CN1070394A - A kind of method of refining long-chain biatomic acid - Google Patents
A kind of method of refining long-chain biatomic acid Download PDFInfo
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Abstract
Use the long-chain alpha omega-dibasic acid of the refining carbon numbers from 11 to 18 of organic solvent such as methyl iso-butyl ketone (MIBK).At first heat organic solvent and dry cake, diprotic acid and impurity such as fermentation thalline etc. are fully dissolved respectively and be suspended in the organic phase.Insulation removes by filter suspended impurity, and filtrate is lowered the temperature through time variable control then, and adds corresponding diprotic acid crystal seed, is cooled to room temperature again, separates out granular diprotic acid crystal, filters at last, promptly gets the purified dicarboxylic acid product.Be characterized in that filtration velocity is fast, the product recovery rate height, the crystalline product granularity is big, the purity height.
Description
The present invention relates to a kind of method with organic solvent refining long-chain α omega-dibasic acid.
The long-chain alpha omega-dibasic acid is to utilize the microbial fermentation long-chain n-praaffin and the purpose meta-bolites that obtains.Because fermented liquid is a kind of heterogeneous system of complexity, it is external except containing zymophyte, also contains meta-bolites, emulsion and residual alkane and substratum etc.With centrifugal separation, filtration method, salting-out process, ion exchange method and membrane separation process etc. or to exist product purity not high, or product recovery rate is low, or problem such as complex disposal process, so just make and separate and the work of refining long-chain α omega-dibasic acid product becomes very difficult.For addressing the above problem, English Patent GB2043052 has proposed the method with Fatty Alcohol(C12-C14 and C12-C18) or ethanol or tetrahydrofuran (THF) or their aqueous solution refining long-chain biatomic acid.It is at first will stop fermented liquid to remove most of fermentation thalline through mechanical filter, then diprotic acid or its salt are settled down from fermented liquid, obtain thick diprotic acid filter cake with drying after filtration, make refining dicarboxylic acid product with organic solvents such as ethanol through heating, dissolving, filtration, cooling, crystallization at last.The problem of its existence is: 1. alcohol organic solvent under heating state can with long-chain biatomic acid generation esterification, or product purity and filtration velocity there is disadvantageous effect when handling with its aqueous solution, alcohols, decreases to the utilization ratio of solvent and the rate of recovery of product than higher to the solubleness of long-chain biatomic acid under the normal temperature.2. product granularity is little.3. secondary mechanical filtration sterilization body means are more loaded down with trivial details.
The objective of the invention is to select for use the method for not lowering the temperature with the employing time variable control and adding corresponding diprotic acid crystal seed, handle the dry cake of fermented liquid without the filtering thalline with the organic solvent of ketone of long-chain alpha omega-dibasic acid generation chemical reaction.Solution product recovery rate and purity descend, granularity is little and filtration velocity reaches problems such as complex operation slowly.
Produce in the long-chain alpha omega-dibasic acid process with the microbial fermentation long-chain n-praaffin, the diprotic acid of generation generally is that the form with its metal salt solution is present in the fermented liquid, and as the diprotic acid sodium salt solution, fermented liquid generally belongs to basic solution.After fermentation stops,, in the thalline in the system of killing, make residual normal paraffin and fermented liquid layering at first with the fermented liquid heating and add an amount of emulsion splitter breakdown of emulsion.At this moment fermented liquid is divided into four layers substantially: residual alkane layer, emulsion layer, supernatant liquid and thalline settled layer.Separate then and remove residual alkane, use mineral acid, as sulfuric acid, the fermentating liquid PH value of removing behind the alkane is transferred to 2-4, and the whole crystallizations of long-chain alpha omega-dibasic acid that metabolism is generated are separated out, after filtration, as Plate Filtration, obtain containing the diprotic acid filter cake of thalline of fermenting, the above-mentioned filter cake of final drying.Again the common heating of dry cake and organic solvent of ketone is fully dissolved respectively and is suspended in the organic phase until impurity such as long-chain alpha omega-dibasic acid and thalline, suspended substances such as above-mentioned thalline are filtered in insulation, then the organic solvent of ketone that contains dissolved long-chain alpha omega-dibasic acid is adopted the time variable control cooling, slowly stir, when temperature drops to solution and enters temperature when being situated between steady district, begin to add an amount of corresponding long-chain alpha omega-dibasic acid crystal seed, continue the time variable control cooling, when reaching certain temperature, improve cooling rate and mixing speed, be cooled to room temperature, filter long-chain alpha omega-dibasic acid crystal at last, promptly get the purified granulated product.
