CN105367368A - Method for preparing high-purity isobutene from C_4 hydrocarbon - Google Patents
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Abstract
The invention relates to a method for preparing high-purity isobutene from C_4 hydrocarbon and mainly solves the technical problems that in the prior art, the utilization rate of C_4 hydrocarbon is not high, and the isobutene separation method is complex. The method includes the following steps that a quadric-carbon material and hydrogen are introduced into the bottom of a reaction segment of a reaction distillation tower, butane-1 is isomerized into butane-2 through hydroisomerization, hydrogen gas is discharged in a gas phase mode, iso-butane and isobutene are extracted in a liquid phase, and heavy components containing normal butane and the butane-2 are obtained through a tower kettle; reaction distillation tower top liquid phase distillate is introduced into the middle of an extraction and rectifying tower, an extraction agent is added from the upper portion of the extraction and rectifying tower, iso-butane distillate is obtained at the top of the tower top, solvent containing distillate of the tower kettle is introduced into the middle of a solvent recycling tower, high-purity Isobutylene distillate is obtained at the tower top, and the solvent of the tower kettle returns to the top of the extraction and rectifying tower for being recycled. The method is reasonable in process, simple in procedure, low in production cost and high in purity of isobutylene products and can be used for industrial application to separation and preparation of high-purity isobutene.
Description
Technical field
The present invention relates to a kind of method preparing high-purity isobutylene from C_4 hydrocarbon.
Background technology
Iso-butylene is a kind of important basic organic chemical industry raw material.Be widely used in the production fields such as isoprene-isobutylene rubber, polyisobutene, methyl methacrylate, tert-butylamine, methacrylonitrile.The production method of current high-purity iso-butylene mainly contains methyl tertiary butyl ether (MTBE) cracking process and the trimethyl carbinol (TBA) evaporation.The shortcoming of MTBE cracking process is that side reaction is many, is to obtain isobutene polymer grade product, needs a large amount of separating devices, and flow process is complicated, investment and energy consumption high.The shortcoming of TBA evaporation is that the ion-exchange resin catalyst thermostability used in reaction is not enough, and intensity reduces at relatively high temperatures, and the catalyzer after cracked causes reactor pressure decrease to become large, reduces transformation efficiency and the yield of iso-butylene.
CN101260016A describes a kind of refining plant by the high-purity iso-butylene of MTBE cracking and processing method, this method for raw material with MTBE splitting gas, adopts absorption, methanol dehydration and refining, iso-butylene to take off light separation with de-six heavy tower continuous rectification technical process and obtains iso-butylene product.CN102020526B and CN102690159A describes a kind of method adopting the trimethyl carbinol to prepare iso-butylene, fixed-bed reactor and rectifying tower are formed a system by this method, reactor is back to, top gaseous phase extraction iso-butylene product from rectifying tower side take-off tertiary butanol and water mixture.
C_4 hydrocarbon is one of Main By product of steam cracking device and catalytic cracking unit.Wherein contain Trimethylmethane, iso-butylene, butene-1, divinyl, normal butane, Trans-2-butene, cis-2-butene, (boiling point is respectively-11.8 DEG C ,-6.9 DEG C ,-6.3 DEG C ,-4.5 DEG C ,-0.5 DEG C, 0.9 DEG C, 3.7 DEG C) etc. that quantity does not wait, these components are broad-spectrum industrial chemicals, particularly C 4 olefin.Along with the continuous growth of carbon four output, the comprehensive utilization of C_4 hydrocarbon has become the strong approach of enterprise's cost efficiency, and especially the extraction and application of each component of C 4 olefin is the key point that C_4 hydrocarbon appreciation utilizes.
The boiling point difference of iso-butylene and Trimethylmethane only has 0.6 DEG C, adopts common distillating method to be difficult to effective separation.Usually on metal catalyst, use a small amount of hydrogen, butene-1 and the reaction of butene-2 generation double-bond isomerism can be made.Association reaction distillation technology, not only can the generation direction of flexible double-bond isomerism reaction, simultaneously can remove the component such as divinyl, sulfocompound that may contain in charging.And the boiling point of Trimethylmethane and iso-butylene also only differs 4.9 DEG C, conventional distillation mode is adopted to be separated, then need high theoretical stage and reflux ratio (in most cases stage number can more than 200, and reflux ratio is more than 100), energy consumption is high, less economical, be not suitable for industrial applications.
