CN105175203A - Method for preparing isobutene by MTBE (Methyl Tertiary Butyl Ether) - Google Patents
Method for preparing isobutene by MTBE (Methyl Tertiary Butyl Ether) Download PDFInfo
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- CN105175203A CN105175203A CN201510565601.1A CN201510565601A CN105175203A CN 105175203 A CN105175203 A CN 105175203A CN 201510565601 A CN201510565601 A CN 201510565601A CN 105175203 A CN105175203 A CN 105175203A
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- butylene
- butyl ether
- tertiary butyl
- methyl alcohol
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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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a method for preparing isobutene by MTBE (Methyl Tertiary Butyl Ether). The method comprises the following steps that the synthesis of MTBE raw materials is performed at the temperature of 55 to 65 DEG C; the separation of the MTBE raw materials is performed in a catalytic distillation column to obtain purified MTBE; the purified MTBE is send to a tubular fixed bed reactor after the purified MTBE is subjected to heat exchange by a heat exchanger, the cracking reaction is performed under the action of an aluminum silicate catalyst to obtain mixed liquor of gas phase isobutylene and liquid phase methyl alcohol; gas-liquid separation is performed; the isobutene of which the methyl alcohol is removed by a methyl alcohol washing tower is sent to two serially connected isobutene light component removal columns for removing light components in the isobutene; the isobutene subjected to light component removal is sent to two serially connected isobutene de-heavy fractionators in sequence to remove heavy components in the isobutene to obtain isobutylene of higher purity; the methyl alcohol is sent to a methyl alcohol recovery tower for recovering the methyl alcohol so as to obtain a methyl alcohol product. According to the method provided by the invention, the isobutene of high purity is prepared, the methyl alcohol can be reused, energy conservation and environment protection can be realized, and the production cost is reduced.
Description
Technical field
The present invention relates to preparation method's technical field of iso-butylene, particularly relate to a kind of method that methyl tertiary butyl ether prepares iso-butylene.
Background technology
Iso-butylene is a kind of important basic organic chemical industry raw material, is widely used in the synthesis multiple Organic Chemicals such as isoprene-isobutylene rubber and polyisobutene and fine chemicals.The iso-butylene product of current 70% is for the synthesis of isoprene-isobutylene rubber and methacrylic ester, and these two kinds of purposes are very high to the requirement of iso-butylene purity, not only iso-butylene purity requirement is greater than 99.7%, and wherein the contained impurity such as MTBE, methyl alcohol, water requires to be not more than 10ppm, dme foreign matter content is not more than 5ppm.
Methyl tertiary butyl ether (MTBE) cracking is a kind of advanced and economically feasible high-purity iso-butylene technology.Also be the technological line of current most popular production high-purity isobutylene.
Chinese patent CN201310532042.5 discloses a kind of technique of cracking isobutene by methyl-tert-butyl ether, this technique comprises after methyl tertiary butyl ether carries out scission reaction in reactor, the split product of gained carries out heat exchange and is cooled to less than 75 DEG C, the cooled product of gained enters packing tower and is separated, after gas-phase product is discharged from sizer top, enter the adsorption tower of the mixture that sorbent molecule sieve and silica gel are housed, the product that adsorption tower top is discharged enters iso-butylene weight-removing column, obtains iso-butylene product.There is long flow path, multitower separation material consumption purity that is large, iso-butylene is not high, and methyl alcohol can not utilize in high efficiente callback, many defects that iso-butylene production cost is high.
In summary, obviously there is inconvenience and defect in actual use in prior art, so be necessary to be improved.
Summary of the invention
For above-mentioned defect, the object of the present invention is to provide a kind of methyl tertiary butyl ether to prepare the method for iso-butylene, it can prepare high-purity isobutylene, recycling methyl alcohol, and energy-conserving and environment-protective, reduce production cost.
