CN117925738A - Method for deacidifying grease by enzymatic method - Google Patents
Method for deacidifying grease by enzymatic method Download PDFInfo
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- CN117925738A CN117925738A CN202410090886.7A CN202410090886A CN117925738A CN 117925738 A CN117925738 A CN 117925738A CN 202410090886 A CN202410090886 A CN 202410090886A CN 117925738 A CN117925738 A CN 117925738A
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- 239000004519 grease Substances 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006911 enzymatic reaction Methods 0.000 title abstract description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol Substances OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 143
- 239000002253 acid Substances 0.000 claims abstract description 80
- 239000004367 Lipase Substances 0.000 claims abstract description 67
- 108090001060 Lipase Proteins 0.000 claims abstract description 66
- 102000004882 Lipase Human genes 0.000 claims abstract description 66
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 235000019421 lipase Nutrition 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000000203 mixture Substances 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 230000002255 enzymatic effect Effects 0.000 claims abstract description 30
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000021588 free fatty acids Nutrition 0.000 claims abstract description 14
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 239000003921 oil Substances 0.000 claims description 57
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 39
- 229930195729 fatty acid Natural products 0.000 claims description 39
- 239000000194 fatty acid Substances 0.000 claims description 39
- 150000004665 fatty acids Chemical class 0.000 claims description 39
- 230000005496 eutectics Effects 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 101000864057 Homo sapiens Serine/threonine-protein kinase SMG1 Proteins 0.000 claims description 3
- 108010048733 Lipozyme Proteins 0.000 claims description 3
- 102100029938 Serine/threonine-protein kinase SMG1 Human genes 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- FCCDDURTIIUXBY-UHFFFAOYSA-N lipoamide Chemical compound NC(=O)CCCCC1CCSS1 FCCDDURTIIUXBY-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 239000003925 fat Substances 0.000 claims 12
- 230000000694 effects Effects 0.000 abstract description 19
- 238000012546 transfer Methods 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 45
- 235000011187 glycerol Nutrition 0.000 description 32
- 108090000790 Enzymes Proteins 0.000 description 16
- 102000004190 Enzymes Human genes 0.000 description 16
- 229940088598 enzyme Drugs 0.000 description 16
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 12
- 235000019774 Rice Bran oil Nutrition 0.000 description 12
- 239000008165 rice bran oil Substances 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 241000238366 Cephalopoda Species 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000010497 wheat germ oil Substances 0.000 description 4
- 238000009874 alkali refining Methods 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000370 acceptor Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 235000013311 vegetables Nutrition 0.000 description 2
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 1
- 102100021851 Calbindin Human genes 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 101000898082 Homo sapiens Calbindin Proteins 0.000 description 1
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101001021643 Pseudozyma antarctica Lipase B Proteins 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079919 digestives enzyme preparation Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 235000019626 lipase activity Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/6445—Glycerides
- C12P7/6454—Glycerides by esterification
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/003—Refining fats or fatty oils by enzymes or microorganisms, living or dead
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Biochemistry (AREA)
- Zoology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for deacidifying grease by an enzymatic method, and belongs to the technical field of deep processing of grease. Taking a blend of proline-glycerol and water as a solvent, adding high acid value grease and free lipase, and then carrying out deacidification reaction under the catalysis of the free lipase. The existence of proline in the reaction system promotes the combination of lipase and free fatty acid, thereby greatly improving the esterification activity of lipase; the existence of water in the system not only improves the activity and stability of free lipase, but also improves the mass transfer of deacidification reaction, thereby greatly improving the deacidification effect of lipase; furthermore, after the reaction of each batch is finished, the addition of the glycerol can improve the stability of the free lipase, and the multi-batch use of the free lipase is realized, so that the application cost of enzymatic deacidification is greatly reduced. The deacidification method has the advantages of high deacidification speed, good effect and low cost, and is an enzymatic deacidification method which can be industrially popularized and applied.
