CN104276922A - Method for producing ethylbenzene by liquid-phase transalkylation - Google Patents

Method for producing ethylbenzene by liquid-phase transalkylation Download PDF

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CN104276922A
CN104276922A CN201310286115.7A CN201310286115A CN104276922A CN 104276922 A CN104276922 A CN 104276922A CN 201310286115 A CN201310286115 A CN 201310286115A CN 104276922 A CN104276922 A CN 104276922A
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ethylbenzene
liquid phase
reaction
method
produced
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宦明耀
杨为民
孙洪敏
张斌
沈震浩
薛明伟
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Abstract

The invention relates to a method for producing ethylbenzene by liquid-phase transalkylation. The invention mainly solves problems of low utilization rate, poor strength and poor activity and stability of a catalyst in the prior art. According to the invention, multi-ethylbenzene and benzene are used as raw materials for a reaction. Under the condition that reaction temperature is 100-260 DEG C, reaction pressure is 2.0-4.5 MPa, weight hourly space velocity of a liquid phase is 1-10 h<-1> and the weight ratio of benzene to multi-ethylbenzene is 1-10, the raw materials for the reaction is contacted with a catalyst to carry out a liquid-phase transalkylation reaction so as to generate ethylbenzene, wherein the catalyst a binder-free Beta type molecular sieve with the molar ratio of SiO2/Al2O3 being 5-200. By the technical scheme, the above problems are solved well. The method provided by the invention can be used in the industrial production of producing ethylbenzene by liquid-phase transalkylation of multi-ethylbenzene and benzene.

Description

The method of ethylbenzene is produced in liquid phase transfer

Technical field

The present invention relates to the method that ethylbenzene is produced in the transfer of a kind of liquid phase.

Background technology

Ethylbenzene is important Organic Chemicals, and industrial main being used as produces cinnamic raw material.Ethylbenzene is obtained by alkylated reaction primarily of benzene and ethene, and its alkylation process is generally divided into gas molecule in space sieve method and liquid phase molecule sieve method.It is no matter the alkylation process of gas molecule in space sieve method or liquid phase molecule sieve method, because reaction product ethylbenzene can equally with benzene feedstock continue to generate many ethylbenzene components such as diethylbenzene, triethyl-benzene, four ethylbenzene with ethene generation alkylated reaction, so all establish independently transalkylation reactor in the ethylbenzene industrial production in modern times, after many ethylbenzene material that this part is separated from alkylation reaction product and benzene mixing, generate ethylbenzene by transalkylation catalyst reaction.Do the generation that not only can reduce side reaction in 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 is vapor-phase transalkylation technique, the catalyst activity component adopted is ZSM-5 molecular sieve, have employed unmodified HZSM-5, the HZSM-5 molecular sieve of steam-treated, element phosphor modification and steam-treated respectively and is aided with the HZSM-5 molecular sieve of organic acid process modification.This makes the performance of gas phase alkyl catalyst obtain significantly to improve.But the strength of acid that transalkylation reaction needs is higher than alkylated reaction, simultaneously in order under keeping reaction mass to be in gas phase condition, vapor-phase transalkylation reaction all needs very high temperature of reaction, is generally greater than 400 DEG C.The side reaction which results in vapor-phase transalkylation reaction is many, and the comparision contents of dimethylbenzene and impurity is high, and catalyst life is shorter.Meanwhile, in order to maintain high selectivity, the transformation efficiency of vapor-phase transalkylation is all lower, and most high maintenance is 60%.

