CN116854591B - Synthesis method of fatty acid ester alkoxylate and application of Ru/MgO catalyst - Google Patents
Synthesis method of fatty acid ester alkoxylate and application of Ru/MgO catalyst Download PDFInfo
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- CN116854591B CN116854591B CN202310656446.9A CN202310656446A CN116854591B CN 116854591 B CN116854591 B CN 116854591B CN 202310656446 A CN202310656446 A CN 202310656446A CN 116854591 B CN116854591 B CN 116854591B
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- fatty acid
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- acid ester
- alkylene oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 73
- 239000000194 fatty acid Substances 0.000 title claims abstract description 73
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 73
- -1 fatty acid ester Chemical class 0.000 title claims abstract description 68
- 238000001308 synthesis method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 90
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 71
- 239000011261 inert gas Substances 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 230000000977 initiatory effect Effects 0.000 claims abstract description 9
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 27
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 21
- 150000002148 esters Chemical group 0.000 claims description 20
- 150000004665 fatty acids Chemical class 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- IREVRWRNACELSM-UHFFFAOYSA-J ruthenium(4+);tetrachloride Chemical compound Cl[Ru](Cl)(Cl)Cl IREVRWRNACELSM-UHFFFAOYSA-J 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 150000003303 ruthenium Chemical class 0.000 claims description 2
- 238000007670 refining Methods 0.000 abstract description 9
- 238000007599 discharging Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000001413 cellular effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 238000009826 distribution Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- 238000001914 filtration Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- 238000007046 ethoxylation reaction Methods 0.000 description 8
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 229940071160 cocoate Drugs 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 229960004592 isopropanol Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003023 Mg-Al Inorganic materials 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009954 braiding Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 231100000584 environmental toxicity Toxicity 0.000 description 1
- FMMOOAYVCKXGMF-MURFETPASA-N ethyl linoleate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)OCC FMMOOAYVCKXGMF-MURFETPASA-N 0.000 description 1
- 229940031016 ethyl linoleate Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
- 150000002338 glycosides Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FMMOOAYVCKXGMF-UHFFFAOYSA-N linoleic acid ethyl ester Natural products CCCCCC=CCC=CCCCCCCCC(=O)OCC FMMOOAYVCKXGMF-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2615—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/266—Metallic elements not covered by group C08G65/2648 - C08G65/2645, or compounds thereof
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthesis method of fatty acid ester alkoxylate and application of Ru/MgO catalyst, wherein the synthesis method comprises the following steps: (1) placing Ru/MgO catalyst in a reaction system; (2) feeding a fatty acid ester into the reaction system; (3) The inert gas cleans the cavity of the reactor and heats up to the initiation temperature, and the first part of alkylene oxide is fed into the reaction system to initiate reaction; (4) Continuously adding a second part of alkylene oxide, maintaining the reaction temperature, and then cooling to discharge a liquid phase substance to obtain a fatty acid ester alkoxylate; wherein the Ru/MgO catalyst is a sheet-like or honeycomb-like heterogeneous catalyst. According to the invention, the synthesis of the fatty acid ester alkoxylate is carried out based on the flaky or cellular heterogeneous Ru/MgO catalyst, the refining step of removing the catalyst is not needed after the reaction is completed, the fatty acid ester alkoxylate product can be directly prepared by cooling and discharging, and the product has clear and transparent appearance and excellent performance.
Description
Technical Field
The invention relates to the technical field of ester alkoxylates, in particular to a synthesis method of a fatty acid ester alkoxylate and application of a Ru/MgO catalyst.
Background
Fatty acid ester alkoxylates (such as fatty acid methyl ester ethoxylate FMEE) are a novel class of ether-ester nonionic surfactants that are not only comparable to alcohol ethers (such as fatty alcohol polyoxyethylene ether AEO) in surface activity, detergency, biodegradability and hard water resistance, but also less irritating, comparable to the green surfactants alkyl polyglycosides (such as alkyl glycoside APG), and even better in skin compatibility and ecotoxicity than alkyl polyglycosides. Compared with alcohol ether, the fatty acid ester alkoxylate has the characteristics of cheap raw materials, low foam, high water-solubility, strong oil solubilization capacity, small skin irritation, good biodegradability and the like, is a green and environment-friendly surfactant, has a production process which is less than that of the alcohol ether by one step of hydrogenation, reduces the pollution of chemical production process to the environment, has low foam and easy rinsing when in use, has more advantages than the alcohol ether in the industrial field, is more favorable for saving water as civil products, and has better comprehensive performance than the alcohol ether. From the development trend, the fatty acid ester alkoxylate can possibly replace alcohol ether in a plurality of industries to cause the further transformation of the nonionic surface activity industry, and is clearly one of the important development varieties by the national light industry regulation and vibration planning.
FMEE contains no active hydrogen and requires special inserted catalysts for one-step synthesis. In patent WO 02/38269, isopropanol, calcium acetate, calcium lactate and/or other low molecular carboxylic acid or calcium salt of hydroxycarboxylic acid and/or hydrate of the former are reacted with sulfuric acid to prepare the catalyst, and the synthesized FMEE has the advantages of narrow molecular weight distribution and low content of free fatty acid methyl ester. However, the isopropyl alcohol used in this patent is not removed and the subsequent product may contain impurities or odors.
