CN111269113A - Method for treating mixture containing long-chain dibasic acid, dibutyl long-chain dibasic acid mixture and application thereof - Google Patents
Method for treating mixture containing long-chain dibasic acid, dibutyl long-chain dibasic acid mixture and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Abstract
The invention provides a processing method of a mixture containing long-chain dibasic acid, a long-chain dibasic acid dibutyl ester mixture and application thereof. The mixture containing the long-chain dicarboxylic acid discharged in the process of extracting and refining the long-chain dicarboxylic acid by using the long-chain dicarboxylic acid fermentation liquor is effectively utilized, and the resource waste is avoided. The dibutyl long-chain dibasic acid mixture obtained by carrying out butylation reaction and purification on the mixture containing the long-chain dibasic acid has low chroma, can be directly applied to a cold-resistant plasticizer, and can effectively improve the low-temperature flexibility of the polymer. The method for treating the mixture containing the long-chain dibasic acid is suitable for industrial large-scale production, has low requirement on equipment, is simple and convenient to operate, solves the problem of treatment and reutilization of effluent in the production process of the long-chain dibasic acid, and has economic value.
Description
Technical Field
The invention relates to a method for recycling a mixture containing long-chain dibasic acid.
Background
Plasticizers (plastisizers) generally refer to a class of small molecular substances with high boiling points, low volatility and miscibility with polymers, having the behavior of modifying the mechanical properties of the polymer. The main function of the plasticizer is to weaken the secondary bond between polymer molecules, namely Van der Waals force, so that the mobility of polymer molecular chains is increased, the crystallinity of the polymer molecular chains is reduced, and the plasticity of the polymer is increased, which is represented by that the hardness, modulus, softening temperature and brittle temperature of the polymer are reduced, and the elongation, flexibility and flexibility of the polymer are improved. Plasticizers can be high boiling, difficult to volatilize viscous liquids or low melting solids that do not generally chemically react with the polymer.
At present, the plasticizer widely used in the domestic market is still phthalate plasticizer (such as dioctyl phthalate DOP), and the most key factor causing the current situation is the low price of the product. Although phthalate ester as a main plasticizer has relatively good use performance, in recent years, phthalate ester has potential harm to human bodies and pollution to the environment, and a series of laws and regulations are set up in various countries or regions or a series of policies are set out to limit the use of phthalate ester in the fields of toys for children, medical plastics, food and the like. With increasingly strict requirements on sanitary safety in China, the replacement of the traditional plasticizer by the novel environment-friendly plasticizer has become a trend. Plasticizers are currently being developed towards relatively high molecular weight, environmentally friendly and easily degradable. In recent years, researches on citric acid esters, epoxy vegetable oil-based plasticizers and polyol ester plasticizers which replace phthalate ester plasticizers have been rapidly developed, and deep researches on green and environment-friendly plasticizer products and large-scale industrialization have come.
Long Chain Dicarboxylic Acids (LCDA), which have the structural formula: HOOC- (CH)2) n-COOH (n ═ 8-16), abbreviated as: DC10-DC18 is an important organic intermediate and is widely applied to the fields of chemical industry, light industry, pesticides, medicines, new materials and the like. The most common method for preparing long-chain dicarboxylic acid at present is to ferment long-chain alkane, fatty acid ester or fatty acid salt under a specific strain. The mixture containing the long-chain dicarboxylic acid discharged in the process of preparing the long-chain dicarboxylic acid by fermentation is often abandoned or stacked, thereby causing resource waste. If the mixture containing the long-chain dibasic acid is subjected to methyl esterification, the methyl esterification product of the mixture containing the long-chain dibasic acid is an intermediate, and further deep processing such as alkaline hydrolysis, ester exchange reaction and the like is required to generate the corresponding long-chain dibasic mixed acid or an ester of the long-chain dibasic mixed acid. Such a process is complicated and the treatment cost is high. Thus containing a long chain for a long chain dibasic acidThe research on the esterification reaction (such as the butylation reaction) for converting and reusing the mixture of the dibasic acid has more important practical significance.
Disclosure of Invention
The invention provides a method for treating a mixture containing long-chain dibasic acid, which comprises the following steps: and (3) butyl esterifying the mixture containing the long-chain dibasic acid to synthesize the mixture of the long-chain dibutyl dibasic acid. The butyl esterification technology is suitable for industrial production, the problem of resource waste of a mixture containing long-chain dicarboxylic acid discharged in the industrial fermentation preparation process of the long-chain dicarboxylic acid can be solved, and the mixed long-chain dibutyl dicarboxylate generated by conversion after butyl esterification reaction can be directly used for products such as cold-resistant plasticizers.
The invention provides a method for processing a mixture containing long-chain dibasic acid, which comprises the following steps: and carrying out butylation reaction on the mixture containing the long-chain dibasic acid.
Further, the method for processing the mixture containing the long-chain dibasic acid comprises the following steps:
(1) uniformly mixing a mixture containing long-chain dibasic acid, n-butyl alcohol and a catalyst, and carrying out a butylation reaction;
(2) washing a product after the butylation reaction with alkali liquor;
(3) distilling and purifying to obtain the mixture of the long-chain dibutyl dibasic acid.
The mixture containing the long-chain dibasic acid in the present invention may include: the method comprises the following steps of extracting a long-chain dicarboxylic acid-containing material discharged in the process of extracting and refining the long-chain dicarboxylic acid by using a fermentation liquor of the long-chain dicarboxylic acid, or recovering most of a solvent from the material, or obtaining long-chain dicarboxylic acid precipitate by long-term precipitation accumulation in a long-chain dicarboxylic acid sewage treatment workshop.
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 is preferably candida. The substrate is substantially completely consumed by fermentation.
The extraction and refining method of the long-chain dicarboxylic acid fermentation liquor can be a method known in the field.
The "long-chain dibasic acid" in the "extracting and refining of long-chain dibasic acid from a long-chain dibasic acid fermentation broth" is understood by those skilled in the art to be a long-chain dibasic acid with the same length as the carbon chain of a fermentation substrate, and can also be referred to as a target long-chain dibasic acid.
Further, the mixture containing the long-chain dibasic acid in the present invention includes:
(1) dissolving a long-chain dicarboxylic acid crude product obtained from a long-chain dicarboxylic acid fermentation liquor in a solvent, and cooling, crystallizing and separating out a material left after long-chain dicarboxylic acid precipitation;
or (2) the remainder of the material obtained in the step (1) after most of the solvent is recovered;
or (3) acidifying and crystallizing the fermentation liquor of the long-chain dibasic acid, extracting the acidified crystallization liquor by using a solvent, separating liquid, cooling and crystallizing an organic phase containing the long-chain dibasic acid, and separating a material remained after the long-chain dibasic acid is precipitated;
or (4), the remainder of the material obtained in the step (3) after most of the solvent is recovered;
or (5) long-chain diacid sediment obtained by long-term sediment accumulation in a long-chain diacid sewage treatment workshop.
