CN100441295C - Supported catalyst for preparing propylene by propane selective oxidization and its prepn. - Google Patents
Supported catalyst for preparing propylene by propane selective oxidization and its prepn. Download PDFInfo
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- CN100441295C CN100441295C CNB2007100086407A CN200710008640A CN100441295C CN 100441295 C CN100441295 C CN 100441295C CN B2007100086407 A CNB2007100086407 A CN B2007100086407A CN 200710008640 A CN200710008640 A CN 200710008640A CN 100441295 C CN100441295 C CN 100441295C
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Abstract
The invention relates to a method for preparing acrolein load catalyst via propane selective oxidization and sol-gel method, wherein the catalyst is MoVTeNbO/SiO2, while Mo is 0.61-3.68%, V is 0.18-1.10%, Te is 0.14-0.85%, Nb is 0-0.37%, and Si is 94-99%. And the preparation comprises that preparing ethyl silicate, lower alcohol and water into solution I, preparing ammonium vanadate, ammonium molybdate and telluric acid into solution II, preparing oxalic acid niobium into solution III, adding II and III into I, adjusting pH value, heating in water bath to obtain sol, aging into gel, drying, baking to obtain catalyst. The invention has simple process, high repeatability, stability and mechanical strength, large specific surface area, high catalysis property and 18.3% acrolein recycle rate.
Description
Technical field
The present invention relates to a kind of supported catalyst for preparing propylene by propane selective oxidization.
Background technology
Low-carbon alkanes extensively is present in natural gas, oil liquefied gas and the refinery gas, main as fuel, service efficiency is lower, caused a large amount of and unnecessary energy waste. low-carbon alkanes face the research that oxygen is catalytically conveted to important industrial chemicals aspects such as alkene and oxygen-bearing organic matter, for utilizing resourceful natural gas and coal bed gas as the non-oil base energy and industrial chemicals, under current international energy, particularly oil supply and demand situation with keen competition, has the important strategic meaning.
Methacrylaldehyde and acrylic acid are important Organic Chemicals, has purposes widely, methacrylaldehyde can be used as the raw material of chemical products such as acrylic acid synthesizing, methionine, glycerine and pentanediol, and industrial employing propylene is a raw material selective oxidation acrolein, and methacrylaldehyde further is oxidized to acrylic acid again.Propylene is mainly derived from the accessory substance of oil base hydrocarbon pyrolysis system ethene, and its price is higher, is 3～4 times of propane, along with the minimizing day by day of petroleum resources, adds that propylene was becoming tight because of the day that serves many purposes, and the gap on this price will further enlarge.Therefore, replacing propylene with propane is that raw material selective oxidation acrolein can shorten process conditions, cuts down the consumption of energy, and reduces the production cost of methacrylaldehyde greatly, has potential great economic benefit.
At present the preparing propylene by propane selective oxidization catalyst of report mainly is multi-component composite oxide catalysts, generally contain V or (with) the Mo element, as U.S. Pat 4472314, US6809219, US6541664; Europe patent EP1642879; Japan Patent JP2005298376; Chinese patent CN1159960A, CN1500553A.Moro-oka etc. (Moro-oka etal.Chem.Lett., 1989,531) adopt Ag
0.01Bi
0.85V
0.45Mo
0.55O
4Catalyst can obtain 7.8% methacrylaldehyde productive rate.Shishido etc. (Shishido et al.Catal.Today, 2001,71:77) adopt the MoVSbO catalyst, conversion of propane was 6.8% when reaction temperature was 430 ℃, the methacrylaldehyde selectivity is 20.8%.In patent of having reported or the document some catalyst exist difficultly repeat, mechanical strength is relatively poor, the shortcoming that the methacrylaldehyde one-pass yield is lower has limited this method in industrial application.
Summary of the invention
The object of the present invention is to provide have supported catalyst for preparing propylene by propane selective oxidization of preferable catalytic performance and preparation method thereof a kind of the preparation by sol-gel process.
Its general formula of supported catalyst for preparing propylene by propane selective oxidization of the present invention can be expressed as MoVTeNbO/SiO
2, the molar content of each component is respectively: Mo is 0.61%～3.68%, and V is 0.18%～1.10%, and Te is 0.14%～0.85%, and Nb is 0～0.37%, Si is 94%～99%.
The preparation method of supported catalyst for preparing propylene by propane selective oxidization of the present invention may further comprise the steps:
1) according to the constituent content of catalyst, ethyl orthosilicate, lower alcohol and distilled water are at room temperature stirred by proportioning, be mixed with solution I, wherein ethyl orthosilicate: lower alcohol: the volume ratio of distilled water is 1: 0.5～3: 2; Described lower alcohol is an ethanol, ethylene glycol, isopropyl alcohol, preferred ethylene glycol;
2) ammonium metavanadate, ammonium molybdate, telluric acid are mixed with solution II by the component mol ratio under 50～100 ℃;
3) by the component mol ratio niobium oxalate is dissolved in distilled water under room temperature and is mixed with solution III;
4) solution II and solution III are added in the solution I, mixing the back is 2～12 with 1%～5% weak aqua ammonia or rare nitric acid regulator solution pH value of 0.2%～1%, in 50～120 ℃ water-bath, be heated to then and form transparent colloidal sol, move to 20～50 ℃ of following ageings to forming gel;
5) in 80～150 ℃ of drying 4～12h, be warming up to 400～650 ℃ of roasting 2～6h in 2～10 ℃/min then, promptly get required catalyst.
