CN101972646A - Toluene liquid-phase selective oxidation catalyst and preparation method thereof - Google Patents
Toluene liquid-phase selective oxidation catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a toluene liquid-phase selective oxidation catalyst and a preparation method thereof. The catalyst is transition metal or rare earth vanadate which has the composition shown by MexVyO, wherein Me is one of transition metals of VIB, VIIB or VIIIB group; V is vanadium; and the molar ratio x/y of Me to V is 0.1 to 10. The catalyst provided by the invention can be used for toluene liquid-phase oxidation reaction, the conversion rate of the toluene is high and the main product is benzaldehyde; by changing the composition and modulating reaction conditions of the catalyst, the proportion of the benzaldehyde to benzoic acid in the product can be changed; the catalyst does not pollute equipment and environment; and a solved used in the reaction can be recovered and rational resource utilization is basically realized.
Description
Technical field
The present invention relates to a kind of be used for toluene liquid phase selective oxidation production benzaldehyde, phenmethylol and benzoic Catalysts and its preparation method and application, belong to Preparation of Catalyst and applied technical field thereof.
Background technology
Phenmethylol, benzaldehyde and benzoic acid all are important fine chemical material and products, have considerable market prospects and economic benefit.With the benzaldehyde is example, it is predicted, and a few years from now on, China's benzaldehyde demand will be with the speed increase in every year about 7%; By 2015, the market demand of China's benzaldehyde will reach about 30,000 tons/year, and " no chlorine " benzaldehyde demand accounts for 46% of benzaldehyde aggregate demand.Although China's benzaldehyde production capacity can satisfy the market aggregate demand of benzaldehyde,, " no chlorine " benzaldehyde still needs a large amount of imports, and a year import volume is about about half of the market demand.
In PETROLEUM PROCESSING and Coal Chemical Industry product, generate a large amount of toluene.The toluene deep processing is become high value-added product,, become one of important channel of toluene deep processing and utilization as generating product phenmethylol, benzaldehyde and benzoic acid etc. through selective oxidation.At present, adopting toluene is that raw material production phenmethylol, benzaldehyde and benzoic main method have: chlorination toluene Hydrolyze method, gas phase oxidation of toluene method and toluene liquid phase oxidation.
Benzoic acid and by-product benzaldehyde and phenmethylol are produced in industrial common employing " chlorination toluene Hydrolyze method ".But this technological process is long, product separation difficulty, discharging corrosive gas and debirs.In addition, contain chloride or chlorion in products benzene formaldehyde, benzoic acid and the phenmethylol, limited their utilizations in medicine, spices greatly.
" gas phase oxidation of toluene method " part has overcome the deficiency of " chlorination toluene Hydrolyze method ", but and fails to make the industrial production of " gas phase oxidation of toluene method " to obtain breakthrough.The major defect of this method is: toluene conversion is low, and the concentration ratio of toluene in reaction end gas is lower, thereby makes the recycling difficulty of toluene; Benzoic acid is that the yield of primary product and benzaldehyde and phenmethylol is very low, and generates the deep oxidation product of a great deal of.These technical defectives cause " gas phase oxidation of toluene method " production cost higher, and economic benefit is undesirable.
In recent years, toluene liquid phase selective oxidation producing benzaldehyde, benzoic acid and phenmethylol have caused the extensive interest of researcher and enterprise.It is raw material with toluene at present that this method is considered to, under relatively mild reaction condition, and the most attractive synthetic method of the generation of high selectivity " no chlorine " benzaldehyde, benzoic acid or phenmethylol.The key problem in technology of realizing the selective oxidation of toluene liquid phase is the research and development effective catalysts.At present, developed multiple toluene liquid phase selective oxidation catalyst, main type has: (1) transition metal oxide and loaded catalyst thereof; (2) heteropoly acid and loaded catalyst thereof; (3) transition metal complex and loaded catalyst etc. thereof.
Chinese patent 200410007341 has been reported a kind of toluene liquid phase selective oxidation cobalt-Mn catalyst, and this catalyst has higher benzaldehyde selectivity.140 g toluene, 0.85 g manganous bromide, 0.7 g, four water cobalt acetates and 42 g glacial acetic acid are mixed; 120
oThe C aerating oxygen is then 130
oC, 1.0Mpa reacted 240 minutes down, and toluene conversion is 39.4 mol%, and benzaldehyde selectivity 20.39 mol%, benzyl alcohol selective are 5.3 mol%, and the benzoic acid selectivity is 73.09 mol%.
