Calcium-magnesium adsorbent as well as preparation method and application thereof

Abstract

The invention relates to a calcium and magnesium adsorbent, which is prepared by mixing lignin, disulfate and soybean as raw materials and reacting. According to the calcium and magnesium adsorbent provided by the invention, lignin and disulfate are combined with soybeans, so that the calcium and magnesium adsorbent has a relatively strong adsorption effect on calcium and magnesium ions, and the adsorbent provided by the invention has excellent selection specificity on calcium and magnesium aiming at the ion type and content of manganese sulfate in a battery production process, and does not cause the problem that the Mn recovery rate is reduced.

Description

Technical Field

[0001] The invention relates to an adsorbent and a preparation method and application thereof, in particular to a calcium and magnesium adsorbent and a preparation method and application thereof, belonging to the technical field of solution impurity removal. Background Art

[0002] High-purity manganese sulfate is an important raw material for the preparation of lithium nickel-cobalt-manganese oxide and nickel-cobalt-manganese battery positive electrode materials. It is also the basic raw material for battery-grade high-purity manganese tetraoxide and high-purity manganese dioxide. With the country's strong support for the new energy industry, the new energy industry is about to usher in a period of explosive growth, and the demand for high-purity manganese sulfate will show explosive growth in the future.

[0003] The key to the preparation of high-purity manganese sulfate is the separation of Mg / Ca. At present, the separation of calcium and magnesium in manganese sulfate solution can be divided into three methods: chemical precipitation, solvent extraction, and solvent extraction-chemical precipitation. 1) Chemical precipitation, that is, fluorination, uses MnF2 as the fluorinating agent. However, since the generation of CaF2 and MgF2 requires an aging process, this process takes a long time, usually 36h to 48h. Secondly, since the particle size of CaF2 and MgF2 is extremely fine, it is difficult to filter. In this process, due to the need to add excessive fluorinating agent, F in the system - Exceeding the standard, it is necessary to use an extraction method to remove F-, which increases production costs. Since the Mg / Ca removal process requires a long time and process, it is very easy to cause unstable product quality. 2) Solvent extraction method. The solvent extraction method here refers to the use of forward extraction, that is, directly extracting Mn from the solution. However, the solution used in related studies is a self-prepared solution or a solution after dissolving industrial-grade manganese sulfate, and its Na, Mg, K, and Ca contents are lower than those in actual production, which does not meet the actual application requirements. 3) Solvent extraction solvent extraction-chemical precipitation combined method. P204 (di(2-ethylhexyl) phosphate) and P507 (2-ethylhexyl phosphate mono-2-ethylhexyl ester) are used to separate Ca from the solution, and then fluorination is used to separate Mg. Although the time is shortened compared to the single chemical precipitation method, part of Mn will be extracted while extracting Ca, resulting in a decrease in the Mn recovery rate.

[0004] Among the three methods of separating calcium and magnesium, the fluorination method is currently used in industry. However, since the generation of CaF2 and MgF2 requires an aging process, this process takes a long time, usually 36h to 48h. Secondly, since the particle size of CaF2 and MgF2 is extremely fine, it is difficult to filter. In this process, due to the need to add excessive fluorinating agent, F in the system - Exceeding the limit, therefore extraction method is required to remove F - , increasing production costs. Since the removal of Mg / Ca requires a long time and process, it is very easy to cause unstable product quality. Summary of the invention

[0005] In view of the problems that it is difficult to separate calcium and magnesium from manganese sulfate solution in the prior art, the prior method is time-consuming, difficult to filter, easily leads to excessive fluorine content in the solution, and increases production costs, the present invention adopts lignin to prepare an adsorbent with strong adsorption capacity for calcium and magnesium, and uses soybeans to modify the lignin to remove calcium and magnesium ions in the manganese sulfate solution. The method has a wide source of raw materials and is cheap. The obtained adsorbent has strong adsorption capacity and specificity. When it is used to remove calcium and magnesium in manganese sulfate, no new impurities are introduced, and low-cost, short-process and stable separation of calcium and magnesium in manganese sulfate solution can be achieved.

[0006] According to a first embodiment of the present invention, a calcium and magnesium adsorbent is provided.

[0007] A calcium and magnesium adsorbent is prepared by mixing lignin, soybeans and additives as raw materials.

[0008] Preferably, the additive is a bisulfate, preferably one or both of potassium bisulfate and sodium bisulfate.

[0009] Preferably, in the mixing reaction, the amount of hydrogen sulfate added is 0.5% to 2.4% of the mass of the lignin, preferably 1.0% to 2.0%.

[0010] Preferably, when modifying lignin with soybean, the liquid-to-solid ratio of soybean extract to lignin is 30-467 mL:1 g, preferably 80-240 mL:1 g.

[0011] According to a second embodiment of the present invention, a method for preparing a calcium and magnesium adsorbent is provided.

[0012] 1) mixing lignin and concentrated soybean extract, heating them, adding additives, stirring and reacting them to obtain a solid adsorbent product;

[0013] The preparation process of the concentrated soybean extract is as follows:

[0014] A) grinding soybeans into powder to obtain soybean powder, stirring and leaching the soybean powder with a solvent, and then centrifuging to obtain an extract and a leaching residue;

[0015] B) concentrating the leachate obtained in step A) to obtain a concentrated leachate.

