CN102584591A - Method for preparing tributyl citrate through diatomite immobilized titanium sulfate used as catalyst - Google Patents
Method for preparing tributyl citrate through diatomite immobilized titanium sulfate used as catalyst Download PDFInfo
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- CN102584591A CN102584591A CN2011104523086A CN201110452308A CN102584591A CN 102584591 A CN102584591 A CN 102584591A CN 2011104523086 A CN2011104523086 A CN 2011104523086A CN 201110452308 A CN201110452308 A CN 201110452308A CN 102584591 A CN102584591 A CN 102584591A
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- titanium sulfate
- tributyl citrate
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- zeyssatite
- esterification
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Abstract
The invention provides a method for preparing tributyl citrate through diatomite immobilized titanium sulfate used as a catalyst. According to the method, diatomite immobilized titanium sulfate is used as the catalyst, and citric acid and n-butyl alcohol take esterification reaction for synthesizing the tributyl citrate. The method has the advantages that the diatomite immobilized titanium sulfate is used as the catalyst, obvious corrosivity does not exist, in addition, the recovery and the repeated utilization are easy, and the activity is basically maintained unchanged; the esterification reaction efficiency is improved, and the product yield can reach 99.5 percent to the highest degree; reactants of the n-butyl alcohol are used as water-carrying agents, the use of noxious solvents such as methylbenzene and the like is avoided, and in addition, the aftertreatment process is simplified; and the esterification reaction condition is mild, the process is simple, and the method is suitable for industrial production.
Description
Technical field
The invention belongs to chemical field, specifically, relate to a kind of method with the immobilized titanium sulfate catalytic preparation of zeyssatite tributyl citrate.
Background technology
It is phthalate that softening agent commonly used is gone up in industry at present, and because of it can bring out carcinogenicly, strict abroad control is used, and actively searching can replace the non-toxic plasticizer of phthalate.China has also formulated relevant laws and regulations, with progressively superseded its use in packaging material for food, medical utensil, toy, and recommends to use tributyl citrate.Tributyl citrate has that consistency is good, plasticizing efficiency is high, nontoxic, volatility is little, winter hardiness, mould resistance, photostabilization, characteristics such as have excellent water-resistance are especially used in fields such as food product pack, toy for children, medical articles and are had significant meliority.Therefore, tributyl citrate is one of phthalic ester plasticizer best " green " substitute.In the traditional technology, the synthesizing citric acid tri-n-butyl is catalyzer usually with the vitriol oil, but there are many, the refining difficulties of side reaction in this catalyzer, and equipment corrosion is serious, drawbacks such as aftertreatment technology complicacy and spent acid contaminate environment, and its application has received very big restriction.Studied some more catalyzer afterwards, for example solid super-strong acid has catalytic activity preferably to this reaction, however its complicated process of preparation, and cost is high, is unfavorable for industrial production.
Summary of the invention
A kind of economic environmental protection that the objective of the invention is to be directed against the prior art deficiency and provide with the method for the immobilized titanium sulfate catalytic preparation of zeyssatite tributyl citrate.
In order to realize the object of the invention; A kind of method of the present invention with the immobilized titanium sulfate catalytic preparation of zeyssatite tributyl citrate; May further comprise the steps: 1) combining of titanium sulfate and fixation support: zeyssatite is joined in the titanium sulfate solution, stir evaporating water in 40-70 ℃ (preferred 60 ℃) down; The gained solid promptly gets the immobilization titanium sulfate through high-temperature roasting; 2) esterification: in the mixed system of Hydrocerol A and propyl carbinol, add the immobilization titanium sulfate of step 1), reflux stirs, and gets the tributyl citrate bullion; 3) system after product purification: with step 2) reaction finishes is filtered, and filtrating obtains the pure article of tributyl citrate after neutralization, underpressure distillation.
Wherein, the weight ratio of zeyssatite and titanium sulfate is 1-4.5 in the step 1): 1, and preferred 1.5: 1.
