CN113493378A - Long-chain dicarboxylic acid product and refining process thereof - Google Patents
Long-chain dicarboxylic acid product and refining process thereof Download PDFInfo
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- CN113493378A CN113493378A CN202010250414.5A CN202010250414A CN113493378A CN 113493378 A CN113493378 A CN 113493378A CN 202010250414 A CN202010250414 A CN 202010250414A CN 113493378 A CN113493378 A CN 113493378A
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000007670 refining Methods 0.000 title claims abstract description 11
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- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
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- 239000004831 Hot glue Substances 0.000 claims abstract description 25
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- 238000006243 chemical reaction Methods 0.000 claims description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 5
- 238000002834 transmittance Methods 0.000 claims description 5
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 claims description 4
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- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 claims description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 claims description 4
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 230000007774 longterm Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
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- 229910052799 carbon Inorganic materials 0.000 claims description 2
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- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 claims description 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 241001052560 Thallis Species 0.000 description 1
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- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
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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
-
- 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
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- 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
- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
- C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a long-chain dicarboxylic acid product and a refining process thereof, wherein the refining process comprises the following steps: heating and melting a mixture containing long-chain dibasic acid, and then carrying out first distillation to obtain a first distillation product; and mixing the first distillation product with an oxidant, reacting at the temperature of no higher than 240 ℃, and further carrying out multiple times of distillation treatment such as second distillation, third distillation treatment and the like on the obtained oxidation product to purify the long-chain dicarboxylic acid. The process does not need to consume a large amount of acid, alkali and solvent, and does not generate a large amount of waste liquid. Impurities which are difficult to remove by conventional evaporation techniques are removed by oxidizing the impurities by oxidation treatment to change the boiling point or volatility of the impurities in combination with multi-stage distillation. The long-chain dicarboxylic acid product obtained by the method has the advantages of good quality, high product yield, low ash content and low impurity content. The long-chain dicarboxylic acid product has wide application prospect, and particularly, the hot melt adhesive product prepared when the long-chain dicarboxylic acid product is applied to the hot melt adhesive has good quality.
Description
Technical Field
The invention relates to a long-chain dibasic acid and a refining process thereof.
Background
Long chain dicarboxylic acids (LCDA, abbreviated as DCn, n is 10-18) are important organic intermediates, and are widely used in the fields of chemical industry, light industry, pesticides, medicines, new materials and the like. The extraction and purification technology of the long-chain dibasic acid also influences the cost of the dibasic acid in final industrial production, so that the development of the simple and efficient extraction and purification technology of the dibasic acid can promote the popularization and application of the fermentation process technology.
In the existing scheme for extracting the long-chain dibasic acid, a mixture containing the long-chain dibasic acid is dissolved by using alkali and then acidified to separate out the long-chain dibasic acid, so that the long-chain dibasic acid is usually dissolved by using the alkali and precipitated by using the acid for multiple times, a large amount of alkali and acid are consumed, on one hand, the environment is greatly influenced, and the crystallization mother liquor is difficult to post-treat due to high salt content. On the other hand, the extraction method has poor pigment removal effect, and the obtained product has dark color and high impurity content.
However, in the method for extracting the long-chain dicarboxylic acid by using repeated solvent recrystallization, impurities are removed by using solubility difference, some impurities have similar solubility with the long-chain dicarboxylic acid, and the solubility difference between different long-chain dicarboxylic acids, monoacids and unsaturated acids is small, so that even if the long-chain dicarboxylic acid is purified by repeated recrystallization, the impurities with similar solubility are difficult to remove fundamentally, and some long-chain dicarboxylic acids are still dissolved in the solvent after recrystallization, so that yield loss is caused, and the production cost is high, and the market acceptance is difficult. In addition, it is difficult to crystallize a raw material containing many impurities, and it is difficult to purify such a raw material. In addition, the organic solvent is inflammable, volatile and toxic, a fireproof, explosion-proof and toxic-proof device is required during post-treatment, the organic solvent is expensive, volatile and easy to lose, and the cost is high.
Disclosure of Invention
The invention aims to provide a long-chain dicarboxylic acid product.
The total acid content of the long-chain dicarboxylic acid product is more than or equal to 97%, and further more than or equal to 97.5%, such as more than 98.0%, more than 98.2% and more than 98.5%.
The light transmittance of the long-chain dicarboxylic acid product is more than or equal to 80%, and further more than or equal to 85%, for example, more than 87%, more than 90%, more than 91%, and more than 94%.
The long-chain dicarboxylic acid product has an ash content of 30ppm or less, further 25ppm or less, for example, 20ppm or less, 17ppm or less, 15ppm or less, and 13ppm or less.
The nitrogen content of the long-chain dicarboxylic acid product is less than or equal to 50ppm, and further less than or equal to 40ppm, such as less than 35ppm, less than 30ppm, and less than 28 ppm.
The content of unsaturated dibasic acid in the long-chain dibasic acid product is less than or equal to 0.5 percent, and further less than or equal to 0.35 percent, such as less than 0.3 percent and less than 0.25 percent.
The saturated long-chain dicarboxylic acid content of the long-chain dicarboxylic acid product is more than or equal to 90%, further more than or equal to 91%, further more than or equal to 93%, further more than or equal to 94%, for example, more than 95% and more than 96%.
