CN1159280C - Separation and purification method of dodecanedioic acid - Google Patents
Separation and purification method of dodecanedioic acid Download PDFInfo
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- CN1159280C CN1159280C CNB01113271XA CN01113271A CN1159280C CN 1159280 C CN1159280 C CN 1159280C CN B01113271X A CNB01113271X A CN B01113271XA CN 01113271 A CN01113271 A CN 01113271A CN 1159280 C CN1159280 C CN 1159280C
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Abstract
The present invention relates to a separation and purification method of dodecanedioic acid, which comprises the steps that a fermentation solution biologically fermented is decolored by activated carbon and filtered; chitosan and ethylenediaminetetraacetic acid are added into the filtrate to be combined with impurities in the fermentation solution to form suspended substances which are removed by micro-filtration; the impurities are further removed by ultrafiltration to purify the solution; acid is added into the ultrafiltration penetrating solution to precipitate the dodecanedioic acid; the product of dodecanedioic acid is prepared by filtration and drying. The present invention has the advantages of simple and convenient technology, easy operation at normal temperature and low pressure, no phase change, easy control of the operation, no secondary pollution in the process of production, no amplification effect because of membrane separation technique, convenient industrial application, low production cost and high product purity.
Description
One, technical field
The present invention relates to a kind of separating and purifying method of dodecanedioic acid, relate to a kind of method of the fermentative Production dodecanedioic acid being separated purification or rather.
Two, background technology
Dodecanedioic acid (Dodecanedioie Acid is called for short DDDA) has another name called the bay diacid, is the important industrial chemicals of manufacturing engineering plastics, nylon 12, nylon hot-melt adhesive, spices, coating, optical cable etc., and purposes is extremely extensive.The production of dodecanedioic acid generally has chemosynthesis and two kinds of methods of biological fermentation.But because chemical synthesis exists that hydrogenation reaction need be prevented fires, explosion-proof, gas defence, in addition must be under high temperature, condition of high voltage harsh reaction conditionss such as catalysis is synthetic, environmental pollution seriously reaches problems such as production cost height, has therefore limited its industrial application.In recent years, the suitability for industrialized production of dodecanedioic acid generally adopts biological fermentation process.Biological fermentation process is produced dodecanedioic acid with respect to chemical synthesis, have an enormous advantage at production technique, security and economic aspect, but at present because the aftertreatment technology imperfection of leavened prod causes product purity not high, these the perfect of further research work that await from now on.
In prior art, Japanese kokai publication sho 58-193694 discloses a kind of aftertreatment technology of fermentative Production dodecanedioic acid, it has adopted the extracting of mixed solvent high temperature to separate the purification dodecanedioic acid with the crystallisation by cooling method, product purity reaches 99%, nitrogen content＜100ppm, but this method complex process need circulation extracting under 100 ℃ of temperature in the purification process, the energy consumption height, and the recovery of solvent is also more complicated.
A kind of aftertreatment technology (modern chemical industry of handling long-chain tridecanyldicarboxylic acid fermented liquid has been introduced by Fushun petrochemical industry research institute, 1996,1:22～24), this process using solventless method is purified, sepn process is simpler, and remove mycelium with micro-filtration, but this article there is not further to disclose detailed technical scheme.
Three, summary of the invention
The purpose of this invention is to provide the easy biological fermentation process of a kind of technology and produce the separating and purifying method of dodecanedioic acid, by adding sequestrant commonly used and flocculation agent, remove protein and heavy metal ion in the fermented liquid simultaneously, the purity of product is greatly improved.
The present invention realizes like this.The separating and purifying method of dodecanedioic acid of the present invention comprises following operation steps:
(1) the dodecanedioic acid fermented liquid behind the biological fermentation, the fermented liquid temperature is controlled at 70～90 ℃, adds gac, stirs, and filters, and gets filtrate,
(2) under agitation add chitosan and ethylenediamine tetraacetic acid (EDTA) in the filtrate that step (1) obtains, the filtrate temperature remains on 30～40 ℃, and described chitosan add-on is 5～20 mg/litre filtrates, and the ethylenediamine tetraacetic acid (EDTA) add-on is 1～15 mg/litre filtrate,
(3) liquid after the stirring is removed suspended substance through micro-filtration, gets filtrate,
(4) filtrate that step (3) is obtained feeds in the ultra-fine filter carries out ultrafiltration, gets ultrafiltration and sees through liquid, and the working pressure of described ultra-fine filter is 0.08～1.0MPa, and service temperature is 30～60 ℃, and face speed is 1.2～3m/s,
(5) ultrafiltration that obtains of heating steps (4) sees through liquid to 70～90 ℃, sees through to ultrafiltration under agitation that to add sulfuric acid or hydrochloric acid to pH value of solution in the liquid be to stop to add acid at 3～4 o'clock, and dodecanedioic acid is separated out, and filters, and drying promptly gets the dodecanedioic acid product.
The separating and purifying method of dodecanedioic acid of the present invention, fermentation back activated carbon decolorizing, the filtrate of gained after filtering, its impurity major part is removed, then by adding sequestrant and flocculation agent to remove heavy metal ion (mainly being iron ion) and the protein in the fermented liquid.The ethylenediamine tetraacetic acid (EDTA) that the present invention adopts is a kind of typical sequestrant, its with metal ion-chelant after the metal salt complex of the stable ethylenediamine tetraacetic acid (EDTA) of formation, the molecular weight of this complex compound can be removed by membrane sepn greater than the molecular weight of dodecanedioic acid.The present invention forms floss by the protein effect of adding in flocculation agent chitosan and the fermented liquid, removes by membrane sepn then.The suitable addition of sequestrant and flocculation agent also is one of important research content of the present invention, the optimum addition of ethylenediamine tetraacetic acid (EDTA) and chitosan is not have residue fully with the impurity chelating of fermented liquid, so both can reach the purifying purpose, it is minimum that processing cost is increased.If addition is excessive, not too much with the residual quantity of impurity effect, can influence the purity of product on the contrary.Method chitosan add-on of the present invention is 5～20 mg/litre filtrates, and preferable add-on is 10～15 mg/litre filtrates; The ethylenediamine tetraacetic acid (EDTA) add-on is 1～15 mg/litre filtrate, and preferable add-on is 5～10 mg/litre filtrates.The addition sequence of ethylenediamine tetraacetic acid (EDTA) and chitosan is different, does not influence quality product.
Through the liquid that sequestrant and flocculation agent were handled, remove suspended substance with millipore filter, obtain clarifying filtrate, the aperture of microfiltration membrane can be controlled at 0.1～3 μ m.
The filtrate that micro-filtration is obtained feeds the ultra-fine filter ultrafiltration, so that further purify and partially desalted decolouring, ultrafiltration can also remove the impurity of deproteinize, metallo-chelate and other macromolecule.The membrane module of the ultra-fine filter that the present invention adopts can be plate and frame or tubular type or rolling.The working pressure of described ultra-fine filter of the present invention is 0.08～1.0MPa, preferably 0.1～0.7MPa; Service temperature is 30～60 ℃, preferably 50～60 ℃; Face speed is 1.2～3m/s, preferably 2.0～2.3m/s.The film that ultra-fine filter of the present invention adopts is the polymer organic membrane, and the molecular weight of film is 500～10000 dalton, and the molecular weight of preferable film is 500～3000 dalton.
The ultrafiltration that obtains through ultrafiltration sees through liquid, by to wherein adding sulfuric acid or hydrochloric acid dodecanedioic acid cementation being come out, when the pH of liquid is 3～4, stops to add acid, can think that the dodecanedioic acid displacement fully.When adding acid, ultrafiltration sees through liquid temp and preferably is controlled at 70～90 ℃.Filter then, drying get final product the dodecanedioic acid product.Dodecanedioic acid can also be starched the cleaning filter cake again with deionized water after filtering, and further improves the purity of dodecanedioic acid.The temperature of cleaning the deionized water of filter cake is controlled at 60～90 ℃, wash number 1～4 time.The dodecanedioic acid product purity that obtains like this is generally: total acid is more than 99%, and single acid (dodecanedioic acid) is more than 98%, nitrogen content, Fe
2+, ash reaches the requirement of standard code.
Compared with the prior art the separating and purifying method of dodecanedioic acid of the present invention has the following advantages:
1, separating and purifying method of the present invention adopts adding sequestrant and flocculation agent to combine with membrane separation technique, handles the fermented liquid that biological fermentation process is produced dodecanedioic acid, can make product purity reach higher level, and production cost is low, product yield height.Its product purity total acid can reach more than 99.6%, and single acid (dodecanedioic acid) is more than 98.5%, and foreign matter contents such as nitrogen, iron and ash are lower, the content of nitrogen minimum can≤50ppm, Fe
2+≤ 2.4ppm, ash≤100ppm.
2, method of the present invention does not adopt organic solvent, has saved complicated solvent recuperation process, and production process safety, and the entire operation process is easy to control, and energy consumption is low.
3, method flow of the present invention is simple, under normal temperature low pressure, operate, and no phase transformation, but flow process control fully automated adopts membrane separation technique not have scale effect, is convenient to industrial applications.
4, method of the present invention does not produce secondary pollution in process of production, is a kind of production process route of cleaning, conforms with the requirement of Sustainable development.
Four, embodiment
Further set forth the present invention below by detailed description, but embodiment not a limitation of the present invention to specific embodiments of the invention.
Embodiment 1:
Get the bio-fermented liquid 1000mL of dodecanedioic acid, add gac 30g down at 70 ℃ and decolour, stir, filter, get filtrate.The filtrate temperature remains on 40 ℃, adds ethylenediamine tetraacetic acid (EDTA) 11mg, stirs 20 minutes, then adds chitosan 14mg again, restir 20 minutes, and stirring velocity is 50～60 rev/mins.The millipore filter filtration that this treatment solution is fed 0.3 μ m obtains micro-filtrate.Filter and finish, the filter residue in the strainer replaces twice with 40 ℃ deionized water, each water 500mL, and this moment, filtered liquid was about 1940mL, wherein contained the displacement liquid of 60mL in the filter residue approximately.This filtered liquid enters the tubular type ultra-fine filter ultrafiltration that diameter is 100mm, and the molecular weight of this ultra-fine filter film is 1000 dalton, and working pressure is 0.2MPa, and service temperature is 40 ℃, and face speed is 2.0m/s.Ultrafiltration finishes to obtain ultrafiltration and sees through the about 1900mL of liquid, and with 40 ℃ of deionized water displacements twice, each water consumption 50mL obtains the about 2000mL of solution amount at last.Heated solution under agitation adds sulfuric acid dodecanedioic acid is separated out to about 70 ℃ in this solution, when adding acid to the pH=3 of solution, add sour replacement(metathesis)reaction and finish.To add solid-liquid mixtures that acid displacement obtains and send in the strainer and filter, after the drying dodecanedioic acid product 48.18g.Analyze this product, total acid 98.6% in this product, single acid (dodecanedioic acid) 96.8%, nitrogen content 160ppm, Fe
2+10ppm, ash 800ppm.
Embodiment 2:
Get the bio-fermented liquid 1000mL of dodecanedioic acid, add gac 30g down at 80 ℃ and decolour, stir, filter, get filtrate.The filtrate temperature remains on 40 ℃, adds ethylenediamine tetraacetic acid (EDTA) 7mg, stirs 20 minutes, then adds chitosan 11mg again, restir 20 minutes, and stirring velocity is 50～60 rev/mins.This treatment solution is fed the millipore filter micro-filtration of 0.1 μ m.Filter and finish, the filter residue in strainer replaces twice with 40 ℃ deionized water, each water 500mL, and this moment, filtered liquid was about 1940mL.This filtered liquid enters flat ultra-fine filter ultrafiltration, and the molecular weight of this ultra-fine filter film is 1000 dalton, and working pressure is 0.2MPa, and service temperature is 40 ℃, and face speed is 2.0m/s.Ultrafiltration finishes to obtain ultrafiltration and sees through the about 1900mL of liquid, and with 40 ℃ of deionized water displacements twice, each water consumption 50mL obtains the about 2000mL of solution amount at last.This solution is heated to 90 ℃, under agitation adds sulfuric acid dodecanedioic acid is separated out, when adding acid, add sour replacement(metathesis)reaction and finish to the pH=4 of solution.To add solid-liquid mixtures that acid displacement obtains and send into a filter rinsed and filter, and with about 70 ℃ washed with de-ionized water filter cake three times, about 1: 2 of the ratio (weight) of control filter cake and deionized water must dodecanedioic acid product 47.18g after the drying.Analyze, total acid 99.68% in this product, single acid (dodecanedioic acid) 98.5%, nitrogen content 48ppm, Fe
2+2.4ppm, ash 100ppm.
Embodiment 3:
Remove and when the filtrate temperature is 30 ℃, add chitosan 5mg, ethylenediamine tetraacetic acid (EDTA) 10mg respectively, the molecular weight of ultra-fine filter film is 500 dalton, working pressure is 0.02MPa, service temperature is 30 ℃, face speed is 1.2m/s, ultrafiltration sees through liquid salt Acid precipitation dodecanedioic acid, outside about 60 ℃ washed with de-ionized water filter cake 4 times, all the other operations get dodecanedioic acid product 46.84g with embodiment 2 after the drying, analyze, total acid 99.64% in this product, single acid (dodecanedioic acid) 98.40%, nitrogen content 50ppm, Fe
2+3ppm, ash 100ppm.
Embodiment 4:
Remove and when the filtrate temperature is 35 ℃, add chitosan 20mg and ethylenediamine tetraacetic acid (EDTA) 15mg, the molecular weight of ultra-fine filter film is 5000 dalton, working pressure is 1.0MPa, service temperature is 35 ℃, face speed is 3.0m/s, ultrafiltration sees through liquid salt Acid precipitation dodecanedioic acid, outside about 80 ℃ washed with de-ionized water filter cake 1 time, all the other operations get dodecanedioic acid product 46.91g with embodiment 2 after the drying, analyze, total acid 98.94% in this product, single acid (dodecanedioic acid) 97.55%, nitrogen content 200ppm, Fe
2+9ppm, ash 1300ppm.
Embodiment 5:
Remove and when the filtrate temperature is 60 ℃, add chitosan 15mg and ethylenediamine tetraacetic acid (EDTA) 1mg, the molecular weight of ultra-fine filter film is 10000 dalton, working pressure is 0.7MPa, service temperature is 60 ℃, face speed is 1.5m/s, ultrafiltration sees through liquid sulfuric acid precipitation dodecanedioic acid, outside about 90 ℃ washed with de-ionized water filter cake 2 times, all the other operations get dodecanedioic acid product 47.20g with embodiment 2 after the drying, analyze, total acid 98.2% in this product, single acid (dodecanedioic acid) 96.80%, nitrogen content 150ppm, Fe
2+17ppm, ash 1100ppm.
Embodiment 6:
Remove and when the filtrate temperature is 50 ℃, add chitosan 10mg and ethylenediamine tetraacetic acid (EDTA) 5mg, the molecular weight of ultra-fine filter film is 3000 dalton, working pressure is 0.4MPa, service temperature is 50 ℃, face speed is 2.5m/s, ultrafiltration sees through liquid sulfuric acid precipitation dodecanedioic acid, outside about 65 ℃ washed with de-ionized water filter cake 3 times, all the other operations get dodecanedioic acid product 47.16g with embodiment 2 after the drying, analyze, total acid 98.7% in this product, single acid (dodecanedioic acid) 97.35%, nitrogen content 68ppm, Fe
2+4.2ppm, ash 180ppm.
