CN1022404C - Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst - Google Patents

Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst Download PDF

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CN1022404C
CN1022404C CN87105054A CN87105054A CN1022404C CN 1022404 C CN1022404 C CN 1022404C CN 87105054 A CN87105054 A CN 87105054A CN 87105054 A CN87105054 A CN 87105054A CN 1022404 C CN1022404 C CN 1022404C
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zeolite
ammonium
ethylene
catalyst
ethylbenzene
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CN1031072A (en
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王清遐
张淑蓉
蔡光宇
魏永祯
李峰
黄祖贤
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NO 2 PETROLEUM FACTORY FUSHUN
Dalian Institute of Chemical Physics of CAS
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NO 2 PETROLEUM FACTORY FUSHUN
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)

Abstract

The present invention relates to a Pentasil-type silicon-aluminum zeolite catalyst which comprises a rare-earth element and is used for the alkylation reaction of benzene and ethylene, particularly to used for a phenylating reaction process with the raw material of the ethylene with low concentration. With the utilization of the catalyst, refinery tail gas (containing 10% to 20% of the ethylene) containing the impurities of hydrogen sulphide, water, etc. can be directly used as a raw material to react with the benzene for preparing ethylbenzene. Compared with a congener catalyst used in current industries, the catalyst of the present invention has favorable reacting performance, operational stability of the reaction and simple production technique.

