CN1040360A - The new preparation method of methyl tertiary butyl ether (MTBE) - Google Patents
The new preparation method of methyl tertiary butyl ether (MTBE) Download PDFInfo
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- CN1040360A CN1040360A CN 89105325 CN89105325A CN1040360A CN 1040360 A CN1040360 A CN 1040360A CN 89105325 CN89105325 CN 89105325 CN 89105325 A CN89105325 A CN 89105325A CN 1040360 A CN1040360 A CN 1040360A
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Abstract
A kind of new MTBE preparation method adopts conventional catalyzer, it is characterized in that reactor does not need inner heat-exchange equipment, do not need outer loop refrigerative equipment yet, simple in structure, invest low, easy to operate, can significantly cut down the consumption of energy, transformation efficiency still meets design requirement.The present invention can also be applicable to modernizing and expanding the existing factory of prior art except that being applicable to newly-built MTBE device, and is applicable to production isopropyl benzene and the trimethyl carbinol and other similar art production process.
Description
The invention belongs to a kind of new method of synthetic MTBE, MTBE is as a kind of gasoline dope that improves gasoline octane rating, and its manufacture method is widely used in the petrochemical production process.
Technical background:
By C
4Iso-butylene and methyl alcohol react in the synthesize methyl tert-butyl ether technology of (being called for short MTBE) in the cut, the general fixed-bed reactor that adopt, under liquid phase state, react,, adopt traditional shell and tube reactor or reaction mass outer circulation refrigerative cartridge reactor more for solving the taking-up of reaction heat.The equipment complexity, investment is big, and the energy consumption height has been developed to shell and tube reactor as Italian Snam company and West Germany Huls company, passes to water coolant in the shell side of reactor, with control reaction temperature.U.S. ARCO company has been developed to cartridge type outer circulation reactor technology (U.S.P4198530), it be reaction product through the cooling after, loop back reactor inlet, control reaction temperature.But, also reduced reaction efficiency because of isobutylene concentration is recycled the material dilution.IFP has been developed liquid phase expanded bed reaction technology (being so-called IFP technology), (Fr2455019, Fr2440931) characteristics of this reaction technology are the focuses of having eliminated in the reactor, but material is back-mixing in reactor, reduced concentration of reactants, thereby reaction efficiency, the CR﹠amp of the U.S. have been reduced; It is the new technique of making MTBE that C/NC company (U.S.P.4439350) and main office of China Petrochemical Industry (Chinese patent 88109705.5) have been developed to catalytic distillation technology, but because of catalyst loading structure more complicated, so be affected in the practical application.
Purpose of the present invention:
For solving the problem of aforementioned existence, the objective of the invention is to adopt a kind of new method, change vapour, liquid two phase reaction into by homogeneous reaction, allow reaction heat be absorbed, thereby can cancel the consumption of heat exchange cooling apparatus and water coolant by the vaporization of part material, do not need simultaneously reactor outer loop part material to get back to reactor yet, thereby equipment is simple, reduced investment, and energy consumption is low, and is easy to operate, not only can be used for the design of newly-built factory, also can be used for the transformation of old technology factory.
General introduction of the present invention:
The present invention is according to the characteristics of MTBE building-up reactions, makes in the bubble point that is reflected at material and the dew-point temperature scope to carry out.The reaction heat that reaction process is emitted can make material partly vaporize and be absorbed, and carries out so that be reflected under the predetermined temperature.Therefore the present invention is different from traditional liquid phase reaction, and reaction is carried out under vapour-liquid mixed phase reaction conditions, and reactor is an insulation fix bed reactor.Use a bed when iso-butylene content is low in raw material.When iso-butylene content is higher, can be divided into two or three to four beds to catalyzer, raw material is except that mainly entering the reactor with the reactor end, other tells the cold raw material of 1-3 thigh and enters the further temperature of reaction of adjusting between the beds by side line respectively, therefore without any need for additional heat-obtaining measure, reaction heat can utilize fully, simple in structure, reduced investment, energy consumption is low.
Technical process and explanation (seeing accompanying drawing 1)
Raw material C
4(1) by pump (2), methyl alcohol (3) is squeezed into reactor inlet pipeline (5) by pump (4), mix back and hot to certain temperature at mixing tank (6) through giving, enter reactor (7), go out reactor through macropore sulfuric acid resin beds (8) after reacting, the time go into separation column (9).Vapor phase product is ejected by separation column, after voltage-controlled variable valve (10) and condenser (11) coagulate entirely, enters return tank (12), and part overhead condensation liquid is back to separation column (9) top, all the other C through reflux pump (13)
4Liquid goes out device through pipeline (14).MTBE product at the bottom of the tower, part is returned separation column after reboiler (15) is heated at the bottom of, all the other products float controller valve (16) and pipeline (17) at the bottom of tower go out device.
