CN112679526B - Method for recovering D-7-ACA from D-7-ACA crystallization mother liquor - Google Patents
Method for recovering D-7-ACA from D-7-ACA crystallization mother liquor Download PDFInfo
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Abstract
The invention provides a method for recovering D-7-ACA from D-7-ACA crystallization mother liquor, belonging to the technical field of medicines. The method comprises the following steps: (1) and (4) nanofiltration: taking D-7-ACA crystallization mother liquor, and carrying out nanofiltration concentration; (2) resin adsorption: adsorbing the concentrated D-7-ACA crystallization mother liquor by macroporous adsorption resin to obtain macroporous adsorption resin containing D-7-ACA; (3) and (3) analysis: resolving the macroporous adsorption resin containing D-7-ACA; (4) and (3) ultrafiltration: carrying out ultrafiltration on the resolution solution; (5) and (3) decoloring: decolorizing the ultrafiltered feed liquid; (6) and (3) crystallization: crystallizing the decolorized feed liquid, filtering, and drying to obtain the final product. The D-7-ACA is prepared according to a specific method, the process flow is short, and the operation is simple; meanwhile, the obtained D-7-ACA has high yield, high purity and stable product quality, and can be directly used as a product; in addition, the method reduces COD discharge, reduces environmental pollution and reduces production cost. The invention realizes green production of D-7-ACA, has great economic and social benefits and good application prospect.
Description
Technical Field
The invention belongs to the technical field of medicines, relates to preparation of D-7-ACA, and particularly relates to a method for recovering D-7-ACA from D-7-ACA crystallization mother liquor.
Background
D-7-ACA (3-deacetyl-7-aminocephalosporanic acid) is used as a novel intermediate of cephalosporin antibiotics, compared with 7-ACA (7-aminocephalosporanic acid), acetyl at the 3-position is removed, so that the production process route can be simplified in the process of synthesizing part of cephalosporin varieties, and the D-7-ACA has the characteristics of simple modification, easy purification, good finished product quality, reduction of production cost and the like, and the development of D-7-ACA provides a new choice for developing the third generation, the fourth generation and the forthcoming fifth generation of cephalosporin in China. And the application of the D-7-ACA in cephalosporin antibiotics products such as cefuroxime, cefoxitin, cefpodoxime proxetil and the like has the characteristics of high yield, high quality and the like.
The domestic D-7-ACA production basically realizes the enzyme production. The process route uses cephalosporin C as a raw material, enzymatic cracking is carried out, the cracking solution is crystallized to obtain D-7-ACA, a large amount of crystallization mother liquor is generated in the production process, the residual content of the D-7-ACA crystallization mother liquor is about 1.5g/L, and for the D-7-ACA with the residual content of about 1.5g/L in the crystallization mother liquor, if the D-7-ACA is directly discharged to an environment-friendly treatment link without recovery, huge waste is caused, huge COD is generated, the treatment cost is increased, a method capable of recovering the D-7-ACA in the D-7-ACA crystallization mother liquor is urgently needed, the production cost is reduced, the COD discharge is reduced, and green production is realized.
At present, no report on the method for directly recovering the D-7-ACA from the D-7-ACA crystallization mother liquor exists in China.
Disclosure of Invention
In view of the above, the invention provides a method for directly recovering D-7-ACA from D-7-ACA crystallization mother liquor, which improves the yield of D-7-ACA produced by the prior art, reduces COD discharge and reduces the production cost.
In order to achieve the above object, the present invention provides a method for recovering D-7-ACA from a D-7-ACA crystallization mother liquor, comprising the steps of:
(1) and (4) nanofiltration: taking D-7-ACA crystallization mother liquor, and carrying out nanofiltration concentration;
(2) resin adsorption: adsorbing the concentrated D-7-ACA crystallization mother liquor by macroporous adsorption resin to obtain macroporous adsorption resin containing D-7-ACA;
(3) and (3) analysis: resolving the macroporous adsorption resin containing D-7-ACA;
(4) and (3) ultrafiltration: carrying out ultrafiltration on the resolution solution;
(5) and (3) decoloring: decolorizing the ultrafiltered feed liquid;
(6) and (3) crystallization: crystallizing the decolorized feed liquid, filtering, and drying to obtain the final product.