To achieve these goals, the invention provides a kind of method that methyl tertiary butyl ether prepares iso-butylene, it is characterized in that, comprise the following steps:
A. the synthesis of methyl tertiary butyl ether raw material;
B. the separation of methyl tertiary butyl ether raw material;
C. the cracking of methyl tertiary butyl ether;
D. gas-liquid separation;
E. the purification of iso-butylene;
F. the purification of methyl alcohol.
As preferred technical scheme, in described step c: by the refining methyl tertiary butyl ether that obtains in step b after interchanger heat exchange, temperature of reaction be 200 DEG C ~ 240 DEG C, pressure is 0.6MPa ~ 0.8MPa, the liquid hourly space velocity of refining methyl tertiary butyl ether is 2h
-1~ 4.5h
-1condition under, the refining methyl tertiary butyl ether after heat exchange is sent in calandria type fixed bed reactor, under alumina silicate catalyst effect, carries out scission reaction, obtain the mixed solution of gas phase iso-butylene and Liquid Phase Methanol.
As preferred technical scheme, in described step e: gas phase iso-butylene in steps d is got rid of the rear methyl alcohol sent into methyl alcohol water wash column removal iso-butylene from knockout drum, iso-butylene after removal methyl alcohol is sent into successively the light constituent in two iso-butylene lightness-removing columns removal iso-butylenes of series connection, send into two iso-butylene weight-removing columns of connecting successively after iso-butylene dehydrogenation component and remove heavy constituent in iso-butylenes, obtain high-purity isobutylene.
As preferred technical scheme, in described a step: under temperature is 55 DEG C ~ 65 DEG C conditions, the iso-butylene and methyl alcohol that contain C-4-fraction are added in reactor, under the katalysis of storng-acid cation exchange resin, carry out etherification reaction, obtain methyl tertiary butyl ether, unreacted iso-butylene, unreacted methyl alcohol and unreacted carbon four.
As preferred technical scheme, in described b step: the methyl tertiary butyl ether obtained in step a, unreacted iso-butylene, unreacted methyl alcohol and unreacted carbon four are sent into catalytic rectifying tower and carries out catalytic distillation, obtain refining methyl tertiary butyl ether, obtain unreacted methyl alcohol and unreacted carbon four from catalytic distillation column overhead to send into methyl alcohol water wash column and carry out methyl alcohol drip washing, at the bottom of catalytic rectifying tower tower, obtain methanol aqueous solution send into methanol distillation column and reclaim.
As preferred technical scheme, in described Step d: the mixed solution of the gas phase iso-butylene obtained in step c and Liquid Phase Methanol is sent into knockout drum and carry out being separated of gas phase iso-butylene and Liquid Phase Methanol;
In described f step: Liquid Phase Methanol in steps d is sent into the methanol distillation column obtained in step b and reclaim methyl alcohol, the methanol distillation column that the methanol aqueous solution in the methyl alcohol water wash column obtained is sent in step b is reclaimed methyl alcohol, obtain methanol product in step e.
As preferred technical scheme, the pedal number of the lightness-removing column of iso-butylene described in step e is 40 pieces ~ 50 pieces.
As preferred technical scheme, in step b, catalytic rectifying tower is provided with 12 layers of beds between stripping section and rectifying section, is provided with two separate tower tray above every layer of bed.
As preferred technical scheme, in step a, temperature is 60 DEG C.
As preferred technical scheme, in step c, temperature is 220 DEG C, and pressure is 0.7MPa.
The present invention compared with prior art has the following advantages:
1, the present invention is utilized to prepare the method for iso-butylene, by the iso-butylene obtained after the cracking of methyl tertiary butyl ether successively by two the iso-butylene dehydrogenation towers be connected in series and two the iso-butylene weight-removing columns be connected in series, light constituent in removing iso-butylene and heavy constituent, obtain high-purity isobutylene.
2, reacted methyl alcohol is carried out recycle and reuse, reduce the production cost of iso-butylene.
3, methyl tertiary butyl ether carries out scission reaction in calandria type fixed bed reactor, more further can improve catalytic effect, improves the production efficiency of iso-butylene.
