A method for ion sieve activation regeneration

Abstract

The application provides a method for ion sieve activation and regeneration, and the method comprises the following steps: step one, acid treatment, HCl solution is added to soak the aged ion sieve, the soaking temperature is 40-90 DEG C, the soaking time is 1h-48h, and the water washing step is performed after filtration, the ion sieve is water washed until the pH of the eluent is neutral, and ion sieve A is obtained; step two, alkali treatment, NaOH solution is added to soak the ion sieve A, the soaking temperature is 40-90 DEG C, the soaking time is 1h-6h, and the water washing step is performed after filtration, the ion sieve A is water washed until the pH of the eluent is neutral, and ion sieve B is obtained; step three, regeneration, the ion sieve B is placed in a circulating water machine, Na2CO3 and NaHCO3 aqueous solution are added to the circulating water machine, the circulating treatment time is 0-36h, filtration is performed, the ion sieve B is washed with flowing water for 0-12h, and natural air drying is performed, and the ion sieve B is obtained.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of ion sieve materials, and particularly relates to a method for activating and regenerating ion sieve. BACKGROUND

[0002] Water in nature exists in the form of water molecule clusters. The so-called water molecule cluster refers to: due to the polarity of water molecules, the oxygen of a water molecule is connected to the hydrogen of another water molecule by a hydrogen chain to form water like a large associated molecule cluster. The large molecule cluster water is generally associated by more than 10 water molecules, and the small molecule cluster is associated by only 3-9 water molecules. In a long-term static condition, water can form clusters of up to dozens of water molecules. The solubility and permeability are very low, and it is not easy to be absorbed by plants and humans, becoming "dead water clusters". These amorphous structure molecule clusters can be treated by certain physical and chemical methods to become smaller molecule clusters.

[0003] Utilize 17 The O nuclear magnetic resonance half-peak width can reflect the average relative size of the liquid water cluster structure. The wider the spectrum line, the larger the cluster, and the narrower the spectrum line, the smaller the cluster (Journal of Environmental Sciences, 2004, 24(1), 6-9). Generally, the half-peak width of large molecule cluster water is 100-130 Hz, and the half-peak width of small molecule cluster water is 40-60 Hz.

[0004] The principle of using nuclear magnetic resonance spectrum line width to represent the average relative size of the liquid water cluster structure is as follows: the absorption or emission of any kind of spectrum does not occur at a certain frequency, but presents a distribution with a certain width. The width of the spectrum line is measured by the full width at half maximum intensity (FWHM).

[0005] The width of the nuclear magnetic resonance spectrum line can reflect the average relative size of the liquid water cluster structure. The wider the spectrum line, the larger the cluster; the narrower the spectrum line, the smaller the cluster. Chinese patent CN104229926B discloses a composite material applied to water molecule cluster cutting reaction and a preparation method thereof. When the material is applied to water treatment, it can decompose large molecule cluster water into small molecule cluster water to realize the reactivation of water. The components and mass fractions of the raw materials are as follows: 12-21% of 800-1200 mesh tourmaline powder, 10-16% of 100-400 mesh tourmaline powder, 2-4% of 100-150 nm tourmaline powder, 22-28% of diatomite, 15-20% of montmorillonite, 22-28% of attapulgite clay, 0.1-0.2% of cerium nitrate, and 0.1-0.2% of lanthanum nitrate.

[0006] The activation of water by the ion sieve prepared by CN104229926B is due to the high electric field strength and high far infrared emission ability of its surface, which can decompose large molecular group water into small molecular group water containing only a few water molecules, realizing the reactivation of water. The ion sieve can remove calcium and magnesium ions in water by generating a large number of hydroxyl anions through its micro-electrolysis ability, so that the calcium and magnesium ions in water and the inorganic dissolved substances of calcium bicarbonate and magnesium bicarbonate can be changed into calcium carbonate and magnesium hydroxide precipitates to crystallize and precipitate, thereby softening the water.

[0007] However, the ion sieve also has problems such as aging when it is used for a long time. When the service life of the ion sieve reaches 3-5 years, a large amount of heavy metal ions and macromolecular organic colloidal impurities are adsorbed on the surface of the ion sieve, which seriously affects its use efficiency, that is, the ion sieve ages. Therefore, it is of great significance to effectively improve the efficiency and prolong the service life of the ion sieve by decontamination and regeneration of the aged ion sieve.