Chinese patent 200310119470.1, report is a catalyst with the Ca-Zr-Cu-Co-Al-O composite oxides, at 0.47 mol toluene, 1.0 g catalyst, 0.04 g pyridine, 190
oReaction is 120 minutes under the condition of C, 1.0 MPa, and toluene conversion is 7.4 mol%, and the benzaldehyde selectivity is up to 85.89 mol%.
U.S. Pat 6743952 has been reported a kind of toluene liquid-phase oxidation catalyst system that comprises major catalyst, co-catalyst and co-catalyst; Wherein, major catalyst is composite oxides or the salt that contains iron, manganese, cobalt, molybdenum, nickel element, and co-catalyst is manganese or mantoquita, and co-catalyst is cobaltous bromide, sodium bromide, sodium chloride or zinc bromide etc.For example, in about 130 mL of toluene, cobalt acetate 0.01 gmol/L, manganese acetate 0.008 gmol/L, sodium bromide 0.0036 gmol/L, air velocity 2 L/min, reaction pressure 10 bar, reaction temperature 120
oReaction is 1 hour under the condition of C, and the conversion ratio of toluene is about 10%, and the benzaldehyde selectivity is 40 %-50 %.After catalyst carried out the circulation of 10 secondary responses, toluene conversion and benzaldehyde selectivity were constant substantially.But, after each reaction finishes, need in reaction system, to replenish 5% of cobalt acetate and manganese acetate initial content respectively, and the sodium bromide initial content 100%.
U.S. Pat 20070213566 reports are catalyst with manganese acetate, stannic chloride (perhaps aluminium chloride, manganese chloride etc.), and NaBr is that initator, acetic acid are solvent, is 120 in temperature
oCarry out the toluene liquid phase oxidation reaction under the condition of C, 48 ~ 274. 6 kPa, primary product is a benzaldehyde, in addition, also generates a spot of benzoic acid and phenmethylol.For example, at 0.11 mol toluene, 0.0021 mol manganese acetate, 0.0011 mol stannic chloride, 0.0011 mol sodium bromide, 50 mL acetate, 120
oReaction is 4 hours under the condition of C, 250 pis (about 1.72 MPa), and the conversion ratio of toluene is 18%, and the selectivity of benzaldehyde is 68%.Under the constant situation of other condition, if reduce the consumption of manganese acetate, then the conversion ratio of toluene reduces in the reaction, and the selectivity of benzaldehyde increases.
Contain the selective oxidation reaction that barium oxide or vanadic salts catalyst are widely used in hydro carbons, and show catalytic activity preferably.In recent years, catalytic component based on vanadium is also attempted being used for the toluene liquid phase oxidation reaction.
Wu etc. have relatively studied V/Al
2O
3, Mo/Al
2O
3And Mo-V/Al
2O
3Catalyst be used for the performance that liquid phase oxidation toluene generates benzaldehyde (
Chem. Res. Chin. Univ.2007,23:585-591.).Discover, at V/Al
2O
3The character of catalyst of having added the remarkable modulation of Mo in the catalyst, thus its catalytic performance influenced.Mo-V/Al
2O
3The unbodied vanadium oxygen of catalyst surface species help generating benzaldehyde, have V
2O
5Species can promote toluene to transform but reduce the selectivity of benzaldehyde; Catalyst surface AlVMoO
7Species help the generation of toluene conversion and cresols.The yield of benzaldehyde and catalyst surface O/Al and Mo/V ratio are closely related; When catalyst surface O/Al=3.0 and Mo/V=0.7, the yield of benzaldehyde the highest (13.2%), at this moment, the selectivity of benzaldehyde is 79.5%.
