CN102020527A - Method for producing isopropylbenzene by diisopropylbenzene transalkylation - Google Patents
Method for producing isopropylbenzene by diisopropylbenzene transalkylation Download PDFInfo
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- CN102020527A CN102020527A CN2009100931125A CN200910093112A CN102020527A CN 102020527 A CN102020527 A CN 102020527A CN 2009100931125 A CN2009100931125 A CN 2009100931125A CN 200910093112 A CN200910093112 A CN 200910093112A CN 102020527 A CN102020527 A CN 102020527A
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- molecular sieve
- mww
- diisopropylbenzene
- laminate structure
- dipb
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- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 title claims abstract description 56
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000010555 transalkylation reaction Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000002808 molecular sieve Substances 0.000 claims abstract description 47
- 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 47
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical group [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 3
- 239000010439 graphite Substances 0.000 claims abstract description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 3
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 claims abstract 5
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 claims abstract 5
- 229910002796 Si–Al Inorganic materials 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 21
- 239000011734 sodium Substances 0.000 claims description 17
- 238000010792 warming Methods 0.000 claims description 17
- 229910021536 Zeolite Inorganic materials 0.000 claims description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 15
- 239000010457 zeolite Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002425 crystallisation Methods 0.000 claims description 12
- 230000008025 crystallization Effects 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 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 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 244000275012 Sesbania cannabina Species 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004898 kneading Methods 0.000 abstract description 3
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 4
- 230000003197 catalytic effect Effects 0.000 description 10
- 230000009466 transformation Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 241000219782 Sesbania Species 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 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
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- Catalysts (AREA)
Abstract
The invention relates to a method for producing isopropylbenzene by diisopropylbenzene transalkylation, wherein benzene and diisopropylbenzene are in a molar ratio of 8 and an airspeed of the diisopropylbenzene of 2-6h-1Carrying out catalytic reaction at the reaction temperature of 180-220 ℃ and under the pressure of 3.5 MPa; the catalyst is prepared by mixing 70-90% of H-type nanoscale MWW layered structure silicon-aluminum molecular sieve and 10-30% of binder according to 100% by weight, adding additive, kneading, drying and roasting at 500-600 ℃; the binder is pseudo-boehmite, alumina, silicon oxide, graphite or zirconia; the H-type nano MWW layered structure silicon-aluminum molecular sieve silicon-aluminum molar ratio is 25-35, the molecular sieve silicon-aluminum2(ii) per gram, total pore volume is 0.4-0.6 ml/g; the initial conversion rate of DIPB and the yield of IPB reach more than 80%.
Description
Technical field:
The present invention relates to a kind of zeolite catalysts and carry out the method that the diisopropylbenzene(DIPB) transalkylation is produced isopropyl benzene.
Background technology:
Isopropyl benzene is important basic Organic Chemicals, and the raw material of phenol, acetone, methyl phenyl ketone, alpha-methyl styrene and aviation fuel oil is produced in conduct in petroleum industry.Phenol more than 90% adopts cumene method production in the world at present.
The synthetic of industrial isopropyl benzene is raw material with benzene and propylene mainly, prepares through alkylated reaction under catalyst action.The traditional method of industrial production isopropyl benzene has the solid phosphoric acid method (SPA method) of UOP (UOP) and the improvement AlCl of Monsanto/Lummus Crest company
3Method.Wherein, molecular sieve liquid phase alkylation methods because reaction conditions mitigations, transformation efficiency height, selectivity is good, impurity is few, pollution-free, do not have corrosion, mainly the by product polyisopropylbenzene can change isopropyl benzene into by transalkylation, makes the isopropyl benzene productive rate up to more than 99%.
Molecular sieve liquid phase alkylation methods synthesizing iso-propylbenzene technology comprises alkylation and two technological processs of transalkylation.In the technological process of alkylation synthesizing iso-propylbenzene (IPB), be accompanied by the generation of a certain amount of diisopropylbenzene(DIPB) (DIPB), caused the decline of isopropyl benzene yield.Industrial employing alkyl transfering process makes diisopropylbenzene(DIPB) and benzene transalkylation generate isopropyl benzene under the molecular sieve catalytic effect, to improve the isopropyl benzene yield.Disclosed isopropyl benzene transalkylation catalyst comprises BETA, Y, ZSM-5, MOR zeolite, MCM-22, MCM-49 and handles the above-mentioned zeolite catalyst that obtains through phosphorus modification, rare earth modified, dealuminzation modification.
