CN115703068B - Spherical isobutane dehydrogenation catalyst and preparation method and application thereof - Google Patents
Spherical isobutane dehydrogenation catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN115703068B CN115703068B CN202110914004.0A CN202110914004A CN115703068B CN 115703068 B CN115703068 B CN 115703068B CN 202110914004 A CN202110914004 A CN 202110914004A CN 115703068 B CN115703068 B CN 115703068B
- Authority
- CN
- China
- Prior art keywords
- spherical
- hms
- dehydrogenation catalyst
- isobutane dehydrogenation
- composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 246
- 239000003054 catalyst Substances 0.000 title claims abstract description 157
- 239000001282 iso-butane Substances 0.000 title claims abstract description 123
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 89
- 229910052751 metal Inorganic materials 0.000 claims abstract description 70
- 239000002184 metal Substances 0.000 claims abstract description 70
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000002808 molecular sieve Substances 0.000 claims abstract description 55
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 55
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 49
- 239000010703 silicon Substances 0.000 claims abstract description 47
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 42
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000002243 precursor Substances 0.000 claims abstract description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 62
- 239000003921 oil Substances 0.000 claims description 54
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 238000000498 ball milling Methods 0.000 claims description 37
- 229910021529 ammonia Inorganic materials 0.000 claims description 32
- 150000003839 salts Chemical class 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 239000012265 solid product Substances 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 21
- 239000012752 auxiliary agent Substances 0.000 claims description 21
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 19
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 239000011135 tin Substances 0.000 claims description 14
- 229910052718 tin Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920000428 triblock copolymer Polymers 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 239000002736 nonionic surfactant Substances 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims description 2
- 229910001593 boehmite Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 2
- 229940057995 liquid paraffin Drugs 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 229940024546 aluminum hydroxide gel Drugs 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 239000012847 fine chemical Substances 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000001914 filtration Methods 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
- 230000005484 gravity Effects 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000009257 reactivity Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004231 fluid catalytic cracking Methods 0.000 description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000002383 small-angle X-ray diffraction data Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000012798 spherical particle Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
- 101000880960 Homo sapiens Desmocollin-3 Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 229910017299 Mo—O Inorganic materials 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 125000000123 silicon containing inorganic group Chemical group 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to the field of fine chemical engineering, and discloses a spherical isobutane dehydrogenation catalyst and a preparation method and application thereof. The catalyst comprises Al 2 O 3 -HMS composite spherical support, active metal component supported on the composite spherical support; the composite spherical carrier comprises an alumina precursor and an HMS full-silicon mesoporous molecular sieve, wherein the specific surface area of the HMS full-silicon mesoporous molecular sieve is 700-1300m 2 Per gram, pore volume of 0.7-1.3cm 3 /g, average pore size of 2-5nm; and the content of the composite spherical carrier is 95-99.9 wt% and the content of the active metal component is 0.1-1 wt% based on the total weight of the catalyst. The catalyst not only has higher mechanical strength and better particle surface uniformity, but also can obtain better dehydrogenation activity, selectivity, stability and carbon deposit resistance in the reaction of preparing isobutene by isobutane dehydrogenation.
Description
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a spherical isobutane dehydrogenation catalyst and a preparation method thereof, and application of the catalyst in a reaction for preparing isobutene by isobutane dehydrogenation.
Background
Isobutene is an important organic chemical raw material, and is mainly used for preparing various organic raw materials and fine chemicals such as methyl tertiary butyl ether, butyl rubber, methyl ethyl ketone, polyisobutylene, methyl methacrylate, isoprene, tert-butylphenol, tert-butylamine, 1, 4-butanediol, ABS resin and the like. The main sources of isobutene are the by-product C4 fraction from the ethylene plant by steam cracking of naphtha, the by-product C4 fraction from the Fluid Catalytic Cracking (FCC) plant and the by-product tert-butanol (TAB) from the synthesis of epoxyisobutane by the Halcon process. In recent years, along with the development and utilization of products downstream of isobutene, the demand of isobutene is increased year by year, and the traditional isobutene production cannot meet the huge demand of isobutene in the chemical industry, so that the research and development work of new technology of isobutene production becomes a great hotspot in the chemical industry. Among the most competitive technologies are isobutane dehydrogenation, n-butene skeletal isomerization, and the production of isobutene by new FCC units. Among these methods, the reaction of directly dehydrogenating isobutane to prepare isobutene has been studied earlier, and industrial production has been achieved. China has abundant C4 resources, but the chemical utilization rate of C4 fractions in China is lower, most isobutane is directly used as fuel, and the waste is serious. The reasonable utilization of C4 resources is an urgent task facing the field of petrochemical engineering research. Therefore, the preparation of isobutene by isobutane dehydrogenation has great development prospect in China.
The catalysts for preparing isobutene by isobutane dehydrogenation mainly have two types: oxide catalysts and noble metal catalysts. The oxide catalyst mainly comprises Cr 2 O 3 、V 2 O 5 、Fe 2 O 3 、MoO 3 ZnO, etc., and their composite oxides V-Sb-O, V-Mo-O, ni-V-O, V-Nb-O, cr-Ce-O, molybdate, etc. Oxide catalysts are less expensive than noble metal catalysts. However, the catalyst is easy to accumulate carbon, and has low catalytic activity, selectivity and stability. In addition, most oxide catalysts contain components with high toxicity, which is not beneficial to environmental protection. Dehydrogenation studies on noble metal catalysts have been a long history, and noble metal catalysts have higher activity, better selectivity, and are more environmentally friendly than other metal oxide catalysts. The process for preparing olefin Oleflex by dehydrogenating low-carbon alkane developed by UOP company in the United states has been industrially applied in the beginning of the 90 th century. The process adopts 3-4 series adiabatic moving bed reactors, and the catalyst used is spherical alumina supported Pt DeH series catalyst. In order to meet the special requirements of the moving bed production mode, the DeH catalyst has extremely severe performance requirements on spherical alumina. The molding method of the industrial spherical alumina carrier mainly comprises a rolling ball method and an oil column method. The surface uniformity degree, the particle strength after high-temperature treatment and the particle sphericity of the alumina carrier obtained by the ball method can not meet the requirements of a moving bed process. Thus, UOP corporation used the oil column forming method to prepare spherical alumina supports. However, alumina has too many surface hydroxyl groups and too strong acidity, and the use of such a carrier for preparing propane dehydrogenation catalysts is prone to carbon deposition on the catalyst surface during the reaction, thereby leading to rapid deactivation.
Thus, the catalytic properties of heterogeneous catalysts, such as activity, selectivity and stability, depend on both the catalytic characteristics of the active components and on the structure of the catalyst support. Therefore, it is urgent to develop a noble metal-based isobutane dehydrogenation catalyst to obtain a high-quality spherical support.
Disclosure of Invention
The invention aims to overcome the defects of complex preparation process, higher production cost, lower production efficiency, uneven surface of spherical particles and low mechanical strength and abrasion strength of the spherical particles of the conventional isobutane dehydrogenation catalyst carrier, and provides a spherical isobutane dehydrogenation catalyst, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides a spherical isobutane dehydrogenation catalyst, wherein the spherical isobutane dehydrogenation catalyst comprises Al 2 O 3 -HMS composite spherical support and supported on said Al 2 O 3 -an active metal component on a HMS composite spherical support; wherein the Al is 2 O 3 The HMS composite spherical carrier comprises an alumina precursor and an HMS all-silicon mesoporous molecular sieve, wherein the specific surface area of the HMS all-silicon mesoporous molecular sieve is 700-1300m 2 Per gram, pore volume of 0.7-1.3cm 3 /g, average pore size of 2-5nm; and based on the total weight of the catalyst, the Al 2 O 3 -HMS composite spherical support in a content of 95-99.9 wt% and said active metal component in a content of 0.1-1 wt%.
The second aspect of the invention provides a preparation method of the spherical isobutane dehydrogenation catalyst, wherein the method comprises the following steps: al is added with 2 O 3 The HMS composite spherical carrier is contacted with an aqueous solution of acid or salt containing active metal components, an optional aqueous solution of salt containing a first metal auxiliary agent and an optional aqueous solution of salt containing a second metal auxiliary agent for reaction, and then solid products are obtained after separation, and the solid products are dried and roasted to obtain the spherical isobutane dehydrogenation catalyst.
The third aspect of the invention provides an application of the spherical isobutane dehydrogenation catalyst in the reaction of preparing isobutene by isobutane dehydrogenation.
Through the technical scheme, compared with the prior art, the technical scheme provided by the invention has the following advantages:
(1) The spherical isobutane dehydrogenation catalyst has the advantages of good sphericity, smooth and uniform surface, uniform size, high mechanical strength of particles and high abrasion strength.