[0016] Preferably, the additive in step 1) is a bisulfate, preferably one or both of potassium bisulfate and sodium bisulfate.

[0017] Preferably, in step 1), the liquid-to-solid ratio of the concentrated soybean extract to lignin is 4.5-14 mL:1 g, preferably 8-12 mL:1 g.

[0018] Preferably, the heating temperature in step 1) is 60-95°C, preferably 70-85°C.

[0019] Preferably, the stirring speed in step 1) is 100 to 450 rpm, preferably 200 to 350 rpm.

[0020] Preferably, the additive added in step 1) is in the range of 0.5% to 2.4%, preferably 1.0% to 2.0%, of the lignin mass.

[0021] Preferably, the reaction time in step 1) is 2 to 8 hours, preferably 4 to 6 hours.

[0022] Preferably, the solvent in step A) is deionized water.

[0023] Preferably, the liquid-to-solid ratio of the solvent to soybeans in step A) is 1-5 mL:1 g, preferably 2-4 mL:1 g.

[0024] Preferably, the average particle size of the soybean powder in step A) is 500-800 μm, preferably 600-700 μm.

[0025] Preferably, the stirring speed in step A) is 150-450 rpm, preferably 200-400 rpm.

[0026] Preferably, the leaching temperature in step A) is 50-90°C, preferably 60-80°C.

[0027] Preferably, the leaching time in step A) is 4 to 8 hours, preferably 5 to 7 hours.

[0028] Preferably, the centrifugal speed of the centrifugation in step A) is 1000-1500 rpm, preferably 1100-1400 rpm.

[0029] Preferably, the centrifugation time in step A) is 5 to 20 min, preferably 10 to 15 min.

[0030] Preferably, the volume of the concentrated leachate in step B) is 3% to 15%, preferably 5% to 10%, of the volume of the leachate.

[0031] Preferably, the step 1) is specifically as follows: lignin and concentrated soybean extract are mixed in a liquid-solid ratio of 4.5-14 mL: 1 g (preferably 8-12 mL: 1 g), then heated to 60-95° C. (preferably 70-85° C.), and then 0.5%-2.4% (preferably 1.0%-2.0%) of hydrogen sulfate by weight of lignin is added, and the mixture is stirred at a speed of 100-450 rpm (preferably 200-350 rpm) for 2-8 h (preferably 4-6 h) to obtain a solid adsorbent product.

[0032] Preferably, the step A) is specifically as follows: grinding soybeans into soybean powder with an average particle size of 500-800 μm (preferably 600-700 μm), and leaching with deionized water at a liquid-solid ratio of 1-5 mg:1 g (preferably 2-4 mg:1 g) at 50-90° C. (preferably 60-80° C.) for 4-8 h (preferably 5-7 h), and after leaching, centrifuging the solution at a speed of 1000-1500 rpm (preferably 1100-1400 rpm) for 5-20 min (preferably 10-15 min) to obtain an leaching solution and a leaching residue; and / or

[0033] The step B) specifically comprises: concentrating the leaching solution obtained in the step A) to 3% to 15% (preferably 5% to 10%) of the original volume to obtain a concentrated leaching solution.

[0034] According to a third embodiment of the present invention, a method for separating calcium and magnesium from manganese sulfate is provided.

[0035] An application of a calcium and magnesium adsorbent, the method comprising the following steps:

[0036] a) adding the solid adsorbent product obtained in step 1) to a manganese sulfate solution, adjusting the pH value to acidic, and filtering after the reaction is completed to obtain a manganese sulfate solution after impurities are removed.

[0037] Preferably, the amount of the solid adsorbent product added in step a) is 1-5 g / 100 mL, preferably 2-4 g / 100 mL.

[0038] Preferably, the acidity in step a) is a pH value of 2 to 6, preferably 3 to 5.

[0039] Preferably, the reaction time in step a) is 5 to 15 hours, preferably 7 to 13 hours.

[0040] Preferably, the step a) is specifically: adding the solid adsorbent product obtained in step 1) to the manganese sulfate solution at a mass of 1-5 g / 100 mL (preferably 2-4 g / 100 mL), adjusting the pH value of the solution to 2-6 (preferably 3-5), reacting for 5-15 h (preferably 7-13 h) and then filtering to obtain a manganese sulfate solution after impurities are removed.

[0041] In the present invention, since lignin has a certain adsorption capacity, it has a good adsorption effect on heavy metal ions. The present invention mixes lignin with soybeans and additives to obtain a solid adsorbent. The present invention uses lignin as a carrier and soybeans containing a large amount of phytic acid to modify lignin for the type and content of ions in the manganese sulfate solution during the battery production process. Lignin, as a carrier, is insoluble in acid solution and has a certain adsorption capacity for heavy metal ions. In addition, according to the hard and soft acid-base theory, calcium and magnesium ions and phytic acid are both particles with a higher charge density, that is, calcium and magnesium ions are hard acids, and phytic acid is a hard base. Phytic acid has a strong binding force on calcium and magnesium ions, and the hydroxyl groups in lignin can react with phytic acid to achieve the modification of lignin. After lignin is modified with phytic acid, the two synergistically adsorb calcium and magnesium ions in the solution, thereby improving the adsorption of lignin on calcium and magnesium ions and the specificity for calcium and magnesium ions.

