CN114409719A - Method for extracting phytosterol from rice bran oil deodorizer distillate - Google Patents
Method for extracting phytosterol from rice bran oil deodorizer distillate Download PDFInfo
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- rice bran
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- 235000019774 Rice Bran oil Nutrition 0.000 title claims abstract description 47
- 239000008165 rice bran oil Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000003921 oil Substances 0.000 claims abstract description 54
- 235000019198 oils Nutrition 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 15
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 claims abstract description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 25
- 230000032050 esterification Effects 0.000 abstract description 21
- 239000003377 acid catalyst Substances 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 6
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 2
- 239000000194 fatty acid Substances 0.000 abstract description 2
- 229930195729 fatty acid Natural products 0.000 abstract description 2
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- 239000012071 phase Substances 0.000 abstract 5
- 239000008346 aqueous phase Substances 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 19
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 18
- 239000000376 reactant Substances 0.000 description 10
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 235000021588 free fatty acids Nutrition 0.000 description 8
- 238000004332 deodorization Methods 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 229930182558 Sterol Natural products 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 150000003432 sterols Chemical class 0.000 description 2
- 235000003702 sterols Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FPFSGDXIBUDDKZ-UHFFFAOYSA-N 3-decyl-2-hydroxycyclopent-2-en-1-one Chemical compound CCCCCCCCCCC1=C(O)C(=O)CC1 FPFSGDXIBUDDKZ-UHFFFAOYSA-N 0.000 description 1
- 240000002791 Brassica napus Species 0.000 description 1
- 235000004977 Brassica sinapistrum Nutrition 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000004367 Lipase Substances 0.000 description 1
- 102000004882 Lipase Human genes 0.000 description 1
- 108090001060 Lipase Proteins 0.000 description 1
- 229930003427 Vitamin E Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 235000019421 lipase Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J75/00—Processes for the preparation of steroids in general
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Steroid Compounds (AREA)
Abstract
The invention discloses a method for extracting phytosterol from rice bran oil deodorizer distillate, which comprises the following steps: adding the rice bran oil deodorized distillate and anhydrous methanol into a container, adding a catalyst, and placing in a constant-temperature water bath to stir and react for a period of time. After the reaction is finished, taking the upper oil phase, and repeatedly washing the upper oil phase with hot water until oil droplets are not entrained in the water phase after standing and layering. The aqueous phase was discharged, and the oil phase was dried over anhydrous sodium sulfate and crystallized by cooling. And filtering the oil phase after crystallization is finished, and obtaining a filter cake which is the phytosterol. The method adopts a novel heterogeneous acid catalyst, particularly ferric sulfate and ammonium ferric sulfate, to convert fatty acid in the deodorized distillate of the rice bran oil into fatty acid methyl ester, the esterification rate can reach 98.07 +/-0.23 percent, and methanol and the catalyst can be recovered from reaction products for recycling only by simple liquid separation and filtration operations, so that the cost is reduced, and the energy is saved and the environment is protected.
Description
Technical Field
The invention relates to the technical field of esterification of deodorized distillates, in particular to a method for extracting phytosterol from rice bran oil deodorized distillates.
Background
In the refining process of rice bran oil, the by-product separated from the deodorization procedure is called rice bran oil deodorization distillate, and mainly comprises phytosterol, tocopherol, free fatty acid, glyceride and the like. Due to the differences of raw materials (rapeseed, soybean or cottonseed), refining methods (chemical refining or physical refining) and process parameters, the properties, values and applications of deodorized distillates are different, but the deodorized distillates are high-quality raw materials for extracting phytosterol.
The physical and chemical properties of each component in the grease deodorization distillate are very close, so that the raw materials need to be pretreated by methods such as esterification, saponification, sulfation, ion exchange and the like, so as to expand the difference between the melting point, the boiling point, the adsorbability and the solubility of each component, and achieve the purposes of concentration and purification. Esterification can convert free fatty acid into fatty acid methyl ester, so that the boiling point difference between the fatty acid methyl ester and vitamin E reaches above 60 ℃, and simultaneously, the viscosity of the system is reduced, so that the phytosterol can be separated by cooling crystallization. Therefore, the esterification of the grease deodorized distillate is a key step for separating and purifying the phytosterol, and the conversion rate of free fatty acid in the esterification process directly influences the yield and the purity of the phytosterol.
