CN112777633B - Method for purifying vanadyl sulfate by melt crystallization - Google Patents
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Abstract
A method for purifying vanadyl sulfate by melt crystallization, belonging to the technical field of chemical industry and materials. Heating a low-purity vanadyl sulfate raw material to a molten state, performing primary crystallization and primary filtration to obtain a crude vanadyl sulfate crystallization product and a crystallization residual liquid, performing sweating purification and centrifugal filtration on the crude vanadyl sulfate crystallization product to obtain a high-purity vanadyl sulfate product and a sweating residual liquid, and finally collecting and cooling the crystallization residual liquid and the sweating residual liquid to obtain a crude vanadyl sulfate byproduct. Other flux is not used in the whole process, so that secondary pollution is avoided. The melting crystallization method comprises two stages of crystallization purification and sweating purification, high-melting-point and low-melting-point impurities in vanadyl sulfate can be removed in stages, centrifugal filtration is combined after sweating purification, a high-purity vanadyl sulfate crystallization product can be effectively separated, impurity residual liquid which is mixed, occluded and adhered to the inner part and the surface of the crystallization product is avoided, the cost is reduced, and the flow is shortened; the purposes of high efficiency, cleanness, energy conservation and purification are achieved.
Description
Technical Field
The invention relates to the technical field of chemical engineering and materials, in particular to a method for purifying vanadyl sulfate by melt crystallization.
Background
Vanadyl sulfate (VOSO)4) The vanadium oxide is an important industrial vanadium product, is an important raw material for preparing vanadium battery electrolyte and advanced glass manufacture, and is widely applied to the fields of chemical industry, materials, new energy, medicines and the like. At present, vanadyl sulfate is mostly prepared from industrial vanadic anhydride, and has low quality and high impurity content, so that the vanadyl sulfate can not meet the high standard requirements in the fields of batteries and the like. Therefore, how to prepare high-purity vanadyl sulfate with low cost and high efficiency becomes one of the key points of sustainable development in multiple fields such as new energy and the like.
At present, the preparation method of high-purity vanadyl sulfate is mainly a solution purification method. The Chinese patent application number is searched as follows: CN201510698603.8, application date: 20151023, inventive name: the application discloses a preparation method of a high-purity vanadyl sulfate solution, which comprises the following steps: a) fe2+Oxidation of (2); b) fe3+Removing; c) removing chromium ions and preparing vanadyl hydroxide; d) preparing a high-purity vanadyl sulfate solution; the crude vanadyl sulfate solution is vanadyl sulfate solution with chromium content being more than or equal to 550.3mg/L and iron content being more than or equal to 269.6 mg/L. The vanadyl sulfate solution obtained by the method has the chromium content of less than or equal to 0.002 percent and the iron content of less than or equal to 0.0027 g/L.
The Chinese patent application number is searched as follows: CN201210108878.8, application date: 20120412, title of invention: a method for preparing vanadyl sulfate electrolyte of an all-vanadium redox flow battery. The method is characterized in that vanadyl sulfate solution obtained by leaching, back-extracting and resin analysis of vanadium slag and stone coal is adjusted in pH by using alkali metal or alkaline earth metal oxide or hydroxide, and an inorganic reducing agent is added; performing multi-stage countercurrent extraction by using P204 or P507, TBP and sulfonated kerosene extraction agent, and washing a vanadium-loaded organic phase after two-phase separation; carrying out multistage countercurrent back extraction on the vanadium-loaded organic phase by using a sulfuric acid solution at 2-5 stages to prepare vanadyl sulfate back extraction liquid; adjusting the pH value of the vanadyl sulfate back-extraction liquid, adding an organic reducing agent to adjust the potential value of the solution, extracting by using the extracting agent, separating two phases, washing the vanadium-loaded organic phase by using a sulfuric acid solution, and carrying out multi-stage counter-current back extraction by using the sulfuric acid solution to obtain a vanadyl sulfate solution; distilling to the concentration required by the all-vanadium redox flow battery. The method can prepare vanadyl sulfate with certain purity, but has a long preparation process, and simultaneously needs to add additives, reducing agents and the like with certain content, so that the improvement of the product purity is limited.
