CN111960444A - Method for preparing lithium carbonate by utilizing manganese-containing wastewater and waste lithium battery lithium-rich solution - Google Patents
Method for preparing lithium carbonate by utilizing manganese-containing wastewater and waste lithium battery lithium-rich solution Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 110
- 239000002351 wastewater Substances 0.000 title claims abstract description 60
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 44
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 40
- 239000011572 manganese Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000002699 waste material Substances 0.000 title claims abstract description 27
- 230000009615 deamination Effects 0.000 claims abstract description 34
- 238000006481 deamination reaction Methods 0.000 claims abstract description 34
- 239000011777 magnesium Substances 0.000 claims abstract description 25
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 24
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011737 fluorine Substances 0.000 claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 16
- 239000011575 calcium Substances 0.000 claims abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 10
- 238000004064 recycling Methods 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 63
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 54
- 239000000706 filtrate Substances 0.000 claims description 49
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 33
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 32
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 27
- 229910021529 ammonia Inorganic materials 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 23
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 22
- 229910001424 calcium ion Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- 239000001569 carbon dioxide Substances 0.000 claims description 16
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 13
- 239000011656 manganese carbonate Substances 0.000 claims description 13
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 12
- 229910001437 manganese ion Inorganic materials 0.000 claims description 12
- 229940093474 manganese carbonate Drugs 0.000 claims description 11
- 235000006748 manganese carbonate Nutrition 0.000 claims description 11
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000000920 calcium hydroxide Substances 0.000 claims description 9
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000005273 aeration Methods 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 230000001105 regulatory effect Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000909 electrodialysis Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000003014 ion exchange membrane Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- VQBIMXHWYSRDLF-UHFFFAOYSA-M sodium;azane;hydrogen carbonate Chemical group [NH4+].[Na+].[O-]C([O-])=O VQBIMXHWYSRDLF-UHFFFAOYSA-M 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 3
- 231100000719 pollutant Toxicity 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 12
- 238000011084 recovery Methods 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 5
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 239000013064 chemical raw material Substances 0.000 description 3
- 238000006115 defluorination reaction Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for preparing lithium carbonate by utilizing manganese-containing wastewater and a waste lithium battery lithium-rich solution. In the method, in the deamination wastewater obtained from the bottom of the negative pressure deamination tower, the manganese content is less than or equal to 1mg/L, the ammonia nitrogen content is less than or equal to 10mg/L, the total hardness of the wastewater is less than or equal to 50mg/L and is lower than GB 31573 2015 inorganic chemical industry pollutant discharge standard, and the treated wastewater can reach the standard to be discharged or can be returned to a production system for recycling. In the method, the purity of the obtained lithium carbonate product is more than 99.6 wt%, the content of magnesium is less than 0.006 wt%, the content of calcium is less than 0.004 wt%, the content of iron is less than 0.001 wt%, and the content of fluorine is less than 0.009 wt%.
Description
Technical Field
The invention relates to the field of wastewater treatment and resource recovery, in particular to a method for preparing lithium carbonate by utilizing manganese-containing wastewater and a waste lithium battery lithium-rich solution.
More particularly, the present invention relates to a method for preparing lithium carbonate, in which manganese dioxide is used to remove Fe from a lithium-rich solution using manganese dioxide, ammonia gas and carbon dioxide generated during the recovery of manganese-containing wastewater2+And introducing ammonia gas and carbon dioxide into the lithium-rich solution to precipitate lithium carbonate crystals.
Background
According to statistics, over 1000 million tons of manganese ore is mined in China every year, a large amount of manganese-containing ammonia nitrogen wastewater is generated in the deep processing process of the manganese ore, the wastewater is complex in water quality, contains a large amount of pollutants such as manganese ions, sulfate, ammonia nitrogen and the like, also contains a small amount of metal ions such as magnesium, calcium and the like, and can leak to an external environment if the wastewater is not processed in time, so that the water quality of the surrounding environment is seriously harmed, the ecological balance is damaged, and the human health is harmed.
