CN105622391B - A kind of method of purification of long chain dicarboxylic acid - Google Patents
A kind of method of purification of long chain dicarboxylic acid Download PDFInfo
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- CN105622391B CN105622391B CN201410585416.4A CN201410585416A CN105622391B CN 105622391 B CN105622391 B CN 105622391B CN 201410585416 A CN201410585416 A CN 201410585416A CN 105622391 B CN105622391 B CN 105622391B
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Abstract
The invention discloses a kind of method of purification of long chain dicarboxylic acid, including：I, zymotic fluid heat inactivation will be terminated；II, the solid impurities such as bacteria residue are removed, reclaim alkane；III, appropriate polyethylene glycol and glucan are added into zymotic fluid, each material is dissolved in zymotic fluid, double-aqueous phase system is made；IV, above-mentioned double-aqueous phase system is carried out to hypergravity processing, two-phase is rapidly separated mixed system up and down after hypergravity is handled, and the impurity such as albumen is dissolved in phase, and product dicarboxylate is dissolved in lower phase；V, lower phase, acidifying in step IV is taken to separate out dicarboxylic acid crystallizates, cool down, filter, being dried to obtain refined dicarboxylic acid product.The inventive method is combined the refined dicarboxylic acids of processing with hypergravity using aqueous two-phase extraction, not only shortens technological process, saves the input such as equipment, time and energy consumption, and can obtain the purified product that purity is high, total nitrogen content is low, is more suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of method of purification of long chain dicarboxylic acid, high purity long chain dicarboxyl is particularly obtained from zymotic fluid
The method of acid.
Background technology
Long chain dicarboxylic acid general molecular formula is CnH2n-2O4, wherein n is 10-18, is that microorganism is fermented and obtained using liquid wax etc.
Metabolite.Its zymotic fluid is complicated heterogeneous system, wherein containing unreacted carbon source, microbial cell and fragment, not
The culture medium and metabolite that utilize and the secretion of microorganism etc., especially wherein contain a large amount of protein, pigment and ash
Grade impurity, has a strong impact on purity and the application of product, and the extraction to the species dicarboxylic acids brings difficulty with refined.
The method of extraction long chain dicarboxylic acid is generally divided into solvent method and Aqueous phase at present.Although solvent method can solve above-mentioned
Problem, but because solvent method is present, investment is big, and equipment corrosion is serious, and solvent and alkane and production security are remained in product
And the problems such as environmental pollution, the use of this method are greatly limited.Although traditional aqueous phase method of purification overcomes solvent
The defects of method, but its product purity and yield can not reach compared with high target.
In long chain dicarboxylic acid process for purification disclosed in CN01142806.6, using long chain dicarboxylic acid dry powder as raw material, third is used
Ketone, methanol and ethanol as solvent refining long-chain dicarboxylic acids.Dicarboxylic acids in method zymotic fluid first first after charcoal absorption, then
Acidizing crystal, filtering, washing and dry dicarboxylic acid crystallizates filter cake obtain long chain dicarboxylic acid dry powder, are then carried out using organic solvent
It is refined.The refined raw material of this method obtains dicarboxylic acids dry powder after drying for aqueous filter cake, the limitation drop to feed moisture content
The low operating flexibility of this method, the equipment that thick acid is dried is added, causes this technological process longer, adds production cost.
And this method is in the aqueous solution of the alkaline dicarboxylic acids sodium salt before obtaining dicarboxylic acid crystallizates filter cake and in solvent refining processes,
The processing of charcoal absorption twice has been carried out altogether, and those skilled in the relevant art know about, and increase an activated carbon processing procedure, meeting
Increase equipment investment and production cost, and activated carbon dosage is directly proportional to the loss of product, and activated carbon dosage is bigger, production
The yield of product is lower.And when organic solvent refines dicarboxylic acids, can typically reach the requirement of decolouring using adsorbent, but still compared with
Hardly possible removes small molecular protein therein, makes total nitrogen content undesirable.
CN1255483A discloses a kind of method of Aqueous phase separation dicarboxylic acids：Zymotic fluid heating will be terminated and remove unreacted
Alkane, then add diatom filtration sterilization；Filtrate is through adjusting pH value to obtain sour cake and filtrate；Filtrate adds activated carbon decolorizing again, then mistake
Filter；The sour cake obtained before with the filtrate dissolving after decolouring again, acidifying；Crystallization is finally obtained, drying obtains dicarboxylic acid product.