Along with advantage studied personnel's understanding gradually of liquid phase method low-temp reaction, the method for molecular sieve liquid phase transfer is developed successively.US4774377 discloses a kind of liquid phase transfer process, and adopt the reactor of upper entering and lower leaving, bottom in and top out or horizontal positioned, its catalyzer can adopt X, Y type, L-type, USY, omega zeolite and mordenite, recommends to adopt mordenite.Patent US3551510 disclosed a kind of product by being separated gas phase alkylation process, obtains product ethylbenzene, isolated many ethylbenzene and benzene is carried out separately the technique of reacting with a top-down transalkylation reactor simultaneously, liquid air speed 1.0 hours -1, temperature 250 DEG C, under pressure 3.4MPa condition, adopt mordenite use as transalkylation catalyst.Adopt mordenite temperature of reaction higher in these patents, material air speed is also lower simultaneously, and described catalyzer all for there being the molecular sieve of binding agent, causes catalyst utilization lower.

CA2022982 describes the technological process of concrete liquid phase transfer, adopts y-type zeolite to use as transalkylation catalyst.US4169111 describes in detail and adopts independent transalkylation process from bottom to top, recommends to adopt Na 2o content 0.2%, the Y molecular sieve of water vapor super stabilizing process uses as transalkylation catalyst.Be recommended in temperature 232 ~ 343 DEG C, 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.Can find out in this patent that after adopting the Y molecular sieve of water vapor super stabilizing process to do transalkylation catalyst, 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, adopts the Y zeolite of ferro element modification, but this catalyzer is with containing H before the reaction 2and H 2the gas of S carries out pre-treatment, the preprocessing process more complicated before catalyzer uses.CN1323739A describes a kind of Y zeolite for many ethylbenzene and benzene liquid phase transfer process, prepared molecular sieve is by DEG C process 0.5 ~ 4 hour in room temperature ~ 650 under ammonia atmosphere of at least one step, and preferably 150 ~ 600 DEG C process the step of 1 ~ 3 hour and obtain.CN1359752A describes a kind of for the catalyzer by polyalkylbenzene and benzene manufacture order alkylbenzene, by SiO 2/ Al 2o 3mol ratio is HY zeolite and the inert component formation of 8 ~ 20, wherein Y zeolite weight range is 40 ~ 90%, and all the other are one or more the auxiliary element being selected from P, alkali and alkaline earth metal ions element of inert component and 0.01 ~ 5% (weight).This catalyzer is used for multi-ethyl phenenyl and benzene liquid phase transfer process produces ethylbenzene, and the transformation efficiency of multi-ethyl phenenyl is greater than 60%, and the selectivity generating ethylbenzene is greater than 99%, xylene content < 120ppm in ethylbenzene.CN1373006A describes a kind of catalyzer for being produced ethylbenzene by multi-ethyl phenenyl and benzene, by SiO 2/ Al 2o 3mol ratio is Y zeolite and the inert formation of 8 ~ 20, and wherein Y zeolite weight range is 40 ~ 90%, and all the other are inert.The sour feature of this catalyzer is the ratio at middle strong acid center (330 ~ 600 DEG C of ammonia desorption relative acid centers) and weak acid center (150 ~ 330 DEG C of ammonia desorption relative acid centers) is 65: 35 ~ 35: 65.This catalyzer is used for multi-ethyl phenenyl and benzene liquid phase transfer process produces ethylbenzene, and the transformation efficiency of multi-ethyl phenenyl is greater than 70%, and the selectivity generating ethylbenzene is more than or equal to 98%.

US4891458, CN1096025A respectively describe the technological process adopting β zeolite to use as liquid-phase alkylation and liquid phase transfer catalyst.CN101146752A describes and adopts the β zeolite of phosphoric modification to use as liquid phase transfer catalyst.CN1096025A describes and adopts H β zeolite to use as liquid phase transfer catalyst.CN1373004A describes a kind of SiO 2/ Al 2o 3molar ratio range is 25 ~ 60, and the β zeolite through halogens modification uses as many ethylbenzene and benzene liquid phase transfer catalyst.CN1207960A describes a kind of rare earth or alkali-earth metal modified β zeolite uses as liquid phase transfer catalyst.The catalyzer that above-mentioned patent is mentioned all adopts the catalyzer containing certain proportion binding agent, and the existence of binding agent reduces the mass transfer ability of catalyzer, causes catalyst utilization low, intensity difference.Simultaneously due to the crucial rate-determining steps that liquid phase method reaction mass transfer is reaction, the inactivation of catalyzer is mainly that the pollution in catalyzer aperture is relevant with catalyzer duct heavy deposition component.Reactant reacts fast and leaves catalyzer microchannel is fast the key that catalyst stability improves.

