CN102600886A - Catalyst for preparing iso-olefins by isomerizing straight-chain olefins and preparation method of catalyst - Google Patents
Catalyst for preparing iso-olefins by isomerizing straight-chain olefins and preparation method of catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 18
- 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 18
- 239000010457 zeolite Substances 0.000 claims abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001657 ferrierite group Inorganic materials 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 abstract description 26
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000006317 isomerization reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000004230 steam cracking Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004523 catalytic cracking Methods 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- -1 ether compound Chemical class 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing iso-olefins by isomerizing straight-chain olefins and a preparation method of the catalyst. The catalyst uses the FER (ferrierite) zeolite raw powder as a main active body, wherein the silica-alumina ratio (SiO2/Al2O3) (molar ratio) is less than 50. The preparation method comprises the following steps: mixing FER zeolite raw powder, silica sol and/or alumina sol, organic acid and water evenly; carrying out molding, drying and calcinaton, and soaking in a VIII group metal oxide solution; and carrying out drying and calcination to obtain the catalyst. For the isomerization of straight-chain olefins, the catalyst is good in activity and stability, high in both conversion rate of straight-chain olefins and selectivity to iso-olefins and can be applied to the field of industrial production of the iso-olefins, such as the industrial production of isobutene and isoamylene.
Description
Technical field
The present invention relates to the Catalysts and its preparation method that a kind of isomerizating straight-chain prepares different olefine.
Background technology
Different olefine such as isobutene and iso-amylene are important basic organic.Isobutene is mainly used in the production of gasoline additive methyl tertiary butyl ether(MTBE) (MTBE), polyisobutene etc.; Isobutene also is the primary raw material of synthetic rubber such as butyl rubber, and simultaneously isobutene still is the raw material of multiple Organic Chemicals such as the tert-butyl alcohol, methacrylonitrile, antioxidant etc.Iso-amylene then is one of main intermediate of producing by agricultural chemicals, medicine and spices.
Different olefine generally separates acquisition from the accessory substance of steam cracking device or plant catalytic cracking unit (FCC), then from mix carbon five, separate obtaining from mixed c 4, iso-amylene like isobutene.According to the difference of different olefine relative volatility, divide the method for divorce olefine also to be not quite similar.Can be through usual manners such as conventional distillation and extracting rectifyings, also can through with separate again after alcohols such as methyl alcohol generates ether compound, as isobutene can through with methyl alcohol reaction generation methyl tertiary butyl ether(MTBE) (MTBE) after separate again.
Linear alkene or mixture of linear olefins mainly come from the accessory substance of steam cracking device or refinery's device.According to the difference of raw material, reaction depth and catalyst, accessory substance composition and output that steam cracking device or refinery's device are produced are also different.For example the mixed c 4 of steam cracking device by-product composition (weight) is about under the usual conditions: alkane: isobutene 3%: butene-1 22%: butene-2 14%: butadiene 11%: 50%.The mixed c 4 of plant catalytic cracking unit by-product is formed (weight) and is about: iso-butane: 34%, and normal butane: 10%, isobutene: 15%, butene-1: 13%, butene-2: 28%.On total amount, the mixed c 4 of catalytic cracking unit by-product is approximately the 9%-12% (weight) of device fresh feed generally speaking, and the mixed c 4 of steam cracking device by-product is approximately about 40% of ethene ability.
In China; In the mixed c 4 of steam cracking device or plant catalytic cracking unit by-product and the mixing carbon five; Except that butadiene, isobutene, iso-amylene etc. obtained preferably chemical utilization, all the other major parts comprised that linear alkene etc. is used as fuel and uses, and the chemical industry added value is lower.
By the end of the year 2009, Chinese crude oil time processing ability reaches 4.77 hundred million tons, and over the past two years, China be constructed and put into operation can reach 5000 with the refining capacity of building surplus ten thousand tons, building or the steam cracking device scale of planning construction also considerable.Therefore, a large amount of mixed c 4s will be arranged future and mix carbon five appearance, the chemical utilization that how to improve linear alkene wherein is worth has high realistic meaning, particularly under the environment of soaring oil prices.