The activity of such catalysts evaluation response carries out in the fixed bed quartz tube reactor of continuous feed, volume at propane and air is 0.2, reaction temperature is 560 ℃, the reaction gas air speed is under the reaction condition of 3000ml/min, obtaining conversion of propane is 39.9%, the methacrylaldehyde selectivity is 45.9%, and the methacrylaldehyde yield can reach 18.3%.
The present invention has following outstanding advantage: 1) preparation method is simple, good reproducibility; 2) catalyst need not any processing before reaction, and technology is simple, and is easy to operate; 3) catalyst is a carrier with the silica of sol-gel process preparation, and it is big to have specific area, and mechanical strength is strong, the advantage of good stability; 4) surface active composition concentration is lower, can realize preferably that the dispersion of catalyst activity component on carrier separates with the activated centre; 5) under optimized reaction conditions, catalyst also has higher methacrylaldehyde selectivity when having higher conversion of propane.
The specific embodiment
Below by the further sets forth in detail the present invention of embodiment.
Embodiment 1
(1) Preparation of Catalyst
With the 40ml ethyl orthosilicate, 80ml ethylene glycol and 80ml distilled water at room temperature stir, be mixed with solution I, with the 0.353g ammonium molybdate, 0.070g ammonium metavanadate and 0.106g telluric acid are dissolved in the 20ml distilled water in 80 ℃ and are mixed with solution II, again the 0.119g niobium oxalate is dissolved in 2ml distilled water in room temperature and is mixed with solution III, constantly stir down and respectively solution II and solution III are added in the solution I, mixing the back is 6 with weak aqua ammonia regulator solution pH value, in 70 ℃ water-bath, be heated to then and form transparent colloidal sol, move under the room temperature ageing to forming gel.Sample behind 110 ℃ of dry 10h is warming up to 600 ℃ of roasting 2h in the speed of 2 ℃/min can obtains catalyst MoVTeNbO/SiO
2
(2) appreciation condition
Catalyst amount is 0.2g, places the fixed bed quartz tube reactor (internal diameter is 6mm) of continuous feed, at C
3H
8/ O
2//N
2=1/1/4,560 ℃ of reaction temperatures, reaction gas air speed are 3000mlg
-1H
-1Reaction condition under carry out catalytic performance test, reaction result sees Table 1.By reaction evaluating result (referring to table 1) as can be seen, adopt the made catalyst of the present invention to have preparing propylene by propane selective oxidization productive rate preferably.
Embodiment 2:
In embodiment 1, with the 80ml ethylene glycol in the Preparation of Catalyst (1) change into the 20ml isopropyl alcohol present embodiment.The performance evaluation of catalyst the results are shown in Table 1.
Embodiment 3:
In embodiment 1, with the 80ml ethylene glycol in the Preparation of Catalyst (1) change into 40ml ethanol present embodiment.
Embodiment 4:
In embodiment 1, with the 80ml ethylene glycol in the Preparation of Catalyst (1) change into 120ml ethylene glycol present embodiment.
Embodiment 5:
In embodiment 1, with the regulator solution pH value in the Preparation of Catalyst (1) be 6 change into rare nitric acid regulator solution pH value of 1% be 2 present embodiment.
Embodiment 6:
In embodiment 1, with the regulator solution pH value in the Preparation of Catalyst (1) be 6 change into regulator solution pH value be 8 present embodiment.
Embodiment 7:
In embodiment 1, with the regulator solution pH value in the Preparation of Catalyst (1) be 6 change into the pH value be 12 present embodiment.
Embodiment 8:
In embodiment 1, with the speed of 2 ℃/min in the Preparation of Catalyst (1) heat up the speed that changes 5 ℃/min into heat up present embodiment.
Embodiment 9:
In embodiment 1, with the speed of 2 ℃/min in the Preparation of Catalyst (1) heat up the speed that changes 10 ℃/min into heat up present embodiment.
Embodiment 10:
In embodiment 1, change the 0.119g niobium oxalate in the Preparation of Catalyst (1) into 0g, present embodiment.
Embodiment 11:
In embodiment 1, change the 0.353g ammonium molybdate in the Preparation of Catalyst (1) into the 0.177g ammonium molybdate, the 0.070g ammonium metavanadate changes the 0.035g ammonium metavanadate into, and the 0.106g telluric acid changes the 0.053g telluric acid into, 0.119g niobium oxalate changes the 0.060g niobium oxalate into, present embodiment.
