CN105367368B - The method that high-purity isobutylene is prepared from C_4 hydrocarbon - Google Patents
The method that high-purity isobutylene is prepared from C_4 hydrocarbon Download PDFInfo
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Abstract
The present invention relates to a kind of method that high-purity isobutylene is prepared from C_4 hydrocarbon, mainly solve that C_4 hydrocarbon utilization rate in the prior art is not high, the complicated technical problem of isobutene separation method.The present invention is by using following steps：C 4 materials and hydrogen are passed into reactive distillation column conversion zone bottom, butylene 1 is isomerized to butylene 2, gas phase discharge hydrogen, liquid phase extraction iso-butane and isobutene by hydro-isomerization, tower reactor must contain normal butane, the heavy constituent of butylene 2；Reactive distillation tower top liquid phase distillate is passed into the middle part of extractive distillation column, extractant is added from extractive distillation column top, tower top obtains iso-butane distillate, solvent of the tower reactor containing isobutene is passed through in the middle part of solvent recovery tower, tower top obtains high-purity isobutylene distillate, tower reactor solvent returns to extracting rectifying top of tower, recycles.Rationally, flow is simple, and production cost is low for present invention process, and isobutene product purity is high, in the commercial Application that high-purity isobutylene is prepared available for separation.
Description
Technical field
The present invention relates to a kind of method that high-purity isobutylene is prepared from C_4 hydrocarbon.
Background technology
Isobutene is a kind of important basic organic chemical industry raw material.It is widely used in butyl rubber, polyisobutene, methyl-prop
The production fields such as e pioic acid methyl ester, tert-butylamine, methacrylonitrile.The production method of current high-purity isobutene mainly has methyl- tert fourth
Base ether (MTBE) cracking process and the tert-butyl alcohol (TBA) evaporation.The shortcoming of MTBE cracking process is that side reaction is more, different to obtain polymer grade
Butylene product is, it is necessary to substantial amounts of separation equipment, flow complexity, investment and high energy consumption.The shortcoming of TBA evaporations is used in reacting
Ion-exchange resin catalyst heat endurance it is not enough, intensity decreases at relatively high temperatures, the catalyst after fragmentation causes reaction
Device pressure drop becomes big, reduces the conversion ratio and yield of isobutene.
CN101260016A describes a kind of refining plant and process for being cracked by MTBE and making high-purity isobutene, the method
Using MTBE cracking gases as raw material, six tower continuous rectification techniques of light and de- weight are taken off using absorption, methanol dehydration and refined, isobutene
Flow separation obtains isobutene product.CN102020526B and CN102690159A describe one kind and prepare isobutyl using the tert-butyl alcohol
Fixed bed reactors and rectifying column are constituted a system by the method for alkene, the method, mixed from rectifying column side take-off tertiary butanol and water
Compound is back to reactor, top gaseous phase extraction isobutene product.
C_4 hydrocarbon is one of Main By product of steam cracking device and catalytic cracking unit.Do not waited containing quantity wherein
Iso-butane, isobutene, butene-1, butadiene, 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., these components are widely used industrial chemicals, particularly
C 4 olefin.With the continuous growth of the yield of carbon four, the comprehensive utilization of C_4 hydrocarbon turns into the strong approach of enterprise's cost efficiency,
The separation utilization of especially C 4 olefin each component is the key point that C_4 hydrocarbon appreciation is utilized.
Only 0.6 DEG C of the boiling point difference of isobutene and iso-butane, is difficult to efficiently separate using common distillating method.Generally
A small amount of hydrogen is used on metallic catalyst, butene-1 and butene-2 can be made to occur double-bond isomerism reaction.Association reaction distillation technology,
The generation direction that can be not only reacted with flexible modulation double-bond isomerism, while the butadiene that may contain in charging can be removed, contained
The components such as sulphur compound.And the boiling point of iso-butane and isobutene also differs only by 4.9 DEG C, separated, then needed using conventional distillation mode
(number of plates can be more than 200 in most cases, and reflux ratio is more than 100), high energy consumption, economy for high theoretical stage and reflux ratio
Difference, unsuitable industrial applications.
