CN114058859A - Method for preparing nickel vanadate from petroleum POX slag - Google Patents
Method for preparing nickel vanadate from petroleum POX slag Download PDFInfo
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- CN114058859A CN114058859A CN202111411878.0A CN202111411878A CN114058859A CN 114058859 A CN114058859 A CN 114058859A CN 202111411878 A CN202111411878 A CN 202111411878A CN 114058859 A CN114058859 A CN 114058859A
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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
- C22B7/04—Working-up slag
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by dry processes
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0438—Nitric acids or salts thereof
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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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
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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
- C22B7/001—Dry processes
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- 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
Abstract
The invention provides a method for preparing nickel vanadate from petroleum POX slag, which comprises the following steps: sequentially carrying out roasting decarburization, crushing, acid leaching, solid-liquid separation, impurity removal on an acid leaching solution and hydrothermal synthesis treatment on the petroleum POX slag to obtain nickel vanadate, wherein the pH value of the acid leaching solution in the impurity removal process is 1.5-2.5. In the invention, valuable elements vanadium and nickel in the petroleum POX slag are fully utilized, and meanwhile, a nickel vanadate product with high added value can be prepared.
Description
Technical Field
The invention belongs to the technical field of petrochemical metallurgy, and relates to a method for preparing nickel vanadate from petroleum POX slag.
Background
With the rapid development of the oil industry, a large amount of sludge is inevitably produced during oil extraction, transportation, storage and processing. Most of the oil sludge contains high crude oil (mineral oil) content and valuable metal elements such as vanadium and nickel, so that the direct discharge of the oil sludge not only brings serious harm to the environment and human health, but also causes waste of resources. The comprehensive treatment of harmlessly and cleanly treating the oily sludge and recovering resources in the oily sludge becomes one of the key points of environmental protection and petroleum industry at home and abroad. A series of waste residues generated in petroleum processing such as oil sludge residue, deoiled asphalt, catalytic oil slurry, ethylene tar and the like contain valuable resources such as vanadium and nickel, and have obvious economic and environmental benefits for harmless and resource treatment. Generally, a POX (partial oxidation technology) technology is adopted to carry out harmless and clean treatment on waste residues, so that cheap hydrogen, clean electric energy and steam are provided for refineries, and obtained ash residues are further recycled. Therefore, the obtained petroleum ash contains heavy metals such as vanadium, nickel and the like, if the heavy metals are directly stabilized, the heavy metals cannot be recovered, so that the resource waste is caused, and the direct stabilization treatment has larger energy consumption and great harm.
CN112301227A discloses a recycling method of a hydrogenation waste catalyst, which comprises the steps of mixing a deoiling hydrogenation waste catalyst with soda ash, roasting in a rotary kiln to obtain a roasted material, adding water, ball-milling, and filtering to obtain a filtrate and leaching residues; adding ammonium chloride into the leachate, stirring, and filtering to obtain ammonium metavanadate; adjusting the pH value of the vanadium-removing filtrate to 2 by using sulfuric acid, stirring, heating and filtering to obtain molybdic acid; adding sodium hydroxide and water into the leached residues, stirring uniformly, roasting in a tunnel kiln to obtain a roasted material, adding water into the roasted material, stirring and leaching to obtain a sodium aluminate solution and nickel-rich residues, packaging and selling the nickel-rich residues, adjusting the pH value of the sodium aluminate solution to 7.5 by adopting sulfuric acid, stirring and filtering to obtain the aluminum hydroxide. In the method, the recovery rate of molybdenum is 93%, the recovery rate of nickel is 98% and the recovery rate of aluminum is 85%.
CN111321296A discloses a method for recovering vanadium and nickel from waste petroleum catalysts, which adopts a roasting process to remove organic matters containing carbon and sulfur, then crushes residues, volatilizes the crushed residues through vacuum heating to respectively obtain high-vanadium and high-nickel intermediate products, dissolves the intermediate products through a weak acid dissolution method, and removes impurity elements such as aluminum and the like through adjusting a pH value, wherein the recovery rate of vanadium and nickel in the method reaches more than 90 percent, and the purity is higher.