CN101160274A describes the double bond hydroisomerization of butylene, carbon four logistics that butadiene content is first not more than 1% (weight) by this method passes into fixed bed hydroisomerization reactor, make butadiene hydrogenation, part butene-1 isomery turns to butene-2 simultaneously, again reactor outlet material is passed into catalytic distillation tower, make the further isomery of remaining butene-1 turn to butene-2, obtain in tower reactor the material being rich in butene-2, catalyzer is load precious metal on alumina.CN101885660A describes a kind of method of C 4 hydrocarbon catalysis isobutylene separation and butene-2, C_4 hydrocarbon is passed into reactive distillation column by this method, in tower, butene-1 isomery turns to butene-2, overhead extraction Trimethylmethane and iso-butylene, tower reactor extraction contains the heavy constituent of butene-2, normal butane, and catalyzer is load nickel-base catalyst on alumina.Above-mentioned two sections of patents all do not relate to how being separated Trimethylmethane and iso-butylene.CN102070391A describes the method for comprehensive utilization mixed c 4 preparing isobutene, divinyl in this method first selective hydrogenation removing mixed c 4, then catalytic distillation technology is adopted, butene-1 isomery is made to turn to butene-2, tower top light constituent Trimethylmethane and iso-butylene are separated by ether-based device and obtain MTBE and then cracking obtains high-purity isobutylene, and technical process is long, cost is high.
Summary of the invention
The present invention relates to a kind of method preparing high-purity isobutylene from C_4 hydrocarbon.Technical problem to be solved by this invention is that in prior art, C_4 hydrocarbon utilization ratio is not high, the technical problem of iso-butylene separation method complexity.Provide a kind of method being prepared high-purity isobutylene by C_4 hydrocarbon newly.The method has that butene-1 isomerization rate is high, iso-butylene be separated simple, iso-butylene product purity is high, can obtain the feature of high-purity isobutane simultaneously.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method preparing high-purity isobutylene from C_4 hydrocarbon, comprise the following steps: (a) with the carbon four containing normal butane, Trimethylmethane, iso-butylene, butene-1 and butene-2 for raw material, carbon four and hydrogen are passed into bottom reactive distillation column conversion zone, butene-1 isomery is made to turn to butene-2 by hydro-isomerization, simultaneously rectifying makes again heavy constituent containing normal butane, butene-2 in tower reactor enrichment, and light constituent Trimethylmethane, iso-butylene, hydrogen are in tower top enrichment; B () reactive distillation tower top arranges partial condenser, hydrogen is discharged at top, and bottom extraction contains the liquid phase overhead product of Trimethylmethane and iso-butylene; C () above-mentioned liquid phase overhead product is passed in the middle part of extractive distillation column, extraction agent adds from extractive distillation column top, overhead extraction Trimethylmethane, and tower reactor must contain the tower reactor overhead product of iso-butylene and extraction agent; D () above-mentioned tower reactor overhead product is passed in the middle part of solvent recovery tower, tower top obtains high-purity isobutylene, and the extraction agent that tower reactor obtains is back to extractive distillation column top and recycles; Extraction agent is selected from least one in N-Methyl pyrrolidone, dimethyl formamide, acetonitrile and methylethylketone.
In technique scheme, C_4 hydrocarbon raw material is from one or more mixtures in catalytically cracked C four, carbon-4 or selec-tive hydrogenation carbon four.Described C_4 hydrocarbon is containing normal butane, Trimethylmethane, iso-butylene, butene-1, butene-2 and a small amount of divinyl.
Reactive distillation column is followed successively by rectifying section, conversion zone, stripping section from top to bottom, conversion zone is not limited to a beds, conversion zone is arranged on the top of tower, with guarantee isomerization be in be conducive to generate butene-2 reaction district in, carbon four raw material and hydrogen enter bottom conversion zone, catalyzer be preferably load on the alumina support comprise at least one be selected from nickel, zinc or palladium.In tower, except catalyzer, rest part is common fractional distillation filling-material.
