CN112939314A - Method for treating folic acid extraction and water separation mother liquor and folic acid refining method - Google Patents
Method for treating folic acid extraction and water separation mother liquor and folic acid refining method Download PDFInfo
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/00—Treatment of water, waste water, or sewage
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- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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Abstract
The invention relates to the technical field of chemical wastewater treatment, in particular to a treatment method of acid extraction elutriation mother liquor and a folic acid refining method. The method comprises the steps of sequentially neutralizing folic acid by calcium oxide, removing calcium by carbon dioxide and decoloringThe agent is used for decoloring, SO that SO in the folic acid water extraction and precipitation mother liquor is effectively reduced4 2‑Content of impurities, etc.; meanwhile, the acid extraction circulating liquid obtained by treatment is used for the water separation of the folic acid crude product, so that the process water is reduced, the continuous reuse of the acid extraction water separation mother liquid is realized, namely the wastewater is recycled, and the method has remarkable economic and social benefits.
Description
Technical Field
The invention relates to the technical field of chemical wastewater treatment, in particular to a treatment method of acid extraction elutriation mother liquor and a folic acid refining method.
Background
Folic acid is a water-soluble B-group vitamin, is a coenzyme of carbon unit transferase system in human body biochemical reaction, plays a role of a carbon unit transfersome, and is a substance necessary for promoting the growth and reproduction of body cells. For example, the lack of folic acid in human beings can cause megaloblastic anemia and leukopenia, and the natural folic acid is extremely unstable and is easily damaged by factors such as sunlight, temperature, acid and alkali, so that the amount of folic acid which can be actually obtained from food by the human body is very limited; the synthesized folic acid can be kept stable for a long time, is easy to be absorbed by human bodies and has high utilization rate.
Folic acid has been produced for over 30 years in China, and during the period, through the efforts of researchers, the production process of folic acid is continuously improved and enhanced, and the amount of wastewater generated in the production process is reduced from 500 tons of wastewater generated by the first ton of products to 250 tons of wastewater at present. At present, the folic acid is produced industrially by a chemical synthesis method, the main process mainly adopts three main raw materials of N-p-aminobenzoyl-L-glutamic acid, 2,4, 5-triamino-6-hydroxypyrimidine sulfate, 1, 3-trichloroacetone and the like to synthesize a crude folic acid product, and the crude folic acid product is prepared by two refining procedures of acid extraction and water separation, alkali dissolution and acid separation and the like.
In the production process of the folic acid process, a large amount of high-salinity waste acid water is generated, and particularly, the acid extraction and water separation mother liquor contains nitrogen-containing organic matters such as dihydrofolic acid, 5-chlorofolic acid, pteroic acid, isofolic acid, a small amount of folic acid and the like. The difficulty of post-treatment of wastewater is high, the environmental protection treatment cost is high, and the normal production of folic acid is restricted.
The methods provided by CN101323614A, CN106565050A, CN107129088A, CN101323614A, CN106565050A, CN101973995A and the like have the advantages of high production cost, complex process and high operation difficulty, and can not radically reduce the generation of waste water.
The folic acid wastewater treatment processes disclosed in CN105174563A, CN106565050A, CN107162347A and the like have non-exhaustive data in the description of the examples, and are difficult to achieve the expected effects in the specific implementation.
In the actual production of folic acid, the way of treating the wastewater mainly adopts a method of combining neutralization, centrifugation, dilution and biochemistry, and the final data index of the wastewater can reach the national wastewater discharge standard only at relatively high treatment cost. The process method for realizing mother liquor recycling has the defects of high implementation difficulty, high cost and the like, so a more reasonable and scientific treatment method needs to be explored to solve the pollution problems of folic acid cyclization waste water and folic acid extraction mother liquor.
CN110790426A discloses a method for treating cyclization waste water generated in the production process of folic acid, wherein the cyclization waste water is subjected to calcium hydroxide neutralization and macroporous resin adsorption treatment, and is continuously applied for cyclization reaction, so that the cyclization reaction can be continuously treated for 8 times, and the purity and yield of crude folic acid are not influenced. However, the method discloses the use of cyclization waste water in the preparation of crude folic acid.
