CN102247884A - Catalyst used in process of preparing vinyl chloride from 1,2-ethylene dichloride and preparation method of catalyst - Google Patents
Catalyst used in process of preparing vinyl chloride from 1,2-ethylene dichloride and preparation method of catalyst Download PDFInfo
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- CN102247884A CN102247884A CN 201110131342 CN201110131342A CN102247884A CN 102247884 A CN102247884 A CN 102247884A CN 201110131342 CN201110131342 CN 201110131342 CN 201110131342 A CN201110131342 A CN 201110131342A CN 102247884 A CN102247884 A CN 102247884A
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Abstract
The invention provides a catalyst used in the process of preparing vinyl chloride from 1,2-ethylene dichloride and a preparation method of the catalyst. The catalyst consists of 10.0 to 80.0 weight percent of zeolite and 20.0 to 90.0 weight percent of inorganic oxide substrate, wherein the zeolite is a zeolite socony mobil-5 (ZSM-5) molecular sieve which comprises a rare earth element and has a melt flow index (MFI) structure; the rare earth element is 1 to 15 weight percent based on RE2O3; RE represents the rare earth element; and the inorganic oxide substrate can be a pure oxide or a complex of a plurality of oxides. In the preparation method, the catalyst is prepared by a spray drying forming method. Compared with the conventional thermal cracking technology, the method has the advantages that: energy consumption can be greatly reduced, production cost is reduced, and the catalyst is suitable for a fluidized bed reaction device.
Description
Technical field
The present invention relates to catalyst technical field, relate in particular to and be used for 1, the catalyst of 2-dichloroethanes preparing chloroethylene.
Background technology
Vinyl chloride (being called for short VCM) is a kind of very important chemical raw material, is mainly used in synthesizing polyvinyl chloride resin (PVC) and vinylidene chloride, refrigerant or the like.The VCM in the whole world 99% all is used to produce polyvinyl chloride.The production technology of vinyl chloride mainly contains carbide acetylene method, new technologies such as equilibrium oxygen chloridising and ethene direct chlorination/chloration hydro-oxidation and the direct oxychlorination of ethane at present.And the output that adopts the equilibrium oxygen chloridising to produce VCM accounts for more than 90% of VCM total output, is to adopt maximum VCM production methods.
The reaction process of equilibrium oxygen chloridising is divided into ethene direct chlorination, ethylene oxychlorination and 1,2-dichloroethanes (being called for short EDC) 3 parts of cracking, its device mainly is made up of technique units such as direct chlorination unit, oxychlorination unit, EDC cracking unit, EDC refined unit and VCM refined units.The EDC cracking technology adopts thermal-cracking method at present, reaction when cracking temperature is 450～550 ℃, and 1, the 2-dichloroethanes is converted into vinyl chloride and hydrogen chloride and other accessory substance.This reaction need be used a large amount of natural gases in process of production, and a large amount of cokings in the course of reaction, needs regular parking coke cleaning, and the normal operation of producing is made a big impact.
U.S. Pat P 5008225 discloses a kind of catalytic pyrolysis 1, the catalyst of 2-dichloroethanes preparing chloroethylene.Be by rare earth element is loaded on HFZ-20, HFZ-30, catalytic pyrolysis 1 on the HFZ-55 molecular sieve, and the 2-dichloroethanes makes vinyl chloride.1,2-dichloroethanes conversion ratio is 35.8% o'clock, and the selectivity of VCM is 90.1% to the maximum, is not very high.
Summary of the invention
What the purpose of this invention is to provide a kind of suitable suitability for industrialized production can be with 1, and the 2-dichloroethanes is catalytically conveted to the catalyst of vinyl chloride.
For achieving the above object, catalyst provided by the invention is made up of active component zeolite and inorganic oxide matrix, again the composite catalyst that can be used for fluidized bed reaction of spray-dried preparation.
This catalyst is made up of the zeolite of 10.0～80.0wt% and the inorganic oxide matrix of 20.0～90.0wt% by weight percentage, active component zeolite wherein is the ZSM-5 molecular sieve with MFI structure that contains rare earth element, and wherein ree content is with RE
2O
3Count 1～15wt%, RE represents rare earth element, preferably contains the ZSM-5 molecular sieve with MFI structure of rare earth 3～8wt%.
