CN114605256A - Extraction method of fish oil intermediate EPA70 - Google Patents
Extraction method of fish oil intermediate EPA70 Download PDFInfo
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- CN114605256A CN114605256A CN202210243893.7A CN202210243893A CN114605256A CN 114605256 A CN114605256 A CN 114605256A CN 202210243893 A CN202210243893 A CN 202210243893A CN 114605256 A CN114605256 A CN 114605256A
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- 235000021323 fish oil Nutrition 0.000 title claims abstract description 64
- 238000000605 extraction Methods 0.000 title claims abstract description 21
- 238000000199 molecular distillation Methods 0.000 claims abstract description 33
- 239000012159 carrier gas Substances 0.000 claims abstract description 25
- 238000004821 distillation Methods 0.000 claims description 87
- 238000010992 reflux Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 9
- 238000005886 esterification reaction Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 abstract description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 abstract description 2
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 66
- JAZBEHYOTPTENJ-JLNKQSITSA-N all-cis-5,8,11,14,17-icosapentaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O JAZBEHYOTPTENJ-JLNKQSITSA-N 0.000 description 55
- 235000020673 eicosapentaenoic acid Nutrition 0.000 description 55
- 229960005135 eicosapentaenoic acid Drugs 0.000 description 55
- JAZBEHYOTPTENJ-UHFFFAOYSA-N eicosapentaenoic acid Natural products CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O JAZBEHYOTPTENJ-UHFFFAOYSA-N 0.000 description 55
- 235000020669 docosahexaenoic acid Nutrition 0.000 description 34
- 229940090949 docosahexaenoic acid Drugs 0.000 description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 5
- 125000004494 ethyl ester group Chemical group 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000000194 supercritical-fluid extraction Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 3
- 229920000064 Ethyl eicosapentaenoic acid Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 235000013402 health food Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DVSZKTAMJJTWFG-SKCDLICFSA-N (2e,4e,6e,8e,10e,12e)-docosa-2,4,6,8,10,12-hexaenoic acid Chemical compound CCCCCCCCC\C=C\C=C\C=C\C=C\C=C\C=C\C(O)=O DVSZKTAMJJTWFG-SKCDLICFSA-N 0.000 description 1
- GZJLLYHBALOKEX-UHFFFAOYSA-N 6-Ketone, O18-Me-Ussuriedine Natural products CC=CCC=CCC=CCC=CCC=CCC=CCCCC(O)=O GZJLLYHBALOKEX-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 201000001320 Atherosclerosis Diseases 0.000 description 1
- 206010008132 Cerebral thrombosis Diseases 0.000 description 1
- 206010020772 Hypertension Diseases 0.000 description 1
- 201000001429 Intracranial Thrombosis Diseases 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000004641 brain development Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- KAUVQQXNCKESLC-UHFFFAOYSA-N docosahexaenoic acid (DHA) Natural products COC(=O)C(C)NOCC1=CC=CC=C1 KAUVQQXNCKESLC-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- DTMGIJFHGGCSLO-FIAQIACWSA-N ethyl (4z,7z,10z,13z,16z,19z)-docosa-4,7,10,13,16,19-hexaenoate;ethyl (5z,8z,11z,14z,17z)-icosa-5,8,11,14,17-pentaenoate Chemical class CCOC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC.CCOC(=O)CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC DTMGIJFHGGCSLO-FIAQIACWSA-N 0.000 description 1
- SSQPWTVBQMWLSZ-AAQCHOMXSA-N ethyl (5Z,8Z,11Z,14Z,17Z)-icosapentaenoate Chemical compound CCOC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CC SSQPWTVBQMWLSZ-AAQCHOMXSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 210000003754 fetus Anatomy 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 208000006575 hypertriglyceridemia Diseases 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000021281 monounsaturated fatty acids Nutrition 0.000 description 1
- 235000020660 omega-3 fatty acid Nutrition 0.000 description 1
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 230000002207 retinal effect Effects 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- -1 urea fatty acid Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of purification of marine unsaturated fatty acid, and provides an extraction method of a fish oil intermediate EPA 70. The extraction method provided by the invention has the advantages that the ethylated fish oil is preheated to 120-170 ℃, primary steam stripping rectification is carried out under the carrying of carrier gas at 210-260 ℃, C14-C16 in the ethylated fish oil can be removed, and the EPA content in the obtained first heavy component reaches 40-50% by mass; heating the first heavy component to 170-180 ℃, carrying out secondary steam stripping rectification under the carrying of carrier gas at 210-260 ℃, and removing C18-C20 in the second heavy component, wherein the EPA mass content in the obtained second heavy component is more than or equal to 65%; carrying out six-stage molecular distillation to optimize the proportion of EPA and DHA, and finally obtaining EPA70, wherein the EPA mass content is more than or equal to 70%; meanwhile, the total mass content of EPA and DHA is 74-83%.