Summary of the invention

Technical problem to be solved by this invention is that to there is catalyst utilization in prior art lower, and catalyst strength is poor, and the problem of active, poor stability, provides a kind of new liquid phase to shift the method for producing ethylbenzene.It is high that the method has reactive behavior, the feature that catalyst stability is good, intensity is good.

For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for ethylbenzene is produced in the transfer of a kind of liquid phase, with multi-ethyl phenenyl and benzene for reaction raw materials, temperature of reaction 100 ~ 260 DEG C, reaction pressure 2.0 ~ 4.5MPa, liquid phase weight air speed 1 ~ 10 hour -1, under the condition of benzene/multi-ethyl phenenyl weight ratio 1 ~ 10, reaction raw materials and catalyst exposure generation liquid phase shift reaction generate ethylbenzene; Wherein, described catalyzer is SiO 2/ Al 2o 3mol ratio is the binder free Beta type molecular sieve of 5 ~ 200.

In technique scheme, preferably, in described binder free Beta type molecular sieve, the content of molecular sieve is greater than 95 % by weight.

In technique scheme, preferably, described binder free Beta type molecular sieve SiO 2/ Al 2o 3mol ratio is 20 ~ 60.

In technique scheme, preferably, described binder free Beta type molecular sieve is through steam-treated.More preferably, steam-treated is carried out under containing the water vapour atmosphere of 10 ~ 100 % by weight, and treatment temp is 400 ~ 800 DEG C, and the treatment time is 0.5 ~ 24 hour, and the weight space velocity of water vapour is 1 ~ 10 hour -1.

In technique scheme, preferably, temperature of reaction is 150 ~ 240 DEG C.

In technique scheme, preferably, reaction pressure is 2.5 ~ 4.0MPa.

In technique scheme, preferably, liquid phase weight air speed is 1 ~ 5 hour -1.

In technique scheme, preferably, benzene/multi-ethyl phenenyl weight ratio is 1 ~ 5.

In technique scheme, preferably, the many ethylbenzene of raw material is pure ethylene method, rare ethylene process or alcohol legal system be for the many ethylbenzene produced in ethylbenzene.

Binder free Beta type molecular sieve in the inventive method is by SiO 2/ Al 2o 3mol ratio is that the Beta type molecular screen primary powder of 5 ~ 200 is according to the alkaline matter of butt weight 20 ~ 80% and 0.1 ~ 15%, the compound of aluminium of 0.1 ~ 10% and the compound of the silicon of 10 ~ 80% and water mixing, grind shaping, extrusion, dry, obtain through aftertreatment again after roasting.Wherein, described alkaline matter is selected from sodium hydroxide, and the compound of aluminium is selected from sodium metaaluminate, and the compound of silicon is selected from silicon-dioxide.The optimum ratio of raw material is: Beta type molecular screen primary powder according to the alkaline matter of butt weight 50 ~ 60% and 0.5 ~ 5%, the compound of aluminium of 1 ~ 5 and the compound of the silicon of 40 ~ 60%.

Above-mentioned post-processing step comprises:

A, is placed in Autoclaves for synthesis by above-mentioned strip catalyst, and synthesis reactor bottom loads deionized water, catalyzer is placed on stainless (steel) wire, and ensures that catalyzer does not contact with the water of autoclave base, sealing autoclave.Static crystallization 5 ~ 200 hours at 90 ~ 200 DEG C of temperature, opens the catalyzer after still taking-up crystallization.Wherein, the optimum condition of crystallization is: 100 ~ 180 DEG C, crystallization 10 ~ 30 hours.