Separate or the emulsion and the fermentation thalline that filter in the above-mentioned fermented liquid are very difficult with common mechanical separation method.If microbiological contamination is arranged in the fermenting process slightly, just have a lot of thick liquid and generate, not only Residual oil separates badly, and separates the very difficulty that becomes between fermentation thalline and the fermented liquid.And do not filter the zymophyte body, directly with fermented liquid acidifying, crystallization, at this moment filtration velocity is very fast, has both made that microbiological contamination is arranged in the fermenting process slightly also is like this.
According to the similar principle that mixes of material, the solvent-applied recrystallization method can extract required material from solid or liquid mixture.It is that utilize product and the solubleness of impurity in solvent and partition ratio different reach to separate and purify or the purposes of purifying.Therefore, selecting the solvent of which kind of type and character is very important to refining desired product.
The long-chain alpha omega-dibasic acid is a kind of organic acid, and it has bigger solubleness in some organic solvent, even and in aqueous solvent under the heating state its solubleness also very low, therefore, it is only selecting organic solvent for use.
The present invention adopts three kinds of technique means:
1, selects the organic solvent of ketone of moderate boiling point for use
During generally with organic solvent dissolution long-chain alpha omega-dibasic acid, its consumption is the several times of long-chain alpha omega-dibasic acid treatment capacity, consumption of organic solvent is very big, when adopting lower boiling organic solvent such as ethanol, the loss of solvent is very important, especially in technical scale, often because the loss of organic solvent causes the cost of producing diprotic acid to improve greatly, and also be serious to the pollution of environment, therefore, it is favourable adopting the organic solvent of moderate boiling point.
Mainly consider following index when selecting organic solvent:
1) during high temperature, organic solvent is big to the solubleness of diprotic acid, and solubleness is little under the room temperature, and viscosity is little, easily filters.
2) there is Jie of broad surely to distinguish.
3) and product chemical reaction does not take place.
4) cost is low or moderate, and toxicity is little, and safety coefficient is big.
The present invention is directed to These parameters, mainly selected C for use
3-C
6Organic solvent of ketone, particularly methyl iso-butyl ketone (MIBK).Investigate as a comparison, also selected the ethanol organic solvent for use.
Acetone, butanone, methyl iso-butyl ketone (MIBK) and ethanol all have bigger solubleness to the long-chain alpha omega-dibasic acid, under equal temperature, ethanol is to the solubleness maximum of long-chain alpha omega-dibasic acid, but esterification easily takes place in ethanol and long-chain alpha omega-dibasic acid under the situation of heating, product purity and filtration velocity all there is bad influence, though and aqueous ethanolic solution and long-chain alpha omega-dibasic acid are difficult for taking place esterification, but after it and long-chain alpha omega-dibasic acid dissolved fully, filtration velocity but obviously slowed down.The acetone boiling point is lower, and is volatile, compare with methyl iso-butyl ketone (MIBK) with butanone, the effect respective differences some.Use C
3-C
6Organic solvent of ketone refining long-chain α omega-dibasic acid, the granularity of product and color and luster are all good than ethanol.Particularly effect is best during the refining α ω of methyl iso-butyl ketone (MIBK)-tridecanyldicarboxylic acid.C
3-C
6The organic solvent of ketone long-chain alpha omega-dibasic acid high more to carbon number, its solubleness is big more.Use C
3-C
6Behind the organic solvent of ketone dissolving dry cake, its filtration velocity is: fast with the solvent that the high solvent ratio carbon number of carbon number is low.As dissolve α ω-tridecanyldicarboxylic acid, methyl iso-butyl ketone (MIBK) is faster than the filtration velocity of butanone, acetone.Under 20 ℃, to the solubleness of long-chain alpha omega-dibasic acid be in proper order: ethanol＞acetone＞butanone＞methyl iso-butyl ketone (MIBK).The former solubleness is 7 times of latter's solubleness.Filtration velocity is smoothly: methyl iso-butyl ketone (MIBK)＞butanone＞acetone＞ethanol.When especially using aqueous ethanolic solution, filtration velocity is slower.Filtration velocity when methyl iso-butyl ketone (MIBK) is made solvent approximately is alcoholic acid 1.5-3 times, and methyl iso-butyl ketone (MIBK) is big to normal paraffin solubleness in addition, and is very complete to reclaiming alkane residual in the dry cake, and ethanol reclaims residual alkane poor ability.Because the methyl iso-butyl ketone (MIBK) boiling point is than ethanol height, it is easier than ethanol to reclaim the gasiform methyl iso-butyl ketone (MIBK).From filtration velocity and product color, purity, the rate of recovery and reclaim on the solubleness under organic solvent and the room temperature, select C for use
3-C
6Ketones solvent is relatively good, but preferably selects methyl iso-butyl ketone (MIBK).