CN111196811A discloses an environment-friendly folic acid refining method, which comprises the steps of dissolving a folic acid crude product in a sulfuric acid solution, adding water, stirring to separate out a yellow solid, and filtering to obtain a folic acid refined product and a filtrate; adding activated carbon into the filtrate for adsorption and further performing nanofiltration treatment; concentrated sulfuric acid is added into the filtrate for recycling for 3-5 times, and the consumption of the concentrated sulfuric acid is saved by more than 60%. However, this method discloses the use of the filtrate (acid extraction elutriation mother liquor) in the acid extraction process of crude folic acid.
In addition, CN110790426A and CN111196811A are respectively used in filtering and adsorbing facilities such as macroporous resin, nanofiltration membrane and the like which are difficult to post-treat, and the recycling frequency is also obviously limited.
Therefore, how to recycle and reuse a large amount of acid extraction and elutriation mother liquor generated in the production process of folic acid is a basic requirement for realizing green synthesis of folic acid.
Disclosure of Invention
The invention aims to solve the problems of large treatment capacity, complex treatment process, limited cycle times and the like of acid extraction elutriation mother liquor generated in the existing folic acid refining process, and provides a treatment method of the acid extraction elutriation mother liquor and a folic acid refining method, wherein the treatment method is simple and convenient, and reduces the treatment difficulty of folic acid wastewater; the recycling method realizes the continuous recycling of the acid extraction elutriation mother liquor and reduces the discharge of waste liquid.
In order to achieve the above object, a first aspect of the present invention provides a method for treating a folic acid elution mother liquor, the method comprising:
(1) mixing folic acid extraction water precipitation mother liquor with calcium oxide, adjusting the pH value to 7-10, and performing hot filtration to obtain filtrate;
(2) introducing carbon dioxide into the filtrate, adjusting the pH value to 6-7, adding a decolorizing agent for decolorizing, and filtering to obtain an acid extraction circulating solution;
wherein the folic acid is used for extracting SO from the mother liquor4 2-The content is 30000-50000 mg/L.
In a second aspect, the present invention provides a method for refining folic acid, the method comprising: contacting the folic acid crude product with a sulfuric acid solution for acid extraction, adding an acid extraction circulating solution and optional water into the obtained product for water separation and filtration to obtain a folic acid refined product and a folic acid extraction water separation mother solution;
wherein the acid extraction circulating liquid is the acid extraction circulating liquid obtained by the treatment of the method provided by the first aspect.
Through the technical scheme, the folic acid water extraction mother liquor is subjected to calcium oxide neutralization, carbon dioxide calcium removal and decoloration by a decolorant in sequence, SO that SO in the folic acid water extraction mother liquor is effectively reduced4 2-Content of impurities, etc.; at the same time, the method simplifies folic acidThe treatment difficulty of the water extraction and precipitation mother liquor is convenient for industrial production.
Meanwhile, the invention also provides a recycling method of the folic acid water extraction elution mother liquor, the method uses the treated acid extraction circulation liquor for the elution of folic acid crude products, reduces the process water, realizes the continuous recycling of the folic acid water extraction elution mother liquor, namely the reuse of waste water, and has obvious economic and social benefits.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for treating folic acid water-out mother liquor, which comprises the following steps:
(1) mixing folic acid extraction water precipitation mother liquor with calcium oxide, adjusting the pH value to 7-10, and performing hot filtration to obtain filtrate;
(2) introducing carbon dioxide into the filtrate, adjusting the pH value to 6-7, adding a decolorizing agent for decolorizing, and filtering to obtain an acid extraction circulating solution;
wherein the folic acid is used for extracting SO from the mother liquor4 2-The content is 30000-50000 mg/L.
The inventor of the invention researches and discovers that the folic acid is subjected to calcium oxide neutralization, carbon dioxide calcium removal and decoloration by a decolorant to obtain the folic acid with low SO content4 2-The acid extraction circulating liquid with low content and low impurity content greatly reduces the treatment difficulty of the folic acid extraction elutriation mother liquor; meanwhile, the acid extraction circulating liquid is used in the elutriation process for refining folic acid, so that the continuous application of folic acid extraction elutriation mother liquid is realized, the folic acid content in folic acid fine products is ensured, the wastewater treatment capacity is reduced, the process water is reduced, and the economic benefit and the social benefit are remarkable.
In the invention, the folic acid extraction and water separation mother liquor is a filtrate generated in the folic acid crude product refining process without special condition.
