CN100519498C - Phrcess of coproducing methyl tert-butyl ether and tert-butyl alcohol - Google Patents
Phrcess of coproducing methyl tert-butyl ether and tert-butyl alcohol Download PDFInfo
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- CN100519498C CN100519498C CNB2006101048766A CN200610104876A CN100519498C CN 100519498 C CN100519498 C CN 100519498C CN B2006101048766 A CNB2006101048766 A CN B2006101048766A CN 200610104876 A CN200610104876 A CN 200610104876A CN 100519498 C CN100519498 C CN 100519498C
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- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 title claims abstract description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 192
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 238000000605 extraction Methods 0.000 claims description 45
- 230000003197 catalytic effect Effects 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 20
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 19
- 241000282326 Felis catus Species 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006266 etherification reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 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 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The present invention relates to process of co-producing methyl tert-butyl ether and tert-butyl alcohol with isobutene and methanol in C4 fraction. The present invention features that two kinds of product are produced in an identical equipment with reduced investment, and that separation is completed through several reactions, resulting in simplified equipment and facilitated separation.
Description
Technical field
The present invention relates to the production method of a kind of methyl tertiary butyl ether and the trimethyl carbinol, relate in particular to the iso-butylene in the C-4-fraction and the production method of the methanol-water coproducing methyl tertbutyl ether and the trimethyl carbinol.
Background technology
The methyl tertiary butyl ether (being called for short MTBE) and the trimethyl carbinol (being called for short TBA) are a kind of petroleum chemicals, can be used as industrial chemicals, also can be used as gasoline dope.At present, both at home and abroad general what adopt is " anti-three towers " production model to the production method of the existing MTBE of production, and one instead promptly is reactor, and three towers promptly are azeotrope column, extraction tower (claim not only water wash column) and methanol distillation column (but also claiming methanol rectifying tower).Typical technical process is as follows:
Referring to Fig. 2, C-4-fraction and methyl alcohol is incoming stock jar of V10, V11 respectively, enter reactor T10 bottom (or top) through mixing, preheating by a certain percentage after pump P1, the P2 pressurization respectively again, under the effect of catalyzer, iso-butylene in the C-4-fraction and methyl alcohol carry out etherification reaction and generate MTBE.In reactor V10, conversion for isobutene is about 90～95%.For preventing the reactor overtemperature, return again after can extracting reactant flow out heat-obtaining from the reactor stage casing, also can the outer circulation heat-obtaining, reactant flow is extracted out from reactor, through turning back to the inlet circulating reaction of reactor after the condenser cooling again, with control reaction temperature.
Material behind the etherification reaction (carbon four and MTBE behind the ether) is flowed out by reactor T10 top (or bottom), after interchanger E11 and MTBE heat exchange, enter azeotrope column from azeotrope column T11 bottom, through azeotropic separation, MTBE wherein flows out from the azeotrope column bottom, after the material heat exchange behind interchanger E11 and the above-mentioned etherification reaction, cool off device through condenser E12 again, distillate from the top of azeotrope column T11 and contain carbon four behind the ether of small amount of methanol, after overhead condenser E13 condensation, enter return tank V12, extract out from return tank V12 by reflux pump P3 again, separated into two parts then, a part is returned the azeotrope column cat head as backflow, and another part removes extraction tower T12 after water cooler E14 cooling.Azeotrope column T11 also can be designed to catalytic rectifying tower, further continues reactive distillation at Ta Nei and unreacted iso-butylene by replenishing methyl alcohol, to improve conversion for isobutene.
Enter C-4-fraction behind the ether that contains methyl alcohol of extraction tower T12 bottom and extraction water reverse contact in extraction tower from extraction tower top, with the methyl alcohol in the carbon four behind the extraction ether, remove purification C-4-fraction behind the methyl alcohol and overflow to flow into by extraction tower T12 top and purify C-4-fraction jar V13, then by pump P4 carrying device.
