CN102344333A - Method for preparing isobutene by sulfuric acid method - Google Patents
Method for preparing isobutene by sulfuric acid method Download PDFInfo
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- CN102344333A CN102344333A CN2011102111255A CN201110211125A CN102344333A CN 102344333 A CN102344333 A CN 102344333A CN 2011102111255 A CN2011102111255 A CN 2011102111255A CN 201110211125 A CN201110211125 A CN 201110211125A CN 102344333 A CN102344333 A CN 102344333A
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Abstract
The invention discloses a method for preparing isobutene by a sulfuric acid method. The invention is characterized in that 50%-65% sulfuric acid is used, and acidic tert-butyl sulfate generated during the reaction is decomposed under a condition with water dilution and a high temperature (80-100 DEG C) so as to simultaneously obtain isobutene and tert-butyl alcohol. The tert-butyl alcohol can be further dehydrated to generate isobutene in the presence of acids. This is one of the best methods for preparing isobutene.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to the preparation method of chemical intermediate.The present invention adopts sulfuric acid process to prepare iso-butylene, under water dilution and high temperature (80～100 ℃) condition, decomposes, and obtains the iso-butylene and the trimethyl carbinol simultaneously.The trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again.
Background technology
Iso-butylene (CH3) 2C=CH2 claim the 2-methacrylic again.Inflammable, explosion hazard gases (limits of explosion 1.7%～9.0% volume), boiling point-6.90 ℃, 144.75 ℃ of critical temperatures, emergent pressure 4.00MPa.In the industry, iso-butylene nearly all is by obtaining in refinery gas and the c4 cleavage cut (seeing C-4-fraction).The content of iso-butylene is generally 5%～12% in the refinery gas, is generally 20%～30% in the c4 cleavage cut.Make by catalytic dehydrogenation of isobutane with chromic oxide-on-alumina catalyst under the few cases.When to be raw material with conjugated oxidation produced propylene oxide with propylene and Trimethylmethane, iso-butylene was its co-product.
By the C-4-fraction isobutylene separation, tell formerly normally that wherein divinyl carries out later on.The most frequently used isobutylene separation method is a sulfuric acid absorption method, gained iso-butylene purity＞99%, and the rate of recovery reaches 92%.Molecular sieve adsorption, the molecular sieve of employing certain pore size scope (about 3～10) is optionally isolated butylene and normal butane from the C 4 fraction raffinate, and gained iso-butylene purity reaches 99%.Ion-exchange-resin process also can get high-purity isobutylene, but because of reaction efficiency is low, uses wideless.In addition; Also having with the Zeo-karb is catalyzer; Generate methyl tertiary butyl ether with isobutene reaction in methyl alcohol and the C 4 fraction; And the trimer that under an acidic catalyst effect, isobutene oligomerisation is generated diisobutylene and iso-butylene, thereby method such as separate with other components in the C 4 fraction raffinate.Methyl tertiary butyl ether method more promising (seeing that C-4-fraction separates).The high density iso-butylene is mainly used in to be produced polyisobutene and produces isoprene-isobutylene rubber with isoprene copolymer.Iso-butylene and Trimethylmethane carry out alkylated reaction; Can produce the high-octane rating gasoline alkylate; Reacting the gained methyl tertiary butyl ether with methyl alcohol is good gasoline dope, and oligomerisation gained dipolymer and trimer are the additive of vaporizer fuel behind hydrogenation, also are applicable to the raw material for alkylation of making aromatic hydrocarbons.Diisobutylene also can be used as the raw material production isononyl alcohol of oxo process, further makes softening agent.
In addition, iso-butylene can get methacrylic acid through oxidation, gets methacrylonitrile through ammoxidation, and hydration can make the trimethyl carbinol again.Original technology is to adopt isopropylcarbinol at 360～370 ℃; 0.304～0.405MPa (carries out dehydration reaction (catalyzer is an activated alumina) and can get 86%～87% thick iso-butylene, can make with extra care iso-butylene through rectifying and after removing acetaldehyde, ether, organic acid then under 3～4atm).Its production cost is very high, and facility investment is big, and corrodibility is high, is difficult to be fit to large-scale industrial production.
