CN115404245A - Method for producing fatty acid and fatty acid - Google Patents
Method for producing fatty acid and fatty acid Download PDFInfo
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- CN115404245A CN115404245A CN202110583254.0A CN202110583254A CN115404245A CN 115404245 A CN115404245 A CN 115404245A CN 202110583254 A CN202110583254 A CN 202110583254A CN 115404245 A CN115404245 A CN 115404245A
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- acid
- soapstock
- hydrolase
- fatty acid
- enzymolysis
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 85
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 85
- 239000000194 fatty acid Substances 0.000 title claims abstract description 85
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 104
- 239000002253 acid Substances 0.000 claims abstract description 73
- 230000020477 pH reduction Effects 0.000 claims abstract description 45
- 239000000344 soap Substances 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 69
- 125000005456 glyceride group Chemical group 0.000 claims description 56
- 239000003921 oil Substances 0.000 claims description 47
- 235000019198 oils Nutrition 0.000 claims description 47
- 239000003549 soybean oil Substances 0.000 claims description 39
- 235000012424 soybean oil Nutrition 0.000 claims description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 37
- 229910052708 sodium Inorganic materials 0.000 claims description 26
- 239000011734 sodium Substances 0.000 claims description 26
- -1 sodium fatty acid Chemical class 0.000 claims description 25
- 235000021588 free fatty acids Nutrition 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 12
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 12
- 150000003904 phospholipids Chemical class 0.000 claims description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 12
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000003995 emulsifying agent Substances 0.000 claims description 9
- 230000007071 enzymatic hydrolysis Effects 0.000 claims description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims description 6
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003760 tallow Substances 0.000 claims description 5
- 240000006439 Aspergillus oryzae Species 0.000 claims description 4
- 235000002247 Aspergillus oryzae Nutrition 0.000 claims description 4
- 241001291474 Malassezia globosa Species 0.000 claims description 4
- 244000271379 Penicillium camembertii Species 0.000 claims description 4
- 235000002245 Penicillium camembertii Nutrition 0.000 claims description 4
- 241000228245 Aspergillus niger Species 0.000 claims description 3
- 241000222175 Diutina rugosa Species 0.000 claims description 3
- 241001661345 Moesziomyces antarcticus Species 0.000 claims description 3
- 235000019483 Peanut oil Nutrition 0.000 claims description 3
- 241000228143 Penicillium Species 0.000 claims description 3
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 3
- 241000235403 Rhizomucor miehei Species 0.000 claims description 3
- 235000019774 Rice Bran oil Nutrition 0.000 claims description 3
- 235000019486 Sunflower oil Nutrition 0.000 claims description 3
- 241000223258 Thermomyces lanuginosus Species 0.000 claims description 3
- 235000015278 beef Nutrition 0.000 claims description 3
- 239000002285 corn oil Substances 0.000 claims description 3
- 235000005687 corn oil Nutrition 0.000 claims description 3
- 235000012343 cottonseed oil Nutrition 0.000 claims description 3
- 239000002385 cottonseed oil Substances 0.000 claims description 3
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 229960000448 lactic acid Drugs 0.000 claims description 3
- 239000000312 peanut oil Substances 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 239000008165 rice bran oil Substances 0.000 claims description 3
- 239000004334 sorbic acid Substances 0.000 claims description 3
- 235000010199 sorbic acid Nutrition 0.000 claims description 3
- 229940075582 sorbic acid Drugs 0.000 claims description 3
- 239000002600 sunflower oil Substances 0.000 claims description 3
- 229940005605 valeric acid Drugs 0.000 claims description 3
- 241000589516 Pseudomonas Species 0.000 claims description 2
- 102000004190 Enzymes Human genes 0.000 abstract description 28
- 108090000790 Enzymes Proteins 0.000 abstract description 28
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 20
- 230000007062 hydrolysis Effects 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 7
- 108090000604 Hydrolases Proteins 0.000 description 47
- 102000004157 Hydrolases Human genes 0.000 description 47
- 239000012071 phase Substances 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000003925 fat Substances 0.000 description 17
- 238000000926 separation method Methods 0.000 description 16
- 238000003756 stirring Methods 0.000 description 13
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 12
- 238000003760 magnetic stirring Methods 0.000 description 12
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 9
- 230000003301 hydrolyzing effect Effects 0.000 description 9
- 229960000583 acetic acid Drugs 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000002479 acid--base titration Methods 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 235000011187 glycerol Nutrition 0.000 description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 4
- 239000005642 Oleic acid Substances 0.000 description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000006911 enzymatic reaction Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 238000003811 acetone extraction Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 3
- 239000008158 vegetable oil Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 239000000787 lecithin Substances 0.000 description 2
- 229940067606 lecithin Drugs 0.000 description 2
- 235000010445 lecithin Nutrition 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 108090000371 Esterases Proteins 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 241001507683 Penicillium aurantiogriseum Species 0.000 description 1
- 241000589774 Pseudomonas sp. Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003568 Sodium, potassium and calcium salts of fatty acids Substances 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000010699 lard oil Substances 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 238000000526 short-path distillation Methods 0.000 description 1
- 235000013875 sodium salts of fatty acid Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009283 thermal hydrolysis 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
- C12P7/6409—Fatty acids
- C12P7/6418—Fatty acids by hydrolysis of fatty acid esters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (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 provides a method for producing fatty acid and fatty acid. The method for producing a fatty acid of the present invention comprises: a pretreatment step of contacting the soapstock with a first acid to obtain a pretreated soapstock, wherein the ratio of fatty substances to soap in the pretreated soapstock is 1; an enzymolysis reaction step, in which the pretreated soapstock is contacted with hydrolase to carry out enzymolysis reaction, so as to obtain an enzymolysis mixture; and an acidification reaction step, wherein the enzymolysis mixture obtained in the enzymolysis reaction step is contacted with a second acid for acidification reaction. The preparation method can greatly reduce the enzyme dosage and the enzymolysis time in the enzymolysis reaction, remarkably improve the hydrolysis efficiency, and can obtain the fatty acid with high conversion rate by using a small amount of enzyme in a short time.