CN 1596151 discloses a class twelve-ring structure two-phase coexisting molecular sieve and a synthetic method thereof, comprising the two-pack transalkylation catalyst of dealuminium mordenite with second zeolite component composition with twelve-ring, second zeolite component is preferable over MCM-22, MCM-49, MCM-56, BETA, ZSM-12 etc., wherein preferred BETA molecular sieve.US 5557024 discloses the technological process of benzene and ethene, propylene alkylation and transalkylation synthesizing ethyl benzene and isopropyl benzene, and its transalkylation catalyst is preferably from MCM-22, X, Y, MOR, BETA, wherein preferred BETA molecular sieve.Above-mentioned two patents (CN 1596151, and US 5557024) all point out to have the MCM-22 of MWW laminate structure and the transalkylation catalytic activity that the MCM-49 molecular sieve has diisopropylbenzene(DIPB), but do not have the relevant catalyst preparation technology and the elaboration of catalytic performance aspect.
US 5371310 discloses and has adopted MCM-49 and MCM-22 molecular sieve as the technology of diisopropylbenzene(DIPB) transalkylation catalyst, comprises catalyst preparation technology and catalytic performance test result.Wherein, the preparation of MCM-49 and MCM-22 molecular sieve can be adopted static state or the synthetic two kinds of methods of dynamic hydro-thermal, and its dynamic hydrothermal synthesis method adopts stirring-type autoclave.The details that does not relate to grain-size, specific surface area and the pore structure aspect of prepared MCM-22 or MCM-49 molecular sieve in the above-mentioned patent.
Summary of the invention:
The nano zeolite catalyst that the object of the present invention is to provide a kind of application to have the MWW laminate structure carries out the method that the diisopropylbenzene(DIPB) transalkylation is produced isopropyl benzene.The diisopropylbenzene(DIPB) transalkylation activity of this nano zeolite catalyst and catalytic stability are higher than the micron zeolite catalyzer that has the MWW laminate structure equally.
Benzene and diisopropylbenzene(DIPB) be in mol ratio 8, air speed 2～6h
-1, 180～220 ℃ of temperature of reaction, pressure 3.5MPa condition under carry out catalyzed reaction;
Catalyzer is that 100% binding agent by 70～90%H type nano level MWW laminate structure Si-Al molecular sieve and 10～30% constitutes by weight, add total catalyst weight 6～8% concentration and be rare nitric acid of 2～7%, 0.5～1.5% sesbania powder and 1.0～2.5% citric acid additive, through mediating, drying, place following 500 ℃～600 ℃ roasting 4～6h of retort furnace air atmosphere to make;
Nanometer MWW laminate structure Si-Al molecular sieve sial is 25～35 in molar ratio, is the hexagonal flake monocrystalline, and crystal diameter is 50～900nm, and thickness is 20～200nm, specific surface area 〉=400m
2/ g, total pore volume 0.4～0.6ml/g;
Binding agent is pseudo-boehmite, aluminum oxide, silicon oxide, graphite or zirconium white.
