CN102863311A - Method for producing isopropylbenzene by transalkylation - Google Patents
Method for producing isopropylbenzene by transalkylation Download PDFInfo
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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 50
- 238000010555 transalkylation reaction Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- LGXAANYJEHLUEM-UHFFFAOYSA-N 1,2,3-tri(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1C(C)C LGXAANYJEHLUEM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 35
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 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 claims abstract description 21
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 13
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 12
- 238000001125 extrusion Methods 0.000 claims abstract description 11
- 238000005469 granulation Methods 0.000 claims abstract description 11
- 230000003179 granulation Effects 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 5
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 5
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004327 boric acid Substances 0.000 claims abstract description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 5
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 4
- 239000001923 methylcellulose Substances 0.000 claims abstract description 4
- 244000275012 Sesbania cannabina Species 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 42
- 238000000034 method Methods 0.000 claims description 25
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 claims description 20
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000000465 moulding Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 abstract description 21
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005096 rolling process Methods 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 abstract 1
- 241000219782 Sesbania Species 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000029936 alkylation Effects 0.000 description 4
- 238000005804 alkylation reaction Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 2
- 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
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000282346 Meles meles Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000009992 mercerising Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for producing isopropylbenzene by transalkylation; the transalkylation catalyst is prepared by uniformly mixing H beta/HMCM-49 composite molecular sieve raw powder with an auxiliary agent, a binder, a pore-forming agent and a lubricant in proportion, and performing rolling, granulation, extrusion, drying, roasting and cooling, wherein the auxiliary agent is SB powder or one of the SB powder and phosphoric acid, ammonium phosphate and boric acid, the binder is sesbania powder, the pore-forming agent is one of methylcellulose, citric acid and oxalic acid, and the lubricant is one or two of nitric acid with the concentration of 0.5-15% and phosphoric acid with the concentration of 0.5-15%; the raw materials are diisopropylbenzene or/and triisopropylbenzene and benzene; the transalkylation catalyst has good activity, high selectivity and long service life, and the yield of the cumene reaches 72.1 to 94.1 percent.
Description
Technical field:
The present invention relates to diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene and carry out the method that transalkylation is produced isopropyl benzene.
Background technology:
Isopropyl benzene is organic chemical industry's important source material.It is the raw material of phenol, acetone, methyl phenyl ketone and alpha-methyl styrene.Present phenol production more than 90% all is to adopt cumene method production, and this method is take benzene and propylene as raw material, in the effect of an acidic catalyst, carries out alkylated reaction and synthesizes and form; The polyisopropylbenzenes such as while by-product diisopropylbenzene(DIPB), tri-isopropyl benzene; Reduce the isopropyl benzene yield, in order to improve raw material availability, reduced production costs, with diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene reaction, carried out transalkylation, produced isopropyl benzene, improved the yield of isopropyl benzene.
Industrial, the isopropyl benzene production technique all is alkylation and transalkylation circulation method.Early stage method is the solid phosphoric acid method of UOP (UOP) and the AlCl of Monsanto/Lummus Grest company
3Method.There is the shortcoming serious to equipment corrosion in these two kinds of methods.Along with the development of synthetic molecular sieve, the catalyzer of synthesizing iso-propylbenzene develops rapidly thereupon.At present, divide according to the synthesizing iso-propylbenzene catalyst type, the isopropyl benzene production technique is mainly divided three classes: the one, Enichem technique, take the BETA molecular sieve as catalyzer, adopt fixed bed liquid phase method technique, processing condition are benzene/propylene=4,150 ℃ of temperature, pressure 3.0Mpa, alkylation liquid in a large number circulates, every three months, need hot benzene regeneration once; The 2nd, Dow/Kellog technique, adopting high performance dealuminzation mercerising molecular sieve is catalyzer, and the content of by product n-proplbenzene in product drops to 0.01%, and alkylation liquid and catalyst regeneration in a large number circulate; The 3rd is Mobil/Badger technique, adopt the Mobil MCM-22 of company molecular sieve catalyst, selectivity, Activity and stabill further improve, catalyst life 2 years regeneration periods, is regenerated convenient as long as five years, the device running efficiency is high, throughput significantly improves, environmentally safe, to equipment without corrosion.On the development trend of the catalyzer of synthesizing iso-propylbenzene, the catalyzer of synthetic propylbenzene is MCM type catalyst series, and it is low that MCM type catalyst series has temperature of reaction, and benzene/propylene is than low characteristic, but contain diisopropylbenzene(DIPB), tri-isopropyl benzene and polyisopropylbenzene in the reaction product, affect the reduction of cost.From producing on the isopropyl benzene technique, transalkylation catalyst also is the integral part of producing isopropyl benzene, is to reduce production costs, improve isopropyl benzene production technology important step.The development of transalkylation catalyst also is the progress of isopropyl benzene production technology.
