CN104418721A - Long-chain binary acid continuous crystallization method - Google Patents
Long-chain binary acid continuous crystallization method Download PDFInfo
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Abstract
The invention provides a long-chain binary acid continuous crystallization method and an application thereof. The continuous crystallization method comprises the step that multi-stage crystallization, preferably three-stage crystallization, is sequentially carried out on an organic solution containing a binary acid. Compared with a batch crystallization device, the crystallization method disclosed by the invention is high in industrial automatic degree, and stable in product quality on the premise that the same product quality is obtained; meanwhile, the operating personnel are greatly reduced; and the investment cost is reduced by over 50% (on the product scale of 10,000t/year) in comparison with a batch crystallization device, and therefore, the high-quality long-chain binary acid crystal can be efficiently obtained through the continuous crystallization equipment; the equipment investment is reduced; the fluctuation in production is reduced; and the long-chain binary acid continuous crystallization method is an ideal long-chain binary acid crystallization method, and can be suitable for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of purification process of chemical, particularly relate in a kind of long-chain biatomic acid production process the method for carrying out long-chain biatomic acid and refining, the method that especially long-chain biatomic acid of biological fermentation production is refining.
Background technology
Long-chain biatomic acid (Long chain dicarboxy acids) refers to the aliphatic dibasic acid (being called for short DCn) containing 9 and above carbon atom in carbochain, comprise saturated and unsaturated dibasic acid, being the fine chemical product that a class has important and extensive industrial use, is synthesize the important source material such as fine perfumery, high performance engineering plastics, high-temperature electric medium, high-grade hot melt adhesive, cold resistant plasticizer, senior lubricant, senior paint and coating in chemical industry.
Long-chain biatomic acid does not exist at occurring in nature, can synthesize the long-chain biatomic acid of some kind by chemical synthesis.Such as can adopt Viscotrol C in the presence of a base heating hydrolysis produce ricinolic acid soda soap, then generate ricinolic acid with sulfuric acid acidation, then in the presence of a diluent with alkali blend mixture heating pyrolyze, obtain sebacic acid disodium, after acidifying, obtain sebacic acid finished product.Divinyl trimerization such as can be adopted again to obtain cyclododecatriene, dodecane is obtained again through Hydrogenation, SL-AH (IndustrialOrganic Chemistry is obtained through cyclododecanone again with nitric acid oxidation, Third Completely Revised Edition, Klaus Weissermel, Hans-Jurgen Arpe, VCH, 1997).But produce long-chain biatomic acid by chemical synthesis and there is technology, equipment requirements, the shortcomings such as high energy consumption is large, and some long-chain biatomic acids are also difficult to chemically prepare.
Microbe fermentation method be the seventies rise microbial fermentation technology in the application of petrochemical industry, be subject to most attention at home and abroad.The production of current long-chain biatomic acid progressively adopts microbe fermentation method to carry out.
Production by Microorganism Fermentation long-chain biatomic acid is an emerging green bio chemical industry, Applied Biotechnology method, with petroleum by-product light wax oil or lipid acid and derivative thereof for raw material, microbial fermentation processes is adopted to produce long carbochain biatomic acid, its technique is simple, and working condition is gentle, and production process can be carried out at normal temperatures and pressures, yield is high, cost is low, is a kind of Green Chemistry industry not having environmental pollution.
Prepare in the process of long-chain biatomic acid at microbe fermentation method, the fermented liquid usually obtained biological fermentation process carries out a series of process to obtain long-chain biatomic acid product.
CN103030550A discloses a kind of method of purifying long-chain biatomic acid and salt thereof, and the raw material containing long-chain biatomic acid or its salt is carried out acidifying, then alkaline solution neutralization, heating, acidifying again; To precipitate heating for multiple times and remove impurity, crystallisation by cooling obtains long-chain biatomic acid crystal.But the crystallization of melt should not control, often wrap up a large amount of impurity, and frequent heated solution produces by product.In the commercial run of existing production long-chain biatomic acid, for obtaining the long-chain biatomic acid of high-quality, the technique of solvent crystallization is generally all adopted to carry out refining dicarboxylic acid product.The method of existing employing solvent crystallization is produced in the process of long carbochain biatomic acid, needs to utilize crystallizer (disclosed in CN20236650U crystallizer) to make long carbochain biatomic acid crystallization.As:
" process for purification of tridecanyldicarboxylic acid " (beautiful beautiful, Zhang Yanli, Wang Chonghui. meticulous and specialty chemicals, 2002,20 (10): 13-14) method of process is divided into Aqueous phase, esterification process and solvent method in a literary composition.The solvent method of broad sense comprises extraction process and crystallization process, and wherein, extraction process refers to: the difference utilizing solute solubleness in immiscible solvent, working method solute extracted from the solution that another solvent forms with a kind of solvent; Crystallization process refers to: utilize the difference of the differing temps solubleness in a solvent of different components in mixture to realize the working method of separation and purification.
