CN103316696A - Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method - Google Patents
Preparation method of acetyl tri-n-butyl citrate and catalyst used in preparation method Download PDFInfo
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- CN103316696A CN103316696A CN2013102784273A CN201310278427A CN103316696A CN 103316696 A CN103316696 A CN 103316696A CN 2013102784273 A CN2013102784273 A CN 2013102784273A CN 201310278427 A CN201310278427 A CN 201310278427A CN 103316696 A CN103316696 A CN 103316696A
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Abstract
The invention discloses a preparation method of acetyl tri-n-butyl citrate. The solid super acid SO-42-/ZrO2-WO3 prepared in the invention is used as a catalyst in the preparation method. The preparation method comprises the following steps sequentially: 1), reacting citric acid and n-butyl alcohol which are used as the raw material with the catalyst for 3-4hours in a solvent under the condition of circumfluence to repel water; 2), reducing the temperature of the reactant obtained in the step 1) to normal temperature, adding acetic anhydride with the amount that is equal to the molar weight of the citric acid used in the step 1) and adding catalyst, reacting for 1-3hours at normal temperature; after the reaction is finished, firstly filtering to remove the catalyst, and then subjecting the filtrate to reduced pressure distillation in order to remove the solvent, the n-butyl alcohol which does not participate in the reaction and the acetic acid generated during the reaction, so as to obtain the acetyl tri-n-butyl citrate. The acetyl tri-n-butyl citrate prepared by the method disclosed by the invention has the characteristics of high production efficiency, easy and convenient operation, environment-friendly production and the like.
Description
Technical field
The present invention relates to a kind of organic compound--the preparation method of-ATBC and used catalyst.
Background technology
ATBC is called for short ATBC, and its molecular formula is C
20H
34O
8, its structural formula is shown in S-1, and its pure product are colourless, tasteless oily liquids, 343 ℃ of boiling points; Be a kind of novel asepsis environment-protecting plasticizer, have nonpoisonous and tasteless, compatibility good, plasticizing efficiency is high, easily by advantage such as biodegradation and volatility be little, cold resistance, light resistance and have excellent water-resistance alternative phthalate conventional plasticizers.Can be used as polyvinyl chloride, celluosic resin and elastomeric plasticizer, be used for nontoxic PVC granulation, food container, the toy for children goods, medical product, goods such as film, sheet material, cellulose paint, also can be used as the stabilizing agent of polyvinylidene chloride etc., is a kind of important chemical product.
S-1
The preparation of ATBC mainly is that the esterification by tri-n-butyl citrate (be called for short TBC) prepares.China's citric acid output is bigger, and supply exceed demand, but the catalyst that the synthetic TBC method of tradition adopts mostly is the concentrated sulfuric acid, though this method productive rate height, the sulfuric acid low price exists side reaction many, product colour is dark, quality is low, the spent acid contaminated environment, severe corrosion equipment, post processing complexity, labour intensity is big, formation efficiency is low, shortcomings such as cost height, and the synthetic of TBC is that the raw material esterification makes with citric acid and butanols mainly.Its reaction principle is mainly shown in S-2.
S-2
Used catalyst roughly has at present: (1) p-methyl benzenesulfonic acid, benzene sulfonic acid, pyrovinic acid, (2) sulfamic acid of sulfamic acid and replacement replaces uncle's dithiocarbamic acid sulfate, (3) potassium acid sulfate, niter cake, (4) strong acid ion exchange resin, (5) solid super-strong acid.The research that is used for the solid super-strong acid of catalysis generation TBC is mainly TiO
2And SiO
2The research of solid super-strong acid and modification thereof, and to ZrO
2The solid super-strong acid research of type is less, and finding is used for the ZrO of ATBC at present
2The solid super-strong acid of type is only seen S
2O
8 2-/ ZrO
2, S
2O
8 2-/ TiO
2-ZrO
2, SO
4 2-/ ZrO
2-Al
2O
3-Fe
3O
4,Zr (SO
4)
24H
2The O/SBA-15 mesoporous molecular sieve catalyst, SO
4 2-/ ZrO
2-MCM-41 etc.And the used solid super-strong acid SO of the present invention
4 2-/ ZrO
2-WO
3(SZW) do not appear in the newspapers.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of ATBC and used solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW); The present invention has characteristics such as production efficiency height, easy and simple to handle, environmental protection production.
