CN1217310A - Process for producing alkylbenzene - Google Patents
Process for producing alkylbenzene Download PDFInfo
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- CN1217310A CN1217310A CN 97106708 CN97106708A CN1217310A CN 1217310 A CN1217310 A CN 1217310A CN 97106708 CN97106708 CN 97106708 CN 97106708 A CN97106708 A CN 97106708A CN 1217310 A CN1217310 A CN 1217310A
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- benzene
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- alkylation reactor
- alkylbenzene
- alkylation
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Abstract
The production process of alkylbenzene is characterized by that in the presence of alkylation catalyst the raw material benzene is fed into alkylation reactor at least having two stages, and at least the raw material benzene fed into first stage of alkylation reactor is reacted with raw material olefine fed into every stage of alkylation reactor to form alkylbenzene. Adopting external circulation mode a part of the reactant liquor is returned into the alkylation reactor, and every stage of the alkylation reactor adopts intermediate heat-exchanger staged heating technique. Said invented process has the advantages of low reaction system operation pressure, low benzene-hydrocarbon ratio and high reaction heat utilization rate, etc.,and can be used in industrial production.
Description
The present invention relates to the production technique of alkylbenzene, the alkylbenzene production technique of particularly outer circulation mode.
Ethylbenzene in the alkylbenzene, isopropyl benzene are important Organic Chemicals, and wherein isopropyl benzene also is an important intermediate raw material of producing phenol, acetone and alpha-methyl styrene.Phenol more than 90% is to adopt cumene method production in the world at present, and this method is when producing phenol, also in the another kind of important organic raw material acetone of 1: 0.6 ratio coproduction.
Industrial traditional method with propylene and benzene production isopropyl benzene has solid phosphoric acid gas phase alkylation methods (SPA method) and improved AlCl
3The liquid phase alkylation methods, and based on solid phosphoric acid gas phase alkylation methods.With AlCl
3Method is compared, and the SPA method has low pollution, weak corrosive advantage, but part is not to the utmost also arranged, and promptly operational condition is comparatively harsh, and impurity is many, can not improve the productive rate of isopropyl benzene by reverse alkylation.And AlCl
3Though method has than the demulcent reaction conditions, and can improve the productive rate of isopropyl benzene by reverse alkylation, deep-etching, high pollution and numerous and diverse aftertreatment are its shortcomings that is difficult to overcome.
Molecular sieve liquid phase alkylation methods is because reaction conditions mitigation, transformation efficiency height, selectivity is good, impurity is few, pollution-free, no burn into by-product polyisopropylbenzene (diisopropylbenzene(DIPB), tri-isopropyl benzene) can change isopropyl benzene into by reverse alkylation; make the isopropyl benzene productive rate up to more than 99%; be each institute of big industrial group company common concern of the world in recent years, an and cleaner technology of development research competitively, this technology technical indicator advanced person, significant to environment protection.Particularly near, over 2 years, molecular sieve liquid phase hydrocarbonylation technology the anti-carbon performance of catalyzer and stable aspect obtained break through after, this technology has realized industrialization soon in the transformation of new device and old device.Compare with traditional technology, showed very strong competitive capacity.
Often be used at present the technical process of producing isopropyl benzene and be raw material propylene and new recycle benzene of replenishing before sending into reactor earlier by interchanger with deep fat or steam preheating, the material that reactor comes out enters two sections flash distillation plants, the major part of recycle benzene is all separated from this flash distillation plant, enters the depropanizing distilling period.Then rich isopropyl benzene steam enters the benzene tower, isolates residual recycle benzene at this.Use the clay treatment isopropyl benzene then.Remove a small amount of heavies that generates by side reaction in the removal of alkylation reaction in the final carclazyte contact treating distillation.The still liquid that comes out from this final distiller is higher aromatics, mainly is diisopropylbenzene(DIPB) (DIPB).DIPB reacts in the transalkylation workshop section of device again and generates isopropyl benzene.The inventor thinks that this technology mainly exists reactive system working pressure height, the problem that the heat of reaction utilization ratio is low.Introduced a kind of production benzene process in the document WO 89/10910, the flow process of this technology mainly is made of alkylation reactor, transalkylation reactor, benzene recovery tower, isopropyl benzene treating tower, five parts of polyisopropylbenzene recovery tower as shown in Figure 1.Wherein alkylation reactor is an adiabatic reactor reactor that beds is divided at least two conversion zones, all be mounted with alkylation catalyst in each conversion zone, benzene is fed at least behind first section reactor with fresh raw material olefin reaction and generates alkylbenzene.The inventor thinks that this technology exists reactive system working pressure height, the shortcoming that the reaction energy utilization ratio is low equally.