CN101160274A describes the double bond hydroisomerization of butylene, and butadiene content is first not more than 1% (weight by the method
Amount) the logistics of carbon four be passed through fixed bed hydroisomerization reactor, make butadiene hydrogenation, while part butene-1 is isomerized to fourth
Alkene -2, then reactor outlet material is passed through to catalytic distillation tower, remaining butene-1 is further isomerized to butene-2,
Tower reactor obtains the material rich in butene-2, noble metal of the catalyst for load on alumina.CN101885660A describes one
C_4 hydrocarbon is passed through reactive distillation column by the method for planting C 4 hydrocarbon catalysis separation isobutene and butene-2, the method, the butene-1 in tower
It is isomerized to butene-2, overhead extraction iso-butane and isobutene, heavy constituent of the tower reactor extraction containing butene-2, normal butane, catalysis
Nickel-base catalyst of the agent for load on alumina.Above-mentioned two patents are not directed to how to separate iso-butane and isobutene.
The method that CN102070391A describes the comprehensive utilization mixing preparing isobutene of carbon four, method elder generation selective hydrogenation removes mixing carbon four
Middle butadiene, then using catalytic distillation technology, makes butene-1 be isomerized to butene-2, tower top light component iso-butane and isobutene
High-purity isobutylene is obtained by the isolated MTBE of ether-based device and then cracking, technological process length, cost are high.
The content of the invention
The present invention relates to a kind of method that high-purity isobutylene is prepared from C_4 hydrocarbon.The technical problems to be solved by the invention
It is that C_4 hydrocarbon utilization rate is not high in the prior art, the complicated technical problem of isobutene separation method.There is provided a kind of new by carbon
The method that four hydrocarbon prepare high-purity isobutylene.There is this method butene-1 isomerization rate height, isobutene to separate simple, isobutene production
Product purity is high, while the characteristics of obtaining high-purity isobutane.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：It is a kind of to prepare high-purity from C_4 hydrocarbon
The method of isobutene, comprises the following steps：(a) with the carbon four containing normal butane, iso-butane, isobutene, butene-1 and butene-2
For raw material, carbon four and hydrogen are passed into reactive distillation column conversion zone bottom, butene-1 is isomerized to fourth by hydro-isomerization
Alkene -2, while rectifying makes the heavy constituent containing normal butane, butene-2 be enriched with tower reactor again, light component iso-butane, isobutene, hydrogen exist
Tower top is enriched with；(b) reactive distillation tower top sets segregator, top discharge hydrogen, liquid of the bottom extraction containing iso-butane and isobutene
Phase distillate；(c) above-mentioned liquid phase distillate is passed into the middle part of extractive distillation column, and extractant is added from extractive distillation column top, tower
Top extraction iso-butane, tower reactor must contain the tower reactor distillate of isobutene and extractant；(d) above-mentioned tower reactor distillate is passed into solvent and returned
Receive in the middle part of tower, tower top obtains high-purity isobutylene, the extractant that tower reactor is obtained is back to the recycling of extractive distillation column top；Extraction
Agent is selected from least one of 1-METHYLPYRROLIDONE, dimethylformamide, acetonitrile and MEK.
In the above-mentioned technical solutions, C_4 hydrocarbon raw material is in catalytically cracked C four, carbon-4 or selection hydrogenating carbon four
One or more of mixtures.The C_4 hydrocarbon contains normal butane, iso-butane, isobutene, butene-1, butene-2 and a small amount of fourth two
Alkene.
Reactive distillation column is followed successively by rectifying section, conversion zone, stripping section from top to bottom, and conversion zone is not limited to a catalyst bed
Layer, conversion zone is arranged on the top of tower, to ensure that isomerization is in the area for being conducive to generating butene-2 reaction, the raw material of carbon four and
Hydrogen from conversion zone bottom enter, catalyst be preferably load on the alumina support include in nickel, zinc or palladium extremely
Few one kind.Remainder is common fractional distillation filling-material in addition to catalyst in tower.