Lion king Co., ltd., CN107921421A reacted with calcium acetate monohydrate and 2-propanol to obtain a dispersion, and then sulfuric acid was added dropwise to the dispersion for 1 hour, followed by a reaction for 2 hours to obtain a reaction product. After the separation operation and the washing operation are repeated twice, the catalyst is obtained after drying at 50 ℃ for 2 hours. Compared with Al-Mg catalyst and sodium hydroxide catalyst, the catalyst has the advantages of low content of high molecular PEG and narrow molecular weight distribution of the product. However, the catalyst needs to be subjected to two separation and washing operations, the operation is complicated, and more solvent is generated and needs to be treated.
Patent US9056828 uses barium oxide and sulfuric acid as catalysts to prepare fatty acid methyl ester ethoxylate, and has the defect of long induction period. Barium oxide is also toxic. U.S. patent No. 6008392 discloses a fatty acid methyl ester ethoxylation catalyst which is mainly composed of Al/Mg hydrotalcite and a small amount of LiOH or SnO 2. U.S. patent No. 5220246 discloses an active calcium aluminum alkoxide composite catalyst for ethoxylation of methyl cocoate with an average addition number of 8. Chinese patent CN105268428a discloses a method for preparing fatty acid methyl ester ethoxylation catalyst, firstly, mixing carboxylic anhydride and fatty alcohol polyoxyethylene ether, then adding alkaline earth metal salt and rare earth metal salt into the mixture, regulating pH of the mixture with concentrated sulfuric acid, and vacuum drying at below 100 deg.c to obtain the described catalyst. Chinese patent CN107282135A discloses a fatty acid methyl ester ethoxylation catalyst, which is obtained by mixing alkaline earth metal carboxylate, transition metal salt, sulfuric acid and alcohol to obtain a mixture, then performing a closed heat treatment, and cooling to obtain the catalyst. Chinese patent CN105268481a discloses a fatty acid methyl ester ethoxylation catalyst, which is prepared by mixing alkaline earth metal carboxylate, powdery rare earth oxide, 5A molecular sieve and water to obtain a mixture, then performing a closed heat treatment, and drying and cooling. Chinese patent CN107442173a discloses a preparation method of fatty acid methyl ester ethoxylation catalyst, which is to mix alkaline earth metal sulfonate, lanthanide metal salt, carboxylic acid and alcohol to obtain a mixture, then to carry out a closed heat treatment, and then to obtain the catalyst after drying and cooling. Chinese patent CN105498842A discloses a preparation method of a fatty acid methyl ester ethoxylation catalyst, which comprises the steps of mixing at least one of alkaline earth metal carboxylate and Zn salt Cd salt and N-hydroxyimide with water to obtain a mixture, performing closed heat treatment, and drying and cooling to obtain the catalyst.
The catalysts in the above patents can be used for alkoxylation of fatty acid esters such as ethoxylation, but if the FMEE product in the above patent is not subjected to refining filtration, the catalyst remains in the product, the product becomes turbid and layered, the high ion content limits the application in many fields, and the refining filtration brings about product yield loss and solid waste. Therefore, how to develop a preparation method of fatty acid ester alkoxylate to overcome the above-mentioned drawbacks is a technical problem to be solved.
Disclosure of Invention
The invention provides a synthesis method of a fatty acid ester alkoxylate and application of a Ru/MgO catalyst, and aims to simplify the preparation process of the fatty acid ester alkoxylate so as to better prepare the fatty acid ester alkoxylate.
In one aspect, the present invention relates to a method for synthesizing a fatty acid ester alkoxylate, comprising the steps of: (1) placing Ru/MgO catalyst in a reaction system; (2) feeding a fatty acid ester to the reaction system; (3) Cleaning a reactor cavity by inert gas, heating to an initiation temperature, and feeding a first part of alkylene oxide into the reaction system to initiate reaction; (4) Continuously adding a second part of alkylene oxide, maintaining the reaction temperature, and then cooling to discharge a liquid phase substance to obtain the fatty acid ester alkoxylate; wherein the Ru/MgO catalyst is a sheet-like or honeycomb-like heterogeneous catalyst.
Optionally, in step (1), placing the Ru/MgO catalyst in the reaction system comprises: and fixing the Ru/MgO catalyst on the stirrer of the high-pressure polymerization reaction kettle or the inner wall of the reaction kettle.
Optionally, the Ru/MgO catalyst uses metal magnesium as a matrix, the surface of the metal magnesium is three-dimensional porous MgO, and Ru nano particles are loaded on the surface of MgO and in the pore canal.
Optionally, the dosage of the Ru/MgO catalyst is 0.05-1 per mill of the total discharging mass of the fatty acid ester alkoxylate.
Optionally, in step (2), the fatty acid ester is selected from esters of C6-C18 fatty acids with C1-C4 alcohols.
