CN107652157A - A kind of method of butadiene in methanol removal olefin process using reactive distillation - Google Patents
A kind of method of butadiene in methanol removal olefin process using reactive distillation Download PDFInfo
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- CN107652157A CN107652157A CN201710686248.1A CN201710686248A CN107652157A CN 107652157 A CN107652157 A CN 107652157A CN 201710686248 A CN201710686248 A CN 201710686248A CN 107652157 A CN107652157 A CN 107652157A
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- butadiene
- reaction zone
- reactive distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a kind of method of butadiene in methanol removal olefin process using reactive distillation, comprise the following steps：(1) raw material containing C4 and above component enters reactive distillation column after being mixed with hydrogen, and butadiene hydrogenation reaction generation n-butene occurs in the first reaction zone；(2) light component enters rectifying section, and heavy constituent enters stripping section；(3) second reaction zone is entered by the light component of rectifying section, in second reaction zone hydrogenation reaction further occurs for butadiene.The knockout tower of carbon four and hydrogenation reaction are coupled into reactive distillation column by the invention, effectively reduce concentration of the butadiene in the component of carbon four, solve the problems, such as the higher heated autohemagglutination of knockout tower internal cause butadiene concentration of carbon four；Meanwhile by reaction and rectifying coupling within one device, the equipment such as storage tank and the pump of hydrogenation reactor and its correlation are saved, reasonably the heat by butadiene hydrogenation release separates for mass transfer, both saves equipment investment and operation energy consumption, reduces cost of investment.
Description
Technical field
The present invention relates to a kind of method applied to methanol-to-olefins field removing butadiene, utilized more particularly, to one kind
The method of butadiene in reactive distillation methanol removal olefin process.
Background technology
In recent years, New Coal Chemical project has formed scale, and MTO technology is as weight in New Coal Chemical project
The process route wanted, faster development is also obtained.With the development of MTO technology, the problem of it is present, is also increasingly bright
It is aobvious, high energy consumption and the development with high investment for constraining it to a certain extent, therefore process optimization is extremely urgent.
Methanol-to-olefins are to utilize the synthesis gas production methanol after coal gasification, and methanol passes through fixed bed or fluidized-bed reaction
Device, using molecular sieve as catalyst, generate alkane and alkene including C1~C8, what wherein content was most is propylene, ethene
Take second place, also extremely a small amount of butadiene, though butadiene content is few, if separation not in time, the butadiene meeting of accumulation
Forming autopolymer influences continuously running for equipment, while influences the deep processing of the product of carbon four.
Butadiene is simplest conjugated diene, has very high activity, extremely easily polymerization, in process of production by
Polymerizing butadiene generation autopolymer, Peroxidize auto-polymer etc. can be caused in temperature rise, because these density polymers are more than in system
Other materials, longtime running can cause these materials to accumulate in the dead band of equipment and pipeline, if equipment and pipeline are impacted and anxious
Play heating can cause polymer decomposition nature to set off an explosion, and the thing of butadiene peroxid self-polymer accumulation blast once occurred in the country
Part, therefore butadiene must be removed by certain method, just can guarantee that the safe and reliable operating of system；The content of butadiene compared with
There is negative effect in high deep-processing process and downstream product to C-4-fraction, for example isobutene etherification reaction prepares methyl- tert fourth
If base ether butadiene content is higher, oligomerisation reaction generation colloid occurs easily on etherified resin for butadiene, and colloid can accumulate in
On catalyst duct, catalyst activity is reduced, or even make its inactivation；It is higher for the alkylated reaction of butylene, butadiene content
Sour dosage increase can be caused, alkylated reaction requires general control in below 100ppmw butadiene content；Therefore must be in time
Remove the butadiene in carbon four.
Because the boiling point and 1- butylene and isobutene of butadiene are very close, the rectificating method using routine is difficult by its point
From separating technology main at present has two kinds, and one kind is to take extraction rectification technique to separate butadiene, and one kind is using selectivity
The method of hydrogenation, remove the butadiene in the component of carbon four.In recent years, because extracting rectifying energy consumption is higher, loss of material is more, and
Need optional equipment separate and recovery extractant, economic benefit is relatively low, this method progressively by selective hydrogenation technique
Substitution.