[0008] In "Preparation of functional porous purple clay particles and water activation performance thereof", Mo et al. mentioned the preparation and water activation performance of the ceramic particles, but did not mention the problem of aging after repeated use of the material. Journal of Hebei University of Technology, 2018(47), 70-74. There are documents in the prior art that mention de-scaling treatment of aged ion sieve. After the ceramic particles lose the ability to adsorb heavy metal ions, 0.1 mol / L HCl solution is used to desorb the ceramic particles. At this time, the heavy metal ions adsorbed on the ceramic particles are completely dissolved, and the ceramic particles are regenerated. However, it is found in actual experiments that the ion sieve treated with hydrochloric acid loses the ability to activate water.

[0009] Therefore, there is a need in the prior art for a method for activating and regenerating aged ion sieve to improve the efficiency and prolong the service life of the ion sieve. SUMMARY

[0010] To solve the above problems, the purpose of the present application is to provide a method for activating and regenerating ion sieve, which can solve the problem of ion sieve aging. The heavy metal ions and macromolecular organic colloidal impurities on the surface of the aged ion sieve are removed by acid treatment, the water activation ability of the ion sieve is restored by alkali treatment, and finally the water activation ability is enhanced by regeneration treatment.

[0011] Therefore, the present application provides a method for activating and regenerating aged ion sieve, which comprises the following steps:

[0012] Step 1, acid treatment

[0013] HCl solution is added to the aged ion sieve and soaked, the soaking temperature is 40-90℃, the soaking time is 1-48h, and after filtration, water washing step is carried out, the ion sieve is washed until the pH of the eluate is neutral, to obtain ion sieve A;

[0014] Step 2, alkali treatment

[0015] The ion sieve A is soaked in a NaOH solution, the soaking temperature is 40-90℃, the soaking time is 1h-6h, after filtration, the water washing step, the water washing ion sieve A until the eluent pH is neutral, to obtain ion sieve B;

[0016] Step three, regeneration

[0017] The ion sieve B is placed in a circulating water machine, Na2CO3 and NaHCO3 aqueous solution is added in the circulating water machine, the circulating treatment time is 0h-36h, filtration, the ion sieve B is washed with flowing water for 0h-12h, and then naturally air-dried.

[0018] In step one, the concentration of the HCl solution is 0.1%-15%, preferably 1%-7.3%, more preferably 1% HCl, 3.7% HCl or 7.3% HCl, and most preferably 1% HCl; the soaking time in step one is 2h-23h, preferably 4h-23h, further preferably 6h-23h, and more preferably 6h; the water washing step time in step one is 0.5h-24h, preferably 1h-22.5h, further preferably 2h-3h, and more preferably 3h; the heating temperature in step one is 70-80℃; the soaking time in step one is 2h-23h, preferably 4h-6h, and further preferably 6h; the water washing step time in step one is 1h-24h, preferably 1h-22.5h, further preferably 2h-3h, and more preferably 3h. In step one, the volume weight ratio of the HCl solution to the aged ion sieve is 2-6mL / g.

[0019] In step two, the mass fraction of the NaOH solution is 0.01%-8%, preferably 0.02%-4%, further preferably 0.02%-0.5%, more preferably 0.04%-0.5%, and most preferably 0.5%; the soaking temperature in step two is 70-80℃; the soaking time in step two is 1h-3h, preferably 1h-2h, and further preferably 2h; the water washing time in step two is 0.5h-4h, preferably 0.5h-1h, and further preferably 0.5h. In step two, the volume weight ratio of the NaOH solution to the ion sieve A is 2-6mL / g; in step three, the volume weight ratio of the Na2CO3 and NaHCO3 aqueous solution to the ion sieve B is 1-6mL / g.

[0020] The concentration of the Na2CO3 and NaHCO3 aqueous solution in step three is respectively 2.86%-20.03% and 7.56%-2.52%, preferably the concentration of the Na2CO3 and NaHCO3 aqueous solution is respectively 5.72%-17.17% and 6.72%-3.36%; further preferably the concentration of the Na2CO3 and NaHCO3 aqueous solution is respectively 8.59%-14.31% and 5.80%-4.20%; more preferably the concentration of the Na2CO3 and NaHCO3 aqueous solution is respectively 11.45%-14.31% and 5.04%-4.20%; most preferably the concentration of the Na2CO3 and NaHCO3 aqueous solution is respectively 11.45% and 5.04%; the circulation treatment time is 0-32h, preferably 0h-24h;

[0021] The flowing water cleaning ion sieve time is 2h-12h, preferably 2h.

