CN102416340A - Method for converting n-butene into isobutene by using gold-loaded molecular sieve catalyst - Google Patents
Method for converting n-butene into isobutene by using gold-loaded molecular sieve catalyst Download PDFInfo
- Publication number
- CN102416340A CN102416340A CN2011103241307A CN201110324130A CN102416340A CN 102416340 A CN102416340 A CN 102416340A CN 2011103241307 A CN2011103241307 A CN 2011103241307A CN 201110324130 A CN201110324130 A CN 201110324130A CN 102416340 A CN102416340 A CN 102416340A
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- China
- Prior art keywords
- catalyst
- zeolite
- butene
- carrier
- negative pressure
- 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.)
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- 239000003054 catalyst Substances 0.000 title claims abstract description 188
- 239000010931 gold Substances 0.000 title claims abstract description 140
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 119
- 238000000034 method Methods 0.000 title claims abstract description 114
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 102
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 239000002808 molecular sieve Substances 0.000 title abstract description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title abstract description 23
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 104
- 239000010457 zeolite Substances 0.000 claims abstract description 104
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 101
- 238000006317 isomerization reaction Methods 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 36
- 239000002243 precursor Substances 0.000 claims abstract description 34
- 238000001556 precipitation Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 238000007872 degassing Methods 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 83
- 239000000243 solution Substances 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 41
- 239000007787 solid Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 28
- 239000003153 chemical reaction reagent Substances 0.000 claims description 22
- 230000001376 precipitating effect Effects 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 20
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 150000003863 ammonium salts Chemical class 0.000 claims description 17
- 239000001273 butane Substances 0.000 claims description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 239000012159 carrier gas Substances 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 239000004215 Carbon black (E152) Substances 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims description 12
- 238000012545 processing Methods 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
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- 230000008021 deposition Effects 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 238000012805 post-processing Methods 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 7
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- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 239000003595 mist Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- 238000013019 agitation Methods 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 40
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 9
- 229910018557 Si O Inorganic materials 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract 2
- 125000005372 silanol group Chemical group 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 31
- 230000008859 change Effects 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 238000001802 infusion Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical group [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000011943 nanocatalyst Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- 238000003795 desorption Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 238000000975 co-precipitation Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
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- 229910052906 cristobalite Inorganic materials 0.000 description 4
- 229910001657 ferrierite group Inorganic materials 0.000 description 4
- 229910052733 gallium Inorganic materials 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
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- 239000000126 substance Substances 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 244000309464 bull Species 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
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- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
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- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
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- 230000001737 promoting effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003235 pyrrolidines Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- WMXCDAVJEZZYLT-UHFFFAOYSA-N tert-butylthiol Chemical compound CC(C)(C)S WMXCDAVJEZZYLT-UHFFFAOYSA-N 0.000 description 1
- -1 tetramethyl ethyl diamines Chemical class 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for converting n-butene into isobutene by using a gold-loaded molecular sieve catalyst, which belongs to the technical field of catalysts. It is appropriate to use a metal-acid bi-functional catalyst for isomerization of n-butene. According to the invention, after a molecular sieve fully undergoes negative pressure degasification and purification, a gold precursor and a second metal precursor are loaded on a carrier of the molecular sieve by using the negative pressure deposition-precipitation method so as to form a Si-O(H)-Au structure, wherein, the molecular sieve refers to a silicon-rich zeolite molecular sieve; preparation of the gold-loaded catalyst by using the deposition-precipitation method under the condition of negative pressure is beneficial for purification of the internal and external surfaces and tunnels of the molecular sieve and enables Au to easily enter into the tunnels of the molecular sieve, to be highly dispersed and to compound with silanol groups on the internal and external surfaces of the molecular sieve to form the Si-O(H)-Au structure. The method provided in the invention enables n-butene to undergo skeletal isomerization under the action of the double functions of metal and the carrier so as to produce isobutene.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of molecular sieve catalyst of load gold that uses and transform the method for n-butene as isobutene.
Background technology
Isobutene is one of important source material of petrochemical industry, and its source mainly contains, catalytic cracking, thermal cracking, n-butene skeletal isomerization and the dehydrogenation of normal butane isomery etc.The n-butene isomerization has purposes widely.For example, n-butene is converted into isobutene, can be used for the production high octane gasoline component; Butene rubber, polyisobutene, butanone and methyl tertiary butyl ether(MTBE), the tert-butyl alcohol, butylphenol, tert-butyl mercaptan or the like.The early stage isomerization of butene catalyst sulfuric acid type (H that uses
2SO
4), halide type (HF) and non-halide type (phosphoric acid, boric acid and boron phosphate) though etc. acid strong, reaction temperature is low, and strong corrosivity and toxicity are arranged.Last century the seventies, phosphoric acid, metal halide, aluminium oxide etc. are used as the isomerization of butene catalyst and use.Though phosphoric acid, the active height of metal halide, reaction temperature is also lower, selectivity and poor stability, and same existence corrosion and pollution problem.Afterwards, the introducing of solid heterogeneous catalysts such as ferrierite had overcome the shortcoming of liquid acid catalyst, and better active, reaction temperature is lower, but the non-precious metal catalyst poor selectivity, easy carbon distribution inactivation, noble metal catalyst are easy to poison.Therefore, development of new efficiently isomerization catalyst be that the researcher dreams of.
Following Patent publish the isomerized catalyst of n-butene.
Patent CN1676214A (2005) has disclosed a kind of preparation method and application of n-butene isomerization catalyst.It is characterized in that: adopt infusion process that precious metals pt and Pd are carried on the complex carrier of aluminium oxide, Beta zeolite and modenite composition and prepare catalyst.
Patent CN1522175A (2004) has disclosed a kind of n-butene isomerization preparing isobutene catalyst.It is characterized in that: with Pt or Pd active component.With magnesia is carrier, adopts the normal pressure infusion process.
Patent WO02096843A1 (2002.) has disclosed catalyst and the application thereof that isobutene is produced in a kind of n-butene isomerization.It is characterized in that: be the magnesium alkali zeolite catalyst of active component with Mg.
Patent US5182247A (1993.) has disclosed a kind of n-butene isomerization catalyst and application thereof.It is characterized in that: with aluminium oxide and silica is that mix with sulfuric acid in the activated centre, adopts the immersion process for preparing catalyst under the sulfuric acid existence.
Patent WO9323353A1 (1993) has disclosed a kind of n-butene isomerization catalyst and preparation method thereof.It is characterized in that: the mixture with ZSM-23 and ZSM-35 is a carrier, adopts the method for oxalic acid preliminary treatment carrier to prepare catalyst.
Patent AU1805292A (1993) has disclosed a kind of n-butene isomerization preparing isobutene catalyst.It is characterized in that: adopt infusion process that precious metals pt and Pd are carried on the complex carrier of aluminium oxide, SAPO-11 and modenite composition and prepare catalyst.
Patent US5095169 (1992) has disclosed linear paraffin isomerization reaction method.It is characterized in that: be active component with Pt, Beta and MCM-22 molecular sieve are the preparing carriers catalyst.
Patent US5107054 (1992) has disclosed linear paraffin isomerization reaction method.It is characterized in that: be active component with Pt, the Beta molecular sieve is the preparing carriers catalyst.
Patent US5057471 (1991) has disclosed the reaction method of linear paraffin hysomer.It is characterized in that: with Pt is active component, is the preparing carriers catalyst with the modenite.
Patent CN86106388 (1988) has disclosed a kind of preparation method of alkane isomerization catalyst.It is characterized in that: with precious metals pt, Pd is active component, and modenite is a carrier, adopts the conventional ion exchange process to prepare catalyst.
Patent CN86102384A (1986) has disclosed a kind of catalyst of normal alkane isomerization.It is characterized in that: with platinum, palladium and nickel is active component, and modenite is a carrier, adopts base exchange method to prepare catalyst.
Also have a lot of patents to relate to catalyst for normal paraffin isomerization, as:
Relate to platinum, palladium is the catalyst patent of active component: US2010056839A1 (2011), EP2331488A2 (2011), WO2010028267A2 (2010), WO2010028267A3 (2010), US4132745A (1979).
Patent EP0706984A1 (1996) relates to the catalyst that gallium is an active component.
Relating to zirconium is the catalyst patent of active component: CN101171213A (2008), CN101172248A (2008), CN1544400A (2004), RU2236291C1 (2004), CN1194883A (1998), CN1164509A (1997), US4409418A (1983).
The catalyst patent that relates to other active component is following: US7915468B2 (2011); CN101831319A (2010); US2009192339A1 (2010); US7553999B2 (2009); CN101500968A (2009); CN101514135A (2009); US2008146858A1 (2008); CN100379712C (2008); CN101121121A (2008); US6852901B2 (2005); EP1513788A1 (2005); US2004106836A1 (2004); EP0854125B1 (2003); WO02094433A1 (2002); RU2156755C2 (2002); CA2448532A1 (2002); US6323384B1 (2001); US6111160A (2000); US5902920A (1999); US5969203A (1999); CA2183713A1 (1998); AU694675B2 (1998); AU682461B2 (1997); EP0641299B1 (1997); JP9136847A (1997); US5510560A (1996); US5516959A (1996); US5523511A (1996); US5491276A (1996); AU667547B2 (1996); JP8176020A (1996); EP0664775A1 (1995); EP0664775B1 (1995); EP0667184B1 (1995); EP0641299A1 (1995); WO9528372A1 (1995); US5449851A (1995); CA2141585A1 (1994); EP0641299A4 (1994); AU3484793 (1994); US5321194A (1994); WO9408920A1 (1994); US5191146A (1993); US5237121A (1993); EP0523838B1 (1993); EP0523838A2 (1993); AU4289593A (1993); US5177281A (1993); US5132484A (1992); US5146035A (1992); CA1238925A1 (1988); US4587375A (1986); US4433191A (1984); HU34419A2 (1983); US4410754A (1983); US3800003A (1974); US2220693A (1940).But, the related catalyst activity metal component of these patents is not a gold.
