CN100381546C - Process for producing monoglyceride-containing composition - Google Patents
Process for producing monoglyceride-containing composition Download PDFInfo
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- CN100381546C CN100381546C CNB2004800142914A CN200480014291A CN100381546C CN 100381546 C CN100381546 C CN 100381546C CN B2004800142914 A CNB2004800142914 A CN B2004800142914A CN 200480014291 A CN200480014291 A CN 200480014291A CN 100381546 C CN100381546 C CN 100381546C
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- monoglyceride
- glycerine
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- manufacture method
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- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 123
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 229910052742 iron Inorganic materials 0.000 claims abstract description 16
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 54
- 235000011187 glycerol Nutrition 0.000 claims description 53
- 150000002632 lipids Chemical class 0.000 claims description 41
- 230000009466 transformation Effects 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 125000005908 glyceryl ester group Chemical group 0.000 claims description 12
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000002314 glycerols Chemical class 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 7
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 6
- 229930195729 fatty acid Natural products 0.000 abstract description 6
- 239000000194 fatty acid Substances 0.000 abstract description 6
- 150000004665 fatty acids Chemical class 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- -1 glycerol ester Chemical class 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 11
- 238000004821 distillation Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 235000019484 Rapeseed oil Nutrition 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- FRVCGRDGKAINSV-UHFFFAOYSA-L iron(2+);octadecanoate Chemical compound [Fe+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRVCGRDGKAINSV-UHFFFAOYSA-L 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000000998 batch distillation Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- AMFIJXSMYBKJQV-UHFFFAOYSA-L cobalt(2+);octadecanoate Chemical compound [Co+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AMFIJXSMYBKJQV-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- HOIQWTMREPWSJY-GNOQXXQHSA-K iron(3+);(z)-octadec-9-enoate Chemical compound [Fe+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O HOIQWTMREPWSJY-GNOQXXQHSA-K 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- HEAFJVLUNSWSQJ-UHFFFAOYSA-N iron;propanoic acid Chemical compound [Fe].CCC(O)=O HEAFJVLUNSWSQJ-UHFFFAOYSA-N 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- SZINCDDYCOIOJQ-UHFFFAOYSA-L manganese(2+);octadecanoate Chemical compound [Mn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SZINCDDYCOIOJQ-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000199 molecular distillation Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 150000004685 tetrahydrates Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Fats And Perfumes (AREA)
Abstract
A process for producing a monoglyceride-containing composition which comprises reacting glycerol with at least one acylated compound selected among fatty acids and glycerol esters, wherein the reaction is conducted in the presence of a catalyst comprising at least one metal selected among iron, cobalt, and manganese, the catalyst being used in an amount of 0.1 to 60 ppm (of the total weight of the glycerol and the acylated compound) in terms of metal amount. Also provided is the process for producing a monoglyceride-containing composition which includes a step in which the amount of water contained in the reaction system is kept at 500 to 5,000 ppm either after the conversion in the reaction of glycerol with a fatty acid has reached 90% or higher in terms of the conversion of the fatty acid or during the transesterification of glycerol with a glycerol ester.
Description
Technical field
The present invention relates to the manufacture method of the high composition that contains monoglyceride of a kind of content of monoglyceride.
Background technology
The monoglyceride that is widely used as the finish etc. of makeup, food, industrial emulsifying agent or lubricating oil is to make by the esterification of glycerine and lipid acid or glycerine and greasy transesterification reaction.These reactions are carried out not having catalyzer to exist or having in the presence of the catalyzer, generally produce the mixture of glycerine, monoglyceride, diglyceride and tri-glyceride.Reaction system is nonhomogeneous system normally, because the amount of the monoglyceride that generated is subjected to glycerine at lipid acid mutually or generate the influence of the solubleness of ester in mutually, so even the amounts of glycerol of merely increasing input can not improve the content of monoglyceride.For this reason, under the situation of wishing to get the higher highly purified monoglyceride just of performance, utilize molecular distillation to make with extra care usually.
The method that promotes under the situation of catalyzer with greasy transesterification reaction in U.S. Patent application US-A 2474740 and US-A 2478354 aqueous glycerol of using 5～l5% is disclosed and is not having.
In addition, in U.S. Patent application US-A 2206167, disclose by make the method for monoglyceride by glycerine and grease as the transesterification reaction of catalyzer with alkali soaps such as Na.
