CN104370676A - Method for producing propylene and coproducing ethylene from C4 olefins - Google Patents
Method for producing propylene and coproducing ethylene from C4 olefins Download PDFInfo
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- CN104370676A CN104370676A CN201410643822.1A CN201410643822A CN104370676A CN 104370676 A CN104370676 A CN 104370676A CN 201410643822 A CN201410643822 A CN 201410643822A CN 104370676 A CN104370676 A CN 104370676A
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- olefin
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- disproportionation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
Abstract
The invention provides a method for producing propylene and coproducing ethylene from C4 olefins, which comprises the following steps: filling the mixture of an olefin disproportionation catalyst and a catalytic cracking catalyst in one reactor or sectionally filling the olefin disproportionation catalyst and catalytic cracking catalyst in differential reactors which are connected in series, and passing a C4 olefin raw material through the olefin disproportionation catalyst and catalytic cracking catalyst to carry out C4 olefin disproportionation reaction and low-carbon olefin cracking reaction, thereby generating the propylene and ethylene. The method couples a low-carbon olefin disproportionation technique with a low-carbon olefin deep catalytic cracking technique, and adopts an appropriate combination mode for the olefin disproportionation catalyst and olefin cracking catalyst, thereby achieving the goal of enhancing the yields of the propylene and ethylene.
Description
Technical field
The present invention relates to a kind of take C 4 olefin as the method for raw material production propylene by-product ethene, specifically, relates to one C 4 olefin and makes raw material, adopts olefin metathesis and olefins by catalytic cracking coupling technique to produce propylene and the method for by-product ethene.
Background technology
Propylene is one of most important Organic Chemicals being only second to ethene, and it is mainly for the production of products such as polypropylene, vinyl cyanide and vinylformic acid.By the impact of acryloyl derivative demand growth, the whole world increases severely year by year to the demand of propylene.The up-to-date research report of CMAI is pointed out, the average growth rate per annum of whole world propylene demand is about 5.2%, the market requirement vigorous (Liu little Bo, Wang Dingbo, Ma Zhiyuan etc. the research [J] of C_5 olefins propylene and ethene. petrochemical complex, 2005.34 (supplementary issue): 97-99).
The production technique of propylene is different from other chemical, often obtains with coproduction or by-product form.Current global propylene nearly 67% is from the coproduction of preparing ethylene by steam cracking, and 30% from refinery's (mainly FCC apparatus) by-product, also has 3% from techniques such as dehydrogenating propane, preparing propylene from methanol, low-carbon alkene disproportionation and olefin crackings.
In " main product " propylene technology, naphtha steam cracking, crude oil catalytic cracking, oil field gas reclaim, ethylene oligomerization and with coal and Sweet natural gas for raw material all produces a large amount of low-carbon alkenes through the device of preparing propylene by methanol transformation, its chemical utilization rate is very low.Olefin metathesis and olefin cracking preparation of propylene are all emerging " main product " propylene technology, and object is not only excessive, the cheap low-carbon alkene resource of efficiency utilization, is increased its added value, are also propylene enhancings, ethene the important technology of meeting the need of market.
Preparing propylene through olefin disproportionation is an important channel of propylene enhancing, mainly contains two operational paths: one is the operational path of butylene and ethene disproportionation propylene, and two is operational paths of butylene (comprising 1-butylene and 2-butylene) self disproportionation propylene; Olefin disproportionation catalyst is mainly divided into that W (tungsten) is catalyst based, Re (rhenium) is catalyst based and Mo (molybdenum) is catalyst based, respectively has its relative merits.
Adopt raw material butylene and ethene to carry out disproportionation reaction, under the katalysis of olefin disproportionation catalyst, the principal reaction occurred in system is the disproportionation reaction of ethene and 2-butylene:
CH
2-CH＝CH-CH
2+CH
2＝CH
2→2CH
2＝CH-CH
3
Because catalyzer has acidity, in system, the side reactions such as isomerisation of olefin, secondary disproportionation and polymerization also may be there is.