(2) The preparation method of the spherical isobutane dehydrogenation catalyst has the advantages of simple process, high yield, low preparation cost and good preparation repeatability.
(3) The spherical isobutane dehydrogenation catalyst can be used as an isobutene preparation catalyst for isobutane dehydrogenation, not only can each performance index completely meet the requirements of a moving bed process, but also has good dehydrogenation activity, high isobutene selectivity, low carbon deposition and good catalyst stability.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
FIG. 1 is a small angle XRD spectrum of HMS all-silicon mesoporous molecular sieve A of the present invention;
FIG. 2 is an Al layer prepared in example 1 of the present invention 2 O 3 -small angle XRD spectrum of HMS composite spherical support a;
FIG. 3 is an Al layer prepared in example 1 of the present invention 2 O 3 -wide angle XRD spectrum of HMS composite spherical carrier a;
FIG. 4 is an Al layer prepared in example 1 of the present invention 2 O 3 -pore size distribution profile of HMS composite spherical support a.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the invention provides a spherical isobutane dehydrogenation catalyst, wherein the spherical isobutane dehydrogenation catalyst comprises Al 2 O 3 -HMS composite spherical support and supported on said Al 2 O 3 -an active metal component on a HMS composite spherical support; wherein the Al is 2 O 3 The HMS composite spherical carrier comprises an alumina precursor and HMS full siliconMesoporous molecular sieve, wherein the specific surface area of the HMS all-silicon mesoporous molecular sieve is 700-1300m 2 Per gram, pore volume of 0.7-1.3cm 3 /g, average pore size of 2-5nm; and based on the total weight of the catalyst, the Al 2 O 3 -HMS composite spherical support in a content of 95-99.9 wt% and said active metal component in a content of 0.1-1 wt%.
The inventors of the present invention found that: the carrier structure of noble metal catalyst (including physical structure such as specific surface area, pore volume, pore diameter distribution, etc. and chemical structure such as surface acidity position, electronic property, etc.) has important influence on the dispersity of the supported active metal component, and also directly influences mass transfer and diffusion in the reaction process. Thus, the catalytic properties such as activity, selectivity and stability of heterogeneous catalysts depend on both the catalytic characteristics of the active components and on the characteristics of the catalyst support. Most commercially available activated alumina has too many surface hydroxyl groups and too much acidity. The alumina is used as a carrier for preparing a dehydrogenation catalyst, and carbon is easy to accumulate on the surface of the catalyst in the reaction process, so that the catalyst is deactivated rapidly.
Under the condition of unchanged raw materials and formulas, different molding methods and processes of the catalyst or the catalyst carrier often lead to different use effects of the catalyst. The moving bed Oleflex technology developed by UOP company in the United states is used for preparing low-carbon olefin by dehydrogenation of low-carbon alkane, and the DeH series of catalysts used are Pt-based catalysts supported on spherical alumina carriers. In order to match the production characteristics of the moving bed process, deH series of catalysts have extremely severe performance requirements on spherical alumina, and specific parameters are as follows: the diameter of the spherical alumina particles is 1.5-1.9mm, the average particle diameter is 1.6-1.8mm, the bulk density is 0.58-0.65g/ml, the average particle strength is higher than 25N, and the specific surface area is higher than 80m 2 And/g, the pore volume is between 0.5 and 0.7 ml/g. The molding method of the industrial spherical alumina carrier in the prior art mainly comprises a rolling ball method and an oil column method. The surface of the alumina carrier obtained by the rolling ball method is not uniform enough, the mechanical strength of the particles after high-temperature treatment is poor, and the performances such as bulk density, abrasion strength and the like can not meet the indexes of the moving bed process requirement.
In order to solve the above problems, the inventors of the present invention found that: the all-silicon mesoporous molecular sieve has large specific surface area and pore volume, does not contain strong acid groups on the surface, and is suitable for being used as a carrier of an isobutane dehydrogenation catalyst. However, mesoporous molecular sieves have poor viscosity, are difficult to form, and are difficult to apply to industrial production. And if the HMS all-silicon mesoporous molecular sieve is compounded with an alumina material with better viscosity, the standard spherical carrier can be prepared by an oil ammonia column forming method. And further loading an active metal component, an optional first metal auxiliary agent and an optional second metal auxiliary agent to obtain the spherical isobutane dehydrogenation catalyst with excellent performance. The catalyst not only has higher mechanical strength and better particle surface uniformity, but also can obtain better dehydrogenation activity, selectivity, stability and carbon deposit resistance in the reaction of preparing isobutene by isobutane dehydrogenation.
According to the present invention, preferably, the Al is based on the total weight of the spherical isobutane dehydrogenation catalyst 2 O 3 -the content of HMS composite spherical support is 97-99.5 wt%, the content of active metal component is 0.2-0.5 wt%; more preferably, the Al is based on the total weight of the spherical isobutane dehydrogenation catalyst 2 O 3 -HMS composite spherical support in a content of 98-99 wt% and said active metal component in a content of 0.2-0.4 wt%. In the present invention, the Al 2 O 3 The content of the HMS composite spherical carrier and the content of the active metal component are limited to be within the range, so that the prepared catalyst can obtain better dehydrogenation activity, selectivity, stability and carbon deposit resistance in the reaction of preparing isobutene by dehydrogenating isobutane.
According to the present invention, the active metal component is selected from one or more of platinum, palladium and ruthenium; preferably, the active metal component is platinum.
According to the invention, the spherical isobutane dehydrogenation catalyst further comprises an alumina supported on the Al 2 O 3 -a first metal promoter and a second metal promoter on a HMS composite spherical support; and/or, based on the total weight of the spherical isobutane dehydrogenation catalyst, the first metal promoter The content is 0 to 3 wt%, preferably 0.1 to 2.0 wt%, in terms of metal element; the content of the second metal auxiliary agent is 0-2 wt%, preferably 0.1-1.2 wt% calculated by metal element; in the invention, the contents of the first metal auxiliary agent and the second metal auxiliary agent are limited to be within the range, so that the prepared catalyst can obtain better dehydrogenation activity, selectivity, stability and carbon deposit resistance in the reaction of preparing isobutene by dehydrogenating isobutane.
According to the invention, the first metal auxiliary is selected from one or more of tin, zinc, calcium, iron, lanthanum, cobalt and manganese; preferably, the first metal auxiliary is selected from one or more of tin, zinc, iron and lanthanum; and/or the second metal auxiliary agent is selected from one or more of sodium, potassium, lithium and strontium; preferably, the second metal promoter is selected from sodium and/or potassium.
According to the invention, the Al 2 O 3 The specific surface area of the HMS composite spherical carrier is 400-900m 2 Per gram, pore volume of 0.4-1cm 3 Per gram, bulk density of 0.5-0.7g/ml, average particle diameter of 1-3mm, average particle strength of 20-80N; preferably, the Al 2 O 3 The specific surface area of the HMS composite spherical carrier is 500-750m 2 Per gram, pore volume of 0.5-0.8cm 3 Per gram, bulk density of 0.53-0.68g/ml, average particle diameter of 1.2-2.0mm, average particle strength of 25-70N; more preferably, the Al 2 O 3 The specific surface area of the HMS composite spherical carrier is 539-647m 2 Per gram, pore volume of 0.61-0.74cm 3 Per gram, bulk density of 0.58-0.63g/ml, average particle diameter of 1.6-1.8mm, and average particle strength of 29.4-37.3N. In the present invention, the above-specified definition of the Al is adopted 2 O 3 The HMS composite spherical carrier can ensure that the prepared catalyst has higher mechanical strength and better particle surface uniformity, and can also obtain better catalytic performance in the reaction of preparing isobutene by dehydrogenating isobutane.
According to the invention, the Al 2 O 3 The preparation method of the HMS composite spherical carrier comprises the following steps:
(1) Mixing an alumina precursor with an HMS all-silicon mesoporous molecular sieve for ball milling, mixing powder obtained after ball milling with an acidic aqueous solution to prepare sol, dripping the sol into an oil ammonia column forming device, and performing a balling and aging process to obtain a spherical precursor;
(2) Washing, drying and roasting the spherical precursor to obtain Al 2 O 3 -HMS composite spherical support.
According to the invention, in step (1), the alumina precursor is selected from one or more of pseudo-boehmite, aluminium hydroxide gel, aluminium sol, gibbsite and boehmite, preferably pseudo-boehmite; in the present invention, the alumina precursor may be commercially available. In the present invention, specifically, the pseudo-boehmite is more preferably: pseudo-boehmite powder (produced by Shandong aluminum Co., ltd., specific surface area of 286 m) of type P-DF-09-LSi 2 Per gram, pore volume of 1.08cm 3 Per g), pseudo-boehmite powder (specific surface area 249m, manufactured by Shandong aluminum Co., ltd., model P-DF-07-LSi) 2 Per gram, pore volume of 0.82cm 3 Per g), macroporous pseudo-boehmite powder (manufactured by Zibo constant Ji Fen New Material Co., ltd., specific surface area: 327 m) with the model PB-0101 2 Per gram, pore volume of 1.02cm 3 /g)。
According to the invention, in the step (1), the HMS all-silicon mesoporous molecular sieve can be a commercial HMS all-silicon mesoporous molecular sieve product or a self-made HMS all-silicon mesoporous molecular sieve. Preferably, the specific surface area of the HMS all-silicon mesoporous molecular sieve is 800-1100m 2 Per gram, pore volume of 0.9-1.1cm 3 And/g, the average pore diameter is 3-4nm.