Optionally, in the step (3), the inert gas cleaning the reactor cavity is performed 2-5 times, and the initiation temperature is 90-130 ℃.
Optionally, the synthesis method further comprises the following steps between step (3) and step (4): and after the pressure of the reaction system is reduced and the temperature is increased, continuously adding the second part of alkylene oxide, and keeping the pressure of the reaction system to be less than or equal to 0.5MPa.
Optionally, the first portion of alkylene oxide in step (3), and the second portion of alkylene oxide in step (4), each independently selected from the group consisting of one or more of ethylene oxide, propylene oxide, and butylene oxide.
Alternatively, in step (4), where the second portion of alkylene oxide is a combination of a plurality of ethylene oxide, propylene oxide and butylene oxide, each alkylene oxide is added alone or in a mixture of a plurality.
Alternatively, the ratio of the moles of the fatty acid ester to the total moles of the first portion of alkylene oxide and the second portion of alkylene oxide is from 1:1 to 100.
Optionally, in step (4), maintaining the reaction temperature comprises: maintaining the temperature of the reaction system at 90-180 ℃ during the continuous addition of the second portion of alkylene oxide; after the second part of alkylene oxide is added, the temperature of the reaction system is kept at 90-180 ℃ for 20-60 min.
In another aspect, the invention relates to the use of a Ru/MgO catalyst in the alkoxylation of fatty acid esters, said Ru/MgO catalyst being a platelet-shaped or honeycomb-shaped heterogeneous catalyst.
The beneficial effects are that:
according to the invention, the synthesis of the fatty acid ester alkoxylate is carried out based on the flaky or cellular heterogeneous Ru/MgO catalyst, the refining step of removing the catalyst is not needed after the reaction is completed, the fatty acid ester alkoxylate product can be directly prepared by cooling and discharging, and the product is clear and transparent in appearance, extremely low in ion content and excellent in performance.
Detailed Description
The present application will be described in further detail by way of examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
In one aspect, the present invention relates to a method for synthesizing a fatty acid ester alkoxylate, comprising the steps of: (1) placing Ru/MgO catalyst in a reaction system; (2) feeding a fatty acid ester to the reaction system; (3) Cleaning a reactor cavity by inert gas, heating to an initiation temperature, and feeding a first part of alkylene oxide into the reaction system to initiate reaction; (4) Continuously adding a second part of alkylene oxide, maintaining the reaction temperature, and then cooling to discharge a liquid phase substance to obtain the fatty acid ester alkoxylate; wherein the Ru/MgO catalyst is a sheet-like or honeycomb-like heterogeneous catalyst.
It should be noted that, in the preparation of fatty acid ester alkoxylates in the prior art, a separation process is also required to remove the catalyst after the reaction is completed. According to the synthesis method of the fatty acid ester alkoxylate, the Ru/MgO catalyst is a flaky or honeycomb heterogeneous catalyst, and the catalyst does not enter a product, so that the catalyst is not required to be refined and removed in the synthesis method, and the fatty acid ester alkoxylate can be directly obtained by discharging a liquid phase after reaction.
In addition, the prepared fatty acid ester alkoxylate is clear and transparent in appearance, has extremely low ion content, simplifies the preparation process, improves the production efficiency and the product yield, and has important significance for the production of the fatty acid ester alkoxylate.
In addition, the synthetic method of the invention has stable whole technological process, and can directly synthesize the fatty acid ester alkoxylate product with excellent performance by a one-step method in the stable technological process.
In one specific embodiment of the synthesis method according to the present invention, in the step (1), placing the Ru/MgO catalyst in the reaction system includes: and fixing the Ru/MgO catalyst on the stirrer of the high-pressure polymerization reaction kettle or the inner wall of the reaction kettle.
In the synthesis method of the present invention, the Ru/MgO catalyst may be fixed to the stirrer of the high-pressure polymerization reactor or the inner wall of the reactor, and the Ru/MgO catalyst may be fixed to the stirrer by a mechanical connection means such as binding, or may be fixed to the inner wall of the reactor by a mechanical connection means such as bonding. The Ru/MgO catalyst needs to be replaced when being fixed on the inner wall of the reaction kettle, so that the catalyst is prevented from colliding with the stirrer. The fatty acid ester alkoxylate is synthesized by the one-step method, and a clear and transparent high-performance fatty acid ester alkoxylate product can be obtained without refining treatment.
According to another specific embodiment of the synthesis method, the Ru/MgO catalyst takes magnesium metal as a matrix, the surface of the magnesium metal is three-dimensional porous MgO, and Ru nano particles are loaded on the surface of MgO and in pore channels.
