CN102249916A - Continuous production process for tributyl citrate - Google Patents
Continuous production process for tributyl citrate Download PDFInfo
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- CN102249916A CN102249916A CN2011101380131A CN201110138013A CN102249916A CN 102249916 A CN102249916 A CN 102249916A CN 2011101380131 A CN2011101380131 A CN 2011101380131A CN 201110138013 A CN201110138013 A CN 201110138013A CN 102249916 A CN102249916 A CN 102249916A
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Abstract
The invention relates to a continuous production process for tributyl citrate, in particular to a continuous production process for refining the tributyl citrate by a membrane separation technology, and belongs to the technical field of chemical engineering. In esterification, a solid acid catalyst with the granularity of 10 to 100nm is adopted and has high activity and high reaction speed. The traditional neutralization washing, catalyst separation and reduced pressure dealcholization process is improved by the membrane separation technology, the whole technological process is continuously and automatically operated, the production efficiency is high, the product quality is stable. The catalyst separation process and the esterification process are coupled in the same system, and the problem that a fine suspended catalyst is seriously lost in the separating and recycling process is solved. By membrane separation, the energy consumption is low and the recovery efficiency of butanol is high. The equipment investment is small, and the process is suitable for large-scale production.
Description
Technical field
The present invention relates to a kind of continuous production technology of tributyl citrate, especially a kind of continuous production technology with the refining tributyl citrate of membrane separation technique belongs to technical field of chemical engineering.
Background technology
Tributyl citrate (being called for short TBC) is as a kind of novel " green " environmentally-friendly plastic softening agent, have nonpoisonous and tasteless, consistency good, plasticizing efficiency is high, easily by advantage such as biological degradation and volatility be little, winter hardiness, photostabilization and have excellent water-resistance, and anti-fungi performance is arranged, alternative phthalate conventional plasticizers in resin.Therefore TBC is widely used in fields such as food and medical instrumentation package, makeup, daily necessities, toy, personal hygiene article, also is the important chemical intermediate simultaneously.
Traditional TBC production technique generally is to be that esterification is synthetic under the effect of catalyzer at the vitriol oil by citric acid and propyl carbinol, and the aftertreatment of reaction product will obtain finished product at last through alkali neutralization, washing, distillation dealcoholysis dehydration, decolouring.Its reaction principle is the reaction equation of face as follows.
Adopt traditional technology to produce tributyl citrate, though quality product is more stable, can be up to state standards, also there is obvious defects in the method for this production tributyl citrate, as:
Though 1. sulfuric acid low price, the catalytic activity height, there are a lot of shortcomings in it: the production cycle is long, and transformation efficiency is low; And because vitriolic dehydration, esterification and oxygenizement, by product is many, and this refining and recovery to reaction product all brings difficulty; In addition, sulfuric acid is severe corrosion equipment also, increases production cost.
2. the aftertreatment of traditional technology mainly comprises steps such as neutralization, washing, decompression dealcoholysis, decolouring press filtration, belongs to periodical operation, and process is discontinuous, and labour intensity is bigger; Alkali neutralizes, washes and remove the sulfuric acid as catalyzer, causes complex process, and it is big to produce wastewater flow rate, and separation efficiency is low, causes product to run off; Underpressure distillation dealcoholysis energy consumption will just can reach requirement through multistage dealcoholysis than higher, complicated operation, and separation efficiency is low, long flow path, it is more to produce the three wastes; Device has high input, and industrial scale is little, has reduced production efficiency.
Adopt solid acid catalyst to replace vitriol oil synthesizing citric acid tri-n-butyl, can solve liquid acid pollution of ecological environment, etching apparatus and harm production operation safety problem in the esterification technique.Generally speaking, granules of catalyst is thin more, and speed of reaction is fast more, but the separation of small grain size catalyzer is more difficult.Separation methods such as traditional gravity settling, centrifugation, flotation, cake filtration, Depth Filtration all can not effectively be separated it from liquid-phase product fully, cause catalyst loss serious, and can influence degree of purity of production.
In addition; country is more and more higher for the restriction and the environmental protection requirement of softening agent; for this reason; press for the traditional technology of producing tributyl citrate is reformed; work out a kind of new, production technique rational, advanced, environmental protection as early as possible, to satisfy the heavy demand of current domestic and international market to tributyl citrate.