Description

Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst
The present invention a kind ofly is used for benzene and ethene carries out alkylated reaction, is applicable to that particularly directly benefiting from low-concentration ethane is benzene alkylation reaction process catalyst system therefor of raw material and preparation method thereof.
Ethylbenzene is the critical materials of producing polystyrene plastic.So far, the industrial making method of ethylbenzene mainly contains two kinds, and is a kind of for the carbon eight fraction fractionation by petroleum reforming oil get, and another kind of more main method is to be produced through catalytic alkylation reaction by benzene and ethene.A kind of method in back has developed multiple commercial run with different characteristics since the beginning industrialization of the '30s end.But the overwhelming majority in these methods all is that the ethene of employing high density (even polymerization-grade) is raw material, and certain limitation is arranged.
Along with the development of petroleum refining industry, discharge the refinery exhaust that contains low-concentration ethane (content 10～20%) in a large number day by day; For the utilization of ethene in these tail gas, from the fifties end, developed and severally produced the method for ethylbenzene by it, these methods are mainly as U.S. Pat 2,939,890; US3,691,245; US3,702,886; US3,848,012; US4,107,224; US4,459,426; English Patent BP827,830; BP1,162,481; Deutsches Reichs-Patent DE2,756,221; And Romanian patent RO.51, patents such as 253 are reported.Their catalyst system therefors roughly can be divided into three types: AlCl 3, BF 3Perhaps crystalline silico-alumino zeolite.Main with ZSM-5 type zeolite in Si-Al zeolite, this prepare zeolite is to do crystallization promotor with the tetrapropyl ammonium compound.
But the H of these processes to being contained in the unstripped gas 2S, H 2O, CO, CO 2And O 2Deng foreign matter content strict requirement is arranged all, need be removed to the ppm level in advance, alkylation process is normally carried out.Because in these impurity, what have will make AlCl 3The catalyst consumption amount is order of magnitude ground to be increased so that inactivation, makes BF 3Poisoning of catalyst inactivation and hydrolysis produce hydrofluoric acid and cause the equipment heavy corrosion, perhaps can accelerate the aging speed of ZSM-5 type zeolite catalyst, shorten the operational cycle greatly.Therefore, these methods all will additionally be set up the pre-refining device of unstripped gas, thereby bring shortcomings such as complex procedures, operational difficulty.
The objective of the invention is to prepare a kind of benzene alkylation with ethylene, particularly be applicable to the catalyzer that adopts the refinery exhaust (as catalytic cracked dry gas) contain low-concentration ethane to use for the benzene alkylation processes of reaction raw materials, this catalyzer not only has activity and selectivity preferably, and the H that exists in raw material 2S and H 2Under the condition that detrimental impurity such as O do not need to remove in advance, still have advantages of higher stability, the long operational cycle, thereby can improve the process economy benefit and improve its adaptability.
Catalyzer of the present invention is to be the primary activity component with Pentasil type Si-Al zeolite, the type zeolite system is synthesized during by crystallization promotor with ammonium hydroxide or diamine, and when synthetic the direct halogenation salt of interpolation rare earth element, in the crystalline silico-alumino zeolite that makes, add 30～70% binding agent kneading and compactings then, change Hydrogen into through ammonium salt exchange and roasting, handle making finished catalyst again through further upgrading.
The present invention adopts chemistry and physics upgrading treatment process, to regulate the intensity and the quantity of zeolite catalyst surface acid center.In addition, also adopt the super stabilizing means, to strengthen the operation stability of zeolite catalyst.For ease of to the control of zeolite surface tart, adopt conventional adsorb ammonia temperature programmed desorption(TPD) (TPD) method to detect and control device as main.At last catalyzer being carried out prevulcanized and handle, specifically is to adopt the wet method method for pre-sulphuration, introduces the sulphur component, with selectivity and the stability of improving zeolite catalyst.
The weight percent that zeolite catalyst of the present invention is formed is: mishmetal 0.3～6% or lanthanum 0.2～3%, sulphur 0.05～0.2%, zeolite (its SiO 2/ Al 2O 3Ratio 40～100) content 30～70%, and Al 2O 3Content 70～30%.
The preparation process of zeolite catalyst is:
One, zeolite is synthetic
With water glass (or water glass) and ammonium hydroxide (or diamine); Tai-Ace S 150 (or sodium metaaluminate), sulfuric acid and rare earth halide, be hybridly prepared into solution respectively, under violent stirring, two solution are mixed into glue, colloid moves into crystallization in the autoclave, crystallization condition is a crystallization 10 hours to 7 days under 100～200 ℃ of conditions, is preferably in 110-170 ℃ of following crystallization 3～4 days.After crystallization is finished, filter, wash and drying, can obtain containing the Pentasil Si-Al zeolite of rare earth.The physico-chemical property of this zeolite is: SiO 2/ Al 2O 3(molecular ratio) 40～100, content of rare earth 0.3～6%Wt or lanthanum 0.2～3%Wt, surface-area 340～380m 2/ g.The loading capacity of normal hexane, hexanaphthene and water is respectively: 9～11.5%wt, 4～5%Wt and 7～9%Wt.