In order to solve the problems of the technologies described above, the invention provides a kind of solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW), its preparation method is for carrying out following steps successively:
1., take by weighing the ZrOCl of 5g
28H
2O is dissolved in the deionized water, is made into mass ratio M (ZrOCl
2): M (H
2O)=1:7.8 ~ 8.2(is preferably 1:8) ZrOCl
2The aqueous solution; Utilize ammoniacal liquor (slowly adding ammoniacal liquor) to regulate ZrOCl
2The pH to 8.9 of the aqueous solution ~ 9.1(is preferably 9);
2., with step 1. the mixed liquor of gained after stirring 20 ~ 30 min under the room temperature, be preferably 80 ℃ of ageing 36 h in 75 ~ 85 ℃ of ageing 34 ~ 38h(); Filter, the filter cake of gained washs to there not being Cl with clear water
-The back is preferably 550 ℃ of following roasting 12 h in 500 ~ 600 ℃ of roasting 10 ~ 14 h();
3., after 2. gains are cooled to room temperature after the roasting of gained with step, grind to form the powder that to cross 100 orders (that is, can cross 100 purposes sieves); Place the ammonium metatungstate aqueous solution 13 ~ 18ml that contains 0.8 ~ 1.2g ammonium metatungstate [to be preferably and to contain 1g ammonium metatungstate ((NH then
4)
6H
2W
12O
40) ammonium metatungstate aqueous solution (15ml)] dipping 24 h; Filter, the filter cake of gained is preferably 600 ℃ of roasting 3h in 550 ~ 650 ℃ of roasting 2.5 ~ 3.5h();
4., after 3. gains are cooled to room temperature after the roasting of gained with step, grind to form and to cross 100 purpose powder; Placing 30 ~ 70ml(to be preferably 50ml then) concentration is the H of l mol/L
2SO
4Dipping 24 h in the solution; Filter, the filter cake of gained is preferably 550 ℃ of roasting 3 h in 500 ~ 600 ℃ of roasting 2.5 ~ 3.5h(); After being cooled to room temperature, get pulverous solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW).
Solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) aperture is 11nm, and specific area is 225 ~ 245 m
2/ g.
Remarks explanation: H in this step
2SO
4Consumption can guarantee that powder all is immersed in H
2SO
4In the solution.
The present invention also provides a kind of preparation method of ATBC, utilize method for preparing and solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW), carry out following steps successively:
1), will be as the citric acid of raw material and n-butanol and as the solid super-strong acid SO of catalyst
4 2-/ ZrO
2-WO
3(SZW) in solvent, under the reflux water-dividing condition, react 3 ~ 7h; The mol ratio of described citric acid and n-butanol is 1:3 ~ 3.5; The solid super-strong acid SO of citric acid adapted 0.1 ~ 0.3g of every 0.1mol
4 2-/ ZrO
2-WO
3(SZW);
2), after the reaction gains of step 1) are cooled to room temperature, add with the aceticanhydride of the used citric acid equimolar amounts of step 1) and add solid super-strong acid SO as catalyst
4 2-/ ZrO
2-WO
3(SZW) under room temperature, reacted 1 ~ 3 hour; Solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) with step 1) in the amount ratio of citric acid be: 0.03 ~ 0.10g solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW)/citric acid of 0.1mol;
After reaction finishes, filter to remove the solid super-strong acid SO as catalyst earlier
4 2-/ ZrO
2-WO
3(SZW), filtrate decompression distillation (for example be 0.02MPa, 80 ℃), get final product product---ATBC (ATBC).
Remarks explanations: above-mentioned decompression distillation purpose is for desolventizing, participates in the n-butanol of reaction and the acetic acid (as accessory substance) that reaction produces fully,
Improvement as the preparation method of ATBC of the present invention: the solvent in the step 1) is toluene.Generally speaking, the solvent of every 0.1mol citric acid adapted 50 ~ 200ml.
