A method for preparing a sulfonated x-type molecular sieve with high efficiency of screening potassium ions and sodium ions

Abstract

The application discloses a preparation method of sulfonated X-type molecular sieve for efficiently screening potassium ions and sodium ions, and the method is as follows: (1) placing NaX molecular sieve in a beaker; (2) adding deionized water to stir, and then pouring out waste liquid after washing after natural settlement; (3) re-adding deionized water to repeat (2) to sufficiently wash the molecular sieve; (4) drying the washed molecular sieve to obtain a molecular sieve to be modified; (5) placing the molecular sieve to be modified in a beaker, adding sulfuric acid solution to stir at room temperature; (6) after the stirring is completed, after the molecular sieve is completely settled, pouring out reaction waste liquid; (7) adding deionized water to stir to sufficiently wash the molecular sieve, and then standing; (8) repeating (7) until the pH of the washing liquid is 7; (9) drying the washed molecular sieve to obtain the sulfonated X-type molecular sieve after modification. The raw material cost of the application is low, the synthesis and molding are easy, and the application is suitable for industrialized large-scale production.

Description

TECHNICAL FIELD

[0001] The present application relates to a kind of molecular sieve, and specifically to a kind of preparation method of high-efficiency sieving potassium ion and sodium ion sulfonated X-type molecular sieve. BACKGROUND

[0002] As an important raw material of traditional chemical industry and new energy industry, monovalent cation resources are concerned. Most of them are stored in seawater, salt lake, etc. Effective enrichment and separation of monovalent cations in them has become one of the most challenging projects today. Especially for the extraction of potassium ion and sodium ion in abundant seawater resources, the two are similar in nature and structure, and it is very difficult to separate them. The concentration of sodium ion in seawater is more than 20 times that of potassium ion, and the enrichment of potassium ion is an important step for potassium extraction. The hydrated radius of sodium ion and potassium ion differs by angstrom level. To accurately screen, the size of the separation channel should be controlled, and the cost of COF membrane with angstrom level is huge, which is not suitable for industrial production. And the preparation of waste liquid is toxic and pollutes the environment. SUMMARY

[0003] In order to make up for the defects of the prior art, the present application provides a preparation method of high-efficiency sieving potassium ion and sodium ion sulfonated X-type molecular sieve. The method uses X-type molecular sieve with appropriate pore size, and the pore size is about 13 angstrom. By sulfonating the X-type molecular sieve, the size of the pore is further modified, so that it is between the intermediate value of hydrated potassium ion and hydrated sodium ion, thereby realizing the effective screening of potassium ion and sodium ion. The raw material cost of the present application is low, easy to synthesize and form, and suitable for industrial large-scale production.

[0004] The purpose of the present application is achieved by the following technical scheme:

[0005] A preparation method of high-efficiency sieving potassium ion and sodium ion sulfonated X-type molecular sieve, comprising the following steps:

[0006] Step (1) place 40-60g industrialized NaX molecular sieve in a beaker or sieve after ball milling;

[0007] Step (2) add 2-4 times the mass of deionized water to the molecular sieve and stir, then pour out the waste liquid after washing, control the stirring speed at 100-500 revolutions per minute, and the time is 5-15 minutes;

[0008] Step (3) add 2-4 times the mass of deionized water to the molecular sieve, repeat step (2) until there is no impurity in the deionized water, and the molecular sieve is washed thoroughly;

[0009] Step (4) dry the washed molecular sieve to obtain the modified molecular sieve, control the drying temperature at 60-80℃, and the time is 10-30h;

[0010] Step (5) places the molecular sieve to be modified in a beaker, adds a sulfuric acid solution of 3-5 times the mass of the molecular sieve, stirs at room temperature, controls the stirring speed to be 500-1000 revolutions per minute, the time is 30-120 minutes, and the concentration of the sulfuric acid solution is 0.1-1 mol / L;

[0011] Step (6) after stirring, stands for 5-15 minutes, pours out the reaction waste liquid after the molecular sieve is completely settled;

[0012] Step (7) adds deionized water of 3-5 times the mass of the molecular sieve to stir and sufficiently wash the molecular sieve, stands, tests the pH value of the washing liquid, and controls the stirring speed to be 100-500 revolutions per minute, and the time is 5-15 minutes;

[0013] Step (8) repeats the above step (7) until the pH value of the washing liquid is 7, and the washing of the molecular sieve is completed;

[0014] Step (9) pours out the washing liquid, dries the washed molecular sieve, and obtains the modified sulfonated X-type molecular sieve, controls the drying temperature to be 60-80 DEG C, and the time is 20-30 hours.