Under certain operating conditions, butadiene hydrogenation a small amount of in reactive distillation column, the sulfur-containing compound that may contain
The heavier sulfide compound of generation, butene-1 is isomerized to butene-2, and tower top must contain the light component of iso-butane, isobutene, hydrogen,
By dephlegmator of top of the tower, gas phase discharge hydrogen, liquid phase extraction iso-butane and isobutene, containing normal butane, butene-2 heavy constituent from
Tower reactor is discharged.The total number of theoretical plate 50~100 of reactive distillation column, rectifying section 3~10, conversion zone equivalent to 5~20 pieces theories of height
Plate.Tower top operating pressure 0.3MPaG~1.0MPaG, preferably 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 iso-butane and isobutene distillate enter in the middle part of extractive distillation column, and extractant is from tower top
Add, extractant is at least one of 1-METHYLPYRROLIDONE, dimethylformamide, acetonitrile, MEK, when using dimethyl
Good result beyong contemplation, wherein dimethylformamide and second are achieved when the mixture of formamide and acetonitrile is as extractant
The quality proportioning of nitrile is 1/10~10/1, preferably 2/8~8/2.Extracting rectifying tower top obtains the iso-butane cut of high-purity, tower reactor
Mixture containing isobutene and extractant enters in the middle part of solvent recovery tower, and tower top obtains high-purity isobutylene product, tower reactor extractant
Extractive distillation column top is returned to, is recycled, and supplement fresh extractant in right amount as needed.The total number of theoretical plate of extractive distillation column
40~60, operating pressure 0.3MPaG~0.9MPaG, preferably 0.5MPaG~0.7MPaG, solvent is than 5~15, reflux ratio 2~10.
The total number of theoretical plate 5~20 of solvent recovery tower, operating pressure 0.3MPaG~0.9MPaG, preferably 0.5MPaG~0.7MPaG, backflow
Than 1~10.
The present invention has reached that separation prepares height from C_4 hydrocarbon by using reactive distillation and the group technology of extracting rectifying
The purpose of purity isobutylene, flow is simple, high income, achieves preferable technique effect.
Brief description of the drawings
Fig. 1 is the process flow diagram that the present invention prepares high-purity isobutylene from C_4 hydrocarbon.
C1 is reactive distillation column in Fig. 1, and C2 is extractive distillation column, and C3 is solvent recovery tower, and D1 is segregator, and I is rectifying
Section, II is conversion zone, and III is stripping section, and 1 is C_4 hydrocarbon, and 2 be reactive distillation tower overhead gas phase distillate, and 3 be reactive distillation tower top
Phegma, 4 be the discharging of reactive distillation tower top liquid phase, and 5 be reactive distillation tower top fixed gas, and 6 be the discharging of reactive distillation tower reactor, and 7 are
Extractive distillation column ejection material, 8 be the discharging of extracting rectifying tower reactor, and 9 be that solvent recovery tower ejects material, and 10 be that solvent recovery tower reactor is circulated
Extractant, 11 be relief liquor, H2For hydrogen, S is extractant.
Flow as shown in Figure 1, C_4 hydrocarbon 1 and hydrogen H2Enter from reactive distillation column C1 conversion zone II bottoms, anti-
It is butene-1/butene-2 to answer butadiene hydrogenation in rectifying column, and butene-1 is isomerized to butene-2, the sulfide conversion that may contain
For thioether, tower top obtain containing iso-butane, isobutene, hydrogen gas phase distillate 2, tower reactor obtained containing the weight such as normal butane, butene-2
Component distillate 6.Gas phase distillate 2 passes through segregator D1 partial condensations, and fixed gas 5 is discharged from top, partial condensation liquid conduct
The return reactive distillation column C1 of phegma 3, partly enters in the middle part of extractive distillation column C2, extractant S is smart from extraction as tower top discharging 4
The addition of tower C2 tops is evaporated, overhead 7 is iso-butane, and tower reactor distillate 8 is the mixture containing isobutene and extractant.Tower reactor
Distillate 8 enters solvent recovery tower C3, and tower top obtains the isobutene product 9 of high-purity, and tower reactor extractant 10 enters extracting rectifying
Tower C2 tops, are recycled.
