CN112079713B - Method for treating mixtures containing long-chain dibasic acids and use thereof - Google Patents
Method for treating mixtures containing long-chain dibasic acids and use thereof Download PDFInfo
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
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- C10M105/36—Esters of polycarboxylic acids
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
- C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
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Abstract
The invention provides a method for treating a mixture containing long-chain dicarboxylic acid, which comprises the step of performing octyl esterification on the mixture containing long-chain dicarboxylic acid to obtain a mixed dioctyl long-chain dicarboxylic acid. The long-chain dicarboxylic acid dioctyl ester mixture obtained by the mixture containing the long-chain dicarboxylic acid through the octyl esterification reaction and purification can be applied to the base oil of the synthetic ester lubricating oil, and the performance of the mixture is comparable with that of the existing lubricating oil phase. Realizes the effective utilization of the mixture containing long-chain dicarboxylic acid discharged in the process of extracting and refining long-chain dicarboxylic acid from long-chain dicarboxylic acid fermentation liquid. The method for treating the mixture containing the long-chain dibasic acid is suitable for industrial application, has low equipment requirement and simple and convenient operation, solves the problems of treatment and reutilization of the effluent in the production process of the long-chain dibasic 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 oil film protecting effect. The polarity of the ester molecules can enable the ester molecules to be adsorbed on the metal surface to form an oil layer of an adhesive molecular oil film, and the adhesive molecular oil film capable of realizing liquid lubrication can exist between the two metal surfaces even after the engine stops working, so that uninterrupted protection is provided for the engine. At present, qualified internal combustion engine oil can be produced by taking pure synthetic ester oil as base oil; however, if the base oil is made of poly-a-olefin (PAO, group IV base oil), a certain amount of synthetic ester oil (more than 10%) must be added to improve the solvency of the finished oil, improve its detergent dispersibility and overcome the shrinkage of the rubber seal caused by 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, which are one of the most widely used synthetic oils at present, because of their excellent lubricating properties and viscosity-temperature characteristics.
The polyacid synthesized ester base oil has been successfully applied to lubrication of mechanical equipment working under boundary lubrication conditions for a long time in industries such as aviation, metallurgy, rail transit, wind power generation and the like due to the characteristics of excellent high and low temperature performance, good tribological characteristics, adjustable molecular structure, environmental friendliness and the like.
Long chain dibasic acid (Long chain dicarboxylic acids, LCDA) having the general 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, pesticide, medicine, new materials and the like. The most conventional preparation method of long-chain dibasic acid at present is to prepare long-chain alkane and fat by long-chain alkane and fatThe acid, fatty acid ester or fatty acid salt is obtained by fermenting under specific strain. The mixture containing long-chain dibasic acid discharged in the fermentation preparation process of long-chain dibasic acid cannot be fully utilized, so that resource waste is caused. If the mixture containing long-chain dibasic acid in the process of preparing long-chain dibasic acid by fermentation is subjected to methyl esterification, usually the methyl esterified product containing the mixture of long-chain dibasic acid is an intermediate, and further processing such as alkaline hydrolysis or transesterification is required to produce the corresponding long-chain dibasic acid or an esterified product of the long-chain dibasic acid, etc. Such a process is complicated and the processing cost is high. Therefore, the method has more important practical significance for researching the esterification reaction (such as octyl esterification reaction) of converting and reutilizing the mixture containing 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) performing a octyl esterification reaction on the mixture containing the long-chain dibasic acid to synthesize a mixture of the long-chain dibasic acid dioctyl ester. The octyl esterification technology of the mixture containing the long-chain dibasic acid is suitable for industrial application, solves the problem that the long-chain dibasic acid mixture discharged in the process of extracting and refining the long-chain dibasic acid fermentation liquid cannot be effectively utilized for resource waste, and the mixed long-chain dibasic acid dioctyl ester converted after the octyl esterification reaction can be applied to products such as synthetic ester base oil and the like.
The invention provides a method for treating a mixture containing long-chain dibasic acid, which comprises the following steps: performing 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 with isooctyl alcohol and a catalyst, and performing a octyl esterification reaction;
(2) Washing the product after the octyl esterification reaction with alkali liquor;
(3) And distilling and purifying to obtain the mixture of long-chain dicarboxylic acid dioctyl ester.
The mixture comprising long chain dibasic acids of the present invention may comprise: the long-chain dicarboxylic acid precipitate is obtained by extracting long-chain dicarboxylic acid-containing materials discharged in the process of refining long-chain dicarboxylic acid fermentation broth, or recycling most of the solvent from the materials, or accumulating long-chain dicarboxylic acid precipitate in long-term precipitation in a long-chain dicarboxylic acid sewage treatment workshop.
The long-chain dibasic acid fermentation broth is fermentation broth obtained by taking alkane, fatty acid and derivatives thereof as substrates and utilizing a microbial fermentation method. The microorganism can oxidize alkane, fatty acid and derivative terminal methyl of fatty acid 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 dibasic acid fermentation broth can be a method known in the art.
