CN116444105B - High-hardness and high-mineralization coal mine water recycling pretreatment method and device - Google Patents
High-hardness and high-mineralization coal mine water recycling pretreatment method and device Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000003245 coal Substances 0.000 title claims abstract description 44
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 238000002203 pretreatment Methods 0.000 title claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 50
- 238000002425 crystallisation Methods 0.000 claims abstract description 43
- 230000008025 crystallization Effects 0.000 claims abstract description 43
- 238000005469 granulation Methods 0.000 claims abstract description 43
- 230000003179 granulation Effects 0.000 claims abstract description 43
- 238000005352 clarification Methods 0.000 claims abstract description 33
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 33
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010802 sludge Substances 0.000 claims abstract description 32
- 239000002351 wastewater Substances 0.000 claims abstract description 31
- 238000005345 coagulation Methods 0.000 claims abstract description 30
- 230000015271 coagulation Effects 0.000 claims abstract description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011575 calcium Substances 0.000 claims abstract description 27
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 20
- 238000004062 sedimentation Methods 0.000 claims abstract description 18
- 239000012528 membrane Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 238000005189 flocculation Methods 0.000 claims abstract description 11
- 230000016615 flocculation Effects 0.000 claims abstract description 11
- 230000033558 biomineral tissue development Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000011084 recovery Methods 0.000 claims abstract description 5
- 238000011069 regeneration method Methods 0.000 claims description 26
- 230000008929 regeneration Effects 0.000 claims description 25
- 230000001105 regulatory effect Effects 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 239000000835 fiber Substances 0.000 claims description 6
- 238000012544 monitoring process Methods 0.000 claims description 3
- 230000001954 sterilising effect Effects 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 21
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 21
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 15
- 229910052708 sodium Inorganic materials 0.000 abstract description 15
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 13
- 230000008569 process Effects 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 32
- 229910000019 calcium carbonate Inorganic materials 0.000 description 16
- 239000000701 coagulant Substances 0.000 description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 14
- 239000013078 crystal Substances 0.000 description 14
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 8
- 229920002401 polyacrylamide Polymers 0.000 description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 description 7
- 238000011001 backwashing Methods 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 6
- 238000004891 communication Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 239000008394 flocculating agent Substances 0.000 description 6
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 6
- 239000000347 magnesium hydroxide Substances 0.000 description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 6
- 239000011859 microparticle Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000002817 coal dust Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
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- 239000013049 sediment Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- 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
- C02F5/02—Softening water by precipitation of the hardness
Abstract
The application provides a high-hardness high-mineralization coal mine water recycling pretreatment method, which comprises the steps of firstly carrying out coagulation clarification treatment, then mixing with alkaline agent and the like, entering a chemical crystallization circulating granulation fluidized bed, carrying out calcium removal treatment under the condition that the pH value is 8.8-9.2, and recovering CaCO generated by reaction 3 And (3) crystallizing particles, further filtering the effluent, adjusting the pH value to 7.8-8.3, then entering a sodium ion exchanger for magnesium removal treatment, and concentrating and enriching magnesium ions by using resin. And (3) enabling the sodium bed effluent to enter a subsequent advanced treatment system, and performing flocculation precipitation reaction on the sodium bed regenerated wastewater by a high-density sedimentation tank to obtain magnesium-rich sludge. The application also provides a high-hardness high-mineralization coal mine water recycling pretreatment device. The pretreatment method provided by the application has the advantages of simple process flow, low cost and stable softening effect, can realize the step-by-step recovery of calcium and magnesium ions, achieves the aim of recycling, and can realize the zero emission of mine water with high hardness and high mineralization degree by combining with a membrane method.
Description
Technical Field
The application relates to the technical field of wastewater treatment, in particular to a method and a device for recycling and pre-treating high-hardness and high-mineralization coal mine water.
Background
The mine water with high hardness and high mineralization is derived from deep underground water, and the salt content is high, generally in the range of 1500-4000 mg/L, and can reach 5000mgL at most. In addition, the total hardness and the calcium hardness are also very high, and the total hardness is generally in the range of 1000-2000 mg/L in terms of calcium carbonate. The high-concentration salt-containing wastewater permeates into farmlands, so that the soil structure can be damaged, the soil salinization is caused, and the yield and quality of agricultural products are reduced. Therefore, in order to promote the recycling of mine water and the development of industry with high quality, mine drainage is required to reach the surface water III class standard or the zero emission standard in multiple areas.
