CN1230533A - External circulation process to synthesize methyl tert-butyl ether - Google Patents
External circulation process to synthesize methyl tert-butyl ether Download PDFInfo
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- CN1230533A CN1230533A CN 98110743 CN98110743A CN1230533A CN 1230533 A CN1230533 A CN 1230533A CN 98110743 CN98110743 CN 98110743 CN 98110743 A CN98110743 A CN 98110743A CN 1230533 A CN1230533 A CN 1230533A
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- butyl ether
- tertiary butyl
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- methyl tertiary
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Abstract
Methyl t-butyl ether is produced using methanol and mixed C4 fraction as raw material and cathionic exchange resin as catalyst by the external circulation process in fixed bed reactor. In the said process, reaction material is tapped from the middle of the reactor and part of tapped material, after being cooled, is re-fed to the entrance of the reactor and another part of that fed to post-catalyst bed layer. The technological process has the following features: low adiabatic temperature rise in catalyst bed layer, low side product MSBE content in synthesized methyl tert-butyl ether, high isobutylene conversion and high effective utilization rate of catalyst. Even in the condition of 70% deactivation rate of catalyst, relatively high isobutylene conversion may be obtained. The process may be used in industrial production.
Description
The present invention relates to the synthesis technique of methyl tertiary butyl ether, particularly about methyl tertiary butyl ether outer circulation synthesis technique.
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.Its concrete finished product index request is by weight percentage: MTBE＞99%, MSBE＜0.1%, C
4＜0.01%, CH
3OH＜0.1%, TBA＜0.3%, LP＜0.1%, moisture: 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 present domestic 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 does not meet the ingredient requirement that cracking process prepares 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 does not meet the ingredient requirement that cracking process prepares iso-butylene yet, can not satisfy the needs that isoprene-isobutylene rubber is produced.In the EP0600632A document, its first reactor etherification temperature is 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, also belongs to the high temperature modification etherification reaction, can only prepare oil refining type MTBE product.A kind of cartridge type outer circulation reactor technology is disclosed in the document US 4198530, it be the reaction not the end reaction product through the cooling after, loop back reactor inlet, with control reaction temperature, though circulation can be alleviated the thermal insulation warming of reactor like this, can not effectively control the generation of by product MSBE.Chinese patent 95113372.1 discloses a kind of generation method that can effectively control MSBE in synthetic MTBE process, it is by controlling certain transformation efficiency, the incompatible realization of best group of searching raw material air speed and temperature of reaction, but this technology is owing to be subjected to the restriction of air speed, in order to extend manufacture cycle, need to increase reactor platform number.
The objective of the invention is to obtain chemical industry type MTBE product and isobutene conversion height and the high shortcoming of catalyzer effective rate of utilization in order to overcome to satisfy simultaneously in the above-mentioned document, a kind of new synthesize methyl tert-butyl ether technology is provided, and this technology can satisfy the processing requirement of chemical industry type, oil refining type MTBE simultaneously.The methyl tertiary butyl ether that generates can meet and produce the ingredient requirement of isoprene-isobutylene rubber with high-purity iso-butylene, and promptly the content of by-product MSBE has isobutene conversion height in the reaction process, the characteristics that the catalyzer effective rate of utilization is high simultaneously less than 0.1%.
The objective of the invention is to realize by following technical scheme: a kind of methyl tertiary butyl ether synthesis technique, with methyl alcohol and mixed C
4Iso-butylene in the fraction is a raw material, and acidic ion exchange resin is made catalyzer, and reaction pressure is 0.6～3.0MPa, and the molecular ratio of methyl alcohol and iso-butylene is 0.8～2.5, and the raw material air speed is 0.5～10 hour
-1Temperature of reaction is 25～80 ℃, in fixed-bed reactor, carry out, beds can be established at least two sections, and extract material out at second section beds place side line at least, after cooling, extract out the material part by outer circulation to Reactor inlet, the outer circulation ratio is 0.1～5, and another part is extracted material out and entered the rear catalyst bed.
Acidic ion exchange resin catalyst adopts storng-acid cation exchange resin in the technique scheme, the preferable range of reaction pressure is 0.8～1.5MPa, the molecular ratio preferable range of methyl alcohol and iso-butylene is 0.85～1.5, and raw material air speed preferable range is 1.0～8 hours
-1, the temperature of reaction preferable range is 30～65 ℃, and side line is extracted the outer circulation of material part out to Reactor inlet, and the beds preferable range is 2～6 sections, and it is 1～6 that the material side line is extracted a mouthful preferable range out, extracting a mouthful position out can change with the catalyzer service condition.Side line is extracted out in the material, and another part material enters back one beds.The preferable range of outer circulation ratio is 0.5～3.0, and outer circulation is than being meant the material that is recycled into Reactor inlet and the weight ratio of reactor outlet material.
