CN103201238B - Benzene alkylation - Google Patents
Benzene alkylation Download PDFInfo
- Publication number
- CN103201238B CN103201238B CN201180050138.7A CN201180050138A CN103201238B CN 103201238 B CN103201238 B CN 103201238B CN 201180050138 A CN201180050138 A CN 201180050138A CN 103201238 B CN103201238 B CN 103201238B
- Authority
- CN
- China
- Prior art keywords
- benzene
- tops
- distillation reactor
- catalytic distillation
- reactor assembly
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 441
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 40
- 230000029936 alkylation Effects 0.000 title claims abstract description 35
- 238000004821 distillation Methods 0.000 claims abstract description 126
- 238000006243 chemical reaction Methods 0.000 claims abstract description 99
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 95
- 230000003197 catalytic effect Effects 0.000 claims abstract description 90
- 238000000034 method Methods 0.000 claims abstract description 57
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 238000010555 transalkylation reaction Methods 0.000 claims abstract description 25
- 239000011541 reaction mixture Substances 0.000 claims abstract description 8
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims abstract description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical group CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 44
- RWGFKTVRMDUZSP-UHFFFAOYSA-N isopropyl-benzene Natural products CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 42
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 239000007791 liquid phase Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 12
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 8
- 238000005194 fractionation Methods 0.000 claims description 8
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 4
- 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 description 3
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005844 autocatalytic reaction Methods 0.000 claims 4
- 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 1
- 101000648997 Homo sapiens Tripartite motif-containing protein 44 Proteins 0.000 claims 1
- 102100028017 Tripartite motif-containing protein 44 Human genes 0.000 claims 1
- 150000001908 cumenes Chemical class 0.000 claims 1
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000001983 dialkylethers Chemical class 0.000 abstract 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 16
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- 239000010457 zeolite Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000002808 molecular sieve Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910017119 AlPO Inorganic materials 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000003442 catalytic alkylation reaction Methods 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/862—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms
- C07C2/864—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only oxygen as hetero-atoms the non-hydrocarbon is an alcohol
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
- C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
- C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/205—Organic compounds not containing metal atoms by reaction with hydrocarbons added to the hydrocarbon oil
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1096—Aromatics or polyaromatics
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4087—Catalytic distillation
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
-
- 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
- Y02P20/10—Process efficiency
Abstract
A process for the production of alkylbenzene, the process including: feeding a Ci to C6 alcohol and benzene to a catalytic distillation reactor system comprising an upper reaction zone containing an alkylation catalyst and a lower reaction zone containing a transalkylation catalyst, which may be the same or different than the alkylation catalyst; concurrently in the catalytic distillation reactor system: reacting a portion of the alcohol with the benzene within the upper reaction zone to form a reaction mixture containing water, alkylbenzene, dialkyl ether, unreacted alcohol, unreacted benzene, and polyalkylate including dialkylbenzene; reacting a portion of the polyalkylate with benzene in the lower reaction zone to form additional alkylbenzene; and fractionally distilling the reaction mixture; recovering an overheads fraction from the catalytic distillation reactor system comprising benzene, unreacted alcohol, water, and dialkyl ether; recovering a bottoms fraction from the catalytic distillation reactor system comprising benzene, alkylbenzene, and polyalkylate.
Description
Technical field
The present invention relates generally to the preparation method of alkylbenzene, comprising ethylbenzene and cumene.
Background technology
Current ethylbenzene and cumene be by benzene respectively with alkene, namely ethene or propylene react preparation under acid catalysis.Recently, benzene alkylation processes adopts corresponding alcohols as alkylating reagent.Cumene, is also isopropyl benzene, can be used as preparing phenol, acetone and vinyl toluene.Ethylbenzene can be used as preparing vinylbenzene.The aromatic hydrocarbons that alkyl replaces also can be used as high-octane transport fuel.The method having had multiple alkylaromatic hydrocarbon to prepare is in the news.
The existing method preparing ethylbenzene and cumene also unavoidably can produce many alkylates while obtaining the monoalkylated product wanted.Therefore usually many alkylates and benzene can be carried out transalkylation reaction to produce more monoalkylated benzenes, transalkylation reaction is generally many alkylates are back in alkylation reactor or are transported in other transalkylation reactor by many alkylates to go to carry out.But these programs need extra separating and treating apparatus or independently transalkylation reactor, this can the complicacy of remarkable increase program, the quantity of parts, the step of operation and cost.
Summary of the invention
Contriver finds, by integrating distillation, catalytic alkylation reaction and catalysis transalkylation reaction system, can improve the alkylation process of benzene and alcohol.Such as, catalytic distillation reactor assembly may be used for the reaction of ethanol and benzene synthesizing styrene.Benzene can mix with withdrawing fluid and be brought to distillation tower top.Fresh ethanol, unreacted ethanol, by product ether (being also a kind of alkylating reagent) and issuable partially recycled benzene and many alkylated benzenes can be transported between the transalkylation catalyst of alkylation catalyst on tower top and tower bottom.Like this, distillation, alkylation and these three reactive systems transalkylating just can be unified in a reaction tower, be reduced by least one preparing the main reactor used in ethylbenzene conventional process with this.Cumene and other alkylbenzenes also can adopt similar fashion to use corresponding alcohols to prepare.
