CN111778404A - Leaching separation method of nickel-cobalt-molybdenum-phosphorus-vanadium alloy material - Google Patents
Leaching separation method of nickel-cobalt-molybdenum-phosphorus-vanadium alloy material Download PDFInfo
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Abstract
The invention discloses a leaching and separating method of a nickel-cobalt-molybdenum-phosphorus-vanadium alloy material, which comprises the following steps: s1: raw material treatment, S2: batch slurrying reaction, S3: pressure oxidation alkaline leaching, S4: and fourthly, performing slurrying reaction on the ingredients to enable molybdenum, phosphorus and vanadium in the alloy material to react with alkali to generate corresponding molybdate radical, phosphate radical and vanadate ions, entering the solution, then performing pressure oxidation and alkaline leaching, controlling the amount and the rate of oxygen introduced by controlling the pressure parameter index in the reaction kettle, and controlling the reaction temperature in the reaction kettle in a matching manner to enable the molybdenum, phosphorus and vanadium in the feed liquid to react with the alkali to be completely converted into sodium molybdate, sodium phosphate and sodium vanadate, and enable nickel, cobalt and iron to enter slag in a precipitation manner, so that valuable metals including molybdenum, phosphorus and vanadium in the feed liquid can fully enter filtrate for subsequent separation and recycling, and full recycling of valuable metal resources in the alloy material is realized.
Description
Technical Field
The invention relates to the technical field of metallurgy and chemical industry, in particular to a leaching separation method of a nickel-cobalt-molybdenum-phosphorus-vanadium alloy material.
Background
At present, nickel-cobalt alloy is a strategic metal with ferromagnetism, is widely used for producing stainless steel, high-temperature alloy, magnetic materials, catalysts and the like, and has application fields including petrochemical industry, aerospace, military industry, electronics and the like. The quantity of waste catalysts, nickel-cobalt high-temperature alloys and other alloy wastes is increasing day by day. The waste materials are not only large in quantity, but also contain high-content rare metals, including valuable metals such as nickel (Ni), cobalt (Co), molybdenum (Mo), phosphorus (P), vanadium (V) and the like. If the rare metal is disposed at will, the environment is seriously polluted and the waste of most rare metal resources is caused. The catalyst is used as a secondary resource to be recycled, so that certain economic benefit can be directly obtained, the utilization rate of the resource can be improved, the environmental problem caused by the catalyst is avoided, and sustainable development is realized.
In order to fully recycle rare valuable metal resources in the alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, the common recycling method at present generally adopts normal-pressure acid leaching, sulfuric acid, hydrochloric acid or nitric acid and an oxidant are added, various metal elements in the waste catalyst are leached under the conditions of high temperature and high acid, the metal elements enter a solution, the molybdenum, cobalt and nickel are extracted and purified respectively by adopting a step-by-step extraction mode, and various metals are recycled by evaporation crystallization and the like. The method is quick in leaching, but the cobalt and the nickel can be leached only by high acid and high temperature under the condition that the acid concentration reaches 2 mol/L. In this case, the leachate has relatively high levels of nickel, cobalt, iron, and molybdenum, and also has relatively high acidity. In the process of adding the oxidant to remove iron, iron is oxidized into trivalent iron, and the iron is very easy to react with molybdenum and vanadium to form iron molybdate and iron vanadate which enter slag, so that the recovery rate of valuable metals such as molybdenum and vanadium is low. In the subsequent extraction process, because molybdenum exists in the form of molybdate radical, and cobalt and nickel exist in the form of cation, the extraction process is very complicated to control, and the industrial production is difficult; the final metal recovery rate is low, and generally can only reach 80-85%.
The Chinese patent with application number CN109517988A discloses a leaching separation method of a cobalt-nickel alloy material containing molybdenum and vanadium, which separates metals such as cobalt, nickel, molybdenum and vanadium from iron slag through pressure acid leaching and oxygen enrichment, effectively avoids the loss of molybdenum and vanadium metal elements caused by the reaction of trivalent iron after oxidation and molybdenum vanadate radical ions, and finally leaches molybdenum and vanadium from nickel and cobalt step by step in an acid solution. By the method, the recovery rate of molybdenum and vanadium is improved to more than 97 percent, but the method has the technical defects that: the molybdenum and vanadium in the acidic cobalt-nickel solution need to be extracted for multiple times, so that part of molybdenum contains vanadium, and part of vanadium contains nickel, and further separation is difficult, so that the final molybdenum-vanadium recovery rate is not high.
Disclosure of Invention
The invention aims to overcome the defects of low recovery rate of molybdenum and vanadium in a cobalt-nickel alloy containing molybdenum and vanadium, complex process operation, long time consumption, high process cost and the like in the prior art, and provides a leaching and separating method of a nickel-cobalt-molybdenum-phosphorus-vanadium alloy material.
In order to achieve the above purpose, the invention provides the following technical scheme:
a leaching separation method of alloy materials comprises the following steps:
s1, raw material treatment: preparing alloy waste into alloy powder; the alloy waste contains iron, cobalt, nickel, molybdenum, phosphorus and vanadium elements;
s2, batching and slurrying reaction: mixing alloy powder and alkaline solution according to a solid-liquid mass ratio of 1: 7-15, stirring at 70-90 ℃, and performing slurrying reaction for 0.5-1 h; the mass ratio of liquid alkali or flake alkali to alloy powder in the alkaline solution is 1.2-3.5: 1;
s3, pressure oxidation alkaline leaching: pumping the reacted feed liquid in the S2 into a reaction kettle, introducing oxygen to increase the pressure to 1.8-2.8 MPa, and reacting for 2-8h at the temperature of 160-; after the reaction is finished, adjusting the pH value of the slurry to 7-9, and filtering to obtain filter residue and filtrate, wherein the filter residue contains iron, cobalt and nickel elements, and the filtrate contains molybdate ions, phosphate ions and vanadate ions;
s4, multi-metal separation: separating iron, cobalt and nickel elements in the S3 filter residue, and separating molybdenum, phosphorus and vanadium elements in the S3 filter solution.
