CN100443175C - Catalyst for preparing propylene through olefin disproportionation - Google Patents
Catalyst for preparing propylene through olefin disproportionation Download PDFInfo
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- CN100443175C CN100443175C CNB2005100287905A CN200510028790A CN100443175C CN 100443175 C CN100443175 C CN 100443175C CN B2005100287905 A CNB2005100287905 A CN B2005100287905A CN 200510028790 A CN200510028790 A CN 200510028790A CN 100443175 C CN100443175 C CN 100443175C
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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
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
A catalyst for preparing propene by dismutating olefin is composed of the MCM-48 molecular sieve with 3D crossed arteries used as carrier and the active component chosen from tungsten oxide, molybdenum oxide and rhenium oxide. It has high catalytic activity and reaction space rate.
Description
Technical field
The present invention relates to a kind of catalyst of preparing propylene through olefin disproportionation.
Background technology
Olefin disproportionation is a kind of conversion of olefines process.Utilize olefin dismutation reaction, superfluous, that added value is lower relatively alkene can be converted into the high added value olefin product.
The key of olefin dismutation reaction is a catalyst, and catalyst can be homogeneous catalyst and heterogeneous catalyst.Heterogeneous olefin disproportionation catalyst is generally the compound loaded on inert carrier of W, Mo, Re etc.Inert carrier is generally SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3, ZrO
2Aluminophosphates.
US5300718 has reported the technology of butene-2 and ethene generation disproportionated reaction system propylene, and the catalyst that uses is MgO and WO
3/ SiO
2Mixed bed.
EP0489585 has proposed butylene disproportionation Preparation of catalysts method, and catalyst is WO
3/ inert carrier, wherein carrier is SiO
2With MgO or SiO
2With TiO
2What form is cogelled, and the catalyst by method for preparing can make propylene disproportionation system ethene and butylene; The activity of ethene and butene-2 disproportionation system propylene increases.
US5138791 has reported the preparation method of olefin disproportionation catalyst, and its catalyst consists of B
2O
3-Re
2O
7/ Al
2O
3-SiO
2, with amorphous aluminum silicide as catalyst carrier, and with Al
2O
3Or SiO
2Compare for the catalyst of carrier, the activity of olefin dismutation reaction improves greatly.
This shows that the character of carrier has important effect to the performance of olefin disproportionation catalyst.
Mesoporous material has a kind of new material of nanoscale homogeneous pore passage structure and high surface area, is a kind of good catalyst carrier, by load or direct synthesizing active component being introduced mesoporous carrier, can provide catalytic reaction needed active sites.Compare with conventional carrier, the active component decentralization on the mesoporous material is better, and reactant is more abundant with contacting of activated centre, especially is fit to the reaction system of big flow, high-speed.
US5672556 has reported a series of transition metal species has been incorporated into synthetic method in the MCM-41 mesoporous material skeleton that these transition metal species comprise Ti, V, Sn, Zr, Zn, Cu, Co, Cr etc.
US6391278 has reported that with electroneutral primary amine or diamines be the synthetic HMS series mesoporous material that contains transition metal species under the template agent room temperature, and these transition metal species comprise Ti, V, Sn, Zr, Zn, Cu, Cr etc.
Chinese patent 03115307.0 has been reported the work of synthetic tungstenic SBA-15 mesopore molecular sieve, and this tungsten-containing catalyst is that original position is introduced the tungsten oxide component and made in the process of synthetic SBA-15 type total silicon mesoporous molecular sieve.The characteristics of this catalyst are the superelevation load capacity of active component high degree of dispersion and tungsten oxide, are applied in the catalytic selective oxidation reaction of cyclopentene.
More than the carrier that adopts in the report be mesopore molecular sieve with one dimension hexagonal hole road (MCM-41, SBA-15) or the mesoporous material in vermiform duct (HMS).All exist the catalyst activity low in these documents, the problem that reaction velocity is low.
Summary of the invention
Technical problem to be solved by this invention is to exist the catalyst activity lower in the document in the past, and the problem that reaction velocity is low provides a kind of catalyst of new preparing propylene through olefin disproportionation.This catalyst is used for olefin dismutation reaction, and it is active high to have olefin(e) disproportionation, the advantage that reaction velocity 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 catalyst of preparing propylene through olefin disproportionation by weight percentage, comprises following component:
A) 60～99% carrier, carrier is selected from the MCM-48 mesopore molecular sieve;
B) 5～15% be selected from metal at least a among W, Mo or the Re or its oxide;
Wherein be selected from metal at least a among W, Mo or the Re or it is oxide carried in carrier surface, the weight percent content sum of each component is 100% in the catalyst.