CN1410408A discloses a kind of process for purification of C11-C18 long-chain biatomic acid, first petroleum fermentation product is carried out salt-forming reaction, and other impurity is removed in extraction, then acidifying, crystallization.
CN102617320A discloses a kind of method processed the reaction solution containing long-chain biatomic acid salt, by reaction solution acidifying so that described long-chain biatomic acid salt is converted into long-chain biatomic acid, add extraction agent to extract the long-chain biatomic acid generated, isolate the phase being rich in long-chain biatomic acid, and isolate long-chain biatomic acid further.
CN1570124A discloses a kind of method that solvent method prepares long-chain biatomic acid, after dibasic acid fermentation liquor fermentative production obtained is degerming, add activated carbon to decolour, acidifying is separated out diprotic acid and is obtained crude product, and then adopt and add acetate solvate and dissolve, add gac to be deviate from by pigment, then carry out decrease temperature crystalline precipitation, separating, washing drying obtains finished product.
CN1221510C discloses a kind of process for purification of long-chain biatomic acid, by after breakdown of emulsion tunning heating, make diprotic acid melting, thus with other magazins' layout in the aqueous solution, then oil reservoir is added water and carries out crystallization.
Crystallization processes directly has influence on the granular size of long-chain biatomic acid crystal, and then affects the purity of long-chain biatomic acid.Particle is too little, then specific grain surface amasss conference adsorbing contaminant, has influence on the application of long-chain biatomic acid, particularly in the application of polymerization field.The crystallization processes of prior art is generally directly that linear or Temperature fall is to target temperature, and these methods exist the shortcomings such as production efficiency is low, production cost is high, unstable product quality.
Therefore, those skilled in the art wish there is a kind of new crystallization method, can improve existing crystallisation problems.
Summary of the invention
In order to solve the problem existing for current long-chain biatomic acid crystallization method, the invention provides a kind of long-chain biatomic acid continuous crystallisation process, being realized by the mode of multistage crystallization.
The present invention first aspect is to provide a kind of long-chain biatomic acid continuous crystallisation process, and step comprises:
Organic solution containing long-chain biatomic acid is carried out multistage crystallization.
Specifically, long-chain biatomic acid partial crystallization is separated out the organic solution cooling containing long-chain biatomic acid, crystalline mother solution is lowered the temperature further, to make undecomposed long-chain biatomic acid at least part of crystallization in crystallisation process in organic solution.
Wherein, be preferably after completing prime crystallization, directly or at once carry out next stage crystallisation step.
In continuous crystallisation process of the present invention, preferably carry out at least three grades of crystallizations.
Wherein, preferably, in described multistage crystallization process, temperature during rear class crystallization is lower than temperature during prime crystallization.
In a kind of preferred embodiment of continuous crystallisation process of the present invention, preferably carry out at least three grades of crystallizations, second stage Tc is higher than first step Tc, and third stage Tc is higher than second stage Tc.
In preferred embodiment of the present invention, be more preferably, the Tc of first step crystallization is lower 1 ~ 10 DEG C than long-chain biatomic acid Precipitation Temperature in described organic solution, is preferably 2 ~ 8 DEG C.
Wherein, long-chain biatomic acid Precipitation Temperature in described organic solution refers to that long-chain biatomic acid starts temperature when separating out in described organic solution, can be recorded by those skilled in the art according to prior art.
In first step crystallisation process of the present invention, can there is certain fluctuation in Tc, but fluctuation range is preferably within the scope of ± 2 DEG C, is more preferably ± 1 DEG C within the scope of.
In preferred embodiment of the present invention, the Tc of second stage crystallization is lower than first step Tc 5 ~ 15 DEG C, is preferably 8 ~ 12 DEG C.
In the crystallisation process of the second stage of the present invention, can there is certain fluctuation in Tc, but fluctuation range is preferably within the scope of ± 3 DEG C, is more preferably ± 2 DEG C within the scope of.