Further, in the manner of (1) obtaining the crude long-chain dicarboxylic acid from the fermentation broth of the long-chain dicarboxylic acid, the crude long-chain dicarboxylic acid can be obtained by acidifying and crystallizing the fermentation broth of the long-chain dicarboxylic acid and then separating out the precipitate. Optionally, the fermentation broth is directly subjected to acidification crystallization. Optionally, before acidification and crystallization, removing thallus in the fermentation liquid by centrifugation or membrane filtration to obtain clear dibasic acid solution. Whether the activated carbon decolorization step is carried out before acidification and crystallization can be selected according to the condition of the diacid clear liquid.
Further, the separation means (1) or (3) includes centrifugation and/or filtration.
It can be understood that: through the recrystallization of the step (1), most of impurities (including cell tissues and pigments of fermenting microorganisms) in the crude product of the long-chain dicarboxylic acidOne or more of them), and most of acids other than the target long-chain dibasic acid (including a heteropolyacid and a long-chain dibasic acid having a carbon chain length different from that of the fermentation substrate). The heteropolyacids include, but are not limited to, the formula R2-COOH, wherein said R is selected from the group consisting of2Is CH3(CH2)n-, n is 8 to 16. ) Dissolved in a solvent to be separated from the target long-chain dibasic acid. In the recrystallization process, the crude long-chain dibasic 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 dibasic acid is also dissolved in the solvent. The solvent containing the impurities, the heteropolyacid and the long-chain dibasic acid (including the long-chain dibasic acid with the same carbon chain length as the fermentation substrate and the long-chain dibasic acid with the same carbon chain length as the fermentation substrate) is collectively called as 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 a large amount of solvent.
Further, the recovery of a large amount of solvent may be carried out by a method known in the art, such as evaporation or distillation. Further, the solvent includes: one or more of water, alcohols, organic monoacids, ketones, ethers, esters and benzene; more preferably one of methanol, ethanol, isopropanol, n-butanol, acetic acid, acetone, diethyl ether, ethyl acetate, butyl acetate and toluene.
Preferably, hydrochloric acid and/or sulfuric acid may be used for the "acidified crystallization" in (3). Preferably, the acidification crystallization is to adjust the pH end point to 2-5 by acid. It should be understood that: optionally, the fermentation broth is directly subjected to acidification crystallization. Optionally, before acidification and crystallization, removing thallus in the fermentation liquid by centrifugation or membrane filtration to obtain clear dibasic acid solution. Whether the activated carbon decolorization step is carried out before acidification and crystallization can be selected according to the condition of the diacid clear liquid.
Method of treatment of a mixture comprising long chain dibasic acids according to any of the preceding claims, the composition of the mixture comprising long chain dibasic acids comprising at least: effective acids including long chain dibasic acids (including long chain dibasic acids having a carbon chain length equal to that of the fermentation substrate and long chain dibasic acids having a carbon chain length different from that of the fermentation substrate). Further, the effective acid comprises long-chain dibasic acid and heteropolyacid.
Further, the mixture comprising long chain dibasic acids comprises: effective acid and pigment. Still further, the mixture comprising long chain dibasic acids comprises: effective acid, cell tissue of fermenting microorganism, and pigment. Mixtures containing long chain diacids may also include very small amounts of water. The content of said pigments is generally between 1 and 20% by weight, said percentages being percentages of the dry matter of the mixture comprising long-chain diacids. The content of said cellular tissue is generally between 1 and 20% by weight, said percentage being the percentage of dry matter of the mixture comprising long-chain diacids.
Further, the long-chain dibasic acid in the effective acid is represented by the general formula HOOC-R1-COOH, wherein said R is selected from the group consisting of1Is- (CH)2)m-and 8. ltoreq. m.ltoreq.16;
further, the effective acid accounts for 30-90% of the dry matter of the mixture containing the long-chain dibasic acid, and the mass percentage of the effective acid is generally considered as follows: the higher the effective acid content, the more advantageous the treatment process of the invention. In general, the effective acid content may be 50 wt% or more, 55 wt% or more, 60 wt% or more, 65 wt% or more, 70 wt% or more, and the like, based on the dry matter of the mixture containing the long-chain dibasic acid. Of course, it may be 50 wt% or less.
Further, the mass of the long-chain dibasic acid in the effective acid is 0.1 times or more, preferably 0.5 times or more, and preferably 1 time or more of the mass of the heteropolyacid. The above-mentioned mass ratio characteristic is one of the most important characteristics that the composition of a mixture containing a long-chain dibasic acid is different from that of a raw fermentation broth of a long-chain dibasic acid. The fermentation liquor is mainly long-chain dibasic acid (the mass of the long-chain dibasic acid accounts for at least 90 wt% of the total mass of the acid) with the same carbon number as that of the substrate.
Further, n-butanol may be additionally added during the butylation reaction in step (1).
Further, during the butylation reaction in step (1), the catalyst can be supplemented.
The process according to any of the above, wherein the n-butanol is added in an amount of 0.2 to 3 times, preferably 0.5 to 3 times, more preferably 1 to 2 times the mass of the effective acid.
The method of any one of the above, the catalyst comprising: one or more of concentrated sulfuric acid, sodium bisulfate, p-toluenesulfonic acid monohydrate and tetrabutyl titanate; preferably, the catalyst comprises: one or more of p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate and concentrated sulfuric acid; more preferably, the catalyst comprises: p-toluenesulfonic acid monohydrate, concentrated sulfuric acid; still more preferably, the catalyst is p-toluenesulfonic acid monohydrate. Preferably, the mass fraction of the concentrated sulfuric acid is more than or equal to 70%, preferably more than or equal to 90%.
The process according to any one of the preceding claims, wherein the total amount of catalyst used is from 1 to 10%, preferably from 3 to 8%, more preferably from 3 to 7% of the mass of the effective acid.
The process according to any one of the preceding claims, the temperature of the butylation reaction is 50-180 ℃; and/or the butyl esterification time is 3-15 h;
preferably, the temperature of the butylation reaction is 80-150 ℃; and/or the butylation time is preferably 5 to 15 h. More preferably, the temperature of the butylation reaction is 100-130 ℃; and/or the butyl esterification time is 7-13 h. The temperature of butyl esterification is controlled in a reasonable area, so that a better butyl esterification effect can be realized; both too low and too high temperatures are detrimental to the butylation reaction. The temperature is the liquid phase temperature in the esterification apparatus.
According to any one of the above processes, n-butanol is recovered before the product after the butylation reaction is washed with a lye. The means for recovering n-butanol is preferably distillation. Further preferably, distillation under reduced pressure is carried out.
Further, the temperature of the reduced pressure distillation is 50 to 180 ℃, preferably 80 to 160 ℃, more preferably 100 ℃ to 150 ℃.
Further, the pressure of the reduced pressure distillation is 1 to 10kPa, preferably 2 to 8kPa, more preferably 2 to 5 kPa.
