CN117586831A - Fatty acid continuous separation system - Google Patents
Fatty acid continuous separation system Download PDFInfo
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- CN117586831A CN117586831A CN202311562448.8A CN202311562448A CN117586831A CN 117586831 A CN117586831 A CN 117586831A CN 202311562448 A CN202311562448 A CN 202311562448A CN 117586831 A CN117586831 A CN 117586831A
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- 238000000926 separation method Methods 0.000 title claims abstract description 532
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 102
- 239000000194 fatty acid Substances 0.000 title claims abstract description 102
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 102
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 99
- 150000004671 saturated fatty acids Chemical class 0.000 claims abstract description 68
- 239000000463 material Substances 0.000 claims abstract description 64
- 235000020777 polyunsaturated fatty acids Nutrition 0.000 claims abstract description 62
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims abstract description 53
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims abstract description 53
- 235000021281 monounsaturated fatty acids Nutrition 0.000 claims abstract description 45
- 238000001179 sorption measurement Methods 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000010828 elution Methods 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000004140 cleaning Methods 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 26
- 230000008569 process Effects 0.000 claims description 25
- 230000008878 coupling Effects 0.000 claims description 20
- 238000010168 coupling process Methods 0.000 claims description 20
- 238000005859 coupling reaction Methods 0.000 claims description 20
- 230000005540 biological transmission Effects 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- -1 polydimethylsiloxane Polymers 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- 230000000536 complexating effect Effects 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 230000002572 peristaltic effect Effects 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 5
- 230000033001 locomotion Effects 0.000 claims description 5
- 230000000274 adsorptive effect Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 description 18
- 239000003480 eluent Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- 238000005194 fractionation Methods 0.000 description 7
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 description 7
- 235000003441 saturated fatty acids Nutrition 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920000263 Rubber seed oil Polymers 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000001289 litsea cubeba fruit oil Substances 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 240000002262 Litsea cubeba Species 0.000 description 2
- 235000012854 Litsea cubeba Nutrition 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000199 molecular distillation Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 235000021313 oleic acid Nutrition 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000000194 supercritical-fluid extraction Methods 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/10—Refining fats or fatty oils by adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- 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)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a continuous fatty acid separation system, which utilizes the characteristic that different separation adsorption materials have different adsorption capacities on fatty acids with different saturation degrees to realize continuous separation of fatty acids on a separation device, thereby achieving accurate separation of C12-C24 fatty acids with different carbon chain lengths and fatty acids with different double bond numbers. The system can separate saturated fatty acid, unsaturated fatty acid, monounsaturated fatty acid and polyunsaturated fatty acid from fatty acid gradually and continuously; the separation rate of saturated fatty acid is up to more than 85%, the separation rate of unsaturated fatty acid is up to more than 90%, the separation rate of monounsaturated fatty acid is up to more than 85%, the separation rate of polyunsaturated fatty acid is up to more than 85%, and the method has excellent market application prospect.
Description
Technical Field
The invention belongs to the field of fatty acid purification and separation, and particularly relates to a continuous fatty acid separation system.
Background
Fatty acids refer to long aliphatic hydrocarbon chains containing one carboxyl group at one end. The fatty acid has various kinds and can be classified into saturated fatty acid, monounsaturated fatty acid and polyunsaturated fatty acid, wherein the saturated fatty acid is mainly used for manufacturing industries such as cleaning agent, medicine and food; the monounsaturated fatty acid is mainly used in the industries of soap, paint, plastics, rubber and the like; polyunsaturated fatty acids are mainly used in health products, cosmetics, medicines, foods, etc. The woody industrial oil plant seed oil represented by the rubber tree seed oil, the light bark tree seed oil, the agilawood seed oil and the litsea cubeba seed oil contains saturated fatty acids such as palmitic acid, stearic acid and the like, and is also rich in unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid and the like. If the mixed fatty acid prepared by taking the mixed fatty acid as a raw material is separated, even further separation and purification of monounsaturated fatty acid (such as oleic acid) and polyunsaturated fatty acid (such as linoleic acid and linolenic acid) are key to development of high-added value chemicals and health care products of woody industrial oil.
Numerous fatty acid separation techniques such as urea inclusion, low temperature crystallization, solvent extraction, molecular distillation, supercritical extraction, etc. have been developed by current researchers. At present, each separation technology only can realize partial separation of fatty acid, and can not separate saturated fatty acid, monounsaturated fatty acid and polyunsaturated fatty acid in a grading way. For example, urea inclusion can only separate polyunsaturated fatty acids and cannot separate saturated fatty acids from monounsaturated fatty acids; low temperature crystallization is often used to separate saturated fatty acids from unsaturated fatty acids, which cannot be fractionated from polyunsaturated fatty acids; in addition, the molecular distillation method has long operation time and high temperature, so that the fatty acid is easy to cause thermosensitive reaction, and the quality and the efficiency of the product are affected; the supercritical extraction is complex in production process and low in efficiency because the equipment is intermittent extraction equipment; by adopting the separation technology, most of fatty acid is lost, so that the fatty acid separation efficiency is low, continuous separation of fatty acid cannot be realized, continuous fractionation of fatty acid cannot be realized, the production efficiency is low, and the industrialized popularization is not facilitated.
For example, the invention patent application CN102811781a discloses a simulated moving bed chromatographic separation process for purifying polyunsaturated fatty acids, which process comprises introducing the feed mixture into a simulated or actual moving bed chromatographic apparatus having a plurality of connected chromatographic columns containing aqueous alcohol as eluent, wherein the apparatus has a plurality of zones comprising at least a first zone and a second zone, each zone having a draw stream and a raffinate stream, from which liquids from the plurality of connected chromatographic columns can be collected, and wherein (a) a raffinate stream comprising PUFA product together with more polar components is collected from a column in the first zone and introduced into a non-adjacent column in the second zone, and/or (b) a extract stream comprising PUFA product together with less polar components is collected from a column in the second zone and introduced into a non-adjacent column in the first zone, whereby the PUFA product is separated from the feed mixture in each zone.
The method is only suitable for separating binary mixtures, namely, strong-polarity fatty acid and weak-polarity fatty acid are separated, saturated fatty acid and unsaturated fatty acid cannot be separated, the separation range is limited, liquid collected by the extraction liquid flow or the raffinate flow needs to be recycled to the first area or the second area for continuous repeated separation, repeated cyclic separation is carried out, and the operation is complicated.