In addition, there are many open source literatures also to report the isomerized catalyst of n-butene.As:
Open source literature Applied Clay Science.2005 (29): 117-123 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with Al, Cr, Ni and Fe is active component, is carrier with the bentonite, adopts the method for ion-exchange to prepare catalyst.
Open source literature Applied Catalysis A:General2003 (239): 59-70 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with Cs and K is active component, is carrier with the X zeolite, adopts ion-exchange and immersion process for preparing catalyst.
Open source literature Applied Catalysis A:General2003 (255): 349-354 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with silica alumina ratio is that 90 HZSM-5 is a catalyst.
Open source literature Applied Catalysis A:General2001 (206): 57-66 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with silica alumina ratio is that 17 and 170 HZSM-5 is a catalyst.
Open source literature petrochemical industry 2001 (30) 2:210-212 have reported n-butene skeletal isomerization preparing isobutene Preparation of catalysts and application thereof.It is characterized in that: with pyridine, pyrrolidines and tetramethyl ethyl diamines is that template or mixed templates prepare ZSM-35, and it is catalyst that exchange of process ammonia and sour reaming make HZSM-35.
Open source literature Xiamen University journal 2000 (39) 4:571-575 have reported the preparation and the application thereof of n-butene isomerization catalyst.It is characterized in that: be active component with Mg, adding a small amount of ZSM-23 with ferrierite is carrier, preparation ferrierite composite catalyst.
Open source literature Applied Catalysis A:General.1998 (168): 171-177 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with Mg and K is active component, is carrier with the HZSM-22 zeolite, adopts ion-exchange and immersion process for preparing catalyst.
Open source literature Applied Catalysis A:General.1998 (174): 163-175 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with Ga and Fe is active component, is carrier with the HZSM-22 zeolite, introduces heteroatomic method in the employing building-up process and prepares catalyst.
Open source literature Catalysis Today.1998 (44): 215-222 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with F/Al
2O
3With the MFI zeolite be catalyst.
Open source literature Applied Catalysis A:General.1997 (164): 291-301 has reported n-butene isomerization preparing isobutene catalyst and application thereof.It is characterized in that: with Mg, Mn, Cu and Ca is active component, is carrier with the HZSM-22 zeolite, adopts ion-exchange and immersion process for preparing catalyst.
Open source literature Xiamen University journal (natural science edition) 1997 (36) 5:723-727 have reported the isomerized catalyst of n-butene.The document is with HZSM-23, Al
2O
3Or HZSM-23 and Al
2O
3Mixture be catalyst.
Open source literature Acta PhySico-Chimica Sinica 1995 (11) 1:9-13 have reported the isomerized non-precious metal catalyst of n-butene.The document is an active component with Ce, with SiO
2Be carrier, adopt the immersion process for preparing catalyst.
In addition, the following discloses document has also been introduced catalyst for normal paraffin isomerization.
What relate to platinum, palladium and be active component has a following discloses document: Catalysis Today 73 (2002) 167-176; Journal of Molecular Catalysis A:2007 (264): 192-201; Chemical Engineering Journal 2007 (134) 1-3:106-110; Microporous and Mesoporous Materials 2000 (38): 221-237;
What relate to zirconium and be active component has a following discloses document: Applied CatalysisA:General, 2004 (274): 159-165; J.Chem.Soc.Faraday Trans.1997 (93) 23:4201-4206;
What relate to cobalt and molybdenum and be active component has a following discloses document: Journal of Molecular Catalysis A:2011 (335): 112-120; Chemical industry journal 1988 (3): 698-706; J.Chem.Soc.Faraday Trans.11987 (83): 1213-1226; Peking University's journal (natural science edition) 1986 (6): 17-28;
What relate to zinc and be active component has a following discloses document: Acta PhySico-Chimica Sinica 2003 (19) 3:216-220; Petrochemical industry 1984 (13): 578-582; Catalysis Letters 1998 (55): 173-176.
What relate to nickel, tungsten and be active component has a following discloses document: Catalysis Communications 2011 (12) 368-374; Applied CatalysisA:General1999 (187): 141-146;
Oil refining and chemical industry 2010 (21) 10; Industrial Catalysis 2007 (15) 2:22-25; Industrial Catalysis 2004 (12) 8:15-18.
What relate to magnesium and be active component has a following discloses document: Xiamen University's journal (natural science edition) 2000 (39) 4:570-576; Petrochemical technology 1999 (6) 4:246-249;
What relate to other active component has a following discloses document: Journal of Catalysis 2011 (277) 173-195; Petrochemical technology 2010 (17) 4:39; Industrial Catalysis 2008 (16) 11:53-57; Petrochemical industry 2006 (35) 4:314-318; Catalysis journal 2004 (25) 2:158-162; Applied CatalysisA:General2003 (255): 349-354; Journal of Molecular Catalysis A:2002 (178): 147-160; Journal of Molecular Catalysis A:2000 (158): 5-17; Technical progress 2000 (6): 16-19; Chemical industry progress 2000 (6) 16-19; Applied CatalysisA:General1999 (183): 155-165; Industrial Catalysis 1999 (2): 3-10; Catal.Lett1999 (58) 231; Catalysis Today1998 (44) 215-222; Scientific and technological information exploitation and economic 1998 (6): 32-33; Journal of Catalysis 1998 (179) 581; Applied CatalysisA:General1998 (174): 207; Applied CatalysisA:General1998 (174): 163; Applied CatalysisA:General1997 (150): 101; Journal of Catalysis 1997 (168) 334; Stud.Surf.Sci.Ctal., 1997 (105): 1373; Institution of higher education's chemistry is learned 1996 (17) 4:635-637; Catal.Lett1996 (36) 249; Petroleum journal (PETROLEUM PROCESSING) 1996 (12) 2:38-43; Petrochemical technology economy 1996 (3): 33-37; Petrochemical industry dynamic 1995 (6): 35-42; Petrochemical technology economy 1995 (11): 14-21; Microp.Mat.1994:477; Newspaper petrochemical industry 1989 (2) 18:75:79; Peking University's journal (natural science edition) 1984 (5) 58-64;
It has been generally acknowledged that the butylene skeletal isomerization is the reaction of a complicacy, from the thermodynamics angle, low temperature helps isomerization of butene and produces isobutene, but low temperature will cause side reaction and reduce selective isobutene.Except reaction temperature, the acid site is also very important.Isomerization of butene needs certain acid amount, need have the acid catalyst of strong acid center, with sulfuric acid type (H
2SO
4), when halide type (HF) and non-halide type (phosphoric acid, boric acid and boron phosphate) etc. are catalyst, can cause metal erosion and contaminated environment.During with the solid acid catalyst of supporting Pt and halogens, very responsive to water, reaction raw materials needs strict dehydration.During with the solid acid catalyst of ferrierite representative, have poor stability, inactivation is fast, is prone to shortcomings such as carbon distribution.Therefore, development of new efficiently catalyst be necessary.
In the catalyst research of being reported, the metal component of load mainly concentrates on Zn, Ga, and Pt, Pd, Ti, Ni, Cu, Cr etc., and be that active component is used for the n-butene isomerization report is not arranged with Au.
The preparation of nano catalyst and application are the great discoveries of catalysis field.Always gold is considered to catalytically inactive, but with its load on carry out high dispersive on the oxide carrier after, just demonstrate unique catalytic activity.Nano catalyst is at catalysis CO oxidation, ozone decomposition, water gas shift reaction, NO
xReduction, acetylene hydrochlorination, epoxidation of propylene, fuel cell, field of petrochemical industry demonstrate application prospect (Catal.Rev.-Sci.Eng, 1999,41 (3) 319-388).
The preparation method of nano catalyst is divided into two kinds: the one, and carrier and golden precursor coprecipitation; The one, golden precursor is loaded to infusion process and deposition-precipitation method on the good carrier of prepared beforehand.The preparation method of early stage load type gold catalyst infusion process commonly used.It is lower that infusion process is generally used for preparing active component content, and need the catalyst of sufficient mechanical strength.With the preparation process of this method nano catalyst be, at first with carrier impregnation in the salting liquid that contains gold, and then carry out drying, roasting and reduction processing, method is simple.It is carrier that infusion process can be selected various metal or nonmetal oxide and molecular sieve etc. for use.The commonly used golden precursor of preparation nano catalyst is gold chloride (HAuCl
4.3H
2O) and chlorauride (AuCl
3) and gold complex KAu (CN)
2[Au (en)
2] Cl
3(en is an ethylenediamine) etc.
Coprecipitation is the effective ways of preparation high capacity amount Au catalyst; Typical preparation process is: with the precursor salt solution and the golden precursor salt solution mix of carrier; Precipitate with precipitating reagent then, leave standstill again, filter, wash, drying and high-temperature roasting handle.The advantage of coprecipitation is the preparation good reproducibility, and shortcoming is that the part gold grain can be buried in carrier inside, and the utilization rate of gold is low, is not suitable for carriers such as titanium oxide, zeolite molecular sieve.The control of pH value is technological difficulties when using the precipitation method.
