CN101492335A - Combination method for comprehensive utilization of mix C4 - Google Patents
Combination method for comprehensive utilization of mix C4 Download PDFInfo
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- CN101492335A CN101492335A CNA200810032930XA CN200810032930A CN101492335A CN 101492335 A CN101492335 A CN 101492335A CN A200810032930X A CNA200810032930X A CN A200810032930XA CN 200810032930 A CN200810032930 A CN 200810032930A CN 101492335 A CN101492335 A CN 101492335A
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Abstract
The invention relates to a combination method for using mixed C4 comprehensively. The method mainly solves the problem that the chemical industrial utilization added value and the comprehensive utilization rate of a byproduct of the mixed C4 of a steam cracking device and the byproduct of the mixed C4 of an FCC device in the prior art are low. The method solves the problem well by the technical proposal which comprises the steps as follows: 1) extraction technology is adopted to obtain butadiene separating; 2) catalytic distillation technology is used for ensuring that butylene-1 in C4 which is remained after being extracted in step 1 is isomerized into butylene-2 and is also separated to obtain isobutene; 3) olefin disproportionation technology is used for disproportionating the butylene-2 in the rest of the mixed C4 in step 2 and ethene to produce propylene; and 4) the remained mixed C4 in step 3 is recycled as a cracking raw material. The invention can be used in the industrial production for increasing the production of the propylene and improving the comprehensive utilization value of the mixed C4.
Description
Technical field
The present invention relates to a kind of combined method that fully utilizes mixed c 4.
Background technology
Mixed c 4 means the by-product C of steam cracking device
4The by-product C of cut and catalytic cracking unit
4Cut, the mixed c 4 of steam cracking device by-product generally utilizes iso-butylene through extracting divinyl, MTBE device at present, though last remaining mixed c 4 contains a large amount of butene-1s and butene-2, most of at present as the liquefied gas use, part is produced house can separation purification butene-1.And the mixed C of catalytic cracking unit by-product
4Basically use as liquefied gas.Therefore, most mixed c 4 does not all make full use of their chemical industry added value, and comprehensive utilization ratio is extremely low.In recent years, it is very many how to fully utilize the research of mixed c 4.
To obtain divinyl be at present more common one of the method for utilizing to extracting and separating from mixed c 4, adopts extraction agent that the butadiene extraction in the mixed c 4 is come out, and extraction tower (1) cat head distilled butane, butene mixture be utilization again after washing.And still liquid is divinyl, a small amount of alkynes and acetonitrile solution at the bottom of the extraction Tata, separates by a rectifying tower (2).Rectifying tower (2) cat head obtains divinyl and alkynes, separates alkynes by another one rectifying tower (3), and obtains product butadiene.Still liquid is acetonitrile at the bottom of rectifying tower (2) tower, enters extraction tower (1) and recycle after cooling.
The method of utilizing that another one is commonly used is the synthetic MTBE of iso-butylene that utilizes in the mixed c 4, and C 4 mixture and methyl alcohol are mixed in proportion, and enter methyltertiarvbutyl ether reactor and react.Reaction product is separated by a rectifying tower, and cat head obtains unreacted carbon four and methyl alcohol, obtains the MTBE product at the bottom of the tower.The unreacted carbon four that cat head obtains obtains unreacted carbon four and methyl alcohol respectively with the azeotrope of methyl alcohol behind eparating methanol tower and methanol distillation column, unreacted carbon four is utilized again, and methanol loop is sent to reactor.
Utilizing mixed c 4 to produce propylene is to have one of solution than hi-tech economy.Propylene is one of important basic Organic Chemicals.Propylene is mainly used in many products such as producing polypropylene, isopropyl benzene, propylene oxide, vinyl cyanide, vinylformic acid.As important light olefin, propylene year demand in continuous growth.But the general overview of the technology of producing propylene is byproduct technology and proprietary technology.Byproduct technology mainly is meant the propylene that obtains by steam cracking and catalytic cracking system ethylene unit.Proprietary technology refers to the technology of special Development and Production propylene, mainly contains Technologies such as dehydrogenating propane at present.Utilize mixed c 4 to produce propylene, not only improved mixed c 4 chemical industry added value, also satisfied the demand of market to a certain extent propylene.