In preferred embodiment of the present invention, the Tc of third stage crystallization is lower than second stage Tc 5 ~ 70 DEG C, preferably 5 ~ 50 DEG C, more preferably 5 ~ 30 DEG C, most preferably is 8 ~ 12 DEG C.Be more preferably, the Tc of third stage crystallization, close to normal temperature, as 15 ~ 35 DEG C, is preferably 20 ~ 30 DEG C, is more preferably 25 ~ 30 DEG C, as 30 DEG C.
In third stage crystallisation process of the present invention, can there is certain fluctuation in Tc, but fluctuation range is preferably within the scope of ± 3 DEG C, is more preferably ± 2 DEG C within the scope of.
In continuous crystallisation process of the present invention, described multistage crystallization by realizing the organic solution containing long-chain biatomic acid by every one-level crystallizer Step crystallization successively in multistage crystallization equipment.
In the one of continuous crystallisation process of the present invention is preferably implemented, described continuous crystallisation is three grades of crystallizations, and the slurry with crystallization after previous stage crystallization directly enters next stage crystallizer.
Wherein, the residence time in every one-level crystallizer is preferably >=1 hour, is more preferably 1 ~ 5 hour, is more preferably 1 ~ 3 hour.
In continuous crystallisation process of the present invention, can be adopt continuously feeding or intermittent type charging, and be preferably continuously feeding.In described continuously feeding process, input concentration (weight ratio containing di-carboxylic acid and solvent in long-chain biatomic acid organic solution) is 1:2.5 ~ 5(w/w), input concentration fluctuation is preferably in ± 2% scope.
In continuous crystallisation process of the present invention, long-chain biatomic acid of the present invention be preferably carboxyl at the two ends of carbochain, there is the saturated of 9 to 18 carbon atoms or unsaturated Straight chain diatomic acid.It can be any one or a few the mixture in above-mentioned diprotic acid.
In continuous crystallisation process of the present invention, described long-chain biatomic acid can be any one or a few the mixture in saturated or unsaturated long-chain biatomic acid, wherein, described unsaturated long-chain biatomic acid is preferably containing at least one unconjugated double bond, described unconjugated double bond is preferably non-conjugated C=C double bond or C ≡ C triple bond, and is preferably C=C double bond.
Preferably, long-chain biatomic acid of the present invention can be selected from: any one or a few the mixture in nonane diacid, sebacic acid, DC11, SL-AH, tridecanyldicarboxylic acid, DC14,15 carbon dicarboxylic acids, 16-dicarboxylic acid, DC17, DC18,9-alkene-ten eight carbon diacid.
In continuous crystallisation process of the present invention, the described organic solution containing long-chain biatomic acid refers to the organic solution containing long-chain biatomic acid and impurity.This solution can be that biological process obtains long-chain biatomic acid fermented liquid and prepares after treatment, also can be the organic solvent dissolution liquid that chemical method obtains reaction solution.
In some embodiments of the invention, the organic solution of described long-chain biatomic acid can from long-chain biatomic acid fermented liquid or long-chain biatomic acid fermentation treatment fluid, the long-chain biatomic acid extraction solution that the mode such as acidified, extraction obtains.Wherein, generally, moisture, fermentation substrate remnants, long-chain biatomic acid salt, thalline and other impurity is comprised in long-chain biatomic acid fermented liquid.Fermentation treatment fluid is the liquid obtained after removing one or more other components except long-chain biatomic acid salt except in fermented liquid or reduction one or more other component concentrations except long-chain biatomic acid salt.Wherein, or described component concentration can be reduced obtain fermentation treatment fluid by one or more other components in the means such as ceramic membrane filter, whizzer, flocculation filtration, activated carbon filtration removing fermented liquid except long-chain biatomic acid salt.Chinese patent literature (application number 201210027749.6) discloses a kind of method preparing long-chain biatomic acid organic solution.
In a kind of preferred embodiment of continuous crystallisation process of the present invention, in described acidization, fermented liquid pH value can adjust according to the difference of diprotic acid kind, but be preferably adjusted to 1 ~ 5 in the present invention, be more preferably 2 ~ 5, be more preferably 3 ~ 4, make the dicarboxylate in fermented liquid all change into diprotic acid, to guarantee carrying out smoothly of extraction.
Wherein, in described acidization, adjust ph can use mineral acid usually, and example hydrochloric acid, sulfuric acid, nitric acid etc., being more preferably sulfuric acid, can be the vitriol oil, as the vitriol oil of weight concentration 97%.