Claims (8)
1, a kind of separating and purifying method of dodecanedioic acid, this method comprises following operation steps:
(1) the dodecanedioic acid fermented liquid behind the biological fermentation, the fermented liquid temperature is controlled at 70～90 ℃, adds gac, stirs, and filters, and gets filtrate,
(2) under agitation add chitosan and ethylenediamine tetraacetic acid (EDTA) in the filtrate that step (1) obtains, the filtrate temperature remains on 30～40 ℃, and described chitosan add-on is 5～20 mg/litre filtrates, and the ethylenediamine tetraacetic acid (EDTA) add-on is 1～15 mg/litre filtrate,
(3) liquid after the stirring is removed suspended substance through micro-filtration, gets filtrate,
(4) filtrate that step (3) is obtained feeds in the ultra-fine filter carries out ultrafiltration, gets ultrafiltration and sees through liquid, and the working pressure of described ultra-fine filter is 0.08～1.0MPa, and service temperature is 30～60 ℃, and face speed is 1.2～3m/s,
(5) ultrafiltration that obtains of heating steps (4) sees through liquid to 70～90 ℃, sees through to ultrafiltration under agitation that to add sulfuric acid or hydrochloric acid to pH value of solution in the liquid be to stop to add acid at 3～4 o'clock, and dodecanedioic acid is separated out, and filters, and drying promptly gets the dodecanedioic acid product.
2, separating and purifying method as claimed in claim 1 is characterized in that described chitosan add-on is 10～15 mg/litre filtrates, and the ethylenediamine tetraacetic acid (EDTA) add-on is 5～10 mg/litre filtrates.
3, separating and purifying method as claimed in claim 1, when it is characterized in that described micro-filtration, the aperture of microfiltration membrane is 0.1～3 μ m.
4, separating and purifying method as claimed in claim 1, the working pressure that it is characterized in that described ultra-fine filter is 0.1～0.7MPa, and service temperature is 50～60 ℃, and face speed is 2.0～2.3m/s.
5, as claim 1 or 4 described separating and purifying method, the ultra-filtration membrane molecular weight that it is characterized in that described ultra-fine filter is 500～10000 dalton.
6, as claim 1 or 4 described separating and purifying method, the ultra-filtration membrane molecular weight that it is characterized in that described ultra-fine filter is 500～3000 dalton.
7, separating and purifying method as claimed in claim 1 is characterized in that the filter cake after the dodecanedioic acid that will go out with acid out filters, and starches the cleaning filter cake again with deionized water, and the temperature of deionized water is controlled at 60～90 ℃.
8, separating and purifying method as claimed in claim 7 is characterized in that starching the cleaning filter cake again 1～4 time with deionized water.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB01113271XA CN1159280C (en) | 2001-07-06 | 2001-07-06 | Separation and purification method of dodecanedioic acid |
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| CNB01113271XA CN1159280C (en) | 2001-07-06 | 2001-07-06 | Separation and purification method of dodecanedioic acid |
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| CN1159280C true CN1159280C (en) | 2004-07-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795984A (en) * | 2012-08-28 | 2012-11-28 | 淄博广通化工有限责任公司 | Production method of mixed binary acid with long carbon chain |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445257C (en) * | 2006-07-18 | 2008-12-24 | 南京工业大学 | Method for separating and extracting succinic acid from anaerobic fermentation broth |
| CN102329224B (en) * | 2011-09-13 | 2013-11-06 | 中国石油化工股份有限公司 | Method for purifying dodecanedioic acid |
| CN110642707B (en) * | 2019-10-22 | 2022-04-19 | 成都市科隆化学品有限公司 | Purification production method of low-cost environment-friendly sodium salicylate |
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2001
- 2001-07-06 CN CNB01113271XA patent/CN1159280C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102795984A (en) * | 2012-08-28 | 2012-11-28 | 淄博广通化工有限责任公司 | Production method of mixed binary acid with long carbon chain |
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| CN1394842A (en) | 2003-02-05 |
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