CN1151433A - Method of synthesizing mixed methyl aliphatic ester using cotton seed oil soap bottoms as raw material - Google Patents
Method of synthesizing mixed methyl aliphatic ester using cotton seed oil soap bottoms as raw material Download PDFInfo
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- CN1151433A CN1151433A CN95112260A CN95112260A CN1151433A CN 1151433 A CN1151433 A CN 1151433A CN 95112260 A CN95112260 A CN 95112260A CN 95112260 A CN95112260 A CN 95112260A CN 1151433 A CN1151433 A CN 1151433A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
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Abstract
A process for synthesizing mixed methyl aliphatic ester with the bottoms of cotton seed oil soap includes such steps as: stirring said bottoms with concentrated sulfuric acid in reactor while heating for acidification, washing the resultant fatty matter and dewatering, esterifying reaction of said fatty matter, methanol and concentrated sulfuric acid in reactor to obtain crude ester, addition of sodium carbonate for deacidification, heating and pressure reducing distillation of deacidified crude ester in distiller to obtain mixed methyl aliphatic ester. It features simple and reliable technology, less consumption of acid and alkali, high yield and low cost.
Description
The invention provides a kind of method of producing mixed methyl aliphatic ester with the byproduct cotton oil distillation residues in the Oleum Gossypii semen production process.
Mixed methyl aliphatic ester is a basic raw material of producing the pure and mild octadecanol of 16 carbon, also be the direct material of producing tensio-active agents such as fatty acid triethanol amine, fatty acid diethanolamine, lipid acid Monoethanolamine MEA BASF, alpha-sulfo fatty acid methyl ester, the application in other organic chemistry industry is also very extensive.At present the main technique route of the mixed methyl aliphatic ester of the pure and mild octadecanol of domestic production 16 carbon is to be that raw material carries out transesterification reaction with vegetable and animals oils such as Oleum Gossypii semen, lards, is that raw material carries out esterification and makes with the refining mixed fatty acid of the pure and mild octadecanol of 16 carbon perhaps.In recent years, because the price of Oleum Gossypii semen and animal grease and lipid acid constantly raises up, the production cost of fatty acid methyl ester is improved greatly.China produces cotton big country, and oil cotton source mill in various places all will give off a large amount of cotton oil distillation residues when oil refining, wherein contain fatty things such as available lipid acid, neutral oil, the single, double glyceryl ester of lipid acid, and cheap and easy to get.Therefore, someone once utilized cotton oil distillation residues to be the feedstock production mixed methyl aliphatic ester, its operational path is, earlier with cotton oil distillation residues highly basic saponification, make whole glycerine one fatty acid ester, dialycerides fat acid fat and neutral oil in the cotton oil distillation residues be converted into soap, the soap acidifying is a mixed fatty acid, again the mixed fatty acid underpressure distillation is refining mixed fatty acid.With the esterification and prepare mixed methyl aliphatic ester under sulphuric acid catalysis of refining mixed fatty acid and methyl alcohol, underpressure distillation obtains smart ester again.This method, complex process not only, and certainly will increase the consumption of alkali and acid in the reaction process through saponification, and there is 20 percent to percent 25 lipid acid in still-process, to be polymerized to black glue and to have reduced yield in the underpressure distillation, improved cost.
The purpose of this invention is to provide a kind of is the method for raw material synthesizing mixed methyl aliphatic ester with the cotton oil distillation residues, to reduce production costs, improves yield, alleviates the cotton oil distillation residues pollution on the environment.
The present invention realizes like this, mixed fatty acid methyl alcohol is through acidifying by cotton oil distillation residues, esterification, depickling, underpressure distillation is made, by weight with cotton oil distillation residues: the ratio of dense carbonic acid=10: 0.5～1.5 drops in the reactor and stirs, heat up, when temperature is increased to 105 ℃, the pH value of inspection by sampling lower floor solution, with cotton oil distillation residues pH value is adjusted in 2～3 then, insulation reaction 0.5 hour, stop heating and stirring, left standstill 0.5～1 hour, lower floor's acid solution is put into storage vessel or reuse, add isopyknic tap water washing in the fatty thing on upper strata, repetitive scrubbing to the pH value of emitting water liquid is till 4～5, stirring heating then, in vacuum tightness is to be heated to 250 ℃ under the 600mm/Hg to keep 0.5 hour, carries out processed, and water content is reduced to below 3/10000ths; In esterification, by weight with methyl alcohol: fatty thing=1.5～2.5 after the dehydration: 1 ratio is put in the reactor, be methyl alcohol again with weight with dehydration after 2%～5% the vitriol oil of fatty thing gross weight be added in the reactor, under agitation be heated to reflux temperature (being about 65～70 ℃), insulation back flow reaction 15 hours changes reflux into water distilling apparatus, heat temperature raising then, excessive methyl alcohol is steamed reuse, when temperature is raised to 110 ℃, stop heating; In deacidification, in the thick ester that esterification obtains, add till isopyknic tap water repetitive scrubbing to the pH value of the aqueous solution of emitting is bordering at 7 o'clock, the acid number of the thick ester of sampling and measuring then, add excessive 5% yellow soda ash according to acid number, under agitation be rapidly heated to 100～120 ℃ of afterreactions got final product in 10 minutes; In vacuum distillation process, after thick ester after the depickling is preheated to 200 ℃ with conduit and still kettle connection, connect a valve on the conduit, add thermal distillation, temperature control is between 220～230 ℃, and vacuum tightness is 750mm/Hg, then, slowly open duct valve, feed intake and carry out underpressure distillation, the distilled material is mixed methyl aliphatic ester.