With the rapid development of lithium ion battery technology, the yield of lithium ion batteries shows a rapid increase trend, the re-resource of waste lithium ion batteries becomes a research hotspot, a wet recovery technology is mainly adopted at present, in the wet recovery technology, waste lithium batteries are subjected to the procedures of discharging disassembly, crushing and screening, acidic leaching, purification and impurity removal, precursor precipitation and the like to obtain precipitate containing lithium fluoride, the precipitate is dissolved in hydrochloric acid to prepare a lithium-rich solution, and the lithium-rich solution contains a large amount of impurity ions such as iron (ferrous ions), magnesium, calcium, fluorine and the like, so that the difficulty in recovering lithium elements is large, and the quality of recovered lithium carbonate is low. Therefore, in consideration of the economical efficiency of lithium recovery, most lithium battery recovery enterprises adopting the traditional wet recovery technology choose to abandon the recovery of lithium, which causes great waste of lithium resources.
How to reduce the pollution of the manganese-containing wastewater to the environment and recover the manganese resource therein, and how to recover the lithium resource of the waste lithium battery lithium-rich solution and improve the quality of lithium carbonate becomes a realistic problem which needs to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing lithium carbonate by utilizing manganese-containing wastewater and a waste lithium battery lithium-rich solution, and the method can recover manganese dioxide, ammonia gas and carbon dioxide from the manganese-containing wastewater, and the manganese dioxide, ammonia gas and carbon dioxide are used as raw materials to be added into the lithium-rich solution treatment process to prepare high-quality lithium carbonate.
In order to achieve the purpose, the invention provides the following technical scheme:
the invention provides a method for preparing lithium carbonate by utilizing manganese-containing wastewater and waste lithium battery lithium-rich solution, which comprises the following steps:
adding carbonate into the manganese-containing ammonia nitrogen wastewater, and performing solid-liquid separation to obtain manganese carbonate precipitate and primary filtrate; calcining manganese carbonate to obtain manganese dioxide and carbon dioxide;
adding Ca (OH) to the primary filtrate2Generating hydroxide and calcium sulfate precipitates which are insoluble in water, introducing air for aeration and stripping at the same time to separate part of free ammonia, collecting ammonia-containing gas, and performing solid-liquid separation to obtain secondary filtrate;
adding a composition of sodium carbonate and ammonium carbonate into the secondary filtrate, removing residual calcium ions in the filtrate, and carrying out solid-liquid separation to obtain a third filtrate;
adding a pH regulator into the third filtrate, preheating and heating the filtrate, then feeding the filtrate into the top of a negative pressure deamination tower, allowing ammonia-containing wastewater in the negative pressure deamination tower to flow downwards and to be in countercurrent contact with high-temperature steam directly introduced into the bottom of the negative pressure deamination tower, obtaining deamination wastewater meeting the emission standard at the bottom of the negative pressure deamination tower, allowing ammonia-containing gas to escape from the top of the negative pressure deamination tower, and mixing the ammonia-containing gas obtained after aeration stripping for later use;
passing the lithium-rich solution through a filter containing manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
adding sodium carbonate into the concentrated lithium-rich solution to remove most of magnesium and calcium ions, then adding a mixture of sodium hydroxide and sodium carbonate to further remove the rest of magnesium and calcium ions to obtain the lithium-rich solution after impurity removal;
electrodialysis is carried out on the lithium-rich solution after impurity removal by utilizing a monovalent ion permselective ion exchange membrane to obtain a purified lithium-rich solution;
and introducing ammonia gas and carbon dioxide into the purified lithium-rich solution, separating lithium carbonate crystals out, carrying out solid-liquid separation, and carrying out flash evaporation drying to obtain a lithium carbonate product.
In a specific embodiment, the concentrated lithium-rich solution is subjected to fluorine removal treatment by using the existing fluorine removal methods, such as fluorine removal by extraction, fluorine removal by precipitation, and the like, and then the steps of magnesium and calcium removal are carried out.
In a specific embodiment, the carbonate is any one of sodium carbonate and potassium carbonate, and the molar ratio of the carbonate to the manganese ions is 1-3: 1, reacting carbonate with manganese ions in the wastewater to generate manganese carbonate precipitate which is insoluble in water, and recycling manganese dioxide and carbon dioxide generated after pyrolysis.
