CN119100927A - Preparation method of diglyceride - Google Patents
Preparation method of diglyceride Download PDFInfo
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- CN119100927A CN119100927A CN202411236101.9A CN202411236101A CN119100927A CN 119100927 A CN119100927 A CN 119100927A CN 202411236101 A CN202411236101 A CN 202411236101A CN 119100927 A CN119100927 A CN 119100927A
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- Prior art keywords
- chloride
- acid
- diglyceride
- eutectic solvent
- molar ratio
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- 238000002360 preparation method Methods 0.000 title claims description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 117
- 239000002904 solvent Substances 0.000 claims abstract description 73
- 230000005496 eutectics Effects 0.000 claims abstract description 63
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 33
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 33
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 33
- 229960003178 choline chloride Drugs 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 33
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 14
- 229930195729 fatty acid Natural products 0.000 claims abstract description 14
- 239000000194 fatty acid Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 235000011187 glycerol Nutrition 0.000 claims description 47
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical group [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 41
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 40
- 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 claims description 38
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 38
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 38
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 38
- 235000005074 zinc chloride Nutrition 0.000 claims description 22
- 239000011592 zinc chloride Substances 0.000 claims description 22
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 19
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 19
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 19
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 19
- 239000005642 Oleic acid Substances 0.000 claims description 19
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 19
- 235000021314 Palmitic acid Nutrition 0.000 claims description 19
- 235000021355 Stearic acid Nutrition 0.000 claims description 19
- 235000020669 docosahexaenoic acid Nutrition 0.000 claims description 19
- 229940090949 docosahexaenoic acid Drugs 0.000 claims description 19
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 19
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 19
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 19
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 19
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 19
- 229960002446 octanoic acid Drugs 0.000 claims description 19
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 19
- 235000021313 oleic acid Nutrition 0.000 claims description 19
- 239000008117 stearic acid Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 11
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 claims description 8
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 claims description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 claims description 2
- 229940005605 valeric acid Drugs 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 33
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 30
- 239000000047 product Substances 0.000 description 29
- 239000003921 oil Substances 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 229960002969 oleic acid Drugs 0.000 description 17
- 229940098695 palmitic acid Drugs 0.000 description 17
- 229960004274 stearic acid Drugs 0.000 description 17
- 238000007036 catalytic synthesis reaction Methods 0.000 description 15
- 238000000199 molecular distillation Methods 0.000 description 15
- 238000004451 qualitative analysis Methods 0.000 description 15
- 238000004445 quantitative analysis Methods 0.000 description 15
- 238000000926 separation method Methods 0.000 description 15
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 11
- 238000005886 esterification reaction Methods 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 7
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 7
- 229960003237 betaine Drugs 0.000 description 7
- 230000032050 esterification Effects 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 102000004882 Lipase Human genes 0.000 description 4
- 108090001060 Lipase Proteins 0.000 description 4
- 239000004367 Lipase Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 235000019421 lipase Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 102100021851 Calbindin Human genes 0.000 description 3
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- 101000898082 Homo sapiens Calbindin Proteins 0.000 description 3
- 101001021643 Pseudozyma antarctica Lipase B Proteins 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000002255 enzymatic effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000006911 enzymatic reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- -1 carbon chain fatty acid Chemical class 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229940112042 peripherally acting choline derivative muscle relaxants Drugs 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000004666 short chain fatty acids Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/27—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a liquid or molten state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明公开了一种甘油二酯的制备方法，其是将摩尔比1～2：1～2：2～4的氯化胆碱、金属氯化物和甘油在水浴中加热直至形成透明液体状的溶剂，得到低共熔溶剂；再将低共熔溶剂与脂肪酸混合，于油浴中进行搅拌反应，离心分离，分子蒸馏，即得甘油二酯。本发明利用氯化胆碱、与金属氯化物与甘油制备的低共熔溶剂作为催化剂，高效催化脂肪酸合成甘油二酯，产物易分离纯化，产物得率高，且催化剂可批次回收，具有更好的经济性和环保性。The present invention discloses a method for preparing diglyceride, which comprises heating choline chloride, metal chloride and glycerol in a molar ratio of 1 to 2: 1 to 2: 2 to 4 in a water bath until a transparent liquid solvent is formed to obtain a low eutectic solvent; then the low eutectic solvent is mixed with fatty acids, stirred and reacted in an oil bath, centrifuged and molecularly distilled to obtain diglyceride. The present invention uses choline chloride, a low eutectic solvent prepared from metal chloride and glycerol as a catalyst to efficiently catalyze fatty acids to synthesize diglyceride, the product is easy to separate and purify, the product yield is high, and the catalyst can be recovered in batches, which has better economy and environmental protection.
