CN117756323A - Vanadium chemical industry high-salt ammonia nitrogen wastewater treatment method - Google Patents
Vanadium chemical industry high-salt ammonia nitrogen wastewater treatment method Download PDFInfo
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- CN117756323A CN117756323A CN202311769973.7A CN202311769973A CN117756323A CN 117756323 A CN117756323 A CN 117756323A CN 202311769973 A CN202311769973 A CN 202311769973A CN 117756323 A CN117756323 A CN 117756323A
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- ammonia nitrogen
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- ammonium
- salt
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- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 70
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000000126 substance Substances 0.000 title claims abstract description 17
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 99
- 238000000034 method Methods 0.000 claims abstract description 68
- 239000002351 wastewater Substances 0.000 claims abstract description 42
- 230000008569 process Effects 0.000 claims abstract description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 37
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 34
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 32
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 30
- 230000002308 calcification Effects 0.000 claims abstract description 30
- 238000004176 ammonification Methods 0.000 claims abstract description 29
- 238000003763 carbonization Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000007790 solid phase Substances 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 23
- 239000011575 calcium Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 16
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 16
- 230000009466 transformation Effects 0.000 claims abstract description 16
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 15
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 15
- 230000023556 desulfurization Effects 0.000 claims abstract description 15
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 13
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 13
- 239000011651 chromium Substances 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- VWBLQUSTSLXQON-UHFFFAOYSA-N N.[V+5] Chemical compound N.[V+5] VWBLQUSTSLXQON-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 19
- 230000008020 evaporation Effects 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 12
- 239000001099 ammonium carbonate Substances 0.000 claims description 12
- 239000002893 slag Substances 0.000 claims description 12
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- -1 ammonium ions Chemical class 0.000 claims description 4
- 238000012824 chemical production Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000009615 deamination Effects 0.000 abstract description 3
- 238000006481 deamination reaction Methods 0.000 abstract description 3
- 238000010979 pH adjustment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 39
- 239000000706 filtrate Substances 0.000 description 14
- 239000002002 slurry Substances 0.000 description 11
- 238000002386 leaching Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 238000000926 separation method Methods 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical class [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The invention relates to a method for treating vanadium chemical high-salt ammonia nitrogen wastewater, which comprises the following steps: adding a calcification agent into the high-salt ammonia nitrogen wastewater for calcification desulfurization treatment to obtain a calcium sulfate solid phase and an ammonia-containing NaOH solution, adding calcium sulfate into water, and introducing an ammonification carbonization agent for ammonification carbonization transformation reaction to obtain a calcium carbonate precipitate and an ammonium sulfate solution; the ammonium sulfate solution is sent to a front-end ammonium salt vanadium precipitation process, calcium carbonate solid phase is calcined at high temperature to obtain calcium oxide and carbon dioxide gas, the calcium oxide is sent to a desulfurization process for recycling, the carbon dioxide gas is sent to an ammonification carbonization transformation process, the ammonia-containing NaOH solution is sent to a front-end chromium removal process for pH adjustment after deamination, and the obtained ammonia gas is sent to the ammonification carbonization transformation process. The invention realizes the recycling of elements such as sodium, ammonium, calcium, sulfur, carbon and the like, has short and simple process flow and good wastewater treatment effect, is suitable for industrial production, and has good economic benefit and application prospect.
Description
Technical Field
The invention relates to the field of environmental protection, in particular to a vanadium chemical industry high-salt ammonia nitrogen wastewater treatment method.
Background
Vanadium (Vanadium), a silvery white metal, atomic number 23, atomic weight 50.9414, melting point 1890 ℃, boiling point 3380 ℃, density 6.110g/cm, is refractory metal with niobium, tantalum, tungsten, molybdenum. Vanadium is called as vitamin in steel due to its good toughness, strength and other characteristics, and vanadium (metal) has good ductility, hard quality, no magnetism, difficult oxidation in air and difficult corrosion. The vanadium slag is a main raw material for extracting vanadium, and at present, the sodium oxide roasting-water leaching vanadium extraction process of the vanadium slag is a main process for extracting vanadium from the vanadium slag at home and abroad. The vanadium slag is sodium-oxidized and roasted by a rotary kiln or a multi-hearth furnace, the sodium of low-valence vanadium is converted into water-soluble high-valence vanadate, purified vanadium liquid is obtained after water leaching and impurity removal, and ammonium vanadate and ammonium sulfate are precipitated to obtain ammonium vanadate and vanadium precipitation wastewater.