Compared with the separation technology, the ion complexing technology taking pi bond complexing as a theoretical basis is a fatty acid separation technology hopeful to realize industrialized application due to the advantages of simple operation process, mild operation condition, easy realization of continuous separation and the like. Therefore, according to the characteristics of the structure and the performance of saturated fatty acid and unsaturated fatty acid in fatty acid, the unsaturation degree of unsaturated fatty acid and the like, a continuous separation process is developed, and the potential market demand is provided.
Disclosure of Invention
The invention aims to solve the problems of the prior fatty acid continuous separation, and provides a fatty acid continuous separation system which is beneficial to the industrialized popularization of fatty acid fractionation by carrying out the sectional grading of a chromatographic column according to the characteristics of different fatty acids and adsorbents with different adsorption separation performances so as to realize the continuous coupling separation of fatty acids.
The specific scheme is as follows:
the continuous fatty acid separation system comprises a separation device, wherein the separation device comprises a power device and a transmission shaft connected with the center of the power device, the power device is fixedly connected with a frame, and the power device drives the transmission shaft to rotate so as to drive a separation column connected with the transmission shaft to do circular motion; the center of the turntable is sleeved on the transmission shaft, round holes corresponding to the number and the size of the separation columns are formed along the periphery of the turntable, and the plurality of separation columns sequentially penetrate through the round holes of the turntable, so that the separation columns rotate along with the turntable when the transmission shaft drives the turntable;
the separating column is provided with a feeding hole and a discharging hole, the feeding hole is connected with a valve plate arranged at the top of the separating column, the valve plate is electrically connected with the digital display control device and is communicated with a piping panel, and the piping panel is provided with a plurality of feeding holes and a plurality of discharging holes for inputting and outputting materials and corresponds to the separating column one by one; the distributing plate is connected with the feed inlet of the distributing pipe panel through a hose, the feed outlet of the separating column is connected with the discharge outlet of the distributing pipe panel through a hose, and the distributing pipe panel is connected with the feed inlets or the feed outlets of different separating columns according to the separation process during operation; the tubing panel is also provided with a pump port, the pump port is connected with a peristaltic pump, and the peristaltic pump is used for controlling the flow speed of the material;
Feeding the material to be separated into the separation device, and dividing the separation columns of the separation device into at least 2 separation systems according to the arrangement sequence, wherein each separation system comprises: an adsorption separation zone, an elution zone and a washing zone; the adsorption separation zone is used for carrying out adsorption separation on the input materials, and the liquid flowing out after passing through the adsorption separation zone is an unsaturated fatty acid product;
the unsaturated fatty acid product enters an elution zone, the liquid flowing out after the elution treatment of the elution zone is a saturated fatty acid product, and the saturated fatty acid product enters a cleaning zone and flows out of a system after the cleaning treatment, so that single-system continuous separation is realized; or the unsaturated fatty acid product as a raw material enters a next separation system, and flows out of the system after being treated by the adsorption separation zone, the elution zone and the cleaning zone respectively, so that continuous coupling separation is realized.
Further, the separation system consists of a separation system 1 and a separation system 2, wherein the separation column, the feed inlet and the discharge outlet are respectively numbered as 1,2 and … … N-1,2N in sequence according to the arrangement sequence, wherein N is a positive integer, and preferably 10 < N < 20;
The separation system 1 consists of a separation column with a single number, the separation system 2 consists of a separation column with a double number, the separation column 1 corresponds to the feed inlet 1 before the separation device operates, and the separation column is connected with the next feed inlet of the same system every time the valve plate rotates for 1 time; when the first separation column of the separation system 1 reaches the N-number discharge port, the separation system 2 starts to work;
when the separation system 2 starts to work, the N-1 separation column is connected with the No. 2 feed inlet, and the No. 2 feed inlet is connected with the N discharge outlet before the separation system 2 runs, so that the non-adsorbed unsaturated fatty acid flows into the separation system 2 after passing through the separation system 1, and the separation column for adsorbing the saturated fatty acid in the separation system 1 enters an elution zone in the separation system 1, so that the saturated fatty acid and the unsaturated fatty acid are separated, and the grading continuous coupling separation is realized;
after saturated fatty acid is washed out by an elution zone in the separation system 1, unsaturated fatty acid enters a separation zone of the separation system 2, when a 1 st separation column of the separation system 2 reaches a last 1 material port N+1 number discharge port of the separation zone, unadsorbed monounsaturated fatty acid flows out, a separation column for adsorbing polyunsaturated fatty acid in the separation system 2 enters an elution zone in the separation system 2, so that the monounsaturated fatty acid is separated from the polyunsaturated fatty acid, and the monounsaturated fatty acid flows out of the system after being eluted by the elution zone in the separation system 2.
Further, 3-8 fixed end valve ports are connected in series in the adsorption separation area of the separation system 1 and used for inputting and outputting materials, the separation column is filled with a composite separation material of melamine and polydimethylsiloxane, and the eluting liquid in the eluting area is ethyl acetate or n-hexane, and the flow rate is 5-10ml/min.
Further, 2-5 fixed end valve ports connected in series in the adsorption separation area of the separation system 2 are used for inputting and outputting materials, the separation column is filled with metal complexing adsorption separation materials, preferably silver and aluminum complexing bimetallic complexing adsorption separation materials, and the eluting liquid in the eluting area is acetone or 1-hexene, and the flow rate is 5-10ml/min.
Further, the cleaning areas of the separation system 1 and/or the separation system 2 are connected with 1-2 fixed end valve ports in series for inputting and outputting materials, the cleaning liquid is methanol, and the liquid flow rate is 5-10ml/min.
Further, the adsorptive separation zone of the separation system 1 and/or separation system 2 contains 3-5 separation columns, the elution zone contains 2-4 separation columns, and the washing zone contains 1-2 separation columns, each separation column being filled with 50-150g of adsorptive separation material.
Further, the operation of the separation device is that the valve plate rotates clockwise, the separation columns rotate anticlockwise, each time the separation columns rotate and move for 2-5 steps, one step corresponds to one separation column, each time the separation columns rotate for 1 time for 20-60min, namely the separation time for completing the same process node between the adjacent separation columns is 20-60min.