In the invention, the preparation of the HMS all-silicon mesoporous molecular sieve comprises the following steps:
under the condition of preparing the adhesive tape by hydrolysis, mixing and contacting a template agent, ethanol and water, and dripping a silicon source into the mixture to obtain a gel mixture; crystallizing the gel mixture; and then filtering, washing, drying and roasting the crystallized product to obtain the HMS all-silicon mesoporous molecular sieve.
The template agent is a neutral surfactant; preferably, the template agent is a long-chain primary amine surfactant; more preferably one or more of dodecyl amine, hexadecyl amine and octadecyl amine.
The silicon source is a silicon-containing organic compound or a silicon-containing inorganic compound; preferably a silicon-containing organic compound; more preferably one or more of ethyl orthosilicate, methyl orthosilicate or butyl orthosilicate.
The conditions of the contacting include: the temperature is 10-80 ℃, preferably 20-60 ℃; the time is 0.5-5h, preferably 1-3h. Preferably, the contacting may be performed under stirring in order to uniformly mix the template, ethanol, water and silicon source.
The weight ratio of the amounts of the template agent, the ethanol, the water and the silicon source is 1: (1-30): (2-20): (1-12); preferably 1: (3-15): (4-10): (2-8).
The crystallization conditions include: the temperature is 10-80 ℃, preferably 20-60 ℃; the time is 3-48 hours, preferably 5-30 hours.
The filtration process is not particularly limited and may be in a manner known in the art, including gravity filtration, pressure filtration, vacuum filtration or centrifugal filtration. Preferably, the filtering process specifically includes: vacuum-pumping the bottom of the funnel by using a suction bottle or filtering by using a centrifugal filter.
The washing process may include: after filtration, a solid product is obtained, which is repeatedly washed with distilled water or ethanol (the washing times may be 5-10 times), and then suction filtration is performed.
The drying conditions include: the temperature is 50-150deg.C, preferably 60-120deg.C; the time is 1-24 hours, preferably 3-16 hours.
The roasting conditions include: the temperature is 450-700 ℃, preferably 500-650 ℃; the time is 4-30 hours, preferably 6-20 hours.
According to the invention, in step (1), the ball milling is carried out in a ball mill, wherein the diameter of the grinding balls in the ball mill may be 2-3mm; the number of grinding balls can be reasonably selected according to the size of the ball milling tank, and for the ball milling tank with the size of 100-300mL, 3-8 grinding balls can be generally used; the material of the grinding balls can be agate, polytetrafluoroethylene and the like, and agate is preferable. The ball milling conditions include: the rotating speed of the grinding balls can be 300-500r/min, the temperature in the ball milling tank can be 30-80 ℃, and the ball milling time can be 2-30h.
According to the present invention, in the step (1), the acidic aqueous solution may be an aqueous organic acid solution or an aqueous inorganic acid solution, preferably one or more of an aqueous formic acid solution, an aqueous acetic acid solution, an aqueous citric acid solution, an aqueous nitric acid solution, and an aqueous hydrochloric acid solution, and more preferably an aqueous nitric acid solution or an aqueous citric acid solution; the mass concentration of the acidic aqueous solution may be 0.2 to 10%, preferably 0.5 to 5%.
According to the invention, in the step (1), the weight ratio of the dosages of the alumina precursor, the HMS all-silicon mesoporous molecular sieve and the acidic aqueous solution is 1: (0.05-0.9): (1-5), preferably 1: (0.3-0.7): (2-4).
According to the invention, in the oil ammonia column forming device, an oil ammonia column is arranged in the oil ammonia column forming device, and the oil ammonia column forming device is a carrier forming device which utilizes the surface tension of liquid to shrink sol into balls in an oil layer and dehydrate and shape in an alkaline water layer. In the present invention, the surface tension is sufficient as long as sol molding can be ensured; in addition, dehydration relies on the reaction of ammonia in the oil column with acid in the sol to remove excess water from the raw material balls under certain temperature conditions. In the present invention, the inventors of the present invention used the oil ammonia column forming method for the first time for Al 2 O 3 -in the process of forming the HMS composite spherical support. The surface tension and dehydration are the principle of the oil ammonia column forming method, and the ball forming and dehydration are realized by means of the conditions of sol preparation, acid addition amount, proportion, speed during stirring and ball dripping, temperature, oil phase and water phase proportion and the like in the forming process.
In the invention, the oil ammonia column forming device is an XF1616 type oil ammonia column forming test device manufactured by Sichuan research technology Co.
According to the invention, in the step (1), the oil phase of the oil ammonia column forming device can be one of transformer oil, silicone oil, vacuum pump oil, liquid paraffin, white oil and petroleum etherOne or more, preferably one or more of transformer oil, vacuum pump oil or silicone oil; the water phase of the oil ammonia column forming device is an ammonia water solution containing nonionic surfactant. The nonionic surfactant can be one or more of fatty alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, preferably peregal O-25 (fatty alcohol polyoxyethylene ether, molecular formula is C 62～68 H 126～138 O 26 ) P123 (a triblock copolymer, collectively: the specific molecular formula of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is as follows: EO (ethylene oxide) film 20 PO 70 EO 20 Molecular weight 5800), F108 (a triblock copolymer, collectively: the specific molecular formula of the polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is as follows: EO (ethylene oxide) film 133 PO 50 EO 133 Molecular weight 14600).
According to the present invention, in step (1), the conditions for the balling may include: the speed of the sol drop balls is 10-300 drops/min, preferably 30-150 drops/min; the temperature of the oil ammonia column is 20-120 ℃, preferably 30-90 ℃.
According to the present invention, in step (1), the aging conditions may include: the temperature is 20-120deg.C, preferably 30-90deg.C; the time is 1-20h, preferably 3-12h.
According to the present invention, in the step (2), the washing method is not particularly limited, and the spherical product may be washed with deionized water a plurality of times to a pH of 7 of the eluate. Preferably, the number of washes with deionized water is from 5 to 10.
According to the present invention, in step (2), the drying conditions may include: the temperature is 70-150deg.C, preferably 100-130deg.C; the time is 2-20h, preferably 3-16h.
According to the present invention, in the step (2), the conditions of the firing may include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-24 hours, preferably 5-12 hours.
In a second aspect, the invention provides a preparation method of the spherical isobutane dehydrogenation catalyst, wherein,the method comprises the following steps: al is added with 2 O 3 The HMS composite spherical carrier is contacted with an aqueous solution of acid or salt containing active metal components, an optional aqueous solution of salt containing a first metal auxiliary agent and an optional aqueous solution of salt containing a second metal auxiliary agent for reaction, and then solid products are obtained after separation, and the solid products are dried and roasted to obtain the spherical isobutane dehydrogenation catalyst.
In the present invention, in the above-mentioned production method, the spherical composite support and the aqueous solution of the acid or salt containing the active metal component, the optional aqueous solution of the salt containing the first metal auxiliary agent, and the optional aqueous solution of the salt containing the second metal auxiliary agent may be contacted together or may be contacted stepwise, and the order of the contacting is not particularly limited.
According to the present invention, the active metal component-containing acid or salt is one or more of a chloride, nitrate or inorganic acid of the active metal component, preferably the active metal component-containing acid or salt is chloroplatinic acid or ammonium chloroplatinate.
According to the present invention, the salt of the salt containing the first metal auxiliary is one or more of carbonate, chloride, sulfate and nitrate of the first metal auxiliary, preferably the salt of the salt containing the first metal auxiliary is selected from SnCl 4 ·5H 2 O、Zn(NO 3 ) 2 ·6H 2 O and La (NO) 3 ) 3 ·6H 2 One or more of O.
According to the present invention, the salt of the salt containing the second metal auxiliary is one or more of carbonate, chloride, sulfate and nitrate of the second metal auxiliary, preferably the salt of the salt containing the second metal auxiliary is NaNO 3 、NaCl、KNO 3 And/or KCl.
According to the invention, the active metal component-containing salt is used in an amount of (0.04-0.14) g, the first metal auxiliary-containing salt is used in an amount of (0-0.5) g, and the second metal auxiliary-containing salt is used in an amount of (0-0.3) g, relative to 100ml of water.
