CN112010494A - Method for treating wastewater generated by synthesizing para-ester by mercaptoethanol method - Google Patents
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Abstract
The invention belongs to the field of environment-friendly wastewater treatment, and particularly relates to a method for treating wastewater generated by synthesizing a dye intermediate p- (beta-sulfate ethyl sulfone) aniline (commonly called para-ester) by a mercaptoethanol method p-nitrochlorobenzene route. The wastewater generated by synthesizing the para-ester is subjected to catalytic wet oxidation-biochemical treatment, and the treated wastewater reaches GB8978-96 three-level discharge standard; the waste water and the catalyst are mixed and enter a tube pass of a heat exchanger to exchange heat with the reacted high-temperature oxidation waste water, and then the waste water is heated to the reaction temperature by high-temperature heat conduction oil through a preheater and enters an oxidation reactor to realize catalytic wet oxidation reaction. The catalytic wet oxidation-biochemical combined treatment process developed by the invention aims at the characteristics of high content of DMF (dimethyl formamide) and other difficultly biodegradable substances, high chroma, organic sulfide malodor and the like of para-nitrochlorobenzene synthesized by a mercaptoethanol method, has the advantages of simple process flow, high treatment efficiency, no generation of solid waste and the like, and the treated wastewater reaches the GB8978-96 three-level discharge standard.
Description
Technical Field
The invention belongs to the field of environment-friendly wastewater treatment, and particularly relates to a method for treating wastewater generated by synthesizing a dye intermediate p- (beta-sulfate ethyl sulfone) aniline (commonly called para-ester) by a mercaptoethanol method p-nitrochlorobenzene route.
Background
The para-ester as the intermediate of the dye is one of the main raw materials for producing the active dye, the domestic demand is large, more than 10 enterprises for producing the para-ester in China are reached, and the yield is the first in the world. The synthetic route of the para-ester mainly comprises two routes of acetanilide and para-nitrochlorobenzene. The p-nitrochlorobenzene route of the mercaptoethanol method is to obtain para-ester by condensation, oxidation, reduction and sulfation of p-nitrochlorobenzene and mercaptoethanol, the total yield can reach 86-87%, in the reaction process, the reaction has fewer byproducts in each step, the amount of waste water is less, the price of raw materials is advantageous, and the defects are that DMF is used as a solvent in the condensation reaction, the DMF has high cost and toxicity, the waste water contains mercaptoethanol, the odor is generated, and the difficulty in waste water treatment is high.
Patent CN109867388A discloses a sewage treatment method for synthesizing para-ester by a para-nitrochlorobenzene route, which only solves the problem of DMF in wastewater, basically has no treatment effect on substances such as mercaptoethanol in wastewater, and the like, and calcium formate is difficult to be used as a byproduct without refining in the actual operation process, so that the whole treatment effect is limited.
Patent CN107758966A discloses a photocatalytic treatment method for para-ester production wastewater, which improves the biodegradability of the wastewater by flocculation precipitation and photocatalytic oxidation methods, and has low treatment efficiency and limited COD removal rate.
Therefore, at present, a feasible, economically feasible treatment technology for para-ester synthetic wastewater is urgently needed. In particular, the process wastewater for synthesizing para-ester by a mercaptoethanol method para-nitrochlorobenzene route has the characteristics of high concentration, high toxicity, difficult degradation and large treatment difficulty, and the problem of relevant wastewater treatment needs to be solved by technical breakthrough.
The invention aims to provide a complete and efficient treatment process for wastewater which is generated by synthesizing para-ester by a mercaptoethanol method and has high COD concentration, contains DMF (dimethyl formamide) and other refractory organic matters, contains malodor existing in thiol compounds and other difficulties, and the treated wastewater reaches GB8978-96 three-level discharge standard.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a method for processing the waste water that the mercaptoethanol method synthesizes and positions ester to produce, synthesize the waste water that positions ester to produce through catalyzing the wet oxidation-biochemical treatment, the waste water reaches GB8978-96 three-grade discharge standard after processing; the wastewater and the catalyst are mixed and enter a heat exchanger tube pass to exchange heat with the reacted high-temperature oxidation wastewater, catalytic wet oxidation pretreatment is carried out, and then the wastewater is heated to the reaction temperature through high-temperature heat conducting oil by a preheater and enters an oxidation reactor to realize catalytic wet oxidation reaction.