[0015] Compared with the prior art, the present application has the following advantages:

[0016] 1. The present application uses industrialized NaX molecular sieve as raw material, and the cost is low. The wet modification is used when the molecular sieve is modified, and the modification purpose can be achieved at room temperature, the operation is safe, and the synthesis is easy.

[0017] 2. The present application modifies the sulfonic acid group on the original pore of the NaX molecular sieve, changes the original pore size, makes it between the hydrated potassium ion and the hydrated sodium ion, and realizes the effective screening of the potassium ion and the sodium ion.

[0018] 3. The present application uses sulfuric acid as the raw material for sulfonation, and the sufficient hydrogen ion can exist as the cation for balancing the negative charge in the molecular sieve, so that most of the sodium ions in the molecular sieve are exchanged, which does not affect the subsequent ion screening process, and the hydrogen ion as the cation for balancing the charge can improve the original pore volume compared with the sodium ion. DETAILED DESCRIPTION

[0019] The technical scheme of the present application is further described below in combination with examples, but is not limited thereto. Any modification or equivalent replacement to the technical scheme of the present application without departing from the spirit and scope of the present application shall be covered in the protection scope of the present application.

[0020] Example 1

[0021] The present embodiment provides a sulfonated X-type molecular sieve which can efficiently screen potassium ions and sodium ions, and the sulfonated X-type molecular sieve is prepared by using NaX-type molecular sieve, 0.5 mol / L sulfuric acid as raw materials, and the specific method is as follows: -1 The present embodiment provides a sulfonated X-type molecular sieve which can efficiently screen potassium ions and sodium ions, and the sulfonated X-type molecular sieve is prepared by using NaX-type molecular sieve, 0.5 mol / L sulfuric acid as raw materials, and the specific method is as follows:

[0022] Step (1) 50g of industrialized NaX molecular sieve is placed in a 250ml beaker.

[0023] Step (2) 200ml of deionized water is added and stirred on the stirring table at a speed of 200r / min for 10min, the beaker is taken out and allowed to settle naturally, and the waste liquid after washing is poured out.

[0024] Step (3) 200ml of deionized water is added again, and the above step (2) is repeated three times until there is no impurity in the deionized water, and the molecular sieve is washed thoroughly.

[0025] Step (4) the washed molecular sieve is placed in a blast drying oven and dried at 60℃ for 24h until completely dry, obtaining the modified molecular sieve.

[0026] Step (5) the modified molecular sieve is placed in a 250ml beaker, and a 0.5mol / L sulfuric acid solution is prepared, 200ml of which is added in the beaker and placed on the stirring table, and stirred at a speed of 500r / min at room temperature for 60min.

[0027] Step (6) after stirring, it is allowed to stand for 10min, and after the molecular sieve is completely settled, the reaction waste liquid is poured out.

[0028] Step (7) 200ml of deionized water is added and stirred on the stirring table at a speed of 200r / min for 5min to wash the molecular sieve thoroughly, and after stirring, it is taken out and allowed to stand, and the pH value of the washing liquid is tested.

[0029] Step (8) the above step (7) is repeated until the pH value of the washing liquid after washing and settling is 7, which proves that the washing of the molecular sieve is completed.

[0030] Step (9) part of the washing liquid is taken out, centrifuged, and the content of sodium element therein is tested by icp, which proves that the sodium in the molecular sieve is completely exchanged.

[0031] Step (10) the washing liquid is poured out, and the washed molecular sieve is placed in a blast drying oven and dried at 60℃ for 24h until completely dry, obtaining the modified sulfonated X-type molecular sieve.

