WO2024037041A1 - Desulfurization wastewater treatment system and method - Google Patents
Desulfurization wastewater treatment system and method Download PDFInfo
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- WO2024037041A1 WO2024037041A1 PCT/CN2023/091495 CN2023091495W WO2024037041A1 WO 2024037041 A1 WO2024037041 A1 WO 2024037041A1 CN 2023091495 W CN2023091495 W CN 2023091495W WO 2024037041 A1 WO2024037041 A1 WO 2024037041A1
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- WIPO (PCT)
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- hydrogen
- desulfurization wastewater
- gas
- deoxygenation
- liquid
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 72
- 230000023556 desulfurization Effects 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 97
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 97
- 239000007788 liquid Substances 0.000 claims abstract description 76
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000002351 wastewater Substances 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 33
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 26
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 20
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 17
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000006392 deoxygenation reaction Methods 0.000 claims description 61
- 239000002253 acid Substances 0.000 claims description 29
- 239000003513 alkali Substances 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 22
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 20
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 238000005189 flocculation Methods 0.000 claims description 13
- 230000016615 flocculation Effects 0.000 claims description 13
- 238000004062 sedimentation Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 3
- 239000003830 anthracite Substances 0.000 claims description 3
- 239000002699 waste material Substances 0.000 abstract description 4
- 230000000382 dechlorinating effect Effects 0.000 abstract 1
- 238000005554 pickling Methods 0.000 description 26
- 238000001704 evaporation Methods 0.000 description 7
- 230000008020 evaporation Effects 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007921 spray Substances 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
- B01D53/04—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 by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
-
- 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
- B01D53/22—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 by diffusion
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- 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
- B01D53/68—Halogens or halogen compounds
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/501—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by diffusion
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/506—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/508—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by selective and reversible uptake by an appropriate medium, i.e. the uptake being based on physical or chemical sorption phenomena or on reversible chemical reactions
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/52—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
- C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/01—Electrolytic cells characterised by shape or form
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/01—Electrolytic cells characterised by shape or form
- C25B9/015—Cylindrical cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
- B01D45/16—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces generated by the winding course of the gas stream, the centrifugal forces being generated solely or partly by mechanical means, e.g. fixed swirl vanes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0405—Purification by membrane separation
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0415—Purification by absorption in liquids
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/042—Purification by adsorption on solids
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0435—Catalytic purification
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- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F1/5281—Installations for water purification using chemical agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/18—Nature of the water, waste water, sewage or sludge to be treated from the purification of gaseous effluents
Definitions
- the present invention relates to the technical field of desulfurization wastewater treatment, and in particular to a desulfurization wastewater treatment system and method.
- wet desulfurization wastewater generally adopts a drug-added flocculation and sedimentation process. After most of the divalent ions are removed through flocculation and sedimentation, the pH value is adjusted by adding acid/alkali before being discharged into the receiving water body. With the gradual improvement of the country's environmental protection requirements, more and more production companies require zero discharge of pollutants.
- desulfurization wastewater contains a large amount of chloride ions and sodium ions. In order to meet the zero discharge requirements, an evaporation process is generally used.
- the desulfurization wastewater evaporation process means that after the desulfurization wastewater is pretreated, the water in the desulfurization wastewater is evaporated to dryness by heating to achieve zero discharge of desulfurization wastewater.
- the conventional process route of this technology is: pretreatment + membrane concentration + evaporation crystallization ( MVR or MED), the evaporation process can achieve zero discharge of desulfurization wastewater, and there are already successful engineering cases.
- MVR or MED membrane concentration + evaporation crystallization
- this method has the following shortcomings: due to the use of membrane concentration and evaporation crystallization processes, the entire system occupies a large area, and this The investment cost and operating cost of this process are high; moreover, the salt produced by evaporation and crystallization is generally miscellaneous salt, which is difficult to reuse and difficult to process. There is still the discharge of pollutants, but it has changed from waste water to solid waste.
- the purpose of the present invention is to provide a new desulfurization wastewater treatment system in order to overcome the problems existing in the existing desulfurization wastewater treatment system such as large system footprint, high process investment costs, high operating costs, and difficulty in processing miscellaneous salts generated during the evaporation process. Systems and methods.
- the present invention provides a desulfurization wastewater treatment system, which system includes:
- a pretreatment device used to pretreat desulfurization wastewater to remove divalent ions in the desulfurization wastewater
- Electrolysis device for electrolysis of pretreated desulfurization wastewater
- a gas-liquid separation device used for gas-liquid separation of the gas-liquid mixture produced in the electrolysis device
- a dechlorination device used to dechlorinate the hydrogen separated in the gas-liquid separation device
- a hydrogen pressurizing device for pressurizing, cooling and drying dechlorinated hydrogen
- Hydrogen deoxygenation device is used to deoxygenate hydrogen after pressurization, cooling and drying.
- the pretreatment device includes a pH adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
- the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector.
- the main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet, and the mixing
- the auxiliary liquid inlet end of the device is connected to the acid solution dosing device and the alkali solution dosing device
- the pH detector is arranged between the outlet of the mixer and the liquid inlet of the box.
- the sedimentation tank includes a box body, a central liquid inlet pipe and an overflow weir.
- the lower outlet of the central liquid inlet pipe is 10-30cm away from the bottom of the tank body.
- the overflow weir is arranged around the tank. The upper part of the inner wall of the body.
- the upper edge of the overflow weir has a zigzag structure.
- the filter material filled inside the multi-media filter is one or any combination of at least two of quartz sand, activated carbon and anthracite.
- the electrolytic cell used in the electrolysis device is a plate electrode tube electrolytic cell, a plate mesh electrode plate electrolytic cell or a concentric tube electrolytic cell.
- the system further includes an acid cleaning device for cleaning the scaling generated during the operation of the electrolysis device.
- the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit and a secondary hydrogen deoxygenation unit.
- the primary hydrogen deoxygenation unit uses a gas separation membrane for deoxidation
- the secondary hydrogen deoxygenation unit uses a palladium catalyst for deoxidation.
- the hydrogen deoxygenation device further includes a tertiary hydrogen deoxygenation unit arranged behind the secondary hydrogen deoxygenation unit, and the tertiary hydrogen deoxygenation unit uses a temperature swing and pressure swing adsorption device for deoxygenation.
- the invention also provides a method for treating desulfurization wastewater, which method includes the following steps:
- the deoxidation process includes:
- a temperature swing and pressure swing adsorption device can be used for three deoxygenations.
- the desulfurization wastewater is pretreated, and most of the divalent ions are removed through flocculation and precipitation.
- the remaining ones in the water body are basically sodium ions and chloride ions, and then electrolysis can Convert chloride ions into sodium hypochlorite, which can be used for factory disinfection.
- the hydrogen generated during the electrolysis process is dechlorinated, pressurized, cooled, dried, and deoxygenated to obtain pure hydrogen. Therefore, when desulfurization wastewater is treated according to the technical solution of the present invention, the overall process will not produce any waste, and the entire system will occupy a small area, and the process investment cost and operating cost will be low.
- FIG. 1 is a schematic diagram of the desulfurization wastewater treatment system according to the present invention.
- Figure 2 is a schematic diagram of the pretreatment device in the desulfurization wastewater treatment system of the present invention.
- FIG. 3 is a flow chart of the desulfurization wastewater treatment method according to the present invention.
- the desulfurization wastewater treatment system of the present invention includes a pretreatment device, an electrolysis device, a gas-liquid separation device, a dechlorination device, a hydrogen pressurization device and a hydrogen deoxygenation device connected in sequence.
- the pretreatment device is used to pretreat the desulfurization wastewater to remove divalent ions in the desulfurization wastewater.
- the pretreatment device includes a pH value adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
- the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector.
- the main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet
- the auxiliary liquid inlet end of the mixer is connected to the acid liquid dosing device and the alkali liquid dosing device
- the pH detector is installed on the mixing between the outlet of the mixer and the liquid inlet of the box.
- the pH detector is disposed at the connection between the mixer and the box.
- the acid liquid dosing device includes an acid liquid metering pump, the inlet of the acid liquid dosing device is connected to the acid liquid storage tank, and the acid liquid is injected into the mixer through the acid liquid metering pump.
- the liquid reducing dosing device includes an alkali metering pump, and the inlet connection of the alkali dosing device It is connected to the alkali liquid storage tank, and the alkali liquid is injected into the mixer through the alkali liquid metering pump.