The bulk density of actual measurement dry cake is about 0.39-0.43g/cm
3For the long-chain alpha omega-dibasic acid all is dissolved in the ketone organic phase, the most important thing is to select suitable liquid-solid this (weight ratio of organic solvent and dry cake).When liquid-solid ratio is 0.8-2.4: in the time of 1, be prone to supersaturation, cause blocking pipeline and problems such as filtration velocity descends for the second time, granularity is little.And select liquid-solid ratio for use is 3.0-6.0: 1 o'clock, just can address the above problem.Consider the economy of application, preferably select 3-4 for use: 1.
When organic solvent dissolution long-chain alpha omega-dibasic acid, all improve solvent temperature as far as possible.In short dissolution time, use the methyl iso-butyl ketone (MIBK) organic solvent, the rate of recovery of long-chain alpha omega-dibasic acid is the highest.As dissolution time is 0.5 hour, and the rate of recovery ethanol of α ω-tridecanyldicarboxylic acid is 85%, and butanone is 90%, and methyl iso-butyl ketone (MIBK)+ethanol is 94%, and methyl iso-butyl ketone (MIBK) is 97%.The effect of selecting methyl iso-butyl ketone (MIBK) for use is exactly to improve the product purity and the rate of recovery, reduces solvent loss.Help improving filtration velocity simultaneously.
2, time variable control cooling
After organic solvent of ketone and dry cake heating and the dissolving, contain the impurity such as thalline of the fermentation usefulness of dissolved long-chain alpha omega-dibasic acid and suspension in the organic solvent, the sex change of thalline at this moment particularly is easy to filter in methyl isobutyl ketone solvent.The organic solvent of ketone that contains dissolving long-chain alpha omega-dibasic acid is as filtrate, in insulation is pushed down into crystallizer.Adopt the time variable control cool-down method, when slowly cooling off the certain temperature interval, add a spot of long-chain alpha omega-dibasic acid crystal seed, be cooled to room temperature then.
The time variable control cool-down method designs according to diprotic acid relation of the solubleness under differing temps in organic solvent.It is a speed of cooling of controlling organic solvent by the temperature of regulating water indirectly, thereby the organic solution of avoiding containing the long-chain alpha omega-dibasic acid enters the supersaturation district, but make solution be in the steady district of Jie, at this moment can spontaneously not produce nucleus in the solution, if but in solution, add a spot of diprotic acid crystal seed, crystal seed will be grown up, and forms the bigger diprotic acid crystal of granularity at last.
When using the refining α ω of methyl iso-butyl ketone (MIBK) organic solvent-tridecanyldicarboxylic acid, programed temperature is as follows:
In the time of 90 ℃, begin to adopt the time variable control cooling, simultaneously slow stirred solution, because no surfusion, so can avoid producing on the tank skin " brilliant crust ".Approximately, entered the steady district that is situated between when solution temperature drops to 57-59 ℃, preferably in the time of 58 ℃, added an amount of long-chain alpha omega-dibasic acid crystal seed, continued the control cooling rate, in about 0.5-1.5 hour, reduced to 55 ℃ through 3-4 hour cooling control.Cool to room temperature with quicker slightly speed of cooling time variable control then, the time is approximately 2-3 hour.
