CN103242156A - Method for treating a reaction solution containing a long-chain dicarboxylate - Google Patents
Method for treating a reaction solution containing a long-chain dicarboxylate Download PDFInfo
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- CN103242156A CN103242156A CN2012100277320A CN201210027732A CN103242156A CN 103242156 A CN103242156 A CN 103242156A CN 2012100277320 A CN2012100277320 A CN 2012100277320A CN 201210027732 A CN201210027732 A CN 201210027732A CN 103242156 A CN103242156 A CN 103242156A
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- C07—ORGANIC CHEMISTRY
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- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The invention relates to a method for treating a reaction solution containing a long-chain dicarboxylate, comprising: acidifying the reaction solution, to converting the long-chain dicarboxylate into a corresponding long-chain diacid; extracting the long-chain diacid by an ester solution; and separating out an organic phase rich in a long-chain diacid, aftertreating the long-chain diacid, to obtain the long-chain diacid product. The method of the invention has advantages of short technology route, short operation period, small occupation equipment, high production efficiency, high product yield, good product quality, high product purity and shallow product color, and the ester solvent can be recycled and reused, and is in favor of resource saving and environment protection.
Description
Technical field
The present invention relates to contain the treatment process of the reaction solution of long-chain biatomic acid salt.
Background technology
Long-chain biatomic acid is the base monomer raw material of a series of extraordinary synthetic materialss, long-chain biatomic acid and derivative monomer thereof can be produced extraordinary nylon, polycarbonate, powder coating, spices, hot melt adhesive, extraordinary lubricant etc., are the important source material of synthetic perfume, engineering plastics, cold resistant plasticizer, senior lubricant and products such as polyamide hot, powder coating.
Long-chain biatomic acid does not exist at occurring in nature, can synthesize the long-chain biatomic acid of some kind, for example sebacic acid and SL-AH with chemical method.In addition, can also produce long-chain biatomic acid by biological process.Microbe fermentation method transforms and produces long-chain biatomic acid is that the biochemical industry of nineteen seventies rise is in the application of petrochemical industry.Biological process can provide C
9～C
18Serial long-chain biatomic acid monomer.
It is substrate that microbe fermentation method transforms with alkane or lipid acid, utilize microbial fermentation to transform and produce the fermented liquid that contains long-chain biatomic acid salt, in the described fermented liquid except long-chain biatomic acid salt, also comprise impurity such as thalline, residual alkane and fatty heteroacid, therefore need handle that long-chain biatomic acid hydrochloric acid is wherein changed into long-chain biatomic acid to fermented liquid, and with the long-chain biatomic acid purifies and separates.
The method that obtains at present long-chain biatomic acid from fermented liquid comprises that pre-treatment, acidizing crystal, filtration obtain dicarboxylic acid product, further carry out aftertreatment purifying such as recrystallization then and obtain target product, this method steps is tediously long, and yield is low, energy consumption and production cost are higher.
Chinese patent application 200410018255.7 discloses a kind of production method of positive long-chain biatomic acid, wherein to fermented liquid carry out centrifuging or membrane filter method except thalline, add a series of processing such as activated carbon decolorizing, acidizing crystal, Plate Filtration, obtain dicarboxylic acid product, then dicarboxylic acid product is distilled a series of aftertreatment purifies and separates such as refining or secondary solvent method crystal refining, obtain qualified target product.
The existing processes route has following shortcoming: 1, operational path complexity, and the operational cycle is long, takies a large amount of equipment, and production efficiency is low; 2 yields are low, need before the acidifying through complicated pretreatment, and the yield of the dicarboxylic acid product that acidizing crystal obtains generally has only 93～95%; 3, acidizing crystal poor product quality, the dicarboxylic acid product saliferous height, the color that obtain are dark, must be through just obtaining qualified product such as a series of aftertreatment purifies and separates such as recrystallizations; 4, consume a large amount of gacs, the usage quantity of gac is up to 5～10% of product, and is not recyclable because of the gac after the decolouring, causes the wasting of resources and environmental pollution.
Therefore wish to have a kind of novel method of the reaction solution that contains long-chain biatomic acid salt directly being handled and can high productivity be obtained the long-chain biatomic acid qualified product always.
