CN101270045A - Method for synthesizing triester citrate with hydrophobic solid acid as catalyst - Google Patents
Method for synthesizing triester citrate with hydrophobic solid acid as catalyst Download PDFInfo
- Publication number
- CN101270045A CN101270045A CNA2007100646447A CN200710064644A CN101270045A CN 101270045 A CN101270045 A CN 101270045A CN A2007100646447 A CNA2007100646447 A CN A2007100646447A CN 200710064644 A CN200710064644 A CN 200710064644A CN 101270045 A CN101270045 A CN 101270045A
- Authority
- CN
- China
- Prior art keywords
- citric acid
- acid
- hydrophobic solid
- ester
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a method used for synthesizing citric triester with hydrophobic solid acid which is used as a catalyst. The method is characterized in that: (1) the hydrophobic solid acid is used as the catalyst, has high catalytic efficiency, can be recycled for repeated use, and can be easily separated; the post treatment is simple; (2) the citric trimester of alcohol with 1 to 3 carbon atoms is prepared; a water-carrying agent is added in the reaction process; and the fractionated sampling method is used so as to reduce the consumption of reactants with low melting points and to reduce the cost; (3) the citric trimester of alcohol with 4 to 18 carbon atoms is prepared; toxic water-carrying agents are avoided in the reaction process so as to simplify the process of post treatment; (4) the method has no corrosion to the equipment, no environmental pollution or other problems; the corrosion-resistant requirements for the equipment are low; the process is short; the production process is conducive to the environment; and the equipment investment and operating cost are low.
Description
Technical field:
The present invention relates to the organic chemistry synthesis technical field, more particularly, the present invention relates to a kind of is the new method and new technology of catalyzer synthesizing citric acid three esters with novel hydrophobic solid acid.Technology environmental protection of the present invention, no waste water, waste gas, refuse " three wastes " pollutes; The hydrophobic solid acid catalyst efficient height that uses can reclaim repeated use, and easily separated, and aftertreatment technology is simple; The product that obtains is through infrared spectra, gas chromatographic detection, and the spectrogram that obtains is consistent with the standard spectrogram; The quality product achromaticity and clarification is transparent, and yield can reach 97%～98%.
Technical background:
The citrate series products is as a kind of novel " green " environmentally-friendly plastic softening agent, and nonpoisonous and tasteless, alternative phthalate conventional plasticizers is widely used in aspects such as food product pack, medical apparatus, toy for children and Personal hygiene product.Principal item has triethyl citrate, tributyl citrate and acetylize tributyl citrate etc.Triethyl citrate and acetylize tributyl citrate all have fabulous intermiscibility to all kinds of Mierocrystalline celluloses, and some natural resins are had good dissolving power, can be used as vinyl-acetic ester and other various cellulosic solvent-type plasticizers.In addition, since very low to the solubleness of oils, can in the prescription of grease resistance, use.In non-toxic plasticizer, citric acid ester type all is a kind of softening agent of less expensive from price and effect.Because therefore odorlessness can be used for more sensitive milk-product packing, the bottle stopper of beverage, the sealing-ring of bottled food etc.Consider from security standpoint, more be applicable to and make soft toy for children, to replace having the phthalate plasticizers of potentially dangerous.Citric acid ester type has stabilization to most resins, can be used as a kind of good versatility softening agent.
China is world citric acid production big country, and present domestic citric acid device overall throughput can reach 400,000 tons/year, rank first in the world, and consumption only has 110,000 tons/year, and major part is used for outlet.And developed more advanced fermentation technique in recent years, and the level that is in a leading position in the world, the quality of product improves constantly, and this has created favourable material condition for the nontoxic citrate plasticizer of exploitation of softening agent industry and research.Therefore, development and exploitation citrate for the deep processing field of widening citric acid, have important practical significance undoubtedly for plastics industry provides the new green environment protection softening agent.