Summary of the invention
Problem to be solved by this invention is; The deficiency that overcomes prior art provides a kind of method that adopts sulfuric acid process to prepare iso-butylene; It is characterized in that iso-butylene and 45%～65% sulfuric acid reaction generate tertiary butyl sulfuric ester; Under water dilution and 80～100 ℃ of conditions, decompose; Obtain the iso-butylene and the trimethyl carbinol simultaneously, the trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again; 45%～65% sulfuric acid process is isolated iso-butylene from C 4 fraction, mainly contain four operations: reaction, regeneration, compression, refining.Carry out as follows:
1. the reaction process reaction process mainly contains three the vertical reactor of chuck, three intersegmental coolers and three subsiders, three acid circulating pumps of having.Every reactor is equipped with subsider, and acid is circulated in a large number, and C 4 fraction is from front to back successively through each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front; The surplus C4 that comes together also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than the surplus C4 of 1.0% collection through alkali cleaning and washing;
2. step for regeneration: this operation key equipment is regenerator column and reboiler, acid cooler and flashing tower; The sulfuric ester that the autoreaction operation is come is introduced into flashing tower, removes a small amount of C4 of dissolved in the sulfuric ester, gets into the middle part of regenerator column again, carries out sulfuric ester decomposition and trimethyl carbinol dehydration, and cat head obtains the iso-butylene and the trimethyl carbinol, obtains 45-65% sulfuric acid at the bottom of the tower.After overcooling, recycle; C4 that the vacuum flashing of flashing tower top is come out is through alkali cleaning, neutralize the acid mist of being carried secretly after, extract out by vacuum pump and to drain into torch;
3. compression, refining step: the gas phase iso-butylene is through after the compressor compresses; Pass through condenser condenses again; Get into the iso-butylene rectifying tower; Cat head obtains finished product 99% above iso-butylene; Be that the trimethyl carbinol and water present method ultimate principle are that iso-butylene and sulfuric acid reaction generate tertiary butyl sulfuric ester at the bottom of the tower; But the alkene in sulfuric acid and the C 4 fraction all can generate sulfuric ester, and sulfuric acid has good selectivity under lesser temps (15～40 ℃), and 45%～65% sulfuric acid is higher than 1-butylene to the absorption rate of iso-butylene.Initial use 65% sulfuric acid of this method was succeeded in developing again afterwards and was used 50% sulfuric acid, and 50% sulfuric acid and 1-butylene speed of response only are and 1/60 of iso-butylene.The acid tertiary butyl sulfuric ester that reaction generates decomposes under water dilution and high temperature (80～100 ℃) condition, obtains the iso-butylene and the trimethyl carbinol simultaneously.The trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again.50% sulfuric acid process is isolated iso-butylene from C 4 fraction, mainly contain four operations: reaction, regeneration, compression, refining.
Its preferred step is following:
1. the reaction process reaction process mainly contains three the vertical reactor of chuck, three intersegmental coolers and three subsiders, three acid circulating pumps of having.Every reactor is equipped with subsider, and acid is circulated in a large number, and C 4 fraction is from front to back successively through each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front.
The surplus C4 that comes together also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than the surplus C4 of 1.0% collection through alkali cleaning and washing.Mainly be 1-butylene and 2-butylene, butane, C 5 fraction and a spot of C3 cut, separablely go out 1-butylene, also can do the raw material of oxydehydrogenation system divinyl as comonomer.
The temperature of reactor by preceding to after, three are respectively 38 ℃, 27 ℃, 17 ℃.
2. this operation of step for regeneration key equipment is regenerator column and reboiler, acid cooler and flashing tower.
The sulfuric ester that the autoreaction operation is come is introduced into flashing tower, removes a small amount of C4 of dissolved in the sulfuric ester, gets into the middle part of regenerator column again, carries out sulfuric ester decomposition and trimethyl carbinol dehydration, and cat head obtains the iso-butylene and the trimethyl carbinol.Obtain 50% sulfuric acid at the bottom of the tower.After overcooling, recycle.
After the trimethyl carbinol and the alkali cleaning of iso-butylene process, a small amount of sulfuric acid that neutralization is carried secretly, through condenser, the trimethyl carbinol and water are condensed into liquid, and iso-butylene is a gas phase, and is settlement separate through separator tank.The thick iso-butylene of upper gaseous phase is delivered to compressor, the separator tank bottom contain tertiary butanol aqueous solution, through water wash column, the trimethyl carbinol is dissolved in the water, a small amount of by-product dipolymer is water-soluble hardly, assembles extraction regularly on water wash column top.Contain tertiary butanol aqueous solution, get into rectifying tower, carry densely through the trimethyl carbinol, cat head obtains 85% the trimethyl carbinol and the azeotrope of water.For containing the water of alcohol hardly, recycle at the bottom of the tower.
C4 that the vacuum flashing of flashing tower top is come out is through alkali cleaning, neutralize the acid mist of being carried secretly after, extract out by vacuum pump and to drain into torch.
3. compression, refining step gas phase iso-butylene pass through condenser condenses again through after the compressor compresses, get into the iso-butylene rectifying tower, and cat head obtains finished product iso-butylene (more than 99%), is the trimethyl carbinol and water at the bottom of the tower.Production equipment leak out acid all through in the alkali and after the dirty pipe network of entering.
Description of drawings:
Fig. 1 is the sulfuric acid process general flow chart.
