CN104693165A - Method for producing long-chain diacid cyclic ethylene ester - Google Patents
Method for producing long-chain diacid cyclic ethylene ester Download PDFInfo
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- -1 cyclic ethylene ester Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 239000005977 Ethylene Substances 0.000 title abstract description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 239000002253 acid Substances 0.000 claims abstract description 92
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000000855 fermentation Methods 0.000 claims abstract description 12
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- 239000012535 impurity Substances 0.000 claims abstract description 11
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- 238000000926 separation method Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 45
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 150000007520 diprotic acids Chemical class 0.000 claims description 9
- 239000008247 solid mixture Substances 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003916 acid precipitation Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 12
- 235000013599 spices Nutrition 0.000 abstract description 9
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 238000006116 polymerization reaction Methods 0.000 description 18
- FRXSZNDVFUDTIR-UHFFFAOYSA-N 6-methoxy-1,2,3,4-tetrahydroquinoline Chemical compound N1CCCC2=CC(OC)=CC=C21 FRXSZNDVFUDTIR-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 244000153234 Hibiscus abelmoschus Species 0.000 description 11
- 230000006837 decompression Effects 0.000 description 9
- 239000003120 macrolide antibiotic agent Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000003205 fragrance Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 241000402754 Erythranthe moschata Species 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 102100028175 Abasic site processing protein HMCES Human genes 0.000 description 3
- 101001006387 Homo sapiens Abasic site processing protein HMCES Proteins 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
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- 150000002632 lipids Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 230000031018 biological processes and functions Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000012691 depolymerization reaction Methods 0.000 description 2
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000008451 emotion Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000796 flavoring agent Substances 0.000 description 2
- 235000019634 flavors Nutrition 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- 238000007254 oxidation reaction Methods 0.000 description 2
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- 238000010025 steaming Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
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- 102100022210 COX assembly mitochondrial protein 2 homolog Human genes 0.000 description 1
- 101000900446 Homo sapiens COX assembly mitochondrial protein 2 homolog Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
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- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 230000000762 glandular Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 150000007517 lewis acids Chemical class 0.000 description 1
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- 231100000252 nontoxic Toxicity 0.000 description 1
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- 238000002360 preparation method Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000003248 secreting effect Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for producing long-chain diacid cyclic ethylene ester. The method comprises the following steps without a special substrate alkane separation step: directly carrying out acidification precipitation on a biological fermentation solution which contains long-chain dibasic acid to realize the synergistic treatment of demulsification and solid impurity removal; and directly preparing a long-chain dibasic acid ethanol solution as a reaction raw material from the biological fermentation solution by using ethanediol, and then reacting to obtain a finished spice product. Compared with the traditional process for producing the long-chain diacid cyclic ethylene ester, the method provided by the invention can be used for omitting the step of extracting alkane residues, omitting the steps of temperature reduction and crystallization of the long-chain dibasic acid and saving the solvent and the production cost and is shorter in process flow and higher in product yield.
Description
Technical field
The present invention relates to a kind of production method of macrolide spices, particularly relate to a kind of method of being produced macrolide by the bio-fermented liquid containing long-chain biatomic acid.
Background technology
Moschus is the secretory product of the glandular sac between the navel of male musk deer and sexual organ, a kind of valuable animal property spices, diffustivity and valence extremely strong, there is the special soft and fragrance of gracefulness, renowned in the world together with rose, Flower of Arabian Jasmine essential oil, no matter be east or west, people have great interest to it always.The aromatic flavour of Moschus, does not prolongedly fall apart, and having the psychology of people and physiological system affects extremely significantly, has very important value in perfume industry and medicine industry.
Moschus has good Titian effect and splendid fixation ability, and in blending, if lack the animality spices such as Moschus, its fragrance will lack dynamic emotion; Only have by animality fragrance applications in formulas such as essence, just play fixation, set off by contrast, mellow and full with balance whole fragrance effect, bring vigor to whole fragrance, and compose with moving emotion.