Summary of the invention
The objective of the invention is to overcome the shortcoming that prior art exists, provide to the simple high-efficient treatment method to the reaction solution that contains long-chain biatomic acid salt, to obtain the long-chain biatomic acid qualified product with high yield.
For achieving the above object, the invention provides a kind for the treatment of process to the reaction solution that contains long-chain biatomic acid salt, it is characterized in that the reaction solution acidifying so that described long-chain biatomic acid salt is converted into corresponding long-chain biatomic acid, by the solvent extraction long-chain biatomic acid, obtain qualified long-chain biatomic acid product by simple aftertreatment at last then.
Particularly, the invention provides following technical scheme:
1, contain the treatment process of the reaction solution of long-chain biatomic acid salt, it may further comprise the steps:
1) with the reaction solution acidifying, so that long-chain biatomic acid salt is converted into corresponding long-chain biatomic acid;
2) with esters solvent extraction step 1) long-chain biatomic acid that obtains;
3) isolate the organic phase that is rich in long-chain biatomic acid, and it carried out aftertreatment, obtain the long-chain biatomic acid product,
Wherein extract to the temperature that is lower than the phase boiling point that is rich in long-chain biatomic acid at normal temperature, condition is that extraction temperature is lower than 100 ℃, and wherein extracts under less than 5 condition at PH.
2, according to technical scheme 1 described method, wherein said reaction solution is the fermented liquid that biological process is produced long-chain biatomic acid.
3, according to technical scheme 2 described methods, be fermentation treatment fluid with described fermentation liquor pretreatment wherein, described fermentation treatment fluid is to remove one or more of other components except long-chain biatomic acid salt in the fermented liquid or reduce the liquid that obtains behind its content.
4, according to each described method among the technical scheme 1-3, wherein said long-chain biatomic acid is carboxyl at the two ends of chain, has the saturated or unsaturated straight chain diprotic acid of 9 to 18 carbon atoms, is preferably selected from nonane diacid, sebacic acid, 11 carbon dicarboxylic acids, SL-AH, tridecanyldicarboxylic acid, ten four-carbon dicarboxylic acids, 15 carbon dicarboxylic acids, 16-dicarboxylic acid, 17 carbon dicarboxylic acids, 18 carbon dicarboxylic acids and 9-alkene-18 carbon diacid.
5, according to each described method among the technical scheme 1-4, wherein said esters solvent is the C of one or more of formic acid or acetic acid
2-C
8Alcohol ester is preferably selected from butyl formate, propyl acetate, Isoamyl Acetate FCC, isobutyl acetate, isopropyl acetate, n-amyl acetate, and is one or more of in ethyl acetate, butylacetate, octyl acetate, 2-ethyl hexyl ethanoate, the sec-octyl acetate.
6, according to each described method among the technical scheme 1-5, wherein extract to the temperature of the organic phase boiling point that is rich in long-chain biatomic acid at 60 ℃, condition is that extraction temperature is lower than 100 ℃.
7, according to each described method among the technical scheme 1-6, be 2～5 at PH wherein, preferred 3～5, more preferably extract under 3.5～4.5 the condition.
8, according to each described method among the technical scheme 1-7, wherein the pure content in the esters solvent is not higher than 5 weight %.
9, according to each described method among the technical scheme 1-8, wherein adopt mineral acid, preferred hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, more preferably sulfuric acid is the reaction solution acidifying.
10, according to each described method among the technical scheme 1-9, wherein said aftertreatment comprises further isolates long-chain biatomic acid with what be rich in that the cooling mutually of long-chain biatomic acid and precipitation separation go out that long-chain biatomic acid or heating be rich in long-chain biatomic acid with the evaporation extraction agent.
Embodiment
The invention provides a kind for the treatment of process to the reaction solution that contains long-chain biatomic acid salt, it may further comprise the steps:
1) with the reaction solution acidifying, so that long-chain biatomic acid salt is converted into corresponding long-chain biatomic acid;
2) with esters solvent extraction step 1) long-chain biatomic acid that obtains;
3) isolate the organic phase that is rich in long-chain biatomic acid, and it carried out aftertreatment, obtain the long-chain biatomic acid product,
Wherein extract to the temperature that is lower than the organic phase boiling point that is rich in long-chain biatomic acid at normal temperature, condition is that extraction temperature is lower than 100 ℃, and wherein extracts under less than 5 condition at PH.