It should be understood by those skilled in the art that the "long-chain diacid" in the "extracting and refining long-chain diacid from long-chain diacid fermentation broth" is a long-chain diacid having the same carbon chain length as the fermentation substrate, and may also be referred to as a target long-chain diacid.
Further, the mixture containing long chain dibasic acid in the present invention comprises:
(1) Dissolving a long-chain dibasic acid crude product obtained from fermentation liquor of the long-chain dibasic acid in a solvent, cooling, crystallizing and separating out a residual material after long-chain dibasic acid precipitation;
or (2) recycling the material of (1) to the remainder of the solvent for a substantial portion thereof;
or (3) acidifying and crystallizing the fermentation liquor of the long-chain dibasic acid, extracting the acidified crystallization liquor with a solvent, separating the liquid, cooling and crystallizing the organic phase containing the long-chain dibasic acid, and separating out the residual materials after the long-chain dibasic acid is precipitated;
or (4) recycling most of the solvent from the material of (3) to the remainder;
or (5) long-chain diacid sediment obtained by long-term sediment accumulation in a long-chain diacid sewage treatment workshop.
Further, (1) the method of obtaining the long-chain dicarboxylic acid crude product from the fermentation broth of the long-chain dicarboxylic acid can obtain the long-chain dicarboxylic acid crude product by separating out the precipitate after acidifying and crystallizing the fermentation broth of the long-chain dicarboxylic acid. Alternatively, the fermentation broth may be directly subjected to acidification crystallization. Or removing thallus in the fermentation liquor by centrifugation or membrane filtration before acidification and crystallization to obtain clear solution of dibasic acid. Whether the activated carbon decolorization step is performed before the acidification crystallization can be selected according to the condition of the clear solution of the dibasic acid.
Further, the separation means of (1) or (3) comprises centrifugation and/or filtration.
It can be understood that: through the recrystallization of (1), most of impurities (including one or more of cell tissues and pigments of fermenting microorganism) in the crude long-chain dibasic acid, most of acids (including hetero acid and long-chain dibasic acid with unequal carbon chain length with fermenting substrate) except the target long-chain dibasic acid, wherein the hetero acid comprises but is not limited to a general formula R 2 -COOH, wherein said R 2 Is CH 3 (CH 2 ) n-, n=8-16. ) Is dissolved in a solvent to be separated from the target long-chain dibasic acid. In the recrystallization process, the crude long-chain dicarboxylic acid is dissolved in the solvent, and then cooled (the temperature is preferably controlled below 50 ℃ but higher than 20 ℃) to separate out, so that part of target long-chain dicarboxylic acid is also dissolved in the solvent. The above-mentioned solvents containing impurities, hetero acids and long-chain dibasic acids (including long-chain dibasic acids having the same carbon chain length as the fermentation substrate and long-chain dibasic acids having different carbon chain lengths as the fermentation substrate) are collectively referred to as solvent mother liquor. The mixture comprising long chain dibasic acids described in the present invention may be, for example, a solvent mother liquor. The solvent mother liquor may be the remainder after a large amount of solvent is recovered.
Further, the recovery of the large amount of solvent may be performed by a method known in the art, such as evaporation or rectification. Further, the solvent includes: one or more of water, alcohols, organic monobasic acids, ketones, ethers, esters and benzenes; 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 crystals" described in (3). Preferably, the "acidified crystallization" is an acid to adjust the pH endpoint to 2-5. It should be understood that: alternatively, the fermentation broth may be directly subjected to acidification crystallization. Or removing thallus in the fermentation liquor by centrifugation or membrane filtration before acidification and crystallization to obtain clear solution of dibasic acid. Whether the activated carbon decolorization step is performed before the acidification crystallization can be selected according to the condition of the clear solution of the dibasic acid.
The method for treating a mixture containing a long-chain dibasic acid according to any one of the above (hereinafter referred to as a treatment method), the composition of the mixture containing a long-chain dibasic acid comprising: an effective acid comprising a long chain diacid (including a long chain diacid of equal carbon chain length to the fermentation substrate, a long chain diacid of unequal carbon chain length to the fermentation substrate). Further, the effective acid includes long chain dibasic acid and hetero acid.
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 fermentation microorganism, and pigment. The pigment is typically present in an amount of 1 to 20wt%, the percentage being the percentage of dry matter of the mixture comprising long chain dibasic acids. The amount of tissue is typically 1-20wt%, the percentage being the percentage of dry matter of the mixture comprising long chain dibasic acids.
The composition of any of the above claims comprising a mixture of long chain dibasic acids. Mixtures containing long chain dibasic acids may also include very small amounts of water.