Description
Technical Field
The invention belongs to the technical field of oil modification, and in particular relates to a method for catalyzing and synthesizing diglyceride by using a eutectic solvent.
Background
Diglycerides are the most abundant components in natural oils and fats except triglycerides, have different digestion and metabolism modes from TAG, are not easy to store in the body in the form of fat, and are now recognized as safe and novel healthy oils and fats.
The preparation method of diglyceride mainly comprises an enzymatic method and a chemical method, wherein the enzymatic method for preparing diglyceride mainly comprises a direct esterification method, a glycerolysis method, a hydrolysis method and an ester exchange method. The esterification reaction is a simple and direct method, but the process needs to remove water generated in the reaction process in time, and the reaction process is longer, so that the energy consumption is increased. In the process of preparing diglyceride by hydrolysis of the oleolipase method, a large amount of by-product fatty acid is usually generated, and procedures of dehydration, recovery of free fatty acid by-product and the like are added after hydrolysis, so that the condition of realizing large-scale production is difficult to meet. The transesterification efficiency of the enzymatic transesterification for preparing diglyceride is low, the product yield is low, and the reaction conditions are required to be strictly controlled to prevent side reactions such as hydrolysis and the like. Therefore, the enzyme method for synthesizing diglyceride has the problems of more side reactions, difficult control of conditions, high cost and the like due to the multiple catalytic property of lipase, and is difficult to meet the industrial mass production. In comparison, the chemical method has lower synthesis industrialization cost and larger application potential. However, the chemical catalytic reaction generally adopts acid or alkali as a catalyst to catalyze the esterification reaction to synthesize diglyceride, and the operation needs to be performed at high temperature, so that the problems of high energy consumption and the like exist. Therefore, searching for a green and safe chemical process to replace the traditional technology is a technical bottleneck for synthesizing diglyceride by chemical catalytic esterification at present.
The eutectic solvent is a green solvent with good application prospect, and the components of the eutectic solvent are solvents formed by substances such as choline derivatives, alcohols, saccharides, urea and the like of micromolecular metabolites in organisms, and the eutectic solvent has the advantages of safety, no toxicity, biodegradability and 100% of atomic utilization rate. The eutectic solvent is used as a novel solvent with designability and has good application potential in the oil industry. However, only the eutectic solvent is used as an auxiliary agent, and the combined enzyme method for preparing diglyceride is reported, and no research on preparing diglyceride by using the eutectic solvent alone as a catalyst is reported.
Therefore, the design of the eutectic solvent with the catalytic function for esterification synthesis of diglyceride has very important significance.
Disclosure of Invention
Based on the above, the invention aims to provide a preparation method of diglyceride, which utilizes the eutectic solvent with a catalytic function to synthesize the diglyceride through esterification, has high catalytic efficiency, simple process and strong operability.
The specific technical scheme for achieving the aim of the invention comprises the following steps.
In a first aspect of the invention, the invention provides an application of a eutectic solvent as a catalyst in the preparation of diglycerides, wherein the eutectic solvent is prepared from choline chloride, metal chloride and glycerol in a molar ratio of 1-2:1-2:2-4.
In a second aspect of the present invention, there is provided a process for the preparation of diglycerides comprising the steps of:
(1) Heating choline chloride, metal chloride and glycerin in a molar ratio of 1-2:1-2:2-4 in a water bath until a transparent liquid solvent is formed, and obtaining a eutectic solvent;
(2) Mixing the eutectic solvent in the step (1) with fatty acid, stirring in an oil bath for reaction, centrifuging, and distilling the molecules to obtain diglyceride.