Embodiment:
Below in conjunction with embodiment the present invention is described; The scheme of embodiment described here; Do not limit the present invention; One of skill in the art can make improvements and change according to spirit of the present invention; Described these improvement and variation all should be considered as within the scope of the invention, and scope of the present invention and essence are limited claim.
Embodiment 1
Iso-butylene and 45% sulfuric acid reaction are generated tertiary butyl sulfuric ester, under water dilution and 80 ℃ of conditions, decompose, obtain the iso-butylene and the trimethyl carbinol simultaneously, the trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again;
Four operations wherein: react, regenerate, compress, make with extra care and carry out as follows:
1. the reaction process reaction process mainly contains three the vertical reactor of chuck, three intersegmental coolers and three subsiders, three acid circulating pumps of having; Every reactor is equipped with subsider, and acid is circulated in a large number, and C 4 fraction is from front to back successively through each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front; The surplus C4 that comes together also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than the surplus C4 of 1.0% collection through alkali cleaning and washing;
2. step for regeneration: this operation key equipment is regenerator column and reboiler, acid cooler and flashing tower; The sulfuric ester that the autoreaction operation is come is introduced into flashing tower, removes a small amount of C4 of dissolved in the sulfuric ester, gets into the middle part of regenerator column again, carries out sulfuric ester decomposition and trimethyl carbinol dehydration, and cat head obtains the iso-butylene and the trimethyl carbinol, obtains 45% sulfuric acid at the bottom of the tower; After overcooling, recycle; C4 that the vacuum flashing of flashing tower top is come out is through alkali cleaning, neutralize the acid mist of being carried secretly after, extract out by vacuum pump and to drain into torch;
3. compression, refining step: the gas phase iso-butylene passes through condenser condenses again through after the compressor compresses, gets into the iso-butylene rectifying tower, and cat head obtains finished product 99% above iso-butylene, is the trimethyl carbinol and water at the bottom of the tower.The sulfuric acid process general flow chart is seen Fig. 1.
Embodiment 2
Iso-butylene and 50% sulfuric acid reaction are generated tertiary butyl sulfuric ester, under water dilution and 100 ℃ of conditions, decompose, obtain the iso-butylene and the trimethyl carbinol simultaneously, the trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again;
Four operations wherein: react, regenerate, compress, make with extra care and carry out as follows:
1. the reaction process reaction process mainly contains three the vertical reactor of chuck, three intersegmental coolers and three subsiders, three acid circulating pumps of having; Every reactor is equipped with subsider, and acid is circulated in a large number, and C 4 fraction is from front to back successively through each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front; The surplus C4 that comes together also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than the surplus C4 of 1.0% collection through alkali cleaning and washing;
2. step for regeneration: this operation key equipment is regenerator column and reboiler, acid cooler and flashing tower; The sulfuric ester that the autoreaction operation is come is introduced into flashing tower, removes a small amount of C4 of dissolved in the sulfuric ester, gets into the middle part of regenerator column again, carries out sulfuric ester decomposition and trimethyl carbinol dehydration, and cat head obtains the iso-butylene and the trimethyl carbinol, obtains 50% sulfuric acid at the bottom of the tower; After overcooling, recycle; C4 that the vacuum flashing of flashing tower top is come out is through alkali cleaning, neutralize the acid mist of being carried secretly after, extract out by vacuum pump and to drain into torch;
3. compression, refining step: the gas phase iso-butylene passes through condenser condenses again through after the compressor compresses, gets into the iso-butylene rectifying tower, and cat head obtains finished product 99.2% above iso-butylene, is the trimethyl carbinol and water at the bottom of the tower.The sulfuric acid process general flow chart is seen Fig. 1.
Embodiment 3
Iso-butylene and 50% sulfuric acid reaction are generated tertiary butyl sulfuric ester, under water dilution and 100 ℃ of conditions, decompose, obtain the iso-butylene and the trimethyl carbinol simultaneously, the trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again;
Four operations wherein: react, regenerate, compress, make with extra care and carry out as follows:
1. the reaction process reaction process mainly contains three the vertical reactor of chuck, three intersegmental coolers and three subsiders, three acid circulating pumps of having; Every reactor is equipped with subsider, and acid is circulated in a large number, and C 4 fraction is from front to back successively through each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front; The surplus C4 that comes together also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than the surplus C4 of 1.0% collection through alkali cleaning and washing;
2. step for regeneration: this operation key equipment is regenerator column and reboiler, acid cooler and flashing tower; The sulfuric ester that the autoreaction operation is come is introduced into flashing tower, removes a small amount of C4 of dissolved in the sulfuric ester, gets into the middle part of regenerator column again, carries out sulfuric ester decomposition and trimethyl carbinol dehydration, and cat head obtains the iso-butylene and the trimethyl carbinol, obtains 60% sulfuric acid at the bottom of the tower; After overcooling, recycle; C4 that the vacuum flashing of flashing tower top is come out is through alkali cleaning, neutralize the acid mist of being carried secretly after, extract out by vacuum pump and to drain into torch;
3. compression, refining step: the gas phase iso-butylene passes through condenser condenses again through after the compressor compresses, gets into the iso-butylene rectifying tower, and cat head obtains finished product 99.34% above iso-butylene, is the trimethyl carbinol and water at the bottom of the tower.The sulfuric acid process general flow chart is seen Fig. 1.
