CN1221510C - Refining method for long-chain biatomic acid - Google Patents
Refining method for long-chain biatomic acid Download PDFInfo
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- CN1221510C CN1221510C CN 03133560 CN03133560A CN1221510C CN 1221510 C CN1221510 C CN 1221510C CN 03133560 CN03133560 CN 03133560 CN 03133560 A CN03133560 A CN 03133560A CN 1221510 C CN1221510 C CN 1221510C
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Abstract
The present invention relates to a method for refining long-chain diacid. The method has the following steps that firstly, the terminated long-chain diacid fermentation liquor is directly heated to break emulsion, and the unreacted alkane is separated and recovered; then, the pH value of the fermentation liquor is adjusted by inorganic acid, and the fermentation liquor is acidified and crystallized; the long-chain diacid is heated to be melted into a molten state in inorganic salt water solution, and thus, an oil layer is formed to float above the water solution; inorganic salts, thalli, pigments and other impurities are remained in the water solution; the diacid in the molten state is separated, and stirred by adding water simultenously , and the diacid is crystallized, filtered and dried. The method can effectively separate and prepare long-chain diacid with high purity from the fermentation liquor, solve the problem that the sterilized and filtered diacid is washed by an amount of water when crystallized, greatly simplify the technological process, shorten the operation cycle, enhance the product yield, and reduce the product cost.
Description
Technical field
The present invention relates to a kind of from fermented liquid, the extraction and the method for refining long-chain biatomic acid.
Background technology
Long-chain alpha, omega-dibasic acid (hereinafter said " diprotic acid " all refers to " long-chain alpha, omega-dibasic acid ") are to utilize the normal paraffin of the high carbon number of microbial fermentation and the meta-bolites that obtains, has application widely at aspects such as synthetic perfume, engineering plastics, hot melt adhesive, coating, liquid crystal, yet want Separation and Recovery long-chain biatomic acid from fermented liquid, need complicated last handling process.High carbon number normal paraffin fermentation back gained fermented liquid is except that containing long-chain biatomic acid, also contain fermentation thalline, substratum and unfermentable normal paraffin etc., pretreatment processs such as the general centrifugal separation that adopts, Plate Filtration method, salting-out process, and then make with extra care through methods such as water method, organic solvent extractionprocess, esterification process.
The pretreated method of long-chain biatomic acid is: with the terminated fermented liquid through heating demulsification type, separate unconverted alkane, filtration sterilization, acidizing crystal, filtered binary acid, dry thick long-chain biatomic acid.The key that this pretreatment process influences diprotic acid purity and yield is the filtration sterilization step.The fermented liquid thickness, thalli granule is small, and filtration sterilization is difficulty very, brings very burden to operation, and is all the more so when especially fermented liquid has assorted bacterium, and filtering thalline contains the filtrate height, and product loss is big.Acidizing crystal also is a difficult point of handling fermented liquid, the fermented liquid of filtration sterilization need heat the back with mineral acid transfer PH to 4 or below, crystallisation by cooling, filtering for crystallizing.Mineral acid is easily being wrapped up in the diprotic acid crystallization, filtering diprotic acid crystallization needs a large amount of water washings, making diprotic acid crystalline pH value is 5～7, mineral acid washing in the diprotic acid crystallization is not thorough, influence the quality and the yield of subsequent product, impurity in the water washing process waterpipe and the inorganic salt in the water also are the processes that makes the diprotic acid secondary pollution.All there is above problem in pretreatment processs such as centrifugal separation, Plate Filtration method, salting-out process, all can't solve filtration sterilization difficulty, product loss is big, yield is low and purity is low problem.
The treatment process of JP 56-260193, JP 56-260194 is that the terminated fermented liquid is left standstill under alkaline condition, bactofugation, add thalline and some impurity that diatomite adsorption is not removed, filter, add acid, acid out crystallization, filtration and drying then, obtain the diprotic acid crystal at last.The subject matter of aforesaid method is that fermented liquid leaves standstill under alkaline condition and has aqtocytolysis, cell protein is flowed in the fermented liquid, increased the fermented liquid foreign matter content, thereby influenced product purity, and still contain bulk fermentation liquid in the centrifugal thalline of removing, reduced the yield of product.