In the present invention, the calcium oxide is intended to reduce SO in the folic acid-extracted mother liquor4 2-And (4) content. Preferably, the dosage ratio of the folic acid extraction water-out mother liquor to the calcium oxide is 100 mL: 0.5-5g, preferably 100 mL: 2.5-3.5 g. Wherein the dosage ratio refers to the dosage of folic acid water-extraction mother liquor of 100mL, and the addition amount of calcium oxide is 0.5-5g, preferably 2.5-3.5 g.
In the invention, the mixing aims to fully contact the folic acid extraction elutriation mother liquor with calcium oxide and remove SO in the folic acid extraction mother liquor4 2-. Preferably, the mixing conditions include: the temperature is 40-70 ℃, preferably 50-60 ℃; the time is 0.1-5h, preferably 0.5-2 h. The preferable conditions are adopted, SO that the SO in the folic acid water extraction and separation mother liquor is more favorably removed4 2-。
According to a preferred embodiment of the invention, the folic acid extraction elutriation mother liquor and calcium oxide are mixed for 0.1 to 5 hours at a constant temperature of 40 to 70 ℃.
In the present invention, the pH of step (1) is adjusted to 7 to 10 by adding an excess of calcium oxide, i.e., the most part of SO is removed from the folic acid-extracted mother liquor4 2-。
In some embodiments of the invention, preferably, the folate elutriation mother liquor is heated to 40-70 ℃, preferably 50-60 ℃ prior to the mixing. At the temperature, SO is removed as far as possible on the premise of ensuring stable folic acid property4 2-。
According to the invention, the temperature of the hot filtration is preferably between 40 and 70 ℃, preferably between 50 and 60 ℃. At this filtration temperature, CaSO4The solubility of the folic acid is low, and other impurities in the folic acid are easy to separate out and remove.
According to a preferred embodiment of the invention, the folic acid extraction elutriation mother liquor and calcium oxide are mixed for 0.1 to 5 hours at a constant temperature of 40 to 70 ℃, the pH of the mixed liquor is adjusted to 7 to 10, and then the mixed liquor is subjected to thermal filtration at 40 to 70 ℃ to remove calcium sulfate solids, so that filtrate is obtained.
In the invention, step (2) is to introduce carbon dioxide and adjust the pH of the filtrate to 6-7, aiming at removing the residual Ca in the filtrate2+。
According to the invention, the gas flow rate of the carbon dioxide is preferably between 2 and 20 mL/min-kg, preferably between 8 and 12 mL/min-kg. By controlling the gas flow rate of the carbon dioxide, the residual Ca in the filtrate can be removed more conveniently2+。
According to the present invention, preferably, the decolorizing reaction conditions include: the temperature is 40-70 ℃, preferably 50-60 ℃; the time is 0.1-5h, preferably 0.5-2 h. And the preferable conditions are adopted, so that the impurity removal and the decoloration are more facilitated.
According to the invention, preferably, the dosage ratio of the folic acid mother liquor to the decolorant is 100 mL: 0.1-2g, preferably 100 mL: 0.1-1 g. Wherein the dosage ratio refers to that the dosage of folic acid is 100mL, the addition of the decolorizing agent is 0.1-2g, preferably 0.1-1 g.
According to the invention, preferably, the decolorizing agent is selected from at least one of a flocculation decolorizing agent, an oxidation decolorizing agent and an adsorption decolorizing agent, preferably from an adsorption decolorizing agent.
In some embodiments of the present invention, preferably, the decolorizing agent is selected from at least one of activated carbon, clay, and adsorbent resin; more preferably activated carbon.
In the present invention, the filtration described in step (2) is directed to the calcium carbonate solids containing impurities and the decolorizing agent. In the present invention, there is a wide range of options for the manner of filtering.
According to the present invention, preferably, SO in the acid extraction circulation liquid4 25000mg/L of Ca in an amount of 1000-2+The content is 500-1000 mg/L. By adopting the method provided by the invention, SO in the folic acid water-extraction mother liquor can be effectively reduced4 2Content and impurity content, obtaining a low SO4 2-acid extraction recycle liquor of low content and low impurity content.
