CN112079713A - Method for treating mixtures containing long-chain dicarboxylic acids and use thereof - Google Patents
Method for treating mixtures containing long-chain dicarboxylic acids and use thereof Download PDFInfo
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
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Abstract
The invention provides a method for processing a mixture containing long-chain dibasic acid, which comprises the step of carrying out octanesis esterification on the mixture containing the long-chain dibasic acid to obtain mixed long-chain dibasic dioctyl ester. The long-chain binary dioctyl phthalate mixture obtained by performing octyl esterification reaction and purification on the mixture containing the long-chain binary acid can be applied to synthetic ester lubricating oil base oil, and the performance of the long-chain binary dioctyl phthalate mixture can be comparable to that of the existing lubricating oil phase. The effective utilization of the mixture containing the long-chain dicarboxylic acid discharged in the process of extracting and refining the long-chain dicarboxylic acid by the long-chain dicarboxylic acid fermentation liquor is realized. The method for treating the mixture containing the long-chain dicarboxylic acid is suitable for industrial application, 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 dicarboxylic acid, and has remarkable economic value.
Description
Technical Field
The invention relates to a recycling technology of a mixture containing long-chain dibasic acid.
Background
The synthetic ester base oil has super-strong oil film protection effect. The polarity of the ester molecules can enable the ester molecules to be adsorbed on the metal surfaces to form an oil layer of an adhesion molecule oil film, and the adhesion molecule oil film capable of achieving liquid lubrication can exist between the two metal surfaces even after the engine stops working, so that the engine is protected uninterruptedly. At present, qualified internal combustion engine oil can be produced by taking pure synthetic ester oil as base oil; however, if the poly-alpha-olefin (PAO, IV base oil) is used as the base oil, a certain amount of synthetic ester oil (more than 10 percent) must be added to improve the dissolving capacity of the finished oil, improve the clean dispersing performance of the finished oil and overcome the shrinkage of the rubber sealing element caused by the PAO. Synthetic ester lubricating oils are widely used as internal combustion engine oils, compressor oils, refrigerator oils, high-speed gear oils, metal working fluids, grease base oils, and the like, and are one of the most widely used synthetic oils at present, because of their excellent lubricating properties and viscosity-temperature characteristics.
The polybasic acid synthetic ester base oil has been successfully applied to the lubrication of mechanical equipment working under boundary lubrication conditions for a long time in the industries of aviation, metallurgy, rail transit, wind power generation and the like due to the characteristics of excellent high and low temperature performance, good tribology characteristics, controllability of molecular structure, environmental friendliness and the like.
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 fermentation preparation process of the long-chain dicarboxylic acid cannot be fully utilized, so that the resource waste is caused. If the mixture containing the long-chain dibasic acid in the long-chain dibasic acid fermentation preparation process 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 esterified substance of the long-chain dibasic mixed acid. Such a process is complicated and the treatment cost is high. Therefore, the method has more important practical significance for the research of the esterification reaction (such as the octyl esterification reaction) for converting and reusing the mixture of the long-chain dibasic acid and the long-chain dibasic acid.
Disclosure of Invention
The invention provides a method for treating a mixture containing long-chain dibasic acid, which comprises the following steps: and (3) carrying out an octyl esterification reaction on the mixture containing the long-chain dibasic acid to synthesize the mixture of the long-chain dibasic dioctyl ester. The technology for esterifying the mixture containing the long-chain dibasic acid is suitable for industrial application, solves the problem of resource waste that the mixture of the long-chain dibasic acid discharged in the process of extracting and refining the long-chain dibasic acid fermentation liquor cannot be effectively utilized, and can be used for synthesizing products such as ester base oil and the like.
The invention provides a method for processing a mixture containing long-chain dibasic acid, which comprises the following steps: and carrying out an octyl esterification reaction on the mixture containing the long-chain dibasic acid.
Further, the processing method comprises the following steps:
(1) uniformly mixing a mixture containing long-chain dibasic acid, isooctyl alcohol and a catalyst, and carrying out an octyl esterification reaction;
(2) washing the product after the octyl esterification reaction with alkali liquor;
(3) distilling and purifying to obtain the mixture of the long-chain binary dioctyl phthalate.