Description
Technical Field
The invention relates to the field of grease processing, relates to a method for preparing fatty acid and the fatty acid, and particularly relates to a method for preparing the fatty acid by hydrolyzing soapstock by an enzyme method and the fatty acid prepared by the method.
Background
The soapstock is a byproduct in the oil refining process, the total amount of the soapstock accounts for 5-6% of the oil yield, and the soapstock mainly comprises the following components: water, neutral oil (glyceride), soap (sodium fatty acid), free fatty acid, phospholipid, lipoid, pigment and other matters, wherein the neutral oil and the sodium fatty acid account for 35-50% of the mass of the soapstock. Thus, soapstock is a suitable raw material for the production of mixed fatty acids, in which fatty acids in the form of sodium salts of fatty acids can be decomposed by sulfuric acid and fatty acids in the form of neutral oils can be decomposed by hydrolysis, so that there are mainly three methods for the production of fatty acids from soapstock, namely hydrolytic acidification, saponification acidolysis and acidification hydrolysis. Compared with other two methods, the acidification hydrolysis method is more adopted in production.
The traditional acidification hydrolysis method for preparing fatty acid comprises the steps of heating soapstock at high temperature to be above 90 ℃, adding 6-8% concentrated sulfuric acid for acidification and stratification for hours or even days to obtain acidified oil, washing the acidified oil with water, hydrolyzing by adopting a high-temperature high-pressure hydrolysis method to hydrolyze glyceride in the acidified oil into free fatty acid, and distilling to obtain a crude fatty acid product. Although the process is adopted in more production, the process has the disadvantages of high energy consumption, serious pollution, high requirement on equipment for hydrolysis reaction, easy occurrence of side reaction in the hydrolysis process and the like, and the quality and the yield of the fatty acid product are reduced.
Therefore, in order to overcome the defects of the acidification and hydrolysis methods, many documents report some new methods, such as a thermal hydrolysis and acidification method (patent application CN 201780003789.8), a subcritical acetic acid method (patent application CN 201210340293.9), a short-path distillation and acidification method (patent application CN 200610086288.4) and the like, but the methods all have the defects of complex process flow, difficult catalyst acquisition or high cost and the like. In addition, the neutral oil in the soapstock is completely hydrolyzed by adopting an enzyme method, and then is subjected to an acidification reaction, so that the soapstock can be directly changed into fatty acid in one step, and the high-temperature and high-pressure hydrolysis reaction of the acidified oil is avoided, so that the energy consumption is greatly reduced, and the process is an environment-friendly process, but in the methods for hydrolyzing the grease or the soapstock by adopting the enzyme method, the hydrolysis time is as long as 36 hours, the use amount of the enzyme is large, and the conversion rate of glyceride in the soapstock is low as reported by patent application CN200810110995.1 and patent application CN 201310185942.7.
Disclosure of Invention
Problems to be solved by the invention
The existing enzymatic hydrolysis of lipid substances has the defects of low hydrolysis rate (for example, about 70 percent of the hydrolysis rate is common), long reaction time (for example, 1 to 3 days), high enzyme cost (large enzyme consumption) and the like, so the invention aims to provide a method for preparing fatty acid, which directly prepares the fatty acid by pretreating soapstock and then performing enzymatic hydrolysis and high-temperature acidification one-pot method. The preparation method can greatly reduce the enzyme dosage and the enzymolysis time in the enzymolysis reaction, obviously improve the hydrolysis efficiency, and can obtain the fatty acid with high conversion rate by using a small amount of enzyme in a short time.
Means for solving the problems
The present inventors have intensively studied to achieve the above object, and as a result, have found that the above object can be achieved by carrying out the following means.
Namely, the present invention is as follows.
[1] A method of making a fatty acid, the method comprising:
a pretreatment step of contacting the soapstock with a first acid to obtain a pretreated soapstock, wherein the mass ratio of fatty substances (calculated by glyceride and free fatty acid) to soap (calculated by sodium fatty acid) in the pretreated soapstock is 1;
an enzymolysis reaction step, in which the pretreated soapstock is contacted with hydrolase to carry out enzymolysis reaction, so as to obtain an enzymolysis mixture; and
and an acidification reaction step, wherein the enzymolysis mixture obtained in the enzymolysis reaction step is contacted with a second acid for acidification reaction.
