CN109954476B - Manganese-doped double-shell calcium carbonate hollow microsphere CO2Method for preparing adsorbent - Google Patents
Manganese-doped double-shell calcium carbonate hollow microsphere CO2Method for preparing adsorbent Download PDFInfo
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Abstract
The invention relates to a manganese-doped double-shell calcium carbonate hollow microsphere CO2A preparation method of the adsorbent. The method comprises the following steps: firstly, preparing carbon spheres by using the steps of hydrothermal reaction of a sucrose solution and the like, then adding the carbon spheres serving as sacrificial templates into a mixed solution of calcium salt and manganese salt, and then performing water bath, drying, roasting and the like to obtain the manganese-doped double-shell calcium carbonate hollow microspheres CO2An adsorbent. According to the invention, by modulating the calcium-manganese ratio, the carbon sphere template and the solvent composition, the shell thickness, the microsphere size and the calcium-manganese ratio of the manganese-doped double-shell hollow calcium carbonate microsphere can be accurately regulated. The prepared adsorbent shows higher adsorption capacity and good stability in adsorption and desorption cycles, wherein the initial adsorption capacity of the adsorbent with the optimal performance reaches 0.62g of CO at most2Per g adsorbent, maintained at 0.53g CO after 25 cycles2/g adsorbent。
Description
Technical Field
The invention relates to inert component doped calcium oxide-based CO with a special morphology2A preparation method of an adsorbent, belonging to CO2The field of high-temperature capture and material preparation.
Background
In recent years, as fossil fuels are increasingly used by humans, combustion thereof generates a large amount of CO2。CO2As one of the major greenhouse gases, environmental problems due to the greenhouse effect have been increasingly serious. CO currently produced by human activity2Most of the flue gas comes from the flue gas in a coal-fired power plant, and the calcium-based adsorbent can directly react to CO in the flue gas due to the higher operating temperature of the calcium-based adsorbent2The flue gas is collected without being cooled, so that energy can be saved, and the flue gas is collectedThe method has the advantages of large adsorption capacity, wide raw material source, low cost and the like, and becomes one of the most application-promising carbon dioxide capture technologies at present.
However, the main application difficulty of the calcium-based adsorbent is easy sintering deactivation in use process, on one hand, because of CaCO3The Taman temperature is low, on the other hand, because of CaO and CaCO3The difference of the molar volume of the adsorbent is large, and the mechanical stress generated by the volume change in the adsorption and desorption cycle generates continuous impact on the structure of the adsorbent, so that the collapse and sintering of the structure of the adsorbent are aggravated, and the inactivation is initiated. In view of these problems, the current technical method is to dope the calcium-based adsorbent with an inert component having a high melting point, and the doping method is mainly a more conventional technical method, such as a sol-gel method, a wet mixing method, an impregnation method, and the like, which cannot achieve the purpose of avoiding sintering of the calcium-based adsorbent by designing the structure of the adsorbent, so that the problem of sintering of the calcium-based adsorbent can be dealt with from the viewpoint of the structure design of the calcium-based adsorbent.
Disclosure of Invention
The invention aims to provide a manganese-doped double-shell calcium carbonate hollow microsphere CO aiming at the problem that the conventional calcium-based adsorbent is easy to sinter and quickly inactivate2A preparation method of the adsorbent. The method is characterized in that a manganese inert component is uniquely introduced on the basis of adopting a multi-shell hollow microsphere structure, and the method has the function of improving the adsorption capacity and stability of the adsorbent in the aspects of reducing the size of calcium carbonate grains, increasing the shell strength, improving the sphericity of the adsorbent, forming effective physical barrier and the like.