[0022] The method of the application, most preferably, the steps are as follows:

[0023] Step one, acid treatment

[0024] 4kg of aged ion sieve is placed in 16L of 1% HCl solution, heated to 70-80℃, soaked for 6h, filtered, and washed with water for 3h to obtain ion sieve A;

[0025] Step two, alkali treatment

[0026] 4kg of ion sieve A is placed in 16L of 0.5% NaOH solution, the ion sieve is soaked, heated to 70-80℃, soaked for 2h, filtered, and washed with water for 0.5h to obtain ion sieve B;

[0027] Step three, regeneration

[0028] 4kg of ion sieve B is placed in a water machine, 8L of 11.45% Na2CO3 and 5.04% NaHCO3 aqueous solution is added, and the ion sieve is treated for 24h, filtered, and washed with flowing water for 2h to obtain regenerated ion sieve.

[0029] In the method of the application, the water machine components are a container, a regulating valve, a pressurizing pump and a four-stage filter pipe, and the above components are connected in series through a PE pipe; a regulating valve is arranged between the container and the pressurizing pump; the container is provided with a liquid inlet at the top and a liquid outlet at the bottom, the PE pipe specification is 2min, the filter pipe outer diameter is 6cm, length is 32cm, and filter pipe thickness is 1-3mm; one end of the filter pipe can be unscrewed, and the filter pipe can be filled with ion sieve, and the filter pipe two ends are provided with a mesh spacer.

[0030] In the method, the ion sieve is prepared from 800-1200 mesh tourmaline powder, 100-400 mesh tourmaline powder, 100-150 nm tourmaline powder, diatomite, montmorillonite, attapulgite clay, cerium nitrate and lanthanum nitrate, which can be purchased or prepared according to the prior art, for example, by the following method:

[0031] 1) The raw materials are weighed, and the components and mass fractions are as follows: 12-21% of 800-1200 mesh tourmaline powder, 10-16% of 100-400 mesh tourmaline powder, 2-4% of 100-150 nm tourmaline powder, 22-28% of diatomite, 15-20% of montmorillonite, 22-28% of attapulgite clay, 0.1-0.2% of cerium nitrate, and 0.1-0.2% of lanthanum nitrate;

[0032] 2) The cerium nitrate and lanthanum nitrate are mixed and dissolved in the spray water to prepare a mixed spray solution;

[0033] 3) The tourmaline powder, tourmaline powder, diatomite, montmorillonite and attapulgite clay are mixed, the spray humidity of the mixed spray solution is adjusted, and the mixed powder is prepared into a ball under the action of the mixed spray solution;

[0034] 4) The ball is sintered, and the ion sieve is obtained after cooling.

[0035] In the method, the aged ion sieve is an ion sieve activated by water, for example, an ion sieve that has not been subjected to any physical and chemical treatment for 3-5 years after being activated by water for 3-5 years, and is used for preparing small molecule water. The indicators of the aged ion sieve are pH, conductivity and 17 O nuclear magnetic resonance half-peak width. Before the experiment, we accelerated the re-aging of the aged ion sieve by using a water treatment device, and in principle, until the half-peak width of the treated water is greater than about 60. 17 O half-peak width is greater than about 60. The accelerated aging ion sieve ball meets the standard and can be used for regeneration experiment.

[0036] The following is an explanation and description of the terms of the present application:

[0037] The aged ion sieve is prepared according to the preparation method of Example 1, Example 2 or Example 3 of CN104229926B specification, and the aged ion sieve is obtained after the prepared ion sieve is used to filter mineral water for 3-6 years, preferably for 3 years, 4 years or 5 years. Due to the limited space, the preparation method of Example 1, Example 2 or Example 3 of CN104229926B specification is referred to the patent document;

[0038] The water machine comprises a container, a regulating valve, a pressurizing pump and a four-stage filter pipe, which are connected in series through a PE pipe; a regulating valve is arranged between the container and the pressurizing pump; a liquid inlet and a liquid outlet are arranged above and below the container respectively, the PE pipe is 2 inches in specification, the filter pipe is 6 cm in outer diameter, 32 cm in length and 1-3 mm in thickness, one end of the filter pipe can be screwed open, the filter pipe can be filled with ion sieve, and the filter pipe is provided with a mesh spacer at two ends.

[0039] Obviously, according to the above content of the present application, according to the ordinary technical knowledge and common means in the art, other various forms of modifications, replacements or changes can be made without departing from the above basic technical idea of the present application.

[0040] The beneficial technical effects of the present application are as follows:

[0041] 1. The aged ion sieve is treated by an acid treatment liquid, and the effect of activating water is very low, while the ion sieve treated by an acid-alkali treatment liquid can restore good water activating capacity. It is shown that the heavy metal ions and macromolecular organic colloid impurities on the surface of the aged ion sieve can be removed by acid treatment, and the water activating capacity of the ion sieve can be restored by alkali treatment.

