CN115521011A - 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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- CN115521011A CN115521011A CN202211210039.7A CN202211210039A CN115521011A CN 115521011 A CN115521011 A CN 115521011A CN 202211210039 A CN202211210039 A CN 202211210039A CN 115521011 A CN115521011 A CN 115521011A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 318
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000000926 separation method Methods 0.000 claims abstract description 87
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 77
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 76
- 238000003795 desorption Methods 0.000 claims abstract description 68
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 238000010521 absorption reaction Methods 0.000 claims abstract description 45
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 41
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 claims abstract description 27
- 238000011084 recovery Methods 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims description 71
- 238000004519 manufacturing process Methods 0.000 claims description 56
- 239000007789 gas Substances 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 54
- 230000003647 oxidation Effects 0.000 claims description 49
- 238000007254 oxidation reaction Methods 0.000 claims description 49
- 238000001704 evaporation Methods 0.000 claims description 44
- 230000008020 evaporation Effects 0.000 claims description 40
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 36
- 239000003463 adsorbent Substances 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 33
- 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 25
- 239000000126 substance Substances 0.000 claims description 21
- 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 18
- 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 17
- 239000000725 suspension Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
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- 239000000463 material Substances 0.000 claims description 13
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- 239000012141 concentrate Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical group [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 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
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 7
- 238000004140 cleaning Methods 0.000 description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 208000028659 discharge Diseases 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 238000011010 flushing procedure Methods 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
- 239000011777 magnesium Substances 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000000605 extraction Methods 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
- 239000010865 sewage Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 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
- 238000007664 blowing Methods 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000013043 chemical agent 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
- 239000000284 extract Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 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
- 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
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- -1 bromine ions Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003729 cation exchange resin 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
- 238000010586 diagram Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012535 impurity Substances 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
- 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
- 239000010413 mother solution Substances 0.000 description 1
- 239000010841 municipal wastewater 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
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 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
- 239000011550 stock solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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
-
- 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
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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
- 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
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to the technical field of shale gas produced water treatment, in particular to a zero-emission and resource utilization treatment system and a method for shale gas produced water, wherein the treatment system comprises a mixed salt separation unit, a bromine recovery unit, a lithium recovery unit and a sodium chloride salt separation unit; the produced water of the shale gas enters a miscellaneous salt separation unit, the bromine recovery unit comprises a stripping tower, an absorption tower and a distillation tower, the effluent of the miscellaneous 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 out bromine, 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 treatment method can treat the shale gas produced water to reach the standard and recycle the treated water, realize zero emission, and can also realize the recycling of bromine, lithium carbonate and sodium chloride in the shale gas produced water.
Description
Technical Field
The invention relates to a zero-emission and resource utilization treatment system and method for shale gas produced water, and belongs to the technical field of shale gas produced water treatment.
Background
The shale gas production process is accompanied by the production of a large amount of produced water, and the components of the produced water are complex except a large amount of Na + 、Cl - 、Ca 2+ 、Mg 2+ The method is characterized in that the method is rich in lithium, bromine and other substances besides pollutants such as COD (chemical oxygen demand), wherein the content of lithium ions is generally between 20 and 280mg/L, the content of bromine is between 50 and 450mg/L, the conventional treatment method is that the produced water is reinjected after being treated by the processes of air floatation, coagulating sedimentation and filtering, or the produced water is discharged or recycled after the pollutants in the water are removed by the processes of pretreatment, membrane concentration, advanced oxidation and evaporation, and the produced water reaches the standard, so that the substances of useful resources (such as lithium, bromine and the like) in the water are not recycled on the whole, but are directly used as impurities for treatment.
In order to realize the important targets of the double-carbon strategy of 'carbon peak reaching and carbon neutralization', low-carbon economy becomes the main direction of the current and future development of China, under the background, the development of the new energy automobile industry is very rapid, the market demand of lithium batteries is increased explosively, at present, the price of domestic lithium carbonate is as high as about 40-50 ten thousand per ton, the existing lithium carbonate is mainly obtained by two modes of ore lithium extraction and salt lake lithium extraction, and obviously, the supply and demand are not met.
Meanwhile, in recent years, bromine is widely applied to the fields of fire retardants, medicines, pesticides, military industry and the like as an important chemical raw material, the demand volume of the bromine increases suddenly along with the development of global industry, obviously, the bromine resource in China is also very short, the price of the existing bromine is as high as about 5 ten thousand per ton, the existing bromine is generally obtained through underground brine and concentrated seawater, the preparation efficiency is low, and the production cost is high.
In combination with the current situation of the treatment of the produced water and the current situation of the shortage of lithium and bromine resources in China, the extraction of lithium carbonate and bromine has great industrial value, and a treatment technology for zero discharge and resource utilization of the shale gas produced water needs to be designed to solve the problems.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a zero-emission and resource utilization treatment system and method for the produced water of shale gas, which can realize the recycling of bromine, lithium carbonate and sodium chloride in the produced water of shale gas, extract the recyclable substances in the water to the maximum extent and reduce the production cost.