The Ru/MgO catalyst can be prepared by a microplasma oxidation method and can be prepared by a method described in patent CN 109289846B. Specifically, the preparation method of the Ru/MgO catalyst can comprise the following steps:
(1) Providing or preparing a honeycomb structure woven by metal magnesium sheets or magnesium wires; the size of the metal magnesium sheet can be about 4cm multiplied by 2mm, and the honeycomb structure can be formed by weaving magnesium wires with the length of 1m and the diameter of 500 mu m;
(2) Dissolving ruthenium salt in an acid solution to obtain a ruthenium tetrachloride solution;
(3) Providing or preparing an electrolyte; the electrolyte consists of sodium silicate solution with the concentration of 8 g/ml-36 g/ml, potassium fluoride solution with the concentration of 2 g/ml-16 g/ml and potassium hydroxide solution with the concentration of 4 g/ml-16 g/ml in a volume ratio of 1:1:1;
(4) Mixing ruthenium tetrachloride solution with electrolyte to obtain mixed solution; the concentration of ruthenium tetrachloride in the mixed solution is 1 x 10 -3～1*10-2 mol/L;
(5) Keeping the temperature of the mixed solution at 0-25 ℃, taking metal magnesium as an anode, performing a microplasma oxidation process to obtain a Ru/MgO catalyst, and washing and drying the catalyst;
the parameters of the microplasma oxidation process are as follows: the pulse width is 200-1000 mu s, the pulse number is 24-120 Hz, the pulse current density is 0.4-2A/cm 2, and the action time is 1-3 min; liquid nitrogen is used to pour the anode metal magnesium during the process.
According to a specific embodiment of the synthesis method, the dosage of the Ru/MgO catalyst is 0.05-1 per mill of the total discharge mass of the fatty acid ester alkoxylate.
It should be noted that, preferably, the dosage of the Ru/MgO catalyst is 0.05 to 0.1 mill of the total discharging mass of the fatty acid ester alkoxylate, specifically, may be 0.07 mill, 0.08 mill, 0.09 mill, etc., the dosage of the catalyst seriously affects the price of the product, the lowest dosage of the catalyst, and the best catalyst efficiency is beneficial to cost control.
According to one embodiment of the synthesis method of the present invention, in step (2), the fatty acid ester is selected from esters of fatty acids of C6 to C18 with alcohols of C1 to C4.
The fatty acid of C6-C18 is selected from linear or branched saturated or unsaturated fatty acid; the C1-C4 alcohol is selected from linear or branched saturated fatty alcohol. Preferably, the fatty acid ester is selected from esters of C8-C18 fatty acids with methanol or ethanol, more preferably esters of C12-C18 fatty acids with methanol or ethanol. The fatty acid of C12-C18 has wide sources, and the steric hindrance of the ester formed by the fatty acid and methanol or ethanol is small, thereby being more beneficial to the alkoxylation reaction.
In addition, in the step (2), after the fatty acid ester is fed to the reaction system such as a high-pressure reaction vessel, the reaction vessel may be closed at this time.
According to another embodiment of the synthesis method of the present invention, in the step (3), the inert gas purging of the reactor cavity is performed 2 to 5 times, and the initiation temperature is 90 to 130 ℃.
The inert gas may be used to clean the reactor cavity with an inert gas such as N 2, preferably, the initiation temperature is 110 to 130 ℃, specifically 115 ℃, 120 ℃, 125 ℃ and the like, which is beneficial to reducing the induction period and shortening the overall reaction time.
According to a specific embodiment of the synthesis method according to the invention, the synthesis method further comprises the following steps between step (3) and step (4): and after the pressure of the reaction system is reduced and the temperature is increased, continuously adding the second part of alkylene oxide, and keeping the pressure of the reaction system to be less than or equal to 0.5MPa.
In the synthesis method of the invention, after a small amount of first part of alkylene oxide is added to initiate reaction, when the pressure of the reaction system is reduced and the temperature is increased, the second part of alkylene oxide is continuously added until the design quality is achieved, the pressure of the reaction system is kept to be less than or equal to 0.5MPa, and the pressure of the reaction system is kept to be less than or equal to 0.5MPa in the whole process of adding the second part of alkylene oxide, so that the whole process can be carried out more stably, and the fatty acid ester alkoxylate product with excellent performance can be prepared better.
According to a specific embodiment of the synthesis process according to the present invention, the first portion of alkylene oxide in step (3) and the second portion of alkylene oxide in step (4) are each independently selected from the group consisting of one or more of ethylene oxide, propylene oxide and butylene oxide.
The first portion of alkylene oxide was used to initiate the reaction, and the second portion of alkylene oxide was continuously added until the design quality was reached.
According to one embodiment of the synthesis method of the present invention, when the second portion of alkylene oxide is a combination of a plurality of ethylene oxide, propylene oxide and butylene oxide, each alkylene oxide is added alone or in a mixture of a plurality of alkylene oxides.
In this embodiment, when the second portion of alkylene oxide is added, each of the alkylene oxides may be continuously added while maintaining the pressure of the reaction system at 0.5MPa or less; the reaction temperature is maintained during each alkylene oxide addition, one alkylene oxide addition may be maintained at the reaction temperature for a period of time, such as 20-40 minutes, after the addition of one alkylene oxide is completed, and then the continuous addition of the other alkylene oxide is begun, and maintained at the reaction temperature for a period of time, such as 20-40 minutes, after the addition of the other alkylene oxide is completed.
