CN102179261A - Catalyst for preparing crylic acid from propane through selective oxidation and preparation method thereof - Google Patents
Catalyst for preparing crylic acid from propane through selective oxidation and preparation method thereof Download PDFInfo
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- CN102179261A CN102179261A CN 201110079695 CN201110079695A CN102179261A CN 102179261 A CN102179261 A CN 102179261A CN 201110079695 CN201110079695 CN 201110079695 CN 201110079695 A CN201110079695 A CN 201110079695A CN 102179261 A CN102179261 A CN 102179261A
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Abstract
The invention relates to a compound metal oxide type catalyst for preparing crylic acid from propane through selective oxidation and a preparation method thereof. The general formula of the catalyst is MoVTeNbO, wherein Mo, V, Te and Nb are active ingredients, and an atomic molar ratio of the four metal elements and oxygen thereof is 1:(0.1-1.0):(0.2-1.0):(0.2-0.9):(20-60). When the catalyst is adopted for preparing the crylic acid, the conversion rate of the propane and the once through yield of the crylic acid are high, and a template synthesis method for preparing the compound metal oxide type catalyst with a periodically arranged ordered structure from the propane through selective oxidation is provided; and the catalyst prepared by the method has good controllability, the size, appearance, structure, arrangement and the like of the compound catalyst material can be controlled by the space limiting effect of the catalyst and the debugging effect of a template agent, and the catalyst has small particles and high catalytic activity.
Description
Technical field
The present invention relates to a kind of propane selective oxidation method to prepare propenoic acid used composite metal oxide type catalyst and this Preparation of catalysts method thereof.
Background technology
Propane is the key component in casing-head gas, natural gas and the refinery gas, and the source is abundant, and is cheap.Price is about 1/3rd of propylene, does not also obtain more efficiently development and utilization at present.The reserves of current global range lower paraffin hydrocarbon are abundant, and China is the country of propane resource than horn of plenty, contains 6% approximately as propane in the casing-head gas such as grand celebration, Central Plains and Tarim Basin, contains 3～6% propane in the condensate approximately.Propane accounts in liquefied petroleum gas about 60%, can reach 15% in natural gas.If can realize that the oxidation step process produces acrylic acid, then can simplify process route, cut down the consumption of energy, will have huge economic benefit, and will drive developing rapidly of downstream industry.
Acrylic acid is important Organic Chemicals and oilfield chemistry reagent, is widely used in the production of coating, chemical fibre, weaving and light industrial goods, also is used for industries such as oil exploitation, oil dope.Acrylic acid and ester are the very high petrochemical industry deep processed products of added value, can further process many fine chemical products.Acrylic acid is mainly used to produce esters of acrylic acid industrial.Obtain application more and more widely at aspects such as coating, synthetic fibers, synthetic rubber and daily chemical products.Acrylic acid can be used for producing oil-field brines such as Sodium Polyacrylate, polyacrylic acid quaternary ammonium salt and copolymer thereof and handles flocculant commonly used.Polypropylene and acrylic copolymer also can be used for producing super absorbent resin and help washing agent.
Present industrial direct oxidation of propylene method or the propylene two-step reaction method used produced acrylic acid, though once through yield is very high, equipment and raw material investment are also higher, and income is restricted.Because the cost height of propylene adopts propane cheap and easy to get to replace direct oxidation of propylene system acrylic acid, becomes one of research focus of low-carbon alkanes development and use, has potential great economic benefit and extensive market prospects.The research success of this project will further be extended the oil field industry chain (supply chain) to the deep processing of casing-head gas, tower overhead gas, set up the fine chemical product industrial chain, and it is significant to increase value-added content of product.
At present, in selective oxidation of propane system acrylic acid process, there is three types catalyst system: (1) industrial normal butane Selective Oxidation maleic anhydride catalyst: VPO series catalysts; (2) alkanes oxidative dehydrogenation catalyst: heteropoly acid and saline catalyst H thereof
xCs
3-xPMo
12O
40(x=0～3); (3) propane ammoxidation, alkanes oxidative dehydrogenation catalyst: mixed-metal oxides (MMO) catalyst.The acrylic acid catalyst of selective oxidation of propane system derives from this three kinds of catalyst systems mostly.Present result of study shows that wherein mixed-metal oxides is one of more catalyst of research, and the most effective also is O composite metallic oxide catalyst.Mainly contain several in the elements such as Mo, V, Te, Sb and Nb with the composition of the used mixed-metal oxides type of selective oxidation of propane system acrylic acid catalyst in the prior art.
