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CN103058848A - Method for separating organic acid by using pseudo-homogeneous weak-base anion exchange resin - Google Patents

Method for separating organic acid by using pseudo-homogeneous weak-base anion exchange resin Download PDF

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CN103058848A
CN103058848A CN2012104285909A CN201210428590A CN103058848A CN 103058848 A CN103058848 A CN 103058848A CN 2012104285909 A CN2012104285909 A CN 2012104285909A CN 201210428590 A CN201210428590 A CN 201210428590A CN 103058848 A CN103058848 A CN 103058848A
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organic acid
exchange resin
resin
base anion
acid
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CN103058848B (en
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刘晓宁
雷文
姜岷
魏荣卿
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Nanjing Tech University
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Nanjing Tech University
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Abstract

A method for separating organic acid by pseudo-homogeneous weak-base anion exchange resin belongs to the technical field of biochemical engineering. The exchange resin is represented by MKF-D30X. The method comprises the steps of statically adsorbing an organic acid standard solution or a fermentation clear liquid thereof by MKF-D30X resin, detecting the adsorbed solution by a High Performance Liquid Chromatography (HPLC) method, desorbing the adsorbed resin by using a hydrochloric acid desorption solution, and detecting the desorption solution by the HPLC method. When the concentration of the organic acid solution is 1-50 g.L-1The MKF-D30X resin has an adsorption capacity of 70-455 mg g-1. Using 0.4-1.5 mol.L-1Hydrochloric acid solution is used as eluent, and the desorption rate is 85-98%. The method has the advantages of high organic acid adsorption amount, high desorption rate and good reusability of the resin.