At present, China rare production citric acid ester type producer uses the vitriol oil as catalyzer mostly, although the vitriol oil has the ideal catalytic activity as esterifying catalyst, has following shortcoming: (1＞vitriol oil is acid strong, equipment corrosion is serious in the production process, has increased production cost; (2) vitriol oil oxidisability is strong, causes pure dehydration generation ether and produces burnt matter, influences quality product; (3) produce a large amount of spent acid, contaminated wastewater environment in the production process; (4) vitriol oil make catalyzer can not regeneration, the corresponding production cost that increased; (4) vitriol oil and product are not easily separated, and postprocessing working procedures is more, and product cost improves.In view of the various drawbacks of sulphuric acid catalysis esterification, the development of new catalyzer makes synthesis technique simply be convenient to aftertreatment to improve yield, esterification yield, minimizing pollution, becomes the focus of exploitation citrate new synthetic process.
Summary of the invention:
The objective of the invention is catalyst preparation process complexity at the prior art existence, active ingredient easily runs off, and with the difficult isolating shortcoming of product, adopt a kind of green environment close friend's hydrophobic solid acid catalyst, this Preparation of Catalyst is simple, shows excellent catalytic activity in the reaction system of preparation citric acid three ester, selectivity and water tolerance, and it is short to have the reaction times, and aftertreatment is simple, catalyzer can be well from reaction system Separation and Recovery advantage such as recycle.And etching apparatus not, non-environmental-pollution.
Technical scheme:
The present invention prepares the following description of concrete grammar of citric acid three ester:
1, the citric acid three ester of the alcohol of 1～3 C atom of preparation, described method is carried out successively as follows: esterification: with hydrophobic solid acid catalyst, band aqua with dissolve completely with alcohol that citric acid joins in the esterifier, the band aqua in the water trap recycles; Carry out heated and stirred then and reflux, then take the gradation sampling system in reactor, to add alcohol, anhydrous stopped reaction when entering again in the water trap.
The purifying of product: catalyzer is separated from post reaction mixture, waited to reuse.It is extremely neutral with the saturated common salt water washing to isolate mixture of catalysts; Standing demix removes upper strata liquid to alcohol, water and band aqua, gets citric acid three ester.
2, the citric acid three ester of the alcohol of 4～18 C atoms of preparation, described method is carried out successively as follows: esterification: with hydrophobic solid acid catalyst, band aqua with dissolve completely citric acid with alcohol and join and carry out heated and stirred in the esterifier and reflux, the water that generates in the reaction process is constantly told by water trap distillation, anhydrous stopped reaction when entering again in the water trap.
The purifying of product: catalyzer is separated from post reaction mixture, waited to reuse.It is extremely neutral with the saturated common salt water washing to isolate mixture of catalysts; Standing demix removes upper strata liquid to alcohol, water and band aqua, gets citric acid three ester.
In the above-mentioned method for preparing citrate, the hydrophobic solid acid catalyst of step 1 and 2 described preparation citrates, it is characterized in that carrier degassing dehydration, the dissolving of active constituent metal inorganic salt is made into certain density solution, dipping, by normal temperature dipping method and backflow pickling process active constituent is flooded to carrier, drying is calcined certain hour at a certain temperature and is prepared the hydrophobic solid acid catalyst; This catalyzer is repeatedly used the catalytic activity and the selectivity that still can keep high in the reaction that the preparation citrate has water to participate in, simplified the aftertreatment technology of product, has reduced corrosion and environmental protection to equipment.
In the hydrophobic solid acid catalyst of above-mentioned preparation citrate, the active ingredient of hydrophobic solid acid is one or more in phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, tetrahydrated zirconium sulfate, sal epsom, ferric sulfate hydrate, iron(ic) chloride, two hydrated stannous chlorides, tosic acid, four water cesium sulfates, the titanium sulfate;
In the hydrophobic solid acid catalyst of above-mentioned preparation citrate, the carrier of hydrophobic solid acid is gac, silicon oxide, HZSM-5, diatomite, silica gel, aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, polynite, wilkinite, ion exchange resin, TiO
2-ZrO
2, among the ZnO, ferric oxide one or more.