Deposition-the precipitation method also are the supported catalyst preparation methods who uses always, and it has the advantage of the infusion process and the precipitation method concurrently.The canonical process for preparing Au catalyst with the deposition-precipitation method is: with metal or nonmetal oxide and molecular sieve etc. in carrier the joins golden precursor solution; Continuous stirring also dropwise adds precipitating reagent under the certain reaction temperature; Solution reaction is carried out, fully under suitable pH value until deposition.And then solid content carried out sedimentation, filtration, washing, drying, roasting or activation processing.
As a rule, after the load gold catalyst drying of the preparation that ins all sorts of ways, exist with+3 valency oxidation state forms, most gold atoms become zeroth order after high-temperature heat treatment.In order to make load gold catalyst have high activity, it is crucial adopting appropriate preparation method to make gold particle high dispersive on carrier.
Now, existing many Patent publish the preparation method of load type nano gold catalyst.As:
Patent CN101530814A (2009) has disclosed a kind of preparation method of load type nano gold catalyst.It is characterized in that: the HTS of-micropore composite construction mesoporous to have is a carrier, and carrying method is a deposition-precipitation method, loads under the normal pressure and carries out, and is the precursor of gold with the gold chloride.
Patent CN101237931A (2008) has disclosed a kind of preparation method of load gold catalyst.It is characterized in that: be carrier with the porous metal oxide, gold chloride is a precursor, and carrying method is conventional infusion process, is immersed under the normal pressure to carry out.
Patent CN101204655A (2008) has disclosed a kind of preparation method of nano catalyst.It is characterized in that: with aluminium oxide, silica, pottery, TiO
2Deng being carrier, gold chloride is golden precursor, and carrying method is an infusion process, is immersed under the condition of ultrasonic wave or ultrasonic wave and vacuum coexistence to carry out.
Patent CN1795985A (2006) has disclosed a kind of method for preparing load type gold catalyst.It is characterized in that: be the co-precipitation carrier with the ferric nitrate, the chloric acid gold is a precursor, is precipitating reagent with sodium carbonate, and carrying method is a coprecipitation, and co-precipitation is carried out under normal pressure.
Patent CN1565727A (2005) has disclosed a kind of preparation method of load type nano gold catalyst.It is characterized in that: with SiO
2, Al
2O
3, TiO
2Deng oxide is carrier, and the chloric acid gold is a precursor, and carrying method is an infusion process, and dipping carries out under normal pressure with isopyknic mode.
Following patent has also disclosed the preparation method of load type gold catalyst.
Relate to SiO
2Carrier loaded Au catalyst has following patent: CN101797514A (2010); CN101862660A (2010); CN101574654A (2009); US6821923 (2004); EP1044067B1 (2004); EP1027153B1 (2004); US6486093 (2002); US6303537 (2001); US6174531 (2001); EP0906151B1 (2001); US6114571 (2000); CN1251323A (2000); WO030818A1 (1999); WO062633A1 (1999); WO062632A1 (1999); US5693586 (1997).
Relate to Al
2O
3The load gold catalyst of carrier has following patent: CN101618328A (2010), US0010278A1 (2010), EP1309536B1 (2010), US0221849A1 (2009), US0088319A1 (2009), CN101147862A (2008), CN101049561A (2007), CN101036887A (2007), WO065138A1 (2006), US7119225 (2006), CN1827213A (2006), WO016298A1 (2002), EP0909213B1 (2001), EP0653401B1 (1997).
Relate to TiO
2The load gold catalyst of carrier has following patent: CN101711982A (2010), EP1309536B1 (2010), CN101380575A (2009), WO076137A3R4 (2008), WO003450A1 (2006), US7119225 (2006), US6821923 (2004), WO016298A1 (2002), CN1349430A (2002).
Relate to ZrO
2The load gold catalyst of carrier has following patent: US0190347A1 (2007), WO0465145 (2006), US0276741A1 (2005), WO046255A1 (1999), US5895772 (1999).
In addition, patent CN101683619A (2009) relates to Fe
2O
3Load gold catalyst for carrier.
It is the load gold catalyst of carrier that patent CN101722009A (2010) relates to CuO.
The load gold catalyst that relates to composite oxide carrier has following patent: CN101822990A (2010), CN101822981A (2010), CN101612578A (2009), CN101376107A (2009), US02410381A1 (2008), US0193354A1 (2008), CN1724153A (2006), US0065355A1 (2005), CN1698932A (2005), US0127353A1 (2004), US0060643A1 (2003), USP4839327, USP4837219.
The load gold catalyst patent that relates to carbon carrier in addition: CN101631610A (2010), CN101648137A (2010), CN101785997A (2010), CN101804347A (2010), CN101829567A (2010).
But existing patent all prepares load gold catalyst with non-pressure process.
In addition, many open source literatures have also related to the preparation method of load type nano gold catalyst.As:
Open source literature Appl.Catal.A:Gen.291 (2005) 62, J.Catal.231 (2005) 105 and Geochem.Intern.11 (1985) 1656 have reported the influence that acidity (pH) prepares load type gold catalyst to deposition-precipitation method, and carrier is TiO
2The result shows that pH has considerable influence to the activity of nano catalyst.This mainly is because under different pH values, the hydrolysis degree of golden precursor compound is different.Along with the rising of pH value, golden precursor compound (AuCl
4)
-Progressively be hydrolyzed to AuCl
3(H
2O), (AuCl
3(OH))
-, (AuCl
2(OH)
2)
-, (AuCl (OH)
3)
-(Au (OH)
4)
-
Different golden precursors are hydrolyzed to because of nature differences such as adsorption capacities, and load gold catalyst is exerted an influence.The deposition-precipitation method that this open source literature adopts carries out under condition of normal pressure.
Open source literature Appl Catal A:Gen, 291 (2005) 162 have reported a kind of method for preparing load gold catalyst.Its technical characterictic is: with Y, β and modenite is carrier, with HAuCl
4Be golden precursor, use NaOH to be precipitating reagent, adopt deposition-precipitation method, operate under the normal pressure and carry out.
Open source literature Appl Catal B:Env, 41 (2003) 83 have reported a kind of method for preparing load gold catalyst.Its technical characterictic is: with Y, β and modenite is carrier, with HAuCl
4Be golden precursor, use NaOH to be precipitating reagent, adopt deposition-precipitation method, operate under the normal pressure and carry out.
Open source literature Appl.Catal.A:Gen.240 (2003) 243 has reported a kind of method for preparing load gold catalyst.Its technical characterictic is: with Ti-MCM-41 is carrier, is precipitating reagent with NaOH, adopts deposition-precipitation method, operates under the normal pressure and carries out.
Open source literature J.Catal.209 (2002) 331 has reported a kind of method of load gold catalyst.Its technical characterictic is: with Ti-MCM-48 is carrier, is precipitating reagent with NaOH, adopts deposition-precipitation method, operates under the normal pressure and carries out.
Open source literature Appl.Cattal.A:Gen.226 (2002) has reported that 1. deposition-precipitation method prepares the principles of chemistry of nano catalyst.Precipitating reagent is a urea, TiO
2Be carrier.This open source literature adopts TiO
2For carrier and urea are precipitating reagent, deposition-precipitation method operates under the condition of normal pressure and carries out.
Open source literature App.Catal.A:Gen.190 (2000) 43 has reported a kind of method for preparing load gold catalyst.Its technical characterictic is: with Ti-MCM-41 is carrier, is precipitating reagent with NaOH, adopts deposition-precipitation method, operates under the normal pressure and carries out.
In addition, the following discloses document also relates to the preparation method of load type gold catalyst: J.Catal, 2006,237:303-313; Catal.Today, 2006,111 (1-2): 22-33; J.Phys.Chem, B:2005,109:2321-2330; Catal.Lett, 2005,99 (3-4): 235-239; J.PhysChem, B:2005,109:3956-3965; Appl.Catal; B:Environ; 2005,61:201-207; Appl.Catal, A:Gen, 2005,191:222-229; Appl.Catal.A:Gen, 2004,267:191-201; Appl.Catal, A:Gen, 2004,277:31-40; J.Am.Chem.Soc, 2004,126:38-39; J.Catal, 2004,226:156-170; J.Catal, 2003,216 (1-2): 213-222; Catal.Lett, 2003,86:1-8; Oxid.Commun, 2003,26 (4): 492; Appl.Catal, A:Gen, 2003,246:29-38; Appl.Catal, A:Gen, 2003,243:25-33; Appl.Catal.A:Gen., 2002,226:1-13; Appl.Catal, A:Gen, 226 (2002) 1; Chemical progress 2002 (5): 360-367.J.Phys.Chem, J.Catal, 2002,209:331-340; B:2002,106 (31): 7634-7642; Catal.Today, 2002,74:265-269; Gold Bull, 34 (2001) 4:11; Appl.Catal, A:Gen, 2001,215:137-148; Appl.Catal, A:Gen, 2001,209:291-300; Catal.Today, 2001,64 (1): 69-81; Appl.Catal, B:Environ, 2001,33:217-222; Appl.Catal, A:Gen, 2001,222:427-437; Appl.Catal, B:Environ, 2000,28:245-251; J.Phys.Chem, B:2000,104:11153-11156; J.Catal, 2000,191:332-347; J.Catal, 2000,191:430-437; Catal.Rev-Sci.Eng, 1999,41 (3): 319-388; Catal.Today, 1999,54:31-38; Gold.Bull, 1998,31:105-106; Gold Bull, 31 (1998) 4:111-118; J.Catal, 1998,178:566-575; Catal.Lett. (1997) 43 (1-2): 51-54; Catal.Today, 36 (1997) 153; Catal.Today, 1996,29:443-447; Surf.Sci.Catal, 91 (1995) 227; " Preparation of catalysts V " Edit., 1991, Amsterdam, 695-704; J.Catal., 1989,115:301-309; Stud.Surf.Sci.Catal, 44 (1988) 33; Chem.Lett, 2 (1987) 405; J.Chem.Soc.Faraday Trans, 175 (1979) 385.