CN105274343A discloses a method for extracting tungsten and nickel from petroleum hydrogenation waste catalyst, the method comprises the steps of oxidizing roasting, sodium treatment roasting and leaching test; the oxidation roasting is to remove the water content of the waste catalyst in a vacuum drying oven and then put the waste catalyst into a sealed test sample preparation crusher for crushing; putting the ground and screened waste catalyst with a certain mass into a muffle furnace, oxidizing and roasting for 3-5 hours to convert sulfide into oxide; the waste catalyst and sodium carbonate are placed in a muffle furnace according to a certain proportion for high-temperature roasting, and tungsten oxide can be converted into soluble sodium tungstate; the method can reduce environmental pollution, realize the recycling of resources, is beneficial to catalyst production enterprises to reduce production cost, improves the technical service level and the market competitiveness of products, and the recycled tungsten and nickel have great recycling value and economic benefit.
It can be seen from the presently disclosed method that vanadium is currently recovered in the form of ammonium metavanadate or vanadium pentoxide, nickel is currently recovered in the form of nickel-rich slag, and deep processing of the recovered vanadium and nickel is required to prepare vanadium and nickel products with high added values, which inevitably results in a complex process flow and poor economy. The nickel vanadate is a kind of lithium ion battery cathode material with advantages, and has the advantages of high electrode specific capacity, low cost, environmental friendliness and the like. At present, the main preparation method of nickel vanadate is to firstly prepare a precursor by adopting a precipitation method, a hydrothermal synthesis method, a solvothermal method or a sol method and the like, and then to obtain a final active phase for electrochemical performance test after roasting at 400-500 ℃. However, in the existing methods for preparing nickel vanadate, purified ammonium metavanadate or vanadium pentoxide is used as a vanadium source, and purified nickel chloride or nickel nitrate or nickel sulfate is used as a nickel source for synthesis, so that the existing process for preparing nickel vanadate from vanadium-containing and nickel-containing raw materials has the defect of long process flow, and a process for preparing nickel vanadate from vanadium-containing and nickel-containing raw materials in a short process is required to be developed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing nickel vanadate from petroleum POX slag.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for preparing nickel vanadate from petroleum POX slag, which comprises the following steps:
and sequentially carrying out roasting decarburization, crushing, acid leaching, solid-liquid separation, impurity removal on the acid leaching solution and hydrothermal synthesis treatment on the petroleum POX slag to obtain the nickel vanadate.
The method for obtaining the nickel vanadate by sequentially carrying out roasting decarburization, crushing, acid leaching, solid-liquid separation, impurity removal on the acid leaching solution and hydrothermal synthesis treatment on the petroleum POX slag can realize harmless treatment and resource utilization of the petroleum POX slag, and can efficiently recover vanadium and nickel and prepare a vanadium-nickel product with a high added value; compared with the traditional treatment process, the method can simultaneously recover the nickel vanadium, and realize the direct preparation of the nickel vanadate from the waste, thereby greatly shortening the preparation process of the nickel vanadate.
The pH of the pickle liquor during the impurity removal process is 1.5 to 2.5, and may be, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, or 2.5, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
The pH value of the pickle liquor impurity removal process is particularly limited to be 1.5-2.5, because the removal rate of iron is highest and the precipitation loss rate of vanadium is low in the pH value range, when the pH value of the pickle liquor impurity removal process exceeds the limit value of 2.5, the vanadium can be hydrolyzed and precipitated to cause the loss of vanadium; when the pH during the removal of the pickling liquid is below the limit of 1.5, incomplete precipitation of iron may result, since partial dissolution may occur due to the increased solubility of iron oxalate when the pH is too low.
In the invention, valuable elements vanadium and nickel in the petroleum POX slag are fully utilized, and meanwhile, a nickel vanadate product with high added value can be prepared.
In a preferred embodiment of the present invention, the temperature of the roasting decarburization process is 600 to 800 ℃, and may be, for example, 600 ℃, 620 ℃, 640 ℃, 660 ℃, 680 ℃, 700 ℃, 720 ℃, 740 ℃, 760 ℃, 780 ℃, 800 ℃, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are also applicable.
