CN104086420B - Produce the method for high-quality pentaerythrite high-carbon fatty acid ester with extraction process - Google Patents
Produce the method for high-quality pentaerythrite high-carbon fatty acid ester with extraction process Download PDFInfo
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- CN104086420B CN104086420B CN201410307114.0A CN201410307114A CN104086420B CN 104086420 B CN104086420 B CN 104086420B CN 201410307114 A CN201410307114 A CN 201410307114A CN 104086420 B CN104086420 B CN 104086420B
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- pentaerythrite
- fatty acid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/003—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fatty acids with alcohols
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
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Abstract
The invention discloses a kind of method of producing high-quality pentaerythrite high-carbon fatty acid ester with extraction process, comprise select materials, esterification, filtration, extraction, precipitation step, the link of selecting materials is to select higher aliphatic acid, pentaerythrite and zinc powder; In the time of esterification, adopt zinc powder to make catalyst, not only easily from product isolated by filtration out, and zinc powder can also react with higher aliphatic acid and produce Microamounts of Hydrogen ion, can produce strong decolorization, and product colour can not be deepened, totally comfortable; Filtering out after zinc powder, at the methyl alcohol of 5-15%, the thick ester of pentaerythrite high-carbon fatty acid ester after filtering is fully uniformly mixed with volumetric(al) moisture content, higher aliphatic acid is dissolved in methyl alcohol, and pentaerythrite high-carbon fatty acid ester can not be dissolved in methyl alcohol, after quiescent setting, methanol solution floats on upper strata because of light specific gravity, and pentaerythrite high-carbon fatty acid ester is than great and fall to lower floor, remove methanol solution, obtain high-quality pentaerythrite high-carbon fatty acid ester.
Description
Technical field
The present invention relates to one is that raw material is produced pentaerythrite high-carbon through esterification with higher aliphatic acid and pentaerythriteThe method of fatty acid ester, especially relates to a kind of new process with extraction process purification pentaerythrite high-carbon fatty acid ester.
Background technology
With the ester that higher aliphatic acid (aliphatic acid of carbochain >=18) and pentaerythrite esterification generate be engine lubricating oil, goldBelong to the important additives such as high temperature process oil, flame resistance hydraulic oil, preparation medium, also can be used as the base oil of high temperature heat conductive oil. ItsFeature is that low (<-60 DEG C of > low temperature flows are good, and high-flash (>=340 DEG C) heat resistance is splendid for congealing point. Its reaction equation is:
But pentaerythrite has four hydroxyls, after esterification, in product, contain one, two, three, four high-carbon fatty acid ester,And the flash-point of one, two, three esters is on the low side, only have pentaerythrite four high-carbon fatty acid esters just to there is flash-point high, low temperature flow is goodFine quality. In order to obtain four esters, must in the time of esterification, increase the consumption of higher aliphatic acid, with being greater than theoretical value10%, esterification is moved to the direction that generates four fat. But product medium high carbon content of fatty acid is higher, if do not removed, produceProduct have corrosion to metallic article, and therefore the residual quantity of product medium high carbon aliphatic acid must be controlled in 0.5%.
To from carboxylate, remove free higher aliphatic acid, can not use alkali refining method, the fat because this product viscosity is large, after alkali refiningFat acid soda soap and ester layering difficulty, cannot carry out production operation. Remove higher aliphatic acid with distillating method, because of vapo(u)rizing temperature largeIn 250 DEG C, can cause product cracking, produce peculiar smell.
Summary of the invention
The present invention is directed to the technical problem existing in above-mentioned prior art, provide a kind of with the extraction process Ji Wusi that purifiesThe new process of alcohol high-carbon fatty acid ester, the method is to utilize moisture methyl alcohol to higher aliphatic acid and pentaerythrite high-carbon fatThe characteristic of the different solubilities of fat acid esters, separates whole operation to higher aliphatic acid, pentaerythrite high-carbon fatty acid esterJourney is easy to carry out, and cracking can not occur product, produces peculiar smell, thereby has improved product quality.
