Resin for adsorbing vanadium in acidic vanadium-containing solution and preparation method thereof

Abstract

The invention relates to resin for adsorbing vanadium in an acidic vanadium-containing solution and a preparation method of the resin. According to the technical scheme, macroporous anion exchange resin and phytic acid are mixed according to the solid-to-liquid ratio of 1: (15-30) Kg / L, and a mixture I is obtained; stirring the mixture I for the first time under the condition that the temperature is 30-90 DEG C, and carrying out solid-liquid separation to obtain resin to be treated and pretreatment liquid; mixing the resin to be treated with oxalic acid according to a solid-to-liquid ratio of 1: (18-32) Kg / L to obtain a mixture II, stirring the mixture II for the second time at the temperature of 40-80 DEG C, and carrying out solid-liquid separation to obtain treated resin and modified residual liquid; and standing the treated resin to prepare the resin for adsorbing vanadium in the acidic vanadium-containing solution. The resin for adsorbing vanadium in the acidic vanadium-containing solution has the characteristics of large saturated adsorption capacity, high vanadium adsorption rate and wide pH application range when the resin is used for adsorbing vanadium in the acidic vanadium-containing solution.

Description

Technical Field

[0001] The present invention belongs to the technical field of preparing resins for absorbing vanadium in vanadium-containing solutions, and specifically relates to a resin for absorbing vanadium in acidic vanadium-containing solutions and a preparation method thereof. Background Art

[0002] Ion exchange method for vanadium extraction mainly uses resin to adsorb and desorb vanadium ions, and then treats the obtained desorption liquid to recover vanadium. Compared with other methods, ion exchange method has the advantages of high recovery rate and simple operation. Ion exchange method can achieve good adsorption of vanadium in acidic solution. Commonly used vanadium extraction resins are macroporous anion exchange resins and chelating resins.

[0003] The patented technology of "Modified aminophosphate chelating resin for treating vanadium-containing solution and preparation method thereof" (CN114133468B) uses oxalic acid solution as a modifier to modify the aminophosphate chelating resin. The obtained "modified aminophosphate chelating resin for treating vanadium-containing solution" has a good adsorption effect on vanadium in acidic vanadium-containing solution when the pH value is 0.5-2.0, but for solutions with a pH value of 0-0.5, the adsorption performance of the chelating resin is poor, and the applicable range of pH for the chelating resin is narrow.

[0004] The patented technology of "a chelating resin and its preparation method and application" (CN 109384872 B) uses chloromethylated styrene resin beads as a matrix, reacts the chloromethyl group with piperazine to introduce an amino group, and then reacts with chloroacetic acid to introduce a carboxyl group. Although the chelating resin prepared by this method has good selectivity for vanadium ions and good adsorption of vanadium in acidic vanadium-containing solutions, the saturated adsorption capacity of the prepared chelating resin is low, only 45 to 86 mg / g.

[0005] The patented technology of "a modified resin for extracting vanadium from a vanadium-containing solution with high acidity and a preparation method thereof" (CN116851043A) uses aminosulfonic acid as a modifier to modify aminophosphoric acid chelating resin to obtain a modified resin for extracting vanadium from a vanadium-containing solution with high acidity. Although the prepared modified resin for extracting vanadium from a vanadium-containing solution with high acidity has a high adsorption capacity and a wide pH range for adsorbing vanadium from an acidic vanadium-containing solution, the prepared "modified resin for extracting vanadium from a vanadium-containing solution with high acidity" has a low adsorption rate for vanadium, which is only 80-85%.

[0006] In summary, the existing resin for adsorbing vanadium in acidic vanadium-containing solutions has the disadvantages of small saturated adsorption capacity and low vanadium adsorption rate, and the pH application range of the resin when adsorbing vanadium in acidic vanadium-containing solutions is narrow. 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 a resin for adsorbing vanadium in an acidic vanadium-containing solution. The resin for adsorbing vanadium in an acidic vanadium-containing solution prepared by the method has the characteristics of large saturated adsorption capacity, high vanadium adsorption rate and wide pH applicable range when adsorbing vanadium in an acidic vanadium-containing solution.

[0008] To achieve the above purpose, the specific steps of the technical solution adopted by the present invention are:

[0009] Step 1: Mix a macroporous anion exchange resin and phytic acid at a solid-liquid ratio of 1: (15-30) Kg / L to obtain a mixture I; then stir the mixture I for the first time at a temperature of 30-90° C. to separate the solid and liquid to obtain a resin to be treated and a pretreatment liquid.

