CN1044900C - Process for synthesis of chemical industry type methyl t-butyl ether - Google Patents

Process for synthesis of chemical industry type methyl t-butyl ether Download PDF

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Publication number
CN1044900C
CN1044900C CN95113372A CN95113372A CN1044900C CN 1044900 C CN1044900 C CN 1044900C CN 95113372 A CN95113372 A CN 95113372A CN 95113372 A CN95113372 A CN 95113372A CN 1044900 C CN1044900 C CN 1044900C
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reaction
mtbe
butyl ether
methyl
chemical industry
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CN95113372A
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CN1153163A (en
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方永成
冯志豪
戴德斌
侯万宝
顾军民
熊勤
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SYNTHETIC RUBBER PLANT BEIJING
Sinopec Shanghai Research Institute of Petrochemical Technology
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SYNTHETIC RUBBER PLANT BEIJING
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a process for synthesizing chemical methyl tert-butyl ether. In the process, methyl alcohol and isobutylene in mixed C4 fractions are used as raw materials, strong-acidic cationic exchange resin is used as a catalyst, and the raw materials react under the conditions that reaction pressure is from 0.6 to 3.0MPa (gauge pressure), a ratio of alcohol to isobutylene is from 0.8 to 1.5, the space velocity of the raw materials is from 1.0 to 10 hr<-1> and a reaction temperature is from 40 to 65 DEG C. The technique has the characteristic of less by-methyl sec-butyl ether (MSBE) less than 0.1w t%, and synthesized MTBE can meet the requirements of the raw materials of high-purity isobutylene for preparing butyl rubber; the present invention can be used for the preparation of chemical MTBE.

