CN1373003A - Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof - Google Patents
Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof Download PDFInfo
- Publication number
- CN1373003A CN1373003A CN01104359A CN01104359A CN1373003A CN 1373003 A CN1373003 A CN 1373003A CN 01104359 A CN01104359 A CN 01104359A CN 01104359 A CN01104359 A CN 01104359A CN 1373003 A CN1373003 A CN 1373003A
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- benzene
- zeolite
- halogen
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A zeolite catalyst for preparing alkylbenzene from olefine and benzene is composed of beta-zeolite (25-90%), halogen (0.05-0.48%) and inertial component (the rest). When it is used to prepare the ethylbenzene by liquid-phase alkylation of ethylene and benzene, it has features of low cost, high quality of product, and high purity of product (more than 99.8%).
Description
The present invention relates to a kind of being used for produces the catalyzer that alkylbenzene is used by alkene and benzene.A kind of catalyzer and Preparation of catalysts method thereof that ethylbenzene and/or isopropyl benzene process are produced in benzene and rare ethene under the liquid-phase condition and/or rare propylene alkylation that be suitable for particularly is provided.
Alkylaromatic hydrocarbon is the intermediates with extensive use, and wherein most importantly as the ethylbenzene and the isopropyl benzene of Chemical Manufacture critical materials, in recent ten years, ethylbenzene throughput in the world doubles many, and ultimate production reaches 2,000 ten thousand tons/year.
Having developed multiple since later 1930s is the catalyzer and the corresponding processing method of raw material system ethylbenzene with ethene and benzene.
USP4107224, Patent publish such as CN1201017 a kind of in the presence of the ZSM-5 zeolite catalyst, be the method that raw material gas phase legal system is got ethylbenzene with rare ethene, rare ethene also can be taken from the tail gas of the catalytic cracking unit of refinery, but need remove H as this tail gas before the raw material
2S, CO
2, H
2O and C
2Above residue.
Disclosing a kind of among the CN1154957A is catalyzer with rare earth/ZSM-5/ZSM-11, is raw material with the catalytic cracked dry gas that contains low-concentration ethane, and vapor phase process is produced the method for ethylbenzene.Wherein used rare ethylene raw should not contain free-water, H
2S content is less than 3000mg/M
3, C
3 =And C
4 =Content is less than 1%, CO
2Content is not more than 4%, does not need special purified in advance direct segmentation to enter multistage, ethylbenzene is produced in the hydrocarbonylation of Quench alkylation reaction device gas phase.
The reaction of alkene and aromatic hydrocarbons is produced alkylaromatic hydrocarbon and is adopted the vapor phase process process, because the temperature of reaction height, and the easy coking and deactivation of catalyzer not only, and than being easier to take place side reaction, the reduction quality product; Adopt the liquid phase method process, it is low to have temperature of reaction, characteristics such as reactor product quality height.
It is raw material that CN1128249A has disclosed a kind of pure ethylene, is catalyzer with the beta molecular sieve, is that 3.5Mpa, temperature of reaction are that the liquid phase method fixed bed reaction is produced the technological process of ethylbenzene under 230～300 ℃ the condition in reaction pressure.The characteristics of the catalyzer that this process adopted are: the SiO of 30～70%% (weights)
2/ Al
2O
3It is 20～40 H β zeolite; The fluorine or chlorine of～10% 0.5 (weight); Surplus is γ-Al
2O
3
USP3929672, it is raw material that USP4169111, USP4459426, USP5600048, USP4891458 etc. have disclosed with the pure ethylene, is that 3.0Mpa, temperature of reaction are that liquid phase method is produced the technological process of ethylbenzene under 230～300 ℃ the condition in reaction pressure.The catalyzer that is applied to this process can be MCM-22, MCM-56, MCM-49, H β, Y zeolite.
Present inventors have disclosed a kind of alkene in Chinese patent (application number is 99122630.5) and aromatic hydrocarbons reacts the method for producing alkylaromatic hydrocarbon, be in the presence of the powdery zeolite catalyzer, raw material olefin (as ethene and/or propylene) and aromatic hydrocarbons (as benzene) carry out alkylated reaction in slurry attitude bed.But utilize above-mentioned catalytic materials, lower to the selectivity of alkylbenzene product.
The purpose of this invention is to provide a kind of catalyzer that alkene and alkylating aromatic hydrocarbon are produced alkylaromatic hydrocarbon that is used for, provide a kind of energy to be fit to catalyzer and this Preparation of catalysts method that low-concentration olefinic and alkylation reaction of arene under the liquid-phase condition are produced alkylaromatic hydrocarbon especially.It is that 10～90% ethene is that raw material and benzene carry out alkylated reaction that this catalyzer is applied to concentration range, produces purity greater than 99.8% ethylbenzene, and the content of dimethylbenzene is less than 100ppm in the ethylbenzene product.
