CN115521011B - Shale gas produced water zero emission and resource utilization treatment system and method - Google Patents
Shale gas produced water zero emission and resource utilization treatment system and method Download PDFInfo
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- CN115521011B CN115521011B CN202211210039.7A CN202211210039A CN115521011B CN 115521011 B CN115521011 B CN 115521011B CN 202211210039 A CN202211210039 A CN 202211210039A CN 115521011 B CN115521011 B CN 115521011B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 338
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000926 separation method Methods 0.000 claims abstract description 88
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 80
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 238000003795 desorption Methods 0.000 claims abstract description 68
- 238000001179 sorption measurement Methods 0.000 claims abstract description 56
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 47
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 45
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 44
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 39
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 39
- 238000010521 absorption reaction Methods 0.000 claims abstract description 36
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 25
- 239000000126 substance Substances 0.000 claims abstract description 22
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 238000004064 recycling Methods 0.000 claims abstract description 17
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims description 69
- 239000007789 gas Substances 0.000 claims description 52
- 230000003647 oxidation Effects 0.000 claims description 52
- 238000007254 oxidation reaction Methods 0.000 claims description 52
- 238000001704 evaporation Methods 0.000 claims description 46
- 230000008020 evaporation Effects 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- 238000004519 manufacturing process Methods 0.000 claims description 36
- 239000003463 adsorbent Substances 0.000 claims description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000001728 nano-filtration Methods 0.000 claims description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001416 lithium ion Inorganic materials 0.000 claims description 20
- 239000012466 permeate Substances 0.000 claims description 20
- 239000012141 concentrate Substances 0.000 claims description 19
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 18
- 239000002250 absorbent Substances 0.000 claims description 17
- 230000002745 absorbent Effects 0.000 claims description 17
- 229920006395 saturated elastomer Polymers 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000008394 flocculating agent Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 238000004140 cleaning Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 7
- 239000011949 solid catalyst Substances 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000008235 industrial water Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical group [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- -1 bromine ions Chemical class 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000012459 cleaning agent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the technical field of shale gas produced water treatment, in particular to a shale gas produced water zero emission and resource utilization treatment system and method, wherein the treatment system comprises a hetero-salt separation unit, a bromine recovery unit, a lithium recovery unit and a sodium chloride salt separation unit; the shale gas produced water enters a mixed salt separation unit, a bromine recovery unit comprises a stripping tower, an absorption tower and a distillation tower, the water outlet of the mixed salt separation unit is connected with the water inlet of the stripping tower through a pipeline, the gas outlet of the stripping tower is communicated with the gas inlet of the absorption tower, the water outlet of the absorption tower is communicated with the distillation tower, the distillation tower separates bromine simple substances, and the water outlet of the stripping tower is communicated with the lithium recovery unit; the lithium recovery unit comprises an adsorption and desorption reactor, a precipitation reactor and a solid-liquid separation device. The treatment system and the method can treat the shale gas produced water to reach the standard and then recycle the shale gas produced water, realize zero emission, and also realize recycling of bromine, lithium carbonate and sodium chloride in the shale gas produced water.
Description
Technical Field
The invention relates to a shale gas produced water zero emission and resource utilization treatment system and method, and belongs to the technical field of shale gas produced water treatment.
Background
The method is characterized in that a large amount of produced water is produced in the shale gas exploitation process, the components of the produced water are complex, besides a large amount of pollutants such as Na +、Cl-、Ca2+、Mg2+ and COD, the produced water is rich in substances such as lithium and bromine, wherein the content of lithium ions is generally between 20 and 280mg/L, the content of bromine is generally between 50 and 450mg/L, the conventional treatment method is to treat the produced water by adopting an air floatation, coagulating sedimentation and filtering process and then reinject the produced water, or remove the pollutants in the water by adopting a pretreatment, membrane concentration, advanced oxidation and evaporation process and then discharge or recycle the produced water after reaching standards, and generally, the substances such as lithium and bromine in the water are not recycled and are directly treated as impurities.
In order to achieve the important targets of carbon peak, carbon neutralization and double carbon strategy, low-carbon economy becomes the main direction of current and future development in China, under the background, the development of new energy automobile industry is very rapid, the market demand of lithium batteries is in explosive growth, at present, the domestic lithium carbonate price is about 40-50 ten thousand/ton, the existing lithium carbonate is mainly obtained by two modes of extracting lithium from ores and extracting lithium from salt lakes, and the supply and the demand are obvious.
Meanwhile, in recent years, bromine is widely applied to fields of flame retardants, medicines, pesticides, military industry and the like as an important chemical raw material, the demand of the bromine is suddenly increased along with the development of global industry, and obviously bromine resources in China are also very short, the price of the bromine is about 5 ten thousand per ton at present, and the existing bromine is generally obtained through underground brine and concentrated seawater, so that the preparation efficiency is low, and the production cost is high.
The extraction of lithium carbonate and bromine has great industrial value by combining the current problem of the treatment of the produced water and the current problem of lack of lithium and bromine resources in China, and a treatment technology of zero emission and resource utilization of shale gas produced water is necessary to be designed to solve the problems.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a shale gas produced water zero-emission and resource utilization treatment system and method, which can realize the recycling of bromine, lithium carbonate and sodium chloride in shale gas produced water, extract substances capable of being recycled in water to the greatest extent and reduce the production cost.
The technical scheme for solving the technical problems is as follows: the shale gas produced water zero emission and resource utilization treatment system comprises a mixed salt separation unit, a bromine recovery unit, a lithium recovery unit and a sodium chloride salt separation unit; shale gas produced water enters the impurity salt separation unit, and effluent water of the impurity salt separation unit enters the bromine recovery unit;
The bromine recovery unit comprises a stripping tower, an absorption tower and a distillation tower, wherein the effluent of the impurity salt separation unit is connected with the water inlet of the stripping tower through a pipeline, the gas outlet of the stripping tower is communicated with the gas inlet of the absorption tower, the water outlet of the absorption tower is communicated with the distillation tower, the distillation tower separates bromine simple substances, and the water outlet of the stripping tower is communicated with the lithium recovery unit;
The lithium recovery unit comprises an adsorption and desorption reactor, a precipitation reactor and a solid-liquid separation device, wherein the water outlet of the stripping tower is communicated with the water inlet of the adsorption and desorption reactor, adsorption water produced in the adsorption and desorption reactor enters the sodium chloride salt separation unit, desorption liquid in the adsorption and desorption reactor enters the precipitation reactor, the water outlet of the precipitation reactor is communicated with the solid-liquid separation device, lithium carbonate is separated by the solid-liquid separation device, the water outlet of the solid-liquid separation device is communicated with the sodium chloride salt separation unit, and sodium chloride salt is separated by the sodium chloride salt separation unit.