Further, the carbonate is sodium carbonate, and the molar ratio of the sodium carbonate to the manganese ions is 1-1.
In the present invention, since MgCO3Solubility product of KSPIs 6.82X 10-6，CaCO3Solubility product of KSPIs 3.36 multiplied by 10-9，MnCO3Solubility product of KSPIs 2.24X 10-11Adding carbonate into the manganese-containing ammonia nitrogen wastewater, wherein the manganese carbonate is preferentially precipitated.
In a specific embodiment, a calcium hydroxide solution with the mass fraction of 10% -30% is adopted, and the molar ratio of calcium hydroxide to sulfate radical is 1-3: 1, the molar ratio is more than 1: 1, reacting calcium hydroxide with residual metal ions such as manganese ions and sulfate radicals to generate hydroxide precipitates and calcium sulfate precipitates.
In a specific embodiment, the molar ratio of the sodium carbonate to the ammonium carbonate is 0.1-10: 1.
in a specific embodiment, the pH regulator adopts any one of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the pH value of the filtrate is regulated to be more than or equal to 10.8.
Further, sodium hydroxide is used as the pH regulator.
In a specific embodiment, the filtrate and high-temperature effluent at the bottom of the negative-pressure deamination tower exchange heat in a preheater, and the filtrate enters the top of the negative-pressure deamination tower after being preheated and heated.
In a specific embodiment, the content of manganese in the deamination wastewater obtained from the bottom of the negative pressure deamination tower is less than or equal to 1mg/L, the content of ammonia nitrogen is less than or equal to 10mg/L, and the total hardness of the wastewater is less than or equal to 50 mg/L.
Under acidic condition, the lithium-rich solution contains a large amount of Fe2+Manganese dioxide being Fe2+Conversion to Fe3+Good catalyst of (2), Fe produced3+Hydrolysis to Fe (OH)3The precipitate was immediately removed by filtration.
In a specific embodiment, stoichiometric amounts of sodium carbonate are added according to the amount of magnesium and calcium ions in the lithium-rich solution, and after sufficient reaction, the precipitate is filtered to remove most of the magnesium and calcium ions.
In a specific embodiment, a mixture of sodium hydroxide and sodium carbonate is added to adjust the pH of the lithium-rich solution to 13, the mass concentration of sodium hydroxide is 10% to 20%, and the mass concentration of sodium carbonate is 40% to 60%.
In the present invention, LiCO is used as a base material3Solubility product KSPIs 8.15 multiplied by 10-4，CaCO3Solubility product of KSPIs 3.36 multiplied by 10-9，MgCO3Solubility product of KSPIs 6.82X 10-6Therefore, stoichiometric sodium carbonate is added into the lithium-rich solution, and no lithium carbonate is separated out; due to Mg (OH)2Solubility product of KSPIs 1.8X 10-11Thus, sodium hydroxide was added to deeply remove magnesium ions.
In a specific embodiment, the lithium concentration in the purified lithium-rich solution is between 10g/L and 200 g/L.
In a specific embodiment, ammonia and carbon dioxide are passed into the purified lithium-rich solution to control NH3The mol ratio of Li to Li is 1-1.6; CO 22The molar ratio of Li to Li is 0.8-1.2.
In a specific embodiment, in the step of precipitating lithium carbonate crystals, ammonium chloride contained in the filtrate obtained by solid-liquid separation is recycled to obtain an ammonium chloride product as a chemical raw material.
The chemical reaction equation mainly related to the invention is as follows:
CO3 2-+Mn2+→MnCO3↓ (1)
OH-+Mn2+→Mn(OH)2↓ (2)
SO4 2-+Ca2+→CaSO4↓ (3)
CO3 2-+Ca2+→CaCO3↓ (4)
CO3 2-+Mg2+→MgCO3↓ (5)
OH-+Mg2+→Mg(OH)2↓ (6)
NH3·H2O→NH3↑+H2O (7)
NH4 ++HO-→NH3·H2O (8)
4H++2Fe2++MnO2→Mn2++2Fe3++2H2O (9)
2OH-+Fe2+→Fe(OH)2↓; complete precipitation pH 9.7 (10)
3OH-+Fe3+→Fe(OH)3↓; complete precipitation pH 4.1 (11)
2LiCl+2NH4OH+CO2→Li2CO3↓+2NH4Cl+H2O (12)
Compared with the prior art, the invention has the beneficial technical effects that:
(1) the invention provides a method for preparing lithium carbonate by utilizing manganese-containing wastewater and a waste lithium battery lithium-rich solution.
