CN105251538A - Preparation method of catalyst H6P2W15Mo3O62/TiO2 and n-pentyl acetate - Google Patents

Preparation method of catalyst H6P2W15Mo3O62/TiO2 and n-pentyl acetate Download PDF

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CN105251538A
CN105251538A CN201510712923.4A CN201510712923A CN105251538A CN 105251538 A CN105251538 A CN 105251538A CN 201510712923 A CN201510712923 A CN 201510712923A CN 105251538 A CN105251538 A CN 105251538A
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吕宝兰
陈都
龚文朋
何云鹏
杨水金
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Hubei Normal University
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Abstract

The invention discloses a preparation method of catalyst H6P2W15Mo3O62/TiO2 and n-pentyl acetate. Dawson H6P2W15Mo3O62 is prepared with a hydrothermal method, then TiO2 loaded Dawson type P-W-Mo-heteropolyacid catalyst H6P2W15Mo3O62/TiO2 is prepared with an impregnation method, the structure of the TiO2 loaded Dawson type P-W-Mo-heteropolyacid catalyst H6P2W15Mo3O62/TiO2 is characterized with FT-IR and XRD methods, and the catalytic activity of catalytic activity on esterification reaction is studied. The optimized conditions for preparing the catalyst are that the activation temperature is 150 DEG C, the calcination time is 4.5 h, and the load of the H6P2W15Mo3O62/TiO2 is 40%. The n-pentyl acetate synthesized by the catalyst of the H6P2W15Mo3O62/TiO2 has the advantages of excellent catalytic activity, mild reaction condition, high product yield, no environmental pollution and better recycling performance. Therefore, the H6P2W15Mo3O62/TiO2 is an excellent catalyst for synthesizing the n-pentyl acetate and has an excellent application prospect.

Description

A kind of catalyst H 6p 2w 15mo 3o 62/ TiO 2with the preparation method of n-amyl acetate
Technical field
The present invention relates to a kind of catalyst process, particularly relate to a kind of catalyst H 6p 2w 15mo 3o 62/ TiO 2with the preparation method of n-amyl acetate.
Background technology
N-amyl acetate is the liquid that water white transparency has banana and pears fragrance, is important synthetic perfume and organic solvent.Be slightly soluble in water, can be miscible with alcohol ether.Main as solvent in Chemical Manufacture, timber industry is for the manufacture of paint, leather industry is for the manufacture of artificial leather, photosensitive industry is for the manufacture of film, national defense industry is for the manufacture of gunpowder, daily chemical industry is for the manufacture of cosmetics, and medical industry is used as the extractant of penicillin, is used as chemical reagent in analytical chemistry.Can be used for plastics textile industry in addition.Along with people are to the pay attention to day by day of living environment, the research emphasis of organic synthesis is placed on the few green syt of environmental pollution by increasing researcher, green syt requires to adopt nontoxic reagent, solvent or catalyst in building-up process, the pollutant of course of reaction discharge is minimum, and productivity requirements is high as far as possible simultaneously.
Usually this compounds be under the catalysis of the concentrated sulfuric acid with glacial acetic acid and n-amyl alcohol for raw material is synthesized by esterification, but this reaction yield is low, and side reaction is many and equipment corrosion serious, is not desirable experimental program.On the basis of this problem, researchers have carried out again a large amount of discussion work, the new catalyst of continuous searching is to improve the synthesis of this compounds, therefore solid super-strong acid is developed, stannous oxide, Cericammoniumsulfate, sulfonation silica gel, niter cake, the catalyst such as solid-carrying heteropolyacid, have good catalytic action to esterification.But above method also exists catalyst recovery difficulty, post-reaction treatment complex process, the deficiencies such as product and unreacting material loss, are thus difficult to obtain further Application and Development.
Summary of the invention
Object of the present invention is just to provide a kind of catalyst H to solve the problem 6p 2w 15mo 3o 62/ TiO 2with the preparation method of n-amyl acetate.