According to the invention, the reaction conditions include: the temperature is 15-90 ℃ and the time is 3-10h.
According to the invention, the drying conditions include: the temperature is 90-160 ℃ and the time is 1-20h; preferably, the temperature is 100-130 ℃ and the time is 4-10h.
According to the invention, the conditions of the calcination include: roasting for 2-15h at 500-700 ℃; preferably, the temperature is 550-650 ℃ and the time is 3-10h.
According to the present invention, a method for preparing a spherical isobutane dehydrogenation catalyst is not particularly limited, and the impregnation method may be selected conventionally in the art, for example, may be one of a co-impregnation method or a stepwise impregnation method.
According to the present invention, a method for preparing a spherical isobutane dehydrogenation catalyst, the embodiment for removing the solvent is not particularly limited, and may be a conventional embodiment in the art, for example, a rotary evaporator or a method using heating evaporation may be employed.
According to the present invention, a method for preparing a spherical isobutane dehydrogenation catalyst, the drying conditions in the above-mentioned method for preparing a spherical isobutane dehydrogenation catalyst are not particularly limited, and may be conventional conditions in the art. Preferably, the drying conditions include: the temperature is 90-160 ℃, preferably 100-130 ℃; the time is 1-20h, preferably 2-5h.
According to the present invention, a method for preparing a spherical isobutane dehydrogenation catalyst, the conditions for the calcination in the above-mentioned method for preparing a spherical isobutane dehydrogenation catalyst are not particularly limited, and may be conventional conditions in the art. Preferably, the roasting conditions include: the temperature is 500-700 ℃, preferably 550-650 ℃; the time is 2-15 hours, preferably 3-10 hours.
The third aspect of the invention provides an application of the spherical isobutane dehydrogenation catalyst in the reaction of preparing isobutene by isobutane dehydrogenation.
According to the invention, the reaction for preparing isobutene by dehydrogenating isobutane comprises the following steps: isobutane and hydrogen were simultaneously contacted with a spherical isobutane dehydrogenation catalyst.
According to the inventionThe conditions of the contacting include: the contact temperature can be 500-650 ℃, the partial pressure of raw material gas is 0.02-0.5MPa, the mol ratio of isobutane to hydrogen in the raw material is 0.1-5, and the mass airspeed of isobutane is 1.0-10.0h -1 。
The present invention will be described in detail by examples.
In the following examples and comparative examples:
the pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. The sample was vacuum degassed at 350 ℃ for 4 hours prior to measurement, the specific surface area of the sample was calculated using the BET method, and the pore volume was calculated using the BJH model. Elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX, inc. of America.
The oil ammonia column forming device is an XF1616 type oil ammonia column forming test device manufactured by Sichuan research technology Co.
The rotary evaporator is manufactured by IKA corporation of Germany and has the model RV10 digital.
The drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
Pseudo-boehmite powder with the model of P-DF-09-LSi and the model of P-DF-07-LSi are purchased from Shandong aluminum industry Limited liability company, and macroporous pseudo-boehmite powder with the model of PB-0101 is purchased from Zibo constant Ji Fen body New Material Co. The reagents used in examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
Example 1
(1)Al 2 O 3 Preparation of HMS composite spherical support
10.0g of ethylenediamine was dissolved in a mixed solution of 72.0g of ethanol and 63.0g of distilled water, heated to 40℃and stirred for 30 minutes, after which 42.0g of Tetraethylorthosilicate (TEOS) was added dropwise. Stirring is continued in the dropping process, and the dropping step lasts for 2 hours. After the completion of the dropwise addition, the mixture was stirred and crystallized at 40℃for 20 hours. Separating solid product from mother liquor by filtration after crystallizationWashing the solid product with water and ethanol for 8 times, drying at 90 ℃ for 5 hours, and roasting at 600 ℃ for 12 hours to obtain the HMS all-silicon mesoporous molecular sieve A. The specific surface area of the HMS all-silicon mesoporous molecular sieve A is 1021m 2 Per gram, pore volume of 1.02cm 3 And/g, average pore diameter of 3.3nm.
Fig. 1 is an XRD spectrum of the HMS all-silicon mesoporous molecular sieve a, and as can be seen from fig. 1, the XRD spectrum shows a single diffraction peak, the peak value is between 2θ=2° and 3 °, and the XRD spectrum is a characteristic diffraction peak of the (100) crystal face. This illustrates that the sample has a typical hexagonal worm-like pore structure.
80g of pseudo-boehmite with the model of P-DF-09-LSi and 40g of HMS all-silicon mesoporous molecular sieve A are mixed and transferred to a 200mL ball milling tank, and 5 agate grinding balls with the diameter of 2mm are placed into the ball milling tank to start ball milling. The temperature in the ball milling tank is controlled to be 50 ℃, the rotating speed of the grinding balls is 400r/min, and the ball milling time is 20h. The powder obtained after ball milling is mixed with 245g of dilute nitric acid with the concentration of 2.0 percent and stirred for 4 hours to prepare sol. The sol is dripped into an oil ammonia column forming device, the speed of the sol dripping ball is 90 drops/min, the oil phase of the oil ammonia column forming device is 25# transformer oil, the water phase is ammonia water solution containing peregal, and the temperature of the oil ammonia column is 40 ℃. After the completion of the sol dripping, the sol is aged for 10 hours at 40 ℃ to obtain a spherical precursor. Washing spherical precursor with distilled water for 8 times, drying at 110deg.C for 12 hr, and calcining at 600deg.C for 8 hr to obtain Al 2 O 3 -HMS sphere composite carrier a. With Al 2 O 3 The alumina content was 58.3% by weight and the HMS mesoporous molecular sieve content was 41.7% by weight, based on the total weight of the HMS spherical composite support a.
Al 2 O 3 The HMS spherical composite carrier B is white, has smooth surface, uniform particles and uniform size. For Al 2 O 3 The HMS spherical composite support A was characterized and its structural parameters are shown in Table 1.
FIG. 2 is Al prepared in example 1 2 O 3 -small angle XRD spectrum of HMS composite spherical support a. The FIG. 2 is similar to FIG. 1 and shows that Al 2 O 3 After the HMS spherical composite carrier A is roasted at 600 ℃, the HMS mesoporous molecular sieve crystalline phase is not obviously changed, and typical hexagonal worm-like medium is still maintainedPore channel structure.
FIG. 3 is Al prepared in example 1 2 O 3 -wide angle XRD spectrum of HMS composite spherical support a. Al (Al) 2 O 3 The XRD wide-angle diffraction pattern of HMS composite spherical support a is exactly the same as that of alumina, since mesoporous materials have no diffraction signal in the wide-angle part. The x-ray diffraction angles are mainly: 2θ≡37.6 °, 39.4 °, 45.8 °, 60.7 ° and 66.8 °, these five diffraction signals are related to γ -Al 2 O 3 The diffraction patterns are consistent, showing that Al 2 O 3 The HMS composite spherical carrier A shows typical gamma-Al after being dehydrated by pseudo-boehmite with the model of P-DF-09-LSi after being roasted at 600 DEG C 2 O 3 A crystalline phase.
FIG. 4 is Al prepared in example 1 2 O 3 The pore size distribution diagram of the HMS composite spherical support a, as can be seen from fig. 4, the pore size of the sample is in a bimodal distribution, the first most probable pore size is 3.2nm, and is mainly contributed by the HMS mesoporous molecular sieve; the second most probable pore size is 14.4nm, contributed mainly by alumina.
(2) Preparation of spherical isobutane dehydrogenation catalyst
Will be 0.080g H 2 PtCl 6 ·6H 2 O、0.236g SnCl 4 ·5H 2 O and 0.077g KCl are dissolved in 100ml deionized water, and the mixture is mixed with 10g Al prepared in the step (1) 2 O 3 The HMS composite spherical carrier A is mixed and continuously stirred for reaction for 5 hours at room temperature. And (3) evaporating solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a dry box at 120 ℃ and dried for 5 hours. Then, the mixture was calcined in a muffle furnace at 600℃for 6 hours to obtain a spherical isobutane dehydrogenation catalyst A.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst A is as follows: 0.3 wt% of a platinum component in terms of platinum element, 0.8 wt% of a tin component in terms of tin element, 0.4 wt% of a potassium component in terms of potassium element, and the balance being a carrier.
(3) Evaluation of catalyst reactivity
0.5g of spherical isobutane dehydrogenation catalyst A was charged into a fixed bed quartz reactor, the reaction temperature was controlled to 590 deg.c, The reaction pressure was 0.1MPa, isobutane: the molar ratio of hydrogen is 1:1, isobutane mass space velocity of 4.0h -1 The reaction time was 24h. Through Al 2 O 3 The reaction product separated by the S molecular sieve column was directly fed to an agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis. Isobutane conversion, isobutylene selectivity and isobutylene yield were calculated from the reaction data. The carbon deposition of the catalyst after the reaction was measured on a TGA/DSC1 thermogravimetric analyzer manufactured by Mettler-Toledo company. About 20mg of the reacted catalyst sample was warmed from room temperature to 800℃under an air flow of 50ml/min at a warming rate of 10℃per minute, and the weight loss was calculated from the weight loss curve. The experimental results are shown in table 2.
