CN103285890A - Cr-doped catalyst for preparing acrylic acid by catalytically oxidizing propane and preparation method of Cr-doped catalyst - Google Patents
Cr-doped catalyst for preparing acrylic acid by catalytically oxidizing propane and preparation method of Cr-doped catalyst Download PDFInfo
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- CN103285890A CN103285890A CN2013101980799A CN201310198079A CN103285890A CN 103285890 A CN103285890 A CN 103285890A CN 2013101980799 A CN2013101980799 A CN 2013101980799A CN 201310198079 A CN201310198079 A CN 201310198079A CN 103285890 A CN103285890 A CN 103285890A
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- propane
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- catalytic oxidation
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Abstract
The invention relates to a modified catalyst for preparing acrylic acid by catalytically oxidizing propane, and in particular relates to a catalyst containing Mo, V, Te and Nb elements as active ingredients and metallic oxide with Cr element properly added, and a preparation method of the catalyst. The modified catalyst for preparing acrylic acid by catalytically oxidizing propane is an unsupported multi-ingredient metallic oxide and adopts the Mo, V, Te and Nb elements as the main active ingredients, and proper Cr element is added; the ingredient content in molar ratio is that CrxMo7.82V1.18Te0.94Nb10y (x ranges from 0 to 0.01). The catalyst is suitably used for preparing acrylic acid by selectively oxidizing propane; no processing is done before reaction, so that the process is simple, and the operation is convenient; the raw gas is basically composed of propane/oxygen at a (volume) ratio of 0.4 to 0.7; and the reaction is carried out at 380 to 420 DEG C at normal pressure along with the inlet flow of 0.3 to 0.65ml/h and air speed of 1,200 to 4,000ml/(g.h).
Description
Technical field
The present invention relates to a kind of catalytic oxidation of propane and produce acrylic acid modified catalyst, what be specifically related to is to contain with Mo, V, Te, Nb element to be the activity of such catalysts component, suitably to add the Catalysts and its preparation method of the metal oxide of Cr element.
Background technology
Propane is a kind of low chain saturated alkane, is one of main component of natural gas, liquefied petroleum gas, coal bed gas, and content on earth is abundant relatively.But the natural gas resource that the current overwhelming majority has been exploited mainly utilizes and acts as a fuel, and is then less relatively for the natural gas resource that is chemically converted into the high added value compound, is not fully utilized.Acrylic acid is the broad-spectrum organic intermediate of a class, is widely used in industries such as coating, chemical fibre, weaving, light industry, and it is mainly used to produce esters of acrylic acid industrial.Acrylic acid and ester are the very high petrochemical industry deep processed products of added value, can a step process many fine chemical products.In addition, acrylic acid can be used for producing Sodium Polyacrylate, polyacrylic acid quaternary ammonium salt and copolymer thereof, can be used as various dispersants, flocculant and thickener.Polypropylene and acrylic copolymer also can be used for producing super absorbent resin and help washing agent, provide bright prospect for expanding the acrylic acid purposes, and have promoted the acrylic acid industrial expansion.
It is the technical process such as Reppe method, acrylonitrile hydrolysis method, cyanoethanol method and oxidation of propylene of raw material that the acrylic acid industrial production has experienced with acetylene and CO, first three methods is all higher with certain toxicity and cost, replaced by the direct oxidation of propylene method gradually, propylene gas phase two-step oxidation rule is to produce acrylic acid unique channel at present.But the propylene main source is the byproduct of petroleum cracking ethene processed and the byproduct of catalytically cracked gasoline, and because the supply day that serves many purposes is becoming tight, price is far above propane.If can replace propylene with propane cheap and easy to get is raw material, from propane catalytic oxidation one step generation acrylic acid, cost of material will reduce greatly so.So, prepare acrylic acid by selective oxidation of propane and will produce huge economic benefit.
The catalytic oxidation of propane of studying is at present produced in acrylic acid catalyst, be some composite metal oxides mostly, mainly based on MoVTe(Sb) Nb, but that different researchers prepares the acrylic acid yield difference of MoVTeNb catalyst is very big, and MIT has reported and has developed MoVTeNbO
xThe yield of System Catalyst reaches 48%, and the acrylic acid yield of domestic report all is lower than this level.