At present, openly transalkylation catalyst has BETA, Y, ZSM-5, MOR float stone, MCM-22, MCM-49 and phosphoric acid modification, rare earth modified, Dealumination processing molecular sieve catalyst.The CN1596151 patent discloses two coexisting molecular sieves of a class twelve-ring and synthetic method thereof, the transalkylation catalyst that wherein relates to dealuminium mordenite and the two-pack of the second zeolite with twelve-ring, the second component zeolite comprises MCM-22, MCM-49, MCM-56, BETA and ZSM-12 equimolecular sieve, and it is more excellent to be BETA.The technological process of the open benzene of patent US5557024 and ethene, propylene alkylation and transalkylation catalyst synthesizing ethyl benzene and isopropyl benzene, its transalkylation catalyst that relates to is MCM-22, X, Y, MOR and BETA molecular sieve, what it was more excellent is the BETA molecular sieve.This two patent thinks that all BETA molecular sieve p-Diisopropylbenzene transalkylation is more excellent.Patent US5371310 discloses the technology that adopts MCM-22 and MCM-49 molecular sieve transalkylation catalyst.Above-mentioned three patents are all thought MCM-22 and the MCM-49 molecular sieve with MWW structure, and the p-Diisopropylbenzene transalkylation has catalytic activity.But the catalyst technology that does not all relate to the tri-isopropyl benzene transalkylation; Do not relate to and add acidic site and the strength of acid that auxiliary agent comes regulating catalyst; Do not relate to and add the inner duct that pore-forming material improves catalyzer, promote the macromolecular diffusion of space resistance.
Patent US5236575 relates to a kind of MCM-49 Zeolite synthesis method of MWW structure.The CN1191198C patent relates to a kind of nanometer MCM-49 molecular sieve and synthetic method, and the MCM-49 molecular sieve slip that these two patents all do not relate to after the crystallization carries out O
3Or H
2O
2Oxide treatment is improved electron distributions in the molecular sieve.
Since tri-isopropyl benzene be on phenyl ring with three cumyls, its molecular diameter is larger, space resistance is larger, therefore carrying out transalkylation reacts required catalyzer inner duct, compares with the required catalyzer inner duct of the transalkylation reaction of diisopropylbenzene(DIPB) and wants large; It is many that want the acid sites position of catalyzer.Transalkylation reaction to the diisopropylbenzene(DIPB) that contains tri-isopropyl benzene uses any one molecular sieve catalyst among single MCM-22, MCM-49, ZMS-5, X, Y, MOR and the BETA, and catalytic effect is undesirable.In addition because the molecular weight of tri-isopropyl benzene is large, on temperature of reaction, tri-isopropyl benzene and benzene carry out that transalkylation is higher than the temperature of the transalkylation of diisopropylbenzene(DIPB), and energy consumption is high in the production, so low temperature, high reactivity polyalkylbenzene catalyzer are the development trends of transalkylation catalyst.
Summary of the invention:
The object of the present invention is to provide a kind of transalkylation to produce the method for isopropyl benzene.Employed a kind of composite molecular sieve catalyst is higher than similar transalkylation catalyst to low temperature active and the stability of polyalkylbenzene (one or both in diisopropylbenzene(DIPB), the tri-isopropyl benzene) transalkylation.