For overcoming the deficiency that above-mentioned document exists, the purpose of this invention is to provide a kind of alkylbenzene new process of production, it is low that this technology has a reactive system working pressure, and benzene hydrocarbon is than low, the advantage that the heat of reaction utilization ratio is high.
The objective of the invention is to realize: a kind of production technique of alkylbenzene by following technical scheme, in the presence of alkylation catalyst, benzene feedstock enters and contains two sections alkylation reactor at least, each section of alkylation reactor all is mounted with alkylation catalyst, at least the benzene feedstock that enters first section of alkylation reactor generates alkylbenzene with the raw material olefin reaction that enters each section of alkylation reactor, wherein the discharging part of alkylation reactor is back into alkylation reactor with external circulation mode, and each section of alkylation reactor adopts intermediate heat segmentation heat-obtaining.
Alkylation reactor is the adiabatic reactor reactor in the technique scheme, and benzene feedstock can be recovery benzene or its mixture of fresh benzene, follow-up workshop section.Benzene feedstock can be separately or with the bottom that enters first section bed of alkylation reactor after raw material olefin mixes, also can divide several parts to enter the bottom of each section bed in the alkylation reactor respectively.Raw material olefin is C
2～C
6Alkene, its preferred version is C
2～C
3Alkene.Raw material olefin can be recovery alkene or its mixture of fresh alkene, follow-up workshop section.The discharging of alkylation reactor can divide several parts of each conversion zone bottoms that are back into alkylation reactor respectively with external circulation mode, but at least must beyond Recycle design be back into first section reaction bed of alkylation reactor, the outer circulation ratio is 0.5～4.It is three sections that the conversion zone bed of alkylation reactor is counted preferred version.
The temperature of reaction of alkylation reactor is 130～300 ℃, and its preferable range is 150～270 ℃, is 230～270 ℃ to generating the ethylbenzene temperature of reaction; To generating the isopropyl benzene temperature of reaction is 180～210 ℃; To generating the hexyl benzene temperature of reaction is 150～200 ℃.The reaction pressure of alkylation reactor is 1.5～4.0MPa, its preferable range is 1.8～3.5MPa, reaction pressure to generation ethylbenzene is 3.0～3.8MPa, is 2.0～3.0MPa to the reaction pressure that generates isopropyl benzene, is 1.5～2.5MPa to the reaction pressure that generates hexyl benzene.
Because the present invention adopts external circulation process, can not only effectively reduce the hop count of reaction bed, and the outer circulation material diluted the concentration of material propylene, the working pressure of reactive system is minimized, reduced power consumption simultaneously, reduced the thermal insulation warming of bed.In addition, also strengthened heat transfer, reduced the heat transfer area of interchanger, when normal operation, by the segmentation heat-obtaining, the net effect of outer circulation and flash distillation makes reaction heat all be used as the distillation thermal source of raw material preheating and recovery benzene, improve the utilising efficiency of reaction heat, reduced the benzene hydrocarbon ratio simultaneously.General outer circulation can be saved steam more than 15% than the technology that does not adopt outer circulation, has obtained good effect.
Accompanying drawing 1 is the technical process of producing alkylbenzene in the document WO 89/10911.
