CN102267854A - Method for preparing isobutylene by virtue of sulfuric acid extraction method - Google Patents
Method for preparing isobutylene by virtue of sulfuric acid extraction method Download PDFInfo
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- CN102267854A CN102267854A CN2011102317718A CN201110231771A CN102267854A CN 102267854 A CN102267854 A CN 102267854A CN 2011102317718 A CN2011102317718 A CN 2011102317718A CN 201110231771 A CN201110231771 A CN 201110231771A CN 102267854 A CN102267854 A CN 102267854A
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Abstract
The invention discloses a method for preparing isobutylene by virtue of a sulfuric acid extraction method, and the method comprises: reacting isobutylene with sulfuric acid to generate tert-butyl sulfate, wherein 65% sulfuric acid and olefins in C4 fractions can react to generate sulfate; decomposing the generated tert-butyl sulfate under the conditions of diluting with water and high temperature (80-100 DEG C) so as to simultaneously obtain isobutylene and tert-butanol; and further dehydrating tert-butanol in the presence of an acid to generate isobutylene. The method disclosed by the invention is reasonable in process and is simple to operate, and is the simplest and most ideal technology for the preparation of isobutylene.
Description
Technical field
The present invention relates to a kind of Chemicals, particularly a kind of sulfuric acid extraction process prepares the technology of iso-butylene, is suitable for producing iso-butylene.
Background technology
(CH3) 2C=CH2 claims 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.Industrial, 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 a 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 adopts the certain pore size scope (approximately
) molecular sieve, from the C 4 fraction raffinate, optionally isolate butylene and normal butane, 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).
Industrial high density iso-butylene is mainly used in produces polyisobutene and and isoprene copolymer production isoprene-isobutylene rubber.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, the rehydrated trimethyl carbinol that makes.
Summary of the invention
Problem to be solved by this invention is, overcome the deficiencies in the prior art, original technology is that isopropylcarbinol is at 360～370 ℃, 0.304～0.405MPa (carries out dehydration reaction (catalyzer is an activated alumina) and can get 86%～87% thick iso-butylene under 3～4atm), can make with extra care iso-butylene through rectifying and after removing acetaldehyde, ether, organic acid then, original method temperature of reaction height, the energy consumption height, product is single.
A kind of sulfuric acid extraction process prepares the method for iso-butylene, it is that iso-butylene and sulfuric acid reaction generate tertiary butyl sulfuric ester, iso-butylene wherein: vitriolic weight fraction ratio is 1: 1-5, vitriolic concentration 45%-65%, the acid tertiary butyl sulfuric ester that reaction generates, under water dilution and 80-100 ℃ of condition, 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.
This law can obtain iso-butylene and two kinds of products of the trimethyl carbinol simultaneously, also can adjust the ratio of two kinds of products as required.。The invention discloses the technology that a kind of sulfuric acid extraction process prepares iso-butylene, in Sweet natural gas, oil field gas and crude oil, do not contain iso-butylene substantially, a large amount of iso-butylenes is mainly from refinery gas and petrochemical complex gas, and it is maximum wherein to contain iso-butylene in the C 4 fraction with catalytic cracking unit by-product in the refinery.Following table is that some typical refinery gass are formed.
Refinery gas composition/% (massfraction)
| Project | Air distillation | Catalytic cracking | Catalytic reforming | Hydrocracking | Hydrofining | Delayed coking | Viscosity breaking |
| H 2 | - | 0.6 | 1.5 | 1.4 | 3.0 | 0.6 | 0.3 |
| CH 4 | 8.5 | 7.9 | 6.0 | 21.8 | 24.0 | 23.3 | 8.1 |
| C 2H 6 | 15.4 | 11.5 | 17.5 | 4.4 | 70.0 | 15.8 | 6.8 |
| C 2H 4 | - | 3.6 | - | - | - | 2.7 | 1.5 |
| C 3H 8 | 30.2 | 14.0 | 31.5 | 15.3 | 3.0 | 18.1 | 8.6 |
| C 3H 6 | - | 16.9 | - | - | - | 6.9 | 4.8 |
| C 4H 10 | 45.9 | 21.3 | 43.5 | 57.1 | - | 18.8 | 36.4 |
| C 4H 8 | - | 24.2 | - | - | - | 13.8 | 33.5 |
| Add up to | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
In petrochemical process, produce as hydrocarbon cracking in the technological process of ethene, also there is a certain amount of iso-butylene to generate, but comparatively small amt generally is not separated into pure component, and with other C4 hydro carbons, or return, or dispatch from the factory as product (liquefied gas) as the raw material of cracking of ethylene.The iso-butylene of these by-products all is to mix with other C4 components, forms C 4 fraction.The iso-butylene that obtains higher degree need be taked some special separation methods.Adopt general rectificating method just the hydro carbons of C4 hydro carbons with other carbon numbers can be separated, but will obtain highly purified iso-butylene from the hybrid C 4 hydro carbons need separate according to the composition of hybrid C 4 hydro carbons.Following table is the boiling point of C4 hydro carbons, can see that the boiling point between them is very approaching from table, and especially 1-butylene and iso-butylene only differ from 0.6 ℃, is not that a general rectificating method energy is isolating.