Under certain operating conditions, butadiene hydrogenation a small amount of in reactive distillation column, the sulfocompound that may contain generate heavier sulfide compound, butene-1 isomery turns to butene-2, tower top must contain the light constituent of Trimethylmethane, iso-butylene, hydrogen, through dephlegmator of top of the tower, gas phase discharges hydrogen, and liquid phase extraction Trimethylmethane and iso-butylene, the heavy constituent containing normal butane, butene-2 is discharged from tower reactor.The total number of theoretical plate 50 ~ 100 of reactive distillation column, rectifying section 3 ~ 10, conversion zone height is equivalent to 5 ~ 20 pieces of theoretical stages.Tower top working pressure 0.3MPaG ~ 1.0MPaG, preferred 0.5MPaG ~ 0.7MPaG, hydrogen alkene mol ratio (hydrogen/n-butene) 0.01 ~ 0.06, reflux ratio 5 ~ 60.
Reactive distillation tower top liquid phase Trimethylmethane and iso-butylene overhead product enter in the middle part of extractive distillation column, extraction agent adds from tower top, extraction agent is at least one in N-Methyl pyrrolidone, dimethyl formamide, acetonitrile, methylethylketone, when using the mixture of dimethyl formamide and acetonitrile as achieving good result beyong contemplation during extraction agent, wherein the quality proportioning of dimethyl formamide and acetonitrile is 1/10 ~ 10/1, preferably 2/8 ~ 8/2.Extracting rectifying tower top obtains highly purified Trimethylmethane cut, tower reactor enters in the middle part of solvent recovery tower containing the mixture of iso-butylene and extraction agent, and tower top obtains high-purity isobutylene product, and tower reactor extraction agent returns to extractive distillation column top, recycle, and supplement fresh extraction agent in right amount as required.The total number of theoretical plate 40 ~ 60 of extractive distillation column, working pressure 0.3MPaG ~ 0.9MPaG, preferred 0.5MPaG ~ 0.7MPaG, solvent ratio 5 ~ 15, reflux ratio 2 ~ 10.The total number of theoretical plate 5 ~ 20 of solvent recovery tower, working pressure 0.3MPaG ~ 0.9MPaG, preferred 0.5MPaG ~ 0.7MPaG, reflux ratio 1 ~ 10.
The present invention is by adopting the combination process of reactive distillation and extracting rectifying, and reach the object being separated from C_4 hydrocarbon and preparing high-purity isobutylene, flow process is simple, yield is high, achieves good technique effect.
Accompanying drawing explanation
Fig. 1 is that the present invention prepares the process flow diagram of high-purity isobutylene from C_4 hydrocarbon.
In Fig. 1, C1 is reactive distillation column, C2 is extractive distillation column, C3 is solvent recovery tower, and D1 is partial condenser, and I is rectifying section, II is conversion zone, III is stripping section, and 1 is C_4 hydrocarbon, and 2 is reactive distillation overhead gas phase overhead product, 3 is reactive distillation tower top phegma, 4 is the discharging of reactive distillation tower top liquid phase, and 5 is reactive distillation tower top non-condensable gas, and 6 is the discharging of reactive distillation tower reactor, 7 eject material for extractive distillation column, 8 is the discharging of extracting rectifying tower reactor, and 9 eject material for solvent recovery tower, and 10 is the agent of solvent recuperation tower reactor cycling extraction, 11 is relief liquor, H
2for hydrogen, S is extraction agent.
By the flow process shown in Fig. 1, C_4 hydrocarbon 1 and hydrogen H
2enter bottom the conversion zone II of reactive distillation column C1, in reactive distillation column, butadiene hydrogenation is butene-1/butene-2, butene-1 isomery turns to butene-2, the sulphidic conversion that may contain is thioether, tower top obtains the gas phase overhead product 2 containing Trimethylmethane, iso-butylene, hydrogen, and tower reactor obtains containing the heavy constituent such as normal butane, butene-2 overhead product 6.Gas phase overhead product 2 is through partial condenser D1 partial condensation, non-condensable gas 5 is discharged from top, partial condensation liquid returns reactive distillation column C1 as phegma 3, part enters in the middle part of extractive distillation column C2 as tower top discharging 4, extraction agent S adds from extractive distillation column C2 top, overhead product 7 is Trimethylmethane, and tower reactor overhead product 8 is the mixture containing iso-butylene and extraction agent.Tower reactor overhead product 8 enters solvent recovery tower C3, and tower top obtains highly purified iso-butylene product 9, and tower reactor extraction agent 10 enters extractive distillation column C2 top, recycles.
Below by specific embodiment, the present invention is further illustrated, but scope of the present invention has more than the scope being limited to embodiment and covering.
