CN103030513A - Method for preparing hexene by butylene disproportionation reaction - Google Patents
Method for preparing hexene by butylene disproportionation reaction Download PDFInfo
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- CN103030513A CN103030513A CN2011103006190A CN201110300619A CN103030513A CN 103030513 A CN103030513 A CN 103030513A CN 2011103006190 A CN2011103006190 A CN 2011103006190A CN 201110300619 A CN201110300619 A CN 201110300619A CN 103030513 A CN103030513 A CN 103030513A
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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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- 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 invention relates to a method for preparing hexene by butylene disproportionation reaction, which mainly solves the problem of high reaction temperature in the prior art. Aiming at well solving the problem, the method adopts the technical scheme that 1-butylene is used as a raw material, and the raw material comes into contact with a catalyst to react and generate an effluent containing the hexene in a fixed bed reactor when the temperature is 20 to 120 DEG C, the reaction pressure is 0 to 1 MPa by the absolute pressure, and the weight hourly space velocity is 6 to 20 h<-1>, wherein the catalyst comprises the following raw materials in parts by weight: 1 to 30 parts of rhenium oxide and 70 to 99 parts of alumina carrier. The method can be used for the industrial production of the hexene prepared by the butylene disproportionation reaction.
Description
Technical field
The present invention relates to a kind of method for preparing hexane by disproportionating butylene.
Background technology
As a kind of olefin product of high added value, the synthetic of hexene paid attention to very much.The conventional preparation method of present industrial hexene generates the 1-hexene by ethylene polymerization, and the catalyzer of employing is alkylating metal catalyst.By the olefin metathesis technology, C4 conversion of olefines that can relative surplus is low value-added becomes hexene and the ethene of high added value.
Olefin metathesis (Olefin metathesis) is a kind of conversion of olefines process.By under the effect of transition-metal catalyst (such as W, Mo, Re etc.), the fracture of the two keys of C=C and again formation in the alkene, thus can obtain new olefin product.We can represent simply from following reaction formula the dismutation of alkene:
The control of self disproportionation reaction of 1-butylene is the most key, because the 1-butylene double bond isomerization reaction generates 2-butylene, and 1-butylene and 2-butylene cross disproportionation cause hexene optionally to reduce, so the key of this technology is to suppress in the raw material 1-butylene at the double-bond isomerization of catalyst surface.
WO02059066 has reported the automatic disproportionation technology of 1-butylene.The catalyzer that this technology adopts is that Tungsten oxide 99.999 loads on the silicon oxide, and under 200 ℃～350 ℃ temperature, 1-butylene self disproportionation generates ethene and 3-hexene.The 3-hexene is converted into the 1-hexene in isomerization reaction subsequently.This patent points out, adds the 2-amylene in the reactant and is conducive to that the 3-hexene optionally improves in the product.
WO03076371A1 has reported the technology for preparing propylene and hexene take butylene as raw material.The catalyzer that this technology adopts is that Tungsten oxide 99.999 loads on the silicon oxide, and temperature of reaction is 343 ℃, and reaction pressure is 5bar.
All there is the high problem of temperature of reaction in method in the above document when being used for the reaction of preparing hexane by disproportionating butylene.
Summary of the invention
Technical problem to be solved by this invention is the high problem of temperature of reaction that exists in the prior art, and a kind of method of new preparing hexane by disproportionating butylene is provided.When the method is used for the butylene disproportionation reaction, have advantages of that catalyst activity is high, temperature of reaction is low.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing hexane by disproportionating butylene take 1-butylene as raw material, is 20～120 ℃ in temperature of reaction, and reaction pressure is counted 0～1MPa with absolute pressure, and weight space velocity is 6～20 hours
-1Under the condition, raw material generates hexene by beds, and wherein catalyst system therefor comprises following component in parts by weight:
A) 1～30 part of rhenium oxide;
B) 70～99 parts of alumina supporters.
In the technique scheme, the preferable range of temperature of reaction is 30～100 ℃, and more preferably scope is 40～80 ℃; The reaction pressure preferable range is 0.2～0.8MPa, and more preferably scope is 0.4～0.6MPa; Liquid phase air speed preferable range is 8～16 hours
-1, more preferably scope is 10～16 hours
-1The preferable range of rhenium oxide consumption parts by weight is 2～25 parts, and more preferably scope is 4～20 parts, and most preferred range is 8～15 parts; The carrier of catalyzer is preferably γ-Al
2O
3
Catalyzer of the present invention can adopt dipping, chemisorption, electroless plating, ion-exchange, the preparation of the methods such as physical mixed, the rhenium source can be perrhenic acid or rhenate among the present invention, the rhenium source is ammonium perrhenate preferably, preferred version is that the aqueous solution in rhenium-containing source is immersed on the carrier, concrete scheme is for to put into stirrer with the aqueous solution and the carrier in rhenium-containing source, and adding aluminium colloidal sol and sesbania powder, stir to mediate and make it to put into banded extruder behind the Load Balanced, it is dry after the definite shape that extrusion becomes, under air atmosphere, make finished product after the roasting, the temperature of roasting is 500～700 ℃, and roasting time is 2～8 hours.
The catalyzer of technique scheme preparation is used for the automatic disproportionation reaction of alkene, and the embodiment of the invention is that butylene disproportionation generates hexene.Reaction conditions is as follows: in the fixed-bed reactor, temperature of reaction is 20～120 ℃, and reaction pressure is counted 0～1MPa with absolute pressure, and the mass space velocity of 1-butylene is 6～20 hours
-1
The present invention adopts rhenium oxide as active ingredient, makes catalyzer have at low temperatures good disproportionation active.Be 20～120 ℃ in temperature of reaction, reaction pressure is counted 0～1MPa with absolute pressure, and the mass space velocity of 1-butylene is 6～20 hours
-1Under the condition, with catalyzer and butylene contact reacts, the transformation efficiency of its 1-butylene can reach 60%, and the weight yield of hexene can reach 26%, and yield can improve and reaches about 6%, has obtained preferably technique effect.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 1 kilogram of γ-Al
2O
3With stirring in the 10 gram sesbania powder adding stirrers 45 minutes, add 400 gram aluminium colloidal sols and 36 gram ammonium perrhenates after mediating evenly, add simultaneously 1 kilogram deionized water, kneading, extrusion, drying, later on 550 ℃ of lower roastings 4 hours, obtain the catalyzer finished product, the content 4% of rhenium oxide.The evaluation of catalyzer is carried out at the olefin metathesis evaluating apparatus, and raw material is that weight content is 99.9% 1-butylene.Reaction is to be 40 ℃ in temperature, and pressure is 0.5MPa, and the weight space velocity of 1-butylene is 8 hours
-1Condition under estimate, evaluation result is as shown in table 1, is designated as SL-1.
[embodiment 2]
Press each step among the embodiment 1, only change ammonium perrhenate and be 72 grams, the charge capacity of the catalyst oxidation rhenium that makes is 8%, and changing in the reaction conditions temperature of reaction and be 80 ℃, reaction pressure is that 0.2MPa and weight space velocity are 10 hours
-1, evaluation result is as shown in table 1, is designated as SL-2.
[embodiment 3]
Press each step among the embodiment 1, only change ammonium perrhenate and be 108 grams, the charge capacity of the catalyst oxidation rhenium that makes is 12%, and changing in the reaction conditions temperature of reaction and be 100 ℃, reaction pressure is that 0.4MPa and weight space velocity are 16 hours
-1, evaluation result is as shown in table 1, is designated as SL-3.
[embodiment 4]
Press each step among the embodiment 1, only change ammonium perrhenate and be 135 grams, the charge capacity of the catalyst oxidation rhenium that makes is 15%, and changing in the reaction conditions temperature of reaction and be 30 ℃, reaction pressure is that 1MPa and weight space velocity are 20 hours
-1, evaluation result is as shown in table 1, is designated as SL-4.
[embodiment 5]
Press each step among the embodiment 1, only change ammonium perrhenate and be 181 grams, the charge capacity of the catalyst oxidation rhenium that makes is 20%, and changing in the reaction conditions temperature of reaction and be 120 ℃, reaction pressure is that 0.8MPa and air speed are 12 hours
-1, evaluation result is as shown in table 1, is designated as SL-5.
[embodiment 6]
Press each step among the embodiment 1, only change ammonium perrhenate and be 18 grams, the charge capacity of the catalyst oxidation rhenium that makes is 2%, and changing in the reaction conditions temperature of reaction and be 20 ℃, reaction pressure is that 0.6MPa and weight space velocity are 6 hours
-1, evaluation result is as shown in table 1, is designated as SL-6.
[embodiment 7]
Press each step among the embodiment 1, only change ammonium perrhenate and be 9 grams, the charge capacity of the catalyst oxidation rhenium that makes is 1%, and changing in the reaction conditions temperature of reaction and be 35 ℃, reaction pressure is that 0.7MPa and weight space velocity are 15 hours
-1Evaluation result is as shown in table 1, is designated as SL-7.
[embodiment 8]
Press each step among the embodiment 1, only changing ammonium perrhenate is 225 grams, and the charge capacity of the catalyst oxidation rhenium that makes is 25%, and changing reaction pressure is that 0.1MPa and weight space velocity are 12 hours
-1, evaluation result is as shown in table 1, is designated as SL-8.
[embodiment 9]
Press each step among the embodiment 1, only changing ammonium perrhenate is 271 grams, and the charge capacity of the catalyst oxidation rhenium that makes is 30%, and the weight space velocity that changes iso-butylene is 18 hours
-1, evaluation result is as shown in table 1, is designated as SL-9.
[embodiment 10]
With 1 kilogram of γ-Al
2O
3With stirring in the 10 gram sesbania powder adding stirrers 45 minutes, add 400 gram aluminium colloidal sols, 36 gram ammonium perrhenates and 2 gram ammonium dimolybdates after mediating evenly, the deionized water that adds simultaneously 1 kilogram, kneading, extrusion, drying, later on 550 ℃ of lower roastings 4 hours, obtain the catalyzer finished product, the content 4% of rhenium oxide.Appreciation condition is identical with embodiment 1, and evaluation result is as shown in table 1, is designated as SL-10.
[comparative example 1]
1 kilogram of 200 purpose chromatographic silica gel and 10 gram sesbania powder are added in the stirrers stirred 45 minutes, add 400 gram silicon sol and 55 gram ammonium metawolframates after mediating evenly, the deionized water that adds simultaneously 1 kilogram, kneading, extrusion, drying, later on 550 ℃ of lower roastings 4 hours, obtain flaxen catalyzer finished product, the content 4% of Tungsten oxide 99.999 is designated as BJL-1.The evaluation of catalyzer is carried out at the olefin metathesis evaluating apparatus, and raw material is the 1-butylene of weight content 99.9%.Reaction is to be 350 ℃ in temperature, and pressure is 0.5MPa, and the weight space velocity of 1-butylene is 8 hours
-1Condition under estimate, evaluation result is as shown in table 2.
[comparative example 2]
Press each step Kaolinite Preparation of Catalyst in the comparative example 1, the add-on that changes ammonium metawolframate is 110 grams, and the content of Tungsten oxide 99.999 is 8%, is designated as BJL-2.Changing in the reaction conditions temperature of reaction and be 300 ℃, reaction pressure is 0.2MPa, and the weight space velocity of 1-butylene is 10 hours
-1, evaluation result is as shown in table 2.
[comparative example 3]
Press each step Kaolinite Preparation of Catalyst in the comparative example 1, the add-on that changes ammonium metawolframate is 165 grams, and the content of Tungsten oxide 99.999 is 12% to be designated as BJL-3.Changing in the reaction conditions temperature of reaction and be 100 ℃, reaction pressure is 0.4MPa, and the weight space velocity of 1-butylene is 16 hours
-1Evaluation result is as shown in table 3.
Table 1
Table 2
Example and comparative example in the his-and-hers watches 2 compare, and rhenium oxide has preferably disproportionation activity at low temperature, under identical reaction conditions, compares the comparative example catalyzer, and the yield of hexene improves more than 6%.
Claims (7)
1. the method for a preparing hexane by disproportionating butylene take 1-butylene as raw material, is 20～120 ℃ in temperature of reaction, and reaction pressure is counted 0～1MPa with absolute pressure, and weight space velocity is 6～20 hours
-1Under the condition, raw material generates hexene by beds, and wherein catalyst system therefor comprises following component in parts by weight:
A) 1～30 part of rhenium oxide;
B) 70～99 parts of alumina supporters.
2. the method for preparing hexane by disproportionating butylene according to claim 1 is characterized in that temperature of reaction is 30～100 ℃, and reaction pressure is counted 0.2～0.8MPa with absolute pressure, and weight space velocity is 8～16 hours
-1
3. the method for preparing hexane by disproportionating butylene according to claim 2 is characterized in that temperature of reaction is 40～80 ℃, and reaction pressure is 0.4～0.6MPa, and weight space velocity is 10～16 hours
-1
4. the method for preparing hexane by disproportionating butylene according to claim 1 is characterized in that take parts by weight rhenium oxide consumption as 2～25 parts.
5. the method for preparing hexane by disproportionating butylene according to claim 4 is characterized in that take parts by weight rhenium oxide consumption as 4～20 parts.
6. the method for preparing hexane by disproportionating butylene according to claim 1 is characterized in that take parts by weight rhenium oxide consumption as 8～15 parts.
7. the method for preparing hexane by disproportionating butylene according to claim 1, the carrier that it is characterized in that catalyzer is γ-Al
2O
3
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| CN201110300619.0A CN103030513B (en) | 2011-09-29 | 2011-09-29 | Method for preparing hexene by butylene disproportionation reaction |
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| CN201110300619.0A CN103030513B (en) | 2011-09-29 | 2011-09-29 | Method for preparing hexene by butylene disproportionation reaction |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108080021A (en) * | 2017-12-18 | 2018-05-29 | 陕西省石油化工研究设计院 | It is a kind of to be used for oligomeric catalyst for preparing 1- hexenes of butylene disproportionation and its preparation method and application |
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| US20020183572A1 (en) * | 2001-01-25 | 2002-12-05 | Gartside Robert J. | Process for the production of linear alpha olefins and ethylene |
| CN1915938A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for producing ethene and hexene through dismutation of butylene |
| CN101148391A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for producing propylene by butylene and ethylene dismutation |
| EP2157071A2 (en) * | 2002-03-07 | 2010-02-24 | Lummus Technology Inc. | Process for producing propylene and hexene from C4 olefin streams |
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2011
- 2011-09-29 CN CN201110300619.0A patent/CN103030513B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020183572A1 (en) * | 2001-01-25 | 2002-12-05 | Gartside Robert J. | Process for the production of linear alpha olefins and ethylene |
| EP2157071A2 (en) * | 2002-03-07 | 2010-02-24 | Lummus Technology Inc. | Process for producing propylene and hexene from C4 olefin streams |
| CN1915938A (en) * | 2005-08-15 | 2007-02-21 | 中国石油化工股份有限公司 | Method for producing ethene and hexene through dismutation of butylene |
| CN101148391A (en) * | 2006-09-20 | 2008-03-26 | 中国石油化工股份有限公司 | Method for producing propylene by butylene and ethylene dismutation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108080021A (en) * | 2017-12-18 | 2018-05-29 | 陕西省石油化工研究设计院 | It is a kind of to be used for oligomeric catalyst for preparing 1- hexenes of butylene disproportionation and its preparation method and application |
| CN108080021B (en) * | 2017-12-18 | 2020-11-17 | 陕西省石油化工研究设计院 | Catalyst for preparing 1-hexene through butene disproportionation and oligomerization, and preparation method and application thereof |
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