CN209872651U - Treatment device for desulfurization wastewater quality-divided crystallization - Google Patents
Treatment device for desulfurization wastewater quality-divided crystallization Download PDFInfo
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- CN209872651U CN209872651U CN201920428227.4U CN201920428227U CN209872651U CN 209872651 U CN209872651 U CN 209872651U CN 201920428227 U CN201920428227 U CN 201920428227U CN 209872651 U CN209872651 U CN 209872651U
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Abstract
The utility model provides a desulfurization waste water divides processing apparatus of matter crystallization. The device comprises a magnetic separation unit, an ultrafiltration unit, a reverse osmosis unit, a nanofiltration unit and a concentration and crystallization unit, wherein the magnetic separation unit is used for carrying out magnetic separation treatment on the desulfurization wastewater to obtain a precipitate and a supernatant; the ultrafiltration unit is used for carrying out ultrafiltration treatment on the supernatant to obtain concentrated water; the reverse osmosis unit is used for performing reverse osmosis treatment on the concentrated water to obtain reverse osmosis concentrated solution; the nanofiltration unit is used for carrying out nanofiltration treatment on the reverse osmosis concentrated solution to obtain nanofiltration produced water containing sodium chloride and nanofiltration concentrated water containing sodium sulfate; and the concentration and crystallization unit is used for sequentially carrying out concentration treatment and crystallization treatment on the nanofiltration produced water to obtain sodium chloride crystals, and sequentially carrying out concentration treatment and crystallization treatment on the nanofiltration concentrated water to obtain sodium sulfate decahydrate crystals. The utility model provides a heavy metal ion when present desulfurization waste water divides matter crystallization treatment influence effect, the big scheduling problem of salt crystallization treatment scale.
Description
Technical Field
The utility model relates to a waste water treatment field particularly, relates to a processing apparatus of desulfurization waste water branch matter crystallization.
Background
The limestone-gypsum wet flue gas desulfurization process is a high-efficiency desulfurization technology which is most widely applied in the world and is also the mainstream process of flue gas desulfurization in China. The main principle of the process is to absorb SO in the flue gas by using alkaline slurry2And byproducts such as gypsum and the like are generated, but a large amount of desulfurization wastewater can be generated in the desulfurization process, and the desulfurization wastewater contains suspended matters, supersaturated sulfite, sulfate, heavy metals and other impurities, so that the desulfurization wastewater is difficult to treat, and meanwhile, some impurities belong to the first pollutants required to be controlled in the national environmental protection standard and have extremely strong environmental pollution.
In the traditional desulfurization wastewater treatment process, a three-header process is firstly adopted for pre-sedimentation treatment, then neutralization, flocculation and sedimentation treatment are carried out on the pre-sedimentation treatment to remove impurities such as suspended matters, heavy metals and the like in the desulfurization wastewater, and then effluent obtained after a series of treatment is directly used for ash flushing of a power plant. However, with the continuous improvement of environmental requirements, the desulfurization wastewater is subjected to advanced treatment and recycling to realize zero discharge of wastewater, and the method gradually becomes a development trend of the industry. However, the effluent obtained in the conventional desulfurization wastewater treatment process still has high salt content and cannot be directly recycled, so that desalination treatment needs to be performed on the desulfurization wastewater.
At present, the desulfurization wastewater zero-discharge process mainly comprises a chemical hardness removal pretreatment system, a membrane concentration reduction system, an evaporative crystallization system and other process sections. The pretreatment section adopts traditional chemical dosing for hardness removal and softening, the dosing amount is large, the sludge yield is large, and the operation is complicated; the membrane concentration reduction section adopts direct evaporation crystallization after membrane concentration, so that the energy consumption is high, the equipment is easy to scale, and only mixed salt of sodium chloride and sodium sulfate can be generated, so that the recycling is difficult. In some improved processes, nanofiltration is adopted for separating salt and then concentrating, only nanofiltration produced water is evaporated and crystallized, and nanofiltration concentrated water returns to a system along with concentrated solution, and mass separation and crystallization are not realized.
Patent document CN106946395A "a method and a device for fractional crystallization treatment of desulfurization wastewater" discloses a fractional crystallization technique for desulfurization wastewater, but the treatment process does not remove heavy metal ions, so that salt crystals and effluent obtained subsequently are affected; secondly, the recovery rate of the concentrated water is low, resulting in a large scale of the crystallization treatment.
SUMMERY OF THE UTILITY MODEL
The utility model discloses a main aim at provides a processing apparatus of desulfurization waste water branch matter crystallization to there are heavy metal ion to influence the treatment effect in solving among the prior art desulfurization waste water branch matter crystallization process, the great scheduling problem of salt crystallization treatment scale.
In order to achieve the above object, one aspect of the present invention provides a desulfurization wastewater treatment device for fractional crystallization, comprising: a magnetic separation unit having a desulfurization wastewater inlet, and having a first pH adjustor inlet, an organic sulfur agent inlet, and an iron ore particle inlet, the magnetic separation unit serving to subject the desulfurization wastewater to a magnetic separation treatment to obtain a precipitate and a supernatant; the ultrafiltration unit is connected with the outlet of the magnetic separation unit and is provided with a second pH regulator inlet, and the ultrafiltration unit is used for carrying out ultrafiltration treatment on the supernatant to obtain concentrated water; the reverse osmosis unit is connected with the outlet of the ultrafiltration unit and is used for performing reverse osmosis treatment on the concentrated water to obtain reverse osmosis concentrated solution; the nanofiltration unit is connected with an outlet of the reverse osmosis unit and is used for carrying out nanofiltration treatment on the reverse osmosis concentrated solution to obtain nanofiltration produced water containing sodium chloride and nanofiltration concentrated water containing sodium sulfate; and the concentration and crystallization unit is connected with an outlet of the nanofiltration unit and is used for sequentially carrying out concentration treatment and crystallization treatment on nanofiltration produced water to obtain sodium chloride crystals and sequentially carrying out concentration treatment and crystallization treatment on the nanofiltration concentrated water to obtain sodium sulfate decahydrate crystals.
Further, the magnetic separation unit comprises: the first reaction device is provided with a desulfurization wastewater inlet, a first pH regulator inlet, an organic sulfur agent inlet and an iron ore inlet, and is used for providing a place for magnetic separation treatment of desulfurization wastewater; the first feeding device is connected with the pH regulator inlet and is used for providing one or more of liquid caustic soda, calcined soda, lime and magnesium agents as a first pH regulator; a second supply device connected to the organosulfur agent inlet for supplying TMT-15 as the organosulfur agent; a third feeding device connected to the iron ore particle inlet, the third feeding device for supplying iron ore particles; and the magnetic separation device is arranged in the first reaction device and is used for performing magnetic separation treatment on the desulfurization wastewater to obtain sediment and supernatant.