Composite molecular sieve catalyst of the present invention is to add auxiliary agent, binding agent, pore-forming material and lubricant with the former powder of H β/HMCM-49 composite molecular screen, through rolling, granulation, extrusion, drying, roasting, make catalyzer.The HMCM-49 molecular sieve has the MWW topological framework, and laminate structure is arranged; The H beta-molecular sieve is the twelve-ring basket structure, has the molecular sieve of these two kinds of structures, is fit to diisopropylbenzene(DIPB) and tri-isopropyl benzene transalkylation; The acidic site and the strength of acid that add the auxiliary agent regulating catalyst; Add pore-forming material, increase the duct between catalyst molecule sieve body, increase the through hole of catalyzer inside, be more suitable for molecule space resistance large tri-isopropyl benzene diffusion and absorption, reduce large molecule residence time on the active centre of space resistance, keep the quantity in catalyzer internal surface active centre; The adding lubricant improves the quality of shaping of catalyst.This catalyzer is fit to diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene and carries out transalkylation reaction, is the transalkylation catalyst that a kind of activity is good, selectivity is high, the life-span is long.
The present invention is achieved through the following technical solutions:
The present invention adopts H β/former powder of HMCM-49 composite molecular screen and auxiliary agent, binding agent, pore-forming material and mix lubricant even, through rolling, granulation, extrusion, drying, roasting and cooling, make transalkylation catalyst.
H β/HMCM-49 composite molecular screen, HMCM-49 are the 10-150% of H β quality, more excellent 35-95%.
Auxiliary agent can use separately the SB powder, also can use a kind of mixing the in SB powder and phosphoric acid, ammonium phosphate, the boric acid, and promoter addition accounts for the 15-50% of H β/former opaque amount of HMCM-49 composite molecular screen, and more excellent is 20-35%; Use the mixture auxiliary agent of SB powder, the SB powder accounts for the 55-95% of auxiliary agent quality.
Binding agent is the sesbania powder, and add-on accounts for the 0.1-5% of H β/former opaque amount of HMCM-49 composite molecular screen, and more excellent is 0.5-3.5%.
Pore-forming material is a kind of in methylcellulose gum, citric acid, the oxalic acid, and its add-on accounts for the 0.1-5% of H β/former opaque amount of HMCM-49 composite molecular screen.
Lubricant is one or both of mass concentration 0.1-15% aqueous nitric acid, mass concentration 0.1-15% phosphate aqueous solution, its add-on: the former powder of 100gH β/MCM-49 composite molecular screen adds lubricant 120-200ml.When adding two kinds of lubricants, wherein nitric acid, phosphoric acid quality are than being 10-50: 1.
(1) mixes according to above proportion scale, place on the roller, roll 20-60min, according to the wet degree of doing of material, regulate with 0.1-15% nitric acid, 0.1-15% phosphoric acid.Wet feed after rolling carries out granulation, particle size range 0.1-5mm.
(2) wet feed after the granulation joins banded extruder, extrusion pressure control 10-20MPa, the percentage of open area 0.1-10% of orifice plate, the hole be shaped as circle or trifolium-shaped, the aperture is 1.0-2.0mm.
(3) bar after the moulding is put baking oven into, carries out drying.Drying temperature 100-150 ℃, time of drying 4-8h.
Dried billot carries out roasting.Rate of roasting rises to 120 ℃ from room temperature and is 30min; At 120 ℃ of constant temperature 20min; Be warming up to 400 ℃ from 120 ℃ and be 40min; At 400 ℃ of constant temperature 30min; Be warming up to 540-600 ℃ from 400 ℃ and be 30min, then constant temperature 240-500min; Naturally be cooled to room temperature, make catalyzer.
The 10g catalyzer is packed in the reactor, and reactor is Φ 25*2*900mm stainless steel tubular type reactor.With volume pump raw material is squeezed in the reactor, carried out transalkylation reaction.Reaction pressure 2.0-3.0MPa, total liquid air speed 0.5-3h
-1, evaluation result: diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene carry out transalkylation reaction, and its mass ratio is 5-15: 2-10: 75-93, during 190 ℃ of temperature of reaction, the transformation efficiency of diisopropylbenzene(DIPB) reaches 76.8%, and the transformation efficiency of tri-isopropyl benzene reaches 47.8%, and the yield of isopropyl benzene reaches 72.1%.Tri-isopropyl benzene and benzene carry out transalkylation reaction, during 190 ℃ of its temperature of reaction, and tri-isopropyl benzene transformation efficiency 54.8%, isopropyl benzene selectivity 94.1%.
