CN113249414A - Preparation method of low-content low-carbon-chain long-chain binary acid - Google Patents
Preparation method of low-content low-carbon-chain long-chain binary acid Download PDFInfo
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Abstract
The invention discloses a preparation method of low-content low-carbon chain long-chain binary acid, which has the technical scheme that: the method comprises the following steps: step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures; demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 2-5h, and removing residual oil; the growth speed and size of the dibasic acid crystal are effectively controlled to form crystal slurry with uniform particle size, and the dried product has uniform particles, high bulk density, low protein and impurity content, high product purity and good color, so that the long-chain dibasic acid crystal prepared by the method meets the quality standard of polymer-grade products.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a preparation method of low-content low-carbon-chain long-chain binary acid.
Background
At present, the preparation method of the long-chain dicarboxylic acid is generally divided into two main types of solvent method and water phase method. The solvent method has a great limitation in use due to large equipment investment, high production cost, residual solvent in the product, environmental pollution and safety problems. Although the water phase method overcomes the defects of the solvent method, the product has low purity, poor color, uneven crystal granularity and high content of protein and other impurities, and cannot meet the requirements of polymer-grade products.
Reference may be made to chinese patent publication No. CN111592456A, which discloses a method for extracting mixed long-chain dibasic acid and the mixed long-chain dibasic acid. The extraction method of the mixed long-chain dibasic acid comprises the step of subjecting the mixed long-chain dibasic acid salt solution to be refined to electrodialysis through an electrodialysis device to obtain a purified mixed long-chain dibasic acid salt solution. The extraction method effectively solves the difficult problems of extraction and purification of the mixture containing the long-chain dicarboxylic acid discharged in the processes of extracting and refining the long-chain dicarboxylic acid fermentation liquor. The invention obtains the high-quality mixed long-chain dicarboxylic acid finished product which has light color and good quality. Has wide application prospect in the fields of plasticizer, lubricant, antirust agent and the like. The alkali liquor and the acid liquor obtained from the concentration chamber after the electrodialysis can be used in the next mixed dibasic acid extraction process for pH adjustment in the dissolving and separating-out processes of the mixed dibasic acid.
The above patent has the advantage of realizing atom recycling, but it also has drawbacks such as: the process flow is long, the operation is complicated, the product yield is low, the product purity is low, the color is poor, and the method cannot be applied to large-scale processing production.
Disclosure of Invention
The invention aims to provide a preparation method of low-content low-carbon-chain long-chain binary acid, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of low-content low-carbon chain long-chain binary acid comprises the following steps:
step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures;
demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 2-5h, removing residual oil, and separating candida tropicalis strain residues, dibasic acid clear liquid and residual substrate by using a membrane filtration method;
step three, decoloring and diluting: adding a decolorizer into the clear dibasic acid solution obtained in the second step for decolorization, continuously performing for 50min, filtering again by using a filtering device after the decolorization is finished to obtain a decolorized dibasic acid solution, then adding deionized water into the decolorized dibasic acid solution for dilution, and controlling the salinity of the decolorized dibasic acid solution after dilution to be 3-7;
step four, adding acid: adding dilute sulfuric acid with the mass concentration of 30-50% into the dibasic acid diluent obtained in the step three, then injecting the mixed dibasic acid diluent into a microchannel reactor for mixing and reaction crystallization, and obtaining a mixture after full reaction;
step five, heating: putting the mixture obtained in the fourth step into a reaction kettle, heating to 85-120 ℃, thoroughly eliminating microcrystals in the mixture, and obtaining dibasic acid slurry after the reaction is finished;
step six, crystallization: and (4) injecting the dibasic acid slurry obtained in the fifth step into a crystallization kettle for curing, cooling to obtain primary crystals after curing, then placing the primary crystals into a centrifuge for centrifugal separation, repeatedly washing the separated crystals with purified water until the pH value is 5.5-7.5, and finally drying with drying equipment to obtain the long-chain dibasic acid crystals.
Preferably, the decolorant comprises activated carbon particles, the salinity of the clear dibasic acid solution is adjusted to 6-10% before decoloration, and the addition amount of the decolorant is 0.2-0.8% of the mass of the clear dibasic acid solution.