Further, the first reaction device has a precipitate outlet, and the magnetic separation unit further includes: the third reaction device is connected with the sediment outlet and is used for providing a place for separating and recovering iron ore particles; and the cyclone device is arranged in the third reaction device and is used for performing cyclone separation on the sediment so as to recover iron ore particles.
Further, the ultrafiltration unit comprises: the second reaction device is provided with a second pH regulator inlet and is used for providing a place for the supernatant to carry out second pH regulation; the fourth feeding device is connected with the second pH regulator inlet and is used for providing acid as a second pH regulator; and the ultrafiltration device is connected with the outlet of the second reaction device and is provided with a concentrated water outlet, and the ultrafiltration device is used for performing ultrafiltration treatment on the supernatant to obtain concentrated water.
Further, ultrafiltration product water is obtained in the step of ultrafiltration treatment, the ultrafiltration device is also provided with an ultrafiltration product water outlet, the first reaction device is provided with a backwash water inlet, and the ultrafiltration unit further comprises: the first recovery device is respectively connected with the ultrafiltration water outlet and the backwashing water inlet.
Further, the reverse osmosis unit comprises: and the reverse osmosis device is connected with the concentrated water outlet and is provided with a reverse osmosis concentrated solution outlet, and the reverse osmosis device is used for performing reverse osmosis concentration on the concentrated water to obtain reverse osmosis concentrated solution.
Further, the reverse osmosis apparatus comprises: a reverse osmosis membrane for performing reverse osmosis, preferably the reverse osmosis membrane is selected from a disk tube reverse osmosis membrane; and the vibration device is connected with the reverse osmosis membrane and is used for providing vibration elasticity for the reverse osmosis membrane so that the reverse osmosis membrane can perform reverse osmosis in a dynamic mode.
Further, the reverse osmosis concentration process also produces reverse osmosis produced water, and reverse osmosis unit has the reverse osmosis and produces the water export, and reverse osmosis unit still includes: and the second recovery device is connected with the reverse osmosis water production outlet and is used for recovering reverse osmosis water production.
Further, the nanofiltration unit comprises: and the nanofiltration device is connected with the reverse osmosis concentrated solution outlet and is provided with a nanofiltration water production outlet and a nanofiltration concentrated water outlet, and the nanofiltration device is used for performing nanofiltration treatment on the reverse osmosis concentrated solution to respectively obtain nanofiltration water production containing sodium chloride and nanofiltration concentrated water containing sodium sulfate.
Further, the concentration crystallization unit comprises: the first concentration device is connected with the nanofiltration water production outlet and is provided with a sodium chloride solution outlet, and the first concentration device is used for concentrating the nanofiltration water production containing sodium chloride to obtain a sodium chloride solution; the second concentration device is connected with the nanofiltration concentrated water outlet and is provided with a sodium sulfate solution outlet, and the second concentration device is used for concentrating the nanofiltration concentrated water containing sodium sulfate to obtain a sodium sulfate solution; the first crystallization device is connected with the sodium chloride solution outlet and is used for crystallizing the sodium chloride solution to obtain sodium chloride crystals; and the second crystallizing device is connected with the sodium sulfate solution outlet and is used for crystallizing the sodium sulfate solution to obtain sodium sulfate decahydrate crystals.
Further, the first concentration device and the second concentration device both comprise high-pressure flat membranes for concentration treatment; the first crystallization device is an evaporation crystallization device, and the second crystallization device is a freezing crystallization device.
Further, the step of carrying out crystallization treatment on the sodium sulfate crystal also produces a denitration liquid, the second crystallization device is provided with a denitration liquid outlet, the reverse osmosis device is provided with a denitration backwash liquid inlet, and the concentration and crystallization unit further comprises: and the third recovery device is respectively connected with the denitration liquid outlet and the denitration backwash liquid inlet, and is used for recycling the denitration liquid.
Further, the processing apparatus further comprises: and the homogenizing unit is connected with the desulfurization wastewater inlet and is used for carrying out homogenizing treatment on the desulfurization wastewater.
Further, the homogenizing unit includes: the adjusting tank is connected with the desulfurization wastewater inlet and is used for carrying out homogenization treatment on the desulfurization wastewater; and the stirring device is connected with the regulating tank and is used for stirring the desulfurization wastewater in the regulating tank.
Use the technical scheme of the utility model, at first carry out the first regulation to the pH of desulfurization waste water, can get rid of supersaturated sulphite and sulfate impurity in the waste water, get rid of magnesium ion and partial heavy metal ion in the waste water simultaneously. And then, adding an organic sulfur medicament and iron ore particles, wherein the organic sulfur medicament can generate a water-insoluble stable chelate with heavy metal ions which cannot be removed by hydroxyl, and the iron ore particles are used as magnetic seeds to endow the heavy metal ions with magnetism, so that the heavy metal ions are further treated and removed by magnetic separation, the use amount of the traditional medicament (such as a flocculating agent and a high polymer) for removing the heavy metal ions is reduced, the treatment cost is also saved, and the problem that the flocculating agent and the high polymer pollute a subsequent ultrafiltration and nanofiltration system is solved. And then, carrying out secondary adjustment on the pH value of the supernatant obtained by magnetic separation treatment, and then carrying out ultrafiltration treatment to remove suspended matters in the desulfurization wastewater to obtain concentrated water. And the concentrated water is subjected to reverse osmosis concentration, so that the reduction of the concentrated water is realized, and the scale of subsequent crystallization treatment is reduced. Then the obtained reverse osmosis concentrated solution is subjected to nanofiltration treatment, so that the salt separation of sodium chloride and sodium sulfate is realized. And finally, sequentially carrying out concentration and crystallization treatment on the nanofiltration produced water containing sodium chloride to obtain sodium chloride crystals, and sequentially carrying out concentration and crystallization treatment on the nanofiltration concentrated water containing sodium sulfate to obtain sodium sulfate decahydrate crystals, thereby realizing the quality-divided crystallization of the desulfurization wastewater.
Drawings
The accompanying drawings, which form a part of the present application, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. In the drawings:
fig. 1 is a block diagram illustrating a desulfurization waste water fractional crystallization treatment apparatus according to a preferred embodiment of the present invention.