Summary of the invention
The object of the invention provides a kind of energy catalytic oxidation of propane prepare acrylic acid Catalysts and its preparation method, at the MoVTeNbO of certain active component ratio
xProper C r element in the System Catalyst makes acrylic acid selective and yield improve greatly under certain reaction condition, and the high selectivity of acrylic acid can be near 80%, and productive rate can reach more than 50%, above present relevant report both domestic and external.
Concrete preparation method of the present invention is as follows:
The present invention is that a kind of catalytic oxidation of propane is produced acrylic acid modified catalyst, is many components metal oxide of non-loading type, is the main active component of catalyst with Mo, V, Te, Nb element, adds The addition of C r element, and its component content mol ratio is: Cr
xMo
7.82V
1.18Te
0.94Nb
1O
y(0≤x≤0.01).
As further improvement, Mo content of the present invention is mol ratio 7.82.
As further improvement, V content of the present invention is mol ratio 1.18.
As further improvement, Te content of the present invention is mol ratio 0.94.
As further improvement, Nb content of the present invention is mol ratio 1.
As further improvement, Cr micronutrient levels of the present invention is mol ratio 0 ~ 0.01.
The present invention a kind ofly produces acrylic acid modified Preparation of catalysts method according to the described catalytic oxidation of propane of claim 1, adopt dissolving-coprecipitation: press certain mol proportion preparation molybdate, metavanadate, telluric acid, niobium oxalate and chromium nitrate solution, mix back constant temperature evaporate to dryness, 150 ℃ and 600 ℃ of each roastings are 2 hours under blanket of nitrogen.
The present invention a kind ofly is applicable to that according to the described catalyst of claim 1 catalytic oxidation of propane produces acrylic acid reaction, the base stock of described reaction is propane and oxygen, reaction condition is that unstripped gas basic composition is: the volume ratio of propane and oxygen is 0.4 ~ 0.7, reaction temperature is 380 ~ 420 ℃, carry out under the normal pressure, flow of inlet water is 0.3 ~ 0.65 ml/h, and air speed is 1200 ~ 4000 ml/ (g.h).
Beneficial effect of the present invention is as follows:
Catalyst of the present invention is applicable to that the propane selective oxidation prepares acrylic acid, need not to carry out any processing before reaction, and technology is simple, easy to operate.Unstripped gas basic composition is propane/oxygen (volume) than being 0.4 ~ 0.7, and reaction temperature is 380 ~ 420 ℃, carries out under the normal pressure, and flow of inlet water is 0.3 ~ 0.65 ml/h, and air speed is 1200 ~ 4000 ml/ (g. h).
The specific embodiment
Catalytic oxidation of propane provided by the invention prepares acrylic acid catalyst, and its general formula can be expressed as:
Cr
xMo
7.82V
1.18Te
0.94Nb
1O
y（0≤x≤0.01）
Catalyst adopts the preparation of dissolving-coprecipitation: each component is prepared molybdate, metavanadate, telluric acid and niobium oxalate solution and chromium nitrate solution according to the above ratio, mix the back in 80 ℃ of evaporates to dryness and drying, 150 ℃ and 600 ℃ of roastings 2 hours under blanket of nitrogen again can obtain required catalyst.Below by specific embodiment technical scheme of the present invention is described in further detail.
Embodiment 1
Dissolving-coprecipitation prepares catalyst of the present invention:
Raw material: ammonium molybdate: (NH
4)
6Mo
7O
244H
2O
Ammonium metavanadate: NH
4VO
3
Telluric acid: H
2TeO
4H
2O
Niobium oxalate: C
12H
7NbO
24
Chromic nitrate: Cr (NO
3)
3
Press catalyst (Mo
7.82V
1.18Te
0.94NbO
28.9) ratio, with ammonium molybdate, ammonium metavanadate, the mixture of telluric acid add the lysed niobium oxalate solution of 20 ml again 80 ℃ of stirring and dissolving with 20 ml distilled water, add then behind a certain proportion of chromium nitrate solution at 80 ℃ of evaporates to dryness and dry 12 h.Under nitrogen protection, can obtain this catalyst in 2 hours 150 ℃ and 600 ℃ of each roastings respectively.