Further, the long-chain dicarboxylic acid product is applied to the hot melt adhesive.
Further, the long-chain dicarboxylic acid product is used for preparing the hot melt adhesive.
Further, the long-chain dibasic acid is prepared by any one of the following methods.
The other purpose of the invention is to provide a refining process of long-chain dibasic acid, which is used for extracting and refining the long-chain dibasic acid from a mixture containing the long-chain dibasic acid.
The refining process comprises the following steps:
(1) heating and melting a mixture containing long-chain dibasic acid, performing first distillation, and collecting distillate to obtain a first distillation product;
(2) and mixing the first distillation product with an oxidant, and reacting at the temperature of not higher than 240 ℃ to obtain an oxidation product.
According to some embodiments of the invention, the mixture comprising long chain dibasic acids includes, but is not limited to: the long-chain dicarboxylic acid crude product, residues after most of the solvent is recovered from the recrystallization mother liquor of the long-chain dicarboxylic acid crude product, and long-chain dicarboxylic acid precipitates accumulated in a long-term long-chain dicarboxylic acid sewage treatment workshop.
According to some embodiments of the invention, the long chain dibasic acid is biologically produced. Obtained by using alkane, fatty acid and derivatives thereof as substrates and utilizing a microbial fermentation method. The microorganism can oxidize the terminal methyl of alkane, fatty acid and fatty acid derivative into carboxyl to generate long-chain dibasic acid.
According to some embodiments of the invention, the long chain dicarboxylic acid is a saturated long chain dicarboxylic acid.
According to some embodiments of the invention, the mixture comprising long chain dibasic acids comprises saturated long chain dibasic acids.
Further, the number of carbon atoms of the saturated long-chain dibasic acid is 10-18. Further, the saturated long-chain dibasic acid has a carboxyl group at both ends. Further, the molecular chain of the saturated long-chain dibasic acid is a straight chain, and the chemical formula of the molecular chain is HOOC (CH)2) mCOOH, m is an integer selected from 8-16. DCn is used for short, and n is an integer selected from 10-18. For example, DC10 represents a dodecanedioic acid, and DC18 represents an octadecadioic acid.
Further, the saturated long-chain dibasic acid is selected from one or a combination of more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid.
According to some embodiments of the invention, the mixture comprising long-chain dibasic acids contains saturated long-chain dibasic acids in an amount of 10 to 98 wt%, further 10 to 90 wt%, such as 20 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 70 wt%, 75 wt%, 80 wt%.
According to some embodiments of the invention, the mixture comprising the long-chain dicarboxylic acid comprises an unsaturated dicarboxylic acid in an amount of 0.1 to 40 wt%, further 1 to 30%, such as 5%, 8%, 10%, 15%, 20%, 25%.
According to some embodiments of the invention, the oxidizing agent comprises a neutral oxidizing agent, an acidic oxidizing agent, a basic oxidizing agent.
According to some embodiments of the invention, the oxidizing agent comprises potassium permanganate, ozone, air, 60 wt% or more nitric acid.
According to some embodiments of the invention, the oxidation product is second distilled, a distillate of the second distillation is collected to obtain a second distillation product, and then the second distillation product is subjected to a third distillation, a distillate of the third distillation is removed, and a remainder of the third distillation is collected to obtain a third distillation product.
According to some embodiments of the present invention, the oxidation product is subjected to a third distillation without being subjected to a second distillation treatment, a distillate of the third distillation is removed, and a distillation residue is collected to obtain a third distillation product.
According to some embodiments of the invention, the third distillation product is subjected to a fourth distillation, and the distillate is collected to yield a fourth distillation product.
According to some embodiments of the present invention, the fourth distillation product may be subjected to N additional distillations in order to further purify the product. N is more than or equal to 1. Specifically, the distillate after each distillation is used as the raw material for the next distillation until the distillation is completed for N times, and the distillate after the distillation for N times is collected to obtain the 4+ N distillation product. In any one distillation process, the vacuum degree is less than or equal to 100pa, the temperature is 220-250 ℃, and further 180-280 ℃.
According to some embodiments of the invention, the degree of vacuum of the first distillation in step (1) is 100pa or less, further 80pa or less, such as 65pa or less, 50pa or less, 30pa or less, and 15pa or less. The temperature of the first distillation is 180 to 280 ℃, further 180 to 260 ℃, such as 200 ℃, 210 ℃,220 ℃, 230 ℃,240 ℃, 250 ℃.
Further, in the step (2), the content of the oxidizing agent is converted to 100 wt%, and the amount of the oxidizing agent of 100 wt% used per 100 g of the first distillation product is 1 to 20g, and further 1 to 10g, for example, 3g, 4g, 5g, 6g, 7g, 8g, 9g, 12g, 15g, 17 g.
When the oxidizing agent is air, the content of the oxidizing agent is converted to 100% by weight, which means that the content of oxygen in air is converted to 100% by weight.
According to some embodiments of the present invention, the temperature of the (oxidation) reaction in step (2) is 140 to 240 ℃, further 160 to 220 ℃, such as 175 ℃,180 ℃, 193 ℃, 195 ℃. The (oxidation) reaction in the step (2) is carried out for 0.5-6 h, further 0.5-3 h, such as 1h, 1.5h, 2h, 2.5h, 3.5h, and 4 h.