Based on the design experience of the eutectic solvent, the inventor of the invention discovers that only choline chloride (serving as a hydrogen bond donor), metal chloride (zinc chloride, aluminum chloride and ferric chloride serving as catalysts) and glycerin (serving as a hydrogen bond acceptor) are taken as raw materials, the liquid eutectic solvent (the eutectic solvent prepared by using other hydrogen bond donors is semi-solid or solid) can be prepared, and the eutectic solvent can be used for directly and efficiently catalyzing fatty acid to synthesize diglyceride (without using lipase), so that the product is easy to separate and purify, the product yield is high, and the catalyst can be recovered in batches, and has better economy and environmental protection.
The preparation method of diglyceride has simple process and is environment-friendly.
Detailed Description
The present invention will be described more fully hereinafter in order to facilitate an understanding of the present invention. This invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Unless otherwise indicated, all examples are given under conventional experimental conditions or according to the manufacturer's instructions, the raw materials and reagents used in the present invention are commercially available, and any biological material may be provided for external research.
In some embodiments of the invention, an application of a eutectic solvent as a catalyst in the preparation of diglycerides is disclosed, wherein the eutectic solvent is prepared from choline chloride, metal chloride and glycerol in a molar ratio of 1-2:1-2:2-4.
In some embodiments, the molar ratio of the choline chloride, the metal chloride and the glycerol is 1-2:1-2:3-4.
In some embodiments, the molar ratio of the choline chloride, the metal chloride and the glycerol is 1-2:2:3 or 2:1:4.
In some of these embodiments, the metal chloride is zinc chloride, ferric chloride, or aluminum chloride.
In some embodiments of the invention, a process for preparing diglycerides is disclosed, comprising the steps of:
(1) Heating choline chloride, metal chloride and glycerin in a molar ratio of 1-2:1-2:2-4 in a water bath until a transparent liquid solvent is formed, and obtaining a eutectic solvent;
(2) Mixing the eutectic solvent in the step (1) with fatty acid, stirring in an oil bath for reaction, centrifuging, and distilling the molecules to obtain diglyceride.
In some embodiments, the molar ratio of the choline chloride to the metal chloride to the glycerol is 1-2:1-2:3-4, and preferably, the molar ratio of the choline chloride to the metal chloride to the glycerol is 1-2:2:3 or 2:1:4.
In some of these embodiments, the metal chloride is zinc chloride, ferric chloride, or aluminum chloride.
In some embodiments, the temperature of the water bath in step (1) is 80 ℃ to 100 ℃.
In some embodiments, the temperature of the oil bath in the step (2) is 140 ℃ to 180 ℃, and the time of the oil bath is 10min to 30min.
In some of these embodiments, the fatty acid in step (2) is butyric acid, valeric acid, caprylic acid, capric acid, stearic acid, myristic acid, palmitic acid, oleic acid, or docosahexaenoic acid.
In some embodiments, the weight ratio of the eutectic solvent to the fatty acid in the step (2) is 1-3:7-9.
In the following examples, butyric acid, caprylic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid were all commercially available, and choline chloride, glycerol, zinc chloride, betaine, aluminum chloride and ferric chloride were all purchased from Shanghai Ala Biochemical technologies Co.
The present invention will be described in detail with reference to specific examples.