Further, the long chain dibasic acid in the effective acid is represented by a general formula HOOC-R 1 -COOH, wherein said R is one or more of 1 Is- (CH) 2 ) m -and m is 8-16;
further, the effective acid accounts for 30-90% of the dry matter of the mixture containing the long-chain dibasic acid, and 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 is 50wt% or more, or 55wt% or more, or 60wt% or more, or 65wt% or more, or 70wt% or more, of the dry matter of the mixture containing the long-chain dibasic acid. Of course, it is also possible to be 50% by weight 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 hetero acid. The mass ratio characteristic is one of the most main characteristics that the composition of the mixture containing the long-chain dibasic acid is different from the composition of the original fermentation liquid of the long-chain dibasic acid. The fermentation liquid is mainly long-chain dibasic acid with the same carbon number as the substrate (the mass of the long-chain dibasic acid accounts for at least 90wt% of the total acid mass).
Further, isooctanol may be added during the octyl esterification reaction in step (1).
Further, in the process of performing the octyl esterification reaction in the step (1), a catalyst may be additionally added.
The treatment process according to any of the preceding claims, wherein the total amount of isooctanol is 0.2-3 times, preferably 0.5-3 times, more preferably 1-2 times the effective acid mass.
A process according to any preceding claim, 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 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 course of the octyl esterification reaction is 1 to 10%, preferably 3 to 8%, more preferably 3 to 7% of the effective acid mass.
The treatment method according to any one of the above, wherein the temperature of the octanoyl esterification reaction is 150-200 ℃; and/or the time of the octanoyl esterification reaction is 3-15h;
preferably, the temperature of the octanoyl esterification reaction is 155-195 ℃; and/or, the time of the octyl esterification is preferably 5-13h. More preferably, the temperature of the octanoyl esterification reaction is 160-190 ℃; and/or, the time of the octyl esterification is 6-9h. The temperature of the octanoyl esterification is controlled in a reasonable area, so that a better octanoyl esterification effect can be realized; too low a temperature and too high a temperature are unfavorable for the octyl esterification reaction. The temperature of the octyl esterification is the liquid phase temperature in the esterification equipment.
According to the treatment method of any one of the above, isooctanol is recovered before washing the product after the octanol esterification reaction with an alkali solution. The mode of recovering isooctanol is preferably distillation. Further preferably, distillation under reduced pressure is performed.
Further, the temperature of the reduced pressure distillation is 180 to 210 ℃, preferably 190 to 200 ℃, more preferably 195 to 200 ℃.
While further, the pressure of the reduced pressure distillation is 1 to 10kPa, preferably 2 to 8kPa, more preferably 2 to 5kPa.
Further, the reduced pressure distillation time is 2 to 12 hours, preferably 3 to 10 hours, more preferably 4 to 8 hours.
The process according to any one of the preceding claims, wherein in step (2) the alkali in the lye comprises one or more of sodium hydroxide, sodium bicarbonate and sodium carbonate, preferably sodium bicarbonate or sodium carbonate, more preferably sodium carbonate. The lye is preferably an aqueous solution of the above-mentioned base.
Further, the mass fraction of the alkali in the alkali liquid is 1 to 20wt%, preferably 3 to 10wt%, more preferably 4 to 6wt%.
According to the treatment method of any one of the above, in the step (2), the number of washing with alkali solution may be 1 or 2 or more.
The treatment method according to any one of the above, wherein in the step (2), the acid value of the organic phase at the end of the lye 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 the temperature at the time of washing with alkali solution in the step (2) is 0 to 100 ℃, preferably 50 to 95 ℃, more preferably 70 to 90 ℃.
The process according to any of the preceding claims, wherein in step (2) the alkaline washing is carried out for a period of time ranging from 5 to 80 minutes, preferably from 20 to 80 minutes.
The catalyst, long chain dibasic acid and/or hetero acid which do not carry out the octyl esterification reaction and monooctyl ester of 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 the alkali washing. To remove possible residual base in the organic phase. The saturated brine is preferably saturated saline.
According to the treatment method of any one of the above, the step (3) may be performed before distillation purification, and dried over anhydrous sodium sulfate. To remove residual water in the organic phase.
The treatment method according to any one of the above, wherein the distillation in step (3) is reduced pressure distillation, preferably wiped film distillation, more preferably molecular distillation.
Further, the pressure of the main evaporator is 10-1000Pa during molecular distillation, and/or the evaporating surface temperature of the main evaporator is 150-260 ℃.
Further, the temperature of the condensation surface of the main evaporator of the molecular distillation is-10 to 50 ℃, preferably-5 to 30 ℃, more preferably-5 to 5 ℃.
Further, the main evaporator of the molecular distillation has a scraper rotation speed of 200 to 400rpm, preferably 250 to 350rpm, more preferably 290 to 310rpm.
Further, the temperature of the feed inlet of the molecular still is 20 to 100 ℃, preferably 25 to 60 ℃, more preferably 25 to 40 ℃.