(2) In the method, in the deamination wastewater obtained from the bottom of the negative pressure deamination tower, the manganese content is less than or equal to 1mg/L, the ammonia nitrogen content is less than or equal to 10mg/L, the total hardness of the wastewater is less than or equal to 50mg/L and is lower than GB 31573 2015 inorganic chemical industry pollutant discharge standard, and the treated wastewater can reach the standard to be discharged or can be returned to a production system for recycling.
(3) In the method, the purity of the obtained lithium carbonate product is more than 99.6 wt%, the content of magnesium is less than 0.006 wt%, the content of calcium is less than 0.004 wt%, the content of iron is less than 0.001 wt%, and the content of fluorine is less than 0.009 wt%.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
Fig. 1 is a process flow chart of the method for preparing lithium carbonate by using manganese-containing wastewater and waste lithium battery lithium-rich solution.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by those skilled in the art without any creative work based on the embodiments of the present invention belong to the protection scope of the present invention.
The experimental procedures described in the following examples are conventional unless otherwise specified, and the reagents and materials described therein are commercially available without further specification.
In the embodiment of the invention, the inlet water of the manganese-containing ammonia nitrogen wastewater is as follows: the ammonia nitrogen content is 200-30000 mg/L; the manganese ion content is 200-10000 mg/L; the sulfate radical content is 1000-30000 mg/L; the content of magnesium ions is 100-20000 mg/L; the content of calcium ions is 200-2000 mg/L; the total hardness of water is 200-22000 mg/L, and the pH is 2-7.
Waste lithium battery lithium-rich solution: the lithium ion content is 500-5000 mg/L; the content of fluorine ions is 150-500 mg/L; the content of iron ions is 100-900 mg/L; the content of calcium ions is 100-900 mg/L; the content of magnesium ions is 100-900 mg/L.
Example 1
The method for preparing lithium carbonate by using manganese-containing wastewater and waste lithium battery lithium-rich solution in the embodiment comprises the following steps:
(1) the manganese-containing ammonia nitrogen wastewater firstly enters a regulating reservoir, the water quantity and the water quality are regulated and uniform, then the manganese-containing ammonia nitrogen wastewater enters a wastewater treatment system, sodium carbonate is added into the manganese-containing ammonia nitrogen wastewater, and the molar ratio of the sodium carbonate to manganese ions is 1: 1, generating carbonate sediment which is insoluble in water, and performing solid-liquid separation to obtain manganese carbonate sediment and primary filtrate; calcining manganese carbonate to obtain manganese dioxide and carbon dioxide;
(2) to the primary filtrate was added calcium hydroxide (20% calcium hydroxide solution) in a molar ratio of calcium hydroxide to sulfate of 2: 1, generating hydroxide and calcium sulfate precipitates which are insoluble in water, introducing air for aeration and stripping at the same time to separate part of free ammonia, collecting ammonia-containing gas, and performing solid-liquid separation to obtain secondary filtrate;
(3) adding a composition of sodium carbonate and ammonium carbonate (the molar ratio is 1: 1) into the secondary filtrate, removing residual calcium ions in the filtrate, carrying out solid-liquid separation to obtain a third filtrate, carrying out filter pressing on the precipitate through a filter press, and reasonably stacking the obtained filter cakes;
(4) adding sodium hydroxide into the third filtrate to adjust the pH value of the filtrate to be more than or equal to 10.8, so that ionic ammonium in the filtrate is converted into molecular ammonia, carrying out heat exchange on the filtrate and high-temperature effluent at the bottom of a negative-pressure deamination tower in a preheater, preheating and heating the filtrate, then feeding the filtrate into the top of the negative-pressure deamination tower, enabling ammonia-containing wastewater in the negative-pressure deamination tower to flow downwards and to be in countercurrent contact with high-temperature steam directly introduced into the bottom of the tower, gradually reducing the ammonia content in the wastewater under the alkaline and high-temperature conditions and the power action, obtaining deamination wastewater meeting the discharge standard at the bottom of the negative-pressure deamination tower, discharging the deamination wastewater as required, and recycling the ammonia-containing gas to a production workshop, wherein the ammonia;
(5) passing the waste lithium battery lithium-rich solution through a filtering device filled with manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