The high-temperature roasting temperature is 200-800 ℃ in the step 1), preferred 400 ℃.
The weight ratio of Hydrocerol A, propyl carbinol and immobilization titanium sulfate is 200 in the esterification: 231-347: 1-4, preferred 100: 135: 1.
Esterification reaction temperature is 110-130 ℃, preferred 120 ℃.
What neutralization filtrate used in the step 3) is sodium hydrogen carbonate solution.
Particularly, the object of the invention can adopt following technical measures further to realize.
Comprise step:
1) combining of titanium sulfate and fixation support: get 4-10g zeyssatite and join in the titanium sulfate solution that mass percent is 2-5%; And be placed under the 40-70 ℃ of condition and stir 2h; Vacuum-evaporation moisture; Remaining solid behind dry 24h under 100 ℃ of conditions, roasting 2-8h under 200-800 ℃ of condition.
2) esterification: (weight ratio is 200: 231-347: 1-4) in the reactor drum that has induction stirring, TM, reflux condensing tube, water trap, to add Hydrocerol A, propyl carbinol and immobilization titanium sulfate; 110-130 ℃ of reflux stirs; The water that reaction produces is told from water trap; Reaction stops when getting into water trap again to anhydrous, the tributyl citrate bullion.
3) catalyst recovery and product purification: the tributyl citrate bullion is filtered, and the catalyzer that leaches directly is used for secondary response down; Filtrating is distilled through normal pressure, reclaims excessive propyl carbinol; To be cooled to room temperature, use mass percent extremely neutral as the washing of 3-8% sodium hydrogen carbonate solution, it is residual to remove Hydrocerol A; Again through underpressure distillation dewater, impurity such as propyl carbinol, promptly get the pure article of tributyl citrate.
The invention has the beneficial effects as follows:
(1) the present invention is a catalyzer with the immobilized titanium sulfate of zeyssatite, do not have obvious corrodibility and be easy to and reclaim and reuse, and activity remains unchanged basically.
(2) improved esterification efficient, product yield reaches as high as 99.5%.
(3) serve as the band aqua with the reactant propyl carbinol, not only avoided noxious solvents such as use toluene, and simplified aftertreatment technology.
(4) esterification mild condition, technology is simple, is fit to suitability for industrialized production.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.If do not specialize, the percentage sign that relates among the embodiment " % " is meant mass percent; But the per-cent of solution except as otherwise herein provided, is meant the gram number that contains solute in the 100ml solution.
Embodiment 1
1) Preparation of catalysts
Getting 6g zeyssatite, to join the 100mL massfraction be in 4% the titanium sulfate solution, and be placed under 60 ℃ of conditions and stir 2h, vacuum-evaporation moisture, remaining solid behind dry 24h under 100 ℃ of conditions, roasting 6h under 400 ℃ of conditions.
2) esterification
In the reactor drum that has induction stirring, TM, reflux condensing tube, water trap, add 270g propyl carbinol, 200g Hydrocerol A and 2g catalyzer; 120 ℃ of reflux stir; The water that reaction produces is told from water trap; Reaction stops when getting into water trap again to anhydrous, the tributyl citrate bullion.
3) catalyst recovery and product purification
The tributyl citrate bullion is filtered, and the catalyzer that leaches directly is used for secondary response down; Filtrating is distilled through normal pressure, reclaims excessive propyl carbinol; To be cooled to room temperature, using mass percent is that 5% sodium hydrogen carbonate solution washs the tributyl citrate bullion twice with 1: 1 volume ratio; Again through underpressure distillation dewater, impurity such as propyl carbinol, water white transparency product tributyl citrate, productive rate is 99.5%.
Embodiment 2-4
Only change the propyl carbinol consumption, all the other are with embodiment 1.The result is as shown in table 1.
Table 1
Embodiment 5-7
Only change esterification reaction temperature, all the other are with embodiment 1.The result is as shown in table 2.
Table 2
Embodiment 8-10
Only change the zeyssatite consumption, all the other are with embodiment 1.The result is as shown in table 3.