Various C
4The boiling point of hydro carbons
| The hydro carbons title | Boiling point/K | Boiling point/℃ | The hydro carbons title | Boiling point/K | Boiling point/℃ |
| Trimethylmethane | 261.42 | 11.73 | Along 2 butylene | 276.85 | 3.7 |
| Normal butane | 272.65 | 0.5 | Anti-2 butylene | 274.05 | 0.9 |
| Iso-butylene | 266.25 | 6.9 | 1,3 divinyl | 268.74 | 4.41 |
| 1-butylene | 266.85 | 6.3 | 1,2 divinyl | 284.00 | 10.85 |
Iso-butylene also can be in the presence of hydrogen, with the method acquisition of acetylene polymerization.Dehydrogenation of isobutane also can obtain iso-butylene.In addition, synthetic or isopropylcarbinol dehydration all can obtain iso-butylene from carbon monoxide and hydrogen.
The technology of the present invention is that iso-butylene and sulfuric acid reaction generate tertiary butyl sulfuric ester, but the alkene in sulfuric acid and the C 4 fraction all can generate sulfuric ester, 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, See Figure.Initial use 50% sulfuric acid of this method is because 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.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 by each reactor, and fresh acid is passed through each reactor with the C 4 fraction adverse current from back to front.Raffinate C4 also can carry small amount of acid secretly through settlement separate after last subsider flows out, just obtain containing iso-butylene less than 1.0% raffinate C4 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 from front to back, 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, enters 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, enter 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, enter 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 with 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 by claim.
Embodiment 1
It is that iso-butylene and sulfuric acid reaction generate tertiary butyl sulfuric ester, iso-butylene wherein: vitriolic weight fraction ratio is 1: 1, vitriolic concentration 50%, the acid tertiary butyl sulfuric ester that reaction generates, 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.Specifically see schema 1.
It is that iso-butylene and sulfuric acid reaction generate tertiary butyl sulfuric ester, iso-butylene wherein: vitriolic weight fraction ratio is 1: 2, vitriolic concentration 65%, the acid tertiary butyl sulfuric ester that reaction generates, 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.Specifically see schema 1.
Embodiment 3
It is that iso-butylene and sulfuric acid reaction generate tertiary butyl sulfuric ester, iso-butylene wherein: vitriolic weight fraction ratio is 1: 5, vitriolic concentration 65%, the acid tertiary butyl sulfuric ester that reaction generates, 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.Specifically see schema 1.
Claims (1)
1. a sulfuric acid extraction process prepares the method for iso-butylene, it is that iso-butylene and sulfuric acid reaction generate tertiary butyl sulfuric ester, iso-butylene wherein: vitriolic weight fraction ratio is 1: 1-5, vitriolic concentration 45%-65%, the acid tertiary butyl sulfuric ester that reaction generates, under water dilution and 80-100 ℃ of condition, 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.
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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 |
| CN115228403A (en) * | 2022-07-12 | 2022-10-25 | 安徽益沣石化有限公司 | Desorption system of reactant desorption sulfuric acid fat in four production technologies in carbon |
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Cited By (3)
| 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 |
| CN115228403A (en) * | 2022-07-12 | 2022-10-25 | 安徽益沣石化有限公司 | Desorption system of reactant desorption sulfuric acid fat in four production technologies in carbon |
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Application publication date: 20111207 |