In addition, the melting crystallization method can also purify the substance, and the principle is that the property of the substance to be purified, which is different from the melting point of the impurity, is utilized, and the crystallization of the substance and the separation of the impurity are promoted under the driving force of the supersaturation degree or the supercooling degree in the crystallization process, so that the effect of improving the purity is achieved. The method does not need to add any dissolving (melting) agent and is environment-friendlyHigh efficiency, low energy consumption, short process flow and high product purity, and can be widely applied to the field of chemical industry. The vanadyl sulfate has a melting point as low as 105 ℃, contains impurity elements such as Fe, Al, Mn, Cr, Si and the like, and has a melting point with VOSO4The melting points are different greatly, the high-efficiency purification can be realized by adopting a melt crystallization method, and the high-efficiency separation can be realized by adopting centrifugal filtration on the sweating liquid, so that the impurity removal is enhanced.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to solve the problems of long and complicated technological process, high cost and the like of vanadyl sulfate purification in the prior art, and provides a method for purifying vanadyl sulfate by melting crystallization. Meanwhile, collecting and cooling the crystallization residual liquid and the sweating liquid to obtain a crude vanadyl sulfate byproduct.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
heating a vanadyl sulfate raw material to a molten state, performing primary crystallization and primary filtration to obtain a crude vanadyl sulfate crystallization product and a crystallization residual liquid, performing sweating purification and centrifugal filtration on the crude vanadyl sulfate crystallization product to obtain a high-purity vanadyl sulfate product and a sweating residual liquid, and finally collecting and cooling the crystallization residual liquid and the sweating residual liquid to obtain a crude vanadyl sulfate byproduct.
Preferably, the specific steps are as follows:
the first step is as follows: melting
Heating vanadyl sulfate to temperature T1And keeping the temperature t at the temperature1Obtaining a molten liquid;
the second step is that: purification by crystallization
Cooling the molten liquid obtained in the step one at a cooling speed V1Cooling to a temperature T2And keeping the temperature t2Time; then filtering, separating to obtain knotCrystal products and crystallization residual liquid;
the third step: purification of sweating
Sweating and purifying the crystallized product obtained in the step two at the temperature of T2Rise to T3Temperature rise rate is V2And at T3Temperature t at temperature3Time; then carrying out centrifugal filtration treatment, and separating to obtain high-purity vanadyl sulfate and sweat-producing residues;
the fourth step: cooling down
And (4) collecting and cooling the crystallization residual liquid obtained in the step two and the sweating residual liquid obtained in the step three to obtain a cooling crystallization product, namely crude vanadyl sulfate.
Preferably, the temperature T in the first step1Between 105 and 120 ℃ and the heat preservation time t1The range is 30-120 min.
Preferably, the temperature T in the second step2At a cooling rate V of 50-104 DEG C10.01-5 ℃/min, and the heat preservation time t2The range is 5-120 min.
Preferably, the temperature T in the third step3At a temperature of 100-150 deg.C and a temperature raising rate V20.01-5 ℃/min, and the heat preservation time t3The range is 5-120 min.
Preferably, the purity of the vanadyl sulfate is 95-98%.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) heating a vanadyl sulfate raw material to a molten state, crystallizing and filtering to obtain a crystallized product, namely crude vanadyl sulfate and a crystallized residual liquid, sweating, purifying and centrifugally filtering the crystallized product, namely the crude vanadyl sulfate to obtain a high-purity vanadyl sulfate crystallized product and a sweating residual liquid, and finally collecting and cooling the crystallized residual liquid and the sweating residual liquid to obtain the crude vanadyl sulfate; the vanadyl sulfate with low purity is used as a raw material for carrying out melting crystallization refining, other fluxes are not used in the whole process, so that the secondary pollution caused by other fluxes is avoided, the problems of cost and recovery of the added fluxes are not considered, the preparation cost of the vanadyl sulfate with high purity is effectively reduced, and the flow is shortened;
(2) the invention relates to a method for purifying vanadyl sulfate by melt crystallization, which comprises two stages of crystallization purification and sweating purification, can remove high-melting-point and low-melting-point impurities in vanadyl sulfate in stages, and can effectively separate high-purity vanadyl sulfate crystal products by combining centrifugal filtration after sweating purification, thereby avoiding impurity residual liquid which is mixed, occluded and adhered to the inner part and the surface of the crystal products, avoiding cost increase caused by repeated melt refining, and achieving the purposes of high efficiency, cleanness and energy-saving purification;
drawings
FIG. 1 is a flow chart of a method for purifying vanadyl sulfate by melt crystallization according to the invention.
