CN219489779U - Desulfurization wastewater zero release processing system based on freezing crystallization technology - Google Patents
Desulfurization wastewater zero release processing system based on freezing crystallization technology Download PDFInfo
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Abstract
The utility model discloses a desulfurization wastewater zero-emission treatment system based on a freezing crystallization technology, and belongs to the technical field of wastewater treatment. The system sequentially comprises a pretreatment unit, an ultrafiltration unit, a nanofiltration unit, a reverse osmosis unit, a freezing crystallization unit and an evaporation crystallization unit, wherein the freezing crystallization unit is connected with the nanofiltration unit through a pipeline, the evaporation crystallization unit is connected with the reverse osmosis unit through a pipeline, the freezing crystallization unit comprises a freezing crystallizer, a first backflow pipeline is arranged on the freezing crystallizer, ice crystals obtained in the freezing crystallizer flow back to the front end of the nanofiltration unit through the first backflow pipeline, the evaporation crystallization unit comprises an evaporation crystallizer, a second backflow pipeline is arranged on the evaporation crystallizer, and condensed water used for processing of the evaporation crystallizer flows back to the front end of the reverse osmosis unit through the second backflow pipeline. By applying the freezing crystallization technology to zero discharge of desulfurization wastewater, not only is mirabilite in the wastewater recycled, but also the running cost is reduced.
Description
Technical Field
The utility model belongs to the technical field of wastewater treatment, and particularly relates to a desulfurization wastewater zero-emission treatment system based on a freezing crystallization technology.
Background
At present, most coal-fired power plants in China mainly adopt a wet desulfurization process to effectively control flue gas pollutants, the process is stable in operation and mature in technology, and desulfurization wastewater produced by the process has the characteristics of large water quantity, high turbidity, high hardness, high chloride ion concentration and the like. Based on the increasingly severe environmental protection requirements, the zero emission treatment of the power plant wastewater has become a trend, the zero emission refers to that any wastewater is not discharged into the environment, the process water is recycled, part of salt in the wastewater can be recycled, and the rest is subjected to the concentration crystallization treatment to obtain harmless treatment.
The main process route of the desulfurization wastewater zero emission project at the present stage is pretreatment, membrane concentration and evaporation, wherein the pretreatment mainly adopts a chemical dosing precipitation method to remove hardness such as calcium, magnesium and the like in the wastewater, the membrane concentration mainly adopts Reverse Osmosis (RO) or butterfly tube type reverse osmosis (DTRO) to further concentrate the wastewater quantity, the water recycling rate is improved, the evaporation unit heats the membrane concentrate by steam to further concentrate and crystallize, condensed water is recycled after reverse osmosis treatment, and soluble solids in the wastewater are separated out by concentration and crystallization.
The amount of the concentrated solution after the concentration of the DTRO is still larger, the TDS is lower, a general evaporation unit adopts a two-stage evaporation process such as 'falling film evaporation+forced circulation evaporation', the investment of process equipment is larger, the concentration of chloride ions in the concentrated solution is high, corrosion is more easy to occur in a high-temperature and high-pressure environment in an evaporator, the service life of a heat exchanger is shortened, and the heat exchanger is further concentrated and crystallized completely through steam, so that the steam consumption is large. And the salt separated out by crystallization is relatively impurity, and can be recycled by further purification. Thus, the investment and operation costs are greatly increased.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems of large concentrated solution amount, low purity of crystallized salt and high investment and cost of process equipment in the existing desulfurization wastewater zero discharge technology, the utility model provides a desulfurization wastewater zero discharge treatment system based on a freezing crystallization technology. According to the system, the freezing crystallization technology is applied to zero discharge of desulfurization wastewater, and the freezing crystallization is added at the front end of the evaporation unit, so that mirabilite in the wastewater is recycled, mother liquor after freezing concentration is further concentrated, the treatment capacity of the evaporation system is greatly reduced, and therefore, the energy consumption of process equipment is reduced, and the process investment and the operation cost are reduced.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the utility model is as follows:
the utility model relates to a desulfurization wastewater zero-emission treatment system based on a freezing crystallization technology, which sequentially comprises a pretreatment unit, an ultrafiltration unit, a nanofiltration unit and a reverse osmosis unit; the device also comprises a freezing crystallization unit and an evaporation crystallization unit, wherein the freezing crystallization unit is connected with the nanofiltration unit through a pipeline, and the evaporation crystallization unit is connected with the reverse osmosis unit through a pipeline; the freezing crystallization unit comprises a freezing crystallizer, a first backflow pipeline is arranged on the freezing crystallizer, and ice crystals obtained in the freezing crystallizer flow back to the front end of the nanofiltration unit through the first backflow pipeline; the evaporation crystallization unit comprises an evaporation crystallizer, a second backflow pipeline is arranged on the evaporation crystallizer, and condensed water used for processing the evaporation crystallizer flows back to the front end of the reverse osmosis unit through the second backflow pipeline.
