CN1511814A - Process for preparing tertiary butanol - Google Patents
Process for preparing tertiary butanol Download PDFInfo
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- CN1511814A CN1511814A CNA021515441A CN02151544A CN1511814A CN 1511814 A CN1511814 A CN 1511814A CN A021515441 A CNA021515441 A CN A021515441A CN 02151544 A CN02151544 A CN 02151544A CN 1511814 A CN1511814 A CN 1511814A
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- trimethyl carbinol
- water
- carbon
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006703 hydration reaction Methods 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 30
- 229920000570 polyether Polymers 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000004821 distillation Methods 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- 230000003197 catalytic effect Effects 0.000 claims description 22
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 15
- 239000003456 ion exchange resin Substances 0.000 claims description 15
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 15
- 239000004094 surface-active agent Substances 0.000 claims description 13
- -1 styryl phenol Chemical compound 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 4
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 claims description 3
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 238000004230 steam cracking Methods 0.000 claims description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004359 castor oil Substances 0.000 claims description 2
- 235000019438 castor oil Nutrition 0.000 claims description 2
- WTWBUQJHJGUZCY-UHFFFAOYSA-N cuminaldehyde Chemical compound CC(C)C1=CC=C(C=O)C=C1 WTWBUQJHJGUZCY-UHFFFAOYSA-N 0.000 claims description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-IGMARMGPSA-N Carbon-12 Chemical compound [12C] OKTJSMMVPCPJKN-IGMARMGPSA-N 0.000 claims 1
- GPWDPLKISXZVIE-UHFFFAOYSA-N cyclo[18]carbon Chemical compound C1#CC#CC#CC#CC#CC#CC#CC#CC#C1 GPWDPLKISXZVIE-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 abstract description 21
- 239000003054 catalyst Substances 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000004721 Polyphenylene oxide Substances 0.000 abstract 1
- 239000002736 nonionic surfactant Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 25
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002904 solvent Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 241000282326 Felis catus Species 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000005261 decarburization Methods 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000007039 two-step reaction Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The present invention relates to preparation process of tertiary butanol and the preparation process is hydration process of C4 mixture containing isobutylene. The present invention features that isobutylene in C4 mixture fraction and water produce hydration to produce tertiary butanol in the presence of catalyst and polyether of viscosity-average molecular weight 200-800 as non-ionic surfactant. The said preparation process has high isobutylene converting rate, high tertiary butanol selectivity and low tertiary butanol producing cost.
Description
Technical field
The present invention relates to a kind of method for preparing the trimethyl carbinol, particularly a kind of method of utilizing the preparing tert-butanol by isobutene hydration in the mixed c 4 cut.
Background technology
The trimethyl carbinol is clear crystal or liquid, has been widely used in field of fine chemical.Resin hydration method is the universal method of producing the trimethyl carbinol, this method is catalyzer with the sulfonic acid ion exchange resin, utilization contains the mixed c 4 cut hydration of iso-butylene and produces the trimethyl carbinol, because carbon four does not dissolve each other with water, not only cause conversion for isobutene lower, be generally 30%～50%, and cause butene polymerization, thereby reduce the work-ing life of catalyzer and the productive rate of the trimethyl carbinol.
In order to improve the transformation efficiency and the selectivity of resin hydration method, people have done many research, discovery adds the mutual solubility that some solvents can improve water and carbon four in hydration reaction, and then the raising conversion for isobutene, used solvent has acetate, ethylene glycol, glycol ether, ethylene glycol diether, neo-pentyl type polyvalent alcohol etc.Though the adding of these solvents has improved transformation efficiency, also brought some problems, as equipment corrosion, solvent recuperation etc., its results of industrial application is not satisfactory.CN1283174 discloses a kind of method of producing the trimethyl carbinol, it is characterized in that with the trimethyl carbinol as solvent, thereby having overcome with other organism is the side reaction that causes of solvent and the separation problem that brings thus, but because the trimethyl carbinol shared part by weight in reaction solution is bigger, process cost is higher; It is the trimethyl carbinol preparation method of solvent with acetate that JP59802176 discloses a kind of, and conversion for isobutene is greater than 90%, but equipment such as reactor and distillation tower must adopt anticorrosion material.In addition, people have also done deep research to the pattern of hydration reaction, USP4982022 discloses a kind of method of catalytic distillation hydration preparing tert-butanol, it is characterized in that advancing a certain amount of water on catalytic distillation tower conversion zone top, to improve conversion for isobutene, owing to do not add other solvent in the reaction solution, therefore, unavoidably have the aggregation problem of butylene in the hydration reaction.
Summary of the invention
The purpose of this invention is to provide a kind of new mixed c 4 to contain iso-butylene is raw material, the method for preparing the trimethyl carbinol by hydration reaction, it is characterized in that iso-butylene in the mixed c 4 cut and water carry out hydration reaction and generates the trimethyl carbinol in the presence of catalyzer and viscosity-average molecular weight are polyethers nonionic surface active agent in 200～800 scopes.
Among the present invention because to have viscosity-average molecular weight be polyethers nonionic surface active agent in 200～800 scopes, thereby improved the mixed effect of water and carbon four in the hydration reaction process, and the polyethers nonionic surface active agent chemical property that is added is stable, consumption is considerably less, the side reaction, solvent recuperation and the trimethyl carbinol separation problem that bring when therefore not having other organism for solvent.
Mixed c 4 cut of the present invention is meant the mixed c 4 that the mixed c 4 that removes the preparing ethylene by steam cracking process by-product behind the divinyl or refinery catalytic cracking are produced, and iso-butylene content wherein is 15%～60 weight %.
Catalyzer of the present invention is that granularity is the macropore sulfonic acid ion exchange resin of Φ 0.3～1.2mm, also can be the sulfonic acid ion exchange resin of macrobead shape, and its shape comprises column, Raschig ring shape, wheel shape.
Viscosity-average molecular weight of the present invention is that the polyethers nonionic surface active agent in 200～800 scopes can be two or more a mixture of alkylphenol polyoxyethylene polyoxypropylene ether, styryl phenol polyoxyethylene polyoxypropylene ether, cumic aldehyde phenol polyethenoxy ether, dodecyl phenol polyethenoxy ether, castor oil polyoxyethylene ether, fatty alcohol-polyoxyethylene ether, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether or its.Viscosity-average molecular weight is measured can be with reference to GB1632-79.
Method provided by the invention is that iso-butylene in the mixed c 4 cut and water carry out hydration reaction and generates the trimethyl carbinol in the presence of catalyzer and viscosity-average molecular weight are polyethers nonionic surface active agent in 200～800 scopes.Hydration reaction described here can be finished in fixed-bed reactor, also can finish in catalytic distillation tower, can also finish in two steps in fixed-bed reactor and catalytic distillation tower.
If adopt fixed-bed reactor to realize the present invention, may further comprise the steps:
(a) the mixed c 4 cut that will contain iso-butylene is with after the water that contains the polyethers nonionic surface active agent mixes, send into the fixed bed hydration reactor, the water that maybe will contain the mixed c 4 cut of iso-butylene and contain the polyethers nonionic surface active agent is sent into the fixed bed hydration reactor respectively, under the effect of catalyzer, iso-butylene in the mixed c 4 and water reaction generate the trimethyl carbinol.
(b) material that step (a) is come out is sent into decarburization four towers, and unreacted C-4-fraction is discharged from cat head, contains tertiary butanol aqueous solution and discharges at the bottom of tower.
(c) trimethyl carbinol aqueous solution that contains that comes out from step (b) enters trimethyl carbinol treating tower, obtains the trimethyl carbinol product of purity 〉=85% from the cat head of trimethyl carbinol treating tower.
The recirculated water that the above-mentioned water that goes out from the trimethyl carbinol treating tower tower bottom flow of step (c) can be used as the fixed bed hydration reactor uses.
If adopt two-step reaction realization the present invention that fixed bed hydration reactor and catalytic distillation tower are combined, may further comprise the steps:
(a) the mixed c 4 cut that will contain iso-butylene is with after the water that contains the polyethers nonionic surface active agent mixes, send into the fixed bed hydration reactor, the water that maybe will contain the mixed c 4 cut of iso-butylene and contain the polyethers nonionic surface active agent is sent into the fixed bed hydration reactor respectively, under the effect of catalyzer, iso-butylene in the mixed c 4 and water reaction generate the trimethyl carbinol.
(b) material that step (a) is come out is sent into catalytic distillation tower, and under the effect of catalyzer, iso-butylene in the material and water continue reaction and generates the trimethyl carbinol, finish carbon four and trimethyl carbinol separation of water solution simultaneously.
(c) trimethyl carbinol aqueous solution that comes out from step (b) enters trimethyl carbinol treating tower, obtains the trimethyl carbinol product of purity 〉=85% from the cat head of trimethyl carbinol treating tower.
The recirculated water that the above-mentioned water that goes out from the trimethyl carbinol treating tower tower bottom flow of step (c) can be used as fixed bed hydration reactor and catalytic distillation tower uses.
Separately the two-step reaction that fixed bed hydration reactor and catalytic distillation tower combine is similar with the technology of a catalytic distillation tower and employing, just removed the fixed bed hydration reactor of front.
The drawing explanation
Accompanying drawing 1 is the present invention finishes reaction with the fixed bed hydration reactor a process flow diagram.
Accompanying drawing 2 is that the present invention combines the process flow diagram of finishing reaction with fixed bed hydration reactor and catalytic distillation tower.
Below in conjunction with accompanying drawing that tert-butyl alcohol preparation method more detailed description of the present invention is as follows:
Accompanying drawing 1 technology is 200～800 for the viscosity average molecular weigh that adds 0.01%～0.5% (weight) in water The polyethers nonionic surface active agent, will contain isobutene mixing carbon four (1), contain polyethers water (2) with follow Ring water (15) enters fixed bed reactors (4) after static mixer (3) mixes and is preheating to uniform temperature, in reaction The catalyst of packing in the device (4) is that granularity is the macropore sulfonic acid ion exchange resin of Φ 0.3～1.2mm, also can To be the sulfonic acid ion exchange resin that is shaped as the bulky grain shape of column, Raschig ring shape or wheel shape, at this Under the effect of catalyst, the isobutene hydration generates the tert-butyl alcohol. The suitable operating conditions of fixed bed reactors (4) is: 40～80 ℃ of inlet temperatures, pressure 0.6～2.5MPa, carbon four liquid phase air speeds 0.2～1.0h-1, water and carbon four The ratio of volume flow be 0.5～3: 1.
Material (5) after flowing out from reactor (4) directly enters decarburization four towers (6), unreacted C-4-fraction (8) from Cat head is discharged, and at a certain amount of water of upper supplementary (7) of decarburization four towers (6), discharges from decarburization four towers (6) bottom The aqueous solution (9) that contains the tert-butyl alcohol. The suitable operating conditions of decarburization four towers (6) is: pressure 0.4～0.9MPa, Reflux ratio be 0.5: 1～3.0: 1, supplementing water and the volume flow ratio that advances reactor carbon four be 1: 3～1: 10, Tower top temperature is that 40～70 ℃, column bottom temperature are 110～160 ℃.
The rare pure water (9) that goes out from decarburization four towers (6) tower bottom flow directly enters tert-butyl alcohol treating column (10) and carries out rectifying, essence The operating pressure of tower processed (10) is normal pressure, and reflux ratio is 1.5: 1, is purity greater than 85% from what cat head flowed out Tert-butyl alcohol product (15), the water (12) that goes out from a tower bottom flow part (13) discharger, another part (15) is through negative and positive After filtering, ion exchange bed (14) continues to use as recirculated water.
Accompanying drawing 2 technologies are 200～800 for the viscosity average molecular weigh that adds 0.01%～0.5% (weight) in water The polyethers nonionic surface active agent, will contain isobutene mixing carbon four (1), contain polyethers water (2) with follow Ring water (20) enters fixed bed reactors (4) after static mixer (3) mixes and is preheating to uniform temperature, in reaction The catalyst grain size of packing in the device (4) is the macropore sulfonic acid ion exchange resin of Φ 0.3～1.2mm, also can Be the sulfonic acid ion exchange resin that is shaped as the bulky grain shape of column, Raschig ring shape or wheel shape, urge at this Change under the effect of agent, 50%～75% isobutene hydration generates the tert-butyl alcohol. The suitable behaviour of fixed bed reactors (4) As condition be: 40～80 ℃ of inlet temperatures, pressure 0.6～2.5MPa, carbon four liquid phase air speeds 0.2～1.0h-1, Water is 0.5～3: 1 with the ratio of the volume flow of carbon four.
Material (5) after flowing out from reactor (4) directly enters the bottom of catalytic distillation tower (6) conversion zone (7), instead Should the middle catalyst that loads of section (7) be that granularity is the macropore sulfonic acid ion exchange resin of Φ 0.3～1.2mm, also Can be the sulfonic acid ion exchange resin that is shaped as the bulky grain shape of column, Raschig ring shape or wheel shape, Under the effect of this catalyst, isobutene continues to generate the tert-butyl alcohol with the water reaction, unreacted C-4-fraction (9) from Cat head is discharged and is advanced collecting tank through condensation rear portion (10), and a part (11) is converged through static mixer with recirculated water (19) (12) enter the top of conversion zone (7) after mixing, a certain amount of the going of upper supplementary of catalytic distillation tower (6) rectifying section Ionized water (8), what discharge from catalytic distillation tower (6) bottom is the aqueous solution (13) that contains the tert-butyl alcohol. Catalytic distillation tower (6) Suitable operating conditions be: pressure 0.4～0.9MPa, reflux ratio are 0.5: 1～3.0: 1, backflow carbon four With the ratio of the volume flow of water be 2.0: 1～0.5: 1, supplementing water and the volume flow ratio that advances reactor carbon four Be that 1: 3～1: 10, tower top temperature are that 40～70 ℃, column bottom temperature are 110～160 ℃.
The rare pure water (13) that goes out from catalytic distillation tower (6) tower bottom flow directly enters tert-butyl alcohol treating column (14) and carries out rectifying, The operating pressure for the treatment of column (14) is normal pressure, and reflux ratio is 1.5: 1, is purity greater than 85% from what cat head flowed out Tert-butyl alcohol product (15), the water (16) that goes out from a tower bottom flow part (17) discharger, another part through negative and positive from After filtering, son exchange bed (18) continues to use as recirculated water.
Tert-butyl alcohol preparation method provided by the present invention compared with prior art has the following advantages: the one, and at water In added specific polyethers nonionic surface active agent, greatly improved the mixed effect of water and carbon four, Thoroughly the butene polymerization side reaction in the hydration reaction process has been eliminated at the end, the hydration reaction tert-butyl alcohol selectively greater than 99%, two, obviously improved the conversion ratio (60%～95%) of isobutene, increased the productive rate of the tert-butyl alcohol, fall Low production cost.
By means of embodiment effect of the present invention is described below.
Embodiment
Embodiment 1:
The C-4-fraction of producing with the refinery catalytic cracking is the raw material production trimethyl carbinol, and iso-butylene content is 25.5% (weight) in the carbon four, and the adding viscosity-average molecular weight is 600 dodecyl phenol polyethenoxy ether in the water, and add-on is 0.06% (weight).The granularity of packing in the reactor is the macropore sulfonic acid ion exchange resin of Φ 0.3～1.2mm.Table 1 has been listed the operational condition and the result of fixed-bed reactor.
Table 1 catalytically cracked C four synthetic trimethyl carbinol test-results
Project result
Carbon four liquid phase air speeds, h
-10.32
The water yield/carbon four amounts, v/v 1.2: 1
Temperature in, ℃ 62
Pressure, MPa 1.6
Trimethyl carbinol selectivity, % 99.4
Isobutene conversion, % 65.5
Material after flowing out from reactor enters decarburization four towers, and the operational condition of this tower is: pressure 0.8MPa, reflux ratio are that 1: 1, make up water and the volume flow ratio that advances reactor carbon four are that 1: 7, tower top temperature are that 62 ℃, column bottom temperature are 160 ℃.Unreacted C-4-fraction is discharged from cat head, what discharge from the bottom is to contain tertiary butanol aqueous solution directly to enter trimethyl carbinol distillation tower, the working pressure of trimethyl carbinol distillation tower is a normal pressure, reflux ratio is 2.5: 1, tower top temperature is 78 ℃, column bottom temperature is 105 ℃, and a water part that goes out from trimethyl carbinol distillation tower tower bottom flow recycles after filtering through zwitterion exchange bed, from the effusive purity that is of trimethyl carbinol distillation tower cat head greater than 85% trimethyl carbinol product.
Embodiment 2:
With the preparing ethylene by steam cracking process by-product mixed c 4 that removes behind the divinyl is the raw material production trimethyl carbinol, the iso-butylene weight content is 48.5% (weight) in the carbon four, the adding viscosity-average molecular weight is 300 ten four carbon alcohols Soxylat A 25-7s in the water, add-on is 0.1% (weight), the mean particle size of packing in the fixed bed hydration reactor is the macropore sulfonic acid ion exchange resin of Φ 0.45mm, and what the catalytic distillation tower conversion zone was adorned is the sulfonic acid ion exchange resin that is shaped as column.Table 2 has been listed the operational condition and the result of fixed-bed reactor and catalytic distillation tower.
Table 2 ethylene cracker by-product carbon four synthetic trimethyl carbinol test-results
Project result
Fixed-bed reactor
Carbon four liquid phase air speeds, h
-10.45
The water yield/carbon four amounts, v/v 1.5: 1
Temperature in, ℃ 55
Pressure, MPa 1.5
Trimethyl carbinol selectivity, % 99.6
Isobutene conversion, % 71.5
Catalytic distillation tower
Reflux ratio 1.1: 1
Pressure, MPa 0.7
Temperature, ℃
Cat head 52
At the bottom of the tower 147
The backflow carbon four amount/water yields, v/v 1: 1
Rate of water make-up/material carbon four amounts, v/v 1: 4
Cat head is formed, % (m/m)
Iso-butylene 6.53
Form % (m/m) at the bottom of the tower
The trimethyl carbinol 13.15
Water 86.81
Other is 0.04 years old
Total conversion rate, % 92.58
Overall selectivity, % 99.5
The diluted alcohol aqueous solution that goes out from the catalytic distillation tower tower bottom flow enters trimethyl carbinol treating tower, the working pressure of trimethyl carbinol treating tower is a normal pressure, reflux ratio is 1.5: 1, tower top temperature is 78 ℃, column bottom temperature is 105 ℃, return fixed-bed reactor after a water part that goes out from trimethyl carbinol treating tower tower bottom flow is filtered through zwitterion exchange bed and catalytic distillation tower continues to use, from the effusive purity that is of trimethyl carbinol treating tower cat head greater than 85% trimethyl carbinol product.
Claims (10)
1, a kind of method for preparing the trimethyl carbinol is characterized in that iso-butylene in the mixed c 4 cut and water carry out hydration reaction and generates the trimethyl carbinol in the presence of catalyzer and viscosity-average molecular weight are polyethers nonionic surface active agent in 200～800 scopes.
2, in accordance with the method for claim 1, mixed c 4 cut wherein is meant the mixed c 4 that the mixed c 4 that removes the preparing ethylene by steam cracking process by-product behind the divinyl or refinery catalytic cracking are produced.
3, in accordance with the method for claim 2, iso-butylene content is 15%～60 weight % in the mixed c 4 cut wherein.
4,, it is characterized in that described catalyzer refers to that granularity is the macropore sulfonic acid ion exchange resin of Φ 0.3～1.2mm according to claim 1,2 or 3 described methods.
5,, it is characterized in that described catalyzer is the sulfonic acid ion exchange resin of macrobead shape according to claim 1,2 or 3 described methods.
6, in accordance with the method for claim 5, the shape that it is characterized in that the sulfonic acid ion exchange resin of described macrobead shape comprises column, Raschig ring shape or wheel shape.
7,, it is characterized in that described polyethers is alkylphenol polyoxyethylene polyoxypropylene ether, styryl phenol polyoxyethylene polyoxypropylene ether, cumic aldehyde phenol polyethenoxy ether, dodecyl phenol polyethenoxy ether, castor oil polyoxyethylene ether, carbon 12 to two or more mixture of the fatty alcohol-polyoxyethylene ether of carbon 18, polyoxyethylene nonylphenol ether, polyoxyethylene octylphenol ether or its according to claim 1,2 or 3 described methods.
8,, it is characterized in that described hydration reaction finishes in fixed-bed reactor according to claim 1,2 or 3 described methods.
9,, it is characterized in that described hydration reaction finishes in catalytic distillation tower according to claim 1,2 or 3 described methods.
10,, it is characterized in that described hydration reaction finishes in fixed-bed reactor and catalytic distillation tower according to claim 1,2 or 3 described methods.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02151544 CN1221506C (en) | 2002-12-31 | 2002-12-31 | Process for preparing tertiary butanol |
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|---|---|---|---|
| CN 02151544 CN1221506C (en) | 2002-12-31 | 2002-12-31 | Process for preparing tertiary butanol |
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| CN1511814A true CN1511814A (en) | 2004-07-14 |
| CN1221506C CN1221506C (en) | 2005-10-05 |
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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 |
| CN101402549B (en) * | 2008-11-11 | 2011-11-30 | 中国石油兰州石油化工公司 | Improved process for producing low carbon alcohol with direct hydration of light olefins |
| US8637716B2 (en) | 2005-11-01 | 2014-01-28 | Asahi Kasei Chemicals Corporation | Processes for production of isobutene and tertiary butanol |
| CN103664520A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing isopropyl alcohol through hydration reaction of propylene |
| CN104478657A (en) * | 2014-11-20 | 2015-04-01 | 北京恩泽福莱科技有限公司 | Method for preparing tertiary butanol by using hydration of isobutene in mixed C4 |
| CN110551002A (en) * | 2019-10-11 | 2019-12-10 | 丹东明珠特种树脂有限公司 | Method for preparing tert-butyl alcohol by hydrating carbon tetraisobutylene component and preparation system thereof |
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2002
- 2002-12-31 CN CN 02151544 patent/CN1221506C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8637716B2 (en) | 2005-11-01 | 2014-01-28 | Asahi Kasei Chemicals Corporation | Processes for production of isobutene and tertiary butanol |
| TWI483922B (en) * | 2005-11-01 | 2015-05-11 | Asahi Kasei Chemicals Corp | Method for producing tertiary butanol and continuous manufacturing device for tertiary butanol |
| US9145342B2 (en) | 2005-11-01 | 2015-09-29 | Asahi Kasei Chemicals Corporation | Processes for production of isobutene and tertiary butanol |
| US9919283B2 (en) | 2005-11-01 | 2018-03-20 | Asahi Kasei Chemicals Corporation | Processes for production of isobutene and tertiary butanol |
| CN100519498C (en) * | 2006-11-08 | 2009-07-29 | 褚雅志 | Phrcess of coproducing methyl tert-butyl ether and tert-butyl alcohol |
| CN101402549B (en) * | 2008-11-11 | 2011-11-30 | 中国石油兰州石油化工公司 | Improved process for producing low carbon alcohol with direct hydration of light olefins |
| CN103664520A (en) * | 2012-09-20 | 2014-03-26 | 中国石油化工股份有限公司 | Method for preparing isopropyl alcohol through hydration reaction of propylene |
| CN103664520B (en) * | 2012-09-20 | 2015-08-19 | 中国石油化工股份有限公司 | The method of Virahol is prepared in a kind of propylene hydration reaction |
| CN104478657A (en) * | 2014-11-20 | 2015-04-01 | 北京恩泽福莱科技有限公司 | Method for preparing tertiary butanol by using hydration of isobutene in mixed C4 |
| CN104478657B (en) * | 2014-11-20 | 2017-02-22 | 北京恩泽福莱科技有限公司 | Method for preparing tertiary butanol by using hydration of isobutene in mixed C4 |
| CN110551002A (en) * | 2019-10-11 | 2019-12-10 | 丹东明珠特种树脂有限公司 | Method for preparing tert-butyl alcohol by hydrating carbon tetraisobutylene component and preparation system thereof |
| CN110551002B (en) * | 2019-10-11 | 2023-10-13 | 丹东明珠特种树脂有限公司 | Method and system for preparing tertiary butanol by hydration of carbon tetraisobutene component |
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