Two, Preparation of catalysts
1. with above-mentioned synthetic zeolite and a certain amount of aluminum oxide, it is kneaded and formed to add an amount of diluted nitric acid aqueous solution again, oven dry, roasting under the condition of inert gas and progressively intensification;
2. with above-mentioned zeolite product ammonium salt (the most handy ammonium nitrate and the ammonium hydroxide mix) aqueous solution, exchange becomes the ammonium type, and 80～90 ℃ of ion-exchange temperatures are so that this half-finished sodium content is brought down below 0.05～0.02%Wt;
With above-mentioned ammonium type zeolite product at inert gas and changing into again under the full air, in 450～540 ℃, roasting is more than 6 hours;
4. above-mentioned h-type zeolite product is then carried out hydrothermal treatment consists, condition is flooding quantity 2～20ml/g sample, hour, 500～650 ℃ of temperature and time are more than 2～10 hours;
5. the Pentasil type zeolite catalyst after above-mentioned processing is again with sulfidizing, dry method or wet method all can, vulcanizing agent such as H 2S, SO 2And ammonium sulfide all can, but preferably adopt the wet method sulfidizing, the employing ammonium sulfide is a vulcanizing agent, uses hydrogen treat subsequently again, get final product finished product Pentasil type zeolite catalyst.
Embodiment 1: prepare zeolite
Get 2889 milliliters and contain Na 2O62.58mg/ml and SiO 2193.21mg/ml water glass solution, 1980 ml pure waters and 244 the gram concentration 98% quadrols mix; Other gets content is 99% Al 2(SO 4) 318H 2The O69.3 gram, 482 milliliters in 4M sulfuric acid, content are 99%LaCl 36H 22000 milliliters of O29.9 gram and pure water, and mix; Under violent stirring, two solution are mixed into glue, present and continue again behind the glue to stir 30 minutes, gelatigenous object is transferred in rotary (or stirring-type) stainless steel autoclave that volume is 10 liters.At first under 110 ℃ of conditions, left standstill aging 12 hours, crystallization 50 hours under 165 ℃ of conditions again, the rotation of crystallization process mesohigh still (or stirring) speed is 13 cels.After crystallization process was finished, product was cooled off rapidly, and inclining mother liquor, again with pure water washing for several times, was 8～9 until the pH value of solution, filter, 120 ℃ dry 10 hours down, promptly get and contain lanthanum Penuasil type Si-Al zeolite.The SiO of this finished product 2/ Al 2O 3(molecular ratio) is 50, contains lanthanum 2.01%Wt, 25 ℃ of normal hexane loading capacity 10.20%Wt(adsorption conditionses, normal hexane dividing potential drop 20mmHg).
Embodiment 2: the preparation of zeolite catalyst
With alumina trihydrate and concentration is 33% aqueous nitric acid and example 1 dry good zeolite product, mixes also to mix and pinches evenly, and the consumption of alumina trihydrate is so that butt Al 3O 3With the weight ratio of zeolite be 35%/65%, the consumption of aqueous nitric acid is looked to mix and is pinched thing and do wet appropriateness and be advisable, it is rectangular to be extruded into φ 2m/m then, dry more than 24 hours under 110～120 ℃ of conditions, again that drying is good bar is cut into cylindrical particle.This cylindrical material slowly rises to 450 ℃ with 3～4 ℃/minute of heat-up rates in nitrogen gas stream, 450 ℃ of roastings 1 hour, 500 ° of roastings 1 hour, and 540 ℃ of roastings 2 hours, then under airflow 540 ℃ continue roasting 3 hours.Take out after being chilled to room temperature, use 1NNH 4NO 2And 0.5NNH 4The OH mixing solutions carries out the ammonium ion exchange operation; After finishing, exchange washs to there not being NO with pure water - 2, filter and 110 ℃ of dryings more than 24 hours.The sodium of products therefrom contains＜0.05%Wt.
Will be exsiccant ammonium type zeolite sample pack in the tube furnace, (so that the oxygen level of mixed gas is about 1%) slowly heats up in nitrogen and Air mixing air-flow, 540 ℃ of roastings 4 hours, cut off source of the gas subsequently, improve pure water and intensification simultaneously, flooding quantity is 5～10 a milliliters/gram sample, hour, under 580～600 ℃ of temperature condition, kept 4 hours.After hydrothermal treatment consists operation is finished, change again with dry air and purge cooling, take out to room temperature.
Embodiment 3: the sulfuration of catalyzer
Get example 2 and make zeolite 100 grams, with concentration is 100 milliliters of dip treating of ammonium sulfide solution of 0.5%wt, filter and remove redundant solution, drying is 3 hours under 110～120 ℃ of conditions, handled 1.5 hours under hydrogen stream and 450～480 ℃ of conditions, getting product contains lanthanum and sulphur Pentasil type Si-Al zeolite catalyzer again.This product contains lanthanum 1.25%Wt, sulphur 0.1%Wt, and the medium tenacity acid site that the TPD method is measured in its 325～450 ℃ of scopes accounts for (to total acid site amount of sample) about 65%.
Embodiment 4:
Replace 29.9 gram Lanthanum trichlorides in the above-mentioned example 1 with chlorination mishmetal 37.0 gram, all the other conditions and method and example 1 identical makes and contains the Pentasil type Si-Al zeolite that mixes rare earth.The SiO of this product 2/ Al 2O 3(molecular ratio) is 47, contains to mix rare earth content 2.51%Wt, surface-area 362m 2/ g, and normal hexane loading capacity 9.5%Wt.
Embodiment 5:
With the zeolite product of above-mentioned example 4,, promptly make the finished product zeolite catalyst that contains mixing rare earth and sulphur through further handling with above-mentioned example 2 and example 3 identical conditions and method.This finished product contains and mixes rare earth 1.56%Wt, sulphur 0.1%Wt, and the acid site that the TPD method is measured medium tenacity in its 325～450 ℃ of scopes accounts for (to total acid site amount of sample) about 60%.
Embodiment 6:
Be on 5 milliliters the continuous flow fixed bed reactor at the zeolite catalyst device, and at reaction pressure 7kg/cm 2(gauge pressure), 375 ℃ of temperature of reaction, ethylene content 20%(body in the work material ethylene gas body) (all the other are 20%H 2, 60%N 2), ethene (pure) weight space velocity 1.0hr -1, the reaction result of the zeolite catalyst of use-case 3 is mainly: conversion of ethylene 98.4%Wt, benzene transformation efficiency 20.5%Wt, ethylbenzene selectivity 91.1%, and ethylbenzene ten diethylbenzene selectivity 99.0%.
Embodiment 7:
In reaction unit described in the example 6 and under the identical reaction conditions, the zeolite catalyst reaction result of example 5 is mainly: conversion of ethylene 98.0%Wt, benzene transformation efficiency 19.8%Wt, ethylbenzene selectivity 88.7%, and ethylbenzene ten diethylbenzene selectivity 98.0%.
Embodiment 8:
On reaction unit described in the example 6, adopting the pure ethylene of concentration＞99% is unstripped gas, at pressure 10kg/cm 2, 400 ℃ of temperature of reaction, weight ethylene air speed 2.0hr -1And benzene/ethene (molecular ratio) is that the reaction result of the zeolite catalyst of use-case 3 is mainly: conversion of ethylene＞99.5%Wt, ethylbenzene selectivity 91.0%, ethylbenzene ten diethylbenzene selectivity＞99.0%Wt under 5 the reaction conditions.
Embodiment 9:
Adopt the zeolite catalyst of example 3 and the reaction unit of example 6, but unstripped gas is used catalytic cracked dry gas instead, this dry gas consist of (%V), ethene 19.6, propylene 3.5, butylene 4-5, hydrogen 10, oxygen 1, carbonic acid gas 5-6, carbon monoxide 2, hydrogen sulfide 5000-6000ppm, surplus is N 1And C 1～C 4Saturated hydrocarbons.At reaction pressure 10kg/cm 2(gauge pressure), 375 ℃ of temperature of reaction, weight ethylene air speed 2.4hr -1And benzene/ethene (molecular ratio) is under 3 the condition, conversion of ethylene 90%, and propylene conversion 85% and butene conversion 84%, ethylbenzene selectivity are more than 82%, and the selectivity of ethylbenzene ten diethylbenzene is more than 98%; In addition, also have propyl benzene and butylbenzene and 1% left and right sides C + 5Alkane alkene generates.
Embodiment 10:
Under the condition of example 9, the reaction process parameter of having carried out system changes test.Think at reaction pressure 7～11kg/cm 2(gauge pressure), 375～450 ℃ of temperature of reaction, ethylene feed weight space velocity 1.0～3.0hr -1, the processing condition of benzene/ethene (molecular ratio) 3～6 are relatively more suitable.In these scopes, more than the conversion of ethylene 83%Wt, ethylbenzene selectivity is more than 82%, and the selectivity of ethylbenzene ten diethylbenzene is more than 98%.The main technique condition test result such as the following table of the catalyzer of example 3 are listed.
(table is seen the literary composition back)
Embodiment 11:
Adopt 100 milliliters of the zeolite catalysts of example 3 and be on 150 milliliters the heat-insulating continuous flow fixed bed reactor in scale, and the catalytic cracked dry gas of use-case 9 is reactor feed gas, at pressure 7kg/cm 2(gauge pressure), weight ethylene air speed 1.0, benzene/ethene (molecular ratio) be 5 and the reaction conditions of 350 ℃ of beds temperature ins and 430 ℃ of bed temperature outs under, on-line continuous operation 31 days, conversion of ethylene is kept 95～90%Wt, the transformation efficiency of propylene and butylene also more than 90%Wt, the selectivity about 90% of ethylbenzene ten diethylbenzene.Adopt the way that improves temperature in gradually from being operated to 32 yuan, keep more than the per pass conversion 90%Wt of ethene, the running of the on-line continuous of this zeolite catalyst can reach 60 days.
Of the present invention contain lanthanum or contain mix rare earth Pentasil type Si-Al zeolite catalyzer, be applicable to that benzene and ethene carry out alkylated reaction, the particularly suitable H that contains 2S and H 2The refinery exhaust of impurity such as O (as catalytic cracked dry gas) is the benzene alkylation reaction process of raw material.Compare catalyzer of the present invention with the method that present industry is adopted, not only demonstrate good reactivity worth and operation stability, and production technique is simple and easy has a remarkable economic efficiency.
Test reaction pressure reacting ethylene heavy benzol ethene ethylbenzene ethylbenzene 12
Numbering kg/cm 2Temperature amount air speed/conversion of ethylene selectivity ethylbenzene is selected
(divide
№ (gauge pressure) ℃ hr -1The son ratio) %Wt % %
1 10 350 1.8 3 89.16 78.51 98.37
2 10 375 1.8 3 97.59 82.33 98.37
3 10 400 1.8 3 98.19 86.57 98.84
4 10 425 1.8 3 97.75 88.88 98.78
5 10 450 1.8 3 96.50 89.89 98.31
6 5 375 1.8 3 89.40 82.37 98.00
7 15 375 1.8 3 98.12 82.92 98.45
8 20 375 1.8 3 98.51 84.74 98.69
9 10 375 2.4 3 90.09 82.09 98.68
10 10 375 3.0 3 84.23 80.76 98.14
11 10 375 3.6 3 72.97 80.56 98.95
12 10 375 2 2 96.22 76.84 98.53
13 10 375 1.8 4 94.33 85.01 98.51
14 10 375 1.8 5 92.45 87.75 98.39
15 10 375 1.8 6 91.15 87.47 98.84