The present invention is achieved through the following technical solutions above-mentioned purpose:
The present invention includes reagent: sodium tungstate [Na 2wO 42H 2o], sodium molybdate [Na 2moO 4h 2o], sodium hydrogen phosphate [Na 2hPO 42H 2o], tetrabutyl titanate, the concentrated sulfuric acid, absolute ether, glacial acetic acid, n-amyl alcohol, cyclohexane, saturated aqueous common salt, anhydrous calcium chloride; Instrument: measure organic preparing instrument, electric mixer, PKW-III type electric energy-saving temperature controller, Abbe refractometer, electronic balance, Nicolet5700 type infrared Raman spectrometer, powder diffraction analysis D8ADVANCE type x-ray diffractometer in beam ground;
Described catalyst H 6p 2w 15mo 3o 62/ TiO 2preparation method:
Hydro-thermal method prepares Dawson phosphotungstomolybdic acid H 6p 2w 15mo 3o 62
A: the Na taking 7.3g 2moO 4h 2o and 51.1gNa 2wO 42H 2o is dissolved in the water of 12.5mL and 80mL respectively, is then mixed by two kinds of solution;
B: by the Na of 5.8g 2hPO 42H 2o is dissolved in 12.5mL water, is added in the middle of above-mentioned mixed solution by the solution of dissolving, after being heated to 100 DEG C, slowly drips the dense H of 20mL 2sO 4, with the thermotonus 8h of 160 DEG C in water heating kettle, be cooled to room temperature, obtain yellow solid;
C: be dissolved in 50mL distilled water, with absolute ether extraction, separates the compound of lower floor's ether, at room temperature dry 12h, then puts into drying box and can obtain H with 12h dry under the condition of 60 DEG C 6p 2w 15mo 3o 62;
Hydro-thermal method prepares carrier TiO 2
The tetrabutyl titanate of 6.6mL is under agitation dropwise added in the distilled water of 65mL slowly, after stirring 30min, at 180 DEG C of Water Under thermal response 10h, be cooled to room temperature and obtain white precipitate, through filtering and washing 3 times, after natural subsidence 2 times, dry at 70 DEG C, namely porphyrize obtains titania powder;
The synthesis of n-amyl acetate:
A: be furnished with electric mixer, by necessarily measuring than adding glacial acetic acid and n-amyl alcohol in the 150mL three-necked bottle of air lock and water knockout drum, water entrainer and a certain amount of catalyst, load onto thermometer, water knockout drum and reflux condensing tube, adds hot reflux a period of time, slightly cold;
B: merged by organic layer, use saturated common salt water washing, then use the dry 15min of anhydrous calcium chloride, distillation organic phase, collects the cut of more than 130 DEG C, obtains water white transparency and have fruital taste fluid product, weigh and measure index of refraction, calculated yield.
Improve as one, described catalyst H 6p 2w 15mo 3o 62/ TiO 2preparation method infusion process can be adopted to prepare H 6p 2w 15mo 3o 62/ TiO 2substitute, be specially:
Take a certain amount of H 6p 2w 15mo 3o 62and TiO 2in the beaker filling certain water gaging, with the little fiery evaporate to dryness of crucible after stirred at ambient temperature 12h, put into Muffle furnace for subsequent use to grind after certain temperature calcination regular hour, obtain H 6p 2w 15mo 3o 62/ TiO 2catalyst.
Beneficial effect of the present invention is:
The present invention is a kind of catalyst H 6p 2w 15mo 3o 62/ TiO 2with the preparation method of n-amyl acetate, compared with prior art, the present invention's infusion process has prepared Dawson type structure phosphorus tungsten loaded by heteropoly acid TiO 2catalyst H 6p 2w 15mo 3o 62/ TiO 2, by infrared spectrum, X-ray powder diffraction means, its structure is characterized, optimizes the optimum experimental condition determining Sythesis of n-amyl acetate.The optimal conditions of catalyst preparing is: activation temperature 150 DEG C, calcination time 4.5h, H 6p 2w 15mo 3o 62load capacity 40%.When fixing acetic acid consumption is 0.1mol, n (n-amyl alcohol): n (glacial acetic acid)=1.4:1, catalyst amount accounts for 0.5% of reaction mass gross mass, reaction time 90min, water entrainer cyclohexane consumption is 8mL, and the average yield of n-amyl acetate can reach 85.4%.With H 6p 2w 15mo 3o 62/ TiO 2for catalyst Sythesis of n-amyl acetate has good catalytic activity, the advantages such as its reaction condition is gentle, and product yield is high, non-environmental-pollution, and recycling performance is better.Therefore H 6p 2w 15mo 3o 62/ TiO 2be the good catalyst of Sythesis of n-amyl acetate, have a good application prospect.
