CN114015882A - Method for recovering vanadium and nickel from POX carbon black - Google Patents
Method for recovering vanadium and nickel from POX carbon black Download PDFInfo
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- CN114015882A CN114015882A CN202111268250.XA CN202111268250A CN114015882A CN 114015882 A CN114015882 A CN 114015882A CN 202111268250 A CN202111268250 A CN 202111268250A CN 114015882 A CN114015882 A CN 114015882A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 112
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 57
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000006229 carbon black Substances 0.000 title claims abstract description 17
- 238000002386 leaching Methods 0.000 claims abstract description 44
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 33
- 238000000605 extraction Methods 0.000 claims abstract description 30
- 239000012074 organic phase Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 20
- 239000002893 slag Substances 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 239000008346 aqueous phase Substances 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- HBVFXTAPOLSOPB-UHFFFAOYSA-N nickel vanadium Chemical compound [V].[Ni] HBVFXTAPOLSOPB-UHFFFAOYSA-N 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000005261 decarburization Methods 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- -1 iron ions Chemical class 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000007127 saponification reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000284 extract Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 27
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 239000011550 stock solution Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002956 ash Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010881 fly ash Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 2
- 229940041260 vanadyl sulfate Drugs 0.000 description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- WUJISAYEUPRJOG-UHFFFAOYSA-N molybdenum vanadium Chemical compound [V].[Mo] WUJISAYEUPRJOG-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for recovering vanadium and nickel from POX carbon black, which comprises the following steps: 1) sequentially drying, dehydrating, roasting, desulfurizing and decarbonizing the POX carbon black to obtain decarbonized slag; 2) crushing the decarbonized slag, leaching with acid liquor, and performing solid-liquid separation to obtain vanadium-containing nickel leaching solution and leaching slag; 3) adopting a first extractant containing vanadium and nickel in the leaching solution to obtain a first organic phase and a first water phase, and performing back extraction on the first organic phase to obtain a vanadium-rich solution; 4) and removing impurities from the first water phase by using P204, extracting nickel by using a second extracting agent and performing back extraction to obtain a nickel-enriched liquid. The method can effectively extract and separate vanadium and nickel in the POX carbon black, and has the advantages of high product purity, short operation flow and low process cost.
Description
Technical Field
The invention belongs to the field of petrochemical metallurgy, and relates to a method for recovering vanadium and nickel from POX carbon black.
Background
After oil sludge, asphalt and the like generated in the petroleum industry are subjected to hydrogen production by a POX oxidation process, valuable metals such as vanadium and nickel are enriched in the generated carbon black (POX carbon black), and the POX carbon black is subjected to harmless and resource treatment, so that the method has important economic and environmental protection significance.
Methods for extracting vanadium and nickel from petroleum-based materials have been disclosed.
Patent CN102971439 discloses a process for recovering metals from refinery residues, which comprises pyrolyzing and combusting said residues at temperatures up to 900 ℃ to produce ash, converting the ash into an aqueous slurry, first dissolving vanadium, molybdenum in water using sodium hydroxide, nickel remaining in the slag, effecting the separation of vanadium molybdenum from nickel, then precipitating ammonium metavanadate and ammonium molybdate, respectively, separating vanadium from molybdenum; the nickel in the slag is leached as nickel sulphate using sulphuric acid and converted to nickel hydroxide with alkali and further to nickel acetate using acetic acid.
Patent CN106367601B discloses a method for extracting valuable metals by wet processing of fuel fly ash, which mainly comprises the following steps: putting fuel oil fly ash into water, adding ammonia water to adjust the pH value to 7-9, adding an oxidant to oxidize vanadium into pentavalent vanadium, allowing vanadium to enter a solid phase, leaving nickel in a liquid phase, filtering and separating, extracting nickel from filtrate to obtain nickel sulfide, further performing ion exchange and alkali-adding deammoniation, and discharging; dissolving the vanadium-containing filter cake in hot water, filtering and precipitating vanadium to obtain ammonium metavanadate crystals.
