CN112812058A - Method for recovering organic matters in nicotinic acid production wastewater - Google Patents
Method for recovering organic matters in nicotinic acid production wastewater Download PDFInfo
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- CN112812058A CN112812058A CN202110069466.7A CN202110069466A CN112812058A CN 112812058 A CN112812058 A CN 112812058A CN 202110069466 A CN202110069466 A CN 202110069466A CN 112812058 A CN112812058 A CN 112812058A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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Abstract
The invention discloses a method for recovering organic matters in nicotinic acid production wastewater, which comprises the following steps: treating the nicotinic acid production wastewater to enable the concentration of anhydrous sodium sulfate to reach saturation, then cooling, crystallizing, filtering, washing, further concentrating the filtrate until the concentration of organic matters is 10-20 wt%, then decoloring, filtering, adjusting the pH value of the filtrate, standing, centrifugally filtering, recovering the filtrate, entering the next cycle, and drying a filter cake to obtain the recovered organic matters. The invention can treat the wastewater of nicotinic acid production in an efficient and low-cost way and recover organic matters with higher value in the wastewater.
Description
Technical Field
The invention relates to a method for treating nicotinic acid wastewater, in particular to a method for recovering organic matters in nicotinic acid production wastewater by combining concentration and cooling crystallization phases.
Background
Nicotinic acid is an important vitamin, is mainly used for feed additives, can improve the utilization rate of feed protein, and can improve the milk yield of cows and the meat yield and quality of fishes, chickens, ducks, cows, sheep and other livestock. Nicotinic acid is a widely used medical intermediate, and can be used as a raw material to synthesize various medicines, such as nicotemide, inositol nicotinate and the like. In addition, nicotinic acid also plays an irreplaceable role in the fields of luminescent materials, dyes, electroplating industries and the like.
At present, a large amount of high-salt organic wastewater is generated in the production process of nicotinic acid and is treated by evaporation and concentration, so that the problems of high energy consumption, high cost, incapability of recycling organic matters with high value and the like exist. The method comprises the steps of forming saturated solution by sodium sulfate in the sodium sulfate, slowly cooling to precipitate sodium sulfate decahydrate crystals, removing salt and a large amount of water, concentrating organic matters, further treating until the concentration of the organic matters meets the requirement, decoloring by using activated carbon to remove colored impurities, adding acid to adjust the pH value to precipitate the organic matters, filtering, recovering and refining to obtain pure organic acid products, and enabling filtrate to enter the next cycle. The method has low energy consumption and simple operation, can effectively recover the organic acid, and is beneficial to the environment and the economic benefits of enterprises.
Disclosure of Invention
An object of the present invention is to solve at least the above problems and/or disadvantages and to provide at least the advantages described hereinafter.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for recovering organics from nicotinic acid production wastewater, comprising the steps of:
treating the nicotinic acid production wastewater to enable the concentration of anhydrous sodium sulfate to reach saturation, then cooling, crystallizing, filtering, washing, further concentrating the filtrate until the concentration of organic matters is 10-20 wt%, then decoloring, filtering, adjusting the pH value of the filtrate, standing, centrifugally filtering, recovering the filtrate, entering the next cycle, and drying a filter cake to obtain the recovered organic matters.
Preferably, the content of organic matters in the wastewater from nicotinic acid production is 1-3 wt%, the content of sodium sulfate is 10-25 wt%, and the pH value is 7-8.
Preferably, the anhydrous sodium sulfate concentration is saturated by adding anhydrous sodium sulfate or concentrating under reduced pressure.
Preferably, the added anhydrous sodium sulfate is a byproduct in the production process of the nicotinic acid; the concentration under reduced pressure is carried out at 45-65 ℃ and 10-25 KPa.
Preferably, the cooling crystallization temperature is 2-20 ℃, stirring is applied in the cooling crystallization process, and the stirring speed is 30-500 r/min.
Preferably, the method for further concentrating the filtrate until the concentration of the organic matters is 10-20 wt% comprises adding anhydrous sodium sulfate or concentrating under reduced pressure; the added anhydrous sodium sulfate is a byproduct in the production process of the nicotinic acid; the concentration under reduced pressure is carried out at 45-65 ℃ and 10-25 KPa.
Preferably, the decoloring process is as follows: transferring the concentrated filtrate into a reflux kettle, adding active carbon, and keeping the temperature at 90-100 ℃ for 10-30 min.