[2] The production process according to [1], the soapstock comprising at least one selected from the group consisting of soybean oil soapstock, cottonseed oil soapstock, corn oil soapstock, rapeseed oil soapstock, sunflower oil soapstock, peanut oil soapstock, rice bran oil soapstock, lard soapstock, beef tallow soapstock and mutton tallow soapstock;
preferably, the moisture content of the soapstock is 40-60%.
[3] The production process according to [1] or [2], the first acid comprising a strong acid having a pKa of less than 1 and/or a weak acid having a pKa of more than 4;
preferably, the strong acid having a pKa of less than 1 comprises at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid and trichloroacetic acid;
the weak acid having a pKa of greater than 4 comprises at least one selected from the group consisting of acetic acid, citric acid, propionic acid, butyric acid, valeric acid, sorbic acid, and lactic acid.
[4] The production process according to any one of [1] to [3], wherein the mass ratio of the fatty material (in terms of glyceride and free fatty acid) to the total emulsifier (in terms of soap and phospholipid) in the pretreated soapstock is 1.
[5] The production method according to any one of [1] to [4], wherein the first acid is used in an amount of 1 to 3 mass% based on the total amount of soapstock.
[6] The production process according to any one of [1] to [5], wherein the hydrolase comprises a triglyceride hydrolase and/or a partial glyceride hydrolase;
preferably, the glycerol triester hydrolase comprises a glycerol triester hydrolase derived from at least one member of the group consisting of thermomyces lanuginosus, candida antarctica, rhizomucor miehei, aspergillus niger, candida rugosa, and pseudomonas;
the partial glyceride hydrolase includes a partial glyceride hydrolase derived from at least one member of the group consisting of Penicillium camemberti, penicillium circulans, aspergillus oryzae, and Malassezia globosa.
[7] The production method according to any one of [1] to [6], wherein the amount of the hydrolase to be used is 0.01 to 0.05 mass% based on the total amount of the soapstock;
preferably, the pretreated soapstock and the hydrolase are subjected to an enzymolysis reaction at 30-50 ℃;
the time of the enzymolysis reaction is 2-4 h.
[8] The production method according to any one of [1] to [7], wherein the second acid comprises a strong acid having a pKa of less than 1;
preferably, the second acid includes at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, and trichloroacetic acid;
preferably, the second acid is used in an amount of 2 to 5 mass% relative to the total amount of the soapstock;
preferably, the enzymatic hydrolysis mixture is reacted with the second acid at 80-100 ℃ for 4-6 h.
[9] The production method according to any one of [1] to [8], wherein the soapstock is heated to 30 to 50 ℃ before the pretreatment step.
[10] A fatty acid obtained by the production method according to any one of [1] to [9 ].
ADVANTAGEOUS EFFECTS OF INVENTION
Through the implementation of the technical scheme, the invention can obtain the following technical effects:
(1) The method can greatly reduce the enzyme dosage in the enzymolysis reaction, and the enzyme cost is obviously reduced; the enzymolysis time can be greatly shortened to 2-4 h from 24-36 h of the traditional enzymolysis method; the enzymolysis efficiency is obviously improved. The present invention enables fatty acids to be obtained at a high conversion rate in a short time using a small amount of enzyme.
(2) The method for preparing fatty acid by directly carrying out enzymolysis reaction on the nigre and then carrying out high-temperature acidification is adopted, and the final fatty acid yield is obviously higher than that of a method for preparing fatty acid by firstly acidifying the nigre to prepare acidified oil and then carrying out high-temperature high-pressure hydrolysis. Meanwhile, the invention also avoids the defects of low quality and yield of the fatty acid product and high energy consumption caused by side reaction easily generated in the process of preparing the fatty acid by hydrolyzing the acidified oil at high temperature and high pressure.
(3) The preparation method provided by the invention is simple in process, energy-saving and environment-friendly, can obviously improve the yield of fatty acid compared with a soapstock acidification hydrolysis method, can greatly reduce the generation of high-acid wastewater, and has important economic benefits.
(4) The method makes full use of the byproduct nigre in the oil refining process, increases the utilization of the byproduct, and has great practical significance for improving the value of an industrial chain.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples. It should be noted that:
in the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end points of numerical values a and B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the term "optional" or "optional" is used to indicate that certain substances, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.
In the present specification, the term "plurality" means two or more than two unless otherwise specified.
Reference in the specification to "some specific/preferred embodiments," "other specific/preferred embodiments," "embodiments," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
< first aspect >
In a first aspect of the present invention, there is provided a method for producing a fatty acid, the method comprising:
a pretreatment step of contacting the soapstock with a first acid to obtain a pretreated soapstock, wherein the mass ratio of fat (calculated by glyceride and free fatty acid) to soap (calculated by sodium fatty acid) in the pretreated soapstock is (1);
an enzymolysis reaction step, in which the pretreated soapstock is contacted with hydrolase to carry out enzymolysis reaction to obtain an enzymolysis mixture; and
and an acidification reaction step, wherein the enzymolysis mixture obtained in the enzymolysis reaction step is contacted with a second acid for acidification reaction.
In the present invention, the fats are calculated by glyceride and free fatty acid, the soap is calculated by sodium fatty acid, and the contact system is a mixed system of soapstock and first acid.