Selective hydrogenation is by hydrogenation reaction, butadiene hydrogenation is converted into only son's alkene or butane, catalyst is expensive
Metallic catalyst.U.S.Pat.NO.5,955,640 propose a kind of method that butadiene and alkynes are removed from carbon four, raw material
Reactor is introduced into, hydrogenation reaction occurs in reactor for butadiene and alkynes, enters back into rectifying column and purifies to obtain n-butene production
Product, this method can effectively reduce the content of butadiene and alkynes, but additional reactor improves cost of investment.Carbon at present
Mainly there are catalytic cracking, steam cracking and a MTO technology in the source of four raw materials, but current butadiene removal technique
Primarily directed to petroleum cracking technique, the composition gap of carbon four of petroleum cracking technique and MTO technology is larger, especially
Butadiene content differs greatly.For the carbon four of methanol-to-olefins field by-product, the wherein content of butadiene in PPM levels,
Content is less, but the flux of carbon four is larger, according to such a technique, reactor size can be caused larger, improves equipment investment
Cost, while need larger floor space.
The content of the invention
In view of this, the invention is directed to one kind and utilizes butadiene in reactive distillation methanol removal olefin process
Method, with overcome the deficiencies in the prior art, the knockout tower of carbon four and hydrogenation reaction are coupled into reactive distillation column, make in the component of carbon four
Butadiene hydrogenation reaction occurs in tower, it is converted into monoolefine or butane, effectively reduce butadiene in carbon four
Concentration in component, butadiene component content is reduced between 1-100PPM, it is dense to solve the knockout tower internal cause butadiene of carbon four
The problem of spending higher heated autohemagglutination.Meanwhile by reaction and rectifying coupling within one device, save hydrogenation reactor and its phase
The equipment such as the storage tank and pump of pass, reasonably the heat that butadiene hydrogenation discharges is separated for mass transfer, both saves equipment investment,
Operation energy consumption is reduced again, effectively reduces cost of investment.
To reach above-mentioned purpose, what the technical scheme of the invention was realized in：
The method of butadiene, comprises the following steps in a kind of methanol removal olefin process using reactive distillation：
(1) raw material containing C4 and above component enters reactive distillation column after being mixed with hydrogen, occurs in the first reaction zone
Butadiene hydrogenation reaction generation n-butene；
(2) light component enters rectifying section, and heavy constituent enters stripping section；
(3) second reaction zone is entered by the light component of rectifying section, butadiene is further hydrogenated with second reaction zone
Reaction.
Further, overhead condenser is entered by the gas phase of carbon four of the second reaction zone, the condensate liquid of carbon four is divided into two
Stock：One is as reactive distillation column liquid-phase reflux, another burst of product of carbon four extraction；The reactive distillation column tower is left in tower reactor extraction
Kettle is also classified into two strands later：One enters tower reactor reboiler as tower reactor reboiler liquid phase feeding, after reboiler gasifies
Gas phase is back to reactive distillation column, another burst of heavy constituent of carbon more than four extraction.
Further, the raw material in the step (1) refers to that butadiene content includes C4 between 1000-5000ppm
~C8 alkane and the mixture of alkene.
Further, the raw material of the step (1) is the product gas by methanol-to-olefins device reaction workshop section by multistage
Compression, washing, alkali cleaning, dry after enter high and low pressure depropanizer tower, will C3 following components and more than C4 components separate after obtain
More than C4 components.
Further, by the raw material in the step (1) be cooled to 30~50 DEG C between after enter the reactive distillation column,
Butadiene and hydrogen mol ratio are 1.0~1.2 in the raw material.
Further, the number of theoretical plate of the reactive distillation column is 30~50,0.45~0.7Mpa of operating pressure；
First reaction zone between the 18th~25 piece of theoretical cam curve, the temperature control of the first reaction zone 60~
Between 70 DEG C；
The second reaction zone is between the 1st~5 piece of theoretical cam curve, and second reaction zone temperature control is at 55~60 DEG C
Between.
Further, the reflux ratio of the reactive distillation column overhead is controlled between 2.0~5.0, and tower top temperature control exists
40-60 DEG C, bottom temperature is controlled at 90-120 DEG C,.
Further, after the first reaction zone of the reactive distillation column and second reaction zone, in the product of tower top carbon four
The content of butadiene is reduced to below 100ppm.
Further, what first reaction zone and second reaction zone were carried out is selective hydrogenation reaction, first reaction
Catalyst is provided with area and the second reaction zone.