Below by specific embodiment, the present invention is further illustrated, still, and the scope of the present invention is not only limited in
The scope that embodiment is covered.
Embodiment
【Embodiment 1】
The total number of theoretical plate 70 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section are theoretical
Equivalent to 10 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.6MPaG,
Reflux ratio 20, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 45, tower top operating pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase distillate enters from the 22nd block of plate, extraction
Agent MEK is taken to enter from the 2nd block of plate, solvent compares 5, and tower top obtains iso-butane mixture, the Grams Per Hour of load 10.Solvent recovery
The total number of theoretical plate 10 of tower, operating pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top is obtained
To higher degree isobutene, the Grams Per Hour of load 163, tower reactor distillate containing extractant returns to extracting rectifying tower top after cooling
Portion, is recycled.
The conversion ratio 99.86% of butene-1, isobutene purity 98.56%, the isobutene rate of recovery 96.17%.
Related logistics composition is shown in Table 1.
Table 1
【Embodiment 2】
The total number of theoretical plate 70 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section are theoretical
Equivalent to 10 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.6MPaG,
Reflux ratio 20, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 45, tower top operating pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase distillate enters from the 22nd block of plate, extraction
Agent 1-METHYLPYRROLIDONE is taken to enter from the 2nd block of plate, solvent compares 5, and tower top obtains iso-butane mixture, the Grams Per Hour of load 10.
The total number of theoretical plate 10 of solvent recovery tower, operating pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate
Enter, tower top obtains higher degree isobutene, the Grams Per Hour of load 163, tower reactor distillate containing extractant returns to extraction after cooling
At the top of rectifying column, recycle.
The conversion ratio 99.86% of butene-1, isobutene purity 98.78%, the isobutene rate of recovery 96.39%.
Related logistics composition is shown in Table 2.
Table 2
【Embodiment 3】
The total number of theoretical plate 70 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section are theoretical
Equivalent to 10 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.6MPaG,
Reflux ratio 20, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 45, tower top operating pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase distillate enters from the 22nd block of plate, extraction
Agent dimethylformamide is taken to enter from the 2nd block of plate, solvent compares 5, and tower top obtains iso-butane mixture, the Grams Per Hour of load 10.It is molten
The total number of theoretical plate 10 of agent recovery tower, operating pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate,
Tower top obtains higher degree isobutene, the Grams Per Hour of load 163, and tower reactor distillate containing extractant returns to extraction essence after cooling
Top of tower is evaporated, is recycled.
The conversion ratio 99.86% of butene-1, isobutene purity 99.11%, the isobutene rate of recovery 96.71%.
Related logistics composition is shown in Table 3.
Table 3
【Embodiment 4】
The total number of theoretical plate 70 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section are theoretical
Equivalent to 10 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.6MPaG,
Reflux ratio 20, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 45, tower top operating pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase distillate enters from the 22nd block of plate, extraction
Agent acetonitrile is taken to enter from the 2nd block of plate, solvent compares 5, and tower top obtains iso-butane mixture, the Grams Per Hour of load 10.Solvent recovery tower
Total number of theoretical plate 10, operating pressure 0.5MPaG, reflux ratio 5, extractive distillation column reactor distillate enters from the 5th block of plate, and tower top is obtained
Higher degree isobutene, the Grams Per Hour of load 163, tower reactor distillate containing extractant returns to extracting rectifying top of tower after cooling,
Recycle.
The conversion ratio 99.86% of butene-1, isobutene purity 99.08%, the isobutene rate of recovery 96.68%.
Related logistics composition is shown in Table 4.