In addition, as a preferable embodiment, the second portion of alkylene oxide includes ethylene oxide and propylene oxide added before and after each other, or propylene oxide and ethylene oxide added before and after each other; in this preferred embodiment, the first portion of alkylene oxide used to initiate the reaction may be ethylene oxide or propylene oxide to produce fatty acid ester alkoxylates of block combinations of ethylene oxide and propylene oxide in different ways.
According to one embodiment of the synthesis method of the present invention, the ratio of the number of moles of the fatty acid ester to the total number of moles of the first portion of alkylene oxide and the second portion of alkylene oxide is 1:1 to 100.
The ratio of the mole number of the fatty acid ester to the total mole number of the first portion of alkylene oxide and the second portion of alkylene oxide is preferably 1:7 to 40, more preferably 1:7 to 20, which is advantageous for adjusting the HLB value (hydrophile-lipophile balance value) and ensuring optimal catalyst efficiency. Specifically, the ratio of the mole number of the fatty acid ester to the total mole number of the first portion of alkylene oxide and the second portion of alkylene oxide may also be 1: 10. 1: 15. 1: 25. 1: 30. 1: 35. 1: 45. 1: 50. 1: 60. 1:70, etc.
According to one embodiment of the synthesis method of the present invention, in step (4), maintaining the reaction temperature comprises: maintaining the temperature of the reaction system at 90-180 ℃ during the continuous addition of the second portion of alkylene oxide; after the second part of alkylene oxide is added, the temperature of the reaction system is kept at 90-180 ℃ for 20-60 min.
The period of time during which the second portion of alkylene oxide is continuously fed is a reaction time, and the period of time during which the second portion of alkylene oxide is maintained after the completion of the feeding may be referred to as an aging process or a curing process. Preferably, the reaction temperature and aging temperature are 140 to 160 ℃, more preferably 150 to 155 ℃, which is advantageous in avoiding the formation of byproducts and the control of the color of the product, and in preparing a product with better performance.
In another aspect, the invention relates to the use of a Ru/MgO catalyst in the alkoxylation of fatty acid esters, said Ru/MgO catalyst being a platelet-shaped or honeycomb-shaped heterogeneous catalyst.
In this application, the Ru/MgO catalyst uses magnesium metal as a matrix, the surface of the magnesium metal is three-dimensional porous MgO, and Ru nanoparticles are supported on the surface of MgO and in the pores. The preparation method of the Ru/MgO catalyst may be the method of steps (1) to (5) as described above.
The synthesis method of the fatty acid ester alkoxylate or the application of the Ru/MgO catalyst in the alkoxylation of fatty acid ester is characterized in that the Ru/MgO catalyst is a heterogeneous catalyst, can be fixed in a reaction kettle and does not enter a product, and the product has the advantages of clear and transparent appearance, extremely low ion content and the like without refining treatment, does not need neutralization, has basically zero water content and basically zero ion content, and can be widely applied to a plurality of fields such as cleaning of precise parts.
The present invention will be further described in detail by way of examples, which may be commercially available, except for the specific descriptions, of reagents and the like used in the examples below. The catalyst in the following examples may be fixed to the agitator of the autoclave by binding or the like.
Example 2 in CN 109289846B the Ru/MgO catalyst preparation procedure is as follows:
(1) Braiding magnesium wires with the diameter of 500 mu m and the length of 1m into a metal geometric body with a honeycomb structure, ultrasonically cleaning the metal geometric body in ethanol for 30min, and drying and storing the metal geometric body in an oven;
(2) Diluting concentrated hydrochloric acid to prepare 0.024mol/L dilute hydrochloric acid; 1g of ruthenium trichloride is dissolved in 1.2ml of dilute hydrochloric acid solution, the volume is fixed to 20ml, and the concentration of the finally formed ruthenium tetrachloride solution is 0.24mol/L;
(3) Preparing electrolyte, namely adding sodium silicate, potassium fluoride and potassium hydroxide into 500ml of water respectively, and dissolving; the concentration of the potassium fluoride and the potassium hydroxide are respectively 15g/ml of sodium silicate, 8g/ml of potassium fluoride and 8g/ml of potassium hydroxide;
(4) Adding 10ml of the prepared ruthenium tetrachloride solution into the electrolyte, and uniformly mixing, wherein the final concentration of ruthenium tetrachloride is 8 x 10 -3 mol/L;
(5) Carrying out liquid nitrogen cooling treatment on the electrolyte added with ruthenium tetrachloride, so that the temperature of the electrolyte added with ruthenium tetrachloride is kept between 5 and 10 ℃;
(6) Taking a honeycomb metal geometry as an anode for microplasma oxidation treatment, wherein the pulse width is 600 mu s, the pulse number is 40Hz, the pulse current density is 1A/cm 2, and the action time is 3min;
(7) In the microplasma oxidation process, cooling treatment and casting are carried out on the magnesium honeycomb substrate by using liquid nitrogen, wherein the frequency is 20 s/time;
(8) After the experiment was completed, the Ru/MgO-loaded honeycomb magnesium base was rinsed 5 times with ultrapure water and stored dry in an oven.