Detailed Description
The detailed description and exemplary embodiments of the invention will be better understood when read in conjunction with the appended drawings, where the elements and features of the invention are identified by reference numerals.
Example 1
Referring to fig. 1, the method for separating vanadyl sulfate by two-stage melting crystallization in this embodiment includes the following steps: heating vanadyl sulfate raw materials to a molten state, performing primary crystallization and primary filtration to obtain a crude vanadyl sulfate crystallization product and a crystallization residual liquid, then performing sweating purification and centrifugal filtration on the crude vanadyl sulfate crystallization product to obtain a high-purity vanadyl sulfate product and a sweating residual liquid, and finally collecting and cooling the crystallization residual liquid and the sweating residual liquid to obtain a crude vanadyl sulfate byproduct. The method comprises the following specific steps:
the first step is as follows: melting
Heating vanadyl sulfate to 105 ℃, and preserving heat at the temperature for 30min to obtain molten liquid;
the second step is that: purification by crystallization
Cooling the molten liquid obtained in the step one to 104 ℃ at a cooling speed of 5 ℃/min, and preserving heat for 10 min; then filtering, and separating to obtain a crystallization product and a crystallization residual liquid;
the third step: purification of sweating
Sweating and purifying the crystallization product obtained in the step two, heating the temperature from 104 ℃ to 150 ℃, heating at the speed of 0.01 ℃/min, and keeping the temperature at 150 ℃ for 5 min; then carrying out centrifugal filtration treatment, and separating to obtain high-purity vanadyl sulfate and sweat-producing residues;
the fourth step: cooling down
And (4) collecting and cooling the crystallization residual liquid obtained in the step two and the sweating residual liquid obtained in the step three to obtain a cooling crystallization product, namely crude vanadyl sulfate. Crystallizing and filtering to obtain a crystallized product, namely crude vanadyl sulfate and a crystallized residual liquid, then sweating, purifying and centrifugally filtering the crystallized product, namely the crude vanadyl sulfate to obtain a high-purity vanadyl sulfate crystallized product and a sweating residual liquid, and finally collecting and cooling the crystallized residual liquid and the sweating residual liquid to obtain the crude vanadyl sulfate; the vanadyl sulfate with low purity is used as a raw material for carrying out melting crystallization refining, other fluxes are not used in the whole process, so that the secondary pollution caused by other fluxes is avoided, the problems of cost and recovery of the added fluxes are not considered, the preparation cost of the vanadyl sulfate with high purity is effectively reduced, and the flow is shortened; meanwhile, the melting crystallization method provided by the invention comprises two stages of crystallization purification and sweating purification, and can remove high-melting-point and low-melting-point impurities in vanadyl sulfate in stages, and further, the high-purity vanadyl sulfate crystal product can be effectively separated by combining centrifugal filtration after sweating purification, so that impurity residual liquid which is mixed, occluded and adhered to the inner part and the surface of the crystal product is avoided, the cost increase caused by repeated melting refining is also avoided, and the purposes of high efficiency, cleanness and energy-saving purification are achieved; the purity of the high-purity vanadyl sulfate extracted by the embodiment reaches 99.999%, and the yield of the high-purity vanadium pentoxide is 95%.