(6) adding sodium carbonate into the concentrated lithium-rich solution, adding stoichiometric sodium carbonate according to the amount of magnesium and calcium ions in the lithium-rich solution to remove most of magnesium and calcium ions, then adding a mixture of sodium hydroxide (with the mass concentration of 15%) and sodium carbonate (with the mass concentration of 45%), adjusting the pH value of the lithium-rich solution to 13, and further removing the residual magnesium and calcium ions to obtain the lithium-rich solution after impurity removal;
(7) electrodialysis is carried out on the lithium-rich solution after impurity removal by utilizing a monovalent ion permselective ion exchange membrane to obtain a purified lithium-rich solution (the lithium concentration is 10 g/L-200 g/L);
(8) introducing ammonia gas and carbon dioxide into the purified lithium-rich solution, and controlling NH3The molar ratio/Li is 1.2: 1; CO 22The molar ratio/Li is 1: 1, precipitating lithium carbonate crystals, carrying out solid-liquid separation, and then carrying out flash evaporation drying to obtain a lithium carbonate product, wherein ammonium chloride contained in filtrate obtained by the solid-liquid separation is recycled to obtain an ammonium chloride product which is used as a chemical raw material.
In the deamination wastewater obtained in the embodiment 1, the content of manganese ions is 0.9 mg/L; the ammonia nitrogen content is 8.6 mg/L; the sulfate content is 274 mg/L; the total hardness of water is 48mg/L, and the pH value is 6-9.
In the lithium carbonate product obtained in example 1, the purity of the lithium carbonate product was 99.8 wt%, the content of magnesium was 0.004 wt%, the content of calcium was 0.002 wt%, the content of iron was 0.0006 wt%, and the content of fluorine was 0.006 wt%.
Example 2
The method for preparing lithium carbonate by using manganese-containing wastewater and waste lithium battery lithium-rich solution in the embodiment comprises the following steps:
(1) the manganese-containing ammonia nitrogen wastewater firstly enters a regulating reservoir, the water quantity and the water quality are regulated and uniform, then the manganese-containing ammonia nitrogen wastewater enters a wastewater treatment system, and then sodium carbonate is added into the manganese-containing ammonia nitrogen wastewater, wherein the molar ratio of the sodium carbonate to manganese ions is 2: 1, generating carbonate sediment which is insoluble in water, and performing solid-liquid separation to obtain manganese carbonate sediment and primary filtrate; calcining manganese carbonate to obtain manganese dioxide and carbon dioxide;
(2) to the primary filtrate was added calcium hydroxide (10% calcium hydroxide solution) in a molar ratio of calcium hydroxide to sulfate of 1: 1, generating hydroxide and calcium sulfate precipitates which are insoluble in water, introducing air for aeration and stripping at the same time to separate part of free ammonia, collecting ammonia-containing gas, and performing solid-liquid separation to obtain secondary filtrate;
(3) adding a composition of sodium carbonate and ammonium carbonate (the molar ratio is 10: 1) into the secondary filtrate, removing residual calcium ions in the filtrate, carrying out solid-liquid separation to obtain a third filtrate, carrying out filter pressing on the precipitate through a filter press, and reasonably stacking the obtained filter cakes;
(4) adding sodium hydroxide into the third filtrate to adjust the pH value of the filtrate to be more than or equal to 10.8, so that ionic ammonium in the filtrate is converted into molecular ammonia, carrying out heat exchange on the filtrate and high-temperature effluent at the bottom of a negative-pressure deamination tower in a preheater, preheating and heating the filtrate, then feeding the filtrate into the top of the negative-pressure deamination tower, enabling ammonia-containing wastewater in the negative-pressure deamination tower to flow downwards and to be in countercurrent contact with high-temperature steam directly introduced into the bottom of the tower, gradually reducing the ammonia content in the wastewater under the alkaline and high-temperature conditions and the power action, obtaining deamination wastewater meeting the discharge standard at the bottom of the negative-pressure deamination tower, discharging the deamination wastewater as required, and recycling the ammonia-containing gas to a production workshop, wherein the ammonia;
(5) passing the waste lithium battery lithium-rich solution through a filtering device filled with manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
(6) adding sodium carbonate into the concentrated lithium-rich solution, adding stoichiometric sodium carbonate according to the amount of magnesium and calcium ions in the lithium-rich solution to remove most of magnesium and calcium ions, then adding a mixture of sodium hydroxide (with the mass concentration of 20%) and sodium carbonate (with the mass concentration of 50%), adjusting the pH value of the lithium-rich solution to 13, and further removing the residual magnesium and calcium ions to obtain the lithium-rich solution after impurity removal;
