CN1088055C - Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it - Google Patents
Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it Download PDFInfo
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- CN1088055C CN1088055C CN99113296A CN99113296A CN1088055C CN 1088055 C CN1088055 C CN 1088055C CN 99113296 A CN99113296 A CN 99113296A CN 99113296 A CN99113296 A CN 99113296A CN 1088055 C CN1088055 C CN 1088055C
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- fermented liquid
- acid
- straight chain
- dicarboxylic acid
- aliphaticdicarboxylic
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Abstract
The present invention discloses a method for extracting refined long chain dicarboxylic acids from fermentation liquid. After an extraction solvent is used for processing fermentation liquid, a back extraction method is used for transferring a dicarboxylic acid product to a water phase from an organic phase, and then, the dicarboxylic acid product is obtained by adopting the steps of acid precipitation, filtration, drying, etc. Compared with the prior art, the present invention has the advantages of simplified process steps, shortened operation cycle, reduced energy consumption, improved working environment and operational safety, reduced solvent consumption and lightened air pollution.
Description
The present invention relates to a kind of refining α, method of omega-long chain dicarboxylic acid from fermented liquid, extracted.
At present, generally adopt bio-oxidation process to produce long chain dicarboxylic acid both at home and abroad, utilize the normal paraffin of different carbon numbers to obtain corresponding meta-bolites α through bio-oxidation, the omega-long chain dicarboxylic acid, from fermented liquid, extract the refining purity high product that obtains then, utilize conventional method (as filter, centrifugal, crystallization, membrane sepn etc.) make with extra care that to purify be very difficult, the product purity that obtains, yield are all not high.Japanese Patent JP56-15695 discloses a kind of with toluene solvant extracts, the organic phase spent glycol is stripped method, its way is at first the filtering fermentation liquor degerming to be obtained clear liquid, use the HCl acidizing crystal, with the toluene extraction, organic phase is stripped with the ethylene glycol of equivalent then.The main drawback of this method is the fermented liquid thickness, and thalli granule is small, and filtration sterilization is difficulty very, brings very burden to operation, and especially fermented liquid dyes when assorted bacterium is arranged all the more so.And the difficult filter of filter cake thickness is dried, and product loss is big, and yield is not high.Chinese patent CN1070394 discloses a kind of with the extractive method of ketones solvent, and its purpose is that the solution product recovery rate is low, problems such as filtration difficulty.To stop fermented liquid through heating, breakdown of emulsion, the unconverted alkane of separation, acidizing crystal, filtration drying obtains dried filter cake (major ingredient is dicarboxylic acid and thalline), under heating condition, use the dicarboxylic acid in the ketones solvent dissolving filter cake then, remove thalline and insolubles more after filtration, decrease temperature crystalline refilters branch and desolvates, and dry cake obtains dicarboxylic acid product.Though this method has improved the yield of product, the subject matter that exists is: (1) fermented liquid is at first wanted acidizing crystal, filtration, drying after separating unconverted alkane, just carries out extracting then, and process is numerous and diverse like this, the operational cycle is long, expense is high; (2) because directly crystallization from solvent of product is filtered in the filter cake of back and contained many solvents, this part solvent has all vapored away when drying, has both caused solvent loss, has polluted environment again.
The objective of the invention is provides a kind of whole beer solvent extraction method in order to overcome above-mentioned the deficiencies in the prior art, simplifies technological process, shortens the operational cycle, reduces solvent consumption and process cost, thereby product cost is reduced.
Realize that technical scheme of purpose of the present invention can be:
Main process of the present invention comprises:
(1) unconverted normal paraffin is removed in separation from stop fermented liquid;
(2) handle (1) step gained with organic solvent extraction and contain α, the fermented liquid of omega-long chain dicarboxylic acid and thalline obtains being dissolved with the organic layer of purpose product;
(3) insoluble impurities that carries in thalline and the solvent phase is removed in the filtered while hot separation;
(4) with the reextraction method dicarboxylic acid product is transferred to aqueous phase from organic phase;
(5) obtain the crystallisate of long chain dicarboxylic acid from gained aqueous phase acid out;
(6) separation, dry above-mentioned crystallisate obtain dicarboxylic acid product.