Preferably, the long-chain dibasic acid comprises one or more of C9-C22 long-chain dibasic acid, C9-C18 long-chain dibasic acid, dodecanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, and hexadecanedioic acid.
Preferably, the microchannel reactor comprises a Y-type microchannel reactor and a T-type microchannel reactor, the diameter of the microchannel reactor is 280-850 mu m, the reaction temperature is controlled to be 45-65 ℃, and the reaction pH value is controlled to be 3.4-4.5 when the reaction endpoint is reached.
Preferably, the layering in step two includes alkane layer, emulsion layer, supernatant layer and subsides layer, alkane layer the emulsion layer the supernatant layer and the subsides layer distributes in the container from last to down in proper order.
Preferably, the heating in the fifth step comprises steam sleeve heating, oil bath heating and electric heating, and simultaneously, steam condensate water obtained in the heating process is recycled and used for microbial fermentation and dilution of fermentation clear liquid.
Preferably, in the sixth step, the rotating speed of the crystallization kettle is adjusted to 35-60r/min, then the rotating speed of the crystallization kettle is increased to 50-85r/min after natural cooling is carried out for 20min, then a cooling system of the crystallization kettle is opened, the temperature is reduced to 85-95 ℃ at the cooling speed of 5-8 ℃/h, and the temperature is kept for 30 min.
Preferably, the oxidation procedure in the first step is specifically as follows: when the n-alkane enters the candida tropicalis strain cells, the n-alkane is catalyzed by reductase in strain cytochrome to generate fatty alcohol, then the fatty alcohol is reduced to be catalyzed into fatty aldehyde under the action of fatty alcohol oxidase, fatty acid is catalyzed by fatty aldehyde dehydrogenase to generate fatty acid, and finally the fatty acid is oxidized in series to generate dibasic acid; the mutagenesis procedure comprises adding a nitrosoguanidine mutagen to the candida tropicalis species.
Preferably, after the sixth step, the prepared long-chain dicarboxylic acid crystals are quantitatively weighed and packaged into bags, the long-chain dicarboxylic acid crystals packaged into the bags are subjected to sampling inspection, if the inspection result is qualified, the long-chain dicarboxylic acid crystals are packaged and put in storage, and if the inspection result is unqualified, the technology is improved until the inspection is qualified.
Preferably, the demulsifier includes one or more of an AP-type demulsifier, an AE-type demulsifier, an AR-type demulsifier, and urea.
Compared with the prior art, the invention has the beneficial effects that:
the preparation method of the low-content low-carbon chain long-chain binary acid uses candida tropicalis as a strain to prepare the long-chain binary acid through biosynthesis, has mild conditions in the preparation process, can be carried out at normal temperature and normal pressure, has no harmful by-products, effectively protects the ecological environment, uses petroleum by-product n-alkane as a raw material, can generate the binary acid by adding four oxygen atoms in one step under the action of biological enzyme, has simple steps, less working procedures, high acid yield, lower cost and higher yield, and can be suitable for large-scale chemical production; through the steps of adding acid, heating and crystallizing, the growth speed and size of the dibasic acid crystal can be effectively controlled, crystal mush with uniform particle size is formed, and the dried product has uniform particles, high bulk density, less protein and impurity content, high product purity and good color, so that the long-chain dibasic acid crystal prepared by the method meets the quality standard of polymer-grade products.
Drawings
FIG. 1 is a block diagram of the method of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Please refer to FIG. 1
Example 1
A preparation method of low-content low-carbon chain long-chain binary acid comprises the following steps:
step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures;
demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 4 hours, removing residual oil, and separating candida tropicalis strain residues, dibasic acid clear liquid and residual substrate by using a membrane filtration method;
step three, decoloring and diluting: adding a decolorizer into the clear dibasic acid solution obtained in the second step for decolorization, continuously performing for 50min, filtering again by using a filtering device after the decolorization is finished to obtain a decolorized dibasic acid solution, then adding deionized water into the decolorized dibasic acid solution for dilution, and controlling the salinity of the decolorized dibasic acid solution after dilution to be 5;
step four, adding acid: adding dilute sulfuric acid with the mass concentration of 35% into the dibasic acid diluent obtained in the step three, then injecting the mixed dibasic acid diluent into a microchannel reactor for mixing and reaction crystallization, and obtaining a mixture after full reaction;
step five, heating: putting the mixture obtained in the step four into a reaction kettle, heating to 100 ℃, thoroughly eliminating microcrystals in the mixture, and obtaining dibasic acid slurry after the reaction is finished;
step six, crystallization: and (4) injecting the dibasic acid slurry obtained in the fifth step into a crystallization kettle for curing, cooling to obtain primary crystals after curing, then placing the primary crystals into a centrifuge for centrifugal separation, repeatedly washing the separated crystals with purified water until the pH value is 5.5, and finally drying with drying equipment to obtain the long-chain dibasic acid crystals.