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 art.
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 one or more of cell tissues and pigments of the fermentation microorganisms) in the crude long-chain dibasic acid, most of acids (including the mixed acid and the long-chain dibasic acid with the carbon chain length unequal to that of the fermentation substrate) except the target long-chain dibasic acid, wherein the mixed acid comprises but is not limited to the general formula R2-COOH, wherein said R is selected from the group consisting of2Is CH3(CH2) n-, n-8-16. ) Dissolved in a solvent to be separated from the target long-chain dibasic acid. Because the recrystallization process adopts the method of dissolving the crude long-chain dibasic acid in the solvent and then cooling (preferably controlling the temperature below 50 ℃ but higher than 20 ℃) for precipitation, the solvent also containsPart of the target long-chain dibasic acid is dissolved. 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.
The method for treating a mixture containing a long-chain dibasic acid according to any one of the above methods (hereinafter referred to as a treatment method), wherein the composition of the mixture containing a long-chain dibasic acid comprises: 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. 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.
Composition of a mixture comprising a long chain dibasic acid according to any of the above. Mixtures containing long chain diacids may also include very small amounts of water.
Further, the long-chain dibasic acid in the effective acid is represented by the general formula HOOC-R1-COOH, wherein 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 0.5 times or more, preferably 1 time or more, preferably 2 times or more, preferably 3 times or more of that of the heteropolyacid. The above 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 the composition of the original fermentation broth of the 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, isooctanol may be supplemented during the octylation reaction in step (1).
Further, during the octyl esterification reaction in the step (1), a catalyst can be supplemented.
The treatment according to any one of the above, wherein the total amount of isooctanols used is 0.2 to 3 times, preferably 0.5 to 3 times, more preferably 1 to 3 times, and still more preferably 1 to 2 times the mass of the effective acid.
The treatment process according to any one of the preceding claims, 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 concentrated sulfuric acid, paratoluenesulfonic acid monohydrate and tetrabutyl titanate; 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 treatment method according to any one of the preceding claims, wherein the total amount of catalyst used in the octylation reaction process is 1-10%, preferably 3-8%, more preferably 3-7% of the effective acid mass.
The treatment method according to any one of the above, wherein the temperature of the octylation reaction is 150-200 ℃; and/or the octyl esterification reaction time is 3-15 h;
preferably, the temperature of the octylation reaction is 155-195 ℃; and/or the octa-esterification time is preferably 5-13 h. More preferably, the temperature of the octylation reaction is 160-190 ℃; and/or the octyl esterification time is 6-9 h. The temperature of the octyl esterification is controlled in a reasonable area, so that a better octyl esterification effect can be realized; both too low and too high temperatures are detrimental to the octylation reaction. The temperature of the octyl esterification is the liquid phase temperature in the esterification equipment.
The treatment according to any of the above, wherein the isooctanol is recovered before the product after the octylation reaction is washed with a lye. The isooctanol recovery means is preferably distillation. Further preferably, distillation under reduced pressure is carried out.
Further, the temperature of the reduced pressure distillation is 180-210 ℃, preferably 190-200 ℃, and more preferably 195-200 ℃.
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 treatment method according to any one of the above items, 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 treatment method according to any of the above, wherein in the step (2), the number of washing with the alkali solution may be 1, 2 or more.
According to any of the above-mentioned processing methods, 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 treatment method according to any one of the above, wherein in the step (2), the temperature of the alkali washing is 0 to 100 ℃, preferably 50 to 95 ℃, and more preferably 70 to 90 ℃.
The treatment method according to any one of the above, wherein in the step (2), the washing time with the alkali liquor is 5 to 80 minutes, preferably 20 to 80 minutes.
The catalyst, the long-chain dibasic acid and/or the mixed acid which is not subjected to the octyl esterification reaction and the mono-octyl ester of the dibasic acid can be removed by washing with alkali liquor.
The treatment method according to any one of the above, wherein the step (2) further comprises a step of washing with a saturated brine after washing with a lye. To remove possible residual alkali in the organic phase. The saturated saline water is preferably saturated saline water.