In the above process, the reaction between the feed liquid and the alkaline solution is as follows:
MoO3+2NaOH＝＝Na2MoO4+H2O
V2O5+2NaOH＝＝2NaVO3+H2O
P2O5+6NaOH＝＝2Na3PO4+3H2O
the leaching separation method comprises the steps of carrying out pulping reaction on an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium through the ingredients to enable molybdenum, phosphorus and vanadium in the alloy material to react with alkali to generate corresponding molybdate radical, phosphate radical and vanadate radical ions to enter a solution, pumping the material liquid obtained after pulping reaction of the ingredients into a reaction kettle, controlling the pressure parameter index in the reaction kettle, introducing the amount and the introduction rate of oxygen, and controlling the reaction temperature in the reaction kettle in a matching manner to enable the molybdenum, phosphorus, vanadium and alkali in the material liquid to react and be completely converted into sodium molybdate, sodium phosphate and sodium vanadate, and enable nickel, cobalt and iron to enter slag in a precipitation manner. Valuable metals including molybdenum, phosphorus and vanadium in the feed liquid can be ensured to fully enter the filtrate for subsequent separation and recycling, and the valuable metal resources in the alloy material can be fully recycled. The metals such as molybdenum, phosphorus, vanadium and the like are separated from the alkaline filtrate, the process is simple, the time consumption is short, and the purity of each separated metal is good.
In the alloy material, the weight percentage of each element is as follows:
the content of molybdenum is 9-30%; the content of phosphorus is 5-20%; the content of vanadium is 5-20%; the content of nickel is 10-40%; the content of cobalt is 5-30%;
experimental research proves that the content of the valuable metals such as molybdenum, phosphorus and vanadium in the filter residue obtained after the burdening slurrying reaction and the pressure leaching reaction can be controlled to be below 0.1% at most, so that the valuable metals in the alloy feed liquid almost completely enter the filtrate for later separation and recycling.
As a preferable scheme of the invention, the separation of molybdenum, phosphorus and vanadium elements in the S4 filtrate comprises the following steps:
s411, low-temperature dephosphorization: performing low-temperature crystallization, water washing and filtration on the mixed filtrate in the S3 to obtain sodium phosphate crystals and a second filtrate, wherein the low-temperature crystallization temperature is 1-5 ℃;
s412a, molybdenum separation: adjusting the pH of the filtrate obtained in the step S411 to 7.0-9.0, and adsorbing the second filtrate at 25-60 ℃ by molybdenum adsorption resin to obtain filtrate after molybdenum ions are removed; after the molybdenum absorption resin is absorbed and saturated, resolving to obtain a molybdate solution;
s413a, separation of vanadium: and adsorbing the filtrate subjected to molybdenum ion removal by using vanadium-absorbing resin, and resolving after the vanadium-absorbing resin is saturated in adsorption to obtain a vanadate solution.
Wherein the speed of the filtrate of S411 passing through the molybdenum-absorbing resin is 5-10 m3H; the speed of the filtrate subjected to molybdenum ion removal in the step S412 when the filtrate passes through the vanadium absorbing resin is 5-10 m3/h。
And precipitating and recovering the separated molybdenum and vanadium metals to obtain molybdenum and vanadium products.
Precipitating the molybdate solution separated by the molybdenum adsorption resin in the step S412a by using flocculant magnesium sulfate to remove silicon, then adjusting the pH value to about 1-2 by using hydrochloric acid, and precipitating an industrial-grade molybdic acid product at 30-50 ℃;
and (4) precipitating the vanadate solution separated from the vanadium absorbing resin in the step (S413 a) by using flocculant aluminum sulfate to remove silicon, adjusting the pH of the solution to be about 1.5-3.5 at 70-80 ℃, and precipitating an industrial-grade ammonium metavanadate product by using ammonium chloride.
In a preferred embodiment of the present invention, the analyzing solutions used in the analyzing processes of step S412a and step S413a are sodium hydroxide solutions with a mass fraction of 10 to 20%.
In a preferred embodiment of the present invention, the molybdenum-adsorbing resin is any one of ZGD314, D352 and PDM.
As a preferable scheme of the invention, the model of the vanadium absorbing resin is ZGD231 or LS-32.
And (3) flushing and regenerating the desorbed molybdenum-absorbing resin and vanadium-absorbing resin by using a sulfuric acid solution with the mass fraction of 5-20% and pure water until the pH value of effluent reaches 2.0-5.0, and recycling.
