CN102746096A - Method for liquid phase transalkylation of polyethylbenzene and benzene - Google Patents
Method for liquid phase transalkylation of polyethylbenzene and benzene Download PDFInfo
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- CN102746096A CN102746096A CN201110100160XA CN201110100160A CN102746096A CN 102746096 A CN102746096 A CN 102746096A CN 201110100160X A CN201110100160X A CN 201110100160XA CN 201110100160 A CN201110100160 A CN 201110100160A CN 102746096 A CN102746096 A CN 102746096A
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Abstract
The invention relates to a method for liquid phase transalkylation of polyethylbenzene and benzene, and mainly solves the problems of high initial reaction temperature, poor catalyst stability, and short regeneration cycle in the prior art. The method of the invention consists of: adopting polyethylbenzene and benzene as reaction raw materials, and under the conditions of a reaction temperature of 100-260DEG C, a reaction pressure of 2.0-4.5MPa, a liquid phase weight hourly space velocity of 1-10h<-1>, and a weight ratio of benzene to polyethylbenzene of 1-10, contacting the reaction raw materials with a catalyst to undergo a liquid phase transalkylation reaction so as to produce ethylbenzene. Specifically, the catalyst comprises the following components by weight: a) 30-90 parts of a Y type molecular sieve; and b) 10-70 parts of a binder, wherein the Y type molecular sieve is obtained by making Y type molecular sieve raw powder undergo steps including at least one alkali treatment. The technical scheme employed in the invention well solves the problems, and can be used for the industrial production of ethylbenzene through liquid phase transalkylation of polyethylbenzene and benzene.
Description
Technical field
The present invention relates to the method for a kind of multi-ethyl phenenyl and benzene liquid phase transalkylation.
Background technology
Ethylbenzene is important Organic Chemicals, and is main as producing cinnamic raw material in the industry.Ethylbenzene is mainly made through alkylated reaction by benzene and ethene, and its alkylation process generally is divided into gas molecule in space sieve method and liquid phase sieve method.No matter be the gas molecule in space sieve method or the alkylation process of liquid phase sieve method; Because reaction product ethylbenzene can equally with benzene feedstock continue and many ethylbenzene components such as ethene generation alkylated reaction generation diethylbenzene, triethyl-benzene, tetrem benzene; So all set up independently transalkylation reactor in the modern ethylbenzene industrial production, generated ethylbenzene to this part many ethylbenzene of from alkylation reaction product, separating material and benzene mixing back through the transalkylation catalyst reaction.Do the generation that not only can reduce side reaction in the alkylated reaction like this, improve the life-span of alkylation catalyst, also can improve the productive rate of ethylbenzene.
What early stage patent US3751504, US4016218, US3962364 and CN1310051 selected for use is the gas phase alkyl transfering process; The catalyst activity component that adopts is the ZSM-5 molecular sieve, has adopted HZSM-5 molecular sieve, element phosphor modification processing and the steam-treated of unmodified HZSM-5, steam-treated respectively and has been aided with the HZSM-5 molecular sieve that organic acid is handled modification.This makes that the performance of gas phase alkyl catalyst has obtained significantly improving.But the strength of acid that transalkylation reaction needs is higher than alkylated reaction, and simultaneously in order to keep reaction mass to be under the gas phase condition, the gas phase transalkylation reaction all needs very high temperature of reaction, generally greater than 400 ℃.This has caused the side reaction of gas phase transalkylation reaction many, and the content of YLENE and impurity is than higher, and catalyst life is shorter.Simultaneously, in order to keep high selectivity, the transformation efficiency of gas phase transalkylation is all lower, and high maintenance is 60%.
Along with the advantage of liquid phase method low-temp reaction is studied personnel's understanding gradually, the method for molecular sieve liquid phase transalkylation is developed successively.US4774377 discloses a kind of liquid phase transalkylation process, adopts enterprisingly to go out on going out down, advancing down or the reactor drum of horizontal positioned, and its catalyzer can adopt X, Y type, L type, USY, omega zeolite and mordenite, recommends to adopt mordenite.Patent US3551510 discloses and has a kind ofly obtained product ethylbenzene through separating the product of vapor-phase alkylation process, simultaneously isolated many ethylbenzene and the independent technology of reacting with a top-down transalkylation reactor of benzene, liquid air speed 1.0 hours
-1, 250 ℃ of temperature, under the pressure 3.4MPa condition, adopt mordenite to use as transalkylation catalyst.Adopt the mordenite temperature of reaction higher in these patents, the material air speed is also lower simultaneously.
