CN1045284C - Liquid phase alkylation process of benzene - Google Patents
Liquid phase alkylation process of benzene Download PDFInfo
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- CN1045284C CN1045284C CN95101006A CN95101006A CN1045284C CN 1045284 C CN1045284 C CN 1045284C CN 95101006 A CN95101006 A CN 95101006A CN 95101006 A CN95101006 A CN 95101006A CN 1045284 C CN1045284 C CN 1045284C
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Abstract
The present invention discloses a liquid phase alkylation process of benzene in the presence of a zeolite catalyst. In a one-stage cyclic reactor, a mixture of fresh benzene, recovered benzene, fresh alkene and partial effluent after the alkylation reaction is used as a reaction raw material, and the reaction is carried out under the condition that the molar ratio of the benzene to the alkene is from 1.5 to 8, and the weight ratio of cyclic materials to reactor effluent is from 1.5 to 12. The technology preferably adopts the catalyst which comprises the following components: 30 to 70 wt% of H beta zeolite whose silica alumina ratio is from 20 to 40, 0.5 to 10 wt% of fluorine or chlorine and balance of gamma-Al2O3. The process is especially suitable for preparing ethylbenzene and cumene.
Description
The invention relates to the processing method of in the presence of alkylation catalyst, producing alkylbenzene by the liquid phase reaction of benzene and alkene.The present invention is particularly about producing the alkylation process of ethylbenzene or isopropyl benzene by the liquid phase reaction of benzene and ethene or propylene in first stage reactor in the presence of zeolite catalyst.
Produce the processing method of alkylbenzene two classes are arranged containing alkene and benzene reaction in the presence of the alkylation catalyst of zeolite: the liquid phase method of the employing macropore super stable molecular sieve catalyzer of the vapor phase process of the employing mesopore ZSM-5 zeolite catalyst of Mobil/Badger company exploitation and the exploitation of Lummus/Unocal company.This two classes technology respectively has its relative merits, and state of the art is close: the former charging air speed height, and required reactor size is little, but the temperature of reaction height, benzene feedstock needs gas propose dehydration, xylene content height in the product when producing ethylbenzene; The latter then temperature of reaction is low, and benzene feedstock need not dewatered, when producing ethylbenzene in the product xylene content low, but the charging air speed is low, required reactor size is big.This two classes technology is all constantly improved in the process of industrial implementation at present.
The typical process flow of liquid phase method is: raw material olefin and benzene enter the multistage alkylation reactor that zeolite catalyst is housed, reacted effluent separates and reclaims, and obtains purpose product monoalkylated benzenes and reaction remaining excessive benzene in back and by product polyalkylbenzene.The excessive benzene that reclaims or be sent to transalkylation reactor or be recycled to the alkylation reaction device and go to change into alkylbenzene with olefine reaction, the by product polyalkylbenzene then can enter transalkylation reactor and remove to be converted into monoalkylated benzenes.
Lummus company is at USP5, described such liquid-phase alkylation process in detail in 003,119: at least two sections zeolite catalyst alkylation bed, be that raw material carries out alkylated reaction with the recycle benzene and the fresh alkene of fresh benzene and recovery.React required all benzene and all introduce from first conversion zone basically, alkene then injects each conversion zone respectively, and in each conversion zone basically complete reaction fall.Each conversion zone all is an adiabatic, and each section temperature keeps identical substantially, and the temperature rise of each section is no more than 100 °F (38 ℃), preferably is no more than 75 °F (24 ℃), need cool off between each conversion zone for this reason.The total benzene of alkylated reaction and the mol ratio of alkene are about 2～15: 1, temperature of reaction is 150～900 °F (66～482 ℃), best 200～600 (93～316 ℃), reaction pressure are 150～2000Psig (1.02～13.6MPa, best 250～1000Psig (1.7～6.8MPa).The effluent of alkylation reactor can be taked different flow processs, for example: the effluent that contains monoalkylated benzenes and polyalkylbenzene directly enters transalkylation reactor together with the round-robin polyalkylbenzene and the part polyalkylbenzene is converted into the monoalkyl benzo reclaims it, and unconverted polyalkylbenzene carries out recirculation; And for example: the effluent that contains monoalkylated benzenes and polyalkylbenzene enters fractionating system and isolates monoalkylated benzenes product and polyalkylbenzene, and polyalkylbenzene and benzene are mixed into transalkylation reactor and carry out transalkylation reaction, and its effluent enters above-mentioned same fractionating system.The temperature of transalkylation reaction is 150～900 °F (66～482 ℃), best 300～550 °F (149～288 ℃), reaction pressure is 150～2000Psig (1.02～13.6MPa), best 250～1000Psig (1.7～6.8MPa), the mol ratio of phenyl and alkyl is 2～50 during reaction, best 4～25.
