CN117378071A - Method for treating sodium sulfate-containing residue process streams of battery manufacturing facilities, battery recycling facilities or steel production plants - Google Patents
Method for treating sodium sulfate-containing residue process streams of battery manufacturing facilities, battery recycling facilities or steel production plants Download PDFInfo
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- CN117378071A CN117378071A CN202280037513.2A CN202280037513A CN117378071A CN 117378071 A CN117378071 A CN 117378071A CN 202280037513 A CN202280037513 A CN 202280037513A CN 117378071 A CN117378071 A CN 117378071A
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- potassium chloride
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- water
- lithium
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- 238000000034 method Methods 0.000 title claims abstract description 195
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 96
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 38
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 36
- 239000010959 steel Substances 0.000 title claims abstract description 36
- 238000004064 recycling Methods 0.000 title claims abstract description 34
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 33
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 33
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 140
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 75
- 239000001103 potassium chloride Substances 0.000 claims abstract description 70
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 35
- 229910052939 potassium sulfate Inorganic materials 0.000 claims abstract description 20
- 235000011151 potassium sulphates Nutrition 0.000 claims abstract description 20
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000003337 fertilizer Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 40
- 238000002156 mixing Methods 0.000 claims description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- 239000011780 sodium chloride Substances 0.000 claims description 20
- 229910052720 vanadium Inorganic materials 0.000 claims description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 17
- 238000011084 recovery Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 10
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000001120 potassium sulphate Substances 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims description 6
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 6
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims description 6
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001164 aluminium sulphate Substances 0.000 claims description 3
- 235000011128 aluminium sulphate Nutrition 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 12
- 239000002351 wastewater Substances 0.000 description 11
- 239000011734 sodium Substances 0.000 description 10
- 239000002699 waste material Substances 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 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 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000007514 bases Chemical class 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012993 chemical processing Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Secondary Cells (AREA)
Abstract
The present invention relates to a method for producing a fertilizer composition comprising potassium sulfate from a sodium sulfate-containing residue process stream of a battery manufacturing facility, a battery recycling facility or a steel production plant, wherein a residue process stream from a battery manufacturing facility, a battery recycling facility or a steel production plant is provided; optionally providing water; providing potassium chloride; and providing a reaction mixture comprising the optional water, potassium chloride and a residual process stream, and reacting the same, wherein potassium sulfate is obtained.
Description
Technical Field
The present invention relates to a method for providing value added products from a residue process stream from a battery production or recycling facility or steel production plant.
Background
Today, there is increasing interest in providing more sustainable products and methods. Different industries aim to better utilize the earth's limited resources.
Today, there is great interest in increasing awareness of climate change and limited supply of fossil fuels.
The awareness and limited supply facilitate finding alternative energy sources for e.g. the operation of a vehicle. The demand for batteries based on lithium ion technology is rapidly increasing. This also means that emissions, solid and liquid residues from cell production increase. Thus, recycling and material optimization have become related problems in recent years. Resource optimization has become a necessity for continued use of lithium ion batteries in today's and future's most countries.
Many industries want to improve the sustainability of their products and processes and, for example, limit the amount of waste generated by a facility.
The battery manufacturing industry is continually striving to minimize the provision of residue and aims to recover process-essential chemicals like cobalt, lithium and manganese, which helps to reduce the operating costs of the facility. Residues from the cell manufacturing process may be aqueous wastewater streams, ammonia, n-methyl pyrrolidone, and hazardous wastes such as cell metal components. However, since the residue stream, particularly the waste water stream, can be quite bulky, it is desirable to reduce the amount of residue and provide value added components from the stream categorized as waste to improve the overall operation of the battery manufacturing facility in terms of cost and raw material usage, and to allow reuse of the earth limited resources. Furthermore, local or national regulations may influence whether battery production is allowed or not, taking into account residues and emissions provided from the process, in particular with regard to emissions to the water receiver. Undesirable elements like sulphate and sodium can be provided at high levels in different production processes, such as steel production in steel works, or battery production or recovery, and said undesirable elements negatively affect the residual process streams, as they are expensive to handle and if forwarded directly to sewer and/or wastewater treatment plants they can put a great stress on said downstream processes. Today, the presence or the possibility of the presence of large amounts of sulphate and sodium will prevent approval of the establishment of a battery production facility or a battery recycling facility. Sodium sulfate is a problematic by-product to be treated by battery manufacturers, battery recycling companies, or steel manufacturers. In view of throughput, the cost of processing sodium sulfate can be significant and not addressing chemical processing can prevent a company from obtaining the license required to continue its production or obtaining new licenses to increase production or build new production facilities.