The preparation method of nano level MWW laminate structure Si-Al molecular sieve of the present invention is as follows:
1) preparation of Na type nano level MWW laminate structure Si-Al molecular sieve
At first, sodium metaaluminate and template hexamethylene imine are dissolved in an amount of distilled water, under the violent stirring condition, slowly splash into silicon sol, it is standby that gained magma violent stirring 0.5～5h is made colloid, this colloid is transferred to horizontal in transverse axis roller crystallizing kettle, be warming up to 130～180 ℃ under the dynamic crystallization condition, crystallization 48～96h, stirring velocity 40～80rpm, after crystallization finishes, products therefrom filtration and thorough washing is extremely neutral, and oven dry is spent the night under 120 ℃, gets molecular sieve crystal, molecular sieve crystal is placed retort furnace, the 3h internal program is warming up to 538 ℃, and constant temperature calcining 8h thoroughly removes template and carbon deposit and gets Na type nano level MWW laminate structure Si-Al molecular sieve;
2) preparation of H type nano level MWW laminate structure Si-Al molecular sieve
Above-mentioned synthetic good Na type nano level MWW laminate structure Si-Al molecular sieve and ammonium nitrate solution are exchanged, 80～95 ℃ of exchange temperature, liquid-solid ratio is 25ml/g, ammonium nitrate concn is 0.5～2 mol, after 3 exchanges, makes the alkalimetal ion weight content less than 50ppm, the qualified zeolite of exchange is placed retort furnace, the 3h internal program is warming up to 538 ℃, and roasting 6h gets H type nano level MWW laminate structure Si-Al molecular sieve;
Evaluate catalysts performance in the little inverse spectra system of fixed bed high pressure, adopting stainless steel tubular type fixed-bed reactor internal diameter is 10mm, the catalyst filling amount is 1g (40～60 order), catalyzer is filled inertia quartz sand up and down, reaction solution flows through beds from top to bottom, before the reaction beginning, adopt high pure nitrogen to flow and purge deactivated catalyst bed 3h for following 200 ℃ in normal pressure, then temperature of reactor is adjusted to 180～220 ℃ of the temperature of reaction of setting, with high pure nitrogen system is pressurized to 3.5MPa, and in reactor, pumps into the mixture of diisopropylbenzene(DIPB) and benzene.Reaction product is collected through cold-trap.Behind the reaction beginning 2h, extract reaction solution every 1h and to carry out stratographic analysis.
Gas chromatography analysis method: product analysis carries out hydrogen flame detector on Shimadzu GC-14B gas chromatograph.The Shimadzu Fused SilicaCapillary Column of chromatographic column adopting island Tianjin company, column length 50m, internal diameter 0.22mm, model C BP1-M50-025, the non-polar column of coat-thickness 0.25Micron.Chromatographiccondition: pressure 1MPa before the post; Tail blow pressure power 0.50MPa; Column temperature adopts temperature programming (80 ℃ of initial temperature, residence time 5min, 10 ℃/min of temperature rise rate; 140 ℃ of constant temperature 5min; Warm eventually 180 ℃ and constant temperature 15min); 200 ℃ of sensing chamber's temperature; 210 ℃ of temperature of vaporization chamber.Adopt Shimadzu C-R6A totalizing instrument to carry out data processing, adopt area normalization method that product is carried out quantitative Analysis, correction factor is measured by experiment.
Embodiment:
Embodiment 1
Preparation of catalysts: 17.4g sodium metaaluminate and 51mL HMI at first are dissolved in the 450mL distilled water, slowly splash into the 638g silicon sol under the violent stirring condition then.Gained magma is continued violent stirring 1h, make it full and uniform.Transfer to horizontally in transverse axis roller crystallizing kettle then, be heated to 170 ℃ under the dynamic condition, crystallization 72h, stirring velocity 60rpm.After crystallization finishes, that products therefrom filtration and thorough washing is extremely neutral.Oven dry is spent the night under 120 ℃, gets the former powder of nano level MWW laminate structure Si-Al molecular sieve.This molecular screen primary powder is placed retort furnace, and the 3h internal program is warming up to 538 ℃ of roasting 8h, thoroughly removes template and carbon deposit and gets Na type nano level MWW laminate structure Si-Al molecular sieve.Silica alumina ratio (the SiO of gained molecular sieve
2/ Al
2O
3) be 25, be the hexagonal flake monocrystalline, crystal diameter is 300～500nm, and thickness is 25～50nm, and pore volume is 0.46ml/g.Get above-mentioned synthetic good Na type nano level MWW laminate structure Si-Al molecular sieve 20g and add among the 0.6 mol ammonium nitrate solution 500ml, be warming up to 95 ℃ and exchange 5h, exchange repeatedly 3 times, make the alkalimetal ion weight content less than 50ppm.The qualified zeolite of exchange is placed retort furnace, and the 3h internal program is warming up to 538 ℃, and roasting 6h gets H type nano level MWW laminate structure Si-Al molecular sieve.Above-mentioned H type molecular sieve 13g and 3.9 gram pseudo-boehmites are mixed, add salpeter solution, 0.2g sesbania powder and the 0.4g citric acid of 24ml weight percent 6%, extruded moulding behind the kneading 2h.In 120 ℃ of oven dry 12h, place retort furnace under air atmosphere, to be warming up to 540 ℃ of constant temperature calcining 6h the catalyzer of forming, finished catalyst.
