CN103769207B - A kind of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst and its preparation method and application - Google Patents
A kind of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst and its preparation method and application Download PDFInfo
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- CN103769207B CN103769207B CN201210408243.XA CN201210408243A CN103769207B CN 103769207 B CN103769207 B CN 103769207B CN 201210408243 A CN201210408243 A CN 201210408243A CN 103769207 B CN103769207 B CN 103769207B
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 25
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 16
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims description 14
- 239000002808 molecular sieve Substances 0.000 claims abstract description 65
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010970 precious metal Substances 0.000 claims abstract description 10
- 239000011734 sodium Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 by weight percentage Substances 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000007493 shaping process Methods 0.000 claims description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 claims description 2
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 claims description 2
- 238000005554 pickling Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 11
- 239000010457 zeolite Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000004846 x-ray emission Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst, this catalyzer is made up of molecular sieve-4 A, molecular sieve B, precious metal and binding agent, the gross weight content of catalyzer Middle molecule sieve A and molecular sieve B is 50 ~ 90%, and the weight ratio of molecular sieve-4 A and molecular sieve B is 1:9 ~ 9:1; The weight content of precious metal is 0.001 ~ 0.05%; Wherein said molecular sieve-4 A is sodium potassium Hydrogen FER type molecular sieve, by weight percentage, and Na in molecular sieve-4 A
2o content is 0.1%-0.4%, K
2o content is 4.5%-6.3%, and molecular sieve B is HZSM-5 molecular sieve, and precious metal is platinum or palladium.The method, while raising iso-butylene yield, makes propene yield significantly improve.
Description
Technical field
The present invention relates to a kind of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst and its preparation method and application.
Background technology
Along with market is to the continuous growth of stop bracket gasoline demand, the demand of the methyl tertiary butyl ether as octane enhancers mixed (MTBE) is also increased thereupon.Such as China's gasoline production in 2011 8141.1 ten thousand tons, on average mixes different substances together aggregate demand than 4.5%, MTBE more than 3,500,000 tons in MTBE.The high market requirement of MTBE will certainly pull the demand to raw material iso-butylene, and the iso-butylene adopting traditional catalytic cracking and cracking of ethylene route to produce is difficult to meet the need of market.And on the other hand, the utilization ratio of the n-butene after MTBE by-product ether in carbon four is lower, is often mixed in civil liquefied gas and burns.
Normal butylenes in carbon after ether four can be iso-butylene by n-butene skeletal isomerization preparing isobutene technique, and recirculation is as MTBE raw material.This technique have raw materials cost low and be easy to get, technique is simple and invest low feature.Both can be the iso-butylene of high added value by the low value normal butylenes in carbon four after the ether of refinery and petrochemical plant, solve again the problem that the utilization ratio of carbon four is low after ether.
US 5,510,560 discloses a kind of Hydrogen FER zeolite catalyst for linear chain olefin skeleton isomerism, and with adopting, silicon-dioxide, clay or binder free are shaping to be compared, and the iso-butylene productive rate of the catalyzer adopting aluminum oxide to obtain as binding agent is higher.US 5,523,510 discloses a kind of linear chain olefin skeleton isomerism catalyzer, and this catalyzer for active ingredient, by steam and cleanup acid treatment, can improve catalyzer iso-butylene productive rate with Hydrogen FER zeolite.It is the preparation method of the zeolite catalyst of isoolefine that CN1142787A discloses a kind of isomerizating straight-chain that makes, with Hydrogen FER zeolite for catalyzer group main component, the wherein Na of FER zeolite
2o weight content is lower than 0.05%.CN1860320A discloses the catalyzer that a kind of normal olefine isomery becomes isoolefine, this catalyzer with Hydrogen FER zeolite for main component, the wherein Na of FER zeolite
2o weight content is lower than 0.1%.EP 0,501,577, US 5,499,851 also individually disclose a kind of n-butene skeletal isomerization preparing isobutene Catalysts and its preparation method being catalyzer with FER type molecular sieve.In above-mentioned patent, all adopt Hydrogen FER zeolite as catalyzer, Hydrogen FER zeolite adopts conventional ammonium ion exchange method, usually (60 ~ 95 DEG C) exchange at a higher temperature, often need to regulate the pH value exchanging liquid, and need repeatedly exchange, carry out more complete to make ammonium exchange.
