CN101597199B - Method for producing propylene - Google Patents
Method for producing propylene Download PDFInfo
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- CN101597199B CN101597199B CN2009100654936A CN200910065493A CN101597199B CN 101597199 B CN101597199 B CN 101597199B CN 2009100654936 A CN2009100654936 A CN 2009100654936A CN 200910065493 A CN200910065493 A CN 200910065493A CN 101597199 B CN101597199 B CN 101597199B
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- propylene
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- butylene
- butene
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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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a method for producing propylene, solving the deficiencies of low rate of production of propylene, no full utilization of unreacted C4 olefin and the like of the prior art. The method comprises the following steps: alcohol generates material containing ethene under the action of ZSM-5 molecular sieve based catalyst whose Si/Al mol-ratio is 20-90; disproportionation reaction is carried out on the material containing ethene and n-butene material containing 2-butylene to generate material containing propylene; the material containing propylene is separated, separated propylene serves as the product, and separated unreacted ethane material serves as the product or returns back to serve as the feed of disproportionation reaction; isomerization reaction is carried out on separated unreatced n-butene material to generate material containing 2-butylene which returns back to serve as the feed of disproportionation reaction. The method of the invention can convert C4 olefin into propylene products at most.
Description
Technical field
The invention belongs to the refining of petroleum field, particularly a kind of method of utilizing ethanol and C 4 olefin to produce propylene.
Background technology
The existing maturation process of producing propylene has: hydro carbons is by thermal conversion processes preparing ethylene, the propylene of free radical reaction, such as the tube furnace steam cracking process of lighter hydrocarbons; Catalytic cracking or the Deep Catalytic Cracking process of the heavy hydrocarbon by carbonium ion mechanism can a certain amount of propylene of by-product and a small amount of ethene; Produce propylene by the propane high-temperature dehydrogenation.
In addition, adopt olefin dismutation reaction also can produce propylene.
Olefin disproportionation is under catalyst action, and the two bond ruptures of the C=C in the alkene and restructuring obtain new olefin product.Alkene has 1 mole 2-butylene and 1 mole ethylene reaction can obtain 2 moles propylene through the reaction process that disproportionation obtains propylene, the 1-butylene reaction of 1 mole 2-butylene and 1 mole can obtain 1 mole propylene and 1 mole amylene, the 2-butylene reaction of 1 mole iso-butylene and 1 mole can obtain 1 mole propylene and 1 amylene, in the process of these disproportionation reaction preparing propones, what productivity of propylene was the highest is 2-butylene and ethylene reaction process.
US6271430 discloses the method by 1-butylene and 2-butylene producing propylene with dismutation and amylene, and the catalyzer that the method adopts is with Re
2O
7Be main active component.The problem that this technique exists is that catalyzer is relatively more expensive, and the productivity ratio of propylene is lower.
CN02137460.0 discloses a kind of method of preparing propylene by butene disproportionation, and its method is take butylene as raw material, adopt take silicon-dioxide as carrier, and the fixed bed catalyst of load Tungsten oxide 99.999, and specific surface area of catalyst is 270～550 meters
2/ gram, 250～450 ℃ of temperature of reaction, reaction pressure is 0～10MPa, the liquid phase air speed is 0.1～1.0 hour
-1React under the condition.CN03150733.6 discloses a kind of olefin disproportionation catalyst, preparing propylene by butene disproportionation catalyzer particularly, and disclosed catalyzer is with the mesoporous SiO of the HMS of tungstenic
2Molecular sieve is active main body, the catalyzer of making take silicon sol as binding agent.But the problem that these two patents exist is that Propylene Selectivity is lower, generally is no more than 38%.
CN101279879A discloses a kind of method that mixed c 4 is produced propylene that fully utilizes, and this technique obtains propylene, ethene with the mixed c 4 catalytic pyrolysis first under 400～600 ℃ condition, and the ethene that separation is obtained carries out disproportionation propylene processed with carbon four again.But this method need to obtain participating in the ethene of disproportionation reaction under higher reaction temperatures, severe reaction conditions, and productivity of propylene is low.