Catalysts commonly used in the esterification step include acids, bases and enzymes. However, it has been found that lipase is very sensitive to methanol during the catalytic process, and therefore methanol in the reaction system should be kept at a relatively low concentration to ensure the activity of the enzyme. Obviously, acid catalysts and base catalysts are more suitable for industrial production than enzymes. The alkali catalyst can obtain fatty acid methyl ester with high purity and high yield in a short time (30-60 min), but has certain requirements on the content of free fatty acid in reactants. Generally, only refined vegetable oils with free fatty acid content less than 0.5% can be used as reactants of the base catalyst, and the presence of a large amount of free fatty acid will cause saponification, making the subsequent separation of the product difficult. And for the grease deodorized distillate with the free fatty acid content higher than 10%, the acid catalyst is a better choice. However, the traditional acid catalyst generally has strong corrosivity, high-cost stainless steel equipment is required in the industrial production process, and the traditional acid catalyst is difficult to recycle, so that the heterogeneous acid catalyst is considered to be used for catalyzing the esterification reaction of the grease deodorization distillate.
Disclosure of Invention
The invention aims to provide a method for extracting phytosterol from rice bran oil deodorized distillate, which not only has higher esterification rate and is convenient for the subsequent separation and purification of the phytosterol, but also can recover methanol and ferric sulfate (or ammonium ferric sulfate) from reaction products for recycling only by simple operation, thereby reducing the cost, saving energy and protecting the environment.
The specific technical scheme is as follows:
a method for extracting phytosterol from rice bran oil deodorizer distillate, comprising the steps of:
(1) adding the rice bran oil deodorized distillate and anhydrous methanol into a container, adding a catalyst, and placing in a constant-temperature water bath for reaction for a period of time;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing with hot water until oil droplets are not entrained in the water phase after standing and layering;
(3) discharging the water phase, drying the oil phase by using anhydrous sodium sulfate, cooling and crystallizing, and filtering the oil phase after crystallization is finished to obtain a filter cake, namely the phytosterol.
Preferably, in the step (1), the feed-liquid ratio of the rice bran oil deodorized distillate to the anhydrous methanol is 10: 1-1: 12 w/w.
Preferably, in the step (1), the catalyst is ferric sulfate, ammonium ferric sulfate or concentrated sulfuric acid.
Preferably, in the step (1), the addition amount of the catalyst is 1-15% of the total mass of the rice bran oil deodorized distillate and the anhydrous methanol.
Preferably, in the step (1), the reaction temperature is 55-70 ℃.
Preferably, in the step (1), the reaction time is 0.5-5.5 h.
Preferably, in the step (1), the reaction is carried out under stirring.
Preferably, in the step (2), the temperature of the hot water for repeated washing is 60 to 90 ℃.
Preferably, in the step (3), the cooling crystallization conditions are as follows: and (5) cooling and crystallizing for 12 hours in an environment at 0 ℃.
Preferably, after step (3), the phytosterol is purified by the following method: adding the phytosterol obtained in the step (3) into a mixed solvent obtained by mixing acetone-ethanol according to the volume ratio of 4: 1, treating for 1.5min by using 75W ultrasonic power, and then placing the solution in an environment with the temperature of 4 ℃ for crystal growth for 2h to obtain the purified phytosterol.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a novel multi-phase acid catalyst, particularly ferric sulfate and ammonium ferric sulfate, optimizes the types and dosage parameters of the additives aiming at the material composition of the rice bran oil deodorized distillate, efficiently converts fatty acid in the rice bran oil deodorized distillate into fatty acid methyl ester, and facilitates the subsequent separation and purification of phytosterol. Compared with the traditional catalyst, the novel catalyst has the characteristics of recycling, low corrosion resistance requirement of equipment and the like.
(2) The esterification rate obtained by the method can reach 98.07 +/-0.23 percent, and the subsequent separation and purification of the phytosterol are facilitated.