(JPA11226408, JPA10230164, JPA11285636 and JPA10137585 etc.) acrylic acid productive rate is only between 10%～21% in most research results.Though acrylic acid yield is up to 42% in European patent EP 0608838 and EP0962253, a lot of research groups of US and European all do not repeat out above result.The preparation method of MoVTeNbO composite oxide catalysts has a significant impact its crystal structure, grain size and the catalytic performance in the reaction of selective oxidation of propane system acrylic acid thereof, and this also is one of major reason of this composite catalyst performance poor reproducibility.And the preparation method of the O composite metallic oxide catalyst in patent of having reported or document adopts solwution method or seasoning, catalyst bad mechanical strength, the particle that obtains is big, structure is inhomogeneous, it is irregular to arrange, catalytic activity is low and poor reproducibility etc., the conversion ratio of propane and the lower shortcoming of acrylic acid once through yield have limited O composite metallic oxide catalyst in industrial application.
Summary of the invention
In order to solve the problem that exists in the background technology, the invention provides the used catalyst of a kind of propane selective oxidation method to prepare propenoic acid, the conversion ratio of propane and acrylic acid once through yield height when adopting this Preparation of Catalyst acrylic acid, and provide the method for selective oxidation of propane system acrylic acid O composite metallic oxide catalyst that has the ordered structure of periodic arrangement with template synthesis method preparation, catalyst with this method preparation has good controllability, can utilize the size of the debugging effect of its spatial constraints effect and template agent to the composite catalyzing agent material, pattern, structure and arranging etc. is controlled, and this catalyst granules is little, the catalytic activity height.
The technical solution adopted in the present invention is: its general formula of catalyst of the present invention is expressed as MoVTeNbO, wherein Mo, V, Te, Nb are active component, and the atomic molar ratio of four kinds of metallic elements and oxygen thereof is respectively 1:0.1～1.0:0.2～1.0:0.2～0.9:20～60.
The invention provides this Preparation of catalysts method and comprise the steps, each raw material by weight ratio:
A, in water bath with thermostatic control, place a there-necked flask, connect electric mixer, condensing unit, constant pressure funnel respectively; Get 100 parts～1000 parts deionized waters, add in the there-necked flask, and the temperature that makes water bath with thermostatic control is raised to 50～90 ℃, the emulsifying agent benzene sulfonic acid sodium salt or the lauryl sodium sulfate that add 0.15 part～0.26 part then, add 0.1 part～0.5 part of buffer sodium acid carbonate, open electric mixer, it is mixed, after 5～30 minutes, add 10 parts～50 parts template agent monomers with constant pressure funnel, react after 3～6 hours, add 0.1 part～0.5 part of initiator potassium persulfate, polymerisation 18～24 hours obtains monodispersity latex balloon template preferably;
B, take by weighing 2.0 parts～6.0 parts anhydrous oxalic acids and be dissolved in the flask that fills 100 ml deionized water, stir 40～60 ℃ of water-bath heating; After treating that anhydrous oxalic acid dissolves fully, add 0.5 part～3.0 parts niobium hydroxides, continue to stir, be cooled to 25～40 ℃, obtain colourless solution 1.; Take by weighing 8.0 parts～40.0 parts amine molybdates and be dissolved in the flask that fills 100 parts of deionized waters, stir, 60～80 ℃ of water-bath heating get colourless solution; Add 1.0 parts～7.0 parts metavanadic acid amine, solution becomes orange-yellow, continues to stir 60～80 ℃ of water-bath heating; Add 1.5 parts～6.0 parts telluric acids again, obtain red solution 2.; Under constantly stirring, with solution 2. add solution 1. in, mixing the back, to regulate pH value be 4～8, formation Mo-V-Te-Nb-O composite metal oxide colloidal sol;
C, under magnetic agitation, composite metal oxide colloidal sol is slowly joined in the emulsion particle emulsion that obtains among the step a; Then with mixed liquor magnetic agitation 1～3 hour at room temperature; Then, 110～140 ℃ of drying 8～18h in vacuum drying chamber, dried sample is calcined, concrete is is warming up to 200～300 ℃ with the heating rate of 2～5 ℃/min, constant temperature 1～3 h in the time of 200-300 ℃, the heating rate with 5～10 ℃/min is warming up to 500～700 ℃ again, constant temperature 3～8 h in the time of 500～700 ℃, latex balloon is decomposed fully, obtain porous, the regular Mo-V-Te-Nb-O O composite metallic oxide catalyst of distribution.