Isomerization reaction:
CH
3-CH＝CH-CH
3→CH
2＝CH-CH
2-CH
3
CH
3-CH＝CH-CH
3→CH
3＝C(CH
3)-CH
3
Secondary disproportionation reaction:
Polyreaction:
nCH
2＝CH
2→(-CH
2-CH
2-)
n
nCH
2CH＝CHCH
2→(-CH
2-CH
2-CH
2-CH
2-)
n
At present industrialized is in the world the operational path that is raw material disproportionation propylene with butylene and ethene, i.e. OCT C4 disproportionation processes (Jochief G.E.Oil and Gas [J] .1999 of ABBLummus-Phillips company, 77 (38): 62-66), the raw material adopted is 2-butylene and ethene, and catalyzer is WO
3/ SiO
2, isomerization catalyst is MgO.Temperature of reaction 200 ~ 400 DEG C, air speed 6 ~ 40h
-1, pressure 30 ~ 100psig (1psig=6.894kPa), residence time 0.5s ~ 0.5h, reaction can be carried out under liquid phase or gas phase condition.This technique ethylene conversion is the selectivity nearly 100% of propylene, and butenc is the selectivity of propylene is 97%, butylene total conversion rate 85% ~ 92% (in butene feed 1-butylene massfraction 50% ~ 95%).The technique (US Patent No. 2004/077909) of the ethene that IFP (IFP) and Taiwan Zhong You company develop and producing propene from butylene by disproportion, what adopt is rhenium-based catalyst, this technique is run on a set of demonstration unit of the Zhong You company of Taiwan Province in Kaohsiung, 8600h is run altogether from September in April, 1988 to nineteen ninety, comprise the life experiment of 5700h, catalyst regeneration 76 times, the physical and chemical performance of catalyzer has no significant change, but does not have industrialization so far.US Patent No. 5120894 reports the catalyzer that ethene and butylene carry out disproportionation reaction propylene, this catalyzer is the oxide carried on aluminum oxide, silicon-dioxide, alkalimetal oxide and alkaline earth metal oxide carrier of molybdenum, tungsten or rhenium, but Propylene Selectivity is poor.US Patent No. 4795734 reports olefin metathesis rhenium-containing catalysts, is to support perrhenic acid with gamma-aluminium oxide carrier in embodiment, and then roasting obtains Re
2o
7/ Al
2o
3catalyzer, for propylene disproportionation reaction, but transformation efficiency is not high, only has about 20%.US Patent No. 2002/0143222 reports C4 olefin metathesis catalyzer, and this catalyzer take rhenium oxide as active ingredient, and caesium is promotor, and gama-alumina is carrier, is 180m in embodiment with specific surface area
2the aluminum oxide of/g is supported carrier perrhenic acid and cesium nitrate, and then caesium modification Re is prepared in roasting
2o
7/ Al
2o
3catalyzer, temperature of reaction be 60 DEG C, butylene heavy time total air speed be about 1h
-1ethene is applied to and butylene disproportionation reacts under condition, but butene conversion is not high, after catalyzer reacts 12h online, the transformation efficiency of 1-butylene, 2-butylene and iso-butylene is respectively 34%, 62% and 15%, in addition, the more ethene of reaction needed, ethene and 2-butylene mol ratio are up to 11.The DaLian, China Chemistry and Physics Institute (Huang Shengjun, Xin Wenjie, Bai Jie etc. ethene and 2-butylene disproportionation propylene [J] on molybdenum loaded catalyst. petrochemical complex, 2003,32 (3): 191-194) what carry out producing propylene with dismutation employing with ethene and 2-butylene is catalyst with base of molybdenum; China University Of Petroleum Beijing has carried out systematic study to preparing propylene through olefin disproportionation and has had a lot of achievement in research to report (HuaDerun, Chen Shengli, Yuan Guimei et al.Metathesis of butene to propene and pentene overWO
3/ MTS-9.Microporous and Mesoporous Materials, 2011,143 (2-3): 320-325; SangLei, Chen Shengli, Yuan Guimei et al.Preparation of mesoporous alumina with large poresize and their supported rhenium oxide catalysts in metathesis of 1-butene and 2-butene topropene.Journal of Natural Gas Chemistry.2012,21 (3): 352-359; Zhao Qin peak .WO
3-SiO
22-butylene and ethene disproportionation propylene on catalyzer: [Ph.D. Dissertation], China University Of Petroleum Beijing, Beijing: 2009), the catalyzer adopted has rhenium-based catalyst, tungsten-based catalyst etc., and the raw material of employing is butylene and ethene or butylene (comprising 1-butylene and 2-butylene).
Although the disproportionation reaction of ethene and 2-butylene reacts principal product only have propylene, producing 1mol propylene needs to consume 0.5mol ethene in theory.In addition, this reaction is balanced reaction, wants to make the productivity of propylene of reaction to increase, often needs ethene excessive.For this reason, the valuable chemical material ethylene that the need of production consumption of this propylene is a large amount of, this is that this operational path produces that propylene faces and insurmountable significant problem, is the major limitation of this process exploitation.
Butylene carries out the technique that self disproportionation reaction produces propylene under the effect of catalyzer, not consumption of ethylene, and only adopt butylene to be raw material, its equation that mainly reacts is as follows:
Although the disproportionation reaction of 1-butylene and 2-butylene not consumption of ethylene, while producing propylene, also produce the little amylene of using value, namely produce 1mol propylene and also produce 1mol amylene in theory, therefore the yield of propylene reduces greatly.Only have an appointment 20% with propylene once through yield during tungsten-based catalyst, only have an appointment 30% with propylene once through yield during rhenium-based catalyst.How the amylene of residual carbon alkatetraenes and generation being converted into the low-carbon alkene of high value, is the vital problem that this olefin metathesis is produced propylene reaction scheme and faced.