Document WO 03078364 has been introduced the method that a kind of mixed c 4 or carbon five are converted into propylene.This technology is divided into two big steps, and step 1 is earlier oligomeric mixed olefins, then oligopolymer is carried out cracking and generates propylene.This method side reaction is many, the product complexity of generation, and the selectivity of propylene is not high, and the purification difficulty is big.Simultaneously, this technology is not mentioned the utilization of the higher composition of added value in the mixed c 4 such as divinyl, iso-butylene.
Document CA2297301 has introduced a kind of method that improves carbon four and carbon four above mixtures value.This method is feedstock conversion a low-carbon alkene directly by adopting zeolite molecular sieve, and separation obtains propylene, ethene.But this technology subsequent separation process contains two catalytic pyrolysis unit, a selective hydrogenation unit, an etherificate unit, the flow process complexity, and the propylene and ethylene yield is not high, and Technological Economy is relatively poor.
The described technology of above-mentioned document all is to the utilization of mixed c 4 or carbon five, relates to olefin cracking, produces propylene and ethylene.But all the higher composition of added value in the mixed c 4 such as divinyl, iso-butylene are not separated, the residue butane does not have further chemical utilization, and the comprehensive economy of mixed c 4 does not find full expression.
Summary of the invention
Technical problem to be solved by this invention is steam cracking device by-product mixed c 4 and the chemical utilization added value of FCC apparatus by-product mixed c 4 and the problem of making a low multiple use in the conventional art, and a kind of combined method of new comprehensive utilization mixed c 4 is provided.This method has and adopts extraction extraction technique, catalytic distillation technology, isomerization of butene technology, olefin metathesis technology that mixed c 4 is fully utilized, and separates the advantage that obtains divinyl, iso-butylene, pyrolyzer raw material and generate propylene.
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 combined method that fully utilizes mixed c 4 may further comprise the steps:
(1) the liquid phase feed mixed c 4 enters extraction tower, and by extraction agent extraction extracting, the mixture stream passes 1 for butylene, butane that the extraction tower cat head obtains enters catalytic distillation tower; Extraction Tata still is the mixture stream passes 2 of divinyl, extraction agent, obtains butadiene stream 3 through further separating;
(2) at the catalytic distillation tower conversion zone, butene-1 is turned to butene-2 by isomery, and this column overhead separation simultaneously obtains isobutene logistic 4, and this Tata end still liquid enters the butylene disproportionation unit for residue mixed c 4 logistics 5;
(3) butene-2 in ethene and the logistics 5 carries out disproportionation reaction generation propylene in the butylene disproportionation reactor, and the disproportionation reaction product obtains propylene product, unreacting ethylene and unreacted mixed c 4 logistics 6 after separating.
In the technique scheme, liquid-phase mixing carbon four preferred versions are the middle part that enters extraction tower, and the extraction agent preferred version is the top that enters extraction tower; The extraction agent preferred version is acetonitrile or dimethyl formamide; The extraction tower preferred version is sieve-tray tower, valve tray column or packing tower, and cat head working pressure preferable range is 0.38～0.65MPa; Logistics 1 preferred version is the below that enters the catalytic distillation tower conversion zone, and the catalyst reaction section preferred version is the middle and upper part that is positioned at catalytic distillation tower; The catalyzer preferred version that the catalytic distillation tower conversion zone adopts is alumina load palladium metal or nickel, and the rectifying section preferred version is valve tray column, sieve-tray tower or packing tower; Catalytic distillation column overhead working pressure preferable range is 0.4～1.2MPa, and catalyzed reaction temperature preferable range is 40～100 ℃, and catalyzed reaction air speed preferable range is 1～15 hour
-1The unreacting ethylene preferred version enters disproportionation reactor for circulation; Disproportionation reactor catalyzer preferred version is a metal oxide; Disproportionation reaction temperature preferable range is 260～330 ℃, and the reaction pressure preferable range is 2.0～3.5MPa, and the reaction velocity preferable range is 5～20 hours
-1Logistics 6 circulations enter the cracking stock of steam cracking device as pyrolyzer.
