platinum 0.16 mass% + palladium 0.34 ((M) Pt +M Pd ) 0.50 mass% of/M2). Times.100, 2.0 mass% of phosphorus (M) P 2.0 mass% of/M2). Times.100, the remainder being ZSM- 5。
(production of liquefied Petroleum gas)
The catalyst for synthesis of liquefied petroleum gas is a mixture of the molded body composed of the cu—zn catalyst material obtained in the above and the molded body composed of the MFI-type zeolite catalyst material obtained in the above. A catalyst was used in which the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass (M2) of the mass (M1) of the mixed Cu-Zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material was 0.50, the temperature (synthesis temperature) was 320℃and the GHSV was 2000h -1 . Otherwise, the same operations as in example 7 were performed. The evaluation was carried out for 25 days.
Comparative example 6 ]
The same operations as in example 12 were carried out, except that a specific catalyst was used and the temperature (synthesis temperature) was set to 320 ℃, which was: a catalyst was used which was obtained by mixing a mixture of a molded article composed of a cu—zn catalyst material and a molded article composed of an MFI-type zeolite catalyst material in the same manner as in example 12, so that the ratio (M1/(m1+m2)) of the mass (M1) of the cu—zn catalyst material to the total mass of the mass (M1) of the mixed cu—zn catalyst material and the mass (M2) of the MFI-type zeolite catalyst material was 0.20.
TABLE 2
TABLE 3
TABLE 4
As is clear from tables 1 to 4 and fig. 4 to 5, if the ratio (M1/(m1+m2)) is increased, the middle-term performance and the long-term performance of the catalyst for liquefied petroleum gas synthesis can be improved. In particular, the catalysts for synthesis of liquefied petroleum gas of examples 7 to 12 are less likely to deteriorate at a temperature of about 320 ℃ and can stably produce propane for a long period of time.
Claims (12)
1. A catalyst for synthesis of liquefied petroleum gas, comprising:
a Cu-Zn-based catalyst material; and
An MFI-type zeolite catalyst material carrying Pt; and, in addition, the processing unit,
the ratio (M1/(M1+M2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass (M2) of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI zeolite catalyst material is 0.30 to 0.95.
2. The catalyst for synthesis of liquefied petroleum gas according to claim 1, wherein a ratio (M1/(m1+m2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI zeolite catalyst material is 0.30 or more and less than 0.70.
3. The catalyst for synthesis of liquefied petroleum gas according to claim 1, wherein a ratio (M1/(m1+m2)) of the mass (M1) of the Cu-Zn catalyst material to the total mass of the mass (M1) of the Cu-Zn catalyst material and the mass (M2) of the MFI zeolite catalyst material is 0.50 to 0.95.
4. The catalyst for synthesis of liquefied petroleum gas according to any one of claims 1 to 3, wherein the MFI-type zeolite catalyst material carries Pt alone.
5. The catalyst for synthesis of liquefied petroleum gas according to any one of claims 1 to 3, wherein the MFI-type zeolite catalyst material further carries Pd.
6. According to the weightsThe catalyst for synthesis of liquefied petroleum gas according to claim 5, wherein Pd supported on the MFI-type zeolite catalyst material has a mass (M Pd ) Mass relative to Pt (M Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) Ratio (M) Pd /(M Pt +M Pd ) 0.70 or less.
7. The catalyst for synthesis of liquefied petroleum gas according to claim 5 or 6, wherein the mass (M2) of Pt in the MFI-type zeolite catalyst material is equal to the mass (M2 Pt ) Mass to Pd (M Pd ) Is the total mass (M) Pt +M Pd ) Is 0.1 mass% or more and 1.0 mass% or less.
8. The catalyst for synthesis of liquefied petroleum gas according to any one of claims 1 to 7, wherein the Cu-Zn catalyst material and the MFI-type zeolite catalyst material are present independently of each other,
the Cu-Zn catalyst material and the MFI-type zeolite catalyst material are both a powder or a molded body.
9. A method for producing liquefied petroleum gas, comprising:
a reduction treatment step of subjecting the catalyst for liquefied petroleum gas synthesis described in any one of claims 1 to 8 to a reduction treatment;
a supply step of supplying carbon monoxide and hydrogen to the catalyst for synthesizing liquefied petroleum gas after the reduction treatment in the reduction treatment step; and
And a synthesis step of synthesizing liquefied petroleum gas by reacting carbon monoxide and hydrogen supplied in the supply step with the catalyst for synthesizing liquefied petroleum gas after the reduction treatment.
10. The method for producing liquefied petroleum gas according to claim 9, wherein in the step of supplying, a gas space velocity (GHSV) at which carbon monoxide and hydrogen are supplied is 300/h or more and 20000/h or less.
11. The method for producing liquefied petroleum gas according to claim 9 or 10, wherein in the synthesis step, carbon monoxide and hydrogen are reacted at a temperature of 260 ℃ or higher and 360 ℃ or lower.
12. The method for producing liquefied petroleum gas according to any one of claims 9 to 11, wherein in the aforementioned synthesis step, carbon monoxide and hydrogen are reacted at a pressure of 2.0MPa to 6.0 MPa.
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| JP2021-111072 | 2021-07-02 | ||
| JP2022-067955 | 2022-04-15 | ||
| JP2022067955 | 2022-04-15 | ||
| PCT/JP2022/026507 WO2023277187A1 (en) | 2021-07-02 | 2022-07-01 | Catalyst for synthesizing liquefied petroleum gas and method for producing liquefied petroleum gas |
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