Embodiment 2
The catalytic perfomance of different Cr content catalyst:
Method with reference to embodiment 1, in No. 1 beaker, add 3.5310 gram ammonium molybdates, 0.3530 gram ammonium metavanadate, 0.5520 gram telluric acid and 20 ml water make it 80 ℃ of dissolvings, add 1.6063 gram niobium oxalates and 20 ml distilled water make it 80 ℃ of dissolvings at No. 2 beakers, drips of solution in No. 2 beakers is added in No. 1 beaker, forms 4 component mixed liquors.Add 2.557 * 10 respectively
-3The chromium nitrate solution of mol/l is 2 ml, 4 ml, 6 ml, 8 ml and 10 ml, continues adding distil water to 80 ml, at 80 ℃ of evaporates to dryness and dry 12 h.Again under nitrogen protection respectively 150 ℃ and 600 ℃ of roastings 2 hours, can make the composite metal oxide that contains many components.
Catalytic reaction condition: propane/oxygen=1/2, reaction temperature are 390 ℃, carry out under the normal pressure, and air speed is 1922 ml/ (g.h), and the flow of water is 0.3 ml/h.Water gasifies afterwards and propane and oxygen mix through 170 ℃ heating tube.Be reflected in the fixed bed quartz tube reactor of continuous feed and carry out.The evaluation result of catalyst such as following table:
Table 1
Embodiment 3
The catalytic perfomance of differential responses temperature:
Preparation of Catalyst: with reference to the method for embodiment 1 with embodiment 2, make the Cr that contains element Cr
0.002Mo
7.82V
1.18Te
0.94Nb
1O
yThe composite metal oxide of many components.
Reaction condition: propane/oxygen=1/2, reaction temperature are 390 ~ 420 ℃, carry out under the normal pressure, and air speed is 3197 ml/ (g.h), and the flow of water is 0.5 ml/h.Water is through 170 ℃ heating tube gasification back and propane and oxygen mix, is reflected in the fixed bed quartz tube reactor of continuous feed to carry out.The appraisal result of catalyst such as following table:
Table 2
Embodiment 4
The catalytic perfomance of different air speeds:
Preparation of Catalyst: with reference to the method for embodiment 1 with embodiment 2, make the Cr that contains element Cr
0.002Mo
7.82V
1.18Te
0.94Nb
1O
yThe composite metal oxide of many components.
Examination condition: propane/oxygen=1/2.Reaction temperature is 400 ℃, carries out under the normal pressure.Water gasifies afterwards and propane and oxygen mix through 170 ℃ heating tube.Be reflected in the fixed bed quartz tube reactor of continuous feed and carry out.Reactivity worth appraisal result such as the following table of catalyst under the different air speeds:
Table 3
Embodiment 5
The catalytic perfomance of different inflows:
Preparation of Catalyst: with reference to the method for embodiment 1 with embodiment 2, make the Cr that contains element Cr
0.002Mo
7.82V
1.18Te
0.94Nb
1O
yThe composite metal oxide of many components.
Examination condition: propane/oxygen=1/2.Reaction temperature is 400 ℃, carries out under the normal pressure.Water is through 170 ℃ heating tube gasification back and propane and oxygen mix, is reflected in the fixed bed quartz tube reactor of continuous feed to carry out.Reactivity worth appraisal result such as the following table of catalyst under the different inflows:
Table 4
Embodiment 6
The catalytic perfomance of different material gas ratio:
Preparation of Catalyst: with reference to the method for embodiment 1 with embodiment 2, make the Cr that contains element Cr
0.002Mo
7.82V
1.18Te
0.94Nb
1O
yThe composite metal oxide of many components.
Examination condition: propane/oxygen=2/5 ~ 2/3.Reaction temperature is 400 ℃, carries out under the normal pressure, and air speed is 3197 ml/ (g.h), and the flow of water is 0.5 ml/h.Water is through 170 ℃ heating tube gasification back and propane and oxygen mix, is reflected in the fixed bed quartz tube reactor of continuous feed to carry out.The appraisal result of catalyst such as following table:
Table 5
What more than enumerate only is part specific embodiment of the present invention; obviously, the invention is not restricted to above embodiment, many distortion can also be arranged; all distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (8)
1. a catalytic oxidation of propane is produced acrylic acid modified catalyst, is many components metal oxide of non-loading type, it is characterized in that with Mo, V, Te, Nb element be the main active component of catalyst, adds The addition of C r element, and its component content mol ratio is: Cr
xMo
7.82V
1.18Te
0.94Nb
1O
y(0≤x≤0.01).