The main component of natural musk is megacyclic musk, comprises the cyclic ketones of C13-19, macrolide, heterogeneous ring compound etc., stable performance, nontoxic, is therefore also the focus that people study.Macrolide Moschus compound is a kind of very important musk odorant, " king of spices " good reputation is have in field of perfumery, its elegant in smell luxurious, lasting is lasting, be applied in spices and there is Titian, circle perfume and fixation effect, usually modifier and fixative is used as, macrolide is the material of the senior perfuming cosmetic of allotment Moschus series, is also the important food flavour of the beverage/food such as wine blend, brandy, is also widely used in soap class, the hair washing field such as skin care, washing composition.
Preparing macrolide spices principal item is at present undecane dicarboxylic acid ring ethylene ester and dodecanedioic acid ring ethylene ester, their raw material mainly long-chain biatomic acid and ethylene glycol, conventional synthetic method is that alcoholic acid esterification forms linear polyester, and then depolymerization is cyclized into macrolide.The domestic exploitation that patent reports synthesis technique, the manufacture method of macrolide Moschus compound disclosed in CN1174976C, prepared by polycondensation and depolymerization cyclisation step, also have the exploitation Moschus disclosed in CN1085956A that patent reports product type to mix large ring dilactone compound.
The raw material long-chain biatomic acid of synthesis macrolide, mainly utilizes biofermentation method to produce at present, with normal paraffin, lipid acid and derivative thereof for carbon source, utilizes the function of microorganism diterminal oxidation to produce long-chain biatomic acid, then extract.Form the four phase system comprising air, alkane, water and thalline during fermentable, by the mode such as mechanical stirring, emulsifying agent, carbon source will be formed little oil droplet during the fermentation, microorganism just can touch carbon source, utilizes and oxidation carbon source generation diprotic acid; Therefore, aqueous phase, oil phase (substrate is remaining), solid phase (thalline residual protein etc.) is contained in long-chain biatomic acid fermented liquid, emulsion wherein between profit Two Liquid Phases adds the complicacy of alternate mixing, and this brings difficulty to the purifying of long-chain biatomic acid.
Biological fermentation is prepared in the process of long-chain biatomic acid, and the substrate of fermentation comprises alkane, lipid acid (or ester), and these are not all allowed with water, needs emulsification when fermentation, all wants breakdown of emulsion, cause production efficiency low when extraction.As Chinese patent CN1108286A discloses a kind of process for purification of long-chain biatomic acid, and the long-chain biatomic acid that can contain solvent wets, cake prepares astrotone as raw material.This method needs first to remove remaining fermentation substrate alkane, due to oil-water emulsion in fermented liquid, removes alkane more difficult, causes many, the consuming time length of step, efficiency low.
The clear 56-15695A of Japanese Patent JP discloses a kind of solvent extraction method and carries out extraction long-chain biatomic acid, but extraction process solvent evaporates is serious, and toxicity is large, causes waste on the one hand, on the other hand contaminate environment.
Summary of the invention
The problem that the extraction efficiency extracted for long-chain biatomic acid in current bio-fermented liquid and exist in application is low, the invention provides a kind of method being prepared ring ethylene ester by the bio-fermented liquid containing described long-chain biatomic acid.
The present invention first aspect provides a kind of production method of long-chain biatomic acid ring ethylene ester, the mixture of the one or both of described long-chain biatomic acid the most in SL-AH, tridecanyldicarboxylic acid; Described method comprises the steps:
Step 1, the bio-fermented liquid containing long-chain biatomic acid is directly carried out acid precipitation, and carries out solid-liquid separation, obtain solid mixture, it is≤5% that described solid mixture is dried to moisture weight content;
Step 2, dissolves described solid mixture with the ethylene glycol that moisture weight content is≤3%, filters and removes impurity;
Step 3, the long-chain biatomic acid ethylene glycol solution after filtration, by obtaining long-chain biatomic acid ring ethylene ester after the polycondensation of long-chain biatomic acid and ethylene glycol, depolymerization cyclisation.