[0042] In the present invention, soybean is selected as the source of phytic acid. Soybean is widely available and low in price, and is an excellent modifier suitable for modifying lignin. Among them, the liquid-solid ratio of solvent to soybean, the volume ratio of concentration, and the liquid-solid ratio of concentrated extract to lignin will all affect the final usage ratio of soybean to lignin. Based on a large number of experiments, this scheme finally determined that the liquid-to-solid ratio of solvent to soybean is 1-5mL:1g (for example, 1mL:1g, 1.2mL:1g, 1.4mL:1g, 1.6mL:1g, 1.8mL:1g, 2mL:1g, 2.4mL:1g, 2.8mL:1g, 3.2mL:1g, 3.6mL:1g, 4.0mL:1g, 4.2mL:1g, 4.4mL:1g, 4.6mL:1g, 4.8mL:1g, 5.0mL:1g), and the volume of concentrated leachate is 3%-15% of the volume of the original leachate (for example, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80 15%), the liquid-solid ratio of the concentrated extract to lignin is 4.5-14mL:1g (for example, 4.5mL:1g, 5mL:1g, 5.5mL:1g, 6mL:1g, 6.5mL:1g, 7mL:1g, 7.5mL:1g, 8mL:1g, 8.5mL:1g, 9mL:1g, 9.5mL:1g, 10mL:1g, 10.5mL:1g, 11mL:1g, 11.5mL:1g, 12mL:1g, 12.5mL:1g, 13mL:1g, 14mL:1g), within the above ratio range, the modification of lignin by soybean can greatly improve the adsorption of lignin to calcium and magnesium ions, as well as the selective specificity for calcium and magnesium ions.

[0043] In the present invention, compared with phosphoric acid, the present invention adopts the method of leaching and concentration to prepare soybean extract, and then adds the concentrated extract to lignin for modification to obtain an adsorbent. The adsorbent has high selectivity for calcium and magnesium ions, and basically does not adsorb other metal ions in the solution, while also avoiding the introduction of new impurities into the solution. Moreover, the adsorbent can be separated by filtration or centrifugation after adsorbing calcium and magnesium ions, and the operation is simple.

[0044] In the present invention, hydrogen sulfate is selected as an additive to accelerate the reaction rate during the modification of lignin. The amount of hydrogen sulfate added is limited to 0.5% to 2.4% of the mass of lignin (e.g., 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2.0%, 2.1%, 2.2%, 2.3%, 2.4%).

[0045] In the present invention, in the process of preparing the concentrated soybean extract, the soybean needs to be leached at 50-90° C. for 4-8 hours and then centrifuged to fully extract the phytic acid in the soybean.

[0046] In the present invention, the prepared solid adsorbent product is added to a manganese sulfate solution, and the pH value of the solution is adjusted to 2-6. Under acidic conditions, the lignin modified by phytic acid adsorbs calcium and magnesium ions in the manganese sulfate solution, and the lignin after adsorbing calcium and magnesium ions is filtered to obtain a manganese sulfate solution after impurities are removed.

[0047] In the present invention, the lignin and soybean in the adsorbent raw materials are widely available and low in price, and the prepared adsorbent material has cost advantages and good application prospects. The lignin used in the present invention is applicable to all types of lignin, including guaiacol lignin, guaiacol-sinapyl lignin, guaiacol-sinapyl lignin-p-hydroxyphenyl lignin. All coniferous wood lignin, broadleaf wood lignin, and gramineous lignin can be used in the process of the present invention.

[0048] Compared with the prior art, the present invention has the following beneficial effects:

[0049] 1. The present invention provides a calcium and magnesium adsorbent, which is a solid adsorbent made of lignin, soybeans and additives. It has a strong adsorption effect on calcium and magnesium ions. In addition, with respect to the type and content of ions in the manganese sulfate solution during the battery production process, the adsorbent provided by the present invention has excellent selectivity for calcium and magnesium, and will not cause the problem of decreased Mn recovery rate.

[0050] 2. The present invention provides a method for preparing a calcium and magnesium adsorbent. The raw materials lignin and soybean are widely available and low in price. The prepared adsorbent material has cost advantages, a simple preparation process, easy operation, and good application prospects.

[0051] 3. The application of the calcium and magnesium adsorbent provided by the present invention is simple in method and has good impurity removal effect on calcium and magnesium in manganese sulfate solution. DETAILED DESCRIPTION

[0052] The technical solution of the present invention is illustrated below by way of example, and the scope of protection requested by the present invention includes but is not limited to the following embodiments.

[0053] According to a first embodiment of the present invention, a calcium and magnesium adsorbent is provided.

[0054] A calcium and magnesium adsorbent is prepared by mixing lignin, soybeans and additives as raw materials.

