CN109701530A - A kind of catalyst and preparation method of preparing isobutene through dehydrogenation of iso-butane - Google Patents
A kind of catalyst and preparation method of preparing isobutene through dehydrogenation of iso-butane Download PDFInfo
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000001282 iso-butane Substances 0.000 title claims abstract description 38
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 235000013847 iso-butane Nutrition 0.000 title abstract 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052718 tin Inorganic materials 0.000 claims abstract description 23
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 22
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 19
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 18
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 239000012018 catalyst precursor Substances 0.000 claims description 25
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 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 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000002243 precursor Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 235000010333 potassium nitrate Nutrition 0.000 description 5
- 239000004323 potassium nitrate Substances 0.000 description 5
- 238000002390 rotary evaporation Methods 0.000 description 5
- 239000001119 stannous chloride Substances 0.000 description 5
- 235000011150 stannous chloride Nutrition 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 229910008897 Sn—La Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst of preparing isobutene through dehydrogenation of iso-butane and preparation methods.Catalyst includes carrier and the active component being supported on carrier and auxiliary agent；Active component is platinum group metal, and it is in terms of 100% by overall catalyst weight, the content of auxiliary agent is 0.001-30% that the auxiliary agent, which includes lanthanide series, alkali metal, tin and carbon,.The content of carrier is 69-99.9%；The content of active component is 0.001-5%；The content of lanthanide series metal is 0.001-15%；Alkali metal element content is 0.001-5%；The content of tin is 0.001-5%；The content of carbon is 0.001-1%.Iso-butane conversion ratio and selective isobutene can be improved in catalyst of the invention, has good technique application prospect.
Description
Technical Field
The technical field of C4, and further relates to a catalyst for preparing isobutene by isobutane dehydrogenation and a preparation method thereof.
Background
Isobutene is an important organic chemical raw material and is widely applied to chemical products such as polyisobutene, butyl rubber, methyl tert-butyl ether and the like. The methyl tert-butyl ether can be used as an additive for improving the octane number, and the market demand is huge, so that the isobutene market is short of supply. Isobutene is mainly derived from the catalytic cracking process of ethylene preparation by naphtha steam cracking and petroleum refining. In order to increase the conversion rate of isobutane dehydrogenation, a higher reaction temperature is needed, and the higher reaction temperature is easy to cause other side reactions, so that the reaction selectivity is reduced, and the catalyst is accelerated to be deactivated.
At present, isobutane dehydrogenation is industrialized, and the existing processes mainly comprise an Oleflex process of UOP company, a Catofin process of LUMMUS company, a Star process of UHDE company and the like. At present, the industrialized isobutane catalytic dehydrogenation catalyst mainly comprises two types of platinum-series catalysts and chromium-series catalysts. Wherein, the chromium catalyst has fast inactivation and is not beneficial to the health of human body and environmental protection; the platinum catalyst is a research hotspot due to the characteristics of high activity, low pollution, low wear rate and capability of operating under severe conditions. However, the platinum group catalyst tends to rapidly decrease the reaction activity due to the surface carbon deposition of the catalytically active sites in the reaction atmosphere. Therefore, when platinum is used as a main active component, a series of auxiliary agents are often required to be added to improve the isobutane conversion rate and the isobutene selectivity.
Zhang et al earlier found (DOI:10.1016/S0167-2991(08)62627-0) that tin can inhibit the formation of carbon on the platinum surface in the alkane dehydrogenation reaction, and can better improve the stability of the catalyst.
Wan et al found (DOI:10.1021/ie1023518) that the addition of lanthanum had a very good promoting effect on the platinum catalyst. A proper amount of lanthanum can reduce the carbon deposition amount on the surface of the catalyst and improve the dispersion degree of platinum, but more lanthanum can also cause the agglomeration and deactivation of the platinum.
Zhang et al found that addition of a small amount of zinc (DOI:10.1016/j. furproc.2011.12.040) not only increased the platinum dispersion but also reduced the formation of carbon. The addition of zinc can effectively enhance the interaction between the tin auxiliary agent and the tin oxide in the body, thereby enhancing the reduction resistance of the surface tin oxide.