And further, the time of the reduced pressure distillation is 2 to 12 hours, preferably 3 to 10 hours, and more preferably 4 to 8 hours.
The method according to any one of the above, in step (2), the alkali in the alkali liquor comprises one or more of sodium hydroxide, sodium bicarbonate and sodium carbonate, preferably sodium bicarbonate or sodium carbonate, and more preferably sodium carbonate. The lye is preferably an aqueous solution of the abovementioned bases.
Further, the mass fraction of the alkali in the alkali liquor is 1-20 wt%, preferably 3-10 wt%, and more preferably 4-6 wt%.
The method according to any of the above, wherein in step (2), the number of washing with the alkali solution may be 1, 2 or more.
According to the method described in any of the above, in the step (2), the acid value of the organic phase at the end of the alkali washing is 2mgKOH/g or less, and may be 1.5mgKOH/g or less, 1mgKOH/g or less, 0.5mgKOH/g or less, or 0.3mgKOH/g or less.
The method according to any one of the above, wherein in the step (2), the temperature of the alkali liquor washing is 0-100 ℃, preferably 50-95 ℃, and more preferably 70-90 ℃.
The method according to any of the preceding claims, wherein in step (2) the washing with lye is carried out for a period of time of from 5 to 80 minutes, preferably from 20 to 80 minutes.
The catalyst, the long-chain dibasic acid and/or the mixed acid which is not subjected to the butylation reaction and the monobutyl ester of the long-chain dibasic acid can be removed by washing with alkali liquor.
The method according to any one of the preceding claims, wherein step (2) further comprises the step of washing with saturated brine after washing with lye. To remove possible residual alkali in the organic phase. The saturated saline water is preferably saturated saline water.
The method according to any one of the above, wherein the purification by distillation in step (3) is carried out before drying over anhydrous sodium sulfate. To remove residual water from the organic phase.
The process according to any one of the preceding claims, wherein the distillation in step (3) is a reduced pressure distillation, preferably a wiped film distillation, more preferably a molecular distillation.
Further, the pressure of the main evaporator is 10-1000Pa during molecular distillation, and/or the temperature of the evaporation surface of the main evaporator is 100-250 ℃.
Furthermore, the condensation surface temperature of the main evaporator for molecular distillation is-10 to 50 ℃, preferably-5 to 30 ℃, and more preferably-5 to 5 ℃.
Further, the scraper rotation speed of the main evaporator for molecular distillation is 200-.
Further, the temperature of the feed inlet of the molecular still is 20-100 ℃, preferably 25-60 ℃, and more preferably 25-40 ℃.
Further, the molecular distillation comprises the following steps:
(A) controlling the pressure of the main evaporator to be 300-1000Pa, and collecting fraction 1 when the temperature of the evaporation surface of the main evaporator of the molecular distillation main evaporator is 100-160 ℃;
(B) controlling the pressure of the main evaporator to be 10-200Pa, and collecting fraction 2 when the temperature of the evaporation surface of the molecular distillation main evaporator is 150-250 ℃ to obtain the long-chain dibutyl dibasic acid mixture.
Said fraction 1 collected in step (A) comprises n-butanol and butylates of heteropolyacids.
Fraction 2 collected in step (B) comprises: any of C10-C18 long-chain dibutyl dibasic acid.
Preferably, the pressure of the main evaporator for molecular distillation in the step (A) is 400-800Pa, and/or the temperature of the evaporation surface of the main evaporator for molecular distillation in the step (A) is 130-160 ℃;
more preferably, the pressure of the main evaporator of the molecular distillation in the step (A) is 500-700Pa, and/or the temperature of the evaporation surface of the main evaporator of the molecular distillation in the step (A) is 140-160 ℃.
Preferably, the pressure of the main evaporator for molecular distillation in the step (B) is 10-200Pa, and/or the temperature of the evaporation surface of the main evaporator for molecular distillation in the step (B) is 160-220 ℃;
more preferably, the pressure of the main evaporator of the molecular distillation in the step (B) is 50-150Pa, and/or the temperature of the evaporation surface of the main evaporator of the molecular distillation in the step (B) is 170-200 ℃.
The method according to any one of the above, wherein the mixture of the long-chain dibutyl dibasic acid ester is a mixture of any several of dibutyl dibasic acid esters with 10-18 carbon atoms.
The method according to any of the above claims, wherein the mixture comprising the long chain dicarboxylic acid is dried before the butylation. Drying to a moisture content of 5 wt% or less, preferably 3 wt% or less.
Still further, the temperature of the drying is 80 to 130 ℃, preferably 90 to 120 ℃, more preferably 110 ℃.
Still further, the drying time is 1 to 8 hours, preferably 2 to 5 hours, more preferably 2.5 to 4 hours.
Before the step (1), the mixture containing the long-chain dibasic acid is dried, and the main purpose of the drying is to remove water possibly existing in the mixture containing the long-chain dibasic acid, so that the esterification rate in the butyl esterification process is increased.
The invention also provides a mixture of the long-chain dibasic acid dibutyl ester, which is prepared by using the method for treating the mixture containing the long-chain dibasic acid in the process of extracting and refining the long-chain dibasic acid fermentation liquor.
The invention also provides a long-chain dibutyl glycol mixture and application thereof in a cold-resistant plasticizer. The polymer species used include: polyvinyl chloride, cellulose nitrate, ethyl cellulose, synthetic rubber, and other resins. The cold-resistant composite material is particularly suitable for manufacturing cold-resistant wire and cable materials, preservative films, artificial leather, films, conveyor belts, plates, sheets and the like. The mixture of the long-chain dibutyl dibasic acid can be used together with any one or more of a phthalate plasticizer, a vegetable oil-based plasticizer and a polyester plasticizer. Further, the phthalate plasticizer includes dioctyl phthalate (DOP), dibutyl phthalate (DBP). The vegetable oil-based plasticizer comprises plasticizer synthesized from natural oil (such as castor oil, soybean oil, etc.) and fatty acid (mainly composed of fatty acid with eighteen carbon atoms) obtained by processing glycerol. The polyester plasticizer comprises a linear high molecular polymer obtained by the polycondensation reaction of dihydric alcohol or polyhydric alcohol and dibasic acid or polybasic acid.
The invention has the beneficial effects that:
1. the dibutyl long-chain dibasic acid mixture obtained by carrying out butylation reaction and purification on the mixture containing the long-chain dibasic acid has low chroma, can be directly applied to a cold-resistant plasticizer, and can effectively improve the low-temperature flexibility of the polymer. The mixture containing the long-chain dicarboxylic acid discharged in the process of extracting and refining the long-chain dicarboxylic acid by using the long-chain dicarboxylic acid fermentation liquor is effectively utilized, and the waste is avoided.
2. The method for treating the mixture containing the long-chain dicarboxylic acid in the process of extracting and refining the long-chain dicarboxylic acid fermentation liquor is suitable for industrial large-scale production, has low requirement on equipment, is simple and convenient to operate, solves the problem of treatment and reutilization of wastes in the process of producing the long-chain dicarboxylic acid, and has economic value.
