CN102827699A - Method for hydrolyzing soap stock to extract fatty acid by adopting sub-critical acetic acid way - Google Patents
Method for hydrolyzing soap stock to extract fatty acid by adopting sub-critical acetic acid way Download PDFInfo
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- CN102827699A CN102827699A CN2012103402939A CN201210340293A CN102827699A CN 102827699 A CN102827699 A CN 102827699A CN 2012103402939 A CN2012103402939 A CN 2012103402939A CN 201210340293 A CN201210340293 A CN 201210340293A CN 102827699 A CN102827699 A CN 102827699A
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Abstract
The invention discloses a method for hydrolyzing soap stock to extract fatty acid by adopting a sub-critical acetic acid way, belongs to the field of byproduct processing during the alkali refining of animal and vegetable oil and fat, and aims to provide a method for performing hydrolysis to produce the fatty acid under a sub-critical condition by using the soap stock produced in a soybean oil refining process as a raw material. The method specifically comprises the following steps of: mixing the soap stock and an acetate solution, transferring a mixed solution into a high-pressure magnetic stirred autoclave, introducing nitrogen, and performing sub-critical hydrolysis under the conditions of certain temperature, feed-liquid ratio, reaction pressure and reaction time, wherein hydrolysis temperature is 180 to 280 DEG C, the feed-liquid ratio is 0.2:1 to 2:1, the hydrolysis time is 5 to 30min, and the hydrolysis pressure is 5 to 20MP. According to the method for hydrolyzing the soap stock to extract the fatty acid by adopting the sub-critical acetic acid way, the acidizing process of the conventional method is eliminated, a reaction process is simplified, and the hydrolysis time is shortened; and the addition of any chemical reagent in a hydrolysis process is avoided, so that the problems of recovery and residues of solvent are not required to be considered.
Description
Technical field
Sub product manufacture field when the invention belongs to the alkali refining animal-plant oil is specifically related to a kind of technology that adopts the subcritical hydrolysis Chinese honey locust to extract lipid acid, the selection of especially subcritical acetic acid and hydrolysising condition.
Background technology
Sub product when soap stock is the alkali refining animal-plant oil, press its quantity and content: it is most worthy in the oil and fat refining sub product.The all fatty acids that in soap stock, contains raw oil material, and exist with the form of soap.The lipid acid of various grease soap stocks is formed same basically oil fatty acid.Lipid acid is the important chemical basic material, is widely used in the industry such as rubber, plastics, weaving, washing, papermaking medicine and food.Total fatty acid content reaches 40%～45% in the cheap VT 18 soap stock, is the desirable feedstock of producing lipid acid, thus from the VT 18 soap stock separation and Extraction lipid acid, become the focus in the lipid acid manufacture gradually.
Defectives such as separation and Extraction lipid acid generally adopts acidification hydrolization technology in the VT 18 soap stock, and the traditional method percent hydrolysis is low longer with hydrolysis time, and operating process is loaded down with trivial details, and extraction yield is low make its range of application receive certain limitation.
Summary of the invention
The purpose of this invention is to provide a kind of is raw material with the soap stock that produces in the VT 18 refining process; Under undercritical conditions, be hydrolyzed and produce the method for lipid acid; Extract lipid acid technology through the subcritical hydrolysis soap stock, exempted the process of traditional method acidification, simplified reaction process and shortened hydrolysis time; Hydrolytic process is not added any chemical reagent, need not consider the recovery and the residue problem of solvent.
The objective of the invention is to realize through following technical scheme:
Soap stock mixes with 1 ~ 5% acetum; Transfer in the high-pressure magnetic stirred autoclave, pour nitrogen, under certain temperature, solid-liquid ratio, reaction pressure and reaction times condition, carry out subcritical hydrolysis; Wherein: hydrolysis temperature is 180 ~ 280 ℃; Solid-liquid ratio is 0.2:1 ~ 2:1, and hydrolysis time is 5 ~ 30min, and hydrolysis pressure is 5 ~ 20MP.