Catalyzer provided by the invention has the following advantages:
The MWW structure that this acidity of catalyst position is many, strength of acid suits, have a HMCM-49 has again H
The structure of the twelve-ring cage of β, through hole is many, and applicable diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene carry out transalkylation reaction simultaneously, and temperature of reaction is low, and air speed is large.
Embodiment:
Embodiment 1
The preparation of catalyzer: weigh HMCM-49/H β mass ratio and be 45% the H β/former powder 75g of HMCM-49 composite molecular screen (exploitation of research institute of Jilin Petrochemical company), SB powder 25g, sesbania powder 2.0g, methylcellulose gum 3.5g, mix evenly with 15% nitric acid 120ml, rolled 20 minutes; Carry out granulation; Carry out extrusion at banded extruder, wet billot places on the enamel tray, puts baking oven into, is warming up to 130 ℃, and dry 5.5h after the drying, carries out roasting in muffle furnace: rise to 120 ℃ from room temperature and be 30min; At 120 ℃ of constant temperature 20min; Be warming up to 400 ℃ from 120 ℃ and be 40min; At 400 ℃ of constant temperature 30min; Be warming up to 580 ℃ from 400 ℃ and be 30min, then constant temperature 300min; Naturally be cooled to room temperature, make catalyzer.Catalyst activity is estimated: catalyzer is packed in the tubular reactor, and reactor is Φ 25*2*900mm, carries out the reaction of tri-isopropyl benzene and benzene, the mass percent of tri-isopropyl benzene and benzene 90: 10, always liquid air speed 1.4-1.6h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table one.
Table one
Embodiment 2
The preparation of catalyzer: weigh HMCM-49/H β mass ratio and be 58% H β/former powder 75g of HMCM-49 composite molecular screen (exploitation of research institute of Jilin Petrochemical company), SB powder 12g, ammonium phosphate 8g, sesbania powder 1.5g, citric acid 2g.Mix evenly with 15% aqueous nitric acid 125ml, rolled 30 minutes at rolling machine, carry out granulation with tablets press, carry out extrusion at banded extruder, wet billot places on the enamel tray, under 120 ℃, and dry 5h; After the drying, move in the roasting dish, in muffle furnace, carry out roasting, rise to 120 ℃ from room temperature and be 30min; At 120 ℃ of constant temperature 20min; Be warming up to 400 ℃ from 120 ℃ and be 40min; At 400 ℃ of constant temperature 30min; Be warming up to 560 ℃ from 400 ℃ and be 30min, then constant temperature 300min; Naturally be cooled to room temperature, make catalyzer.
Catalyst activity is estimated: catalyzer is packed in the tubular reactor, reactor is Φ 25*2*900mm, carry out the reaction of diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene, the mass percent of tri-isopropyl benzene, diisopropylbenzene(DIPB) and benzene 3.5: 7.2: 89.3, total liquid air speed 1.4-1.6h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table two.
Table two
Embodiment 3
The preparation of catalyzer: weigh HMCM-49/H β mass ratio and be 72% H β-former powder 75g of HMCM-49 composite molecular screen (exploitation of research institute of Jilin Petrochemical company), SB powder 18g, boric acid 2g, sesbania powder 2.5g, oxalic acid 1.5g, mix evenly with 15% phosphate aqueous solution 130ml, rolled 30 minutes at rolling machine, carry out granulation with tablets press, carry out extrusion at banded extruder, wet billot places on the enamel tray, under 120 ℃, and dry 6h; After the drying, move in the roasting dish, in muffle furnace, carry out roasting and rise to 120 ℃ for 30min from room temperature; At 120 ℃ of constant temperature 20min; Be warming up to 400 ℃ from 120 ℃ and be 40min; At 400 ℃ of constant temperature 30min; Be warming up to 545 ℃ from 400 ℃ and be 30min, then constant temperature 300min; Naturally be cooled to room temperature, make catalyzer.