Further, the molecular distillation comprises the steps of: (A) Controlling the pressure of the main evaporator to be 300-1000Pa, and collecting fraction 1 when the evaporation surface temperature of the main evaporator is 150-200 ℃; (B) Controlling the pressure of the main evaporator to be 10-200Pa, and collecting the fraction 2 when the evaporating surface temperature of the main evaporator is 200-260 ℃ to obtain the long-chain dicarboxylic acid dioctyl ester mixture.
The fraction 1 collected in step (a) comprises octyl esters of isooctanol and a hetero acid.
Fraction 2 collected in step (B) comprises: any of several kinds of C10-C18 long-chain dicarboxylic acid dioctyl esters.
Preferably, the pressure of the main evaporator of the molecular distillation in the step (A) is 400-800Pa, and/or the evaporation surface temperature of the main evaporator of the molecular distillation in the step (A) is 160-200 ℃; more preferably, the pressure of the main evaporator of the molecular distillation of step (A) is 500-700Pa, and/or the evaporation surface temperature of the main evaporator of the molecular distillation of 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 evaporation surface temperature 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 of step (B) is 50 to 150Pa, and/or the evaporation surface temperature of the main evaporator of the molecular distillation of step (B) is 220 to 250 ℃.
The method according to any one of the above, wherein the mixture of long-chain dioctyl dibasic acid esters is a mixture of any of dioctyl dibasic acid esters having 10 to 18 carbon atoms.
The process according to any of the preceding claims, wherein the mixture comprising long chain dibasic acid is dried prior to octyl esterification. Drying to a moisture content of 5wt% or less, preferably 3wt% or less.
Still further, the drying temperature is 80-130 ℃, preferably 90-120 ℃, more preferably 110 ℃.
The mixture comprising long chain dibasic acid is dried prior to step (1), the main purpose of the drying being to remove water that may be present in the mixture comprising long chain dibasic acid, thereby increasing the esterification rate during the octyl esterification.
The invention also provides a mixture of long-chain dicarboxylic acid dioctyl ester, which is prepared by the treatment method of the mixture containing long-chain dicarboxylic acid.
The invention also provides a long-chain dicarboxylic acid dioctyl ester 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 mixture containing long-chain dicarboxylic acid is subjected to a octyl esterification reaction and purified to obtain a long-chain dicarboxylic acid dioctyl ester mixture which can be directly applied to the synthesis of ester base oil. Realizes the effective utilization of long-chain dibasic acid discharged in the process of extracting and refining long-chain dibasic acid fermentation liquor, and avoids waste.
2. The method for treating the mixture containing the long-chain dibasic acid is suitable for industrialized mass production, has low equipment requirement and simple and convenient operation, solves the problems of waste treatment and reutilization in the production process of the long-chain dibasic acid, and has remarkable economic value.
Detailed Description
The test methods in the examples are described below:
acid value measurement: the cold solvent method is adopted in GB/T5530-2005 'determination of acidity and acid value of animal and vegetable fat'.
Gas chromatography: a Shimadzu GC-2014 gas chromatograph, shimadzu corporation, japan was used.
Platinum cobalt chromaticity: the chromaticity measurement is carried out by using a GB/T3143 platinum cobalt method.
Kinematic viscosity (40 ℃ and 100 ℃): the test was performed according to ASTM D445-17.
Viscosity index: the test was performed according to ASTM D2270.
Pour point: the test was performed according to ASTM D97.
Flash point (COC): the test was performed according to ASTM D92.
The mixture containing long-chain dibasic acid discharged in the process of extracting and refining DC10-DC18 from the DC10-DC18 fermentation liquid comprises the following components:
(1) Dissolving a crude product of DC10-DC18 obtained from fermentation broth of DC10-DC18 in a solvent, cooling, crystallizing, and separating out a material remained after DC10-DC18 precipitation;
or (2) recycling the material of (1) to the remainder of the solvent for a substantial portion thereof;
or (3) acidifying and crystallizing the fermentation liquor of the DC10-DC18, extracting the acidified crystallization liquor with a solvent, separating the liquid, cooling and crystallizing the organic phase containing the DC10-DC18, and separating out the residual materials after the DC10-DC18 is precipitated;
or (4) recycling most of the solvent from the material of (3) to the remainder;
or (5) long-term precipitation accumulation of long-chain binary acid sewage treatment workshops to obtain DC10-DC18 precipitation.
The DC10-DC18 fermentation broth is fermentation broth obtained by taking alkane with 10-18 carbon atoms, fatty acid and derivatives thereof as substrates and utilizing a microbial fermentation method. The microorganism can oxidize alkane, fatty acid and derivative terminal methyl of fatty acid into carboxyl to generate DC10-DC 18.