Technical scheme of the present invention is achieved in that
The method of producing high-quality pentaerythrite high-carbon fatty acid ester with extraction process, step is as follows:
1., select materials: select acid value 190-200, the higher aliphatic acid of iodine value 80-100, purity >=98% season
Penta tetrol, 200 order zinc powders of purity >=99.5%; The weight portion proportioning of above-mentioned each raw material consists of:
80～120 parts of higher aliphatic acids
9～15 parts of pentaerythrites
0.4～0.7 part of zinc powder;
2., esterification: process conditions: esterification reaction temperature is controlled at 180-230 DEG C,
Vacuum: 100～1000pa, reaction time 4-8 hour;
Under vacuum state, outside the water vapor extraction still that esterification generates, when esterification reaction temperature is raised to 210 DEG C, vacuumDegree≤500pa, while extraction out without steam, esterification finishes;
3., filter: leach while hot zinc powder, filtration temperature is at 180-200 DEG C, cooling stand-by;
4., extraction: the thick ester after filtration adds the methyl alcohol that the water content of 20～40 weight portions is 5-15%, at rotating speed isUnder the speed of 110～130 revs/min, stir 25～40 minutes, then stratification, isolates methanol solution, and Methanol Recovery repeatsUse; Thick ester adds methyl alcohol again, repeats aforesaid operations, until content < 0.5% of thick ester medium high carbon aliphatic acid;
5., precipitation: the thick ester after extraction is warming up to 100 DEG C, vacuumizes, in the time of vacuum residual voltage≤2000pa, be warming up to120 DEG C, in the time overflowing without methanol gas, stop heating, be cooled to normal temperature and obtain finished product.
As preferably, step 1. in, the weight portion proportioning of each raw material consists of:
100～120 parts of higher aliphatic acids
11～13 parts of pentaerythrites
0.4～0.6 part of zinc powder.
Adopt the invention has the beneficial effects as follows of technique scheme:
First the present invention adopts zinc powder to make catalyst in the time of esterification, urges with acidity such as adopting phosphoric acid, p-methyl benzenesulfonic acidAgent is compared, not only easily from product isolated by filtration out, and zinc powder can also react with higher aliphatic acid produce traceHydrogen ion, can produce strong decolorization, and product colour can not be deepened, totally comfortable; Moreover zinc powder does not have corruption to equipmentErosion property, therefore reaction kettle of the esterification can be used common stainless steel manufacture, and equipment investment is little; Without acid as catalyst, produce without spent acid, waste waterRaw.
Filtering out after zinc powder, with volumetric(al) moisture content at the methyl alcohol of 5-15% to the pentaerythrite higher aliphatic acid after filteringThe thick ester of ester is fully uniformly mixed, and why adopts aqueous methanol, is in order to prevent that a small amount of carboxylate from dissolving wherein, adoptedAqueous methanol is dissolved in methyl alcohol higher aliphatic acid, and pentaerythrite high-carbon fatty acid ester can not be dissolved in methyl alcohol, staticAfter precipitation, methanol solution floats on upper strata because of light specific gravity, and pentaerythrite high-carbon fatty acid ester, than great and fall to lower floor, is removed firstAlcoholic solution, carries out several repeatedly; Until higher aliphatic acid content ﹤ 0.5%, Methanol Recovery recycling; Whole operating process is easyIn carrying out, do not produce waste water, waste gas, and be to operate at normal temperatures, do not need heat energy, solve higher the asking of acid content in productTopic, product is to metallic article non-corrosiveness, and simultaneously because four ester contents are high, product flash-point is just high, and therefore heat resistance is better; ProductCan there is not cracking, produce peculiar smell, thereby improved product quality; And it is low to extract energy consumption under normal temperature, after Methanol Recovery, circulation makesWith, extract higher aliphatic acid re-uses, without three wastes.