The manufacture method of catalyst of the present invention may further comprise the steps:
1, the preparation of HZSM-5 molecular sieve:
With Na-ZSM-5 molecular screen primary powder (commodity zeolite or synthetic according to a conventional method obtaining), add in quantitative ammonium chloride (2.3M) solution, molecular screen primary powder (g) is 1: 10 with the ratio of ammonium chloride (2.3M) liquor capacity (ml), 85 ℃ of following ion-exchanges 4 hours, exchange altogether 3 times, spend deionised water after each the exchange, after exchange was finished, the sodium in the usefulness atomic absorption spectroscopy zeolite was (with Na
2O meter) content is less than 0.02wt%, and at 110 ℃ down after dry 12 hours, 500 ℃ of roastings 6 hours obtain the HZSM-5 molecular sieve;
2, rare earth element dipping:
The HZSM-5 molecular sieve is added in the quantitative lanthanum chloride solution, and normal temperature down dipping filtered after 8 hours, and after 110 ℃ of following dryings, 500 ℃ of roastings 6 hours obtain containing the La/HZSM-5 molecular sieve of rare earth, and wherein content of rare earth is 3～8%;
3, shaping of catalyst:
At first with the precursor of inorganic oxide such as boehmite, Ludox or their mixture and La/HZSM-5 molecular sieve in accordance with regulations proportioning mix, after stirring, homogeneous, spray drying forming, 500 ℃ of following roastings 6 hours, obtain containing the finished catalyst of rare earth element;
The catalyst of the present invention's preparation can be with 1, and the 2-dichloroethanes is catalytically conveted to vinyl chloride, and 1,2-dichloroethanes conversion ratio reaches 55.6%, and the vinyl chloride selectivity is greater than 98%.
The specific embodiment
The present invention is described further below by example.
Being prepared as follows of HZSM-5 molecular screen primary powder among the embodiment:
Get 500 gram Na-ZSM-5 molecular sieves (silica alumina ratio 38), add in the ammonium chloride solution of 5000ml 2.3M, 85 ℃ of following ion-exchanges 4 hours, exchange altogether 3 times, spend deionised water after each the exchange, after the filtration, 110 ℃ down after dry 12 hours, 500 ℃ of roastings 6 hours obtain the HZSM-5 molecular sieve.
Embodiment one
Take by weighing 300g HZSM-5 molecular sieve (silica alumina ratio 38) and join in the 1500g lanthanum chloride solution, La loading 5%, normal temperature down dipping filtered after 8 hours, and after 110 ℃ of following dryings, 500 ℃ of roastings 6 hours obtain containing the La/HZSM-5 molecular sieve of rare earth.With 200g Ludox (SiO
2Content 30wt%) and the 140gLa/HZSM-5 molecular sieve join successively in the quantitative deionized water, stir 20min after, centrifugal spray drying, the rotating speed of atomizer is 40Hz, 240 ℃ of inlet temperatures, 130 ℃ of outlet temperatures, 500 ℃ of roastings of the product that obtains promptly got required catalyst finished product in 6 hours.
Embodiment two
Carry out the preparation of La/HZSM-5 molecular sieve by embodiment one.Then with 267g Ludox (SiO
2Content 30wt%) and the 120gLa/HZSM-5 molecular sieve join successively in the quantitative deionized water, stir 20min after, centrifugal spray drying, the rotating speed of atomizer is 40Hz, 240 ℃ of inlet temperatures, 130 ℃ of outlet temperatures, 500 ℃ of roastings of the product that obtains promptly got required catalyst finished product in 6 hours.
Embodiment three
Carry out the preparation of La/HZSM-5 molecular sieve by embodiment one.Then with the 334g Ludox (SiO that measures
2Content 30wt%) and the 100gLa/HZSM-5 molecular sieve join successively in the quantitative deionized water, stir 20min after, centrifugal spray drying, the rotating speed of atomizer is 40Hz, 240 ℃ of inlet temperatures, 130 ℃ of outlet temperatures, 500 ℃ of roastings of the product that obtains promptly got required catalyst finished product in 6 hours.