Embodiment
In order to make object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
Embodiment one:
The invention provides a kind of method that methyl tertiary butyl ether prepares iso-butylene, comprise the following steps:
A. the synthesis of methyl tertiary butyl ether raw material
Under temperature is 55 DEG C ~ 65 DEG C conditions, the iso-butylene and methyl alcohol that contain C-4-fraction are added in reactor, under the katalysis of storng-acid cation exchange resin, carry out etherification reaction, obtain methyl tertiary butyl ether, unreacted iso-butylene, unreacted methyl alcohol and unreacted carbon four;
B. the separation of methyl tertiary butyl ether raw material
The methyl tertiary butyl ether obtained in step a, unreacted iso-butylene, unreacted methyl alcohol and unreacted carbon four are sent into catalytic rectifying tower and carries out catalytic distillation, obtain refining methyl tertiary butyl ether, obtain unreacted methyl alcohol and unreacted carbon four from catalytic distillation column overhead to send into methyl alcohol water wash column and carry out methyl alcohol drip washing, at the bottom of catalytic rectifying tower tower, obtain methanol aqueous solution send into methanol distillation column and reclaim;
C. the cracking of methyl tertiary butyl ether
By the refining methyl tertiary butyl ether that obtains in step b after interchanger heat exchange, temperature of reaction be 200 DEG C ~ 240 DEG C, pressure is 0.6MPa ~ 0.8MPa, the liquid hourly space velocity of refining methyl tertiary butyl ether is 2h
-1~ 4.5h
-1condition under, the refining methyl tertiary butyl ether after heat exchange is sent in calandria type fixed bed reactor, under alumina silicate catalyst effect, carries out scission reaction, obtain the mixed solution of gas phase iso-butylene and Liquid Phase Methanol;
D. gas-liquid separation
The mixed solution of the gas phase iso-butylene obtained in step c and Liquid Phase Methanol is sent into knockout drum and carry out being separated of gas phase iso-butylene and Liquid Phase Methanol;
E. the purification of iso-butylene
Gas phase iso-butylene in steps d is got rid of the rear methyl alcohol sent into methyl alcohol water wash column removal iso-butylene from knockout drum, iso-butylene after removal methyl alcohol is sent into successively the light constituent in two iso-butylene lightness-removing columns removal iso-butylenes of series connection, send into two iso-butylene weight-removing columns of connecting successively after iso-butylene dehydrogenation component and remove heavy constituent in iso-butylenes, obtain high-purity isobutylene;
F. the purification of methyl alcohol
The methanol distillation column sent into by Liquid Phase Methanol in steps d in step b reclaims methyl alcohol, and the methanol distillation column sent into by the methanol aqueous solution in the methyl alcohol water wash column in step e in step b reclaims methyl alcohol, obtains methanol product.
Preferably, the pedal number of the lightness-removing column of iso-butylene described in step e is 40 pieces ~ 50 pieces.
Preferably, in step b, catalytic rectifying tower is provided with 12 layers of beds between stripping section and rectifying section, is provided with two separate tower tray above every layer of bed.
Preferably, in step a, temperature is 60 DEG C.
Preferably, in step b, temperature is 220 DEG C, and pressure is 0.7MPa.
