CN111233084A - Ion sieve for adsorbing cesium ions and preparation method thereof - Google Patents
Ion sieve for adsorbing cesium ions and preparation method thereof Download PDFInfo
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- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 46
- 150000002500 ions Chemical class 0.000 title claims abstract description 35
- -1 cesium ions Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 29
- 239000010936 titanium Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 15
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 25
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 10
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 10
- OTNGJPUGTXULBS-UHFFFAOYSA-N cesium titanium Chemical compound [Ti][Cs] OTNGJPUGTXULBS-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000013535 sea water Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 abstract description 10
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000010532 solid phase synthesis reaction Methods 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005470 impregnation Methods 0.000 abstract description 2
- 238000002441 X-ray diffraction Methods 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910001417 caesium ion Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910001410 inorganic ion Inorganic materials 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000209499 Lemna Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FJAAKDGALOFQSO-UHFFFAOYSA-N [K].[Ni] Chemical compound [K].[Ni] FJAAKDGALOFQSO-UHFFFAOYSA-N 0.000 description 1
- KYNKUCOQLYEJPH-UHFFFAOYSA-N [K][Ti] Chemical compound [K][Ti] KYNKUCOQLYEJPH-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- LRGKLCMGBJZMTB-UHFFFAOYSA-J hydrogen phosphate;tin(4+) Chemical compound [Sn+4].OP([O-])([O-])=O.OP([O-])([O-])=O LRGKLCMGBJZMTB-UHFFFAOYSA-J 0.000 description 1
- BJRNKVDFDLYUGJ-RMPHRYRLSA-N hydroquinone O-beta-D-glucopyranoside Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CC=C(O)C=C1 BJRNKVDFDLYUGJ-RMPHRYRLSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
Abstract
The invention belongs to the technical field of ion sieves, and discloses an ion sieve for adsorbing cesium ions and a preparation method thereof. The invention provides an ionic sieve for adsorbing cesium ions and a preparation method thereof, wherein a precursor Cs of the ionic sieve is finally obtained by taking titanium hydroxide as a titanium source2Ti6O13And then adding the solution into an acid solution for impregnation to obtain the cesium-adsorbed ionic sieve. The cesium ion sieve controllably prepared by the high-temperature solid phase method has good ion exchange selectivity on Cs +, high saturated exchange capacity, high crystallinity, pure product and good crystallization effect.
Description
Technical Field
The invention relates to an ion sieve, in particular to an ion sieve for adsorbing cesium ions and a preparation method thereof.
Background
Cesium and its compounds are widely used in high-tech fields such as optical crystals, medicines, catalysts, nuclear energy, information industry, aerospace industry, fluorescent materials, electronic technology, automation and the like, and also used in cesium atomic clocks, photocells and the like, and the demand is steadily increasing. Cesium is a scarce resource, the average content of cesium in the earth crust is 3.0mg/L, and seawater also contains cesium (the content is about 3.0X 10-4mg/L, the total amount is large, and the concentration is low). In China, a lot of salt lake brine contains cesium resources and is mainly distributed in Qinghai, Tibet, Hubei and other places, and Cs is contained in salt lake brine, geothermal water and hot springs of Zambu salt lake and other salt lake in Tibet plateau+The mother liquor for extracting lithium often contains Cs+. Cs-containing salts of Zambu salt lake and Binmao salt lake+The amount is 12.15-34.5mg/L, and the method has mining value. The nuclear reaction waste liquid contains a large amount of radioactive Cs137, and needs to be treatedThe solidified Cs137 is extracted and recovered therefrom.
