CN110512213B - Purification method of long-chain mixed dibasic acid - Google Patents
Purification method of long-chain mixed dibasic acid Download PDFInfo
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Abstract
The invention relates to a method for extracting long-chain mixed dibasic acid, which comprises the steps of (1) adding mixed dibasic acid solid into water, heating, adding alkali to adjust the pH value of a solution, dissolving the mixed dibasic acid, cooling to separate out a precipitate, and separating to obtain solid I; (2) putting the solid I into water, heating, adding alkali, dissolving the solid I, and adding an oxidant for oxidation; (3) and adding acid into the solution obtained by oxidation to adjust the pH value of the solution, separating out the long-chain mixed dibasic acid, separating out the solid, washing with water and drying to obtain the long-chain mixed dibasic acid finished product. The invention combines the secondary precipitation and the oxidation process in the water phase to obtain a high-quality long-chain mixed dibasic acid finished product which is white in color, good in quality and low in content of high-carbon number dibasic acid (dibasic acid with more than C16), and is particularly suitable for the application in the field of rust prevention; the extraction process is simple and effective in solving the problem of discharge of by-products in the production of long-chain dicarboxylic acid, thereby not only protecting the environment, but also increasing the income of enterprises.
Description
Technical Field
The invention relates to a method for treating mixed long-chain dibasic acid, in particular to a purification method for decolorizing and oxidizing the mixed long-chain dibasic acid.
Background
Long chain dicarboxylic acids (Long chain dicarboxylic acids) refer to aliphatic dicarboxylic acids (DCn for short) with more than 10 carbon atoms in the carbon chain, including saturated and unsaturated dicarboxylic acids, are a class of fine chemical products with important and wide industrial application, and are important basic raw materials 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. Due to the wide development potential of downstream products of the long-chain dibasic acid, the demand of the long-chain dibasic acid is continuously increased at home and abroad, and the market potential is extremely high.
The production of long-chain dicarboxylic acid by biological method (fermentation method) is the application of microbial technology in petrochemical industry, which has emerged in the last 70 th century. The method is characterized in that abundant petroleum resources are used as raw materials, two methyl groups at two ends of long-chain n-alkane are respectively oxidized under normal temperature and normal pressure by utilizing the specific oxidizing capacity of microorganisms and the action of intracellular enzymes of the microorganisms, and four oxygen atoms are added in one step to generate various long-chain dibasic acids with corresponding chain lengths; the biological method for producing the long-chain dibasic acid overcomes various defects of a simple chemical synthesis method and a vegetable oil cracking preparation method, and opens up a new way for the mass production of the long-chain dibasic acid. Compared with chemical synthesis methods, biological methods for producing long carbon chain dibasic acids have undoubted advantages and are generally regarded at home and abroad. The biological method can not only provide the series of long carbon chain dibasic acid monomers from C9 to C18, even C22, but also can produce long chain dibasic acid (such as long chain dibasic acid with the length of more than C13) which can not be produced by the chemical synthesis method, thereby greatly expanding the application of the dibasic acid in the industrial field.
The long carbon chain mixed dibasic acid is a mixture of two or more than two of C9-C22 dibasic acids, and mainly comes from by-products of C11-C16 dibasic acids prepared by a biological method and the biological preparation of mixed alkane and mixed fatty acid.
Generally, these long carbon chain mixed dibasic acids are often discarded or stacked during the refining process to produce single dibasic acids, which not only pollutes the environment, but also causes waste of resources. In recent years, along with the continuous development of downstream products of dibasic acid, the application of long carbon chain mixed dibasic acid and the advantages of the long carbon chain mixed dibasic acid in synthesizing certain fine chemical products are gradually known, products such as spice, antirust agent and the like synthesized by the long carbon chain mixed dibasic acid are superior to similar products synthesized by single long chain dibasic acid in certain performances, and the long carbon chain mixed dibasic acid can be used as a high-performance antirust agent and provides an antirust agent with excellent antirust effect for the metal processing industry; compared with the antirust agent produced by using a single variety of dibasic acid, the long carbon chain mixed dibasic acid has irreplaceable excellent performance. Therefore, research and development of a resource utilization technology are carried out to recycle the by-products, so that the problems of environmental pollution and resource waste can be solved, the requirements of green chemistry are met, and the method has important social and economic significance.