The addition sequence that it will be understood by those skilled in the art that the acid that acidifying is used in the inventive method and the esters solvent agent that extracts usefulness does not have particular requirement, can or add acid and esters solvent simultaneously by any order.
Reaction solution described in the present invention can be to be the mixture that obtains after reaction medium reacts with water.In an embodiment of the invention, the reaction solution that uses in the inventive method can be that biological process is produced in the long-chain biatomic acid, the fermented liquid that obtains through microbial fermentation.Except the product long-chain biatomic acid salt that contains fermentation, also comprise thalline usually and such as impurity such as residual alkane and fatty heteroacid in the described reaction solution.
In an embodiment of the invention, can be fermentation treatment fluid with fermentation liquor pretreatment, described fermentation treatment fluid is to remove one or more of other components except long-chain biatomic acid salt in the fermented liquid or reduce the liquid that obtains behind its content.Can effectively remove one or more of other components beyond the long-chain biatomic acid salt or reduce its content by known technology (for example by ceramic membrane filter or whizzer or flocculation filtration or activated carbon filtration etc.).
The purpose of acidifying is to make the long-chain biatomic acid salt in the reaction solution fully change into long-chain biatomic acid, with carrying out smoothly of guaranteeing to extract.
Usually adopt mineral acid that reaction solution is carried out acidifying, preferred mineral acid example includes but not limited to hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid etc., more preferably sulfuric acid.
In the inventive method, with the resulting long-chain biatomic acid of reaction solution acidifying can be carboxyl at the two ends of chain, have a saturated or unsaturated straight chain diprotic acid of 9 to 18 carbon atoms.In a preferred implementation, described long-chain biatomic acid can be selected from nonane diacid, sebacic acid, 11 carbon dicarboxylic acids, SL-AH, tridecanyldicarboxylic acid, ten four-carbon dicarboxylic acids, 15 carbon dicarboxylic acids, 16-dicarboxylic acid, 17 carbon dicarboxylic acids, 18 carbon dicarboxylic acids and 9-alkene-18 carbon diacid.
The characteristics of the esters solvent that uses in the inventive method are not dissolve each other with water on the one hand; Under the high temperature, with the diprotic acid reaction, simultaneously long-chain biatomic acid there is not good solubility on the other hand.The esters solvent that is appropriate to the inventive method for example is the C of formic acid or acetic acid
2-C
8Alcohol ester.Preferred esters solvent includes but not limited to butyl formate, propyl acetate, Isoamyl Acetate FCC, isobutyl acetate, isopropyl acetate, n-amyl acetate, ethyl acetate, butylacetate, octyl acetate, 2-ethyl hexyl ethanoate, sec-octyl acetate etc.Can be used alone esters solvent or use the mixture of two or more esters solvents.
In one embodiment, described esters solvent is the mixed solution of butylacetate and isobutyl acetate.
Generally contain part alcohols impurity in the esters solvent, there are two aspects in the source of these alcohols impurity, contains on the one hand the pure impurity of certain content in the commercially available esters solvent raw material, and the content of this alcohol impurity is generally lower, is no more than 0.5 weight %; In the process of extraction long-chain biatomic acid, because the degraded of esters solvent produces a certain amount of alcohol, cause pure content to raise on the other hand, this part content is applied mechanically with the distill repeatedly of solvent and is continued to increase, and can reach one at last than higher level.
The inventor finds, esterification can at high temperature take place with long-chain biatomic acid with the alcohol that mixes in the esters solvent in extraction, generate long-chain biatomic acid monoesters or dibasic acid esters, this reduces the yield of final long-chain biatomic acid on the one hand, and the quality of product is suffered damage.
Therefore the impurity alcohol content of controlling in the esters solvent is conducive to improve purity and the quality that extracts yield and extracted products.
In a preferred implementation, the pure content in the esters solvent that uses in the control extraction process is not higher than 5 weight %.
Be used for extraction esters solvent amount for dissolving long-chain biatomic acid significant quantity or more than.
Term used herein " dissolving long-chain biatomic acid significant quantity " refers under extraction temperature the quantity of solvent of the long-chain biatomic acid that generates after the acidifying in the effective solubilizing reaction liquid.
By the mensuration to long-chain biatomic acid salts contg in the reaction solution, those skilled in the art determine dissolving long-chain biatomic acid significant quantity easily.