CN200680042187 discloses a kind of manufacture method that contains the propylene of the carbon that derives from biological organism, the method is that the moisture of the ethene that obtains by the ethanol that derives from biological organism and generation is from rear, carry out refining with adsorbents, carry out efficiently replacement(metathesis)reaction.Its shortcoming is because disproportionation reaction does not occur for 1-butylene and ethene, so 1-butylene is not used in this process.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing ethanol and C 4 olefin to produce propylene, low with productivity of propylene in the solution prior art, to shortcomings such as unreacted C 4 olefin do not take full advantage of.
The invention provides a kind of method of producing propylene, the steps include:
(1) feed ethanol is to generate under 20～90 the ZSM-5 molecular sieve catalyst action to contain ethylene feed at silica alumina ratio;
(2) the disproportionation reaction generation occurs with the n-butene material that contains 2-butylene and contains the propylene material in the ethylene feed that contains from step (1) under molybdenum, tungsten catalyst effect;
(3) the propylene material that contains from step (2) separates, isolated propylene is as product, isolated unreacting ethylene material or as product or return step (2), the isomerization reaction generation occurs and contains the 2-butylene material in isolated unreacted n-butene material under the aluminium oxide catalyst effect that is loaded with alkaline earth metal oxide, contain the 2-butylene material and return step (2).
The temperature of reaction of described step (1) is 180～430 ℃, and reaction pressure is 0.01～0.80MPa, and weight hourly space velocity is 0.5～10h
-1
The catalyzer of described step (2), its support of the catalyst are that to be selected from diatomite, kaolin, activated carbon and silica alumina ratio be more than one mixtures in 100～350 ZSM-5 molecular sieves.
The temperature of reaction of described step (2) is 200～450 ℃, and reaction pressure is 0.01～4.00MPa, and weight hourly space velocity is 0.5～10h
-1
The temperature of reaction of described step (3) isomerization reaction is 220～410 ℃, and reaction pressure is 0.01～4.00MPa, and weight hourly space velocity is 0.5～10h
-1
The present invention compared with prior art has following advantage:
1) the present invention utilizes ethanol and C 4 olefin to prepare propylene for raw material, and the product ethene of can holding concurrently as required, has realized the C 4 olefin maximization is converted into the purpose of propylene, ethylene product.
2) the present invention's ethanol of participating in reacting can be obtained by renewable resources-biomass, and therefore these biomass such as plant amylum, plant straw and saccharide biomass etc. utilize this technique indirectly to obtain propylene product by biomass.
3) because process of the present invention is provided with isomerization steps, unreacted n-butene material (wherein major part is 1-butylene) isomery can be turned to the 2-butylene freshening, therefore compare with CN200680042187, the butylene utilization ratio is high, and productivity of propylene is high.
Describe the present invention in detail below by the drawings and specific embodiments, but do not limit the scope of the invention:
Accompanying drawing and description of drawings
Fig. 1 is a kind of simple flow chart of producing propylene of the present invention.
Fig. 2 is the another kind of simple flow chart of producing propylene of the present invention.
Among the figure: the 1-feed ethanol, 2-contains ethylene feed, and 3-contains the n-butene material of 2-butylene, and 4-contains the propylene material, the 5-propylene, 6-unreacting ethylene material, 7-unreacted n-butene material, 8-contains the 2-butylene material, 9-the first reactor, 10-the second reactor, 11-the 3rd reactor, 12-separation system.