Embodiment
[embodiment 1]
The total number of theoretical plate 70 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section number of theoretical plate 55, conversion zone are equivalent to 10 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.6MPaG, reflux ratio 20, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 45 of extractive distillation column, tower top working pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase overhead product enters from the 22nd block of plate, and extraction agent methylethylketone enters from the 2nd block of plate, solvent ratio 5, tower top obtains Trimethylmethane mixture, load 10 Grams Per Hour.The total number of theoretical plate 10 of solvent recovery tower, working pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top obtains higher degree iso-butylene, load 163 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.86% of butene-1, iso-butylene purity 98.56%, the iso-butylene rate of recovery 96.17%.
Relevant logistics composition is in table 1.
Table 1
[embodiment 2]
The total number of theoretical plate 70 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section number of theoretical plate 55, conversion zone are equivalent to 10 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.6MPaG, reflux ratio 20, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 45 of extractive distillation column, tower top working pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase overhead product enters from the 22nd block of plate, and extraction agent N-Methyl pyrrolidone enters from the 2nd block of plate, solvent ratio 5, tower top obtains Trimethylmethane mixture, load 10 Grams Per Hour.The total number of theoretical plate 10 of solvent recovery tower, working pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top obtains higher degree iso-butylene, load 163 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.86% of butene-1, iso-butylene purity 98.78%, the iso-butylene rate of recovery 96.39%.
Relevant logistics composition is in table 2.
Table 2
[embodiment 3]
The total number of theoretical plate 70 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section number of theoretical plate 55, conversion zone are equivalent to 10 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.6MPaG, reflux ratio 20, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 45 of extractive distillation column, tower top working pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase overhead product enters from the 22nd block of plate, and extraction agent dimethyl formamide enters from the 2nd block of plate, solvent ratio 5, tower top obtains Trimethylmethane mixture, load 10 Grams Per Hour.The total number of theoretical plate 10 of solvent recovery tower, working pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top obtains higher degree iso-butylene, load 163 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.86% of butene-1, iso-butylene purity 99.11%, the iso-butylene rate of recovery 96.71%.
Relevant logistics composition is in table 3.
Table 3
[embodiment 4]
The total number of theoretical plate 70 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section number of theoretical plate 55, conversion zone are equivalent to 10 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.6MPaG, reflux ratio 20, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 45 of extractive distillation column, tower top working pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase overhead product enters from the 22nd block of plate, and extraction agent acetonitrile enters from the 2nd block of plate, solvent ratio 5, and tower top obtains Trimethylmethane mixture, load 10 Grams Per Hour.The total number of theoretical plate 10 of solvent recovery tower, working pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top obtains higher degree iso-butylene, load 163 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.86% of butene-1, iso-butylene purity 99.08%, the iso-butylene rate of recovery 96.68%.
Relevant logistics composition is in table 4.
Table 4
[embodiment 5]
The total number of theoretical plate 70 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section number of theoretical plate 55, conversion zone are equivalent to 10 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.6MPaG, reflux ratio 20, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 45 of extractive distillation column, tower top working pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase overhead product enters from the 22nd block of plate, the mixture (mass ratio 8:2) of extraction agent dimethyl formamide and acetonitrile enters from the 2nd block of plate, solvent ratio 5, tower top obtains higher degree Trimethylmethane, load 10 Grams Per Hour.The total number of theoretical plate 10 of solvent recovery tower, working pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top obtains high-purity isobutylene, load 163 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.86% of butene-1, iso-butylene purity 99.68%, the iso-butylene rate of recovery 97.27%.
Relevant logistics composition is in table 5.
Table 5
[embodiment 6]
The total number of theoretical plate 70 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section number of theoretical plate 55, conversion zone are equivalent to 10 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.6MPaG, reflux ratio 20, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 45 of extractive distillation column, tower top working pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase overhead product enters from the 22nd block of plate, the mixture (mass ratio 5:5) of extraction agent dimethyl formamide and acetonitrile enters from the 2nd block of plate, solvent ratio 5, tower top obtains higher degree Trimethylmethane, load 10 Grams Per Hour.The total number of theoretical plate 10 of solvent recovery tower, working pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top obtains high-purity isobutylene, load 163 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.86% of butene-1, iso-butylene purity 99.66%, the iso-butylene rate of recovery 97.27%.
Relevant logistics composition is in table 6.