EXAMPLE 1 Process for the preparation of diglycerides
This example provides a process for preparing diglycerides comprising the steps of:
1. Heating choline chloride, zinc chloride and glycerin in a molar ratio of 1:1:3 in a water bath at 100 ℃ until a transparent liquid eutectic solvent is formed;
2. taking 20g of eutectic solvent, and respectively placing the eutectic solvent, 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid into different reaction kettles;
3. placing in 140 ℃ oil bath, stirring for 30min, and stopping the reaction;
4. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain high purity diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
EXAMPLE 2 Process for the preparation of diglycerides
This example provides a process for preparing diglycerides comprising the steps of:
1. Heating choline chloride, ferric chloride and glycerin in a molar ratio of 1:2:2 in a water bath at 100 ℃ until a transparent liquid eutectic solvent is formed;
2. taking 20g of eutectic solvent, and respectively placing the eutectic solvent, 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid into different reaction kettles;
3. placing in 140 ℃ oil bath, stirring for 30min, and stopping the reaction;
4. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain high purity diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
EXAMPLE 3 preparation of diglyceride
This example provides a process for preparing diglycerides comprising the steps of:
1. Heating choline chloride, aluminum chloride and glycerin in a molar ratio of 1:2:3 in a water bath at 100 ℃ until a transparent liquid eutectic solvent is formed;
2. taking 20g of eutectic solvent, and respectively placing the eutectic solvent, 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid into different reaction kettles;
3. stirring in 160 deg.C oil bath for 30min, and stopping reaction;
4. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain high purity diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
EXAMPLE 4 preparation method of diglyceride
This example provides a process for preparing diglycerides comprising the steps of:
1. Heating choline chloride, zinc chloride and glycerin in a molar ratio of 1:2:3 in a water bath at 100 ℃ until a transparent liquid eutectic solvent is formed;
2. taking 20g of eutectic solvent, and respectively placing the eutectic solvent, 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid into different reaction kettles;
3. Stirring in 180 deg.C oil bath for 10min, and stopping reaction;
4. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain high purity diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
EXAMPLE 5 preparation of diglyceride
This example provides a process for preparing diglycerides comprising the steps of:
1. heating choline chloride, zinc chloride and glycerin in a molar ratio of 2:1:4 in a water bath at 100 ℃ until a transparent liquid eutectic solvent is formed;
2. taking 10g of eutectic solvent, and respectively placing the eutectic solvent, 90g of butyric acid, caprylic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid into different reaction kettles;
3. stirring in 160 deg.C oil bath for 20min, and stopping reaction;
4. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain high purity diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
EXAMPLE 6 preparation of diglyceride
This example provides a process for preparing diglycerides comprising the steps of:
1. Heating choline chloride, ferric chloride and glycerin in a molar ratio of 2:1:1 in a water bath at 100 ℃ until a transparent liquid eutectic solvent is formed;
2. taking 20g of eutectic solvent, and respectively placing the eutectic solvent, 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid into different reaction kettles;
3. stirring in 160 deg.C oil bath for 20min, and stopping reaction;
4. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain high purity diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 1
The procedure of example 1 was followed except that the eutectic solvent used in the preparation of diglycerides was prepared from betaine, zinc chloride and glycerol in a molar ratio of 2:1:3.
Comparative example 2
The procedure of example 1 was followed except that the eutectic solvent used in the preparation of diglycerides was prepared from betaine, ferric chloride and glycerol in a molar ratio of 1:1:1.
Comparative example 3
The procedure of example 1 was followed except that the eutectic solvent used in the preparation of diglycerides was prepared from betaine, aluminum chloride and glycerol in a molar ratio of 1:1:3.
Comparative example 4
The procedure of example 1 was followed except that the eutectic solvent used in the preparation of diglycerides was prepared from betaine, zinc chloride and glycerol in a molar ratio of 1:1:2.
Comparative example 5
The method for preparing diglyceride provided in this comparative example comprises the following steps:
1. 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid are respectively mixed with 20g of glycerin in different reaction kettles, and then 50g of tertiary butanol is added into each reaction kettle as an auxiliary agent;
2. Adding 5g of lipase CALB, stirring the mixture in an oil bath at 60 ℃ for reaction for 24 hours, and centrifuging to obtain a supernatant, namely diglyceride.