In the technique scheme, be selected from metal at least a among W, Mo or the Re or its oxide preferred version is W or WO
3
One of method for preparing catalyst of the present invention is as follows: the mesoporous silica molecular sieve of tungstenic in the directly synthetic skeleton, with softex kw (CTAB) is template, with ethyl orthosilicate (TEOS), waterglass, Ludox or white carbon is the silicon source, with the compound that is selected from ammonium metatungstate, ammonium paratungstate, wolframic acid or tungsten hexachloride is the tungsten source, and feed molar is formed proportioning and is:
1SiO
2∶(0.10～0.60)CTAB∶(0.20～0.35)NaOH/NH
3·H
2O∶0.00～0.05(WO
3)∶(50～150)H
2O
The MCM-48 catalyst of tungstenic is synthetic in the technique scheme, is to carry out crystallization after at room temperature mixing by said ratio, and crystallization temperature is 20 ℃～170 ℃, the spontaneous pressure of pressure gel mixture, and crystallization time is 6～240 hours.
The MCM-48 of synthetic tungstenic needs to handle through the roasting removed template method in the technique scheme, and calcination process can be chosen at Muffle furnace or carry out in tube furnace; The roasting heating mode can be selected in temperature programming under the inert atmosphere, and programming rate is at 1～10 ℃, and sintering temperature can be chosen 350 ℃～800 ℃, preferred 500 ℃～750 ℃.Roasting time 1～24 hour, preferred 3～10 hours; Calcination atmosphere is inert atmosphere 1～20 hour, oxidizing atmosphere 1～10 hour.
Preparation of Catalyst side of the present invention two as follows: with the method for dipping with the component uniform load of tungsten on the MCM-48 total silicon mesopore molecular sieve after the roasting, after in 350 ℃～800 ℃ following oxidizing atmosphere roasting 1～24 hour the MCM-48 mesoporous silica molecular sieve of tungstenic, WO
3Load capacity be 1～40%.Preferred 500～750 ℃ of sintering temperature, preferred 1～8 hour of roasting time, load capacity is preferred 5～30%, and more preferably scope is 5～15%.
The synthetic of MCM-48 total silicon mesopore molecular sieve is template with softex kw (CTAB), is the silicon source with ethyl orthosilicate (TEOS), waterglass, Ludox or white carbon, and be synthetic under alkali condition, and feed molar is formed proportioning and is:
1SiO
2∶(0.10～0.60)CTAB∶(0.20～0.35)NaOH/NH
3·H
2O∶(50～150)H
2O
Total silicon MCM-48 needs to handle through the roasting removed template method, and calcination process can be chosen at Muffle furnace or carry out in tube furnace; The roasting heating mode can be selected in temperature programming under the inert atmosphere, and programming rate is at 1～10 ℃, and sintering temperature can be chosen 350 ℃～800 ℃, preferred 500 ℃～750 ℃.Roasting time 1～24 hour, preferred 3～10 hours; Calcination atmosphere is inert atmosphere 1～20 hour, oxidizing atmosphere 1～10 hour.
The mesopore molecular sieve of synthetic tungstenic can be selected spin, extruding slivering for use among above-mentioned two kinds of preparation methods, and method moulding such as compressing tablet should add binding agent in the forming process, and binding agent can be selected Ludox for use.
The tungsten-contained mesic porous SiO 2 molecular sieve catalyst that adopts above-mentioned two kinds of preparation methods to make can use in the preparing propylene through olefin disproportionation reaction, and embodiments of the invention are butylene and ethene disproportionated reaction system propylene.Reaction condition is as follows: in the fixed bed reactors, reaction temperature is 0～550 ℃, reaction pressure is 0～35MPa, and the liquid phase air speed is 0.1～10 hour
-1Under the condition, ethene and butylene disproportionation reaction generate propylene.
The present invention is by introducing tungsten on the skeleton of mesoporous MCM-48 molecular sieve, or adopt the carrier of mesoporous MCM-48 as tungsten oxide, specific surface area of catalyst is improved greatly, the decentralization of the tungsten that has increased, 3 D pore canal has improved the diffusion of material simultaneously, the conversion ratio of 1-butylene can reach more than 80%, and selectivity has obtained better technical effect more than 97%.