B, the catalyzer deionized water wash taken out by step a at least one times, is dried, roasting.

C, carries out conventional ammonium ion exchange at least one times, preferably four times by above-mentioned Adhesive-free Molecular Sieve; Steam roasting process.

D, repeating step c once, namely obtain the binder free Beta type molecular sieve after crystallization.

In above-mentioned steps, bake out temperature is 100 ~ 150 DEG C, and drying time is 1 ~ 10 hour; Maturing temperature is 400 ~ 600 DEG C, and roasting time is 1 ~ 10 hour.

In the inventive method, ammonium ion exchange treatment process is the conventional method adopted in prior art, and the present invention has no particular limits it.Such as use the ammonium salt solution of weight concentration 1 ~ 20%, under 0 ~ 100 DEG C of condition, process 0.5 ~ 24 hour.Described ammonium salt is selected from least one in ammonium nitrate, ammonium chloride, ammonium oxalate, ammonium sulfate or ammonium citrate.Described exchange generally also comprises filtration, water-washing step.In the present invention, steam roasting treatment process is the conventional method adopted in prior art, and the present invention has no particular limits it.Such as at 400 ~ 800 DEG C, under containing the water vapour atmosphere of 10 ~ 100%, carry out steam roasting process 0.5 ~ 24 hour.

The inventive method can be used for the liquid phase transfer process of many ethylbenzene component and the benzene produced by the rare ethylbenzene manufactured from ethylene alkylation process in ethene or catalytic cracked dry gas, also can be used for the liquid phase transfer process of many ethylbenzene component and the benzene produced by alcohol legal system ethylbenzene alkylation process.

The inventive method adopts binder free Beta type molecular sieve as liquid phase transfer catalyst, binder free Beta type molecular sieve adds the content of wherein Beta type molecular sieve, eliminating binding agent parcel, to cover the activity brought of active ingredient low, the unfavorable factor of expanding restriction, molecular sieve intergrowth simultaneously, the content of molecular sieve can reach more than 98%, thus substantially increases the intensity of catalyzer.Adopt the inventive method, catalyst utilization is high, and activity can up to 81.5%, good stability, and catalyst regeneration cycle can reach more than 2 years, achieves good technique effect.

Further instruction is given to the present invention below by embodiment.

Embodiment

[embodiment 1]

Take the former powder (SiO of Beta type 2/ Al 2o 3than being 25) 40g, sodium aluminate 5.217g, sodium hydroxide 2g, silica 1 0.5g, deionized water 24g, sesbania powder 4g.Be put in ceramic mortar and mix.Extruded moulding.Dry in 110 DEG C of baking ovens and spend the night, roasting 6 hours in 550 DEG C of retort furnaces.Be placed in Autoclaves for synthesis, bottom synthesis reactor, fill deionized water, put shaping catalyzer with stainless (steel) wire on reactor top, ensure that catalyzer does not contact with water.Then 150 DEG C of crystallization 10 hours.Use deionized water wash 2 times after taking out, dry, for subsequent use after roasting.

Catalyzer subsequently after roasting is in the ammonium nitrate solution of 5% in weight concentration, stirs 4 hours, centrifuging at 90 DEG C, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 4 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Then stop passing into water vapor, be down to room temperature, then be the aqueous ammonium nitrate solution of 5% with weight concentration, stirring 4 hours at 90 DEG C, with deionized water wash 2 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Namely finished catalyst is obtained.

 

[embodiment 2 ~ 9]

With [embodiment 1], just shaping ratio is different with the condition of Crystallizing treatment.Specifically in table 1.

Table 1

[embodiment 10]

Investigate catalyst reaction performance with fixed-bed reactor from bottom to top, reactor is the stainless steel tube of internal diameter 28 millimeters, length 800 millimeters.Loaded catalyst is 3 grams, and is diluted to 10ml with granulated glass sphere.