Further, (1) the method for obtaining the crude product of the DC10-DC18 from the fermentation liquid of the DC10-DC18 is that the fermentation liquid of the DC10-DC18 is acidified and crystallized, and then the precipitate of the DC10-DC18 is separated, thus obtaining the crude product of the long-chain dibasic acid. Alternatively, the fermentation broth may be directly subjected to acidification crystallization. Or removing thallus in the fermentation liquor by centrifugation or membrane filtration before acidification and crystallization to obtain clear solution of dibasic acid. Whether the activated carbon decolorization step is performed before the acidification crystallization can be selected according to the condition of the clear solution of the dibasic acid.
(1) Or (3) the separation means is centrifugation and/or filtration.
Through the recrystallization of (1), most of impurities (one or two of cell tissues and pigments of fermentation microorganisms) in the crude long-chain dibasic acid, and most of acids except the target long-chain dibasic acid (including hetero acid and long-chain dibasic acid with different carbon chain lengths from fermentation substrates; the hetero acid comprises a general formula R 2 -COOH, wherein said R 2 Is CH 3 (CH 2 ) n-, n=8-16. ) Is dissolved in a solvent to be separated from the target long chain dibasic acid (DC 10-DC 18). In the recrystallization process, the crude long-chain dicarboxylic acid is dissolved in the solvent, and then cooled (the temperature is preferably controlled below 50 ℃ but higher than 20 ℃) to separate out, so that part of target long-chain dicarboxylic acid is also dissolved in the solvent. The above-mentioned solvents containing impurities, hetero acids and long-chain dibasic acids (including long-chain dibasic acids having the same carbon chain length as the fermentation substrate and long-chain dibasic acids having different carbon chain lengths as the fermentation substrate) are collectively referred to as solvent mother liquor. The invention comprises a long chain IIThe mixture of polyacids may be, for example, a solvent mother liquor.
(3) The "acidified crystals" described in (a) use hydrochloric acid and/or sulfuric acid. The "acidification crystallization" is to crystallize DC10-DC18 by adjusting the pH end point to 2-5 with acid.
The above method for recovering a large amount of solvent adopts an evaporation method or a rectification method. The solvent comprises: any one of methanol, ethanol, isopropanol, n-butanol, acetic acid, acetone, diethyl ether, ethyl acetate, butyl acetate and toluene.
Extraction and purification example 1 of DC10-DC18 fermentation broth
(1) Extracting: heating any one of the fermentation liquids of DC10-DC18 to 60-100 ℃, centrifugally removing thalli, adding 0.05-5% (percent of the volume of the clear liquid) of activated carbon into the obtained clear liquid for decolorization, filtering to remove the activated carbon, heating the decolorized liquid to 50-100 ℃, adjusting 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 acetic acid solution with the mass fraction of more than 90%, decolorizing with or without decolorizing with activated carbon, cooling and crystallizing, and separating to obtain DC10-DC18 product and solvent mother liquor;
(3) The acetic acid in the solvent mother liquor is recycled after being recovered by a rectifying tower, and the bottom material of the tower is a mixture containing long-chain dibasic acid. The pigment content is generally 1-20wt% and the cell tissue content is generally 1-20wt% in the dry matter of the mixture.
Extraction and purification example 2 of DC10-DC18 fermentation broth
(1) Extracting: heating any one of the fermentation liquids of DC10-DC18 to 60-100 ℃, centrifugally removing thalli, adding 0.05-5% (percent of the volume of the clear liquid) of activated carbon into the obtained clear liquid for decolorization, filtering to remove the activated carbon, heating the decolorized liquid to 50-100 ℃, and then adjusting pH to 3-4 for acidification and crystallization to obtain a DC10-DC18 crude product;
(2) Extracting the DC10-DC18 crude product with methanol to obtain DC10-DC18 product, and recovering water from the residue to obtain mixture containing long chain dibasic acid. The pigment content is generally 1-20wt% and the cell tissue content is generally 1-20wt% in the dry matter of the mixture.
Example 1
DC12 after extraction and purification of DC12, the mixture containing long chain dibasic acid (extraction and purification example 1) was dried at 110℃to a water content of 0.66% by weight, to give 1.611kg of a dry matter. Wherein the effective acid content is 80.91wt%, the long-chain dicarboxylic acid content is 71.59wt% (the compositions of the long-chain dicarboxylic acids are DC10, DC12, DC11, DC13, DC14 and DC 15), the hetero-acid content is 9.32wt%, and the mass ratio of the long-chain dicarboxylic acid to the hetero-acid is 7.7:1.
The above dry matter was charged into a 5L reactor while adding 1.77kg of isooctanol and 56g of p-toluenesulfonic acid monohydrate. Esterifying for 5h at 168 ℃ in liquid phase temperature, separating out 154g of water, and detecting the acid value of the reaction liquid, wherein the esterification rate is 80.1%.
And (3) distilling under reduced pressure to recover unreacted isooctanol under the conditions of a vacuum degree of 2kPa and a liquid phase temperature of 197 ℃ for 5 hours.