Embodiment four
Carry out the preparation of La/HZSM-5 molecular sieve by embodiment one.In the shaping of catalyst process, with 233g Ludox (SiO
2Content 30wt%), 45.4g boehmite (Al
2O
3Content 64.6wt%), join successively in the quantitative deionized water, behind the stirring 20min, centrifugal spray drying, the rotating speed of atomizer are 42Hz, 230 ℃ of inlet temperatures, and 120 ℃ of outlet temperatures, 500 ℃ of roastings of the product that obtains promptly got required catalyst finished product in 6 hours.
Catalyst performance evaluation is carried out on fixed fluidized bed, catalyst loading amount 15g, and 350 ℃ of reaction temperatures, reaction pressure are normal pressure, liquid weight air speed 1.5h
-1React 2 hours the results are shown in Table one:
Table one
Claims (7)
1. one kind is used for 1, the catalyst of 2-dichloroethanes preparing chloroethylene, it is characterized in that this catalyst is made up of the zeolite of 10.0～80.0wt% and the inorganic oxide matrix of 20.0～90.0wt% by weight percentage, inorganic oxide matrix can be pure-oxide or several mixtures.
2. according to the described catalyst of claim 1, it is characterized in that zeolite wherein is the ZSM-5 molecular sieve with MFI structure that contains rare earth element, wherein ree content is with RE
2O
3Count 1～20wt%, RE represents rare earth element, preferably contains the ZSM-5 molecular sieve with MFI structure of rare earth 3～8wt%.
3. according to the described catalyst of claim 1, it is characterized in that described rare earth is selected from lanthanum chloride.
4. according to the described catalyst of claim 1, the silica alumina ratio that it is characterized in that described ZSM-5 molecular sieve is 25～200.
5. according to the described catalyst of claim 1, it is characterized in that inorganic oxide matrix is selected from Ludox, Al
2O
3Or their mixture.
6. according to the described catalyst of claim 5, Al
2O
3Be selected from boehmite.
7. one kind is used for 1, and the manufacture method of the catalyst of 2-dichloroethanes preparing chloroethylene is characterized in that may further comprise the steps:
The preparation of a, HZSM-5 molecular sieve: with the Na-ZSM-5 molecular screen primary powder, add in quantitative ammonium chloride (2.3M) solution, molecular screen primary powder (g) is 1: 10 with the ratio of ammonium chloride (2.3M) liquor capacity (ml), 85 ℃ of following ion-exchanges 4 hours, exchange altogether 3 times, spend deionised water after each the exchange, after exchange was finished, the sodium in the usefulness atomic absorption spectroscopy zeolite was (with Na
2O meter) content is less than 0.02wt%, and at 110 ℃ down after dry 12 hours, 500 ℃ of roastings 6 hours obtain the HZSM-5 molecular sieve;
B, rare earth element dipping: the HZSM-5 molecular sieve is added in the quantitative lanthanum chloride solution, and normal temperature dipping down filtered after 8 hours, and after 110 ℃ of following dryings, 500 ℃ of roastings 6 hours obtain containing the La/HZSM-5 molecular sieve of rare earth, and wherein content of rare earth is 3～8%;
C, shaping of catalyst: at first with the precursor of inorganic oxide such as boehmite, Ludox or their mixture and La/HZSM-5 molecular sieve in accordance with regulations proportioning mix, after stirring, homogeneous, spray drying forming, 500 ℃ of following roastings 6 hours, obtain containing the finished catalyst of rare earth element.