The technical scheme of the invention is as follows:
manganese-doped double-shell calcium carbonate hollow microsphere CO2The preparation method of the adsorbent comprises the following steps:
1) placing the sucrose solution in a crystallization kettle, carrying out hydrothermal crystallization reaction for 1.5-3 hours at 160-230 ℃, then carrying out suction filtration on the obtained product, alternately washing the obtained filter cake with ethanol and water, drying for 8-16 hours at 60-120 ℃, and grinding to obtain carbon spheres with the diameter of 1-4 microns;
wherein the concentration of the sucrose solution is 0.5M-2M;
2) adding metal salt into a solvent, stirring and dissolving to obtain a metal salt solution, and then adding the carbon spheres prepared in the step 1) to obtain a suspension; ultrasonically dispersing the suspension for 5-30 minutes, magnetically stirring in a water bath at 25-60 ℃ for 5-15 hours, filtering and washing the obtained filter cake, and drying at 60-120 ℃ for 8-24 hours;
wherein the metal salt is calcium nitrate, or calcium nitrate and manganese acetate, and the molar ratio of calcium nitrate: manganese acetate ═ 1: 0 to 0.01; the solvent is water or a mixed solution of ethanol and water, and the volume ratio of water to ethanol is 1: 0 to 5; in the metal salt solution, the concentration of calcium nitrate is 1-4M; adding 300-1200 mg of carbon spheres into every 30ml of metal salt solution;
3) grinding the dried product obtained in the step 2), placing the ground product into a muffle furnace, heating to 380-420 ℃ at a first heating rate in an air atmosphere, heating to 490-510 ℃ at a second heating rate, and roasting for 1-3 hours to obtain the manganese-doped double-shell calcium carbonate hollow microsphere CO2An adsorbent;
the first heating rate in the step 3) is 1-10 ℃/min, and the second heating rate is 25-75% of the first heating rate.
In the step 2), when the solvent is a mixed solution of ethanol and water, the volume ratio of the solvent to the ethanol is preferably 1: 1 to 5.
In the step 2), when the metal salts are calcium nitrate and manganese acetate, the molar ratio of calcium nitrate to manganese acetate is preferably 1: 0.01 to 0.5.
The invention has the beneficial effects that:
1. the invention successfully prepares a novel manganese-doped calcium-based adsorbent with a double-layer hollow microsphere structure, and figure 4 shows a scanning electron microscope image of a typical manganese-doped double-shell calcium carbonate hollow microsphere, and the image shows that the product has uniform particle size and good balling degree. FIG. 1 is a transmission electron microscope image of four adsorbents with different Ca/Mn ratios, and it can be seen that the four products with different Ca/Mn ratios all form clear double-layer hollow microsphere structures.
2. With the current most partCompared with the adsorption performance of the calcium-based adsorbent reported in the literature, the manganese-doped double-layer hollow calcium carbonate microsphere adsorbent prepared by the invention has higher adsorption capacity and stability, and the adsorption performance of the adsorbent is remarkably improved by the manganese doping, wherein when the microsphere size is 500nm and the calcium-manganese molar ratio is 12-1, the initial adsorption capacity of the adsorbent is as high as 0.62g-CO2The/g-adsorbent has 30 percent higher adsorption performance than the adsorbent without manganese doping, and can still maintain 0.53g-CO after 25 cycles2The/g-adsorbent has 130% higher adsorption performance than the adsorbent without manganese doping, and shows excellent stability of adsorption performance.
3. The synthesis process of the invention does not involve the use of any organic solvent, initiator and surfactant, and has the advantages of environmental protection, no toxicity, simple and easy operation, uniform particle size of the obtained product and the like.
4. The invention can accurately realize the regulation and control of the shell thickness, the microsphere size and the calcium-manganese ratio of the manganese-doped double-shell hollow calcium carbonate microsphere by regulating the solvent composition, the carbon sphere size and the calcium-manganese ratio.