In a preferred embodiment of the present invention, the particle size of the petroleum POX slag after the grinding process is less than 74 μm, for example, 73.9 μm, 73.8 μm, 73.6 μm, 73 μm, 72 μm, 71 μm, 60 μm, 50 μm, 40 μm, 30 μm, 10 μm, but the particle size is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the leaching temperature in the acid leaching process is 80 to 100 ℃, and may be, for example, 80 ℃, 82 ℃, 84 ℃, 86 ℃, 88 ℃, 90 ℃, 92 ℃, 94 ℃, 96 ℃, 98 ℃ and 100 ℃, but the present invention is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
Preferably, the leaching time of the acid leaching process is 2-4 h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the acid solution in the acid leaching process is a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution.
Preferably, the concentration of hydrogen ions in the acidic solution is 3 to 6mol/L, for example, 3mol/L, 4mol/L, 5mol/L, 6mol/L, but not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferred technical scheme, the pickle liquor and the leaching residue are obtained after the process of removing impurities from the pickle liquor.
As a preferable technical scheme of the invention, the impurity removing agent adopted in the impurity removing process is oxalate.
Preferably, the ratio of the amount of oxalate ions to the amount of iron ions in the oxalate is (3-8): for example, 1 is 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, but is not limited to the recited values, and other values not recited in the above range are also applicable.
Preferably, the oxalate is any one or a combination of two or more of oxalic acid, sodium oxalate or sodium hydrogen oxalate.
As a preferable technical scheme, the pH value of the pickle liquor is adjusted by adopting a sodium hydroxide solution in the impurity removal process, and the iron-containing slag and the purified liquor containing vanadium and nickel are obtained through stirring and solid-liquid separation.
Preferably, the pH is 1.5 to 2.5, and may be, for example, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the sodium hydroxide solution is stirred during the process of adjusting the pH.
Preferably, the temperature during the stirring process is 50 to 60 ℃, for example, 50 ℃, 52 ℃, 54 ℃, 56 ℃, 58 ℃ and 60 ℃, but the temperature is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the stirring process is carried out for 1-2 hours, such as 1 hour, 1.2 hours, 1.4 hours, 1.6 hours, 1.8 hours, and 2 hours, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferable technical scheme of the invention, the hydrothermal synthesis process is carried out in a reaction kettle.
Preferably, before the hydrothermal synthesis process, nickel salt or vanadate is added into the purified solution containing vanadium and nickel, and the molar ratio of vanadium to nickel in the solution is adjusted to 1: 1.
Preferably, the pH of the vanadium-and nickel-containing purified solution after adding the nickel salt is 4-5.5, for example, 4, 4.2, 4.4, 4.6, 4.8, 5, 5.1, 5.2, 5.3, 5.4, 5.5, but is not limited to the values listed, and other values not listed in the range of the values are also applicable.
Preferably, the reaction temperature in the hydrothermal synthesis process is 220 to 280 ℃, for example, 220 ℃, 240 ℃, 260 ℃ and 280 ℃, but the reaction temperature is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
Preferably, the reaction time of the hydrothermal synthesis process is 4-8 h, for example, 4h, 5h, 6h, 7h, and 8h, but is not limited to the recited values, and other values not recited in the range of the recited values are also applicable.
As a preferable technical scheme of the invention, after the hydrothermal synthesis process, the nickel vanadate is obtained by cooling, washing and drying.
Preferably, the washing process employs deionized water.
Preferably, the drying process is carried out in a vacuum drying oven.
