Method for rapidly realizing harmless treatment of chlorophenol industrial hazardous waste

Abstract

The invention discloses a method for rapidly realizing harmless treatment of chlorophenol industrial hazardous waste, which is characterized in that the chlorophenol industrial hazardous waste is subjected to catalytic hydrogenation treatment by taking Raney Ni as a catalyst and hydrogen as a hydrogen source, and the chlorophenol industrial hazardous waste can be rapidly and completely dechlorinated under the conditions that the reaction pressure is 0.1-2.0 MPa, the temperature is 25-80 DEG C and the reaction pH is controlled to be 6.0-9.0. Phenol and cyclohexanone are obtained; the reaction conditions are mild, the dechlorination speed is high, harmless treatment of the high-concentration chlorophenol hazardous waste is achieved, operation is easy to control, and the cost is low.

Description

Technical Field

[0001] The present invention relates to the technical field of the treatment of industrial hazardous wastes containing chlorophenols. Specifically, it is a method for rapidly realizing the harmless treatment of industrial hazardous wastes containing chlorophenols, which can effectively dechlorinate industrial hazardous wastes containing chlorophenols to produce phenol and cyclohexanone. Background Art

[0002] Chlorophenol compounds are important chemical raw materials and are widely used in industries such as chemical engineering, medicine, and pesticides. Chlorobenzene phenol compounds are also a class of organic compounds that are difficult to degrade in the environment, polluting the ecological environment. At the same time, they are considered to have carcinogenic, teratogenic, and mutagenic effects, and also have a great impact on the health of the general population.

[0003] Chlorophenol substances are mainly produced by the free radical chlorination process of phenol. Due to the existence of multiple chlorination positions on the benzene ring, it is difficult to achieve directional conversion. Therefore, during the production process, a variety of isomers and homologues with phenol as the parent body will be formed, and finally a large amount of industrial rectification waste residues and mother liquors containing various chlorophenols will be produced. For example, in the production of 2,4,6-trichlorophenol, 5-10% of waste residues or mother liquors containing various chlorophenol homologues such as 2-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, and 2,4,6-trichlorophenol will be generated. At present, high-temperature incineration is the main method for treating industrial hazardous wastes containing chlorophenols, but there are problems of high energy consumption and secondary pollution of dioxin generation; at the same time, with the proposal of the goals of "carbon neutrality and carbon peak", high-temperature incineration will lead to a large amount of CO2 emissions, which is not conducive to the achievement of the "dual carbon" goals. Summary of the Invention

[0004] The purpose of the present invention is to overcome the deficiencies of the above-mentioned existing technologies and provide a method for rapidly realizing the harmless treatment of industrial hazardous wastes containing chlorophenols.

[0005] The technical solution provided by the present invention is: a method for rapidly realizing the harmless treatment of industrial hazardous wastes containing chlorophenols, which is characterized in that using Raney Ni as a catalyst and hydrogen as a hydrogen source, catalytic hydrogenation treatment is carried out on industrial hazardous wastes containing chlorophenols. Under the conditions of a reaction pressure of 0.1-2.0 MPa, a temperature of 25-80 °C, and a controlled reaction pH of 6.0-9.0, the industrial hazardous wastes containing chlorophenols can rapidly achieve complete dechlorination to obtain phenol and cyclohexanone.

[0006] Further, the Raney Ni catalyst is prepared through the following process: adding an auxiliary agent and mixing evenly in an NaOH solution; adding the NiAl alloy to the above alkali solution and reacting at 20-80 °C for 1-3 hours, and the solid obtained by filtration is the Raney Ni catalyst.

[0007] Furthermore, the mass concentration of the NaOH solution is 5-20%; the amount of the additive added is 0.1-5.0% of the weight of the NaOH solution, and the additive is polyvinylpyrrolidone or polyethylene glycol; the Ni / Al molar ratio of the NiAl alloy is 60 / 40-40 / 60, and the particle size of the NiAl alloy is 60-200 mesh.

[0008] Furthermore, the Ni / Al molar ratio of the NiAl alloy is 50 / 50.

[0009] Furthermore, the average molecular weight of the polyvinylpyrrolidone is 6000-100000; the average molecular weight of the polyethylene glycol is 200-8000.

[0010] Furthermore, when the average molecular weight of the polyvinylpyrrolidone is 8000-60000 and the added amount is 1% of the weight of the NaOH solution, the catalytic activity of the Raney Ni catalyst shows the best.