Vanadium and chromium are recovered from the vanadium precipitation wastewater through Na 2 CO 3 Or adjusting the pH value by liquid alkali, quantitatively adding polymeric ferric sulfate to precipitate vanadium, and recycling. By SO 2 Gas or sodium metabisulfite to convert Cr 6+ Reduction to Cr 3+ . With Na 2 CO 3 Or the pH value of the liquid alkali is regulated, and simultaneously, a metal chelating agent or polymeric ferric sulfate and a biological flocculant are added to precipitate and recycle chromium mud. The wastewater after vanadium and chromium removal forms high-salt ammonia nitrogen wastewater. The wastewater has complex components and high treatment difficulty, and has great influence on the environment and human health, so the recycling treatment and recycling of the vanadium precipitation wastewater are urgent demands of related enterprises.
Patent 2022106349716 discloses a method for preparing urea by recycling vanadium precipitation wastewater, wherein vanadium slag after vanadium extraction is subjected to sodium roasting method to extract V in the first step 2 O 5 Will extract V 2 O 5 The vanadium precipitation wastewater is subjected to gradient roasting, and then is added with a reducing agent and reacts for 1.5 to 2 hours at the temperature of 1000 to 1150 ℃ to obtain solid containing sodium sulfide and SO 2 、NH 3 、CO 2 A gas; second step SO 2 After absorption, CO is added again 2 And NH 3 Separating; third step of CO 2 NH is purified and compressed 3 And cooling and condensing, and then carrying out a carbon dioxide stripping method to produce urea. Although the method can realize recycling of the vanadium precipitation wastewater to prepare urea, the method has high treatment cost, and the process is not easy to control and is not suitable for industrial production.
Patent 2022114099534 discloses a method for cooperatively treating gas desulfurization waste residue and sodium-treatment vanadium precipitation wastewater, which comprises the following steps: a. adding the gas desulfurization waste residue into the sodium vanadium precipitation wastewater under the stirring effect, fully reacting, and carrying out solid-liquid separation to obtain supernatant and sludge; b. the supernatant fluid obtained in the step (a) flows into an activated carbon filter for adsorption treatment, and the supernatant fluid is obtained after filtration; c. sending the filtered clear liquid in the step (b) to an alkaline regulating tank, and adding NaOH to regulate the pH value of the filtered clear liquid in the step (b) to be alkaline; d. adding sulfuric acid into the filtrate obtained in the step (c) in an acid regulating tank to regulate the pH value of the solution to be acidic; e. pumping the acidic solution obtained in the step (d) into an evaporation system, discharging the acidic solution to a crystallization system, and performing solid-liquid separation to obtain anhydrous sodium sulfate and ammonium thiocyanate. The method has the advantages of more added agents, mixed salts of sodium thiocyanate, ammonium thiocyanate and the like, large accumulation amount, high treatment difficulty and high cost.
Patent 2022110706256 discloses a method for purifying alkaline vanadium liquid. The method comprises the following steps: adding water into the desulfurized gypsum for pulping, and adding polyvinyl alcohol in the pulping process to prepare slurry; wherein the desulfurization gypsum is a byproduct obtained by desulfurizing and purifying the flue gas generated after the combustion of the sulfur-containing fuel, and is prepared according to CaSO 4 ·2H 2 O, the purity of the desulfurized gypsum is at least 75%; mixing and stirring alkaline vanadium liquid and the slurry to enable the alkaline vanadium liquid and the slurry to react and obtain a reacted material; wherein the alkaline vanadium liquid is vanadium slag sodium roasting clinker leaching liquid; and filtering and washing the reacted material to obtain purified vanadium liquid and impurity-removed slag.