- the mixer may be selected from static mixers, dynamic agitation mixers and pipe mixers.
- the reaction box includes a chemical dosing metering pump.
- the medicine added by the medicine adding metering pump can be sodium carbonate, sodium hydroxide, etc., and the medicine adding metering pump is correspondingly connected to the respective liquid storage tank.
- the flocculation box includes a flocculant dosing metering pump.
- the flocculant dosing metering pump is connected to the flocculant storage tank.
- the flocculant used can be a conventional choice in this field, for example, it can be polyaluminum chloride, ferric chloride, ferrous sulfate, alum and aluminum sulfate. At least one.
- the sedimentation tank includes a box, a liquid inlet central pipe and an overflow weir.
- the lower outlet of the liquid inlet central pipe is 10-30cm away from the bottom of the box, so
- the overflow weir is arranged around the upper part of the inner wall of the box.
- the structural form of the upper edge of the overflow weir is not particularly limited.
- the upper edge of the overflow weir has a zigzag structure. This zigzag structure overcomes the surface tension of water and promotes uniform water flow.
- the zigzag shape forming the upper edge of the overflow weir may be square, semicircular, triangular, etc.
- the multi-media filter includes a tank body and filter material filled in the tank body.
- the tank body may be made of fiberglass, carbon steel lined with plastic, or other materials.
- the filter material filled inside the multi-media filter is preferably one or any combination of at least two of quartz sand, activated carbon and anthracite.
- the electrolysis device is used to treat pre-treated The desulfurization wastewater is electrolyzed to generate sodium hypochlorite solution and hydrogen gas.
- the electrolysis device includes an electrolysis tank and a power supply.
- the electrolytic cell is preferably a plate electrode tube electrolytic cell, a plate mesh electrode plate electrolytic cell or a concentric tube electrolytic cell.
- the power supply may adopt a high-frequency steady-current switching voltage or a silicon-controlled rectified power supply.
- the electrolytic tank and the power supply are preferably connected through cables or copper bars.
- the system further includes an acid cleaning device for cleaning the scaling generated during the operation of the electrolysis device.
- the pickling device includes a pickling tank, an acid unloading pump, a pickling pump and an acid mist absorber.
- the pickling tank can use a PE material tank, a glass fiber reinforced plastic tank, or a steel-lined rubber tank.
- the acid unloading pump can be a magnetic pump or a centrifugal pump.
- the pickling pump can be a magnetic pump or a centrifugal pump.
- the inside of the acid mist absorber can be filled with fillers such as Raschig rings and filled with sodium hydroxide solution.
- the inlet of the acid unloading pump is connected to the pickling solution tank, and the outlet of the acid unloading pump is connected to the pickling tank.
- the inlet of the pickling pump is connected to the pickling tank, the outlet of the pickling pump is connected to the inlet of the electrolytic tank, and the pickling solution outlet of the electrolytic tank is connected to the pickling tank.
- the inlet of the acid mist absorber is connected with the gas phase outlet at the top of the pickling tank.
- the gas-liquid separation device is used to separate the gas-liquid mixture generated in the electrolysis device.
- the inlet of the gas-liquid separation device is connected to the outlet of the electrolytic cell of the electrolysis device, the liquid outlet of the gas-liquid separation device is connected to the sodium hypochlorite solution storage tank, and the gas outlet of the gas-liquid separation device is connected to the dechlorination device. connected to the air inlet.
- the interior of the gas-liquid separation device is a spiral structure, and the liquid entering the gas-liquid separation device is centrifuged along the spiral structure of the gas-liquid separation device. Movement to achieve centrifugal separation of gas and liquid, and separate them into sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase.
- the dechlorination device is used to dechlorinate the hydrogen separated in the gas-liquid separation device.
- the dechlorination device includes a dechlorination tower, an alkali tank and an alkali pump.
- the dechlorination tower adopts a barrel-shaped tank, and spray pipes are evenly distributed inside the dechlorination tower;
- the alkali tank can be made of a material resistant to sodium hypochlorite corrosion;
- the alkali pump can be a stainless steel centrifugal pump .
- the inlet of the alkali liquid pump is connected to the alkali liquid tank, and the outlet of the alkali liquid pump is connected to the spray pipe inside the dechlorination tower.
- the hydrogen pressurizing device is used to pressurize, cool and dry the dechlorinated hydrogen.
- the hydrogen pressurizing device may use a hydrogen compressor or a gas booster pump.
- the inlet of the hydrogen pressurizing device is connected with the gas outlet of the dechlorination device.
- the gas pressurizing device also includes a hydrogen cooling and drying device, which can be cooled by a gas air cooler or a cold dryer.
- the hydrogen deoxygenation device is used to deoxygenate the hydrogen gas that has been pressurized, cooled and dried.
- the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit, a secondary hydrogen deoxygenation unit and an optional tertiary hydrogen deoxygenation unit, wherein the primary hydrogen deoxygenation unit uses a gas separation membrane to deoxygenate, separate hydrogen and Oxygen, the inlet of the primary hydrogen deoxygenation unit is connected to the outlet of the hydrogen pressurizing device; the secondary hydrogen deoxygenation unit uses a palladium catalyst for deoxidation, and the inlet of the secondary hydrogen deoxygenation unit is connected to the outlet of the primary hydrogen deoxygenation unit.
- the outlets are connected; the tertiary hydrogen deoxygenation unit uses a temperature swing and pressure swing adsorption device for deoxygenation, and the inlet of the tertiary hydrogen deoxygenation unit is connected to the outlet of the secondary hydrogen deoxygenation unit.
- the invention also provides a desulfurization wastewater treatment method, as shown in Figure 3.
- the method includes the following steps:
- the desulfurization wastewater treatment method is implemented using the desulfurization wastewater treatment system described above.
- the deoxygenation process includes:
- a temperature swing and pressure swing adsorption device can be used for three deoxygenations.
- sodium hypochlorite solution and relatively pure hydrogen product can be obtained, and the entire process will not produce any waste waste.
- the shedding wastewater used in the following examples contains chloride ions 18g/L, sodium ions 11.4g/L, sulfate ions 0.2g/L, calcium ions 0.2g/L and magnesium ions 0.05g/L.
- the desulfurization wastewater treatment system used in this embodiment includes a pretreatment device, an electrolysis device, a gas-liquid separation device, a dechlorination device, a hydrogen pressurization device and a hydrogen deoxygenation device connected in sequence, as well as a device for A pickling device for cleaning the electrolytic device, wherein the pretreatment device includes a pH adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
- the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector.
- the main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet, and the auxiliary end of the mixer is connected to the desulfurization wastewater inlet.
- the liquid inlet end is connected to the acid solution dosing device and the alkali solution dosing device, and the pH detector is arranged at the connection between the mixer and the box.
- the sedimentation tank includes a box body, a liquid inlet central pipe and an overflow weir.
- the lower outlet of the liquid inlet central pipe is 10-30cm away from the bottom of the box.
- the overflow weir is arranged around the inner wall of the box. In the upper part, the upper edge of the overflow weir has a zigzag structure.
- the multi-media filter includes a tank body and filter material filled in the tank body.
- the filter material is quartz sand.
- the electrolysis device includes an electrolytic cell and a power supply, wherein the electrolytic cell is a plate electrode tube electrolytic cell.
- the pickling device includes a pickling tank, an acid unloading pump, a pickling pump and an acid mist absorber.
- the inlet of the pump is connected to the pickling solution tank, the outlet of the acid unloading pump is connected to the pickling tank, the inlet of the pickling pump is connected to the pickling tank, and the outlet of the pickling pump is connected to the pickling tank.
- the inlet of the electrolytic tank is connected, the pickling solution outlet of the electrolytic tank is connected with the pickling tank, and the inlet of the acid mist absorber is connected with the gas phase outlet on the top of the pickling tank.
- the inlet of the gas-liquid separation device is connected to the outlet of the electrolytic cell of the electrolysis device, the liquid outlet of the gas-liquid separation device is connected to the sodium hypochlorite solution storage tank, and the gas outlet of the gas-liquid separation device is connected to the dechlorination device. connected to the air inlet.
- the dechlorination device includes a dechlorination tower, an alkali tank and an alkali pump. Spray pipes are evenly distributed inside the dechlorination tower.
- the inlet of the alkali pump is connected to the alkali tank.
- the alkali tank The outlet of the pump is connected to the spray pipe inside the dechlorination tower.