Further improvement as the preparation method of ATBC of the present invention:
In the step 1): the mol ratio of citric acid and n-butanol is 1:3.2; The solid super-strong acid SO of the citric acid adapted 0.1g of every 0.1mol
4 2-/ ZrO
2-WO
3Reaction time is 5h,
Step 2) in: solid super-strong acid SO
4 2-/ ZrO
2-WO
3With the amount ratio of citric acid in the step 1) be: 0.03g solid super-strong acid SO
4 2-/ ZrO
2-WO
3/ citric acid of 0.1mol; Reaction time is 3 hours.
Among the present invention, ammoniacal liquor is conventional industrial ammonia, namely contains the aqueous solution of ammonia 25%～28%.
Room temperature refers to 10 ~ 25 ℃.
The present invention has following technical advantage:
1, prepared a kind of catalyst--solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW), first Application has solved equipment corrosion, waste water handling problem that traditional handicraft produces with sulfuric acid in the esterification of citric acid and n-butanol, and easy to prepare, renewable repeated use, and is environmentally friendly, environmental protection.
2, use solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) make catalyst, reaction is control easily, and catalyst separates with product simply, and the catalytic activity height has reduced production cost.
3, adopt SO
4 2-/ ZrO
2The solid super-strong acid SO of system
4 2-/ ZrO
2-WO
3(SZW) replace that the advantage of the synthetic TBC of the concentrated sulfuric acid mainly is that corrosivity is little, " three wastes " discharging less, renewable repeated use, catalyst separate with product simply, catalytic activity is high and selectively well etc.
4, the present invention passes through at SO
4 2-/ ZrO
2Add component W(tungsten in the solid super-strong acid), with raising life of catalyst and stability, and be used for preparing TBC and ATBC with the esterification catalytic of citric acid and n-butanol, obtained a kind of production efficiency height, easy and simple to handle, the production new technique of environmental protection.
The specific embodiment
Embodiment 1, a kind of organic compound--the preparation method of-ATBC is raw material with citric acid, n-butanol, carries out following steps successively:
1), as the solid super-strong acid SO of catalyst
4 2-/ ZrO
2-WO
3(SZW) preparation, carry out following steps successively:
1., take by weighing the ZrOCl of 5g
28H
2O is dissolved in the deionized water (about 20ml), is made into mass ratio M (ZrOCl
2): M (H
2O)=ZrOCl of 1:8
2The aqueous solution; Ammoniacal liquor is slowly added in the above-mentioned solution, regulate pH to 9.
2., with step 1. the mixed liquor of gained after stirring 25 min under the room temperature, put into baking oven, in 80 ℃ of following ageing 36 h; Filter, the filter cake of gained washs to there not being Cl with clear water
-After, place Muffle furnace, in 550 ℃ of roasting 12 h.
3., after 2. gains are cooled to room temperature after the roasting of gained with step, grind to form the powder that to cross 100 orders (can cross 100 purposes sieves); Place then and contain 1g ammonium metatungstate ((NH
4)
6H
2W
12O
40) ammonium metatungstate aqueous solution (15ml) in dipping 24 h, filter, the filter cake of gained is 600 ℃ of following roasting 3h in Muffle furnace.
4., after 3. gains are cooled to room temperature after the roasting of gained with step, grind to form and to cross 100 purpose powder; Placing concentration then is the H of l mol/L
2SO
4Dipping 24 h among the solution 50ml; Filter, the filter cake of gained places Muffle furnace in 550 ℃ of roasting 3 h, be cooled to room temperature after, get pulverous solid super-strong acid SO
4 2-/ ZrO
2-WO
3
Final gained catalyst aperture is about 11nm, and specific area is 240 m
2About/g.
2), with the 0.1mol citric acid, the 0.3mol n-butanol, the SZW of 0.10g and 100ml toluene react under the reflux water-dividing condition in the there-necked flask (flask is furnished with condenser, water knockout drum and thermometer) of 250ml, constantly divide water outlet in the course of reaction.Stop reaction behind the reaction 5h, reactant liquor is cooled to room temperature.