The technical scheme for solving the technical problems is as follows: a zero-emission and resource utilization treatment system for shale gas produced water comprises a mixed salt separation unit, a bromine recovery unit, a lithium recovery unit and a sodium chloride salt separation unit; the shale gas produced water enters the miscellaneous salt separation unit, and the effluent of the miscellaneous salt separation unit enters the bromine recovery unit;
the bromine recovery unit comprises an air stripping tower, an absorption tower and a distillation tower, the effluent of the miscellaneous salt separation unit is connected with the water inlet of the air stripping tower through a pipeline, the air outlet of the air stripping tower is communicated with the air inlet of the absorption tower, the water outlet of the absorption tower is communicated with the distillation tower, the distillation tower separates out a bromine simple substance, and the water outlet of the air stripping tower is communicated with the lithium recovery unit;
the lithium recovery unit is including adsorbing desorption reactor, precipitation reactor and solid-liquid separation equipment, the delivery port intercommunication of air stripping tower adsorb desorption reactor water inlet, the absorption product water in the absorption desorption reactor enters into sodium chloride salt separating element, desorption liquid in the absorption desorption reactor enters into in the precipitation reactor, precipitation reactor's delivery port intercommunication solid-liquid separation equipment, solid-liquid separation equipment separates the lithium carbonate, solid-liquid separation equipment's delivery port intercommunication sodium chloride salt separating element, sodium chloride salt separating element separates the sodium chloride salt.
Furthermore, the treatment system comprises a pretreatment unit, the pretreatment unit comprises a pretreatment reactor, a water inlet of the pretreatment reactor is communicated with the shale gas raw water tank through a pump, a demulsifier and a flocculant 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 miscellaneous salt separation unit.
Further, the miscellaneous salt separation unit comprises a nanofiltration separation device, a salt separation water production tank, an evaporation concentration device and a drying device, the pretreatment water production tank is communicated with the nanofiltration separation device through a pump, permeate 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 a pump, concentrate of the nanofiltration separation device enters the evaporation concentration device for concentration treatment, and the concentrate is treated by the evaporation concentration device and then enters the drying device for drying treatment, so that separated miscellaneous 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.
Furthermore, chlorine gas is introduced into the stripping tower, air is introduced into the stripping tower to blow free bromine into the absorption tower, and the bromine is absorbed into the solution by spraying a sodium carbonate solution as an absorbent in the absorption tower.
And the water outlet of the absorption tower is communicated with the inlet of an 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 evaporated out by the distillation tower to obtain bromine.
Introducing chlorine into wastewater containing bromide ions to displace bromine, blowing out bromine with air, absorbing with sodium carbonate aqueous solution, acidifying with sulfuric acid to obtain bromine and water, and purifying by distillation. The method involves the following reactions: (1) cl 2 +2Br - ＝Br 2 +2Cl - ；②3Br 2 +3CO 3 2- ＝BrO 3- +5Br-+3CO 2 ↑；③BrO 3- +5Br - +6H + ＝3Br 2 +3H 2 And (O). Wherein, br 2 The molar ratio of the sodium carbonate to the sulfuric acid is 1 (1-2): (1-2).
Furthermore, the input amount of chlorine in the stripping tower is 1.1 to 1.3 times of the mole fraction of bromide ions.
Further, the delivery port of the air stripping tower is communicated with a pump through a bromine removal water production tank to adsorb a desorption reactor water inlet, an adsorbent is placed in an adsorption 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 solution, the lithium-rich desorption solution enters a precipitation reactor, a sodium carbonate solution is added into the precipitation reactor to obtain a lithium carbonate suspension, the lithium carbonate suspension enters a solid-liquid separation device to be treated to obtain a lithium carbonate product, and the water discharged from the solid-liquid separation device enters the lithium removal water production tank.
Furthermore, the adsorption and desorption reactor adopts a mode of two parallel-series alternate operation, and two sections of equipment alternately operate to ensure continuous operation
Further, the sodium chloride salt separation unit comprises an oxidation reactor, an oxidation water production tank, a membrane concentration device and an evaporation reactor;
and the water in the lithium-removing 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 membrane concentration equipment for concentration, a concentrated solution of the membrane concentration equipment enters an evaporation reactor, and the evaporation reactor is subjected to evaporation treatment to obtain a sodium chloride product.
Further, the oxidation reactor is oxidized by HCFenton, the oxidant is hydrogen peroxide, the specific oxidation process is that hydrogen peroxide is added, 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 the oxidation reactor, the filling ratio is 40-60%, and the hydrogen peroxide: the mass ratio of Δ COD is (1-2): 1, and Δ COD represents the amount of COD consumed in the oxidation process.
Furthermore, the evaporation reactor is an MVR evaporator, stock solution is added from a tube box on a heat exchanger, the material is distributed into each heat exchange tube through a liquid distributor, an even liquid film is formed along the inner wall of each heat exchange tube, and the liquid film in the tubes is heated by heating steam on a shell pass in the downflow process, flows downwards while boiling 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 channel, and the secondary steam enters a gas-liquid separator. Liquid droplets carried by secondary steam in the gas-liquid separator are removed, pure secondary evaporation is conveyed to a compressor from the separator, and the compressor compresses the secondary steam and conveys the compressed secondary steam as heating steam to a shell pass of a heat exchanger to be used as a heat source of an evaporator, so that continuous evaporation is realized.
Further, the membrane concentration equipment comprises a DTRO membrane device, a DTRO water production tank, a DTRO concentration tank, an RO membrane device and an RO water production tank;
the water pitcher is produced in the oxidation passes through the pump intercommunication the water inlet of DTRO membrane device, the product water of DTRO membrane device enters into the water pitcher is produced to the DTRO, the concentrate of DTRO membrane device enters into the concentrated jar of DTRO, the water pitcher is produced to the DTRO passes through the pump intercommunication the water inlet of RO membrane device, the product water of RO membrane device enters into the water pitcher is produced to the RO, the concentrate of RO membrane device returns to in the water pitcher is produced in the oxidation, the concentrated jar of DTRO passes through the pump intercommunication evaporation reactor, and the comdenstion water of evaporation reactor enters into the water pitcher is produced to the DTRO.
