CN100999695A - Processing method of high acid value greasy - Google Patents
Processing method of high acid value greasy Download PDFInfo
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- CN100999695A CN100999695A CN 200610132349 CN200610132349A CN100999695A CN 100999695 A CN100999695 A CN 100999695A CN 200610132349 CN200610132349 CN 200610132349 CN 200610132349 A CN200610132349 A CN 200610132349A CN 100999695 A CN100999695 A CN 100999695A
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Abstract
The present invention relates to high acid number oil processing method. Enzyme or acid chemical catalyst is added into the mixture of high acid number oil and lower alcohol, and through selective esterification reaction, the oil has the free fatty acid content lowered to below 1-5 wt%. Most of the residual free fatty acid is converted into soap for separating out to obtain soap-eliminating oil; and the soap-eliminating oil is further processed through drying, decolorizing and deodorizing to form refined oil. The present invention raises the product oil quality and value, and has high application value to refining bran oil, corn oil, cotton seed oil and other high acid number oil.
Description
Technical field
The present invention relates to a kind of working method, particularly a kind of working method of high-acid value grease.
Background technology
Chemical refining is a kind of oil and fat refining method of widespread use, it has the advantage that versatility is good, product quality is high, but for the refining of high acid value oil, produce a large amount of soap stocks with technology in traditional chemical refining, cause a large amount of losses and the severe environmental protection pressure of neutral oil.For solving the big shortcoming of chemical refining loss, people generally adopt physical refining processing highly acidic valency grease, have improved refining yield, have alleviated environmental protection pressure greatly.In the physical refining, generally do not produce soap stock, lacked the absorption of soap stock to impurity such as phosphatide, the quality of refining oil descends greatly.In physical refining, need to rely on the free fatty acids in the high temperature removal grease, mainly have following shortcoming: 1) deodorization time is long, causes that color with oil color is dark, the trans acids increase, often can't produce high-quality edible oil; 2) energy consumption height; 3) lipid acid at high temperature has certain corrodibility to equipment, equipment material is required high.
Summary of the invention
The objective of the invention is to above-mentioned shortcoming, a kind of working method of high-acid value grease is provided,, promote the quality of refining oil to improve the reliability that promotes grease processing technique at the prior art existence.
The working method of high-acid value grease of the present invention comprises the following steps:
(1) high-acid value grease and lower alcohol mixture are through lipase or esterase catalyzed reaction, and temperature of reaction is 30～80 ℃, react to the grease free fatty acid content and count 1～5% by its weight;
Described high-acid value grease is meant in the grease that free fatty acid content is greater than 8% grease; The mol ratio of free lipid acid and lower alcohol is 1: 1.5～20 in the reaction system;
(2) add the free fatty acids in the gained reactant in the alkali neutralization procedure (1), temperature of reaction is 50～90 ℃, makes that the free fatty acids in the grease generates soap 50% or more, and the total amount of generation soap is not less than 0.8% of grease weight, and the separation soap, must take off soap oil;
(3) step (2) gained is taken off soap oil drying, decolouring, distillation deodorization procedures, get refining oil.
The mixture of one or more in described high-acid value grease preferably rice oil, Semen Maydis oil, Oleum Gossypii semen, plam oil, algae oil, the fungal oil.
Described lower alcohol is one or more the mixture in methyl alcohol, ethanol, the Virahol.
In the step (1), the mol ratio of free lipid acid and lower alcohol is 1: 3～10 in the described reaction system.
React to the grease free fatty acid content in the step (1) and count 1～3% by its weight.
In the step (1), reaction with one or more the mixture in sulfuric acid, sulfonic acid class, phosphoric acid, the storng-acid cation exchange resin as catalyzer.
In the step (1), reaction with one or more the mixture in hydrochloric acid, heteropolyacid, the solid acid super acids as catalyzer.
In the step (2), make that the free fatty acids in the grease generates soap more than 90%.
Usually, free fatty acid content in the crude oil is 0.5～3%, as common soybean oil, rapeseed oil, peanut wet goods, be no more than this acid value scope, but, have also that to comprise the processing of highly active lipase or grease in some oil plants improper, often run into high acid value grease, than being easier to take place the problem that acid value rises, high acid value grease described in the present invention is meant that free lipid acid in the grease is greater than 8% grease as greases such as Rice pollard oil, Semen Maydis oil, Oleum Gossypii semen, plam oil, algae oil, fungal oils.