Comparative example 6
The comparative example provides a process for preparing diglycerides comprising the steps of:
1. heating proline and glycerol in a molar ratio of 2:1 in a water bath at 100 ℃ until a transparent liquid eutectic solvent is formed;
2. Respectively placing 80g of butyric acid, caprylic acid, stearic acid, palmitic acid, oleic acid and docosahexaenoic acid in different reaction kettles, and sequentially adding 20g of eutectic solvent and 5g of ferric chloride;
3. Stirring in 150 deg.C oil bath for 30min, and stopping reaction;
4. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 7
This comparative example provides a method of synthesizing diglycerides comprising the steps of:
1. Respectively mixing 80g of butyric acid, caprylic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 20g of glycerin in different reaction kettles, and sequentially adding 5g of proline and 5g of aluminum chloride;
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 8
This comparative example provides a method of synthesizing diglycerides comprising the steps of:
1. Respectively mixing 80g of butyric acid, caprylic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 20g of glycerin in different reaction kettles, and sequentially adding 5g of proline and 5g of zinc chloride;
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 9
The comparative example provides a process for preparing diglycerides comprising the steps of:
1. Mixing 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 8.3g of glycerin in different reaction kettles, and sequentially adding 4.2g of choline chloride and 4.1g of zinc chloride (the molar ratio of choline chloride to zinc chloride to glycerin is 1:1:3);
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 10
The comparative example provides a process for preparing diglycerides comprising the steps of:
1. Mixing 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 8.3g of glycerin in different reaction kettles, and sequentially adding 4.2g of choline chloride and 4.0g of aluminum chloride (the molar ratio of choline chloride to aluminum chloride to glycerin is 1:1:3);
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 11
The comparative example provides a process for preparing diglycerides comprising the steps of:
1. Mixing 80g of butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 8.3g of glycerin in different reaction kettles, and sequentially adding 4.2g of choline chloride and 4.9g of ferric chloride solvent (the molar ratio of choline chloride to ferric chloride to glycerin is 1:1:3);
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 12
The comparative example provides a process for preparing diglycerides comprising the steps of:
1. Respectively mixing 80g of butyric acid, caprylic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 20g of glycerin in different reaction kettles, and adding 10g of zinc chloride;
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 13
The comparative example provides a process for preparing diglycerides comprising the steps of:
1. Respectively mixing butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 20g of glycerin in different reaction kettles, and adding 10g of ferric chloride;
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
Comparative example 14
The comparative example provides a process for preparing diglycerides comprising the steps of:
1. Mixing butyric acid, octanoic acid, stearic acid, palmitic acid, oleic acid, docosahexaenoic acid and 20g of glycerin in different reaction kettles respectively, and adding 10g of aluminum chloride;
2. stirring in 150 deg.C oil bath for 30min, and stopping reaction;
3. Centrifugal separation, further molecular distillation, GC-MS qualitative analysis to obtain diglyceride, GC-MS quantitative analysis to calculate the catalytic synthesis efficiency and product yield of diglyceride.
The catalytic efficiency and the product yield of the preparation methods of diglycerides of examples 1 to 6 and comparative examples 1 to 14 were counted, and whether the catalytic system could be used in batches was analyzed, and the results are shown in tables 1 to 3, respectively.
TABLE 1 catalytic efficiency of diglycerides
TABLE 2 product yield of diglycerides
Table 3 catalytic system batch utilization analysis
From tables 1-3, the eutectic solvent prepared from choline chloride, metal chloride (zinc chloride, ferric chloride or aluminum chloride) and glycerin can be used as a catalyst, has substrate universality, can catalyze fatty acids with different chain lengths to synthesize diglycerides, has high catalytic efficiency and high product yield, and the catalytic system can be utilized in batches, so that the use efficiency of the eutectic solvent is improved, the influence on the environment is effectively reduced, and the production is more in accordance with the green subject (examples 1-6), wherein the butyric acid is short-chain fatty acid, is easy to volatilize due to heating in the reaction process, and has relatively low catalytic efficiency and product yield.