300g of 5.5wt% sodium carbonate aqueous solution was added to the residual organic phase by distillation under reduced pressure while maintaining the temperature at 90℃and stirred for 30 minutes. Standing and layering at 90 ℃ to separate out a lower water phase. The alkaline washing process is repeated: the organic phase is washed once more with 300g of 5.5% by weight aqueous sodium carbonate solution, with the temperature kept at 90 ℃. The acid value of the organic phase was found to be 0.13mgKOH/g. The organic phase was then dried over anhydrous sodium sulfate and filtered to give a crude mixture of long chain dioctyl phthalate in dark brown.
The crude mixture of the dark brown long-chain dicarboxylic acid dioctyl ester is distilled by a molecular distiller. Molecular distillation was carried out by vacuum pumping and raising the temperature under conditions of a feed inlet temperature of 30℃and a main evaporator condensation surface temperature of 0℃and a main evaporator scraper rotation speed of 300 rpm. The feed rate was controlled to 1kg/h at a vacuum of 550Pa and the evaporation surface temperature of the main evaporator of 200℃to collect 105g of a low boiling fraction. And controlling the feeding speed to be 0.5KG/h under the condition that the vacuum degree is 120Pa and the temperature of the evaporation surface of the main evaporator is 235 ℃, collecting product fractions to be light yellow oily matters, and obtaining a mixture of 1.530KG of long-chain dioctyl dibasic acid and the purity of the dioctyl long-chain dibasic acid is 99.64%. The mixture of long chain dicarboxylic acid dioctyl ester was subjected to platinum-cobalt color and acid number measurement, and the test results are shown in Table 1.
Example 2
After DC13 was purified by extraction from the DC13 fermentation broth, the mixture containing long chain dibasic acid (extraction and purification example 1) was dried at 110℃to a water content of 0.43% by weight, to give 1.853kg of a dry matter. Wherein the effective acid content is 71.49wt%, the long-chain dicarboxylic acid content is 61.21wt% (the long-chain dicarboxylic acid composition is DC11, DC12, DC13, DC14 and DC 15), the hetero-acid content is 10.28wt%, and the mass ratio of the long-chain dicarboxylic acid to the hetero-acid 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. Esterifying for 5h at 168 ℃ to obtain 171g of water, and detecting the acid value of the reaction solution to obtain the esterification rate of 79.6%.
And (3) distilling under reduced pressure to recover unreacted isooctanol under the conditions of a vacuum degree of 2kPa and a liquid phase temperature of 200 ℃ for 5 hours.
300g of 5.5wt% sodium carbonate aqueous solution was added to the residual organic phase by distillation under reduced pressure while maintaining the temperature at 90℃and stirred for 30 minutes. Standing and layering at 90 ℃ to separate out a lower water phase. The alkaline washing process is repeated: the organic phase is washed once more with 300g of 5.5% by weight sodium carbonate solution, with the temperature kept at 90 ℃. The acid value of the organic phase was found to be 0.22mgKOH/g. The organic phase was then dried over anhydrous sodium sulfate and filtered to give a crude mixture of long chain dioctyl phthalate in dark brown.
The crude mixture of the dark brown long-chain dicarboxylic acid dioctyl ester is distilled by a molecular distiller. Molecular distillation was carried out by vacuum pumping and raising the temperature under conditions of a feed inlet temperature of 30℃and a main evaporator condensation surface temperature of 0℃and a main evaporator scraper rotation speed of 300 rpm. 185g of low-boiling fraction was collected under a vacuum of 550Pa and a temperature of the evaporation surface of the main evaporator of 200℃at a feed rate of 1 kg/h. And controlling the feeding speed to be 0.5KG/h under the condition that the vacuum degree is 120Pa and the temperature of the evaporation surface of the main evaporator is 235 ℃, collecting product fractions to be light yellow oily matters, and obtaining a mixture of 1.602KG of the dioctyl long-chain dibasic acid and the purity of the dioctyl long-chain dibasic acid to be 99.86%. The mixture of long chain dicarboxylic acid dioctyl esters was subjected to platinum-cobalt color and acid number measurements. The test results are shown in Table 1.
Example 3
After DC11 was purified by extraction from the DC11 fermentation broth, the mixture containing long chain dibasic acid (extraction and purification example 1) was dried at 110℃to a water content of 0.65% by weight, to give 1.968kg of a dry matter. Wherein the effective acid content is 78.24wt%, the long-chain dicarboxylic acid content is 65.98wt% (the long-chain dicarboxylic acid composition is DC10, DC11, DC12, DC13, DC14 and DC 15), and the hetero-acid content is 12.26wt%, and the mass ratio of the long-chain dicarboxylic acid to the hetero-acid is 5.4:1.
The above dry matter was charged into a 5L reactor while adding 2.155kg of isooctanol and 65g of p-toluenesulfonic acid monohydrate. Esterifying for 5h at 168 ℃ in liquid phase temperature, separating 178g of water, and detecting the acid value of the reaction liquid, wherein the esterification rate is 80.8%.