The purpose of this invention is to provide a kind of processing method of on one section zeolite catalyst bed, producing alkylbenzene by the liquid-phase alkylation of benzene and alkene.Another object of the present invention provides a kind of processing method of producing alkylbenzene on one section bed of particular zeolite catalyzer by the liquid-phase alkylation of benzene and alkene.
Processing method provided by the invention is: in one section recirculation reactor that contains zeolite catalyst, with by fresh benzene, reclaiming part behind benzene, fresh alkene and the alkylated reaction, to flow out the mixture that material forms be reaction raw materials, is 1.5～8 in the mol ratio of benzene and alkene, the weight ratio of recycle stock and reactor discharging is to carry out alkylated reaction under 1.5～12 the condition.Used zeolite catalyst can be the employed different zeolites that contains in the prior art, as the alkylation catalyst of faujusite, zeolite L, ZSM-5 zeolite, β zeolite.What be suitable for the most is the zeolite catalyst with following composition: the silica alumina ratio of 30～70 heavy % is 20～40 H β zeolite; 0.5 the fluorine or chlorine of～10 heavy % and the γ-Al of surplus
2O
3
According to processing method provided by the invention, it is to carry out in one section recirculation reactor that contains zeolite catalyst that this liquid phase is burnt basicization process, reaction raw materials flows out the mixture that material is formed by fresh benzene, the part that reclaims behind benzene, fresh alkene and the alkylated reaction, each component of this raw material respectively by with the compatible circulating-pump outlet place injecting reactor source line of reactor, raw material olefin is dissolved in the raw material aromatic hydrocarbons fully.Alkylating reaction conditions is as follows: the mol ratio of benzene and alkene is 1.5～8; The weight ratio of recycle stock and reactor discharging is 1.5～12; Temperature of reaction is 100～400 ℃ and is preferably 150～300 ℃; Reaction pressure is 1.5～12 MPas, is preferably 2～6.4 MPas; Total liquid hourly space velocity of benzene feed and recycle stock is 2～50 o'clock
-1, be preferably at 4～30 o'clock
-1Be reflected under the adiabatic condition and carry out, temperature rise surpasses 40 ℃ down in the bed, preferably is no more than 20 ℃.By the part in the effusive effluent that contains excessive benzene, monoalkylated benzenes and polyalkylbenzene of reactor outlet by recycle pump together with fresh benzene, reclaim benzene, fresh alkene is gone into reactor and is reacted, another part then enters separation and recovery system excessive benzene, purpose product monoalkylated benzenes, the intermediate product polyalkylbenzene of Separation and Recovery successively.A part that reclaims in the benzene is used as the alkylated reaction raw material, and another part then enters transalkylation reactor with polyalkylbenzene and fresh benzene polyalkylbenzene is converted into purpose product monoalkylated benzenes.Enter above-mentioned same separating and reclaiming device from the effusive effluent that contains excessive benzene, monoalkylated benzenes and a small amount of polyalkylbenzene of transalkylation reactor outlet and carry out Separation and Recovery with the alkylation reactor effluent.To be converted into the temperature of reaction of monoalkylated benzenes be 150～450 ℃ to polyalkylbenzene in transalkylation reactor, is preferably 200～350 ℃; Reaction pressure is 1.5～12 MPas, is preferably 2～6.4 MPas; Total liquid hourly space velocity of reaction mass is 1～40 o'clock
-1, be preferably at 2～20 o'clock
-1The mol ratio of phenyl and alkyl is 2～40 in the material, is preferably 3～20.