The treatment method according to any one of the above, wherein the drying step (3) may be carried out with anhydrous sodium sulfate before the distillation purification. 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 150-260 ℃.
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 is 150-200 ℃; (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 main evaporator is 200-260 ℃ to obtain the long-chain binary dioctyl phthalate mixture.
The fraction 1 collected in step (a) comprises isooctyl alcohol and an octyl ester of a heteropolyacid.
Fraction 2 collected in step (B) comprises: any of C10-C18 long chain dioctyl 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 160-200 ℃; 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 180-200 ℃.
Preferably, the pressure of the main evaporator of the molecular distillation in the step (B) is 10-200Pa, and/or the temperature of the evaporation surface of the main evaporator of the molecular distillation in the step (B) is 210-250 ℃; 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 220-250 ℃.
The treatment method according to any one of the above, wherein the mixture of the long-chain binary dioctyl phthalate is a mixture of any several of binary dioctyl phthalate with 10-18 carbon atoms.
The treatment method according to any one of the above, wherein the mixture containing the long-chain dibasic acid is dried before being octylated. 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 ℃.
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 esterification process of the octyl phthalate is increased.
The invention also provides a mixture of the long-chain binary dioctyl phthalate, which is prepared by using the method for treating the mixture containing the long-chain binary acid.
The invention also provides a long-chain dioctyl dibasic acid mixture and application thereof in synthesizing ester base oil. Application categories include, but are not limited to: internal combustion engine oil, compressor oil, refrigerator oil, high-speed gear oil, metal working fluid, grease base oil, and the like.
The invention has the beneficial effects that:
1. the long-chain dioctyl phthalate mixture obtained by the mixture containing the long-chain dibasic acid through the octyl reaction and purification can be directly applied to the synthesis of ester base oil. The effective utilization of the discharged long-chain dicarboxylic acid in the process of extracting and refining the long-chain dicarboxylic acid fermentation liquor is realized, and the waste is avoided.
2. The method for treating the mixture containing the long-chain dicarboxylic 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 wastes in the production process of the long-chain dicarboxylic acid, and has remarkable economic value.
Detailed Description
The test methods in the examples are described below:
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.
Kinematic viscosity (40 ℃ and 100 ℃): testing was performed according to ASTM D445-17.
Viscosity index: testing was performed according to ASTM D2270.
Pour point: testing was performed according to ASTM D97.
Flash point (COC): testing was performed according to ASTM D92.
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 product and most of acids (including the heteropolyacid and the long-chain dibasic acid with unequal carbon chain length with the fermentation substrate) except the target long-chain dibasic acid are obtained, wherein the heteropolyacid comprises a general formula R2-COOH, wherein said R is selected from the group consisting of2Is CH3(CH2) n-, n-8-16. ) Dissolved in a solvent to be separated from the target long-chain dibasic acid (DC10-DC 18). 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 extraction and purification of fermentation broth DC10-DC18
(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 broth DC10-DC18
(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
DC12 extraction refining DC12 after which the mixture containing long chain dibasic acid (extraction refining example 1) was dried at 110 ℃ to a water content of 0.66 wt% to give 1.611kg of dry matter. Wherein the effective acid content is 80.91 wt%, the long-chain dibasic acid content is 71.59 wt% (the long-chain dibasic acid comprises DC10, DC12, DC11, DC13, DC14 and DC15), the heteropolyacid content is 9.32 wt%, and the mass ratio of the long-chain dibasic acid to the heteropolyacid is 7.7: 1.
The above dry matter was charged into a 5L reactor, to which were simultaneously added 1.77kg of isooctanol and 56g of p-toluenesulfonic acid monohydrate. Esterifying for 5h at the liquid phase temperature of 168 deg.C, and separating 154g water, wherein the esterification rate is 80.1% by acid value detection.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 197 ℃, unreacted isooctyl alcohol is recovered by reduced pressure distillation, and the distillation time is 5 h.