And (3) distilling under reduced pressure to recover unreacted isooctanol under the conditions of a vacuum degree of 2kPa and a liquid phase temperature of 200 ℃ for 5 hours.
300g of 5.5% by weight sodium carbonate solution was added to the residual organic phase by distillation under reduced pressure while maintaining the temperature at 90℃and stirred for 30 minutes. Standing and layering at 90 ℃ to separate out a lower water phase. The alkaline washing process is repeated: the organic phase is washed once more with 300g of 5.5% by weight sodium carbonate solution, with the temperature kept at 90 ℃. The acid value of the organic phase was found to be 0.25mgKOH/g. The organic phase was then dried over anhydrous sodium sulfate and filtered to give a crude mixture of long chain dioctyl phthalate in dark brown.
The crude mixture of the dark brown long-chain dicarboxylic acid dioctyl ester is distilled by a molecular distiller. Molecular distillation was carried out by vacuum pumping and raising the temperature under conditions of a feed inlet temperature of 30℃and a main evaporator condensation surface temperature of 0℃and a main evaporator scraper rotation speed of 300 rpm. The low boiling fraction was collected at a vacuum of 550Pa and a main evaporator evaporation surface temperature of 200℃at a feed rate of 1 kg/h. And controlling the feeding speed to be 0.5KG/h under the condition that the vacuum degree is 120Pa and the temperature of the evaporation surface of the main evaporator is 235 ℃, collecting product fractions to be light yellow oily matters, and obtaining a mixture of 1.616KG of the dioctyl long-chain dibasic acid and the purity of the dioctyl long-chain dibasic acid to be 99.63%. The mixture of long chain dicarboxylic acid dioctyl ester was subjected to platinum-cobalt color and acid number measurement, and the test results are shown in Table 1.
Example 4
Substantially the same as in example 3, except that 60g of 98% concentrated sulfuric acid was used as the catalyst in example 4.
Example 5
After DC12 was purified by extraction from the DC12 fermentation broth, the mixture containing long chain dibasic acid (extraction and purification example 1) was dried at 110℃to a water content of 0.61% by weight, to obtain 598kg of a dry matter. Wherein the effective acid content is 79.89wt%, the long-chain dicarboxylic acid content is 70.97wt% (the long-chain dicarboxylic acid composition is DC10, DC11, DC12, DC13, DC14 and DC 15), the hetero-acid content is 8.92wt%, and the mass ratio of the long-chain dicarboxylic acid to the hetero-acid is 8:1.
The above dry matter was charged into a 2000L reactor with isooctanol 649KG and p-toluenesulfonic acid monohydrate 21.5KG. Esterifying for 10h at 168 ℃ to obtain 56.3kg of water, and detecting the acid value of the reaction liquid to obtain the esterification rate of 79.0%.
And (3) distilling under reduced pressure to recover unreacted isooctanol under the conditions of a vacuum degree of 2kPa and a liquid phase temperature of 195 ℃ for 8 hours.
100kg of 5.5wt% sodium carbonate solution was added to the residual organic phase by distillation under reduced pressure while maintaining the temperature at 90℃and stirred for 30 minutes. Standing and layering at 90 ℃ to separate out a lower water phase. The alkaline washing process is repeated: the organic phase is washed once more with 100kg of a 5.5% by weight sodium carbonate solution, with the temperature kept at 90 ℃. The acid value of the organic phase was found to be 0.09mgKOH/g. The organic phase was then dried over anhydrous sodium sulfate and filtered to give a crude mixture of long chain dioctyl phthalate in dark brown.
The crude mixture of the dark brown long-chain dicarboxylic acid dioctyl ester is distilled by a molecular distiller. Molecular distillation was carried out by vacuum pumping and raising the temperature under conditions of a feed inlet temperature of 30℃and a main evaporator condensation surface temperature of 0℃and a main evaporator scraper rotation speed of 300 rpm. The feed rate was controlled at 150kg/h at a vacuum level of 550Pa and a temperature of the evaporation surface of the main evaporator of 200℃to collect 42.5kg of a low boiling fraction. Controlling the feeding speed to be 75KG/h under the condition that the vacuum degree is 120Pa and the temperature of the evaporation surface of the main evaporator is 230 ℃, collecting product fractions to be light yellow oily matters, and obtaining 551KG of long-chain dioctyl dibasic acid mixture with the purity of 99.67 percent. The mixture of long chain dicarboxylic acid dioctyl ester was subjected to platinum-cobalt color and acid number measurement, and the test results are shown in Table 1.