Temperature requirement to extraction is not harsh, as long as can have good solubleness just passable to long-chain biatomic acid.Can extract to the temperature that is lower than the organic phase boiling point that is rich in long-chain biatomic acid at normal temperature, condition is that extraction temperature is lower than 100 ℃.Under comparatively high temps, extract, because the solubleness height of long-chain biatomic acid in extraction agent, thereby be conducive to taking full advantage of of extraction agent, reduced the consumption of extraction agent.Therefore from saving solvent load, improve the extraction efficiency aspect and consider, preferably under higher temperature, extract.In a preferred implementation, extract to the temperature that is lower than the organic phase boiling point that is rich in long-chain biatomic acid at 60 ℃, condition is that extraction temperature is lower than 100 ℃.When under extraction temperature of the present invention, extracting, realized good layering between water and the organic phase.In one embodiment, extraction temperature is not less than 70 ℃.In another embodiment, extraction temperature is not less than 75 ℃.In another embodiment, extraction temperature is not less than 80 ℃.In another embodiment, extraction temperature is not less than 85 ℃.In another embodiment, extraction temperature is not less than 90 ℃.In another embodiment, extraction temperature is not less than 95 ℃.
Because of the relation of solubleness, be rich in the organic extraction mutually of esters solvent and long-chain biatomic acid and also may contain a spot of water.Term used herein " is rich in the phase boiling point of long-chain biatomic acid " and refers to the azeotropic point (if there are azeotropic point in this esters solvent and water) of boiling point (under the situation of the azeotropic point that does not have this esters solvent and water) or this esters solvent and the water of employed esters solvent in the extraction process.
Concrete extraction temperature and the time of adopting, because of the difference of the esters solvent of concrete use and the long-chain biatomic acid that extracts different.The enough esters solvents of general adding are heated to suitable extraction temperature, to guarantee that long-chain biatomic acid can fully be dissolved in the organic phase.The extraction time can fully contact with water to guarantee organic phase, and extraction is entirely good, and the extraction time can be several minutes to a few hours, and generally under agitation condition, the extraction time was not less than 5 minutes.
The inventor finds, in extraction process, because of contacting of organic phase and water, can cause the degraded of esters solvent.As everyone knows, generate organic acid and alcohol after the organic ester hydrolysis.Especially, the inventor finds that the degradation speed of esters solvent is subjected to the considerable influence of extraction conditions in the organic phase.The degradation speed of esters solvent is accelerated along with the rising of reduction, the temperature of extraction PH and/or the prolongation of extraction time.The solvent loss that this can cause in the extraction process reduces the economy of extraction process.
So, for loss, minimizing long-chain biatomic acid generation esterification side reaction, the preferably degradation speed of control esters solvent in extraction process that reduces solvent in the extraction process.
In the extraction process, the degradation speed of esters solvent and residing chemical environment are closely related.In the extraction process of long-chain biatomic acid, can reduce the temperature of extraction and reduce the extraction time by the amount of suitable increase esters solvent, avoid the excessive degradation of esters solvent in extraction process.
But from saving solvent load, improve the economy angle of extraction process, sometimes preferably under higher extraction temperature, extract, in this case, by under extraction temperature, especially higher extraction temperature, for example 60 ℃ or higher, down the PH ten minutes of control extraction environment is favourable as 60～95 ℃, and suitable PH control can significantly alleviate even avoid the degraded of esters solvent.
Usually, become long-chain biatomic acid in order to make the abundant acidifying of long-chain biatomic acid salt (such as but not limited to the long-chain biatomic acid sodium salt) in the reaction solution, the PH that preferably controls aqueous reaction solution is lower than about 5.
In extraction process, especially for example 60 ℃ or higher of higher temperature, in 60～95 ℃ of following extraction processes, for fear of the too fast degraded of esters solvent, before the adding esters solvent extracted, preferably the PH control with the aqueous solution had been not less than about 2.
In a kind of embodiment, preferably about 2～about 5, more preferably from about 3～about 5, extract under especially preferred about PH of 3.5～about 4.5.
In a kind of illustrative embodiments, can control PH by adding mineral acid (such as but not limited to sulfuric acid), the addition sequence of acid and organic solvent can exchange, and can add acid earlier in reaction solution and regulate PH, adds esters solvent then; Also can add esters solvent earlier, add acid then and regulate PH.But consider to add sour process to the influence of esters solvent, the preferred PH that adds sour conditioned reaction liquid earlier adds esters solvent then and extracts.