Shijina etc. have investigated supported vanadium-based catalyst VO
x/ g-Al
2O
3Be used for the toluene liquid phase oxidation catalytic performance (
Kinet. Catal. Lett. 2008,94 (2): 261-270.).The load capacity of vanadium influences catalyst toluene liquid phase oxidation performance on the catalyst.When the vanadium load capacity was low, vanadium oxygen species high dispersive was in g-Al on the catalyst
2O
3The surface; Along with the increase of vanadium load capacity, vanadium oxygen species reduce gradually at the decentralization of catalyst surface, V occurs
2O
5Phase; Simultaneously, the conversion ratio of toluene increases, and the selectivity of benzaldehyde increases reduction more earlier in the product; Promptly for the acquisition benzaldehyde of high yield, catalyst need have suitable vanadium load capacity.With 17 wt.%V
2O
5/ Al
2O
3(AV17) be catalyst, in catalyst amount 0.1 g, toluene 27.5 mmol, hydrogen peroxide consumption 202.88 mmol, acetonitrile 10 mL, reaction temperature 50
oReaction is 3 hours under the condition of C, and the maximum conversion of toluene is 30%, and the selectivity of benzaldehyde is 79.0%.
Discoveries such as Wang with the acetate vanadium be catalyst, hydrogen peroxide be oxidant, when glacial acetic acid is solvent, oxide side chain reaction mainly takes place in toluene, and benzaldehyde be reaction primary product (
J. Phys. Chem. C2009,113:14270-14278.).The consumption of catalyst acetate vanadium and the yield of reaction temperatures affect benzaldehyde.When acetate vanadium consumption is 0.1 mmol, the conversion ratio of toluene the highest (19.8%); When acetate vanadium consumption is 0.03 mmol, the selectivity of benzaldehyde the highest (72.8%); Along with the rising of reaction temperature, the selectivity of toluene conversion and benzaldehyde increases; When 363 K, the conversion ratio of toluene the highest (15.4%), simultaneously, the selectivity of benzaldehyde also the highest (63%) continues rising reaction temperature hydrogen peroxide and decomposes, and causes the benzaldehyde yield to reduce.
Subrahmanyama etc. relatively studied V-AIPO, V-MCM-48, V-MCM-41, V-Al-Beta and VS-1 porous catalyst be used for toluene liquid phase selective oxidation performance (
Appl. Catal. A2005,282:67-71.).With hydrogen peroxide (H
2O
2) be oxidant, at catalyst 100
Mg, toluene/H
2O
2(30%)/acetonitrile=3/1/10(mol ratio) reaction condition under, the catalytic activity of V-AIPO is the highest, the conversion ratio of toluene is 28.4%, the selectivity of benzaldehyde is 64.4%.Under similar condition, the TBHP with 70% (TBHP) is an oxidant, and the conversion ratio of toluene is 21.5% on the V-AIPO catalyst, and the selectivity of benzaldehyde is 73.3%, and the selectivity of phenmethylol is 3.95%, and benzoic selectivity is 22.8%.TBHP (TBHP) is that oxidant is unlike using H
2O
2For oxidant has advantage, because use TBHP homogeneous catalytic reaction not to take place as oxidant.V in the catalyst
5+/ V
4+It may be the reactive activity center.Use solvent such as acetonitrile, acetone or methyl alcohol that toluene selective oxidation performance is also had a significant effect in the reaction system, when wherein using acetone as solvent on the catalyst conversion ratio of toluene the highest.Increase polarity of solvent, can increase benzoic yield in the product.
Venkateswara etc. have relatively studied phosphato-molybdic heteropolyacid (MPVA) and Nb that phosphato-molybdic heteropolyacid (MPA), V mix
2O
5Phosphato-molybdic heteropolyacid (the MPVA/Nb that the V of load mixes
2O
5) catalyst be used for the toluene liquid phase oxidation catalytic performance (
J. Mol. Catal. A2009,303:84-89.).In MPA, add the catalytic activity that V can improve catalyst, MPVA/Nb
2O
5Catalyst has the highest toluene liquid phase oxidation catalytic performance; With MPVA/Nb
2O
5Be catalyst, (t-butyl hydroperoxide is under the condition of oxidant, 50 mg catalyst TBHP), and the conversion ratio of toluene is 22%, and the selectivity of benzaldehyde is 76% at room temperature, normal pressure, 10 mmol toluene, 8 mmol TBHPs.The V that mixes has entered the heteropoly acid primary structure of MPA; The oxidation-reduction character that contains vanadium ion in the character of vanadium heteropolyacid catalyst and the heteropoly acid primary structure is closely related.