Detailed Description
Acid value measurement: adopts a cold solvent method in GB/T5530-2005 'acidity and acid value determination of animal and vegetable oil'.
Gas chromatography: the Shimadzu GC-2014 gas chromatograph, Shimadzu, Japan, was used.
Platinum-cobalt chroma: and measuring the chromaticity by using a GB/T3143 platinum-cobalt method.
Plastic weight loss and thermal stability test: the test was carried out in accordance with BG/T2951.7-1997 "test methods for weight loss and thermal stability of plastics".
Impact embrittlement temperature test: the test was carried out according to GB/5T470-1985 "test method for impact embrittlement temperature of plastics".
Drying equipment: adopts a DHG-9240A type electric heating constant temperature blast drying box of Shanghai essence macro experimental equipment Co.
Molecular distillation equipment: molecular distillation equipment of Germany VTA laboratory type (VKL70-5) and FZL-15 production type molecular distillation equipment of Tianjin Junge molecular distillation equipment limited company are adopted.
A scraper distillation device: a DEA-BM-10 model experimental scraper film evaporator from Shanghai De Datian one Equipment Co., Ltd is used.
XG-C type thermal aging test box: jiangsu Qidong county test instrument factory
The mixture containing long-chain dibasic acid discharged in the process of extracting and refining DC10-DC18 by the DC10-DC18 fermentation liquor comprises:
(1) dissolving a crude product of DC10-DC18 obtained from a fermentation liquid of DC10-DC18 in a solvent, and separating out a material remained after DC10-DC18 precipitation through cooling crystallization;
or (2) the remainder of the material obtained in the step (1) after most of the solvent is recovered;
or (3) acidifying and crystallizing the fermentation liquor of DC10-DC18, extracting the acidified crystallization liquor by using a solvent, separating liquid, cooling and crystallizing an organic phase containing DC10-DC18, and separating out the material remained after DC10-DC18 precipitation;
or (4), the remainder of the material obtained in the step (3) after most of the solvent is recovered;
or (5) the long-term sediment accumulation of the long-chain dibasic acid sewage treatment plant obtains DC10-DC18 sediment.
The DC10-DC18 fermentation liquid is obtained by taking alkane with 10-18 carbon atoms, fatty acid and derivatives thereof as substrates and adopting a microbial fermentation method. The microorganism may oxidize terminal methyl group of alkane, fatty acid or fatty acid derivative to carboxyl group to produce DC10-DC 18.
Further, the mode of (1) obtaining the crude product of DC10-DC18 from the fermentation liquid of DC10-DC18 is to acidify and crystallize the fermentation liquid of DC10-DC18 and separate the precipitate of DC10-DC18, thus obtaining the crude product of long-chain dibasic acid. Optionally, the fermentation broth is directly subjected to acidification crystallization. Optionally, before acidification and crystallization, removing thallus in the fermentation liquid by centrifugation or membrane filtration to obtain clear dibasic acid solution. Whether the activated carbon decolorization step is carried out before acidification and crystallization can be selected according to the condition of the diacid clear liquid.
(1) Or (3) the separation mode is centrifugation and/or filtration.
Through the recrystallization of the step (1), most of impurities (one or two of cell tissues and pigments of the fermentation microorganisms) in the crude long-chain dibasic acid and most of acids (including the mixed acid and the carbon chain of the fermentation substrate) except the target long-chain dibasic acidLong chain diacids of varying lengths. The heteropolyacid comprises the general formula R2-COOH, wherein said R is selected from the group consisting of2Is CH3(CH2)n-, n is 8 to 16. ) Dissolved in a solvent to be separated from the target long-chain dibasic acid. In the recrystallization process, the crude long-chain dibasic 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 dibasic acid is also dissolved in the solvent. The solvent containing the impurities, the heteropolyacid and the long-chain dibasic acid (comprising the long-chain dibasic acid with the same carbon chain length as the fermentation substrate and the long-chain dibasic acid with the different carbon chain length from the fermentation substrate) is collectively called as solvent mother liquor. The mixture containing the long-chain dibasic acid in the present invention may be, for example, a solvent mother liquor.
(3) The "acidification crystallization" in (1) uses hydrochloric acid and/or sulfuric acid. And the acidification crystallization is to adjust the pH end point to 2-5 by using acid so as to crystallize DC10-DC 18.
The above-mentioned recovery of a large amount of solvent adopts evaporation method or rectification method. The solvent comprises: any one of methanol, ethanol, isopropanol, n-butanol, acetic acid, acetone, diethyl ether, ethyl acetate, butyl acetate and toluene.
Example 1 of purification of fermentation liquid of DC10-DC18
The method comprises the following steps:
(1) extraction: heating any one of fermentation liquors of DC10-DC18 to 60-100 ℃, centrifuging to remove thalli, adding 0.05-5% (volume percentage of the clear liquor) of activated carbon into the obtained clear liquor for decoloring, filtering to remove the activated carbon, heating the decolored liquor to 50-100 ℃, adjusting the pH to 3-4 for acidification and crystallization, and separating to obtain a crude product of DC10-DC 18;
(2) dissolving the crude product of DC10-DC18 in an acetic acid solution with the mass fraction of more than 90%, decoloring with activated carbon or not, cooling, crystallizing and separating to obtain a DC10-DC18 product and a solvent mother liquor;
(3) acetic acid in the solvent mother liquor is recycled after being recycled by a rectifying tower, and the tower bottom material is a mixture containing long-chain dibasic acid. The content of said pigments is generally between 1 and 20% by weight and the content of cellular tissue is generally between 1 and 20% by weight of the dry matter of the mixture.
Example 2 of extraction and purification of fermentation liquid of DC10-DC18
The method comprises the following steps:
(1) extraction: heating any one of fermentation liquors of DC10-DC18 to 60-100 ℃, centrifuging to remove thalli, adding 0.05-5% (volume percentage of the clear liquor) of activated carbon into the obtained clear liquor for decoloring, filtering to remove the activated carbon, heating the decolored liquor to 50-100 ℃, adjusting the pH of the decolored liquor to 3-4, and carrying out acidification and crystallization to obtain a crude product of DC10-DC 18;
(2) and (3) extracting the crude products of DC10-DC18 by methanol to obtain products of DC10-DC18, and recovering water from residues to obtain a mixture containing long-chain dibasic acid. The content of said pigments is generally between 1 and 20% by weight and the content of cellular tissue is generally between 1 and 20% by weight of the dry matter of the mixture.
Example 1
Taking a DC12 (dodecanedioic acid) fermentation liquor, extracting and refining DC12, and then drying a mixture (extraction and refining example 1) containing long-chain dibasic acid at 110 ℃ until the water content is 1 wt% to obtain 1.626kg of dry matter, wherein the effective acid content in the dry matter is 81.34 wt%, the content of the long-chain dibasic acid (the components of DC10, DC11, DC12, DC13, DC14 and DC15) is 71.76%, and the content of the mixed acid is 9.58%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 7.5: 1.