In the methods of the invention, can adopt the extraction separation long-chain biatomic acid of simple post-processing technology known in the art from organic extraction mutually.
In one embodiment, described aftertreatment includes but not limited to, be rich in the cooling mutually of long-chain biatomic acid and precipitation separation go out long-chain biatomic acid or heating be rich in long-chain biatomic acid with the evaporation extraction agent, to obtain product.
The esters solvent that uses in recyclable recycling the inventive method.
Utilize long-chain biatomic acid product that the inventive method obtains in aspect good quality such as purity, color and lusters, need not further to make with extra care purifying just as the qualified product that meet industrial use.Certainly, according to specific application requiring, also can further make with extra care purifying to the product of the inventive method, with its quality of further raising.
Beneficial effect
1, utilizes the inventive method, need not pre-treatment is carried out in the reaction of biological process production long-chain biatomic acid, to remove thalline and impurity such as residual alkane or fatty heteroacid wherein, just can directly carry out acidifying and extraction treatment to reaction solution, obtain the qualified product in aspect excellences such as purity, color and lusters.
In the extraction phase that the inventive method obtains the content of long-chain biatomic acid up to about 99% or more than.
Utilize long-chain biatomic acid product that the direct acidifying of the present invention, extraction process obtain than conventional filter earlier, decolour, acidifying then, cooling filter the product that obtains in aspect excellences such as purity, color and lusters.
2, the inventive method has been avoided resource and the cost waste that a large amount of use activated carbon decolorizings cause, and has improved the yield of long-chain biatomic acid simultaneously.
3, the inventive method operational path is short, the operational cycle is short, the equipment that takies is few, production efficiency is high; The product yield height that extraction obtains; Good product quality, purity height, of light color that extraction obtains; The recyclable recycling of employed esters solvent is conducive to saving and the environment protection of resource.
Embodiment
The present invention is described in detail below by embodiment, so that the features and advantages of the present invention are clearer, but the present invention is not limited to the embodiment that lists herein.Among the listed embodiment, can use the well-known ordinary method of those skilled in the art to measure every index in this article, for example use following testing method:
1, diprotic acid gas chromatographic detection:
Mensuration with reference to lipid acid in GB5413.27-2010 infant or baby food and the dairy products.
2, ash content detects:
Get testing sample calcination in crucible, calcination 2 hours in 700～800 ℃ of retort furnaces then, gravimetry after the cooling constant weight calculates percent by weight.
3, determination of total nitrogen content:
Adopt Kjeldahl determination.
4, determination of light transmittance:
The diprotic acid sample dissolution is become 5% sodium-salt aqueous solution, and UV detects the transmittance under the 430nm then.
5, solvent and dirt content test thereof:
The capillary column gas chromatography method.For example referring to the industrial ethyl acetate of standard GBT3728-2007
6, the mensuration of diprotic acid esterification:
Adopt the nuclear magnetic resonance, instrument to detect near the charateristic avsorption band of the long-chain biatomic acid ester of 4.1ppm.
The fermented liquid that uses among following comparative example and the embodiment, fermented liquid are crossed the preparation method of ceramic membrane clear liquid, fermented liquid centrifugal clear liquid can be referring to patent ZL200410018255.7.
The comparative example 1
Get the SL-AH fermented liquid 100L of fermentation ends among the patent ZL200410018255.7 embodiment 4, wherein diprotic acid content 168g/L is heated to 70 ℃ by vapor heat exchanger, adds alkali then and regulates pH to 8.5, remove thalline by ceramic membrane filter, obtain SL-AH film clear liquid.In the film clear liquid, add Powdered Activated Carbon, the gac add-on be in the solution diprotic acid gross weight 6%, stirred 60 minutes, filter, obtain SL-AH decolouring feed liquid.Add sulfuric acid in destainer, regulate pH to 3, filter, obtain the SL-AH product, product yield is 94%, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 1
Get the SL-AH fermented liquid of patent ZL200410018255.7 embodiment 4 fermentation ends, wherein diprotic acid content 168g/L.Regulate pH with 98% vitriol oil and reach 4.2.Then about 700g butylacetate (containing butanols 5%) is added in about 600ml SL-AH fermented liquid, insulated and stirred is 2 hours in 85 ℃ water-bath.Then, separate with separating funnel.