The effect of time variable control cooling is exactly to avoid spontaneously occurring meticulous diprotic acid nucleus to separate out, and after adding crystal seed, diprotic acid is separated out and grown up on crystal seed, and filtering rate provides in advance necessary in order to form particulate state diprotic acid crystal and to improve for the second time.
3, add long-chain alpha omega-dibasic acid crystal seed
The granularity of purified long-chain alpha omega-dibasic acid is one of index of long-chain alpha omega-dibasic acid visual appearance.Meticulous long-chain alpha omega-dibasic acid crystal can make for the second time that filtering rate reduces, and can increase the organic solvent content in the purified long-chain alpha omega-dibasic acid product, simultaneously to packing, transport and use unfavorable.
When Jie who reaches solution in time variable control cooling surely distinguishes, should add corresponding long chain α omega-dibasic acid crystal seed.During as refining α ω-tridecanyldicarboxylic acid, add α ω-tridecanyldicarboxylic acid crystal seed; When making with extra care blended long-chain alpha omega-dibasic acid, add corresponding long-chain alpha omega-dibasic acid crystal seed, and add by different temperature respectively.The purity of crystal seed and granularity order number are respectively greater than 99% and 80, and add-on is the 1/1000-10/1000 of dry cake weight.
The effect that adds crystal seed is exactly the granularity that improves refining long-chain α omega-dibasic acid product, improves filtration velocity, reduces the content of organic solvent in crystalline product.
Can finish the present invention by following step:
1, with the termination fermented liquid of production long-chain alpha omega-dibasic acid, the filter cake and the C that obtain through heating, breakdown of emulsion, branch oil, acidizing crystal, filtration, drying
3-C
6Organic solvent of ketone, be 3-4 by liquid-solid ratio: 1 takes by weighing weight, and joins in the dissolving vessel.If in order to increase decolorizing effect, can add the powdered activated carbon that is equivalent to dry cake weight 3%.
2, with water vapor (as water vapor) indirect heating dissolving vessel with 120 ℃, preferably low fully solvent boiling point 5-15 ℃ of Heating temperature, after treating that long-chain alpha omega-dibasic acid and impurity such as fermentation thalline etc. dissolve respectively with finishing and are suspended in the organic solvent, with the nitrogen of 0.2-0.6MPa with the solution in the dissolving vessel in insulation is pushed down into hay tank, hay tank and line of pipes all are to be incubated indirectly with above-mentioned water vapor, filter cloth is equipped with in the hay tank bottom, removes by filter impurity such as fermentation thalline by filter cloth.
3, the organic solution that contains dissolving long-chain alpha omega-dibasic acid is sent in the recrystallization jar as filtrate, and also with the aforesaid method insulation, pressure medium still is above-mentioned nitrogen for recrystallization jar and line of pipes.Temperature with solution in thermometer or the temperature indicating instrument indication recrystallization jar.At first adopt the speed of cooling of solution in the indirect water controlling tank of time variable control cool-down method, slowly a stirred solution and a maintenance jar internal-external temperature difference are no more than 8 ℃ simultaneously, when slow cooling makes solution enter into the steady district of Jie, not having long-chain alpha omega-dibasic acid nucleus this moment occurs, add corresponding long chain α omega-dibasic acid crystal seed, continue slowly to stir and cooling solution, crystal seed begins to grow up, after 0.5-1.5 hour, suitably accelerate speed of cooling, make organic solution be cooled to room temperature, long-chain alpha omega-dibasic acid crystal after filtration, make it to separate with organic solvent, organic solvent is transported in the organic solvent storage tank.Blow away residual organic solvent in the long-chain alpha omega-dibasic acid crystal with pressurized air, the evaporable organic solvent steam reclaims these organic solvents, and sends back in the organic solvent storage tank by in the vacuum pump suction deep cooler in all treating processess after the condensation.If alkane residual in the organic solvent is more, the alkane of complexing is removed in available amount of urea complexing after the layering.Take out long-chain alpha omega-dibasic acid crystal, make suitable drying, promptly get purified finished product long-chain alpha omega-dibasic acid.