On the one hand, the present invention relates to the preparation method about alkylbenzene, the method comprises: by C
1-C
6alcohol and benzene are transported in catalytic distillation reactive system, this system comprises one containing the high reaction zone of alkylation catalyst and one the low reaction district containing transalkylation catalyst (itself and alkylation catalyst identical or different), reaction below simultaneously occurring in this catalytic distillation reactor assembly: a part of alcohol and benzene react forming reactions mixture in high reaction zone, wherein comprise dialkyl benzene containing water, alkylbenzene, alkyl oxide, unreacted alcohol, unreacted benzene and many alkylide; Reaction forms more alkylbenzene in low reaction district for the many alkylide of a part and benzene; Then by reaction mixture fractionation; Reclaim the overhead fraction in catalytic distillation reactor assembly, comprise benzene, unreacted alcohol, water and alkyl oxide, reclaim the end cut in catalytic distillation reactor assembly, comprise benzene, alkylbenzene and many alkylide.
On the other hand, the present invention relates to the preparation method about ethylbenzene, the method comprises: ethanol and benzene are transported in catalytic distillation system, this system comprises one containing the high reaction zone of alkylation catalyst and one the low reaction district containing transalkylation catalyst (itself and alkylation catalyst identical or different), reaction below simultaneously occurring in this catalytic distillation reactor assembly: a part of ethanol and benzene react forming reactions mixture in high reaction zone, wherein containing water, ethylbenzene, ether, unreacted ethanol, unreacted benzene and many alkylide comprise diethylbenzene, reaction forms more ethylbenzene in low reaction district for the many alkylide of a part and benzene, then by reaction mixture fractionation, reclaim the overhead fraction in catalytic distillation reactor assembly, comprise benzene, ethanol, water and ether, reclaim the end cut in catalytic distillation reactor assembly, comprise benzene, ethylbenzene and many alkylide, overhead fraction is concentrated and is separated and form the first liquid cut containing benzene and the second liquid cut containing water, ethanol and ether, tower bottom distillate in catalytic distillation reactor assembly is separated in the first distillation tower, reclaims the overhead fraction containing benzene and contain the tower bottom distillate of ethylbenzene and many alkylide, to be transported in catalytic distillation reactor assembly and reflux by first liquid cut at least partially, second liquid cut is separated in second column, reclaims the overhead fraction containing ethanol and ether and the tower bottom distillate containing water, in the middle of ethanol and the high reaction zone being transported to catalytic distillation reactor assembly from the overhead fraction of second column at least partially and low reaction district.
On the other hand, the present invention relates to the preparation method about cumene, the method comprises: Virahol and benzene are transported in catalytic distillation system, this system comprises one containing the high reaction zone of alkylation catalyst and one the low reaction district containing transalkylation catalyst (itself and alkylation catalyst identical or different), reaction below simultaneously occurring in this catalytic distillation reactor assembly: a part of Virahol and benzene react forming reactions mixture in high reaction zone, wherein containing water, isopropyl benzene, isopropyl ether, unreacted Virahol, unreacted benzene and many alkylide comprise diisopropyl benzene, reaction forms more isopropyl benzene in low reaction district for the many alkylide of a part and benzene, then by reaction mixture fractionation, reclaim the overhead fraction in catalytic distillation reactor assembly, comprise benzene, Virahol, water and isopropyl ether, reclaim the end cut in catalytic distillation reactor assembly, comprise benzene, isopropyl benzene and many alkylide, overhead fraction is concentrated and is separated and form the first liquid cut containing benzene and the second liquid cut containing water, Virahol and isopropyl ether, tower bottom distillate in catalytic distillation reactor assembly is separated in the first distillation tower, reclaims the overhead fraction containing benzene and contain the tower bottom distillate of isopropyl benzene and many alkylide, to be transported in catalytic distillation reactor assembly and reflux by first liquid cut at least partially, second liquid cut is separated in second column, reclaims the overhead fraction containing Virahol and isopropyl ether and the tower bottom distillate containing water, in the middle of Virahol and the high reaction zone being transported to catalytic distillation reactor assembly from the overhead fraction of second column at least partially and low reaction district.
Other aspects of the present invention and advantage illustrate in following description and additional claim.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the benzene alkylation simplified according to one embodiment of present invention.
Fig. 2 is the process flow sheet of the benzene alkylation simplified according to one embodiment of present invention.
Fig. 3 is the some processes schema of the benzene alkylation simplified according to one embodiment of present invention.
Fig. 4 is the process flow sheet of the benzene alkylation simplified according to one embodiment of present invention.
Fig. 5 is the process flow sheet of the benzene alkylation simplified according to one embodiment of present invention.
Embodiment
In the scope of the application, " catalytic distillation reactor assembly " represents a kind of instrument, and wherein catalyzed reaction and product separation at least carry out local simultaneously.This instrument comprises a traditional catalytic distillation tower reactor, under boiling conditions, reaction and distillation inside can be carried out simultaneously, or distillation column is effectively connected with at least one side reaction device, sideing stream in distillation tower can be used as the raw material of side reaction device, product after simultaneous reactions flow back into again in distillation tower, and this side reaction device is equivalent to Liquid-phase reactor, Gas-phase reactor or a boiling point reactors.Two kinds of described catalytic distillation reactor assemblies can be better than traditional liquid phase reaction and add follow-up lock out operation, catalytic distillation column type reactor at minimizing device, reduce costs, thermal discharge efficiency high (reaction liberated heat may the evaporation of mixed thing absorb), and make the aspects such as the ability of balanced sequence have advantage.For the distillation tower that many parts are separated, if a part for distillation tower comprises catalytic distillation structure, also can use, also be called " catalytic distillation reactor assembly " at this.
Method disclosed herein comprises the reactor of any amount, comprises the catalytic distillation reactor assembly of upflowing and downflow system.Utilize catalytic distillation reactor assembly can preventing pollution thing and heavy catalyzer poison contact catalyst in course of conveying.In addition, clean phegma knows from experience lasting cleaning catalysis region.These factors combine the long-term effectiveness that can maintain catalyzer.Reaction heat makes liquid evaporation, the gas of evaporation in overhead condenser condensation to form more withdrawing fluid.Naturally temperature distribution defines the catalyst bed of an almost isothermal in fractional column, and the temperature of traditional fixed-bed reactor can raise.