Example 2
(1)Al 2 O 3 Preparation of HMS composite spherical support
10.0g of hexadecylamine was dissolved in a mixed solution of 30.0g of ethanol and 40.0g of distilled water, heated to 60℃and stirred for 20 minutes, after which 20.0g of methyl orthosilicate (TMOS) was added dropwise. Stirring was continued during the dropping, and the dropping step was continued for 40 minutes. After the completion of the dropwise addition, the mixture was stirred and crystallized at 60℃for 5 hours. Separating the solid product from the mother liquor by a filtering method after crystallization, washing the solid product for 10 times by distilled water, drying the solid product at 120 ℃ for 3 hours, and roasting the solid product at 500 ℃ for 20 hours to obtain the HMS all-silicon mesoporous molecular sieve B. The specific surface area of the HMS all-silicon mesoporous molecular sieve B is 926m 2 Per gram, pore volume of 0.94cm 3 And/g, average pore diameter of 3.5nm.
100g of pseudo-boehmite with the model of P-DF-07-LSi and 30g of HMS all-silicon mesoporous molecular sieve B are mixed and transferred to a 200mL ball milling tank, and 3 agate grinding balls with the diameter of 2mm are put into the ball milling tank to start ball milling. The temperature in the ball milling tank is controlled to be 30 ℃, the rotating speed of the grinding balls is 500r/min, and the ball milling time is 6h. The powder obtained after ball milling is mixed with 270g of citric acid with the concentration of 2 percent and stirred for 12 hours to prepare sol. The sol is dripped into an oil ammonia column forming device, the speed of the sol dripping ball is 150 drops/min, the oil phase of the oil ammonia column forming device is silicone oil, the water phase is ammonia water solution containing P123, and the temperature of the oil ammonia column is 90 ℃. After the sol dripping is completed, the sol is aged for 3 hours at 90 ℃,spherical precursors are obtained. Washing the spherical precursor with deionized water for 6 times, drying at 100deg.C for 16 hr, and calcining at 650deg.C for 5 hr to obtain Al 2 O 3 -HMS sphere composite support B. Al (Al) 2 O 3 The HMS spherical composite carrier B is white, has smooth surface, uniform particles and uniform size. With Al 2 O 3 The alumina content was 70.0 wt.% and the HMS molecular sieve content was 30.0 wt.%, based on the total weight of the HMS spherical composite support B.
For Al 2 O 3 The HMS spherical composite support B was characterized and its structural parameters are shown in Table 1.
(2) Preparation of spherical isobutane dehydrogenation catalyst
(a) 0.367g Zn (NO) 3 ) 2 ·6H 2 O is dissolved in 100ml deionized water, and 10g Al prepared in the step (1) is added 2 O 3 The HMS composite spherical carrier B is mixed and continuously stirred for reaction for 5 hours at room temperature. And (3) evaporating solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 100℃and dried for 5 hours. Then baked in a muffle furnace at 650 ℃ for 3 hours. (b) Will be 0.107g H 2 PtCl 6 ·6H 2 O and 0.185g NaNO 3 Dissolved in 100ml deionized water, mixed with the above calcined product, and reacted under continuous stirring at room temperature for 5 hours. And (3) evaporating solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 100℃and dried for 5 hours. Then baked in a muffle furnace at 650 ℃ for 3 hours. Spherical isobutane dehydrogenation catalyst B was obtained.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst B is as follows: 0.4 wt% of platinum component calculated as platinum element, 0.8 wt% of zinc component calculated as zinc element, 0.5 wt% of sodium component calculated as sodium element, and the balance of spherical composite carrier B.
(3) Evaluation of catalyst reactivity
The catalytic performance of spherical isobutane dehydrogenation catalyst B in the reaction of producing isobutylene by dehydrogenation of isobutane was evaluated in the same manner as in step (3) in example 1. The results are shown in Table 2.
Example 3
(1)Al 2 O 3 Preparation of HMS composite spherical support
10.0g of octadecylamine was dissolved in a mixed solution of 150.0g of ethanol and 100.0g of distilled water, and after stirring at 20℃for 1 hour, 80.0g of butyl orthosilicate was added dropwise. Stirring is continued in the dropping process, and the dropping step lasts for 2 hours. After the completion of the dropwise addition, the mixture was stirred and crystallized at 20℃for 30 hours. And after crystallization, separating the solid product from the mother liquor by a filtering method, washing the solid product with ethanol for 5 times, drying at 60 ℃ for 16 hours, and roasting at 650 ℃ for 6 hours to obtain the HMS all-silicon mesoporous molecular sieve C. The specific surface area of the HMS all-silicon mesoporous molecular sieve C is 973m 2 Per gram, pore volume of 0.97cm 3 And/g, average pore diameter of 3.4nm.
50g of pseudo-boehmite with the model PB-0101 and 35g of HMS all-silicon mesoporous molecular sieve C are mixed and transferred to a 200mL ball milling tank, and 5 agate grinding balls with the diameter of 3mm are placed into the ball milling tank to start ball milling. The temperature in the ball milling tank is controlled to be 80 ℃, the rotating speed of the grinding balls is 300r/min, and the ball milling time is 10h. The powder obtained after ball milling is mixed with 180g of dilute nitric acid with the concentration of 0.5 percent and stirred for 16 hours to prepare sol. The sol is dripped into an oil ammonia column forming device, the speed of the sol dripping ball is 30 drops/min, the oil phase of the oil ammonia column forming device is vacuum pump oil, the water phase is ammonia water solution containing F108, and the temperature of the oil ammonia column is 30 ℃. After the completion of the sol dripping, the sol is aged for 12 hours at 30 ℃ to obtain a spherical precursor. Washing spherical precursor with deionized water for 5 times, drying at 130deg.C for 3 hr, and calcining at 500deg.C for 12 hr to obtain Al 2 O 3 -HMS sphere composite carrier C. Al (Al) 2 O 3 The HMS spherical composite carrier C is white, smooth in surface, uniform in particles and uniform in size. With Al 2 O 3 The alumina content was 50.0% by weight and the HMS mesoporous molecular sieve content was 50.0% by weight, based on the total weight of the HMS spherical composite support C.
For Al 2 O 3 The HMS spherical composite support C was characterized and its structural parameters are shown in Table 1.
(2) Preparation of spherical isobutane dehydrogenation catalyst
Will be 0.053g H 2 PtCl 6 ·6H 2 O、0.350gLa(NO 3 ) 3 ·6H 2 O and 0.076g NaCl are dissolved in 100ml deionized water, and 10g Al prepared in step (1) 2 O 3 The HMS composite spherical support C was mixed and reacted for 5 hours with continuous stirring at room temperature. And (3) evaporating solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was placed in a drying oven at 130 ℃ and dried for 2 hours. Then, the mixture was calcined in a muffle furnace at 550℃for 10 hours to obtain a spherical isobutane dehydrogenation catalyst C.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst C is as follows: 0.2 wt% of platinum component calculated as platinum element, 1.1 wt% of lanthanum component calculated as lanthanum element, 0.3 wt% of sodium component calculated as sodium element, and the balance being carrier.
(3) Evaluation of catalyst reactivity
The catalytic performance of the spherical isobutane dehydrogenation catalyst C in the reaction of producing isobutylene by dehydrogenation of isobutane was evaluated in the same manner as in step (3) in example 1. The results are shown in Table 2.
Example 4
A spherical isobutane dehydrogenation catalyst was prepared in the same manner as in example 1 except that in step (2): will be 0.027g H 2 PtCl 6 ·6H 2 O、0.651g SnCl 4 ·5H 2 O and 0.259g NaNO 3 Dissolving in 100ml deionized water, and mixing with 10g Al prepared in step (1) 2 O 3 -HMS composite spherical support a mix.
Spherical isobutane dehydrogenation catalyst D was obtained.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst D is as follows: 0.1% by weight of a platinum component in terms of platinum element, 2.2% by weight of a tin component in terms of tin element, 0.7% by weight of a sodium component in terms of sodium element, the remainder being a carrier.
Example 5
A spherical isobutane dehydrogenation catalyst was prepared in the same manner as in example 1 except that in step (2): will be 0.133g H 2 PtCl 6 ·6H 2 O、0.413g SnCl 4 ·5H 2 O and 0058g KCl was dissolved in 100ml deionized water, and 10g Al was prepared in step (1) 2 O 3 -HMS composite spherical support a mix.