The above dry matter was charged into a 5L reactor, while adding 1.25kg of n-butanol and 58g of p-toluenesulfonic acid monohydrate. Refluxing and esterifying for 5h at the liquid phase temperature of 120 ℃, separating 460g of mixed solution of n-butanol and water, and detecting the reaction solution by acid value to obtain the esterification rate of 60.2%. And adding 500g of n-butanol, continuously refluxing and esterifying for 3 hours at 120 ℃, separating 348g of mixed solution of the n-butanol and water, measuring the acid value of the reaction solution, and calculating the esterification rate.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 130 ℃, the unreacted n-butanol is recovered by reduced pressure distillation, and the distillation time is 4 h.
While the temperature was kept at 85 ℃, 300g of a 5.65 wt% aqueous solution of sodium carbonate was added to the remaining organic phase by distillation under reduced pressure, and the mixture was stirred for 25 minutes. Keeping the temperature at 85 ℃ and standing for layering, and separating out a lower water phase. Repeating the alkali washing process: the organic phase was washed once more with 300g of a 5.65% strength by weight aqueous sodium carbonate solution, while maintaining the temperature at 85 ℃. The acid value of the organic phase was determined to be 0.15 mgKOH/g. Then drying the mixture by anhydrous sodium sulfate and filtering the dried mixture to obtain a dark brown crude mixture of the long-chain dibutyl glycol.
Distilling the dark brown crude mixture of the long-chain dibutyl dibasic acid by a molecular distiller. And (3) vacuumizing and raising the temperature to perform molecular distillation under the conditions that the temperature of a feed inlet is 29 ℃, the temperature of a condensation surface of a main evaporator is 0 ℃ and the scraper rotating speed of the main evaporator is 295 rpm. Under the conditions that the vacuum degree is 550Pa and the temperature of an evaporation surface of a main evaporator is 145 ℃, the feeding speed is controlled to be 1kg/h, and 85g of low boiling fraction is collected. Under the conditions that the vacuum degree is 120Pa and the temperature of an evaporation surface of a main evaporator is 180 ℃, the feeding speed is controlled to be 0.5KG/h, product fractions are collected to be light yellow oily substances, and a mixture 1.292KG of long-chain binary dibutyl esters is obtained (the components are dibutyl sebacate, dibutyl undecanoate, dibutyl dodecanoate, dibutyl tridecanoate, dibutyl tetradecanoate and dibutyl pentadecate). And detecting the platinum-cobalt chromaticity and the acid value of the mixture of the long-chain dibutyl dibasic acid.
Example 2
Taking a DC13 (tridecanedioic acid) fermentation liquor, extracting and refining DC13, and then drying a mixture (extraction and refining example 1) containing long-chain dibasic acid at 110 ℃ until the water content is 1 wt% to obtain 1.205kg of dry matter, wherein the effective acid content is 73.18 wt%, the long-chain dibasic acid content is 62.35% (comprising DC11, DC12, DC13, DC14 and DC15), and the content of the heteropolyacid is 10.83%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 5.8:15.8: 1.
The above dry matter was charged into a 5L reactor, to which 1.755kg of n-butanol and 51g of p-toluenesulfonic acid monohydrate were simultaneously added. Refluxing and esterifying at 125 deg.C for 7h to obtain mixed solution 582g of n-butanol and water, detecting the acid value of the reaction solution, and calculating the esterification rate.
Recovering unreacted n-butanol by vacuum distillation under the conditions of vacuum degree of 3kPa and liquid phase temperature of 135 deg.C, and distilling for 5 h.
The residual organic phase distilled under reduced pressure was then subjected to alkaline water washing. 290g of 5.01 wt% aqueous sodium carbonate solution was added while keeping the liquid phase temperature at 90 ℃ and stirred for 20 minutes. Standing at 90 deg.C for layering, and separating lower water phase. Repeating the alkali washing process: the organic phase was washed twice more with 290g of a 5.01 wt% aqueous sodium carbonate solution, while the temperature of the liquid phase was maintained at 90 ℃. The acid value of the organic phase was determined to be 0.09 mgKOH/g. The organic phase was washed once with 300g of saturated brine, then dried over anhydrous sodium sulfate and filtered to give a crude dark brown mixture of long-chain dibutyl glycol.
And (3) distilling and purifying the dark brown crude mixture of the long-chain dibutyl dibasic acid by a molecular distiller. And (3) vacuumizing and raising the temperature to perform molecular distillation under the conditions that the temperature of a feed inlet is 35 ℃, the temperature of a condensation surface of a main evaporator is-5 ℃ and the rotating speed of a scraper of the main evaporator is 300 rpm. Under the conditions that the vacuum degree is 500Pa and the temperature of an evaporation surface of a main evaporator is 140 ℃, the feeding speed is controlled to be 1kg/h, and 68g of low boiling fraction is collected. Under the conditions that the vacuum degree is 130Pa and the temperature of an evaporation surface of a main evaporator is 190 ℃, the feeding speed is controlled to be 0.5kg/h, product fractions and light yellow oily substances are collected, and a mixture 846G of the long-chain binary dibutyl ester is obtained (the mixture comprises the undecyl binary dibutyl ester, the dodecyl binary dibutyl ester, the tridecyl binary dibutyl ester, the tetradecyl binary dibutyl ester and the pentadecyl binary dibutyl ester). And detecting the platinum-cobalt chromaticity and the acid value of the mixture of the long-chain dibutyl dibasic acid.
Example 3
Taking a DC11 (undecanedioic acid) fermentation broth, extracting and refining DC11, and then drying a mixture (extraction and refining example 1) containing long-chain dibasic acid at 110 ℃ until the water content is 1 wt% to obtain 1.931kg of dry matter, wherein the dry matter contains 78.04 wt% of effective acid, 51.94% of long-chain dibasic acid (the components are DC10, DC11, DC12, DC13, DC14 and DC15), and the content of mixed acid is 26.1%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 2: 1.
The above dry matter was charged into a 5L reactor, while adding 1.855kg of n-butanol and 60g of 98% concentrated sulfuric acid. Refluxing and esterifying at the liquid phase temperature of 118 deg.C for 4h to obtain 665g mixed solution of n-butanol and water, and detecting the acid value of the reaction solution to obtain 68.9% esterification rate. Adding 700g of n-butanol, continuously refluxing and esterifying for 3h at 120 ℃, separating 477g of a mixed solution of the n-butanol and water, and calculating the esterification rate of the reaction solution by acid value measurement.
Recovering unreacted n-butanol by vacuum distillation under the conditions of vacuum degree of 2.5kPa and liquid phase temperature of 132 deg.C, and distilling for 5 h.