Because generating the etherification reaction of MTBE and MSBE is parallel reaction, and the speed of reaction of MTBE is far longer than MSBE, so in the presence of the excess resin catalyzer, the MTBE formation reaction reaches equal amount, and when being subjected to thermodynamic(al)equilibrium control, MSBE also reaches balance far away, and continuation and methyl alcohol reaction generation MSBE, be the process of a kinetic control, so under the certain condition of catalytic activity, air speed, temperature of reaction etc. all is important factors of control MSBE growing amount.The present invention adopts rational temperature of reaction and air speed processing condition on the basis of Chinese patent 95113372.1, coordinated the mutual relationship of thermodynamics and dynamics in the etherification procedure, in guaranteeing the methyl tertiary butyl ether reaction product MSBE content less than 0.1% in, invented the reaction process that variable bed sections, side line are extracted heat-obtaining in the middle of material and the outer circulation out.Adopt the stage casing side line to extract material out, through the outer circulation of cooled extraction material part to Reactor inlet, another part is extracted the method that material enters the rear catalyst bed out, under the constant condition of catalyzer total amount, more effectively reduce the growing amount of MSBE and controlled the thermal insulation warming in the reaction process, improved the effective rate of utilization of catalyzer, simultaneously C
4Iso-butylene in the fraction still can keep higher transformation efficiency, has obtained effect preferably.
Fig. 1 extracts material external circulation process figure out for the stage casing side line.
Fig. 2 is bottom material external circulation process figure.
Fig. 1 flow process is: C
4Fraction and methanol mixed raw material 1 input reactor 2, through macropore sulfuric acid resin beds 3-1,3-2, after 3-3 reacts, product goes out in reactor 2 processes by pipeline 8, and the reaction discharging is extracted out by pipeline 4-1 or 4-2 from least the second bed of reactor 2, and a part of by pump 6 pipeline 7-1 Returning reactor imports after water cooler 5 coolings, another part enters the rear catalyst bed by pipeline 7-3 or 7-2, and wherein side line extraction position can be regulated as required.
Fig. 2 flow process is: C
4Fraction and methanol mixed raw material 1 input reactor 2 are through macropore sulfuric acid resin beds 3-1,3-2, after 3-3 reacts, a product part goes out reactor 2 by pipeline 8, and another part passes through pipeline 4 after water cooler 5 coolings, Recycle design Returning reactor import in addition.
The present invention is further elaborated below by embodiment.[embodiment 1]
As Fig. 1 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the stage casing outer circulation reactor of 30cm, extracts mouth out apart from bed ingress 15cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 1.5 hours
-1
Reaction pressure 1.1MPa
45 ℃ of temperature of reaction (upper and lower conversion zone temperature in), 22 ℃ of epimere temperature rises
Recycle ratio 1.5
Reactor outlet MSBE/MTBE is 0.022%, iC
4 =Transformation efficiency is 95.9%.[embodiment 2]
As Fig. 1 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the stage casing extraction outer circulation reactor of 15cm, extracts mouth out apart from bed ingress 7.5cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 3.0 hours
-1
Reaction pressure 1.1MPa
55 ℃ of temperature of reaction (upper and lower conversion zone temperature in), 16 ℃ of epimere temperature rises
Recycle ratio 2.0
Reactor outlet iC
4 =Transformation efficiency is 94.5%, and MSBE/MTBE is 0.039% in the product.[embodiment 3]
As Fig. 1 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the outer circulation reactor of 7.5cm, extracts mouth out apart from bed ingress 3.8cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 6.0 hours
-1
Reaction pressure 1.1MPa
60 ℃ of temperature of reaction (upper and lower conversion zone temperature in), 9 ℃ of epimere temperature rises
Recycle ratio 2.0
Reactor outlet iC
4 =Transformation efficiency is 91.1%, and MSBE/MTBE is 0.063% in the product.[embodiment 4]
As Fig. 1 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the outer circulation stage casing extraction reactor of 30cm, extracts mouth out apart from bed ingress 15cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 3.0 hours