Detect and separate the waste water that obtains, wherein diprotic acid content is less than 0.2%, and butanol concentration is 0.1%.Detect organic phase, the concentration of butanols is 5.6%, and the esterified ratio of long-chain biatomic acid is 0.5%.Known that by detected result the total degradation rate of butylacetate in water and organic phase is 1.1%, diprotic acid extraction yield is greater than 98%.The organic phase that separation is obtained cools to room temperature, filters, and obtains dicarboxylic acid product, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 2
Get the tridecanyldicarboxylic acid fermented liquid of fermentation ends among the patent ZL200410018255.7 embodiment 5, wherein diprotic acid content 165g/L regulates pH with 98% vitriol oil and reaches 1.5.Then about 500g butylacetate (containing butanols 0.5%) is added in about 500ml tridecanyldicarboxylic acid fermented liquid, insulated and stirred is 2 hours in 93 ℃ water-bath.Then, separate with separating funnel.
Detect and separate the waste water that obtains, wherein diprotic acid content is less than 0.2%, and butanol concentration is 0.1%.Detect organic phase, the concentration of butanols is 3.2%, and the esterified ratio of long-chain biatomic acid is 0.6%.Known that by detected result the total degradation rate of butylacetate in water and organic phase is 4.5%, diprotic acid extraction yield is greater than 98%.The organic phase that separation is obtained cools to room temperature, filters, and obtains dicarboxylic acid product, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 3
Get the tridecanyldicarboxylic acid fermented liquid of fermentation ends among the patent ZL200410018255.7 embodiment 5, wherein diprotic acid content 165g/L regulates pH with 98% vitriol oil and reaches 3.6.Then about 500g ethyl acetate (containing ethanol 0.2%) is added in about 500ml tridecanyldicarboxylic acid fermented liquid, insulated and stirred is 1 hour in 74 ℃ water-bath.Then, separate with separating funnel.
Detect and separate the waste water that obtains, wherein diprotic acid content is less than 0.2%, and alcohol concn is 0.1%.Detect organic phase, concentration of ethanol is 0.28%, and the esterified ratio of long-chain biatomic acid is lower than detectability (0.1%).Known that by detected result the total degradation rate of ethyl acetate in water and organic phase is less than 1%, diprotic acid extraction yield is greater than 98%.The organic phase that separation is obtained cools to room temperature, filters, and obtains dicarboxylic acid product, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 4
Get 11 carbon dicarboxylic acid fermentation liquid of fermentation ends among the patent ZL200410018255.7 embodiment 3, ceramic membrane filter obtains binary sorrel clear liquid content 120g/L except thalline.Regulate pH with 98% vitriol oil and reach 4.0.Then about 400g n-amyl acetate (containing amylalcohol 0.3%) is added in about 400ml 11 carbon dicarboxylic acid film clear liquids, insulated and stirred is 20 minutes in 75 ℃ water-bath.Then, separate with separating funnel.
Detect and separate the waste water that obtains, amylalcohol concentration is less than 0.1%.Detect organic phase, the concentration of amylalcohol is 0.3%, does not detect the degraded of esters solvent.It is esterified not detect long-chain biatomic acid.The organic phase that separation is obtained cools to room temperature, filters, and obtains dicarboxylic acid product, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 5
Get 15 carbon dicarboxylic acid fermentation liquid of fermentation ends among the patent ZL200410018255.7 embodiment 7, the bactofugation body obtains except thalline fermented liquid, wherein diprotic acid content 142g/L.Regulate pH with 98% vitriol oil and reach 4.3.Then about 700g butyl formate (containing butanols 0.2%) is added in about 500ml 15 carbon dicarboxylic acid degerming body fluid, insulated and stirred is 20 minutes in 80 ℃ water-bath.Then, separate with separating funnel.