In the above-mentioned method for preparing citrate, citric acid described in the step 1 and 2 is the mixing of Citric Acid, usp, Anhydrous Powder, Citric acid monohydrate Food grade or two kinds.
In the above-mentioned method for preparing citrate, the band aqua described in the step 1 is the alkane of toluene, dimethylbenzene, benzene, hexanaphthene, pentane, hexane, heptane, octane, iso-pentane, isohexane, isoheptane, octane-iso, 10 carbon or 11 carbon or 12 carbon and one or more the mixing in the isoparaffin.
In the above-mentioned method for preparing citrate, raw materials used mol ratio is a citric acid in the step 1: alcohol: band aqua=1: 1: 0.2～1: 8: 8, temperature of reaction: 50 ℃～180 ℃, the reaction times is 1～10 hour.
In the above-mentioned method for preparing citrate, raw materials used mol ratio is a citric acid in the step 2: alcohol=1: 1～1: 8, temperature of reaction: 100 ℃～300 ℃, the reaction times is 1～10 hour.
In the above-mentioned method for preparing citrate, catalyst levels accounts for 0.2%～10% of reaction raw materials total mass in the step 1 and 2.
Technical superiority of the present invention is:
(1) reaction conditions gentleness, the reaction times is short, and the citrate good product quality that obtains: achromaticity and clarification is transparent; Productive rate height: 97.6%～98.3%;
(2) the hydrophobic solid acid catalyst of preparation citrate employing, preparation is simple, and it has certain strength of acid and hydrophobicity simultaneously, and is stable to water, has avoided the loss of active ingredient, can use repeatedly;
(3) solid acid catalyst of preparation citrate employing finishes the back in reaction and is in two phases with reactant and product, is easy to the recovery of catalyzer, has prolonged the work-ing life of catalyzer.
(4) problems such as no equipment corrosion and environmental pollution require lowly to equipment is corrosion-resistant, and technical process is short, the production process environmental friendliness, and facility investment and process cost are low;
(5) in method 1, the band aqua of water-taker recycles, and has saved the consumption of band aqua, has reduced cost.
(6) in method 2, avoid using deleterious band aqua toluene, simplified aftertreatment technology.
The chemical principle of institute of the present invention foundation is as follows:
Description of drawings:
Fig. 1: the fourier-transform infrared spectrogram (FTIR) of the triethyl citrate that makes by embodiment 3.
Embodiment:
Embodiment 1:
(1) esterification: having thermometer, reflux condensing tube, water trap, add the 0.033mol citric acid in the 100mL three-necked bottle of magneton, 5ml ethanol, add the toluene that accounts for water trap volume 7/8 in the water trap, three-necked bottle is placed on carries out heated and stirred in the magnetic agitation heating jacket, after treating that citric acid is molten entirely, adding 1.18g load tetrahydrated zirconium sulfate, to account for the total catalyst massfraction be 30% gac, 5ml toluene, carrying out the normal pressure reflux stirs, the water that question response produces is when water trap is told, pick up counting, 88 ℃～95 ℃ of temperature of reaction, then add ethanol 1.5ml every 25min, the total alcohol amount that adds in the three-necked bottle is 15.5ml, and reaction to the anhydrous water trap that enters again stops reaction times 3.5h, obtain the thick product 10.3g of citric acid three alcohol esters, sampling and measuring acid number, the mensuration of acid number are pressed GB/T1668-1995 and are measured, and the transformation efficiency of citric acid is 97.5%;
(2) purifying of the separation of catalyzer and product: the thick product of citric acid three alcohol esters is filtered, the catalyzer that leaches can be directly used in down secondary response, filtrate adds saturated aqueous common salt 30ml washing, upper strata product after the washing is shifted out, steam excessive pure and mild unnecessary toluene and water under normal pressure, be cooled to room temperature then, sampling is done fourier infrared and is detected and gas chromatographic analysis, wherein the selectivity of triethyl citrate accounts for 98%, and the yield of triethyl citrate is 95.6%.