On the one hand, the present invention relates to the preparation method about alkylbenzene, wherein comprise ethylbenzene and cumene.The alkylated reaction of benzene and certain alcohol can represent with following reaction.The alkylated reaction of benzene and other alcohols carries out in a similar manner, produces water and corresponding alkylide.
Benzene+methyl alcohol → toluene+water (I)
Benzene+ethanol → ethylbenzene+water (II)
Benzene+Virahol → cumene+water (III)
When needing, the alkylated reaction of toluene also can be realized by similarity method.
The preparation method of alkylbenzene is by C
1-C
8alcohol and benzene are transported in catalytic distillation system, and this system comprises one containing the high reaction zone of alkylation catalyst and one the low reaction district containing transalkylation catalyst (itself and alkylation catalyst identical or different).Such as, high reaction zone may be positioned at the rectification zone of distillation tower and low reaction district may be positioned at the stripping zone of distillation tower.
In catalytic distillation reactor assembly, have at least a part of benzene and alcohol upwards to distill in tower, benzene and alcohol produce alkylbenzene and water in alkylation catalyst surface reaction.Alcohol also id reaction may form alkyl oxide.In addition, alkylbenzene may proceed alkylated reaction and produce dialkyl benzene under alkylation catalyst effect, trialkyl benzene, or more much higher alkylbenzene.The alkylbenzene produced in high reaction zone and many alkyl products then may be downward through distillation tower, contact and alkylbenzene and polyalkylbenzene are reclaimed as end cut with transalkylation catalyst.Benzene in low reaction district can carry out transalkylation reaction with many alkyl products and produce more monoalkylated product.In addition, benzene may react under transalkylation catalyst effect with alcohol or alkyl oxide, the more monoalkylated product of same generation.
Above-mentioned reaction occurs simultaneously, feed composition and reaction product are (stepwise distillations) separately in catalytic distillation reactor assembly.Benzene, unreacted alcohol, water and alkyl oxide reclaim as overhead fraction in tower, and benzene, alkylbenzene and polyalkylbenzene reclaim as tower bottom distillate.
In order to meet benzene and alcohol reaches suitable reaction condition at the alkylated reaction of reaction zone, need to control the appointed condition of catalytic distillation.In certain embodiments, reaction zone temperature remains on 200 °F to 700 °F (93 DEG C to 371 DEG C); 200 °F to 400 °F in other embodiments (93 DEG C to 204 DEG C).
The raw materials components mole ratio of alcohol and benzene is from 0.1: 1 to 10: 1 in certain embodiments; In a further embodiment 0.8: 1 to 2: 1; From 0.9: 1 to 1.1: 1 in further embodiments.
Alcohols used in the embodiment disclosed herein comprises C
1to C
6firsts and seconds alcohol.Such as the embodiment disclosed herein comprises methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol and the trimethyl carbinol.
Any be used for catalysis benzene and alcohol carry out the catalyzer of alkylated reaction and/or transalkylation reaction can with in the method for the invention.Such as, molecular sieve or zeolitic catalyst just can be used for the alkylated reaction of catalysis benzene and/or transalkylation reaction.The molecular sieve used in the embodiment disclosed herein comprises the three-dimensional aluminosilicate of porous crystalline in Zeolite mineral system.Its crystalline structure is formed by surrounding four Sauerstoffatoms around each Siliciumatom and aluminium atom.This term of molecular sieve may be used for representing the zeolite of natural formation and the zeolite of synthetic.Its pore size of the zeolite of natural formation is irregular, does not usually think the zeolite being equal to synthetic.Also non-amorphous silicon dioxide and the aluminum oxide of synthetic can be used.
Synthetic zeolite is generally prepared in sodium form resin, and wherein the tight close sodium cation of each aluminium tetrahedron is with this balancing charge.At present, seven kinds of important molecular sieves have been had to be in the news, i.e. A, X, Y, L, erionite, omega zeolite and mordenite.Type A zeolite has relatively little effective pore radius (diameter).The comparatively large and Al in the aperture of X and y-type zeolite
2o
3and SiO
2ratio different, its Al of zeolite L
2o
3and SiO
2ratio higher.
In one group of embodiment, the catalyzer used in disclosed method contains a kind of zeolite and is sometimes also called mesopore or ZSM-5 type zeolite.In other embodiments, zeolite used can be a kind of mesopore shape selective acid metal hetero-atom molecular-sieve zeolite, comprise ZSM-5 from some, H-ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, choose in Y and the Beta zeolite of ZSM-50, MCM-22 and larger aperture.In one group of embodiment, the beta catalyzer of proton form is found to be a kind of special catalyst that effectively can promote benzene alkylation and transalkylation reaction.
The catalyzer that in the disclosed embodiments, other are used also comprises phosphorus-modified zeolite, aluminum oxide and silicon-dioxide.Such as, used in the disclosed embodiment a kind of special catalyst is AlPO
4.AlPO in another embodiment
4can load on alumina.
In order to promote fractionation and improve catalytic activity, catalyzer described above can be prepared into distillation structure form.Catalytic distillation structure must also have the function of mass transfer medium by existing catalyzer.Catalyzer must be suitably immobilized in a distillation column and separate, and just can play the effect of catalytic distillation structure.
