CN112724012B - Method for refining long-chain dibasic acid - Google Patents
Method for refining long-chain dibasic acid Download PDFInfo
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- 238000010438 heat treatment Methods 0.000 claims abstract description 10
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- 238000001816 cooling Methods 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000002425 crystallisation Methods 0.000 claims description 10
- 230000008025 crystallization Effects 0.000 claims description 10
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 4
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 4
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002207 metabolite Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- 244000005700 microbiome Species 0.000 claims description 2
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- 230000004151 fermentation Effects 0.000 description 13
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- 239000008346 aqueous phase Substances 0.000 description 9
- 239000012264 purified product Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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Classifications
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- 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
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for refining long-chain binary acid, which comprises the steps of heating a long-chain binary acid crude product, water and a mixed solvent, extracting, preserving heat, standing and then cutting off a lower water phase; adding alkali and water, back mixing, standing, and cutting off lower water phase; adding water, back mixing, standing, and cutting off lower water phase; cooling and crystallizing the solvent phase, filtering and drying to obtain a refined product. The method solves the problems of large solvent consumption, high cost and the like in the process of refining long-chain dibasic acid by a solvent method.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a method for producing long-chain dibasic acid by a refining fermentation method.
Background
The long-chain dicarboxylic acid refers to aliphatic dicarboxylic acid (DCn or DCA for short) containing more than 10 carbon atoms in a carbon chain, and the aliphatic dicarboxylic acid comprises saturated and unsaturated dicarboxylic acid, is a fine chemical product with important and wide industrial application, and is an important raw material for synthesizing high-grade perfume, high-performance nylon engineering plastics, high-grade nylon hot melt adhesives, high-temperature dielectrics, high-grade paints and coatings, high-grade lubricating oil, cold-resistant plasticizers, resins, medicines, pesticides and the like in the chemical industry.
In the fermentation production and refining process of long-chain dibasic acid, the components of fermentation liquor are complex, and besides dibasic acid, the fermentation liquor mainly comprises thalli, proteins, macromolecular pigments, inorganic salts and other intermediate metabolites, and the process flow for separating the long-chain dibasic acid from the fermentation liquor is complex, so that the separation cost of the long-chain dibasic acid is very large in proportion of production cost.
Currently, the refining methods of dibasic acid mainly comprise an aqueous phase method and a solvent method. Compared with the solvent method, the aqueous phase method has the advantages of less investment, no need of using organic solvent, safe process and simple operation, but the refining effect is poorer than that of the solvent method, the product can not meet the polymerization grade requirement, and the corresponding method and process are still in the research and development stage at present. Compared with the water phase method, the solvent method has high product purity, good color and uniform crystal granularity, and can be directly used for synthesizing the downstream products. The separation process of the dibasic acid mostly adopts a solvent recrystallization method.
CN105272842a discloses a purification method for producing dodecadiacid by biological fermentation, heating the fermentation stopping liquid of the dodecadiacid to break emulsion, filtering by a ceramic membrane and an ultrafiltration membrane to remove solid particles, macromolecular proteins and pigments, and obtaining ultrafiltrate; mixing the obtained ultrafiltrate with isoamyl alcohol to obtain mixed liquid, and heating to 40-90 ℃; preserving heat, adding concentrated sulfuric acid into the ultrafiltrate at the bottom of the mixed liquid to adjust the pH value of the ultrafiltrate to 2-6, stirring and mixing, and standing; and taking the upper layer extract phase for cooling crystallization, filtering, and cleaning and drying the crystal obtained after filtering to obtain the dodecadiacid crystal. The invention uses isoamyl alcohol as a recrystallization solvent, and adds isoamyl alcohol after acidification of the treated fermentation liquor, extracts dibasic acid into an upper solvent layer, then cools and crystallizes the extract liquid, and the total acid value of the product after purification is more than 99 percent, and the total nitrogen content is less than 30mg/kg. Wherein the mass volume of the dibasic acid and the isoamyl alcohol is 1:5, the dosage of the isoamyl alcohol is large, and the isoamyl alcohol has mutagenicity for acute toxicity.
At present, the national diacid is refined by adopting an acetic acid recrystallization method generally by main production enterprises, and public data show that the mass volume of the diacid and acetic acid is 1:12.5, the solvent consumption is large, the acetic acid corrosivity is extremely strong, the manufacturing and maintenance cost of production equipment is high, and the energy consumption is high when the acetic acid solvent is recycled.