In a second aspect, the present invention provides a method for refining folic acid, the method comprising: contacting the folic acid crude product with a sulfuric acid solution for acid extraction, adding an acid extraction circulating solution and optional water into the obtained product for water separation and filtration to obtain a folic acid refined product and a folic acid extraction water separation mother solution;
wherein the acid extraction circulating liquid is the acid extraction circulating liquid obtained by the treatment of the method provided by the first aspect.
In the invention, the acid extraction circulating liquid provided by the first aspect is used for water used in a elutriation process in a folic acid refining process, so that the folic acid extraction elutriation mother liquor is recycled; meanwhile, the folic acid extraction elutriation mother liquor obtained in the folic acid refining process can be subjected to the treatment method repeatedly, so that the continuous application of the acid extraction circulating liquor is realized.
According to the invention, the acid extraction circulating liquid can be continuously used for more than 20 times.
In the present invention, the standard for continuous use is not specifically defined as the content of the acid extract (folic acid refined product) of not less than 90 wt%, preferably not less than 93 wt%. Wherein, the folic acid content in the folic acid refined product is measured by an HPLC liquid phase method.
According to the invention, the folic acid content of the crude folic acid is less than or equal to 85 wt%, preferably 80-85 wt% based on the total weight of the crude folic acid. Wherein, the content of folic acid in the crude folic acid is measured by an HPLC liquid phase method.
In some embodiments of the present invention, preferably, the weight ratio of the crude folic acid to the sulfuric acid solution is 1: 2-10, preferably 1: 3-8. The optimized conditions are adopted, so that the acid extraction efficiency of the crude folic acid is improved.
According to the invention, the sulfuric acid content of the sulfuric acid solution is preferably 30 to 60 wt.%, preferably 35 to 55 wt.%.
According to the present invention, preferably, the acid extraction conditions include: the temperature is 40-70 ℃, preferably 50-60 ℃; the time is 0.1-5h, preferably 0.5-2 h.
In some embodiments of the present invention, preferably, the weight ratio of the acid extraction circulation liquid to the crude folic acid is 20-30: 1, preferably 23 to 28: 1. the preferable conditions are adopted, so that the elutriation efficiency of the crude folic acid is improved.
According to the present invention, preferably, the conditions of the elutriation include: the temperature is 40-70 ℃, preferably 50-60 ℃; the time is 0.1-5h, preferably 0.5-2 h.
In some embodiments of the present invention, preferably, the weight ratio of the water to the crude folic acid is 0-5: 1, preferably 0 to 3: 1.
in the present invention, the water is not particularly limited. Preferably, the water is purified water, but the present invention is not limited thereto.
Preferably, the method further comprises: and drying the product obtained by filtering to obtain the refined folic acid.
In the present invention, there is a wide range of selection of the drying conditions as long as the filtered product is dried. Preferably, the drying conditions include: the temperature is 60-120 ℃, preferably 80-100 ℃; the time is 1-15h, preferably 1-10 h.
The present invention will be described in detail below by way of examples.
The folic acid content in the folic acid crude product and the folic acid content in the folic acid refined product (acid extract) are measured by an HPLC liquid phase method.
Example 1
Method for treating folic acid extraction and water precipitation mother liquor：
(1) 600mL of folic acid was extracted and a mother liquor (SO) was separated4 241000mg/L) into a 1000mL three-necked flask, heating to 50 ℃, adding 9g of calcium oxide solid, mixing at 50 ℃ for 1h, adjusting the pH of the mixed solution to 9, and performing heat filtration at 50 ℃ to obtain a filtrate;
(2) introducing carbon dioxide (the gas flow rate is 10 mL/min. kg) into the filtrate, adjusting the pH of the filtrate to 6, adding 2.5g of activated carbon for decolorization, and filtering to obtain an acid extraction circulating solution S1, wherein the decolorization conditions comprise: the temperature is 50 ℃ and the time is 1 h;
wherein SO in the acid extraction circulating liquid S14 2Ca at a content of 2500mg/L2+The content was 650 mg/L.
Method for refining folic acid：
Putting 20g of folic acid crude product (with the folic acid content of 82.1 wt%) into a 1000mL three-necked bottle, and adding 80g of sulfuric acid solution with the sulfuric acid content of 50 wt% for acid extraction (at the temperature of 50 ℃, for 0.5 h); then 500g of acid extraction circulating liquid S1 is added for water precipitation (the temperature is 50 ℃, the time is 0.5h), filtration and drying are carried out, 16.2g of folic acid refined product P1 is obtained, and the folic acid content is 95.5 wt%.