The method for extracting cesium from the solution with low cesium content such as seawater, nuclear waste liquid, salt lake brine and geothermal water comprises precipitation method, extraction method and ion exchange method (including inorganic ion exchange method and organic ion exchange method), etc., wherein the ion exchange method is suitable for extracting Cs from the dilute solution such as seawater, nuclear waste liquid, etc. due to low cesium content, the selective inorganic ion exchange method is to extract Cs from the dilute solution such as seawater, nuclear waste liquid, etc+The preferred method adopts an inorganic ion exchange method, and has the characteristic of environmental protection. The research of extracting cesium by adopting an inorganic ion exchange method is more, and Cs is adsorbed and separated by phosphomolybdate, potassium titanium ferrocyanide, potassium nickel ferrocyanide, sodium silicotitanate and other materials in Xueshiping, Yubo, Xijiali, Yongwu and the like+The ion exchange performance is measured, and the exchange capacity is up to 1.74mmolCs+The research of extracting potassium, rubidium and cesium by clinoptilolite is carried out on/g sodium silicotitanate, Gaoyang and the like, stannic phosphate selective to cesium is prepared by Huang Wenyan and the like, zirconium pyrophosphoromolybdate and W-doped zirconium pyrophosphoromolybdate are prepared by Lemna ursi, Lukai and the like, and the maximum exchange capacity is 1.66mmol Cs+/g。
The controllable preparation of the titanium-containing oxide type mesoporous material Cs2xTiyO (2x + y) is not yet taken into consideration, the controllable preparation method of the Cs2xTiyO (2x + y) in the prior art is complicated in steps, such as a sol-gel method, the reaction process is slow, the experiment period is long, a surfactant is needed, an aging step is needed, an eluent and the like are needed in the preparation process, and further such as a high-temperature solid phase method, the synthesized mesoporous material Cs2xTiyO (2x + y) is not single in component, complex in composition and poor in stability, is not suitable for further exploration of cesium saturation adsorption quantity and the like, and cannot realize selective separation of cesium ions; in the test process, the inventor unexpectedly finds that a proper titanium source is adopted, a preparation method of the ion sieve for adsorbing cesium ions is provided, a single ion sieve can be successfully synthesized, and the ion sieve is expected to make new progress and breakthrough on three key indexes of saturated exchange capacity, selectivity and stability.
Disclosure of Invention
In order to solve the technical problems of complicated preparation method, and poor saturated exchange capacity, selectivity and stability of the cesium ion sieve in the prior art, the invention provides a preparation method of an ion sieve for adsorbing cesium ions.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of an ion sieve for adsorbing cesium ions comprises the following steps:
S1taking the titanium hydroxide as a titanium source, mixing with cesium salt, and grinding to obtain a cesium-titanium compound;
S2roasting the cesium-titanium composite to obtain an ionic sieve precursor Cs2Ti6O13；
S3And subjecting the ionic sieve precursor Cs2Ti6O13And adding the solution into an acid solution for soaking to obtain the cesium-adsorbed ionic sieve.
The titanium hydroxide can be prepared by adopting a conventional preparation method, and preferably, the preparation method of the titanium hydroxide disclosed by the invention comprises the following steps: according to Ti4 +：NH4 +Preparing a titanium sulfate solution and ammonia water according to a molar ratio of 1: 4; and after the heating reaction is finished, filtering, washing and drying the titanium hydroxide precipitate to obtain pure titanium hydroxide.
Preferably, the molar ratio of the titanium hydroxide to the cesium carbonate is 3: 2.
According to the preparation method of the ion sieve for adsorbing cesium ions, the initial temperature of roasting is 20 ℃, and the temperature is increased to 100 ℃ by adopting the temperature increase speed of 8 ℃/min; heating from 100min to 400 ℃ at a heating rate of 3 ℃/min, and staying at 400 ℃ for 120 min; finally, the temperature rise speed is changed, the temperature reaches 800 ℃ after 180min, and the temperature stays at 800 ℃ for 4 h.
Preferably, the calcination is carried out in a tube furnace capable of programmed temperature rise.
The acid solution can be selected from acid solutions commonly used in the field, and preferably, the acid solution is a hydrochloric acid solution, and the molar concentration of the hydrochloric acid solution is 0.2 mol/L; the method can place the acid solution in a constant-temperature water bath oscillator, dip the acid solution for a week, filter, wash and dry the precursor of the ion sieve after acid modification to obtain the cesium-adsorbing ion sieve.
It is another object of the present invention to provide an ionic sieve adsorbing cesium ions, which is prepared by the above-mentioned method for preparing an ionic sieve.
Finally, the cesium ion sieve provided by the invention is applied to selective adsorption of cesium ions in seawater, nuclear waste liquid, salt lake brine and geothermal water.
