CN112266017B - Method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste - Google Patents
Method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste Download PDFInfo
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- CN112266017B CN112266017B CN202010954177.0A CN202010954177A CN112266017B CN 112266017 B CN112266017 B CN 112266017B CN 202010954177 A CN202010954177 A CN 202010954177A CN 112266017 B CN112266017 B CN 112266017B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
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Abstract
The invention provides a method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste, which comprises the following steps: adding solid waste containing vanadium and phosphorus into sodium hydroxide solution, uniformly mixing, heating, stirring and leaching under an oxidizing atmosphere, adding a precipitator step by step, carrying out solid-liquid separation, and crystallizing to obtain sodium vanadate. The method for leaching the vanadium-phosphorus-containing solid waste under alkaline conditions by oxidizing is favorable for fully oxidizing and converting vanadium into sodium vanadate, improves the leaching rate of vanadium, and simultaneously improves the separation effect of vanadium and phosphorus by adopting a fractional precipitation impurity removal mode, thereby ensuring the quality of the prepared sodium vanadate product, the recovery rate of vanadium is more than 86 percent, the purity of the sodium vanadate product is more than 98 percent, and the method does not need a high-temperature roasting mode, has simple process and low energy consumption, does not generate dust and tail gas, is a green method for recycling the vanadium-phosphorus-containing solid waste with low cost, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of sodium vanadate preparation, in particular to a method for preparing sodium vanadate by utilizing solid wastes containing vanadium and phosphorus.
Background
The reserves of the low-grade vanadium titano-magnetite in China are large, and the low-grade vanadium titano-magnetite is generated in steelmaking, petroleum refining, alumina production and power stationsVanadium-containing titano-magnetite is used in many industrial processes such as electricity, and therefore, a large amount of vanadium-containing solid waste is produced each year. Wherein the VPO catalyst (also known as vanadyl pyrophosphate (VO) 2 P 2 O 7 ) Is a tetravalent vanadium phosphate, and is mainly used as a catalyst for preparing maleic anhydride by selective oxidation of C4 hydrocarbon in industry. Currently, there are many methods for controlling the flow of liquid. The annual failure of the VPO catalyst can reach thousands of tons, if the VPO catalyst is not treated, the VPO catalyst not only can cause great waste of vanadium resources, but also has certain toxicity, and can bring great pollution to the environment and influence the health of human beings. Therefore, finding a way to recycle vanadium in the VPO catalyst is of great importance.
At present, the main process for recovering vanadium in the VPO catalyst in China is a sodium roasting method, and the method uses sodium salts such as carbonate, sodium chloride or sodium sulfate, and the like, and the sodium salts are calcined together with the VPO catalyst in an air atmosphere to oxidize vanadium into pentavalent vanadium, so that a mixture of sodium vanadate and sodium phosphate is formed, and the mixture is leached by water, and vanadium and phosphorus are separated and extracted to prepare a vanadium product. However, the VPO solid catalyst and sodium salt have poor contact, so that the reactivity of the VPO solid catalyst and the sodium salt is poor, vanadium cannot be fully converted into sodium vanadate, and meanwhile, the vanadium-phosphorus separation effect is poor, so that the defects of poor vanadium extraction rate, poor purity of vanadium products and the like are caused. In addition, the process has the problems of high roasting energy consumption, large amount of generated tail gas and dust, serious pollution and the like. Therefore, it is important to find a green recycling method of the VPO catalyst which can reduce the energy consumption of treatment and has high vanadium utilization rate and is suitable for the recycling of industrial production.
Disclosure of Invention
Aiming at the problems of high energy consumption in the treatment of the existing vanadium-phosphorus-containing solid waste, high vanadium loss rate and low purity of the prepared vanadium product, the invention provides a method for preparing sodium vanadate by using the vanadium-phosphorus-containing solid waste.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste comprises the following steps:
adding solid waste containing vanadium and phosphorus into sodium hydroxide solution, uniformly mixing, heating, stirring and leaching under an oxidizing atmosphere, adding a precipitator step by step, carrying out solid-liquid separation, and crystallizing to obtain sodium vanadate.