In the process of treating the long-chain diacid heavy component, Chinese patent application CN102010318A discloses a method of decoloring twice or more and then acidifying, and mixed diacid with higher purity can be obtained. The disadvantages are that: the process requires two or more decolorizations with activated carbon, resulting in a large loss of dibasic acid and a low yield. Meanwhile, the mixed long-chain dibasic acid contains excessive high-carbon number dibasic acid (more than sixteen carbons), so that the solubility of the product in the formula of the antirust agent is poor, and the antirust effect and the use of customers are influenced. The Chinese patent application CN102795984A takes the recombination of dodecanedioic acid refined by ethanol as a raw material to react with excessive liquid alkali to generate long-carbon-chain diacid, the process has the defect of esterification of the diacid and the ethanol caused by an ethanol process, and pigment and impurities cannot be effectively removed only by decoloring with activated carbon, the product appearance is poor, and the recovery of a solvent is relatively complicated. Also, this product has a problem of too high content of high carbon number dibasic acid, which affects the final application of the product.
Disclosure of Invention
The invention aims to provide a method for extracting waste-long-chain mixed dibasic acid in long-chain dibasic acid production, which aims to solve the problems in the prior art. The extraction method combines secondary precipitation and oxidation processes in a water phase to obtain a high-quality long-chain mixed dibasic acid finished product, the product is white in color, good in quality, low in content of high-carbon number dibasic acid (dibasic acid with more than C16), and particularly suitable for the field of rust prevention; the extraction process is simple and effective in solving the problem of discharge of byproducts in the production of long-chain dicarboxylic acid, thereby not only protecting the environment, but also increasing the income of enterprises.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for extracting long-chain mixed dibasic acid comprises the following steps:
(1) adding mixed dibasic acid solid into water, heating, adding alkali to adjust the pH value of the solution to dissolve the mixed dibasic acid, then cooling to separate out precipitate, and separating to obtain solid I;
(2) putting the solid I into water, heating, dissolving the solid I, and adding an oxidant for oxidation;
(3) and adding acid into the solution obtained by oxidation to adjust the pH value of the solution, separating out the long-chain mixed dibasic acid, separating out the solid, washing with water and drying to obtain the long-chain mixed dibasic acid finished product.
The long-chain dibasic acid provided by the invention can be a saturated or unsaturated straight-chain dibasic acid with 9 to 18 carbon atoms, wherein the carboxyl is arranged at two ends of a carbon chain. The long chain dibasic acid may be selected from azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid and 9-ene-octadecanedioic acid.
The mixed dibasic acid of the invention refers to a byproduct obtained in the processes of fermentation and extraction of long-chain dibasic acid, and the main component of the mixed dibasic acid is dibasic acid of C7-C18. The composition of the mixed dibasic acid is relatively complex, and the components of the mixed dibasic acid are correspondingly changed due to different fermentation strains, types of the produced long-chain dibasic acid and processes for extracting the long-chain dibasic acid.
Preferably, in step (1), the mixed dibasic acid is added to water and heated to a temperature of 60 ℃ or higher, preferably 80 ℃ or higher and a boiling point or lower.
Preferably, in the step (1), alkali is added, and the pH value of the solution is controlled to be 5.6-7.2, preferably 5.8-6.7.
Preferably, in the step (1), after the mixed dibasic acid is dissolved after the alkali is added, the weight percentage concentration of the mixed dibasic acid in the mixed dibasic acid solution is controlled to be 5-40%, and preferably 10-30% (gas chromatography internal standard method).
Preferably, the base used in step (1) may be a commonly used inorganic base, including but not limited to sodium hydroxide, potassium hydroxide, etc., or an inorganic base solution, such as a 30% by weight aqueous solution of sodium hydroxide, etc.
According to the requirement, the mixed dibasic acid solution in the step (1) may be subjected to impurity removal and decolorization treatment, for example, the mixed dibasic acid solution may be filtered, or activated carbon may be added for decolorization and filtration to remove insoluble impurities and part of colored substances, before the mixed dibasic acid is cooled to precipitate. The skilled person knows how to select the type and amount of activated carbon to be used. If the source of the mixed dibasic acid is pure, the mixed dibasic acid can be directly used in the next operation procedure without filtering. Preferably, the filtration is carried out by using macroporous powdered sugar carbon.