Further, in the step (1), the pH of the D-7-ACA crystallization mother liquor is adjusted to 6.5-7.5 before nanofiltration concentration; and/or in the step (1), the temperature of the D-7-ACA crystallization mother liquor before nanofiltration concentration is 5-12 ℃;
preferably, in the step (1), the D-7-ACA crystallization mother liquor before nanofiltration concentration is adjusted to pH 7.1; and/or, in the step (1), the temperature of the D-7-ACA crystallization mother liquor before nanofiltration concentration is 11 ℃;
more preferably, in the step (1), ammonia is used for the pH adjustment.
Further, in the step (1), the titer of the D-7-ACA crystallization mother liquor after nanofiltration concentration is 6000-10000 mug/ml;
preferably, in the step (1), the titer of the D-7-ACA crystallization mother liquor after nanofiltration concentration is 9000 mu g/ml.
Further, in the step (2), the flow rate is 0.5-1.0 BV/h when the adsorbent is adsorbed by macroporous adsorbent resin; and/or in the step (2), when the adsorbent is adsorbed by macroporous adsorption resin, the adsorption capacity is 10-15 g/L;
preferably, in the step (2), the flow rate is 1.0BV/h when the macroporous adsorption resin is used for adsorption; and/or in the step (2), the adsorption capacity is 13g/L when the macroporous adsorption resin is used for adsorption.
Further, in the step (2), the macroporous resin is LXT series resin;
preferably, in step (2), the macroporous resin is LXT-036.
Further, in the step (3), the resolving agent used in the resolving is selected from one of sodium bicarbonate, sodium acetate and sodium carbonate; and/or in the step (3), the volume of the resolving agent during resolving is 0.5-2.0 BV; and/or in the step (3), the flow speed of the resolving agent during resolving is 0.3-0.5 BV/h; and/or in the step (3), the temperature during analysis is 8-12 ℃;
preferably, in the step (3), the analysis agent used in the analysis is selected from one of sodium bicarbonate, sodium acetate and sodium carbonate with the concentration of 0.5-2.0%; and/or in the step (3), the volume of the resolving agent during resolving is 0.8-1.5 BV;
more preferably, the resolving agent used in the resolving is selected from sodium bicarbonate with a concentration of 1%; and/or in the step (3), the volume of the resolving agent during resolving is 1.3 BV; and/or in the step (3), the flow rate of the resolving agent during resolving is 0.5 BV/h.
Furthermore, the adsorption and/or desorption of the macroporous adsorption resin are carried out in a top-down mode.
Further, in the step (4), the ultrafiltration membrane used for ultrafiltration has a molecular weight cutoff of 5000 daltons.
Further, in the step (5), activated carbon is used for decoloring;
preferably, the volume of the activated carbon is 2-3 per mill of the volume of the feed liquid;
more preferably, the volume of the activated carbon is 3 per mill of the volume of the feed liquid.
Further, in the step (6), the pH is adjusted to 4.5-5.5 during crystallization; and/or in the step (6), the temperature during crystallization is 5-10 ℃;
preferably, in the step (6), the pH is adjusted to 5.2 during the crystallization;
more preferably, in step (6), the pH is adjusted using 10% hydrochloric acid.
In the present invention, the filtration and drying are performed by using general filtration and drying equipment.
In the invention, the D-7-ACA crystallization mother liquor is feed liquor containing a small amount of D-7-ACA generated in the normal crystallization process.
The nanofiltration membrane group consists of 16 nanofiltration membrane systems, and the nanofiltration membrane system consists of a material delivery pump, an ultrafiltration membrane core, a membrane shell and a control system. The ultrafiltration membrane used for ultrafiltration consists of 3 ultrafiltration membrane systems, and each ultrafiltration membrane system consists of a delivery pump, an ultrafiltration membrane core, a membrane shell and a control system.