The two patents are based on solid treatment, but not high-purity product production, and ammonium metavanadate is precipitated in a solution rich in impurity ions, so that the impurity ions are inevitably carried, and the high-purity ammonium metavanadate product is difficult to obtain.
Content of the specification
The invention aims to provide a method for recovering vanadium and nickel from POX carbon black, which has the advantages of high vanadium and nickel recovery rate, high product purity, simple operation and environmental protection.
The invention has the following beneficial effects:
(1) by adopting the direct acid leaching method, the leaching rates of vanadium and nickel can reach more than 90 percent, the leaching rate of iron and silicon impurities is less than 30 percent, and the vanadium and the nickel are effectively leached out;
(2) the extraction method is adopted to extract vanadium and nickel, the separation effect from impurities is good, the product purity is high, the obtained vanadium-rich and nickel-rich products can be directly sold, and the extractant can be recycled and is environment-friendly;
(3) the method has the advantages that the direct yield of vanadium and nickel can reach more than 85 percent, and the direct yield is high.
Content of the specification
1. A method for recovering vanadium and nickel from POX carbon black comprises the following steps:
1) sequentially drying, dehydrating, roasting, desulfurizing and decarbonizing the POX carbon black to obtain decarbonized slag;
2) leaching the decarbonized slag by adopting acid liquor, and performing solid-liquid separation to obtain vanadium-containing nickel leaching solution and leaching slag;
3) extracting vanadium in the vanadium-nickel-containing leaching solution by using a first extracting agent to obtain a first organic phase and a first water phase, and performing back extraction on the first organic phase to obtain a vanadium-rich solution;
4) and removing impurities from the first water phase by using P204, extracting nickel by using a second extracting agent and performing back extraction to obtain a nickel-enriched liquid.
As a preferable method of the invention, the dehydration mode in the step (1) can be drying by a low-temperature dryer, preferably, the drying temperature is 50-75 ℃, and preferably, the moisture content of the dried ash is 25-50%.
As a preferable method of the invention, the roasting decarburization device in the step (1) comprises a rotary kiln or a tunnel kiln; preferably, the roasting temperature is 500-850 ℃.
As a preferable method of the invention, the acid used for leaching the decarbonized residue in the step (2) by using acid liquor comprises hydrochloric acid or sulfuric acid; preferably, the solid-liquid ratio of the leaching solution is 1: 2-10; preferably, the leaching temperature is 60-100 ℃; preferably, the leaching time is 2-8 h; preferably, the acid concentration is 2-6 mol/L.
As a preferable method of the invention, the vanadium-nickel-containing leaching solution in the step (3) contains iron ions, and the first extracting agent is P204. Preferably, before the first extractant is used for extracting vanadium from the leaching solution, the ferric iron in the leaching solution is reduced into ferrous iron, and the pH value of the leaching solution is adjusted; preferably, the reducing agent used for the reduction comprises one or at least two of sodium sulfite, sodium thiosulfate and iron powder; preferably, the addition amount of the reducing agent is 1.2-2.5 times of the theoretical amount; preferably, the pH value of the leaching solution is controlled to be 1.0-2.5.
P204 extraction of metal ion sequence Fe in the invention3+>V4+>V5+>Fe2+Therefore, before P204 extracts vanadium, ferric iron is reduced into ferrous iron, so that the extraction of iron is reduced.
As a preferable method of the invention, the first extractant in step (3) is saponified before extracting vanadium in the leaching solution, and then is extracted, and after extraction, the first extractant is kept still for phase separation to obtain a first organic phase and a first aqueous phase; preferably, the volume fraction of the first extracting agent is 15-25%; preferably, the diluent of the first extracting agent comprises one or any two of Escaid 110, dodecane, solvent naphtha and sulfonated kerosene; preferably, the saponifying agent used for saponification is one or a combination of NaOH and ammonia water; preferably, the equilibrium pH value of the first water phase is controlled to be 1.5-2.2.
As a preferable method of the invention, the first organic phase in the step (3) contains vanadium and iron, a first stripping agent is adopted to strip to obtain a vanadium-rich solution, and then a second stripping agent is adopted to strip iron to obtain a regenerated organic phase for recycling. The first stripping agent is sulfuric acid, and the second stripping agent is one or the combination of hydrochloric acid and oxalic acid. Preferably, the concentration of the first stripping agent is 1.5-3.5 mol/L; preferably, the concentration of the second stripping agent is 4-6 mol/L; preferably, the back extraction times are 1 or more.