Extraction tower T12 is rich in the bottom methanol in water and enters the methanol rectifying tower middle part from the water bottom the methanol rectifying tower T13 after interchanger E15 heat exchange.The methanol rectifying tower bottom water, is returned extraction tower as extraction agent again and is recycled after interchanger E15 and the methanol-water heat exchange from the extraction tower bottom through pump P5 pressurization after extraction water aftercooler E16 cooling.The methyl alcohol of purity 〉=99.5% is distillated by recovery tower T13 top, after overhead condenser E17 condensation, enter methanol eddy jar V14, after extracting out, return tank V14 is divided into two-way by reflux pump P6 again, a part is returned the Methanol Recovery cat head as backflow, and another part is transmitted back to the methanol feedstock jar as the methyl alcohol that reclaims.
Above-mentioned " anti-three towers " method is to produce the more sophisticated method of MTBE at present.Its subject matter is: the chemical reaction that does not make full use of in the flow process between the logistics carries out feed separation, thereby makes technical process concise inadequately, has increased equipment and input.Wherein comparatively obviously step is that the methanol-water of C-4-fraction needs to separate and reclaim methyl alcohol with methanol distillation column behind the extraction tower extraction ether, and do not utilize chemical reaction to come separation of methanol, therefore, it has increased the support equipment of methanol distillation column and tower, has also increased input.
In addition, on 40～44 pages of " chemical industry Technological Economy " the 21st the 2nd phases of volume, reported the production method of producing TBA with direct hydration method, it adopts storng-acid cation exchange resin is catalyzer, at 40～100 ℃, 1.5 under the reaction conditions of～2.5Mpa, the iso-butylene of C-4-fraction and water is synthetic TBA under the effect of catalyzer, and this method flow is short, simple to operate, is the main method of the present domestic production trimethyl carbinol.But not seeing the report of coproduction MTBE and uncle TBA production method in reported in literature as yet, generally all is per unit area yield MTBE and per unit area yield TBA.Each architectonical of per unit area yield technology, equipment each other can not be used, and therefore, it is more than the equipment of joint process, has high input.
Summary of the invention
The objective of the invention is in order to overcome the shortcoming of prior art, providing a kind of can make full use of reaction and carry out the coproducing methyl tertbutyl ether of feed separation and the production method of the trimethyl carbinol, make not only that Production Flow Chart is concise, the equipment less investment, but also can pass through three kinds of petroleum chemicals of a technical process output, i.e. MTBE, TBA and MTBE and TBA mixture.
For achieving the above object, production stage of the present invention is achieved in that
This production method at least by before, during and after move in the system that constitutes of reactor, trimethyl carbinol rectifying tower, catalytic rectifying tower and extraction tower, implementation step is:
One, the C-4-fraction that will contain iso-butylene is preheating to 80 ± 5 ℃, bottom through reactor before entering after the pre-treatment, and will extract the top that the methanol-water that comes out at the bottom of the Tata returns preceding reactor, with the C-4-fraction counter current contact, under the effect of catalyzer, methyl alcohol reaction generation methyl tertiary butyl ether in the preferential and methanol-water of iso-butylene in the C-4-fraction, to remove the methyl alcohol in the methanol-water, simultaneously, iso-butylene in the C-4-fraction also with methanol-water in water reaction generate the trimethyl carbinol, the working pressure of preceding reactor is 1.5 ± 0.5MPa, and service temperature is 80 ± 10 ℃.
Two, the reaction product in preceding reactor is through settlement separate, the wherein lighter oil phase that mainly contains unreacted C-4-fraction and methyl tertiary butyl ether reactor head in the past overflows, and the water of heavier main moisture and trimethyl carbinol the past reactor bottom flows out from compressing into into trimethyl carbinol rectifying tower middle part, distillate about 85% trimethyl carbinol water azeotrope from cat head, the water that comes out at the bottom of the tower enters extraction tower as extraction agent after cooling off, the working pressure of trimethyl carbinol rectifying tower maintains 0.12～0.25MPa, and service temperature is 110.9 ± 10 ℃.
Three, the in the past oil phase that overflows of reactor head and enter middle reactor bottom from behind about 85% the trimethyl carbinol water azeotrope at trimethyl carbinol rectifying tower top heat exchange to 80 together ℃ ± 5 ℃, under the effect of catalyzer, less water in iso-butylene in the C-4-fraction and the trimethyl carbinol water azeotrope continues reaction and generates the trimethyl carbinol, the working pressure of middle reactor is 1.2 ± 0.5MPa, and service temperature is 80 ± 10 ℃.
