CN103420755B - Method for propylene preparation through butane disproportionation - Google Patents

Method for propylene preparation through butane disproportionation Download PDF

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CN103420755B
CN103420755B CN201210150313.6A CN201210150313A CN103420755B CN 103420755 B CN103420755 B CN 103420755B CN 201210150313 A CN201210150313 A CN 201210150313A CN 103420755 B CN103420755 B CN 103420755B
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reaction
disproportionation
propylene
butene
parts
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CN103420755A (en
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王仰东
宣东
刘苏
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The present invention relates to a method for propylene preparation through butane disproportionation, wherein the problem of low catalyst activity in the prior art is mainly solved with the present invention. The technical scheme comprises that: 1-butene and 2-butene are adopted as raw materials, and the raw materials and a catalyst are subjected to a contact reaction in a fixed bed reactor at a reaction temperature of 200-450 DEG C under reaction pressure of 0-5 MPa (calculated as absolute pressure) at a butane weight space velocity of 1-10 h<-1> to produce a propylene-containing effluent, wherein the catalyst comprises the following components, by weight, a) 5-50 parts of tungsten oxide, and b) 50-95 parts of a magnesium oxide carrier. With the technical scheme, the problem in the prior art is well solved, and the method can be used for industrial production of propylene preparation through butane disproportionation.

Description

For the method for preparing propylene by butene disproportionation
Technical field
The present invention relates to a kind of method for preparing propylene by butene disproportionation.
Background technology
Propylene is scale inferior to one of most important basic organic of ethene, and its maximum purposes produces polypropylene (accounting for the half of its total amount), is secondly produce vinyl cyanide, propylene oxide, Virahol, isopropyl benzene, oxo-alcohols, vinylformic acid, oligomerization of propene thing.
Traditional ethene coproduction and refinery's Propylene recovery method are obviously difficult to meet growing propylene demand, adopt olefin metathesis technology can digest C while not reducing naphtha cracking severity 4cut, and can propylene enhancing, thus the research and development of preparing propylene through olefin disproportionation technology is not only to the output improving propylene, simultaneously to the low value-added C of promotion 4the comprehensive utilization of cut all has great significance, and butylene disproportionation wherein involved in the present invention is produced third and rarely made a kind of up-and-coming technique.
Olefin dismutation reaction is also called olefinic double bonds replacement(metathesis)reaction, it is a kind of conversion of olefines phenomenon found the sixties in 20th century, olefin dismutation reaction just becomes a class significant process of conversion of olefines since then, utilizes olefin dismutation reaction some comparatively cheap, abundant olefin feedstocks can be converted into the higher olefin product of multiple added value.Olefin dismutation reaction process can be represented with following formula:
Wherein R and R ' represents alkyl or hydrogen atom.The simplest olefin dismutation reaction is that propylene disproportionation generates ethene and butene-2.
US5300718 reports the route by the butene-2 raw material production propylene containing butene-1 and oxygenatedchemicals.This technique comprises: first raw material is passed through alumina removal oxygenatedchemicals; Under the effect that in raw material, butylene is urged at magnesium oxide, isomery turns to butene-2; Butene-2 and ethene disproportionation generate third rare three steps.The catalyzer that wherein butene-2 and ethene disproportionation use is MgO and WO 3/ SiO 2mixed bed.
A kind of technique being obtained the third rare and amylene by butene-1 and butene-2 disproportionation is proposed in US6271430.This technique adopts tank reactor, and catalyzer is Re 2o 7/ Al 2o 3, temperature of reaction is 0 ~ 150 DEG C, and reaction pressure is 2 ~ 200bar.
WO00014038 describes a kind of method of preparing propylene by butene disproportionation.Raw material butylene is butene-1, butene-2 or its mixture, and catalyzer is WO 3/ SiO 2, common temperature of reaction is 500-550 DEG C, and reaction pressure is 1atm.
US513891 reports the preparation method of olefin disproportionation catalyst, and its catalyzer consists of B 2o 3-Re 2o 7/ Al 2o 3/ SiO 2, using amorphous aluminum silicide as support of the catalyst, the activity of olefin dismutation reaction improves greatly.
EP0152112 reports and modifies WO with Ti 3/ SiO 2support of the catalyst; US5905055 reports and modifies WO with Nb 3/ SiO 2support of the catalyst, olefin metathesis activity all obtains raising.
When for preparing propylene by butene disproportionation, all there is the problem that catalyst activity is low in the method in above document.
Summary of the invention
Technical problem to be solved by this invention is the problem that the catalyst activity that exists in prior art is low, provides a kind of method of new preparing propylene by butene disproportionation.When the method is used for butylene disproportionation reaction, there is the advantage that catalyst activity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing propylene by butene disproportionation, with 1-butylene and 2-butylene for raw material, in fixed-bed reactor, temperature of reaction is 200 ~ 450 DEG C, reaction pressure counts 0 ~ 5MPa with absolute pressure, and the weight space velocity of butylene is 1 ~ 10 hour -1, raw material and catalyst exposure reaction generate the effluent containing propylene, and wherein used catalyst is with weight parts, comprises following component: a) Tungsten oxide 99.999 of 5 ~ 50 parts; B) magnesium oxide carrier of 50 ~ 95 parts.
In technique scheme, the preferred version of temperature of reaction is 250 ~ 400 DEG C, more preferably scheme 250 ~ 350 DEG C; Reaction pressure preferred version is 1 ~ 4MPa, and more preferably scheme is 2.5 ~ 3.5MPa; The preferred version of butylene weight space velocity is 2 ~ 8 hours -1, more preferably scheme is 2 ~ 6 hours -1; Be 8 ~ 30 parts with the consumption preferred version of weight parts Tungsten oxide 99.999, more preferably scheme is 10 ~ 20 parts.
Disproportionation catalyst in the present invention can adopt the method such as dipping, chemisorption, electroless plating, ion-exchange, physical mixed to prepare, preferred version is add magnesium oxide carrier in the aqueous solution containing active ingredient, wherein active ingredient is tungsten source, add field mountain valley with clumps of trees and bamboo powder after stirring for some time, kneading, extrusion obtain finished product.In air atmosphere, roasting obtains catalyzer after drying, and the temperature of roasting is 500 ~ 700 DEG C, and roasting time is 2 ~ 8 hours.
In the present invention during tungsten source, can be the one in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, good tungsten source is ammonium metawolframate.
Catalyzer prepared by technique scheme is for olefin dismutation reaction, and the embodiment of the present invention is that butylene and ethene disproportionation reaction generate propylene.Reaction conditions is as follows: in fixed-bed reactor, and temperature of reaction is 200 ~ 450 DEG C, and reaction pressure counts 0 ~ 5MPa with absolute pressure, and the weight space velocity of 1-butylene and 2-butylene is 1 ~ 10 hour -1.
The present invention is by load active component Tungsten oxide 99.999 on magnesium oxide, make catalyzer and existing disproportionation activity, again there is isomerization performance, in reaction process, 1-butylene isomery is turned to 2-butylene by carrier magnesium oxide, disproportionation reaction is then carried out on active ingredient Tungsten oxide 99.999, and relative regular oxidation tungsten catalyst, has better reactive behavior.Use method of the present invention, be 200 ~ 450 DEG C in temperature of reaction, reaction pressure counts 0 ~ 5MPa with absolute pressure, and the weight space velocity of butylene is 1 ~ 10 hour -1condition under, by catalyzer and butylene contact reacts, the transformation efficiency of its butylene can reach 64%, contrast WO 3/ SiO 2the most high energy of the transformation efficiency of its butylene of catalyzer improves 6%, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Take 500 grams of commodity MgO, add 2.5 liters of deionized waters, the white opacity solution obtained is in 80 DEG C of heated and stirred after 5 hours, and moisture in suction filtration solution, product dries 6 hours to obtain magnesium oxide carrier at 120 DEG C.
The carrier magnesium oxide of 200 grams and the sesbania powder of 1% are mixed evenly and put into stirrer, stir and add 19 grams of ammonium metawolframates after 12 minutes, then add 250 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as SL-1.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and calculate by massfraction, raw material is the butene-1 of 60% and the 2-butylene of 40%.Reaction is 300 DEG C in temperature, and pressure counts 3MPa with absolute pressure, and the weight space velocity of butylene is 4.8 hours -1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 2]
Take 500 grams of commodity MgO, add 2 liters of deionized waters, the white opacity solution obtained leaves standstill 2 hours in 60 DEG C of heated and stirred after 4 hours, moisture in suction filtration solution, and product dries 4 hours to obtain magnesium oxide carrier at 120 DEG C.
The carrier magnesium oxide of 200 grams and the sesbania powder of 1% are mixed evenly and put into stirrer, stir and add 24 grams of ammonium metawolframates after 30 minutes, then add 150 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as SL-2.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 350 DEG C in temperature, and pressure counts 2.5MPa with absolute pressure, and the weight space velocity of butylene is 6 hours -1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 3]
Take 500 grams of commodity MgO, add 1.5 liters of deionized waters, the white opacity solution obtained leaves standstill 2 hours in 100 DEG C of heated and stirred after 2 hours, moisture in suction filtration solution, and product dries 8 hours to obtain magnesium oxide carrier at 100 DEG C.
The carrier magnesium oxide of 200 grams and the sesbania powder of 1% are mixed evenly and put into stirrer, stir and add 48 grams of ammonium metawolframates after 20 minutes, then add 180 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as SL-3.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 250 DEG C in temperature, and pressure counts 1MPa with absolute pressure, and the weight space velocity of butylene is 2 hours -1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 4]
By each step in embodiment 1, the content changing active ingredient ammonium metawolframate is 72 grams.Catalyzer is designated as SL-4.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 200 DEG C in temperature, and pressure counts 0.1MPa with absolute pressure, and the weight space velocity of butylene is 1 hour -1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 5]
By each step in embodiment 1, the content changing active ingredient ammonium metawolframate is 12 grams.Catalyzer is designated as SL-5.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 450 DEG C in temperature, and pressure counts 5MPa with absolute pressure, and the weight space velocity of butylene is 10 hours -1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 6]
By each step in embodiment 1, the content changing active ingredient ammonium metawolframate is 120 grams.Catalyzer is designated as SL-6.
The evaluation of catalyzer is carried out on olefin metathesis evaluating apparatus, and reaction is 400 DEG C in temperature, and pressure is 4MPa, and the weight space velocity of butylene is 8 hours -1condition under evaluate, evaluation result is as shown in table 1.
[embodiment 7]
By each step in embodiment 1, the active ingredient added is 19 grams of ammonium metawolframates and 5 grams of ammonium molybdates.Catalyzer is designated as SL-7.
Appreciation condition is identical with embodiment 1, and evaluation result is as shown in table 1.
[comparative example 1]
The sesbania powder of the Support Silica of 200 grams and 1% is mixed evenly and puts into stirrer, stirs and add 19 grams of ammonium metawolframates after 12 minutes, then add 250 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as BJL-1.
Appreciation condition is with example 1, and evaluation result is as shown in table 2.
[comparative example 2]
The sesbania powder of the Support Silica of 200 grams and 1% is mixed evenly and puts into stirrer, stirs and add 24 grams of ammonium metawolframates after 30 minutes, then add 150 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be denoted as BJL-2.
Appreciation condition is with example 2, and evaluation result is as shown in table 2.
[comparative example 3]
The sesbania powder of the Support Silica of 200 grams and 1% is mixed evenly and puts into stirrer, stirs and add 48 grams of ammonium metawolframates after 20 minutes, then add 180 grams of deionized waters, after kneading, extrusion, drying at 550 DEG C roasting 4 hours obtained catalyzer, be designated as BJL-3.
Appreciation condition is with example 3, and evaluation result is as shown in table 2.
Table 1
Table 2

Claims (4)

1., for a method for preparing propylene by butene disproportionation, with 1-butylene and 2-butylene for raw material, in fixed-bed reactor, temperature of reaction is 250 ~ 400 DEG C, and reaction pressure counts 1 ~ 4MPa with absolute pressure, and weight space velocity is 2 ~ 8 hours -1condition under, raw material and catalyst exposure reaction generate containing the effluent of propylene, and wherein used catalyst is with weight parts, composed of the following components: a) Tungsten oxide 99.999 of 5 ~ 50 parts; B) magnesium oxide carrier of 50 ~ 95 parts.
2. the method for preparing propylene by butene disproportionation according to claim 1, it is characterized in that temperature of reaction is 250 ~ 350 DEG C, reaction pressure counts 2.5 ~ 3.5MPa with absolute pressure, and weight space velocity is 2 ~ 6 hours -1.
3. the method for preparing propylene by butene disproportionation according to claim 1, is characterized in that catalyzer is 8 ~ 30 parts with the consumption of weight parts Tungsten oxide 99.999.
4. the method for preparing propylene by butene disproportionation according to claim 3, is characterized in that catalyzer is 10 ~ 20 parts with the consumption of weight parts Tungsten oxide 99.999.
CN201210150313.6A 2012-05-16 2012-05-16 Method for propylene preparation through butane disproportionation Active CN103420755B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1490289A (en) * 2002-10-16 2004-04-21 中国石油化工股份有限公司 Method for preparing propylene by butene disproportionation
CN1639091A (en) * 2002-03-07 2005-07-13 Abb拉默斯环球有限公司 Process for producing propylene and hexene from C4 olefin streams
CN1277608C (en) * 2002-10-16 2006-10-04 中国石油化工股份有限公司 Fixed bed catalyst for producing propene from butylene by disproportion

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8704029B2 (en) * 2010-03-30 2014-04-22 Uop Llc Conversion of butylene to propylene under olefin metathesis conditions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1639091A (en) * 2002-03-07 2005-07-13 Abb拉默斯环球有限公司 Process for producing propylene and hexene from C4 olefin streams
CN1490289A (en) * 2002-10-16 2004-04-21 中国石油化工股份有限公司 Method for preparing propylene by butene disproportionation
CN1277608C (en) * 2002-10-16 2006-10-04 中国石油化工股份有限公司 Fixed bed catalyst for producing propene from butylene by disproportion

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