Detailed description of the invention
The specific embodiment of the present invention is as follows:
Embodiment 1: produce the method for high-quality pentaerythrite high-carbon fatty acid ester with extraction process, step is as follows:
1., select materials: select acid value 190-200, the higher aliphatic acid of iodine value 80-100, purity >=98% pentaerythrite is pure200 order zinc powders of degree >=99.5%; The proportioning of above-mentioned each raw material consists of:
Higher aliphatic acid double centner
12 kilograms of pentaerythrites
0.5 kilogram of zinc powder;
2. esterification: process conditions: esterification reaction temperature is controlled at 180-200 DEG C,
Vacuum :≤1000pa, 6 hours reaction time;
Under vacuum state, outside the water vapor extraction still that esterification generates, when esterification reaction temperature is raised to 210 DEG C, vacuumDegree≤500pa, while extraction out without steam, esterification finishes;
3. filter: leach while hot zinc powder, filtration temperature is at 180-200 DEG C, cooling stand-by;
4. extraction: the thick ester after filtration adds the methyl alcohol that the volumetric(al) moisture content of 30 kilograms is 12%, is 120 at rotating speedRev/min speed under stir 30 minutes, then stratification, isolates methanol solution, Methanol Recovery is reused; Thick ester adds againEnter methyl alcohol, repeat aforesaid operations, until content < 0.5% of thick ester medium high carbon aliphatic acid;
5. precipitation: adopt the way of distillation, the thick ester after extraction is warming up to 100 DEG C, vacuumize, as vacuum residual voltage≤2000paTime, be warming up to 120 DEG C, in the time overflowing without methanol gas, stop heating, be cooled to normal temperature and obtain finished product.
Embodiment 2: produce the method for high-quality pentaerythrite high-carbon fatty acid ester with extraction process, step is as follows:
1., select materials: select acid value 190-200, the higher aliphatic acid of iodine value 80-100, purity >=98% pentaerythrite is pure200 order zinc powders of degree >=99.5%; The proportioning of above-mentioned each raw material consists of:
110 kilograms of higher aliphatic acids
12 kilograms of pentaerythrites
0.6 kilogram of zinc powder;
2., esterification: process conditions: esterification reaction temperature is controlled at 210 DEG C,
Vacuum :≤1000pa, 7 hours reaction time;
Under vacuum state, outside the water vapor extraction still that esterification generates, when esterification reaction temperature is raised to 210 DEG C, vacuumDegree≤500pa, while extraction out without steam, esterification finishes;
3., filter: leach while hot zinc powder, filtration temperature is at 180-200 DEG C, cooling stand-by;
4., extraction: the thick ester after filtration adds the methyl alcohol that the water content of 35 kilograms is 100%, at rotating speed be 120 turn/Under the speed of dividing, stir 40 minutes, then stratification, isolates methanol solution, and Methanol Recovery is reused; Thick ester adds againMethyl alcohol, repeats aforesaid operations, until content < 0.5% of thick ester medium high carbon aliphatic acid;
5., precipitation: the thick ester after extraction is warming up to 100 DEG C, vacuumizes, in the time of vacuum residual voltage≤2000pa, be warming up to120 DEG C, in the time overflowing without methanol gas, stop heating, be cooled to normal temperature and obtain finished product.
The pentaerythrite high-carbon fatty acid ester quality index of utilizing method of the present invention to make is as follows:
Outward appearance: light yellow transparent liquid
Represent the impact of lower each raw material consumption on esterification yield below by list:
Table 1: pentaerythrite, the impact of higher aliphatic acid weight ratio on esterification yield
Catalyst amount (alcohol, sour total amount meter) %:0.5, reaction temperature: 210 DEG C, the reaction time: 5 hours;
| Alcohol, sour weight ratio | 12：90 | 12：100 | 12：110 | 12：120 3 --> |
| Esterification yield % | 83.2％ | 90.5％ | 98.7％ | 98.8％ |
Table 2: the impact of catalyst amount on esterification yield
At alcohol, sour weight ratio: 12:110, reaction temperature: 210 DEG C, the reaction time: under the condition of 5 hours:
Table 3: the impact of reaction temperature on esterification yield