Above open source literature has adopted distinct methods and different oxides and zeolite molecular sieve preparing carriers load gold catalyst.But the common feature of these methods is that operation is all carried out under normal pressure during load.Prepared catalyst is easy to reunite through roasting.When adopting ZSM-5 to be carrier, can only obtain the load type gold catalyst that gold grain is 40-50nm, can not obtain more short grained Au/ZSM-5 catalyst.
Summary of the invention
The invention provides the method that a kind of load type nano gold catalyst is used for the n-butene isomerization reaction.The n-butene isomerization should be used metal-sour bifunctional catalyst.
We are through discovering, when being carried on nm of gold on the silica-rich zeolite, gold can with the silicon hydroxyl generation strong interaction in the silica-rich zeolite, thereby form Si-O (H)-Au structure.Because the polarization of Au makes this Si-O (H)-Au ol group have strong protonic acid property.What is interesting is also had metallicity simultaneously, thereby formed metal-sour bifunctional catalyst by the gold of load.Because the highly acid of Si-O (H)-Au structure so the acidity of carrier is not weakened behind the load gold, but has obvious reinforcement, make catalyst align the isomerization of butene reaction and have low temperature active.Through studying further discovery; The carrying method of Au plays crucial effect for producing above-mentioned acid ol group; After zeolite carried out sufficient negative pressure degasification purified treatment, adopt the negative pressure deposition-precipitation method to load to golden precursor on the carrier again, help forming Si-O (H)-Au structure most.In addition, we make golden high dispersive through introducing second metal, prevent the gold particle gathering.Second metal that is added also plays the effect of the lewis acidity that strengthens catalyst, and load gold catalyst is played promoting catalysis.Generally speaking, i.e. load gold load second metal again can increase the Bronsted acid and the lewis acidic acidity of carrier simultaneously.Said zeolite refers to the silica-rich zeolite molecular sieve; Especially S-1, ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2, and ZSM-12, beta-zeolite, modenite and TS-1 molecular sieve or the above-mentioned zeolite that process is metal-modified and other methods were handled.Said golden precursor mainly refers to HAuCl
4, precipitating reagent mainly refers to urea.If the second master metal Zn, Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag and Cu.Under condition of negative pressure, prepare load gold catalyst and help purifying zeolite surfaces externally and internally and duct, make Au be easy to get in the duct, reach high dispersive and combine to form Si-O (H)-Au structure with the silicon hydroxyl of surfaces externally and internally with deposition-precipitation method.
Load type gold catalyst through this invention preparation has required strong acid center of n-butene isomerization and metal active center, can make n-butene under the difunctional effect of metal and acid, and skeletal isomerization generates isobutene.
Technical scheme of the present invention is following:
1. the preparation of load gold catalyst
The first step is carried out preliminary treatment to the silica-rich zeolite carrier.
(1). the silica-rich zeolite carrier is carried out calcination process.Sintering temperature selects 300～700 ℃, preferred 400～600 ℃; Roasting time is 4～20 hours, preferred 3～8 hours.The silica alumina ratio of said silica-rich zeolite is 10～∞, like ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2, ZSM-12, beta-zeolite, modenite, TS-1 and pure silicon zeolite or through above-mentioned zeolite metal-modified and that other methods were handled.The grain size of zeolite is between 5nm～30 μ m.
The synthetic of above carrier can adopt the prescription in disclosed patent and the document to carry out.Like patent US3702886 (1972); US3941871 (1976); US4061724 (1977); US4166099 (1979); CN1086792A (1994); CN1219571A (1999); CN1056818C (2000); CN100457622A (2001); WO0138224A (2001); CN1212892A (2002); CN1328960A (2002); CN1088406C (2002); CN1417116A (2003); CN1530323A (2004); CN1699173A (2005); CN1686801A (2005); CN100344375A (2005); CN1715186A (2006); CN101007637A (2007); CN1307102C (2007); CN101279746A (2008); CN101214971 (2008); CN101613114 (2009); CN101554592A (2009); CN101559955A (2009); CN101428818B (2010); CN101993091A (2011) CN101417810A (2009); CN 101468800 (2009); CN 101519216 (2009); CN101554592A (2009); CN101618337A (2010); US20100298598A1 (2010); CN101801848A (2010); CN10204023A (2010); CN101973560A (2011); US7883686B2 (2011); WO2011061204A1 (2011); Microporous and Mesoporous Materials 31 (1999) 241-251; Journal of Materials Chemistry 12 (2002) 369-373; Journal of Molecular Catalysis B:Enzymatic 22 (2003) 119-133; Journal of Catalysis 255 (2008) 68-78.The engineer who is familiar with this area all can adopt the technical method of reporting in existing open source literature and the patent, carries out the synthetic of carrier.
(2). the ammonium exchange is handled: baked zeolite is carried out ion-exchange treatment with ammonium salt solution under suitable temperature.Then, spend deionised water, dry again, roasting obtains h-type zeolite.Ammonium exchange process major control Na+ content makes it can not be higher than 1.0%, is preferably lower than 0.8%.Any in the optional ammonium nitrate of described ammonium salt, ammonium chloride, the ammonium carbonate etc., ammonium salt solution concentration is 0.05～1.0mol/L, the liquid-solid volume ratio of catalyst and ammonium salt solution is 1: 1～20: 1, preferred 3: 1～10: 1; The exchange temperature is 20～80 ℃, preferred 20～60 ℃; Be 0.2～100 hour swap time, preferred 0.5～4 hour; Exchange number of times 1～5 time.80～200 ℃ of baking temperatures, 1～100 hour drying time; Because the strong complexing power among NH4+ → NH3+H+ between NH3 and the proton H+ requires roasting process to need fully, so sintering temperature selects 300～700 ℃, preferred 400～600 ℃; Roasting time is 4～20 hours, preferred 3～8 hours.Said Na+ Determination on content method can adopt flame photometer, and Inductively Coupled Plasma (ICP) measures.The engineer who is familiar with this area can carry out Na+ with reference to specification and measure.
(3). sour reaming is handled: h-type zeolite is carried out sour reaming handle under suitable acid concentration and temperature.Spend deionised water then to neutral, dry again, roasting obtains carrier.The optional HCl of said acid, HNO
3, H
2SO
4Or any in the citric acid, preferred HNO
3And citric acid.Because adopt HCl can introduce Cl
-, and H
2SO
4Decompose difficulty, be difficult for removing.Acid concentration is 0.05～6mol/L, the liquid-solid volume ratio of acid solution and catalyst 1: 1～20: 1, preferred 3: 1～10: 1; Acid is 30min～100 hour in the reaming processing time, preferred 1～5 hour; Treatment temperature is 20～80 ℃.Baking temperature is 50～200 ℃, and be 3～20 hours drying time, and sintering temperature selects 300～600 ℃, and roasting time is 1～4 hour.
The purpose of acid reaming is to remove the inner unformed impurity of HZSM-5, increases the diffusion rate in duct.In fact the h-type zeolite that obtains after the ammonium exchange just can directly be used as carrier.But sour reaming helps improving activity of such catalysts.
In second step, under condition of negative pressure, adopt deposition-precipitation method to prepare load gold catalyst.
(1). golden with the load of negative pressure deposition-precipitation method: as will to pass through pretreated h-type zeolite carrier and under uniform temperature, carry out the negative pressure degasification purified treatment.Treatment temperature is 20～90 ℃, and the degassing time is 0.5～12 hour, range of negative pressure is-0.01～-0.1Mpa; Under fully stirring, keep temperature and negative pressure state then, earlier with golden precursor solution contact carrier, and then in mixture, add precipitating reagent through negative pressure deposition sedimentation reaction load gold, the reaction time is 2～30 hours; Though higher vacuum is favourable to purifying, can increase the catalyst cost of manufacture.
(2). the sediment to the load gold carries out post processing: comprise Separation of Solid and Liquid, spend deionised water to there not being Cl
-And the drying of solid content and roasting.Wherein, optional 80～200 ℃ of baking temperature, optional 0.5～100 hour of drying time, optional 200 ℃～600 ℃ of sintering temperature, optional 0.5～100 hour of roasting time, the optional air of calcination atmosphere, nitrogen, helium, argon gas and oxygen.
In the 3rd step, under condition of negative pressure, adopt infusion process load second active component.
(1). with negative pressure impregnation second metal: the load type gold catalyst that will pass through the preparation of negative pressure deposition-precipitation method carries out described negative pressure degasification purified treatment at a certain temperature.Under fully stirring, keep temperature and negative pressure state, then through negative pressure impregnation method load second metal.Said second metal is Zn, Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag or Cu.Second preferred metal is introduced with nitrate, also acceptable salts hydrochlorate, and suitable concentration is 0.1～2mol/L, the volume ratio of golden precursor solution and carrier is 1: 1～10: 1, optional 20～90 ℃ of dipping temperature, optional 0.5～24 hour of dip time.
(2) solid content is carried out post processing: comprise Separation of Solid and Liquid, and the drying of solid content and roasting.Wherein, optional 80～200 ℃ of baking temperature, optional 0.5～100 hour of drying time, optional 200～600 ℃ of sintering temperature, optional 0.5～100 hour of roasting time, the optional air of calcination atmosphere, nitrogen, helium, argon gas and oxygen.