The residual organic phase distilled under reduced pressure was then subjected to alkaline water washing. 400g of a 4.78 wt% aqueous solution of sodium carbonate was added while keeping the liquid phase temperature at 80 ℃ and stirred for 30 minutes. Standing at 80 deg.C for layering, and separating lower water phase. Repeating the alkali washing process: the organic phase was washed once more with 400g of a 4.78% by weight aqueous sodium carbonate solution, while the temperature of the liquid phase was maintained at 80 ℃. The acid value of the organic phase was determined to be 0.19 mgKOH/g. The organic phase was washed once with 400g of saturated brine, then dried over anhydrous sodium sulfate and filtered to give a crude dark brown mixture of long-chain dibutyl glycol.
And (3) distilling and purifying the dark brown crude mixture of the long-chain dibutyl dibasic acid by a molecular distiller. The molecular distillation was carried out by evacuating and raising the temperature under the conditions that the temperature of the feed port was 30 ℃, the temperature of the condensation surface of the main evaporator was 0 ℃ and the scraper rotation speed of the main evaporator was 305 rpm. Under the conditions that the vacuum degree is 550Pa and the temperature of an evaporation surface of a main evaporator is 145 ℃, the feeding speed is controlled to be 1kg/h, and 80g of low boiling fraction is collected. Under the conditions that the vacuum degree is 100Pa and the temperature of an evaporation surface of a main evaporator is 178 ℃, the feeding speed is controlled to be 0.5KG/h, and product fractions, light yellow oily substances and a mixture of long-chain binary dibutyl esters are collected, wherein the mixture comprises 1.331KG (the composition is dibutyl sebacate, dibutyl undecanoate, dibutyl dodecanoate, dibutyl tridecanoate, dibutyl tetradecanoate and dibutyl pentadecate). And detecting the platinum-cobalt chromaticity and the acid value of the mixture of the long-chain dibutyl dibasic acid.
Example 4
The same as example 3 except that in this example 4, 60g of p-toluenesulfonic acid monohydrate was used as the catalyst.
Example 5
Taking a DC12 (dodecanedioic acid) fermentation liquor, extracting and refining DC12, and then drying a mixture (extraction and refining example 1) containing long-chain dibasic acid at 110 ℃ until the water content is 1 wt% to obtain 1.811kg of dry matter, wherein the effective acid content is 74.97 wt%, the long-chain dibasic acid content is 63.06% (comprising DC10, DC11, DC12, DC13, DC14 and DC15), and the content of the mixed acid is 11.91%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 5.3: 1.
The above dry matter was charged into a 5L reactor, while adding 1.785kg of n-butanol and 40g of p-toluenesulfonic acid monohydrate. Refluxing and esterifying at 120 deg.C for 5 hr to obtain 588g of mixed solution of n-butanol and water, and detecting the acid value of the reaction solution to obtain esterification rate of 58.9%. Then 600g of n-butanol and 40g of 98% concentrated sulfuric acid are added, reflux esterification is carried out for 3 hours at 125 ℃, 495g of mixed liquid of the n-butanol and the water is separated, and the esterification rate is calculated by measuring the acid value of the reaction liquid.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 130 ℃, the unreacted n-butanol is recovered by reduced pressure distillation, and the distillation time is 4 h.
The residual organic phase distilled under reduced pressure was then subjected to alkaline water washing. 350g of 5.46 wt% aqueous sodium carbonate solution was added while keeping the liquid phase temperature at 85 ℃ and stirred for 25 minutes. Standing at 85 deg.C for layering, and separating lower water phase. Repeating the alkali washing process: the organic phase was washed twice more with 350g of a 5.46% by weight aqueous sodium carbonate solution, while the temperature of the liquid phase was maintained at 85 ℃. The acid value of the organic phase was determined to be 0.05 mgKOH/g. The organic phase was washed once with 350g of saturated brine, then dried over anhydrous sodium sulfate and filtered to give a crude dark brown mixture of long-chain dibutyl glycol.
And (3) distilling and purifying the dark brown crude mixture of the long-chain dibutyl dibasic acid by a molecular distiller. And (3) vacuumizing and raising the temperature to perform molecular distillation under the conditions that the temperature of a feed inlet is 35 ℃, the temperature of a condensation surface of a main evaporator is 0 ℃ and the scraper rotating speed of the main evaporator is 300 rpm. Under the conditions that the vacuum degree is 550Pa and the temperature of an evaporation surface of a main evaporator is 145 ℃, the feeding speed is controlled to be 1kg/h, and 67g of low boiling fraction is collected. Under the conditions that the vacuum degree is 120Pa and the temperature of an evaporation surface of a main evaporator is 180 ℃, the feeding speed is controlled to be 0.5KG/h, product fractions and light yellow oily substances are collected, and a mixture of long-chain binary dibutyl esters is obtained, wherein the mixture comprises 1.465KG of dibutyl sebacate, dibutyl undecanoate, dibutyl dodecanoate, dibutyl tridecanoate, dibutyl tetradecanoate and dibutyl pentadecate. And detecting the platinum-cobalt chromaticity and the acid value of the mixture of the long-chain dibutyl dibasic acid.
Example 6
Taking a DC10 (dodecanedioic acid) fermentation broth, extracting and refining DC10, and then drying a mixture (extraction and refining example 1) containing long-chain dibasic acid at 110 ℃ until the water content is 1 wt% to obtain 1.536kg of dry matter, wherein the effective acid content is 53.03 wt%, the long-chain dibasic acid content is 35.12% (the compositions are DC10, DC11, DC12, DC13 and DC14), and the content of the mixed acid is 17.91%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 2: 1.
The above dry matter was charged into a 5L reactor, while adding 1.2kg of n-butanol and 55g of p-toluenesulfonic acid monohydrate. Refluxing and esterifying at 120 deg.C for 5 hr to obtain a mixture of n-butanol and water 401g, and detecting the acid value of the reaction solution to obtain esterification rate of 55%. Adding 490g of n-butanol, continuously refluxing and esterifying for 3h at 120 ℃, separating 308g of a mixed solution of n-butanol and water, measuring the acid value of the reaction solution, and calculating the esterification rate.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 130 ℃, the unreacted n-butanol is recovered by reduced pressure distillation, and the distillation time is 4 h.
While the temperature was kept at 85 ℃, 300g of a 5.88 wt% aqueous solution of sodium carbonate was added to the remaining organic phase by distillation under reduced pressure, and the mixture was stirred for 25 minutes. Keeping the temperature at 85 ℃ and standing for layering, and separating out a lower water phase. Repeating the alkali washing process: the organic phase is washed once more with 300g of a 5.88% strength by weight aqueous sodium carbonate solution, while the temperature is maintained at 85 ℃. The acid value of the organic phase was determined to be 0.12 mgKOH/g. Then drying the mixture by anhydrous sodium sulfate and filtering the dried mixture to obtain a dark brown crude mixture of the long-chain dibutyl glycol.