[0042] 2. The heavy metal ions and macromolecular organic colloid impurities on the surface of the aged ion sieve are removed by acid treatment, the water activating capacity of the ion sieve is restored by alkali treatment, and the water activating capacity of the ion sieve is enhanced by treatment with a water solution of regenerant Na2CO3 and NaHCO3. By optimizing the concentration of the reagent and the treatment time during the treatment process, the optimal parameter conditions are found, which provides certain reference for production practice. BRIEF DESCRIPTION OF DRAWINGS

[0043] Figure 1 : ion sieve A washed after acid treatment (A1 is ion sieve washed after 3.7% HCl acid treatment, and A2 is ion sieve washed after 7.3% HCl acid treatment);

[0044] Figure 2Ion sieve B after 8% NaOH base treatment, surface damage was found (B1 is ion sieve after 3.7% HCl acid treatment, rinsing clean and then base treatment, B2 is ion sieve after 7.3% HCl acid treatment, rinsing clean and then base treatment);

[0045] Figure 3 : Figure 3 The structure of the water machine. DETAILED DESCRIPTION

[0046] The present application is further illustrated by the following examples, but not as a limitation to the present application.

[0047] Experimental reagents and instruments: sodium carbonate (analytical pure), sodium bicarbonate (analytical pure), sodium chloride (analytical pure), sodium hydroxide (analytical pure), Mettler multifunctional tester (including pH / mV module, ion module, conductivity module), constant temperature water bath, balance, nuclear magnetic resonance spectrometer (Bruker, 400MHz).

[0048] Ion sieve: ion sieve was prepared according to Chinese patent CN104229926B (invention name: a composite material applied to water molecule cluster cutting reaction and its preparation method), which can be prepared by any one of example 1, example 2, example 3 in the specification of CN104229926B.

[0049] Aged ion sieve: the ion sieve prepared by Chinese patent CN104229926B was used to prepare small molecular water for 3-6 years to obtain the aged ion sieve;

[0050] Experimental example 1: optimization of acid treatment step conditions

[0051] Take 4 portions of 100g aged ion sieve respectively, add 400ml of 1% HCl, 3.7% HCl, 7.3% HCl and deionized water respectively, heat to 70-80℃, and measure Ca 2+ , pH value and conductivity in the solution at 0h, 2h, 4h, 6h, 23h after soaking respectively. Then filter and wash the filter with water until the eluate pH is neutral to obtain ion sieve A. The detection results of Ca 2+ , pH value and conductivity at each time point during the soaking experiment are shown in Tables 1-3.

[0052] Table 1 Ca 2+ (mg / L)

[0053]

[0054] Table 2 pH value of acid treatment solution

[0055]

[0056] Table 3 Conductivity of acid treatment solution (mS / cm)

[0057]

[0058] Conclusion: From Table 1, Table 2 and Table 3, it can be seen that after the ion sieve was added into 1% HC1, 3.7% HC1, 7.3% HC1 and deionized water, the Ca 2+ concentration increased with the increase of soaking time, and reached the maximum value at 23h. The size relationship of three experimental groups was: 7.3% HC1 > 3.7% HC1 > 1% HC1, which indicated that the higher the HC1 concentration, the better the treatment effect. The pH value of the treatment solution increased slightly with the extension of soaking time, which indicated that the treatment solution still maintained good treatment ability. Since the reaction speed became slow at 6h, the samples of 3.7% HC1 and 7.3% HC1 groups were selected as the acid treatment solution, and the treatment time was set to 6h.

[0059] The detection results of Ca 2+ , pH value and conductivity at each time point during water washing process are shown in Table 4-6.

[0060] Table 4 Ca 2+ (mg / L) of solution after flushing ion sieve

[0061]

[0062] Table 5 pH value of solution after flushing ion sieve

[0063]

[0064] Table 6 Conductivity (mS / cm) of solution after flushing ion sieve

[0065]

[0066] From Table 4, Table 5 and Table 6, it can be seen that when the water washing time was 3h, the Ca 2+ concentration, pH value and conductivity of the flushing solution remained basically unchanged, which indicated that the water washing was clean, and therefore the water washing time was determined to be 3h.

[0067] Experimental Example 2 Optimization of conditions of alkali treatment step

[0068] Take 6 100g ion exchange A, respectively, add 400ml mass fraction of 0.01% NaOH, 0.02% NaOH, 0.05% NaOH, 0.2% NaOH, 0.5% NaOH, 8% NaOH, heated to 70-80℃, respectively, after soaking 0h, 1h, 2h, the pH value, conductivity of the solution. Filtration, water washing filter to get ion exchange until the eluent pH is neutral, get ion exchange B.