Adopt Hydrogen FER zeolite as catalyzer in aforesaid method, there is n-butene one way utilization ratio low, except the generation iso-butylene of highly selective, also generate the propylene of a small amount of high added value, ethene and amylene, such as EP 0,501, in 577, the productivity ratio of propylene and iso-butylene is 0.02; US 5,499, in 851, the productivity ratio of propylene and iso-butylene is up to 0.03.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst and its preparation method and application.The method, while raising iso-butylene yield, makes propene yield significantly improve.
A kind of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst, be made up of molecular sieve-4 A, molecular sieve B, precious metal and binding agent, the gross weight content of catalyzer Middle molecule sieve A and molecular sieve B is 50 ~ 90%, the weight ratio of molecular sieve-4 A and molecular sieve B is 1:9 ~ 9:1, preferred 1:1 ~ 9:1; The weight content of precious metal is 0.001 ~ 0.05%, is preferably 0.005 ~ 0.02%; Wherein said molecular sieve-4 A is sodium potassium Hydrogen FER type molecular sieve, by weight percentage, and Na in molecular sieve-4 A
2o content is 0.1%-0.4%, K
2o content is 4.5%-6.3%, and molecular sieve B is HZSM-5 molecular sieve, and precious metal is platinum or palladium.
In catalyzer of the present invention, described FER type molecular sieve SiO
2/ Al
2o
3mol ratio is 8-50, is preferably 15-20.FER type molecular sieve is ferrierite, ZSM-35, NU-23 or FU-9, can adopt commercial goods or prepare by existing scheme.
A kind of preparation method of n-butene skeletal isomerization preparing isobutene co-production propylene catalyst, first sodium potassium Hydrogen FER molecular sieve and HZSM-5 molecular sieve are mixed, support required noble metal component by pickling process, then mediate with binding agent and mix shaping, drying, roasting obtain final catalyzer.
In the inventive method, the concrete preparation method of sodium potassium Hydrogen FER type molecular sieve comprises the steps: that sodium potassium type FER type molecular sieve is pulled an oar with ammonium salt solution and mixes, under temperature is 20 ~ 95 DEG C of conditions preferably under 20 ~ 60 DEG C of conditions, exchange 1 ~ 2 hour, exchange disposed slurry after filtration, the thorough drip washing of filter cake deionized water, oven dry, roasting obtain sodium potassium Hydrogen FER type molecular sieve.Wherein, in ion-exchange slurries, the concentration of ammonium ion is 0.01 ~ 0.05 mol/L; FER type molecular sieve solid is 1:10 to 1:30 with exchanging liquid mass ratio.The ammonium salt used is ammonium nitrate, one or more mixtures in ammonium sulfate, ammonium chloride, ammonium acetate, ammonium phosphate, wherein preferably ammonium nitrate and ammonium chloride.The ion-exchange degree of FER molecular sieve is controlled by changing inorganic ammonium salt concentration of aqueous solution (without the need to regulating and controlling pH value).
In the inventive method, shaping of catalyst can adopt extrusion process, pressed disc method, drip ball or spin comminution granulation, and wherein preferably extrusion process is shaping.Catalyzer dries 5-20 hour, roasting 2-15 hour at being 400-600 DEG C, the preferred 450-650 DEG C of maturing temperature in 80-150 DEG C after shaping.
An application for n-butene skeletal isomerization preparing isobutene co-production propylene catalyst, wherein said n-butene comprises any one or more mixture in 1-butylene, trans-2-butene and cis-2-butene.N-butene can come from carbon four after refinery or petrochemical plant ether, also can come from methanol-to-olefins by-product carbon four.Suitable reaction conditions n-butene being produced to iso-butylene co-production propylene comprises: temperature of reaction is 300 ~ 550 DEG C, preferably 350 ~ 450 DEG C; Stagnation pressure is 0 ~ 0.5MPa, preferably 0.05 ~ 0.25MPa; Weight hourly space velocity is 0.1 ~ 20h
-1, preferably 0.5 ~ 15h
-1.Can inactive thinner be contained, as N in above-mentioned n-butene feedstream
2, H
2or alkane etc.