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| CN201110131342A CN102247884B (en) | 2011-05-20 | 2011-05-20 | Catalyst used in process of preparing vinyl chloride from 1,2-ethylene dichloride and preparation method of catalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008144A (en) * | 2016-06-08 | 2016-10-12 | 刘家容 | Method for producing vinyl chloride through catalytic cracking |
| JP2018127403A (en) * | 2017-02-06 | 2018-08-16 | 学校法人 関西大学 | Method for producing 1-chloro-2,2-difluoroethylene |
| WO2021114175A1 (en) | 2019-12-12 | 2021-06-17 | 中国科学院大连化学物理研究所 | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane, and preparation method, use, and regeneration method |
| CN112973764A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane, preparation method, application and regeneration method |
| CN115666785A (en) * | 2020-05-29 | 2023-01-31 | 巴斯夫欧洲公司 | Catalyst for hydrogen chloride oxidation and production thereof |
| CN116493041A (en) * | 2023-05-30 | 2023-07-28 | 天津大沽化工股份有限公司 | Composite catalyst for preparing chloroethylene from 1, 2-dichloroethane and preparation method thereof |
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| CN1093952A (en) * | 1993-04-10 | 1994-10-26 | 中国科学院长春应用化学研究所 | Hydrothermal preparation method of high-exchange-degree rare earth ZSM-5 zeolite |
| CN1117518A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司 | Double Zeolite Catalyst for Preparation of Light Olefins |
-
2011
- 2011-05-20 CN CN201110131342A patent/CN102247884B/en active Active
Patent Citations (2)
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| CN1093952A (en) * | 1993-04-10 | 1994-10-26 | 中国科学院长春应用化学研究所 | Hydrothermal preparation method of high-exchange-degree rare earth ZSM-5 zeolite |
| CN1117518A (en) * | 1994-08-22 | 1996-02-28 | 中国石油化工总公司 | Double Zeolite Catalyst for Preparation of Light Olefins |
Non-Patent Citations (1)
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| 《Journal of Molecular Catalysis(CHINA)》 20061031 Gao Qiang et al. Synthesis of Lanthanum-silicate Molecular Sieve with MFI Structure 第405-406页 2-6 第20卷, 第5期 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008144A (en) * | 2016-06-08 | 2016-10-12 | 刘家容 | Method for producing vinyl chloride through catalytic cracking |
| JP2018127403A (en) * | 2017-02-06 | 2018-08-16 | 学校法人 関西大学 | Method for producing 1-chloro-2,2-difluoroethylene |
| WO2021114175A1 (en) | 2019-12-12 | 2021-06-17 | 中国科学院大连化学物理研究所 | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane, and preparation method, use, and regeneration method |
| CN112973764A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Catalyst for preparing vinyl chloride by cracking 1, 2-dichloroethane, preparation method, application and regeneration method |
| KR20220101713A (en) * | 2019-12-12 | 2022-07-19 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Catalyst for decomposing 1,2-dichloroethane to produce vinyl chloride and its preparation method, application and regeneration method |
| EP4066939A4 (en) * | 2019-12-12 | 2022-12-28 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for preparing vinyl chloride by cracking 1,2-dichloroethane, and preparation method, use, and regeneration method |
| JP2023505709A (en) * | 2019-12-12 | 2023-02-10 | 中国科学院大▲連▼化学物理研究所 | Catalyst for vinyl chloride production by decomposition of 1,2-dichloroethane, production method, use and regeneration method |
| JP7360551B2 (en) | 2019-12-12 | 2023-10-12 | 中国科学院大▲連▼化学物理研究所 | Catalyst and manufacturing method for producing vinyl chloride by decomposition of 1,2-dichloroethane |
| KR102798943B1 (en) | 2019-12-12 | 2025-04-21 | 달리안 인스티튜트 오브 케미컬 피직스, 차이니즈 아카데미 오브 사이언시즈 | Catalyst for producing vinyl chloride by decomposing 1,2-dichloroethane and its production method, application and regeneration method |
| CN115666785A (en) * | 2020-05-29 | 2023-01-31 | 巴斯夫欧洲公司 | Catalyst for hydrogen chloride oxidation and production thereof |
| CN116493041A (en) * | 2023-05-30 | 2023-07-28 | 天津大沽化工股份有限公司 | Composite catalyst for preparing chloroethylene from 1, 2-dichloroethane and preparation method thereof |
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Effective date of registration: 20221115 Address after: No. 99, Chuangxin Road, Nangang Industrial Zone, Binhai New Area, Tianjin 300280 Patentee after: Tianjin Bohua Chemical Development Co.,Ltd. Address before: 300455 No. 1, Xinghua Road, Tanggu District, Tianjin Patentee before: TIANJIN DAGU CHEMICAL Co.,Ltd. |
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