2. produce acrylic acid catalyst according to the described catalytic oxidation of propane of claim 1, it is characterized in that described Mo content is mol ratio 7.82.
3. produce acrylic acid catalyst according to the described catalytic oxidation of propane of claim 1, it is characterized in that described V content is mol ratio 1.18.
4. produce acrylic acid catalyst according to the described catalytic oxidation of propane of claim 1, it is characterized in that described Te content is mol ratio 0.94.
5. produce acrylic acid catalyst according to the described catalytic oxidation of propane of claim 1, it is characterized in that described Nb content is mol ratio 1.
6. produce the catalyst of methacrylaldehyde according to the described catalytic oxidation of propane of claim 1, it is characterized in that described Cr micronutrient levels is mol ratio 0 ~ 0.01.
7. produce acrylic acid modified Preparation of catalysts method according to the described catalytic oxidation of propane of claim 1 for one kind, it is characterized in that adopting dissolving-coprecipitation: press certain mol proportion preparation molybdate, metavanadate, telluric acid, niobium oxalate and chromium nitrate solution, mix back constant temperature evaporate to dryness, 150 ℃ and 600 ℃ of each roastings are 2 hours under blanket of nitrogen.
8. one kind is applicable to that according to the described catalyst of claim 1 catalytic oxidation of propane produces acrylic acid reaction, the base stock that it is characterized in that described reaction is propane and oxygen, reaction condition is that unstripped gas basic composition is: the volume ratio of propane and oxygen is 0.4 ~ 0.7, reaction temperature is 380 ~ 420 ℃, carry out under the normal pressure, flow of inlet water is 0.3 ~ 0.65 ml/h, and air speed is 1200 ~ 4000 ml/ (g.h).
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|---|---|---|---|
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983422A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Catalyst for catalytically oxidizing propane for preparing acrylic acid, and preparation method thereof |
| CN111468136A (en) * | 2020-05-19 | 2020-07-31 | 西南化工研究设计院有限公司 | Catalyst for preparing acrylic acid by oxidizing propane and preparation method thereof |
| CN114534750A (en) * | 2020-11-24 | 2022-05-27 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing acrylic acid by selective oxidation of propane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009106474A2 (en) * | 2008-02-25 | 2009-09-03 | Olaf Timpe | Phase-enriched movtenb mixed oxide catalyst and methods for the preparation thereof |
| CN102476057A (en) * | 2010-11-25 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of MoVTeNbO catalyst for reaction of preparing acrylic acid by propane oxidation |
-
2013
- 2013-05-26 CN CN2013101980799A patent/CN103285890A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009106474A2 (en) * | 2008-02-25 | 2009-09-03 | Olaf Timpe | Phase-enriched movtenb mixed oxide catalyst and methods for the preparation thereof |
| CN102476057A (en) * | 2010-11-25 | 2012-05-30 | 中国科学院大连化学物理研究所 | Preparation method of MoVTeNbO catalyst for reaction of preparing acrylic acid by propane oxidation |
Non-Patent Citations (1)
| Title |
|---|
| F. CAVANI，ET AL.: "Rutile-type metal (Cr, V) niobates as catalysts for propane ammoxidation to nitriles: In situ characterization and operando reactivity", 《CATALYSIS TODAY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983422A (en) * | 2015-02-02 | 2016-10-05 | 中国石油天然气股份有限公司 | Catalyst for catalytically oxidizing propane for preparing acrylic acid, and preparation method thereof |
| CN111468136A (en) * | 2020-05-19 | 2020-07-31 | 西南化工研究设计院有限公司 | Catalyst for preparing acrylic acid by oxidizing propane and preparation method thereof |
| CN114534750A (en) * | 2020-11-24 | 2022-05-27 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing acrylic acid by selective oxidation of propane |
| CN114534750B (en) * | 2020-11-24 | 2024-03-01 | 中国石油天然气股份有限公司 | Preparation method of catalyst for preparing acrylic acid by selective oxidation of propane |
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Application publication date: 20130911 |