(7) electrodialysis is carried out on the lithium-rich solution after impurity removal by utilizing a monovalent ion permselective ion exchange membrane to obtain a purified lithium-rich solution;
(8) introducing ammonia gas and carbon dioxide into the purified lithium-rich solution, and controlling NH3The molar ratio/Li is 1.6: 1; CO 22Molar ratio/Li of 0.8: 1, precipitating lithium carbonate crystals, carrying out solid-liquid separation, and then carrying out flash evaporation drying to obtain a lithium carbonate product, wherein ammonium chloride contained in filtrate obtained by the solid-liquid separation is recycled to obtain an ammonium chloride product which is used as a chemical raw material.
In the deamination wastewater obtained in the embodiment 2, the content of manganese ions is 0.8 mg/L; the ammonia nitrogen content is 9.2 mg/L; the sulfate radical content is 235 mg/L; the total hardness of water is 52mg/L, and the pH value is 6-9.
In the lithium carbonate product obtained in example 2, the purity of the lithium carbonate product was 99.6 wt%, the content of magnesium was 0.005 wt%, the content of calcium was 0.003 wt%, the content of iron was 0.0009 wt%, and the content of fluorine was 0.008 wt%.
Example 3
The preparation method is the same as that of example 1, and only differs from the following steps: the concentrated lithium-rich solution is subjected to defluorination treatment by adopting the existing defluorination method (defluorination by extraction method, application number: 201010584552.3), and then the steps of magnesium and calcium removal are carried out.
In the lithium carbonate product obtained in example 3, the purity of the lithium carbonate product was 99.9 wt%, the content of magnesium was 0.0045 wt%, the content of calcium was 0.0028 wt%, the content of iron was 0.0008 wt%, and the content of fluorine was 0.002 wt%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. Modifications and variations that may occur to those skilled in the art without departing from the spirit and scope of the invention are to be considered as within the scope of the invention.
Claims (10)
1. A method for preparing lithium carbonate by utilizing manganese-containing wastewater and waste lithium battery lithium-rich solution is characterized by comprising the following steps:
adding carbonate into the manganese-containing ammonia nitrogen wastewater, and performing solid-liquid separation to obtain manganese carbonate precipitate and primary filtrate; calcining manganese carbonate to obtain manganese dioxide and carbon dioxide;
adding Ca (OH) to the primary filtrate2Generating hydroxide and calcium sulfate precipitates which are insoluble in water, introducing air for aeration and stripping at the same time to separate part of free ammonia, collecting ammonia-containing gas, and performing solid-liquid separation to obtain secondary filtrate;
adding a composition of sodium carbonate and ammonium carbonate into the secondary filtrate, removing residual calcium ions in the filtrate, and carrying out solid-liquid separation to obtain a third filtrate;
adding a pH regulator into the third filtrate, preheating and heating the filtrate, then feeding the filtrate into the top of a negative pressure deamination tower, allowing ammonia-containing wastewater in the negative pressure deamination tower to flow downwards and to be in countercurrent contact with high-temperature steam directly introduced into the bottom of the negative pressure deamination tower, obtaining deamination wastewater meeting the emission standard at the bottom of the negative pressure deamination tower, allowing ammonia-containing gas to escape from the top of the negative pressure deamination tower, and mixing the ammonia-containing gas obtained after aeration stripping for later use;
passing the lithium-rich solution through a filter containing manganese dioxide to remove Fe2+Conversion to Fe3+Converting the lithium-rich solution into hydroxide precipitate, evaporating and concentrating, and carrying out solid-liquid separation to obtain a concentrated lithium-rich solution;
adding sodium carbonate into the concentrated lithium-rich solution to remove most of magnesium and calcium ions, then adding a mixture of sodium hydroxide and sodium carbonate to further remove the rest of magnesium and calcium ions to obtain the lithium-rich solution after impurity removal;
electrodialysis is carried out on the lithium-rich solution after impurity removal by utilizing a monovalent ion permselective ion exchange membrane to obtain a purified lithium-rich solution;
and introducing ammonia gas and carbon dioxide into the purified lithium-rich solution, separating lithium carbonate crystals out, carrying out solid-liquid separation, and carrying out flash evaporation drying to obtain a lithium carbonate product.