Description
Technical Field
The invention belongs to the technical field of deep processing of grease, and particularly relates to a method for deacidifying grease by an enzymatic method.
Background
Free fatty acid is inevitably generated in the production process of the grease, the property of the free fatty acid is unstable, the grease is easy to oxidize to cause rancidity, and the storage stability and the edible quality of the grease are seriously affected. In order to ensure the quality of the edible oil, the national standard prescribes the acid value standard of the edible oil. Therefore, the removal of free fatty acids in the grease and the reduction of the acid value of the grease are a crucial step in the grease refining process.
In the traditional oil processing industry, chemical alkali refining is generally adopted to remove free fatty acid in oil, a large amount of soap is generated in the chemical alkali refining, neutral oil is adsorbed by the generated soap to reduce the oil refining yield, and a large amount of industrial wastewater is generated by washing the soap after centrifugation. Furthermore, chemical alkali refining is not suitable for deacidification of oils and fats with high acid value. Physical distillation deacidification is also a common oil deacidification method, but physical distillation deacidification requires low phosphorus content of raw materials, and has high temperature and high energy consumption, thereby increasing the production risk of lipid risk factors and deacidification cost in the deacidification process. The methods such as solvent extraction deacidification and membrane filtration deacidification are common grease deacidification methods, but are limited to deacidification effects, deacidification cost and the like, and are not popularized and applied in a large scale. Compared with the method, the novel enzymatic deacidification is efficient, green and environment-friendly, the reaction condition is mild, the oil refining yield is high, the quality of the deacidified oil is good, and the method is a mainstream development direction in the field of oil deacidification.
Solvent systems have an indispensable effect on most chemical reactions. In the enzymatic deacidification reaction process, although a solvent-free system is simple and safe, the accumulation of byproduct water gradually slows down the reaction process along with the progress of the reaction, so that the deacidification time is prolonged, and the deacidification effect is reduced. The reaction system with the best enzymatic deacidification effect is an organic solvent system, and the organic solvent can increase the solubility of a substrate, reduce the polarity of the reaction system, and accelerate the separation of byproduct water so as to improve the efficiency and the effect of enzymatic deacidification. However, the organic solvent has the problems of high toxicity, inflammability, explosiveness and the like, so that the organic solvent is full of environmental protection and safety. At present, an enzyme preparation adopted by the enzymatic deacidification is mainly immobilized lipase, and the enzymatic deacidification efficiency in an organic solvent system is low and the cost is high due to the limitation of reaction mass transfer and the high application cost of the immobilized lipase.
CN105802730a discloses a method for deacidifying rice bran oil by immobilized lipase, which comprises mixing rice bran oil with glycerin, adding immobilized lipase Lipozyme 435 accounting for 2% -7% of the total mass of the substrate, reacting in a vacuum device at a reaction temperature of 40-80 ℃ and a vacuum degree of 40-60 mbar for 5-7 h, cooling by a nitrogen cooling device, and centrifuging to obtain deacidified rice bran oil; CN106566658a discloses an enzymatic deacidification method of high acid value grease, which comprises the steps of mixing glycerol and high acid value grease, using a mutant of partial glyceride lipase LIPASE SMG1 as a catalyst, carrying out esterification reaction on the glycerol and free fatty acid in the high acid value grease, separating reaction products, and recovering an oil phase to obtain the enzymatic deacidification grease. The free fatty acid removal rate of the invention can reach more than 90%, the neutral grease has no side reaction, and the reaction product is easy to separate and purify. CN113061486a discloses a method for removing free fatty acid in grease by enzyme catalysis, which comprises mixing a eutectic solvent composed of polyalcohol and choline chloride or betaine with vegetable crude oil, adding lipase, stirring for reaction, and centrifuging after the reaction is finished, wherein the upper layer oil phase is the vegetable crude oil for removing free fatty acid. The invention shortens the deacidification reaction time of the enzyme method, the product is easy to separate and purify, and the enzyme can be recycled for a plurality of times.