According to above-mentioned steps, when temperature is 60 DEG C, the iso-butylene and methyl alcohol that contain C-4-fraction are added in reactor, under the katalysis of storng-acid cation exchange resin, carry out etherification reaction, obtain the product such as methyl tertiary butyl ether and unreacted methyl alcohol, wherein methyl tertbutyl ether yield is maximum, methyl tertiary butyl ether feeding catalytic rectifying tower will be obtained and carry out catalytic distillation, obtain refining methyl tertiary butyl ether, methyl tertiary butyl ether will be refined after interchanger heat exchange, temperature of reaction be 220 DEG C, pressure is 0.7MPa, the liquid hourly space velocity of refining methyl tertiary butyl ether is 2h
-1~ 4.5h
-1condition under, send in calandria type fixed bed reactor, under alumina silicate catalyst effect, carry out scission reaction, obtain the mixed solution of gas phase iso-butylene and Liquid Phase Methanol; Mixed solution is sent into knockout drum and carry out being separated of gas phase iso-butylene and Liquid Phase Methanol; Separation is obtained iso-butylene, and secondary feeding methyl alcohol water wash column, two iso-butylene lightness-removing columns be connected in series and two iso-butylene weight-removing columns be connected in series carry out the removal of impurity, obtain high-purity isobutylene.The methyl alcohol unreacted methyl alcohol in methyl tertiary butyl ether building-up process is sent into methyl alcohol that the methanol-water, the methyl tertiary butyl ether catalytic rectifying tower that obtain after water wash column carries out methyl alcohol drip washing obtain, obtaining in Liquid Phase Methanol that methyl tertiary butyl ether cracking obtains and isobutene purification process sends into methanol distillation column, reclaim methyl alcohol, obtain methanol product, methanol product can be carried out recycle of the present invention and also can be carried out other reactions or utilize.By method of the present invention, the transformation efficiency of methyl tertiary butyl ether can reach 99.5% ~ 99.7%, and the selectivity of iso-butylene is greater than 99.0%, and the purity of iso-butylene is greater than 99.9%.
In sum, the invention provides a kind of method that methyl tertiary butyl ether prepares iso-butylene, the present invention is utilized to prepare the method for iso-butylene, by the iso-butylene obtained after the cracking of methyl tertiary butyl ether successively by two the iso-butylene dehydrogenation towers be connected in series and two the iso-butylene weight-removing columns be connected in series, light constituent in removing iso-butylene and heavy constituent, obtain high-purity isobutylene; Reacted methyl alcohol is carried out recycle and reuse, reduces the production cost of iso-butylene; Methyl tertiary butyl ether carries out scission reaction in calandria type fixed bed reactor, more further can improve catalytic effect, improves the production efficiency of iso-butylene.
Certainly; the present invention also can have other various embodiments; when not deviating from the present invention's spirit and essence thereof; those of ordinary skill in the art are when making various corresponding change and distortion according to the present invention, but these change accordingly and are out of shape the protection domain that all should belong to the claim appended by the present invention.
Claims (10)
1. methyl tertiary butyl ether prepares a method for iso-butylene, it is characterized in that, comprises the following steps:
A. the synthesis of methyl tertiary butyl ether raw material;
B. the separation of methyl tertiary butyl ether raw material;
C. the cracking of methyl tertiary butyl ether;
D. gas-liquid separation;
E. the purification of iso-butylene;
F. the purification of methyl alcohol.
2. a kind of methyl tertiary butyl ether as claimed in claim 1 prepares the method for iso-butylene, it is characterized in that, in described step c: by the refining methyl tertiary butyl ether that obtains in step b after interchanger heat exchange, temperature of reaction be 200 DEG C ~ 240 DEG C, pressure is 0.6MPa ~ 0.8MPa, the liquid hourly space velocity of refining methyl tertiary butyl ether is 2h
-1~ 4.5h
-1condition under, the refining methyl tertiary butyl ether after heat exchange is sent in calandria type fixed bed reactor, under alumina silicate catalyst effect, carries out scission reaction, obtain the mixed solution of gas phase iso-butylene and Liquid Phase Methanol.
3. a kind of methyl tertiary butyl ether as claimed in claim 1 prepares the method for iso-butylene, it is characterized in that, in described step e: gas phase iso-butylene in steps d is got rid of the rear methyl alcohol sent into methyl alcohol water wash column removal iso-butylene from knockout drum, iso-butylene after removal methyl alcohol is sent into successively the light constituent in two iso-butylene lightness-removing columns removal iso-butylenes of series connection, send into two iso-butylene weight-removing columns of connecting successively after iso-butylene dehydrogenation component and remove heavy constituent in iso-butylenes, obtain high-purity isobutylene.
4. a kind of methyl tertiary butyl ether as claimed in claim 1 prepares the method for iso-butylene, it is characterized in that, in described a step: under temperature is 55 DEG C ~ 65 DEG C conditions, the iso-butylene and methyl alcohol that contain C-4-fraction are added in reactor, under the katalysis of storng-acid cation exchange resin, carry out etherification reaction, obtain methyl tertiary butyl ether, unreacted iso-butylene, unreacted methyl alcohol and unreacted carbon four.