The gas-liquid mixture after oxidation in the oxidation reactor returns to the shell pass of the heat exchanger, exchanges heat with the wastewater containing the catalyst before oxidation in the tube pass of the heat exchanger, is heated to reaction temperature by high-temperature heat conducting oil through a preheater after heat exchange, enters the oxidation reactor, and is introduced with air to perform oxidation reaction by controlling pressure through a pressure reducing valve;
after the heat exchange, the gas-liquid mixture oxidized in the shell pass is subjected to pH value adjustment to be alkaline, the oxidized gas-liquid mixture is decompressed to normal pressure in a separator through a decompression valve, air is supplemented in the separator for flash evaporation to remove dimethylamine, liquid-phase wastewater is subjected to biochemical treatment to reach the GB8978-96 three-level discharge standard, and the wastewater treatment is realized.
The active component of the catalyst is one or more of copper salt, ferric salt and manganese salt;
wherein the copper salt is copper sulfate, copper nitrate or copper chloride; the ferric salt is ferric sulfate, ferric chloride or ferric nitrate; the manganese salt is manganese sulfate, manganese nitrate or manganese chloride.
The final concentration of the catalyst in the solution formed by mixing the catalyst and the wastewater is 100-500 ppm.
The wastewater and the catalyst are subjected to oxidation reaction in an oxidation reactor under the existence of compressed air, the reaction temperature is 200-300 ℃, the reaction time is 0.5-2 hours, and the reaction pressure is 4-12 MPa.
Adjusting the pH value of the oxidized wastewater in the shell layer of the heat exchanger to 9-11, reducing the pressure by a pressure reducing valve, feeding the reduced wastewater into a gas-liquid separator for flash evaporation, introducing air into the bottom of the separator, and cooling and absorbing the gas phase by an absorption tower to obtain a dimethylamine aqueous solution as a byproduct; the liquid phase is discharged into a biochemical regulating tank through a cooler.
The pressure of the pressure reducing valve is normal pressure after pressure reduction; the volume ratio of the air flow to the wastewater flow introduced into the separator is 75: 1.
mixing the liquid-phase wastewater and low-concentration plant wastewater in an adjusting tank, treating the mixed liquid-phase wastewater through an AO biochemical system, and then treating the mixed liquid-phase wastewater through a sedimentation tank to obtain effluent which is standard wastewater and directly discharging the effluent; wherein, the AO biochemical system comprises two parts of hydrolysis acidification and aerobic biochemistry.
Introducing the mixed wastewater in the regulating tank into a hydrolysis acidification tank, stirring and homogenizing by adopting plug flow, and keeping for 4-6 hours; after homogenizing treatment, the wastewater enters an aerobic tank, a contact oxidation process is adopted for aerobic biochemical treatment, air aeration is carried out, and the retention time is 16-24 hours; then biochemical effluent enters a secondary sedimentation tank for sludge-water separation; and (4) directly discharging the sorted effluent, namely the standard-reaching wastewater, refluxing a part of mud obtained by separation to a hydrolysis acidification tank, and discharging a part of mud.
The reflux ratio of the hydrolysis acidification tank to the aerobic tank is 2-4: 1.