In this example, it is preferable that the decolorizer includes activated carbon particles, the salinity of the clear dibasic acid solution is adjusted to 8% before decolorization, and the addition amount of the decolorizer is 0.4% of the mass of the clear dibasic acid solution.
In this embodiment, it is preferable that the long-chain dibasic acid includes a dodecanedioic acid.
In this embodiment, it is preferable that the microchannel reactor comprises a Y-type microchannel reactor and a T-type microchannel reactor, the diameter of the microchannel reactor is 500 μm, the reaction temperature is controlled to 65 ℃, and the reaction pH is controlled to 4.5 at the end of the reaction.
In this embodiment, preferably, the layering in the second step includes an alkane layer, an emulsion layer, a supernatant layer, and a sediment layer, and the alkane layer, the emulsion layer, the supernatant layer, and the sediment layer are sequentially distributed in the container from top to bottom.
In this embodiment, preferably, the heating in the fifth step includes steam jacket heating, oil bath heating and electric heating, and the steam condensate obtained in the heating process is recycled for microbial fermentation and dilution of the fermentation liquor.
In this example, preferably, in the sixth step, the rotation speed of the crystallization kettle is adjusted to 60r/min, then the rotation speed of the crystallization kettle is increased to 85r/min after natural cooling is performed for 20min, then the cooling system of the crystallization kettle is opened, the temperature is reduced to 95 ℃ at the cooling speed of 6 ℃/h, and the temperature is kept for 30 min.
In this embodiment, preferably, the oxidation procedure in the first step is specifically as follows: when n-alkane enters candida tropicalis strain cells, reductase in strain cytochrome catalyzes the n-alkane to generate fatty alcohol, then the fatty alcohol is reduced to be catalyzed into fatty aldehyde under the action of fatty alcohol oxidase, fatty acid is catalyzed by fatty aldehyde dehydrogenase to generate fatty acid, and finally the fatty acid is oxidized in series to generate dibasic acid; the mutagenesis procedure included the addition of a nitrosoguanidine mutagen to Candida tropicalis species.
In this example, preferably, after the sixth step, the prepared long-chain dicarboxylic acid crystals are quantitatively weighed and packaged into bags, the long-chain dicarboxylic acid crystals packaged into the bags are subjected to sampling inspection, if the inspection result is qualified, the long-chain dicarboxylic acid crystals are packaged and put in storage, and if the inspection result is unqualified, the technology is improved until the inspection is qualified.
In this embodiment, the demulsifier preferably comprises urea.
The working principle and the using process of the invention are as follows:
the preparation method of the low-content low-carbon chain long-chain binary acid uses candida tropicalis as a strain to prepare the long-chain binary acid through biosynthesis, has mild conditions in the preparation process, can be carried out at normal temperature and normal pressure, has no harmful by-products, effectively protects the ecological environment, uses petroleum by-product n-alkane as a raw material, can generate the binary acid by adding four oxygen atoms in one step under the action of biological enzyme, has simple steps, less working procedures, high acid yield, lower cost and higher yield, and can be suitable for large-scale chemical production; through the steps of adding acid, heating and crystallizing, the growth speed and size of the dibasic acid crystal can be effectively controlled, crystal mush with uniform particle size is formed, and the dried product has uniform particles, high bulk density, less protein and impurity content, high product purity and good color, so that the long-chain dibasic acid crystal prepared by the method meets the quality standard of polymer-grade products.