Table 4
【Embodiment 5】
The total number of theoretical plate 70 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section are theoretical
Equivalent to 10 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.6MPaG,
Reflux ratio 20, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 45, tower top operating pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase distillate enters from the 22nd block of plate, extraction
Take the mixture (mass ratio 8 of agent dimethylformamide and acetonitrile:2) enter from the 2nd block of plate, solvent compares 5, and tower top obtains more high-purity
Spend iso-butane, the Grams Per Hour of load 10.The total number of theoretical plate 10 of solvent recovery tower, operating pressure 0.5MPaG, reflux ratio 5, extraction
Rectifying tower reactor distillate enters from the 5th block of plate, and tower top obtains high-purity isobutylene, and the Grams Per Hour of load 163, tower reactor contains extraction
Agent distillate returns to extracting rectifying top of tower after cooling, recycles.
The conversion ratio 99.86% of butene-1, isobutene purity 99.68%, the isobutene rate of recovery 97.27%.
Related logistics composition is shown in Table 5.
Table 5
【Embodiment 6】
The total number of theoretical plate 70 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section are theoretical
Equivalent to 10 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.6MPaG,
Reflux ratio 20, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 45, tower top operating pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase distillate enters from the 22nd block of plate, extraction
Take the mixture (mass ratio 5 of agent dimethylformamide and acetonitrile:5) enter from the 2nd block of plate, solvent compares 5, and tower top obtains more high-purity
Spend iso-butane, the Grams Per Hour of load 10.The total number of theoretical plate 10 of solvent recovery tower, operating pressure 0.5MPaG, reflux ratio 5, extraction
Rectifying tower reactor distillate enters from the 5th block of plate, and tower top obtains high-purity isobutylene, and the Grams Per Hour of load 163, tower reactor contains extraction
Agent distillate returns to extracting rectifying top of tower after cooling, recycles.
The conversion ratio 99.86% of butene-1, isobutene purity 99.66%, the isobutene rate of recovery 97.27%.
Related logistics composition is shown in Table 6.
Table 6
【Embodiment 7】
The total number of theoretical plate 70 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 5, stripping section are theoretical
Equivalent to 10 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.6MPaG,
Reflux ratio 20, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 45, tower top operating pressure 0.5MPaG, reflux ratio 4, reactive distillation tower top liquid phase distillate enters from the 22nd block of plate, extraction
Take the mixture (mass ratio 2 of agent dimethylformamide and acetonitrile:8) enter from the 2nd block of plate, solvent compares 5, and tower top obtains more high-purity
Spend iso-butane, the Grams Per Hour of load 10.The total number of theoretical plate 10 of solvent recovery tower, operating pressure 0.5MPaG, reflux ratio 5, extraction
Rectifying tower reactor distillate enters from the 5th block of plate, and tower top obtains high-purity isobutylene, and the Grams Per Hour of load 163, tower reactor contains extraction
Agent distillate returns to extracting rectifying top of tower after cooling, recycles.
The conversion ratio 99.86% of butene-1, isobutene purity 99.65%, the isobutene rate of recovery 97.24%.
Related logistics composition is shown in Table 7.
Table 7
【Embodiment 8】
The total number of theoretical plate 75 of reactive distillation column (counting from top to bottom, as follows), theoretical number of plates of rectifying section 8, stripping section are theoretical
Equivalent to 12 pieces height equivalent to a theoretical plate of plate number 55, conversion zone, conversion zone loads the nickel-base catalyst using aluminum oxide as carrier, its remaining part
Stainless steel triangle helical packing is filled out in packing, and C_4 hydrocarbon and hydrogen enter from tower conversion zone bottom, tower top operating pressure 0.5MPaG,
Reflux ratio 28, hydrogen alkene compares 0.02, the Grams Per Hour of inlet amount 360, the Grams Per Hour of tower top liquid phase produced quantity 175.Extractive distillation column premier
By plate number 48, tower top operating pressure 0.4MPaG, reflux ratio 5, reactive distillation tower top liquid phase distillate enters from the 25th block of plate, extraction
Take the mixture (mass ratio 4 of agent dimethylformamide and acetonitrile:6) enter from the 2nd block of plate, solvent compares 7, and tower top obtains more high-purity
Spend iso-butane, the Grams Per Hour of load 10.The total number of theoretical plate 12 of solvent recovery tower, operating pressure 0.4MPaG, reflux ratio 6, extraction
Rectifying tower reactor distillate enters from the 6th block of plate, and tower top obtains high-purity isobutylene, and the Grams Per Hour of load 164, tower reactor contains extraction
Agent distillate returns to extracting rectifying top of tower after cooling, recycles.