After the catalyst loading of [embodiment 1 ~ 9] is entered reactor, under nitrogen protection catalyzer is activated, at 400 DEG C, activate 1 hour.Then be cooled to less than 40 DEG C, stop nitrogen purging, start into transalkylation material, after the value that pressure reaches set, start to be warming up to temperature of reaction.

Reaction conditions is: temperature 250 DEG C, pressure 4.0MPa, total liquid phase air speed 1.5 hours -1, benzene and diethylbenzene weight ratio 1:1.After system stability, timing is got product liquid and is carried out stratographic analysis.Following data are all the charging stable data of 10 hours, specifically in table 2.

 

[comparative example 1]

Take the former powder (SiO of Beta type 2/ Al 2o 3than being 25) 40g, sesbania powder 4g, the dust technology 22g of 5% and aluminum oxide are that 80:20 is shaping according to butt weight ratio, with post-drying, roasting.

In weight concentration be subsequently 5% ammonium nitrate solution in, to stir 4 hours at 90 DEG C, centrifuging, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 4 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Then stop passing into water vapor, be down to room temperature, then be the aqueous ammonium nitrate solution of 5% with weight concentration, stirring 4 hours at 90 DEG C, with deionized water wash 2 times.Subsequently in 650 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Namely finished catalyst is obtained.Then investigate catalyzer initial activity with [embodiment 10], the results are shown in Table 2.

Table 2

Catalyzer Diethylbenzene transformation efficiency, % Ethylbenzene selectivity, % Catalyst strength, N/cm Embodiment 1 81.50 98.11 115 Embodiment 2 78.23 98.25 98 Embodiment 3 76.26 98.82 87 Embodiment 4 80.91 98.66 92 Embodiment 5 79.87 98.84 93 Embodiment 6 75.43 96.43 109 Embodiment 7 73.45 97.10 94 Embodiment 8 72.77 98.42 91 Embodiment 9 50.56 90.15 75 Comparative example 1 52.45 96.33 47

By carrying out XRD spectra analysis to the catalyzer before and after crystallization, can find that the degree of crystallinity of crystallization rear catalyst increases; This shows that the binding agent part between molecular sieve there occurs conversion, and the molecular sieve content of catalyzer is added.As can be seen from Table 2, the catalyzer of identical weight, binder free catalyzer due to the content of molecular sieve high, mass transfer velocity is fast, and catalyzer can bear higher air speed, and the intensity of catalyzer have also been obtained and significantly improves simultaneously.

 

[comparative example 2]

Take industrial raw powder (SiO 2/ Al 2o 3than being 30) Beta type molecular screen primary powder 40g, be that 80:20 is shaping with aluminum oxide according to butt weight ratio, with post-drying, roasting.

By weight concentration be subsequently 10% ammonium nitrate solution in, to stir 4 hours at 90 DEG C, centrifuging, and with deionized water wash 2 times.Repeat above-mentioned ammonium ion exchange process 4 times.Subsequently in 550 DEG C, under the water vapour atmosphere of 100%, process 4 hours.Then stop passing into water vapor, be down to room temperature, then be the aqueous ammonium nitrate solution of 10% with weight concentration, stirring 4 hours at 90 DEG C, with deionized water wash 2 times.

 

[embodiment 11]

Investigate catalyst reaction performance with fixed-bed reactor from bottom to top, reactor is the stainless steel tube of internal diameter 28 millimeters, length 800 millimeters.Loaded catalyst is 3 grams, and is diluted to 10ml with granulated glass sphere.

After the catalyst loading of [embodiment 1 ~ 9], [comparative example 1,2] is entered reactor, under nitrogen protection catalyzer is activated, at 400 DEG C, activate 1 hour.Then be cooled to less than 40 DEG C, stop nitrogen purging, start into transalkylation material, after the value that pressure reaches set, start to be warming up to temperature of reaction.