Raw material C
4Pass through the reactor catalyst bed with carbinol mixture, under the effect of general catalyzer macropore sulfuric acid resin, iso-butylene and methyl alcohol react, and generate MTBE, and this reaction is reversible exothermic reaction.
The reaction liberated heat, absorb by partial material vaporization control reaction temperature.And use by the cold raw material that side line enters between each beds in the reactor and regulated, carry out so that be reflected under the predetermined temperature condition.This temperature of reaction is in the bubble point and dew-point temperature scope of material, and bubble point and dew point are decided by reaction pressure.Therefore adjusting working pressure gets final product control reaction temperature.
The molecular ratio of methyl alcohol and iso-butylene is 0.9～2.5 in the reaction mass, and reaction velocity was generally 1～30 o'clock
-1Reactor inlet temperature is generally 25～80 ℃, and reaction temperature out (stable reaction temperature) is generally 60～120 ℃, and reaction outlet top temperature should be controlled within the top temperature of catalyzer permission.The optimum reaction conditions is: air speed 4-20
-1, temperature in 30-70 ℃, equilibrium temperature 60-90 ℃, methyl alcohol/pib molecule compares 0.9-2.
When MTBE synthesis technique and alkylation process associating, iC
= 4Transformation efficiency reaches 90～92% and can meet the requirements, and in this case, one section mixed phase reaction can reach requirement, as Fig. 1.
When in order to produce high-purity butene-1, or when producing the raw material of divinyl as oxydehydrogenation, iC
= 4Transformation efficiency require to reach more than 99%, can adopt the two-stage reaction flow process, as shown in Figure 2, promptly reach equilibrium conversion through one section mixed phase reaction after, enter the MTBE that separation column is told generation, residue C
4Enter the second mixed phase reactor (7) again after giving heat, further react, total conversion rate is reached more than 99%, and then enter after-fractionating tower (9), tell the MTBE of generation at the bottom of tower, cat head obtains iso-butylene content and is lower than 0.5% residue C
4Can also react the new catalytic distillation technique of inventing with my institute with mixed phase of the present invention, (its application number is a Chinese patent 88109705.5) combines, form new technical process, as Fig. 3, promptly through after one section mixed phase bed (7) reaction, product enters in the catalytic distillation reaction tower (9) of synthetic MTBE, under reacting section catalyst (8) effect, carry out secondary reaction, cat head obtains containing iC
= 4Be less than 0.5% residue C
4, get the MTBE product at the bottom of the tower.
The effect of invention:
Aforesaid goal of the invention all reaches, because being reflected at the vapour-liquid two-phase is to carry out under the mixed phase condition, can cancel facilities such as cooling heat-obtaining and outer circulation heat-obtaining, simplify structure of reactor, simplified the operation, reduced investment, reactant directly enters separation column, reaction heat is utilized fully, can cancel water coolant again, thereby can significantly cut down the consumption of energy.One section reaction conversion ratio can reach to 90～92%, meets the requirements.As required, further the degree of depth transforms, and makes iC
= 4Transformation efficiency reaches more than 99%, reaction back residue C
4Middle iso-butylene content＜0.5% can be produced divinyl behind the separating methanol, the raw material of n-butene-1 or other products.
According to same reaction principle, the present invention also is applicable to other similar art production process such as the isopropyl benzene and the trimethyl carbinol except that being applicable to that MTBE produces.
Claims (3)
1, a kind of by C
4The synthetic new reaction method of MTBE of iso-butylene and methyl alcohol uses catalyzer commonly used in the cut, it is characterized in that:
A. reaction is at vapour--carry out under the liquid mixed phase condition,
B. reactor is the fixed bed pattern, and inside can cancel cold exchange device, beds can establish 1～and several.
C. can cancel reactant outer circulation cooling infrastructure in the reaction process,
D. when iso-butylene content was higher in the raw material, catalyst reactor can be divided into two to several beds, and can tell the cold raw material of part and entered between the beds by side line.