In order to further optimize the dosage of the solvent, the inventor finds that vanadium element precipitation is directly carried out on the filtrate after phosphorus removal by adopting an ammonium sulfate solution to obtain metavanadate, and then the solution after vanadium removal is reacted with a perchloric acid solution to obtain molybdenum trioxide precipitation. By adopting the method, the problem that excessive alkaline analytic solution is needed to analyze the vanadium element and the molybdenum element from the resin after the resin adsorbs the vanadium element and the molybdenum element is avoided, and then the vanadium-adsorbing resin and the molybdenum-adsorbing resin are recovered by the acid solution to be recovered to the initial state for recycling. Further saving the use of acidic and alkaline solutions. Further reducing the cost. Therefore, it is further preferred that the second filtrate obtained in S411 is separated in the following manner:
s412b, preparation of industrial ammonium metavanadate: adjusting the pH of the second filtrate to 7.0-9.5 by using an aqueous solution of ammonium sulfate with the mass fraction of 25% -35%, stirring at 20-75 ℃, and filtering to obtain industrial-grade ammonium metavanadate and fourth filtrate containing sodium molybdate;
s413b, and preparation of molybdenum trioxide: and (3) regulating the pH of the fourth filtrate containing sodium molybdate obtained in the step (S412) to 0.5-4.5 by using 60-70% by mass of perchloric acid, stirring at 30-80 ℃, filtering and drying to obtain molybdenum trioxide.
Wherein, in the process of separating the molybdenum element from the vanadium element, the chemical reaction equation is as follows:
2NaVO3+(NH4)2SO4＝＝2NH4VO3↓+Na2SO4
Na2MoO4+H2O+2HClO4＝＝MoO3(H2O)2+2NaClO4
MoO3(H2O)2＝＝MoO3+2H2O
as a preferable scheme of the invention, the separation of iron, cobalt and nickel elements in the filter residue of S4 comprises the following steps:
s421, pressure oxidation acid leaching: and mixing the filter residue containing iron, cobalt and nickel elements in the S3 with an acidic solution according to a solid-liquid mass ratio of 1: 6-15, preparing a feed liquid, stirring at 70-90 ℃, performing slurrying reaction for 1-5h, pumping the slurry into a reaction kettle, pressurizing to 1-2.8Mpa, reacting for 2-8h, and filtering to obtain iron slag and a filtrate, wherein the filtrate contains nickel ions and cobalt ions;
s422, extracting and separating nickel and cobalt elements, and sequentially carrying out chemical impurity removal and extraction on the filtrate in the S421 to obtain a cobalt sulfate solution and a nickel sulfate solution; the extractant is P507;
the mass ratio of sulfuric acid in the acid solution to the slag containing iron, cobalt and nickel metal is 1.5-3.5: 1.
removing trace impurities such as Zn, Mn, Cu, Fe, Ca and the like in the solution by P204 extraction, and respectively evaporating, concentrating, crystallizing and recovering the extracted nickel sulfate and cobalt sulfate solution to obtain battery-grade cobalt sulfate and battery-grade nickel sulfate products.
In the preferable scheme of the invention, in the step S421, the pH of the feed liquid after the reaction is adjusted to 2.0-4.0, and the iron slag and the filtrate containing nickel ions and cobalt ions are obtained by filtering.
As a preferable scheme of the invention, at least two times of reverse washing are carried out before the separation of iron, cobalt and nickel metals in the S4 slag, until the pH value of the filtrate in the washing process is 7.0-8.0.
The 'reverse washing' method specifically refers to a circulating reverse washing mode which is used for washing the new slag for the second time by using clean water for the second time, and is used as a preparation liquid in the material mixing and slurrying reaction in the first washing water recycling step S1. According to the 2-time reverse washing mode, the pH value of the washing liquid in the whole circulation washing process is controlled to be 8.0-14.0 by an alkali adding regulation mode, on one hand, the contents of valuable metals such as molybdenum, phosphorus and vanadium in the alloy material can be further leached, so that the valuable metals enter the solution and then return to the step of batching and slurrying for full separation, leaching and recovery, on the other hand, the problem of environmental pollution caused by the discharge of washing waste liquid can be effectively avoided, and the process operation is more environment-friendly.
As a preferable scheme of the invention, the granularity of the alloy powder is 100-200 meshes.
The alloy material is finely ground and sieved in advance until the granularity is about 100 meshes, so that the specific surface area of the alloy material can be increased, the contact area of subsequent reaction is increased, and the full reaction is facilitated.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the method, after the cobalt-nickel alloy material containing molybdenum and vanadium is subjected to the batching and slurrying reaction in the step S2, in the step S3 of adding alkali and pressurizing and leaching molybdenum, phosphorus and vanadium, the reaction parameters in the reaction kettle are optimally controlled, so that molybdenum, phosphorus and vanadate ions in the material liquid react with the alkali, the valuable metals of molybdenum, phosphorus and vanadium in the material liquid can be ensured to fully enter the filtrate for subsequent separation and recycling, and the full recycling of valuable metal resources in the alloy material is realized.
2. According to the scheme of the invention, the mixed solution of high-purity solid sodium phosphate, sodium molybdate and sodium vanadate is obtained by washing and removing phosphorus at low temperature, and the recovery rate of phosphorus is more than 98.5 percent.
3. According to the scheme of the invention, molybdenum and vanadium metals are separated by resin, after the molybdenum absorption resin and the vanadium absorption resin are adsorbed and saturated, a molybdate solution and a vanadate solution are respectively obtained by resolving with a resolving liquid, and the total recovery rate of molybdenum and vanadium is more than 98.5%.
4. According to the scheme of the invention, the total recovery rate of nickel and cobalt can reach more than 99%, and valuable metals are basically and completely recovered.
5. According to the scheme of the invention, the separation process of molybdenum, phosphorus and vanadium metals in the alkaline solution is simpler, the separation is more thorough, and the purity of each separated metal is high.
6. In the process means of respectively extracting molybdenum element and vanadium element by a chemical precipitation method, vanadium is precipitated by ammonium sulfate to generate industrial-grade ammonium metavanadate, molybdenum is precipitated by perchloric acid and is dried to generate molybdenum trioxide, the recovery rate and the purity of molybdenum and vanadium are high, the process flow of a resin column is reduced, and certain acid and alkali consumption can be reduced.