Example 2
A preparation method of low-content low-carbon chain long-chain binary acid comprises the following steps:
step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures;
demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 5 hours, removing residual oil, and separating candida tropicalis strain residues, dibasic acid clear liquid and residual substrate by using a membrane filtration method;
step three, decoloring and diluting: adding a decolorizer into the clear dibasic acid solution obtained in the second step for decolorization, continuously performing for 50min, filtering again by using a filtering device after the decolorization is finished to obtain a decolorized dibasic acid solution, then adding deionized water into the decolorized dibasic acid solution for dilution, and controlling the salinity of the decolorized dibasic acid solution after dilution to be 3;
step four, adding acid: adding dilute sulfuric acid with the mass concentration of 30% into the dibasic acid diluent obtained in the step three, then injecting the mixed dibasic acid diluent into a microchannel reactor for mixing and reaction crystallization, and obtaining a mixture after full reaction;
step five, heating: putting the mixture obtained in the fourth step into a reaction kettle, heating to 85 ℃, thoroughly eliminating microcrystals in the mixture, and obtaining dibasic acid slurry after the reaction is finished;
step six, crystallization: and (4) injecting the dibasic acid slurry obtained in the fifth step into a crystallization kettle for curing, cooling to obtain primary crystals after curing, then placing the primary crystals into a centrifuge for centrifugal separation, repeatedly washing the separated crystals with purified water until the pH value is 5.5, and finally drying with drying equipment to obtain the long-chain dibasic acid crystals.
In this example, it is preferable that the decolorizer includes activated carbon particles, the salinity of the clear dibasic acid solution is adjusted to 6% before decolorization, and the addition amount of the decolorizer is 0.2% of the mass of the clear dibasic acid solution.
In this embodiment, the long chain dibasic acid preferably comprises a C9-C22 long chain dibasic acid.
In this embodiment, it is preferable that the microchannel reactor comprises a Y-type microchannel reactor and a T-type microchannel reactor, the diameter of the microchannel reactor is 280 μm, the reaction temperature is controlled at 45 ℃, and the reaction pH is controlled at 3.4 at the end of the reaction.
In this embodiment, preferably, the layering in the second step includes an alkane layer, an emulsion layer, a supernatant layer, and a sediment layer, and the alkane layer, the emulsion layer, the supernatant layer, and the sediment layer are sequentially distributed in the container from top to bottom.
In this embodiment, preferably, the heating in the fifth step includes steam jacket heating, oil bath heating and electric heating, and the steam condensate obtained in the heating process is recycled for microbial fermentation and dilution of the fermentation liquor.
In this example, preferably, in the sixth step, the rotation speed of the crystallization kettle is adjusted to 35r/min, then the rotation speed of the crystallization kettle is increased to 50r/min after natural cooling is performed for 20min, then the cooling system of the crystallization kettle is opened, the temperature is reduced to 85 ℃ at the cooling speed of 5 ℃/h, and the temperature is kept for 30 min.
In this embodiment, preferably, the oxidation procedure in the first step is specifically as follows: when n-alkane enters candida tropicalis strain cells, reductase in strain cytochrome catalyzes the n-alkane to generate fatty alcohol, then the fatty alcohol is reduced to be catalyzed into fatty aldehyde under the action of fatty alcohol oxidase, fatty acid is catalyzed by fatty aldehyde dehydrogenase to generate fatty acid, and finally the fatty acid is oxidized in series to generate dibasic acid; the mutagenesis procedure included the addition of a nitrosoguanidine mutagen to Candida tropicalis species.
In this example, preferably, after the sixth step, the prepared long-chain dicarboxylic acid crystals are quantitatively weighed and packaged into bags, the long-chain dicarboxylic acid crystals packaged into the bags are subjected to sampling inspection, if the inspection result is qualified, the long-chain dicarboxylic acid crystals are packaged and put in storage, and if the inspection result is unqualified, the technology is improved until the inspection is qualified.
In this embodiment, the demulsifier is preferably included in urea.