Further, after the material to be separated passes through the separation system 1, the saturated fatty acid and the unsaturated fatty acid are separated, the separation rate of the saturated fatty acid is 85-95%, and the separation rate of the unsaturated fatty acid is 90-95%.
Further, after the unsaturated fatty acid passes through the separation system 2, the monounsaturated fatty acid and the polyunsaturated fatty acid are separated, the separation rate of the monounsaturated fatty acid is 85-90%, and the separation rate of the polyunsaturated fatty acid is 85-94%.
The beneficial effects are that: compared with the traditional method, the fatty acid continuous separation system provided by the invention creatively utilizes different separation materials to assemble fatty acids with different adsorption separation performances, realizes continuous and coupled adsorption separation of fatty acids, has a separation efficiency of saturated fatty acids of more than 85%, has a separation rate of unsaturated fatty acids of more than 90%, has a separation rate of monounsaturated fatty acids of more than 85%, and has an adsorption separation efficiency of polyunsaturated fatty acids of more than 85%.
More importantly, the system realizes continuous fractionation of saturated fatty acid and unsaturated fatty acid, monounsaturated fatty acid and polyunsaturated fatty acid, and can achieve accurate separation of C12-C24 fatty acid with different carbon chain lengths and fatty acid with different double bond numbers by adopting different eluents, thereby improving the value and application space of the fatty acid.
The prior fatty acid separation, such as CN102811781A, has the theoretical basis that the polarity of the fatty acid component influences the adsorption performance of the solid adsorbent, namely the stronger the polarity of the fatty acid is, the weaker the adsorption is, and conversely, the weaker the polarity is, the stronger the adsorption is, so that the separation is realized when the fatty acid flows through a chromatographic column; the rate at which liquid collected via the draw and raffinate streams in each zone is recycled back to the same zone is simultaneously adjusted so that the PUFA product can be separated from different components of the feed mixture in each zone.
The theoretical basis of the invention for realizing fatty acid separation is that the unsaturated degree of fatty acid affects the adsorption performance of a solid adsorbent, a chromatographic column in a separation area in a first circulation system is filled with melamine composite polydimethylsiloxane adsorption separation material, the separation material adsorbs saturated fatty acid, the separation of saturated fatty acid and unsaturated fatty acid is realized through the first circulation system, and a chromatographic column in a separation area in a second circulation system is filled with Ag + -Al 3+ The separation material adsorbs polyunsaturated fatty acid, and the separation of monounsaturated fatty acid and polyunsaturated fatty acid is realized through a second circulation system.
Furthermore, the invention innovates a specific separation method, the chromatographic column is divided into different circulation systems according to requirements, and the separation liquid or eluent separated by each system (namely the liquid collected by the extraction liquid flow or the raffinate flow mentioned in the patent CN 102811781A) is not required to be circulated back to the system for continuous repeated separation, so that the primary separation or fractionation is realized. The liquid collected by the liquid extraction flow or the raffinate flow of the first area and the second area in the invention patent CN102811781A needs to be circulated back to the first area or the second area to be continuously and repeatedly separated, and the use is inconvenient.
In addition, the invention innovates the design of the separation area (or system), for example, in the embodiment of the invention, the separation device is provided with 30 chromatographic columns (which can be not limited to 30), each column is randomly classified into each separation system according to the requirements of the separation process and the step number, the column number of each separation system is not fixed, each column is not an adjacent column, and each separation system comprises separation, elution and cleaning functions. In the invention patent CN102811781a, the moving bed chromatography apparatus has 15 chromatographic columns (or more chromatographic columns), the number of columns in the first zone and the second zone are fixed and similar, and each column is an adjacent column; each zone includes a separation and elution function.
Finally, from the standpoint of separation suitability, the prior art is generally only suitable for separating binary mixtures, i.e., fatty acids having strong polarity from fatty acids having weak polarity, and it is not possible to separate saturated fatty acids from unsaturated fatty acids, for example, patent CN102811781a.
The method is suitable for the fractionation of the mixed fatty acid (containing saturated fatty acid, monounsaturated fatty acid and polyunsaturated fatty acid), can realize the fractionation of the saturated fatty acid, monounsaturated fatty acid and polyunsaturated fatty acid, and has higher separation degree and wider applicability.
Drawings
In order to more clearly illustrate the technical solutions of the present invention, the following brief description will be made on the accompanying drawings, which are given by way of illustration only and not limitation of the present invention.
FIG. 1 is a schematic view showing the overall structure of a separation device according to an embodiment of the present invention;
FIG. 2 is a schematic illustration of a continuous coupling separation provided by one embodiment of the present invention;
FIG. 3 is a specific flow chart (step 2/time) for continuous coupling and separation of fatty acids according to one embodiment of the present invention;
FIG. 4 is a schematic diagram of the operational flow of a separation system 1 provided in one embodiment of the present invention;
Fig. 5 is a schematic diagram of the operational flow of the separation system 2 provided in one embodiment of the present invention.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. The specific techniques or conditions are not identified in the examples and are performed according to techniques or conditions described in the literature in this field or according to the product specifications. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In the following examples, "%" refers to mass percent unless explicitly stated otherwise.
The main adsorbent materials used in the following examples were as follows:
melamine composite polydimethylsiloxane adsorption separation material Mel-PDMS, specifically prepared as follows:
stirring melamine and ethanol at 70 ℃ for 1 hour to form a uniform solution, regulating the pH value of the solution to 8.0, adding dimethyl siloxane and triethylamine, wherein the mass ratio of the melamine to the dimethyl siloxane to the triethylamine is 4:1:0.02, reacting for 3 hours, washing with deionized water to be neutral, and vacuum drying at 80 ℃ for 5 hours to obtain the melamine composite dimethyl siloxane adsorption separation material, namely Mel-PDMS.
Bimetallic complex adsorption separation material Ag + -Al 3+ The specific preparation method of the SCA-DE is as follows:
1) Adding Diatomite (DE) with a certain mass into hexane at 50 ℃, stirring uniformly and sufficiently for 4 hours, slowly dripping an N, N-diethyl-3-aminopropyl trimethoxysilane ethanol solution into the mixed solution, wherein the total mass ratio of the diatomite to the N, N-diethyl-3-aminopropyl trimethoxysilane is 1:8, refluxing for 12 hours at 80 ℃, washing with absolute ethanol, and filtering repeatedly for three times. Drying at 100deg.C for 12 hr to obtain SCA-DE material.