In certain embodiments, catalyzer comprises a kind of structure, and this structure is disclosed by United States Patent (USP) 5730843, is merged into here in quoting.In other embodiments, one or more catalyzer described above may be present in the metallic mesh tube closed several one end, and pipe is laid on piece of metal web material as on silk screen applicator.Then sheet and pipe are rolled into a bundle to be fixed on distillation column reactor.This embodiment also has description in such as United States Patent (USP) 5431890, here with quote merging.Other catalytic distillation structures used have open in United States Patent (USP) 4302356,4443559,4731229,5073236,5431890,5266546 and 5730843, have been merged into all respectively in quoting.
As mentioned above, alcohol dewaters and forms alkyl oxide by product under the effect of alkylation catalyst.Alkyl oxide is a kind of alkylating reagent, can react form alkylbenzene under the effect of alkylation catalyst or transalkylation catalyst with benzene.The alkyl oxide reclaimed from overhead product can be recycled in tower and react with benzene.Like this, generation and the consumption of alkyl oxide reach balance, thus unclean surplus alkyl oxide produces.
With reference to figure 1, as shown be a simplification of flowsheet figure of the production alkylbenzene described according to the embodiment disclosed herein.Fresh alcohol raw material enters catalytic distillation reactor assembly 10 by pipeline 12.Fresh benzene enters catalytic distillation reactor assembly 10 by pipeline 14.In certain embodiments, benzene can be added by independent liquid stream (not marking in figure) in catalytic distillation reactor assembly 10, such as when the benzene separately added or the local benzene added flow contribute to tower work reach optimized time.Catalytic distillation reactor assembly 10 comprises one containing the high reaction zone 16 spreading alkylation catalyst, and a low reaction district 18 spreading transalkylation catalyst.
In high reaction zone 16, benzene and alcohol contact with alkylation catalyst and react and generates alkylbenzene, water and by product, as dialkyl benzene, trialkyl benzene and other polyalkylbenzene products, also have alcohol dewater under alkylation catalyst effect produce alkyl oxide.The rectification zone (on the intake zone of alcohol) of tower also can by alkylbenzene and polyalkylbenzene and unreacted benzene, and unreacted alcohol, water and alkyl oxide separately, and are reclaimed by pipeline 20 as overhead fraction from catalytic distillation reactor assembly 10.
In low reaction district 18, benzene and alkyl oxide and/or alcohol generation alkylated reaction.In addition, benzene can also react with polyalkylbenzene and form more monoalkylated product.The stripping zone (under alcohol intake zone) of tower also can be used for lighter composition (water, alcohol and alkyl oxide) to separate from alkylbenzene product.Unreacted benzene, alkylbenzene and polyalkylbenzene can be reclaimed as end cut from catalytic distillation reactor assembly 10 by pipeline 22.
In FIG, benzene flows downward in catalytic distillation reactor assembly 10.In this case, fresh benzene and the various liquid mixing circulated, as backflow raw material in catalytic distillation reactor assembly 10.In other embodiments, a part of tops can, as return line, be transmitted back in tower by pipeline 14, and fresh benzene is then introduced at lower opening for feed, in the middle of such as wherein possible Shi Gao reaction zone, position and low reaction district.
Fig. 1 also illustrates and alcohol is incorporated into catalytic distillation reactor assembly 10 in the middle of height reaction zone.In certain embodiments, may use two kinds or more of raw polyol, the opening for feed along tower limit adds raw polyol.Local determining alcohol can be prevented so too high, thus reduce dehydration reaction degree.Introduce fresh raw polyol in tower too with the multiple liquid mixing circulated, related embodiment is described below.
With reference to figure 2, as shown be the simplification of flowsheet figure preparing alkylbenzene described according to the embodiment disclosed herein, wherein each position numeral.Wherein general flowchart is identical with Fig. 1, and fresh benzene enters from pipeline 14 from tower top, mixes with Cycle Component, and fresh alcohol is added by pipeline 12 in the middle of height reaction zone, mixes with Cycle Component.
The end cut reclaimed from catalytic distillation reactor assembly 10 by pipeline 22 contains benzene, alkylbenzene and polyalkylbenzene, comprises dialkyl benzene, the alkylbenzene of trialkyl benzene and Geng Gao.Next end cut is transported in first knockout tower 24 to be separated from alkylbenzene and polyalkylbenzene by benzene.Isolated benzene is reclaimed by pipeline 26 from tower 24 as tops.Recovery benzene is circulated back in catalytic distillation reactor assembly 10 by pipeline 26 and again passes through reaction zone.
First alkylbenzene and polyalkylbenzene can be reclaimed from knockout tower 24 by pipeline 28 as end cut.Then alkylbenzene and polyalkylbenzene are transported in the second knockout tower 30 and are separated with polyalkylbenzene by alkylbenzene.As shown in Figure 2, alkylbenzene is reclaimed by pipeline 32 as tops from the second knockout tower 30, dialkyl benzene or dialkyl benzene and trialkyl benzene to be reclaimed by pipeline 34 as sideing stream from the second knockout tower 30, and heavier polyalkylbenzene is reclaimed by pipeline 36 as end cut from the second knockout tower 30.If necessary, side stream can be circulated back in catalytic distillation reactor assembly 10 to continue to react in the low reaction district of tower and benzene and produce more alkylbenzene.
From the tops that catalytic distillation reactor assembly reclaims, benzene, alcohol, alkyl oxide and water is contained by pipeline 20.Tops is then carried out condensation by the such as device such as indirect heat exchanger and settling drum 40 and is separated.In order to reach suitable liquid-liquid separation, condensation product must be cooled to 50 DEG C or lower.The upper liquid be separated is a kind of hydrocarbon liquids component, may containing benzene and some alkyl oxides and/or alcohol, and bottom is aqueous composition, may contain water, alcohol and alkyl oxide.Upper liquid component, mainly benzene, can be reclaimed by pipeline 42 from settling drum 40, and wherein a part can be recycled to Ta Nei and fresh benzene is mixed into withdrawing fluid, is a part ofly recycled in tower together with fresh alcohol raw material.So as shown in the figure, reflux line 44 contains fresh benzene, the benzene reclaimed from the first knockout tower 24 and the benzene reclaimed from settling drum 40.