It is with termination fermented liquid direct heating breakdown of emulsion that CN 1064951C has introduced a kind of method of handling fermented liquid, and the unreacted alkane of Separation and Recovery is again with the fermented liquid acidizing crystal, filtered binary acid and thalline, the filter cake of alkalization dissolving diprotic acid, thalline transfers to 8～12 with the pH value, add salting-out agent, heating for dissolving, cold filtration dicarboxylate, again dissolve dicarboxylate in the water again, heat 40 ℃～60 ℃, cooling is filtered, acidizing crystal, filter crystal and washing, drying.This method reclaims behind the unreacted alkane directly with the fermented liquid acidizing crystal, and the diprotic acid crystalline particle is little to be filtered simultaneously with thalline, has increased filtration difficulty; Need to add salting-out agent in this process in addition, make operation more loaded down with trivial details.
CN 1088055C has introduced a kind of fermented liquid solvent extraction method, to stop fermented liquid direct heating breakdown of emulsion, reclaim unreacted alkane, handle fermented liquid with organic solvent, obtain containing the organic layer of diprotic acid, water and organic phase are filtered simultaneously, with the reextraction method diprotic acid is transferred to the water from organic phase, acidizing crystal filters crystal, washs then and drying.This method is filtered water and organic phase simultaneously, the thalline filtration difficulty of aqueous phase, and filtration velocity is slow, has prolonged the entire operation time, and the loss of organic solvent has improved production cost of products.
It is with 50 ℃～100 ℃ breakdowns of emulsion of termination fermented liquid direct heating that CN 1049688C has introduced a kind of method of handling fermented liquid, the unreacted alkane of refrigerated separation, and the flocculating aids that adds 2wt%～5wt% filters, and washing bacterium cake, acidizing crystal filters crystal and washing, drying.Its shortcoming is to adopt the granularity of 100～200 order pearl salt flocculating aidss own just very thin, adds the heavy-gravity thalline, need be in press filtration under 0.1～0.2Mpa, and filtrate is filtered unclean, certainly will cause the slow and low problem of product yield of filtration velocity like this.
Summary of the invention
At the deficiencies in the prior art, the object of the present invention is to provide a kind of method with the purifying high-purity long-chain biatomic acid of getting from fermented liquid effectively, break away from filtration sterilization, a large amount of water washing problem of filtering diprotic acid crystallization needs, simplified technological process greatly, shorten the operational cycle, improve product yield, thereby reduced the cost of product.
Method of the present invention may further comprise the steps:
A, with terminated long-chain biatomic acid fermented liquid direct heating breakdown of emulsion, the unreacted alkane of Separation and Recovery;
The fermented liquid acidizing crystal that b, step a obtain, heating makes long-chain biatomic acid fuse into molten state in the aqueous solution of inorganic salt then, float on above the aqueous solution and form oil reservoir, inorganic salt, thalline, pigment and other impurity are stayed in the aqueous solution, kept best 20～60 minutes 20～120 minutes;
C, isolate the diprotic acid of molten state among the step b, add 20～90 ℃ water then while stirring, diprotic acid crystallization, filtration and drying; Perhaps after step b, directly cooling makes the molten state diprotic acid form solid layer and separate with aqueous layer, takes out solid binary acid.
The Heating temperature that makes long-chain biatomic acid fuse into molten state among the above-mentioned steps b in the aqueous solution of inorganic salt is 90～120 ℃; Before step c, preferably with 3～20 ℃ of the liquid of step b gained coolings, keep diprotic acid to be in molten state fully simultaneously and be still in above the aqueous solution, kept 10～60 minutes, in order to avoid the ebullient bubble is sneaked into impurity in the diprotic acid of molten state.