However, the existing enzymatic deacidification technology mainly improves the enzymatic deacidification efficiency, improves the enzymatic deacidification effect, improves the oil yield, reduces the enzymatic deacidification cost and the like by changing a reaction device, enzyme preparation types, reaction solvent types, acyl acceptors and the like. Because most of enzyme preparations commonly used in enzymatic deacidification are immobilized lipase, the application cost is high, and the deacidification efficiency is low; the adoption of free lipase deacidification can improve the mass transfer effect and the deacidification efficiency, but is limited by the application times of the free lipase, and the application cost of the free lipase deacidification is not accepted by enterprises. Aiming at the technical bottlenecks of low deacidification efficiency, poor effect, high cost and the like faced by the oil lipase deacidification method, the enzyme deacidification technology capable of being industrially applied is urgently required to be upgraded or researched and developed.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the method for deacidifying the grease by the enzymatic method, which has the advantages of low cost, high speed and good effect, and has good economic benefit and industrial application prospect.
The invention is realized by the following technical scheme:
the enzymatic deacidification method of the grease comprises the following steps:
step 1: adding high acid value grease into a blend of the eutectic solvent proline-glycerol and water, uniformly stirring, heating, adding free lipase, and carrying out esterification reaction; after the reaction is finished, carrying out centrifugal treatment, and respectively collecting a blend of proline-glycerol, water and free lipase and deacidified grease;
Step 2: supplementing glycerol to the blend obtained in the step 1, carrying out ultrasonic dispersion treatment, continuously adding pretreated high-acid-value grease, carrying out esterification reaction under the reaction condition of the step 1, and respectively collecting the blend of amino acid-glycerol, water and free lipase and deacidified grease after the reaction is finished;
Step 3: and (3) repeating the step (2) until the fatty acid removal rate of the high acid value grease is reduced to a preset value.
Preferably, in the step 1, the molar ratio of proline to glycerol in the eutectic solvent proline-glycerol is 1:2-5.
Preferably, in the step 1, in the blend of the eutectic solvent proline-glycerol and water, the water is deionized water, and the addition amount of the deionized water is 5-20% of the mass of the proline-glycerol.
Further preferably, in step 1, when a blend of proline-glycerol, a eutectic solvent, and water is prepared, deionized water is added to the proline-glycerol, and then the mixture is treated at an ultrasonic frequency of 20 to 40kHz at a temperature of 40 to 60 ℃ for 1 to 2 minutes.
Preferably, in the step 1, the high acid value grease is subjected to degumming and dewaxing pretreatment, and the mass ratio of the high acid value grease to the blend is 2-4:1.
Preferably, in step 1, the free lipase is a lipaseCALB L, lecitase Ultra, lipozyme TL 100L, palatase 20000L, lipase G "Amano"50, LIPASE SMG1 or Lipase AOL, the addition amount of free Lipase is 1% -5% of the sum of the mass of the high acid value grease and the mass of the glycerol.
Preferably, in the step 1, the temperature of the esterification reaction is 20-50 ℃ and the reaction time is 0.5-1 h.
Preferably, in the step 2, the relation between the added amount m 1 of the glycerol and the mass m and the acid value AV of the high acid value grease is as follows:
m1＝1.2～1.3*(92*m*AV)/(1.6833*105)。
preferably, in step 2, after glycerol addition, the mixture is treated at an ultrasonic frequency of 20 to 40kHz and a temperature of 40 to 60 ℃ for 3 to 6 minutes.
Preferably, in step 3, the fatty acid removal rate= (free fatty acid before deacidification-free fatty acid content after deacidification)/free fatty acid content before deacidification.