Compared with prior art, the present invention has improved the purity and the rate of recovery of long-chain alpha omega-dibasic acid product owing to selected the methyl iso-butyl ketone (MIBK) organic solvent employing time variable control cooling of moderate boiling point for use and the method for adding diprotic acid crystal seed; Improved the granularity of filtration velocity and product widely, the organic solvent loss is little, and working method is easy, executes reality easily.Filtration velocity can improve 1.5-3.0 doubly.Product purity reaches more than 98%, and the rate of recovery reaches 95%, and Granularity Distribution is: 10-20 order: 20-25%, and 20-40 order: 25-35%, 40-60 order: 25-35%, 60-80 order: 5-10%, 80 orders are above to be 4-10%.
Embodiment 1
To make substrate with positive structure n-tridecane hydrocarbon, produce the termination fermented liquid of α ω-tridecanyldicarboxylic acid with the fermentation of candida tropicalis mutant strain, behind heating, breakdown of emulsion separating residual alkane, regulate fermented liquid PH to 3 with sulfuric acid, the whole crystallizations of α ω-tridecanyldicarboxylic acid that metabolism generates are separated out, filter the final drying filter cake with flame filter press.α ω-tridecanyldicarboxylic acid content is 92.2%.Take by weighing about 800 liters of above-mentioned dry cake of 200kg and 640kg() the methyl iso-butyl ketone (MIBK) organic solvent, be enclosed in the stainless steel dissolving vessel of φ 1200 * 1500mm.With 0.1MPa, 121 ℃ water vapor by material in the chuck heating tank.Heating makes a jar interior solution temperature reach 90 ℃.Then with 0.1MPa, 99% nitrogen with above-mentioned hot solution in the insulation situation is pushed down into the stainless steel hay tank of φ 1200 * 500mm, filter cloth is equipped with in the hay tank bottom, filtration area is 0.5m
2Initially with the solution in the above-mentioned nitrogen pressure hay tank of 0.3MPa, use the nitrogen pressure of 0.5MPa at last, remove by filter impurity such as microorganism cells, filter under being incubated 90 ℃ for the first time and carry out, filtration time is 4 hours, and amount of filtrate is 970 liters.Filtrate is pressed in the stainless steel recrystallization jar of φ 1000 * 2000mm, still keeps 90 ℃ of temperature in the recrystallization jar.Enter the flow of mixing tank by the control water and steam, thereby regulate the temperature of cooling WATER AS FLOW MEDIUM, and keep a jar internal-external temperature difference and be no more than 8 ℃.Stirred solution simultaneously slowly, rotating speed is 60 rev/mins, reduces to 58 ℃ through solution temperature after 3 hours.At this moment add α ω-tridecanyldicarboxylic acid crystal seed, crystal seed purity is 99%, and granularity is the 80-100 order, and add-on is that 1kg(promptly accounts for 5/1000).Keep above-mentioned stirring velocity, programmed cooling to 55 ℃, the time is 0.6 hour.Improve rotating speed to 80 rev/min, continue the time variable control cooling, drop to 20 ℃ at last, the time is 3 hours.Filter α ω-tridecanyldicarboxylic acid crystal, filtration area is 0.5m
2, operation pressure reduction is 0.3MPa, filtration time is 10 minutes for the second time.Methyl iso-butyl ketone (MIBK) organic solvent as filtrate is recovered in the stainless steel basin of φ 1000 * 2000mm about 720 liters.With the filtering pressurized air of 0.2MPa blow down methyl iso-butyl ketone (MIBK) residual in the crystal filtering layer and and device in remaining gaseous state methyl iso-butyl ketone (MIBK) deliver to together in-5 ℃ the icy salt solution condensing works and reclaim.Take out purified α ω-tridecanyldicarboxylic acid product at last.Result of implementation tabulation 1.