Drawings
Fig. 1 is a transmission electron microscope image (TEM) of a double-layered hollow calcium carbonate microsphere adsorbent of four different calcium manganese molar ratios, wherein fig. 1a, fig. 1b, fig. 1c and fig. 1d are transmission electron microscope images (TEM) of pure calcium carbonate and double-layered hollow calcium carbonate microspheres with actual calcium manganese molar ratios of 30/1, 12/1 and 7/1, respectively;
FIG. 2 shows the results of adsorption cycle testing of four adsorbents with different molar ratios of Ca and Mn;
FIG. 3 is a TEM image of manganese-doped double-layered hollow calcium carbonate microspheres of the thin shell layer prepared in example 2;
FIG. 4 is a Scanning Electron Microscope (SEM) image of a 500nm manganese-doped double-layered hollow calcium carbonate microsphere prepared in example 3;
FIG. 5 is a TEM image of a manganese-doped double-layered hollow calcium carbonate microsphere prepared in example 3 at 500 nm;
FIG. 6 shows adsorption cycle tests of 3 different sizes of manganese-doped double-layered hollow calcium carbonate microsphere adsorbents;
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Example 1
(1) Preparing a carbon sphere template: and (2) putting a 1M sucrose aqueous solution into a crystallization kettle, carrying out hydrothermal crystallization reaction at 200 ℃ for 120min, carrying out suction filtration on the obtained product after crystallization is finished, alternately washing the obtained filter cake with ethanol and water, drying the obtained product at 80 ℃ for 12h, and then grinding the product to obtain carbon spheres with the diameter of 2 mu M.
(2) Collecting 20ml anhydrous ethanol and 10ml deionized water to obtain mixed solvent, mixing 14.169g Ca (NO)3)2·4H2O and 0.588g of Mn (CH)3COO)2·4H2Adding O (namely the concentration of calcium ions is 2mol/L, the molar ratio of fed calcium and manganese ions is 25/1, the molar ratio of the calcium and manganese ions actually measured in the finally obtained adsorbent is 12/1) into the solvent to obtain a metal salt solution A, adding 600mg of the carbon sphere template prepared in the step 1) into the metal salt solution A to obtain a suspension B, performing ultrasonic dispersion on the suspension B for 30 minutes, performing magnetic stirring on the suspension B in a water bath at 40 ℃ for 8 hours, filtering, washing, and drying the filter cake at 80 ℃ for 12 hours.
(3) And (3) grinding the dried product obtained in the step (2), roasting the ground product under the condition of air atmosphere, heating to 400 ℃ at 2 ℃ per minute in a muffle furnace, immediately switching the heating rate, heating to 500 ℃ at 1 ℃ per minute, and finally roasting at 500 ℃ for 2 hours to obtain the final product. The actual calcium to manganese ratio of the resulting product was determined by ICP to be 12:1 and was designated Ca12Mn 1.
Example 2
(1) Preparing a carbon sphere template: and (2) putting a 1M sucrose aqueous solution into a crystallization kettle, carrying out hydrothermal crystallization reaction at 200 ℃ for 110min, carrying out suction filtration on the obtained product after crystallization is finished, alternately washing the obtained filter cake with ethanol and water for multiple times, then drying at 80 ℃ for 12h, and grinding to obtain carbon spheres with the diameter of 1 mu M.
(2) Taking 20ml of absolute ethyl alcohol and 10ml of deionized water to obtainMixing the solvents, mixing 14.169g of Ca (NO)3)2·4H2O and 0.588g of Mn (CH)3COO)2·4H2Adding O (namely the concentration of calcium ions is 2mol/L, the molar ratio of fed calcium and manganese ions is 25/1, the molar ratio of the calcium and manganese ions actually measured in the finally obtained adsorbent is 12/1) into the solvent to obtain a metal salt solution A, adding 600mg of the carbon sphere template prepared in the step 1) into the metal salt solution A to obtain a suspension B, performing ultrasonic dispersion on the suspension B for 30 minutes, performing magnetic stirring on the suspension B in a water bath at 40 ℃ for 8 hours, filtering, washing, and drying the filter cake at 80 ℃ for 12 hours.
3) Grinding the dried product obtained in the step 2), roasting after grinding, wherein the roasting condition is an air atmosphere, heating to 400 ℃ at 2 ℃ per minute in a muffle furnace, then switching the heating rate, heating to 500 ℃ at 1 ℃ per minute, and finally roasting for 2 hours at 500 ℃ to obtain the final product. The product obtained was named Ca12Mn1-500 according to the actual molar ratio of calcium to manganese as determined by ICP.