In the step (1), the mixed dibasic acid solution is cooled, and precipitates are separated out, wherein the precipitates mainly comprise long-chain dibasic acid sodium salts and a small amount of long-chain dibasic acid. The inventor surprisingly finds that in a certain condition, in the process of cooling and separating out the mixed dibasic acid solution, the long-chain mixed dibasic acid is not separated out in a crystal form but is gathered in the solution in an oil drop form in the initial stage, and the oil drop is gradually solidified to form a precipitate along with the reduction of the temperature, so that the long-chain mixed dibasic acid solid precipitate I which is light white in color, low in impurity content and easy to filter can be obtained.
In the step (1), mixing a binary acid solution for cooling and precipitating, wherein the cooling end point is below 50 ℃ and is 5-50 ℃; preferably below 40 ℃ and 5-40 ℃. The yield of the product obtained by cooling is mainly related to the initial concentration of the mixed dibasic acid in the solution and the cooling end point. The mixed dibasic acid solution is preferably maintained for 0.5 to 2 hours after being cooled.
It is readily understood here that when the initial concentration of the solution is low, further concentration may be performed prior to the temperature reduction to increase the yield of the temperature-reduced precipitation process.
The comparative experimental results show that when the experimental conditions are not operated within the range of the above-mentioned optimized experimental conditions of the present invention, the solution obtained by cooling is pasty, there is substantially no crystal formation, and the paste cannot be filtered, and there is no industrial value.
After obtaining the precipitate (solid I) of the long-chain mixed dibasic acid and the salt thereof, the solid I is obtained by separation. The separation method includes but is not limited to conventional separation processes such as centrifugation and filtration. The separated solid I can be properly washed to obtain a solid with better quality; preferably, the washing is carried out by using cold water, and the temperature of the cold water is preferably 10-40 ℃.
The obtained solid I can be dried or directly enters the next operation procedure without being dried.
Preferably, the solid I in the step (2) is put into water and heated to 60-80 ℃.
Preferably, in the step (2), the obtained solid I is put into water, heated to dissolve the solid, and the weight percentage concentration of the long-chain mixed dibasic acid in the dissolved solution is controlled to be 40% or less, preferably 5 to 40%, more preferably 20% or less, and still more preferably 5 to 20% (gas chromatography internal standard method).
In the step (2), in the process of putting the solid I into water for heating and dissolving, the solid I can not be dissolved frequently. In this case, an appropriate amount of base is added to promote dissolution of the solid. The amount of the base added may be determined depending on the dissolution of the solid I. Namely, in the step (2), the solid I is put into water, heated, added with alkali to dissolve the solid I, and then oxidized by adding an oxidizing agent.
If the solid I is dissolved, a light yellow or yellow solution is obtained, in order to further improve the quality of the dissolved long-chain mixed binary acid solution, the long-chain mixed binary acid solution can be decolorized by activated carbon or resin, and then an oxidation step is carried out. There is no particular requirement for the activated carbon decolorization or resin decolorization treatment, and one skilled in the art would know how to determine the specific activated carbon, type of resin, and amount used.
And (3) adding an oxidant for oxidation in the step (2), wherein the oxidant is preferably ozone and/or hydrogen peroxide. In one embodiment, ozone is introduced for oxidation, in another embodiment, hydrogen peroxide is added for oxidation, and in another embodiment, ozone and hydrogen peroxide are added for combined oxidation.
The invention surprisingly found that after oxidation with an oxidizing agent, on the one hand, the color of the solution is further improved, and on the other hand, the content of the high carbon number dibasic acid (which refers to dibasic acid with the carbon number of more than 16) in the solution is greatly reduced, and the high carbon number dibasic acid is basically decomposed completely along with the increase of the adding amount of the oxidizing agent. According to the trial condition of customers, the solubility of the long-chain mixed dibasic acid product obtained by oxidation in the antirust formula is greatly improved, and the antirust effect is obviously enhanced.
In the step (2), the solution in which the solid I is dissolved or the solution in which the solid I is dissolved and decolorized is oxidized with ozone, generally, as long as it is ensured that the long-chain dibasic acid is substantially dissolved. At the same time, a moderately alkaline pH value in the solution is more conducive to the oxidation process.
In the present invention, the temperature of oxidizing with the oxidizing agent is preferably 30 ℃ or higher, and the initial pH of the solution is preferably not less than 8.0. The amount of the oxidant added is not less than 1% of the oven dry weight of the solid I. More preferably, the oxidizing temperature of the oxidizing agent is 30-95 ℃, and the initial pH value of the solution is 8.0-9.0.