The method is complex for operation step, and running cost is high, and dicarboxylic acid product yield is too low, and purity is not also high, and the alkane rate of recovery is low.
The content of the invention
In view of the shortcomings of the prior art, the invention provides a kind of method of purification of long chain dicarboxylic acid.The inventive method is adopted
The refined dicarboxylic acids of processing is combined with hypergravity with aqueous two-phase extraction, technological process is not only shortened, saves equipment, time and energy
The input such as consumption, and the purified product that purity is high, total nitrogen content is low can be obtained, it is more suitable for industrialized production.
The method of purification of long chain dicarboxylic acid of the present invention, including herein below：
I, zymotic fluid heat inactivation will be terminated；
II, the solid impurities such as bacteria residue are removed, reclaim alkane；
III, appropriate polyethylene glycol and glucan are added into zymotic fluid, each material is dissolved in zymotic fluid, be made double
Aqueous phase system；
IV, above-mentioned double-aqueous phase system is carried out to hypergravity processing, two-phase is rapid up and down after hypergravity is handled for mixed system
The impurity such as separation, albumen are dissolved in phase, and product dicarboxylate is dissolved in lower phase；
V, lower phase, acidifying in step IV is taken to separate out dicarboxylic acid crystallizates, cool down, filter, being dried to obtain refined dicarboxylic acids
Product.
It is microorganism metabolite obtained from liquid wax fermentation that zymotic fluid is terminated in the inventive method, described in step I,
The dicarboxylic acid molecule formula wherein contained is CnH2n-2O4, wherein n is 10-18, and dicarboxylic acids can be a kind of single dicarboxylic acids,
It can be mixed dicarboxylic acid.Described zymotic fluid heat inactivation temperature is generally 75 DEG C~100 DEG C.
In the inventive method, step II can use the conventional methods such as centrifugation or membrane filtration and equipment to carry out removing thalline etc.
The operation of impurity.
In the inventive method, the molecular weight of the polyethylene glycol described in step III for 4000~40000, preferably 4000~
20000, mass fraction is 2%~8%, preferably 3%~6%；The molecular weight of glucan is 100000~500000, is preferably
300000~500000, mass fraction is 3%~10%, preferably 5%~8%.Utilize the impurity such as albumen, foreign protein pigment, nucleic acid
Distribution coefficient difference with product two-phase in aqueous two-phase is so as to carrying out product extraction.In the present invention, one can also be added simultaneously
Quantitative phosphate, concentration is in 0.005~0.02mol/L.Phosphate can be sodium ascorbyl phosphate or potassium phosphate, preferably phosphoric acid hydrogen
Disodium or dipotassium hydrogen phosphate.The phosphate that wherein adds on the one hand can as the pH of buffer regulation system, on the one hand due to
The different valence state acid group of phosphoric acid is different in the distribution coefficient of double-aqueous phase system, thus can by add different phosphate ratios and
Interphase potential is poor adjusting for concentration, so as to influence the distribution of material.
In the inventive method, the hypergravity level of step IV hypergravities processing is 10~650g（G be acceleration of gravity=
9.8m/s2）, the mean residence time of hypergravity processing is 0.2~10s, and hypergravity equipment is high gravity rotating packed bed, baffling
The conventional hypergravity rotating devices such as formula, screw path type, rotating compact disc formula and fixed-rotator type, preferably hypergravity rotation filling
Bed.Hypergravity level refers to the size of centrifugal acceleration caused by rotor rotation in supergravity reactor, is generally accelerated with gravity
The multiple for spending g represents, main relevant with the rotating speed of rotor and the internal-and external diameter of rotor.
In the inventive method, acidifying can be using conventional method progress in step V.The pH value of the acidifying be 2.0~
4.0, heating-up temperature is 80~100 DEG C.Acid used in the above-mentioned acidifying of the present invention can be the H of any concentration2SO4、HNO3、HCl
Or H3PO4。
In the inventive method, untill crystallisation by cooling temperature generally makes dicarboxylic acids sufficient crystallising in step V, temperature is generally
10~30 DEG C.Filtration step in step V can use membrane filtration, such as NF membrane or microfiltration membranes, available membrane aperture scope
For 10-3μm~10 μm.