Spherical isobutane dehydrogenation catalyst E was obtained.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst E is as follows: 0.5 wt% of platinum component calculated as platinum element, 1.4 wt% of tin component calculated as tin element, 0.3 wt% of potassium component calculated as potassium element, and the balance being carrier.
Comparative example 1
(1)Al 2 O 3 Preparation of HMS spherical composite supports
10.0g of ethylenediamine was dissolved in a mixed solution of 72.0g of ethanol and 63.0g of distilled water, heated to 40℃and stirred for 30 minutes, after which 42.0g of Tetraethylorthosilicate (TEOS) was added dropwise. Stirring is continued in the dropping process, and the dropping step lasts for 2 hours. After the completion of the dropwise addition, the mixture was stirred and crystallized at 40℃for 20 hours. And after crystallization, separating the solid product from the mother liquor by a filtering method, washing the solid product with absolute ethyl alcohol for 8 times, drying at 90 ℃ for 5 hours, and roasting at 600 ℃ for 12 hours to obtain the HMS all-silicon mesoporous molecular sieve A.
40g of pseudo-boehmite with the model of P-DF-09-LSi and 80g of HMS all-silicon mesoporous molecular sieve A are mixed and transferred to a 200mL ball milling tank, and 5 agate grinding balls with the diameter of 2mm are placed into the ball milling tank to start ball milling. The temperature in the ball milling tank is controlled to be 50 ℃, the rotating speed of the grinding balls is 400r/min, and the ball milling time is 20h. The powder obtained after ball milling is mixed with 245g of dilute nitric acid with the concentration of 2.0 percent and stirred for 4 hours to prepare sol. The sol is dripped into an oil ammonia column forming device, the speed of the sol dripping ball is 90 drops/min, the oil phase of the oil ammonia column forming device is 25# transformer oil, the water phase is ammonia water solution containing peregal, and the temperature of the oil ammonia column is 40 ℃. After the completion of the sol dripping, the sol is aged for 10 hours at 40 ℃ to obtain a spherical precursor. Washing spherical precursor with distilled water for 8 times, drying at 110deg.C for 12 hr, and calcining at 600deg.C for 8 hr to obtain Al 2 O 3 -HMS sphere composite carrier D1. With Al 2 O 3 The alumina content was 25.9% by weight and the HMS mesoporous molecular sieve content was 74.1% by weight, based on the total weight of the HMS spherical composite support D1.
Al 2 O 3 The HMS spherical composite support D1 is white, rough in surface and uneven in particle size. For Al 2 O 3 The HMS spherical composite support D1 was characterized and its structural parameters are shown in Table 1.
(2) Preparation of spherical isobutane dehydrogenation catalyst
Spherical isobutane dehydrogenation catalyst D1 was prepared according to the method of step (2) in example 1.
The specific gravity of each component of the dehydrogenation catalyst D1 is as follows: 0.3 wt% of a platinum component in terms of platinum element, 0.8 wt% of a tin component in terms of tin element, 0.4 wt% of a potassium component in terms of potassium element, and the balance being a carrier.
(3) Evaluation of catalyst reactivity
The catalytic performance of the spherical isobutane dehydrogenation catalyst D1 in the reaction of producing isobutylene by dehydrogenation of isobutane was evaluated in the same manner as in step (3) in example 1. The results are shown in Table 2.
Comparative example 2
(1)Al 2 O 3 Preparation of HMS spherical composite supports
HMS all-silicon mesoporous molecular sieve A was prepared by the method of step (1) of example 1.
80g of pseudo-boehmite with the model of P-DF-09-LSi, 40g of HMS all-silicon mesoporous molecular sieve A, 58g of dilute nitric acid with the concentration of 5 percent and 8g of sesbania powder are mixed, spherical precursors are prepared by adopting a rolling ball method, and the spherical precursors with the size of 1.7mm are screened. Drying the spherical precursor at 110deg.C for 8 hr, and calcining at 600deg.C for 15 hr to obtain Al 2 O 3 -HMS sphere composite carrier D2.
Al 2 O 3 The HMS spherical composite carrier D2 is white, has a non-smooth surface and has poor sphericity. For Al 2 O 3 The HMS spherical composite support D2 was characterized and its structural parameters are shown in Table 1.
(2) Preparation of spherical isobutane dehydrogenation catalyst
Spherical isobutane dehydrogenation catalyst D2 was prepared according to the method of step (2) in example 1.
The specific gravity of each component of the dehydrogenation catalyst D2 is as follows: 0.3 wt% of a platinum component in terms of platinum element, 0.8 wt% of a tin component in terms of tin element, 0.4 wt% of a potassium component in terms of potassium element, and the balance being a carrier.
(3) Evaluation of catalyst reactivity
The catalytic performance of the spherical isobutane dehydrogenation catalyst D2 in the reaction of producing isobutylene by dehydrogenation of isobutane was evaluated in the same manner as in step (3) in example 1. The results are shown in Table 2.
Comparative example 3
A spherical isobutane dehydrogenation catalyst was prepared in the same manner as in example 1 except that in step (2): will be 0.013g H 2 PtCl 6 ·6H 2 O and 0.483g KCl were dissolved in 100ml deionized water, and mixed with 10g Al prepared in step (1) 2 O 3 -HMS composite spherical support a mix.
Spherical isobutane dehydrogenation catalyst D3 was obtained.
The specific gravity of each component of the spherical isobutane dehydrogenation catalyst D3 is as follows: 0.05 wt% of platinum component calculated as platinum element, 2.5 wt% of potassium component calculated as potassium element, and the balance being carrier.
Comparative example 4
A spherical isobutane dehydrogenation catalyst was prepared in the same manner as in example 1 except that "Al" was used 2 O 3 The HMS composite spherical support is "modified to" pseudo-boehmite ", i.e. without Al 2 O 3 -HMS composite spherical support, specifically, "80g pseudo-boehmite model P-DF-09-LSi" in example 1 and "40 g HMS all-silica mesoporous molecular sieve a" were modified to "137g pseudo-boehmite model P-DF-09-LSi".
Spherical isobutane dehydrogenation catalyst D4 was obtained.
Comparative example 5
A spherical isobutane dehydrogenation catalyst D5 was prepared in the same manner as in example 1 except that 40g of hms all-silicon mesoporous molecular sieve a was replaced with 40g of hms all-silicon mesoporous molecular sieve D. The specific surface area of the HMS all-silicon mesoporous molecular sieve D is 648m 2 Per gram, pore volume of 0.64cm 3 And/g, average pore diameter of 4.3nm.
Spherical isobutane dehydrogenation catalyst D5 was obtained.
TABLE 1
As can be seen from Table 1, al prepared by the method provided by the invention 2 O 3 The average particle size of the HMS composite spherical carrier can be kept in the range of 1.6-1.8mm, and the mechanical strength of the particles can reach above 29N.
Comparative example 1 and comparative example 1 it can be seen that if the ratio of alumina precursor and HMS all-silica mesoporous molecular sieve is not within the scope of the claims, al is prepared 2 O 3 The strength of the HMS composite spherical carrier particles is only 13.8N, and the yield is low.
As can be seen from comparative examples 1 and 2, the particle strength of the spherical composite carrier prepared by the ball forming method is far lower than that of the product of the invention, and the requirement standard of the moving bed process condition is not met.
As can be seen from comparative examples 1 and 4, if the spherical carrier contains only alumina and no HMS all-silica mesoporous molecular sieve, the obtained carrier particles have higher strength, but lower specific surface area and pore volume, and do not meet the carrier standard.
As can be seen from comparative examples 1 and 5, if the HMS all-silicon mesoporous molecular sieve is replaced with a sample with poor index, al is prepared 2 O 3 The HMS composite spherical support particles have better strength but lower specific surface area and pore volume, not meeting the support standards.
Al obtained in examples 1 to 3 2 O 3 The HMS composite spherical carrier products all meet the requirements of the moving bed process, the average particle diameter of particles is between 1.6 and 1.8mm, the bulk density is between 0.58 and 0.65g/ml, the average particle strength is higher than 25N, and the pore volume is higher than 0.6ml/g.
TABLE 2
| Catalyst | Average conversion of isobutane (%) | Average selectivity of isobutene (%) | Carbon deposition (wt%) |
| Catalyst A | 39.4 | 96.1 | 2.87 |
| Catalyst B | 39.0 | 96.0 | 2.94 |
| Catalyst C | 39.3 | 95.9 | 3.02 |
| Catalyst D | 37.2 | 94.7 | 3.58 |
| Catalyst E | 38.0 | 95.3 | 3.37 |
| Catalyst D1 | 33.8 | 92.6 | 5.83 |
| Catalyst D2 | 34.1 | 93.1 | 5.14 |
| Catalyst D3 | 31.7 | 92.0 | 8.01 |
| Catalyst D4 | 32.0 | 92.4 | 7.15 |
| Catalyst D5 | 33.1 | 92.7 | 6.58 |
As can be seen from the results in Table 2, the spherical isobutane dehydrogenation catalyst prepared by the method is used in the reaction of preparing isobutene by isobutane dehydrogenation, so that the catalyst has higher mechanical strength and better uniformity of particle surfaces, better dehydrogenation activity, isobutene selectivity and catalyst stability can be obtained, and the carbon deposition amount is reduced.