the invention has the advantages that:
1. the invention creatively applies the catalytic wet oxidation pretreatment technology aiming at the para-ester high-concentration process wastewater, and the treatment process flow is simple; the device occupies a small area, and the total occupied area is about 400 square meters calculated by 200 tons per day of treatment scale; the treatment efficiency is high, the reaction time is about 1 hour, and the COD removal rate reaches more than 90%; no solid waste is generated in the treatment process; the odor of the treated wastewater disappears; the biodegradability of the treated wastewater is obviously improved, BOD5The COD is increased from 0.1 to more than 0.4; the self heat release of the oxidation reaction can be recycled, so the operation cost is low, about 2 yuan/kgCOD;
2. the invention effectively combines the catalytic wet oxidation gas-liquid separation process and the ammonia stripping process, and not only realizes the separation of air and wastewater, but also realizes the separation and collection of ammonia substances in the gas-liquid separator through process innovation, so that the ammonia substances can be recycled;
3. the catalytic wet oxidation-biochemical combined treatment process provided by the invention has the advantages that the whole process is simple and efficient, the flow is simple and continuous, most of COD is removed through catalytic wet oxidation pretreatment, DMF is decomposed, the biodegradability is improved, and the deodorizing and decoloring effects are achieved; meanwhile, the combined design of the flash evaporation unit in the process fully utilizes the catalytic wet oxidation heat to separate and recycle dimethylamine after DMF decomposition, so that the heat full utilization and dimethylamine recycling can be realized; in the process, an AO biochemical treatment device is used for realizing effective treatment of the pre-treated mercaptoethanol method para-ester synthetic wastewater and reaching the GB8978-96 standard, wherein COD is less than 500 mg/L.
Drawings
FIG. 1 is a flow chart of a wastewater treatment process provided by an embodiment of the invention.
The specific implementation mode is as follows:
the technical solution of the present invention will be described in further detail below with reference to examples.
The treatment process comprises the steps of firstly inputting the para-ester production wastewater into a catalytic wet oxidation system through a high-pressure pump, adding liquid alkali into the wastewater after oxidation treatment to adjust the pH value to 9-11, carrying out flash evaporation and stripping, absorbing tail gas with water to form a dimethylamine aqueous solution byproduct, feeding the wastewater after wet oxidation treatment into a distribution tank, mixing the wastewater with low-concentration wastewater in a plant area uniformly, adding nutrient salt, feeding the wastewater into an AO biochemical device, and carrying out mud-water separation on aerobic effluent through a sedimentation tank to achieve the standard and discharging. The invention develops a catalytic wet oxidation-biochemical combined treatment process aiming at the characteristics of high content of DMF (dimethyl formamide) and other difficultly biodegradable substances, high chroma, organic sulfide malodor and the like in para-nitrochlorobenzene synthesized by a mercaptoethanol method, and has the advantages of simple process flow, high treatment efficiency, no generation of solid waste and the like, and the treated wastewater reaches the GB8978-96 three-level discharge standard.
Example 1
A process device for wastewater treatment is shown in figure 1, and comprises a heat exchanger, a preheater and a reactor (oxidation reactor) which are connected in sequence through pipelines; the other end of the reactor is connected with an air compressor 1 through a pipeline; meanwhile, the water outlet of the reactor is communicated with the shell inlet of the heat exchanger through a pipeline; the other end of the heat exchanger is connected with a waste water storage tank through a pipeline, a high-pressure pump and a catalyst storage tank are arranged on an inlet pipeline, and a flow pump is arranged behind the catalyst storage tank; the preheater is communicated with the hot oil furnace through a pipeline;
the water outlet of the heat exchanger is connected with the gas-liquid separator through a pipeline, a pressure reducing valve is arranged on the pipeline, and the other end of the condenser is connected with the condenser 2 and the regulating tank through pipelines in sequence; a liquid caustic soda storage tank is arranged between the heat exchanger and the pressure reducing valve, and a high-pressure metering pump is arranged at the outlet of the liquid caustic soda storage tank; the other end of the gas-liquid separator is sequentially connected with the cooler 1 and the absorption tower through pipelines; the other end of the adjusting tank is connected with the hydrolysis acidification tank, the aerobic biochemical tank, the secondary sedimentation tank and the water outlet tank in sequence through pipelines.