Example 2
Method for treating folic acid extraction and water precipitation mother liquor：
(1) 500mL of mother liquor (SO) is extracted by folic acid for 20 th time4 2-46000mg/L) is poured into a 1000mL three-necked bottle, heated to 50 ℃, 7.5g of calcium oxide solid is added to be mixed for 1h at the constant temperature of 50 ℃, the pH value of the mixed solution is adjusted to 8, and then heat filtration is carried out at the temperature of 50 ℃ to obtain filtrate;
(2) introducing carbon dioxide (the gas flow rate is 8 mL/min. kg) into the filtrate, adjusting the pH of the filtrate to 7, adding 2.5g of activated carbon for decolorization, and filtering to obtain an acid extraction circulating solution S2, wherein the decolorization conditions comprise: the temperature is 50 ℃ and the time is 1 h;
wherein SO in the acid extraction circulating liquid S24 2Ca at a content of 4800mg/L2+The content is 810 mg/L.
Method for refining folic acid：
Putting 20g of folic acid crude product (with the folic acid content of 82.1 wt%) into a 1000mL three-necked bottle, and adding 80g of sulfuric acid solution with the sulfuric acid content of 50 wt% for acid extraction (at the temperature of 50 ℃, for 0.5 h); then 450g of acid extraction circulating liquid S2 and 50g of purified water are added for water precipitation (the temperature is 50 ℃, the time is 0.5h), filtration and drying are carried out, and 16.5g of refined folic acid P2 with the folic acid content of 93.3 wt% are obtained.
Example 3
Method for treating folic acid extraction and water precipitation mother liquor：
(1) 500mL of folic acid was extracted with water to separate out a mother liquor (SO)4 240000mg/L) into a 1000mL three-necked flask, heating to 55 deg.C, adding 10g of calcium oxide solid, mixing at 55 deg.C for 2 hr, adjusting pH to 7.5, and cooling to 55 deg.CCarrying out hot filtration to obtain filtrate;
(2) introducing carbon dioxide (the gas flow rate is 12 mL/min-kg) into the filtrate, adjusting the pH of the filtrate to 6.5, adding 0.5g of activated carbon for decolorization, and filtering to obtain an acid extraction circulating solution S3, wherein the decolorization conditions comprise: the temperature is 55 ℃, and the time is 0.5 h;
wherein SO in the acid extraction circulating liquid S34 2-The content is 3200mg/L, Ca2+The content was 760 mg/L.
Method for refining folic acid：
Putting 20g of folic acid crude product (with the folic acid content of 82.1 wt%) into a 1000mL three-necked bottle, and adding 100g of sulfuric acid solution with the sulfuric acid content of 45 wt% for acid extraction (at the temperature of 50 ℃ for 0.5 h); then 600g of acid extraction circulating liquid S3 is added for water precipitation (the temperature is 50 ℃, the time is 0.5h), filtration and drying are carried out, 15.6g of folic acid refined product P3 is obtained, and the folic acid content is 94.7 wt%.
Example 4
The same procedure as in example 1, except that in the treatment of the folic acid hydrolysis mother liquor, the mass of calcium oxide solid was changed to 3g, was followed to obtain an acid extraction circulating liquid S4, in which SO was contained in the acid extraction circulating liquid S44 2-The content is 6300 mg/L;
the acid extraction circulating liquid S4 is used for folic acid refining to obtain 16.7g folic acid refined product P4 with folic acid content of 92.7 wt%.
Example 5
The same procedure as in example 1, except that the folic acid hydrolysis mother liquor was mixed with the calcium oxide solid without heating in the treatment method of the folic acid hydrolysis mother liquor, was carried out to obtain an acid extraction circulation liquid S5, wherein SO was contained in the acid extraction circulation liquid S54 2-The content is 4600 mg/L;
the acid extraction circulating liquid S5 is used for folic acid refining to obtain 16.3g folic acid refined product P5, the folic acid content of which is 94.6 wt%.