-1
Reaction pressure 1.1MPa
53 ℃ of temperature of reaction (upper and lower conversion zone temperature in), 14 ℃ of epimere temperature rises
Recycle ratio 2.0
Reactor outlet MSBE/MTBE is 0.028%, iC
4 =Transformation efficiency is 93.9%.[embodiment 5]
As Fig. 1 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, entering diameter is that φ 2.8cm, bed height are the outer circulation stage casing extraction reactor of 30cm, extracts mouth out apart from bed ingress 22.5cm, and catalyst in reactor is a macropore sulfuric acid resin, catalyst deactivation 75%, reaction conditions is as follows:
Loaded catalyst 70g
Reaction pressure 1.1MPa
58 ℃ of temperature of reaction (upper and lower conversion zone temperature in), 11 ℃ of epimere temperature rises
Recycle ratio 2.0
Reactor outlet MSBE/MTBE is 0.031%, iC
4 =Transformation efficiency is 90.0%.[comparative example 1]
As Fig. 2 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the outer circulation reactor of 30cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 1.5 hours
-1
Reaction pressure 1.1MPa
45 ℃ of temperature of reaction (bed temperature in), 31 ℃ of bed temperature rises
Recycle ratio 1.5
Reactor outlet MSBE/MTBE is 0.063%, iC
4 =Transformation efficiency is 94.5%.[comparative example 2]
As Fig. 2 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the outer circulation reactor of 15cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 3.0 hours
-1
Reaction pressure 1.1MPa
55 ℃ of temperature of reaction (bed temperature in), 22 ℃ of bed temperature rises
Recycle ratio 2.0
Reactor outlet iC
4 =Transformation efficiency is 91.8%, and MSBE/MTBE is 0.078%.[comparative example 3]
As Fig. 2 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the outer circulation reactor of 7.5cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 6.0 hours
-1
Reaction pressure 1.1MPa
60 ℃ of temperature of reaction (bed temperature in), 15 ℃ of bed temperature rises
Recycle ratio 2.0
Reactor outlet iC
4 =Transformation efficiency is 85.5%, and MSBE/MTBE is 0.092%.[comparative example 4]
As Fig. 2 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the outer circulation reactor of 15cm, and catalyst in reactor is a macropore sulfuric acid resin, and reaction conditions is as follows:
Air speed WHSV 3.0 hours-1
Reaction pressure 1.1MPa
53 ℃ of temperature of reaction (bed temperature in), 24 ℃ of bed temperature rises
Recycle ratio 2.0
Reactor outlet MSBE/MTBE is 0.042%, iC
4 =Transformation efficiency is 90.5%.[comparative example 5]
As Fig. 2 iC
4 =Content is the raw material C of 25% (weight)
4Press 1: 1 (methyl alcohol/iC with methyl alcohol
4 =The mol ratio) proportioning mixes, and entering diameter is that φ 2.8cm, bed height are the outer circulation reactor of 30cm, and catalyst in reactor is a macropore sulfuric acid resin, catalyst deactivation 75%, and reaction conditions is as follows:
Loaded catalyst 70g
Reaction pressure 1.1MPa
58 ℃ of temperature of reaction (bed temperature in), 16 ℃ of bed temperature rises
Recycle ratio 2.0
Reactor outlet MSBE/MTBE is 0.032%, iC
4 =Transformation efficiency is 83.1%.
Claims (10)
1, a kind of methyl tertiary butyl ether synthesis technique is with methyl alcohol and mixed C
4Iso-butylene in the fraction is a raw material, and acidic ion exchange resin is made catalyzer, and reaction pressure is 0.6～3.0MPa, and the molecular ratio of methyl alcohol and iso-butylene is 0.8～2.5, and the raw material air speed is 0.5～10 hour
-1Temperature of reaction is 25～80 ℃, in fixed-bed reactor, carry out, beds can be established at least two sections, it is characterized in that extracting material out, after cooling, extract the outer circulation of material part out to Reactor inlet at least the second section beds place side line, the outer circulation ratio is 0.1～5, and another part is extracted material out and entered the rear catalyst bed.
2,, it is characterized in that acidic ion exchange resin catalyst is a storng-acid cation exchange resin according to the described methyl tertiary butyl ether synthesis technique of claim 1.
3,, it is characterized in that reaction pressure is 0.8～1.5MPa according to the described methyl tertiary butyl ether synthesis technique of claim 1.
4, according to the described methyl tertiary butyl ether synthesis technique of claim 1, the molecular ratio that it is characterized in that methyl alcohol and iso-butylene is 0.85～1.5.