Distilling the dark brown crude mixture of the long-chain dibutyl dibasic acid by a molecular distiller. And (3) vacuumizing and raising the temperature to perform molecular distillation under the conditions that the temperature of a feed inlet is 32 ℃, the temperature of a condensation surface of a main evaporator is 0 ℃ and the scraper rotating speed of the main evaporator is 300 rpm. Under the conditions that the vacuum degree is 450Pa and the temperature of an evaporation surface of a main evaporator is 140 ℃, the feeding speed is controlled to be 1kg/h, and 88g of low boiling fraction is collected. Under the conditions that the vacuum degree is 100Pa and the temperature of an evaporation surface of a main evaporator is 178 ℃, the feeding speed is controlled to be 0.5kg/h, product fractions and light yellow oily substances are collected, and a mixture 881G (with the composition of dibutyl sebacate, dibutyl undecanoate, dibutyl dodecanoate, dibutyl tridecanoate and dibutyl tetradecanoate) of long-chain dibutyl dibasic acid is obtained. And detecting the platinum-cobalt chromaticity and the acid value of the mixture of the long-chain dibutyl dibasic acid.
Example 7
The only difference was that in example 7, a mixture containing a long-chain dibasic acid after extraction purification of DC11 was used (as in example 1). The mixture containing the long chain dibasic acid was dried at 110 ℃ to a water content of 1 wt% to give 1.536kg of dry matter with an effective acid content of 78.04 wt%, a long chain dibasic acid content of 51.94% (composition DC10, DC11, DC12, DC13, DC14 and DC15) and a heteropolyacid content of 26.1%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 2: 1. The remaining procedure was the same as in example 6.
Example 8(2000L reactor)
Taking a DC12 (dodecanedioic acid) fermentation liquor, extracting and refining DC12, and then drying a mixture (extraction and refining example 1) containing long-chain dibasic acid at 110 ℃ until the water content is 1 wt% to obtain 604kg of dry matter, wherein the effective acid content is 85.16 wt%, the long-chain dibasic acid content is 67.99% (comprising DC10, DC11, DC12, DC13, DC14 and DC15), and the content of the mixed acid is 17.17%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 4: 1.
The above dry matter was charged into a 2000L reactor, while 460kg of n-butanol and 21.5kg of p-toluenesulfonic acid monohydrate were added. Refluxing and esterifying at 120 deg.C for 8 hr to obtain a mixture of n-butanol and water (175 kg), and detecting the acid value of the reaction solution to obtain esterification rate of 61%. Adding 150kg of n-butanol, continuously refluxing and esterifying at 120 ℃ for 5h, separating 135kg of mixed solution of n-butanol and water, measuring the acid value of the reaction solution, and calculating the esterification rate.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 135 ℃, recovering unreacted n-butanol by reduced pressure distillation for 4 h.
While the temperature was maintained at 90 ℃, 110kg of a 5.46 wt% aqueous solution of sodium carbonate was added to the remaining organic phase by distillation under reduced pressure, and the mixture was stirred for 30 minutes. Keeping the temperature at 90 ℃ and standing for layering, and separating out a lower water phase. Repeating the alkali washing process: the organic phase was washed once more with 100kg of a 5.46% strength by weight aqueous sodium carbonate solution, while maintaining the temperature at 90 ℃. The acid value of the organic phase was determined to be 0.09 mgKOH/g. Then drying the mixture by anhydrous sodium sulfate and filtering the mixture to obtain a dark brown crude mixture of the long-chain dibutyl dibasic acid.
Distilling the dark brown crude mixture of the long-chain dibutyl dibasic acid by a molecular distiller. And (3) vacuumizing and raising the temperature to perform molecular distillation under the conditions that the temperature of a feed inlet is 35 ℃, the temperature of a condensation surface of a main evaporator is 0 ℃ and the scraper rotating speed of the main evaporator is 300 rpm. Under the conditions that the vacuum degree is 500Pa and the temperature of an evaporation surface of a main evaporator is 145 ℃, the feeding speed is controlled to be 150kg/h, and 30kg of low boiling point fraction is collected. Under the conditions that the vacuum degree is 110Pa and the temperature of an evaporation surface of a main evaporator is 180 ℃, the feeding speed is controlled to be 75kg/h, product fractions and light yellow oily substances are collected, and 482kg of a mixture of the long-chain dibutyl dibasic acid and the long-chain dibutyl dibasic acid is obtained (the composition of the mixture is dibutyl sebacate, dibutyl undecanoate, dibutyl dodecanoate, dibutyl tridecanoate, dibutyl tetradecanoate and dibutyl pentadecanoate). And detecting the platinum-cobalt chromaticity and the acid value of the mixture of the long-chain dibutyl dibasic acid.
Example 9 (ordinary vacuum distillation)
Taking a DC12 (dodecanedioic acid) fermentation liquor, extracting and refining DC12, and then drying a mixture (extraction and refining example 1) containing long-chain dibasic acid at 110 ℃ until the water content is 1 wt% to obtain 1.626kg of dry matter, wherein the effective acid content is 81.34 wt%, the long-chain dibasic acid content is 71.76% (the components are DC10, DC11, DC12, DC13, DC14 and DC15), and the content of the mixed acid is 9.58%. The mass ratio of the long-chain dibasic acid to the heteropolyacid is 7.5: 1.
The above dry matter was charged into a 5L reactor, while adding 1.25kg of n-butanol and 58g of p-toluenesulfonic acid monohydrate. Refluxing and esterifying for 5h at the liquid phase temperature of 120 ℃, separating 460g of mixed solution of n-butanol and water, and detecting the reaction solution by acid value to obtain the esterification rate of 60.2%. And adding 500g of n-butanol, continuously refluxing and esterifying for 3 hours at 120 ℃, separating 348g of mixed solution of the n-butanol and water, measuring the acid value of the reaction solution, and calculating the esterification rate.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 130 ℃, the unreacted n-butanol is recovered by reduced pressure distillation, and the distillation time is 4 h.
While the temperature was kept at 85 ℃, 300g of a 5.65 wt% aqueous solution of sodium carbonate was added to the remaining organic phase by distillation under reduced pressure, and the mixture was stirred for 25 minutes. Keeping the temperature at 85 ℃ and standing for layering, and separating out a lower water phase. Repeating the alkali washing process: the organic phase was washed once more with 300g of a 5.65% strength by weight aqueous sodium carbonate solution, while maintaining the temperature at 85 ℃. The acid value of the organic phase was determined to be 0.15 mgKOH/g. Then drying the mixture by anhydrous sodium sulfate and filtering the dried mixture to obtain a dark brown crude mixture of the long-chain dibutyl glycol.
The crude dark brown mixture of dibutyl long chain dibasic acid is distilled under reduced pressure. Under the conditions that the vacuum degree is 650Pa and the temperature of the evaporation surface of the main evaporator is 175-210 ℃, 86g of low boiling fraction is collected. Under the conditions that the vacuum degree is 260Pa and the temperature of an evaporation surface of the main evaporator is 235-250 ℃, collecting product fractions and deep yellow oily substances to obtain a mixture of long-chain binary dibutyl esters of 1.19KG (the components are dibutyl sebacate, dibutyl undecylate, dibutyl dodecacarbonate, dibutyl tridecanoate, dibutyl tetradecanoate and dibutyl pentadecanoate). And detecting the platinum-cobalt chromaticity and the acid value of the mixture of the long-chain dibutyl dibasic acid.