The said long-chain biatomic acid of the present invention is meant C
9～C
13The straight chain aliphatic dibasic acid of single component has general general molecular formula: HOOC (CH
2)
nCOOH (n=7～11) also can be C
9～C
16Any component that two or more mixing normal paraffin is produced, the mixing straight chain aliphatic dibasic acid of arbitrary proportion.
Compared with prior art, the inventive method has the following advantages and characteristics:
1, breaks away from the committed step-filtration sterilization that influences diprotic acid purity and yield, simplified technological process;
2, having broken away from filtering diprotic acid crystallization needs a large amount of water washings, has avoided diprotic acid secondary pollution process;
3, the inventive method is because processing step is few, and facility investment is few, and is with short production cycle, thereby production cost is greatly reduced;
4, the inventive method adopts the long-chain biatomic acid fermented liquid directly to handle, need not pre-treatment, and purity reaches more than the 96wt%, and product recovery rate can reach more than the 96wt%;
5, the inventive method is not used any organic solvent, flocculating aids, salting-out agent etc., has avoided the pollution of environment and the waste of chemical reagent.
Embodiment
The concrete operations of method of the present invention may further comprise the steps:
A, terminated long-chain biatomic acid fermented liquid direct heating to 50～100 ℃ is carried out breakdown of emulsion, be preferably between 80～95 ℃, constant temperature 1～5 hour is cooled to 30～50 ℃, after static again 1～5 hour, and the unreacted alkane of Separation and Recovery;
The temperature of b, fermented liquid that step a is obtained is heated to 40～80 ℃, be preferably between 60～70 ℃, regulate with mineral acid between pH value to 1～7 of fermented liquid, be preferably between 3～5 acidizing crystal, be heated to 90～120 ℃ then, make long-chain biatomic acid fuse into molten state in the aqueous solution of inorganic salt, float on above the aqueous solution and form oil reservoir, inorganic salt, thalline, pigment and other impurity are stayed in the aqueous solution, kept best 30～60 minutes 20～120 minutes; 3～20 ℃ of the liquid coolings that obtains above-mentioned keep diprotic acid to be in molten state fully simultaneously and are still in above the aqueous solution, and the hold-time is 10～60 minutes;
C, isolate the diprotic acid of the molten state among the step c, add 20～90 ℃ water while stirring, diprotic acid crystallization, filtration and drying; Or after step c, directly cooling makes the molten state diprotic acid form solid layer and separate with aqueous layer, bleeds off aqueous layer, washes the diprotic acid solid surface with water, takes out solid binary acid, dispels the water of solid binary acid surfaces.
Isolate the diprotic acid of the molten state among the step b among the described step c, can adopt following any method: first kind is to carry out in same container, directly bleed off aqueous layer, the most handy a spot of 80～100 ℃ of water washing molten state diprotic acid are 1～3 time before adding the water stirring, bleed off the aqueous solution then; Second kind is that diprotic acid with molten state is separated in another container, adds 20～90 ℃ water then while stirring, and diprotic acid is carried out crystallization, filtration and drying.The purpose of washing molten state diprotic acid is flush away molten state diprotic acid and aqueous solution contact surface adsorbed thalline and impurity, and the thalline and the impurity that are adsorbed on inner surface of container.
The present invention is further elaborated below in conjunction with specific embodiment.
Embodiment 1
Preparation undecane diprotic acid.
A, positive structure undecane hydrocarbon obtain containing the fermented liquid of undecane diacid behind biological fermentation, unreacted reactant content 11.5wt%, cell concentration are that 10g/L, acid concentration are that 105g/L, pH value are 7.6 in the fermented liquid.1000 milliliters of direct heating to 80 of terminated undecane dibasic acid fermentation liquor ℃ are carried out breakdown of emulsion, and constant temperature 3 hours is cooled to 30 ℃, after static again 2.5 hours, and the unreacted alkane of Separation and Recovery;
Undecane dibasic acid fermentation liquor after b, the separation of alkane is heated to 40 ℃, being 6 hydrochloric acid with equivalent concentration transfers to 3 with the pH value of fermented liquid, acidizing crystal, be heated to 108 ℃, make the undecane diprotic acid in the aqueous solution of inorganic salt, fuse into molten state, float on above the aqueous solution and form oil reservoir, inorganic salt, thalline, pigment and other impurity are stayed in the aqueous solution, keep 100 minutes; The above-mentioned liquid that obtains is cooled to 98 ℃, kept 30 minutes, make the undecane diprotic acid be in molten state fully, and float on above the aqueous solution;
The undecane diprotic acid of c, the molten state that directly step b obtained is assigned in other retort, add 60 ℃ 1000 milliliters in water while stirring, with the crystallization of undecane diprotic acid, filter then and drying, obtaining total acid content is the undecane diprotic acid of 97.3wt%, and product recovery rate is 96.7wt%.