The invention will be further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
Total silicon MCM-48's is synthetic
Take by weighing CTAB 10 grams, NaOH 4.5 grams are dissolved in 286 ml deionized water, stir until clarification under the room temperature, obtain solution A.47.24 milliliters of TEOS slowly are added drop-wise among the A,, obtain milky suspension B in 30 ℃ of following vigorous stirring 1 hour.Gel B is poured in the stainless steel still that contains polytetrafluoroethylene bushing, in 100 ℃ of baking ovens, left standstill 24 hours.Spend deionised water behind the solidliquid mixture matter suction filtration that obtains to neutral, place the oven dry of spending the night of 80 ℃ of baking ovens, obtain synthetic sample.
[embodiment 2]
WOx/MCM-48's is directly synthetic
3.10 gram CTAB and 1.111 gram NaOH are dissolved in 47 ml deionized water, obtain settled solution A.Take by weighing the Ludox of 8.333 grams 40% (weight), slowly drop among the A, stirring is after 5 minutes down in 30 ℃, and at adding 1.20 gram ammonium metatungstates, vigorous stirring 1 hour obtains white suspension B.Gel B is poured in the stainless steel still that contains polytetrafluoroethylene bushing, in 100 ℃ of baking ovens, left standstill 24 hours.Spend deionised water behind the solidliquid mixture matter suction filtration that obtains to neutral, place the oven dry of spending the night of 80 ℃ of baking ovens, obtain synthetic sample.Its tungstenic amount is 12% (weight).
[embodiment 3]
WOx/MCM-48's is directly synthetic
3.10 gram CTAB and 1.111 gram NaOH are dissolved in 47 ml deionized water, obtain settled solution A.Take by weighing the Ludox of 8.333 grams 40%, slowly drop among the A, stirring is after 5 minutes down in 30 ℃, and at adding 0.80 gram ammonium metatungstate, vigorous stirring 1 hour obtains white suspension B.Suspension B is poured in the stainless steel still that contains polytetrafluoroethylene bushing, in 100 ℃ of baking ovens, left standstill 24 hours.Spend deionised water behind the solidliquid mixture matter suction filtration that obtains to neutral, place the oven dry of spending the night of 80 ℃ of baking ovens, obtain synthetic sample.Its tungstenic amount is 8%.
[embodiment 4]
The roasting of synthetic sample
Get above-mentioned dried sample and place tube furnace, feed nitrogen with gas flow rate 1 ml/min, rise to 550 ℃ with 2 ℃/minute programming rates by room temperature, and under the condition that feeds nitrogen, 550 ℃ kept 1 hour, then in Muffle furnace 550 ℃ continued roasting 5 hours, obtain the sample after the roasting.
[embodiment 5]
Immersion process for preparing WO
X/ MCM-48 sample
Take by weighing total silicon MCM-48 molecular sieve 5 grams after the roasting.0.723 gram ammonium metatungstate is dissolved in 32 deionized waters, after stirring,, at room temperature dries, place 80 ℃ of baking ovens to spend the night then with this solution impregnation MCM-48 molecular sieve.The 550 ℃ of roastings in Muffle furnace of the sample of oven dry obtained after 2 hours is that to carry a tungsten amount be the MCM-48 of 12% (weight).
[embodiment 6]
Immersion process for preparing WO
X/ MCM-48 sample
Take by weighing total silicon MCM-48 molecular sieve 5 grams after the roasting.0.723 gram ammonium metatungstate is dissolved in 32 deionized waters, after stirring,, at room temperature dries, place 80 ℃ of baking ovens to spend the night then with this solution impregnation MCM-48 molecular sieve.The 550 ℃ of roastings in Muffle furnace of the sample of oven dry obtained after 2 hours is that to carry the tungsten amount be 8% MCM-48.
[embodiment 7]
The moulding of the MCM-48 sample of tungstenic and disproportionated reaction system propylene
With MCM-48 powdered samples compressing tablet, the grinding of tungstenic, wherein 10～20 purpose particles are stand-by in screening.