Accompanying drawing illustrates alkylation process flow process provided by the invention.Fresh benzene and recovery benzene from pipeline [1] and pipeline [2] together through the source line [7] of alkylation reactor [6] enters reactor in the remittance of the exit of recycle pump [4] from the fresh alkene of pipeline [5] and by the effusive partially alkylated liquid of circulating-pump outlet through pipeline [3] respectively.Part by the effusive alkylation liquid of reactor outlet pipeline [8] enters recycle pump, and another part enters debenzolizing tower [10] by pipeline [9].Enter recovery benzene basin [12] through non-condensable gases such as isolated benzene of debenzolizing tower and alkane through pipeline [11], liquid benzene enters pipeline [2] or as the alkylated reaction raw material or as the transalkylation reaction raw material, burns hydrocarbon non-condensable gas and institute's a small amount of benzene of taking thereof by pipeline [14] importing dealkylate tower [15] through pipeline [13].Have in the dealkylate tower non-condensable gas such as alkane derive from cat head, the benzene that reclaims at the bottom of the tower then enters pipeline [2] through pipeline [16].The material that contains monoalkylated benzenes and polyalkylbenzene that is gone out by the debenzolizing tower tower bottom flow imports monoalkylated benzenes tower [18] by pipeline [17], and purpose product monoalkylated benzenes is derived from this column overhead, and the material at the bottom of the tower then enters polyalkylbenzene tower [20] through pipeline [19].Isolate the high boiling material tail oil at the bottom of the tower of polyalkylbenzene tower, polyalkylbenzene then enters transalkylation reactor [22] through pipeline [21] makes its major part be converted into purpose product monoalkylated benzenes.Streams behind the transalkylation reaction imports debenzolizing tower by pipeline [23], carries out Separation and Recovery with the alkylation liquid from alkylation reactor.
In liquid phase alkylation process provided by the invention, the employed zeolite catalyst of alkylated reaction and transalkylation reaction can be the employed different zeolites that contains in the prior art, as the alkylation catalyst of faujusite, zeolite L, ZSM-5 zeolite, β zeolite, but what be suitable for the most is the zeolite catalyst with following composition: the silica alumina ratio of 30～70 heavy % is 20～40 H β zeolite; 0.5～10 heavy %, the fluorine or chlorine of best 1～5 heavy % and the γ-Al of surplus
2O
3This catalyzer is preparation like this: with H β zeolite and γ-Al
2O
3Precursor, mix as pseudo-boehmite, boehmite, add the water soluble salt of fluorine or chlorine again, mix as Neutral ammonium fluoride, ammonium chloride etc. pinch, moulding, can add an amount of peptizing agent and/or extrusion aid as needs, dry after 450～550 ℃ of roastings promptly get the catalyzer finished product.
Liquid phase alkylation process provided by the invention is applicable to all kinds of alkylated reactions of benzene, and being specially adapted to ethene or propylene is the alkylated reaction of alkylating agent, and this technology has following advantage:
1. only adopt a first stage reactor, thereby make the reactive system process simplification, reduce investment outlay;
2. benzene feedstock is directly injected directly absorption reaction heat of recycle stock, has improved thermo-efficiency, has reduced the energy consumption of raw material preheating;
Recycle ratio by adjusting reaction mass can be easily with the temperature rise control of conversion zone in suitable scope, and can guarantee that alkene is dissolved in the aromatic hydrocarbons fully;
4. circulating reaction system can reduce the benzene/alkene mol ratio of whole reaction system, thereby has reduced the operating load of reactive system itself and benzene recovery tower, has saved investment and energy consumption.
Other advantage of the present invention can embody from following example, and example also will be further specified the present invention, but not thereby limiting the invention.
Example 1～3
These example explanations adopt alkylation process provided by the invention to produce ethylbenzene.
Experiment be one high 800 millimeters, carry out in the reactor that internal diameter is 25 millimeters.The middle part of reactor be equipped with the dilution of 3 millimeters inert ceramic balls of 90 milliliters of Φ, 30 milliliters consist of 49 heavy %H β, 48 heavy %Al
2O
3, 3 heavy % fluorine the bar shaped catalyst of 1.2～1.3 * 2～3 millimeters of Φ.Fill with the inert ceramic balls of 3～4 millimeters of Φ the upper and lower of reactor.Between Reactor inlet pipeline and outlet line, be equipped with recycle pump, so that the partial reaction material circulates.Raw material ethene and benzene are through mixing with the recycle stock of circulating-pump outlet, and ethene is dissolved in benzene feedstock and the recycle stock fully.The reaction raw materials that mixes after dissolving each other enters reactor from reactor lower part, and a material part of coming out from reactor head in the reaction back is introduced separation and recovery system as product, and another part enters recycle pump.The alkylation liquid that comes out from recycle pump with enter reactor after benzene feedstock and ethene are mixed and carry out alkylated reaction.