Table 1: results of test of esterification rate of octanoyl esterification reaction, platinum-cobalt chromaticity and acid value of mixture of long-chain dicarboxylic acid dioctyl ester
The mixture containing the long-chain dibasic acid is subjected to octyl esterification to synthesize the dioctyl ester of the mixed long-chain dibasic acid, and the dioctyl ester can be used for synthesizing ester lubricating oil base oil. Solves the problems of resource waste and environmental pollution caused by the fact that the mixture containing the long-chain dibasic acid is often piled up in the long-chain dibasic acid fermentation process. 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 dioctyl dibasic acid has better chromaticity and meets the requirement of the lubricating oil base oil on chromaticity. In addition, the method for treating the mixture containing the long-chain dibasic acid is not only suitable for laboratory research and development orders, but also completely suitable for treating the mixture containing the long-chain dibasic acid in a factory order, and has great application value.
Table 2: results of Performance test of mixtures of Dioctyl long chain dibasic acid
As can be seen from the experimental results in Table 2, the mixed long-chain dioctyl dibasic acid is used as the base oil of lubricating oil, and the viscosity performance of the mixed long-chain dioctyl dibasic acid is superior to that of the adipic base oil of mobil (A34, A32). Pour point can be comparable with that of adipic ester base oil phase of mobil. The flash point is higher than that of the mobil oil, the safety is higher, and the volatility loss of the base oil serving as the lubricating oil is reduced by the higher flash point, so that the performance change caused by component volatilization of the base oil after long-term use of the lubricating oil is delayed to a certain extent.
The foregoing describes alternative embodiments of the present invention to teach those skilled in the art how to implement and reproduce the invention. In order to teach the technical solution of the present invention, some conventional aspects have been simplified or omitted. After reading the present specification, one skilled in the art can easily devise variations or alternatives of the technical solution of the present invention that can achieve the object of the present invention according to the common general knowledge in the chemical field, and it should be understood by those skilled in the art that variations or alternatives derived from these embodiments will fall within the scope of the present invention.
Claims (8)
1. A method of treating a mixture comprising long chain dibasic acids comprising the steps of:
(1) Uniformly mixing a mixture containing long-chain dibasic acid with isooctyl alcohol and a catalyst, and performing a octyl esterification reaction;
(2) Washing the product after the octyl esterification reaction with alkali liquor;
(3) Distilling and purifying to obtain a mixture of long-chain dicarboxylic acid dioctyl ester;
the distillation is a molecular distillation and is carried out,
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 evaporation surface temperature of the main evaporator is 150-200 ℃;
(B) Controlling the pressure of the main evaporator to be 10-200Pa, and collecting the fraction 2 when the temperature of the evaporation surface of the main evaporator is 200-260 ℃ to obtain a long-chain dicarboxylic acid dioctyl ester mixture;
the mixture comprising long chain dibasic acids comprises: long-chain diacid containing materials discharged in the process of extracting and refining long-chain diacid by fermentation liquor of the long-chain diacid, or residues obtained after most of solvents are recovered from the materials, or long-chain diacid precipitates obtained by long-term precipitation accumulation in a long-chain diacid sewage treatment workshop; and the mixture comprising long chain dibasic acids comprises: the organic acid-free organic acid composite material comprises effective acid, cell tissues of fermentation microorganisms and pigment, wherein the content of the pigment is 1-20wt%, the content of the cell tissues of the fermentation microorganisms is 1-20wt%, the content of the effective acid is 30-90wt%, the percentage is the percentage of the dry matter of the mixture containing long-chain dibasic acid, and the mass of the long-chain dibasic acid in the effective acid is more than 0.5 times of that of the mixed acid.
2. The method of claim 1, the mixture comprising long chain dibasic acids comprising: an effective acid comprising a long chain dibasic acid of the formula HOOC-R 1 -COOH, wherein said R is one or more of 1 Is- (CH) 2 ) m-and m is more than or equal to 8 and less than or equal to 16.
3. The method of claim 1, wherein the total amount of isooctanol used during the octanol reaction is 0.2-3 times the effective acid mass; and/or, the total amount of catalyst used in the process of the octyl esterification reaction is 1-10% of the mass of the effective acid.
4. The method of claim 1, the catalyst comprising: one or more of concentrated sulfuric acid, sodium bisulfate, p-toluenesulfonic acid monohydrate and tetrabutyl titanate.
5. The process of claim 1, wherein the temperature of the octanoyl esterification reaction is 150-200 ℃; and/or the time of the octanoyl esterification reaction is 3-15h.
6. The method according to claim 1, wherein the isooctanol is recovered before washing the product obtained after the octyl esterification reaction with alkali liquor; and/or (2) the acid value of the alkaline liquid washing-finished phase reaches below 2mgKOH/g.
7. The process of claim 1, wherein the mixture comprising long chain dibasic acid is dried to a moisture content of less than 5wt% prior to octyl esterification.
8. The method of claim 1, wherein the mixture of long chain dioctyl dibasic acid esters is a mixture of any of dioctyl dibasic acid esters having 10 to 18 carbon atoms.
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| 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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