CN110918050A - Zeolite material adsorbent and preparation method thereof - Google Patents
Zeolite material adsorbent and preparation method thereof Download PDFInfo
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- CN110918050A CN110918050A CN201911202453.1A CN201911202453A CN110918050A CN 110918050 A CN110918050 A CN 110918050A CN 201911202453 A CN201911202453 A CN 201911202453A CN 110918050 A CN110918050 A CN 110918050A
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
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Abstract
The invention provides a zeolite material adsorbent and a preparation method thereof, wherein the zeolite material adsorbent is a basalt-based zeolite material, and the basalt-based zeolite material is prepared by blending, melting and processing basalt and alkali at a high temperature of 500-800 ℃ and then crystallizing. The invention firstly utilizes the three-dimensional tetrahedral structure of the basalt mesoporous and microporous structures to obtain the novel inorganic material with higher crystal integrity. The basalt-based X-type zeolite material is uniform in particle size distribution, complete in crystal form and 2-3 mu m in size; has strong uranium adsorption capacity when being used for absorbing uranium in wastewater. The maximum adsorption capacity of the basalt-based X-type zeolite material on uranium reaches 2442mg/g, which is 10 times of that of a common adsorption material on uranium.
Description
Technical Field
The invention belongs to the field of resource utilization and environmental protection, and particularly relates to a zeolite material adsorbent and a preparation method thereof.
Background
In recent years, with the development of nuclear energy, the amount of radioactive nuclear waste is increasing, which causes heavy burden and serious crisis to the environment and ecology. Therefore, how to properly deal with radioactive nuclear pollution has become a global environmental protection problem. At present, methods for removing radioactive elements in water environments include: chemical precipitation, ion exchange, solvent extraction, adsorption, and the like. Among them, the adsorption method has been widely used in actual wastewater treatment because of its advantages of high efficiency, low cost, simple treatment process, and low possibility of causing secondary pollution.
Zeolite is a three-dimensional tetrahedral hydrated aluminosilicate mineral with a mesoporous and microporous structure, and is widely applied to the fields of separation and oil refining industry, feed additives and the like. ES in animal husbandry, adsorbent in wastewater treatment for removal of heavy metal cations, anions and dyes. However, the industrially synthesized zeolite comes from chemical sources and its cost is high, which limits its application to a large extent.
The invention patent CN201510407036.6 relates to a uranium-containing wastewater decontaminant, which is composed of zeolite with the particle size of 40-150 meshes and phosphate with the particle size of less than 60 meshes, wherein the volume ratio of the zeolite to the phosphate is 50-75: 1, and the zeolite comprises natural green zeolite and artificial zeolite; after the uranium-containing radioactive wastewater with certain conditions flows through the reaction bed filled with the decontaminant at a proper flow rate, uranium ions in the wastewater are removed, so that a water body with uranium element content reaching the national emission standard is obtained; the removed uranium elements are trapped in the reaction bed layer and form a shaped secondary uranium-bearing mineral, and the generated secondary uranium-bearing mineral can be refined and utilized through acid leaching; the method can simultaneously achieve the purposes of removing pollution and recycling uranium elements, and has great popularization and application values.
Patent application CN201810938366.1 discloses an ecological purification treatment system and a treatment method for uranium-containing low-level radioactive wastewater. The ecological purification treatment system for the uranium-containing low-emission wastewater is of a layered structure and comprises an enrichment plant absorption layer, a modified zeolite purification layer and a gravel water collection layer, wherein the enrichment plant absorption layer is 20-30 cm from top to bottom, the modified zeolite purification layer is 20-30 cm from top to bottom, and a 1cm PVC drip irrigation pipe is arranged on the enrichment plant absorption layer, and a drip irrigation pipe network is formed by the interval of 50cm between pipes; the gravel water collecting layer is provided with a perforated drain pipe. The uranium-containing low-emission wastewater is treated and purified for 3-5 hours through an enrichment plant absorption layer, a modified zeolite purification layer and a gravel water collection layer from top to bottom through a drip irrigation pipe network, and the purified water is discharged through a perforated drain pipe in the gravel water collection layer. The method can effectively solve the problem of dual pollution of radioactivity of uranium and heavy metal toxicity in radioactive polluted water bodies such as uranium mining and metallurgy, uranium tailings and the like at low cost.
However, the above-mentioned solutions have a limited effect on the treatment of wastewater containing radioactive elements or the treatment system is too complicated. Therefore, there is still a need in the art for a zeolite adsorbent having excellent adsorption effect on radioactive elements and a method for preparing the same.