The invention provides a method for recovering D-7-ACA in D-7-ACA crystallization mother liquor, which only comprises the steps of nanofiltration, resin adsorption, resolution, ultrafiltration, decoloration, crystallization, filtration and drying, and has short process flow and simple operation; meanwhile, the D-7-ACA recovered from the D-7-ACA crystallization mother liquor by the method has high yield, high purity and stable product quality, can be directly used as a product, and improves the yield of the D-7-ACA produced by the prior art; in addition, the method reduces COD discharge, reduces environmental pollution and reduces production cost. The method for recovering the D-7-ACA from the D-7-ACA crystallization mother liquor realizes the purification while recovering the D-7-ACA, realizes the green production of the D-7-ACA, has great economic and social benefits and has good application prospect.
Obviously, many modifications, substitutions, and variations are possible in light of the above teachings of the invention, without departing from the basic technical spirit of the invention, as defined by the following claims.
The present invention will be described in further detail with reference to the following examples. This should not be understood as limiting the scope of the above-described subject matter of the present invention to the following examples. All the technologies realized based on the above contents of the present invention belong to the scope of the present invention.
Detailed Description
The raw materials and equipment used in the embodiment of the present invention are known products and obtained by purchasing commercially available products.
Example 1 Process for recovering D-7-ACA from mother liquor of D-7-ACA crystallization
The method specifically comprises the following steps:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 6.9 with ammonia water, controlling feed liquid temperature at 9 deg.C, nano-filtering, concentrating to 7000 μ g/ml titer;
(2) according to the adsorption capacity of 10g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 0.5BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) resolving 1.0BV of 0.6% sodium bicarbonate solution with the flow rate of 0.3BV/h by using the macroporous adsorption resin containing D-7-ACA obtained in the step (2), and collecting a resolving solution;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding 2 per mill of active carbon in the volume of the solution for decolorization, adjusting the pH value of the decolorized solution to 4.7 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.7%; the yield thereof was found to be 61.25%.
Example 2 Process for recovering D-7-ACA from mother liquor of D-7-ACA crystallization
The method specifically comprises the following steps:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 7.0 with ammonia water, controlling feed liquid temperature at 10 deg.C, nano-filtering, concentrating to 8000 μ g/ml titer;
(2) according to the adsorption capacity of 11g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 0.7BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) carrying out desorption on 1.1BV of 0.7 percent sodium bicarbonate solution through the D-7-ACA-containing macroporous adsorption resin in the step (2) at the flow rate of 0.4BV/h, and collecting desorption solution;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding 2.5 per mill of active carbon in the volume of the solution for decolorization, adjusting the pH value of the decolorized solution to 4.9 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.6%; the yield thereof was found to be 62.21%.
Example 3 Process for recovering D-7-ACA from mother liquor of D-7-ACA crystallization
The method specifically comprises the following steps:
(1) adjusting the pH value of D-7-ACA crystallization mother liquor to 7.1 by ammonia water, controlling the temperature of feed liquid to 11 ℃, and then carrying out nanofiltration concentration to concentrate the titer to 9000 mu g/ml;
(2) according to the adsorption capacity of 13g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 1BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) analyzing 1.3BV of 1% sodium bicarbonate solution at the flow rate of 0.5BV/h by the macroporous adsorption resin containing D-7-ACA in the step (2), and collecting an analysis solution;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding activated carbon with the volume of 3 per mill of the solution for decolorization, adjusting the pH value of the decolorized solution to 5.2 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.8%; the yield thereof was found to be 64.52%.
Example 4 Process for recovering D-7-ACA from mother liquor of D-7-ACA crystallization
The method specifically comprises the following steps:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 7.5 with ammonia water, controlling feed liquid temperature at 12 deg.C, nano-filtering, concentrating to obtain concentrate with titer of 10000 μ g/ml;
(2) according to the adsorption capacity of 15g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 1.0BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) carrying out desorption on 1.5BV of sodium bicarbonate solution with the concentration of 2% through the D-7-ACA-containing macroporous adsorption resin in the step (2) at the flow rate of 0.5BV/h, and collecting desorption solution;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding 2.8 per mill of active carbon in the volume of the solution for decolorization, adjusting the pH value of the decolorized solution to 5.5 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.5%; the yield thereof was found to be 60.14%.
