CN114212935A - Zero-emission device and method for recycling high-quality sodium sulfate from lead-containing wastewater - Google Patents
Zero-emission device and method for recycling high-quality sodium sulfate from lead-containing wastewater Download PDFInfo
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- CN114212935A CN114212935A CN202111444960.3A CN202111444960A CN114212935A CN 114212935 A CN114212935 A CN 114212935A CN 202111444960 A CN202111444960 A CN 202111444960A CN 114212935 A CN114212935 A CN 114212935A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 54
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 53
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 51
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004064 recycling Methods 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 38
- 238000011084 recovery Methods 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 289
- 238000001223 reverse osmosis Methods 0.000 claims description 188
- 238000000909 electrodialysis Methods 0.000 claims description 36
- 238000000108 ultra-filtration Methods 0.000 claims description 34
- 239000000047 product Substances 0.000 claims description 30
- 239000012528 membrane Substances 0.000 claims description 27
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 17
- 239000012466 permeate Substances 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 9
- 239000013505 freshwater Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 5
- 238000003860 storage Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000003014 ion exchange membrane Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 10
- 239000011575 calcium Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000003814 drug Substances 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 10
- 230000008020 evaporation Effects 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000012141 concentrate Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000011133 lead Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 5
- 239000003456 ion exchange resin Substances 0.000 description 5
- 229920003303 ion-exchange polymer Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229940079593 drug Drugs 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- -1 electric power Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
- C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of a commercial heavy truck intercooling system, and discloses a zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater. The invention also discloses a recovery method of the zero-discharge device for recovering the high-quality sodium sulfate from the lead-containing wastewater. The zero discharge device and the recovery method for recovering the high-quality sodium sulfate from the lead-containing wastewater realize the zero discharge standard of the lead-containing wastewater and the recovery of the high-quality sodium sulfate in the actual production process of a factory.
Description
Technical Field
The invention relates to the technical field of zero discharge of wastewater, in particular to a zero discharge device and a recovery method for recovering high-quality sodium sulfate from lead-containing wastewater.
Background
The shortage of water resources becomes an important factor for restricting the development of economy and society in China. The industrial water intake accounts for 20% of the national water intake, and the main high water consumption industries are thermal power generation, textile, paper making, steel and petrochemical industries. In recent years, coal chemical industry has occupied an important position in the fields of Chinese energy and chemical industry because the price of petroleum is high. The development of the coal chemical industry plays an important role in relieving the contradiction between supply and demand of high-quality energy sources such as petroleum, natural gas and the like in China and promoting the development of steel, chemical industry, light industry and agriculture. However, the "surge phenomenon" developed by the coal chemical industry has put tremendous pressure on the environment and resources. In order to further strengthen the industrial water-saving work, relieve the contradiction between supply and demand of water resources in China, restrain the trend of water environment deterioration and promote the coordinated development of industrial economy, water resources and environment.
The Chinese water-saving technical policy outline issued in 2005 firstly puts forward the requirements for developing the technology of recycling discharged wastewater and zero emission. The newly issued national environmental protection 'one-tenth-five' plan in 11 months in 2007 clearly requires that wastewater recycling is promoted in key industries such as steel, electric power, chemical industry and coal, and the like, and the aim of realizing less wastewater discharge or zero wastewater discharge is fulfilled.
The wastewater treated by the traditional method is concentrated to about 8 percent by adopting reverse osmosis saline wastewater, and then is evaporated and concentrated to reach the emission standard, however, the method has large equipment investment and high equipment operation cost, and the sodium sulfate solid obtained by the traditional method contains lead exceeding standard and belongs to dangerous waste, and the treatment is difficult.
Therefore, in order to reduce the pressure of wastewater treatment, a set of zero-discharge process system for recovering high-quality sodium sulfate from lead-containing wastewater needs to be developed so as to achieve the purposes of lead removal and high-quality sodium sulfate recovery.
Disclosure of Invention
The invention aims to provide a zero discharge device and a recovery method for recovering high-quality sodium sulfate from lead-containing wastewater, aiming at the defects of the technology, so that the zero discharge standard of the lead-containing wastewater is achieved in the actual production process of a factory, and the high-quality sodium sulfate is recovered.