Accompanying drawing explanation
Fig. 1 is H of the present invention 6p 2w 15mo 3o 62/ TiO 2, TiO 2, H 6p 2w 15mo 3o 62infared spectrum
Fig. 2 is H of the present invention 6p 2w 15mo 3o 62/ TiO 2, TiO 2, H 6p 2w 15mo 3o 62xRD collection of illustrative plates.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described:
The present invention includes reagent: sodium tungstate [Na 2wO 42H 2o], sodium molybdate [Na 2moO 4h 2o], sodium hydrogen phosphate [Na 2hPO 42H 2o], tetrabutyl titanate, the concentrated sulfuric acid, absolute ether, glacial acetic acid, n-amyl alcohol, cyclohexane, saturated aqueous common salt, anhydrous calcium chloride; Instrument: measure organic preparing instrument, electric mixer, PKW-III type electric energy-saving temperature controller, Abbe refractometer, electronic balance, Nicolet5700 type infrared Raman spectrometer, powder diffraction analysis D8ADVANCE type x-ray diffractometer in beam ground;
Described catalyst H 6p 2w 15mo 3o 62/ TiO 2preparation method:
Hydro-thermal method prepares Dawson phosphotungstomolybdic acid H 6p 2w 15mo 3o 62
A: the Na taking 7.3g 2moO 4h 2o and 51.1gNa 2wO 42H 2o is dissolved in the water of 12.5mL and 80mL respectively, is then mixed by two kinds of solution;
B: by the Na of 5.8g 2hPO 42H 2o is dissolved in 12.5mL water, is added in the middle of above-mentioned mixed solution by the solution of dissolving, after being heated to 100 DEG C, slowly drips the dense H of 20mL 2sO 4, with the thermotonus 8h of 160 DEG C in water heating kettle, be cooled to room temperature, obtain yellow solid;
C: be dissolved in 50mL distilled water, with absolute ether extraction, separates the compound of lower floor's ether, at room temperature dry 12h, then puts into drying box and can obtain H with 12h dry under the condition of 60 DEG C 6p 2w 15mo 3o 62;
Hydro-thermal method prepares carrier TiO 2
The tetrabutyl titanate of 6.6mL is under agitation dropwise added in the distilled water of 65mL slowly, after stirring 30min, at 180 DEG C of Water Under thermal response 10h, be cooled to room temperature and obtain white precipitate, through filtering and washing 3 times, after natural subsidence 2 times, dry at 70 DEG C, namely porphyrize obtains titania powder;
The synthesis of n-amyl acetate:
A: be furnished with electric mixer, by necessarily measuring than adding glacial acetic acid and n-amyl alcohol in the 150mL three-necked bottle of air lock and water knockout drum, water entrainer and a certain amount of catalyst, load onto thermometer, water knockout drum and reflux condensing tube, adds hot reflux a period of time, slightly cold;
B: merged by organic layer, use saturated common salt water washing, then use the dry 15min of anhydrous calcium chloride, distillation organic phase, collects the cut of more than 130 DEG C, obtains water white transparency and have fruital taste fluid product, weigh and measure index of refraction, calculated yield.
Improve as one, described catalyst H 6p 2w 15mo 3o 62/ TiO 2preparation method infusion process can be adopted to prepare H 6p 2w 15mo 3o 62/ TiO 2substitute, be specially:
Take a certain amount of H 6p 2w 15mo 3o 62and TiO 2in the beaker filling certain water gaging, with the little fiery evaporate to dryness of crucible after stirred at ambient temperature 12h, put into Muffle furnace for subsequent use to grind after certain temperature calcination regular hour, obtain H 6p 2w 15mo 3o 62/ TiO 2catalyst.
Experimental result and analysis:
Catalyst H 6p 2w 15mo 3o 62/ TiO 2sign
The IR spectrum of catalyst: H 6p 2w 15mo 3o 62/ TiO 2, TiO 2, H 6p 2w 15mo 3o 62infrared spectrogram as shown in Figure 1, in figure: H 6p 2w 15mo 3o 62/ TiO 2(a) TiO 2(b), H 6p 2w 15mo 3o 62(c)
Found out by Fig. 1, self-control H 6p 2w 15mo 3o 621086.9,962.7,898.3,762.7cm -1there is Dawson architectural feature absworption peak in place, and v as(P-O a) the relative phosphotungstic acid red shift in position of absworption peak, and v as(M=O d) (M=W, Mo) blue shift occurs [19], show that Mo enters coordination atom position, can determine that synthetic is Dawson type phosphorus tungsten heteropoly acid H 6p 2w 15mo 3o 62.Load rear catalyst H 6p 2w 15mo 3o 62/ TiO 2principal character absworption peak be H 6p 2w 15mo 3o 621081.6cm -1v as(P-O a), 984.6cm -1v as(W=O d) and 887.0cm -1v as(W-O b-Mo) absworption peak.