Lower liquid component, comprises water, alcohol and alkyl oxide, can be reclaimed from settling drum 40 by pipeline 46 and be transported in the 3rd knockout tower 48 water and alcohol and alkyl oxide to be separated.Water can be reclaimed as end cut from the 3rd knockout tower 48 by pipeline 50, processes as required to it.Alcohol and alkyl oxide can be reclaimed to be looped back in catalytic distillation reactor assembly 10 by pipeline 54 from pipeline 52 again and continue reaction from the 3rd knockout tower 48.Therefore, as shown in the figure, containing fresh alcohol raw material in the transport pipe 56 of tower, from the benzene that settling drum 40 reclaims, the alcohol reclaimed from the 3rd knockout tower 48 and alkyl oxide and the polyalkylbenzene reclaimed from the second knockout tower 30.
In the 3rd knockout tower 48, carry out a point defection to water, alkyl oxide and alcohol make in tops containing water.Such as, when this three-part system forms a kind of azeotropic mixture, water can be reclaimed with by pipeline by tops.In order to controlled circulation is to the water yield of catalytic distillation reactor assembly 10, separation system as shown in Figure 3 be used.The aqueous composition reclaimed from settling drum 40 by pipeline 46 is transported in the 3rd knockout tower 48 to carry out above-mentioned separation.In the present embodiment, the tops reclaimed by pipeline 52 comprises water, alcohol and alkyl oxide.Tops then mixes with the liquid stream 58 containing benzene, such as part or all fresh benzene stream 14, part or all benzene reclaimed from the first knockout tower 24 by pipeline 26, or part or all upper liquid component reclaimed from settling drum 40 by pipeline 42, or the two kinds or more of mixing of these liquid streams or wherein part mix.Mixed liquid is then separated in settling drum 60, wherein hydrocarbon component, comprises benzene, alcohol and alkyl oxide, is reclaimed by pipeline 62, and aqueous composition is reclaimed by pipeline 64.This aqueous composition may comprise alcohol and alkyl oxide, and can be recycled in the 3rd knockout tower 48 continue be separated and the alcohol reclaimed wherein and alkyl oxide.
With reference to figure 4, as shown be the simplification of flowsheet figure preparing alkylbenzene described according to the embodiment disclosed herein, wherein each parts numeral.Benzene raw materials fresh in this embodiment and fresh raw polyol are introduced and carry out reacting/distilling in the middle of high and low reaction zone 16,18, as shown in Figure 1.The tops reclaimed from catalytic distillation reactor assembly 10 by pipeline 20 is by indirect heat exchanger 38 and settling drum 40 condensation and be separated, as mentioned above.Lower liquid phase component is reclaimed by pipeline 46 and is transported in knockout tower 48 separation carried out as shown in Figure 3.As shown in the figure, the tops being transported to settling drum 60 from the 3rd knockout tower 48 mixes with fresh benzene 14 with as the recycle benzene that tops is reclaimed from knockout tower 24 by pipeline 26.
The liquid phase component on part top is reclaimed by pipeline 42 and is transported in catalytic distillation reactor assembly 10 as withdrawing fluid by pipeline 70.Remaining upper aqueous phase component is with the hydrocarbon component reclaimed from settling drum 60 by pipeline 62 and merged by the fresh alcohol raw material that pipeline 12 is carried, and is introduced in tower by pipeline 56 as raw material.
The end cut reclaimed from catalytic distillation reactor assembly 10 by pipeline 22 also can carry out flow process described above, is recovered and recycled in tower by dialkyl benzene as sideing stream.Alkylbenzene is optionally reclaimed by pipeline 32 as tops, and polyalkylbenzene, comprises dialkyl benzene and trialkyl benzene can be reclaimed from the second knockout tower 30 by pipeline 72 as end cut.Polyalkylbenzene reacts subsequently, is separated, if or be applicable to production unit, can be used as fuel feedstocks.
With reference to figure 5, be a simple process figure of a production alkylbenzene according to the embodiment disclosed herein description as shown in the figure, wherein each parts numeral.The tops reclaimed from catalytic distillation reactor assembly 10 carries out the reaction of similar Fig. 4 description, wherein a part of upper liquid component 42 is used as reflux in tower 70, and fresh benzene 14 merges with the tops 52 reclaimed from the 3rd knockout tower 48 and carrys out controlled circulation to the water yield catalytic distillation reactor assembly 10.
In this embodiment, in order to ensure to be less than 0.03wt.% from the benzene content the end cut of pipeline 22 recovery, catalytic distillation reactor assembly 10 needs to remain in working order.End cut then can directly be transported in knockout tower 30, thus alkylbenzene is separated by pipeline 32 as tops, and polyalkylbenzene then reclaims as end cut 36.As Fig. 2 describes, if needed, side stream and can be reclaimed from tower 30 by pipeline 24, this sides stream containing dialkyl benzene and trialkyl benzene, can be recycled in catalytic distillation reactor assembly 10 and be used for producing more alkylbenzene.Wherein end cut contains the benzene of little concentration, the alkylbenzene containing purity at least 99.95wt.% in final alkylbenzene product liquid 32.
