CN112794799B - Method for reducing solvent evaporation amount in binary acid refining process - Google Patents
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- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 claims description 4
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 claims description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 4
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 claims description 4
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
-
- 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
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
-
- 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
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The invention relates to a method for reducing solvent evaporation capacity in a dibasic acid refining process, which comprises the steps of heating and inactivating fermentation liquor, and obtaining dibasic acid crystal liquid after acidification; mixing the dibasic acid crystal liquid or a filter cake obtained by filtering with an ether solvent, adding dimethyl sulfoxide, and carrying out solvent phase and water phase separation after reaction; solid matters are absorbed and removed; cooling the solvent phase until the binary acid is crystallized and separated out, filtering and drying to obtain a refined product. The dimethyl sulfoxide is added into the long-chain binary acid refining system of the ether solvent, so that the vapor-liquid equilibrium property is changed, the evaporation capacity of the ether solvent is reduced, and the refining cost is reduced.
Description
Technical Field
The invention belongs to the technical field of biochemical engineering, and particularly relates to a method for reducing the evaporation capacity of a solvent in a refining process of producing long-chain dicarboxylic acid by a fermentation method.
Background
The long-chain dicarboxylic acid refers to aliphatic dicarboxylic acid (DCn or DCA for short) with more than 10 carbon atoms in the carbon chain, and 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 spices, 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 the long-chain dibasic acid, the components of the fermentation liquor are complex, the fermentation liquor mainly comprises thalli, protein, macromolecular pigment, inorganic salt and other intermediate metabolites besides the dibasic acid, the process flow for separating the long-chain dibasic acid from the fermentation liquor is complex, and particularly, the polymerization-grade product is prepared by separation and refining, and the ratio of the cost in the production cost is usually higher than 50%.
At present, the refining methods of the dibasic acid mainly comprise a water phase method and a solvent method. The investment of the water phase method is less than that of the solvent method, an organic solvent is not needed, the process is safe, the operation is simple, but the refining effect is poorer than that of the solvent method, the product cannot meet the requirement of polymerization grade, and the corresponding method and process are still in the research and development stage at present. Compared with the water phase method, the product prepared by the solvent method has high purity, good color and luster and uniform crystal granularity, and can be directly used for synthesizing middle and lower-stream products.
CN104418725A discloses a preparation method of a long-chain dicarboxylic acid finished product, 1) a long-chain dicarboxylic acid composition is treated by a solvent method to obtain a long-chain dicarboxylic acid crystal; 2) washing and drying the long-chain dicarboxylic acid crystal obtained in the step 1), heating the long-chain dicarboxylic acid crystal to a molten state under a reduced pressure state, preserving heat, and cooling to obtain a long-chain dicarboxylic acid finished product, wherein the content of a residual solvent in the long-chain dicarboxylic acid finished product is 50-400 ppm; the residual solvent is acetic acid, acetic acid C1-C6 alcohol ester or a mixture thereof; wherein the heating temperature is 135-200 ℃, and the absolute pressure is less than or equal to 0.07 MPa; the long-chain dicarboxylic acid composition is a long-chain dicarboxylic acid crude product, and the long-chain dicarboxylic acid crude product is obtained by pretreating a long-chain dicarboxylic acid fermentation liquid or a long-chain dicarboxylic acid fermentation treatment liquid. The invention refines the dibasic acid by the acetic acid method, which is a method generally adopted by domestic dibasic acid production enterprises at present. However, due to the strong corrosivity of acetic acid, the equipment investment and the distillation dehydration energy consumption for solvent recycling are high, and particularly, the evaporation amount and the single-pass loss amount of the solvent in the refining process are large, so that the cost is increased.
In addition to the acetic acid process, phase transfer extraction processes based on ethereal solvents also have good results, and patent CN102911036A discloses a process for obtaining high purity dicarboxylic acids, comprising: i, heating and inactivating terminated fermentation liquor; II, acidifying to crystallize and separate out dicarboxylic acid, and filtering to obtain a dicarboxylic acid filter cake; III, mixing the dicarboxylic acid filter cake with an ether solvent to dissolve the 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 solid matters; and V, cooling the organic phase obtained in the step IV until 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 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. Compared with an acetic acid method, the ether solvent reduces the cost related to equipment investment and solvent recycling energy consumption, but the using time of the solvent in the refining process is often higher than 70% of the total refining time, the solvent operated for a long time not only increases the evaporation capacity, but also increases the energy consumption of a tail gas recovery system in the process flow, and the cost is increased.