Technique effect of the present invention is: the selective oxidation of propane system acrylic acid O composite metallic oxide catalyst that the present invention has the ordered structure of periodic arrangement with the preparation of template synthetic method, catalyst with this method preparation has good controllability, can utilize the size of the debugging effect of its spatial constraints effect and template agent to the composite catalyzing agent material, pattern, structure and arranging etc. is controlled, because fenestra pore size unanimity, it is identical that the composite of preparation has the aperture equally, monodispersed structure, by forerunner's species piling up around template, assembling, setting, remove template by calcination at last, the formation homogeneous, Mo-V-Te-Nb-O composite with regular pore structure.Mo-V-Te-Nb-O composite catalyst provided by the invention prepares in the acrylic acid reaction at selective oxidation of propane, shows very high catalytic activity, conversion of propane and acrylic acid once through yield.
Description of drawings
Fig. 1 schemes for the SEM of the latex balloon template that the present invention synthesizes;
Fig. 2 removes the preceding SEM figure of latex balloon template for MoVTeNbO composite catalyst of the present invention;
Fig. 3 is the SEM figure after MoVTeNbO composite catalyst of the present invention removes the latex balloon template;
Fig. 4 is the XRD spectra of MoVTeNbO composite catalyst of the present invention.
The specific embodiment:
Below by embodiment the present invention is specifically described.
1, Preparation of catalysts:
Embodiment 1:
A, in water bath with thermostatic control, place a there-necked flask, connect electric mixer, condensing unit, constant pressure funnel respectively, add 500 g deionized waters in flask, 65 ℃ of water-bath heating add 0.24g lauryl sodium sulfate (SDS) and sodium acid carbonate 0.35g then, stir after 5～30 minutes, add 26 g styrene monomers with constant pressure funnel, react after 5 hours, add potassium peroxydisulfate 0.25g, polymerisation 20 hours obtains monodispersity polystyrene spheres emulsion template preferably.B, take by weighing the 4.198g anhydrous oxalic acid and be dissolved in the flask that fills the 100ml deionized water, stir 40 ℃ of water-bath heating; After treating that anhydrous oxalic acid dissolves fully, add the 1.715g niobium hydroxide, continue to stir, be cooled to 25 ℃, obtain colourless solution 1.; Take by weighing the 14.2g amine molybdate, 2.283 g metavanadic acid amine and 4.25g telluric acid are dissolved in the 100 g deionized waters and are mixed with solution 2.; Under constantly stirring, with solution 2. add solution 1. in, mixing the back, to regulate pH value be 6,80 ℃ of water-bath heating, formation colloidal sol.C, under constantly stirring, this colloidal sol is slowly joined in the polystyrene emulsion template, and mixed liquor was at room temperature stirred 3 hours, then, sample in 120 ℃ of vacuum drying chambers behind the dry 10h is warming up to 200 ℃ with the heating rate of 3 ℃/min, and constant temperature 1h; Heating rate with 5 ℃/min is warming up to 500 ℃ again, and constant temperature 5h, and the polystyrene latex ball is decomposed fully.Obtain porous, the regular Mo-V-Te-Nb-O O composite metallic oxide catalyst of distribution, the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 2:
Change the 0.24g lauryl sodium sulfate (SDS) among the embodiment 1 benzene sulfonic acid sodium salt of 0.15g into, all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 3:
Change the 0.24g lauryl sodium sulfate (SDS) among the embodiment 1 into 0.18g lauryl sodium sulfate (SDS), all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 4:
Change the sodium acid carbonate 0.35g among the embodiment 1 into sodium acid carbonate 0.1g, all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 5:
Change the 0.24g lauryl sodium sulfate (SDS) among the embodiment 1 into 0.20g lauryl sodium sulfate (SDS), all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 6:
Change the 0.24g lauryl sodium sulfate (SDS) among the embodiment 1 into 0.18g lauryl sodium sulfate (SDS), all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 7:
Change the 0.24g lauryl sodium sulfate (SDS) among the embodiment 1 into 0.16g lauryl sodium sulfate (SDS), all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 8:
Change the 26g styrene monomer (PS) among the embodiment 1 into 23g methyl methacrylate monomer (PMMA), all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 9:
Change the 26g styrene monomer (PS) among the embodiment 1 into 33g ethyl acrylate monomer, all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 10:
Change the 0.24g lauryl sodium sulfate (SDS) among the embodiment 1 into the 0.15g benzene sulfonic acid sodium salt, 26g styrene monomer (PS) changes 23g methyl methacrylate monomer (PMMA) into, all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
Embodiment 11:
Change the 0.24g lauryl sodium sulfate (SDS) among the embodiment 1 into the 0.15g benzene sulfonic acid sodium salt, 26ml styrene monomer (PS) changes the 24ml ethyl acrylate into, and all the other are identical with the preparation method of embodiment 1, and the performance evaluation of catalyst the results are shown in Table 1.
2, embodiment 1～embodiment 11 prepared catalyst are detected:
Raw material: propane; Catalyst amount: 8.0 g; Reaction pressure: normal pressure; Reaction temperature: 350～450 ℃; Reaction gas air speed: 1800ml.g
-1.h
-1Evaluating apparatus: the WF-4 type that Tianjin roc Xiang Science and Technology Ltd. produces multi-functional little anti-/ long-pending anti-evaluating apparatus.This device is the stainless steel continuous flow reactor of fixed bed, reactor total length 528mm, internal diameter 13.5mm, external diameter 25mm.
3, the analysis of product:
(1) gas-chromatography: GC112-A, PONA post, 50m * 0.2mm * 0.5 μ m, fid detector; (2) testing conditions: stainless steel packed column, 170 ℃ of detector column temperature temperature, 210 ℃ of injector temperature, 300 ℃ of detector temperatures, flow rate of carrier gas (N
2): 30ml/min.Reaction result sees Table 1.
Reaction result among table 1 embodiment
| Embodiment | Conversion of propane (%) | Acrylic acid yield (%) |
| 1 | 68.3 | 45.2 |
| 2 | 58.1 | 32.9 |
| 3 | 59.8 | 35.8 |
| 4 | 61.4 | 34.6 |
| 5 | 56.1 | 32.4 |
| 6 | 53.3 | 29.8 |
| 7 | 51.2 | 28.5 |
| 8 | 49.7 | 27.8 |
| 9 | 48.6 | 26.9 |
| 10 | 46.3 | 23.4 |
| 11 | 45.2 | 19.7 |
Claims (3)
1. catalyst for propane selective oxidation method to prepare propenoic acid, its general formula is expressed as MoVTeNbO, wherein Mo, V, Te, Nb are active component, and the atomic molar ratio of four kinds of metallic elements and oxygen thereof is respectively 1:(0.1～1.0): (0.2～1.0): (0.2～0.9): (20～60).