Example 6
The procedure of example 1 is followed except that the folic acid is subjected to aqueous precipitationIn the mother liquor treatment method, the mass of the activated carbon is replaced by 0.6g, and the rest steps are the same, SO that acid extraction circulating liquid S6 is obtained, wherein SO in the acid extraction circulating liquid S64 2-The content is 3800 mg/L;
the acid extraction circulating liquid S6 is used for folic acid refining to obtain 16.4g of folic acid refined product P6, the folic acid content of which is 94.9 wt%.
Example 7
The procedure of example 1 was followed except that, in the folic acid purification process, the amount of the acid extraction circulating liquid was changed to 400g, and the remaining steps were the same, to give 15.8g of refined folic acid P7 having a folic acid content of 95.4 wt%.
Example 8
The method of example 1 was followed, except that in the method of treating the folic acid hydrolysis mother liquor, the pH of the mixed liquor in the step (1) was adjusted to 8.5, and the rest of the steps were the same, to obtain an acid extraction circulation liquor S8, wherein SO in the acid extraction circulation liquor S84 2-The content is 2600 mg/L;
the acid extraction circulating liquid S8 was used for folic acid refinement to obtain 16.3g folic acid refined product P8 with folic acid content of 95.1 wt%.
Comparative example 1
The procedure of example 1 was followed except that, in the method for treating the folic acid hydrolysis mother liquor, the pH of the filtrate in the step (2) was adjusted to 5.5, and the remaining steps were the same, to obtain an acid extraction circulation liquid DS1, wherein SO in the acid extraction circulation liquid DS14 2-The content is 5500 mg/L;
the acid extraction circulating liquid DS1 was used for folic acid refinement to obtain 16.4g folic acid refined DP1 with folic acid content of 93.1 wt%.
Comparative example 2
The procedure of example 1 was followed except that, in the method for treating the folic acid hydrolysis mother liquor, the temperature of the filtration in the step (1) was changed to 25 ℃ and the remaining steps were the same, to obtain an acid extraction circulation liquor DS2, wherein SO in the acid extraction circulation liquor DS24 2-The content is 5800 mg/L;
the acid extraction circulating liquid DS2 was used for folic acid refinement to obtain 15.8g folic acid refined DP2 with folic acid content of 93.0 wt%.
Comparative example 3
The same procedure as in example 1, except that in the treatment of the folic acid hydrolysis mother liquor, the activated carbon in the step (2) was replaced with a large-pore size resin, and the rest of the procedures were the same, was conducted to obtain an acid extraction circulation liquid DS3, in which SO in the acid extraction circulation liquid DS4 was contained4 2-The content is 4600 mg/L;
the acid extraction circulating liquid DS3 was used for folic acid refining to obtain 15.7g folic acid refined DP3 with folic acid content of 94.6 wt%.
Comparative example 4
According to the method disclosed in CN111196811A, activated carbon adsorption and nanofiltration treatment are sequentially carried out on the folic acid extraction mother liquor to obtain an acid extraction circulating liquid DS4, wherein SO in the acid extraction circulating liquid DS44 2-The content is 5100 mg/L;
the acid extraction circulating liquid DS4 was used for folic acid refinement to obtain 16.4g folic acid refined DP4 with folic acid content of 95.2 wt%.
Comparative example 5
Method for refining folic acid：
Putting 20g of folic acid crude product (with the folic acid content of 82.1 wt%) into a 1000mL three-necked bottle, and adding 80g of sulfuric acid solution with the sulfuric acid content of 50 wt% for acid extraction (at the temperature of 50 ℃, for 0.5 h); then 500g of purified water is added for water precipitation (the temperature is 50 ℃, the time is 0.5h), filtration and drying are carried out, 16.3g of folic acid refined product DP5 is obtained, and the folic acid content is 95.7 wt%.
As can be seen by comparing the data of examples 1-8 and comparative examples 1-5, the low SO content can be obtained by treating the folic acid water-stripping mother liquor by the method of the present invention4 2-Acid extraction circulating liquid with low content of impurities; meanwhile, the acid extraction circulating liquid obtained by the treatment of the invention is used for refining folic acid, so that the water used in the acid extraction and elutriation process is reduced and the discharge of waste water is greatly reduced on the premise of ensuring the content of folic acid in a refined folic acid product.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for treating folic acid water extraction mother liquor is characterized by comprising the following steps:
(1) mixing folic acid extraction water precipitation mother liquor with calcium oxide, adjusting the pH value to 7-10, and performing hot filtration to obtain filtrate;
(2) introducing carbon dioxide into the filtrate, adjusting the pH value to 6-7, adding a decolorizing agent for decolorizing, and filtering to obtain an acid extraction circulating solution;
wherein the folic acid is used for extracting SO from the mother liquor4 2-The content is 30000-50000 mg/L.
