CN116444106B - High-hardness high-sulfate type coal mine water treatment method and device - Google Patents
High-hardness high-sulfate type coal mine water treatment method and device Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 337
- 239000003245 coal Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 77
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 66
- 238000001728 nano-filtration Methods 0.000 claims abstract description 64
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 48
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 238000001914 filtration Methods 0.000 claims abstract description 45
- 238000002425 crystallisation Methods 0.000 claims abstract description 40
- 230000008025 crystallization Effects 0.000 claims abstract description 40
- 239000011575 calcium Substances 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 29
- 238000005352 clarification Methods 0.000 claims abstract description 28
- 239000011777 magnesium Substances 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 238000005345 coagulation Methods 0.000 claims abstract description 25
- 230000015271 coagulation Effects 0.000 claims abstract description 25
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 238000010612 desalination reaction Methods 0.000 claims abstract description 15
- 230000001360 synchronised effect Effects 0.000 claims abstract description 10
- 238000005341 cation exchange Methods 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 238000004062 sedimentation Methods 0.000 claims description 18
- 150000001768 cations Chemical class 0.000 claims description 17
- 238000001704 evaporation Methods 0.000 claims description 15
- 238000005469 granulation Methods 0.000 claims description 15
- 230000003179 granulation Effects 0.000 claims description 15
- 230000008020 evaporation Effects 0.000 claims description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 13
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 239000000835 fiber Substances 0.000 claims description 5
- 238000012544 monitoring process Methods 0.000 claims description 3
- 208000028659 discharge Diseases 0.000 claims description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims 1
- 229910001415 sodium ion Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 10
- 239000000084 colloidal system Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002817 coal dust Substances 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 58
- 239000012528 membrane Substances 0.000 description 35
- 239000013078 crystal Substances 0.000 description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 28
- 239000013505 freshwater Substances 0.000 description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000701 coagulant Substances 0.000 description 16
- 229920002401 polyacrylamide Polymers 0.000 description 14
- 230000001105 regulatory effect Effects 0.000 description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 239000010802 sludge Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 239000003814 drug Substances 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000002455 scale inhibitor Substances 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- 229910001425 magnesium ion Inorganic materials 0.000 description 9
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 230000001976 improved effect Effects 0.000 description 7
- 229910019440 Mg(OH) Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000011859 microparticle Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000008394 flocculating agent Substances 0.000 description 5
- 238000005189 flocculation Methods 0.000 description 5
- 230000016615 flocculation Effects 0.000 description 5
- 229910001629 magnesium chloride Inorganic materials 0.000 description 5
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 238000011001 backwashing Methods 0.000 description 4
- 239000003250 coal slurry Substances 0.000 description 4
- 238000004891 communication Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012510 hollow fiber Substances 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 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 2
- 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 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000009395 breeding Methods 0.000 description 2
- 230000001488 breeding effect Effects 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 238000011112 process operation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910021532 Calcite Inorganic materials 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 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
- C02F1/02—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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- 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
- C02F1/52—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention provides a short-flow zero-emission treatment method and device for high-hardness high-sulfate type 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 removing calcium, magnesium and silicon through chemical softening, further filtering effluent, adjusting the pH value to 7.8-8.3, and then sequentially carrying out ultrafiltration, weak acid cation exchange, carbon dioxide removal, reverse osmosis desalination, dish tube nanofiltration synchronous salt separation, concentration and evaporative crystallization, thereby realizing the zero emission of the high-hardness high-sulfate type coal mine water. Aiming at the characteristics of high hardness, high sulfate, low COD and low chlorine radical of the water quality of the mine water of the coal mine, the invention adopts a short zero-emission process flow, saves investment, has stable and reliable system operation, ensures that the water quality of the effluent meets the standard requirements of industrial and agricultural reuse water, realizes the recycling of salt and achieves the aim of zero emission of the mine water.
Description
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method and a device for short-flow zero-emission treatment of high-hardness high-sulfate mine water.
Background
The high-hardness high-sulfate mine water is derived from deep underground water, and the sulfur content in coal and gangue in a high-sulfur coal mining area is high, so that the sulfate content of the mine water is high and generally in the range of 1000-2500 mg/L and can reach 3000mgL at most after complex chemical action. In addition, the total hardness and the calcium hardness are also high, and the total hardness is generally in the range of 1000-2000 mg/L. Meanwhile, the wastewater has the characteristics of low chloride and low COD. Sulfate ions have potential harm to human bodies and ecological environments, and when sulfate wastewater with high concentration permeates into farmlands, soil structures can be damaged, soil salinization is caused, and yield and quality of agricultural products are reduced. Therefore, in order to promote the recycling of mine water and the development of high quality industry, mine drainage is required to reach the surface water III standard in multiple areas, and SO is clearly required 4 2- Not higher than 250 mg/L.
The prior art discloses a plurality of mine water zero emission technologies of coal mines, wherein the membrane technology is an important research object in the mine water zero emission field, but the existing technology for treating mine water by adopting the membrane technology has a series of outstanding problems of unstable pretreatment effect, complex flow of a membrane technology system, outstanding membrane fouling phenomenon, high investment and running cost, complex maintenance operation and the like.
Disclosure of Invention
In view of the above, the application aims to provide the high-hardness high-sulfate type coal mine water short-process zero-emission treatment method and device.
The application provides a short-process zero-emission treatment method for high-hardness high-sulfate coal mine water, which comprises the following steps:
a) Coagulating and clarifying the high-hardness high-sulfate type coal mine water;
b) C), chemically softening the effluent obtained in the step a) to remove calcium, magnesium and silicon;
c) Filtering the effluent obtained in the step b), and then adjusting the pH value to 7.8-8.3;
d) Sequentially carrying out ultrafiltration, weak acid cation exchange, carbon dioxide removal, reverse osmosis desalination, dish tube nanofiltration synchronous salt separation, concentration and evaporative crystallization on the effluent obtained in the step c).
The treatment method provided by the application carries out zero emission treatment on the high-hardness high-sulfate type coal mine water, and after calcium, magnesium and silicon in the water are removed, ultrafiltration, weak acid cation exchange, carbon dioxide removal, reverse osmosis desalination, dish tube type nanofiltration synchronous salt separation, concentration, evaporative crystallization and the like are sequentially carried out, so that zero emission is realized. In some specific implementation modes, the high-hardness high-sulfate type coal mine water inlet turbidity is 50-300 NTU, the salt content is about 3000-5000 mg/L, the total hardness is 800-1500 mg/L, the calcium ions are 300-800 mg/L, the magnesium ions are 30-70 mg/L, the sulfate radicals are 2000-350 mg/L, and the chloride radicals are 40-100 mg/L. In some specific implementation modes, the high-hardness high-sulfate type coal mine water inlet turbidity is 60-180 NTU, the salt content is about 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, the high-hardness high-sulfate type coal mine water inlet turbidity is 100-250 NTU, the salt content is about 4500mg/L, the total hardness is 1100-1300 mg/L, the calcium ions are 500-600 mg/L, the magnesium ions are 50-65 mg/L, the sulfate radicals are 2650-3000 mg/L, and the chloride radicals are 60-75 mg/L.
In some specific implementation modes, the high-hardness high-sulfate type coal mine water is firstly regulated before coagulation and clarification, and the water quality and the water quantity are regulated, so that the treatment system is stably operated.
And after the water quantity is stable, coagulating and clarifying the high-hardness high-sulfate type coal mine water, namely adding flocculating agent, coagulant aid and the like into the mine water to perform coagulating reaction, clarifying and separating, and removing substances such as coal dust, colloid and the like in the 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.
And (3) after coagulation and clarification, carrying out chemical softening treatment on the effluent to remove calcium, magnesium and silicon. In some specific implementations, the effluent from coagulation clarification is first passed through a clarifier and then chemically softened.
In some specific implementations, the coagulated and clarified bottom coal slurry is further processed, for example, discharged into a coal slurry pond for sedimentation, the settled coal slurry is dehydrated, and the separated water and supernatant of the coal slurry pond are returned to the coagulation and clarification stage or the conditioning stage for recycling.
The chemical softening treatment adopts flocculation precipitation or crystallization and other methods to remove calcium, magnesium and silicon in mine water, and can simultaneously remove calcium, magnesium and silicon, and can also remove calcium and magnesium and silicon step by step. In some specific implementations, the chemical softening treatment is a method of flocculation precipitation to remove magnesium, calcium and silicon simultaneously. In the specific scheme, the pH value of the reaction is controlled to be 10.8-11.3 by adding an alkaline agent, and the effluent contains 1.0-2.5 mmol/L of excessive carbonate, preferably 1.5-2.0 mmol/L of excessive carbonate. Ca (Ca) 2+ 、Mg 2+ The ions undergo chemical reaction to produce CaCO 3 /Mg(OH) 2 Precipitating, adding magnesium salt, flocculant and coagulant aid, and removing silicon dioxide in water by adsorption and coprecipitation of a large amount of magnesium hydroxide flocs. In some specific embodiments, 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. In some specific embodiments, the magnesium salt is magnesium chloride. 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 polymeric ferric sulfate and the coagulant aid is polyacrylamide. In the invention, the addition amount of the alkaline agent is required to keep the pH value of the chemical softening reaction at 10.8-11.3, so as to ensure the sufficient precipitation removal of calcium and magnesium ions in mine water.
In some embodiments, the chemical softening treatment is a crystallization process with simultaneous removal of magnesium and calcium, e.g., chemicalAnd softening the material by using a circulating granulation fluid bed for chemical crystallization. In the implementation mode, the pH value of a chemical crystallization circulating granulation fluidized bed is controlled to be 10.8-11.3 by adding an alkaline agent and seed crystals, so that Ca is obtained 2+ 、Mg 2+ The ions undergo chemical reaction to produce CaCO 3 /Mg(OH) 2 /SiO 2 The composite crystal is attached to the surface of the seed crystal, so that the hardness of calcium and magnesium and silicon in water are removed, and no sludge difficult to treat is generated. 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. In some specific implementations, the seed crystal includes, but is not limited to, calcium carbonate crystals, quartz sand, garnet, calcite, striation, etc., preferably calcium carbonate crystals. In the invention, the addition amount of the alkaline agent is required to keep the pH value of the hardness removal reaction at 10.8-11.3, so as to ensure the sufficient crystallization removal of calcium, magnesium and silicon in mine water. In some specific implementations, the amount of the alkaline agent added is required to keep the pH value of the chemical softening reaction at 10.8-11.3, and the effluent water treated by the chemical crystallization circulating granulation fluidized bed contains 1.0-2.5 mmol/L of excess carbonate, preferably 1.5-2.0 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. And (3) discharging the obtained calcium carbonate crystal particles after treatment of a chemical crystallization circulating granulation fluidized bed, wherein the particle size of the calcium carbonate crystal particles is 2-3 mm, and the purity is more than 90%.
The method filters the effluent after chemical softening, adjusts the pH value to 7.8-8.3 and then carries out subsequent treatment. The effluent of the chemical softening treatment still contains a certain amount of suspended microparticles such as unsettled calcium carbonate, magnesium hydroxide and the like, and the pH value is adjusted back before filtration, so that 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 filtration, and the turbidity of the filtered effluent and the SDI of the subsequent ultrafiltration product water are caused 15 The ultra-filtration membrane is blocked more highly, and free calcium and magnesium dissolved out by the microparticles also increase the operation load of the weak acid cation exchanger, so that the hardness of the effluent is higher, and the effluent is made to be laterThe continuous reverse osmosis device cannot stably operate in a high recovery state. Therefore, the pH callback site of the chemical softening effluent is placed after the filtration treatment, so that the filtration treatment fully intercepts unsettled particles in the chemical softening unit, and the hardness of calcium and magnesium remained 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 residual hardness and alkalinity in the water can be thoroughly removed by the follow-up weak acid cation exchanger and the carbon removal device.
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.
In some specific implementations, sulfuric acid may be used to adjust the pH of the filtered effluent. In some specific implementations, the pH is adjusted and then subjected to an adjustment process, such as introducing it into a softening pond for adjustment of water volume, water quality, etc., before proceeding to a subsequent process.
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 method further comprises sterilizing the effluent after the pH adjustment before the subsequent treatment or the adjustment.
After chemical softening, filtering and pH value adjustment, the obtained effluent is sequentially subjected to ultrafiltration, weak acid cation exchange, carbon dioxide removal, reverse osmosis desalination, dish tube nanofiltration synchronous salt separation, concentration and evaporative crystallization, so that zero emission treatment of mine water can be realized.
In some specific implementations, the ultrafiltration can further depth filter, reducing the burden of subsequent system operation. In some specific implementations, the ultrafiltration treatment may be performed using a ceramic membrane treatment or a hollow fiber membrane treatment, which is not particularly limited in the present application.
In some specific implementations, further comprising backwashing the ultrafiltration device, the backwash water is preferably recycled to the coagulation clarification stage or to the re-clarification stage for recycling.
In some specific implementations, the turbidity of the effluent after ultrafiltration is less than 0.1NTU, SDI 15 Less than 3, and creates conditions for high recovery rate of subsequent treatment.
After ultrafiltration treatment, weak acid cation exchange is carried out on the obtained effluent, and the hardness and alkali of the effluent are deeply removed. In some embodiments, the ultrafiltration effluent is preferably collected and the amount of water is adjusted prior to entering the weak acid cation exchanger.
After weak acid cation exchange, the obtained effluent is subjected to carbon dioxide removal treatment. The carbon removal treatment is not limited, and for example, the carbon dioxide can be treated in a carbon dioxide remover under the action of a fan.
After the decarbonizing treatment, the obtained effluent is subjected to reverse osmosis desalination treatment to remove salt. In some specific implementation modes, the pH value of the effluent after removing carbon dioxide is preferably adjusted to 8.5-9.0, and reverse osmosis desalination is performed.
In some specific implementation modes, in the effluent after carbon dioxide removal treatment, the hardness is basically 0, the alkalinity is basically 0, and the reverse osmosis device operates under weak alkaline conditions of no hardness and pH value of 8.5-9.0, so that saponification or weak ionization of organic matters is facilitated, adhesion of the organic matters on the surface of a membrane is avoided, and in addition, the silicon solubility is increased along with the increase of the pH value, so that the silicon scaling limit is obviously improved. At this time, the risk of reverse osmosis membrane scaling and fouling is greatly reduced, and the water recovery rate can be as high as 90% or even higher. The reverse osmosis process operation mode can effectively solve the problems of organic pollution and microorganism breeding, and can realize high recovery rate, high desalination rate, economical system and stable operation.
Under the high recovery rate of more than 90 percent, the reverse osmosis concentrated water yield is greatly reduced, which is beneficial to reducing the treatment scale of the subsequent salt separation and concentration system and reducing the investment cost. Meanwhile, the salt content of RO concentrated water is obviously improved, and the higher the salt content of inlet water is, the nanofiltration membrane is used for Cl - The more likely a negative rejection rate occurs. This phenomenon is caused by the effect of the ions in the dawn, na, as the salt content of the feed water increases + Increased transmittance, monovalent Cl - Speed of penetrationThe ratio is more than bivalent SO 4 2- Large, to maintain the neutrality of the two sides of the film, more Cl is generated - The better the salt separating effect of nanofiltration is through the membrane.
In some specific implementations, before the reverse osmosis membrane treatment, the effluent after the carbon removal treatment is mixed with an alkaline agent, a reverse osmosis scale inhibitor, a reducing agent and the like, and then enters a reverse osmosis device for desalination treatment.
After reverse osmosis desalination treatment, the fresh water is recovered to reach the industrial and agricultural reuse water standard. The reverse osmosis concentrated water enters a disc tube type nanofiltration device and is subjected to salt separation and deep concentration treatment synchronously. In some specific implementations, the recovery rate of the disc tube nanofiltration device is 70% -80%. The dish tubular nanofiltration is a novel membrane component combining nanofiltration membrane materials and dish tubular components, has the characteristics of wide flow channel, short flow path and turbulent flow operation, and further has the advantages of low water inlet requirement, small operating pressure, high water recovery rate, pollution resistance, easy cleaning, long service life and the like. The nanofiltration membrane and the disc tube type component are combined, so that the advantages of the nanofiltration membrane and the disc tube type component can be fully utilized, the ideal synchronous salt separation and concentration effects are achieved, and the process flow is greatly simplified. In addition, the monovalent ion concentration on the nanofiltration concentrated water side can be effectively reduced by improving the water recovery rate, and the Cl is improved - The separation ratio and the higher recovery rate are beneficial to improving the purity of the sodium sulfate crystal salt at the concentrated water side.
In some specific implementations, the reverse osmosis concentrated water and the nanofiltration scale inhibitor are mixed and then enter a disc tube nanofiltration device for salt separation and concentration treatment.
After nanofiltration treatment, fresh water is recovered. Evaporating and crystallizing the nanofiltration concentrated water to obtain sodium sulfate crystal salt and distilled water, wherein the purity of the sodium sulfate crystal salt is not lower than 98.5%, and recovering the distilled water. In some specific implementations, the evaporative crystallization process may be Mechanical Vapor Recompression (MVR), thermal Vapor Recompression (TVR), multiple effect evaporation (MED), multiple Stage Flash (MSF), etc., as the invention is not particularly limited.
The invention provides a high-hardness high-sulfate coal mine water short-process zero-emission treatment device, which comprises:
the coagulation clarification unit is provided with a high-hardness high-sulfate type coal mine water inlet;
a chemical softening unit communicated with the water outlet of the coagulation clarification unit;
a filtering unit communicated with the water outlet of the chemical softening unit;
a pH value adjusting unit communicated with the water outlet of the filtering unit;
the ultrafiltration device is communicated with the water outlet of the pH value adjusting unit;
A weak acid cation exchanger communicated with the water outlet of the ultrafiltration device;
a decarbonizing device communicated with the water outlet of the weak acid cation exchange device;
a reverse osmosis device communicated with the water outlet of the carbon removing device;
a dish tube type nanofiltration device connected with the concentrated water outlet of the reverse osmosis device;
and the evaporation crystallization device is connected with the concentrated water outlet of the disc tube type nanofiltration device.
The treatment device provided by the application comprises a coagulation clarification unit 4 provided with a high-hardness high-sulfate type coal mine water inlet, which is used for carrying out coagulation reaction and clarification separation to obtain effluent and coal slime, and removing substances such as coal dust, colloid and the like in mine water through chemical coagulation and high-efficiency clarification or cyclone separation principles.
In some specific implementations, the processing device further includes: the flocculant adding device is used for adding flocculant into the coagulating and clarifying unit, 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 treatment device further comprises an adjusting tank for balancing water quality and adjusting water quantity of the high-hardness high-sulfate type coal mine water, the adjusting tank is provided with a high-hardness high-sulfate type coal mine water inlet, a water inlet of the coagulation clarification unit is communicated with a water outlet of the adjusting tank, and effluent water treated by the adjusting tank enters the coagulation clarification unit and is subjected to coagulation reaction, clarification separation and the like through a flocculant adding device, a coagulant aid adding device and the like.
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 treatment 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 5 and water removed by the dehydrator flow back to the regulating tank 1.
In some specific implementations, the treatment device further includes a clarifier tank in communication with the water outlet of the coagulation clarifier unit.
The treatment device comprises a chemical softening unit, and the chemical softening unit is used for removing calcium and magnesium hardness in mine water. In some specific implementations, the chemical softening unit is one or more of a high density sedimentation tank, a chemical crystallization circulating granulation fluidized bed, and the like.
In some specific implementations, the chemical softening unit is a high density sedimentation tank that removes magnesium and calcium simultaneously. In the specific scheme, naOH and Na are added 2 CO 3 Controlling the pH value of the high-density sedimentation tank to be 10.8-11.3 to ensure that Ca 2+ 、Mg 2+ The ions undergo chemical reaction to produce CaCO 3 /Mg(OH) 2 Precipitation, simultaneous addition of MgCl 2 And (3) removing silicon dioxide in the water by utilizing adsorption and coprecipitation of a large amount of magnesium hydroxide flocs. At this time, the sodium hydroxide dosing device, the sodium carbonate dosing device and the magnesium chloride dosing device are respectively communicated with the chemical softening unit and are used for dosing agents such as sodium hydroxide, sodium carbonate and magnesium chloride to the chemical softening unit. In some specific embodiments, the chemical softening unit can also comprise a flocculating agent dosing device and a coagulant aid dosing device which are respectively communicated with the chemical softening unit and used for dosing flocculating agent, coagulant aid and other medicaments to the chemical softening unit.
In the specific scheme, the high-density sedimentation tank is provided with an online pH meter and an online alkalinity analyzer, and the dosage of sodium hydroxide and sodium carbonate can be timely fed back and adjusted according to the real-time change of the concentration of hydroxide radicals and the concentration of carbonate radicals of discharged water so as to stably control the hardness of calcium ions and magnesium ions of softened discharged water and simultaneously ensure that the water contains residual carbonate radical content of 1.5-2.0 mmol/L.
In the specific scheme, the treatment device comprises a sludge dewatering device which is communicated with a sludge outlet of the chemical softening unit and is used for treating the formed calcium-magnesium-containing sludge.
In some specific implementations, the chemical softening unit is a chemical crystallization circulating granulation fluidized bed that simultaneously removes magnesium and calcium. In the implementation mode, a chemical crystallization circulating granulation fluidized bed is communicated with a water outlet of a clarifying water tank, and NaOH and Na are added 2 CO 3 And under the action of seed crystal, controlling the pH value of the high-density sedimentation tank to be 10.8-11.3, so that Ca is obtained 2+ 、Mg 2+ The ions undergo chemical reaction to produce CaCO 3 /Mg(OH) 2 /SiO 2 The composite crystal is attached to the surface of the seed crystal, so that the hardness and silicon in the water are removed, the sludge difficult to treat is not generated, and the particle size of the generated composite crystal particles is 2-3 mm and can be recycled. At this time, the sodium hydroxide dosing device, the sodium carbonate dosing device and the seed crystal dosing device are respectively communicated with the chemical softening unit and are used for dosing the chemical softening unit with the sodium hydroxide, the sodium carbonate, the seed crystal and other medicaments.
In the specific scheme, the chemical crystallization circulating granulation fluidized bed can be further provided with an online pH meter and an online alkalinity analyzer, and the dosage of sodium hydroxide and sodium carbonate can be timely fed back and adjusted according to the real-time change of the concentration of the hydroxide radical and the concentration of the carbonate radical of the discharged water so as to stably control the hardness of calcium ions and magnesium ions of softened water and simultaneously ensure that the water contains 1.5-2.0 mmol/L of residual carbonate radical.
In this embodiment, the treatment device comprises a particulate storage device in communication with the sludge outlet of the chemical softening unit for storing the calcium-magnesium crystals formed.
The treatment device further comprises a filtering unit which is communicated with the water outlet of the chemical softening unit and is used for removing non-settled solid particles in the water outlet of the chemical softening unit, 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 may be backwashed in the form of acid addition, with backwash wastewater being recycled to the conditioning tank.
In some specific implementations, the treatment device further includes a softening tank in communication with the water outlet of the filtration unit for quality equalization and water volume regulation of mine water.
The treatment device comprises an acid adding device and a sodium hypochlorite adding device, is communicated with a pipeline between the water outlet of the filtering unit and the water inlet of the softening pond, and is used for adjusting the pH value of the water outlet of the filtering unit and carrying out sterilization treatment on the water outlet of the filtering unit. In some specific implementations, the pH of the effluent from the filtration unit is adjusted to 7.8-8.3, even if the effluent from the chemical softening unit is filtered through the filtration unit before the pH is adjusted to 7.6-8.3. The effluent of the chemical softening unit still contains a certain amount of suspended microparticles such as unsettled calcium carbonate, magnesium hydroxide and the like, and the pH is adjusted back before the filtration of the filtering unit, so that the microparticles (including organic flocs) such as the calcium carbonate, the magnesium hydroxide and the like in the water are dissolved or partially disintegrated to generate finer particles, which cannot be effectively trapped in the filtration treatment, thereby leading to turbidity of the filtered effluent and SDI (ultrafiltration produced water) 15 The ultrafiltration membrane is blocked and aggravated, and meanwhile, the free calcium and magnesium dissolved out by the microparticles also increase the operation burden of the weak acid cation exchanger, so that the hardness of the effluent is higher, and the subsequent reverse osmosis device cannot stably operate in a high recovery rate state. Therefore, the pH callback site of the effluent of the chemical softening unit is placed after the filtration treatment, so that the filtration unit fully intercepts the unsettled particulate matters in the chemical softening unit,effectively reduces the hardness of the residual calcium and magnesium in water. 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 residual hardness and alkalinity of the follow-up weak acid cation exchanger and the carbon dioxide remover can be thoroughly removed.
In some specific implementations, the acid adding device may be in communication with a backwash water inlet line of the filtration unit, and backwash the filtration unit after pH adjustment.
The treatment device comprises an ultrafiltration device which is communicated with the water outlet of the first softening water tank and is used for carrying out deep filtration treatment on mine water from which calcium and magnesium ions are removed. In some specific implementations, the backwash water of the ultrafiltration device is recycled to the clarifier for reuse. In some specific implementations, the turbidity of the effluent from the ultrafiltration device 17 is less than 0.1NTU, SDI 15 Less than 3, and creates conditions for the high recovery rate operation of the subsequent reverse osmosis device. In some specific implementations, the ultrafiltration device may be a ceramic membrane module. In some specific implementations, the ultrafiltration device may be a hollow fiber membrane module.
In some specific implementations, the treatment device includes an ultrafiltration basin that is connected to the water outlet of the ultrafiltration device. In some specific implementations, the effluent from the ultrafiltration basin may be used to backwash the ultrafiltration device 17.
The treatment device comprises a weak acid cation exchanger which is used for deeply removing hardness and alkali from mine water.
The treatment device comprises a carbon removal unit, wherein the carbon removal unit comprises a carbon dioxide remover, a carbon removal fan arranged at the bottom of the carbon dioxide remover and a carbon removal water tank connected with a water outlet of the carbon dioxide remover. The carbon dioxide remover is communicated with the water outlet of the weak acid cation exchanger and is used for removing carbon under the action of the carbon removal fan. The hardness of the effluent after being treated by the weak acid cation exchanger and the decarbonizing unit is basically 0, and the alkalinity is basically 0, thus creating conditions for the high recovery rate operation of the subsequent reverse osmosis device.
The treatment device comprises a reverse osmosis device which is communicated with the water outlet of the carbon removal water tank. In some specific implementations, the reverse osmosis scale inhibition dosing device, the reverse osmosis reducing agent dosing device and the water inlets of the reverse osmosis devices are respectively communicated.
In some specific implementations, the treatment device further comprises a sodium hydroxide dosing device arranged on a pipeline between the water inlet of the reverse osmosis device and the water outlet of the decarbonizing water tank, and the pH value of the water inlet of the reverse osmosis device is adjusted to be 8.5-9.0. The reverse osmosis device runs under the conditions of no hardness and weak alkalinity, is favorable for saponification or weak ionization of organic matters, avoids the organic matters from adhering to the surface of the membrane, and in addition, the silicon solubility is increased along with the increase of the pH value, so that the silicon scaling limit is obviously improved. At this time, the risk of reverse osmosis membrane scaling and fouling is greatly reduced, and the water recovery rate can be as high as 90% or even higher. The reverse osmosis process operation mode can effectively solve the problems of organic pollution and microorganism breeding, and can realize high recovery rate, high desalination rate, economical system and stable operation.
The treatment device comprises a fresh water pond communicated with a fresh water outlet of the reverse osmosis device and a reverse osmosis concentrated water pond communicated with a concentrated water outlet of the reverse osmosis device. The fresh water in the fresh water tank can reach the industrial and agricultural reuse water standard.
The reverse osmosis concentrated water yield is greatly reduced under the condition of high recovery rate, which is beneficial to reducing the treatment scale of the subsequent salt separation and concentration system and reducing the investment cost. Meanwhile, the salt content of RO concentrated water is obviously improved, and the higher the salt content of inlet water is, the nanofiltration membrane is used for Cl - The more easily the negative retention rate is generated, the phenomenon is caused by the effect of the NaN ions, and along with the increase of the salt content of the inlet water, the Na + Increase in transmittance, cl - Transmittance rate is higher than SO 4 2- Large, to maintain the neutrality of the two sides of the film, more Cl is generated - Through the membrane, thereby improving the salt separation effect of nanofiltration.
The treatment device comprises a disc tube type nanofiltration device communicated with the water outlet of the reverse osmosis concentrated water tank, the disc tube type nanofiltration device carries out salt separation and deep concentration treatment on the reverse osmosis concentrated water, fresh water enters the fresh water tank, and the concentrated water enters the nanofiltration concentrated water tank. In some specific implementations, the nanofiltration scale inhibitor dosing device is communicated with a pipeline between the water outlet of the reverse osmosis concentrated water tank and the water inlet of the nanofiltration device for dosing the nanofiltration scale inhibitor.
In some specific implementations, the recovery rate of the disc tube nanofiltration device is 70% -80%. The dish tubular nanofiltration combines nanofiltration membrane materials with dish tubular components, has the characteristics of wide flow passage, short flow path and turbulent flow operation, and further has the advantages of low water inlet requirement, low operating pressure, high water recovery rate, pollution resistance, easy cleaning, long service life and the like. The nanofiltration membrane and the disc tube type component are combined, so that the advantages of the nanofiltration membrane and the disc tube type component can be fully utilized, the ideal synchronous salt separation and concentration effects are achieved, and the process flow is greatly simplified. In addition, the monovalent ion concentration on the nanofiltration concentrated water side can be effectively reduced by improving the water recovery rate, and the Cl is improved - The separation ratio and the higher recovery rate are beneficial to improving the purity of the sodium sulfate crystal salt at the concentrated water side.
The treatment device provided by the invention further comprises an evaporation crystallization device which is communicated with the concentrated water outlet of the dish-type nanofiltration device, the nanofiltration concentrated water is subjected to evaporation crystallization to generate sodium sulfate crystal salt, and distilled water enters a fresh water tank, so that the aim of zero emission of mine water is finally achieved. In some specific implementations, the purity of the sodium sulfate crystalline salt is not less than 98%.
In some specific implementations, the evaporative crystallization device is a mechanical vapor recompression device (MVR), a thermal vapor recompression device (TVR), a multiple effect evaporation device (MED), or a multi-stage flash device (MSF).
The method for zero emission treatment of high-hardness high-sulfate mine water comprises the steps of firstly carrying out coagulation clarification treatment, removing substances such as coal dust and colloid, then carrying out chemical softening to remove calcium, magnesium and silicon, further filtering the softened effluent, adjusting the pH value to 7.8-8.3, and then sequentially carrying out ultrafiltration, weak acid cation exchange, carbon dioxide removal, reverse osmosis desalination, dish tube nanofiltration synchronous salt separation, concentration and evaporative crystallization, thereby realizing zero emission. Aiming at the characteristics of high hardness, high sulfate, low COD and low chlorine radical of the water quality of the mine water of the coal mine, the invention adopts a short zero-emission process flow, saves investment, has stable and reliable system operation, ensures that the water quality of the effluent meets the standard requirements of industrial and agricultural reuse water, realizes the recycling of salt and achieves the aim of zero emission of the mine water.
According to the treatment method provided by the application, the content of residual carbonate in water is ensured to be 1.5-2.0 mmol/L after chemical softening treatment, and then the pH callback site of the chemical softening effluent is placed after filtering treatment, so that unsettled particles are fully trapped, and the operation burden of subsequent ultrafiltration and weak acid cation beds 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, and the weak acid cation bed and carbon dioxide remover process can thoroughly remove the residual hardness and alkalinity. In addition, the reverse osmosis device runs under the conditions of no hardness and weak alkalinity, so that the membrane fouling degree can be effectively relieved, the recovery rate reaches more than 90%, and the produced water meets the water quality requirement of the reuse water. The RO concentrated water quantity is greatly reduced under the condition of high recovery rate, so that the treatment scale of a subsequent salt separation and concentration system is reduced, and the investment cost is saved. Meanwhile, the salt content of RO concentrated water is obviously increased, which is beneficial to improving the subsequent nanofiltration salt separation effect. Furthermore, the nanofiltration adopts a dish tubular nanofiltration membrane technology, so that the advantages of the dish tubular nanofiltration membrane and the dish tubular nanofiltration membrane can be fully utilized, the ideal synchronous salt separation and concentration effects are achieved, and the process flow is greatly simplified. Under the condition of higher water recovery rate of 70% -80%, the monovalent ion concentration on the nanofiltration concentrated water side can be effectively reduced, and Cl is improved - The purity of the sodium sulfate crystal salt on the concentrated water side is higher than that of the sodium sulfate crystal salt on the concentrated water side.
Drawings
Fig. 1 is a schematic structural diagram of a short-flow zero-discharge treatment device for high-hardness high-sulfate coal mine water, 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 high-sulfate type coal mine water short-process zero-emission treatment device provided by embodiment 1 of the present application, wherein: 1 is an adjusting tank, a water inlet of which is communicated with water in a high-hardness high-sulfate coal mine and is used for adjusting water quality and water quantity; 4 is a coagulating and clarifying unit, in particular to a high-efficiency cyclone purifier, the water inlet of which is communicated with the water outlet of the regulating tank 1 and is used for removing suspended matters and colloid substances in mine water; 2 is a flocculating agent dosing device, 3 is a coagulant aid dosing device, and is respectively communicated with a pipeline between the water outlet of the regulating tank 1 and the water inlet of the coagulation clarification unit 4 and is respectively used for dosing flocculating agent and coagulant aid; 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 and is used for clarifying mine water again; 11 is a chemical softening unit, in particular a high-density sedimentation tank, the water inlet of which is communicated with the water outlet of the clarifying water tank 7 and is used for removing calcium, magnesium and silicon in water, thereby creating conditions for the subsequent membrane treatment; the high-density sedimentation tank is provided with an online pH meter and an online alkalinity analyzer (not shown in the figure); 8 is a sodium hydroxide dosing device, 9 is a sodium carbonate dosing device and 10 is a magnesium chloride dosing device, which are respectively communicated with pipelines between the water outlet of the clarification tank 7 and the water inlet of the chemical softening unit 11, and corresponding medicaments are added into the chemical softening unit 11; meanwhile, the pipeline between the water outlet of the clear water tank 7 and the water inlet of the chemical softening unit 11 is also communicated with the flocculant adding device 2 and the medicament outlet of the coagulant aid adding device 1; 12 is a chemical sludge pond which is communicated with a sludge outlet of the chemical softening unit 11 and is used for discharging sludge; 13 is a filtering unit, in particular a V-shaped filtering tank, and a water inlet of the filtering unit is communicated with a water outlet of the chemical softening unit 11; the V-shaped filter outlet is provided with an online pH meter (not shown in the figure); 16 is a softening water tank, and the water inlet of the softening water tank is communicated with the water outlet of the filtering unit 13; the sulfuric acid adding device is 14, is communicated with a pipeline for water outlet of the filtering unit 13 and water inlet of the softening water tank 16, and is subjected to pH adjustment before entering the softening water tank after filtering; 15 is sodium hypochlorite adding device which is communicated with the pipeline of the water outlet of the filtering unit 13 and the water inlet of the softening water tank 16 and is used for sterilizing after the pH value is adjusted; the ultrafiltration device 17 is communicated with the water outlet of the softening water tank 16 and is used for carrying out deep filtration treatment on mine water; an ultrafiltration water tank 18 is communicated with a water outlet of the ultrafiltration device 17; 19 is a weak acid cation exchanger which is communicated with the water outlet of the ultrafiltration water tank 18 and is used for deeply removing hardness and alkali from mine water; 20 is a carbon dioxide remover which is communicated with the water outlet of the weak acid cation exchanger and is used for decarburizing mine water; 21 is a carbon removing fan which is arranged at the lower part of the carbon dioxide remover 20; a carbon removing water tank 22 is communicated with a water outlet of the carbon dioxide remover 20; the reverse osmosis device 25 is communicated with the water outlet of the decarbonization water tank 22 and is used for carrying out reverse osmosis membrane treatment on mine water to achieve the desalting effect; 23 is a reverse osmosis scale inhibitor dosing device, 24 is a reverse osmosis reducing agent dosing device, 8 is a sodium hydroxide dosing device, and is respectively communicated with pipelines between water inlet of the reverse osmosis device 25 and water outlet of the carbon removal water tank 22 for dosing the medicament; 26 is a fresh water pond which is communicated with a fresh water outlet of the reverse osmosis device 25, a fresh water outlet of the disc tube type nanofiltration device 29 and a distilled water outlet of the evaporative crystallization device 31 and is used for storing fresh water; 27 is a reverse osmosis concentrated water tank which is communicated with a concentrated water outlet of the reverse osmosis device 25; 29 is a dish tube type nanofiltration device which is communicated with the water outlet of the reverse osmosis concentrated water tank 27 and is used for synchronously separating salt and concentrating the reverse osmosis concentrated water; the nano-filtration scale inhibitor adding device is 28 communicated with a pipeline between water inlet of the disc-tube type nano-filtration device 29 and water outlet of the reverse osmosis concentrated water tank 27 and is used for adding a medicament; a nanofiltration concentrated water tank 30 is communicated with a concentrated water outlet of the disc tube type nanofiltration device 29; and 31 is an evaporation crystallization device, which is communicated with the water outlet of the nanofiltration concentrated water tank 30 and is used for performing evaporation crystallization treatment on nanofiltration concentrated water.
Example 2
The device provided in example 1 was used to treat mine water:
the turbidity of the water inlet of the coal mine is 60-180 NTU, the salt content is about 4000mg/L, the total hardness is 900-1150 mg/L, the calcium ion is 400-500 mg/L, the magnesium ion is 40-55 mg/L, the sulfate radical is 2300-2700 mg/L, and the chloride radical is 45-60 mg/L.
The water quantity and the water quality of the mine water of the coal mine are regulated by a regulating tank to enter a high-efficiency cyclone purifier, and simultaneously polyaluminum chloride PAC and polyacrylamide PAM are added into a water inlet of the high-efficiency cyclone purifier to carry out 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 high-density sedimentation tank for softening treatment, and sodium hydroxide, sodium carbonate, magnesium chloride, polymeric ferric sulfate PFS, polyacrylamide PAM and other medicaments are added into the high-density sedimentation tank for flocculation sedimentation reaction. The pH value of the high-density sedimentation tank is controlled to be 10.8-11.3, and the effluent contains 1.5-2.0 mmol/L of excessive carbonate.
After the treatment by a high-density sedimentation tank, the total hardness removal rate of mine water is more than 90 percent, and the hardness in the water is less than 100mgCaCO 3 and/L, and the water contains 1.5-2.0 mmol/L of excessive carbonate content. And the effluent of the high-density sedimentation tank enters a V-shaped filter tank for filtering treatment, and the turbidity of the effluent is less than 2 NTU. And then adding sulfuric acid into the effluent to adjust the pH value to 7.8-8.3, adding sodium hypochlorite to perform sterilization treatment, and then entering a softening water tank. The V-shaped filter tank is backwashed in a form of backwashing and sulfuric acid adding, and backwashed waste water is recycled to the regulating tank. The softened water pool water enters a ceramic membrane ultrafiltration device for deep filtration treatment, and the ceramic membrane ultrafiltration device adopts inorganic alpha-Al 2 O 3 The average pore diameter of the ceramic membrane component is 30nm. The ultrafiltration backwash water is recycled to a clarified water tank, ultrafiltration produced water enters an ultrafiltration water tank, the turbidity of the ultrafiltration backwash water is less than 0.1NTU, and the SDI 15 Less than 3. The water in the ultrafiltration water tank enters a weak acid cation exchanger for deep hardness removal and alkali removal, then enters a carbon dioxide remover, enters a carbon removal water tank after carbon removal treatment, the hardness of the water outlet is about 0, the alkalinity of the water outlet is about 0, sodium hydroxide is firstly added into the water outlet of the carbon removal water tank to adjust the pH value to 8.5-9.0, and then RO scale inhibitor and reducer are added into a reverse osmosis device for desalination treatment; reverse osmosis unit recoveryThe water recovery rate is about 90% by using a first-stage two-stage interstage supercharging structure. The produced water of the reverse osmosis device enters a fresh water tank, and the concentrated water enters a reverse osmosis concentrated water tank. The reverse osmosis concentrated water is firstly added with NF scale inhibitor and then enters a disc tube type nanofiltration device to synchronously carry out salt separation and deep concentration treatment, the disc tube type nanofiltration device adopts a primary second section and an intersegmental supercharging structure, and the recovery rate is about 75 percent. The produced water of the disc tube type nanofiltration device enters a fresh water tank, and the concentrated water enters a nanofiltration concentrated water tank. The nanofiltration concentrated water enters a Mechanical Vapor Recompression (MVR) evaporative crystallization system to finally produce qualified distilled water and high-quality sodium sulfate crystal salt with purity not less than 98.5 percent. The freshwater pool fresh water solubility solid is less than 500mg/L, the total hardness is less than 10mg/L, the turbidity is less than 1NTU, the sulfate ion is less than 200mg/L, the standard of industrial and agricultural reuse water is completely satisfied, and the aims of zero emission and resource utilization of mine water are realized.
Example 3
Compared with the embodiment 1, the embodiment provides a high-hardness high-sulfate type coal mine water short-flow zero-emission treatment device, which is characterized in that a chemical softening unit 11 is a chemical crystallization circulating granulation fluidized bed, correspondingly, 8 is a sodium hydroxide dosing device, 9 is a sodium carbonate dosing device and 10 is a seed crystal dosing device, and the chemical softening unit 11 is respectively communicated with a pipeline between the water outlet of a clarification water tank 7 and the water inlet of the chemical softening unit 11, and corresponding medicaments are added into the chemical softening unit 11; 12 is a particle storage device, which is communicated with the crystal outlet of the chemical softening unit 11 and is used for storing the obtained crystals; reference numeral 13 denotes a filter unit, specifically a high-efficiency fiber filter.
Example 4
The device provided in example 2 was used to treat mine water:
the turbidity of the water inlet of the coal mine is 100-250 NTU, the salt content is about 4500mg/L, the total hardness is 1100-1300 mg/L, the calcium ion is 500-600 mg/L, the magnesium ion is 50-65 mg/L, the sulfate radical is 2650-3000 mg/L, and the chloride radical is 60-75 mg/L.
The water quantity and the water quality of the mine water of the coal mine are regulated by a regulating tank to enter a high-efficiency cyclone purifier, and simultaneously polyaluminum chloride PAC and polyacrylamide PAM are added into a water inlet of the high-efficiency cyclone purifier to carry out 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 for softening treatment, calcium carbonate seed crystals are added into the effluent to serve as a crystal inducing carrier, and sodium hydroxide and sodium carbonate are added simultaneously to enable Ca to be obtained 2+ 、Mg 2+ The ions undergo chemical reaction to produce CaCO 3 /Mg(OH) 2 /SiO 2 The composite crystal is attached to the surface of the seed crystal, so that the hardness and silicon in the water are removed, and the sludge difficult to treat is not generated; the pH value of the reaction of the chemical crystallization circulating granulation fluidized bed is controlled to be 10.8-11.3, and the effluent contains 1.5-2.0 mmol/L of excessive carbonate. The rising flow rate of the materials in the chemical crystallization circulating granulation fluidized bed is 60-100 m/h, and discharged CaCO 3 /Mg(OH) 2 /SiO 2 The composite crystal particles are 2-3 mm and can be recycled.
After treatment by a chemical crystallization circulating granulation fluidized bed, the total hardness removal rate is more than 90%, and the hardness of the yielding water is less than 100mgCaCO 3 and/L, and the water contains 1.5-2.0 mmol/L of excessive carbonate content. The effluent enters a high-efficiency fiber filter for filtering, and the turbidity of the effluent of the filter is less than 2 NTU. And then adding sulfuric acid into the effluent to adjust the pH value to 7.8-8.3, adding sodium hypochlorite to perform sterilization treatment, and then entering a 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 softened water pool water enters an immersed ultrafiltration device for deep filtration treatment, and an ultrafiltration membrane adopted by the immersed ultrafiltration device is a hollow fiber membrane with the aperture of 0.02 microns. The ultrafiltration backwash water is recycled to a clarified water tank, ultrafiltration produced water enters an ultrafiltration water tank, the turbidity is less than 0.1NTU, and the SDI 15 Less than 3. The water in the ultrafiltration water tank enters a weak acid cation exchanger for deep hardness removal and alkali removal, the effluent enters a carbon dioxide remover, the hardness of the effluent after carbon removal treatment is about 0, the alkalinity of the effluent is about 0, and the effluent enters a carbon removal water tank. Adding sodium hydroxide into the effluent of the carbon removal water tank to adjust the pH to 8.5-9.0, adding RO scale inhibitor and reducer, and entering a reverse osmosis device for desalination treatment; the reverse osmosis device adoptsThe water recovery rate of the first-stage second-stage and inter-stage supercharging structure is about 90%. The produced water of the reverse osmosis device enters a fresh water tank, and the concentrated water enters a reverse osmosis concentrated water tank. The reverse osmosis concentrated water is firstly added with NF scale inhibitor and then enters a disc tube type nanofiltration device for synchronous salt separation and concentration treatment. The disc tube type nanofiltration device adopts a primary two-stage pressure boosting structure between stages, and the water recovery rate is about 70%. The produced water of the disc tube type nanofiltration device enters a fresh water tank, and the concentrated water enters a nanofiltration concentrated water tank. The nanofiltration concentrated water enters a multi-effect evaporation crystallization system (MED) to finally produce qualified distilled water and high-quality sodium sulfate crystal salt with purity not lower than 98.5 percent. The freshwater pool fresh water solubility solid is less than 500mg/L, the total hardness is less than 10mg/L, the turbidity is less than 1NTU, the sulfate ion is less than 200mg/L, the standard of industrial and agricultural reuse water is completely satisfied, and the aims of zero emission and resource utilization of mine water are realized.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. 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 invention. Thus, the present invention 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 treating coal mine water with high hardness and high sulfate content by short-process zero emission comprises the following steps:
a) Coagulating and clarifying the high-hardness high-sulfate type coal mine water;
b) C), chemically softening the effluent obtained in the step a) to remove calcium, magnesium and silicon;
c) Filtering the effluent obtained in the step b), and then adjusting the pH value to 7.8-8.3;
d) Sequentially carrying out ultrafiltration, weak acid cation exchange, carbon dioxide removal, reverse osmosis desalination, dish tube nanofiltration synchronous salt separation, concentration and evaporative crystallization on the effluent obtained in the step c);
in the step b), the pH value of the chemical softening treatment is 10.8-11.3;
The effluent obtained in the step b) contains 1.5-2.0 mmol/L carbonate;
the hardness of the effluent after removing carbon dioxide is 0, and the alkalinity is 0;
before reverse osmosis desalination, the pH value of the effluent after carbon dioxide removal is adjusted to 8.5-9.0;
the recovery rate of the reverse osmosis device is 90% -95%;
in the step d), the recovery rate of the disc tube type nanofiltration device is 70-80%.
2. A high hardness high sulfate type coal mine water short-process zero-discharge treatment apparatus as claimed in claim 1, comprising:
the coagulation clarification unit is provided with a high-hardness high-sulfate type coal mine water inlet;
a chemical softening unit communicated with the water outlet of the coagulation clarification unit;
a filtering unit communicated with the water outlet of the chemical softening unit;
a pH value adjusting unit communicated with the water outlet of the filtering unit;
the ultrafiltration device is communicated with the water outlet of the pH value adjusting unit;
a weak acid cation exchanger communicated with the water outlet of the ultrafiltration device;
a carbon removal device communicated with the water outlet of the weak acid cation exchanger;
a reverse osmosis device communicated with the water outlet of the carbon removing device;
A dish tube type nanofiltration device connected with the concentrated water outlet of the reverse osmosis device;
the evaporation crystallization device is connected with the concentrated water outlet of the disc tube type nanofiltration device;
and the chemical softening unit is also provided with an online pH meter for monitoring the pH value and an online alkalinity analyzer for monitoring carbonate radicals.
3. The apparatus of claim 2, wherein the chemical softening unit is one or more of a high density sedimentation tank, a chemical crystallization circulating granulation fluidized bed, or a sodium ion exchanger.
4. The apparatus of claim 2, 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;
the evaporation crystallization device is a mechanical vapor recompression evaporation crystallization device, a thermal vapor recompression evaporation crystallization device, a multi-effect evaporation crystallization device or a multi-stage flash evaporation crystallization device.
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