CN101555197A - Comprehensive use method of mixed C-4 - Google Patents
Comprehensive use method of mixed C-4 Download PDFInfo
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- CN101555197A CN101555197A CNA2008100432508A CN200810043250A CN101555197A CN 101555197 A CN101555197 A CN 101555197A CN A2008100432508 A CNA2008100432508 A CN A2008100432508A CN 200810043250 A CN200810043250 A CN 200810043250A CN 101555197 A CN101555197 A CN 101555197A
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Abstract
The invention relates to a comprehensive use method of mixed C-4, which mainly aims at solving the problem that the comprehensive utilization ratio of mixed C-4 by-products generated by a steam cracking device and an FCC device is low in the prior art. The method comprises the following steps: (1) adopting an extract technology to obtain butadiene through separation; (2) adopting an etherification technology to synthesize MTBE by using isobutene remained in the C-4 undergoing the extraction in the first step; (3) separating water, ether and alcohol in the C-4 undergoing the etherification in the second step by adopting a refining and separating technology; (4) producing propylene through the disproportionating reaction between the mixed C-4 which is purified in the third step and ethylene by adopting an olefine disproportionation technology; and (5) cyclically taking the mixed C-4 which is left after the reaction in the fourth step as the raw material of a cracking furnace. Such a technical scheme better solves the problem and can be used in the industrial production for increasing the propylene production and the comprehensive value of the mixed C-4.
Description
Technical field
The present invention relates to a kind of method of comprehensive utilization of mixed c 4.
Background technology
The present invention relates to the by-product C that a kind of mixed c 4 means 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 utilization, 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 not high problem of FCC apparatus by-product mixed c 4 comprehensive utilization ratio in the conventional art, and a kind of new mixed c 4 method of comprehensive utilization is provided.This method has and adopts extraction extraction technique, etherificate 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 method of comprehensive utilization of 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 extraction tower cat head obtains containing the mixture stream passes 1 of butylene, butane, enters the etherificate unit; Extraction Tata still obtains containing the mixture stream passes 2 of divinyl, extraction agent, obtains butadiene stream 3 through further separating;
(2) in the etherificate unit, MTBE is produced in iso-butylene in the logistics 1 and methyl alcohol reaction; The etherification reaction product obtains MTBE product and residue mixed c 4 logistics 4 through separation;
(3) by refining isolation technique, isolate water, ether and alcohol in the logistics 4, the mixed c 4 logistics 5 after purifying enters the butylene disproportionation unit;
(4) in the disproportionation unit, butene-2 in the logistics 5 and ethene carry out disproportionation reaction, generate propylene; The disproportionation reaction product obtains propylene product, unreacting ethylene and unreacted mixed c 4 logistics 6 through separation.
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; The catalyzer preferred version that etherification reaction adopts is a large hole cation exchanger resin, and the temperature of reaction preferable range is 25～80 ℃, and the reaction pressure preferable range is 0.8～2.0MPa, and the reaction velocity preferable range is 1～30 hour
-1Disproportionation reactor preferable range in the disproportionation unit is for dividing two sections, and the epimere preferred version is the filling isomerization catalyst, and the hypomere preferred version is the filling disproportionation catalyst; Lower section catalyst is 1～10: 1 with the epimere catalyst weight than preferable range; Butene-1 preferred version in the logistics 5 turns to butene-2 for first isomery in disproportionation reactor; The unreacting ethylene preferred version enters disproportionation reactor for circulation; Disproportionation reactor epimere catalyzer preferred version is metal oxide or strongly-acid molecular sieve, and the lower section catalyst 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-1.Logistics 6 circulations enter the cracking stock of steam cracking device as pyrolyzer.
The inventive method adopts comprehensive utilization extraction extraction technique, etherificate 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, the reaction of chemical industry added value and generated MTBE, propylene, 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 4s).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.
Fig. 1, A is a methyl alcohol among Fig. 2 or Fig. 3, and B is light boiling point polar material, and C is the high boiling point polar material, D is refining separating unit, and 1 is the raw material mixed c 4, and 2 is extraction agent, 3 is MTBE, 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 the etherificate unit, 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 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 etherificate unit 13; The bottom is butadiene, extractant mixture. Through the etherificate unit, isobutene with The methyl alcohol reaction generates MTBE; Residual carbon four after the etherificate enters refining separative element D, and isolates light boiling point polar substances B and higher boiling polar substances C; Through the mixing carbon four behind the refining separating-purifying with enter disproportionated reaction after ethene (5+6) mixes Device 7 carries out isomerization reaction and disproportionated reaction, and product separates by separative element 8 and obtains: unreacting ethylene 6, propylene 9, Unreacted mixing carbon 4 10, circulation mix carbon 4 11. Unreacting ethylene 6 circulates as reaction raw materials unreacted mixing carbon 4 10 deliver to steam cracking device as cracking stock.