Further, the pretreatment system comprises a pretreatment unit, the pretreatment unit comprises a pretreatment reactor, a water inlet of the pretreatment reactor is communicated with a shale gas raw water tank through a pump, a demulsifier and a flocculating agent are added into the pretreatment reactor, a water outlet of the pretreatment reactor is communicated with a pretreatment water production tank, and the pretreatment water production tank is communicated with the impurity salt separation unit.
Further, the impurity salt separation unit comprises a nanofiltration separation device, a salt separation water production tank, an evaporation concentration device and a drying device, wherein the pretreatment water production tank is communicated with the nanofiltration separation device through a pump, the permeate liquid of the nanofiltration separation device enters the salt separation water production tank, the salt separation water production tank is communicated with the stripping tower through the pump, the concentrate of the nanofiltration separation device enters the evaporation concentration device for concentration treatment, and the concentrate enters the drying device for drying treatment after being treated by the evaporation concentration device, so that the separated impurity salt is obtained.
Preferably, the drying device is a vacuum low-temperature dryer, the material is driven by a screw to move and dry, the temperature in the vacuum low-temperature dryer is 37-55 ℃, and the vacuum degree is-90-70 kPa.
Further, chlorine is introduced into the stripping tower, air is introduced into the stripping tower, free bromine is blown into the absorption tower, and the absorption tower is used for absorbing bromine into solution by spraying sodium carbonate solution as an absorbent.
The water outlet of the absorption tower is communicated with the inlet of the absorption saturated water tank, sulfuric acid is added into the absorption saturated water tank, the water outlet of the absorption saturated water tank is communicated with the distillation tower through a pump, and bromine in the solution is distilled out by the distillation tower to obtain bromine.
Introducing chlorine into wastewater containing bromide ions to displace bromine, blowing out the bromine by using air, absorbing the bromine by using sodium carbonate aqueous solution, acidifying the solution by using sulfuric acid to obtain bromine simple substance and water, and purifying the bromine by distillation. The method involves a reaction ：①Cl2+2Br-＝Br2+2Cl-;②3Br2+3CO3 2-＝BrO3-+5Br-+3CO2↑;③BrO3-+5Br-+6H+＝3Br2+3H2O. in which the molar ratio of Br 2, sodium carbonate and sulfuric acid is 1 (1-2): (1-2).
Further, the chlorine gas in the stripping tower is introduced in an amount which is 1.1 to 1.3 times of the mole fraction of the bromide ions.
Further, the water outlet of the stripping tower is communicated with the water inlet of the adsorption and desorption reactor through a bromine removal water production tank and a pump, an adsorbent is placed in the adsorption and desorption reactor, the adsorbent adsorbs lithium ions in water, the produced water adsorbed by the adsorbent enters a sodium chloride salt separation unit through a lithium removal water production tank, the adsorbed adsorbent is desorbed by a desorption agent to obtain a lithium-rich desorption liquid, the lithium-rich desorption liquid enters a precipitation reactor, sodium carbonate solution is added into the precipitation reactor to obtain lithium carbonate suspension, the lithium carbonate suspension enters a solid-liquid separation device for treatment to obtain a lithium carbonate product, and the effluent of the solid-liquid separation device enters the lithium removal water production tank.
Furthermore, the adsorption and desorption reactor adopts a mode of alternately running two by two and two strings, and two sections of equipment alternately run to ensure continuous running
Further, the sodium chloride salt separation unit comprises an oxidation reactor, an oxidation water production tank, membrane concentration equipment and an evaporation reactor;
And the water in the lithium removal water production tank enters an oxidation reactor, an oxidant is added into the oxidation reactor for oxidation treatment to obtain oxidation water production, a water outlet of the oxidation reactor is communicated with the oxidation water production tank, the water in the oxidation water production tank enters a membrane concentration device for concentration, the concentrated solution of the membrane concentration device enters an evaporation reactor, and the evaporation reactor performs evaporation treatment to obtain a sodium chloride product.
Furthermore, HCFenton oxidation is adopted in the oxidation reactor, the oxidant is hydrogen peroxide, the specific oxidation process is to add hydrogen peroxide, catalytic oxidation is carried out under the action of a solid catalyst, the solid catalyst is an alumina-based catalyst, and the main active components are metal salts such as manganese, iron, copper, nickel and the like. The solid catalyst is directly filled in an oxidation reactor, the filling ratio is 40-60%, and hydrogen peroxide is used for preparing the catalyst: the mass ratio of DeltaCOD is (1-2): 1, deltaCOD represents the amount of COD consumed in the oxidation process.
Further, the evaporation reactor is an MVR evaporator, stock solution is added from an upper tube box of the heat exchanger, materials are distributed into each heat exchange tube through a liquid distributor, a uniform liquid film is formed along the inner wall of the heat exchange tube, and the liquid film in the tube is heated by heating steam of a shell side in the downward flow process, flows downwards and boils and evaporates. The materials at the bottom end of the heat exchange tube become concentrated solution and secondary steam. The concentrated solution falls into a lower pipe box, and the secondary steam enters a gas-liquid separator. Liquid droplets entrained by the secondary steam in the gas-liquid separator are removed, pure secondary evaporation is conveyed from the separator to the compressor, and the compressor compresses the secondary steam and conveys the compressed secondary steam as heating steam to the shell side of the heat exchanger for being used as a heat source of the evaporator, so that continuous evaporation is realized.
