CN103772107B - The method of preparing propylene by butene disproportionation - Google Patents

The method of preparing propylene by butene disproportionation Download PDF

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CN103772107B
CN103772107B CN201210412602.9A CN201210412602A CN103772107B CN 103772107 B CN103772107 B CN 103772107B CN 201210412602 A CN201210412602 A CN 201210412602A CN 103772107 B CN103772107 B CN 103772107B
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butylene
disproportionation
reaction
propylene
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CN103772107A (en
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董静
王仰东
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The present invention relates to a kind of method of preparing propylene by butene disproportionation, mainly solve the problem that there is poor catalyst stability in conventional art.The present invention is by adopting with butylene and ethene for raw material, and be 200 ~ 450 DEG C in temperature of reaction, reaction pressure counts 0 ~ 5MPa with absolute pressure, and weight space velocity is 1 ~ 50 hour -1the weight ratio 1: 0.5 ~ 5 of butylene and ethene is under condition, raw material passes through beds, generate target product propylene, wherein used catalyst is the disproportionation catalyst of load tungsten and the alkaline earth metal oxide auxiliary agent through acidolysis modification, the mass ratio of the two mixing is the technical scheme of 1: 1 ~ 15, solves this problem preferably, can be used for the industrial production that butylene disproportionation prepares propylene.