Compared with the prior art, the invention has the following beneficial technical effects:
The invention discloses a deacidification method of grease by an enzyme method, which is characterized in that water is added into proline-glycerin which is a eutectic solvent for ultrasonic treatment to obtain a blend, and the blend is used as a reaction solvent, and deacidification reaction is carried out after high-acid-value grease and free lipase are added. When the hydrogen bond donor of the eutectic solvent is glycerol, changing the hydrogen bond acceptor, the free lipase shows different catalytic activities in the formed eutectic solvent, and compared with a solvent-free system, the catalytic activity of the free lipase in a proline-glycerol system is obviously improved; this is because the presence of proline increases the nucleophilicity of the free lipase serine in the lipase-catalyzed deacidification reaction, thereby increasing the catalytic activity of the free lipase. The blend formed after the water is added can further improve the catalytic activity of the free enzyme, and is mainly because water molecules can maintain the active conformation of the lipase and the flexibility of an enzyme active center through the action of hydrogen bonds, thereby being beneficial to the exertion of the lipase activity, and on the other hand, the addition of the water molecules enhances the mass transfer of the reaction, thereby improving the catalytic activity and the stability of the free enzyme. Under the combined action of the two aspects, the deacidification efficiency of the free lipase is greatly improved under the system, the deacidification effect is obviously improved, and the removal rate of 98 percent of fatty acid can be realized within 1 h. In addition, the glycerol adding strategy of the invention can supplement the glycerol consumed in the step 1, ensure that the glycerol fully interacts with proline and free lipase, and can maintain the activity of the free lipase, and ensure that the system is repeatedly and efficiently utilized, thereby greatly reducing the application cost of enzymatic deacidification. The invention has high deacidification efficiency, good effect, low deacidification cost and good economic benefit and industrial application prospect.
Further, the reaction solvent is a blend of proline-glycerol and water, and the molar ratio of proline-glycerol and the addition amount and mode of water can ensure high speed and high fatty acid removal rate when free enzyme deacidifies.
Furthermore, the enzyme preparation for deacidification is free lipase, so that on one hand, good deacidification mass transfer effect can be ensured, and on the other hand, the economy of the reaction can be ensured.
Furthermore, the addition amount and mode of glycerol after each batch of reaction are finished can maintain the active conformation and stability of free enzyme on one hand and greatly reduce the application cost of enzymatic deacidification on the other hand.
Further, the esterification reaction conditions ensure higher enzymatic activity, stability and free fatty acid removal rate.
Drawings
FIG. 1 is a technical flow chart of the present invention.
Detailed Description
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention. All percentages are mass percentages, unless otherwise indicated.
Fig. 1 is a technical flow chart of the invention, adding deionized water into a eutectic solvent composed of proline-glycerin, performing ultrasonic treatment to obtain a proline-glycerin and water blend, then adding degummed and dewaxed high acid value grease and free lipase, performing deacidification reaction, recovering a blend of upper deacidified grease and lower solvent, water and free lipase after the reaction is finished, adding glycerin and degummed and dewaxed high acid value grease into the blend of solvent, water and free lipase, continuing deacidification reaction, and repeating circularly until the deacidification effect is remarkably reduced, and stopping the reaction. In actual production, the different high acid value oils or the same high acid value oils have different requirements on fatty acid removal rate due to different fatty acid compositions or different acid values, so that the preset values are different, and taking the following examples of the invention as examples, the preset values of the fatty acid removal rate are 97.65%, 97.84%, 96.27%, 96.06%, 97.45%, 97.65% and 97.45%, respectively.