Realize that another scheme of the present invention can be:
(1) unconverted normal paraffin is removed in separation from stop fermented liquid;
(2) handle with organic solvent and contain α, the fermented liquid of omega-long chain dicarboxylic acid and thalline obtains being dissolved with the organic layer of purpose product;
(3) handle above-mentioned organic layer with decolorizing adsorbent;
(4) insolubless such as decolorizing adsorbent, thalline, organic salt are removed in the filtered while hot separation;
(5) with the reextraction method dicarboxylic acid product is transferred to aqueous phase from organic phase;
(6) obtain the crystallisate of long chain dicarboxylic acid from gained aqueous phase acid out;
(7) separation, dry above-mentioned crystallisate obtain dicarboxylic acid product.
Below the concrete steps of above-mentioned two schemes are elaborated.
Separating the method for removing unconverted normal paraffin can be:
Termination fermented liquid after the fermentation ends is heated to 80～100 ℃, leaves standstill then, make unconverted alkane and fermented liquid layering, the upper strata is an alkane, and lower floor is fermented liquid and thalline, divides and removes upper strata alkane.
Extraction step can be carried out by the following method:
Add extraction solvent in the fermented liquid after separation of alkane, be heated to 80～100 ℃ under stirring and extract, dicarboxylic acid is transferred in the solvent phase from fermented liquid.In order to reduce the solubleness of dicarboxylic acid at aqueous phase, make extraction more complete, alleviate emulsifying effect simultaneously, be better than the pH value that the mineral acid (as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid etc.) of dicarboxylic acid is regulated fermented liquid with acidity, make it to reach 4.5～3.0, then standing demix under being incubated, the upper strata is the solvent phase that is dissolved with dicarboxylic acid, lower floor is an aqueous phase layer, and thalline has been stayed in the aqueous phase layer, separates the solvent phase that obtains containing dicarboxylic acid then.In order to extract fully, also can adopt twice or method of extraction repeatedly, the solvent phase with twice or repeatedly extraction merges then.
In above-mentioned extraction process, extraction temperature is advisable to be no more than 100 ℃, is preferably 85～90 ℃, and mixing speed preferably keeps 20～50r/min.
When regulating the pH value, the concentration of mineral acid is preferably 5～10N.
For employed solvent, should have following character:
(1) do not dissolve each other with water, and under high and low temperature, solubleness and solvent the solubleness in water of water in solvent is all little;
(2) when high temperature, the solubleness of dicarboxylic acid is wanted big, and solubleness is little when low temperature;
(3) under operational condition not with dicarboxylic acid generation chemical reaction;
(4) price is low or moderate, and safety coefficient is big.
Such organic solvent has ketones solvent, as methyl iso-butyl ketone (MIBK), butanone etc., or in esters solvent such as N-BUTYL ACETATE, the isobutyl acetate etc. one or more.
The usage quantity of organic solvent is decided according to the dicarboxylic acid content in the fermented liquid, so that the dicarboxylic acid in the fermented liquid can dissolve fully or more slightly getting final product, is generally fermented liquid: solvent (v/v)=1: 0.5～1.2, preferably 1: 0.6～0.8.
Decolorizing adsorbent handle organic layer process can for:
In the resulting solvent phase of said process, add an amount of decolorizing adsorbent, to remove the impurity such as middle dissolved organic pigment and soluble proteins that desolvate, keep 90～120 ℃ of temperature, the absorption of under stirring condition, decolouring, the time is 1h at least, be preferably 1～2h, filtered while hot is removed some insoluble impuritiess of carrying secretly in decolorizing adsorbent, a spot of thalline and the solvent then, obtains the water white organic solution that contains dicarboxylic acid.The service temperature of sepn process preferably remains on 90～100 ℃.
Decolorizing adsorbent is gac or the atlapulgite with vesicular structure, and gac is preferably selected the macroporous type powdered carbon for use.For atlapulgite, its requirement is a water content 5.0～10.0%, is preferably 6.5～8.0%, and granularity is that 120 mesh sieve throughputs are more than 95%.The add-on of decolorizing adsorbent is determined according to the shade of solvent phase, is generally 1.0～6.5%, is preferably 3.0～5.5%.