The invention provides an ionic sieve for adsorbing cesium ions and a preparation method thereof, wherein a precursor Cs of the ionic sieve is finally obtained by taking titanium hydroxide as a titanium source2Ti6O13And then adding the solution into an acid solution for impregnation to obtain the cesium-adsorbed ionic sieve. The cesium ion sieve with a stable crystal structure, high selectivity to cesium and good stability is controllably prepared by a high-temperature solid phase method, and can preferentially adsorb Cs +, and the ion sieve has good ion exchange selectivity to Cs +; the ion sieve has high saturated exchange capacity for Cs +; in addition, titanium hydroxide is selected as a titanium source, Cs + and Ti4+ are completely combined together, the reaction completion degree is good, the crystallinity is high, the product is pure, and the crystallization effect is good.
Drawings
FIG. 1 shows a cesium-containing ionic sieve precursor Cs provided by the present invention2Ti6O13SEM picture of (1);
FIG. 2 shows a cesium-containing ionic sieve precursor Cs provided by the present invention2Ti6O13A TEM image of (B);
FIG. 3 shows an ionic sieve precursor Cs provided in example 1 of the present invention2Ti6O13An XRD pattern of (a);
fig. 4 is an XRD pattern of the ionic sieve precursor provided in comparative example 1;
fig. 5 is an XRD pattern of the ionic sieve precursor provided in comparative example 2.
Detailed Description
The invention discloses an ion sieve for adsorbing cesium ions and a preparation method thereof, and a person skilled in the art can realize the adsorption by properly improving process parameters by referring to the content. It is expressly intended that all such similar substitutes and modifications which would be obvious to those skilled in the art are deemed to be included in the invention. While the methods and applications of this invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications in the methods and applications described herein, as well as other suitable variations and combinations, may be made to implement and use the techniques of this invention without departing from the spirit and scope of the invention.
The following detailed description of the invention refers to specific embodiments thereof for better understanding by those skilled in the art.
Example 1
S1And (3) mixing the titanium hydroxide and the cesium carbonate according to a molar ratio of 3:2, mixing and fully grinding to obtain a cesium-titanium compound;
S2placing the ground compound in a tubular furnace capable of raising the temperature by a program to roast at a high temperature; the initial temperature is 20 ℃, the temperature is increased to 100 ℃ after 10min by adopting the temperature increasing speed of 8 ℃/min; heating to 400 deg.C at a heating rate of 3 deg.C/min for 100min, and standing at 400 deg.C for 120 min; then changing the temperature rise speed, reaching 800 ℃ after 180min, and staying at 800 ℃ for 4h to obtain the ion sieve precursor Cs with stable structure and large specific surface area2Ti6O13；
S3Step S2The obtained cesium-containing ionic sieve precursor Cs2Ti6O13Adding the precursor into 0.2mol/L hydrochloric acid solution, placing the solution in a constant-temperature water bath oscillator, soaking for a week, filtering, washing and drying the precursor of the ion sieve subjected to acid modification to obtain the ion sieve capable of highly selectively adsorbing cesium.
Will step S2The obtained cesium-containing ionic sieve precursor Cs2Ti6O13And (2) performing a Scanning Electron Microscope (SEM) test, wherein an SEM image is shown in figure 1, and figure 1 shows that figure 1(a) is an SEM image magnified by 10000 times, figure 1(b) is an SEM image magnified by 20000 times, the cesium ion sieve presents a scaly structure under the magnification of 20000 times, and is distributed uniformly, and the layered structure is favorable for increasing the contact area of solid and liquid and improving the adsorption performance of the ion sieve.
Will step S2The obtained cesium-containing ionic sieve precursor Cs2Ti6O13And (2) carrying out a Transmission Electron Microscope (TEM) test, wherein a TEM image is shown in FIG. 2, a TEM image of 40000 times is shown in FIG. 2(a), a TEM image of 6000 times is shown in FIG. 2(b), and FIG. 2 shows that the precursors of the ion sieve prepared by the high-temperature solid phase method provided by the invention are all in a scale-like structure, are uniformly distributed, are basically consistent with the scanning electron microscope image, and have stable structure.