According to some embodiments of the invention, the degree of vacuum of the second distillation of step (2) is 100Pa or less, further 80Pa or less, such as 65Pa or less, 50Pa or less, 30Pa or less, and 15Pa or less. The temperature of the second distillation is 180 to 280 ℃, and further 180 to 260 ℃, for example, 200 ℃,220 ℃,240 ℃.
According to some embodiments of the invention, the vacuum of the third distillation is 100pa or less, further 80pa or less, such as 65pa or less, 50pa or less, 30pa or less, 15pa or less. The temperature of the third distillation is 150-240 deg.C, further 150-220 deg.C, such as 170 deg.C, 180 deg.C, 190 deg.C, 200 deg.C.
According to some embodiments of the invention, the third distillation may be a distillation with a vacuum of 100pa or less, further 80pa or less, such as 65pa or less, 50pa or less, 30pa or less, 15pa or less; the number of the plates is 2 to 24, further 3 to 12, for example, 4,5, 6. The temperature of the tower kettle is 150-230 ℃, and further 150-220 ℃, such as 170 ℃,180 ℃,190 ℃,200 ℃ and 210 ℃. The temperature at the top of the tower is 120-195 ℃, and further 120-190 ℃, such as 140 ℃,150 ℃, 160 ℃, 170 ℃ and 175 ℃.
According to some embodiments of the invention, the fourth distillation has a vacuum of 100pa or less, further 80pa or less, such as 65pa, 50pa or less, 30pa or less, 15pa or less. The temperature of the fourth distillation is 180-280 ℃, further 180-260 ℃, such as 200 ℃, 205 ℃, 215 ℃, 225 ℃,240 ℃ and 250 ℃.
According to some embodiments of the invention, the fourth distillation may be a distillation with a vacuum of 100pa or less, further 80pa or less, such as 65pa or less, 50pa or less, 30pa or less, 15pa or less. The number of plates is 3 to 24, further 3 to 12, for example 4,5, 6. The temperature of the tower kettle is 200-280 ℃, and further 200-260 ℃, such as 210 ℃,220 ℃, 225 ℃ and 230 ℃; the temperature at the top of the tower is 180-230 ℃, and further 180-225 ℃, such as 190 ℃, 195 ℃,200 ℃, 205 ℃ and 210 ℃.
According to some embodiments of the invention, the remainder of the second distillation and the remainder of the fourth distillation are returned to the first distillation for recycling.
The distillate in the distillation or rectification process is low-boiling-point substances, and the remainder of the distillation or rectification is high-boiling-point substances.
The first distillation is used to remove most of the high boilers and salts. The obtained fraction contains saturated long-chain dicarboxylic acid as main component, and also contains small amount of unsaturated acid and low-carbon chain acid. While most of the high boiling point impurities such as inorganic salts, pigments, proteins, saccharides, etc. remain in the distillation residue, but a small amount of impurities such as pigments, etc. may still be present in the distillate. Meanwhile, the solubility of some impurities in the distillate is close to that of saturated long-chain dibasic acid, so that the impurities cannot be removed by recrystallization or acidification crystallization after alkali dissolution.
The oxidant is introduced to oxidize the easily oxidized impurities, so that the boiling point or the volatility of the impurities is changed, and the saturated long-chain dibasic acid is difficult to oxidize. For example, an acid or non-acid impurity containing an unsaturated bond is oxidized to break the double bond.
And removing the residual oxidant after oxidation by using second distillation. And further removing high boiling point substances, including pigments, high boiling point substances generated after oxidation reaction and the like.
Further, low boiling point substances generated after the oxidation reaction, such as low carbon chain compounds formed by breaking molecular chains after the oxidation reaction, and unsaturated acids and monoacids impurities can be removed by using the third distillation. Further, the fourth distillation can be used for further removing high boiling point substances and purifying the product.
According to some embodiments of the invention, the refining process may further comprise a step of a decolorization treatment. The product quality can be further improved by decolorization.
Specifically, the distillation product at any time is contacted with a decoloring agent to be subjected to decoloring treatment. For example: and (4) contacting the fourth distillation product with a decoloring agent for decoloring. The decoloring treatment may be, for example: passing the material to be decolorized through a decolorizing agent, and collecting the effluent as a decolorized product. For example: the material to be decolorized is passed through the decolorizing agent in the molten state. And removing the decolorizing agent after the decolorizing treatment to obtain the decolorized material.
The decompression distillation product is decolored in a molten state, so that the energy consumption of heating can be reduced, and the process flow is simplified.
According to some embodiments of the invention, the decolorizing agent is used in an amount of 3 to 40 wt%, further 5 to 30 wt%, such as 7 wt%, 20 wt%, 25 wt% of the material to be decolorized. The decolorizing temperature is 130-180 deg.C, further 140-160 deg.C, such as 170 deg.C. The decolorization time is 3-120 min, and further 5-60 min, such as 10min, 15min, 20min, 45min, 75min, and 100 min.