Preferably, the drying temperature is 60 to 80 ℃, for example, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
As a preferred technical solution of the present invention, the method includes: sequentially carrying out roasting decarburization, crushing, acid leaching, solid-liquid separation, impurity removal on acid leaching liquid and hydrothermal synthesis treatment on petroleum POX slag to obtain nickel vanadate, wherein the petroleum POX slag comprises iron, vanadium and nickel, the mass fraction of the iron is 0.5-2%, the mass fraction of the vanadium is 1-2%, the mass fraction of the nickel is 0.5-1.5% and the pH value of the acid leaching liquid in the impurity removal process is 1.5-2.5 calculated by taking the mass of the petroleum POX slag as 100%;
the temperature in the roasting decarburization process is 600-800 ℃, after the crushing process, the grain size of the petroleum POX slag is less than 74 micrometers, the leaching temperature in the acid leaching process is 80-100 ℃, the leaching time in the acid leaching process is 2-4 hours, the acid solution in the acid leaching process is a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution, and the hydrogen ion concentration in the acid solution is 3-6 mol/L;
and after the process of removing impurities from the pickle liquor, obtaining the pickle liquor and leaching slag, wherein the impurity removing agent adopted in the impurity removing process is oxalate, and the mass ratio of oxalate ions to iron ions in the oxalate is (3-8): 1, the oxalate is any one or a combination of two or more of oxalic acid, sodium oxalate or sodium hydrogen oxalate, the pH value of the pickle liquor is adjusted by adopting a sodium hydroxide solution in the impurity removal process, and the pickle liquor containing iron slag and vanadium and nickel is obtained through stirring and solid-liquid separation, wherein the pH value is 1.5-2.5, the process of adjusting the pH value by using the sodium hydroxide solution needs stirring, the temperature in the stirring process is 50-60 ℃, and the time in the stirring process is 1-2 hours;
the hydrothermal synthesis process is carried out in a reaction kettle, before the hydrothermal synthesis process, nickel salt or vanadate is added into the vanadium-nickel-containing purification solution, the molar ratio of vanadium to nickel is 1:1, the pH of the vanadium-nickel-containing purification solution after nickel salt addition is 4-5.5, the reaction temperature in the hydrothermal synthesis process is 220-280 ℃, the reaction time in the hydrothermal synthesis process is 4-8 h, after the hydrothermal synthesis process, nickel vanadate is obtained through cooling, washing and drying, deionized water is adopted in the washing process, the drying process is carried out in a vacuum drying oven, and the drying temperature is 60-80 ℃.
Compared with the prior art, the invention has the beneficial effects that:
in the invention, valuable elements vanadium and nickel in the petroleum POX slag are fully utilized, and meanwhile, a nickel vanadate product with high added value can be prepared.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
In one embodiment, the invention provides a method for preparing nickel vanadate from petroleum POX slag, which comprises the following steps:
the method for preparing the nickel vanadate comprises the steps of sequentially carrying out roasting decarburization, crushing, acid leaching, solid-liquid separation, impurity removal on acid leaching liquid and hydrothermal synthesis on petroleum POX slag to obtain the nickel vanadate; compared with the traditional extraction process, the method can simultaneously recover the nickel vanadium, and realize the direct preparation of the nickel vanadate from the waste, thereby greatly shortening the preparation process of the nickel vanadate.
The pH value of the acid leaching solution in the impurity removal process is 1.5-2.5, the pH value of the acid leaching solution in the impurity removal process is particularly limited to be 1.5-2.5, because the removal rate of iron is highest and the precipitation loss rate of vanadium is low in the pH value range, when the pH value of the acid leaching solution in the impurity removal process exceeds the limit value of 2.5, the vanadium is hydrolyzed and precipitated to cause the loss of vanadium; when the pH during the removal of the pickling liquid is below the limit of 1.5, incomplete precipitation of iron may result, since partial dissolution may occur due to the increased solubility of iron oxalate when the pH is too low.
In the invention, valuable elements vanadium and nickel in the petroleum POX slag are fully utilized, and meanwhile, a nickel vanadate product with high added value can be prepared.
The temperature of the roasting decarburization process is 600-800 ℃, after the crushing process, the grain size of the petroleum POX slag is less than 74 μm, the leaching temperature of the acid leaching process is 80-100 ℃, the leaching time of the acid leaching process is 2-4 h, further, the acid solution in the acid leaching process is sulfuric acid solution, hydrochloric acid solution or nitric acid solution, and the hydrogen ion concentration in the acid solution is 3-6 mol/L.
After the process of removing impurities from the pickle liquor, obtaining the pickle liquor and leaching slag, removing impurities from the pickle liquor by using an oxalate removing agent, wherein the mass ratio of oxalate ions to iron ions in oxalate is (3-8): 1, the oxalate is any one or a combination of two or more of oxalic acid, sodium oxalate or sodium hydrogen oxalate, the pH value of the pickle liquor is adjusted by adopting a sodium hydroxide solution in the impurity removal process, and the pickle liquor containing iron slag and vanadium and nickel is obtained through stirring and solid-liquid separation, and further the pH value is 1.5-2.5.