Example 1
Ru/MgO catalyst, 0.05g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 300g of methyl palmitate (chain length distribution of fatty acid C16-C18, chain length of ester C1) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 695g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 40min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-1, and the raw material proportion and evaluation index are shown in Table 1.
Example 2
Ru/MgO catalyst, 0.07g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high pressure polymerization vessel stirrer. 245g of methyl cocoate (chain length distribution of fatty acid C12-C14 and chain length of ester C1) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 750g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 30min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-2, and the raw material proportion and evaluation index are shown in Table 1.
Example 3
Ru/MgO catalyst, 0.05g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 480g of methyl palmitate (chain length distribution of fatty acid C16-C18, chain length of ester C1) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 110 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 515g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 140-150 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 140-150 ℃ for 40min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-3, and the raw material proportion and evaluation index are shown in Table 1.
Example 4
Ru/MgO catalyst, 0.05g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 470g of methyl palmitate (fatty acid chain length distribution C16-C18, chain length C1 of ester) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 110 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 420g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 140-150 ℃. After the addition of ethylene oxide is completed, the mixture is kept at 140-150 ℃ for 20min. Continuously adding 110g of propylene oxide under the condition that the pressure is not more than 0.5MPa, wherein the reaction temperature is 140-150 ℃, and keeping the temperature at 140-150 ℃ for 40min after the propylene oxide is completely added. Cooling and discharging to obtain a clear and transparent FMEE product, which is marked as FMEE-4, and the proportion and evaluation index of the raw materials are shown in Table 1.
Example 5
Ru/MgO catalyst, 0.05g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 470g of methyl palmitate (fatty acid chain length distribution C16-C18, chain length C1 of ester) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 110 ℃, and initiated by the addition of 5g propylene oxide. After the pressure is reduced and the temperature is increased, 105g of propylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 140-150 ℃. After the addition of propylene oxide is completed, the mixture is kept at 140-150 ℃ for 20min. Continuously adding 420g of ethylene oxide under the condition that the pressure is not more than 0.5MPa, wherein the reaction temperature is 140-150 ℃, and keeping the temperature at 140-150 ℃ for 40min after the ethylene oxide is completely added. Cooling and discharging to obtain a clear and transparent FMEE product, which is marked as FMEE-5, and the proportion and evaluation index of the raw materials are shown in Table 1.
Example 6
Ru/MgO catalyst 0.09g was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 200g of methyl cocoate (chain length distribution of fatty acid C12-C14, chain length of ester C1) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 795g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 30min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-6, and the raw material proportion and evaluation index are shown in Table 1.
Example 7
Ru/MgO catalyst, 0.1g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 210g of methyl palmitate (chain length distribution of fatty acid C16-C18, chain length of ester C1) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 785g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 40min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-7, and the raw material proportion and evaluation index are shown in Table 1.
Example 8
Ru/MgO catalyst, 0.1g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 110g of methyl cocoate (chain length distribution of fatty acid C12-C14, chain length of ester C1) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 120 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 885g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 150-160 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 150-160 ℃ for 30min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-8, and the raw material proportion and evaluation index are shown in Table 1.
Example 9
Ru/MgO catalyst, 0.1g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 200g of ethyl linoleate (fatty acid chain length distribution C18, chain length C2 of ester) is put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 795g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 30min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-9, and the raw material proportion and evaluation index are shown in Table 1.
Example 10
Ru/MgO catalyst, 0.1g, was prepared according to example 2 of patent CN 109289846B and was fixed to a high-pressure polymerization vessel stirrer. 455g of butyl stearate (fatty acid chain length distribution C18, chain length C4 of ester) are put into a high-pressure polymerization reaction kettle, and the reaction kettle is closed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 545g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 30min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that a clear and transparent FMEE product is obtained and is marked as FMEE-10, and the raw material proportion and evaluation index are shown in Table 1.
Comparative example 1
1G of catalyst was synthesized as in example 3 of patent CN107921421A, and the catalyst and 300g of methyl palmitate (fatty acid chain length distribution C16-C18, chain length C1 of ester) were put into a high-pressure polymerization reactor, and the reactor was closed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 695g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 40min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that the FMEE product with turbid appearance is obtained, which is marked as FMEE-11, and the raw material proportion and evaluation index are shown in Table 1.
Comparative example 2
Commercial Mg-Al oxide catalyst (KW 300, kyowa Chemical IndustryCo., ltd.) is purchased, 3g of the catalyst and 300g of methyl palmitate (chain length of fatty acid is distributed from C16 to C18, chain length of ester C1) are taken after calcination treatment at about 500-900 ℃ and put into a high-pressure polymerization reaction kettle, and the reaction kettle is sealed; the reactor cavity was purged three times with inert gas, warmed to 130 ℃, and initiated by the addition of 5g of ethylene oxide. After the pressure is reduced and the temperature is increased, 695g of ethylene oxide is continuously added under the condition that the pressure is less than or equal to 0.5MPa, and the reaction temperature is 160-170 ℃. After the addition of the ethylene oxide is completed, the temperature is kept at 160-170 ℃ for 40min until the pressure is not reduced any more, the temperature is reduced, and the material is discharged, so that the FMEE product with turbid appearance is obtained, which is marked as FMEE-12, and the raw material proportion and evaluation index are shown in Table 1.
