CN1590354A - Method of raising butene disproportionation reaction activity - Google Patents
Method of raising butene disproportionation reaction activity Download PDFInfo
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- CN1590354A CN1590354A CNA031507344A CN03150734A CN1590354A CN 1590354 A CN1590354 A CN 1590354A CN A031507344 A CNA031507344 A CN A031507344A CN 03150734 A CN03150734 A CN 03150734A CN 1590354 A CN1590354 A CN 1590354A
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- molecular sieve
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- reactive behavior
- disproportionation
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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
A method for increasing the activity of butene in disproportionation reaction features that in the disproportionation reaction of butene, the catalyst which uses the W-contained mesoporous SiO2 molecular sieve MCM-41 as its active component and silica sol as its adhesive is used.
Description
Technical field
The present invention relates to improve the method for butylene disproportionation reactive behavior.
Background technology
Olefin dismutation reaction is a kind of conversion of olefines process.Utilizing olefin dismutation reaction, can be the high added value olefin product with superfluous, that added value is lower relatively conversion of olefines, is that ethene and butylene are carried out cross disproportionation reaction generation propylene as the OCT technology of ABB Lummus company and the meta-4 technology of IFP.
The key of olefin dismutation reaction is a catalyzer, and its composition is generally the compound loaded on inert support of W, Mo, Re etc.Inert support is generally SiO
2, Al
2O
3, TiO
2, SiO
2-Al
2O
3, aluminophosphates.By the modulation of catalyzer, can improve the olefin dismutation reaction performance.
US5300718 has reported the technology of butene-2 and ethene generation disproportionation reaction system propylene, and the catalyzer that uses is MgO and WO
3/ SiO
2Mixed bed.EP0489585 has proposed butylene disproportionation Preparation of catalysts method, and catalyzer is WO
3/ inert support, wherein carrier is SiO
2With MgO or SiO
2With TiO
2What form is cogelled, and the catalyzer 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 catalyzer consists of B
2O
3-Re
2O
7/ Al
2O
3-SiO
2, with amorphous aluminum silicide as support of the catalyst, and with Al
2O
3Or SiO
2Compare for the catalyzer of carrier, the activity of olefin dismutation reaction improves greatly.EP0152112 has reported with Ti and has modified WO
3/ SiO
2Support of the catalyst; US5905055 has reported with Nb and has modified WO
3/ SiO
2Support of the catalyst, olefin metathesis activity all obtain to improve.
In olefin disproportionation catalyst, the highly dispersed state transition metal oxide is the reactive activity component, and the transition metal oxide dispersion state is relevant with the physico-chemical property of carrier, and wherein carrier has high-specific surface area, helps the dispersion of active ingredient.
MCM-41 is the crystal form SiO with homogeneous pore passage structure, bigger serface
2Mesoporous material is the excellent carrier of catalyzer.The US5098684 play-by-play this type of SiO
2The synthetic method of mesoporous material.US5672556 has reported that falling a series of transition metal species is incorporated into synthetic method in the MCM-41 mesoporous material skeleton, and these transition metal species comprise Ti, V, Sn, Zr, Zn, Cu, Cr etc.
With mesoporous WO
X/ MCM-41 molecular sieve is that olefin disproportionation catalyst does not appear in the newspapers.
Summary of the invention
Technical problem to be solved by this invention is to exist the olefin disproportionation catalyst specific surface area little in the conventional art, the bad dispersibility of Tungsten oxide 99.999 in the catalyzer, the active low problem of olefin metathesis when causing olefin dismutation reaction provides a kind of method of new raising butylene disproportionation reactive behavior.This method has the active high characteristics of olefin metathesis.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that improves the butylene disproportionation reactive behavior is a raw material with the butylene, with the mesopore molecular sieve is catalyzer, in temperature of reaction is 0～500 ℃, and reaction pressure is 0～10MPa, and the liquid phase weight space velocity is 0.1～3 hour
-1Condition issue Centime alkene disproportionation reaction and generate propylene, ethene and hexene, use therein mesoporous molecular sieve catalyst comprises following component by weight percentage:
A) 50～78% have the homogeneous duct, and mean pore size is 3～10 nanometers, and specific surface area is 700～1200 meters
2The mesoporous SiO of MCM-41 of/gram
2Molecular sieve; With carry thereon
B) 2～20% transition metal oxide;
C) 20～48% binding agent.