Isolate benzene, ethylbenzene, diethylbenzene one triethyl-benzene, the several cuts that grade of recombinating by separation and recovery system, wherein ethylbenzene is product, benzene recycles as alkylation and transalkylation reaction raw material, the mixture of diethylbenzene and triethyl-benzene carries out transalkylation reaction with same catalyzer in the presence of excessive benzene, the overwhelming majority wherein changes purpose product ethylbenzene into.
Listed the reaction conditions of alkylation and transalkylation and each component distribution of product that records with chromatographic instrument in the table 1, the liquid hourly space velocity in the table is benzene and the volume numerical value of recycle stock under 20 ℃; Recycle ratio is the weight ratio of recycle stock and reactor discharging; Overall yield is the productive rate behind alkylation and transalkylation reaction.
Example 4
The explanation of this example adopts alkylation process provided by the invention to produce isopropyl benzene.
Experiment equipment therefor and catalyzer only change the alkene in the reaction raw materials into propylene with example 1～3, are benzene, isopropyl benzene, diisopropylbenzene(DIPB), heavy constituent by the isolated several cuts of separation and recovery system, and purpose product wherein is an isopropyl benzene.
The reaction conditions of alkylation and transalkylation and each component distribution of product that records with chromatographic instrument have been listed in the table 2.
Table 1
| Example 1 | Example 2 | Example 3 | |
| Alkylation reaction condition benzene/ethene (mol ratio) temperature of reaction, ℃ reaction pressure, the MPa liquid hourly space velocity, the time -1The recycle ratio conversion of ethylene, heavy % alkylation selectivity, heavy % ethylbenzene diethylbenzene triethyl-benzene unknown material transalkylation reaction conditions: phenyl/alkyl (mol ratio) temperature of reaction, ℃ reaction pressure, the MPa liquid hourly space velocity, the time -1Overall yield, the heavy constituent of heavy % ethylbenzene light constituent | 5.91 250 3.5 12 3.13 100 91.0 7.8 0.5 0.7 9.95 260 3.8 3 97.5 0.5 2.0 | 5.98 235 3.5 12 3.11 100 89.0 9.9 0.7 0.4 9.89 260 3.8 3 97.3 0.5 2.2 | 4.13 235 3.5 12 4.23 100 85.0 12.4 1.2 1.4 10.01 260 3.8 3 97.0 0.5 2.5 |
Table 2
| Example 4 | |
| Alkylation reaction condition benzene/propylene (mol ratio) temperature of reaction, ℃ reaction pressure, the MPa liquid hourly space velocity, the time -1The recycle ratio propylene conversion, heavy % alkylation selectivity, heavy % isopropyl benzene diisopropylbenzene(DIPB) unknown material transalkylation reaction conditions: phenyl/alkyl (mol ratio) temperature of reaction, ℃ reaction pressure, the MPa liquid hourly space velocity, the time -1Overall yield, the heavy constituent of heavy % isopropyl benzene light constituent | 6.25 200 3.5 8 2.84 100 92.5 5.5 2.0 10.05 250 3.5 3 97.0 0.5 2.5 |
Claims (8)
1. the liquid phase alkylation process of a benzene in the presence of zeolite catalyst, comprise with fresh alkene, the mixture of fresh benzene and recovery benzene is a raw material, in adiabatic reactor, carry out catalytic conversion reaction, it is characterized in that: reaction is in one section recirculation reactor, with by fresh benzene, reclaim benzene, it is that the mixture that recycle stock is formed is a reaction raw materials that part behind fresh alkene and the alkylated reaction flows out material, is 1.5～8 in the mol ratio of benzene and alkene, the weight ratio that recycle stock and alkylated reaction post-reactor always flow out material is to carry out under 1.5～12 the condition.
2. in accordance with the method for claim 1, it is characterized in that catalyst system therefor has following composition in the said reactor: the silica alumina ratio of 30～70 heavy % is 20～40 H β zeolite; 0.5 the fluorine or chlorine of～10 heavy % and the γ-Al of surplus
2O
3
3. in accordance with the method for claim 1, it is characterized in that said alkene is ethene or propylene.