Four, methanol feedstock and from the reaction product on middle reactor top heat exchange to 43 together ℃ ± 5 ℃, after mixing, enter post-reactor again, under the effect of catalyzer, less water preferential reaction in the C-4-fraction in remaining iso-butylene and the trimethyl carbinol water generates the trimethyl carbinol, iso-butylene continues and excessive methanol feedstock reaction generation methyl tertiary butyl ether simultaneously, the working pressure of post-reactor is 1 ± 0.5MPa, and service temperature is 55 ± 10 ℃.
Five, enter catalytic rectifying tower (T02) middle part from the effusive reaction product in post-reactor top, introduce methyl alcohol at the tower rectifying section simultaneously, this tower section is equipped with catalyzer, the amount of introducing methyl alcohol is a C-4-fraction 0.5～3% (mol) behind the ether, under the effect of rectifying section catalyzer, unreacted isobutene reaction in the C-4-fraction behind methyl alcohol continuation and the ether, come out to contain the bottom that C-4-fraction behind the ether of small amount of methanol removes extraction tower from the rectifying of catalytic distillation cat head, carry at the bottom of the tower and distillate methyl tertiary butyl ether and trimethyl carbinol mix product, the catalytic rectifying tower working pressure is 0.7 ± 0.2MPa, and column bottom temperature is 130 ± 10 ℃.
Six, enter C-4-fraction behind the ether that contains methyl alcohol of extraction tower respectively and water that returns at the bottom of the trimethyl carbinol rectifying tower tower and fresh de-salted water counter-current extraction methyl alcohol, C-4-fraction behind the ether that is purified of extraction tower cat head then, and going out to be rich in the water of methyl alcohol, tower bottom flow returns preceding reactor, form circulation, the extraction tower working pressure is 0.55 ± 0.1MPa, and service temperature is 40 ± 10 ℃.
The further improvement of the present invention scheme is as follows:
One, the methyl tertiary butyl ether of above-mentioned catalytic distillation tower bottom output being introduced the knockout tower middle part with trimethyl carbinol mix product separates, go out pure methyl tertbutyl ether product by cat head rectifying, the tower still is carried and is distillated pure trimethyl carbinol product, the knockout tower working pressure is 0.15 ± 0.05MPa, and service temperature is 95 ± 5 ℃.
Two, from the catalytic distillation column overhead draw a part of phegma enter respectively before, during and after reactor, be used to control the temperature of reaction of each reactor.
By above-mentioned solution as can be seen, method of the present invention can be with a covering device coproducing methyl tertbutyl ether and two kinds of products of the trimethyl carbinol, save energy, than building two covering device saving investment more than 45%, if these two kinds of products all are used for gasoline dope, the mixture of the methyl tertiary butyl ether and the trimethyl carbinol can also not done to separate, directly with their mixture as the gasoline dope product.The present invention also carries out feed separation by the reaction between following three logistics, thereby further concise technical process, has saved the equipment input:
1, in preceding reactor, utilizes small amount of methanol preferential reaction in a large amount of iso-butylenes and the methanol-water removing the methyl alcohol in the methanol-water, thereby omitted the methanol distillation column that generally adopts and the support equipment of tower both at home and abroad.
2, in middle reactor, utilize less water preferential reaction in a large amount of iso-butylenes and the trimethyl carbinol water to remove the moisture content in the trimethyl carbinol water, thereby avoided having saved a large amount of separating devices because there is the caused separating difficulty of azeotropism (trimethyl carbinol azeotropic concentration is 85%) in trimethyl carbinol water.
3, a small amount of unreacted isobutene reaction in the C-4-fraction after catalytic rectifying tower replenishes amount of methanol and ether, to remove the wherein iso-butylene of trace, for the n-butene in the carbon four behind the separation ether provides favourable condition (only 0.6 ℃ of the boiling-point difference of n-butene and iso-butylene adopts conventional distillation to be difficult to separate).
Description of drawings
Fig. 1, Production Flow Chart sketch of the present invention.
Fig. 2, domestic and international common MTBE Production Flow Chart sketch.