The existence of free fatty acids is the main difficult point of high acid value oil processing, how to reduce acid value and lipid acid is changed into glyceryl ester or other that to be easy to isolating ester be the basic ideas of dealing with problems.Lipid acid and glycerine are carried out esterification, and to generate glyceryl ester be one of thinking, adopt chemical catalyst to carry out esterification, the discovery esterification need at high temperature be carried out, the processed oil color is produced detrimentally affect, and there is the catalyzer safety issue, can not solves the processing problems of high acid value oil well.
Another thinking that reduces free fatty acids is the low-carbon-ester that just lipid acid is converted into lipid acid, and lower alcohol of the present invention comprises methyl alcohol, ethanol and Virahol.The inventor discovers that further high-acid value grease and lower alcohol are under the effect of special catalyst, and lower alcohol reacts the free fatty acids in preferential and the system, generates corresponding fatty acid ester.The contriver finds that through exploitative experiment when the content of free fatty acids was higher than 5%, the esterification high-priority betided between lower alcohol and lipid acid, and significantly reaction takes place for the lower alcohol and the glyceryl ester of getting along well; When free fatty acids was lower than 3%, the speed of response of lower alcohol between glyceryl ester just obviously improved; When free fatty acids was lower than 1%, a large amount of glyceryl ester and lower alcohol reacted.
Step (1), (2) are the most crucial technology of the present invention, promptly at first by selective esterification reaction, make that the free fatty acids in the grease is reduced to 1～5%, then remaining free fatty acids are converted into soap more than 50%.The technology of the present invention has realized following characteristic, at first, has reduced the acid value in the grease, helps following process; Secondly, keep the generation of soap,, guaranteed oil quality by taking off the impurity in the soap operation removal grease; Once more, lipid acid is converted into its low-carbon-ester, can promotes by-product value.
The material that can serve as catalyst for esterification reaction of the present invention comprises biological catalyst or chemical catalyst.Biological catalyst is mainly lipase or esterase, and this type of catalyzer biggest advantage is natural safety, but general cost is than the chemical catalyst height; Chemical catalyst is preferably chemical an acidic catalyst, nearly all acid with certain intensity all has catalytic effect, in an acidic catalyst, have most practical value with sulfuric acid, phosphoric acid, sulfonic acid class, Zeo-karb, the mixture of one or more in the preferred above-mentioned substance of the present invention is as catalyzer.Still there is other acidic chemical catalyzer also can be used for the technology of the present invention and implements example hydrochloric acid, heteropolyacid, solid acid super acids etc.Esterification reaction temperature of the present invention is 30～80 ℃, is lower than this temperature range, and speed of response is affected, and is higher than this temperature range, can deepen color with oil color, and brings the problem of energy consumption and equipment aspect.
From economic considerations, should consider the recovery of catalyzer as far as possible, for with sulfuric acid, phosphoric acid, sulfonic acid class situation as catalyzer, the recovery of catalyzer is uneconomic, can no longer consider to reclaim, for the situation that adopts heterogeneous catalyst such as lipase, Zeo-karb and solid acid, should consider to reclaim.Because these catalyzer are solid phase, and reaction system is liquid, adopts filtering method to be easy to reclaim, and this operation is easy to be grasped and use by those skilled in the art, and concrete recovery method does not elaborate and limits.
Through esterification, still residual a part of free fatty acids in the grease, the present invention utilizes this partial fatty acid and alkali generation neutralization reaction to generate soap.Neutralization reaction is one of traditional operation operation of oil and fat refining, and neutral temperature generally adopts 50～90 ℃, and the neutralization operation process may relate to the evaporation of lower alcohol, for the lower alcohol that evaporates, should carry out condensation and reclaim.The vital role that generates soap is the impurity of assisting to remove in the grease, as phosphatide, pigment and metal ion etc.The present invention finds to have the free fatty acids more than 50% to generate the reliability that soap just can ensure subsequent technique at least, preferably, makes 90% above free fatty acids generate soap, more preferably, makes whole free fatty acidies generate soap.Another benefit that most of free fatty acids is transformed into soap is the acid value that can reduce in the byproduct lower alcohol fatty acid esters, helps promoting by-product value.
The separation of soap can be adopted the operation of intermittent type natural sedimentation among the present invention, also can adopt continuous-flow centrifugation to separate, and belongs to the unit operation of oil and fat refining routine.
When greasy processing is to be purpose to obtain refining oil, and technical characterictic of the present invention also comprises step (3), takes off the processing of soap oil through super-dry, decolouring, distillation deodorization procedures with what step (2) obtained, obtains refining oil.Greasy drying, decolouring, distillation deodorization procedures are the conventional arts in the grease processing.