And, in U.S. Patent application US-A 2628967, disclose make glycerine or ethylene glycol and lipid acid or glycerine polyester in the presence of with the specific transition-metal catalyst headed by the iron, under high temperature, react the method for making monoglyceride.
Summary of the invention
The invention provides a kind of manufacture method that contains the composition of monoglyceride; it is that glycerine and at least a acylated compound that has that is selected from lipid acid and the glyceryl ester are reacted; this method uses the catalyzer that contains at least a metal in chosen from Fe, cobalt and the manganese to react; described catalyzer is counted 0.1～60ppm (with respect to glycerine with have the weight ratio of the gross weight of acylated compound, below identical) with metal.
And; the invention provides a kind of manufacture method that contains the composition of monoglyceride; it is that glycerine and at least a acylated compound that has that is selected from lipid acid and the glyceryl ester are reacted; this reaction has following operation: in the reaction of glycerine and lipid acid; with lipid acid be the transformation efficiency of benchmark reach 90% or above after or when glycerine and glyceryl ester carry out transesterification reaction, the moisture content in the reaction system is remained in the scope of 500～5000ppm.
Embodiment
Have following problem in U.S. Patent application US-A 2474740 and US-A 2478354: in order to keep moisture content system is formed outside the pressurized systems, also residual have a large amount of unreacted lipid acid.
In addition, in U.S. Patent application US-A 2206167, have following problem: removing by distillation after the reaction under the situation of unreacted glycerine, reduction for the content that stops the monoglyceride that causes owing to reversed reaction, must be in advance neutralization bases composition at high temperature, in addition, even also remaining in resultant have can not isolating neutralized salt by filtering.
And, in U.S. Patent application US-A 2628967, have following problem: although do not need catalyst neutralisation, because the usage quantity of catalyzer is counted 80～1700ppm with metal, so insoluble composition is more and be difficult to use under situation about directly using.In addition, when utilizing the distillation deglycerizin, also promote the reduction of the caused monoglyceride content of reversed reaction, therefore must after cooling, utilize filtration or decant to come separating catalyst in advance.And have in the filtration under the residual state that glycerine arranged, filtration velocity is slow, the problem of the poor yields in the decant.Also there is following problem in addition:, not preferred for the operation that must heat again utilizing distillation to remove under the situation of unreacted glycerine.
The objective of the invention is to, provide a kind of expensive concentrating unit such as molecular still or special high speed rotating of not using to stir shears, make the manufacture method of the high composition that contains monoglyceride of the content of monoglyceride by glycerine and lipid acid or glyceryl ester.
The objective of the invention is to, provide a kind of expensive concentrating unit such as molecular still or special high speed rotating of not using to stir shears, easily make the manufacture method of the high composition that contains monoglyceride of the content of monoglyceride by glycerine and lipid acid or glyceryl ester.
Employed glycerine is not particularly limited among the present invention, and preferred purity is 95 weight % or above glycerine.
Among the present invention employed be selected from lipid acid and glyceryl ester to have acylated compound can be side chain, straight chain, any in saturated, unsaturated has acylated compound; consider from the viewpoint that makes effect of the present invention become clearer and more definite; the carbon number of preferred acyl group is 12～30, and more preferably the carbon number of acyl group is 14～22.
Concrete example as employed lipid acid among the present invention, can list single lipid acid of planting such as lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, oleic acid, elaidic acid, linolic acid, linolenic acid, perhaps soya fatty acid, mixed fatty acids such as rape seed oil lipid acid, ready denier oil acid.Consider that from the viewpoint of the low-temperature fluidity relevant preferred iodine value is 80 or above lipid acid, more preferably 130 or above lipid acid with the operability of the composition that contains monoglyceride.Specifically, be preferably oleic acid, linolic acid, linolenic acid, soya fatty acid, rape seed oil lipid acid, ready denier oil acid.
As employed glyceryl ester among the present invention, can list with above-mentioned lipid acid and glycerine is three esters, diester of composition and composition thereof.In addition, also can contain monoesters.
Among the present invention; the viewpoint that improves every batch productivity is considered from the high composition that contains monoglyceride of the content that obtains monoglyceride, simultaneously; glycerine with the reaction ratio with acylated compound is; with respect to the 1 mole of acyl group that contains acylated compound; preferably glycerine be 1 mole or more than; more preferably 1～3 mole, be preferably 1.5～3 moles especially.