The inventive method adopts comprehensive utilization extraction extraction technique, catalytic distillation technology, isomerization of butene technology and butylene disproportionation technology, made full use of the higher component of added value in the mixed c 4, not only directly obtain higher divinyl, iso-butylene and the propylene of chemical industry added value, also obtained pyrolyzer cracking stock preferably.Utilize the inventive method, above above iso-butylene, the acquisition 25% (weight of divinyl, 92% (weight) of 95% (weight) in the recyclable mixed c 4, at the raw material mixed c 4) above propylene and the pyrolyzer cracking stock that obtains 10%-30% (weight is at the raw material mixed c 4).Therefore, the inventive method has greatly improved the value of mixed c 4, has obtained better technical effect.
Description of drawings
Fig. 1 is the inventive method process flow diagram;
Fig. 2 is a document CA2297301 process flow diagram;
Fig. 3 is document WO 03078364 process flow diagram.
1 is the raw material mixed c 4 among Fig. 1, Fig. 2 or Fig. 3,2 is extraction agent, and 3 is iso-butylene, and 4 is divinyl, extractant mixture, 5 is fresh ethylene, 6 is cyclic ethylene, and 7 is disproportionation reactor, and 8 is the disproportionation products separating unit, 9 is propylene, 10 is the unreacted mixed c 4, and 11 are the circulation mixed c 4, and 12 are the extraction extraction tower, 13 is catalytic distillation tower, 14 is the first catalytic cracking reaction device, and 15 is the second catalytic cracking reaction device, and 16 is first rectifying tower, 17 is the selective hydrogenation device, 18 is methyltertiarvbutyl ether reactor, and 19 is second rectifying tower, and 20 is light constituent (CH
4Deng), 21 is the ethene cut, and 22 is the propylene cut, and 23 is C 4 mixture, and 24 are heavy constituent, and 25 is methyl alcohol, and 26 is MTBE, and 30 is oligomerization reactor, and 31 is oligomerization product, and 32 is the catalytic pyrolysis product, and 33 is C
3Following cut, 34 is rectifying tower, 35 is C
5Above cut, 36 are the circulation mixed c 4.
Among Fig. 1, mix carbon 41 and in extractive distillation tower 12, come out through the extractant extract and separate, tower 12 tops distillate butylene, Butane mixture enters catalytic distillation tower 13; The bottom is butadiene, extractant mixture. Through behind the catalytic distillation, big section Divide butene-1 to be turned to butene-2 by isomery, isobutene 3 is separated this tower bottom branch from catalytic distillation tower 13 tops simultaneously From the mixing carbon four that goes out to be rich in butene-2. This partially mixed carbon four with enter disproportionation reactor 7 after ethene (5+6) mixes and carry out Disproportionated reaction, product is separated into by separative element 8: unreacting ethylene 6, propylene 9, unreacted mixing carbon 4 10, follow Ring mixes carbon 4 11. Unreacting ethylene 6 circulations are as reaction raw materials, and unreacted mixing carbon 4 10 is delivered to steam cracking device As cracking stock.
The present invention is further elaborated below by embodiment.
Embodiment
[comparative example 1]
By shown in Figure 2, mixed c 4 is formed (weight %) and is: divinyl: 40.0%, and iso-butylene: 12.0%, butene-1: 18.0%, butene-2: 18.2%, butane: 11.8%.Adopt document CA2297301 technical process, catalytic cracking catalyst employing silica alumina ratio is 280 Si-Al molecular sieve, and the temperature of reaction of the first catalytic cracking reaction device and the second catalytic cracking reaction device is 550 ℃, and reaction pressure is 0.1MPa; First rectifying tower 16 is a valve tray column, and stage number is 110, and tower top pressure is 1.2MPa; Selective hydrogenation catalyst is the palladium metal series catalysts, and temperature of reaction is 60 ℃, and reaction pressure is 3.0MPa; Catalyst for etherification is an ion exchange resin, and temperature of reaction is 40 ℃, and reaction pressure is 1.2MPa; Second rectifying tower 19 is a sieve-tray tower, and stage number is 60, and tower top pressure is 0.4MPa.Experimental results show that acquisition propylene and ethene are respectively 15% and 5% (weight is at raw material mixed c 4 1).