2. prepare the method for the described catalyst for propane selective oxidation method to prepare propenoic acid of claim 1, comprise the steps, each raw material by weight ratio:
A, in water bath with thermostatic control, place a there-necked flask, connect electric mixer, condensing unit, constant pressure funnel respectively; Get 100 parts～1000 parts deionized waters, add in the there-necked flask, and the temperature that makes water bath with thermostatic control is raised to 50～90 ℃, the emulsifying agent benzene sulfonic acid sodium salt or the lauryl sodium sulfate that add 0.15 part～0.26 part then, add 0.1 part～0.5 part of buffer sodium acid carbonate, open electric mixer, it is mixed, after 5～30 minutes, add 10 parts～50 parts template agent monomers with constant pressure funnel, react after 3～6 hours, add 0.1 part～0.5 part of initiator potassium persulfate, polymerisation 18～24 hours obtains monodispersity latex balloon template preferably;
B, take by weighing 2.0 parts～6.0 parts anhydrous oxalic acids and be dissolved in the flask that fills 100 ml deionized water, stir 40～60 ℃ of water-bath heating; After treating that anhydrous oxalic acid dissolves fully, add 0.5 part～3.0 parts niobium hydroxides, continue to stir, be cooled to 25～40 ℃, obtain colourless solution 1.; Take by weighing 8.0 parts～40.0 parts amine molybdates and be dissolved in the flask that fills 100 parts of deionized waters, stir, 60～80 ℃ of water-bath heating get colourless solution; Add 1.0 parts～7.0 parts metavanadic acid amine, solution becomes orange-yellow, continues to stir 60～80 ℃ of water-bath heating; Add 1.5 parts～6.0 parts telluric acids again, obtain red solution 2.; Under constantly stirring, with solution 2. add solution 1. in, mixing the back, to regulate pH value be 4～8, formation Mo-V-Te-Nb-O composite metal oxide colloidal sol;
C, under magnetic agitation, composite metal oxide colloidal sol is slowly joined in the emulsion particle emulsion that obtains among the step a; Then with mixed liquor magnetic agitation 1～3 hour at room temperature; Then, 110～140 ℃ of drying 8～18h in vacuum drying chamber, dried sample is calcined, concrete is is warming up to 200～300 ℃ with the heating rate of 2～5 ℃/min, constant temperature 1～3 h in the time of 200-300 ℃, the heating rate with 5～10 ℃/min is warming up to 500～700 ℃ again, constant temperature 3～8 h in the time of 500～700 ℃, latex balloon is decomposed fully, obtain porous, the regular Mo-V-Te-Nb-O O composite metallic oxide catalyst of distribution.
3. according to the method for the described catalyst for propane selective oxidation method to prepare propenoic acid of claim 2, it is characterized in that: described step a template agent monomer is a kind of in styrene, methyl methacrylate or the ethyl acrylate, and the latex that correspondence obtains is followed successively by polystyrene, polymethyl methacrylate or polyethyl acrylate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983421A (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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101214445A (en) * | 2008-01-21 | 2008-07-09 | 大庆石油管理局 | Catalyst for propane selective oxidation method to prepare propenoic acid and preparation thereof |
| US20080249328A1 (en) * | 2007-04-03 | 2008-10-09 | Kaduk James A | Mixed metal oxide catalysts and catalytic conversions of lower alkane hydrocarbons |
| WO2009073171A2 (en) * | 2007-12-04 | 2009-06-11 | Ineos Usa Llc | Method of making mixed metal oxide catalysts for ammoxidation and/or oxidation of lower alkane hydrocarbons |
| CN101733110A (en) * | 2008-11-07 | 2010-06-16 | 中国石油大学(北京) | Three-dimensional ordered macroporous oxide catalyst for diesel soot purification and preparation method thereof |
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2011
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080249328A1 (en) * | 2007-04-03 | 2008-10-09 | Kaduk James A | Mixed metal oxide catalysts and catalytic conversions of lower alkane hydrocarbons |
| WO2009073171A2 (en) * | 2007-12-04 | 2009-06-11 | Ineos Usa Llc | Method of making mixed metal oxide catalysts for ammoxidation and/or oxidation of lower alkane hydrocarbons |
| CN101214445A (en) * | 2008-01-21 | 2008-07-09 | 大庆石油管理局 | Catalyst for propane selective oxidation method to prepare propenoic acid and preparation thereof |
| CN101733110A (en) * | 2008-11-07 | 2010-06-16 | 中国石油大学(北京) | Three-dimensional ordered macroporous oxide catalyst for diesel soot purification and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983421A (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 |
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