5,, it is characterized in that the raw material air speed is 1.0～8 hours according to the described methyl tertiary butyl ether synthesis technique of claim 1
-1
6,, it is characterized in that temperature of reaction is 30～65 ℃ according to the described methyl tertiary butyl ether synthesis technique of claim 1.
7,, it is characterized in that the outer circulation of part extraction material is to Reactor inlet according to the described methyl tertiary butyl ether synthesis technique of claim 1.
8, according to the described methyl tertiary butyl ether synthesis technique of claim 1, it is characterized in that extracting out material outer circulation to the outer circulation ratio of Reactor inlet is 0.5～3.0.
9,, it is characterized in that another part of extracting material out enters back one beds according to the described methyl tertiary butyl ether synthesis technique of claim 1.
10, according to the described methyl tertiary butyl ether synthesis technique of claim 1, it is characterized in that beds is 2～6 sections, it is 1～6 that the material side line is extracted mouth out, extracting a mouthful position out can change with the catalyzer service condition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110743A CN1073072C (en) | 1998-03-30 | 1998-03-30 | External circulation process to synthesize methyl tert-butyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98110743A CN1073072C (en) | 1998-03-30 | 1998-03-30 | External circulation process to synthesize methyl tert-butyl ether |
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| Publication Number | Publication Date |
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| CN1230533A true CN1230533A (en) | 1999-10-06 |
| CN1073072C CN1073072C (en) | 2001-10-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98110743A Expired - Lifetime CN1073072C (en) | 1998-03-30 | 1998-03-30 | External circulation process to synthesize methyl tert-butyl ether |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768053B (en) * | 2008-12-30 | 2013-09-25 | 丹东明珠特种树脂有限公司 | Reactor for synthesizing methyl tert-butyl ether and application thereof |
| CN107382677A (en) * | 2017-07-20 | 2017-11-24 | 山东京博石油化工有限公司 | A kind of method that MTBE devices go into operation |
| CN108558612A (en) * | 2018-04-25 | 2018-09-21 | 陈久仓 | A kind of preparation method of methyl tertiary butyl ether(MTBE) |
| CN108834410A (en) * | 2017-01-06 | 2018-11-16 | 株式会社Lg化学 | The preparation method of methyl tertiary butyl ether(MTBE) |
| CN110075774A (en) * | 2019-06-14 | 2019-08-02 | 长岭炼化岳阳工程设计有限公司 | Change products the MTBE device and its automatic control method of heat bodied oil with safety auto-controlled system |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4198503A (en) * | 1974-11-05 | 1980-04-15 | Beecham Group Limited | 3-Carbamoyl substituted-7-ureido substituted cephalosporins |
| ES2049417T3 (en) * | 1989-03-30 | 1994-04-16 | Chemical Res & Licensin | COMBINED ETERIFICATION AND RENTAL PROCEDURE. |
| DE69123223T2 (en) * | 1990-11-07 | 1997-03-13 | Chemical Res & Licensin | Process of making MTBE |
| CN1044900C (en) * | 1995-12-26 | 1999-09-01 | 中国石油化工总公司上海石油化工研究院 | Process for synthesis of chemical industry type methyl t-butyl ether |
-
1998
- 1998-03-30 CN CN98110743A patent/CN1073072C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768053B (en) * | 2008-12-30 | 2013-09-25 | 丹东明珠特种树脂有限公司 | Reactor for synthesizing methyl tert-butyl ether and application thereof |
| CN108834410A (en) * | 2017-01-06 | 2018-11-16 | 株式会社Lg化学 | The preparation method of methyl tertiary butyl ether(MTBE) |
| CN108834410B (en) * | 2017-01-06 | 2021-09-14 | 株式会社Lg化学 | Process for preparing methyl tert-butyl ether |
| CN107382677A (en) * | 2017-07-20 | 2017-11-24 | 山东京博石油化工有限公司 | A kind of method that MTBE devices go into operation |
| CN108558612A (en) * | 2018-04-25 | 2018-09-21 | 陈久仓 | A kind of preparation method of methyl tertiary butyl ether(MTBE) |
| CN110075774A (en) * | 2019-06-14 | 2019-08-02 | 长岭炼化岳阳工程设计有限公司 | Change products the MTBE device and its automatic control method of heat bodied oil with safety auto-controlled system |
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| CN1073072C (en) | 2001-10-17 |
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