2) Weighing a proper amount of modified diatomite SCA-DE, dissolving in dioxane, mixing SCA-DE material and dioxane at a mass ratio of 1:5, and adding anhydrous AlCl with carbon disulfide 3 The ethanol solution is fully stirred, filtered, washed by dioxane and deionized water and detected to be free of Cl - Vacuum drying to obtain Al 3+ SCA-DE material.
3) Taking a proper amount of Al 3+ Adding an SCA-DE material into acetone, adding AgF with a certain mass 4 Stirring for 10-16 hr under shade, filtering, washing with acetone and deionized water, and detecting no F - Vacuum drying at 70deg.C for 6 hr to obtain Ag + -Al 3+ A double-metal complex adsorption separation material of SCA-DE.
Example 1
A fatty acid continuous coupling and separating device, as shown in fig. 1: the device comprises a power device 1 and a transmission shaft 2 connected with the center of the power device, wherein the transmission shaft 2 is fixedly connected with a frame 4, and the power device 1 drives the transmission shaft 2 to rotate so as to drive a separation column 5 to do circular motion.
The center cover of carousel 6 is established on transmission shaft 2, has the round hole corresponding with separation post 5 quantity and size along the periphery of carousel 6, and separation post 5 wears to locate the carousel round hole in proper order to when transmission shaft 2 drove the rotation of separation post, carousel 6 rotates along with it, and separation post backing ring plays the steady support effect with carousel 6 to separation post 5. Each separation column 5 is provided with an upper material opening and a lower material opening, the material opening of the separation column 5 is connected with a valve plate 7 arranged at the top, the valve plate 7 is connected with a material inlet 10 of a piping panel 9 through a hose, the material outlet of the separation column 5 is connected with a material outlet 11 of the piping panel 9 through a hose, and the material openings of different separation columns 5 are flexibly connected according to a separation process through the piping panel 9 during operation, so that the separation columns are distributed to different separation systems.
In order to ensure a stable separation effect, a temperature control belt is arranged at the bottom of the separation column 5 and is used for heating or insulating the separation column 5.
The valve plate 7 is electrically connected with the digital display control device 8 and is simultaneously communicated with the piping panel 9, the piping panel 9 is provided with a plurality of feed inlets 10 and a plurality of discharge outlets 11 for inputting and outputting materials, and the feed inlets 10 are communicated with the top of the separation column 5 through the valve plate 7 so as to finish feeding; the bottom of the separation column 5 is communicated with a discharge port 11 so as to output a product obtained by separation or realize the sectional grading of different separation systems. The piping panel 9 is also provided with a pump port 12, the pump port 12 is connected with a peristaltic pump 13, and the peristaltic pump 13 controls the flow speed of the material.
The device operates as follows: the mixed fatty acid to be separated enters the system through the feed inlet 10, is conveyed into a certain separation column 5 through the valve plate 7 under the action of the peristaltic pump 13 to be subjected to adsorption, elution and other treatments, and is output through the discharge outlet 11 after the treatment.
Example 2
This example further describes, based on example 1, a fatty acid continuous coupling separation apparatus comprising 30 separation columns 5, numbered sequentially from 1 to 30.
Correspondingly, the device comprises 30 feed inlets, and the serial numbers of the feed inlets are 1-30 in sequence; 30 discharge ports are numbered 1-30 in sequence.
The continuous fatty acid separation method by adopting the separation device specifically comprises the following steps:
1) Feeding the mixed fatty acid into a fatty acid continuous coupling and separating device rotating anticlockwise;
2) According to the requirement of the separation process, the fixed end material port of the valve plate of the fatty acid continuous coupling and separating device is sequentially divided into a sectional grading separation area, an elution area and a cleaning area according to the anticlockwise direction, and the separation columns are all in an anticlockwise column feeding mode. The inlet and outlet of the valve plate are marked anticlockwise, the valve plate rotates clockwise, and the valve plate is opposite to the inlet direction.
As shown in fig. 2, the separation columns are classified into 2 separation systems, i.e., a separation system 1 and a separation system 2, according to the process requirements. The fixed end of the valve plate is correspondingly provided with a material port to divide a functional area according to the number of separation stages and the number of rotation steps (steps/times) each time, and unsaturated fatty acid separated in the separation system 1 flows into the separation system 2 through a material outlet, and at the moment, the unsaturated fatty acid is separated from saturated fatty acid. The adsorbed saturated fatty acid moves along with the separation column in the separation system 1, enters an elution zone, the saturated fatty acid is eluted, the separation column in the separation system 1 continues to move, enters a cleaning zone, impurities in the separation column are washed out, and the separation system 1 finishes the separation process of the saturated fatty acid. Unsaturated fatty acid flowing into the separation system 2 enters a separation area of the separation system 2, after adsorption and separation, monounsaturated fatty acid flows out, polyunsaturated fatty acid is adsorbed and moves along with a separation column to enter an elution area of the separation system 2, polyunsaturated fatty acid is eluted out, the separation column in the separation system 2 continues to move and enters a cleaning area, impurities in the separation column are washed out, and thus, the separation system 2 completes a separation process of monounsaturated fatty acid and polyunsaturated fatty acid.
FIG. 3 is a specific flow chart of continuous coupling separation of fatty acids, wherein Mel-PDM separation material is filled into a separation column in a separation system 1, and the separation material Ag is adsorbed by bimetallic complex + -Al 3+ The separation column in the separation system 2 is filled with SCA-DE, and then the separation equipment starts to operate, and the specific separation process is as follows:
the mixed fatty acid is conveyed into a sectional grading separation area through a No. 1 feed inlet, unsaturated fatty acid flows out from a No. 15 discharge port after passing through a separation column in a separation system 1, and enters a separation system 2 through a No. 2 feed inlet to be continuously subjected to grading separation. The saturated fatty acid adsorbed in the separation system 1 enters an elution zone along with a separation column, eluent flows into the separation system 1 from a feed inlet such as No. 17, the saturated fatty acid is eluted from the separation column, and the saturated fatty acid flows out from a discharge outlet such as No. 25, is collected and distilled to obtain high-purity saturated fatty acid; the separation column in the separation system 1 continues to move to the cleaning zone, after cleaning, to the staged separation zone, and still starts a new round of separation in the form of the separation system 1.