[0011] Furthermore, when the average molecular weight of the polyethylene glycol is 500-5000 and the added amount is 3% of the weight of the NaOH solution, the selectivity and stability of the Raney Ni catalyst show the best.

[0012] Furthermore, the reaction pH is controlled to be 6.5-7.5, and the base for controlling the pH range is NaOH or KOH or Ca(OH)2.

[0013] Furthermore, the reaction pressure is 0.1-0.5 Mpa, and the reaction temperature is 45-65 °C.

[0014] Furthermore, the chlorophenol industrial hazardous waste is industrial residues and waste liquids containing 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol and 2,4,6-trichlorophenol formed during the industrial production of 2,4-dichlorophenol or 2,4,6-trichlorophenol.

[0015] Advantages of the present invention: 1. The Raney Ni catalyst modified by the additive has high activity, good selectivity and stability, can significantly reduce the poisoning of HCl during the Raney Ni hydrodechlorination process, and at the same time improves the problem of slow mass transfer of chlorophenol hazardous waste in the medium, and efficiently and quickly realizes the hydrodechlorination treatment of chlorophenol industrial hazardous waste; 2. The wet reduction method of the catalyst has mild operating conditions, can be directly filtered, and is easy to be scaled up industrially, and can significantly improve the inactivation caused by oxidation problems during the catalyst treatment process; 3. It effectively realizes the effective dechlorination of chlorophenol waste residues, high-concentration chlorophenol waste liquids and waste water, generates phenol and cyclohexanone, and realizes the harmless treatment and resource utilization of chlorophenol hazardous waste. Specific embodiments

[0016] The present invention will be further described below in conjunction with specific embodiments, but the present invention is not limited to these specific embodiments. Those skilled in the art should recognize that the present invention covers all alternative solutions, improvement solutions, and equivalent solutions that may be included within the scope of the claims. Example 1

[0017] Weigh 200 g of NaOH and dissolve it in 800 mL of distilled water. Add 10 g of polyvinylpyrrolidone (average molecular weight 8000). Under slow stirring at 20 °C, then add 50 g of 200-mesh NiAl (Ni / Al = 50:50) alloy in three portions. Then heat to 50 °C and react for 2 hours. Filter, wash the precipitate three times with water and then three times with ethanol to obtain Raney nickel catalyst RPV-1. To avoid surface oxidation due to long-term exposure to air, this catalyst can be stored in ethanol.

[0018] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 0.1 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the base for controlling the pH range is NaOH. React for 2 h. At this time, all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 0.5% of cyclohexanone is formed.

[0019] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is 8.0 - 9.0, and the base for controlling the pH range is NaOH. React for 1 h. At this time, all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 5% of cyclohexanone is formed.

[0020] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 80 °C, the operating pressure is 0.1 MPa, the initial pH of the reaction is 10.5 - 11.5, and the base for controlling the pH range is NaOH. React for 5 h, and the chlorine atom removal rate is 85%.

[0021] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 25 °C, the operating pressure is 2.0 MPa, the initial pH of the reaction is 12.5 - 13.5, and the base for controlling the pH range is NaOH. React for 8 h; the chlorine atom removal rate is 95%.

[0022] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 15%. The reaction temperature is 70 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the base for controlling the pH range is NaOH. React for 3 h; all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 15% of cyclohexanone is formed.

[0023] As can be seen from Example 1, when treating chlorophenol hazardous waste, after the reaction pH > 10.0, the reaction time is also extended, and the dechlorination effect of chlorophenol hazardous waste is poor. Therefore, a pH range of 6.0 - 9.0 is selected during the treatment process. Example 2

[0024] Weigh 200 g of NaOH and dissolve it in 800 mL of distilled water. Add 10 g of polyvinylpyrrolidone (average molecular weight 30000). Under slow stirring at 20 °C, then add 50 g of 200-mesh NiAl (Ni / Al = 50:50) alloy in three portions. Then heat to 50 °C and react for 2 hours. Filter, wash the precipitate three times with water and then three times with ethanol to obtain Raney nickel catalyst RPV-2; to avoid surface oxidation caused by long-term exposure to air, this catalyst can be stored in ethanol.

[0025] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the base for controlling the pH range is KOH. React for 1 h; all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 12% of cyclohexanone is formed.

[0026] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the base for controlling the pH range is KOH. React for 1 h; all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 23% of cyclohexanone is formed.