Preferably, the pretreatment unit comprises a homogenizing and adjusting tank and a softening and reacting tank, wherein the homogenizing and adjusting tank is connected with the softening and reacting tank through a pipeline, and an outlet of the softening and reacting tank is connected with an inlet of the ultrafiltration unit through a pipeline.
Preferably, the ultrafiltration unit is an ultrafiltration membrane device, and a tubular softening membrane is arranged in the ultrafiltration membrane device.
Preferably, the nanofiltration unit is a butterfly pipe type nanofiltration device, a concentrated water outlet and a nanofiltration water outlet are arranged at the bottom of the butterfly pipe type nanofiltration device, the concentrated water outlet is connected with the freezing crystallization unit through a concentrated water pipeline, and the nanofiltration water outlet is connected with the reverse osmosis unit through a nanofiltration water outlet pipeline.
Preferably, the reverse osmosis unit is a butterfly pipe type reverse osmosis filter device, a reverse osmosis water outlet and a strong brine outlet are arranged at the bottom of the butterfly pipe type reverse osmosis filter device, and the strong brine outlet is connected with the evaporation crystallization unit through a strong brine pipeline.
Preferably, the freezing crystallization unit sequentially comprises a freezing crystallizer, a centrifugal separator and a dryer, wherein the crystallized salt obtained in the freezing crystallizer is connected to the centrifugal separator through a pipeline for separation and purification, and then the separated and purified crystallized salt enters the dryer through the pipeline for drying.
Preferably, the first return pipeline is an ice crystal return pipeline, and ice crystals obtained in the freezing crystallizer return to the inlet of the nanofiltration unit through the ice crystal return pipeline; the second return pipeline is a condensate water return pipeline, and condensate water used for the treatment of the evaporative crystallizer flows back to the inlet of the reverse osmosis unit through the condensate water return pipeline.
Preferably, a low-temperature negative pressure evaporator is arranged in the evaporative crystallization unit.
Preferably, an orbital stirring rod is arranged in the freezing crystallizer.
3. Advantageous effects
Compared with the prior art, the utility model has the beneficial effects that:
(1) According to the desulfurization wastewater zero-emission treatment system based on the freezing crystallization technology, the freezing crystallization unit is applied to desulfurization wastewater treatment to purify mirabilite to obtain a mirabilite product with higher purity, the rejection rate of the nanofiltration unit to sulfate radicals is 97%, and the mirabilite product with 99% purity can be obtained after the treatment of freezing crystallization and centrifugal drying, so that the desulfurization wastewater zero-emission treatment system has higher economic value compared with the traditional process;
(2) According to the desulfurization wastewater zero-emission treatment system based on the freezing crystallization technology, a small amount of calcium and magnesium ions can be further accumulated after reverse osmosis treatment, in order to prevent scaling, a low-temperature negative pressure evaporator is adopted, the working temperature is 68-98 ℃, the energy consumption is greatly reduced through a mature low-temperature heat pump, the risk of scaling on the surface of the evaporator is reduced at low temperature, and the system maintenance is simpler;
(3) According to the treatment process of the desulfurization wastewater zero-emission treatment system based on the freezing crystallization technology, reverse osmosis inflow water comes from water production of the nanofiltration unit on one hand, and condensed water evaporated at low temperature and negative pressure from the evaporation crystallization unit on the other hand, ice crystals (mixed with part of sodium sulfate solution) of a freezing crystallizer are dissolved and enter the front end of the nanofiltration unit for treatment again, and the process combination optimization can greatly improve the water production recovery rate, so that the maximum utilization of water resources is achieved, and the water production recovery rate can reach more than 95%;
(4) According to the treatment process of the desulfurization wastewater zero-emission treatment system based on the freezing crystallization technology, aiming at the characteristics of high sulfate radical and high chloride ion of desulfurization wastewater, the concentration of the chloride ion is multiplied after membrane concentration, and the corrosion of equipment can be delayed through freezing concentration and low-temperature negative pressure evaporation, so that the service life is prolonged.
Drawings
FIG. 1 is a schematic structural diagram of a desulfurization wastewater zero-emission treatment system based on a freezing crystallization technology;
FIG. 2 is a schematic diagram of the stirring principle of a track rod evaporator employed in the freeze crystallizer of the present utility model;
FIG. 3 is a schematic diagram of a treatment process flow of a desulfurization wastewater zero-emission treatment system based on a freezing crystallization technology;
in the figure:
100. a homogenizing regulating tank; 200. a softening reaction tank; 300. an ultrafiltration membrane device;
400. butterfly tube nanofiltration device; 401. a concentrated water outlet; 402. a nanofiltration product water outlet;
410. a concentrated water pipeline; 420. nanofiltration water production pipeline; 500. freezing the crystallizer;
510. an ice crystal return tube; 600. a centrifuge; 700. a dryer;
800. butterfly tube type reverse osmosis filter device; 801. a reverse osmosis produced water outlet;
802. a strong brine outlet; 810. concentrated brine pipeline; 820. a condensate water return pipe;
900. a low-temperature negative pressure evaporator.
Detailed Description
The utility model is further described below in connection with specific embodiments.
As shown in fig. 1, the desulfurization wastewater zero-emission treatment system based on the freezing crystallization technology of the embodiment sequentially comprises a pretreatment unit, an ultrafiltration unit, a nanofiltration unit, a reverse osmosis unit, a freezing crystallization unit and an evaporation crystallization unit, wherein the freezing crystallization unit is connected with the nanofiltration unit through a pipeline, and the evaporation crystallization unit is connected with the reverse osmosis unit through a pipeline; the pretreatment unit comprises a homogenizing and adjusting tank 100 and a softening and reacting tank 200, wherein the homogenizing and adjusting tank 100 is connected with the softening and reacting tank 200 through a pipeline, and an outlet of the softening and reacting tank 200 is connected with an inlet of the ultrafiltration unit through a pipeline;
the ultrafiltration unit is an ultrafiltration membrane device 300, and a tubular softening membrane is arranged in the ultrafiltration membrane device 300; the nanofiltration unit is a butterfly pipe type nanofiltration device 400, a concentrated water outlet 401 and a nanofiltration water outlet 402 are arranged at the bottom of the butterfly pipe type nanofiltration device 400, the concentrated water outlet 401 is connected with the freezing crystallization unit through a concentrated water pipeline 410, and the nanofiltration water outlet 402 is connected with the reverse osmosis unit through a nanofiltration water outlet pipeline 420; the reverse osmosis unit is a butterfly pipe type reverse osmosis filter device 800, a reverse osmosis water outlet 801 and a strong brine outlet 802 are arranged at the bottom of the butterfly pipe type reverse osmosis filter device 800, the strong brine outlet 802 is connected with the evaporative crystallization unit through a strong brine pipeline 810, and the reverse osmosis water outlet 801 is used for recycling water through a pipeline;
the freezing crystallization unit comprises a freezing crystallizer, preferably comprises a freezing crystallizer 500, a centrifugal separator 600 and a dryer 700 in sequence, wherein the crystallized salt obtained in the freezing crystallizer 500 is connected to the centrifugal separator 600 through a pipeline for separation and purification, and then the separated and purified crystallized salt enters the dryer 700 through the pipeline for drying; the freezing crystallizer is provided with a first return pipeline, namely an ice crystal return pipe 510, and ice crystals obtained in the freezing crystallizer return to the inlet of the nanofiltration unit through the ice crystal return pipe 510; the evaporative crystallization unit comprises an evaporative crystallizer, a second backflow pipeline, namely a condensate water backflow pipeline 820 is arranged on the evaporative crystallizer, and condensate water used for processing the evaporative crystallizer flows back to an inlet of the reverse osmosis unit through the condensate water backflow pipeline 820.
The freezing crystallizer 500 is provided therein with a track rod evaporator, and this integrated stirring rod crystal generation technology enhances the heat transfer efficiency of the multi-tube heat exchanger. The effect of such a stirring rod, as shown in figure 2, is to apply a fluid wave around the inner circle of the tube, which stirring enhances the membrane coefficient by mixing the falling film solution, creating very intense turbulence. Assuming that such mixing can produce sufficient subcooled liquid, the subcooled liquid is then reduced by the formation of the crystalline salt. Thus, the stirring fluid produced by the rotating stirring rod within the tube prevents the crystalline salt from adhering to the heat exchanger surface, and on the wetted surface the solution acts as a lubricant, ensuring that the stirring rod does not come into contact with the tube. Therefore, the stirring rod has an inherent self-adjusting capacity and minimum abrasion, the process is matched with the efficient evaporator and the efficient condenser, the energy consumption of the system is low, the efficiency is averagely improved by more than 20 percent compared with the traditional ice storage mode, and the risk of ice crystal wall hanging of the freezing crystallizer can be greatly reduced.
In addition, a low-temperature negative pressure evaporator 900 is arranged in the evaporation crystallization unit. The low-temperature negative pressure evaporator is adopted, the evaporation temperature is set to 68-98 ℃, the evaporator is pumped into a negative pressure state by a vacuum pump, the evaporation process of evaporating the boiling point of liquid is reduced, the general operation temperature is lower than 100 ℃, and the pressure and the temperature of secondary steam are improved by utilizing the high-energy-efficiency steam compressor to compress and evaporate the secondary steam generated. The secondary steam with heat energy increased is pumped into the heater to heat the stock solution, and the heated stock solution is continuously evaporated to generate secondary steam, so that a continuous evaporation state is realized. The condensed hot water exchanges heat with the raw materials, so that heat is further recovered, full utilization of latent heat is realized, evaporation energy consumption is reduced, and operation cost is saved.
As shown in fig. 3, the system of the embodiment is used for carrying out the desulfurization wastewater zero-emission treatment process, which comprises the following steps:
s10, the desulfurization wastewater enters a pretreatment unit, and is firstly subjected to uniform treatmentHomogenizing in a mass adjusting tank 100, and introducing into a softening reaction tank 200 via a pipeline, wherein Ca (OH) is used 2 +Na 2 CO 3 Softening the desulfurization wastewater by a double-alkali method, and controlling the pH value of the desulfurization wastewater to be 10.5-11.0 after dosing;
s20, directly pumping softened wastewater into an ultrafiltration membrane device 300 without clarifying to carry out ultrafiltration treatment, and removing fine particle suspended matters in the wastewater;
s30, the desulfurization wastewater after ultrafiltration treatment enters a butterfly tube type nanofiltration device 400 for salt separation treatment, and monovalent salt solution and divalent salt solution are separated, wherein sodium sulfate can be purified in the step, and the sodium sulfate solution is mainly intercepted into concentrated water by a nanofiltration membrane to obtain concentrated water solution containing high-purity sodium sulfate and nanofiltration water solution mainly containing sodium chloride;
s40, the concentrated aqueous solution obtained in the step S30 is introduced into a freezing crystallizer 500 of a freezing and crystallizing unit through a concentrated water outlet 401 and a concentrated water pipeline 410, and is subjected to low-temperature crystallization to obtain sodium sulfate crystals (Na 2 SO 4 ·10H 2 O) precipitation to obtain sodium sulfate crystals (Na 2 SO 4 ·10H 2 O), and sodium sulfate crystals (Na) are further purified by centrifugal separation by the centrifugal separator 600 2 SO 4 ·10H 2 O), and then drying by a dryer 700 to obtain industrial product mirabilite;
in addition, the nanofiltration product water solution obtained in the step S30 enters a butterfly pipe type reverse osmosis filter device 800 of a reverse osmosis unit through a nanofiltration product water pipeline 420 through a nanofiltration product water outlet 402 for concentration reduction treatment, so as to obtain reverse osmosis concentrated solution, wherein the nanofiltration product water solution is reduced to 10%; and then the reverse osmosis produced water is recycled to the water supplementing of the power plant water dissolving system through a reverse osmosis produced water outlet 801;
s50, enabling the reverse osmosis concentrated solution obtained in the step S40 to enter a low-temperature negative pressure evaporator 900 of an evaporative crystallization unit through a concentrated salt water pipeline 810 through a concentrated salt water outlet 802, and performing low-temperature negative pressure evaporation treatment to obtain industrial sodium chloride, wherein the temperature of the low-temperature negative pressure evaporation treatment is 68-98 ℃.