The inventive method passes through condition, particularly ammonium concentration and ion-exchange temperature, the ion-exchange time etc. of control FER type molecular sieve exchange process, can obtain the sodium potassium Hydrogen FER type molecular sieve of suitable exchange degree.The catalyzer that sodium potassium Hydrogen FER type molecular sieve and ZSM-5 molecular sieve mixing back loading active metal obtain
Produce in iso-butylene process for n-butene skeletal isomerization, under the same reaction conditions, while raising iso-butylene yield, propene yield is significantly improved (see embodiment 7 and comparative example 1).
Embodiment
Below by embodiment, the present invention is set forth further.
Ferrerite Molecular sieve raw material used in embodiment and comparative example, adopts the SiO of x-ray fluorescence spectrometry ferrerite
2/ Al
2o
3mol ratio 16.5, by weight percentage, Na
2o content is 0.90%, K
2o content is 6.32%, is provided by eastern Cao Da (Shanghai) trade Co., Ltd.The chemical reagent used, as indicated without special, is analytical reagent.Catalyst preparing binding agent used is SW-17 type aluminium hydrate powder, and pore volume is 0.47-0.53 ml/g, is greater than 250 m than table
2/ g, mean pore size is 7.5-8.5 nm, and by Zibo, safe photoinitiator chemical company limited provides.
Embodiment 1 ~ 3
The preparation of sodium potassium Hydrogen FER molecular sieve.
By the NH of the concentration of ferrerite molecular sieve and different ammonium ion
4cl aqueous solution is evenly pulled an oar, change ferrerite molecular sieve solid and exchange liquid mass ratio, stir 2 hours under differing temps, filter, gained filter cake 30 times of deionized water cleaning downs to ferrerite molecular sieve butt weight, dry and 550 DEG C of roastings through 110 DEG C, obtain sodium potassium Hydrogen FER molecular sieve, be labeled as NaKH-1, NaKH-2 and NaKH-3 respectively.By weight percentage, the Na of the sodium potassium Hydrogen FER molecular sieve adopting x-ray fluorescence spectrometry to obtain
2o and K
2o content.Preparation condition and the Na recording sodium potassium Hydrogen FER molecular sieve
2o and K
2o content is in table 1.
The preparation of table 1 sodium potassium Hydrogen FER molecular sieve
| Title | NH 4 +Concentration (mol/L) | Sieve/liquor ratio * (g/g) | Exchange temperature ( oC） | Na 2O content | K 2O content |
| NaKH-1 | 0.01 | 1/30 | 60 | 0.38 | 6.23 |
| NaKH-2 | 0.02 | 1/20 | 40 | 0.23 | 5.68 |
| NaKH-3 | 0.05 | 1/10 | 25 | 0.18 | 4.74 |
* ferrerite molecular sieve solid and exchange liquid mass ratio, content is weight content.
Embodiment 4
HZSM-5 molecular sieve.
In high pressure water thermal synthesis still, add 1 part of sodium hydroxide, 1.5 parts of Tai-Ace S 150,1.8 parts of TPAOH, 30 parts of silicon sol are (containing the SiO of weight ratio 26%
2) and 40 parts of water, stir, 180 DEG C of crystallization 72 hours, wash after filtration, 110 DEG C of oven dry, prior to roasting in 550 DEG C of nitrogen atmospheres 6 hours, to be then in 550 DEG C of air atmosphere roasting 6 hours, the obtained former powder of ZSM-5.By the NH of the ZSM-5 molecular sieve of 200 g, 214 g
4cl and 4000 g deionized waters mix making beating, stir 2 hours at 75 DEG C, filter, above-mentioned exchange process 3-5 time is repeated again at 75 DEG C, through filtering after exchange, gained filter cake 30 times of deionized water cleaning downs to ZSM-5 molecular sieve butt weight, through 110 DEG C of oven dry and 550 DEG C of roastings, obtain Hydrogen ZSM-5 molecular sieve, be designated as HZSM-5.The SiO of the HZSM-5 adopting x-ray fluorescence spectrometry to obtain
2/ Al
2o
3mol ratio 18.6.
Embodiment 5 ~ 8
Catalyst preparing.
After HZSM-5 molecular sieve dried bean noodles prepared by the NaKH-FER molecular sieve powder prepare embodiment 1 ~ 3 and embodiment 4 mixes, obtained Different Weight is than the mixed molecular sieve of NaKH-FER/HZSM-5 weight ratio.Adopt Palladous chloride-hydrochloric acid soln incipient impregnation mixed molecular sieve powder, flood 8 hours under room temperature, then dry 24 hours in 110 DEG C, then in 550 DEG C of roastings 5 hours, what finally obtain different palladium content contained palladium mixed molecular sieve.Then obtained is contained palladium mixed molecular sieve, mediate the dense thick paste body of formation with SW-17 aluminium hydrate powder, sesbania powder, nitric acid and deionized water at CD4X1TS type polyfunctional catalyst forming machine, adopt the stainless steel moulded board extrusion molding in 1.5 mm holes.Gained extrudate prior to drying under room temperature 24 hours, then is dried 24 hours in 110 DEG C, and finally in 600 DEG C of roastings 12 hours, obtain final catalyzer, respective markers is C-1, C-2, C-3 and C-4.Adopt inductively coupled plasma emission spectrography to record the Pd metal content of a catalyzer, in weight content, the composition of catalyzer is in table 2.
Comparative example 1
With embodiment 7, just NaKH type FER molecular sieve is replaced with Hydrogen HFER, the preparation process of HFER molecular sieve is as follows: by the ferrerite molecular sieve of 200 g, the NH of 214 g
4cl and 4000 g deionized waters mix making beating, stir 2 hours at 75 DEG C, filter, repeat above-mentioned exchange process at least 5 times, through filtering after exchange, the 30 times of thorough drip washing of deionized water to NaK-FER zeolite butt weight of gained filter cake, dry and 550 DEG C of roastings through 110 DEG C, obtain HFER.Adopt embodiment 7 same procedure, carrying metal Pd, extrusion molding, obtained whole catalyzer, is labeled as C-5, in table 2.
Table 2 catalyzer forms
* ferrerite molecular sieve solid and exchange liquid mass ratio; Content in form is weight percentage.
Embodiment 9
Adopt the performance of n-butene skeletal isomerization reaction evaluating catalyzer.Reaction is being carried out close on the micro-trans-chromatogram arrangement of continuous flow fixed bed of normal pressure, 1 g is crushed to the stainless steel reaction pipe flat-temperature zone that 20-40 object catalyzer loads internal diameter 10 mm, fill 20-40 object quartz sand up and down, in order to support catalyst bed, and make flow of feed gas radial distribution even.Before each evaluating catalyst, by catalyzer first pre-treatment 2 hours in the High Purity Nitrogen atmosphere of 500 DEG C, then temperature of reaction need be cooled to.Unstripped gas be containing 1-butylene volume fraction be 10% 1-butylene and the gas mixture that forms of high pure nitrogen.Reaction product adopts the on-line analysis of Agilent 7890 type gas-chromatography.N-butene skeletal isomerization reaction conditions: temperature is 350 DEG C, stagnation pressure 0.15 MPa, weight hourly space velocity is 4h
-1.
Catalyzer in above-described embodiment in the little reactivity worth constantly of reaction 10 in table 3.
The reactivity worth of table 3 catalyzer
| Catalyzer | N-butene conversion (%) | Propylene Selectivity (%) | Selective isobutene (%) | Productivity of propylene (%) | Iso-butylene productive rate (%) | Diene productive rate (%) |
| C-1 | 36.6 | 1.7 | 93.9 | 0.6 | 34.4 | 35.0 |
| C-2 | 50.8 | 15.2 | 81.5 | 7.7 | 41.4 | 49.1 |
| C-3 | 61.8 | 20.4 | 54.2 | 12.6 | 33.5 | 46.1 |
| C-4 | 70.1 | 31.5 | 28.6 | 22.1 | 20.0 | 42.1 |
| C-5 | 68.4 | 33.5 | 27.5 | 22.9 | 18.8 | 41.7 |
As shown in Table 3, under the same reaction conditions, catalyzer of the present invention, while raising iso-butylene yield, makes propene yield significantly improve (see embodiment 7 and comparative example 1).