In addition, the battery recycling industry is continually striving to minimize the provision of residue. As is the steel production industry.
Today, sodium sulfate present in the residual process stream may be discharged through drains or drains, for example, to a waste water system, or to a landfill site or separated from the residual stream and sold as a low grade chemical. The sodium sulfate-containing residue process stream from the cell production facility is primarily derived from the oxidation step of cathode production. The sodium sulfate-containing residual process stream from steel plants is mainly derived from vanadium recovery. Even if sodium sulfate is considered a waste material, it may be a valuable asset if it is provided for use as sodium sulfate may be present in large amounts. Sodium sulfate obtained by treatment is considered to be a problem for battery manufacturing facilities, battery recycling facilities, or steel plants. However, if sodium sulfate can be fully utilized, it may become a value-added product in the overall process.
A problem with the current residual process streams of battery manufacturing facilities is that potentially valuable chemicals are not recovered or recovered therefrom. In practice, large amounts of chemicals are always discharged to landfills, or disposed of as low grade chemicals, or sent to waste water systems. The same is true in the case of battery recycling facilities, such as in the case of handling lithium batteries, e.g., electric Vehicle (EV) batteries, for recycling purposes, for example. This is another concern of the present invention. Furthermore, for steel production plants, there may be no chemicals of possible value from which to retrieve or recover the residual process stream. In addition, in reality, large amounts of chemicals may be discharged to landfills, or disposed of as low grade chemicals, or sent to wastewater systems.
Nowadays, more attention is also put on obtaining environmentally sustainable processes and obtaining as many value added or recyclable products from the process as possible in order to avoid as much wastage and loss as possible.
Thus, there is a need to obtain a more efficient method. There is a need for a method to reduce the need to place materials in landfills and to discharge valuable chemicals into wastewater systems. There is also a need to provide additional value added products from waste from battery manufacturing facilities, battery recycling facilities or steel plants, which improves the economics of the whole battery manufacturing facilities, the whole battery recycling facilities or the whole steel plants, respectively.
Disclosure of Invention
By the method of the invention, a high value product can be obtained and at the same time a more environmentally sustainable solution for waste disposal is provided. By providing value added products that are in need of and may be sold in the market, the overall economy of the battery production facility, the battery recycling facility, or the steel plant is improved and the natural resources are also carefully used. Furthermore, the method is able to meet the requirements and legislative possibilities associated with waste treatment of battery manufacturing or recycling.
The residual process stream from battery manufacture used in the method of the invention may be from an oxidation step of cathode production in (lithium ion) battery manufacture, in which step sodium sulphate is formed. The residual process stream may be wastewater from an oxidation step of cathode production. According to the invention, the residue process stream from battery manufacturing, which is nowadays forwarded to landfill sites or waste water systems, or concentrated to produce solid residues, can be treated with potassium chloride to produce high value fertilizers K 2 SO 4 And by-product NaCl, which can be used for different applications such as road salt. The sodium sulfate-containing residue process stream from the oxidation step of cathode production of lithium ion batteries may be in the form of an aqueous waste streamIn the form of water. Such wastewater may be concentrated by evaporating at least a portion of the water content prior to carrying out the process of the present invention. Such wastewater can be dried to provide a dried residue process stream.
The residual process stream from battery recovery may result from the disposal of lithium-containing batteries. The residual process stream may be obtained from a black block material comprising lithium iron phosphate.
The residual process stream from steel production may come from slag processing involving vanadium recovery.
By the present invention, a large amount of chemicals (i.e., sodium sulfate) present in the residue process stream (from battery manufacturing, battery recycling, or steel production as described herein) can be used and negative environmental impact from the battery manufacturing residue process stream, battery recycling residue process stream, or steel production plant residue process stream can be eliminated. As a result of the high grade fertiliser obtained by the present invention, it is also possible to transfer the nutritional chemicals to plants in need thereof, rather than to transfer them to gutters or drains, or to landfill sites or to separate as low grade chemicals.