Summary of the invention
The purpose of this invention is to provide a kind of transition metal vanadate catalyst, this catalyst can be under the reaction condition of gentleness, and is benzoic acid, benzaldehyde and phenmethylol than high selectivity and higher yields with the toluene liquid phase oxidation.
Another object of the present invention is to provide above-mentioned Preparation of catalysts method, the catalyst that adopts different preparation methods and condition to make, in the toluene liquid phase oxidation reaction, have different catalytic activitys, and the different selectivity of para Toluic Acid, benzaldehyde and phenmethylol.
For realizing above-mentioned target, technical scheme of the present invention is as follows:
A kind of catalyst that is used for the selective oxidation of toluene liquid phase is characterized in that: catalyst is transition metal or rare-earth vanadate, consists of Me
xV
yO, wherein Me is transition metal or rare earth element, V is a vanadium, Me/V mol ratio x/y=0.1～10.Described Me be IB, IIB,
B,
B,
B or
B transition metal or rare earth element, as nickel, manganese, cobalt, iron, titanium, cerium, copper or zinc, the Me/V mol ratio is x/y=0.5～2.
Form Me
xV
yAmong the O, the simplest ratio of metal, vanadium and oxygen is to get 1 and the mol ratio that draws metal and vanadium is 0.1～10 with oxygen, can prepare x/y and be 0.5,1,2,5,10 catalyst.
Above-mentioned catalyst can also be carrier-borne transition metal vanadate catalyst Me
xV
yO/S, carrier S is aluminium oxide, silica, magnesia, zirconia, active carbon, CNT or various Si-Al molecular sieve such as HZSM-5, HZSM-22, Y, SAPO series molecular sieve, MCM-41, MCM-22, SBA-15, transition metal vanadate catalyst Me
xV
yThe load capacity of O is the 1-15 quality % of catalyst quality, preferred 3-10 quality %, and its surplus is the quality of carrier.
Transition metal vanadate catalyst (Me provided by the invention
xV
yO) can adopt coprecipitation, the preparation of gel-sol method.
Adopt the coprecipitation preparation to comprise the steps:
(1) with soluble vanadium acid salt aqueous solution and transition metal or rare earth element soluble metallic salt aqueous solution, regulator solution acidity makes mixed liquor keep solution state and does not have precipitation and separate out;
(2) under agitation, adding alkaline solution in above-mentioned mixed liquor, until precipitation fully, is under 10～11 the condition in the pH value, still aging precipitation 4-6 hour;
(3) filtration, washing obtain solid product, 110-150
oDry 4-8 hour of C is again in 550-850
oC roasting 4-8 hour makes transition metal vanadate or rare-earth vanadate catalyst.
Alkaline solution described in the preparation method of the present invention is that mass concentration is 10 ~ 25% the ammoniacal liquor and/or the mixed solution of organic amine, and organic amine is selected from ethamine, ethylenediamine, propylamine, tetraethyl ammonium hydroxide.
Adopt the sol-gel process preparation to comprise the steps:
(1) with soluble vanadium acid salt aqueous solution and transition metal or rare earth element soluble metallic salt aqueous solution, regulator solution acidity makes mixed liquor still keep solution state and does not have precipitation and separate out;
(2) cationic surfactant or organic polymer are joined in the above-mentioned mixed liquor, stir until forming thick colloid, the mol ratio of metal M e is 0.01～1 in the addition of cationic surfactant or organic polymer and the catalyst;
(3) with after the still aging 4-12 of colloid hour, after filtration, obtain solid product after the washing;
(4) solid product is at 110-150
oDry 4-8 hour of C is at 550-850
oC roasting 4-8 hour makes transition metal vanadate catalyst.
Described cationic surfactant is selected from softex kw, sodium cetanesulfonate, hexadecylamine, preferred softex kw; Organic polymer is selected from polyethylene glycol, polyvinyl alcohol, acid polyethylene, polyacrylic acid, polyoxyethylene, preferred polyethylene glycol or polyvinyl alcohol.