[comparative example 2]
By shown in Figure 3, mixed c 4 is formed (weight %) and is: divinyl: 40.0%, and iso-butylene: 12.0%, butene-1: 18.0%, butene-2: 18.2%, butane: 11.8%.Adopt document WO 03078364 technical process, olefin oligomerization catalyst adopts solid phosphoric acid, and temperature of reaction is 160 ℃, and reaction pressure is 4.0MPa; Catalytic cracking catalyst adopts the small-bore zeolite molecular sieve, and temperature of reaction is 510 ℃, and reaction pressure is 0.15MPa; Rectifying tower 34 is a valve tray column, and stage number is 80, and tower top pressure is 0.6MPa.Experimental results show that and to obtain propylene and ethene is respectively 10.1% and 3.8% (weight is at raw material mixed c 4 1).
[embodiment 1]
By shown in Figure 1, mixed c 4 is formed (weight %) and is: divinyl: 40.0%, and iso-butylene: 12.0%, butene-1: 18.0%, butene-2: 18.2%, butane: 11.8%.Adopt technical process of the present invention, extraction agent 2 adopts acetonitrile; Introduce as background technology, extraction extracting butadiene unit comprises extraction tower, water wash column, rectifying tower (2) and rectifying tower (3).Extraction tower is a valve tray column, and stage number is 60, and the cat head working pressure is 0.45MPa; Water wash column is a valve tray column, and stage number is 50, and the cat head working pressure is 0.6MPa; Rectifying tower (2) is a valve tray column, and stage number is 40, and the cat head working pressure is 0.5MPa; Rectifying tower (3) is a valve tray column, and stage number is 60, and the cat head working pressure is 0.8MPa.The catalyzer that the catalytic distillation tower conversion zone adopts is the alumina load palladium metal, and rectifying section is a valve tray column, and stage number is 50; The catalytic distillation tower tower top pressure is 0.5MPa, and the catalyzed reaction temperature is 40 ℃, and the catalyzed reaction air speed is 2 hours
-1Disproportionation reaction catalyzer is a Tungsten oxide 99.999, and temperature of reaction is 280 ℃, and reaction pressure is 3.2MPa, and reaction velocity is 8 hours
-1Experimental installation proves recyclable 98% divinyl, 95% iso-butylene, and obtaining propylene simultaneously is the pyrolyzer cracking stock of 27.3% (weight is at raw material mixed c 4 1) and 15% (weight is at raw material mixed c 4 1).
[embodiment 2]
By shown in Figure 1, mixed c 4 is formed (weight %) and is: divinyl: 30.0%, and iso-butylene: 12.0%, butene-1: 18.0%, butene-2: 18.2%, butane: 21.8%.Adopt technical process of the present invention, extraction agent 2 adopts dimethyl formamide; Introduce as background technology, extraction extracting butadiene unit comprises extraction tower, water wash column, rectifying tower (2) and rectifying tower (3).Extraction tower is a sieve-tray tower, and stage number is 80, and the cat head working pressure is 0.5MPa; Water wash column is a sieve-tray tower, and stage number is 60, and the cat head working pressure is 0.5MPa; Rectifying tower (2) is a sieve-tray tower, and stage number is 60, and the cat head working pressure is 0.6MPa; Rectifying tower (3) is a sieve-tray tower, and stage number is 68, and the cat head working pressure is 0.6MPa.The catalyzer that the catalytic distillation tower conversion zone adopts is the alumina load metallic nickel, and rectifying section is a sieve-tray tower, and stage number is 65; The catalytic distillation tower tower top pressure is 0.65MPa, and the catalyzed reaction temperature is 70 ℃, and the catalyzed reaction air speed is 8 hours
-1Disproportionation reaction catalyzer is magnesium oxide+Tungsten oxide 99.999 (Tungsten oxide 99.999 and magnesium oxide weight ratio are 3), and temperature of reaction is 300 ℃, and reaction pressure is 3.0MPa, and reaction velocity is 15 hours
-1Experimental installation proves recyclable 99% divinyl, 92% iso-butylene, and obtaining propylene simultaneously is the pyrolyzer cracking stock of 30.5% (weight is at raw material mixed c 4 1) and 22% (weight is at the raw material mixed c 4).
[embodiment 3]
By shown in Figure 1, mixed c 4 is formed (weight %) and is: divinyl: 20.0%, and iso-butylene: 15.0%, butene-1: 18.0%, butene-2: 18.2%, butane: 28.8%.Adopt technical process of the present invention, extraction agent 2 adopts dimethyl formamide; Introduce as background technology, extraction extracting butadiene unit comprises extraction tower, water wash column, rectifying tower (2) and rectifying tower (3).Extraction tower is a packing tower, and packed height is 30 meters, and the cat head working pressure is 0.8MPa; Water wash column is a packing tower, and packed height is 20 meters, and the cat head working pressure is 0.4MPa; Rectifying tower (2) is a packing tower, and packed height is 20 meters, and the cat head working pressure is 0.8MPa; Rectifying tower (3) is a sieve-tray tower, and stage number is 68, and the cat head working pressure is 0.6MPa.The catalyzer that the catalytic distillation tower conversion zone adopts is the alumina load metallic nickel, and rectifying section is a packing tower, and packed height is 30 meters; The catalytic distillation tower tower top pressure is 0.55MPa, and the catalyzed reaction temperature is 100 ℃, and the catalyzed reaction air speed is 12 hours
-1Disproportionation reaction catalyzer is magnesium oxide+Tungsten oxide 99.999 (Tungsten oxide 99.999 and magnesium oxide weight ratio are 5), and temperature of reaction is 260 ℃, and reaction pressure is 3.0MPa, and reaction velocity is 5 hours
-1Experimental installation proves recyclable 95% divinyl, 96% iso-butylene, and obtaining propylene simultaneously is the pyrolyzer cracking stock of 25.8% (weight is at raw material mixed c 4 1) and 28% (weight is at the raw material mixed c 4).
Claims (10)
1, a kind of combined method that fully utilizes mixed c 4 may further comprise the steps:
(1) the liquid phase feed mixed c 4 enters extraction tower, and by extraction agent extraction extracting, the mixture stream passes 1 for butylene, butane that the extraction tower cat head obtains enters catalytic distillation tower; Extraction Tata still is the mixture stream passes 2 of divinyl, extraction agent, obtains butadiene stream 3 through further separating;
(2) at the catalytic distillation tower conversion zone, butene-1 is turned to butene-2 by isomery, and this column overhead separation simultaneously obtains isobutene logistic 4, and this Tata end still liquid enters the butylene disproportionation unit for residue mixed c 4 logistics 5;
(3) butene-2 in ethene and the logistics 5 carries out disproportionation reaction generation propylene in the butylene disproportionation reactor, and the disproportionation reaction product obtains propylene product, unreacting ethylene and unreacted mixed c 4 logistics 6 after separating.
2, according to the combined method of the described comprehensive utilization mixed c 4 of claim 1, it is characterized in that liquid-phase mixing carbon four enters the middle part of extraction tower, extraction agent enters the top of extraction tower.
3,, it is characterized in that extraction agent is acetonitrile or dimethyl formamide according to the combined method of the described comprehensive utilization mixed c 4 of claim 1.
4, according to the combined method of the described comprehensive utilization mixed c 4 of claim 1, it is characterized in that extraction tower is sieve-tray tower, valve tray column or packing tower, the cat head working pressure is 0.38～0.65MPa.
5, according to the combined method of the described comprehensive utilization mixed c 4 of claim 1, it is characterized in that logistics 1 enters the below of catalytic distillation tower conversion zone, catalyst reaction section is positioned at the middle and upper part of catalytic distillation tower.
6, according to the combined method of the described comprehensive utilization mixed c 4 of claim 1, it is characterized in that the catalyzer that the catalytic distillation tower conversion zone adopts is alumina load palladium metal or nickel, rectifying section is valve tray column, sieve-tray tower or packing tower.
7, according to the combined method of the described comprehensive utilization mixed c 4 of claim 1, it is characterized in that catalytic distillation column overhead working pressure is 0.4～1.2MPa, the catalyzed reaction temperature is 40～100 ℃, the catalyzed reaction air speed is 1～15 hour
-1
8,, it is characterized in that the unreacting ethylene circulation enters disproportionation reactor according to the combined method of the described comprehensive utilization mixed c 4 of claim 1; Logistics 6 circulations enter the cracking stock of steam cracking device as pyrolyzer.
9,, it is characterized in that the disproportionation reactor catalyzer is a metal oxide according to the combined method of the described comprehensive utilization mixed c 4 of claim 1.
