CN119191625A - An integrated comprehensive treatment method and device for waste salt and carbon dioxide in the steel industry - Google Patents
An integrated comprehensive treatment method and device for waste salt and carbon dioxide in the steel industry Download PDFInfo
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- CN119191625A CN119191625A CN202411532879.4A CN202411532879A CN119191625A CN 119191625 A CN119191625 A CN 119191625A CN 202411532879 A CN202411532879 A CN 202411532879A CN 119191625 A CN119191625 A CN 119191625A
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- sodium bicarbonate
- salt
- sodium
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000011282 treatment Methods 0.000 title claims abstract description 65
- 150000003839 salts Chemical class 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 46
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 43
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 43
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 42
- 239000010959 steel Substances 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 37
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 104
- 239000000243 solution Substances 0.000 claims abstract description 95
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 52
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 52
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 38
- 238000000909 electrodialysis Methods 0.000 claims abstract description 23
- 239000012266 salt solution Substances 0.000 claims abstract description 22
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 21
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 19
- 239000012267 brine Substances 0.000 claims abstract description 19
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 18
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 18
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003546 flue gas Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011575 calcium Substances 0.000 claims abstract description 12
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 239000011777 magnesium Substances 0.000 claims abstract description 12
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 239000002440 industrial waste Substances 0.000 claims abstract description 10
- 239000012265 solid product Substances 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000000605 extraction Methods 0.000 claims abstract description 8
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 238000004939 coking Methods 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 56
- 235000002639 sodium chloride Nutrition 0.000 claims description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012535 impurity Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 238000001728 nano-filtration Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 238000000108 ultra-filtration Methods 0.000 claims description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000000712 assembly Effects 0.000 claims description 6
- 238000000429 assembly Methods 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 102000015863 Nuclear Factor 90 Proteins Human genes 0.000 claims description 4
- 108010010424 Nuclear Factor 90 Proteins Proteins 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 230000010354 integration Effects 0.000 claims description 2
- 238000004064 recycling Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 9
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 239000012141 concentrate Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 20
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000000126 substance Substances 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000012510 hollow fiber Substances 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 235000019738 Limestone Nutrition 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 125000006850 spacer group Chemical group 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/02—Preparation by double decomposition
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
本发明属于工业废物处理技术领域，具体涉及一种钢铁行业废盐和二氧化碳一体化综合治理方法，包括：将钢厂产生的工业废盐水集中后，进行预处理以及钠盐提取的处理步骤，获得COD值低于10mg/L的钠盐溶液；将焦化后的剩余氨水通入经处理后的热风炉二氧化碳烟气，获得含碳酸氢铵溶液；将钠盐溶液和含碳酸氢铵溶液通入电渗析模块进行离子交换，生成碳酸氢钠稀溶液和铵盐稀溶液；采用反渗透系统对碳酸氢钠稀溶液进行浓缩，获得碳酸氢钠浓溶液；对碳酸氢钠浓溶液进行除钙镁处理，将处理后的碳酸氢钠浓溶液经加热罐加热至190～270℃，后再次通入热风炉二氧化碳烟气，获得纯度大于等于98.5％碳酸氢钠固体产品。实现了杂盐资源化与二氧化碳吸附利用的有机结合，提高了经济效益和环境效益。
The invention belongs to the technical field of industrial waste treatment, and specifically relates to an integrated comprehensive treatment method for waste salt and carbon dioxide in the steel industry, comprising: after the industrial waste brine generated by the steel plant is concentrated, pretreatment and sodium salt extraction are performed to obtain a sodium salt solution with a COD value lower than 10 mg/L; the residual ammonia water after coking is introduced into the treated carbon dioxide flue gas of the hot blast furnace to obtain an ammonium bicarbonate solution; the sodium salt solution and the ammonium bicarbonate solution are introduced into an electrodialysis module for ion exchange to generate a sodium bicarbonate dilute solution and an ammonium salt dilute solution; a reverse osmosis system is used to concentrate the sodium bicarbonate dilute solution to obtain a sodium bicarbonate concentrated solution; the sodium bicarbonate concentrated solution is treated to remove calcium and magnesium, and the treated sodium bicarbonate concentrated solution is heated to 190-270° C. in a heating tank, and then introduced into the hot blast furnace carbon dioxide flue gas again to obtain a sodium bicarbonate solid product with a purity greater than or equal to 98.5%. The organic combination of the recycling of miscellaneous salts and the adsorption and utilization of carbon dioxide is achieved, and the economic and environmental benefits are improved.