Claims (10)
1. a n-butene skeletal isomerization preparing isobutene co-production propylene catalyst, it is characterized in that: this catalyzer is made up of molecular sieve-4 A, molecular sieve B, precious metal and binding agent, the gross weight content of catalyzer Middle molecule sieve A and molecular sieve B is 50 ~ 90%, and the weight ratio of molecular sieve-4 A and molecular sieve B is 1:9 ~ 9:1; The weight content of precious metal is 0.001 ~ 0.05%; Wherein said molecular sieve-4 A is sodium potassium Hydrogen FER type molecular sieve, by weight percentage, and Na in molecular sieve-4 A
2o content is 0.1%-0.4%, K
2o content is 4.5%-6.3%, and molecular sieve B is HZSM-5 molecular sieve, and precious metal is platinum or palladium.
2. catalyzer according to claim 1, is characterized in that: the weight ratio of catalyzer Middle molecule sieve A and molecular sieve B is 1:1 ~ 9:1; The weight content of precious metal is 0.005 ~ 0.02%.
3. catalyzer according to claim 1, is characterized in that: described FER type molecular sieve SiO
2/ Al
2o
3mol ratio is 8-50.
4. the catalyzer according to claim 1 or 3, is characterized in that: FER type molecular sieve is ferrierite, ZSM-35, NU-23 or FU-9.
5. the preparation method of catalyzer described in claim 1, it is characterized in that: first sodium potassium Hydrogen FER type molecular sieve and HZSM-5 molecular sieve are mixed, support required noble metal component by pickling process, then mediate with binding agent and mix shaping, drying, roasting obtain final catalyzer.
6. method according to claim 5, it is characterized in that: the preparation of sodium potassium Hydrogen FER type molecular sieve comprises the steps: that sodium potassium type FER type molecular sieve is pulled an oar with ammonium salt solution and mixes, under temperature is 20 ~ 95 DEG C of conditions, exchange 1 ~ 2 hour, exchange disposed slurry after filtration, the thorough drip washing of filter cake deionized water, oven dry, roasting obtain sodium potassium Hydrogen FER type molecular sieve.
7. method according to claim 6, is characterized in that: in ion-exchange slurries, the concentration of ammonium ion is 0.01 ~ 0.05 mol/L; FER type molecular sieve solid is 1:10 to 1:30 with exchanging liquid mass ratio.
8. the application of catalyzer described in claim 1 in n-butene skeletal isomerization preparing isobutene co-production propylene catalyst, is characterized in that: described n-butene comprises any one or more mixture in 1-butylene, trans-2-butene and cis-2-butene.
9. application according to claim 8, is characterized in that: temperature of reaction is 300 ~ 550 DEG C; N-butene dividing potential drop is 0 ~ 0.5 MPa; Weight hourly space velocity is 0.1 ~ 20 h
-1.
10. application according to claim 9, is characterized in that: temperature of reaction is 350 ~ 450 DEG C; N-butene dividing potential drop is 0.05 ~ 0.25 MPa; Weight hourly space velocity is 0.5 ~ 15h
-1.
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| CN105461500A (en) * | 2014-09-05 | 2016-04-06 | 中国科学院生态环境研究中心 | Synthetic method for 2-butene through isomerization of 1-butene by catalyzing at room temperature |
| CN105983435B (en) * | 2015-03-03 | 2019-05-07 | 卓润生 | A kind of isomerization of butene catalyst and its preparation method and application |
| CN106673945B (en) * | 2015-11-09 | 2019-04-12 | 中国石油化工股份有限公司 | A kind of method that n-butene prepares propylene |
| CN106673937B (en) * | 2015-11-09 | 2019-06-11 | 中国石油化工股份有限公司 | A kind of method that n-butene catalytic pyrolysis prepares propylene |
| CN112439443B (en) * | 2019-09-04 | 2023-07-14 | 中国石油化工股份有限公司 | Light olefin skeleton conversion catalyst and preparation method thereof |
| CN113559916A (en) * | 2021-08-27 | 2021-10-29 | 中国科学院山西煤炭化学研究所 | A kind of molecular sieve encapsulated precious metal catalyst and its preparation method and application |
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