The XRD spectrum of catalyst: H 6p 2w 15mo 3o 62/ TiO 2, TiO 2, H 6p 2w 15mo 3o 62xRD spectrum figure as shown in Figure 2.In figure: H 6p 2w 15mo 3o 62/ TiO 2(a), TiO 2(b), H 6p 2w 15mo 3o 62(c)
Fig. 2 is known, H 6p 2w 15mo 3o 62be 10 °, 21 °, 26 °, 35 ° at 2 θ to locate to occur strong characteristic diffraction peak, be also occur diffraction maximum in 40 ~ 60 ° at 2 θ, be 25 ° at 2 θ and also occur anatase diffraction maximum, the catalyst H after load 6p 2w 15mo 3o 62/ TiO 2be 26 ° at 2 θ and occur TiO 2, there is faint H at 10 °, 35 ° places in characteristic diffraction peak simultaneously 6p 2w 15mo 3o 62characteristic diffraction peak, illustrates H 6p 2w 15mo 3o 62effectively be dispersed in carrier TiO 2on.
H 6p 2w 15mo 3o 62/ TiO 2the optimization of preparation condition
For determining the optimal conditions of catalyst preparing, high spot reviews calcining heat, soak time and H 6p 2w 15mo 3o 62load capacity.To catalyze and synthesize n-amyl acetate for probe reaction, probe reaction condition is: n (n-amyl alcohol): n (glacial acetic acid)=1.3:1, the consumption of catalyst accounts for 0.5% of reaction mass gross mass, and cyclohexane consumption is 8mL, and the reaction time is 75min.
Calcining heat is on the impact of catalyst activity
Be 4h at fixing soak time, load capacity is 30%, by changing calcining heat, has investigated the impact of calcining heat on catalyst activity.It is as shown in table 1 that it affects result.
Table 1 calcining heat is on the impact of catalyst activity
As shown in Table 1: the catalytic activity of calcining heat on catalyst has impact, calcining heat is 150 DEG C time, and product yield is the highest, and catalytic activity is best.So select 150 DEG C as optimum calcinating temperature.
Soak time is on the impact of catalyst activity
Be 150 DEG C in fixing calcining heat, load capacity is 30%, and by changing soak time, investigated the impact of soak time on catalyst activity, its result is as shown in table 2.
Table 2 soak time is on the impact of catalyst activity
As shown in Table 2: soak time has impact to catalyst activity, peak when 4.5h.Therefore catalyst optimum activating time is 4.5h.
Load capacity is on the impact of catalyst activity
Be 150 DEG C in fixing calcining heat, soak time is 4.5h, by changing H 6p 2w 15mo 3o 62load capacity, has investigated H 6p 2w 15mo 3o 62load capacity on the impact of catalyst activity, shown in its result table 3.
Table 3H 6p 2w 15mo 3o 62load capacity is on the impact of catalyst activity
Table3EffectofH 6P 2W 15Mo 3O 62loadingontheactivityofcatalyst
As shown in Table 3: H 6p 2w 15mo 3o 62load capacity has a certain impact to catalyst activity, along with H during beginning 6p 2w 15mo 3o 62the increase of load capacity, product yield has rising.After load capacity reaches 40%, along with H 6p 2w 15mo 3o 62the continuation of load capacity increases, and product yield reduces.Its reason is that load capacity is too little, and the catalytic active center provided is just few, and catalytic activity is lower; But load capacity is excessive, just easily cause the reunion of heteropoly acid, specific area is little, and the catalytic performance of catalyst reduces.Therefore select 40% as best H 6p 2w 15mo 3o 62load capacity.
From table 1, table 2, table 3, the optimal conditions of catalyst preparing is: activation temperature 150 DEG C, calcination time 4.5h, H 6p 2w 15mo 3o 62load capacity 40%.
The optimization of n-amyl acetate reaction condition:
Molar ratio of alcohol to acid is on the impact of yield
When fixing acetic acid consumption is 0.1mol, the consumption of catalyst accounts for 0.5% of reaction mass gross mass, and cyclohexane consumption is 8mL, and the reaction time is 75min, changes molar ratio of alcohol to acid, inquires into molar ratio of alcohol to acid to the impact of yield, the results are shown in Table 4.