Description
Technical Field
The invention relates to the technical field of purification of marine unsaturated fatty acid, in particular to an extraction method of a fish oil intermediate EPA 70.
Background
Marine fish oil is the best source for preparing high-purity polyunsaturated fatty acids, two active ingredients of which are eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). EPA can prevent atherosclerosis, cerebral thrombosis and hypertension, and especially has good therapeutic effect on hypertriglyceridemia; DHA can promote brain development of fetus and infant, improve memory of teenagers, improve retinal reflex, inhibit vision deterioration, and prevent and treat senile dementia. However, the human body cannot synthesize these two fatty acids by itself, and must ingest them from the outside, and fish oil is the main source of ingestion from the outside. At present, fish oil is mainly classified into fish oil for health food and pharmaceutical grade fish oil. The content of EPA and DHA in the fish oil for the health food is less than 75 percent; the pharmaceutical-grade fish oil has higher purity, the content of EPA and DHA is more than 80%, and the content of total Omega-3 polyunsaturated fatty acid containing EPA and DHA is more than 90%. The pharmaceutical-grade fish oil mainly comprises domestic polyenoic acid ethyl ester (EPA + DHA is more than or equal to 84 percent) and foreign Omega-3-acid ethyl esters 90.
In recent years, pure EPA products, which are continuously increasing in market sales, are first marketed in japan in 2012, in the united states, and in europe in 2021, and it is expected that in 2022, the drug will be marketed in china, at which time the amount of pure EPA products sold in the world will increase dramatically.
The EPA pure product is prepared from eicosapentaenoic acid (EPA) ethyl ester, and EPA70 (the content of EPA is more than or equal to 70%) is an intermediate for preparing EPA ethyl ester. In the prior art, the method for preparing EPA70 mainly comprises the following steps: urea inclusion method and supercritical fluid extraction technology. The urea inclusion method comprises the following steps: after the fish oil is esterified by ethyl, most of saturated fatty acid and monounsaturated fatty acid are removed by a urea inclusion method, and the EPA/DHA ratio is optimized by molecular distillation, so that the EPA70 is obtained. In the process, the consumption of urea and solvent is high, the process steps are multiple, ammonia nitrogen wastewater and urea fatty acid solid waste residue which are difficult to treat are generated in the production process, and the environment-friendly pressure is higher. For the supercritical fluid extraction technology, research shows that when the content of EPA + DHA in the raw materials is 40%, the supercritical fluid extraction technology and the molecular distillation separation result are similar, the total content of EPA + DHA is difficult to reach more than 70%, the equipment investment is large, the reflux amount in the extraction process is large, the weight ratio of the separated sample to the used supercritical carbon dioxide is close to 1: 1000, the amount of supercritical carbon dioxide used is too large to be suitable for industrialization. Although the total content of EPA + DHA in the mixture obtained by the supercritical fluid extraction technology can reach more than 90% by silver ion complexation and silver ion silica gel column chromatography technology, the silver ion is expensive, and the silver ion is difficult to recover, so that the method is not suitable for industrial application.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for extracting fish oil intermediate EPA 70. The extraction method provided by the invention is simple to operate, does not use a solvent, is low in cost and is suitable for industrialization.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an extraction method of a fish oil intermediate EPA70, which comprises the following steps:
preheating the ethylated fish oil, and performing primary steam stripping rectification to obtain a first heavy component;
preheating the first heavy component, and performing secondary steam stripping rectification to obtain a second heavy component;
subjecting said second heavy component to multi-stage molecular distillation to obtain said fish oil intermediate EPA 70;
preheating the ethyl esterification fish oil at the temperature of 120-170 ℃;
the preheating temperature of the first heavy component is 170-180 ℃;
the temperature of the carrier gas of the primary steam stripping rectification and the temperature of the carrier gas of the secondary steam stripping rectification are 210-260 ℃ independently;
the number of stages of the multi-stage molecular distillation is more than or equal to 6 stages.