The inventive method can obtain the dicarboxylic acid product of the single kind of high-purity, it is also possible to obtain mixed dicarboxylic acid produces
Product.
Compared with prior art, the present invention has advantages below：
（1）Long chain dicarboxylic acid is purified using aqueous two-phase extraction, using impurity to be separated and product dicarboxylic acids in aqueous two-phase
The distribution coefficient difference of two-phase realizes that product extracts, avoid extract by solvents introduce the production security that brings of organic solvent and
The problems such as environmental pollution, while the product purity for solving the problems, such as Aqueous phase extraction is difficult to reach high requirement.
（2）Long chain dicarboxylic acid is extracted with the method that hypergravity processing is combined using aqueous two-phase extraction, utilizes hypergravity mistake
Cheng great great enhances interphase mass transfer, effectively improves effect of extracting so that impurity and the product such as albumen, foreign protein pigment, nucleic acid
It is preferably alternate separated two；Hypergravity, which is handled, simultaneously causes extraction and the time of split-phase to greatly shorten, and saves time input.
（3）The process route of use is easy to industrial amplification, and operating condition is gentle, can save energy consumption and material consumption.
Embodiment
Further the inventive method is explained below by embodiment.
Embodiment 1
Using n-dodecane hydrocarbon as substrate, the carbon dicarboxylic acids of candida tropicalis fermenting and producing 12 is utilized.Two during fermentation ends
Carboxylic acid concentration is 164.3 g/L, pH 7.4.Zymotic fluid 1000ml is taken, is heated to 80 DEG C, stands 2h, recovery upper strata is unreacted
Alkane, it is 10 with membrane aperture-2μm membrane filtration, remove somatic cells, fragment.Mass fraction 5% is added into zymotic fluid, is divided
Son amount is the glucan that 4 000 polyethylene glycol and mass fraction 8%, molecular weight are 300 000, and stirring is dissolved in each material
In zymotic fluid, double-aqueous phase system is formed.System is sent into hypergravity equipment and carries out hypergravity processing, hypergravity level is
150g, the mean residence time of hypergravity processing is 5s, the static 20min of system that will be handled by hypergravity, by upper and lower two-phase
Separation, removes phase, to 3 and is heated to 85 DEG C with 6M sulphur acid for adjusting pH, constant temperature 1h.Crystallizing at room temperature is at the uniform velocity down to 15 DEG C/h,
It is 10 with membrane aperture-2μm ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, dry cake obtains product.Product matter
Amount is shown in Table 1.
Embodiment 2
Using n-dodecane hydrocarbon as substrate, the carbon dicarboxylic acids of candida tropicalis fermenting and producing 12 is utilized.Two during fermentation ends
Carboxylic acid concentration is 158 g/L, pH 7.3.Zymotic fluid 1000ml is taken, is heated to 95 DEG C, stands 2h, reclaims the unreacted alkane in upper strata
Hydrocarbon, it is 10 with membrane aperture-1μm micro-filtrate membrane filtration, remove somatic cells, fragment.The molecule of mass fraction 3% is added into zymotic fluid
The glucan for being 500 000 for 20 000 polyethylene glycol and the molecular weight of mass fraction 5% is measured, stirring makes each material be dissolved in hair
In zymotic fluid, double-aqueous phase system is formed.System to be sent into hypergravity equipment and carries out hypergravity processing, hypergravity level is 200g,
The mean residence time of hypergravity processing be 8s, the static 30min of system that will be handled by hypergravity, by upper and lower two-phase laminated flow,
Phase is removed, to 2 and is heated to 90 DEG C with 5M sulphur acid for adjusting pH, constant temperature 1h.Crystallizing at room temperature is at the uniform velocity down to 20 DEG C/h, uses fenestra
Footpath is 10-2μm ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, dry cake obtains product.Product quality is shown in Table
1。
Embodiment 3
Using n-tridecane hydrocarbon as substrate, the carbon dicarboxylic acids of candida tropicalis fermenting and producing 13 is utilized.Two during fermentation ends
Carboxylic acid concentration is 154.3 g/L, pH 7.5.Zymotic fluid 1000ml is taken, is heated to 80 DEG C, stands 2h, recovery upper strata is unreacted
Alkane, it is 10 with membrane aperture-2μm ultrafiltration membrance filter, remove somatic cells, fragment.Mass fraction 4% is added into zymotic fluid to divide
Son amount is the glucan that 10 000 polyethylene glycol and the molecular weight of mass fraction 6% are 400 000, and stirring is dissolved in each material
In zymotic fluid, double-aqueous phase system is formed.System is sent into hypergravity equipment and carries out hypergravity processing, hypergravity level is
300g, the mean residence time of hypergravity processing is 3s, the static 30min of system that will be handled by hypergravity, by upper and lower two-phase
Separation, removes phase, to 2.5 and is heated to 95 DEG C with 8M sulphur acid for adjusting pH, constant temperature 1h.Room temperature knot is at the uniform velocity down to 18 DEG C/h
Crystalline substance, it is 10 with membrane aperture-2μm ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, dry cake obtains product.Product
Quality is shown in Table 1.