The sulfuric acid that in acidization, adds mainly be with cotton oil distillation residues in the sodium soap reactant salt, generate the water insoluble lipid acid that also is insoluble to dilute sulphuric acid, it emanates from solution with fatty things such as the neutral oil that does not react with dilute sulphuric acid, lipid acid one, two glyceryl ester.After leaving standstill, whole solution is divided into three layers, and the upper strata is fatty thing, and the centre is a colloid, and lower floor is a waste acid water solution.
Adopt the sulphuric acid catalysis esterification, fatty thing under sulphuric acid catalysis and the main chemical reactions that takes place of methyl alcohol be:
R: the saturated or unsaturated alkyl that is 15 carbon or 17 carbon
From as can be seen above, the transesterification reaction that the esterification that existing lipid acid and methyl alcohol take place in the above-mentioned reaction also has neutral oil, lipid acid one, two glyceryl ester and methyl alcohol to take place, it is completely different that the base catalysis esterification legal system with grease is equipped with fatty acid methyl ester and same lipid acid in this, the methanolic acid catalysis method prepares fatty acid methyl ester.
From the mechanism of esterification, sulfuric acid mainly plays two effects, the one, catalyzer.That is: there is the Electron Affinities that has increased carbonyl in vitriolic, is beneficial to methyl alcohol the reaction that addition generates ester takes place to the carbonyl attack.The 2nd, absorb the water that generates in the esterification, promote reversible reaction to carry out to positive dirction.
Because esterification is a reversible, in the thick ester of finishing esterification and after washing, preparing, still be mixed with the lipid acid of small-amount free, its existence directly influences the acid number of smart ester after the thick ester underpressure distillation, therefore must remove the free fatty acids that exists in the thick ester as far as possible.Test shows that the yellow soda ash effect is best.The optimal temperature of deacidifying process is 100～120 ℃.In the acid number of thick ester, the alkali number of adding if in surpassing fully and the required theoretical amount of free fatty acids 5%.At this moment, the loss amount minimum of ester.
Adopt the aforesaid method synthesizing mixed methyl aliphatic ester, the direct acidifying of cotton oil distillation residues esterification then can obtain finished product through a underpressure distillation, and technology is simple, reliable, and the consumption of alkali and acid is low, yield height, low cost of manufacture.
The technical indicator of the mixed methyl aliphatic ester of aforesaid method manufacturing below is provided.