Description of the drawings:
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is another process flow diagram of the present invention.
Detailed Description
The present invention will be described in further detail with reference to test examples and specific embodiments. It should be understood that the scope of the above-described subject matter is not limited to the following examples, and any techniques implemented based on the disclosure of the present invention are within the scope of the present invention.
Example 1
As shown in fig. 1, taking a nickel-containing cobalt-molybdenum-phosphorus-vanadium alloy material obtained by electric furnace mixed reduction smelting, taking 1kg of the material as an example, the nickel-containing cobalt-molybdenum-phosphorus-vanadium alloy material obtained by electric furnace mixed reduction smelting is detected to contain:
the content of Co is 9.36%, the content of Ni is 30.15%, the content of Mo is 15.65%, the content of Fe is 14.23%, the content of V is 9.4%, and the content of P is 12.35%; the alloy material is processed as follows:
the alloy material is ground and sieved to about 100 meshes, and the solid-liquid mass ratio is 1: 10 and alkali material mass ratio 2:1, adding water and liquid caustic soda into the alloy material to obtain slurried feed liquid, and then stirring and reacting for 3 hours at 75 ℃.
Pressure oxidation alkaline leaching: pumping the material liquid after the slurrying reaction into a pressurized reaction kettle, sealing the reaction kettle, starting steam for heating, introducing oxygen to increase the pressure in the kettle to 1.2MPa, slowing the oxygen introduction speed, slowly increasing the pressure to 1.9MPa within 60 minutes, closing a steam valve after the temperature is increased to 180 ℃ in the pressure increasing process, starting timing and preserving heat for 2 hours, controlling the pressure between 1.90 and 2.0Mpa in the heat preservation process, opening a steam valve to heat to maintain the temperature between 220 and 250 ℃, preserving the heat for 2 hours, after the heat preservation is finished, closing the steam valve, closing the oxygen valve, then slowly opening the emptying valve, opening the cooling water of the reaction kettle, and (3) reducing the pressure in the reaction kettle to normal pressure, pumping the slurry in the reaction kettle into a normal-pressure reaction tank after the temperature in the reaction kettle is reduced to 80 ℃, and filtering to obtain the nickel-cobalt-containing iron slag and a mixed solution containing sodium molybdate, sodium phosphate and sodium vanadate.
And carrying out low-temperature dephosphorization on the obtained mixed solution of sodium molybdate, sodium phosphate and sodium vanadate, washing the obtained mixed solution containing sodium molybdate, sodium phosphate and sodium vanadate at low temperature, controlling the temperature of the low-temperature water to be about 2 ℃, and filtering to obtain the mixed solution of solid high-purity sodium phosphate, sodium molybdate and sodium vanadate.
Through detection, the content of each metal in the leachate obtained after filtration is as follows: mo: 13.45g/L, P: 12.87g/L, V: 8.5g/L, and the slag rate is about 80 percent. The solid sodium phosphate obtained after low-temperature water washing contains the following metals: mo: 0.0023%, V: 0.0045%, P: 19.28 percent, can be sent to a phosphate fertilizer plant for recycling.
Taking the filtered mixed solution of sodium molybdate and sodium vanadate, adjusting the pH to about 8.0, and controlling the temperature at 40 ℃ at 7m per hour3Until ZGD324 absorbs molybdenum resin to saturation. Through detection, the content of each metal in the solution after the molybdenum resin is adsorbed by the ZGD324 is as follows: mo: 0.002g/L, V: 8.06 g/L.
And controlling the solution after the molybdenum resin is adsorbed by the ZGD324 to pass through the ZGD201 vanadium adsorption resin at the flow rate of 8m3 until the ZGD201 vanadium adsorption resin is saturated. Through detection, the content of each metal in the solution after the solution is saturated by the ZGD201 vanadium absorption resin is as follows: mo: 0.0001g/L, V: 0.001 g/L.
And after the resin is saturated, respectively using 10% sodium hydroxide solution as an analysis solution, and backwashing the saturated ZGD324 molybdenum absorption resin and the saturated ZGD324 molybdenum absorption resin to respectively obtain sodium molybdate solution and sodium vanadate solution.
Through detection: the molybdenum content in the sodium molybdate solution obtained by analysis is 80 g/L; the vanadium content in the sodium vanadate solution obtained by analysis is 64 g/L.
Further, the resolved resin is washed and regenerated by 6 percent sulfuric acid solution respectively, and then washed by pure water until the pH value of the effluent water is 7.0, and the resin can be recycled for standby.
Further, continuously adding acid into the alkaline leaching alloy material, pressurizing and oxidizing, and respectively mixing the obtained nickel-cobalt-iron-containing slag according to a solid-liquid mass ratio of 1: 10 and acid material mass ratio of 2.5: 1, adding water and sulfuric acid into the alloy material to obtain slurried feed liquid; and then stirring and reacting for 4 hours at 70 ℃, pumping the material liquid after the slurrying reaction into a pressurized reaction kettle, starting steam for heating, introducing oxygen, raising the pressure in the kettle to 1.0MPa, slowing down the oxygen introduction speed, slowly raising the pressure to 2.8MPa, controlling the temperature in the reaction kettle to 230 ℃, after keeping the temperature for reaction for 3 hours, opening an emptying valve to reduce the pressure in the reaction kettle to a normal pressure state, adjusting the pH value to 2.5 by using sodium carbonate, and filtering to obtain the recovered iron slag and the nickel-cobalt-containing filtrate. After filtration, the nickel-cobalt-containing filtrate is taken, and the Co content, the Ni content and the Fe content in the liquid are respectively 8.69g/L, 26.35g/L and 4.75 g/L.