Example 5 Process for recovering D-7-ACA from mother liquor of D-7-ACA crystallization
The method specifically comprises the following steps:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 6.5 with ammonia water, controlling feed liquid temperature at 5 deg.C, nano-filtering, concentrating to obtain titer of 6000 μ g/ml;
(2) according to the adsorption capacity of 10g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 0.5BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) 0.8BV of 0.5 percent sodium bicarbonate solution is resolved by the macroporous absorption resin containing D-7-ACA in the step (2) at the flow rate of 0.3BV/h, and the resolved solution is collected;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding 2.2 per mill of active carbon in the volume of the solution for decolorization, adjusting the pH value of the decolorized solution to 4.5 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.7%; the yield thereof was found to be 62.51%.
Comparative example 1 other method for recovering D-7-ACA from D-7-ACA crystallization mother liquor
The method comprises the following steps of adsorption, desorption, nanofiltration, ultrafiltration, decolorization, crystallization, filtration and drying:
(1) adjusting the pH value of D-7-ACA crystallization mother liquor to 7.0 by ammonia water, controlling the temperature of feed liquid at 12 ℃, and controlling the titer of the crystallization mother liquor to 1530 mu g/ml;
(2) according to the adsorption capacity of 10g/L, carrying out adsorption treatment on the D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 0.8BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) carrying out desorption on 1.3BV of sodium bicarbonate solution with the concentration of 1.5% through the macroporous adsorption resin containing the D-7-ACA in the step (2) at the flow rate of 0.4BV/h, and collecting desorption solution;
(4) concentrating the analytic solution collected in the step (3) to 10125 mug/ml through a nanofiltration membrane group, passing through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding active carbon with the volume of 2.8 per mill of the material liquid for decolorization, adjusting the pH value of the decolorized solution to 5.5 by using 10% hydrochloric acid to obtain D-7-ACA crystals, filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.3%; the yield thereof was found to be 51.02%.
Comparative example 2 other method for recovering D-7-ACA from D-7-ACA crystallization mother liquor
The method comprises the following steps of nanofiltration, adsorption, water washing, resolution, ultrafiltration, decolorization, crystallization, filtration and drying:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 6.8 with ammonia water, controlling feed liquid temperature at 10 deg.C, nano-filtering, concentrating to 7000 μ g/ml titer;
(2) according to the adsorption capacity of 13g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 0.8BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) washing with purified water of 2.0BV at the flow rate of 0.5BV/h through the macroporous adsorption resin containing D-7-ACA in the step (2), washing with sodium bicarbonate solution of which the concentration is 1.0 percent at the flow rate of 0.4BV/h through water, resolving the macroporous adsorption resin containing D-7-ACA, and collecting resolving liquid;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding 2.5 per mill of active carbon in the volume of the solution for decolorization, adjusting the pH value of the decolorized solution to 4.7 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.9%; the yield thereof was found to be 56.72%.
Comparative example 3 other method for recovering D-7-ACA from D-7-ACA crystallization mother liquor
The method adopts low concentration titer and low adsorption capacity, and specifically comprises the following steps:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 7.2 with ammonia water, controlling feed liquid temperature at 9 deg.C, nano-filtering, concentrating to titer of 3000 μ g/ml;
(2) according to the adsorption capacity of 8g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 0.5BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) 0.6BV of 0.4 percent sodium bicarbonate solution is resolved by the macroporous absorption resin containing D-7-ACA in the step (2) at the flow rate of 0.3BV/h, and the resolved solution is collected;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding 2.0 per mill of active carbon in the volume of the solution for decolorization, adjusting the pH value of the decolorized solution to 5.0 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying the D-7-ACA crystals to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.7%; the yield thereof was found to be 51.21%.
