CN108623092B - Method for treating wastewater generated in preparation of p-aminophenol - Google Patents
Method for treating wastewater generated in preparation of p-aminophenol 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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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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- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
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- C—CHEMISTRY; METALLURGY
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- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- C02F3/00—Biological treatment of water, waste water, or sewage
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Abstract
本发明涉及一种处理制备对氨基苯酚产生的废水的方法，即在制备对氨基苯酚产生的废水中首先加入氯化钙，氯化钙与废水中的焦亚硫酸钠生成焦亚硫酸钙沉淀下来；抽滤出沉淀物后，再加入强的酸，与对氨基苯酚成盐；采用蒸馏或精馏的方法脱水，脱出的水无色，前期含乙醇，且COD高，占废水总量的5％～15％的废水回收套用到对氨基苯酚的制备过程中，后期蒸出的废水进入生化处理池处理。该方法不仅操作工艺简单，而且避免了直接脱水会有对氨基苯酚带出，也容易实现大规模工业化生产。The invention relates to a method for treating waste water produced by the preparation of p-aminophenol, that is, calcium chloride is firstly added to the waste water produced by the preparation of p-aminophenol, and calcium chloride and sodium metabisulfite in the waste water form calcium metabisulfite and precipitate; After filtering out the precipitate, add a strong acid to form a salt with p-aminophenol; use distillation or rectification to dehydrate, and the dehydrated water is colorless, contains ethanol in the early stage, and has high COD, accounting for 5% of the total wastewater. 15% of the waste water is recycled and applied to the preparation process of p-aminophenol, and the waste water distilled in the later stage enters the biochemical treatment tank for treatment. The method not only has a simple operation process, but also avoids the carrying out of p-aminophenol by direct dehydration, and is also easy to realize large-scale industrial production.
Description
Technical Field
The invention relates to a technology of wastewater treatment, in particular to a treatment of wastewater generated in the preparation of p-aminophenol, namely the wastewater generated in the reduction production of p-aminophenol by p-nitrophenol.
Background
P-aminophenol, also known as para-hydroxyaniline, p-aminophenol, having the formula:
para-aminophenol is an intermediate of fine chemicals such as medicines, dyes and the like, and can be used for producing drugs such as paracetamol, azo dyes, sulfur dyes, developers and the like.
The preparation method of p-aminophenol reported in literature can be divided into three methods, namely a p-nitrophenol reduction method, a nitrobenzene reduction rearrangement method and a phenol nitrosation reduction method according to different synthetic raw materials, wherein the p-nitrophenol reduction method is a method generally adopted in the current industrialization. The p-nitrophenol is reduced into p-aminophenol, and the prior chemical reduction method such as iron powder is mainly adopted for hydrogenation reduction due to serious pollution.
The p-nitrophenol is hydrogenated and reduced into the p-aminophenol, and the solvent is a mixed solvent of ethanol and water. After the reaction is finished, most products are generally separated out through cooling crystallization, and after most ethanol is separated through distillation, a small amount of ethanol and p-aminophenol are remained, the COD (chemical oxygen demand) sometimes reaches about 10 ten thousand, the black wastewater is obtained, and the amount of the wastewater is large. In addition, since p-aminophenol is easily oxidized and does not affect the quality of the product, it is common to add an inorganic antioxidant to the reaction system after the reaction is completed, and sodium metabisulfite is used to suppress the oxidation of p-aminophenol, so that sodium metabisulfite is also contained in such wastewater.
The direct discharge of such waste water would cause great harm to the environment and would require disposal before discharge. With the continuous increase of the yield of p-aminophenol in China, the treatment of p-aminophenol wastewater becomes very important.
Common treatment methods reported in the literature for organic wastewater include physical adsorption, or sedimentation, chemical oxidation, and complex microbial treatment. The composite microbial treatment method cannot treat wastewater with high COD. Physical adsorption methods, including resin adsorption methods and activated carbon adsorption methods, have the problems that no adsorbent can meet the requirements on the adsorption effect of para-aminophenol, and the treatment of the used adsorbent has the problems of link pollution and higher cost; the oxidation method, whether hydrogen peroxide oxidation or ozone oxidation, has the disadvantages of high process requirements, especially large-scale industrialized devices, relatively high cost, and the need to find a proper catalyst.