And (3) extracting and separating nickel and cobalt: the method comprises the steps of firstly extracting a solution containing nickel and cobalt by P204 to remove trace impurities such as Zn, Mn, Cu, Fe, Ca and the like in the solution, then sequentially extracting nickel and cobalt in the solution by utilizing different extraction and separation coefficients of P507 to the nickel and cobalt, and respectively carrying out back extraction by using sulfuric acid to obtain a high-purity nickel sulfate solution and a high-purity cobalt sulfate solution. Further, the extracted organic phase can be returned for reuse.
Evaporating, concentrating and crystallizing to recover nickel sulfate and cobalt sulfate products, and respectively evaporating, concentrating and crystallizing the obtained cobalt sulfate solution and nickel sulfate solution to obtain battery-grade cobalt sulfate and battery-grade nickel sulfate products. After the treatment of the whole treatment process, the contents of all elements in percentage by weight are calculated by analysis:
the cobalt recovery rate is as follows: 99.12 percent; the nickel recovery rate is as follows: 99.27 percent; the recovery rate of molybdenum is 99.06%; the phosphorus recovery rate is 98.58 percent; the vanadium recovery was 98.93%.
Example 2
Taking an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, which is obtained by mixing, reducing and smelting in an electric furnace, taking 1kg of the alloy material as an example, the alloy material is detected to contain:
the content of Co is 10.01%, the content of Ni is 30.9%, the content of Mo is 13.52%, the content of Fe is 13.51%, and the content of V is 8.48%; the alloy material is processed as follows:
the specific procedure was as described in example 1. The differences are only that:
pressure oxidation alkaline leaching: pumping the material liquid after the slurrying reaction into a pressurized reaction kettle, sealing the reaction kettle, starting steam for heating, introducing oxygen to increase the pressure in the kettle to 1.6MPa, slowing the oxygen introduction speed, slowly increasing the pressure to 2.5MPa within 60 minutes, closing a steam valve after the temperature is increased to 190 ℃ in the pressure increasing process, starting timing and preserving heat for 1 hour, controlling the pressure between 2.5 and 2.6Mpa in the heat preservation process, opening a steam valve to heat to maintain the temperature between 190 ℃ and 230 ℃, preserving the heat for 1 hour, after the heat preservation is finished, closing the steam valve, closing the oxygen valve, then slowly opening the emptying valve, opening the cooling water of the reaction kettle, and (3) reducing the pressure in the reaction kettle to normal pressure, pumping the slurry in the reaction kettle into a normal-pressure reaction tank after the temperature in the reaction kettle is reduced to 80 ℃, and filtering to obtain the nickel-cobalt-containing iron slag and a mixed solution containing sodium molybdate, sodium phosphate and sodium vanadate.
After the treatment of the whole treatment process, the contents of all elements in percentage by weight are calculated by analysis:
the cobalt recovery rate is as follows: 99.25 percent; the nickel recovery rate is as follows: 99.30 percent; the recovery rate of molybdenum is 99.27%; the phosphorus recovery rate is 98.62 percent; the recovery rate of vanadium was 99.14%.
Example 3
Taking an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, which is obtained by mixing, reducing and smelting in an electric furnace, taking 1kg of the alloy material as an example, the alloy material is detected to contain:
the content of Co is 9.82%, the content of Ni is 31.55%, the content of Mo is 14.86%, the content of Fe is 13.38%, and the content of V is 8.76%; the alloy material is processed as follows:
the specific procedure was as described in example 1. The differences are only that:
pressure oxidation alkaline leaching: pumping the material liquid after the slurrying reaction into a pressurized reaction kettle, sealing the reaction kettle, starting steam for heating, introducing oxygen to increase the pressure in the kettle to 1.2MPa, slowing the oxygen introduction speed, slowly increasing the pressure to 1.7MPa within 60 minutes, closing a steam valve after the temperature is increased to 180 ℃ in the pressure increasing process, starting timing and preserving heat for 2.5 hours, controlling the pressure between 1.7 and 1.9Mpa in the heat preservation process, opening a steam valve to heat to maintain the temperature between 180 ℃ and 220 ℃, preserving the heat for 2.5 hours, after the heat preservation is finished, closing the steam valve, closing the oxygen valve, then slowly opening the emptying valve, opening the cooling water of the reaction kettle, and (3) reducing the pressure in the reaction kettle to normal pressure, pumping the slurry in the reaction kettle into a normal-pressure reaction tank after the temperature in the reaction kettle is reduced to 80 ℃, and filtering to obtain the nickel-cobalt-containing iron slag and a mixed solution containing sodium molybdate, sodium phosphate and sodium vanadate.
After the treatment of the whole treatment process, the contents of all elements in percentage by weight are calculated by analysis:
the cobalt recovery rate is as follows: 99.39 percent; the nickel recovery rate is as follows: 99.58 percent; the recovery rate of molybdenum is 99.81 percent; the phosphorus recovery rate is 99.68 percent; the vanadium recovery was 99.18%.
Example 4
Taking an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, which is obtained by mixing, reducing and smelting in an electric furnace, taking 1kg of the alloy material as an example, the alloy material is detected to contain:
the content of Co is 9.25%, the content of Ni is 30.58%, the content of Mo is 15.82%, the content of Fe is 14.37%, and the content of V is 9.06%; the alloy material is processed as follows:
the specific process method is shown in fig. 2, and the process is different from the process described in example 1 only in that:
respectively extracting molybdenum and vanadium: and (2) using an aqueous solution of ammonium sulfate with the mass fraction of 30% to adjust the pH value to 8.5, stirring for 2h at 70 ℃, filtering to obtain industrial ammonium metavanadate and filtrate containing sodium molybdate, adjusting the pH value of the filtrate containing sodium molybdate to 0.5-4.5 by using 70% perchloric acid, stirring for 2h at 75 ℃, filtering, and drying to obtain the molybdenum trioxide.