The conversion ratio 99.98% of butene-1, isobutene purity 99.75%, the isobutene rate of recovery 97.93%.
Related logistics composition is shown in Table 8.
Table 8
Claims (7)
1. a kind of method that isobutene is prepared from C_4 hydrocarbon, comprises the following steps：
(a) it is raw material with the carbon four containing normal butane, iso-butane, isobutene, butene-1 and butene-2, carbon four and hydrogen is passed through
To reactive distillation column conversion zone bottom, butene-1 is set to be isomerized to butene-2 by hydro-isomerization, while rectifying makes to contain positive fourth again
Alkane, the heavy constituent of butene-2 are enriched with tower reactor, and light component iso-butane, isobutene, hydrogen are enriched with tower top；
(b) reactive distillation tower top sets segregator, and top discharge hydrogen, bottom liquid phase of the extraction containing iso-butane and isobutene is distillated
Thing；
(c) above-mentioned liquid phase distillate is passed into the middle part of extractive distillation column, and extractant is added from extractive distillation column top, overhead extraction
Iso-butane, tower reactor must contain the tower reactor distillate of isobutene and extractant；
(d) above-mentioned tower reactor distillate is passed into the middle part of solvent recovery tower, and tower top obtains high-purity isobutylene, the extractant that tower reactor is obtained
It is back to the recycling of extractive distillation column top；
Reactive distillation column overhead operating pressure 0.3MPaG-1.0MPaG, hydrogen alkene mol ratio 0.01-0.06, reflux ratio 5-20；
Extractant is the mixture of dimethylformamide and acetonitrile, and its mass ratio is 10/1~1/10；
In reactive distillation column conversion zone load catalyst for load on the alumina support include in nickel, zinc or palladium extremely
Few one kind；Remainder is common fractional distillation filling-material in addition to catalyst in tower.
2. the method for isobutene is prepared from C_4 hydrocarbon according to claim 1, it is characterised in that the total theoretical plate of extractive distillation column
Number 40~60, operating pressure 0.3MPaG~0.9MPaG, solvent is than 5~15, reflux ratio 2~10.
3. the method for isobutene is prepared from C_4 hydrocarbon according to claim 1, it is characterised in that the total theoretical plate of solvent recovery tower
Number 5~20, operating pressure 0.3MPaG~0.9MPaG, reflux ratio 1~10.
4. the method for isobutene is prepared from C_4 hydrocarbon according to claim 1, it is characterised in that extractive distillation column is using continuous
Extracting operation, extractant is recycled.
5. the method for isobutene is prepared from C_4 hydrocarbon according to claim 1, it is characterised in that C_4 hydrocarbon raw material carrys out self-catalysis
One or more of mixtures in cracking carbon four, carbon-4 or selection hydrogenating carbon four.
6. the method for isobutene is prepared from C_4 hydrocarbon according to claim 1, it is characterised in that reactive distillation column is from top to bottom
It is made up of rectifying section, conversion zone, stripping section, conversion zone is not limited to a beds, and conversion zone is arranged on the upper of tower
Portion.
7. the method for isobutene is prepared from C_4 hydrocarbon according to claim 1, it is characterised in that the total theoretical plate of reactive distillation column
Number 50~100, rectifying section 3~10, conversion zone equivalent to 5~20 pieces theoretical plates of height.
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