Olefins by catalytic cracking technique is with C4-C8 alkene for raw material, under molecular sieve catalyst effect, is produced the technique of propylene and ethene by fixed bed or fluidized-bed process.Relatively typical process has Propylur technique (Bolt H V Glanz S.Increase propylene yields cost-effectively [J] .Hydrocarbonprocessing of German Lurgi company, 2002, 81 (12): 77-80), Superflex technique (the LeyshonD.W. of ARCO chemical company, Cozzone, G.E..Production of olefins from a mixture of olefins and paraffins.USPatent, 5043522, 1991), MOI (the Mobil Olefine Interconversion) technique of Mobil company (river woods. by-product C4 and C5 changes into the technical progress [J] of propylene and ethene. ethylene industry, 2002.14 (3): 11-15), the OCP technique (GLOVER B.The ATOFINA/UOP Olefin Cracking Process forLight Olefin Production.in JPI Petroleum Refining Conference.2004) of AtoFina/UOP and the OCC technique (Teng Jiawei of domestic Shanghai Petroleum Chemical Engineering Institute, Wang Yangdong, Liu's red magnitude. the increasing output of ethylene/propylene new technology of Sinopec Shanghai institute exploitation. [J]. the 16 national ethene annual meeting, 201208:534-537), the C _ 4 alkene catalytic pyrolysis technique of Lanzhou Petrochemical, BOC technique (the Wang Bin of Beijing Chemical Research Institute, high-strength, Suo Ji bolt .C4/C5 alkene preparing ethylene and propylene catalysis technique progress [J]. Journal of Molecular Catalysis, 2006, 20 (002): 188-192) etc.Olefins by catalytic cracking catalysts is zeolite molecular sieve, and conventional is have unique shape selectivity and acid ZSM-5 molecular sieve catalyzer, and temperature of reaction 500-650 DEG C, reaction pressure is 0.1-0.5Mpa, air speed 1-5h
-1.The difficult point of technology is that temperature of reaction is high, the easy coking and deactivation of catalyzer.For this reason, often adopt the measure adding water vapor (water vapor/hydrocarbon is 0.5-3:1) in reaction raw materials to improve reaction yield, reduce catalyst carbon deposit inactivation, but therefore too increase operation burden and the energy consumption of equipment.In addition, the molecular sieve catalyst that preparation is more suitable, prolongation olefin cracking catalyst life, the selectivity improving propylene and yield are all Important Problems that this technology needs to solve.
In sum, preparing propylene through olefin disproportionation and olefin cracking produce propylene, by-product ethene is two kinds of different processing methodes, all there are respective relative merits.The report two kinds of techniques combined is not had in prior art.
Summary of the invention
It take C 4 olefin as the processing method of raw material production propylene by-product ethene that main purpose of the present invention is to provide a kind of, and make operational path reasonable, stable operation, propene yield is high.
In order to realize foregoing invention object, inventor is by conscientious research, carry out olefin metathesis with tungsten-based catalyst, carry out low-carbon alkene cracking with ZSM-5 equimolecular sieve catalyst, C 4 olefin disproportionation and olefins by catalytic cracking technique are carried out coupling to produce propylene by-product ethene, the amylene that C 4 olefin disproportionation reaction can be produced and above olefin cracking are propylene and ethene, and can by further for unreacted raw material cracking, reduce amylene and above olefin(e) centent in product, improve feed stock conversion, reach the object of propylene enhancing and by-product ethene.
Specifically, the invention provides a kind of take C 4 olefin as the method for raw material production propylene by-product ethene, and the method comprises:
By olefin disproportionation catalyst and catalytic cracking catalyst mixing or segmentation be seated in the different reactor of same reactor or series connection, make C 4 olefin feedstream through olefin disproportionation catalyst and catalytic cracking catalyst, carry out C 4 olefin disproportionation reaction and low-carbon alkene scission reaction, generate propylene and ethene.
According to specific embodiment of the invention scheme, of the present invention is in the method for raw material production propylene by-product ethene with C 4 olefin, and described olefin disproportionation catalyst is the tungsten-based catalyst of active ingredient tungsten comprising silica support and support; Wherein carrier specific surface area is 200 ~ 900m
2g
-1, pore volume is 0.5 ~ 1.5cm
3g
-1, aperture is 3 ~ 15nm (preferably having Jie's micropore and part macropore), and acid amount is 0.2 ~ 1.5mmol NH
3g
-1; In catalyzer, active ingredient is with WO
3meter mass content is 5 ~ 15%.
The active ingredient of olefin disproportionation catalyst of the present invention, mainly based on tungsten, also further containing other active ingredients such as molybdenums, or can comprise the modified components such as magnesium further.The loading method of active ingredient can carry out with reference to the routine operation in affiliated field, such as, can be adopt equi-volume impregnating, by the presoma of active ingredient (such as, ammonium metawolframate can be selected in tungsten source) supporting satisfactory carrier (can pressed powder, broken sieve, choosing granularity is 20 ~ 40 object carriers) on, then at 50 DEG C, 6h is dried, continue to dry at 100 DEG C again, last be warmed up to 350 DEG C with given pace at roasting 3h, then be warmed up to 550 DEG C of roasting 6h and namely obtain catalyzer of the present invention.