CN102911036a is a refining method based on an ether solvent, and includes: i, heating and inactivating the fermentation stopping liquid; II, acidifying to crystallize and separate out the dicarboxylic acid, and filtering to obtain a dicarboxylic acid filter cake; III, mixing the dicarboxylic acid filter cake with an ether solvent to dissolve dicarboxylic acid, and separating an organic phase from a water phase, wherein the ether solvent is diethyl ether, propyl ether, butyl ether, amyl ether or hexyl ether; IV, adding an adsorbent into the organic phase obtained in the step III, and filtering to remove solids; and V, cooling the organic phase obtained in the step IV until the dicarboxylic acid is crystallized and separated out, filtering to obtain a dicarboxylic acid crystallization filter cake, and drying the dicarboxylic acid crystallization filter cake to obtain the high-purity dicarboxylic acid with the dicarboxylic acid purity of more than 98.5% by weight and the total nitrogen of less than 30ppm, so that the requirement of a polymerization-grade product is met. Taking diethyl ether (0.7134 g/mL) with the minimum density in the solvent as an example, the mass ratio of the dicarboxylic acid dry basis mass to the volume of the treatment solvent is 1:4.2-21 (g/mL) through 1:3-15, and the solvent use amount is high.
The solvent recrystallization method diacid refining technology can obtain a diacid refined product with low impurity content and high purity, but the solvent is large in use amount due to the fact that the carrying capacity of the solvent on the diacid is not high, and the refining cost is too high in the total production cost.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for refining long-chain dibasic acid. The method solves the problems of large solvent consumption, high cost and the like in the process of refining long-chain dibasic acid by a solvent method.
The method for refining long-chain dibasic acid provided by the invention comprises the following steps:
(1) Heating the long-chain binary acid crude product, water and a mixed solvent, extracting, preserving heat, standing and cutting off a lower water phase; the mixed solvent is a mixed solvent of an alcohol solvent and an ether solvent;
(2) Adding alkali and water, back mixing, standing, and cutting off lower water phase;
(3) Adding water, back mixing, standing, and cutting off lower water phase;
(4) Cooling and crystallizing the solvent phase, filtering and drying to obtain a refined product.
In the invention, in the mixed solvent in the step (1), the volume ratio of the alcohol solvent to the ether solvent is 1:5-1:100, preferably 1:10-1:20. The alcohol solvent can be at least one of ethanol, propanol, butanol and the like. The ether solvent can be at least one of propyl ether, butyl ether, amyl ether, hexyl ether and the like.
In the invention, the mass-volume ratio of the crude diacid product to the mixed solvent in the step (1) is 1:1 to 3 (g: mL).
In the invention, the long-chain dicarboxylic acid crude product in the step (1) is a dicarboxylic acid crude product prepared by heating, filtering, decoloring and acidifying long-chain dicarboxylic acid fermentation liquor, in particular to a long-chain dicarboxylic acidAnd heating the fermentation liquor to 70-80 ℃, removing thalli and partial impurities after microfiltration and ultrafiltration, adding an adsorbent for decolorization and filtration, and acidizing and filtering to obtain a long-chain binary acid crude product. The long-chain dibasic acid fermentation liquid is a metabolite obtained by fermenting microorganism by alkane, wherein the molecular general formula of the long-chain dibasic acid is C n H 2n-2 O 4 Wherein n is 10-18.
In the invention, the mass-volume ratio of the long-chain dibasic acid crude product to water in the step (1) is 1:1-1:2 (g: mL).
In the invention, the long-chain binary acid crude product in the step (1) is uniformly mixed with water and then heated to 88-97 ℃.
In the invention, the whole extraction process in the step (1) is controlled at 88-97 ℃, and the reaction is carried out for 30-60min under stirring. Standing for 30-60min after extraction is completed, and cutting off lower water phase. Further, a certain amount of dimethyl sulfoxide is added in the extraction process, and the addition amount of the dimethyl sulfoxide accounts for 5-20% of the addition amount of the ether solvent.
In the invention, the addition amount of the alkali in the step (2) is 0.5-1% of the mass of the crude product of the dibasic acid; the alkali is at least one of sodium hydroxide, calcium hydroxide and the like. The mass of the added water is 0.5 to 1 time of the mass of the crude product of the dibasic acid. Adding alkali and water, back mixing for 30-60min, standing for 30-60min, and cutting off the lower water phase.
In the invention, the mass of the added water in the step (3) is 1-2 times of the mass of the crude product of the dibasic acid. Adding water, back mixing for 30-60min, standing for 30-60min, and cutting off the lower water phase.
In the present invention, the temperature of the cooling crystallization in the step (4) is generally not more than 40 ℃ until the dibasic acid is sufficiently crystallized.
In the invention, the filtering adopts a rotary drum, centrifugation or plate frame filtering, and the drying equipment can use a hot air rotary drum and other drying equipment, and the drying temperature is 95-100 ℃.
The invention can obtain single kind long chain diacid product with high purity, and also can obtain mixed long chain diacid product.