The present invention may be applied and practiced in any battery manufacturing facility, battery recycling facility or steel plant that provides a residue process stream or processes a residue process stream in a residue process treatment system, the residue process stream comprising sodium sulfate, such as an aqueous residue process stream or processes an aqueous residue process stream in a residue process treatment system, the residue process stream comprising sodium sulfate.
The scope of the invention is consistent with the appended claims.
The invention relates to a method for producing potassium sulphate K from a residual process stream of a battery manufacturing plant, a battery recycling plant or a steel production plant 2 SO 4 Wherein a residue process stream from a battery manufacturing facility, a battery recycling facility, or a steel production plant is provided; optionally providing water if the residual process stream is free of water or does not contain sufficient water; providing potassium chloride; and providing a mixture comprising the optional water, potassium chloride and residue process stream, andreacting them, wherein potassium sulfate is obtained.
According to one embodiment, the potassium chloride and residue process streams are provided in any order or simultaneously to provide the mixture. The potassium chloride, optional water and residue process streams may be provided in any order or simultaneously and mixed to provide the mixture. The residue process stream, potassium chloride, and optionally water, may be provided in any order or simultaneously, and the components may be contacted in any order or simultaneously, and mixed to provide the mixture. The mixture of potassium chloride, the residual process stream and optionally water may be provided by simultaneous addition or sequential addition in any order and mixed to provide the mixture. The mixture may be obtained by first mixing the provided residue process stream and optionally water, and thereafter mixing potassium chloride. Alternatively, the mixture may be obtained by first mixing the provided residue process stream with potassium chloride and thereafter mixing the optional water. Alternatively, the mixture may be obtained by first mixing the provided optional water and potassium chloride, and thereafter mixing the residue process stream. Alternatively, the mixture may be obtained by first mixing the provided residue process stream and optionally water, and thereafter mixing potassium chloride, optionally with further optional water. The optional water and residue process streams are preferably added prior to potassium chloride. Both the residual process stream and potassium chloride may be combined with optional water (i.e., the residual process stream, potassium chloride, and optional water) prior to combining and mixing with each other to form the mixture. In a preferred embodiment, the residual process stream is combined and mixed with any optional water prior to contact with potassium chloride and mixing to form the mixture.
According to one embodiment, the acid is mixed into the mixture. Sulfuric acid and/or hydrochloric acid are preferably used, more preferably sulfuric acid. The acid is preferably added before the potassium chloride is added. Such addition may be performed to adjust the pH of the mixture.
According to one embodiment, the residual process stream is contacted with potassium chloride.
The sodium sulfate containing residue process stream from a cell manufacturing, cell recycling or steel manufacturing plant may contain, be mixed with, or be at least partially dissolved in water. The residual process stream may be a solution. The residue process stream may be pretreated in an evaporation step to produce a dried residue process stream. This pretreated dry residue process stream may then be contacted with water and thereafter with potassium chloride. Alternatively, such pretreated dry residue process stream may then be contacted with potassium chloride and thereafter contacted with water. Alternatively, such pretreated dry residue process stream may then be contacted with potassium chloride, which has been contacted with water.
According to one embodiment, sodium hydroxide and/or potassium hydroxide is added to the water, potassium chloride and residue process stream mixture. This is done in order to adjust the pH, for example if an acid has been added.
According to one embodiment, glaserite is obtained by reaction of water, potassium chloride and a residual process stream, which glaserite is removed and mixed with additional potassium chloride and/or leached with water to provide potassium sulfate. The potassium sulfate can then be removed for further use or sale. It is noted that the mixing of potassium chloride and leaching with water may be performed in any order. However, in a preferred embodiment, the reaction with potassium chloride is performed first, followed by leaching with water.
According to one embodiment, the remaining mixture after removal of potassium sulfate is concentrated, wherein after removal of any sodium chloride present, for example for further use.
According to one embodiment, the removed sodium chloride is transferred to a membrane tank process (cell membrane process) which converts it to sodium hydroxide, hydrogen and chlorine.
According to one embodiment, the removed sodium chloride is transferred to a membrane tank process, which converts it to sodium hydroxide, hydrogen and chlorine.