Although the solvent method is the currently preferred purification technology capable of producing products meeting the requirements of polymer grade, the evaporation capacity and the single-pass loss of the solvent are important factors of the cost of the refining process. In actual production, the excessive evaporation capacity of the solvent often causes the sudden increase and paralysis of the pressure of the whole subsequent recovery system, and the solvent is easy to leak, causes pollution to the ambient air, and even leads to the shutdown and maintenance of production enterprises in serious cases, thereby affecting the benefit. Therefore, the tail gas emission can be reduced by reducing the evaporation capacity of the solvent, so that the cost and the pressure of a subsequent recovery system are reduced, the amount of the solvent leaked into the air is reduced, and the method has good economic benefit and environmental benefit.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a method for reducing the evaporation amount of a solvent in a dibasic acid refining process. The dimethyl sulfoxide is added into the long-chain binary acid refining system of the ether solvent, so that the vapor-liquid equilibrium property is changed, the evaporation capacity of the ether solvent is reduced, and the refining cost is reduced.
The method for reducing the solvent evaporation capacity in the refining process of the long-chain dicarboxylic acid comprises the following steps:
(1) heating and inactivating the terminated fermentation liquor, and acidifying to crystallize and separate out the dibasic acid to obtain a dibasic acid crystal liquid;
(2) Mixing the dibasic acid crystal liquid or a filter cake obtained by filtering with an ether solvent, adding dimethyl sulfoxide, and carrying out solvent phase and water phase separation after reaction;
(3) adding an adsorbent into the solvent phase, and filtering to remove solid matters;
(4) cooling the solvent phase until the binary acid is crystallized and separated out, filtering and drying to obtain a refined product.
In the invention, the fermentation liquid for stopping fermentation in the step (1) is a metabolite obtained by fermenting microorganisms by using alkane and the like, wherein the molecular general formula of the contained long-chain dibasic acid is C n H 2n-2 O 4 Wherein n is 10-18, and the dibasic acid can be a single dibasic acid or a mixed dibasic acid.
In the invention, the heating inactivation temperature in the step (1) is generally 75-100 ℃. After the fermentation liquor is heated and inactivated, impurities such as thalli and the like can be filtered and removed, and conventional methods and equipment such as membrane filtration and the like can be adopted for filtering.
In the invention, the pH value of the acidification in the step (1) is 2.0-4.0, and the temperature is 80-100 ℃. The acid used for acidification may be any concentration of H 2 SO 4 、HNO 3 HCl or H 3 PO 4 。
In the present invention, the ether solvent used in the step (2) may be at least one selected from n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, n-pentyl ether, isopentyl ether, and hexyl ether.
In the invention, the weight ratio of the ether solvent in the step (2) to the binary acid dry basis is 3: 1-15: 1, preferably 4: 1-7: 1. The dibasic acid crystal liquid or filter cake and the ether organic solvent are preferably dissolved under heating conditions, wherein the heating temperature is generally 80-150 ℃, preferably 90-120 ℃, specifically determined according to the boiling point of the selected solvent, and is generally lower than the boiling point temperature of the used solvent.
In the invention, the addition amount of the dimethyl sulfoxide in the step (2) accounts for 10-20% of the addition amount of the ether solvent.
In the invention, the adsorbent in the step (3) is active carbon, active clay and the like, the addition amount of the adsorbent is 0.1-20% of the dry weight of the dibasic acid, and the adsorption time is 30-60 min.
In the present invention, the cooling crystallization temperature in the step (4) is usually 10 to 40 ℃ until the dicarboxylic acid is sufficiently crystallized. The filtration adopts a rotary drum, centrifugation or plate-and-frame filtration and the like, the drying equipment can use drying equipment such as a hot air rotary drum and the like, and the drying temperature is 100-105 ℃.
In the method, the solvent phase obtained by filtering in the step (4) can be recycled. Or the recycled solvent is used after recycling treatment, specifically, alkali and water are added into the recycled solvent, the temperature is heated to 80-100 ℃, the water phase is cut after reaction for 1-5h, the water phase is directly used after cooling, and the dosage of fresh reagents is reduced.
Compared with the prior art, the method has the following beneficial effects:
(1) the invention changes the gas-liquid phase equilibrium property by adding dimethyl sulfoxide, thereby reducing the evaporation amount of the ether solvent in the process of refining the dibasic acid, and the solvent volatilization amount is reduced by more than 30 percent compared with the solvent only using the ether solvent under the same condition.
(2) The thermal stability of the dimethyl sulfoxide adopted by the invention is superior to that of most ether solvents, the chemical stability of the dimethyl sulfoxide is similar to that of most ether solvents, the dimethyl sulfoxide can be directly recycled with the ether solvents without being separated independently, and the use amounts of the ether solvents and the dimethyl sulfoxide are reduced.
Detailed Description
The method and effects of the present invention will be further described with reference to the following examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments. In the present invention, wt% is a mass fraction and vt% is a volume fraction.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The test materials used in the following examples were purchased from biochemical reagent stores unless otherwise specified.
In the invention, the total acid content is measured and calculated by adopting an acid-base titration method, the monoacid content is measured and calculated by adopting a gas chromatography peak area normalization method, and the total nitrogen content is detected by adopting a boat sample injection chemiluminescence method. Solvent loss amount = (total added solvent amount-solvent remaining amount after completion of crystallization)/total added solvent amount × 100%.
Example 1
Taking 200mL of the hot zoneC obtained by fermentation of candida 12 H 22 O 4 Fermentation liquor with concentration of 150 g/L. Heating to 90 deg.C, standing to remove residual liquid wax, filtering to remove thallus to obtain C 12 H 22 O 4 Fermenting the clear liquid, heating to 90 ℃, and adjusting the pH value to 3.0 by hydrochloric acid to obtain a dibasic acid crystal liquid.
Mixing the binary acid crystal with n-propyl ether (n-propyl ether and C) 12 H 22 O 4 The weight ratio of dry basis is 6: 1), heating and mixing, adding dimethyl sulfoxide accounting for 10 percent of the volume of the ether solvent until all the dibasic acid crystals are dissolved in the solvent phase (the dissolving temperature is 90 ℃), standing and layering, and then separating the lower aqueous phase. Adding activated carbon adsorbent into the solvent phase, wherein the addition amount of the adsorbent is 5% of the dry basis weight of the dibasic acid, the adsorption time is 60min, and filtering to remove solid matters. Cooling the solvent phase to 20 ℃, filtering and collecting residual solvent after crystallization is finished, and drying a filter cake to obtain the product. The product quality and the loss of ether solvent are shown in Table 1.
Example 2
Taking 200mL of C obtained by fermenting Candida tropicalis 12 H 22 O 4 The fermentation broth with a concentration of 154 g/L. Heating to 75 deg.C, standing to remove residual liquid wax, filtering to remove thallus to obtain C 12 H 22 O 4 Fermenting the clear liquid, heating to 85 ℃, and adjusting the pH value to 3.0 by hydrochloric acid to obtain a dibasic acid crystal liquid.
Mixing the dibasic acid crystal liquid with n-butyl ether (n-butyl ether and C) 12 H 22 O 4 The weight ratio of dry basis is 5: 1), heating and mixing, adding dimethyl sulfoxide accounting for 15 percent of the volume of the ether solvent until all the dibasic acid crystals are dissolved in the solvent phase (the dissolving temperature is 100 ℃), standing and layering, and then separating the lower aqueous phase. Adding an active carbon adsorbent into the solvent phase, wherein the addition amount of the adsorbent is 5 percent of the dry basis weight of the dibasic acid, the adsorption time is 60min, and filtering to remove solid matters. Cooling the solvent phase to 15 ℃, finishing crystallization, filtering and collecting residual solvent, and drying a filter cake to obtain the product. The product quality and the loss of ether solvent are shown in Table 1.
Example 3
Taking 200mL of C obtained by fermenting Candida tropicalis 12 H 22 O 4 Fermentation liquor with concentration of 158 g/L. Heating to 95 deg.C, standing to remove residual liquid wax, filtering to remove thallus to obtain C 12 H 22 O 4 Fermenting the clear liquid, heating to 95 ℃, and adjusting the pH value to 2.0 by hydrochloric acid to obtain a dibasic acid crystal liquid.
Mixing the binary acid crystal liquid with isoamyl ether (isoamyl ether and C) 12 H 22 O 4 Dry basis weight ratio of 4: 1), heating and mixing, adding dimethyl sulfoxide accounting for 20% of the volume of the ether solvent until all the dibasic acid crystals are dissolved in the solvent phase (the dissolving temperature is 120 ℃), standing and layering, and then separating a lower water phase. Adding active carbon adsorbent into the solvent phase, wherein the addition amount of the adsorbent is 10% of the dry basis weight of the dibasic acid, the adsorption time is 30min, and filtering to remove solid matters. Cooling the solvent phase to 10 ℃, finishing crystallization, filtering and collecting residual solvent, and drying a filter cake to obtain the product. The product quality and the loss of ether solvent are shown in Table 1.
Example 4
200mL of 145g/L C was taken 14 H 26 O 4 Heating the fermentation liquor to 85 ℃, filtering by a ceramic microfiltration membrane, and removing thalli and residual liquid wax to obtain a filtrate. Heating to 95 deg.C, adding H to the filtrate 2 SO 4 Adjusting the pH to 4.0 to obtain C 14 H 26 O 4 And (4) crystallizing the solution.
C is to be 14 H 26 O 4 The crystal liquid and isopropyl ether (isopropyl ether and C) 14 H 26 O 4 Mixing according to the dry weight ratio of 7: 1), adding dimethyl sulfoxide accounting for 10% of the volume of the ether solvent until all the dibasic acid crystals are dissolved in the solvent phase (the dissolving temperature is 80 ℃), standing for layering, and then separating out the lower aqueous phase. Adding activated carbon adsorbent into the solvent phase, wherein the addition amount of the adsorbent is 5% of the dry basis weight of the dibasic acid, the adsorption time is 60min, and filtering to remove solid matters. Cooling the solvent phase to 10 ℃, finishing crystallization, filtering and collecting residual solvent, and drying a filter cake to obtain the product. The product quality and the loss of ether solvent are shown in Table 1.
Comparative example 1
The difference from example 1 is that: no dimethyl sulfoxide was added. The product quality and the loss of ether solvent are shown in Table 1.
Comparative example 2
The difference from example 4 is that: no dimethyl sulfoxide was added. The product quality and the loss of ether solvent are shown in Table 1.
TABLE 1
As can be seen from Table 1, the solvent loss of the present invention is only about 20%, whereas the solvent loss without the use of the present invention is higher than 30%.
Claims (9)
1. A method for reducing the evaporation capacity of a solvent in a refining process of long-chain dicarboxylic acid is characterized by comprising the following steps: (1) heating and inactivating the terminated fermentation liquor, and acidifying to crystallize and separate out the dibasic acid to obtain a dibasic acid crystal liquid; the fermentation stopping liquid is a metabolite obtained by fermenting microorganism by utilizing alkane, and the molecular general formula of long-chain dibasic acid contained in the fermentation stopping liquid is C n H 2n-2 O 4 Wherein n is 10-18, and the dibasic acid is a single dibasic acid or a mixed dibasic acid; (2) mixing the dibasic acid crystal liquid or a filter cake obtained by filtering with an ether solvent, adding dimethyl sulfoxide, and carrying out solvent phase and water phase separation after reaction; the ether solvent is at least one of n-propyl ether, isopropyl ether, n-butyl ether, isobutyl ether, n-amyl ether, isoamyl ether and hexyl ether; the weight ratio of the ether solvent to the binary acid dry base is 4: 1-7: 1; the addition amount of the dimethyl sulfoxide accounts for 10-20% of the addition amount of the ether solvent; (3) adding an adsorbent into the solvent phase, and filtering to remove solid matters; (4) cooling the solvent phase until the binary acid is crystallized and separated out, filtering and drying to obtain a refined product.
2. The method of claim 1, wherein: heating and inactivating at 75-100 deg.c; heating to inactivate, filtering to remove thallus, and filtering with membrane.
3. The method of claim 1, wherein: the pH value of the acidification in the step (1) is 2.0-4.0, and the temperature is 80-100 ℃.
4. A method according to claim 1 or 3, characterized in that: step (1) acidification adopts H with any concentration 2 SO 4 、HNO 3 HCl or H 3 PO 4 。
5. The method of claim 1, wherein: the binary acid crystal liquid or filter cake and ether organic solvent are dissolved under the heating condition, and the heating temperature is 80-150 ℃.
6. The method of claim 5, wherein: the heating temperature is 90-120 ℃.
7. The method of claim 1, wherein: the adsorbent in the step (3) is activated carbon or/and activated clay, the addition amount of the adsorbent is 0.1-20% of the dry basis weight of the dibasic acid, and the adsorption time is 30-60 min.
8. The method of claim 1, wherein: the cooling crystallization temperature in the step (4) is 10-40 ℃; the filtration is carried out by adopting a rotary drum, centrifugation or plate-and-frame filtration, and the drying temperature is 100-105 ℃.
9. The method of claim 1, wherein: filtering the solvent phase obtained in the step (4) for recycling; or the recycled solvent is used after recycling treatment, specifically, alkali and water are added into the recycled solvent, the temperature is heated to 80-100 ℃, the water phase is cut after reaction for 1-5h, the water phase is directly used after cooling, and the dosage of fresh reagents is reduced.
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| WO2001004337A1 (en) * | 1999-07-09 | 2001-01-18 | Cognis Corporation | Separation and purification of carboxylic acids from fermentation broths |
| 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 |
| CN104592004A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Long chain organic acid refining method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2001004337A1 (en) * | 1999-07-09 | 2001-01-18 | Cognis Corporation | Separation and purification of carboxylic acids from fermentation broths |
| 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 |
| CN104592004A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Long chain organic acid refining method |
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