Reactive behavior test: be 8 in benzene and diisopropylbenzene(DIPB) mol ratio, pressure is under the condition of 3.5MPa, respectively at diisopropylbenzene(DIPB) air speed 2～6h
-1With carried out the activity of such catalysts test in the condition and range of 180～220 ℃ of temperature of reaction.Diisopropylbenzene(DIPB) transformation efficiency and isopropyl benzene yield see the following form 1 and table 2 in the reaction solution.
Table 1
Reaction conditions: T=200 ℃ of Con.=transformation efficiency T.O.S=reaction times Yiel.=yield
As can be seen from the results, under 200 ℃, example 1 catalyzer shows very high initial activity (DIPB initial conversion about 85%, isopropyl benzene yield about 90%).Along with the prolongation in reaction times and the increase of DIPB air speed, catalytic activity reduces, and the IPB yield reduces.When the DIPB air speed at 2h
-1The time, catalytic activity keeps stable in 20h.
Table 2
Reaction conditions: DIPB WHSV=6h
-1T.O.S (h)=3h
As can be seen from the results, example 1 catalyzer is in 180～220 ℃ of temperature ranges, and the DIPB transformation efficiency is higher than 50%, and more than 200 ℃, DIPB initial conversion and IPB yield reach more than 80%.
Embodiment 2
Preparation of Catalyst: 12.4g sodium metaaluminate and 51mL HMI at first are dissolved in the 550mL distilled water, slowly splash into the 638g silicon sol under the violent stirring condition then.Gained magma is continued violent stirring 1h, make it full and uniform.Transfer to horizontally in transverse axis roller crystallizing kettle then, be heated to 170 ℃ under the dynamic condition, crystallization 72h, stirring velocity 60rpm.After crystallization finishes, that products therefrom filtration and thorough washing is extremely neutral.Oven dry is spent the night under 120 ℃, gets zeolite powder.Zeolite powder is placed retort furnace, and the 3h internal program is warming up to 538 ℃ of roasting 8h, thoroughly removes template and carbon deposit and gets Na type nano level MWW laminate structure Si-Al molecular sieve, its silica alumina ratio (SiO
2/ Al
2O
3) be 35, hexagonal flake monocrystalline, crystal diameter are 300～500nm, and thickness is 25～50nm, and pore volume is 0.46ml/g.Get above-mentioned synthetic good Na type nano level MWW laminate structure Si-Al molecular sieve 20g and add among the 0.6 mol ammonium nitrate solution 500ml, be warming up to 95 ℃ and exchange 5h, exchange repeatedly 3 times, make the alkalimetal ion weight content less than 50ppm.The qualified zeolite of exchange is placed retort furnace, and the 3h internal program is warming up to 538 ℃ of roasting 6h, gets H type nano level MWW laminate structure Si-Al molecular sieve.Above-mentioned H type molecular sieve 13g and 3.9 gram pseudo-boehmites are mixed, add salpeter solution, 0.2g sesbania powder and the 0.4g citric acid of 24ml weight percent 6%, extruded moulding behind the kneading 2h.In 120 ℃ of oven dry 12h, place retort furnace under air atmosphere, to be warming up to 540 ℃ of constant temperature calcining 6h the catalyzer of forming, finished catalyst.
Reactive behavior test: undertaken by method I.Be 8 in benzene and diisopropylbenzene(DIPB) mol ratio, pressure is under the condition of 3.5MPa, respectively at diisopropylbenzene(DIPB) air speed 6h
-1With carried out the activity of such catalysts test in the condition and range of 200 ℃ of temperature of reaction.Diisopropylbenzene(DIPB) transformation efficiency and isopropyl benzene yield see Table 3 in the reaction solution.