Preferably, the filtrate is adjusted to a pH of 2.5 to 4.0, the acidifying agent used being 98% by weight of concentrated sulfuric acid.
Preferably, before cooling and crystallizing, sealed pressurized ultrasound is applied for 10-15 min, and the process parameters are as follows: stopping ultrasound for 2min at intervals after every 3-5 min of ultrasound reaction, wherein the pressure is 0.3-1.2 MPa, and the frequency is 80-120 KHz.
The invention at least comprises the following beneficial effects: the invention can treat the wastewater of nicotinic acid production in an efficient and low-cost way and recover organic matters with higher value in the wastewater.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to examples so that those skilled in the art can practice the invention with reference to the description.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a method for recovering organic matters in wastewater from nicotinic acid production comprises the following steps:
100Kg of waste water from nicotinic acid production (2.1 wt% of total amount of nicotinic acid and other organic matters, 15.7 wt% of sodium sulfate and 82.2 wt% of water) is put into an MVR reduced pressure evaporator, reduced pressure distillation is carried out at 50 ℃ and 13KPa, 50Kg of water is distilled out, a small amount of solid is contained in residual liquid, condensed water is recycled, the residual liquid is transferred into a crystallization kettle, slowly cooling to 2 deg.C with refrigerant at 100r/min, cooling, crystallizing, belt filtering, washing with 3Kg of 2 deg.C cold water, mixing filtrates, transferring the filtrate into MVR pressure-reducing evaporator, distilling under reduced pressure at 50 ℃ and 13KPa to evaporate 10Kg of water, wherein the content of organic matters in the residual liquid is 18 percent, transferring the residual liquid into a reflux kettle, adding 100g of active carbon, keeping the temperature at the slight boiling temperature for 0.5h, filtering, transferring the filtrate into a crystallization kettle, dropwise adding sulfuric acid to adjust the pH value to 3.4, standing for 12h, centrifugally filtering, transferring the filtrate into the next cycle, drying the filter cake at 80 ℃, and recrystallizing to obtain 1.4Kg of pure nicotinic acid; the single pass recovery of nicotinic acid was 66.7%.
Example 2:
adding 24Kg of anhydrous sodium sulfate into 100Kg of waste water from nicotinic acid production (2.0 wt% of total amount of nicotinic acid and other organic matters, 16.7 wt% of sodium sulfate and 81.2 wt% of water), slightly heating to dissolve, transferring to a crystallization kettle, slowly cooling to 2 ℃ by a refrigerant at the rotation speed of 80r/min to cool and crystallize, belt filtering, washing with 6Kg of cold water at 2 ℃, merging filtrates, adding 18Kg of anhydrous sodium sulfate, slightly heating to dissolve, transferring to the crystallization kettle, slowly cooling to 2 ℃ by the refrigerant at the rotation speed of 80r/min to cool and crystallize, belt filtering, washing with 1Kg of cold water at 2 ℃, merging filtrates, adjusting the content of organic matters in the filtrates to 14.4%, dropwise adding sulfuric acid to adjust the pH to 3.4, standing for 12h, centrifuging, transferring the filtrates to the next cycle, drying a filter cake at 80 ℃, and recrystallizing to obtain 1.17Kg of pure nicotinic acid. The single pass recovery of nicotinic acid was 58.5%.
Example 3:
adding 24Kg of anhydrous sodium sulfate into 100Kg of waste water from nicotinic acid production (2.0 wt% of total amount of nicotinic acid and other organic matters, 16.7 wt% of sodium sulfate and 81.2 wt% of water), slightly heating to dissolve, transferring to a crystallization kettle, slowly cooling to 2 ℃ by a refrigerant at the rotating speed of 80r/min to cool and crystallize, belt filtering, washing with 6Kg of cold water at 2 ℃, merging the filtrates, transferring the filtrates to an MVR reduced pressure evaporator, distilling at 50 ℃ and 13KPa under reduced pressure to evaporate 30Kg of water, keeping the organic matter content in the raffinate at 19.1%, transferring the raffinate to a reflux kettle, adding 100g of activated carbon, keeping the temperature at slight boiling for 0.5h, filtering, transferring the filtrate to the crystallization kettle, dropwise adding sulfuric acid to adjust the pH to 3.4, standing for 12h, centrifugally filtering, transferring the filtrate to the next cycle, drying the filter cake at 80 ℃, and recrystallizing to obtain 1.32Kg of pure nicotinic. The single pass recovery of nicotinic acid was 66.0%.