To achieve these goals, of the present invention being used for produced the alkylaromatic hydrocarbon catalyzer by low-concentration olefinic and benzene, is made of β zeolite, halogen and inertia component, it is characterized in that:
(1) SiO
2/ Al
2O
3Molar ratio is 15～45 β zeolite, and its weight content is 25～90%,
(2) the halogen weight content is 0.05～0.48%,
(3) all the other components in the catalyzer are one or more inert materials in alchlor, silicon-dioxide, clay, the diatomite.
In above-mentioned catalyzer, further its acid characteristics are: every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 10 * 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 80: 20～60: 40.
In above-mentioned catalyzer, Na in the further catalyzer
2O content is smaller or equal to 0.05% (weight).
In above-mentioned catalyzer, further halogen is F or Cl in the catalyzer.
The catalyzer that the present invention is used, its preparation method is: at first get SiO
2/ Al
2O
3Ratio is 15～45 Na β zeolite and the mixed according to a certain percentage pinching bar moulding of inert material, after 100～140 ℃ of oven dry, 400～600 ℃ of roastings 1～10 hour; The gained bar is exchanged 2～5 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, 100～140 ℃ of oven dry; With halogen solution aforementioned oven dry thing is carried out vacuum impregnation; Dipping back bar made described catalyzer in 1～10 hour 400～600 ℃ of roastings after 100～140 ℃ of oven dry.
Catalyst acid of the present invention 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 chromatographically under the desorption is quantitative.
Catalyzer provided by the present invention, the content of modifying element is smaller, mainly is to consider in the use of catalyzer, and modifying element can appear in the product because take place to run off, and has reduced quality product.
The activation that need under inert gas atmosphere, heat up before the catalyst reaction provided by the present invention, the activation condition of catalyzer is: 300～500 ℃ of temperature, 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, Ar, one or more mixtures among the He.
Production alkylbenzene catalyzer of the present invention, reaction is produced the reaction conditions of ethylbenzene and is to low-concentration ethane and benzene: reaction pressure 0.7～6.0Mpa, temperature of reaction is lower than the aromatic hydrocarbons boiling temperature (150～350 ℃) under the specified pressure, weight ethylene air speed 0.05～0.5h
-1, the molecular ratio of benzene and ethene is 1～10: 1, the concentration range of ethene is 10～90%.
Production alkylbenzene catalyzer provided by the present invention can be applied to various types of reactors such as fixed bed, slurry attitude bed, catalytic distillation.Below provide embodiment, do not limit its scope because of embodiment.
Embodiment 1: get SiO
2/ Al
2O
3Be 38 Na β zeolite and Al
2O
3Powder mixes the moulding of pinching bar according to 80: 20 weight ratio, after 120 ℃ of oven dry 540 ℃ of roastings 3 hours; The gained bar is exchanged 2 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, 120 ℃ of oven dry; With 0.5%HF solution aforementioned oven dry thing is carried out vacuum impregnation; Dipping back bar made catalyst A in 2 hours 470 ℃ of roastings after 120 ℃ of oven dry, wherein F content is 0.42%, Na
2O content is 0.04%, and every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 13.2 * 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 71: 29.
Embodiment 2: get SiO
2/ Al
2O
3Be that 20 Na β zeolite and clay powder mix the moulding of pinching bar according to 50: 50 weight ratio, after 120 ℃ of oven dry 510 ℃ of roastings 4 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 0.5%HCl solution aforementioned oven dry thing is carried out vacuum impregnation; Dipping back bar made catalyst B in 3 hours 490 ℃ of roastings after 120 ℃ of oven dry, wherein Cl content is 0.25%, Na
2O content is 0.02%, and every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 16.7 * 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 64: 36.
Comparative example 1: get SiO
2/ Al
2O
3Be 35 Na β zeolite and Al
2O
3Powder mixes the moulding of pinching bar according to 80: 20 weight ratio, after 120 ℃ of oven dry 540 ℃ of roastings 3 hours; The gained bar is exchanged 2 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, after 120 ℃ of oven dry, made catalyzer C, wherein Na in 2 hours 470 ℃ of roastings
2O content is 0.03%, and every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid center) 18.9 * 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 75: 25.