2. The method according to claim 1, wherein the dosage ratio of the folic acid water-extraction mother liquor to the calcium oxide is 100 mL: 0.5-5g, preferably 100 mL: 2.5-3.5 g.
3. The method of claim 1 or 2, wherein the conditions of mixing comprise: the temperature is 40-70 ℃, preferably 50-60 ℃; the time is 0.1 to 5 hours, preferably 0.5 to 2 hours;
preferably, the folate elutriation mother liquor is heated to 40-70 ℃, preferably 50-60 ℃ prior to the mixing.
4. A process according to any one of claims 1 to 3, wherein the temperature of the hot filtration is 40 to 70 ℃, preferably 50 to 60 ℃.
5. The method according to any one of claims 1-4, wherein the carbon dioxide has a gas flow rate of 2-20 mL/min-kg, preferably 8-12 mL/min-kg;
preferably, the decolorizing reaction conditions include: the temperature is 40-70 ℃, preferably 50-60 ℃; the time is 0.1-5h, preferably 0.5-2 h.
6. The method of any one of claims 1-5, wherein the ratio of folic acid mother liquor to decolorant is 100 mL: 0.1-2g, preferably 100 mL: 0.1-1 g;
preferably, the decolorizing agent is selected from at least one of a flocculation decolorizing agent, an oxidation decolorizing agent and an adsorption decolorizing agent, preferably from an adsorption decolorizing agent;
preferably, the decolorizing agent is selected from at least one of activated carbon, clay, and adsorbent resin;
preferably, SO in the acid extraction circulating liquid4 2-The content of Ca is 1000-5000mg/L2+The content is 500-1000 mg/L.
7. A method for refining folic acid, which is characterized by comprising the following steps: contacting the folic acid crude product with a sulfuric acid solution for acid extraction, adding an acid extraction circulating solution and optional water into the obtained product for water separation and filtration to obtain a folic acid refined product and a folic acid extraction water separation mother solution;
wherein the acid extraction circulating liquid is obtained by the method of any one of claims 1 to 6.
8. The method according to claim 7, wherein the acid extraction circulating liquid can be continuously used for more than 20 times.
9. The method according to claim 7 or 8, wherein the crude folic acid has a folic acid content of less than or equal to 85 wt%, preferably 80-85 wt%, based on the total weight of the crude folic acid;
preferably, the weight ratio of the folic acid crude product to the sulfuric acid solution is 1: 2-10, preferably 1: 3-8;
preferably, the sulfuric acid content of the sulfuric acid solution is 30-60 wt%, preferably 35-55 wt%.
10. The method according to any one of claims 6-9, wherein the weight ratio of the acid extraction circulating liquid to the crude folic acid is 20-30: 1, preferably 23 to 28: 1;
preferably, the weight ratio of the water to the crude folic acid is 0-5: 1, preferably 0 to 3: 1;
preferably, the method further comprises: and drying the product obtained by filtering to obtain the refined folic acid.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304096A (en) * | 1988-06-02 | 1989-12-07 | Kurita Water Ind Ltd | Water treatment |
| AU2009214118A1 (en) * | 2008-02-11 | 2009-08-20 | Nanologica Ab | Method for manufacturing mesoporous materials, materials so produced and use of mesoporous materials |
| CN101962250A (en) * | 2010-08-23 | 2011-02-02 | 张超 | Method and device for treating sulfate-containing wastewater in phenylglycine production process |
| CN101973995A (en) * | 2010-07-20 | 2011-02-16 | 上海华理生物医药有限公司 | Method for recycling waste water in production of folic acid |