Example 3
A preparation method of low-content low-carbon chain long-chain binary acid comprises the following steps:
step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures;
demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 2 hours, removing residual oil, and separating candida tropicalis strain residues, dibasic acid clear liquid and residual substrate by using a membrane filtration method;
step three, decoloring and diluting: adding a decolorizer into the clear dibasic acid solution obtained in the second step for decolorization, continuously performing for 50min, filtering again by using a filtering device after the decolorization is finished to obtain a decolorized dibasic acid solution, then adding deionized water into the decolorized dibasic acid solution for dilution, and controlling the salinity of the decolorized dibasic acid solution after dilution to be 7;
step four, adding acid: adding dilute sulfuric acid with the mass concentration of 50% into the dibasic acid diluent obtained in the step three, then injecting the mixed dibasic acid diluent into a microchannel reactor for mixing and reaction crystallization, and obtaining a mixture after full reaction;
step five, heating: putting the mixture obtained in the fourth step into a reaction kettle, heating to 120 ℃, thoroughly eliminating microcrystals in the mixture, and obtaining dibasic acid slurry after the reaction is finished;
step six, crystallization: and (4) injecting the dibasic acid slurry obtained in the fifth step into a crystallization kettle for curing, cooling to obtain primary crystals after curing, then placing the primary crystals into a centrifuge for centrifugal separation, repeatedly washing the separated crystals with purified water until the pH value is 7.5, and finally drying with drying equipment to obtain the long-chain dibasic acid crystals.
In this example, it is preferable that the decolorizer includes activated carbon particles, the salinity of the clear dibasic acid solution is adjusted to 10% before the decolorization, and the addition amount of the decolorizer is 0.8% of the mass of the clear dibasic acid solution.
In this embodiment, the long chain dibasic acid preferably comprises a C9-C18 long chain dibasic acid.
In this embodiment, it is preferable that the microchannel reactor comprises a Y-type microchannel reactor and a T-type microchannel reactor, the diameter of the microchannel reactor is 850 μm, the reaction temperature is controlled to 65 ℃, and the reaction pH is controlled to 4.5 at the end of the reaction.
In this embodiment, preferably, the layering in the second step includes an alkane layer, an emulsion layer, a supernatant layer, and a sediment layer, and the alkane layer, the emulsion layer, the supernatant layer, and the sediment layer are sequentially distributed in the container from top to bottom.
In this embodiment, preferably, the heating in the fifth step includes steam jacket heating, oil bath heating and electric heating, and the steam condensate obtained in the heating process is recycled for microbial fermentation and dilution of the fermentation liquor.
In this example, preferably, in the sixth step, the rotation speed of the crystallization kettle is adjusted to 60r/min, then the rotation speed of the crystallization kettle is increased to 85r/min after natural cooling is performed for 20min, then the cooling system of the crystallization kettle is opened, the temperature is reduced to 95 ℃ at the cooling speed of 8 ℃/h, and the temperature is kept for 30 min.
In this embodiment, preferably, the oxidation procedure in the first step is specifically as follows: when n-alkane enters candida tropicalis strain cells, reductase in strain cytochrome catalyzes the n-alkane to generate fatty alcohol, then the fatty alcohol is reduced to be catalyzed into fatty aldehyde under the action of fatty alcohol oxidase, fatty acid is catalyzed by fatty aldehyde dehydrogenase to generate fatty acid, and finally the fatty acid is oxidized in series to generate dibasic acid; the mutagenesis procedure included the addition of a nitrosoguanidine mutagen to Candida tropicalis species.
In this example, preferably, after the sixth step, the prepared long-chain dicarboxylic acid crystals are quantitatively weighed and packaged into bags, the long-chain dicarboxylic acid crystals packaged into the bags are subjected to sampling inspection, if the inspection result is qualified, the long-chain dicarboxylic acid crystals are packaged and put in storage, and if the inspection result is unqualified, the technology is improved until the inspection is qualified.
In this embodiment, the demulsifier preferably comprises an AP-type demulsifier.
