CN113698043B - Resource utilization and advanced treatment method for raw material medicine production process wastewater - Google Patents

Resource utilization and advanced treatment method for raw material medicine production process wastewater Download PDF

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CN113698043B
CN113698043B CN202111048400.6A CN202111048400A CN113698043B CN 113698043 B CN113698043 B CN 113698043B CN 202111048400 A CN202111048400 A CN 202111048400A CN 113698043 B CN113698043 B CN 113698043B
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CN113698043A (en
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许建国
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Nanjing Southeast University Energy Engineering Design Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/30—Treatment of water, waste water, or sewage by irradiation
    • C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/28—Anaerobic digestion processes
    • C02F3/2846—Anaerobic digestion processes using upflow anaerobic sludge blanket [UASB] reactors
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes

Abstract

The invention discloses a resource utilization and advanced treatment method of raw material medicine production process wastewater, which is divided into four types of organic strong salt wastewater, low salt wastewater, light salt wastewater and inorganic strong salt wastewater according to the water quality according to the wastewater conditions generated in different links of the production process of aminomethylbenzoic acid. According to the invention, through wastewater quality-based treatment, the operation mode and the process parameters are adjusted according to different inlet water quality and outlet water quality requirements, so that the purpose of efficient wastewater treatment is achieved, the finally discharged water reaches the discharge standard, and meanwhile, resource utilization is effectively realized, and the device is convenient to operate and manage and flexible to operate.

Description

Resource utilization and advanced treatment method for raw material medicine production process wastewater
Technical Field
The invention relates to a resource utilization and advanced treatment method of raw material medicine production process wastewater, which is particularly suitable for raw material medicine wastewater treatment containing chlorination, ammoniation and ethanol refining processes. In particular, it is particularly effective for aminomethylbenzoic acid production wastewater. The method belongs to the technical field of environmental protection wastewater treatment.
Background
The waste water produced in the pharmaceutical industry is one of the waste water which is difficult to treat in China, and has complex components, high toxicity and difficult biochemical degradation. Taking Aminomethylbenzoic Acid as an example, a p-Aminomethylbenzoic Acid (p-Aminomethylbenzoic Acid) drug substance is used in China to prepare a Aminomethylbenzoic Acid injection or a Aminomethylbenzoic Acid tablet, which is a medicine for clinical application as a hemostatic. The production process principle of aminomethylbenzoic acid mainly includes chlorination reaction, ammoniation reaction and refining, in the chlorination reaction p-methylbenzoic acid is used as initial raw material, chlorobenzene is used as carrier, under the action of catalyst and chlorine gas the chlorination reaction can be made to produce intermediate, the reaction liquor produced by chlorination reaction and prepared ammonia water can be made to produce aminomethylbenzoic acid by means of ammoniation reaction, and the purity of the product aminomethylbenzoic acid is very high, so that it is required to use ethyl alcohol to make refining. Therefore, the wastewater generated in the production process of the aminomethylbenzoic acid contains chlorobenzene, ammonium chloride, halogenated hydrocarbon impurities, ammonia, ethanol and other toxic and harmful substances, and the regenerated wastewater generated in the mixed bed process contains a large amount of salt, so that the wastewater generated in the aminomethylbenzoic acid production line belongs to highly difficult-to-treat wastewater with high organic matter, high salt and high chlorobenzene. At present, no report is found on a series of treatment processes of wastewater generated by raw material medicines containing chlorination, ammoniation and refining production processes.
Disclosure of Invention
The invention provides a resource utilization and deep treatment method of raw material drug production process wastewater, which comprises the steps of pretreating the four types of wastewater according to wastewater conditions generated in different links of a raw material drug production process and according to water quality, pretreating the four types of wastewater, and carrying out multi-effect combined deep treatment on the pretreated organic strong salt wastewater and low salt wastewater to ensure that finally discharged water reaches a discharge standard and the pretreated inorganic strong salt wastewater and the light salt wastewater are recycled.
In order to achieve the purpose, the invention adopts the following technical scheme: a resource utilization and advanced treatment method of raw material drug production process wastewater is characterized in that according to wastewater conditions generated in different links of a raw material drug production process, the raw material drug production process is divided into four types of organic strong salt wastewater, low salt wastewater, light salt wastewater and inorganic strong salt wastewater according to water quality, the organic strong salt wastewater and the low salt wastewater are pretreated and then sent to a comprehensive wastewater treatment station for advanced treatment, and the inorganic strong salt wastewater and the light salt wastewater are pretreated and then recycled;
the comprehensive wastewater treatment station comprises an adjusting tank, a UASB (upflow anaerobic sludge blanket), a two-stage OA (anaerobic-anoxic sludge blanket), an MBR (membrane bioreactor) tank and a photooxidation tank, wherein the adjusting tank, the UASB, the two-stage OA tank, the MBR tank and the photooxidation tank are sequentially connected, the MBR tank is connected with a loop formed by the two-stage OA tank, and the adjusting tank is also connected with the two-stage OA tank;
the organic strong-salt wastewater is pretreated by a rectifying tower and a second triple-effect evaporator in sequence to obtain distillate and condensed organic wastewater, various salts in the organic strong-salt wastewater are mainly removed, volatile organic matters are recycled, the distillate is methanol or ethanol and can be reused for production, and the condensed organic wastewater enters an adjusting tank;
the low-salt wastewater also enters a regulating tank;
wherein, the organic strong brine wastewater is wastewater generated by recovering mother liquor and ethanol from the production of aminomethylbenzoic acid and acetone, the low-salt wastewater is wastewater and domestic sewage generated by backflushing a multi-media filter, the inorganic strong brine wastewater is regenerated wastewater generated by a mixed bed process, and the light-salt wastewater is wastewater generated by circulating water pollution discharge, reverse osmosis concentration and boiler pollution discharge.
Furthermore, the two-stage OA pool comprises a first-stage O pool, a first-stage A pool, a second-stage O pool and a second-stage A pool which are connected in sequence, the UASB is connected with the first-stage O pool, the MBR pool is connected with the first-stage O pool in a loop mode, and the adjusting pool is connected with the first-stage A pool and the second-stage A pool respectively.
Further, the condensed organic wastewater is firstly sent to an adjusting tank of the comprehensive wastewater treatment station, the pH value is adjusted to be neutral, and the condensed organic wastewater stays for a period of time; the low-salt wastewater enters a regulating tank and is mixed with condensed organic wastewater; the method comprises the following steps that 85% -98% of wastewater in an adjusting tank enters UASB (upflow anaerobic sludge blanket) from the water outlet of the adjusting tank, a small amount of ethanol or methanol contained in the wastewater, a small amount of products brought out in the production process of raw medicines and reaction intermediate products are reduced, the retention time is 1-10 days, and the wastewater from the UASB enters a primary O tank, a primary A tank, a secondary O tank and a secondary A tank in sequence to remove nitrogen and organic matters; 2% -15% of wastewater in the adjusting tank respectively enters a primary A tank and a secondary A tank from the adjusting tank, mixed reaction is carried out, then water flows out of the secondary A tank and enters an MBR tank, the organic matters in the wastewater are further reduced, denitrification is carried out again, membrane permeation liquid in the MBR tank enters a photo-oxidation tank, aeration time is 1-12 h, after the residual organic matters in the water are removed, the standard is reached, the discharge is carried out, and trapped liquid in the MBR tank enters a primary O tank.
Furthermore, the retention time of the regulating tank is 5-24 hours to stabilize the quality of the inlet water.
Furthermore, 2% -15% of the wastewater in the regulating pond enters the primary A pond and the secondary A pond in a ratio of 5: 1-1: 1.
Furthermore, the two-stage OA tank comprises a nitrification tank and a reverse digestion tank, wherein an aeration device is arranged in the nitrification tank, the retention time of each stage of OA tank is 3-24 h, the dissolved oxygen content of the nitrification tank is 1-6 mg/L, and the dissolved oxygen content of the reverse nitrification tank is 0-0.8 mg/L.
Furthermore, an ultraviolet lamp tube is arranged in the photo-oxidation pool, and the oxidant is hydrogen peroxide.
Furthermore, the amount of hydrogen peroxide added in the photo-oxidation tank is 20-1000 mg/L, and the ultraviolet light intensity is 10-200W/m 2 。
Further, pretreatment of the organic strong brine wastewater: conveying the organic strong-salt wastewater of the wastewater tank to a rectifying tower in a closed way through a pipeline, adjusting the pH value to weak acidity, recovering volatile organic matters such as methanol, ethanol and acetone in the organic strong-salt wastewater by using the rectifying tower, controlling the temperature to be 80 ℃, conveying the liquid in the rectifying tower after distillation into a second three-effect evaporator for evaporation and concentration, removing the volatile organic matters in the organic strong-salt wastewater, condensing the evaporated liquid by using a condenser to form condensed organic wastewater, cooling and crystallizing the evaporated residual liquid by using circulating water, separating by using a centrifuge, drying the separated crystallized salt by using a turbine thin-layer sludge drier, conveying the separated centrifugal liquid into a wastewater tank for evaporation and concentration again, and performing multi-effect combined treatment on the condensed organic wastewater by using a comprehensive wastewater treatment station;
wherein the condenser of the second three-effect evaporator is a complete condenser.
The invention also comprises the pretreatment of the light salt wastewater and the inorganic strong salt wastewater: the light salt wastewater is subjected to concentration treatment sequentially through a flocculation sedimentation tank, a multi-media filter and a membrane processor, is separated into reclaimed water and concentrated water, and is subjected to removal of suspended matters in the light salt wastewater, wherein the reclaimed water is sent into a reclaimed water tank and can be recycled in a workshop;
the concentrated water and the inorganic strong salt wastewater are pretreated by the first three-effect evaporator to obtain condensate, various salts in the inorganic strong salt wastewater and the concentrated light salt wastewater are mainly removed, and the condensate obtained after pretreatment is sent to a condensate storage tank and can be recycled in a workshop.
Further, the concentration treatment of the light salt wastewater comprises the following steps: the method comprises the following steps of firstly enabling light salt wastewater to pass through a flocculation sedimentation tank, adding a flocculating agent into the flocculation sedimentation tank, enabling suspended particles in the light salt wastewater to form suspended matters for sedimentation and removal, then further removing smaller suspended matters through a multi-media filter, then concentrating through RO (reverse osmosis) membranes in sequence, enabling liquid penetrating through the RO membranes to be reclaimed water, enabling the intercepted liquid to be concentrated water, sending the reclaimed water into a reclaimed water tank, sending the concentrated water into a concentrated water tank, wherein the reclaimed water can be used for back flushing the multi-media filter, flushing wastewater generated by the back flushing enters the flocculation sedimentation tank, and sending the concentrated water and inorganic concentrated salt wastewater into a condensate storage tank for storage and recycling after pretreatment.
Further, the concentration treatment of the light salt wastewater comprises the following steps: the light salt waste water is through the flocculation and precipitation pond earlier, adds the flocculating agent in to the flocculation and precipitation pond, then through many medium filter, then carries out concentrated processing through RO membrane concentration in proper order and electricity membrane of driving, and the liquid that sees through RO membrane and electricity membrane is the normal water, and the liquid of holding back down is the dense water, and the normal water is sent into the normal water jar, and the dense water is sent into the dense water jar, wherein, the normal water can carry out the back flush to many medium filter, and the washing waste water that the back flush produced gets into the flocculation and precipitation pond, dense water and inorganic strong salt waste water are sent into the interior storage and retrieval and utilization of condensate storage tank after the preliminary treatment.
Further, pretreatment of inorganic strong salt wastewater and concentrated water: inorganic strong brine waste water is collected through the collection tank after, directly squeezes into the dense water jar and mixes with the dense water, send into the preheating tank through the force (forcing) pump after and preheat to 90~95 ℃, send into in the first triple effect evaporimeter again and carry out evaporative concentration, the operating pressure of the evaporimeter of first triple effect evaporimeter is 0.045~0.098MPa, the heat source vapor pressure of first triple effect evaporimeter is 0.6~0.8MPa, the steam condensate gets into the flash drum through the steam trap, the condensate after the flash distillation forms the condensate after cooling to 30~40 ℃ through the circulating water, the condensate is sent into the condensate storage tank, the evaporation raffinate is crystallized with the circulating water cooling, after through the centrifuge separation, the crystal salt that separates is through the mummification of turbine thin layer sludge drier, the centrifugal liquid that separates is sent into the dense water jar and is evaporated concentration once more.
In addition, the treatment method can flexibly adjust the process parameters according to the water quality fluctuation conditions of the wastewater generated in different links of the production process of the raw material medicines.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention aims at the waste water conditions generated in different links of the production process of the raw material medicine, and the waste water is divided into four types of organic strong salt waste water, low salt waste water, light salt waste water and inorganic strong salt waste water according to water quality, wherein the four types of waste water are pretreated to remove high salt, the organic strong salt waste water and the low salt waste water are pretreated and then are subjected to multi-effect combined advanced treatment in a comprehensive waste water treatment station, so that finally discharged water reaches the discharge standard, and the inorganic strong salt waste water and the light salt waste water are pretreated and then are recycled.
2. According to the invention, through the quality-divided treatment of the wastewater, the resource utilization can be effectively realized, the methanol or the ethanol is recycled and reused for production, and the subsequent cost is reduced.
3. The invention fully realizes the cooperative treatment of all organic matters, fully reduces easily degradable carbon sources by utilizing anaerobism and aerobism, reduces and breaks chains and opens rings for the hardly degradable organic matters which are mainly organic chlorides, and reduces dechlorination and breaks chains and opens rings, thereby improving the treatment effect of the waste water; by utilizing a two-stage OA process, pollutants in a biochemical section are nitrified and then denitrified, and two-stage denitrification is realized by utilizing sectional water inlet and the alkalinity balance in the wastewater is kept; the MBR is utilized to improve the concentration of the nitrifying bacteria and ensure that the whole biochemical reaction has good treatment effect.
4. The coupling of MBR and photooxidation is realized, a small amount of difficultly degraded chlorobenzene and halogenated hydrocarbon substances remained in the effluent are deeply degraded by utilizing hydrogen peroxide in cooperation with photooxidation, the content of characteristic organic matters can be obviously reduced, the toxicity of the wastewater is reduced, and the effect of tail water disinfection is achieved.
5. The invention has convenient operation management and flexible operation, can adjust the operation mode and the process parameters according to different requirements of the inlet water quality and the outlet water quality, and furthest exerts the treatment capacity of the treatment device and the treatment structure.
6. Because the existing single treatment technology is difficult to meet the water quality discharge requirement, and bottlenecks exist in aspects of treatment scale, operation cost, continuous and stable tail water reaching standards and the like, the invention reasonably adopts coupling and cooperative treatment of multiple technologies, so that the raw material medicine production wastewater can be effectively treated, and the final effluent quality is ensured to meet the specified discharge requirement.
Drawings
FIG. 1 is a flow chart of the treatment process of organic salt wastewater and low-salt wastewater in the production process of bulk drugs.
Fig. 2 is a process flow chart of the invention for treating inorganic concentrated salt wastewater and light salt wastewater in the production process of raw material medicines.
Detailed Description
In order to more clearly and completely illustrate the present invention, the following examples are given by way of illustration of the present invention, and are not intended to limit the present invention.
According to the wastewater conditions generated in different links of the technical process of producing the aminomethylbenzoic acid, the wastewater is divided into four types of organic strong salt wastewater, low salt wastewater, light salt wastewater and inorganic strong salt wastewater according to water quality, wherein the organic strong salt wastewater is from waste mother liquor water for producing the aminomethylbenzoic acid, ethanol recovery tower bottom wastewater and acetone recovery wastewater; the low-salt wastewater mainly comes from filter back flushing water and domestic sewage; the light salt wastewater mainly comes from circulating water sewage wastewater, reverse osmosis concentrated water and boiler sewage wastewater; the inorganic concentrated salt wastewater comes from mixed bed regeneration wastewater.
Example 1
In this embodiment, a method for resource utilization and advanced treatment of organic strong salt wastewater and low salt wastewater in raw material drug production process wastewater comprises the following steps:
organic strong salt wastewater: and (3) conveying the organic strong-salt wastewater stored in the wastewater tank to a rectifying tower in a sealed way through a pipeline, adjusting the pH value to weak acidity, and recovering volatile organic matters of methanol, ethanol or acetone in the organic strong-salt wastewater by using the rectifying tower. A total of 3 pieces of 5 m are arranged 3 The rectifying tower is controlled at 80 ℃, when one rectifying tower finishes distillation (when a little liquid is discharged from a condenser), the rectifying tower is switched to the other rectifying tower for distillation, when organic strong salt wastewater enters the rectifying tower, extruded waste gas and distilled fractions are condensed and recovered by the condenser, non-condensable gas is pumped into organic waste gas treatment equipment, the liquid in the rectifying tower after distillation is sent into a second three-effect evaporator for evaporation and concentration, the liquid in the rectifying tower after distillation passes through a second first effect evaporator, a second effect evaporator and a second third-stage evaporator in sequence, the evaporated liquid is condensed by the condenser to form condensed organic wastewater, the condensed organic wastewater is sent into a comprehensive wastewater treatment station, the condensed organic wastewater is a mixed liquid of water and a small amount of organic matters such as methanol, ethanol, chlorobenzene, azodiisobutyronitrile and the like, and the organic strong salt wastewater is subjected to distillation pretreatment, the condenser of the second three-effect evaporator is a full condenser, the evaporation residual liquid after evaporation and concentration is cooled and crystallized by circulating water and then is separatedSeparating by a heart device, treating the separated crystal salt as dangerous waste, and returning the separated centrifugal liquid to the waste water tank for evaporation and concentration again.
The condensed organic wastewater is firstly sent to an adjusting tank of a comprehensive wastewater treatment station, the pH is adjusted to be neutral, and the retention time is 5 hours, so as to stabilize the quality of the inlet water; the low-salt wastewater enters a regulating tank and is mixed with the condensed organic wastewater; the method comprises the following steps that 85% of wastewater in an adjusting tank enters UASB (upflow anaerobic sludge blanket) from water discharged from the adjusting tank, so that a small amount of ethanol or methanol contained in the wastewater, a small amount of products and reaction intermediate products brought out in the production process of raw material medicines are reduced, the retention time is 1 d, the effluent from the UASB enters two-stage anaerobic aerobic tanks (two-stage OA tanks) of a nitrification tank and a reverse digestion tank, the retention time of each-stage OA tank is 3h, and the effluent sequentially passes through a first-stage O tank, a first-stage A tank, a second-stage O tank and a second-stage A tank, wherein the dissolved oxygen content of the nitrification tank is 1mg/L, and the dissolved oxygen content of the reverse nitrification tank is 0.8mg/L, so that nitrogen is removed and organic matters are further removed; respectively feeding 15% of wastewater in the regulating tank into a primary A tank and a secondary A tank from the regulating tank according to the ratio of 5:1, mixing and reacting, then discharging water from the secondary A tank into a membrane biological reaction tank (MBR tank), further reducing organic matters in the wastewater, simultaneously denitrifying again, feeding membrane permeation liquid in the MBR tank into a photooxidation tank provided with an ultraviolet lamp tube and hydrogen peroxide as an oxidant, wherein the feeding amount of the hydrogen peroxide is 20-1000 mg/L, and the ultraviolet light intensity is 10-200W/m 2 And the aeration time is 1-12 h, after removing residual organic matters in water, the residual organic matters reach the standard, discharging, and allowing trapped liquid in the MBR tank to enter a first-level O tank. The final effluent discharged by the photooxidation pond is detected, the result is shown in the table I, and all indexes of the effluent meet the requirements of the first-class A standard of Integrated wastewater discharge Standard (GB 8978-1996) and pollutant discharge Standard of municipal wastewater treatment plant (GB 18918-2002).
Watch 1
Index (I) Final effluent (mg/L) after treatment
Chemical Oxygen Demand (COD) 34.1
Biochemical oxygen demand (BOD 5) 7.5
Suspended Substance (SS) 1.3
Total nitrogen (in N) 13.9
Ammonia nitrogen (in terms of N) 3.8
Total phosphorus (measured as P) 0.3
Example 2
In this embodiment, a method for resource utilization and advanced treatment of organic strong salt wastewater and low salt wastewater in raw material drug production process wastewater comprises the following steps:
the organic strong salt waste water is transported to a waste water tank through a closed pipeline, organic solvent is evaporated from a rectifying still, methanol and ethanol are recycled, residual liquid in the rectifying still is sent to a second triple-effect evaporator for treatment, the specific distillation process refers to the evaporation concentration in the example 1, condensed organic waste water is obtained, the condensed liquid contains about 1% of methanol or ethanol, the COD is high, the biodegradability is strong, and the condensed organic waste water is sent to comprehensive waste water treatment equipment.
Sending the condensed organic wastewater into an adjusting tank of a comprehensive wastewater treatment station, adjusting the pH to be neutral, and keeping the pH for 16 h; the low-salt wastewater enters a regulating tank and is mixed with condensed organic wastewater; 90 percent of wastewater in the regulating reservoir flows into UASB from the effluent of the regulating reservoir, so that the content of wastewater is reducedA small amount of ethanol or methanol, a small amount of products and reaction intermediate products brought out in the production process of the bulk drugs, the retention time is 5 d, effluent from UASB enters two-stage OA tanks of a nitrification tank and a reverse digestion tank, the retention time of each stage of OA tank is 16h, wherein the dissolved oxygen content of the nitrification tank is 3.2mg/L, the dissolved oxygen content of the reverse nitrification tank is 0.4mg/L, and nitrogen removal and further organic matter removal are carried out; 10% of wastewater in the regulating reservoir respectively enters a first-stage A pool and a second-stage A pool from the regulating reservoir according to the ratio of 2.5:1, the wastewater is mixed and reacted, then the effluent from the second-stage A pool enters an MBR pool, the organic matters in the wastewater are further reduced and simultaneously denitrified again, the membrane permeation liquid in the MBR pool enters a photo-oxidation pool, the adding amount of hydrogen peroxide is 20-1000 mg/L, the ultraviolet light intensity is 10-200W/m 2 And the aeration time is 1-12 h, the standard is reached, the wastewater is discharged, and the trapped fluid in the MBR tank enters the first-stage O tank. The final effluent discharged by the photooxidation pond is detected, the result is shown in the table II, and all indexes of the effluent meet the requirements of the first-class A standard of Integrated wastewater discharge Standard (GB 8978-1996) and pollutant discharge Standard of municipal wastewater treatment plant (GB 18918-2002).
Watch two
Index (I) Final effluent (mg/L) after treatment
Chemical Oxygen Demand (COD) 25.5
Biochemical oxygen demand (BOD 5) 5.9
Suspended Substance (SS) 3.1
Total nitrogen (in N) 10.2
Ammonia nitrogen (in N) 3.2
Total phosphorus (measured as P) 0.2
Example 3
In this embodiment, a method for resource utilization and advanced treatment of organic strong salt wastewater and low salt wastewater in raw material drug production process wastewater comprises the following steps:
the organic strong salt waste water is transported to a waste water tank through a closed pipeline, organic solvent is evaporated from a rectifying still, methanol and ethanol are recycled, residual liquid in the rectifying still is sent to a second triple-effect evaporator for treatment, the specific distillation process refers to the evaporation concentration in the example 1, condensed organic waste water is obtained, the condensed liquid contains about 1% of methanol or ethanol, the COD is high, the biodegradability is strong, and the condensed organic waste water is sent to comprehensive waste water treatment equipment.
Sending the condensed organic wastewater into an adjusting tank of a comprehensive wastewater treatment station, adjusting the pH to be neutral, and keeping the time for 24 hours; the low-salt wastewater enters a regulating tank and is mixed with the condensed organic wastewater; the wastewater in 98% of the regulating reservoir enters UASB from the effluent of the regulating reservoir, so that a small amount of ethanol or methanol contained in the wastewater, a small amount of products and reaction intermediate products brought out in the production process of the raw material medicines are reduced, the retention time is 10 d, the effluent of the UASB enters two-stage OA tanks of a nitrification tank and a reverse digestion tank, the retention time of each-stage OA tank is 24h, wherein the dissolved oxygen content of the nitrification tank is 6mg/L, the dissolved oxygen content of the reverse nitrification tank is 0mg/L, and the wastewater is denitrified and further organic matters are removed; 2 percent of wastewater in the regulating reservoir respectively enters a first-stage A pool and a second-stage A pool from the regulating reservoir according to the ratio of 1:1, the wastewater is mixed and reacted, then the effluent from the second-stage A pool enters an MBR pool, the organic matters in the wastewater are further reduced, simultaneously, denitrification is carried out again, then membrane permeation liquid in the MBR pool enters a photo-oxidation pool, and the adding amount of hydrogen peroxide is that20-1000 mg/L, ultraviolet light intensity of 10-200W/m 2 And the aeration time is 1-12 h, the standard is reached, the wastewater is discharged, and the trapped fluid in the MBR tank enters the first-stage O tank. The final effluent discharged by the clean water tank is detected, the result is shown in Table III, and all indexes of the effluent meet the requirements of the primary A standard of Integrated wastewater discharge Standard (GB 8978-1996) and pollutant discharge Standard of urban wastewater treatment plant (GB 18918-2002).
Watch III
Index (I) Final effluent (mg/L) after treatment
Chemical Oxygen Demand (COD) 19.4
Biochemical oxygen demand (BOD 5) 4.2
Suspended Substance (SS) 2.6
Total nitrogen (in N) 10.2
Ammonia nitrogen (in N) 2.8
Total phosphorus (in terms of P) 0.4
Example 4
In this embodiment, a resource utilization treatment method for weak salt wastewater and inorganic strong salt wastewater in raw material drug production process wastewater comprises the following steps:
the method comprises the steps of collecting light salt wastewater into a coagulating sedimentation tank, adding a flocculating agent (such as polyacrylamide and the like) into the coagulating sedimentation tank, enabling suspended particles in the light salt wastewater to form suspended matters for precipitation removal, sending the suspended matters into a multi-media filter by using a lifting pump, further removing smaller suspended matters, then sending the suspended matters into a reverse osmosis membrane (RO membrane) after pressurization by using a pressurizing pump, selecting a seawater desalination membrane as the RO membrane, enabling the salt content of permeable water to be about 200 mg/L and the water yield to be 70%, sending reclaimed water produced by the RO membrane into a reclaimed water tank for storage, sending concentrated water into a concentrated water tank for storage, enabling the salt content in the concentrated water to be not less than 3 times of the salt content in the light salt wastewater, carrying out back washing by using the reclaimed water produced by the RO membrane for the multi-media filter, and discharging washing wastewater produced by washing into the coagulating sedimentation tank.
Inorganic concentrated brine is collected by a recovery tank, is directly pumped into a concentrated water tank, is mixed with the concentrated water in the concentrated water tank, is sent into a preheating device by a pressure pump to be preheated to 95 ℃, and then is sent into a first three-effect evaporation tower and is firstly sent into the middle part of a first-effect evaporator, the operating pressure of the evaporator is 0.098Mpa, the reboiler adopts forced circulation, the steam pressure of a heat source is 0.6 MPa, steam condensate enters a flash evaporation tank through a steam trap, the steam which is flashed out is sent into a reboiler of the first third-effect evaporator to be used as the heat source, the condensate which is flashed is cooled to 35 ℃ by circulating water to form condensate, the steam pressure of the steam which is sent out from the first-effect evaporator is 0.098MPa and is sent into the reboiler of a first second-effect evaporator, and the solution at the bottom of the first-effect evaporator flows into the first second-effect evaporator by means of gravity; the operating pressure of the evaporator of the first second-effect evaporator is 0.07 MPa, in order to reduce the blockage of the reboiler and strengthen the forced circulation of the heat transfer solution by a pump, the steam pressure of the steam coming out of the first second-effect evaporator is 0.07 MPa and enters the reboiler of the third-effect evaporation crystallization tower, the solution of the evaporator is forced circulated by the pump, the steam condensate is cooled to 40 ℃ by a steam trap and circulating water to form condensate, and the solution at the bottom of the first second-effect evaporator flows into the first third-effect evaporator by gravity; the solution entering a reboiler from an evaporator of a first third-effect evaporator is forcibly circulated by a pump, the condensate from the reboiler is cooled to 35 ℃ by a steam trap and circulating water to form condensate, the steam pressure of the steam from the first third-effect evaporator is 0.046 MPa, the steam enters a circulating water cooler to be cooled to 35 ℃ and enters a separator, the separated non-condensable gas and the steam at the saturation temperature enter a water vacuum ejector to generate vacuum, the separated condensable gas is cooled and enters a reclaimed water tank, the evaporated residual liquid is cooled and crystallized by the circulating water and then is separated by the centrifuge, the separated crystallized salt is crystallized by a turbine thin-layer sludge drier, the separated centrifugal liquid is sent to a concentrated water tank to be evaporated and concentrated again, the condensate is sent to a condensate storage tank, and the condensate in the condensate storage tank and the reclaimed water in the reclaimed water tank are dried and reused in a workshop.
Example 5
In this embodiment, a resource utilization treatment method for weak salt wastewater and inorganic strong salt wastewater in raw material drug production process wastewater comprises the following steps:
the method comprises the following steps of firstly concentrating the light salt wastewater by an RO membrane and concentrating by an electric membrane, obtaining reclaimed water and concentrated water after two-step concentration, wherein the salt content of the concentrated water is more than 100000 mg/L, sending the reclaimed water into a reclaimed water tank, sending the reclaimed water into a workshop for recycling, and sending the concentrated water into a concentrated water tank for storage; and (3) mixing concentrated water and inorganic concentrated brine, preheating, and then feeding the mixture into a first three-effect evaporator, wherein the specific evaporation process refers to the evaporation concentration process in the embodiment 2, so as to obtain condensate, feeding the condensate into a condensate storage tank, and feeding the condensate in the condensate storage tank back to a workshop for recycling.
Finally, it should be noted that the above embodiments are only used for illustrating and not limiting the technical solutions of the present invention, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the present invention without departing from the spirit and scope of the present invention, and all modifications or partial substitutions should be covered by the scope of the claims of the present invention.

Claims (6)

1. A resource utilization and advanced treatment method of raw material drug production process wastewater is characterized in that the raw material drug production process wastewater is divided into four types of organic strong salt wastewater, low salt wastewater, light salt wastewater and inorganic strong salt wastewater according to water quality according to wastewater conditions generated in different links of the raw material drug production process, the organic strong salt wastewater and the low salt wastewater are sent into a comprehensive wastewater treatment station for advanced treatment after being pretreated, and the inorganic strong salt wastewater and the light salt wastewater are recycled after being pretreated;
the comprehensive wastewater treatment station comprises an adjusting tank, a UASB (upflow anaerobic sludge blanket), a two-stage OA (anaerobic-anoxic sludge blanket), an MBR (membrane bioreactor) tank and a photooxidation tank, wherein the adjusting tank, the UASB, the two-stage OA tank, the MBR tank and the photooxidation tank are sequentially connected, the two-stage OA tank comprises a first-stage O tank, a first-stage A tank, a second-stage O tank and a second-stage A tank which are sequentially connected, the UASB is connected with the first-stage O tank, the MBR tank is connected with the first-stage O tank in a loop, and the adjusting tank is respectively connected with the first-stage A tank and the second-stage A tank;
pretreating the organic strong-salt wastewater by a rectifying tower and a second triple-effect evaporator in sequence to obtain distillate and condensed organic wastewater, wherein the distillate is methanol or ethanol, and the condensed organic wastewater enters an adjusting tank;
the low-salt wastewater also enters a regulating tank;
the light salt wastewater is sequentially concentrated by a flocculation sedimentation tank, a multi-media filter and a membrane processor and separated into reclaimed water and concentrated water, and the reclaimed water is sent into a reclaimed water tank for reuse;
pretreating concentrated water and inorganic concentrated salt wastewater by a first triple-effect evaporator to obtain condensate, and feeding the condensate into a condensate storage tank for reuse;
sending the condensed organic wastewater into an adjusting tank of a comprehensive wastewater treatment station, adjusting the pH to be neutral, and staying for a period of time; the low-salt wastewater enters a regulating tank and is mixed with condensed organic wastewater; 85% -98% of wastewater in the adjusting tank enters UASB from the effluent of the adjusting tank, the retention time is 1-10 d, the effluent of the UASB enters two-stage OA tanks which are sequentially connected with a primary O tank, a primary A tank, a secondary O tank and a secondary A tank, the retention time of each-stage OA tank is 3-24 h, 2% -15% of wastewater in the adjusting tank enters the primary A tank and the secondary A tank from the adjusting tank respectively, the wastewater is subjected to mixing reaction, then the effluent of the secondary A tank enters an MBR tank, the organic matters in the wastewater are further reduced and simultaneously denitrified again, membrane permeation liquid in the MBR tank enters a photo-oxidation tank, the aeration time is 1-12 h, and the retention liquid in the MBR tank enters the primary O tank.
2. The resource utilization and advanced treatment method for raw material drug production process wastewater according to claim 1, characterized in that the retention time of the regulating reservoir is 5-24 h.
3. The resource utilization and advanced treatment method for raw material drug production process wastewater according to claim 1, characterized in that the ratio of 2% -15% of wastewater in the regulating reservoir to enter the primary A pool and the secondary A pool is 5: 1-1: 1.
4. The resource utilization and advanced treatment method of raw material drug production process wastewater according to claim 1, characterized in that an ultraviolet lamp tube is arranged in the photo-oxidation tank, and the oxidant is hydrogen peroxide.
5. The resource utilization and advanced treatment method for wastewater of raw material drug production process according to claim 4, characterized in that the dosage of hydrogen peroxide in the photooxidation tank is 20-1000 mg/L, and the ultraviolet light intensity is 10-200W/m 2 。
6. The bulk drug production process wastewater resource utilization and advanced treatment method according to claim 1, wherein the two-stage OA tank comprises a nitrification tank and a denitrification tank, and an aeration device is arranged in the nitrification tank, wherein the dissolved oxygen content of the nitrification tank is 1-6 mg/L, and the dissolved oxygen content of the denitrification tank is 0-0.8 mg/L.
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