Accompanying drawing 2 is technical process that the present invention produces alkylbenzene.
1 is alkylation reactor, 2 is transalkylation reactor, 3 is the transalkylation reactor top discharge, 4 is the benzene recovery tower, 5 is the alkylbenzene treating tower, and 6 is the polyalkylbenzene recovery tower, and 7 eject material for the benzene recovery tower, 8 eject material for the alkylbenzene treating tower, 9 for the polyalkylbenzene recovery tower ejects material, and 10 is the discharging of polyalkylbenzene recovery tower still, and 11 is fresh feed benzene, 12,13,14 is raw material olefin, and 15 is the alkylation reactor top discharge, 16 is the alkylation reactor bottom feed, and 17 is alkylation reactor top outer circulation material.
The raw material olefin of benzene feedstock, first conversion zone and mix from the recovery benzene of benzene recovery tower 4, behind heat exchanger with first, After the two conversion zone outlet material heat exchange, be preheating to certain temperature through heat exchanger by transalkylation reactor 2 outlet materials again, Enter first conversion zone of alkylation reactor 1 with the recycle stock from alkylation reactor 1 outlet. Alkene is in mistake Under the existence of amount benzene, complete reaction generates alkylbenzene and a small amount of polyalkylbenzene.
One section product is removed partial reaction heat through the external refrigeration heat exchanger, and controls certain temperature and second conversion zone Raw material olefin is mixed into second conversion zone of alkylation reactor 1, alkene equally in the presence of excessive benzene, complete reaction Generate alkylbenzene and a certain amount of polyalkylbenzene.
The second-stage reaction product is removed partial reaction heat through the external refrigeration heat exchanger, and controls certain temperature and the 3rd conversion zone Raw material olefin is mixed into the 3rd conversion zone of alkylation reactor 1, finishes same reaction, and hop count, the material of back are walked To the same front of situation.
The product that goes out to suck alkylbenzene, polyalkylbenzene and excessive benzene of alkylation reactor 1, a part is pressed through circulating pump Certain recycle ratio is returned into first conversion zone in the mode of " outer circulation ". Another part with from polyalkylbenzene recovery tower 6 Polyalkylbenzene mix after, directly send into the transalkylation reactor 2 that molecular sieve catalyst is housed, in the presence of excessive benzene, Most of polyalkylbenzene is converted into alkylbenzene.
Two strands of vapour, liquid phase stream from flash tank are directly sent into benzene recovery tower 4, discharge the non-condensable gasess of being brought into by raw material olefin such as alkane from return tank of top of the tower, and rectifying section side line liquid phase is extracted out and reclaimed benzene, for recycling.
The thick alkylbenzene that benzene recovery tower 4 tower stills do not contain benzene directly is sent to alkylbenzene decompression treating tower 5, steams the finished product alkylbenzene from cat head.Alkylbenzene treating tower 5 tower stills contain the polyalkylbenzene of a small amount of heavy component, directly be sent to polyalkylbenzene reclaim under reduced pressure tower 6, reclaim polyalkylbenzene and remove heavy component, steam polyalkylbenzene from cat head, foldback transalkylation reactor 2, the heavy component that the tower still is discharged can be made fuel and use.