Example 1
Adding 100G of eutectic solvent (proline-glycerol, proline: glycerol=1:2, molar ratio) into a 1L reaction bottle, adding 5G of deionized water, treating for 1min at 40 ℃ and ultrasonic frequency of 40kHz to obtain proline-glycerol and water blend, adding 210G of degummed and dewaxed high acid value rice bran oil, heating to 20 ℃ after stirring uniformly, adding 2.72G of free Lipase G 'Amano', starting timing after reaction, centrifuging to separate a reaction mixture after 1h, obtaining the upper layer of deacidified oil, measuring the acid value of the deacidified oil, and measuring the acid value of the deacidified oil to be 0.21mg KOH/G and the fatty acid removal rate to be 99.64%; setting the preset value of the fatty acid removal rate to be 97.65%, and continuing to recycle the obtained lower layer: after 8.02g of glycerol is added into a mixture of solvent, water and free lipase, the mixture is treated for 3min at 40 ℃ and 40kHz ultrasonic frequency, then 210g of degummed and dewaxed rice bran oil with high acid value (acid value is 58.22mg KOH/g) is added, deacidification reaction is circularly carried out, and after 50 batches of the mixture are circularly carried out, the fatty acid removal rate is 98.12 percent and is still higher than a preset value.
Example 2
Adding 100g of eutectic solvent (proline-glycerol, proline: glycerol=1:5, molar ratio) into a 1.5L reaction bottle, adding 20g of deionized water, treating at 60 ℃ and ultrasonic frequency of 20kHz for 2min to obtain proline-glycerol and water blend, adding 480g of degummed and dewaxed rice bran oil with high acid value of 58.22mg KOH/g, stirring uniformly, heating to 50 ℃, and adding 28g of free lipaseAfter CALB L, the reaction starts timing, after 0.5h of reaction, centrifugally separating the reaction mixture, wherein the upper layer is deacidified oil, and performing acid value measurement on the deacidified oil obtained by separation, wherein the acid value of the deacidified oil is 0.10mg KOH/g, and the fatty acid removal rate is 99.83%; setting the preset value of the fatty acid removal rate to be 97.84%, and continuing to recycle the obtained lower layer: after 19.86g of glycerol is added into a mixture of solvent, water and free lipase, the mixture is treated for 6min at 60 ℃ and 20kHz ultrasonic frequency, 480g of degummed and dewaxed rice bran oil with high acid value (acid value is 58.22mg KOH/g) is added, deacidification reaction is circularly carried out, and after 50 batches are circulated, the fatty acid removal rate is 98.55 percent and is still higher than a preset value.
Example 3
Adding 100g of eutectic solvent (proline-glycerol, proline: glycerol=1:3, molar ratio) into a 1.5L reaction bottle, adding 10g of deionized water, treating for 1.5min at 50 ℃ and 30kHz ultrasonic frequency to obtain a proline-glycerol and water blend, adding 330g of degummed and dewaxed high-acid-value squid oil, heating to 40 ℃ after uniform stirring, adding 12.02g of free lipase Lecitase Ultra, starting timing the reaction, reacting for 50min, centrifuging to separate the reaction mixture, obtaining the upper layer of deacidified oil, measuring the acid value of the deacidified oil, wherein the acid value of the deacidified oil is 0.33mg KOH/g, and the fatty acid removal rate is 98.23%; setting the preset value of the fatty acid removal rate to 96.27%, and continuing to recycle the obtained lower layer: after adding 4.21g of glycerol to the mixture of solvent, water and free lipase, treating for 4min at 50 ℃ and 30kHz ultrasonic frequency, then adding 330g of degummed and dewaxed squid oil with high acid value (acid value is 18.68mg KOH/g, carrying out deacidification reaction circularly, and after 50 batches of circulation, the fatty acid removal rate is 96.41 percent and is still higher than a preset value.