Further, the membrane concentration equipment comprises a DTRO membrane device, a DTRO water producing tank, a DTRO concentration tank, an RO membrane device and an RO water producing tank;
The water inlet of the DTRO membrane device is communicated with the oxidation water producing tank through a pump, the produced water of the DTRO membrane device enters the DTRO water producing tank, the concentrated solution of the DTRO membrane device enters the DTRO concentration tank, the DTRO water producing tank is communicated with the water inlet of the RO membrane device through the pump, the produced water of the RO membrane device enters the RO water producing tank, the concentrated solution of the RO membrane device returns to the oxidation water producing tank, the DTRO concentration tank is communicated with the evaporation reactor through the pump, and the condensed water of the evaporation reactor enters the DTRO water producing tank.
Further, the nanofiltration separation device and the DTRO membrane device are both disc-type structures, the molecular weight cut-off of the DTRO is 120-150 daltons, the operating pressure is 45-90bar, the molecular weight cut-off of the nanofiltration device is 150-300, and the operating pressure is 25-70bar.
Furthermore, the DTRO membrane device adopts a high-pressure reverse osmosis membrane, the disc-tube type reverse osmosis membrane has high desalination rate and anti-pollutant performance, small molecular organic matters, ammonia nitrogen, chlorides and the like in water can be trapped in concentrated solution under the operating pressure condition of 20-90bar, a large amount of water molecules and a small amount of small molecular substances permeate through the membrane to form produced water, the recovery rate of the produced water reaches 60-80%, and the produced water is collected and then recycled to the RO membrane device at the rear end.
Further, the RO membrane device adopts a roll type membrane, the interception and separation amount is 100-130, and the system operating pressure is 6-40bar. The small molecular substances in the permeate water produced by the DTRO membrane device are intercepted, the recovery rate can reach more than 90 percent, and the produced water of the coiled membrane can be directly recycled after being collected for production.
Furthermore, the nanofiltration separation device, the DTRO membrane device and the RO membrane device are all provided with a flushing system and a chemical cleaning system, the flushing system is used for flushing with clear water when the equipment is stopped, the flushing time is 20 minutes, the flushing period is 1-3 days, the chemical cleaning system is used for chemically cleaning the equipment by using a medicine agent when the equipment is blocked, the chemical agent comprises an acidic cleaning agent and an alkaline cleaning agent, and the chemical cleaning period is 20-30 days.
The invention also discloses a shale gas produced water zero emission and resource utilization treatment method, which comprises the following steps:
S1, introducing shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier and a flocculating agent, and removing solid suspended matters and oil in the shale gas produced water to obtain pretreated produced water;
S2, introducing the pretreated produced water into a salt separation unit, and concentrating COD, ca 2+、Mg2+、SO4 2- and the like in the pretreated produced water to obtain a permeate and a concentrate;
s3, drying the concentrated solution in the step S2 to obtain solid residues of the mixed salt;
s4, introducing the permeate liquid in the step S2 into a stripping tower for stripping to obtain bromine-containing air and bromine-removing produced water;
s5, introducing the bromine-containing air in the step S4 into an absorption tower, spraying the bromine-containing air by using an absorbent, and dissolving bromine in the bromine-containing air into the absorbent to obtain a saturated absorbent;
S6, introducing the saturated absorbent in the step S5 into a distillation tower, adding a reactant, displacing bromine in water, and evaporating to obtain bromine; the reactant is sulfuric acid.
S7, introducing the bromine-removed produced water in the step S4 into an adsorption and desorption reactor, and adsorbing lithium ions in the bromine-removed produced water by using an adsorbent to obtain adsorbed produced water;
s8, adding the adsorbent subjected to adsorption in the step S7 for desorption to obtain a lithium-rich desorption solution;
s9, introducing the lithium-rich desorption solution in the step S8 into a precipitation reactor, and adding a sodium carbonate solution to obtain a lithium carbonate suspension; the addition amount of Na 2CO3 is 110-150% of the theoretical addition amount, the stirring speed is 600rpm, the reaction temperature is 80 ℃, and the concentration of LiCl solution is 3-5mol/L;
s10, introducing the lithium carbonate suspension in the step S9 into a solid-liquid separation device, and separating the lithium carbonate suspension into solid lithium carbonate and filtrate;
s11, introducing the adsorption produced water in the step S7 into an oxidation reactor, and oxidizing organic matters in the water to obtain oxidation produced water;
S12, adding a reducing agent into the oxidized water produced in the step S11 for reduction, and then, introducing the reduced water into a DTRO membrane device to concentrate salt to obtain a DTRO permeate and a DTRO concentrate; the DTRO permeate enters an RO membrane device, ions in water are further filtered out to obtain RO permeate and RO concentrate, the RO concentrate is continuously pumped to the front end of the DTRO membrane for treatment, and the RO membrane is used for recycling after producing a hydration lattice; the reducing agent is sodium sulfite or sodium bisulfite, and the adding amount of the reducing agent is 10-30mg/L.
And S13, introducing the DTRO concentrated solution in the step S12 into an evaporation reactor to obtain sodium chloride.
In the step S1, the flocculant is polyaluminum chloride and polyacrylamide;
Introducing shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier, wherein the adding amount of the demulsifier is 10-80mg/L, separating oil and water in the emulsified oil-water mixed solution by utilizing the chemical action of the demulsifier, reacting for 0.2-0.4 h, and separating oil in the water from the produced water; then adding polyaluminum chloride, wherein the usage amount of the polyaluminum chloride is 25-35mg/L, after reacting for 0.1-0.3h, separating mud from water, the water becomes clear, adding polyacrylamide, wherein the addition amount of the polyacrylamide is 0.4-0.5mg/L, after reacting for 0.1-0.3h, separating mud from water is more obvious, and the oil content of the produced water is reduced by at least 90% after filtering.
Further, in the step S5, the absorbent is sodium carbonate aqueous solution, and the concentration of the sodium carbonate aqueous solution is 8% -15%;
In step S6, the reactant is sulfuric acid, and concentrated sulfuric acid may be directly used as the sulfuric acid.
In step S7, the adsorbent is a manganese series lithium ion sieve adsorbent or an organic-inorganic nano hybrid adsorption material, the water content of the organic-inorganic nano hybrid adsorption material is 40.0-58.0%, the granularity range (0.315-1.25) is more than or equal to 95%, and the wet apparent density is 0.7-1.0g/mL; the adsorption capacity of the adsorbent for lithium ions is 30-40 mgLi/g;
In the step S7, the temperature of the adsorption and desorption reactor is 20-60 ℃, and the flow rate of bromine removal water produced in the adsorption and desorption reactor is 50 mL/(min.L) -150 mL/(min.L).