Strip stage can adopt following method: in the organic hot solvent that contains dicarboxylic acid that above-mentioned steps obtains, the hot water (80～90 ℃ of temperature) that adds 1.2～2 times of volumes under the stirring at low speed, NaOH solution with 6～10N alkalizes, make the pH value of water reach 9～12, and reduce temperature to room temperature, make the dicarboxylic acid in the solvent phase transfer to aqueous phase, standing demix.The upper strata is that solvent can directly return for using next time, and lower floor is the aqueous phase layer that contains the dicarboxylic acid sodium salt.
The used hot water of stripping preferably uses the pure water that purified, and relatively poor water quality can form the metal-salt of dicarboxylic acid in treating processes, residue in the product, influences the use properties of product.
The acid out step can be with reference to following method:
The sodium salt solution of above-mentioned dicarboxylic acid is heated to 80～95 ℃, stirs the mineral acid (as sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid etc.) that drips 2～8N down, the pH value of regulator solution reaches 4.5～3.0, and dicarboxylic acid is existed with the free state form.Control cooling rate then and slowly lower the temperature, stirring at low speed, cooling rate can be 3～15 ℃/h, rotating speed can be 20～50r/min, and dicarboxylic acid partial crystallization from solution is come out, and reduces to and continues after the room temperature to keep 5～10h, is beneficial to generate good crystal habit.
Separate above-mentioned crystallisate and can adopt methods such as filtration or centrifugation, dicarboxylic acid is separated from crystal solution, obtain wet crystal.
The wet crystal of dicarboxylic acid is carried out drying, and drying temperature＜100 ℃ are preferably 50～70 ℃.Promptly obtain purified α after the drying, omega-long chain dicarboxylic acid product, outward appearance are white powder.
Said α, the omega-long chain dicarboxylic acid is meant C
11～C
18The straight chain aliphaticdicarboxylic acid, molecular formula is HOOC (CH
2)
nCOOH (n=9～16) both can be the dicarboxylic acid of single component, also can be the mixed dicarboxylic acid of any component, arbitrary proportion.The content of the dicarboxylic acid in the fermented liquid is 20～180g/l.
The present invention compared with prior art has the following advantages:
(1) owing to be the whole beer extraction, directly extracted products from fermented liquid has been saved preprocessing process such as acidizing crystal, filtration, drying, has simplified processing step, has shortened the operational cycle, has reduced energy consumption;
(2) the decolouring adsorption step has been removed impurity such as organic pigment in the solvent and soluble proteins, the purity of the dicarboxylic acid product that subsequent processes obtains was guaranteed, can make recovered solvent lighter color, impurity few again, can directly return repeated use, remove tediously long solvent reclamation process from.
(3) because the back several steps all carries out at aqueous phase, be convenient to operation, improved Working environment and processing safety;
(4) product directly from the aqueous phase crystallization, has reduced solvent consumption, has alleviated atmospheric pollution, and the boiling point of water is low, is easy to volatilization, is convenient to reduce energy consumption for drying, shortens time of drying, can residual solvent in the product.
Technological process of the present invention is simple, and energy consumption is low, and product cost is low, helps mass industrialized production.
Embodiment 1
Get the termination fermented liquid 400ml that makes substrate with positive structure n-tridecane hydrocarbon, wherein the content of undecane dicarboxylic acid is 96g/l, is heated to 90～100 ℃ under stirring, and standing demix separates and removes unconverted alkane then.Add the 240ml N-BUTYL ACETATE, be heated to 90～95 ℃ under stirring, (stirring velocity 40～50r/min), the H of dropping 6N
2SO
4, the pH value of fermented liquid to be transferred end about 4.0, insulation is standing demix down, and the two-phase layer separates up and down.The N-BUTYL ACETATE that adds 100～120ml in lower floor has the aqueous phase layer of thalline, extraction once merges the solvent phase of twice extraction again.Add the 13g powdered carbon, be heated to about 100 ℃ under stirring, decolouring absorption 1.5h, heat filtering under insulation then.Resulting hot filtrate adds 70～80 ℃ pure water 400ml under the continuation insulation, the pH value of regulating water with the NaOH solution about 6N is 10, and standing demix and cool to room temperature divide and go the upper strata solvent for use next time.Lower floor's aqueous phase layer is the H of (stirring velocity 25r/min) dropping 4N under agitation
2SO
4Adjust pH ends 4.0～3.0, is heated to and makes the solution becomes clarification about 90 ℃.Control is cooled to room temperature then, about 5～10 ℃/h of cooling rate.In temperature-fall period, dicarboxylic acid product is slowly separated out with crystalline form from solution, obtains the dicarboxylic acid filter cake after the filtration, obtains the white powder undecane dicarboxylic acid 60 ℃ of following dryings, product yield 96.1%, purity 95.6%, total acid content＞99.0%.
Embodiment 2
Get the termination fermented liquid 400ml that makes substrate with positive structure tridecane, wherein the content of undecane dicarboxylic acid is 127g/l, is heated to 90 ℃ under stirring, and standing demix divides and removes unconverted n-tridecane.Add 320ml respectively and the 140ml methyl iso-butyl ketone (MIBK) is carried out twice extraction.Compare with embodiment 1, except that not having the decolouring adsorption step, other operation steps and condition are identical.The product appearance that obtains is a white powder, the rate of recovery 97.4% of undecane dicarboxylic acid, purity 96.3%, total acid content＞99.0%.
Embodiment 3～4
Get respectively and contain Thapsic acid and contain C
12～C
16(it consists of mixed dicarboxylic acid: C
12Dicarboxylic acid 6.8%, C
13Dicarboxylic acid 41.7%, C
14Dicarboxylic acid 38.5%, C
15Dicarboxylic acid 9.2%, C
16Dicarboxylic acid 3.6%) termination fermented liquid extracts, and solvent is a N-BUTYL ACETATE, and decolorizing adsorbent is a gac, and operation steps and method are with embodiment 1, and operational condition is listed in table 1, and result of implementation is listed in table 2.
Table 1
| Embodiment | Fermentating liquid volume ml | Product | Acid content g/l | Solvent adding amount ml | Decolorizing adsorbent add-on g |
| 3 | 500 | C 16Dicarboxylic acid | 96 | 450 | 16 |
| 4 | 500 | C 12～C 16Mixed dicarboxylic acid | 105 (total acids) | 500 | 21 |
Table 2
| Embodiment | Product purity % | Total acid content % | Outward appearance | 95% ethanolic soln | Product recovery rate % |
| 3 | 95.8 | ＞99.0 | White powder | Water white transparency | 96.4 |
| 4 | ＞99.0 | White powder | Water white transparency | 95.0 |
Claims (7)
1. one kind is extracted refining α, ω-C from fermented liquid
11～C
18The method of straight chain aliphaticdicarboxylic acid comprises following step:
(1) unconverted normal paraffin is removed in separation from stop fermented liquid;
(2) handle (1) step gained with organic solvent extraction and contain α, ω-C
11～C
18The fermented liquid of straight chain aliphaticdicarboxylic acid and thalline obtains being dissolved with the organic layer of purpose product;
(3) insoluble impurities of carrying secretly in thalline and the solvent phase is removed in the filtered while hot separation;
(4) with the reextraction method dicarboxylic acid product is transferred to aqueous phase from organic phase;
(5) obtain C from gained aqueous phase acid out
11～C
18The crystallisate of straight chain aliphaticdicarboxylic acid;
(6) separation, dry above-mentioned crystallisate obtain dicarboxylic acid product.
2. according to described refining α, the ω-C of from fermented liquid, extracting of claim 1
11～C
18The method of straight chain aliphaticdicarboxylic acid is characterized in that in described extraction process, and behind the adding extraction agent, the pH value of regulating fermented liquid is in 3.0～4.5 scope.
3. according to described refining α, the ω-C of from fermented liquid, extracting of claim 1
11～C
18The method of straight chain aliphaticdicarboxylic acid is characterized in that described extraction agent is one or more in methyl iso-butyl ketone (MIBK), butanone, N-BUTYL ACETATE, the isobutyl acetate.
4. one kind is extracted refining α, ω-C from fermented liquid
11～C
18The method of straight chain aliphaticdicarboxylic acid comprises following step:
(1) unconverted normal paraffin is removed in separation from stop fermented liquid;
(2) contain α, ω-C with the organic solvent processing
11～C
18The fermented liquid of straight chain aliphaticdicarboxylic acid and thalline obtains being dissolved with the organic layer of purpose product;
(3) handle above-mentioned organic layer with decolorizing adsorbent;
(4) insolubless such as decolorizing adsorbent, thalline, organic salt are removed in the filtered while hot separation;
(5) with the reextraction method dicarboxylic acid product is transferred to aqueous phase from organic phase;
(6) obtain C from gained aqueous phase acid out
11～C
18The crystallisate of straight chain aliphaticdicarboxylic acid;
(7) filtration, dry above-mentioned crystallisate obtain dicarboxylic acid product.
5. according to described refining α, the ω-C of from fermented liquid, extracting of claim 4
11～C
18The method of straight chain aliphaticdicarboxylic acid is characterized in that in described extraction process, and behind the adding extraction agent, the pH value of regulating fermented liquid is in 3.0～4.5 scope.
6. according to described refining α, the ω-C of from fermented liquid, extracting of claim 4
11～C
18The method of straight chain aliphaticdicarboxylic acid is characterized in that described extraction agent is one or more in methyl iso-butyl ketone (MIBK), butanone, N-BUTYL ACETATE, the isobutyl acetate.
7. according to described refining α, the ω-C of from fermented liquid, extracting of claim 4
11～C
18The method of straight chain aliphaticdicarboxylic acid is characterized in that described decolorizing adsorbent is gac or the atlapulgite with vesicular structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113296A CN1088055C (en) | 1999-09-29 | 1999-09-29 | Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99113296A CN1088055C (en) | 1999-09-29 | 1999-09-29 | Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it |
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| Publication Number | Publication Date |
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| CN1289757A CN1289757A (en) | 2001-04-04 |
| CN1088055C true CN1088055C (en) | 2002-07-24 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6660505B2 (en) * | 2000-06-22 | 2003-12-09 | Cognis Corporation | Isolation of carboxylic acids from fermentation broth |
| CN102617320A (en) * | 2012-02-08 | 2012-08-01 | 上海凯赛生物技术研发中心有限公司 | Method for treating reaction solution containing long chain dicarboxylate |
| CN107011147A (en) * | 2012-02-08 | 2017-08-04 | 上海凯赛生物技术研发中心有限公司 | The processing method of the reaction solution of the salt containing long-chain biatomic acid |
| CN103804174B (en) * | 2012-11-08 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of organic acid process for purification |
| TWI525074B (en) * | 2014-04-30 | 2016-03-11 | 財團法人工業技術研究院 | Method for purifying an organic acid |
| CN108947809B (en) * | 2017-05-18 | 2021-08-06 | 中国石油化工股份有限公司 | Method for extracting and refining long-chain dicarboxylic acid from fermentation liquor |
| CN107382708B (en) * | 2017-08-10 | 2020-11-20 | 中国科学院成都生物研究所 | Method for extracting medium-chain fatty acid caproic acid |
| CN111099987B (en) * | 2018-10-26 | 2023-02-03 | 中国石油化工股份有限公司 | Refining method of long-chain dicarboxylic acid in fermentation liquor |
| CN113264823B (en) * | 2021-05-31 | 2023-07-11 | 丰益高分子材料（连云港）有限公司 | Method for improving stability of sebacic acid |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5615695A (en) * | 1979-07-19 | 1981-02-14 | Mitsui Petrochem Ind Ltd | Recovery of dicarboxylic acid |
| JPS5626194A (en) * | 1979-08-09 | 1981-03-13 | Nippon Mining Co Ltd | Purification of long-chain dicarboxylic acid produced by fermentation |
| JPS57102191A (en) * | 1980-12-16 | 1982-06-25 | Mitsui Petrochem Ind Ltd | Separating method of dicarboxylic acid |
| CN1070394A (en) * | 1991-09-11 | 1993-03-31 | 中国石油化工总公司抚顺石油化工研究院 | A kind of method of refining long-chain biatomic acid |
-
1999
- 1999-09-29 CN CN99113296A patent/CN1088055C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5615695A (en) * | 1979-07-19 | 1981-02-14 | Mitsui Petrochem Ind Ltd | Recovery of dicarboxylic acid |
| JPS5626194A (en) * | 1979-08-09 | 1981-03-13 | Nippon Mining Co Ltd | Purification of long-chain dicarboxylic acid produced by fermentation |
| JPS57102191A (en) * | 1980-12-16 | 1982-06-25 | Mitsui Petrochem Ind Ltd | Separating method of dicarboxylic acid |
| CN1070394A (en) * | 1991-09-11 | 1993-03-31 | 中国石油化工总公司抚顺石油化工研究院 | A kind of method of refining long-chain biatomic acid |
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