According to one embodiment, the residue process stream from the battery manufacturing facility originates from a lithium battery manufacturing facility, such as from a battery manufacturing facility producing a battery selected from lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium iron phosphate, lithium nickel cobalt aluminum oxide, lithium titanate, or any combination thereof, preferably from a battery manufacturing facility producing a lithium nickel manganese cobalt oxide battery.
According to one embodiment, the residue process stream from the battery recycling facility originates from the battery recycling facility for lithium-containing batteries. The recovered lithium-containing battery may be selected from batteries comprising lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium iron phosphate, lithium nickel cobalt aluminum oxide, lithium titanate, or any combination thereof, preferably from batteries comprising lithium nickel manganese cobalt oxide.
According to one embodiment, the sodium sulfate containing residue process stream from a steel production plant is derived from the treatment of slag for vanadium recovery. Vanadium recovery may include vanadium purification by addition of sodium hydroxide, which in turn provides vanadium pentoxide as one product stream and a sodium sulfate-containing residue process stream as another product stream. The sulphate-containing residual process stream from the steel production plant may be obtained by adding sulphuric acid and/or aluminium sulphate after vanadium purification.
According to one embodiment, the potassium chloride added to the residue process stream has been subjected to a pretreatment step comprising washing with water and optionally subsequent evaporation to remove any impurities present in the potassium chloride.
The invention also relates to the use of the method according to the invention for producing a fertilizer comprising potassium sulphate.
Drawings
Fig. 1 discloses a schematic embodiment of the process of the present invention.
Fig. 2 discloses a schematic diagram of the cathode oxidation step in the production of a battery and wherein sodium sulfate is transferred to the process of the invention.
Detailed Description
The present invention relates to providing valuable components from a battery manufacturing, battery recycling or steel manufacturing plant residue process stream. By the invention, high-value fertilizer K is obtained 2 SO 4 And, in addition, a by-product NaCl is also available, which can be used for different applications such as road salt.
In particular, it relates to a lithium-derived materialResidual process streams for ion battery manufacture or battery recovery, e.g. selected from lithium cobalt oxide (LiCoO) 2 Or LCO), lithium manganese oxide (LiMn) 2 O 4 Or LMO), lithium nickel manganese cobalt oxide (LiNiMnCoO 2 Or NMC), lithium iron phosphate (LiFePO) 4 Or LFP), lithium nickel cobalt aluminum oxide (LiNiCoAlO) 2 Or NCA), lithium titanate (Li 2 TiO 3 Or LTO). In particular, the present invention relates to a method for producing a lithium nickel manganese cobalt oxide (LiNiMnCoO 2 Or NMC) cell manufacturing or cell recycling residue process streams provide valuable components.
As mentioned above, the residue process stream from battery manufacturing used in the method of the invention may be from an oxidation step of cathode production in (lithium ion) battery manufacturing, in which step sodium sulfate is formed. The residual process stream may be wastewater from an oxidation step of cathode production. The residual process stream used in the method of the invention is preferably obtained from a cathode production step in a battery manufacturing process, more specifically the residual process stream is provided by an oxidation step of cathode production. In the cathode production step, sodium hydroxide and sulfuric acid are used. The residual process stream from the battery manufacturing facility contains mainly sodium, sulphate and trace amounts of several metals and elements, nickel, cobalt, ammonia and lithium. Fig. 2 discloses a schematic diagram of the cathode production step.
As should be appreciated from the foregoing, lithium-containing batteries are an important area of the invention. Further, according to another embodiment, the residue process stream from the battery recycling facility is obtained from a black block material comprising lithium iron phosphate. Furthermore, according to yet another embodiment, the concentration of lithium is preferably increased relative to the total amount of lithium, iron and phosphate by separating the iron and/or phosphate prior to providing the process stream as a residue from the battery recovery facility.
The residue process stream from a steel production plant used in the method of the present invention may be a sodium sulfate-containing residue process stream from slag treatment involving vanadium recovery. In this respect, it may also be mentioned that, according to one embodiment, the sodium sulphate-containing residue process stream originates from the treatment of slag for vanadium recovery. Furthermore, according to yet another embodiment, vanadium recovery comprises vanadium purification by addition of sodium hydroxide, which in turn provides vanadium pentoxide as one product stream and a sodium sulfate containing residue process stream as another product stream. Furthermore, according to a specific embodiment, the sulphate-containing residue process stream is obtained by adding sulphuric acid and/or aluminium sulphate after vanadium purification.