[H] in the subcritical acetum near strong acid, so self have acid catalysis and function, can make some acid-base catalyzed reaction needn't add acid base catalysator; Subcritical water has enough little specific inductivity, simultaneously dissolved organic matter and inorganics.In addition, subcritical water also has advantages such as excellent mass transferring performance and environmental protection, has therefore obtained than extensive studies in fields such as organic synthesis, waste renewable resources.
Principle and technology that subcritical method of acetic acid hydrolysis soap stock of the present invention extracts lipid acid are following:
Soap stock chemical equation of hydrolysis in subcritical water is as follows, and under undercritical conditions, not only the water self-ionization goes out hydrogen ion, and subcritical state promoted the ionization of acetic acid, produces more hydrogen ion, participates in hydrolysis reaction.And the sodium hydroxide that reaction generates can be generated salt by the neutralization of the acetic acid of reactant, make reaction more fully forward carry out.R mainly is meant the alkyl chain of C11 ~ C17 in the reaction equation.In the high-pressure magnetic stirred autoclave, react, reaction system is heated control reaction temperature, the water-bath cooling through tin bath.After cooling finished, adding doubled the long-pending zero(ppm) water of gained liquid, in Rotary Evaporators, steamed and took off acetic acid and unnecessary water, confirmed percent hydrolysis through the acid number of measuring product at last.The equation that relates in the reaction is following:
Key of the present invention is confirming of subcritical acetum hydrolysising condition; Comprise temperature of reaction, solid-liquid ratio, reaction times, reaction pressure; Fig. 1-4 is seen in its influence to the subcritical hydrolysis rate, has finally confirmed The optimum reaction conditions through condition optimizing, and final percent hydrolysis can reach about 95 ~ 97%.Pass through H
2The character of O under subcritical state, H
2The intermolecular hydrogen bond of O destroys, and makes the H nucleus exposed outside, in addition under undercritical conditions weak acid acetic acid to ionization more fully, through therefore, [H] concentration in the solution got significantly to be increased, and has strengthened the acidity of solution.Therefore the effect that has similar proton has high energy, attacks soap stock staple sodium soap, destroys original chemical bond, generates lipid acid, and owing to the polarity of subcritical water a little less than, make lipid acid be dissolved in wherein.
The present invention adopts subcritical acetic acid in the time of extracting homo(io)thermism, almost not have energy consumption; Its action effect is rapid and energy expenditure is less, need not catalyzer, also need not add strong acid and carry out acidifying; Also can not introduce other impurity, for follow-up separation, purifying bring convenience.As a kind of novel extractive technique, it has short, advantages such as efficient is high, excellent mass transferring performance and environmental protection of extraction time, and the industrialization production of extracting lipid acid for the above characteristic hydrolysis soap stock that utilizes subcritical water provides the theory and practice guidance.
Description of drawings
Fig. 1 is the influence of temperature of reaction to the subcritical hydrolysis rate;
Fig. 2 is the influence of reaction pressure to the subcritical hydrolysis rate;
Fig. 3 is the influence of reaction times to the subcritical hydrolysis rate;
Fig. 4 is the influence of solid-liquid ratio to the subcritical hydrolysis rate.
Embodiment
Embodiment one: this embodiment adopts subcritical acetolysis Chinese honey locust to extract lipid acid according to following steps: soybean degummed oil → excess base saponification → spinning → soap stock → warm water washing → subcritical hydrolysis → cooling → rotary evaporation → adipic acid solution, and specific requirement is following:
Step 1: accurately take by weighing the 10g soap stock of super-dry pulverization process, transfer in the high-pressure magnetic stirred autoclave, under certain temperature, solid-liquid ratio and reaction times condition, pour nitrogen, carry out subcritical hydrolysis, measure percent hydrolysis;
Step 2: selecting the temperature of tin pot in the hydrolytic process is 180 ~ 280 ℃, and the same step 1 of process is confirmed the temperature of subcritical hydrolysis;
Step 3: select that solid-liquid ratio (g/ml) is 0.2:1 ~ 2:1 in the subcritical hydrolysis process, the same step 1 of process is confirmed the solid-liquid ratio of subcritical hydrolysis;
Step 4: selecting the time of subcritical hydrolysis is 5 ~ 30min, and the same step 1 of process is confirmed time of subcritical hydrolysis;
Step 5: selecting the pressure of subcritical hydrolysis is 5 ~ 20MPa, and the same step 1 of process is confirmed the pressure of subcritical hydrolysis.