In preferred specific embodiments of the present invention, disproportionation catalyst used is tungsten base/magnesium-modified composite catalyst of molybdenum base.Wherein carrier is SiO
2, specific surface area 300 ~ 500m
2/ g, pore volume 0.5 ~ 1.5cm
3g
-1, aperture 3 ~ 13nm, acid amount is 0.2 ~ 1.0mmolNH
3g
-1; Active ingredient WO in catalyzer
3mass content 5 ~ 15%, MoO
3mass content 3 ~ 15%, content of magnesia are 5 ~ 10%.In more particular embodiment of the present invention, carrier S iO in disproportionation catalyst used
2specific surface area be 395.3m
2/ g, pore volume is 0.87cm
3g
-1, aperture is 8.66nm, and acid amount is 0.41mmolNH
3g
-1; Active ingredient is supported, active ingredient WO in catalyzer with equi-volume impregnating
3mass content is 8%, MoO
3mass content is 5%, content of magnesia is 6%.
According to specific embodiment of the invention scheme, of the present invention is in the method for raw material production propylene by-product ethene with C 4 olefin, and described olefin cracking catalyzer is the ZSM-5 of non-modified or modification.Its specific surface area is 200 ~ 400m
2g
-1, pore volume is 0.1 ~ 0.5cm
3g
-1, aperture is 2 ~ 10nm, and acid amount is 0.2 ~ 1.5mmol NH
3g
-1.Preferably there is the ZSM-5 molecular sieve of the mesoporous and macropore of micropore, part.
According to preferred version of the present invention, the first-selected ZSM-5 molecular sieve with small crystal grains of low-carbon alkene catalyst for cracking that the present invention is used, its preparation method can adopt in-situ crystallization synthesis method, the universal method synthesis such as crystal seed synthesis method, the raw material adopted generally has water glass, kaolin, sheet kaolin, spinel or silicon sol, silochrom, tetraethoxy, pseudo-boehmite, Tai-Ace S 150, sodium metaaluminate, aluminum isopropylate etc., the template adopted can be TPAOH (TPAOH), 4-propyl bromide, propyl carbinol, ethylene glycol, potato starch, wheat starch, Zulkovsky starch, dextrin, sucrose, polyoxyethylene glycol etc.The sodium form ZSM-5 molecular sieve of preparation generally adopts certain density NH
4cl or NH
4nO
3exchange, obtain Hydrogen ZSM-5 molecular sieve, be i.e. low-carbon alkene catalytic cracking reaction used in the present invention.In the present invention, catalyst for cracking Hydrogen ZSM-5 molecular sieve used also can carry out modification, such as, can carry out hydrothermal modification, and in hydrothermal modification process, the four-coordination Al hydrolyzable in zeolite framework generates Al (OH)
3depart from skeleton, thus the acid site of zeolite is reduced.In addition also can carry out rare earth modified, P Modification, potassium modification, fluorine richness etc., to adjust the Acidity of ZSM-5 molecular sieve, make it meet in the present invention and (0.2 ~ 1.5mmol NH is required to the acid amount of molecular sieve catalyst
3g
-1).
In preferred specific embodiments of the present invention, catalyst for cracking used is phosphorous modified ZSM-5 molecular sieve, and wherein phosphorus content is 1 ~ 3%.In more particular embodiment of the present invention, phosphorous modified ZSM-5 molecular sieve specific surface area used is 322.3m
2/ g, pore volume is 0.2172cm
3/ g, aperture is 2.695nm, and acid amount is 0.55mmolNH
3/ g
-1; It is by ZSM-5 molecular sieve and SiO
2, Al
2o
3after mechanically mixing, add binding agent, compression molding roasting, then carry out P Modification with equi-volume impregnating to shaping molecular sieve catalyst and be prepared from, wherein phosphorus content is 2%.
According to preferred specific embodiments of the present invention, of the present invention is in the method for raw material production propylene by-product ethene with C 4 olefin, C 4 olefin raw material can be made to carry out disproportionation and scission reaction simultaneously, also can first carry out disproportionation and carry out scission reaction again, or first carrying out cracking carries out disproportionation reaction again.Preferably, of the present invention is in the method for raw material production propylene by-product ethene with C 4 olefin, makes C 4 olefin raw material first under olefin disproportionation catalyst existence condition, carry out olefin dismutation reaction, obtains the streams containing propylene and ethene; The streams making C 4 olefin disproportionation reaction obtain again carries out olefin cracking reaction under olefin cracking catalyzer existence condition, and other alkene in streams except ethene, propylene is carried out all or part of reaction, makes it change into propylene and ethene.Carry out the streams after disproportionation and scission reaction and can carry out subsequent disposal according to the routine operation in affiliated field, such as, isolate propylene and/or ethene.
According to preferred specific embodiments of the present invention, of the present invention is that in the method for raw material production propylene by-product ethene, the mass ratio of olefin disproportionation catalyst and olefin cracking catalyzer is preferably 1:1 ~ 5:1 with C 4 olefin.