Example 4
Adding 100g of eutectic solvent (proline-glycerol, proline: glycerol=1:4, molar ratio) into a 1L reaction bottle, adding 15g of deionized water, treating at 40 ℃ and 20kHz ultrasonic frequency for 2min to obtain proline-glycerol and water blend, adding 287.5g of degummed and dewaxed high acid value squid oil, heating to 30 ℃ after stirring uniformly, adding LIPASE SMG g of free lipase LIPASE SMG, starting timing the reaction, reacting for 40min, centrifuging to separate a reaction mixture, obtaining deacidified oil at the upper layer, measuring the acid value of the deacidified oil obtained by separation, and measuring the acid value of the deacidified oil to be 0.37mg KOH/g and the fatty acid removal rate to be 98.02%; setting the preset value of the fatty acid removal rate to be 96.06 percent, and continuing to recycle the obtained lower layer: after 3.76g of glycerol is added into the mixture of solvent, water and free lipase, the mixture is treated for 3min at 45 ℃ and ultrasonic frequency of 35kHz, 287.5g of degummed and dewaxed squid oil (acid value is 18.68mg KOH/g) with high acid value is added, deacidification reaction is circularly carried out, and after 50 batches are circularly carried out, the fatty acid removal rate is 96.41 percent and is still higher than a preset value.
Example 5
Adding 100g of eutectic solvent (proline-glycerol, proline: glycerol=1:2.5 in molar ratio) into a 1.5L reaction bottle, adding 12g of deionized water, treating for 1.5min at 60 ℃ and 30kHz ultrasonic frequency to obtain a proline-glycerol and water blend, adding 392g of degummed and dewaxed wheat germ oil with high acid value, heating to 35 ℃ after uniform stirring, adding 16.05g of free lipase TL 100L, starting timing the reaction, centrifuging the reaction mixture after the reaction for 35min, obtaining the upper layer of deacidified oil, measuring the acid value of the deacidified oil, wherein the acid value of the deacidified oil is 0.17mg KOH/g, and the fatty acid removal rate is 99.44%; setting the preset value of the fatty acid removal rate to be 97.45%, and continuing to recycle the obtained lower layer: after adding 4.96g of glycerol to a mixture of solvent, water and free lipase, treating for 5min at 55 ℃ and ultrasonic frequency of 25kHz, adding 392g of degummed and dewaxed wheat germ oil with high acid value (acid value is 30.55mg KOH/g), and carrying out deacidification reaction in a circulating way, wherein after 50 batches are circulated, the fatty acid removal rate is 96.87 percent and is still higher than a preset value.
Example 6
Adding 100g of eutectic solvent (proline-glycerol, proline: glycerol=1:3.5, molar ratio) into a 1.5L reaction bottle, adding 16g of deionized water, treating for 1.5min at 50 ℃ and 30kHz ultrasonic frequency to obtain a proline-glycerol and water blend, adding 324.8g of degummed and dewaxed wheat germ oil with high acid value, heating to 45 ℃ after uniform stirring, adding 15.14g of free lipase Palatase 20000L, starting timing the reaction, centrifuging the reaction mixture after 30min, separating the upper layer to obtain deacidified oil, measuring the acid value of the deacidified oil, wherein the acid value of the deacidified oil is 0.11mg KOH/g, and the fatty acid removal rate is 99.64%; setting the preset value of the fatty acid removal rate to be 97.65%, and continuing to recycle the obtained lower layer: after 6.56g of glycerol is added into the mixture of solvent, water and free lipase, the mixture is treated for 5min at 50 ℃ and 20kHz ultrasonic frequency, then 324.8g of degummed and dewaxed wheat germ oil with high acid value (acid value is 30.55mg KOH/g, deacidification reaction is circularly carried out, and after 50 batches are circularly carried out, the fatty acid removal rate is 97.72 percent and is still higher than a preset value.
Example 7
Adding 100g of eutectic solvent (proline-glycerol, proline: glycerol=1:4.5, molar ratio) into a 1.5L reaction bottle, adding 16g of deionized water, treating for 1.5min at 50 ℃ and 30kHz ultrasonic frequency to obtain a proline-glycerol and water blend, adding 359.6g of degummed and dewaxed rice bran oil with high acid value, heating to 30 ℃ after uniform stirring, adding 21.02g of free Lipase AOL, starting timing the reaction, centrifuging the reaction mixture after 30min, separating the upper layer to obtain deacidified oil, measuring the acid value of the deacidified oil, wherein the acid value of the deacidified oil is 0.08mg KOH/g, and the fatty acid removal rate is 99.44%; setting the preset value of the fatty acid removal rate to be 97.45%, and continuing to recycle the obtained lower layer: after adding 3.61g of glycerol to the mixture of solvent, water and free lipase, the mixture was treated at 40℃and an ultrasonic frequency of 20kHz for 6min, 359.6g of degummed and dewaxed rice bran oil with a high acid value (acid value: 14.26mg KOH/g) was added, and the deacidification reaction was carried out in a cycle, wherein after 50 batches of the cycle, the fatty acid removal rate was 97.49%, which was still higher than the preset value.