Stirring is needed in the process of adjusting the pH value of a sodium hydroxide solution, the temperature in the stirring process is 50-60 ℃, the time in the stirring process is 1-2 hours, the hydrothermal synthesis process is carried out in a reaction kettle, nickel salt or vanadate is added into a purifying solution containing vanadium and nickel before the hydrothermal synthesis process, the molar ratio of vanadium to nickel in the adjusted solution is 1:1, the pH value of the purifying solution is adjusted to be 4-5.5, the reaction temperature in the hydrothermal synthesis process is 220-280 ℃, and the reaction time in the hydrothermal synthesis process is 4-8 hours. After the hydrothermal synthesis process, cooling, washing and drying to obtain nickel vanadate, further adopting deionized water in the washing process, and carrying out the drying process in a vacuum drying oven, further, the drying temperature is 60-80 ℃.
Example 1
The embodiment provides a method for preparing nickel vanadate from petroleum POX slag, wherein the method comprises the following steps:
the POX slag as the test raw material contains 0.5 wt% of iron, 1 wt% of vanadium and 0.5 wt% of nickel. Roasting and decarbonizing the POX slag at 600 ℃, leaching for 2 hours at 80 ℃ by using 3mol/L hydrochloric acid solution, and then carrying out solid-liquid separation to obtain pickle liquor and leaching slag. According to the mass ratio of oxalate ions to iron ions of 3:1 adding sodium oxalate into the pickle liquor, adjusting the pH value of the pickle liquor to 1.5 by adopting sodium hydroxide, controlling the reaction temperature to be 50 ℃, stirring for 1 hour, and carrying out solid-liquid separation to obtain iron-containing slag and a purified solution containing vanadium and nickel. Adding nickel salt into the purified solution, adjusting the molar ratio of vanadium to nickel to be 1:1, adjusting the pH of the purified solution to 4.0, and reacting at 220 ℃ for 4 h. And filtering the reacted slurry, washing the slurry by deionized water, and drying the slurry in a vacuum drying oven.
Analysis and detection prove that the vanadium leaching rate is 83.58 percent, the nickel leaching rate is 67.52 percent, and the purity of the prepared nickel vanadate is 98.37 percent.
Example 2
The embodiment provides a method for preparing nickel vanadate from petroleum POX slag, wherein the method comprises the following steps:
the POX slag as the test raw material contains 0.8 wt% of iron, 1.2 wt% of vanadium and 0.7 wt% of nickel. Roasting and decarbonizing the POX slag at 650 ℃, leaching for 2.5 hours at 80 ℃ by using 3.5mol/L nitric acid solution, and then carrying out solid-liquid separation to obtain pickle liquor and leaching slag. According to the mass ratio of oxalate ions to iron ions, the ratio is 4:1 adding oxalic acid into the pickle liquor, adjusting the pH value of the pickle liquor to 1.8 by adopting sodium hydroxide, controlling the reaction temperature to be 52 ℃, stirring for 1.2h, and carrying out solid-liquid separation to obtain iron-containing slag and a purified solution containing vanadium and nickel. Adding nickel salt into the purified solution, adjusting the molar ratio of vanadium to nickel to be 1:1, adjusting the pH of the purified solution to 4.3, and reacting at 240 ℃ for 5 h. And filtering the reacted slurry, washing the slurry by deionized water, and drying the slurry in a vacuum drying oven.
Analysis and detection prove that the vanadium leaching rate is 89.42 percent, the nickel leaching rate is 73.25 percent, and the purity of the prepared nickel vanadate is 98.89 percent.
Example 3
The embodiment provides a method for preparing nickel vanadate from petroleum POX slag, wherein the method comprises the following steps:
the POX slag as the test raw material contains 1.0 wt% of iron, 1.5 wt% of vanadium and 1.0 wt% of nickel. Roasting and decarbonizing the POX slag at 700 ℃, leaching for 3.0 hours at 90 ℃ by adopting 2.0mol/L sulfuric acid solution, and then carrying out solid-liquid separation to obtain pickle liquor and leaching slag. According to the mass ratio of oxalate ions to iron ions of 5:1 adding sodium hydrogen oxalate into the pickle liquor, adjusting the pH value of the pickle liquor to 2.0 by adopting sodium hydroxide, controlling the reaction temperature to 54 ℃, stirring for 1.5h, and carrying out solid-liquid separation to obtain iron-containing slag and a purified solution containing vanadium and nickel. Adding nickel salt into the purified solution, adjusting the molar ratio of vanadium to nickel to be 1:1, adjusting the pH of the purified solution to 4.8, and reacting at 250 ℃ for 5.5 h. And filtering the reacted slurry, washing the slurry by deionized water, and drying the slurry in a vacuum drying oven.