In order to achieve the purpose, the zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater comprises a raw water tank 1, wherein the raw water tank 1 is sequentially connected with a submersible pump 2, a self-cleaning filter 3, an ultrafiltration device 4, an ultrafiltration product water tank 5 and a primary RO reverse osmosis device 6 through pipelines, a concentrated water outlet of the primary RO reverse osmosis device 6 is connected with an RO reverse osmosis concentrated water tank 10, a water outlet of the RO reverse osmosis concentrated water tank 10 is sequentially connected with a softener 11, a softening water tank 12, an RO concentrated water reverse osmosis device 13, an ED electrodialysis water inlet tank 14, an ED electrodialysis device 15, an ED electrodialysis concentrated water tank 16, a triple-effect evaporator 17 and a crystallization device 18 through pipelines, a product water outlet of the primary RO reverse osmosis device 6 is connected with a primary RO reverse osmosis product water tank 7, and the primary RO reverse osmosis product water tank 7 is connected with a secondary RO reverse osmosis device 8 through pipelines, and a water production outlet of the second-stage RO reverse osmosis device 8 is connected with a second-stage RO reverse osmosis water production tank 9 through a pipeline.
Preferably, the concentrate outlet of the secondary RO reverse osmosis device 8 is communicated with the ultrafiltration water production tank 5 through a pipeline.
Preferably, the condensed water outlet of the triple effect evaporator 17 is communicated with the primary RO reverse osmosis water production tank 7 through a pump.
Preferably, the produced water outlet of the RO concentrated water reverse osmosis device 13 is communicated with the primary RO reverse osmosis water producing tank 7 through a pipeline.
Preferably, the fresh water outlet of the ED electrodialysis device 15 is in communication with the softened water tank 12 through a pipe.
Preferably, ion exchange membrane resin special for lead removal is arranged in the softener 11.
A recovery method of a zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater comprises the following steps:
1) collecting wastewater to be treated into the raw water tank 1, pumping the wastewater into the self-cleaning filter 3 by virtue of a pressurizing pump 2 to carry out primary filtration treatment to remove large-particle impurities, allowing filtrate to enter the ultrafiltration device 4 for treatment, allowing product water permeating through an ultrafiltration membrane to enter the ultrafiltration product water tank 5 for storage at the pressure of 0.6-0.8 MPa and the temperature of 25-30 ℃, then conveying the product water into the primary RO reverse osmosis device 6 by virtue of a pressurizing pump, allowing the product water permeating through an RO membrane of the primary RO reverse osmosis device 6 to enter the primary RO reverse osmosis product water tank 7 at the pressure of 0.7-1.2 MPa and the temperature of 28-32 ℃, and recycling the product water as reuse water;
2) concentrated water which does not permeate the RO reverse osmosis membrane of the primary RO reverse osmosis device 6 enters the RO reverse osmosis concentrated water tank 10 for treatment, the concentrated water enters the softener 11 for softening through a pipeline under the pressure of 0.2MPa to 0.5MPa and the temperature of 31 ℃ to 35 ℃, calcium and magnesium ions in the concentrated water react with carbonate ions under the weak acid condition to generate precipitation so as to remove the calcium and magnesium ions, meanwhile, the ion exchange resin in the softener 11 has enrichment effect on lead ions, but has no influence on sodium ions in water, thereby removing lead ions in the wastewater, leading the treated concentrated water to enter the softened water tank 12 for collection, and leading the concentrated water to enter the RO reverse osmosis device 13 for treatment through a pipeline, concentrated water which does not permeate the RO reverse osmosis membrane of the concentrated water RO reverse osmosis device 13 under the pressure of 0.7MPa to 1.1MPa and the temperature of 23 ℃ to 28 ℃ enters the ED electrodialysis water inlet tank 14 for collection;
3) the concentrated water in the ED electrodialysis water inlet tank 14 is pressurized by a pump and enters the ED electrodialysis device 15, and the concentrated water permeating under the pressure of 0.3 MPa-0.7 MPa and the temperature of 32-35 ℃ enters the ED electrodialysis concentrated water tank 16 for collection;
4) concentrated water of the ED electrodialysis concentrated water tank 16 enters the triple-effect evaporator 17 through pump pressurization, crystallization starts to be generated when the solution reaches supersaturated concentration, sodium sulfate solid is collected through crystallization of the crystallization device 18, the purity of the sodium sulfate solid is high, and the sodium sulfate solid can be used as chemical raw materials for recovery treatment.