The present invention can use or not use catalyzer, under situation about using, preferably contains the catalyzer of at least a metal in chosen from Fe, cobalt and the manganese, can list metal simple-substance or its compound selected from iron, cobalt or manganese.Specifically, as the catalyzer that contains iron, can list reduced iron simple substance, ferric oxide (Fe
2O
3), Z 250 (Fe
3O
4), metallic soap, iron protochloride (II), iron(ic) chloride muriates such as (III) etc. such as ironic hydroxide oxide compounds such as (FeOOH) and oxyhydroxide, iron acetate, propionic acid iron, iron stearate, iron oleate.As the catalyzer that contains cobalt, can list cobalt simple substance, cobalt monoxide (CoO), tricobalt tetroxide (Co
3O
4), cobaltous carbonate, cobalt stearate, cobalt chloride (II) etc.As the catalyzer that contains manganese, can list manganese simple substance, Manganse Dioxide, trimanganese tetroxide, manganese stearate etc.Consider from viewpoints such as catalyst activity, operability, availabilities, preferably contain the catalyzer of iron, preferred especially ironic hydroxide.From the minimizing in reaction times, filter viewpoint such as alleviating of load and consider that the usage quantity of catalyzer is preferably 0.1～60ppm in metal, more preferably 0.5～10ppm is preferably 0.5～5ppm especially.
In the present invention, the viewpoint that reduces free lipid acid amount is considered from the content that improves monoglyceride, simultaneously, in the reaction of glycerine and lipid acid be with lipid acid the transformation efficiency (with following general formula (I) expression) of benchmark reach 90% or more than, and compare with esterification, after transesterification reaction becomes the mastery reaction; Perhaps when glycerine and glyceryl ester carry out transesterification reaction, the viewpoint that reduces free lipid acid amount is considered from the content that improves monoglyceride, simultaneously, with the moisture content in the reaction system preferably be controlled at 500～5000ppm, more preferably 600～4000ppm, further in the scope of preferred 600～3000ppm, preferred especially 1000～3000ppm.Although the moisture role in the method for the present invention is indeterminate, be speculated as: make glyceryl ester carry out micro-hydrolysis and make lipid acid free, water plays the katalysis of transesterify.
The control of moisture content is undertaken by following: Yi Bian use moisture content tester, the moisture content of assaying reaction liquid in time, import in the reaction solution rare gas elementes such as nitrogen and/or the space segment on reaction solution top on one side, and regulate the import volume of rare gas element in reactive tank, carry out the control of moisture content thus.Rare gas element can be supplied with continuously or off and on.In addition, have only under the situation of hydropenic reactions such as reaction of glycerine and glyceryl ester, can add entry in advance, cooperate with rare gas elementes such as in reactive tank, importing nitrogen as required the moisture content in the system is controlled at above-mentioned value.
From improving the solubleness of glycerine to oil reservoir; improving the viewpoint of the speed of esterification and transesterification reaction simultaneously considers; glycerine and contain the temperature of reaction of acylated compound preferred 180 ℃ or more than; from suppressing generation aspect consideration as the Glycerol dimer of by product; preferred 270 ℃ or following of temperature of reaction, specifically, preferred 180～270 ℃; more preferably 200～260 ℃, preferred especially 240～255 ℃.Because long-time heating at high temperature, can increase as the secondary growing amount of the Glycerol dimer of the condenses of glycerine, so will take into account with temperature, but at 250 ℃ or when above, reaction times is preferably at 12 hours or following, more preferably at 7 hours or following, particularly preferably in 5 hours or following.
The composition that contain monoglyceride high by the content of the resulting monoglyceride of the inventive method can directly use, but under the situation of using glycerine and catalyzer, preferably removes the catalyzer that contains metal.Under the situation of deglycerizin and the catalyzer that contains metal, consider from the viewpoint of productivity, preferably deglycerizin in the presence of the catalyzer that contains metal.Just, when will the distillation deglycerizin before, when filtration contains the catalyzer of metal, consider from the problem of the removal of the thermotolerance of filtering material and catalyzer, the operation that then has following trouble: in case be cooled to 100 ℃ or following, behind the filtering catalyst, must form high temperature again and distill deglycerizin, yet can avoid this trouble in the present invention.In addition, behind the distillation deglycerizin, the advantage of filtering the method for the catalyzer that contains metal is, do not have the high glycerine of viscosity during owing to filtration, thereby filtration velocity is accelerated.Concrete is, after the reaction, distills deglycerizin under the condition of decompression, supplies with water vapour again under the condition of decompression as required, behind the distillation deglycerizin, by removing by filter the catalyzer that contains metal.