[0069] Select 3.7% HCl and 7.3% HCl group as acid treatment solution, treatment time is 6h, after washing clean ion exchange A, ion exchange A is larger, with the strength of new ion exchange, see the specification attached figure Figure 1 . Add 8% NaOH, found that the ion exchange after alkali treatment has been damaged, the surface of the ion exchange at each stage during the experiment, see the specification attached figure Figure 2 . Therefore, the concentration of acid and alkali treatment solution are reduced, and the experiment is carried out.

[0070] Select 1% HCl and 3.7% HCl group as acid treatment solution, treatment time is 6h, after washing clean ion exchange A, add 0.01% NaOH, 0.02% NaOH, 0.05% NaOH, 0.2% NaOH, 0.5% NaOH, soak the pH value, conductivity detection results at each time point during the experiment as shown in table 7-8.

[0071] Table 7 pH value of alkali treatment solution

[0072]

[0073]

[0074] Table 8 conductivity of alkali treatment solution (mS / cm)

[0075]

[0076] Table 7 and table 8 experimental data show that: after ion exchange is added to the alkali treatment solution, the pH value of the soaking solution of three groups is less than 9, which is contrary to the expected function of the material, so it is abandoned, and the remaining 5 groups of alkali treatment solution are selected, namely 1% HCl treated with 0.02%, 0.05%, 0.2%, 0.5% NaOH and 3.7% HCl treated with 0.05% NaOH. The pH value of the treatment solution is basically unchanged at 2h, so the alkali treatment process is set to 2h.

[0077] According to the above experimental process, the Na +The pH value, conductivity detection results are shown in Tables 9-11.

[0078] Table 9 Na concentration of solution after washing ion exchange + (mg / L)

[0079]

[0080] Table 10 pH value of solution after washing ion exchange

[0081]

[0082]

[0083] Table 11 Conductivity (mS / cm) of solution after washing ion exchange

[0084]

[0085] The experimental data of Table 9, Table 10 and Table 11 show that when the washing time is 0.5h, the Na + concentration, pH value and conductivity of the washing solution remain basically unchanged, indicating that the washing is clean, so the washing time is determined to be 0.5h.

[0086] Experimental Example 3 Comparison of effects of acid-base treatment and activation water

[0087] The ion exchange after being treated with 1% HCl and then treated with 0.02%, 0.05%, 0.2%, 0.5% NaOH and the ion exchange after being treated with 3.7% HCl and then treated with 0.05% NaOH are selected as ion exchange B, and a static activation water experiment is carried out. The experimental process is as follows: a certain amount of each ion exchange above is weighed in a beaker, and 6 times the amount of tap water is added. After soaking for 1h, filtration is performed, and the pH and 17 O nuclear magnetic resonance half-peak width reflects the activation water effect of ion exchange. The pH of the test water is tested, and the results are shown in Table 12.

[0088] Table 12 Static activation water experiment

[0089]

[0090] Note: The pH of the control group tap water is 7.174

[0091] Table 12 data shows that the ability of 5 groups of alkaline treatment solution experimental group, the optimal three groups of tap water treatment is: 1% HC1 after treatment with 0.05%, 0.2%, 0.5% NaOH treated ion exchange, so the follow-up experiment selected the three optimal experimental group. And control aging ion exchange and acid treated ion exchange A to carry out static activation water experiment, static activation water experiment process as follows: weighing a certain amount of the above ion exchange in beaker, then add 6 times the amount of tap water, soak 1 h after filtration, take supernatant test water pH and 17 O nuclear magnetic resonance half peak width reflects the effect of ion exchange activated water. The results are shown in Table 13.

[0092] Table 13 static activation water experiment

[0093]

[0094] Note: the control group tap water pH = 7.174, 17 O-NMR half peak width 103.08

[0095] Table 13 data shows that the ion exchange treated by acid, the effect of activated water is very low, and the ion exchange treated by acid and alkali, can restore the better activated water capacity. It is proved that through the acid treatment can remove the heavy metal ions on the surface of the aging ion exchange, macromolecular organic colloid impurities, and then through the alkali treatment can restore the activated water capacity of ion exchange. Static activation water experiment proved that the optimal condition is 1% HC1 treatment with 0.5% NaOH treated ion exchange for subsequent screening.