In the process of the present invention, the residue process stream, the optional water and the potassium chloride may be provided and mixed in any order or simultaneously to provide a mixture, i.e. the residue process stream, the optional water and the potassium chloride may be contacted and mixed in any order or simultaneously to provide a mixture. The mixture may be provided by:
potassium chloride, optionally water and the residue process stream are provided and mixed simultaneously,
providing a residue process stream and optionally water and mixing, then mixing potassium chloride,
providing a residue process stream and potassium chloride and mixing, then mixing optional water,
providing and mixing the residual process stream and optionally water, and providing and mixing potassium chloride and optionally water, and then mixing the potassium chloride and optionally water with the residual process stream and optionally water, or
Potassium chloride and optionally water are provided and mixed, then the residue process stream is mixed.
A residual process stream comprising sodium sulfate from a battery manufacturing, battery recycling, or steel production plant may be mixed with and at least partially dissolved in water. Preferably the residual process stream is a solution. Preferably dissolving the components of the residual process stream. The aqueous mixture of the residual process stream may optionally be treated with an acid, preferably sulfuric acid. The optional use of the acid may depend on the composition of the residue process stream.
The residual process stream may vary in chemical content and may contain the following impurities:
·Na 2 SO 4 nickel, cobalt, ammonia, lithium and NaOH-if the residual process stream is provided by a battery manufacturing facility,
·Na 2 SO 4 calcium, lithium, aluminum, iron, and manganese if the residue process stream is provided by a battery recovery facility, or
·Na 2 SO 4 Silicon, iron, potassium and calcium-if the residue process stream is provided by a steel production plant.
A subsequent step of pH adjustment using basic compounds may optionally be used, for example if the above-mentioned acids have been added in the process. KOH and/or NaOH are preferably used as basic compound. The addition of basic compounds can be used to increase the pH and achieve a pH of K 2 SO 4 And the correct stoichiometry of NaCl.
Potassium chloride KCl is added to the aqueous mixture comprising the residual process stream in order to obtain potassium sulphate. The solid phase obtained in the process may comprise a salt called glaserite (K) consisting of potassium and sodium sulphate 3 Na(SO 4 ) 2 ). In one embodiment, the intermediate product obtained in the process of the present invention after the first addition of potassium chloride is glaserite.
The obtained glaserite salt is removed from the treated residue process stream (liquid remainder of the mixture) and may be further treated with KCl to produce K 2 SO 4 . Thereafter the obtained K can be removed 2 SO 4 。
The reaction is used for producing intermediate glaserite and K 2 SO 4 Which is disclosed hereinafter.
Glaserite:
6KCl+4Na 2 SO 4 →2K 3 Na(SO 4 ) 2 +6NaCl
K 2 SO 4 ：
2KCl+2K 3 Na(SO 4 ) 2 →4K 2 SO 4 +2NaCl
as an alternative treatment, the obtained glaserite salt may be leached in water after removal from the treated residue process stream to provide K 2 SO 4 。
However, in another embodiment, the process of the invention may comprise two of the mentioned treatment steps for glaseriteSteps are combined in any order. The obtained glaserite salt may then be first treated with KCl and thereafter leached in water to produce K 2 SO 4 Or vice versa.
The potassium chloride used in the process of the present invention may be subjected to a pretreatment step, including washing and optionally evaporation, prior to addition to the residue process stream. Pretreatment by washing with water allows removal of the by-products or impurities present. Potassium chloride products available on the market generally contain some by-products or impurities, such as sodium chloride. By subjecting the potassium chloride to water washing, any impurities present can be removed from the potassium chloride and thereby improve the quality of the potassium chloride to be added to the residue process stream. By pretreatment with water washing and optionally subsequent evaporation of the water, the quality of the potassium chloride can be increased, for example, from containing about 4wt% sodium chloride to containing up to 1wt% sodium chloride. This increase in the purity of the potassium chloride used in the process of the present invention increases the yield of potassium sulfate obtained in the conversion step by at least five times when the conversion to potassium sulfate is carried out at a pH of about 5-9, such as about 6 to 8, and preferably about 6-7.