10, according to the combined method of the described comprehensive utilization mixed c 4 of claim 1, it is characterized in that the disproportionation reaction temperature is 260～330 ℃, reaction pressure is 2.0～3.5MPa, reaction velocity is 5～20 hours
-1
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| CN102070390A (en) * | 2011-01-12 | 2011-05-25 | 王伟跃 | Method for preparing propylene from refinery mixed C4 |
| CN103420760A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing propylene through C4 and ethylene disproportionation |
| CN103420756A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing propylene from C4 olefin |
| CN104053752A (en) * | 2012-01-11 | 2014-09-17 | 巴斯夫欧洲公司 | Method for providing a purified crude gaseous C4 fraction as an input stream for an extractive distillation using a selective solvent |
| US10358399B2 (en) | 2014-11-03 | 2019-07-23 | Basf Se | Process for preparing 1,3-butadiene from n-butenes by oxidative dehydrogenation |
| US10384990B2 (en) | 2014-11-14 | 2019-08-20 | Basf Se | Method for producing 1,3-butadiene by dehydrogenating n-butenes, a material flow containing butanes and 2-butenes being provided |
| CN110526796A (en) * | 2019-08-30 | 2019-12-03 | 凯瑞环保科技股份有限公司 | It is a kind of to provide the device and method of four raw material of carbon for MTBE downstream unit |
| US11124470B2 (en) | 2017-04-03 | 2021-09-21 | Sabic Global Technologies B.V. | Systems and methods of producing methyl tertiary butyl ether and propylene |
| CN113501742A (en) * | 2021-05-28 | 2021-10-15 | 中国石油化工股份有限公司 | Utilization method of ethylene cracking C4 |
Family Cites Families (2)
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| US6420619B1 (en) * | 2001-01-25 | 2002-07-16 | Robert J. Gartside | Cracked gas processing and conversion for propylene production |
| FR2837199B1 (en) * | 2002-03-15 | 2005-09-16 | Inst Francais Du Petrole | METHOD FOR CONVERTING INTO MULTIPLE STEPS A LOAD COMPRISING FOUR OLEFINS, FIVE ATOMS OF CARBON OR MORE, FOR PRODUCING PROPYLENE |
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| CN102070390B (en) * | 2011-01-12 | 2016-03-16 | 王伟跃 | The method of refinery's mixed c 4 propylene |
| CN102070390A (en) * | 2011-01-12 | 2011-05-25 | 王伟跃 | Method for preparing propylene from refinery mixed C4 |
| CN104053752B (en) * | 2012-01-11 | 2016-08-31 | 巴斯夫欧洲公司 | The gaseous state C of purification is provided4thick fraction is as the method for the feed stream using selective solvent extractive distillation |
| CN104053752A (en) * | 2012-01-11 | 2014-09-17 | 巴斯夫欧洲公司 | Method for providing a purified crude gaseous C4 fraction as an input stream for an extractive distillation using a selective solvent |
| CN103420756B (en) * | 2012-05-16 | 2016-05-18 | 中国石油化工股份有限公司 | The method of preparing propylene from C 4 olefins |
| CN103420760B (en) * | 2012-05-16 | 2015-09-09 | 中国石油化工股份有限公司 | The method of carbon four and ethene disproportionation propylene |
| CN103420756A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing propylene from C4 olefin |
| CN103420760A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing propylene through C4 and ethylene disproportionation |
| US10358399B2 (en) | 2014-11-03 | 2019-07-23 | Basf Se | Process for preparing 1,3-butadiene from n-butenes by oxidative dehydrogenation |
| US10384990B2 (en) | 2014-11-14 | 2019-08-20 | Basf Se | Method for producing 1,3-butadiene by dehydrogenating n-butenes, a material flow containing butanes and 2-butenes being provided |
| US11124470B2 (en) | 2017-04-03 | 2021-09-21 | Sabic Global Technologies B.V. | Systems and methods of producing methyl tertiary butyl ether and propylene |
| CN110526796A (en) * | 2019-08-30 | 2019-12-03 | 凯瑞环保科技股份有限公司 | It is a kind of to provide the device and method of four raw material of carbon for MTBE downstream unit |
| CN110526796B (en) * | 2019-08-30 | 2024-02-06 | 凯瑞环保科技股份有限公司 | Device and method capable of providing four-carbon raw materials for MTBE downstream device |
| CN113501742A (en) * | 2021-05-28 | 2021-10-15 | 中国石油化工股份有限公司 | Utilization method of ethylene cracking C4 |
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