Comparative example 1
210G of degummed and dewaxed rice bran oil with high acid value and acid value of 58.22mg KOH/G and 61.54G of glycerin (the adding amount of glycerin is the same as that in the embodiment 1) are added into a 500mL reaction bottle, after the mixture is stirred uniformly, the mixture is heated to 20 ℃, 2.72G of free Lipase G 'Amano' 50 is added, the reaction starts to time, after the reaction starts for 1h, the reaction mixture is centrifugally separated, the upper layer is the deacidified oil, the acid value of the deacidified oil obtained by separation is measured, the acid value of the deacidified oil is measured to be 30.64mg KOH/G, and the removal rate of fatty acid is 47.37%. Compared with example 1, the deacidification of the grease is carried out in a solvent-free system in comparative example 1, the fatty acid removal rate is greatly reduced (47.37% vs 99.64%) in comparative example 1 compared with the deacidification of the grease in a proline-glycerin water blend in example 1, and the free Lipase G 'Amano' 50 is difficult to recycle.
Comparative example 2
Adding 100G of eutectic solvent (proline-glycerol, proline: glycerol=1:2, molar ratio), continuously adding 210G of degummed and dewaxed rice bran oil with high acid value, wherein the acid value is 58.22mg KOH/G, stirring uniformly, heating to 20 ℃, adding 2.72G of free Lipase G 'Amano' 50, starting to time the reaction, reacting for 1h, centrifuging to separate a reaction mixture, obtaining the upper layer of deacidified oil, measuring the acid value of the separated deacidified oil, and obtaining the acid value of the deacidified oil to be 12.31mg KOH/G and the fatty acid removal rate to be 78.86%; the recovered lower proline-glycerin and enzyme mixture can be used for a new batch of enzymatic deacidification reaction after new high-acid-value grease is added. In comparison with example 1, comparative document 2 was subjected to deacidification in the eutectic solvent proline-glycerin, and deionized water was not added to the proline-glycerin system, and although the eutectic solvent proline-glycerin could be recovered and reused after the end of the reaction, the fatty acid removal rate (78.86%) was significantly lower than that in example 1 (99.64%).
Comparative example 3
Adding 100G of eutectic solvent (proline-glycerol-deionized water, proline: glycerol: deionized water=1:2:0.85, wherein the adding amount of deionized water is equivalent to 5G), continuously adding 210G of degummed and dewaxed rice bran oil with high acid value, wherein the acid value is 58.22mg KOH/G, heating to 20 ℃ after stirring uniformly, adding 2.72G of free Lipase G 'Amano' 50, starting timing the reaction, reacting for 1h, centrifuging to separate a reaction mixture, obtaining deacidified grease at the upper layer, measuring the acid value of the deacidified grease obtained by separation, and measuring the acid value of the deacidified grease to be 7.43mg KOH/G and the fatty acid removal rate to be 87.24%; the recovered lower proline-glycerol-deionized water and enzyme mixture can be used for a new batch of enzyme deacidification reaction after new high-acid-value grease is added. In comparison with example 1, comparative document 3 was subjected to deacidification in the eutectic solvent proline-glycerin-water, the timing of the addition of water was such that water was added at the time of the eutectic solvent preparation, that is, water was one of the components of the eutectic solvent, and although the eutectic solvent proline-glycerin could be recovered and reused after the end of the reaction, the fatty acid removal rate (87.24%) was significantly lower than that in example 1 (99.64%).