Summary of the invention
The continuous production technology that the purpose of this invention is to provide a kind of tributyl citrate, use this technology can successfully adopt the mineral membrane isolation technique to realize product purification, the separation of subparticle solid catalyst can be effectively solved, dealcoholysis and dewatering efficiency can be improved; Simultaneously can also improve product purity, cut down the consumption of energy, reduce wastewater discharge, continuous automatic production is raised the efficiency, and strengthens industrial scale.
Technical scheme of the present invention is:
A kind of continuous production technology of tributyl citrate is characterized in that comprising step:
(1) esterification of citric acid and butanols: citric acid, propyl carbinol and solid catalyst are added in the reactor according to a certain percentage, under the reaction process condition of routine, carry out esterification.
Wherein, described solid catalyst be interpreted as any in the prior art can the catalysis citric acid and the solid catalyst of propyl carbinol generation esterification.In the present invention, described solid catalyst is a solid acid, includes but not limited to molecular sieve catalyst, super acidic catalyst and heteropolyacid catalyst; The particle diameter of catalyzer is 10～100 nm.
The mol ratio of described citric acid and propyl carbinol is 1:4～1:6; It is 1%～3% that described solid catalyst accounts for the citric acid mass percent; Described enzymatic synthesis condition is: 100～140 ℃ were reacted 2～4 hours down.
(2) in the embrane method and washing: after esterification finishes, add in the alkaline solution and after, leave standstill and make the ester water stratification, getting upper strata ester layer adds water continuously and enters hydrophilic porous membrane module together, carry out aqueous phase separation, until the ester layer is washed till neutrality, obtain holding back the concentrated material of survey, mainly comprise propyl carbinol, tributyl citrate and catalyzer; Per-meate side is separated water outlet to wastewater treatment.
Wherein, described alkaline solution is yellow soda ash, sodium hydroxide or potassium hydroxide solution, and concentration is 3%～5%.
Described hydrophilic porous membrane module is the tubular type mineral membrane; It is the symmetry or the asymmetric membrane of pottery, metal or its matrix material formation of 5～500 nm that described mineral membrane adopts mean pore size; Single tube or hyperchannel all can.
Described membrane sepn operating parameters is: cross-flow velocity 1～5 m/s, working pressure 0.1～0.5 MPa.
(3) embrane method catalyst separating: the concentrated material of holding back side enters lipophilicity porous-film assembly and carries out solid-liquid separation, and wherein propyl carbinol and tributyl citrate are separated through per-meate side, and the solid catalyst of holding back reclaims.
Wherein, described lipophilicity porous-film assembly is the modified ceramic film, and it is the symmetry or the asymmetric membrane of the pottery formation of 5～500 nm that ceramic membrane adopts mean pore size; Single tube or hyperchannel all can; The modification of used ceramic membrane adopts organo silane coupling agent that ceramic membrane is carried out chemical modification, and the contact angle of water droplet on the film surface is 90～170 degree.
Described membrane sepn operating parameters is: cross-flow velocity 1～7m/s, working pressure 0.1～0.6 MPa.
(4) infiltration evaporation dealcoholysis: the mixture of propyl carbinol and tributyl citrate is delivered into infiltration vaporization membrane module, and propyl carbinol is isolated and is reclaimed from per-meate side, obtains spissated tributyl citrate.
Wherein, the supporting layer of described infiltrating and vaporizing membrane is an aluminum oxide, and separating layer is a polydimethylsiloxane.
(5) the decolouring press filtration obtains tributyl citrate.
Beneficial effect of the present invention is:
1. the present invention has realized the continuous operation of whole technological process, the level of automation height, and labour intensity is little, and is easy to operate, the production efficiency height.
2. the present invention has realized continuous operation, has solved the separation problem of fine suspended state catalyzer in the esterification, and " reaction-separation-reuse " of catalyzer can be carried out continuously; Technology is succinct, and facility investment is few, has reduced the loss of catalyzer, and production can be carried out continuously, enhances productivity.
3. the present invention adopts the nanoscale solids acid catalyst, has accelerated speed of response, shortens the reaction times, and esterification yield reaches more than 97% simultaneously.
4. the present invention adopts in the embrane method and washing process, and the separation efficiency height can move in serialization, and little than the traditional technology wastewater discharge, environmental pollution is little.
5. the present invention adopts infiltration evaporation to remove butanols, and energy consumption is low, and is pollution-free, satisfies environmental requirement, the separation efficiency height, and operation is simple continuously, and has realized " reclaiming-utilize again " continuous process of butanols.
