CN103316696B - 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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- CN103316696B CN103316696B CN201310278427.3A CN201310278427A CN103316696B CN 103316696 B CN103316696 B CN 103316696B CN 201310278427 A CN201310278427 A CN 201310278427A CN 103316696 B CN103316696 B CN 103316696B
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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 catalyzer used.
Background technology
ATBC, be called for short ATBC, its molecular formula is C
20h
34o
8, its structural formula is as shown in S-1, and its sterling is colourless, tasteless oily liquids, boiling point 343 DEG C; For a kind of novel asepsis environment-protecting softening agent, have nonpoisonous and tasteless, consistency good, plasticizing efficiency is high, be easily biodegradable and the advantage such as volatility is little, winter hardiness, photostabilization and have excellent water-resistance, alternative phthalate conventional plasticizers.Can be used as polyvinyl chloride, celluosic resin and elastomeric softening agent, for nontoxic PVC granulation, food container, toy for children goods, medical product, the goods such as film, sheet material, cellulose paint, also can be used as the stablizer etc. of polyvinylidene dichloride, is a kind of important Chemicals.
S-1
The preparation of ATBC is mainly prepared by the esterification of tri-n-butyl citrate (being called for short TBC).China's citric acid output is comparatively large, and supply exceed demand, but the catalyzer that conventional synthesis TBC method adopts mostly is the vitriol oil, though the method productive rate is high, there is side reaction many in sulfuric acid low price, product colour is dark, quality is low, spent acid contaminate environment, severe corrosion equipment, aftertreatment is complicated, labour intensity is large, formation efficiency is low, high in cost of production shortcoming, the synthesis of TBC mainly with citric acid and butanols for raw material esterification obtains.Its reaction principle is mainly as shown in S-2.
S-2
Catalyzer used at present roughly has: (1) p-methyl benzenesulfonic acid, Phenylsulfonic acid, methylsulphonic acid, (2) thionamic acid of thionamic acid and replacement, replaces tertiary dithiocarbamic acid vitriol, (3) sal enixum, sodium pyrosulfate, (4) strong acid ion exchange resin, (5) solid super-strong acid.The research generating the solid super-strong acid of TBC for catalysis 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 current finding is used for the ZrO of tributyl citrate
2the solid super-strong acid of type is only shown in there is 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
2o/SBA-15 mesoporous molecular sieve catalyst, SO
4 2-/ ZrO
2-MCM-41 etc.And the solid super-strong acid SO that the present invention is used
4 2-/ ZrO
2-WO
3(SZW) report is had no.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation method of ATBC and solid super-strong acid SO used
4 2-/ ZrO
2-WO
3(SZW); The present invention has the features such as production efficiency is high, 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 carry out following steps successively:
1. the ZrOCl of 5g, is taken
28H
2o is dissolved in 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; Ammoniacal liquor (slowly adding ammoniacal liquor) is utilized to regulate ZrOCl
2pH to the 8.9 ~ 9.1(of the aqueous solution is preferably 9);
2., by the mixed solution of step 1. gained after stirred at ambient temperature 20 ~ 30 min, 80 DEG C of ageings 36 are preferably h) in 75 ~ 85 DEG C of ageing 34 ~ 38h(; Filter, the filter cake of gained washs extremely without Cl with clear water
-after at 500 ~ 600 DEG C of roasting 10 ~ 14 h(are preferably 550 DEG C, roasting 12 is h);
3., by after gains are cooled to room temperature after the roasting of step 2. gained, the powder crossing 100 orders (that is, 100 objects can be crossed to sieve) is ground to form; Then the ammonium metatungstate aqueous solution 13 ~ 18ml be placed in containing 0.8 ~ 1.2g ammonium metawolframate [is preferably containing 1g ammonium metawolframate ((NH
4)
6h
2w
12o
40) ammonium metatungstate aqueous solution (15ml)] flood 24 h; Filter, the filter cake of gained is preferably 600 DEG C of roasting 3h in 550 ~ 650 DEG C of roasting 2.5 ~ 3.5h();
4., by after gains are cooled to room temperature after the roasting of step 3. gained, grind to form and can cross 100 object powder; Then being placed in 30 ~ 70ml(and being preferably 50ml) concentration is the H of l mol/L
2sO
424 h are flooded in solution; Filter, the filter cake of gained is preferably 550 DEG C of roastings 3 h) in 500 ~ 600 DEG C of roasting 2.5 ~ 3.5h(; After being cooled to room temperature, obtain 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 surface area is 225 ~ 245m
2/ g.