The invention will be further elaborated below by embodiment: [embodiment 1]
Press the reaction process of accompanying drawing 2, benzene and propylene reaction generate isopropyl benzene, adopt syllogic adiabatic reactor reactor, catalyst system therefor is a molecular sieve catalyst, isopropyl benzene content 21% in the reaction solution, the outer circulation ratio is 1, every section is reacted 30 ℃ of thermal insulation warmings, 180 ℃ of reactor inlet temperatures, 210 ℃ of temperature outs, reaction preference: propyl group selectivity 〉=99%, n-proplbenzene≤350ppm in the isopropyl benzene, reaction pressure: 2.6～3.0MPa, steam consumption quantity are 0.37 ton of/ton isopropyl benzene.[embodiment 2]
Press the reaction process of accompanying drawing 2, benzene and propylene reaction generate isopropyl benzene, adopt syllogic adiabatic reactor reactor, catalyst system therefor is a molecular sieve catalyst, isopropyl benzene content 23% in the reaction solution, the outer circulation ratio is 3,12 ℃ of reaction thermal insulation warmings, 180 ℃ of reactor inlet temperatures, 192 ℃ of temperature outs, reaction preference: propyl group selectivity 〉=99.0%, n-proplbenzene≤250ppm in the isopropyl benzene, reaction pressure: 2.3～2.6MPa, steam consumption quantity are 0.32 ton of/ton isopropyl benzene.[embodiment 3]
Press the reaction process of accompanying drawing 2, benzene and ethylene reaction generate ethylbenzene, adopt syllogic adiabatic reactor reactor, catalyst system therefor is a molecular sieve catalyst, ethyl-benzene level 20% in the reaction solution, and the outer circulation ratio is 2,17 ℃ of reaction thermal insulation warmings, 233 ℃ of reactor inlet temperatures, 250 ℃ of temperature outs, reaction preference: ethyl selectivity 〉=99%, dimethylbenzene≤50ppm in the ethylbenzene, reaction pressure: 3.2～3.5MPa, steam consumption quantity are 0.30 ton of/ton ethylbenzene.[embodiment 4]
Press the reaction process of accompanying drawing 2, benzene and hexene reaction generate hexyl benzene, adopt two-section type adiabatic reactor reactor, and catalyst system therefor is a molecular sieve catalyst, hexyl benzene content 16% in the reaction solution, the outer circulation ratio is 1,26 ℃ of reaction thermal insulation warmings, 160 ℃ of reactor inlet temperatures, 186 ℃ of temperature outs, reaction preference: hexyl selectivity 〉=99%, reaction pressure: 1.7～2.0MPa, steam consumption quantity are 0.44 ton of/ton hexyl benzene.[comparative example 1]
Press the reaction process of accompanying drawing 1, benzene and propylene reaction generate isopropyl benzene, adopt four-part form adiabatic reactor reactor, and catalyst system therefor is a molecular sieve catalyst, isopropyl benzene content 14% in the reaction solution, 30 ℃ of reaction thermal insulation warmings, 180 ℃ of reactor inlet temperatures, 210 ℃ of temperature outs, reaction preference: propyl group selectivity 〉=99%, n-proplbenzene≤350ppm in the isopropyl benzene, reaction pressure: 2.9～3.3MPa, steam consumption quantity are 0.44 ton of/ton isopropyl benzene.[comparative example 2]
Press the reaction process of accompanying drawing 1, benzene and ethylene reaction generate ethylbenzene, adopt four-part form adiabatic reactor reactor, and catalyst system therefor is a molecular sieve catalyst, ethyl-benzene level 13% in the reaction solution, 23 ℃ of reaction thermal insulation warmings, 230 ℃ of reactor inlet temperatures, 253 ℃ of temperature outs, reaction preference: ethyl selectivity 〉=99%, dimethylbenzene≤50ppm in the ethylbenzene, reaction pressure: 4.0～4.5MPa, steam consumption quantity are 0.35 ton of/ton ethylbenzene.[comparative example 3]
Press the reaction process of accompanying drawing 1, benzene and hexene reaction generate hexyl benzene, adopt four-part form adiabatic reactor reactor, catalyst system therefor is a molecular sieve catalyst, hexyl benzene content 16% in the reaction solution, 26 ℃ of reaction thermal insulation warmings, 160 ℃ of reactor inlet temperatures, 186 ℃ of temperature outs, reaction preference: hexyl selectivity 〉=99%, reaction pressure: 1.7～2.0MPa, steam consumption quantity are 0.51 ton of/ton hexyl benzene.