Embodiment 4
Using n-tridecane hydrocarbon as substrate, the carbon dicarboxylic acids of candida tropicalis fermenting and producing 13 is utilized.Two during fermentation ends
Carboxylic acid concentration is 158.8g/L, pH 7.2.Zymotic fluid 1000ml is taken, is heated to 95 DEG C, stands 1.5h, reclaims upper strata unreacted
Alkane, with membrane aperture be 10-2μm ultrafiltration membrance filter, remove somatic cells, fragment.Mass fraction 6% is added into zymotic fluid
The glucan that the polyethylene glycol and the molecular weight of mass fraction 7% that molecular weight is 6 000 are 300 000, stirring are dissolved in each material
In zymotic fluid, double-aqueous phase system is formed.System is sent into hypergravity equipment and carries out hypergravity processing, hypergravity level is
350g, the mean residence time of hypergravity processing is 4s, the static 30min of system that will be handled by hypergravity, by upper and lower two-phase
Separation, removes phase, to 3.5 and is heated to 90 DEG C with 5M sulphur acid for adjusting pH, constant temperature 1h.Room temperature knot is at the uniform velocity down to 16 DEG C/h
Crystalline substance, it is 10 with membrane aperture-2μm ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, dry cake obtains product.Product
Quality is shown in Table 1.
Embodiment 5
Using n-dodecane hydrocarbon as substrate, the carbon dicarboxylic acids of candida tropicalis fermenting and producing 12 is utilized.Two during fermentation ends
Carboxylic acid concentration is 155.6g/L, pH 7.6.Zymotic fluid 1000ml is taken, is heated to 92 DEG C, stands 1.5h, reclaims upper strata unreacted
Alkane, with membrane aperture be 10-2μm ultrafiltration membrance filter, remove somatic cells, fragment.Mass fraction 6% is added into zymotic fluid
The glucan that the polyethylene glycol and the molecular weight of mass fraction 8% that molecular weight is 10 000 are 300 000, stirring dissolve each material
In zymotic fluid, double-aqueous phase system is formed.System is sent into hypergravity equipment and carries out hypergravity processing, hypergravity level is
400g, the mean residence time of hypergravity processing is 2s, the static 20min of system that will be handled by hypergravity, by upper and lower two-phase
Separation, removes phase, to 4.0 and is heated to 95 DEG C with 7M sulphur acid for adjusting pH, constant temperature 1h.Room temperature knot is at the uniform velocity down to 20 DEG C/h
Crystalline substance, it is 10 with membrane aperture-2μm ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, dry cake obtains product.Product
Quality is shown in Table 1.
Embodiment 6
Molar concentration 0.005mol/L dipotassium hydrogen phosphate is added into zymotic fluid, remaining condition is the same as embodiment 1.Product matter
Amount is shown in Table 1.
Embodiment 7
Molar concentration 0.02mol/L disodium hydrogen phosphate is added into zymotic fluid, remaining condition is the same as embodiment 2.Product matter
Amount is shown in Table 1.