Embodiment 2～4:
Except for the following differences, all the other are identical with embodiment 1, and citric acid and ethanol mol ratio are as shown in table 1:
Table 1
| Embodiment | Acid alcohol is than (mole) | Triethyl citrate yield/% |
| 2 | 1∶3 | 77.1％ |
| 3 | 1∶4 | 86.5％ |
| 4 | 1∶5 | 97.6％ |
Embodiment 5～7:
Except for the following differences, all the other are identical with embodiment 1, and catalyst levels (accounting for total reaction system quality mark %) is as shown in table 2:
Table 2
| Embodiment | Catalyst levels accounts for total reaction system quality mark %) | Triethyl citrate yield/% |
| 5 | 2％ | 92.1％ |
| 6 | 3％ | 95.2％ |
| 7 | 4％ | 96.4％ |
Embodiment 8～10:
Except for the following differences, all the other are identical with embodiment 1, and the influence that catalyzer is reused reaction the results are shown in Table 3
Table 3
| Embodiment | The catalyst recovery number of times | Triethyl citrate yield/% |
| 8 | 1 | 95.1％ |
| 9 | 2 | 89.1％ |
| 10 | 3 | 85.2％ |
Embodiment 11:
(1) esterification:: having thermometer, reflux condensing tube, water trap, add the 0.033mol citric acid in the 100mL three-necked bottle of magneton, 15.5mL propyl carbinol, three-necked bottle is placed on carries out heated and stirred in the magnetic agitation heating jacket, after treating that citric acid is molten entirely, adding 0.9695g load tetrahydrated zirconium sulfate, to account for the total catalyst massfraction be 30% gac, carrying out the normal pressure reflux stirs, the water that question response produces is when water trap is told, pick up counting, 110 ℃～130 ℃ of temperature of reaction, reaction to the anhydrous water trap that enters again stops, reaction times 1.5h, obtain the thick product 15.3g of tributyl citrate, sampling and measuring acid number, the mensuration of acid number are pressed GB/T1668-1995 and are measured, and the transformation efficiency of citric acid is 99%;
(2) purifying of the separation of catalyzer and product: thick product is filtered, the catalyzer that leaches can be directly used in down secondary response, filtrate adds saturated aqueous common salt 30ml washing, upper strata product after the washing is shifted out, under normal pressure, steam excessive fourth alcohol and water, be cooled to room temperature then, do fourier infrared and detect and gas chromatographic analysis, wherein the selectivity of tributyl citrate accounts for 98.5%, and the yield of tributyl citrate is 97.5%.
Embodiment 12:
(1) esterification:: having thermometer, reflux condensing tube, water trap, add the 0.033mol citric acid in the 100mL three-necked bottle of magneton, 15.8mL n-Octanol, three-necked bottle is placed on carries out heated and stirred in the magnetic agitation heating jacket, after treating that citric acid is molten entirely, adding 1g load tetrahydrated zirconium sulfate, to account for the total catalyst massfraction be 30% gac, carrying out the normal pressure reflux stirs, the water that question response produces is when water trap is told, pick up counting, 120 ℃～144 ℃ of temperature of reaction, reaction to the anhydrous water trap that enters again stops, reaction times 1h, obtain the thick product 16.9g of trioctyl lemon acid, sampling and measuring acid number, the mensuration of acid number are pressed GB/T1668-1995 and are measured, and the transformation efficiency of citric acid is 97.4;
The separation of catalyzer and the purifying of product: thick product is filtered, the catalyzer that leaches can be directly used in down secondary response, filtrate adds saturated aqueous common salt 30ml washing, upper strata product after the washing is shifted out, under normal pressure, steam excessive hot alcohol and water, be cooled to room temperature then, do fourier infrared and detect and gas chromatographic analysis, wherein the selectivity of trioctyl lemon acid accounts for 98.6%, and the yield of trioctyl lemon acid is 96.0%.
Claims (9)
1. one kind is the novel method that catalyst prepares citric acid three ester with the hydrophobic solid acid, it is characterized in that: adopting the alcohol of citric acid and 1～18 C atom is raw material, adding the band aqua or do not adding under the condition of being with aqua esterification takes place, make catalyzer with hydrophobic solid acid in the reaction process, after reaction finishes, catalyzer is separated from post reaction mixture and reusable, removed mixture behind the catalyzer through distillation, washing, dry citric acid three ester.Described alcohol is disposable to join in the reactor, or gradation joins in the reactor.
2. described according to claim 1 is the novel method that catalyst prepares citric acid three ester with the hydrophobic solid acid, and it is characterized in that: the active ingredient of hydrophobic solid acid is one or more in phospho-wolframic acid, silicotungstic acid, phospho-molybdic acid, tetrahydrated zirconium sulfate, sal epsom, ferric sulfate hydrate, iron(ic) chloride, two hydrated stannous chlorides, tosic acid, four water cesium sulfates, the titanium sulfate; The carrier of hydrophobic solid acid is gac, silicon oxide, HZSM-5, diatomite, silica gel, aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve, polynite, wilkinite, ion exchange resin, TiO
2-ZrO
2, among the ZnO, ferric oxide one or more.
3. according to claim 1 is the method that catalyst prepares citric acid three ester with the hydrophobic solid acid, it is characterized in that: the band aqua is the alkane of toluene, dimethylbenzene, benzene, hexanaphthene, pentane, hexane, heptane, octane, iso-pentane, isohexane, isoheptane, octane-iso, 10 carbon or 11 carbon or 12 carbon and one or more the mixing in the isoparaffin.
4. according to claim 1 is the method that catalyst prepares citric acid three ester with the hydrophobic solid acid, it is characterized in that: citric acid is the mixing of Citric Acid, usp, Anhydrous Powder, Citric acid monohydrate Food grade or two kinds.
5. according to claim 1 is the method that catalyst prepares citric acid three ester with the hydrophobic solid acid, and it is characterized in that: catalyst levels accounts for 0.2%～10% of reaction raw materials total mass.
6. described according to claim 1 is the method that catalyst prepares citric acid three ester with the hydrophobic solid acid, it is characterized in that: the method for the citric acid three ester of the alcohol of 1～3 C atom of preparation, make catalyzer with hydrophobic solid acid in the reaction process, after reaction finishes, catalyzer is separated from reaction mixture and reused, described alcohol adopts the gradation sampling system to join in the reactor, adds band aqua and pump around circuit in reactor and the water trap and uses.
7. described according to claim 1 is the method that catalyst prepares citric acid three ester with the hydrophobic solid acid, it is characterized in that: the method for the citric acid three ester of the alcohol of 4～18 C atoms of preparation, make catalyzer with hydrophobic solid acid in the reaction process, after reaction finishes, catalyzer is separated from reaction mixture and reused, described alcohol is disposable to join in the reactor, does not add the band aqua in the reaction process, and the water that generates in the reaction process is constantly told by the water trap distillation.
8. according to claim 6 is the method that catalyst prepares citric acid three ester with the hydrophobic solid acid, it is characterized in that: raw materials used mol ratio is a citric acid: alcohol: band aqua=1: 1: 0.2～1: 8: 8, temperature of reaction: 50 ℃～180 ℃, the reaction times is 1～10 hour.