The present invention compared with prior art has following advantage:
1) reduces distillation temperature, promoted oil quality;
2) value of lifting overhead product byproduct;
Technology of the present invention is particularly useful for the processing of Rice pollard oil, also has higher using value for Semen Maydis oil, Oleum Gossypii semen, plam oil, algae oil, the fungal oil of some high acid value.
Embodiment
Introduce enforcement of the present invention by the following examples in more detail.In described embodiment, unless specified otherwise, all per-cents all by weight.
Embodiment 1
5000g Rice pollard oil (contain free fatty acids 10.5%, the molecular-weight average of lipid acid is in 280) adds ethanol 125g, makes that lipid acid and alcoholic acid mol ratio are 1: 1.5, add the 5g vitriol oil again.In the 10L reactor, be heated to 75 ℃, back flow reaction 1h under stirring condition, stopped reaction, cooling back sampling and measuring acid number, this moment, the free fatty acid content of oil sample was 3.3%.It is that 15% NaOH solution neutralizes that reaction product adds concentration, and 75 ℃ of heat-retaining conditions slowly stir surveys that free lipid acid is 1.6% in the oil after the 15min neutralization reaction, and soap stock is removed in centrifugation, uses 10% the centrifugal washing of soft water again, obtains taking off soap oil.
Take off soap oil and be preheated to oily 3% the carclazyte that weighs of adding after 90 ℃, stir decolouring 20min after-filtration under the vacuum, bleached oil is again under 240 ℃, the condition of vacuum tightness 100～200Pa, feeding water vapor distills, be reduced to below 0.1% until free fatty acids, constantly isolate acid byproduct fatty low-carbon-ester overhead product, obtain refining oil 1, grease key index such as table 1.
Embodiment 2
5000g Rice pollard oil (contain free fatty acids 16.8%, the molecular-weight average of lipid acid is in 280) adds methyl alcohol and makes that the mol ratio of lipid acid and methyl alcohol is 1: 20, adds the 8g vitriol oil again.In the 10L reactor, be heated to 60 ℃, back flow reaction 1h under stirring condition, stopped reaction, cooling back sampling and measuring acid number, this moment, the free fatty acid content of oil sample was 1.5%.Reaction product adds 300g water, methyl alcohol is reclaimed in the evaporation that heats up, adding concentration again and be 15% NaOH solution neutralizes, 75 ℃ of heat-retaining conditions slowly stir surveys that free lipid acid is 0.2% in the oil after the 15min neutralization reaction, soap stock is removed in centrifugation, use 10% the centrifugal washing of soft water again, obtain taking off soap oil.Take off soap oil according to the operation of embodiment 1 method, obtain refining oil 2, grease key index such as table 1.
Embodiment 3
5000g Semen Maydis oil (contain free fatty acids 8.3%, the molecular-weight average of lipid acid is in 280) adds methyl alcohol and makes that the mol ratio of fatty acid and methyl alcohol is 1: 10, adds the 30g thionamic acid again.In the 10L reactor, be heated to 60 ℃, back flow reaction 3h under stirring condition, stopped reaction, cooling back sampling and measuring acid number, this moment, the free fatty acid content of oil sample was 2.6%.Reaction product heats up to evaporate and reclaims methyl alcohol, remove by filter solid-state thionamic acid, adding concentration again and be 15% NaOH solution neutralizes, 75 ℃ of heat-retaining conditions slowly stir surveys that free lipid acid is 0.5% in the oil after the 15min neutralization reaction, soap stock is removed in centrifugation, use 10% the centrifugal washing of soft water again, obtain taking off soap oil.Take off soap oil through 90 ℃ of vacuum-dryings, the back added 2% carclazyte decoloring reaction 20 minutes, entered deodorization procedures after filtration, and 240 ℃ of deodorization temperatures, fatty acid methyl ester and free fatty acids are removed in that deodorization procedures is separated, obtain refining oil 3, grease key index such as table 1.