[0055] Preferably, the additive is a bisulfate, preferably one or both of potassium bisulfate and sodium bisulfate.

[0056] Preferably, in the mixing reaction, the amount of hydrogen sulfate added is 0.5% to 2.4% of the mass of the lignin, preferably 1.0% to 2.0%.

[0057] Preferably, when modifying lignin with soybean, the liquid-to-solid ratio of soybean extract to lignin is 30-467 mL:1 g, preferably 80-240 mL:1 g.

[0058] According to a second embodiment of the present invention, a method for preparing a calcium and magnesium adsorbent is provided.

[0059] 1) mixing lignin and concentrated soybean extract, heating them, adding additives, stirring and reacting them to obtain a solid adsorbent product;

[0060] The preparation process of the concentrated soybean extract is as follows:

[0061] A) grinding soybeans into powder to obtain soybean powder, stirring and leaching the soybean powder with a solvent, and then centrifuging to obtain an extract and a leaching residue;

[0062] B) concentrating the leachate obtained in step A) to obtain a concentrated leachate.

[0063] Preferably, the additive in step 1) is a bisulfate, preferably one or both of potassium bisulfate and sodium bisulfate.

[0064] Preferably, in step 1), the liquid-to-solid ratio of the concentrated soybean extract to lignin is 4.5-14 mL:1 g, preferably 8-12 mL:1 g.

[0065] Preferably, the heating temperature in step 1) is 60-95°C, preferably 70-85°C.

[0066] Preferably, the stirring speed in step 1) is 100 to 450 rpm, preferably 200 to 350 rpm.

[0067] Preferably, the additive added in step 1) is in the range of 0.5% to 2.4%, preferably 1.0% to 2.0%, of the lignin mass.

[0068] Preferably, the reaction time in step 1) is 2 to 8 hours, preferably 4 to 6 hours.

[0069] Preferably, the solvent in step A) is deionized water.

[0070] Preferably, the liquid-to-solid ratio of the solvent to soybeans in step A) is 1-5 mL:1 g, preferably 2-4 mL:1 g.

[0071] Preferably, the average particle size of the soybean powder in step A) is 500-800 μm, preferably 600-700 μm.

[0072] Preferably, the stirring speed in step A) is 150-450 rpm, preferably 200-400 rpm.

[0073] Preferably, the leaching temperature in step A) is 50-90°C, preferably 60-80°C.

[0074] Preferably, the leaching time in step A) is 4 to 8 hours, preferably 5 to 7 hours.

[0075] Preferably, the centrifugal speed of the centrifugation in step A) is 1000-1500 rpm, preferably 1100-1400 rpm.

[0076] Preferably, the centrifugation time in step A) is 5 to 20 min, preferably 10 to 15 min.

[0077] Preferably, the volume of the concentrated leachate in step B) is 3% to 15%, preferably 5% to 10%, of the volume of the leachate.

[0078] Preferably, the step 1) is specifically as follows: lignin and concentrated soybean extract are mixed in a liquid-solid ratio of 4.5-14 mL: 1 g (preferably 8-12 mL: 1 g), then heated to 60-95° C. (preferably 70-85° C.), and then 0.5%-2.4% (preferably 1.0%-2.0%) of hydrogen sulfate by weight of lignin is added, and the mixture is stirred at a speed of 100-450 rpm (preferably 200-350 rpm) for 2-8 h (preferably 4-6 h) to obtain a solid adsorbent product.

[0079] Preferably, the step A) is specifically as follows: grinding soybeans into soybean powder with an average particle size of 500-800 μm (preferably 600-700 μm), and leaching with deionized water at a liquid-solid ratio of 1-5 mg:1 g (preferably 2-4 mg:1 g) at 50-90° C. (preferably 60-80° C.) for 4-8 h (preferably 5-7 h), and after leaching, centrifuging the solution at a speed of 1000-1500 rpm (preferably 1100-1400 rpm) for 5-20 min (preferably 10-15 min) to obtain an leaching solution and a leaching residue; and / or

[0080] The step B) specifically comprises: concentrating the leaching solution obtained in the step A) to 3% to 15% (preferably 5% to 10%) of the original volume to obtain a concentrated leaching solution.

[0081] According to a third embodiment of the present invention, a method for separating calcium and magnesium from manganese sulfate is provided.

[0082] An application of a calcium and magnesium adsorbent, the method comprising the following steps:

[0083] a) adding the solid adsorbent product obtained in step 1) to a manganese sulfate solution, adjusting the pH value to acidic, and filtering after the reaction is completed to obtain a manganese sulfate solution after impurities are removed.

[0084] Preferably, the amount of the solid adsorbent product added in step a) is 1-5 g / 100 mL, preferably 2-4 g / 100 mL.

[0085] Preferably, the acidity in step a) is a pH value of 2 to 6, preferably 3 to 5.

[0086] Preferably, the reaction time in step a) is 5 to 15 hours, preferably 7 to 13 hours.