CA2022982 has described the technological process of concrete liquid phase transalkylation, adopts y-type zeolite to use as transalkylation catalyst.US4169111 has introduced in detail and has adopted independent transalkylation process from bottom to top, recommends to adopt Na
2O content 0.2%, the Y molecular sieve handled of water vapor super stabilizing uses as transalkylation catalyst.Be recommended in 232～343 ℃ of temperature, pressure 2.8～6.9MPa, total quality of material air speed was at 2～10 hours
-1, benzene and diethylbenzene mol ratio are reacted under 2～5 conditions.After can finding out that the Y molecular sieve that adopts the water vapor super stabilizing to handle in this patent is done transalkylation catalyst, the material air speed increases, but temperature of reaction is still higher.Japanese Patent JP1135728 discloses the preparation method of diethylbenzene and benzene transalkylation catalyst under a kind of liquid-phase condition, adopt the Y zeolite of ferro element modification, but this catalyzer will be with containing H before reaction
2And H
2The gas of S carries out pre-treatment, the preprocessing process more complicated before catalyzer uses.CN1323739A has described a kind of Y zeolite and has been used for many ethylbenzene and benzene liquid phase transalkylation process; Prepared molecular sieve was handled 0.5～4 hour in room temperature～650 ℃ under ammonia atmosphere through at least one step, handled 1～3 hour step and obtained for preferred 150～600 ℃.CN1359752A has described a kind of catalyzer of being used by polyalkylbenzene and benzene manufacture order korenyl of being used for, by SiO
2/ Al
2O
3Mol ratio is that 8～20 HY zeolite and inerts e constitute, and wherein the Y zeolite weight range is 40～90%, and all the other are one or more the auxiliary element that is selected from P, basic metal and alkali earth metal of inerts e and 0.01～5% (weight).This catalyzer is used for multi-ethyl phenenyl and benzene liquid phase transalkylation process and produces ethylbenzene, and the transformation efficiency of multi-ethyl phenenyl is greater than 60%, and the selectivity that generates ethylbenzene is greater than 99%, xylene content＜120ppm in the ethylbenzene.CN1373006A has described a kind of catalyzer that is used for being produced by multi-ethyl phenenyl and benzene ethylbenzene, by SiO
2/ Al
2O
3Mol ratio is 8～20 Y zeolite and inertia component formation, and wherein the Y zeolite weight range is 40～90%, and all the other are the inertia component.The sour characteristics of this catalyzer are that the ratio at middle strong acid center (330～600 ℃ of ammonia desorption relative acid centers) and weak acid center (150～330 ℃ of ammonia desorption relative acid centers) is 65: 35～35: 65.This catalyzer is used for multi-ethyl phenenyl and benzene liquid phase transalkylation process is produced ethylbenzene, and the transformation efficiency of multi-ethyl phenenyl is greater than 70%, and the selectivity that generates ethylbenzene is more than or equal to 98%.The common ground of above-mentioned patent has all been mentioned the ammonium ion exchange of Y zeolite and the modification of water vapour super stabilizing has been handled; But the liquid phase transalkylation reaction that is used for multi-ethyl phenenyl and benzene through the Y zeolite after handling like this; Still exist initial reaction temperature higher, the problem of less stable.
Summary of the invention
Technical problem to be solved by this invention is to exist initial reaction temperature higher in the prior art, and poor catalyst stability, short problem of regeneration period provide a kind of new multi-ethyl phenenyl and the method for benzene liquid phase transalkylation.It is low that this method has an initial reaction temperature, the characteristics that catalyst stability is good, the regeneration period is long.
For solving the problems of the technologies described above; The technical scheme that the present invention adopts is following: the method for a kind of multi-ethyl phenenyl and benzene liquid phase transalkylation is a reaction raw materials with multi-ethyl phenenyl and benzene, 100～260 ℃ of temperature of reaction; Reaction pressure 2.0～4.5MPa, liquid phase weight space velocity 1～10 hour
-1, under the condition of benzene/multi-ethyl phenenyl weight ratio 1～10, reaction raw materials contacts with catalyzer liquid phase transalkylation reaction generation ethylbenzene takes place; Said catalyzer comprises following component in parts by weight: a) 30～90 parts Y zeolite; B) 10～70 parts sticker;
Wherein, said Y zeolite is that the former powder of Y zeolite is obtained through the step that comprises alkaline purification at least; Alkali treatment method may further comprise the steps: according to former dried bean noodles base of Y zeolite and alkaline solution weight ratio is that 1～20 making beating mixes, and under 0～100 ℃ of stirring, handles 0.1～24 hour; Said alkaline concentration is 001～10 weight %.