6. the tributyl citrate product performance that obtain of the present invention are stable, Functionality, quality and appealing design.
7. membrane separation unit facility investment of the present invention is little, and energy consumption is low, easily forms large-scale production.
Description of drawings
Fig. 1 is the operational flowchart of tributyl citrate continuous production technology of the present invention.
Embodiment
Below in conjunction with the description of drawings embodiments of the present invention.
Embodiment 1
1, esterification step
Citric acid and the propyl carbinol mol ratio according to 1:4.5 is dropped in the reactor, adds the mass percent that 1.5%(accounts for citric acid) solid super acid catalyst 50 nm, close dog-house, open chuck heating steam valve, control steam＜0.6 MPa(gauge pressure).Note the water outlet situation, strict control still internal pressure (gauge pressure)＜0.015 MPa, in order to avoid cause towards material, the control of reaction top temperature is less than 120 ℃, reaction reaches 2 hours, get final product sample examination, per half an hour sampling then once, when the acid number of thick ester liquid is less than 0.02 mg KOH/g, can think that esterification finishes, close chuck heating steam valve, close reverse flow valve, stop to stir.Open the cooling of reactor condenser.
2, in the embrane method and washing step
After reaction finishes, the resultant of reaction material that is mixed with catalyzer is exported with pump, metering back material enters neutralization tank, the Na with 3%
2CO
3The alkaline solution neutralization is left standstill then and is made the ester water stratification, and water is in the bottom of neutralization tank, by putting into and water collecting tank after the metering.The ester layer is exported by pump, and adds washing continuously simultaneously, enters hydrophilic porous ceramic film component together, carries out aqueous phase separation, is washed till neutrality.The concentrated material of holding back side mainly comprises propyl carbinol, tributyl citrate and catalyzer, enters relay tank 1 and regulates pressure, and per-meate side is isolated water to the wastewater collection jar.Adopting the aperture is the tubular ceramic membrane of 0.03 μ m, 19 passages, passage internal diameter 4 mm, cross-flow velocity 1m/s, working pressure 0.4 MPa, membrane permeation flux 0.5m
3M
-2H
-1
3, embrane method catalyst separating operation
Material in the relay tank 1 enters close organic rerum natura porous ceramic film assembly via pump, and wherein propyl carbinol and tributyl citrate are separated through per-meate side and entered relay tank 2.Catalyzer is trapped, and when being concentrated to solid content when reaching 15%, sepn process is finished, and returns esterifying kettle and is used for secondary response down.Adopting the aperture is the ceramic membrane of 0.02 μ m, 7 passages, and the modification of used ceramic membrane adopts organo silane coupling agent that ceramic membrane is carried out chemical modification, and the contact angle of water droplet on the film surface is 90～170 degree; Passage internal diameter 6mm, cross-flow velocity 1m/s, working pressure 0.3MPa, membrane permeation flux 0.1m
3M
-2H
-1
4, infiltration evaporation dealcoholysis operation and decolouring press filtration operation
Material in the relay tank 2 enters infiltration vaporization membrane module with pump delivery, and propyl carbinol is preferentially separated, and returns esterifying kettle and continues recycle, and spissated tributyl citrate is packaged to be finished product through decolouring, press filtration.The yield of tributyl citrate is 97.5%.Adopt polydimethylsiloxane (PDMS)/aluminum oxide infiltrating and vaporizing membrane, working pressure 0.2 MPa, membrane permeation flux 4kgm
-2H
-1
Embodiment 2
1, esterification step
Citric acid and the propyl carbinol mol ratio according to 1:4 is dropped in the reactor, adds the mass percent that 1%(accounts for citric acid) molecular sieve catalyst 10 nm, close dog-house, open chuck heating steam valve, control steam＜0.6 MPa(gauge pressure).Note the water outlet situation, strict control still internal pressure (gauge pressure)＜0.015 MPa, in order to avoid cause towards material, the control of reaction top temperature is less than 100 ℃, reaction reaches 3 hours, sample examination, per half an hour sampling then once, when the acid number of thick ester liquid is less than 0.02mgKOH/g, can think that esterification finishes, close chuck heating steam valve, close reverse flow valve, stop to stir.Open the cooling of reactor condenser.