The method for treating the wastewater by using the device comprises the following steps:
the mercaptoethanol p-chloronitrobenzene line p-ester synthetic wastewater from the wastewater reservoir passes through a high-pressure pump at a pressure of 4m3The wastewater COD is 48000mg/L, and is mixed with 10L/h 20% catalyst water solution pumped by a metering pump at the position of a pump inlet pipeline, the wastewater enters a shell-and-tube heat exchanger tube pass and a preheater tube pass in sequence, the temperature is raised to 240 ℃, the wastewater enters a reactor, and is mixed with air provided by an air compressor to carry out oxidation reaction in the oxidation reactor, the air flow is 15Nm3Min, controlling the reaction pressure to be 6MPa by a pressure reducing valve, reacting for 1h, allowing the oxidized wastewater to enter the shell side of the heat exchanger to perform heat exchange with catalyst-containing wastewater pumped into the tube side, cooling the oxidized wastewater to about 150 ℃, mixing the oxidized wastewater with 30% liquid caustic soda (sodium hydroxide solution) pumped by a high-pressure metering pump in a pipeline, adjusting the pH value of the oxidized wastewater to be about 10.5 by the liquid caustic soda flow of 100L/h, reducing the pressure of the oxidized gas-liquid mixture to the normal pressure in a separator by the pressure reducing valve, supplementing air into the separator, and controlling the flow to be 5Nm3Min, cooling the gas by cooler 1, absorbing with water, evacuating, cooling the liquid phase by cooler 2Then discharged into a biochemical regulating tank. Mixing the waste water after liquid phase oxidation in the regulating reservoir with low-concentration waste water, wherein the total water amount is about 200 tons/day, the COD is about 2000mg/L, the waste water in the regulating reservoir automatically flows into an AO biochemical pool, the waste water stays for 4 hours in a hydrolysis acidification pool (A pool), the waste water stays for 20 hours in an aerobic biochemical pool (O pool), the O pool forces the waste water to flow back to the A pool by a pump, and the flow is 25m3And h, feeding biochemical effluent into a secondary sedimentation tank for mud-water separation, pumping part of sludge back to the tank A by a screw pump, performing filter pressing on part of sludge in a dewatering room, and feeding the effluent of the secondary sedimentation tank into a water outlet tank for standard discharge. The effect of each unit treatment is shown in table 1.
The AO biochemical treatment process is carried out according to the prior art, which is referred to as the application of the A-O biochemical process in the coking wastewater treatment in the 12 th stage of 2018 of Henan chemical industry.
The catalyst is copper sulfate and manganese sulfate mixed salt, and the mass ratio is 2: 1.
TABLE 1
Example 2
The mercaptoethanol p-chloronitrobenzene line p-ester synthetic wastewater from the wastewater reservoir passes through a high-pressure pump at a pressure of 4m3The wastewater COD is 48000mg/L, and is mixed with 8L/h 20% catalyst water solution pumped by a metering pump at the position of a pump inlet pipeline, the wastewater enters a shell-and-tube heat exchanger tube pass and a preheater tube pass in sequence, the temperature is raised to 250 ℃, the wastewater enters a reactor, and is mixed with air provided by an air compressor to carry out oxidation reaction in the oxidation reactor, the air flow is 15Nm3Min, controlling the reaction pressure by a pressure reducing valve to be 7MPa, reacting for 2h, allowing the oxidized wastewater to enter the shell side of the heat exchanger to perform heat exchange with catalyst-containing wastewater pumped into the tube side, cooling the oxidized wastewater to about 150 ℃, mixing the oxidized wastewater with 30% liquid caustic soda (sodium hydroxide solution) pumped by a high-pressure metering pump in a pipeline, adjusting the pH value of the oxidized wastewater to be about 10.5, reducing the pressure of the oxidized gas-liquid mixture in a separator to be normal pressure by the pressure reducing valve, supplementing air into the separator, and allowing the flow to be 5Nm3Min, gasThe liquid phase is discharged into a biochemical regulating tank after being cooled by a cooler 2. Mixing the waste water after liquid phase oxidation in the regulating reservoir with low-concentration waste water, wherein the total water amount is about 200 tons/day, the COD is about 2000mg/L, the waste water in the regulating reservoir automatically flows into an AO biochemical pool, the waste water stays for 4 hours in a hydrolysis acidification pool (A pool), the waste water stays for 20 hours in an aerobic biochemical pool (O pool), the O pool forces the waste water to flow back to the A pool by a pump, and the flow is 25m3And h, feeding biochemical effluent into a secondary sedimentation tank for mud-water separation, pumping part of sludge back to the tank A by a screw pump, performing filter pressing on part of sludge in a dewatering room, and feeding the effluent of the secondary sedimentation tank into a water outlet tank for standard discharge. The processing effect of each unit is shown in table 2.