Soluble vanadium hydrochlorate of the present invention can be that ammonium metavanadate, acetic acid vanadium etc. or they contain the compound and the vanadic anhydride of the crystallization water.
Soluble M e slaine of the present invention be IB, IIB,
B,
B,
B or
B transition metal or rare earth element soluble-salt, the soluble-salt of preferred Ni, Mn, Co, Fe, Ti, Ce, Cu, Zn can be their soluble nitrate, acetate, sulfate, halide or they contain the compound of the crystallization water.
Carrier-borne transition metal vanadate catalyst (Me provided by the invention
xV
yO/S) preparation method comprises the steps:
(1) with transition metal vanadate or rare-earth vanadate Me
xV
yO is dispersed in alcohol or the alcohol-water mixed solution;
(2) under stirring condition, support powder or particle joined in the above-mentioned mixed liquor flood;
(3) mixture behind the dipping is at 110-120
oDry 4-6 hour of C is at 450-850
oC roasting 4-8 hour makes catalyst.
Described alcohol is selected from ethanol, propyl alcohol, butanols, phenmethylol; Described alcohol-water solution is the aqueous solution of ethanol, propyl alcohol or butanols, and alcohol is 1～5 with the volume ratio of water.
Catalyst of the present invention is used for the selective oxidation of toluene liquid phase, and reaction condition is as follows: reaction system is by catalyst, toluene, oxidant, solvent composition, and reaction temperature is 30 ~ 120
oC, 1～4 hour reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.Oxidant is oxygen, air, hydrogen peroxide or TBHP in the reaction system; Solvent is selected from acetonitrile, glacial acetic acid, water.In the reaction system, the volume ratio of solvent and toluene is 1～6, and the mol ratio of oxidant and toluene is 1～6, and the mass ratio of catalyst and toluene is 0.01～0.1.
The advantage that catalyst provided by the invention is used for the toluene liquid phase oxidation reaction is: the conversion ratio height of toluene, and primary product is a benzaldehyde; Form and the modulation reaction condition by changing catalyst, can change benzaldehyde and benzoic ratio in the product; Catalyst is to equipment and environmental nonpollution; The murder by poisoning ion undopes in the product; Catalyst is recyclable; The solvent that uses in the reaction can reclaim, and has realized resource rational utilization basically.
Description of drawings
Fig. 1 adopts the Co-V-O catalyst X-ray powder diffraction pattern of sol-gel process preparation;
Fig. 2 adopts the Co-V-O catalyst infrared spectrogram of sol-gel process preparation.
The specific embodiment
The present invention will be described with instantiation below, but the present invention is not limited to this.
The used chemical reagent of the embodiment of the invention is as follows: ammonium metavanadate (NH
4VO
3), vanadic anhydride (V
2O
5), nickel nitrate (Ni (NO
3)
2, manganese nitrate (Mn (NO
3)
24H
2O), ferric nitrate (Fe (NO
3)
39H
2O), cobalt nitrate (Co (NO
3)
26H
2O), cerous nitrate (Ce (NO
3)
36H
2O), titanium trichloride (TiCl
3).
Embodiment 1-6
Different transition metal Me are selected in embodiment 1-6 explanation, the transition metal vanadate catalyst (Me that adopt coprecipitation, prepares under different condition
xV
yO) and the catalytic performance when being used for the selective oxidation of toluene liquid phase.Each Preparation of catalysts method is as follows: (1) determines Me
xV
yThe mol ratio of Me/V is 1/1 in the O catalyst; The corresponding soluble metallic salt of weighing in view of the above; And it is just dissolved with proper amount of deionized water, obtain clear solutions.(2) under quick stirring condition, with the aqueous solution of above-mentioned Me and the aqueous solution of V, and (concentration: 1 mol) the pH value of adjusting mixed solution makes mixed solution keep clear state to adopt salpeter solution.(3) with the 25%(quality) ammonia spirit slowly be added drop-wise in the above-mentioned mixed liquor of quick stirring, stir while dripping, fully until precipitation.Then, be under the condition of 10-11, room temperature in the pH value, static ageing precipitation 4-6 hour.At last, will obtain solid product after sedimentation and filtration, the washing.(4) solid product is at 110-150
oDry 4-8 hour of C is at 550-850
oC roasting 4-8 hour makes transition metal vanadate catalyst.The composition and the preparation method of each component of the described catalyst of embodiment 1-6 are as shown in table 1.