In the another kind of preferred embodiment of continuous crystallisation process of the present invention, in described extraction process, available extraction solvent can be selected from ketone, alcohol, ester, varsol, be preferably solvent long-chain binary hydroxy acid to good solubility, and the solvent preferably do not dissolved each other with water, be more preferably the solvent at high temperature do not reacted with diprotic acid, the example of concrete extraction solvent comprises, but be not limited to butanols, isopropylcarbinol, amylalcohol, toluene, tetrachloroethylene, methyl iso-butyl ketone (MIBK) (MIBK), ethyl acetate, propyl acetate, isopropyl acetate, butylacetate, isobutyl acetate, n-amyl acetate, Isoamyl Acetate FCC etc., or any mixed solvent of above-mentioned solvent, as isobutyl acetate and butanols mixed solvent.Wherein, the volume ratio of isobutyl acetate and butanols is preferably (0.1 ~ 10): (0.1 ~ 20).
Wherein, in the fermented liquid that extract, the weight ratio of di-carboxylic acid and extraction solvent is preferably 1: (2.5 ~ 5).
Wherein, extraction temperature and time, because of extraction agent and diprotic acid difference and slightly distinguish.
Generally will add enough extraction agents, be heated to suitable extraction temperature, to ensure that diprotic acid can all be dissolved in organic phase, preferred extraction temperature is at 60 DEG C to 95 DEG C.
Extraction time guaranteeing that organic phase can fully contact with aqueous phase, extract and be entirely good, generally under agitation, extraction time is not less than 5 minutes.
In the continuous crystallisation process that the present invention is above-mentioned, extraction and acidifying order can exchange, and such as, can first add sulfuric acid adjust ph, then add extraction solvent in fermented liquid; Also first extraction solvent can be added, then adjust ph.The adjustment adding order does not affect final effect of extracting.
In continuous crystallisation process of the present invention, the lysate that the described organic solution containing long-chain binary hydroxy acid can also be formed in organic solvent from long-chain biatomic acid dissolving crude product.
Wherein, described long-chain biatomic acid crude product is obtained by long-chain biatomic acid fermented liquid or the pre-treatment of long-chain biatomic acid fermentation treatment fluid.Pre-treatment can adopt method well known in the art, such as, and " the process for refining research of SL-AH " (Li Zhanchao, Master's thesis, Beijing University of Chemical Technology, 2009) disclosed pretreatment process; The disclosed pretreatment process obtaining long-chain biatomic acid crude product through breakdown of emulsion, point oil, acidifying, filtration of " process for purification of tridecanyldicarboxylic acid " (Xie Lijuan etc., meticulous and specialty chemicals, the 20th phase in 2002,13-14 page); In addition, the Chinese patent literature CN1292072C(patent No.: ZL200410018255.7) disclose fermented liquid is added alkali adjust ph to 8 ~ 12, be heated to 60 ~ 100 DEG C, then centrifuging or membrane filter method separating thallus is utilized, diprotic acid clear liquid and fermentation substrate remnants, then clear liquid is heated to 60 ~ 100 DEG C, and with acid for adjusting pH value to 2 ~ 5 acidizing crystal, after Plate Filtration, obtains diprotic acid crude product.
Wherein, in the lysate that described long-chain biatomic acid dissolving crude product is formed in organic solvent, described organic solvent is preferably when temperature is at 60 DEG C to 95 DEG C, the organic solvent of saturation solubility between 20 grams/100 grams to 40 grams/100 grams of long-chain biatomic acid.
More preferably, described organic solvent is preferably alcohol, monoprotic acid or monobasic acid ester, two or more mixture wherein, is more preferably acetic acid, acetic acid C1-C6 alcohol ester, C1-C6 alcohol or two or more mixture wherein.The citing of described organic solvent including, but not limited to acetic acid, ritalin, vinyl acetic monomer, propyl acetate, n-butyl acetate, amyl acetate-n, isoamyl acetate, capryl acetate, or two or more mixture in them.Described organic solvent is more preferably acetic acid, N-BUTYL ACETATE or primary isoamyl alcohol.
Wherein, in lysate, the part by weight of long-chain biatomic acid and described organic solvent is preferably 1: (2.5 ~ 5), and solvent temperature is at 60 DEG C to 95 DEG C.
In continuous crystallisation process of the present invention, also comprise the step of crystal separation.Described separation step can be any solid-liquid separating method, as centrifugal, filtration etc.