- the hydrogen pressurizing device adopts a hydrogen compressor, and the inlet of the hydrogen pressurizing device is connected to the gas outlet of the dechlorination device.
- the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit, a secondary hydrogen deoxygenation unit and a tertiary hydrogen deoxygenation unit.
- the primary hydrogen deoxygenation unit uses a gas separation membrane to deoxygenate and separate hydrogen and oxygen.
- the inlet of the primary hydrogen deoxygenation unit is connected to The outlet of the hydrogen pressurizing device is connected; the hydrogen secondary deoxygenation unit uses a palladium catalyst for deoxygenation, and the inlet of the hydrogen secondary deoxygenation unit is connected to the outlet of the hydrogen primary deoxygenation unit; the hydrogen tertiary deoxygenation unit adopts variable temperature
- the pressure swing adsorption device performs deoxygenation, and the inlet of the tertiary hydrogen deoxygenation unit is connected to the outlet of the secondary hydrogen deoxygenation unit.
- the process of desulfurization wastewater treatment is: inject the desulfurization wastewater into the above-mentioned desulfurization wastewater treatment system for treatment.
- the pretreatment device add flocculant polyaluminum chloride (purchased from Jinan Jiayang Chemical Co., Ltd., in which Al 2 O 3 ⁇ 28%), to remove divalent ions in the desulfurization wastewater through flocculation and precipitation; then, the pretreated desulfurization wastewater is electrolyzed in an electrolysis device to generate a gas-liquid mixture containing sodium hypochlorite solution and hydrogen.
- the gas-liquid mixture is separated into a sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase; secondly, the separated hydrogen is dechlorinated to remove trace amounts of chlorine entrained in the hydrogen. ; Subsequently, the hydrogen after dechlorination is pressurized, cooled and dried; then, the hydrogen after pressurized, cooled and dried is deoxygenated three times.
- the purity of the hydrogen prepared according to this method is 99.999%, the concentration of the sodium hypochlorite solution is 8g/L, and the amount of hydrogen produced is 1800L per cubic meter of desulfurization wastewater.
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Abstract
A desulfurization wastewater treatment system and method. The desulfurization wastewater treatment system comprises a pretreatment device used for pretreating desulfurization wastewater, so as to remove divalent ions in the desulfurization wastewater; an electrolysis device used for electrolyzing the pretreated desulfurization wastewater; a gas-liquid separation device used for carrying out gas-liquid separation on a gas-liquid mixture generated in the electrolysis device; a dechlorination device used for dechlorinating hydrogen separated out in the gas-liquid separation device; a hydrogen pressurization device used for performing pressurization and cooling drying on the dechlorinated hydrogen; and a hydrogen deoxidation device used for deoxidizing the hydrogen subjected to the pressurization and cooling drying. The present invention treats desulfurization wastewater and can produce a sodium hypochlorite solution and hydrogen; the whole process does not generate and discharge waste.
Description
相关申请的交叉引用Cross-references to related applications
本申请要求2022年08月19日提交的中国专利申请202211001269.2的权益，该申请的内容通过引用被合并于本文。This application claims the rights and interests of Chinese patent application 202211001269.2 submitted on August 19, 2022. The contents of this application are incorporated herein by reference.
本发明涉及脱硫废水处理技术领域，具体涉及一种脱硫废水处理系统和方法。The present invention relates to the technical field of desulfurization wastewater treatment, and in particular to a desulfurization wastewater treatment system and method.
目前，湿法脱硫废水一般采用加药絮凝沉淀工艺，经过絮凝沉淀去除大部分二价离子后，通过加酸/碱调平pH值后，排入受纳水体。随着国家对环保要求的逐步提高，越来越多的生产企业要求污染物的零排放，脱硫废水经常规处理后，含有大量的氯离子和钠离子，为了达到零排要求，一般采用蒸发工艺，脱硫废水蒸发工艺是指脱硫废水经预处理后，通过加热将脱硫废水中的水分蒸干，以实现脱硫废水零排放，这种技术常规的工艺路线为：预处理+膜浓缩+蒸发结晶(MVR或MED)，蒸发工艺可以实现脱硫废水的零排放，而且已经有成功运行的工程案例，但是这种方法存在以下不足：由于采用膜浓缩和蒸发结晶工艺，整个系统占地面积大，且这种工艺投资成本及运行成本高；而且，蒸发结晶产生的盐一般为杂盐，很难再被利用，处理困难，
依旧存在污染物的排放，只是由废水变成了废固。At present, wet desulfurization wastewater generally adopts a drug-added flocculation and sedimentation process. After most of the divalent ions are removed through flocculation and sedimentation, the pH value is adjusted by adding acid/alkali before being discharged into the receiving water body. With the gradual improvement of the country's environmental protection requirements, more and more production companies require zero discharge of pollutants. After conventional treatment, desulfurization wastewater contains a large amount of chloride ions and sodium ions. In order to meet the zero discharge requirements, an evaporation process is generally used. The desulfurization wastewater evaporation process means that after the desulfurization wastewater is pretreated, the water in the desulfurization wastewater is evaporated to dryness by heating to achieve zero discharge of desulfurization wastewater. The conventional process route of this technology is: pretreatment + membrane concentration + evaporation crystallization ( MVR or MED), the evaporation process can achieve zero discharge of desulfurization wastewater, and there are already successful engineering cases. However, this method has the following shortcomings: due to the use of membrane concentration and evaporation crystallization processes, the entire system occupies a large area, and this The investment cost and operating cost of this process are high; moreover, the salt produced by evaporation and crystallization is generally miscellaneous salt, which is difficult to reuse and difficult to process. There is still the discharge of pollutants, but it has changed from waste water to solid waste.
发明内容Contents of the invention
本发明的目的是为了克服现有的脱硫废水处理系统存在的系统占地面积大、工艺投资成本高、运行成本高、蒸发过程产生的杂盐处理困难等问题，提供一种新的脱硫废水处理系统和方法。The purpose of the present invention is to provide a new desulfurization wastewater treatment system in order to overcome the problems existing in the existing desulfurization wastewater treatment system such as large system footprint, high process investment costs, high operating costs, and difficulty in processing miscellaneous salts generated during the evaporation process. Systems and methods.
为了实现上述目的，本发明提供了一种脱硫废水处理系统，该系统包括：In order to achieve the above objects, the present invention provides a desulfurization wastewater treatment system, which system includes:
预处理装置，用于对脱硫废水进行预处理，以脱除所述脱硫废水中的二价离子；A pretreatment device used to pretreat desulfurization wastewater to remove divalent ions in the desulfurization wastewater;
电解装置，用于对经过预处理后的脱硫废水进行电解；Electrolysis device for electrolysis of pretreated desulfurization wastewater;
气液分离装置，用于对所述电解装置中产生的气液混合物进行气液分离；A gas-liquid separation device, used for gas-liquid separation of the gas-liquid mixture produced in the electrolysis device;
脱氯装置，用于对所述气液分离装置中分离出的氢气进行脱氯；A dechlorination device used to dechlorinate the hydrogen separated in the gas-liquid separation device;
氢气加压装置，用于对经过脱氯后的氢气进行加压和冷却干燥；以及A hydrogen pressurizing device for pressurizing, cooling and drying dechlorinated hydrogen; and
氢气脱氧装置，用于对经过加压和冷却干燥后的氢气进行脱氧。Hydrogen deoxygenation device is used to deoxygenate hydrogen after pressurization, cooling and drying.
优选地，所述预处理装置包括依次连接的pH值调节箱、反应箱、絮凝箱、沉淀箱和多介质过滤器。Preferably, the pretreatment device includes a pH adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
优选地，所述pH值调节箱包括箱体、混合器、酸液投加装置、碱液投加装置和pH检测仪，所述混合器的主进液端与脱硫废水进口连接，所述混合器的辅进液端连接至所述酸液投加装置和碱液投加装
置，所述pH检测仪设置于所述混合器的出口与所述箱体的进液口之间。Preferably, the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector. The main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet, and the mixing The auxiliary liquid inlet end of the device is connected to the acid solution dosing device and the alkali solution dosing device The pH detector is arranged between the outlet of the mixer and the liquid inlet of the box.
优选地，所述沉淀箱包括箱体、进液中心管和溢流堰，所述进液中心管的下端出口距离所述箱体底部10-30cm，所述溢流堰环绕设置于所述箱体的内壁上部。Preferably, the sedimentation tank includes a box body, a central liquid inlet pipe and an overflow weir. The lower outlet of the central liquid inlet pipe is 10-30cm away from the bottom of the tank body. The overflow weir is arranged around the tank. The upper part of the inner wall of the body.