The described catalyst of embodiment 1-6 is used for the selective oxidation of toluene liquid phase.Reaction condition is as follows: reaction system is by catalyst, toluene, oxidant, solvent composition.Be reflected at the reaction temperature that is heated to appointment under the condition of continuous stirring and react, continue in the reaction to stir continuous backflow.Reaction is normal pressure, and reaction temperature is 30 ~ 120
oC, reaction time 1-4 hour.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.In the reaction system, the volume ratio of solvent and toluene is 1-6; The mol ratio of oxidant and toluene is 1-6; The mass ratio of catalyst and toluene is 0.01-0.1.Reaction condition and catalytic performance when above-mentioned catalyst is used for the toluene liquid phase oxidation are as shown in table 1.
Reaction condition and catalytic performance when the catalyst of table 1 embodiment 1-6 preparation is used for the toluene liquid phase oxidation
Embodiment 7-9
Embodiment 7-9 explanation, the catalytic performance when adopting coprecipitation, under different condition, prepare the Ni-V-O catalyst and being used for the selective oxidation of toluene liquid phase.Each Preparation of catalysts method is as follows: (1) determines Me
xV
yThe mol ratio of Me/V is 1/2,1/1 and 2/1 in the O catalyst; The corresponding soluble metallic salt of weighing in view of the above; And it is just dissolved with proper amount of deionized water, obtain clear solutions.(2) under quick stirring condition, with the aqueous solution of above-mentioned Me and the aqueous solution of V, and (concentration: 1 mol) the pH value of adjusting mixed solution makes mixed solution keep clear state to adopt salpeter solution.(3) with the 25%(quality) ammonia spirit slowly be added drop-wise in the above-mentioned mixed liquor of quick stirring, stir while dripping, fully until precipitation.Then, be 11 in the pH value, under the condition of room temperature, static ageing precipitation 6 hours.At last, will obtain solid product after sedimentation and filtration, the washing.(4) solid product is 110
oDry 8 hours of C is 800
oC roasting 8 hours makes transition metal vanadate catalyst.The composition and the preparation method of each component of the described catalyst of embodiment 7-9 are as shown in table 2.
The described catalyst of embodiment 7-9 is used for the selective oxidation of toluene liquid phase.Reaction condition is as follows: reaction system is by catalyst, toluene, oxidant, solvent composition.Be reflected at the reaction temperature that is heated to appointment under the condition of continuous stirring and react, continue in the reaction to stir continuous backflow.Reaction is normal pressure, and reaction temperature is 60
oC, 3 hours reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.Reaction condition and catalytic performance when above-mentioned catalyst is used for the toluene liquid phase oxidation are as shown in table 2.
Reaction condition and catalytic performance when the catalyst of table 2 embodiment 7-9 preparation is used for the toluene liquid phase oxidation
Embodiment 10-12
Sol-gel process is adopted in embodiment 10-12 explanation, Co-V-O catalyst for preparing under different condition and the catalytic performance when being used for the selective oxidation of toluene liquid phase thereof.Method for preparing catalyst is as follows: under quick stirring condition, according to the catalytic component proportioning, a certain amount of soluble vanadium saline solution is mixed with soluble M e aqueous metal salt, regulate the pH value, make mixed liquor still keep solution state.Then, under quick stirring condition, in the above-mentioned mixed liquor that an amount of surfactant or organic polymer are joined, stir while adding, until forming thick colloid.Then, with the static ageing 4-12 of colloid hour.At last, colloid after filtration, the washing after obtain solid product.Solid product is at 110-150
oDry 4-8 hour of C is at 550-850
oC roasting 4-8 hour makes transition metal vanadate catalyst.The composition and the preparation method of each component of the described catalyst of embodiment 10-12 are as shown in table 3.Accompanying drawing 1 and accompanying drawing 2 are respectively the X light powder diffraction spectrogram and the infrared spectrogram of the Co-V-O catalyst that adopts Prepared by Sol Gel Method.