(3) The method can recycle methanol and ferric sulfate (or ammonium ferric sulfate) from reaction products for recycling through simple liquid separation and filtration operations, and achieves the purposes of saving energy and protecting environment while reducing cost.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, which are carried out in accordance with the technical solutions of the present invention and give detailed embodiments and operation procedures, but the scope of the present invention is not limited to the following examples. The experimental methods in the following examples, which are not specified under specific conditions, are generally performed under conventional conditions.
The free fatty acid content of the sample, calculated as oleic acid, was calculated as follows:
wherein, VKOHIs the volume of KOH solution consumed by titration (mL); cKOHIs the molar concentration (mol/L) of the KOH solution; m is the relative molecular mass of oleic acid; w is the mass (g) of the sample.
The esterification rate of the sample was calculated as follows:
in step (3) of all the following examples, part of the oil sample in step (2) was weighed and the esterification rate was calculated by the above-described method. Meanwhile, the rest mixed liquor in the step (2) is treated as follows:
and (3) discharging the water phase in the step (2), drying the oil phase by using anhydrous sodium sulfate, putting the dried oil phase into an environment with the temperature of 0 ℃, cooling and crystallizing for 12 hours, and filtering the oil phase after crystallization is finished to obtain a filter cake, namely a crude phytosterol product.
Example 1
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at a feed-liquid ratio of 1: 7.9(w/w) into a container, adding ferric sulfate catalyst corresponding to 8.6% (w/w) of reactant, and placing the container in a constant-temperature water bath at 65 ℃ to stir and react for 2.0 h;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing the upper oil phase with hot water at 60 ℃ until oil droplets are not entrained in the water phase after standing and layering; (3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so as to obtain the esterification rate of 98.07 +/-0.23%.
Example 2
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at a feed liquid ratio of 1: 10(w/w) into a container, adding concentrated sulfuric acid catalyst corresponding to 8% (w/w) of reactant, and placing the container in a constant temperature water bath at 65 ℃ to stir and react for 1.5 h;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing the upper oil phase with hot water at 60 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so that the esterification rate of 94.78 +/-0.90% is obtained.
Example 3
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at a feed liquid ratio of 1: 10(w/w) into a container, adding ferric ammonium sulfate catalyst corresponding to 8% (w/w) of reactant, and stirring the container in a constant temperature water bath at 65 deg.C for 1.5 h;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing the upper oil phase with hot water at 60 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so that the esterification rate of 88.78 +/-0.47% is obtained.
Example 4
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at a feed-liquid ratio of 1: 2(w/w) into a container, adding a ferric sulfate catalyst corresponding to 6% (w/w) of the reactant, and placing the container in a constant-temperature water bath at 65 ℃ to stir and react for 1.5 h;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing the upper oil phase with hot water at 60 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so that the esterification rate of 83.59 +/-0.64% is obtained.
Example 5
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at feed liquid ratio of 1: 12(w/w) into a container, adding ferric sulfate catalyst corresponding to 6% (w/w) of reactant, and placing the container in a constant temperature water bath at 65 deg.C for stirring reaction for 1.5 h;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing the upper oil phase with hot water at 60 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so that the esterification rate of the esterification reaction is 94.45 +/-0.23%.
Example 6
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at feed liquid ratio of 1: 6(w/w) into a container, adding ferric sulfate catalyst corresponding to 2% (w/w) of reactant, and placing the container in a constant temperature water bath at 65 deg.C for stirring reaction for 1.5 h;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing the upper oil phase with hot water at 60 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so that the esterification rate of 76.33 +/-0.87% is obtained.
Example 7
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at feed liquid ratio of 1: 6(w/w) into a container, adding ferric sulfate catalyst equivalent to 12% (w/w) of reactant, and placing the container in a constant temperature water bath at 65 deg.C for stirring reaction for 1.5 h;
(2) after the reaction is finished, taking the upper oil phase, repeatedly washing the upper oil phase with hot water at 90 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so that the esterification rate of 95.09 +/-0.52% is obtained.
Example 8
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at feed liquid ratio of 1: 6(w/w) into a container, adding 6% (w/w) ferric sulfate catalyst, and stirring the container in a constant temperature water bath at 65 deg.C for 0.5 hr;
(2) after the reaction is finished, taking the upper oil phase, repeatedly washing the upper oil phase with hot water at 90 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so that the esterification rate of the esterification reaction is 71.18 +/-0.86%.
Example 9
A method for extracting phytosterol from rice bran oil deodorizer distillate comprises the following specific steps:
(1) adding deodorized distillate of rice bran oil and anhydrous methanol at a feed-liquid ratio of 1: 6(w/w) into a container, adding a ferric sulfate catalyst corresponding to 6% (w/w) of the reactant, and placing the container in a constant-temperature water bath at 65 ℃ to stir and react for 3.0 h;
(2) after the reaction is finished, taking the upper oil phase, repeatedly washing the upper oil phase with hot water at 90 ℃ until oil droplets are not entrained in the water phase after standing and layering;
(3) weighing 2g of oil sample into a 150mL conical flask, adding 50mL of neutral diethyl ether-ethanol mixed solvent (2: 1, v/v), shaking to dissolve the sample, adding three drops of 1% phenolphthalein indicator, and titrating with 0.1mol/L potassium hydroxide solution until reddish color appears and no color change occurs within 30s, so as to obtain the esterification rate of 95.14 +/-0.55%.
As can be seen from the comparison of the above examples, when ferric sulfate is used as a catalyst, the feed-to-liquid ratio of the rice bran oil deodorized distillate to anhydrous methanol is 1: 7.9(w/w), the addition amount of the ferric sulfate catalyst is 8.6% (w/w), the reaction temperature is 65 ℃ and the reaction time is 2.2 hours, the esterification rate of the esterification reaction is up to 98.07 +/-0.23%, and the purity of the oil phase is 52.58 +/-1.16%, which is the filter cake obtained by standing, drying with anhydrous sodium sulfate, cooling, crystallizing and centrifuging and filtering. Further adopting acetone-ethanol mixed solvent (4: 1v/v) as crystallization solvent, treating with 75W ultrasonic power for 1.5min, placing the solution in refrigerator at 4 deg.C for crystal growth for 2h, wherein the purity of refined sterol is 96.81 + -1.39%, and the yield of sterol is 82.40 + -1.21%.
Claims (10)
1. A method for extracting phytosterol from rice bran oil deodorizer distillate is characterized by comprising the following steps:
(1) adding the rice bran oil deodorized distillate and anhydrous methanol into a container, adding a catalyst, and placing in a constant-temperature water bath for reaction for a period of time;
(2) after the reaction is finished, taking the upper oil phase, and repeatedly washing with hot water until oil droplets are not entrained in the water phase after standing and layering;
(3) discharging the water phase, drying the oil phase by using anhydrous sodium sulfate, cooling and crystallizing, and filtering the oil phase after crystallization is finished to obtain a filter cake, namely the phytosterol.
2. The method for extracting phytosterol from rice bran oil deodorizer distillate as claimed in claim 1, wherein in the step (1), the feed-to-liquid ratio of the rice bran oil deodorizer distillate to anhydrous methanol is 10: 1-1: 12 w/w.
3. The method for extracting phytosterol from rice bran oil deodorizer distillate as claimed in claim 1, wherein in step (1), the catalyst is ferric sulfate, ammonium ferric sulfate or concentrated sulfuric acid.
4. The method for extracting phytosterol from rice bran oil deodorizer distillate as claimed in claim 1, wherein in the step (1), the addition amount of the catalyst is 1-15% of the total mass of the rice bran oil deodorizer distillate and anhydrous methanol.
5. The method for extracting phytosterol from rice bran oil deodorizer distillate according to claim 1, wherein in the step (1), the reaction temperature is 55-70 ℃.
6. The method for extracting phytosterol from rice bran oil deodorizer distillate according to claim 1, wherein in the step (1), the reaction time is 0.5-5.5 h.
7. The method for extracting phytosterol from rice bran oil deodorizer distillate as claimed in claim 1, wherein in step (1), the reaction is carried out under stirring.
8. The method for extracting phytosterol from rice bran oil deodorizer distillate according to claim 1, wherein in the step (2), the temperature of hot water for repeated water washing is 60-90 ℃.
