CN103058848B - A kind of method intending homogeneous phase weak base anion-exchange resin separating organic acid - Google Patents
A kind of method intending homogeneous phase weak base anion-exchange resin separating organic acid Download PDFInfo
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- CN103058848B CN103058848B CN201210428590.9A CN201210428590A CN103058848B CN 103058848 B CN103058848 B CN 103058848B CN 201210428590 A CN201210428590 A CN 201210428590A CN 103058848 B CN103058848 B CN 103058848B
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- exchange resin
- organic acid
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Abstract
Intend a method for homogeneous phase weak base anion-exchange resin separating organic acid, belong to technical field of biochemical industry.This exchange resin represents with MKF-D30X.Organic acid standardized solution or its fermentation clear liquid are carried out Static Adsorption by MKF-D30X resin by the present invention, solution after absorption detects through high performance liquid chromatography (HPLC) method, resin hydrochloric acid elutriant after absorption carries out desorb, and stripping liquid detects through HPLC method.When the concentration of organic acid soln is 1 ~ 50gL
-1time, the loading capacity of MKF-D30X resin is 70 ~ 455mgg
-1.With 0.4 ~ 1.5molL
-1hydrochloric acid soln make eluent, desorption rate is 85% ~ 98%.The organic acid adsorptive capacity of the method is high, and desorption efficiency is high, and the reusability of resin is good.
Description
(1) technical field
The present invention relates to a kind of method intending homogeneous phase weak base anion-exchange resin separating organic acid, be specifically related to a kind of MKF-D30X resin and organic acid in succinic acid or oxysuccinic acid or citric acid or its fermented liquid is separated.
(2) background technology
In recent years along with the oil crisis that petroleum resources are in short supply, price rises to be caused, and the increasing the weight of of the problem of environmental pollution that causes of petrochemical complex, chemical synthesis is restricted due to raw material, pollution, economic problems.Microbe fermentation method utilizes microbial strains, and with agriculture product corn, cassava, stalk etc. for organic acid produced by basic raw material, and biomass resource abundance, pollute few, therefore fermentative Production organic acid gains great popularity.
Organic acid separation method mainly contains calcium salt precipitation method, liquid-liquid solvent extraction method, membrane separation process etc.Calcium salt method extraction can produce calcium sulfate waste; Solvent extration needs to consume a large amount of expensive organic solvent in the process extracted, and the toxicity of residual solvent has detrimentally affect to quality product; Membrane separating method process cost is high, as the power consumption in the consumption of ionic membrane and electrodialysis, and can not process divalent cation.And resin absorption partition method has advantages such as adsorption selectivity is high, simple to operate, energy consumption is low, resin can recycle, oneself is widely used in the aspects such as organic acid, amino acid, purification of pharmaceuticals.
Organic acid can participate in the vital process of animals and plants metabolism, is the intermediate product of metabolism, has significant biological activity, can prevent and cure diseases, can as the raw material of organic synthesis, industrial and agricultural production and medicine industry.Such as, succinic acid or oxysuccinic acid or citric acid are all some important organic compound, can be used as the intermediate of Organic Chemicals and synthesis complex organic compound, be widely used in medicine, food, synthetic plastics, rubber, protective coating, dyestuff and other industry.
The resin exploring a kind of high-adsorption-capacity is significant for organic acid separation and purification, and the systematic Study at present about anionite-exchange resin Adsorption organic acid is seldom reported, and (D301 resin, when succinic acid concentration is 20g/1, adsorptive capacity is 380/mgg
-1(Li Song, Yao Zhong, Liu Hui, etc. basic resin is separated succinic acid character research [J]. food and fermentation industries, 2007,33 (7): 54-57); NERCB04 resin, when succinic acid concentration is 31g/l, adsorptive capacity is 378.8/mgg
-1(QiangLi, Wang-liangLi, DanWang.pHNeutralizationwhileSuccinicAcidAdsorptionontoA nion-ExchangeResins.ApplBiochemBiotechnol.2010,160:438445)).The present invention carries out organic acid Static Adsorption with a kind of plan homogeneous phase weak base anion-exchange resin (MKF-D30X) of high-adsorption-capacity.This resin is the weakly alkaline tertiary amine-type anionite-exchange resin that carry out the comb-like graft of glycidyl methacrylate and acrylamide with atom transfer radical polymerization (ATRP) method on crosslinked chloracetylated polystyrene microballoon after, reamination obtains, and has the Pectinate flexible chain structure of certain length and the large advantage of degree of freedom.