In some embodiments, the temperature of the ozonation is preferably above 30 ℃ and the initial pH of the solution is preferably no less than 8.0. The amount of ozone added is not less than 1% of the oven dry weight of the solid I. More preferably, the temperature of the ozone oxidation is 30-95 ℃, and the initial pH value of the solution is 8.0-9.0.
In some embodiments, the solution of the solid I after dissolution or the solution after dissolution and decoloration can also be oxidized by adding hydrogen peroxide. The oxidation condition of the hydrogen peroxide is close to that of the ozone. In the present invention, the temperature of the hydrogen peroxide oxidation is preferably 30 ℃ or higher, and the initial pH of the solution is preferably not less than 8.0. The adding amount of the hydrogen peroxide is not less than 1 percent of the absolute dry weight of the solid I. More preferably, the temperature of the hydrogen peroxide is 30-80 ℃, and the initial pH value of the solution is 8.0-9.0.
In some embodiments, the dissolved solution of the solid I or the dissolved and decolored solution, ozone can also be used in combination with hydrogen peroxide for the oxidative decoloration of the solution. The temperature and the pH value of the combined use are consistent with the respective use conditions of the single oxidant.
The oxidized solution can be further decolorized by activated carbon if necessary, or can be directly carried out in the next operation procedure without decolorization.
And (3) adding inorganic acid into the oxidized solution, and adjusting the pH value of the solution to precipitate and separate out the long-chain mixed dibasic acid.
The inorganic acid used herein means a commonly used inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, etc.
In the step (3), adjusting the pH value of the solution by acidification, wherein the pH value of the end point is required to be controlled to be less than 4.5 and is 2-4.5; preferably, the pH value of the final point is below 4 and is 2-4, so that the long-chain dicarboxylic acid is acidified and precipitated.
In the step (3), the separated long-chain mixed dibasic acid is separated from the aqueous solution in a separation mode including but not limited to conventional separation processes such as centrifugation, filtration and the like, and the separation temperature needs to be reduced to below 50 ℃ preferably but higher than 20 ℃.
And (3) separating the obtained long-chain mixed dibasic acid solid, and further drying to obtain a long-chain mixed dibasic acid finished product.
The long-chain mixed dibasic acid solid obtained by the steps is white or light yellow in appearance, good in quality and low in content of high-carbon number dibasic acid (dibasic acid with the carbon number of more than C16), and can completely meet the product quality requirements of fields such as synthetic spices and antirust agents on the long-chain mixed dibasic acid. Of course, according to different application fields, the quality of the long-chain mixed dibasic acid finished product obtained by the invention can be further improved by further processing, such as acetic acid solution crystallization, ethanol solution crystallization and the like, and finally the requirements of different customers are met.
Compared with the prior art, the invention has the following beneficial effects:
the invention has the advantages that the high-quality long-chain mixed dibasic acid finished product is obtained by combining the secondary precipitation and the oxidation process in the water phase, the product has white color and good quality, the content of high-carbon number dibasic acid (dibasic acid with more than C16) is low, and the invention is particularly suitable for the application in the field of rust prevention. The extraction process is simple and effectively solves the problem of discharge of byproducts in the production of the long-chain dicarboxylic acid, thereby not only protecting the environment, but also increasing the income of enterprises.
Detailed Description
The present invention will be described in detail below by way of examples to make the features and advantages of the present invention clearer, but the present invention is not limited to the examples set forth herein.
The following comparative examples and examples refer to patent ZL200410018255.7 for the preparation of fermentation broths.
The test methods used in the comparative examples and examples of the present invention are as follows:
1. and (3) detecting by using a binary acid gas chromatography:
reference is made to the determination of fatty acids in infant food and milk of GB5413.27-2010, using standard diacid samples as controls.
2. And (3) total nitrogen determination:
the Kjeldahl method is adopted.
3. And (3) light transmittance measurement:
the dibasic acid sample was dissolved in an aqueous solution of sodium salt at a concentration of 5% by weight, and then the light transmittance at 430nm was measured by UV.
Comparative example 1
Taking 100 g of byproduct mixed dibasic acid obtained in the extraction process of the dodecanedioic acid, adding 1000 g of water, heating to 70 ℃, adding caustic soda, adjusting the pH to be more than 8.0, stirring, and almost completely dissolving the mixed dibasic acid.
10 g of macroporous powdered sugar carbon is added into the solution, stirred for 1 hour and filtered while the solution is hot to obtain filtrate.
And adding 10 g of macroporous powdered sugar carbon into the filtrate, stirring for 1 hour, and filtering while the filtrate is hot to obtain the filtrate.