Weighing 1 part of step S30.1000g of the obtained cesium ion sieve modified with acid was subjected to addition of 50ml of Na+、K+、Cs+、Li+、Mg2+、Ca2+In a mixed solution (pH 10) having a concentration of 0.100mol/L, the mixture was shaken at a constant temperature of 25 ℃ for one week to measure the concentration of each ion in the supernatant, and the adsorption amount of each ion by the ion sieve was calculated to analyze the ion exchange selectivity of the ion sieve, which is shown in table 1.
TABLE 1 exchange Capacity of ions
As can be seen, in Cs+、K+、Na+、Li+、Mg2+、Ca2+In the solution with the same concentration, the ion sieve provided by the invention is used for pairing Cs+The exchange capacity of the ion sieve reaches 321.39mg/g, and the ion sieve preferentially adsorbs Cs+Ion sieve pair Cs+Has better ion exchange selectivity.
Accurately weighing S3Placing 0.1000g of the obtained acid-modified cesium ion sieve in a 0.100mol/L Cs + solution (pH 10), immersing at 25 ℃ under constant temperature shaking for one week, measuring the ion concentration in the supernatant, calculating the saturated exchange capacity of cesium ions according to the decrease of cesium ions, and finally obtaining the saturated exchange capacity of cesium ions of 471.59 mg/g; the calculation formula is as follows:
wherein, Q: saturated exchange capacity, mg/g
C0The content of Cs + in the initial solution, mg/L
C, content of Cs + in exchange solution, mg/L
V volume of solution, L
W is the amount of exchanger, g.
The saturated exchange capacity of 471.59mg/g of the cesium ions obtained by the method is measured to be 88.22% of the theoretical value of 534.59mg/g (the theoretical value of the saturated exchange capacity of the cesium ions), and the data show that the cesium ions provided by the method have higher saturated exchange capacity.
Will step S2The obtained ionic sieve precursor Cs2Ti6O13The XRD pattern of the X-ray diffraction analysis is shown in figure 3, and figure 3 shows that the ionic sieve precursor Cs obtained by the invention2Ti6O13The characteristic peak is generally obvious, the peak shape is good, the number of mixed peaks is small, the peak shape and the position of the diffraction angle of the diffraction peak are compared with the data of the standard spectrogram PDF38-0170, the result is basically consistent, and the result shows that the Cs is similar to the standard spectrogram PDF38-0170+With Ti4+The reaction is completely combined, the reaction completion degree is better, the crystallinity is high, and the product is more ideal.
Comparative example 1
S1And mixing the titanium oxide and cesium carbonate according to a molar ratio of 3:2, mixing and fully grinding to obtain a cesium-titanium compound;
S2placing the ground compound in a tubular furnace capable of raising the temperature by a program to roast at a high temperature; the initial temperature is 20 ℃, the temperature is increased to 100 ℃ after 10min by adopting the temperature increasing speed of 8 ℃/min; heating to 400 deg.C at a heating rate of 3 deg.C/min for 100min, and standing at 400 deg.C for 120 min; and then changing the temperature rise speed, reaching 800 ℃ after 180min, and staying at 800 ℃ for 4h to obtain the product ion sieve precursor.
Carrying out X-ray diffraction analysis on the ionic sieve precursor, wherein the XRD pattern is shown in figure 4, the topmost pattern in figure 4 is the XRD pattern of the ionic sieve precursor of titanium dioxide and cesium carbonate reaction, the PDF #29-1360 pattern is the XRD pattern of titanium dioxide standard spectrum, and the PDF #38-170 pattern is Cs2Ti6O13FIG. 4 shows the oxidation of dioxideThe reaction product of titanium and cesium carbonate is mainly titanium dioxide, which indicates that titanium dioxide does not react with cesium carbonate, and the reason for analyzing the reaction product is probably that titanium dioxide has high stability and is not easy to react with other substances, so titanium dioxide is not selected as a titanium source to prepare the ion sieve for adsorbing cesium ions.