[0096] 17 O nuclear magnetic resonance half peak width can reflect the average relative size of liquid water cluster structure, the wider the spectrum, the larger the cluster, the narrower the spectrum, the smaller the cluster. Therefore, the change of 17 O nuclear magnetic resonance half peak width to characterize the efficiency of ion exchange activated water:

[0097] 17 O nuclear magnetic resonance half peak width reduction rate = (treated water 17 O nuclear magnetic resonance half peak width - treated water 17 O nuclear magnetic resonance half peak width) / treated water 17 O nuclear magnetic resonance half peak width x 100%.

[0098] Table 14 sample loss rate

[0099]

[0100] The data shown in Table 14 indicates that the treated ion exchange is basically no damage rate after drying, and the regeneration loss rate is less than 2.5%, and the results are shown in Table 14.

[0101] Experimental example 4 regeneration method optimization and activated water effect comparison

[0102] Take 4 kg of ion sieve B, put it in the water machine, add 8 L of Na2CO3 and NaHCO3 aqueous solution, and circulate for 24 h. Drain the treatment liquid, continue to wash the ion sieve with flowing water for 2 h, and dry naturally to obtain.

[0103] After regeneration treatment, static verification experiments were conducted on the ion sieve after regeneration treatment. The pH and 17 O-NMR half-peak width of water samples were measured respectively, and the results are shown in Table 16.

[0104] Table 15: Content and percentage of each substance in formulations 1-7

[0105]

[0106] Example 1

[0107] Take 4 kg of ion sieve B, put it in the water machine, add 8 L of Na2CO3 and NaHCO3 aqueous solution, and circulate for 24 h. Drain the treatment liquid, continue to wash the ion sieve with flowing water for 2 h, and dry naturally to obtain. 17 O-NMR half-peak width of water samples were measured respectively, and the results are shown in Table 16.

[0108] Example 2

[0109] Take 4 kg of ion sieve B, put it in the water machine, add 8 L of Na2CO3 and NaHCO3 aqueous solution, and circulate for 24 h. Drain the treatment liquid, continue to wash the ion sieve with flowing water for 2 h, and dry naturally to obtain. 17 O-NMR half-peak width of water samples were measured respectively, and the results are shown in Table 16.

[0110] Example 3

[0111] The aged ion exchange resin 4 kg was placed in 16 L of 1% by mass HCl solution, heated to 70-80°C, soaked for 6 h, filtered, and washed with water for 3 h to obtain ion exchange resin A. The ion exchange resin A 4 kg was placed in 16 L of 0.5% by mass NaOH solution, soaked the ion exchange resin, heated to 70-80°C, soaked for 2 h, filtered, and washed with water for 0.5 h to obtain ion exchange resin B. 4 kg of ion exchange resin B was weighed, and the ion exchange resin B was placed in a water machine, 8 L of aqueous solution of formula 3 (8.59% by mass Na2CO3 and 5.80% by mass NaHCO3) was added, and the treatment was performed for 24 h, filtered, and the ion exchange resin was washed with flowing water for 2 h, and naturally air-dried to obtain the regenerated ion exchange resin. The ion exchange resin after the regeneration treatment was subjected to a static verification experiment, and the pH and conductivity of the water sample were measured, respectively. 17 O-NMR half-peak width, see Table 16.

[0112] Example 4

[0113] The aged ion exchange resin 4 kg was placed in 16 L of 1% by mass HCl solution, heated to 70-80°C, soaked for 6 h, filtered, and washed with water for 3 h to obtain ion exchange resin A. The ion exchange resin A 4 kg was placed in 16 L of 0.5% by mass NaOH solution, soaked the ion exchange resin, heated to 70-80°C, soaked for 2 h, filtered, and washed with water for 0.5 h to obtain ion exchange resin B. 4 kg of ion exchange resin B was weighed, and the ion exchange resin B was placed in a water machine, 8 L of aqueous solution of formula 4 (11.45% by mass Na2CO3 and 5.04% by mass NaHCO3) was added, and the treatment was performed for 24 h, filtered, and the ion exchange resin was washed with flowing water for 2 h, and naturally air-dried to obtain the regenerated ion exchange resin. The ion exchange resin after the regeneration treatment was subjected to a static verification experiment, and the pH and conductivity of the water sample were measured, respectively. 17 O-NMR half-peak width, see Table 16.