Bio-fermented liquid containing long-chain biatomic acid is the multiphase mixture obtained after Production of Long Chain Dicarboxylic Acids Through Micro-Biological Fermen terminates, comprise moisture, fermentation substrate remnants, long-chain biatomic acid salt, thalline and other impurity, also can be after long-chain biatomic acid fermentation ends, to fermented liquid through process, one or more other components except long-chain biatomic acid salt in removing fermented liquid or the multiphase mixture (i.e. the treatment solution of fermented liquid) obtained after reducing its content.The described bio-fermented liquid containing long-chain biatomic acid can be patent document CN2091272C disclosed with alkane, lipid acid for substrate, biological process transforms the long-chain biatomic acid fermented liquid obtained; The described bio-fermented liquid containing long-chain biatomic acid can be patent document CN101121653B disclosed be substrate with derivative of fatty acid, biological process transforms the long-chain biatomic acid fermented liquid obtained.
In a kind of preferred embodiment of the present invention, solid-liquid separation described in step 1 generally adopts to filter removes liquid, wherein, in certain embodiments, and described method of filtering employing Plate Filtration.
During long-chain biatomic acid fermentation ends, the pH value of fermented liquid is generally more than 7.0, and long-chain biatomic acid is dissolved in long-chain biatomic acid fermented liquid with the form of salt.Long-chain biatomic acid is substantially water insoluble at normal temperatures, and in industrial production, long-chain biatomic acid fermented liquid makes long-chain biatomic acid precipitate by acidifying.
In one preferred embodiment of the invention, described acidifying is implemented preferably by interpolation mineral acid.
Wherein, the addition of described mineral acid is realized by control ph, and in the present invention, fermented liquid pH value being adjusted to pH value is less than 4.0 or 4.0 (under room temperature conditions).
Wherein, described mineral acid can be any one or a few the mixture in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid etc., and is preferably sulfuric acid.
The special requirement of the concentration of described mineral acid, only otherwise destroy the molecular structure of long-chain biatomic acid.
Bio-fermented liquid containing long-chain biatomic acid adds mineral acid, and after long-chain biatomic acid precipitation, generating with long-chain biatomic acid and thalline is the mixing solutions of main insolubles.Solid-liquid separation is carried out to this solution, obtains long-chain biatomic acid and thalline is the blended solid of main body.Conventional solid-liquid separation method comprises centrifugal, filtration etc.
Before be separated long-chain biatomic acid and thalline from fermented liquid, for improving the efficiency be separated, can take to carry out the treatment process such as heating to fermented liquid.
After obtaining the mixture of long-chain biatomic acid and thalline, need to carry out further processed to this solid mixture, by most of moisture evaporation wherein, control the moisture content (w/w) below 5% of dry rear solid.
In a kind of preferred embodiment of the present invention, solid mixture described in step 1 is dried to moisture weight content≤3%.
After obtaining dry solid mixture, add ethylene glycol, heat up, dissolve long-chain biatomic acid.
Contriver finds, because the impurity in fermented liquid is complicated, has a large amount of colloidal material to exist, is having under moisture existent condition, and thalline viscosity is very large, extremely sad filter.This can cause the ethylene glycol solution viscosity of long-chain biatomic acid large, and thalline is difficult to removing.Contriver finds unexpectedly, by controlling the moisture content of long-chain biatomic acid and thalline blended solid, then controlling the moisture content of the ethylene glycol added, obtaining the long-chain biatomic acid ethylene glycol solution that moisture content is lower, effectively can alleviate, even thoroughly solve the problem of the sad filter of thalline.Long-chain biatomic acid ethylene glycol solution under condition of the present invention, the impurity based on thalline is easily separated, and obtains the long-chain biatomic acid ethylene glycol solution clarified.Long-chain biatomic acid ethylene glycol solution is separated with the impurity based on thalline, can commonly use conventional industrial process for separating, as the mode such as filtered, centrifugal.