Reaction conditions is: temperature 250 DEG C, pressure 4.0MPa, total liquid phase air speed 7.0 hours -1, benzene and diethylbenzene weight ratio 1:1.After system stability, timing is got product liquid and is carried out stratographic analysis.Following data are all the charging stable data of 10 hours, specifically in table 3.

Table 3

Catalyzer Diethylbenzene transformation efficiency, % Ethylbenzene selectivity, % Deactivation rate, %/h Embodiment 1 72.11 97.11 0.105 Embodiment 2 69.35 97.00 0.186 Embodiment 3 70.71 98.12 0.175 Embodiment 4 65.50 97.36 0.192 Embodiment 5 61.55 98.13 0.210 Embodiment 6 66.39 97.22 0.109 Embodiment 7 64.15 97.14 0.300 Embodiment 8 64.17 98.62 0.391 Embodiment 9 40.26 95.55 0.386 Comparative example 1 38.02 97.54 0.422 Comparative example 2 48.02 94.68 0.435

As can be seen from Table 3, because the active component content of binder free catalyzer is high, active better, simultaneously without covering and the parcel of binding agent, the mass transfer ability of catalyzer improves, and product is easier to diffuse out, and be unlikely to accumulation inactivation, so activity stability is better.

Claims (10)

1. the method for ethylbenzene is produced in liquid phase transfer, with multi-ethyl phenenyl and benzene for reaction raw materials, temperature of reaction 100 ~ 260 DEG C, and reaction pressure 2.0 ~ 4.5MPa, liquid phase weight air speed 1 ~ 10 hour -1, under the condition of benzene/multi-ethyl phenenyl weight ratio 1 ~ 10, reaction raw materials and catalyst exposure generation liquid phase shift reaction generate ethylbenzene; Wherein, described catalyzer is SiO 2/ Al 2o 3mol ratio is the binder free Beta type molecular sieve of 5 ~ 200.
2. the method for ethylbenzene is produced in liquid phase transfer according to claim 1, it is characterized in that in described binder free Beta type molecular sieve, the content of molecular sieve is greater than 95 % by weight.
3. the method for ethylbenzene is produced in liquid phase transfer according to claim 1, it is characterized in that described binder free Beta type molecular sieve SiO 2/ Al 2o 3mol ratio is 20 ~ 60.
4. the method for ethylbenzene is produced in liquid phase transfer according to claim 1, it is characterized in that described binder free Beta type molecular sieve is through steam-treated.
5. the method for ethylbenzene is produced in liquid phase transfer according to claim 4, it is characterized in that steam-treated is carried out under containing the water vapour atmosphere of 10 ~ 100 % by weight, treatment temp is 400 ~ 800 DEG C, and the treatment time is 0.5 ~ 24 hour, and the weight space velocity of water vapour is 1 ~ 10 hour -1.
6. the method for ethylbenzene is produced in liquid phase transfer according to claim 1, it is characterized in that temperature of reaction is 150 ~ 240 DEG C.
7. the method for ethylbenzene is produced in liquid phase transfer according to claim 1, it is characterized in that reaction pressure is 2.5 ~ 4.0MPa.
8. the method for ethylbenzene is produced in liquid phase transfer according to claim 1, it is characterized in that liquid phase weight air speed is 1 ~ 5 hour -1.
9. the method for ethylbenzene is produced in liquid phase transfer according to claim 1, it is characterized in that benzene/multi-ethyl phenenyl weight ratio is 1 ~ 5.
10. the method for ethylbenzene is produced in liquid phase according to claim 1 transfer, it is characterized in that the many ethylbenzene of raw material is pure ethylene method, rare ethylene process or alcohol legal system be for the many ethylbenzene produced in ethylbenzene.
CN201310286115.7A 2013-07-09 2013-07-09 Method for producing ethylbenzene by liquid-phase transalkylation CN104276922A (en)

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CN107511173A (en) * 2016-06-18 2017-12-26 中国石油化工股份有限公司 The production method of alkylbenzene

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Application publication date: 20150114

RJ01 Rejection of invention patent application after publication