After the treatment of the whole treatment process, the contents of all elements in percentage by weight are calculated by analysis:
the cobalt recovery rate is as follows: 99.38 percent; the nickel recovery rate is as follows: 99.59 percent; the recovery rate of molybdenum is 99.90 percent; the phosphorus recovery rate is 99.67 percent; the vanadium recovery was 99.33%.
Example 5
Taking an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, which is obtained by mixing, reducing and smelting in an electric furnace, taking 1kg of the alloy material as an example, the alloy material is detected to contain:
the content of Co is 10.06%, the content of Ni is 31.02%, the content of Mo is 13.94%, the content of Fe is 14.68%, and the content of V is 8.95%; the alloy material is processed as follows:
the specific process method is shown in fig. 2, and the process is different from the process described in example 2 only in that:
respectively extracting molybdenum and vanadium: and (2) using 30 mass percent of aqueous solution of ammonium sulfate to adjust the pH value of the molybdenum vanadium solution after freezing and dephosphorization to 7.0-9.5, stirring for 2h at 25 ℃, filtering to obtain industrial ammonium metavanadate and filtrate containing sodium molybdate, adjusting the pH value of the filtrate containing sodium molybdate to 0.5-4.5 by using 60% perchloric acid, stirring for 2h at 40 ℃, filtering, and drying to obtain molybdenum trioxide.
After the treatment of the whole treatment process, the contents of all elements in percentage by weight are calculated by analysis:
the cobalt recovery rate is as follows: 99.41 percent; the nickel recovery rate is as follows: 99.63 percent; the recovery rate of molybdenum is 99.92%; the phosphorus recovery rate is 99.77%; the vanadium recovery was 99.43%.
Comparative example 1
Taking an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, which is obtained by mixing, reducing and smelting in an electric furnace, taking 1kg of the alloy material as an example, the alloy material is detected to contain:
the content of Co is 9.98%, the content of Ni is 29.84%, the content of Mo is 12.58%, the content of Fe is 13.63%, and the content of V is 7.76%; the alloy material is processed as follows:
the specific procedure was as described in example 1. The differences are only that:
pressure oxidation alkaline leaching: pumping the material liquid after the slurrying reaction into a pressurized reaction kettle, sealing the reaction kettle, starting steam for heating, introducing oxygen to increase the pressure in the kettle to 1.0MPa, slowing the oxygen introduction speed, slowly increasing the pressure to 1.5MPa within 60 minutes, closing a steam valve after the temperature is increased to 180 ℃ in the pressure increasing process, starting timing and preserving heat for 2.5 hours, controlling the pressure between 1.5 and 1.7Mpa in the heat preservation process, opening a steam valve to heat to maintain the temperature between 160 ℃ and 190 ℃, preserving the heat for 2.5 hours, after the heat preservation is finished, closing the steam valve, closing the oxygen valve, then slowly opening the emptying valve, opening the cooling water of the reaction kettle, and (3) reducing the pressure in the reaction kettle to normal pressure, pumping the slurry in the reaction kettle into a normal-pressure reaction tank after the temperature in the reaction kettle is reduced to 80 ℃, and filtering to obtain the nickel-cobalt-containing iron slag and a mixed solution containing sodium molybdate, sodium phosphate and sodium vanadate.
After the treatment of the whole treatment process, the contents of all elements in percentage by weight are calculated by analysis:
the cobalt recovery rate is as follows: 88.12 percent; the nickel recovery rate is as follows: 73.28 percent; the molybdenum recovery rate is 78.36 percent; the phosphorus recovery rate is 82.94%; the recovery rate of vanadium was 70.48%.
Comparative example 2
Taking an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, which is obtained by mixing, reducing and smelting in an electric furnace, taking 1kg of the alloy material as an example, the alloy material is detected to contain:
the content of Co is 9.67%, the content of Ni is 28.64%, the content of Mo is 14.46%, the content of Fe is 13.41%, the content of P is 11.95%, and the content of V is 9.52%; the alloy material is processed as follows:
the specific procedure was as described in example 1. The difference is that in the process of separating iron, cobalt and nickel, the parameters in the process of adding acid and pressurizing oxidation are adjusted:
adding acid into the filter residue of the alkaline leaching alloy material, pressurizing and oxidizing, and respectively mixing the obtained nickel-cobalt-iron-containing slag according to the solid-liquid mass ratio of 1: 10 and acid material mass ratio of 2.5: 1, adding water and sulfuric acid into the alloy material to obtain slurried feed liquid; and then stirring and reacting for 4 hours at 70 ℃, pumping the material liquid after the slurrying reaction into a pressurized reaction kettle, starting steam for heating, introducing oxygen, raising the pressure in the kettle to 0.5MPa, slowing down the oxygen introduction speed, slowly raising the pressure to 1.2MPa, controlling the temperature in the reaction kettle to be 150 ℃, after keeping the temperature for reacting for 3 hours, starting an emptying valve to reduce the pressure in the reaction kettle to a normal pressure state, adjusting the pH value to 2.5 by using sodium carbonate, and filtering to obtain the recovered iron slag and the nickel-cobalt-containing filtrate. After filtration, the nickel-cobalt-containing filtrate is taken, and the Co content, the Ni content and the Fe content in the liquid are respectively 5.31g/L, 11.29g/L and 3.68 g/L.