Comparative example 3
FMEE-11 prepared in comparative example 1 was filtered according to the following filtration method of patent CN107921421A to give FMEE-13, and the evaluation index is shown in Table 1.
Comparative example 4
FMEE-12 prepared in comparative example 2 was filtered according to the following filtration method of patent CN107921421A to give FMEE-14, and the evaluation index is shown in Table 1.
CN107921421a filtration method description:
To a separable flask having a capacity of 1L, a material to be filtered such as FMEE-11 prepared in comparative example 1 was charged, followed by adding 0.01 part by mass of aluminum sulfate as an agglutinant to the material to be filtered and 10 parts by mass of water to the material to be filtered, and mixing the mixture at a temperature of 80℃with a paddle stirring blade at 420rpm for 1 hour, thereby forming agglutinates, and a mixed solution containing the agglutinates was obtained.
Then, 1mol/L aqueous potassium hydroxide (special grade chemical, manufactured by Kanto chemical Co., ltd.) was added to the mixture to adjust the pH to 7.0, and the mixture was cooled to 50 ℃.
Next, 200g of the mixture was added to a pressure filter equipped with a filter 123B (manufactured by 3M Japanese Co., ltd., filtration accuracy lum) having a diameter of 4cm, and the mixture was pressure-filtered under 0.1MPa with nitrogen gas to separate aggregates from the material to be filtered, thereby obtaining FMEE-13 of comparative example 3.
TABLE 1
The calculation method comprises the following steps:
1. Catalytic efficiency calculation: catalytic efficiency = total mass of alkylene oxide/(catalyst mass x time to charge the second portion of alkylene oxide);
2. product yield calculation: product yield = mass after filtration ∈ mass before filtration x 100%;
3. the total discharge mass of the fatty acid ester alkoxylate is calculated according to the following formula:
Total discharge mass = fatty acid ester mass + first portion alkylene oxide mass + second portion alkylene oxide.
In the above-mentioned feed ratios in table 1, the alkylene oxide refers to the total number of moles of the first portion of alkylene oxide and the second portion of alkylene oxide in the molar ratio of alkylene oxide to ester. In the above formula for calculating the catalytic efficiency, the total mass of alkylene oxide represents the total mass of the first portion of alkylene oxide and the second portion of alkylene oxide for initiating the reaction, the feeding time of the second portion of alkylene oxide represents the time for which the second portion of alkylene oxide is continuously added, and in addition, the time for which the second portion of alkylene oxide is continuously added can be reversely calculated by the catalytic efficiency, the total mass of alkylene oxide and the catalyst mass.
As can be seen from the results in Table 1, compared with comparative examples 1 and 2, the synthesis method of the present invention adopts Ru/MgO catalyst with substantially the same catalytic efficiency, the catalyst amount is extremely low, no refining filtration is required, the product appearance is clear and transparent, no ion residue is substantially generated, the product yield is high, and the economic use value is high. The catalysts used in comparative examples 1 and 2 are in powder form, and the catalyst enters the product after the reaction, so that the product directly prepared is not subjected to filtration refining, and the product with good performance can be obtained after the filtration refining, and has turbid appearance and high ion content.
In addition, it was found through experiments that the products prepared based on the methods of patent CN 109289846B, such as the Ru/MgO catalysts prepared in example 1, example 3, example 4, and the fatty acid ester alkoxylates prepared according to the methods of the present application have the same good properties as the products prepared in the above examples.
The application has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the application can be subjected to various substitutions and improvements, and all fall within the protection scope of the application.
Claims (9)
1. A method for synthesizing a fatty acid ester alkoxylate, which is characterized by comprising the following steps:
(1) Placing Ru/MgO catalyst in a reaction system;
(2) Feeding fatty acid ester into the reaction system; the fatty acid ester is selected from esters of fatty acids of C6-C18 and alcohols of C1-C4;
(3) Cleaning a reactor cavity by inert gas, heating to an initiation temperature, and feeding a first part of alkylene oxide into the reaction system to initiate reaction;
(4) Continuously adding a second part of alkylene oxide, maintaining the reaction temperature, and then cooling to discharge a liquid phase substance to obtain the fatty acid ester alkoxylate;
The first portion of alkylene oxide, the second portion of alkylene oxide are each independently selected from the group consisting of one or more of ethylene oxide, propylene oxide, and butylene oxide;
The Ru/MgO catalyst is a sheet-shaped or honeycomb-shaped heterogeneous catalyst, and the preparation method of the Ru/MgO catalyst comprises the following steps: (S1) providing or preparing a metal magnesium sheet or magnesium wire woven honeycomb structure; (S2) dissolving ruthenium salt in an acid solution to obtain a ruthenium tetrachloride solution; (S3) providing or preparing an electrolyte; the electrolyte consists of a sodium silicate solution with the concentration of 8 g/ml-36 g/ml, a potassium fluoride solution with the concentration of 2 g/ml-16 g/ml and a potassium hydroxide solution with the concentration of 4 g/ml-16 g/ml in a volume ratio of 1:1:1; (S4) mixing the ruthenium tetrachloride solution with the electrolyte to obtain a mixed solution; (S5) maintaining the temperature of the mixed solution at 0-25 ℃, taking metal magnesium as an anode, performing a microplasma oxidation process to obtain a Ru/MgO catalyst, and washing and drying the catalyst; the parameters of the microplasma oxidation process are as follows: the pulse width is 200-1000 mu s, the pulse number is 24-120 Hz, the pulse current density is 0.4-2A/cm 2, and the action time is 1-3 min; liquid nitrogen is used to pour the anode metal magnesium during the process.