Acidity with the Au catalyst of method for preparing can adopt temperature programmed desorption of ammonia (NH
3-TPD) characterize with vibration absorption infrared method.Wherein, temperature programmed desorption of ammonia (NH
3-TPD) condition is, 0.14g sample (40-60 order) is placed the U type quartz tube reactor of internal diameter 5mm, He atmosphere and 600 ℃ of following activation 1 hour, reduces to 150 ℃ then, injects NH
3To saturated, remove the NH of physical absorption through He air-blowing cleaning
3After, being warmed up to 600 ℃ with the speed program of 15 ℃/min, the He gas velocity is 20ml/min in this process, the NH that desorption gets off
3Analyze with GC7890F type gas chromatograph, TCD detects.
Hydroxyl with the infrared spectrum characterization catalyst with acid specific practice is: will grind the self-supporting thin slice that thin sample Au catalyst powder is pressed into about 10mg, and in infrared pond, progressively be warming up to 300 ℃ and vacuumize degassing, at condition of high vacuum degree (10
-3Pa) find time under desorption 4 hours is reduced to room temperature then, tests the infrared hydroxyl spectrogram of pyridine at ambient temperature.Obtained behind the infrared hydroxyl spectrogram under the room temperature absorption pyridine 0.5 hour, desorption by heating, cool to room temperature record corresponding absorption infrared hydroxyl spectrogram of pyridine and pyridine infrared spectrum behind 150 ℃, 250 ℃, 300 ℃ and 450 ℃ of following desorptions respectively.
2. the bifunctional catalyst with the load gold carries out n-butene isomerization production isobutene.
Reaction raw materials is the mixture of n-butene, n-butene and isobutene and the mixture of n-butene, isobutene and butane; Can contain in the raw material less than carbon four with greater than the alkane and the alkene of carbon four, but the content of reactant n-butene preferably is not less than 50%.Reaction can and have under the situation of carrier gas in no carrier gas to be carried out.Described carrier gas is H
2, N
2, CO
2, CH
4, C
2H
6Or its any mixture, carrier gas/hydrocarbon ratio is 0～100.
(1) on fixed bed reactors, carry out the n-butene isomerization and produce isobutene: catalyst adopts conventional extruded moulding; Reaction temperature is 100～800 ℃, and preferred 150～600 ℃, reaction pressure is normal pressure～10MPa; Preferred 0.3～3.0MPa, weight space velocity are 0.5～20h
-1
(2) on moving-burden bed reactor, carry out the n-butene isomerization and produce isobutene: catalyst adopts conventional wear-resisting bead, and reaction temperature is 100～800 ℃, and preferred 150～600 ℃, reaction pressure is 0.1～0.5MPa, and weight space velocity is 0.5～20h
-1
(3) on fluidized-bed reactor, carry out the n-butene isomerization and produce isobutene: catalyst adopts the mist projection granulating moulding, and particle size range is the 20-120 micron.100～800 ℃ of reaction temperatures, preferred 150～600 ℃, reaction pressure is 0.1～0.3MPa, agent hydrocarbon ratio is 0.5～5.
The invention has the beneficial effects as follows, the load gold catalyst through the method preparation and the catalyst of bimetallic-modified have the preparation method simply, the acidity of gold particle high dispersive, carrier advantage such as be significantly improved.Can obtain acid strong metal-sour bifunctional molecule sieve catalyst.In the isomerization catalytic reaction, has active height, the advantage that reaction temperature is low.
Description of drawings
Fig. 1 is the temperature programmed desorption of ammonia (NH of the catalyst of the embodiment of the invention 1 preparation
3-TPD) spectrogram.
Fig. 2 is the pyridine adsorption infrared spectrum of the catalyst of the embodiment of the invention 1 preparation.
The specific embodiment
Through embodiment the present invention is further specified below, but the present invention does not receive the restriction of these embodiment.
The comparative example 1:
On fixed bed reactors, carry out the n-butene isomerization and produce isobutene.
(1). the method that discloses with reference to patent CN100364890C synthesizes the ZSM-5 zeolite powder, and the zeolite grain degree is less than 50nm.Obtained the ZSM-5 zeolite in 4 hours 540 ℃ of following roastings then.
(2). the ammonium exchange is handled: baked zeolite is carried out ion-exchange treatment with ammonium salt solution under suitable temperature.Then, spend deionised water, dry again, roasting obtains h-type zeolite.Said ammonium salt is an ammonium nitrate, and ammonium salt solution concentration is 0.6mol/L, and the liquid-solid volume ratio of ammonium salt solution and zeolite is 5: 1, and the exchange temperature is 30 ℃, and be 1 hour swap time, exchange number of times 2 times.110 ℃ of baking temperatures, 12 hours drying times, sintering temperature is 540 ℃, roasting time is 6 hours.Exchange back Na
+Content is not higher than 0.5%.
(3). sour reaming is handled: h-type zeolite is carried out sour reaming handle under suitable acid concentration and temperature.Spend deionised water then to neutral, dry again, roasting obtains carrier.Said acid is HNO
3Acid concentration is 0.6mol/L, the liquid-solid volume ratio of acid solution and zeolite 5: 1, and the sour reaming processing time is 24 hours, treatment temperature is 30 ℃.Baking temperature is 110 ℃, and be 12 hours drying time, and sintering temperature selects 540 ℃, and roasting time is 3 hours, obtains the HZSM-5 zeolite catalyst.This catalyst is carried out NH
3TPD and infrared spectrum acidity characterize, and the result sees to attach Fig. 1 and 2.
(4) the HZSM-5 zeolite is pressed the conventional method extruded moulding with boehmite, the zeolite catalysis agent content is 80%, and the reaction time catalizer loadings is 2g, and raw material is a n-butene, and n-butene purity is 99.5%, and the charging air speed is 1.0h
-1, reaction temperature is 350 ℃, is reflected under no carrier gas and the normal pressure to carry out.The reaction procatalyst purged 30 minutes with nitrogen under reaction temperature, reacted then, reacted sample analysis after 4 hours.Then the n-butene conversion ratio is 65%, and selective isobutene is 30%.
Embodiment 1:
The preparation of 0.1%Au/HZSM-5:
(1). the method that discloses with reference to patent CN100364890C synthesizes the ZSM-5 zeolite powder, and the zeolite grain degree is less than 50nm.Obtained the ZSM-5 zeolite in 4 hours 540 ℃ of following roastings then.
(2). the ammonium exchange is handled: baked zeolite is carried out ion-exchange treatment with ammonium salt solution under suitable temperature.Then, spend deionised water, dry again, roasting obtains h-type zeolite.Said ammonium salt is an ammonium nitrate, and ammonium salt solution concentration is 0.6mol/L, and the liquid-solid volume ratio of ammonium salt solution and zeolite is 5: 1, and the exchange temperature is 30 ℃, and be 1 hour swap time, exchange number of times 2 times.110 ℃ of baking temperatures, 12 hours drying times, sintering temperature is 540 ℃, roasting time is 6 hours.Exchange back Na
+Content is not higher than 0.5%.
(3). sour reaming is handled: h-type zeolite is carried out sour reaming handle under suitable acid concentration and temperature.Spend deionised water then to neutral, dry again, roasting obtains Zeolite support.Said acid is HNO
3Acid concentration is 0.6mol/L, the liquid-solid volume ratio of acid solution and zeolite 5: 1, and the sour reaming processing time is 24 hours, treatment temperature is 30 ℃.Baking temperature is 110 ℃, and be 12 hours drying time, and sintering temperature selects 540 ℃, and roasting time is 3 hours.
In fact the h-type zeolite that obtains after the ammonium exchange just can directly be used as carrier.But sour reaming helps improving activity of such catalysts.
(4). golden with the load of negative pressure deposition-precipitation method: as will to pass through pretreated h-type zeolite carrier and under uniform temperature, carry out the negative pressure degasification purified treatment.Specifically: good carrier 5g carries out the negative pressure degasification processing to get preliminary treatment.The negative pressure degasification treatment temperature is 80 ℃, and the degassing time is 5 hours, and pressure is-0.05MPa.Under fully stirring, keep temperature and negative pressure state then,, in mixture, add precipitating reagent again through negative pressure deposition sedimentation reaction load gold earlier with golden precursor solution contact carrier.The gold precursor is HAuCl
4, concentration is 5～50mmol/L, and the volume ratio of golden precursor solution and molecular sieve carrier is 1: 1～1: 10, and described precipitating reagent is a urea, and using urea regulator solution pH value is 4～9.Specific practice is to get the HAuCl that concentration is 24.26mmol/L
4Solution 1.26ml thin up is to 10ml, and the volume ratio that makes golden precursor solution and carrier is 2: 1; Using urea regulator solution pH value is 8; The deposition sedimentation reaction temperature is 80 ℃, and the reaction time is 20 hours, leaves standstill 4 hours after reaction stops.
(5). the solid content to the load gold carries out post processing: comprise Separation of Solid and Liquid, spend deionised water to there not being Cl
-And the drying of solid content and roasting.Wherein, baking temperature is 100 ℃, 12 hours drying times; 400 ℃ of sintering temperatures, roasting time 4 hours, calcination atmosphere is an air.Obtain the support type Au/HZSM-5 zeolite molecular sieve catalyst A-1 of particle diameter less than 10nm.This sample has been carried out NH
3-TPD and infrared spectrum characterization.Spectrogram is seen accompanying drawing 1 and Fig. 2.