The unsaturated fatty acid enters the separation system 2 through the No. 2 feed inlet, flows out of the separation column of the separation system 2 through the No. 16 discharge outlet, is collected and distilled to finally obtain high-purity unsaturated fatty acid, the adsorbed polyunsaturated fatty acid enters an elution zone of the separation system 2 along with the separation column, the eluent enters the No. 18 feed inlet, the polyunsaturated fatty acid is eluted through the No. 26 discharge outlet, is collected and distilled to obtain high-purity polyunsaturated fatty acid, the separation column in the separation system 2 continuously moves to a cleaning zone, and moves to a sectional grading separation zone after cleaning, and a new round of separation is started in the form of the separation system 2.
Fig. 4 is a schematic diagram of the working flow of the separation system 1, and the separation system 1 shown in fig. 4 distributes 8 separation columns (column numbers, 1,3,5,7,9, 11, 13, 15), the Mel-PDM separation material is filled into the separation columns in the separation system 1, and each separation column moves anticlockwise every 2 steps when the separation device is operated. The number of the separation columns and the number of each step can be flexibly adjusted according to the specific separation process requirements. The specific working conditions are as follows:
the mixed fatty acid is input into the separation columns of the sectional grading separation area from the No. 1 feed inlet, the sequence of the separation columns is shown in the figure, the separation columns sequentially enter the sectional grading separation area, after 14 steps, the last No. 15 column of the separation column enters the sectional grading separation area, and at the moment, all the separation columns enter the sectional grading separation area. At this time, the residence time of the No. 1 separation column in the zone is 14/2 (min) of each movement interval time, the adsorption separation of the mixed fatty acid is completed, the saturated fatty acid is adsorbed, and the unsaturated fatty acid flows into the separation system 2 through the No. 15 discharge port. The No. 1 separation column continuously moves, after 2 steps, the No. 1 separation column enters an elution zone, eluent enters the separation column 1 from a No. 17 feed inlet, adsorbed saturated fatty acid starts to be eluted, and is sequentially connected with 19, 21, 23 and 25 feed inlets for elution when 2 steps are performed each time, after 8 steps, the No. 1 separation column moves to the final stage of the elution zone, namely the junction of the elution zone and a cleaning zone, at the moment, liquid containing the saturated fatty acid and the eluent eluted from the No. 1 separation column flows out from a No. 25 discharge outlet, namely the fatty acid 1, and high-purity saturated fatty acid can be obtained through collection and distillation treatment; the No. 1 separation column continuously moves, after 2 steps, the No. 1 separation column enters a cleaning area, cleaning liquid flows into the No. 1 separation column from the No. 27 and No. 29 feed inlets and is discharged through the No. 29 discharge outlet, at this time, the No. 1 separation column completes a complete separation process of the separation system 1, and other separation columns sequentially undergo the same separation, elution and cleaning processes as the No. 1 separation column. When each separation column completes a complete separation process, the separation columns sequentially move to the sectional grading separation area from the cleaning area through 2 steps, and a new separation work flow of the separation system 1 is started.
FIG. 5 is a schematic diagram showing the working flow of the separation system 2. The separation system 2 shown in FIG. 5 is provided with 8 separation columns (column numbers, 14, 16, 18, 20, 22, 24, 26, 28) and the bimetallic complex adsorption separation material Ag + -Al 3+ The separation columns in the separation system 2 are filled with SCA-DE, and each separation column is moved counterclockwise 2 steps at a time when the separation apparatus is operated. The number of the separation columns and the number of each step can be flexibly adjusted according to the specific separation process requirements. The specific working conditions are as follows:
the unsaturated fatty acid liquid flowing out of the 15 # discharge port of the separation system 1 is conveyed into the separation columns of the 2-stage grading separation zone of the separation system through the 2 # feed port, the separation columns sequentially enter the stage grading separation zone as shown in the figure, after 14 steps, the last 28 # column of the separation column enters the stage grading separation zone, and at the moment, all the separation columns enter the stage grading separation zone. The retention time of the No. 14 separation column in the area is 14/2 (min) of each movement interval time, the monounsaturated fatty acid is adsorbed and separated, polyunsaturated fatty acid is adsorbed, and the monounsaturated fatty acid flows out through a No. 16 discharge port, namely, the fatty acid 2 is subjected to collection and distillation treatment, so that the high-purity monounsaturated fatty acid can be obtained; the No. 14 separation column continuously moves, after 2 steps, the No. 14 separation column enters an elution zone, eluent enters the separation column 14 from a No. 18 feed inlet, adsorbed polyunsaturated fatty acid starts to be eluted, and is sequentially connected with No. 20 feed inlets, no. 22 feed inlets, no. 24 feed inlets and No. 26 feed inlets for elution when 2 steps are performed, after 8 steps, the No. 14 separation column moves to the final stage of the elution zone, namely the junction of the elution zone and a cleaning zone, at the moment, liquid which is eluted from the No. 14 separation column and contains polyunsaturated fatty acid and eluent flows out from a No. 26 discharge outlet, namely fatty acid 3, and high-purity polyunsaturated fatty acid can be obtained through collection and distillation treatment; the No. 14 separation column continuously moves, after 2 steps, the No. 14 separation column enters a cleaning area, cleaning liquid flows into the No. 14 separation column from the No. 28 and No. 30 feed inlets and is discharged through the No. 30 discharge outlet, at this time, the No. 14 separation column completes a complete separation process of the separation system 2, and other separation columns sequentially undergo the same separation, elution and cleaning processes as the No. 14 separation column. When each separation column completes a complete separation process, the separation columns sequentially move to the sectional grading separation area from the cleaning area through 2 steps, and a new separation work flow of the separation system 2 is started.
Through the separation process, continuous coupling separation of fatty acid can be realized, and accurate separation of C12-C24 fatty acid with different carbon chain lengths and fatty acid with different double bond numbers can be achieved.