Embodiment 4
5000g Rice pollard oil (contain free fatty acids 16.8%, the molecular-weight average of lipid acid is in 280) adds methyl alcohol and makes that the mol ratio of lipid acid and methyl alcohol is 1: 2, adds 40g immobilized lipase Lipozyme TL IM again.In the 10L reactor, keep 30 ℃ and under stirring condition, react 3h, stopped reaction, cooling back sampling and measuring acid number, this moment, the free fatty acid content of oil sample was 5.0%.Methyl alcohol was reclaimed in the intensification evaporation after reaction product reclaimed lipase after filtration, adding concentration again and be 15% NaOH solution neutralizes, 75 ℃ of heat-retaining conditions slowly stir surveys that free lipid acid is 2.1% in the oil after the 15min neutralization reaction, soap stock is removed in centrifugation, use 10% the centrifugal washing of soft water again, obtain taking off soap oil.Take off soap oil according to the operation of embodiment 1 method, obtain refining oil 4, grease key index such as table 1.
Embodiment 5
5000g Rice pollard oil (contain free fatty acids 18.3%, the molecular-weight average of lipid acid is in 280) adds Virahol and makes that the mol ratio of lipid acid and Virahol is 1: 3, and adding the 100g strongly acidic styrene again is I type Zeo-karb.In the 10L reactor, keep 30 ℃ and under stirring condition, react 5h, stopped reaction, cooling back sampling and measuring acid number, this moment, the free fatty acid content of oil sample was 2.9%.Methyl alcohol was reclaimed in the intensification evaporation after reaction product reclaimed resin after filtration, adding concentration again and be 15% NaOH solution neutralizes, 80 ℃ of heat-retaining conditions slowly stir surveys that free lipid acid is 0.3% in the oil after the 15min neutralization reaction, soap stock is removed in centrifugation, use 10% the centrifugal washing of soft water again, obtain taking off soap oil.Take off soap oil by the operation of embodiment 1 method, obtain refining oil 5, grease key index such as table 1.
Embodiment 6
5000g Rice pollard oil (contain free fatty acids 16.8%, the molecular-weight average of lipid acid is in 280) adds methyl alcohol and makes that the mol ratio of lipid acid and methyl alcohol is 1: 8, adds 10g concentration again and be 80% phosphoric acid.In the 10L reactor, be heated to 60 ℃, back flow reaction 2h under stirring condition, stopped reaction, cooling back sampling and measuring acid number, this moment, the free fatty acid content of oil sample was 3.5%.Reaction product adds 100g water, methyl alcohol is reclaimed in the evaporation that heats up, adding concentration again and be 15% NaOH solution neutralizes, 75 ℃ of heat-retaining conditions slowly stir surveys that free lipid acid is 0.2% in the oil after the 15min neutralization reaction, soap stock is removed in centrifugation, use 10% the centrifugal washing of soft water again, obtain taking off soap oil.Take off soap oil according to the operation of embodiment 1 method, obtain refining oil 6, grease key index such as table 1.
The comparative example
The 5000g Rice pollard oil is according to traditional physical refining method operation (containing free fatty acids 10.5%), concrete steps are as follows, the rice bran crude oil is heated to 80 ℃, added 0.3% (about 15g) concentration and be 80% phosphatase reaction 30 minutes, add 5% water centrifugation again, through super-dry, decolouring and deodorization operation, obtain refining oil 7, grease key index such as table 1 then.
Table 1
| Refining oil | Color and luster | Trans acids (%) |
| Refining oil 1 | Yellow 25 red 3.1 (133.4mm groove mensuration) | 2.1 |
| Refining oil 2 | Yellow 35 red 4.8 (133.4mm groove mensuration) | 1.6 |
| Refining oil 3 | Yellow 25 red 3.1 (133.4mm groove mensuration) | 2.0 |
| Refining oil 4 | Yellow 30 red 3.3 (133.4mm groove mensuration) | 2.8 |
| Refining oil 5 | Yellow 35 red 3.2 (133.4mm groove mensuration) | 1.9 |
| Refining oil 6 | Yellow 30 red 3.3 (133.4mm groove mensuration) | 1.8 |
| Refining oil 7 | 133.4mm groove can not be surveyed yellow 30 red 4.3 (25.4mm groove mensuration) | 5.2 |
By table 1 result as seen, adopt the inventive method can significantly reduce greasy color and trans acids, help to improve oil quality.
Claims (8)
1, a kind of working method of high-acid value grease is characterized in that comprising the following steps:
(1) high-acid value grease and lower alcohol mixture are through lipase or esterase catalyzed reaction, and temperature of reaction is 30～80 ℃, react to the grease free fatty acid content and count 1～5% by its weight;
Described high-acid value grease is meant in the grease that free fatty acid content is greater than 8% grease; The mol ratio of free lipid acid and lower alcohol is 1: 1.5～20 in the reaction system;
(2) add the free fatty acids in the gained reactant in the alkali neutralization procedure (1), temperature of reaction is 50～90 ℃, makes that the free fatty acids in the grease generates soap 50% or more, and the total amount of generation soap is not less than 0.8% of grease weight, and the separation soap, must take off soap oil;
(3) step (2) gained is taken off soap oil drying, decolouring, distillation deodorization procedures, get refining oil.