优选地，所述溢流堰的上沿为锯齿形结构。Preferably, the upper edge of the overflow weir has a zigzag structure.
优选地，所述多介质过滤器内部填充的过滤材料为石英砂、活性炭和无烟煤中一种或至少两种以上的任意组合。Preferably, the filter material filled inside the multi-media filter is one or any combination of at least two of quartz sand, activated carbon and anthracite.
优选地，所述电解装置所采用的电解槽为板式电极管式电解槽、板网式电极板式电解槽或同心圆管式电解槽。Preferably, the electrolytic cell used in the electrolysis device is a plate electrode tube electrolytic cell, a plate mesh electrode plate electrolytic cell or a concentric tube electrolytic cell.
优选地，所述系统还包括酸洗装置，用于对所述电解装置运行过程中产生的结垢进行清理。Preferably, the system further includes an acid cleaning device for cleaning the scaling generated during the operation of the electrolysis device.
优选地，所述氢气脱氧装置包括氢气一次脱氧单元和氢气二次脱氧单元，所述氢气一次脱氧单元采用气体分离膜脱氧，所述氢气二次脱氧单元采用钯催化剂脱氧。Preferably, the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit and a secondary hydrogen deoxygenation unit. The primary hydrogen deoxygenation unit uses a gas separation membrane for deoxidation, and the secondary hydrogen deoxygenation unit uses a palladium catalyst for deoxidation.
优选地，所述氢气脱氧装置还包括设置在所述氢气二次脱氧单元后面的氢气三次脱氧单元，所述氢气三次脱氧单元采用变温变压吸附装置进行脱氧。Preferably, the hydrogen deoxygenation device further includes a tertiary hydrogen deoxygenation unit arranged behind the secondary hydrogen deoxygenation unit, and the tertiary hydrogen deoxygenation unit uses a temperature swing and pressure swing adsorption device for deoxygenation.
本发明还提供了一种脱硫废水处理方法，该方法包括以下步骤：The invention also provides a method for treating desulfurization wastewater, which method includes the following steps:
(1)对脱硫废水进行预处理，通过絮凝、沉淀以脱除所述脱硫废水中的二价离子；(1) Pretreat desulfurization wastewater and remove divalent ions in the desulfurization wastewater through flocculation and precipitation;
(2)对经过预处理后的脱硫废水进行电解，生成包含次氯酸钠
溶液和氢气的气液混合物；(2) Electrolysis of pretreated desulfurization wastewater to generate sodium hypochlorite A gas-liquid mixture of solution and hydrogen;
(3)对所述气液混合物进行气液分离，分离成作为液相的次氯酸钠溶液和作为气相的氢气；(3) Perform gas-liquid separation on the gas-liquid mixture, and separate it into sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase;
(4)对分离出的所述氢气进行脱氯，以去除所述氢气中夹带的氯气；(4) Dechlorinate the separated hydrogen to remove chlorine entrained in the hydrogen;
(5)对经过脱氯后的氢气进行加压和冷却干燥；以及(5) Pressurize, cool and dry the dechlorinated hydrogen; and
(6)对经过加压和冷却干燥后的氢气进行脱氧。(6) Deoxygenate the hydrogen gas that has been pressurized, cooled and dried.
优选地，所述脱氧的过程包括：Preferably, the deoxidation process includes:
采用气体分离膜进行一次脱氧；Use gas separation membrane for primary deoxidation;
采用钯催化剂进行二次脱氧；以及Secondary deoxygenation using a palladium catalyst; and
可选地采用变温变压吸附装置进行三次脱氧。Optionally, a temperature swing and pressure swing adsorption device can be used for three deoxygenations.
按照本发明所述的脱硫废水的处理方法和系统，对脱硫废水进行预处理，通过絮凝、沉淀去除大部分的二价离子，剩余在水体中的基本为钠离子和氯离子，接着通过电解可以将氯离子转化为次氯酸钠，次氯酸钠可供厂区消毒使用，电解过程中产生的氢气通过脱氯、加压并冷却干燥以及脱氧，可以获得纯净的氢气。因此，按照本发明所述的技术方案对脱硫废水进行处理，整体工艺不会产生外排废弃物，而且整个系统占地面积小、工艺投资成本和运行成本均较低。According to the desulfurization wastewater treatment method and system of the present invention, the desulfurization wastewater is pretreated, and most of the divalent ions are removed through flocculation and precipitation. The remaining ones in the water body are basically sodium ions and chloride ions, and then electrolysis can Convert chloride ions into sodium hypochlorite, which can be used for factory disinfection. The hydrogen generated during the electrolysis process is dechlorinated, pressurized, cooled, dried, and deoxygenated to obtain pure hydrogen. Therefore, when desulfurization wastewater is treated according to the technical solution of the present invention, the overall process will not produce any waste, and the entire system will occupy a small area, and the process investment cost and operating cost will be low.
图1是本发明所述的脱硫废水处理系统的示意图；Figure 1 is a schematic diagram of the desulfurization wastewater treatment system according to the present invention;
图2是本发明所述的脱硫废水处理系统中预处理装置的示意图；
Figure 2 is a schematic diagram of the pretreatment device in the desulfurization wastewater treatment system of the present invention;
图3是本发明所述的脱硫废水处理方法的流程图。Figure 3 is a flow chart of the desulfurization wastewater treatment method according to the present invention.
以下结合附图对本发明的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本发明，并不用于限制本发明。Specific embodiments of the present invention will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present invention, and are not intended to limit the present invention.
如图1所示，本发明所述的脱硫废水处理系统包括依次连接的预处理装置、电解装置、气液分离装置、脱氯装置、氢气加压装置和氢气脱氧装置。As shown in Figure 1, the desulfurization wastewater treatment system of the present invention includes a pretreatment device, an electrolysis device, a gas-liquid separation device, a dechlorination device, a hydrogen pressurization device and a hydrogen deoxygenation device connected in sequence.
在所述脱硫废水处理系统中，所述预处理装置用于对脱硫废水进行预处理，以脱除所述脱硫废水中的二价离子。在一种具体实施方式中，如图2所示，所述预处理装置包括依次连接的pH值调节箱、反应箱、絮凝箱、沉淀箱和多介质过滤器。In the desulfurization wastewater treatment system, the pretreatment device is used to pretreat the desulfurization wastewater to remove divalent ions in the desulfurization wastewater. In a specific implementation, as shown in Figure 2, the pretreatment device includes a pH value adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
在所述预处理装置中，所述pH值调节箱包括箱体、混合器、酸液投加装置、碱液投加装置和pH检测仪。所述混合器的主进液端与脱硫废水进口连接，所述混合器的辅进液端连接至所述酸液投加装置和碱液投加装置，所述pH检测仪设置于所述混合器的出口与所述箱体的进液口之间，具体地，所述pH检测仪设置于所述混合器与所述箱体的连接处。In the pretreatment device, the pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector. The main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet, the auxiliary liquid inlet end of the mixer is connected to the acid liquid dosing device and the alkali liquid dosing device, and the pH detector is installed on the mixing between the outlet of the mixer and the liquid inlet of the box. Specifically, the pH detector is disposed at the connection between the mixer and the box.
所述酸液投加装置包括酸液计量泵，所述酸液投加装置的进口连接至酸液存储罐，并且酸液通过酸液计量泵注入所述混合器中。The acid liquid dosing device includes an acid liquid metering pump, the inlet of the acid liquid dosing device is connected to the acid liquid storage tank, and the acid liquid is injected into the mixer through the acid liquid metering pump.
所述减液投加装置包括碱液计量泵，所述碱液投加装置的进口连
接至碱液存储罐，并且碱液通过碱液计量泵注入所述混合器中。The liquid reducing dosing device includes an alkali metering pump, and the inlet connection of the alkali dosing device It is connected to the alkali liquid storage tank, and the alkali liquid is injected into the mixer through the alkali liquid metering pump.
所述混合器可以选自静态混合器、动力搅拌混合器和管道混合器。The mixer may be selected from static mixers, dynamic agitation mixers and pipe mixers.