Example 3
2 sets of separation systems are adopted to separate the rubber seed oil mixed fatty acid (17% of saturated fatty acid content, 29% of monounsaturated fatty acid content and 54% of polyunsaturated fatty acid content), the feeding amount of the rubber seed oil mixed fatty acid is 5ml/min, 3 chromatographic columns are adopted in each separation system separation zone, 2 chromatographic columns can be eluted simultaneously in an elution zone, 2 chromatographic columns can be washed simultaneously in a washing zone, and the rubber seed oil mixed fatty acid is separated under normal temperature conditions, wherein:
separation system 1: each separation column was filled with 100g of Mel-PDMS, and the product saturated fatty acids were eluted with ethyl acetate at a feed rate of 5ml/min (the process was such that saturated fatty acids were adsorbed, unsaturated fatty acids were discharged from the separation column into the separation system 2, the same applies hereinafter), and washed with methanol at a feed rate of 5 ml/min.
Separation system 2: each separation column was packed with 100g of Ag + -Al 3+ The product polyunsaturated fatty acids (which are eluted by the process of single unsaturated fatty acid bleed, polyunsaturated fatty acids adsorbed, the same applies below) are eluted with acetone at a feed rate of 5ml/min and washed with methanol at a feed rate of 5 ml/min.
The specific operation is as follows: when the rubber seed oil mixed fatty acid is separated, the fatty acid continuous coupling separation chromatographic column rotates anticlockwise, each time is 5 steps, each time is rotated for 1 time every 30min, the whole separation system completes 1 complete process time for about 3h, and the process interval time between adjacent columns is 30min. Each of the separated products was collected and purified by distillation under reduced pressure.
Under the raw material consumption and process conditions, the feeding amount of the mixed fatty acid of the rubber seed oil is 300ml per 1h, 44ml of saturated fatty acid and 225ml of unsaturated fatty acid are separated after passing through the separation system 1, the separation rate of the saturated fatty acid is 86.3%, and the separation rate of the unsaturated fatty acid is 90.3%; after passing through the separation system 2, 75.8ml of monounsaturated fatty acid and 145ml of polyunsaturated fatty acid can be separated, the separation rate of monounsaturated fatty acid is 87.1%, and the separation rate of polyunsaturated fatty acid is 89.5%.
Example 4
The separation device in example 2 was used to separate the mixed fatty acids of the curcas seed oil (saturated fatty acid content 14%, monounsaturated fatty acid content 22% and polyunsaturated fatty acid content 64%) by using 2 sets of separation systems, the feeding amount of the mixed fatty acids of the curcas seed oil was 10ml/min, the separation zone of each separation system adopts 8 chromatographic columns, the elution zone can elute 5 chromatographic columns simultaneously, the washing zone can wash 2 chromatographic columns simultaneously, and separation is performed under normal temperature conditions, wherein:
Separation system 1: each separation column is filled with 100g of Mel-PDMS separation adsorption material, and the saturated fatty acid of the separated product is eluted by using 10ml/min of n-hexane, and is washed by using 10ml/min of methanol.
Separation system 2: each separation column was packed with 100g of Ag + -Al 3+ Separating and adsorbing material by SCA-DE, eluting and separating polyunsaturated fatty acid by 1-hexene with feed amount of 10ml/min, and cleaning with methanol with feed amount of 10 ml/min.
The specific operation is as follows: when the mixed fatty acid of the curcas seed oil is separated, the fatty acid continuous coupling separation chromatographic column rotates anticlockwise, each time the chromatographic column rotates for 1 time every 30min for 2 steps, the whole separation system completes 1 complete process time for about 7.5h, and the process interval time between adjacent columns is 30min. Each of the separated products was collected and purified by distillation under reduced pressure.
Under the raw material consumption and the process conditions, the feeding amount of the mixed fatty acid of the curcas seed oil is 10ml/min, 600ml is fed per hour, 74.3ml of saturated fatty acid and 482ml of unsaturated fatty acid are separated out after the mixture passes through a separation system 1, the separation rate of the saturated fatty acid is 88.5%, and the separation rate of the unsaturated fatty acid is 93.4%; 114.8ml of monounsaturated fatty acid, 357.5ml of polyunsaturated fatty acid can be separated out after passing through the separation system 2, the separation rate of the monounsaturated fatty acid is 86.9%, and the separation rate of the polyunsaturated fatty acid is 93.1%.
Example 5
The separation device in example 2 was adopted, 2 sets of separation systems were used to separate the agilawood seed oil mixed fatty acid (saturated fatty acid content 18%, monounsaturated fatty acid content 76%, polyunsaturated fatty acid content 6%), the feeding amount of the agilawood seed oil mixed fatty acid was 8ml/min, 5 chromatographic columns were adopted in each separation system separation zone, 3 chromatographic columns were simultaneously eluted in elution zone, 2 chromatographic columns were simultaneously eluted in washing zone, separation was performed under normal temperature conditions, wherein:
separation system 1: each separation column is filled with 100g of Mel-PDMS separation adsorption material, and the saturated fatty acid of the separated product is eluted by using ethyl acetate with the feeding amount of 8ml/min, and is washed by using methanol with the feeding amount of 8 ml/min.
Separation system 2: each separation column was packed with 100g of Ag + -Al 3+ Separating the adsorption material by SCA-DE, eluting and separating polyunsaturated fatty acid by 1-hexene with the feeding amount of 8ml/min, and cleaning by methanol with the feeding amount of 8 ml/min.
The specific operation is as follows: when the mixed fatty acid of the agilawood seed oil is separated, the fatty acid continuous coupling separation chromatographic column rotates anticlockwise, 3 steps are performed each time, 1 time is performed every 30 minutes, the whole separation system completes 1 complete process time for about 5 hours, and the process interval time between adjacent columns is 30 minutes. Each of the separated products was collected and purified by distillation under reduced pressure.
Under the raw material consumption and the process conditions, the feeding amount of the agilawood seed oil mixed fatty acid is 8ml/min, 480ml per hour is obtained, 74ml of saturated fatty acid can be separated out after passing through the separation system 1, 356.3ml of unsaturated fatty acid is obtained, the separation rate of the saturated fatty acid is 85.6%, and the separation rate of the unsaturated fatty acid is 90.5%; 322.6ml of monounsaturated fatty acid, 24.7ml of polyunsaturated fatty acid and the separation rate of the monounsaturated fatty acid of 88.4% and the separation rate of the polyunsaturated fatty acid of 85.7% can be separated after passing through the separation system 2.