In view of the problems of the common wastewater treatment method for treating the p-aminophenol wastewater, the existing enterprises adopt a distillation or rectification dehydration method for treating the p-aminophenol wastewater, and adopt a simple distillation or rectification method for treatment, after most of ethanol is evaporated in the early stage, the water evaporated in the later stage still has high COD, and the color becomes dark after the water is placed in the air for a period of time, because the steam pressure of the p-aminophenol is low and the water is easy to be oxidized and blackened; in addition, sodium pyrosulfite is seriously decomposed in the later stage of distillation, and sulfur dioxide is generated. There is a need for reasonably efficient wastewater treatment techniques.
Disclosure of Invention
The invention aims to overcome the defects of the existing p-aminophenol wastewater treatment method, provides a novel method for treating wastewater generated by preparing p-aminophenol, thoroughly solves the problem of treatment of p-aminophenol wastewater, and can ensure that the treated water is colorless, most of COD (chemical oxygen demand) is lower than 3000, and the treated water can enter a biochemical treatment tank. The method has simple process and is suitable for large-scale industrial production.
The realization of the object of the invention comprises the following steps:
(1) adding calcium chloride into the wastewater, precipitating the calcium metabisulfite generated by the sodium metabisulfite and the calcium chloride in the wastewater, and separating out the precipitate to obtain a liquid material.
(2) And (2) adding strong acid into the liquid material obtained in the step (1), and uniformly mixing to salify the p-aminophenol in the wastewater.
(3) And (3) distilling or rectifying and dehydrating the wastewater treated in the step (2), wherein the COD evaporated at the early stage is higher, the wastewater accounting for 5-15% of the total amount of the wastewater is recycled and applied to the preparation process of the p-aminophenol, and the wastewater evaporated at the later stage can enter a biochemical treatment tank for treatment.
The adding amount of the calcium chloride in the step (1) is determined according to the amount of sodium metabisulfite, the molar weight ratio of the calcium chloride to the sodium metabisulfite is 1.0: 1.0-1.2: 1.0, the calcium chloride is fully stirred after being added, and the solid-liquid separation is carried out after standing and settling.
The strong acid added in the step (2) is one or a mixture of more of sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and formic acid with various concentrations.
The amount of the acid added in the step (2) is the amount of the acid when the pH value of the p-aminophenol wastewater after the acid is added is 2-7.
Preferably, the amount of the acid added in the step (2) is the amount of the acid when the pH of the p-aminophenol wastewater after the acid addition is 3 to 5.
Has the advantages that: the method is suitable for treating the wastewater generated by preparing the p-aminophenol. The color of the treated water is colorless, the part with high ethanol content can be recycled and applied to the preparation process of p-aminophenol, most of the rest COD is lower than 2000, and the weakly acidic wastewater enters a biochemical treatment tank for treatment. The method has simple process and is easy to realize industrial production.
Detailed description of the invention
The present application is described below by way of example and further understood with reference to specific examples, but the examples are given by way of example only and are not to be construed as limiting the overall technical aspects of the present invention. All the simple changes or substitutions with the same or similar technical characteristics belong to the protection scope of the invention.
Example 1
At room temperature, 5L of p-aminophenol wastewater with COD of 98020 is taken, 80.00g of calcium chloride solid is added under stirring, the stirring is continued for 30min, precipitate is generated, and 61.91g of solid is obtained by suction filtration. 50.0mL of concentrated sulfuric acid is added into the filtrate, and the mixture is stirred to fully salify the sulfuric acid and the p-aminophenol, wherein the pH value is about 4. Standing at room temperature for 3 hr to precipitate solid, and vacuum filtering to obtain 43.96g solid.