[0032] The molecular sieve of the embodiment is subjected to performance test, 50 g of the molecular sieve is placed in a zeolite exchange column with filter membrane on the top and bottom to prevent powder leakage. A solution is prepared according to the concentration of potassium ions and sodium ions in seawater, and is passed through the zeolite exchange column from top to bottom. The solution after exchange is taken out and subjected to icp test for three times. Most of the potassium ions are intercepted by the molecular sieve, and the ratio of potassium ions to sodium ions in the molecular sieve is about 1:2.2, which is much higher than the ratio in seawater, and the efficient enrichment of potassium ions is realized.

[0033] Embodiment 2

[0034] The embodiment provides a low-sulfonated X-type molecular sieve for efficiently screening potassium ions and sodium ions. The low-sulfonated X-type molecular sieve is prepared from NaX-type molecular sieve, 0.1 mol / L sulfuric acid as raw material, and the specific method is as follows: -1

[0035] Step (1) 50 g of industrialized NaX molecular sieve is placed in a 250 ml beaker.

[0036] Step (2) 200 ml of deionized water is added and stirred on a stirring table at a speed of 200 revolutions per minute for 10 minutes. The beaker is taken out and allowed to naturally settle, and the waste liquid after washing is poured out.

[0037] Step (3) 200 ml of deionized water is added again, and the above step (2) is repeated three times until there is no impurity in the deionized water, and the molecular sieve is washed thoroughly.

[0038] Step (4) the washed molecular sieve is placed in a blast drying oven and dried at 60°C for 24 hours until completely dry, to obtain the modified molecular sieve.

[0039] Step (5) the modified molecular sieve is placed in a 250 ml beaker, and a 0.1 mol / L sulfuric acid solution is prepared and added to the beaker at 200 ml. It is placed on a stirring table and stirred at a speed of 500 revolutions per minute at room temperature for 60 minutes.

[0040] Step (6) after stirring, it is allowed to stand for 10 minutes, and after the molecular sieve is completely settled, the reaction waste liquid is poured out.

[0041] Step (7) 200 ml of deionized water is added and stirred on a stirring table at a speed of 200 revolutions per minute for 5 minutes to thoroughly wash the molecular sieve. After stirring, it is taken out and allowed to stand, and the pH value of the washing liquid is tested.

[0042] Step (8) the above step (7) is repeated until the pH value of the washing liquid after washing and settling is 7, which proves that the washing of the molecular sieve is completed.

[0043] Step (9) part of the washing liquid is taken out, centrifuged, and the content of sodium element therein is tested by icp to prove that the sodium in the molecular sieve is completely exchanged.​

[0044] Step (10) pour out the washing liquid, and place the washed molecular sieve into a blast drying oven, dry at 60°C for 24h until completely dry, to obtain the modified sulfonated X-type molecular sieve.

[0045] The performance of the molecular sieve of the present embodiment was tested. 50g of the molecular sieve was placed into a filter membrane from top to bottom to prevent powder leakage, and was placed into a zeolite exchange column. A solution was prepared according to the concentration of potassium ions and sodium ions in seawater, and was passed through the zeolite exchange column from top to bottom. The solution after exchange was taken out and tested by ICP three times. Most of the potassium ions were intercepted by the molecular sieve, and the ratio of potassium ions to sodium ions in the molecular sieve was about 1:1.8, which was much higher than the ratio in seawater, and high-efficiency enrichment of potassium ions was achieved.

[0046] Embodiment 3

[0047] The present embodiment provides a high-efficiency potassium ion and sodium ion screening sulfonated X-type molecular sieve with high sulfonation degree, which is prepared from NaX-type molecular sieve, 1mol / L sulfuric acid as raw material, and the specific method is as follows: -1

[0048] Step (1) 50g of industrialized NaX molecular sieve was placed in a 250ml beaker.

[0049] Step (2) 200ml of deionized water was added and stirred on the stirring table at a speed of 200rpm for 10min, the beaker was taken out and allowed to settle naturally, and the waste liquid after washing was poured out.

[0050] Step (3) 200ml of deionized water was added again, and the above step (2) was repeated three times until there was no impurity in the deionized water, and the molecular sieve was washed thoroughly.

[0051] Step (4) the washed molecular sieve was placed into a blast drying oven, dried at 60°C for 24h until completely dry, to obtain the modified molecular sieve.