Compared with the traditional enzymatic hydrolysis, the method controls the mass ratio of the fatty substances (counted by the total amount of glyceride and free fatty acid) to the soap (counted by sodium fatty acid) in the soapstock to be 1.15-0.55 by pretreating the soapstock, so that the enzyme dosage and the enzymolysis time in the enzymolysis reaction can be greatly reduced, and the enzymolysis can be carried out with high enzymolysis efficiency by using small enzyme dosage in a short time. In addition, the preparation method disclosed by the invention is simple in process, energy-saving and environment-friendly, can obviously improve the yield of fatty acid compared with the traditional soapstock acidification hydrolysis method, greatly reduces the generation of high-acid wastewater, and has important economic benefits.
(pretreatment step)
In some preferred embodiments of the present invention, the soapstock may comprise vegetable oil soapstock and/or animal oil soapstock. Specific examples thereof include: soybean oil soapstock, cotton seed oil soapstock, corn oil soapstock, rapeseed oil soapstock, sunflower oil soapstock, peanut oil soapstock, rice bran oil soapstock, lard oil soapstock, beef tallow soapstock, mutton tallow soapstock and the like. These may be used alone or in combination of two or more.
In some preferred embodiments of the present invention, it is preferred to control the moisture content of the soapstock in the range of 40 to 60%. When the moisture content of the soapstock is less than 40%, the soapstock is a semisolid system and is not suitable for operation. When the moisture content of the soapstock is more than 60%, the moisture content of the soapstock is too high, the total fat content is too low, and the industrial production of fatty acids using the soapstock is uneconomical.
In some preferred embodiments of the present invention, the soapstock is preferably heated to a temperature of 30-50 ℃ prior to contacting the soapstock with the first acid to better perform the enzymatic hydrolysis reaction described below.
In some preferred embodiments of the present invention, the first acid may be a strong acid having a pKa of less than 1 and/or a weak acid having a pKa of greater than 4.
Examples of strong acids having a pKa of less than 1 include: sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, and the like. These may be used alone or in combination of two or more.
Examples of weak acids having a pKa greater than 4 include: acetic acid, citric acid, propionic acid, butyric acid, valeric acid, sorbic acid, lactic acid, and the like. These may be used alone or in combination of two or more.
In the present invention, the pH of the contact system is adjusted to 6 to 7.5 by contacting the soapstock with the first acid, thereby providing a suitable reaction pH range for the enzymatic reaction described later. In the present invention, the first acid comprises a strong acid having a pKa of less than 1, and the strong acid having a pKa of less than 1, in addition to the function of adjusting the pH range of the contact system, may react with sodium fatty acid in the soapstock to generate fatty acid and sodium sulfate, and therefore, the strong acid having a pKa of less than 1 may also function to adjust the ratio of fatty matter (glyceride and free fatty acid) to soap (sodium fatty acid) in the soapstock, thereby controlling the ratio of fatty matter (glyceride and free fatty acid) to soap (sodium fatty acid) to 1.15 to 0.55 to promote the enzymatic reaction efficiency described later. Weak acids with pKa greater than 4 act to adjust the pH of the system.
Generally, the ratio of fatty matter to soap in the non-pretreated soapstock is generally about 1. By setting the ratio of the fatty material (in terms of glyceride and free fatty acid) to the soap (in terms of sodium fatty acid) within the above range, the amount of enzyme used and the time for enzymatic hydrolysis, which will be described later, can be significantly reduced. For example, the enzymolysis time of the invention can be greatly shortened from 24-36 h of the traditional enzymolysis method to 2-4 h, the enzymolysis efficiency is obviously improved, and the invention can prepare fatty acid with high conversion rate by using small amount of enzyme in short time. Under the same reaction time, the ratio of the fatty substances (calculated by glyceride and free fatty acid) to the soap (calculated by sodium fatty acid) in the pretreated soapstock is adopted, the subsequent enzymolysis reaction effect is obviously improved, and the conversion rate of the fatty acid is obviously improved.
In some preferred embodiments of the invention, the mass ratio of fatty matter (in terms of glycerides and free fatty acids) to total emulsifier (in terms of sodium fatty acid, phospholipids, etc.) in the pretreated soapstock is 1. By setting the ratio of the fats (in terms of glycerides and free fatty acids) to the total emulsifiers (in terms of sodium fatty acid, phospholipids, and the like) in the pretreated soapstock to the above range, the subsequent enzymatic hydrolysis efficiency can be improved even more. The total emulsifier is calculated by fatty acid sodium and phospholipid.
The amount of fatty matter (in glycerides and free fatty acids) in the soapstock was determined as follows: according to the determination rule of the production process of the LST1208-1992 vegetable oil 5.2.13 oil (soap) foot oil content determination, the content W1 of fatty substances in the soap foot is determined by adopting acetone extraction.
The soap content (in terms of sodium fatty acid) in the soapstock was determined by: adding strong acid into the soapstock for complete acidification, extracting with acetone to determine the total fatty acid content W2 in the soapstock, subtracting the fatty matter content W1 determined by the soapstock, and converting into the amount of fatty acid (W2-W1) converted from the sodium fatty acid in the soapstock. For example, sodium fatty acid mass = (W2-W1) × 304.44/282.46 in terms of sodium oleate.