Preferably, the concentrated water outlet of the second-stage RO reverse osmosis device 8 is communicated with the ultrafiltration water production tank 5 through a pipeline, in the step 1), the produced water in the first-stage RO reverse osmosis water production tank 7 enters the second-stage RO reverse osmosis device 8 through the pressurization of a booster pump for filtration, the produced water permeating the RO reverse osmosis membrane of the second-stage RO reverse osmosis device 8 enters the second-stage RO water production tank 9 for pure water at the pressure of 0.8MPa to 1.2MPa and the temperature of 25 ℃ to 28 ℃, and the concentrated water permeating the RO reverse osmosis membrane of the second-stage RO reverse osmosis device 8 enters the ultrafiltration water production tank 5 for reverse osmosis treatment again.
Preferably, the water outlet of the RO concentrated water reverse osmosis device 13 is connected with the primary RO reverse osmosis water production tank 7 through a pipeline, and in the step 2), the water produced by the RO reverse osmosis membrane of the concentrated water RO reverse osmosis device 13 is recycled into the primary RO reverse osmosis water production tank 7 for reuse water treatment.
Preferably, a fresh water outlet of the ED electrodialysis device 15 is communicated with the softened water tank 12 through a pipeline, in the step 3), fresh water of water produced by the ED electrodialysis device 15 returns to the softened water tank 12 for a second circulation treatment, a condensed water outlet of the triple-effect evaporator 17 is communicated with the primary RO reverse osmosis water production tank 7 through a pump, and in the step 4), condensed water evaporated by the triple-effect evaporator 17 is recycled to the primary RO reverse osmosis water production tank 7 for reuse water treatment.
Compared with the prior art, the invention has the following advantages:
1. the produced water can be recycled through multi-stage reverse osmosis treatment, the treatment capacity of concentrated water is greatly reduced by only one twentieth of the original treatment capacity, most of impurities (such as calcium, magnesium, lead and other heavy metal ions) are enriched in the concentrated water, and the medicament consumption and the scale of subsequent treatment equipment can be reduced through centralized treatment so as to facilitate subsequent treatment;
2. most of impurities (such as calcium, magnesium, lead and other heavy metal ions) in the concentrated water are removed to more than 99% through gradual multi-stage treatment, suspended impurities (such as lead slime and the like) in the wastewater are removed through ultrafiltration, the concentrated water contains higher calcium, magnesium, lead and other heavy metal ions after multi-stage reverse osmosis, the impurities can be removed by more than 90% through softening by adding a medicament and filtering by a softener, and the concentrated water is further treated by ion exchange resin (special high-salt-resistant resin, such as Dusheng resin CH90), so that the comprehensive removal rate is more than 99%;
3. on one hand, high-purity sodium sulfate can be obtained after impurity removal and can be sold as a first-class product of industrial-grade sodium sulfate to realize recycling of waste salt, on the other hand, the scaling problem in the subsequent operation process of an ED (organic light-emitting diode) and a triple-effect evaporator can be effectively prevented after impurity removal, and compared with the triple-effect evaporator which is concentrated through ED, the energy consumption can be effectively saved;
4. the main process flow of the invention is in loop-locked, mutual authentication and interaction, so that the high-quality sodium sulfate is recovered from the lead-containing wastewater, the treated sodium sulfate wastewater can be reused, the pure water obtained by the reverse osmosis treatment of the reuse water can be stored and sold, the reasonable utilization of resources is realized, and the aim of zero discharge is achieved.
Drawings
FIG. 1 is a schematic structural diagram of a zero-emission device for recovering high-quality sodium sulfate from lead-containing wastewater according to the present invention.