In continuous crystallisation process of the present invention, the step of being carried out by the crystal of separation washing can also be comprised.
Wherein, in described water-washing step, the consumption of water is preferably 1 ~ 3 times of long-chain biatomic acid crystal weight, is more preferably 1 times.
In continuous crystallisation process of the present invention, can also comprise and the crystal of the crystal of separation or washing is carried out dry step.
Wherein, in described drying process, temperature preferably controls at 95 ~ 120 DEG C, to be more preferably 100 ~ 110 DEG C, as 105 DEG C.
Wherein, the process of drying can also be comprised between washing and drying.
In continuous crystallisation process of the present invention, the long-chain biatomic acid that the described organic solution containing long-chain binary hydroxy acid can also be prepared by chemical method is dissolved in that chemical solvents prepares.Described chemical solvents can be ketone, acetic acid, acetic acid C1-C6 alcohol ester, alkane one or more.
The present invention second aspect is to provide a kind of device for long-chain biatomic acid continuous crystallisation, comprises the multistage crystallization equipment of connecting successively, and every one-level crystallizer is equipped with heat sink.
Wherein, in the device of described continuous crystallisation, described heat sink can adopt conventional cool-down method, as interchanger cooling, or flash distillation cooling.
Wherein, in the device of described continuous crystallisation, every one-level crystallizer opening for feed is on top, and discharge port is in bottom, and previous stage crystallizer bottom discharge mouth is connected with the upper feed inlet of rear stage crystallizer.
Wherein, in the device of described continuous crystallisation, the design of crystallizer can adopt various ways, as being with the crystallizer of diversing bucket, or the crystallizer of band elutriation leg, to optimize the crystalline environment of each step further, guarantee the size composition of the finished product.
In a kind of preferred embodiment of the device of continuous crystallisation of the present invention, described continuous crystallisation device is three grades of crystallization apparatus.
Third aspect of the present invention is to provide a kind of method of producing long-chain biatomic acid, and step comprises:
Step 1, obtains the organic solution containing long-chain biatomic acid by biological process or chemical synthesis;
Step 2, adopts any one above-mentioned method to carry out crystallization to the described organic solution containing long-chain biatomic acid.
The present invention the 4th aspect is to provide a kind of method using long-chain biatomic acid synthetic polymer, and wherein said polymkeric substance can be polyester or polymeric amide, and is preferably polymeric amide.
The method of the present invention the 4th described in aspect, step comprises:
Step 1, adopts any one method above-mentioned to carry out crystallization to long-chain biatomic acid raw material, obtains long-chain biatomic acid product;
Step 2, is polymerized gained long-chain biatomic acid product with comonomer.
Wherein, described long-chain biatomic acid raw material is can be solid or the organic solution containing diprotic acid, when described long-chain biatomic acid is solid, will be prepared into the organic solution containing diprotic acid after described long-chain binary hydroxy acid material dissolution.
Described long-chain biatomic acid raw material is for can be from long-chain biatomic acid fermented liquid or long-chain biatomic acid fermentation treatment fluid, or described in the lysate formed in organic solvent from long-chain biatomic acid dissolving crude product, long-chain biatomic acid crude product is obtained by long-chain biatomic acid fermented liquid or the pre-treatment of long-chain biatomic acid fermentation treatment fluid; As described above.
Wherein, described in step 2, polymerization is preferably condensation polymerization.
Wherein, described comonomer is preferably polyamine or polyvalent alcohol.
Described polyvalent alcohol is preferably dibasic alcohol, as the dibasic alcohol of C2-C20, is more preferably C2-C10 dibasic alcohol, is more preferably C2-C6 dibasic alcohol, as ethylene glycol, butyleneglycol etc.
Wherein, described polyamine is preferably diamine, as the diamine of C2-C20, is more preferably C2-C10, is more preferably the diamine of C4-C6, as pentanediol, hexanediamine etc.
Compared with intermittent type crystallization apparatus, the above-mentioned crystallization method of the present invention is under the prerequisite obtaining like products quality, and industrial automatization is high, constant product quality.Meanwhile, operator significantly reduce, and investment cost has the saving (10000 tons/year of product scales) of more than 50% relative to periodic crystallisation device.
Therefore, the present invention, by continuous crystallisation equipment, can obtain the long-chain biatomic acid crystal of high-quality efficiently, and reducing facility investment, reduce fluctuation, is a kind of desirable long-chain biatomic acid crystallization method.