The distillation deglycerizin can use intermittent type or use film type distiller to adopt continous way and carry out.Under situation, preferably use following condition: preferred 200 ℃ or following of temperature, more preferably 180 ℃ or following, the preferred 53kPa of pressure or following, more preferably 2.7kPa or following by the batch distillation deglycerizin.For filtration, can use the adsorbing zeta-potential strainer that has that produces owing to so-called dependence zeta-potential (phase boundary potential is poor) to carry out simply.
The content of the monoglyceride among the present invention is meant, utilize gpc analysis (gel permeation chromatography), the value of trying to achieve according to following formula (II) is just with respect to the area ratio in the gpc analysis of the monoglyceride of the total amount of monoglyceride, diglyceride and tri-glyceride.
The area of the monoglyceride of MG:GPC
The area of the diglyceride of DG:GPC
The area of the tri-glyceride of TG:GPC
The content that utilizes method of the present invention can obtain monoglyceride is 55 area % or the above so-called high-load composition that contains monoglyceride.Consider that from the viewpoint of productivity the content of monoglyceride can reach the high-content of 75 area %.Specifically, can make the content of monoglyceride at 55～75 area % scopes, the more preferably composition of 60～75 area % scopes.
Embodiment
The content of monoglyceride utilizes gpc analysis to try to achieve.TSK gel G2000HXL and TSK gel G1000HXL that Tosoh (Co., Ltd.) is made are connected in series as chromatographic column, use RI (differential refractive index meter) as detector, use THF (tetrahydrofuran (THF)) as eluant.
In addition, the content of glycerine and Glycerol dimer utilizes GC analysis (gas chromatograph) to carry out quantitatively, and the content of iron utilizes icp analysis (inductive couple plasma luminescence analysis) to carry out quantitatively.
Embodiment 1
With glycerine 480g, ready denier oil acid 750g pack into (glycerine/lipid acid (mol ratio)=2.0) in the 2L four-hole boiling flask that has stirrer, dehydrating tube-cooling tube, thermometer, nitrogen ingress pipe, be added on the ironic hydroxide of outstanding turbid formation in the less water, wherein addition is counted 2ppm with iron, on one side nitrogen is flow to liquid upper space portion with 100mL/ minute speed, under the stirring of 400r/min, be warmed up to 250 ℃ on one side with about 1.5 hours.After reaching 250 ℃, reaction is 4 hours under this temperature.Content to acid number, moisture content and monoglyceride is analyzed in time, consequently, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content range in 700～1900ppm.The content of the monoglyceride in the reacted resultant is 67 area %.
Then, by under reduced pressure, making reaction mixture refluxed, be cooled to 170 ℃, directly glycerine underpressure distillation under 2.7kPa or following pressure is removed, under 150 ℃, 2kPa, supply with again after 2 hours the water vapour, use ZETA plus 30S (CUNO (strain) manufacturing), adsorption filtration under pressurized conditions obtains containing the composition of monoglyceride.The content of the monoglyceride in the composition is 64 area %, and acid number is 0.2mgKOH/g, the content 0.3 weight % of glycerine, and the content of Glycerol dimer is 0.3 weight %, the content of iron is 0.1ppm or following.
Embodiment 2
Except ironic hydroxide is replaced with the iron stearate, react similarly to Example 1, similarly deglycerizin and carry out adsorption filtration.The content of the monoglyceride in the reacted resultant is 65 area %, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content in 600～1300ppm scope, change.In addition, the content of the monoglyceride in the composition after the adsorption filtration is 62 area %, and acid number is 0.2mgKOH/g, the content 0.4 weight % of glycerine, and the content of Glycerol dimer is 0.4 weight %, the content of iron is 0.1ppm or following.
Embodiment 3
Except the speed of nitrogen with 100mL/ minute is blown in the liquid, carry out reacting similarly to Example 1 outside 6 hours the reaction, similarly deglycerizin and carry out adsorption filtration.The content of the monoglyceride in the reacted resultant is 63 area %, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content in 300～400ppm scope, change.In addition, the content of the monoglyceride in the composition after the adsorption filtration is 61 area %, and acid number is 0.3mgKOH/g, the content 0.4 weight % of glycerine, and the content of Glycerol dimer is 0.5 weight %, the content of iron is 0.1ppm or following.