(3) summary of the invention
Current ion exchange resin is applied widely in the industrial sector that each are different, and the novel ion exchange resin of development research has profound significance.MKF-D30X resin of the present invention; carry out the comb-like graft of glycidyl methacrylate with ATRP method on crosslinked chloracetylated polystyrene microballoon after; the weakly alkaline tertiary amine-type anionite-exchange resin obtained after amination, and it is applied to the organic acid in absorption fermented liquid.Concrete synthesis step is as follows:
On crosslinked chloracetylated polystyrene microballoon with Transfer Radical Polymerization or ATRP method carry out glycidyl methacrylate or and acrylamide copolymerization or and acrylic ester copolymer comb-like graft after the weakly alkaline tertiary amine-type anionite-exchange resin that obtains of reamination.
MKF-D30X resin has the flexible pectination chain structure of certain length and the large advantage of degree of freedom, when Adsorption organic acid due to its special structure (pectination side chain, flexibility, extensibility are good), functional group is to the star-shaped diffusion of surrounding and have larger degree of freedom, and add and effectively contact with organic acid, in better affinity, therefore easier Adsorption organic acid.
A kind of method intending homogeneous phase weak base anion-exchange resin separating organic acid provided by the invention, undertaken by following operation steps:
(1) configure 40mL, concentration is 1 ~ 50gL
-1, the organic acid standardized solution of pH about 7.2 ~ 2.1 or its fermented liquid are in Erlenmeyer flask.
(2) (a certain amount of dried resin is immersed in 10h in 95% ethanolic soln to take 0.2 ~ 3gMKF-D30X resin, pure water is washed till without ethanol taste, 2h is soaked with 5%HCl (v/v), pure water is washed till pH neutrality, 2 ~ 4%NaOH (w/v) is used to soak 2h again, pure water is washed till pH neutrality, stand-by) be added in organic acid soln;
MKF-D30X exchange capacity of resin is 2.2 ~ 4.1mmo1g
-1, degree of crosslinking 2 ~ 15%, particle diameter 20 ~ 220 order.
(3) organic acid soln that step (2) obtains is placed in 20 ~ 60 DEG C of water bath with thermostatic control shaking tables and shakes absorption 1 ~ 3h, after absorption, raffinate detects through high performance liquid chromatography (HPLC);
(4) the MKF-D30X resin after absorption is moved to 10 ~ 40ml in Erlenmeyer flask, 0.4 ~ 1.5mo1L
-1the desorb of hydrochloric acid elutriant;
(5) elutriant that step (4) obtains is placed in 45 ~ 80 DEG C of water bath with thermostatic control shaking table concussion desorb 1 ~ 4h, filters its stripping liquid and detect through HPLC.
(4) accompanying drawing explanation
Accompanying drawing is a kind of infared spectrum intending homogeneous phase weak base anion-exchange resin in the present invention.
(5) embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
Adsorption conditions: configuration 1gL
-1succinic acid standardized solution 40mL (pH about 3.2), in Erlenmeyer flask, takes 0.2g, and exchange capacity is 2.0mmo1g
-1, degree of crosslinking is 2%, particle diameter be 20 object MKF-D30X resins in succinic acid standardized solution, be placed on concussion absorption 2h in 20 DEG C of water bath with thermostatic control shaking tables, the solution after absorption detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 10ml, 1.5molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 45 DEG C of water bath with thermostatic control shaking table concussion desorb 1h, stripping liquid detects through HPLC.Loading capacity is 100mgg
-1, desorption rate reaches 85%.