We also find to utilize described by complete distillation, alkylation and transalkylating system, the demand of equipment is reduced greatly.Such as, in order to the temperature reducing the tops reclaimed from catalytic distillation reactor assembly 10 can be passed through this tops and the end cut reclaimed from the 3rd separator 48 by pipeline 50, and carry out indirect heat exchange by the tops that pipeline 26 reclaims from the second separator 24.In addition, tops can be carried out indirect heat exchange with water/steam and be produced the higher water of temperature or low pressure or Central Asia steam, and use other parts of this technique, such as can be used for carrying out indirect heat exchange with the tops reclaimed from the 3rd separator 48 by pipeline 52 and making its condensation.Also first can be utilized from the lower liquid phase component that settling drum 40 reclaims by pipeline 46 and be transported to again the 3rd separator 48 after the 3rd separator 48 reclaims end cut heating by pipeline 50.Utilize the integrated advantage of the heat of this technique effectively can reduce or eliminate the demand for water coolant, and all heats that alkylated reaction heat release in technical process produces can be utilized.
As mentioned above, ethylbenzene and cumene is prepared by the distillation of catalytic distillation technology set of procedures, catalytic alkylation and the transalkylating system of catalysis in the embodiment disclosed herein.Relative to the traditional technology structure disclosure embodiment preparing alkylbenzene, there is following several respects advantage:
● reduce by the energy expenditure of 45% relative to the alkylation process based on traditional ethanol or now commercial ethene.The energy expenditure of the reboiler and condenser that are specially catalytic distillation reactor assembly can reduce to 50%, benzene recovery tower energy expenditure reduces to 50%, benzene recovery tower condenser energy expenditure reduces to 40%, and this system does not need transalkylating reaction feed well heater.
● decrease equipment unit quantity, be also reduced to 60% relative to its cost of alkylation process based on existing commercial ethene.Equipment unit in the technique that can eliminate is specially following: (1) reorganizer, (2) transalkylating reactor, (3) diethylbenzene/triethylbenzene distillation tower, (4) lighting end stripping tower, (5) vent absorber, (6) ethylene compressor, (7) all relevant utility appliance such as pump, reboiler, condenser, settling drum and the Controlling System relevant to (1) to (6).
● relative to existing commercial ethylene alkylation process system, power consumption can be reduced to 50%.Concrete, the quantity of pump can reduce by more than 50, and does not need compressor.
● cooling water amount can reduce to 100%, the generation low-pressure steam and water coolant can be used effectively.
● the size of upstream device can reduce
● catalyst utilization and cycle index improve compared to fixed-bed process, and the latter reduces due to coking and the poisoning utilization ratio that makes.In catalytic distillation reactor assembly, because in tower, liquid-flow catalyzer is cleaned always, in tower, hot spot can not be there is.Therefore, catalyst life and system works are stablized.
● operation cost can be reduced to 50% or more.Save operation cost and the use of cancelled items of equipment
In sum, method described here is that the alkylation of benzene provides a kind of new process program, and less energy, devices consume and lower cost can be utilized effectively to prepare highly purified alkylbenzene.
Although the scheme of the disclosure only includes the embodiment of limited quantity, in order to make those skilled in the art can differentiate that other are no more than the embodiment of disclosure aspects by disclosure scheme, this protection domain is subject to the restriction of following appended claims specification sheets.
Claims (29)
1. prepare a method for alkylbenzene, the method comprises:
By C
1to C
6alcohol and benzene are input in catalytic distillation reactor assembly, and this system comprises high reaction zone and the low reaction district containing transalkylation catalyst that contains alkylation catalyst, and wherein transalkylation catalyst and alkylation catalyst can be identical or different;
Carry out in catalytic distillation reactor assembly simultaneously:
Part alcohol and benzene generate mixture in the reaction of high reaction zone, wherein containing water, alkylbenzene, alkyl oxide, unreacted alcohol, unreacted benzene and the many alkylates comprising dialkyl benzene;
The many alkylates of a part and benzene react in low reaction district and form more alkylbenzene; And
Fractionation is carried out to reaction mixture;
Tops is reclaimed, comprising benzene, unreacted alcohol, water and alkyl oxide from catalytic distillation reactor assembly;
End cut is reclaimed, comprising benzene, alkylbenzene and polyalkylbenzene from catalytic distillation reactor assembly.
2. method according to claim 1, wherein alcohol is ethanol, and alkylbenzene is ethylbenzene.
3. method according to claim 1, wherein alcohol is Virahol, and alkylbenzene is cumene.
4. method according to claim 1, comprises further:
Control catalytic distillation reactor assembly end cut to be contained be less than 0.03wt.% benzene; And
End cut fractionation is reclaimed the tops containing alkylbenzene and benzene and the end cut containing many alkyl products.
5. method according to claim 4, wherein tops comprises the ethylbenzene containing at least 99.95wt.% alkylbenzene.
6. a preparation method for ethylbenzene, the method comprises:
Ethanol and benzene are input in catalytic distillation reactor assembly, this system comprises one containing the high reaction zone of alkylation catalyst and a low reaction district containing transalkylation catalyst, described transalkylation catalyst and described alkylation catalyst identical or different;
Carry out in this catalytic distillation reactor assembly simultaneously:
Part alcohol and benzene generate mixture in the reaction of high reaction zone, wherein containing water, ethylbenzene, ether, unreacted ethanol, unreacted benzene and the many alkylates comprising diethylbenzene;
The many alkylates of a part and benzene react in low reaction district and form more ethylbenzene; And
Fractionation is carried out to reaction mixture;
Tops is reclaimed, comprising benzene, ethanol, water and ether from catalytic distillation reactor assembly;
End cut is reclaimed, comprising benzene, ethylbenzene and many alkylates from catalytic distillation reactor assembly;
By tops condensation and be separated the first liquid phase component formed containing benzene and the second liquid phase component containing water, ethanol and ether;
The end cut of the distillation reactor of autocatalysis in the future system is separated in the first distillation tower, reclaims the tops containing benzene and contains the end cut of ethylbenzene and many alkylates;
Conveying at least partially in the first liquid phase component to catalytic distillation reactor assembly as backflow;
In second column, be separated second liquid phase component, reclaim the tops containing ethanol and ether and the end cut containing water;
Conveying raw polyol and at least partially from second column reclaim tops in the middle of the high and low reaction zone of catalytic distillation reactor assembly.