[0114] Example 5

[0115] The aged ion exchange resin 4 kg was placed in 16 L of 1% by mass HCl solution, heated to 70-80°C, soaked for 6 h, filtered, and washed with water for 3 h to obtain ion exchange resin A. The ion exchange resin A 4 kg was placed in 16 L of 0.5% by mass NaOH solution, soaked for 2 h, filtered, and washed with water for 0.5 h to obtain ion exchange resin B. The ion exchange resin B 4 kg was placed in a water machine, 8 L of aqueous solution of formula 5 (14.31% by mass Na2CO3 and 4.20% by mass NaHCO3 aqueous solution) was added, and the treatment was performed for 24 h. The ion exchange resin was filtered, washed with flowing water for 2 h, and naturally dried to obtain the regenerated ion exchange resin. The ion exchange resin after the regeneration treatment was subjected to a static verification experiment, and the pH and conductivity of the water sample were measured, respectively. 17 O-NMR half-peak width, see Table 16.

[0116] Example 6

[0117] The aged ion exchange resin 4 kg was placed in 16 L of 1% by mass HCl solution, heated to 70-80°C, soaked for 6 h, filtered, and washed with water for 3 h to obtain ion exchange resin A. The ion exchange resin A 4 kg was placed in 16 L of 0.5% by mass NaOH solution, soaked for 2 h, filtered, and washed with water for 0.5 h to obtain ion exchange resin B. The ion exchange resin B 4 kg was placed in a water machine, 8 L of aqueous solution of formula 6 (17.17% by mass Na2CO3 and 3.36% by mass NaHCO3 aqueous solution) was added, and the treatment was performed for 24 h. The ion exchange resin was filtered, washed with flowing water for 2 h, and naturally dried to obtain the regenerated ion exchange resin. The ion exchange resin after the regeneration treatment was subjected to a static verification experiment, and the pH and conductivity of the water sample were measured, respectively. 17 O-NMR half-peak width, see Table 16.

[0118] Example 7

[0119] The aged ion exchange resin 4 kg was placed in 16 L of 1% by mass HCl solution, heated to 70-80°C, soaked for 6 h, filtered, and washed with water for 3 h to obtain ion exchange resin A. The ion exchange resin A 4 kg was placed in 16 L of 0.5% by mass NaOH solution, soaked for 2 h, filtered, and washed with water for 0.5 h to obtain ion exchange resin B. The ion exchange resin B 4 kg was placed in a water machine, 8 L of aqueous solution of formula 7 (20.03% by mass Na2CO3 and 2.52% by mass NaHCO3 aqueous solution) was added, and the treatment was performed for 24 h. The ion exchange resin was filtered, washed with flowing water for 2 h, and naturally dried to obtain the regenerated ion exchange resin. The ion exchange resin after the regeneration treatment was subjected to a static verification experiment, and the pH and conductivity of the water sample were measured, respectively. 17O-NMR half-peak width, see Table 16.

[0120] Table 16 Static activation water experiment

[0121]

[0122] Note: the pH of the control group tap water = 7.174, 17 O nuclear magnetic half-peak width 103.08

[0123] Static verification experiments were carried out on the ion exchange resin after regeneration treatment, aged ion exchange resin and ion exchange resin B, and the pH and 17 O-NMR half-peak width, test data in Table 16, based on the above examples and Table 16 data, the activation ability of ion exchange resin treated by Example 4 formula 4 is the strongest.

[0124] The experimental data of the present application show that the heavy metal ions and macromolecular organic colloidal impurities on the surface of the aged ion exchange resin are removed by acid treatment, the activation water ability of the ion exchange resin is restored by alkali treatment, and finally the activation water ability is enhanced by the aqueous solution of the regenerant Na2CO3 and NaHCO3. Through acid treatment, alkali treatment and regeneration treatment of the ion exchange resin, the concentration of the reagent and the treatment time during the treatment process are optimized.

[0125] The above description is only the preferred specific embodiment of the present application, but the protection scope of the present application is not limited to this. Any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, which should be covered in the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for ion-sieve activation regeneration, characterized by, The method comprises the following steps: Step one, acid treatment adding HCl solution to the aged ion exchange resin for soaking, the soaking temperature is 40-90℃, the soaking time is 1-48h, after filtration, water washing step is carried out, the ion exchange resin is washed until the pH of the eluate is neutral, to obtain ion exchange resin A; Step two, alkali treatment adding NaOH solution to the ion exchange resin A for soaking, the soaking temperature is 40-90℃, the soaking time is 1h-6h, after filtration, water washing step is carried out, the ion exchange resin A is washed until the pH of the eluate is neutral, to obtain ion exchange resin B; Step three, regeneration placing the ion exchange resin B in a circulating water machine, adding Na2CO3 and NaHCO3 aqueous solution in the circulating water machine, the circulating treatment time is 24h-36h, after filtration, the ion exchange resin B is washed with flowing water for 0h-12h, and then naturally air-drying is carried out, to obtain the product. The mass fraction of the HCl solution in step one is 1%, the mass fraction of the NaOH solution in step two is 0.5%, and the mass fractions of the Na2CO3 and NaHCO3 aqueous solution in step three are 11.45% and 5.04% respectively. The aged ion exchange resin is obtained after using ion exchange resin to treat mineral spring water for 3-5 years, and the ion exchange resin is a composite material used for water molecule cluster cutting reaction.

