CN1597110A - Catalyst for producing ethyl benzene from multi ethyl benzene and benzene - Google Patents

Catalyst for producing ethyl benzene from multi ethyl benzene and benzene Download PDF

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Publication number
CN1597110A
CN1597110A CNA031588824A CN03158882A CN1597110A CN 1597110 A CN1597110 A CN 1597110A CN A031588824 A CNA031588824 A CN A031588824A CN 03158882 A CN03158882 A CN 03158882A CN 1597110 A CN1597110 A CN 1597110A
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catalyzer
benzene
molecular sieve
ethylbenzene
oven dry
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徐龙伢
谢素娟
王清遐
刘盛林
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

A catalyst for preparing ethylbenzene from polyethylene benzene and benzene by liquid-phase alkyl transfer reaction is prepared from the MCM-22 molecular sieve whose mole ratio of SiO2 to Al2O3 is 20-50, halogen and inertial component. It is acidic catalyst.

Description

A kind of multi-ethyl phenenyl and benzene are produced the catalyzer of ethylbenzene
Technical field
The present invention relates to a kind of catalyzer, specifically, relate to a kind of being used for to produce the ethylbenzene catalyzer, be particularly suitable under the liquid-phase condition multi-ethyl phenenyl and benzene by the process of transalkylation reaction production ethylbenzene by multi-ethyl phenenyl and benzene.
Background technology
Alkylaromatic hydrocarbon is the intermediates with extensive use, wherein topmost as the Chemical Manufacture critical materials be ethylbenzene, the ethylbenzene ultimate production reaches 2,000 ten thousand tons/year in the world.Having developed multiple since later 1930s is the catalyzer and the corresponding processing method of raw material system ethylbenzene with ethene and benzene.
Producing in the process of alkylaromatic hydrocarbon by alkene and benzene alkylation, because the characteristics of alkylated reaction itself, exist a certain amount of many alkylaromatic hydrocarbons in the alkylate, this has not only reduced the utilization ratio of olefin feedstock, and the purity of product is descended, best method is that many alkylaromatic hydrocarbons and benzene are carried out transalkylation reaction manufacture order alkylaromatic hydrocarbon, thereby improves the output of monoalkyl aromatic hydrocarbons.
USP5600048 has disclosed a kind of liquid-phase alkylation-gas phase transalkylation and has produced the ethylbenzene process, and the transalkylation catalyst that is adopted is the ZSM-5 molecular sieve, and the per pass conversion of multi-ethyl phenenyl is 45%.
CN1139658A has disclosed the process that diethylbenzene and benzene are produced ethylbenzene under a kind of gas phase condition by transalkylation.Catalyzer is the silico-aluminate of atomic ratio between 50 and 150 of Si/Al, the characteristics of catalyzer be average mean crystal size less than 0.5 μ m, and wherein about 90% crystal has the granularity less than 0.70 μ m; Its maximum diameter of hole is between 100 to 180 nanometers.
Disclosed a kind of paste state bed reactor technology among the CN1058011A, the transalkylation process of the polyalkylbenzene under liquid-phase condition, the catalyzer of employing are phosphoric acid, AlCl 3, BF 3/ HF and commercial with y-type zeolite etc.
Disclosed a kind ofly in autoclave among the CN1097187A, diethylbenzene and triethyl-benzene are at AlCl under 160 ℃ of conditions 3Transalkylation reaction takes place down in the effect of-vinylchlorid, and the multi-ethyl phenenyl transformation efficiency is less than 30%.
CN11811367A, CN1199727A, USP5030786 etc. have reported in succession under liquid-phase condition, multi-ethyl phenenyl and benzene are produced the method for ethylbenzene by transalkylation reaction, catalyzer is a Y zeolite, at the transformation efficiency that guarantees can reach by attemperation and pressure under the liquid-phase condition corresponding multi-ethyl phenenyl.
CN1096025A, USP4891458 etc. have reported that benzene and diethylbenzene reaction under the liquid-phase condition produces the process of ethylbenzene, and adopting the H beta-molecular sieve is catalyzer, and under 3.5MPa, 260 ℃ condition, the transformation efficiency of diethylbenzene is 57%.
USP5600050, CN1128249A, CN1096470A have disclosed a kind of liquid-phase alkylation-liquid phase transalkylation and have produced the ethylbenzene process, and the catalyzer that its transalkylation process adopted is identical with alkylation catalyst, it is characterized by: catalyzer is with Si 2O/Al 2O 3Be that 20～40 H beta-molecular sieve is an active constituent, contain the chlorine or the fluorine of 0.5～10% (weight), all the other components are γ-Al 2O 3Transalkylation conditions is: reaction pressure 3.8MPa, and 260 ℃ of temperature of reaction, benzene/alkylbenzene molecular ratio is 5～10, the liquid weight air speed is 3h -1