Disclosure of Invention
The problem of adsorbent among the prior art to the radioactive element adsorption effect limited in the waste water is solved in order to solve, perhaps solve the too high problem of cost of adsorption system among the prior art. The invention firstly provides a novel zeolite material adsorbent and a preparation method thereof.
Basalt is a solid waste with pollution property, has fine particles, is easy to float when meeting wind, and causes dust pollution to the environment. The utilization of basalt is not only a method for solving dust pollution, but also one of the ways for improving solid waste recycling. At present, the comprehensive utilization rate of dust all over the world is between 3% and 57%, and the average utilization rate is 16%. The large amount of basalt reserves in China make the basalt become a material with high quality and low price.
The inventor of the invention finds that the basalt-based X-type zeolite material is prepared from the basalt waste through an alkali fusion-hydrothermal crystallization method through experiments. And enabling the basalt-based X-type zeolite material to be capable of greatly adsorbing uranium in uranium-containing wastewater under the participation of ultrasound.
In a particular embodiment, the basalt-based type X zeolite material is a hydrated aluminosilicate mineral.
Therefore, the invention firstly provides a zeolite material adsorbent, wherein the zeolite material adsorbent is a basalt-based zeolite material, and the basalt-based zeolite material is prepared by blending, melting and processing basalt and alkali at a high temperature of 500-800 ℃ and then crystallizing.
In a specific embodiment, the basalt is subjected to acid washing, then subjected to high-temperature blending and melting treatment with alkali, and then subjected to hydrothermal crystallization to obtain the adsorbent.
In a specific embodiment, the acid used in the acid washing process is hydrochloric acid and the base is sodium hydroxide.
In a specific embodiment, the mass ratio of basalt to hydrochloric acid is 1: 0.001 to 1, preferably 1: 0.01-0.5, wherein the mass ratio of the pickled basalt material to the sodium hydroxide is 1: 0.1 to 3, preferably 1: 0.3 to 2.
In the present invention, the hydrochloric acid in the mass ratio of basalt to hydrochloric acid means the mass of hydrogen chloride in hydrochloric acid, and in fact, in the acid washing process, a hydrochloric acid aqueous solution having a concentration of 5 to 38 wt% is generally used.
The invention also provides a preparation method of the zeolite material adsorbent, which comprises the steps of firstly pickling basalt powder, then blending and melting the pickled basalt material and alkali at the high temperature of 500-800 ℃, wherein the blending and melting treatment temperature is preferably 600-700 ℃, and then performing hydrothermal crystallization in a closed reaction kettle at the temperature of 90-150 ℃, and the hydrothermal crystallization temperature is preferably 110-130 ℃, so as to obtain the basalt-based zeolite material.
In a specific embodiment, the hydrothermal crystallization process is carried out under the autogenous pressure of a closed reaction kettle, and the solid material after the hydrothermal crystallization is washed to be neutral by using deionized water and dried to obtain the basalt-based zeolite material.
In a specific embodiment, the blending and melting treatment time of the basalt material and alkali at high temperature is more than 1 hour, preferably 2.5-4 hours; the hydrothermal crystallization time is 2 hours or more, preferably 10 hours or more.
In a specific embodiment, the acid-washed basalt material is washed to be neutral by deionized water, and is subjected to blending and melting treatment with alkali after being dried.
In a specific embodiment, the blended and melted material is aged in water, and then subjected to hydrothermal crystallization treatment to obtain the adsorbent, wherein the aging time is more than 2 hours.
In a specific embodiment, the substance after hydrothermal crystallization is subjected to centrifugal separation and washing, and after liquid and lower gray solid are discarded, the obtained upper white solid is the adsorbent.
The invention also provides a method for treating the wastewater containing the radioactive elements by using the zeolite material, wherein the zeolite material adsorbent is a basalt-based zeolite material, and the basalt-based zeolite material is prepared by blending, melting and treating basalt and alkali at a high temperature of 500-800 ℃ and then crystallizing.
In a specific embodiment, the radioactive element is one or more of uranium, thorium and radium, and ultrasonic dispersion is used during or before the wastewater treatment to allow the radioactive element-containing wastewater to be in sufficient contact with the adsorbent.
In a specific embodiment, the time for ultrasonic dispersion is 2min or more, preferably 3 to 30 minutes, and more preferably 5 to 20 minutes.
In a specific embodiment, the adsorbent and the wastewater are in adsorption contact for more than 1 hour, preferably 2 to 20 hours, and the wastewater has a pH value of 5 to 8, preferably 5 to 7.
In a specific embodiment, the temperature of the wastewater during the adsorption process is maintained at 20 to 50 ℃, preferably 30 to 45 ℃.
The invention at least has the following characteristics and beneficial effects:
1) the invention firstly utilizes the three-dimensional tetrahedral structure of (basalt) mesoporous and microporous structures to obtain a novel inorganic material with higher crystal integrity, in particular to X-type zeolite with higher crystallinity. The basalt-based X-type zeolite material is uniform in particle size distribution, complete in crystal form and 2-3 mu m in size; the basalt-based X-type zeolite material has strong uranium adsorption capacity when being used for absorbing uranium from wastewater.
2) In the invention, when uranium-containing wastewater is treated, a solid-liquid interface of an adsorption system is broken by means of ultrasonic energy, so that an adsorbent (basalt-based X-type zeolite material) and a solution (uranium-containing wastewater) are quickly mixed, and the adsorption speed of the adsorbent on uranium ions is accelerated.
3) The basalt-based X-type zeolite material provided by the invention well utilizes the high-efficiency adsorption capacity of mesoporous and microporous structures of zeolite on heavy metal ions. Compared with common adsorbents, the adsorption capacity of the basalt-based X-type zeolite material is remarkably improved, and the maximum adsorption capacity of the basalt-based X-type zeolite material to uranium reaches 2442mg/g, which is 10 times of that of common adsorption materials to uranium.
4) The application of the basalt-based X-type zeolite material in uranium-containing wastewater treatment has the advantages of simple process, convenience in operation, high reaction speed and easiness in process control, and is suitable for large-scale industrial production and application.
5) In the preparation method of the adsorbent, the basalt is used as the raw material to synthesize the zeolite, and the obtained zeolite adsorbent has higher use value and reduces the cost of synthesizing the zeolite in the traditional industry.
Drawings
Fig. 1 is an SEM image of a sample of the adsorbent in example 1 of the present invention, where fig. a and b are SEM images before adsorption of uranyl ions, and fig. c and d are SEM images after adsorption of uranyl ions; and wherein figures a and c are SEM images in a field of view with a scale of 100nm, and figures b and d are SEM images in a field of view with a scale of 1 micron.
Fig. 2 is an XRD pattern of the adsorbent sample of example 1 of the present invention, where the lower line is the XRD line before adsorption of uranyl ions and the upper line is the XRD line after adsorption of uranyl ions.
Fig. 3 is an FI-IR diagram of a sample of the adsorbent in example 1 of the present invention, where a is the FI-IR diagram before adsorption of uranyl ions and b is the FI-IR diagram after adsorption of uranyl ions.
Fig. 4 is an EDS diagram of an adsorbent sample in example 1 of the present invention, where a is the EDS diagram before adsorption of uranyl ions and b is the EDS diagram after adsorption of uranyl ions.
FIG. 5 is a graph showing the effect of the time for which the adsorbent of the present invention participates in the adsorption reaction on the adsorption result.
FIG. 6 is a graph showing the effect of pH on adsorption results of the adsorbents of the present invention participating in adsorption reactions.
FIG. 7 is a graph showing the effect of temperature of the adsorbent of the present invention participating in the adsorption reaction on the adsorption results.
FIG. 8 is a schematic diagram of adsorption results of different cycle adsorption times of the adsorbent participating in adsorption reaction according to the present invention.
Fig. 9 is a process flow diagram corresponding to the preparation method of the adsorbent of the present invention.
Detailed Description
The present invention is described in detail by the following examples and the accompanying drawings, but the scope of the present invention is not limited thereto, and the scope of the present invention is defined by the claims.
Example 1
According to m (basalt material): m (hydrochloric acid) ═ 10: 1, m (acid-washed basalt material): m (sodium hydroxide) ═ 1: 1, respectively weighing 40g of basalt material and dissolving the basalt material in 50ml of hydrochloric acid solution; 10g of the pickled, washed and dried basalt material and 10g of the sodium hydroxide particles are uniformly mixed and placed in a crucible, and the mixture is roasted for 3 hours at the temperature of 650 ℃ in a muffle furnace. And then taking out the roasted solid, adding 50ml of deionized water, aging for 10h under the condition of magnetic stirring at 150r/min, transferring the mixture into a polytetrafluoroethylene autoclave, putting the polytetrafluoroethylene autoclave into an oven, crystallizing at the constant temperature of 120 ℃ for 12h, taking out the autoclave, and cooling to the room temperature. Washing the obtained precipitate with deionized water to neutrality, performing centrifugal separation on solid and liquid, taking the upper layer solid, placing in a thermostat, and drying at 60 ℃ for 12h to obtain the product. Wherein the white solid at the upper layer in the centrifugal product is dried to obtain the adsorbent product of the invention, while the gray solid at the lower layer is waste after alkali fusion, and the white solid and the activation product are put into an autoclave together for hydrothermal crystallization in the crystallization process.
And putting a certain amount of the prepared basalt-based X-type zeolite material adsorbent into uranium-containing wastewater, firstly dispersing for 5-15 minutes by ultrasonic assistance, and then putting into a constant-temperature water bath shaking table for adsorption reaction. And after adsorption, taking supernatant, filtering by using a 0.45-micrometer microporous filter membrane, and detecting the uranium ion concentration by using an ultraviolet spectrophotometer.
FIGS. 1-4 show the characterization spectra of the samples at various stages in example 1.
FIG. 1 is an SEM photograph of a sample, wherein a and b are SEM photographs of a basalt-based high-purity X-type zeolite; and c and d are SEM pictures of the basalt-based high-purity X-type zeolite after adsorbing uranium ions. The comparison shows that the structure of the adsorbent is not changed. After the material adsorbs uranium solution, the surface is rich in a large amount of uranium ions and becomes a rough surface, and the width of the adsorbed material is wider than that of the material before adsorption. It can be seen that the uranium was successfully adsorbed by the material.
In fig. 2, the line at the bottom is the XRD pattern of the basalt-based high-purity type X zeolite; the upper spectral line is an XRD (X-ray diffraction) spectrum of the basalt-based high-purity X-type zeolite for adsorbing uranium. In the upper line of fig. 2, two characteristic peaks (reading on the abscissa visible to the moving cursor when detected) of 2 θ 46 and 54 are characteristic peaks of uranium. Because the surface of the material is rich in a large amount of uranium elements, the outer surface of the adsorbent is covered with a thick uranium ion layer, and compared with the prior art, the characteristic peaks 2 theta of the adsorbent are reduced by 10, 12, 32 and 24.
In FIG. 3, a is the FT-IR spectrum of basalt-based type X zeolite; and b is an FT-IR spectrum of the basalt-based X-type zeolite after uranium ions are adsorbed. Comparing a and b in fig. 3 shows that the peaks around 1464, 673, and 564 were changed after uranium adsorption, and we concluded that the adsorption of uranium by the basalt-based type X zeolite was successful.
In fig. 4, a is an EDS analysis spectrum of the basalt-based high-purity X-type zeolite; and b is an EDS analysis map of the basalt-based high-purity X-type zeolite after uranium ions are adsorbed. The spectrum of the basalt based X-type zeolite b in fig. 4 adsorbing uranium ions shows a peak of uranium with a uranium content of 27.60 wt%. The results show that the basalt-based X-type zeolite successfully adsorbs uranium.
Fig. 5 is a graph showing the change with time of the adsorption amount and adsorption percentage of uranium ions by the basalt-based type X zeolite obtained in example 1. From the start of timing of the constant temperature water bath after the ultrasound, the adsorption conditions 1h to 14h after the constant temperature water bath adsorption were examined. The initial concentration of uranium-containing wastewater in the experiment shown in fig. 5 was 35mg.L-1(simulating the content of uranium in industrial wastewater), the pH value is 6, the temperature of the wastewater is 30 ℃, the volume of the uranium-containing wastewater for the test is 340mL, and the dosage of an adsorbent, namely the basalt-based X-type zeolite, in the wastewater is 0.005 g.
As can be seen from FIG. 5, the adsorption capacity of the basalt-based X-type zeolite prepared in example 1 of the present invention to uranium ions in wastewater reaches 2153mg/g, that is, each gram of the material can adsorb 2.153g of uranium. As can be seen from the data of the adsorption percentage in fig. 5, the material of the present invention can reach the adsorption equilibrium in a relatively fast time, for example, about 12 hours, and can adsorb uranium ions with a certain concentration in the wastewater nearly to one hundred percent (the specific adsorption percentage is 96.48%). Therefore, the invention develops a uranium-bearing wastewater treatment method with high adsorption effect on uranium ions in wastewater.