The evaporation crystallization section adopts a low-temperature negative pressure evaporation process, negative pressure is generated by pumping negative pressure through the low-temperature negative pressure evaporator 900 to reduce the boiling point of concentrated solution, the coking and solidification of materials containing organic matters in the evaporator can be prevented, and when the reduction of the mother solution of the evaporator reaches a design value, the mother solution of the evaporator is conveyed to a low-temperature drying system for drying, and the dried residues are conveyed to a landfill.
It should be further noted that, in step S40, the water fed from the reverse osmosis unit is from the nanofiltration product water solution of the nanofiltration unit on one hand, and from the condensed water evaporated at low temperature and negative pressure of the evaporation crystallization unit on the other hand, the condensed water enters the front end inlet of the reverse osmosis unit through the condensed water return pipe 820 provided on the evaporation crystallizer; in addition, in step S40, ice crystals (occluded part of sodium sulfate solution) generated in the freeze crystallizer may be subjected to nanofiltration salt separation treatment once again by being dissolved through the ice crystal return tube 510 into the front end inlet of the nanofiltration unit.
Example 1
The desulfurization wastewater zero-emission treatment process based on the freezing crystallization technology in this embodiment has the following initial water quality of desulfurization wastewater:
TABLE 1 initial Water quality of desulfurization wastewater
The specific process steps are as follows:
s10, the desulfurization wastewater enters a homogenizing and regulating tank 100 to carry out homogenizing and regulating on the water quantity and the water quality, and then Ca (OH) is adopted in a softening reaction tank 200 2 +Na 2 CO 3 Softening treatment by a double-alkali method, and controlling the pH value of desulfurization wastewater to be about 10.5-11.0 after dosing;
s20, filtering the wastewater after the chemical adding and softening reaction tank 200 in a tubular ultrafiltration device 300 to remove most of colloid, suspended matters and other substances, and softening and filtering Ca in the wastewater 2+ 、Mg 2+ The mass fraction of ions is reduced to 0.005%o and 0.001%o respectively, wherein the filtration flux of the tubular ultrafiltration adopted in the embodiment is 2-3 times that of the traditional organic membrane, and the tubular ultrafiltration does not need to be subjected to the processClarifying by a clarifying tank, so that occupied space can be greatly saved;
s30, introducing the desulfurization wastewater subjected to ultrafiltration treatment into a butterfly tube type nanofiltration device 400 for salt separation treatment, and purifying a sodium sulfate solution in the wastewater by utilizing the characteristic of nanofiltration salt separation to obtain a sodium sulfate concentrated aqueous solution with higher purity, wherein the nanofiltration product aqueous solution is mainly NaCl-based solution;
s40, carrying out low-temperature crystallization treatment on the concentrated aqueous solution of sodium sulfate in the step S30 through a freezing crystallizer 500, separating out sodium sulfate (Na 2 SO4.10H2O) crystals from the concentrated aqueous solution, discharging the sodium sulfate (Na 2 SO4.10H2O) crystals into a centrifugal machine 600 for centrifugal separation after deposition at the bottom of the freezing crystallizer 500, and drying the sodium sulfate crystals through a dryer 700 to obtain industrial product mirabilite; the nanofiltration water production solution is subjected to concentration decrement treatment by a butterfly pipe type reverse osmosis 800, and the reverse osmosis concentrated solution is reduced to 10% of inflow water;
s50, treating the reverse osmosis concentrated solution by a low-temperature negative pressure evaporator 900 to obtain purer industrial NaCl. Through detection, the purities of the sodium sulfate and the sodium chloride obtained in the embodiment are 98 percent and 97.5 percent respectively, which reach the standards above national class II salt, and the harmless treatment of sulfate radical in desulfurization wastewater is realized.