According to specific embodiment of the invention scheme, C 4 olefin disproportionation and catalytic pyrolysis coupling technique can adopt multiple feasible coupled modes, such as:
Olefin disproportionation catalyst and olefin cracking catalyzer to be mixed by the mass ratio of 1:1 ~ 5:1 or segmentation alternate combinations is packed in same fixed-bed reactor, C 4 olefin disproportionation reaction and low-carbon alkene scission reaction are carried out under same reactor, same reaction conditions; Or
Olefin disproportionation catalyst and olefin cracking catalyzer to be loaded respectively by the mass ratio of 1:1 ~ 5:1 or segmentation alternate combinations is seated in the different fixed-bed reactor of series connection, C 4 olefin disproportionation reaction and low-carbon alkene scission reaction are carried out under different reactor, differential responses condition.
Particularly, described catalyst combination loading form is selected from one of under type: flow to by reaction mass and be followed successively by olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer, olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer-quartz sand-olefin disproportionation catalyst or olefin cracking catalyzer-quartz sand-olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer.
According to specific embodiment of the invention scheme, preferably controlling C 4 olefin disproportionation reaction temperature is 20 ~ 500 DEG C, and reaction gauge pressure is 0 ~ 5MPa, and weight hourly space velocity is 0.1 ~ 10h
-1; Controlling low-carbon alkene scission reaction temperature is 450 ~ 650 DEG C, and reaction gauge pressure is 0 ~ 0.5MPa, and weight hourly space velocity is 1 ~ 20h
-1.
As the preferred technical scheme of the present invention, controlling C 4 olefin disproportionation reaction temperature is 250 ~ 500 DEG C, and reaction gauge pressure is 0 ~ 3MPa, and weight hourly space velocity is 1 ~ 6h
-1; Controlling low-carbon alkene scission reaction temperature is 500 ~ 650 DEG C, and reaction gauge pressure is 0 ~ 0.3MPa, and weight hourly space velocity is 6 ~ 12h
-1.
According to specific embodiment of the invention scheme, described C 4 olefin raw material can comprise separate the C 4 olefin cut after C5 fraction from one or more streams following: reclaim from naphtha steam cracking, crude oil catalytic cracking, oil field gas, ethylene oligomerization or with coal and Sweet natural gas for raw material is through the streams of the device of methanol conversion ethene, propylene.Preferably, in described C 4 olefin raw material composition, the content summation of 1-butylene, 2-butylene is more than or equal to 50%; Do not need in reaction raw materials to add water vapor or the rare gas element such as nitrogen, helium dilutes raw material.In addition, in C 4 olefin raw material, content should control below 1% oxygenatedchemicals (moisture, methyl alcohol, ether etc.), can be that C 4 olefin raw material is carried out olefin dismutation reaction of the present invention and scission reaction through Adsorption oxygenatedchemicals more in advance after content is below 1%.
In sum, the invention provides a kind of take C 4 olefin as the processing method of raw material production propylene by-product ethene, production propylene route of the present invention not consumption of ethylene, with the C 4 olefin (mainly 1-butylene and 2-butylene) in liquefied gas for raw material, low-carbon alkene disproportionation processes and low-carbon alkene Deep Catalytic Cracking process are coupled, adopt suitable olefin metathesis and olefin cracking catalyzer and array mode, particularly educt flow does not need ethene and the propylene of isolating generation, but last technique can be produced containing ethene, the educt flow of propylene all enters in next technique, ethene is removed by streams, other alkene that concentration beyond propylene is lower carries out all or part of reaction, it is made to change into propylene and ethene.Method of the present invention can improve material carbon alkatetraenes transformation efficiency, promotes the carbon five that disproportionation reaction produces and the further cracking of above alkene, propylene and yield of ethene are significantly improved.Thus olefin metathesis technique and olefin cracking technique are coupled by the present invention, carry out the innovation of catalyzer and technique, open up new, the production propylene of high yield, a technological line for by-product ethene.
Accompanying drawing explanation
Fig. 1 adopts C 4 olefin disproportionation and catalyst for cracking to be distributed in the reactor of different series connection, carries out the process flow sheet reacted under differential responses condition.
Fig. 2 is butylene disproportionation reactivity worth analysis of experimental data figure in comparative example 1.
Fig. 3 is butene cracking reactivity worth analysis of experimental data figure in comparative example 2.
Fig. 4 is the butylene disproportionation/cracking coupling reaction performance test data analysis figure of embodiment 1.
Fig. 5 is the comparative analysis figure of the butylene disproportionation/cracking coupling of embodiment 1 and comparative example 1 disproportionation, comparative example 2 scission reaction performance separately separately.
Fig. 6 is the butylene disproportionation/cracking coupling reaction performance test data analysis figure of embodiment 2.
Fig. 7 is the butylene disproportionation/cracking coupling reaction performance test data analysis figure of embodiment 3.
Fig. 8 is the butylene disproportionation/cracking coupling reaction performance test data analysis figure of embodiment 4.
Fig. 9 is the catalyst life comparative analysis figure of the disproportionation/cracking coupling of embodiment 5 and comparative example 1 disproportionation, comparative example 2 scission reaction separately separately.