Detect and separate the waste water that obtains, butanol concentration is less than 0.1%.Detect organic phase, the concentration of amylalcohol is 0.2%, does not detect the degraded of esters solvent.It is esterified not detect long-chain biatomic acid.The organic phase that separation is obtained cools to room temperature, filters, and obtains dicarboxylic acid product, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 6
Get the SL-AH fermented liquid of fermentation ends among the patent ZL200410018255.7 embodiment 4, wherein diprotic acid content 47.7g/L.Regulate pH with 98% vitriol oil and reach 3.8.Then about 200g butylacetate (containing butanols 0.2%) and 200 is restrained in the about 1300ml SL-AH fermented liquid of isobutyl acetate (containing isopropylcarbinol 0.15%) mixed solvents adding, insulated and stirred is 0.5 hour in 85 ℃ water-bath.Then, separate with separating funnel.Do not detect the degraded of esters solvent.It is esterified not detect long-chain biatomic acid.
The organic phase that separation is obtained cools to room temperature, filters, and obtains dicarboxylic acid product, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 7
Get the 18 carbon dicarboxylic acid fermentation liquid of the ZL200410018255.7 embodiment 2 of fermentation ends, wherein diprotic acid content 7.75%.Regulate pH with 98% vitriol oil and reach 4.0.Then about 150g 2-ethyl hexyl ethanoate (containing isooctyl alcohol 0.2%) is added in about 200ml 18 carbon dicarboxylic acid fermentation liquid, insulated and stirred is 0.5 hour in 85 ℃ water-bath.Then, separate with separating funnel.Do not detect the degraded of esters solvent.It is esterified not detect long-chain biatomic acid.
The organic phase that separation is obtained cools to room temperature, filters, and obtains dicarboxylic acid product, and products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Embodiment 8
Get ten four-carbon dicarboxylic acid fermentation liquid of fermentation ends among the patent ZL200410018255.7 embodiment 6, wherein diprotic acid content 195g/L.Regulate PH3.7 with 50% hydrochloric acid, then about 1600g butylacetate is joined in the 200ml ten four-carbon dicarboxylic acid fermentation liquid, insulated and stirred is 10 minutes in 30 ℃ water-bath.Then, separate with separating funnel.Organic phase evaporation concentration to 120 gram with separation obtains 60 ℃ of following filtered while hot, obtains product.Do not detect the degraded of esters solvent.It is esterified not detect long-chain biatomic acid.
Products obtained therefrom is carried out diprotic acid content, ash oontent, nitrogen content and determination of light transmittance, the results are shown in Table 1.
Quality product among each embodiment of table 1
By above with embodiment of the invention 1-8 and comparative example 1 more as can be known, the inventive method can utilize the short period to realize effective processing to the reaction solution that contains long-chain biatomic acid, the production efficiency height obtains yield height, the good product quality of product.
Yield described here refer to be rich in long-chain biatomic acid mutually in the amount of long-chain biatomic acid with respect to the weight percentage of the amount of long-chain biatomic acid contained in the reaction solution.
The long-chain biatomic acid product that adopts the present invention to obtain, its color, foreign matter content all have significantly improvement than former extraction process.Be limited to the downstream client to the requirement of long-chain biatomic acid quality product, former extraction process products obtained therefrom must just can reach the requirement of downstream application such as spices, polymer production through further purification.And the production technique that adopts the present invention to propose can obtain high-quality product once going on foot, and product performance satisfy most of long-chain biatomic acid downstream requirement of client.
By above with embodiment of the invention 3-8 and embodiment 1-2 more as can be known, when under comparatively high temps, extracting, butanol content in the PH during the control extraction and the extraction liquid, when being conducive to avoid extracting, organic solvent is degraded in a large number, has improved the economy of technology; In addition, product has been avoided the generation of byproduct in the extraction process by the alcohols material esterification when being conducive to avoid extracting.
Fermented liquid, fermented liquid are crossed the ceramic membrane clear liquid, the fermented liquid centrifugal clear liquid describes the inventive method though only adopt in the embodiment of the invention, but those skilled in the art can be understood that, the inventive method is not limited to fermented liquid, fermented liquid is crossed ceramic membrane clear liquid, fermented liquid centrifugal clear liquid, can be used for comprising other reaction solution of long-chain biatomic acid salt equally.
Optional embodiment of the present invention has more than been described, to instruct those skilled in the art how to implement and to reproduce the present invention.In order to instruct technical solution of the present invention, simplified or omitted some conventional aspects.After reading specification sheets of the present invention, those skilled in the art can easily expect reaching modification or the alternative of the technical solution of the present invention of the object of the invention according to the common practise in the chemical field, and the present invention those skilled in the art should understand that the modification or the alternative that are derived from these embodiments will fall within the scope of the invention.