Table 3
As can be seen from the results, example 2 catalyzer show transalkylation activity under these conditions, but catalytic activity and stable phase all are lower than example 1 catalyzer.
Comparative Examples 1
Preparation of Catalyst: under room temperature, the vigorous stirring, the 125mL hexamethylene imine is once joined in the 1600mL distilled water that is dissolved with 240g sodium metaaluminate and 10.1g sodium hydroxide, add the NaCl crystal of half molar weight of sodium hydroxide as required, add the white carbon black of 134g in again in 0.5h, and add the crystal seed that is equivalent to gel quality affects 0.2%, continue to stir 1h then.Reaction solution is transferred in the stainless steel reactor, in 150 ℃ of static crystallization 72h.After crystallization finishes, be cooled to room temperature, with the product suction filtration, washing, and under 120 ℃ of conditions dry 12h, the gained white powder is put into retort furnace, be warming up to 538 ℃ of roasting 8h with the speed of 3 ℃/min and get Na type micron order MWW laminate structure Si-Al molecular sieve.Get above-mentioned synthetic good Na type micron order MWW laminate structure Si-Al molecular sieve 20g and add among the 0.6 mol ammonium nitrate solution 500ml, be warming up to 95 ℃ and exchange 5h, exchange repeatedly 3 times, make the alkalimetal ion weight content less than 50ppm.The qualified zeolite of exchange is placed retort furnace, and the 3h internal program is warming up to 538 ℃ of roasting 6h, gets H type micron order MWW laminate structure Si-Al molecular sieve.The H type micron order MWW laminate structure Si-Al molecular sieve of getting above-mentioned stationary method preparation is total to 13g, adopts with example 1 same procedure to prepare catalyzer.Be that with the difference of embodiment 1 example 3 catalyzer adopt stainless steel crystallizing kettle static hydrothermal synthetic method, the molecular screen primary powder that is obtained is the round pie crystal that multilayer is formed by connecting, and diameter is 3 μ m, and thickness is 1 μ m.
Reactive behavior test: be 8 in benzene and diisopropylbenzene(DIPB) mol ratio, pressure is under the condition of 3.5MPa, respectively at diisopropylbenzene(DIPB) air speed 6h
-1With carried out the activity of such catalysts test in the condition and range of 200 ℃ of temperature of reaction.Diisopropylbenzene(DIPB) transformation efficiency and isopropyl benzene yield see Table 4 in the reaction solution:
Table 4
Comparing result shows that the initial DIPB transformation efficiency of the nm-class catalyst of example 1 reaches 82.8%, compares with the micron order catalyzer of Comparative Examples 1 and shows higher initial activity.Along with the prolongation in reaction times, the catalytic activity of two kinds of samples is all on a declining curve, and the nanocatalyst catalytic activity fall off rate of example 1 is lower than the micron order catalyzer of Comparative Examples 1.
Claims (2)
1. a diisopropylbenzene(DIPB) transalkylation is produced the method for isopropyl benzene, it is characterized in that: adopting stainless steel tubular type fixed-bed reactor internal diameter is 10mm, and the catalyst filling amount is 1g, and benzene and diisopropylbenzene(DIPB) be in mol ratio 8, diisopropylbenzene(DIPB) air speed 2～6h
-1, 180～220 ℃ of temperature of reaction, pressure 3.5MPa condition under carry out catalyzed reaction and generate isopropyl benzene;
Catalyzer is that 100% binding agent with 70～90%H type nano level MWW laminate structure Si-Al molecular sieve and 10～30% mixes by weight, add total catalyst weight 6～8% concentration and be rare nitric acid of 2～7%, 0.5～1.5% sesbania powder and 1.0～2.5% citric acid additive, through mediating, drying, place following 500 ℃～600 ℃ roasting 4～6h of retort furnace air atmosphere to make;
Binding agent is pseudo-boehmite, aluminum oxide, silicon oxide, graphite or zirconium white;
H type nanometer MWW laminate structure Si-Al molecular sieve sial is 25～35 in molar ratio, is the hexagonal flake monocrystalline, and crystal diameter is 50～900nm, and thickness is 20～200nm, specific surface area 〉=400m
2/ g, total pore volume 0.4～0.6ml/g.