Embodiment
Below by embodiment, the present invention is described in detail, and to make the features and advantages of the present invention clearer, but the present invention is not limited to the embodiment listed herein.
In this article in listed embodiment, use following testing method:
1, long-chain biatomic acid gas chromatographic detection:
Employing standard long-chain biatomic acid sample in contrast, with reference to fatty acid determination in GB5413.27-2010 infant or baby food and dairy products.
2, ash content detects:
Get testing sample calcination in crucible, then calcination 2 hours in 700 ~ 800 DEG C of retort furnaces, gravimetry after cooling constant weight, calculates percent by weight.
3, determination of total nitrogen content:
Adopt Kjeldahl determination.
4, determination of light transmittance:
Long-chain biatomic acid sample dissolution is become the sodium-salt aqueous solution of 5%, the transmittance then under UV detection 430nm.
Below by embodiment, the present invention is described in detail, and to make the features and advantages of the present invention clearer, but the present invention is not limited to the embodiment listed herein.
Comparative example 1
Prepare DC12 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and washing is dried and obtained long-chain biatomic acid crude product.Add the acetum (moisture 13%) of long-chain biatomic acid amount 3 times of weight, stir, keep temperature 92 DEG C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Above-mentioned acetum enters industrialization periodic crystallisation device.Crystallization apparatus band stirs, mixing speed 40 revs/min.Slow cooling in crystallizer, after 12 hours, drops to 30 DEG C, is incubated more than 2 hours.
From the crystallization mixture that periodic crystallisation device obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Comparative example 2
Prepare DC12 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and washing is dried and obtained long-chain biatomic acid crude product.Add the acetum (moisture 13%) of long-chain biatomic acid amount 3 times of weight, stir, keep temperature 92 DEG C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Above-mentioned acetum enters industrialization periodic crystallisation device.Crystallization apparatus band stirs, mixing speed 40 revs/min.Slow cooling in crystallizer, after 3 hours, drops to 30 DEG C, holding temperature more than 1 hour.
From the crystallization mixture that periodic crystallisation device obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Embodiment 1
Prepare DC12 fermented liquid according to method disclosed in patent documentation ZL200410018255.7, fermented liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, is heated to 80 DEG C.Add the N-BUTYL ACETATE of contained long-chain biatomic acid amount 4 times of weight, stir, in direct extractive fermentation liquid, long-chain biatomic acid is to organic phase.Keep 80 DEG C, be separated organic phase, organic phase adds 3% activated carbon decolorizing (weight ratio of relative diprotic acid), filters and obtains clear liquid.
N-BUTYL ACETATE solution enters continuous crystallisation device.Continuous crystallisation apparatus, with stirs, mixing speed 50 revs/min.The first step of continuous crystallisation device controls 68 ± 1 DEG C, mean residence time 2 hours; The second stage of continuous crystallisation device controls 60 ± 2 DEG C, mean residence time 1 hour; The third stage of continuous crystallisation device controls 32 ± 2 DEG C, mean residence time 2.5 hours.
From the crystallization mixture that continuous crystallizer obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Embodiment 2
Prepare DC12 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and dries and obtains long-chain biatomic acid crude product.Add the isoamyl acetate of long-chain biatomic acid amount 3 times of weight, stir, keep temperature 90 DEG C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Isoamyl acetate solution enters continuous crystallisation device.Continuous crystallisation apparatus, with stirs, mixing speed 50 revs/min.The first step of continuous crystallisation device controls 72 ± 1 DEG C, mean residence time 2 hours; The second stage of continuous crystallisation device controls 57 ± 2 DEG C, mean residence time 1 hour; The third stage of continuous crystallisation device controls 30 ± 2 DEG C, mean residence time 2.5 hours.
From the crystallization mixture that continuous crystallizer obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Embodiment 3
Prepare DC12 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and washing is dried and obtained long-chain biatomic acid crude product.Add the primary isoamyl alcohol of long-chain biatomic acid amount 2.5 times of weight, stir, keep temperature 75 DEG C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Isoamyl alcohol enters continuous crystallisation device.Continuous crystallisation apparatus, with stirs, mixing speed 40 revs/min.The first step of continuous crystallisation device controls 55 ± 1 DEG C, mean residence time 3 hours; The second stage of continuous crystallisation device controls 48 ± 2 DEG C, mean residence time 1 hour; The third stage of continuous crystallisation device controls 25 ± 2 DEG C, mean residence time 3 hours.