Isolation K 2 SO 4 The treated residual process stream remaining after may be further treated, for example by a cooling step to precipitate sodium sulphate and by returning the sulphate to the process to increase sulphate production.
Isolation K 2 SO 4 The treated residual process stream remaining after this may be further processed, for example by evaporation in order to precipitate sodium chloride (NaCl), which may be removed as a solid phase. Which can then be used as e.g. road salt.
The invention can be further supplemented by using a membrane tank process which can convert the obtained NaCl into NaOH, H 2 And Cl 2 . NaOH is a valuable chemical and is used by battery manufacturers, battery recycling plants or steel production plants, for example in the purification of vanadium in steel production plants. Two other products H 2 And Cl 2 Can be collected and used as energy source in the case of H2 or sold to third parties to improve the economics and overall process of the battery processProfitability.
In this way, more value added product than produced fertilizer can be obtained and reused or sold in a battery manufacturing process, a battery recycling process, or an entire steel production process, or other processes.
Referring to fig. 1, a mixing of the residual process stream and water in step 1 is shown. The water addition may be optional if the residual process stream already contains a sufficient amount of water. Alternatively, if the residual process stream already contains a certain amount of water, only a small amount of water may be added. In one embodiment, the residue process stream and water may be replaced by or combined with waste from a pretreatment residue process stream treatment system. Alternatively, an acid, such as sulfuric acid, may also be added in step 1.
The mixture comprising the residual process stream may optionally be mixed with KOH and/or NaOH in step 2, wherein the pH of the mixture is raised and the solution can reach the desired K 2 SO 4 And the correct stoichiometry of NaCl. In step 2, no basic compound may be needed, for example if no acid is added in step 1.
Thereafter in step 3, the residual process stream mixture is mixed with KCl to obtain K 2 SO 4 . This process may produce a mixed salt of potassium and sodium sulfate, known as glaserite. This glaserite salt can then be removed and forwarded to the next step 4, where it is allowed to react with additional KCl in an aqueous solution and can then be leached further in step 5 in water to yield the final product K 2 SO 4 . It is noted that either of steps 4 and 5 may be used alone or in combination. K in solid phase 2 SO 4 Separated from the treated residual process stream, which may be recovered.
The remaining liquid of steps 3, 4 and 5 may be recycled back to the previous step of the process in countercurrent flow with the precipitated salt. In step 3, where glaserite may be formed, the treated residue process stream from this step is forwarded to a cooling step 6 in order to precipitate more sulphate which is separated and recycled back to step 3.
The remaining solution after cooling step 6, which has small amounts of sodium and potassium sulphate but also sodium and chloride, is sent to an evaporation step 7, where water is removed in order to increase the salt concentration and precipitate the NaCl as a solid phase and separate the salt from the solution. The water discharged in the evaporation step, in which the NaCl precipitates and is removed from the solution, can be recycled into the process to shut down the system and be used to dilute the waste or dissolve new residual process streams.
To further enhance the reaction of glaserite to potassium sulfate in step 4, the impurities in KCl are washed and removed to produce high purity KCl, which increases the yield in step 4 by up to 5 times.
Almost all reactions occur at room temperature or slightly above and therefore the energy requirements of the process according to the invention are not very high, except for evaporation of water in the NaCl precipitation step 7.
The membrane tank process may be additionally added to the process of the present invention to provide NaOH from the produced by-product NaCl to a battery production facility, a battery recovery facility or a steel production plant, such as in vanadium purification.
Claims (17)
1. A process for producing a fertilizer composition containing potassium sulfate from a sodium sulfate-containing residue process stream of a battery manufacturing facility, a battery recycling facility, or a steel production plant, wherein,
providing the residue process stream from a battery manufacturing facility, a battery recycling facility, or a steel production plant;
optionally providing water;
providing potassium chloride; and
providing a mixture comprising the optional water, potassium chloride and a residual process stream, and reacting the mixture, wherein potassium sulfate is obtained.