Description
Technical Field
The invention relates to the technical field of industrial waste treatment, in particular to an integrated comprehensive treatment method and device for waste salt and carbon dioxide in the steel industry.
Background
The iron and steel industry produces waste brine and carbon dioxide during production. The waste brine has complex components and difficult treatment, and mainly comprises inorganic salts, heavy metals, chemicals used in the desalination process and the like. According to the analysis of the composition of the waste salt in the steel industry, the inorganic salt may contain sodium chloride, sodium sulfate, sodium sulfite, sodium nitrate, sodium carbonate, sodium bromide and other salts. Wet desulfurization waste water or acid washing waste water generated in the steel sintering process generally contains a large amount of suspended matters, chloride ions, sulfate radicals, ammonia nitrogen, a certain amount of calcium and magnesium and a small amount of heavy metal ions. The steel industry is one of the main sources of global carbon dioxide emission, particularly in China, the carbon emission of the steel industry accounts for about 15% of the total national carbon emission, and the contribution of China exceeds 60% of the carbon emission of the global steel industry.
The treatment and recycling of waste salt are of great significance for environmental protection and sustainable development. The current method for recycling the waste salt comprises a molten salt chlorination byproduct waste salt recycling technology, a waste salt solid waste recycling technology coupling technology and equipment for removing pollutant element levels, a high-salt wastewater treatment complete technology, a steel comprehensive wastewater strong brine reduction and recycling combination method and system and the like. In the traditional process, sodium chloride and sodium sulfate are the end points of zero emission of industrial wastewater. However, both of these products are inexpensive and even high purity products have no good sales and prices. The economic benefit of the waste salt treatment in the steel industry is poor at present.
The carbon dioxide treatment method in the steel industry mostly adopts an alkali preparation technology, the treatment difficulty is high, and the technology is immature. In the existing alkali preparation process, the circulating alkali preparation method has the advantages of relatively high energy consumption and product purity, but needs to be provided with a refrigerating device in the production process, so that the investment of equipment is relatively large, the production cost is relatively high, the key problem of low primary Na+ utilization rate cannot be improved, the organic amine alkali preparation method is relatively simple in process compared with the circulating alkali preparation method, the primary Na+ utilization rate can be greatly improved, the process of recycling organic amine is relatively difficult, the equipment and energy consumption are relatively large, the economy is not realized, the Proton Circulating Membrane Electrolysis (PCME) method combined with the electrochemical technology is used for producing sodium carbonate, the product purity is high, the calcination of limestone in the Soxhlet method is avoided, the energy consumption is greatly reduced, the obvious energy advantage is realized, and the absorption reaction rate of CO 2 is relatively low.
Disclosure of Invention
Aiming at the technical problems, the integrated comprehensive treatment method and the integrated comprehensive treatment device for the waste salt and the carbon dioxide in the steel industry are provided, so that the treatment efficiency and the economic efficiency are improved.
In a first aspect, an embodiment of the present invention provides a method for integrated comprehensive treatment of waste salt and carbon dioxide in the steel industry, including:
after concentrating industrial waste brine produced by a steel mill, carrying out pretreatment and sodium salt extraction treatment steps to obtain sodium salt solution with COD value lower than 10 mg/L;
Introducing the sodium salt solution and the ammonium bicarbonate-containing solution into an electrodialysis module for ion exchange to generate sodium bicarbonate dilute solution and ammonium salt dilute solution;
concentrating the sodium bicarbonate dilute solution by adopting a reverse osmosis system to obtain sodium bicarbonate concentrated solution;
And (3) performing calcium and magnesium removal treatment on the sodium bicarbonate concentrated solution, heating the treated sodium bicarbonate concentrated solution to 180-270 ℃ through a heating tank, and then, introducing hot blast stove carbon dioxide flue gas again to obtain a sodium bicarbonate solid product with the purity of more than or equal to 98.5%.
In combination with the first aspect, in an embodiment, the ammonium salt dilute solution is concentrated by adopting a reverse osmosis system to obtain an ammonium salt concentrated solution, and the ammonium salt concentrated solution is introduced into a cooling precipitation tank to be cooled to obtain ammonium sulfate solid crystals.
In combination with the first aspect, in one embodiment, the pretreatment comprises a treatment step of removing impurities, wherein the treatment step comprises the steps of removing insoluble impurities in the waste brine by adopting an air floatation method, and preliminarily removing heavy metal ions and organic impurities, so that the COD content of the waste brine is less than 50mg/L.
With reference to the first aspect, in one embodiment, the treatment step for removing organic matters includes filtering organic matters in the waste brine by adopting an ultrafiltration membrane, and separating an aqueous solution containing sodium salt on a water producing side;
the organic matter is oxidized by an ozone advanced oxidation method, and the COD value of the sodium salt-containing aqueous solution is reduced to below 10 mg/L.
In combination with the first aspect, in one embodiment, the obtained sodium salt-containing aqueous solution is subjected to separation treatment by using a nanofiltration membrane group to obtain a monovalent sodium salt solution and a divalent sodium salt solution, and the obtained monovalent sodium salt solution and divalent sodium salt solution are concentrated to 9-10g/L for standby.
With reference to the first aspect, in an embodiment, the nanofiltration membrane group includes an NF150 membrane group, an NF90 membrane group, and an NF210 membrane group, and the NaCl solution and the Na 2SO4 solution are obtained after separation treatment.
In combination with the first aspect, in an embodiment, the concentrated sodium bicarbonate solution is subjected to calcium and magnesium removal treatment, and the treated concentrated sodium bicarbonate solution is heated to 170-200 ℃ by a heating tank, so that a sodium carbonate solid product with the purity of more than or equal to 99% is obtained.
In combination with the first aspect, in an embodiment, the electrodialysis module adopts four-chamber electrodialysis and comprises ten groups of homogeneous membrane assemblies, each group of homogeneous membrane assemblies comprises a cathode membrane, a Yang Mo membrane and a separator, and the electrode solution adopts 4% -5% Na 2SO4 solution.
With reference to the first aspect, in an embodiment, the concentrating the dilute sodium bicarbonate solution using a reverse osmosis system includes:
and concentrating for a plurality of times by adopting a DTRO reverse osmosis system to reach the concentration of 25-35%.
In a second aspect, the embodiment of the invention also provides a waste salt and carbon dioxide integrated comprehensive treatment device in the steel industry, which comprises a mixing and precipitating tank, a water treatment tank and a water treatment tank, wherein the mixing and precipitating tank is used for carrying out pretreatment and sodium salt extraction after concentrating industrial waste salt water generated by a steel mill;
the carbonization reaction tank is used for introducing residual ammonia water after coking into the carbon dioxide flue gas of the hot blast stove after treatment to carry out carbonization reaction to obtain an ammonium bicarbonate-containing solution;
the electrodialysis module is used for introducing the sodium salt solution and the ammonium bicarbonate-containing solution into the electrodialysis module for ion exchange to generate a sodium bicarbonate dilute solution and an ammonium salt dilute solution;
the mixing reaction tank is used for heating and decarbonizing the sodium bicarbonate concentrated solution obtained after concentration and calcium and magnesium removal treatment, and a sodium bicarbonate solid product;
And cooling the crystallization tank, and purifying and crystallizing the ammonium salt dilute solution to obtain ammonium sulfate solid crystals.