Embodiment
As shown in Figure 1, feed ethanol 1 enters the first reactor 9, at silica alumina ratio is to react to generate under the effect of 20～90 ZSM-5 molecular sieve catalyzer to contain ethylene feed 2; To contain ethylene feed 2 and send into the second reactor 10 from the n-butene material 3 that contains 2-butylene outside the battery limit (BL), the disproportionation reaction generation occurs and contains propylene material 4 in ethene and n-butene under the effect of molybdenum, tungsten catalyst; Containing propylene material 4 enters separation system 12 and separates, isolated propylene 5 and unreacting ethylene material 6 go out device as product, isolated unreacted n-butene material 7 enters the 3rd reactor 11, the isomerization reaction generation occurs under the aluminium oxide catalyst effect that is loaded with alkaline earth metal oxide contain 2-butylene material 8, contain the entrance that 2-butylene material 8 returns the second reactor 10 and carry out freshening, to improve the output of propylene.
Fig. 2 is that from the different of Fig. 1 separation system 12 isolated unreacting ethylene materials 6 return the entrance of the second reactor 10.
Described reactor is fixed-bed reactor, moving-burden bed reactor or fluidized-bed reactor.
The temperature of reaction of described the first reactor 9 is 180～430 ℃, and reaction pressure is 0.01～0.80MPa, and weight hourly space velocity is 0.5～10h
-1
Catalyzer in described the second reactor 10, its support of the catalyst are that diatomite, kaolin, activated carbon and silica alumina ratio are more than one mixture in 100～350 the ZSM-5 molecular sieve.
The temperature of reaction of described the second reactor 10 is 200～450 ℃, and reaction pressure is 0.01～4.00MPa, and weight hourly space velocity is 0.5～10h
-1
The temperature of reaction of described the 3rd reactor 11 is 220～410 ℃, and reaction pressure is 0.01～4.00MPa, and weight hourly space velocity is 0.5～10h
-1
The below describes the present invention in detail with embodiment, but embodiment does not limit the scope of the invention.
Embodiment 1
Be that the ethanol material 1 of 95 % by weight is sent into the first reactor 9 with ethanol content, ethanol is that at 220～430 ℃, reaction pressure is 0.05MPa under 75 the ZM-5 molecular sieve catalyst effect at silica alumina ratio, and weight hourly space velocity is 0.8h
-1Under the condition reaction obtain ethylene content be 98 % by weight contain ethylene feed 2; To contain ethylene feed 2 and 2-butylene content and be 75% from sending into the second reactor 10 after n-butene material 3 mixes containing outside the battery limit (BL), ethene and 2-butylene are in containing under 10 % by weight Tungsten oxide 99.999s, the 2 % by weight molybdenum oxide catalyst effects take diatomite as carrier, at 280～380 ℃, reaction pressure is 1.00MPa, and weight hourly space velocity is 0.5h
-1Reaction obtains containing propylene material 4 under the condition; To contain propylene material 4 sends into separation system 12 and obtains propylene 5, propylene is sent as product, unreacting ethylene material 6 is sent as product, unreacted n-butene material 7 is sent into the 3rd reactor 11, in containing under 5 % by weight magnesium oxide, the 2 % by weight calcium oxide catalyst effects take aluminum oxide as carrier, at 310～390 ℃, reaction pressure is 1.100MPa, and weight hourly space velocity is 0.9h
-1Isomerization reaction occurs under the condition generate the material 8 that contains 2-butylene, the entrance that the material 8 that will contain 2-butylene returns the second reactor 10 carries out freshening, and to improve the output of propylene, first, second, and third reactor is fixed-bed reactor.This process can obtain ethene, propylene product simultaneously, and productivity of propylene is 85 % by weight (with respect to the charging 2-butylene).
Be that the ethanol material 1 of 85 % by weight is sent into the first reactor 9 with ethanol content, ethanol is that at 240～350 ℃, reaction pressure is 0.07MPa under 45 the ZM-5 molecular sieve catalyst effect at silica alumina ratio, and weight hourly space velocity is 1.5h
-1Under the condition reaction obtain ethylene content be 98.5% contain ethylene feed 2; To contain ethylene feed 2 and 2-butylene content and be 65 % by weight from sending into the second reactor 10 after n-butene material 3 mixes containing outside the battery limit (BL), ethene and 2-butylene are take ZSM-5 molecular sieve the containing 7 % by weight Tungsten oxide 99.999s, 12 % by weight molybdenum oxide catalyst effects under as carrier of silica alumina ratio as 260, at 310～410 ℃, reaction pressure is 1.50MPa, and weight hourly space velocity is 0.9h
-1Reaction obtains containing propylene material 4 under the condition; To contain propylene material 4 and send into separation system 12 and obtain propylene 5, propylene is sent as product, and the entrance that unreacting ethylene material 6 returns the second reactor 10 carries out freshening, the maximum production of propylene product; Unreacted n-butene material 7 is sent into the 3rd reactor 11, and in containing under 1% magnesium oxide, the 5% calcium oxide catalyst effect take aluminum oxide as carrier, at 320～395 ℃, reaction pressure is 0.90MPa, and air speed is 1.2h
-1Isomerization reaction occurs under the condition generate and contain 2-butylene material 8, will contain the entrance that 2-butylene material 8 returns the second reactor 10 and carry out freshening, to improve the output of propylene, first, second, and third reactor is fixed-bed reactor.This process can obtain with minimum ethanol and n-butene the propylene product of maximum, and productivity of propylene is 93 % by weight (with respect to the charging 2-butylene).
Claims (1)
1. a method of producing propylene is characterized in that comprising the steps:
(1) feed ethanol is to generate under 20～90 the ZSM-5 molecular sieve catalyst action to contain ethylene feed at silica alumina ratio;
(2) the disproportionation reaction generation occurs with the n-butene material that contains 2-butylene and contains the propylene material in the ethylene feed that contains from step (1) under molybdenum, tungsten catalyst effect;
(3) the propylene material that contains from step (2) is separated, isolated propylene is as product, isolated unreacting ethylene material or as product or return step (2), isomerization reaction occurs and generates the material that contains 2-butylene in isolated unreacted n-butene material under the aluminium oxide catalyst effect that is loaded with alkaline earth metal oxide, the material that contains 2-butylene returns step (2);
The temperature of reaction of described step (1) is 180～430 ℃, and reaction pressure is 0.01～0.80MPa, and weight hourly space velocity is 0.5～10h
-1
The catalyzer of described step (2), its support of the catalyst are that diatomite, kaolin, activated carbon and silica alumina ratio are more than one mixtures in 100～350 ZSM-5 molecular sieves;
The temperature of reaction of described step (2) is 200～450 ℃, and reaction pressure is 0.01～4.00MPa, and weight hourly space velocity is 0.5～10h
-1
The temperature of reaction of described step (3) is 220～410 ℃, and reaction pressure is 0.01～4.00MPa, and weight hourly space velocity is 0.5～10h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100654936A CN101597199B (en) | 2009-07-22 | 2009-07-22 | Method for producing propylene |
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|---|---|---|---|
| CN2009100654936A CN101597199B (en) | 2009-07-22 | 2009-07-22 | Method for producing propylene |
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| CN101597199B true CN101597199B (en) | 2013-01-02 |
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| CN110922291B (en) * | 2019-11-22 | 2021-09-21 | 中国石油大学(北京) | Method for producing propylene by using bio-based ethanol and butanol mixed solution |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121121A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Olefines double bond isomerizing catalyst and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101121121A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Olefines double bond isomerizing catalyst and its preparation method |
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Address after: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant after: China Petrochemical Group Corp. Co-applicant after: Luoyang Petrochemical Engineering Corporation /SINOPEC Address before: 100728 Beijing, Chaoyangmen, North Street, No. 22, No. Applicant before: China Petrochemical Group Corp. Co-applicant before: Luoyang Petrochemical Engineering Co., China Petrochemical Group |
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