Disclosure of Invention
In view of the defects existing in the prior art, the invention provides a vanadium chemical industry high-salt ammonia nitrogen wastewater treatment method, which is a recycling method. The utilization method of the vanadium precipitation wastewater realizes the recycling of elements such as sodium, ammonium, calcium, sulfur, carbon and the like through the procedures of calcification desulfurization, ammonification transformation, solution deamination, high-temperature calcination of calcium carbonate and the like, has short and simple process flow and good wastewater treatment effect, is suitable for industrial production, and has good economic benefit and application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
(1) Adding a calcification agent into the high-salt ammonia nitrogen wastewater to perform calcification desulfurization treatment to obtain calcium sulfate precipitate and an ammonia-containing NaOH solution; the high-salt ammonia nitrogen wastewater is vanadium chemical production wastewater, and contains NH 4+ 、SO 4 2- And Na (Na) - The method comprises the steps of carrying out a first treatment on the surface of the And also contains OH - V, cr and Cl elements;
(2) Adding the calcium sulfate obtained in the step (1) into water, adding an ammonification carbonization agent, and performing ammonification carbonization transformation reaction to obtain a calcium carbonate solid phase and an ammonium sulfate solution.
The calcification agent in the step (1) is one or more of calcium oxide, calcium hydroxide and calcium chloride, and is preferably calcium oxide.
The calcification reaction in step (1) of the invention is carried out at a temperature of 30-95 ℃ and the ratio Ca/SO of the molar amount of calcium in the calcification agent to the molar amount of sulfate radical in the solution 4 2- 0.8-1.8, calcification time 20-120min, and stirring speed 10-500r/min.
The chemical reactions that occur include:
Na 2 SO 4 +Ca(OH) 2 =CaSO 4 +2NaOH
(NH 4 ) 2 SO 4 +Ca(OH) 2 =2NH 3 ↑+2H 2 O+CaSO 4 ↓
the ammonia water obtained by the first-effect evaporation of the ammonia-containing NaOH solution obtained in the step (1) is sent to an ammonification carbonization transformation process, the once concentrated NaOH solution is sent to a second-effect evaporation and a third-effect evaporation to obtain production water, and the NaOH solution after the third-effect evaporation is sent to a front-end chromium removal process for pH adjustment.
The ammonifying carbonization agent in the step (2) is one or more of ammonium carbonate, ammonium bicarbonate and (ammonia+carbon dioxide), and is preferably ammonium carbonate or (ammonia+carbon dioxide).
The chemical reactions that occur include:
CaSO 4 +(NH 4 ) 2 CO 3 =CaCO 3 ↓+(NH 4 ) 2 SO 4
CaSO 4 +2NH 3 +CO 2 +H 2 O = (NH 4 ) 2 SO 4 +CaCO 3 ↓
the temperature of the ammonification and carbonization reaction in the step (2) is 40-95 ℃, the reaction time is 20-150min, and the stirring speed is 10-500r/min.
In the invention, if the ammonification carbonization agent is ammonium carbonate and ammonium bicarbonate, the ratio NH of the mole amount of ammonium ions to the mole amount of sulfate ions in the calcium sulfate solid phase in the ammonification carbonization agent 4 + /SO 4 2- 1.6 to 3.4, if the ammonification carbonizer is ammonia gas+carbon dioxide, the ratio NH of the molar amount of ammonium ions in the ammonification carbonizer to the molar amount of sulfate ions in the calcium sulfate solid phase 4 + /SO 4 2- 1.6-3.4 CO 3 2- /Ca 2+ 0.9 to 1.3;
the vanadium chemical production process is that the purified vanadium liquid in the existing vanadium slag sodium roasting process is subjected to an ammonium salt vanadium precipitation process to obtain ammonium polyvanadate and wastewater, and the wastewater is subjected to a vanadium removal process and a chromium removal process to obtain high-salt ammonia nitrogen wastewater.