Preferably, the weight content of EPA in the ethyl esterification fish oil is more than or equal to 18 percent, and the weight content of DHA in the ethyl esterification fish oil is less than or equal to 6 percent.
Preferably, in the primary stripping and rectifying process, the feeding flow of the ethylated fish oil is 50-60L/h.
Preferably, the vacuum degrees of the primary stripping rectification and the secondary stripping rectification are independently 3-6 kPa.
Preferably, the first-stage stripping rectification also obtains a first light component; the reflux ratio of the first light component is 0.5-1.
Preferably, the reflux temperature of the first light component is 100-120 ℃; the reflux flow rate of the first light component is 25-35L/h.
Preferably, in the secondary stripping and rectifying process, the feeding flow of the first heavy component is 22-30L/h.
Preferably, the second-stage stripping rectification also obtains a second light component; the reflux ratio of the second light component is 0.5-1.
Preferably, the reflux temperature of the second light component is 130-140 ℃; and the reflux flow rate of the second light component is 13-20L/h.
Preferably, the multistage molecular distillation six-stage molecular distillation comprises sequentially performing a first distillation, a second distillation, a third distillation, a fourth distillation, a fifth distillation, and a sixth distillation; the temperature of the first distillation is 80-100 ℃, the temperature of the second distillation is 110-120 ℃, the temperature of the third distillation is 115-125 ℃, the temperature of the fourth distillation is 130-140 ℃, the temperature of the fifth distillation is 150-160 ℃, and the temperature of the sixth distillation is 160-175 ℃.
The invention provides an extraction method of a fish oil intermediate EPA70, which comprises the following steps: preheating the ethylated fish oil, and performing primary steam stripping rectification to obtain a first heavy component; preheating the first heavy component, and performing secondary steam stripping rectification to obtain a second heavy component; subjecting the second heavy component to multi-stage molecular distillation to obtain the fish oil intermediate EPA 70; preheating the ethyl esterification fish oil at the temperature of 120-170 ℃; the preheating temperature of the first heavy component is 170-180 ℃; the temperature of the carrier gas of the primary steam stripping rectification and the temperature of the carrier gas of the secondary steam stripping rectification are 210-260 ℃ independently; the number of stages of the multi-stage molecular distillation is more than or equal to 6 stages. The method comprises the steps of preheating the ethylated fish oil to 120-170 ℃, carrying out primary steam stripping rectification under the carrying of carrier gas at 210-260 ℃, removing C14-C16 components in the ethylated fish oil, and enabling the EPA mass content in the obtained first heavy component to reach 40-50%; heating the first heavy component to 170-180 ℃, carrying out secondary stripping rectification under the carrying of carrier gas at 210-260 ℃, and removing C18-C20 in the second heavy component, wherein the EPA content in the obtained second heavy component is more than or equal to 65% by mass; then, the proportion of EPA and DHA is optimized through multi-stage molecular distillation, and finally the EPA70 is obtained, wherein the EPA mass content is more than or equal to 70%; meanwhile, the total mass content of EPA and DHA is 74-83%. The invention adopts the first-stage steam stripping rectification and the second-stage steam stripping rectification, does not use solvent, has low cost and simple operation, and is suitable for industrial production.