Embodiment two: this embodiment is that with embodiment one difference in the step 2 temperature of reaction is controlled at 200 ~ 280 ℃, other composition is identical with embodiment one with step.
Embodiment three: this embodiment is that with embodiment one difference temperature of reaction is controlled at 180 ~ 220 ℃ in the step 2, and other composition is identical with embodiment one with step.
Embodiment four: this embodiment is that with embodiment one difference the step 2 temperature of reaction is controlled at 200 ~ 250 ℃, and other composition is identical with embodiment one with step.
Embodiment five: this embodiment is that with embodiment one ~ four difference solid-liquid ratio is controlled at 0.4:1 ~ 1:1 in the step 3, and other composition is identical with embodiment one ~ four with step.
Embodiment six: this embodiment is that with embodiment one ~ four difference solid-liquid ratio is controlled at 1:1 ~ 2:1 in the step 3, and other composition is identical with embodiment one ~ four with step.
Embodiment seven: this embodiment is that with embodiment one ~ six difference hydrolysis time is controlled at 15 ~ 25min in the step 4, and other composition and step and embodiment one ~ six phase are together.
Embodiment eight: this embodiment is with embodiment one ~ six difference, in the step 4 hydrolysis time is controlled at 10 ~ 20min, and other composition and step and embodiment one ~ six phase are together.
Embodiment nine: this embodiment is that with embodiment one ~ eight difference reaction pressure is controlled at 10 ~ 20MPa in the step 5, and other composition is identical with embodiment one ~ eight with step.
Embodiment ten: this embodiment is that with embodiment one ~ eight difference reaction pressure is controlled at 5 ~ 15MPa in the step 5, and other composition is identical with embodiment one ~ eight with step.
Embodiment 11: accurately take by weighing the 10g soap stock of super-dry pulverization process, sneak into the 22mL acetum, transfer in the high-pressure magnetic stirred autoclave; Pour nitrogen, making reaction pressure is 14Mpa, is placed on the tin bath pot that is heated to 240 ℃ and heats 26min; Reaction finishes and treats to emit nitrogen after the water-bath cooling; Opening unit takes out reaction solution, after washing separates drying, obtains croude fatty acids, and percent hydrolysis is 96.5%.
Embodiment 12: accurately take by weighing the 10g soap stock of super-dry pulverization process, sneak into the 22mL acetum after, transfer in the high-pressure magnetic stirred autoclave; Pour nitrogen, reaction pressure is 11MPa, is placed on the tin bath pot that is heated to 239 ℃ to heat 26min; Reaction finishes and treats to emit nitrogen after the water-bath cooling; Opening unit takes out reaction solution, after washing separates drying, obtains croude fatty acids, and percent hydrolysis is 90.1%.
Embodiment 13: accurately take by weighing the 10g soap stock of super-dry pulverization process, sneaking into 22mL acetum afterreaction pressure is 14MPa, transfers in the high-pressure magnetic stirred autoclave; Pour nitrogen; Be placed on the tin bath pot that is heated to 200 ℃ and heat 26min, reaction finishes and treats to emit nitrogen after the water-bath cooling, and opening unit takes out reaction solution; After washing separates drying, obtain croude fatty acids, percent hydrolysis is 92.2%.
Embodiment 14: accurately take by weighing the 10g soap stock of super-dry pulverization process, sneaking into 22mL acetum afterreaction pressure is 14MPa, transfers in the high-pressure magnetic stirred autoclave; Pour nitrogen; Be placed on the tin bath pot that is heated to 240 ℃ and heat 20min, reaction finishes and treats to emit nitrogen after the water-bath cooling, and opening unit takes out reaction solution; After washing separates drying, obtain croude fatty acids, percent hydrolysis is 89.2%.