Embodiment
Describe the beneficial effect of implementation process of the present invention and generation below by way of specific embodiment in detail, be intended to help reader to understand essence of the present invention and feature better, not as can the restriction of practical range to this case.
Comparative example 1
Experiment disproportionation catalyst is tungsten base/magnesium-modified composite catalyst of molybdenum base.Wherein carrier S iO
2specific surface area be 395.3m
2/ g, pore volume is 0.87cm
3g
-1, aperture is 8.66nm, and acid amount is 0.41mmolNH
3g
-1; Active ingredient is supported, active ingredient WO in catalyzer with equi-volume impregnating
3mass content is 8%, MoO
3mass content is 5%, content of magnesia is 6%.
The refinery of C 4 olefin material choice oil of SPC raffinates oil, and wherein butene content is greater than 80%, and cis-butylene 2 and trans-butylene 2 total content are greater than 70%.
Be passed in the low-carbon alkene disproportionation reaction device of filling above-mentioned tungsten base/magnesium-modified composite catalyst of molybdenum base with the volumetric flow rate of 5mL/h by C 4 olefin raw material with double plunger micro pump, temperature of reaction is 320 DEG C, and weight hourly space velocity is 3h
-1, reaction pressure is 0.6MPa.Product after disproportionation reaction enters gas-chromatography analysis.
Adopt Beijing Analytical Instrument Factory SP-3420 type gas chromatograph (Pona post 45m × 0.20mm × 0.4 μm, FID detect), analysis condition is: column temperature 35 DEG C, vaporizer 180 DEG C, adopts area normalization method to calculate the content of each material composition.With the total conversion rate of butylene (X) and generate propylene, activity that the selectivity (S) of disproportionation reaction of ethene represents catalyzer, calculation formula is as follows:
Owing to containing a certain amount of butane in reaction raw materials, and butane is inert component at butylene in disproportionation preparation of propene system, so will deduct the amount of butane in computation process.In formula,
for butane massfraction in raw material;
for 1-butylene massfraction in reaction product;
for 2-butylene massfraction in reaction product;
for mass fraction of ethylene in reaction product;
for propylene massfraction in reaction product;
for amylene massfraction in reaction product;
the massfraction of the alkene of 5 is greater than for carbon number in reaction product.
Analytical results is shown in Figure 2.Experimental result shows, after disproportionation reaction, butene conversion is about 45%, and Propylene Selectivity is about 40%, and final propene yield can reach about 20%.In product, ethylene content is little, and C_5 olefins content is higher, about 14%.Final ethene and propylene total recovery are about 20%.
Comparative example 2
Experiment catalyst for cracking selects phosphorous modified ZSM-5 molecular sieve, and it is by ZSM-5 molecular sieve and SiO
2, Al
2o
3after mechanically mixing, add binding agent, compression molding roasting, then carry out P Modification with equi-volume impregnating to shaping catalyzer and be prepared from, wherein phosphorus content is 2%.This phosphorous modified ZSM-5 molecular sieve specific surface area is 322.3m
2/ g, pore volume is 0.2172cm
3/ g, aperture is 2.695nm, and acid amount is 0.55mmolNH
3/ g
-1.
The refinery of C 4 olefin material choice oil of SPC raffinates oil, and wherein butene content is greater than 80%, and cis-butylene 2 and trans-butylene 2 total content are greater than 70%.
To be passed into the volumetric flow rate of 7.5mL/h by C 4 olefin raw material in the low-carbon alkene catalytic cracking reaction device loading above-mentioned phosphorous modified ZSM-5 molecular sieve with double plunger micro pump, temperature of reaction is 550 DEG C, and weight hourly space velocity is 9h
-1, reaction pressure is normal pressure.Product after scission reaction enters gas-chromatography analysis.Analytical results is shown in Figure 3.
Experimental result shows, after scission reaction, C 4 olefin transformation efficiency is about 88%, and Propylene Selectivity is about 35%, and propene yield is about 30%.Ethylene selectivity and yield are about 20%.Ethene and propylene total recovery are about 50%.
Embodiment 1
Experiment olefin disproportionation catalyst is tungsten base/magnesium-modified composite catalyst of molybdenum base.Wherein carrier S iO
2specific surface area be 395.3m
2/ g, pore volume is 0.87cm
3g
-1, aperture is 8.66nm, and acid amount is 0.41mmolNH
3g
-1; Active ingredient is supported, active ingredient WO in catalyzer with equi-volume impregnating
3mass content is 8%, MoO
3mass content is 5%, content of magnesia is 6%.
Olefin cracking catalyst choice phosphorous modified ZSM-5 molecular sieve, it is by ZSM-5 molecular sieve and SiO
2, Al
2o
3after mechanically mixing, add binding agent, compression molding roasting, then carry out P Modification with equi-volume impregnating to shaping catalyzer and be prepared from, wherein phosphorus content is 2%.This phosphorous modified ZSM-5 molecular sieve specific surface area is 322.3m
2/ g, pore volume is 0.2172cm
3/ g, aperture is 2.695nm, and acid amount is 0.55mmolNH
3/ g
-1.