According to some embodiments of the invention, the decolorizing agent includes, but is not limited to, activated carbon, activated clay, diatomaceous earth, bentonite.
The invention has the technical effects that:
1. the process is different from the traditional process of acidifying and precipitating after long-chain dibasic acid is dissolved by adding alkali, so that a large amount of acid and alkali are not required to be consumed, and the process is different from a solvent recrystallization purification method and requires a solvent to be consumed, so that a large amount of waste liquid is not generated.
2. Impurities which are difficult to remove by the conventional evaporation technology are removed by adopting an oxidation process combined with multi-stage distillation.
3. The long-chain dicarboxylic acid has good product quality, high product yield, low impurity content and wide application prospect, and particularly, the hot melt adhesive prepared by the method is good in quality when being applied to hot melt adhesives.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Mixtures comprising long chain diacids include, but are not limited to: the long-chain dicarboxylic acid crude product, residues after most of the solvent is recovered from the recrystallization mother liquor of the long-chain dicarboxylic acid crude product, and long-chain dicarboxylic acid precipitates accumulated in a long-term long-chain dicarboxylic acid sewage treatment workshop.
For example: extracting DCn crude product from DCn fermentation liquor:
heating any one of fermentation liquors of DC 10-DC 18 to 60-100 ℃, removing thalli by centrifugation or membrane filtration, adding activated carbon with the volume of 0.05-5 wt% of that of the clear liquor into the obtained clear liquor for decolorization, filtering to remove the activated carbon, heating the decolorized liquor to 50-100 ℃, adjusting the pH to 2-5 for acidification and crystallization, and carrying out solid-liquid separation to obtain crude products of DC 10-DC 18.
The long-chain dibasic acid fermentation liquor is obtained by taking alkane, fatty acid and derivatives thereof as substrates and utilizing a microbial fermentation method. The microorganism can oxidize the terminal methyl of alkane, fatty acid and fatty acid derivative into carboxyl to generate long-chain dibasic acid. The microorganism may be, for example, candida.
The recrystallization refining process of the DC 10-DC 18 crude product comprises the following steps:
recrystallizing the crude product of DC 10-DC 18 by using more than 90 wt% of acetic acid solution, and filtering crystals to obtain DC 10-DC 18 crystallized products and acetic acid mother liquor. Acetic acid in the acetic acid mother liquor is recycled after being recovered by a rectifying tower, and tower bottom materials (namely residues after the acetic acid mother liquor is rectified and recovered) are a mixture containing long-chain dibasic acid.
After recrystallization, most of impurities (including pigments, sugars, inorganic salts, cell tissues of fermentation microorganisms, proteins and the like) and most of heteropolyacids (including saturated long-chain dibasic acids which are generated as byproducts in the fermentation process and have unequal carbon chain lengths with fermentation substrates, some short-chain saturated dibasic acids, unsaturated dibasic acids and the like) in the long-chain dibasic acid crude product are dissolved in a solvent so as to be separated from main long-chain dibasic acids (namely, long-chain dibasic acid objects refined in the recrystallization process, namely, target long-chain dibasic acids for short) in the long-chain dibasic acid crude product. In the recrystallization process, the crude long-chain dicarboxylic acid is dissolved in the solvent, and then the solution is cooled (preferably, the temperature is controlled below 50 ℃ but higher than 20 ℃) to be precipitated, so that part of the target long-chain dicarboxylic acid is also dissolved in the mother solution of the solvent. Recrystallizing the crude long-chain dicarboxylic acid in a solvent, and filtering the crystals to obtain a remainder as a solvent mother liquor. The mixture containing the long-chain dibasic acid in the present invention may be, for example, a solvent mother liquor. Or the remainder of the solvent mother liquor after recovering most of the solvent, for example, the bottom material of the column after recovering the solvent by using a rectifying column. Bottoms often appear brown due to the presence of pigments; in addition to pigments, they contain impurities such as inorganic salts, cell tissues of the fermenting microorganisms, proteins, etc., which result in melting points often lower than those of pure long-chain dibasic acids.
The detection method of the long-chain dicarboxylic acid product index in the embodiment comprises the following steps:
1. and (3) ash content detection: and (3) burning a sample to be detected in a crucible, then burning in a muffle furnace at 700-800 ℃ for 2 hours, cooling to constant weight, measuring the weight, and calculating to obtain the percentage weight.
2. And (3) nitrogen content detection: kjeldahl method.
3. And (3) detecting the light transmittance: the light transmittance at 440nm of a 25% solution of dimethyl sulfoxide in the sample was measured using a spectrophotometer.
Example 1
500kg of tower bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating for melting, distilling at 250 ℃ under the vacuum degree of 10pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 470kg of first distillation products.
And heating the first distillation product to 180 ℃, and reacting the first distillation product with 20kg of potassium permanganate powder at 180 ℃ for 2h under the condition of stirring under normal pressure to obtain an oxidation product. The oxidation product was subjected to second distillation at a vacuum degree of 10pa and a temperature of 250 ℃ until no distillate was produced as a distillation end point, and the distillate was collected to obtain 435kg of a second distillation product.
And carrying out third distillation on the second distillation product under the vacuum degree of 10pa at 215 ℃, collecting distillate, and obtaining 422kg of third distillation product as the remainder of the third distillation product.