Embodiment 4
Except ironic hydroxide being replaced with iron protochloride (II) tetrahydrate and changing to the 10ppm, react similarly to Example 1, similarly deglycerizin and carry out adsorption filtration in the addition of iron.The content of the monoglyceride in the reacted resultant is 66 area %, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content in 600～1500ppm scope, change.In addition, the content of the monoglyceride in the composition after the adsorption filtration is 63 area %, and acid number is 0.2mgKOH/g, the content 0.5 weight % of glycerine, and the content of Glycerol dimer is 0.3 weight %, the content of iron is 0.1ppm or following.
Embodiment 5
Ready denier oil acid is replaced with soybean oil; 1 mole of acyl group that the add-on of glycerine is changed to respect to soybean oil is 2 moles; the addition of ironic hydroxide changed to iron count 10ppm; to change in the reaction times outside 10 hours; react similarly to Example 1, similarly deglycerizin and carry out adsorption filtration.The content of the monoglyceride in the reacted resultant is 64 area %, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content in 600～1400ppm scope, change.In addition, the content of the monoglyceride in the composition after the adsorption filtration is 61 area %, and acid number is 0.4mgKOH/g, the content 04 weight % of glycerine, and the content of Glycerol dimer is 0.9 weight %, the content of iron is 0.1ppm or following.
Embodiment 6
With glycerine 480g, ready denier oil acid 750g pack into (glycerine/lipid acid (mol ratio)=2.0) in the 2L four-hole boiling flask that has stirrer, dehydrating tube-cooling tube, thermometer, nitrogen ingress pipe, on one side nitrogen is flowed into liquid upper space portion in the flask with 100mL/ minute speed, under the stirring of 400r/min, be warmed up to 250 ℃ on one side with about 1.5 hours.After reaching 250 ℃, reaction is 6 hours under this temperature.Content to acid number, moisture content and monoglyceride is analyzed in time, consequently, when reaching 250 ℃ is that the transformation efficiency of benchmark is 93% with lipid acid, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content at 700～2200ppm, transformation efficiency when reaction finishes is 99%, and the content of monoglyceride is 61 area %.
Embodiment 7
Outside being blown in the liquid with 30mL/ minute speed nitrogen, other and embodiment 6 are in the same manner 250 ℃ of reactions 6 hours down.When reaching 250 ℃ is that the transformation efficiency of benchmark is 93% with lipid acid, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content at 600～900ppm, transformation efficiency when reaction finishes is 99%, and the content of monoglyceride is 60 area %.
Comparative example 1
Do not add ironic hydroxide, other reacts similarly to Example 3, similarly deglycerizin and carry out adsorption filtration.The content of the monoglyceride in the reacted resultant is 54 area %, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content in 300～400ppm scope, change.In addition, the content of the monoglyceride in the composition after the adsorption filtration is 51 area %, and acid number is 0.3mgKOH/g, the content 0.4 weight % of glycerine, and the content of Glycerol dimer is 0.7 weight %.
Comparative example 2
Ironic hydroxide is replaced with sodium hydroxide, and its addition counts 10ppm with sodium, in addition, react, do not neutralize and deglycerizin under underpressure distillation with embodiment 3 usefulness sample ground.The content of the monoglyceride in the reacted resultant is 62 area %, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content in 300～400ppm scope, change.In addition, the content of the monoglyceride in the composition behind the glycerol distillation is 48 area %, the content 3.1 weight % of glycerine, and the content of Glycerol dimer is 0.7 weight %.
Comparative example 3
Outside being blown in the liquid with 100mL/ minute speed nitrogen, similarly to Example 6 250 ℃ of reactions 6 hours down.The transformation efficiency that when reaching 250 ℃ with lipid acid is benchmark is 94%, the transformation efficiency that with lipid acid is benchmark be 90% or above condition under moisture content at 300～400ppm, the transformation efficiency when reaction finishes is 99%, the content of monoglyceride is 54 area %.
Claims (8)
1. manufacture method that contains the composition of monoglyceride; it is to make glycerine and be selected from least a in lipid acid and the glyceryl ester and have acylated compound and react and make the composition that contains monoglyceride; wherein this method uses the catalyzer that contains at least a metal in chosen from Fe, cobalt and the manganese to react, and described catalyzer is counted 0.1～60ppm with respect to glycerine and the weight ratio with gross weight of acylated compound with metal.