2. The method according to claim 1, wherein: the soaking time in step one is 2h-23h; the water washing step time in step one is 0.5h-24h; the soaking temperature in step one is 70-80℃.

3. The method according to any one of claims 1-2, wherein: the soaking temperature in step two is 70-80℃; the soaking time in step two is 1h-3h; the water washing time in step two is 0.5h-4h.

4. The method according to any one of claims 1-2, wherein: the circulating treatment time in step three is 24h-32h, the flowing water washing time of the ion exchange resin in step three is 2h-12h.

5. The method according to claim 1, wherein: the soaking time in step one is 4h-23h, and the water washing step time in step one is 1h-22.5h, and / or, the soaking time in step two is 1h-2h, and the water washing time in step two is 0.5h-1h.

6. The method according to claim 1, wherein: the soaking time in step one is 6h-23h, and the water washing step time in step one is 2h-3h, and / or, the soaking time in step two is 2h, and the water washing time in step two is 0.5h, and / or, the flowing water washing time of the ion exchange resin in step three is 2h.

7. The method of claim 1, wherein: the soaking time in step one is 6h, and the water washing step time in step one is 3h.

8. The method of claim 1, wherein: the volume / weight ratio of the HCl solution to the aged ion exchange resin in step one is 2-6 mL / g, the volume / weight ratio of the NaOH solution to the ion exchange resin A in step two is 2-6 mL / g, and the volume / weight ratio of the Na2CO3 and NaHCO3 aqueous solution to the ion exchange resin B in step three is 1-6 mL / g.

9. The method of claim 1, wherein: The ion sieve component is 800-1200 mesh tourmaline powder, 100-400 mesh tourmaline powder, 100-150 nm tourmaline powder, diatomite, montmorillonite, attapulgite clay, cerium nitrate and lanthanum nitrate.

10. The method of claim 1, wherein: The preparation method of the ion sieve is as follows: 1) weigh the raw materials, and the components and mass fractions are respectively: 12-21% of 800-1200 mesh tourmaline powder, 10-16% of 100-400 mesh tourmaline powder, 2-4% of 100-150 nm tourmaline powder, 22-28% of diatomite, 15-20% of montmorillonite, 22-28% of attapulgite clay, 0.1-0.2% of cerium nitrate, and 0.1-0.2% of lanthanum nitrate; 2) mix the cerium nitrate and lanthanum nitrate uniformly, and dissolve them into the spraying water to prepare a mixed spraying solution; 3) mix the tourmaline powder, tourmaline powder, diatomite, montmorillonite and attapulgite clay uniformly, adjust the spraying humidity of the mixed spraying solution, and prepare the mixed powder into a ball under the action of the mixed spraying solution; 4) sinter the ball, and obtain the ion sieve after cooling.

11. The method of claim 1, wherein: Step one, acid treatment Put 4 kg of aged ion sieve into 16 L of 1% HCl solution, heat to 70-80℃, soak for 6 h, filter, and wash with water for 3 h to obtain ion sieve A; Step two, alkali treatment Put 4 kg of ion sieve A into 16 L of 0.5% NaOH solution, soak the ion sieve, heat to 70-80℃, soak for 2 h, filter, and wash with water for 0.5 h to obtain ion sieve B; Step three, regeneration Put 4 kg of ion sieve B into a circulating water machine, add 8 L of 11.45% Na2CO3 and 5.04% NaHCO3 aqueous solution, circulate for 24 h, filter, and wash the ion sieve with flowing water for 2 h, and obtain the regenerated ion sieve after natural drying.

12. The method of claim 1, wherein: The circulating water machine components are a container, a regulating valve, a pressurizing pump and a four-stage filter pipe, the circulating water machine components are connected in series through a PE pipe; a regulating valve is arranged between the container and the pressurizing pump; a liquid inlet and a liquid outlet are arranged above and below the container respectively, the specification of the PE pipe is 2 minutes, the outer diameter of the filter pipe is 6 cm, the length of the filter pipe is 32 cm, and the thickness of the filter pipe is 1-3 mm; one end of the filter pipe can be twisted off, the filter pipe can be filled with ion sieve, and mesh spacers are arranged at both ends of the filter pipe.

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