The phospholipid content of the soapstock was determined as follows: drying the soapstock, performing microwave digestion, determining the phosphorus content in the soapstock by using ICP-OES, and converting into phospholipid content: phospholipid content = p × 26.31, p being the phosphorus content.
In some preferred embodiments of the present invention, the first acid is added in an amount of 1 to 3 mass%, preferably 1.5 to 2.5 mass%, relative to the total amount of the soapstock (soapstock before the pretreatment). By setting the content of the first acid in such a range, the ratio of the fatty matter (in terms of glycerides and free fatty acids) to the soap (in terms of sodium fatty acid) in the soapstock is controlled to be 1 to 0.15 to 1, and the pH of the contact system is controlled to be 6 to 7.5.
The method of contacting the soapstock with the first acid is not particularly limited, and a conventional contacting method such as a stirrer or a magnetic stirrer may be used.
The contact time and temperature are not particularly limited, and from the viewpoint of sufficient contact and controlling the mass ratio of fatty matter (in terms of glycerides and free fatty acids) to soap (in terms of sodium fatty acid) in the pretreated soapstock to be 1.15 to 0.55, it is preferable to slowly add the first acid to the soapstock at 30 to 50 ℃ and stir for 1 to 2 hours.
(enzymatic hydrolysis reaction step)
As the hydrolase, lipase; preferably, the hydrolase is a glycerol triester hydrolase and/or a partial glyceride hydrolase.
Examples of the hydrolase include: glycerin esterase enzymes derived from Thermomyces lanuginosus, candida antarctica, rhizomucor miehei, aspergillus niger, candida rugosa and Pseudomonas sp; partial glyceride hydrolase derived from Penicillium camembertii (Penicillium camembertii), penicillium circulans (Penicillium cyclopium), aspergillus oryzae (Aspergillus oryzae), and Malassezia globosa (Malassezia globosa), and the like. These hydrolases may be used alone in 1 kind or in combination of two or more kinds.
In some preferred embodiments of the present invention, the amount of the hydrolytic enzyme is 0.01 to 0.05 mass%, preferably 0.01 to 0.03 mass%, relative to the total amount of the soapstock (soapstock before pretreatment). By setting the amount of the hydrolase in such a range, the efficiency of the enzymatic hydrolysis can be improved and the cost of the enzyme can be reduced.
In the method, because the soapstock is pretreated, the ratio of the fatty substances (counted by glyceride and free fatty acid) to the soap (counted by sodium fatty acid) in the pretreated soapstock is 1.15-0.55, compared with the traditional method for hydrolyzing the soapstock by an enzyme method, the method can greatly reduce the dosage of hydrolase, can realize enzymolysis reaction with high enzymolysis efficiency by a small amount of hydrolase, and obviously reduces the enzyme cost.
In some preferred embodiments of the present invention, the enzymatic reaction time is preferably 2 to 4 hours, more preferably 2 to 3 hours. In the method, because the soapstock is pretreated, the ratio of the fat (calculated by glyceride and free fatty acid) to the soap (calculated by sodium fatty acid) in the pretreated soapstock is 1: 0.15-0.55, compared with the traditional method for hydrolyzing the soapstock by the enzyme method, the method can greatly shorten the enzymolysis time, can carry out enzymolysis reaction with high enzymolysis efficiency in short enzymolysis time, and has important economic benefits.
The temperature of the enzymatic hydrolysis is not particularly limited, and may be a temperature at which the enzyme is not inactivated, and from the viewpoint of sufficient reaction, it is preferable to react the pretreated soapstock with the hydrolase at 30 to 50 ℃.
The contact method of the pretreated soapstock and the hydrolytic enzyme is not particularly limited, and a conventional contact method such as a stirrer or a magnetic stirrer may be used.
(acidification reaction step)
In the acidification reaction process, the enzymolysis mixture obtained in the enzymolysis reaction process is contacted with second acid for acidification reaction.
In some preferred embodiments of the invention, the second acid preferably comprises a strong acid having a pKa of less than 1. Examples of strong acids having a pKa of less than 1 include: sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trichloroacetic acid, and the like. These acids may be used alone in 1 kind or in combination of two or more kinds.
In some preferred embodiments of the present invention, the second acid is used in an amount of 2 to 5 mass%, preferably 2.5 to 4 mass%, relative to the total amount of soapstock before pretreatment. By setting the amount of the second acid within such a range, the acidification reaction can be promoted to be effectively performed, the fatty acid can be obtained with high yield, and the layering speed is increased, so that the layering speed of the fatty acid oil phase and the aqueous phase is higher, and the industrial operation is facilitated.
The temperature and time of the acidification reaction are not particularly limited. In some preferred embodiments of the present invention, it is preferable to react the enzymatic mixture obtained in the above enzymatic reaction step with a second acid at 80 to 100 ℃ for 4 to 6 hours from the viewpoint of sufficient reaction.
In some other embodiments of the present invention, the manufacturing method of the present invention preferably further comprises a separation process after the acidification reaction process. The fatty acid is separated and recovered by a separation step.
The separation method is not particularly limited, and means such as centrifugation and separation may be used alone or in combination depending on the specific condition of the system after the actual contact.