In conclusion, in the existing process of preparing isobutene by dehydrogenating isobutane, the isobutane dehydrogenation reaction catalyst taking platinum as a main active component is technically improved by mainly taking an auxiliary agent type as a breakthrough in the prior art, but the technical problems of deactivation of a platinum group catalyst system and low conversion rate and isobutene selectivity are not fundamentally solved.
Disclosure of Invention
The invention provides a catalyst for preparing isobutene by isobutane dehydrogenation and a preparation method thereof, and aims to solve the problems of low isobutane conversion rate and low isobutene selectivity in the process of preparing isobutene by isobutane dehydrogenation in the prior art. The catalyst of the invention can improve the isobutane conversion rate and the isobutene selectivity.
The invention aims to provide a catalyst for preparing isobutene by dehydrogenating isobutane.
The catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier;
the active component is a platinum group metal, the auxiliary agent comprises lanthanide, alkali metal, tin and carbon,
the content of the auxiliary agent is 0.001-30% based on the total weight of the catalyst as 100%.
Wherein,
based on the total weight of the catalyst as 100 percent,
the content of the carrier is 69-99.9%; preferably 82.5 to 99.6%; more preferably 89.2-98.4%;
the content of active components is 0.001-5%; preferably 0.1 to 1%; more preferably 0.3-0.5%;
the content of lanthanide metal is 0.001-15%; preferably 0.01 to 10%; more preferably 0.1 to 5%; (ii) a
The content of alkali metal element is 0.001-5%; preferably 0.01 to 4%; more preferably 0.1 to 3%;
the content of tin is 0.001-5%; preferably 0.1 to 4%; more preferably 1.0-2.0%;
the content of carbon is 0.001-1%; preferably 0.01-0.5%; more preferably 0.1 to 0.3%.
Preferably:
the carrier is alumina, silicon dioxide, zirconium dioxide, titanium dioxide, magnesium oxide or zinc oxide;
the active component is at least one of ruthenium, rhodium, palladium, osmium, iridium and platinum;
the alkali metal is one of lithium, sodium, potassium, rubidium and cesium;
the lanthanide is one of lanthanum, cerium, praseodymium and neodymium.
The second purpose of the invention is to provide a preparation method of the catalyst for preparing isobutene by isobutane dehydrogenation.
Comprises that
(1) Loading an active component, a lanthanide metal component, an alkali metal component and a tin component on a carrier by adopting an impregnation method to obtain a catalyst precursor I;
(2) roasting the catalyst precursor I in a mixed atmosphere of hydrocarbon and hydrogen to obtain a catalyst precursor II;
(3) and reducing the catalyst precursor II under hydrogen-containing atmosphere to obtain the catalyst.
Among them, preferred are:
step (2), the hydrocarbon is methane or ethylene.
Step (2), the ratio of hydrogen to hydrocarbon is 1: 1-30;
the roasting temperature is 300-500 ℃, and the roasting time is 1-30 min.
The invention can adopt the following technical scheme:
the invention provides a catalyst for preparing isobutene through isobutane dehydrogenation, which comprises a carrier, an active component and an auxiliary agent, wherein the active component and the auxiliary agent are loaded on the carrier, the carrier is alumina, the active component is a platinum group metal, the auxiliary agent comprises lanthanide series metal, alkali metal, tin and carbon, and the mass content of the auxiliary agent is 0.001-30% based on the total mass of the catalyst.
According to the invention, in order to further improve the isobutane conversion rate and the isobutene selectivity, the mass content of the carrier is 69-99.9%, preferably 82.5.5-99.7%, more preferably 89.2-98.5% based on the total mass of the catalyst; the mass content of the active component is 0.001-5%, preferably 0.1-1%, and more preferably 0.3-0.5%; the mass content of the lanthanide metal is 0.001-15%, preferably 0.01-10%, more preferably 0.1-5%; the content of the alkali metal element is 0.001-5%, preferably 0.01-4%, and more preferably 0.1-3%; the mass content of the tin is 0.001-5%, preferably 0.1-4%, more preferably 1.0-2.0%; the carbon content is 0.001 to 1% by mass, preferably 0.01 to 0.5% by mass, more preferably 0.1 to 0.3% by mass.