Embodiment 2:
Repeat embodiment 1, but change the chlorauric acid solution consumption into the 3.14ml thin up to 10ml, sintering temperature is 300 ℃.Obtain the 0.3%Au/HZSM-5 load type gold catalyst.Be designated as: A-2.
Embodiment 3:
Repeat embodiment 1, but vacuum is changed into-0.01MPa, the chlorauric acid solution consumption changes 10.46ml into, and thin up obtains the 1.0%Au/HZSM-5 load type gold catalyst to 20ml.Be designated as: A-3.
Embodiment 4:
Repeat embodiment 1, but change the chlorauric acid solution consumption into 20.93.ml, thin up is to 25ml, and sintering temperature is 500 ℃.Obtain the 2.0%Au/HZSM-5 load type gold catalyst.Be designated as: A-4.
Embodiment 5:
Repeat embodiment 1, but vacuum is changed into-0.06MPa, the chlorauric acid solution consumption is 41.86ml, and thin up is to 50ml, and sintering temperature is 600 ℃.Obtain the 3.0%Au/HZSM-5 load type gold catalyst.Be designated as: A-5.
Embodiment 6:
Repeat embodiment 1, but change sintering temperature into 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃ respectively, calcination atmosphere is a nitrogen.Obtain the load type gold catalyst after the different temperatures roasting, catalyst is carried out NH
3-TPD characterizes, and the acid amount increases 10-50%.Then the optimum sintering temperature is 300～600 ℃.
Embodiment 7:
Repeating embodiment 1, is the big grain ZSM-5 of 5 μ m but synthesize grain size according to following method, and changes the consumption of urea precipitating reagent, makes the pH value be respectively 3,5,6,8,9 and 10.The method of synthetic ZSM-5 zeolite is: take by weighing certain amount of industrial aluminum sulfate earlier and use deionized water dissolving, then after wherein adding sulfuric acid, stirring, as A solution; Take by weighing a certain amount of waterglass again and be diluted with water to B solution.Then, under vigorous stirring, A solution slowly is added drop-wise in the B solution; The reinforced back that finishes adds a certain amount of crystal seed, and (the crystal seed synthetic method is with reference to patent: ZL200510200328.9); Continue to stir 2h, obtain even gel, the mole of gel is consisted of: SiO2/Al2O3=50; Na2O/SiO2=0.078; H2O/SiO2=900; Amount of seed is 5% (mass percent of SiO2 in the synthetic system).With the gained gel crystallization in the stainless steel crystallizing kettle of packing into.Crystallization temperature is 170 ℃, and crystallization time is 18h.After crystallization finished, suction method was removed mother liquor and filter cake is washed till neutrality, in 110 ℃ of oven dry down, obtained Na type ZSM-5 zeolite powder.Load type gold catalyst is carried out NH3-TPD characterize, the acid amount is compared with parent increases 10-55%.
Embodiment 8:
Repeat embodiment 3, but will the reaction time change 0.5,1,2,5 respectively into, 10,15,20,25,30,35 hours, obtain the 1.0Au/HZSM-5 catalyst under the differential responses time.NH
3-TPD result shows: the reaction time is too short, and carrier surface can only form a small amount of Au-O (H)-Si structure.Along with the prolongation of time, the pH value increases gradually, and the gold particle number of generation increases, thereby forms more Au-O (H)-Si structure at carrier surface.The optimum reaction time is 2～30 hours.
Embodiment 9:
Repeat embodiment 1, but vacuum is changed into respectively-0.01MPa ,-0.03MPa ,-0.05MPa ,-0.07MPa ,-0.1MPa.Obtain the load type gold catalyst under the different vacuums, catalyst is carried out NH
3-TPD characterizes, and the acid amount increases 10-53%.
Embodiment 10:
Repeat embodiment 1, but carrier is changed to the HZSM-8 zeolite, the ZSM-8 zeolite is synthetic with reference to the method that patent CN101703944A (2010) discloses, then 540 ℃ of following roastings 4 hours.Obtain the 0.1%Au/HZSM-8 load type gold catalyst.Be designated as: A-6.
Embodiment 11:
Repeat embodiment 2, but carrier is changed to the HZSM-11 zeolite, the ZSM-11 zeolite is synthetic with reference to the method that patent CN1367758 (2002) discloses, then 540 ℃ of following roastings 4 hours.Change sintering temperature into 400 ℃ simultaneously.Obtain the 0.3%Au/HZSM-11 load type gold catalyst.Be designated as: A-7.
Embodiment 12:
Repeat embodiment 2, but carrier is changed to the HZSM-12 zeolite, the ZSM-12 zeolite is synthetic with reference to the method that patent CN1774398 (2006) discloses, then 540 ℃ of following roastings 4 hours.Change sintering temperature into 400 ℃ simultaneously.Obtain the 0.3%Au/HZSM-12 load type gold catalyst.Be designated as: A-8.
Embodiment 13:
Repeat embodiment 3, but carrier is changed to the MCM-22 zeolite, the MCM-22 zeolite is synthetic with reference to the method that patent CN1328960A (2002) discloses, then 540 ℃ of following roastings 4 hours.Simultaneously vacuum is changed into-0.05MPa.Obtain the 1.0%Au/MCM-22 load type gold catalyst.Be designated as: A-9.
Embodiment 14:
Repeat embodiment 4, but carrier is changed to the MCM-49 zeolite, the MCM-49 zeolite is synthetic with reference to the method that patent CN101468800 (2009) discloses, then 540 ℃ of following roastings 4 hours.Simultaneously vacuum is changed into-0.06MPa.Obtain the 2.0%Au/MCM-49 load type gold catalyst.Be designated as: A-10.
Embodiment 15:
Embodiment 16:
Repeat embodiment 1, but carrier is changed to the ITQ-2 zeolite, the ITQ-2 zeolite is synthetic with reference to the method that patent CN101973560A (2011) discloses, then 540 ℃ of following roastings 4 hours.Change the chlorauric acid solution consumption into 15.70ml simultaneously, thin up is to 20ml.Obtain the 1.5%Au/ITQ-2 load type gold catalyst.Be designated as: A-12.
Embodiment 17:
Repeat embodiment 3, but carrier is changed to H β zeolite, H β zeolite is synthetic with reference to the method that patent CN1086792A (1994) discloses, then 540 ℃ of following roastings 4 hours.Simultaneously vacuum is changed into-0.05MPa.Obtain 1.0%Au/H β load type gold catalyst.Be designated as: A-13.
Embodiment 18:
Repeat embodiment 1, but carrier is changed to the S-1 zeolite, the S-1 zeolite is with reference to open source literature Microporous and Mesoporous Materials, and the method that 1999 (28) 3:387-393 disclose is synthetic, then 540 ℃ of following roastings 4 hours.Simultaneously vacuum is changed into-0.045MPa, the chlorauric acid solution consumption changes 6.28ml into, and thin up is to 10ml.Obtain the 0.5%Au/S-1 load type gold catalyst.Be designated as: A-14.
Embodiment 19:
Repeat embodiment 18, but carrier is changed to the TS-1 zeolite, the TS-1 zeolite is synthetic with reference to the method that patent CN100457622A (2001) discloses, then 540 ℃ of following roastings 4 hours.Obtain the 0.5%Au/TS-1 load type gold catalyst.Be designated as: A-15.
Embodiment 20:
Repeat embodiment 18, but carrier is changed to the ZSM-22 zeolite, the ZSM-22 zeolite is synthetic with reference to the method that patent US5783168A (1998) discloses, then 540 ℃ of following roastings 4 hours.Obtain the 0.5%Au/ZSM-22 load type gold catalyst.Be designated as: A-16.
Embodiment 21:
Repeat embodiment 4, but change the precipitating reagent consumption, making the pH value is 7, and vacuum changes into-0.04MPa, and sintering temperature changes 400 ℃ into.Obtain the 2.0%Au/HZSM-5 load type gold catalyst.Be designated as: A-17.
Embodiment 22:
Repeating embodiment 21, is the strip ZSM-5 zeolite of 10 μ m but use the synthetic grain size of following method, changes the precipitating reagent consumption simultaneously, and making the pH value is 5.The method of synthetic zeolite is: take by weighing certain amount of industrial aluminum sulfate and use deionized water dissolving, then after wherein adding sulfuric acid, stirring, as A solution; Take by weighing a certain amount of waterglass again and be diluted with water to B solution.Then, under vigorous stirring, A solution and the absolute ethyl alcohol that measures slowly are added drop-wise in the B solution successively, the reinforced continued that finishes stirs 2h, and the mole that obtains even gel consists of: SiO
2/ Al
2O
3=60; Na
2O/SiO
2=0.1; Ethanol/SiO
2=1.5; H
2O/SiO
2=900; Amount of seed is 5% (SiO in the synthetic system
2Mass percent).With the gained gel crystallization in the stainless steel crystallizing kettle of packing into.Crystallization temperature is 170 ℃, and crystallization time is 20h.After crystallization finishes, remove mother liquor and filter cake is washed till neutrality,, obtain the former powder of Na type ZSM-5 zeolite molecular sieve in 110 ℃ of oven dry down with suction method.Obtain the 2.0%Au/HZSM-5 load type gold catalyst.Be designated as: A-18.
Embodiment 23:
The preparation of 0.1%Au-3.0%Zn/HZSM-5:
(1). the method that discloses with reference to patent CN100364890C synthesizes the ZSM-5 zeolite powder, and grain size is less than 50nm.Then 540 ℃ of following roastings 4 hours.