CN1207960A has disclosed a kind of liquid-phase alkylation-liquid phase transalkylation and has produced the ethylbenzene process, its transalkylation process catalyzer is through rare earth or alkali-earth metal modified beta-molecular sieve, 230～280 ℃ of temperature, pressure 2.3～4.3MPa, benzene/many ethylbenzene mol ratio is 8～12, and benzene and many ethylbenzene weight space velocity are 6～10h -1Condition under, the transformation efficiency of multi-ethyl phenenyl is about 45%.
Present patent application contriver once proposed the method at rare ethene and/or propylene system ethylbenzene and/or isopropyl benzene in Chinese patent (application number is respectively 97115471.1 and 99112833.8), it is respectively Fixed Bed Gas Phase alkylation-gas phase transalkylation process and vapor-phase alkylation-liquid phase transalkylation process, and the catalyzer of having invented the liquid phase transalkylation in Chinese patent (application number is respectively 01104361.x and 01104362.8) is beta-molecular sieve catalyzer and Y molecular sieve catalyzer, by producing the industrial application of 30,000 tons of ethylbenzene scales per year, obtain good result, produced remarkable economic efficiency and social benefit.
Summary of the invention
The object of the present invention is to provide multi-ethyl phenenyl and benzene under a kind of liquid-phase condition to produce the MCM-22 molecular sieve catalyst of ethylbenzene by transalkylation reaction, this catalyzer has production cost and the better catalyst reaction performance lower than beta-molecular sieve catalyzer, be used for multi-ethyl phenenyl and benzene and produce the ethylbenzene process by the liquid phase transalkylation reaction, the per pass conversion of multi-ethyl phenenyl is greater than 70%, the selectivity that generates ethylbenzene is more than 99%, thereby increased ethylbenzene output.
Another object of the present invention is to provide above-mentioned Preparation of catalysts method.
For achieving the above object, provided by the invention being used for produced the ethylbenzene catalyzer by multi-ethyl phenenyl and benzene, constitute by MCM-22 molecular sieve, halogen and inertia component, wherein:
SiO 2/ Al 2O 3Mol ratio is that 20～50 the weight of MCM-22 molecular sieve in catalyzer is 20～90%;
The weight of halogen is 0～5%;
All the other are in inert material alchlor, silicon-dioxide, clay and the diatomite one or more.
The acid characteristics of above-mentioned catalyzer are: every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 5 * 10 20～20 * 10 20Individual, the ratio at wherein 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.
Above-mentioned catalyst acid center number NH 3-TPD method is measured.With He is carrier gas, flow 20ml/min, and catalyst levels 140mg, granular size is 40～60 orders.Sample is at room temperature inhaled earlier ammonia to saturated, is warming up to 600 ℃ of activation 120min then, reduces to room temperature then and inhales ammonia to saturated.After the ammonia of physical adsorption is removed in He air-blowing cleaning, carry out desorption with 20 ℃/min temperature rise rate, after reaching 600 ℃, desorption temperature keeps 30min, and the ammonia under the desorption is analyzed quantitatively with chromatogram (thermal conductivity cell detector).
Na in the above-mentioned catalyzer 2O content is by weight smaller or equal to 0.05%.
Halogen in the above-mentioned catalyzer is preferably fluorine or chlorine.
The method of the above-mentioned catalyzer of preparation provided by the invention is:
A) with MCM-22 molecular sieve and inert material kneading and compacting in proportion, after 100～140 ℃ of oven dry, 400～600 ℃ of roastings 1～20 hour;
B) with step a gained forming composition with ammonium salt solution 80～90 ℃ of exchanges, then with deionized water wash to neutral, 100～140 ℃ of oven dry;
C) with the resulting product of step b 400～600 ℃ of roastings 1～10 hour;
D) the prepared product of step c was handled 1～10 hour with saturated steam at 250～500 ℃, made finished catalyst.
Among the above-mentioned preparation method, step b products therefrom can also be carried out vacuum impregnation with halogen solution, after 100～140 ℃ of oven dry, c and steps d are prepared set by step again, get finished catalyst.
Catalyzer provided by the present invention reacts the activation that need heat up before under inert gas atmosphere, the activation condition of catalyzer is: 300～500 ℃ of temperature, and pressure 0.1～1.0Mpa, the flow of rare gas element are per hour 0.1～10 liter of every milliliter of catalyzer; Rare gas element is N 2, one or more the mixture among Ar and the He.