3), in being cooled to the reactant liquor of room temperature, add the aceticanhydride of 0.1mol and the SZW of 0.05g, react 2h under the room temperature.
Reaction filters out catalyst S ZW, reuse after finishing.The acetic acid (as accessory substance) that produces in toluene, a small amount of unreacted n-butanol and the reaction is removed in filtrate decompression (0.02MPa) distillation (80 ℃), and still liquid is ATBC (ATBC) 33.61g, yield 83.5%.Its purity is 99.7%.
The preparation method of embodiment 2, a kind of organic compound----ATBC, with citric acid, n-butanol is raw material, carries out following steps successively:
1), as the solid super-strong acid SO of catalyst
4 2-/ ZrO
2-WO
3(SZW) preparation:
With embodiment 1.
2), with the 0.1mol citric acid, the 0.3mol butanols, the SZW of 0.10g and 100ml toluene react under the reflux water-dividing condition in the there-necked flask of 250ml, constantly divide water outlet in the course of reaction.Stop reaction behind the reaction 3h, reactant liquor is cooled to room temperature.
3), in being cooled to the reactant liquor of room temperature, add aceticanhydride and the 0.05g SZW of 0.1mol, react 1h under the room temperature.Filter out catalyst, reuse.The acetic acid that produces in toluene, a small amount of unreacted n-butanol and the reaction is removed in the filtrate decompression distillation, and still liquid is ATBC (ATBC) 31.92g, yield 79.3%.Its purity is 99.6%.
The preparation method of embodiment 3, a kind of organic compound----ATBC, with citric acid, n-butanol is raw material, carries out following steps successively:
1), solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) Preparation of Catalyst:
With embodiment 1.
2), with the 0.1mol citric acid, the 0.35mol n-butanol, 0.20g SZW and 100ml toluene react under the reflux water-dividing condition in the there-necked flask of 250ml, constantly divide water outlet in the course of reaction.React stop after 5 hours the reaction, reactant liquor is cooled to room temperature.
3), in being cooled to the reactant liquor of room temperature, add aceticanhydride and the 0.05g SZW of 0.1mol, react 2h under the room temperature.Filter out catalyst, reuse.The acetic acid that produces in toluene, a small amount of unreacted n-butanol and the reaction is removed in the filtrate decompression distillation, and still liquid is ATBC (ATBC) 35.90g, yield 89.2%.Its purity is 99.8%.
Embodiment 4, a kind of organic compound--the preparation method of-ATBC, with citric acid, n-butanol is raw material, carries out following steps successively:
1), solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) Preparation of Catalyst:
With embodiment 1.
2), with the 0.1mol citric acid, the 0.30mol butanols, 0.10g SZW and 100ml toluene react under the reflux water-dividing condition in the there-necked flask of 250ml, constantly divide water outlet in the course of reaction.Stop reaction behind the reaction 3h, reactant liquor is cooled to room temperature.
3), in being cooled to the reactant liquor of room temperature, add aceticanhydride and the 0.03g SZW of 0.1mol, react 1h under the room temperature.Filter out catalyst, reuse.The acetic acid that produces in toluene, a small amount of unreacted n-butanol and the reaction is removed in the filtrate decompression distillation, and still liquid is ATBC (ATBC) 28.74g, yield 71.4%.Its purity is 99.5%.
Material proportion, catalyst amount, step 2 among embodiment 5 ~ embodiment 13, the change embodiment 1) and the step 3) reaction time, thereby obtain corresponding embodiment 5 ~ embodiment 13, final gained product---the yield of ATBC is as shown in table 1.
The remarks explanation: the Preparation of catalysts method is with embodiment 1; The consumption of citric acid is constant.
Table 1 SZW catalytic synthesis of acetyl tri-n-butyl citrate
Comparative Examples 1, make the SZW in the Comparative Examples 11 into SO
4 2-/ WO
3-ZrO
2, all the other are equal to embodiment 11.
ATBC (ATBC) 29.62g of final gained, yield 73.6%.Its purity is 99.3%.