Detailed Description
The invention provides an extraction method of a fish oil intermediate EPA70, which comprises the following steps:
preheating the ethylated fish oil, and performing primary steam stripping rectification to obtain a first heavy component;
preheating the first heavy component, and performing secondary steam stripping rectification to obtain a second heavy component;
subjecting said second heavy component to multi-stage molecular distillation to obtain said fish oil intermediate EPA 70;
preheating the ethyl esterification fish oil at 120-170 ℃;
the preheating temperature of the first heavy component is 170-180 ℃;
the temperature of the carrier gas of the first-stage steam stripping rectification and the temperature of the carrier gas of the second-stage steam stripping rectification are 210-260 ℃ independently;
the number of stages of the multi-stage molecular distillation is more than or equal to 6 stages.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
According to the invention, the first heavy component is obtained by preheating the ethylated fish oil and then carrying out first-stage steam stripping rectification.
In the invention, the weight content of EPA in the ethyl esterification fish oil is preferably more than or equal to 18 percent, and the weight content of DHA in the ethyl esterification fish oil is preferably less than or equal to 6 percent. In the invention, the ethylated fish oil is preferably obtained by performing acid ester exchange on the coarse fish oil and absolute ethyl alcohol, or performing alkali ester exchange on the coarse fish oil and the absolute ethyl alcohol, or is an ethylated fish oil fraction generated in a fish oil production process.
In the invention, the preheating temperature of the ethyl esterification fish oil is 120-170 ℃, preferably 130-165 ℃ and further preferably 150-160 ℃.
In the invention, the temperature of the carrier gas of the first-stage stripping rectification is 210-260 ℃, preferably 220-250 ℃, and further preferably 230-240 ℃. In the invention, the flow of the carrier gas of the primary stripping rectification is preferably 1500-1700 m3H, more preferably 1600m3/h。
In the invention, in the primary stripping and rectifying process, the feeding flow rate of the ethylated fish oil is preferably 50-60L/h, more preferably 52-58L/h, and even more preferably 54-56L/h.
In the invention, the vacuum degree of the primary stripping rectification is preferably 3-6 kPa, and more preferably 4-5 kPa.
After the first-stage stripping rectification, the first light component is preferably obtained. In the present invention, the first lights are preferably refluxed to the first stripping distillation. In the present invention, the reflux ratio of the first light component is preferably 0.5 to 1, more preferably 0.6 to 0.9, and still more preferably 0.7 to 0.8. In the invention, the reflux temperature of the first light component is preferably 100-120 ℃, more preferably 105-115 ℃, and even more preferably 110 ℃. In the invention, the reflux flow rate of the first light component is preferably 25-35L/h, more preferably 27-33L/h, and more preferably 29-31L/h.
In the invention, the first-stage stripping rectification can remove C14-C16 components in the ethylated fish oil, and the EPA mass content in the obtained first heavy component reaches 40-50%. Further, the obtained first light component is refluxed, so that the yield of the first heavy component is improved, and the yield of EPA is further improved.
After the first heavy component is obtained, the invention preheats the first heavy component and carries out secondary steam stripping rectification to obtain the second heavy component.
In the invention, the preheating temperature of the first heavy component is 170-180 ℃, more preferably 172-178 ℃, and still more preferably 174-176 ℃.
In the invention, the temperature of the carrier gas of the secondary stripping rectification is 210-260 ℃, preferably 220-250 ℃, and further preferably 230-240 ℃. In the invention, the flow of the carrier gas for the secondary stripping rectification is preferably 1300-1500 m3H, more preferably 1400m3/h。
In the invention, in the process of the secondary stripping and rectification, the feeding flow rate of the first heavy component is preferably 22-30L/h, more preferably 24-28L/h, and even more preferably 25-26L/h.