In some embodiments of the present invention, the system after the acidification step may be centrifuged to separate the fatty acids from the mixed system obtained in the acidification step. More specifically, the mixed system obtained in the acidification reaction step is centrifuged to separate the oil phase and the aqueous phase, and the upper oil phase is separated to obtain the fatty acid.
In some embodiments of the invention, the centrifugation process may use a centrifuge to separate the above-described system to provide a system comprising an oil phase and an aqueous phase. The centrifugation conditions are not particularly limited, and for example, a centrifugation rate of 5000 to 10000rpm/min and a centrifugation time of 1 to 10min can be used.
In the production method of the present invention, the conversion rate of the soapstock (more specifically, glyceride in soapstock) into fatty acid is 90% or more, preferably 91% or more, more preferably 92% or more, and still more preferably 93% or more. Compared with the traditional method for preparing fatty acid from soapstock, the preparation method of the invention can obtain fatty acid with high conversion rate in a short time by using a small amount of hydrolase, and has important economic benefit.
< second aspect >
In a second aspect of the invention, the invention provides a fatty acid. The fatty acid of the present invention can be obtained by the method disclosed in < first aspect > of the present invention. The fatty acid obtained by the method has the characteristics of high quality and the like, and can be widely used in industries such as washing, medicine, food, textile printing and dyeing, daily chemical industry, petrochemical industry, rubber and plastic processing, mining, transportation, casting, metal processing, printing ink, paint, pigment and the like.
Examples
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The materials or apparatuses used are, unless otherwise specified, conventional products commercially available may be used.
Determination of the fatty matter content (in glycerides and free fatty acids) in the soapstock: the oil content of the oil (soapstock) foot is determined according to the determination rule of the production process of the LST1208-1992 vegetable oil 5.2.13, and the content of the fatty substances in the soapstock W1 is determined by adopting acetone extraction.
The method for detecting the content of the sodium aliphatate in the soapstock comprises the following steps: adding strong acid into the soapstock for complete acidification, and then, measuring the total fatty acid content W2 in the soapstock by acetone extraction and subtracting the fatty matter content W1 measured by the soapstock to obtain the fatty acid amount (W2-W1) converted from the sodium fatty acid in the soapstock, wherein the fatty acid amount is converted into the amount of the sodium fatty acid. For example, sodium fatty acid mass = (W2-W1) × 304.44/282.46 by sodium oleate.
And (3) measuring the content of phospholipid in the nigre: drying the soapstock, performing microwave digestion, determining the phosphorus content in the soapstock by using ICP-OES, and converting into phospholipid content: phospholipid content = p × 26.31, p being the phosphorus content.
Example 1
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 3g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at the speed of 200rpm, the pH value of a soapstock system is 6.0, and the mass ratio of fat to soap in the pretreated soapstock is 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 2g of 98% concentrated sulfuric acid is added, and the acidification reaction is carried out for 4 hours. After the reaction, centrifugal separation is carried out at 5000rpm, the content of triglyceride in the upper oil phase is 0.95 percent, the content of diglyceride is 1.11 percent and the content of monoglyceride is 0.79 percent through gas chromatography, the acid value of the oil phase is 192.39mgKOH/g through acid-base titration, and the conversion rate of the glyceride is 93.98 percent.
Example 2
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 2.5g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at the speed of 200rpm, the pH value of a soapstock system is 6.7, and the ratio of fat to soap in the pretreated soapstock is 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 2.5g of 98% concentrated sulfuric acid is added, and the acidification reaction is carried out for 4 hours. After the reaction, centrifugal separation was carried out at 5000rpm, and the content of triglyceride in the upper oil phase was 1.33%, the content of diglyceride was 1.10%, the content of monoglyceride was 0.74%, the acid value of the oil phase was 191.06mgKOH/g, and the conversion rate of glyceride was 93.31% as measured by gas chromatography.
Example 3
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 2g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at the speed of 200rpm, the pH value of a soapstock system is 7.1, and the ratio of fat to soap in the pretreated soapstock is 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 3g of 98% concentrated sulfuric acid is added, and the acidification reaction is carried out for 4 hours. After the reaction, centrifugal separation was carried out at 5000rpm, and the content of triglyceride in the upper oil phase was 1.43%, the content of diglyceride was 1.22%, and the content of monoglyceride was 0.62% as determined by gas chromatography, and the acid value of the oil phase was 190.33mgKOH/g and the conversion rate of glyceride was 93.10% as determined by acid-base titration.
Example 4
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 1.5g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at the speed of 200rpm, the pH value of a soapstock system is 7.5, and the ratio of fat to soap in the pretreated soapstock is 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 3.5g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 1.89% as determined by gas chromatography, the content of diglyceride is 1.31%, the content of monoglyceride is 1.04%, the acid value of the oil phase is 189.21mgKOH/g as determined by an acid-base titration method, and the conversion rate of the glyceride is 91.01%.
Comparative example 1
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 3g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at the speed of 200rpm, the pH value of a soapstock system is 6.0, 10g of oleic acid is simultaneously added, and the ratio of fat to soap in the soapstock is adjusted to be 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 2g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 11.64 percent, the content of diglyceride is 1.12 percent, the content of monoglyceride is 1.18 percent, the acid value of the oil phase is 168.34mgKOH/g and the conversion rate of the glyceride is 69.28 percent as measured by a gas chromatography.