Table 3
Embodiment 11-13
Only change the mass percent of titanium sulfate solution, all the other are with embodiment 1.The result is as shown in table 4.
Table 4
Embodiment 14-16
Only change the whipping temp in the catalyst preparation process, all the other are with embodiment 1.The result is as shown in table 5.
Table 5
Embodiment 17-19
Only change the high-temperature roasting temperature in the catalyst preparation process, all the other are with embodiment 1.The result is as shown in table 6.
Table 6
Embodiment 20-22
Only change the high-temperature roasting time in the catalyst preparation process, all the other are with embodiment 1.The result is as shown in table 7.
Table 7
Embodiment 23-25
The catalyst recirculation access times to reaction to influence the result as shown in table 8.
Table 8
Though, the present invention has been done detailed description in the preceding text with general explanation and specific embodiments, on basis of the present invention, can to some modifications of do or improvement, this will be apparent to those skilled in the art.Therefore, these modifications or the improvement on the basis of not departing from spirit of the present invention, made all belong to the scope that requirement of the present invention is protected.
Claims (10)
1. the method with the immobilized titanium sulfate catalytic preparation of zeyssatite tributyl citrate is characterized in that, comprises step:
1) combining of titanium sulfate and fixation support: zeyssatite is joined in the titanium sulfate solution, stir down in 40-70 ℃, evaporating water, the gained solid promptly gets the immobilization titanium sulfate through high-temperature roasting;
2) esterification: in the mixed system of Hydrocerol A and propyl carbinol, add the immobilization titanium sulfate of step 1), reflux stirs, and gets the tributyl citrate bullion;
3) system after product purification: with step 2) reaction finishes is filtered, and filtrating obtains the pure article of tributyl citrate after neutralization, underpressure distillation.
2. method according to claim 1 is characterized in that, the weight ratio of zeyssatite and titanium sulfate is 1-4.5 in the step 1): 1.
3. method according to claim 2 is characterized in that, the weight ratio of zeyssatite and titanium sulfate is 1.5: 1 in the step 1).
4. method according to claim 1 is characterized in that, the high-temperature roasting temperature is 200-800 ℃ in the step 1).
5. method according to claim 4 is characterized in that, the high-temperature roasting temperature is 400 ℃ in the step 1).
6. according to each described method of claim 1-3, it is characterized in that the weight ratio of Hydrocerol A, propyl carbinol and immobilization titanium sulfate is 200 in the esterification: 231-347: 1-4.
7. method according to claim 6 is characterized in that, the weight ratio of Hydrocerol A, propyl carbinol and immobilization titanium sulfate is 100: 135: 1 in the esterification.
8. according to each described method of claim 1-3, it is characterized in that esterification reaction temperature is 110-130 ℃.
9. method according to claim 8 is characterized in that, esterification reaction temperature is 120 ℃.
10. according to each described method of claim 1-3, it is characterized in that what neutralization filtrate used in the step 3) is that mass percent is 5% sodium hydrogen carbonate solution.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669443A (en) * | 2015-12-31 | 2016-06-15 | 江苏瑞佳化学有限公司 | Method of preparing tributyl citrate with nano-scale intercalated hydrotalcite catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270051A (en) * | 2008-04-25 | 2008-09-24 | 杜晓晗 | Method for preparing tri-n-butyl citrate |
| CN101270045A (en) * | 2007-03-22 | 2008-09-24 | 北京化工大学 | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101270045A (en) * | 2007-03-22 | 2008-09-24 | 北京化工大学 | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst |
| CN101270051A (en) * | 2008-04-25 | 2008-09-24 | 杜晓晗 | Method for preparing tri-n-butyl citrate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105669443A (en) * | 2015-12-31 | 2016-06-15 | 江苏瑞佳化学有限公司 | Method of preparing tributyl citrate with nano-scale intercalated hydrotalcite catalyst |
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Application publication date: 20120718 |