| Project | Standard index (Q/SBHOO1-1994) | Accessible index |
| Saponification value (mgKOH/g) | 190～205 | 196 |
| Acid number (mgKOH/g) | 5 | 3.7 |
| Color and luster (iodine), number | 20 | ∠10 |
Claims (1)
- A kind of is the synthetic mixed fatty acid formicester method of raw material with the cotton oil distillation residues, it is characterized in that, described mixed methyl aliphatic ester is that cotton oil distillation residues is through acidifying, esterification, depickling, underpressure distillation is made, in acidization, by weight with cotton oil distillation residues: the ratio of the vitriol oil=10: 0.5～1.5 drops in the reactor and stirs, heat up, when temperature is increased to 105 ℃, the pH value of inspection by sampling lower floor solution, with cotton oil distillation residues pH value is adjusted in 2～3 then, insulation reaction 0.5 hour, stop heating and stirring, left standstill 0.5～1 hour, lower floor's acid solution is put into storage vessel or reuse, add isopyknic tap water washing in the fatty thing on upper strata, repetitive scrubbing to the pH value of emitting water liquid is till 4～5, stirring heating then, in vacuum tightness is to be heated to 250 ℃ under the 600mm/Hg to keep 0.5 hour, carries out processed, and water content is reduced to below 3/10000ths; In esterification, by weight with methyl alcohol: fatty thing=1.5～2.5 after the dehydration: 1 ratio is put in the reactor, be methyl alcohol again with weight with dehydration after 2%～5% the vitriol oil of fatty thing gross weight be added in the reactor, under agitation be heated to reflux temperature (65～70 ℃), insulation back flow reaction 15 hours changes reflux into water distilling apparatus, heat temperature raising then, excessive methyl alcohol is steamed reuse, when temperature is raised to 110 ℃, stop heating; In deacidification, in the thick ester that esterification obtains, add till isopyknic tap water repetitive scrubbing to the pH value of the aqueous solution of emitting is bordering at 7 o'clock, the acid number of the thick ester of sampling and measuring then, add excessive 5% yellow soda ash according to acid number, under agitation be rapidly heated to 100～120 ℃ of afterreactions got final product in 10 minutes; In vacuum distillation process, after thick ester after the depickling is preheated to 200 ℃ with conduit and still kettle connection, connect a valve on the conduit, add thermal distillation, temperature control is between 220～230 ℃, and vacuum tightness is 750mm/Hg, then, slowly open duct valve, feed intake and carry out underpressure distillation, the distilled material is mixed methyl aliphatic ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112260A CN1151433A (en) | 1995-12-02 | 1995-12-02 | Method of synthesizing mixed methyl aliphatic ester using cotton seed oil soap bottoms as raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95112260A CN1151433A (en) | 1995-12-02 | 1995-12-02 | Method of synthesizing mixed methyl aliphatic ester using cotton seed oil soap bottoms as raw material |
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| Publication Number | Publication Date |
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| CN1151433A true CN1151433A (en) | 1997-06-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95112260A Pending CN1151433A (en) | 1995-12-02 | 1995-12-02 | Method of synthesizing mixed methyl aliphatic ester using cotton seed oil soap bottoms as raw material |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816642A (en) * | 2012-09-06 | 2012-12-12 | 如皋市双马化工有限公司 | Method for producing glycerin monostearate vegetable pitch |
| CN102965200A (en) * | 2012-11-29 | 2013-03-13 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel from nigre |
| CN103435468A (en) * | 2013-08-26 | 2013-12-11 | 苏勇 | Method for producing stearic acid by utilizing cottonseed oil soapstock |
| CN103509651A (en) * | 2012-06-27 | 2014-01-15 | 浙江海洋学院 | Method for extracting ethyl ester enriched fish oil from fish oil refining byproduct |
| CN104818125A (en) * | 2015-05-04 | 2015-08-05 | 浙江大学 | Method for using waste oil and grease as raw material to prepare fatty acid methyl ester |
| CN104862018A (en) * | 2015-04-13 | 2015-08-26 | 内乡县龙翔生物科技有限公司 | Production process of antioxidant biodiesel |
| CN111149796A (en) * | 2019-12-31 | 2020-05-15 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
-
1995
- 1995-12-02 CN CN95112260A patent/CN1151433A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103509651A (en) * | 2012-06-27 | 2014-01-15 | 浙江海洋学院 | Method for extracting ethyl ester enriched fish oil from fish oil refining byproduct |
| CN103509651B (en) * | 2012-06-27 | 2015-01-07 | 浙江海洋学院 | Method for extracting ethyl ester enriched fish oil from fish oil refining byproduct |
| CN102816642A (en) * | 2012-09-06 | 2012-12-12 | 如皋市双马化工有限公司 | Method for producing glycerin monostearate vegetable pitch |
| CN102816642B (en) * | 2012-09-06 | 2013-07-10 | 如皋市双马化工有限公司 | Method for producing glycerin monostearate vegetable pitch |
| CN102965200A (en) * | 2012-11-29 | 2013-03-13 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel from nigre |
| CN102965200B (en) * | 2012-11-29 | 2014-08-13 | 青岛福瑞斯生物能源科技开发有限公司 | Method for preparing biodiesel from nigre |
| CN103435468A (en) * | 2013-08-26 | 2013-12-11 | 苏勇 | Method for producing stearic acid by utilizing cottonseed oil soapstock |
| CN104862018A (en) * | 2015-04-13 | 2015-08-26 | 内乡县龙翔生物科技有限公司 | Production process of antioxidant biodiesel |
| CN104818125A (en) * | 2015-05-04 | 2015-08-05 | 浙江大学 | Method for using waste oil and grease as raw material to prepare fatty acid methyl ester |
| CN111149796A (en) * | 2019-12-31 | 2020-05-15 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
| CN111149796B (en) * | 2019-12-31 | 2021-10-22 | 苏州丰倍生物科技有限公司 | Pesticide solvent and preparation method and application thereof |
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