In other experiments, when the content of uranium in the uranium-containing wastewater reaches 200mg/L, the adsorption capacity of the basalt-based X-type zeolite prepared by the method of the invention on uranium ions in the wastewater can reach 2442mg/g to the maximum, and the adsorption percentage reaches 61.65%. The analytical reason should be that uranium (VI) in solution is almost completely adsorbed by the zeolite when the initial uranium concentration is low. As the initial concentration of the uranium solution increases, the active adsorption sites are continuously occupied until the uranium ions in the solution reach 200mg/L and the maximum adsorption capacity reaches 2442 mg/g.
Example 2
In this example, the adsorption condition of the basalt-based X-type zeolite material on uranium-containing wastewater with different pH values is examined. The initial concentration of uranium-containing wastewater in the experiment shown in FIG. 6 was 35mg.L-1The adsorption time is 8 hours, the temperature of the wastewater is 30 ℃, the volume of the uranium-containing wastewater for the test is 340mL, the dosage of the adsorbent in the wastewater is 0.005g, and the pH value of the wastewater is 3-10.
As can be seen from FIG. 6, the waste waterThe pH value of the composite material is within the range of 5-7, and the adsorption capacity of the composite material to uranium in uranium-containing wastewater is high. As can be seen from FIG. 6, the pH 6 of the uranium-bearing wastewater to be treated is that the basalt-based X-type zeolite material adsorbs UO2 2+The adsorption effect of the pH value data point is obviously better than that of the wastewater at other pH values.
Example 3
This example is to examine the adsorption of the basalt-based X-type zeolite material to uranium-containing wastewater as a function of temperature. The initial concentration of uranium-containing wastewater in the experiment shown in FIG. 7 was 35mg.L-1The adsorption temperature is 25-45 ℃, the pH value of the wastewater is 6, the volume of the uranium-containing wastewater for the test is 340mL, the dosage of the adsorbent in the wastewater is 0.005g, and the adsorption time of the wastewater is 12 h.
As can be seen from FIG. 7, at a temperature of 30 ℃, the adsorption amount of the basalt-based X-type zeolite material to uranium in uranium-containing wastewater reaches the maximum (the adsorption amount is 2268mg/g, and the adsorption rate is 95.33%). As can be seen from FIG. 7, the optimum adsorption temperature was obtained when the adsorption temperature was 30 ℃. It is also clear from FIG. 7 that the adsorption amount of uranium can be maintained at 2100mg/g or more even at a temperature of 30 to 45 ℃ for adsorption of wastewater, which means that the temperature of wastewater does not greatly affect the adsorption.
The data points represented by squares in fig. 5-7 all correspond to adsorption capacity data on the left ordinate, and the data points represented by triangles all correspond to adsorption rate data on the right ordinate.
Example 4
This example examines the desorption and reusability of the basalt based type X zeolite material adsorbent. FIG. 8 is an adsorption performance of the basalt-based X-type zeolite adsorbent in recycling. In the figure, 20mL of 2mol.L is used-1NaOH is used as eluent for desorbing UO from basalt-based X-type zeolite material2 2+Experiments have shown that this is the most suitable eluent. As can be seen from fig. 8, the adsorption capacity of the basalt-based X-type zeolite material was reduced from 93.06% in the first cycle to 80.13% in the fifth cycle. It is clear that the performance of the adsorbent is not significantly reduced after five cycles of repeated use and regeneration, which indicates that the basalt-based type X zeolite material may potentially beIn situ for the adsorption of UO from aqueous solutions2 2+。
The uranium in the wastewater is generally in a complex or ion state, the chemical valence state of the uranium is generally not changed in the adsorption treatment process of the uranium-containing wastewater, and the uranium is not reduced under the action of the basalt-based X-type zeolite material.
In the invention, under the action of ultrasonic waves, the basalt-based X-type zeolite material is fully contacted with uranium-containing wastewater, a solid-liquid interface is broken, and uranium in the wastewater can be smoothly adsorbed by the basalt-based X-type zeolite material.
The foregoing is a more detailed description of the present invention in connection with specific preferred embodiments, and it is not intended that the practice of the invention be limited to these descriptions. For those skilled in the art to which the invention pertains, several simple deductions and substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. The zeolite material adsorbent is a basalt-based zeolite material, and the basalt-based zeolite material is prepared by blending, melting and processing basalt and alkali at a high temperature of 500-800 ℃ and then crystallizing.