The sodium roasting production process of vanadium slag is a process for extracting vanadium which is used by 80% of vanadium production enterprises in the world, sodium salt (mainly sodium carbonate) is added into the vanadium slag as an additive, and polyvalent vanadium in the vanadium slag is converted into sodium salt (Na) of water-soluble pentavalent vanadium through oxidative roasting 2 O.nV 2 O 5 ) The method comprises the steps of carrying out a first treatment on the surface of the Directly leaching the sodium roasting product to obtain leaching solution containing vanadium and a small amount of impurities; removing impurities from the leaching solution, adding ammonium salt, adding sulfuric acid to adjust the solution to a certain pH value, precipitating vanadium to obtain ammonium metavanadate or ammonium polyvanadate and wastewater, and thermally decomposing to obtain vanadium pentoxide.
The ammonium sulfate solution obtained in the step (2) is sent to a front-end ammonium salt vanadium precipitation procedure; the obtained calcium carbonate solid phase is calcined at high temperature to obtain calcium oxide and carbon dioxide gas, the calcium oxide is sent to a desulfurization process for recycling, and the carbon dioxide gas is sent to an ammonification carbonization transformation process.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) Firstly, removing sulfur in the vanadium chemical wastewater containing high-salt ammonia nitrogen through calcification desulfurization reaction to obtain calcium sulfate precipitate and an ammonia-containing NaOH solution. The ammonia water prepared by the ammonia-containing NaOH solution through one-effect evaporation can be used for ammoniation carbonization transformation of calcium sulfate; the residual NaOH solution can be subjected to double-triple effect evaporation to obtain production water, the water consumption for vanadium product production is reduced, the high-concentration NaOH solution can be used for adjusting the pH value of the front-end chromium removal process, and the production cost is further lowered.
(2) Adding calcium sulfate obtained by calcification desulfurization treatment into water, adding ammonium carbonization agent, and addingPerforming an ammonification carbonization transformation reaction to obtain a calcium carbonate solid phase and an ammonium sulfate solution. Calcining solid calcium carbonate at high temperature to obtain calcium oxide and CO 2 Can be continuously used for calcification desulfurization and carbonization ammoniation transformation, realizes the high-efficiency recycling of byproducts, and has simple process flow and lower cost.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
To facilitate an understanding of the present invention, the present invention is exemplified in connection with fig. 1 as follows. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
(1) 40L of wastewater containing high-salt ammonia nitrogen is taken, and NH is contained in the solution 4 + The concentration is 5.48g/L, na + The concentration is 26.74g/L, SO 4 2- The concentration is 28.88g/L, calcium oxide is added for calcification reaction, the temperature is 95 ℃, and the ratio Ca/SO of the molar quantity of calcium in the calcification agent to the molar quantity of sulfate radical in the solution 4 2- 1.8, time 120min, stirring speed 500/min, and then separating liquid from solid to obtain a solid phase 1 and a filtrate 1 of calcium sulfate and NaOH containing ammonia;
(2) Adding the solid phase 1 into water to prepare slurry, introducing ammonia gas and carbon dioxide into the slurry to carry out ammonification and carbonization reaction, wherein the temperature is 90 ℃, and the NH is 4 + /SO 4 2- 3.4 CO 3 2- /Ca 2+ 1.3, leaching for 20min at a stirring speed of 500r/min, and then performing liquid-solid separation to obtain filtrate 2 mainly containing ammonium sulfate and solid phase 2 mainly containing calcium carbonate;
(3) Evaporating filtrate 1 at 80-100deg.C, collecting condensate water, and detecting condensate water NH 3 -N concentration of 21.9g/L; and the rest is NaOH solution, then the NaOH solution is subjected to double-triple effect evaporation, and the obtained condensed water and concentrated NaOH solution are detected to have Na concentration of 180g/L.