7. method according to claim 6, comprises in the middle of conveying a part of first liquid phase component to the high and low reaction zone of catalytic distillation reactor assembly further.
8. method according to claim 6, is included in by the end fraction seperation of the first distillation tower in the 3rd distillation tower further, reclaims the overhead fraction containing ethylbenzene and the end cut containing many alkylates.
9. method according to claim 6, comprises the end fraction seperation from the first distillation tower further, reclaims the tops containing ethylbenzene, sideing stream and containing the end cut of many alkylates containing diethylbenzene.
10. method according to claim 9, comprises conveying further and sides stream at least partially in the middle of the high and low reaction zone of catalytic distillation reactor assembly.
11. methods according to claim 10, wherein side stream and comprise triethylbenzene further.
12. methods according to claim 9, comprise further and utilize the end cut containing many alkylates as fuel feedstocks.
13. methods according to claim 6, wherein the condensation and being separated of the tops tops that comprises the distillation reactor of autocatalysis in the future system carries out indirect heat exchange by a kind of mode at least below:
End cut moisture at least partially,
At least partially from the tops of second column;
Water; With
Steam.
14. methods according to claim 6, wherein the catalyzer of high reaction zone is identical with the catalyzer in low reaction district.
15. methods according to claim 6, comprise conveying benzene raw material further, at least partially the first liquid phase component and at least partially from the tops of the first distillation tower in catalytic distillation reactor assembly as backflow.
16. methods according to claim 6, comprise further:
By benzene and at least partially from second column tops merge to form mixture;
This mixture is separated reclaim the 3rd liquid phase component, comprising benzene, ethanol and ether and a kind of 4th liquid phase component, wherein containing water, ethanol and diethyl ether;
4th liquid phase component is recycled in second column; And
Carry in the middle of the 3rd liquid phase component and a part of first liquid phase component to the high and low reaction zone of catalytic distillation reactor assembly.
17. methods according to claim 16, comprise merging at least partially from the tops in the tops in the first distillation tower, benzene, at least partially second column to form mixture.
The preparation method of 18. 1 kinds of cumenes, the method comprises:
Virahol and benzene are input in catalytic distillation reactor assembly, this system comprises one containing the high reaction zone of alkylation catalyst and a low reaction district containing transalkylation catalyst, described transalkylation catalyst and described alkylation catalyst identical or different;
Carry out in this catalytic distillation reactor assembly simultaneously:
Part Virahol and benzene generate mixture in the reaction of high reaction zone, wherein containing water, cumene, isopropyl ether, unreacted Virahol, unreacted benzene and the many alkylates comprising diisopropylbenzene(DIPB);
The many alkylates of a part and benzene react in low reaction district and form more cumene; And
Fractionation is carried out to reaction mixture;
Tops is reclaimed, comprising benzene, Virahol, water and isopropyl ether from catalytic distillation reactor assembly;
End cut is reclaimed, comprising benzene, cumene and many alkylates from catalytic distillation reactor assembly; By tops condensation and be separated the first liquid phase component formed containing benzene and the second liquid phase component containing water, Virahol and isopropyl ether;
End cut in the distillation reactor of autocatalysis in the future system is separated the tops reclaimed containing benzene and the end cut containing cumene and many alkylates in the first distillation tower;
Conveying at least partially in the first liquid phase component to catalytic distillation reactor assembly as backflow;
In second column, be separated second liquid phase component, reclaim the tops containing Virahol and isopropyl ether and the end cut containing water;
Virahol raw material is carried and at least partially in the middle of tops to the high and low reaction zone of catalytic distillation reactor assembly from second column.
19. methods according to claim 18, comprise in the middle of conveying a part of first liquid phase component to the high and low reaction zone of catalytic distillation reactor assembly further.
20. methods according to claim 18, are included in by the end fraction seperation from the first distillation tower in the 3rd distillation tower further, reclaim the overhead fraction containing cumene and the end cut containing many alkylates.
21. methods according to claim 18, comprise the end fraction seperation from the first distillation tower further, reclaim the tops containing cumene, sideing stream and containing the end cut of many alkylates containing diisopropyl benzene.
22. methods according to claim 21, comprise conveying further and side stream at least partially in the middle of the high and low reaction zone of catalytic distillation reactor assembly.
23. methods according to claim 22, wherein side stream and comprise triisopropylbenzene further.
24. methods according to claim 21, comprise further and utilize the end cut containing many alkylates as fuel feedstocks.
25. methods according to claim 18, wherein the condensation and being separated of the tops tops that comprises the distillation reactor of autocatalysis in the future system carries out indirect heat exchange by a kind of mode at least below:
End cut moisture at least partially,
At least partially from the tops of second column;
Water; With
Steam.
26. methods according to claim 18, wherein the catalyzer of high reaction zone is identical with the catalyzer in low reaction district.
27. methods according to claim 18, comprise conveying benzene raw material further, at least partially the first liquid phase component and at least partially from the tops of the first distillation tower in catalytic distillation reactor assembly as backflow.
28. methods according to claim 18, comprise further:
By benzene and at least partially from second column tops merge to form mixture;
This mixture is separated reclaim the 3rd liquid phase component, comprising benzene, Virahol and diisopropyl ether and a kind of 4th liquid phase component, wherein containing water, ethanol and diisopropyl ether;
4th liquid phase component is recycled in second column; And
Carry in the middle of the 3rd liquid phase component and a part of first liquid phase component to the high and low reaction zone of catalytic distillation reactor assembly.
