CN1151883C - Catalyst for disproportionation reaction of ethylene and butene to prepare propylene and its prepn - Google Patents
Catalyst for disproportionation reaction of ethylene and butene to prepare propylene and its prepn Download PDFInfo
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- CN1151883C CN1151883C CNB011308656A CN01130865A CN1151883C CN 1151883 C CN1151883 C CN 1151883C CN B011308656 A CNB011308656 A CN B011308656A CN 01130865 A CN01130865 A CN 01130865A CN 1151883 C CN1151883 C CN 1151883C
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- catalyst
- reaction
- butene
- preparing propylene
- carrier
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Abstract
The present invention relates to a catalyst used for preparing propylene by a disproportionation reaction of ethylene and butene. The present invention comprises A-R/D. An as an active component is one kind of tungsten oxide compounds, molybdenum oxide compounds or rhenium oxide compounds, or several kinds of the tungsten oxide compounds, the molybdenum oxide compounds or the rhenium oxide compounds, and the weight carrying capacity of A is equal to 0.5 to 20%. R as an auxiliary agent is alkali metal or alkali metal elements, and the weight carrying capacity of D is equal to 0.05 to 10%. D as a carrier is a mixture, a main component of D is a molecular sieve (which mainly comprises Y, beta, SAPO series, ZSM series and MCM series, the weight content of the molecular sieve is greater than or equal to 50%), other components are one kind of aluminum oxide, silicon oxide, clay, etc., or several kinds of the aluminum oxide, the silicon oxide, the clay, etc. The catalyst is used in a reaction for preparing propylene by disproportionation of ethylene and butene. The reaction can be carried out in a reactor, such as fixed beds, fluidized beds, slurry beds, etc. The catalyst provided by the present invention is used in the reaction for preparing propylene by disproportionation of ethylene and butene, and the catalyst has the characteristics of high selectivity, high conversion rate and high stability.
Description
Technical field
The present invention relates to a kind of being used for by ethene and preparing propylene by butene disproportionation catalyst for reaction, use catalyst provided by the invention can high conversion, high selectivity and high stability ground produces propylene.
Background technology
Propylene is one of important foundation raw material of development petrochemical industry, also is the petrochemical industry product that demand growth is the fastest in the world, and world's propylene demand from 1,800 ten thousand tons of nearly 5,000 ten thousand tons of increasing to 2000 in 1980, expects 2010 and will reach 75,000,000 tons.It with ethene and butene reaction system propylene one of method that increases propone output, because supply exceed demand for butylene at present, especially the butene-2 shortage is effectively utilized approach, so suit measures to local conditions to adopt this course of reaction can reasonably regulate the product layout of ethene, propylene and butylene.There is part to contain the crude ethylene of methane, ethane and small quantity of hydrogen in addition in the product of heavy oil catalytic pyrolysis, itself and butene reaction are made propylene, both can improve the output of propylene, and can reduce the energy consumption of cryogenic separation again, and this course of reaction is more favourable than propylene disproportionation as can be known by calculation of thermodynamics.This is a process with practicality and novelty, and it is succeeded in developing and can produce remarkable economic efficiency and social benefit.
United States Patent (USP) (USP5,877,365) has been reported C
4Cut is converted into polyisobutene and propylene process.This process comprises following three steps: (1) butene-1 tautomerizes to butene-2; (2) isobutene polymerisation becomes polyisobutene; (3) butene-2 and ethene disproportionation system propylene.Butene-2 and ethene disproportionation system propylene catalyst system therefor are the oxide carried on mixed oxide of rhenium (0.01-20wt%), this mixed oxide comprises at least 75% aluminium oxide, other is a sieve and silica-sesquioxide, one or both in the oxide of molecular sieve and 0.01-30% niobium and tantalum.Reaction temperature is between 0-200 ℃, and pressure is higher than the saturated vapor pressure of gaseous mixture under the respective reaction temperature.
United States Patent (USP) (USP5,120,894) reported the catalyst of ethene and preparing propylene by butene disproportionation, this catalyst is that Mo, W and Re are compound loaded on carriers such as aluminium oxide, silica, alkali metal oxide and alkaline earth oxide, but above-mentioned catalyst is used for the reaction by ethene and butylene system propylene, and its activity of such catalysts is lower and selectivity is relatively poor.
Chinese patent (application number is 01104355.5) has been reported the catalyst of ethene and preparing propylene by butene disproportionation, and this catalyst is that Mo. W and Re are compound loaded on molecular sieve carrier, and molecular sieve comprises Y, β, SAPO series, ZSM series and MCM series.Be reflected in fixed bed or the fluidized-bed reactor and carry out, reaction temperature 0-300 ℃; Weight space velocity: 0.01-3h
-1C in the reactor feed gas
2H
4/ C
4H
8-2 ratios: 0.2～4; Reaction pressure: 0.1-2.0MPa.
Summary of the invention
The purpose of this invention is to provide a kind of being used for by ethene and preparing propylene by butene disproportionation catalyst for reaction and this Preparation of catalysts method, use catalyst provided by the invention can high conversion, high selectivity and high stability ground produces propylene.
The invention provides a kind of being used for by ethene and preparing propylene by butene disproportionation catalyst for reaction, it consists of A-R/D, and active constituent A is one or more in the oxide of tungsten, molybdenum and rhenium, and its weight content is 0.5-20%; Auxiliary agent R is alkali metal Li, Na or K or alkali earth metal Be, Mg, Ca, Ba or Sr, and its weight content is 0.05-10%; Carrier D is the mixture of molecular sieve and inertia component, molecular sieve mainly comprises Y, β, SAPO series, ZSM series or MCM series, the inertia component comprises aluminium oxide, one or more in silica and the clay, and molecular sieve content is more than or equal to 50% of vehicle weight.
Catalyst provided by the present invention, its preparation method is: the mixture carrier that at first prepares the certain granules degree with conventional method, with the solution impregnation aforementioned particles that contains soluble alkali metal or alkali earth metal, dry and in 400-800 ℃ of roasting, use the solution impregnation aforementioned particles of molybdenum, tungsten or the rhenium element of solubility then, dry and in 400-800 ℃ of roasting, can also change above-mentioned impregnation sequence and repeat above-mentioned impregnation steps arbitrarily.The solution of described soluble metal element can be with solubility salts such as metallic nitrate, acetate or this metal acid ammoniums.
Catalyst of the present invention is used for ethene and preparing propylene by butene disproportionation reaction time spent, and reaction condition is: temperature 0-300 ℃; Pressure: 0.1-3.0MPa; Butylene weight space velocity: 0.01-3h
-1Ethylene/butylene ratio in the reactor feed gas: 0.2～10.
Catalyst of the present invention is used for ethene and preparing propylene by butene disproportionation reaction time spent, course of reaction is: contain butene-1, butene-2, normal butane, iso-butane, the unstripped gas of the butylene of gas such as methane, ethane at first tautomerizes to butene-2 (butene-1 tautomerizes to the conversion ratio of butene-2 greater than 70%) by isomerization catalyst with butene-1 wherein, enters with ethene then and carries out disproportionated reaction in the reactor that contains above-mentioned disproportionation catalyst.
Description of drawings
Fig. 1 be the different catalysts reactivity over time.
The specific embodiment
Below in conjunction with embodiment the present invention is further elaborated, but the present invention is not produced any restriction.
Embodiment 1
H-70 β-the 30Al that has the certain granules degree with the conventional method preparation
2O
3Carrier (H represents that molecular sieve is the H type, and the percentage by weight of 70 and 30 expression molecular sieves and other components is respectively 70 and 30, and following method for expressing is similar, no longer explanation).Get 10 gram H-70 β-30Al
2O
3Carrier is with Mg (NO
3)
2Solution carries out vacuum impregnation to it, particle behind the dipping was through 100 ℃ of oven dry and 550 ℃ of roastings 3 hours, the gained calcining matter carries out vacuum impregnation with ammonium molybdate solution, then through 110 ℃ of oven dry and 550 ℃ of roastings 3 hours, make required catalyst A, wherein the weight content of Mg and Mo is respectively 2% and 6%.
Embodiment 2
The H-80MCM-22-20SiO that has the certain granules degree with the conventional method preparation
2Carrier.Get 10 gram H-80MCM-22-20SiO
2Carrier is with K (NO
3) solution carries out vacuum impregnation to it, particle behind the dipping was through 120 ℃ of oven dry and 600 ℃ of roastings 3 hours, the gained calcining matter carries out vacuum impregnation with ammonium molybdate solution, then through 120 ℃ of oven dry and 600 ℃ of roastings 3 hours, make required catalyst B, wherein the weight content of K and Mo is respectively 1% and 8%.
Embodiment 3
Has the H-70ZSM-35-30 clay carrier of certain granules degree with the conventional method preparation.Get 10 gram H-70ZSM-35-30 clay carrier with Ca (NO
3)
2Solution carries out vacuum impregnation to it, and the particle behind the dipping was through 100 ℃ of oven dry and 650 ℃ of roastings 3 hours, and the gained calcining matter carries out vacuum impregnation with ammonium tungstate solution; Through 110 ℃ of oven dry and 650 ℃ of roastings 3 hours, make required catalyst C then, wherein the weight content of Ca and W is respectively 3% and 8%.
Embodiment 4
The H-70Beta-30Al that has the certain granules degree with the conventional method preparation
2O
3Carrier.Get 10 gram H-70 β-30Al
2O
3Carrier carries out vacuum impregnation with ammonium molybdate solution to it, and the particle behind the dipping was through 100 ℃ of oven dry and 550 ℃ of roastings 3 hours, and the gained calcining matter is with Ba (NO
3)
2Solution carries out vacuum impregnation, through 110 ℃ of oven dry and 550 ℃ of roastings 3 hours, makes required catalyst D then, and wherein the weight content of Ba and Mo is respectively 2% and 6%.
Comparative example 1
The H-70Beta-30Al that has the certain granules degree with the conventional method preparation
2O
3Carrier.Get 10 gram H-70Beta-30Al
2O
3Carrier carries out vacuum impregnation with ammonium molybdate solution to it, and the particle behind the dipping makes required catalyst E through 100 ℃ of oven dry and 550 ℃ of roastings 3 hours, and wherein the weight content of Mo is 6%.
Embodiment 5
Is in the stainless steel fixed bed reactors of 10mm, at N with 5g according to the catalyst of the embodiment method preparation internal diameter of packing into
2Atmosphere in be warmed up to 550 ℃, preliminary treatment 1 hour is then at N
2Atmosphere drop to 125 ℃.With nitrogen reacting system pressure is raised to 1.0MPa, switching nitrogen is ethene and butylene gaseous mixture, and at first by isomerization reaction zone, the butene-1 about 70% changes into butene-2 to gaseous mixture, enters the disproportionated reaction district then and carries out disproportionated reaction.A, B, C, D, the reactivity of five kinds of catalyst of E rule is over time seen Fig. 1.As can be seen from Fig. 1, the catalyst that adds alkali metal and/or alkaline-earth metal has improved the stability of catalyst on the basis that guarantees catalyst activity.
Claims (6)
1. catalyst that is used for by ethene and preparing propylene by butene disproportionation, it is characterized in that: catalyst consists of A-R/D, and active constituent A is one or more in the oxide of tungsten, molybdenum or rhenium, and its weight content is 0.5-20%; Auxiliary agent R is alkali metal Li, Na or K or alkali earth metal Be, Mg, Ca, Sr or Ba, and its weight content is 0.05-10%; Carrier D is a mixture carrier, and wherein main component is a molecular sieve, and other component is one or more in aluminium oxide, silica and the clay.
2. by described ethene and the preparing propylene by butene disproportionation catalyst for reaction of being used for of claim 1, it is characterized in that: active constituent A weight content is 1-15%.
3. by described ethene and the preparing propylene by butene disproportionation catalyst for reaction of being used for of claim 1, it is characterized in that: auxiliary agent R weight content is 0.1-8%.
4. by described ethene and the preparing propylene by butene disproportionation catalyst for reaction of being used for of claim 1, it is characterized in that: molecular sieve is Y, β, SAPO series, ZSM series or MCM series among the carrier D, and its weight content is more than or equal to 50% of carrier D.
5. a preparation method who is used for ethene and preparing propylene by butene disproportionation catalyst for reaction is: at first prepare mixture carrier, with the solution impregnation that contains soluble alkali metal or alkali earth metal aforementioned particles is provided, dry and in 400-800 ℃ of roasting, then with containing the solution impregnation aforementioned particles of soluble molybdenum, tungsten or rhenium element, dry and in 400-800 ℃ of roasting 2-4 hour.
6. according to by the described preparation method of claim 5, the described solution that contains soluble alkali metal, alkaline-earth metal, molybdenum, tungsten or rhenium is the ammonium salt of the nitrate, acetate or this metal acid that contain this metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011308656A CN1151883C (en) | 2001-08-29 | 2001-08-29 | Catalyst for disproportionation reaction of ethylene and butene to prepare propylene and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011308656A CN1151883C (en) | 2001-08-29 | 2001-08-29 | Catalyst for disproportionation reaction of ethylene and butene to prepare propylene and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403198A CN1403198A (en) | 2003-03-19 |
| CN1151883C true CN1151883C (en) | 2004-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011308656A Expired - Fee Related CN1151883C (en) | 2001-08-29 | 2001-08-29 | Catalyst for disproportionation reaction of ethylene and butene to prepare propylene and its prepn |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CZ297691B6 (en) * | 2003-05-05 | 2007-03-07 | Ústav fyzikální chemie J. Heyrovského AV CR, v.v.i. | Mesoporous catalyst of olefin metathesis and process for preparing thereof |
| CN1314486C (en) * | 2003-11-19 | 2007-05-09 | 中国石油化工股份有限公司 | Catalyst for disproportionation of butylene to produce propylene |
| CN1326817C (en) * | 2004-07-13 | 2007-07-18 | 中国科学院大连化学物理研究所 | Process for preparing propylene by assimilation of ethylene and butylene on moving bed |
| CN101165024B (en) * | 2006-10-20 | 2010-06-16 | 中国石油化工股份有限公司 | Method for increasing selectivity and yield of propylene |
| CN101190869B (en) * | 2006-11-21 | 2010-10-06 | 中国石油化工股份有限公司 | Production increasing method for propylene |
| CN101992119B (en) * | 2009-08-31 | 2013-04-03 | 中国石油化工股份有限公司 | Catalyst for preparing propylene from butane and ethylene and preparation method thereof |
| EP2786978B1 (en) * | 2013-04-03 | 2016-12-07 | Scg Chemicals Co. Ltd. | Process for converting paraffin to olefin and catalyst for use therein |
| 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 |
| CN108059580B (en) * | 2016-11-09 | 2020-01-14 | 中国科学院大连化学物理研究所 | Catalyst for preparing hexene/ethylene by self-disproportionation of 1-butene and preparation method thereof |
-
2001
- 2001-08-29 CN CNB011308656A patent/CN1151883C/en not_active Expired - Fee Related
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