Embodiment 4: adopting through the catalytic cracked dry gas of dehydration and the benzene of reformer production is raw material, (the volume %) composed as follows of this dry gas: CH
430.0, C
2H
424.5, C
2H
615.4, C
3H
65.4, C
3H
82.5, H
29.2, N
27.5, CO1.1, CO3.9, O
20.5, H
2S2800mg/M
3, H
2O10ppm; Benzene purity 99.8%.Comprise at a Φ 80mm caliber in the alkylated reaction tower of catalytic distillation and absorption catalyst reaction section being divided into two responding layers that the integer catalyst A of packing into is divided into two equal portions after raw material dry gas and benzene mix and enters each responding layer in every layer.Reaction conditions and the results are shown in Table 1.
The result of table 1 catalyst A in catalytic distillation and absorption combination process
Reaction tower pressure (Mpa) 1.1 2.5
The alkylation reaction zone temperature (℃) 175～186 236～238
The rectifying section head temperature (℃) 123 155
The stripping section bottom temp (℃) 260 320
The absorber portion temperature (℃) 40 40
Alkene air speed (h
-1, heavy) and 0.03 0.1
Benzene/alkene (molecule) 23
C
= 2Transformation efficiency (%) 100 100
C
= 3Transformation efficiency (%) 100 100
C
= 2Generate ethylbenzene and diethylbenzene overall selectivity (%)＞99＞99
Isopropyl benzene/(just+different) propyl benzene (%) 99.3 99.0
Benzene in the rectifying section top discharge (%) 99.5 99.2
Benzene in the stripping section bottom discharge (%) 0.02 0.03
The benzene rate of recovery (%) 99.5 99.1 in the absorber portion tail gas
Xylene content in the ethylbenzene (ppm) 53 47
Embodiment 5: with 1 liter of scale continous way slurry attitude bed is alkylation reactor, gives benzene/ethylbenzene mixing solutions of adorning 600 milliliters of certain mol proportions in reactor, and 500 rev/mins of stirring velocitys are used N
2Make reactive system be raised to predetermined pressure and be warmed up to corresponding temperature, switch the raw material dry gas identical with embodiment 4, with benzene generation alkylated reaction, reaction result sees Table 2.
The result of table 2 different catalysts in catalytic cracked dry gas and benzene slurry attitude bed alkylated reaction
| Reaction conditions | Catalyst A | Catalyst B | Catalyzer C | |
| Reaction pressure (MPa) | ????1.0 | ????2.0 | ????0.7 | ????1.0 |
| Temperature of reaction (℃) | ????170 | ????220 | ????150 | ????170 |
| Ethene air speed (h -1) | ????0.15 | ????0.35 | ????0.05 | ????0.15 |
| Benzene/alkene mol ratio | ????5∶1 | ????6∶1 | ????4∶1 | ????5∶1 |
| Conversion of ethylene (%) | ????95 | ????97 | ????99 | ????99 |
| Propylene conversion (%) | ????100 | ????100 | ????100 | ????100 |
| Ethene generates ethylbenzene+diethylbenzene selectivity (%) | ????99 | ????99 | ????99 | ????97 |
| Propylene generates isopropyl benzene selectivity (%) | ????98 | ????98 | ????99 | ????97 |
| Xylene content (ppm) | ????29 | ????36 | ????32 | ????53 |
Can be seen by The above results, use the liquid phase alkylation reaction of catalyst ethene of the present invention and benzene, the purity of its product ethylbenzene is greater than 99.8%, and xylene content is less than 100ppm, and this catalyzer is suitable for using in industrial production.
Claims (6)
1. one kind is used for producing the alkylaromatic hydrocarbon catalyzer by low-concentration olefinic and benzene, is made of β zeolite, halogen and inertia component, it is characterized in that:
(1) SiO
2/ Al
2O
3Molar ratio is 15～45 β zeolite, and its weight content is 25～90%,
(2) the halogen weight content is 0.05～0.48%,
(3) all the other components in the catalyzer are one or more inert materials in alchlor, silicon-dioxide, clay, the diatomite.
2. according to the described catalyzer of claim 1, it is characterized in that its acid characteristics are that every gram catalyzer total acid content is (150～600 ℃ of ammonia desorption relative acid centers) 10 * 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 80: 20～60: 40.
3. according to the described catalyzer of claim 1, it is characterized in that Na in the catalyzer
2The O weight content is smaller or equal to 0.05%.
4. according to the described catalyzer of claim 1, it is characterized in that halogen is F or Cl in the catalyzer.
5. one kind according to the described Preparation of catalysts method of claim 1 is:
(1) Na β zeolite and inert material are mixed extrusion forming according to a certain percentage, after 100～140 ℃ of oven dry, 400～600 ℃ of roastings 1～10 hour;
(2) (1) gained shaping thing is exchanged 2～5 times at 80～90 ℃ with ammonium salt solution, extremely neutral with deionized water wash then, 100～140 ℃ of oven dry;
(3) (2) gained shaping thing is carried out vacuum impregnation with halogen solution;
(4) with (3) gained shaping thing after 100～140 ℃ of oven dry, 400～600 ℃ of roastings 1～10 hour.