2, working method according to claim 1 is characterized in that described high-acid value grease is one or more the mixture in Rice pollard oil, Semen Maydis oil, Oleum Gossypii semen, plam oil, algae oil, the fungal oil.
3, working method according to claim 1 is characterized in that described lower alcohol is one or more the mixture in methyl alcohol, ethanol, the Virahol.
4,, it is characterized in that in the step (1) that the mol ratio of free lipid acid and lower alcohol is 1: 3～10 in the described reaction system according to each described working method of claim 1 to 3.
5,, it is characterized in that reacting in the step (1) to the grease free fatty acid content and count 1～3% by its weight according to each described working method of claim 1 to 3.
6, according to each described working method of claim 1 to 3, it is characterized in that in the step (1), reaction with one or more the mixture in sulfuric acid, sulfonic acid class, phosphoric acid, the storng-acid cation exchange resin as catalyzer.
7, according to each described working method of claim 1 to 3, it is characterized in that in the step (1), reaction with one or more the mixture in hydrochloric acid, heteropolyacid, the solid acid super acids as catalyzer.
8, according to each described working method of claim 1 to 3, it is characterized in that in the step (2), make that the free fatty acids in the grease generates soap more than 90%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418253B (en) * | 2008-12-02 | 2010-06-02 | 太仓市宝马油脂设备有限公司 | Grease distillation tower |
| CN101974575A (en) * | 2010-10-28 | 2011-02-16 | 江南大学 | Preparation method of rice bran oil rich in diacylglycerol |
| CN102268464A (en) * | 2010-06-02 | 2011-12-07 | 河南工业大学 | Method for producing diglyceride with rice bran oil of high acid value |
| CN102584585A (en) * | 2012-01-11 | 2012-07-18 | 河北欣奇典生物科技有限公司 | Method for deacidifying alpha-ethylli-nolenate solvent |
| CN103436360A (en) * | 2009-09-07 | 2013-12-11 | 日清奥利友集团株式会社 | Method for producing glyceride compositions |
| CN112662645A (en) * | 2021-01-19 | 2021-04-16 | 华南理工大学 | Sphingomyelinase D mutant and application thereof |
| CN116445223A (en) * | 2023-04-19 | 2023-07-18 | 脂代生物科技(杭州)有限公司 | Preparation method of propoxyl glycerin fatty acid ester |
-
2006
- 2006-12-27 CN CN 200610132349 patent/CN100999695A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418253B (en) * | 2008-12-02 | 2010-06-02 | 太仓市宝马油脂设备有限公司 | Grease distillation tower |
| CN103436360A (en) * | 2009-09-07 | 2013-12-11 | 日清奥利友集团株式会社 | Method for producing glyceride compositions |
| CN103436360B (en) * | 2009-09-07 | 2015-04-22 | 日清奥利友集团株式会社 | Method for producing glyceride compositions |
| CN102268464A (en) * | 2010-06-02 | 2011-12-07 | 河南工业大学 | Method for producing diglyceride with rice bran oil of high acid value |
| CN102268464B (en) * | 2010-06-02 | 2013-05-01 | 河南工业大学 | Method for producing diglyceride with rice bran oil of high acid value |
| CN101974575A (en) * | 2010-10-28 | 2011-02-16 | 江南大学 | Preparation method of rice bran oil rich in diacylglycerol |
| CN101974575B (en) * | 2010-10-28 | 2012-06-27 | 江南大学 | Preparation method of rice bran oil rich in diacylglycerol |
| CN102584585A (en) * | 2012-01-11 | 2012-07-18 | 河北欣奇典生物科技有限公司 | Method for deacidifying alpha-ethylli-nolenate solvent |
| CN112662645A (en) * | 2021-01-19 | 2021-04-16 | 华南理工大学 | Sphingomyelinase D mutant and application thereof |
| CN112662645B (en) * | 2021-01-19 | 2022-04-22 | 华南理工大学 | Sphingomyelinase D mutant and application thereof |
| CN116445223A (en) * | 2023-04-19 | 2023-07-18 | 脂代生物科技(杭州)有限公司 | Preparation method of propoxyl glycerin fatty acid ester |
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