Through analysis and detection, the vanadium leaching rate is 92.75 percent, the nickel leaching rate is 80.28 percent, and the purity of the prepared nickel vanadate is 99.13 percent.
Example 4
The embodiment provides a method for preparing nickel vanadate from petroleum POX slag, wherein the method comprises the following steps:
the POX slag as a test raw material contains 1.5 wt% of iron, 1.7 wt% of vanadium and 1.7 wt% of nickel. Roasting and decarbonizing the POX slag at 750 ℃, leaching for 3.5 hours at 95 ℃ by adopting 2.5mol/L sulfuric acid solution, and then carrying out solid-liquid separation to obtain pickle liquor and leaching slag. According to the mass ratio of oxalate ions to iron ions of 6:1 adding sodium oxalate into the pickle liquor, adjusting the pH value of the pickle liquor to 2.2 by adopting sodium hydroxide, controlling the reaction temperature to 56 ℃, stirring for 1.7h, and carrying out solid-liquid separation to obtain iron-containing slag and a purified solution containing vanadium and nickel. Adding nickel salt into the purified solution, adjusting the molar ratio of vanadium to nickel to be 1:1, adjusting the pH of the purified solution to 5.1, and reacting at 270 ℃ for 7 h. And filtering the reacted slurry, washing the slurry by deionized water, and drying the slurry in a vacuum drying oven.
Through analysis and detection, the vanadium leaching rate is 95.75 percent, the nickel leaching rate is 89.28 percent, and the purity of the prepared nickel vanadate is 99.41 percent.
Example 5
The embodiment provides a method for preparing nickel vanadate from petroleum POX slag, wherein the method comprises the following steps:
the POX slag as the test raw material contains 2.0 wt% of iron, 2.0 wt% of vanadium and 1.5 wt% of nickel. Roasting and decarbonizing the POX slag at 800 ℃, leaching for 4 hours at 100 ℃ by adopting 6mol/L hydrochloric acid solution, and then carrying out solid-liquid separation to obtain pickle liquor and leaching slag. According to the mass ratio of oxalate ions to iron ions being 8:1 adding sodium oxalate into the pickle liquor, adjusting the pH value of the pickle liquor to 2.5 by adopting sodium hydroxide, controlling the reaction temperature to be 60 ℃, stirring for 2.0h, and carrying out solid-liquid separation to obtain iron-containing slag and a purified solution containing vanadium and nickel. Adding nickel salt into the purified solution, adjusting the molar ratio of vanadium to nickel to be 1:1, adjusting the pH of the purified solution to 5.5, and reacting at 280 ℃ for 8 h. And filtering the reacted slurry, washing the slurry by deionized water, and drying the slurry in a vacuum drying oven.
Through analysis and detection, the vanadium leaching rate is 99.97%, the nickel leaching rate is 96.29%, and the purity of the prepared nickel vanadate is 99.57%.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. A method for preparing nickel vanadate from petroleum POX slag is characterized by comprising the following steps:
sequentially carrying out roasting decarburization, crushing, acid leaching, solid-liquid separation, impurity removal on an acid leaching solution and hydrothermal synthesis treatment on the petroleum POX slag to obtain nickel vanadate, wherein the pH value of the acid leaching solution in the impurity removal process is 1.5-2.5.
2. The method according to claim 1, wherein the temperature of the roasting process is 600-800 ℃.
3. The process according to claim 1 or 2, characterized in that after the comminution process the particle size of the petroleum POX slag is <74 μ ι η.
4. The method according to any one of claims 1 to 3, wherein the leaching temperature of the acid leaching process is 80 to 100 ℃;
preferably, the leaching time of the acid leaching process is 2-4 h.
5. The method according to any one of claims 1 to 4, wherein the acidic solution in the acid leaching process is a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution;
preferably, the concentration of hydrogen ions in the acidic solution is 3-6 mol/L.
6. The method according to any one of claims 1 to 5, characterized in that the pickle liquor and the leached residue are obtained after the process of removing impurities from the pickle liquor.