In comparative example 1, however, al 2 O 3 The HMS composite spherical support has too high a specific surface area, too high a pore volume, too low a bulk density, and too low an average particle strength. Because the composite spherical carrier contains too many HMS mesoporous molecular sieves, the particle strength and bulk density of the catalyst per se can not meet the requirements of a moving bed process. In this case, even if the catalyst is excellent in reactivityAnd cannot be industrially applied. In addition, because the content of the HMS mesoporous molecular sieve is too high, the components in the carrier are unevenly mixed, so that active components cannot be well dispersed on the carrier, the average conversion rate of isobutane is low, and the average selectivity of isobutene is low.
In comparative example 2, the method of the present invention was not adopted, but a rolling ball method was adopted, and since the surface of the support obtained by the rolling ball method was not smooth, the sphericity of the particles was poor, and the bulk density and the strength of the particles were poor, the catalyst was easily disintegrated after being prepared, and it was difficult to apply industrially. In addition, because of the problem of loose adhesion among the microparticles in the spherical carrier prepared by the rolling ball method, the effect of uniform impregnation cannot be achieved in the process of loading active components and auxiliary agents, and the average conversion rate of isobutane and the average selectivity of isobutene are low.
In comparative example 3, the contents of the active component and the auxiliary agent in the catalyst were not within the scope of claims, resulting in low average conversion of isobutane and low average selectivity of isobutene.
In comparative example 4, if the spherical carrier contains only alumina and does not contain HMS all-silicon mesoporous molecular sieve, the obtained carrier particles have higher strength, but the specific surface area and the pore volume are lower, and the requirements of the moving bed process are not met. In this case, the active ingredient cannot be uniformly dispersed on the carrier, resulting in low average conversion of isobutane and low average selectivity of isobutene.
In comparative example 5, if HMS all-silicon mesoporous molecular sieve is replaced with a sample with poor index, al is prepared 2 O 3 The HMS composite spherical support particles have better strength but lower specific surface area and pore volume, which is detrimental to good dispersion of the active ingredient on the support, thus resulting in low average conversion of isobutane and low average selectivity of isobutene.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (24)
1. A spherical isobutane dehydrogenation catalyst, characterized in that the spherical isobutane dehydrogenation catalyst comprises Al 2 O 3 -HMS composite spherical support and supported on said Al 2 O 3 -an active metal component on a HMS composite spherical support; wherein the Al is 2 O 3 The HMS composite spherical carrier comprises an alumina precursor and an HMS all-silicon mesoporous molecular sieve, wherein the specific surface area of the HMS all-silicon mesoporous molecular sieve is 700-1300m 2 Per gram, pore volume of 0.7-1.3cm 3 /g, average pore size of 2-5nm; and based on the total weight of the catalyst, the Al 2 O 3 -the content of HMS composite spherical support is 95-99.9 wt%, the content of active metal component is 0.1-1 wt%;
the Al is 2 O 3 The preparation method of the HMS composite spherical carrier comprises the following steps:
(1) Mixing an alumina precursor with an HMS all-silicon mesoporous molecular sieve for ball milling, mixing powder obtained after ball milling with an acidic aqueous solution to prepare sol, dripping the sol into an oil ammonia column forming device, and performing a balling and aging process to obtain a spherical precursor;
(2) Washing, drying and roasting the spherical precursor to obtain Al 2 O 3 -HMS composite spherical support.
2. The spherical isobutane dehydrogenation catalyst of claim 1, wherein the Al is based on the total weight of the spherical isobutane dehydrogenation catalyst 2 O 3 -the content of HMS composite spherical support is 97-99.5 wt%, the content of active metal component is 0.2-0.5 wt%;
and/or the active metal component is selected from one or more of platinum, palladium and ruthenium.
3. The spherical isobutane dehydrogenation catalyst according to claim 1 or 2, whereinThe spherical isobutane dehydrogenation catalyst further comprises an Al supported on the catalyst 2 O 3 -a first metal promoter and a second metal promoter on a HMS composite spherical support;
the content of the first metal auxiliary agent is 0-3 wt% based on the total weight of the spherical isobutane dehydrogenation catalyst; the content of the second metal auxiliary agent is 0-2 wt% calculated by metal element;
the first metal auxiliary agent is selected from one or more of tin, zinc, calcium, iron, lanthanum, cobalt and manganese;
the second metal auxiliary agent is selected from one or more of sodium, potassium, lithium and strontium.
4. The spherical isobutane dehydrogenation catalyst according to claim 3, wherein the first metal auxiliary agent is contained in an amount of 0.1 to 2.0 wt% in terms of metal element based on the total weight of the spherical isobutane dehydrogenation catalyst; the content of the second metal auxiliary agent is 0.1-1.2 wt% calculated by metal element;
The first metal auxiliary agent is selected from one or more of tin, zinc, iron and lanthanum;
the second metal auxiliary is selected from sodium and/or potassium.
5. The spherical isobutane dehydrogenation catalyst of claim 1 or 2, wherein the Al 2 O 3 The specific surface area of the HMS composite spherical carrier is 400-900m 2 Per gram, pore volume of 0.4-1cm 3 Per gram, bulk density of 0.5-0.7g/ml, average particle diameter of 1-3mm, and average particle strength of 20-80N.
6. The spherical isobutane dehydrogenation catalyst according to claim 5, wherein the Al 2 O 3 The specific surface area of the HMS composite spherical carrier is 500-750m 2 Per gram, pore volume of 0.5-0.8cm 3 Per gram, bulk density of 0.53-0.68g/ml, average particle diameter of 1.2-2.0mm, and average particle strength of 25-70N.
7. According to claim 6The spherical isobutane dehydrogenation catalyst, wherein the Al 2 O 3 The specific surface area of the HMS composite spherical carrier is 539-647m 2 Per gram, pore volume of 0.61-0.74cm 3 Per gram, bulk density of 0.58-0.63g/ml, average particle diameter of 1.6-1.8mm, and average particle strength of 29.4-37.3N.
8. The spherical isobutane dehydrogenation catalyst of claim 1, wherein in step (1), the alumina precursor is selected from one or more of pseudoboehmite, aluminum hydroxide gel, aluminum sol, gibbsite, and boehmite;
And/or, in the step (1), the weight ratio of the dosages of the alumina precursor, the HMS all-silicon mesoporous molecular sieve and the acidic aqueous solution is 1: (0.05-0.9): (1-5).
9. The spherical isobutane dehydrogenation catalyst of claim 8, wherein the alumina precursor is pseudo-boehmite;
and/or the weight ratio of the dosages of the alumina precursor, the HMS all-silicon mesoporous molecular sieve and the acidic aqueous solution is 1: (0.3-0.7): (2-4).
10. The spherical isobutane dehydrogenation catalyst according to claim 1, wherein in step (1), the conditions of the ball milling include: the temperature in the ball milling tank is 30-80 ℃, and the ball milling time is 2-30 hours.
11. The spherical isobutane dehydrogenation catalyst according to claim 1, wherein in step (1), the acidic aqueous solution is an aqueous organic acid solution or an aqueous inorganic acid solution; the mass concentration of the acidic aqueous solution is 0.2-10%.
12. The spherical isobutane dehydrogenation catalyst of claim 11, wherein the acidic aqueous solution is one or more of an aqueous formic acid solution, an aqueous acetic acid solution, an aqueous citric acid solution, an aqueous nitric acid solution, and an aqueous hydrochloric acid solution; the mass concentration of the acidic aqueous solution is 0.5-5%.
13. The spherical isobutane dehydrogenation catalyst of claim 12, wherein the acidic aqueous solution is an aqueous nitric acid solution and/or an aqueous citric acid solution.
14. The spherical isobutane dehydrogenation catalyst according to claim 1, wherein in step (1), the oil phase of the oil ammonia column forming device is selected from one or more of transformer oil, silicone oil, vacuum pump oil, liquid paraffin, white oil and petroleum ether; and/or the water phase of the oil ammonia column forming device is an ammonia water solution containing nonionic surfactant.
15. The spherical isobutane dehydrogenation catalyst of claim 14, wherein the nonionic surfactant is selected from one or more of a fatty alcohol polyoxyethylene ether, an alkylphenol polyoxyethylene ether, and a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer.