[0052] Step (5) the modified molecular sieve was placed in a 250ml beaker, and a 1mol / L sulfuric acid solution was prepared, 200ml of which was added into the beaker and placed on the stirring table, and stirred at a speed of 500rpm at room temperature for 60min.

[0053] Step (6) after stirring, it was allowed to stand for 10min, and after the molecular sieve was completely settled, the reaction waste liquid was poured out.

[0054] Step (7) 200ml of deionized water was added and stirred on the stirring table at a speed of 200rpm for 5min to wash the molecular sieve thoroughly, and after stirring, it was taken out and allowed to stand, and the pH value of the washing liquid was tested.

[0055] ​Step (8) Repeat step (7) until the pH of the washing liquid after the washing sedimentation is 7, which proves that the molecular sieve washing is completed.

[0056] Step (9) Take part of the washing liquid, centrifuge, and then test the content of sodium element in it by icp, which proves that the sodium in the molecular sieve is completely exchanged.

[0057] Step (10) Pour out the washing liquid, and put the washed molecular sieve into a blast drying oven, dry at 60℃ for 24h until completely dry, to obtain the modified sulfonated X-type molecular sieve.

[0058] The performance of the molecular sieve of the present embodiment is tested, 50g of the molecular sieve is placed in a zeolite exchange column with filter membrane on top and bottom to prevent powder leakage. The solution is prepared according to the concentration of potassium ions and sodium ions in seawater, and passed through the zeolite exchange column from top to bottom. Repeat three times, take the exchanged solution, and test by icp. Most of the potassium ions are intercepted by the molecular sieve, and the ratio of potassium ions to sodium ions in the molecular sieve is about 1:2.6, which is much higher than the ratio in seawater, realizing efficient enrichment of potassium ions.

[0059] Example 4

[0060] The present embodiment provides a sulfonated X-type powder molecular sieve which can efficiently screen potassium ions and sodium ions. The sulfonated X-type powder molecular sieve is prepared from NaX-type molecular sieve, 0.5mol / L sulfuric acid as raw material, and the specific method is as follows: -1

[0061] Step (1) Put 50g of industrialized NaX molecular sieve into a ball mill for ball milling and crushing, and then put it into a 250ml beaker after grinding and sieving.

[0062] Step (2) Add 200ml of deionized water to the beaker and stir at 200rpm for 10min, take out the beaker and let it settle naturally, and then pour out the waste liquid after washing.

[0063] Step (3) Add 200ml of deionized water again, repeat step (2) three times until there is no impurity in the deionized water, and the molecular sieve is washed thoroughly.

[0064] Step (4) Put the washed molecular sieve into a blast drying oven, dry at 60℃ for 24h until completely dry, to obtain the modified molecular sieve.

[0065] Step (5) Put the modified molecular sieve into a 250ml beaker, prepare a 0.5mol / L sulfuric acid solution, add 200ml into the beaker, and stir on the stirring table at 500rpm at room temperature for 60min.

[0066] ​After the stirring of step (6) is completed, stand for 10 min, and after the molecular sieve is completely settled, pour out the reaction waste liquid.

[0067] Step (7) Add 200 ml of deionized water, stir at 200 rpm for 5 min, and then take it off and stand after stirring to test the pH value of the washing liquid.

[0068] Step (8) Repeat step (7) until the pH of the washing liquid after settlement is 7, which proves that the molecular sieve is washed completely.

[0069] Step (9) Take part of the washing liquid, centrifuge, and then test the content of sodium element in it by ICP to prove that the sodium in the molecular sieve is completely exchanged.

[0070] Step (10) Pour out the washing liquid, put the washed molecular sieve into a blast drying oven, dry at 60°C for 24 h until completely dry, and obtain the modified sulfonated X-type powder molecular sieve.

[0071] The performance of the molecular sieve of the present embodiment is tested. 50 g of the molecular sieve is placed in a zeolite exchange column with filter membranes on the top and bottom to prevent powder leakage. A solution is prepared according to the concentration of potassium ions and sodium ions in seawater, and passed through the zeolite exchange column from top to bottom. Repeat three times, and take the exchanged solution. Most of the potassium ions are intercepted by the molecular sieve, and the ratio of potassium ions to sodium ions in the molecular sieve is about 1:2.8, which is much higher than the ratio in seawater, realizing efficient enrichment of potassium ions.

[0072] Example 5

[0073] The present embodiment provides a low-sulfonated X-type powder molecular sieve for efficiently screening potassium ions and sodium ions. The sulfonated X-type powder molecular sieve is prepared from NaX-type molecular sieve, 0.1 mol / L sulfuric acid as raw material, and the specific method is as follows: -1

[0074] Step (1) Put 50 g of industrialized NaX molecular sieve into a ball mill for ball milling and crushing, and then place it in a 250 ml beaker after grinding and sieving.

[0075] Step (2) Add 200 ml of deionized water and stir at 200 rpm for 10 min, then take out the beaker and let it settle naturally, and pour out the waste liquid after washing.

[0076] Step (3) Add 200 ml of deionized water again, and repeat step (2) three times until there is no impurity in the deionized water, and the molecular sieve is washed thoroughly.

[0077] Step (4) Put the washed molecular sieve into a blast drying oven, dry at 60°C for 24 h until completely dry, and obtain the modified molecular sieve.​

[0078] Step (5) Put the molecular sieve to be modified into a 250ml beaker, configure a 0.5mol / L sulfuric acid solution, add 200ml into the beaker, and place it on a stirring table, stirring at 500rpm at room temperature for 60min.

[0079] Step (6) After stirring, stand for 10min, and after the molecular sieve is completely settled, pour out the reaction waste liquid.

[0080] Step (7) Add 200ml of deionized water, and place it on a stirring table at a speed of 200rpm for 5min to fully wash the molecular sieve. After stirring, take it off and stand, and test the pH value of the washing liquid.

[0081] Step (8) Repeat the above step (7) until the pH of the washing liquid after washing and settling is 7, which proves that the washing of the molecular sieve is completed.

[0082] Step (9) Take part of the washing liquid, centrifuge, and test the content of sodium element in it by icp, which proves that the sodium in the molecular sieve is completely exchanged.

[0083] Step (10) Pour out the washing liquid, and put the washed molecular sieve into a blast drying oven, dry at 60℃ for 24h until completely dry, to obtain the modified sulfonated X type powder molecular sieve.

[0084] The performance of the molecular sieve of the present embodiment is tested, 50g of the molecular sieve is placed in a zeolite exchange column with filter membrane on top and bottom to prevent powder leakage. A solution is configured according to the concentration of potassium ions and sodium ions in seawater, and passed through the zeolite exchange column from top to bottom. Repeat three times, take the exchanged solution, and test by icp. Most of the potassium ions are intercepted by the molecular sieve, and the ratio of potassium ions to sodium ions in the molecular sieve is about 1:3.6, which is much higher than the ratio in seawater, realizing efficient enrichment of potassium ions.

[0085] Example 6

[0086] The present embodiment provides a high-efficiency potassium ion and sodium ion screening sulfonated X type powder molecular sieve with high sulfonation degree, which is prepared from NaX type molecular sieve, 1mol / L sulfuric acid as raw material, and the specific method is as follows: -1

[0087] Step (1) Put 50g of industrialized NaX molecular sieve into a ball mill for ball milling and crushing, and after grinding and sieving, place it in a 250ml beaker.

[0088] Step (2) Add 200ml of deionized water, and place it on a stirring table at a speed of 200rpm for 10min, take out the beaker, and pour out the waste liquid after washing. ​

[0089] Step (3) re-join 200 ml of deionized water, repeat the above step (2) three times until the deionized water is free of impurities, and the molecular sieve is washed thoroughly.

[0090] Step (4) the washed molecular sieve is placed in a forced air drying oven, dried at 60°C for 24h until completely dry, to obtain the modified molecular sieve.

[0091] Step (5) the modified molecular sieve is placed in a 250ml beaker, and a 1mol / L sulfuric acid solution is prepared, 200ml is added to the beaker, and placed on a stirring table, stirred at 500rpm at room temperature for 60min.

[0092] Step (6) after stirring, stand for 10min, after the molecular sieve is completely settled, pour out the reaction waste liquid.

[0093] Step (7) add 200ml of deionized water, stir at 200rpm on the stirring table for 5min to wash the molecular sieve thoroughly, remove after stirring, stand, and test the pH value of the washing liquid.

[0094] Step (8) repeat the above step (7) until the pH of the washing liquid after washing and settling is 7, which proves that the molecular sieve is washed completely.

[0095] Step (9) take part of the washing liquid, centrifuge, and test the content of sodium element in it by icp, which proves that the sodium in the molecular sieve is completely exchanged.

[0096] Step (10) pour out the washing liquid, and place the washed molecular sieve in a forced air drying oven, dry at 60°C for 24h until completely dry, to obtain the modified sulfonated X-type powder molecular sieve.

[0097] The performance of the molecular sieve of the present embodiment is tested, 50g of molecular sieve is placed in a zeolite exchange column with filter membrane on top and bottom to prevent powder leakage. A solution is prepared according to the concentration of potassium ions and sodium ions in seawater, and passed through the zeolite exchange column from top to bottom. Repeat three times, take the exchanged solution, and test by icp. Most of the potassium ions are trapped by the molecular sieve, and the ratio of potassium ions to sodium ions in the molecular sieve is about 1:3.6, which is much higher than the ratio in seawater, realizing efficient enrichment of potassium ions.

Claims

1. Use of a sulfonated X molecular sieve for efficiently sieving potassium ions from sodium ions, characterized in that The preparation method of the sulfonated X-type molecular sieve comprises the following steps: Step (1) placing the industrial NaX molecular sieve in a beaker or placing the sieved ball-milled one in a beaker; Step (2) adding deionized water and stirring, and then pouring out the waste liquid after washing; Step (3) adding deionized water again, and repeating step (2) until no impurities are present in the deionized water and the molecular sieve is washed thoroughly; Step (4) drying the washed molecular sieve to obtain a molecular sieve to be modified; Step (5) placing the molecular sieve to be modified in a beaker, adding a sulfuric acid solution, stirring at room temperature, the added amount of the sulfuric acid solution being 3-5 times the mass of the molecular sieve, the concentration of the sulfuric acid solution being 0.1-1 mol / L, the stirring speed being 500-1000 rpm, and the time being 30-120 min; Step (6) after stirring, standing, and then pouring out the reaction waste liquid after the molecular sieve is completely settled; Step (7) adding deionized water and stirring to wash the molecular sieve thoroughly, standing, and testing the pH value of the washing liquid; Step (8) repeating step (7) until the pH value of the washing liquid is 7, and the molecular sieve is washed completely; Step (9) pouring out the washing liquid, drying the washed molecular sieve, and obtaining the sulfonated X-type molecular sieve after modification.

2. Use of the sulfonated X-type molecular sieve according to claim 1 for efficiently separating potassium ions from sodium ions, characterized in that In step (2), the added amount of the deionized water is 2-4 times the mass of the molecular sieve, the stirring speed is 100-500 rpm, and the time is 5-15 min.

3. Use of the sulfonated X-type molecular sieve according to claim 1 for efficiently separating potassium ions from sodium ions, characterized in that In step (3), the added amount of the deionized water is 2-4 times the mass of the molecular sieve.

4. Use of the sulfonated X molecular sieve according to claim 1 for efficiently separating potassium ions from sodium ions, characterized in that In step (4), the drying temperature is 60-80℃, and the time is 10-30 h.

5. Use of the sulfonated X molecular sieve according to claim 1 for efficiently separating potassium ions from sodium ions, characterized in that In step (6), the standing time is 5-15 min.

6. Use of the sulfonated X-type molecular sieve according to claim 1 for efficiently separating potassium ions from sodium ions, characterized in that In step (7), the added amount of the deionized water is 3-5 times the mass of the molecular sieve, the stirring speed is 100-500 rpm, and the time is 5-15 min.

7. Use of the sulfonated X-type molecular sieve according to claim 1 for efficiently separating potassium ions from sodium ions, characterized in that In step (9), the drying temperature is controlled to be 60-80℃, and the time is 20-30 h.