And (3) carrying out fourth distillation on the third distillation product at the temperature of 240 ℃ and the vacuum degree of 8pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 380kg of fourth distillation product, namely the obtained product.
And returning the remainder of the second distillation and the remainder of the fourth distillation to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 2
500kg of tower bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating for melting, distilling at 250 ℃ under the vacuum degree of 10pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 470kg of first distillation products.
Heating the first distillation product to 150 ℃, and reacting the first distillation product with 51kg of ozone at 150 ℃ for 2h under the condition of stirring at normal pressure to obtain an oxidation product, wherein the ozone is introduced at the speed of 200L/min. And carrying out second distillation on the oxidation product at the vacuum degree of 10pa and the temperature of 250 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 438kg of second distillation product.
And carrying out third distillation on the second distillation product under the condition of vacuum degree of 10pa and 215 ℃, collecting distillate, and obtaining 425kg of third distillation product as the remainder.
And performing fourth distillation on the third distillation product at the temperature of 240 ℃ and the vacuum degree of 8pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 384kg of the fourth distillation product as the obtained product.
And returning the remainder of the second distillation and the remainder of the fourth distillation to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 3
500kg of tower bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating to melt, distilling at 250 ℃ under the vacuum degree of 15pa until no fraction is produced as a distillation end point, and collecting the distillate to obtain 468kg of first distillation products.
And heating the first distillation product to 190 ℃, and reacting the first distillation product with 20kg of nitric acid with the mass fraction of 95% at 190 ℃ for 2h under the condition of stirring at normal pressure to obtain an oxidation product. And carrying out second distillation on the oxidation product at the vacuum degree of 10pa and the temperature of 250 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 445kg of a second distillation product.
And carrying out third distillation on the second distillation product under the condition of vacuum degree of 10pa and 215 ℃, collecting distillate, and obtaining 425kg of third distillation product as the remainder.
And (3) carrying out fourth distillation on the third distillation product at the temperature of 240 ℃ and the vacuum degree of 8pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 382kg of a fourth distillation product, namely the obtained product.
And returning the remainder of the second distillation and the remainder of the fourth distillation to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 4
500kg of tower bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating to be molten, distilling at 240 ℃ under the vacuum degree of 8pa until no fraction is produced as a distillation end point, and collecting the distillate to obtain 466kg of first distillation products.
The first distillation product was heated to 180 ℃ and reacted with 77.58kg of air at 180 ℃ for 2h under stirring at atmospheric pressure to give an oxidized product, wherein the air was introduced at a rate of 500L/min. And carrying out second distillation on the oxidation product at the vacuum degree of 10pa and the temperature of 250 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 433kg of second distillation product.
And carrying out third distillation on the second distillation product under the vacuum degree of 10pa at 216 ℃, collecting distillate, and obtaining 420kg of third distillation product as the remainder.
And (3) carrying out fourth distillation on the third distillation product at the temperature of 240 ℃ and the vacuum degree of 8pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 377kg of a fourth distillation product, namely the obtained product.
And returning the remainder of the second distillation and the remainder of the fourth distillation to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 5
500kg of tower bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating to be molten, distilling at 240 ℃ under the vacuum degree of 8pa until no fraction is produced as a distillation end point, and collecting the distillate to obtain 466kg of first distillation products.
The first distillation product was heated to 200 ℃ and reacted with 93.096kg of air at 200 ℃ for 2h under stirring at atmospheric pressure to give an oxidized product, the rate of introduction of air being 600L/min. And carrying out second distillation on the oxidation product at the vacuum degree of 8pa and the temperature of 240 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 437kg of a second distillation product.
And carrying out third distillation on the second distillation product under the vacuum degree of 8pa at 216 ℃, collecting distillate, and obtaining 420kg of third distillation product as the remainder.
And (3) carrying out fourth distillation on the third distillation product at the temperature of 240 ℃ and the vacuum degree of 5pa until no fraction is generated as a distillation end point, collecting the distillate to obtain 378kg of the fourth distillation product, and contacting the fourth distillation product with activated carbon for decolorization at the temperature of 150 ℃ for 30min, wherein the use amount of the activated carbon accounts for 8% of the weight of the fourth distillation product. The activated carbon was removed and the decolorized product was collected to yield 359 kg.
And returning the remainder of the second distillation and the remainder of the fourth distillation to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 6
500kg of column bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating to melt, distilling at 250 ℃ under the vacuum degree of 5pa until no fraction is produced as a distillation end point, and collecting distillate to obtain 475kg of a first distillation product.
The first distillation product was heated to 200 ℃ and reacted with 155.16kg of air at 200 ℃ for 2h under stirring at atmospheric pressure to give an oxidized product, wherein the rate of air introduction was 1000L/min. And carrying out second distillation on the oxidation product at the vacuum degree of 5pa and the temperature of 250 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 442kg of second distillation product.
And performing third rectification on the second distillation product, wherein the vacuum degree is 8pa, the tower bottom temperature is 216 ℃, the tower top temperature is 182 ℃, the number of tower plates of the rectification tower is 8, collecting distillate, and obtaining 427kg of a third rectification product as the remainder.