Example 2
Referring to fig. 1, the method for separating vanadyl sulfate by two-stage melting crystallization in this embodiment includes the following steps: heating vanadyl sulfate raw materials to a molten state, performing primary crystallization and primary filtration to obtain a crude vanadyl sulfate crystallization product and a crystallization residual liquid, then performing sweating purification and centrifugal filtration on the crude vanadyl sulfate crystallization product to obtain a high-purity vanadyl sulfate product and a sweating residual liquid, and finally collecting and cooling the crystallization residual liquid and the sweating residual liquid to obtain a crude vanadyl sulfate byproduct. The method comprises the following specific steps:
the first step is as follows: melting
Heating vanadyl sulfate to 110 ℃, and preserving heat at the temperature for 60min to obtain molten liquid;
the second step is that: purification by crystallization
Cooling the molten liquid obtained in the step one to 100 ℃ at a cooling speed of 0.1 ℃/min, and keeping the temperature for 100 min; then filtering, and separating to obtain a crystallization product and a crystallization residual liquid;
the third step: purification of sweating
Sweating and purifying the crystallization product obtained in the step two, heating the temperature from 100 ℃ to 120 ℃, heating the temperature at the speed of 0.1 ℃/min, and keeping the temperature at 150 ℃ for 30 min; then carrying out centrifugal filtration treatment, and separating to obtain high-purity vanadyl sulfate and sweat-producing residues;
the fourth step: cooling down
And (4) collecting and cooling the crystallization residual liquid obtained in the step two and the sweating residual liquid obtained in the step three to obtain a cooling crystallization product, namely crude vanadyl sulfate. Crystallizing and filtering to obtain a crystallized product, namely crude vanadyl sulfate and a crystallized residual liquid, then sweating, purifying and centrifugally filtering the crystallized product, namely the crude vanadyl sulfate to obtain a high-purity vanadyl sulfate crystallized product and a sweating residual liquid, and finally collecting and cooling the crystallized residual liquid and the sweating residual liquid to obtain the crude vanadyl sulfate; the vanadyl sulfate with low purity is used as a raw material for carrying out melting crystallization refining, other fluxes are not used in the whole process, so that the secondary pollution caused by other fluxes is avoided, the problems of cost and recovery of the added fluxes are not considered, the preparation cost of the vanadyl sulfate with high purity is effectively reduced, and the flow is shortened; meanwhile, the melting crystallization method provided by the invention comprises two stages of crystallization purification and sweating purification, and can remove high-melting-point and low-melting-point impurities in vanadyl sulfate in stages, and further, the high-purity vanadyl sulfate crystal product can be effectively separated by combining centrifugal filtration after sweating purification, so that impurity residual liquid which is mixed, occluded and adhered to the inner part and the surface of the crystal product is avoided, the cost increase caused by repeated melting refining is also avoided, and the purposes of high efficiency, cleanness and energy-saving purification are achieved; the purity of the high-purity vanadyl sulfate extracted by the embodiment reaches 99.999%, and the yield of the high-purity vanadium pentoxide is 98%.