[0027] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the base for controlling the pH range is KOH. React for 1 h; all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 12% of cyclohexanone is formed. Example 3

[0028] Weigh 200 g of NaOH and dissolve it in 800 mL of distilled water. Add 10 g of polyvinylpyrrolidone (average molecular weight 60,000). Under slow stirring at 20 °C, add 50 g of 200-mesh NiAl (Ni / Al = 50:50) alloy in three portions. Then heat to 50 °C and react for 2 hours. Filter, wash the precipitate three times with water and then three times with ethanol to obtain the Raney nickel catalyst RPV-3. To avoid surface oxidation due to long-term exposure to air, this catalyst can be stored in ethanol.

[0029] Add 2.0 g of the above catalyst to a batch reactor and perform hydrotreating on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the base for controlling the pH range is Ca(OH)2. React for 1.5 h. All chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 8% of cyclohexanone is formed.

[0030] Add 2.0 g of the above catalyst to a batch reactor and perform hydrotreating on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the base for controlling the pH range is Ca(OH)2. React for 2 h. All chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 18% of cyclohexanone is formed.

[0031] Add 2.0 g of the above catalyst to a batch reactor and perform hydrotreating on 400 mL of 5% mass concentration of 2,4-dichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the base for controlling the pH range is Ca(OH)2. React for 1.5 h. All chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 9% of cyclohexanone is formed. Example 4

[0032] Weigh 200 g of NaOH and dissolve it in 800 mL of distilled water. Add 50 g of polyvinylpyrrolidone (average molecular weight 100,000). Directly add 50 g of 100-mesh NiAl (Ni / Al = 50:50) alloy. Then heat to 60 °C and react for 1 hour. Then filter to obtain the precipitate, wash it three times with water and then three times with ethanol to obtain the Raney nickel catalyst RPV-4. To avoid surface oxidation due to long-term exposure to air, this catalyst can be stored in ethanol.

[0033] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 2 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0034] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol, and 25% cyclohexanone is generated simultaneously.

[0035] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 30 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 3 h; all chlorophenols are completely dechlorinated and converted into phenol, and 5% cyclohexanone is generated simultaneously.

[0036] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 70 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol, and 6.5% cyclohexanone is generated simultaneously.

[0037] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol, and 10.5% cyclohexanone is generated simultaneously. Example 5

[0038] Weigh 100 g of NaOH and dissolve it in 900 mL of distilled water. Add 10 g of polyvinylpyrrolidone (average molecular weight 6000) and mix well. Then directly add 50 g of 100-mesh NiAl (Ni / Al = 50:50) alloy, and then heat to 50 °C and react for 3 hours. Then filter to obtain a precipitate, wash it three times with water, and then wash it three times with ethanol to obtain Raney nickel catalyst RPV-5; to avoid surface oxidation caused by long-term exposure to air, this catalyst can be stored in ethanol.

[0039] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.1 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 7 h; all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 3.5% cyclohexanone is generated.

[0040] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 5 h; all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 15% cyclohexanone is generated.

[0041] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 3 h; all chlorophenols are completely dechlorinated and converted into phenol, and at the same time, 17% cyclohexanone is generated. Example 6

[0042] Weigh 50 g of NaOH and dissolve it in 950 mL of distilled water. Add 30 g of polyethylene glycol (average molecular weight 500), and stir slowly at 20 °C. Directly add 50 g of 60-mesh NiAl (Ni / Al = 60:40) alloy, then heat to 50 °C, react for 3 hours, then filter to obtain a precipitate, wash it three times with water, and then wash it three times with ethanol to obtain Raney nickel catalyst RPE-1.

[0043] Add 1.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.0 and 7.0, and the reaction lasts for 2 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0044] Add 1.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 65 °C, the operating pressure is 0.1 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 3 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0045] Add 1.0 g of the above catalyst to a batch reactor, and perform hydrogenation treatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 45 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 2 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0046] Add 1.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 80 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 10.0 and 11.0, and the reaction lasts for 5 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0047] Add 1.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 15%. The reaction temperature is 25 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 3 h; all chlorophenols are completely dechlorinated and converted into phenol. Example 7

[0048] Weigh 200 g of NaOH and dissolve it in 800 mL of distilled water. Add 30 g of polyethylene glycol (average molecular weight 5000) and mix well. Stir slowly at 20 °C, add 50 g of 100-mesh NiAl (Ni / Al = 50:50) alloy in 3 batches, then heat to 80 °C and react for 3 hours. Then filter to obtain a precipitate, wash it three times with water and then three times with ethanol to obtain Raney nickel catalyst RPE-2; to avoid surface oxidation caused by long-term existence in air, this catalyst can be stored in ethanol.