(2). the ammonium exchange is handled: baked zeolite is carried out ion-exchange treatment with ammonium salt solution under suitable temperature.Then, spend deionised water, dry again, roasting obtains h-type zeolite.Said ammonium salt is an ammonium nitrate, and ammonium salt solution concentration is 0.6mol/L, and the liquid-solid volume ratio of ammonium salt solution and zeolite is 5: 1, and the exchange temperature is 30 ℃, and be 1 hour swap time, exchange number of times 2 times.110 ℃ of baking temperatures, 12 hours drying times, sintering temperature is 540 ℃, roasting time is 6 hours.Exchange back Na
+Content is not higher than 0.5%.
(3). sour reaming is handled: h-type zeolite is carried out sour reaming handle under suitable acid concentration and temperature.Spend deionised water then to neutral, dry again, roasting obtains carrier.Said acid is HNO
3Acid concentration is 0.6mol/L, the liquid-solid volume ratio of acid solution and zeolite 5: 1, and the sour reaming processing time is 24 hours, treatment temperature is 30 ℃.Baking temperature is 110 ℃, and be 12 hours drying time, and sintering temperature is 540 ℃, and roasting time is 3 hours.
In fact the h-type zeolite that obtains after the ammonium exchange just can directly be used as carrier.But sour reaming helps improving activity of such catalysts.
(4). golden with the load of negative pressure deposition-precipitation method: as will to pass through pretreated h-type zeolite carrier and under uniform temperature, carry out the negative pressure degasification purified treatment.Specifically: good carrier 5g carries out the negative pressure degasification processing to get preliminary treatment.The negative pressure degasification treatment temperature is 80 ℃, and the degassing time is 5 hours, and pressure is-0.05MPa.Under fully stirring, keep temperature and negative pressure state then,, in mixture, add precipitating reagent again through negative pressure deposition sedimentation reaction load gold earlier with golden precursor solution contact carrier.The gold precursor is HAuCl
4, concentration is 5～50mmol/L, and the volume ratio of golden precursor solution and molecular sieve carrier is 1: 1～1: 10, and described precipitating reagent is a urea, and using urea regulator solution pH value is 4～9.Specific practice is to get the HAuCl that concentration is 24.26mmol/L
4Solution 1.26ml thin up is to 10ml, and the volume ratio that makes golden precursor solution and carrier is 2: 1; Using urea regulator solution pH value is 8; The deposition sedimentation reaction temperature is 80 ℃, and the reaction time is 20 hours, leaves standstill 4 hours after reaction stops.
(5). the solid content to the load gold carries out post processing: comprise Separation of Solid and Liquid, spend deionised water to there not being Cl
-And the drying of solid content and roasting.Wherein, baking temperature is 100 ℃, 12 hours drying times; 200 ℃ of sintering temperatures, roasting time 6 hours, calcination atmosphere is a helium.
(6). with negative pressure impregnation second metal: the load type gold catalyst that will pass through the preparation of negative pressure deposition-precipitation method carries out the negative pressure degasification purified treatment at a certain temperature.Specifically: get the 5g load type gold catalyst and carry out the negative pressure degasification processing.The negative pressure degasification treatment temperature is 80 ℃, and the degassing time is 5 hours, and pressure is-0.05MPa.Under fully stirring, keep temperature and negative pressure state then, use the zinc nitrate solution contact catalyst.The nitric acid zinc concentration is 0.77mol/L, and the volume ratio of zinc nitrate solution and catalyst is 1: 1,30 ℃ of dipping temperatures, dip time 24 hours.
(7). the bimetallic solid content of load regulation is carried out post processing: comprise Separation of Solid and Liquid, and the drying of solid content and roasting.Wherein, optional 80 ℃ of baking temperature, 48 hours drying times, 400 ℃ of sintering temperatures, roasting time 60 hours, calcination atmosphere is a nitrogen.Obtain the 0.1%Au-3.0%Zn/HZSM-5 catalyst, be designated as A-19.
Embodiment 24:
Repeat embodiment 23, but change the chlorauric acid solution consumption into 20.93.ml, thin up obtains the 1.96%Au-2.94%Zn/HZSM-5 catalyst to 25ml, is designated as A-20.This sample has been carried out NH
3-TPD and infrared spectrum characterization, the result shows, the while load gold and second metallic zinc on the HZSM-5 zeolite, total acid content increases, and acid strength strengthens, and not only Bronsted acid increases enhancing, and Louis's acid solution also increases enhancing.
Embodiment 25:
Repeat embodiment 23, but change second activity component metal into Fe, Co, Ni, Ga, Cu successively, second metal is introduced with nitrate; Load capacity changes 1.0% into; Obtain load type gold catalyst 0.1%Au-1.0%Fe/HZSM-5 successively, 0.1%Au-1.0%Co/HZSM-5,0.1%Au-1.0%Ni/HZSM-5; 0.1%Au-1.0%Ga/HZSM-5,0.1%Au-1.0%Cu/HZSM-5.Be designated as: A-21～A-25.
Embodiment 26:
On fixed bed reactors, carry out the n-butene isomerization and produce isobutene.
The A-1 catalyst sample of above-mentioned preparation is pressed the conventional method extruded moulding with boehmite, and the zeolite catalysis agent content is 80%, and the reaction time catalizer loadings is 2g, and raw material is a n-butene, and n-butene purity is 99.5%, and the charging air speed is 1.0h
-1, reaction temperature is 350 ℃, is reflected under no carrier gas and the normal pressure to carry out.The reaction procatalyst purged 30 minutes with nitrogen under reaction temperature, reacted then, reacted sample analysis after 4 hours.Then the n-butene conversion ratio is 75%, and selective isobutene is 60%.
Embodiment 27:
Repeat embodiment 26, but change catalyst into A-3, reaction temperature changes 400 ℃ into, and then the n-butene conversion ratio is 78%, and selective isobutene is 69%.
Embodiment 28:
Repeat embodiment 26, but change catalyst into A-4, reaction temperature changes 260 ℃ into, and then the n-butene conversion ratio is 53%, and selective isobutene is 86%.
Embodiment 29:
Repeat embodiment 26, but change catalyst into A-6, reaction temperature changes 200 ℃ into, and reaction pressure changes 1.5MPa into, and the charging air speed changes 10h into
-1, then the n-butene conversion ratio is 45%, selective isobutene is 82%.
Embodiment 30:
Repeat embodiment 26, but change catalyst into A-7, reaction temperature changes 500 ℃ into, and reaction pressure changes 3.0MPa into, and the charging air speed changes 20h into
-1, then the n-butene conversion ratio is 85%, selective isobutene is 67%.
Embodiment 31:
Repeat embodiment 26, but change catalyst into A-8, reaction temperature changes 300 ℃ into, is reflected to face under the hydrogen situation to carry out, and hydrogen/hydrocarbon volume ratio is 10/1, and then the n-butene conversion ratio is 78%, and selective isobutene is 88%.
Embodiment 32:
Repeat embodiment 26, but change catalyst into A-9, reaction pressure changes 1.6MPa into, is reflected under the condition that nitrogen is carrier gas to carry out, and the volume ratio of nitrogen/hydrocarbon is 50/1, and then the n-butene conversion ratio is 95%, and selective isobutene is 80%.
Embodiment 33:
Repeat embodiment 26, but with catalyst change into A-11, A-12, A-13, A-14, A-15, A-18 then the n-butene conversion ratio be followed successively by 81%, 79%, 77%, 55%, 60%, 83%; Selective isobutene is followed successively by 68%, 70%, and 62%, 86%, 89%, 72%.
Embodiment 34:
Repeat embodiment 26, but change catalyst into A-19, A-20 successively, then the n-butene conversion ratio is followed successively by 85%, 90%; Selective isobutene is followed successively by 75%, 82%.
Embodiment 35:
Repeat embodiment 26, but change catalyst into A-21 successively, A-22, A-23, A-24, A-25, then all between 80-85%, selective isobutene is all between 70-80% for the n-butene conversion ratio.
Embodiment 36:
Repeat embodiment 26, but change catalyst into A-20, reaction temperature changes 300 ℃ into; Reaction pressure changes 1.6MPa into, is reflected under the hydro condition to carry out, and hydrogen/hydrocarbon volume ratio is 100/1; Reaction raw materials changes mixed butene into; Its n-butene and isobutene proportioning are 85%: 15%, and then the n-butene conversion ratio is 85%, and selective isobutene is 83%.
Embodiment 37:
Repeat embodiment 36, but reaction raw materials is changed into mixed c 4; Wherein n-butene content is 55%, isobutene content 1.5%, butane content 35%; Less than butane and alkene sum is 3.5%; Greater than butane and alkene sum is 5%, and then the n-butene conversion ratio is 60%, and selective isobutene is 77%.
Embodiment 38:
Repeat embodiment 37, but will react the mixture that carrier gas changes hydrogen and methane, ethane into, wherein the content of hydrogen is 60%, and always the volume ratio of carrier gas/hydrocarbon is 100/1, and then the n-butene conversion ratio is 55%, and selective isobutene is 80%.
Embodiment 39:
On moving-burden bed reactor, carry out the n-butene isomerization and produce isobutene.
The A-20 catalyst sample of above-mentioned preparation is processed wear-resisting bead; The wear-resisting pellet catalyst of 1000 grams is packed in the small-sized moving bed testing equipment, and raw material is a mixed c 4, and wherein n-butene content is 55%; Isobutene content 1.5%; Butane content 35% is 3.5% less than butane and alkene sum, is 5% greater than butane and alkene sum; Reaction temperature is 400 ℃, and reaction pressure is 0.5MPa, and the charging air speed is 3h
-1, hydrogen is carrier gas, hydrogen/hydrocarbon volume ratio is 50/1.Then the n-butene conversion ratio is 80%, and selective isobutene is 65%.