The refinery of C 4 olefin material choice oil of SPC raffinates oil, and wherein butene content is greater than 80%, and cis-butylene 2 and trans-butylene 2 total content are greater than 70%.
Shown in Figure 1, butylene disproportionation/cracking coupling reaction the device of the present embodiment comprises the low-carbon alkene disproportionation reaction device 1 and low-carbon alkene cat-cracker 2 that are arranged in series, also comprise head tank 3, adsorber 4, and the reducing valve 5 arranged as required, metal filter screen 6, flow gauge 7, check valve 8, back pressure valve 9 and temperature monitor, pressure monitor etc.The described olefin disproportionation catalyst of filling in low-carbon alkene disproportionation reaction device, the described olefin cracking catalyzer of filling in low-carbon alkene cracker, catalyst filling ratio is 3:1.Be passed in low-carbon alkene disproportionation reaction device by C 4 olefin raw material with the volumetric flow rate of 7.5mL/h with doubleplunger pump, temperature of reaction is 320 DEG C, and weight hourly space velocity is 3h
-1, reaction pressure is 0.6MPa.Whole materials after disproportionation reaction directly pass in low-carbon alkene cat-cracker, and scission reaction temperature is 550 DEG C, and weight hourly space velocity is 9h
-1, pressure is normal pressure, reaction product air inlet analysis of hplc.
Butylene disproportionation/cracking coupling reaction performance test the data results of the present embodiment is see Fig. 4, and the contrast of the independent disproportionation of butylene disproportionation/cracking coupling and comparative example 1, the independent scission reaction performance of comparative example 2 is see Fig. 5.Experimental result shows, by after disproportionation/cracking technology coupling in the present invention, butene conversion can reach more than 90%, and Propylene Selectivity is about 40%, and ethylene selectivity is about 30%, and final ethene and propylene total recovery can reach 60%, and yield is higher.
Embodiment 2
The present embodiment is compared with the technique of embodiment 1, difference is that C 4 olefin raw material is passed in low-carbon alkene disproportionation reaction device with the volumetric flow rate of 5ml/h, in another control olefins by catalytic cracking device, scission reaction temperature is 500 DEG C, and other processing condition are with embodiment 1.Reaction product air inlet analysis of hplc.Analytical results is see Fig. 6.
Embodiment 3
The present embodiment is compared with the technique of embodiment 1, difference is that C 4 olefin raw material is passed in low-carbon alkene disproportionation reaction device with the volumetric flow rate of 5ml/h, disproportionation and scission reaction catalyst filling ratio are 3:2, and to control low-carbon alkene disproportionation reaction temperature be 320 DEG C, and weight hourly space velocity is 6h
-1, reaction pressure is 0.6MPa; All the other processing condition are with embodiment 1.Reaction product air inlet analysis of hplc.Analytical results is see Fig. 7.
Embodiment 4
The present embodiment is compared with the technique of embodiment 1, difference is that C 4 olefin raw material is passed in low-carbon alkene disproportionation reaction device with the volumetric flow rate of 5ml/h, disproportionation and scission reaction catalyst filling ratio are 2:1, and to control low-carbon alkene disproportionation reaction temperature be 320 DEG C, and weight hourly space velocity is 6h
-1, reaction pressure is 0.6MPa; Controlling olefin cracking temperature of reaction is 550 DEG C, and weight hourly space velocity is 12h
-1, pressure is normal pressure; All the other processing condition are with embodiment 1.Reaction product air inlet analysis of hplc.Analytical results is see Fig. 8.
Embodiment 5
In the present embodiment, C 4 olefin disproportionation/cracking technology condition, with embodiment 4, is intended to the change investigating the coupling reaction rear catalyst life-span.Reaction product air inlet analysis of hplc.Analytical results is see Fig. 9.Experimental result shows, by after disproportionation/cracking coupling reaction in the present invention, and life during the independent cracking of catalyst life than the independent disproportionation of comparative example 1 or comparative example 2.
Claims (9)
1. be a method for raw material production propylene by-product ethene with C 4 olefin, the method comprises:
By olefin disproportionation catalyst and catalytic cracking catalyst mixing or segmentation be seated in the different reactor of same reactor or series connection, make C 4 olefin feedstream through olefin disproportionation catalyst and catalytic cracking catalyst, carry out C 4 olefin disproportionation reaction and low-carbon alkene scission reaction, generate propylene and ethene;
Wherein, described olefin disproportionation catalyst is the tungsten-based catalyst of active ingredient tungsten comprising silica support and support; Wherein carrier specific surface area is 200 ~ 900m
2g
-1, pore volume is 0.5 ~ 1.5cm
3g
-1, aperture is 3 ~ 15nm, and acid amount is 0.2 ~ 1.5mmol NH
3g
-1; In catalyzer, active ingredient is with WO
3meter mass content is 5 ~ 15%;
Described olefin cracking catalyzer is the ZSM-5 of non-modified or modification, and its specific surface area is 200 ~ 400m
2g
-1, pore volume is 0.1 ~ 0.5cm
3g
-1, aperture is 2 ~ 10nm, and acid amount is 0.2 ~ 1.5mmol NH
3g
-1;
Further, controlling C 4 olefin disproportionation reaction temperature is 20 ~ 500 DEG C, and reaction gauge pressure is 0 ~ 5MPa, and weight hourly space velocity is 0.1 ~ 10h
-1; Controlling low-carbon alkene scission reaction temperature is 450 ~ 650 DEG C, and reaction gauge pressure is 0 ~ 0.5MPa, and weight hourly space velocity is 1 ~ 20h
-1.