Embodiment
Referring to Fig. 1, move in the production method of the present invention system shown in the figure, reactor R01A, R01B, R01C, trimethyl carbinol rectifying tower T01, catalytic rectifying tower T02, extraction tower T04 and knockout tower T03 and their support equipment before, during and after this system comprises, concrete implementation step of the present invention is as follows:
One, utilize preferential and the principle that methyl alcohol reacts in methanol-water (wherein methanol content is 6 ± 4%) of iso-butylene in the C-4-fraction, C-4-fraction is preheating to 80 ± 5 ℃ through preheater E01, the bottom of reactor R01A before entering after process pretreater V01 takes off and subtracts again, and the top of reactor before the methanol-water that comes out at the bottom of the extraction tower T04 tower turned back to, with the C-4-fraction counter current contact, under the effect of catalyzer (catalyzer adopts acidic resins usually), methyl alcohol reaction generation MTBE in the preferential and methanol-water of iso-butylene in the C-4-fraction, to remove the methyl alcohol in the methanol-water, simultaneously, iso-butylene in the C-4-fraction also with methanol-water in water reaction generate TBA, the working pressure of preceding reactor R01A is 1.5 ± 0.5MPa, and service temperature is 80 ± 10 ℃.
Two, reaction product in preceding reactor R01A is through settlement separate, the wherein lighter oil phase that mainly contains unreacted C-4-fraction and MTBE overflows at reactor R01A top in the past, the water of heavier main moisture and TBA reactor bottom outflow in the past separates from compressing into into trimethyl carbinol rectifying tower T01 middle part, cooling enters return tank V02 through condenser E04 to go out about 85% trimethyl carbinol water azeotrope from cat head rectifying, after coming out from return tank, a part passes back into rectifying tower T01 cat head, remainder is delivered to interchanger E03, the water that comes out at the bottom of the tower goes extraction tower T04 as extraction agent after water cooler E10 cooling, the working pressure of trimethyl carbinol rectifying tower T01 maintains 0.12～0.25MPa, service temperature is 110.9 ± 10 ℃, and this tower thermal source is supplied with by the reboiler E07 of tower bottom.
Three, in the past the oil phase that overflows at the top of reactor R01A and from about 85% the trimethyl carbinol water at trimethyl carbinol rectifying tower T01 top together through interchanger E03 heat exchange to 80 ± 5 ℃, the bottom of reactor in entering after mixing through mixing tank MIO2 again, under the effect of catalyzer, less water in iso-butylene in the C-4-fraction and the trimethyl carbinol water azeotrope continues reaction and gives birth to the trimethyl carbinol, the working pressure of middle reactor R01B is 1.2 ± 0.5MPa, service temperature is 80 ± 10 ℃.
Four, material benzenemethanol and from the reaction product on middle reactor R01B top by interchanger E02 heat exchange to 43.5 ± 5 ℃, behind mixing tank MI01 thorough mixing, enter post-reactor R01C again, under the effect of catalyzer, wherein a large amount of iso-butylene and less water preferential reaction in the trimethyl carbinol water generates the trimethyl carbinol in the unreacted C-4-fraction, to remove the moisture in the trimethyl carbinol water, avoided because there is the caused separating difficulty of azeotropism in trimethyl carbinol water, simultaneously, iso-butylene also continues to generate MTBE with little excessive methyl alcohol reaction in the unreacted C-4-fraction, makes iso-butylene meet the requirements of transformation efficiency.The working pressure of post-reactor R01C is 1 ± 0.5MPa, and service temperature is 55 ± 10 ℃.