The components in the figures are numbered as follows:
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
As shown in figure 1, the zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater comprises a raw water tank 1, wherein the raw water tank 1 is sequentially connected with a submersible pump 2, a self-cleaning filter 3, an ultrafiltration device 4, an ultrafiltration product water tank 5 and a primary RO reverse osmosis device 6 through pipelines, a concentrated water outlet of the primary RO reverse osmosis device 6 is connected with an RO reverse osmosis concentrated water tank 10, a water outlet of the RO reverse osmosis concentrated water tank 10 is sequentially connected with a softener 11 and a softening water tank 12 through pipelines, RO dense water reverse osmosis unit 13, ED electrodialysis are intake case 14, ED electrodialysis device 15, ED electrodialysis dense water case 16, triple effect evaporimeter 17 and crystallization unit 18, and the product water outlet of one-level RO reverse osmosis unit 6 even has one-level RO reverse osmosis product water case 7, and the product water case 7 of one-level RO reverse osmosis even has second grade RO reverse osmosis unit 8 through the pipeline, and the product water outlet of second grade RO reverse osmosis unit 8 even has second grade RO reverse osmosis product water case 9 through the pipeline.
Wherein, the dense water export of second grade RO reverse osmosis unit 8 is through pipeline and ultrafiltration product water tank 5 intercommunication, and the comdenstion water export of triple effect evaporimeter 17 is through pump and the product water tank 7 intercommunication of one-level RO reverse osmosis, and the product water export of RO dense water reverse osmosis unit 13 is through pipeline and the product water tank 7 of one-level RO reverse osmosis, and the fresh water export of ED electrodialysis device 15 is through pipeline and softened water tank 12 intercommunication, is equipped with the special ion exchange membrane resin of deleading in the demineralizer 11.
The recycling method of the zero discharge device for recycling the high-quality sodium sulfate from the lead-containing wastewater comprises the following steps:
1) collecting wastewater to be treated to a raw water tank 1, pumping the wastewater into a self-cleaning filter 3 by a submersible pump 2 under a pressure boost condition to carry out primary filtration treatment to remove large-particle impurities, allowing filtrate to enter an ultrafiltration device 4 for treatment, allowing the produced water passing through an ultrafiltration membrane to enter an ultrafiltration produced water tank 5 for storage under the pressure of 0.6 MPa-0.8 MPa and the temperature of 25-30 ℃, then conveying the produced water into a primary RO reverse osmosis device 6 by a booster pump, allowing the produced water passing through an RO reverse osmosis membrane of the primary RO reverse osmosis device 6 to enter a primary RO reverse osmosis produced water tank 7 at the pressure of 0.7 MPa-1.2 MPa and the temperature of 28-32 ℃, and recycling the produced water as reuse water;
2) concentrated water which does not permeate the RO reverse osmosis membrane of the primary RO reverse osmosis device 6 enters an RO reverse osmosis concentrated water tank 10 for treatment, the concentrated water enters a softener 11 for softening through a pipeline at the pressure of 0.2MPa to 0.5MPa and the temperature of 31 ℃ to 35 ℃, the treated concentrated water enters a softening water tank 12 for collection, and enters a concentrated water RO reverse osmosis device 13 for treatment through a pipeline, and the concentrated water which does not permeate the RO reverse osmosis membrane of the concentrated water RO reverse osmosis device 13 at the pressure of 0.7MPa to 1.1MPa and the temperature of 23 ℃ to 28 ℃ enters an ED electrodialysis water inlet tank 14 for collection;
3) the concentrated water in the ED electrodialysis water inlet tank 14 is pressurized by a pump and enters an ED electrodialysis device 15, and the permeated concentrated water under the pressure of 0.3 MPa-0.7 MPa and the temperature of 32-35 ℃ enters an ED electrodialysis concentrated water tank 16 for collection;
4) concentrated water in an ED electrodialysis concentrated water tank 16 enters a three-effect evaporator 17 through pump pressurization, crystallization starts to occur when the solution reaches supersaturated concentration, and sodium sulfate solid is crystallized and collected through a crystallization device 18.
Wherein, because the dense water export of second grade RO reverse osmosis unit 8 is through pipeline and ultrafiltration product water tank 5 intercommunication, in step 1), the product water in the first grade RO reverse osmosis product water tank 7 gets into second grade RO reverse osmosis unit 8 through the booster pump pressure boost and filters, at 0.8MPa ~ 1.2MPa pressure, the product water that permeates the RO reverse osmosis membrane of second grade RO reverse osmosis unit 8 gets into second grade RO product water tank 9 and is used as the pure water under 25 ℃ -28 ℃ temperature, for the dense water that permeates the RO reverse osmosis membrane of second grade RO reverse osmosis unit 8 gets into ultrafiltration product water tank 5 and carries out reverse osmosis treatment once more.