Description

The chemical industry type methyl t-butyl ether preparation method
The present invention relates to the PREPARATION OF METHYL TERTIARY BUTYL ETHER method, particularly about the preparation method of chemical industry type methyl t-butyl ether.
Methyl tertiary butyl ether is called for short MTBE, and it is the raising gasoline octane rating, regulates the ideal blending component of gasoline oxygen level, is again to produce the important source material of isoprene-isobutylene rubber with high-purity iso-butylene.Divide by purposes, the branch of oil refining type and chemical industry type MTBE is often arranged.The finished product index of chemical industry type MTBE is to methyl sec-butyl ether (being called for short MSBE) and total carbon four (C 4), foreign matter contents such as the trimethyl carbinol (TBA), oligopolymer (LP), methyl alcohol all have strict requirement, concrete finished product index request to be by weight percentage: MTBE＞99%, MSBE＜0.1%, C 4＜0.01%C, CH 3OH＜0.1%, TBA＜0.1%, LP＜0.1%, moisture content: no free-water.In these indexs, MSBE is owing to be the isomer of MTBE, and its boiling point and MTBE are very approaching, so in a single day generate in the reaction process, just is difficult to remove with isolating method.The MTBE that at present domestic and international oil refining type device is produced, its MSBE content is 0.6～1.2%.U.S. Pat 3979461 and Chinese patent CN1040360A have introduced the technology of producing MTBE, but and the content of not shown by-product MSBE.Document CN1058582A has introduced by isomeric olefine and Fatty Alcohol(C12-C14 and C12-C18) and has prepared tert-alkyl ether, the technology of methyl tertiary butyl ether (MTBE) particularly, and its best temperature range is 45～50 ℃, isobutene conversion requires greater than 95%.The MTBE of its preparation can not be used for cracking process and prepare iso-butylene.The disclosed two-stage reaction technology of CN1040360A its objective is in order to prepare high-purity butylene-1 or to be used as the raw material that butylene oxidation-dehydrogenation is produced divinyl, need make conversion for isobutene reach 99%.The MTBE of its preparation can not be used for cracking process and prepare iso-butylene, satisfies the needs that isoprene-isobutylene rubber is produced.Its first reactor etherification temperature of EP0600632A1 is preferably 80～140 ℃, belongs to the high temperature modification etherification reaction, can only prepare oil refining type MTBE product.EP0451394A1 reactor etherification temperature is 150～250 °F, is preferably 165～170 °F, belongs to the high temperature modification etherification reaction, can only prepare oil refining type MTBE product.In order to overcome in the present production, the shortcoming of MSBE too high levels in the MTBE product, provide a kind of in the MTBE building-up process, the content of by-product MSBE is less than 0.1% technology, the MTBE that produces can be satisfied produce the ingredient requirement of isoprene-isobutylene rubber with high-purity iso-butylene, we have invented the novel method of the synthetic MTBE of a kind of chemical industry type.
We find that the generation of MTBE and MSBE is a parallel reaction in practice, and under the active high situation of resin catalyst, the speed of reaction of MTBE is far longer than MSBE.Reach equal amount in the MTBE formation reaction, when being subjected to thermodynamic(al)equilibrium control, MSBE does not also reach balance.Iso-butylene continues to generate MSBE with the methyl alcohol reaction under the effect of high activated catalyst, is the process of a kinetic control; So under certain catalytic activity condition, air speed, temperature of reaction etc. all is important factors of control MSBE growing amount.
The objective of the invention is to realize: with methyl alcohol and mixed C by following technical scheme 4Iso-butylene in the fraction is a raw material, makes catalyzer with strongly acidic cation-exchange, and reaction pressure is counted 0.6～3.0MPa with gauge pressure, and the mol ratio of methyl alcohol/iso-butylene is 0.8～1.5, and the raw material air speed is 1.0～10hr -1, temperature of reaction is 40～65 ℃, methyl alcohol and the mixed C that contains iso-butylene 4The synthetic MTBE of reaction.
Reaction pressure is 0.8～1.5MPa in the gauge pressure preferable range in the technique scheme, and the mol ratio preferable range of methyl alcohol/iso-butylene is 1.0～1.2, and raw material air speed preferable range is 5～8hr -1, the temperature of reaction preferable range is 50～55 ℃.
Among the present invention, owing to adopted rational temperature of reaction and air speed processing condition, coordinated the mutual relationship of thermodynamics and dynamics in the etherification procedure, the content of having guaranteed the MSBE in the methyl tertiary butyl ether reaction product is less than 0.1% (weight percent), MSBE content makes synthetic MTBE product index meet the ingredient requirement of chemical industry type MTBE less than 800ppm among the MTBE after testing.
[embodiment 1]
The raw material mixed C 4In, consist of Trimethylmethane: normal butane 0.43%: anti-butene-2 2.10%: iso-butylene 8.55%: n-butene 21.30%: 45.85%, maleic-2:6.15%, methyl alcohol: 15.32%, the alfin mol ratio is 1.05: 1 in the reaction, reaction pressure is counted 0.8MPa with gauge pressure, and reaction velocity is 6.0hr -1, temperature of reaction is 53 ℃, and reaction finishes after check and analysis, and MSBE content is 0.021% (wt) among the MTBE, and conversion for isobutene is 75.1%.[embodiment 2]
Raw material mixed C according to embodiment 1 4Form, the alfin mol ratio is 1.10: 1 in the reaction, and reaction pressure is counted 1.0MPa with gauge pressure, and reaction velocity is 7.0hr -1, temperature of reaction is 56 ℃, and reaction finishes after check and analysis, and MSBE content is 0.034% (wt) among the MTBE, and conversion for isobutene is 82.4%.[embodiment 3]
Raw material mixed C according to embodiment 1 4Form, the alfin mol ratio is 1.20: 1 in the reaction, and reaction pressure is counted 1.1MPa with gauge pressure, and reaction velocity is 4.8hr -1, temperature of reaction is 59 ℃, and reaction finishes after check and analysis, and MSBE content is 0.068% (wt) among the MTBE, and conversion for isobutene is 93.3%.[embodiment 4]
Raw material mixed C according to embodiment 1 4Form, the alfin mol ratio is 1.30: 1 in the reaction, and reaction pressure is counted 1.6MPa with gauge pressure, and reaction velocity is 2.5hr -1, temperature of reaction is 50 ℃, and reaction finishes after check and analysis, and MSBE content is 0.076% (wt) among the MTBE, and conversion for isobutene is 92.6%.