Alcohol, sour weight ratio: 12:110; The catalyst amount %:0.5 reaction time: 5 hours
| Reaction temperature: DEG C | 180 | 190 | 200 | 210 | 220 | 230 |
| Esterification yield % | 82.3 | 90.6 | 95.8 | 98.8 | 98.7 | 97.5 |
Table 4: the impact of reaction time on esterification yield
Alcohol, sour weight ratio: 12:110 catalyst amount %:0.5 reaction temperature: 210 DEG C
Table 5: the impact (weight ratio) of methyl alcohol water content on effect of extracting
Claims (2)
1. produce the method for pentaerythrite high-carbon fatty acid ester with extraction process, it is characterized in that step is as follows:
1., select materials: select acid value 190-200, iodine value 80-100, the higher aliphatic acid of carbochain >=18, purity >=98% season penta 4Alcohol, 200 order zinc powders of purity >=99.5%; The weight portion proportioning of above-mentioned each raw material consists of:
80～120 parts of higher aliphatic acids
9～15 parts of pentaerythrites
0.4～0.7 part of zinc powder;
2. esterification: process conditions: esterification reaction temperature is controlled at 180-230 DEG C,
Vacuum: 100～1000pa, reaction time 4-8 hour;
Under vacuum state, outside the water vapor extraction still that esterification generates, when esterification reaction temperature is raised to 210 DEG C, vacuum≤500pa, while extraction out without steam, esterification finishes;
3. filter: leach while hot zinc powder, filtration temperature is at 180-200 DEG C, cooling stand-by;
4. extraction: the thick ester after filtration adds the methyl alcohol that the water content of 20～40 weight portions is 5-15%, be 110 at rotating speed～Under the speed of 130 revs/min, stir 25～40 minutes, then stratification, isolates methanol solution, and Methanol Recovery is reused;Thick ester adds methyl alcohol again, repeats aforesaid operations, until content < 0.5% of thick ester medium high carbon aliphatic acid;
5. precipitation: the thick ester after extraction is warming up to 100 DEG C, vacuumizes, in the time of vacuum residual voltage≤2000pa, be warming up to 120 DEG C,In the time overflowing without methanol gas, stop heating, be cooled to normal temperature and obtain finished product.
2. the method for producing pentaerythrite high-carbon fatty acid ester with extraction process according to claim 1, is characterized in that:Step 1. in, the weight portion proportioning of each raw material consists of:
100～120 parts of higher aliphatic acids
11～13 parts of pentaerythrites
0.4～0.6 part of zinc powder.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410307114.0A CN104086420B (en) | 2014-06-30 | 2014-06-30 | Produce the method for high-quality pentaerythrite high-carbon fatty acid ester with extraction process |
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| CN201410307114.0A CN104086420B (en) | 2014-06-30 | 2014-06-30 | Produce the method for high-quality pentaerythrite high-carbon fatty acid ester with extraction process |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373119A (en) * | 2002-02-07 | 2002-10-09 | 华北工学院 | Process for synthesis of pentaerythritol tetraheptanoate by catalysis of phosphotungstic acid |
| JP2004217775A (en) * | 2003-01-14 | 2004-08-05 | Showa Denko Kk | Macromolecular compound having high-degree branched structure and monomer compound |
| CN101050399A (en) * | 2007-05-21 | 2007-10-10 | 武汉工业学院 | Parallel methyl ester method for fats and oils in high acid value |
| CN101245006A (en) * | 2008-03-14 | 2008-08-20 | 江南大学 | Process for producing pentaerythritol oleate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373119A (en) * | 2002-02-07 | 2002-10-09 | 华北工学院 | Process for synthesis of pentaerythritol tetraheptanoate by catalysis of phosphotungstic acid |
| JP2004217775A (en) * | 2003-01-14 | 2004-08-05 | Showa Denko Kk | Macromolecular compound having high-degree branched structure and monomer compound |
| CN101050399A (en) * | 2007-05-21 | 2007-10-10 | 武汉工业学院 | Parallel methyl ester method for fats and oils in high acid value |
| CN101245006A (en) * | 2008-03-14 | 2008-08-20 | 江南大学 | Process for producing pentaerythritol oleate |
Non-Patent Citations (2)
| Title |
|---|
| 季戊四醇酯合成工艺研究进展;马楷等;《合成润滑材料》;20140620;第41卷(第2期);第34-40页 * |
| 油酸季戊四醇酯的合成;陈小刚等;《化学与生物工程》;20060625(第09期);第16-17页 * |
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