Comparative example 2
S1And (3) mixing the titanium sulfate and cesium carbonate according to a molar ratio of 3:2, mixing and fully grinding to obtain a cesium-titanium compound;
S2placing the ground compound in a tubular furnace capable of raising the temperature by a program to roast at a high temperature; the initial temperature is 20 ℃, the temperature is increased to 100 ℃ after 10min by adopting the temperature increasing speed of 8 ℃/min; heating to 400 deg.C at a heating rate of 3 deg.C/min for 100min, and standing at 400 deg.C for 120 min; and then changing the temperature rise speed, reaching 800 ℃ after 180min, and staying at 800 ℃ for 4h to obtain the product ion sieve precursor.
Performing X-ray diffraction analysis on the ionic sieve precursor, wherein an XRD (X-ray diffraction) pattern is shown in figure 5, the topmost pattern in figure 5 is an XRD pattern of the ionic sieve precursor obtained by titanium sulfate and cesium carbonate, and a PDF #38-0170 pattern is Cs2Ti6O13The XRD pattern of the standard spectrum of (1) and FIG. 5 show that the XRD pattern of the precursor of the ionic sieve, which is the product of the reaction of titanium sulfate and cesium carbonate, after X-ray diffraction is compared with the standard spectrum, the characteristic peak is not obvious, the peak shape is not good, the number of the miscellaneous peaks is large, the reaction completion degree is not good, the crystallinity is not high, and the product is not ideal, so that the titanium sulfate is not selected as a titanium source to prepare the ionic sieve for adsorbing cesium ions.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. The preparation method of the ion sieve for adsorbing cesium ions is characterized by comprising the following steps of:
S1the titanium hydroxide is used as a titanium source and is mixed with cesium saltGrinding to obtain a cesium-titanium compound;
S2roasting the cesium-titanium composite to obtain an ionic sieve precursor Cs2Ti6O13；
S3And subjecting the ionic sieve precursor Cs2Ti6O13And adding the solution into an acid solution for soaking to obtain the cesium-adsorbed ionic sieve.
2. The method of preparing the ionic sieve of claim 1, wherein the titanium hydroxide and cesium carbonate are in a molar ratio of 3: 2.
3. The method for preparing the ionic sieve of claim 1, wherein the initial temperature of roasting is 20 ℃, and the temperature is raised to 100 ℃ by adopting a temperature raising speed of 8 ℃/min; heating from 100min to 400 ℃ at a heating rate of 3 ℃/min, and staying at 400 ℃ for 120 min; finally, the temperature rise speed is changed, the temperature reaches 800 ℃ after 180min, and the temperature stays at 800 ℃ for 4 h.
4. The method of claim 3, wherein the calcining is performed in a tube furnace capable of programmed temperature rise.
5. The method of preparing an ionic sieve of claim 1, wherein the acid solution is a hydrochloric acid solution; the molar concentration of the hydrochloric acid solution is 0.2 mol/L.
6. The method for preparing the ionic sieve of claim 1 or 5, wherein the acid solution is placed in a constant-temperature water bath oscillator and is soaked for one week, and the precursor of the ionic sieve modified by the acid is filtered, washed and dried to obtain the cesium-adsorbed ionic sieve.
7. An ionic sieve adsorbing cesium ions produced by the method for producing an ionic sieve according to any one of claims 1 to 6.
8. The ionic sieve of claim 7, which is used for selectively adsorbing cesium ions in seawater, nuclear waste, salt lake brine and geothermal water.
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| CN104692406A (en) * | 2015-03-05 | 2015-06-10 | 中南大学 | Preparation method of adsorbent for selectively separating cesium ions from salt lake brine |
| CN106622170A (en) * | 2016-12-21 | 2017-05-10 | 江苏大学 | Preparation method and application of lithium-titanium type ion sieve composite membrane |
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Patent Citations (2)
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|---|---|---|---|---|
| CN104692406A (en) * | 2015-03-05 | 2015-06-10 | 中南大学 | Preparation method of adsorbent for selectively separating cesium ions from salt lake brine |
| CN106622170A (en) * | 2016-12-21 | 2017-05-10 | 江苏大学 | Preparation method and application of lithium-titanium type ion sieve composite membrane |
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