In a kind of preferred embodiment of the present invention, in step 2, the consumption of ethylene glycol is generally advisable with the long-chain biatomic acid effectively dissolved in blended solid.In the present invention, the consumption of ethylene glycol is generally not less than 3 times of (being more than or equal to) long-chain biatomic acid weight, and preferred 3-5 doubly.
In a kind of preferred embodiment of the present invention, ethylene glycol dissolves the temperature of long-chain biatomic acid, generally should lower than 70 DEG C (>=70 DEG C), preferred 75-95 DEG C, more preferably 75-90 DEG C.
In a kind of preferred embodiment of the present invention, before the ethylene glycol solution filtration of long-chain biatomic acid, deimpurity means can also be gone by activated carbon decolorizing etc., to remove the impurity in long-chain biatomic acid solution further.
In a kind of preferred embodiment of the present invention, the method that long-chain biatomic acid ring ethylene ester is prepared in step 3 polycondensation, depolymerization cyclisation can be adopt any existing method, a kind of method preparing macrocyclic ester compound of musk disclosed in Chinese patent CN1174976C; Again such as, the preparation method of a kind of large ring dilactone compound disclosed in Chinese patent CN1085956A.
In a kind of preferred embodiment of the present invention, polycondensation process described in step 3 generally divides polymerization under atmospheric pressure, decompression polymerization two step is carried out, the step of wherein said polymerization under atmospheric pressure is: under rare gas element (as nitrogen, argon gas, helium etc.) environment, when temperature of charge starts to stir to 100 DEG C, continue to heat up, make temperature of charge be warmed up to 180 DEG C-190 DEG C by 150 DEG C through 3 hours; After keeping 4 hours at 180 DEG C-190 DEG C, polymerization under atmospheric pressure reaction terminates.Described decompression polymerization procedure is: at 180 DEG C-190 DEG C, vacuum tightness 300Pa(absolute pressure) below (more low better), decompression polymerization terminates for about 2 hours.
The reaction conditions of depolymerization cyclisation in step 3 of the present invention is 250-350 DEG C and≤0.001MPa(absolute pressure).
Step 3 gained long-chain biatomic acid ring ethylene ester of the present invention can also carry out further rectifying and obtain finished product.
Should be understood that, the above-mentioned all respects of the present invention and various preferred embodiment thereof, in case of no particular description, arbitrary combination can be carried out by those skilled in the art are unrestricted.
In the present invention, spent glycol directly produces long-chain biatomic acid ethylene glycol solution as reaction raw materials from fermented liquid, is then obtained by reacting spices finished product.And existing technique is from diprotic acid purified product, be obtained by reacting spices finished product.This technique is compared with existing long-chain biatomic acid ring ethylene ester production technique, realize the associated treatment of breakdown of emulsion and removal solid impurity, decrease the step of special extraction alkane remnants, decrease the decrease temperature crystalline step of long-chain biatomic acid simultaneously, solvent and productive expense are saved, technical process is shorter, and product yield is higher.
Embodiment
Part term of the present invention is defined as follows
" transesterification reaction " refers to the catalyzed chemical reaction that vegetables oil and alcohol generate fatty acid monoester and glycerine, and transesterification reaction can be carried out under acid catalysis, base catalysis or enzymatic condition.
" distillation " is the difference utilizing each component volatilization degree in liquid mixture, makes liquid mixture components vaporize and makes vapor portion condensation thereupon, thus realizing the separation of component contained by it.It is a kind of unit operation belonging to mass transfer and be separated.Be widely used in the fields such as oil refining, chemical industry, light industry.
" polycondensation " refers to the repeatedly condensation and be polymerized the reaction of the linear polyester obtained of long-chain biatomic acid and ethylene glycol.The catalyzer of contracting ester reaction generally can be divided into homogeneous catalyst and heterogeneous catalyst.Homogeneous catalyst mainly contains Lewis acid, organometallics.Heterogeneous catalyst is some supported solid catalysts mainly.
" depolymerization cyclization " refers to the repeatedly condensation and be polymerized the reaction that the linear polyester obtained carries out separating coalescence cyclisation of SL-AH and ethylene glycol.
The technique means realized for making the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with embodiment, setting forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Ratio and per-cent based on weight, unless stated otherwise.
Comparative example 1
DC12(SL-AH is prepared according to method disclosed in patent documentation CN1570124A) fermented liquid.DC12 fermented liquid directly adds the sulfuric acid of concentration 98%, and being acidified to pH value is after 2.0, Plate Filtration, dries solid to moisture weight content 3.0%.
Contrast 1) get 100 grams of above-mentioned solids, add 400 grams of ethylene glycol (moisture content 2%, weight ratio), dissolve when being heated to 95 DEG C, filter, within about 5 minutes, filtered (water pump suction filtration, diameter 7 centimetres of Medium speed filter papers).
Contrast 2) get 100 grams of above-mentioned solids, add 400 grams of ethylene glycol (moisture content 15%, weight ratio), dissolve when being heated to 95 DEG C, filter, filter after 10 minutes and obtain 100 grams of filtrates (water pump suction filtration, diameter 7 centimetres of Medium speed filter papers).Because filtration velocity is excessively slow, temperature cannot keep, and abandons continuing suction filtration.
Visible, the separation of solvent comprises water amount on impurity such as thalline of dissolved solids has important impact, when water content 2%, obviously more easily filter, and when high-moisture, slower owing to filtering, when not extra heating, the heat filtering continued even can not carried out.
Embodiment 1, synthesis SL-AH ring ethylene ester (Moschus 14)
Prepare DC12 fermented liquid according to method disclosed in patent documentation CN1570124A, carry out acidizing crystal by the sulfuric acid adjust ph to 3.2 of weight concentration 98%, acidizing crystal liquid filters at 60 DEG C, wash, 105 DEG C of oven dry, are dried to moisture content 5wt%.
Add the pure ethylene glycol of treble amount in solid, be warmed up to 95 DEG C, dissolve diprotic acid.The insulation of diprotic acid solution is filtered, removing thalline and other solid impurity.In the long-chain biatomic acid ethylene glycol solution obtained, add 3%(relative to long-chain biatomic acid weight) gac, 95 DEG C stir half an hour, filter obtain clear liquid.
By above-mentioned ethylene glycol solution, add in polycondensation vessel, cool to normal temperature, build charging opening.
Close the valve between vacuum pump and polymeric kettle, in polymeric kettle, inflated with nitrogen is to normal pressure.Close nitrogen valve, slowly open the valve between vacuum pump and polymeric kettle, be evacuated to negative pressure, replace twice.In polymeric kettle after inflated with nitrogen to normal pressure, switch to nitrogen protection state, control nitrogen flow.
Polymerization process divides polymerization under atmospheric pressure, decompression polymerization two step is carried out:
Start polymeric kettle temperature control instrument, when temperature of charge starts to stir to 100 DEG C, continue to heat up, make temperature of charge be warmed up to 180 DEG C-190 DEG C by 150 DEG C through 3 hours.After keeping 4 hours at 180 DEG C-190 DEG C, polymerization under atmospheric pressure reaction terminates.
Conscientiously check the opened condition of each associated valve, make it to be in decompression state, start polymerization vacuum pump.According to vacuum tightness change in polymeric kettle and the changing conditions of heating up in a steamer temperature out, slowly close the blow-off valve on surge tank, progressively gas clean-up, to vacuum tightness 100Pa(absolute pressure), decompression polymerization terminates for about 2 hours, and in polymeric kettle, inflated with nitrogen is to normal pressure.
By relative for 2%(diprotic acid weight) depolymerization catalyst Dibutyltin oxide join in polymeric kettle.Build charging opening, again reduce pressure, to vacuum tightness 300Pa(absolute pressure), terminate through 1 hours.
The linear polyester that polyreaction obtains proceeds in depolymerization reaction still, starts stirring, continues to heat up.Linear polyester is in temperature 260 DEG C, pressure 100Pa(absolute pressure), carry out solution coalescence under depolymerization catalyst effect and be cyclized into object product Moschus 14(SL-AH ring ethylene ester).Progressively increase the temperature to 320 DEG C, maintain after 3 hours, when steaming without gas-phase product, reaction terminates.Whole depolymehzation process about needs 10-40 hour.