2. A zeolite adsorbent as claimed in claim 1, wherein the basalt is subjected to acid washing, then subjected to high temperature blending and melting with alkali, and then subjected to hydrothermal crystallization to obtain the adsorbent.
3. A zeolitic material adsorbent according to claim 2, characterized in that the acid used in the acid washing process is hydrochloric acid and the base is sodium hydroxide.
4. A zeolitic material adsorbent according to claim 3, characterized in that the mass ratio of basalt to hydrochloric acid is 1: 0.001 to 1, preferably 1: 0.01-0.5, wherein the mass ratio of the pickled basalt material to the sodium hydroxide is 1: 0.1 to 3, preferably 1: 0.3 to 2.
5. A preparation method of the zeolite material adsorbent as claimed in any one of claims 1 to 4, comprising the steps of firstly, carrying out acid washing on basalt powder, then carrying out blending and melting treatment on the acid-washed basalt material and alkali at a high temperature of 500-800 ℃, wherein the blending and melting treatment temperature is preferably 600-700 ℃, and then carrying out hydrothermal crystallization in a closed reaction kettle at a temperature of 90-150 ℃, wherein the hydrothermal crystallization temperature is preferably 110-130 ℃, so as to obtain the basalt-based zeolite material.
6. The preparation method according to claim 5, wherein the hydrothermal crystallization process is carried out under the autogenous pressure of a closed reaction kettle, and the solid material after the hydrothermal crystallization is washed to be neutral by using deionized water and dried to obtain the basalt-based zeolite material.
7. The preparation method according to claim 5, characterized in that the time for the blending and melting treatment of the basalt material and the alkali at high temperature is more than 1 hour, preferably 2.5 to 4 hours; the hydrothermal crystallization time is 2 hours or more, preferably 10 hours or more.
8. The method according to claim 5, wherein the acid-washed basalt material is washed with deionized water to neutrality and then subjected to a blending melting treatment with alkali after being dried.
9. The method according to claim 8, wherein the blended and melted material is aged in water and then subjected to hydrothermal crystallization to obtain the adsorbent, wherein the aging time is 2 hours or more.
10. The preparation method according to any one of claims 5 to 9, characterized in that the substance after hydrothermal crystallization is centrifugally separated and washed, and after the liquid and the lower gray solid are discarded, the upper white solid is the adsorbent.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112495339A (en) * | 2020-10-13 | 2021-03-16 | 核工业北京化工冶金研究院 | Method for adsorbing manganese ions by modified zeolite |
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| KR20130027299A (en) * | 2011-09-07 | 2013-03-15 | 유림엔마텍(주) | Obataining method and the apparatus for water treatment formal zeolite using hydrothermal reaction in an autoclave |
| JP2013164407A (en) * | 2012-02-09 | 2013-08-22 | Eigado:Kk | Method for decontaminating radioactive material |
| CN103446994A (en) * | 2012-05-30 | 2013-12-18 | 李剑 | Method for adsorption treatment of uranium-containing wastewater through using iron modified attapulgite adsorbent |
| CN105413653A (en) * | 2015-11-11 | 2016-03-23 | 胡倾成 | Greystone fiber modified porous light active calcium silicate highly radioactive wastewater treatment agent and preparation method |
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- 2019-11-29 CN CN201911202453.1A patent/CN110918050A/en not_active Withdrawn
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| KR20130027299A (en) * | 2011-09-07 | 2013-03-15 | 유림엔마텍(주) | Obataining method and the apparatus for water treatment formal zeolite using hydrothermal reaction in an autoclave |
| JP2013164407A (en) * | 2012-02-09 | 2013-08-22 | Eigado:Kk | Method for decontaminating radioactive material |
| CN103446994A (en) * | 2012-05-30 | 2013-12-18 | 李剑 | Method for adsorption treatment of uranium-containing wastewater through using iron modified attapulgite adsorbent |
| CN105413653A (en) * | 2015-11-11 | 2016-03-23 | 胡倾成 | Greystone fiber modified porous light active calcium silicate highly radioactive wastewater treatment agent and preparation method |
Non-Patent Citations (1)
| Title |
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| KE GUOJUN ET AL.: ""Synthesis of X-Zeolite from Waste Basalt Powder and its Influencing Factors and Synthesis Mechanism"", 《MATERIALS》 * |
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| CN112495339A (en) * | 2020-10-13 | 2021-03-16 | 核工业北京化工冶金研究院 | Method for adsorbing manganese ions by modified zeolite |
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