Five, enter catalytic rectifying tower T02 middle part from the effusive reaction product in post-reactor top (this product be methyl tertiary butyl ether and trimethyl carbinol mixture and the ether that contains methyl alcohol after C-4-fraction), and the amount that accounts for C-4-fraction 0.5～3% (mol) behind the ether with methyl alcohol is replenished methanol feedstock from the tower epimere, rectifying section at catalytic rectifying tower T02 is equipped with catalyzer, under the effect of catalyzer, methyl alcohol is continued and ether after unreacted isobutene reaction in the C-4-fraction, further remove the iso-butylene in the C-4-fraction behind the ether, C-4-fraction comes out through entering return tank V03 after the condenser E05 cooling from the rectifying of catalytic rectifying tower T02 cat head after wherein containing the ether of methyl alcohol, after coming out from return tank, a part is returned catalytic rectifying tower T02 top as backflow, before a part is returned respectively, in, post-reactor R01A, R01B, R01C, be used for the dilution and the cooling reaction mass come the conditioned reaction temperature, another part enters extraction tower T04 extraction methyl alcohol wherein, the catalytic rectifying tower working pressure is 0.7 ± 0.2MPa, service temperature is 130 ± 10 ℃, promptly, make tower still temperature maintenance at 130 ± 10 ℃ by the reboiler E08 heating of tower bottom.Carry at the bottom of the catalytic rectifying tower T02 tower and distillate methyl tertiary butyl ether and trimethyl carbinol mix product goes out device, this mix product can be directly as gasoline dope, further separate if desired, the middle part that methyl tertiary butyl ether and trimethyl carbinol mixture are introduced knockout tower T03 can be separated, go out pure methyl tertbutyl ether product by cat head rectifying, after condenser E06 cooling, enter return tank V04, a methyl tertbutyl ether product part of coming out from return tank is back to the knockout tower cat head, another part goes out device, purity 〉=98% is carried at the bottom of the tower and is distillated the pure trimethyl carbinol and go out device, its purity 〉=98%.Knockout tower T03 working pressure is 0.15 ± 0.05MPa, and service temperature is 95 ± 5 ℃, and promptly the reboiler E09 by tower bottom controls column bottom temperature.
More than the temperature of reaction of each reactor be to control by interchanger E01, interchanger E02 and interchanger E03 and from the phegma at catalytic rectifying tower T02 top, be that each interchanger will enter temperature of reactor and be heated to required preheating temperature, when the temperature of reaction of reactor raises above service temperature, can directly dilute and cool off reaction mass by described phegma, thereby temperature of reaction is lowered; Certainly, this temperature of reaction also can be controlled with traditional modes such as outer circulation.
Six, from catalytic rectifying tower T02 cat head come out a road contain the ether of methyl alcohol after C-4-fraction enter pars infrasegmentalis under the extraction tower T04, make counter-current operation with the water that comes out in trimethyl carbinol rectifying tower T01 bottom, with the methyl alcohol in the C-4-fraction behind the extraction ether, C-4-fraction continues to rise to extraction tower T04 epimere behind the ether behind the extraction methyl alcohol, the fresh de-salted water that replenishes with the epimere top continues to do counter-current extraction, makes that the methanol content≤50ppm in the C-4-fraction goes out device behind the ether.Circulation was formed at the top of reactor before the methanol-water that comes out in extraction tower T04 hypomere bottom continued to turn back to, and extraction tower T04 working pressure is 0.55 ± 0.1MPa, and service temperature is 40 ± 10 ℃.
In order to simplify narration, omitted pump in the system of Fig. 1.