This SO
4 2-/ WO
3-ZrO
2The preparation method be: according to publishing in Hebei chemical industry 2012 the 35th " SO of the 7th phase of volume
4 2-/ WO
3-ZrO
2Catalyze and synthesize butyl acetate " be prepared.
Comparative Examples 2, make the SZW in the Comparative Examples 11 into SO
4 2-/ WO
3-TiO
2, all the other are equal to embodiment 11.。
ATBC (ATBC) 28.70g of final gained, yield 71.3%.Its purity is 99.3%.
SO
4 2-/ WO
3-TiO
2The preparation method be prepared according to " the mixed-metal oxides catalyzed with solid supported heteropolyacid synthesizing citric acid tributyl " published in using 2005 the 101st the 34th phases of volume of chemical industry.
Comparative Examples 3, with " the solid super-strong acid SO in the Comparative Examples 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in ammonium metatungstate ((NH
4)
6H
2W
12O
40) consumption make 1.3g into by 1g; All the other are with embodiment 11.
ATBC (ATBC) 32.48g of final gained, yield 80.7%.Its purity is 99.5%.
Comparative Examples 4, with " the solid super-strong acid SO in the Comparative Examples 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in ammonium metatungstate ((NH
4)
6H
2W
12O
40) consumption make 0.7g into by 1g; All the other are with embodiment 11.
ATBC (ATBC) 29.22g of final gained, yield 72.6%.Its purity is 99.4%.
Comparative Examples 5, with " the solid super-strong acid SO in the Comparative Examples 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in soak the sulfuric acid solution of (dipping) concentration change into and use 0.5mol/L; All the other are with embodiment 11.
ATBC (ATBC) 29.14g of final gained, yield 72.4%.Its purity is 99.1%.
Comparative Examples 6, with " the solid super-strong acid SO in the Comparative Examples 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in (dipping) the sulfuric acid time of soaking change 12h into; All the other are with embodiment 11.
ATBC (ATBC) 31.59g of final gained, yield 78.5%.Its purity is 99.4%.
Comparative Examples 7, with " the solid super-strong acid SO in the Comparative Examples 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " 3. the grinding in 4. all made 50 mesh sieves into to step with step; All the other are with embodiment 11.
ATBC (ATBC) 26.89g of final gained, yield 66.8%.Its purity is 99.1%.
At last, it is also to be noted that what more than enumerate only is several specific embodiments 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 (5)
1. solid super-strong acid SO
4 2-/ ZrO
2-WO
3, it is characterized in that: the preparation method is for carrying out following steps successively:
1., take by weighing the ZrOCl of 5g
28H
2O is dissolved in the deionized water, is made into mass ratio ZrOCl
2: H
2The ZrOCl of O=1:7.8 ~ 8.2
2The aqueous solution; Utilize ammoniacal liquor to regulate ZrOCl
2The pH to 8.9 of the aqueous solution ~ 9.1;
2., with step 1. the mixed liquor of gained after stirring 20 ~ 30 min under the room temperature, in 75 ~ 85 ℃ of ageing 34 ~ 38h; Filter, the filter cake of gained washs to there not being Cl with clear water
-The back is in 500 ~ 600 ℃ of roasting 10 ~ 14 h;
3., after 2. gains are cooled to room temperature after the roasting of gained with step, grind to form and to cross 100 purpose powder; Place ammonium metatungstate aqueous solution 13 ~ 18ml dipping 24 h that contain 0.8 ~ 1.2g ammonium metatungstate then; Filter, the filter cake of gained is in 550 ~ 650 ℃ of roasting 2.5 ~ 3.5h;
4., after 3. gains are cooled to room temperature after the roasting of gained with step, grind to form and to cross 100 purpose powder; Placing 30 ~ 70ml concentration then is the H of l mol/L
2SO
4Dipping 24 h in the solution; Filter, the filter cake of gained is in 500 ~ 600 ℃ of roasting 2.5 ~ 3.5h; After being cooled to room temperature, get pulverous solid super-strong acid SO
4 2-/ ZrO
2-WO
3
2. the preparation method of ATBC is characterized in that: utilize claim 1 preparation and solid super-strong acid SO
4 2-/ ZrO
2-WO
3, carry out following steps successively:
1), will be as the citric acid of raw material and n-butanol and as the solid super-strong acid SO of catalyst
4 2-/ ZrO
2-WO
3In solvent, under the reflux water-dividing condition, react 3 ~ 7h; The mol ratio of described citric acid and n-butanol is 1:3 ~ 3.5; The solid super-strong acid SO of citric acid adapted 0.1 ~ 0.3g of every 0.1mol
4 2-/ ZrO
2-WO
3
2), after the reaction gains of step 1) are cooled to room temperature, add with the aceticanhydride of the used citric acid equimolar amounts of step 1) and add solid super-strong acid SO as catalyst
4 2-/ ZrO
2-WO
3Under room temperature, reacted 1 ~ 3 hour; Described solid super-strong acid SO
4 2-/ ZrO
2-WO
3With the amount ratio of citric acid in the step 1) be: 0.03 ~ 0.10g solid super-strong acid SO
4 2-/ ZrO
2-WO
3/ citric acid of 0.1mol;
After reaction finishes, filter to remove the solid super-strong acid SO as catalyst earlier
4 2-/ ZrO
2-WO
3, the filtrate decompression distillation gets ATBC.