Embodiment 8
Molar concentration 0.01mol/L dipotassium hydrogen phosphate is added into zymotic fluid, remaining condition is the same as embodiment 3.Product matter
Amount is shown in Table 1.
Comparative example 1
Double-aqueous phase system is handled without hypergravity, and with common centrifugal treating, centrifugation time 5min, centrifugal rotational speed
5000rpm, with embodiment 1, product quality is shown in Table 1 for remaining.
The long chain dicarboxylic acid product quality of table 1
As shown in Table 1, the long chain dicarboxylic acid product purity that prepared by the inventive method is high, and total nitrogen content is low, preferably
In industrialized production.
Claims (11)
1. a kind of method of purification of long chain dicarboxylic acid, it is characterised in that including herein below：
I, zymotic fluid heat inactivation will be terminated, zymotic fluid is microorganism metabolite obtained from liquid wax fermentation；
II, bacteria residue solid impurity is removed, reclaim alkane；
III, appropriate polyethylene glycol and glucan are added into zymotic fluid, each material is dissolved in zymotic fluid, aqueous two-phase is made
System；
IV, above-mentioned double-aqueous phase system being carried out to hypergravity processing, two-phase is rapidly separated mixed system up and down after hypergravity is handled,
Protein impurities are dissolved in phase, and product dicarboxylate is dissolved in lower phase；
V, lower phase, acidifying in step IV is taken to separate out dicarboxylic acid crystallizates, cool down, filter, being dried to obtain refined dicarboxylic acid product.
2. in accordance with the method for claim 1, it is characterised in that：The dicarboxylic acids point contained in zymotic fluid is terminated described in step I
Sub- formula is CnH2n-2O4, wherein n is 10-18, and dicarboxylic acids can be single a kind of dicarboxylic acids or mixed dicarboxylic acid.
3. in accordance with the method for claim 1, it is characterised in that：Zymotic fluid heat inactivation temperature described in step I is 75 DEG C
~100 DEG C.
4. in accordance with the method for claim 1, it is characterised in that：The molecular weight of polyethylene glycol described in step III is 4000
~40000, mass fraction is 2%~8%；The molecular weight of glucan is 100000~500000, and mass fraction is 3%~10%.
5. in accordance with the method for claim 4, it is characterised in that：The molecular weight of polyethylene glycol described in step III is 4000
~20000, mass fraction is 3%~6%；The molecular weight of glucan is 300000~500000, and mass fraction is 5%~8%.
6. in accordance with the method for claim 1, it is characterised in that：One is added in double-aqueous phase system described in step III simultaneously
Quantitative phosphate, concentration are 0.005~0.02mol/L.
7. in accordance with the method for claim 6, it is characterised in that：Phosphate is sodium ascorbyl phosphate or potassium phosphate.
8. in accordance with the method for claim 1, it is characterised in that：The hypergravity of step IV hypergravities processing it is horizontal for 10~
650g, wherein g are acceleration of gravity 9.8m/s2, the mean residence time of hypergravity processing is 0.2~10s, and hypergravity equipment is
High gravity rotating packed bed, deflector type, screw path type, rotating compact disc formula or fixed-rotator type hypergravity rotating device.
9. in accordance with the method for claim 1, it is characterised in that：The pH value being acidified described in step V is 2.0~4.0, heating
Temperature is 80~100 DEG C；Acidifying acid used is the H of any concentration2SO4、HNO3, HCl or H3PO4。
10. in accordance with the method for claim 1, it is characterised in that：Crystallisation by cooling temperature is 10~30 DEG C in step V.
11. in accordance with the method for claim 1, it is characterised in that：Filtering in step V uses NF membrane or microfiltration membranes, film
Pore diameter range is 10-3μm~10 μm.
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| CN102796775A (en) * | 2011-05-26 | 2012-11-28 | 中国科学院城市环境研究所 | Method for extracting lactic acid fermentation product of kitchen waste |
| CN102911036A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for obtaining high pure dicarboxylic acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796775A (en) * | 2011-05-26 | 2012-11-28 | 中国科学院城市环境研究所 | Method for extracting lactic acid fermentation product of kitchen waste |
| CN102911036A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Method for obtaining high pure dicarboxylic acid |
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Effective date of registration: 20230818 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |