Process for treating pharmaceutical intermediate wastewater

Abstract

A pharmaceutical intermediate wastewater treatment process, comprising the following steps: homogeneous conditioning for 22-26 hours; after homogeneous conditioning, directly entering the ozone catalytic oxidation system for COD degradation; the ozone catalytic oxidation system generates extremely strong hydroxyl radicals through the action of ozone on solid catalyst, which decomposes organic matter into mineralized carbon dioxide and water; PH is adjusted to 3-4; COD is degraded for the second time; impurities are removed; activated carbon adsorption; MVR evaporation treatment: the produced water enters the MVR system for evaporation treatment to obtain condensate and mixed salt; COD is degraded for the third time; organic matter is degraded; filtration; finally the turbidity of the produced water is less than or equal to 1 NTU, and the final produced water quality meets the industrial circulating water make-up water quality requirement, effectively treating the pharmaceutical intermediate wastewater.

Description

Technical Field

[0001] The present invention relates to the field of water treatment, in particular to a process for treating pharmaceutical intermediate wastewater. Background Art

[0002] Based on an analysis of the development trends of the high-efficiency, innovative pharmaceutical industry both domestically and internationally, and in response to current market demand and technological advancements in pharmaceutical intermediates, there is an urgent need for new technologies to produce efficient and environmentally friendly pharmaceutical intermediates and achieve industrialization. Pharmaceutical intermediates include intermediates for antibacterial drugs, antipyretics, analgesics, cardiovascular drugs, and anticancer drugs. Pharmaceutical intermediate wastewater is characterized by high pollutant concentrations, high salinity, complex composition, poor biodegradability, and significant toxicity. Furthermore, it is difficult to treat. Failure to treat or inadequate treatment will not only exacerbate water pollution but also pose a serious threat to public health. Pharmaceutical intermediate wastewater contains nearly 13% sodium chloride and 15,000 mg / L of COD. Directly feeding this high COD concentration into the evaporation system would cause foaming and disrupt stable operation. Furthermore, the resulting sodium chloride, high in organic matter, cannot be reused and must be treated as hazardous waste. Summary of the Invention

[0003] The LCO ozone catalyst used in the present invention is an ozone catalyst provided by Guangzhou Sunny Environmental Protection Technology Co., Ltd. The present invention provides a pharmaceutical intermediate wastewater treatment process, the final water quality of which meets the water quality requirements of industrial circulating water replenishment, and effectively treats pharmaceutical intermediate wastewater, comprising the following steps:

[0004] Step 1: Homogenization and adjustment: The raw water of pharmaceutical intermediates enters the regulating tank for homogenization and adjustment for 22-26 hours;

[0005] Step 2: Primary COD degradation: After homogenization, the wastewater directly enters the ozone catalytic oxidation system for COD degradation. The ozone catalytic oxidation system uses ozone to generate hydroxyl radicals with strong oxidizing ability under the action of a solid catalyst, decomposing organic matter into mineralized carbon dioxide and water. The oxidation potential of hydroxyl radicals is 2.80V, making it the second strongest oxidant in nature after fluorine (3.06V).

[0006] Step 3, pH adjustment: After ozone catalytic oxidation, the produced water enters the pH adjustment tank and adjusts the pH value to 3-4;

[0007] Step 4: Secondary degradation of COD: The produced water after pH adjustment enters the electrolytic catalytic oxidation system for secondary degradation of COD;

[0008] Step 5: Impurity removal: The secondary degradation water is directly overflowed into the coagulation sedimentation tank, and NaOH, PAC, and PAM are added to precipitate the suspended colloids, particulate impurities, and residual Fe ions in the water. The sediment is sent to the sludge storage tank for concentration and then pressed. The mud cake is stored as solid waste, and the supernatant and filtrate are returned to the regulating tank for recycling treatment.

[0009] Send the settled water into the sedimentation water tank;

[0010] The coagulation sedimentation tank employed in this invention is a compact, efficient, and flexible new sewage treatment process with wide application, including drinking water production, sewage treatment, industrial wastewater treatment, and sludge treatment. A high-density sedimentation tank is a water purification structure that utilizes the contact, adsorption, and precipitation of sludge residue with coagulants and impurity particles in the raw water to achieve mud-water separation. It offers high treatment efficiency, high water yield per unit area, strong adaptability, and stable treatment results.

[0011] The high-density sedimentation tank is mainly divided into three areas: coagulation reaction area, flocculation reaction area, and sedimentation and clarification area.

[0012] Step 6, activated carbon adsorption: The water produced in the sedimentation water production tank is pumped into the activated carbon adsorption device to adsorb the organic matter in the water and reduce the turbidity of the water. At this time, the organic matter in the water has been reduced by 70%-80% and can enter the MVR evaporation system for evaporation treatment;

[0013] Step 7, MVR evaporation treatment: The produced water enters the MVR system for evaporation treatment to obtain condensate. The condensate has a low salt content but still contains highly toxic COD, which requires secondary treatment. The sodium chloride in the raw water is precipitated in solid form through concentration and centrifugation. The final salt water content is less than 8%, and mixed salt is obtained after drying.

[0014] Step 8, tertiary COD degradation: The condensate is pumped into the ozone catalytic oxidation system again to open the COD chain and degrade the toxicity of organic matter. It then enters the hydrolysis and acidification tank for hydrolysis and acidification treatment to further degrade organic matter and improve B / C. Hydrolysis and acidification are two stages of the anaerobic nitrification process. Hydrolytic bacteria and acidifying bacteria are used to hydrolyze insoluble organic matter in water into soluble organic matter, and convert difficult-to-biodegrade macromolecules into easily biodegradable small molecules.

[0015] Step 9: Degradation of organic matter: The water produced after three degradations enters the water production pool and is mixed with domestic sewage. The mixed sewage enters the A / O biochemical system to degrade the organic matter.

[0016] Step 10, filtration: The produced water after the degradation of organic matter is finally filtered through the MBR system using the MBR process to make the turbidity of the produced water less than or equal to 1NTU.

[0017] Moreover, the activated carbon adsorption device is an activated carbon filter, which mainly utilizes activated carbon organic flocs with high carbon content, large molecular weight and large specific surface area to physically adsorb impurities in the water to meet water quality requirements. When water flows through the pores of the activated carbon, various suspended particles, organic matter, etc. are adsorbed in the pores of the activated carbon under the action of van der Waals force; at the same time, the chlorine (hypochlorous acid) adsorbed on the surface of the activated carbon undergoes a chemical reaction on the carbon surface and is reduced to chloride ions, thereby effectively removing chlorine and ensuring that the residual chlorine content in the effluent is less than 0.1ppm.

[0018] As time goes by, the retained matter in the pores and between the particles of the activated carbon gradually increases, causing the pressure difference before and after the filter to increase until it fails. Under normal circumstances, based on the pressure difference before and after the filter, the filter material is backwashed with reverse water flow, so that most of the retained matter adsorbed in the pores of the activated carbon is stripped off and carried away by the water flow, restoring the adsorption function. When the activated carbon reaches its saturated adsorption capacity and completely fails, the activated carbon should be regenerated or replaced to meet the requirements.

[0019] Moreover, the ozone catalytic oxidation system is an ozone generator. The core of the ozone generator adopts advanced dielectric barrier double-gap discharge technology. The raw gas flows through the narrow gap between the insulating medium and the high-voltage electrode, and between the insulating medium layer and the grounding electrode of the ozone generator tank. The high-voltage electric field between the two annular gaps discharges on both sides, converting the oxygen passing through into ozone, and the ozone production efficiency is high. The surface and cavities of the catalytic ozone oxidation catalyst can enrich and adsorb ozone and organic pollutants in water, increasing the local concentration of ozone and pollutants. The catalytic effect increases the conversion efficiency of ozone to hydroxyl radicals, greatly improving the concentration of hydroxyl radicals. The oxidizing properties of hydroxyl radicals are non-selective and highly efficient, making the reaction faster and the degradation of organic matter more thorough.

[0020] Moreover, the MVR evaporation process adopts falling film mechanical vapor compression recirculation evaporation technology, and the process flow is as follows:

[0021] 1) First, the sewage to be treated enters the liquid tank and is pumped into the heat exchanger. The final plate heat exchanger uses fresh steam to bring the water temperature to the boiling point. The MVR uses boiling point feed;

[0022] 2) The heated sewage uses steam to pass through the deaerator to remove oxygen, carbon dioxide, and non-condensable gases in the water, reducing corrosion and scaling hazards to the evaporator system;

[0023] 3) The sewage enters the bottom tank of the concentrator and is mixed with the high-salt sewage circulating inside the concentrator, and then sent to the water distribution device on the top of the heat exchanger for membrane coating.

[0024] The brine flows into the pipe through the liquid distributor on the top of the heat exchange pipe, is evenly distributed on the inner wall of the pipe, flows down to the bottom tank in a film shape; the high-salt sewage flows down along the pipe wall and exchanges heat with the steam in the shell side to concentrate and evaporate, and the steam and the unevaporated high-salt sewage drop to the bottom tank together; the secondary steam generated by evaporation enters the steam compressor through the demister, and the compressed steam enters the heat exchanger shell side after the temperature and pressure of the steam are increased by compression; the compressed steam is condensed in the shell side heat exchange, releases latent heat, heats the brine film with lower temperature which drops along the inner wall of the pipe, and makes part of the brine evaporate.

[0025] After the compressed steam releases latent heat, it is condensed into water on the outer wall of the heat exchange pipe, drops along the pipe wall, and accumulates at the bottom of the heating chamber, and then is pumped to the first plate heat exchanger; when the condensed water flows through the heat exchanger, it heats the high-salt sewage, and then the high-salt sewage is heated by the steam plate to near the boiling point of the liquid and enters the evaporation system. A small amount of high-salt sewage is discharged to control the concentration of the brine in the evaporation concentrator.

[0026] In addition to the need for external steam during startup, the liquid feed still needs a certain amount of steam to make the liquid reach the boiling point. During normal operation, the heat energy required for evaporation of sewage is mainly provided by the heat released or exchanged during steam condensation and condensate cooling. Electricity is mainly used as a heat source during the evaporation process instead of steam.

[0027] Moreover, the electrolytic catalytic oxidation system adopts FCM catalytic self-electrolysis process to oxidize, reduce, flocculate, adsorb and precipitate COD, ammonia nitrogen, cyanide, phenol and organic sulfides, so as to achieve the removal effect.

[0028] Moreover, the A / O biochemical system adopts A / O new ecological denitrification and decarburization process, the core of which is high-efficiency denitrification filler, which is made of organic and inorganic composite materials, has a large specific surface area, is hydrophilic and microorganism-friendly, and has a film quantity of 15-20 g / L.

[0029] In the high-efficiency denitrification filler, first, in the outermost aerobic layer, carbonization bacteria can convert organic matter into easily degradable organic matter and CO2, and at the same time, nitrosation bacteria and nitrification bacteria can convert NH3-N into NO2-N and NO3-N; second, in the anoxic layer, NO2-N and NO3-N can be denitrified into N2; third, in the innermost anaerobic layer, the non-easily degradable organic matter can be converted into easily degradable organic matter as a denitrification carbon source, and anaerobic ammonia oxidation can also occur in this layer.

[0030] Moreover, the MBR process adopts an immersed membrane.

[0031] The MBR process is a wastewater treatment technology that combines suspended growth biological treatment with submerged membrane filtration. The MBR membrane acts as the solid-liquid separation step in the treatment process, replacing traditional secondary clarifiers and tertiary filters. Because the pore size of the MBR membrane is sufficiently small, solid particles are prevented from passing through the membrane, resulting in very high permeate (filtrate) performance.

[0032] MBR combines membrane filtration technology with the same biological treatment found in traditional activated sludge processes. As in traditional activated sludge processes, wastewater is treated by activated sludge in an aerated reactor shell. The sludge contains enzymatic potential to convert harmful pollutants in the wastewater, such as nitrogen and carbon compounds, into less harmful substances. To promote stable biological activity in the reactor, an adequate supply of oxygen must be provided to the system via air aeration tubes. In the final separation step, the membrane acts as a physical barrier between the mixed liquor and the purified water; vacuum is applied to the membrane. The pressure difference between the outside and inside of the membrane is called the transmembrane pressure (TMP). The clean water, known as "permeate," can be collected in a production water tank for further recycling or discharged directly.

[0033] Moreover, the solid catalyst is an LCO ozone catalyst.

[0034] Moreover, hydrolysis and acidification reactions are two stages of the anaerobic nitrification process, which use hydrolytic bacteria and acidifying bacteria to hydrolyze insoluble organic matter in water into soluble organic matter, and convert difficult-to-biodegrade macromolecules into easily biodegradable small molecules.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] 1. The present invention undergoes three COD degradation processes in the ozone catalytic oxidation system, the electrolytic catalytic oxidation system, and the ozone catalytic oxidation system. The turbidity of the produced water is less than or equal to 1 NTU, and the final produced water quality meets the requirements for industrial circulating water replenishment, effectively treating pharmaceutical intermediate wastewater.

[0037] 2. The present invention concentrates and centrifuges sodium chloride in pharmaceutical intermediate wastewater to precipitate mixed salts, which can be recycled and reused, which is economical and environmentally friendly.

[0038] 3. The process technology selected by the present invention is advanced and mature, has strong adaptability to changes in water quality, is stable in operation and easy to manage, and adopts advanced, reasonable and reliable treatment technology. On the premise of ensuring the treatment effect, the process flow is simple, the operation is simple, the management is convenient, the land occupation is small, the investment is low and the operating cost is low.