Preferably, the method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste specifically comprises the following steps:
crushing solid wastes containing vanadium and phosphorus, adding the crushed solid wastes into a sodium hydroxide solution, and uniformly mixing to obtain mixed slurry; introducing oxidizing gas into the mixed slurry, heating, stirring and leaching, and carrying out solid-liquid separation to obtain vanadium-containing leaching solution;
step two, adding a first precipitator into the vanadium-containing leaching solution, heating for reaction, and performing solid-liquid separation to obtain primary purified liquid; adding a second precipitant into the primary purifying liquid, heating for reaction, and carrying out solid-liquid separation to obtain vanadium-containing purifying liquid; wherein the first precipitant is soluble magnesium salt and/or soluble aluminum salt, and the second precipitant is an alkaline calcium compound;
and thirdly, cooling and crystallizing the vanadium-containing purifying liquid, and carrying out solid-liquid separation to obtain sodium vanadate.
Compared with the prior art, the method has the advantages that the vanadium in the vanadium-phosphorus-containing solid waste is leached out while being oxidized under the alkaline condition by adopting the way of oxidizing the vanadium-phosphorus-containing solid waste in the sodium hydroxide solution, so that the reactivity of the vanadium is improved, the full oxidation and conversion of the vanadium into sodium vanadate are facilitated, the leaching rate of the vanadium is improved, and meanwhile, the separation effect of the vanadium and phosphorus is improved by adopting the way of step-by-step precipitation and impurity removal, so that the quality of the prepared sodium vanadate product is ensured. The method for preparing the sodium vanadate by utilizing the vanadium-phosphorus-containing solid waste can ensure that the recovery rate of vanadium is more than 86%, the purity of the prepared sodium vanadate product is more than 98%, the method does not need to adopt a high-temperature roasting mode, has the advantages of simple process and low energy consumption, does not generate dust and tail gas, and is a low-cost green method for recycling the vanadium-phosphorus-containing solid waste, thereby being suitable for large-scale industrial production.
Preferably, the vanadium-phosphorus-containing solid waste is a VPO waste catalyst.
Preferably, in the first step, the vanadium-phosphorus-containing solid waste is crushed to 50-200 meshes.
The preferable crushing fineness is beneficial to the full oxidation leaching of vanadium in the vanadium-phosphorus-containing solid waste.
Preferably, in the first step, the oxidizing gas is oxygen or compressed air.
Preferably, in the first step, the flow rate of the oxidizing gas is 0.1 to 0.5m 3 /h。
The preferred flow rate is advantageous for fully oxidizing vanadium in the vanadium-phosphorus-containing solid waste.
Preferably, in the first step, the mass concentration of the sodium hydroxide solution is 5-15 wt%, and the mass volume ratio of the vanadium-phosphorus-containing solid waste to the sodium hydroxide solution is 1:3-6, wherein the mass unit is gram and the volume unit is milliliter.
The concentration and the addition amount of the sodium hydroxide solution are favorable for improving the reactivity of vanadium, fully converting the vanadium into sodium vanadate and improving the leaching rate of the vanadium.
Preferably, in the first step, the temperature of heating and stirring leaching is 85-120 ℃, and the leaching time is 1-4h.
The preferential heating temperature is favorable for fully oxidizing vanadium in the vanadium-phosphorus-containing solid waste, and is favorable for improving the leaching rate and shortening the leaching time.
Preferably, in the second step, the first precipitant is at least one of magnesium sulfate, magnesium chloride, aluminum sulfate or aluminum chloride.
Preferably, in the second step, the second precipitant is one or two of calcium oxide and calcium hydroxide.
Preferably, in the second step, the adding amount of the first precipitant is 5-8 g/L, and the adding amount of the second precipitant is 0.5-2 g/L.
The first precipitant and the second precipitant are preferably added in a specific sequence, so that the vanadium-phosphorus separation effect can be improved, and the vanadium loss can be reduced.
Preferably, in the second step, the temperature of heating after adding the first precipitator is 80-95 ℃ and the reaction time is 0.5-1 h; the temperature of heating after adding the second precipitant is 80-95 ℃ and the reaction time is 0.5-1 h.
The preferred reaction temperature and time are favorable for fully removing impurities and improving the purity of the sodium vanadate product.
In the third step, the temperature of the cooling crystallization is 0-40 ℃ and the time is 1-4h.
The purity of the sodium vanadate product can be improved by the preferable cooling crystallization temperature and time.