Table 1: table of results of tests of esterification rate, platinum-cobalt chromaticity of mixture of long chain dibutyl dibasic acid, and acid value
As is clear from Table 1, the mixed long-chain dibasic acid of the present invention has a high esterification rate. The obtained mixed long-chain dibasic acid dibutyl ester has low chroma, and the low chroma ester can better meet the requirements of light-color high polymer materials. The method for processing the mixture containing the long-chain dibasic acid can effectively separate the long-chain dibasic acid dibutyl ester, the butyl ester compound of the mixed acid, the residual long-chain dibasic acid, the mixed acid and the impurities from the fermentation liquor to obtain the high-quality mixture of the long-chain dibasic acid dibutyl ester, is more suitable for the plasticizer of the high polymer material, and realizes the purpose of changing waste into valuable.
In addition, the method for treating the mixture containing the long-chain dicarboxylic acid is completely suitable for treating the mixture containing the long-chain dicarboxylic acid in a factory level, and has great application value.
Mixed dibutyl long chain dicarboxylate for plasticizer testing:
weighing the following components: 100 parts of PVC material, 35 parts of dioctyl phthalate (DOP), 10 parts of mixed dibasic acid n-butyl ester product or DBS reference substance, 4.5 parts of dibasic lead phosphite, 0.4 part of barium stearate, 0.5 part of lubricant and 2 parts of calcium carbonate. Mixing the above components, plasticating for 5-10min at 160 + -5 deg.C in a rubber mixing machine, drawing into sheet, pressing for 15-20min in a pressure forming machine at 160 + -5 deg.C, molding to obtain test piece with thickness of 1mm, and demolding. The test piece is punched into the piece to be tested by a punch according to different testing requirements for standby. And respectively testing the ageing resistance and the low-temperature brittleness of the PVC test piece. The test results are shown in Table 2.
Table 2: PVC sheet performance test result table
The experimental results in Table 2 show that when the mixed long-chain dibutyl dibasic acid is used as a plasticizer, the destruction rate of the PVC test piece is about 50 percent at the temperature of-41 ℃, the mixed long-chain dibutyl dibasic acid can be compared favorably with DBS (dibutyl sebacate), and the low-temperature flexibility of the polymer can be effectively improved. The weight loss after aging of the PVC test piece obtained by using the mixed long-chain dibasic acid dibutyl ester as the cold-resistant plasticizer is low, only the aging weight loss of the example 9 is larger, probably because the separation can be completed only by using higher temperature in the common reduced pressure distillation, and the stability is reduced when the mixed long-chain dibasic acid butyl ester compound is partially decomposed at long-time high temperature.
The previous description of the disclosed embodiments is provided to teach any person skilled in the art how to make and use the present invention. Some conventional aspects have been simplified or omitted for the purpose of teaching the present invention. Modifications or alterations to the embodiments of the invention which achieve the objects of the invention will become apparent to those skilled in the art from the common general knowledge in the chemical arts after reading the description of the invention, and it will be understood by those skilled in the art that modifications or alterations derived from these embodiments will fall within the scope of the invention.
Claims (18)
1. A method of processing a mixture comprising a long chain dibasic acid, comprising the steps of:
and carrying out butylation reaction on the mixture containing the long-chain dibasic acid.
2. A method for processing a mixture containing long-chain dicarboxylic acid in the process of extracting and refining long-chain dicarboxylic acid fermentation liquor comprises the following steps:
(1) uniformly mixing a mixture containing long-chain dibasic acid, n-butyl alcohol and a catalyst, and carrying out a butylation reaction;
(2) washing a product after the butylation reaction with alkali liquor;
(3) distilling and purifying to obtain the mixture of the long-chain dibutyl dibasic acid.
3. The method of claim 1 or 2, the mixture comprising long chain dibasic acids comprising:
an effective acid comprising a long chain dibasic acid.
4. The method of claim 3, wherein the long chain dibasic acid is one or more of the compounds represented by the general formula HOOC-R1-COOH, wherein R is1Is- (CH)2)m-and 8. ltoreq. m.ltoreq.16.
5. The process according to claim 1 or 2, wherein the total amount of n-butanol added during the butylation reaction is 0.2-3 times the mass of the effective acid.
6. The method of claim 2, the catalyst comprising: one or more of concentrated sulfuric acid, sodium bisulfate, p-toluenesulfonic acid monohydrate and tetrabutyl titanate.
7. The method of claim 2, wherein the total amount of catalyst is 1-10% by mass of the effective acid.
8. The process according to claim 1 or 2, wherein the temperature of the butylation reaction is 50-180 ℃ and/or the butylation time is 3-15 h.
9. The process of claim 2, recovering the n-butanol before washing the product after the butylation reaction with a caustic solution.
10. The method according to claim 2, wherein the acid value of the organic phase at the end of the washing with lye of step (2) is less than 2 mgKOH/g.
11. The process of claim 2, wherein the distillation of step (3) is a reduced pressure distillation, preferably a wiped film distillation, more preferably a molecular distillation.
12. The method as claimed in claim 11, wherein the pressure of the main evaporator during the molecular distillation is 10-1000Pa, and/or the temperature of the evaporation surface of the main evaporator is 100-250 ℃.
13. The method of claim 11, wherein the temperature of the condensation surface of the primary evaporator of the molecular distillation is-10-50 ℃; and/or the scraper blade rotating speed of the main evaporator for molecular distillation is 200-400 rpm; and/or the temperature of the feed inlet of the molecular distiller is 20-100 ℃.
14. The method according to claim 11 or 12 or 13, the molecular distillation comprising the steps of:
(A) controlling the pressure of the main evaporator to be 300-1000Pa, and collecting fraction 1 when the temperature of the evaporation surface of the main evaporator of the molecular distillation main evaporator is 100-160 ℃;
(B) controlling the pressure of the main evaporator to be 10-200Pa, and collecting fraction 2 when the temperature of the evaporation surface of the molecular distillation main evaporator is 150-250 ℃ to obtain the long-chain dibutyl dibasic acid mixture.
15. The process according to claim 1 or 2, wherein the mixture comprising the long-chain dicarboxylic acid is dried to a moisture content of less than 5 wt.% before the butylation.
16. The method according to claim 2 or 14, wherein the mixture of dibutyl long chain dicarboxylate is a mixture of any of dibutyl long chain dicarboxylate having 10-18 carbon atoms.
17. A mixture of long chain dibutyl glycols characterized by: prepared using the method of any one of claims 1-16.
18. Use of a mixture of long chain dibutyl diesters according to claim 17 in cold-resistant plasticizers for polyvinyl chloride, cellulose nitrate, ethyl cellulose, rubber.
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