Example 3
(1) Preparing a carbon sphere template: and (2) putting the sucrose aqueous solution with the concentration of 1M into a crystallization kettle, carrying out hydrothermal crystallization reaction at 200 ℃ for 120min, carrying out suction filtration on the obtained product after crystallization is finished, alternately washing the obtained filter cake with ethanol and water for multiple times, then drying at 80 ℃ for 12h, and grinding to obtain carbon spheres with the diameter of 2 mu M.
(2) 30ml of deionized water is taken to obtain a mixed solvent, and 14.169g of Ca (NO) is added3)2·4H2O and 0.588g of Mn (CH)3COO)2·4H2Adding O (namely the concentration of calcium ions is 2mol/L, the molar ratio of fed calcium and manganese ions is 25/1, the molar ratio of the calcium and manganese ions actually measured in the finally obtained adsorbent is 12/1) into the solvent to obtain a metal salt solution A, adding 600mg of the carbon sphere template prepared in the step 1) into the metal salt solution A to obtain a suspension B, performing ultrasonic dispersion on the suspension B for 30 minutes, performing magnetic stirring on the suspension B in a water bath at 40 ℃ for 8 hours, filtering, washing, and drying the filter cake at 80 ℃ for 12 hours.
3) Grinding the dried product obtained in the step 2), roasting after grinding, wherein the roasting condition is an air atmosphere, heating to 400 ℃ at 2 ℃ per minute in a muffle furnace, then switching the heating rate, heating to 500 ℃ at 1 ℃ per minute, and finally roasting for 2 hours at 500 ℃ to obtain the final product. According to the actual molar ratio of calcium to manganese measured by ICP, the obtained product is Ca12Mn1 adsorbent with a thin shell layer.
Example 4
The other steps are the same as example 1 except that Mn (CH)3COO)2·4H2The addition amount of O is 0.196g, namely the molar ratio of the fed calcium to the fed manganese is 75: 1, actual calcium manganese molar ratio by ICP of 30: 1, named Ca30Mn 1.
Example 5
The other steps are the same as example 1 except that Mn (CH)3COO)2·4H2The addition amount of O is 1.471g, namely the molar ratio of the fed calcium to the fed manganese is 10: 1, actual calcium manganese molar ratio by ICP of 7: 1, named Ca7Mn 1.
The calcium to manganese ratios of the adsorbents referred to in the figures are all actual calcium to manganese molar ratios as measured by ICP.
From fig. 1 we can see that the four products with different calcium-manganese ratios all form a clear double-layer hollow microsphere structure.
FIG. 2 is a CO analysis of four different calcium/manganese molar ratios of two-layer hollow microsphere adsorbents2And (5) evaluating the adsorption performance. The evaluation was performed on a thermogravimetric analyzer (STA449F 3). For evaluation, approximately 5mg of the product was placed on a crucible under N2Heating to 600 ℃ at a heating rate of 10 ℃/min in the atmosphere, and then switching the atmosphere to 50 vol% CO2/50vol％N2Then, adsorption was performed for 45 min. After the adsorption is finished, the temperature is raised to 700 ℃ at the heating rate of 10 ℃/min under the nitrogen atmosphere, and the desorption is carried out for 20min under the nitrogen atmosphere. After the desorption is finished, the temperature is reduced to 600 ℃ at the cooling rate of 10 ℃/min under the nitrogen atmosphere for adsorption. The cycle test of the adsorption and desorption performance is completed for many times in such a cycle. As can be seen from fig. 2, the three adsorbents doped with manganese all performed better than the adsorbent not doped with manganese. Wherein the initial adsorption capacity of the manganese-free adsorbent is 0.45 g-CO2Per g-ads, after 25 cycles down to 0.23g-CO2The stability is poor. To forWhen the ratio of calcium to manganese is 30-1, the initial adsorption capacity is increased to 0.67g-CO2G-ads, however the adsorption performance is still not very stable. When the calcium-manganese ratio is reduced to 12-1 and 10-1, the initial adsorption capacity of the adsorbent reaches 0.56g-CO respectively2(g-ads) and 0.47g-CO2Per g-ads, there was a slight decrease in adsorption capacity after 25 cycles, showing excellent stability. The addition of manganese can improve the adsorption capacity of the adsorbent, and the addition of sufficient manganese can obviously improve the adsorption stability of the adsorbent.