Example 2
(1) 40L of wastewater containing high-salt ammonia nitrogen is taken, and NH is contained in the solution 4 + The concentration is 5.48g/L, na + The concentration is 26.74g/L, SO 4 2- The concentration is 28.88g/L, calcium oxide is added for calcification reaction, the temperature is 90 ℃, and the ratio Ca/SO of the molar quantity of calcium in the calcification agent to the molar quantity of sulfate radical in the solution 4 2- 1.5, time 100min, stirring speed 400/min, and then separating liquid from solid to obtain a solid phase 1 and a filtrate 1 of calcium sulfate and NaOH containing ammonia;
(2) Adding the solid phase 1 into water to prepare slurry, adding ammonium carbonate into the slurry to carry out ammonification and carbonization reaction, wherein the temperature is 95 ℃ and the NH is 4 + /SO 4 2- 3.0, leaching for 120min, stirring at 400r/min, and performing liquid-solid separation to obtain filtrate 2 mainly containing ammonium sulfate and solid phase 2 mainly containing calcium carbonate;
(3) Evaporating filtrate 1 at 80-100deg.C, collecting condensate water, and detecting condensate water NH 3 -N concentration of 18.2g/L; and the rest is NaOH solution, then the NaOH solution is subjected to double-triple effect evaporation, and the obtained condensed water and concentrated NaOH solution are detected to have Na concentration of 162g/L.
Example 3
(1) 40L of wastewater containing high-salt ammonia nitrogen is taken, and NH is contained in the solution 4 + The concentration is 5.48g/L, na + The concentration is 26.74g/L, SO 4 2- Calcium hydroxide is added to carry out calcification reaction at the concentration of 28.88g/L and the temperature of 95 ℃ and the ratio of the molar quantity of calcium in the calcification agent to the molar quantity of sulfate radical in the solution of Ca/SO 4 2- 1.8, time 20min, stirring speed 500/min, and then separating liquid from solid to obtain a solid phase 1 and a filtrate 1 of calcium sulfate and NaOH containing ammonia;
(2) Adding the solid phase 1 into water to prepare slurry, introducing ammonia gas and carbon dioxide into the slurry to carry out ammonification and carbonization reaction, wherein the temperature is 40 ℃, and the NH is 4 + /SO 4 2- 3.4 CO 3 2- /Ca 2+ 1.3, leaching for 150min at a stirring speed of 500r/min, and then performing liquid-solid separation to obtain filtrate 2 mainly containing ammonium sulfate and solid phase 2 mainly containing calcium carbonate;
(3) Carrying out one-effect evaporation on the filtrate 1 at 80-100 ℃, collecting condensed water, and detecting that the concentration of NH3-N in the condensed water is 21.9g/L; and the rest is NaOH solution, then the NaOH solution is subjected to double-triple effect evaporation, and the obtained condensed water and concentrated NaOH solution are detected to have Na concentration of 180g/L.
Example 4
(1) 40L of wastewater containing high-salt ammonia nitrogen is taken, and NH is contained in the solution 4 + The concentration is 5.48g/L, na + The concentration is 26.74g/L, SO 4 2- The concentration is 28.88g/L, calcium chloride is added for calcification reaction, the temperature is 30 ℃, and the ratio Ca/SO of the molar quantity of calcium in the calcification agent to the molar quantity of sulfate radical in the solution 4 2- 0.8, 60min, stirring at 10/min, and separating liquid from solid to obtain solid phase 1 and filtrate 1 containing calcium sulfate and ammonia NaOH;
(2) Adding the solid phase 1 into water to prepare slurry, introducing ammonium bicarbonate into the slurry to carry out ammonification and carbonization reaction, wherein the temperature is 90 ℃, and the NH is 4 + /SO 4 2- 1.6, leaching for 20min at a stirring speed of 300r/min, and then performing liquid-solid separation to obtain filtrate 2 mainly containing ammonium sulfate and solid phase 2 mainly containing calcium carbonate; the filtrate 2 mainly containing ammonium sulfate can be used for an ammonium salt vanadium precipitation process, the solid phase 2 mainly containing calcium carbonate is calcined to generate calcium oxide which can be used for a calcification desulfurization process, and simultaneously, the generated carbon dioxide can be used for an ammonification carbonization transformation process;
(3) Evaporating filtrate 1 at 80-100deg.C, collecting condensate water, and detecting condensate water NH 3 -N concentration of 19.6g/L; and the rest is NaOH solution, then the NaOH solution is subjected to double-triple effect evaporation, and the obtained condensed water and concentrated NaOH solution are detected to have Na concentration of 140g/L. The concentrated NaOH solution can be used for the chromium removal process, and condensed water NH 3 -N goes to an ammonification carbonization transformation process.