According to the present invention, the support is not particularly limited, and may be a support known to those skilled in the art, and may be, for example, alumina, silica, zirconia, titania, magnesia, zinc oxide, or the like. Preferably, the support is alumina, more preferably gamma-alumina.
In the catalyst provided by the present invention, the active ingredient is not particularly limited as long as it has dehydrogenation catalytic activity, and may be an active ingredient known to those skilled in the art, for example, a platinum group metal, which may be at least one selected from ruthenium, rhodium, palladium, osmium, iridium, and platinum, preferably platinum.
In the catalyst provided by the invention, the lanthanide metal is selected from at least one of lanthanum and cerium, and is preferably lanthanum.
In the catalyst provided by the invention, the alkali metal is selected from one of lithium, sodium, potassium, rubidium and cesium, and preferably lithium, sodium and potassium.
The method for preparing the catalyst is not particularly limited, and a method conventionally used in the art may be used, for example, an impregnation method, a coprecipitation method, etc., and preferably an impregnation method, and in a specific embodiment, the method for preparing the catalyst may include the steps of:
(1) loading an active component, a lanthanide metal component, an alkali metal component and a tin component on a carrier by adopting an impregnation method to obtain a catalyst precursor I;
(2) roasting the catalyst precursor I in a mixed atmosphere containing hydrocarbon to obtain a catalyst precursor II;
(3) and reducing the catalyst precursor II under hydrogen-containing atmosphere to obtain the catalyst.
Wherein the process of loading the active component, the lanthanide metal component and the tin component on the carrier by adopting an impregnation method in the step (1) comprises the following steps:
(a) loading a precursor of an active component and a precursor of lanthanide metal on the carrier by adopting an impregnation method, and then drying and roasting;
(b) loading a precursor of tin on the catalyst precursor obtained in the step (a) by adopting an impregnation method, and then drying and roasting to obtain the catalyst precursor I.
According to the present invention, in the step (1), the impregnation conditions are not particularly limited, and may be conventional conditions in the art, for example, impregnation may be performed at room temperature for 0.5 to 1 hour. Wherein, the precursor of the active component is acid or salt containing the active component, preferably at least one of chloroplatinic acid, ammonium hexachloroplatinate and ammonium tetrachloroplatinate, and more preferably chloroplatinic acid; the precursor of the lanthanide metal is at least one of nitrate, chloride, carbonate and acetate of the lanthanide metal, preferably at least one of lanthanum nitrate, lanthanum chloride and lanthanum acetate, and more preferably lanthanum nitrate; the precursor of the alkali metal is one of nitrate, nitrite, chloride and acetate of the alkali metal, preferably potassium nitrate, sodium nitrate and sodium carbonate, and more preferably potassium nitrate; the precursor of the tin is stannous chloride or stannous sulfate, preferably stannous chloride, so that in the precursor solution containing tin, the tin exists in an oxidation state, and the tin in the oxidation state can increase the dispersion degree of the active components, thereby being beneficial to improving the dehydrogenation performance of the catalyst.
According to the present invention, in the steps (a) and (b), the drying may be performed using a method conventional in the art, such as a rotary evaporation drying method; the calcination may also be carried out according to conventional methods, and the conditions may include: the roasting temperature is 450-650 ℃ and the time is 2-6 hours.
According to the present invention, in step (2), the catalyst precursor I obtained from step (1) needs to be calcined in a mixed atmosphere containing a hydrocarbon to support carbon on the catalyst precursor I to obtain a catalyst precursor II. The hydrocarbon-containing mixed atmosphere is not particularly limited in the present invention, and may be, for example, H2And C2H4Roasting in mixed atmosphere; in the present invention, the conditions for the calcination are not particularly limited, and may be, for example, H2And C2H4The volume ratio of (1: 1) - (30), the roasting temperature of 300-.
