A method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution

Abstract

The present invention relates to a method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution. The technical scheme comprises the following steps: first, the high-acidity vanadium-containing solution is passed through n first ion exchange columns, and then through m second ion exchange columns; when the vanadium concentration in the adsorption residual liquid exiting the last m second ion exchange columns is 3-5% of the vanadium concentration in the high-acidity vanadium-containing solution, the flow of the high-acidity vanadium-containing solution is stopped, thereby obtaining a loaded resin. Deionized water is then passed countercurrently through the second ion exchange columns, and then countercurrently into the first ion exchange columns for washing; a desorbent is passed countercurrently through the second ion exchange columns and then countercurrently into the first ion exchange columns for desorption, thereby obtaining a desorbed resin and a vanadium-rich solution. The vanadium-rich solution is then passed through a vanadium-rich solution pretreatment system to obtain a vanadium precipitation stock solution; ammonium chloride is mixed and stirred with the vanadium precipitation stock solution, and the ammonium vanadate obtained by solid-liquid separation is roasted to obtain the vanadium pentoxide product. The process is short, environmentally friendly, and requires minimal reagents.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparing vanadium pentoxide, and specifically relates to a method for preparing vanadium pentoxide by using a high-acidity vanadium-containing solution. Background Art

[0002] Vanadium-containing shale, a key vanadium resource, is an important raw material for the production of vanadium pentoxide. Currently, vanadium can be extracted from shale through direct sulfuric acid leaching, yielding a vanadium-containing acid leaching solution. Shale vanadium extraction acid leaching solutions are characterized by low pH, low vanadium concentration, and high levels of impurity ions, resulting in highly acidic and complex vanadium-containing solutions. Due to the complex process involved in preparing high-purity vanadium pentoxide from these low-vanadium, high-impregnation, and highly acidic solutions, these solutions have attracted considerable attention from those skilled in the art.

[0003] The patented technology "A Method for Preparing Vanadium Pentoxide" (CN 110467222 B) uses concentrated sulfuric acid to leach vanadium-containing shale to produce a vanadic acid solution. This solution is then leached with ammonium bicarbonate or ammonium sulfate to remove impurities. After adjusting the pH of the solution, an oxidizing agent is added for oxidation, followed by solid-liquid separation to produce a first solution. This solution is then enriched through an ion exchange process and eluted with sodium hydroxide to produce a vanadium-rich solution. Finally, impurities are removed, vanadium is precipitated, and calcined to produce vanadium pentoxide. This process for producing vanadium pentoxide from the vanadic acid solution is lengthy, consumes a lot of reagents, and produces a large amount of neutralization slag during the pH adjustment process.

[0004] The patented technology, "A Method for Clean Vanadium Extraction from Vanadium-Containing Solutions" (CN 114293016A), involves adding a calcium-containing vanadium precipitant to a vanadium-containing solution to adjust the pH, resulting in a calcium vanadate precipitate. The calcium vanadate precipitate is then stirred with water, and sulfuric acid is added to adjust the pH, resulting in a calcium sulfate precipitate and a vanadium-containing solution. Sulfuric acid is then added to the vanadium-containing solution to adjust the pH, followed by heating and stirring, followed by solid-liquid separation to obtain high-calcium hydrated vanadium and a vanadium extraction solution. Finally, the high-calcium hydrated vanadium is stirred with water, an acidic ammonium salt is added, and solid-liquid separation is performed to obtain ammonium polyvanadate. The ammonium polyvanadate is then calcined to produce vanadium pentoxide. This method requires repeated addition of reagents and pH adjustment, resulting in a lengthy process and the generation of a large amount of neutralization slag, which is environmentally unfriendly.

[0005] The patented technology, "A Method for Recovering Vanadium from an Acidic Solution Containing Silicon and Phosphorus" (CN 102864318 A), involves adjusting the pH of a vanadium-containing solution to 1.0-2.5, then using an anion exchange resin for adsorption. The resin is then desorbed with a strong alkaline solution to obtain a vanadium-rich solution. The vanadium-rich solution is then treated with a soluble magnesium or calcium salt for impurities removal, and finally vanadium precipitation is performed with an ammonium salt to obtain ammonium vanadate, which is then calcined to produce vanadium pentoxide. This technology requires not only pH adjustment but also impurity removal of the resulting vanadium-rich solution, resulting in high reagent consumption, a lengthy process, and the production of neutralization slag.

[0006] In summary, when preparing vanadium pentoxide from a high-acidity vanadium-containing solution, the pH of the high-acidity vanadium-containing solution needs to be adjusted. This process produces neutralization slag, which is not conducive to environmental protection, and has the problems of high reagent consumption and long process. Summary of the Invention

[0007] The present invention aims to overcome the defects of the prior art and aims to provide a method for preparing vanadium pentoxide from a high-acidity vanadium-containing solution. The method has a short process, is environmentally friendly and consumes less reagents.

[0008] To achieve the above object, the method for preparing vanadium pentoxide of the present invention is that steps 1 and 2 are carried out using a system for separating and extracting vanadium, and step 3 is carried out using a vanadium-rich liquid pretreatment system:

[0009] Step 1: Resin adsorption

[0010] The resin adsorption method comprises the following steps: simultaneously flowing a high-acidity vanadium-containing solution into a first ion exchange column 1, a first ion exchange column 2, ..., and a first ion exchange column n of a first part of ion exchange columns at a flow rate of 1 to 1.5 BV / h; the preliminarily adsorbed high-acidity vanadium-containing solution flowing out of the first part of ion exchange columns then flows through a second ion exchange column 1, a second ion exchange column 2, ..., and a second ion exchange column m of a second part of ion exchange columns at a flow rate of 1 to 1.5 BV / h, which is n times the flow rate; and stopping flowing the high-acidity vanadium-containing solution when the vanadium concentration of the adsorption residual solution flowing out of the second ion exchange column m is 3 to 5% of the vanadium concentration in the high-acidity vanadium-containing solution, thereby obtaining a loaded resin and an adsorption residual solution.

[0011] The high-acidity vanadium-containing solution has a pH of 0-1, a V(V) concentration of less than 4.5 g / L, and a Fe(III) concentration of less than 8 g / L.

[0012] The resin filled in the first part of the ion exchange column is "a modified resin for extracting vanadium from a high-acidity vanadium-containing solution". The volume of the resin filled in the first part of the ion exchange column is 1BV, 1BV = 0.20 ~ 3.53m 3 The resin filled in the second part of the ion exchange column is the same as the resin filled in the first part of the ion exchange column, and the volume of the resin filled in the second part of the ion exchange column is 2BV.

[0013] The preparation method of the modified resin for extracting vanadium from a high-acidity vanadium-containing solution comprises the following steps: preparing ingredients according to a solid-liquid ratio of aminophosphoric acid-type chelating resin to ethanol of 1:(5-10) kg / L, mixing to obtain a mixture, then ultrasonically dispersing the mixture for 5-15 minutes, and performing solid-liquid separation to obtain a resin to be treated and a pretreatment liquid; adding aminosulfonic acid at a uniform speed to the resin to be treated at a temperature of 40-80°C and a rotation speed of 240-400 r / min, wherein the volume of the aminosulfonic acid added is 5-8 times the volume of the resin to be treated; continuing stirring for 20-36 hours, and performing solid-liquid separation to obtain a modified residual liquid and a treated resin; and allowing the treated resin to stand for 24-36 hours and washing with deionized water until the pH of the washing liquid is 6-7, thereby obtaining the modified resin for extracting vanadium from a high-acidity vanadium-containing solution.

[0014] The functional group of the aminophosphoric acid type chelating resin is -CH2NHCH2PO3 2- .

[0015] The power of the ultrasonic wave is 60-120W.

[0016] Step 2: Resin desorption

[0017] The resin desorption method is as follows: first, 10 to 40 BV of deionized water is countercurrently passed through the second ion exchange column m, the second ion exchange column m-1, ..., the second ion exchange column 1 at a flow rate of 3 to 5 BV / h, the first section of washing wastewater flowing out of the second ion exchange column 1 is countercurrently passed through n first ion exchange columns at a flow rate of 1 / n times 3 to 5 BV / h for washing, thereby obtaining resin to be desorbed and the second section of washing wastewater; then, 5 to 20 BV of desorbent is countercurrently passed through the second ion exchange column m, the second ion exchange column m-1, ..., the second ion exchange column 1 at a flow rate of 0.2 to 0.5 BV / h, the desorption liquid flowing out of the second ion exchange column 1 is countercurrently passed through n first ion exchange columns at a flow rate of 1 / n times 0.2 to 0.5 BV / h for desorption, thereby obtaining desorbed resin and vanadium-rich liquid.

[0018] The desorbent is a mixed solution of NaOH solution and NaCl solution, the molar ratio of NaOH solution:NaCl solution is (5-8):1; the concentration of the NaOH solution is 3-6 mol / L, and the concentration of the NaCl solution is 0.6-0.75 mol / L.

[0019] Step 3: Preparation of vanadium pentoxide

[0020] The vanadium-rich liquid is first pretreated using a vanadium-rich liquid pretreatment system, wherein the vanadium-rich liquid pretreatment system is composed of k third ion exchange columns connected in series, where k is any natural number of 1, 2, or 3. The vanadium-rich liquid pretreatment method is as follows:

[0021] When k is 1, that is, the vanadium-rich liquid pretreatment system is only the third ion exchange column 1, and the vanadium-rich liquid is flowed into the third ion exchange column 1 at a flow rate of 2 to 3 BV / h. If the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 1 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 1 is 9.5 to 11. The pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0022] When k is 2, that is, the vanadium-rich liquid pretreatment system consists of a third ion exchange column 1 and a third ion exchange column 2 connected in series, the vanadium-rich liquid is flowed into the third ion exchange column 1 and the third ion exchange column 2 at a flow rate of 2 to 3 BV / h. If the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 2 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 2 is 9.5 to 11, at which time the pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0023] When k is 3, that is, the vanadium-rich liquid pretreatment system consists of a third ion exchange column 1, a third ion exchange column 2, and a third ion exchange column 3 connected in series, the vanadium-rich liquid is flowed into the third ion exchange column 1, the third ion exchange column 2, and the third ion exchange column 3 at a flow rate of 2 to 3 BV / h. If the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 3 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 3 is 9.5 to 11, at which time the pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0024] The ammonium chloride and the vanadium precipitation solution are then mixed at a molar ratio of ammonium chloride to the vanadium content in the vanadium precipitation solution of (2-6):1 to obtain a mixture; the mixture is stirred at 25-35° C. for 30-120 minutes, and the solid-liquid is separated to obtain ammonium vanadate and a vanadium precipitation mother solution; and the ammonium vanadate is then calcined at 500-600° C. for 120-180 minutes to obtain vanadium pentoxide.

[0025] The resin filled in the third ion exchange column is a macroporous strongly acidic cation exchange resin, and the filling volume is 1 BV.

[0026] The system for separating and extracting vanadium is composed of two parts of ion exchange columns. The first part of the ion exchange columns is composed of n first ion exchange columns connected in parallel, and the second part of the ion exchange columns is composed of m second ion exchange columns connected in series; wherein: n is any natural number among 2, 3, 4, and m is any natural number among 2, 3, ..., 7, 8.

[0027] The stirring speed is 200-400 r / min.

[0028] The diameter of the first ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the first ion exchange column is (1 to 2):1; the diameter of the second ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the second ion exchange column is (2 to 4):1; the diameter of the third ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the third ion exchange column is (1 to 2):1.

[0029] The concentration of the aminosulfonic acid is 0.2-0.85 mol / L.

[0030] Compared with the prior art, the present invention has the following positive effects:

[0031] 1. The present invention directly uses a high-acidity vanadium-containing solution as the adsorption stock solution, eliminating the process of using alkaline agents such as sodium hydroxide and calcium hydroxide to adjust the pH. No neutralization slag is produced, which is beneficial to environmental protection. The resin filled in the first ion exchange column and the second ion exchange column of the present invention is a modified resin. The modified resin can extract vanadium from a high-acidity vanadium-containing solution with a pH of 0 to 1. Under high acidity conditions, vanadium exists in the solution in the form of VO2 + , the modified resin is easy to react with VO2 under acidic conditions + Chelation has higher selectivity for vanadium. In addition, the phosphate group on the modified resin is a strong acidic cationic group that can react with VO2 in the solution. + The modification changes the properties of the amino group (-NH) of the aminophosphoric acid type chelating resin functional group, which greatly reduces the chelation effect between the modified resin and iron in the solution, thereby enhancing the separation effect of vanadium and impurity iron.

[0032] 2. The present invention utilizes a first ion exchange column and a second ion exchange column to purify and enrich the high-acidity vanadium-containing solution. The first ion exchange column is connected in parallel, initially adsorbing vanadium from the high-acidity vanadium-containing solution at a flow rate of 1 to 1.5 BV / h. The second ion exchange column is connected in series, re-adsorbing the high-acidity vanadium-containing solution flowing out of the first ion exchange column at a flow rate n times that of the first ion exchange column. Through multi-stage adsorption, a vanadium adsorption rate of >99% is achieved. The adsorption pattern of vanadium by modified resin is rapid first, followed by slow adsorption to equilibrium. Therefore, the present invention first utilizes two ion exchange columns for adsorption. The first ion exchange column has a slow adsorption flow rate, allowing sufficient contact time between the modified resin and the vanadium. The second ion exchange column has a faster adsorption flow rate and a higher number of stages, providing the modified resin with sufficient adsorption sites for vanadium adsorption, thereby achieving a vanadium adsorption rate of >99%. The mixed solution of sodium hydroxide and sodium chloride is used to desorb the resin to be desorbed. Sodium hydroxide is an alkaline desorbent. When it flows through the two parts of the ion exchange column, the pH environment of the resin to be desorbed is changed, so that the vanadium on the resin to be desorbed is removed from VO2 +The cationic form is converted into the vanadate anion form and is desorbed into the vanadium-rich solution, achieving a vanadium desorption rate of >98%. The iron content in the vanadium-rich solution is less than 0.12g / L, and the vanadium-iron separation effect is good; the V2O5 concentration in the vanadium-rich solution is 23-30g / L, and the vanadium enrichment effect is good.

[0033] 3. The present invention uses a third ion exchange column to remove sodium ions from the vanadium-rich solution and adjust the pH of the vanadium-rich solution at the same time, thereby reducing the use of acidic pH regulators and reducing reagent consumption. The resin filled in the third ion exchange column is a macroporous strongly acidic cationic resin, which has excellent ion exchange performance with sodium ions. When the vanadium-rich solution flows through the third ion exchange column, the sodium ions are adsorbed by the macroporous strongly acidic cationic resin, and the H + It is exchanged into the vanadium-rich solution to adjust the pH of the vanadium-rich solution; ammonium chloride is added to the vanadium-rich solution to form ammonium vanadate precipitate, and the obtained ammonium vanadate is roasted and deaminated to convert the ammonium vanadate into vanadium pentoxide. The purity of the obtained vanadium pentoxide product is over 98%.

[0034] Therefore, the present invention has the characteristics of being environmentally friendly, having a short process and low drug consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 It is a resin adsorption system of the system for separating and extracting vanadium of the present invention;

[0036] Figure 2 It is a resin desorption system of the system for separating and extracting vanadium of the present invention;

[0037] Figure 3 It is a vanadium-rich liquid pretreatment system of the present invention;

[0038] Figure 4 It is another vanadium-rich liquid pretreatment system of the present invention;

[0039] Figure 5 This is another vanadium-rich liquid pretreatment system of the present invention. DETAILED DESCRIPTION

[0040] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, which does not limit the scope of protection thereof.

[0041] A method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution. The method for preparing vanadium pentoxide described in this embodiment is that steps one and two are performed using a system for separating and extracting vanadium, and step three is performed using a vanadium-rich solution pretreatment system.

[0042] Step 1: Resin adsorption

[0043] like Figure 1 and Figure 2As shown, the system for separating and extracting vanadium is composed of two parts of ion exchange columns. The first part of the ion exchange column is composed of n first ion exchange columns connected in parallel, and the second part of the ion exchange column is composed of m second ion exchange columns connected in series; wherein: n is any natural number among 2, 3, 4, and m is any natural number among 2, 3, ..., 7, 8.

[0044] The resin adsorption method is to use Figure 1 In the resin adsorption system shown, a high-acidity vanadium-containing solution is simultaneously fed into the first ion exchange column 1, the first ion exchange column 2, ..., and the first ion exchange column n of the first ion exchange column at a flow rate of 1 to 1.5 BV / h. The preliminarily adsorbed high-acidity vanadium-containing solution flowing out of the first ion exchange column then flows sequentially through the second ion exchange column 1, the second ion exchange column 2, ..., and the second ion exchange column m of the second ion exchange column at a flow rate n times that of 1 to 1.5 BV / h. When the vanadium concentration of the adsorption residual solution flowing out of the second ion exchange column m is 3 to 5% of the vanadium concentration in the high-acidity vanadium-containing solution, the flow of the high-acidity vanadium-containing solution is stopped, thereby obtaining a loaded resin and the adsorption residual solution.

[0045] The high-acidity vanadium-containing solution has a pH of 0-1, a V(V) concentration of less than 4.5 g / L, and a Fe(III) concentration of less than 8 g / L.

[0046] The resin filled in the first part of the ion exchange column is "a modified resin for extracting vanadium from a high-acidity vanadium-containing solution". The volume of the resin filled in the first part of the ion exchange column is 1BV, 1BV = 0.20 ~ 3.53m 3 The resin filled in the second part of the ion exchange column is the same as the resin filled in the first part of the ion exchange column, and the volume of the resin filled in the second part of the ion exchange column is 2BV.

[0047] The preparation method of the modified resin for extracting vanadium from a high-acidity vanadium-containing solution comprises the following steps: preparing ingredients according to a solid-liquid ratio of aminophosphoric acid-type chelating resin to ethanol of 1:(5-10) kg / L, mixing to obtain a mixture, then ultrasonically dispersing the mixture for 5-15 minutes, and performing solid-liquid separation to obtain a resin to be treated and a pretreatment liquid; adding aminosulfonic acid at a uniform speed to the resin to be treated at a temperature of 40-80°C and a rotation speed of 240-400 r / min, wherein the volume of the aminosulfonic acid added is 5-8 times the volume of the resin to be treated; continuing stirring for 20-36 hours, and performing solid-liquid separation to obtain a modified residual liquid and a treated resin; and allowing the treated resin to stand for 24-36 hours and washing with deionized water until the pH of the washing liquid is 6-7, thereby obtaining the modified resin for extracting vanadium from a high-acidity vanadium-containing solution.

[0048] The power of the ultrasonic wave is 60-120W.

[0049] Step 2: Resin desorption

[0050] The resin desorption method is to use Figure 2 In the resin desorption system shown, 10 to 40 BV of deionized water is first countercurrently passed through the second ion exchange column m, the second ion exchange column m-1, ..., the second ion exchange column 1 at a flow rate of 3 to 5 BV / h. The first-stage washing wastewater flowing out of the second ion exchange column 1 is then countercurrently passed through n first ion exchange columns at a flow rate of 1 / n times 3 to 5 BV / h for washing, thereby obtaining the resin to be desorbed and the second-stage washing wastewater.

[0051] Then, 5 to 20 BV of the desorbent is countercurrently passed through the second ion exchange column m, the second ion exchange column m-1, ..., the second ion exchange column 1 at a flow rate of 0.2 to 0.5 BV / h. The desorbent flowing out of the second ion exchange column 1 is countercurrently passed through n first ion exchange columns at a flow rate of 1 / n times 0.2 to 0.5 BV / h for desorption, thereby obtaining a desorbed resin and a vanadium-rich solution.

[0052] The desorbent is a mixed solution of NaOH solution and NaCl solution, the molar ratio of NaOH solution:NaCl solution is (5-8):1; the concentration of the NaOH solution is 3-6 mol / L, and the concentration of the NaCl solution is 0.6-0.75 mol / L.

[0053] Step 3: Preparation of vanadium pentoxide

[0054] The vanadium-rich liquid is first pretreated using a vanadium-rich liquid pretreatment system, wherein the vanadium-rich liquid pretreatment system is composed of k third ion exchange columns connected in series, where k is any natural number of 1, 2, or 3. The vanadium-rich liquid pretreatment method is as follows:

[0055] When k is 1, that is, the vanadium-rich liquid pretreatment system is only the third ion exchange column 1; the vanadium-rich liquid is flowed into the third ion exchange column 1 at a flow rate of 2 to 3 BV / h. If the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 1 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 1 is 9.5 to 11. The pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0056] When k is 2, that is, the vanadium-rich liquid pretreatment system consists of a third ion exchange column 1 and a third ion exchange column 2 connected in series; the vanadium-rich liquid is flowed into the third ion exchange column 1 and the third ion exchange column 2 at a flow rate of 2 to 3 BV / h. If the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 2 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 2 is 9.5 to 11. The pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0057] When k is 3, that is, the vanadium-rich liquid pretreatment system consists of a third ion exchange column 1, a third ion exchange column 2, and a third ion exchange column 3 connected in series; the vanadium-rich liquid is flowed into the third ion exchange column 1, the third ion exchange column 2, and the third ion exchange column 3 at a flow rate of 2 to 3 BV / h. If the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 3 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 3 is 9.5 to 11, at which time the pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0058] The ammonium chloride and the vanadium precipitation solution are then mixed at a molar ratio of ammonium chloride to the vanadium content in the vanadium precipitation solution of (2-6):1 to obtain a mixture; the mixture is stirred at 25-35° C. for 30-120 minutes, and the solid-liquid is separated to obtain ammonium vanadate and a vanadium precipitation mother solution; and the ammonium vanadate is then calcined at 500-600° C. for 120-180 minutes to obtain vanadium pentoxide.

[0059] like Figure 3 、 Figure 4 and Figure 5 As shown, the vanadium-rich liquid pretreatment system is composed of one third ion exchange column, or two third ion exchange columns connected in series, or three third ion exchange columns connected in series.

[0060] The stirring speed is 200-400 r / min.

[0061] The diameter of the first ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the first ion exchange column is (1 to 2):1; the diameter of the second ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the second ion exchange column is (2 to 4):1; the diameter of the third ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the third ion exchange column is (1 to 2):1.

[0062] The concentration of the aminosulfonic acid is 0.2-0.85 mol / L.

[0063] In this specific implementation mode:

[0064] The functional group of the aminophosphoric acid type chelating resin is -CH2NHCH2PO3 2- ;

[0065] The resin filled in the third ion exchange column is a macroporous strongly acidic cation exchange resin, and the filling volume is 1 BV.

[0066] The details will not be described in detail in the embodiments.

[0067] Example 1

[0068] A method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution. The method for preparing vanadium pentoxide comprises steps 1 and 2 being performed using a system for separating and extracting vanadium, and step 3 being performed using a vanadium-rich solution pretreatment system:

[0069] like Figure 1 and Figure 2 As shown, the system for separating and extracting vanadium is composed of two parts of ion exchange columns. The first part of the ion exchange column is composed of n first ion exchange columns connected in parallel, and the second part of the ion exchange column is composed of m second ion exchange columns connected in series; in this embodiment: n=2; m=2.

[0070] Step 1: Resin adsorption

[0071] The resin adsorption method is to use Figure 1 In the resin adsorption system shown, a high-acidity vanadium-containing solution is simultaneously fed into the first ion exchange column 1 and the first ion exchange column 2 of the first ion exchange column at a flow rate of 1.5 BV / h. The preliminarily adsorbed high-acidity vanadium-containing solution flowing out of the first ion exchange column then flows sequentially through the second ion exchange column 1 and the second ion exchange column 2 of the second ion exchange column at a flow rate twice that of 1.5 BV / h. When the vanadium concentration of the adsorption residual solution flowing out of the second ion exchange column 2 reaches 3% of the vanadium concentration in the high-acidity vanadium-containing solution, the flow of the high-acidity vanadium-containing solution is stopped, thereby obtaining a loaded resin and the adsorption residual solution.

[0072] The high-acidity vanadium-containing solution has a pH of 0, a V(V) concentration of 1.2 g / L, and a Fe(III) concentration of 1 g / L.

[0073] The resin filled in the first part of the ion exchange column is "modified resin for extracting vanadium from high-acidity vanadium-containing solution", and the volume of the resin filled in the first part of the ion exchange column is 1BV, 1BV = 0.20m 3 The resin filled in the second part of the ion exchange column is the same as the resin filled in the first part of the ion exchange column, and the volume of the resin filled in the second part of the ion exchange column is 2BV.

[0074] The preparation method of the "modified resin for extracting vanadium from a high-acidity vanadium-containing solution" is as follows: ingredients are prepared according to a solid-liquid ratio of aminophosphoric acid-type chelating resin to ethanol of 1:5 kg / L, mixed to obtain a mixture, and then ultrasonically disperse the mixture for 5 minutes, solid-liquid separation, to obtain a resin to be treated and a pretreatment liquid; aminosulfonic acid is uniformly added to the resin to be treated at a temperature of 40°C and a rotation speed of 240 r / min, the volume of the added aminosulfonic acid being 5 times the volume of the resin to be treated; stirring is continued for 20 hours, solid-liquid separation is carried out, to obtain a modified residual liquid and a treated resin; the treated resin is allowed to stand for 24 hours, and washed with deionized water until the pH of the washing liquid reaches 6, to obtain a modified resin for extracting vanadium from a high-acidity vanadium-containing solution.

[0075] The power of the ultrasonic wave is 60W.

[0076] Step 2: Resin desorption

[0077] Resin desorption method uses Figure 2 In the resin desorption system shown, 10 BV of deionized water is first countercurrently passed through the second ion exchange column 2 and the second ion exchange column 1 at a flow rate of 5 BV / h, and the first section of washing wastewater flowing out of the second ion exchange column 1 is countercurrently passed through the two first ion exchange columns at a flow rate of 1 / 2 times 5 BV / h for washing, thereby obtaining the resin to be desorbed and the second section of washing wastewater; then 5 BV of desorbent is countercurrently passed through the second ion exchange column 2 and the second ion exchange column 1 at a flow rate of 0.5 BV / h, and the desorption liquid flowing out of the second ion exchange column 1 is countercurrently passed through the two first ion exchange columns at a flow rate of 1 / 2 times 0.5 BV / h for desorption, thereby obtaining the desorbed resin and vanadium-rich liquid.

[0078] The desorbent is a mixed solution of NaOH solution and NaCl solution, and the molar ratio of NaOH solution:NaCl solution is 5:1; the concentration of the NaOH solution is 3 mol / L, and the concentration of the NaCl solution is 0.6 mol / L.

[0079] Step 3: Preparation of vanadium pentoxide

[0080] First, the vanadium-rich liquid is pretreated using a vanadium-rich liquid pretreatment system. The vanadium-rich liquid pretreatment system is as follows: Figure 3 As shown, the vanadium-rich liquid pretreatment system is only the third ion exchange column 1. The pretreatment method of the vanadium-rich liquid is:

[0081] The vanadium-rich solution is flowed into the third ion exchange column 1 at a flow rate of 3 BV / h. When the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 1 is greater than 11, the pretreated vanadium-rich solution is returned to the vanadium-rich solution. The above process is repeated until the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 1 is 10.8. The pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0082] The ammonium chloride is then mixed with the vanadium precipitation solution at a molar ratio of ammonium chloride to the vanadium content in the vanadium precipitation solution of 2:1 to obtain a mixture; the mixture is stirred at 25° C. for 30 minutes, and the solid-liquid separation is performed to obtain ammonium vanadate and a vanadium precipitation mother liquor; and the ammonium vanadate is then calcined at 500° C. for 120 minutes to obtain vanadium pentoxide.

[0083] The stirring speed is 200 r / min.

[0084] The diameter of the first ion exchange column is 0.5m, and the ratio of the height to the diameter of the first ion exchange column is 1:1; the diameter of the second ion exchange column is 0.5m, and the ratio of the height to the diameter of the second ion exchange column is 2:1; the diameter of the third ion exchange column is 0.5m, and the ratio of the height to the diameter of the third ion exchange column is 1:1.

[0085] The concentration of the sulfamic acid is 0.2 mol / L.

[0086] In this embodiment, the V adsorption rate in the high-acidity vanadium-containing solution is 99.33%; the V desorption rate is 98.55%; the V2O5 concentration in the vanadium-rich solution is 25.55 g / L; the Fe concentration is 0.11 g / L; and the purity of the vanadium pentoxide product is 98.03%.

[0087] Example 2

[0088] A method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution. The method for preparing vanadium pentoxide comprises steps 1 and 2 being performed using a system for separating and extracting vanadium, and step 3 being performed using a vanadium-rich solution pretreatment system:

[0089] like Figure 1 and Figure 2 As shown, the system for separating and extracting vanadium is composed of two parts of ion exchange columns. The first part of the ion exchange column is composed of n first ion exchange columns connected in parallel, and the second part of the ion exchange column is composed of m second ion exchange columns connected in series; in this embodiment: n=3; m=4.

[0090] Step 1: Resin adsorption

[0091] The resin adsorption method is to use Figure 1In the resin adsorption system shown, a high-acidity vanadium-containing solution is simultaneously flowed into the first ion exchange column 1, the first ion exchange column 2, and the first ion exchange column 3 of the first ion exchange column at a flow rate of 1.25 BV / h. The preliminarily adsorbed high-acidity vanadium-containing solution flowing out of the first ion exchange column then flows through the second ion exchange column 1, the second ion exchange column 2, and the second ion exchange column 4 of the second ion exchange column at a flow rate three times that of 1.25 BV / h. When the vanadium concentration of the adsorption residual solution flowing out of the second ion exchange column 4 reaches 4% of the vanadium concentration in the high-acidity vanadium-containing solution, the flow of the high-acidity vanadium-containing solution is stopped, thereby obtaining a loaded resin and the adsorption residual solution.

[0092] The high-acidity vanadium-containing solution has a pH of 0.4, a V(V) concentration of 2.5 g / L, and a Fe(III) concentration of 4.5 g / L.

[0093] The resin filled in the first part of the ion exchange column is "modified resin for extracting vanadium from high-acidity vanadium-containing solution", and the volume of the resin filled in the first part of the ion exchange column is 1BV, 1BV = 2.00m 3 The resin filled in the second part of the ion exchange column is the same as the resin filled in the first part of the ion exchange column, and the volume of the resin filled in the second part of the ion exchange column is 2BV.

[0094] The preparation method of the "modified resin for extracting vanadium from a high-acidity vanadium-containing solution" is as follows: ingredients are prepared according to a solid-liquid ratio of aminophosphoric acid-type chelating resin to ethanol of 1:7 kg / L, mixed to obtain a mixture, and then ultrasonically disperse the mixture for 10 minutes, solid-liquid separation, to obtain a resin to be treated and a pretreatment liquid; aminosulfonic acid is uniformly added to the resin to be treated at a temperature of 60°C and a rotation speed of 320 r / min, with the volume of the aminosulfonic acid added being 6 times the volume of the resin to be treated; stirring is continued for 28 hours, solid-liquid separation is carried out, to obtain a modified residual liquid and a treated resin; the treated resin is allowed to stand for 30 hours, and washed with deionized water until the pH of the washing liquid reaches 6.5, to obtain a modified resin for extracting vanadium from a high-acidity vanadium-containing solution.

[0095] The power of the ultrasonic wave is 90W.

[0096] Step 2: Resin desorption

[0097] The resin desorption method is to use Figure 2In the resin desorption system shown, 25 BV of deionized water is first countercurrently passed through the second ion exchange column 4, the second ion exchange column 3, ..., and the second ion exchange column 1 at a flow rate of 4 BV / h. The first section of washing wastewater flowing out of the second ion exchange column 1 is then countercurrently passed through the three first ion exchange columns at a flow rate of 1 / 3 times 4 BV / h for washing to obtain the resin to be desorbed and the second section of washing wastewater; then 12 BV of desorbent is countercurrently passed through the second ion exchange column 4, the second ion exchange column 3, ..., and the second ion exchange column 1 at a flow rate of 0.3 BV / h. The desorption liquid flowing out of the second ion exchange column 1 is then countercurrently passed through the three first ion exchange columns at a flow rate of 1 / 3 times 0.3 BV / h for desorption to obtain the desorbed resin and vanadium-rich liquid.

[0098] The desorbent is a mixed solution of NaOH solution and NaCl solution, and the molar ratio of NaOH solution:NaCl solution is 7:1; the concentration of the NaOH solution is 4.5 mol / L, and the concentration of the NaCl solution is 0.64 mol / L.

[0099] Step 3: Preparation of vanadium pentoxide

[0100] First, the vanadium-rich liquid is pretreated using a vanadium-rich liquid pretreatment system. The vanadium-rich liquid pretreatment system is as follows: Figure 4 As shown, the vanadium-rich liquid pretreatment system is composed of a third ion exchange column 1 and a third ion exchange column 2 connected in series. The pretreatment method of the vanadium-rich liquid is:

[0101] The vanadium-rich solution is flowed into the third ion exchange column 1 and the third ion exchange column 2 at a flow rate of 2.5 BV / h. When the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 2 is greater than 11, the pretreated vanadium-rich solution is returned to the vanadium-rich solution, and the above process is repeated until the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 2 is 10. The pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0102] The ammonium chloride and the vanadium precipitation solution are then mixed at a molar ratio of ammonium chloride to the vanadium content in the vanadium precipitation solution of 4:1 to obtain a mixture; the mixture is stirred at 30° C. for 75 minutes, and the solid-liquid separation is performed to obtain ammonium vanadate and a vanadium precipitation mother liquor; and the ammonium vanadate is then calcined at 550° C. for 150 minutes to obtain vanadium pentoxide.

[0103] The stirring speed is 300 r / min.

[0104] The diameter of the first ion exchange column is 1.0 m, and the ratio of the height to the diameter of the first ion exchange column is 1.5:1; the diameter of the second ion exchange column is 1.0 m, and the ratio of the height to the diameter of the second ion exchange column is 3:1; the diameter of the third ion exchange column is 1.0 m, and the ratio of the height to the diameter of the third ion exchange column is 1.5:1.

[0105] The concentration of the sulfamic acid is 0.55 mol / L.

[0106] In this embodiment, the V adsorption rate in the high-acidity vanadium-containing solution is 99.47%; the V desorption rate is 98.67%; the V2O5 concentration in the vanadium-rich solution is 27.96 g / L; the Fe concentration is 0.10 g / L; and the purity of the vanadium pentoxide product is 98.17%.

[0107] Example 3

[0108] A method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution. The method for preparing vanadium pentoxide described in this embodiment is that steps one and two are performed using a system for separating and extracting vanadium, and step three is performed using a vanadium-rich solution pretreatment system:

[0109] like Figure 1 and Figure 2 As shown, the system for separating and extracting vanadium is composed of two parts of ion exchange columns. The first part of the ion exchange column is composed of n first ion exchange columns connected in parallel, and the second part of the ion exchange column is composed of m second ion exchange columns connected in series; in this embodiment: n=4; m=8.

[0110] Step 1: Resin adsorption

[0111] The resin adsorption method is to use Figure 1 In the resin adsorption system shown, a high-acidity vanadium-containing solution is simultaneously fed into the first ion exchange column 1, the first ion exchange column 2, ..., and the first ion exchange column 4 of the first ion exchange column at a flow rate of 1.0 BV / h. The preliminarily adsorbed high-acidity vanadium-containing solution flowing out of the first ion exchange column then flows sequentially through the second ion exchange column 1, the second ion exchange column 2, ..., and the second ion exchange column 8 of the second ion exchange column at a flow rate four times that of 1.0 BV / h. When the vanadium concentration of the adsorption residual solution flowing out of the second ion exchange column 8 reaches 5% of the vanadium concentration in the high-acidity vanadium-containing solution, the flow of the high-acidity vanadium-containing solution is stopped, thereby obtaining a loaded resin and the adsorption residual solution.

[0112] The high-acidity vanadium-containing solution has a pH of 0.8, a V(V) concentration of 4.4 g / L, and a Fe(III) concentration of 7.5 g / L.

[0113] The resin filled in the first part of the ion exchange column is "modified resin for extracting vanadium from high-acidity vanadium-containing solution", and the volume of the resin filled in the first part of the ion exchange column is 1BV, 1BV = 3.53m 3 The resin filled in the second part of the ion exchange column is the same as the resin filled in the first part of the ion exchange column, and the volume of the resin filled in the second part of the ion exchange column is 2BV.

[0114] The preparation method of the "modified resin for extracting vanadium from a high-acidity vanadium-containing solution" is as follows: ingredients are prepared according to a solid-liquid ratio of aminophosphoric acid-type chelating resin to ethanol of 1:10 kg / L, mixed to obtain a mixture, and then ultrasonically disperse the mixture for 15 minutes, solid-liquid separation, to obtain a resin to be treated and a pretreatment liquid; aminosulfonic acid is uniformly added to the resin to be treated at a temperature of 80°C and a rotation speed of 400 r / min, the volume of the added aminosulfonic acid being 8 times the volume of the resin to be treated; stirring is continued for 36 hours, solid-liquid separation is carried out, to obtain a modified residual liquid and a treated resin; the treated resin is allowed to stand for 36 hours, and washed with deionized water until the pH of the washing liquid reaches 7, to obtain the modified resin for extracting vanadium from a high-acidity vanadium-containing solution.

[0115] The power of the ultrasonic wave is 120W.

[0116] Step 2: Resin desorption

[0117] The resin desorption method is to use Figure 2 In the resin desorption system shown, 40BV of deionized water is first countercurrently passed through the second ion exchange column 8, the second ion exchange column 7, ..., and the second ion exchange column 1 at a flow rate of 3BV / h. The first section of washing wastewater flowing out of the second ion exchange column 1 is then countercurrently passed through the four first ion exchange columns at a flow rate of 1 / 4 times 3BV / h for washing, thereby obtaining the resin to be desorbed and the second section of washing wastewater. Then, 20BV of desorbent is countercurrently passed through the second ion exchange column 8, the second ion exchange column 7, ..., and the second ion exchange column 1 at a flow rate of 0.2BV / h. The desorption liquid flowing out of the second ion exchange column 1 is then countercurrently passed through the four first ion exchange columns at a flow rate of 1 / 4 times 0.2BV / h for desorption, thereby obtaining the desorbed resin and vanadium-rich liquid.

[0118] The desorbent is a mixed solution of NaOH solution and NaCl solution, and the molar ratio of NaOH solution:NaCl solution is 8:1; the concentration of the NaOH solution is 6 mol / L, and the concentration of the NaCl solution is 0.75 mol / L.

[0119] Step 3: Preparation of vanadium pentoxide

[0120] First, the vanadium-rich liquid is pretreated using a vanadium-rich liquid pretreatment system. The vanadium-rich liquid pretreatment system is as follows: Figure 5 As shown, the vanadium-rich liquid pretreatment system is composed of a third ion exchange column 1, a third ion exchange column 2 and a third ion exchange column 3 connected in series. The pretreatment method of the vanadium-rich liquid is:

[0121] The vanadium-rich solution is flowed into the third ion exchange column 1, the third ion exchange column 2 and the third ion exchange column 3 at a flow rate of 2 BV / h. When the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 3 is greater than 11, the pretreated vanadium-rich solution is returned to the vanadium-rich solution, and the above process is repeated until the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 3 is 9.6. The pretreatment is stopped to obtain a vanadium precipitation stock solution.

[0122] The ammonium chloride and the vanadium precipitation solution are then mixed at a molar ratio of ammonium chloride to the vanadium content in the vanadium precipitation solution of 6:1 to obtain a mixture; the mixture is stirred at 35° C. for 120 minutes, and the solid-liquid separation is performed to obtain ammonium vanadate and a vanadium precipitation mother liquor; and the ammonium vanadate is then calcined at 600° C. for 180 minutes to obtain vanadium pentoxide.

[0123] The stirring speed is 400 r / min.

[0124] The diameter of the first ion exchange column is 1.5m, and the ratio of the height to the diameter of the first ion exchange column is 2:1; the diameter of the second ion exchange column is 1.5m, and the ratio of the height to the diameter of the second ion exchange column is 4:1; the diameter of the third ion exchange column is 1.5m, and the ratio of the height to the diameter of the third ion exchange column is 2:1.

[0125] The concentration of the sulfamic acid is 0.85 mol / L.

[0126] In this embodiment, the V adsorption rate in the high-acidity vanadium-containing solution is 99.79%; the V desorption rate is 99.51%; the V2O5 concentration in the vanadium-rich solution is 29.68 g / L; the Fe concentration is 0.08 g / L; and the purity of the vanadium pentoxide product is 98.22%.

[0127] Compared with the prior art, this embodiment has the following positive effects:

[0128] 1. This specific embodiment directly uses a high-acidity vanadium-containing solution as the adsorption stock solution; it reduces the process of using alkaline agents such as sodium hydroxide and calcium hydroxide to adjust the pH, and no neutralization slag is produced, which is beneficial to environmental protection. The resin filled in the first ion exchange column and the second ion exchange column in this specific embodiment is a modified resin. The modified resin can extract vanadium from a high-acidity vanadium-containing solution with a pH of 0 to 1. Under high acidity conditions, vanadium exists in the solution in the form of VO2 + , the modified resin is easy to react with VO2 under acidic conditions + Chelation has higher selectivity for vanadium. In addition, the phosphate group on the modified resin is a strong acidic cationic group that can react with VO2 in the solution. +The modification changes the properties of the amino group (-NH) of the aminophosphoric acid type chelating resin functional group, which greatly reduces the chelation effect between the modified resin and iron in the solution, thereby enhancing the separation effect of vanadium and impurity iron.

[0129] 2. This specific embodiment utilizes a first ion exchange column and a second ion exchange column to purify and enrich the highly acidic vanadium-containing solution. The first ion exchange column is connected in parallel, initially adsorbing vanadium from the highly acidic vanadium-containing solution at a flow rate of 1 to 1.5 BV / h. The second ion exchange column is connected in series, re-adsorbing the highly acidic vanadium-containing solution flowing out of the first ion exchange column at a flow rate n times that of the first ion exchange column. Through multi-stage adsorption, a vanadium adsorption rate exceeding 99% is achieved. The adsorption behavior of modified resin for vanadium is characterized by rapid initial adsorption followed by slow adsorption to equilibrium. Therefore, this specific embodiment initially utilizes two ion exchange columns for adsorption. The first ion exchange column has a slow adsorption flow rate, allowing sufficient contact time between the modified resin and the vanadium. The second ion exchange column has a faster adsorption flow rate and a higher number of stages, providing the modified resin with sufficient adsorption sites for vanadium adsorption, thereby achieving a vanadium adsorption rate exceeding 99%. The mixed solution of sodium hydroxide and sodium chloride is used to desorb the resin to be desorbed. Sodium hydroxide is an alkaline desorbent. When it flows through the two parts of the ion exchange column, the pH environment of the resin to be desorbed is changed, so that the vanadium on the resin to be desorbed is removed from VO2 + The cationic form is converted into the vanadate anion form and is desorbed into the vanadium-rich solution, achieving a vanadium desorption rate of >98%. The iron content in the vanadium-rich solution is less than 0.12g / L, and the vanadium-iron separation effect is good; the V2O5 concentration in the vanadium-rich solution is 23-30g / L, and the vanadium enrichment effect is good.

[0130] 3. This specific embodiment uses a third ion exchange column to remove sodium ions from the vanadium-rich solution and adjust the pH of the vanadium-rich solution at the same time, which reduces the use of acidic pH regulators and reduces reagent consumption. The resin filled in the third ion exchange column is a macroporous strong acidic cationic resin. This type of resin has excellent ion exchange performance with sodium ions. When the vanadium-rich solution flows through the third ion exchange column, the sodium ions are adsorbed by the macroporous strong acidic cationic resin, and the H on the macroporous strong acidic cationic resin is absorbed. + It is exchanged into the vanadium-rich solution to adjust the pH of the vanadium-rich solution; ammonium chloride is added to the vanadium-rich solution to form ammonium vanadate precipitate, and the obtained ammonium vanadate is roasted and deaminated to convert the ammonium vanadate into vanadium pentoxide. The purity of the obtained vanadium pentoxide product is over 98%.

[0131] Therefore, this specific embodiment has the characteristics of being environmentally friendly, having a short process and low drug consumption.

Claims

1. A method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution, characterized in that The method for preparing vanadium pentoxide is that steps 1 and 2 are performed using a system for separating and extracting vanadium, and step 3 is performed using a vanadium-rich liquid pretreatment system: Step 1: Resin adsorption The resin adsorption method comprises the following steps: simultaneously flowing a high-acidity vanadium-containing solution into a first ion exchange column 1, a first ion exchange column 2, ..., and a first ion exchange column n of a first part of ion exchange columns at a flow rate of 1 to 1.5 BV / h; the preliminarily adsorbed high-acidity vanadium-containing solution flowing out of the first part of ion exchange columns then flows through a second ion exchange column 1, a second ion exchange column 2, ..., and a second ion exchange column m of a second part of ion exchange columns at a flow rate of 1 to 1.5 BV / h, which is n times the flow rate; and stopping the flow of the high-acidity vanadium-containing solution when the vanadium concentration of the adsorption residual solution flowing out of the second ion exchange column m is 3 to 5% of the vanadium concentration in the high-acidity vanadium-containing solution, thereby obtaining a loaded resin and an adsorption residual solution. The high-acidity vanadium-containing solution has a pH of 0-1, a V(V) concentration of <4.5 g / L, and a Fe(III) concentration of <8 g / L. The resin filled in the first part of the ion exchange column is a modified resin for extracting vanadium from a high-acidity vanadium-containing solution. The volume of the resin filled in the first part of the ion exchange column is 1BV, where 1BV = 0.20 to 3.53m 3 The second part of the ion exchange column is filled with the same resin as the first part of the ion exchange column, and the volume of the second part of the ion exchange column is 2BV; The preparation method of the modified resin for extracting vanadium from a high-acidity vanadium-containing solution comprises the following steps: preparing ingredients according to a solid-liquid ratio of aminophosphoric acid-type chelating resin to ethanol of 1:(5-10) kg / L, mixing to obtain a mixture, then ultrasonically dispersing the mixture for 5-15 minutes, and performing solid-liquid separation to obtain a resin to be treated and a pretreatment solution; adding aminosulfonic acid at a uniform rate to the resin to be treated at a temperature of 40-80° C. and a rotation speed of 240-400 r / min, wherein the volume of the aminosulfonic acid added is 5-8 times the volume of the resin to be treated; continuing stirring for 20-36 hours, and performing solid-liquid separation to obtain a modified residual solution and a treated resin; allowing the treated resin to stand for 24-36 hours, and washing with deionized water until the pH of the washing solution is 6-7, thereby obtaining the modified resin for extracting vanadium from a high-acidity vanadium-containing solution; The functional group of the aminophosphoric acid type chelating resin is -CH2NHCH2PO3 2- ; The power of the ultrasonic wave is 60 to 120W; Step 2: Resin desorption The resin desorption method comprises the following steps: first, 10 to 40 BV of deionized water is countercurrently passed through a second ion exchange column m, a second ion exchange column m-1, ..., and a second ion exchange column 1 at a flow rate of 3 to 5 BV / h; the first-stage washing wastewater flowing out of the second ion exchange column 1 is countercurrently passed through n first ion exchange columns at a flow rate of 1 / n times 3 to 5 BV / h for washing, thereby obtaining a resin to be desorbed and a second-stage washing wastewater; then, 5 to 20 BV of a desorbent is countercurrently passed through the second ion exchange column m, a second ion exchange column m-1, ..., and a second ion exchange column 1 at a flow rate of 0.2 to 0.5 BV / h; the desorption liquid flowing out of the second ion exchange column 1 is countercurrently passed through n first ion exchange columns at a flow rate of 1 / n times 0.2 to 0.5 BV / h for desorption, thereby obtaining a desorbed resin and a vanadium-rich solution; The desorbent is a mixed solution of NaOH solution and NaCl solution, the molar ratio of NaOH solution:NaCl solution is (5-8):1; the concentration of the NaOH solution is 3-6 mol / L, and the concentration of the NaCl solution is 0.6-0.75 mol / L; Step 3: Preparation of vanadium pentoxide The vanadium-rich liquid is first pretreated using a vanadium-rich liquid pretreatment system, wherein the vanadium-rich liquid pretreatment system is composed of k third ion exchange columns connected in series, where k is any natural number of 1, 2, or 3. The vanadium-rich liquid pretreatment method is as follows: When k is 1, that is, the vanadium-rich solution pretreatment system is only the third ion exchange column 1, and the vanadium-rich solution is flowed into the third ion exchange column 1 at a flow rate of 2 to 3 BV / h; if the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 1 is greater than 11, the pretreated vanadium-rich solution is returned to the vanadium-rich solution, and the above process is repeated until the pH of the pretreated vanadium-rich solution flowing out of the third ion exchange column 1 is 9.5 to 11, at which time the pretreatment is stopped to obtain a vanadium precipitation stock solution; When k is 2, that is, the vanadium-rich liquid pretreatment system consists of a third ion exchange column 1 and a third ion exchange column 2 connected in series, and the vanadium-rich liquid is flowed into the third ion exchange column 1 and the third ion exchange column 2 at a flow rate of 2 to 3 BV / h; if the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 2 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 2 is 9.5 to 11, and the pretreatment is stopped to obtain a vanadium precipitation stock solution; When k is 3, that is, when the vanadium-rich liquid pretreatment system consists of the third ion exchange column 1, the third ion exchange column 2, and the third ion exchange column 3 connected in series, the vanadium-rich liquid is flowed into the third ion exchange column 1, the third ion exchange column 2, and the third ion exchange column 3 at a flow rate of 2 to 3 BV / h; if the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 3 is greater than 11, the pretreated vanadium-rich liquid is returned to the vanadium-rich liquid, and the above process is repeated until the pH of the pretreated vanadium-rich liquid flowing out of the third ion exchange column 3 is 9.5 to 11, at which time the pretreatment is stopped to obtain a vanadium precipitation stock solution; The ammonium chloride and the vanadium precipitation solution are then mixed at a molar ratio of ammonium chloride to the vanadium content in the vanadium precipitation solution of (2-6):1 to obtain a mixture; the mixture is stirred at 25-35° C. for 30-120 minutes, and the solid-liquid separation is performed to obtain ammonium vanadate and a vanadium precipitation mother solution; the ammonium vanadate is then roasted at 500-600° C. for 120-180 minutes to obtain vanadium pentoxide; The resin filled in the third ion exchange column is a macroporous strongly acidic cation exchange resin, and the filling volume is 1BV; The system for separating and extracting vanadium is composed of two parts of ion exchange columns. The first part of the ion exchange columns is composed of n first ion exchange columns connected in parallel, and the second part of the ion exchange columns is composed of m second ion exchange columns connected in series; wherein: n is any natural number among 2, 3, 4, and m is any natural number among 2, 3, ..., 7, 8.

2. The method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution according to claim 1, characterized in that The stirring speed is 200-400 r / min.

3. The method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution according to claim 1, characterized in that The diameter of the first ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the first ion exchange column is (1 to 2):1; the diameter of the second ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the second ion exchange column is (2 to 4):1; the diameter of the third ion exchange column is 0.5 to 1.5 m, and the ratio of the height to the diameter of the third ion exchange column is (1 to 2):

1.

4. The method for preparing vanadium pentoxide using a high-acidity vanadium-containing solution according to claim 1, characterized in that The concentration of the aminosulfonic acid is 0.2-0.85 mol / L.

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