Embodiment 2
Refining α ω-16-dicarboxylic acid.α ω-16-dicarboxylic acid content is 87%.Take by weighing dry cake 1kg, about 4 liters of methyl iso-butyl ketone (MIBK) 3.2kg().Pack into 10 liters stainless steel dissolving vessel.The volume of hay tank and recrystallization jar and filtration area are 10 liters and 0.03m
216-dicarboxylic acid crystal seed purity is 99%, granularity is the 80-100 order, and add-on is that 1g(promptly accounts for 1/1000), the temperature when adding crystal seed is 54 ℃.Its method is with embodiment 1.Dissolution time is 3.0 hours, and filtration time is 22.0 minutes for the first time, and amount of filtrate is 4.80 liters; Filtration time is 57 seconds for the second time, and amount of filtrate is 3.76 liters.Table 2 is results of implementation.
The size-grade distribution of product, %(W/W)
More than 10-20 order 20-40 order 40-60 order 60-80 order 80 orders
22.1 30.6 32.4 10.4 4.5
Embodiment 3
Refining α ω-12,13 and 16 carbon mixed dibasic acids.Total acid content is 90.2%, and content is respectively separately: 36.2%, 42.7% and 11.3%.The purity of above-mentioned diprotic acid crystal seed and granularity difference 99% and 80-100 order.Their add-on is respectively 3.21g, 3.79g, 1.0g, and gross weight is that 8g(promptly accounts for 8/1000).Add fashionable temperature and be respectively 60 ℃, 58 ℃, 54 ℃.Its method is with embodiment 2.Dissolution time is 3.5 hours.Filtration time is 21.1 minutes for the first time, and amount of filtrate is 4.82 liters; Filtration time is 65 seconds for the second time, and amount of filtrate is 3.75 liters, and result of implementation is listed table 3 in.
Embodiment 4
Implementation method is made with extra care α ω-tridecanyldicarboxylic acid with embodiment 2; Use butanone instead.Dissolution time is 3.0 hours.Filtration time is 23.1 minutes for the first time, and amount of filtrate is 4.81 liters; Filtration time is 62 seconds for the second time, and amount of filtrate is 3.75 liters.Result of implementation is listed table 4 in.
Table 4 butanone is made the result of implementation of solvent
Average for the first time for the second time average product product product solvent
The filtering rate filtering rate purity rate of recovery color and luster rate of recovery
L/m·h L/m·h % %
416 7,258 98 96.1 whites 93.7
The size-grade distribution of product, %(W/W)
More than 10-20 order 20-40 order 40-60 order 60-80 order 80 orders
17.5 25.4 30.0 15.7 11.4
Comparative example 1
Method is made with extra care α ω-tridecanyldicarboxylic acid with embodiment 2.Use 95% ethanol organic solvent instead.70 ℃ of Heating temperatures, dissolution time are 2.5 hours.In the time of 46 ℃, add crystal seed.Filtration time is 104 minutes for the first time, 4.70 liters of amount of filtrate; Filtration time is 118 seconds for the second time, and amount of filtrate is 3.20 liters.Result of implementation is listed table 5 in.
Comparative example 2
Method is with embodiment 2.Refining α ω-tridecanyldicarboxylic acid does not add crystal seed.Dissolution time 3.0 hours, filtration time is 21.6 minutes for the first time, amount of filtrate is 4.78 liters; Filtration time is 97 seconds for the second time; Amount of filtrate is 3.75 liters.Result of implementation is listed table 6 in.
Comparative example 3
Method is with embodiment 2.Refining α ω-tridecanyldicarboxylic acid, service routine is not controlled the method for lowering the temperature and adding crystal seed, and dissolution time is 3.1 hours, water cooling, when reducing to 20 ℃ by 90 ℃, the time is 1.4 hours.Filtration time is 22.1 minutes for the first time, and amount of filtrate is 4.80 liters; Filtration time is 118 seconds for the second time, and amount of filtrate is 3.76 liters.Result of implementation is listed table 7 in.
Claims (9)
1, a kind of method with organic solvent refining long-chain α omega-dibasic acid.The long-chain alpha omega-dibasic acid is stopped fermented liquid through heating, breakdown of emulsion, branch oil, acidizing crystal, filtration and drying, obtain dried filter cake.It is characterized in that this filter cake and organic solvent of ketone are heated jointly, the long-chain alpha omega-dibasic acid is dissolved fully, filter the method that the back is adopted the time variable control cooling and added corresponding long chain α omega-dibasic acid crystal seed, finish the refining of separate impurities such as fermentation thalline and diprotic acid simultaneously.