In the technique scheme, the alkaline purification optimum condition is: the weight ratio according to former dried bean noodles base of Y zeolite and alkaline solution is 0.05～1, and its alkali purification temp is 20～95 ℃, and the alkaline purification time is 1～10 hour, and alkaline concentration is 0.05～5 weight %.Said alkaline solution preferred version is to be selected from least a in NaOH solution or the KOH solution.Said sticker preferred version is to be selected from least a in aluminum oxide, silicon-dioxide, clay or the zeyssatite.Said Y zeolite preferred version be with the former powder of Y zeolite through comprising at least alkaline purification, and then carry out at least ammonium ion exchange and handle with the step of at least steam-treated and obtain; More preferably scheme be with the former powder of Y zeolite successively through comprising at least alkaline purification, at least twice ammonium ion exchange is handled, at least twice steam-treated, at least twice ammonium ion exchange is handled with the step of twice steam-treated obtain at least again.
Molecular screen primary powder described in the present invention is meant the product that after hydro-thermal is synthetic, obtains, without roasting.
The ammonium ion exchange treatment process is the conventional method that adopts in the prior art among the present invention, and the present invention has no particular limits it.For example use the ammonium salt solution of weight concentration 1～20%, under 0～100 ℃ of condition, handled 0.5～24 hour.Said ammonium salt is selected from least a in an ammonium nitrate, ammonium chloride, ammonium oxalate, ammonium sulfate or the ammonium citrate.Said exchange generally also comprises filtration, water-washing step.Steam treatment process is the conventional method that adopts in the prior art among the present invention, and the present invention has no particular limits it.For example at 400～800 ℃, carried out steam-treated 0.5～24 hour containing under 10～100% the water vapour atmosphere.
Preparation of catalysts method among the present invention can may further comprise the steps:
A) preparation weight concentration scope is that 1～20 making beating mixes at 0.01～10% alkaline solution according to Y zeolite butt and alkaline solution weight ratio, and processing 0.1～24 hour under 0～100 ℃ of stirring.Carry out dope filtration subsequently, and with deionized water wash to pH less than 10.This alkaline solution treating processes at least once.
B) Y zeolite after the step a) processing is carried out ammonium ion exchange at least 2 times, oven dry, roasting.
C) with the Y zeolite steam-treated after the step b) processing.
D) Y zeolite after the step c) processing is carried out ammonium ion exchange at least 2 times, oven dry, roasting.
E) with the Y zeolite steam-treated after the step d) processing.
F) with Y zeolite and sticker extruded moulding after the step e) processing, oven dry, roasting obtains said catalyzer.
Catalyzer among the present invention carries out ammonium ion exchange at least 2 times before use, oven dry, roasting.
In the above-mentioned steps, bake out temperature is 100～150 ℃, and drying time is 1～10 hour; Maturing temperature is 400～600 ℃, and roasting time is 1～10 hour.
The inventive method can be used for also being can be used for by the many ethylbenzene component of alcohol legal system ethylbenzene alkylation process generation and the liquid phase transalkylation process of benzene by the many ethylbenzene component of the rare ethylbenzene manufactured from ethylene alkylation process generation in ethene or the catalytic cracked dry gas and the liquid phase transalkylation process of benzene.
The molecular sieve that the inventive method adopted is at first the synthetic good former powder of Y zeolite to be carried out the dilute alkaline soln pre-treatment, carries out conventional ammonium ion exchange processing and water vapor super stabilizing subsequently again and handles.The dilute alkaline soln pre-treatment can be modified molecular sieve outer surface on the one hand, can carry out desiliconization to the catalyzer aperture on the other hand and modify.This makes molecular sieve on the basis that keeps original structure, obtain flourishing more secondary pore again, makes reactant and product be easy to pass in and out the duct.The aperture of plane of crystal is modified through desiliconization and is able to enlarge simultaneously, and some sodium ions also are easy to exchanged.Dilute alkaline soln is handled to handle to be placed in the same equipment with ammonium ion exchange and is carried out in the industrial production, therefore also is easy to the industriallization operation.After the Y zeolite moulding after handling in this way; The catalyzer that makes is used for the catalysis multi-ethyl phenenyl and benzene liquid phase transalkylation reaction has shown excellent catalytic performance; Can make initial reaction temperature be reduced to 120 ℃; Stability is better, and the catalyst regeneration cycle reached more than 2 years, had obtained better technical effect.
Give further explanation through embodiment to the present invention below.