2, in the embrane method and washing step
After reaction finishes, the resultant of reaction material that is mixed with catalyzer is exported with pump, metering back material enters neutralization tank, and the NaOH alkaline solution neutralization with 5% is left standstill then and made the ester water stratification, and water is in the bottom of neutralization tank, by putting into and water collecting tank after the metering.The ester layer is exported by pump, and adds washing continuously simultaneously, enters hydrophilic porous ceramic film component together, carries out aqueous phase separation, is washed till neutrality.The concentrated material of holding back side mainly comprises propyl carbinol, tributyl citrate and catalyzer, enters relay tank 1 and regulates pressure, and per-meate side is isolated water to the wastewater collection jar.Adopting the aperture is the tube type metal film of 0.005 μ m, 19 passages, passage internal diameter 4mm, cross-flow velocity 5m/s, working pressure 0.1MPa, membrane permeation flux 0.05m
3M
-2H
-1
3, embrane method catalyst separating operation
Material in the relay tank 1 enters close organic rerum natura porous ceramic film assembly via pump, and wherein propyl carbinol and tributyl citrate are separated through per-meate side and entered relay tank 2.Catalyzer is trapped, and when being concentrated to solid content when reaching 15%, sepn process is finished, and returns esterifying kettle and is used for secondary response down.Adopting the aperture is the ceramic membrane of 0.5 μ m, 7 passages, and the modification of used ceramic membrane adopts organo silane coupling agent that ceramic membrane is carried out chemical modification, and the contact angle of water droplet on the film surface is 90～170 degree; Passage internal diameter 6mm, cross-flow velocity 7 m/s, working pressure 0.6MPa, membrane permeation flux 0.8m
3M
-2H
-1
4, infiltration evaporation dealcoholysis operation and decolouring press filtration operation
Material in the relay tank 2 enters infiltration vaporization membrane module with pump delivery, and propyl carbinol is preferentially separated, and returns esterifying kettle and continues recycle, and spissated tributyl citrate is packaged to be finished product through decolouring, press filtration.The yield of tributyl citrate is 97.0%.Adopt polydimethylsiloxane (PDMS)/aluminum oxide infiltrating and vaporizing membrane, working pressure 0.2 MPa, membrane permeation flux 4kgm
-2H
-1
Embodiment 3
1, esterification step
Citric acid and the propyl carbinol mol ratio according to 1:6 is dropped in the reactor, adds the mass percent that 3%(accounts for citric acid) heteropolyacid catalyst 100 nm, close dog-house, open chuck heating steam valve, control steam＜0.6 MPa(gauge pressure).Note the water outlet situation, strict control still internal pressure (gauge pressure)＜0.015 MPa, in order to avoid cause towards material, the control of reaction top temperature is less than 140 ℃, reaction reaches 4 hours, sample examination, per half an hour sampling then once, when the acid number of thick ester liquid is less than 0.02mgKOH/g, can think that esterification finishes, close chuck heating steam valve, close reverse flow valve, stop to stir.Open the cooling of reactor condenser.
2, in the embrane method and washing step
After reaction finishes, the resultant of reaction material that is mixed with catalyzer is exported with pump, metering back material enters neutralization tank, and the KOH alkaline solution neutralization with 4% is left standstill then and made the ester water stratification, and water is in the bottom of neutralization tank, by putting into and water collecting tank after the metering.The ester layer is exported by pump, and adds washing continuously simultaneously, enters hydrophilic porous ceramic film component together, carries out aqueous phase separation, is washed till neutrality.The concentrated material of holding back side mainly comprises propyl carbinol, tributyl citrate and catalyzer, enters relay tank 1 and regulates pressure, and per-meate side is isolated water to the wastewater collection jar.Adopting the aperture is the ceramic-metal composite film of 0.5 μ m, 19 passages, passage internal diameter 4mm, cross-flow velocity 3m/s, working pressure 0.5MPa, membrane permeation flux 0.5m
3M
-2H
-1
3, embrane method catalyst separating operation
Material in the relay tank 1 enters close organic rerum natura porous ceramic film assembly via pump, and wherein propyl carbinol and tributyl citrate are separated through per-meate side and entered relay tank 2.Catalyzer is trapped, and when being concentrated to solid content when reaching 15%, sepn process is finished, and returns esterifying kettle and is used for secondary response down.Adopting the aperture is the ceramic membrane of 0.005 μ m, 7 passages, and the modification of used ceramic membrane adopts organo silane coupling agent that ceramic membrane is carried out chemical modification, and the contact angle of water droplet on the film surface is 90～170 degree; Passage internal diameter 6mm, cross-flow velocity 2 m/s, working pressure 0.1MPa, membrane permeation flux 0.02 m