Adding sulfuric acid with the concentration of 98 percent by mass into the obtained filtrate, adjusting the pH to be less than 3, cooling to 45 ℃, filtering to obtain a wet solid of the long-chain mixed dibasic acid, and drying to obtain a comparative product.
And (4) measuring indexes such as content, total nitrogen, light transmission and the like of the product.
Example 1
Taking 100 g of by-product mixed dibasic acid obtained in the extraction process of the dodecanedioic acid, adding 1800 g of water, heating to 90 ℃, adding caustic soda, adjusting the pH to 5.7, stirring, and almost completely dissolving the mixed dibasic acid.
3 g of macroporous powdered sugar carbon is added into the solution, stirred for 1 hour and filtered while the solution is hot to obtain filtrate.
The obtained filtrate is stirred and cooled to room temperature for precipitation. After the temperature was decreased to 40 ℃, it was maintained for one hour, and then filtered to obtain a precipitate of large particles. Washed with 50 grams of cold water.
The obtained precipitate was added to 1000 g of water, heated to 80 ℃, stirred, and after 7 g of sodium hydroxide was added, the precipitate was completely dissolved.
Ozone is introduced into the solution for oxidation, the amount of the introduced ozone is controlled to be 2% of the absolute dry weight of the solid I, and the oxidation temperature is 70 ℃.
Adding 30 mass percent sulfuric acid into the oxidized filtrate, adjusting the pH to 3.0, cooling to 50 ℃, filtering to obtain a long-chain mixed dibasic acid wet solid, washing with 100 g of 50 ℃ water, and drying the solid to obtain a finished product.
And (4) measuring indexes such as content, total nitrogen, light transmission and the like of the product.
Example 2
Taking 100 g of by-product mixed dibasic acid obtained in the extraction process of the dodecanedioic acid, adding 400 g of water, heating to 90 ℃, adding caustic soda, adjusting the pH to 6.7, stirring, and almost completely dissolving the mixed dibasic acid.
The obtained filtrate is stirred and cooled to room temperature for precipitation. After the temperature was decreased to 30 ℃, it was maintained for one hour, and then filtered to obtain a precipitate of large particles. Washed with 50 grams of cold water.
The obtained precipitate was added to 1200 g of water, heated to 80 ℃, stirred, and after 2 g of sodium hydroxide was added, the precipitate was completely dissolved. To the resulting solution was added 3 g of macroporous powdered sugar charcoal, stirred for 1 hour, and filtered while hot to obtain a filtrate.
Ozone is introduced into the solution for oxidation, the amount of the introduced ozone is controlled to be 5% of the absolute dry weight of the solid I, and the oxidation temperature is 90 ℃.
Adding 95% sulfuric acid in percentage concentration by mass into the oxidized filtrate, adjusting the pH to 3.5, cooling to 40 ℃, filtering to obtain a long-chain mixed dibasic acid wet solid, washing with 100 g of 50 ℃ water, and drying the solid to obtain a finished product.
And (4) measuring indexes such as total nitrogen, light transmission and the like of the product.
Example 3
Taking 100 g of by-product mixed dibasic acid obtained in the extraction process of the dodecanedioic acid, adding 200 g of water, heating to 95 ℃, adding caustic soda, adjusting the pH to 6.2, stirring, and almost completely dissolving the mixed dibasic acid.
1 g of macroporous powdered sugar carbon is added into the solution, stirred for 1 hour and filtered while the solution is hot to obtain filtrate.
The obtained filtrate is stirred and cooled to room temperature for precipitation. After the temperature was decreased to 40 ℃, it was maintained for one hour, and then filtered to obtain a precipitate of large particles. Washed with 50 grams of cold water.
The obtained precipitate was added to 1000 g of water, heated to 80 ℃, stirred, and after 5 g of sodium hydroxide was added, the precipitate was completely dissolved.
And (3) introducing ozone into the solution for oxidation, controlling the amount of the introduced ozone to be 8% of the absolute dry weight of the solid I, controlling the oxidation temperature to be 85 ℃, adding 3 g of macroporous powder carbonhydrate into the oxidized solution, stirring for 1 hour, and filtering while the solution is hot to obtain a filtrate.
Adding sulfuric acid with the concentration of 98 percent by mass into the obtained filtrate, adjusting the pH to 3.2, cooling to 50 ℃, filtering to obtain wet solid of the long-chain mixed dibasic acid, washing with 100 g of water at 50 ℃, and drying the solid to obtain a finished product.