2. a kind of diisopropylbenzene(DIPB) transalkylation according to claim 1 is produced the method for isopropyl benzene, and it is characterized in that: the preparation method of H type nano level MWW laminate structure Si-Al molecular sieve is as follows:
1) preparation of Na type nano level MWW laminate structure Si-Al molecular sieve
At first, sodium metaaluminate and template hexamethylene imine are dissolved in an amount of distilled water, under the violent stirring condition, slowly splash into silicon sol, it is standby that gained magma violent stirring 0.5～5h is made colloid, this colloid is transferred to horizontal in transverse axis roller crystallizing kettle, be warming up to 130～180 ℃ under the dynamic crystallization condition, crystallization 48～96h, stirring velocity 40～80rpm, after crystallization finishes, products therefrom filtration and thorough washing is extremely neutral, and oven dry is spent the night under 120 ℃, gets molecular sieve crystal, molecular sieve crystal is placed retort furnace, the 3h internal program is warming up to 538 ℃, and constant temperature calcining 8h thoroughly removes template and carbon deposit and gets Na type nano level MWW laminate structure Si-Al molecular sieve;
2) preparation of H type nano level MWW laminate structure Si-Al molecular sieve
Above-mentioned synthetic good Na type nano level MWW laminate structure Si-Al molecular sieve and ammonium nitrate solution are exchanged, 80～95 ℃ of exchange temperature, liquid-solid ratio is 25ml/g, ammonium nitrate concn is 0.5～2 mol, after 3 exchanges, makes the alkalimetal ion weight content less than 50ppm, the qualified zeolite of exchange is placed retort furnace, the 3h internal program is warming up to 538 ℃, and roasting 6h gets H type nano level MWW laminate structure Si-Al molecular sieve.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863311A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | Method for producing isopropylbenzene by transalkylation |
| CN105130728A (en) * | 2015-08-21 | 2015-12-09 | 中石化炼化工程（集团）股份有限公司 | Method for preparing xylene from methanol, and apparatus thereof |
| CN113600226A (en) * | 2021-08-30 | 2021-11-05 | 南京克米斯璀新能源科技有限公司 | Heavy alkylbenzene anti-alkylation catalyst and preparation method and application thereof |
| CN115532306A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Composite catalyst for transalkylation and preparation method and application thereof |
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| US5371310A (en) * | 1991-06-19 | 1994-12-06 | Mobil Oil Corp. | Process for preparing short chain alkyl aromatic compounds |
| CN1397494A (en) * | 2002-06-28 | 2003-02-19 | 吉林大学 | Nano-class molecular sieve and its synthesizing process |
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| US5371310A (en) * | 1991-06-19 | 1994-12-06 | Mobil Oil Corp. | Process for preparing short chain alkyl aromatic compounds |
| CN1397494A (en) * | 2002-06-28 | 2003-02-19 | 吉林大学 | Nano-class molecular sieve and its synthesizing process |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102863311A (en) * | 2011-07-08 | 2013-01-09 | 中国石油天然气股份有限公司 | Method for producing isopropylbenzene by transalkylation |
| CN105130728A (en) * | 2015-08-21 | 2015-12-09 | 中石化炼化工程（集团）股份有限公司 | Method for preparing xylene from methanol, and apparatus thereof |
| CN105130728B (en) * | 2015-08-21 | 2018-06-29 | 中石化炼化工程（集团）股份有限公司 | A kind of method and device that dimethylbenzene is prepared using methanol |
| CN115532306A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Composite catalyst for transalkylation and preparation method and application thereof |
| CN115532306B (en) * | 2021-06-30 | 2024-01-30 | 中国石油化工股份有限公司 | Composite catalyst for alkyl transfer and preparation method and application thereof |
| CN113600226A (en) * | 2021-08-30 | 2021-11-05 | 南京克米斯璀新能源科技有限公司 | Heavy alkylbenzene anti-alkylation catalyst and preparation method and application thereof |
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