Table 6
[embodiment 7]
The total number of theoretical plate 70 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section number of theoretical plate 55, conversion zone are equivalent to 10 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.6MPaG, reflux ratio 20, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 45 of extractive distillation column, tower top working pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase overhead product enters from the 22nd block of plate, the mixture (mass ratio 2:8) of extraction agent dimethyl formamide and acetonitrile enters from the 2nd block of plate, solvent ratio 5, tower top obtains higher degree Trimethylmethane, load 10 Grams Per Hour.The total number of theoretical plate 10 of solvent recovery tower, working pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top obtains high-purity isobutylene, load 163 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.86% of butene-1, iso-butylene purity 99.65%, the iso-butylene rate of recovery 97.24%.
Relevant logistics composition is in table 7.
Table 7
[embodiment 8]
The total number of theoretical plate 75 of reactive distillation column (number from top to bottom, as follows), theoretical number of plates of rectifying section 8, stripping section number of theoretical plate 55, conversion zone are equivalent to 12 pieces of height equivalent to a theoretical plate, and conversion zone filling take aluminum oxide as the nickel-base catalyst of carrier, the helical packing of rest part filling stainless steel triangle, C_4 hydrocarbon and hydrogen enter bottom tower conversion zone, tower top working pressure 0.5MPaG, reflux ratio 28, hydrogen alkene is than 0.02, inlet amount 360 Grams Per Hour, tower top liquid phase produced quantity 175 Grams Per Hour.The total number of theoretical plate 48 of extractive distillation column, tower top working pressure 0.4MPaG, reflux ratio 5, reactive distillation tower top liquid phase overhead product enters from the 25th block of plate, the mixture (mass ratio 4:6) of extraction agent dimethyl formamide and acetonitrile enters from the 2nd block of plate, solvent ratio 7, tower top obtains higher degree Trimethylmethane, load 10 Grams Per Hour.The total number of theoretical plate 12 of solvent recovery tower, working pressure 0.4MPaG, reflux ratio 6, extractive distillation column reactor distillate enters from the 6th block of plate, and tower top obtains high-purity isobutylene, load 164 Grams Per Hour, tower reactor returns extracting rectifying top of tower containing extraction agent overhead product after cooling, recycles.
The transformation efficiency 99.98% of butene-1, iso-butylene purity 99.75%, the iso-butylene rate of recovery 97.93%.
Relevant logistics composition is in table 8.
Table 8
Claims (9)
1. prepare a method for high-purity isobutylene from C_4 hydrocarbon, comprise the following steps:
(a) with the carbon four containing normal butane, Trimethylmethane, iso-butylene, butene-1 and butene-2 for raw material, carbon four and hydrogen are passed into bottom reactive distillation column conversion zone, butene-1 isomery is made to turn to butene-2 by hydro-isomerization, simultaneously rectifying makes again heavy constituent containing normal butane, butene-2 in tower reactor enrichment, and light constituent Trimethylmethane, iso-butylene, hydrogen are in tower top enrichment;
B () reactive distillation tower top arranges partial condenser, hydrogen is discharged at top, and bottom extraction contains the liquid phase overhead product of Trimethylmethane and iso-butylene;
C () above-mentioned liquid phase overhead product is passed in the middle part of extractive distillation column, extraction agent adds from extractive distillation column top, overhead extraction Trimethylmethane, and tower reactor must contain the tower reactor overhead product of iso-butylene and extraction agent;
D () above-mentioned tower reactor overhead product is passed in the middle part of solvent recovery tower, tower top obtains high-purity isobutylene, and the extraction agent that tower reactor obtains is back to extractive distillation column top and recycles;
Extraction agent is selected from least one in N-Methyl pyrrolidone, dimethyl formamide, acetonitrile and methylethylketone.
2. prepare the method for high-purity isobutylene according to claim 1 from C_4 hydrocarbon, it is characterized in that extraction agent is the mixture of dimethyl formamide and acetonitrile, its ratio is 10/1 ~ 1/10.
3. prepare the method for high-purity isobutylene according to claim 1 from C_4 hydrocarbon, it is characterized in that the total number of theoretical plate 40 ~ 60 of extractive distillation column, working pressure 0.3MPaG ~ 0.9MPaG, solvent ratio 5 ~ 15, reflux ratio 2 ~ 10.