Document US 5648585 has been introduced a kind of catalyst for preparing different olefine from linear alkene.It is catalyst body that this catalyst adopts zeolite such as ferrierite, ZSM-22 or the ZSM-23 of one dimension pore structure, and aluminium oxide is the binding agent of catalyst; Catalyst comprises metal such as palladium or the platinum that is up to 15% (weight) in addition.The isomerisation temperature of this technology is about 200-650 ℃, and the dividing potential drop of linear alkene is greater than 0.5Bar in the charging; Hydrogen in the charging is 0-30 (mole) with the ratio of hydrocarbon mixture.The embodiment of this document shows that adopting n-butene is raw material, and the obtainable selective isobutene of this catalyst is up to 88% (butene conversion of this moment is 40%), and the conversion ratio of butylene is up to 50% (selective isobutene of this moment is 75%); The one way life-span of catalyst is about 100-300 hour.This catalyst can obtain the conversion ratio of different preferably olefine selectivity and linear alkene, but has adopted the modified with noble metals catalyst of higher concentration, and cost is higher; Possibly face hydrogen in the reaction feed simultaneously, increase technology operating cost.
It is linear alkene such as n-butene skeletal isomerization the catalyst of different olefine that document US 5449851 has been introduced a kind of highly selective.This catalyst is ZSM-35, is preferably through the HZSM-35 like the rare earth ion modification.The isomerisation temperature of this catalyst is about 390-550 ℃, and the dividing potential drop of linear alkene is 50-150KPa in the charging, and the weight (hourly) space velocity (WHSV) of charging is 30-250 hour 1.The embodiment of this document shows that adopting n-butene is raw material, and the butene conversion of this catalyst is about 30%-40% (weight), and the selectivity of isobutene is about 90-99%; The catalyst line duration that embodiment shows is very short, and several hrs only can't be explained the stability of this catalyst.Though the catalyst of this document introduction can obtain higher different olefine selectivity, the conversion ratio of linear alkene is lower in the raw material, and the stability of catalyst can't be described.
Summary of the invention
The present invention relates to the Catalysts and its preparation method that a kind of isomerizating straight-chain prepares different olefine, be mainly used in the production of different olefine.
Problem to be solved by this invention be in the past in the technology isomerizating straight-chain be that the catalyst reaction activity of different olefine is lower, the purpose selectivity of product is not high and technical problem such as poor catalyst stability, a kind of new Catalysts and its preparation method is provided.It is active with stability, higher one way linear alkene conversion ratio with to the advantages such as selectivity of different olefine that this catalyst has good isomerizating straight-chain.
In order to solve the problems of the technologies described above, the technical scheme that the present invention adopts is following: a kind of isomerizating straight-chain prepares the Catalysts and its preparation method of different olefine, it is characterized in that this catalyst is with silica alumina ratio (SiO
2/ Al
2O
3) (mole) be active main body less than 50 FER zeolite powder; FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are evenly mixed; After moulding, the dry also roasting, impregnated in the VIII family metal oxide solution, after drying, roasting, make again.
In the technique scheme, the FER zeolite powder is preferably ferrierite, ZSM-35, FU-9 or ISI-6, more preferably silica alumina ratio (SiO
2/ Al
2O
3) (mole) less than 30 ferrierite or ZSM-35.
The mixed proportion (weight) of Ludox and/or aluminium colloidal sol and FER zeolite powder is preferably 1: 1-10.
Organic acid is preferably formic acid, acetate, citric acid, oxalic acid or maleic acid.The mixed proportion of organic acid and FER zeolite powder (weight) is preferably 1: 10-300.
The mixed proportion of water and FER zeolite powder (weight) is preferably 1: 1-10.
VIII family metal oxide solution is preferably the inorganic salt solution of Metal Palladium, platinum, cobalt or nickel.
This Preparation of catalysts is preferably and may further comprise the steps:
Step 1: FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are mixed in proportion, stir 10 minutes to 60 minutes aftershapings, then in 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
Step 2: the catalyst soakage that step 1 is obtained in VIII family metal oxide solution 1-6 hour, the ratio of catalyst and metal oxide solution (weight) is 3-1: 1.