9. The method for extracting phytosterol from rice bran oil deodorizer distillate as claimed in claim 1, wherein in step (3), the cooling crystallization conditions are as follows: and (5) cooling and crystallizing for 12 hours in an environment at 0 ℃.
10. The method for extracting phytosterol from rice bran oil deodorizer distillate as claimed in claim 1, wherein after step (3), the phytosterol is further purified by the following method:
adding the phytosterol into a mixed solvent obtained by mixing acetone-ethanol according to the volume ratio of 4: 1, treating for 1.5min by using 75W of ultrasonic power, and then placing the solution in an environment with the temperature of 4 ℃ for crystal growing for 2h to obtain the purified phytosterol.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074217A (en) * | 1993-01-14 | 1993-07-14 | 清华大学 | From the vegetable oil refining by product, extract the novel process of vitamin-E and sterol |
| CN1263103A (en) * | 1999-11-19 | 2000-08-16 | 上海交通大学 | Supercritical fluid extraction method of high-purity sterol |
| CN1418877A (en) * | 2002-12-06 | 2003-05-21 | 武汉凯迪精细化工有限公司 | Process for extracting vitamin E from plant-oil debrominated distillate |
| CN101033243A (en) * | 2007-04-10 | 2007-09-12 | 山东理工大学 | Method of coproducting phytosterol, biological diesel oil and vitamin E |
| CN102824348A (en) * | 2012-03-13 | 2012-12-19 | 哈尔滨天通农业科技开发有限公司 | New technology for extracting sterol from corn germ oil deodorization distillate |
| CN102898491A (en) * | 2012-09-20 | 2013-01-30 | 浙江银河药业有限公司 | Preparation technology for extracting phytosterols from rice bran crude oil |
| CN103045664A (en) * | 2012-12-15 | 2013-04-17 | 华中科技大学 | Method for producing biodiesel, sterol and vitamin E from deodorized distillate |
| CN103497171A (en) * | 2013-10-15 | 2014-01-08 | 大丰市佳丰油脂有限责任公司 | Device and method for extracting V<E> (vitamin E) in enhanced manner by means of ultrasonically pre-treating deodorized and distilled products of plant oil |
| CN103708992A (en) * | 2013-12-27 | 2014-04-09 | 合肥工业大学 | Method for extracting squalene in vegetable oil deodorizer distillate through two-stage column chromatography |
| CN103804337A (en) * | 2012-11-12 | 2014-05-21 | 天津润亿生医药健康科技股份有限公司 | Novel technology for extracting vitamin E and squalene by employing multi-stage counter-current liquid-liquid extraction method |
| CN104046516A (en) * | 2014-07-03 | 2014-09-17 | 江苏大学 | Method for preparing biodiesel through esterification reaction of ultrasonic-assisted soybean oil deodorization distillate |
| CN105001297A (en) * | 2015-08-03 | 2015-10-28 | 刘火成 | Method for extracting phytosterol from plant pitch |
| CN106892791A (en) * | 2015-12-18 | 2017-06-27 | 中粮集团有限公司 | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application |
| CN107474093A (en) * | 2017-08-23 | 2017-12-15 | 福建省格兰尼生物工程股份有限公司 | A kind of deodorization distillate continuous production VE, sterol, methyl esters, glycerine, the method for squalene and high-boiling components |
| CN108299373A (en) * | 2018-05-07 | 2018-07-20 | 宜春大海龟生命科学有限公司 | The method that natural VE is extracted from rice bran oil deodorization distillate |
| CN111875659A (en) * | 2020-08-21 | 2020-11-03 | 宜春大海龟生命科学有限公司 | Method for purifying phytosterol |
| CN112300238A (en) * | 2020-09-23 | 2021-02-02 | 福建福迩金生物科技有限公司 | Method for extracting phytosterol from soybeans |
-
2022