Preferably, the crystallization mother liquor obtained by solid-liquid separation after crystallization in the third step is used for preparing sodium hydroxide solution in the first step.
The generated liquid phase is returned to the leaching process for recycling, no wastewater is discharged, the wastewater treatment components are reduced, and the economic and environmental benefits of the process are improved.
The method for preparing sodium vanadate by utilizing the vanadium-phosphorus-containing solid waste provided by the invention does not need high-temperature roasting, has the advantages of low reaction temperature, simple process, easiness in operation, high vanadium extraction rate, high impurity removal efficiency and good impurity removal effect, can effectively reduce vanadium loss, improve the quality of sodium vanadate products, can save energy consumption, does not generate dust and tail gas polluting the environment, has obvious economic benefit and environmental benefit, and has wide application prospect.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The vanadium content of the spent VPO catalyst in the examples below was 27wt% and the phosphorus content was 19wt%.
Example 1
A method for preparing sodium vanadate by using a VPO waste catalyst comprises the following steps:
crushing 100g of VPO waste catalyst to 50-200 meshes, adding 400mL of 10wt% sodium hydroxide solution, uniformly mixing, adding the mixed material into a reaction kettle, and adding the catalyst into the reaction kettle at a concentration of 0.1m 3 Introducing compressed air into the flow of/h, heating to 90 ℃, stirring and leaching for 3h, and filtering to obtain vanadium-containing leaching solution; vanadium-containing leachingThe vanadium in the liquid is 24.6g/L, the phosphorus is 18.2g/L, and the leaching rate of vanadium is 95.9%;
adding 7.5g/L aluminum sulfate into the vanadium-containing leaching solution, heating to 95 ℃ to react for 0.5h, filtering, adding 0.5g/L calcium oxide into the filtrate, heating to 95 ℃ to react for 0.5h, and filtering to obtain vanadium-containing purifying liquid; the phosphorus content in the vanadium-containing purifying liquid is 0.078g/L, the vanadium content is 23.8g/L, and the vanadium recovery rate is 88.1%;
and thirdly, cooling the vanadium-containing purifying liquid to 0 ℃ for crystallization for 1h, and filtering to obtain sodium vanadate. The HPLC purity of sodium vanadate was 98.3%.
Example 2
A method for preparing sodium vanadate by using a VPO waste catalyst comprises the following steps:
crushing 100g of VPO waste catalyst to 50-200 meshes, adding 300mL of sodium hydroxide solution with the mass concentration of 15wt%, uniformly mixing, adding the mixed material into a reaction kettle, and adding the mixture into the reaction kettle at the concentration of 0.5m 3 Introducing oxygen into the flow of/h, heating to 85 ℃, stirring and leaching for 4h, and filtering to obtain vanadium-containing leaching solution; the vanadium in the leaching solution containing vanadium is 26.8g/L, the phosphorus is 17.6g/L, and the leaching rate of vanadium is 96.2%;
adding 8g/L of a mixture of magnesium chloride and aluminum sulfate (the mass ratio is 1:1) into the vanadium-containing leaching solution, heating to 90 ℃ for reaction for 1h, filtering, adding 1.5g/L of calcium hydroxide into the filtrate, heating to 80 ℃ for reaction for 1h, and filtering to obtain vanadium-containing purified solution; the phosphorus content in the vanadium-containing purifying liquid is 0.064g/L, the vanadium content is 26.1g/L, and the vanadium recovery rate is 86.9%;
and thirdly, cooling the vanadium-containing purifying liquid to 10 ℃ for crystallization for 2 hours, and filtering to obtain sodium vanadate. The HPLC purity of sodium vanadate was 98.8%.