The contact reaction of isobutane with the catalyst according to the present invention may be carried out in reactors commonly used in the art, for example in fixed bed reactors, fluidized bed reactors or moving bedsIn a moving bed reactor, preferably a fixed bed reactor. In addition, because the isobutane catalytic dehydrogenation reaction is thermodynamically an endothermic and reversible reaction with an increased number of molecules, the conversion rate depends on thermodynamic equilibrium, and increasing the reaction temperature and decreasing the reaction pressure are favorable for the reaction to proceed toward dehydrogenation. However, too high a temperature may aggravate deep dehydrogenation of isobutane, resulting in a decrease in reaction selectivity, while a high temperature may aggravate a cracking reaction, which accelerates carbon deposition on the surface of the catalyst, thereby accelerating deactivation of the catalyst. Thus, the operating conditions of the contact reaction may be carried out according to conventional conditions. In one embodiment, the contact reaction is carried out in a fixed bed reactor, with a reactor inlet temperature of 400-; the volume space velocity of the isobutane is 300-3000h-1Preferably 500--1And the pressure of the contact reaction is not more than 0.05MPa at most.
In the present invention, the pressures are gauge pressures.
The isobutane dehydrogenation catalyst prepared by the invention takes platinum group metal as an active component and takes lanthanide, tin, alkali metal and carbon as auxiliaries. The catalyst has improved isobutane conversion rate, isobutene selectivity and carbon deposition resistance, and thus has good industrial application prospect.
Detailed Description
The present invention will be further described with reference to the following examples.
Examples
This example illustrates the preparation of the catalyst for the dehydrogenation of isobutane to isobutene as provided by the present invention.
Preparation: 60g of gamma-alumina (Shandong aluminum industry) is soaked in 0.15mol/L lanthanum nitrate solution at 75 ℃, and is dried for 0.5h at 75 ℃ by rotary evaporation. Chloroplatinic acid (national chemical group chemical Co., Ltd.), potassium nitrate and 0.3mol/L of potassium nitrate are addedIn a stannous chloride (Tibet shin-Suffi chemical research institute), drying the stannous chloride in a water solution at 75 ℃ for 0.5h by rotary evaporation, placing the material into a muffle furnace, and roasting the material for 3h in an air atmosphere at 450 ℃ to obtain a catalyst precursor I. Wherein the volume of the solution is measured according to the mass content of the catalyst component to obtain the catalyst precursor I. The catalyst precursor I was taken out and placed in a tube furnace in H2And C2H4And roasting for 15min in a mixed atmosphere with the volume ratio of 1:1 at the roasting temperature of 500 ℃ to obtain a catalyst precursor II. Finally, the catalyst precursor II is reduced by hydrogen for 1h at 580 ℃ to obtain the catalyst 1, the composition of which is Pt-Sn-La-C/Al2O3。
The preparation of catalysts 2 to 5 was carried out in a similar manner to catalyst 1, with the proportions of the active components of the added catalysts differing, and the mass contents of the components in the catalysts, based on the total mass of the catalyst, being as indicated in Table 1.
Comparative example
Preparation: 60g of gamma-alumina (Shandong aluminum industry) is soaked in 0.15mol/L lanthanum nitrate solution at 75 ℃, and is dried for 0.5h at 75 ℃ by rotary evaporation. Putting chloroplatinic acid (national medicine group chemical reagent Co., Ltd.), potassium nitrate and 0.3mol/L stannous chloride (shin-Su Fine chemical research institute of Tianjin) aqueous solution, drying at 75 ℃ for 0.5h by rotary evaporation, placing the materials into a muffle furnace, and roasting at 450 ℃ for 3h in an air atmosphere to obtain the catalyst precursor I. Wherein the volume of the solution is measured according to the mass content of the catalyst component to obtain the catalyst precursor I. Reducing the catalyst precursor I with hydrogen at 580 ℃ for 1h to obtain a catalyst 6 with the composition of Pt-Sn-La/Al2O3。
The added catalyst active components of the catalysts 6-10 are based on the total mass of the catalysts, and the mass content of each component in the catalysts is respectively the same as that of the catalysts 1-5.
The isobutane dehydrogenation experiment is completed on a fixed bed, wherein the filling volume of the catalyst is 30ml, and the volume airspeed of isobutane is 500-2000h-1The reaction pressure was atmospheric pressure and the reactor inlet temperature was 5 deg.CAnd (3) analyzing the isobutane dehydrogenation product at the temperature of 40-620 ℃ by adopting an HP7890 gas chromatography, wherein the experimental results of the experiment time reaching 3 hours are detailed in table 1.