Claims (3)
1, the production method of a kind of coproducing methyl tertbutyl ether and the trimethyl carbinol, this production method at least by before, during and after move in the system that constitutes of three reactors (R01A, R01B, R01C), trimethyl carbinol rectifying tower (T01), catalytic rectifying tower (T02) and extraction tower (T04), implementation step is:
1.1, the C-4-fraction that will contain iso-butylene is preheating to 80 ± 5 ℃, through entering the bottom of preceding reactor (R01A) after the pre-treatment, and the methanol-water that comes out at the bottom of extraction tower (T04) still is returned the top of preceding reactor (R01A), with the C-4-fraction counter current contact, under the effect of catalyzer, methyl alcohol reaction generation methyl tertiary butyl ether in the preferential and methanol-water of iso-butylene in the C-4-fraction, to remove the methyl alcohol in the methanol-water, simultaneously, iso-butylene in the C-4-fraction also with methanol-water in water reaction generate the trimethyl carbinol, the working pressure of preceding reactor (R01A) is 1.5 ± 0.5MPa, and service temperature is 80 ± 10 ℃;
1.2, reaction product in preceding reactor (R01A) is through settlement separate, the wherein lighter oil phase that mainly contains unreacted C-4-fraction and methyl tertiary butyl ether reactor (R01A) top in the past overflows, and the water of the heavier main moisture and trimethyl carbinol flows out from compressing into into trimethyl carbinol rectifying tower (T01) middle part reactor (R01A) bottom in the past, distillate about 85% trimethyl carbinol water azeotrope from cat head, the water that comes out at the bottom of the tower enters extraction tower (T04) as extraction agent after cooling off, the working pressure of trimethyl carbinol rectifying tower (T01) maintains 0.12～0.25MPa, and service temperature is 110.9 ± 10 ℃;
1.3, the in the past oil phase that overflows of reactor (R01A) top and enter middle reactor (R01B) bottom from behind about 85% the trimethyl carbinol water azeotrope at trimethyl carbinol rectifying tower (T01) top heat exchange to 80 together ℃ ± 5 ℃, under the effect of catalyzer, less water in iso-butylene in the C-4-fraction and the trimethyl carbinol water azeotrope continues reaction and generates the trimethyl carbinol, middle reactor (R01B) working pressure is 1.2 ± 0.5MPa, and service temperature is 80 ± 10 ℃;
1.4, methanol feedstock and from the reaction product on middle reactor (R01B) top heat exchange to 43 together ℃ ± 5 ℃, after mixing, enter post-reactor (R01C) again, under the effect of catalyzer, less water preferential reaction in the C-4-fraction in remaining iso-butylene and the trimethyl carbinol water generates the trimethyl carbinol, iso-butylene continues and excessive methanol feedstock reaction generation methyl tertiary butyl ether simultaneously, the working pressure of post-reactor (R01C) is 1 ± 0.5MPa, and service temperature is 55 ± 10 ℃;
1.5, enter catalytic rectifying tower (T02) middle part from the effusive reaction product in post-reactor (R01C) top, introduce methyl alcohol at the tower rectifying section simultaneously, this tower section is equipped with catalyzer, the amount of introducing methyl alcohol is a C-4-fraction 0.5～3% (mol) behind the ether, under the effect of rectifying section catalyzer, methyl alcohol continue and ether after the isobutene reaction of answering after not in the C-4-fraction, come out to contain the bottom that C-4-fraction behind the ether of small amount of methanol removes extraction tower (T04) from the rectifying of catalytic distillation cat head, carry at the bottom of the tower and distillate methyl tertiary butyl ether and trimethyl carbinol mix product, the catalytic rectifying tower working pressure is 0.7 ± 0.2MPa, and column bottom temperature is 130 ± 10 ℃;
1.6, enter C-4-fraction behind the ether that contains methyl alcohol of extraction tower (T04) respectively and water that returns at the bottom of trimethyl carbinol rectifying tower (T01) tower and fresh de-salted water counter-current extraction methyl alcohol, C-4-fraction behind the ether that is purified of extraction tower (T04) cat head then, and going out to be rich in the water of methyl alcohol, tower bottom flow returns preceding reactor (R01A), form circulation, extraction tower (T04) working pressure is 0.55 ± 0.1MPa, and service temperature is 40 ± 10 ℃.
2, the production method of the coproducing methyl tertbutyl ether according to claim 1 and the trimethyl carbinol, it is characterized in that: rectifying separation is carried out at the methyl tertiary butyl ether and trimethyl carbinol mix product introducing knockout tower (T03) middle part of catalytic rectifying tower (T02) bottom output, go out pure methyl tertbutyl ether product by cat head rectifying, the tower still is carried and is distillated pure trimethyl carbinol product, knockout tower (T03) working pressure is 0.15 ± 0.05MPa, and service temperature is 95 ± 5 ℃.
3, the production method of the coproducing methyl tertbutyl ether according to claim 1 and 2 and the trimethyl carbinol, it is characterized in that: from catalytic rectifying tower (T02) cat head draw a part of phegma enter respectively before, during and after reactor (R01A, R01B, R01C), be used to control the temperature of reaction of each reactor.