4. in accordance with the method for claim 1, it is characterized in that this alkylated reaction is is that 100～400 ℃, pressure are that total liquid hourly space velocity of 1.5～12 MPas, benzene feed and recycle stock is in temperature at 2～50 o'clock
-1, temperature rise is no more than and carries out under 40 ℃ the condition.
5. in accordance with the method for claim 4, it is characterized in that said alkylated reaction is is that 150～300 ℃, pressure are that total liquid hourly space velocity of 2.0～6.4 MPas, benzene feed and recycle stock is in temperature at 4～30 o'clock
-1, temperature rise is no more than and carries out under 20 ℃ the condition.
6. in accordance with the method for claim 2, it is characterized in that containing in the said catalyzer fluorine or chlorine of 1～5 heavy %.
7. in accordance with the method for claim 1, it is characterized in that this method comprises that further part behind the alkylated reaction flows out material and enters separation and recovery system, it is that 150～450 ℃, pressure are that total liquid hourly space velocity of 1.5～12 MPas, reaction mass is 1～40 o'clock in temperature that the polyalkylbenzene of gained enters transalkylation reactor
-1, the mol ratio of phenyl and alkyl is to be converted into monoalkylated benzenes under 2～20 the condition in the material.
8. in accordance with the method for claim 7, it is characterized in that the conversion condition of said polyalkylbenzene in transalkylation reactor is: total liquid hourly space velocity 2～20 of 200～350 ℃ of temperature of reaction, reaction pressure 2.0～6.4 MPas, reaction mass o'clock
-1, phenyl and alkyl mol ratio 3～20 in the material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101006A CN1045284C (en) | 1995-01-03 | 1995-01-03 | Liquid phase alkylation process of benzene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95101006A CN1045284C (en) | 1995-01-03 | 1995-01-03 | Liquid phase alkylation process of benzene |
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|---|---|
| CN1128249A CN1128249A (en) | 1996-08-07 |
| CN1045284C true CN1045284C (en) | 1999-09-29 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404486C (en) * | 2002-08-29 | 2008-07-23 | 中国石油化工股份有限公司 | Preparation method of alkylbenzene |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479721B1 (en) | 1997-06-16 | 2002-11-12 | Uop Llc | Alkylation process operating at low olefin ratios |
| CN101239883B (en) * | 2008-03-12 | 2010-09-01 | 江苏工业学院 | Method for catalytically synthesizing ethyl benzene by using benzene and diethyl oxalate as raw material |
| CN103030519B (en) * | 2011-09-29 | 2015-05-13 | 中国石油化工股份有限公司 | Production method for alkylbenzene |
| CN103030515B (en) * | 2011-09-30 | 2016-01-13 | 中国石油化工股份有限公司 | Alkylbenzene production method |
| 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 |
| CN110776391B (en) * | 2019-11-11 | 2022-05-31 | 山东京博石油化工有限公司 | Device and method for preparing ethylbenzene from dry gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144280A (en) * | 1977-05-31 | 1979-03-13 | Uop Inc. | Vapor circulation in hydrocarbon conversion processes |
| US4237328A (en) * | 1979-10-09 | 1980-12-02 | Uop Inc. | Process for HF-catalyzed alkylation of aromatic hydrocarbons |
| US4503277A (en) * | 1983-11-30 | 1985-03-05 | Uop Inc. | HF regeneration in aromatic hydrocarbon alkylation process |
-
1995
- 1995-01-03 CN CN95101006A patent/CN1045284C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4144280A (en) * | 1977-05-31 | 1979-03-13 | Uop Inc. | Vapor circulation in hydrocarbon conversion processes |
| US4237328A (en) * | 1979-10-09 | 1980-12-02 | Uop Inc. | Process for HF-catalyzed alkylation of aromatic hydrocarbons |
| US4503277A (en) * | 1983-11-30 | 1985-03-05 | Uop Inc. | HF regeneration in aromatic hydrocarbon alkylation process |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404486C (en) * | 2002-08-29 | 2008-07-23 | 中国石油化工股份有限公司 | Preparation method of alkylbenzene |
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| CN1128249A (en) | 1996-08-07 |
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