E. the molecular ratio of methyl alcohol and iso-butylene is generally 0.9～2.5.
F. reaction velocity was generally 1～30 o'clock
-1
G. temperature of reaction: inlet: 25-80 ℃
Stable: 60-120 ℃
H. when requiring isobutene conversion to reach 99% when above, can adopt two sections mixed phases reactions and two tower fractionation process, as Fig. 2, i.e. the C that ejects by first separation column
4After fraction is mended a certain amount of methyl alcohol, enter the second mixed phase reactor, the time one the step carry out etherification reaction, isobutene conversion is reached more than 99%.The reaction product of being come out by the second mixed phase reactor enters the after-fractionating tower.
I. when requiring isobutene conversion to reach to 99% when above, also can combine flow process such as Fig. 3 with catalytic distillation technology (Chinese patent 88109705.5 application numbers).The mixed phase bed is used as and is given reactor, directly enters the synthetic MTBE catalytic distillation device that catalyzer is housed without fractionation through reacted reaction product.
2, by claim 1, described method is characterized in that The optimum reaction conditions: during air speed 4-20
-1, temperature in 30-70 ℃, equilibrium temperature 60-90 ℃, methyl alcohol/pib molecule compares 0.9-2.
3, by the described method of claim 1-2, it is characterized in that removing and be applicable to the MTBE production, also be applicable to, other similar art production process such as isopropyl benzene and the trimethyl carbinol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105325 CN1026580C (en) | 1989-06-28 | 1989-06-28 | Prepn. of methyl tertiarybutyl ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105325 CN1026580C (en) | 1989-06-28 | 1989-06-28 | Prepn. of methyl tertiarybutyl ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040360A true CN1040360A (en) | 1990-03-14 |
| CN1026580C CN1026580C (en) | 1994-11-16 |
Family
ID=4856089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89105325 Expired - Lifetime CN1026580C (en) | 1989-06-28 | 1989-06-28 | Prepn. of methyl tertiarybutyl ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1026580C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519498C (en) * | 2006-11-08 | 2009-07-29 | 褚雅志 | Phrcess of coproducing methyl tert-butyl ether and tert-butyl alcohol |
| CN103145533A (en) * | 2013-03-21 | 2013-06-12 | 岳阳兴长石化股份有限公司 | Process and device for producing MTBE (Methyl Tertiary Butyl Ether) through blending and refining high-concentration isobutene |
| CN103641693A (en) * | 2013-12-05 | 2014-03-19 | 河北海特伟业石化有限公司 | Low-energy-consumption MTBE (methyl tert-butyl ether) production method |
| CN104672065A (en) * | 2013-12-03 | 2015-06-03 | 上海东化环境工程有限公司 | Method for producing MTBE from high-concentration isobutene by adopting mixed phase bed reactor |
| CN107473917A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | Mix the technique that carbon four produces diisobutylene |
-
1989
- 1989-06-28 CN CN 89105325 patent/CN1026580C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100519498C (en) * | 2006-11-08 | 2009-07-29 | 褚雅志 | Phrcess of coproducing methyl tert-butyl ether and tert-butyl alcohol |
| CN103145533A (en) * | 2013-03-21 | 2013-06-12 | 岳阳兴长石化股份有限公司 | Process and device for producing MTBE (Methyl Tertiary Butyl Ether) through blending and refining high-concentration isobutene |
| CN104672065A (en) * | 2013-12-03 | 2015-06-03 | 上海东化环境工程有限公司 | Method for producing MTBE from high-concentration isobutene by adopting mixed phase bed reactor |
| CN103641693A (en) * | 2013-12-05 | 2014-03-19 | 河北海特伟业石化有限公司 | Low-energy-consumption MTBE (methyl tert-butyl ether) production method |
| CN107473917A (en) * | 2016-06-07 | 2017-12-15 | 中国石油化工股份有限公司 | Mix the technique that carbon four produces diisobutylene |
| CN107473917B (en) * | 2016-06-07 | 2020-10-27 | 中国石油化工股份有限公司 | Process for producing diisobutylene by mixing C4 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1026580C (en) | 1994-11-16 |
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Owner name: CHINA PETROLEUM & CHEMICAL CORPORATION Free format text: FORMER NAME OR ADDRESS: INST. OF QILU PETRO-CHEMICAL INDUSTRY CO. |
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Address after: 100029, No. 6, Xin Xin Street East, Beijing, Chaoyang District Patentee after: Sinopec Corp. Address before: 129 mailbox, Zibo City, Shandong Province Patentee before: Inst. of Qilu Petro-Chemical Co. |
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