And performing fourth rectification on the third rectification product, wherein the vacuum degree is 5pa, the temperature of the tower bottom is 240 ℃, the temperature of the tower top is 215 ℃, the number of plates of the rectification tower is 8, and when no fraction is generated, the rectification end point is reached, collecting the distillate to obtain 383kg of a fourth rectification product, namely the obtained product.
And returning the residues of the second distillation and the fourth rectification to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 7
500kg of column bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating to melt, distilling at 250 ℃ under the vacuum degree of 5pa until no fraction is produced as a distillation end point, and collecting distillate to obtain 475kg of a first distillation product.
The first distillation product was heated to 200 ℃ and reacted with 155.16kg of air at 200 ℃ for 2h under stirring at atmospheric pressure to give an oxidized product, wherein the rate of air introduction was 1000L/min. And carrying out second distillation on the oxidation product at the vacuum degree of 5pa and the temperature of 250 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 442kg of second distillation product.
And performing third rectification on the second distillation product, wherein the vacuum degree is 8pa, the tower bottom temperature is 216 ℃, the tower top temperature is 182 ℃, the number of tower plates of the rectification tower is 8, collecting distillate, and obtaining 427kg of a third rectification product as the remainder.
And performing fourth rectification on the third rectification product, wherein the vacuum degree is 5pa, the temperature of a tower kettle is 240 ℃, the temperature of a tower top is 215 ℃, the number of tower plates of a rectification tower is 8, no fraction is generated as the rectification end point, collecting distillate to obtain 383kg of the fourth rectification product, and contacting the fourth rectification product with activated carbon for decolorization, wherein the decolorization temperature is 150 ℃, the decolorization time is 30min, and the using amount of the activated carbon accounts for 10% of the weight of the fourth rectification product. Removing the active carbon, and collecting the product after decoloration to obtain 363kg of the product.
And returning the residues of the second distillation and the fourth rectification to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 8
500kg of tower bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating to melt, distilling at 235 ℃ under the vacuum degree of 5pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 461kg of a first distillation product.
The first distillation product was heated to 190 ℃ and reacted with 155.16kg of air at 200 ℃ for 2h under stirring at atmospheric pressure to give an oxidized product, wherein the rate of air introduction was 1000L/min. And (3) carrying out second distillation on the oxidation product at the vacuum degree of 8pa and the temperature of 255 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 426kg of second distillation product which is a long-chain dicarboxylic acid product.
Example 9
500kg of column bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating to melt, distilling at 250 ℃ under the vacuum degree of 5pa until no fraction is produced as a distillation end point, and collecting distillate to obtain 475kg of a first distillation product.
The first distillation product was heated to 200 ℃ and reacted with 155.16kg of air at 200 ℃ for 2h under stirring at atmospheric pressure to give an oxidized product, wherein the rate of air introduction was 1000L/min.
And (3) directly performing third rectification on the oxidation product, wherein the vacuum degree is 8pa, the temperature of the tower bottom is 216 ℃, the temperature of the tower top is 182 ℃, the number of tower plates of the rectification tower is 8, collecting distillate, and obtaining 436kg of third rectification product as the remainder.
And carrying out fourth distillation on the third distillation product at the vacuum degree of 8pa and the temperature of 240 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 387kg of a fourth distillation product, namely the obtained product.
Wherein, the remainder of the fourth rectification is returned to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Example 10
850kg of column bottoms (wherein the content of DC 10-DC 18 is 53 wt%, and the content of unsaturated dibasic acid is 18 wt%) were heated to be molten, and then distilled at 250 ℃ under the vacuum degree of 5pa until no distillate was produced as a distillation end point, and the distillate was collected to obtain 670kg of a first distillation product.
The first distillation product was heated to 200 ℃ and reacted with 310.32kg of air at 200 ℃ for 2h under stirring at atmospheric pressure to give an oxidized product, wherein the rate of air introduction was 2000L/min. And carrying out second distillation on the oxidation product at the vacuum degree of 5pa and the temperature of 250 ℃ until no fraction is generated as a distillation end point, and collecting the distillate to obtain 640kg of a second distillation product.
And performing third rectification on the second distillation product, wherein the vacuum degree is 8pa, the tower bottom temperature is 216 ℃, the tower top temperature is 182 ℃, the number of tower plates of the rectification tower is 8, collecting distillate, and obtaining 438kg of third rectification product as the remainder.
And performing fourth rectification on the third rectification product, wherein the vacuum degree is 5pa, the temperature of the tower bottom is 240 ℃, the temperature of the tower top is 215 ℃, the number of tower plates of the rectification tower is 8, and 395kg of fourth rectification product is obtained as the obtained product when no fraction is generated as the rectification end point, and collecting the distillate.
And returning the residues of the second distillation and the fourth rectification to the first distillation for recycling.
The product was tested and the results are shown in table 1.
Comparative example 1
500kg of tower bottom materials (wherein the content of DC 10-DC 18 is 82 wt%, the content of unsaturated dibasic acid is 3 wt%), heating for melting, distilling at 250 ℃ under the vacuum degree of 10pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 470kg of first distillation products.