Wherein the figures include the following reference numerals:
10. a homogenizing unit; 11. a regulating tank; 12. a stirring device; 20. a magnetic separation unit; 21. a first reaction device; 22. a first feeding device; 23. a second feeding device; 24. a third feeding device; 25. a magnetic separation device; 30. an ultrafiltration unit; 31. a second reaction device; 32. a fourth supply device; 33. an ultrafiltration device; 34. a first recycling device; 40. a reverse osmosis unit; 41. a reverse osmosis unit; 42. a second recovery device; 50. a nanofiltration unit; 51. a nanofiltration device; 60. a concentration and crystallization unit; 61. a first concentration device; 62. a second concentration device; 63. a first crystallization device; 64. a second crystallization device; 65. and a third recovery device.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
As described in the background art, the treatment effect is influenced by heavy metal ions in the quality-divided crystallization treatment process of the desulfurization wastewater in the prior art, and the salt crystallization treatment scale is large. In order to solve the technical problem, the utility model provides a processing apparatus of desulfurization waste water branch matter crystallization, as shown in fig. 1, this processing apparatus includes: a magnetic separation unit 20, an ultrafiltration unit 30, a reverse osmosis unit 40, a nanofiltration unit 50, and a concentration crystallization unit 60. Wherein the magnetic separation unit 20 has an inlet for the desulfurization waste water, and has an inlet for the first pH adjusting agent, an inlet for the organic sulfur agent, and an inlet for the iron ore, and the magnetic separation unit 20 serves to subject the desulfurization waste water to a magnetic separation treatment to obtain a precipitate and a supernatant; the ultrafiltration unit 30 is connected with the outlet of the magnetic separation unit 20 and is provided with a second pH regulator inlet, and the ultrafiltration unit 30 is used for performing ultrafiltration treatment on the supernatant to obtain concentrated water; the reverse osmosis unit 40 is connected with the outlet of the ultrafiltration unit 30, and the reverse osmosis unit 40 is used for performing reverse osmosis treatment on the concentrated water to obtain reverse osmosis concentrated solution; the nanofiltration unit 50 is connected with an outlet of the reverse osmosis unit 40, and the nanofiltration unit 50 is used for performing nanofiltration treatment on the reverse osmosis concentrated solution to obtain nanofiltration product water containing sodium chloride and nanofiltration concentrated water containing sodium sulfate; the concentration and crystallization unit 60 is connected with an outlet of the nanofiltration unit 50, and the concentration and crystallization unit 60 is used for sequentially performing concentration treatment and crystallization treatment on nanofiltration produced water to obtain sodium chloride crystals, and sequentially performing concentration treatment and crystallization treatment on the nanofiltration concentrated water to obtain sodium sulfate decahydrate crystals.
The utility model discloses at first carry out the first regulation to the pH of desulfurization waste water, can get rid of supersaturated sulphite and sulfate impurity in the waste water, get rid of magnesium ion and partial heavy metal ion in the waste water simultaneously. And then, adding an organic sulfur medicament and iron ore particles, wherein the organic sulfur medicament can generate a water-insoluble stable chelate with heavy metal ions which cannot be removed by hydroxyl, and the iron ore particles are used as magnetic seeds to endow the heavy metal ions with magnetism, so that the heavy metal ions are further treated and removed by magnetic separation, the use amount of the traditional medicament (such as a flocculating agent and a high polymer) for removing the heavy metal ions is reduced, the treatment cost is also saved, and the problem that the flocculating agent and the high polymer pollute a subsequent ultrafiltration and nanofiltration system is solved. And then, carrying out secondary adjustment on the pH value of the supernatant obtained by magnetic separation treatment, and then carrying out ultrafiltration treatment to remove suspended matters in the desulfurization wastewater to obtain concentrated water. And the concentrated water is subjected to reverse osmosis concentration, so that the reduction of the concentrated water is realized, and the scale of subsequent crystallization treatment is reduced. Then the obtained reverse osmosis concentrated solution is subjected to nanofiltration treatment, so that the salt separation of sodium chloride and sodium sulfate is realized. And finally, sequentially carrying out concentration and crystallization treatment on the nanofiltration produced water containing sodium chloride to obtain sodium chloride crystals, and sequentially carrying out concentration and crystallization treatment on the nanofiltration concentrated water containing sodium sulfate to obtain sodium sulfate decahydrate crystals, thereby realizing the quality-divided crystallization of the desulfurization wastewater. In a word, the device effectively solves the problems that heavy metal ions influence the treatment effect, the salt crystallization treatment scale is large and the like in the desulfurization wastewater quality-grading crystallization treatment process, and can more effectively carry out quality-grading crystallization treatment on the desulfurization wastewater.
In a preferred embodiment, as shown in FIG. 1, the magnetic separation unit 20 comprises: a first reaction device 21, a first supply device 22, a second supply device 23, a third supply device 24 and a magnetic separation device 25. The first reaction device 21 is provided with a desulfurization wastewater inlet, a first pH regulator inlet, an organic sulfur agent inlet and an iron ore inlet, and the first reaction device 21 is used for providing a place for magnetic separation treatment of desulfurization wastewater; the first feeding device 22 is connected with the pH regulator inlet, and the first feeding device 22 is used for providing one or more of liquid caustic soda, calcined soda, lime and magnesium agents as a first pH regulator; a second supply means 23 connected to the organosulfur agent inlet, the second supply means 23 being for supplying TMT-15 as the organosulfur agent; a third feeding device 24 is connected to the iron ore inlet, the third feeding device 24 is used for providing iron ore; a magnetic separation device 25 is arranged in the first reaction device 21, and the magnetic separation device 25 is used for performing magnetic separation treatment on the desulfurization wastewater to obtain sediment and supernatant. And (3) removing supersaturated sulfite, sulfate and part of heavy metal ion impurities in the desulfurization wastewater in the first reaction device by adding one or more of liquid caustic soda, soda ash, lime or magnesium agents. Then, iron ore is added to carry out magnetic separation treatment, so that heavy metal ions which cannot be removed by hydroxide ions are further removed.
In a preferred embodiment, as shown in fig. 1, the first reaction device 21 has a sediment outlet, and the magnetic separation unit 20 further comprises a third reaction device and a cyclone device. Wherein the third reaction device is connected with the sediment outlet and is used for providing a place for separating and recovering the iron ores; and the cyclone device is arranged in the third reaction device and is used for performing cyclone separation on the sediment so as to recover iron ore particles. And iron ore particles in the sediment obtained by the magnetic separation treatment are separated and recovered through the cyclone device, so that the reasonable utilization of resources is realized.
In a preferred embodiment, as shown in fig. 1, the ultrafiltration unit 30 comprises a second reaction device 31, a fourth feed device 32 and an ultrafiltration device 33. Wherein, the second reaction device 31 is provided with a second pH regulator inlet, and the second reaction device 31 is used for providing a place for the second pH regulation of the supernatant; the fourth feeding device 32 is connected with the second pH regulator inlet and is used for providing acid as a second pH regulator; the ultrafiltration device 33 is connected with the outlet of the second reaction device 31 and is provided with a concentrated water outlet, and the ultrafiltration device 33 is used for performing ultrafiltration treatment on the supernatant to obtain concentrated water. And adding acid into the second reaction device through the first feeding device to adjust the pH value of the supernatant to 6.5-7.5, so that the supernatant tends to be neutral. And then the adjusted supernatant is subjected to ultrafiltration treatment by an ultrafiltration device, so that suspended matters in the desulfurization wastewater can be removed.