5. a kind of methyl tertiary butyl ether as claimed in claim 4 prepares the method for iso-butylene, it is characterized in that, in described b step: the methyl tertiary butyl ether obtained in step a, unreacted iso-butylene, unreacted methyl alcohol and unreacted carbon four are sent into catalytic rectifying tower and carries out catalytic distillation, obtain refining methyl tertiary butyl ether, obtain unreacted methyl alcohol and unreacted carbon four from catalytic distillation column overhead to send into methyl alcohol water wash column and carry out methyl alcohol drip washing, at the bottom of catalytic rectifying tower tower, obtain methanol aqueous solution send into methanol distillation column and reclaim.
6. a kind of methyl tertiary butyl ether as claimed in claim 1 prepares the method for iso-butylene, it is characterized in that, in described Step d: the mixed solution of the gas phase iso-butylene obtained in step c and Liquid Phase Methanol is sent into knockout drum and carry out being separated of gas phase iso-butylene and Liquid Phase Methanol;
In described f step: Liquid Phase Methanol in steps d is sent into the methanol distillation column obtained in step b and reclaim methyl alcohol, the methanol distillation column that the methanol aqueous solution in the methyl alcohol water wash column obtained is sent in step b is reclaimed methyl alcohol, obtain methanol product in step e.
7. methyl tertiary butyl ether according to claim 3 prepares the method for iso-butylene, it is characterized in that, the pedal number of the lightness-removing column of iso-butylene described in step e is 40 pieces ~ 50 pieces.
8. methyl tertiary butyl ether according to claim 5 prepares the method for iso-butylene, it is characterized in that, in step b, catalytic rectifying tower is provided with 12 layers of beds between stripping section and rectifying section, is provided with two separate tower tray above every layer of bed.
9. methyl tertiary butyl ether according to claim 4 prepares the method for iso-butylene, it is characterized in that, in step a, temperature is 60 DEG C.
10. methyl tertiary butyl ether according to claim 2 prepares the method for iso-butylene, it is characterized in that, in step c, temperature is 220 DEG C, and pressure is 0.7MPa.
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| CN201510565601.1A CN105175203A (en) | 2015-09-08 | 2015-09-08 | Method for preparing isobutene by MTBE (Methyl Tertiary Butyl Ether) |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107382681A (en) * | 2017-08-01 | 2017-11-24 | 山东滨庆新能源开发有限公司 | After the washing of MTBE devices methanol after ether carbon four into azeotropy rectification column reflux technique |
| CN107457001A (en) * | 2016-06-03 | 2017-12-12 | 万华化学集团股份有限公司 | A kind of polystyrene sulfonic acid resin catalyst and its preparation method and application |
| CN110078591A (en) * | 2019-05-08 | 2019-08-02 | 深圳市前海博扬研究院有限公司 | The method of refining crude glycerin |
-
2015
- 2015-09-08 CN CN201510565601.1A patent/CN105175203A/en active Pending
Non-Patent Citations (1)
| Title |
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| 杨志毅等: "甲基叔丁基醚裂解制异丁烯技术进展", 《广东化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107457001A (en) * | 2016-06-03 | 2017-12-12 | 万华化学集团股份有限公司 | A kind of polystyrene sulfonic acid resin catalyst and its preparation method and application |
| CN107457001B (en) * | 2016-06-03 | 2019-09-20 | 万华化学集团股份有限公司 | A kind of polystyrene sulfonic acid resin catalyst and its preparation method and application |
| CN107382681A (en) * | 2017-08-01 | 2017-11-24 | 山东滨庆新能源开发有限公司 | After the washing of MTBE devices methanol after ether carbon four into azeotropy rectification column reflux technique |
| CN110078591A (en) * | 2019-05-08 | 2019-08-02 | 深圳市前海博扬研究院有限公司 | The method of refining crude glycerin |
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