TABLE 1
TABLE 2
Comparing the above examples 1 to 5 with the comparative examples 1 to 5, it can be seen that in the process of preparing isobutene by dehydrogenating isobutane, the conversion rate of isobutane and the selectivity of isobutene in the process of preparing isobutene by dehydrogenating isobutane can be improved by introducing auxiliary agents of lanthanide metal, alkali metal, tin and carbon into the dehydrogenation catalyst.
Claims (8)
1. A catalyst for preparing isobutene by isobutane dehydrogenation is characterized in that:
the catalyst comprises a carrier, and an active component and an auxiliary agent which are loaded on the carrier;
the active component is a platinum group metal, the auxiliary agent comprises lanthanide, alkali metal, tin and carbon,
the content of the auxiliary agent is 0.001-30% based on the total weight of the catalyst as 100%.
2. The catalyst for dehydrogenating isobutane to produce isobutene according to claim 1, wherein:
based on the total weight of the catalyst as 100 percent,
the content of the carrier is 69-99.9%;
the content of active components is 0.001-5%;
the content of lanthanide metal is 0.001-15%;
the content of alkali metal element is 0.001-5%;
the content of tin is 0.001-5%;
the carbon content is 0.001-1%.
3. The catalyst for dehydrogenating isobutane to produce isobutene according to claim 2, wherein:
based on the total weight of the catalyst as 100 percent,
the content of the carrier is 82.5-99.6%;
the content of active components is 0.1-1%;
the content of lanthanide metal is 0.01-10%;
the content of alkali metal elements is 0.01-4%;
the content of tin is 0.1-4%;
the carbon content is 0.01-0.5%.
4. The catalyst for dehydrogenating isobutane to produce isobutene according to claim 3, wherein:
based on the total weight of the catalyst as 100 percent,
the content of the carrier is 89.2-98.4%;
the content of active components is 0.3-0.5%;
the content of lanthanide metal is 0.1-5%;
the content of alkali metal elements is 0.1-3%;
the content of tin is 1.0-2.0%;
the carbon content is 0.1-0.3%.
5. The catalyst for dehydrogenating isobutane to produce isobutene according to claim 1, wherein:
the carrier is alumina, silicon dioxide, zirconium dioxide, titanium dioxide, magnesium oxide or zinc oxide;
the active component is at least one of ruthenium, rhodium, palladium, osmium, iridium and platinum;
the alkali metal is one of lithium, sodium, potassium, rubidium and cesium;
the lanthanide is one of lanthanum, cerium, praseodymium and neodymium.
6. A method for preparing the catalyst for preparing isobutene through isobutane dehydrogenation according to any one of claims 1 to 5, wherein the method comprises the following steps:
(1) loading an active component, a lanthanide metal component, an alkali metal component and a tin component on a carrier by adopting an impregnation method to obtain a catalyst precursor I;
(2) roasting the catalyst precursor I in a mixed atmosphere of hydrocarbon and hydrogen to obtain a catalyst precursor II;
(3) and reducing the catalyst precursor II under hydrogen-containing atmosphere to obtain the catalyst.
7. The method of claim 6, wherein:
and (2) the hydrocarbon is methane or ethylene.
8. The method of claim 6, wherein:
step (2), the ratio of hydrogen to hydrocarbon is 1 (1-30);
the roasting temperature is 300-500 ℃, and the roasting time is 1-30 min.
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| CN102775262A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for preparing olefin by dehydrogenating low-carbon alkane |
| CN106582629A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing propene through dehydrogenating propane, preparation method for catalyst and application of catalyst |
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| CN102775262A (en) * | 2011-05-13 | 2012-11-14 | 中国石油天然气股份有限公司 | Method for preparing olefin by dehydrogenating low-carbon alkane |
| CN106582629A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for preparing propene through dehydrogenating propane, preparation method for catalyst and application of catalyst |
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| CN113877577A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for improving alkane conversion rate |
| CN113877577B (en) * | 2020-07-02 | 2024-01-30 | 中国石油化工股份有限公司 | Catalyst, preparation method thereof and method for improving alkane conversion rate |
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