The membrane technology is an important research object in the field of mine water zero emission, and a common membrane system needs to be provided with a softening pretreatment process to remove calcium and magnesium hardness in water so as to reduce the risk of system scaling. However, the existing softening pretreatment process basically removes the hardness of calcium and magnesium synchronously, a large amount of flocculating agents, coagulant aids and the like are needed to be added, the operation cost is high, the softening effect is unstable, the produced chemical sludge is difficult to realize the recycling of calcium and magnesium ions, and the operation cost of enterprises is greatly increased when the chemical sludge is used as industrial solid waste for disposal.
Disclosure of Invention
In view of the above, the application aims to provide a pretreatment method and a pretreatment device for recycling mine water of a high-hardness and high-mineralization mine.
The application provides a high-hardness and high-mineralization pretreatment method for mine water of a coal mine, which comprises the following steps:
a) Performing coagulation clarification treatment on the high-hardness and high-mineralization coal mine water;
b) Mixing the effluent obtained in the step a) with an alkaline agent, feeding the mixture into a chemical crystallization circulating granulation fluidized bed for calcium removal treatment, and recovering CaCO generated by the reaction 3 The pH value of the calcium removal treatment is 8.8-9.2;
c) Filtering the effluent obtained in the step b), regulating the pH value to 7.8-8.3, and introducing the filtered effluent into a sodium ion exchanger for magnesium removal treatment to obtain qualified pretreated effluent;
d) And c) carrying out regeneration treatment on the sodium ion exchanger in the step c), and carrying out flocculation precipitation reaction on the obtained regenerated wastewater in a high-density precipitation tank to obtain a magnesium-rich product.
The pretreatment method provided by the application is used for pretreating the high-hardness and high-mineralization coal mine water, so that the calcium and magnesium hardness in the water is removed, and the risk of scaling of a membrane system in the subsequent advanced treatment is reduced. In some specific implementation modes, the salt content of the mine water of the high-hardness and high-mineralization coal mine is 1500-5000 mg/L, and the total hardness is 500-2000 mg/L. In some specific implementation modes, the water turbidity of the high-hardness and high-mineralization coal mine water is 100-150 NTU, the salt content is 2000-4500 mg/L, the total hardness is 800-1500 mg/L, the calcium ions are 300-800 mg/L, the magnesium ions are 30-100 mg/L, the sulfate radical is 2000-3000 mg/L, and the chloride radical is 30-100 mg/L. In some specific implementation modes, the water turbidity of the high-hardness and high-mineralization coal mine water is 60-180 NTU, the salt content is 4000mg/L, the total hardness is 900-1150 mg/L, the calcium ions are 400-500 mg/L, the magnesium ions are 40-55 mg/L, the sulfate radicals are 2300-2700 mg/L, and the chloride radicals are 45-60 mg/L.
In some specific implementation modes, before the high-hardness and high-mineralization coal mine water is subjected to coagulation clarification treatment, the water quality and the water quantity are regulated, so that the pretreatment system is stably operated.
And after the water quantity is stable, carrying out coagulation clarification treatment on the high-hardness and high-mineralization coal mine water, namely adding flocculating agent, coagulant aid and the like into the coal mine water to carry out coagulation reaction, clarify and separate, and removing substances such as coal dust, colloid and the like in the coal mine water. In some specific implementations, the flocculant includes, but is not limited to, polyaluminum chloride (PAC), polyaluminum sulfate (PAS), polyaluminum chloride (PFC), polyaluminum sulfate (PFS), polyaluminum silicate chloride, polyaluminum silicate sulfate, polyphosphoric aluminum chloride, polyphosphoric ferric chloride, polyacrylamide (PAM), and the like, which may be one or more thereof. In some specific implementations, the coagulant aid includes, but is not limited to, sulfuric acid, phosphoric acid, lime, chlorine, polyacrylamide, activated silica, sodium alginate, and the like, and may be one or more thereof. In some specific implementations, the flocculant is polyaluminum chloride and the coagulant aid is polyacrylamide. The amounts of the flocculant and the coagulant aid to be added are not particularly limited in the present application, and those skilled in the art can adjust the amounts of suspended particles and colloidal substances in the influent water.
After coagulation and clarification, the effluent is mixed with alkaline agent and the like and enters a chemical crystallization circulating granulation fluidized bed for calcium removal treatment. In some specific implementations, the effluent obtained by coagulation clarification treatment passes through a clarified water tank and then is mixed with alkaline agent and the like to enter a chemical crystallization circulation granulation fluidized bed for calcium removal treatment.
In some specific implementations, the coagulated and clarified bottom slime is further processed, for example, discharged into a slime pond for sedimentation, the settled slime is dehydrated, and the separated water and supernatant of the slime pond are returned to a coagulating and clarifying treatment stage or a regulating stage for recycling.
And mixing the effluent after the secondary clarification treatment with an alkaline agent, and then carrying out calcium removal treatment in a chemical crystallization circulating granulation fluidized bed. In some specific implementations, the alkaline agent includes, but is not limited to, lime, sodium hydroxide, sodium carbonate, sodium metaaluminate, and the like, preferably sodium hydroxide and sodium carbonate. During the chemical crystallization circulating granulation fluidized bed decalcification treatment, seed crystals are also added, including but not limited to calcium carbonate crystals, quartz sand, garnet, calcite, striate, etc., preferably calcium carbonate crystals. In the application, the addition amount of the alkaline agent is required to keep the pH value of the calcium removal reaction at 8.8-9.2, so that the calcium ions in the mine water are fully crystallized and removed, and a large amount of the alkaline agent is not required to be added, thereby reducing the addition of the medicament. In some specific implementations, the amount of the alkaline agent added is required to keep the pH value of the decalcification reaction at 8.8-9.2, and the effluent water treated by the chemical crystallization circulating granulation fluidized bed contains 0.1-1.5 mmol/L of excess carbonate, preferably 0.5-1.0 mmol/L of excess carbonate. In some specific implementations, the ascending flow rate of the material in the chemical crystallization circulating granulation fluid bed is 50-150 m/h, preferably 60-100 m/h.
After the chemical crystallization circulating granulation fluidized bed treatment, the removal rate of calcium in water is more than 90%, and the obtained calcium carbonate crystal particles are discharged and recovered. The grain diameter of the calcium carbonate crystal grain is 2-3 mm, and the purity is more than 90%.
Filtering the effluent treated by the chemical crystallization circulating granulation fluidized bed, adjusting the pH value to 7.8-8.3, and then entering a sodium ion exchanger for magnesium removal treatment. The effluent of the chemical crystallization circulating granulation fluidized bed still contains a certain amount of suspended microparticles such as unsettled calcium carbonate and the like, and when the pH value is adjusted back before filtration, the microparticles (including organic flocs) such as calcium carbonate and the like in the water are dissolved or partially disintegrated to generate finer particles, which cannot be effectively trapped in the filtration, so that the turbidity of the filtered effluent is higher, and meanwhile, the free calcium ions dissolved by the microparticles also increase the operation burden of a sodium bed in a subsequent sodium ion exchanger, and simultaneously, the calcium type proportion in resin at the end of the operation is higher. Therefore, the pH value callback site of the effluent of the chemical crystallization circulating granulation fluidized bed is placed after the filtration treatment, so that the filtration treatment fully entraps unsettled particles, and the residual calcium hardness in the water is effectively reduced.
In some specific implementations, the filtration process may be performed by a V-bank filter, a multi-media filter, a fibrous filter, or the like. And (3) filtering the effluent to adjust the pH value to 7.8-8.3, and then enabling the effluent to enter a sodium ion exchanger for magnesium removal reaction.
In some specific implementations, sulfuric acid may be used to adjust the pH of the filtered water. In some specific implementations, the pH is adjusted and then subjected to an adjustment treatment, such as introducing it into a first softening tank for adjustment of water volume, water quality, etc., before entering the sodium ion exchanger for magnesium removal.
In some embodiments, the conditioned water may be continuously acidified for backwashing the filter apparatus, as the application is not particularly limited.
In some specific implementations, the mine water is ion exchanged in a sodium ion exchanger, magnesium ions are concentrated and enriched by using resin, and the removal rate of hardness in the water is more than 99%. The effluent of the sodium ion exchanger may be subjected to subsequent further treatment, such as membrane treatment.
In some specific implementations, the magnesium-removed effluent is conditioned, for example, introduced into a second softening tank for conditioning and equalizing the water volume and quality, and then subjected to subsequent further treatment.
In some specific implementations, the magnesium-depleted effluent is first sterilized and then conditioned, such as by sodium hypochlorite.