Example 3
A method for preparing sodium vanadate by using a VPO waste catalyst comprises the following steps:
crushing 100g of VPO waste catalyst to 50-200 meshes, adding 600mL of sodium hydroxide solution with the mass concentration of 5wt%, uniformly mixing, adding the mixed material into a reaction kettle, and adding the mixture into the reaction kettle at the concentration of 0.3m 3 Introducing oxygen into the flow of/h, heating to 120 ℃, stirring and leaching for 1h, and filtering to obtain vanadium-containing leaching liquid; in leaching solution containing vanadiumThe vanadium content is 25.7g/L, the phosphorus content is 18.5g/L, and the vanadium leaching rate is 95.9%;
adding 5g/L magnesium sulfate into the vanadium-containing leaching solution, heating to 80 ℃ for reaction for 1h, filtering, adding 2g/L calcium oxide into the filtrate, heating to 90 ℃ for reaction for 1h, and filtering to obtain vanadium-containing purified liquid; the phosphorus content in the vanadium-containing purifying liquid is 0.067g/L, the vanadium content is 24.5g/L, and the vanadium recovery rate is 87.5%;
and thirdly, cooling the vanadium-containing purifying liquid to 40 ℃ for crystallization for 4 hours, and filtering to obtain sodium vanadate. The HPLC purity of sodium vanadate was 98.5%.
In the above examples 1 to 3, the mother liquor obtained by solid-liquid separation after crystallization in the third step may be used for preparing sodium hydroxide solution in the first step.
In summary, the method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste provided by the invention has the advantages that the impurities in the leaching solution are effectively removed on the premise of ensuring that vanadium in the vanadium-phosphorus-containing solid waste is fully leached by controlling various process parameters, the quality of subsequent sodium vanadate products is ensured, high-temperature roasting is not needed, the process operation is simple and convenient, the cost is reduced, and the method has a wide application prospect.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (7)
1. The method for preparing the sodium vanadate from the vanadium-phosphorus-containing solid waste is characterized by comprising the following steps of:
crushing solid wastes containing vanadium and phosphorus, adding the crushed solid wastes into a sodium hydroxide solution, and uniformly mixing to obtain mixed slurry; introducing oxidizing gas into the mixed slurry, heating, stirring and leaching, and carrying out solid-liquid separation to obtain vanadium-containing leaching solution;
step two, adding a first precipitator into the vanadium-containing leaching solution, heating for reaction, and performing solid-liquid separation to obtain primary purified liquid; adding a second precipitant into the primary purifying liquid, heating for reaction, and carrying out solid-liquid separation to obtain vanadium-containing purifying liquid; wherein the first precipitant is soluble magnesium salt and/or soluble aluminum salt, and the second precipitant is an alkaline calcium compound;
step three, cooling and crystallizing the vanadium-containing purifying liquid, and carrying out solid-liquid separation to obtain sodium vanadate;
wherein the vanadium-phosphorus-containing solid waste is a VPO waste catalyst, the adding amount of the first precipitant is 5-8 g/L, and the adding amount of the second precipitant is 0.5-2 g/L.
2. The method for preparing sodium vanadate from solid waste containing vanadium and phosphorus according to claim 1, wherein in the first step, the solid waste containing vanadium and phosphorus is crushed to 50-200 meshes; and/or
In the first step, the oxidizing gas is oxygen or compressed air.
3. The method for preparing sodium vanadate from vanadium-phosphorus-containing solid waste according to claim 1, wherein in the first step, the mass concentration of the sodium hydroxide solution is 5-15 wt%, and the mass-volume ratio of the vanadium-phosphorus-containing solid waste to the sodium hydroxide solution is 1:3-6, wherein the mass unit is gram and the volume unit is milliliter; and/or
In the first step, the flow rate of the oxidizing gas is 0.1-0.5 m 3 /h。
4. The method for preparing sodium vanadate from solid waste containing vanadium and phosphorus according to claim 1, wherein in the first step, the temperature of heating and stirring leaching is 85-120 ℃, and the leaching time is 1-4h.
5. The method for preparing sodium vanadate from solid waste containing vanadium and phosphorus according to claim 1, wherein in the second step, the first precipitant is at least one of magnesium sulfate, magnesium chloride, aluminum sulfate or aluminum chloride; and/or
In the second step, the second precipitant is one or two of calcium oxide and calcium hydroxide.
6. The method for preparing sodium vanadate from solid waste containing vanadium and phosphorus according to claim 5, wherein in the second step, the temperature of heating after adding the first precipitant is 80-95 ℃, and the reaction time is 0.5-1 h; the temperature of heating after adding the second precipitant is 80-95 ℃ and the reaction time is 0.5-1 h.
7. The method for preparing sodium vanadate from solid waste containing vanadium and phosphorus according to claim 1, wherein in the third step, the temperature of the cooling crystallization is 0-40 ℃ and the time is 1-4h.
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