2,, it is characterized in that before stopping the processing of fermented liquid acidizing crystal, needn't removing by filter the fermentation thalline according to the method for claim 1.
3, according to the method for claim 1, the carbon number that it is characterized in that organic solvent of ketone is 3-6.
4, according to claim 1,3 method is characterized in that preferably methyl iso-butyl ketone (MIBK) of ketones solvent.
5, according to the method for claim 1, the carbon number that it is characterized in that the long-chain alpha omega-dibasic acid is 11-18.
6, according to claim 1,5 method is characterized in that the first acid of preferably refining α ω-13 carbon.
7, according to the method for claim 1, it is characterized in that preferably 90-105 ℃ of heating for dissolving temperature, adopt the time variable control cooling then, begin to add crystal seed when cooling to 57-59 ℃, preferably 58 ℃, reduce to room temperature at last.
8, according to the method for claim 1, the granularity order number that it is characterized in that adding crystal seed is greater than 80, and the crystal seed add-on is 1 with the ratio of dry cake weight: 1000-10: 1000, and purity is greater than 99%.
9, according to claim 1,3 method, the weight ratio that it is characterized in that organic solvent of ketone and filter cake is 3-6: 1,3-4 preferably: 1.
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| CN91108814A CN1029842C (en) | 1991-09-11 | 1991-09-11 | Method for refining long-chain binary acid |
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| CN1049688C (en) * | 1995-10-05 | 2000-02-23 | 中国石油化工总公司 | Method for treatment of alpha, omega dibasic acid fermentation liquor |
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- 1991-09-11 CN CN91108814A patent/CN1029842C/en not_active Expired - Lifetime
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|---|---|---|---|---|
| CN1049688C (en) * | 1995-10-05 | 2000-02-23 | 中国石油化工总公司 | Method for treatment of alpha, omega dibasic acid fermentation liquor |
| CN1056882C (en) * | 1996-10-09 | 2000-09-27 | 中国石油化工总公司抚顺石油化工研究院 | Process for preparing high purity long chain dicarboxylic acid and its ester |
| CN1064951C (en) * | 1997-12-08 | 2001-04-25 | 中国石油化工总公司抚顺石油化工研究院 | Method for refining long-chain bibasic acid |
| CN1079389C (en) * | 1998-12-03 | 2002-02-20 | 中国石油化工集团公司 | Process for refining long-chain biatomic acid |
| CN1088055C (en) * | 1999-09-29 | 2002-07-24 | 中国石油化工集团公司 | Process for extracting alpha-or omege-alkadicarboxylic acid from fermented liquid and refining it |
| CN101955424B (en) * | 2010-04-30 | 2013-05-08 | 山东瀚霖生物技术有限公司 | Solvent recovery device of long-carbon-chain binary acid refining production process |
| CN101955424A (en) * | 2010-04-30 | 2011-01-26 | 山东瀚霖生物技术有限公司 | Solvent recovery device of long-carbon-chain binary acid refining production process |
| 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 |
| CN103242156A (en) * | 2012-02-08 | 2013-08-14 | 上海凯赛生物技术研发中心有限公司 | Method for treating a reaction solution containing a long-chain dicarboxylate |
| CN103113209A (en) * | 2013-02-05 | 2013-05-22 | 徐杰 | Method for removing organic amine nitrogen impurities from long chain binary acid produced by using microbiological method |
| WO2014121427A1 (en) * | 2013-02-05 | 2014-08-14 | Xu Jie | Method for removing organic amine nitrogen impurities in long-chain binary acids produced by microbiological method |
| CN103113209B (en) * | 2013-02-05 | 2015-05-06 | 徐杰 | Method for removing organic amine nitrogen impurities from long chain binary acid produced by using microbiological method |
| CN113249414A (en) * | 2021-05-19 | 2021-08-13 | 江苏达成生物科技有限公司 | Preparation method of low-content low-carbon-chain long-chain binary acid |
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|---|---|
| CN1029842C (en) | 1995-09-27 |
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