The described catalyst of embodiment 10-12 is used for the selective oxidation of toluene liquid phase.Reaction condition is as follows: reaction system is by catalyst, toluene, oxidant, solvent composition.Be reflected at the reaction temperature that is heated to appointment under the condition of continuous stirring and react, continue in the reaction to stir continuous backflow.Reaction is normal pressure, and reaction temperature is 60
oC, 3 hours reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.Reaction condition and catalytic performance when above-mentioned catalyst is used for the toluene liquid phase oxidation are as shown in table 3.
Reaction condition and catalytic performance when the catalyst of table 3 embodiment 10-12 preparation is used for the toluene liquid phase oxidation
Carrier at 110-120
oDry 4-6 hour of C is at 450-850
oC roasting 4-8 hour makes catalyst.The composition and the preparation method of each component of the described catalyst of embodiment 13-16 are as shown in table 4.
The described catalyst of embodiment 13-16 is used for the selective oxidation of toluene liquid phase.Reaction condition is as follows: reaction system is by catalyst, toluene, oxidant, solvent composition.Be reflected at the reaction temperature that is heated to appointment under the condition of continuous stirring and react, continue in the reaction to stir continuous backflow.Reaction is normal pressure, and reaction temperature is 60
oC, 3 hours reaction time.Reaction back product is lowered the temperature naturally.Reactant mixture carries out qualitative, quantitative analysis on gas chromatograph.Reaction condition and catalytic performance when above-mentioned catalyst is used for the toluene liquid phase oxidation are as shown in table 4.
Reaction condition and catalytic performance when the catalyst of table 4 embodiment 13-16 preparation is used for the toluene liquid phase oxidation
Claims (10)
1. toluene liquid phase selective oxidation catalyst, it is characterized in that: catalyst is transition metal vanadate or rare-earth vanadate, consists of Me
xV
yO, wherein Me is transition metal or rare earth element, V is a vanadium, Me/V mol ratio x/y=0.1～10.
2. toluene liquid phase selective oxidation catalyst according to claim 1, it is characterized in that: Me is nickel, manganese, cobalt, iron, titanium, cerium, copper or zinc, the Me/V mol ratio is x/y=0.5～2.
3. toluene liquid phase selective oxidation catalyst according to claim 1 is characterized in that: described catalyst is carrier-borne transition metal vanadate catalyst Me
xV
yO/S, carrier S is aluminium oxide, silica, magnesia, zirconia, active carbon, CNT or Si-Al molecular sieve, transition metal vanadate catalyst Me
xV
yThe load capacity of O is the 1-15 quality % of catalyst quality.
4. the described toluene liquid phase of claim 1 selective oxidation Preparation of catalysts method is characterized in that adopting the coprecipitation preparation, comprises the steps:
(1) with soluble vanadium acid salt aqueous solution and transition metal or rare earth element soluble metallic salt aqueous solution, regulator solution acidity makes mixed liquor keep solution state and does not have precipitation and separate out;
(2) under agitation, adding alkaline solution in above-mentioned mixed liquor, until precipitation fully, is 10～11 still aging precipitations 4～6 hours in the pH value;
(3) filtration, washing obtain solid product, 110～150
oC drying 4～8 hours is again in 550～850
oC roasting 4-8 hour makes catalyst.
5. the described toluene liquid phase of claim 1 selective oxidation Preparation of catalysts method is characterized in that adopting the sol-gel process preparation, comprises the steps:
(1) with soluble vanadium acid salt aqueous solution and transition metal or rare earth element soluble metallic salt aqueous solution, regulator solution acidity makes mixed liquor still keep solution state and does not have precipitation and separate out;
(2) cationic surfactant or organic polymer are joined in the above-mentioned mixed liquor, stir until forming thick colloid, the mol ratio of metal M e is 0.01～1 in the addition of surfactant or organic polymer and the catalyst;
(3) with colloid after still aging 4～12 hours, after filtration, obtain solid product after the washing;
(4) solid product is 110～150
oC drying 4～8 hours is 550～850
oC roasting 4-8 hour makes catalyst.
6. toluene liquid phase selective oxidation Preparation of catalysts method according to claim 5, it is characterized in that: described cationic surfactant is selected from softex kw, sodium cetanesulfonate, hexadecylamine; Organic polymer is selected from polyethylene glycol, polyvinyl alcohol, acid polyethylene, polyacrylic acid, polyoxyethylene.