Example 6
The separation device in the embodiment 2 is adopted, 2 sets of separation systems are utilized to separate agilawood seed oil mixed fatty acid (the saturated fatty acid content is 18%, the monounsaturated fatty acid content is 76%, and the polyunsaturated fatty acid content is 6%), the feeding amount of the litsea cubeba seed oil mixed fatty acid is 8ml/min, 5 chromatographic columns are adopted in the separation areas of each separation system, 3 chromatographic columns can be eluted simultaneously in the elution areas, 2 chromatographic columns can be cleaned simultaneously in the cleaning areas, and the separation is carried out under the condition of 45 ℃, wherein:
separation system 1: each separation column is filled with 100g of Mel-PDMS separation adsorption material, and the saturated fatty acid of the separated product is eluted by using 8ml/min of n-hexane, and is washed by using 8ml/min of methanol.
Separation system 2: each separation column was packed with 100g of Ag + -Al 3+ Separating the adsorption material by SCA-DE, eluting and separating polyunsaturated fatty acid by 1-hexene with the feeding amount of 8ml/min, and cleaning by methanol with the feeding amount of 8 ml/min.
The specific operation is as follows: when the mixed fatty acid of the agilawood seed oil is separated, the fatty acid continuous coupling separation chromatographic column rotates anticlockwise, 3 steps are performed each time, 1 time is performed every 30 minutes, the whole separation system completes 1 complete process time for about 5 hours, and the process interval time between adjacent columns is 30 minutes. Each of the separated products was collected and purified by distillation under reduced pressure.
Under the raw material consumption and process conditions, the feeding amount of mixed fatty acid of agilawood seed oil per 1h is 480ml, 82ml of saturated fatty acid and 362.5ml of unsaturated fatty acid can be separated after passing through a separation system 1, the separation rate of the saturated fatty acid is 94.9%, and the separation rate of the unsaturated fatty acid is 92.1%; 329.5ml of monounsaturated fatty acid, 25.7ml of polyunsaturated fatty acid and 89.4% of polyunsaturated fatty acid can be separated out after passing through the separation system 2.
Example 7
The separation device in the embodiment 2 is adopted, the litsea cubeba oil mixed fatty acid (the saturated fatty acid content is 69%, the monounsaturated fatty acid content is 23% and the polyunsaturated fatty acid content is 8%) is separated by using 2 sets of separation systems, the feeding amount of the litsea cubeba oil mixed fatty acid is 5ml/min, the separation area of each separation system adopts 5 chromatographic columns and an elution area, 3 chromatographic columns can be eluted simultaneously, 2 chromatographic columns can be washed simultaneously in a washing area, and the separation is carried out under the condition of 45 ℃, wherein:
Separation system 1: each separation column is filled with 100g of Mel-PDMS separation adsorption material, and the saturated fatty acid of the separated product is eluted by using 5ml/min of n-hexane, and is washed by using 5ml/min of methanol.
Separation system 2: each separation column was packed with 100g of Ag + -Al 3+ Separating the adsorption material by SCA-DE, eluting and separating polyunsaturated fatty acid by 1-hexene with the feeding amount of 5ml/min, and cleaning by methanol with the feeding amount of 5 ml/min.
The specific operation is as follows: when the separation of the litsea cubeba oil mixed fatty acid is started, the fatty acid continuous coupling separation chromatographic column rotates anticlockwise, 3 steps are performed each time, 1 time is performed every 30 minutes, the whole separation system completes 1 complete process time for about 5 hours, and the process interval time between adjacent columns is 30 minutes. Each of the separated products was collected and purified by distillation under reduced pressure.
Under the conditions of the raw material consumption and the process, the feeding amount of the mixed fatty acid of the litsea cubeba oil is 300ml every 1h, and after passing through the separation system 1, 181.5ml of saturated fatty acid and 87.5ml of unsaturated fatty acid can be separated, the separation rate of the saturated fatty acid is 87.6%, and the separation rate of the unsaturated fatty acid is 94.1%; 59ml of monounsaturated fatty acid, 20.5ml of polyunsaturated fatty acid and 85.5% of polyunsaturated fatty acid can be separated out after passing through the separation system 2, and the separation rate of monounsaturated fatty acid is 85.4%.
Comparative example
On the basis of example 4, the following operations were explored:
1) Other conditions are unchanged, and when the feeding amount of the mixed fatty acid of the curcas seed oil is 15 ml/min:
the separation rate of the separated saturated fatty acid is 87.5 percent, and the separation rate of the unsaturated fatty acid is 82.2 percent; the monounsaturated fatty acid separation rate was 76.7%, and the polyunsaturated fatty acid separation rate was 72.6%.
2) Other conditions are unchanged, when 4 chromatographic columns are adopted in the separation areas of the 2 separation systems, 3 chromatographic columns can be eluted in the elution area, and 2 chromatographic columns can be simultaneously washed in the washing area:
the separation rate of the separated saturated fatty acid is 92.6 percent, and the separation rate of the unsaturated fatty acid is 74.5 percent; the monounsaturated fatty acid separation rate was 65.3%, and the polyunsaturated fatty acid separation rate was 63.2%.
3) Other conditions are unchanged, when the fatty acid continuous coupling separation chromatographic column rotates anticlockwise, 3 steps are performed each time, and 1 time is performed every 70 min:
the separation rate of the separated saturated fatty acid is 80.5 percent, and the separation rate of the unsaturated fatty acid is 89.7 percent; the monounsaturated fatty acid separation rate was 63.6%, and the polyunsaturated fatty acid separation rate was 71.9%.
4) Other conditions are unchanged, when the fatty acid continuous coupling separation chromatographic column rotates anticlockwise, every 15min rotates 1 time:
The separation rate of the separated saturated fatty acid is 66.7 percent, and the separation rate of the unsaturated fatty acid is 60.2 percent; the monounsaturated fatty acid separation rate was 72.5%, and the polyunsaturated fatty acid separation rate was 56.1%.