[0010] Step 2: Mix the resin to be treated and oxalic acid at a solid-liquid ratio of 1: (18-32) kg / L to obtain a mixture II, and then stir the mixture II for a second time at a temperature of 40-80° C. to separate the solid and liquid to obtain a treated resin and a modified residual liquid.

[0011] Step 3: allowing the treated resin to stand to obtain a resin for adsorbing vanadium in an acidic vanadium-containing solution.

[0012] The functional group of the macroporous anion exchange resin is [-N(CH3)3OH].

[0013] The concentration of the phytic acid is 0.03-0.13 mol / L.

[0014] The concentration of the oxalic acid is 0.1-0.5 mol / L.

[0015] The stirring time of the first stirring is 20 to 40 hours, and the rotation speed of the first stirring is 100 to 300 r / min.

[0016] The stirring time of the second stirring is 20 to 36 hours, and the rotation speed of the second stirring is 100 to 300 r / min.

[0017] The standing time is 24 to 36 hours.

[0018] Compared with the prior art, the present invention has the following positive effects:

[0019] 1. The resin for adsorbing vanadium in an acidic vanadium-containing solution prepared by the present invention is prepared by modifying an existing macroporous anion exchange resin, using phytic acid as a modifier and oxalic acid as a group exchange agent. Phytic acid is used as a first-stage modifier to modify the nitrogen-containing functional groups on the macroporous anion exchange resin, and to graft phosphorus-containing functional groups that are easily combined with vanadium ions, and then oxalic acid is used for second-stage modification to give the macroporous anion exchange resin surface a more reactive and more active negative charge type group and density. Therefore, the prepared resin for adsorbing vanadium in an acidic vanadium-containing solution is tested to have a saturated adsorption capacity of 112 to 118 mg / g, which is large.

[0020] 2. The resin for adsorbing vanadium in an acidic vanadium-containing solution prepared by the present invention can extract vanadium from an acidic vanadium-containing solution with a pH of 0 to 2.5, while the existing macroporous anion exchange resin can only be applied to an acidic environment with a pH of 1.8 to 2.0, and the existing chelating resin can only be applied to an acidic environment with a pH of 0.5 to 2.0. The resin for adsorbing vanadium in an acidic vanadium-containing solution prepared by the present invention can extract vanadium from a vanadium-containing solution with a pH of 0 to 2.5, and the prepared product has a wider pH adaptability range when adsorbing vanadium in an acidic vanadium-containing solution.

[0021] 3. In the present invention, when pH=0-1, the vanadium in the acidic vanadium-containing solution is mainly in the form of VO2 + The phosphorus-containing groups in the prepared resin for adsorbing vanadium in the acidic vanadium-containing solution exchange cations with the vanadium in the acidic vanadium-containing solution; when the pH is 1-2, the vanadium in the acidic vanadium-containing solution is mainly in the form of VO2 + There are many forms such as polyvanadate anions, VO2 + The vanadium in the form of polyvanadate anions is exchanged with the phosphorus-containing group for cations, and the vanadium in the form of polyvanadate anions is exchanged with the nitrogen-containing group for anions; when pH=2-2.5, the vanadium in the acidic vanadium-containing solution mainly exists in the form of polyvanadate anions, and the prepared resin for adsorbing vanadium in the acidic vanadium-containing solution is exchanged with the vanadium through the nitrogen-containing group. Therefore, the resin for adsorbing vanadium in the acidic vanadium-containing solution prepared by the present invention has a wider pH adaptability range when adsorbing vanadium in the acidic vanadium-containing solution, and has a high vanadium adsorption rate. After detection, the vanadium adsorption rate is 86-90%.

[0022] Therefore, the resin prepared by the present invention for adsorbing vanadium in an acidic vanadium-containing solution has the characteristics of large saturated adsorption capacity, high vanadium adsorption rate and wide pH applicable range when adsorbing vanadium in an acidic vanadium-containing solution. DETAILED DESCRIPTION

[0023] The present invention is further described below in conjunction with specific implementation modes, but is not intended to limit the protection scope thereof.

[0024] A resin for adsorbing vanadium in an acidic vanadium-containing solution and a preparation method thereof. The preparation method described in this specific embodiment is:

[0025] Step 1: Mix a macroporous anion exchange resin and phytic acid at a solid-liquid ratio of 1: (15-30) Kg / L to obtain a mixture I; then stir the mixture I for the first time at a temperature of 30-90° C. to separate the solid and liquid to obtain a resin to be treated and a pretreatment liquid.

[0026] Step 2: Mix the resin to be treated and oxalic acid at a solid-liquid ratio of 1: (18-32) kg / L to obtain a mixture II, and then stir the mixture II for a second time at a temperature of 40-80° C. to separate the solid and liquid to obtain a treated resin and a modified residual liquid.

[0027] Step 3: allowing the treated resin to stand to obtain a resin for adsorbing vanadium in an acidic vanadium-containing solution.

[0028] The concentration of the phytic acid is 0.03-0.13 mol / L.

[0029] The concentration of the oxalic acid is 0.1-0.5 mol / L.

[0030] The stirring time of the first stirring is 20 to 40 hours, and the rotation speed of the first stirring is 100 to 300 r / min.

[0031] The stirring time of the second stirring is 20 to 36 hours, and the rotation speed of the second stirring is 100 to 300 r / min.

[0032] The standing time is 24 to 36 hours.

[0033] In this specific implementation mode:

[0034] The functional group of the macroporous anion exchange resin is [-N(CH3)3OH].

[0035] This will not be described in detail in the embodiments.

[0036] Example 1

[0037] A resin for adsorbing vanadium in an acidic vanadium-containing solution and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0038] Step 1: Mix macroporous anion exchange resin and phytic acid at a solid-liquid ratio of 1:15 kg / L to obtain a mixture I; then stir the mixture I for the first time at a temperature of 30° C. to separate the solid and liquid to obtain a resin to be treated and a pre-treated liquid.

[0039] Step 2: Mix the resin to be treated and oxalic acid at a solid-liquid ratio of 1:18 kg / L to obtain a mixture II, and then stir the mixture II for a second time at a temperature of 40° C. to separate the solid and liquid to obtain a treated resin and a modified residual liquid.

[0040] Step 3: allowing the treated resin to stand to obtain a resin for adsorbing vanadium in an acidic vanadium-containing solution.

[0041] The concentration of the phytic acid is 0.13 mol / L.

[0042] The concentration of the oxalic acid is 0.5 mol / L.

[0043] The stirring time of the first stirring is 20 hours, and the rotation speed of the first stirring is 100 r / min.

[0044] The stirring time of the second stirring is 20 hours, and the rotation speed of the second stirring is 100 r / min.

[0045] The standing time is 24h.

[0046] The resin prepared in this example for adsorbing vanadium in an acidic vanadium-containing solution was mixed with the acidic vanadium-containing solution at a solid-liquid ratio of 1:10 kg / L, and then placed in a constant temperature oscillator at a temperature of 25°C and a rotation speed of 200 r / min for adsorption for 2 hours. After testing, the saturated adsorption capacity of the prepared product was 112 mg / g, and the vanadium adsorption rate was 86.05%.

[0047] The acidic vanadium-containing solution has: pH=0; V concentration is 1.5 g / L.

[0048] Example 2

[0049] A resin for adsorbing vanadium in an acidic vanadium-containing solution and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0050] Step 1: Mix macroporous anion exchange resin and phytic acid at a solid-liquid ratio of 1:20 kg / L to obtain a mixture I; then stir the mixture I for the first time at a temperature of 50° C. to separate the solid and liquid to obtain a resin to be treated and a pre-treated liquid.

[0051] Step 2: Mix the resin to be treated and oxalic acid at a solid-liquid ratio of 1:23 kg / L to obtain a mixture II, and then stir the mixture II for a second time at a temperature of 54° C. to separate the solid and liquid to obtain a treated resin and a modified residual liquid.

[0052] Step 3: allowing the treated resin to stand to obtain a resin for adsorbing vanadium in an acidic vanadium-containing solution.

[0053] The concentration of the phytic acid is 0.1 mol / L.

[0054] The concentration of the oxalic acid is 0.37 mol / L.

[0055] The stirring time of the first stirring is 27 hours, and the rotation speed of the first stirring is 167 r / min.

[0056] The stirring time of the second stirring is 25 hours, and the rotation speed of the second stirring is 167 r / min.

[0057] The standing time is 28 hours.

[0058] The resin prepared in this example for adsorbing vanadium in an acidic vanadium-containing solution was mixed with the acidic vanadium-containing solution at a solid-liquid ratio of 1:10 kg / L, and then placed in a constant temperature oscillator at a temperature of 25°C and a rotation speed of 200 r / min for adsorption for 2 hours. After testing, the saturated adsorption capacity of the prepared product was 113 mg / g, and the vanadium adsorption rate was 88.30%.

[0059] The acidic vanadium-containing solution has a pH of 0.83 and a V concentration of 1.5 g / L.

[0060] Example 3

[0061] A resin for adsorbing vanadium in an acidic vanadium-containing solution and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0062] Step 1: Mix macroporous anion exchange resin and phytic acid at a solid-liquid ratio of 1:25 kg / L to obtain a mixture I; then stir the mixture I for the first time at a temperature of 70° C. to separate the solid and liquid to obtain a resin to be treated and a pre-treated liquid.

[0063] Step 2: Mix the resin to be treated and oxalic acid at a solid-liquid ratio of 1:28 kg / L to obtain a mixture II, and then stir the mixture II for a second time at a temperature of 67° C. to separate the solid and liquid to obtain a treated resin and a modified residual liquid.

[0064] Step 3: allowing the treated resin to stand to obtain a resin for adsorbing vanadium in an acidic vanadium-containing solution.

[0065] The concentration of the phytic acid is 0.06 mol / L.

[0066] The concentration of the oxalic acid is 0.23 mol / L.

[0067] The stirring time of the first stirring is 33 h, and the rotation speed of the first stirring is 233 r / min.

[0068] The stirring time of the second stirring is 31 hours, and the rotation speed of the second stirring is 233 r / min.

[0069] The standing time is 32h.

[0070] The resin prepared in this example for adsorbing vanadium in an acidic vanadium-containing solution was mixed with the acidic vanadium-containing solution at a solid-liquid ratio of 1:10 kg / L, and then placed in a constant temperature oscillator at a temperature of 25°C and a rotation speed of 200 r / min for adsorption for 2 hours. After testing, the saturated adsorption capacity of the prepared product was 115 mg / g, and the vanadium adsorption rate was 89.00%.

[0071] The acidic vanadium-containing solution has a pH of 1.67 and a V concentration of 1.5 g / L.

[0072] Example 4

[0073] A resin for adsorbing vanadium in an acidic vanadium-containing solution and a preparation method thereof. The steps of the preparation method described in this embodiment are:

[0074] Step 1: Mix macroporous anion exchange resin and phytic acid at a solid-liquid ratio of 1:30 kg / L to obtain a mixture I; then stir the mixture I for the first time at a temperature of 90° C. to separate the solid and liquid to obtain a resin to be treated and a pre-treated liquid.

[0075] Step 2: Mix the resin to be treated and oxalic acid at a solid-liquid ratio of 1:32 kg / L to obtain a mixture II, and then stir the mixture II for a second time at a temperature of 80° C. to separate the solid and liquid to obtain a treated resin and a modified residual liquid.

[0076] Step 3: allowing the treated resin to stand to obtain a resin for adsorbing vanadium in an acidic vanadium-containing solution.

[0077] The concentration of the phytic acid is 0.03 mol / L.

[0078] The concentration of the oxalic acid is 0.1 mol / L.

[0079] The stirring time of the first stirring is 40 hours, and the rotation speed of the first stirring is 300 r / min.

[0080] The stirring time of the second stirring is 36 hours, and the rotation speed of the second stirring is 300 r / min.

[0081] The standing time is 36 hours.

[0082] The resin prepared in this example for adsorbing vanadium in an acidic vanadium-containing solution was mixed with the acidic vanadium-containing solution at a solid-liquid ratio of 1:10 kg / L, and then placed in a constant temperature oscillator at a temperature of 25°C and a rotation speed of 200 r / min for adsorption for 2 hours. After testing, the saturated adsorption capacity of the prepared product was 118 mg / g, and the vanadium adsorption rate was 90.05%.

[0083] The acidic vanadium-containing solution has a pH of 2.5 and a V concentration of 1.5 g / L.

[0084] Compared with the prior art, the specific implementation method has the following positive effects:

[0085] 1. The resin for adsorbing vanadium in an acidic vanadium-containing solution prepared in this specific embodiment is prepared by modifying an existing macroporous anion exchange resin, using phytic acid as a modifier and oxalic acid as a group exchange agent. Phytic acid is used as a first-stage modifier to modify the nitrogen-containing functional groups on the macroporous anion exchange resin, and to graft phosphorus-containing functional groups that are easily combined with vanadium ions, and then oxalic acid is used for second-stage modification to give the macroporous anion exchange resin surface a more reactive and more active negative charge type group and density. Therefore, the prepared resin for adsorbing vanadium in an acidic vanadium-containing solution is tested to have a saturated adsorption capacity of 112 to 118 mg / g, which is large.

[0086] 2. The resin for adsorbing vanadium in an acidic vanadium-containing solution prepared by the specific implementation method can extract vanadium from an acidic vanadium-containing solution with a pH of 0 to 2.5, while the existing macroporous anion exchange resin can only be applied to an acidic environment with a pH of 1.8-2.0, and the existing chelating resin can only be applied to an acidic environment with a pH of 0.5-2.0. The resin for adsorbing vanadium in an acidic vanadium-containing solution prepared by the specific implementation method can extract vanadium from a vanadium-containing solution with a pH of 0 to 2.5, and the prepared product has a wider pH adaptability range when adsorbing vanadium in an acidic vanadium-containing solution.

[0087] 3. In this specific implementation method: when pH = 0-1, the vanadium in the acidic vanadium-containing solution is mainly in the form of VO2 + The phosphorus-containing groups in the prepared resin for adsorbing vanadium in the acidic vanadium-containing solution exchange cations with the vanadium in the acidic vanadium-containing solution; when the pH is 1-2, the vanadium in the acidic vanadium-containing solution is mainly in the form of VO2 + There are many forms such as polyvanadate anions, VO2 +The vanadium in the form of polyvanadate anions is exchanged with the phosphorus-containing groups for cations, and the vanadium in the form of polyvanadate anions is exchanged with the nitrogen-containing groups for anions; when pH=2-2.5, the vanadium in the acidic vanadium-containing solution mainly exists in the form of polyvanadate anions, and the prepared resin for adsorbing vanadium in the acidic vanadium-containing solution is exchanged with the vanadium through the nitrogen-containing groups. Therefore, the resin for adsorbing vanadium in the acidic vanadium-containing solution prepared by the specific implementation method has a wider pH adaptability range when adsorbing vanadium in the acidic vanadium-containing solution, and has a high vanadium adsorption rate. After testing, the vanadium adsorption rate is 86-90%.

[0088] Therefore, the resin for adsorbing vanadium in an acidic vanadium-containing solution prepared in this specific embodiment has the characteristics of large saturated adsorption capacity, high vanadium adsorption rate and wide pH applicable range when adsorbing vanadium in an acidic vanadium-containing solution.

Claims

1. A method for preparing a resin for adsorbing vanadium in an acidic vanadium-containing solution, characterized in that The specific steps of the preparation method are: Step 1, mixing a macroporous anion exchange resin and phytic acid at a solid-liquid ratio of 1: (15-30) kg / L to obtain a mixture I; then stirring the mixture I for the first time at a temperature of 30-90° C., separating the solid and the liquid, and obtaining a resin to be treated and a pre-treated liquid; Step 2, mixing the resin to be treated and oxalic acid at a solid-liquid ratio of 1: (18-32) kg / L to obtain a mixture II, and then stirring the mixture II for a second time at a temperature of 40-80° C. to separate the solid and liquid to obtain a treated resin and a modified residual liquid; Step 3: allowing the treated resin to stand to obtain a resin for adsorbing vanadium in an acidic vanadium-containing solution.

2. The method for preparing the resin for adsorbing vanadium in an acidic vanadium-containing solution according to claim 1, characterized in that: The functional group of the macroporous anion exchange resin is [-N(CH3)3OH].

3. The method for preparing the resin for adsorbing vanadium in an acidic vanadium-containing solution according to claim 1, characterized in that: The concentration of the phytic acid is 0.03-0.13 mol / L.

4. The method for preparing the resin for adsorbing vanadium in an acidic vanadium-containing solution according to claim 1, characterized in that: The concentration of the oxalic acid is 0.1-0.5 mol / L.

5. The method for preparing the resin for adsorbing vanadium in an acidic vanadium-containing solution according to claim 1, characterized in that: The stirring time of the first stirring is 20 to 40 hours, and the rotation speed of the first stirring is 100 to 300 r / min.

6. The method for preparing the resin for adsorbing vanadium in an acidic vanadium-containing solution according to claim 1, characterized in that: The stirring time of the second stirring is 20 to 36 hours, and the rotation speed of the second stirring is 100 to 300 r / min.

7. The method for preparing the resin for adsorbing vanadium in an acidic vanadium-containing solution according to claim 1, characterized in that: The standing time is 24 to 36 hours.

8. A resin for adsorbing vanadium in an acidic vanadium-containing solution, characterized in that: The resin for adsorbing vanadium in an acidic vanadium-containing solution is a resin for adsorbing vanadium in an acidic vanadium-containing solution prepared according to the method for preparing a resin for adsorbing vanadium in an acidic vanadium-containing solution according to any one of claims 1 to 7.