Example 3
Referring to fig. 1, the method for separating vanadyl sulfate by two-stage melting crystallization in this embodiment includes the following steps: heating vanadyl sulfate raw materials to a molten state, performing primary crystallization and primary filtration to obtain a crude vanadyl sulfate crystallization product and a crystallization residual liquid, then performing sweating purification and centrifugal filtration on the crude vanadyl sulfate crystallization product to obtain a high-purity vanadyl sulfate product and a sweating residual liquid, and finally collecting and cooling the crystallization residual liquid and the sweating residual liquid to obtain a crude vanadyl sulfate byproduct. The method comprises the following specific steps:
the first step is as follows: melting
Heating vanadyl sulfate to 117 ℃, and preserving heat at the temperature for 105min to obtain molten liquid;
the second step is that: purification by crystallization
Cooling the molten liquid obtained in the step one to 85 ℃ at a cooling speed of 4.5 ℃/min, and preserving the temperature for 45 min; then filtering, and separating to obtain a crystallization product and a crystallization residual liquid;
the third step: purification of sweating
Sweating and purifying the crystallization product obtained in the step two, heating the temperature from 85 ℃ to 135 ℃, heating at the speed of 4.5 ℃/min, and keeping the temperature at 135 ℃ for 100 min; then carrying out centrifugal filtration treatment, and separating to obtain high-purity vanadyl sulfate and sweat-producing residues;
the fourth step: cooling down
And (4) collecting and cooling the crystallization residual liquid obtained in the step two and the sweating residual liquid obtained in the step three to obtain a cooling crystallization product, namely crude vanadyl sulfate. Crystallizing and filtering to obtain a crystallized product, namely crude vanadyl sulfate and a crystallized residual liquid, then sweating, purifying and centrifugally filtering the crystallized product, namely the crude vanadyl sulfate to obtain a high-purity vanadyl sulfate crystallized product and a sweating residual liquid, and finally collecting and cooling the crystallized residual liquid and the sweating residual liquid to obtain the crude vanadyl sulfate; the vanadyl sulfate with low purity is used as a raw material for carrying out melting crystallization refining, other fluxes are not used in the whole process, so that the secondary pollution caused by other fluxes is avoided, the problems of cost and recovery of the added fluxes are not considered, the preparation cost of the vanadyl sulfate with high purity is effectively reduced, and the flow is shortened; meanwhile, the melting crystallization method provided by the invention comprises two stages of crystallization purification and sweating purification, and can remove high-melting-point and low-melting-point impurities in vanadyl sulfate in stages, and further, the high-purity vanadyl sulfate crystal product can be effectively separated by combining centrifugal filtration after sweating purification, so that impurity residual liquid which is mixed, occluded and adhered to the inner part and the surface of the crystal product is avoided, the cost increase caused by repeated melting refining is also avoided, and the purposes of high efficiency, cleanness and energy-saving purification are achieved; the purity of the high-purity vanadyl sulfate extracted by the embodiment reaches 99.999%, and the yield of the high-purity vanadium pentoxide is 96.5%.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
Claims (2)
1. A method for purifying vanadyl sulfate by melt crystallization is characterized in that a vanadyl sulfate raw material is heated to a molten state, primary crystallization and primary filtration are carried out to obtain a crude vanadyl sulfate crystallization product and a crystallization residual liquid, then the crude vanadyl sulfate crystallization product is subjected to sweating purification and centrifugal filtration to obtain a high-purity vanadyl sulfate product and a sweating residual liquid, and finally the crystallization residual liquid and the sweating residual liquid are collected and cooled to obtain a crude vanadyl sulfate byproduct;
the method comprises the following specific steps:
the first step is as follows: melting
Heating vanadyl sulfate to temperature T1And keeping the temperature t at the temperature1Obtaining a molten liquid;
the second step is that: purification by crystallization
Cooling the molten liquid obtained in the step one at a cooling speed V1Cooling to a temperature T2And keeping the temperature t2Time; then filtering, and separating to obtain a crystallization product and a crystallization residual liquid;
the third step: purification of sweating
Sweating and purifying the crystallized product obtained in the step two at the temperature of T2Rise to T3Temperature rise rate is V2And at T3Temperature t at temperature3Time; then carrying out centrifugal filtration treatment, and separating to obtain high-purity vanadyl sulfate and sweat-producing residues;
the fourth step: cooling down
Collecting and cooling the crystallization residual liquid obtained in the step two and the sweating residual liquid obtained in the step three to obtain a cooling crystallization product, namely crude vanadyl sulfate;
temperature T in the first step1Between 105 and 120 ℃ and the heat preservation time t1The range is 30-120 min;
temperature T in the second step2At a cooling rate V of 50-104 DEG C10.01-5 ℃/min, and the heat preservation time t2The range is 5-120 min;
temperature T in the third step3At a temperature of 100-150 deg.C and a temperature raising rate V20.01-5 ℃/min, and the heat preservation time t3The range is 5-120 min.
2. The method for purifying vanadyl sulfate by melt crystallization as claimed in claim 1, wherein: the purity of the vanadyl sulfate raw material is 95-98%.
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