Because the produced water outlet of the RO concentrated water reverse osmosis device 13 passes through the pipeline and the first-stage RO reverse osmosis water production tank 7, in the step 2), the produced water of the RO reverse osmosis membrane penetrating through the concentrated water RO reverse osmosis device 13 is recycled into the first-stage RO reverse osmosis water production tank 7 to be treated as the reuse water.
Because the fresh water outlet of the ED electrodialysis device 15 is communicated with the softened water tank 12 through a pipeline, in the step 3), the fresh water of the water produced by the ED electrodialysis device 15 returns to the softened water tank 12 to be subjected to the secondary circulation treatment, the condensed water outlet of the triple-effect evaporator 17 is communicated with the primary RO reverse osmosis water production tank 7 through a pump, and in the step 4), the condensed water evaporated by the triple-effect evaporator 17 is recycled to the primary RO reverse osmosis water production tank 7 to be subjected to the reuse water treatment.
Two experiments were performed using this example, experiment 1 was as follows:
s1 preparation of pure water:
the raw water tank 1 water quality data is shown in the following table:
1) collecting wastewater to be treated into a raw water tank 1, pressurizing the wastewater by a submersible pump 2, introducing the wastewater into a self-cleaning filter 3 for primary filtration treatment to remove large-particle impurities, and introducing the produced water of an ultrafiltration membrane into an ultrafiltration water production tank 5 for storage under the pressure of 0.6-0.8 MPa and the temperature of 25-30 ℃;
2) after collecting a certain amount of ultrafiltration produced water, the produced water enters a first-stage RO reverse osmosis device 6 through a pipeline, and the produced water penetrating through the low-pressure side of a reverse osmosis membrane enters a first-stage RO reverse osmosis water production tank 7 for collection at the pressure of 0.7 MPa-1.2 MPa and the temperature of 28 ℃ -32 ℃ for treatment of reuse water, wherein the quality data of the reuse water are shown in the following table:
3) the obtained reuse water enters a secondary RO reverse osmosis device 8 for further treatment under the pressure of 0.8MPa to 1.2MPa and the temperature of 25 ℃ to 28 ℃, the produced water enters a secondary RO reverse osmosis water production tank 9 for collection and pure water treatment, and the quality data of the pure water are as follows:
s2 concentrated water hardness reduction and lead ion removal:
the concentrate that does not permeate the RO reverse osmosis membrane of the first-stage RO reverse osmosis device 6 enters the RO reverse osmosis concentrate tank 10, and the concentrate data is as follows:
1) in the softener 11, after the concentrated water is added with drugs and stirred, calcium and magnesium ions are converted into magnesium carbonate, calcium carbonate precipitates are separated out, and the hardness is further reduced, wherein the names and the concentrations of the added drugs are shown in the following table:
| name of medicament | Sodium carbonate solution | Sodium hydroxide solution | Sulfuric acid solution | Technical grade hydrochloric |
| Mass fraction | ||||
| 10％ | 15％ | 20％ | 31％ |
The concentrated water data after the dosing treatment is as follows:
2) the concentrated water is treated by ion exchange resin of a concentrated water RO reverse osmosis device 13 to remove lead ions under the pressure of 0.7MPa to 1.1MPa and the temperature of 23 ℃ to 28 ℃, and the treated data is as follows:
s3 preparation of sodium sulfate crystal:
the solid sodium sulfate is prepared by adopting the process scheme of evaporation concentration and cooling crystallization, and the method comprises the following specific steps:
a. and (3) evaporation and concentration: introducing the concentrated water into a triple-effect evaporator 17 for evaporation and concentration, so that the wastewater forms a sodium sulfate supersaturated solution;
b. cooling and crystallizing: the supersaturated solution is introduced into a crystallization device 18 for stirring and cooling, and then is introduced into a centrifugal pump for dehydration to obtain sodium sulfate crystals
In the step a, the density of the sodium sulfate solution is monitored, and when the density of the solution reaches 1.34g/mL, the solution can be discharged into a crystallization device for cooling and crystallization treatment.
The evaporation temperature data are as follows:
| item | I effect | II effects | III effect |
| Evaporation temperature (. degree.C.) | 84 | 75 | 62 |
| Vacuum degree (MPa) | -0.07 | -0.08 | -0.09 |
And b, introducing circulating cooling water into the crystallization device for cooling, wherein the water inlet temperature of the cooling water is 16 ℃, and the stirring speed is 60 r/min.
The data for the crystalline sodium sulfate salt prepared is as follows:
s1 preparation of pure water:
the raw water tank 1 water quality data is shown in the following table:
1) collecting wastewater to be treated into a raw water tank 1, pressurizing the wastewater by a submersible pump 2, introducing the wastewater into a self-cleaning filter 3 for primary filtration treatment to remove large-particle impurities, and introducing the produced water of an ultrafiltration membrane into an ultrafiltration water production tank 5 for storage under the pressure of 0.6-0.8 MPa and the temperature of 25-30 ℃;
2) after collecting a certain amount of ultrafiltration produced water, the produced water enters a first-stage RO reverse osmosis device 6 through a pipeline, and the produced water penetrating through the low-pressure side of a reverse osmosis membrane enters a first-stage RO reverse osmosis water production tank 7 for collection at the pressure of 0.7 MPa-1.2 MPa and the temperature of 28 ℃ -32 ℃ for treatment of reuse water, wherein the quality data of the reuse water are shown in the following table:
3) the obtained reuse water enters a secondary RO reverse osmosis device 8 for further treatment under the pressure of 0.8MPa to 1.2MPa and the temperature of 25 ℃ to 28 ℃, the produced water enters a secondary RO reverse osmosis water production tank 9 for collection and pure water treatment, and the quality data of the pure water are as follows:
s2 concentrated water hardness reduction and lead ion removal:
the concentrate that does not permeate the RO reverse osmosis membrane of the first-stage RO reverse osmosis device 6 enters the RO reverse osmosis concentrate tank 10, and the concentrate data is as follows:
1) in the softener 11, after the concentrated water is added with drugs and stirred, calcium and magnesium ions are converted into magnesium carbonate, calcium carbonate precipitates are separated out, and the hardness is further reduced, wherein the names and the concentrations of the added drugs are shown in the following table:
| name of medicament | Sodium carbonate solution | Sodium hydroxide solution | Sulfuric acid solution | Technical grade hydrochloric |
| Mass fraction | ||||
| 10％ | 15％ | 20％ | 31％ |
The concentrated water data after the dosing treatment is as follows:
2) the concentrated water is treated by ion exchange resin of a concentrated water RO reverse osmosis device 13 to remove lead ions under the pressure of 0.7MPa to 1.1MPa and the temperature of 23 ℃ to 28 ℃, and the treated data is as follows:
s3 preparation of sodium sulfate crystal:
the solid sodium sulfate is prepared by adopting the process scheme of evaporation concentration and cooling crystallization, and the method comprises the following specific steps:
a. and (3) evaporation and concentration: introducing the concentrated water into a triple-effect evaporator 17 for evaporation and concentration, so that the wastewater forms a sodium sulfate supersaturated solution;
b. cooling and crystallizing: the supersaturated solution is introduced into a crystallization device 18 for stirring and cooling, and then is introduced into a centrifugal pump for dehydration to obtain sodium sulfate crystals
In the step a, the density of the sodium sulfate solution is monitored, and when the density of the solution reaches 1.34g/mL, the solution can be discharged into a crystallization device for cooling and crystallization treatment.
The evaporation temperature data are as follows:
| item | I effect | II effects | III effect |
| Evaporation temperature (. degree.C.) | 91 | 74 | 65 |
| Vacuum degree (MPa) | -0.07 | -0.08 | -0.09 |
And b, introducing circulating cooling water into the crystallization device for cooling, wherein the water inlet temperature of the cooling water is 16 ℃, and the stirring speed is 60 r/min.