Compared with examples 1-6, the catalyst efficiency and the product yield of the esterification of fatty acid substrates with different chain lengths to synthesize diglycerides are obviously reduced by adopting the eutectic solvent prepared from betaine, metal chloride (zinc chloride, ferric chloride or aluminum chloride) and glycerin or adopting the eutectic solvent prepared from proline and glycerin to be matched with the metal chloride, and the catalyst system cannot be utilized in batches (comparative examples 1-4 and comparative example 6). The method is likely to be because the eutectic solvent prepared from choline chloride, metal chloride (zinc chloride, ferric chloride or aluminum chloride) and glycerin is a liquid solvent, can be fully contacted with a substrate in the catalysis process, and has good catalysis performance, while the eutectic solvent prepared from betaine, metal chloride (zinc chloride, ferric chloride or aluminum chloride) and glycerin is a solid or semisolid system, and is insufficiently contacted with the substrate, the efficiency and the product yield of esterification synthesis of diglyceride are obviously reduced, and the solid or semisolid catalysis system is not easy to separate, so that batch utilization of the solvent cannot be realized. The catalytic metal chloride of comparative example 6 was also present as solid particles, and its catalytic efficiency was limited, resulting in low product yield and system failure to realize batch utilization.
In the comparative example 5, the enzymatic synthesis of diglyceride is adopted, on one hand, CALB lipase has specificity to a substrate and has reduced catalytic efficiency to the substrate with carbon chain more than 18, on the other hand, because CALB is liquid enzyme, the system moisture can inhibit the reaction from proceeding to the direction of the product without dehydration, and meanwhile, the substrate solubility is also related to the catalytic efficiency without auxiliary agent, and in addition, the product of the enzymatic process is monoglyceride as well as monoglyceride, therefore, the catalytic efficiency and the product yield of diglyceride are lower by adopting the preparation method of the comparative example 5.
Comparative examples 7 to 8 used proline, metal chlorides (zinc chloride, aluminum chloride and ferric chloride) and glycerin as a mixture (non-eutectic solvent), comparative examples 9 to 11 used choline chloride, metal chlorides (zinc chloride, aluminum chloride and ferric chloride) and glycerin as a mixture (non-eutectic solvent), comparative examples 12 to 14 used metal chlorides (zinc chloride, aluminum chloride and ferric chloride) and glycerin as a mixture (non-eutectic solvent), and the catalyst efficiency was low when the catalyst was added to different carbon chain fatty acid substrates for esterification synthesis of diglyceride, and the main reason probably was that the metal chlorides having catalytic effect were present as solid particles, the catalyst efficiency was limited, and thus the product yield was also low, and the system could not realize batch utilization.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The application of the eutectic solvent in preparing diglyceride as a catalyst is characterized in that the eutectic solvent is prepared from choline chloride, metal chloride and glycerol in a molar ratio of 1-2:1-2:2-4.
2. The use according to claim 1, wherein the molar ratio of choline chloride, metal chloride and glycerol is 1-2:1-2:3-4.
3. The use according to claim 2, wherein the molar ratio of choline chloride, metal chloride and glycerol is 1:1-2:3 or 2:1:4.
4. The use according to any one of claims 1 to 3, wherein the metal chloride is zinc chloride, iron chloride or aluminum chloride.
5. A process for the preparation of diglycerides, comprising the steps of:
(1) Heating choline chloride, metal chloride and glycerin in a molar ratio of 1-2:1-2:2-4 in a water bath until a transparent liquid solvent is formed, and obtaining a eutectic solvent;
(2) Mixing the eutectic solvent in the step (1) with fatty acid, stirring in an oil bath for reaction, centrifuging, and distilling the molecules to obtain diglyceride.
6. The preparation method according to claim 5, wherein the molar ratio of the choline chloride, the metal chloride and the glycerol in the step (1) is 1-2:1-2:3-4, and preferably the molar ratio of the choline chloride, the metal chloride and the glycerol is 1:1-2:3 or 2:1:4.
7. The method of claim 6, wherein the metal chloride is zinc chloride, ferric chloride or aluminum chloride.
8. The preparation method according to claim 5, wherein the temperature of the water bath in the step (1) is 80-100 ℃, and/or the temperature of the oil bath in the step (2) is 140-180 ℃, and the time of the oil bath is 10-30 min.
9. The method according to claim 5, wherein the fatty acid in the step (2) is butyric acid, valeric acid, caprylic acid, capric acid, stearic acid, myristic acid, palmitic acid, oleic acid or docosahexaenoic acid.
10. The preparation method according to claim 5, wherein the weight ratio of the eutectic solvent to the fatty acid in the step (2) is 1-3:7-9.
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