Description

A kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid
(1) technical field
The present invention relates to a kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid, be specifically related to a kind of MKF-D30X resin organic acid in Succinic Acid or oxysuccinic acid or citric acid or its fermented liquid is separated.
(2) background technology
Increasing the weight of of the problem of environmental pollution that the in recent years soaring oil crisis that causes of, price in short supply along with petroleum resources, and petrochemical complex causes, chemical synthesis is owing to raw material, pollution, economic problems are restricted.Microbe fermentation method utilizes microbial strains, produce organic acid take agriculture product corn, cassava, stalk etc. as basic raw material, and the biomass resource source is abundant, pollution is few, so the fermentative Production organic acid gains great popularity.
The organic acid separation method mainly contains calcium salt precipitation method, liquid-liquid solvent extraction method, membrane separation process etc.Calcium salt method extracts and can produce the calcium sulfate waste; Solvent extration needs to consume the organic solvent of a large amount of costlinesses in the process of extracting, the toxicity of residual solvent has detrimentally affect to quality product; The membrane separating method process cost is high, such as the consumption of ionic membrane and the power consumption in the electrodialysis, and can not process divalent cation.And the resin absorption partition method has adsorption selectivity height, simple to operate, the advantage such as energy consumption is low, resin can recycle, and 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, and can be used as the raw material of organic synthesis, industrial and agricultural production and medicine industry.For example, Succinic Acid or oxysuccinic acid or citric acid all are some important organic compound, can be used as the intermediate of Organic Chemicals and synthetic complex organic compound, be widely used in medicine, food, synthetic plastics, rubber, protective coating, dyestuff and other industry.
The resin of exploring a kind of high-adsorption-capacity is significant for the organic acid separation and purification, reports seldom that about the systematic Study of anionite-exchange resin Adsorption organic acid (the D301 resin, when Succinic Acid concentration was 20g/1, adsorptive capacity was 380/mgg at present -1(Li Song, Yao Zhong, Liu Hui, etc. basic resin separates Succinic Acid property research [J]. food and fermentation industries, 2007,33 (7): 54-57); The NERCB04 resin, when Succinic Acid concentration was 31g/l, adsorptive capacity was 378.8/mgg -1(Qiang Li, Wang-liang Li, Dan Wang.pH Neutralization while Succinic Acid Adsorption onto Anion-Exchange Resins.Appl Biochem Biotechnol.2010,160:438445)).The present invention carries out the 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 reamination obtains after the pectination grafting of carrying out glycidyl methacrylate and acrylamide on the crosslinked chloroacetylation polystyrene microsphere with atom transfer radical polymerization (ATRP) method, has the pectination flexible chain structure of certain-length and the large advantage of degree of freedom.
(3) summary of the invention
Ion exchange resin is used in each different industrial sector widely at present, and the novel ion exchange resin of development research has profound significance.MKF-D30X resin of the present invention; after carrying out the pectination grafting of glycidyl methacrylate with the ATRP method on the crosslinked chloroacetylation polystyrene microsphere; the weakly alkaline tertiary amine-type anionite-exchange resin that after amination, obtains, and it is applied to adsorb organic acid in the fermented liquid.Concrete synthesis step is as follows:
Carry out with Transfer Radical Polymerization or ATRP method on the crosslinked chloroacetylation polystyrene microsphere glycidyl methacrylate or and the acrylamide copolymerization or and the pectination grafting of acrylic ester copolymer after the weakly alkaline tertiary amine-type anionite-exchange resin that obtains of reamination.
The MKF-D30X resin has the flexible pectination chain structure of certain-length and the large advantage of degree of freedom, when Adsorption organic acid because its special structure (pectination side chain, flexibility, extensibility are good), functional group is to star-shaped diffusion all around and have larger degree of freedom, effectively contact and increased with organic acid, be better affinity, therefore easier Adsorption organic acid.
A kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid provided by the invention, undertaken by following operation steps:
(1) configuration 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 by weighing 0.2~3g MKF-D30X resin, pure water is washed till without ethanol and distinguishes the flavor of, soak 2h with 5%HCl (v/v), pure water is washed till pH neutrality, use again 2~4%NaOH (w/v) to soak 2h, pure water is washed till pH neutrality, and is stand-by) be added in the organic acid soln;
The MKF-D30X exchange capacity of resin is 2.2~4.1mmo1g -1, degree of crosslinking 2~15%, particle diameter 20~220 orders.
(3) organic acid soln that step (2) is obtained places 20~60 ℃ of water bath with thermostatic control shaking table concussion absorption 1~3h, and raffinate detects through high performance liquid chromatography (HPLC) after the absorption;
(4) the MKF-D30X resin after will adsorbing moves in the Erlenmeyer flask with 10~40ml, 0.4~1.5mo1L -1The desorb of hydrochloric acid elutriant;
(5) elutriant that step (4) is obtained places 45~80 ℃ of water bath with thermostatic control shaking table concussion desorb 1~4h, filters its stripping liquid and detects through HPLC.
(4) description of drawings
Accompanying drawing is a kind of infared spectrum of intending the homogeneous phase weak base anion-exchange resin among the present invention.
(5) embodiment