Example 4
A preparation method of low-content low-carbon chain long-chain binary acid comprises the following steps:
step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures;
demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 2 hours, removing residual oil, and separating candida tropicalis strain residues, dibasic acid clear liquid and residual substrate by using a membrane filtration method;
step three, decoloring and diluting: adding a decolorizer into the clear dibasic acid solution obtained in the second step for decolorization, continuously performing for 50min, filtering again by using a filtering device after the decolorization is finished to obtain a decolorized dibasic acid solution, then adding deionized water into the decolorized dibasic acid solution for dilution, and controlling the salinity of the decolorized dibasic acid solution after dilution to be 6;
step four, adding acid: adding dilute sulfuric acid with the mass concentration of 40% into the dibasic acid diluent obtained in the step three, then injecting the mixed dibasic acid diluent into a microchannel reactor for mixing and reaction crystallization, and obtaining a mixture after full reaction;
step five, heating: putting the mixture obtained in the step four into a reaction kettle, heating to 100 ℃, thoroughly eliminating microcrystals in the mixture, and obtaining dibasic acid slurry after the reaction is finished;
step six, crystallization: and (4) injecting the dibasic acid slurry obtained in the fifth step into a crystallization kettle for curing, cooling to obtain primary crystals after curing, then placing the primary crystals into a centrifuge for centrifugal separation, repeatedly washing the separated crystals with purified water until the pH value is 6, and finally drying with drying equipment to obtain the long-chain dibasic acid crystals.
In this example, it is preferable that the decolorizer includes activated carbon particles, the salinity of the clear dibasic acid solution is adjusted to 8% before decolorization, and the addition amount of the decolorizer is 0.5% of the mass of the clear dibasic acid solution.
In this embodiment, it is preferable that the long-chain dibasic acid includes dodecanedioic acid.
In this embodiment, it is preferable that the microchannel reactor comprises a Y-type microchannel reactor and a T-type microchannel reactor, the diameter of the microchannel reactor is 550 μm, the reaction temperature is controlled to 55 ℃, and the reaction pH is controlled to 4.5 at the end of the reaction.
In this embodiment, preferably, the layering in the second step includes an alkane layer, an emulsion layer, a supernatant layer, and a sediment layer, and the alkane layer, the emulsion layer, the supernatant layer, and the sediment layer are sequentially distributed in the container from top to bottom.
In this embodiment, preferably, the heating in the fifth step includes steam jacket heating, oil bath heating and electric heating, and the steam condensate obtained in the heating process is recycled for microbial fermentation and dilution of the fermentation liquor.
In this embodiment, preferably, in the sixth step, the rotation speed of the crystallization kettle is adjusted to 60r/min, then the rotation speed of the crystallization kettle is increased to 85r/min after natural cooling for 20min, then the cooling system of the crystallization kettle is opened, the temperature is reduced to 95 ℃ at the cooling speed of 5 ℃/h, and the temperature is maintained for 30 min.
In this embodiment, preferably, the oxidation procedure in the first step is specifically as follows: when n-alkane enters candida tropicalis strain cells, reductase in strain cytochrome catalyzes the n-alkane to generate fatty alcohol, then the fatty alcohol is reduced to be catalyzed into fatty aldehyde under the action of fatty alcohol oxidase, fatty acid is catalyzed by fatty aldehyde dehydrogenase to generate fatty acid, and finally the fatty acid is oxidized in series to generate dibasic acid; the mutagenesis procedure included the addition of a nitrosoguanidine mutagen to Candida tropicalis species.
In this example, preferably, after the sixth step, the prepared long-chain dicarboxylic acid crystals are quantitatively weighed and packaged into bags, the long-chain dicarboxylic acid crystals packaged into the bags are subjected to sampling inspection, if the inspection result is qualified, the long-chain dicarboxylic acid crystals are packaged and put in storage, and if the inspection result is unqualified, the technology is improved until the inspection is qualified.
In this embodiment, the demulsifier preferably comprises an AE-type demulsifier.
Example 5
A preparation method of low-content low-carbon chain long-chain binary acid comprises the following steps:
step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures;
demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 2 hours, removing residual oil, and separating candida tropicalis strain residues, dibasic acid clear liquid and residual substrate by using a membrane filtration method;
step three, decoloring and diluting: adding a decolorizer into the clear dibasic acid solution obtained in the second step for decolorization, continuously performing for 50min, filtering again by using a filtering device after the decolorization is finished to obtain a decolorized dibasic acid solution, then adding deionized water into the decolorized dibasic acid solution for dilution, and controlling the salinity of the decolorized dibasic acid solution after dilution to be 6;
step four, adding acid: adding dilute sulfuric acid with the mass concentration of 50% into the dibasic acid diluent obtained in the step three, then injecting the mixed dibasic acid diluent into a microchannel reactor for mixing and reaction crystallization, and obtaining a mixture after full reaction;
step five, heating: putting the mixture obtained in the fourth step into a reaction kettle, heating to 120 ℃, thoroughly eliminating microcrystals in the mixture, and obtaining dibasic acid slurry after the reaction is finished;
step six, crystallization: and (4) injecting the dibasic acid slurry obtained in the fifth step into a crystallization kettle for curing, cooling to obtain primary crystals after curing, then placing the primary crystals into a centrifuge for centrifugal separation, repeatedly washing the separated crystals with purified water until the pH value is 7.5, and finally drying with drying equipment to obtain the long-chain dibasic acid crystals.