Furthermore, the nanofiltration separation device and the DTRO membrane device are both of 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 selects a high-pressure reverse osmosis membrane, the disc-tube reverse osmosis membrane has high desalination rate and anti-pollution 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 penetrate through the membrane to form produced water, the recovery rate of the produced water reaches 60-80%, and the produced water is collected and recycled to the RO membrane device at the rear end.
Furthermore, the RO membrane device adopts a roll-type membrane, the interception and separation capacity is 100-130, and the system operating pressure is 6-40bar. The small molecular substances in the permeate liquid produced water of the DTRO membrane device are intercepted, the recovery rate can reach more than 90 percent, and the produced water of the roll-type membrane can be directly recycled for production after being collected.
Furthermore, the nanofiltration separation device, the DTRO membrane device and the RO membrane device are provided with a flushing system and a chemical cleaning system, the flushing system is flushed with clear water when the equipment is shut down, the flushing time is 20 minutes, the flushing period is 1-3 days, the chemical cleaning system is used for chemically cleaning the equipment with a chemical agent when the equipment is dirty and 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 zero-emission and resource utilization treatment method for the shale gas produced water, which comprises the following steps:
s1, introducing the shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier and a flocculant, 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 mixed salt separation unit, and introducing COD (chemical oxygen demand) and Ca (calcium) in the pretreated produced water 2+ 、Mg 2+ 、SO 4 2- Concentrating to obtain permeate and concentrated solution;
s3, drying the concentrated solution obtained in the step S2 to obtain solid residues of mixed salts;
s4, introducing the permeate liquid obtained in the step S2 into a stripping tower for stripping to obtain bromine-containing air and bromine-removed 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 obtained in the step S5 into a distillation tower, adding a reactant, replacing bromine in water, and evaporating to obtain bromine; the reactant is sulfuric acid.
S7, introducing the bromine-removed water produced in the step S4 into an adsorption and desorption reactor, and adsorbing lithium ions in the bromine-removed water produced by using an adsorbent to obtain adsorbed water produced;
s8, adding the adsorbent which is completely adsorbed in the step S7 for desorption to obtain a lithium-rich desorption solution;
s9, introducing the lithium-rich desorption solution obtained in the step S8 into a precipitation reactor, and adding a sodium carbonate solution to obtain a lithium carbonate suspension; na (Na) 2 CO 3 The adding amount is 110-150% of the theoretical adding amount, the stirring speed is 600rpm, the reaction temperature is 80 ℃, and the concentration of the LiCl solution is 3-5mol/L;
s10, introducing the lithium carbonate suspension in the step S9 into a solid-liquid separation device, and dividing the lithium carbonate suspension into solid lithium carbonate and filtrate;
s11, introducing the water produced by adsorption in the step S7 into an oxidation reactor, and oxidizing organic matters in the water to obtain oxidized water;
s12, adding a reducing agent into the oxidation product water obtained in the step S11 for reduction, introducing the reduction product water into a DTRO membrane device, and concentrating salt to obtain DTRO permeate and DTRO concentrate; the DTRO permeate liquid enters an RO membrane device, ions in water are further filtered to obtain RO permeate liquid and RO concentrated liquid, the RO concentrated liquid is continuously sprayed to the front end of the DTRO membrane for treatment, and the water produced by the RO membrane is recycled after being qualified; the reducing agent is sodium sulfite or sodium bisulfite, and the addition amount of the reducing agent is 10-30mg/L.
And S13, introducing the DTRO concentrated solution obtained in the step S12 into an evaporation reactor to obtain sodium chloride.
Further, in the step S1, the flocculant adopted is polyaluminium chloride and polyacrylamide;
introducing the shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier, wherein the addition amount of the demulsifier is 10-80mg/L, separating oil and water in emulsified oil-water mixed liquid by utilizing the chemical action of the demulsifier, reacting for 0.2-0.4 h, and separating the oil in the water from the water; then adding polyaluminum chloride, wherein the using amount of the polyaluminum chloride is 25-35mg/L, reacting for 0.1-0.3h, separating mud from water, wherein the water can become clear, adding polyacrylamide, wherein the adding amount of the polyacrylamide is 0.4-0.5mg/L, reacting for 0.1-0.3h, more obviously separating mud from water, and reducing the oil content of the produced water by at least 90% after filtering.
Further, in step S5, the absorbent is a sodium carbonate aqueous solution, and the concentration of the sodium carbonate aqueous solution is 8% to 15%;
in step S6, the reactant is sulfuric acid, and concentrated sulfuric acid may be directly used as sulfuric acid.
Further, in step S7, the adsorbent is a manganese-based lithium ion sieve adsorbent or an organic-inorganic nano-hybrid adsorbent, the organic-inorganic nano-hybrid adsorbent contains 40.0-58.0% of water, has a particle size range (0.315-1.25) of not less than 95%, and has a wet apparent density of 0.7-1.0g/mL; the adsorption capacity to lithium ions is 30-40mgLi/g adsorbent;
in the step S7, the temperature of the adsorption and desorption reactor is 20-60 ℃, and the flow rate of the water produced by removing bromine in the adsorption and desorption reactor is 50 mL/(min. L) -150 mL/(min. L).
Further, in step S8, a desorption agent is used for desorption, the desorption agent is any one of aqueous solutions of hydrochloric acid, nitric acid, sulfuric acid and ammonium sulfate, the concentration of the desorption agent is 0.4mol/L-1mol/L, and the desorption time is 1h. In step S9, the concentration of the sodium carbonate solution is 8-15%.
The invention has the beneficial effects that:
1) According to the invention, through 'pretreatment + nanofiltration + oxidation + membrane concentration', the finally obtained produced water after shale gas produced water treatment can reach the standard of 'quality of municipal wastewater recycling industrial water' (GBT 19923-2005), all produced water can be recycled after reaching the standard, and pollutants in the water are finally dried into solid residues, so that zero emission of the shale gas produced water is realized.
2) According to the invention, lithium ions in the water produced from the shale gas are made into lithium carbonate by a process method of 'adsorption and desorption + multi-effect precipitation reactor', so that the lithium carbonate meets the standard of 'lithium carbonate' (GB/T11075-2013); bromine ions in the water produced by the shale gas are prepared into bromine by a process method of 'a stripping tower, an absorption tower and a distillation tower', and the bromine meets the standard of 'industrial bromine' (QB 2021-1994); and (3) evaporating NaCl in the shale gas produced water to obtain a NaCl salt product by the DTRO concentrated solution through an MVR evaporation process method, so that the standard of a refined industrial salt first-grade product in Industrial salt (GB/T5462-2015) is met. The invention extracts the 3 chemical products from the shale gas wastewater to the maximum extent, changes waste into valuable, realizes resource utilization and reduces production cost.
3) Two parallel-series alternating operation modes are adopted in the lithium adsorption and desorption process, the service life of the equipment is prolonged, the defect that lithium ions cannot be adsorbed during desorption is overcome, continuous production/operation is realized, and the production efficiency is improved.
Drawings
FIG. 1 is a schematic view of a processing system according to embodiment 1;
FIG. 2 is a process flow diagram of the treatment process described in example 1;
in the figure, 1, a shale gas crude water tank; 2. a pretreatment reactor; 3. pretreating a water production tank; 4. a nanofiltration separation device; 5. a 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. a bromine removal water production tank; 13. an adsorption and desorption reactor; 14. a precipitation reactor; 15. a solid-liquid separation device; 16. a lithium removal water production tank; 17. a DTRO membrane unit; 18. a DTRO water producing tank; 19. a DTRO concentration tank; 20. an RO membrane device; 21. an RO water producing tank; 22. an oxidation reactor; 23. oxidizing a water production tank; 24. the reactor was evaporated.
Detailed Description
The following is a detailed description of specific embodiments of the invention. This invention can be embodied in many different forms than those herein described and many modifications may be made by those skilled in the art without departing from the spirit of the invention and the scope of the invention is therefore 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.
A treatment system for zero discharge and resource utilization of shale gas produced water comprises a pretreatment unit, a mixed 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 mixed salt separation unit, and the effluent of the mixed salt separation unit enters the bromine recovery unit;
the bromine recovery unit comprises an air stripping tower 8, an absorption tower 9 and a distillation tower 11, the effluent of the miscellaneous salt separation unit is connected with the water inlet of the air stripping tower 8 through a pipeline, the air outlet of the air 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 out bromine, and the water outlet of the air stripping tower 8 is communicated with the lithium recovery unit;
the lithium recovery unit is including adsorbing desorption reactor 13, precipitation reactor 14 and solid-liquid separation equipment 15, the delivery port intercommunication of air stripping tower 8 adsorb desorption reactor 13 water inlet, it produces water and enters into sodium chloride salt separating element to adsorb the absorption in the desorption reactor 13, it enters into to adsorb desorption liquid in the desorption reactor 13 in the precipitation reactor 14, precipitation reactor 14's delivery port intercommunication solid-liquid separation equipment 15, lithium carbonate is separated out to solid-liquid separation equipment 15, solid-liquid separation equipment 15's delivery port intercommunication sodium chloride salt separating element, sodium chloride salt separating element separates out the sodium chloride salt.
In this embodiment, the pretreatment unit includes a pretreatment reactor 2, a water inlet of the pretreatment reactor 2 is communicated with a shale gas crude water tank 1 through a pump, a demulsifier and a flocculant are added into the pretreatment reactor 2, a water outlet of the pretreatment reactor 2 is communicated with a pretreatment water tank 3, and the pretreatment water tank 3 is communicated with the miscellaneous salt separation unit.
In this embodiment, the miscellaneous salt separation unit includes nanofiltration separation device 4, salt separation water production tank 5, evaporation concentration device 6 and drying device 7, pretreatment water production tank 3 communicates through the pump nanofiltration separation device 4, the permeate liquid of nanofiltration separation device 4 enters into salt separation water production tank 5, salt separation water production tank 5 communicates through the pump stripping tower 8, the concentrate of nanofiltration separation device 4 enters into evaporation concentration device 6 for concentration treatment, the concentrate is treated by evaporation concentration device 6 and then enters into drying device 7 for drying treatment, and the miscellaneous salt that separates is obtained.
In this embodiment, chlorine gas is introduced into the stripping tower 8, air is further introduced into the stripping tower 8 to blow free bromine into the absorption tower 9, and bromine is absorbed into the solution in the absorption tower 9 by spraying a sodium carbonate solution as an absorbent.
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 through the distillation tower 11 to obtain bromine.
The specific principle is as follows: introducing chlorine into the wastewater containing bromide ions to displace bromine, blowing out bromine with air, and absorbing with sodium carbonate aqueous solution. Finally, acidifying with sulfuric acid to obtain bromine and water, and purifying by distillation. The method involves the following reactions: (1) cl 2 +2Br - ＝Br 2 +2Cl - ；②3Br 2 +3CO 3 2- ＝BrO 3- +5Br-+3CO 2 ↑；③BrO 3- +5Br - +6H + ＝3Br 2 +3H 2 And O. In this example, br 2 And the molar ratio of sodium carbonate to sulfuric acid is 1:1.2:1.2, adding various substances according to a molar ratio.
In this embodiment, the delivery port of the air stripping tower 8 is communicated with the pump through the bromine removal water production tank 12 to adsorb the water inlet of the desorption reactor 13, an adsorbent is placed in the adsorption desorption reactor 13, the adsorbent adsorbs lithium ions in water, the produced water adsorbed by the adsorbent enters the sodium chloride salt separation unit through the lithium removal water production tank 16, the adsorbed adsorbent is desorbed by the desorbent to obtain a lithium-rich desorption solution, the lithium-rich desorption solution enters the 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 the 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 production tank 16. The solid-liquid separation device 15 is a centrifuge.
The adsorption and desorption reactor 13 is in a two-in-two series alternate operation mode, two sections of equipment alternately operate to ensure continuous operation, the mode is that when the equipment A is started, the equipment B is standby, when the equipment A is adsorbed and saturated and then is desorbed, the equipment B is started, the equipment A is stopped for standby after desorption is finished, when the equipment B is adsorbed and finishes waiting for desorption, the equipment A is started, two sets of equipment alternately operate to ensure continuous operation, 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 production tank 23, and an evaporation reactor 24;
and (3) feeding the water in the lithium removal water production tank 16 into an oxidation reactor 22, adding an oxidant into the oxidation reactor 22, carrying out oxidation treatment to obtain oxidation water production, communicating a water outlet of the oxidation reactor 22 with the oxidation water production tank 23, feeding the water in the oxidation water production tank 23 into a membrane concentration device for concentration, feeding the concentrated solution of the membrane concentration device into an evaporation reactor 24, and carrying out evaporation treatment on the evaporation reactor 24 to obtain a sodium chloride product.
The evaporation reactor 24 adopts a forced circulation evaporator (MVR evaporation crystallization), a regulator is added into evaporation inlet water to prevent bubbling in the evaporator and overproof water quality of condensed water, the regulator is hydrochloric acid or sodium hydroxide, the pH of the waste water is controlled to be 4-7, then the waste water enters the evaporator and is evaporated at the temperature of 65-110 ℃, the condensed water generated by evaporation is discharged out of a system from the top unit of the evaporator, and the condensed water enters the RO membrane device 20 after being cooled to below 35 ℃ and is recycled after being treated; and (4) discharging the evaporated concentrated solution (mother solution) slurry from the bottom unit out of the system, and drying to obtain the sodium chloride solid salt.
In this embodiment, the membrane concentration apparatus includes a DTRO membrane device 17, a DTRO product water tank 18, a DTRO concentration tank 19, an RO membrane device 20, and an RO product water tank 21;
the oxidation product water tank 23 is communicated with a water inlet of the DTRO membrane device 17 through a pump, the product water of the DTRO membrane device 17 enters the DTRO product water tank 18, the concentrated solution of the DTRO membrane device 17 enters the DTRO concentrated tank 19, the DTRO product water tank 18 is communicated with a water inlet of the RO membrane device 20 through a pump, the product water of the RO membrane device 20 enters the RO product water tank 21, the concentrated solution of the RO membrane device 20 returns to the oxidation product water tank 23, the DTRO concentrated tank 19 is communicated with the evaporation reactor 24 through a pump, and the condensed water of the evaporation reactor 24 enters the DTRO product water tank 18.
The zero-emission and resource utilization treatment method for the shale gas produced water comprises the following steps:
s1, introducing the shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier and a flocculant, 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 mixed salt separation unit, and concentrating bivalent and higher ions such as COD (chemical oxygen demand) and calcium, magnesium, sulfate radicals and the like in the pretreated produced water to obtain a permeate and a concentrated solution;
s3, drying the concentrated solution obtained in the step S2 to obtain solid residues of the miscellaneous salt;
s4, introducing the permeate liquid obtained in the step S2 into a stripping tower 8 for stripping to obtain bromine-containing air and bromine-removed 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 a sodium carbonate aqueous solution with the concentration of 10 percent;
s6, introducing the saturated absorbent obtained 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 water product obtained in the step S4 into an adsorption and desorption reactor 13, and adsorbing lithium ions in the bromine-removed water product by using an adsorbent to obtain adsorbed water product;
s8, adding the adsorbent which is completely adsorbed in the step S7 for desorption to obtain a lithium-rich desorption solution;
s9, introducing the lithium-rich desorption solution obtained in the step S8 into a precipitation reactor 14, detecting that the concentration of a 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 a lithium carbonate suspension, wherein Na is contained in the lithium carbonate suspension 2 CO 3 The adding amount is 110 percent of the theoretical reaction mass;
s10, introducing the lithium carbonate suspension in the step S9 into a solid-liquid separation device 15, and dividing the lithium carbonate suspension into solid lithium carbonate and filtrate;
s11, introducing the water produced by adsorption in the step S7 into an oxidation reactor 22, and oxidizing organic matters in the water to obtain oxidized water; the oxidation process adopts HCFenton oxidation (Heterogeneous Catalytic Fenton oxidation), the oxidation process is to add hydrogen peroxide and carry out Catalytic oxidation under the action of a solid catalyst, the solid catalyst is an alumina-based catalyst (Shandong Senyang environmental technology limited, the specification of the catalyst is 3-6mm, the carrier is a porous loaded noble metal material, the strength is more than 150N/particle, and the specific gravity is 1.2 kg/L), and the solid catalyst is directly filled in the oxidation reactor 22, and the filling ratio is 50%. Wherein the mass ratio of hydrogen peroxide to Δ COD is 1.5.
S12, adding 20mg/L of sodium sulfite reducing agent into the oxidation product water in the step S11 for reduction, introducing into a DTRO membrane device 17, and concentrating salt to obtain a DTRO permeating liquid and a DTRO concentrated liquid; the DTRO permeate enters an RO membrane device 20, ions in water are further filtered to obtain RO permeate and RO concentrated liquid, the RO concentrated liquid is continuously sprayed to the front end of the DTRO membrane for treatment, and the water produced by the RO membrane is recycled after being qualified;
and S13, introducing the DTRO concentrated solution in the step S12 into an evaporation reactor 24 to obtain sodium chloride.
In the step S1, the shale gas produced water is introduced into a pretreatment unit for pretreatment, a demulsifier (JS-601A of Jiangsu Lishui environmental protection science and technology Limited company) 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 polyaluminium chloride with the usage amount of 30mg/L for reaction for 0.2h, separating mud from water, then adding polyacrylamide with the dosage of 0.45mg/L for reaction for 0.2h, and filtering.
In step S7, the adsorbent is an organic-inorganic nano-hybrid adsorbing material HPL700 (manufacturer: jiangsu Hepu functional materials Co., ltd.), the water content of the organic-inorganic nano-hybrid adsorbing material is 40.0-58.0%, the particle size 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 to lithium ions is 30-40mgLi/g adsorbent;
in the step S7, the temperature of the adsorption and desorption reactor 13 is 50 ℃, and the flow rate of the water produced by removing bromine in the adsorption and desorption reactor 13 is 100 mL/(min · L);
in the step S8, a desorption agent is used for desorption operation, wherein the desorption agent is hydrochloric acid, and the concentration of the desorption agent is 0.8mol/L.
The treatment system and process of example 1 were continuously and stably operated for 30 days, and the nanofiltration separation device 4 was cleaned.
The conductivity of the shale gas produced water treated in the embodiment 1 is 45000us/cm, the total hardness is 4700mg/L, the lithium ion concentration is 125mg/L, the COD is 1150mg/L, the ammonia nitrogen is 20mg/L, the oil content is 310mg/L, the SS is 800mg/L, and the water content is 1200 t/day.
After the treatment system and process of this example 1 were adopted, the final lithium carbonate content was > 99.5%, the reuse water satisfied the reuse index, and the inlet and outlet water quality was as shown in table 1:
TABLE 1 quality of inlet and outlet water of each unit of example 1
As can be seen from the data in table 1, after the zero discharge treatment of the shale gas produced water in example 1, the quality of the produced water meets the reuse index of the urban sewage recycling industrial water quality standard (GBT 19923-2005), and can be directly reused, and meanwhile, the extracted lithium carbonate meets the lithium carbonate standard (GB/T11075-2013).
Example 2
The shale gas produced water is subjected to resource utilization treatment by adopting the same treatment system and process as in the embodiment 1, and the difference is that: in step S7, the adsorbent is manganese-based lithium ion sieve adsorbent MnO 2 ·0.5H 2 O。
After the treatment system and process of example 2 were used, the final lithium carbonate content was > 99.5%, the reuse water met the reuse index, and the inlet and outlet water quality is shown in table 2:
table 2 water quality of inlet and outlet water of each unit of example 2
As can be seen from the data in table 2, after the zero discharge treatment of the shale gas produced water in example 2, the quality of the produced water meets the reuse index of the urban sewage recycling industrial water quality standard (GBT 19923-2005), and can be directly reused, and meanwhile, the extracted lithium carbonate meets the lithium carbonate standard (GB/T11075-2013).
Comparative example 1
The shale gas produced water is subjected to resource utilization treatment 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 × 7 strong acid cation exchange resin (environmental protection technologies ltd., tsuzhou lube 2815634.
After the treatment system and process of the comparative example 1 were adopted, the final lithium carbonate content was 98.0%, the reuse water satisfied the reuse index, and the inlet and outlet water quality was as shown in table 3:
TABLE 3 quality of inlet and outlet water of each unit of comparative example 1
As can be seen from the comparison of the data of comparative example 1 and example 1, the recovered lithium salt content is low by using the conventional adsorbent, and the standard of lithium carbonate (GB/T11075-2013) cannot be met. Moreover, it can be seen from the detection data of water produced by removing lithium, that lithium in the shale gas produced water is not completely recovered in the comparative example 1, and it can be seen that the organic-inorganic nano hybrid adsorbing material is more beneficial to the recovery of lithium salt.
The organic-inorganic nano hybrid adsorbing material HPL700 is prepared by depositing an inorganic nano active material into a polymer pore channel by a liquid phase deposition technology, and the material uses a lithium ion imprinting technology, so that the adsorbing agent has a memory effect on lithium ions, and the high selectivity of the adsorbing material on the lithium ions is ensured. The polymer nano-pores of the adsorbing 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 adsorbing material HPL700, and is more beneficial to recycling.
The adsorption of the conventional resin used in this comparative example 1 was carried out by the cation Na in the resin material + Exchange with cations in water, not only lithium ions, but also Ca 2+ 、Mg 2+ And the various cations are not selective, thereby leading to low content of the final lithium salt product.
Comparative example 2
The shale gas produced water is subjected to resource utilization treatment by adopting the same treatment system and process as in the embodiment 1, and the difference is that: the pretreatment unit is not added, the membrane is treated by the integral system, and the long-term operation shows that when the pretreatment system is not set up, the chemical cleaning period of the membrane in the rear-end nanofiltration salt separation device 4 is 0.5 day, and the water quality data of effluent is shown in table 4:
table 2 water quality of inlet and outlet water of each unit of example 2
As can be seen from the cases of comparative example 2 and example 1: the shale gas produced water directly enters the rear-end nano-filtration salt separation device 4 without independently establishing a pretreatment unit, the chemical cleaning period is only 0.5 day, the membrane fouling is rapid and serious, and the membrane fouling is difficult to clean thoroughly after fouling, compared with 30 days in the embodiment 1, the chemical cleaning period is obviously reduced, but the effluent can still meet the standard of urban sewage recycling industrial water quality (GBT 19923-2005) and can be directly recycled, so that the pretreatment system is not independently established, the final effluent quality is not influenced, the chemical cleaning period is seriously shortened, the cleaning cost is increased, and the equipment shutdown seriously influences the production. The raw water of the shale gas produced water contains more solid suspended matters and oil (the detection data of the raw water can also show that SS can reach 800mg/L, COD is 1150mg/L and oil content is 310 mg/L), the aperture of a nanofiltration membrane used in a nanofiltration salt separation device is generally 1-2nm, the solid suspended matters and the oil in the system can be intercepted by the nanofiltration membrane, if the raw water is not pretreated, a large amount of the solid suspended matters and the oil can be gathered on the surface of the nanofiltration membrane, so that the nanofiltration membrane can be blocked quickly, the permeation of water can not be realized, and the raw water can be used continuously only by chemical cleaning, so that the cleaning cost is increased.
Any combination of the technical features of the above embodiments may be performed, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not exhaustive, but should be considered as being within the scope of the present disclosure as long as no contradiction exists between the combinations of the technical features.
It will be apparent to those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention, as defined in the following claims.
Claims (10)
1. A zero-emission and resource utilization treatment system for shale gas produced water is characterized by comprising a miscellaneous salt separation unit, a bromine recovery unit, a lithium recovery unit and a sodium chloride salt separation unit; the shale gas produced water enters the mixed salt separation unit, and the effluent of the mixed salt separation unit enters the bromine recovery unit;
the bromine recovery unit comprises an air stripping tower (8), an absorption tower (9) and a distillation tower (11), the effluent of the miscellaneous salt separation unit is connected with the water inlet of the air stripping tower (8) through a pipeline, the gas outlet of the air stripping tower (8) is communicated with the gas inlet of the absorption tower (9), the water outlet of the absorption tower (9) is communicated with the distillation tower (11), bromine is separated out by the distillation tower (11), and the water outlet of the air stripping tower (8) is communicated with the lithium recovery unit;
the lithium recovery unit includes absorption desorption reactor (13), precipitation reactor (14) and solid-liquid separation equipment (15), blow off the delivery port intercommunication of tower (8) absorption desorption reactor (13) water inlet, the absorption product water in absorption desorption reactor (13) enters into sodium chloride salt separating element, desorption liquid in absorption desorption reactor (13) enters into in precipitation reactor (14), the delivery port intercommunication of precipitation reactor (14) solid-liquid separation equipment (15), lithium carbonate is separated out in solid-liquid separation equipment (15), the delivery port intercommunication of solid-liquid separation equipment (15) sodium chloride salt separating element, sodium chloride salt separating element separates out the sodium chloride salt.
2. The shale gas produced water zero-emission and resource utilization treatment system according to claim 1, wherein the treatment 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 flocculant 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 miscellaneous salt separation unit.
3. The shale gas produced water zero-emission and resource utilization processing system according to claim 2, characterized in that the miscellaneous salt separation unit comprises a nanofiltration separation device (4), a salt separation water production tank (5), an evaporation concentration device (6) and a drying device (7), the pretreatment water production tank (3) is communicated with the nanofiltration separation device (4) through a pump, a permeate of the nanofiltration separation device (4) enters the salt separation water production tank (5), the salt separation water production tank (5) is communicated with the stripping tower (8) through a pump, a concentrated solution of the nanofiltration separation device (4) enters the evaporation concentration device (6) for concentration, the concentrated solution is treated by the evaporation concentration device (6) and then enters the drying device (7) for drying, and separated miscellaneous salts are obtained.
4. The shale gas produced water zero-emission and resource utilization treatment system according to claim 1, wherein chlorine gas is introduced into the stripping tower (8), air is introduced into the stripping tower (8) to blow free bromine into the absorption tower (9), and the bromine is absorbed into the solution in the absorption tower (9) by spraying a sodium carbonate solution as an absorbent.
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 through the distillation tower (11) to obtain bromine.
5. The shale gas produced water zero-emission and resource utilization processing system according to claim 1, wherein a water outlet of the blow-off tower (8) is communicated with a water inlet of the adsorption and desorption reactor (13) through a bromine removal water production tank (12) and a pump, an adsorbent is placed in the adsorption and desorption reactor (13), the adsorbent adsorbs lithium ions in water, produced water adsorbed by the adsorbent enters a sodium chloride salt separation unit through a lithium removal water production tank (16), the adsorbed adsorbent is desorbed by a desorption agent to obtain a lithium-rich desorption solution, the lithium-rich desorption solution 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 effluent of the solid-liquid separation device (15) enters the lithium removal water production tank (16).
6. The shale gas produced water zero-emission and resource utilization treatment system according to claim 5, wherein the sodium chloride salt separation unit comprises an oxidation reactor (22), an oxidation water production tank (23), a membrane concentration device and an evaporation reactor (24);
the water in the lithium-removing water production tank (16) enters an oxidation reactor (22) and is added with an oxidant for oxidation treatment to obtain oxidized water production, a water outlet of the oxidation reactor (22) is communicated with the oxidized water production tank (23), the water in the oxidized water production tank (23) enters membrane concentration equipment for concentration, a concentrated solution of the membrane concentration equipment enters an evaporation reactor (24), and the evaporation reactor (24) is subjected to evaporation treatment to obtain a sodium chloride product.
7. The shale gas produced water zero-emission and resource utilization treatment system according to claim 6, wherein the membrane concentration equipment comprises a DTRO membrane device (17), a DTRO water production tank (18), a DTRO concentration tank (19), an RO membrane device (20) and an RO water production tank (21);
the water tank (23) is produced through the pump intercommunication in the oxidation the water inlet of DTRO membrane device (17), the product water of DTRO membrane device (17) enters into water tank (18) is produced to the DTRO, the concentrate of DTRO membrane device (17) enters into concentrated jar (19) of DTRO, water tank (18) is produced through the pump intercommunication in the DTRO the water inlet of RO membrane device (20), the product water of RO membrane device (20) enters into water tank (21) is produced to the RO, the concentrate of RO membrane device (20) returns to in the water tank (23) is produced to the oxidation, concentrated jar (19) of DTRO passes through the pump intercommunication evaporation reactor (24), the comdenstion water of evaporation reactor (24) enters into water tank (18) is produced to the DTRO.
8. A zero-emission and resource utilization treatment method for shale gas produced water is characterized by comprising the following steps:
s1, introducing the shale gas produced water into a pretreatment unit for pretreatment, adding a demulsifier and a flocculant, and removing suspended solids and oil in the shale gas produced water to obtain pretreated produced water;
s2, introducing the pretreated produced water into a mixed salt separation unit, and introducing COD (chemical oxygen demand) and Ca (calcium oxide) in the pretreated produced water 2+ 、Mg 2+ 、SO 4 2- Concentrating to obtain permeate and concentrated solution;
s3, drying the concentrated solution obtained in the step S2 to obtain solid residues of mixed salts;
s4, introducing the permeate liquid obtained in the step S2 into a stripping tower (8) for stripping to obtain bromine-containing air and bromine-removed 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 obtained in the step S5 into a distillation tower (11), adding a reactant, replacing bromine in water, and evaporating to obtain bromine;
s7, introducing the bromine-removed water produced in the step S4 into an adsorption and desorption reactor (13), and adsorbing lithium ions in the bromine-removed water produced by using an adsorbent to obtain adsorbed water produced;
s8, adding the adsorbent which is completely adsorbed in the step S7 for desorption to obtain a lithium-rich desorption solution;
s9, introducing the lithium-rich desorption solution obtained 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 dividing the lithium carbonate suspension into solid lithium carbonate and filtrate;
s11, introducing the water produced by adsorption in the step S7 into an oxidation reactor (22), and oxidizing organic matters in the water to obtain oxidized water;
s12, adding a reducing agent into the oxidation product water obtained in the step S11 for reduction, introducing the reduction solution into a DTRO membrane device (17), and concentrating salt to obtain DTRO permeate and DTRO concentrate; the DTRO permeate enters an RO membrane device (20), ions in water are further removed to obtain RO permeate and RO concentrated solution, the RO concentrated solution is continuously pumped to the front end of the DTRO membrane for treatment, and the water produced by the RO membrane is recycled after passing;
and S13, introducing the DTRO concentrated solution in the step S12 into an evaporation reactor (24) to obtain sodium chloride.
9. The zero emission and resource utilization treatment method for the shale gas produced water according to claim 8, wherein in the step S1, the shale gas produced water is introduced into a pretreatment unit for pretreatment, a demulsifier is added for reaction for 0.2h to 0.4h, and oil in the water is separated from the produced water; then adding polyaluminium chloride, wherein the usage amount of the polyaluminium chloride is 25-35mg/L, reacting for 0.1-0.3h, separating mud from water, then adding polyacrylamide, wherein the addition amount of the polyacrylamide is 0.4-0.5mg/L, and reacting for 0.1-0.3 h.
10. The shale gas produced water zero-emission and resource utilization treatment method according to claim 5, wherein in step S7, the adsorbent is a manganese-based lithium ion sieve adsorbent or an organic-inorganic nano hybrid adsorption material, the water content of the adsorbent is 40.0-58.0%, the particle size range (0.315-1.25) is greater than or equal to 95%, and the wet apparent density is 0.7-1.0g/mL; the adsorption capacity to lithium ion is 30-40mgLi/g adsorbent;
in the step S7, the temperature of the adsorption and desorption reactor (13) is 20-60 ℃, and the flow rate of the water produced by removing bromine in the adsorption and desorption reactor (13) is 50 mL/(min & L) -150 mL/(min & L);
in the step S8, a desorption agent is used for desorption operation, 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 0.4-1 mol/L.
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