Example 4:
adding 19Kg of anhydrous sodium sulfate into 100Kg of waste water from nicotinic acid production (2.5 wt% of total amount of nicotinic acid and other organic matters, 20.7 wt% of sodium sulfate and 76.8 wt% of water), slightly heating to dissolve, transferring to a crystallization kettle, slowly cooling to 2 ℃ by a refrigerant at the rotation speed of 90r/min to cool and crystallize, belt filtering, washing with 6Kg of cold water at 2 ℃, merging the filtrates, transferring the filtrates to an MVR reduced pressure evaporator, distilling at 50 ℃ and 13KPa under reduced pressure to evaporate 25Kg of water, keeping the organic matter content in the raffinate at 16%, transferring the raffinate to a reflux kettle, adding 100g of active carbon, keeping the temperature at a slight boiling point for 0.5h, filtering, transferring to the crystallization kettle, dropwise adding sulfuric acid to adjust the pH to 3.4, standing for 12h, centrifugally filtering, drying the filter cake at 80 ℃, and recrystallizing to obtain 1.42Kg of pure nicotinic. The single pass recovery of nicotinic acid was 56.8%.
Example 5:
adding 24Kg of anhydrous sodium sulfate into 100Kg of wastewater from nicotinic acid production (2.0 wt% of total amount of nicotinic acid and other organic matters, 16.7 wt% of sodium sulfate, and 81.2 wt% of water), slightly heating to dissolve, and then applying ultrasonic sealing and pressurizing for 10min, wherein the process parameters are as follows: stopping ultrasound for 2min at intervals after every 5min of ultrasound reaction, wherein the pressure is 0.5MPa, and the frequency is 80 KHz; then transferring to a crystallization kettle, slowly cooling to 2 ℃ by a refrigerant at the rotating speed of 80r/min, cooling for crystallization, belt filtering, washing 6Kg of cold water at the temperature of 2 ℃, combining filtrates, adding 18Kg of anhydrous sodium sulfate, slightly heating to dissolve the anhydrous sodium sulfate, transferring to the crystallization kettle, slowly cooling to 2 ℃ by the refrigerant at the rotating speed of 80r/min, cooling for crystallization, belt filtering, washing with 1Kg of cold water at the temperature of 2 ℃, combining filtrates, dripping sulfuric acid to adjust the pH value to 3.4, standing for 12h, centrifugally filtering, transferring the filtrate to the next cycle, drying a filter cake at the temperature of 80 ℃, and recrystallizing to obtain 1.4Kg of pure nicotinic acid. The single pass recovery of nicotinic acid was 70%.
Example 6:
adding 24Kg of anhydrous sodium sulfate into 100Kg of wastewater from nicotinic acid production (2.0 wt% of total amount of nicotinic acid and other organic matters, 16.7 wt% of sodium sulfate, and 81.2 wt% of water), slightly heating to dissolve, and then applying sealing and pressurizing ultrasound for 15min, wherein the process parameters are as follows: stopping ultrasound for 2min at intervals after every 5min of ultrasound reaction, wherein the pressure is 0.5MPa, and the frequency is 80 KHz; transferring into crystallization kettle, slowly cooling to 2 deg.C by refrigerant at 80r/min, cooling for crystallization, belt filtering, washing with 6Kg2 deg.C cold water, mixing filtrates, transferring the filtrate into MVR reduced pressure evaporator, distilling at 50 deg.C and 13KPa under reduced pressure to evaporate 30Kg water, the organic matter content in the residual liquid is 19.1%, transferring the residual liquid into reflux kettle, adding 100g active carbon, maintaining at constant temperature for 0.5h under slight boiling, filtering, transferring the filtrate into crystallization kettle, adding dropwise sulfuric acid to adjust pH to 3.4, standing for 12h, centrifuging, filtering, transferring the filtrate into the next cycle, drying the filter cake at 80 deg.C, and recrystallizing to obtain 1.45Kg of pure nicotinic acid. The single pass recovery of nicotinic acid was 72.5%.
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable to various fields of endeavor for which the invention may be embodied with additional modifications as would be readily apparent to those skilled in the art, and the invention is therefore not limited to the details given herein and to the examples shown and described without departing from the generic concept as defined by the claims and their equivalents.