Embodiment 12:
In embodiment 1, change the 0.353g ammonium molybdate in the Preparation of Catalyst (1) into the 0.529g ammonium molybdate, the 0.070g ammonium metavanadate changes the 0.105g ammonium metavanadate into, and the 0.106g telluric acid changes the 0.159g telluric acid into, 0.119g niobium oxalate changes the 0.178g niobium oxalate into, present embodiment.
Embodiment 13:
In embodiment 1, change the 0.353g ammonium molybdate in the Preparation of Catalyst (1) into the 1.059g ammonium molybdate, the 0.070g ammonium metavanadate changes the 0.210g ammonium metavanadate into, and the 0.106g telluric acid changes the 0.318g telluric acid into, 0.119g niobium oxalate changes the 0.357g niobium oxalate into, present embodiment.
The preparing propylene by propane selective oxidization reactivity worth evaluation result of table 1 catalyst
| Embodiment | Conversion of propane (%) | Methacrylaldehyde productive rate (%) |
| 1 | 39.9 | 18.3 |
| 2 | 35.7 | 8.8 |
| 3 | 40.8 | 15.0 |
| 4 | 41.5 | 17.8 |
| 5 | 40.4 | 15.9 |
| 6 | 39.8 | 13.2 |
| 7 | 37.6 | 10.9 |
| 8 | 42.4 | 16.8 |
| 9 | 40.9 | 12.5 |
| 10 | 39.1 | 17.2 |
| 11 | 21.0 | 9.4 |
| 12 | 41.6 | 16.1 |
| 13 | 41.4 | 7.5 |
Claims (3)
1. the preparation method of supported catalyst for preparing propylene by propane selective oxidization, the general formula of described supported catalyst for preparing propylene by propane selective oxidization is expressed as MoVTeNbO/SiO
2, the molar content of each component is respectively that Mo is 0.61%～3.68%, and V is 0.18%～1.10%, and Te is 0.14%～0.85%, and Nb is 0～0.37%, Si is 94%～99%;
It is characterized in that described preparation method may further comprise the steps:
1) according to the constituent content of catalyst, ethyl orthosilicate, lower alcohol and distilled water are at room temperature stirred, be mixed with solution I, wherein ethyl orthosilicate: lower alcohol: the distilled water volume ratio is 1: 0.5～3: 2, described lower alcohol is an ethanol, ethylene glycol or isopropyl alcohol;
2) ammonium metavanadate, ammonium molybdate and telluric acid are mixed with solution II by the component mol ratio under 50～100 ℃;
3) by the component mol ratio niobium oxalate is dissolved in distilled water under room temperature and is mixed with solution III;
4) constantly stir down, respectively solution II and solution III are added in the solution I, mixing back regulator solution pH value is 2～12, is heated to formation colloidal sol then in 50～120 ℃ water-bath, moves to 20～50 ℃ of following ageings to forming gel;
5) in 80～150 ℃ of drying 4～12h, be warming up to 400～650 ℃ of roasting 2～6h in 2～10 ℃/min then, promptly get required catalyst.
2. the preparation method of supported catalyst for preparing propylene by propane selective oxidization as claimed in claim 1 is characterized in that described lower alcohol is an ethylene glycol.
3. the preparation method of supported catalyst for preparing propylene by propane selective oxidization as claimed in claim 1, the pH value that it is characterized in that solution in the step 4) is regulated with 1%～5% weak aqua ammonia or rare nitric acid of 0.2%～1%.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103769172B (en) * | 2012-10-24 | 2016-03-02 | 中国石油化工股份有限公司 | A kind of preparation method of propane partial oxidation acrolein catalyst |
| CN103285888B (en) * | 2013-04-18 | 2016-03-16 | 沈阳化工大学 | A kind of Catalysts and its preparation method preparing acrylic acid reaction for propylene oxidation step |
| CN108114730A (en) * | 2016-11-26 | 2018-06-05 | 中国科学院大连化学物理研究所 | Molybdenum-vanadium-tellurium-niobium catalytic agent composition |
| CN112439441B (en) * | 2019-09-05 | 2023-03-21 | 中石油吉林化工工程有限公司 | Preparation method of catalyst for preparing acrylic acid by acrolein oxidation |
| CN113492017A (en) * | 2020-04-08 | 2021-10-12 | 中国石油天然气股份有限公司 | Supported catalyst for preparing acrylic acid by catalytic oxidation of propane, and preparation method and application thereof |
| CN113813989B (en) * | 2020-06-18 | 2023-05-26 | 中国石油天然气股份有限公司 | Process for preparing acrolein |
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| JP2002292283A (en) * | 2001-04-02 | 2002-10-08 | Mitsubishi Chemicals Corp | Compound metal oxide catalyst and method for gaseous phase catalytic oxidizing reaction using the same |
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Patent Citations (4)
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| JP2002292283A (en) * | 2001-04-02 | 2002-10-08 | Mitsubishi Chemicals Corp | Compound metal oxide catalyst and method for gaseous phase catalytic oxidizing reaction using the same |
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