In a preferred embodiment, as shown in fig. 1, the ultrafiltration treatment step further produces ultrafiltration product water, the ultrafiltration device 33 further has an ultrafiltration product water outlet, the first reaction device 21 has a backwash water inlet, and the ultrafiltration unit 30 further comprises a first recovery device 34 connected to the ultrafiltration product water outlet and the backwash water inlet, respectively. The ultrafiltration water produced in the ultrafiltration treatment process is recycled through the first recovery device and returned to the magnetic separation unit for recycling, and part of medicament is remained in the backwash water, so that the adding amount of the medicament in the subsequent magnetic separation treatment is favorably reduced, the treatment cost is saved, and meanwhile, the water resource is favorably saved.
In a preferred embodiment, as shown in fig. 1, the reverse osmosis unit 40 comprises a reverse osmosis device 41 connected to the concentrate outlet and having a reverse osmosis concentrate outlet, the reverse osmosis device 41 being adapted to reverse osmosis concentrate the concentrate to obtain a reverse osmosis concentrate. The reverse osmosis device is used for carrying out reverse osmosis concentration treatment on the concentrated water, so that the reduction of the concentrated water is favorably realized, and the scale of subsequent crystallization treatment is reduced.
In a preferred embodiment, as shown in fig. 1, the reverse osmosis apparatus 41 comprises: a reverse osmosis membrane and a vibration device. Wherein the reverse osmosis membrane is used for reverse osmosis, preferably the reverse osmosis membrane is selected from a disc tube reverse osmosis membrane; the vibration device is connected with the reverse osmosis membrane and used for providing vibration elasticity for the reverse osmosis membrane so that the reverse osmosis membrane can perform reverse osmosis in a dynamic mode. The disc tube type reverse osmosis membrane is beneficial to increasing the toughness of the reverse osmosis membrane, prolonging the service life of the reverse osmosis membrane and further improving the concentration efficiency. The vibrating device provides vibrating elasticity for the reverse osmosis membrane, and the membrane is subjected to material separation in a dynamic mode, so that impurity particles cannot be enriched on the surface of the reverse osmosis membrane, the flux of the reverse osmosis membrane is maintained without receiving influence, and the problems of reverse osmosis membrane blockage and membrane pollution are avoided.
In a preferred embodiment, shown in figure 1, the reverse osmosis concentration process also produces reverse osmosis product water, the reverse osmosis unit 41 having a reverse osmosis product water outlet, and the reverse osmosis unit 40 further comprising a second recovery unit 42 connected to the reverse osmosis product water outlet for recovering the reverse osmosis product water. The reverse osmosis produced water is recycled through the second recycling device, and part of medicament is remained in the reverse osmosis produced water, so that the adding amount of the medicament in the subsequent magnetic separation treatment is reduced, the treatment cost is saved, and meanwhile, the water resource is saved.
In a preferred embodiment, as shown in fig. 1, nanofiltration unit 50 comprises a nanofiltration device 51 connected to the reverse osmosis concentrate outlet and having a nanofiltration product water outlet and a nanofiltration concentrate water outlet, nanofiltration device 51 being adapted to perform nanofiltration on the reverse osmosis concentrate to obtain a nanofiltration product water containing sodium chloride and a nanofiltration concentrate water containing sodium sulfate, respectively. The nanofiltration treatment is carried out on the reverse osmosis concentrated solution through the nanofiltration device, which is favorable for realizing the salt separation of sodium chloride and sodium sulfate and respectively obtaining nanofiltration produced water containing sodium chloride solution and nanofiltration concentrated water containing sodium sulfate solution. In addition to the nanofiltration device 51, the nanofiltration unit 50 may further include a flow meter for adjusting the inflow rate of the reverse osmosis concentrate.
In a preferred embodiment, as shown in FIG. 1, the concentration crystallization unit 60 comprises: a first concentration device 61, a second concentration device 62, a first crystallization device 63 and a second crystallization device 64. Wherein the first concentration device 61 is connected with the nanofiltration water production outlet and is provided with a sodium chloride solution outlet, and the first concentration device 61 is used for concentrating the nanofiltration water production containing sodium chloride to obtain a sodium chloride solution; the second concentration device 62 is connected with the nanofiltration concentrated water outlet and is provided with a sodium sulfate solution outlet, and the second concentration device 62 is used for concentrating nanofiltration concentrated water containing sodium sulfate to obtain a sodium sulfate solution; the first crystallization device 63 is connected with a sodium chloride solution outlet, and the first crystallization device 63 is used for carrying out crystallization treatment on a sodium chloride solution to obtain sodium chloride crystals; the second crystallizing device 64 is connected to the outlet of the sodium sulfate solution, and the second crystallizing device 64 is used for crystallizing the sodium sulfate solution to obtain sodium sulfate decahydrate crystals. The nanofiltration water containing sodium chloride is subjected to concentration and crystallization treatment through a first concentration device and a first crystallization device which are sequentially connected to obtain high-purity sodium chloride crystals, and the nanofiltration concentrated water containing sodium sulfate is subjected to concentration and crystallization treatment through a second concentration device and a second crystallization device which are sequentially connected to obtain high-purity sodium sulfate decahydrate crystals.
In a preferred embodiment, as shown in fig. 1, the first and second concentrating devices 61 and 62 each comprise a high-pressure flat membrane to perform the concentrating process; the first crystallization device 63 is an evaporation crystallization device, and the second crystallization device 64 is a freezing crystallization device. According to the different solubility properties of sodium sulfide and sodium sulfate, respectively adopting different crystallization devices to respectively carry out freezing crystallization and evaporative crystallization treatment on the sodium sulfide and the sodium sulfate to respectively obtain sodium chloride crystals and sodium sulfate decahydrate crystals
In a preferred embodiment, as shown in fig. 1, the step of crystallizing the sodium sulfate crystals also produces a denitrated liquid, the second crystallizing device 64 has a denitrated liquid outlet, the reverse osmosis device 41 has a denitrated backwash liquid inlet, and the concentration and crystallization unit 60 further comprises a third recovery device 65 connected to the denitrated liquid outlet and the denitrated backwash liquid inlet, respectively, for recovering and reusing the denitrated liquid.
In a preferred embodiment, as shown in fig. 1, the treatment apparatus further comprises a homogenizing unit 10 connected to the inlet of the desulfurization waste water for homogenizing the desulfurization waste water. Carry out the homogeneity through the homogeneity unit to desulfurization waste water and handle, be favorable to making the impurity in the desulfurization waste water realize more even distribution, and then promote the effect of follow-up medicament.
In a preferred embodiment, as shown in FIG. 1, the homogenizing unit 10 includes a conditioning tank 11 and a stirring device 12. Wherein, the regulating tank 11 is connected with the inlet of the desulfurization waste water and is used for carrying out homogenization treatment on the desulfurization waste water; the stirring device 12 is provided in the conditioning tank 11 and serves to stir the desulfurization waste water in the conditioning tank. Carry out intensive mixing through agitating unit to the desulfurization waste water in the equalizing basin, realize the homogeneity and handle, be favorable to making the impurity in the desulfurization waste water realize more even distribution.