In step S8, a desorption operation is performed by using a desorption agent, wherein the desorption agent is any one of hydrochloric acid, nitric acid, sulfuric acid and ammonium sulfate aqueous solution, the concentration of the desorption agent is 0.4mol/L-1mol/L, and the desorption time is 1h. In the step S9, the concentration of the sodium carbonate solution is 8% -15%.
The beneficial effects of the invention are as follows:
1) The invention can treat the shale gas produced water to obtain the produced water which meets the standard of urban sewage recycling industrial water quality (GBT 19923-2005), and the produced water can be completely recycled after reaching the standard, and the pollutants in the water are finally dried to form solid residues, thereby realizing zero emission of the shale gas produced water.
2) According to the invention, lithium ions in shale gas produced water are prepared into lithium carbonate by a process method of adsorption and desorption and multi-effect precipitation reactors, so that the standard of lithium carbonate (GB/T11075-2013) is met; bromine ions in shale gas produced water are prepared into bromine by a process method of a stripping tower, an absorption tower and a distillation tower, so that the bromine meets the standard of industrial bromine (QB 2021-1994); and evaporating NaCl in shale gas produced water to obtain a NaCl salt product by the DTRO concentrated solution through an MVR evaporation process method, wherein the NaCl salt product meets the first-grade industrial salt standard of refining in industrial salt (GB/T5462-2015). According to the invention, the above 3 chemical products are extracted from shale gas wastewater to the greatest extent, so that waste is changed into valuable, the resource utilization is realized, and the production cost is reduced.
3) The mode of two-to-two series alternating operation is adopted in the lithium adsorption and desorption process, so that the service life of equipment is prolonged, the defect that lithium ions cannot be adsorbed during desorption is avoided, continuous production/operation is realized, and the production efficiency is improved.
Drawings
FIG. 1 is a schematic diagram of the processing system of embodiment 1;
FIG. 2 is a process flow diagram of the treatment method described in example 1;
In the figure, 1, a shale gas raw water tank; 2. a pretreatment reactor; 3. pretreating a water producing tank; 4. nanofiltration separation device; 5. salt separating water producing tank; 6. an evaporation concentration device; 7. a drying device; 8. a stripping tower; 9. an absorption tower; 10. an absorption saturated water tank; 11. a distillation column; 12. removing bromine to produce water tank; 13. an adsorption and desorption reactor; 14. a precipitation reactor; 15. a solid-liquid separation device; 16. a lithium removal water producing tank; 17. a DTRO membrane device; 18. a DTRO water producing tank; 19. a DTRO concentration tank; 20. RO membrane device; 21. RO produces the water pitcher; 22. an oxidation reactor; 23. oxidizing a water producing tank; 24. the reactor was evaporated.
Detailed Description
The following describes the present invention in detail. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, so that the invention is not limited to the specific embodiments disclosed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The shale gas produced water zero emission and resource utilization treatment system comprises a pretreatment unit, a salt separation unit, a bromine recovery unit, a lithium recovery unit and a sodium chloride salt separation unit;
The pretreatment unit is provided with a shale gas produced water inlet, the effluent of the pretreatment unit is communicated with the impurity salt separation unit, and the effluent of the impurity salt separation unit enters the bromine recovery unit;
The bromine recovery unit comprises a stripping tower 8, an absorption tower 9 and a distillation tower 11, wherein the effluent of the impurity salt separation unit is connected with the water inlet of the stripping tower 8 through a pipeline, the air outlet of the stripping tower 8 is communicated with the air inlet of the absorption tower 9, the water outlet of the absorption tower 9 is communicated with the distillation tower 11, the distillation tower 11 separates bromine simple substances, and the water outlet of the stripping tower 8 is communicated with the lithium recovery unit;
The lithium recovery unit comprises an adsorption and desorption reactor 13, a precipitation reactor 14 and a solid-liquid separation device 15, the water outlet of the stripping tower 8 is communicated with the water inlet of the adsorption and desorption reactor 13, adsorption water produced in the adsorption and desorption reactor 13 enters a sodium chloride salt separation unit, desorption liquid in the adsorption and desorption reactor 13 enters the precipitation reactor 14, the water outlet of the precipitation reactor 14 is communicated with the solid-liquid separation device 15, lithium carbonate is separated by the solid-liquid separation device 15, the water outlet of the solid-liquid separation device 15 is communicated with the sodium chloride salt separation unit, and sodium chloride salt is separated by the sodium chloride salt separation unit.
In this embodiment, the pretreatment unit includes a pretreatment reactor 2, a water inlet of the pretreatment reactor 2 is communicated with a raw shale gas water tank 1 through a pump, a demulsifier and a flocculating agent are added into the pretreatment reactor 2, a water outlet of the pretreatment reactor 2 is communicated with a pretreatment water production tank 3, and the pretreatment water production tank 3 is communicated with the impurity salt separation unit.
In this embodiment, the salt separation unit includes nanofiltration separation device 4, salt separation water producing tank 5, evaporation concentration device 6 and drying device 7, pretreatment water producing tank 3 passes through the pump intercommunication nanofiltration separation device 4, the permeate of nanofiltration separation device 4 enters into salt separation water producing tank 5, salt separation water producing tank 5 passes through the pump intercommunication stripping tower 8, the concentrate of nanofiltration separation device 4 enters into evaporation concentration device 6 carries out concentration treatment, and the concentrate is passed through evaporation concentration device 6 handles the back and gets into drying device 7 and carries out drying treatment, obtains the salt of the separation.
In this embodiment, chlorine is introduced into the stripping tower 8, and then air is introduced into the stripping tower 8 to blow free bromine into the absorption tower 9, wherein the absorption tower 9 sprays sodium carbonate solution as absorbent to absorb bromine into the solution.
The water outlet of the absorption tower 9 is communicated with the inlet of an absorption saturated water tank 10, sulfuric acid is added into the absorption saturated water tank 10, the water outlet of the absorption saturated water tank 10 is communicated with the distillation tower 11 through a pump, and bromine in the solution is distilled out by the distillation tower 11 to obtain bromine.
The specific principle is as follows: chlorine is introduced into wastewater containing bromide ions to displace bromine, then the bromine is blown out by air, and the bromine is absorbed by sodium carbonate aqueous solution. And finally, acidifying with sulfuric acid to obtain bromine simple substance and water, and purifying by distillation. In this example ：①Cl2+2Br-＝Br2+2Cl-;②3Br2+3CO3 2-＝BrO3-+5Br-+3CO2↑;③BrO3-+5Br-+6H+＝3Br2+3H2O., the reaction involved in this method was that the molar ratio of Br 2, sodium carbonate and sulfuric acid was 1:1.2:1.2, adding various substances according to the mole ratio.
In this embodiment, the water outlet of the stripping tower 8 is connected to the water inlet of the adsorption and desorption reactor 13 through a bromine removal water producing tank 12 and a pump, an adsorbent is placed in the adsorption and desorption reactor 13, the adsorbent adsorbs lithium ions in water, the produced water adsorbed by the adsorbent enters a sodium chloride salt separation unit through a lithium removal water producing tank 16, the adsorbed adsorbent is desorbed by a desorbing agent to obtain a lithium-rich desorption liquid, the lithium-rich desorption liquid enters a precipitation reactor 14, a sodium carbonate solution is added into the precipitation reactor 14 to obtain a lithium carbonate suspension, the lithium carbonate suspension enters a solid-liquid separation device 15 for treatment to obtain a lithium carbonate product, and the effluent of the solid-liquid separation device 15 enters the lithium removal water producing tank 16. The solid-liquid separation device 15 is a centrifuge.
The adsorption-desorption reactor 13 is in a mode of two-in-two-series alternate operation, two sections of equipment alternate operation, continuous operation is guaranteed, the mode is that when equipment A is started, equipment B is standby, when the equipment A is desorbed after adsorption saturation, the equipment B is started, the equipment A is stopped for standby after desorption, when the equipment B is adsorbed and is completely waiting for desorption, the equipment A is started, two sets of equipment alternate operation, continuous operation is guaranteed, and the operation time conditions are as follows:
in this embodiment, the sodium chloride salt separation unit includes a membrane concentration device, an oxidation reactor 22, an oxidation water producing tank 23 and an evaporation reactor 24;
The water in the lithium removal water producing tank 16 enters an oxidation reactor 22, an oxidant is added into the oxidation reactor to perform oxidation treatment to obtain oxidation water producing tank 23, a water outlet of the oxidation reactor 22 is communicated with the oxidation water producing tank 23, the water in the oxidation water producing tank 23 enters a membrane concentration device to be concentrated, concentrated solution of the membrane concentration device enters an evaporation reactor 24, and the evaporation reactor 24 performs evaporation treatment to obtain a sodium chloride product.
The evaporation reactor 24 adopts a forced circulation evaporator (MVR evaporation crystallization), a regulator is needed to be added for evaporation water inflow to prevent foaming in the evaporator and the quality of condensed water exceeding standard, the regulator is hydrochloric acid or sodium hydroxide, the pH value of wastewater is controlled to be 4-7, the wastewater enters the evaporator to be evaporated under the temperature condition of 65-110 ℃, condensed water generated by evaporation is discharged from a top unit of the evaporator to a system, the temperature is reduced to below 35 ℃, and the condensed water enters the RO membrane device 20 to be recycled after being treated; the evaporated thick liquid (mother liquor) slurry is discharged from the bottom unit system, and the sodium chloride solid salt is obtained after drying.
In this embodiment, the membrane concentration device comprises a DTRO membrane device 17, a DTRO water producing tank 18, a DTRO concentration tank 19, a RO membrane device 20, and a RO water producing tank 21;
The water inlet of the DTRO membrane device 17 is communicated with the water producing tank 23 through a pump, the produced water of the DTRO membrane device 17 enters the DTRO water producing tank 18, the concentrated solution of the DTRO membrane device 17 enters the DTRO concentration tank 19, the DTRO water producing tank 18 is communicated with the water inlet of the RO membrane device 20 through a pump, the produced water of the RO membrane device 20 enters the RO water producing tank 21, the concentrated solution of the RO membrane device 20 returns to the water producing tank 23, the DTRO concentration tank 19 is communicated with the evaporation reactor 24 through a pump, and the condensed water of the evaporation reactor 24 enters the DTRO water producing tank 18.
The shale gas produced water zero emission and resource utilization treatment method comprises the following steps:
S1, introducing shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier and a flocculating agent, and removing solid suspended matters and oil in the shale gas produced water to obtain pretreated produced water;
s2, introducing the pretreated produced water into a salt separation unit, and concentrating COD, calcium, magnesium, sulfate radical and other divalent or more ions in the pretreated produced water to obtain a permeate and a concentrate;
s3, drying the concentrated solution in the step S2 to obtain solid residues of the mixed salt;
S4, introducing the permeate liquid in the step S2 into a stripping tower 8 for stripping to obtain bromine-containing air and bromine-removing produced water;
S5, introducing the bromine-containing air in the step S4 into an absorption tower 9, spraying the bromine-containing air by using an absorbent, and dissolving bromine in the bromine-containing air into the absorbent to obtain a saturated absorbent; the absorbent is sodium carbonate aqueous solution with the concentration of 10%;
s6, introducing the saturated absorbent in the step S5 into a distillation tower 11, adding sulfuric acid, replacing bromine in water, and evaporating to obtain bromine, wherein the sulfuric acid is concentrated sulfuric acid;
s7, introducing the bromine-removed produced water in the step S4 into an adsorption and desorption reactor 13, and adsorbing lithium ions in the bromine-removed produced water by using an adsorbent to obtain adsorbed produced water;
s8, adding the adsorbent subjected to adsorption in the step S7 for desorption to obtain a lithium-rich desorption solution;
S9, introducing the lithium-rich desorption solution in the step S8 into a precipitation reactor 14, detecting that the concentration of the lithium chloride solution in the lithium-rich desorption solution is 3.5mol/L, and adding a sodium carbonate aqueous solution, wherein the concentration of the sodium carbonate aqueous solution is 10%; controlling the stirring speed to be 600rpm, and the reaction temperature to be 80 ℃ to obtain lithium carbonate suspension, wherein the addition amount of Na 2CO3 is 110% of the theoretical reaction mass;
S10, introducing the lithium carbonate suspension in the step S9 into a solid-liquid separation device 15, and separating the lithium carbonate suspension into solid lithium carbonate and filtrate;
S11, introducing the adsorption produced water in the step S7 into an oxidation reactor 22, and oxidizing organic matters in the water to obtain oxidation produced water; wherein HCFenton oxidation (Heterogeneous Catalytic Fenton oxidation, i.e. heterogeneous catalytic Fenton oxidation) is adopted in the oxidation process, hydrogen peroxide is added in the oxidation process, catalytic oxidation is carried out under the action of a solid catalyst, the solid catalyst is an alumina-based catalyst (Shandong Senya environmental technology Co., ltd., catalyst specification: 3-6mm, carrier: porous load noble metal material with strength of more than 150N/particle and specific gravity of 1.2 kg/L), and the solid catalyst is directly filled in the oxidation reactor 22, wherein the filling ratio is 50%. Wherein, the mass ratio of the hydrogen peroxide to the delta COD is 1.5:1, and the delta COD represents the amount of COD consumed in the oxidation process.
S12, adding 20mg/L sodium sulfite reducing agent into the oxidized water produced in the step S11 for reduction, and then introducing the reduced water into a DTRO membrane device 17 to concentrate salt to obtain a DTRO permeate and a DTRO concentrate; the DTRO permeate enters an RO membrane device 20, ions in water are further filtered out to obtain RO permeate and RO concentrate, the RO concentrate is continuously pumped to the front end of the DTRO membrane for treatment, and the RO membrane is used for recycling after producing a hydration lattice;
And S13, introducing the DTRO concentrated solution in the step S12 into an evaporation reactor 24 to obtain sodium chloride.
In the step S1, shale gas produced water is introduced into a pretreatment unit for pretreatment, a demulsifier (JS-601A of Jiangsu water environmental protection technology Co., ltd.) is added, the addition amount of the demulsifier is 50mg/L, the reaction is carried out for 0.3h, and oil in the water is separated from the produced water; then adding polyaluminum chloride with the dosage of 30mg/L, reacting for 0.2h, separating mud from water, adding polyacrylamide with the dosage of 0.45mg/L, reacting for 0.2h, and filtering.
In the step S7, the adsorbent is an organic-inorganic nano hybrid adsorbing material HPL700 (manufacturer: jiangsu Hepu functional material Co., ltd.), the water content of the organic-inorganic nano hybrid adsorbing material is 40.0-58.0%, the granularity range (0.315-1.25) is more than or equal to 95%, and the wet apparent density is 0.7-1.0g/mL; the adsorption capacity of the adsorbent for lithium ions is 30-40 mgLi/g;
in the step S7, the temperature of the adsorption and desorption reactor 13 is 50 ℃, and the flow rate of bromine removal and water production in the adsorption and desorption reactor 13 is 100 mL/(min.L);
In the step S8, a desorption operation is performed by using a desorption agent, wherein the desorption agent is hydrochloric acid, and the concentration of the desorption agent is 0.8mol/L.
The treatment system and the process of the embodiment 1 are continuously and stably operated for 30 days, and the nanofiltration separation device 4 is cleaned.
The shale gas produced water treated in this example 1 had a conductivity of 45000us/cm, a total hardness of 4700mg/L, a lithium ion concentration of 125mg/L, a COD of 1150mg/L, an ammonia nitrogen of 20mg/L, an oil content of 310mg/L, an SS of 800mg/L, and a water amount of 1200 t/day.
After the treatment system and the treatment process of the embodiment 1 are adopted, the content of the final lithium carbonate is more than 99.5%, the reuse water meets the reuse index, and the inlet and outlet water quality is shown in the table 1:
TABLE 1 Water quality of Inlet and outlet Water from each Unit of example 1
As can be seen from the data in Table 1, after zero discharge treatment of shale gas produced water in example 1, the water quality of the produced water meets the recycling index of the standard of urban wastewater recycling Industrial Water quality (GBT 19923-2005), the produced water can be directly recycled, and meanwhile, the extracted lithium carbonate meets the standard of lithium carbonate (GB/T11075-2013).
Example 2
The shale gas produced water is recycled by adopting the same treatment system and process as in the embodiment 1, and the difference is that: in the step S7, the adsorbent is manganese-series lithium ion sieve adsorbent MnO 2·0.5H2 O.
After the treatment system and the treatment process of the example 2 are adopted, the content of the final lithium carbonate is more than 99.5%, the reuse water meets the reuse index, and the inlet and outlet water quality is shown in the table 2:
TABLE 2 Water quality of Inlet and outlet Water from each Unit of example 2
As can be seen from the data in Table 2, after zero discharge treatment of shale gas produced water in example 2, the water quality of the produced water meets the recycling index of the standard of urban wastewater recycling Industrial Water quality (GBT 19923-2005), the produced water can be directly recycled, and meanwhile, the extracted lithium carbonate meets the standard of lithium carbonate (GB/T11075-2013).
Comparative example 1
The shale gas produced water is recycled by adopting the same treatment system and process as in the embodiment 1, and the difference is that: in step S7, the adsorbent is cation resin 001 x 7 strong acid cation exchange resin (su run vast environmental protection technology ltd).
After the treatment system and the treatment process of the comparative example 1 are adopted, the content of the final lithium carbonate is 98.0%, the reuse water meets the reuse index, and the inlet and outlet water quality is shown in table 3:
TABLE 3 Water quality of the Inlet and outlet Water from the units of comparative example 1
As can be seen from the comparison of the data of comparative example 1 and example 1, the conventional adsorbent is used, the content of the recovered lithium salt is low, and the standard of lithium carbonate (GB/T11075-2013) cannot be met. Moreover, from the detection data of the water produced by removing lithium, the lithium in the shale gas produced water is not completely recovered in the comparative example 1, so that the organic-inorganic nano hybrid adsorption material is more beneficial to the recovery of lithium salt.
The organic-inorganic nano hybrid adsorption material HPL700 is prepared by depositing inorganic nano active materials into polymer pore canals through a liquid phase deposition technology, and the material adopts a lithium ion imprinting technology, so that the adsorbent has a memory effect on lithium ions, and the high selectivity of the adsorption material on the lithium ions is ensured. The polymer nano holes of the adsorption material form a limited space, and the formation of inorganic nano-sized particles is enhanced, so that the adsorption activity and the adsorption quantity of lithium are improved; in addition, the polymer has good anti-scouring performance and stable physicochemical property, ensures the excellent mechanical strength of the organic-inorganic nano hybrid adsorption material HPL700, and is more beneficial to recycling.
The general resin adsorption used in this comparative example 1 was such that the cation Na + in the resin material was exchanged with the cation in water, not only lithium ions, but also various cations such as Ca 2+、Mg2+ were exchanged simultaneously, and thus the final lithium salt product content was low.
Comparative example 2
The shale gas produced water is recycled by adopting the same treatment system and process as in the embodiment 1, and the difference is that: the pretreatment unit is not added, then the whole system treatment is carried out, and long-term operation shows that when the pretreatment system is not established, the chemical cleaning period of the membrane in the rear end nanofiltration salt separation device 4 is 0.5 day, and the effluent water quality data are shown in Table 4:
TABLE 2 Water quality of Inlet and outlet Water from each Unit of example 2
As can be seen from the cases of comparative example 2 and example 1: the shale gas produced water does not independently set up a pretreatment unit, but directly enters the rear end nanofiltration salt separating device 4, the chemical cleaning period is only 0.5 day, the membrane fouling is fast and serious, and the membrane fouling is difficult to clean thoroughly after the fouling, compared with 30 days in the embodiment 1, the standard of the urban sewage recycling industrial water quality (GBT 19923-2005) is obviously reduced, the produced water can be directly recycled, and therefore, the condition that a pretreatment system is not independently set up is explained, the final effluent water quality is not influenced, the chemical cleaning period is seriously shortened, the cleaning cost is increased, and the production is seriously influenced by equipment shutdown. Because the raw water of shale gas produced water contains more solid suspended matters and oil (as can be seen from the detection data of the raw water, SS can reach 800mg/L, COD is 1150mg/L, oil content is 310 mg/L), the aperture of a nanofiltration membrane used in a nanofiltration salt separation device is generally 1-2nm, and the solid suspended matters and oil in the system are all intercepted by the nanofiltration membrane, if the raw water is not pretreated, a large amount of solid suspended matters and oil are accumulated on the surface of the nanofiltration membrane, so that the nanofiltration membrane is blocked quickly, water permeation cannot be realized, chemical cleaning is needed to be continued, and therefore, the cleaning cost is increased.
The technical features of the above-described embodiments may be arbitrarily combined, and in order to simplify the description, all possible combinations of the technical features in the above-described embodiments are not exhaustive, 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.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the invention as defined in the appended claims.
Claims (8)
1. The shale gas produced water zero emission and resource utilization treatment system is characterized by comprising a hetero-salt separation unit, a bromine recovery unit, a lithium recovery unit and a sodium chloride salt separation unit; shale gas produced water enters the impurity salt separation unit, and effluent water of the impurity salt separation unit enters the bromine recovery unit;
the bromine recovery unit comprises a stripping tower (8), an absorption tower (9) and a distillation tower (11), wherein the effluent of the impurity salt separation unit is connected with the water inlet of the stripping tower (8) through a pipeline, the air outlet of the stripping tower (8) is communicated with the air inlet of the absorption tower (9), the water outlet of the absorption tower (9) is communicated with the distillation tower (11), the distillation tower (11) separates bromine simple substance, and the water outlet of the stripping tower (8) is communicated with the lithium recovery unit;
The lithium recovery unit comprises an adsorption and desorption reactor (13), a precipitation reactor (14) and a solid-liquid separation device (15), wherein the water outlet of the stripping tower (8) is communicated with the water inlet of the adsorption and desorption reactor (13), an adsorbent is placed in the adsorption and desorption reactor (13), the adsorbent adsorbs lithium ions in water, adsorption produced water in the adsorption and desorption reactor (13) enters a sodium chloride salt separation unit, desorption liquid in the adsorption and desorption reactor (13) enters the precipitation reactor (14), the water outlet of the precipitation reactor (14) is communicated with the solid-liquid separation device (15), lithium carbonate is separated by the solid-liquid separation device (15), the water outlet of the solid-liquid separation device (15) is communicated with the sodium chloride salt separation unit, and sodium chloride salt is separated by the sodium chloride salt separation unit;
The adsorbent is a manganese series lithium ion sieve adsorbent or an organic-inorganic nano hybrid adsorption material, the water content of the adsorbent is 40.0-58.0%, the granularity range (0.315-1.25) is more than or equal to 95%, and the wet apparent density is 0.7-1.0g/mL; the adsorption capacity of the adsorbent for lithium ions is 30-40 mgLi/g;
The pretreatment system comprises a pretreatment unit, the pretreatment unit comprises a pretreatment reactor (2), a water inlet of the pretreatment reactor (2) is communicated with a shale gas raw water tank (1) through a pump, a demulsifier and a flocculating agent are added into the pretreatment reactor (2), a water outlet of the pretreatment reactor (2) is communicated with a pretreatment water production tank (3), and the pretreatment water production tank (3) is communicated with the impurity salt separation unit;
The salt separating unit comprises a nanofiltration separating device (4), a salt separating water producing tank (5), an evaporation concentration device (6) and a drying device (7), wherein the pretreatment water producing tank (3) is communicated with the nanofiltration separating device (4) through a pump, the permeate liquid of the nanofiltration separating device (4) enters the salt separating water producing tank (5), the salt separating water producing tank (5) is communicated with the stripping tower (8) through the pump, the concentrated liquid of the nanofiltration separating device (4) enters the evaporation concentration device (6) for concentration treatment, and the concentrated liquid enters the drying device (7) for drying treatment after being treated by the evaporation concentration device (6), so that separated salt is obtained.
2. The shale gas produced water zero emission and recycling treatment system according to claim 1 is characterized in that chlorine is introduced into the stripping tower (8), then air is introduced into the stripping tower (8) to blow free bromine into the absorption tower (9), and the absorption tower (9) absorbs bromine into solution by spraying sodium carbonate solution as an absorbent;
the water outlet of the absorption tower (9) is communicated with the inlet of the absorption saturated water tank (10), sulfuric acid is added into the absorption saturated water tank (10), the water outlet of the absorption saturated water tank (10) is communicated with the distillation tower (11) through a pump, and bromine in the solution is distilled out by the distillation tower (11) to obtain bromine.
3. The shale gas produced water zero emission and recycling treatment system according to claim 1, wherein a water outlet of the stripping tower (8) is communicated with a water inlet of the adsorption and desorption reactor (13) through a bromine removal water producing tank (12) and a pump, produced water adsorbed by an adsorbent enters a sodium chloride salt separation unit through a lithium removal water producing tank (16), the adsorbed adsorbent is desorbed by a desorbing agent to obtain a lithium-rich desorption liquid, the lithium-rich desorption liquid enters a precipitation reactor (14), sodium carbonate solution is added into the precipitation reactor (14) to obtain lithium carbonate suspension, the lithium carbonate suspension enters a solid-liquid separation device (15) to be treated, a lithium carbonate product is obtained, and effluent of the solid-liquid separation device (15) enters the lithium removal water producing tank (16).
4. The shale gas produced water zero emission and recycling treatment system according to claim 3, wherein the sodium chloride salt separation unit comprises an oxidation reactor (22), an oxidation water production tank (23), membrane concentration equipment and an evaporation reactor (24);
The water in the lithium removal water production tank (16) enters an oxidation reactor (22) and is added with an oxidant for oxidation treatment to obtain oxidation water production, a water outlet of the oxidation reactor (22) is communicated with the oxidation water production tank (23), water in the oxidation water production tank (23) enters a membrane concentration device for concentration, concentrated solution of the membrane concentration device enters an evaporation reactor (24), and the evaporation reactor (24) is subjected to evaporation treatment to obtain a sodium chloride product.
5. The shale gas produced water zero emission and recycling treatment system according to claim 4, wherein the membrane concentration equipment comprises a DTRO membrane device (17), a DTRO water producing tank (18), a DTRO concentration tank (19), an RO membrane device (20) and an RO water producing tank (21);
The utility model discloses a water purification device, including water purification device, evaporation reactor (24), water purification device, pump, evaporation reactor (24), water purification device, pump intercommunication are passed through to oxidation water production jar (23) the water inlet of DTRO membrane device (17), the water production of DTRO membrane device (17) is entered into by the pump, the water production of DTRO membrane device (17) is entered into by the water pump DTRO membrane device (18) is entered into the water inlet of RO membrane device (20), the concentrate of RO membrane device (20) returns in the oxidation water production jar (23), the concentrated jar (19) of DTRO is passed through pump intercommunication evaporation reactor (24), the comdenstion water of evaporation reactor (24) enters into DTRO water production jar (18).
6. The shale gas produced water zero emission and resource utilization treatment method is characterized by comprising the following steps of:
S1, introducing shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier and a flocculating agent, and removing solid suspended matters and oil in the shale gas produced water to obtain pretreated produced water;
S2, introducing the pretreated produced water into a salt separation unit, and concentrating COD (chemical oxygen demand) and Ca 2+、Mg2+、SO4 2- in the pretreated produced water to obtain a permeate and a concentrate;
s3, drying the concentrated solution in the step S2 to obtain solid residues of the mixed salt;
S4, introducing the permeate liquid in the step S2 into a stripping tower (8) for stripping to obtain bromine-containing air and bromine-removing produced water;
S5, introducing the bromine-containing air in the step S4 into an absorption tower (9), spraying the bromine-containing air by using an absorbent, and dissolving bromine in the bromine-containing air into the absorbent to obtain a saturated absorbent;
s6, introducing the saturated absorbent in the step S5 into a distillation tower (11), adding a reactant, displacing bromine in water, and evaporating to obtain bromine;
S7, introducing the bromine-removed produced water in the step S4 into an adsorption and desorption reactor (13), and adsorbing lithium ions in the bromine-removed produced water by using an adsorbent to obtain adsorbed produced water;
s8, adding the adsorbent subjected to adsorption in the step S7 for desorption to obtain a lithium-rich desorption solution;
S9, introducing the lithium-rich desorption solution in the step S8 into a precipitation reactor (14), and adding a sodium carbonate solution to obtain a lithium carbonate suspension;
s10, introducing the lithium carbonate suspension in the step S9 into a solid-liquid separation device (15), and separating the lithium carbonate suspension into solid lithium carbonate and filtrate;
s11, introducing the adsorption produced water in the step S7 into an oxidation reactor (22) to oxidize organic matters in the water to obtain oxidation produced water;
S12, adding a reducing agent into the oxidized water produced in the step S11 for reduction, and then introducing the reduced water into a DTRO membrane device (17), and concentrating salt to obtain a DTRO permeate and a DTRO concentrate; the DTRO permeate enters an RO membrane device (20) to further remove ions in water to obtain RO permeate and RO concentrate, and the RO concentrate is continuously sent to the front end of the DTRO membrane for treatment, and the RO membrane is reused after producing a hydration lattice;
and S13, introducing the DTRO concentrated solution in the step S12 into an evaporation reactor (24) to obtain sodium chloride.
7. The shale gas produced water zero emission and recycling treatment method according to claim 6 is characterized in that in the step S1, shale gas produced water is introduced into a pretreatment unit for pretreatment, demulsifier is added for reaction for 0.2-0.4 h, and oil in the water is separated from the produced water; then adding polyaluminum chloride, wherein the usage amount of the polyaluminum chloride is 25-35mg/L, reacting for 0.1-0.3h, separating mud from water, adding polyacrylamide, and reacting for 0.1-0.3h, wherein the dosage of the polyacrylamide is 0.4-0.5 mg/L.
8. The shale gas produced water zero emission and recycling treatment method according to claim 6, wherein in the step S7, the temperature of the adsorption and desorption reactor (13) is 20-60 ℃, and the bromine removal and production water flow rate in the adsorption and desorption reactor (13) is 50 mL/(min.L) -150 mL/(min.L);
in the step S8, a desorption operation is performed by using a desorption agent, wherein the desorption agent is any one of hydrochloric acid, nitric acid, sulfuric acid and ammonium sulfate aqueous solution, and the concentration of the desorption agent is 0.4mol/L-1mol/L.
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