3M
-2H
-1
4, infiltration evaporation dealcoholysis operation and decolouring press filtration operation
Material in the relay tank 2 enters infiltration vaporization membrane module with pump delivery, and propyl carbinol is preferentially separated, and returns esterifying kettle and continues recycle, and spissated tributyl citrate is packaged to be finished product through decolouring, press filtration.The yield of tributyl citrate is 96.8%.Adopt polydimethylsiloxane (PDMS)/aluminum oxide infiltrating and vaporizing membrane, working pressure 0.2 MPa, membrane permeation flux 4kgm
-2H
-1
Claims (10)
1. the continuous production technology of a tributyl citrate is characterized in that comprising step:
(1) esterification of citric acid and butanols: citric acid, propyl carbinol and solid catalyst are added in the reactor, under the reaction process condition of routine, carry out esterification;
(2) in the embrane method and washing: after esterification finishes, add in the alkaline solution and after, leave standstill and make the ester water stratification, getting upper strata ester layer adds water continuously and enters hydrophilic porous membrane module together, carry out aqueous phase separation, until the ester layer is washed till neutrality, obtain holding back the concentrated material of survey, mainly comprise propyl carbinol, tributyl citrate and catalyzer; Per-meate side is separated water outlet to wastewater treatment;
(3) embrane method catalyst separating: the concentrated material of holding back side enters lipophilicity porous-film assembly and carries out solid-liquid separation, and wherein propyl carbinol and tributyl citrate are separated through per-meate side, and the solid catalyst of holding back reclaims;
(4) infiltration evaporation dealcoholysis: the mixture of propyl carbinol and tributyl citrate is delivered into infiltration vaporization membrane module, and propyl carbinol is isolated and is reclaimed from per-meate side, obtains spissated tributyl citrate;
(5) the decolouring press filtration obtains tributyl citrate.
2. the continuous production technology of tributyl citrate according to claim 1 is characterized in that the described solid catalyst of step (1) is a solid acid.
3. the continuous production technology of tributyl citrate according to claim 2 is characterized in that described solid acid is molecular sieve catalyst, super acidic catalyst or heteropolyacid catalyst; The particle diameter of catalyzer is 10～100 nm.
4. the continuous production technology of tributyl citrate according to claim 1 is characterized in that the mol ratio of middle citric acid of described step (1) and propyl carbinol is 1:4～1:6; It is 1%～3% that described solid catalyst accounts for the citric acid mass percent; Described enzymatic synthesis condition is: 100～140 ℃ were reacted 2～4 hours down.
5. the continuous production technology of tributyl citrate according to claim 1, the alkaline solution that it is characterized in that described step (2) is that concentration is 3%～5% yellow soda ash, sodium hydroxide or potassium hydroxide solution.
6. the continuous production technology of tributyl citrate according to claim 1, the hydrophilic porous membrane module that it is characterized in that described step (2) is the tubular type mineral membrane; And it is the symmetry or the asymmetric membrane of pottery, metal or its matrix material formation of 5～500 nm that described mineral membrane adopts mean pore size.
7. the continuous production technology of tributyl citrate according to claim 1 is characterized in that the membrane sepn operating parameters of described step (2) is: cross-flow velocity 1～5 m/s, working pressure 0.1～0.5 MPa.
8. the continuous production technology of tributyl citrate according to claim 1 is characterized in that lipophilicity porous-film assembly is the modified ceramic film in the described step (3); It is the symmetry or the asymmetric membrane of the pottery formation of 5～500 nm that ceramic membrane adopts mean pore size; And the modification of used ceramic membrane adopts organo silane coupling agent that ceramic membrane is carried out chemical modification, and the contact angle of water droplet on the film surface is 90～170 degree.
9. the continuous production technology of tributyl citrate according to claim 1 is characterized in that the membrane sepn operating parameters of described step (3) is: cross-flow velocity 1～7m/s, working pressure 0.1～0.6 MPa.