In another exemplary embodiment, the present application provides a method for treating desulfurized wastewater containing sodium chloride and sodium sulfate by fractional crystallization, comprising: firstly, carrying out primary pH adjustment on the desulfurization wastewater, adjusting the pH of the desulfurization wastewater to 9-12, and then adding an organic sulfur medicament and iron ore particles into the adjusted desulfurization wastewater to carry out magnetic separation treatment to obtain a precipitate and a supernatant; then, carrying out secondary pH adjustment on the supernatant, adjusting the pH of the supernatant to 6.5-7.5, and then carrying out ultrafiltration treatment to obtain concentrated water; then carrying out reverse osmosis treatment on the concentrated water to obtain reverse osmosis concentrated solution; then carrying out nanofiltration treatment on the reverse osmosis concentrated solution to obtain nanofiltration produced water containing sodium chloride and nanofiltration concentrated water containing sodium sulfate; and finally, sequentially carrying out concentration treatment and crystallization treatment on nanofiltration concentrated water to obtain sodium chloride crystals, and sequentially carrying out concentration treatment and crystallization treatment on the nanofiltration concentrated water to obtain sodium sulfate decahydrate crystals.
According to the technical method provided by the application, the pH value of the desulfurization wastewater is adjusted to 9-12, supersaturated sulfite and sulfate impurities in the wastewater can be removed, and magnesium ions and partial heavy metal ions in the wastewater are removed. And then, adding an organic sulfur medicament and iron ore particles, wherein the organic sulfur medicament can generate a water-insoluble stable chelate with heavy metal ions which cannot be removed by hydroxyl, and the iron ore particles are used as magnetic seeds to endow the heavy metal ions with magnetism, so that the heavy metal ions are further treated and removed by magnetic separation, the use amount of the traditional medicament (such as a flocculating agent and a high polymer) for removing the heavy metal ions is reduced, the treatment cost is also saved, and the problem that the flocculating agent and the high polymer pollute a subsequent ultrafiltration and nanofiltration system is solved. And then, adjusting the pH value of the supernatant obtained by magnetic separation to 6.5-7.5, and then performing ultrafiltration treatment to remove suspended matters in the desulfurization wastewater to obtain concentrated water. And the concentrated water is subjected to reverse osmosis concentration, so that the reduction of the concentrated water is realized, and the scale of subsequent crystallization treatment is reduced. Then the obtained reverse osmosis concentrated solution is subjected to nanofiltration treatment, so that the salt separation of sodium chloride and sodium sulfate is realized. And finally, sequentially carrying out concentration and crystallization treatment on the nanofiltration produced water containing sodium chloride to obtain sodium chloride crystals, and sequentially carrying out concentration and crystallization treatment on the nanofiltration concentrated water containing sodium sulfate to obtain sodium sulfate decahydrate crystals, thereby realizing the quality-divided crystallization of the desulfurization wastewater.
In a preferred embodiment, the iron ore particles have a particle size of 45 to 100 μm; preferably, the adding amount of the iron ore particles is 1-3 g/L and the magnetic separation treatment time is 5-10 min relative to the pretreatment amount of the desulfurization wastewater. The iron ore particles act as magnetic species so that the heavy metal ions are given magnetism, thereby enabling the heavy metal ions to be removed by magnetic separation treatment. The particle size of the iron ore particles includes, but is not limited to, the ranges provided above, but the iron ore particles within the ranges are advantageous for increasing the contact area with the heavy metal ions and improving the magnetic imparting effect. The adding amount of the iron ore particles can be properly adjusted according to the actual content of the heavy metal ions in the pretreated desulfurization wastewater, the preferable adding amount is 10-20 g/g, on the other hand, the adding amount of the iron ore particles has certain correlation with the magnetic separation treatment time, and the magnetic separation treatment is carried out for 5-10 min within the adding amount range of the iron ore, so that the removal of the heavy metal ions can be fully realized, and the working period of the treatment process can be shortened.
In a preferred embodiment, the pH regulator used in the first pH adjustment process is selected from one or more of liquid caustic soda, soda ash and lime; preferably, the organosulfur agent is selected from the group consisting of TMT-15; preferably, the pH regulator used in the second pH regulation process is acid, and more preferably, before the step of magnetic separation treatment, a flocculating agent is further added, wherein the flocculating agent is selected from PAC and/or PFS, and the adding amount of the flocculating agent is 3-100 mg/L. The liquid alkali can remove heavy metal ions such as calcium, aluminum, strontium and the like while adjusting the pH. The addition of calcium and magnesium ions in the agent can form sulfate precipitate and remove supersaturated sulfite and sulfate impurities in the wastewater. The addition of hydroxide ions enables the removal of magnesium ions and part of heavy metal ions while adjusting the pH. The addition of soda ash can remove calcium ions in water to form calcium carbonate precipitate. The organic sulfur agent is used for generating chelate with heavy metal ions, preferably TMT-15, and the formed chelate is stable and convenient and easy to obtain. The flocculant and the high molecular polymer are properly added, so that heavy metal ions in the desulfurization wastewater can be further removed, and meanwhile, in order to influence the added flocculant and the high molecular polymer on a subsequent ultrafiltration and nanofiltration system, the addition amount of the flocculant and the high molecular polymer is preferably 3-30 mg/L.
In a preferred embodiment, the ultrafiltration is carried out in a cross-flow manner in the ultrafiltration treatment step, and the hardness of the concentrated water is controlled to be lower than 100 mg/L. The ultrafiltration treatment can further remove suspended matters and colloid impurities in the desulfurization wastewater, and the ultrafiltration mode is not limited to the provided mode, but the cross-flow mode is adopted for ultrafiltration, so that the ultrafiltration efficiency is improved, and the treatment process period is shortened. And the hardness of the obtained concentrated water is controlled below 100mg/L, which is beneficial to the subsequent concentration and crystallization treatment of sodium sulfate and sodium chloride and improves the purity of the crystals.
In a preferred embodiment, ultrafiltration product water is also obtained in the step of ultrafiltration treatment, and the turbidity of concentrated water and the turbidity of the ultrafiltration product water are both lower than 1 NTU; preferably, the processing method further includes: returning the ultrafiltration product water to the magnetic separation treatment step to be used as backwashing water. The turbidity of the concentrated water and the ultrafiltration produced water is controlled, which is further beneficial to the concentration and crystallization treatment of the subsequent sodium sulfate and sodium chloride, and further improves the purity of the crystals. And the ultrafiltration produced water is returned to the magnetic separation treatment as backwash water for recycling, and part of medicament is remained in the backwash water, so that the addition amount of the medicament in the subsequent magnetic separation treatment is reduced, the treatment cost is saved, and the water resource is saved.
In a preferred embodiment, the concentrated water is introduced in a direction perpendicular to the reverse osmosis membrane in the reverse osmosis treatment step, preferably the reverse osmosis membrane is selected from a disk tube reverse osmosis membrane. In the reverse osmosis treatment, concentrated water is introduced from the upper part of the reverse osmosis membrane, preferably in the direction perpendicular to the reverse osmosis membrane, so that the reverse osmosis treatment is favorable for improving the reverse osmosis efficiency. Adopt disc tube formula reverse osmosis membrane can increase reverse osmosis membrane's toughness, improve reverse osmosis membrane's life, still be favorable to further improving concentration efficiency simultaneously.
In a preferred embodiment, the step of reverse osmosis treatment further comprises: the reverse osmosis membrane is provided with vibration elasticity to allow the reverse osmosis membrane to perform reverse osmosis in a dynamic manner. The vibrating device provides vibrating elasticity for the reverse osmosis membrane, and the membrane is subjected to material separation in a dynamic mode, so that impurity particles cannot be enriched on the surface of the reverse osmosis membrane, the flux of the reverse osmosis membrane is maintained without receiving influence, and the problems of reverse osmosis membrane blockage and membrane pollution are avoided.
In a preferred embodiment, the reverse osmosis treatment step further produces reverse osmosis produced water, and the treatment method further comprises the step of recycling the reverse osmosis produced water. The reverse osmosis produced water is recycled, and part of the medicament is remained in the reverse osmosis produced water, so that the adding amount of the medicament in the subsequent magnetic separation treatment is reduced, the treatment cost is saved, and the water resource is saved.
In a preferred embodiment, the sodium chloride solution is obtained in the step of concentrating the nanofiltration water, and the concentration of the sodium chloride solution is more than 13%; and concentrating the nanofiltration concentrated water to obtain a sodium sulfate solution, wherein the concentration of the sodium sulfate solution is more than 17%. After reverse osmosis concentration, nanofiltration produced water and nanofiltration concentrated water are concentrated for the second time, so that the concentrations of a sodium chloride solution and a sodium sulfate solution are further improved, and the steps of subsequent crystallization treatment are simplified.
In a preferred embodiment, the sodium sulfate solution is subjected to a freezing crystallization process to obtain sodium sulfate decahydrate crystals; the sodium chloride solution is subjected to evaporative crystallization treatment to obtain sodium chloride crystals. According to different solubility properties of sodium chloride and sodium sulfate, the sodium chloride and the sodium sulfate are respectively subjected to freezing crystallization and evaporative crystallization to respectively obtain sodium chloride crystals and sodium sulfate decahydrate crystals.
In a preferred embodiment, before the first pH adjustment process, the treatment method further comprises the step of homogenizing the desulfurized wastewater; preferably, the processing method further comprises the step of separating and recovering the iron ore in the precipitate by using an electromagnetic separation technology. Carry out the homogeneity to desulfurization waste water before carrying out pH and adjusting and handle, do benefit to and make the impurity in the desulfurization waste water realize more even distribution, be favorable to improving the utility of follow-up medicament. And the separation and recovery of the iron ore particles realize the reasonable utilization of resources and further reduce the treatment cost.
In a preferred embodiment, the step of freezing and crystallizing treatment further produces denitrated liquid, and the treatment method further comprises returning the denitrated liquid to the step of reverse osmosis treatment for retreatment. And returning the denitrated liquid to the step of reverse osmosis treatment for retreatment, which is favorable for improving the yield of sodium chloride crystals. The denitration liquid is characterized in that: when the sodium sulfate solution is frozen and crystallized, the sodium sulfate is crystallized and separated out in a mirabilite form, and the sulfate solution which does not completely separate out crystals is the denitration solution.
The present invention is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
TABLE 1 Water quality indices of desulfurized waste Water (influent) and recycled Water storage (effluent)
Example 1
And introducing the desulfurization wastewater into a regulating tank, carrying out homogenization treatment by a stirrer, and introducing the desulfurization wastewater subjected to the homogenization treatment into a reaction tank. Adding soda ash and magnesium chloride into the reaction tank to adjust the pH value of the desulfurization wastewater to 10, then introducing the desulfurization wastewater into a precipitation tank, adding TMT-15 and iron ore particles, opening a magnetic separation device for treatment for 8min, and respectively obtaining a precipitate and a supernatant. Wherein the precipitate is transferred into a sedimentation tank, and iron ore particles in the precipitate are separated by a cyclone and recycled. In addition, the hardness of the supernatant was measured to be 3ml/L, hydrochloric acid was added to the supernatant to adjust the pH to 7, and then ultrafiltration was performed through an ultrafilter to filter out suspended substances and colloidal impurities therein, to obtain concentrated water having a turbidity of 0.15 NTU. Adopts a disc tube type reverse osmosis membrane to carry out reverse osmosis concentration treatment on the concentrated water SO as to ensure that SO4 2-、Na+And Cl-And then the filtrate enters reverse osmosis concentrated solution. And simultaneously, discharging the obtained reverse osmosis produced water into a reuse water pool for later use. And performing nanofiltration treatment on the reverse osmosis concentrated solution by using a disc-tube nanofiltration membrane to respectively obtain nanofiltration product water containing a sodium chloride solution and nanofiltration concentrated water containing sodium sulfate, wherein the content of chloride ions in the nanofiltration product water is 25000mg/L, and the content of sodium sulfate ions in the nanofiltration concentrated water is 38000 mg/L. And then, deeply concentrating the nanofiltration produced water and the nanofiltration concentrated water by adopting a high-pressure flat RO (reverse osmosis) membrane to respectively obtain a sodium chloride solution with the mass concentration of 14% and a sodium sulfate solution with the mass concentration of 17%. Freezing and crystallizing the sodium sulfate solution to obtain sodium sulfate decahydrate crystals with the purity of 98.9 percent; and (3) carrying out evaporation crystallization treatment on the sodium chloride solution to obtain sodium chloride crystals with the purity of 96.5%. Wherein, the condensed water in the evaporation crystallization process is discharged into a reuse water pool for standby.
Example 2
And introducing the desulfurization wastewater into a regulating tank, carrying out homogenization treatment by a stirrer, and introducing the desulfurization wastewater subjected to the homogenization treatment into a reaction tank. Adding liquid alkali and lime into the reaction tank to remove the liquid alkali and limeAdjusting the pH value of the desulfurization wastewater to 12, introducing the desulfurization wastewater into a precipitation tank, adding TMT-15 and iron ore particles, opening a magnetic separation device for treatment for 8min, and respectively obtaining a precipitate and a supernatant. Wherein the precipitate is transferred into a sedimentation tank, and iron ore particles in the precipitate are separated by a cyclone and recycled. In addition, the hardness of the supernatant was measured to be 4ml/L, hydrochloric acid was added to the supernatant to adjust the pH to 6.5, and then ultrafiltration was performed through an ultrafilter to filter out suspended substances and colloidal impurities therein, to obtain concentrated water having a turbidity of 0.15 NTU. Adopts a disc tube type reverse osmosis membrane to carry out reverse osmosis concentration treatment on the concentrated water SO as to ensure that SO4 2-、Na+And Cl-And then the filtrate enters reverse osmosis concentrated solution. And simultaneously, discharging the obtained reverse osmosis produced water into a reuse water pool for later use. And performing nanofiltration treatment on the reverse osmosis concentrated solution by using a disc-tube nanofiltration membrane to respectively obtain nanofiltration produced water containing a sodium chloride solution and nanofiltration concentrated water containing sodium sulfate, wherein the content of chloride ions in the nanofiltration produced water is 20000mg/L, and the content of sodium sulfate ions in the nanofiltration concentrated water is 35000 mg/L. And then, deeply concentrating the nanofiltration produced water and the nanofiltration concentrated water by adopting a high-pressure flat RO (reverse osmosis) membrane to respectively obtain a sodium chloride solution with the mass concentration of 14% and a sodium sulfate solution with the mass concentration of 17%. Freezing and crystallizing the sodium sulfate solution to obtain sodium sulfate decahydrate crystals with the purity of 98.5 percent; and (3) carrying out evaporative crystallization treatment on the sodium chloride solution to obtain sodium chloride crystals with the purity of 95.5%. Wherein, the condensed water in the evaporation crystallization process is discharged into a reuse water pool for standby.
Example 3
And introducing the desulfurization wastewater into a regulating tank, carrying out homogenization treatment by a stirrer, and introducing the desulfurization wastewater subjected to the homogenization treatment into a reaction tank. Adding liquid caustic soda and lime into the reaction tank to adjust the pH value of the desulfurization wastewater to 9, then introducing the desulfurization wastewater into a precipitation tank, adding PAC, TMT-15 and iron ore particles, opening a magnetic separation device for treatment for 8min, and respectively obtaining a precipitate and a supernatant. Wherein the precipitate is transferred into a sedimentation tank, and iron ore particles in the precipitate are separated by a cyclone and recycled. Further, the hardness of the supernatant was measured to be 3.5ml/L, and hydrochloric acid was added to the supernatant to adjust the pH to 7.5, followed by passing through a super columnThe filter is used for ultrafiltration, suspended matters and colloid impurities in the water are filtered out, and concentrated water with turbidity of 0.15NTU is obtained. Adopts a disc tube type reverse osmosis membrane to carry out reverse osmosis concentration treatment on the concentrated water SO as to ensure that SO4 2-、Na+And Cl-And then the filtrate enters reverse osmosis concentrated solution. And simultaneously, discharging the obtained reverse osmosis produced water into a reuse water pool for later use. And performing nanofiltration treatment on the reverse osmosis concentrated solution by using a disc-tube nanofiltration membrane to respectively obtain nanofiltration produced water containing a sodium chloride solution and nanofiltration concentrated water containing sodium sulfate, wherein the content of chloride ions in the nanofiltration produced water is 25000mg/L, and the content of sodium sulfate ions in the nanofiltration concentrated water is 35000 mg/L. And then, deeply concentrating the nanofiltration produced water and the nanofiltration concentrated water by adopting a high-pressure flat RO (reverse osmosis) membrane to respectively obtain a sodium chloride solution with the mass concentration of 14% and a sodium sulfate solution with the mass concentration of 17%. Freezing and crystallizing the sodium sulfate solution to obtain sodium sulfate decahydrate crystals with the purity of 97 percent; and (3) carrying out evaporative crystallization treatment on the sodium chloride solution to obtain sodium chloride crystals with the purity of 97%. Wherein, the condensed water in the evaporation crystallization process is discharged into a reuse water pool for standby.
Example 4
And introducing the desulfurization wastewater into a regulating tank, carrying out homogenization treatment by a stirrer, and introducing the desulfurization wastewater subjected to the homogenization treatment into a reaction tank. Adding soda ash and magnesium chloride into the reaction tank to adjust the pH value of the desulfurization wastewater to 10, then introducing the desulfurization wastewater into a precipitation tank, adding TMT-15 and iron ore particles, opening a magnetic separation device for treatment for 10min, and respectively obtaining a precipitate and a supernatant. Wherein the precipitate is transferred into a sedimentation tank, and iron ore particles in the precipitate are separated by a cyclone and recycled. In addition, the hardness of the supernatant was measured to be 3ml/L, hydrochloric acid was added to the supernatant to adjust the pH to 7, and then ultrafiltration was performed through an ultrafilter to filter out suspended substances and colloidal impurities therein, to obtain concentrated water having a turbidity of 0.15 NTU. Adopts a disc tube type reverse osmosis membrane to carry out reverse osmosis concentration treatment on the concentrated water SO as to ensure that SO4 2-、Na+And Cl-And then the filtrate enters reverse osmosis concentrated solution. And simultaneously, discharging the obtained reverse osmosis produced water into a reuse water pool for later use. Next, a disc tube type nanofiltration membrane is adopted to feed reverse osmosis concentrated solutionAnd performing nanofiltration treatment to respectively obtain nanofiltration product water containing a sodium chloride solution and nanofiltration concentrated water containing sodium sulfate, wherein the content of chloride ions in the nanofiltration product water is 25000mg/L, and the content of sodium sulfate ions in the nanofiltration concentrated water is 30000 mg/L. And then, deeply concentrating the nanofiltration produced water and the nanofiltration concentrated water by adopting a high-pressure flat RO (reverse osmosis) membrane to respectively obtain a sodium chloride solution with the mass concentration of 14% and a sodium sulfate solution with the mass concentration of 17%. Freezing and crystallizing the sodium sulfate solution to obtain sodium sulfate decahydrate crystals with the purity of 98.5 percent; and (3) carrying out evaporation crystallization treatment on the sodium chloride solution to obtain sodium chloride crystals with the purity of 96%. Wherein, the condensed water in the evaporation crystallization process is discharged into a reuse water pool for standby.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (14)
1. A treatment device for desulfurization wastewater quality-divided crystallization is characterized by comprising:
a magnetic separation unit (20) having a desulfurization wastewater inlet, and having a first pH adjuster inlet, an organic sulfur agent inlet, and an iron ore particle inlet, the magnetic separation unit (20) serving to subject the desulfurization wastewater to a magnetic separation treatment to obtain a precipitate and a supernatant;
an ultrafiltration unit (30) connected with the outlet of the magnetic separation unit (20) and provided with a second pH regulator inlet, wherein the ultrafiltration unit (30) is used for carrying out ultrafiltration treatment on the supernatant to obtain concentrated water;
a reverse osmosis unit (40) connected to an outlet of the ultrafiltration unit (30), the reverse osmosis unit (40) being configured to subject the concentrate to a reverse osmosis treatment to obtain a reverse osmosis concentrate;
the nanofiltration unit (50) is connected with an outlet of the reverse osmosis unit (40), and the nanofiltration unit (50) is used for carrying out nanofiltration treatment on the reverse osmosis concentrated solution to obtain nanofiltration produced water containing sodium chloride and nanofiltration concentrated water containing sodium sulfate; and
and the concentration and crystallization unit (60) is connected with an outlet of the nanofiltration unit (50), and the concentration and crystallization unit (60) is used for sequentially carrying out concentration treatment and crystallization treatment on the nanofiltration produced water to obtain sodium chloride crystals and sequentially carrying out concentration treatment and crystallization treatment on the nanofiltration concentrated water to obtain sodium sulfate decahydrate crystals.