Claims (10)
1. contain the treatment process of the reaction solution of long-chain biatomic acid salt, it may further comprise the steps:
1) with the reaction solution acidifying, so that long-chain biatomic acid salt is converted into corresponding long-chain biatomic acid;
2) with esters solvent extraction step 1) long-chain biatomic acid that obtains;
3) isolate the organic phase that is rich in long-chain biatomic acid, and it carried out aftertreatment, obtain the long-chain biatomic acid product,
Wherein extract to the temperature that is lower than the phase boiling point that is rich in long-chain biatomic acid at normal temperature, condition is that extraction temperature is lower than 100 ℃, and wherein extracts under less than 5 condition at PH.
2. method according to claim 1, wherein said reaction solution are the fermented liquid that biological process is produced long-chain biatomic acid.
3. method according to claim 2 is fermentation treatment fluid with described fermentation liquor pretreatment wherein, and described fermentation treatment fluid is to remove one or more of other components except long-chain biatomic acid salt in the fermented liquid or reduce the liquid that obtains behind its content.
4. according to each described method among the claim 1-3, wherein said long-chain biatomic acid is carboxyl at the two ends of chain, has the saturated or unsaturated straight chain diprotic acid of 9 to 18 carbon atoms, is preferably selected from nonane diacid, sebacic acid, 11 carbon dicarboxylic acids, SL-AH, tridecanyldicarboxylic acid, ten four-carbon dicarboxylic acids, 15 carbon dicarboxylic acids, 16-dicarboxylic acid, 17 carbon dicarboxylic acids, 18 carbon dicarboxylic acids and 9-alkene-18 carbon diacid.
5. according to each described method among the claim 1-4, wherein said esters solvent is the C of one or more of formic acid or acetic acid
2-C
8Alcohol ester is preferably selected from butyl formate, propyl acetate, Isoamyl Acetate FCC, isobutyl acetate, isopropyl acetate, n-amyl acetate, and is one or more of in ethyl acetate, butylacetate, octyl acetate, 2-ethyl hexyl ethanoate, the sec-octyl acetate.
6. according to each described method among the claim 1-5, wherein extract to the temperature that is lower than the organic phase boiling point that is rich in long-chain biatomic acid at 60 ℃, condition is that extraction temperature is lower than 100 ℃.
7. according to each described method among the claim 1-6, be 2～5 at PH wherein, preferred 3～5, more preferably extract under 3.5～4.5 the condition.
8. according to each described method among the claim 1-7, wherein the pure content in the esters solvent is not higher than 5 weight %.
9. according to each described method among the claim 1-8, wherein adopt mineral acid, preferred hydrochloric acid, sulfuric acid, phosphoric acid or nitric acid, more preferably sulfuric acid is the reaction solution acidifying.
10. according to each described method among the claim 1-9, wherein said aftertreatment comprises further isolates long-chain biatomic acid with what be rich in that the cooling mutually of long-chain biatomic acid and precipitation separation go out that long-chain biatomic acid or heating be rich in long-chain biatomic acid with the evaporation extraction agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107954858A (en) * | 2017-12-13 | 2018-04-24 | 天津大学 | A kind of crystal form of heneicosanedioic acid and preparation method thereof |
| CN108558646A (en) * | 2017-12-13 | 2018-09-21 | 天津大学 | A kind of crystal form of heneicosanedioic acid and preparation method thereof |
| CN113493378A (en) * | 2020-04-01 | 2021-10-12 | 上海凯赛生物技术股份有限公司 | Long-chain dicarboxylic acid product and refining process thereof |
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| CN111592457B (en) * | 2019-02-21 | 2023-06-30 | 上海凯赛生物技术股份有限公司 | Long-chain dibasic acid with concentrated particle size distribution and preparation method thereof |
| CN114524722A (en) * | 2020-10-31 | 2022-05-24 | 中国石油化工股份有限公司 | Method for extracting long-chain dicarboxylic acid |
| CN115028530A (en) * | 2021-03-03 | 2022-09-09 | 上海凯赛生物技术股份有限公司 | Extraction process of long-chain dicarboxylic acid and long-chain dicarboxylic acid product |
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| CN113493378A (en) * | 2020-04-01 | 2021-10-12 | 上海凯赛生物技术股份有限公司 | Long-chain dicarboxylic acid product and refining process thereof |
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