7. The method according to any one of claims 1 to 6, wherein the impurity removing agent adopted in the impurity removing process is oxalate;
preferably, the ratio of the amount of oxalate ions to the amount of iron ions in the oxalate is (3-8): 1;
preferably, the oxalate is any one or a combination of two or more of oxalic acid, sodium oxalate or sodium hydrogen oxalate.
8. The method according to any one of claims 1 to 7, characterized in that the pH value of the pickle liquor is adjusted by sodium hydroxide solution in the process of removing impurities from the pickle liquor, and the pickle liquor is stirred and subjected to solid-liquid separation to obtain iron-containing slag and a purified liquor containing vanadium and nickel;
preferably, the pH is 1.5-2.5;
preferably, the process of adjusting the pH value of the sodium hydroxide solution needs to be stirred;
preferably, the temperature in the stirring process is 50-60 ℃;
preferably, the time of the stirring process is 1-2 h.
9. The method according to any one of claims 1 to 8, wherein the hydrothermal synthesis process is carried out in a reaction kettle;
preferably, before the hydrothermal synthesis process, nickel salt or vanadate is added into the purifying solution containing vanadium and nickel, so that the molar ratio of vanadium to nickel in the solution is 1: 1;
then, the molar ratio of the vanadium to the nickel is 1: 1;
preferably, the pH value of the vanadium-nickel-containing purification solution after nickel salt is added is 4-5.5;
preferably, the reaction temperature in the hydrothermal synthesis process is 220-280 ℃;
preferably, the reaction time of the hydrothermal synthesis process is 4-8 h;
preferably, after the hydrothermal synthesis process, cooling, washing and drying are carried out to obtain nickel vanadate;
preferably, the washing process employs deionized water;
preferably, the drying process is carried out in a vacuum drying oven;
preferably, the drying temperature is 60-80 ℃.
10. The method according to any one of claims 1-9, characterized in that the method comprises: sequentially carrying out roasting decarburization, crushing, acid leaching, solid-liquid separation, impurity removal on an acid leaching solution and hydrothermal synthesis treatment on the petroleum POX slag to obtain nickel vanadate, wherein the pH value of the acid leaching solution in the impurity removal process is 1.5-2.5;
the temperature in the roasting process is 600-800 ℃, after the crushing process, the particle size of the petroleum POX slag is less than 74 micrometers, the leaching temperature in the acid leaching process is 80-100 ℃, the leaching time in the acid leaching process is 2-4 hours, the acid solution in the acid leaching process is a sulfuric acid solution, a hydrochloric acid solution or a nitric acid solution, and the hydrogen ion concentration in the acid solution is 3-6 mol/L;
and after the process of removing impurities from the pickle liquor, obtaining the pickle liquor and leaching slag, wherein the impurity removing agent adopted in the impurity removing process is oxalate, and the mass ratio of oxalate ions to iron ions in the oxalate is (3-8): 1, the oxalate is any one or a combination of two or more of oxalic acid, sodium oxalate or sodium hydrogen oxalate, the pH value of the pickle liquor is adjusted by adopting a sodium hydroxide solution in the impurity removal process, and the pickle liquor containing iron slag and vanadium and nickel is obtained through stirring and solid-liquid separation, wherein the pH value is 1.5-2.5, the process of adjusting the pH value by using the sodium hydroxide solution needs stirring, the temperature in the stirring process is 50-60 ℃, and the time in the stirring process is 1-2 hours;
the hydrothermal synthesis process is carried out in a reaction kettle, and before the hydrothermal synthesis process, nickel salt or vanadate is added into the purifying solution containing vanadium and nickel, so that the molar ratio of vanadium to nickel in the solution is 1:1, the molar ratio of vanadium to nickel is 1:1, the pH of the purified liquid containing vanadium and nickel after adding nickel salt is 4-5.5, the reaction temperature in the hydrothermal synthesis process is 220-280 ℃, the reaction time in the hydrothermal synthesis process is 4-8 h, after the hydrothermal synthesis process, nickel vanadate is obtained by cooling, washing and drying, the washing process adopts deionized water, the drying process is carried out in a vacuum drying oven, and the drying temperature is 60-80 ℃.
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| CN117660767B (en) * | 2024-01-31 | 2024-04-26 | 中国科学院过程工程研究所 | Method for recycling sodium vanadate from nickel-aluminum slag by adopting multi-section microbubbles |
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