In the invention, the vacuum degree of the secondary stripping rectification is preferably 3-6 kPa, and more preferably 4-5 kPa.
After the second-stage stripping rectification, a second light component is preferably obtained. In the present invention, the second lights are preferably refluxed to the secondary stripping distillation. In the present invention, the reflux ratio of the second light component is preferably 0.5 to 1, more preferably 0.6 to 0.9, and still more preferably 0.7 to 0.8. In the invention, the reflux temperature of the second light component is preferably 130-140 ℃, and more preferably 133-138 ℃. In the invention, the reflux flow rate of the second light component is preferably 13-20L/h, and more preferably 14-17L/h.
In the invention, the first heavy component is heated to 170-180 ℃, and the second stripping rectification is carried out under the carrying of carrier gas at 210-260 ℃, so that C18-C20 in the second heavy component can be removed, and the EPA mass content in the obtained second heavy component is more than or equal to 65%. Further, the reflux of the obtained second light component improves the yield of the second heavy component, thereby improving the yield of EPA.
After the second heavy component is obtained, the invention carries out multi-stage molecular distillation on the second heavy component to obtain the fish oil intermediate EPA 70.
In the present invention, the number of stages of the multistage molecular distillation is not less than 6, and six-stage molecular distillation or seven-stage molecular distillation is particularly preferable. In the present invention, the six-stage molecular distillation preferably comprises sequentially performing a first distillation, a second distillation, a third distillation, a fourth distillation, a fifth distillation and a sixth distillation. In the invention, the temperature of the first distillation is 80-100 ℃, and more preferably 85-95 ℃. In the present invention, the temperature of the second distillation is 110 to 120 ℃, and more preferably 113 to 118 ℃. In the invention, the temperature of the third distillation is 115-125 ℃, and more preferably 120-125 ℃. In the present invention, the temperature of the fourth distillation is 130 to 140 ℃, and more preferably 133 to 138 ℃. In the invention, the temperature of the fifth distillation is 150-160 ℃, and more preferably 155-160 ℃. In the invention, the temperature of the sixth distillation is 160-175 ℃, and more preferably 165-175 ℃.
In the present invention, the seven-stage molecular distillation preferably includes a first distillation, a second distillation, a third distillation, a fourth distillation, a fifth distillation, a sixth distillation and a seventh distillation, which are sequentially performed. In the invention, the temperature of the first distillation is 80-100 ℃, and more preferably 85-95 ℃. In the present invention, the temperature of the second distillation is 110 to 120 ℃, and more preferably 113 to 118 ℃. In the invention, the temperature of the third distillation is 115-125 ℃, and more preferably 120-125 ℃. In the present invention, the temperature of the fourth distillation is 130 to 140 ℃, and more preferably 133 to 138 ℃. In the invention, the temperature of the fifth distillation is 150-160 ℃, and more preferably 155-160 ℃. In the invention, the temperature of the sixth distillation is 160-175 ℃. Further preferably 165 to 175 ℃. In the invention, the temperature of the seventh distillation is preferably 168-178 ℃, and more preferably 170-175 ℃.
In the present invention, the multistage molecular distillation is preferably carried out in a short path molecular distillation column.
According to the invention, the obtained second heavy component is subjected to multi-stage molecular distillation to optimize the proportion of EPA and DHA, and finally the EPA70 is obtained, wherein the EPA mass content is more than or equal to 70%; meanwhile, the total mass content of EPA and DHA is 74-83%.