While the temperature was maintained at 90 ℃, 300g of a 5.5 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 is washed once more with 300g of a 5.5% strength by weight aqueous sodium carbonate solution, while the temperature is maintained at 90 ℃. The acid value of the organic phase was determined to be 0.13 mgKOH/g. Then the organic phase is dried by anhydrous sodium sulfate and filtered to obtain a dark brown crude mixture of the long-chain dioctyl dibasic acid.
The crude dark brown mixture of the long-chain dioctyl dibasic acid is distilled 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 30 ℃, 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 200 ℃, the feeding speed is controlled to be 1kg/h, and 105g 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 235 ℃, the feeding speed is controlled to be 0.5KG/h, product fractions are collected to be light yellow oily substances, the mixture of the long-chain binary dioctyl phthalate is obtained at 1.530KG, and the purity of the long-chain binary dioctyl phthalate is 99.64%. Platinum-cobalt chromaticity and acid value measurements were made on the mixture of long chain dioctyl dibasic acid with the results shown in table 1.
Example 2
DC13 fermentation broth was used to refine DC13, and the mixture containing long-chain dibasic acid (example 1) was dried at 110 ℃ until the water content became 0.43 wt%, yielding 1.853kg of dry matter. Wherein the content of the effective acid is 71.49 wt%, the content of the long-chain dibasic acid is 61.21 wt% (the long-chain dibasic acid comprises DC11, DC12, DC13, DC14 and DC15), the content of the heteropolyacid is 10.28 wt%, and the mass ratio of the long-chain dibasic acid to the heteropolyacid is 6.1: 1.
The above dry matter was charged into a 5L reactor while isooctanol 2.038kg and p-toluenesulfonic acid monohydrate 63.6g were added. Esterifying at 168 deg.C for 5h to obtain 171g water, and detecting the acid value of the reaction solution to obtain 79.6% esterification rate.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 200 ℃, unreacted isooctyl alcohol is recovered by reduced pressure distillation, and the distillation time is 5 h.
While the temperature was maintained at 90 ℃, 300g of a 5.5 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 is washed once more with 300g of a 5.5% strength by weight sodium carbonate solution, while the temperature is maintained at 90 ℃. The acid value of the organic phase was determined to be 0.22 mgKOH/g. Then the organic phase is dried by anhydrous sodium sulfate and filtered to obtain a dark brown crude mixture of the long-chain dioctyl dibasic acid.
The crude dark brown mixture of the long-chain dioctyl dibasic acid is distilled 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 30 ℃, 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 200 ℃, the feeding speed is controlled to be 1kg/h, and 185g 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 235 ℃, the feeding speed is controlled to be 0.5KG/h, product fractions are collected to be light yellow oily substances, the mixture of the long-chain binary dioctyl phthalate is obtained at 1.602KG, and the purity of the long-chain binary dioctyl phthalate is 99.86%. Platinum-cobalt color and acid number measurements were performed on mixtures of long chain dioctyl dibasic acids. The test results are shown in Table 1.
Example 3
DC11 fermentation broth extract refining DC11 after which the mixture containing long chain dibasic acid (extract refining example 1) was dried at 110 ℃ to a water content of 0.65 wt% to obtain 1.968kg of dry matter. Wherein the effective acid content is 78.24 wt%, the long-chain dibasic acid content is 65.98 wt% (the long-chain dibasic acid composition is DC10, DC11, DC12, DC13, DC14 and DC15), the content of the heteropolyacid is 12.26 wt%, and the mass ratio of the long-chain dibasic acid to the heteropolyacid is 5.4: 1.
The above dry matter was charged into a 5L reactor, to which were simultaneously added 2.155kg of isooctanol and 65g of p-toluenesulfonic acid monohydrate. Esterifying for 5h at the liquid phase temperature of 168 deg.C to obtain 178g of water, and detecting the acid value of the reaction solution to obtain 80.8% esterification rate.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 200 ℃, unreacted isooctyl alcohol is recovered by reduced pressure distillation, and the distillation time is 5 h.
While the temperature was maintained at 90 ℃, 300g of a 5.5 wt% sodium carbonate solution 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 is washed once more with 300g of a 5.5% strength by weight sodium carbonate solution, while the temperature is maintained at 90 ℃. The acid value of the organic phase was determined to be 0.25 mgKOH/g. Then the organic phase is dried by anhydrous sodium sulfate and filtered to obtain a dark brown crude mixture of the long-chain dioctyl dibasic acid.