Further, second reaction zone, rectifying section, the first reaction zone are followed successively by inside the reactive distillation column from top to bottom
And stripping section
Specifically, the product gas from methanol-to-olefins device reaction workshop section includes C1~C8 alkane and alkene, wherein
Content it is most be propylene, ethene takes second place, and product gas enters height pressure-off third after multi-stage compression, washing, alkali cleaning, drying
Alkane tower, C3 following components and more than C4 components are separated, then more than C4 components after hydrogenation reactor removing butadiene,
Into the knockout tower of carbon four, C4 and C5C6C7 separation is carried out, the present invention divides particularly directed to butadiene hydrogenation reactor and carbon four
From the improvement of tower workshop section, while separation to carbon four, the butadiene of harm system, concrete technology flow process are removed using reactive distillation
It is as follows：
The raw material (1) containing C4 and above component from low pressure depropanizer tower reactor is cooled down by feed cooler (A),
Logistics (2) after cooling enters static mixer (B), is mixed with the hydrogen (3) from Hydrogen Unit, uniformly liquid phase thing after mixing
Stream (4) enters reactive distillation column (C), and reactive distillation column (C) includes four parts：First reaction zone (H), second reaction zone (F),
Board-like rectifying section (G), filler stripping section (I).Liquid phase stream (4) initially enters the first reaction zone (H) generation butadiene after mixing
Hydrogenation reaction generates n-butene, and then light component enters board-like rectifying section (G), and heavy constituent enters filler stripping section (I), reaction essence
Evaporate top of tower and be provided with second reaction zone (F), butadiene further reacts in this region, and the gas phase of tower top carbon four (5) is entered
Enter overhead condenser (D), the condensate liquid of carbon four (6) is divided into two strands：One is as reactive distillation column liquid-phase reflux (7), another strand of carbon
Four products (8) produce, and tower reactor extraction (9) is also classified into two strands after leaving tower bottom of rectifying tower：One is as tower reactor reboiler liquid phase
Charging (10) enters tower reactor reboiler (E), and gas phase (11) is back to reactive distillation column, another strand of carbon after reboiler gasification
More than four heavy constituents (12) produce.
Raw material of the butadiene content between 1000-5000ppm is saturated mode after low pressure depropanizer extraction, temperature
60~80 DEG C, 30~50 DEG C are cooled to through subcooler, is mixed with hydrogen in static mixer, hydrogen and butadiene mol ratio control
System is between 1.0~1.2, and holding hydrogen is somewhat excessive, and excessive hydrogen can cause the fixed gas amount of tower top to increase.Mix laggard
Enter reactive distillation column, the reactive distillation column number of plates is between 30~50 pieces, 0.45~0.7Mpa of operating pressure, reactive distillation column point
For four parts：First reaction zone, second reaction zone, board-like rectifying section, filler stripping section.The temperature control of first reaction zone exists
Between 60~70 DEG C, between the 18th~25 piece of theoretical plate, second reaction zone temperature control is between 55~60 DEG C, positioned at
Between 1~5 piece of theoretical plate, reaction zone is set effectively to utilize feed and return in tower top and feed side, it is high-purity using tower top
Degree carbon four produces to catalyst to be washed away, and on the one hand improves the reactivity worth of catalyst, on the other hand can be controlled by adjusting flow
The temperature of reaction zone processed, overhead reflux is than control between 2-5；The rectifying section is plate column, because butadiene is in this portion
Separating/enriching, in order to improve the operational capacity of tower and separative efficiency, using plate column, the blocking of butadiene polymer can be avoided to ask
Topic；The stripping section is filler stripping section, and using packed tower, this some butadiene content does not almost have, in order to improve tower
Separative efficiency, the packed tower of plate column is higher than using separative efficiency；At 40-60 DEG C, bottom temperature control exists for tower top temperature control
90-120℃.Behind reactive distillation column two-stage reaction area, the content of the butadiene of tower top carbon four can be reduced to below 100ppm.
What first reaction zone and second reaction zone were carried out is selective hydrogenation reaction, it is necessary to passes through preferred catalyst and tune
Whole technological parameter, the generation for preventing deep hydrogenation from reacting.The catalyst of reaction zone is expensive using platinum, palladium, gold, silver, ruthenium, rhodium, osmium etc.
One or more mixtures in metal, co-catalyst can use a kind of or their mixtures such as copper, potassium, magnesium, barium, zinc,
Carrier is using aluminum oxide, silica or molecular sieve etc..
Relative to prior art, the invention has the advantage that：
(1) butadiene hydrogenation reaction is exothermic reaction, and conventional reactor can form superheat region, these heats due to heat release
If not taken away in time, noble metal catalyst surface can be caused to sinter, so as to cause it to lose activity, reaction is coupled with rectifying
In the knockout tower of carbon four, heat caused by reaction can be utilized in time by the gas-liquid mass transfer separation in tower, reduce the energy in coupled
Amount consumption, while reaction zone overtemperature can be avoided, extend catalyst service life.