In this example, it is preferable that the decolorizer includes activated carbon particles, the salinity of the clear dibasic acid solution is adjusted to 10% before decolorization, and the addition amount of the decolorizer is 0.65% of the mass of the clear dibasic acid solution.
In this embodiment, preferably, the long-chain dibasic acid includes tridecane dibasic acid.
In this embodiment, it is preferable that the microchannel reactor comprises a Y-type microchannel reactor and a T-type microchannel reactor, the diameter of the microchannel reactor is 680 μm, the reaction temperature is controlled to 65 ℃, and the reaction pH is controlled to 3.9 at the end of the reaction.
In this embodiment, preferably, the layering in the second step includes an alkane layer, an emulsion layer, a supernatant layer, and a sediment layer, and the alkane layer, the emulsion layer, the supernatant layer, and the sediment layer are sequentially distributed in the container from top to bottom.
In this embodiment, preferably, the heating in the fifth step includes steam jacket heating, oil bath heating and electric heating, and the steam condensate obtained in the heating process is recycled for microbial fermentation and dilution of the fermentation liquor.
In this embodiment, preferably, in the sixth step, the rotation speed of the crystallization kettle is adjusted to 60r/min, then the rotation speed of the crystallization kettle is increased to 85r/min after natural cooling for 20min, then the cooling system of the crystallization kettle is opened, the temperature is reduced to 95 ℃ at the cooling speed of 7 ℃/h, and the temperature is maintained for 30 min.
In this embodiment, preferably, the oxidation procedure in the first step is specifically as follows: when n-alkane enters candida tropicalis strain cells, reductase in strain cytochrome catalyzes the n-alkane to generate fatty alcohol, then the fatty alcohol is reduced to be catalyzed into fatty aldehyde under the action of fatty alcohol oxidase, fatty acid is catalyzed by fatty aldehyde dehydrogenase to generate fatty acid, and finally the fatty acid is oxidized in series to generate dibasic acid; the mutagenesis procedure included the addition of a nitrosoguanidine mutagen to Candida tropicalis species.
In this example, preferably, after the sixth step, the prepared long-chain dicarboxylic acid crystals are quantitatively weighed and packaged into bags, the long-chain dicarboxylic acid crystals packaged into the bags are subjected to sampling inspection, if the inspection result is qualified, the long-chain dicarboxylic acid crystals are packaged and put in storage, and if the inspection result is unqualified, the technology is improved until the inspection is qualified.
In this embodiment, the demulsifier preferably comprises an AR demulsifier.
Comparative example 1, a long-chain dibasic acid crystal was prepared by a general solvent method.
Comparative example 2, crystals of a long chain dibasic acid were obtained by a conventional aqueous phase method.
Comparative example 3, a long-chain dicarboxylic acid crystal was prepared by a vegetable oil cracking method.
Comparative example 4, a long chain dibasic acid crystal was prepared by a chemical synthesis method.