Remarks illustrate: H in this step
2sO
4consumption can guarantee that powder is all immersed in H
2sO
4in solution.
Present invention also offers a kind of preparation method of ATBC, utilize aforesaid method to prepare and the solid super-strong acid SO that obtains
4 2-/ ZrO
2-WO
3(SZW), following steps are carried out successively:
1), using as the citric acid of raw material and propyl carbinol and the solid super-strong acid SO as catalyzer
4 2-/ ZrO
2-WO
3(SZW) in solvent, under reflux water-dividing condition, 3 ~ 7h is reacted; The mol ratio of described citric acid and propyl carbinol is 1:3 ~ 3.5; The solid super-strong acid SO of the 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, the aceticanhydride adding the citric acid equimolar amount used with step 1) and the solid super-strong acid SO added as catalyzer
4 2-/ ZrO
2-WO
3(SZW) react 1 ~ 3 hour under room temperature; Solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) with the amount ratio of the citric acid in step 1) be: 0.03 ~ 0.10g solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW)/citric acid of 0.1mol;
After reaction terminates, first filter to remove the solid super-strong acid SO as catalyzer
4 2-/ ZrO
2-WO
3(SZW), filtrate decompression distillation (be such as 0.02MPa, 80 DEG C), product---ATBC (ATBC).
Remarks illustrate: above-mentioned underpressure distillation object is the acetic acid (as by product) in order to produce except desolventizing, the propyl carbinol not participating in reaction completely and reaction,
Improvement as the preparation method of ATBC of the present invention: the solvent in 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 step 1): the mol ratio of citric acid and propyl carbinol 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
3; Reaction times is 5h,
Step 2) in: solid super-strong acid SO
4 2-/ ZrO
2-WO
3with the amount ratio of the citric acid in step 1) be: 0.03g solid super-strong acid SO
4 2-/ ZrO
2-WO
3/ citric acid of 0.1mol; Reaction times is 3 hours.
In the present invention, ammoniacal liquor is conventional industrial ammonia, namely containing the aqueous solution of ammonia 25% ~ 28%.
Room temperature refers to 10 ~ 25 DEG C.
The present invention has following technical superiority:
1, a kind of catalyzer has been prepared--solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW), first Application, in the esterification of citric acid and propyl carbinol, solves equipment corrosion, waste water handling problem that traditional technology sulfuric acid produces, and easy to prepare, renewablely reuses, environmentally friendly, environmental protection.
2, solid super-strong acid SO is used
4 2-/ ZrO
2-WO
3(SZW) make catalyzer, reaction easily controls, and simply, catalytic activity is high, reduces production cost for catalyzer and product separation.
3, SO is adopted
4 2-/ ZrO
2the solid super-strong acid SO of system
4 2-/ ZrO
2-WO
3(SZW) replace the advantage of vitriol oil synthesis TBC mainly little, " three wastes " discharge of corrodibility less, renewablely to reuse, catalyzer is simple with product separation, catalytic activity height and selectivity good etc.
4, the present invention passes through at SO
4 2-/ ZrO
2component W(tungsten is added in solid super-strong acid), to improve life-span and the stability of catalyzer, and for preparing TBC and ATBC with the esterification catalytic of citric acid and propyl carbinol, obtain a kind of production efficiency high, easy and simple to handle, the new process of production of environmental protection.
Embodiment
Embodiment 1, a kind of organic compound---the preparation method of ATBC, with citric acid, propyl carbinol for raw material, carries out following steps successively:
1), as the solid super-strong acid SO of catalyzer
4 2-/ ZrO
2-WO
3(SZW) preparation, carry out following steps successively:
1. the ZrOCl of 5g, is taken
28H
2o is dissolved in deionized water (about 20ml), is made into mass ratio M (ZrOCl
2): M (H
2the ZrOCl of O)=1:8
2the aqueous solution; Ammoniacal liquor is slowly added in above-mentioned solution, regulate pH to 9.
2., the mixed solution of step 1. gained is put into baking oven, ageing 36 h at 80 DEG C after stirred at ambient temperature 25 min; Filter, the filter cake of gained washs extremely without Cl with clear water
-after, be placed in retort furnace, in 550 DEG C of roasting 12 h.