7. the described toluene liquid phase of claim 3 selective oxidation Preparation of catalysts method is characterized in that adopting immersion process for preparing, comprises the steps:
(1) with transition metal vanadate Me
xV
yO is dispersed in alcohol or the alcohol-water mixed solution;
(2) under stirring condition, support powder or particle joined in the above-mentioned mixed liquor flood;
(3) mixture behind the dipping is at 110-120
oDry 4-6 hour of C is at 450-850
oC roasting 4-8 hour makes catalyst.
8. toluene liquid phase selective oxidation Preparation of catalysts method according to claim 7, it is characterized in that: described alcohol is selected from ethanol, propyl alcohol, butanols, phenmethylol; Described alcohol-water solution is the aqueous solution of ethanol, propyl alcohol or butanols, and alcohol is 1～5 with the volume ratio of water.
9. the described catalyst of claim 1 is as toluene liquid phase selective oxidation Application of Catalyst.
10. application according to claim 9, reaction condition is as follows: reaction system is by catalyst, toluene, oxidant, solvent composition, and reaction temperature is 30 ~ 120
oC, 1～4 hour reaction time; Described oxidant is oxygen, air, hydrogen peroxide or TBHP; Solvent is selected from acetonitrile, glacial acetic acid, water, and the volume ratio of solvent and toluene is 1～6, and the mol ratio of oxidant and toluene is 1～6, and the mass ratio of catalyst and toluene is 0.01～0.1.
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| CN105126860A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Toluene direct oxidation catalyst and preparation method thereof |
| CN105126857A (en) * | 2015-07-31 | 2015-12-09 | 齐国良 | Catalyst for catalyzing direct oxidation of toluene to prepare benzaldehyde and preparation method thereof |
| CN106423294A (en) * | 2015-08-12 | 2017-02-22 | 中国石油化工股份有限公司 | Catalyst for preparing aromatic polycarboxylic acid by liquid phase oxidization |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6743952B2 (en) * | 2002-03-28 | 2004-06-01 | Council Of Scientific And Industrial Research | Selective liquid phase air oxidation of toluene catalysed by composite catalytic system |
| CN1634657A (en) * | 2004-11-26 | 2005-07-06 | 南京大学 | Catalyst for toluene gas-phase oxidation and preparation method and use thereof |
-
2010
- 2010-11-17 CN CN2010105471417A patent/CN101972646B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6743952B2 (en) * | 2002-03-28 | 2004-06-01 | Council Of Scientific And Industrial Research | Selective liquid phase air oxidation of toluene catalysed by composite catalytic system |
| CN1634657A (en) * | 2004-11-26 | 2005-07-06 | 南京大学 | Catalyst for toluene gas-phase oxidation and preparation method and use thereof |
Non-Patent Citations (5)
| Title |
|---|
| JIAZHEN GE ET AL.: "Surface acidic and redox properties of V-Zr-O catalysts for the selective oxidation of toluene to benzaldehyde", 《JOURNAL OF MOLECULAR CATALYSIS A：CHEMICAL》, vol. 278, 7 September 2007 (2007-09-07) * |
| MINGWEI XUE ET AL.: "Surface acidic and redox properties of V-Ag-Ni-O catalysts for the selective oxidation of toluene to benzaldehyde", 《APPLIED CATALYSIS A：GENERAL》, vol. 330, 13 July 2007 (2007-07-13) * |
| WU JUN-PING ET AL.: "Selective Oxidation of Toluene with Hydrogen Peroxide Catalyzed by V-Mo-based Catalyst", 《CHEM.RES.CHINESE U.》, vol. 23, no. 5, 31 December 2007 (2007-12-31), pages 586 - 1 * |
| 照日格图等: "Ni-V-O催化剂上丙烷氧化脱氢制丙烯的反应", 《催化学报》, vol. 21, no. 4, 31 July 2000 (2000-07-31), pages 332 - 1 * |
| 王敏: "液相沉淀法制备钒酸铁纳米光催化剂及其光催化性能研究", 《中国博士学位论文全文数据库（电子期刊）工程科技I辑》, 31 December 2009 (2009-12-31) * |
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