Comparative example 2
100g of soybean oil soapstock with the water content of 53.5% is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 1g of 98% concentrated sulfuric acid is slowly added into the soybean oil soapstock, 2.5g of glacial acetic acid is added at the same time, the stirring is carried out for 2 hours at 200rpm, the pH value of a soapstock system is adjusted to be 6.0, and the ratio of fat to soap in the soapstock is 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 4g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 16.36 percent, the content of diglyceride is 1.42 percent, the content of monoglyceride is 1.05 percent, the acid value of the oil phase is 157.87mgKOH/g and the conversion rate of glyceride is 59.78 percent as measured by a gas-base titration method.
Comparative example 3
100g of soybean oil soapstock with the water content of 53.5% is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 5g of glacial acetic acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at 200rpm, the pH value of a soapstock system is adjusted to be 6.0, and the ratio of fat to soap in the soapstock is 1.15.
To the above-mentioned pretreated soapstock were added 0.01% of a triglyceride hydrolase Eversa 2.0 (manufactured by Novit, evera transform 2.0) and 0.01% of a partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 5g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 26.40% as determined by gas chromatography, the content of diglyceride is 2.37%, the content of monoglyceride is 1.84%, the acid value of the oil phase is 140.35mgKOH/g as determined by an acid-base titration method, and the conversion rate of the glyceride is 40.03%.
Comparative example 4
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 2g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at the speed of 200rpm, the pH value of a soapstock system is 7.1, 70g of oleic acid is simultaneously added, and the ratio of fat to soap in the soapstock is adjusted to be 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50) based on the total amount of soybean oil soapstock, respectively, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 2g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 16.44%, the content of diglyceride is 2.12%, the content of monoglyceride is 1.18%, the acid value of the oil phase is 162.23mgKOH/g and the conversion rate of the glyceride is 61.02% as measured by a gas chromatography.
Comparative example 5
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 1g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, 1.8g of glacial acetic acid is added at the same time, the stirring is carried out for 2 hours at the speed of 200rpm, the pH value of a soapstock system is adjusted to be 7.1, and the ratio of fat to soap in the soapstock is 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50) based on the total amount of soybean oil soapstock, respectively, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 4g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 20.45 percent, the content of diglyceride is 3.41 percent, the content of monoglyceride is 2.26 percent, the acid value of the oil phase is 151.34mgKOH/g and the conversion rate of the glyceride is 49.52 percent as measured by a gas chromatography.
Comparative example 6
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 3.2g of glacial acetic acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at 200rpm, the pH value of a soapstock system is adjusted to 7.1, and the ratio of fat to soap in the soapstock is 1.15.
To the above-mentioned pretreated soapstock were added 0.01% of a triglyceride hydrolase Eversa 2.0 (manufactured by Novit, evera transform 2.0) and 0.01% of a partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 5g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 28.45 percent, the content of diglyceride is 5.49 percent, the content of monoglyceride is 2.03 percent as measured by gas chromatography, the acid value of the oil phase is 134.15mgKOH/g as measured by an acid-base titration method, and the conversion rate of the glyceride is 31.80 percent.
Comparative example 7
100g of soybean oil soapstock with the water content of 53.5 percent is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at the temperature of 40 ℃, 3g of 98 percent concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at 200rpm, the pH value of a soapstock system is 6.0, 10g of oleic acid and 1.7g of lecithin PC are simultaneously added, the ratio of fat to total emulsifier in the soapstock system is adjusted to be 1.
To the pretreated soapstock were added 0.01% triglyceride hydrolase Eversa 2.0 (manufactured by Novexin, eversa transform 2.0) and 0.01% partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 2g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 10.75 percent, the content of diglyceride is 1.35 percent, the content of monoglyceride is 1.68 percent, the acid value of the oil phase is 170.21mgKOH/g and the conversion rate of the glyceride is 70.50 percent as measured by a gas-base chromatography.
Comparative example 8
100g of soybean oil soapstock with the water content of 53.5% is added into a 250mL conical flask, the conical flask is placed in a magnetic stirring water bath kettle at 40 ℃, 2g of 98% concentrated sulfuric acid is slowly added into the soybean oil soapstock, the stirring is carried out for 2 hours at 200rpm, the pH value of the soapstock system is 7.1, 70g of oleic acid and 35g of lecithin PC are simultaneously added, the ratio of fat to total emulsifier in the soapstock is adjusted to be 1.
To the above-mentioned pretreated soapstock were added 0.01% of a triglyceride hydrolase Eversa 2.0 (manufactured by Novit, evera transform 2.0) and 0.01% of a partial glyceride hydrolase G50 (manufactured by Tianye, amano G50), respectively, based on the total amount of soybean oil soapstock, and reacted for 2 hours.
After the enzymolysis reaction is finished, the temperature is raised to 85 ℃, 2g of 98% concentrated sulfuric acid is added, the acidification reaction is carried out for 4 hours, centrifugal separation is carried out at 5000rpm after the reaction is finished, the content of triglyceride in the upper oil phase is 25.21 percent, the content of diglyceride is 2.63 percent, the content of monoglyceride is 1.44 percent, the acid value of the oil phase is 143.01mgKOH/g and the conversion rate of the glyceride is 41.20 percent as measured by a gas-base titration method.