The following examples are provided to illustrate the extraction method of the fish oil intermediate EPA70 provided in the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking the crude fish oil with the EPA/DHA mass content of 21% and 5%, adding 0.8 weight part of absolute ethanol and 0.002 weight part of concentrated sulfuric acid, reacting at 80 ℃ for 20 hours, and evaporating to remove excessive ethanol to obtain the ethylated fish oil; the method comprises the steps of preheating the ethylated fish oil to 165 ℃, feeding the ethylated fish oil into a first rectifying tower at a rate of 56L/h for primary steam stripping rectification, wherein the preheating temperature of carrier gas nitrogen of the primary steam stripping rectification is 250 ℃, and the flow rate of the nitrogen is 1600m3And/h, the vacuum degree is 5kPa, the tower top temperature of the first rectifying tower is measured to be 142 ℃ in the primary steam stripping and rectifying process, a first heavy component and a first light component are obtained, the first light component reflows to the first rectifying tower for primary steam stripping and rectifying, the reflow flow is 30L/h, and the reflow temperature is 115 ℃. In the first heavy component, the content of EPA is 41% by mass and the content of DHA is 10% by mass.
Preheating the obtained first heavy component to 170 ℃, and feeding the first heavy component into a second rectifying tower at a rate of 24L/h for secondary steam stripping rectification, wherein the preheating temperature of carrier gas nitrogen for the secondary steam stripping rectification is 250 ℃, and the flow rate of the nitrogen is 1400m3H, the vacuum degree is 5 kPa; in the process of secondary steam stripping rectification, the tower top temperature of the second rectifying tower is measured to be 151 ℃, and a second heavy component and a second light component are obtained; and refluxing the second light component to a second rectifying tower for secondary stripping rectification, wherein the reflux temperature is 135 ℃, and the reflux flow is 14L/h. In the second heavy component, the content of EPA by mass is 65% and the content of DHA by mass is 15%.
The second heavy component obtained was subjected to 6-stage molecular distillation, the temperature of the first distillation was 90 ℃, the temperature of the second distillation was 115 ℃, the temperature of the third distillation was 123 ℃, the temperature of the fourth distillation was 135 ℃, the temperature of the fifth distillation was 156 ℃ and the temperature of the sixth distillation was 170 ℃, and a fraction of EPA70 was collected, wherein the EPA content by mass was 70%, the DHA content by mass was 11% and the EPA70 yield was 75%.
Example 2
Taking fish oil ethyl ester fractions with EPA/DHA mass content of 25% and 4%, respectively, heating the fish oil ethyl ester fractions to 164 deg.C, introducing into a first rectifying tower at 55L/h for primary stripping rectification, preheating carrier gas nitrogen at 250 deg.C, and nitrogen flow at 1600m3And/h, the vacuum degree is 5kPa, the tower top temperature of the first rectifying tower is 143 ℃ in the primary stripping and rectifying process, a first heavy component and a first light component are obtained, the first light component reflows to the first rectifying tower for primary stripping and rectifying, the reflow flow is 32L/h, and the reflow temperature is 115 ℃. In the first heavy component, the content of EPA by mass is 46% and the content of DHA by mass is 7%.
Preheating the obtained first heavy component to 171 ℃, and feeding the first heavy component into a second rectifying tower at a rate of 23L/h for secondary steam stripping rectification, wherein the preheating temperature of carrier gas nitrogen for the secondary steam stripping rectification is 250 ℃, and the flow rate of the nitrogen is 1400m3H, the vacuum degree is 5 kPa; in the process of the second-stage stripping rectification, the tower top temperature of the second rectifying tower is measured to be 153 ℃, and a second heavy component and a second light component are obtained; and refluxing the second light component to a second rectifying tower for secondary stripping rectification, wherein the reflux temperature is 134 ℃, and the reflux flow is 15L/h. In the second heavy component, the content of EPA by mass is 68% and the content of DHA by mass is 11%.
The second heavy component obtained was subjected to 6-stage molecular distillation at a temperature of 90 ℃ for the first distillation, 113 ℃ for the second distillation, 121 ℃ for the third distillation, 133 ℃ for the fourth distillation, 154 ℃ for the fifth distillation and 170 ℃ for the sixth distillation, and EPA70 fractions were collected, with a EPA content by mass of 71%, a DHA content by mass of 10% and an EPA70 yield of 81%.