3. the preparation method of ATBC according to claim 2, it is characterized in that: the solvent in the described step 1) is toluene.
4. the preparation method of ATBC according to claim 3, it is characterized in that: the filtrate decompression distillation purpose described step 2) is the acetic acid that produces for desolventizing, the n-butanol that has neither part nor lot in reaction and reaction, thereby gets ATBC.
5. the preparation method of ATBC according to claim 4 is characterized in that:
In the described step 1): the mol ratio of citric acid and n-butanol is 1:3.2; The solid super-strong acid SO of the citric acid adapted 0.1g of every 0.1mol
4 2-/ ZrO
2-WO
3Reaction time is 5h,
Described step 2) in: solid super-strong acid SO
4 2-/ ZrO
2-WO
3With the amount ratio of citric acid in the step 1) be: 0.03g solid super-strong acid SO
4 2-/ ZrO
2-WO
3/ citric acid of 0.1mol; Reaction time is 3 hours.
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| CN106278287A (en) * | 2015-06-08 | 2017-01-04 | 深圳大学 | A kind of WO3the preparation of cladding AZO powder body and sintering method thereof |
| CN108440283A (en) * | 2018-03-23 | 2018-08-24 | 陕西师范大学 | SO42-/WO3-ZrO2Application of the catalyst in catalyzed conversion glycerine prepares diacetine |
| CN109569579A (en) * | 2018-12-26 | 2019-04-05 | 淮南安信泰科技有限公司 | A kind of method of the immobilized tungsten oxide preparation tributyl citrate of attapulgite clay |
| CN115487855A (en) * | 2022-09-21 | 2022-12-20 | 新乡市瑞丰新材料股份有限公司 | Preparation method of catalyst for preparing polyol fatty acid ester |
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| CN106278287A (en) * | 2015-06-08 | 2017-01-04 | 深圳大学 | A kind of WO3the preparation of cladding AZO powder body and sintering method thereof |
| CN106278287B (en) * | 2015-06-08 | 2019-04-26 | 深圳大学 | A kind of WO3Coat preparation and its sintering method of AZO powder |
| CN108440283A (en) * | 2018-03-23 | 2018-08-24 | 陕西师范大学 | SO42-/WO3-ZrO2Application of the catalyst in catalyzed conversion glycerine prepares diacetine |
| CN109569579A (en) * | 2018-12-26 | 2019-04-05 | 淮南安信泰科技有限公司 | A kind of method of the immobilized tungsten oxide preparation tributyl citrate of attapulgite clay |
| CN109569579B (en) * | 2018-12-26 | 2021-10-08 | 淮南安信泰科技有限公司 | Method for preparing tributyl citrate from attapulgite clay immobilized tungsten oxide |
| CN115487855A (en) * | 2022-09-21 | 2022-12-20 | 新乡市瑞丰新材料股份有限公司 | Preparation method of catalyst for preparing polyol fatty acid ester |
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