By Moschus 14 crude product obtained, through rectifying tower rectifying, obtain qualified finished product, gas chromatographic purity is greater than 99%, and musky odor is pure, free from extraneous odour.
Embodiment 2, synthesis tridecanyldicarboxylic acid ring ethylene ester (astrotone)
Prepare DC13 fermented liquid according to method disclosed in patent documentation CN1570124A, carry out acidizing crystal by the sulfuric acid adjust ph to 3.2 of weight concentration 98%, acidizing crystal liquid filters at 60 DEG C, wash, 105 DEG C of oven dry, are dried to moisture content 3%.
Add the pure ethylene glycol of five times of weight in solid, be warmed up to 75 DEG C, dissolve diprotic acid.The insulation of diprotic acid solution is filtered, removing thalline.The long-chain biatomic acid ethylene glycol solution obtained, adds 3%(relative to long-chain biatomic acid weight) gac, 75 DEG C stir half an hour, filter obtain clear liquid.
By above-mentioned ethylene glycol solution, add in polycondensation vessel, cool to normal temperature, build charging opening.
Close the valve between vacuum pump and polymeric kettle, in polymeric kettle, inflated with nitrogen is to normal pressure.Close nitrogen valve, slowly open the valve between vacuum pump and polymeric kettle, be evacuated to negative pressure, replace twice.In polymeric kettle after inflated with nitrogen to normal pressure, switch to nitrogen protection state, control nitrogen flow.
Polymerization process divides polymerization under atmospheric pressure, decompression polymerization two step is carried out:
Start polymeric kettle temperature control instrument, when temperature of charge starts to stir to 100 DEG C, continue to heat up, make temperature of charge be warmed up to 180 DEG C-190 DEG C by 150 DEG C through 3 hours.After keeping 6 hours at 180 DEG C-190 DEG C, polymerization under atmospheric pressure reaction terminates.
Conscientiously check the opened condition of each associated valve, make it to be in decompression state, start polymerization vacuum pump.According to vacuum tightness change in polymeric kettle and the changing conditions of heating up in a steamer temperature out, slowly close the blow-off valve on surge tank, progressively gas clean-up, to vacuum tightness 300Pa(absolute pressure) (more low better), decompression polymerization terminates for about 2 hours, and in polymeric kettle, inflated with nitrogen is to normal pressure.
By relative for 2%(diprotic acid weight) depolymerization catalyst Dibutyltin oxide join in polymeric kettle.Build charging opening, again reduce pressure, to vacuum tightness 300Pa(absolute pressure), terminate through 1 hours.
The linear polyester that polyreaction obtains is squeezed in depolymerization reaction still, starts stirring, continues to heat up.Linear polyester is in temperature 260 DEG C, pressure 200Pa(absolute pressure), carry out solution coalescence under depolymerization catalyst effect and be cyclized into object product astrotone (tridecanyldicarboxylic acid ring ethylene ester).Progressively increase the temperature to 320 DEG C, maintain after 3 hours, when steaming without gas-phase product, reaction terminates.Whole depolymehzation process about needs 10-40 hour.
By the astrotone crude product obtained, through rectifying tower rectifying, obtain qualified finished product, gas chromatographic purity is greater than 99%, and musky odor is pure, free from extraneous odour.
Scope of the present invention is not by the restriction of described specific embodiments, and described embodiment only for as the single example of illustrating all respects of the present invention, also comprises method and the component of functional equivalent in the scope of the invention.In fact, except content as herein described, those skilled in the art can easily grasp multiple improvement of the present invention with reference to description above and accompanying drawing.Described improvement also falls within the scope of appended claims.Every section of reference mentioned above is listed in herein as a reference all in full.
Claims (8)
1. a production method for long-chain biatomic acid cyclic lactone, is characterized in that, the mixture of the one or both of described long-chain biatomic acid the most in SL-AH, tridecanyldicarboxylic acid; Described method comprises the steps:
Step 1, the bio-fermented liquid containing long-chain biatomic acid is directly carried out acid precipitation, and carries out solid-liquid separation, obtain solid mixture, it is≤5% that described solid mixture is dried to moisture weight content;
Step 2, dissolves described solid mixture with the ethylene glycol that moisture weight content is≤3%, filters and removes impurity;
Step 3, the long-chain biatomic acid ethylene glycol solution after filtration, by obtaining long-chain biatomic acid cyclic lactone after the polycondensation of long-chain biatomic acid and ethylene glycol, depolymerization cyclisation.
2. method according to claim 1, is characterized in that, the described bio-fermented liquid containing long-chain biatomic acid is that fermentable is produced in diprotic acid technique, the liquid obtained after fermentation ends, or through simply dealt liquid after fermentation ends.
3. method according to claim 1 and 2, is characterized in that, the described bio-fermented liquid containing long-chain biatomic acid contains substrate alkane.
4. method according to claim 1, is characterized in that, in step 1, acidization is implemented by adding mineral acid; Described mineral acid is selected from any one or a few the mixture in hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid etc.
5. method according to claim 4, is characterized in that, and the fermented liquid pH value that mineral acid addition makes is less than 4.0 or 4.0 under being adjusted to room temperature condition.
6. method according to claim 1, is characterized in that, the temperature that ethylene glycol dissolves long-chain biatomic acid is not less than 70 DEG C.
7. method according to claim 1, is characterized in that, the consumption of ethylene glycol is not less than 3 times of long-chain biatomic acid weight.
8. a long-chain biatomic acid cyclic lactone, is characterized in that, described long-chain biatomic acid cyclic lactone is produced by method according to claim 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963990A (en) * | 2019-12-25 | 2020-04-07 | 江西黄岩香料有限公司 | Preparation method of musk C-14 |
| CN111620773A (en) * | 2020-06-16 | 2020-09-04 | 席海红 | Method for preparing dibasic acid by using musk-T kettle residue |
| CN114276229A (en) * | 2021-12-31 | 2022-04-05 | 万华化学集团股份有限公司 | Method for recycling musk T kettle residue |
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| CN1335312A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Method of purifying macrocyclic ester compound of musk |
| CN1351005A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Process for extracting and refining long-chain dicarboxylic acid from bio-fermented liquid |
| CN1570124A (en) * | 2004-05-12 | 2005-01-26 | 上海凯赛生物技术研发中心有限公司 | Long chain normal dibasic acid production method |
| CN101328165A (en) * | 2007-11-23 | 2008-12-24 | 上海凯赛生物技术研发中心有限公司 | Macrolides spice 1,10-dicarboxydecane propylene phthalate and production method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335312A (en) * | 2000-07-24 | 2002-02-13 | 中国石油化工股份有限公司 | Method of purifying macrocyclic ester compound of musk |
| CN1351005A (en) * | 2000-10-26 | 2002-05-29 | 中国石油化工股份有限公司 | Process for extracting and refining long-chain dicarboxylic acid from bio-fermented liquid |
| CN1570124A (en) * | 2004-05-12 | 2005-01-26 | 上海凯赛生物技术研发中心有限公司 | Long chain normal dibasic acid production method |
| CN101328165A (en) * | 2007-11-23 | 2008-12-24 | 上海凯赛生物技术研发中心有限公司 | Macrolides spice 1,10-dicarboxydecane propylene phthalate and production method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110963990A (en) * | 2019-12-25 | 2020-04-07 | 江西黄岩香料有限公司 | Preparation method of musk C-14 |
| CN111620773A (en) * | 2020-06-16 | 2020-09-04 | 席海红 | Method for preparing dibasic acid by using musk-T kettle residue |
| CN114276229A (en) * | 2021-12-31 | 2022-04-05 | 万华化学集团股份有限公司 | Method for recycling musk T kettle residue |
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