Table 4 molar ratio of alcohol to acid is on the impact of yield
As shown in Table 4, along with molar ratio of alcohol to acid increases gradually, yield also increases gradually, and when molar ratio of alcohol to acid is 1.40:1, yield reaches maximum, then increases molar ratio of alcohol to acid, and yield reduces on the contrary.Therefore determine that best molar ratio of alcohol to acid is 1.40:1.
Catalyst amount is on the impact of yield
When fixing acetic acid consumption is 0.1mol, molar ratio of alcohol to acid is 1.40:1, and cyclohexane consumption is 8mL, and the reaction time is 75min, changes catalyst amount, inquires into catalyst amount to the impact of yield, the results are shown in Table 5.
Table 5 catalyst amount is on the impact of yield
As shown in Table 5, along with catalyst amount increases gradually, yield also increases gradually, and when catalyst amount is 0.5% of reaction-ure mixture, yield reaches maximum, then increases catalyst amount, and yield change is little.Therefore determine that optimum catalyst consumption is 0.5%.
The impact of reaction time on yield
When fixing acetic acid consumption is 0.1mol, molar ratio of alcohol to acid 1.40:1, cyclohexane consumption 8mL, reaction time 75min, catalyst amount 0.5%, changes the reaction time, inquires into the impact of reaction time on yield, the results are shown in Table 6.
The impact of table 6 reaction time on yield
As shown in Table 6, along with the reaction time extends, yield also increases gradually, and for yield during 90min reaches maximum when reacted, then extend the reaction time, yield reduces on the contrary.Therefore determine that optimum reacting time is 90min.
3.3.4 water entrainer consumption is on the impact of reaction yield
When fixing acetic acid consumption is 0.1mol, molar ratio of alcohol to acid 1.40:1, reaction time 90min, catalyst amount 0.5%, changes water entrainer cyclohexane consumption, inquires into water entrainer cyclohexane consumption to the impact of yield, the results are shown in Table 7.
Table 7 water entrainer consumption is on the impact of yield
As shown in Table 7, along with water entrainer consumption increases, yield also increases gradually, and when water entrainer consumption is 8mL, yield reaches maximum, then increases water entrainer consumption, and yield reduces on the contrary.Therefore determine that best water entrainer consumption is 8mL.
Consolidated statement 4,5,6,7 known, be 1.40:1 at molar ratio of alcohol to acid, catalyst amount is 0.5%, reaction time 90min, and under the optimal conditions of water entrainer cyclohexane 8mL, the yield of n-amyl acetate is 86.2% reach maximum.Under this optimal conditions, parallel three experiment yields are respectively 86.2%, 85.7%, 84.3%, and average yield is 85.4%.
The recycling Experimental Research of catalyst
With optimal conditions, the stability of catalyst has been investigated.After having reacted, suction filtration goes out catalyst while hot, and with the impurity of its surface attachment of absolute ethyl alcohol eccysis, tested after 110 DEG C of dry 3h by recovery catalyst, result is as shown in table 8 below.
Table 8 catalyst reuse experimental result
As can be seen from Table 8, catalyst reuses 3 times, and the yield of product is followed successively by: 73.1%, 70.1% and 66.9%.Catalytic efficiency has the trend of reduction, and its main cause may be owing to reusing repeatedly, and phosphotungstomolybdic acid partial exfoliation, causes catalytic efficiency to reduce.But after catalyst reuses 3 times, yield still has 66.9%, illustrate that this catalyst has good catalytic effect, there is the advantage of recycling, overcome traditional catalyst and be difficult to recycle, the shortcoming of contaminated environment.
The sign of product:
H 6p 2w 15mo 3o 62/ TiO 2the n-amyl acetate catalyzed and synthesized carries out infrared spectrum analysis.Analysis result shows: the principal character peak of the infrared spectrum of sample: 1741cm -1(C=O), 1239cm -1(C-O-C), has consistent characteristic absorption peak with the standard IR spectrogram of n-amyl acetate.
By the n-amyl acetate that this law is obtained, its index of refraction with literature value [20] substantially conform to, product is colourless transparent liquid, and boiling range is 140 DEG C ~ 149 DEG C, has fruital taste.
More than show and describe general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and description just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.

Claims (2)

1. a catalyst H 6p 2w 15mo 3o 62/ TiO 2preparation method with n-amyl acetate, is characterized in that, comprises reagent: sodium tungstate [Na 2wO 42H 2o], sodium molybdate [Na 2moO 4h 2o], sodium hydrogen phosphate [Na 2hPO 42H 2o], tetrabutyl titanate, the concentrated sulfuric acid, absolute ether, glacial acetic acid, n-amyl alcohol, cyclohexane, saturated aqueous common salt, anhydrous calcium chloride; Instrument: measure organic preparing instrument, electric mixer, PKW-III type electric energy-saving temperature controller, Abbe refractometer, electronic balance, Nicolet5700 type infrared Raman spectrometer, powder diffraction analysis D8ADVANCE type x-ray diffractometer in beam ground;
Described catalyst H 6p 2w 15mo 3o 62/ TiO 2preparation method:
Hydro-thermal method prepares Dawson phosphotungstomolybdic acid H 6p 2w 15mo 3o 62
A: the Na taking 7.3g 2moO 4h 2o and 51.1gNa 2wO 42H 2o is dissolved in the water of 12.5mL and 80mL respectively, is then mixed by two kinds of solution;
B: by the Na of 5.8g 2hPO 42H 2o is dissolved in 12.5mL water, is added in the middle of above-mentioned mixed solution by the solution of dissolving, after being heated to 100 DEG C, slowly drips the dense H of 20mL 2sO 4, with the thermotonus 8h of 160 DEG C in water heating kettle, be cooled to room temperature, obtain yellow solid;
C: be dissolved in 50mL distilled water, with absolute ether extraction, separates the compound of lower floor's ether, at room temperature dry 12h, then puts into drying box and can obtain H with 12h dry under the condition of 60 DEG C 6p 2w 15mo 3o 62;
Hydro-thermal method prepares carrier TiO 2
The tetrabutyl titanate of 6.6mL is under agitation dropwise added in the distilled water of 65mL slowly, after stirring 30min, at 180 DEG C of Water Under thermal response 10h, be cooled to room temperature and obtain white precipitate, through filtering and washing 3 times, after natural subsidence 2 times, dry at 70 DEG C, namely porphyrize obtains titania powder;
The synthesis of n-amyl acetate:
A: be furnished with electric mixer, by necessarily measuring than adding glacial acetic acid and n-amyl alcohol in the 150mL three-necked bottle of air lock and water knockout drum, water entrainer and a certain amount of catalyst, load onto thermometer, water knockout drum and reflux condensing tube, adds hot reflux a period of time, slightly cold;
B: merged by organic layer, use saturated common salt water washing, then use the dry 15min of anhydrous calcium chloride, distillation organic phase, collects the cut of more than 130 DEG C, obtains water white transparency and have fruital taste fluid product, weigh and measure index of refraction, calculated yield.
2. catalyst H according to claim 1 6p 2w 15mo 3o 62/ TiO 2preparation method with n-amyl acetate, is characterized in that: described catalyst H 6p 2w 15mo 3o 62/ TiO 2preparation method infusion process can be adopted to prepare H 6p 2w 15mo 3o 62/ TiO 2substitute, be specially:
Take a certain amount of H 6p 2w 15mo 3o 62and TiO 2in the beaker filling certain water gaging, with the little fiery evaporate to dryness of crucible after stirred at ambient temperature 12h, put into Muffle furnace for subsequent use to grind after certain temperature calcination regular hour, obtain H 6p 2w 15mo 3o 62/ TiO 2catalyst.
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CN108144600A (en) * 2017-12-26 2018-06-12 聊城大学 A kind of preparation method and its usage of-ten two tungsten oxygen cluster catalyst of three core zinc
CN108144600B (en) * 2017-12-26 2020-07-17 聊城大学 Preparation method and application of trinuclear zinc-dodecatungsten oxygen cluster catalyst
CN110120515A (en) * 2019-05-29 2019-08-13 重庆长安新能源汽车科技有限公司 A kind of surface modification lithium-ion battery anode material and preparation method thereof
CN110433874A (en) * 2019-09-06 2019-11-12 温州旭扬膜结构工程有限公司 A kind of phosphotungstomolybdic acid-metal organic frame proton exchange membrane and its preparation method
CN113880712A (en) * 2021-09-16 2022-01-04 泰兴金江化学工业有限公司 Preparation method of ethyl acetate
CN113880712B (en) * 2021-09-16 2023-08-04 泰兴金江化学工业有限公司 Preparation method of ethyl acetate
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