10. the continuous production technology of tributyl citrate according to claim 1, the supporting layer that it is characterized in that the infiltrating and vaporizing membrane of described step (4) is an aluminum oxide, separating layer is a polydimethylsiloxane.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649748A (en) * | 2012-04-11 | 2012-08-29 | 江苏雷蒙化工科技有限公司 | Neutralization and water washing continuation device of citrate |
| CN102701975A (en) * | 2012-04-11 | 2012-10-03 | 江苏雷蒙化工科技有限公司 | Improvement of process for synthesizing acetyl tri-n-butyl citrate by activated carbon supported sulfuric acid |
| CN103553903A (en) * | 2013-11-01 | 2014-02-05 | 桂林甙元生物科技有限公司 | Novel process for extracting not smaller than 98% of natural ferulic acid from rice bran oil processing leftovers |
| CN106543000A (en) * | 2016-10-27 | 2017-03-29 | 南京科技职业学院 | A kind of esterification purifying and cleaning production technology |
| CN108452553A (en) * | 2018-04-01 | 2018-08-28 | 中鸿纳米纤维技术丹阳有限公司 | A kind of aeroge alcohol water recovery device |
| CN109776314A (en) * | 2019-01-31 | 2019-05-21 | 新昌县泰如科技有限公司 | A kind of preparation method of cinnamate |
| CN112679354A (en) * | 2020-12-31 | 2021-04-20 | 浙江物美生物科技有限公司 | Production process of isopropyl myristate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101125814A (en) * | 2007-09-17 | 2008-02-20 | 李祥庆 | Method for synthesizing acetyl tributyl citrate by using ion type catalyst |
| CN101181689A (en) * | 2007-09-13 | 2008-05-21 | 西北师范大学 | Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof |
| CN101255114A (en) * | 2007-09-06 | 2008-09-03 | 兰州理工大学 | Method for preparing oleoyl tributyl citrate plasticizer |
-
2011
- 2011-05-26 CN CN201110138013.1A patent/CN102249916B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255114A (en) * | 2007-09-06 | 2008-09-03 | 兰州理工大学 | Method for preparing oleoyl tributyl citrate plasticizer |
| CN101181689A (en) * | 2007-09-13 | 2008-05-21 | 西北师范大学 | Heteropolyacid catalyst using paligorskite as carrier as well as preparation and uses thereof |
| CN101125814A (en) * | 2007-09-17 | 2008-02-20 | 李祥庆 | Method for synthesizing acetyl tributyl citrate by using ion type catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 李秀瑜: "固体酸催化合成无毒增塑剂柠檬酸三正丁酯", 《精细化工》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102649748A (en) * | 2012-04-11 | 2012-08-29 | 江苏雷蒙化工科技有限公司 | Neutralization and water washing continuation device of citrate |
| CN102701975A (en) * | 2012-04-11 | 2012-10-03 | 江苏雷蒙化工科技有限公司 | Improvement of process for synthesizing acetyl tri-n-butyl citrate by activated carbon supported sulfuric acid |
| CN102649748B (en) * | 2012-04-11 | 2014-04-23 | 江苏雷蒙化工科技有限公司 | Neutralization and water washing continuation device of citrate |
| CN103553903A (en) * | 2013-11-01 | 2014-02-05 | 桂林甙元生物科技有限公司 | Novel process for extracting not smaller than 98% of natural ferulic acid from rice bran oil processing leftovers |
| CN103553903B (en) * | 2013-11-01 | 2015-05-06 | 桂林甙元生物科技有限公司 | Novel process for extracting not smaller than 98% of natural ferulic acid from rice bran oil processing leftovers |
| CN106543000A (en) * | 2016-10-27 | 2017-03-29 | 南京科技职业学院 | A kind of esterification purifying and cleaning production technology |
| CN108452553A (en) * | 2018-04-01 | 2018-08-28 | 中鸿纳米纤维技术丹阳有限公司 | A kind of aeroge alcohol water recovery device |
| CN108452553B (en) * | 2018-04-01 | 2023-12-15 | 重庆梁彬新材料技术有限公司 | Alcohol water recovery unit for aerogel |
| CN109776314A (en) * | 2019-01-31 | 2019-05-21 | 新昌县泰如科技有限公司 | A kind of preparation method of cinnamate |
| CN109776314B (en) * | 2019-01-31 | 2021-11-12 | 新昌县泰如科技有限公司 | Preparation method of cinnamate |
| CN112679354A (en) * | 2020-12-31 | 2021-04-20 | 浙江物美生物科技有限公司 | Production process of isopropyl myristate |
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| CN102249916B (en) | 2014-07-23 |
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