Claims (4)

1. chemical industry type methyl t-butyl ether preparation method is with methyl alcohol and mixed C 4Iso-butylene in the fraction is a raw material, and strongly acidic cation-exchange is made catalyzer, and reaction pressure is counted 0.6～3.0MPa with gauge pressure, and the mol ratio that it is characterized in that methyl alcohol/iso-butylene is 0.8～1.5, the raw material air speed is 1.0～10hr -1, temperature of reaction is 40～65 ℃.
2. chemical industry type methyl t-butyl ether preparation method according to claim 1, the mol ratio that it is characterized in that methyl alcohol/iso-butylene is 1.0～1.2.
3. chemical industry type methyl t-butyl ether preparation method according to claim 1 is characterized in that the raw material air speed is 5～8hr -1, temperature of reaction is 50～55 ℃.
4. chemical industry type methyl t-butyl ether preparation method according to claim 1 is characterized in that reaction pressure counts 0.8～1.5MPa with gauge pressure.
CN95113372A 1995-12-26 1995-12-26 Process for synthesis of chemical industry type methyl t-butyl ether Expired - Lifetime CN1044900C (en)

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Application Number Priority Date Filing Date Title
CN95113372A CN1044900C (en) 1995-12-26 1995-12-26 Process for synthesis of chemical industry type methyl t-butyl ether

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CN1044900C true CN1044900C (en) 1999-09-01

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1073072C (en) * 1998-03-30 2001-10-17 中国石油化工总公司 External circulation process to synthesize methyl tert-butyl ether
CN1307141C (en) * 2004-10-28 2007-03-28 中国石油化工股份有限公司 Etherification method of methanol and isobutene
CN100519498C (en) * 2006-11-08 2009-07-29 褚雅志 Phrcess of coproducing methyl tert-butyl ether and tert-butyl alcohol
CN103739469A (en) * 2013-12-24 2014-04-23 山东滨州裕华化工厂有限公司 Process for preparing MEK (Methyl Ethyl Ketone) by utilizing C4 fraction in etherified liquefied petroleum gas
CN106336348A (en) * 2015-07-09 2017-01-18 上海仙佳化工有限公司 Methyl tert-butyl ether desulphurization method
CN108558612A (en) * 2018-04-25 2018-09-21 陈久仓 A kind of preparation method of methyl tertiary butyl ether(MTBE)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4404409A (en) * 1979-03-05 1983-09-13 Nippon Oil Co., Ltd. Process for preparing methyl tertiary-butyl ether
EP0390596A2 (en) * 1989-03-30 1990-10-03 Chemical Research & Licensing Company Combined etherification and alkylation process
EP0485078A1 (en) * 1990-11-07 1992-05-13 Chemical Research & Licensing Company Process for the production of MTBE
JPH04283532A (en) * 1990-11-19 1992-10-08 Chem Res & Licensing Co Process for producing methyl tertiary butyl ether(mtbe)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4404409A (en) * 1979-03-05 1983-09-13 Nippon Oil Co., Ltd. Process for preparing methyl tertiary-butyl ether
EP0390596A2 (en) * 1989-03-30 1990-10-03 Chemical Research & Licensing Company Combined etherification and alkylation process
EP0485078A1 (en) * 1990-11-07 1992-05-13 Chemical Research & Licensing Company Process for the production of MTBE
JPH04283532A (en) * 1990-11-19 1992-10-08 Chem Res & Licensing Co Process for producing methyl tertiary butyl ether(mtbe)

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