2. The desulfurization wastewater fractional crystallization treatment device according to claim 1, wherein the magnetic separation unit (20) comprises:
a first reaction device (21) having the desulfurization waste water inlet, the first pH adjustor inlet, the organosulfur agent inlet, and the iron ore inlet, the first reaction device (21) being for providing a place for magnetic separation treatment of the desulfurization waste water;
a first feeding device (22) connected with the pH regulator inlet, wherein the first feeding device (22) is used for providing one or more of liquid caustic soda, calcined soda, lime and magnesium agents as a first pH regulator;
a second supply means (23) connected to said organosulfur agent inlet, said second supply means (23) for supplying TMT-15 as the organosulfur agent;
-a third feeding device (24) connected to the iron ore particles inlet, the third feeding device (24) being adapted to provide iron ore particles;
the magnetic separation device (25) is arranged in the first reaction device (21), and the magnetic separation device (25) is used for performing magnetic separation treatment on the desulfurization wastewater to obtain the precipitate and the supernatant.
3. The desulfurization wastewater fractional crystallization treatment device according to claim 2, wherein the first reaction device (21) has a precipitate outlet, and the magnetic separation unit (20) further comprises:
the third reaction device is connected with the sediment outlet and is used for providing a place for separating and recovering the iron ore particles;
and the cyclone device is arranged in the third reaction device and is used for performing cyclone separation on the sediments so as to recover the iron ore particles.
4. The desulfurization wastewater fractional crystallization treatment device according to claim 2 or 3, wherein the ultrafiltration unit (30) comprises:
a second reaction device (31) having an inlet for the second pH adjuster, the second reaction device (31) being adapted to provide a location for a second pH adjustment of the supernatant;
a fourth supply device (32) connected to the second pH adjuster inlet, the fourth supply device (32) for providing acid as the second pH adjuster;
and the ultrafiltration device (33) is connected with the outlet of the second reaction device (31), the ultrafiltration device (33) is provided with a concentrated water outlet, and the ultrafiltration device (33) is used for performing ultrafiltration treatment on the supernatant to obtain the concentrated water.
5. The desulfurization wastewater quality-divided crystallization treatment device according to claim 4, wherein the ultrafiltration treatment step further obtains ultrafiltration product water, the ultrafiltration device (33) further has an ultrafiltration product water outlet, the first reaction device (21) further has a backwash water inlet, and the ultrafiltration unit (30) further comprises:
and the first recovery device (34) is respectively connected with the ultrafiltration produced water outlet and the backwashing water inlet.
6. The desulfurization wastewater fractional crystallization treatment device according to claim 4, wherein the reverse osmosis unit (40) comprises:
a reverse osmosis device (41) connected to the concentrate outlet, the reverse osmosis device (41) having a reverse osmosis concentrate outlet, the reverse osmosis device (41) being configured to reverse osmosis concentrate the concentrate to obtain the reverse osmosis concentrate.
7. The desulfurization wastewater treatment device for fractional crystallization according to claim 6, wherein the reverse osmosis device (41) comprises:
a reverse osmosis membrane for performing reverse osmosis, the reverse osmosis membrane selected from a disc tube reverse osmosis membrane;
and the vibration device is connected with the reverse osmosis membrane and is used for providing vibration elasticity for the reverse osmosis membrane so as to enable the reverse osmosis membrane to be carried out in a dynamic mode.
8. The desulfurization wastewater quality-divided crystallization treatment device according to claim 7, wherein the reverse osmosis concentration process further generates reverse osmosis produced water, the reverse osmosis device (41) further has a reverse osmosis produced water outlet, and the reverse osmosis unit (40) further comprises:
a second recovery device (42) connected to the reverse osmosis produced water outlet, the second recovery device (42) being for recovering the reverse osmosis produced water.
9. The device for treating fractional crystallization of desulfurization wastewater according to claim 6, characterized in that said nanofiltration unit (50) comprises:
and the nanofiltration device (51) is connected with the reverse osmosis concentrated solution outlet and is provided with a nanofiltration water production outlet and a nanofiltration concentrated water outlet, and the nanofiltration device (51) is used for performing nanofiltration treatment on the reverse osmosis concentrated solution to respectively obtain the nanofiltration water production containing sodium chloride and the nanofiltration concentrated water containing sodium sulfate.
10. The desulfurization wastewater quality-divided crystallization treatment device according to claim 9, wherein the concentration crystallization unit (60) comprises:
a first concentration device (61) connected with the nanofiltration water production outlet and provided with a sodium chloride solution outlet, wherein the first concentration device (61) is used for concentrating the nanofiltration water production containing sodium chloride to obtain a sodium chloride solution;
a second concentration device (62) connected with the nanofiltration concentrated water outlet and provided with a sodium sulfate solution outlet, wherein the second concentration device (62) is used for concentrating the nanofiltration concentrated water containing sodium sulfate to obtain a sodium sulfate solution;
the first crystallization device (63) is connected with the sodium chloride solution outlet, and the first crystallization device (63) is used for crystallizing the sodium chloride solution to obtain sodium chloride crystals;
and the second crystallizing device (64) is connected with the sodium sulfate solution outlet, and the second crystallizing device (64) is used for crystallizing the sodium sulfate solution to obtain the sodium sulfate decahydrate crystals.
11. The desulfurization wastewater quality-divided crystallization treatment device according to claim 10, wherein the first concentration device (61) and the second concentration device (62) each comprise a high-pressure flat membrane to perform the concentration treatment; the first crystallization device (63) is an evaporation crystallization device, and the second crystallization device (64) is a freezing crystallization device.
12. The device for treating the desulfurization waste water by fractional crystallization according to claim 11, wherein a denitrated liquid is further generated in the step of crystallizing the sodium sulfate crystals, the second crystallizing device (64) has a denitrated liquid outlet, the reverse osmosis device (41) has a denitrated backwash liquid inlet, and the concentration and crystallization unit (60) further comprises:
and the third recovery device (65) is respectively connected with the denitration liquid outlet and the denitration backwash liquid inlet, and the third recovery device (65) is used for recycling the denitration liquid.
13. The device for treating desulfurization wastewater fractional crystallization according to any one of claims 1 to 3, characterized in that said treatment device further comprises:
and the homogenizing unit (10) is connected with the desulfurization wastewater inlet, and the homogenizing unit (10) is used for homogenizing the desulfurization wastewater.
14. The device for treating desulfurization waste water quality-divided crystallization according to claim 13, characterized in that said homogenizing unit (10) comprises:
the adjusting tank (11) is connected with the desulfurization wastewater inlet, and the adjusting tank (11) is used for carrying out homogenization treatment on the desulfurization wastewater;
and the stirring device (12) is arranged in the adjusting tank (11).
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