16. The spherical isobutane dehydrogenation catalyst according to claim 1, wherein in step (1), the conditions of the balling include: the speed of the sol dropping ball is 10-300 drops/min; the temperature of the oil ammonia column is 20-120 ℃;
and/or, the aging conditions include: the temperature is 20-120 ℃ and the time is 1-20h.
17. The spherical isobutane dehydrogenation catalyst according to claim 1, wherein in step (2), the drying conditions include: the temperature is 70-150 ℃ and the time is 2-20h;
And/or, the roasting conditions include: the temperature is 400-700 ℃ and the time is 2-24h.
18. A process for preparing a spherical isobutane dehydrogenation catalyst according to any one of claims 1 to 17, comprising: al is added with 2 O 3 -HMS composite sphereThe solid product is obtained after separation and is subjected to drying and roasting treatment, so that the spherical isobutane dehydrogenation catalyst is obtained.
19. The method of claim 18, wherein the active metal component-containing acid or salt is one or more of an active metal component chloride, nitrate, and inorganic acid.
20. The production method according to claim 18, wherein the active metal component-containing acid or salt is used in an amount of (0.04-0.14) g, the first metal auxiliary-containing salt is used in an amount of (0-0.5) g, and the second metal auxiliary-containing salt is used in an amount of (0-0.3) g, relative to 100ml of water.
21. The method of preparation of claim 18, wherein the reaction conditions comprise: the temperature is 10-90 ℃ and the time is 0.5-10h.
22. The method of manufacturing according to claim 18, wherein the drying conditions include: the temperature is 90-160 ℃ and the time is 1-20h.
23. The method of claim 18, wherein the firing conditions include: the temperature is 500-700 ℃ and the time is 2-15h.
24. Use of a spherical isobutane dehydrogenation catalyst according to any one of claims 1-17 in a reaction for producing isobutene by dehydrogenation of isobutane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110914004.0A CN115703068B (en) | 2021-08-10 | 2021-08-10 | Spherical isobutane dehydrogenation catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110914004.0A CN115703068B (en) | 2021-08-10 | 2021-08-10 | Spherical isobutane dehydrogenation catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115703068A CN115703068A (en) | 2023-02-17 |
| CN115703068B true CN115703068B (en) | 2024-02-20 |
Family
ID=85179516
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110914004.0A Active CN115703068B (en) | 2021-08-10 | 2021-08-10 | Spherical isobutane dehydrogenation catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115703068B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590424A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof |
| CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
| WO2017197548A1 (en) * | 2016-05-16 | 2017-11-23 | 华电煤业集团有限公司 | Catalyst of methanol or dimethyl ether conversion to prepare aromatic hydrocarbon in situ synthesis method and application |
| CN107398296A (en) * | 2016-05-20 | 2017-11-28 | 青岛科技大学 | A kind of mixing mesoporous supports of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN109746026A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of dehydrogenation and the preparation method and application thereof |
| CN110548535A (en) * | 2018-05-31 | 2019-12-10 | 中国石油化工股份有限公司 | reforming catalyst and preparation method and application thereof |
| CN111068579A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Method for forming dropping ball |
| CN112138705A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | High-temperature and ball-milling modified SBA-15 molecular sieve material and preparation method thereof, propane dehydrogenation catalyst and preparation method and application thereof |
| CN112973771A (en) * | 2021-02-25 | 2021-06-18 | 西南化工研究设计院有限公司 | Spherical catalyst carrier containing molecular sieve and alumina, preparation and application thereof |
-
2021
- 2021-08-10 CN CN202110914004.0A patent/CN115703068B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101590424A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof |
| CN105618026A (en) * | 2016-01-05 | 2016-06-01 | 中国石油大学(华东) | Catalyst for catalytic dehydrogenation of alkane as well as preparation method and application method of catalyst |
| WO2017197548A1 (en) * | 2016-05-16 | 2017-11-23 | 华电煤业集团有限公司 | Catalyst of methanol or dimethyl ether conversion to prepare aromatic hydrocarbon in situ synthesis method and application |
| CN107398296A (en) * | 2016-05-20 | 2017-11-28 | 青岛科技大学 | A kind of mixing mesoporous supports of catalyst for dehydrogenation of low-carbon paraffin and preparation method thereof |
| CN109746026A (en) * | 2017-11-03 | 2019-05-14 | 中国石油化工股份有限公司 | A kind of dehydrogenation and the preparation method and application thereof |
| CN110548535A (en) * | 2018-05-31 | 2019-12-10 | 中国石油化工股份有限公司 | reforming catalyst and preparation method and application thereof |
| CN111068579A (en) * | 2018-10-22 | 2020-04-28 | 中国石油化工股份有限公司 | Method for forming dropping ball |
| CN112138705A (en) * | 2019-06-28 | 2020-12-29 | 中国石油化工股份有限公司 | High-temperature and ball-milling modified SBA-15 molecular sieve material and preparation method thereof, propane dehydrogenation catalyst and preparation method and application thereof |
| CN112973771A (en) * | 2021-02-25 | 2021-06-18 | 西南化工研究设计院有限公司 | Spherical catalyst carrier containing molecular sieve and alumina, preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CrOx/ZSM-5-Al2O3复合载体催化剂对丙烷脱氢性能的影响;潘淑倩 等;《现代化工》;第40卷(第8期);第144-149页 * |
| 毫米级Al2O3-ZSM-5小球载体的研制及负载Ga催化剂芳构化性能;刘建良 等;《石油炼制与化工》;第52卷(第3期);第29-33页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115703068A (en) | 2023-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102513143A (en) | Preparation method of catalyst for catalyzing aromatization modification of gasoline | |
| CN115703068B (en) | Spherical isobutane dehydrogenation catalyst and preparation method and application thereof | |
| CN108722468B (en) | A kind of method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN110732341A (en) | Isobutane dehydrogenation catalyst with spherical aluminum-containing double mesoporous molecular sieve silica gel composite as carrier and preparation method and application thereof | |
| CN109289847A (en) | The method for being catalyzed catalyst of dehydrogenating propane reaction and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN110732342A (en) | Isobutane dehydrogenation catalyst with chlorite composite material with three-dimensional cubic and hexagonal pore channel structure as carrier and preparation method and application thereof | |
| CN116920917A (en) | Shaped dehydrogenation catalyst, preparation method thereof and application thereof in isobutene preparation reaction by isobutane dehydrogenation | |
| WO2021129760A1 (en) | Dlm-1 molecular sieve, manufacturing method therefor, and use thereof | |
| CN110614108B (en) | Isobutane dehydrogenation catalyst with carrier being mesoporous molecular sieve with three-dimensional cage-shaped pore channel distribution structure, preparation method and application | |
| CN115608405B (en) | Millimeter-sized spherical composite carrier, dehydrogenation catalyst, and preparation methods and applications thereof | |
| CN110614110A (en) | Isobutane dehydrogenation catalyst with eggshell-shaped mesoporous material silica gel composite material as carrier, and preparation method and application thereof | |
| CN115487851A (en) | Spherical dehydrogenation catalyst, preparation method thereof and application of spherical dehydrogenation catalyst in reaction for preparing isobutene through isobutane dehydrogenation | |
| CN110496630B (en) | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation | |
| CN110732343A (en) | Isobutane dehydrogenation catalyst with carrier of three-hole hollow spherical mesoporous molecular sieve silica gel composite material and preparation method and application thereof | |
| CN115608406B (en) | Catalyst for synthesizing methyl methacrylate and preparation method and application thereof | |
| CN110813285A (en) | Isobutane dehydrogenation catalyst with spherical surface-surrounded mesoporous material silica gel composite material as carrier and preparation method and application thereof | |
| CN110496634B (en) | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation | |
| CN110614113A (en) | Isobutane dehydrogenation catalyst with rod-shaped mesoporous molecular sieve silica gel composite material as carrier, preparation method and application | |
| CN116851027A (en) | Oil ammonia column forming composite carrier, dehydrogenation catalyst, and preparation method and application thereof | |
| CN110614106A (en) | Isobutane dehydrogenation catalyst with spherical double-mesoporous illite composite material as carrier, preparation method and application | |
| CN110614107A (en) | Isobutane dehydrogenation catalyst with carrier of hollow spherical mesoporous molecular sieve silica gel composite material and preparation method and application thereof | |
| CN113304779B (en) | Carbon tetraolefin cracking propylene yield-increasing catalyst containing all-silicon mesoporous microspheres and preparation method and application thereof | |
| CN114433076B (en) | Supported hydrogenolysis catalyst and preparation method and application thereof | |
| CN110614118A (en) | Isobutane dehydrogenation catalyst with three-hole sepiolite spherical mesoporous composite material as carrier and preparation method and application thereof | |
| CN115487854B (en) | Isobutane dehydrogenation catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |