CN103846084A - Supported tungsten based catalyst for preparing propylene by 1-butene disproportionation as well as preparation method and application of supported tungsten based catalyst - Google Patents
Supported tungsten based catalyst for preparing propylene by 1-butene disproportionation as well as preparation method and application of supported tungsten based catalyst Download PDFInfo
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Abstract
The invention discloses a supported tungsten based catalyst for preparing propylene by 1-butene disproportionation. The supported tungsten based catalyst comprises a carrier and an active component supported to the carrier; the carrier is gamma-Al2O3 deposited with Si, and the deposition amount of Si is 10%-25% of mass of gamma-Al2O3; the active component is oxide of tungsten; the supported amount of tungsten is 2%-10% of the mass of the carrier. Additionally, the invention also discloses a preparation method of the supported tungsten based catalyst as well as the application in preparing propylene by catalyzing 1-butene and disproportionation. The supported tungsten based catalyst provided by the invention can be used for the reaction for preparing propylene by 1-butene disproportionation at lower reaction temperature; the catalyst provided by the invention can be used for preparing propylene by catalyzing 1-butene and disproportionation at low temperature and normal pressure; the 1-butene conversion rate can reach 71.7mol%, and the propylene production rate can reach 20.0mol%.
Description
Technical field
The invention belongs to loaded catalyst technical field, be specifically related to support type tungsten-based catalyst and preparation method and application that a kind of 1-butylene disproportionation is prepared propylene.
Background technology
Alkene is one of most important basic organic being only second to by ethene, and its maximum purposes is to produce polypropylene, accounts for 60% left and right, is secondly to produce acrylonitrile, expoxy propane, isopropylbenzene, isopropyl alcohol, oxo-alcohols and other downstream product.Within 2002, global propylene consumption figure is about 5,350 ten thousand tons, and its global demand average growth rate per annum is 5.6%, and propylene demand growth speed has exceeded ethene (4.6%), and by 2010, global propylene demand will reach 7,500 ten thousand tons.Utilize butylene disproportionation reaction, can be by C relative surplus, that added value is lower
4olefin feedstock is converted into high added value propylene product.1-butylene produces ethene and hexene in self disproportionated reaction process, in the disproportionation stage, to there is double bond isomerization reaction at catalyst surface simultaneously and generate 2-butylene in 1-butylene, 2-butylene and 1-butylene cross disproportionation, a certain amount of propylene of output and amylene, the optionally key that how can improve propylene and amylene is to select suitable catalyst.
United States Patent (USP) WO2004110967 adopts MgO-WO
3/ SiO
2catalyst, 150 DEG C～400 DEG C of reaction temperatures, reaction pressure 1.0MPa～4.0MPa.Butene conversion is 60%, and Propylene Selectivity is 95%, although productivity of propylene is higher, reaction temperature pressure is also higher.Chinese patent (CN1590294A) has been reported the tungsten-based catalyst of butylene disproportionation, and this catalyst is tungsten oxide load or directly introduces in HMS mesopore molecular sieve, reacts in fixed bed reactors, and reaction temperature is 350 DEG C; Reaction pressure is 0.45MPa, and liquid phase air speed is 24mL/min, and butene conversion can reach 84.72mol%, and productivity of propylene can reach 20.87mol%.Chinese patent (CN1827210) adopts MoO
3-MgO/H β-Al
2o
3as carrier, 100 DEG C～300 DEG C of reaction temperatures, pressure 1MPa～3MPa, productivity of propylene can reach 14mol% left and right.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, provides a kind of 1-butylene disproportionation to prepare the support type tungsten-based catalyst of propylene.This support type tungsten-based catalyst can be used for compared with 1-preparing propylene by butene disproportionation reaction under low reaction temperatures, adopt this catalyst under low temperature (80 DEG C～200 DEG C) normal pressure, to prepare propylene by catalysis 1-butylene disproportionation, 1-butene conversion can reach 71.7mol%, and productivity of propylene can reach 20.9mol%.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of 1-butylene disproportionation is prepared the support type tungsten-based catalyst of propylene, comprises carrier and is carried on the active component on carrier, it is characterized in that, described carrier is γ-Al of deposition Si
2o
3, the deposition of Si is γ-Al
2o
310%～25% of quality, the oxide that described active component is tungsten, the load capacity of tungsten is 2%～10% of carrier quality.