Example 3
Taking the crude fish oil with the EPA/DHA mass content of 21% and 5%, adding 0.8 weight part of absolute ethanol and 0.002 weight part of concentrated sulfuric acid, reacting at 80 ℃ for 20 hours, and evaporating to remove excessive ethanol to obtain the ethylated fish oil; the method comprises the steps of preheating the ethylated fish oil to 165 ℃, feeding the ethylated fish oil into a first rectifying tower at a rate of 54L/h for primary steam stripping rectification, wherein the preheating temperature of carrier gas nitrogen of the primary steam stripping rectification is 250 ℃, and the flow rate of the nitrogen is 1600m3And/h, the vacuum degree is 5kPa, the tower top temperature of the first rectifying tower is measured to be 142 ℃ in the primary steam stripping and rectifying process, a first heavy component and a first light component are obtained, the first light component reflows to the first rectifying tower for primary steam stripping and rectifying, the reflow flow is 29L/h, and the reflow temperature is 115 ℃. In the first heavy component, the content of EPA by mass is 42% and the content of DHA by mass is 11%.
Preheating the obtained first heavy component to 175 ℃, and feeding the first heavy component into a second rectifying tower at a rate of 24L/h for secondary steam stripping rectification, wherein the preheating temperature of carrier gas nitrogen for the secondary steam stripping rectification is 250 ℃, and the vacuum degree is 5 kPa; in the process of the second-stage stripping rectification, the tower top temperature of the second rectifying tower is measured to be 154 ℃, and the flow rate of nitrogen is 1400m3H, obtaining a second heavy component and a second light component; and refluxing the second light component to a second rectifying tower for secondary stripping rectification, wherein the reflux temperature is 135 ℃, and the reflux flow is 16L/h. In the second heavy component, the content of EPA by mass is 66% and the content of DHA by mass is 16%.
The second heavy component obtained was subjected to 6-stage molecular distillation at a temperature of 90 ℃ for the first distillation, 115 ℃ for the second distillation, 122 ℃ for the third distillation, 135 ℃ for the fourth distillation, 156 ℃ for the fifth distillation and 170 ℃ for the sixth distillation, and EPA70 fractions were collected, wherein the EPA content by mass was 71%, the DHA content by mass was 11% and the EPA70 yield was 77%.
Example 4
Taking fish oil ethyl ester fractions with EPA/DHA mass content of 28% and 5%, respectively, heating the fish oil ethyl ester fractions to 164 deg.C, introducing into a first rectifying tower at 55L/h for primary stripping rectification, preheating carrier gas nitrogen at 250 deg.C, and flowing nitrogen at 1600m3H, the vacuum degree is 5kPa,in the process of primary steam stripping rectification, the tower top temperature of the first rectifying tower is measured to be 143 ℃, a first heavy component and a first light component are obtained, the first light component reflows to the first rectifying tower for primary steam stripping rectification, the reflow flow is 30L/h, and the reflow temperature is 115 ℃. In the first heavy component, the weight content of EPA is 48%, and the weight content of DHA is 8%.
Preheating the obtained first heavy component to 176 ℃, feeding the first heavy component into a second rectifying tower at a rate of 23L/h for secondary steam stripping rectification, wherein the preheating temperature of carrier gas nitrogen for the secondary steam stripping rectification is 250 ℃, and the flow rate of the nitrogen is 1400m3H, the vacuum degree is 5 kPa; in the process of secondary steam stripping rectification, the tower top temperature of the second rectifying tower is measured to be 151 ℃, and a second heavy component and a second light component are obtained; and refluxing the second light component to a second rectifying tower for secondary stripping rectification, wherein the reflux temperature is 133 ℃, and the reflux flow is 15L/h. In the second heavy component, the content of EPA by mass is 69% and the content of DHA by mass is 11%.