In addition, the water quality of the produced water obtained after the treatment of the embodiment is good, and reaches the direct drainage water quality standard, and the water quality of the produced water is shown in the following table 2:
TABLE 2 quality of treated effluent
The utility model has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will be understood that various modifications and changes may be made without departing from the scope of the utility model as defined by the appended claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and if any such modifications and variations are desired to be included within the scope of the utility model described herein. Furthermore, the background art is intended to illustrate the status and meaning of the development of the technology and is not intended to limit the utility model or the application and field of application of the utility model.
Claims (9)
1. Desulfurization waste water zero release processing system based on freezing crystallization technique includes pretreatment unit, ultrafiltration unit, nanofiltration unit and reverse osmosis unit in proper order, its characterized in that: the device also comprises a freezing crystallization unit and an evaporation crystallization unit, wherein the freezing crystallization unit is connected with the nanofiltration unit through a pipeline, and the evaporation crystallization unit is connected with the reverse osmosis unit through a pipeline; the freezing crystallization unit comprises a freezing crystallizer, a first backflow pipeline is arranged on the freezing crystallizer, and ice crystals obtained in the freezing crystallizer flow back to the front end of the nanofiltration unit through the first backflow pipeline; the evaporation crystallization unit comprises an evaporation crystallizer, a second backflow pipeline is arranged on the evaporation crystallizer, and condensed water used for processing the evaporation crystallizer flows back to the front end of the reverse osmosis unit through the second backflow pipeline.
2. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 1, wherein: the pretreatment unit comprises a homogenizing and adjusting tank (100) and a softening and reacting tank (200), wherein the homogenizing and adjusting tank (100) is connected with the softening and reacting tank (200) through a pipeline, and an outlet of the softening and reacting tank (200) is connected with an inlet of the ultrafiltration unit through a pipeline.
3. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 1, wherein: the ultrafiltration unit is an ultrafiltration membrane device (300), and a tubular softening membrane is arranged in the ultrafiltration membrane device (300).
4. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 1, wherein: the nanofiltration unit is a butterfly pipe nanofiltration device (400), a concentrated water outlet (401) and a nanofiltration water outlet (402) are arranged at the bottom of the butterfly pipe nanofiltration device (400), the concentrated water outlet (401) is connected with the freezing crystallization unit through a concentrated water pipeline (410), and the nanofiltration water outlet (402) is connected with the reverse osmosis unit through a nanofiltration water outlet pipeline (420).
5. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 1, wherein: the reverse osmosis unit is a butterfly pipe type reverse osmosis filter device (800), a reverse osmosis water outlet (801) and a strong brine outlet (802) are arranged at the bottom of the butterfly pipe type reverse osmosis filter device (800), and the strong brine outlet (802) is connected with the evaporation crystallization unit through a strong brine pipeline (810).
6. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 1, wherein: the freezing crystallization unit sequentially comprises a freezing crystallizer (500), a centrifugal separator (600) and a dryer (700), wherein the crystallized salt obtained in the freezing crystallizer (500) is connected to the centrifugal separator (600) through a pipeline for separation and purification, and then the separated and purified crystallized salt enters the dryer (700) through the pipeline for drying.
7. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 1, wherein: the first return pipeline is an ice crystal return pipe (510), and ice crystals obtained in the freezing crystallizer return to the inlet of the nanofiltration unit through the ice crystal return pipe (510); the second return pipeline is a condensate return pipeline (820), and condensate used for the treatment of the evaporative crystallizer flows back to the inlet of the reverse osmosis unit through the condensate return pipeline (820).
8. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 1, wherein: the evaporation crystallization unit is internally provided with a low-temperature negative pressure evaporator (900).
9. The desulfurization wastewater zero release treatment system based on the freezing crystallization technology according to claim 6, wherein: an orbit stirring rod is arranged in the freezing crystallizer (500).
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