(2) method using rectifying and reaction coupling within one device, had both realized the separation of the component of carbon four, realized again
Butadiene is removed by hydrogenation reaction, and the heat that can will be hydrogenated with release is used to promote rectifying action, can avoid fourth two
Alkene excessive concentration autohemagglutination blocks whole system, can reduce cost of investment again, be a kind of coupling technique of efficient energy-saving.
Brief description of the drawings
Fig. 1 reactive distillations remove butadiene flow chart
1- raw materials, raw material, 3- hydrogen, 4- hydrogen and raw material mixed liquor after 2- coolings, the gas phase of 5- tower tops carbon four, 6- carbon four are cold
Lime set, 7- reactive distillation column liquid-phase refluxs, the extraction of the product of 8- carbon four, the extraction of 9- tower reactors, 10- reboiler liquid phase feedings, 10- carbon four
Above heavy constituent, the backflow of 11- reactive distillation column tower reactors gas phase, the heavy constituent of 12- carbon more than four
A- feed coolers, B- static mixers, C- reactive distillation columns, D- overhead condensers, E- tower reactor reboilers, F-
Two reaction zones, the board-like rectifying sections of G-, the reaction zones of H- first, I- filler stripping sections.
Embodiment
In addition to being defined, technical term used has and the invention one of ordinary skill in the art in following examples
The identical meanings being commonly understood by.Test reagent used, is routine biochemistry reagent unless otherwise specified in following examples；
The experimental method, it is conventional method unless otherwise specified.
The invention is described in detail with reference to embodiment.
Embodiment 1
4000~5000ppm of butadiene content in the heavy constituent of carbon more than four, 30~50 DEG C are cooled to through subcooler, is passed through
Static mixer mixes with hydrogen, hydrogen and butadiene mol ratio 1.0~1.2, into the reaction zone of reactive distillation column first, first
Between 18~25 blocks of plates of reaction zone, 60~65 DEG C of temperature, between the plate of 1~5 block of second reaction zone, 54~56 DEG C of temperature, due to fourth
Diene content is higher, and reflux ratio accordingly increases, and to improve the extent of reaction, reflux ratio is controlled between 4~5, and tower top temperature 53~
55 DEG C, 95~105 DEG C of bottom temperature, 50~70ppm of butadiene content in the product of tower top carbon four, the content 0.5% of tower reactor carbon four with
Under.
Embodiment 2
2000~3000ppm of butadiene content in the heavy constituent of carbon more than four, 30~50 DEG C are cooled to through subcooler, is passed through
Static mixer mixes with hydrogen, hydrogen and butadiene mol ratio 1.0~1.2, into the reaction zone of reactive distillation column first, first
Between 18~25 blocks of plates of reaction zone, 60~64 DEG C of temperature, between the plate of 1~5 block of second reaction zone, 54~56 DEG C of temperature, reflux ratio
Control is between 3~4,53~55 DEG C of tower top temperature, 95~105 DEG C of bottom temperature, butadiene content 30 in the product of tower top carbon four
~50ppm, the content of tower reactor carbon four is below 0.5%.
Embodiment 3
1000~2000ppm of butadiene content in the heavy constituent of carbon more than four, 30~50 DEG C are cooled to through subcooler, is passed through
Static mixer mixes with hydrogen, hydrogen and butadiene mol ratio 1.0~1.1, into the reaction zone of reactive distillation column first, first
Between 18~25 blocks of plates of reaction zone, 60~63 DEG C of temperature, between the plate of 1~5 block of second reaction zone, 54~55 DEG C of temperature, reflux ratio
Control is between 2~3,53~55 DEG C of tower top temperature, 95~105 DEG C of bottom temperature, butadiene content 10 in the product of tower top carbon four
~20ppm, the content of tower reactor carbon four is below 0.5%.
The preferred embodiment of the invention is the foregoing is only, is not intended to limit the invention creation, it is all at this
Within the spirit and principle of innovation and creation, any modification, equivalent substitution and improvements made etc., the invention should be included in
Protection domain within.
Claims (9)
1. a kind of method of butadiene in methanol removal olefin process using reactive distillation, it is characterised in that：Including following step
Suddenly：
(1) raw material containing C4 and above component enters reactive distillation column after being mixed with hydrogen, and fourth two occurs in the first reaction zone
Alkene hydrogenation reaction generates n-butene；
(2) light component enters rectifying section, and heavy constituent enters stripping section；
(3) second reaction zone is entered by the light component of rectifying section, in second reaction zone hydrogenation reaction further occurs for butadiene.