The above-mentioned exploration procedure shows that the number of chromatographic columns in the separation system, the rotational speed of the chromatographic columns and the feed flow rate all affect the separation efficiency, so that the proper above-mentioned conditions are needed for different separation objects to obtain a better fractionation effect.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (9)
1. A continuous fatty acid separation system, characterized by: comprises a separation device and a separation device, wherein the separation device comprises a separation device,
the separation device comprises a power device and a transmission shaft connected with the center of the power device, the power device is fixedly connected with the frame, the transmission shaft is driven to rotate through the power device, and then a separation column connected with the transmission shaft is driven to do circular motion; the center of the turntable is sleeved on the transmission shaft, round holes corresponding to the number and the size of the separation columns are formed along the periphery of the turntable, and the plurality of separation columns sequentially penetrate through the round holes of the turntable, so that the separation columns rotate along with the turntable when the transmission shaft drives the turntable;
the separating column is provided with a feeding hole and a discharging hole, the feeding hole is connected with a valve plate arranged at the top of the separating column, the valve plate is electrically connected with the digital display control device and is communicated with a piping panel, and the piping panel is provided with a plurality of feeding holes and a plurality of discharging holes for inputting and outputting materials and corresponds to the separating column one by one; the distributing plate is connected with the feed inlet of the distributing pipe panel through a hose, the feed outlet of the separating column is connected with the discharge outlet of the distributing pipe panel through a hose, and the distributing pipe panel is connected with the feed inlets or the feed outlets of different separating columns according to the separation process during operation; the tubing panel is also provided with a pump port, the pump port is connected with a peristaltic pump, and the peristaltic pump is used for controlling the flow speed of the material;
Feeding the material to be separated into the separation device, and dividing the separation columns of the separation device into at least 2 separation systems according to the arrangement sequence, wherein each separation system comprises: an adsorption separation zone, an elution zone and a washing zone; the adsorption separation zone is used for carrying out adsorption separation on the input materials, and the liquid flowing out after passing through the adsorption separation zone is an unsaturated fatty acid product;
the unsaturated fatty acid product enters an elution zone, the liquid flowing out after the elution treatment of the elution zone is a saturated fatty acid product, and the saturated fatty acid product enters a cleaning zone and flows out of a system after the cleaning treatment, so that single-system continuous separation is realized; or the unsaturated fatty acid product as a raw material enters a next separation system, and flows out of the system after being treated by the adsorption separation zone, the elution zone and the cleaning zone respectively, so that continuous coupling separation is realized.
2. The continuous fatty acid separation system according to claim 1, wherein: the separation system consists of a separation system 1 and a separation system 2, wherein the separation column, the feed inlet and the discharge outlet are respectively numbered as 1,2 and … … N-1,2N in sequence according to the arrangement sequence, wherein N is a positive integer, and preferably 10 < N < 20;
The separation system 1 consists of a separation column with a single number, the separation system 2 consists of a separation column with a double number, the separation column 1 corresponds to the feed inlet 1 before the separation device operates, and the separation column is connected with the next feed inlet of the same system every time the valve plate rotates for 1 time; when the first separation column of the separation system 1 reaches the N-number discharge port, the separation system 2 starts to work;
when the separation system 2 starts to work, the N-1 separation column is connected with the No. 2 feed inlet, and the No. 2 feed inlet is connected with the N discharge outlet before the separation system 2 runs, so that the non-adsorbed unsaturated fatty acid flows into the separation system 2 after passing through the separation system 1, and the separation column for adsorbing the saturated fatty acid in the separation system 1 enters an elution zone in the separation system 1, so that the saturated fatty acid and the unsaturated fatty acid are separated, and the grading continuous coupling separation is realized;
after saturated fatty acid is washed out by an elution zone in the separation system 1, unsaturated fatty acid enters a separation zone of the separation system 2, when a 1 st separation column of the separation system 2 reaches a last 1 material port N+1 number discharge port of the separation zone, unadsorbed monounsaturated fatty acid flows out, a separation column for adsorbing polyunsaturated fatty acid in the separation system 2 enters an elution zone in the separation system 2, so that the monounsaturated fatty acid is separated from the polyunsaturated fatty acid, and the monounsaturated fatty acid flows out of the system after being eluted by the elution zone in the separation system 2.
3. The continuous fatty acid separation system according to claim 2, characterized in that: 3-8 fixed end valve ports are connected in series in the adsorption separation area of the separation system 1 and used for inputting and outputting materials, the separation column is filled with a composite separation material of melamine and polydimethylsiloxane, and the eluting liquid in the eluting area is ethyl acetate or n-hexane, and the flow rate is 5-10ml/min.
4. The continuous fatty acid separation system according to claim 2, characterized in that: the separation system 2 is characterized in that 2-5 fixed end valve ports are connected in series in the adsorption separation area and used for inputting and outputting materials, a separation column is filled with metal complexing adsorption separation materials, preferably silver and aluminum complexing bimetallic complexing adsorption separation materials, and the eluting liquid in the eluting area is acetone or 1-hexene, and the flow rate is 5-10ml/min.
5. The continuous fatty acid separation system according to claim 3 or 4, characterized in that: the cleaning areas of the separation system 1 and/or the separation system 2 are connected with 1-2 fixed end valve ports in series for inputting and outputting materials, the cleaning liquid is methanol, and the liquid flow rate is 5-10ml/min.
6. The continuous fatty acid separation system according to claim 3 or 4, characterized in that: the adsorptive separation zone of the separation system 1 and/or separation system 2 contains 3-5 separation columns, the elution zone contains 2-4 separation columns, and the washing zone contains 1-2 separation columns, each separation column being filled with 50-150g of adsorptive separation material.
7. The continuous fatty acid separation system of claim 6 wherein: the separating device operates in such a way that the valve plate rotates clockwise, the separating columns rotate anticlockwise, each time the separating columns rotate and move for 2-5 steps, one step corresponds to one separating column, each time the separating columns rotate for 1 time every 20-60min, namely the same process node separation time between the adjacent separating columns is 20-60min.
8. The continuous fatty acid separation system of claim 7 wherein: after the separated material passes through the separation system 1, the saturated fatty acid and the unsaturated fatty acid are separated, the separation rate of the saturated fatty acid is 85-95%, and the separation rate of the unsaturated fatty acid is 90-95%.
9. The continuous fatty acid separation system of claim 8 wherein: after the unsaturated fatty acid passes through the separation system 2, the monounsaturated fatty acid and polyunsaturated fatty acid are separated, the separation rate of the monounsaturated fatty acid is 85-90%, and the separation rate of the polyunsaturated fatty acid is 85-94%.
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| CN202311562448.8A CN117586831A (en) | 2023-11-22 | 2023-11-22 | Fatty acid continuous separation system |
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| CN202311562448.8A CN117586831A (en) | 2023-11-22 | 2023-11-22 | Fatty acid continuous separation system |
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