3., by after gains are cooled to room temperature after the roasting of step 2. gained, the powder crossing 100 orders (100 objects can be crossed sieve) is ground to form; Then be placed in containing 1g ammonium metawolframate ((NH
4)
6h
2w
12o
40) ammonium metatungstate aqueous solution (15ml) in dipping 24 h, filter, the filter cake of gained roasting 3h at 600 DEG C in retort furnace.
4., by after gains are cooled to room temperature after the roasting of step 3. gained, grind to form and can cross 100 object powder; Then the H that concentration is l mol/L is placed in
2sO
424 h are flooded in solution 50ml; Filter, the filter cake of gained is placed in retort furnace in 550 DEG C of roasting 3 h, after being cooled to room temperature, obtains pulverous solid super-strong acid SO
4 2-/ ZrO
2-WO
3.
Final gained catalyzer aperture is about 11nm, and specific surface area is 240 m
2about/g.
2), by 0.1mol citric acid, 0.3mol propyl carbinol, SZW and the 100ml toluene of 0.10g reacts in the there-necked flask (flask is furnished with condenser, water trap and thermometer) of 250ml under reflux water-dividing condition, constantly point water outlet in reaction process.Stopped reaction after reaction 5h, reaction solution is cooled to room temperature.
3), in the reaction solution being cooled to room temperature, add the aceticanhydride of 0.1mol and the SZW of 0.05g, under room temperature, react 2h.
After reaction terminates, filter out catalyst S ZW, reuse.The acetic acid (as by product) produced in filtrate decompression (0.02MPa) distillation (80 DEG C) removing toluene, a small amount of unreacted propyl carbinol and reaction, still liquid is ATBC (ATBC) 33.61g, yield 83.5%.Its purity is 99.7%.
Embodiment 2, a kind of organic compound---the preparation method of-ATBC, with citric acid, propyl carbinol is raw material, carries out following steps successively:
1), as the solid super-strong acid SO of catalyzer
4 2-/ ZrO
2-WO
3(SZW) prepare:
With embodiment 1.
2), by 0.1mol citric acid, 0.3mol butanols, SZW and the 100ml toluene of 0.10g reacts in the there-necked flask of 250ml under reflux water-dividing condition, constantly point water outlet in reaction process.Stopped reaction after reaction 3h, is cooled to room temperature by reaction solution.
3), in the reaction solution being cooled to room temperature, add aceticanhydride and the 0.05g SZW of 0.1mol, under room temperature, react 1h.Filter out catalyzer, reuse.The acetic acid produced in filtrate decompression distillation removing toluene, a small amount of unreacted propyl carbinol and reaction, still liquid is ATBC (ATBC) 31.92g, yield 79.3%.Its purity is 99.6%.
Embodiment 3, a kind of organic compound---the preparation method of-ATBC, with citric acid, propyl carbinol is raw material, carries out following steps successively:
1), solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) catalyst preparing:
With embodiment 1.
2), by 0.1mol citric acid, 0.35mol propyl carbinol, 0.20g SZW and 100ml toluene react in the there-necked flask of 250ml under reflux water-dividing condition, constantly point water outlet in reaction process.React stopped reaction after 5 hours, reaction solution is cooled to room temperature.
3), in the reaction solution being cooled to room temperature, add aceticanhydride and the 0.05g SZW of 0.1mol, under room temperature, react 2h.Filter out catalyzer, reuse.The acetic acid produced in filtrate decompression distillation removing toluene, a small amount of unreacted propyl carbinol and reaction, 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, propyl carbinol is raw material, carries out following steps successively:
1), solid super-strong acid SO
4 2-/ ZrO
2-WO
3(SZW) catalyst preparing:
With embodiment 1.
2), by 0.1mol citric acid, 0.30mol butanols, 0.10g SZW and 100ml toluene react in the there-necked flask of 250ml under reflux water-dividing condition, constantly point water outlet in reaction process.Stopped reaction after reaction 3h, is cooled to room temperature by reaction solution.