29. methods according to claim 28, comprise merging at least partially from the tops of the first distillation tower, benzene, at least partially from the tops of second column to form mixture.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39406110P | 2010-10-18 | 2010-10-18 | |
| US61/394,061 | 2010-10-18 | ||
| PCT/US2011/055728 WO2012054260A2 (en) | 2010-10-18 | 2011-10-11 | Benzene alkylation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103201238A CN103201238A (en) | 2013-07-10 |
| CN103201238B true CN103201238B (en) | 2015-03-25 |
Family
ID=45975804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180050138.7A Active CN103201238B (en) | 2010-10-18 | 2011-10-11 | Benzene alkylation |
Country Status (5)
| Country | Link |
|---|---|
| KR (1) | KR101530457B1 (en) |
| CN (1) | CN103201238B (en) |
| MY (1) | MY162925A (en) |
| SG (1) | SG189418A1 (en) |
| WO (1) | WO2012054260A2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111589406B (en) * | 2019-02-21 | 2022-04-12 | 中国石油化工股份有限公司 | Alkylation reaction device, reaction system and liquid acid catalyzed alkylation reaction method |
| CN113384910B (en) * | 2021-07-19 | 2022-04-22 | 南京工程学院 | Multi-effect cumene reaction rectification device and method combined with heat pump |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103444A (en) * | 1987-04-29 | 1988-11-30 | 环球油品公司 | Composite catalyst for paraffin isomerization |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4735929A (en) * | 1985-09-03 | 1988-04-05 | Uop Inc. | Catalytic composition for the isomerization of paraffinic hydrocarbons |
| US4774377A (en) * | 1987-09-11 | 1988-09-27 | Uop Inc. | Alkylation/transalkylation process |
| WO2002062734A1 (en) * | 2001-02-07 | 2002-08-15 | Exxonmobil Chemical Patents Inc. | Production of alkylaromatic compounds |
| US7910785B2 (en) * | 2006-07-28 | 2011-03-22 | Exxonmobil Chemical Patents Inc. | Hydrocarbon conversion process using EMM-10 family molecular sieve |
| US8143466B2 (en) * | 2008-02-26 | 2012-03-27 | Catalytic Distillation Technologies | Process for benzene removal from gasoline |
| US7745674B2 (en) * | 2008-08-20 | 2010-06-29 | Catalytic Distillation Technologies | Alkylation slurry reactor |
-
2011
- 2011-10-11 SG SG2013028311A patent/SG189418A1/en unknown
- 2011-10-11 MY MYPI2013001326A patent/MY162925A/en unknown
- 2011-10-11 CN CN201180050138.7A patent/CN103201238B/en active Active
- 2011-10-11 KR KR1020137011722A patent/KR101530457B1/en active IP Right Grant
- 2011-10-11 WO PCT/US2011/055728 patent/WO2012054260A2/en active Application Filing
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103444A (en) * | 1987-04-29 | 1988-11-30 | 环球油品公司 | Composite catalyst for paraffin isomerization |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012054260A8 (en) | 2013-05-30 |
| CN103201238A (en) | 2013-07-10 |
| MY162925A (en) | 2017-07-31 |
| WO2012054260A3 (en) | 2012-07-26 |
| WO2012054260A2 (en) | 2012-04-26 |
| KR20130097217A (en) | 2013-09-02 |
| KR101530457B1 (en) | 2015-06-19 |
| SG189418A1 (en) | 2013-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102372585B (en) | The bed process of alkylating aromatic hydrocarbon p-Xylol | |
| CN85109128A (en) | Integrated fractionation in recovery of alkylaramatic hydrocarbons | |
| CA2516648C (en) | Process for the production of alkylbenzene | |
| KR101837521B1 (en) | Process for producing cumene | |
| US7488861B2 (en) | Process for the co-production of cumene and secondary butyl benzene | |
| US5177283A (en) | Hydrocarbon conversion process | |
| CN101213158A (en) | Alkylation process using UZM-8 zeolite | |
| CN109963828A (en) | The methylation method of aromatic hydrocarbon | |
| CN101417915A (en) | Integrated production of fcc-produced c3 and cumene | |
| CN101952397B (en) | Process for benzene removal from gasoline | |
| CN103201238B (en) | Benzene alkylation | |
| RU2515979C2 (en) | Method of obtaining alkyl-aromatic compounds | |
| CN1247493C (en) | Aromatic hydrocarbon conversion method | |
| CN104557425A (en) | Catalyst distillation method for producing paraxylene through aryl alkylation | |
| TW200906767A (en) | Process for producing cumene | |
| US7745674B2 (en) | Alkylation slurry reactor | |
| CN104557426A (en) | Aromatic hydrocarbon alkylation slurry bed reaction method | |
| RU2717775C1 (en) | Method of alkylating aromatic hydrocarbons with olefins and a reaction-rectification system for its implementation | |
| TWI586635B (en) | Process for the production of xylenes | |
| US3879487A (en) | Hydrogen fluoride alkylation utilizing a heat exchanger in the settling zone | |
| US5847253A (en) | Alkylation-transalkylation process using stripping to produce a dry transalkylation feed | |
| EP1123261A1 (en) | Alkylation of benzene to form linear alkylbenzenes using fluorine-containing mordenites | |
| CN105523876B (en) | A kind of method by preparing propylene from methanol | |
| CN100404486C (en) | Preparation method of alkylbenzene | |
| CN101550050B (en) | Method and device for alkylating aromatic compounds by olefin by utilizing impure aromatic compound circulation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |