CN102372572B - Method for preparing propylene through C4 disproportionation - Google Patents

Method for preparing propylene through C4 disproportionation Download PDF

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CN102372572B
CN102372572B CN201010261855.1A CN201010261855A CN102372572B CN 102372572 B CN102372572 B CN 102372572B CN 201010261855 A CN201010261855 A CN 201010261855A CN 102372572 B CN102372572 B CN 102372572B
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disproportionation
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propylene
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CN102372572A (en
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宣东
王仰东
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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Abstract

The invention relates to a method for preparing propylene through C4 disproportionation and mainly solves the problems of the past technologies such as the consumption of ethylene and low catalyst activity. In the technical scheme in the method, C4 is used as the raw material and the method comprises the following step: under the conditions that the reaction temperature is 300-520 DEG C, the reaction pressure is 0-2MPa and the weight space velocity is 1-10h<-1>, the raw material passes through a catalyst bed to generate propylene. The catalyst used in the method comprises the following components in parts by weight: 4-30 parts of at least one of tungsten oxide, molybdenum oxide and rhenium oxide and 70-96 parts of SiO2 carrier. By adopting the technical scheme, the problems can be better solved and the method can be used in the propylene industrial production adopting C4 disproportionation.

Description

The method of carbon four disproportionation propylene processed
Technical field
The present invention relates to the method for a kind of carbon four disproportionation propylene processed.
Background technology
In recent years, along with the economic development of third world countries, market will constantly increase the demand of light olefin (comprising ethene, propylene etc.).Propylene is scale inferior to one of most important basic organic of ethene, and its maximum purposes is to produce polypropylene (accounting for the half of its total amount), is secondly to 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 in not reducing naphtha cracking severity 4cut, and can propylene enhancing, thereby the research and development of preparing propylene through olefin disproportionation technology is not only to improving the output of propylene, simultaneously to promoting low value-added C 4the comprehensive utilization of cut all has great significance, and wherein producing propene from butylene by disproportion involved in the present invention is a kind of up-and-coming technique.
Olefin metathesis (Olefin metathesis) is a kind of conversion of olefines process.Under the effect at transition-metal catalyst (as W, Mo, Re etc.), the fracture of the two keys of C=C and formation again in alkene, thus can obtain new olefin product [3].We can represent simply from following reaction formula the dismutation of alkene:
Figure BSA00000242347400011
Figure BSA00000242347400013
r in reaction formula 1, R 2, R 3, R 4represent respectively different alkyl or hydrogen atom.If wherein the disproportionation reaction of same alkene (suc as formula 1) is called self disproportionation (self-metathesis); Disproportionation reaction (formula 2) between different alkene is called cross disproportionation (cross-metathesis).
US5300718 has reported the route by the butene-2 raw material production propylene that contains butene-1 and oxygenatedchemicals.This technique comprises: first raw material is passed through to 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 are used is MgO and WO 3/ SiO 2mixed bed.
WO00014038 has introduced 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, reaction pressure is 1atm.
US513891 has reported 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 has reported and has modified WO with Ti 3/ SiO 2support of the catalyst; US5905055 has reported and has modified WO with Nb 3/ SiO 2support of the catalyst, olefin metathesis activity all obtains raising.
When for butylene or carbon four disproportionation preparation of propene, all there is consumption of ethylene or the low problem of catalyst activity of needing in the method in above document.
Summary of the invention
Technical problem to be solved by this invention be in prior art, exist need consumption of ethylene or the low problem of catalyst activity, a kind of method of new carbon four disproportionation propylene processed is provided.The method when carbon four disproportionation reaction, has advantages of that in the high and product of economic worth, propene yield is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: taking carbon four as raw material, be 300～520 DEG C in temperature of reaction, reaction pressure is 0～2MPa, and weight space velocity is 1～10 hour -1under condition, raw material, by beds, generates propylene, and catalyzer, in parts by weight, comprises following component: a) 4～30 parts of at least one that are selected from Tungsten oxide 99.999, molybdenum oxide or rhenium oxide; B) SiO of 70～96 parts 2carrier.
In technique scheme, preferred raw material is butene-1, the mixture in butene-2 and butane or the C-4-fraction from steam cracking device; The preferable range of temperature of reaction is 320～480 DEG C, and more preferably scope is 360～420 DEG C; Reaction pressure preferable range is 0.1～1MPa, and more preferably scope is 0.2～0.7MPa; Liquid phase air speed preferable range is 5～8 hours -1, more preferably scope is 5.5～7 hours -1; The consumption preferable range of Tungsten oxide 99.999, molybdenum oxide or rhenium oxide is 4～20 parts, and more preferably scope is 8～12 parts; The weight ratio of Tungsten oxide 99.999 and molybdenum oxide is 1: 2～2: 1; The weight ratio of Tungsten oxide 99.999 and rhenium oxide is 1: 2～2: 1.
Disproportionation catalyst in the present invention can adopt the method preparations such as dipping, chemisorption, electroless plating, ion-exchange, physical mixed, preferred version is to add a certain amount of chromatographic silica gel containing in the aqueous solution of active ingredient, wherein active ingredient is at least one in tungsten source, He Lai source, molybdenum source, add 10%～40% silicon sol, stir the field mountain valley with clumps of trees and bamboo powder that adds 0.5%～5% after for some time, mediate, extrusion makes 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.
Tungsten source in the present invention can be the one in wolframic acid, sodium wolframate, ammonium tungstate, ammonium metawolframate, and tungsten source is ammonium metawolframate preferably; Molybdenum source can be the one in molybdic acid, Sodium orthomolybdate, ammonium dimolybdate, ammonium tetramolybdate, Ammonium Heptamolybdate; Rhenium source can be rehenic acid, rehenic acid sodium, rehenic acid ammonium, crosses the one in rehenic acid, ammonium perrhenate.
Catalyzer prepared by technique scheme is for olefin dismutation reaction, and the embodiment of the present invention is that carbon four disproportionations generate propylene.Reaction conditions is as follows: in fixed-bed reactor, and the mixture that consists of butane, alkene-1 and butene-2 of reaction raw materials carbon four, temperature of reaction is 300～520 DEG C, and reaction pressure is 0～1MPa, and the mass space velocity of carbon four is 1～10 o'clock -1.
The present invention, by having reduced reaction raw materials, has reduced the toxic action of impurity to catalyzer in raw material, has regulated the proportioning of active ingredient to improve the yield of product propylene simultaneously.Be 360 DEG C in temperature of reaction, reaction pressure is 0.7MPa, butylene air speed be 7 hours -1under condition, by catalyzer and carbon four contact reactss, the transformation efficiency of its butylene can reach 62%, and the weight yield of propylene can reach 30%, compares yield and improves 7%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
The preparation of disproportionation catalyst: 20 kilograms of chromatographic silica gels and 2 kilograms of field mountain valley with clumps of trees and bamboo powder are put into kneader, after stirring for some time, add active ingredient and 1.5 kilograms of silicon sol of 2.9 kilograms of ammonium metawolframates, add a certain amount of deionized water simultaneously, stir and after 30 minutes, put into banded extruder extrusion and make finished product.In air atmosphere, roasting obtains catalyzer WO after drying 3/ SiO 2, the temperature of roasting is 550 DEG C, and roasting time is 4 hours, and the parts by weight of the active ingredient making are 12 parts.
In fixed-bed reactor, reaction raw materials carbon four consist of 37.5% butane, 5.4% butene-1 and 57.1% butene-2, temperature of reaction is 360 DEG C, reaction pressure is 0.7MPa, the mass space velocity of carbon four is 7 hours -1.The evaluation result of catalyzer is as shown in table 1.
[embodiment 2]
Press each step in embodiment 1, changing active ingredient is the ammonium metawolframate of 1.4 kilograms and the ammonium dimolybdate of 2.1 kilograms, and in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and molybdenum oxide is 1, and the parts by weight of active ingredient are 12 parts, and evaluation result is as shown in table 1.
[embodiment 3]
Press each step in embodiment 1, changing active ingredient is the ammonium metawolframate of 1.4 kilograms and the ammonium perrhenate of 1.2 kilograms, in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and molybdenum oxide is 1, the parts by weight of active ingredient are 12 parts, change temperature of reaction being 480 DEG C is 0.2MPa with reaction pressure, and the mass space velocity of carbon four is 8 hours -1, evaluation result is as shown in table 1.
[embodiment 4]
Press each step in embodiment 1, changing active ingredient is the ammonium metawolframate of 0.64 kilogram and the ammonium dimolybdate of 1.87 kilograms, in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and molybdenum oxide is 1: 2, gross weight umber is 8 parts, change temperature of reaction being 420 DEG C is 0.5MPa with reaction pressure, and the mass space velocity of carbon four is 5.5 hours -1, evaluation result is as shown in table 1.
[embodiment 5]
Press each step in embodiment 1, changing active ingredient is the ammonium metawolframate of 4.8 kilograms and the ammonium dimolybdate of 3.5 kilograms, in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and molybdenum oxide is 2, gross weight umber is 30 parts, change temperature of reaction being 520 DEG C is 0.1MPa with reaction pressure, and the mass space velocity of carbon four is 10 hours -1, evaluation result is as shown in table 1.
[embodiment 6]
Press each step in embodiment 1, changing active ingredient is the ammonium metawolframate of 0.33 kilogram and the ammonium molybdate of 0.54 kilogram, in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and rhenium oxide is 1: 2, gross weight umber is 4 parts, change temperature of reaction being 300 DEG C is 2MPa with reaction pressure, and the mass space velocity of carbon four is 1 hour -1, evaluation result is as shown in table 1.
[embodiment 7]
Press each step in embodiment 1, changing active ingredient is the ammonium metawolframate of 4 kilograms and the ammonium perrhenate of 1.7 kilograms, in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and rhenium oxide is 2, gross weight umber is 20 parts, change temperature of reaction being 400 DEG C is 0.5MPa with reaction pressure, and the mass space velocity of carbon four is 6 hours -1, evaluation result is as shown in table 1.
[comparative example 1]
The preparation of disproportionation catalyst: 20 kilograms of chromatographic silica gels and 2 kilograms of field mountain valley with clumps of trees and bamboo powder are put into kneader, after stirring for some time, add 2.9 kilograms of ammonium metawolframates and 1.5 kilograms of silicon sol, add a certain amount of deionized water simultaneously, stir and after 30 minutes, put into banded extruder extrusion and make finished product.In air atmosphere, roasting obtains catalyzer WO after drying 3/ SiO 2, the temperature of roasting is 550 DEG C, and roasting time is 4 hours, and the parts by weight of the active ingredient making are 12 parts.
In fixed-bed reactor, reaction raw materials is carbon four and ethene, and the mol ratio of carbon four and ethene is 1, carbon four consist of 37.5% butane, 5.4% butene-1 and 57.1% butene-2, temperature of reaction is 360 DEG C, and reaction pressure is 0.7MPa, and the mass space velocity of carbon four is 7 hours -1.The evaluation result of catalyzer is as shown in table 2.
[comparative example 2]
Press each step in comparative example 1, changing active ingredient is the ammonium metawolframate of 4.8 kilograms and the ammonium dimolybdate of 3.5 kilograms, in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and molybdenum oxide is 2, gross weight umber is 30 parts, change temperature of reaction being 520 DEG C is 0.1MPa with reaction pressure, and the mass space velocity of carbon four is 10 hours -1, evaluation result is as shown in table 2.
[comparative example 3]
Press each step in comparative example 1, changing active ingredient is the ammonium metawolframate of 0.33 kilogram and the ammonium molybdate of 0.54 kilogram, in the catalyzer obtaining, the weight ratio of Tungsten oxide 99.999 and rhenium oxide is 1: 2, gross weight umber is 4 parts, change temperature of reaction being 300 DEG C is 2MPa with reaction pressure, and the mass space velocity of carbon four is 1 hour -1, evaluation result is as shown in table 2.
Table 1 reaction conditions is to catalyst activity impact assessment result
Figure BSA00000242347400051
In table 2 reaction raw materials, add the activity rating of catalyst for ethylene
Figure BSA00000242347400052
Comparative example 1～3 in example 1, example 5, example 6 and table 2 in contrast table 1, identical catalyzer is under same appreciation condition, add the yield of the later propylene of a certain amount of ethene to reduce on the contrary, can find out that directly preparing propylene taking carbon four as raw material has better economic worth.

Claims (5)

1. a method for carbon four disproportionation propylene processed, taking carbon four as raw material, is 320～480 DEG C in temperature of reaction, and reaction pressure is 0.1～1MPa, and weight space velocity is 5～8 hours -1under condition, raw material, by beds, generates propylene, and catalyzer, in parts by weight, comprises following component:
A) mixture of 4～30 parts of Tungsten oxide 99.999s and molybdenum oxide, its weight ratio is 1: 2～2: 1;
B) SiO of 70～96 parts 2carrier.
2. the method for a kind of carbon four disproportionation according to claim 1 propylene processed, is characterized in that raw material is butene-1, the mixture in butene-2 and butane or the C-4-fraction from steam cracking device.
3. the method for a kind of carbon four disproportionation according to claim 1 propylene processed, is characterized in that temperature of reaction is 360～420 DEG C, and reaction pressure is 0.2～0.7MPa, and weight space velocity is 5.5～7 hours -1.
4. the method for a kind of carbon four disproportionation according to claim 1 propylene processed, is characterized in that consumption taking parts by weight Tungsten oxide 99.999, molybdenum oxide is as 4～20 parts.
5. the method for a kind of carbon four disproportionation according to claim 4 propylene processed, is characterized in that consumption taking parts by weight Tungsten oxide 99.999, molybdenum oxide is as 8～12 parts.
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CN104109066B (en) * 2013-04-16 2016-06-08 中国石油化工股份有限公司 Method for producing propene from butylene by disproportion
CN104549226B (en) * 2013-10-28 2017-05-10 中国石油化工股份有限公司 Catalyst used for olefin disproportionation
CN104557380B (en) * 2013-10-28 2016-08-17 中国石油化工股份有限公司 The method that extracting carbon four produces propylene
CN105214643B (en) * 2014-07-03 2018-02-13 中国石油化工股份有限公司 Catalyst for metathesis reaction
CN104370676B (en) * 2014-11-11 2016-06-08 中国石油天然气集团公司 A kind of take C 4 olefin as the method for raw material production propylene by-product ethene

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Publication number Priority date Publication date Assignee Title
US3526676A (en) * 1964-11-19 1970-09-01 British Petroleum Co Olefin preparation
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3526676A (en) * 1964-11-19 1970-09-01 British Petroleum Co Olefin preparation
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

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