In the invention, part of iron is synchronously extracted while P204 is extracting vanadium, and iron in the organic phase is not easy to be back-extracted by sulfuric acid, so that the effective separation of vanadium and iron can be realized by adopting low-concentration sulfuric acid to back-extract vanadium.
The preferable method is characterized in that the first aqueous phase in the step (4) is subjected to chemical impurity removal, P204 extraction impurity removal, nickel extraction by the second extractant and back extraction in sequence to obtain the nickel-rich liquid. Preferably, the pH value of the chemical impurity removal solution is adjusted to 3-3.5 by using an alkali solution, and solid-liquid separation is performed to obtain a chemical impurity removal solution; preferably, the volume fraction of the P204 is 15-25%; preferably, the second extractant is one or a combination of two of BC196, CPH88, C272 and P507, and the molecular formula of the CPH88 is shown as formula I:
wherein, C8H17 are all straight-chain alkane groups containing branched chains;
preferably, the stripping agent adopted for the stripping is hydrochloric acid or sulfuric acid, and the concentration is 1.5-6 mol/L
In the invention, when the second extracting agent is P507, C272 is adopted to separate and remove impurities such as magnesium and the like in the nickel-containing solution, and then nickel is extracted, and the pH value of the equilibrium water phase is controlled to be 5.8-6.2; when the second extractant is BC196, the BC196 can directly extract nickel to leave magnesium in raffinate because the nickel is extracted by BC196 before the magnesium, and the pH value of the equilibrium water phase is controlled to be 5.5-6.8; when the second extractant is CPH88, the pH value of the equilibrium water phase is controlled to be 3-3.5.
Drawings
FIG. 1 is a schematic diagram of the process flow for recovering vanadium and nickel from POX carbon black.
Fig. 2 is a graph of the extraction rate of the second extractant CPH88 for metal ions versus the equilibrium pH in the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
Example 1
1) Taking a certain weight of POX carbon black, dehydrating and drying at the drying temperature of 60 ℃ to obtain dehydrated slag with the water content of 30%, and roasting in a roasting furnace at the temperature of 800 ℃ to constant weight to obtain decarbonized slag;
2) fully grinding the decarburization slag, and mixing the materials according to a solid-liquid ratio of 1: 6, adding a sulfuric acid solution with the concentration of 4mol/L, mixing and stirring, controlling the leaching temperature to be 90 ℃, and the leaching time to be 4 hours, and carrying out solid-liquid separation to obtain a vanadium-containing nickel leaching solution (shown in the table 1) and leaching slag;
3) adding sodium sulfite with the theoretical amount of 1.2 times into vanadium-nickel-containing leachate to reduce ferric iron into ferrous iron, adding alkali liquor to adjust the pH value to 1.8 to obtain an extraction stock solution, performing countercurrent extraction on the extraction stock solution by using saponified P204 (the volume fraction of which is 20 percent, Escaid 110 is used as a diluent and a saponifying agent is 10M NaOH solution), controlling the pH value of a balanced aqueous phase to be 1.8 to obtain a vanadium-loaded first organic phase and a nickel-containing first aqueous phase, performing back extraction on the vanadium-loaded first organic phase for 4 times by using 2M sulfuric acid to obtain high-purity vanadyl sulfate for direct sale or preparation of high-purity vanadium pentoxide, and performing back extraction on the organic phase by using 6M HCl to obtain a regenerated organic phase for recycling;
4) adjusting the pH value of the first water phase to 3-3.5, and then extracting and removing impurities from the first water phase by using saponified P204 (volume fraction is 20%, Escaid 110 is used as a diluent, and a saponifying agent is a 10M NaOH solution), so that iron, aluminum, zinc, copper, calcium and the like are extracted into an organic phase, and nickel is left in the P204 impurity-removed raffinate;
5) extracting nickel in the P204 impurity-removed raffinate by using saponified BC196 (the volume fraction of which is 20 percent, Escaid 110 is used as a diluent, and a saponifying agent is a 10M NaOH solution), controlling the pH value of the balanced aqueous phase to be 5.5-7.5, standing for phase splitting to obtain a nickel-loaded organic phase and a magnesium-containing raffinate aqueous phase, and carrying out evaporation and crystallization on the obtained high-purity nickel sulfate by using 2M sulfuric acid to obtain the high-purity nickel sulfate for direct sale.