在所述预处理装置中，所述反应箱包括药剂投加计量泵。所述药剂投加计量泵所投加的药剂可以是碳酸钠、氢氧化钠等，所述药剂投加计量泵对应接至各自的储液箱。In the pretreatment device, the reaction box includes a chemical dosing metering pump. The medicine added by the medicine adding metering pump can be sodium carbonate, sodium hydroxide, etc., and the medicine adding metering pump is correspondingly connected to the respective liquid storage tank.
在所述预处理装置中，所述絮凝箱包括絮凝剂投加计量泵。所述絮凝剂投加计量泵连接至絮凝剂存储箱，所用的絮凝剂可以为本领域的常规选择，例如可以为聚合氯化铝、三氯化铁、硫酸亚铁、明矾和硫酸铝中的至少一种。In the pretreatment device, the flocculation box includes a flocculant dosing metering pump. The flocculant dosing metering pump is connected to the flocculant storage tank. The flocculant used can be a conventional choice in this field, for example, it can be polyaluminum chloride, ferric chloride, ferrous sulfate, alum and aluminum sulfate. At least one.
在所述预处理装置中，在优选情况下，所述沉淀箱包括箱体、进液中心管和溢流堰，所述进液中心管的下端出口距离所述箱体底部10-30cm，所述溢流堰环绕设置于所述箱体的内壁上部。按照上述优选结构的沉淀箱，可以获得较好的絮凝沉淀效果。所述溢流堰的上沿的结构形式没有特别的限定。在较优选的实施方式中，所述溢流堰的上沿为锯齿形结构。这种锯齿形结构能够克服水的表面张力，促进水流均匀。在具体的实施方式中，形成所述溢流堰的上沿的锯齿形可以为方形、半圆形或三角形等。In the pretreatment device, in a preferred case, the sedimentation tank includes a box, a liquid inlet central pipe and an overflow weir. The lower outlet of the liquid inlet central pipe is 10-30cm away from the bottom of the box, so The overflow weir is arranged around the upper part of the inner wall of the box. According to the sedimentation tank with the above preferred structure, better flocculation and sedimentation effect can be obtained. The structural form of the upper edge of the overflow weir is not particularly limited. In a more preferred embodiment, the upper edge of the overflow weir has a zigzag structure. This zigzag structure overcomes the surface tension of water and promotes uniform water flow. In a specific embodiment, the zigzag shape forming the upper edge of the overflow weir may be square, semicircular, triangular, etc.
在所述预处理装置中，所述多介质过滤器包括罐体和填充于罐体内的过滤材料。所述罐体可以是玻璃钢、碳钢衬塑等材质。所述多介质过滤器内部填充的过滤材料优选为石英砂、活性炭和无烟煤中一种或至少两种以上的任意组合。In the pretreatment device, the multi-media filter includes a tank body and filter material filled in the tank body. The tank body may be made of fiberglass, carbon steel lined with plastic, or other materials. The filter material filled inside the multi-media filter is preferably one or any combination of at least two of quartz sand, activated carbon and anthracite.
在所述脱硫废水处理系统中，所述电解装置用于对经过预处理后
的脱硫废水进行电解，以生成次氯酸钠溶液和氢气。所述电解装置包括电解槽和电源。所述电解槽优选为板式电极管式电解槽、板网式电极板式电解槽或同心圆管式电解槽。所述电源可以采用高频稳流开关电压，也可以采用可控硅整流电源。所述电解槽与所述电源优选通过电缆或铜排相连。In the desulfurization wastewater treatment system, the electrolysis device is used to treat pre-treated The desulfurization wastewater is electrolyzed to generate sodium hypochlorite solution and hydrogen gas. The electrolysis device includes an electrolysis tank and a power supply. The electrolytic cell is preferably a plate electrode tube electrolytic cell, a plate mesh electrode plate electrolytic cell or a concentric tube electrolytic cell. The power supply may adopt a high-frequency steady-current switching voltage or a silicon-controlled rectified power supply. The electrolytic tank and the power supply are preferably connected through cables or copper bars.
在所述脱硫废水处理系统中，在优选情况下，所述系统还包括酸洗装置，用于对所述电解装置运行过程中产生的结垢进行清理。在较优选的实施方式中，所述酸洗装置包括酸洗罐、卸酸泵、酸洗泵和酸雾吸收器。所述酸洗罐可以采用PE材质罐体，也可以采用玻璃钢材质罐体，也可以采用钢衬胶材质罐体。所述卸酸泵可以采用磁力泵，也可以采用离心泵。所述酸洗泵可以采用磁力泵，也可以采用离心泵。所述酸雾吸收器的内部可以采用拉西环等填料填充，并填充氢氧化钠溶液。所述卸酸泵的进口与酸洗溶液罐体相连，所述卸酸泵的出口与所述酸洗罐相连。所述酸洗泵的进口与所述酸洗罐相连，所述酸洗泵的出口与所述电解槽的进口相连，所述电解槽的酸洗溶液出口与酸洗罐相连。所述酸雾吸收器的进口与酸洗罐顶部的气相出口相连。In the desulfurization wastewater treatment system, in a preferred case, the system further includes an acid cleaning device for cleaning the scaling generated during the operation of the electrolysis device. In a more preferred embodiment, the pickling device includes a pickling tank, an acid unloading pump, a pickling pump and an acid mist absorber. The pickling tank can use a PE material tank, a glass fiber reinforced plastic tank, or a steel-lined rubber tank. The acid unloading pump can be a magnetic pump or a centrifugal pump. The pickling pump can be a magnetic pump or a centrifugal pump. The inside of the acid mist absorber can be filled with fillers such as Raschig rings and filled with sodium hydroxide solution. The inlet of the acid unloading pump is connected to the pickling solution tank, and the outlet of the acid unloading pump is connected to the pickling tank. The inlet of the pickling pump is connected to the pickling tank, the outlet of the pickling pump is connected to the inlet of the electrolytic tank, and the pickling solution outlet of the electrolytic tank is connected to the pickling tank. The inlet of the acid mist absorber is connected with the gas phase outlet at the top of the pickling tank.
在所述脱硫废水处理系统中，所述气液分离装置用于对所述电解装置中产生的气液混合物进行气液分离。所述气液分离装置的进口与所述电解装置的电解槽的出口相连，所述气液分离装置的出液口与次氯酸钠溶液存储罐相连，所述气液分离装置的出气口与脱氯装置的进气口相连。在较优选的实施方式中，所述气液分离装置的内部为螺旋结构，进入气液分离装置的液体沿气液分离装置的螺旋结构进行离心
运动，实现气体与液体的离心分离，并分离成作为液相的次氯酸钠溶液和作为气相的氢气。In the desulfurization wastewater treatment system, the gas-liquid separation device is used to separate the gas-liquid mixture generated in the electrolysis device. The inlet of the gas-liquid separation device is connected to the outlet of the electrolytic cell of the electrolysis device, the liquid outlet of the gas-liquid separation device is connected to the sodium hypochlorite solution storage tank, and the gas outlet of the gas-liquid separation device is connected to the dechlorination device. connected to the air inlet. In a more preferred embodiment, the interior of the gas-liquid separation device is a spiral structure, and the liquid entering the gas-liquid separation device is centrifuged along the spiral structure of the gas-liquid separation device. Movement to achieve centrifugal separation of gas and liquid, and separate them into sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase.
在所述脱硫废水处理系统中，所述脱氯装置用于对所述气液分离装置中分离出的氢气进行脱氯。所述脱氯装置包括脱氯塔、碱液罐和碱液泵。其中，所述脱氯塔采用圆桶型罐体，所述脱氯塔内部均匀分布有喷淋管；所述碱液罐采用耐次氯酸钠腐蚀材质即可；所述碱液泵可以采用不锈钢离心泵。所述碱液泵的进口与所述碱液罐相连，所述碱液泵的出口与所述脱氯塔内部的喷淋管相连。In the desulfurization wastewater treatment system, the dechlorination device is used to dechlorinate the hydrogen separated in the gas-liquid separation device. The dechlorination device includes a dechlorination tower, an alkali tank and an alkali pump. Among them, the dechlorination tower adopts a barrel-shaped tank, and spray pipes are evenly distributed inside the dechlorination tower; the alkali tank can be made of a material resistant to sodium hypochlorite corrosion; the alkali pump can be a stainless steel centrifugal pump . The inlet of the alkali liquid pump is connected to the alkali liquid tank, and the outlet of the alkali liquid pump is connected to the spray pipe inside the dechlorination tower.