6. be used for alkene and alkylation reaction of arene under the liquid-phase condition according to the described catalyzer of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01104359A CN1123387C (en) | 2001-02-28 | 2001-02-28 | Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN01104359A CN1123387C (en) | 2001-02-28 | 2001-02-28 | Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1373003A true CN1373003A (en) | 2002-10-09 |
| CN1123387C CN1123387C (en) | 2003-10-08 |
Family
ID=4653847
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN01104359A Expired - Fee Related CN1123387C (en) | 2001-02-28 | 2001-02-28 | Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1123387C (en) |
Cited By (3)
| 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 |
| CN100389876C (en) * | 2005-03-31 | 2008-05-28 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethene ethyl benzene from ethene and benzene in dry gas, preparation method and application thereof |
| CN106582844A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Aromatic hydrocarbon alkylation catalyst composition and applications thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100494127C (en) * | 2006-03-08 | 2009-06-03 | 中国科学院大连化学物理研究所 | Method of preparing ethyl benzene by alkylating ethylene and benzene |
-
2001
- 2001-02-28 CN CN01104359A patent/CN1123387C/en not_active Expired - Fee Related
Cited By (4)
| 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 |
| CN100389876C (en) * | 2005-03-31 | 2008-05-28 | 中国科学院大连化学物理研究所 | Catalyst for preparing ethene ethyl benzene from ethene and benzene in dry gas, preparation method and application thereof |
| CN106582844A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Aromatic hydrocarbon alkylation catalyst composition and applications thereof |
| CN106582844B (en) * | 2015-10-19 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of aromatic alkylation catalysts composition and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1123387C (en) | 2003-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6636162B2 (en) | Palladium-based hydrogenation catalyst, method for producing the same, and use thereof | |
| JP5562345B2 (en) | Olefin oligomerization | |
| EP0367873A1 (en) | Hydrocarbon conversion process using a regenerable fluoride-sensitive catalyst | |
| KR102293960B1 (en) | Dual Catalytic Process and Systems for Propylene Production | |
| CN1915923A (en) | Method for preparing propylene through catalytic cracking C4-C12 olefin | |
| CN102746092B (en) | Method for separating and producing 1,3,5-trimethylbenzene through hydrocracking heavy aromatic hydrocarbons | |
| CN101428235A (en) | Regeneration method of molecular sieve catalysts | |
| CN1506342A (en) | Process of catalytically cracking C4 and above olefin to produce propylene | |
| CN102746091B (en) | Method for producing BTX (benzene, toluene and xylol) aromatic hydrocarbons and trimethylbenzene from heavy aromatic hydrocarbons | |
| CN1123387C (en) | Zeolite catalyst for preparing alkylbenzene from olefin and benzene and preparing process thereof | |
| KR20170013988A (en) | Method for preparing paraxylene with co-production of propylene with high selectivity | |
| CN1958739A (en) | Aromatization catalyst, preparation method, and application | |
| CN1233603C (en) | Method for preparing propylene/ethane from catalytic cracking C4-C6 | |
| US10150106B1 (en) | Method for forming a zeolite catalyst and use thereof to form a BTX-rich stream | |
| CN1058284C (en) | Light hydrocarbon aromatization catalyst and its preparing process | |
| CN1123388C (en) | Zeolite catalyst for low-temp liquid-phase alkylation of arylhydrocarbon and preparing process thereof | |
| CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN1189433C (en) | Method for preparing ethene and propylene | |
| CN104109071A (en) | Method for preparing propylene by using cracking C5 fraction | |
| Sedran et al. | Relation between acidity and activity during the transformation of methanol into hydrocarbons on amorphous silica-alumina | |
| CN1087334C (en) | Catalytic distillation selective hydrogenation process for cracking petroleum hydrocarbon vapor for producing C3 fraction composition | |
| CN1589967A (en) | Catalyst for production of ethyl benzene using ethylene and benzene and its preparation method and application | |
| CN1093431C (en) | Catalyst for aromatizing low-carbon paraffin and its preparing process | |
| US3795714A (en) | Isoparaffin alkylation process and catalyst for use therein | |
| CN114057531A (en) | Synthetic method of ethylbenzene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: DALIAN BEISITE DRY GAS PHENYLETHANE CHEMICALS CO. Free format text: FORMER OWNER: DALIAN INST OF CHEMICOPHYSICS, CHINESE ACADEMY OF SCIENCES Effective date: 20051104 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20051104 Address after: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee after: Dalian Best Chemical Co., dry gas to ethylbenzene Address before: 116023 No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |