CN1072353A - Alkene and benzene alkylation solid acid catalyst - Google Patents

Alkene and benzene alkylation solid acid catalyst Download PDF

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Publication number
CN1072353A
CN1072353A CN91108244A CN91108244A CN1072353A CN 1072353 A CN1072353 A CN 1072353A CN 91108244 A CN91108244 A CN 91108244A CN 91108244 A CN91108244 A CN 91108244A CN 1072353 A CN1072353 A CN 1072353A
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benzene
catalyst
temperature
alkene
hours
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CN91108244A
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CN1034276C (en
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许艺
黄日信
吴沛成
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China Petrochemical Corp
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Jinling Petrochemical Co China
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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
    • Y02P20/584—Recycling of catalysts

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

Abstract

The solid acid catalyst system that linear alkene that the present invention is prepared and benzene alkylation reaction are used is made through ion-exchanged by Y zeolite.The ion that is used for modification has alkaline-earth metal Ca, Sr, Ba etc., and rare-earth elements La, Ce or mishmetal.This catalyst adopts binder free and with stick Al 2O 3Two kinds of method moulding, have high conversion ratio and selectivity.
Make decaying catalyst obtain regeneration with process of washing with organic solvent-benzene.

Description

Alkene and benzene alkylation solid acid catalyst
The present invention relates to a kind of be used for linear alkene particularly carbon ten and be used for the method for this catalyst regeneration to the linear alkene of carbon 16 and the solid acid catalyst of benzene alkylation reaction.
Linear alkylbenzene (LAB) is to produce the intermediate that biodegradable detergent is used, and all is at present to use linear olefin and benzene at HF or AlCl 3Catalytic action under synthetic linear alkylbenzene (LAB).Because HF and AlCl 3All have very strong corrosivity, very high to the equipment requirement of producing, acid needs neutralisation treatment, is easy to environment and health of human body are worked the mischief.And heterogeneous solid acid catalyst non-corrosiveness does not work the mischief to the person and environment, and the equipment investment expense is low.Be engaged at present a lot of of alkene and the developmental research of benzene alkylation reaction solid acid catalyst abroad, but majority is the research lower carbon number hydrocarbons.What United States Patent (USP) 4477585,4547605,4717780 reports adopted is ZSM series molecular sieve; What United States Patent (USP) 4075126 was reported is interlinkage imvite series; United States Patent (USP) 4335022,42586828,4368342,4524229 report be that tungstosilicic acid is immersed in synthetic composite catalyst on porous material such as silica, the alumina silicate carrier, but the alkylated reaction that is used for linear alkene, conversion ratio, selectivity, and life of catalyst all undesirable, up to the present big progress is not arranged.
The objective of the invention is to prepare a kind of particularly C of linear olefin that is used for 10-C 16Alkene and the benzene reaction solid acid catalyst that generates linear alkylbenzene (LAB), and the renovation process of this catalyst is to substitute the HF or the AlCl of present industrial usefulness 3Catalyst.This catalyst has very high conversion ratio, selectivity, and can repeatedly regenerate.
The present invention is to be matrix with zeolitic materials such as X type, Y type, modenite, particularly y-type zeolite, carries out ion-exchanged, synthetic catalyst.Used Y zeolite SiO 2/ Al 2O 3In the 3.0-6.0 scope, under 75 ℃ of-95 ℃ of temperature with concentration 1-20Wt.% alkaline-earth metal Ca, Sr, the aqueous solution exchange of Ba compound 1-3 hour, 80 ℃-140 ℃ dry 4-20 hour, 200 ℃-600 ℃ roasting 2-10 hour.Repeated exchanged, drying, roasting once (condition is constant) then.With concentration is 0.1-20Wt.%NH 4Cl and 1-20Wt.% rare-earth elements La, Ce compound water solution be 75 ℃-95 ℃ down exchanges 1-3 hour, 80 ℃-140 ℃ dry 4-20 hour, 200 ℃-600 ℃ roasting 2-10 hour, repeated exchanged, drying, roasting be (condition is constant) once.
The moulding of catalyst is divided into two kinds of methods, and a kind of is the binder free type, and catalyst fines is got the 8-30 order in the pressure lower sheeting moulding of 5-30 ton; Another kind is the adding additives type, and used binding agent is Al 2O 3, kaolin, imvite, silica gel etc., consumption accounts for the 10-50% of gross weight, extruded moulding.