In length is 110 centimetres, and internal diameter is that 2.5 centimetres reactor lower curtate adding volume is 110 centimetres
3, granularity is 10～20 order glass marble fillers; The disproportionation catalyst of 2 gram formings is added reactor, cover one deck double bond isomerizing catalyst MgO again, the weight ratio of disproportionation catalyst and isomerization catalyst is 1: 5, and the catalyst upper end adds 60 centimetres again
3, granularity is 10～20 order glass marble fillers.Reactor is warming up to 550 ℃ under the air conditions of 10 liters/hour of feedings, and after keeping 2 hours under this temperature, uses N then
2Purged 1 hour, and reduced to 350 ℃ of reaction temperatures.
Reactor stops to feed nitrogen, and feeds the 1-butene feedstock of 99.5% weight and the ethylene raw of 99.9% weight from the reactor upper end, and butylene: ethylene molar ratio is 1: 2, and the liquid quality air speed is 0.6 hour
-1, reaction system pressure is by the control valve control of reactor outlet, and pressure is controlled at 30MPa.Product after release by the gas-chromatography on-line analysis.
The result shows that the disproportionation catalyst of the MCM-48 specific activity routine of tungstenic increases.
The MCM-48 activity of table 1 tungstenic and conventional disproportionation catalyst specific activity are
Claims (2)
1, a kind of catalyst of preparing propylene through olefin disproportionation by weight percentage, comprises following component:
A) 60～99% carrier, carrier is selected from the MCM-48 mesopore molecular sieve;
B) 5～15% be selected from metal at least a among W, Mo or the Re or its oxide;
Wherein be selected from metal at least a among W, Mo or the Re or it is oxide carried in carrier surface, the weight percent content sum of each component is 100% in the catalyst.
2, according to the catalyst of the described preparing propylene through olefin disproportionation of claim 1, it is characterized in that being selected from metal at least a among W, Mo or the Re or its oxide is W or WO
3
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|---|---|---|---|
| CNB2005100287905A CN100443175C (en) | 2005-08-15 | 2005-08-15 | Catalyst for preparing propylene through olefin disproportionation |
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| CN100443175C true CN100443175C (en) | 2008-12-17 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733146B (en) * | 2008-11-21 | 2012-09-05 | 中国石油化工股份有限公司 | Catalyst for synthesizing propylene by using ethylene and butylene |
| CN102491867B (en) * | 2011-11-25 | 2014-02-26 | 常州均益新材料科技有限公司 | Method for producing propylene by disproportionation of ethylene and long-chain olefins |
| CN104857953B (en) * | 2015-05-08 | 2018-10-12 | 宁波富德能源有限公司 | A kind of preparation method for the catalyst being disproportionated propylene processed for carbon four and ethylene |
| CN106824169B (en) * | 2015-12-03 | 2019-09-06 | 中国石油化工股份有限公司 | Olefin metathesis catalyst and application thereof |
| CN111111764A (en) * | 2018-10-30 | 2020-05-08 | 中国石油化工股份有限公司 | Catalyst system and use thereof |
| CN111250153B (en) * | 2018-11-30 | 2021-08-10 | 中国科学院大连化学物理研究所 | Al (aluminum)2O3Preparation method of Mo-loaded catalytic material of hierarchical pore molecular sieve and application of Mo-loaded catalytic material in preparation of propylene through disproportionation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672556A (en) * | 1994-08-22 | 1997-09-30 | Board Of Trustees Operating Michigan State University | Crystalline silicate compositions and method of preparation |
| CN1401431A (en) * | 2001-08-24 | 2003-03-12 | 中国科学院大连化学物理研究所 | Methane aromatizing catalyst and use thereof in preparation of arenes |
| CN1680033A (en) * | 2005-02-03 | 2005-10-12 | 复旦大学 | Tungsten-containing mesoporous molecular sieve catalyst for synthesizing glutaraldehyde and its manufacturing method |
-
2005
- 2005-08-15 CN CNB2005100287905A patent/CN100443175C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672556A (en) * | 1994-08-22 | 1997-09-30 | Board Of Trustees Operating Michigan State University | Crystalline silicate compositions and method of preparation |
| CN1401431A (en) * | 2001-08-24 | 2003-03-12 | 中国科学院大连化学物理研究所 | Methane aromatizing catalyst and use thereof in preparation of arenes |
| CN1680033A (en) * | 2005-02-03 | 2005-10-12 | 复旦大学 | Tungsten-containing mesoporous molecular sieve catalyst for synthesizing glutaraldehyde and its manufacturing method |
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|---|---|
| CN1915510A (en) | 2007-02-21 |
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