In the method, the leaching rates of vanadium and nickel are respectively 90.6% and 86.8%, and the direct recovery rates of vanadium and nickel reach 86.5% and 82.5%.
TABLE 1 elemental composition of leachate containing vanadium and nickel
| V | Fe | Ca | Al | Si | P | Ni | Mo | Cr | Mg | |
| content/g/L | 18.03 | 4.86 | 0.15 | 0.3 | 0.018 | 0.10 | 4.93 | 0.33 | 0.029 | 3.21 |
Example 2
1) Taking a certain weight of POX carbon black, dehydrating and drying at the drying temperature of 60 ℃ to obtain dehydrated slag with the water content of 25%, and roasting in a roasting furnace at the temperature of 600 ℃ to constant weight to obtain decarbonized slag;
2) fully grinding the decarburization slag, and mixing the materials according to a solid-liquid ratio of 1: 5, adding a sulfuric acid solution with the concentration of 4.5mol/L, mixing and stirring, controlling the leaching temperature to be 85 ℃ and the leaching time to be 5 hours, and carrying out solid-liquid separation to obtain a vanadium-containing nickel leaching solution (shown in the table 1) and leaching slag;
3) adding sodium thiosulfate with the theoretical amount of 1.8 times of that of a vanadium-nickel-containing leaching solution to reduce ferric iron into ferrous iron, adding alkali liquor to adjust the pH value to 2.0 to obtain an extraction stock solution, performing countercurrent extraction on the extraction stock solution by using saponified P204 (the volume fraction of which is 25 percent, Escaid 110 is used as a diluent and a saponifying agent is 10M NaOH solution), controlling the pH value of an equilibrium water phase to be 2.0 to obtain a vanadium-loaded first organic phase and a nickel-containing first water phase, performing back extraction on the vanadium-loaded first organic phase for 3 times by using 2.5M sulfuric acid to obtain high-purity vanadyl sulfate for direct sale or preparation of high-purity vanadium pentoxide, and performing 6M HCl and 2M H on the organic phase2C2O4The regenerated organic phase obtained after back extraction is recycled;
4) adjusting the pH value of the first water phase to 3-3.5, and then extracting and removing impurities from the first water phase by using saponified P204 (volume fraction is 20%, Escaid 110 is used as a diluent, and a saponifying agent is a 10M NaOH solution), so that iron, aluminum, zinc, copper, calcium and the like are extracted into an organic phase, and nickel is left in the P204 impurity-removed raffinate;
5) extracting nickel in P204 impurity-removed raffinate by using saponified CPH88 (volume fraction is 20%, Escaid 110 is used as a diluent, and a saponifying agent is a 10M NaOH solution), controlling the pH value of a balanced aqueous phase to be 3-3.5, standing for phase splitting to obtain a nickel-loaded organic phase and a magnesium-containing raffinate aqueous phase, and carrying out evaporation and crystallization on the obtained high-purity nickel sulfate by using 3M sulfuric acid to obtain the high-purity nickel sulfate which is directly sold.
In the method, the leaching rates of vanadium and nickel are respectively 90.6% and 86.8%, and the direct recovery rates of vanadium and nickel reach 86.5% and 82.5%.