- 2022-01-24 CN CN202210079102.1A patent/CN114409719B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074217A (en) * | 1993-01-14 | 1993-07-14 | 清华大学 | From the vegetable oil refining by product, extract the novel process of vitamin-E and sterol |
| CN1263103A (en) * | 1999-11-19 | 2000-08-16 | 上海交通大学 | Supercritical fluid extraction method of high-purity sterol |
| CN1418877A (en) * | 2002-12-06 | 2003-05-21 | 武汉凯迪精细化工有限公司 | Process for extracting vitamin E from plant-oil debrominated distillate |
| CN101033243A (en) * | 2007-04-10 | 2007-09-12 | 山东理工大学 | Method of coproducting phytosterol, biological diesel oil and vitamin E |
| CN102824348A (en) * | 2012-03-13 | 2012-12-19 | 哈尔滨天通农业科技开发有限公司 | New technology for extracting sterol from corn germ oil deodorization distillate |
| CN102898491A (en) * | 2012-09-20 | 2013-01-30 | 浙江银河药业有限公司 | Preparation technology for extracting phytosterols from rice bran crude oil |
| CN103804337A (en) * | 2012-11-12 | 2014-05-21 | 天津润亿生医药健康科技股份有限公司 | Novel technology for extracting vitamin E and squalene by employing multi-stage counter-current liquid-liquid extraction method |
| CN103045664A (en) * | 2012-12-15 | 2013-04-17 | 华中科技大学 | Method for producing biodiesel, sterol and vitamin E from deodorized distillate |
| CN103497171A (en) * | 2013-10-15 | 2014-01-08 | 大丰市佳丰油脂有限责任公司 | Device and method for extracting V<E> (vitamin E) in enhanced manner by means of ultrasonically pre-treating deodorized and distilled products of plant oil |
| CN103708992A (en) * | 2013-12-27 | 2014-04-09 | 合肥工业大学 | Method for extracting squalene in vegetable oil deodorizer distillate through two-stage column chromatography |
| CN104046516A (en) * | 2014-07-03 | 2014-09-17 | 江苏大学 | Method for preparing biodiesel through esterification reaction of ultrasonic-assisted soybean oil deodorization distillate |
| CN105001297A (en) * | 2015-08-03 | 2015-10-28 | 刘火成 | Method for extracting phytosterol from plant pitch |
| CN106892791A (en) * | 2015-12-18 | 2017-06-27 | 中粮集团有限公司 | Extract method and the medicine containing squalene of plant source spiny dogfish ene compositions and its preparation method and application |
| CN107474093A (en) * | 2017-08-23 | 2017-12-15 | 福建省格兰尼生物工程股份有限公司 | A kind of deodorization distillate continuous production VE, sterol, methyl esters, glycerine, the method for squalene and high-boiling components |
| CN108299373A (en) * | 2018-05-07 | 2018-07-20 | 宜春大海龟生命科学有限公司 | The method that natural VE is extracted from rice bran oil deodorization distillate |
| WO2019214422A1 (en) * | 2018-05-07 | 2019-11-14 | 宜春大海龟生命科学有限公司 | Method for extracting natural vitamin e from deodorized distillate of rice bran oil |
| CN111875659A (en) * | 2020-08-21 | 2020-11-03 | 宜春大海龟生命科学有限公司 | Method for purifying phytosterol |
| CN112300238A (en) * | 2020-09-23 | 2021-02-02 | 福建福迩金生物科技有限公司 | Method for extracting phytosterol from soybeans |
Non-Patent Citations (6)
| Title |
|---|
| 张莉华等: "油脂加工副产物—脱臭馏出物的综合利用", 《中国食品添加剂》, 15 January 2015 (2015-01-15), pages 157 - 163 * |
| 彭团儿等: "米糠油脱臭馏出物乙酯化工艺条件研究", 《粮油加工》 * |
| 彭团儿等: "米糠油脱臭馏出物乙酯化工艺条件研究", 《粮油加工》, 8 April 2009 (2009-04-08), pages 48 - 51 * |
| 许文林等: "脱臭馏出物中植物甾醇回收的技术经济分析", 《化学工业与工程》 * |
| 许文林等: "脱臭馏出物中植物甾醇回收的技术经济分析", 《化学工业与工程》, 31 August 2002 (2002-08-31), pages 335 - 339 * |
| 赵文军著: "《餐厨垃圾资源化技术研究》", 黑龙江大学出版社, pages: 13 - 14 * |
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