| CN103922517A (en) * | 2014-05-12 | 2014-07-16 | 湘潭大学 | Method for treatment and cyclic utilization of sulfuric acid waste water containing heavy metal |
| CN104261585A (en) * | 2014-09-19 | 2015-01-07 | 湖南淼鑫环保科技有限公司 | Method for treating metallurgy wastewater and recycling resources |
| CN106103360A (en) * | 2014-02-26 | 2016-11-09 | 奥图泰(芬兰)公司 | The method of sulfate is removed from waste water |
| CN106147751A (en) * | 2015-04-27 | 2016-11-23 | 北京化工大学 | The preparation method of a kind of immobilization fluorescence nano sensor and selective determination folic acid |
| CN107352743A (en) * | 2017-08-10 | 2017-11-17 | 西安瑞联新材料股份有限公司 | A kind of processing method of folic acid waste liquor water |
| CN109354311A (en) * | 2018-11-13 | 2019-02-19 | 江苏蓝必盛化工环保股份有限公司 | A method of the processing waste water of pyrazine containing high concentration |
| US20200048665A1 (en) * | 2007-10-28 | 2020-02-13 | Lanzatech New Zealand Limited | Carbon capture in fermentation |
| CN110790426A (en) * | 2019-11-11 | 2020-02-14 | 江苏理工学院 | Method for treating cyclization wastewater generated in folic acid production process |
-
2021
- 2021-02-02 CN CN202110145138.0A patent/CN112939314B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01304096A (en) * | 1988-06-02 | 1989-12-07 | Kurita Water Ind Ltd | Water treatment |
| US20200048665A1 (en) * | 2007-10-28 | 2020-02-13 | Lanzatech New Zealand Limited | Carbon capture in fermentation |
| AU2009214118A1 (en) * | 2008-02-11 | 2009-08-20 | Nanologica Ab | Method for manufacturing mesoporous materials, materials so produced and use of mesoporous materials |
| CN101973995A (en) * | 2010-07-20 | 2011-02-16 | 上海华理生物医药有限公司 | Method for recycling waste water in production of folic acid |
| CN101962250A (en) * | 2010-08-23 | 2011-02-02 | 张超 | Method and device for treating sulfate-containing wastewater in phenylglycine production process |
| CN106103360A (en) * | 2014-02-26 | 2016-11-09 | 奥图泰(芬兰)公司 | The method of sulfate is removed from waste water |
| CN103922517A (en) * | 2014-05-12 | 2014-07-16 | 湘潭大学 | Method for treatment and cyclic utilization of sulfuric acid waste water containing heavy metal |
| CN104261585A (en) * | 2014-09-19 | 2015-01-07 | 湖南淼鑫环保科技有限公司 | Method for treating metallurgy wastewater and recycling resources |
| CN106147751A (en) * | 2015-04-27 | 2016-11-23 | 北京化工大学 | The preparation method of a kind of immobilization fluorescence nano sensor and selective determination folic acid |
| CN107352743A (en) * | 2017-08-10 | 2017-11-17 | 西安瑞联新材料股份有限公司 | A kind of processing method of folic acid waste liquor water |
| CN109354311A (en) * | 2018-11-13 | 2019-02-19 | 江苏蓝必盛化工环保股份有限公司 | A method of the processing waste water of pyrazine containing high concentration |
| CN110790426A (en) * | 2019-11-11 | 2020-02-14 | 江苏理工学院 | Method for treating cyclization wastewater generated in folic acid production process |
Non-Patent Citations (6)
| Title |
|---|
| 刘光良: "硫酸盐浆厂废水的特征及毒性", 《生物质化学工程》, no. 04, 30 April 1979 (1979-04-30) * |
| 岳子男: "关于硫酸厂废水治理的几个问题", 《环境保护》, no. 11, 30 November 1982 (1982-11-30) * |
| 康晶: "燃煤电厂脱硫废水处理工艺研究", 《中国优秀博硕士学位论文全文数据库（硕士） 工程科技I辑》, 15 January 2020 (2020-01-15), pages 3 * |
| 杨晓宇等: "活性炭、离子交换树脂应用于去除水中硫酸根的比较", 《内蒙古石油化工》, no. 5, 30 March 2010 (2010-03-30), pages 3 * |
| 林青山等: "钢铁酸洗废水中酸和铁的回收", 《淮阴工学院学报》, no. 01, 15 February 2018 (2018-02-15) * |
| 陈文华: "叶酸的合成", 《中国医药工业杂志》, no. 6, 30 June 2014 (2014-06-30), pages 2 * |
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