Catalyst activity is estimated: catalyzer is packed in the tubular reactor, reactor is Φ 25*2*900mm, carry out the reaction of diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene, the mass percent of tri-isopropyl benzene, diisopropylbenzene(DIPB) and benzene 3.6: 6.9: 89.5, total liquid air speed 1.4-1.6h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table three
Table three
Embodiment 4
The preparation of catalyzer: weigh HMCM-49/H β mass ratio and be 90% the H β/former powder 75g of HMCM-49 composite molecular screen (exploitation of research institute of Jilin Petrochemical company), SB powder 25g, sesbania powder 1.5g, citric acid 1.5g, mix evenly with 15% aqueous nitric acid 140ml, rolled 30 minutes at rolling machine; Carry out granulation with tablets press; Carry out extrusion at banded extruder; Wet billot places on the enamel tray, under 120 ℃, and dry 5.5h; After the drying, move in the roasting dish, in muffle furnace, carry out roasting, rise to 120 ℃ from room temperature and be 30min; At 120 ℃ of constant temperature 20min; Be warming up to 400 ℃ from 120 ℃ and be 40min; At 400 ℃ of constant temperature 30min; Be warming up to 575 ℃ from 400 ℃ and be 30min, then constant temperature 260min; Naturally be cooled to room temperature, make catalyzer.
Catalyst activity is estimated: catalyzer is packed in the tubular reactor, reactor is Φ 25*2*900mm, carry out the reaction of diisopropylbenzene(DIPB), tri-isopropyl benzene and benzene, the mass percent of tri-isopropyl benzene, diisopropylbenzene(DIPB) and benzene 4.5: 8.3: 87.2, total liquid air speed 1.4-1.6h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table four.
Table four
Embodiment 5
The preparation of catalyzer: weigh HMCM-49/H β mass ratio and be 135% the H β/former powder 75g of HMCM-49 composite molecular screen (exploitation of research institute of Jilin Petrochemical company), SB powder 22g, sesbania powder 1.8g, oxalic acid 2.5g, mix evenly with 15% aqueous nitric acid 100ml and 5% phosphoric acid 35ml, rolled 30 minutes at rolling machine, carry out granulation with tablets press; Carry out extrusion at banded extruder; Wet billot places on the enamel tray, under 120 ℃, and dry 5h; After the drying, move in the roasting dish, in muffle furnace, carry out roasting, rise to 120 ℃ from room temperature and be 30min; At 120 ℃ of constant temperature 20min; Be warming up to 400 ℃ from 120 ℃ and be 40min; At 400 ℃ of constant temperature 30min; Be warming up to 550 ℃ from 400 ℃ and be 30min, then constant temperature 300min; Naturally be cooled to room temperature, make catalyzer.
Catalyst activity is estimated: catalyzer is packed in the tubular reactor, and reactor is Φ 25*2*900mm, carries out the reaction of tri-isopropyl benzene and benzene, the mass percent of tri-isopropyl benzene and benzene 8.3: 91.7, always liquid air speed 1.4-1.6h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table five.
Table five
Embodiment 6
Catalyzer adopts the catalyzer of the method preparation of embodiment 1.
Catalyzer is packed in the tubular reactor, and reactor is Φ 25*2*900mm, carries out the transalkylation reaction of tri-isopropyl benzene and benzene, the mass percent of benzene and tri-isopropyl benzene 65: 35, total liquid air speed 0.8-1.2h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table six.
Table six
Embodiment 7
Catalyzer adopts the catalyzer of the method preparation of embodiment 2.
Catalyzer is packed in the tubular reactor, and reactor is Φ 25*2*900mm, carries out the transalkylation reaction of tri-isopropyl benzene, benzene, and the mass percent of benzene and tri-isopropyl benzene is 65: 35, total liquid air speed 0.8-1.2
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table seven.
Table seven
Embodiment 8
Catalyzer adopts the catalyzer of the method preparation of embodiment 3.
Catalyzer is packed in the tubular reactor, and reactor is Φ 25*2*900mm, carries out the transalkylation reaction of tri-isopropyl benzene and benzene, and the mass percent of benzene and tri-isopropyl benzene is 65: 35, total liquid air speed 0.8-1.2h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table eight.
Table eight
Embodiment 9
Catalyzer adopts the catalyzer of the method preparation of embodiment 4.
Catalyzer is packed in the tubular reactor, and reactor is Φ 25*2*900mm, carries out the transalkylation reaction of tri-isopropyl benzene and benzene, and the mass percent of benzene and tri-isopropyl benzene is 65: 35, total liquid air speed 0.8-1.2h
-1, temperature of reaction 170-250 ℃, reaction pressure 2.5-3.0MPa.Reaction result sees Table nine.