Comparative example 4 other method for recovering D-7-ACA from D-7-ACA crystallization mother liquor
The method adopts high-concentration resolution agent, and specifically comprises the following steps:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 7.2 with ammonia water, controlling feed liquid temperature at 9 deg.C, nano-filtering, concentrating to 8000 μ g/ml;
(2) according to the adsorption capacity of 13g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-036 type macroporous adsorption resin at the flow rate of 0.6BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) 0.8BV of sodium bicarbonate solution with the concentration of 4.0 percent is resolved by the macroporous absorption resin containing D-7-ACA in the step (2) at the flow rate of 0.2BV/h, and the resolved solution is collected;
(4) and (4) passing the analytic solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding active carbon with the volume of 3.0 per mill of the solution volume for decolorization, adjusting the pH value of the decolorized solution to 5.0 by using 10% hydrochloric acid to obtain D-7-ACA crystals, filtering and drying to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 96.9%; the yield thereof was found to be 60.12%.
Comparative example 5 other method for recovering D-7-ACA from D-7-ACA crystallization mother liquor
The resin model is replaced, and the method specifically comprises the following steps:
(1) adjusting pH of D-7-ACA crystallization mother liquor to 7.0 with ammonia water, controlling feed liquid temperature at 11 deg.C, nano-filtering, concentrating to obtain titer of 10000 μ g/ml;
(2) according to the adsorption capacity of 10g/L, carrying out adsorption treatment on the concentrated D-7-ACA crystallization mother liquor by LXT-032 type macroporous adsorption resin at the flow rate of 1BV/h to obtain macroporous adsorption resin containing D-7-ACA;
(3) analyzing 1.0BV of 1% sodium bicarbonate solution at the flow rate of 0.5BV/h by the macroporous adsorption resin containing D-7-ACA in the step (2), and collecting an analysis solution;
(4) and (3) passing the desorption solution collected in the step (3) through an ultrafiltration membrane with the molecular weight cutoff of 5000 daltons, adding 2.5 per mill of active carbon in the volume of the solution for decolorization, adjusting the pH value of the decolorized solution to 5.2 by using 10% hydrochloric acid to obtain D-7-ACA crystals, and then filtering and drying the D-7-ACA crystals to obtain the D-7-ACA finished product.
The adsorption and desorption of the porous adsorption resin are carried out in a top-down mode. Through detection, the purity of the finished product D-7-ACA in the above embodiment is 98.9%; the yield thereof was found to be 55.24%.
The preparation process of the invention in example 3 was repeated to compare the purity and yield with those of comparative examples 1-5, and the results are shown in Table 1.
TABLE 1 purity and yield of finished products of example 3 and comparative examples 1-5D-7-ACA
As can be seen from examples 1 to 5 and Table 1, the D-7-ACA obtained by recovering the D-7-ACA from the D-7-ACA crystallization mother liquor by a specific method has the purity of over 98.5 percent and the yield of over 60 percent. The method described in the embodiment 3 is optimal, the purity of the D-7-ACA finished product prepared in the embodiment 3 is over 98.7 percent, and the yield is over 63.5 percent. If other preparation methods are adopted, such as changing the sequence of preparation steps, omitting or adding steps, or changing raw materials or parameters (comparative examples 1-5), the obtained D-7-ACA effect is not as good as that of the invention, and the yield is obviously inferior to that of the invention. In the field, under the condition of ensuring the purity, the yield is difficult to be improved by 5 percent, and very obvious economic benefit is brought. The D-7-ACA is recovered from the D-7-ACA crystallization mother liquor by adopting a specific method, the yield can be improved by 10% under the condition of ensuring the purity, and the effect is very obvious. The invention shows that the specific preparation method can efficiently recover the effective components in the D-7-ACA crystallization mother liquor on the premise of ensuring the quality.
In conclusion, the method can effectively recover the D-7-ACA in the D-7-ACA crystallization mother liquor through the steps of nanofiltration, resin adsorption, desorption, ultrafiltration, decolorization, crystallization, filtration and drying to obtain the high-purity D-7-ACA which can be directly used as a product, thereby improving the yield of the D-7-ACA produced by the prior art, reducing COD (chemical oxygen demand) emission and lowering the production cost. The method for recovering the D-7-ACA from the D-7-ACA crystallization mother liquor has great economic benefit and good application prospect.
