CN104370676B - A kind of take C 4 olefin as the method for raw material production propylene by-product ethene - Google Patents

Abstract

It take C 4 olefin as the method for raw material production propylene by-product ethene that the present invention provides a kind of, 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. Low-carbon alkene disproportionation processes and low-carbon alkene Deep Catalytic Cracking process are coupled by the method for the present invention, adopt suitable olefin metathesis and olefin cracking catalyzer and array mode, it is possible to reach the object improving propylene, yield of ethene.

Description

A kind of take C 4 olefin as the method for raw material production propylene by-product ethene

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 the 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 demand of propylene is increased severely by the whole world year by year. 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. Whole world propylene nearly 67% is from the coproduction of preparing ethylene by steam cracking at present, 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 all produce a large amount of low-carbon alkenes through the device of preparing propylene by methanol transformation by raw material of coal and Sweet natural gas, and its chemical utilization rate is very low. Olefin metathesis and olefin cracking propylene are all emerging " main product " propylene technology, and object is not only and is efficiently utilized low-carbon alkene resource excessive, cheap, increases its added value, are also propylene enhancing, ethene the important technology met the need of market.

Preparing propylene through olefin disproportionation is an important channel of propylene enhancing, mainly contains two operational paths: one is butylene and the operational path of ethene disproportionation propylene, and two is the operational path 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.

Adopting 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:

CH₂-CH=CH-CH₂+CH₂=CH₂��2CH₂=CH-CH₃

Owing to catalyzer has acidity, system also may occur isomerisation of olefin, two grades of side reactions such as disproportionation and polymerization.

Isomerization reaction:

CH₃-CH=CH-CH₃��CH₂=CH-CH₂-CH₃

CH₃-CH=CH-CH₃��CH₃=C (CH₃)-CH₃

Two grades of disproportionation reactions:

${\mathrm{CH}}_2=\mathrm{CH}-{\mathrm{CH}}_2-{\mathrm{CH}}_3+{\mathrm{CH}}_3-\mathrm{CH}=\mathrm{CH}-{\mathrm{CH}}_3\→{\mathrm{CH}}_2={\mathrm{CH}-\mathrm{CH}}_3+C_5^{=}$

${\mathrm{CH}}_2=\mathrm{CH}-{\mathrm{CH}}_2-{\mathrm{CH}}_3+{\mathrm{CH}}_2=\mathrm{CH}-{\mathrm{CH}}_3\→{\mathrm{CH}}_2={\mathrm{CH}}_2+C_5^{=}$

Polyreaction:

nCH₂=CH₂��(-CH₂-CH₂-)_n

nCH₂CH=CHCH₂��(-CH₂-CH₂-CH₂-CH₂-)_n

At present in the world industrialization be taking butylene and ethene as the operational path of raw material disproportionation propylene, i.e. OCTC4 disproportionation processes (JochiefG.E.OilandGas [J] .1999 of ABBLummus-Phillips company, 77 (38): 62-66), the raw material adopted is 2-butylene and ethene, and catalyzer is WO₃/SiO₂, 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 carry out under liquid phase or gas phase condition. This technique ethylene conversion is the selectivity nearly 100% of propylene, and it is 97% that butylene is converted into the selectivity of propylene, 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 ethene and butylene carries out the catalyzer of 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 with gamma-aluminium oxide carrier load load perrhenic acid in its embodiment, the then obtained Re of roasting₂O₇/Al₂O₃Catalyzer, 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 its embodiment taking specific surface area²The aluminum oxide of/g is supported carrier perrhenic acid and cesium nitrate, and then caesium modification Re is prepared in roasting₂O₇/Al₂O₃Catalyzer, temperature of reaction be 60 DEG C, butylene heavy time total air speed be about 1h^-1Ethene and butylene disproportionation reaction it is applied under condition, but butene conversion is not high, catalyzer react 12h online after 1-butylene, 2-butylene and iso-butylene transformation efficiency be 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; Preparing propylene through olefin disproportionation has been carried out systematic study and has had a lot of achievement in research report (HuaDerun, ChenShengli, YuanGuimeietal.Metathesisofbutenetopropeneandpenteneover WO by China University Of Petroleum Beijing₃/ MTS-9.MicroporousandMesoporousMaterials, 2011,143 (2-3): 320-325;SangLei, ChenShengli, YuanGuimeietal.Preparationofmesoporousaluminawithlargepo resizeandtheirsupportedrheniumoxidecatalystsinmetathesis of1-buteneand2-butenetopropene.JournalofNaturalGasChemis try.2012,21 (3): 352-359; Zhao Qin peak .WO₃-SiO₂2-butylene and ethene disproportionation propylene on catalyzer: [doctorate paper], 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 reaction main product thing only propylene of ethene and 2-butylene, but produce 1mol propylene and need in theory to consume 0.5mol ethene. 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 great problem that is that propylene faces and that cannot solve, is the major limitation of this process exploitation.

Butylene carries out the technique that self disproportionation reaction produces propylene under the effect of catalyzer, and not consumption of ethylene only adopts butylene to be raw material, and it mainly occurs reaction equation as follows:

Although the disproportionation reaction of 1-butylene and 2-butylene not consumption of ethylene, but while producing propylene, also produce the little amylene of using value, namely produce 1mol propylene and also produce 1mol amylene in theory, therefore the receipts rate 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. The low-carbon alkene how amylene of residue C 4 olefin and generation is converted into high value is the most important problem that this olefin metathesis is produced propylene reaction scheme and faced.

Olefins by catalytic cracking technique is taking C4-C8 alkene as 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 (BoltHVGlanzS.Increasepropyleneyieldscost-effectively [J] .Hydrocarbonprocessing of German Lurgi company, 2002, 81 (12): 77-80), Superflex technique (the LeyshonD.W. of the chemical company of ARCO, Cozzone, G.E..Productionofolefinsfromamixtureofolefinsandparaffin s.USPatent, 5043522, 1991), MOI (MobilOlefineInterconversion) technique of Mobil company (river woods. by-product C4 and C5 changes into technology progress [J] of propylene and ethene. ethylene industry, 2002.14 (3): 11-15), the OCP technique (GLOVERB.TheATOFINA/UOPOlefinCrackingProcessforLightOlefi nProduction.inJPIPetroleumRefiningConference.2004) of AtoFina/UOP and the OCC technique (Teng Jiawei of domestic Shanghai Petroleum Chemical Engineering Institute, Wang Yangdong, Liu Hong magnitude. the increasing output of ethylene/propylene new technology of petrochemical industry Shanghai institute of China 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 catalyst, 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 temperature of reaction height, 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, preparing more suitable molecular sieve catalyst, prolongation olefin cracking catalyst life, the selectivity improving propylene and receipts rate is all the emphasis problem that this technology needs to solve.

In sum, preparing propylene through olefin disproportionation produces propylene from olefin cracking, by-product ethene is two kinds of different processing methodes, all there are respective relative merits. Prior art does not have by report that two kinds of techniques combine.

Summary of the invention

It take C 4 olefin as the processing method of raw material production propylene by-product ethene that the main purpose of the present invention is to provide a kind of, makes operational path rationally feasible, stable operation, propene yield height.

In order to realize foregoing invention object, this case contriver 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, amylene and the above olefin cracking that can C 4 olefin disproportionation reaction be produced 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 propylene enhancing and the object of by-product ethene.

Specifically, it take C 4 olefin as the method for raw material production propylene by-product ethene that the present invention provides a kind of, 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, the present invention taking C 4 olefin be raw material production propylene by-product ethene method in, described olefin disproportionation catalyst is the tungsten-based catalyst of active ingredient tungsten comprising silica support and load load; Wherein carrier specific surface area is 200��900m²��g^-1, pore volume is 0.5��1.5cm³��g^-1, aperture is 3��15nm (preferably having Jie's micropore and part macropore), and acid amount is 0.2��1.5mmolNH₃��g^-1; In catalyzer, active ingredient is with WO₃Meter mass content is 5��15%.

The active ingredient of the olefin disproportionation catalyst of the present invention is mainly based on tungsten, it is also possible to further containing other active ingredients such as molybdenums, or comprise the modified components such as magnesium further. The loading method of active ingredient can carry out with reference to the routine operation of art, such as, can be adopt equi-volume impregnating, by the presoma of active ingredient (such as, ammonium metawolframate can be selected in tungsten source) load is downloaded to 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, finally with certain ramp to roasting 3h at 350 DEG C, then it is warmed up to the catalyzer that namely 550 DEG C of roasting 6h obtain the present invention.

In the preferred specific embodiments of the present invention, disproportionation catalyst used is tungsten base/magnesium-modified composite catalyst of molybdenum base. Wherein carrier is SiO₂, specific surface area 300��500m²/ g, pore volume 0.5��1.5cm³��g^-1, aperture 3��13nm, acid amount is 0.2��1.0mmolNH₃��g^-1; Active ingredient WO in catalyzer₃Mass content 5��15%, MoO₃Mass content 3��15%, content of magnesia are 5��10%. In the more particular embodiment of the present invention, carrier S iO in disproportionation catalyst used₂Specific surface area be 395.3m²/ g, pore volume is 0.87cm³��g^-1, aperture is 8.66nm, and acid amount is 0.41mmolNH₃��g^-1; By equi-volume impregnating load load active ingredient, active ingredient WO in catalyzer₃Mass content is 8%, MoO₃Mass content is 5%, content of magnesia is 6%.

According to specific embodiment of the invention scheme, the present invention taking C 4 olefin be raw material production propylene by-product ethene method in, described olefin cracking catalyzer is the ZSM-5 of non-modified or modification. Its specific surface area is 200��400m²��g^-1, pore volume is 0.1��0.5cm³��g^-1, aperture is 2��10nm, and acid amount is 0.2��1.5mmolNH₃��g^-1. Preferably there is the ZSM-5 molecular sieve of micropore, part Jie hole and macropore.

Preferred version according to 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 NH₄Cl or NH₄NO₃Exchange, 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 making zeolite is reduced. In addition rare earth modified, P Modification, potassium modification, fluorine richness etc. can also be carried out, to adjust the acid matter of ZSM-5 molecular sieve so that it is meet in the present invention and the acid amount of molecular sieve catalyst is required (0.2��1.5mmolNH₃��g^-1)��

In the 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 the more particular embodiment of the present invention, phosphorous modified ZSM-5 molecular sieve specific surface area used is 322.3m²/ g, Kong Rongwei 0.2172cm³/ g, aperture is 2.695nm, and acid amount is 0.55mmolNH₃/g^-1; It is by ZSM-5 molecular sieve and SiO₂��Al₂O₃After mechanically mixing, adding binding agent, compression molding roasting, then with equi-volume impregnating, shaping molecular sieve catalyst is carried out P Modification and be prepared from, wherein phosphorus content is 2%.

Preferred specific embodiments according to the present invention, the present invention taking C 4 olefin be raw material production propylene by-product ethene method in, C 4 olefin raw material can be made to carry out disproportionation and scission reaction simultaneously, can also first carry out disproportionation and carry out scission reaction again, or first carrying out cracking carries out disproportionation reaction again.Preferably, the present invention taking C 4 olefin be raw material production propylene by-product ethene method in, make C 4 olefin raw material first carry out olefin dismutation reaction under olefin disproportionation catalyst existence condition, 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, other alkene except ethene, propylene in streams is carried out all or part of reaction so that it is 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 of art, such as, isolate propylene and/or ethene.

Preferred specific embodiments according to the present invention, the present invention taking C 4 olefin be raw material production propylene by-product ethene method in, the mass ratio of olefin disproportionation catalyst and olefin cracking catalyzer be preferably 1:1��5:1.

According to specific embodiment of the invention scheme, C 4 olefin disproportionation and catalytic pyrolysis coupling technique can adopt multiple feasible coupling mode, such as:

Olefin disproportionation catalyst and olefin cracking catalyzer are 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 are 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 is carried out from low-carbon alkene scission reaction under different reactor, different reaction conditions.

Specifically, described catalyst combination loading form is selected from one of under type: flows to by reaction mass and is 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, it is preferable that control 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; Control 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, control 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; Control 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 the C 4 olefin after separating C5 fraction from one or more streams following and evaporate point: reclaim from naphtha steam cracking, crude oil catalytic cracking, oil field gas, ethylene oligomerization or taking coal and Sweet natural gas as 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%; Reaction raw materials does not need to add water vapor or raw material is diluted by the rare gas element such as nitrogen, helium. In addition, in C 4 olefin raw material, oxygenatedchemicals (moisture, methyl alcohol, ether etc.) content should control below 1%, it is possible to be by C 4 olefin raw material in advance through Adsorption oxygenatedchemicals to the olefin dismutation reaction and the scission reaction that carry out the present invention after content is below 1% again.

In sum, it take C 4 olefin as the processing method of raw material production propylene by-product ethene that the present invention provides a kind of, the production propylene route not consumption of ethylene of the present invention, taking the C 4 olefin (mainly 1-butylene and 2-butylene) in liquefied gas as 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 to isolate ethene and the propylene of generation, but ethene can be contained by what a front technique produced, the educt flow of propylene all enters in next technique, streams will be removed ethene, other alkene that concentration beyond propylene is lower carries out all or part of reaction, it is made to change into propylene and ethene. the method of the present invention can improve material carbon four olefin conversion, 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 receipts rate, 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 different reaction conditions.

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

The implementation process of the present invention and the useful effect of generation are described in detail, it is intended to help reader to understand essence and the feature of the present invention better below by way of specific embodiment, 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 iO₂Specific surface area be 395.3m²/ g, pore volume is 0.87cm³��g^-1, aperture is 8.66nm, and acid amount is 0.41mmolNH₃��g^-1; By equi-volume impregnating load load active ingredient, active ingredient WO in catalyzer₃Mass content is 8%, MoO₃Mass content is 5%, content of magnesia is 6%.

The refinery of C 4 olefin material choice Shanghai petrochemical industry raffinates oil, and wherein butene content is greater than 80%, and cis-butylene 2 and trans-butylene 2 total content are greater than 70%.

Being 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 and analyzes.

Adopting Beijing analytical instrument factory SP-3420 type gas chromatograph (Pona post 45m �� 0.20mm �� 0.4 ��m, FID detection), analysis condition is: post temperature 35 DEG C, vaporizer 180 DEG C, adopts area normalization method to calculate the content of each material composition.Represent the activity of catalyzer with the selectivity (S) of the total conversion rate (X) of butylene and the disproportionation reaction generating propylene, ethene, calculation formula is as follows:

$X_{C_4^{=}}=\frac{100-w_{C_4}-w_{1-C_4^{=}}-w_{2-C_4^{=}}}{100-w_{C_4}}\×100\%$

$S_{C_3}=\frac{w_{C_3}}{w_{C_2}+w_{C_3}+w_{C_5}+w_{C_5^{+}}}\×100\%$

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 to be subtracted 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;For in reaction product, carbon number is greater than the massfraction of the alkene of 5.

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 SiO₂��Al₂O₃After mechanically mixing, adding binding agent, compression molding roasting, then with equi-volume impregnating, shaping catalyzer is carried out P Modification and be prepared from, wherein phosphorus content is 2%. This phosphorous modified ZSM-5 molecular sieve specific surface area is 322.3m²/ g, Kong Rongwei 0.2172cm³/ g, aperture is 2.695nm, and acid amount is 0.55mmolNH₃/g^-1��

The refinery of C 4 olefin material choice Shanghai petrochemical industry raffinates oil, and wherein butene content is greater than 80%, and cis-butylene 2 and trans-butylene 2 total content are greater than 70%.

Being passed in the low-carbon alkene catalytic cracking reaction device loading above-mentioned phosphorous modified ZSM-5 molecular sieve with the volumetric flow rate of 7.5mL/h by C 4 olefin raw material 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 and analyzes. 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 receipts rate 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 iO₂Specific surface area be 395.3m²/ g, pore volume is 0.87cm³��g^-1, aperture is 8.66nm, and acid amount is 0.41mmolNH₃��g^-1; By equi-volume impregnating load load active ingredient, active ingredient WO in catalyzer₃Mass content is 8%, MoO₃Mass 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 SiO₂��Al₂O₃After mechanically mixing, adding binding agent, compression molding roasting, then with equi-volume impregnating, shaping catalyzer is carried out P Modification and be prepared from, wherein phosphorus content is 2%. This phosphorous modified ZSM-5 molecular sieve specific surface area is 322.3m²/ g, Kong Rongwei 0.2172cm³/ g, aperture is 2.695nm, and acid amount is 0.55mmolNH₃/g^-1��

The refinery of C 4 olefin material choice Shanghai petrochemical industry 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, the butylene disproportionation of the present embodiment/cracking coupling reaction device 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 monitoring temperature device, 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. Being 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 lead 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.

The butylene disproportionation of the present embodiment/cracking coupling reaction performance test data analysis result 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, after being coupled by disproportionation/cracking technology 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 receipts rate 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; Control 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 is with embodiment 4, it is intended to investigate the change in 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, catalyst life extended than life-span during the independent cracking of the independent disproportionation of comparative example 1 or comparative example 2.

Claims (9)

1. being a method for raw material production propylene by-product ethene taking C 4 olefin, the method comprises:

Olefin disproportionation catalyst and catalytic cracking catalyst segmentation are 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, C 4 olefin raw material first carries out disproportionation, whole materials after disproportionation reaction carry out scission reaction, generate propylene and ethene;

Wherein, described olefin disproportionation catalyst is the tungsten-based catalyst of the active ingredient tungsten comprising silica support and load load; Wherein carrier specific surface area is 200��900m²��g^-1, pore volume is 0.5��1.5cm³��g^-1, aperture is 3��15nm, and acid amount is 0.2��1.5mmolNH₃��g^-1; In catalyzer, active ingredient is with WO₃Meter 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��400m²��g^-1, pore volume is 0.1��0.5cm³��g^-1, aperture is 2��10nm, and acid amount is 0.2��1.5mmolNH₃��g^-1;

Further, control 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; Control 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 first carry out olefin dismutation reaction under olefin disproportionation catalyst existence condition, 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, other alkene except ethene, propylene in streams is carried out all or part of reaction so that it is 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 SiO₂, specific surface area 300��500m²/ g, pore volume 0.5��1.5cm³��g^-1, aperture 3��13nm, acid amount is 0.2��1.0mmolNH₃��g^-1; Active ingredient WO in catalyzer₃Mass content 5��15%, MoO₃Mass 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, control 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; Control 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 are packed in same fixed-bed reactor by the mass ratio segmentation alternate combinations of 1:1��5:1, 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 are 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 is carried out from low-carbon alkene scission reaction under different reactor, different reaction conditions.

6. method according to claim 1 or 2 or 5, wherein, described catalyst combination loading form is selected from one of under type: flows to by reaction mass and is followed successively by olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer or olefin disproportionation catalyst-quartz sand-olefin cracking catalyzer-quartz sand-olefin disproportionation catalyst.

7. method according to claim 1, wherein, described C 4 olefin raw material comprises the C 4 olefin after separating C5 fraction from one or more streams following and evaporates point:

Reclaim from naphtha steam cracking, crude oil catalytic cracking, oil field gas, ethylene oligomerization or taking coal and Sweet natural gas as 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%; Reaction raw materials does not need to add water vapor or raw material is diluted by rare gas element.

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%.