These catalyst fixed bed reactors, 100 ℃-300 ℃ of reaction temperatures, pressure 0.5-5MPa, liquid hourly space velocity (LHSV)=0.5-20Hr -1, benzene/alkene (mol ratio)=5-30, conversion ratio is 99-100%, selectivity is 90-100%.
Renovation process of the present invention is at 100 ℃-300 ℃ of temperature, pressure 1.0-5.0MPa, liquid hourly space velocity (LHSV)=0.1-5.0Hr -1Wash the colloid of flush away polymerization on catalyst surface under the condition with benzene.Regeneration rear catalyst conversion ratio returns to 99-100%.
Product analysis is measured with gas-chromatography and normal potential titration.
The following examples are to explanation of the present invention, are not limiting the scope of the invention.
The former powder of embodiment one 100 gram NaY, SiO 2/ AL 2O 3=4.5, add 800 milliliters of 10Wt.%Ca(NO 3) 2Solution exchange 2 hours, temperature is 90 ± 5 ℃, exchanges back 120 ℃ of dryings 3 hours, 550 ℃ of roastings 4 hours, repeated exchanged, drying, roasting once, condition is constant.Use the NH of 5Wt.% again 4The La(NO of Cl and 5Wt.% 3) 3800 milliliters of the aqueous solution exchange 2 hours, and 90 ± 5 ℃ of temperature exchange back 120 ℃ of dryings 3 hours, and 550 ℃ of roastings are 4 hours then.Repeated exchanged, drying, roasting be (condition is constant) once.The powder that synthesizes is in 10 tons forming under the pressure, and fragmentation is beaten sheet and got the 10-16 order, activates 3 hours down in 350 ℃.
The raw material of reaction is the mixture of benzene and alkane alkene, benzene/alkene (C 10-C 13) (mol ratio)=20,150 ℃ of reaction temperature degree, pressure 1.5MPa, liquid hourly space velocity (LHSV)=2.5Hr -1From reaction result, successive reaction 24 hours, conversion ratio is more than 99%, and selectivity is more than 99%.
The result of table 1 catalytic reaction
Reaction time (hour) 048 12 16 20 24
Olefin conversion % 0 99.9 99.8 99.7 99.8 99.9 99.9
Selectivity % 0 99.3 99.8 99.7 99.4 99.6 99.9
Synthesizing of embodiment two catalyst, but forming method difference with example one.The forming method of this catalyst is as follows: get 10 gram catalyst powder, add 3 gram Al 2O 3, add water furnishing paste, be squeezed into 1.2 * 3mm bar.In air air-dry 12 hours, 120 ℃ dry 4 hours down, 550 ℃ of following roastings 4 hours.Intensity 〉=0.15MPa/ particle.The condition of reaction and raw material are with example one.
The result of table 2 catalytic reaction
Reaction time (hour) 048 12 16 20 24
Olefin conversion % 0 99.8 99.8 99.7 99.6 99.8 99.8
Selectivity % 0 99.1 99.0 99.2 99.7 99.0 99.3
Reaction time (hour) 28 32 36 40 44
Olefin conversion % 99.4 98.8 98.6 96.7 95.2
Selectivity % 99.0 99.3 99.6 99.2 99.2
React regeneration later in 40 hours 24 hours.Renovation process is: 230 ℃ of temperature, under the pressure 3.5MPa condition, with benzene flushing 24 hours, liquid hourly space velocity (LHSV)=0.5Hr -1
Table 3 regeneration back catalytic reaction result
Reaction time (hour) 048 12 16 20 24
Olefin conversion % 0 99.7 99.6 99.6 99.4 99.3 99.4
Selectivity % 0 99.1 99.2 99.2 99.3 99.7 99.6
The former powder of embodiment 3 100 gram NaY, SiO 2/ Al 2O 3=4.5, add 800 milliliters of 10Wt.%SrCl 2Aqueous solution exchange 2 hours, temperature is 90 ± 5 ℃, exchanges back 120 ℃ of dryings 3 hours, 550 ℃ of roastings 4 hours, repeated exchanged, drying, roasting be (condition is constant) once, uses 5Wt.%La(NO again 3) 3800 milliliters of the aqueous solution exchange 2 hours, and 90 ± 5 ℃ of temperature exchange back 120 ℃ of dryings 3 hours, and 550 ℃ of roastings are 4 hours then.Repeated exchanged, drying, roasting be (condition is constant) once.Forming method is with example two.The raw material of reaction is the mixture of benzene and alkane alkene, benzene/alkene (C 10-C 13) (mol ratio)=15.
The result of table 4 catalytic reaction
Reaction time (hour) 08 16 32 38 44 50
Olefin conversion % 0 99.7 99.8 99.8 99.7 99.7 99.7
Selectivity % 0 99.3 99.2 99.7 99.6 99.5 99.6
Reaction time (hour) 56 60 64
Olefin conversion % 99.3 98.0 94.8
Selectivity % 99.3 99.4 99.5
React after 64 hours and regenerated 24 hours, renovation process is with example two.
The result of table 5 regeneration back catalytic reaction
Reaction time (hour) 048 12 16 20 24
Olefin conversion % 0 99.7 99.8 99.4 99.4 99.3 99.3
Selectivity % 0 99.0 99.3 99.7 99.2 99.3 99.7
La(NO in the catalyst in embodiment four examples three 3) 3Use Ce(NO 3) 3Replace, remaining component, give-and-take conditions, exchange concentration and Preparation of Catalyst, forming method are with example three.
Reacted 48 hours, conversion ratio 〉=99%, a conversion ratio reduces to 96% after selectivity 〉=99%, 56 hour, and after 24 hours, conversion ratio returns to more than 99% as the regeneration of example two methods, and sustained response 24 hours, conversion ratio 〉=99%.

Claims (4)

1, a kind of C that is used for 10-C 16Linear alkene and the solid acid catalyst of benzene alkylation reaction, it is characterized in that with the Y zeolite being matrix, through alkaline earth element Ca, Sr, Ba, rare-earth elements La, the Ce modification forms, and a kind of method that makes this catalyst regeneration.
2, according to the described catalyst of claim 1., the Y zeolite SiO that it is used 2/ AL 2O 3In the 3.0-6.0 scope, alkaline earth element Ca, Sr, the exchange concentration of Ba is 1-20Wt.%, temperature 75-95 ℃, rare-earth elements La, the exchange concentration of Ce is 1-20Wt.%, temperature 75-95 ℃.Baking temperature is 100-140 ℃, sintering temperature 200-600 ℃.Added binding agent is AL 2O 3, kaolin, imvite, silica gel, content is the 10-50% of gross weight.
3, according to the described catalyst recovery process of claim 1., it is characterized in that with organic solvent-benzene be irrigation under the 200-300 ℃ of temperature, under the 1.0-5.0MPa pressure, the liquid hourly space velocity (LHSV)=0.1-5.0Hr of benzene -1, the recovery time is 1-48 hour.
4, according to the described catalyst of claim 1., its reaction temperature is 100-300 ℃, and pressure is 0.5-5.0MPa, liquid hourly space velocity (LHSV)=0.5-20Hr -1Benzene/alkene (mol ratio)=5-30.
CN91108244A 1991-11-20 1991-11-20 Solid acid catalyst for olefine hydrocarbons and phenyl alkylate Expired - Fee Related CN1034276C (en)