In the technique scheme, the temperature of reaction preferable range is 300～350 ℃, and the reaction pressure preferable range is 0.3～1.0MPa, and reaction weight space velocity preferable range is 0.3～1.5 hour
-1By weight percentage, the mesoporous SiO of MCM-41
2The consumption preferable range of molecular sieve is 60～70%; The consumption preferable range of transition metal oxide is 6～16% by weight percentage; The consumption preferable range of binding agent is 20～30% by weight percentage.The transition metal oxide preferred version is a Tungsten oxide 99.999, and the binding agent preferred version is a silicon sol.The mesoporous SiO of MCM-41
2The specific surface area preferable range of molecular sieve is 700～1000 meters
2/ gram.The transition metal oxide preferred version is to be distributed on the MCM-41 mesopore molecular sieve with skeleton or high dispersive oxide form, its more preferably scheme be to be introduced directly on the MCM-41 mesopore molecular sieve carrier, another more preferably scheme be to be incorporated on the MCM-41 mesopore molecular sieve carrier with the method for supporting.
Catalyzer can adopt spin, extruding slivering among the present invention, and method moulding such as compressing tablet should add binding agent in the moulding process, and binding agent is a silicon sol, and the binding agent consumption is 20%～30% of a catalyst weight.
The optional water thermal synthesis of method for preparing catalyst, methods such as collosol and gel, ion-exchange, dipping, chemisorption, electroless plating, physical mixed; Preferred version is that the compound of W is introduced directly on the mesoporous MCM-41 material through sol-gel method, and the compound that also can be W is impregnated on the MCM-41.
Adopting the technique scheme reaction conditions is that fixed-bed reactor, temperature of reaction are 0～500 ℃, and reaction pressure is 0～10MPa, and the liquid phase air speed is 0.1～10 hour
-1Under the condition, butene-1 carries out disproportionation reaction.
The present invention passes through WO
3Introduce the skeleton of mesoporous MCM-41, or adopt the carrier loaded WO of mesoporous MCM-41 as catalyzer
3, specific surface area of catalyst improved, the WO that has increased
3Dispersity, thus catalyzer olefin dismutation reaction performance improved, obtained better technical effect.
The invention will be further elaborated below by embodiment.
Embodiment
[embodiment 1～3]
W-MCM-41's is synthetic
Take by weighing hexadecyl trimethyl ammonium bromide (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved hexadecyl trimethyl ammonium bromide fully, wiring solution-forming A.Other gets a beaker, takes by weighing 104 gram tetraethoxys (TEOS), under room temperature, violent stirring, drips the ammonium metatungstate solution of certain volume, concentration, after being added dropwise to complete, and wiring solution-forming B.Under the stirring at room, with solution B, being added drop-wise in the solution A, is that mixture ratio is 1SiO
2: (0.08～0.20) CTAB: (5～9) HCl: 0.00～0.05 (WO
3): (80～150) H
2O, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stirred crystallization 24 hours, centrifugation, solid sample deionized water wash three times, sample is 80 ℃ of oven dry.
Sample is placed tube furnace, with gas space velocity 2000 hours
-1Feed nitrogen, rise to 500 ℃ by room temperature, and under the condition that feeds nitrogen, 500 ℃ kept 4 hours, with gas space velocity 2000 hours with 2 ℃/minute heat-up rates
-1Bubbling air, and 500 ℃ of roastings 6 hours.Add ammonium tungstate solution concentration difference when synthetic, make WO respectively
3Content respectively is 8%, 10%, 12% by weight percentage, and specific surface area respectively is 750 meters
2/ gram, 1000 meters
2/ gram, 950 meters
23 samples such as W-MCM-41 of/gram.
[embodiment 4]
The MCM-41 carrier is synthetic under acidic conditions
Take by weighing hexadecyl trimethyl ammonium bromide (CTAB) 21.5 grams and place beaker, add 900 ml deionized water and 440 milliliters of concentrated hydrochloric acids, stirring at room is dissolved hexadecyl trimethyl ammonium bromide fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 104 gram tetraethoxys (TEOS), becomes solution B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; Temperature is risen to 60 ℃, stir after 24 hours, centrifugation, solid sample deionized water wash three times, sample is 80 ℃ of oven dry, and the gained sample is designated as SA.
[embodiment 5]
The MCM-41 carrier is synthetic under alkaline condition
Take by weighing hexadecyl trimethyl ammonium bromide (CTAB) 10.2 grams and place beaker, add the ethylamine solution of 240 ml deionized water and 19.4 grams 65%, stirring at room is dissolved hexadecyl trimethyl ammonium bromide fully, wiring solution-forming A.
Other gets a beaker, takes by weighing 41.6 gram tetraethoxys (TEOS), becomes solution B.
Under the stirring at room,, be added drop-wise in the solution A solution B, after being added dropwise to complete, stirring at room 2 hours; The material that mixes is put into autoclave, 120 ℃ leave standstill 48 hours after, filter, deionized water wash three times, sample is 80 ℃ of oven dry, the gained sample is designated as SB.
[embodiment 6]
The roasting of synthetic sample
Get above-mentioned dried sample B and place tube furnace, with gas space velocity 2000 hours
-1Feed nitrogen, rise to 500 ℃ by room temperature, and under the condition that feeds nitrogen, 500 ℃ kept 4 hours, with gas space velocity 2000 hours with 2 ℃/minute heat-up rates
-1Bubbling air, and 500 ℃ of roastings 6 hours.
[embodiment 7～8]
Immersion process for preparing WO
X/ MCM-41 sample
Take by weighing the SA sample of 20 grams after the roastings, other takes by weighing ammonium metawolframate 2.89 grams, adds 25 milliliters of deionized waters, under agitation is added drop-wise to respectively in the SA sample, leaves standstill and dries, and 120 ℃ of oven dry 6 hours, places 550 ℃ of roastings of retort furnace 6 hours, sample WSA-imp.
Take by weighing the SB sample of 20 grams after the roastings, other takes by weighing ammonium metawolframate 2.89 grams, adds 25 milliliters of deionized waters, under agitation is added drop-wise to respectively in the SB sample, leaves standstill and dries, and 120 ℃ of oven dry 6 hours, places 550 ℃ of roastings of retort furnace 6 hours, sample WSB-imp.
Take by weighing the prepared powdered sample of 10 gram the foregoing descriptions respectively, behind adding sesbania powder 0.3 gram, silicon sol 10 grams, mediate evenly, extruded moulding after room temperature leaves standstill 24 hours, was dried 6 hours, and was placed 550 ℃ of roastings of retort furnace 6 hours for 120 ℃.
[comparative example 1]
Immersion process for preparing WO
3/ SiO
2Sample
(15 orders, specific surface are 478 meters to take by weighing 20 gram silica gel samples
2/ gram, SiO
2Content is 99.9%), other takes by weighing ammonium metawolframate 2.89 grams, adds 25 milliliters of deionized waters, under agitation is added drop-wise to respectively in the silica gel sample, leaves standstill and dries, and 120 ℃ of oven dry 6 hours, places 550 ℃ of roastings of retort furnace 6 hours, gets sample WO
3/ SiO
2
[embodiment 9～14]
Butylene disproportionation reaction---the influence of catalyzer
In length is 110 centimetres, and internal diameter is that 2.5 centimetres reactor bottom adding volume is 110 centimetres
3, granularity is 15 order glass sphere fillers; 10 gram catalyzer are added reactor, and the catalyzer upper end adds 60 centimetres again
3, granularity is 15 order glass sphere fillers.Be warming up to 550 ℃ under the condition of nitrogen gas that the reactor feeding is 10 liters/hour, and after keeping 2 hours under this temperature, reduce to 350 ℃ of temperature of reaction.
Reactor stops to feed nitrogen, and feeds 99.5% butene-1 raw material from reactor upper end, and raw material flow rate is the variable valve control by reactor outlet of 24 milliliters/hour, reaction system pressure, and pressure-controlling is at 0.49MPa.Reaction product after release by the gas-chromatography on-line analysis.React and reach balance, reaction result such as table 1 after 10 hours.
The butylene disproportionation reactivity worth of table 1 W-MCM-41 sample
Reaction product is formed (mole %)
Sample
Ethylene, propylene butene-2 butene-1 iso-butylene amylene hexene
8％W-MCM-41 2.8 20.29 47.65 13.58 0.15 12.55 2.98
10％W-MCM-41 4.56 27.77 36.86 10.55 0.15 15.37 4.49
12％W-MCM-41 3.30 20.05 46.47 14.22 0.15 12.01 3.80
WSA-imp 4.38 24.58 39.12 11.50 0.15 15.58 4.69
WSB-imp 2.37 22.59 46.47 12.87 0.18 13.25 2.27
WO
3/SiO
2 0.79 11.18 61.11 16.67 0.59 8.49 0.77
[embodiment 15～18]
Butylene disproportionation reaction-different air speeds
Carry out catalyst loading, pre-treatment and butylene disproportionation reaction by the program shown in the embodiment 9, catalyzer is WO
3Weight content is 10% W-MCM-41 catalyzer, reaction conditions such as embodiment 9, and raw material butene feed amount is respectively 6,12,18 milliliters/hour.Reaction product is by the gas-chromatography on-line analysis.React and reach balance, reaction result such as table 2 after 10 hours.
[comparative example 2]
The butylene disproportionation reaction
Carry out catalyst loading, pre-treatment and butylene disproportionation reaction by the program shown in the embodiment 9, catalyzer is WO
3/ SiO
2Catalyzer, reaction conditions such as embodiment 9, raw material butene feed amount is respectively 6 milliliters/hour.Reaction product is by the gas-chromatography on-line analysis.React and reach balance, reaction result such as table 2 after 10 hours.
The influence of table 2 air speed
Butene feed speed responsing product is formed (mole %)
Milliliter/hour ethylene, propylene butene-2 butene-1 iso-butylene amylene hexene
6 5.01 34.21 28.7 9.35 0.15 17.55 5.03
12 5.12 33.1 29.01 9.96 0.15 17.43 5.23
18 4.98 30.11 31.2 11.69 0.16 16.98 4.88
24 4.56 27.77 36.86 10.55 0.15 15.37 4.49
6
* 4.82 32.65 29.85 9.82 2.42 16.58 4.60
24
* 0.79 11.18 61.11 16.67 0.59 8.49 0.77
*: catalyzer is WO
3/ SiO
2
Claims (9)
1, a kind of method that improves the butylene disproportionation reactive behavior is a raw material with the butylene, is catalyzer with the mesopore molecular sieve, and 0～500 ℃ of temperature of reaction, reaction pressure is 0～10MPa, and the liquid phase weight space velocity is 0.1～3 hour
-1Condition issue Centime alkene disproportionation reaction and generate propylene, ethene and hexene, it is characterized in that the mesoporous molecular sieve catalyst that uses by weight percentage, comprises following component:
A) 50～78% have the homogeneous duct, and mean pore size is 3～10 nanometers, and specific surface area is 700～1200 meters
2The mesoporous SiO of MCM-41 of/gram
2Molecular sieve; With carry thereon
B) 2～20% transition metal oxide;
C) 20～48% binding agent.
2, according to the method for the described raising butylene disproportionation of claim 1 reactive behavior, it is characterized in that temperature of reaction is 300～350 ℃, reaction pressure is 0.3～1.0MPa, the reaction weight space velocity is 0.3～1.5 hour
-1
3,, it is characterized in that the mesoporous SiO of MCM-41 by weight percentage according to the method for the described raising butylene disproportionation of claim 1 reactive behavior
2The consumption of molecular sieve is 60～70%.
4, according to the method for the described raising butylene disproportionation of claim 1 reactive behavior, it is characterized in that the consumption of transition metal oxide is 6～16% by weight percentage, the consumption of binding agent is 20～30%.
5, according to the method for the described raising butylene disproportionation of claim 1 reactive behavior, it is characterized in that transition metal oxide is a Tungsten oxide 99.999, binding agent is a silicon sol.
6,, it is characterized in that the mesoporous SiO of MCM-41 according to the method for the described raising butylene disproportionation of claim 1 reactive behavior
2The specific surface area of molecular sieve is 700～1000 meters
2/ gram.
7,, it is characterized in that transition metal oxide is to be distributed on the MCM-41 mesopore molecular sieve with skeleton or high dispersive oxide form according to the method for the described raising butylene disproportionation of claim 1 reactive behavior.
8,, it is characterized in that transition metal oxide is to be introduced directly on the MCM-41 mesopore molecular sieve carrier according to the method for the described raising butylene disproportionation of claim 7 reactive behavior.
9,, it is characterized in that transition metal oxide is to be incorporated on the MCM-41 mesopore molecular sieve carrier with the method for supporting according to the method for the described raising butylene disproportionation of claim 7 reactive behavior.
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|---|---|---|---|
| CNB031507344A CN1241883C (en) | 2003-09-03 | 2003-09-03 | Method of raising butene disproportionation reaction activity |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031507344A CN1241883C (en) | 2003-09-03 | 2003-09-03 | Method of raising butene disproportionation reaction activity |
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|---|---|
| CN1590354A true CN1590354A (en) | 2005-03-09 |
| CN1241883C CN1241883C (en) | 2006-02-15 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875312A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing tetramethylethylene by olefin metathesis in fluidized bed |
| CN101768040B (en) * | 2009-01-07 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene from butylene and ethylene |
| CN103420772A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing hexene from butene |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875308A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for producing propylene and hexene by butene disproportionation |
-
2003
- 2003-09-03 CN CNB031507344A patent/CN1241883C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768040B (en) * | 2009-01-07 | 2013-04-03 | 中国石油化工股份有限公司 | Method for preparing propylene from butylene and ethylene |
| CN102875312A (en) * | 2011-07-12 | 2013-01-16 | 中国石油化工股份有限公司 | Method for preparing tetramethylethylene by olefin metathesis in fluidized bed |
| CN102875312B (en) * | 2011-07-12 | 2014-10-15 | 中国石油化工股份有限公司 | Method for preparing tetramethylethylene by olefin metathesis in fluidized bed |
| CN103420772A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing hexene from butene |
| CN103420772B (en) * | 2012-05-16 | 2015-10-21 | 中国石油化工股份有限公司 | For the method for butylene hexene |
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| Publication number | Publication date |
|---|---|
| CN1241883C (en) | 2006-02-15 |
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