And (4) measuring indexes such as total nitrogen, light transmission and the like of the product.
Example 4
Taking 100 g of byproduct mixed dibasic acid obtained in the extraction process of the tridecanedioic acid, adding 200 g of water, heating to 95 ℃, adding caustic soda, adjusting the pH to 7.0, stirring, and almost completely dissolving the mixed dibasic acid.
1 g of macroporous powdered sugar carbon is added into the solution, stirred for 1 hour and filtered while the solution is hot to obtain filtrate.
The obtained filtrate is stirred and cooled to room temperature for precipitation. After the temperature was decreased to 40 ℃, it was maintained for one hour, and then filtered to obtain a precipitate of large particles. Washed with 50 grams of cold water.
The obtained precipitate was added to 1000 g of water, heated to 80 ℃, stirred, and after 2 g of sodium hydroxide was added, the precipitate was completely dissolved.
And (3) introducing ozone into the solution for oxidation, controlling the amount of the introduced ozone to be 1% of the absolute dry weight of the solid I, controlling the oxidation temperature to be 60 ℃, adding 3 g of macroporous powder carbonhydrate into the oxidized solution, stirring for 1 hour, and filtering while the solution is hot to obtain a filtrate.
Adding sulfuric acid with the concentration of 98 percent by mass into the obtained filtrate, adjusting the pH to 3.2, cooling to 50 ℃, filtering to obtain wet solid of the long-chain mixed dibasic acid, washing with 100 g of water at 50 ℃, and drying the solid to obtain a finished product.
And (4) measuring indexes such as total nitrogen, light transmission and the like of the product.
Example 5
Taking 100 g of byproduct mixed dibasic acid obtained in the extraction process of the tetradecanedioic acid, adding 400 g of water, heating to 95 ℃, adding caustic soda, adjusting the pH to 6.6, stirring, and almost completely dissolving the mixed dibasic acid.
1 g of macroporous powdered sugar carbon is added into the solution, stirred for 1 hour and filtered while the solution is hot to obtain filtrate.
The obtained filtrate is stirred and cooled to room temperature for precipitation. After the temperature was decreased to 40 ℃, it was maintained for one hour, and then filtered to obtain a precipitate of large particles. Washed with 50 grams of cold water.
The obtained precipitate was added to 1000 g of water, heated to 80 ℃, stirred, and after 4 g of sodium hydroxide was added, the precipitate was completely dissolved.
Adding hydrogen peroxide into the solution for oxidation, controlling the amount of the added hydrogen peroxide to be 5% of the absolute dry weight of the solid I, stirring, maintaining the temperature of the solution at 30 ℃ for one hour, then heating to 90 ℃ for half an hour, and completing the oxidation.
After the oxidation was completed, 3 g of macroporous powdered sugar charcoal was added to the resulting solution, stirred for 1 hour, and filtered while hot to obtain a filtrate.
Adding sulfuric acid with the concentration of 98 percent by mass into the obtained filtrate, adjusting the pH to 3.2, cooling to 50 ℃, filtering to obtain wet solid of the long-chain mixed dibasic acid, washing with 100 g of water at 50 ℃, and drying the solid to obtain a finished product.
And (4) measuring indexes such as total nitrogen, light transmission and the like of the product.
Example 6
Taking 100 g of byproduct mixed dibasic acid obtained in the extraction process of the undecane dibasic acid, adding 150 g of water, heating to 97 ℃, adding caustic soda, adjusting the pH to 7.1, stirring, and almost completely dissolving the mixed dibasic acid.
1 g of macroporous powdered sugar carbon is added into the solution, stirred for 1 hour and filtered while the solution is hot to obtain filtrate.
The obtained filtrate is stirred and cooled to room temperature for precipitation. After the temperature was decreased to 30 ℃, it was maintained for one hour, and then filtered to obtain a precipitate of large particles. Washed with 50 grams of cold water.
The obtained precipitate was added to 800 g of water, heated to 80 ℃, stirred, and after 2 g of sodium hydroxide was added, the precipitate was completely dissolved. To the resulting solution was added 3 g of macroporous powdered sugar charcoal, stirred for 1 hour, and filtered while hot to obtain a filtrate.
Adding hydrogen peroxide into the solution for oxidation, controlling the amount of the added hydrogen peroxide to be 2% of the absolute dry weight of the solid I, stirring, maintaining the temperature of the solution at 80 ℃, and keeping the temperature for one hour to finish the oxidation.