Embodiment 4
Iso-butylene and 65% sulfuric acid reaction are generated tertiary butyl sulfuric ester, under water dilution and 95 ℃ of conditions, decompose, obtain the iso-butylene and the trimethyl carbinol simultaneously, the trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again;
Four operations wherein: react, regenerate, compress, make with extra care and carry out as follows:
1. the reaction process reaction process mainly contains three the vertical reactor of chuck, three intersegmental coolers and three subsiders, three acid circulating pumps of having; Every reactor is equipped with subsider, and acid is circulated in a large number, and C 4 fraction is from front to back successively through each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front; The surplus C4 that comes together also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than the surplus C4 of 1.0% collection through alkali cleaning and washing;
2. step for regeneration: this operation key equipment is regenerator column and reboiler, acid cooler and flashing tower; The sulfuric ester that the autoreaction operation is come is introduced into flashing tower, removes a small amount of C4 of dissolved in the sulfuric ester, gets into the middle part of regenerator column again, carries out sulfuric ester decomposition and trimethyl carbinol dehydration, and cat head obtains the iso-butylene and the trimethyl carbinol, obtains 65% sulfuric acid at the bottom of the tower; After overcooling, recycle; C4 that the vacuum flashing of flashing tower top is come out is through alkali cleaning, neutralize the acid mist of being carried secretly after, extract out by vacuum pump and to drain into torch;
3. compression, refining step: the gas phase iso-butylene passes through condenser condenses again through after the compressor compresses, gets into the iso-butylene rectifying tower, and cat head obtains finished product 99.1% above iso-butylene, is the trimethyl carbinol and water at the bottom of the tower.The sulfuric acid process general flow chart is seen Fig. 1.
Claims (2)
1. method that adopts sulfuric acid process to prepare iso-butylene; It is characterized in that iso-butylene and 45%～65% sulfuric acid reaction generate tertiary butyl sulfuric ester; Under water dilution and 80～100 ℃ of conditions, decompose; Obtain the iso-butylene and the trimethyl carbinol simultaneously, the trimethyl carbinol generation iso-butylene that in the presence of acid, can further dewater again; 45%～65% sulfuric acid process is isolated iso-butylene from C 4 fraction, mainly contain four operations: reaction, regeneration, compression, refining.
2. the described preparation method of claim 1, four operations wherein: reaction, regeneration, compression, refiningly carry out as follows:
1. the reaction process reaction process mainly contains three the vertical reactor of chuck, three intersegmental coolers and three subsiders, three acid circulating pumps of having; Every reactor is equipped with subsider, and acid is circulated in a large number, and C 4 fraction is from front to back successively through each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front; The surplus C4 that comes together also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than the surplus C4 of 1.0% collection through alkali cleaning and washing;
2. step for regeneration: this operation key equipment is regenerator column and reboiler, acid cooler and flashing tower; The sulfuric ester that the autoreaction operation is come is introduced into flashing tower, removes a small amount of C4 of dissolved in the sulfuric ester, gets into the middle part of regenerator column again, carries out sulfuric ester decomposition and trimethyl carbinol dehydration, and cat head obtains the iso-butylene and the trimethyl carbinol, obtains 45-65% sulfuric acid at the bottom of the tower; After overcooling, recycle; C4 that the vacuum flashing of flashing tower top is come out is through alkali cleaning, neutralize the acid mist of being carried secretly after, extract out by vacuum pump and to drain into torch;
3. compression, refining step: the gas phase iso-butylene passes through condenser condenses again through after the compressor compresses, gets into the iso-butylene rectifying tower, and cat head obtains finished product 99% above iso-butylene, is the trimethyl carbinol and water at the bottom of the tower.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020786A (en) * | 2018-09-21 | 2018-12-18 | 常熟市滨江化工有限公司 | The recycling processing method of 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes mother liquor |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109020786A (en) * | 2018-09-21 | 2018-12-18 | 常熟市滨江化工有限公司 | The recycling processing method of 2,5- dimethyl -2,5- bis(t-butylperoxy) hexanes mother liquor |
| CN109020786B (en) * | 2018-09-21 | 2022-03-25 | 常熟市滨江化工有限公司 | Resourceful treatment method of 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane mother liquor |
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Application publication date: 20120208 |