The filtrate of the p-aminophenol wastewater is added into a 10L three-port baked cake which is provided with a jacketed rectifying column with the outer diameter of 7 cm, the inner diameter of 3 cm and the height of 30 cm and a rectifying head. The outside of the rectification column is heated by hot water at 70 ℃ through a jacket, and a rectification head is cooled by tap water. The water is distilled under normal pressure, the reflux is only the natural reflux of the rectifying column, and no external reflux exists. The distilled water was colorless. The effluent is divided into 4 parts: the first part is clear and transparent with water outlet volume of 400mL, pH value of 6 and COD of 220300; the second part of the effluent is 300mL, clear and transparent, the pH value is 5-6, and the COD is 2300; 3600mL of water discharged from the third part, clearness and transparency, the pH value is 5, and the COD is 906; the fourth part is 200mL of clear and transparent water, the pH value is 4-5, and the COD is 1560. After the effluent is placed overnight, the fourth part turns into light yellow, and the rest parts do not have any color change; after another 13 days, the solution was checked again and did not change in color or pH.
Example 2
At room temperature, 5L of p-aminophenol wastewater with COD of 98020 is taken, 60.00g of calcium chloride solid is added under stirring, the stirring is continued for 30min, precipitate is generated, and 60.00g of solid is obtained by suction filtration. 42.0mL of concentrated sulfuric acid is added into the filtrate, and the mixture is stirred to fully salify the sulfuric acid and the p-aminophenol. After standing at room temperature for 3 hours, a solid precipitated out, and was filtered under suction to obtain 41.50g of a solid.
The filtrate of the p-aminophenol wastewater is added into a 10L three-port baked cake which is provided with a jacketed rectifying column with the outer diameter of 7 cm, the inner diameter of 3 cm and the height of 30 cm and a rectifying head. The outside of the rectification column is heated by hot water at 70 ℃ through a jacket, and a rectification head is cooled by tap water. The water is distilled under normal pressure, the reflux is only the natural reflux of the rectifying column, and no external reflux exists. The distilled water was colorless. The effluent is divided into 4 parts: 425mL of water in the first part is clear and transparent, the pH value is 4-5, and the COD is 211300; 545mL of second part effluent is clear and transparent, the pH value is 4-5, and the COD is 1981; 3180mL of the third part of effluent, clear and transparent, wherein the pH value is 4-5, and the COD is 898; the fourth part is clear and transparent with water of 260mL, pH value of 4-5 and COD of 1620. After the effluent is placed overnight, the fourth part turns into light yellow, and the rest parts do not have any color change; after another 13 days, the solution was checked again and did not change in color or pH.
Example 3
At room temperature, 5L of p-aminophenol wastewater with COD of 782300 is taken, 45.00g of calcium chloride solid is added under stirring, the stirring is continued for 30min, precipitate is generated, and 52.74g of solid is obtained by suction filtration. Adding 60.0mL of concentrated sulfuric acid into the filtrate, and stirring to fully salify the sulfuric acid and the p-aminophenol. After standing at room temperature for 3 hours, a solid precipitated out, and was filtered under suction to obtain 42.05g of a solid.
The filtrate of the p-aminophenol wastewater is added into a 10L three-port baked cake which is provided with a jacketed rectifying column with the outer diameter of 7 cm, the inner diameter of 3 cm and the height of 30 cm and a rectifying head. The outside of the rectification column is heated by hot water at 70 ℃ through a jacket, and a rectification head is cooled by tap water. The water is distilled under normal pressure, the reflux is only the natural reflux of the rectifying column, and no external reflux exists. The distilled water was colorless. The effluent is divided into 4 parts: 300mL of first part effluent is clear and transparent, the pH value is 6, and the COD is 193400; the second part of the effluent is 350mL, clear and transparent, the pH value is 6, and the COD is 1578; 3775mL of the third part of effluent is clear and transparent, the pH value is 5-6, and the COD is 875; and the fourth part is clear and transparent with water of 300mL, the pH value of 4-5 and the COD of 2057. After the effluent is placed overnight, no color change occurs.