[0049] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.1 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 2 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0050] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0051] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 70 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0052] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 30 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h. All chlorophenols are completely dechlorinated and converted into phenol.

[0053] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 70 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 10.0 and 11.0, and the reaction lasts for 3 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0054] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0055] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 15%. The reaction temperature is 70 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 2 h; all chlorophenols are completely dechlorinated and converted into phenol. Example 8

[0056] Weigh 100 g of NaOH and dissolve it in 900 mL of distilled water. Add 50 g of polyethylene glycol (average molecular weight 8000) and mix well. Then directly add 50 g of 60-mesh Ni-Al (Ni / Al = 40:60), and then heat to 50 °C and react for 2 hours. Then filter to obtain a precipitate, wash it three times with water and then three times with ethanol to obtain Raney nickel catalyst RPE-3; to avoid surface oxidation caused by long-term exposure to air, this catalyst can be stored in ethanol.

[0057] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 5 h; the chlorophenol is completely dechlorinated and converted into phenol.

[0058] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 3 h; the chlorine removal rate of all chlorophenols is 88%.

[0059] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreating on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 5 h; all chlorophenols are completely dechlorinated and converted into phenol. Example 9

[0060] Weigh 100 g of NaOH and dissolve it in 900 mL of distilled water. Add 1 g of polyethylene glycol (average molecular weight 200) and mix well. Directly add 50 g of 200-mesh Ni-Al (Ni / Al = 50:50), then heat to 50 °C and react for 2 hours. Then filter to obtain the precipitate, wash it three times with water and then three times with ethanol to obtain the Raney nickel catalyst RPE-4. To avoid surface oxidation due to long-term exposure to air, this catalyst can be stored in ethanol.

[0061] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 7 h. The removal rate of chlorine in chlorophenol is 62%.

[0062] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4-dichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 7 h. The removal rate of chlorine in chlorophenol is 95%.

[0063] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 70 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 5 h. The removal rate of chlorine in chlorophenol is 88%. Example 10

[0064] Weigh 100 g of NaOH and dissolve it in 900 mL of distilled water. Add 30 g of polyethylene glycol (average molecular weight 3000) and mix well. Directly add 50 g of 100-mesh Ni-Al (Ni / Al = 50:50), then heat to 50 °C and react for 2 hours. Then filter to obtain the precipitate, wash it three times with water and then three times with ethanol to obtain the Raney nickel catalyst RPE-5. To avoid surface oxidation due to long-term exposure to air, this catalyst can be stored in ethanol.

[0065] Add 2.0 g of the above catalyst to a batch reactor and perform hydrogenation treatment on 400 mL of 5% mass concentration of 2,4,6-trichlorophenol hazardous waste. The reaction temperature is 50 °C, the operating pressure is 0.3 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h. All chlorophenols are completely dechlorinated and converted into phenol.

[0066] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0067] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreatment on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 10%. The reaction temperature is 50 °C, the operating pressure is 0.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 1 h; all chlorophenols are completely dechlorinated and converted into phenol. Comparative Example 11

[0068] Weigh 100 g of NaOH and dissolve it in 900 mL of distilled water. Add 50 g of 100-mesh Ni-Al (Ni / Al = 50:50) alloy in three batches at 20 °C, then heat to 50 °C and react for 2 hours. Then filter to obtain a precipitate, wash it three times with water and then three times with ethanol to obtain Raney nickel catalyst R1; to avoid surface oxidation due to long-term exposure to air, this catalyst can be stored in ethanol.

[0069] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 0.1 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 10 h. The chlorine removal rate of chlorophenol is 85%.

[0070] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 5 h; all chlorophenols are completely dechlorinated and converted into phenol.

[0071] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 50 °C, the operating pressure is 1.0 MPa, the pH of the reaction solution is controlled between 8.0 and 9.0, and the reaction lasts for 5 h. The chlorine removal rate is 78%.

[0072] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreatment on 400 mL of 2,4,6-trichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 70 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 11.5 and 12.5, and the reaction lasts for 10 h. The chlorine removal rate is 78%.