From the three embodiments described above, it can be concluded that: the vanadium chemical wastewater containing high-salt ammonia nitrogen can realize the recycling of elements such as sodium, ammonium, calcium, sulfur, carbon and the like through the procedures of calcification desulfurization, ammonification transformation, solution deamination, high-temperature calcination of calcium carbonate and the like, and the method has the advantages of simple process flow and good wastewater treatment effect, and is suitable for industrial production.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The vanadium chemical high-salt ammonia nitrogen wastewater treatment method is characterized by comprising the following steps of:
(1) Adding a calcification agent into the high-salt ammonia nitrogen wastewater to perform calcification desulfurization treatment to obtain calcium sulfate precipitate and an ammonia-containing NaOH solution; the high-salt ammonia nitrogen wastewater is vanadium chemical production wastewater, and contains NH 4+ 、SO 4 2- And Na (Na) - ；
(2) Adding the calcium sulfate obtained in the step (1) into water, adding an ammonification carbonization agent, and performing ammonification carbonization transformation reaction to obtain a calcium carbonate solid phase and an ammonium sulfate solution.
2. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 1, wherein the calcification agent in the step (1) is at least one of calcium oxide, calcium hydroxide and calcium chloride;
the ammonifying carbonizing agent in the step (2) is at least one of ammonium carbonate, ammonium bicarbonate and ammonia and carbon dioxide.
3. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 2, wherein the calcification agent in the step (1) is calcium oxide;
the ammonifying carbonizing agent in the step (2) is ammonium carbonate or ammonia gas plus carbon dioxide.
4. The vanadium chemical high-salt ammonia nitrogen wastewater treatment method according to claim 1The method is characterized in that the temperature of the calcification reaction in the step (1) is 30-95 ℃, and the ratio Ca/SO of the molar quantity of calcium in the calcification agent to the molar quantity of sulfate radical in the high-salt ammonia nitrogen wastewater 4 2- 0.8-1.8, calcification time 20-120min, and stirring speed 10-500r/min.
5. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 1, wherein ammonia water obtained by first-effect evaporation of the ammonia-containing NaOH solution obtained in the step (1) is sent to an ammonification carbonization transformation process, and the first-effect evaporated NaOH solution is sent to second-effect evaporation and third-effect evaporation to obtain production water and NaOH solution.
6. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 1, wherein the temperature of the ammonification and carbonization reaction in the step (2) is 40-95 ℃, the reaction time is 20-150min, and the stirring speed is 10-500r/min.
7. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 2, wherein if the ammonification carbonization agent is ammonium carbonate or ammonium bicarbonate, the ratio NH of the molar amount of ammonium ions in the ammonification carbonization agent to the molar amount of sulfate ions in the calcium sulfate solid phase is 4 + /SO 4 2- 1.6 to 3.4;
if the ammoniated carbonizer is ammonia+carbon dioxide, the ratio NH of the molar amount of ammonium ions in the ammoniated carbonizer to the molar amount of sulfate ions in the calcium sulfate solid phase 4 + /SO 4 2- 1.6-3.4 CO 3 2- /Ca 2+ 0.9-1.3.
8. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 2 or 3, wherein the calcium carbonate solid phase obtained in the step (2) is calcined at a high temperature to obtain calcium oxide and carbon dioxide gas, the calcium oxide is sent to calcification desulfurization treatment for recycling, and the carbon dioxide gas is sent to ammonification carbonization transformation reaction.
9. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 5, wherein the vanadium chemical production process is that the purified vanadium liquid in the existing vanadium slag sodium roasting process is subjected to an ammonium salt vanadium precipitation process to obtain ammonium polyvanadate and wastewater, and the wastewater is subjected to a vanadium removal process and a chromium removal process to obtain high-salt ammonia nitrogen wastewater.
10. The method for treating vanadium chemical high-salt ammonia nitrogen wastewater according to claim 9, wherein NaOH solution obtained by triple effect evaporation is sent to a chromium removal process;
and (3) delivering the ammonium sulfate solution obtained in the step (2) into an ammonium salt vanadium precipitation process.
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