Example 4
At room temperature, 5L of p-aminophenol wastewater with COD of 782300 is taken, 50.00g of calcium chloride solid is added under stirring, the stirring is continued for 30min, precipitate is generated, and 43.15g of solid is obtained through suction filtration. Adding 55.0mL of concentrated sulfuric acid into the filtrate, and stirring to fully salify the sulfuric acid and the p-aminophenol. Standing at room temperature for 3 hr to precipitate solid, and vacuum filtering to obtain 40.12g solid.
The filtrate of the p-aminophenol wastewater is added into a 10L three-port baked cake which is provided with a jacketed rectifying column with the outer diameter of 7 cm, the inner diameter of 3 cm and the height of 30 cm and a rectifying head. The outside of the rectification column is heated by hot water at 70 ℃ through a jacket, and a rectification head is cooled by tap water. The water is distilled under normal pressure, the reflux is only the natural reflux of the rectifying column, and no external reflux exists. The distilled water was colorless. The effluent is divided into 4 parts: the first part is 320mL of water, clear and transparent, the pH value is 6, and the COD is 191200; 260mL of second part effluent is clear and transparent, the pH value is 5, and the COD is 1627; 3500mL of third part effluent, clearness and transparency, pH value of 5 and COD of 892; the fourth part is clear and transparent with water of 300mL, pH value of 4-5 and COD of 1320. After the effluent is placed for three days, no color change occurs.
Claims (5)
1. A method for treating wastewater generated in the preparation of p-aminophenol is characterized by comprising the following steps:
(1) adding calcium chloride into the wastewater, precipitating the calcium metabisulfite generated by the sodium metabisulfite and the calcium chloride in the wastewater, and separating out precipitates to obtain a liquid material;
(2) adding strong acid into the liquid material generated in the step (1), and uniformly mixing to salify p-aminophenol and the acid in the wastewater;
(3) and (3) distilling or rectifying and dehydrating the wastewater treated in the step (2), wherein the COD evaporated at the early stage is high, the wastewater accounting for 5-15% of the total amount of the wastewater is recycled and applied to the preparation process of the p-aminophenol, and the wastewater evaporated at the later stage enters a biochemical treatment tank for treatment.
2. The method for treating wastewater generated in the preparation of p-aminophenol according to claim 1, wherein the amount of calcium chloride added in step (1) is determined according to the amount of sodium metabisulfite contained therein, and the molar weight ratio of calcium chloride to sodium metabisulfite is 1.0: 1.0-1.2: 1.0.
3. A method for treating wastewater from the production of p-aminophenol in accordance with claim 1, wherein said acid added in said step (2) is a mixed acid of one or more acids selected from sulfuric acid, phosphoric acid, hydrochloric acid, nitric acid and formic acid in various concentrations.
4. The method for treating wastewater from the production of p-aminophenol according to claim 1, wherein said acid is added in an amount required for the pH of the p-aminophenol wastewater after the acid addition to be 2 to 7 in said step (2).
5. The method for treating wastewater generated in the preparation of p-aminophenol according to claim 4, wherein said acid is added in said step (2) in an amount required for the pH of the p-aminophenol wastewater to be 3 to 5 after the acid addition.
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| CN112479423B (en) * | 2020-11-18 | 2022-12-27 | 辽东学院 | Wastewater treatment method for producing amino-containing phenolic compounds |
| CN115636522A (en) * | 2022-09-07 | 2023-01-24 | 安徽东至广信农化有限公司 | An integrated treatment process for p-aminophenol production wastewater |
| CN115521014A (en) * | 2022-10-28 | 2022-12-27 | 辽宁世星药化有限公司 | Method for treating wastewater generated in production of p-aminophenol by catalytic hydrogenation of nitrobenzene |
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| CN104211249A (en) * | 2014-09-15 | 2014-12-17 | 陕西华陆化工环保有限公司 | Treatment method of aminophenol wastewater |
| CN104355455B (en) * | 2014-11-20 | 2016-04-13 | 郑州航空工业管理学院 | A kind of Ortho-Aminophenol method of wastewater treatment |
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