The first distillation product was subjected to second distillation under a vacuum of 10pa at a temperature of 250 ℃ until no distillate was produced as a distillation end point, and the distillate was collected to obtain 435kg of a second distillation product.
And carrying out third distillation on the second distillation product under the conditions that the vacuum degree is 10pa and the temperature is 215 ℃, collecting distillate, and obtaining 422kg of third distillation product, wherein the residual high-boiling residues are the third distillation product.
And (3) carrying out fourth distillation on the third distillation product at the temperature of 240 ℃ and the vacuum degree of 8pa until no fraction is generated as a distillation end point, and collecting the distillate to obtain 380kg of fourth distillation product, namely the obtained product.
And returning the remainder of the second distillation and the remainder of the fourth distillation to the first distillation for recycling.
Comparative example 2
And (3) adding 500kg of tower bottom material (wherein the content of DC 10-DC 18 is 82%, and the content of unsaturated dibasic acid is 3 wt%) into a melting tank, melting at 180 ℃ for 1 hour, pumping the material into a wiped film evaporator by using a pump after melting, wherein the material temperature during wiped film evaporation is 176 ℃ and the vacuum degree is 500 pa.
And (3) carrying out short-path distillation on the material after removing the light components, wherein the temperatures of a hot surface and a cold surface of a short-path distillation device are 222-230 ℃ and 134-143 ℃, the vacuum degree is 15-19 pa, the feeding temperature is 180 ℃, and the time is 1 hour. 415kg of long-chain dicarboxylic acid product is obtained.
Comparative example 3
850kg of tower bottom material (wherein the content of DC 10-DC 18 is 53%, the content of unsaturated dibasic acid is 18 wt%) is taken, 1700kg of acetic acid solution with the mass fraction of 95% is added, after the acetic acid solution is dissolved at 95 ℃, 50kg of activated carbon is added, the stirring is carried out for 30min, and then the activated carbon is removed by filtering. And (3) cooling the obtained clarified liquid, wherein the cooling rate is not more than 3 ℃/h, keeping the temperature for 1h after the clarified liquid is cooled until crystals appear, then cooling the clarified liquid to the end temperature of 25 ℃, filtering, washing a filter cake by using 70kg of acetic acid solution with the mass fraction of 95%, then washing by using 700kg of water, and then drying at 80 ℃.
Filtration was found to be difficult during filtration due to the viscous material. The product obtained by drying is yellow, and the yield of the long-chain dicarboxylic acid product is 41%.
Table 1: test result table of long chain dicarboxylic acid product
Application example
The long-chain dicarboxylic acid product is used for preparing the hot melt adhesive, and the preparation process comprises the following steps:
(1) 260g of pentamethylene diamine, 200g of adipic acid, 322g of long-chain dibasic acid, 65g of isophthalic acid, 250g of caprolactam and water were uniformly mixed under a nitrogen atmosphere to prepare an 80 wt.% polyamide salt solution, and the pH value was 7.89 when the concentration of the polyamide salt solution was 10 wt.%.
(2) And (2) filtering the salt solution of the polyamide obtained in the step (1), heating, raising the pressure in the reaction system to 1.7Mpa, exhausting, maintaining the pressure, keeping the temperature of the reaction system at 244 ℃ after the pressure maintaining is finished, reducing the pressure in the reaction system to 0.01Mpa (gauge pressure) after the pressure reducing is finished, keeping for 20min, keeping the temperature of the reaction system at 264 ℃ after the pressure reducing is finished, vacuumizing to be kept at-0.09 Mpa, keeping the vacuum time for 22min, and keeping the temperature after the vacuum at 269 ℃, thus obtaining the melt of the polyamide hot melt adhesive.
(3) Melting and discharging, and granulating by using water; the water temperature of the cooling water is 20 ℃, and the cooling time is 35min, thus obtaining the polyamide hot melt adhesive resin slice.
The hot melt adhesive resin slices were tested for melting point, peel strength, and yellowness index, with the test results shown in table 2.
The test method is as follows:
1. melting point test: differential scanning calorimetry was used.
2. The test method of the peel strength comprises the following steps: reference is made to the Standard FZ/T80007.1-2006 for peel Strength test using an adhesive backing.
3. Yellow index (YI value) test: reference is made to ASTM D6290.
Table 2: hot melt adhesive performance test result table
When the hot melt adhesive is applied in the textile field, the lower the melting point of the hot melt adhesive is, the more convenient the operation is, and the lower application temperature can be simply used by a hot melt adhesive gun and a hot melt adhesive machine. The long-chain dibasic acid product is added into the hot melt adhesive, so that the density of amido bonds and the number of hydrogen bonds are reduced, the crystallinity is reduced, and the melting point is reduced.
When the purity of the long-chain dicarboxylic acid product is reduced, the peeling strength of the hot melt adhesive is obviously reduced, and meanwhile, the yellow index of the hot melt adhesive is obviously improved due to the influence of impurities and unsaturated acid in a system. The difference of the impurity content in the product also influences the composition of the final hot melt adhesive polymer, so that the melting point of the hot melt adhesive is different.
In addition, the hot melt adhesive added with the long-chain dicarboxylic acid product is colorless and transparent, and is suitable for high-end markets such as plastics, toys, electronics, furniture, leather, artware, shoe materials, coating, ceramics and the like and the field of transparent adhesive coating visible outside. Meanwhile, the long-chain dicarboxylic acid product is added into the hot melt adhesive, so that the hydrophobicity of the hot melt adhesive is improved, and the solubility of the hot melt adhesive in an organic solvent is reduced, so that the water washing resistance and the dry cleaning resistance can be improved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (14)
1. A long-chain dicarboxylic acid product is characterized in that the total acid content is more than or equal to 97%, the saturated long-chain dicarboxylic acid content is more than or equal to 90%, the ash content is less than or equal to 30ppm, the nitrogen content is less than or equal to 50ppm, the unsaturated dicarboxylic acid content is less than or equal to 0.5%, and the light transmittance is more than or equal to 80%.
2. The long chain dicarboxylic acid product of claim 1, wherein:
ash content is less than or equal to 25ppm, and/or nitrogen content is less than or equal to 40ppm, and/or unsaturated dibasic acid content is less than or equal to 0.35%, and/or light transmittance is more than or equal to 85%.
3. A refining process of long-chain dibasic acid comprises the following steps:
(1) heating and melting a mixture containing long-chain dibasic acid, performing first distillation, and collecting distillate of the first distillation to obtain a first distillation product;
(2) and mixing the first distillation product with an oxidant, and reacting at the temperature of not higher than 240 ℃ to obtain an oxidation product.
4. The process of claim 3, wherein the oxidizing agent comprises a neutral oxidizing agent, an acidic oxidizing agent, an alkaline oxidizing agent, further comprising potassium permanganate, ozone, air, nitric acid at 60 wt% or more.
5. The process according to claim 3, characterized in that:
the oxidation product was treated as follows:
performing second distillation treatment on the oxidation product, collecting distillate of the second distillation to obtain a second distillation product, performing third distillation on the second distillation product, and collecting distillation residues to obtain a third distillation product;
or (II) directly carrying out third distillation on the oxidation product without second distillation treatment, and collecting distillation residues to obtain a third distillation product.
6. The process according to claim 5, characterized in that it comprises the following steps:
and carrying out fourth distillation on the third distillation product, and collecting distillate of the fourth distillation to obtain a fourth distillation product.
7. The process according to claim 6, comprising the steps of:
distilling the fourth distillation product for N times, using the distillate after each distillation for the raw material of the next distillation until the N times of distillation is finished, and collecting the distillate after the N times of distillation to obtain a 4+ N distillation product; in any one distillation process, the vacuum degree is less than or equal to 100pa, and the temperature is 220-250 ℃; n is more than or equal to 1.
8. The process of any one of claims 3 to 7, comprising the steps of:
and (3) decoloring treatment: contacting the distillation product of any one time with a decoloring agent for decoloring; preferably, the dosage of the decoloring agent is 3-40 wt% of the material to be decolored, and/or the decoloring temperature is 130-180 ℃, and/or the decoloring time is 3-120 min.
9. The process according to claim 3, characterized in that:
the mixture containing the long-chain dicarboxylic acid contains saturated long-chain dicarboxylic acid, and the carbon number of the saturated long-chain dicarboxylic acid is 10-18; further, the saturated long-chain dibasic acid is selected from one or a combination of more of sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid and octadecanedioic acid;
and/or the content of saturated long-chain dicarboxylic acid in the mixture containing the long-chain dicarboxylic acid is 10-98 wt%;
and/or, the vacuum degree of the first distillation in the step (1) is less than or equal to 100pa, and the temperature of the first distillation is 180-280 ℃;
and/or, in the step (2), the content of the oxidizing agent is converted into 100 wt%, and the amount of the 100 wt% oxidizing agent used per 100 g of the first distillation product is 1 to 20g, and further 1 to 10 g;
and/or the reaction in the step (2) is preferably carried out at the temperature of 140-240 ℃;
and/or the reaction in the step (2) is carried out for 0.5-6 h.
10. The process as claimed in claim 5, wherein the vacuum degree of the second distillation is less than or equal to 100pa, and the temperature of the second distillation is 180-280 ℃.
11. The process as claimed in claim 5, wherein the vacuum degree of the third distillation is less than or equal to 100pa, and the temperature is 150-240 ℃; and/or the third distillation is rectification, the vacuum degree is less than or equal to 100pa, the temperature of a tower kettle is 150-230 ℃, and the temperature of a tower top is 120-195 ℃.
12. The process as claimed in claim 6 or 7, wherein the vacuum degree of the fourth distillation is less than or equal to 100pa, and the temperature is 180-280 ℃; and/or the fourth distillation is rectification, the vacuum degree is less than or equal to 100pa, the temperature of a tower kettle is 200-280 ℃, and the temperature of a tower top is 180-230 ℃.
13. The process according to claim 3, characterized in that:
the mixture comprising long chain dibasic acids comprises: the long-chain dicarboxylic acid crude product, residues after most of the solvent is recovered from the recrystallization mother liquor of the long-chain dicarboxylic acid crude product, and long-chain dicarboxylic acid precipitates accumulated in a long-term long-chain dicarboxylic acid sewage treatment workshop.
14. The use of the long chain dicarboxylic acid product of claims 1-13 in hot melt adhesives.
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