From the crystallization mixture that continuous crystallizer obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Embodiment 4
Prepare DC12 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and washing is dried and obtained long-chain biatomic acid crude product.Add the primary isoamyl alcohol of long-chain biatomic acid amount 5 times of weight, stir, keep temperature 60 C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Isoamyl alcohol enters continuous crystallisation device.Continuous crystallisation apparatus, with stirs, mixing speed 40 revs/min.The first step of continuous crystallisation device controls 47 ± 1 DEG C, mean residence time 3 hours; The second stage of continuous crystallisation device controls 42 ± 1 DEG C, mean residence time 1 hour; The third stage of continuous crystallisation device controls 25 ± 2 DEG C, mean residence time 3 hours.
From the crystallization mixture that continuous crystallizer obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Embodiment 5
Prepare DC12 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and washing is dried and obtained long-chain biatomic acid crude product.Add the acetum (moisture 13%) of long-chain biatomic acid amount 3 times of weight, stir, keep temperature 92 DEG C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Above-mentioned acetum enters continuous crystallisation device.Continuous crystallisation apparatus, with stirs, mixing speed 40 revs/min.The first step of continuous crystallisation device controls 73 ± 1 DEG C, mean residence time 2 hours; The second stage of continuous crystallisation device controls 65 ± 1 DEG C, mean residence time 2 hours; The third stage of continuous crystallisation device controls 30 ± 2 DEG C, mean residence time 3 hours.
From the crystallization mixture that continuous crystallizer obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Embodiment 6
Prepare DC13 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and washing is dried and obtained long-chain biatomic acid crude product.Add the acetum (moisture 13%) of long-chain biatomic acid amount 2.5 times of weight, stir, keep temperature 85 DEG C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Above-mentioned acetum enters continuous crystallisation device.Continuous crystallisation apparatus, with stirs, mixing speed 40 revs/min.The first step of continuous crystallisation device controls 66 ± 1 DEG C, mean residence time 2 hours; The second stage of continuous crystallisation device controls 55 ± 1 DEG C, mean residence time 2 hours; The third stage of continuous crystallisation device controls 30 ± 2 DEG C, mean residence time 3 hours.
From the crystallization mixture that continuous crystallizer obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
Embodiment 7
Prepare DC14 film clear liquid according to membrane filtering method disclosed in patent documentation ZL200410018255.7, liquid adds weight concentration 97% sulfuric acid adjust ph to 3.0, filters, and washing is dried and obtained long-chain biatomic acid crude product.Add the acetum (moisture 13%) of long-chain biatomic acid amount 3 times of weight, stir, keep temperature 88 DEG C, add 3% activated carbon decolorizing (weight ratio of relative long-chain biatomic acid), filter and obtain clear liquid.
Above-mentioned acetum enters continuous crystallisation device.Continuous crystallisation apparatus, with stirs, mixing speed 40 revs/min.The first step of continuous crystallisation device controls 69 ± 1 DEG C, mean residence time 2 hours; The second stage of continuous crystallisation device controls 61 ± 1 DEG C, mean residence time 2 hours; The third stage of continuous crystallisation device controls 30 ± 2 DEG C, mean residence time 3 hours.
From the crystallization mixture that continuous crystallizer obtains, adopt 1000rpm centrifuge isolation of crystalline.Crystal adopts a times amount (relative to long-chain biatomic acid weight) water washing then to dry, and enters blade dryer 105 DEG C of dryings, dries and obtains product.
In above-described embodiment 1-7, gained long-chain biatomic acid quality product detected result is as described in Table 1.
The decrease temperature crystalline of long-chain biatomic acid organic solution, needs to control suitable cooling rate, prevents because cooling rate is too fast, causes long-chain biatomic acid to break out and separates out, affect the quality of product.Therefore, in periodic crystallisation device, the time of crystallization is generally greater than more than 10 hours, and can find out in the above embodiment of the present invention 1-7, and crystallization time is substantially all in 5 ~ 7 hours window, and production efficiency significantly improves.
Can be found out by above-described embodiment 1-7 and table 1, the crystallization method of long-chain biatomic acid provided by the present invention, in the large-scale commercial process of such as 10000 tons/year of product scales, gained long-chain biatomic acid product purity also can reach more than 98.7%, reach as high as about 99.5%, there is the higher rate of recovery simultaneously.Therefore, long-chain biatomic acid crystallization method efficiency of the present invention is high, cost is low, is applicable to large-scale industrial production.