The above examples and comparative examples are now tested and the results are given in the following table:
as can be seen from the above table, the preparation methods of examples 1-5 are superior to those of comparative examples 1-4 in all the parameters, and example 1 is the most preferred.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The preparation method of the low-content low-carbon-chain long-chain binary acid is characterized by comprising the following steps of:
step one, strain cultivation: candida tropicalis is selected as a strain, then normal alkane is used as a single carbon source to accelerate the growth speed of the Candida tropicalis, and a long-chain dibasic acid fermentation liquor is finally obtained through oxidation and mutagenesis procedures;
demulsifying and filtering: adding a demulsifier into the long-chain dibasic acid fermentation liquor obtained in the step one to kill candida tropicalis strains, layering the long-chain dibasic acid fermentation liquor, standing for 2-5h, removing residual oil, and separating candida tropicalis strain residues, dibasic acid clear liquid and residual substrate by using a membrane filtration method;
step three, decoloring and diluting: adding a decolorizer into the clear dibasic acid solution obtained in the second step for decolorization, continuously performing for 50min, filtering again by using a filtering device after the decolorization is finished to obtain a decolorized dibasic acid solution, then adding deionized water into the decolorized dibasic acid solution for dilution, and controlling the salinity of the decolorized dibasic acid solution after dilution to be 3-7;
step four, adding acid: adding dilute sulfuric acid with the mass concentration of 30-50% into the dibasic acid diluent obtained in the step three, then injecting the mixed dibasic acid diluent into a microchannel reactor for mixing and reaction crystallization, and obtaining a mixture after full reaction;
step five, heating: putting the mixture obtained in the fourth step into a reaction kettle, heating to 85-120 ℃, thoroughly eliminating microcrystals in the mixture, and obtaining dibasic acid slurry after the reaction is finished;
step six, crystallization: and (4) injecting the dibasic acid slurry obtained in the fifth step into a crystallization kettle for curing, cooling to obtain primary crystals after curing, then placing the primary crystals into a centrifuge for centrifugal separation, repeatedly washing the separated crystals with purified water until the pH value is 5.5-7.5, and finally drying with drying equipment to obtain the long-chain dibasic acid crystals.
2. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: the decolorant comprises activated carbon particles, the salinity of the clear binary acid solution is adjusted to 6-10% before decoloration, and the addition amount of the decolorant is 0.2-0.8% of the mass of the clear binary acid solution.
3. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: the long-chain dibasic acid comprises one or more of C9-C22 long-chain dibasic acid, C9-C18 long-chain dibasic acid, dodecanedioic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid and hexadecanedioic acid.
4. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: the microchannel reactor comprises a Y-shaped microchannel reactor and a T-shaped microchannel reactor, the diameter of the microchannel reactor is 280-850 mu m, the reaction temperature is controlled to be 45-65 ℃, and the reaction pH value is controlled to be 3.4-4.5 when the reaction endpoint is reached.
5. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: the layering in the second step includes alkane layer, emulsion layer, clear solution layer and subsides the layer, the alkane layer the emulsion layer clear solution layer and the subsides the layer from last to distributing in the container down in proper order.
6. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: and the heating in the fifth step comprises steam sleeve heating, oil bath heating and electric heating, and simultaneously, steam condensate water obtained in the heating process is recycled and used for microbial fermentation and diluted fermentation clear liquid.
7. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: and in the sixth step, the rotating speed of the crystallization kettle is adjusted to 35-60r/min, then the rotating speed of the crystallization kettle is increased to 50-85r/min after natural cooling is carried out for 20min, then a cooling system of the crystallization kettle is opened, the temperature is reduced to 85-95 ℃ at the cooling speed of 5-8 ℃/h, and the temperature is kept for 30 min.
8. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: the oxidation procedure in the first step is specifically as follows: when the n-alkane enters the candida tropicalis strain cells, the n-alkane is catalyzed by reductase in strain cytochrome to generate fatty alcohol, then the fatty alcohol is reduced to be catalyzed into fatty aldehyde under the action of fatty alcohol oxidase, fatty acid is catalyzed by fatty aldehyde dehydrogenase to generate fatty acid, and finally the fatty acid is oxidized in series to generate dibasic acid; the mutagenesis procedure comprises adding a nitrosoguanidine mutagen to the candida tropicalis species.
9. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: and sixthly, quantitatively weighing the prepared long-chain dicarboxylic acid crystals, packaging into bags, performing sampling inspection on the packaged long-chain dicarboxylic acid crystals, packaging and warehousing if the inspection result is qualified, and performing technical improvement until the inspection result is qualified.
10. The method for preparing low-content low-carbon chain long-chain dibasic acid as claimed in claim 1, wherein the method comprises the following steps: the demulsifier comprises one or more of an AP type demulsifier, an AE type demulsifier, an AR type demulsifier and urea.
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