在所述脱硫废水处理系统中，所述氢气加压装置用于对经过脱氯后的氢气进行加压和冷却干燥。所述氢气加压装置可以采用氢气压缩机，也可以采用气体增压泵。所述氢气加压装置的进口与所述脱氯装置的气体出口相连。所述气体加压装置还包含氢气冷却干燥装置，可以采用气体空冷器降温，也可以采用冷干机冷却并降温。In the desulfurization wastewater treatment system, the hydrogen pressurizing device is used to pressurize, cool and dry the dechlorinated hydrogen. The hydrogen pressurizing device may use a hydrogen compressor or a gas booster pump. The inlet of the hydrogen pressurizing device is connected with the gas outlet of the dechlorination device. The gas pressurizing device also includes a hydrogen cooling and drying device, which can be cooled by a gas air cooler or a cold dryer.
在所述脱硫废水处理系统中，所述氢气脱氧装置用于对经过加压和冷却干燥后的氢气进行脱氧。在较优选的实施方式中，所述氢气脱氧装置包括氢气一次脱氧单元、氢气二次脱氧单元以及可选的氢气三次脱氧单元，其中，所述氢气一次脱氧单元采用气体分离膜脱氧，分离氢气和氧气，所述氢气一次脱氧单元的进口与所述氢气加压装置的出口相连；所述氢气二次脱氧单元采用钯催化剂脱氧，所述氢气二次脱氧单元的进口与所述氢气一次脱氧单元的出口相连；所述氢气三次脱氧单元采用变温变压吸附装置进行脱氧，所述氢气三次脱氧单元的进口与所述氢气二次脱氧单元的出口相连。
In the desulfurization wastewater treatment system, the hydrogen deoxygenation device is used to deoxygenate the hydrogen gas that has been pressurized, cooled and dried. In a more preferred embodiment, the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit, a secondary hydrogen deoxygenation unit and an optional tertiary hydrogen deoxygenation unit, wherein the primary hydrogen deoxygenation unit uses a gas separation membrane to deoxygenate, separate hydrogen and Oxygen, the inlet of the primary hydrogen deoxygenation unit is connected to the outlet of the hydrogen pressurizing device; the secondary hydrogen deoxygenation unit uses a palladium catalyst for deoxidation, and the inlet of the secondary hydrogen deoxygenation unit is connected to the outlet of the primary hydrogen deoxygenation unit. The outlets are connected; the tertiary hydrogen deoxygenation unit uses a temperature swing and pressure swing adsorption device for deoxygenation, and the inlet of the tertiary hydrogen deoxygenation unit is connected to the outlet of the secondary hydrogen deoxygenation unit.
本发明还提供了一种脱硫废水处理方法，如图3所示，该方法包括以下步骤：The invention also provides a desulfurization wastewater treatment method, as shown in Figure 3. The method includes the following steps:
(1)对脱硫废水进行预处理，通过絮凝、沉淀以脱除所述脱硫废水中的二价离子；(1) Pretreat desulfurization wastewater and remove divalent ions in the desulfurization wastewater through flocculation and precipitation;
(2)对经过预处理后的脱硫废水进行电解，生成包含次氯酸钠溶液和氢气的气液混合物；(2) Electrolyze the pretreated desulfurization wastewater to generate a gas-liquid mixture containing sodium hypochlorite solution and hydrogen;
(3)对所述气液混合物进行气液分离，分离成作为液相的次氯酸钠溶液和作为气相的氢气；(3) Perform gas-liquid separation on the gas-liquid mixture, and separate it into sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase;
(4)对分离出的所述氢气进行脱氯，以去除所述氢气中夹带的氯气；(4) Dechlorinate the separated hydrogen to remove chlorine entrained in the hydrogen;
(5)对经过脱氯后的氢气进行加压和冷却干燥；以及(5) Pressurize, cool and dry the dechlorinated hydrogen; and
(6)对经过加压和冷却干燥后的氢气进行脱氧。(6) Deoxygenate the hydrogen gas that has been pressurized, cooled and dried.
在一种优选实施方式中，所述脱硫废水处理方法采用前文所述的脱硫废水处理系统实施。In a preferred embodiment, the desulfurization wastewater treatment method is implemented using the desulfurization wastewater treatment system described above.
在另一种优选实施方式中，所述脱氧的过程包括：In another preferred embodiment, the deoxygenation process includes:
采用气体分离膜进行一次脱氧；Use gas separation membrane for primary deoxidation;
采用钯催化剂进行二次脱氧；以及Secondary deoxygenation using a palladium catalyst; and
可选地采用变温变压吸附装置进行三次脱氧。Optionally, a temperature swing and pressure swing adsorption device can be used for three deoxygenations.
按照本发明所述的脱硫废水处理方法对脱硫废水进行处理，可以得到次氯酸钠溶液和较纯的氢气产品，整个工艺过程不会产生外排废弃物。By treating desulfurization wastewater according to the desulfurization wastewater treatment method described in the present invention, sodium hypochlorite solution and relatively pure hydrogen product can be obtained, and the entire process will not produce any waste waste.
下面通过实施例来进一步说明本发明所述的脱硫废水处理系统
和方法。实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体操作过程，但本发明的保护范围不限于下述实施例。The following examples will further illustrate the desulfurization wastewater treatment system of the present invention. and methods. The examples are implemented on the premise of the technical solution of the present invention, and detailed implementation modes and specific operating processes are given. However, the protection scope of the present invention is not limited to the following examples.
以下实施例中的实验方法，如无特殊说明，均为本领域常规方法。下述实施例中所用的实验材料，如无特殊说明，均可商购得到。The experimental methods in the following examples are all routine methods in this field unless otherwise specified. The experimental materials used in the following examples are all commercially available unless otherwise specified.
以下实施例中所用的脱落废水中含有氯离子18g/L、钠离子11.4g/L、硫酸根离子0.2g/L、钙离子0.2g/L和镁离子0.05g/L。The shedding wastewater used in the following examples contains chloride ions 18g/L, sodium ions 11.4g/L, sulfate ions 0.2g/L, calcium ions 0.2g/L and magnesium ions 0.05g/L.
实施例1Example 1
如图1-2所示，本实施例所用的脱硫废水处理系统包括依次连接的预处理装置、电解装置、气液分离装置、脱氯装置、氢气加压装置和氢气脱氧装置，以及用于对电解装置进行清理的酸洗装置，其中，所述预处理装置包括依次连接的pH值调节箱、反应箱、絮凝箱、沉淀箱和多介质过滤器。所述pH值调节箱包括箱体、混合器、酸液投加装置、碱液投加装置和pH检测仪，所述混合器的主进液端与脱硫废水进口连接，所述混合器的辅进液端连接至所述酸液投加装置和碱液投加装置，所述pH检测仪设置于所述混合器与所述箱体的连接处。所述沉淀箱包括箱体、进液中心管和溢流堰，所述进液中心管的下端出口距离所述箱体底部10-30cm，所述溢流堰环绕设置于所述箱体的内壁上部，所述溢流堰的上沿为锯齿形结构。所述多介质过滤器包括罐体和填充于罐体内的过滤材料，所述过滤材料为石英砂。所述电解装置包括电解槽和电源，其中，所述电解槽为板式电极管式电解槽。所述酸洗装置包括酸洗罐、卸酸泵、酸洗泵和酸雾吸收器，所述卸酸
泵的进口与酸洗溶液罐体相连，所述卸酸泵的出口与所述酸洗罐相连，所述酸洗泵的进口与所述酸洗罐相连，所述酸洗泵的出口与所述电解槽的进口相连，所述电解槽的酸洗溶液出口与酸洗罐相连，所述酸雾吸收器的进口与酸洗罐顶部的气相出口相连。所述气液分离装置的进口与所述电解装置的电解槽的出口相连，所述气液分离装置的出液口与次氯酸钠溶液存储罐相连，所述气液分离装置的出气口与脱氯装置的进气口相连。所述脱氯装置包括脱氯塔、碱液罐和碱液泵，所述脱氯塔内部均匀分布有喷淋管，所述碱液泵的进口与所述碱液罐相连，所述碱液泵的出口与所述脱氯塔内部的喷淋管相连。所述氢气加压装置采用氢气压缩机，所述氢气加压装置的进口与所述脱氯装置的气体出口相连。所述氢气脱氧装置包括氢气一次脱氧单元、氢气二次脱氧单元以及氢气三次脱氧单元，其中，所述氢气一次脱氧单元采用气体分离膜脱氧，分离氢气和氧气，所述氢气一次脱氧单元的进口与所述氢气加压装置的出口相连；所述氢气二次脱氧单元采用钯催化剂脱氧，所述氢气二次脱氧单元的进口与所述氢气一次脱氧单元的出口相连；所述氢气三次脱氧单元采用变温变压吸附装置进行脱氧，所述氢气三次脱氧单元的进口与所述氢气二次脱氧单元的出口相连。As shown in Figure 1-2, the desulfurization wastewater treatment system used in this embodiment includes a pretreatment device, an electrolysis device, a gas-liquid separation device, a dechlorination device, a hydrogen pressurization device and a hydrogen deoxygenation device connected in sequence, as well as a device for A pickling device for cleaning the electrolytic device, wherein the pretreatment device includes a pH adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence. The pH value adjustment box includes a box, a mixer, an acid solution dosing device, an alkali solution dosing device and a pH detector. The main liquid inlet end of the mixer is connected to the desulfurization wastewater inlet, and the auxiliary end of the mixer is connected to the desulfurization wastewater inlet. The liquid inlet end is connected to the acid solution dosing device and the alkali solution dosing device, and the pH detector is arranged at the connection between the mixer and the box. The sedimentation tank includes a box body, a liquid inlet central pipe and an overflow weir. The lower outlet of the liquid inlet central pipe is 10-30cm away from the bottom of the box. The overflow weir is arranged around the inner wall of the box. In the upper part, the upper edge of the overflow weir has a zigzag structure. The multi-media filter includes a tank body and filter material filled in the tank body. The filter material is quartz sand. The electrolysis device includes an electrolytic cell and a power supply, wherein the electrolytic cell is a plate electrode tube electrolytic cell. The pickling device includes a pickling tank, an acid unloading pump, a pickling pump and an acid mist absorber. The inlet of the pump is connected to the pickling solution tank, the outlet of the acid unloading pump is connected to the pickling tank, the inlet of the pickling pump is connected to the pickling tank, and the outlet of the pickling pump is connected to the pickling tank. The inlet of the electrolytic tank is connected, the pickling solution outlet of the electrolytic tank is connected with the pickling tank, and the inlet of the acid mist absorber is connected with the gas phase outlet on the top of the pickling tank. The inlet of the gas-liquid separation device is connected to the outlet of the electrolytic cell of the electrolysis device, the liquid outlet of the gas-liquid separation device is connected to the sodium hypochlorite solution storage tank, and the gas outlet of the gas-liquid separation device is connected to the dechlorination device. connected to the air inlet. The dechlorination device includes a dechlorination tower, an alkali tank and an alkali pump. Spray pipes are evenly distributed inside the dechlorination tower. The inlet of the alkali pump is connected to the alkali tank. The alkali tank The outlet of the pump is connected to the spray pipe inside the dechlorination tower. The hydrogen pressurizing device adopts a hydrogen compressor, and the inlet of the hydrogen pressurizing device is connected to the gas outlet of the dechlorination device. The hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit, a secondary hydrogen deoxygenation unit and a tertiary hydrogen deoxygenation unit. The primary hydrogen deoxygenation unit uses a gas separation membrane to deoxygenate and separate hydrogen and oxygen. The inlet of the primary hydrogen deoxygenation unit is connected to The outlet of the hydrogen pressurizing device is connected; the hydrogen secondary deoxygenation unit uses a palladium catalyst for deoxygenation, and the inlet of the hydrogen secondary deoxygenation unit is connected to the outlet of the hydrogen primary deoxygenation unit; the hydrogen tertiary deoxygenation unit adopts variable temperature The pressure swing adsorption device performs deoxygenation, and the inlet of the tertiary hydrogen deoxygenation unit is connected to the outlet of the secondary hydrogen deoxygenation unit.
脱硫废水处理的过程为：将脱硫废水注入上述脱硫废水处理系统中进行处理，在所述预处理装置中，投加絮凝剂聚合氯化铝(购自济南嘉阳化工有限公司，其中Al2O3≥28％)，通过絮凝、沉淀以脱除所述脱硫废水中的二价离子；接着，在电解装置中对经过预处理后的脱硫废水进行电解，生成包含次氯酸钠溶液和氢气的气液混合物；再
接着，对所述气液混合物进行气液分离，分离成作为液相的次氯酸钠溶液和作为气相的氢气；其次，对分离出的所述氢气进行脱氯，以去除所述氢气中夹带的微量氯气；随后，对经过脱氯后的氢气进行加压和冷却干燥；然后，对经过加压和冷却干燥后的氢气进行三次脱氧。按照该方法制备的氢气的纯度为99.999％，制得的次氯酸钠溶液的浓度为8g/L，针对每立方米的脱硫废水，制得的氢气的量为1800L。The process of desulfurization wastewater treatment is: inject the desulfurization wastewater into the above-mentioned desulfurization wastewater treatment system for treatment. In the pretreatment device, add flocculant polyaluminum chloride (purchased from Jinan Jiayang Chemical Co., Ltd., in which Al 2 O 3 ≥ 28%), to remove divalent ions in the desulfurization wastewater through flocculation and precipitation; then, the pretreated desulfurization wastewater is electrolyzed in an electrolysis device to generate a gas-liquid mixture containing sodium hypochlorite solution and hydrogen. ;Again Next, the gas-liquid mixture is separated into a sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase; secondly, the separated hydrogen is dechlorinated to remove trace amounts of chlorine entrained in the hydrogen. ; Subsequently, the hydrogen after dechlorination is pressurized, cooled and dried; then, the hydrogen after pressurized, cooled and dried is deoxygenated three times. The purity of the hydrogen prepared according to this method is 99.999%, the concentration of the sodium hypochlorite solution is 8g/L, and the amount of hydrogen produced is 1800L per cubic meter of desulfurization wastewater.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于此。在本发明的技术构思范围内，可以对本发明的技术方案进行多种简单变型，包括各个技术特征以任何其它的合适方式进行组合，这些简单变型和组合同样应当视为本发明所公开的内容，均属于本发明的保护范围。
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical concept of the present invention, many simple modifications can be made to the technical solution of the present invention, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be regarded as the disclosed content of the present invention. All belong to the protection scope of the present invention.
Claims (12)
- 一种脱硫废水处理系统，其特征在于，该系统包括：A desulfurization wastewater treatment system, characterized in that the system includes:预处理装置，用于对脱硫废水进行预处理，以脱除所述脱硫废水中的二价离子；A pretreatment device used to pretreat desulfurization wastewater to remove divalent ions in the desulfurization wastewater;电解装置，用于对经过预处理后的脱硫废水进行电解；Electrolysis device for electrolysis of pretreated desulfurization wastewater;气液分离装置，用于对所述电解装置中产生的气液混合物进行气液分离；A gas-liquid separation device, used for gas-liquid separation of the gas-liquid mixture produced in the electrolysis device;脱氯装置，用于对所述气液分离装置中分离出的氢气进行脱氯；A dechlorination device used to dechlorinate the hydrogen separated in the gas-liquid separation device;氢气加压装置，用于对经过脱氯后的氢气进行加压和冷却干燥；以及A hydrogen pressurizing device for pressurizing, cooling and drying dechlorinated hydrogen; and氢气脱氧装置，用于对经过加压和冷却干燥后的氢气进行脱氧。Hydrogen deoxygenation device is used to deoxygenate hydrogen after pressurization, cooling and drying.
- 根据权利要求1所述的系统，其特征在于，所述预处理装置包括依次连接的pH值调节箱、反应箱、絮凝箱、沉淀箱和多介质过滤器。The system according to claim 1, characterized in that the pretreatment device includes a pH value adjustment box, a reaction box, a flocculation box, a sedimentation box and a multi-media filter connected in sequence.
- 根据权利要求2所述的系统，其特征在于，所述pH值调节箱包括箱体、混合器、酸液投加装置、碱液投加装置和pH检测仪，所述混合器的主进液端与脱硫废水进口连接，所述混合器的辅进液端连接至所述酸液投加装置和碱液投加装置，所述pH检测仪设置于所述混合器的出口与所述箱体的进液口之间。 The system according to claim 2, characterized in that the pH value adjustment box includes a box, a mixer, an acid solution adding device, an alkali solution adding device and a pH detector, and the main liquid inlet of the mixer The end is connected to the desulfurization wastewater inlet, the auxiliary liquid inlet end of the mixer is connected to the acid solution dosing device and the alkali solution dosing device, and the pH detector is arranged between the outlet of the mixer and the box. between the liquid inlets.
- 根据权利要求2所述的系统，其特征在于，所述沉淀箱包括箱体、进液中心管和溢流堰，所述进液中心管的下端出口距离所述箱体底部10-30cm，所述溢流堰环绕设置于所述箱体的内壁上部。The system according to claim 2, characterized in that the sedimentation tank includes a box body, a liquid inlet central pipe and an overflow weir, and the lower end outlet of the liquid inlet central pipe is 10-30cm away from the bottom of the tank, so The overflow weir is arranged around the upper part of the inner wall of the box.
- 根据权利要求4所述的系统，其特征在于，所述溢流堰的上沿为锯齿形结构。The system according to claim 4, characterized in that the upper edge of the overflow weir has a zigzag structure.
- 根据权利要求2所述的系统，其特征在于，所述多介质过滤器内部填充的过滤材料为石英砂、活性炭和无烟煤中一种或至少两种以上的任意组合。The system according to claim 2, wherein the filter material filled inside the multi-media filter is one or any combination of at least two of quartz sand, activated carbon and anthracite.
- 根据权利要求1所述的系统，其特征在于，所述电解装置所采用的电解槽为板式电极管式电解槽、板网式电极板式电解槽或同心圆管式电解槽。The system according to claim 1, characterized in that the electrolytic cell used in the electrolysis device is a plate electrode tube electrolytic cell, a plate mesh electrode plate electrolytic cell or a concentric tube electrolytic cell.
- 根据权利要求1-7中任意一项所述的系统，其特征在于，所述系统还包括酸洗装置，用于对所述电解装置运行过程中产生的结垢进行清理。The system according to any one of claims 1 to 7, characterized in that the system further includes an acid cleaning device for cleaning the scaling generated during the operation of the electrolysis device.
- 根据权利要求1-7中任意一项所述的系统，其特征在于，所述氢气脱氧装置包括氢气一次脱氧单元和氢气二次脱氧单元，所述氢气一次脱氧单元采用气体分离膜脱氧，所述氢气二次脱氧单元采用钯 催化剂脱氧。The system according to any one of claims 1 to 7, wherein the hydrogen deoxygenation device includes a primary hydrogen deoxygenation unit and a secondary hydrogen deoxygenation unit, and the primary hydrogen deoxygenation unit uses a gas separation membrane for deoxygenation, and the The hydrogen secondary deoxygenation unit uses palladium Catalyst deoxygenation.
- 根据权利要求9所述的系统，其特征在于，所述氢气脱氧装置还包括设置在所述氢气二次脱氧单元后面的氢气三次脱氧单元，所述氢气三次脱氧单元采用变温变压吸附装置进行脱氧。The system according to claim 9, wherein the hydrogen deoxygenation device further includes a tertiary hydrogen deoxygenation unit arranged behind the secondary hydrogen deoxygenation unit, and the tertiary hydrogen deoxygenation unit adopts a temperature swing and pressure swing adsorption device for deoxygenation. .
- 一种脱硫废水处理方法，其特征在于，该方法包括以下步骤：A method for treating desulfurization wastewater, characterized in that the method includes the following steps:(1)对脱硫废水进行预处理，通过絮凝、沉淀以脱除所述脱硫废水中的二价离子；(1) Pretreat desulfurization wastewater and remove divalent ions in the desulfurization wastewater through flocculation and precipitation;(2)对经过预处理后的脱硫废水进行电解，生成包含次氯酸钠溶液和氢气的气液混合物；(2) Electrolyze the pretreated desulfurization wastewater to generate a gas-liquid mixture containing sodium hypochlorite solution and hydrogen;(3)对所述气液混合物进行气液分离，分离成作为液相的次氯酸钠溶液和作为气相的氢气；(3) Perform gas-liquid separation on the gas-liquid mixture, and separate it into sodium hypochlorite solution as a liquid phase and hydrogen as a gas phase;(4)对分离出的所述氢气进行脱氯，以去除所述氢气中夹带的氯气；(4) Dechlorinate the separated hydrogen to remove chlorine entrained in the hydrogen;(5)对经过脱氯后的氢气进行加压和冷却干燥；以及(5) Pressurize, cool and dry the dechlorinated hydrogen; and(6)对经过加压和冷却干燥后的氢气进行脱氧。(6) Deoxygenate the hydrogen gas that has been pressurized, cooled and dried.
- 根据权利要求11所述的方法，其特征在于，所述脱氧的过程包括：The method according to claim 11, characterized in that the deoxidation process includes:采用气体分离膜进行一次脱氧；Use gas separation membrane for primary deoxidation;采用钯催化剂进行二次脱氧；以及 Secondary deoxygenation using a palladium catalyst; and可选地采用变温变压吸附装置进行三次脱氧。 Optionally, a temperature swing and pressure swing adsorption device can be used for three deoxygenations.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070138020A1 (en) * | 2005-12-20 | 2007-06-21 | Shekar Balagopal | Electrolytic process to produce sodium hypochlorite using sodium ion conductive ceramic membranes |
| CN105314773A (en) * | 2014-07-10 | 2016-02-10 | 王辛平 | Wet desulphurization wastewater recycling method and apparatus thereof |
| CN205099427U (en) * | 2015-11-06 | 2016-03-23 | 山东大学 | System for utilize electrolysis electrodialysis to handle chlorion in wet flue gas desulfurization system |
| CN106567103A (en) * | 2016-11-08 | 2017-04-19 | 中广核工程有限公司 | Co-production method and system for sodium hypochlorite and high-purity hydrogen |
| CN106967996A (en) * | 2017-04-18 | 2017-07-21 | 碧海舟（北京）节能环保装备有限公司 | The hydrogen manufacturing of clean energy resource seawater and sodium hypochlorite system |
| JP2018035024A (en) * | 2016-08-30 | 2018-03-08 | クボタ環境サ−ビス株式会社 | Method for producing sodium hypochlorite, and sodium hypochlorite production device |
| CN109851137A (en) * | 2018-12-26 | 2019-06-07 | 国电新能源技术研究院有限公司 | A kind of desulfurization wastewater treatment system and method |
| CN111635058A (en) * | 2020-05-29 | 2020-09-08 | 中国电力工程顾问集团华北电力设计院有限公司 | Concentration and reduction device and process for desulfurization wastewater of power plant |
| CN115367930A (en) * | 2022-08-19 | 2022-11-22 | 国家能源集团新能源技术研究院有限公司 | Desulfurization wastewater treatment system and method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042417A (en) * | 2019-05-21 | 2019-07-23 | 中国水利水电科学研究院 | A kind of method and device of electrolytic seawater production javelle water |
-
2022
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2023
- 2023-04-28 WO PCT/CN2023/091495 patent/WO2024037041A1/en unknown
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070138020A1 (en) * | 2005-12-20 | 2007-06-21 | Shekar Balagopal | Electrolytic process to produce sodium hypochlorite using sodium ion conductive ceramic membranes |
| CN105314773A (en) * | 2014-07-10 | 2016-02-10 | 王辛平 | Wet desulphurization wastewater recycling method and apparatus thereof |
| CN205099427U (en) * | 2015-11-06 | 2016-03-23 | 山东大学 | System for utilize electrolysis electrodialysis to handle chlorion in wet flue gas desulfurization system |
| JP2018035024A (en) * | 2016-08-30 | 2018-03-08 | クボタ環境サ−ビス株式会社 | Method for producing sodium hypochlorite, and sodium hypochlorite production device |
| CN106567103A (en) * | 2016-11-08 | 2017-04-19 | 中广核工程有限公司 | Co-production method and system for sodium hypochlorite and high-purity hydrogen |
| CN106967996A (en) * | 2017-04-18 | 2017-07-21 | 碧海舟（北京）节能环保装备有限公司 | The hydrogen manufacturing of clean energy resource seawater and sodium hypochlorite system |
| CN109851137A (en) * | 2018-12-26 | 2019-06-07 | 国电新能源技术研究院有限公司 | A kind of desulfurization wastewater treatment system and method |
| CN111635058A (en) * | 2020-05-29 | 2020-09-08 | 中国电力工程顾问集团华北电力设计院有限公司 | Concentration and reduction device and process for desulfurization wastewater of power plant |
| CN115367930A (en) * | 2022-08-19 | 2022-11-22 | 国家能源集团新能源技术研究院有限公司 | Desulfurization wastewater treatment system and method |
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