[0039] 4. The electrolytic catalytic oxidation system of the present invention adopts the FCM catalytic self-electrolysis process, which has the advantages of wide application range, good treatment effect, low cost, easy operation and maintenance, and no need to consume electricity resources.

[0040] 5. The present invention will produce water after three degradations into the water production pool and mix it with domestic sewage. The mixed sewage will enter the A / O biochemical system to degrade organic matter and finally be filtered and treated.

[0041] The turbidity of the produced water is made less than or equal to 1NTU, and finally meets the standard. It can not only effectively treat the wastewater of pharmaceutical intermediates, but also treat domestic sewage.

[0042] 6. The present invention continuously recycles and treats pharmaceutical intermediate wastewater, ultimately meeting standards, thereby achieving safe, environmentally friendly, clean, and civilized production. The comprehensive treatment of pharmaceutical intermediate wastewater is a major challenge in waste liquid treatment. The process route and treatment method adopted in the present invention can be replicated and constructed on a large scale, with significant social, economic, and environmental benefits. It can also effectively improve the problem of production wastewater pollution, which is of great significance for protecting the production and living environment of residents in the region and promoting harmonious coexistence between man and nature. BRIEF DESCRIPTION OF THE DRAWINGS

[0043] Figure 1 It is a schematic flow diagram of the present invention;

[0044] Figure 2 This is an experimental effect diagram of the present invention. DETAILED DESCRIPTION

[0045] Example 1

[0046] A pharmaceutical intermediate wastewater treatment process comprises the following steps:

[0047] Step 1: Homogenization and adjustment: The raw water of pharmaceutical intermediates enters the regulating tank for homogenization and adjustment for 22 hours;

[0048] Step 2, COD primary degradation: After homogenization and adjustment, it directly enters the ozone catalytic oxidation system for COD degradation; the ozone catalytic oxidation system generates hydroxyl radicals with strong oxidizing ability under the action of ozone on a solid catalyst, decomposing organic matter into mineralized carbon dioxide and water;

[0049] Step 3, pH adjustment: After ozone catalytic oxidation, the produced water enters the pH adjustment tank and the pH value is adjusted to 3;

[0050] Step 4: Secondary degradation of COD: The produced water after pH adjustment enters the electrolytic catalytic oxidation system for secondary degradation of COD;

[0051] Step 5: Impurity removal: The secondary degradation water is directly overflowed into the coagulation sedimentation tank, and NaOH, PAC, and PAM are added to precipitate the suspended colloids, particulate impurities, and residual Fe ions in the water. The sediment is sent to the sludge storage tank for concentration and then pressed. The mud cake is stored as solid waste, and the supernatant and filtrate are returned to the regulating tank for recycling treatment.

[0052] Send the settled water into the sedimentation water tank;

[0053] Step 6, activated carbon adsorption: pump the water produced in the sedimentation water production tank into the activated carbon adsorption device to adsorb organic matter in the water and reduce the turbidity of the water;

[0054] Step 7, MVR evaporation treatment: The produced water enters the MVR system for evaporation treatment to obtain condensate; sodium chloride in the raw water is concentrated and centrifuged to precipitate in solid form, and the final salt water content is 7.5%. After drying, mixed salt is obtained;

[0055] Step 8, COD tertiary degradation: The condensate is pumped into the ozone catalytic oxidation system again to open the COD chain and degrade the toxicity of organic matter. It then enters the hydrolysis and acidification tank for hydrolysis and acidification treatment to further degrade organic matter and improve B / C.

[0056] Step 9: Degradation of organic matter: The water produced after three degradations enters the water production pool and is mixed with domestic sewage. The mixed sewage enters the A / O biochemical system to degrade the organic matter.

[0057] Step 10, filtration: The produced water after the degradation of organic matter is finally filtered through the MBR system using the MBR process to make the turbidity of the produced water equal to 1NTU.

[0058] Furthermore, the coagulation sedimentation tank is a high-density sedimentation tank, which is mainly divided into three areas: a coagulation reaction area, a flocculation reaction area, and a sedimentation and clarification area.

[0059] Furthermore, the activated carbon adsorption device is an activated carbon filter, which uses granular activated carbon with high carbon content, large molecular weight and large specific surface area to physically adsorb residual chlorine, organic matter and suspended impurities remaining in the produced water; at the same time, the chlorine adsorbed on the surface of the activated carbon undergoes a chemical reaction on the carbon surface and is reduced to chloride ions, so that the residual chlorine content in the effluent is less than 0.09ppm.

[0060] Furthermore, the ozone catalytic oxidation system is an ozone generator that adopts dielectric barrier double-gap discharge technology.

[0061] Furthermore, the MVR evaporation process adopts falling film mechanical vapor compression recirculation evaporation technology, and the process flow is as follows:

[0062] 1) First, the sewage to be treated enters the liquid tank and is pumped into the heat exchanger. The final plate heat exchanger uses fresh steam to bring the water temperature to the boiling point. The MVR uses boiling point feed;

[0063] 2) The heated sewage uses steam to pass through a deaerator to remove oxygen, carbon dioxide, and non-condensable gases from the water;

[0064] 3) The sewage enters the bottom tank of the concentrator and is mixed with the high-salt sewage circulating inside the concentrator, and then sent to the water distribution device on the top of the heat exchanger for membrane coating.

[0065] Furthermore, the electrolytic catalytic oxidation system adopts FCM catalytic self-electrolysis process to oxidize, reduce, flocculate, adsorb and precipitate COD, ammonia nitrogen, cyanide, phenol and organic sulfide to achieve the removal effect.

[0066] Furthermore, the A / O biochemical system adopts the A / O new ecological denitrification and decarbonization process. The core of the A / O new ecological denitrification and decarbonization process is a high-efficiency denitrification filler. The high-efficiency denitrification filler adopts an organic and inorganic composite material with a large specific surface area, is hydrophilic and microbial-friendly, and has a biofilm capacity of 15g / L.

[0067] Furthermore, the MBR process uses a submerged membrane.

[0068] Furthermore, the solid catalyst is an LCO ozone catalyst.

[0069] Example 2

[0070] A pharmaceutical intermediate wastewater treatment process comprises the following steps:

[0071] Step 1: Homogenization and adjustment: The raw water of pharmaceutical intermediates enters the regulating tank for homogenization and adjustment for 26 hours;

[0072] Step 2, COD primary degradation: After homogenization and adjustment, it directly enters the ozone catalytic oxidation system for COD degradation; the ozone catalytic oxidation system generates hydroxyl radicals with strong oxidizing ability under the action of ozone on a solid catalyst, decomposing organic matter into mineralized carbon dioxide and water;

[0073] Step 3, pH adjustment: After ozone catalytic oxidation, the produced water enters the pH adjustment tank and the pH value is adjusted to 4;

[0074] Step 4: Secondary degradation of COD: The produced water after pH adjustment enters the electrolytic catalytic oxidation system for secondary degradation of COD;

[0075] Step 5: Impurity removal: The secondary degradation water is directly overflowed into the coagulation sedimentation tank, and NaOH, PAC, and PAM are added to precipitate the suspended colloids, particulate impurities, and residual Fe ions in the water. The sediment is sent to the sludge storage tank for concentration and then pressed. The mud cake is stored as solid waste, and the supernatant and filtrate are returned to the regulating tank for recycling treatment.

[0076] Send the settled water into the sedimentation water tank;

[0077] Step 6, activated carbon adsorption: pump the water produced in the sedimentation water production tank into the activated carbon adsorption device to adsorb organic matter in the water and reduce the turbidity of the water;

[0078] Step 7, MVR evaporation treatment: The produced water enters the MVR system for evaporation treatment to obtain condensate; sodium chloride in the raw water is concentrated and centrifuged to precipitate in solid form, and the final salt water content is 7%. After drying, mixed salt is obtained;

[0079] Step 8, COD tertiary degradation: The condensate is pumped into the ozone catalytic oxidation system again to open the COD chain and degrade the toxicity of organic matter. It then enters the hydrolysis and acidification tank for hydrolysis and acidification treatment to further degrade organic matter and improve B / C.

[0080] Step 9: Degradation of organic matter: The water produced after three degradations enters the water production pool and is mixed with domestic sewage. The mixed sewage enters the A / O biochemical system to degrade the organic matter.

[0081] Step 10, filtration: The produced water after the degradation of organic matter is finally filtered through the MBR system using the MBR process to make the turbidity of the produced water equal to 0.9NTU.

[0082] Furthermore, the coagulation sedimentation tank is a high-density sedimentation tank, which is mainly divided into three areas: a coagulation reaction area, a flocculation reaction area, and a sedimentation and clarification area.

[0083] Furthermore, the activated carbon adsorption device is an activated carbon filter, which uses granular activated carbon with high carbon content, large molecular weight and large specific surface area to physically adsorb residual chlorine, organic matter and suspended impurities remaining in the produced water; at the same time, the chlorine adsorbed on the surface of the activated carbon undergoes a chemical reaction on the carbon surface and is reduced to chloride ions, so that the residual chlorine content in the effluent is 0.08ppm.

[0084] Furthermore, the ozone catalytic oxidation system is an ozone generator that adopts dielectric barrier double-gap discharge technology.

[0085] Furthermore, the MVR evaporation process adopts falling film mechanical vapor compression recirculation evaporation technology, and the process flow is as follows:

[0086] 1) First, the sewage to be treated enters the liquid tank and is pumped into the heat exchanger. The final plate heat exchanger uses fresh steam to bring the water temperature to the boiling point. The MVR uses boiling point feed;

[0087] 2) The heated sewage uses steam to pass through a deaerator to remove oxygen, carbon dioxide, and non-condensable gases from the water;

[0088] 3) The sewage enters the bottom tank of the concentrator and is mixed with the high-salt sewage circulating inside the concentrator, and then sent to the water distribution device on the top of the heat exchanger for membrane coating.

[0089] Furthermore, the electrolytic catalytic oxidation system adopts FCM catalytic self-electrolysis process to oxidize, reduce, flocculate, adsorb and precipitate COD, ammonia nitrogen, cyanide, phenol and organic sulfide to achieve the removal effect.

[0090] Furthermore, the A / O biochemical system adopts the A / O new ecological denitrification and decarbonization process. The core of the A / O new ecological denitrification and decarbonization process is a high-efficiency denitrification filler. The high-efficiency denitrification filler adopts an organic and inorganic composite material with a large specific surface area, hydrophilicity, and affinity to microorganisms, and the biofilm amount is 20g / L.

[0091] Furthermore, the MBR process uses a submerged membrane.

[0092] Furthermore, the solid catalyst is an LCO ozone catalyst.

[0093] Example 3

[0094] A pharmaceutical intermediate wastewater treatment process comprises the following steps:

[0095] Step 1: Homogenization and adjustment: The raw water of pharmaceutical intermediates enters the regulating tank for homogenization and adjustment for 24 hours;

[0096] Step 2, COD primary degradation: After homogenization and adjustment, it directly enters the ozone catalytic oxidation system for COD degradation; the ozone catalytic oxidation system generates hydroxyl radicals with strong oxidizing ability under the action of ozone on a solid catalyst, decomposing organic matter into mineralized carbon dioxide and water;

[0097] Step 3, pH adjustment: After ozone catalytic oxidation, the produced water enters the pH adjustment tank and the pH value is adjusted to 3.5;

[0098] Step 4: Secondary degradation of COD: The produced water after pH adjustment enters the electrolytic catalytic oxidation system for secondary degradation of COD;

[0099] Step 5: Impurity removal: The secondary degradation water is directly overflowed into the coagulation sedimentation tank, and NaOH, PAC, and PAM are added to precipitate the suspended colloids, particulate impurities, and residual Fe ions in the water. The sediment is sent to the sludge storage tank for concentration and then pressed. The mud cake is stored as solid waste, and the supernatant and filtrate are returned to the regulating tank for recycling treatment.

[0100] Send the settled water into the sedimentation water tank;

[0101] Step 6, activated carbon adsorption: pump the water produced in the sedimentation water production tank into the activated carbon adsorption device to adsorb organic matter in the water and reduce the turbidity of the water;

[0102] Step 7, MVR evaporation treatment: The produced water enters the MVR system for evaporation treatment to obtain condensate; sodium chloride in the raw water is concentrated and centrifuged to precipitate in solid form, and the final salt water content is 6.5%. After drying, mixed salt is obtained;

[0103] Step 8, COD tertiary degradation: The condensate is pumped into the ozone catalytic oxidation system again to open the COD chain and degrade the toxicity of organic matter. It then enters the hydrolysis and acidification tank for hydrolysis and acidification treatment to further degrade organic matter and improve B / C.

[0104] Step 9: Degradation of organic matter: The water produced after three degradations enters the water production pool and is mixed with domestic sewage. The mixed sewage enters the A / O biochemical system to degrade the organic matter.

[0105] Step 10, filtration: The produced water after the degradation of organic matter is finally filtered through the MBR system using the MBR process to make the turbidity of the produced water equal to 0.08NTU.

[0106] Furthermore, the coagulation sedimentation tank is a high-density sedimentation tank, which is mainly divided into three areas: a coagulation reaction area, a flocculation reaction area, and a sedimentation and clarification area.

[0107] Furthermore, the activated carbon adsorption device is an activated carbon filter, which uses granular activated carbon with high carbon content, large molecular weight and large specific surface area to physically adsorb residual chlorine, organic matter and suspended impurities remaining in the produced water; at the same time, the chlorine adsorbed on the surface of the activated carbon undergoes a chemical reaction on the carbon surface and is reduced to chloride ions, so that the residual chlorine content in the effluent is 0.07ppm.

[0108] Furthermore, the ozone catalytic oxidation system is an ozone generator that adopts dielectric barrier double-gap discharge technology.

[0109] Furthermore, the MVR evaporation process adopts falling film mechanical vapor compression recirculation evaporation technology, and the process flow is as follows:

[0110] 1) First, the sewage to be treated enters the liquid tank and is pumped into the heat exchanger. The final plate heat exchanger uses fresh steam to bring the water temperature to the boiling point. The MVR uses boiling point feed;

[0111] 2) The heated sewage uses steam to pass through a deaerator to remove oxygen, carbon dioxide, and non-condensable gases from the water;

[0112] 3) The sewage enters the bottom tank of the concentrator and is mixed with the high-salt sewage circulating inside the concentrator, and then sent to the water distribution device on the top of the heat exchanger for membrane coating.

[0113] Furthermore, the electrolytic catalytic oxidation system adopts FCM catalytic self-electrolysis process to oxidize, reduce, flocculate, adsorb and precipitate COD, ammonia nitrogen, cyanide, phenol and organic sulfide to achieve the removal effect.

[0114] Furthermore, the A / O biochemical system adopts the A / O new ecological denitrification and decarbonization process. The core of the A / O new ecological denitrification and decarbonization process is a high-efficiency denitrification filler. The high-efficiency denitrification filler adopts an organic and inorganic composite material with a large specific surface area, is hydrophilic and microbial-friendly, and has a biofilm capacity of 18g / L.

[0115] Furthermore, the MBR process uses a submerged membrane.

[0116] Furthermore, the solid catalyst is an LCO ozone catalyst.

[0117] Experimental part

[0118] Experiment 1:

[0119] Two groups of raw water from pharmaceutical intermediates were taken, and the pH value, TDS, COD and ammonia nitrogen content of the raw water were measured. After ozone catalytic oxidation treatment for 1 hour and 2 hours respectively, the pH value, TDS, COD and ammonia nitrogen content of the treated water were measured again, and the COD removal rate was calculated. The specific experimental data are shown in Table 1.

[0120] Table 1 Ozone catalytic oxidation treatment results

[0121] Water sample indicators raw water Ozone 1h Ozone 2h PH ＞14 ＞14 ＞14 TDS 176500 106500 96200 COD 2219.75 1279.25 1128.25 COD removal rate - 42.36% 49.14% Ammonia nitrogen 29.45 0 0 color dark brown Green-brown Green-brown

[0122] Experiment 2:

[0123] Take 3 groups of raw water for pharmaceutical intermediates, measure the pH value, TDS and COD of the raw water, record the data, and conduct the following experiments on the three groups of raw water:

[0124] Group 1: simulated FCM catalytic self-electrolysis process for 1 hour;

[0125] Group 2: simulated FCM catalytic self-electrolysis process for 2 hours;

[0126] Group 2: simulated FCM catalytic self-electrolysis process for 2 hours followed by simulated MVR evaporation treatment, and the condensate and mother liquor were collected;

[0127] The pH value, TDS and COD of each group of samples after treatment were measured, and the COD removal rate was calculated. The specific experimental data are shown in Table 2.

[0128] Table 2 Results of FCM catalytic self-electrolysis process and MVR evaporation treatment

[0129] Water sample indicators raw water Self-electrolysis 1h Self-electrolysis 2h Electrolysis 2h+MVR / condensate Electrolysis 2h+MVR / mother liquor PH ＞14 8 7.6 7.5 6.5 TDS 176500 87250 87250 449 30500 COD 2219.75 790 677.25 25.58 2190 COD removal rate - 64.41 69.48 98.84 - color dark brown yellow-green yellow-green colorless yellow

[0130] It can be seen from the above experimental data that the ozone catalytic oxidation process, FCM catalytic self-electrolysis process and MVR evaporation adopted in the present invention can play a very good effect on the treatment of pharmaceutical intermediate wastewater, and have a significant effect on COD degradation. The present invention is of great significance for protecting the production and living environment of residents in the region and promoting harmonious coexistence between man and nature.

Claims

1. A pharmaceutical intermediate wastewater treatment process, characterized in that: The steps include: Step 1: Homogenization and adjustment: The raw water of pharmaceutical intermediates enters the regulating tank for homogenization and adjustment for 22-26 hours; Step 2, COD primary degradation: After homogenization adjustment, it directly enters the ozone catalytic oxidation system for COD degradation; the ozone catalytic oxidation system generates hydroxyl free radicals with strong oxidizing ability under the action of ozone on a solid catalyst, decomposing organic matter into mineralized matter; The solid catalyst is an LCO ozone catalyst; The ozone catalytic oxidation system is an ozone generator that adopts dielectric barrier double-gap discharge technology; Step 3, pH adjustment: After ozone catalytic oxidation, the produced water enters the pH adjustment tank and the pH value is adjusted to 3-4; Step 4, COD secondary degradation: The produced water after pH adjustment enters the electrolytic catalytic oxidation system for COD secondary degradation; the electrolytic catalytic oxidation system adopts FCM catalytic self-electrolysis process to oxidize, reduce, flocculate, adsorb and precipitate COD, ammonia nitrogen, cyanide, phenol and organic sulfide to achieve the removal effect; Step 5, impurity removal: The secondary degradation produced water is directly overflowed into the coagulation sedimentation tank, and NaOH, PAC, and PAM are added to settle the suspended colloids, particulate impurities and residual Fe ions in the produced water. The sediment is sent to the sludge storage tank for concentration and then squeezed. The mud cake is stored as solid waste, and the supernatant and filtrate are returned to the regulating tank for recycling treatment; the produced water after sedimentation is sent to the sedimentation water production tank; Step 6, activated carbon adsorption: pump the water produced in the sedimentation water production tank into the activated carbon adsorption device to adsorb organic matter in the water and reduce the turbidity of the water; Step 7, MVR evaporation treatment: the produced water enters the MVR system for evaporation treatment to obtain condensate; Sodium chloride in the raw water is precipitated in solid form by concentration and centrifugation, and the final salt water content is less than 8%. After drying, mixed salt is obtained; Step 8, COD tertiary degradation: The condensate is pumped into the ozone catalytic oxidation system again to open the COD chain and degrade the toxicity of organic matter. It then enters the hydrolysis and acidification tank for hydrolysis and acidification treatment to further degrade organic matter and improve B / C. Step 9, organic matter degradation: After three degradations, the produced water enters the water production pool and is mixed with domestic sewage. The mixed sewage enters the A / O biochemical system to degrade the organic matter; Step 10, filtration: The produced water after the degradation of organic matter is finally filtered through the MBR system using the MBR process to make the turbidity of the produced water less than or equal to 1NTU; The MVR evaporation process adopts falling film mechanical vapor compression recirculation evaporation technology, and the process flow is as follows: 1) First, the sewage to be treated enters the liquid tank and is pumped into the heat exchanger. The final plate heat exchanger uses fresh steam to bring the water temperature to the boiling point. The MVR uses boiling point feed; 2) The heated sewage uses steam to pass through a deaerator to remove oxygen, carbon dioxide, and non-condensable gases from the water; 3) The sewage enters the bottom tank of the concentrator and is mixed with the high-salt sewage circulating inside the concentrator, and then sent to the water distribution device on the top of the heat exchanger for membrane coating.

2. A pharmaceutical intermediate wastewater treatment process according to claim 1, characterized in that: The coagulation sedimentation tank is a high-density sedimentation tank, which is mainly divided into three areas: a coagulation reaction area, a flocculation reaction area, and a sedimentation and clarification area.

3. A pharmaceutical intermediate wastewater treatment process according to claim 1, characterized in that: The activated carbon adsorption device is an activated carbon filter that uses granular activated carbon with high carbon content, large molecular weight and large specific surface area to physically adsorb residual chlorine, organic matter and suspended solids in the produced water; The chlorine adsorbed on the surface of activated carbon undergoes a chemical reaction on the carbon surface and is reduced to chloride ions, making the residual chlorine content in the effluent less than 0.1ppm.

4. A pharmaceutical intermediate wastewater treatment process according to claim 1, characterized in that: The A / O biochemical system adopts the A / O new ecological denitrification and decarbonization process. The core of the A / O new ecological denitrification and decarbonization process is the high-efficiency denitrification filler. The high-efficiency denitrification filler adopts organic and inorganic composite materials, has a large specific surface area, is hydrophilic and microbial-friendly, and has a biofilm capacity of 15-20g / L.

5. A pharmaceutical intermediate wastewater treatment process according to claim 1, characterized in that: The MBR process uses submerged membranes.

6. A pharmaceutical intermediate wastewater treatment process according to claim 1, characterized in that: The minerals are carbon dioxide and water.

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