The pH of the contact system in the pretreatment step of examples 1 to 4 and comparative examples 1 to 8, the mass ratio of fatty material to soap in the pretreated soapstock, the mass ratio of fatty material to total emulsifier in the pretreated soapstock, the acid value of the obtained fatty acid, and the conversion rate of glycerin ester are shown in tables 1 to 2.
TABLE 1
TABLE 2
As can be seen from table 1, in examples 1 to 4, the ratio of the fatty material to the soap in the soapstock is adjusted to be in the range of 1.15 to 1. It can be seen that examples 1 to 4 can obtain fatty acids at a high glyceride conversion rate in a short time using a small amount of enzyme.
In contrast, in comparative examples 1 to 6, since the ratio of fatty material to soap in the soapstock was not in the range of 1.
In addition, although the prior art mentions that the addition of an emulsifier for fat and oil hydrolysis can increase the hydrolysis rate, in comparative examples 7 to 8, since the ratio of fatty matter to soap in soapstock is not in the range of 1.
Industrial applicability
The preparation method can greatly reduce the enzyme dosage in the enzymolysis reaction, and the enzyme cost is obviously reduced; the enzymolysis time can be greatly shortened to 2-4 h from 24-36 h of the traditional enzymolysis method; the enzymolysis efficiency is obviously improved. The present invention enables fatty acids to be obtained at a high conversion rate in a short time using a small amount of enzyme. In addition, the preparation method has simple process, energy conservation and environmental protection, can obviously improve the yield of the fatty acid compared with the soapstock acidification hydrolysis method, can greatly reduce the generation of high-acid wastewater, and has important economic benefit.
Claims (10)
1. A method for producing a fatty acid, comprising:
a pretreatment step of contacting the soapstock with a first acid to obtain a pretreated soapstock, wherein the mass ratio of fatty substances (calculated by glyceride and free fatty acid) to soap (calculated by sodium fatty acid) in the pretreated soapstock is 1;
an enzymolysis reaction process, namely contacting the pretreated soapstock with hydrolase to carry out enzymolysis reaction to obtain an enzymolysis mixture; and
and an acidification reaction step, wherein the enzymolysis mixture obtained in the enzymolysis reaction step is contacted with a second acid for acidification reaction.
2. The manufacturing method according to claim 1, wherein the soapstock comprises at least one selected from the group consisting of soybean oil soapstock, cottonseed oil soapstock, corn oil soapstock, rapeseed oil soapstock, sunflower oil soapstock, peanut oil soapstock, rice bran oil soapstock, lard soapstock, beef tallow soapstock and mutton oil soapstock;
preferably, the moisture content of the soapstock is 40-60%.
3. A method of manufacturing according to claim 1 or 2, characterized in that the first acid comprises a strong acid with a pKa of less than 1 and/or a weak acid with a pKa of more than 4;
preferably, the strong acid having a pKa of less than 1 comprises at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid and trichloroacetic acid;
the weak acid having a pKa of greater than 4 comprises at least one selected from the group consisting of acetic acid, citric acid, propionic acid, butyric acid, valeric acid, sorbic acid, and lactic acid.
4. The process according to any one of claims 1 to 3, wherein the mass ratio of fatty substances (in terms of glycerides and free fatty acids) to total emulsifier (in terms of soap and phospholipids) in the pretreated soapstock is 1.
5. The production method according to any one of claims 1 to 4, wherein the first acid is used in an amount of 1 to 3 mass% based on the total amount of the soapstock.
6. The production method according to any one of claims 1 to 5, wherein the hydrolase comprises a triglyceride hydrolase and/or a partial glyceride hydrolase;
preferably, the glycerol triester hydrolase comprises a glycerol triester hydrolase derived from at least one member of the group consisting of thermomyces lanuginosus, candida antarctica, rhizomucor miehei, aspergillus niger, candida rugosa, and pseudomonas;
the partial glyceride hydrolase includes partial glyceride hydrolase derived from at least one of the group consisting of Penicillium camemberti, penicillium circular arc, aspergillus oryzae and Malassezia globosa.
7. The process according to any one of claims 1 to 6, wherein the hydrolase is used in an amount of 0.01 to 0.05% by mass based on the total amount of the soapstock;
preferably, the pretreated soapstock and the hydrolase are subjected to an enzymolysis reaction at 30-50 ℃;
the time of the enzymolysis reaction is 2-4 h.
8. The production method according to any one of claims 1 to 7, wherein the second acid comprises a strong acid having a pKa of less than 1;
preferably, the second acid includes at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, and trichloroacetic acid;
preferably, the second acid is used in an amount of 2 to 5 mass% relative to the total amount of the soapstock;
preferably, the enzymatic hydrolysis mixture is reacted with the second acid at 80-100 ℃ for 4-6 h.
9. The method according to any one of claims 1 to 8, wherein the soapstock is heated to 30 to 50 ℃ before the pretreatment step.
10. A fatty acid obtained by the production method according to any one of claims 1 to 9.
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