In some specific implementations, the sodium bed in the sodium ion exchanger needs to be regenerated. The regeneration mode can adopt a two-step method: the concentration of the regenerated liquid is diluted and then concentrated, and the regeneration flow is large and then small, namely, the regenerated liquid firstly enters the diluted salt liquid at a large flow and then enters the concentrated salt liquid at a small flow during regeneration; a three-step process may also be employed. The concentration of the regeneration liquid is diluted and then concentrated, the regeneration flow is large and then small, and the CaSO can be effectively avoided 4 The precipitate was precipitated in the resin layer. In some embodiments, the post-depth treated effluent may be used, for example, to contain high concentrations of Na produced by a subsequent membrane concentration system + As the regeneration liquid for regenerating the sodium bed, no additional regeneration system is needed, thus saving the construction cost and the operation cost. The backwash and forward washing drainage generated in the regeneration process are recovered and enterThe coagulation clarification treatment or the adjustment phase before the coagulation clarification treatment is circulated; the high-concentration magnesium-containing regenerated wastewater can be further treated for magnesium recovery, for example, the regenerated wastewater is firstly collected and then subjected to flocculation precipitation reaction by a high-density sedimentation tank, and the added medicaments are alkali and coagulant aids, including but not limited to sodium hydroxide, polyacrylamide and the like. The addition amount of the alkali enables the pH value of flocculation precipitation treatment to be 10.8-11.3, and magnesium ions are enabled to generate magnesium hydroxide, so that precipitation is achieved. And (3) carrying out flocculation precipitation reaction on high-concentration magnesium ions in the regenerated wastewater in a strong alkaline environment, wherein the actual consumption of sodium hydroxide is greatly reduced due to the reduction of the wastewater amount and the improvement of the magnesium ion concentration in the water, so that the running cost is saved, and meanwhile, the effluent after flocculation precipitation is recycled to a chemical crystallization circulation granulation fluidized bed or clarification treatment before the treatment of the chemical crystallization circulation granulation fluidized bed for recycling, and the water is recycled to a coagulation clarification treatment stage or an adjustment stage before the coagulation clarification treatment after the magnesium-rich sludge is dehydrated. In some specific implementations, the magnesium hydroxide in the resulting magnesium-rich sludge has a purity of greater than 95%.
The application adopts the sodium ion exchange resin to concentrate and enrich magnesium ions, fully utilizes the characteristic of the regeneration step sequence of the sodium bed, separately collects the wastewater in the back washing and forward washing stages and the wastewater in the regeneration and replacement stages, reduces the wastewater volume by about 50%, further improves the concentration of magnesium ions in the wastewater, and is beneficial to the efficient recovery of magnesium.
The application also provides a high-hardness and high-mineralization coal mine water recycling pretreatment device, which comprises the following steps:
the coagulation clarification unit is provided with a high-hardness high-mineralization coal mine water inlet;
a chemical crystallization circulating granulation fluidized bed communicated with the water outlet of the coagulation clarification unit;
a filtering unit communicated with a water outlet of the chemical crystallization circulating granulation fluidized bed;
a pH value adjusting unit communicated with the water outlet of the filtering unit;
and the sodium ion exchanger is communicated with the water outlet of the pH value adjusting unit.
The pretreatment device provided by the application comprises a coagulation clarification unit provided with a high-hardness high-mineralization coal mine water inlet, which is used for carrying out coagulation reaction and clarification separation to obtain effluent and coal slime, and substances such as coal dust, colloid and the like in the mine water are removed by chemical coagulation and high-efficiency clarification or cyclone separation principles.
In some specific implementations, the preprocessing device further includes: the flocculant adding device is used for adding flocculant into the coagulating and clarifying unit 4, and a medicine outlet of the flocculant adding device is communicated with the coagulating and clarifying unit; and a coagulant aid dosing device for dosing coagulant aid into the coagulation clarification unit, wherein a drug outlet of the coagulant aid dosing device is communicated with the coagulation clarification unit.
In some specific implementation modes, the pretreatment device further comprises an adjusting tank for balancing water quality and adjusting water quantity of the high-hardness and high-mineralization coal mine water, the adjusting tank is provided with a high-hardness and high-mineralization coal mine water inlet, a water inlet of the coagulation clarification unit is communicated with a water outlet of the adjusting tank, and the effluent after being treated by the adjusting tank enters the coagulation clarification unit, and is subjected to coagulation reaction, clarification and separation by adding a flocculating agent, a coagulant aid and the like through a flocculating agent adding device and a coagulant aid adding device.
In some specific implementations, the coagulation clarification unit may be a mechanical stirring clarification tank, a high density sedimentation tank, a high efficiency cyclone purifier, etc., and the application is not particularly limited.
In some specific implementations, the pretreatment device further comprises a coal slime pond for settling the clarified and separated coal slime, the coal slime pond is communicated with the coal slime outlet of the coagulation and clarification unit, mud discharged from the coal slime pond enters the dehydrator for dehydration, and supernatant liquid of the coal slime pond and water removed by the dehydrator flow back to the regulating tank.
In some specific implementations, the pretreatment device further includes a clarifier tank in communication with the water outlet of the coagulation clarifier unit.
In some specific implementations, the sodium hydroxide dosing device, the sodium carbonate dosing device, the calcium carbonate seed crystal dosing device are respectively communicated with the chemical crystallization circulating granulation fluidized bed and are used for dosing sodium hydroxide, sodium carbonate, calcium carbonate seed crystals and the like to the chemical crystallization circulating granulation fluidized bed.
The pretreatment device also comprises a chemical crystallization circulating granulation fluidized bed which is communicated with the water outlet of the clear water tank, and calcium removal reaction is carried out under the action of sodium hydroxide, sodium carbonate, calcium carbonate seed crystal and the like to form calcium carbonate crystals. In the application, the pH value of the chemical crystallization circulating granulation fluidized bed is controlled to be 8.8-9.2, only calcium is removed, magnesium is not removed, the excessive carbonate content of 0.5-1.0 mmol/L in effluent is ensured, the calcium removal efficiency is improved, for example, the calcium removal efficiency can reach more than 90%, and the addition of a medicament is reduced.
In some specific implementation modes, the chemical crystallization circulating granulation fluidized bed 11 is also provided with an online pH meter and an online alkalinity analyzer, and the calcium hardness of the discharged water can be regulated and controlled in real time through the dosage, and meanwhile, the content of excessive carbonate radicals in the water is ensured to be 0.5-1.0 mmol/L, so that excessive dosage of the medicament is avoided.
In some embodiments, the apparatus further comprises a particle storage device in communication with the solid particle outlet of the circulating granulation fluid bed for chemical crystallization for storing and recovering calcium carbonate crystals formed in the decalcification reaction.
The pretreatment device further comprises a filtering unit which is communicated with the water outlet of the chemical crystallization circulating granulation fluidized bed and is used for removing non-settled solid particles in the effluent of the chemical crystallization circulating granulation fluidized bed, so that the operation burden of subsequent equipment is effectively reduced.
In some embodiments, the filter unit may be a V-bank filter, a multi-media filter, a fiber filter, etc., as the application is not particularly limited.
In some specific implementations, the filter unit is further provided with an online pH meter for monitoring the pH of the filter unit effluent.
In some specific implementations, the filter unit can be backwashed in a form of backwashing water inlet and acid addition, and backwashed waste water is recycled to the regulating tank.
In some specific implementations, the pretreatment device further includes a first softening tank in communication with the water outlet of the filtration unit for quality equalization and water volume regulation of mine water.
The pretreatment device comprises an acid adding device which is communicated with a pipeline between the water outlet of the filtering unit and the water inlet of the first softening water tank and is used for adjusting the pH value of the water outlet of the filtering unit to 7.8-8.3, namely, the water outlet of the chemical crystallization circulating granulation fluidized bed is filtered by the filtering unit and then the pH value of the water outlet of the chemical crystallization circulating granulation fluidized bed is adjusted to 7.8-8.3. The effluent of the chemical crystallization circulating granulation fluidized bed still contains a certain amount of suspended microparticles such as unsettled calcium carbonate and the like, and when the pH value is adjusted back before the filtering unit, the microparticles (including organic flocs) such as the calcium carbonate and the like in the water are dissolved or partially disintegrated to generate finer particles, which cannot be effectively trapped in the filtering unit, so that the turbidity of filtered effluent is higher, and meanwhile, the free calcium ions dissolved by the microparticles also increase the operation burden of a sodium bed in a subsequent sodium ion exchanger, and simultaneously, the calcium type proportion in resin at the end of the operation is higher. Therefore, the pH value callback site of the effluent of the chemical crystallization circulating granulation fluidized bed is arranged behind the filtering unit, so that the filtering unit can fully intercept unsettled particles, and the residual calcium hardness in the water is effectively reduced. And the pH value is adjusted to 7.8-8.3 after filtration, and in the pH value range, all the excessive carbonate in the original water is converted into bicarbonate, so that the scaling risk of a subsequent membrane system is reduced.
In some specific implementations, the acid adding device may be in communication with a backwash water inlet line of the filter unit for adjusting a pH value of backwash water inlet of the filter unit to backwash the filter unit.
The pretreatment device also comprises a sodium ion exchanger which is communicated with the water outlet of the first softening water tank, magnesium ions in mine water are subjected to ion exchange with sodium ions on the sodium ion exchanger resin, and the magnesium ions are concentrated and enriched, so that magnesium ions (including residual calcium ions) in the mine water are removed, and the removal rate of hardness in the water can be more than 99%.
In some specific implementations, the pretreatment device further comprises a second softening water tank communicated with the water outlet of the sodium ion exchanger for water quality equalization and water quantity regulationThe effluent can enter a subsequent advanced treatment system, such as a membrane concentration system for treatment, the membrane concentration system or other advanced treatment systems obtain a product containing high concentration Na + The effluent of (2) can be used as regeneration liquid to regenerate the sodium bed of the sodium ion exchanger.
In some specific implementations, the pretreatment device further includes a sodium hypochlorite dosing device in communication with the conduit between the second softened water basin inlet and the sodium ion exchanger outlet for sterilizing mine water prior to entering the second softened water basin.
Regeneration liquid inlet of sodium ion exchanger, flushing water and advanced treatment system obtained high-concentration Na + Is communicated with the water outlet of the sodium bed, and washes and regenerates the sodium bed. And (5) back washing and forward washing drainage are recycled to the regulating tank, and the regenerated and replaced wastewater is discharged into the wastewater collecting tank.
In some specific implementations, the pretreatment device further includes a high-density sedimentation tank in communication with the water outlet of the wastewater collection tank for treating sodium bed regeneration wastewater.
The high-density sedimentation tank is used for flocculating and settling magnesium ions in the regenerated wastewater to form magnesium-rich sludge, the magnesium-rich sludge is discharged to the sludge tank, and the effluent from which the magnesium ions are removed is returned to the clarification tank 7 for recycling.
In some specific implementations, the pretreatment device further comprises a sodium hydroxide dosing device 8 and a coagulant aid dosing device, which are respectively communicated with the high-density sedimentation tank and used for dosing sodium hydroxide and coagulant aid to flocculate and sediment magnesium ions to form magnesium hydroxide sludge.
The sludge pool further enriches the magnesium-rich sludge, then enters a sludge dewatering device for dewatering to obtain magnesium-containing sludge, and the removed water enters an adjusting pool for recycling.
The application provides a pretreatment method for recycling high-hardness and high-mineralization coal mine water, which comprises the steps of firstly carrying out coagulation clarification treatment, removing substances such as coal dust, colloid and the like, then mixing with alkaline agent and the like, entering a chemical crystallization circulation granulation fluidized bed, carrying out calcium removal treatment under the condition that the pH value is 8.8-9.2, and reacting to generate CaCO (CaCO) 3 And (5) recovering the crystallized particles. Will go outThe pH value of the water is regulated to 7.8-8.3 after the water is further filtered, and then the water enters a sodium ion exchanger for magnesium removal treatment, and magnesium ions are concentrated and enriched by using resin. And (3) allowing the sodium bed effluent after deep hardness removal to enter a subsequent deep treatment system, and performing flocculation precipitation reaction on the sodium bed regenerated wastewater in a high-density precipitation tank to obtain magnesium-rich sludge. The pretreatment method provided by the application has the advantages of simple process flow, low cost and stable softening effect, can realize the step-by-step recovery of calcium and magnesium ions, achieves the aim of recycling, and can realize the zero emission of mine water with high hardness and high mineralization degree by combining with a membrane method.
Drawings
Fig. 1 is a schematic structural diagram of a high-hardness and high-mineralization pretreatment device for mine water recycling in a coal mine, which is provided by the embodiment of the application.
Detailed Description
The technical solutions of the present application will be clearly and completely described in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In order to further illustrate the present application, the following examples are provided.
Example 1
Referring to fig. 1, fig. 1 is a schematic structural diagram of a high hardness and high mineralization pretreatment device for mine water in a coal mine according to embodiment 1 of the present application, wherein: 1 is an adjusting tank, and a water inlet of the adjusting tank is communicated with water in a coal mine; the device is characterized in that the device 4 is a coagulating and clarifying unit, in particular a high-efficiency cyclone purifier, a water inlet of the device is communicated with a water outlet of the regulating tank 1, the device 2 is a flocculating agent dosing device and the device 3 is a coagulant aid dosing device, and the device is respectively communicated with a pipeline between water outlet of the regulating tank 1 and water inlet of the coagulating and clarifying unit 4; 5 is a coal slime pond, and a slime inlet is communicated with a slime outlet of the coagulation clarification unit 4; 6 is a dehydrator, the mud inlet of which is communicated with the mud outlet of the coal slime pond 5, the mud outlet of which is coal slime, and the water outlet of which is communicated with the regulating pond 1; 7 is a clarifying water tank, and the water inlet of the clarifying water tank is communicated with the water outlet of the coagulating and clarifying unit 4; 11 is a chemical crystallization circulating granulation fluidized bed, and the water inlet is communicated with the water outlet of the clarifying basin 7; 8 is a sodium hydroxide dosing device, 9 is a sodium carbonate dosing device and 10 is a calcium carbonate seed crystal dosing device, which are respectively communicated with pipelines between the water outlet of the clarification tank 7 and the water inlet of the chemical crystallization circulating granulation fluidized bed 11; an on-line pH meter and an on-line alkalinity analyzer (not shown in the figure) are arranged on the chemical crystallization circulating granulation fluidized bed 11; and 12 is a particle storage device which is communicated with a solid particle outlet of the chemical crystallization circulating granulation fluidized bed 11. 13 is a filter unit, in particular a high-efficiency fiber filter, the water inlet of which is communicated with the water outlet of the chemical crystallization circulating granulation fluidized bed 11; 15 is a first softening water tank, and the water inlet of the first softening water tank is communicated with the water outlet of the filtering unit 13; 14 is an acid adding device which is communicated with a pipeline for water outlet of the filtering unit 13 and water inlet of the first softening water tank 15; a water inlet of the sodium ion exchanger is communicated with a water outlet of the first softening water tank 15; the sodium hypochlorite dosing device is connected with a pipeline between the water outlet of the first softening water tank 15 and the water inlet of the sodium ion exchanger 16; and 18 is a second softening water tank, the water inlet of the second softening water tank is communicated with the water outlet of the sodium ion exchanger 16, and the water outlet can be directly communicated with a subsequent advanced treatment system. 19 is a waste water collecting tank, the water inlet of which is communicated with the regenerated waste water outlet of the sodium ion exchanger 16; 20 is a high-density sedimentation tank, the water inlet of which is communicated with the water outlet of the wastewater collection tank 19, and a flocculating agent adding device and a coagulant aid adding device are also arranged on a pipeline between the water outlet of the wastewater collection tank 19 and the water inlet of the high-density sedimentation tank 20; 21 is a sludge pond, and a sludge inlet of the sludge pond is communicated with a sludge outlet of the high-density sedimentation pond 20; and 22 is a sludge dewatering device, a sludge inlet of the sludge dewatering device is communicated with a sludge outlet of the high-density sedimentation tank 20, and a water outlet of the sludge dewatering device is communicated with the regulating tank 1.
Example 2
The device provided in example 1 was used to treat mine water:
the turbidity of the inflow water of the mine water of the coal mine is 60-180 NTU, the salt content is about 4000mg/L, and the total hardness is 900-1150 mg CaCO 3 The ratio of the calcium ion to the magnesium ion is 400-500 mg/L, the ratio of the sulfate radical to the magnesium ion is 40-55 mg/L, the ratio of the sulfate radical to the chlorine radical is 2300-2700 mg/L, and the ratio of the chlorine radical to the chlorine radical is 45-60 mg/L.
The water quantity and the water quality of the mine water of the coal mine are regulated by the regulating reservoir and then enter the high-efficiency cyclone purifier, and meanwhile, polyaluminum chloride PAC and polyacrylamide PAM are added into the water inlet of the high-efficiency cyclone purifier for flocculation reaction; the clear water after cyclone separation by the high-efficiency cyclone purifier enters a clear water tank, the bottom coal slime is discharged into a coal slime tank for sedimentation, the sludge discharged from the coal slime tank enters a dehydrator for dehydration, and the supernatant fluid of the coal slime tank and the water removed by the dehydrator return to the regulating tank. The effluent of the clarifying water tank enters a chemical crystallization circulating granulation fluidized bed to carry out a calcium removal reaction, sodium hydroxide, sodium carbonate and calcium carbonate crystals are added into the chemical crystallization circulating granulation fluidized bed, the pH value of the reaction is controlled to be 8.8-9.2, and the effluent contains 0.5-1.0 mmol/L of excessive carbonate radical; the rising flow velocity in the chemical crystallization circulating granulation fluidized bed is 60-100 m/h, and CaCO is generated by reaction 3 The grain size of the crystal grains is 2-3 mm, the purity is more than 90%, and the crystal grains are discharged to a grain storage device for recycling.
After treatment by a chemical crystallization circulating granulation fluidized bed, the calcium ions in the water are less than 50mg/L, the turbidity is less than 5 NTU, and the water contains 0.5-1.0 mmol/L of excessive carbonate content. The effluent enters a high-efficiency fiber filter for filtering treatment, and the calcium ions and turbidity of the filtered effluent are less than 40mg/L and less than 2 NTU respectively. And then adding sulfuric acid into the water to adjust the pH value to 7.8-8.3, and then, entering a first softening water tank. The high-efficiency fiber filter is backwashed in a form of backwashing and sulfuric acid, and backwashed waste water is recycled to the regulating tank. The water in the first softening water tank enters a sodium ion exchanger to perform magnesium removal reaction, and the total hardness of the water discharged is less than 5mgCaCO 3 And (3) the turbidity is less than 1 NTU, and the effluent enters a second softening water tank after being added with sodium hypochlorite for sterilization. The effluent of the pretreatment process completely meets the requirement of the water quality of the inlet water of a subsequent advanced treatment system (such as a membrane concentration system).
The regeneration of the sodium ion exchanger adopts a subsequent membrane concentration system to produce a product containing high concentration Na + The concentrated water of (2) is used as regeneration liquid, and the regeneration mode adopts two steps: the concentration of the regeneration liquid is diluted and then concentrated, the regeneration flow is large and then small, and the CaSO is effectively avoided 4 The precipitate was precipitated in the resin layer. And (3) back washing and forward washing drainage in the sodium bed regeneration process are recovered to the regulating tank, and the regeneration and replacement wastewater enters the wastewater collecting tank. Waste water recoveryThe wastewater from the pool enters a high-density sedimentation tank, magnesium hydroxide flocculation sedimentation reaction is carried out by adding sodium hydroxide and coagulant aid, the high-density sedimentation tank is provided with an online pH meter, the pH value is controlled to be 10.8-11.3 by adjusting the adding amount of the sodium hydroxide, the wastewater is provided with sludge reflux, produced water is recycled to a clarified water tank, magnesium-rich sludge enters a sludge tank, the magnesium-rich sludge is dehydrated and recycled by a sludge dehydration device, the purity of the obtained magnesium hydroxide is more than 95%, and the removed water is recycled to an adjusting tank.
Comparative example 1
In the embodiment 2, calcium ions in water discharged from the chemical crystallization circulating granulation fluid bed are less than 50mg/L, turbidity is less than 5 NTU, and meanwhile, the water contains 0.5-1.0 mmol/L of excessive carbonate content. The pH value of the effluent is adjusted to 7.8-8.3 by adding sulfuric acid, and the effluent enters a high-efficiency fiber filter for filtering treatment. The turbidity of the filtered effluent is greater than 2 NTU and basically between 2 and 5 NTU, and the calcium ion is greater than 40mg/L and basically between 45 and 50 mg/L. The running period of the sodium ion exchanger and the total hardness index of the effluent are basically unchanged, but the turbidity is more than 1 NTU and basically between 1 and 3 NTU, and meanwhile, the purity of magnesium hydroxide in the sludge obtained by flocculating and settling the regenerated wastewater is less than 95 percent and basically between 90 and 93 percent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the application. Thus, the present application is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (4)
1. A method for recycling and preprocessing high-hardness and high-mineralization coal mine water comprises the following steps:
a) Performing coagulation clarification treatment on the high-hardness and high-mineralization coal mine water;
b) Mixing the effluent obtained in the step a) with an alkaline agent, and feeding the mixture into a chemical crystallization circulating granulation fluidized bed for carrying outCalcium removal treatment and recovery of CaCO produced by the reaction 3 The pH value of the calcium removal treatment is 8.8-9.2; the effluent obtained in the step b) contains 0.5-1.0 mmol/L carbonate;
c) Filtering the effluent obtained in the step b), regulating the pH value to 7.8-8.3, and introducing the effluent into a sodium ion exchanger for magnesium removal treatment to obtain pretreated effluent;
d) Sterilizing the effluent obtained in the step c);
further comprises: performing regeneration treatment on the sodium ion exchanger, and performing flocculation precipitation reaction on the obtained regenerated wastewater in a high-density sedimentation tank to obtain a magnesium-rich product; the pH value of the flocculation precipitation reaction is 10.8-11.3.
2. The pretreatment method according to claim 1, wherein the sodium ion exchanger regeneration treatment is performed by a membrane concentration system to produce a solution containing high concentration of Na + The concentrated water is used as regeneration liquid, and the regeneration mode is a two-step or three-step regeneration method.
3. A device for a high hardness and high mineralization pretreatment method of mine water in a coal mine, as claimed in claim 1, comprising:
the coagulation clarification unit is provided with a high-hardness high-mineralization coal mine water inlet;
a chemical crystallization circulating granulation fluidized bed communicated with the water outlet of the coagulation clarification unit; an online pH meter for monitoring the pH value and an online alkalinity analyzer for monitoring carbonate radicals are arranged on the chemical crystallization circulating granulation fluidized bed;
a filtering unit communicated with a water outlet of the chemical crystallization circulating granulation fluidized bed;
a pH value adjusting unit communicated with the water outlet of the filtering unit;
a sodium ion exchanger communicated with the water outlet of the pH value adjusting unit;
a high-density sedimentation tank communicated with the water outlet of the regenerated wastewater collection tank of the sodium ion exchanger;
and the sludge tank is communicated with the sludge outlet of the high-density sedimentation tank.
4. The apparatus of claim 3, wherein the coagulation clarification unit is a mechanically agitated clarifier, a high density settling tank, or a high efficiency cyclone;
the filter unit is a V-shaped filter tank, a multi-medium filter or a fiber filter.
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