Table 1, gained long-chain biatomic acid quality product detected result in embodiment 1-7
Same the inventive method can be used in the production process of synthetic or biological fermentation synthesis long-chain biatomic acid, and can be used for using long-chain binary hydroxy acid to produce in the production process of the polymkeric substance such as polymeric amide, polyester, equally also can enhance productivity.
Be described in detail specific embodiments of the invention above, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and substituting also all among category of the present invention.Therefore, equalization conversion done without departing from the spirit and scope of the invention and amendment, all should contain within the scope of the invention.
Claims (17)
1. a long-chain biatomic acid continuous crystallisation process, is characterized in that, step comprises:
Organic solution containing long-chain biatomic acid is carried out multistage crystallization.
2. long-chain biatomic acid continuous crystallisation process according to claim 1, is characterized in that, described multistage crystallization is three grades of crystallizations, and temperature during rear class crystallization is lower than temperature during prime crystallization.
3. long-chain biatomic acid continuous crystallisation process according to claim 2, is characterized in that, the Tc of first step crystallization is lower 1 ~ 10 DEG C than diprotic acid Precipitation Temperature in described organic solution.
4. long-chain biatomic acid continuous crystallisation process according to claim 3, is characterized in that, in first step crystallisation process, the undulated control of Tc is within the scope of ± 2 DEG C.
5. long-chain biatomic acid continuous crystallisation process according to claim 3, is characterized in that, the Tc of second stage crystallization is lower than first step Tc 5 ~ 15 DEG C.
6. long-chain biatomic acid continuous crystallisation process according to claim 5, is characterized in that, in the crystallisation process of the second stage, the undulated control of Tc is within the scope of ± 3 DEG C.
7. long-chain biatomic acid continuous crystallisation process according to claim 5, is characterized in that, the Tc of third stage crystallization is lower than second stage Tc 5 ~ 70 DEG C.
8. long-chain biatomic acid continuous crystallisation process according to claim 5, is characterized in that, in third stage crystallisation process, the undulated control of Tc is within the scope of ± 3 DEG C.
9. long-chain biatomic acid continuous crystallisation process according to claim 1, is characterized in that, described long-chain biatomic acid is based on biological fermentation process preparation or prepares based on chemical synthesis.
10. long-chain biatomic acid continuous crystallisation process according to claim 1, is characterized in that, the described organic solution containing long-chain biatomic acid is prepared by long-chain biatomic acid fermented liquid or long-chain biatomic acid fermentation treatment fluid, long-chain biatomic acid crude product.
11. long-chain biatomic acid continuous crystallisation process according to claim 1, is characterized in that, the described organic solution containing long-chain biatomic acid is that long-chain biatomic acid prepared by chemical synthesis dissolves the lysate formed in organic solvent
12. long-chain biatomic acid continuous crystallisation process according to claim 1, is characterized in that, after described multistage crystallization, also comprise dry step, in described drying process, temperature controls at 95 ~ 120 DEG C.
13. according to the long-chain biatomic acid continuous crystallisation process in claim 1-12 described in any one, it is characterized in that, described multistage crystallization by realizing the organic solution containing diprotic acid by every one-level crystallizer Step crystallization successively in multistage crystallization equipment, and the residence time in every one-level crystallizer is >=1 hour.
14. 1 kinds, for the long-chain biatomic acid continuous crystallisation device of method according to claim 1, is characterized in that, comprise the multistage crystallization equipment of connecting successively, every one-level crystallizer is equipped with heat sink.
15. long-chain biatomic acid continuous crystallisation devices according to claim 14, is characterized in that, described continuous crystallisation device is three grades of crystallization apparatus.
16. 1 kinds of methods of producing long-chain biatomic acid, it is characterized in that, step comprises:
Step 1, obtains the organic solution containing di-carboxylic acid by fermentable or chemical synthesis;
Step 2, adopts any one method of claim 1-13 to carry out crystallization to the described organic solution containing di-carboxylic acid.
17. 1 kinds of methods using di-carboxylic acid synthetic polymer, it is characterized in that, wherein said polymkeric substance can be polyester or polymeric amide, and step comprises:
Step 1, adopts any one method of claim 1-13 to carry out crystallization to long-chain binary hydroxy acid raw material, obtains long-chain binary hydroxy acid product;
Step 2, is polymerized gained long-chain binary hydroxy acid product with comonomer.
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