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 300 Si-Al molecular sieve, and the temperature of reaction of the first catalytic cracking reaction device and the second catalytic cracking reaction device is 500 ℃, and reaction pressure is 0.3MPa; First rectifying tower 16 is a valve tray column, and stage number is 110, and tower top pressure is 0.8MPa; Selective hydrogenation catalyst is the palladium metal series catalysts, and temperature of reaction is 110, and reaction pressure is 3.0MPa; Catalyst for etherification is an ion exchange resin, and temperature of reaction is 30 ℃, and reaction pressure is 1.5MPa; 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 13% and 3% (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 180 ℃, and reaction pressure is 5.0MPa; Catalytic cracking catalyst adopts the small-bore zeolite molecular sieve, and temperature of reaction is 550 ℃, and reaction pressure is 0.15MPa; Rectifying tower 34 is a valve tray column, and stage number is 80, and tower top pressure is 0.5MPa.Experimental results show that and to obtain propylene and ethene is respectively 8.1% and 1.8% (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 etherificate unit comprises methyltertiarvbutyl ether reactor, rectifying tower, eparating methanol tower and a methanol distillation column.The catalyzer of methyltertiarvbutyl ether reactor filling is a macropore H ion exchange resin, and temperature of reaction is 60 ℃, and reaction pressure is 1.3MPa, and reaction velocity is 8 hours
-1Rectifying tower is a valve tray column, and stage number is 40, and the cat head working pressure is 0.5MPa; Eparating methanol tower is a sieve-tray tower, and stage number is 30, and the cat head working pressure is 0.2MPa; Methanol distillation column is a valve tray column, and stage number is 30, and the cat head working pressure is 0.2MPa.Disproportionation reactor 7 epimere catalyst loading magnesium oxide, lower section catalyst filling Tungsten oxide 99.999; Lower section catalyst is 6: 1 with epimere catalyst weight ratio; 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%, butylene--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 0.65MPa; Water wash column is a sieve-tray tower, and stage number is 60, and the cat head working pressure is 0.4MPa; Rectifying tower (2) is a sieve-tray tower, and stage number is 50, and the cat head working pressure is 0.6MPa; Rectifying tower (3) is a sieve-tray tower, and stage number is 80, and the cat head working pressure is 0.6MPa.The etherificate unit comprises methyltertiarvbutyl ether reactor, rectifying tower, eparating methanol tower and a methanol distillation column.The catalyzer of methyltertiarvbutyl ether reactor filling is a macropore P ion exchange resin, and temperature of reaction is 40 ℃, and reaction pressure is 1.1MPa, and reaction velocity is 10 hours
-1Rectifying tower is a sieve-tray tower, and stage number is 50, and the cat head working pressure is 0.6MPa; Eparating methanol tower is a valve tray column, and stage number is 25, and the cat head working pressure is 0.3MPa; Methanol distillation column is a valve tray column, and stage number is 30, and the cat head working pressure is 0.2MPa.Disproportionation reactor 7 epimere catalyst loading silicon sol, lower section catalyst filling Tungsten oxide 99.999; Lower section catalyst is 2: 1 with epimere catalyst weight ratio; Temperature of reaction is 300 ℃, and reaction pressure is 2.8MPa, and reaction velocity is 5 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 raw material mixed c 4 1).
[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 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 packing tower, and packed height is 30 meters, and the cat head working pressure is 0.55MPa; Water wash column is a packing tower, and packed height is 20, and the cat head working pressure is 0.5MPa; Rectifying tower (2) is a valve tray column, and stage number is 43, and the cat head working pressure is 0.55MPa; Rectifying tower (3) is a packing tower, 22 meters of packed heights, and the cat head working pressure is 0.4MPa.The etherificate unit comprises methyltertiarvbutyl ether reactor, rectifying tower, eparating methanol tower and a methanol distillation column.The catalyzer of methyltertiarvbutyl ether reactor filling is a macropore P ion exchange resin, and temperature of reaction is 80 ℃, and reaction pressure is 1.5MPa, and reaction velocity is 20 hours
-1Rectifying tower is a valve tray column, and stage number is 40, and the cat head working pressure is 0.4MPa; Eparating methanol tower is a packing tower, and packed height is 10 meters, and the cat head working pressure is 0.3MPa; Methanol distillation column is a packing tower, and packed height is 12 meters, and the cat head working pressure is 0.1MPa.Disproportionation reactor 7 epimere catalyst loading magnesium oxide, lower section catalyst filling Tungsten oxide 99.999; Lower section catalyst is 8: 1 with epimere catalyst weight ratio; Temperature of reaction is 330 ℃, and reaction pressure is 3.5MPa, and reaction velocity is 15 hours
-1Experimental installation proves recyclable 95% divinyl, 96% iso-butylene, and obtaining propylene simultaneously is the pyrolyzer cracking stock of 25.1% (weight is at raw material mixed c 4 1) and 28% (weight is at raw material mixed c 4 1).
Claims (10)
1, a kind of method of comprehensive utilization of 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 extraction tower cat head obtains containing the mixture stream passes 1 of butylene, butane, enters the etherificate unit; Extraction Tata still obtains containing the mixture stream passes 2 of divinyl, extraction agent, obtains butadiene stream 3 through further separating;
(2) in the etherificate unit, MTBE is produced in iso-butylene in the logistics 1 and methyl alcohol reaction; The etherification reaction product obtains MTBE product and residue mixed c 4 logistics 4 through separation;
(3) by refining isolation technique, isolate water, ether and alcohol in the logistics 4, the mixed c 4 logistics 5 after purifying enters the butylene disproportionation unit;
(4) in the disproportionation unit, butene-2 in the logistics 5 and ethene carry out disproportionation reaction, generate propylene; The disproportionation reaction product obtains propylene product, unreacting ethylene and unreacted mixed c 4 logistics 6 through separation.
2, according to the method for comprehensive utilization of the described 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 method for comprehensive utilization of the described mixed c 4 of claim 1.
4, according to the method for comprehensive utilization of the described 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 method for comprehensive utilization of the described mixed c 4 of claim 1, it is characterized in that the catalyzer that etherification reaction adopts is a large hole cation exchanger resin, temperature of reaction is 25～80 ℃, and reaction pressure is 0.8～2.0MPa, and reaction velocity is 1～30 hour
-1
6, according to the method for comprehensive utilization of the described mixed c 4 of claim 1, it is characterized in that the disproportionation reactor in the disproportionation unit divides two sections, epimere filling isomerization catalyst, hypomere filling disproportionation catalyst, lower section catalyst is 1～10: 1 with epimere catalyst weight ratio; Butylene in the logistics 5～1 first isomery in disproportionation reactor turns to butene-2.
7,, it is characterized in that the unreacting ethylene circulation enters the disproportionation reactor in the disproportionation unit according to the method for comprehensive utilization of the described mixed c 4 of claim 1.
8, according to the method for comprehensive utilization of the described mixed c 4 of claim 7, it is characterized in that disproportionation reactor epimere catalyzer is metal oxide or strongly-acid molecular sieve, lower section catalyst is a metal oxide.