Embodiment 2
Preparation dodecane diprotic acid.
A, positive structure dodecane hydrocarbon obtain containing the fermented liquid of dodecanedioic acid behind biological fermentation, unreacted reactant content 10.4wt%, cell concentration are that 15g/L, acid concentration are that 110g/L, pH value are 7.8 in the fermented liquid.With 1000 milliliters of direct heating to 95 ℃ breakdowns of emulsion of terminated dodecane dibasic acid fermentation liquor, constant temperature 4 hours is cooled to 35 ℃, after static again 3 hours, and the unreacted alkane of Separation and Recovery;
Dodecane dibasic acid fermentation liquor after b, the separation of alkane is heated to 60 ℃, be that 6 hydrochloric acid transfers to 4 with the pH value with equivalent concentration, acidizing crystal, be heated to 110 ℃, make the dodecane diprotic acid in the aqueous solution of inorganic salt, fuse into molten state, float on above the aqueous solution and form oil reservoir, inorganic salt, thalline, pigment and other impurity are stayed in the aqueous solution, keep 30 minutes; The above-mentioned liquid that obtains is cooled to 105 ℃, kept 50 minutes, the dodecane diprotic acid is in molten state fully and floats on above the aqueous solution;
The dodecane diprotic acid of c, the molten state that directly step b obtained is assigned in other retort, add 40 ℃ 800 milliliters in water while stirring, make the crystallization of dodecane diprotic acid, filter then and dry, obtain the dodecane diprotic acid of total acid content 98.1wt%, product recovery rate 97.3wt%.
Embodiment 3
The preparation mixed dibasic acid.
A, get with C
10～C
15Mix normal paraffin (C
10～C
15Mix normal paraffin proportioning such as table 1) be the fermented liquid of raw material behind biological fermentation, obtain containing the fermented liquid that mixes diprotic acid, unreacted reactant content 10.4wt%, cell concentration are that 15g/L, acid concentration are that 110g/L, pH value are 7.8 in the fermented liquid.With 1000 milliliters of direct heating to 70 ℃ breakdowns of emulsion of terminated mixed dibasic acid fermented liquid, constant temperature 5 hours is cooled to 40 ℃, after static again 4 hours, and the unreacted mixed alkanes of Separation and Recovery;
Mixed dibasic acid fermented liquid after b, the separation of alkane is heated to 80 ℃, be that 6 hydrochloric acid transfers to 6 with the pH value with equivalent concentration, acidizing crystal, be heated to 95 ℃, make mixed dibasic acid in the aqueous solution of inorganic salt, fuse into molten state, float on above the aqueous solution and form oil reservoir, inorganic salt, thalline, pigment and other impurity are stayed in the aqueous solution, keep 90 minutes;
C, bleed off aqueous layer, 90 ℃ of water washing molten state mixed dibasic acids with 50ml, bleed off the aqueous solution, add 50 ℃ 500 milliliters in water while stirring, with the mixed dibasic acid crystallization, filter then and drying, obtain the mixed dibasic acid that total acid content is 97.1wt%, product recovery rate 97.2wt%.
Embodiment 4
Preparation tridecane diprotic acid.
A, positive structure tridecane hydrocarbon obtain containing the fermented liquid of undecane dicarboxylic acid through microbial fermentation, and unreacted reactant content 8wt%, cell concentration are that 12g/L, acid concentration are that 100g/L, pH value are 7.8 in the fermented liquid.Directly 1000 milliliters of tridecane dibasic acid fermentation liquors are heated to 60 ℃ of breakdowns of emulsion, constant temperature 2 hours is cooled to 50 ℃, after static again 2 hours, and the unreacted tridecane hydrocarbon of Separation and Recovery;
Tridecane dibasic acid fermentation liquor after b, the separation of alkane is heated to 70 ℃, be that 6 hydrochloric acid transfers to 4 with the pH value with equivalent concentration, acidizing crystal, be heated to 108 ℃, make the tridecane diprotic acid in the aqueous solution of inorganic salt, fuse into molten state, float on above the aqueous solution and form oil reservoir, inorganic salt, thalline, pigment and other impurity are stayed in the aqueous solution, keep 20 minutes; The above-mentioned liquid that obtains is cooled to 100 ℃, kept 60 minutes, make the tridecane diprotic acid be in molten state fully and float on above the aqueous solution;
C, the liquid that step b is obtained directly cool to 50 ℃, molten state tridecane diprotic acid is formed solid layer and is separated with aqueous layer, bleed off aqueous layer, with twice of 50 milliliters 80 ℃ water washing tridecane diprotic acid solid surface, take out solid tridecane diprotic acid, dispel the water on solid tridecane diprotic acid surface, obtaining total acid content is the tridecane diprotic acid of 96.8wt%, product recovery rate 97.7wt%.
Comparative Examples 1
The method that adopts Chinese patent CN 1049688C to prepare long-chain biatomic acid prepares mixed dibasic acid and tridecane diprotic acid, and its concrete preparation process is seen embodiment 2 and the embodiment 1 among the CN 1049688C, sees Table 2 with comparing result of the present invention.
Table 1 C
10～C
15The proportioning of mixing normal paraffin and fermentation back mixing acid
| Carbon number | C 9 | C 10 | C 11 | C 12 | C 13 | C 14 | C 15 |
| Mixed alkanes, wt% | 0.27 | 2.22 | 9.53 | 30.99 | 49.23 | 6.12 | 1.12 |
| Mixing acid, wt% | 1.34 | 4.60 | 12.03 | 33.75 | 36.38 | 10.95 | 0.72 |
Table 2 the present invention and Chinese patent CN 1049688C comparing result
| DC 13Purity, wt% | DC 13Yield, wt% | DC MixPurity, wt% | DC MixYield, wt% | |
| The present invention | 96.8 | 97.7 | 97.1 | 97.2 |
| CN1049688C | 96 | 94 | 94.7 | 92.9 |
Claims (10)
1, a kind of process for purification of long-chain biatomic acid may further comprise the steps:
A, with terminated long-chain biatomic acid fermented liquid direct heating breakdown of emulsion, the unreacted alkane of Separation and Recovery;
The fermented liquid acidizing crystal that b, step a obtain, heating makes long-chain biatomic acid fuse into molten state in the aqueous solution of inorganic salt then, float on above the aqueous solution and form oil reservoir, inorganic salt, thalline, pigment and other impurity are stayed in the aqueous solution, keep 20～120 minutes;
C, isolate the long-chain biatomic acid of molten state among the step b, add 20～90 ℃ water while stirring, diprotic acid crystallization, filtration and drying; Or directly cooling after step b, make the molten state diprotic acid form solid layer and separate with aqueous layer, take out solid binary acid;
Wherein said long-chain biatomic acid is C
9～C
13The straight chain aliphatic dibasic acid of single component perhaps is C
9～C
16The mixing straight chain aliphatic dibasic acid that two or more mixing normal paraffin is produced.
2, the process for purification of long-chain biatomic acid according to claim 1 is characterized in that the breakdown of emulsion temperature of described step a termination fermented liquid is 50～100 ℃.
3, the process for purification of long-chain biatomic acid according to claim 1 is characterized in that the fermented liquid temperature before the acidifying is 40～80 ℃ among the described step b.
4, the process for purification of long-chain biatomic acid according to claim 1, the acidifying that it is characterized in that fermented liquid among the described step b are to adopt mineral acid to regulate between pH value to 1～7 of fermented liquid.
5, the process for purification of long-chain biatomic acid according to claim 1 is characterized in that the Heating temperature behind the fermented liquid acidizing crystal is 90～120 ℃ among the described step b.
6, the process for purification of long-chain biatomic acid according to claim 1 is characterized in that it is 30～60 minutes that the described long-chain biatomic acid of step b keeps the time of molten state.
7, the process for purification of long-chain biatomic acid according to claim 1 is characterized in that by 3～20 ℃ of the resulting liquid of step b coolings, makes diprotic acid be in molten state fully and is still in above the aqueous solution, keeps 10～60 minutes.
8, the process for purification of long-chain biatomic acid according to claim 1, it is characterized in that the long-chain biatomic acid of molten state among the separating step b adopts following any method: first kind is to carry out in same container, directly bleeds off aqueous layer; Second kind is that diprotic acid with molten state is separated in another container.
9, the process for purification of long-chain biatomic acid according to claim 8 is characterized in that bleeding off after the aqueous layer in first kind of separation method, adds before water stirs, earlier with 80～100 ℃ of water washing molten state diprotic acid 1～3 time.
10, the process for purification of long-chain biatomic acid according to claim 1 when it is characterized in that taking among the step c direct falling temperature method, washed the solid binary acid surfaces with water before taking out solid binary acid.
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|---|---|---|---|
| CN 03133560 CN1221510C (en) | 2003-05-31 | 2003-05-31 | Refining method for long-chain biatomic acid |
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| CN1221510C true CN1221510C (en) | 2005-10-05 |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329212B (en) * | 2011-09-13 | 2014-02-12 | 中国石油化工股份有限公司 | Refining method for long-chain binary acid |
| CN102329211B (en) * | 2011-09-13 | 2014-04-09 | 中国石油化工股份有限公司 | C12-C13 long-chain binary acid refining method |
| CN103030550B (en) | 2011-09-30 | 2017-12-22 | 中国科学院微生物研究所 | The method and product of long-chain biatomic acid purification |
| CN103408448B (en) * | 2013-08-21 | 2015-12-23 | 南京华狮化工有限公司 | A kind of polishing purification method of N-acylamino acid or its salt |
| CN104844440B (en) * | 2014-02-17 | 2019-05-31 | 上海凯赛生物技术研发中心有限公司 | A kind of refining methd of long-chain mixed dibasic acid |
| CN104844441B (en) * | 2014-02-17 | 2019-05-31 | 上海凯赛生物技术研发中心有限公司 | A kind of method of purification of long-chain mixed dibasic acid |
| CN109516913B (en) * | 2017-09-18 | 2022-05-10 | 上海凯赛生物技术股份有限公司 | Aqueous phase melting crystallization process of long-chain dicarboxylic acid |
| CN107954858A (en) * | 2017-12-13 | 2018-04-24 | 天津大学 | A kind of crystal form of heneicosanedioic acid and preparation method thereof |
| CN108558646A (en) * | 2017-12-13 | 2018-09-21 | 天津大学 | A kind of crystal form of heneicosanedioic acid and preparation method thereof |
| CN111039776A (en) * | 2019-12-31 | 2020-04-21 | 淄博广通化工有限责任公司 | High-purity mixed long carbon chain dicarboxylic acid and preparation method thereof |
| CN113461514A (en) * | 2020-03-31 | 2021-10-01 | 上海凯赛生物技术股份有限公司 | Method for extracting long-chain dicarboxylic acid from fermentation liquor |
| CN114478235B (en) * | 2020-10-28 | 2024-05-07 | 中国石油化工股份有限公司 | Method for purifying organic acid in fermentation liquor |
| CN114917850B (en) * | 2022-06-13 | 2024-06-28 | 宁夏恒力生物新材料有限责任公司 | Device and method for purifying long carbon chain dibasic acid fermentation liquor in aqueous phase |
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