Claims (11)
1. A method for recovering D-7-ACA from D-7-ACA crystallization mother liquor is characterized in that: it comprises the following steps:
(1) and (4) nanofiltration: taking D-7-ACA crystallization mother liquor, and carrying out nanofiltration concentration;
(2) resin adsorption: adsorbing the concentrated D-7-ACA crystallization mother liquor by macroporous adsorption resin to obtain macroporous adsorption resin containing D-7-ACA;
(3) and (3) analysis: resolving the macroporous adsorption resin containing D-7-ACA;
(4) and (3) ultrafiltration: carrying out ultrafiltration on the resolution solution;
(5) and (3) decoloring: decolorizing the ultrafiltered feed liquid;
(6) and (3) crystallization: crystallizing the decolorized feed liquid, filtering, and drying to obtain the final product;
the adsorption and/or desorption of the macroporous adsorption resin are carried out in a top-down mode;
in the step (1), the titer of the D-7-ACA crystallization mother liquor after nanofiltration concentration is 6000-10000 mug/ml;
in the step (1), the pH of the D-7-ACA crystallization mother liquor is adjusted to 6.5-7.5 before nanofiltration concentration;
in the step (1), the temperature of the D-7-ACA crystallization mother liquor before nanofiltration concentration is 5-12 ℃;
in the step (2), when the adsorbent is adsorbed by macroporous adsorption resin, the adsorption capacity is 10-15 g/L;
in the step (2), the flow rate is 0.5-1.0 BV/h when the adsorbent is adsorbed by macroporous adsorbent resin;
in the step (2), the macroporous resin is LXT-036;
in the step (3), the analysis agent used in the analysis is selected from one of sodium bicarbonate, sodium acetate and sodium carbonate with the concentration of 0.5-2.0%;
in the step (3), the volume of the resolving agent during resolving is 0.5-2.0 BV;
in the step (3), the flow speed of the resolving agent during resolving is 0.3-0.5 BV/h;
in the step (3), the temperature during analysis is 8-12 ℃;
in the step (4), the ultrafiltration membrane used for ultrafiltration has the molecular weight cutoff of 5000 daltons;
in the step (5), activated carbon is used for decoloring;
in the step (6), the pH value is adjusted to 4.5-5.5 during crystallization;
in the step (6), the temperature during crystallization is 5-10 ℃.
2. The method of claim 1, wherein: in the step (1), the pH of the D-7-ACA crystallization mother liquor is adjusted to 7.1 before nanofiltration concentration; and/or, in the step (1), the temperature of the D-7-ACA crystallization mother liquor before nanofiltration concentration is 11 ℃.
3. The method of claim 2, wherein: in the step (1), ammonia water is used for adjusting the pH value.
4. The method of claim 1, wherein: in the step (1), the titer of the D-7-ACA crystallization mother liquor after nanofiltration concentration is 9000 mu g/ml.
5. The method of claim 1, wherein: in the step (2), the flow rate is 1.0BV/h when the adsorbent is absorbed by macroporous adsorbent resin; and/or in the step (2), the adsorption capacity is 13g/L when the macroporous adsorption resin is used for adsorption.
6. The method of claim 1, wherein: in the step (3), the volume of the resolving agent during resolving is 0.8-1.5 BV.
7. The method of claim 6, wherein: in the step (3), the analysis agent used in the analysis is selected from sodium bicarbonate with the concentration of 1%; and/or in the step (3), the volume of the resolving agent during resolving is 1.3 BV; and/or in the step (3), the flow rate of the resolving agent during resolving is 0.5 BV/h.
8. The method of claim 1, wherein: the volume of the activated carbon is 2-3 per mill of the volume of the feed liquid.
9. The method of claim 8, wherein: the volume of the active carbon is 3 per mill of the volume of the feed liquid.
10. The method of claim 1, wherein: in the step (6), the pH is adjusted to 5.2 during the crystallization.
11. The method of claim 10, wherein: in the step (6), 10% hydrochloric acid is used for adjusting the pH.
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