9, according to the method for comprehensive utilization of the described 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
10,, it is characterized in that logistics 6 circulations enter the cracking stock of steam cracking device as pyrolyzer according to the method for comprehensive utilization of the described mixed c 4 of claim 1.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102285854A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increasing yields of propylene, ethylene and butadiene |
| CN102372608A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Mixed C4 utilization method |
| CN103974941A (en) * | 2011-10-17 | 2014-08-06 | 国际壳牌研究有限公司 | Process for preparing an epoxide from an oxygenate |
| CN104030872A (en) * | 2013-03-04 | 2014-09-10 | 中国石化工程建设有限公司 | Method for improving raffinate product yield of acetonitrile-process 1,3-butadiene extracting apparatus |
| CN105102404A (en) * | 2013-03-28 | 2015-11-25 | 环球油品公司 | Integrated process for increasing butadiene production |
| CN105859530A (en) * | 2015-01-23 | 2016-08-17 | 上海优华系统集成技术有限公司 | Stabilizer tower and MTBE device catalytic distillation column combined cycle system |
| CN106365941A (en) * | 2015-07-22 | 2017-02-01 | 中国石油天然气股份有限公司 | Conversion process of low-carbon hydrocarbon |
| CN106365947A (en) * | 2015-07-22 | 2017-02-01 | 中国石油天然气股份有限公司 | Method for converting light hydrocarbons of topped oil |
| CN106365942A (en) * | 2015-07-22 | 2017-02-01 | 中国石油天然气股份有限公司 | Mixed C4 conversion method |
| CN106866337A (en) * | 2015-12-14 | 2017-06-20 | 中国石油天然气股份有限公司 | Conversion and utilization process of mixed C4 |
| CN107257783A (en) * | 2015-02-19 | 2017-10-17 | 赛贝克环球科技公司 | The system and method relevant with production methyl tertiary butyl ether(MTBE) |
| US11124470B2 (en) | 2017-04-03 | 2021-09-21 | Sabic Global Technologies B.V. | Systems and methods of producing methyl tertiary butyl ether and propylene |
| US11505516B2 (en) | 2017-07-19 | 2022-11-22 | Sabic Global Technologies B.V. | Use of MTBE raffinate in the production of propylene |
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| US5300718A (en) * | 1988-09-19 | 1994-04-05 | Lyondell Petrochemical Company | Olefin conversion process |
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| CN102285854A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increasing yields of propylene, ethylene and butadiene |
| CN102285854B (en) * | 2010-06-18 | 2013-11-06 | 中国石油化工股份有限公司 | Method for increasing yields of propylene, ethylene and butadiene |
| CN102372608A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Mixed C4 utilization method |
| CN103974941A (en) * | 2011-10-17 | 2014-08-06 | 国际壳牌研究有限公司 | Process for preparing an epoxide from an oxygenate |
| CN104030872A (en) * | 2013-03-04 | 2014-09-10 | 中国石化工程建设有限公司 | Method for improving raffinate product yield of acetonitrile-process 1,3-butadiene extracting apparatus |
| CN104030872B (en) * | 2013-03-04 | 2016-01-13 | 中国石化工程建设有限公司 | A kind of method improving acetonitrile method 1,3-butadiene extraction plant raffinate product yield |
| CN105102404A (en) * | 2013-03-28 | 2015-11-25 | 环球油品公司 | Integrated process for increasing butadiene production |
| CN105859530A (en) * | 2015-01-23 | 2016-08-17 | 上海优华系统集成技术有限公司 | Stabilizer tower and MTBE device catalytic distillation column combined cycle system |
| CN105859530B (en) * | 2015-01-23 | 2018-04-06 | 上海优华系统集成技术有限公司 | A kind of stabilizer and MTBE device catalytic rectifying tower combined cycle equipment |
| CN107257783A (en) * | 2015-02-19 | 2017-10-17 | 赛贝克环球科技公司 | The system and method relevant with production methyl tertiary butyl ether(MTBE) |
| CN106365942A (en) * | 2015-07-22 | 2017-02-01 | 中国石油天然气股份有限公司 | Mixed C4 conversion method |
| CN106365947A (en) * | 2015-07-22 | 2017-02-01 | 中国石油天然气股份有限公司 | Method for converting light hydrocarbons of topped oil |
| CN106365941A (en) * | 2015-07-22 | 2017-02-01 | 中国石油天然气股份有限公司 | Conversion process of low-carbon hydrocarbon |
| CN106365947B (en) * | 2015-07-22 | 2019-08-02 | 中国石油天然气股份有限公司 | Method for converting light hydrocarbons of topped oil |
| CN106365941B (en) * | 2015-07-22 | 2019-09-03 | 中国石油天然气股份有限公司 | Conversion process of low-carbon hydrocarbon |
| CN106365942B (en) * | 2015-07-22 | 2020-02-14 | 中国石油天然气股份有限公司 | Mixed C4 conversion method |
| CN106866337A (en) * | 2015-12-14 | 2017-06-20 | 中国石油天然气股份有限公司 | Conversion and utilization process of mixed C4 |
| CN106866337B (en) * | 2015-12-14 | 2019-12-10 | 中国石油天然气股份有限公司 | Conversion and utilization process of mixed C4 |
| US11124470B2 (en) | 2017-04-03 | 2021-09-21 | Sabic Global Technologies B.V. | Systems and methods of producing methyl tertiary butyl ether and propylene |
| US11505516B2 (en) | 2017-07-19 | 2022-11-22 | Sabic Global Technologies B.V. | Use of MTBE raffinate in the production of propylene |
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