The AO biochemical treatment process is carried out according to the prior art, the catalyst is a copper salt (copper nitrate) and manganese salt (manganese nitrate) compound, and the mass ratio is 2: 1.
TABLE 2
Example 3
The mercaptoethanol p-chloronitrobenzene line p-ester synthetic wastewater from the wastewater reservoir passes through a high-pressure pump at a pressure of 4m3The wastewater COD is 48000mg/L, and is mixed with 10L/h 20% catalyst water solution pumped by a metering pump at the position of a pump inlet pipeline, the wastewater enters a shell-and-tube heat exchanger tube pass and a preheater tube pass in sequence, the temperature is raised to 260 ℃, the wastewater enters a reactor, and is mixed with air provided by an air compressor to carry out oxidation reaction in the oxidation reactor, the air flow is 15Nm3Min, controlling the reaction pressure by a pressure reducing valve to be 8MPa, controlling the reaction time to be 0.5h, allowing the oxidized wastewater to enter the shell side of the heat exchanger to exchange heat with catalyst-containing wastewater pumped into the tube side, cooling the oxidized wastewater to about 150 ℃, mixing the oxidized wastewater with 30% liquid caustic soda (sodium hydroxide solution) pumped by a high-pressure metering pump in a pipeline, adjusting the pH value of the oxidized wastewater to be about 10.5, reducing the pressure of the oxidized gas-liquid mixture to be normal pressure by the pressure reducing valve, supplementing air into a separator, and controlling the flow to be 5Nm3Min, cooling the gas by a cooler 1, absorbing the gas by water and emptying the gasAnd the liquid phase is discharged into a biochemical regulating tank after being cooled by the cooler 2. Mixing the waste water after liquid phase oxidation in the regulating reservoir with low-concentration waste water, wherein the total water amount is about 200 tons/day, the COD is about 2000mg/L, the waste water in the regulating reservoir automatically flows into an AO biochemical pool, the waste water stays for 4 hours in a hydrolysis acidification pool (A pool), the waste water stays for 20 hours in an aerobic biochemical pool (O pool), the O pool forces the waste water to flow back to the A pool by a pump, and the flow is 25m3And h, feeding biochemical effluent into a secondary sedimentation tank for mud-water separation, pumping part of sludge back to the tank A by a screw pump, performing filter pressing on part of sludge in a dewatering room, and feeding the effluent of the secondary sedimentation tank into a water outlet tank for standard discharge. The effect of each unit treatment is shown in table 3.
The AO biochemical treatment process is carried out according to the prior art, which is referred to as the application of the A-O biochemical process in the coking wastewater treatment in the 12 th stage of 2018 of Henan chemical industry.
The catalyst is formed by compounding copper salt (copper chloride) and manganese salt (manganese chloride) in a mass ratio of 2: 1.
TABLE 3
The embodiments described above are some of the embodiments of the present invention, and the detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but is merely representative of selected embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (9)
1. A method for treating wastewater generated by synthesizing para-ester by a mercaptoethanol method is characterized by comprising the following steps: the wastewater generated by synthesizing the para-ester is subjected to catalytic wet oxidation-biochemical treatment, and the treated wastewater reaches GB8978-96 three-level discharge standard; the wastewater and the catalyst are mixed and enter a heat exchanger tube pass to exchange heat with the reacted high-temperature oxidation wastewater, catalytic wet oxidation pretreatment is carried out, and then the wastewater is heated to the reaction temperature through high-temperature heat conducting oil by a preheater and enters an oxidation reactor to realize catalytic wet oxidation reaction.