2. A method according to claim 1, wherein the potassium chloride, the residue process stream and optionally water are provided and mixed in any order or simultaneously to provide said mixture, preferably said mixture is provided by:
the potassium chloride, optionally water and the residue process stream are provided and mixed simultaneously,
providing the residue process stream and optionally water and mixing, then mixing the potassium chloride,
providing the residue process stream and potassium chloride and mixing, then mixing optional water,
providing and mixing the residual process stream and optionally water, and providing and mixing the potassium chloride and optionally water, and then mixing the potassium chloride and optionally water with the residual process stream and optionally water, or
Providing and mixing the potassium chloride and optionally water, and then mixing the residual process stream.
3. A process according to claim 1 or 2, wherein the residue process stream and optionally water are added prior to the potassium chloride.
4. A method according to any one of claims 1-3, wherein an acid is mixed into the mixture, preferably before the potassium chloride is added.
5. The method according to any one of claims 1-4, wherein the residue process stream has been pretreated in an evaporation step to produce a dry matter that is contacted with the water and thereafter contacted with the potassium chloride.
6. The method according to any one of claims 1-5, wherein sodium hydroxide and/or potassium hydroxide is added to the water, potassium chloride and residue process stream mixture.
7. A process according to any one of claims 1 to 6, wherein glaserite is obtained by reaction of the water, the potassium chloride and the residue process stream, said glaserite being removed and mixed with additional potassium chloride and/or leached with water to provide potassium sulphate.
8. The process according to claim 7, wherein the remaining mixture after removal of potassium sulphate is concentrated, followed by removal of any sodium chloride present.
9. The method of claim 8, wherein the removed sodium chloride is diverted to a membrane process to convert the sodium chloride to sodium hydroxide, hydrogen and chlorine.
10. The method according to any one of claims 1-9, wherein the residue process stream from a battery manufacturing facility originates from a lithium battery manufacturing facility, preferably from a battery manufacturing facility producing a battery selected from the group consisting of lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium iron phosphate, lithium nickel cobalt aluminum oxide, lithium titanate or any combination thereof, preferably from a battery manufacturing facility producing a lithium nickel manganese cobalt oxide battery.
11. The method according to any one of claims 1-9, wherein the residue process stream from a battery recycling facility originates from a battery recycling facility for lithium-containing batteries.
12. The method of claim 11, wherein the recovered lithium-containing battery is selected from a battery comprising lithium cobalt oxide, lithium manganese oxide, lithium nickel manganese cobalt oxide, lithium iron phosphate, lithium nickel cobalt aluminum oxide, lithium titanate, or any combination thereof, preferably from a battery comprising lithium nickel manganese cobalt oxide.
13. The method according to any one of claims 1-9, wherein the sodium sulphate-containing residue process stream from a steel production plant originates from the treatment of slag for vanadium recovery.
14. The method according to claim 13, wherein the vanadium recovery comprises vanadium purification by addition of sodium hydroxide, thereby providing vanadium pentoxide as one product stream and the sodium sulfate-containing residue process stream as another product stream.
15. The method according to claim 13, wherein the sulphate-containing residue process stream from steel production plants is obtained by adding sulphuric acid and/or aluminium sulphate after the vanadium purification.
16. The method according to any one of claims 1-15, wherein the potassium chloride added to the residue process stream has undergone a pretreatment step comprising washing with water and optionally subsequent evaporation to remove any impurities present in the potassium chloride.
17. Use of the method according to any one of claims 1-16 for producing a fertilizer comprising potassium sulphate.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SE2150661-3 | 2021-05-25 | ||
| SE2151435-1 | 2021-11-25 | ||
| SE2151520-0 | 2021-12-13 | ||
| SE2151520 | 2021-12-13 | ||
| PCT/SE2022/050503 WO2022250599A1 (en) | 2021-05-25 | 2022-05-24 | Process for treatment of a sodium sulfate containing residue process stream of a battery manufacturing facility, a battery recycling facility, or a steel production plant |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117378071A true CN117378071A (en) | 2024-01-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280037513.2A Pending CN117378071A (en) | 2021-05-25 | 2022-05-24 | Method for treating sodium sulfate-containing residue process streams of battery manufacturing facilities, battery recycling facilities or steel production plants |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117378071A (en) |
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2022
- 2022-05-24 CN CN202280037513.2A patent/CN117378071A/en active Pending
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