The reaction conditions that ethylbenzene is produced in multi-ethyl phenenyl of the present invention and benzene reaction is: reaction pressure 1.5～7.0MPa, 150～350 ℃ of temperature of reaction, raw material weight air speed 0.5～8h -1, benzene and multi-ethyl phenenyl molecular ratio be 2～15.
Provided by the present invention by multi-ethyl phenenyl and benzene by transalkylation reaction manufacture order alkylbenzene catalyzer, can be applied to fixed bed, starch various types of reactors such as attitude bed.
Embodiment
Provide embodiment below, do not limit its scope because of embodiment.
Embodiment 1: get SiO 2/ Al 2O 3Mol ratio is 30 NaMCM-22 molecular sieve and Al 2O 3Powder mixes the moulding of pinching bar according to 70: 30 weight ratio, after 120 ℃ of oven dry 540 ℃ of roastings 4 hours; The gained bar is exchanged 3 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, 120 ℃ of oven dry; With 1.1%HF solution aforementioned oven dry thing is carried out vacuum impregnation; Dipping back bar is through, handling 2 hours with saturated steam in 300 ℃ after 2 hours 500 ℃ of roastings after 120 ℃ of oven dry; Make catalyst A, wherein F content is 0.8%, Na 2O content is 0.02%, and every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 10.1 * 10 20Individual, the ratio at wherein 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 60: 40.
Embodiment 2: get SiO 2/ Al 2O 3Mol ratio is that 45 NaMCM-22 molecular sieve and clay powder mix the moulding of pinching bar according to 80: 20 weight ratio, after 120 ℃ of oven dry 530 ℃ of roastings 7 hours; The gained bar is exchanged 4 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, 120 ℃ of oven dry; With 1.8%HCl solution aforementioned bar is carried out vacuum impregnation; Dipping back bar makes catalyst B through handling 2 hours with saturated steam in 320 ℃ after 3 hours 490 ℃ of roastings after 120 ℃ of oven dry, and wherein Cl content is 1.4%, Na 2O content is 0.03%, and every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 14.8 * 10 20Individual, the ratio at wherein 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 63: 37.
Embodiment 3: get SiO 2/ Al 2O 3Mol ratio is 25 NaMCM-22 molecular sieve and Al 2O 3Powder mixes the moulding of pinching bar according to 55: 45 weight ratio, after 120 ℃ of oven dry 550 ℃ of roastings 3 hours; The gained bar is exchanged 3 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, 120 ℃ of oven dry; Aforesaid strip catalyst was handled 3 hours with saturated steam in 490 ℃, made catalyzer C, Na 2O content is 0.04%, and every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 10.3 * 10 20Individual, the ratio at wherein 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 55: 45.
Embodiment 4: get SiO 2/ Al 2O 3Mol ratio is 25 NaMCM-22 molecular sieve and Al 2O 3Powder mixes the moulding of pinching bar according to 30: 70 weight ratio, after 120 ℃ of oven dry 540 ℃ of roastings 3 hours; The gained bar is exchanged 3 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, 120 ℃ of oven dry; With 4.5%HF solution aforementioned oven dry thing is carried out vacuum impregnation; Dipping back bar is through, handling 2 hours with saturated steam in 300 ℃ after 2 hours 500 ℃ of roastings after 120 ℃ of oven dry; Make catalyzer D, wherein F content is 2.5%, Na 2O content is 0.02%, and every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 7.6 * 10 20Individual, wherein middle strong acid center (330～600 ℃ of ammonia desorption relative acid centers) and weak acid center (150～330 ℃ of ammonia desorption relative acid centers) ratio are 45: 55.
Embodiment 5: 100 milliliters of scale fixed beds that with the internal diameter are Φ 20 are reactor, to the 16-20 order catalyzer of wherein packing into, at N 2Lower the temperature behind the activation 1h under atmosphere, 0.3MPa and the 500 ℃ of conditions, when reaction bed temperature is lower than predetermined 10 ℃ of left and right sides of temperature of reaction, use N 2Make reactive system be raised to reaction pressure, and with pump the mixing solutions of preparing according to certain benzene/diethylbenzene mol ratio is sent into reactor, simultaneously temperature is adjusted to temperature of reaction, begin to carry out transalkylation reaction, reaction result sees Table 1.
The liquid phase transalkylation reaction result of table 1 different catalysts
Catalyzer Catalyst A Catalyst B Catalyzer C Catalyzer D
Reaction pressure (MPa) ??3.0 ??2.9 ??3.2 ??3.5
Temperature of reaction (℃) ??230 ??235 ??225 ??265
Raw material weight air speed (h -1) ????1.0 ????1.0 ????2.0 ????4.0
Benzene/diethylbenzene molecular ratio ????6 ????5 ????6 ????10
Diethylbenzene transformation efficiency (%) ????77 ????78 ????75 ????71
Generate ethylbenzene selectivity (%) ????99.1 ????99.1 ????99.2 ????99.0
Xylene content (ppm) ????126 ????123 ????112 ????167

Claims (7)

1, a kind of multi-ethyl phenenyl and benzene are produced the ethylbenzene catalyzer, are made of MCM-22 molecular sieve, halogen and inertia component, it is characterized in that:
SiO 2/ Al 2O 3Mol ratio is that 20～50 the weight of MCM-22 molecular sieve in catalyzer is 20～90%;
The weight of halogen is 0～5%;
All the other are in inert material alchlor, silicon-dioxide, clay and the diatomite one or more.
2, according to the described catalyzer of claim 1, it is characterized in that its acid characteristics are: every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid centers) 5 * 10 20～20 * 10 20Individual, the ratio at wherein 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.
3, according to the described catalyzer of claim 1, it is characterized in that: Na in the catalyzer 2O content is by weight smaller or equal to 0.05%.
4, according to the described catalyzer of claim 1, it is characterized in that: the halogen in the catalyzer is a fluorine or chlorine.
5, a kind of method for preparing each described catalyzer of claim 1-4 is:
A) with MCM-22 molecular sieve and inert material kneading and compacting in proportion, after 100～140 ℃ of oven dry, 400～600 ℃ of roastings 1～20 hour;
B) with step a gained forming composition with ammonium salt solution 80～90 ℃ of exchanges, then with deionized water wash to neutral, 100～140 ℃ of oven dry;
C) with the resulting product of step b 400～600 ℃ of roastings 1～10 hour;
D) the prepared product of step c was handled 1～10 hour with saturated steam at 250～500 ℃, made finished catalyst.
According to the described preparation method of claim 5, it is characterized in that 6, step b products therefrom carries out vacuum impregnation with halogen solution, after 100～140 ℃ of oven dry, and then c and steps d are prepared set by step.
7, according to the application of the described catalyzer of above-mentioned each claim in multi-ethyl phenenyl and benzene production ethylbenzene.
CNA031588824A 2003-09-16 2003-09-16 Catalyst for producing ethyl benzene from multi ethyl benzene and benzene Pending CN1597110A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1296133C (en) * 2004-01-19 2007-01-24 中国石油化工股份有限公司 Catalyst containing MCM-22 zeolite
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
CN114534777A (en) * 2020-11-26 2022-05-27 中国科学院大连化学物理研究所 Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1296133C (en) * 2004-01-19 2007-01-24 中国石油化工股份有限公司 Catalyst containing MCM-22 zeolite
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
CN114534777A (en) * 2020-11-26 2022-05-27 中国科学院大连化学物理研究所 Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene
CN114534777B (en) * 2020-11-26 2023-04-14 中国科学院大连化学物理研究所 Preparation method of molecular sieve catalyst for reaction of polyethylbenzene and benzene

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