The data for the crystalline sodium sulfate salt prepared is as follows:
according to the zero-emission device and the recovery method for recovering high-quality sodium sulfate from the lead-containing wastewater, the produced water can be produced and recycled through multi-stage reverse osmosis treatment, meanwhile, the treatment capacity of the concentrated water is greatly reduced by only one twentieth of the original treatment capacity, most of impurities (such as calcium, magnesium, lead and other heavy metal ions) are enriched in the concentrated water, and the medicament consumption and the scale of subsequent treatment equipment can be reduced through centralized treatment so as to facilitate subsequent treatment; most of impurities (such as calcium, magnesium, lead and other heavy metal ions) in the concentrated water are removed to more than 99% through gradual multi-stage treatment, suspended impurities (such as lead slime and the like) in the wastewater are removed through ultrafiltration, the concentrated water contains higher calcium, magnesium, lead and other heavy metal ions after multi-stage reverse osmosis, the impurities can be removed by more than 90% through softening by adding a medicament and filtering by a softener, and the concentrated water is further treated by ion exchange resin (special high-salt-resistant resin, such as Dusheng resin CH90), so that the comprehensive removal rate is more than 99%; on one hand, high-purity sodium sulfate can be obtained after impurity removal and can be sold as a first-class product of industrial-grade sodium sulfate to realize recycling of waste salt, on the other hand, the scaling problem in the subsequent operation process of an ED (organic light-emitting diode) and a triple-effect evaporator can be effectively prevented after impurity removal, and compared with the triple-effect evaporator which is concentrated through ED, the energy consumption can be effectively saved; the main process flow of the invention is in loop-locked, mutual authentication and interaction, so that the high-quality sodium sulfate is recovered from the lead-containing wastewater, the treated sodium sulfate wastewater can be reused, the pure water obtained by the reverse osmosis treatment of the reuse water can be stored and sold, the reasonable utilization of resources is realized, and the aim of zero discharge is achieved.
Claims (10)
1. The utility model provides a retrieve zero discharge apparatus of high-quality sodium sulfate in lead-containing waste water, includes former basin (1), its characterized in that: the raw water tank (1) is sequentially connected with a submersible pump (2), a self-cleaning filter (3), an ultrafiltration device (4), an ultrafiltration water production tank (5) and a primary RO reverse osmosis device (6) through pipelines, a concentrated water outlet of the primary RO reverse osmosis device (6) is connected with an RO reverse osmosis concentrated water tank (10), a water outlet of the RO reverse osmosis concentrated water tank (10) is sequentially connected with a softener (11), a softening water tank (12), an RO concentrated water reverse osmosis device (13), an ED electrodialysis water inlet tank (14), an ED electrodialysis device (15), an ED electrodialysis concentrated water tank (16), a triple-effect evaporator (17) and a crystallization device (18) through pipelines, a water production outlet of the primary RO reverse osmosis device (6) is connected with a primary RO water production tank (7), and the primary RO reverse osmosis water production tank (7) is connected with a secondary RO reverse osmosis device (8) through pipelines, and a water production outlet of the secondary RO (reverse osmosis) device (8) is connected with a secondary RO water production tank (9) through a pipeline.
2. The zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater according to claim 1, which is characterized in that: and a concentrated water outlet of the secondary RO (reverse osmosis) device (8) is communicated with the ultrafiltration water production tank (5) through a pipeline.
3. The zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater according to claim 1, which is characterized in that: and a condensate water outlet of the three-effect evaporator (17) is communicated with the first-stage RO reverse osmosis water production tank (7) through a pump.
4. The zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater according to claim 1, which is characterized in that: and a water production outlet of the RO concentrated water reverse osmosis device (13) is communicated with the first-stage RO reverse osmosis water production tank (7) through a pipeline.
5. The zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater according to claim 1, which is characterized in that: and a fresh water outlet of the ED electrodialysis device (15) is communicated with the softened water tank (12) through a pipeline.
6. The zero discharge device for recovering high-quality sodium sulfate from lead-containing wastewater according to claim 1, which is characterized in that: the softener (11) is internally provided with ion exchange membrane resin special for removing lead.
7. The recovery method of the zero discharge device for recovering the high-quality sodium sulfate from the lead-containing wastewater according to claim 1, characterized in that: the method comprises the following steps:
1) collecting wastewater to be treated into the raw water tank (1), pumping the wastewater into the self-cleaning filter (3) through the submersible pump (2) under the pressure of 0.6-0.8 MPa for primary filtration treatment to remove large-particle impurities, allowing filtrate to enter the ultrafiltration device (4) for treatment, allowing produced water permeating an ultrafiltration membrane to enter the ultrafiltration produced water tank (5) for storage at the pressure of 0.6-0.8 MPa and the temperature of 25-30 ℃, then conveying the produced water into the primary RO reverse osmosis device (6) through the booster pump, allowing produced water permeating an RO reverse osmosis membrane of the primary RO reverse osmosis device (6) to enter the primary RO reverse osmosis produced water tank (7) at the pressure of 0.7-1.2 MPa and the temperature of 28-32 ℃ for reuse as reuse water;
2) concentrated water which does not permeate the RO reverse osmosis membrane of the primary RO reverse osmosis device (6) enters the RO reverse osmosis concentrated water tank 10 for treatment, the concentrated water enters the softener (11) for softening through a pipeline at the pressure of 0.2 MPa-0.5 MPa and the temperature of 31-35 ℃, the treated concentrated water enters the softened water tank (12) for collection and enters the concentrated water RO reverse osmosis device 13 for treatment through a pipeline, and the concentrated water which does not permeate the RO reverse osmosis membrane of the concentrated water RO reverse osmosis device 13 at the pressure of 0.7 MPa-1.1 MPa and the temperature of 23-28 ℃ enters the ED electrodialysis water inlet tank (14) for collection;
3) concentrated water in the ED electrodialysis water inlet tank (14) is pressurized by a pump and enters the ED electrodialysis device (15), and the concentrated water permeating under the pressure of 0.3-0.7 MPa and the temperature of 32-35 ℃ enters the ED electrodialysis concentrated water tank (16) for collection;
4) concentrated water of the ED electrodialysis concentrated water tank (16) enters the three-effect evaporator (17) through pump pressurization, crystallization starts to be generated when the solution reaches supersaturated concentration, and sodium sulfate solid is crystallized and collected through the crystallization device (18).
8. The recycling method of the zero discharge device for recycling high-quality sodium sulfate from lead-containing wastewater according to claim 7, wherein the recycling method comprises the following steps: the concentrated water outlet of second grade RO reverse osmosis unit (8) pass through the pipeline with water tank (5) intercommunication is produced in the ultrafiltration, in step 1), the product water in water tank (7) is produced in the one-level RO reverse osmosis gets into second grade RO reverse osmosis unit (8) through the booster pump pressure boost and filters, permeates under 0.8MPa ~ 1.2MPa pressure, 25 ~ 28 ℃ temperature the product water of the RO reverse osmosis membrane of second grade RO reverse osmosis unit (8) gets into water tank 9 is produced as the pure water in the second grade RO, for permeating the concentrated water of the RO reverse osmosis membrane of second grade RO reverse osmosis unit (8) gets into water tank (5) is produced in the ultrafiltration carries out reverse osmosis again.
9. The recycling method of the zero discharge device for recycling high-quality sodium sulfate from lead-containing wastewater according to claim 7, wherein the recycling method comprises the following steps: the water outlet of the RO concentrated water reverse osmosis device (13) passes through a pipeline and the one-level RO reverse osmosis water production tank (7), in the step 2), the water produced by the RO reverse osmosis membrane of the concentrated water RO reverse osmosis device (13) is recycled into the one-level RO reverse osmosis water production tank (7) for water reuse treatment.
10. The recycling method of the zero discharge device for recycling high-quality sodium sulfate from lead-containing wastewater according to claim 7, wherein the recycling method comprises the following steps: the fresh water outlet of the ED electrodialysis device (15) is communicated with the softened water tank (12) through a pipeline, in the step 3), the fresh water of the water produced by the ED electrodialysis device (15) returns to the softened water tank (12) to be subjected to secondary circulation treatment, the condensed water outlet of the triple-effect evaporator (17) is communicated with the primary RO reverse osmosis water production tank (7) through a pump, and in the step 4), the condensed water evaporated by the triple-effect evaporator (17) is recycled to the primary RO reverse osmosis water production tank (7) to be subjected to recycled water treatment.
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