2. method according to claim 1, wherein, makes C 4 olefin raw material carry out disproportionation and scission reaction simultaneously or first carries out disproportionation to carry out scission reaction again or first carry out cracking carrying out disproportionation reaction again;
Preferably, make C 4 olefin raw material first under olefin disproportionation catalyst existence condition, carry out olefin dismutation reaction, obtain the streams containing propylene and ethene; The streams making C 4 olefin disproportionation reaction obtain again carries out olefin cracking reaction under olefin cracking catalyzer existence condition, and other alkene in streams except ethene, propylene is carried out all or part of reaction, makes it change into propylene and ethene.
3. method according to claim 1 and 2, wherein, described olefin disproportionation catalyst is tungsten base/magnesium-modified catalyzer of molybdenum base; Wherein carrier is SiO
2, specific surface area 300 ~ 500m
2/ g, pore volume 0.5 ~ 1.5cm
3g
-1, aperture 3 ~ 13nm, acid amount is 0.2 ~ 1.0mmolNH
3g
-1; Active ingredient WO in catalyzer
3mass content 5 ~ 15%, MoO
3mass content 3 ~ 15%, magnesium oxide mass content are 5 ~ 10%;
Described olefin cracking catalyzer is the ZSM-5 of P Modification, and wherein phosphorus content is 1 ~ 3%.
4. method according to claim 1 and 2, wherein, controlling C 4 olefin disproportionation reaction temperature is 250 ~ 500 DEG C, and reaction gauge pressure is 0 ~ 3MPa, and weight hourly space velocity is 1 ~ 6h
-1; Controlling low-carbon alkene scission reaction temperature is 500 ~ 650 DEG C, and reaction gauge pressure is 0 ~ 0.3MPa, and weight hourly space velocity is 6 ~ 12h
-1.
5. method according to claim 1, wherein:
Olefin disproportionation catalyst and olefin cracking catalyzer to be mixed by the mass ratio of 1:1 ~ 5:1 or segmentation alternate combinations is packed in same fixed-bed reactor, C 4 olefin disproportionation reaction and low-carbon alkene scission reaction are carried out under same reactor, same reaction conditions; Or
Olefin disproportionation catalyst and olefin cracking catalyzer to be loaded respectively by the mass ratio of 1:1 ~ 5:1 or segmentation alternate combinations is seated in the different fixed-bed reactor of series connection, C 4 olefin disproportionation reaction and low-carbon alkene scission reaction are carried out under different reactor, differential responses condition.
6. the method according to claim 1 or 2 or 5, wherein, described catalyst combination loading form is selected from one of under type: flow to by reaction mass and be followed successively by olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer, olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer-quartz sand-olefin disproportionation catalyst or olefin cracking catalyzer-quartz sand-olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer.
7. method according to claim 1, wherein, described C 4 olefin raw material comprises separate the C 4 olefin cut after C5 fraction from one or more streams following:
Reclaim from naphtha steam cracking, crude oil catalytic cracking, oil field gas, ethylene oligomerization or with coal and Sweet natural gas for raw material is through the streams of the device of methanol conversion ethene, propylene.
8. method according to claim 1, wherein, in described C 4 olefin raw material composition, the content summation of 1-butylene, 2-butylene is more than or equal to 50%; Do not need in reaction raw materials to add water vapor or rare gas element dilutes raw material.
9. method according to claim 1, wherein, in C 4 olefin raw material, oxygenates level is below 1%, or C 4 olefin raw material carries out olefin dismutation reaction and scission reaction through Adsorption oxygenatedchemicals again after content is below 1%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026936A (en) * | 1989-10-02 | 1991-06-25 | Arco Chemical Technology, Inc. | Enhanced production of propylene from higher hydrocarbons |
| CN102177223A (en) * | 2008-08-12 | 2011-09-07 | 鲁姆斯科技公司 | Integrated propylene production |
| CN102372572A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing propylene through C4 disproportionation |
-
2014
- 2014-11-11 CN CN201410643822.1A patent/CN104370676B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5026936A (en) * | 1989-10-02 | 1991-06-25 | Arco Chemical Technology, Inc. | Enhanced production of propylene from higher hydrocarbons |
| CN102177223A (en) * | 2008-08-12 | 2011-09-07 | 鲁姆斯科技公司 | Integrated propylene production |
| CN102372572A (en) * | 2010-08-23 | 2012-03-14 | 中国石油化工股份有限公司 | Method for preparing propylene through C4 disproportionation |
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