Claims (10)
1. a method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid is characterized in that said method comprises the steps: that soap stock mixes with acetum, transfers in the high-pressure magnetic stirred autoclave; Pour nitrogen; Under certain temperature, solid-liquid ratio, reaction pressure and reaction times condition, carry out subcritical hydrolysis, wherein: hydrolysis temperature is 180 ~ 280 ℃, and solid-liquid ratio is 0.2:1 ~ 2:1; Hydrolysis time is 5 ~ 30min, and hydrolysis pressure is 5 ~ 20MP.
2. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said temperature of reaction is controlled at 200 ~ 280 ℃.
3. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said temperature of reaction is controlled at 180 ~ 220 ℃.
4. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said temperature of reaction is controlled at 200 ~ 250 ℃.
5. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said solid-liquid ratio is controlled at 0.4:1 ~ 1:1.
6. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said solid-liquid ratio is controlled at 1:1 ~ 2:1.
7. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said hydrolysis time is controlled at 15 ~ 25min.
8. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said hydrolysis time is controlled at 10 ~ 20min.
9. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said reaction pressure is controlled at 10 ~ 20MPa.
10. a kind of method that adopts subcritical method of acetic acid hydrolysis soap stock to extract lipid acid according to claim 1 is characterized in that said reaction pressure is controlled at 5 ~ 15MPa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106281722A (en) * | 2016-09-05 | 2017-01-04 | 中国林业科学研究院林产化学工业研究所 | A kind of oil foot and the method for soap stock continuous hydrolyzing |
| CN106701849A (en) * | 2015-07-13 | 2017-05-24 | 清华大学 | Enrichment method of polyunsaturated fatty acids |
| CN107149791A (en) * | 2017-05-02 | 2017-09-12 | 江苏大学 | A kind of method for improving Subcritical Water Extraction efficiency |
| CN110669590A (en) * | 2019-09-30 | 2020-01-10 | 郑州远洋油脂工程技术有限公司 | System and method for continuously producing fatty acid by soapstock |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276413A (en) * | 1999-06-04 | 2000-12-13 | 淄博市周村北安社会福利油酸厂 | Process for preparing fatty acid by hydrolyzing of plant oil soapstock without catalyst |
| CN1687342A (en) * | 2005-05-16 | 2005-10-26 | 浙江大学 | Method for preparing fatty acid through continuous hydrolyzing grease without catalysis in near critical aqueous medium |
-
2012
- 2012-09-14 CN CN2012103402939A patent/CN102827699A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1276413A (en) * | 1999-06-04 | 2000-12-13 | 淄博市周村北安社会福利油酸厂 | Process for preparing fatty acid by hydrolyzing of plant oil soapstock without catalyst |
| CN1687342A (en) * | 2005-05-16 | 2005-10-26 | 浙江大学 | Method for preparing fatty acid through continuous hydrolyzing grease without catalysis in near critical aqueous medium |
Non-Patent Citations (1)
| Title |
|---|
| SHIRO SAKA等: "New process for catalyst-free biodiesel production using subcritical acetic acid and supercritical methanol", 《FUEL》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106701849A (en) * | 2015-07-13 | 2017-05-24 | 清华大学 | Enrichment method of polyunsaturated fatty acids |
| CN106281722A (en) * | 2016-09-05 | 2017-01-04 | 中国林业科学研究院林产化学工业研究所 | A kind of oil foot and the method for soap stock continuous hydrolyzing |
| CN107149791A (en) * | 2017-05-02 | 2017-09-12 | 江苏大学 | A kind of method for improving Subcritical Water Extraction efficiency |
| CN110669590A (en) * | 2019-09-30 | 2020-01-10 | 郑州远洋油脂工程技术有限公司 | System and method for continuously producing fatty acid by soapstock |
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Application publication date: 20121219 |