2. The synthesis method according to claim 1, wherein in the step (1), placing the Ru/MgO catalyst in the reaction system comprises:
And fixing the Ru/MgO catalyst on the stirrer of the high-pressure polymerization reaction kettle or the inner wall of the reaction kettle.
3. The synthesis method according to claim 1 or 2, wherein the Ru/MgO catalyst uses metal magnesium as a matrix, the surface of the metal magnesium is three-dimensional porous MgO, and Ru nanoparticles are supported on the surface of MgO and in pores.
4. The synthesis method according to claim 3, wherein the amount of the Ru/MgO catalyst is 0.05 to 1% by weight of the total discharge mass of the fatty acid ester alkoxylate.
5. The synthesis method according to claim 1 or 2, wherein in the step (3), the inert gas purging of the reactor cavity is performed 2 to 5 times, and the initiation temperature is 90 to 130 ℃.
6. The synthesis method according to claim 1 or 2, wherein the synthesis method further comprises the following steps between step (3) and step (4):
and after the pressure of the reaction system is reduced and the temperature is increased, continuously adding the second part of alkylene oxide, and keeping the pressure of the reaction system to be less than or equal to 0.5MPa.
7. The synthetic method of claim 1, wherein in step (4), the second portion of alkylene oxides are a combination of a plurality of ethylene oxide, propylene oxide and butylene oxide, each alkylene oxide being added alone or in a mixture of a plurality.
8. The synthetic method according to claim 1 or 2, wherein a ratio of a mole number of the fatty acid ester to a total mole number of the first portion of alkylene oxide and the second portion of alkylene oxide is 1:1 to 100.
9. The synthetic method according to claim 1 or 2, wherein, in step (4), maintaining the reaction temperature comprises:
In the process of continuously adding the second part of alkylene oxide, keeping the temperature of the reaction system at 90-180 ℃; and after the second part of alkylene oxide is fed, keeping the temperature of the reaction system at 90-180 ℃ for 20-60 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245129A (en) * | 2012-04-13 | 2014-12-24 | 狮王株式会社 | Alkoxylation catalyst, method for producing catalyst, and method for producing fatty acid alkyl ester alkoxylate using catalyst |
| CN108276279A (en) * | 2017-12-20 | 2018-07-13 | 沈阳化工大学 | The method of one-step synthesis carbonic acid asymmetry ester |
| CN109289846A (en) * | 2018-10-26 | 2019-02-01 | 东北大学 | A kind of Ru/MgO catalyst and its preparation method and application |
| CN109317187A (en) * | 2018-11-19 | 2019-02-12 | 江苏钟山化工有限公司 | Fatty acid ester alkoxylating object catalyst for synthesizing and its application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104245129A (en) * | 2012-04-13 | 2014-12-24 | 狮王株式会社 | Alkoxylation catalyst, method for producing catalyst, and method for producing fatty acid alkyl ester alkoxylate using catalyst |
| CN108276279A (en) * | 2017-12-20 | 2018-07-13 | 沈阳化工大学 | The method of one-step synthesis carbonic acid asymmetry ester |
| CN109289846A (en) * | 2018-10-26 | 2019-02-01 | 东北大学 | A kind of Ru/MgO catalyst and its preparation method and application |
| CN109317187A (en) * | 2018-11-19 | 2019-02-12 | 江苏钟山化工有限公司 | Fatty acid ester alkoxylating object catalyst for synthesizing and its application |
Non-Patent Citations (3)
| Title |
|---|
| Effect of the Acid-Base Properties of the Support on the Performance of Ruthenium Catalysts in the Hydrodeoxygenation of Stearic Acid;Setyoningsih, Isni Putri等;《 AIP Conference Proceedings》;第2175卷(第1期);第 020010.页 * |
| 以镁为基体的贵金属纳米催化剂的制备及催化制氢研究;王玮;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第第04期期);第1-76页 * |
| 羧酸酯插入式乙氧基化反应研究;胡学一;《中国优秀博士学位论文全文数据库工程科技Ⅰ辑》(第09期);第1-109页 * |
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