Following examples are used for explanation 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 by weighing 0.2g, and exchange capacity is 2.0mmo1g -1, degree of crosslinking is 2%, particle diameter be 20 purpose MKF-D30X resins in the Succinic Acid standardized solution, be placed on concussion absorption 2h in 20 ℃ of water bath with thermostatic control shaking tables, the solution after the absorption detects through HPLC, the resin after the absorption moves in the Erlenmeyer flask and uses 10ml, 1.5molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 45 ℃ of water bath with thermostatic control shaking table concussion desorb 1h, and 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 by weighing 0.2g, and exchange capacity is 3.3mmolg -1, degree of crosslinking is 7%, particle diameter be 100 purpose MKF-D30X resins in the Succinic Acid standardized solution, be placed on concussion absorption 3h in 25 ℃ of water bath with thermostatic control shaking tables, the solution after the absorption detects through HPLC, the resin after the absorption moves in the Erlenmeyer flask and uses 40ml, 1.0mo1L -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 60 ℃ of water bath with thermostatic control shaking table concussion desorb 3h, and 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 by weighing 0.2g, and exchange capacity is 4.1mmolg -1, degree of crosslinking is 10%, particle diameter be 220 purpose MKF-D30X resins in Succinic Acid solution, be placed on concussion absorption 3h in 25 ℃ of water bath with thermostatic control shaking tables, solution detects through HPLC after the absorption, the resin after the absorption moves in the Erlenmeyer flask and uses 20ml, 0.4molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 45 ℃ of water bath with thermostatic control shaking table concussion desorb 4h, and 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 by weighing 3g, and exchange capacity is 3.3mmolg -1, degree of crosslinking is 15%, particle diameter be 50 purpose MKF-D30X resins in the Succinic Acid standardized solution, be placed on concussion absorption 1h in 60 ℃ of water bath with thermostatic control shaking tables, the solution after the absorption detects through HPLC, the resin after the absorption moves in the Erlenmeyer flask and uses 20ml, 0.6molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 60 ℃ of water bath with thermostatic control shaking table concussion desorb 2h, and 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 by weighing 2g, and exchange capacity is 3.5mmolg -1, degree of crosslinking is 7%, particle diameter be 100 purpose MKF-D30X resins in the Succinic Acid standardized solution, be placed on concussion absorption 3h in 45 ℃ of water bath with thermostatic control shaking tables, the solution after the absorption detects through HPLC, the resin after the absorption moves in the Erlenmeyer flask and uses 30ml, 1.0molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 70 ℃ of water bath with thermostatic control shaking table concussion desorb 2h, and stripping liquid detects through HPLC.Loading capacity is 200mgg -1, desorption rate reaches 98%.
Embodiment 6
Adsorption conditions: take by weighing 0.2g, exchange capacity is 2.2mmolg -1, degree of crosslinking is 7%, particle diameter is 220 purpose MKF-D30X resins, adds 40mL, 1gL -1(pH about 7.2) citric acid fermentation broth is placed on concussion absorption 2h in 20 ℃ of water bath with thermostatic control shaking tables in Erlenmeyer flask, solution detects through HPLC after the absorption, and the resin after the absorption moves in the Erlenmeyer flask and uses 20ml, 0.4molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 60 ℃ of water bath with thermostatic control shaking table concussion desorb 2h, and stripping liquid detects through HPLC.Loading capacity is 70mgg -1, desorption rate reaches 92%.
Embodiment 7
Adsorption conditions: take by weighing 2.0g, exchange capacity is 3.5mmolg -1, degree of crosslinking is 10%, particle diameter is 100 purpose MKF-D30X resins, adds 40mL, 30gL -1(pH about 6.5) succinic acid fermentation liquor is placed on concussion absorption 1h in 45 ℃ of water bath with thermostatic control shaking tables in Erlenmeyer flask, solution detects through HPLC after the absorption, and the resin after the absorption moves in the Erlenmeyer flask and uses 10ml, 0.6molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 80 ℃ of water bath with thermostatic control shaking table concussion desorb 1h, and stripping liquid detects through HPLC.Loading capacity is 100mgg -1, desorption rate reaches 90%.
Embodiment 8
Adsorption conditions: take by weighing 3.0g, exchange capacity is 4.1mmolg -1, degree of crosslinking is 15%, particle diameter is 50 purpose MKF-D30X resins, adds 40mL, 50gL -1(pH about 6.4) malic acid fermentation liquid is placed on concussion absorption 2h in 60 ℃ of water bath with thermostatic control shaking tables in Erlenmeyer flask, solution detects through HPLC after the absorption, and the resin after the absorption moves in the Erlenmeyer flask and uses 30ml, 1.5molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 45 ℃ of water bath with thermostatic control shaking table concussion desorb 4h, and stripping liquid detects through HPLC.Loading capacity is 80mgg -1, desorption rate reaches 96%.
Embodiment 9
Adsorption conditions: take by weighing 0.2g, exchange capacity is 3.2mmolg -1, degree of crosslinking is 2%, particle diameter is 20 purpose MKF-D30X resins, adds 40mL, 40gL -1(pH about 6.5) succinic acid fermentation liquor is placed on concussion absorption 3h in 25 ℃ of water bath with thermostatic control shaking tables in Erlenmeyer flask, solution detects through HPLC after the absorption, and the resin after the absorption moves in the Erlenmeyer flask and uses 40ml, 1.0molL -1The hydrochloric acid elutriant carries out desorb, and Erlenmeyer flask is placed 60 ℃ of water bath with thermostatic control shaking table concussion desorb 3h, and stripping liquid detects through HPLC.Loading capacity is 271mgg -1, desorption rate reaches 98%.