3), in the reaction solution being cooled to room temperature, add aceticanhydride and the 0.03g SZW of 0.1mol, under room temperature, react 1h.Filter out catalyzer, reuse.The acetic acid produced in filtrate decompression distillation removing toluene, a small amount of unreacted propyl carbinol and reaction, still liquid is ATBC (ATBC) 28.74g, yield 71.4%.Its purity is 99.5%.
Embodiment 5 ~ embodiment 13, material proportion, catalyst levels, the step 2 changed in embodiment 1) and the step 3) reaction times, thus obtaining corresponding embodiment 5 ~ embodiment 13, the yield of the product of final gained---ATBC is as shown in table 1.
Remarks illustrate: the preparation method of catalyzer is with embodiment 1; The consumption of citric acid is constant.
Table 1 SZW catalytic synthesis of acetyl tri-n-butyl citrate
Comparative example 1, make the SZW in comparative example 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
2preparation method be: according to " the SO published in Hebei chemical industry the 35th volume the 7th phase in 2012
4 2-/ WO
3-ZrO
2catalytic Synthesis of n-Butyl Acetate " be prepared.
Comparative example 2, make the SZW in comparative example 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
2preparation method according to publish in application chemical industry the 101st volume the 34th phase in 2005 " mixed metal oxide catalyzed with solid supported heteropolyacid synthesizing citric acid tri-n-butyl " be prepared.
Comparative example 3, by " the solid super-strong acid SO in comparative example 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in ammonium metawolframate ((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 example 4, by " the solid super-strong acid SO in comparative example 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in ammonium metawolframate ((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 example 5, by " the solid super-strong acid SO in comparative example 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in soak (dipping) the concentration of sulphuric acid soln change use 0.5mol/L into; All the other are with embodiment 11.
ATBC (ATBC) 29.14g of final gained, yield 72.4%.Its purity is 99.1%.
Comparative example 6, by " the solid super-strong acid SO in comparative example 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " in soak (dipping) sulfuric acid time 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 example 7, by " the solid super-strong acid SO in comparative example 11
4 2-/ ZrO
2-WO
3(SZW) method for preparing catalyst " step 3. with step 4. in grinding all made 50 mesh sieves into; All the other are with embodiment 11.
ATBC (ATBC) 26.89g of final gained, yield 66.8%.Its purity is 99.1%.
Finally, it is also to be noted that what enumerate above is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be had.All distortion that those of ordinary skill in the art can directly derive from content disclosed by the invention or associate, all should think protection scope of the present invention.
Claims (4)
1. the preparation method of ATBC, is characterized in that carrying out following steps successively:
1), using as the citric acid of raw material and propyl carbinol and the solid super-strong acid SO as catalyzer
4 2-/ ZrO
2-WO
3under reflux water-dividing condition, 3 ~ 7h is reacted in solvent; The mol ratio of described citric acid and propyl carbinol is 1:3 ~ 3.5; The solid super-strong acid SO of the citric acid adapted 0.1 ~ 0.3g of every 0.1mol
4 2-/ ZrO
2-WO
3;
2), step 1) reaction gains be cooled to room temperature after, add and step 1) aceticanhydride of citric acid equimolar amount used and the solid super-strong acid SO that adds as catalyzer
4 2-/ ZrO
2-WO
3react 1 ~ 3 hour under room temperature; Described solid super-strong acid SO
4 2-/ ZrO
2-WO
3with 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/ citric acid of 0.1mol;
After reaction terminates, first filter to remove the solid super-strong acid SO as catalyzer
4 2-/ ZrO
2-WO
3, filtrate decompression is distilled, and obtains ATBC;
Solid super-strong acid SO
4 2-/ ZrO
2-WO
3preparation method for carry out following steps successively:
1. the ZrOCl of 5g, is taken
28H
2o is dissolved in deionized water, is made into mass ratio ZrOCl
2: H
2the ZrOCl of O=1:7.8 ~ 8.2
2the aqueous solution; Ammoniacal liquor is utilized to regulate ZrOCl
2pH to 8.9 ~ 9.1 of the aqueous solution;
2., by the mixed solution of step 1. gained after stirred at ambient temperature 20 ~ 30min, in 75 ~ 85 DEG C of ageing 34 ~ 38h; Filter, the filter cake of gained with clear water washing to without after Cl-in 500 ~ 600 DEG C of roasting 10 ~ 14h;
3., by after gains are cooled to room temperature after the roasting of step 2. gained, grind to form and can cross 100 object powder; Then the ammonium metatungstate aqueous solution 13 ~ 18ml be placed in containing 0.8 ~ 1.2g ammonium metawolframate floods 24h; Filter, the filter cake of gained is in 550 ~ 650 DEG C of roasting 2.5 ~ 3.5h;
4., by after gains are cooled to room temperature after the roasting of step 3. gained, grind to form and can cross 100 object powder; Then the H that 30 ~ 70ml concentration is l mol/L is placed in
2sO
424h is flooded in solution; Filter, the filter cake of gained is in 500 ~ 600 DEG C of roasting 2.5 ~ 3.5h; After being cooled to room temperature, obtain pulverous solid super-strong acid SO
4 2-/ ZrO
2-WO
3.