Adding 98 mass percent sulfuric acid into the obtained oxidation solution, adjusting the pH to 2.5, cooling to 30 ℃, filtering to obtain a long-chain mixed dibasic acid wet solid, washing with 100 g of 30 ℃ water, and drying the solid to obtain a finished product.
And (4) measuring indexes such as total nitrogen, light transmission and the like of the product.
Example 7
Taking 100 g of byproduct mixed dibasic acid obtained in the extraction process of the tridecanedioic acid, adding 500 g of water, heating to 95 ℃, adding caustic soda, adjusting the pH to 6.3, stirring, and almost completely dissolving the mixed dibasic acid.
1 g of macroporous powdered sugar carbon is added into the solution, stirred for 1 hour and filtered while the solution is hot to obtain filtrate.
The obtained filtrate is stirred and cooled to room temperature for precipitation. After the temperature was decreased to 40 ℃, it was maintained for one hour, and then filtered to obtain a precipitate of large particles. Washed with 50 grams of cold water.
The obtained precipitate was added to 1000 g of water, heated to 80 ℃, stirred, and after 6 g of sodium hydroxide was added, the precipitate was completely dissolved.
Adding hydrogen peroxide into the solution for oxidation, controlling the amount of the added hydrogen peroxide to be 3% of the absolute dry weight of the solid I, stirring, maintaining the temperature of the solution at 90 ℃, and keeping the temperature for one hour to finish the oxidation.
To the resulting solution was added 3 g of macroporous powdered sugar charcoal, stirred for 1 hour, and filtered while hot to obtain a filtrate.
Adding hydrochloric acid into the obtained filtrate, adjusting pH to 3.4, cooling to 50 ℃, filtering to obtain a long-chain mixed dibasic acid wet solid, washing with 100 g of 50 ℃ water, and drying the solid to obtain a finished product.
And (4) measuring indexes such as total nitrogen, light transmission and the like of the product.
TABLE 1 quality of the products of the comparative examples and examples
As can be seen from Table 1, the invention combines the secondary precipitation and oxidation processes in the water phase to obtain a high-quality long-chain mixed dibasic acid finished product, which has white color, low total nitrogen content (not higher than 70ppm), high light transmittance (higher than 78%), good quality, and low content (lower than 5.5%) of high-carbon dibasic acid (dibasic acid with more than C16), and is particularly suitable for the application in the field of rust prevention. The extraction process is simple and effectively solves the problem of discharge of byproducts in the production of the long-chain dicarboxylic acid, thereby not only protecting the environment, but also increasing the income of enterprises.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (16)
1. A method for extracting long-chain mixed dibasic acid comprises the following steps:
(1) adding mixed dibasic acid solid into water, heating, adding alkali to adjust the pH value of the solution to dissolve the mixed dibasic acid, then cooling to separate out precipitate, and separating to obtain solid I;
(2) putting the solid I into water, heating, adding alkali, dissolving the solid I, and adding an oxidant for oxidation, wherein the addition amount of the oxidant is 1-5% of the absolute dry weight of the solid I, and the oxidant is ozone and/or hydrogen peroxide;
(3) adding acid into the solution obtained by oxidation to adjust the pH value of the solution, separating out long-chain mixed dibasic acid, separating solid, washing with water and drying to obtain a long-chain mixed dibasic acid finished product;
wherein, in the step (1), adding alkali and controlling the pH value of the solution to be between 5.6 and 7.2;
mixing a binary acid solution in the step (1) for cooling and precipitation, wherein the cooling end point is below 40 ℃; in the step (1), the mixed dibasic acid solution is maintained for 0.5 to 2 hours after being cooled;
the long-chain mixed dibasic acid is a byproduct obtained in the processes of fermentation and extraction of the long-chain dibasic acid, and mainly comprises C7-C18 dibasic acid.
2. The method for extracting a long-chain mixed dibasic acid as claimed in claim 1, wherein in the step (1), the mixed dibasic acid solid is put into water and heated to a temperature of 60 ℃ or higher.
3. The method for extracting a long-chain mixed dibasic acid according to claim 2, wherein in the step (1), the mixed dibasic acid solid is put into water and heated to a temperature of 80 ℃ or higher and a boiling point of the mixed dibasic acid solution or lower.
4. The method for extracting mixed dibasic acid with long chain as claimed in any one of claims 1 to 3, wherein the concentration of the mixed dibasic acid in the solution is 5 to 40% by weight after the mixed dibasic acid is dissolved in the step (1).