Claims (2)

1, a kind ofly be used for the pentasil type Si-Al zeolite catalyzer that benzene and ethene carry out alkylation reaction, feature of the present invention is to contain rare earth and element sulphur in the catalyzer, and it is formed weight percent and is: mishmetal 0.3～6% or lanthanum: 0.2～3%; Sulphur 0.005～0.2%; All the other are zeolite and Al 2O 3, and zeolite and Al 2O 3Mixture in, zeolite: 30～70%; Al 2O 370～30%; The SiO of zeolite 2/ Al 2O 3Be 40～100; Its preparation method is:
(1) the synthetic of zeolite is that Tai-Ace S 150 or sodium metaaluminate and rare earth halide are hybridly prepared into solution respectively with water glass or water glass and ammonium hydroxide or diamine, under violent stirring, two solution are mixed into glue after crystallization get zeolite;
(2) with (1) synthetic zeolite and aluminum oxide and rare nitric acid mixing moulding, oven dry, roasting heats up in inert gas;
(3) (2) zeolite is exchanged into the ammonium type with ammonium salt aqueous solution, 80～90 ℃ of ion-exchange temperatures, in 450～540 ℃ in air ear, roasting is more than 6 hours after the ion-exchange;
(4) zeolite that (3) were handled is at 500～650 ℃ of temperature, flooding quantity 2～20ml/g.Sample, hour condition under carry out hydrothermal treatment consists;
(5) zeolite that (4) were handled carries out obtaining finished catalyst after the sulfidizing.
2, according to the described catalyzer of claim 1, the sulfidizing of zeolite can adopt dry method or wet method, it is characterized in that vulcanizing agent can use hydrogen sulfide, sulfurous gas and ammonium sulfide, and best sulfidizing is to adopt wet method, vulcanizing agent ammonium sulfide.
CN87105054A 1987-08-04 1987-08-04 Process of ethylbenzene by alkylating low-density ethylene and relevant zeolite catalyst Expired - Fee Related CN1022404C (en)

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CN1022404C true CN1022404C (en) 1993-10-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1048655C (en) * 1996-06-24 2000-01-26 中国石油化工总公司 Alkyl catalyst and application thereof

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055075C (en) * 1996-01-16 2000-08-02 中国石油化工总公司 Technology for prepn. of ethyl benzene by reaction of thin ethylene and benzene
CN1079285C (en) * 1997-06-06 2002-02-20 中国石油化工总公司 Catalyst for alkylation of benzene and ethylbenzene manufactured from ethylene
CN1074401C (en) * 1997-09-22 2001-11-07 中国石油化工总公司 Process for preparing ethyl benzene and propyl benzene by reaction of dilute ethylene, propene and benzene
CN1074398C (en) * 1999-08-27 2001-11-07 中国石油天然气集团公司 Combined catalytic rectification and absorption process of preparing alkyl arene through the reaction of low-density olefine and arene
CN1150142C (en) 1999-12-10 2004-05-19 北京服装学院 Benzene and oil refinery dry gas catalyzed alkylation distillation process and equipment of preparing ethylbenzene

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1048655C (en) * 1996-06-24 2000-01-26 中国石油化工总公司 Alkyl catalyst and application thereof

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