Description

The method of preparing propylene by butene disproportionation
Technical field
The present invention relates to a kind of method of butylene and ethene disproportionation propylene.
Background technology
Olefin metathesis is by under the effect of transition metal compound catalyst, makes C=C double bond fracture in alkene and is again formed, to obtain the process of new olefin product.
Utilize the cross disproportionation effect of butylene and ethene, by adding appropriate ethene, by relative surplus, C that added value is lower 4olefin feedstock is converted into high added value propylene product.
Butene feedstock in disproportionation reaction is often from steam cracking or catalytic cracking unit, and containing a small amount of water, oxygenatedchemicals, sulfocompound etc., wherein oxygenatedchemicals mostly is alcohol or ether.These compounds are easy to be combined with the unoccupied orbital of disproportionation catalyst atoms metal occupy active sites, thus cause poisoning of catalyst, and therefore raw material has to pass through purification and just can enter bed and contact with disproportionation catalyst.
Preparing propylene through olefin disproportionation reaction adopts fixed-bed process more, and before raw material enters beds, liquid starting material and gas raw material need be pre-mixed evenly, is conducive to the reaction stability increasing catalyzer like this.
US5898091 and US6166279 reports C 4, C 5olefin treated, wherein in preparing propylene through olefin disproportionation process, the catalyzer adopted is Re 2o 7/ Al 2o 3, reactor is moving-bed.US6358482 proposes one C 4cut hydrocarbon produces the device of iso-butylene and propylene.C 4cut hydrocarbon isolates iso-butylene and 1-butylene and 2-butylene after selec-tive hydrogenation and rectifying, and the 1-butylene separated generates 2-butylene by double-bond isomerization, and rich 2-butylene material and ethene disproportionation reaction generate propylene, and disproportionation reaction catalyzer used is Re 2o 7/ Al 2o 3.What US6743958 introduced is the improving technique of US6358482, and the iso-butylene separated generates n-butene through skeletal isomerization and recycles.WO00014038 describes a kind of method of preparing propylene by butene disproportionation, and raw material butylene is 1-butylene, 2-butylene or its mixture, and catalyzer is WO 3/ SiO 2or Cs +, PO 4 3-deng the WO of modification 3/ SiO 2.When preparing propylene reaction for butylene disproportionation, all there is the problem of poor catalyst stability in the method in above document.
In disproportionation reaction, alkaline earth metal oxide auxiliary agent can produce with disproportionation catalyst and act synergistically, and promotes the carrying out of disproportionation reaction, can also play the impurity in absorption raw material simultaneously, the effect of purification raw material.The report improved about auxiliary agent is had no in above document.Have the report about alkaline earth metal oxide hydration modification in Chinese patent CN200610029981.8, but the stability of modified disproportionation reaction can only reach 360 hours.
Summary of the invention
Technical problem to be solved by this invention is the problem of the poor stability existed in prior art, provides a kind of new butylene disproportionation to prepare the method for propylene.When the method is used for butylene disproportionation reaction, there is the good advantage of stability.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing propylene by butene disproportionation, and with butylene and ethene for raw material, be 200 ~ 450 DEG C in temperature of reaction, reaction pressure is 0 ~ 5MPa(absolute pressure), weight space velocity is 1 ~ 50 hour -1, butylene and ethene weight ratio be under the condition of 1: 0.5 ~ 5, raw material and catalyst exposure react the product generating and comprise propylene, and used catalyst comprises disproportionation catalyst host and the alkaline earth metal oxide auxiliary agent of load tungsten; With host weight parts, host comprises the SiO of a) 85 ~ 95 parts 2or mesopore molecular sieve carrier, and load b thereon) Tungsten oxide 99.999 of 5 ~ 15 parts; The weight ratio of host and auxiliary agent is 1:1 ~ 15; Wherein alkaline earth metal oxide obtains required auxiliary agent through peracid treatment, drying and roasting, and the mol ratio of acid used and alkaline earth metal oxide is 0.1 ~ 5:1.
In technique scheme, the preferable range of temperature of reaction is 200 ~ 400 DEG C, and more preferably scope is 250 ~ 350 DEG C; Reaction pressure is in absolute pressure preferable range for 0.2 ~ 4MPa, and more preferably scope is 0.5 ~ 3MPa; Weight space velocity preferable range is 2 ~ 25 hours -1, more preferably scope is 4 ~ 10 hours -1.
In technique scheme, auxiliary agent treatment condition: acid solution mass concentration is 1 ~ 15%, acid treatment temperature is 20 ~ 100 DEG C, and the acid treatment time is 1 ~ 12 hour; Drying temperature is 60 ~ 120 DEG C, and time of drying is 6 ~ 18 hours; Maturing temperature is 500 ~ 650 DEG C, and roasting time is 3 ~ 10 hours.More preferably scheme is acid solution mass concentration is 3 ~ 10%, and acid treatment temperature is 50 ~ 90 DEG C, and the acid treatment time is 2 ~ 10 hours.The mol ratio preferable range of acid used and alkaline earth metal oxide is 0.5 ~ 3:1,
In technique scheme, the preparation method of disproportionation catalyst host is as follows: the mesoporous supports of aequum and sesbania powder are mixed, add the soluble tungsten salt of aequum after certain hour, after kneading, extrusion, drying, at 450 ~ 650 DEG C, roasting obtains for 2 ~ 8 hours.
Alkaline earth metal oxide and acid solution are had an effect, and generate water-fast alkaline earth salt.High temperature sintering can make alkaline earth salt again dehydration obtain oxide compound.In said process, the Sauerstoffatom of dehydration may be from the Sauerstoffatom in solvent, also may be the Sauerstoffatom from former alkaline earth metal oxide plane of crystal.Therefore, dehydration will cause the surface imperfection of alkaline earth metal oxide, make to there is the positively charged ion of exposure and the negative oxygen ion center of different ligancy on the surface, on limit, angle, cationic omission can form more negative oxygen ion group, alkalescence is improved, and specific surface area also can increase simultaneously, thus is conducive to producing with disproportionation catalyst better acting synergistically, better adsorbing contaminant, thus be conducive to the stability extending reaction.
Adopt technical scheme of the present invention, be 200 ~ 450 DEG C in temperature of reaction, reaction pressure counts 0 ~ 5MPa with absolute pressure, and raw material weight air speed is 1 ~ 50 hour -1condition under, after catalyzer host is mixed with auxiliary agent, with butene feedstock contact reacts, its reaction stability can reach 650 hours, achieve good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
Take 50 grams of commodity MgO, the mass concentration added containing 112.5 grams of oxalic acid is the acid solution of 5%, obtains mixing solutions, after 50 DEG C of heating in water bath stir 5 hours, moisture in suction filtration solution, product is dried 6 hours at 120 DEG C, 500 DEG C of roastings obtain auxiliary agent finished product in 10 hours, are designated as JT-1.
By the mesoporous SiO of load tungsten 8% 2host and JT-1 are with 1: 5(mass ratio) mix, be arranged in the fixed-bed reactor of Φ 25mm, with butylene and ethene for raw material, the two mass ratio is 1: 1, is 4 hours at weight space velocity -1, temperature of reaction is 250 DEG C, and reaction pressure is check and rate catalyst performance under the condition of 1MPa, the results are shown in list 1.
[embodiment 2]
Take 50 grams of commodity MgO, the mass concentration added containing 120.09 grams of citric acids is the solution of 1%, obtains mixing solutions, after 80 DEG C of heating in water bath stir 4 hours, leave standstill 3 hours again, moisture in suction filtration solution, product is 80 DEG C of oven dry, 550 DEG C of roastings obtain auxiliary agent finished product in 8 hours, are designated as JT-2.
By the mesoporous MCM-41 host of load tungsten 5% with JT-2 with 1: 2(mass ratio) mix, be arranged in the fixed-bed reactor of Φ 25mm, with butylene and ethene for raw material, the two mass ratio is 1: 0.5, is 10 hours at weight space velocity -1, temperature of reaction is 300 DEG C, and reaction pressure is check and rate catalyst performance under the condition of 0.5MPa, the results are shown in list 1.
[embodiment 3]
Take 50 grams of commodity CaO, the mass concentration added containing 5.54 grams of carbonic acid is the solution of 10%, obtains mixing solutions, after 90 DEG C of heating in water bath stir 1 hour, leave standstill 3 hours again, moisture in suction filtration solution, product is dried 10 hours at 100 DEG C, 600 DEG C of roastings obtain auxiliary agent finished product in 6 hours, are designated as JT-3.
By the mesoporous MCM-48 host of load tungsten 12% with JT-3 with 1: 10(mass ratio) mix, be arranged in the fixed-bed reactor of Φ 25mm, with butylene and ethene for raw material, the two mass ratio is 1: 2.5, is 25 hours at weight space velocity -1, temperature of reaction is 400 DEG C, and reaction pressure is check and rate catalyst performance under the condition of 3MPa, the results are shown in list 1.
[embodiment 4]
Take 50 grams of commodity BaO, the mass concentration added containing 148.5 grams of oxalic acid is the solution of 15%, obtains mixing solutions, and after stirring 10 hours in 30 DEG C of heating in water bath, moisture in suction filtration solution, product is dried 18 hours at 60 DEG C, and 650 DEG C of roastings are designated as JT-4 in 3 hours.
By the mesoporous SBA-15 host of load tungsten 15% with JT-4 with 1: 15(mass ratio) mix, be arranged in the fixed-bed reactor of Φ 25mm, with butylene and ethene for raw material, the two mass ratio is 1: 5, is 50 hours at weight space velocity -1, temperature of reaction is 450 DEG C, and reaction pressure is check and rate catalyst performance under 5MPa condition, the results are shown in list 1.
[comparative example 1]
By the mesoporous SiO of load tungsten 8% 2host and commodity MgO are with 1: 5(mass ratio) mix, be arranged in the fixed-bed reactor of Φ 25mm, with butylene and ethene for raw material, the two mass ratio is 1: 1, is 4 hours at weight space velocity -1, temperature of reaction is 250 DEG C, and reaction pressure is check and rate catalyst performance under the condition of 1MPa, the results are shown in list 1.
[comparative example 2]
By the mesoporous MCM-48 host of load tungsten 12% with commodity CaO with 1: 10(mass ratio) mix, be arranged in the fixed-bed reactor of Φ 25mm, with butylene and ethene for raw material, the two mass ratio is 1: 2.5, is 25 hours at weight space velocity -1, temperature of reaction is 400 DEG C, and reaction pressure is check and rate catalyst performance under the condition of 3MPa, the results are shown in list 1.
Table 1 catalyst catalytic performance evaluation result
Note: reaction pressure is absolute pressure.
As can be seen from Table 1, under identical reaction conditions, through acid-treated alkaline earth metal oxide auxiliary agent, catalyst stability is significantly improved, 650 hours can be reached, illustrate that preparing propylene for butylene disproportionation reacts, the alkaline earth metal oxide through acidolysis modification is suitable catalyst adjuvant.

Claims (1)

1. the method for a preparing propylene by butene disproportionation, take 50 grams of commodity MgO, the mass concentration added containing 112.5 grams of oxalic acid is the acid solution of 5%, obtain mixing solutions, after 50 DEG C of heating in water bath stir 5 hours, moisture in suction filtration solution, product is dried 6 hours at 120 DEG C, 500 DEG C of roastings obtain auxiliary agent finished product in 10 hours, are designated as JT-1;
By the mesoporous SiO of load tungsten 8% 2host mixes with 1: 5 (mass ratio) with JT-1, is arranged in the fixed-bed reactor of Φ 25mm, and with butylene and ethene for raw material, the two mass ratio is 1: 1, is 4 hours at weight space velocity -1, temperature of reaction is 250 DEG C, and reaction pressure is check and rate catalyst performance under the condition of 1MPa, and the transformation efficiency of result display butylene is 70.1%, and the selectivity of propylene is 99.0%, and stability is 650 hours.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121629A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for preparing propylene by butylene-containing C4 fractioning hydrocarbon dismutation
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
CN101992119A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Catalyst for preparing propylene from butane and ethylene and preparation method thereof
CN102188965A (en) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 Method for preparing catalyst for olefin double bond isomerization

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US20080146856A1 (en) * 2006-12-19 2008-06-19 Leyshon David W Propylene production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101121629A (en) * 2006-08-11 2008-02-13 中国石油化工股份有限公司 Method for preparing propylene by butylene-containing C4 fractioning hydrocarbon dismutation
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
CN101992119A (en) * 2009-08-31 2011-03-30 中国石油化工股份有限公司上海石油化工研究院 Catalyst for preparing propylene from butane and ethylene and preparation method thereof
CN102188965A (en) * 2010-03-03 2011-09-21 中国石油化工股份有限公司 Method for preparing catalyst for olefin double bond isomerization

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