The following table shows the reaction systems used in each of the examples and comparative examples, the free lipase used, the acid value before and after deacidification of the high acid value grease, and the fatty acid removal rate:
The foregoing is only a part of the embodiments of the present invention, and although some terms are used in the present invention, the use of other terms is not excluded. These terms are used merely for convenience of description and to explain the nature of the invention and are to be construed as any additional limitations that are not intended to depart from the spirit of the invention. The foregoing description of the invention is provided by way of example only to facilitate easy understanding, but is not intended to limit the scope of the invention to any particular embodiment or embodiment, and is to be construed as being limited thereto.
Claims (10)
1. The enzymatic deacidification method of the grease is characterized by comprising the following steps of:
step 1: adding high acid value grease into a blend of the eutectic solvent proline-glycerol and water, uniformly stirring, heating, adding free lipase, and carrying out esterification reaction; after the reaction is finished, carrying out centrifugal treatment, and respectively collecting a blend of proline-glycerol, water and free lipase and deacidified grease;
Step 2: supplementing glycerol to the blend obtained in the step 1, carrying out ultrasonic dispersion treatment, continuously adding pretreated high-acid-value grease, carrying out esterification reaction under the reaction condition of the step 1, and respectively collecting the blend of amino acid-glycerol, water and free lipase and deacidified grease after the reaction is finished;
Step 3: and (3) repeating the step (2) until the fatty acid removal rate of the high acid value grease is reduced to a preset value.
2. The method for enzymatic deacidification of oil and fat according to claim 1, wherein in the step 1, the molar ratio of proline to glycerol in the eutectic solvent proline-glycerol is 1:2-5.
3. The method for enzymatic deacidification of oil and fat according to claim 1, wherein in the step 1, in the blend of proline-glycerin as a eutectic solvent and water, the water is deionized water, and the adding amount of the deionized water is 5% -20% of the mass of the proline-glycerin.
4. The method for enzymatic deacidification of fats and oils according to claim 3, wherein in step 1, deionized water is added to proline-glycerol when a blend of proline-glycerol, which is a eutectic solvent, and the mixture is prepared, and the mixture is treated at an ultrasonic frequency of 20 to 40kHz and a temperature of 40 to 60 ℃ for 1 to 2 minutes.
5. The enzymatic deacidification method of oil and fat according to claim 1, wherein in the step 1, the oil and fat with high acid value is pretreated by degumming and dewaxing, and the mass ratio of the oil and fat with high acid value to the blend is 2-4:1.
6. The method for enzymatic deacidification of oil and fat according to claim 1, wherein in step 1, the free lipase is lipaseCALB L, lecitase Ultra, lipozyme TL 100L, palatase 20000L, lipase G "Amano"50, LIPASE SMG1 or Lipase AOL, the addition amount of free Lipase is 1% -5% of the sum of the mass of the high acid value grease and the mass of the glycerol.
7. The method for enzymatic deacidification of oil and fat according to claim 1, wherein in the step 1, the temperature of the esterification reaction is 20-50 ℃ and the reaction time is 0.5-1 h.
8. The method for enzymatic deacidification of oil and fat according to claim 1, wherein in the step 2, the relation between the added amount m 1 of glycerol and the mass m and the acid value AV of the oil and fat with high acid value is:
m1＝1.2～1.3*(92*m*AV)/(1.6833*105)。
9. the method for enzymatic deacidification of fats and oils according to claim 1, wherein in step 2, after glycerol is added, the mixture is treated at an ultrasonic frequency of 20 to 40kHz at a temperature of 40 to 60 ℃ for 3 to 6 minutes.
10. The method for enzymatic deacidification of oil and fat according to claim 1, wherein in step 3, the fatty acid removal rate= (free fatty acid before deacidification-free fatty acid after deacidification)/free fatty acid before deacidification.
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