Embodiment
[embodiment 1]
Take by weighing in the zero(ppm) water of 1 gram dissolution of sodium hydroxide to 999 gram.Take by weighing the former powder 50 gram (SiO of ordinary method synthetic NaY type
2/ Al
2O
3Than 5.53, grain size is between 0.8～1 micron) join in the dilute alkaline soln for preparing, under 90 ℃, with magnetic stirrer 6 hours, centrifugal, filtration was washed till pH less than 10 with deionized water.Dispose weight concentration again and be 10% aqueous ammonium nitrate solution, stirred 1 hour down for 90 ℃ in temperature, centrifuging subsequently, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 2 times.In 110 ℃ of oven dry, 550 ℃ of roastings 3 hours.In 650 ℃, under 100% water vapour atmosphere, handled 4 hours subsequently.Stop to feed water vapor then, reduce to room temperature, using weight concentration again is 10% aqueous ammonium nitrate solution, and 90 ℃ were stirred 1 hour down, centrifuging subsequently, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 2 times.In 110 ℃ of oven dry, 550 ℃ of roastings 3 hours.In 650 ℃, under 100% water vapour atmosphere, handled 4 hours subsequently.Be 80/20 by molecular sieve/aluminum oxide (butt than) at last, extruded moulding, 110 ℃ of oven dry, 550 ℃ of roastings 3 hours promptly obtain finished catalyst.
[embodiment 2～7]
With [embodiment 1], just the condition of alkaline purification is different.Specifically see table 1.
Table 1
[embodiment 8]
Fixed-bed reactor with are from bottom to top investigated the catalyzer initial activity, and reactor drum is the stainless steel tube of 28 millimeters of internal diameters, 800 millimeters of length.Loaded catalyst is 6 grams, and dilutes with granulated glass sphere.
Before catalyzer used, using weight concentration was 10% aqueous ammonium nitrate solution, and 90 ℃ were stirred 1 hour down, with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 2 times.In 110 ℃ of oven dry, 550 ℃ of roastings 3 hours.
After the catalyst loading of [embodiment 1～7] advanced reactor drum, under nitrogen protection, catalyzer is carried out activation, 400 ℃ of following activation 1 hour.Be cooled to then below 40 ℃, stop nitrogen purging, begin into transalkylation material, treat that pressure reaches the value that sets after, begin to be warming up to temperature of reaction.
Reaction conditions is: 180 ℃ of temperature, pressure 3.0MPa, total liquid phase air speed 2 hours
-1, benzene and diethylbenzene weight ratio 8: 1.After treating system stability, regularly getting product liquid carries out stratographic analysis.Following data all are 10 hours stable data of charging, specifically see table 2.
[comparative example 1]
With [embodiment 1],, only handle and steam-treated through ammonium ion exchange just without alkaline purification.Investigate the catalyzer initial activity with [embodiment 8] then, the result sees table 2.
Table 2
[embodiment 9]
With [embodiment 8], just temperature of reaction is 120 ℃.The result sees table 3.
[comparative example 2]
With [embodiment 9], just catalyst system therefor is the catalyzer in [comparative example 1].The result sees table 3.
Table 3
Visible by table 3, under 120 ℃ of the low temperature, adopt still higher activity and the selectivity of tool of the inventive method.And adopt without alkaline purification, only ammonium is handed over and the catalyzer of steam-treated, under the situation of 120 ℃ of low temperature, activity is lower, the diethylbenzene transformation efficiency is 38.14%.Reach effect of the present invention, must bring up to more than 170 ℃ to major general's initial reaction temperature.
[embodiment 10]
Investigate the stability of catalyzer.
With [embodiment 8], just reaction conditions is: 230 ℃ of temperature, pressure 3.0MPa, total liquid phase air speed 6.67 hours
-1, benzene and diethylbenzene weight ratio 2: 1.The result sees table 4.
[comparative example 3]
Investigate the stability of catalyzer in [comparative example 1] with [embodiment 10].The result sees table 4.
Table 4
Claims (8)
1. the method for multi-ethyl phenenyl and benzene liquid phase transalkylation is a reaction raw materials with multi-ethyl phenenyl and benzene, 100～260 ℃ of temperature of reaction, and reaction pressure 2.0～4.5MPa, liquid phase weight space velocity 1～10 hour
-1, under the condition of benzene/multi-ethyl phenenyl weight ratio 1～10, reaction raw materials contacts with catalyzer liquid phase transalkylation reaction generation ethylbenzene takes place; Said catalyzer comprises following component in parts by weight: a) 30～90 parts Y zeolite; B) 10～70 parts sticker;
Wherein, said Y zeolite is that the former powder of Y zeolite is obtained through the step that comprises alkaline purification at least; Alkali treatment method may further comprise the steps: according to former dried bean noodles base of Y zeolite and alkaline solution weight ratio is 0.01～2, and making beating mixes, and under 0～100 ℃ of stirring, handles 0.1～24 hour; Said alkaline concentration is 0.01～10 weight %.