2. the preparation method of ATBC according to claim 1, is characterized in that: described step 1) in solvent be toluene.
3. the preparation method of ATBC according to claim 2, it is characterized in that: described step 2) in filtrate decompression distillation object be in order to except desolventizing, have neither part nor lot in reaction propyl carbinol and reaction produce acetic acid, thus ATBC.
4. the preparation method of ATBC according to claim 3, is characterized in that:
Described step 1) in: the mol ratio of citric acid and propyl carbinol 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
3; Reaction times is 5h,
Described step 2) in: solid super-strong acid SO
4 2-/ ZrO
2-WO
3with step 1) in the amount ratio of citric acid be: 0.03g solid super-strong acid SO
4 2-/ ZrO
2-WO
3/ citric acid of 0.1mol; Reaction times is 3 hours.
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| CN106278287B (en) * | 2015-06-08 | 2019-04-26 | 深圳大学 | A kind of WO3Coat preparation and its sintering method of AZO powder |
| CN108440283B (en) * | 2018-03-23 | 2020-08-25 | 陕西师范大学 | SO42-/WO3-ZrO2Application of catalyst in preparation of diacetin by catalytic conversion of glycerol |
| 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 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067393A (en) * | 1991-06-06 | 1992-12-30 | 北京师范大学 | Presence of compound solid superacid catalyst agent and manufacture method thereof |
| CN101318139A (en) * | 2008-07-22 | 2008-12-10 | 上海应用技术学院 | Composite solid super acidic catalyst and preparation method thereof |
| CN101829559A (en) * | 2009-03-13 | 2010-09-15 | 复旦大学 | Preparation method and application of WO3/ZrO2 solid super acidic catalyst |
| CN102304045A (en) * | 2011-07-11 | 2012-01-04 | 南京工业大学 | Integrated process for synthesizing acetyl tributyl citrate by using activated carbon immobilized sulfuric acid catalyst |
| CN102633640A (en) * | 2012-03-30 | 2012-08-15 | 东营金明工贸有限公司 | Integrated production technique of acetyl tributyl citrate (ATBC) |
| CN103041800A (en) * | 2013-01-03 | 2013-04-17 | 东北石油大学 | Preparation method of WO3/ZrO2 solid super acidic catalyst |
-
2013
- 2013-07-03 CN CN201310278427.3A patent/CN103316696B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1067393A (en) * | 1991-06-06 | 1992-12-30 | 北京师范大学 | Presence of compound solid superacid catalyst agent and manufacture method thereof |
| CN101318139A (en) * | 2008-07-22 | 2008-12-10 | 上海应用技术学院 | Composite solid super acidic catalyst and preparation method thereof |
| CN101829559A (en) * | 2009-03-13 | 2010-09-15 | 复旦大学 | Preparation method and application of WO3/ZrO2 solid super acidic catalyst |
| CN102304045A (en) * | 2011-07-11 | 2012-01-04 | 南京工业大学 | Integrated process for synthesizing acetyl tributyl citrate by using activated carbon immobilized sulfuric acid catalyst |
| CN102633640A (en) * | 2012-03-30 | 2012-08-15 | 东营金明工贸有限公司 | Integrated production technique of acetyl tributyl citrate (ATBC) |
| CN103041800A (en) * | 2013-01-03 | 2013-04-17 | 东北石油大学 | Preparation method of WO3/ZrO2 solid super acidic catalyst |
Non-Patent Citations (1)
| Title |
|---|
| WO3/ZrO2 固体酸催化剂的制备及应用研究进展;李言等;《分子催化》;20111031;第25卷(第5期);476-483 * |
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