The crude dark brown mixture of the long-chain dioctyl dibasic acid is distilled 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 30 ℃, 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 200 ℃, the feeding speed is controlled to be 1kg/h, and 215g 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 235 ℃, the feeding speed is controlled to be 0.5KG/h, product fractions are collected to be light yellow oily substances, the mixture of the long-chain binary dioctyl phthalate is obtained by 1.616KG, and the purity of the long-chain binary dioctyl phthalate is 99.63%. Platinum-cobalt chromaticity and acid value measurements were made on the mixture of long chain dioctyl dibasic acid with the results shown in table 1.
Example 4
Basically the same as example 3, except that in this example 4, 60g of 98% concentrated sulfuric acid was used as the catalyst.
Example 5
DC12 fermentation broth extraction refining DC12 after which the mixture containing long chain dibasic acid (extraction refining example 1) was dried at 110 ℃ to a water content of 0.61 wt%, yielding 598kg of dry matter. Wherein the content of the effective acid is 79.89 wt%, the content of the long-chain dibasic acid is 70.97 wt% (the long-chain dibasic acid comprises DC10, DC11, DC12, DC13, DC14 and DC15), the content of the heteropolyacid is 8.92 wt%, and the mass ratio of the long-chain dibasic acid to the heteropolyacid is 8: 1.
The above dry matter was charged into a 2000L reactor with 649KG of isooctanol and 21.5KG of p-toluenesulfonic acid monohydrate. Esterifying at 168 deg.C for 10h to obtain 56.3kg of water, and detecting the acid value of the reaction solution to obtain 79.0% esterification rate.
Under the conditions of vacuum degree of 2kPa and liquid phase temperature of 195 ℃, unreacted isooctyl alcohol is recovered by reduced pressure distillation, and the distillation time is 8 h.
While the temperature was maintained at 90 ℃, 100kg of 5.5 wt% sodium carbonate solution 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 is washed once more with 100kg of a 5.5% by weight sodium carbonate solution, while the temperature is maintained at 90 ℃. The acid value of the organic phase was determined to be 0.09 mgKOH/g. Then the organic phase is dried by anhydrous sodium sulfate and filtered to obtain a dark brown crude mixture of the long-chain dioctyl dibasic acid.
The crude dark brown mixture of the long-chain dioctyl dibasic acid is distilled 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 30 ℃, 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 200 ℃, the feeding speed is controlled to be 150kg/h, and 42.5kg of low boiling point fraction is collected. Under the conditions that the vacuum degree is 120Pa and the evaporation surface temperature of a main evaporator is 230 ℃, the feeding speed is controlled to be 75KG/h, product fractions are collected to be light yellow oily substances, a mixture 551KG of long-chain binary dioctyl ester is obtained, and the purity of the long-chain binary dioctyl ester is 99.67%. Platinum-cobalt chromaticity and acid value measurements were made on the mixture of long chain dioctyl dibasic acid with the results shown in table 1.
Table 1: esterification rate of octylation reaction, platinum-cobalt color of mixture of long-chain binary dioctyl phthalate, and acid value test result
The mixture containing the long-chain dicarboxylic acid is subjected to octyl esterification to synthesize the dioctyl compound of the mixed long-chain dicarboxylic acid, and the dioctyl compound can be used for synthesizing ester lubricating oil base oil. Solves the problems of resource waste and environmental pollution caused by the frequent dumping of the mixture containing the long-chain dicarboxylic acid in the fermentation process of the long-chain dicarboxylic acid. 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 binary dioctyl phthalate has good chromaticity, and meets the requirement of lubricating oil base oil on chromaticity. In addition, the method for treating the mixture containing the long-chain dicarboxylic acid is not only suitable for research and development in laboratories, but also completely suitable for treatment of the mixture containing the long-chain dicarboxylic acid in factories, and has great application value.