Table nine
Claims (5)
1. a transalkylation is produced the method for isopropyl benzene, it is characterized in that: take diisopropylbenzene(DIPB) or/and tri-isopropyl benzene and benzene generate isopropyl benzene as raw material carries out transalkylation reaction, and reaction pressure 2.0-3.0MPa, total liquid air speed 0.5-3h
-1, 190 ℃ of temperature of reaction;
Catalyzer adopts H β/former powder of HMCM-49 composite molecular screen, auxiliary agent, binding agent, pore-forming material and lubricant to prepare in following ratio and method:
H β/HMCM-49 composite molecular screen, HMCM-49 accounts for the 10-150% of H β quality;
Auxiliary agent is the SB powder, or a kind of in SB powder and phosphoric acid, ammonium phosphate, the boric acid, and add-on accounts for the 15-50% of H β/former opaque amount of HMCM-49 composite molecular screen;
Binding agent is the sesbania powder, and add-on accounts for the 0.1-5% of H β/former opaque amount of HMCM-49 composite molecular screen;
Pore-forming material is a kind of in methylcellulose gum, citric acid, the oxalic acid, and add-on accounts for the 0.1-5% of H β/former opaque amount of HMCM-49 composite molecular screen;
Lubricant is that mass concentration is that 0.1-15% nitric acid, mass concentration are one or both in the 0.1-15% phosphoric acid, and add-on is that the former powder of 100gH β/MCM-49 composite molecular screen adds lubricant 120-200ml;
Step is as follows:
(1) above-mentioned raw materials is mixed in proportion, roll 20-60min, then granulation, particle size range 0.1-5mm;
(2) carry out extrusion, extrusion pressure is controlled at 10-20MPa, the percentage of open area 0.1-10% of orifice plate, the hole be shaped as circle or trifolium-shaped, the aperture is 1.0-2.0mm;
(3) bar after the moulding carries out drying, drying temperature 100-140 ℃, time of drying 4-8h;
(4) dried billot carries out roasting, and heat-up rate is warming up to 120 ℃ when being 30min, constant temperature 20min; 40min is warming up to 400 ℃, constant temperature 30min; 30min is warming up to 540-600 ℃, constant temperature 240-800min, and roasting is cooled to room temperature after finishing naturally, makes catalyzer.
2. the preparation method of a kind of transalkylation catalyst according to claim 1, it is characterized in that: promoter addition accounts for the 20-35% of H β/former opaque amount of HMCM-49 composite molecular screen.
3. the preparation method of a kind of transalkylation catalyst according to claim 1 is characterized in that: use a kind of mixture auxiliary agent in SB powder and phosphoric acid, ammonium phosphate, the boric acid, the SB powder accounts for the 55-95% of auxiliary agent quality.
4. the preparation method of a kind of transalkylation catalyst according to claim 1, it is characterized in that: the binding agent add-on accounts for the 0.5-3.5% of H β/former powder of HMCM-49 composite molecular screen.
5. the preparation method of a kind of transalkylation catalyst according to claim 1 is characterized in that: when adding two kinds of lubricants, wherein nitric acid, phosphoric acid quality are than being 10-50: 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105502430A (en) * | 2014-10-11 | 2016-04-20 | 中国石油化工股份有限公司 | Beta/MCM-49 composite molecular sieve with core-shell structure and preparation method thereof |
| CN116096695A (en) * | 2020-09-30 | 2023-05-09 | 环球油品有限责任公司 | Transalkylation of alkylated phenols |
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| CN102020527A (en) * | 2009-09-18 | 2011-04-20 | 中国石油天然气股份有限公司 | Method for producing isopropylbenzene by diisopropylbenzene transalkylation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102020527A (en) * | 2009-09-18 | 2011-04-20 | 中国石油天然气股份有限公司 | Method for producing isopropylbenzene by diisopropylbenzene transalkylation |
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| 石理: "吉化院开发成功异丙苯生产MCM-49分子筛纳米催化剂", 《石油化工技术与经济》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105502430A (en) * | 2014-10-11 | 2016-04-20 | 中国石油化工股份有限公司 | Beta/MCM-49 composite molecular sieve with core-shell structure and preparation method thereof |
| CN116096695A (en) * | 2020-09-30 | 2023-05-09 | 环球油品有限责任公司 | Transalkylation of alkylated phenols |
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