4. prepare the method for high-purity isobutylene according to claim 1 from C_4 hydrocarbon, it is characterized in that the total number of theoretical plate 5 ~ 20 of solvent recovery tower, working pressure 0.3MPaG ~ 0.9MPaG, reflux ratio 1 ~ 10.
5. prepare the method for high-purity isobutylene according to claim 1 from C_4 hydrocarbon, it is characterized in that extractive distillation column adopts continuous extraction operation, extraction agent recycles.
6. prepare the method for high-purity isobutylene according to claim 1 from C_4 hydrocarbon, it is characterized in that C_4 hydrocarbon raw material is from one or more mixtures in catalytically cracked C four, carbon-4 or selec-tive hydrogenation carbon four.
7. the method for high-purity isobutylene is prepared according to claim 1 from C_4 hydrocarbon, it is characterized in that reactive distillation column is made up of rectifying section, conversion zone, stripping section from top to bottom, conversion zone is not limited to a beds, and conversion zone is arranged on the top of tower.
8. prepare the method for high-purity isobutylene according to claim 1 from C_4 hydrocarbon, it is characterized in that conversion zone in reactive distillation column load catalyzer be load on the alumina support comprise at least one be selected from nickel, zinc or palladium; In tower, except catalyzer, rest part is common fractional distillation filling-material.
9. prepare the method for high-purity isobutylene according to claim 1 from C_4 hydrocarbon, it is characterized in that the total number of theoretical plate 50 ~ 100 of reactive distillation column, rectifying section 3 ~ 10, conversion zone height is equivalent to 5 ~ 20 pieces of theoretical stages; Tower top working pressure 0.3MPaG ~ 1.0MPaG, hydrogen alkene mol ratio (hydrogen/n-butene) 0.01 ~ 0.06, reflux ratio 5 ~ 60.
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| CN110354519A (en) * | 2019-08-19 | 2019-10-22 | 凯瑞环保科技股份有限公司 | A kind of device and method that catalytic distillation process produces isobutene polymer grade |
| CN111072440A (en) * | 2019-12-02 | 2020-04-28 | 浙江信汇新材料股份有限公司 | Method for improving comprehensive utilization rate of isobutene |
| CN112638848A (en) * | 2018-08-02 | 2021-04-09 | Omv下游有限公司 | Method for purifying isobutene from C4 stream and treatment system thereof |
| CN112663078A (en) * | 2020-11-03 | 2021-04-16 | 重庆大学 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
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| CN112638848A (en) * | 2018-08-02 | 2021-04-09 | Omv下游有限公司 | Method for purifying isobutene from C4 stream and treatment system thereof |
| TWI724480B (en) * | 2018-08-02 | 2021-04-11 | 奧地利商Ｏｍｖ下游有限公司 | Process for the purification of isobutene from a c4 stream and processing facility therefor |
| CN109354567A (en) * | 2018-12-13 | 2019-02-19 | 丹东明珠特种树脂有限公司 | The isobutene lamination system device and coincidence process method converted by methyl tertiary butyl ether(MTBE) plant modification |
| CN109354567B (en) * | 2018-12-13 | 2023-11-10 | 丹东明珠特种树脂有限公司 | Superposition process method of isobutene superposition system device reconstructed by methyl tertiary butyl ether device |
| CN110354519A (en) * | 2019-08-19 | 2019-10-22 | 凯瑞环保科技股份有限公司 | A kind of device and method that catalytic distillation process produces isobutene polymer grade |
| CN112679300A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Method for preparing propylene from carbon four raw material |
| CN112759500A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for producing propylene by using carbon tetrahydrocarbon |
| CN112759500B (en) * | 2019-10-21 | 2023-04-07 | 中国石油化工股份有限公司 | Method for producing propylene by using carbon tetrahydrocarbon |
| CN111072440A (en) * | 2019-12-02 | 2020-04-28 | 浙江信汇新材料股份有限公司 | Method for improving comprehensive utilization rate of isobutene |
| CN114436740A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method and system for producing 1-butene by using mixed C4 |
| CN114436740B (en) * | 2020-10-20 | 2024-07-23 | 中国石油化工股份有限公司 | Method and system for producing 1-butene by using mixed carbon four |
| CN112663078A (en) * | 2020-11-03 | 2021-04-16 | 重庆大学 | Device and method for preparing adiponitrile by electrolytic dimerization of acrylonitrile |
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