Compared with the prior art, the method has the following beneficial effects:
the invention adopts the mixed solvent of the alcohol solvent and the ether solvent as the recrystallization solvent, thereby greatly improving the solubility of the dibasic acid and reducing the use amount of the solvent. Compared with the refining method using monoether solvent, the purity of the obtained product is more than 98.5%, the total nitrogen content is less than 30ppm, and the unit refining yield of the mixed solvent is about 2 times of that of a single solvent on the premise of ensuring the quality of the product.
Detailed Description
The method and effect of the present invention will be further illustrated with reference to examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments. In the invention, the weight percent is the mass fraction.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below were purchased from biochemical reagent stores unless otherwise specified.
In the invention, the total acid content is measured and calculated by an acid-base titration method, the monoacid content is measured and calculated by a gas chromatography peak area normalization method, and the total nitrogen content is detected by a boat sample injection chemiluminescence method. The unit refining yield is calculated according to the product quality obtained by treating crude dibasic acid with 100mL of mixed solvent, and the filter cake after filtration is measured by a dry weight detection method.
Example 1
And heating the dodecadiacid fermentation liquor to 80 ℃, carrying out microfiltration and ultrafiltration, decolorizing and filtering by using active carbon, and filtering after acidification by using sulfuric acid to obtain a dodecadiacid crude product.
100g of crude dodecadiacid is taken, 100mL of water is added, 180mL of propyl ether and 18mL of ethanol are added, and after uniform mixing, the mixture is heated to 88 ℃ for reaction for 60min. Keeping the temperature at 88 ℃ and standing for 30min, and cutting off the lower water phase. 0.5g of solid sodium hydroxide and 100g of water were added and back mixed for 30min, and then left to stand for 30min, and the lower aqueous phase was excised. 100g of water was added, stirred for 30min, then allowed to stand for 30min, and the lower aqueous phase was excised. The solvent phase was cooled to below 40℃for crystallization, filtered and dried at 100℃to give 92.18g of a purified product. The product quality and the refined yield are shown in Table 1.
Example 2
100g of the crude dodecadiacid product which is the same as in example 1 is taken, 125mL of water is added, 200mL of propyl ether and 10mL of ethanol are added, and after uniform mixing, the mixture is heated to 92.5 ℃ for reaction for 60min. Keeping the temperature at 92.5 ℃ and standing for 30min, and cutting off the lower water phase. 0.5g of solid sodium hydroxide and 100g of water were added and back mixed for 30min, and then left to stand for 30min, and the lower aqueous phase was excised. 100g of water was added, stirred for 30min, then allowed to stand for 30min, and the lower aqueous phase was excised. The solvent phase was cooled to below 40℃for crystallization, filtered and dried at 100℃to give 93.22g of a purified product. The product quality and the refined yield are shown in Table 1.
Example 3
100g of the crude dodecadiacid product which is the same as in example 1 is taken, 150mL of water is added, 198mL of propyl ether and 2mL of ethanol are added, and after uniform mixing, the mixture is heated to 97 ℃ for reaction for 60min. Standing at 97deg.C for 30min, and removing lower water phase. 1g of solid sodium hydroxide and 100mL of water were added and mixed back for 30min, and then left to stand for 30min, and the lower aqueous phase was excised. 0.5g of solid sodium hydroxide and 100g of water were added and back mixed for 30min, and then left to stand for 30min, and the lower aqueous phase was excised. 100g of water was added, stirred for 30min, then allowed to stand for 30min, and the lower aqueous phase was excised. The solvent phase was cooled to below 40℃for crystallization, filtered and dried at 100℃to give 90.27g of a purified product. The product quality and the refined yield are shown in Table 1.
Example 4
The procedure is as in example 1, except that instead of propyl ether butyl ether is used. After drying, 91.34g of a purified product was obtained. The product quality and the refined yield are shown in Table 1.
Example 5
The procedure is as in example 1, except that instead of propyl ether, amyl ether is used. 92.88g of a purified product was obtained after drying. The product quality and the refined yield are shown in Table 1.
Example 6
The procedure is as in example 1, except that hexyl ether is used instead of propyl ether. 90.23g of a purified product was obtained after drying. The product quality and the refined yield are shown in Table 1.
Example 7
The procedure is as in example 1, except that n-propanol is used instead of ethanol. After drying, 92.29g of a purified product was obtained. The product quality and the refined yield are shown in Table 1.
Example 8
The procedure is as in example 1, except that n-butanol is used instead of ethanol. After drying, 91.9g of a purified product was obtained. The product quality and the refined yield are shown in Table 1.
Example 9
The procedure is as in example 1, except that the process is used for refining hexadecanoic dibasic acid. After drying, 91.3g of a purified product was obtained. The product quality and the refined yield are shown in Table 1.
Example 10
The difference from example 1 is that: during the extraction, a certain amount of dimethyl sulfoxide is added, and the addition amount of the dimethyl sulfoxide accounts for 5% of the addition amount of the ether solvent. The solvent phase is cooled to below 40 ℃ for crystallization, filtered, the residual solvent is collected, and the filter cake is dried at 100 ℃ to obtain 92.16g of refined product. Solvent loss amount= (total amount of added solvent-remaining amount of solvent after filtration after crystallization completion)/total amount of added solvent×100%. The solvent loss after adding dimethyl sulfoxide is about 23% and the solvent loss without adding dimethyl sulfoxide is more than 30% through detection and calculation.
Comparative example 1
The difference from example 1 is that: the ether solvent was used alone, 500mL of the ether solvent was added to the mixture, and 92.30g of the product was obtained after drying. The product quality and the refined yield are shown in Table 1.
Comparative example 2
The difference from example 1 is that: ethanol alone, 300mL of ethanol was added to obtain 72.45g of the product after drying, in order to refine the product as much as possible. The product quality and the refined yield are shown in Table 1.
Comparative example 3
The difference from example 1 is that: acetic acid alone, 1250mL of acetic acid was added to obtain 91.82g of the product after drying, in order to refine the product as much as possible. The product quality and the refined yield are shown in Table 1.
TABLE 1
As is clear from Table 1, the effect of refining yield per unit of the process of the present invention is better.
Claims (11)
1. A method for refining long-chain dibasic acid, which is characterized by comprising the following steps:
(1) Heating the long-chain binary acid crude product, water and a mixed solvent, extracting, preserving heat, standing and cutting off a lower water phase; the mixed solvent is a mixed solvent of an alcohol solvent and an ether solvent; the volume ratio of the alcohol solvent to the ether solvent is 1:5-1:100; the alcohol solvent is at least one of ethanol, propanol and butanol; the ether solvent is at least one of propyl ether, butyl ether, amyl ether and hexyl ether;
(2) Adding alkali and water, back mixing, standing, and cutting off lower water phase;
(3) Adding water, back mixing, standing, and cutting off lower water phase;
(4) Cooling and crystallizing the solvent phase, filtering and drying to obtain a refined product;
the long-chain dibasic acid is a metabolite obtained by fermenting microorganism with alkane, wherein the molecular formula of the long-chain dibasic acid is C n H 2n-2 O 4 Wherein n is 10-18.
2. The method according to claim 1, characterized in that: in the mixed solvent in the step (1), the volume ratio of the alcohol solvent to the ether solvent is 1:10-1:20.
3. The method according to claim 1, characterized in that: the mass volume ratio of the crude diacid to the mixed solvent in the step (1) is 1:1 to 3 (g: mL).
4. The method according to claim 1, characterized in that: the mass volume ratio of the long-chain dicarboxylic acid crude product to water in the step (1) is 1:1-1:2 (g: mL).
5. The method according to claim 1, characterized in that: uniformly mixing the long-chain binary acid crude product in the step (1) with water, and heating to 88-97 ℃; the whole extraction process is controlled at 88-97 ℃ and stirred for 30-60min; standing for 30-60min after extraction is completed, and cutting off lower water phase.
6. The method according to claim 1, characterized in that: dimethyl sulfoxide is added in the extraction process in the step (1), and the addition amount of the dimethyl sulfoxide accounts for 5-20% of the addition amount of the ether solvent.
7. The method according to claim 1, characterized in that: the addition amount of the alkali in the step (2) is 0.5-1% of the mass of the crude product of the dibasic acid; the alkali is at least one of sodium hydroxide and calcium hydroxide.
8. The method according to claim 1, characterized in that: and (2) adding water with the mass which is 0.5-1 time of the mass of the crude product of the dibasic acid.
9. The method according to claim 1, characterized in that: and (2) adding alkali and water, back mixing for 30-60min, standing for 30-60min, and cutting off the lower water phase.
10. The method according to claim 1, characterized in that: the mass of the added water in the step (3) is 1 to 2 times of the mass of the crude product of the dibasic acid; adding water, back mixing for 30-60min, standing for 30-60min, and cutting off the lower water phase.
11. The method according to claim 1, characterized in that: the temperature of the cooling crystallization in the step (4) is not more than 40 ℃ until the dibasic acid is fully crystallized.
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| CN201911032958.8A CN112724012B (en) | 2019-10-28 | 2019-10-28 | Method for refining long-chain dibasic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| JP2014070031A (en) * | 2012-09-28 | 2014-04-21 | Nippon Shokubai Co Ltd | Method for producing long-chain dicarboxylic acid |
| CN103804173A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Fermentation organic acid refining method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| JP2014070031A (en) * | 2012-09-28 | 2014-04-21 | Nippon Shokubai Co Ltd | Method for producing long-chain dicarboxylic acid |
| CN103804173A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Fermentation organic acid refining method |
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