2. the method for multi-ethyl phenenyl according to claim 1 and benzene liquid phase transalkylation; It is characterized in that the weight ratio according to former dried bean noodles base of Y zeolite and alkaline solution is 0.05～1; Its alkali purification temp is 20～95 ℃, and the alkaline purification time is 1～10 hour, and alkaline concentration is 0.05～5 weight %.
3. the method for multi-ethyl phenenyl according to claim 1 and benzene liquid phase transalkylation is characterized in that said alkaline solution is selected from least a in NaOH solution or the KOH solution.
4. the method for multi-ethyl phenenyl according to claim 1 and benzene liquid phase transalkylation is characterized in that said sticker is selected from least a in aluminum oxide, silicon-dioxide, clay or the zeyssatite.
5. the method for multi-ethyl phenenyl according to claim 1 and benzene liquid phase transalkylation; It is characterized in that said Y zeolite be with the former powder of Y zeolite through comprising at least alkaline purification, and then carry out at least ammonium ion exchange and handle with the step of at least steam-treated and obtain.
6. the method for multi-ethyl phenenyl according to claim 5 and benzene liquid phase transalkylation; It is characterized in that said Y zeolite is successively through comprising at least alkaline purification with the former powder of Y zeolite; At least twice ammonium ion exchange is handled; At least twice steam-treated, at least twice ammonium ion exchange is handled with the step of twice steam-treated obtain at least again.
7. according to the method for claim 5 or 6 described multi-ethyl phenenyls and benzene liquid phase transalkylation, it is characterized in that the ammonium ion exchange treatment process is:, under 0～100 ℃ of condition, handled 0.5～24 hour with the ammonium salt solution of weight concentration 1～20%; Said ammonium salt is selected from least a in an ammonium nitrate, ammonium chloride, ammonium oxalate, ammonium sulfate or the ammonium citrate.
8. according to the method for claim 5 or 6 described multi-ethyl phenenyls and benzene liquid phase transalkylation, it is characterized in that steam treatment process is:, carried out steam-treated 0.5～24 hour containing under 10～100% the water vapour atmosphere at 400～800 ℃.
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| CN104230633A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Liquid phase alkyl transfer method |
| CN104276922A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Method for producing ethylbenzene by liquid-phase transalkylation |
| CN105130728A (en) * | 2015-08-21 | 2015-12-09 | 中石化炼化工程（集团）股份有限公司 | Method for preparing xylene from methanol, and apparatus thereof |
| CN105566049A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for liquid-phase transalkylation of polyethylated benzene and benzene |
| CN107777697A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Y type molecular sieve and preparation method thereof |
| CN108698842A (en) * | 2016-02-29 | 2018-10-23 | 勒芬天主教大学 | To the controlled alkali process of molecular sieve |
| CN112707410A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | USY type molecular sieve and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230633A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Liquid phase alkyl transfer method |
| CN104276922A (en) * | 2013-07-09 | 2015-01-14 | 中国石油化工股份有限公司 | Method for producing ethylbenzene by liquid-phase transalkylation |
| CN105566049A (en) * | 2014-10-13 | 2016-05-11 | 中国石油化工股份有限公司 | Method for liquid-phase transalkylation of polyethylated benzene and benzene |
| CN105130728A (en) * | 2015-08-21 | 2015-12-09 | 中石化炼化工程（集团）股份有限公司 | Method for preparing xylene from methanol, and apparatus thereof |
| CN105130728B (en) * | 2015-08-21 | 2018-06-29 | 中石化炼化工程（集团）股份有限公司 | A kind of method and device that dimethylbenzene is prepared using methanol |
| CN108698842A (en) * | 2016-02-29 | 2018-10-23 | 勒芬天主教大学 | To the controlled alkali process of molecular sieve |
| CN108698842B (en) * | 2016-02-29 | 2022-07-19 | 勒芬天主教大学 | Controlled base treatment of molecular sieves |
| CN107777697A (en) * | 2016-08-30 | 2018-03-09 | 中国石油化工股份有限公司 | Y type molecular sieve and preparation method thereof |
| CN107777697B (en) * | 2016-08-30 | 2020-11-03 | 中国石油化工股份有限公司 | Y-type molecular sieve and preparation method thereof |
| CN112707410A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | USY type molecular sieve and preparation method and application thereof |
| CN112707410B (en) * | 2019-10-24 | 2022-08-12 | 中国石油化工股份有限公司 | USY type molecular sieve and preparation method and application thereof |
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Application publication date: 20121024 |