TABLE 2 elemental composition of leachate containing vanadium and nickel
| V | Fe | Ca | Al | Si | P | Ni | Mo | Cr | Mg | |
| content/g/L | 20.12 | 5.01 | 0.19 | 0.38 | 0.021 | 0.13 | 5.23 | 0.42 | 0.031 | 3.45 |
Claims (9)
1. A method for recovering vanadium and nickel from POX carbon black comprises the following steps:
1) sequentially drying, dehydrating, roasting, desulfurizing and decarbonizing the POX carbon black to obtain decarbonized slag;
2) leaching the decarbonized slag by adopting acid liquor, and performing solid-liquid separation to obtain vanadium-containing nickel leaching solution and leaching slag;
3) extracting vanadium in the vanadium-nickel-containing leaching solution by using a first extracting agent to obtain a first organic phase and a first water phase, and performing back extraction on the first organic phase to obtain a vanadium-rich solution;
4) and removing impurities from the first water phase by using P204, extracting nickel by using a second extracting agent and performing back extraction to obtain a nickel-enriched liquid.
2. The method of claim 1, wherein the dehydration of step (1) is carried out by a low temperature dryer;
preferably, the drying temperature is 50-75 ℃;
preferably, the moisture content of the dried ash is 25-50%.
3. The method of claim 1, wherein the roasting decarburization facility of step (1) comprises a rotary kiln or a tunnel kiln;
preferably, the roasting temperature is 500-850 ℃.
4. The method according to claims 1 to 3, wherein the acid used for leaching the decarbonized residue with acid liquor in the step (2) comprises hydrochloric acid or sulfuric acid;
preferably, the solid-liquid ratio of the leaching solution is 1: 2-10;
preferably, the leaching temperature is 60-100 ℃;
preferably, the leaching time is 2-8 h;
preferably, the acid concentration is 2-6 mol/L.
5. The method of claims 1-4, wherein the vanadium-nickel-containing leachate of step (3) contains iron ions, and the first extractant is P204;
preferably, before the first extractant is used for extracting vanadium from the leaching solution, the ferric iron in the leaching solution is reduced into ferrous iron, and the pH value of the leaching solution is adjusted;
preferably, the reducing agent used for the reduction comprises one or at least two of sodium sulfite, sodium thiosulfate and iron powder;
preferably, the addition amount of the reducing agent is 1.2-2.5 times of the theoretical amount;
preferably, the pH value of the leaching solution is controlled to be 1.0-2.5.
6. The method according to claims 1 to 5, wherein the first extractant in step (3) is saponified and then extracted before extracting vanadium from the leachate, and after extraction, the phases are separated by standing to obtain a first organic phase and a first aqueous phase;
preferably, the volume fraction of the first extracting agent is 15-25%;
preferably, the diluent of the first extracting agent comprises one or any two of Escaid 110, dodecane, solvent naphtha and sulfonated kerosene;
preferably, the saponifying agent used for saponification is one or a combination of NaOH and ammonia water;
preferably, the equilibrium pH value of the first water phase is controlled to be 1.5-2.2.
7. The method of claims 1-6, wherein the first organic phase in step (3) contains vanadium and iron, and the first stripping agent is used for stripping to obtain a vanadium-rich solution, and then the second stripping agent is used for stripping iron to obtain a regenerated organic phase for recycling.
8. The method of claim 7, wherein the first stripping agent is sulfuric acid and the second stripping agent is one or a combination of hydrochloric acid and oxalic acid.
Preferably, the concentration of the first stripping agent is 1.5-3.5 mol/L;
preferably, the concentration of the second stripping agent is 4-6 mol/L;
preferably, the back extraction times are 1 or more.
9. The method of claims 1-8, wherein the first aqueous phase of step (4) is subjected to chemical impurity removal, P204 extraction impurity removal, nickel extraction by the second extractant and back extraction in sequence to obtain a nickel-rich solution.
Preferably, the pH value of the chemical impurity removal solution is adjusted to 3-3.5 by using an alkali solution, and solid-liquid separation is performed to obtain a chemical impurity removal solution;
preferably, the volume fraction of the P204 is 15-25%;
preferably, the second extractant is one or a combination of two of BC196, CPH88, C272 and P507, and the molecular formula of the CPH88 is shown as formula I:
wherein, C8H17 are all straight-chain alkane groups containing branched chains;
preferably, the stripping agent adopted for the stripping is hydrochloric acid or sulfuric acid, and the concentration is 1.5-6 mol/L.
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