Claims (8)
1, a kind of dirt production art of alkylbenzene, in the presence of alkylation catalyst, benzene feedstock enters and contains two sections alkylation reactor at least, each section of alkylation reactor all is mounted with alkylation catalyst, at least the benzene feedstock that enters first section of alkylation reactor generates alkylbenzene with the raw material olefin reaction that enters each section of alkylation reactor, a discharging part that it is characterized in that alkylation reactor is back into alkylation reactor with external circulation mode, and each section of alkylation reactor adopts intermediate heat segmentation heat-obtaining.
2,, it is characterized in that alkylation reactor is the adiabatic reactor reactor according to the production technique of the described alkylbenzene of claim 1.
3,, it is characterized in that benzene feedstock is recovery benzene or its mixture of fresh benzene, follow-up workshop section according to the production technique of the described alkylbenzene of claim 1.
4,, it is characterized in that raw material olefin is C according to the production technique of the described alkylbenzene of claim 1
2～C
6Alkene.
5,, it is characterized in that raw material olefin is C according to the production technique of the described alkylbenzene of claim 4
2～C
3Alkene.
6,, it is characterized in that raw material olefin is recovery alkene or its mixture of fresh alkene, follow-up workshop section according to the production technique of the described alkylbenzene of claim 1.
7, according to the production technique of the described alkylbenzene of claim 1, a discharging part that it is characterized in that alkylation reactor is back into first section bed of alkylation reactor at least with external circulation mode, and the outer circulation ratio is 0.5～4.
8,, it is characterized in that alkylation reactor is divided into three sections adiabatic beds according to the production technique of the described alkylbenzene of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106708A CN1055912C (en) | 1997-11-13 | 1997-11-13 | Process for producing alkylbenzene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106708A CN1055912C (en) | 1997-11-13 | 1997-11-13 | Process for producing alkylbenzene |
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| Publication Number | Publication Date |
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| CN1217310A true CN1217310A (en) | 1999-05-26 |
| CN1055912C CN1055912C (en) | 2000-08-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106708A Expired - Lifetime CN1055912C (en) | 1997-11-13 | 1997-11-13 | Process for producing alkylbenzene |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278794A (en) * | 2015-06-04 | 2017-01-04 | 常州瑞华化工工程技术有限公司 | The common liquid-phase alkylation of ethylene, propylene produces ethylbenzene and the method and apparatus of isopropylbenzene |
| CN115838315A (en) * | 2022-12-23 | 2023-03-24 | 常州瑞华化工工程技术股份有限公司 | Process for producing tert-butyl ethylbenzene by low aromatic-to-olefin ratio and tert-butyl ethylbenzene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102442877A (en) * | 2010-10-12 | 2012-05-09 | 中国石油化工股份有限公司 | Method for separating propane from isopropylbenzene production facility |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4046516A (en) * | 1975-12-29 | 1977-09-06 | Uop Inc. | Hydrogen fluoride-catalyzed alkylation apparatus |
| EP0424393B1 (en) * | 1988-05-09 | 1995-08-09 | Abb Lummus Global Inc. | Manufacture of alkylbenzenes |
| US5185485A (en) * | 1991-06-28 | 1993-02-09 | Monsanto Company | Process for preparing alkylbenzene |
-
1997
- 1997-11-13 CN CN97106708A patent/CN1055912C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106278794A (en) * | 2015-06-04 | 2017-01-04 | 常州瑞华化工工程技术有限公司 | The common liquid-phase alkylation of ethylene, propylene produces ethylbenzene and the method and apparatus of isopropylbenzene |
| CN115838315A (en) * | 2022-12-23 | 2023-03-24 | 常州瑞华化工工程技术股份有限公司 | Process for producing tert-butyl ethylbenzene by low aromatic-to-olefin ratio and tert-butyl ethylbenzene |
| CN115838315B (en) * | 2022-12-23 | 2023-11-17 | 常州瑞华化工工程技术股份有限公司 | Process for producing tert-butylethylbenzene by low aromatic alkene ratio and tert-butylethylbenzene |
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| CN1055912C (en) | 2000-08-30 |
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Granted publication date: 20000830 |