[0087] Preferably, the step a) is specifically: adding the solid adsorbent product obtained in step 1) to the manganese sulfate solution at a mass of 1-5 g / 100 mL (preferably 2-4 g / 100 mL), adjusting the pH value of the solution to 2-6 (preferably 3-5), reacting for 5-15 h (preferably 7-13 h) and then filtering to obtain a manganese sulfate solution after impurities are removed.

[0088] Example 1

[0089] A method for separating calcium and magnesium from a manganese sulfate solution comprises the following steps:

[0090] (A) 300 g of soybeans were crushed and ground to obtain soybean powder with an average particle size of 625 μm. 600 mL of deionized water was added to the soybean powder, and the mixture was heated to 70°C and stirred and timed. The stirring speed was 200 rpm and the leaching time was 5 h. After the reaction was completed, the slurry was centrifuged at a centrifuge speed of 1200 rpm and a centrifugation time of 15 min. After centrifugation, 600 mL of leaching solution and 278 g of leaching residue were obtained.

[0091] (B) The leachate is evaporated and concentrated, and the volume of the solution is evaporated to 25 mL, thereby obtaining 25 mL of concentrated leachate.

[0092] (1) 5 g of lignin was placed in a three-necked flask, 25 mL of concentrated extract obtained in step B) was added, and heating was started. After the temperature rose to 70° C., 50 mg of potassium hydrogen sulfate was added, and the stirring device was turned on to start the reaction. The reaction time was 4 h. After the reaction was completed, the solid adsorbent product was obtained by filtering and washing.

[0093] (a) 2 g of the solid adsorbent product was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 3, and the reaction was oscillated for 10 h. After the treatment, the manganese sulfate solution was filtered, and the calcium and magnesium powder contents in the manganese sulfate solution were reduced from 532 mg / L and 1024 mg / L to 32 mg / L and 24 mg / L, respectively.

[0094] Example 2

[0095] A method for separating calcium and magnesium from a manganese sulfate solution comprises the following steps:

[0096] (A) 300 g of soybeans were crushed and ground to obtain soybean powder with an average particle size of 625 μm. 1200 mL of deionized water was added to the soybean powder, and the mixture was heated to 60°C and stirred and timed. The stirring speed was 300 rpm and the leaching time was 6 h. After the reaction was completed, the slurry was centrifuged at a centrifuge speed of 1300 rpm and a centrifugation time of 13 min. After centrifugation, 1200 mL of leaching solution and 246 g of leaching residue were obtained.

[0097] (B) The leachate was concentrated by evaporation, and the volume of the solution was evaporated to 144 mL, thereby obtaining 144 mL of concentrated leachate.

[0098] (1) 5 g of lignin was placed in a three-necked flask, 70 mL of concentrated extract obtained in step B) was added, and heating was started. After the temperature rose to 75° C., 95 mg of potassium hydrogen sulfate was added, and the stirring device was turned on to start the reaction. The reaction time was 5 h. After the reaction was completed, the solid adsorbent product was obtained by filtration and washing.

[0099] (a) 5 g of the solid adsorbent product was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 5, and the reaction was oscillated for 8 hours. After the treatment was completed, the manganese sulfate solution was filtered to obtain a manganese sulfate solution after impurities were removed.

[0100] Example 3

[0101] A method for separating calcium and magnesium from a manganese sulfate solution comprises the following steps:

[0102] (A) 300 g of soybeans were crushed and ground to obtain soybean powder with an average particle size of 625 μm. 750 mL of deionized water was added to the soybean powder, heated to 70°C, stirred and timed, the stirring speed was 250 rpm, and the leaching time was 7 h. After the reaction was completed, the slurry was centrifuged at a centrifuge speed of 1400 rpm and a centrifugation time of 10 min. After centrifugation, 750 mL of leaching solution and 262 g of leaching residue were obtained.

[0103] (B) The leachate is evaporated and concentrated, and the volume of the solution is evaporated to 45 mL, thereby obtaining 45 mL of concentrated leachate.

[0104] (1) 5 g of lignin was placed in a three-necked flask, 45 mL of concentrated extract obtained in step B) was added, and heating was started. After the temperature rose to 85° C., 65 mg of potassium hydrogen sulfate was added, and the stirring device was turned on to start the reaction. The reaction time was 3 h. After the reaction was completed, the solid adsorbent product was obtained by filtration and washing.

[0105] (a) 4 g of the solid adsorbent product was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 2, and the reaction was oscillated for 7 hours. After the treatment was completed, the manganese sulfate solution was filtered to obtain a manganese sulfate solution after impurities were removed.

[0106] Example 4

[0107] A method for separating calcium and magnesium from a manganese sulfate solution comprises the following steps:

[0108] (A) 300 g of soybeans were crushed and ground to obtain soybean powder with an average particle size of 625 μm. 1200 mL of deionized water was added to the soybean powder, and the mixture was heated to 65°C and stirred and timed. The stirring speed was 350 rpm and the leaching time was 5 h. After the reaction was completed, the slurry was centrifuged at a centrifuge speed of 1100 rpm and a centrifugation time of 15 min. After centrifugation, 1200 mL of leaching solution and 249 g of leaching residue were obtained.

[0109] (B) The leachate was concentrated by evaporation, and the volume of the solution was evaporated to 108 mL, thereby obtaining 108 mL of concentrated leachate.

[0110] (1) 5 g of lignin was placed in a three-necked flask, 45 mL of concentrated extract obtained in step B) was added, and heating was started. After the temperature rose to 65° C., 85 mg of potassium hydrogen sulfate was added, and the stirring device was turned on to start the reaction. The reaction time was 4 h. After the reaction was completed, the solid adsorbent product was obtained by filtration and washing.

[0111] (a) 2.5 g of the solid adsorbent product was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 3, and the reaction was oscillated for 10 hours. After the treatment was completed, the manganese sulfate solution was filtered to obtain a manganese sulfate solution after impurities were removed.

[0112] Example 5

[0113] A method for separating calcium and magnesium from a manganese sulfate solution comprises the following steps:

[0114] (A) 300 g of soybeans were crushed and ground to obtain soybean powder with an average particle size of 625 μm. 600 mL of deionized water was added to the soybean powder, and the mixture was heated to 70°C and stirred and timed. The stirring speed was 300 rpm and the leaching time was 6 h. After the reaction was completed, the slurry was centrifuged at a centrifuge speed of 1200 rpm and a centrifugation time of 13 min. After centrifugation, 600 mL of leaching solution and 267 g of leaching residue were obtained.

[0115] (B) The leachate was concentrated by evaporation, and the volume of the solution was evaporated to 48 mL, thereby obtaining 48 mL of concentrated leachate.

[0116] (1) 5 g of lignin was placed in a three-necked flask, 48 mL of concentrated extract obtained in step B) was added, and heating was started. After the temperature rose to 70° C., 75 mg of potassium hydrogen sulfate was added, and the stirring device was turned on to start the reaction. The stirring speed was 300 rpm, and the reaction time was 5 h. After the reaction was completed, the solid adsorbent product was obtained by filtration and washing.

[0117] (a) 3 g of the solid product was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 4, and the reaction was oscillated for 10 h. After the treatment was completed, the manganese sulfate solution was filtered to obtain a manganese sulfate solution after impurities were removed.

[0118] Example 6

[0119] A method for separating calcium and magnesium from a manganese sulfate solution comprises the following steps:

[0120] (A) 300 g of soybeans were crushed and ground to obtain soybean powder with an average particle size of 625 μm. 900 mL of deionized water was added to the soybean powder, and the mixture was heated to 70°C and stirred and timed. The stirring speed was 300 rpm and the leaching time was 6 h. After the reaction was completed, the slurry was centrifuged at a centrifuge speed of 1200 rpm and a centrifugation time of 13 min. After centrifugation, 900 mL of leaching solution and 263 g of leaching residue were obtained.

[0121] (B) The leachate was concentrated by evaporation, and the volume of the solution was evaporated to 72 mL, thereby obtaining 72 mL of concentrated leachate.

[0122] (1) 5 g of lignin was placed in a three-necked flask, 50 mL of concentrated extract obtained in step B) was added, and heating was started. After the temperature rose to 70° C., 75 mg of potassium hydrogen sulfate was added, and the stirring device was turned on to start the reaction. The stirring speed was 300 rpm, and the reaction time was 5 h. After the reaction was completed, the solid adsorbent product was obtained by filtration and washing.

[0123] (a) 3 g of the solid adsorbent product was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 4, and the reaction was oscillated for 10 hours. After the treatment was completed, the manganese sulfate solution was filtered to obtain a manganese sulfate solution after impurities were removed.

[0124] Example 7

[0125] Example 6 was repeated, except that the amount of deionized water added in step A) was 1200 mL, and the volume of the concentrated leachate in step B) was 96 mL.

[0126] Example 8

[0127] Example 6 was repeated, except that the amount of deionized water added in step A) was 300 mL, the volume of the concentrated leachate in step B) was 24 mL, and the amount of the concentrated leachate added in step 1) was 24 mL.

[0128] Example 9

[0129] Example 6 was repeated, except that the amount of deionized water added in step A) was 1500 mL, and the volume of the concentrated leachate in step B) was 120 mL.

[0130] Example 10

[0131] Example 6 was repeated, except that the volume of the concentrated leachate in step B) was 45 mL, and the amount of the concentrated leachate added in step 1) was 45 mL.

[0132] Embodiment 11

[0133] Example 6 was repeated except that the volume of the concentrated leachate in step B) was 90 mL.

[0134] Example 12

[0135] Example 6 was repeated, except that the volume of the concentrated leachate in step B) was 30 mL, and the amount of the concentrated leachate added in step 1) was 30 mL.

[0136] Example 13

[0137] Example 6 was repeated except that the volume of the concentrated leachate in step B) was 135 mL.

[0138] Embodiment 14

[0139] Example 6 was repeated, except that the amount of concentrated leachate added in step 1) was 40 mL.

[0140] Embodiment 15

[0141] Example 6 was repeated, except that the amount of concentrated leachate added in step 1) was 60 mL.

[0142] Example 16

[0143] Example 6 was repeated, except that the amount of concentrated leachate added in step 1) was 25 mL.

[0144] Embodiment 17

[0145] Example 6 was repeated, except that the amount of concentrated leachate added in step 1) was 70 mL.

[0146] Embodiment 18

[0147] Example 6 was repeated, except that the amount of potassium hydrogen sulfate added in step 1) was 50 mg.

[0148] Embodiment 19

[0149] Example 6 was repeated, except that the amount of potassium hydrogen sulfate added in step 1) was 100 mg.

[0150] Embodiment 20

[0151] Example 6 was repeated, except that the amount of potassium hydrogen sulfate added in step 1) was 25 mg.

[0152] Embodiment 21

[0153] Example 6 was repeated, except that the amount of potassium hydrogen sulfate added in step 1) was 120 mg.

[0154] Embodiment 22

[0155] Example 6 was repeated, except that the amount of solid adsorbent product added in step 2) was 2 g.

[0156] Embodiment 23

[0157] Example 6 was repeated except that the amount of solid adsorbent product added in step 2) was 4 g.

[0158] Embodiment 24

[0159] Example 6 was repeated, except that the amount of solid adsorbent product added in step 2) was 1 g.

[0160] Embodiment 25

[0161] Example 6 was repeated, except that the amount of solid adsorbent product added in step 2) was 5 g.

[0162] Comparative Example 1

[0163] Example 6 was repeated except that the concentrated leachate was not added in step 1).

[0164] Comparative Example 2

[0165] Example 6 was repeated except that potassium bisulfate was not added in step 1).

[0166] Comparative Example 3

[0167] (A) 300 g of soybeans were crushed and ground to obtain soybean powder with an average particle size of 625 μm.

[0168] (1) 200 g of soybean powder was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 4, and the reaction was oscillated for 10 hours. After the treatment was completed, the manganese sulfate solution was filtered to obtain a manganese sulfate solution after impurities were removed.

[0169] Comparative Example 4

[0170] Example 6 was repeated, except that the amount of deionized water added in step A) was 2400 mL, and the volume of the concentrated leachate in step B) was 192 mL.

[0171] Comparative Example 5

[0172] Example 6 was repeated, except that the volume of the concentrated leachate in step B) was 27 mL, and the amount of the concentrated leachate added in step 1) was 27 mL.

[0173] Comparative Example 6

[0174] Example 6 was repeated except that the volume of the concentrated leachate in step B) was 144 mL.

[0175] Comparative Example 7

[0176] Example 6 was repeated, except that the amount of concentrated leachate added in step 1) was 15 mL.

[0177] Comparative Example 8

[0178] Example 6 was repeated, except that the amount of the additive added in step 1) was 15 mg.

[0179] Comparative Example 9

[0180] Example 6 was repeated, except that the amount of the additive added in step 1) was 150 mg.

[0181] Comparative Example 10

[0182] Example 6 was repeated, except that the amount of solid adsorbent product added in step 2) was 0.5 g.

[0183] Comparative Example 11

[0184] Example 6 was repeated except that the amount of solid adsorbent product added in step 2) was 7 g.

[0185] Comparative Example 12

[0186] A method for preparing an adsorbent for separating calcium and magnesium comprises the following steps:

[0187] (1) Take 5g of lignin and put it in a three-necked flask, add 10mL of phosphoric acid, start heating, and after the temperature rises to 70°C, add 75mg of potassium hydrogen sulfate, turn on the stirring device to start the reaction, the stirring speed is 300rpm, and the reaction time is 5h. After the reaction is completed, filter and wash to obtain a solid adsorbent product.

[0188] (2) 3 g of the solid adsorbent product was added to 100 mL of manganese sulfate solution, the pH of the solution was adjusted to 4, and the reaction was oscillated for 10 hours. After the treatment was completed, the manganese sulfate solution was filtered to obtain a manganese sulfate solution after impurities were removed.

[0189] Some experimental parameters in Examples 1 to 25 and Comparative Examples 1 to 12 are shown in Table 1.

[0190] The initial contents of various ions in the manganese sulfate solutions described in Examples 1 to 25 and Comparative Examples 1 to 12: Mn 2+ 19.62 g / L, Mg 2+ 1124mg / L, Ca 2+ The Mn content of the manganese sulfate solution after impurities removal is 469 mg / L. 2+ Mg 2+ , Ca 2+ The content of was tested, and the test results are shown in Table 2.

[0191] Table 1

[0192]

[0193]

[0194]

[0195] Table 2

[0196]

[0197]

[0198] According to the above experimental results, the calcium and magnesium adsorbent provided by the present invention improves the adsorption of calcium and magnesium ions and the selectivity of calcium and magnesium ions by modifying lignin with soybeans, and at the same time limits the dosage ratio of each substance, so that the comprehensive performance of the adsorption and selectivity of the prepared adsorbent for calcium and magnesium ions is within the optimal range. Compared with existing adsorbents, the adsorbent provided by the present invention has obvious advantages in the selectivity of calcium and magnesium ions.

Claims

1. A calcium and magnesium adsorbent, characterized in that: The adsorbent is prepared by mixing lignin, soybean and additives as raw materials.

2. The adsorbent according to claim 1, characterized in that: The additive is a bisulfate, preferably one or both of potassium bisulfate and sodium bisulfate.