Fig. 3 is a TEM image corresponding to the product of example 3, and it can be seen that the thickness of the shell layer can be effectively adjusted by changing the solvent to pure water, and manganese-doped double-shell hollow calcium carbonate microspheres with thinner shell layers can be obtained.
Fig. 4 is an SEM image of the product in example 2, and it can be seen that the manganese-doped double-shell hollow microsphere adsorbent prepared by the sacrificial template method using carbon spheres as a template has the characteristics of uniform particle size and good sphericity.
Fig. 5 corresponds to a TEM image of the product in example 2, the adsorbent microsphere has a diameter of 500nm, and it can be seen that manganese-doped double-shell hollow microsphere adsorbent having a smaller diameter can be effectively obtained by using a carbon sphere template having a smaller diameter, and size adjustment of the manganese-doped double-shell hollow microsphere is achieved by using carbon sphere templates of different sizes.
FIG. 6 shows CO of three manganese-doped double-shell hollow microsphere adsorbents with calcium-manganese ratios of 12-1 and diameters of 1500 nm, 1200 nm and 500nm respectively2And (5) evaluating the adsorption performance. The evaluation conditions were the same as those in FIG. 1, and it can be seen that the adsorption capacity was consistently higher for the smaller microsphere diameters, i.e., Ca12Mn1-500, than for the other two larger microsphere adsorbents over 25 cycles. Its initial adsorption capacity was 0.62g-CO2Per g-ads, the adsorption capacity can still be maintained at 0.53g-CO2/g-ads after 25 cycles, showing more excellent CO2And (4) adsorption performance.
The invention is not the best known technology.
Claims (1)
1. Manganese-doped double-shell calcium carbonate hollow structureMicrosphere CO2A method for producing an adsorbent, characterized in that the method comprises the steps of:
1) placing the sucrose solution in a crystallization kettle, carrying out hydrothermal crystallization reaction for 1.5-3 hours at 160-230 ℃, then carrying out suction filtration on the obtained product, alternately washing the obtained filter cake with ethanol and water, drying for 8-16 hours at 60-120 ℃, and grinding to obtain carbon spheres with the diameter of 1-4 microns;
wherein the concentration of the sucrose solution is 0.5M-2M;
2) adding metal salt into a solvent, stirring and dissolving to obtain a metal salt solution, and then adding the carbon spheres prepared in the step 1) to obtain a suspension; ultrasonically dispersing the suspension for 5-30 minutes, magnetically stirring in a water bath at 25-60 ℃ for 5-15 hours, filtering and washing the obtained filter cake, and drying at 60-120 ℃ for 8-24 hours;
wherein, the metal salt is calcium nitrate and manganese acetate, and the molar ratio of the calcium nitrate: manganese acetate ═ 1: 0.01 to 0.5; the solvent is water or a mixed solution of ethanol and water, and the volume ratio of water to ethanol is 1: 1-5; in the metal salt solution, the concentration of calcium nitrate is 1-4M; adding 300-1200 mg of carbon spheres into every 30ml of metal salt solution;
3) grinding the dried product obtained in the step 2), placing the ground product into a muffle furnace, heating to 380-420 ℃ at a first heating rate in an air atmosphere, heating to 490-510 ℃ at a second heating rate, and roasting at the temperature for 1-3 h to obtain the manganese-doped double-shell calcium carbonate hollow microsphere CO2An adsorbent;
the first heating rate in the step 3) is 1-10 ℃/min, and the second heating rate is 25-75% of the first heating rate.
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