According to the integrated comprehensive treatment method and device for the waste salt and the carbon dioxide in the steel industry, provided by the embodiment of the invention, the last kilometer of zero emission in the steel industry is opened by adopting the electrodialysis technology, the treatment difficulty of waste salt recycling and carbon dioxide adsorption in the steel industry is solved, the organic combination of the integration of mixed salt recycling and carbon dioxide adsorption is realized, the current situation of flue gas treatment of a hot blast stove in a steel plant is combined, the carbon dioxide is effectively fixed, and the waste treatment efficiency in the steel plant is improved. The cheap sodium chloride and sodium sulfate can be used as sodium sources, ammonia water collected in the previous working procedure is introduced with cheap and easily obtained carbon dioxide to generate ammonium bicarbonate, and sodium bicarbonate or sodium carbonate products with high economic value are generated. In addition, the byproducts of ammonium sulfate and ammonium chloride can be sold as chemical fertilizers. Improving economic benefit and environmental benefit.
Drawings
FIG. 1 is a schematic diagram of an integrated comprehensive treatment method for waste salt and carbon dioxide in the steel industry in one embodiment;
FIG. 2 is a schematic diagram of the operation of the integrated comprehensive treatment method for waste salt and carbon dioxide in the steel industry in one embodiment;
FIG. 3 is a schematic diagram of an integrated comprehensive treatment device for waste salt and carbon dioxide in the steel industry in one embodiment;
Figure 4 is a schematic diagram of an electrodialysis module in one embodiment.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
As shown in fig. 1, the integrated comprehensive treatment method for waste salt and carbon dioxide in the steel industry provided by the invention comprises the following steps:
S10, carrying out pretreatment and sodium salt extraction after concentrating industrial waste brine generated by a steel mill to obtain sodium salt solution with COD value lower than 10mg/L, and introducing residual ammonia water after coking into carbon dioxide flue gas of a hot blast stove after treatment to obtain ammonium bicarbonate-containing solution.
After being concentrated, the industrial waste brine in the steel mill is subjected to primary treatment by a water treatment center of the whole plant and is concentrated to a sedimentation tank, and the COD is controlled at 110-120mg/L. And performing initial measurement on the concentration of calcium and magnesium ions, silicon and heavy metal ions by using inductively coupled plasma emission spectrometry (ICP-OES).
The pretreatment comprises removing impurities and heavy metals, and step S11, namely removing insoluble impurities in the waste brine by adopting an air floatation method, and preliminarily removing heavy metal ions and organic impurities, so that the COD content of the waste brine is less than 50mg/L.
The pretreatment includes removal of organic matter. And step S121, filtering organic matters in the waste brine by adopting an ultrafiltration membrane, and separating the sodium salt-containing aqueous solution on the water producing side. The water producing side refers to the side where water (i.e., pure water or filtered water) produced after the membrane element treatment is located during the membrane filtration process. In the ultrafiltration technology, the water producing side refers to water filtered by an ultrafiltration membrane. Ultrafiltration membranes are capable of trapping substances of relatively large molecular weight (e.g., proteins, bacteria, etc.), while allowing the passage of water molecules and substances of relatively small molecular weight. Optionally, the ultrafiltration membrane comprises a PVDF (polyvinylidene fluoride) UF membrane, a hollow fiber UF membrane, and an external pressure/internal pressure UF membrane. Preferably hollow fiber UF membrane, has high flux, easy cleaning, easy recovery, etc.
Organic membranes such as ultrafiltration membranes can isolate organic matters and organic salts with larger molecular weight in water at the concentrated water end. The concentrated water end refers to the side where the high concentration solution is formed after impurities, ions or other unwanted substances are trapped by the membrane element during the membrane filtration process. Common organics include carbohydrates, proteins, oils, organic heavy metal compounds (lead, mercury, etc.), phenols, alcohols, aldehydes, ketones, lipids, etc. The organic film can remove 60-90% of the organic matters according to the organic matters components and properties.
The step of obtaining the ammonium bicarbonate-containing solution comprises the steps of introducing residual ammonia water after coking into the flue gas of the hot blast stove after treatment to form a mixed solution of ammonium bicarbonate, ammonium carbonate and ammonium carbamate, and adjusting the concentration to 0.1-0.3mol/L and the pH to 7.5-8.0 for standby. The pH adjustment is mainly realized by using acetic acid (CH 3 COOH) and ammonia water, the concentration is mainly adjusted by adding circulating treatment water, and optionally, the concentration of the residual ammonia water is about 21%, and the ammonia nitrogen content is about 2600mg/L. The CO 2 content in the hot blast stove flue gas is about 18-28%. The concentration of the absorbed CO 2 is about 3%, and the absorption rate is more than 80%.
S122, performing organic oxidation treatment by using an ozone advanced oxidation method, and reducing the COD value of the sodium salt-containing aqueous solution to below 10 mg/L. Ozone advanced oxidation is a water and wastewater treatment technology based on the oxidative nature of ozone (O3). It uses the strong oxidizing nature of ozone to convert organic and inorganic contaminants in water into harmless or more easily removable products. Ozone molecules (O3) can be decomposed into oxygen and elemental oxygen in water, the elemental oxygen is very active and can react with organic substances in the water to generate a series of oxidation products, and the oxidation products can be further decomposed into smaller molecules and finally converted into harmless substances such as carbon dioxide, water and the like, so that the requirements of water quality standards, product standards and long-term operation of membrane systems are met.
The sodium salt extraction step S13 comprises separating different salt components by adopting a nanofiltration membrane group to respectively obtain monovalent sodium salt and divalent sodium salt. According to the difference of inorganic salt ion group chargeability and sieving property, different salt components are separated through a nanofiltration membrane. The selection of nanofiltration membranes is mainly dependent on the specific ionic components in the water sample, and the specific separation membrane groups are selected according to the coagulation state of the ionic functional groups in the water. For example, nanofiltration membrane modules selected for use in a company include NF150, NF90, and NF210 membrane modules. Firstly, monovalent salt and divalent salt in the aqueous solution are separated by adopting an NF150 membrane group, and the monovalent salt and the divalent salt are respectively separated to a water-producing end and a concentrated water end. Monovalent salts include NaCl, KCl, divalent salts include Na2SO4, mgSO4, caSO4. Then, separating NaCl from other monovalent salts by using an NF90 membrane group so that the NaCl is at a concentrated water end and the other monovalent salts are at a water producing end, and separating Na 2SO4 from other divalent salts by using an NF210 membrane group so that Na 2SO4 is at the water producing side and the other divalent salts are at the concentrated water side.
Optionally, step S13 is followed by step S14, and the salt solution separated in step S13 is concentrated to 9-10g/L for later use by adopting a DTRO reverse osmosis system. Optionally, in order to minimize the energy consumption of the whole process, each reverse osmosis system is matched with a turbine type energy recovery device, and the concentrated water pumped at high pressure passes through the turbine type energy recovery device before passing through the membrane assembly. The concentrate here carries a greater pressure potential due to its higher osmotic pressure, which is due to the higher salt content or other impurities. The turbine type energy recovery device utilizes the characteristic of concentrated water, enables the turbine blades to rotate at a high speed, converts a part of kinetic energy into mechanical energy, and then transmits the mechanical energy to the water inlet pump at the low pressure side through the coupling, so that the water inlet pressure is improved, and the power required by the main booster pump is reduced.