Claims (8)

1. method of intending homogeneous phase weak base anion-exchange resin separating organic acid, it is characterized in that this plan homogeneous phase weak base anion-exchange resin or MKF-D30X resin are to be obtained by following preparation method: on crosslinked acetobrom or chloroacetylation polystyrene microsphere with Transfer Radical Polymerization or ATRP method carry out glycidyl methacrylate or and the acrylamide copolymerization or and the pectination grafting of acrylic ester copolymer, then the weakly alkaline tertiary amine-type anionite-exchange resin that obtains of reamination;
The method of its Adsorption organic acid can be carried out according to the following steps: taking by weighing plan homogeneous phase weak base anion-exchange resin or MKF-D30X resin is 1~50gL in 40mL, concentration -1, pH about 7.2~2.1 the organic acid standardized solution or as in Succinic Acid or oxysuccinic acid or the citric acid fermentation broth, solution is placed 20~60 ℃ of water bath with thermostatic control shaking tables concussion absorption, 1~3h, the solution after its absorption detects through HPLC; Resin after the absorption moves to and adds 0.4~1.5molL in the Erlenmeyer flask -1Hydrochloric acid, and this Erlenmeyer flask placed 45~80 ℃ of C water bath with thermostatic control shaking tables concussion desorb, 1~4h filters its stripping liquid and detects through HPLC.
2. a kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid according to claim 1 is characterized in that described organic acid can be Succinic Acid or oxysuccinic acid or citric acid or organic acid fermented liquid or its fermented waste fluid or contain this organic acid recovery liquid.
3. a kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid according to claim 1; it is characterized in that described crosslinked acetobrom or chloroacetylation polystyrene microsphere can be gel or macroporous microsphere; its degree of crosslinking can be 2~15%, and particle diameter is 20~220 orders.
4. a kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid according to claim 1, it is characterized in that describedly after intending homogeneous phase weak base anion-exchange resin or MKF-D30X resin absorption, the loading capacity of organic acid or Succinic Acid or oxysuccinic acid or citric acid is 70~455mg-g -1, desorption efficiency reaches 85%~98% after the desorb.
5. a kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid according to claim 1 is characterized in that described organic acid concentration is 1~50gL -1, pH is about 7.2~2.1, and amount of resin is 0.2~3g, and the concentration of hydrochloric acid elutriant is 0.4~1.5molL -1
6. a kind of method of intending homogeneous phase weak base anion-exchange resin separating organic acid according to claim 1 is characterized in that described adsorption temp is 20~60 ℃, and desorption temperature is 45~80 ℃.
7. a kind of preparation method who intends the homogeneous phase weak base anion-exchange resin according to claim 1 is characterized in that the described pectination percentage of grafting that obtains take Transfer Radical Polymerization or ATRP method is as mass ratio 200%~2000%.
8. a kind of preparation method who intends the homogeneous phase weak base anion-exchange resin according to claim 1 is characterized in that described amination can finish by adding dimethylamine or diethylamine or pyridine, and its tertiary amine group exchange capacity is 2.0~4.1mmolg-1.
CN201210428590.9A 2012-11-01 2012-11-01 Method for separating organic acid by using pseudo-homogeneous weak-base anion exchange resin Expired - Fee Related CN103058848B (en)

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CN112877481A (en) * 2020-12-28 2021-06-01 河北省农林科学院遗传生理研究所(河北省农林科学院农产品质量安全研究中心) Purification treatment method for soluble sugar in fruits and vegetables

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