Embodiment 2
Adsorption conditions: configuration 20gL
-1succinic acid standardized solution 40mL (pH about 2.7), in Erlenmeyer flask, takes 0.2g, and exchange capacity is 3.3mmolg
-1, degree of crosslinking is 7%, particle diameter be 100 object MKF-D30X resins in succinic acid standardized solution, be placed on concussion absorption 3h in 25 DEG C of water bath with thermostatic control shaking tables, the solution after absorption detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 40ml, 1.0mo1L
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 60 DEG C of water bath with thermostatic control shaking table concussion desorb 3h, stripping liquid detects through HPLC.Loading capacity is 421mgg
-1, desorption rate reaches 98%.
Embodiment 3
Adsorption conditions: configuration 50gL
-1succinic acid standardized solution 40mL (pH about 2.1), in Erlenmeyer flask, takes 0.2g, and exchange capacity is 4.1mmolg
-1, degree of crosslinking is 10%, particle diameter be 220 object MKF-D30X resins in succinic acid solution, be placed on concussion absorption 3h in 25 DEG C of water bath with thermostatic control shaking tables, after absorption, solution detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 20ml, 0.4molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 45 DEG C of water bath with thermostatic control shaking table concussion desorb 4h, stripping liquid detects through HPLC.Loading capacity is 455mgg
-1, desorption rate reaches 89%.
Embodiment 4
Adsorption conditions: configuration 20gL
-1oxysuccinic acid standardized solution 40mL (pH about 2.7), in Erlenmeyer flask, takes 3g, and exchange capacity is 3.3mmolg
-1, degree of crosslinking is 15%, particle diameter be 50 object MKF-D30X resins in succinic acid standardized solution, be placed on concussion absorption 1h in 60 DEG C of water bath with thermostatic control shaking tables, the solution after absorption detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 20ml, 0.6molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 60 DEG C of water bath with thermostatic control shaking table concussion desorb 2h, stripping liquid detects through HPLC.Loading capacity is 120mgg
-1, desorption rate reaches 94%.
Embodiment 5
Adsorption conditions: configuration 20gL
-1citric acid standardized solution 40mL (pH about 2.4), in Erlenmeyer flask, takes 2g, and exchange capacity is 3.5mmolg
-1, degree of crosslinking is 7%, particle diameter be 100 object MKF-D30X resins in succinic acid standardized solution, be placed on concussion absorption 3h in 45 DEG C of water bath with thermostatic control shaking tables, the solution after absorption detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 30ml, 1.0molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 70 DEG C of water bath with thermostatic control shaking table concussion desorb 2h, stripping liquid detects through HPLC.Loading capacity is 200mgg
-1, desorption rate reaches 98%.
Embodiment 6
Adsorption conditions: take 0.2g, exchange capacity is 2.2mmolg
-1, degree of crosslinking is 7%, particle diameter is 220 object MKF-D30X resins, adds 40mL, 1gL
-1(pH about 7.2) citric acid fermentation broth is in Erlenmeyer flask, and be placed on concussion absorption 2h in 20 DEG C of water bath with thermostatic control shaking tables, after absorption, solution detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 20ml, 0.4molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 60 DEG C of water bath with thermostatic control shaking table concussion desorb 2h, stripping liquid detects through HPLC.Loading capacity is 70mgg
-1, desorption rate reaches 92%.
Embodiment 7
Adsorption conditions: take 2.0g, exchange capacity is 3.5mmolg
-1, degree of crosslinking is 10%, particle diameter is 100 object MKF-D30X resins, adds 40mL, 30gL
-1(pH about 6.5) succinic acid fermentation liquor is in Erlenmeyer flask, and be placed on concussion absorption 1h in 45 DEG C of water bath with thermostatic control shaking tables, after absorption, solution detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 10ml, 0.6molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 80 DEG C of water bath with thermostatic control shaking table concussion desorb 1h, stripping liquid detects through HPLC.Loading capacity is 100mgg
-1, desorption rate reaches 90%.