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CN91108244A CN1034276C (en) 1991-11-20 1991-11-20 Solid acid catalyst for olefine hydrocarbons and phenyl alkylate

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CN91108244A CN1034276C (en) 1991-11-20 1991-11-20 Solid acid catalyst for olefine hydrocarbons and phenyl alkylate

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CN1034276C CN1034276C (en) 1997-03-19

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055876C (en) * 1996-01-25 2000-08-30 中国石油化工总公司 Alkylated catalyst for preparation of alkylbenzene
CN1077808C (en) * 1996-07-05 2002-01-16 中国科学院大连化学物理研究所 Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application
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
CN106179486A (en) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 A kind of containing noble metal with the renovation process of EUO type molecular sieve catalyst
CN110562995A (en) * 2018-06-06 2019-12-13 中国石油化工股份有限公司 Synthesis method of nano Y zeolite, synthesized nano Y zeolite and application
CN111203287A (en) * 2018-11-21 2020-05-29 内蒙古伊泰煤基新材料研究院有限公司 Regeneration method of benzene alkylation solid acid catalyst
CN113304771A (en) * 2021-06-11 2021-08-27 青岛化赫医药科技有限公司 Catalyst for preparing glycol ether and method for preparing glycol ether by using same

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CN100478705C (en) * 2006-03-06 2009-04-15 中南大学 Signal magnifying multiple circuit with digital control
CN100483152C (en) * 2006-09-01 2009-04-29 中南大学 Multifunctional sender and controller for electrical surveying signal
US7820869B2 (en) 2008-06-30 2010-10-26 Uop Llc Binderless adsorbents and their use in the adsorptive separation of para-xylene
US7812208B2 (en) 2008-09-22 2010-10-12 Uop Llc Binderless adsorbents with improved mass transfer properties and their use in the adsorptive separation of para-xylene

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Publication number Priority date Publication date Assignee Title
US3565964A (en) * 1968-08-05 1971-02-23 Sun Oil Co Alumino-silicate catalyzed reactions of polycyclic aromatic hydrocarbons in the presence of hydrogen
SU973510A1 (en) * 1979-08-27 1982-11-15 Институт теплофизики СО АН СССР Composition for making protective refractory daubing

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1055876C (en) * 1996-01-25 2000-08-30 中国石油化工总公司 Alkylated catalyst for preparation of alkylbenzene
CN1077808C (en) * 1996-07-05 2002-01-16 中国科学院大连化学物理研究所 Catalyst of alkyl benzene with straight chain made by alkylation from benzene and straight chain olefin and its application
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
CN106179486A (en) * 2015-04-29 2016-12-07 中国石油化工股份有限公司 A kind of containing noble metal with the renovation process of EUO type molecular sieve catalyst
CN106179486B (en) * 2015-04-29 2018-06-19 中国石油化工股份有限公司 A kind of regeneration method containing noble metal and EUO type molecular sieve catalyst
CN110562995A (en) * 2018-06-06 2019-12-13 中国石油化工股份有限公司 Synthesis method of nano Y zeolite, synthesized nano Y zeolite and application
CN111203287A (en) * 2018-11-21 2020-05-29 内蒙古伊泰煤基新材料研究院有限公司 Regeneration method of benzene alkylation solid acid catalyst
US11524282B2 (en) 2018-11-21 2022-12-13 Inner Mongolia Yitai Coal-Based New Materials Research Institute Co., Ltd. Regeneration method for benzene alkylation solid acid catalyst
CN113304771A (en) * 2021-06-11 2021-08-27 青岛化赫医药科技有限公司 Catalyst for preparing glycol ether and method for preparing glycol ether by using same

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Owner name: CHINA PETROCHEMICAL CORPORATION

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Address after: 6, Yi Xin East Street, Beijing, Chaoyang District

Patentee after: China Petrochemical Group Corp.

Address before: Suojin village in Nanjing city of Jiangsu Province, No. seventy-eight

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Granted publication date: 19970319

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