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| CN101955418B (en) * | 2009-12-16 | 2013-10-16 | 华东理工大学 | Method for preparing ETBE by coupling separation purification |
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| KR102086563B1 (en) * | 2017-01-06 | 2020-03-09 | 주식회사 엘지화학 | Method for producing methyl tert-butylether |
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| CN113952904B (en) * | 2021-09-29 | 2023-03-03 | 陕西延长石油（集团）有限责任公司 | Transformation and driving method of MTBE (methyl tert-butyl ether) production system |
| CN114380667A (en) * | 2021-12-29 | 2022-04-22 | 宿迁联盛科技股份有限公司 | Method for co-producing 3- (3-tert-butyl-4-hydroxy) methyl phenylpropionate and methyl tert-butyl ether |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4418219A (en) * | 1981-03-02 | 1983-11-29 | National Distillers And Chemical Corporation | Preparation of methyl tertiary-butyl ether |
| US4554386A (en) * | 1983-04-01 | 1985-11-19 | Stamicarbon B.V. | Process for the preparation of methyl tertiary butyl ether |
| CN1040360A (en) * | 1989-06-28 | 1990-03-14 | 齐鲁石油化工公司研究院 | The new preparation method of methyl tertiary butyl ether (MTBE) |
| US4925989A (en) * | 1987-06-01 | 1990-05-15 | Texaco Inc. | MTBE preparation from isobutylene/TBA and methanol in presence of an acid resin catalyst |
| CN1117958A (en) * | 1994-08-30 | 1996-03-06 | 中国石化齐鲁石油化工公司 | Process for producing methyl tert-butyl ether for producing high-purity isobutylene |
| CN1153163A (en) * | 1995-12-26 | 1997-07-02 | 中国石油化工总公司上海石油化工研究院 | Process for synthesis of chemical industry type methyl t-butyl ether |
| CN1304917A (en) * | 2000-09-28 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Process for preparing tert-butanol from isobutylene by hydration |
| US6657090B2 (en) * | 2000-10-19 | 2003-12-02 | Oxeno Olefinchemie Gmbh | Process for preparing highly pure raffinate II and Methyl tert-butyl ether |
| CN1511814A (en) * | 2002-12-31 | 2004-07-14 | 中国石化集团齐鲁石油化工公司 | Process for preparing tertiary butanol |
| CN1835902A (en) * | 2003-08-21 | 2006-09-20 | 三菱丽阳株式会社 | Method for producing tertiary butyl alcohol |
-
2006
- 2006-11-08 CN CNB2006101048766A patent/CN100519498C/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4418219A (en) * | 1981-03-02 | 1983-11-29 | National Distillers And Chemical Corporation | Preparation of methyl tertiary-butyl ether |
| US4554386A (en) * | 1983-04-01 | 1985-11-19 | Stamicarbon B.V. | Process for the preparation of methyl tertiary butyl ether |
| US4925989A (en) * | 1987-06-01 | 1990-05-15 | Texaco Inc. | MTBE preparation from isobutylene/TBA and methanol in presence of an acid resin catalyst |
| CN1040360A (en) * | 1989-06-28 | 1990-03-14 | 齐鲁石油化工公司研究院 | The new preparation method of methyl tertiary butyl ether (MTBE) |
| CN1117958A (en) * | 1994-08-30 | 1996-03-06 | 中国石化齐鲁石油化工公司 | Process for producing methyl tert-butyl ether for producing high-purity isobutylene |
| CN1153163A (en) * | 1995-12-26 | 1997-07-02 | 中国石油化工总公司上海石油化工研究院 | Process for synthesis of chemical industry type methyl t-butyl ether |
| CN1304917A (en) * | 2000-09-28 | 2001-07-25 | 中国石油天然气股份有限公司兰州石化分公司 | Process for preparing tert-butanol from isobutylene by hydration |
| US6657090B2 (en) * | 2000-10-19 | 2003-12-02 | Oxeno Olefinchemie Gmbh | Process for preparing highly pure raffinate II and Methyl tert-butyl ether |
| CN1511814A (en) * | 2002-12-31 | 2004-07-14 | 中国石化集团齐鲁石油化工公司 | Process for preparing tertiary butanol |
| CN1835902A (en) * | 2003-08-21 | 2006-09-20 | 三菱丽阳株式会社 | Method for producing tertiary butyl alcohol |
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