2. manufacture method according to claim 1 wherein with respect to 1 mole of acyl group with acylated compound, uses 1 mole or above glycerine to react.
3. manufacture method according to claim 1 and 2 wherein after making glycerine and having acylated compound and react, is distilled deglycerizin under the condition that the catalyzer that contains metal exists.
4. manufacture method according to claim 1 and 2, wherein metal is an iron.
5. manufacture method according to claim 1 and 2, it has following operation: in the reaction of glycerine and lipid acid, with lipid acid be the transformation efficiency of benchmark reach 90% or above after or when glycerine and glyceryl ester carry out transesterification reaction, the moisture content in the reaction system is remained in the scope of 500～5000ppm.
6. manufacture method according to claim 1 and 2, the carbon number that wherein has the acyl group of acylated compound is 12～30.
7. manufacture method according to claim 1 and 2, wherein temperature of reaction is 180～270 ℃.
8. manufacture method according to claim 1 and 2, wherein in containing the composition of monoglyceride, the content value of trying to achieve by gpc analysis of monoglyceride be 55 area % or more than.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP162066/2003 | 2003-06-06 | ||
| JP162065/2003 | 2003-06-06 | ||
| JP2003162065A JP4230283B2 (en) | 2003-06-06 | 2003-06-06 | Method for producing monoglyceride-containing composition |
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| CN2007101383909A Division CN101092589B (en) | 2003-06-06 | 2004-06-03 | Process for producing a monoglyceride-containing composition |
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| CN1795260A CN1795260A (en) | 2006-06-28 |
| CN100381546C true CN100381546C (en) | 2008-04-16 |
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| CNB2004800142914A Expired - Lifetime CN100381546C (en) | 2003-06-06 | 2004-06-03 | Process for producing monoglyceride-containing composition |
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| JP2007308658A (en) * | 2006-05-22 | 2007-11-29 | Dainippon Toryo Co Ltd | Production method for transesterification product and production method for alkyd resin using the transesterification product |
| JP5576271B2 (en) * | 2007-11-22 | 2014-08-20 | 株式会社日本触媒 | Process for producing fatty acid alkyl ester and / or glycerin from fats and oils |
| JP5305811B2 (en) * | 2008-09-29 | 2013-10-02 | 花王株式会社 | Method for producing long-chain fatty acid triglycerides |
| JP5944303B2 (en) * | 2011-12-08 | 2016-07-05 | 花王株式会社 | A method for producing a fatty acid monoglyceride-containing mixture. |
| CN114106852B (en) * | 2021-11-29 | 2023-08-01 | 广东广益科技实业有限公司 | Preparation method of powder cake emulsifying foaming agent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2628967A (en) * | 1948-11-13 | 1953-02-17 | Givaudan Corp | Process for the preparation of partial esters of polyhydric alcohols with carboxylic acids |
| JPH01268663A (en) * | 1988-04-21 | 1989-10-26 | Lion Corp | Production of monoglyceride |
| JPH0987231A (en) * | 1995-09-20 | 1997-03-31 | Kao Corp | Production of monoglyceride of organic acid containing a reduced amount of free organic acid |
-
2003
- 2003-06-06 JP JP2003162065A patent/JP4230283B2/en not_active Expired - Fee Related
-
2004
- 2004-06-03 CN CN2007101383909A patent/CN101092589B/en not_active Expired - Lifetime
- 2004-06-03 CN CNB2004800142914A patent/CN100381546C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2628967A (en) * | 1948-11-13 | 1953-02-17 | Givaudan Corp | Process for the preparation of partial esters of polyhydric alcohols with carboxylic acids |
| JPH01268663A (en) * | 1988-04-21 | 1989-10-26 | Lion Corp | Production of monoglyceride |
| JPH0987231A (en) * | 1995-09-20 | 1997-03-31 | Kao Corp | Production of monoglyceride of organic acid containing a reduced amount of free organic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101092589B (en) | 2010-06-23 |
| JP2004359884A (en) | 2004-12-24 |
| CN101092589A (en) | 2007-12-26 |
| CN1795260A (en) | 2006-06-28 |
| JP4230283B2 (en) | 2009-02-25 |
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