Claims (9)
1. A method for recovering organic matters in wastewater from nicotinic acid production is characterized by comprising the following steps:
treating the nicotinic acid production wastewater to enable the concentration of anhydrous sodium sulfate to reach saturation, then cooling, crystallizing, filtering, washing, further concentrating the filtrate until the concentration of organic matters is 10-20 wt%, then decoloring, filtering, adjusting the pH value of the filtrate, standing, centrifugally filtering, recovering the filtrate, entering the next cycle, and drying a filter cake to obtain the recovered organic matters.
2. The method for recovering the organic matters in the nicotinic acid production wastewater as claimed in claim 1, wherein the nicotinic acid production wastewater contains 1-3 wt% of the organic matters, 10-25 wt% of sodium sulfate and the balance of water, and the pH value is 7-8.
3. The method of claim 1, wherein the concentration of anhydrous sodium sulfate is saturated by adding anhydrous sodium sulfate or concentrating under reduced pressure.
4. The method for recovering the organics in the wastewater from nicotinic acid production as claimed in claim 3, wherein the added anhydrous sodium sulfate is a byproduct in the process of nicotinic acid production; the concentration under reduced pressure is carried out at 45-65 ℃ and 10-25 KPa.
5. The method for recovering the organic matters in the nicotinic acid production wastewater as claimed in claim 1, wherein the cooling crystallization temperature is 2-20 ℃, and stirring is applied during the cooling crystallization process. The stirring speed is 30-500 r/min.
6. The method for recovering the organic matters in the nicotinic acid production wastewater as claimed in claim 1, wherein the method for further concentrating the filtrate to the organic matter concentration of 10-20 wt% comprises adding anhydrous sodium sulfate or concentrating under reduced pressure; the added anhydrous sodium sulfate is a byproduct in the production process of the nicotinic acid; the concentration under reduced pressure is carried out at 45-65 ℃ and 10-25 KPa.
7. The method for recovering the organic matters in the wastewater from nicotinic acid production according to claim 1, wherein the decolorization process comprises the following steps: transferring the concentrated filtrate into a reflux kettle, adding active carbon, and keeping the temperature at 90-100 ℃ for 10-30 min.
8. The method for recovering organics in nicotinic acid production wastewater as claimed in claim 1, wherein the pH of the filtrate is adjusted to 2.5-4.0, and the acidifying agent used is 98 wt% concentrated sulfuric acid.
9. The method for recovering organic matters in the wastewater from nicotinic acid production according to claim 1, wherein the sealed pressurized ultrasonic treatment is applied for 10-15 min before the cooling crystallization, and the process parameters are as follows: stopping ultrasound for 2min at intervals after every 3-5 min of ultrasound reaction, wherein the pressure is 0.3-1.2 MPa, and the frequency is 80-120 KHz.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101985434A (en) * | 2010-11-12 | 2011-03-16 | 安徽泰格生物技术股份有限公司 | Method for preparing nicotinic acid |
| CN109133467A (en) * | 2018-09-19 | 2019-01-04 | 安徽瑞邦生物科技有限公司 | A method of niacin and ammonium chloride in the washing water of recycling acidization production niacin |
| CN110092747A (en) * | 2019-05-31 | 2019-08-06 | 安徽国星生物化学有限公司 | Niacin recycling, refining methd and wastewater treatment method in one kind waste water containing niacin |
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2021
- 2021-01-19 CN CN202110069466.7A patent/CN112812058B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| GB980356A (en) * | 1962-09-24 | 1965-01-13 | Lobachemie | Improvements in or relating to processes for separating organic compounds |
| CN1141288A (en) * | 1996-04-26 | 1997-01-29 | 清华紫光(集团)总公司 | Process for preparing nicotinic acid |
| CN1386736A (en) * | 2002-06-13 | 2002-12-25 | 浙江大学 | Process for preparing nicotinic acid |
| CN101985434A (en) * | 2010-11-12 | 2011-03-16 | 安徽泰格生物技术股份有限公司 | Method for preparing nicotinic acid |
| CN109133467A (en) * | 2018-09-19 | 2019-01-04 | 安徽瑞邦生物科技有限公司 | A method of niacin and ammonium chloride in the washing water of recycling acidization production niacin |
| CN110092747A (en) * | 2019-05-31 | 2019-08-06 | 安徽国星生物化学有限公司 | Niacin recycling, refining methd and wastewater treatment method in one kind waste water containing niacin |
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