Table 2: performance test results for mixtures of long chain dibasic dioctyl phthalate
From the experimental results shown in Table 2, it is found that the mixed long-chain dioctyl phthalate as a lubricant base oil is superior in viscosity performance to that of an adipate base oil of Mobil (A34, A32). The pour point can be compared with that of the adipate base oil of Mobil. The flash point is higher than Mobil oil, the safety is higher, and the higher flash point reduces the volatility loss of the base oil of the lubricating oil, and delays the performance change caused by component volatilization after the base oil of the lubricating oil is used for a long time to a certain extent.
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 (14)
1. A method of processing a mixture comprising a long chain dibasic acid, comprising the steps of:
and carrying out an octyl esterification reaction on the mixture containing the long-chain dibasic acid.
2. A method of treating a mixture comprising a long chain dibasic acid comprising the steps of:
(1) uniformly mixing a mixture containing long-chain dibasic acid, isooctyl alcohol and a catalyst, and carrying out an octyl esterification reaction;
(2) washing the product after the octyl esterification reaction with alkali liquor;
(3) distilling and purifying to obtain the mixture of the long-chain binary dioctyl phthalate.
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 of the general formula HOOC-R1-COOH, wherein R is selected from the group consisting of1Is- (CH)2) m-is more than or equal to 8 and less than or equal to 16.
4. The method of claim 1 or 2, wherein the total amount of isooctyl alcohol used in the octyization reaction is 0.2 to 3 times the effective acid mass; and/or the total dosage of the catalyst in the octyl esterification reaction process is 1-10% of the mass of the effective acid.
5. The method of claim 2, the catalyst comprising: one or more of concentrated sulfuric acid, sodium bisulfate, p-toluenesulfonic acid monohydrate and tetrabutyl titanate.
6. The process according to claim 1 or 2, wherein the temperature of the octylation reaction is 150-200 ℃; and/or the octyl esterification reaction time is 3-15 h.
7. The method according to claim 2, wherein in the step (2), isooctanol is recovered before the product after the octylation reaction is washed with a lye; and/or, the acid value of the organic phase reaches below 2mgKOH/g when the washing of the alkali liquor in the step (2) is finished.
8. 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.
9. The method of claim 8, wherein the pressure of the primary evaporator during molecular distillation is 10-1000 Pa; and/or the temperature of the evaporation surface of the main evaporator is 150-260 ℃.
10. The method according to claim 8 or 9, 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 is 150-200 ℃;
(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 main evaporator is 200-260 ℃ to obtain the long-chain binary dioctyl phthalate mixture.
11. The method of claim 1 or 2, wherein the mixture comprising the long chain dibasic acid is dried to a moisture content of 5 wt% or less prior to the octylation.
12. The method of claim 2, wherein the mixture of long chain dibasic dioctyl esters is a mixture of any number of dibasic dioctyl esters having 10-18 carbon atoms.
13. A mixture of long chain dioctyl dibasic acids, characterized by: prepared using the method of any one of claims 1-12.
14. Use of a mixture of long chain dioctyl dibasic acid according to claim 13 in the synthesis of an ester base oil.
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| CN1508117A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic dialkyl ester |
| CN103121956A (en) * | 2011-11-21 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing long-chain dibasic acid diester by using long-chain dibasic acid fermentation broth |
| CN104845699A (en) * | 2013-06-05 | 2015-08-19 | 山东瀚霖生物技术有限公司 | Diester lubricant base oil and preparation method thereof |
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| CN1508117A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Method for preparing long-chain dicarboxylic dialkyl ester |
| CN103121956A (en) * | 2011-11-21 | 2013-05-29 | 中国石油化工股份有限公司 | Method for preparing long-chain dibasic acid diester by using long-chain dibasic acid fermentation broth |
| CN104845699A (en) * | 2013-06-05 | 2015-08-19 | 山东瀚霖生物技术有限公司 | Diester lubricant base oil and preparation method thereof |
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| CN114166837A (en) * | 2021-12-15 | 2022-03-11 | 无锡殷达尼龙有限公司 | Method for testing thermal stability of long carbon chain dibasic acid |
| CN114166837B (en) * | 2021-12-15 | 2024-05-03 | 无锡殷达尼龙有限公司 | Method for testing thermal stability of long carbon chain dibasic acid |
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