Comparative example 3
Taking an alloy material containing nickel, cobalt, molybdenum, phosphorus and vanadium, which is obtained by mixing, reducing and smelting in an electric furnace, taking 1kg of the alloy material as an example, the alloy material is detected to contain:
the content of Co is 10.67%, the content of Ni is 29.65%, the content of Mo is 13.46%, the content of Fe is 14.51%, the content of P is 11.35%, and the content of V is 9.12%; the alloy material is processed as follows:
the specific procedure was as described in example 1. The differences are only that:
the technological process includes the first pressurized oxygen-enriched acid leaching:
(1) grinding: the alloy material is ground and sieved to be below 100 meshes, and then the ground and sieved alloy powder is treated as follows:
(2) burdening and slurrying reaction: respectively adding the alloy powder into the alloy powder according to a liquid-solid ratio of 10: 1 and acid material ratio of 2:1, adding water and sulfuric acid, mixing, and reacting at 75 ℃ for 3 hours to obtain slurry material liquid after slurrying reaction.
(3) Pressure leaching for removing iron: and pumping the material liquid after the slurrying reaction into a pressurized reaction kettle, sealing the reaction kettle, starting steam for heating, introducing oxygen, and regulating the pressure to 1.2 Mpa. Then slowly increasing the pressure from 1.2MPa to 1.9MPa in 60 min, and closing the steam valve after the temperature is increased to 180 ℃ in the pressure increasing process. And (3) timing and preserving heat for 2 hours, controlling the pressure to be 1.90-2.0 Mpa in the heat preservation process, controlling the temperature to be 200-230 ℃, preserving heat for 2 hours again, closing a steam valve, closing an oxygen valve, slowly opening an exhaust valve, opening cooling water of the reaction kettle, reducing the pressure in the reaction kettle to normal pressure, pumping slurry in the reaction kettle into a normal-pressure reaction tank after the temperature in the reaction kettle is reduced to 80 ℃, pumping the slurry in the reaction kettle into the normal-pressure reaction tank, slowly adding sodium carbonate, adjusting the pH to be 1.5, and performing liquid-solid separation to obtain recovered iron slag and filtrate. And (3) reversely washing the obtained recovered iron slag for 2 times (the second washing water is used for the first washing, the first washing water is returned to the burdening pulping reaction to be used as a compound liquid, and clear water is added in the second washing), controlling the pH value of the washing liquid to be 3 in the washing process, and obtaining the recovered iron slag after washing. Through detection, the content of each metal in the leachate obtained after filtration is as follows: co: 11.86g/L, Ni: 19.26g/L, Mo: 17.69g/L, V: 11.15 g/L. The content of each metal in the recovered iron slag after washing is as follows: co: 0.03%, Ni: 0.035%, Mo: 1.093%, P1.106%; v: 1.075%; the slag rate is 22.1 percent, and the content of iron is 43.7 percent.
After the treatment of the whole treatment process, the contents of all elements in percentage by weight are calculated by analysis:
the cobalt recovery rate is as follows: 98.12 percent; the nickel recovery rate is as follows: 98.28 percent; the molybdenum recovery rate is 98.36%; the phosphorus recovery rate is 98.04 percent; the recovery rate of vanadium was 98.48%.
The acid leaching prevents molybdenum, phosphorus and vanadium in the alloy material from being leached completely, the content of molybdenum, phosphorus and vanadium in the recovered iron slag is more than 1%, the filtrate after the pressure acid leaching contains cobalt, nickel, molybdenum and vanadium metals, the cobalt and nickel recovery is carried out through a further extraction process after the molybdenum and vanadium metals are recovered through vanadium-absorbing resin and molybdenum-absorbing resin, the operation process is relatively complicated, the molybdenum and vanadium metal elements can be dispersed in the cobalt and nickel, the purity of the cobalt and nickel metal is not high, and the recovery rate of the molybdenum and vanadium is reduced.
Further, in order to achieve the resource-limited treatment, the iron slag needs to be further subjected to pressure oxygen introduction and alkaline leaching to leach out molybdenum, phosphorus and vanadium, so that high-purity iron slag and leaching solution containing molybdenum, phosphorus and vanadium are obtained, and the iron slag can be effectively treated.
In examples 1 to 3, the comprehensive control of the pressure, the reaction temperature and the reaction time of the reaction kettle during the pressure oxidation alkaline leaching process results in the highest separation degree of each metal in the alloy material, and comparative example 1 compared with example 1 reduces the pressure and the reaction temperature of the reaction kettle and prolongs the reaction time, and according to the results, the leaching effect is not ideal. Compared with the example 1, the parameters of the process of carrying out the pressure oxidation acid leaching on the iron, cobalt and nickel filter residues are changed in the comparative example 2, the alloy material is separated in the conventional pressure oxidation acid leaching mode in the comparative example 3, and the data show that the leaching rate of each metal in the alloy material is not high, and meanwhile, the purity of each metal of iron, cobalt and nickel is not high, and the impurities such as molybdenum, vanadium and the like are contained in the alloy material.
The experimental parameters of examples 1-3 and comparative example 1 described above are collated into Table one below:
table 1 is a data summary table of examples 1 to 5 and comparative examples 1 to 3
Acid/base consumption is the total acid/base consumption per kg of alloy material.