2. according to the method for claim 1, it is characterised in that：Enter tower top by the gas phase of carbon four of the second reaction zone
Condenser, the condensate liquid of carbon four are divided into two strands：One is as reactive distillation column liquid-phase reflux, another burst of product of carbon four extraction；Tower reactor
Extraction is also classified into two strands after leaving the reactive distillation column tower reactor：One enters tower reactor again as tower reactor reboiler liquid phase feeding
Device is boiled, gas phase is back to reactive distillation column, another burst of heavy constituent of carbon more than four extraction after reboiler gasification.
3. according to the method for claim 1, it is characterised in that：Raw material in the step (1) refers to that butadiene content exists
The mixture of alkane including C4~C8 and alkene between 1000-5000ppm.
4. according to the method for claim 1, it is characterised in that：The raw material of the step (1) is by methanol-to-olefins device
The product gas for reacting workshop section enters high and low pressure depropanizer tower after multi-stage compression, washing, alkali cleaning, drying, by C3 with the following group
Divide after being separated with more than C4 components obtained more than C4 components.
5. the method described in claim 1, it is characterised in that：Raw material in the step (1) is cooled between 30~50 DEG C
Enter the reactive distillation column afterwards, butadiene and hydrogen mol ratio are 1.0~1.2 in the raw material.
6. according to the method for claim 1, it is characterised in that：
The number of theoretical plate of the reactive distillation column is 30~50,0.45~0.7Mpa of operating pressure；
First reaction zone is between the 18th~25 piece of theoretical cam curve, and the temperature control of the first reaction zone is at 60~70 DEG C
Between；
The second reaction zone between the 1st~5 piece of theoretical cam curve, second reaction zone temperature control 55~60 DEG C it
Between.
7. the method described in claim 1, it is characterised in that：The reflux ratio of the reactive distillation column overhead is controlled 2.0~5.0
Between, at 40-60 DEG C, bottom temperature is controlled at 90-120 DEG C for tower top temperature control.
8. according to the method for claim 1, it is characterised in that：By the first reaction zone of the reactive distillation column and second
After reaction zone, the content of butadiene is reduced to below 100ppm, first reaction zone and the second reaction in the product of tower top carbon four
What area was carried out is selective hydrogenation reaction, and catalyst is provided with first reaction zone and the second reaction zone.
9. according to the method for claim 1, it is characterised in that：Second is followed successively by from top to bottom inside the reactive distillation column
Reaction zone, rectifying section, the first reaction zone and stripping section.
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| CN201710686248.1A CN107652157A (en) | 2017-08-11 | 2017-08-11 | A kind of method of butadiene in methanol removal olefin process using reactive distillation |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917608A (en) * | 2022-06-30 | 2022-08-19 | 中国天辰工程有限公司 | Low-energy-consumption propylene oligomer separation system and separation method |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3342891A (en) * | 1962-11-02 | 1967-09-19 | Shell Oil Co | Removal of vinylacetylenes from alkadienes |
| CN1231654A (en) * | 1996-09-23 | 1999-10-13 | 催化蒸馏技术公司 | Process for concurrent selective hydrogenation of acetylenes and 1,2 butadiene in hydrocarbon streams |
| CN1264355A (en) * | 1997-07-28 | 2000-08-23 | 催化蒸馏技术公司 | Apparatus and method for catalytic distillations |
| CN1345617A (en) * | 2000-09-22 | 2002-04-24 | 中国石化集团齐鲁石油化工公司 | Catalytic reaction distillation equipment |
| CN105152840A (en) * | 2015-09-14 | 2015-12-16 | 中国成达工程有限公司 | Process for refining C-4 hydrocarbon fluid |
-
2017
- 2017-08-11 CN CN201710686248.1A patent/CN107652157A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3342891A (en) * | 1962-11-02 | 1967-09-19 | Shell Oil Co | Removal of vinylacetylenes from alkadienes |
| CN1231654A (en) * | 1996-09-23 | 1999-10-13 | 催化蒸馏技术公司 | Process for concurrent selective hydrogenation of acetylenes and 1,2 butadiene in hydrocarbon streams |
| CN1264355A (en) * | 1997-07-28 | 2000-08-23 | 催化蒸馏技术公司 | Apparatus and method for catalytic distillations |
| CN1345617A (en) * | 2000-09-22 | 2002-04-24 | 中国石化集团齐鲁石油化工公司 | Catalytic reaction distillation equipment |
| CN105152840A (en) * | 2015-09-14 | 2015-12-16 | 中国成达工程有限公司 | Process for refining C-4 hydrocarbon fluid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114917608A (en) * | 2022-06-30 | 2022-08-19 | 中国天辰工程有限公司 | Low-energy-consumption propylene oligomer separation system and separation method |
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