3. The adsorbent according to claim 1 or 2, characterized in that: In the mixed reaction, the amount of hydrogen sulfate added is 0.5% to 2.4% of the lignin mass, preferably 1.0% to 2.0%; and / or When soybean is used to modify lignin, the liquid-to-solid ratio of soybean extract to lignin is 30-467 mL:1 g, preferably 80-240 mL:1 g.

4. A method for preparing a calcium and magnesium adsorbent or a method for preparing the adsorbent according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: 1) mixing lignin and concentrated soybean extract, heating them, adding additives, stirring and reacting them to obtain a solid adsorbent product; The preparation process of the concentrated soybean extract is as follows: A) grinding soybeans into powder to obtain soybean powder, stirring and leaching the soybean powder with a solvent, and then centrifuging to obtain an extract and a leaching residue; B) concentrating the leachate obtained in step A) to obtain a concentrated leachate.

5. The method according to claim 4, characterized in that: The additive in step 1) is a bisulfate, preferably one or both of potassium bisulfate and sodium bisulfate; and / or In the step 1), the liquid-to-solid ratio of the concentrated soybean extract to the lignin is 4.5-14 mL:1 g, preferably 8-12 mL:1 g; and / or The heating temperature in step 1) is 60-95°C, preferably 70-85°C; and / or The stirring speed in step 1) is 100 to 450 rpm, preferably 200 to 350 rpm; and / or The amount of the additive added in step 1) is 0.5% to 2.4% of the lignin mass, preferably 1.0% to 2.0%; and / or The reaction time in step 1) is 2 to 8 hours, preferably 4 to 6 hours.

6. The method according to claim 4 or 5, characterized in that: The solvent in step A) is deionized water; and / or The liquid-to-solid ratio of the solvent to soybean in step A) is 1-5 mL:1 g, preferably 2-4 mL:1 g; and / or The average particle size of the soybean powder in step A) is 500-800 μm, preferably 600-700 μm; and / or The stirring speed in step A) is 150 to 450 rpm, preferably 200 to 400 rpm; and / or The leaching temperature in step A) is 50-90°C, preferably 60-80°C; and / or The leaching time in step A) is 4 to 8 hours, preferably 5 to 7 hours; and / or The centrifugal speed of the centrifugation in step A) is 1000-1500 rpm, preferably 1100-1400 rpm; and / or The centrifugation time in step A) is 5 to 20 minutes, preferably 10 to 15 minutes; and / or The volume of the concentrated leaching solution in step B) is 3% to 15% of the volume of the leaching solution, preferably 5% to 10%.

7. The method according to any one of claims 4 to 6, characterized in that: The step 1) is specifically as follows: lignin and soybean concentrated extract are mixed at a liquid-solid ratio of 4.5-14 mL:1 g (preferably 8-12 mL:1 g), and then heated to 60-95° C. (preferably 70-85° C.), and then 0.5%-2.4% (preferably 1.0%-2.0%) of hydrogen sulfate by weight of lignin is added, and the mixture is stirred at a speed of 100-450 rpm (preferably 200-350 rpm) for 2-8 h (preferably 4-6 h) to obtain a solid adsorbent product; and / or The step A) specifically comprises: grinding soybeans into soybean powder with an average particle size of 500-800 μm (preferably 600-700 μm), and leaching with deionized water at a liquid-solid ratio of 1-5 mg:1 g (preferably 2-4 mg:1 g) at 50-90° C. (preferably 60-80° C.) for 4-8 h (preferably 5-7 h), and after leaching, centrifuging the solution at a speed of 1000-1500 rpm (preferably 1100-1400 rpm) for 5-20 min (preferably 10-15 min) to obtain an leaching solution and a leaching residue; and / or The step B) specifically comprises: concentrating the leaching solution obtained in the step A) to 3% to 15% (preferably 5% to 10%) of the original volume to obtain a concentrated leaching solution.

8. A method for separating calcium and magnesium from a manganese sulfate solution or the use of the calcium and magnesium adsorbent according to any one of claims 1 to 3, characterized in that: The method comprises the following steps: a) adding the solid adsorbent product obtained in step 1) to a manganese sulfate solution, adjusting the pH value to acidic, and filtering after the reaction is completed to obtain a manganese sulfate solution after impurities are removed.

9. The method according to claim 8, characterized in that: The amount of the solid adsorbent product added in step a) is 1 to 5 g / 100 mL, preferably 2 to 4 g / 100 mL; and / or The acidity in step a) is a pH value of 2 to 6, preferably 3 to 5; and / or The reaction time in step a) is 5 to 15 hours, preferably 7 to 13 hours.

10. The method according to claim 8 or 9, characterized in that: The step a) is specifically as follows: adding the solid adsorbent product obtained in step 1) to the manganese sulfate solution at a mass of 1-5 g / 100 mL (preferably 2-4 g / 100 mL), adjusting the pH value of the solution to 2-6 (preferably 3-5), reacting for 5-15 h (preferably 7-13 h) and then filtering to obtain a manganese sulfate solution after impurities are removed.

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