9. according to claim 7 is the method for the citric acid three ester of catalyst preparation with the hydrophobic solid acid, it is characterized in that: raw materials used mol ratio is a citric acid: alcohol=1: 1～1: 8, temperature of reaction: 100 ℃～300 ℃, the reaction times is 1～10 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100646447A CN101270045A (en) | 2007-03-22 | 2007-03-22 | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100646447A CN101270045A (en) | 2007-03-22 | 2007-03-22 | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101270045A true CN101270045A (en) | 2008-09-24 |
Family
ID=40004302
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100646447A Pending CN101270045A (en) | 2007-03-22 | 2007-03-22 | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101270045A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830803A (en) * | 2010-01-25 | 2010-09-15 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
| CN102417452A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Preparation method of citrate |
| CN102584591A (en) * | 2011-12-23 | 2012-07-18 | 蚌埠丰原医药科技发展有限公司 | Method for preparing tributyl citrate through diatomite immobilized titanium sulfate used as catalyst |
| CN102584590A (en) * | 2011-12-21 | 2012-07-18 | 蚌埠丰原医药科技发展有限公司 | Method for synthesizing triethyl citrate |
| CN102659591A (en) * | 2012-04-26 | 2012-09-12 | 凯瑞化工股份有限公司 | Method for continuously catalytically synthesizing triethyl citrate plasticizer |
| CN104437637A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof |
| CN104529774A (en) * | 2014-11-26 | 2015-04-22 | 绍兴文理学院 | Preparation method for tributyl citrate |
| CN104829458A (en) * | 2015-04-01 | 2015-08-12 | 南京林业大学 | Synthetic method of di(glycol monoalkyl ether)terephthalate |
| CN105061204A (en) * | 2015-07-31 | 2015-11-18 | 邵阳学院 | Method for catalytic synthesis of citric acid ester by (NH4)xAgyH3-x-yPW12O40 composite salt |
| CN105772089A (en) * | 2016-04-25 | 2016-07-20 | 张玲 | Preparation method of triethyl citrate catalyst |
| CN106977555A (en) * | 2017-03-28 | 2017-07-25 | 华东师范大学 | A kind of method of complete acetylization of saccharides in presence of solid acid catalyst |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
-
2007
- 2007-03-22 CN CNA2007100646447A patent/CN101270045A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830803A (en) * | 2010-01-25 | 2010-09-15 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
| CN101830803B (en) * | 2010-01-25 | 2013-04-03 | 西北师范大学 | Method for synthesizing citric acid ester type compound |
| CN102417452A (en) * | 2011-12-16 | 2012-04-18 | 中粮生物化学（安徽）股份有限公司 | Preparation method of citrate |
| CN102584590A (en) * | 2011-12-21 | 2012-07-18 | 蚌埠丰原医药科技发展有限公司 | Method for synthesizing triethyl citrate |
| CN102584590B (en) * | 2011-12-21 | 2014-08-27 | 蚌埠丰原医药科技发展有限公司 | Method for synthesizing triethyl citrate |
| CN102584591A (en) * | 2011-12-23 | 2012-07-18 | 蚌埠丰原医药科技发展有限公司 | Method for preparing tributyl citrate through diatomite immobilized titanium sulfate used as catalyst |
| CN102659591A (en) * | 2012-04-26 | 2012-09-12 | 凯瑞化工股份有限公司 | Method for continuously catalytically synthesizing triethyl citrate plasticizer |
| CN104437637A (en) * | 2014-10-31 | 2015-03-25 | 常州大学 | Epoxy resin loaded phosphotungstic acid catalyst as well as preparation method and application thereof |
| CN104529774A (en) * | 2014-11-26 | 2015-04-22 | 绍兴文理学院 | Preparation method for tributyl citrate |
| CN104829458A (en) * | 2015-04-01 | 2015-08-12 | 南京林业大学 | Synthetic method of di(glycol monoalkyl ether)terephthalate |