[0073] Add 2.0 g of the above catalyst to a batch reactor, and perform hydrotreatment on 400 mL of 2,4-dichlorophenol hazardous waste with a mass concentration of 5%. The reaction temperature is 70 °C, the operating pressure is 1.5 MPa, the pH of the reaction solution is controlled between 6.5 and 7.5, and the reaction lasts for 10 h. The chlorine removal rate is 95%.

[0074] It can be seen from Comparative Example 11 that the Raney Ni prepared without adding the additive has certain activity, but compared with the Raney Ni with the additive in Examples 1 to 10, the activity is weaker.

[0075] It should be understood that the technical features not elaborated in detail in this specification all belong to the prior art. Although the embodiments of the present invention have been described above, the present invention is not limited to the above specific embodiments. The above specific embodiments are merely illustrative and not restrictive. Those skilled in the art can, under the inspiration of the present invention and without departing from the spirit and scope protected by the claims of the present invention, also make more forms, and all of these fall within the protection scope of the present invention.

Claims

1. A method for quickly realizing the harmless treatment of industrial hazardous waste containing chlorophenols, characterized in that, Using Raney Ni as a catalyst and hydrogen as a hydrogen source, catalytic hydrogenation treatment is carried out on industrial hazardous waste of chlorophenols. Under the conditions of a reaction pressure of 0.1 - 2.0 MPa, a temperature of 25 - 80 °C, and controlling the reaction pH to be 6.0 - 9.0, the industrial hazardous waste of chlorophenols can rapidly achieve complete dechlorination to obtain phenol and cyclohexanone.

2. A method for quickly realizing harmless treatment of industrial hazardous waste of chlorophenols according to claim 1, characterized in that, The Raney Ni catalyst is prepared through the following process: adding an auxiliary agent and mixing evenly in an NaOH solution; adding the NiAl alloy into the above alkali solution, reacting at 20 - 80 °C for 1 - 3 hours, and the solid obtained by filtration is the Raney Ni catalyst.

3. A method for rapidly realizing harmless treatment of industrial hazardous waste of chlorophenols according to claim 2, characterized in that, The mass concentration of the NaOH solution is 5 - 20%; the amount of the auxiliary agent added is 0.1 - 5.0% of the weight of the NaOH solution, and the auxiliary agent is polyvinylpyrrolidone or polyethylene glycol; the Ni / Al molar ratio of the NiAl alloy is 60 / 40 - 40 / 60, and the particle size of the NiAl alloy is 60 - 200 mesh.

4. A method for rapidly realizing harmless treatment of industrial hazardous waste of chlorophenols according to claim 3, characterized in that, The Ni / Al molar ratio of the NiAl alloy is 50 / 50.

5. A method for rapidly realizing harmless treatment of industrial hazardous waste of chlorophenols according to claim 3, characterized in that, The average molecular weight of the polyvinylpyrrolidone is 6000 - 100000; the average molecular weight of the polyethylene glycol is 200 - 8000.

6. A method for rapidly realizing the harmless treatment of industrial hazardous waste of chlorophenols according to claim 5, characterized in that, When the average molecular weight of the polyvinylpyrrolidone is 8000 - 60000 and the added amount is 1% of the weight of the NaOH solution, the catalytic activity of the Raney Ni catalyst shows the best.

7. A method for rapidly realizing harmless treatment of industrial hazardous waste of chlorophenols according to claim 5, characterized in that, When the average molecular weight of the polyethylene glycol is 500 - 5000 and the added amount is 3% of the weight of the NaOH solution, the selectivity and stability of the Raney Ni catalyst show the best.

8. A method for rapidly realizing harmless treatment of industrial hazardous waste of chlorophenols according to claim 1, characterized in that, The reaction pH is controlled to be 6.5 - 7.5, and the alkali for controlling the pH range is NaOH or KOH or Ca(OH)2.

9. A method for rapidly realizing the harmless treatment of industrial hazardous waste containing chlorophenols according to claim 1, characterized in that, The reaction pressure is 0.1 - 0.5 Mpa, and the reaction temperature is 45 - 65 °C.

10. A method for rapidly realizing harmless treatment of industrial hazardous waste of chlorophenols according to claim 1, characterized in that, The industrial hazardous waste of chlorophenols is industrial residues and waste liquids containing 2-chlorophenol, 4-chlorophenol, 2,4-dichlorophenol, 2,6-dichlorophenol, and 2,4,6-trichlorophenol formed during the industrial production processes of 2,4-dichlorophenol or 2,4,6-trichlorophenol.