Step 3: with the mixture heating evaporation of step 2, then 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
VIII family metal oxide solution metal content is preferably 0.1-10% (weight).
This Application of Catalyst condition is preferably: reaction raw materials is preferably and contains C
4 +The hydrocarbon mixture of linear alkene, wherein C
4 +The content of linear alkene is preferably more than 30% (weight); Reactor is preferably one or more snippets fixed bed reactors, and reaction temperature is preferably 250 ℃-450 ℃, and reaction pressure is preferably 0.05-0.5MPa, and weight (hourly) space velocity (WHSV) is preferably 5-100 hour
-1
The present invention adopts the FER zeolite catalyst, has unique one dimension pore structure, and different olefine is had higher selectivity; It is more even that organic acid helps catalyst granules to disperse, and removes the impurity in the catalyst duct simultaneously, improves activity of such catalysts and stability; The existence of VIII family metal ion has improved the carbon accumulation resisting ability of catalyst, helps keeping the long period stability of catalyst.The linear alkene conversion per pass of catalyst of the present invention is greater than 43% (weight), simultaneously to the selectivity of different olefine greater than 86%, obtained the good technical effect.
Through embodiment the present invention is done further elaboration below.
The specific embodiment
Catalyst sample to all embodiment obtained adopts identical appreciation condition, and appreciation condition is:
Catalyst: 5.0 grams; Raw material is butene-1 and normal butane mixture, and wherein the content of butene-1 (weight) is 80%, and feed rate is 200 Grams Per Hours; Reaction temperature is 400 ℃, and the reactor inlet stagnation pressure is 0.20MPa, adopts individual layer axial restraint bed bioreactor.
The evaluation result of all catalyst samples sees Table 1.
[embodiment 1]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 901 grams of 20 ferrierite, aluminium colloidal sol 107 grams, citric acid 15 grams; Deionized water 203 grams mix; At the uniform velocity stir 30 minutes aftershapings, under 100 ℃ of conditions dry 20 hours then, roasting obtained catalyst sample 1 after 2 hours under 500 ℃ of conditions again.
[embodiment 2]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 885 grams of 20 ferrierite, aluminium colloidal sol 93 grams, citric acid 16 grams, deionized water 196 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in palladium nitrate aqueous solution (weight concentration of palladium is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and palladium nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and palladium nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 2 after 2 hours under 500 ℃ of conditions again.
[embodiment 3]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 916 grams of 20 ferrierite, aluminium colloidal sol 111 grams, citric acid 18 grams, deionized water 213 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in cobalt nitrate aqueous solution (weight concentration of cobalt is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and cobalt nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and cobalt nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 3 after 2 hours under 500 ℃ of conditions again.
[embodiment 4]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 966 grams of 25 ZSM-35, aluminium colloidal sol 118 grams, acetate 11 grams; Deionized water 200 grams mix; At the uniform velocity stir 30 minutes aftershapings, under 100 ℃ of conditions dry 20 hours then, roasting obtained catalyst sample 4 after 2 hours under 500 ℃ of conditions again.
[embodiment 5]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 953 grams of 25 ZSM-35, aluminium colloidal sol 117 grams, acetate 13 grams, deionized water 220 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in palladium nitrate aqueous solution (weight concentration of palladium is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and palladium nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and palladium nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 5 after 2 hours under 500 ℃ of conditions again.
[embodiment 6]
With silica alumina ratio (SiO
2/ Al
2O
3) (mole) be former powder 989 grams of 25 ZSM-35, aluminium colloidal sol 123 grams, acetate 20 grams, deionized water 208 grams mix, and at the uniform velocity stir 30 minutes aftershapings, and under 100 ℃ of conditions dry 20 hours then, roasting 2 hours under 500 ℃ of conditions again.With the catalyst that obtains after the roasting in nickel nitrate aqueous solution (weight concentration of nickel is 5%) in 60 ℃ the dipping 3 hours, wherein the ratio of catalyst and nickel nitrate aqueous solution (weight) is 2; The mixture of heating evaporation catalyst and nickel nitrate solution descended dry 20 hours at 100 ℃ then, and roasting obtains catalyst sample 6 after 2 hours under 500 ℃ of conditions again.