| CN105061204A (en) * | 2015-07-31 | 2015-11-18 | 邵阳学院 | Method for catalytic synthesis of citric acid ester by (NH4)xAgyH3-x-yPW12O40 composite salt |
| CN105061204B (en) * | 2015-07-31 | 2016-09-28 | 邵阳学院 | A kind of method that silver phosphotungstate ammonium compound salt catalyzes and synthesizes citrate |
| CN105772089A (en) * | 2016-04-25 | 2016-07-20 | 张玲 | Preparation method of triethyl citrate catalyst |
| CN106977555A (en) * | 2017-03-28 | 2017-07-25 | 华东师范大学 | A kind of method of complete acetylization of saccharides in presence of solid acid catalyst |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
| CN108892613B (en) * | 2018-07-11 | 2021-02-19 | 广东轻工职业技术学院 | Method for synthesizing tri-n-butyl citrate by using acid modified H-ZMS-5 type molecular sieve |
| CN114369024A (en) * | 2021-12-31 | 2022-04-19 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
| CN114369024B (en) * | 2021-12-31 | 2024-01-30 | 河南金丹乳酸科技股份有限公司 | PTA and BDO esterification process for PBAT production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101270045A (en) | Method for synthesizing triester citrate with hydrophobic solid acid as catalyst | |
| CN103880783B (en) | Reaction control phase transfer catalyst catalysis preparing epoxypropane by epoxidation of propene method | |
| CN101722027A (en) | Esterification catalyst for synthesizing ethylene/propylene glycol ether carboxylate, and preparation method thereof | |
| CN101318880B (en) | Green synthesis process for bornyl alcohol | |
| CN102320970A (en) | With the modified cation-exchange resin is the method for Preparation of Catalyst tributyl citrate | |
| CN103613501A (en) | Method for preparing tributyl citrate by taking macroporous strong-acid cation exchange resin as catalyst | |
| CN101020631B (en) | S2O8 2-/TiO2 Al2 O3 super solid acid catalyzed n-butyl acetate synthesizing process | |
| CN101157053A (en) | Catalyst and use thereof new type solid catalyst as well as its preparing method and usage | |
| CN105152980A (en) | Chiral preparation method for N-t-butyloxycarboryl-(4S)-(p-phenyl phenyl methyl)-4-amino-(2R)-methylbutyric acid | |
| CN103319341A (en) | Method for synthesizing methyl oleate | |
| CN101747187A (en) | Method for preparing iso-octyl palmitate | |
| CN101869847B (en) | Micro-spherical polymer solid acid esterification catalyst and preparation method thereof | |
| CN104829454A (en) | Method of synthesizing tricyclodecenyl isobutyrate spice | |
| CN103694169A (en) | Method for synthesis of 2,2,4-trimethyl-1,2-dihydroquinoline and polymer thereof by utilizing microchannel reactors | |
| CN104961679A (en) | Method for synthesizing ethoxyquinoline | |
| CN106905121A (en) | A kind of preparation method of benzaldehyde | |
| CN107056617A (en) | A kind of rectification process and equipment for producing methyl methacrylate | |
| CN103408413B (en) | Method for preparing deuterated chloroform by using hexachloroacetone as intermediate | |
| CN102627561B (en) | Preparation process for plasticizer-tributyl citrate | |
| CN103387495A (en) | Method for the continuous production of carboxylic acid esters | |
| CN102795976A (en) | Method for preparing diethoxymethane by using active carbon supported solid acid catalyst | |
| CN101434539A (en) | Preparation of benzyl acetate | |
| CN105801376B (en) | Silica gel supported imidazole ion liquid is catalyzed the production method of benzene direct oxidation phenol | |
| CN104447230A (en) | Method for preparing 4-methoxystyrene | |
| CN101429127A (en) | Method for superacid catalysis synthesis of isoamyl salicylate with mesoporous molecular sieve solid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080924 |