Embodiment 8
Adsorption conditions: take 3.0g, exchange capacity is 4.1mmolg
-1, degree of crosslinking is 15%, particle diameter is 50 object MKF-D30X resins, adds 40mL, 50gL
-1(pH about 6.4) malic acid fermentation liquid is in Erlenmeyer flask, and be placed on concussion absorption 2h in 60 DEG C of water bath with thermostatic control shaking tables, after absorption, solution detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 30ml, 1.5molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 45 DEG C of water bath with thermostatic control shaking table concussion desorb 4h, stripping liquid detects through HPLC.Loading capacity is 80mgg
-1, desorption rate reaches 96%.
Embodiment 9
Adsorption conditions: take 0.2g, exchange capacity is 3.2mmolg
-1, degree of crosslinking is 2%, particle diameter is 20 object MKF-D30X resins, adds 40mL, 40gL
-1(pH about 6.5) succinic acid fermentation liquor is in Erlenmeyer flask, and be placed on concussion absorption 3h in 25 DEG C of water bath with thermostatic control shaking tables, after absorption, solution detects through HPLC, and the resin after absorption moves in Erlenmeyer flask with 40ml, 1.0molL
-1hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed in 60 DEG C of water bath with thermostatic control shaking table concussion desorb 3h, stripping liquid detects through HPLC.Loading capacity is 271mgg
-1, desorption rate reaches 98%.
Claims (5)
1. intend the method for homogeneous phase weak base anion-exchange resin Adsorption organic acid for one kind, it is characterized in that this plan homogeneous phase weak base anion-exchange resin is obtained by following preparation method: the comb-like graft carrying out glycidyl methacrylate or glycidyl methacrylate and acrylamide copolymerization or glycidyl methacrylate and acrylic ester copolymer on crosslinked acetobrom or chloracetylated polystyrene microballoon with Transfer Radical Polymerization, then the plan homogeneous phase weakly alkaline tertiary amine-type anionite-exchange resin that obtains of reamination;
The method of its Adsorption organic acid is carried out according to the following steps: take intend homogeneous phase weak base anion-exchange resin 0.2 ~ 3g in 40mL, concentration be 1 ~ 50gL
-1, pH be 7.2 ~ 2.1 succinic acid or oxysuccinic acid or citric acid fermentation broth in, solution is placed in 20 ~ 60 DEG C of water bath with thermostatic control shaking tables and shakes absorption 1 ~ 3h, the solution after its absorption detects through HPLC; Resin after absorption moves in Erlenmeyer flask and adds 0.4 ~ 1.5molL
-1hydrochloric acid, and this Erlenmeyer flask is placed in 45 ~ 80 DEG C of water bath with thermostatic control shaking table concussion desorb 1 ~ 4h, filter its stripping liquid and detect through HPLC.
2. a kind of method intending homogeneous phase weak base anion-exchange resin Adsorption organic acid according to claim 1; it is characterized in that described crosslinked acetobrom or chloracetylated polystyrene microballoon are gel or macroporous microsphere; its degree of crosslinking is 2 ~ 15%, and particle diameter is 20 ~ 220 orders.
3. a kind of method intending homogeneous phase weak base anion-exchange resin Adsorption organic acid according to claim 1, it is characterized in that described after intending the absorption of homogeneous phase weak base anion-exchange resin, the loading capacity of its succinic acid or oxysuccinic acid or citric acid is 70 ~ 455mgg
-1, after desorb, desorption efficiency reaches 85% ~ 98%.
4. a kind of method intending homogeneous phase weak base anion-exchange resin Adsorption organic acid according to claim 1, is characterized in that the described comb-like graft rate obtained with Transfer Radical Polymerization is for mass ratio 200% ~ 2000%.
5. a kind of method intending homogeneous phase weak base anion-exchange resin Adsorption organic acid according to claim 1, it is characterized in that described amination completes by adding dimethylamine or diethylamine or pyridine, its tertiary amine group exchange capacity is 2.0 ~ 4.1mmolg
-1.
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