Above-mentioned 1-butylene disproportionation is prepared the support type tungsten-based catalyst of propylene, and the deposition of described Si is γ-Al
2o
315%～23% of quality, the load capacity of tungsten is 4%～8% of carrier quality.
Above-mentioned 1-butylene disproportionation is prepared the support type tungsten-based catalyst of propylene, and the deposition of described Si is γ-Al
2o
320% of quality, the load capacity of tungsten is 6% of carrier quality.
In addition, the present invention also provides a kind of method of preparing above-mentioned support type tungsten-based catalyst, it is characterized in that, the method comprises the following steps:
Step 1, silicon-containing compound is dissolved in organic solvent and obtains siliceous organic solution, adopt described siliceous organic solution dipping γ-Al
2o
3, then by the γ-Al after dipping
2o
3take out dry, then under air atmosphere by dried γ-Al
2o
3roasting, obtains carrier; The temperature of described roasting is 350 DEG C～750 DEG C, and the time of roasting is 12h～24h;
Step 2, adopt carrier described in soluble tungsten salt solution impregnation step 1, then the carrier after dipping is taken out dry, then under air atmosphere by dried carrier roasting, obtain the support type tungsten-based catalyst that 1-butylene disproportionation is prepared propylene; The temperature of described roasting is 350 DEG C～750 DEG C, and roasting time is 4h～8h.
Above-mentioned method, silicon-containing compound described in step 1 is APTES or 3-aminopropyl trimethoxysilane, described organic solvent is ethanol or methyl alcohol.
Above-mentioned method, the salt of soluble tungsten described in step 2 is ammonium metatungstate or ammonium tungstate.
Above-mentioned method, the time of flooding described in step 2 is 3h～6h.
Further, the present invention also provides a kind of above-mentioned support type tungsten-based catalyst to prepare the application in propylene at catalysis 1-butylene disproportionation.
Above-mentioned application, catalytic condition is: 80 DEG C～200 DEG C of reaction temperatures, reaction pressure 0.1MPa, reactor feed gas is 1-butylene, 1-butylene weight space velocity is 0.6h
-1～2.4h
-1.
Above-mentioned application, the consumption of support type tungsten-based catalyst is every 0.1g～0.5g support type tungsten-based catalyst for 1mL reactor.
The present invention compared with prior art has the following advantages:
1, carrier γ-Al
2o
3acidity a little less than, and and load tungsten oxide between interaction too strong, tungsten oxide thereon degree of scatter is high, is difficult to form the required active specy of butylene disproportionation with 1-butylene while contact at low temperatures, the present invention is by γ-Al
2o
3the Si of upper deposition 10wt%～25wt%, not only can increase support acidity, can also weaken the interaction between carrier and load tungsten oxide, reduce tungsten oxide degree of scatter thereon, while contact with 1-butylene at low temperatures, be conducive to form disproportionation active metal Cabbeen species.
2, support type tungsten-based catalyst of the present invention can be used for compared with 1-preparing propylene by butene disproportionation reaction under low reaction temperatures, adopt catalyst of the present invention under low temperature (80 DEG C～200 DEG C) normal pressure, to prepare propylene by catalysis 1-butylene disproportionation, 1-butene conversion can reach 71.7mol%, and productivity of propylene can reach 20.9mol%.
Below by embodiment, technical solution of the present invention is described in further detail.
Detailed description of the invention
Embodiment 1
The support type tungsten-based catalyst of the present embodiment comprises carrier and is carried on the active component on carrier, and described carrier is γ-Al of deposition Si
2o
3, the deposition of Si is γ-Al
2o
320% of quality, the oxide that described active component is tungsten, the load capacity of tungsten is 6% of carrier quality.
The preparation method of the support type tungsten-based catalyst of the present embodiment is:
Step 1, the APTES of siliceous 0.2g (Aldrich, 99.9%) is dissolved in 10mL absolute ethyl alcohol and obtains siliceous organic solution, by 1g γ-Al
2o
3be placed in siliceous organic solution and stir dipping 2h, then by the γ-Al after dipping
2o
3take out, 100 DEG C of dry 24h, then under air atmosphere by dried γ-Al
2o
3roasting, obtains carrier 20Si/Al; The temperature of described roasting is 550 DEG C, and the time of roasting is 24h;
Step 2, by carrier described in 1g step 1 be placed in 10mL ammonium metatungstate solution (tungstenic 0.06g) stir dipping 5h, then the carrier after dipping is taken out, 100 DEG C of dry 24h, again under air atmosphere by dried carrier roasting, obtain the support type tungsten-based catalyst 6W/20Si/Al that 1-butylene disproportionation is prepared propylene; The temperature of described roasting is 550 DEG C, and roasting time is 8h.
Adopt the catalyst 1-butylene disproportionation of the present embodiment to prepare propylene, method is: 0.2g catalyst is packed in the U-shaped reactor that volume is 1mL, to the argon gas that passes into 50mL/min in reactor, reactor is warming up to 550 DEG C, after insulation 2h, lower the temperature, when question response actuator temperature is down to 180 DEG C, argon gas is switched to 1-butylene (99.5%), under normal pressure (0.1MPa), carry out the reaction of 1-butylene disproportionation, material quality air speed is 2.4h
-1, product, by gas-chromatography on-line analysis, is got a sample analysis for every 1 hour, and reaction initial activity is got the mean value in 3 hours, and reaction result is in table 1.
Embodiment 2
The support type tungsten-based catalyst of the present embodiment comprises carrier and is carried on the active component on carrier, and described carrier is γ-Al of deposition Si
2o
3, the deposition of Si is γ-Al
2o
323% of quality, the oxide that described active component is tungsten, the load capacity of tungsten is 8% of carrier quality.
The preparation method of the support type tungsten-based catalyst of the present embodiment is:
Step 1, the APTES of siliceous 0.23g (Aldrich, 99.9%) is dissolved in 20mL absolute methanol and obtains siliceous organic solution, by 1g γ-Al
2o
3be placed in siliceous organic solution and stir dipping 2h, then by the γ-Al after dipping
2o
3take out, 100 DEG C of dry 24h, then under air atmosphere by dried γ-Al
2o
3roasting, obtains carrier 23Si/Al; The temperature of described roasting is 350 DEG C, and the time of roasting is 24h;
Step 2, by carrier described in 1g step 1 be placed in 10mL ammonium metatungstate solution (tungstenic 0.08g) stir dipping 6h, then the carrier after dipping is taken out, 100 DEG C of dry 24h, again under air atmosphere by dried carrier roasting, obtain the support type tungsten-based catalyst 8W/23Si/Al that 1-butylene disproportionation is prepared propylene; The temperature of described roasting is 350 DEG C, and roasting time is 8h.
Adopt the catalyst 1-butylene disproportionation of the present embodiment to prepare propylene, method is: 0.2g catalyst is packed in the U-shaped reactor that volume is 1mL, to the argon gas that passes into 50mL/min in reactor, reactor is warming up to 550 DEG C, after insulation 2h, lower the temperature, when question response actuator temperature is down to 80 DEG C, argon gas is switched to 1-butylene (99.5%), under normal pressure (0.1MPa), carry out the reaction of 1-butylene disproportionation, material quality air speed is 0.6h
-1, product, by gas-chromatography on-line analysis, is got a sample analysis for every 1 hour, and reaction initial activity is got the mean value in 3 hours, and reaction result is in table 1.
Embodiment 3
The support type tungsten-based catalyst of the present embodiment comprises carrier and is carried on the active component on carrier, and described carrier is γ-Al of deposition Si
2o
3, the deposition of Si is γ-Al
2o
315% of quality, the oxide that described active component is tungsten, the load capacity of tungsten is 4% of carrier quality.
The preparation method of the support type tungsten-based catalyst of the present embodiment is:
Step 1, the 3-aminopropyl trimethoxysilane of siliceous 0.15g (Aldrich, 99.9%) is dissolved in absolute methanol and obtains siliceous organic solution, by 1g γ-Al
2o
3be placed in siliceous organic solution and stir dipping 1h, then by the γ-Al after dipping
2o
3take out, 100 DEG C of dry 24h, then under air atmosphere by dried γ-Al
2o
3roasting, obtains carrier 15Si/Al; The temperature of described roasting is 750 DEG C, and the time of roasting is 12h;
Step 2, by carrier described in 1g step 1 be placed in 10mL ammonium metatungstate solution (tungstenic 0.04g) stir dipping 3h, then the carrier after dipping is taken out, 100 DEG C of dry 24h, again under air atmosphere by dried carrier roasting, obtain the support type tungsten-based catalyst 4W/15Si/Al that 1-butylene disproportionation is prepared propylene; The temperature of described roasting is 750 DEG C, and roasting time is 4h.
Adopt the catalyst 1-butylene disproportionation of the present embodiment to prepare propylene, method is: 0.2g catalyst is packed in the U-shaped reactor that volume is 1mL, to the argon gas that passes into 50mL/min in reactor, reactor is warming up to 550 DEG C, after insulation 2h, lower the temperature, when question response actuator temperature is down to 200 DEG C, argon gas is switched to 1-butylene (99.5%), under normal pressure (0.1MPa), carry out the reaction of 1-butylene disproportionation, material quality air speed is 1.2h
-1, product, by gas-chromatography on-line analysis, is got a sample analysis for every 1 hour, and reaction initial activity is got the mean value in 3 hours, and reaction result is in table 1.
Embodiment 4
The support type tungsten-based catalyst of the present embodiment comprises carrier and is carried on the active component on carrier, and described carrier is γ-Al of deposition Si
2o
3, the deposition of Si is γ-Al
2o
325% of quality, the oxide that described active component is tungsten, the load capacity of tungsten is 2% of carrier quality.
The preparation method of the support type tungsten-based catalyst of the present embodiment is:
Step 1, the APTES of siliceous 0.25g (Aldrich, 99.9%) is dissolved in 20mL absolute ethyl alcohol and obtains siliceous organic solution, by 1g γ-Al
2o
3be placed in siliceous organic solution and stir dipping 1h, then by the γ-Al after dipping
2o
3take out, 100 DEG C of dry 24h, then under air atmosphere by dried γ-Al
2o
3roasting, obtains carrier 25Si/Al; The temperature of described roasting is 600 DEG C, and the time of roasting is 15h;
Step 2, by carrier described in 1g step 1 be placed in 10mL ammonium tungstate solution (tungstenic 0.02g) stir dipping 3h, then the carrier after dipping is taken out, 100 DEG C of dry 24h, again under air atmosphere by dried carrier roasting, obtain the support type tungsten-based catalyst 2W/25Si/Al that 1-butylene disproportionation is prepared propylene; The temperature of described roasting is 500 DEG C, and roasting time is 6h.
Adopt the catalyst 1-butylene disproportionation of the present embodiment to prepare propylene, method is: 0.1g catalyst is packed in the U-shaped reactor that volume is 1mL, to the argon gas that passes into 50mL/min in reactor, reactor is warming up to 550 DEG C, after insulation 2h, lower the temperature, when question response actuator temperature is down to 200 DEG C, argon gas is switched to 1-butylene (99.5%), under normal pressure (0.1MPa), carry out the reaction of 1-butylene disproportionation, material quality air speed is 1.2h
-1, product, by gas-chromatography on-line analysis, is got a sample analysis for every 1 hour, and reaction initial activity is got the mean value in 3 hours, and reaction result is in table 1.
Embodiment 5
The support type tungsten-based catalyst of the present embodiment comprises carrier and is carried on the active component on carrier, and described carrier is γ-Al of deposition Si
2o
3, the deposition of Si is γ-Al
2o
310% of quality, the oxide that described active component is tungsten, the load capacity of tungsten is 10% of carrier quality.
The preparation method of the support type tungsten-based catalyst of the present embodiment is:
Step 1, the 3-aminopropyl trimethoxysilane of siliceous 0.1g (Aldrich, 99.9%) is dissolved in absolute ethyl alcohol and obtains siliceous organic solution, by 1g γ-Al
2o
3be placed in siliceous organic solution and stir dipping 1h, then by the γ-Al after dipping
2o
3take out, 100 DEG C of dry 24h, then under air atmosphere by dried γ-Al
2o
3roasting, obtains carrier 10Si/Al; The temperature of described roasting is 350 DEG C, and the time of roasting is 24h;
Step 2, by carrier described in 1g step 1 be placed in 10mL ammonium tungstate solution (tungstenic 0.1g) stir dipping 6h, then the carrier after dipping is taken out, 100 DEG C of dry 24h, again under air atmosphere by dried carrier roasting, obtain the support type tungsten-based catalyst 10W/10Si/Al that 1-butylene disproportionation is prepared propylene; The temperature of described roasting is 500 DEG C, and roasting time is 4h.
Adopt the catalyst 1-butylene disproportionation of the present embodiment to prepare propylene, method is: 0.5g catalyst is packed in the U-shaped reactor that volume is 1mL, to the argon gas that passes into 50mL/min in reactor, reactor is warming up to 550 DEG C, after insulation 2h, lower the temperature, when question response actuator temperature is down to 200 DEG C, argon gas is switched to 1-butylene (99.5%), under normal pressure (0.1MPa), carry out the reaction of 1-butylene disproportionation, material quality air speed is 1.2h
-1, product, by gas-chromatography on-line analysis, is got a sample analysis for every 1 hour, and reaction initial activity is got the mean value in 3 hours, and reaction result is in table 1.
The catalytic reaction result of table 1 embodiment 1-5
As can be seen from Table 1, support type tungsten-based catalyst of the present invention can be prepared propylene by successful catalysis 1-butylene disproportionation, and the conversion ratio of 1-butylene can reach 71.7mol%, and the productive rate of propylene can reach 20.9mol%.
Comparative example 1
Take a certain amount of ammonium metatungstate and SiO
2in 20mL water, stir at normal temperatures 5h(wet impregnation), 100 DEG C dry 24 hours, and in air atmosphere 550 DEG C of roasting 8h, obtain W weight content and be 6% support type tungsten-based catalyst 6W/SiO
2.
Comparative example 2
Take a certain amount of ammonium metatungstate and γ-Al
2o
3in 20mL water, stir at normal temperatures 5h(wet impregnation), 100 DEG C dry 24 hours, and in air atmosphere 550 DEG C of roasting 8h, obtain W weight content and be 6% support type tungsten-based catalyst 6W/Al
2o
3.
Comparative example 3
Take a certain amount of ammonium metatungstate and commodity SiO
2-Al
2o
3in 20mL water, stir at normal temperatures 5h(wet impregnation), 100 DEG C dry 24 hours, and in air atmosphere 550 DEG C of roasting 8h, obtain W weight content and be 6% support type tungsten-based catalyst 6W/SiO
2-Al
2o
3.
Prepare respectively 6W/10Si/Al, 6W/25Si/Al, 2W/20Si/Al, 4W/20Si/Al, 8W/20Si/Al and 10W/20Si/Al catalyst according to the method for embodiment 1, adopt 6W/10Si/Al, 6W/25Si/Al, 2W/20Si/Al, 4W/20Si/Al, 8W/20Si/Al and the 10W/20Si/Al catalyst of comparative example 1-3 and preparation to prepare propylene according to the catalysis process catalysis 1-butylene disproportionation of embodiment 1, the results are shown in Table 2.
Table 21-butylene disproportionation reactivity worth
As can be seen from Table 2, with 6W/Al
2o
3, 6W/SiO
2and 6W/SiO
2-Al
2o
3catalyst is compared, and tungsten oxide loads on the γ-Al that has deposited Si
2o
3above in the time of 180 DEG C of reactions, activity is high, and productivity of propylene is the highest can reach 20.9mol%; Using 20Si/Al as carrier loaded tungsten oxide, in the time that W content increases, disproportionation is active to be improved in addition, and in the time that W content reaches 6wt%, productivity of propylene is the highest, and continuing increases W content, and productivity of propylene declines on the contrary; Si is deposited on γ-Al
2o
3on content also can affect 1-butylene disproportionation reactivity, in the time that Si content is increased to 20wt% from 10wt%, productivity of propylene increases and in the time that Si content is 20wt%, reaches maximum, continues to increase that Si content disproportionation is active declines, productivity of propylene reduces.
The above; it is only preferred embodiment of the present invention; not the present invention is done to any restriction, every any simple modification of above embodiment being done according to invention technical spirit, change and equivalent structure change, and all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. 1-butylene disproportionation is prepared a support type tungsten-based catalyst for propylene, comprises carrier and is carried on the active component on carrier, it is characterized in that, described carrier is γ-Al of deposition Si
2o
3, the deposition of Si is γ-Al
2o
310%～25% of quality, the oxide that described active component is tungsten, the load capacity of tungsten is 2%～10% of carrier quality.
2. 1-butylene disproportionation according to claim 1 is prepared the support type tungsten-based catalyst of propylene, it is characterized in that, the deposition of described Si is γ-Al
2o
315%～23% of quality, the load capacity of tungsten is 4%～8% of carrier quality.
3. 1-butylene disproportionation according to claim 2 is prepared the support type tungsten-based catalyst of propylene, it is characterized in that, the deposition of described Si is γ-Al
2o
320% of quality, the load capacity of tungsten is 6% of carrier quality.
4. a method of preparing support type tungsten-based catalyst as described in claim 1,2 or 3, is characterized in that, the method comprises the following steps:
Step 1, silicon-containing compound is dissolved in organic solvent and obtains siliceous organic solution, adopt described siliceous organic solution dipping γ-Al
2o
3, then by the γ-Al after dipping
2o
3take out dry, then under air atmosphere by dried γ-Al
2o
3roasting, obtains carrier; The temperature of described roasting is 350 DEG C～750 DEG C, and the time of roasting is 12h～24h;
Step 2, adopt carrier described in soluble tungsten salt solution impregnation step 1, then the carrier after dipping is taken out dry, then under air atmosphere by dried carrier roasting, obtain the support type tungsten-based catalyst that 1-butylene disproportionation is prepared propylene; The temperature of described roasting is 350 DEG C～750 DEG C, and roasting time is 4h～8h.
5. method according to claim 4, is characterized in that, silicon-containing compound described in step 1 is APTES or 3-aminopropyl trimethoxysilane, and described organic solvent is ethanol or methyl alcohol.
6. method according to claim 4, is characterized in that, the salt of soluble tungsten described in step 2 is ammonium metatungstate or ammonium tungstate.
7. method according to claim 4, is characterized in that, the time of flooding described in step 2 is 3h～6h.
One kind as described in claim 1,2 or 3 support type tungsten-based catalyst prepare the application in propylene at catalysis 1-butylene disproportionation.
9. application according to claim 8, is characterized in that, catalytic condition is: 80 DEG C～200 DEG C of reaction temperatures, and reaction pressure 0.1MPa, reactor feed gas is 1-butylene, 1-butylene weight space velocity is 0.6h
-1～2.4h
-1.
10. application according to claim 8, is characterized in that, the consumption of support type tungsten-based catalyst is every 0.1g～0.5g support type tungsten-based catalyst for 1mL reactor.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113351206A (en) * | 2020-03-06 | 2021-09-07 | 中国科学院大连化学物理研究所 | Active material and preparation method and application thereof |
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