Table 1 catalyst sample test result
Claims (10)
1. an isomerizating straight-chain prepares the Catalysts and its preparation method of different olefine, and this catalyst is with silica alumina ratio (SiO
2/ Al
2O
3) (mole) be active main body less than 50 FER zeolite powder; FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are evenly mixed; After moulding, the dry also roasting, impregnated in the VIII family metal oxide solution, after drying, roasting, make again.
2. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that the FER zeolite powder is ferrierite, ZSM-35, FU-9 or ISI-6, more preferably silica alumina ratio (SiO
2/ Al
2O
3) (mole) less than 30 ferrierite or ZSM-35.
3. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that the mixed proportion (weight) of Ludox and/or aluminium colloidal sol and FER zeolite powder is 1: 1-10.
4. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that organic acid is formic acid, acetate, citric acid, oxalic acid or maleic acid.
5. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 4 is characterized in that the mixed proportion (weight) of organic acid and FER zeolite powder is 1: 10-300.
6. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that the mixed proportion (weight) of water and FER zeolite powder is 1: 1-10.
7. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that VIII family metal oxide solution is the inorganic salt solution of Metal Palladium, platinum, cobalt or nickel.
8. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1 is characterized in that this Preparation of catalysts method is:
Step 1: FER zeolite powder, Ludox and/or aluminium colloidal sol, organic acid and water are mixed in proportion, stir 10 minutes to 60 minutes aftershapings, then in 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
Step 2: the catalyst soakage that step 1 is obtained in VIII family metal oxide solution 1-6 hour, the ratio of catalyst and metal oxide solution (weight) is 3-1: 1.
Step 3: with the mixture heating evaporation of step 2, then 80 ℃-120 ℃ dry 10-20 hour down, under 450 ℃ of-650 ℃ of conditions roasting 2-6 hour again.
9. said according to Claim 8 isomerizating straight-chain prepares the catalyst of different olefine, it is characterized in that VIII family metal oxide solution metal content is 0.1-10% (weight).
10. the catalyst for preparing different olefine according to the said isomerizating straight-chain of claim 1, it is characterized in that this Application of Catalyst condition is: reaction raw materials is for containing C
4 +The hydrocarbon mixture of linear alkene, wherein C
4 +The content of linear alkene is greater than 30% (weight); Reactor is one or more snippets fixed bed reactors, and reaction temperature is 250 ℃-450 ℃, and reaction pressure is 0.05-0.5MPa, and weight (hourly) space velocity (WHSV) is 5-100 hour
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105709715A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst used for preparing isobutene, and preparation method thereof |
| CN108246352A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of C5, C6 linear olefin skeletal isomerization catalyst and its preparation method and application |
| CN109701607A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and applications |
| CN109701606A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and its usage |
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| CN109851465A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
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| CN105709715A (en) * | 2014-12-03 | 2016-06-29 | 中国石油化工股份有限公司 | Catalyst used for preparing isobutene, and preparation method thereof |
| CN105709715B (en) * | 2014-12-03 | 2017-11-24 | 中国石油化工股份有限公司 | It is a kind of to be used to prepare catalyst of isobutene and preparation method thereof |
| CN108246352A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of C5, C6 linear olefin skeletal isomerization catalyst and its preparation method and application |
| CN109701607A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and applications |
| CN109701606A (en) * | 2017-10-26 | 2019-05-03 | 中国石油化工股份有限公司 | Skeletal isomerisation catalyst, preparation method and its usage |
| CN109851464A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851465A (en) * | 2017-11-30 | 2019-06-07 | 中国石油化工股份有限公司 | A kind of method and device of n-butene isomerization |
| CN109851464B (en) * | 2017-11-30 | 2021-11-19 | 中国石油化工股份有限公司 | Method and device for isomerizing n-butene |
| CN109851465B (en) * | 2017-11-30 | 2021-11-19 | 中国石油化工股份有限公司 | Method and device for isomerizing n-butene |
| CN116474824A (en) * | 2023-03-09 | 2023-07-25 | 福建森美达生物科技有限公司 | Catalyst, method and device for increasing geranial content in citral |
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