2. The method of treating wastewater from the synthesis of para-esters by mercaptoethanol as claimed in claim 1, wherein: the method comprises the following steps that after oxidation in an oxidation reactor, a gas-liquid mixture returns to the shell pass of a heat exchanger, the gas-liquid mixture exchanges heat with waste water containing a catalyst before oxidation in the tube pass of the heat exchanger, the waste water is heated to a reaction temperature through high-temperature heat conducting oil through a preheater after heat exchange, the waste water enters the oxidation reactor, and air is introduced to perform oxidation reaction through the pressure controlled by a pressure reducing valve;
after the heat exchange, the gas-liquid mixture oxidized in the shell pass is subjected to pH value adjustment to be alkaline, the oxidized gas-liquid mixture is decompressed to normal pressure in a separator through a decompression valve, air is supplemented in the separator for flash evaporation to remove dimethylamine, liquid-phase wastewater is subjected to biochemical treatment to reach the GB8978-96 three-level discharge standard, and the wastewater treatment is realized.
3. The method for treating wastewater generated in the synthesis of para-ester by mercaptoethanol according to claim 1 or 2, characterized in that: the active component of the catalyst is one or more of copper salt, ferric salt and manganese salt;
the final concentration of the catalyst in the solution formed by mixing the catalyst and the wastewater is 100-500 ppm.
4. The method for treating wastewater generated in the synthesis of para-ester by mercaptoethanol according to claim 1 or 2, characterized in that: the wastewater and the catalyst are subjected to oxidation reaction in an oxidation reactor under the existence of compressed air, the reaction temperature is 200-300 ℃, the reaction time is 0.5-2 hours, and the reaction pressure is 4-12 MPa.
5. The method of treating wastewater from the synthesis of para-esters by mercaptoethanol as claimed in claim 2, wherein: adjusting the pH value of the oxidized wastewater in the shell layer of the heat exchanger to 9-11, reducing the pressure by a pressure reducing valve, feeding the reduced wastewater into a gas-liquid separator for flash evaporation, introducing air into the bottom of the separator, and cooling and absorbing the gas phase by an absorption tower to obtain a dimethylamine aqueous solution as a byproduct; the liquid phase is discharged into a biochemical regulating tank through a cooler.
6. The method of treating wastewater from the synthesis of para-esters by mercaptoethanol as claimed in claim 5, wherein: the pressure of the pressure reducing valve is normal pressure after pressure reduction; the volume ratio of the air flow to the wastewater flow introduced into the separator is 75: 1.
7. the method of treating wastewater from the synthesis of para-esters by mercaptoethanol as claimed in claim 5, wherein: mixing the liquid-phase wastewater and low-concentration plant wastewater in an adjusting tank, treating the mixed liquid-phase wastewater through an AO biochemical system, and then treating the mixed liquid-phase wastewater through a sedimentation tank to obtain effluent which is standard wastewater and directly discharging the effluent; wherein, the AO biochemical system comprises two parts of hydrolysis acidification and aerobic biochemistry.
8. The method of treating wastewater from the synthesis of para-esters by mercaptoethanol as claimed in claim 7, wherein: introducing the mixed wastewater in the regulating tank into a hydrolysis acidification tank, stirring and homogenizing by adopting plug flow, and keeping for 4-6 hours; after homogenizing treatment, the wastewater enters an aerobic tank, a contact oxidation process is adopted for aerobic biochemical treatment, air aeration is carried out, and the retention time is 16-24 hours; then biochemical effluent enters a secondary sedimentation tank for sludge-water separation; and (4) directly discharging the sorted effluent, namely the standard-reaching wastewater, refluxing a part of mud obtained by separation to a hydrolysis acidification tank, and discharging a part of mud.
9. The method of treating wastewater from the synthesis of para-esters by mercaptoethanol as claimed in claim 7, wherein: the reflux ratio of the hydrolysis acidification tank to the aerobic tank is 2-4: 1.
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| CN113003768A (en) * | 2021-02-24 | 2021-06-22 | 滨化集团股份有限公司 | Method for treating polyether polyol production wastewater and equipment for implementing method |
| CN113387485A (en) * | 2021-08-18 | 2021-09-14 | 北京惠宇乐邦环保科技有限公司 | Method for treating para-ester production wastewater through complex extraction |
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