CN116875997A - Recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in process of preparing diethyl methylphosphonite - Google Patents
Recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in process of preparing diethyl methylphosphonite Download PDFInfo
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- CN116875997A CN116875997A CN202211547113.4A CN202211547113A CN116875997A CN 116875997 A CN116875997 A CN 116875997A CN 202211547113 A CN202211547113 A CN 202211547113A CN 116875997 A CN116875997 A CN 116875997A
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- China
- Prior art keywords
- aluminum
- phosphite
- sodium
- sodium chloride
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 47
- 239000011574 phosphorus Substances 0.000 title claims abstract description 39
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004064 recycling Methods 0.000 title claims abstract description 36
- 239000002699 waste material Substances 0.000 title claims abstract description 36
- 150000003839 salts Chemical class 0.000 title claims abstract description 28
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 68
- ZCWZYHKKKJLNOQ-UHFFFAOYSA-M aluminum sodium chloride Chemical compound [Na+].[Al+3].[Cl-] ZCWZYHKKKJLNOQ-UHFFFAOYSA-M 0.000 title claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 46
- 239000000243 solution Substances 0.000 claims abstract description 45
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000001590 oxidative effect Effects 0.000 claims abstract description 30
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 21
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000292 calcium oxide Substances 0.000 claims abstract description 14
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 239000003513 alkali Substances 0.000 claims abstract description 13
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 12
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 12
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 239000011787 zinc oxide Substances 0.000 claims abstract description 11
- 238000004090 dissolution Methods 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 5
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 5
- 238000004140 cleaning Methods 0.000 claims abstract description 4
- 239000003814 drug Substances 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 91
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 239000011780 sodium chloride Substances 0.000 claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 239000007789 gas Substances 0.000 claims description 27
- 239000003463 adsorbent Substances 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 23
- 239000000706 filtrate Substances 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 15
- XWKBMOUUGHARTI-UHFFFAOYSA-N tricalcium;diphosphite Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])[O-].[O-]P([O-])[O-] XWKBMOUUGHARTI-UHFFFAOYSA-N 0.000 claims description 15
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007800 oxidant agent Substances 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- 239000012267 brine Substances 0.000 claims description 9
- VSFBSEDSFCLXNI-UHFFFAOYSA-N calcium;zinc;phosphite Chemical compound [Ca+2].[Zn+2].[O-]P([O-])[O-] VSFBSEDSFCLXNI-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- HJJOHHHEKFECQI-UHFFFAOYSA-N aluminum;phosphite Chemical compound [Al+3].[O-]P([O-])[O-] HJJOHHHEKFECQI-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000005341 cation exchange Methods 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 claims 2
- ZSFZQNSWHYVSDP-UHFFFAOYSA-G dialuminum;sodium;heptachloride Chemical compound [Na+].[Al+3].[Al+3].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-] ZSFZQNSWHYVSDP-UHFFFAOYSA-G 0.000 claims 2
- NNCOOIBIVIODKO-UHFFFAOYSA-N aluminum;hypochlorous acid Chemical compound [Al].ClO NNCOOIBIVIODKO-UHFFFAOYSA-N 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000004332 deodorization Methods 0.000 abstract 1
- -1 sodium tetrachloroaluminate Chemical compound 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 12
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 5
- 239000010452 phosphate Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 238000006298 dechlorination reaction Methods 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000009965 odorless effect Effects 0.000 description 4
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 4
- 235000019832 sodium triphosphate Nutrition 0.000 description 4
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 4
- 239000002910 solid waste Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CAYKLJBSARHIDI-UHFFFAOYSA-K trichloroalumane;hydrate Chemical compound O.Cl[Al](Cl)Cl CAYKLJBSARHIDI-UHFFFAOYSA-K 0.000 description 2
- AUTOISGCBLBLBA-UHFFFAOYSA-N trizinc;diphosphite Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])[O-].[O-]P([O-])[O-] AUTOISGCBLBLBA-UHFFFAOYSA-N 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 1
- 238000004069 wastewater sedimentation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/163—Phosphorous acid; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The technology is based on a waste salt of diethyl methylphosphonite, and prepares a large amount of water treatment medicament and new coating material by carrying out fine separation and recycling on the waste salt of high-salt, aluminum-rich, phosphorus-containing and organic matters. The waste salt is subjected to the steps of dissolution, oxidation, stripping, filtration, deodorization and the like, the organic phosphorus is oxidized and converted into phosphite, and the adsorption depth dephosphorization and the phosphite enrichment are adopted. Adding calcium and zinc oxide to prepare phosphite corrosion-resistant coating. And cleaning, dissolving, adsorbing and dephosphorizing and oxidizing organic matters to prepare the low-sodium dephosphorized polyaluminium ferric chloride. The finally collected solution is a low-phosphorus aluminum-free near-saturated salt solution, and water treatment agents such as liquid alkali, sodium hypochlorite and the like are prepared through electrolysis.
Description
Technical Field
The invention belongs to the technical field of recycling treatment, and relates to a recycling treatment process for producing sodium chloride waste salt containing phosphorus and aluminum in the process of preparing diethyl methylphosphonite.
Background
Diethyl methylphosphonite is an important chemical intermediate and can be used for synthesizing a novel efficient herbicide glufosinate-ammonium. At present, the main methods for preparing the diethyl methylphosphonite are an ethanol method, a triethyl phosphite method and a methyl phosphorus dichloride method, wherein phosphorus trichloride, aluminum trichloride and methyl chloride are used as raw materials to prepare ternary complex, and then the ternary complex is directly used for preparing the diethyl methylphosphonite. In particular to sodium chloride solid slag containing phosphorus and aluminum, including sodium tetrachloroaluminate, generated in the production process by adopting aluminum as a reducing agent. Sodium tetrachloroaluminate can become harmful solid waste as an organic chemical catalyst or a by-product in the pharmaceutical industry according to related regulations, has strong corrosiveness, and becomes a pain point in the industry as c-type solid waste. For this reason, there are many documents reporting the treatment and recycling thereof.
The patent 'a recycling process (CN 201510697507.1) of sodium tetrachloroaluminate in the production of glufosinate-ammonium', which is used for preparing aluminum tripolyphosphate from waste residues generated in the production of methyl phosphorus dichloride by a ternary complex method, and the byproduct of aluminum tripolyphosphate is prepared by utilizing phosphorus and aluminum elements in waste generated in the production of methyl phosphorus dichloride. The complex generated by the reaction is reduced under the catalysis of aluminum powder, phosphoric acid or phosphate is added into waste after the product methyl phosphorus dichloride is distilled out, the condensation reaction is carried out at the high temperature of 250-450 ℃, and after the reaction is finished, the aluminum tripolyphosphate product is obtained by washing, drying and micro-crushing, the yield of the byproduct aluminum tripolyphosphate can reach 90%, and the purity can reach 98%.
There are also reports of the preparation of aluminum hypophosphite from waste residues, wherein aluminum hypophosphite is a novel flame retardant, methyl chloride, aluminum trichloride and phosphorus trichloride are used as raw materials, a complex generated by the reaction is reduced under the catalysis of aluminum powder, ethanol is added into waste materials obtained after the product methyl phosphorus dichloride is distilled out for dissolving, then the solution is filtered, sodium hypophosphite solution is added into filtrate for reflux reaction for 3 hours, cooling and filtering are carried out, and a filter cake is dried to obtain an aluminum hypophosphite finished product, wherein the yield of byproduct aluminum hypophosphite can reach more than 80%, and the purity of the product is more than 98%. The process comprises the following steps: 1) Resolving and separating out; 2) Filtering the solid; 3) Cooling and separating out; 4) Reuse: 5) Recycling; 6) And (3) preparing polyaluminum chloride. According to the invention, sodium tetrachloroaluminate solid waste is changed into valuable, and aluminum trichloride obtained after the solution is recycled.
Li Weiwei et al propose a method for innocuous treatment of sodium tetrachloroaluminate. The bulk crystals of sodium tetrachloroaluminate are crushed to increase the specific surface area, so that the harmless treatment speed of sodium tetrachloroaluminate can be improved; adding water in turn to control water: sodium tetrachloroaluminate=1-10:1 weight ratio, and hot water with the temperature of 50-100 ℃ is used for reaction; 2NaAlCl 4 +H 2 O→Cl 2 Al-O-AlCl 2 The substance obtained by +2HCl+2NaCl is polyaluminium chloride, hydrogen chloride and sodium chloride, and hot water is added to accelerate the reaction so as to accelerate the generation of HCl and prevent HCl caused by bubbling phenomenon during cold water reaction from being directly discharged into the environment. Then adding alkali metal hydroxide or sodium bicarbonate to neutralize HCl, and adjusting the pH value to 5-10, wherein the obtained substance is MXCly, (M is alkali metal). Transferring the treated harmless substances such as polyaluminum chloride and MXCly into a wastewater sedimentation tank, utilizing flocculation property of polyaluminum chloride, adsorbing and gathering other substances by Van der Waals force, electrostatic attraction and the like to form larger particles, and accelerating the sedimentation tankThe other materials settle. However, the above treatment does not consider fine separation of aluminum, phosphorus and sodium chloride, and the recovered product has a large amount of impurities and low quality, and the treatment of containing an odor with organic matters and the like is not considered, and the recycling and harmless treatment of high quality cannot be achieved.
Disclosure of Invention
Aiming at the problems, the invention provides a recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite. The invention is based on a waste salt generated in the process of preparing diethyl methylphosphonite, and aims at finely separating the waste salt with high salt content, rich aluminum content, phosphorus content and organic matters, recovering low-sodium phosphorus-free polyaluminium ferric chloride and nearly saturated brine with brine aluminum content less than 100ppb, and carrying out electrolysis to prepare disinfectant and sodium hydroxide. The liquid sodium hydroxide with the effective content of sodium hypochlorite being more than 12 percent and 20 percent is a new material of calcium phosphite and zinc phosphite which is suitable for being used as an anti-corrosion coating, and can realize recycling and utilization.
In order to achieve the above purpose, the present invention adopts the following technical scheme.
A recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite comprises the following steps:
step 1, dissolving, oxidizing, blowing off and filtering waste salt by using water, removing insoluble substances and peculiar smell, and purifying gas; oxidizing the entrained organic matter by the oxidant while oxidizing the organic phosphorus to phosphorous acid; the solution is neutralized by alkali, and the aluminum hydroxide precipitate is recovered by filtration.
Step 2, cleaning, dissolving, adsorbing and dephosphorizing and oxidizing organic matters to prepare low-sodium dephosphorizing polyaluminium ferric chloride; adding calcium oxide and/or zinc oxide into the dealuminated salt solution to prepare a new material of calcium phosphite or calcium zinc phosphite anticorrosive coating; if calcium oxide and zinc oxide are added, the molar ratio of the calcium oxide to the zinc oxide is 1:1.
And 3, precipitating a nearly saturated salt solution for removing aluminum and phosphite, and purifying to prepare alkali liquor and sodium hypochlorite water treatment medicament.
Further, the oxidant in the step 1 is one or two of ozone, hydrogen peroxide or sodium hypochlorite.
Further, when the oxidant in the step 1 is ozone, the outgoing gas is adsorbed and purified in multiple stages by using an active carbon filter bed, and the active carbon filter bed of the first stage adopts a three-way catalyst loaded with vanadium and is leached by water; porous carbon is adopted after the second stage to adsorb small organic molecules; the dissolution rate can be increased by heating but controlled below 50 ℃ to reduce the volatilization of water; the water addition amount is mainly controlled to be completely dissolved, but is controlled to be more than 200 g/l according to the content of sodium chloride.
Further, the insoluble substances obtained after the oxidation and dissolution in the step 1 are mainly impurities such as silicon doped in the raw materials; neutralizing the solution with alkali at pH of 6-8, and filtering to recover aluminum hydroxide precipitate; the final filtrate contains sodium phosphite in addition to sodium chloride and a small amount of aluminum.
Further, the aluminum hydroxide precipitated in the step 2 contains sodium chloride and aluminum phosphite, the sodium chloride is washed by deionized water, and the washing water is recycled and used for dissolution until the conductivity of the washing water of the aluminum hydroxide is below 30 mu s/cm; the solid aluminum hydroxide is dissolved by hydrochloric acid to control the pH value to 3-4; adsorbing and dephosphorizing, wherein the adsorbent adopts hydroxyl aluminum hydroxide prepared by recycling aluminum chloride solution, and dephosphorizing to be less than 10 ppm; adding ferrous chloride and hydrogen peroxide for heating oxidation, further removing organic matters and phosphite radicals, controlling TOC of the organic matters to be 10ppm, supplementing aluminum or iron according to requirements, adding the aluminum or iron, and polymerizing to prepare the polyaluminium ferric chloride.
Further, the dissolved adsorption dephosphorization requires that the backwash liquid of the adsorption dephosphorization column is returned to a precipitation tank for preparing calcium phosphite or calcium zinc phosphite, the backwash liquid is saturated sodium chloride solution, and the precipitate is washed by deionized water and dried at a low temperature until the water conductivity is lower than 30 mu s/cm, so that the phosphite is obtained.
Further, the filtrate required to recover phosphite is close to saturated sodium chloride, an aluminum-based adsorbent is adopted for adsorption and dephosphorization, the adsorption-elution process is the same as that of the adsorption-elution process, secondary sodium chloride is adopted for oxidation and removal of organic matters, TOC reaches below 5ppm, residual chlorine is removed by blowing, and ion activated carbon filtration-cation exchange is carried out to remove hardness such as calcium, magnesium and the like and aluminum, so that the hardness reaches the standard of entering a tank.
Further, the concentration of the brine entering the diaphragm outlet groove is controlled below 80g/l, the current is constant at 3-3.7A, the voltage is 5.0-10V, the electrolysis time is 1-5 hours (can be continuous), the length of the electrode plate is 8.5cm, the width is 5.5cm, and the area is 46.75cm 2 Electrolyzing to prepare sodium hypochlorite with 20% and 12% of liquid sodium hydroxide, and recycling desalted water.
Furthermore, aluminum chloride hydroxide which is mainly utilized by the aluminum-based adsorbent is utilized, the pH value of the aluminum chloride and sodium carbonate purified by the process is adjusted to be 2 in the synthesis process, and organic acid such as citric acid is added under the hydrothermal condition to prepare the adsorbent with a crystal structure and a micrometer scale.
Furthermore, the electrolytic tank adopts a symmetrical ion membrane, and has no characteristics of front and back homogeneity and acid and alkali resistance.
Compared with the prior art, the invention has the beneficial effects that.
Realizes the fine separation and recycling of aluminum, phosphorus and sodium chloride in the final filtrate in the waste residue. The product obtained after the waste residue is treated by the process is rich and comprises polyaluminum, calcium phosphite, zinc phosphite, sodium hypochlorite, sodium hydroxide and the like. Meanwhile, the recycling of gas and liquid in the process is definitely treated, and the waste of resources is caused by direct discharge. The whole process realizes high-quality recycling and harmless treatment.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is an infrared spectrum of calcium phosphite prepared in example 1.
FIG. 3 XRD pattern of the aluminum-based adsorbent of example 1.
FIG. 4 SEM image of an aluminum-based adsorbent of example 1.
FIG. 5 shows a double-sided homography of a symmetric ionic membrane of example 1.
FIG. 6 XPS plot of example 2 vanadium catalyst.
Fig. 7 SEM image of activated carbon of example 2.
FIG. 8 is an infrared spectrum of calcium zinc phosphite prepared in example 2.
Detailed Description
Some embodiments of the invention are disclosed below and one skilled in the art can, based on the disclosure herein, suitably modify the process parameters to achieve this. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those skilled in the relevant art that variations and modifications can be made in the methods and applications described herein, and in the practice and application of the techniques of this invention, without departing from the spirit or scope of the invention.
A recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite comprises the following steps:
step 1, dissolving, oxidizing, blowing off and filtering waste salt by using water, removing insoluble substances and peculiar smell, and purifying gas; oxidizing the entrained organic matter by the oxidant while oxidizing the organic phosphorus to phosphorous acid; the solution is neutralized by alkali, and the aluminum hydroxide precipitate is recovered by filtration.
Step 2, cleaning, dissolving, adsorbing and dephosphorizing and oxidizing organic matters to prepare low-sodium dephosphorizing polyaluminium ferric chloride; adding calcium oxide and/or zinc oxide into the dealuminated salt solution to prepare a new material of calcium phosphite or calcium zinc phosphite anticorrosive coating; if calcium oxide and zinc oxide are added, the molar ratio of the calcium oxide to the zinc oxide is 1:1.
And 3, precipitating a nearly saturated salt solution for removing aluminum and phosphite, and purifying to prepare alkali liquor and sodium hypochlorite water treatment medicament.
Further, the oxidant in the step 1 is one or two of ozone, hydrogen peroxide or sodium hypochlorite.
Further, when the oxidant in the step 1 is ozone, the outgoing gas is adsorbed and purified in multiple stages by using an active carbon filter bed, and the active carbon filter bed of the first stage adopts a three-way catalyst loaded with vanadium and is leached by water; porous carbon is adopted after the second stage to adsorb small organic molecules; the dissolution rate can be increased by heating but controlled below 50 ℃ to reduce the volatilization of water; the water addition amount is mainly controlled to be completely dissolved, but is controlled to be more than 200 g/l according to the content of sodium chloride.
Further, the insoluble substances obtained after the oxidation and dissolution in the step 1 are mainly impurities such as silicon doped in the raw materials; neutralizing the solution with alkali at pH of 6-8, and filtering to recover aluminum hydroxide precipitate; the final filtrate contains sodium phosphite in addition to sodium chloride and a small amount of aluminum.
Further, the aluminum hydroxide precipitated in the step 2 contains sodium chloride and aluminum phosphite, the sodium chloride is washed by deionized water, and the washing water is recycled and used for dissolution until the conductivity of the washing water of the aluminum hydroxide is below 30 mu s/cm; the solid aluminum hydroxide is dissolved by hydrochloric acid to control the pH value to 3-4; adsorbing and dephosphorizing, wherein the adsorbent adopts hydroxyl aluminum hydroxide prepared by recycling aluminum chloride solution, and dephosphorizing to be less than 10 ppm; adding ferrous chloride and hydrogen peroxide for heating oxidation, further removing organic matters and phosphite radicals, controlling TOC of the organic matters to be 10ppm, supplementing aluminum or iron according to requirements, adding the aluminum or iron, and polymerizing to prepare the polyaluminium ferric chloride.
Further, the dissolved adsorption dephosphorization requires that the backwash liquid of the adsorption dephosphorization column is returned to a precipitation tank for preparing calcium phosphite or calcium zinc phosphite, the backwash liquid is saturated sodium chloride solution, and the precipitate is washed by deionized water and dried at a low temperature until the water conductivity is lower than 30 mu s/cm, so that the phosphite is obtained.
Further, the filtrate required to recover phosphite is close to saturated sodium chloride, an aluminum-based adsorbent is adopted for adsorption and dephosphorization, the adsorption-elution process is the same as that of the adsorption-elution process, secondary sodium chloride is adopted for oxidation and removal of organic matters, TOC reaches below 5ppm, residual chlorine is removed by blowing, and ion activated carbon filtration-cation exchange is carried out to remove hardness such as calcium, magnesium and the like and aluminum, so that the hardness reaches the standard of entering a tank.
Further, the concentration of the brine entering the diaphragm outlet groove is controlled below 80g/l, the current is constant at 3-3.7A, the voltage is 5.0-10V, the electrolysis time is 1-5 hours (can be continuous), the length of the electrode plate is 8.5cm, the width is 5.5cm, and the area is 46.75cm 2 Electrolyzing to prepare sodium hypochlorite with 20% and 12% of liquid sodium hydroxide, and desalting waterAnd (5) returning to recycling.
Furthermore, aluminum chloride hydroxide which is mainly utilized by the aluminum-based adsorbent is utilized, the pH value of the aluminum chloride and sodium carbonate purified by the process is adjusted to be 2 in the synthesis process, and organic acid such as citric acid is added under the hydrothermal condition to prepare the adsorbent with a crystal structure and a micrometer scale.
Furthermore, the electrolytic tank adopts a symmetrical ion membrane, and has no characteristics of front and back homogeneity and acid and alkali resistance.
Example 1.
20g of waste residue (Al content 10%, P content 7.2% and NaCl content 66.54%) is weighed, 25ml of aqueous solution is added, the mixture is put into a three-mouth bottle, 5ml of hydrogen peroxide is added as an oxidant, and then 10 mg/L of ozone is introduced. The vanadium-loaded catalyst used by the activated carbon bed of the first stage was collected by gas while water was rinsed. The second stage utilizes porous carbon to adsorb small organic molecules, the two stages of adsorption jointly realize the purification of gas, and the gas release of the odorless gas of the three-mouth bottle is detected after the gas is heated for 1 hour at 40 ℃.
Insoluble matter was removed by filtration to obtain a supernatant (Al content 12%, P content 6.65%, naCl content 210 g/L). The solution ph=6.6 was adjusted with 0.1 mol/L sodium hydroxide so that the aluminum ions in the solution were completely precipitated. The supernatant was filtered to obtain a phosphorus-containing supernatant (P content 9.1%, naCl content 218 g/L) and an aluminum hydroxide precipitate (Al content 90.4%).
Adding calcium oxide into the filtrate to obtain calcium phosphite precipitate, vacuum drying to obtain final product, and infrared spectrum comparing to obtain calcium phosphite, as shown in figure 2.
The obtained aluminum hydroxide precipitate was first washed with water, then dissolved with 0.5mol/L hydrochloric acid at ph=3.8, and ferric salt and hydrogen peroxide were added for secondary oxidation to convert phosphorus into phosphate while further controlling the content of organic matter at 5ppm, and the solution was filtered to obtain a solution (P content 28 mg/L), and a small amount of phosphorus contained in the solution was removed with an adsorbent to finally obtain polyaluminum ferric chloride (P content 3 mg/L).
The adsorbent loaded in the adsorption column is an aluminum-based adsorbent, and the basic component is aluminum hydroxide (prepared by using aluminum potassium sulfate dodecahydrate and urea as raw materials and performing hydrothermal synthesis at 180 ℃) and is characterized in that the adsorption column is prepared from saturated sodium chloride solution for backwashing liquid as shown in fig. 3 and 4.
Collecting the NaCl filtrate, oxidizing sodium hypochlorite to remove organic matters, and detecting TOC as 3ppm; the adsorption dephosphorization method is the same as that of the adsorption dephosphorization method, and the deep dechlorination and other cations such as calcium and magnesium are carried out through ion exchange. Purifying, introducing into symmetric membrane for electrolysis with sodium chloride concentration of 230g/l, electrolysis time of 180 min, constant current of 3.0A, voltage of 5.2V, electrode plate length of 8.5cm, electrode width of 5.5cm, and area of 46.75cm 2 . The concentration of brine in the outlet tank is 79g/l, and the desalted water is returned for recycling. Electrolyzing to prepare 20% sodium hydroxide solution; and introducing chlorine into sodium hydroxide to obtain sodium hypochlorite with the concentration of 12%.
Example 2.
20g of waste residue (Al content 13%, P content 8.9% and NaCl content 56.65%) was weighed, added to 25ml of an aqueous solution, and placed in a three-necked flask. In addition, 5ml of hydrogen peroxide is added as an oxidant, and then 10/mg/L of ozone is introduced. The vanadium-loaded catalyst used by the activated carbon bed of the first stage was collected by gas while water was rinsed. The second stage utilizes porous carbon to adsorb small organic molecules, the two stages of adsorption jointly realize the purification of gas, and the gas release of the odorless gas of the three-mouth bottle is detected after the gas is heated for 1.5 hours at 30 ℃.
Insoluble matter was removed by filtration to obtain a supernatant (Al content 14.2%, P content 7.93%, naCl content 221 g/L). The solution ph=6.8 was adjusted with 0.1 mol/L sodium hydroxide so that the aluminum ions in the solution were completely precipitated. The supernatant was filtered to obtain a phosphorus-containing supernatant (P content 9.1%, naCl content 230 g/L) and an aluminum hydroxide precipitate (Al content 96.9%).
Zinc oxide and calcium oxide (molar ratio 1:1) are added into the filtrate to obtain calcium zinc phosphite precipitate, the precipitate is dried in vacuum to obtain a final product, and the calcium zinc phosphite precipitate is obtained through infrared spectrum comparison, as shown in figure 8.
The obtained aluminum hydroxide precipitate was first washed with sodium chloride filtrate, then dissolved with 0.5mol/L hydrochloric acid at ph=3.8, and ferric salt and hydrogen peroxide were added for secondary oxidation to convert phosphorus into phosphate while further controlling the content of organic matter at 5ppm, and the solution was filtered to obtain a solution (P content 28 mg/L), and a small amount of phosphorus contained in the solution was removed with an adsorbent to finally obtain polyaluminum ferric chloride (P content 3 mg/L).
The adsorbent loaded in the adsorption column is an aluminum-based adsorbent, the basic component is aluminum hydroxide (aluminum potassium sulfate dodecahydrate and urea are used as raw materials for hydrothermal synthesis at 180 ℃), and the backwash liquid is saturated sodium chloride solution.
Collecting the NaCl filtrate, oxidizing sodium hypochlorite to remove organic matters, and detecting TOC to be 3.1ppm; the adsorption dephosphorization method is the same as that of the adsorption dephosphorization method, and the deep dechlorination and other cations such as calcium and magnesium are carried out through ion exchange. Purifying, introducing into symmetric membrane for electrolysis with sodium chloride concentration of 230g/l, electrolysis time of 130 min, constant current of 3.5A, voltage of 7.0-7.2V, electrode plate length of 8.5cm, electrode plate width of 5.5cm, and area of 46.75cm 2 . The brine concentration of the outlet tank is 76.8 g/l. . The concentration of brine in the outlet tank is 67g/l, and the desalted water is returned for recycling. Electrolyzing to prepare 20% sodium hydroxide solution; and introducing chlorine into sodium hydroxide to obtain sodium hypochlorite with the concentration of 12%.
Example 3.
20g of waste residue (Al content 11.3%, P content 9.2% and NaCl content 72.54%) was weighed, added to 25ml of an aqueous solution, and placed in a three-necked flask. In addition, 5ml of hydrogen peroxide is added as an oxidant. The vanadium-loaded catalyst used by the activated carbon bed of the first stage was collected by gas while water was rinsed. The second stage utilizes porous carbon to adsorb small organic molecules, the two stages of adsorption jointly realize the purification of gas, and the gas release of odorless gas at the outlet of the three-port bottle is detected after the gas is heated for 1 hour at 40 ℃.
Insoluble matter was removed by filtration to obtain a supernatant (Al content 14%, P content 10.65%, naCl content 210 g/L). The solution ph=6.3 was adjusted with 0.1 mol/L sodium hydroxide so that the aluminum ions in the solution were completely precipitated. The supernatant was filtered to obtain a phosphorus-containing supernatant (P content 7.3%, naCl content 226 g/L) and an aluminum hydroxide precipitate (Al content 86.2%).
Adding calcium oxide into the filtrate to obtain calcium phosphite precipitate, vacuum drying to obtain the final product, and performing infrared spectrum comparison to obtain the calcium phosphite.
The obtained aluminum hydroxide precipitate was first washed with sodium chloride filtrate, then dissolved with 0.5mol/L hydrochloric acid at ph=3.1, and ferric salt and hydrogen peroxide were added for secondary oxidation to convert phosphorus into phosphate with the organic content at 5ppm, and the solution was filtered to obtain a solution (P content 32 mg/L), and a small amount of phosphorus (P content 1 mg/L) contained in the solution was removed with an adsorbent to finally obtain polyaluminum ferric chloride.
The adsorbent loaded in the adsorption column is an aluminum-based adsorbent, the basic component is aluminum hydroxide (aluminum potassium sulfate dodecahydrate and urea are used as raw materials for hydrothermal synthesis at 180 ℃), and the backwash liquid is saturated sodium chloride solution.
Collecting the NaCl filtrate, oxidizing sodium hypochlorite to remove organic matters, and detecting TOC as 3ppm; the adsorption dephosphorization method is the same as that of the adsorption dephosphorization method, and the deep dechlorination and other cations such as calcium and magnesium are carried out through ion exchange.
After purification, the solution with the concentration of sodium chloride of 247 g/l enters a symmetrical diaphragm for electrolysis. The electrolysis time is 100min, the current is constant at 3.7A, the voltage is between 7.8 and 8.4V, the length of the electrode plate is 8.5cm, the width is 5.5cm, and the area is 46.75cm 2 . The brine concentration of the effluent tank is 79.8g/l. And returning the desalted water for recycling. Electrolyzing to prepare 20% sodium hydroxide solution; and introducing chlorine into sodium hydroxide to obtain sodium hypochlorite with the concentration of 12%.
Example 4.
20g of waste residue (Al content 12.3%, P content 9.5% and NaCl content 58.63%) was weighed, added to 25ml of an aqueous solution, and put into a three-necked flask. 5ml of hydrogen peroxide is additionally added as an oxidant and 8 mg/ozone. The vanadium-loaded catalyst used by the activated carbon bed of the first stage was collected by gas while water was rinsed. The second stage utilizes porous carbon to adsorb small organic molecules, the two stages of adsorption jointly realize the purification of gas, and the gas release of odorless gas at the outlet of the three-port bottle is detected after the gas is heated for 1 hour at 40 ℃.
Insoluble matter was removed by filtration to obtain a supernatant (Al content 13.4%, P content 11.05%, naCl content 190 g/L). The solution ph=6.4 was adjusted with 0.1 mol/L sodium hydroxide so that the aluminum ions in the solution were completely precipitated. The supernatant was filtered to obtain a phosphorus-containing supernatant (P content 8.6%, naCl content 212 g/L) and an aluminum hydroxide precipitate (Al content 85.4%).
Adding calcium oxide into the filtrate to obtain calcium phosphite precipitate, vacuum drying to obtain the final product, and performing infrared spectrum comparison to obtain the calcium phosphite.
The obtained aluminum hydroxide precipitate was first washed with sodium chloride filtrate, then dissolved with 0.5mol/L hydrochloric acid at ph=3.1, and ferric salt and hydrogen peroxide were added for secondary oxidation to convert phosphorus into phosphate with an organic content of 5ppm, and the solution was filtered to obtain a solution (P content 28 mg/L), and a small amount of phosphorus (P content 1 mg/L) contained in the solution was removed with an adsorbent to finally obtain polyaluminum ferric chloride.
The adsorbent loaded in the adsorption column is an aluminum-based adsorbent, the basic component is aluminum hydroxide (aluminum potassium sulfate dodecahydrate and urea are used as raw materials for hydrothermal synthesis at 180 ℃), and the backwash liquid is saturated sodium chloride solution.
Collecting the NaCl filtrate, oxidizing sodium hypochlorite to remove organic matters, and detecting TOC to be 2.6ppm; the adsorption dephosphorization method is the same as that of the adsorption dephosphorization method, and the deep dechlorination and other cations such as calcium and magnesium are carried out through ion exchange.
Collecting NaCl filtrate (TOC of 2ppm and NaCl content of 239.2 g/L), electrolyzing for 90min at constant current of 3.7A and voltage of 8.2-8.8V, and electrode plate length of 8.5cm, width of 5.5cm and area of 46.75cm 2 . The brine concentration of the outlet tank is 76.8 g/l. And returning the desalted water for recycling. Electrolyzing to prepare 20% sodium hydroxide solution; and introducing chlorine into sodium hydroxide to obtain sodium hypochlorite with the concentration of 12%.
Claims (10)
1. A recycling treatment process for producing phosphorus-containing and aluminum-containing sodium chloride waste salt in the process of preparing diethyl methylphosphonite is characterized by comprising the following steps:
step 1, dissolving, oxidizing, blowing off and filtering waste salt by using water, removing insoluble substances and peculiar smell, and purifying gas; oxidizing the entrained organic matter by the oxidant while oxidizing the organic phosphorus to phosphorous acid; neutralizing the solution with alkali, and filtering to recover aluminum hydroxide precipitate;
step 2, cleaning, dissolving, adsorbing and dephosphorizing and oxidizing organic matters to prepare low-sodium dephosphorizing polyaluminium ferric chloride; adding calcium oxide and/or zinc oxide into the dealuminated salt solution to prepare a new material of calcium phosphite or calcium zinc phosphite anticorrosive coating; if calcium oxide and zinc oxide are added, the molar ratio of the calcium oxide to the zinc oxide is 1:1;
and 3, precipitating a nearly saturated salt solution for removing aluminum and phosphite, and purifying to prepare alkali liquor and sodium hypochlorite water treatment medicament.
2. The recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite according to claim 1, wherein the oxidant in the step 1 is one or two of ozone, hydrogen peroxide or sodium hypochlorite.
3. The recycling treatment process for producing waste salt containing phosphorus and sodium aluminum chloride in the process of preparing diethyl methylphosphonite according to claim 2, wherein when the oxidant is ozone, the outgoing gas is adsorbed and purified in multiple stages by an activated carbon filter bed, and the first-stage activated carbon bed adopts a three-way catalyst loaded with vanadium and is leached by water; porous carbon is adopted after the second stage to adsorb small organic molecules; the dissolution rate can be increased by heating but controlled below 50 ℃ to reduce the volatilization of water; the water addition amount is mainly controlled to be completely dissolved, but is controlled to be more than 200 g/l according to the content of sodium chloride.
4. The recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite according to claim 1, wherein the insoluble substances obtained after the oxidation and dissolution in the step 1 are mainly impurities such as silicon doped in raw materials; neutralizing the solution with alkali at pH of 6-8, and filtering to recover aluminum hydroxide precipitate; the final filtrate contains sodium phosphite in addition to sodium chloride and a small amount of aluminum.
5. The recycling treatment process for producing waste sodium chloride salt containing phosphorus and aluminum in the process of preparing diethyl methylphosphonite according to claim 1, wherein the aluminum hydroxide precipitated in the step 2 contains sodium chloride and aluminum phosphite, the sodium chloride is washed by deionized water, and the washing water is recycled and used for dissolution until the conductivity of the washing water of the aluminum hydroxide is below 30 mu s/cm; the solid aluminum hydroxide is dissolved by hydrochloric acid to control the pH value to 3-4; adsorbing and dephosphorizing, wherein the adsorbent adopts hydroxyl aluminum hydroxide prepared by recycling aluminum chloride solution, and dephosphorizing to be less than 10 ppm; adding ferrous chloride and hydrogen peroxide for heating oxidation, further removing organic matters and phosphite radicals, controlling TOC of the organic matters to be 10ppm, supplementing aluminum or iron according to requirements, adding the aluminum or iron, and polymerizing to prepare the polyaluminium ferric chloride.
6. The recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite according to claim 1, wherein the dissolving, adsorbing and dephosphorizing in the step 2 requires that a backwash liquid of an adsorption dephosphorizing column is returned to a precipitation tank for preparing calcium phosphite or calcium zinc phosphite, the backwash liquid is saturated sodium chloride solution, and the precipitate is washed by deionized water and washed until the water conductivity is lower than 30 mu s/cm, and is dried at a low temperature to obtain phosphite.
7. The recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite according to claim 6, wherein the filtrate required to recover phosphite is close to saturated sodium chloride, the adsorption and dephosphorization are carried out by adopting an aluminum-based adsorbent, the adsorption-elution process is the same as that of the adsorption-elution process, the oxidation and removal of organic matters are carried out by adopting sodium hypochlorite, TOC reaches below 5ppm, residual chlorine is removed by blowing, and hardness such as calcium, magnesium and aluminum are removed by ion activated carbon filtration-cation exchange, so that the standard of entering the tank is reached.
8. The recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonate according to claim 7, wherein the concentration of brine entering a diaphragm outlet groove is controlled below 80g/l, the current is constant at 3-3.7A, the voltage is 5.0-10V, the electrolysis time is 1-5 hours, the length of an electrode plate is 8.5cm, the width is 5.5cm, and the area is 46.75cm 2 Electrolyzing to prepare sodium hypochlorite with 20% and 12% of liquid sodium hydroxide, and recycling desalted water.
9. The recycling treatment process for producing phosphorus-containing and sodium aluminum chloride waste salt in the diethyl methylphosphonate preparation process according to claim 7, wherein the aluminum-based adsorbent mainly uses aluminum hydroxychloride, the pH of the aluminum chloride and sodium carbonate purified by the process is adjusted to 2 in the synthesis process, and organic acid such as citric acid is added under hydrothermal condition to prepare the adsorbent with crystal structure and micrometer size.
10. The recycling treatment process for producing waste salt containing phosphorus and aluminum sodium chloride in the process of preparing diethyl methylphosphonite according to claim 8, wherein the electrolytic tank adopts a symmetrical ionic membrane, and has no characteristics of front and back homogeneity and acid and alkali resistance.
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