The second heavy component obtained was subjected to 6-stage molecular distillation at a temperature of 90 ℃ for the first distillation, 114 ℃ for the second distillation, 122 ℃ for the third distillation, 133 ℃ for the fourth distillation, 154 ℃ for the fifth distillation and 170 ℃ for the sixth distillation, and EPA70 fractions were collected, with a EPA content by mass of 72%, a DHA content by mass of 10% and an EPA70 yield of 80%.
Example 5
The differences from example 1 are: the 6-stage molecular distillation was replaced by a 7-stage molecular distillation, the temperature of the first distillation being 90 ℃, the temperature of the second distillation being 115 ℃, the temperature of the third distillation being 123 ℃, the temperature of the fourth distillation being 135 ℃, the temperature of the fifth distillation being 156 ℃, the temperature of the sixth distillation being 162 ℃ and the temperature of the seventh distillation being 170 ℃. Collecting the fraction with EPA content of 70% or more, wherein the EPA content is 71 wt%, the DHA content is 10 wt%, and the EPA70 yield is 77%.
Comparative example 1
The differences from example 1 are: the 6-stage molecular distillation is replaced by 4-stage molecular distillation, the temperature of the first-stage distillation is 90 ℃, the temperature of the second-stage distillation is 115 ℃, the temperature of the third-stage distillation is 125 ℃, and the temperature of the fourth-stage distillation is 135 ℃. An EPA70 fraction was collected, with an EPA mass content of 70%, a DHA mass content of 12% and an EPA70 yield of 62%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The extraction method of the fish oil intermediate EPA70 is characterized by comprising the following steps:
preheating the ethylated fish oil, and performing primary steam stripping rectification to obtain a first heavy component;
preheating the first heavy component, and performing secondary steam stripping rectification to obtain a second heavy component;
subjecting the second heavy component to multi-stage molecular distillation to obtain the fish oil intermediate EPA 70;
preheating the ethyl esterification fish oil at the temperature of 120-170 ℃;
the preheating temperature of the first heavy component is 170-180 ℃;
the temperature of the carrier gas of the primary steam stripping rectification and the temperature of the carrier gas of the secondary steam stripping rectification are 210-260 ℃ independently;
the number of stages of the multi-stage molecular distillation is more than or equal to 6 stages.
2. The extraction method according to claim 1, wherein the ethyl esterified fish oil contains EPA in an amount of 18% by mass or more and DHA in an amount of 6% by mass or less.
3. The extraction method as claimed in claim 1 or 2, wherein the feeding flow rate of the ethylated fish oil in the primary stripping and rectification process is 50-60L/h.
4. The extraction method according to claim 1, wherein the vacuum degree of the primary stripping rectification and the vacuum degree of the secondary stripping rectification are independently 3-6 kPa.
5. The extraction method according to claim 1 or 4, characterized in that the first stage stripping rectification also produces a first light component; the reflux ratio of the first light component is 0.5-1.
6. The extraction method according to claim 5, wherein the reflux temperature of the first light component is 100-120 ℃; the reflux flow rate of the first light component is 25-35L/h.
7. The extraction method according to claim 1, wherein the feeding flow rate of the first heavy component in the secondary stripping and rectification process is 22-30L/h.
8. The extraction process according to claim 1, characterized in that said secondary stripping rectification also produces a second light fraction; the reflux ratio of the second light component is 0.5-1.
9. The extraction method according to claim 8, wherein the reflux temperature of the second light component is 130 to 140 ℃; and the reflux flow rate of the second light component is 13-20L/h.
10. The extraction process according to claim 1, wherein the multistage molecular distillation six-stage molecular distillation comprises performing a first distillation, a second distillation, a third distillation, a fourth distillation, a fifth distillation, and a sixth distillation in this order; the temperature of the first distillation is 80-100 ℃, the temperature of the second distillation is 110-120 ℃, the temperature of the third distillation is 115-125 ℃, the temperature of the fourth distillation is 130-140 ℃, the temperature of the fifth distillation is 150-160 ℃, and the temperature of the sixth distillation is 160-175 ℃.
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