CN115367798B - Method for preparing environment-friendly pigment by utilizing industrial waste vanadium material - Google Patents
Method for preparing environment-friendly pigment by utilizing industrial waste vanadium material Download PDFInfo
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- C01G31/00—Compounds of vanadium
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Abstract
The invention provides a method for preparing environment-friendly pigment by utilizing industrial waste vanadium material, which comprises the following steps: the method comprises the steps of (1) calibrating element types and content of waste vanadium materials, selecting waste vanadium materials with vanadium valence states of pentavalent or tetravalent and vanadium content of 3-20%, adding calcium salt or/and zinc salt, granulating, roasting at 300-550 ℃ for 0.5-5h to obtain vanadium microspheres with a large number of pore structures, adding deionized water into the vanadium microspheres, heating, and adding a reducing agent to leach vanadium ions from the vanadium microspheres; calibrating the concentration and valence state of the leached vanadium ions; dissolving bismuth raw material in nitric acid solution, slowly dripping the bismuth raw material into the leaching solution in an atomization mode to form brown yellow bismuth vanadate precipitate, screening, filtering, rinsing, removing impurity ions, and drying to obtain the bismuth vanadate pigment. The invention extracts and recycles industrial solid waste (crude) vanadium, ensures that the liquid phase of the vanadium solution directly participates in chemical precipitation reaction with bismuth ions to prepare the bismuth vanadate yellow environment-friendly pigment, shortens the preparation process of the bismuth vanadate pigment, and greatly reduces the cost of the bismuth vanadate pigment.
Description
Technical Field
The invention belongs to the technical field of waste vanadium material recovery, and particularly relates to a method for preparing pigment by utilizing recovered industrial waste vanadium material.
Background
The ecological environment-friendly inorganic pigment does not contain toxic and harmful heavy metals, can completely replace traditional lead, cadmium and chromium series products, has more excellent physical and chemical properties such as acid and alkali resistance, corrosion resistance, weather resistance and aging resistance, can be widely applied to the fields of paint, coating, printing ink, plastic cement, ceramics and the like, can accelerate the innovation of downstream products and the lead-free process of industries, and has important significance for environmental protection and personal safety.
The nano bismuth vanadate as a novel yellow inorganic pigment does not contain toxic or harmful chemical elements, can completely replace the traditional lead-cadmium yellow pigment in the market, and has wide market application prospect. However, the V raw material is subject to the adverse factors of high exploitation cost and serious resource waste of vanadium ore resources in China 2 O 5 The price fluctuation factor, the cost for producing bismuth vanadate by taking high-purity vanadium pentoxide, ammonium metavanadate, sodium vanadate and the like as vanadium sources is too high, and the market price of bismuth vanadate is always high and not low to a certain extentThe market popularization and the application of the pigment are restricted, and the lead-free and nontoxic substitution process of the harmful pigment is slowed down. In addition, in the process for extracting vanadium ore in China, the traditional incineration and landfill solid waste treatment mode is adopted, so that the defects of serious secondary pollution, increased carbon emission and the like exist, and great pollution and potential safety hazard are caused to the environment and personal safety.
Patent document CN102491419B discloses a method for comprehensively recycling waste vanadium catalyst, which takes the waste vanadium catalyst as a raw material, firstly transfers vanadium and potassium into liquid phase to realize SiO through reduction acid leaching 2 Separation of precipitate, siO 2 Preparation of liquid sodium silicate by alkali dissolution for recovery of SiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Adding alkali liquor into vanadium and potassium in liquid phase to separate vanadium from potassium, and then respectively preparing V 2 O 5 And K 2 SO 4 . The patent needs to heat 3-40% of sulfuric acid and a reducing agent as leaching liquid, vanadium ions are leached, a large amount of potassium hydroxide and ammonium chloride are heated in the later stage to carry out wet precipitation of ammonium metavanadate, and V is obtained through high-temperature calcination at a temperature of more than 500 DEG C 2 O 5 Although the waste vanadium catalyst can be recovered to a certain extent, a large amount of strong acid, such as sulfuric acid, potassium hydroxide and the like, and strong alkali are used in the process flow, so that the problem of secondary solid waste pollution is caused; meanwhile, vanadium pentoxide is used as a raw material, and alkali is used for dissolution in the later period, so that a vanadium solution is obtained for preparing the bismuth vanadate pigment by a wet method, and the defects of high cost and long process flow exist.
Patent document CN107177737B also discloses a comprehensive recycling method of the waste vanadium catalyst, which sequentially carries out water leaching, reduction acid leaching on the waste vanadium catalyst; the silicon is separated and recovered in the form of leaching slag by alkaline leaching to form sodium silicate; saponification P for leachate 2 O 4 Extracting and separating vanadium and potassium by a single-stage extraction and tail liquid concentrated and independent reextraction vanadium extraction process, evaporating and concentrating a raffinate phase to prepare potassium sulfate and separate potassium, and preparing vanadium pentoxide and recovering vanadium by the steps of back extraction, vanadium precipitation, calcination and the like of an extract phase. The patent uses extractant P 2 O 4 The directional selective extraction is carried out, and the separation of low-concentration vanadium ions is realized by back extraction in the later stage, and the process flow has low efficiencyThe ion exchange resin has the defects of high price and extremely high treatment cost, is difficult to realize large-scale production, and has extremely high recovery difficulty for a large amount of accumulated industrial waste vanadium materials.
Therefore, it is necessary to solve the above-described drawbacks.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for preparing environment-friendly pigment by utilizing industrial waste vanadium.
The invention provides a method for preparing environment-friendly pigment by utilizing industrial waste vanadium materials, which comprises the following steps:
s1, calibrating element types and content of the waste vanadium material, and selecting the waste vanadium material with the vanadium valence state of pentavalent or tetravalent and the vanadium content of 3-20%;
s2, adding a certain amount of calcium salt or/and zinc salt into the selected waste vanadium material, granulating, and roasting at 300-550 ℃ for 0.5-5h to obtain vanadium microspheres with a large number of pore structures;
s3, adding deionized water into the vanadium microspheres, heating, adding a reducing agent solution, and stirring to leach vanadium ions from the vanadium microspheres;
s4, calibrating the vanadium ion concentration and valence state of the leaching solution obtained in the step S3;
s5, weighing a bismuth raw material, dissolving the bismuth raw material in a nitric acid solution with a certain concentration, and slowly dripping the bismuth raw material into the leaching solution in an atomization mode to form brown yellow bismuth vanadate precipitate;
and S6, screening, filtering and rinsing the bismuth vanadate precipitate to remove impurity ions, and drying to obtain the bismuth vanadate pigment.
According to the invention, firstly, the element types and the content of the waste vanadium materials are calibrated, and the waste vanadium materials are added with additives to be pelletized and then baked, so that a large number of microspheres of vanadium with micro-structures in the aperture are obtained, the later vanadium leaching rate is greatly improved, and the baking temperature is reduced; by adding the reducing agent, vanadium elements with different oxidation forms and different valence states can be subjected to oxidation-reduction reaction to obtain low-valence vanadium ions, and the low-valence vanadium ions are quickly combined with bismuth ions in the bismuth raw material in a dropwise manner in an atomization manner to form precipitation, so that the supersaturation degree of the vanadium ions is reduced, the reaction is carried out towards the direction of reducing the supersaturation degree, the leaching rate of vanadium can be accelerated, and finally the bismuth vanadate pigment precipitation is obtained. And acid solution is also introduced in the reduction process, so that byproducts are completely converted into pure bismuth vanadate environment-friendly pigment, and the vanadium conversion rate in the waste vanadium material is further improved.
According to the invention, waste vanadium is used as a raw material, industrial solid waste (crude) vanadium materials are efficiently extracted and recycled through a technological process, the leaching rate of vanadium ions is improved, a vanadium solution liquid phase is directly reacted with bismuth ions in a chemical precipitation reaction, so that the bismuth vanadate yellow environment-friendly pigment with high added value is obtained, the waste vanadium material recovery and bismuth vanadate pigment preparation technological process is greatly shortened, the serious pollution problem caused by accumulation of a large amount of industrial solid waste is solved, the secondary solid waste pollution problem caused by adoption of a large amount of strong acid and strong alkali such as sulfuric acid, potassium hydroxide in the waste vanadium recovery technological process in the prior art is avoided, and the cost of bismuth vanadate pigment is obviously reduced through solid waste recycling and technological process innovation, so that a feasible path is provided for popularization and application of the bismuth vanadate pigment completely replacing the traditional toxic pigment.
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 invention provides a method for preparing pigment by utilizing industrial waste vanadium material, which comprises the following steps:
s1, calibrating element types and content of the waste vanadium material, and selecting the waste vanadium material with the vanadium valence state of pentavalent or tetravalent and the vanadium content of 3-20%.
The method comprises the steps of firstly, calibrating the element types and the content of the recovered industrial waste vanadium materials, calculating the content of vanadium and the amount of low-valence vanadium in the recovered waste vanadium materials by means of component analysis, spectrum analysis and the like, and selecting the waste vanadium materials or the crude vanadium materials of vanadium pentoxide, vanadium tetraoxide, vanadyl sulfate and the like with the vanadium valence of pentavalent or tetravalent and the vanadium content of 3-20% as raw materials for preparing environment-friendly pigment.
S2, adding a certain amount of calcium salt or/and zinc salt into the selected waste vanadium material, granulating, and roasting at 300-550 ℃ for 0.5-5h to obtain vanadium microspheres with a large number of pore structures.
In the step, added calcium salt or/and zinc salt is used as an additive, wherein the calcium salt can be calcium carbonate or calcium oxide, the zinc salt can be zinc carbonate or zinc oxide, and the like, so that vanadium ions in the waste vanadium material and calcium ions in the calcium salt or/and zinc ions in the zinc salt react to form calcium vanadate or zinc vanadate through high-temperature roasting, and the added calcium salt accounts for 5-20% of the waste vanadium material.
Mixing the waste vanadium material with calcium salt or zinc salt, granulating by a granulator to prepare uniform vanadium microspheres with the diameter of 0.1-2cm, and then putting the uniform vanadium microspheres into a high-temperature furnace for roasting at the temperature of 300-550 ℃ for 0.5-5h, preferably 1-2h. Through high-temperature roasting, on one hand, vanadium ions in the waste vanadium materials react with calcium ions and zinc ions in calcium salts or zinc salts to form calcium vanadate and zinc vanadate, the two substances are easy to dissolve in acid, the later stage vanadium leaching efficiency can be improved, on the other hand, after roasting, vanadium microspheres can form a microporous structure, the specific surface area of the vanadium microspheres can be increased, meanwhile, the pores in the vanadium microspheres further increase activation points, so that the rate of the later stage vanadium ion leaching is greatly improved, and the process flow is shortened.
The additive of the step can be added with a certain amount of alkaline earth fluoride besides the added calcium carbonate or calcium oxide, zinc carbonate or zinc oxide, wherein the addition amount of the alkaline earth fluoride is 3-5% of the waste vanadium material, and the alkaline earth fluoride can be calcium fluoride or zinc fluoride. After fluoride is added, fluoride ions can play a role of mineralizer, so that even though the waste vanadium material with a very stable ore structure can form a replacement solid solution with vanadium salt through fluoride, the roasting temperature is lower than 550 ℃, the roasting temperature is greatly reduced, the recovery cost of the waste vanadium material is reduced, the process flow is shortened, and more vanadium ions can be leached.
The roasting temperature in the step is lower than 550 ℃, and vanadium ions can form relatively stable vanadium pentoxide at the temperature higher than the roasting temperature, so that the leaching efficiency of the vanadium ions in the later stage is low, and the reaction is incomplete at the temperature lower than 300 ℃.
S3, adding deionized water into the vanadium microspheres, heating, adding a reducing agent solution, and stirring to leach vanadium ions from the vanadium microspheres.
In the step, deionized water is mixed with vanadium microspheres according to the weight of the vanadium microspheres according to the adding amount of 10ml/g, the heating temperature is 60-90 ℃, the added reducing agent is at least one of oxalic acid and ammonium sulfite, the concentration is 5-20%, preferably 10%, the heating treatment time is 2-5h, and the adding amount of the reducing agent solution is 1-2% of the deionized water.
By adding the reducing agent, vanadium elements with different oxidation forms and different valence states in the vanadium microspheres can be converted into vanadium ions through oxidation-reduction reaction, and high valence vanadium ions are converted into low valence vanadium ions, so that the vanadium ions are separated from the waste vanadium materials (solid-liquid separation). As the vanadium microspheres have more pores, the leaching of vanadium ions is facilitated, and the leaching liquid containing vanadium ions is obtained.
The oxidation-reduction reaction is carried out by heating, so that the oxidation-reduction reaction rate can be increased, and the leaching rate of vanadium ions can be accelerated. The heating temperature range ensures that the vanadium ions in the solution do not exist in the form of polyvanadate complex ions.
And after the leaching reaction is finished, obtaining vanadium-containing leaching solution and vanadium microsphere residues.
S4, calibrating the concentration and valence state of vanadium ions in the leaching solution obtained in the step S3.
As the leaching of vanadium ions is a longer process, and the valence states of vanadium elements in the waste vanadium materials are different, the vanadium ion calibration method is adopted to scale the concentration and valence states of vanadium ions in the leaching solution every half an hour until the values are basically stable, so that the process flow can be shortened.
S5, weighing a bismuth raw material according to the concentration and the content of vanadium ions in the leaching solution, dissolving the bismuth raw material in a nitric acid solution with a certain concentration, and slowly dripping the bismuth raw material into the leaching solution in an atomization mode to form brown yellow bismuth vanadate precipitate.
In the step, bismuth nitrate, bismuth subcarbonate, bismuth oxide or bismuth oxalate is selected as the bismuth raw material, and the bismuth content is higher than 99.5%. Bismuth nitrate is preferred for avoiding the introduction of impurity ions and for reducing the amount of acid used.
The bismuth raw material is dissolved in a nitric acid solution, so that bismuth ions are separated out, the concentration of nitric acid is controlled to be 7-20%, and a bismuth ion clarified solution can be obtained.
The weighed bismuth raw material is used in an amount such that the ratio of vanadium ions to bismuth ions is controlled to be 1:0.9 to 1.1.
Along with continuous leaching and enrichment of vanadium ions, after the reduction reaction is completed, bismuth ions are dropwise added into the leaching solution in the step S3, and the bismuth ions and the vanadium ions are quickly combined to form nano-sized bismuth vanadate precipitate at the moment of contact. However, as the precipitation rate formed when bismuth ions and vanadium ions are combined is high, such as the dripping rate is too high, local agglomeration is easy to generate, the step adopts an atomization mode to slowly drip, the precipitation rate generated by combining bismuth ions and vanadium ions can be slowed down, the solution saturation is reduced, the reaction is carried out towards the direction of reducing the concentration of vanadium ions, the leaching rate of vanadium ions can be accelerated, and the complete leaching of vanadium ions is easier to ensure.
In the reduction process, if oxalic acid is adopted as a reducing agent, bismuth ions in the solution can react with oxalate ions to generate bismuth oxalate precipitates, and Bi 3+ + C 2 O 4 2- =Bi 2 (C 2 O 4 ) 3 That is, a small amount of bismuth oxalate and bismuth vanadate are simultaneously generated, but the bismuth oxalate is a side reaction product, so that the combination of bismuth ions and vanadium ions is reduced. The acid solution is added in the step for adjusting the pH value of the solution, so that bismuth oxalate precipitates can be completely dissolved, bismuth ions are continuously combined with vanadium ions to generate precipitation reaction, finally, the bismuth ions are completely converted into bismuth vanadate precipitates, and the effective rate of converting vanadium into bismuth vanadate is increased.
The added acid can be one or two of hydrochloric acid and nitric acid, and the pH value of the solution is regulated to be within the range of 0.1-1.
And S6, screening, filtering and rinsing the bismuth vanadate precipitate obtained in the step S5 to remove impurity ions, and drying to obtain the bismuth vanadate pigment.
The vanadium microsphere residue is separated from the sediment and the solution by screening, and the screened vanadium microsphere residue still contains a small amount of vanadium ions, so that the vanadium ions can be recovered and leached together with the next batch of vanadium microspheres for recycling; and the precipitation and solution filtration are carried out in a vacuum filtration, press filtration, a spin dryer or a centrifuge mode, then deionized water is used for rinsing until no salt exists, and then vacuum drying is carried out, wherein the drying temperature is 85-100 ℃, thus obtaining the bismuth vanadate environment-friendly pigment.
The invention will be further described in detail with reference to specific examples.
Example 1:
s1, detecting the recovered waste vanadium material through component analysis and spectral analysis, and selecting a waste vanadium material with the vanadium content of 5.5%;
s2, adding 0.25kg of calcium carbonate and 0.15kg of calcium fluoride into 5kg of waste vanadium materials, pelletizing by a pelletizer to prepare uniform vanadium microspheres with the diameter of 1cm, and then putting the uniform vanadium microspheres into a high-temperature furnace to bake for 1h at the temperature of 400 ℃ to obtain vanadium microspheres with a large number of pore structures;
s3, placing 1kg of the roasted vanadium microsphere in a container A, adding 10L of deionized water, heating to 60 ℃, adding 120ml of 5% oxalic acid solution, and stirring for 5 hours to generate oxidation-reduction reaction;
s4, adopting a vanadium ion calibration method, and calibrating the concentration and valence state of vanadium ions in the container A every half an hour until the value is basically stable, so that the final vanadium ion concentration is 4.75g/L;
s5, weighing 0.25kg of bismuth nitrate, dissolving the bismuth nitrate in a nitric acid solution with the concentration of 500 and ml percent and 7 percent, placing the bismuth nitrate into a sprayer, and atomizing and dripping the bismuth nitrate into a container A to quickly form brown-yellow bismuth vanadate precipitate;
after 2 hours, adding 100ml of nitric acid solution with the concentration of 7 percent to ensure that the pH value of the solution is about 0.5, dissolving the side reaction bismuth oxalate precipitate, and finally completely converting into bismuth vanadate precipitate;
s6, screening the obtained bismuth vanadate precipitate, vacuum filtering, rinsing for the second time to remove impurity ions, and drying in a vacuum drying oven at the temperature of 95 ℃ for 2 hours to obtain 160g of primary bismuth vanadate pigment.
The color index is as follows: l is 89.07, a is-1.75, b is 77.28.
Example 2:
s1, detecting the recovered crude vanadium material through component analysis and spectrum analysis, and selecting a crude vanadium material with the vanadium content of 7.3%;
s2, adding 0.35kg of zinc oxide and 0.2kg of zinc fluoride into 5kg of crude vanadium material, pelletizing by a pelletizer to prepare uniform vanadium microspheres with the diameter of 0.5cm, and then putting the uniform vanadium microspheres into a high-temperature furnace to bake for 30min at the temperature of 550 ℃ to obtain vanadium microspheres with a large number of pore structures;
s3, placing 2kg of roasted waste vanadium microspheres in a container A, adding 20L of deionized water, heating to 80 ℃, adding 200ml of 10% oxalic acid solution, and stirring for 3 hours to generate oxidation-reduction reaction;
s4, adopting a vanadium ion calibration method, and calibrating the concentration and valence state of vanadium ions in the container A every half an hour until the value is basically stable, so that the final vanadium ion concentration is 11.3g/L;
s5, weighing 0.55kg of bismuth oxalate, dissolving in 700 ml nitric acid solution with the concentration of 7%, placing in a sprayer, atomizing and dripping into a container A, and rapidly forming brown yellow bismuth vanadate precipitate;
after 2 hours, adding 100ml of nitric acid solution with the concentration of 7 percent to ensure that the pH value of the solution is about 0.6, dissolving the side reaction bismuth oxalate precipitate, and finally completely converting into bismuth vanadate precipitate;
s6, screening the obtained bismuth vanadate precipitate, centrifugally filtering, secondarily rinsing to remove impurity ions, and drying in a vacuum drying oven at the temperature of 95 ℃ for 2 hours to obtain 380g of primary bismuth vanadate pigment.
The color index is as follows: l is 90.12, a is-0.95, and b is 79.53.
Example 3:
s1, detecting the recovered waste vanadium material through component analysis and spectrum analysis, and selecting a crude vanadium material with the vanadium content of 6.5%;
s2, adding 0.5kg of calcium carbonate and 0.25kg of calcium fluoride into 5kg of waste vanadium materials, pelletizing by a pelletizer to prepare uniform vanadium microspheres with the diameter of 2cm, and then putting the uniform vanadium microspheres into a high-temperature furnace to bake for 4 hours at the temperature of 350 ℃ to obtain vanadium microspheres with a large number of pore structures;
s3, placing 3kg of roasted waste vanadium microspheres in a container A, adding 30L of deionized water, heating to 70 ℃, adding 400ml of 15% ammonium sulfite solution, and stirring for 3 hours to generate oxidation-reduction reaction;
s4, adopting a vanadium ion calibration method, and calibrating the concentration and valence state of vanadium ions in the container A every half an hour until the value is basically stable, so that the final vanadium ion concentration is 9.5g/L;
s5, weighing 0.35kg of bismuth nitrate, dissolving the bismuth nitrate in a 700 ml nitric acid solution with the concentration of 7%, placing the bismuth nitrate in a sprayer, and atomizing and dripping the bismuth nitrate into a container A to quickly form brown-yellow bismuth vanadate precipitate;
s6, screening the obtained bismuth vanadate precipitate, centrifugally filtering, secondarily rinsing to remove impurity ions, and drying in a vacuum drying oven at the temperature of 95 ℃ for 2 hours to obtain 380g of primary bismuth vanadate pigment.
The color index is as follows: l is 89.3, a is-1.2, b is 77.53.
The above-described embodiments of the present invention are only some of the preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions and improvements made by those skilled in the art without departing from the spirit of the present invention shall fall within the scope of the present invention.
Claims (6)
1. The method for preparing the environment-friendly pigment by utilizing the industrial waste vanadium material is characterized by comprising the following steps of:
s1, calibrating element types and content of the waste vanadium material, and selecting the waste vanadium material with the vanadium valence state of pentavalent or tetravalent and the vanadium content of 3-20%;
s2, adding a certain amount of calcium salt or/and zinc salt into the selected waste vanadium material, granulating, and roasting at 300-550 ℃ for 0.5-5h to obtain vanadium microspheres with a large number of pore structures; the calcium salt is calcium carbonate or calcium oxide, the zinc salt is zinc carbonate or zinc oxide, and the addition amount of the calcium salt or/and the zinc salt is 5-20% of the waste vanadium material;
s3, adding deionized water into the vanadium microspheres, heating, adding a reducing agent solution, stirring to leach vanadium ions from the vanadium microspheres, wherein the reducing agent is oxalic acid or ammonium sulfite with the concentration of 5-20%, the adding amount of the reducing agent is 1-2% of the deionized water, and the heating temperature is 60-90 ℃ for 2-5 hours;
s4, calibrating the vanadium ion concentration and valence state of the leaching solution obtained in the step S3;
s5, weighing a bismuth raw material, dissolving the bismuth raw material in a nitric acid solution with a certain concentration, and slowly dripping the bismuth raw material into the leaching solution in an atomization mode to form brown yellow bismuth vanadate precipitate; the bismuth raw material is bismuth nitrate, bismuth subcarbonate, bismuth oxide or bismuth oxalate, and the ratio of vanadium ions in the leaching solution to bismuth ions in the bismuth raw material is 1:0.9 to 1.1;
and S6, screening, filtering and rinsing the bismuth vanadate precipitate to remove impurity ions, and drying to obtain the bismuth vanadate pigment.
2. The method for preparing environment-friendly pigment by using industrial waste vanadium material as set forth in claim 1, wherein the waste vanadium material in the step S1 is waste vanadium material or crude vanadium material containing vanadic anhydride, vanadic anhydride or vanadyl sulfate.
3. The method for preparing environment-friendly pigment by using industrial waste vanadium material according to claim 1 or 2, wherein in the step S2, alkaline earth fluoride is further added into the waste vanadium material, and the addition amount of the alkaline earth fluoride is 3-5% of the waste vanadium material.
4. The method for preparing environment-friendly pigment by using industrial waste vanadium according to claim 1, wherein when oxalic acid is used as the reducing agent, an acid solution is added to the solution of the step S5 to make the pH value of the solution be 0.1-1.
5. The method for preparing environment-friendly pigment by using industrial waste vanadium according to claim 4, wherein the acid in the acid solution is one or a mixture of hydrochloric acid and nitric acid.
6. The method for preparing environment-friendly pigment by using industrial waste vanadium according to claim 1, wherein the concentration of the nitric acid solution in the step S5 is 7-20%.
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| CN107601561A (en) * | 2017-09-13 | 2018-01-19 | 佛山市力合通新材料有限公司 | The preparation method of nanometer pucherite yellow uitramarine |
| CN107626297A (en) * | 2017-09-29 | 2018-01-26 | 中南大学 | A kind of tiny balloon shape bismuth/composite bismuth vanadium photocatalyst and its preparation method and application |
| CN114031114A (en) * | 2021-11-12 | 2022-02-11 | 成都先进金属材料产业技术研究院股份有限公司 | Method for preparing bismuth vanadate powder by using failure electrolyte of vanadium battery |
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