5. The method for extracting long-chain mixed dibasic acid as claimed in claim 4, wherein the concentration of the mixed dibasic acid in the solution is 10-30% by weight after the mixed dibasic acid is dissolved in the step (1).
6. The method for extracting long-chain mixed dibasic acid as claimed in any one of claims 1 to 3, wherein the mixed dibasic acid solution is further subjected to impurity removal, decolorization and/or concentration treatment after the mixed dibasic acid is dissolved and before the temperature is reduced in the step (1).
7. The method for extracting long-chain mixed dibasic acid as claimed in claim 1, wherein in the step (2), the solid I is put into water and heated to 60-80 ℃.
8. The method for extracting mixed dibasic acid with long chain as claimed in claim 1, wherein the concentration of the mixed dibasic acid with long chain in the solution after dissolution in the step (2) is 40% or less by weight.
9. The method for extracting long-chain mixed dibasic acid as claimed in claim 8, wherein the concentration of the long-chain mixed dibasic acid in the solution dissolved in the step (2) is 5-20% by weight.
10. The method for extracting a long-chain mixed dibasic acid as claimed in claim 1, wherein the temperature of the oxidation in the step (2) is 30 ℃ or higher.
11. The method for extracting long-chain mixed dibasic acid according to claim 10, wherein the temperature of the oxidation in the step (2) is 30 to 95 ℃.
12. The method for extracting mixed dibasic acid with long chain as claimed in any one of claims 1, 2, 3, 7, 8, 9 and 10, wherein in the step (2), the initial pH of the solution is not lower than 8.0 during the oxidation.
13. The method for extracting mixed dibasic acid with long chain as claimed in claim 12, wherein the initial pH of the solution is 8.0 to 9.0 during the oxidation in the step (2).
14. The method for extracting mixed dibasic acid with long chain as claimed in any one of claims 1, 2, 3, 7, 8, 9 and 10, wherein in the step (3), the pH value of the solution is adjusted by acidification, and the end point pH value is controlled to be less than 4.5.
15. The method for extracting mixed dibasic acid with long chain as claimed in claim 14, wherein the pH of the solution is adjusted by acidification in step (3), and the pH at the end point is controlled to be below 4 to acidify and separate out the dibasic acid with long chain; in the step (3), the temperature is reduced to 20-50 ℃ when the solid is separated.
16. The method for extracting a mixed dibasic acid with a long chain as claimed in any one of claims 1, 2, 3, 7, 8, 9 and 10,
in the step (2), after the solid I is completely dissolved, in order to further improve the quality of the dissolved long-chain mixed binary acid solution, the long-chain mixed binary acid solution is further subjected to activated carbon decolorization or resin decolorization, and then an oxidation step is performed;
and (3) in the step (2), the oxidized solution is further subjected to activated carbon decolorization on the long-chain mixed binary acid solution.
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| CN1255483A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for refining long-chain biatomic acid |
| CN101108928A (en) * | 2006-07-20 | 2008-01-23 | 上海凯赛生物技术研发中心有限公司 | Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride |
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| CN103030550A (en) * | 2011-09-30 | 2013-04-10 | 中国科学院微生物研究所 | Method of purifying and refining long-chain dicarboxylic acids and product |
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| JPS5626193A (en) * | 1979-08-09 | 1981-03-13 | Nippon Mining Co Ltd | Removal of microbial cell from fermentation broth of long-chain dicarboxylic acid |
| CN1064951C (en) * | 1997-12-08 | 2001-04-25 | 中国石油化工总公司抚顺石油化工研究院 | Method for refining long-chain bibasic acid |
| CN1221510C (en) * | 2003-05-31 | 2005-10-05 | 中国石油化工股份有限公司 | Refining method for long-chain biatomic acid |
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| CN1255483A (en) * | 1998-12-03 | 2000-06-07 | 中国石油化工集团公司 | Process for refining long-chain biatomic acid |
| CN101108928A (en) * | 2006-07-20 | 2008-01-23 | 上海凯赛生物技术研发中心有限公司 | Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride |
| CN103030550A (en) * | 2011-09-30 | 2013-04-10 | 中国科学院微生物研究所 | Method of purifying and refining long-chain dicarboxylic acids and product |
| CN102503800A (en) * | 2011-10-12 | 2012-06-20 | 江南大学 | Refining method of C11-C18 long-chain diacid |
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