In the process method, the pressure oxidation alkaline leaching mode is adopted and the parameter ranges are controlled, so that the slurried alloy powder can react with alkali to generate corresponding molybdate, phosphate and vanadate under the coordination of experimental parameters, the molybdate, the phosphate and the vanadate are separated from the iron slag, the content of molybdenum, phosphorus and vanadium in the iron slag is extremely low, the molybdenum, phosphorus and vanadium are separated in a physical or chemical mode, the effect is obvious, the molybdenum, phosphorus and vanadium are leached approximately completely, and the purity of each metal is good. The full recovery and utilization of all metal resources are realized, and the concept of sustainable development is met.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The leaching separation method of the alloy material is characterized by comprising the following steps:
s1, raw material treatment: preparing alloy waste into alloy powder; the alloy waste contains iron, cobalt, nickel, molybdenum, phosphorus and vanadium elements;
s2, batching and slurrying reaction: mixing alloy powder and alkaline solution according to a solid-liquid mass ratio of 1: 7-15, preparing a feed liquid, stirring at 70-90 ℃, and performing slurrying reaction for 1-5 h; the mass ratio of liquid alkali or flake alkali to alloy powder in the alkaline solution is 1.2-3.5: 1;
s3, pressure oxidation alkaline leaching: pumping the material liquid after the S2 reaction into a reaction kettle, introducing oxygen to increase the pressure to 1.8-2.8 MPa, and reacting for 2-8h at the temperature of 160-; after the reaction is finished, adjusting the pH value of the slurry to 7-9, and filtering to obtain filter residue and filtrate, wherein the filter residue contains iron, cobalt and nickel elements, and the filtrate contains molybdate ions, phosphate ions and vanadate ions;
s4, multi-metal separation: and (4) separating iron, cobalt and nickel elements from the filter residue obtained in the step S3, and separating molybdenum, phosphorus and vanadium elements from the filtrate obtained in the step S3.
2. The leaching separation method for the alloy material according to claim 1, wherein the separation process of molybdenum, phosphorus and vanadium elements in the S4 filtrate comprises the following steps:
s411, dephosphorization: crystallizing, washing and filtering the mixed filtrate obtained in the step S3 to obtain sodium phosphate crystals and a second filtrate, wherein the crystallization temperature is 1-5 ℃;
s412a, molybdenum separation: adjusting the pH value of the second filtrate obtained in the step S411 to 7.0-9.0, and adsorbing the second filtrate through molybdenum absorption resin at the temperature of 25-60 ℃ to obtain a third filtrate after molybdenum ions are removed; resolving the molybdenum adsorption resin to obtain a molybdate solution;
s413a, separation of vanadium: and adsorbing the third filtrate after molybdenum ion removal through vanadium-adsorbing resin, and analyzing the vanadium-adsorbing resin to obtain a vanadate solution.
3. The leaching separation method of an alloy material according to claim 2, wherein the resolving solution used in the resolving process in step S412a and step S413a is a sodium hydroxide solution with a mass fraction of 10-20%.
4. The leaching separation method of an alloy material according to claim 2, wherein the model of the molybdenum-adsorbing resin is any one of ZGD314, D352 and PDM.
5. The leaching and separating method of an alloy material as claimed in claim 2, wherein the model of the vanadium-absorbing resin is ZGD231 or LS-32.
6. The leaching separation method of alloy materials according to claim 2, wherein the second filtrate obtained in S411 is separated in the following way:
s412b, preparation of industrial ammonium metavanadate: adjusting the pH of the second filtrate to 7.0-9.5 by using an aqueous solution of ammonium sulfate with the mass fraction of 25% -35%, stirring at 20-75 ℃, and filtering to obtain industrial-grade ammonium metavanadate and fourth filtrate containing sodium molybdate;
s413b, and preparation of molybdenum trioxide: and (3) regulating the pH of the fourth filtrate containing sodium molybdate obtained in the step (S412) to 0.5-4.5 by using 60-70% by mass of perchloric acid, stirring at 30-80 ℃, filtering and drying to obtain molybdenum trioxide.
7. The leaching and separating method of the alloy material according to claim 1, wherein the step of separating iron, cobalt and nickel elements in the filter residue at S4 comprises the following steps:
s421, pressure oxidation acid leaching: and mixing the filter residue obtained in the step S3 with an acidic solution according to a solid-liquid mass ratio of 1: 6-15, preparing a feed liquid, stirring at 70-90 ℃, performing slurrying reaction for 1-5h, pumping the slurry into a reaction kettle, pressurizing to 1-2.8Mpa, reacting for 2-8h, and filtering to obtain iron slag and a fourth filtrate, wherein the fourth filtrate contains nickel ions and cobalt ions; the acid solution is sulfuric acid;
s422, extracting and separating nickel and cobalt elements, and sequentially carrying out chemical impurity removal and extraction on the fourth filtrate obtained in the S421 to obtain a cobalt sulfate solution and a nickel sulfate solution; the extractant is P507;
the mass ratio of the sulfuric acid in the acid solution to the filter residue is 1.5-3.5: 1.
8. the leaching separation method of the alloy material according to claim 6, wherein in S421, the pH of the solution after the reaction is adjusted to 2.0-4.0, and the solution is filtered to obtain the iron slag and a fourth filtrate.
9. The leaching separation method for the alloy material according to claim 1, wherein the filter residue obtained from the step S3 is subjected to reverse washing at least twice until the pH of the filtrate in the washing process is 7.0-8.0.
10. The method as claimed in claim 1, wherein the grain size of the alloy powder is 100-200 mesh.
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| CN115927882A (en) * | 2022-12-23 | 2023-04-07 | 中国科学院过程工程研究所 | Method for separating vanadium and nickel |
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