And S20, introducing the sodium salt solution obtained in the step S10 and the ammonium bicarbonate-containing solution into an electrodialysis module for ion exchange to generate a sodium bicarbonate dilute solution and an ammonium salt dilute solution. Alternatively, the electrodialysis module uses four-compartment electrodialysis. The main structure in the interior is homogeneous membrane assemblies, ten groups are used, and each group of homogeneous membrane assemblies comprises a negative membrane, a Yang Mo membrane and a spacer. Here, the selection of the number of homogeneous membrane groups in electrodialysis mainly depends on the influence of ion conductivity, current density, selectivity, operation stability and economic benefit, and the influence factors are comprehensively considered, so that ten groups of conditions with the daily and hourly treatment capacity of hundred kilograms are selected as optimal conditions. The electrode liquid has the best effect by using 4% -5% of Na 2SO4 solution, and can be selected as a substitute by using sodium chloride solution. Optionally, the concentration of the sodium salt solution used as the raw material is 8-10%, and the concentration of ammonium bicarbonate is 10-12%. Optionally, the concentration of the generated sodium bicarbonate is 7-8%, the purity is not less than 98.5%, and the concentration of ammonium salt is 8-10%. Optionally, the ammonium salt comprises ammonium chloride and ammonium sulfate, and the purity is more than or equal to 98%. The specific type and purity of the catalyst depend on the components of the feed material, and can be specifically adjusted according to the post-treatment mode.
S30, concentrating the sodium bicarbonate dilute solution by adopting a reverse osmosis system to obtain sodium bicarbonate concentrated solution. The generated sodium bicarbonate dilute solution is concentrated for a plurality of times through a DTRO reverse osmosis system to reach the concentration of 25-35 percent. The concentrated sodium bicarbonate solution can be directly recycled in the system until the calcium and magnesium removal process of water treatment, so that full-process carbon fixation and water treatment recycling are realized. Alternatively, the number of times of concentration is 3-6.
Optionally, concentrating the ammonium salt dilute solution by using a reverse osmosis system to obtain an ammonium salt concentrated solution. The generated ammonium salt dilute solution is concentrated for a plurality of times through a DTRO reverse osmosis system, and a concentrated solution with the concentration of 18-23% is obtained. Alternatively, the number of times of concentration is 2-4 times. And (3) introducing the concentrated solution into a cooling precipitation tank for cooling, wherein the lower ammonium sulfate solid crystals can be directly taken out from a lower port for later use or sale. The core of reverse osmosis technology is the application of semipermeable membranes. By semi-permeable membrane is meant a special membrane that allows certain specific substances (typically water molecules) to pass through, while preventing the passage of most solutes. During natural osmosis, a solvent (e.g., water) spontaneously diffuses from a dilute solution side to a concentrated solution side until the two-side concentration reaches equilibrium. In the reverse osmosis process, the natural trend is artificially reversed, namely, by applying enough external pressure on the concentrated solution side, the solvent is forced to reversely permeate the semipermeable membrane to enter the dilute solution side, so that the purpose of concentration is realized. The primary purpose of the multiple use reverse osmosis membranes herein is to allow the concentrated solution to get a near saturated solution at room temperature, thereby minimizing crystallization costs.
And S40, performing calcium and magnesium removal treatment on the sodium bicarbonate concentrated solution, and drying the treated sodium bicarbonate concentrated solution to obtain a sodium bicarbonate solid product. For later use or sale. And heating the sodium bicarbonate concentrated solution to 190-270 ℃ through a heating tank, and then, introducing carbon dioxide smoke of the hot blast stove again to saturate the solution, so that the product is stabilized as sodium bicarbonate. And the carbon dioxide flue gas of the hot blast stove is introduced again, so that the sodium bicarbonate can be prevented from being decomposed into sodium carbonate partially due to unstable existence form after being heated, and the purity and stability of the product are improved. The purity of the product is more than or equal to 98.5 percent, and meets the national standard of industrial sodium bicarbonate. Optionally, the sodium bicarbonate concentrated solution is continuously heated to 170-190 ℃ to obtain a stable sodium carbonate solid product, and the purity of the product is more than or equal to 99%.
Optionally, introducing the concentrated ammonium salt solution into a cooling precipitation tank for cooling to obtain ammonium sulfate solid crystals.
As shown in FIG. 2, the treatment process of the integrated comprehensive treatment method for the waste salt and the carbon dioxide in the steel industry comprises the following steps of carbonizing carbon dioxide flue gas from a hot blast stove and ammonia distillation wastewater from a coking plant in a reactor to fix carbon dioxide and generate ammonium bicarbonate solution. The comprehensive wastewater from the whole factory is pretreated by a water treatment center to obtain purer sodium chloride solution. The ammonium bicarbonate reacts with sodium chloride solution in an electrodialysis module to produce sodium bicarbonate solution and ammonium chloride solution. The sodium bicarbonate solution is subjected to concentration (hot film evaporation) and crystallization steps to obtain a sodium bicarbonate product which accords with national standards, and the sodium bicarbonate product is reused for the steps of decalcification magnesium impurity removal, acid washing neutralization, heat treatment atmosphere control agent and the like in the iron and steel industry or sold to the outside. The ammonium chloride solution is subjected to concentration and crystallization steps to obtain an ammonium chloride product meeting national standards, and the ammonium chloride product is supplied to metallurgical, petroleum, agricultural and other industry requirements.
Compared with the traditional method, the method realizes the organic combination of the resource utilization of the mixed salt and the absorption and utilization of the carbon dioxide, combines the current situation of the flue gas treatment of the hot blast stove in the steel plant, effectively fixes the carbon dioxide, increases the environmental benefit, realizes the absorption and the cyclic utilization of the carbon dioxide in the steel industry, and improves the economic value of the mixed salt treatment.
The invention also provides an integrated comprehensive treatment device for the waste salt and the carbon dioxide in the steel industry, which is shown in figure 3 and comprises:
and the mixing precipitation tank S2 is used for carrying out pretreatment and sodium salt extraction after concentrating industrial waste brine generated by a steel mill.
And the carbonization reaction tank S1 is used for introducing residual ammonia water after coking into the carbon dioxide flue gas of the hot blast stove after treatment to carry out carbonization reaction so as to obtain an ammonium bicarbonate-containing solution.
And the electrodialysis module S3 is used for introducing the sodium salt solution and the ammonium bicarbonate-containing solution into the electrodialysis module for ion exchange to generate sodium bicarbonate dilute solution and ammonium salt dilute solution. The main structure and the reaction logic are shown in figure 4, wherein the electrodialysis device is matched with 5 chambers, one of the chambers is a polar chamber and is mainly responsible for providing stable electronic conversion electricity in the electrodialysis device, and the other four chambers are a raw material chamber 1 and a raw material chamber 2, a product chamber 1 and a product chamber 2 respectively, and the specific position arrangement can be used for exchanging positions. The membrane pore channels in the electrodialysis membrane are alternately arranged, so that stable ion exchange from the raw material to the product end is achieved.
And the mixing reaction tank S5 is used for heating and decarbonizing the sodium bicarbonate concentrated solution obtained after the concentration and calcium and magnesium removal treatment to generate a sodium carbonate solid product. The mixing reaction tank S5 is also used for introducing carbon dioxide into the sodium carbonate generated by decarbonizing again, performing secondary carbonization, completely converting the sodium carbonate into sodium bicarbonate, and then performing crystallization and purification. Thus achieving the maximum carbon sequestration.
The specific limitation of the integrated comprehensive treatment device for the waste salt and the carbon dioxide in the steel industry can be referred to the limitation of the integrated comprehensive treatment method for the waste salt and the carbon dioxide in the steel industry, and the description is omitted here.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The integrated comprehensive treatment method for the waste salt and the carbon dioxide in the steel industry is characterized by comprising the following steps of:
after concentrating industrial waste brine produced by a steel mill, carrying out pretreatment and sodium salt extraction treatment steps to obtain sodium salt solution with COD value lower than 10 mg/L;
Introducing the sodium salt solution and the ammonium bicarbonate-containing solution into an electrodialysis module for ion exchange to generate sodium bicarbonate dilute solution and ammonium salt dilute solution;
concentrating the sodium bicarbonate dilute solution by adopting a reverse osmosis system to obtain sodium bicarbonate concentrated solution;
and (3) performing calcium and magnesium removal treatment on the sodium bicarbonate concentrated solution, heating the treated sodium bicarbonate concentrated solution to 190-270 ℃ through a heating tank, and then, introducing hot blast stove carbon dioxide flue gas again to obtain a sodium bicarbonate solid product with the purity of more than or equal to 98.5%.
2. The method according to claim 1, wherein the ammonium salt dilute solution is concentrated by a reverse osmosis system to obtain an ammonium salt concentrated solution;
And (3) introducing the ammonium salt concentrated solution into a cooling precipitation tank for cooling to obtain ammonium sulfate solid crystals.
3. The method according to claim 1 or 2, wherein the pretreatment comprises a treatment step of removing impurities, including removing insoluble impurities in the waste brine by an air method, primarily removing heavy metal ions and organic impurities, so that the COD content of the waste brine is less than 50mg/L.
4. The method according to claim 3, wherein the treatment step of removing organic matters comprises filtering the organic matters in the waste brine by using an ultrafiltration membrane to separate the sodium salt-containing aqueous solution on the water producing side;
the organic matter is oxidized by an ozone advanced oxidation method, and the COD value of the sodium salt-containing aqueous solution is reduced to below 10 mg/L.
5. The method of claim 4, wherein the obtained aqueous solution containing sodium salt is separated by a nanofiltration membrane group to obtain a monovalent sodium salt solution and a divalent sodium salt solution, and the obtained monovalent sodium salt solution and divalent sodium salt solution are concentrated to 9-10g/L for later use.
6. The method according to claim 5, wherein the nanofiltration membrane group comprises an NF150 membrane group, an NF90 membrane group and an NF210 membrane group, and the NaCl solution and the Na 2SO4 solution are obtained after separation treatment.
7. The method according to claim 1, wherein the concentrated sodium bicarbonate solution is subjected to calcium and magnesium removal treatment, and the treated concentrated sodium bicarbonate solution is heated to 170-190 ℃ by a heating tank, so that a sodium carbonate solid product with purity of more than or equal to 99% is obtained.
8. The method of claim 1, wherein the electrodialysis module comprises four-chamber electrodialysis and comprises ten groups of homogeneous membrane assemblies, each group of homogeneous membrane assemblies comprises a negative membrane, a Yang Mo membrane and a separator, and the electrode solution adopts 4% -5% Na 2SO4 solution.
9. The method of claim 1, wherein concentrating the dilute sodium bicarbonate solution using a reverse osmosis system to obtain a concentrated sodium bicarbonate solution comprises:
and concentrating for a plurality of times by adopting a DTRO reverse osmosis system to reach the concentration of 25-35%.
10. The utility model provides a steel trade salt waste and carbon dioxide integration comprehensive treatment device which characterized in that includes:
the mixing precipitation tank is used for carrying out pretreatment and sodium salt extraction after concentrating industrial waste brine generated by a steel mill;
the carbonization reaction tank is used for introducing residual ammonia water after coking into the carbon dioxide flue gas of the hot blast stove after treatment to carry out carbonization reaction to obtain an ammonium bicarbonate-containing solution;
the electrodialysis module is used for introducing the sodium salt solution and the ammonium bicarbonate-containing solution into the electrodialysis module for ion exchange to generate a sodium bicarbonate dilute solution and an ammonium salt dilute solution;
the mixing reaction tank is used for heating and decarbonizing the sodium bicarbonate concentrated solution obtained after concentration and calcium and magnesium removal treatment, and a sodium bicarbonate solid product;
And cooling the crystallization tank, and purifying and crystallizing the ammonium salt dilute solution to obtain ammonium sulfate solid crystals.
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