CN102329182A - Method for preparing isobutene through direct hydration method - Google Patents
Method for preparing isobutene through direct hydration method Download PDFInfo
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- CN102329182A CN102329182A CN201110217669A CN201110217669A CN102329182A CN 102329182 A CN102329182 A CN 102329182A CN 201110217669 A CN201110217669 A CN 201110217669A CN 201110217669 A CN201110217669 A CN 201110217669A CN 102329182 A CN102329182 A CN 102329182A
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- butylene
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Abstract
The invention discloses a method for preparing isobutene through a direct hydration method. The method for preparing isobutene through separation is carried out by adopting strongly acidic cation exchange resin as a catalyst to separate the isobutene from a C4 mixture through two steps of: firstly, mixing isobutene in the C4 mixture to generate tertiary butyl alcohol through hydration; and secondly, dehydrolyzing the tertiary butyl alcohol to obtain high-purity isobutene. Since the porous strongly acidic cation exchange resin is adopted as the catalyst which has very high selectivity and low possibility of reaction with other alkenes, the purity of the tertiary butyl alcohol is high, and the purity of the isobutene is also high. Gas-phase isobutene is guaranteed to be condensed through circulating water, therefore the operating pressure is generally 0.35-0.4MPa (gauge pressure). The method disclosed by the invention has the advantages of reasonable process and simple preparation, thereby being a simplest, most convenient and ideal method for preparing isobutene.
Description
Technical field
The present invention relates to a kind of Chemicals, particularly a kind of direct hydration method 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.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 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 MTBE 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.MTBE method more promising (seeing that C-4-fraction separates).
The high density iso-butylene is mainly used in and produces polyisobutene and produce butyl rubber with isoprene copolymer in the industry.Iso-butylene and Trimethylmethane carry out alkylated reaction; Can produce the high-octane rating gasoline alkylate; Reacting the gained MTBE 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 methylacrylic acid through oxidation, gets methacrylonitrile through ammoxidation, and hydration can make the trimethyl carbinol again.
Summary of the invention
Problem to be solved by this invention is; Overcome the deficiency of prior art, original technology be 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 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 is high, and energy consumption is high, and product is single.This law can be reduced to 90～95 ℃ with temperature of reaction, and reaction pressure is 0.25～0.35MPa, and air speed is 0.8～1h-1, and dehydration reaction trimethyl carbinol transformation efficiency is 90%～95%, has not only reduced temperature of reaction but also improved reaction conversion ratio.The invention discloses the technology that a kind of direct hydration method prepares iso-butylene; In Sweet natural gas, oil field gas and crude oil, do not contain iso-butylene basically; 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 CCU by-product in the refinery.Following table is that some typical refinery gass are formed.
Refinery gas composition/% (massfraction)
| Project | Air distillation | Catalytic cracking | CR | Hydrogen cracking | Unifining | 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 like hydrocarbon cracking in the technological process of ethene, also there is a certain amount of iso-butylene to generate; But comparatively small amt does not generally separate 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 can the hydro carbons of C4 hydro carbons with other carbon numbers be separated, but will from the hybrid C 4 hydro carbons, obtain highly purified iso-butylene need separate according to the composition of hybrid C 4 hydro carbons.Following table is the boiling point of C4 hydro carbons, from table, can see that the boiling point between them is very approaching, and especially 1-butylene and iso-butylene only differ from 0.6 ℃, is not that a general rectificating method ability is isolating.
The boiling point of various C4 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 | Suitable-2-butylene | 276.85 | 3.7 |
| Normal butane | 272.65 | -0.5 | Instead-2-butylene | 274.05 | 0.9 |
| Iso-butylene | 266.25 | -6.9 | 1,3-butadiene | 268.74 | -4.41 |
| 1-butylene | 266.85 | -6.3 | 1 | 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.
Technology of the present invention is to adopt strongly acidic cationic exchange resin to do the isobutylene separation technology of catalyzer, and isobutylene separation from hybrid C 4 carries out in two steps.Iso-butylene hydration in the first step hybrid C 4 generates the trimethyl carbinol; The dehydration of second Bushu's butanols obtains high-purity isobutylene.Owing to adopt the porous strongly acidic cationic exchange resin to make catalyzer, have very high selectivity, with the rare reaction of other alkene, thereby the purity of the trimethyl carbinol is high, and the purity of iso-butylene is also very high.
Hydration reaction is between two immiscible liquid phases, to carry out, and catalyst resin is very little particle (solid phase), and therefore reaction is in liquid-liquid-solid heterogeneous system, to carry out.Temperature of reaction is about 80 ℃, and pressure is 1.8MPa.In order to make material under temperature of reaction, keep liquid phase, must keep higher pressure, be strictly on guard against that system because of the material vaporization produces bubble, worsens operation.Hydration is a thermopositive reaction, but heat is little, and reaction heat can be taken out of by reacted material basically, need in reactor drum, not cool off.For reaction is carried out smoothly, need C4 and water thorough mixing.
Dehydration reaction is carried out in the presence of adopting with a kind of resin, and charging is to contain 87% the trimethyl carbinol and the azeotrope of water, reacts to be the liquid phase thermo-negative reaction; Every mole of thermal losses is 65.98kJ, and the iso-butylene that the dehydration back generates just obtains highly purified iso-butylene after condensation, washing, rectifying, reduces the reaction dewatering pressure; For generating iso-butylene is favourable; But, need to guarantee that the gas phase iso-butylene carries out condensation with recirculated water, so working pressure is generally 0.35～0.4MPa (gauge pressure) for conserve energy.
1. the partially hydrated reactor drum of iso-butylene hydration is the key equipment of this device, for vertical fixed-bed, and apparatus with catalyst inside.
Raw material C4 and soft water are behind the static mixer thorough mixing; Added by hydration reactor top, water and iso-butylene carry out chemical reaction at this, and the trimethyl carbinol of generation and excessive water come out from the bottom; Be cooled to 25～30 ℃ through brine cooler, in hydration quantizer (being settlement separator), separate.Quantizer top is reacted extraction C4; Mix with fresh soft water through Venturi washing mixing tank, the trimethyl carbinol that will be dissolved among the C4 is extracted in the water, just obtains the surplus C4 that comes together through washing quantizer upper back at last; The bottom is a tertiary butanol aqueous solution, returns hydration reactor.Hydration quantizer lower floor is the aqueous solution that contains alcohol 5%～8%, in flasher, the C4 of oligodynamical in pure water is removed, and sends into trimethyl carbinol rectifying tower again.Through rectifying, cat head obtains containing the azeotrope of the trimethyl carbinol (87%) and water, can do commodity selling, or produces the intermediates of iso-butylene as dehydration.
Hydration reaction is a thermopositive reaction, and the resin thermal conductivity is very poor, therefore must make material uniform distribution in reactor drum, controls the suitable residence time, to prevent the resin bed local superheating, influences the activity of resin, and side reaction is increased.The processing condition of hydration reaction are: temperature of reaction is 80 ℃, and reaction pressure is that (pressure drop is 0.2～0.25MPa) to 1.8MPa, and air speed is 0.7～0.9h-1, and feed water is 1.2～1.5 with C4 amount of substance ratio.
2. trimethyl carbinol dehydration part
The aqueous trimethyl carbinol is heated to 90 ℃ through preheater 13, gets into from the dehydration reactor bottom, fills a certain amount of resin in the reactor drum, and the trimethyl carbinol begins dehydration reaction after getting into resin layer.Generate the iso-butylene gas phase and overflow, after condenser condenses,, make it be back to reactor drum for reclaiming the trimethyl carbinol wherein from reactor drum top.Uncooled iso-butylene is through condensation once more, and condensation is laggard goes into a small amount of trimethyl carbinol that water wash column removes deentrainment.Deliver to the iso-butylene rectifying tower through super-dry then, it is 99.9% finished product iso-butylene that cat head gets purity.
The processing condition of dehydration reaction: temperature of reaction is 90～95 ℃, and reaction pressure is 0.25～0.35MPa, and air speed is 0.8～1h-1, and dehydration reaction trimethyl carbinol transformation efficiency is 90%～95%.
Product iso-butylene specification: iso-butylene purity is 99.9%, t butanol content＜30 μ g/g, and water-content＜100 μ g/g, alkane, alkene amount to＜800 μ g/g.
Description of drawings:
Fig. 1 is a hydration method hydrating process schema; 1-C
4Head tank; The 2-static mixer; The 3-hydration reactor; The 4-brine cooler; 5-hydration quantizer; 6-hydration well heater; 7-Venturi washing mixing tank; 8-washes quantizer; The 9-flasher; 10-alcohol water basin; 11-trimethyl carbinol rectifying tower;
Fig. 2 is a hydration method dehydration process sketch; 12-trimethyl carbinol medial launder wherein; The 13-preheater; The 14-dehydration reactor; 15, the 16-condensing surface; 17-alcohol tank; The 18-water wash column; The thick iso-butylene groove of 19-; The 20-moisture eliminator; 21-iso-butylene rectifying tower.
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, and described these improvement and variation all should be regarded as within the scope of the invention, and scope of the present invention and essence are limited claim.
Embodiment 1
In C 4 fraction, adopt strongly acidic cationic exchange resin to do the isobutylene separation method of catalyzer, isobutylene separation from hybrid C 4 carries out in two steps.Iso-butylene hydration in the first step hybrid C 4 generates the trimethyl carbinol; The dehydration of second Bushu's butanols obtains high-purity isobutylene.Owing to adopt the porous strongly acidic cationic exchange resin to make catalyzer, have very high selectivity, with the rare reaction of other alkene, thereby the purity of the trimethyl carbinol is high, and the purity of iso-butylene is also very high.
Claims (1)
1. a direct hydration method prepares the method for iso-butylene, it is characterized in that in C 4 fraction, adopts strongly acidic cationic exchange resin to do the isobutylene separation method of catalyzer, and isobutylene separation from hybrid C 4 carries out in two steps.Iso-butylene hydration in the first step hybrid C 4 generates the trimethyl carbinol; The dehydration of second Bushu's butanols obtains high-purity isobutylene.Owing to adopt the porous strongly acidic cationic exchange resin to make catalyzer, have very high selectivity, with the rare reaction of other alkene, thereby the purity of the trimethyl carbinol is high, and the purity of iso-butylene is also very high.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633588A (en) * | 2012-03-30 | 2012-08-15 | 北京化工大学 | Method for preparing high-purity isobutene from raffinate C4 by means of separation |
| CN104903455A (en) * | 2012-11-28 | 2015-09-09 | 英威达技术有限责任公司 | Methods for biosynthesis of isobutene |
| 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 |
| CN108863789A (en) * | 2018-06-14 | 2018-11-23 | 西京学院 | A kind of low-purity isobutene prepares the production system and method for methyl methacrylate |
| US10533193B2 (en) | 2013-08-05 | 2020-01-14 | Invista North America S.A.R.L. | Methods for biosynthesis of isobutene |
-
2011
- 2011-08-01 CN CN201110217669A patent/CN102329182A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633588A (en) * | 2012-03-30 | 2012-08-15 | 北京化工大学 | Method for preparing high-purity isobutene from raffinate C4 by means of separation |
| CN102633588B (en) * | 2012-03-30 | 2015-01-28 | 北京化工大学 | Method for preparing high-purity isobutene from raffinate C4 by means of separation |
| CN104903455A (en) * | 2012-11-28 | 2015-09-09 | 英威达技术有限责任公司 | Methods for biosynthesis of isobutene |
| US10533193B2 (en) | 2013-08-05 | 2020-01-14 | Invista North America S.A.R.L. | Methods for biosynthesis of isobutene |
| 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 |
| CN108863789A (en) * | 2018-06-14 | 2018-11-23 | 西京学院 | A kind of low-purity isobutene prepares the production system and method for methyl methacrylate |
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Application publication date: 20120125 |