2. The method for preparing lithium carbonate by using the manganese-containing wastewater and the lithium-rich solution of the waste lithium battery as claimed in claim 1, wherein the concentrated lithium-rich solution is subjected to fluorine removal treatment, and the fluorine removal is performed by using the existing fluorine removal methods, such as fluorine removal by an extraction method and fluorine removal by a precipitation method, and then magnesium and calcium removal is performed.
3. The method for preparing lithium carbonate by using the manganese-containing wastewater and the waste lithium battery lithium-rich solution according to claim 1, wherein the carbonate is any one of sodium carbonate and potassium carbonate, and the molar ratio of the carbonate to manganese ions is 1-3: 1, reacting carbonate with manganese ions in the wastewater to generate manganese carbonate precipitate which is insoluble in water, and recycling manganese dioxide and carbon dioxide generated after pyrolysis.
4. The method for preparing lithium carbonate by using the manganese-containing wastewater and the waste lithium battery lithium-rich solution according to claim 1, wherein a calcium hydroxide solution with the mass fraction of 10% -30% is adopted, and the molar ratio of calcium hydroxide to sulfate radical is 1-3: 1, the molar ratio is more than 1: 1.
5. the method for preparing lithium carbonate by using the manganese-containing wastewater and the waste lithium battery lithium-rich solution according to claim 1, wherein the molar ratio of the sodium carbonate to the ammonium carbonate is 0.1-10: 1.
6. the method for preparing lithium carbonate by using the manganese-containing wastewater and the waste lithium battery lithium-rich solution according to claim 1, wherein the pH regulator is any one of sodium hydroxide, potassium hydroxide and calcium hydroxide, and the pH value of the filtrate is regulated to be more than or equal to 10.8.
7. The method for preparing lithium carbonate by utilizing the manganese-containing wastewater and the lithium-rich solution of the waste lithium battery as claimed in claim 1, wherein stoichiometric sodium carbonate is added according to the amount of magnesium and calcium ions in the lithium-rich solution, and after full reaction, the precipitate is filtered to remove most of the magnesium and calcium ions.
8. The method for preparing lithium carbonate by using the manganese-containing wastewater and the lithium-rich solution of the waste lithium battery as claimed in claim 1, wherein the pH of the lithium-rich solution is adjusted to 13 by adding a mixture of sodium hydroxide and sodium carbonate, the mass concentration of the sodium hydroxide is 10-20%, and the mass concentration of the sodium carbonate is 40-60%.
9. The method for preparing lithium carbonate by using the manganese-containing wastewater and the lithium-rich solution of the waste lithium battery as claimed in claim 1, wherein the lithium concentration in the purified lithium-rich solution is 10 g/L-200 g/L.
10. The method for preparing lithium carbonate by using manganese-containing wastewater and waste lithium battery lithium-rich solution according to claim 1, wherein ammonia gas and carbon dioxide are introduced into the purified lithium-rich solution, and NH is controlled3The mol ratio of Li to Li is 1-1.6; CO 22The molar ratio of Li to Li is 0.8-1.2.
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