Embodiment 40:
Repeat embodiment 39, but be 200 ℃ with reaction temperature, the charging air speed changes 0.5h into
-1, then the n-butene conversion ratio is 50%, selective isobutene is 90%.
Embodiment 41:
Repeat embodiment 39, but change reaction raw materials into rich butylene mixed c 4, wherein n-butene content is 70%; Isobutene content 1.0%; Butane content 25% is 1.5% less than butane and alkene sum, is 2.5% greater than butane and alkene sum; Then the n-butene conversion ratio is 90%, and selective isobutene is 78%.
Embodiment 42:
On fluidized-bed reactor, carry out the n-butene isomerization and produce isobutene.
The A-20 catalyst of above-mentioned preparation is processed the powder of 20-120 micron with the conventional mist projection granulating method of forming.1000 gram catalyst are packed in the small-sized fluidized bed experimental rig, and raw material is a mixed c 4, and wherein n-butene content is 55%; Isobutene content 1.5%; Butane content 35% is 3.5% less than butane and alkene sum, is 5% greater than butane and alkene sum; Reaction temperature is 400 ℃, and reaction pressure is 0.2MPa, and agent/hydrocarbon ratio is 5; The mixture of hydrogen and methane, ethane is carrier gas, and wherein the content of hydrogen is 60%, and the volume ratio of total carrier gas/hydrocarbon is 100/1.Then the n-butene conversion ratio is 70%, and selective isobutene is 75%.
Embodiment 43:
Repeat embodiment 42, but change raw material into rich butylene mixed c 4, wherein n-butene content is 70%; Isobutene content 1.0%; Butane content 25% is 1.5% less than butane and alkene sum, is 2.5% greater than butane and alkene sum; Then the n-butene conversion ratio is 90%, and selective isobutene is 80%.
Embodiment 44:
Repeat embodiment 42, but be 300 ℃ with reaction temperature, then the n-butene conversion ratio is 45%, and selective isobutene is 85%.
Embodiment 45:
Repeat embodiment 42, but be 1 with agent/hydrocarbon ratio, then the n-butene conversion ratio is 50%, and selective isobutene is 82%.
Claims (7)
1. the zeolite catalyst conversion n-butene with the load gold is the method for isobutene, it is characterized in that comprising the steps:
A. the silica-rich zeolite carrier is carried out preliminary treatment
(1) the silica-rich zeolite carrier is carried out calcination process, sintering temperature selects 400～600 ℃, and roasting time is 3～8 hours; The silica alumina ratio of silica-rich zeolite is greater than 10, and the grain size of zeolite is at 5nm～30 μ m;
(2) the ammonium exchange is handled: baked zeolite is carried out ion-exchange treatment with 0.05～1.0mol/L ammonium nitrate, ammonium chloride or sal volatile down in 20～80 ℃, and the liquid-solid volume ratio of ammonium salt solution and zeolite is 3: 1～10: 1; Be 0.2～100 hour swap time, exchange number of times 1～5 time, control Na
+Content is controlled at less than 1.0% its scope; Spend deionised water then, carry out drying and calcination process again and obtain h-type zeolite; 80～200 ℃ of baking temperatures, 1～100 hour drying time; 400～600 ℃ of sintering temperatures, roasting time 3～8 hours;
(3) sour reaming is handled: with HCl, HNO
3, H
2SO
4Or the solution of citric acid carries out sour reaming processing to h-type zeolite; Spend deionised water then to neutral, dry again, roasting obtains carrier; Acid concentration is 0.05～6mol/L, the liquid-solid volume ratio of acid solution and zeolite 3: 1～10: 1, and the sour reaming processing time is 1～5 hour, treatment temperature is 20～80 ℃; Baking temperature is 50～200 ℃, and be 3～20 hours drying time; Sintering temperature is 300～600 ℃, and roasting time is 1～4 hour;
B. under condition of negative pressure, adopt deposition-precipitation method to prepare load gold catalyst
(1) with negative pressure deposition-precipitation method load gold: will pass through pretreated h-type zeolite carrier and carry out the negative pressure degasification purified treatment, treatment temperature is 20～90 ℃, and the degassing time is 0.5～12 hour, range of negative pressure is-0.01～-0.1MPa; Under agitation keep temperature and negative pressure state then, earlier with golden precursor solution contact carrier, and then in mixture, add precipitating reagent through negative pressure deposition sedimentation reaction load gold, the reaction time is 5～100 hours;
(2) sediment to the load gold carries out post processing: comprise Separation of Solid and Liquid, spend deionised water to there not being Cl
-, the drying of solid content and roasting; 80～200 ℃ of baking temperatures, 0.5～100 hour drying time; 300～700 ℃ of sintering temperatures; Roasting time 3～20 hours;
C. isobutene is produced in the n-butene isomerization on reactor
(1) on fixed bed reactors, carry out the n-butene isomerization and produce isobutene: catalyst adopts conventional extruded moulding, and reaction temperature is 150～600 ℃, and reaction pressure is 0.3～3.0MPa, and weight space velocity is 0.5～20h
-1
(2) on moving-burden bed reactor, carry out the n-butene isomerization and produce isobutene: catalyst adopts conventional wear-resisting bead, and reaction temperature is 150～600 ℃, and reaction pressure is 0.1～0.5MPa, and weight space velocity is 0.5～20h
-1
(3) on fluidized-bed reactor, carry out the n-butene isomerization and produce isobutene: catalyst adopts the mist projection granulating moulding, and particle size range is the 20-120 micron; Reaction temperature is 150～600 ℃, and reaction pressure is 0.1～0.3MPa, and agent hydrocarbon ratio is 0.5～5.
2. method according to claim 1 is characterized in that, said silica-rich zeolite is meant ZSM-5, ZSM-8, ZSM-11, MCM-22, MCM-49, MCM-56, ITQ-2, ZSM-12, beta-zeolite, modenite, TS-1 or pure silicon zeolite.
3. method according to claim 1 is characterized in that described golden precursor is HAuCl
4, wherein, HAuCl
4Concentration be 5～50mmol/L, the volume ratio of golden precursor solution and carrier is 1: 1～10: 1.
4. method according to claim 1 is characterized in that described precipitating reagent is a urea, and using precipitating reagent regulator solution pH value is 4～9.
5. according to claim 1,2,3 or 4 described methods, it is characterized in that on the catalyst of load gold with negative pressure impregnation second metal: the negative pressure degasification treatment temperature is 20～90 ℃, and the degassing time is 0.5～2 hour, range of negative pressure is-0.01～-0.1MPa; Under agitation keep temperature and negative pressure state to flood second metal then, second metal is Zn, Fe, Mo, Ni, Ga, Co, Pt, Pd, Ag or Cu; Second metal is introduced with nitrate or hydrochloride, and concentration is 0.1～2mol/L, and the volume ratio of golden precursor solution and carrier is 1: 1～10: 1, dip time 0.5～24 hour; The bimetallic solid content of load regulation is carried out post processing: comprise Separation of Solid and Liquid, the drying of solid content and roasting; Baking temperature is 50～200 ℃, and be 3～20 hours drying time; Sintering temperature selects 300～700 ℃; Roasting time is 3～20 hours.
6. method according to claim 1 is characterized in that described reaction raw materials is the mixture of n-butene, n-butene and isobutene and the mixture of n-butene, isobutene and butane; Contain in the raw material less than carbon four with greater than the alkane and the alkene of carbon four, but the content of reactant n-butene is not less than 50%.
7. method according to claim 5 is characterized in that described reaction is in the presence of carrier gas, to carry out, and described carrier gas is H
2, N
2, CO
2, CH
4, C
2H
6Or its any mixture, carrier gas/hydrocarbon ratio is 0～100.
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| CN103113178A (en) * | 2013-02-07 | 2013-05-22 | 大连理工大学 | Method for converting normal olefine into isomeric olefine with gold-supported molecular sieve catalyst |
| CN103145521A (en) * | 2013-02-07 | 2013-06-12 | 大连理工大学 | Method for converting n-butene into isobutene through using gold supported molecular sieve catalyst |
| CN103145517A (en) * | 2013-02-07 | 2013-06-12 | 大连理工大学 | Method for converting n-butane into isobutane through using gold supported molecular sieve catalyst |
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2011
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103113178A (en) * | 2013-02-07 | 2013-05-22 | 大连理工大学 | Method for converting normal olefine into isomeric olefine with gold-supported molecular sieve catalyst |
| CN103145521A (en) * | 2013-02-07 | 2013-06-12 | 大连理工大学 | Method for converting n-butene into isobutene through using gold supported molecular sieve catalyst |
| CN103145517A (en) * | 2013-02-07 | 2013-06-12 | 大连理工大学 | Method for converting n-butane into isobutane through using gold supported molecular sieve catalyst |
| CN103755512A (en) * | 2013-12-24 | 2014-04-30 | 山东滨州裕华化工厂有限公司 | Process for separating C4 fraction from etherified liquefied gas |
| CN105983435A (en) * | 2015-03-03 | 2016-10-05 | 卓润生 | Butane isomerization catalyst and preparation method and application thereof |
| CN105983435B (en) * | 2015-03-03 | 2019-05-07 | 卓润生 | A kind of isomerization of butene catalyst and its preparation method and application |
| CN113042097A (en) * | 2019-12-26 | 2021-06-29 | 中国石油天然气股份有限公司 | Molecular sieve catalyst, preparation method thereof and application of molecular sieve catalyst |
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