CN113304722B - Ce-K codoped MgO-based medium-temperature CO 2 Adsorbing material and preparation method thereof - Google Patents

Ce-K codoped MgO-based medium-temperature CO 2 Adsorbing material and preparation method thereof Download PDF

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CN113304722B
CN113304722B CN202110515364.3A CN202110515364A CN113304722B CN 113304722 B CN113304722 B CN 113304722B CN 202110515364 A CN202110515364 A CN 202110515364A CN 113304722 B CN113304722 B CN 113304722B
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周志明
崔鸿劼
董航
牛帅
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East China University of Science and Technology
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Abstract

The invention discloses high-performance NaNO 3 Modified Ce-K codoped MgO-based medium-temperature CO 2 Adsorbing the material. The innovation points of the invention are that, firstly, the adsorbing material of the invention has the characteristics of high adsorption capacity, high adsorption rate, simple and convenient preparation method and the like, and has practical application prospect; secondly, the adsorbing material has a unique monodisperse granular structure. At moderate temperature of CO 2 The structure can allow the NaNO to melt in the adsorption process 3 Uniformly distributed on the surface thereof, thereby promoting CO 2 Adsorption performance; thirdly, doping component CeO in the adsorbing material 2 Can provide a certain amount of oxygen vacancy, thereby forming lattice defects in the MgO and facilitating the carbonation reaction of the MgO; and doped KNO 3 Can be dissolved in molten NaNO 3 In the presence of a co-melt, thereby reducing [ Mg ] 2+ ‑O 2‑ ]Lattice energy to promote CO of the material 2 And (4) adsorption performance.

Description

Ce-K codoped MgO-based medium-temperature CO 2 Adsorbing material and preparation method thereof
Technical Field
The invention discloses high-performance NaNO 3 Modified Ce-K codoped MgO-based medium-temperature CO 2 Adsorbent material applicable to CO 2 And (4) a trapping field. The material is prepared by a sol-gel method and a deposition method, one part of the structure of the material is a Ce-K co-doped monodisperse granular MgO carrier with a specific proportion, and the other part of the structure of the material is an auxiliary agent NaNO loaded on the carrier with a specific content 3 。
Background
Since the industrial revolution, the rapid development of human society has been accompanied by a huge consumption of fossil fuels (coal, oil and natural gas), resulting in the greenhouse gas CO 2 The emission of a large amount of gas causes global warming, which has become one of the hot spots of wide concern in countries around the world. The report of the inter-government climate change committee of the united nations shows: global warming caused by human activityGlobal average temperature has risen by 0.8-1.2 ℃ compared to the mid-eighteenth century. The report predicts that if the world continues to emit CO at a carbon emission rate of 2018 2 By 2050, the global average air temperature will rise by 1.5 ℃, which will have a series of malignant effects on the global ecological environment.
Thus, CO is effectively controlled 2 Emissions have become a necessary choice for human sustainable development. CO 2 2 The capture and storage technology is a potential carbon emission control method, mainly burning fossil fuels and CO generated by industrial systems 2 Separating and storing. Based on CO in fossil fuel combustion processes 2 The stage of trapping can be divided into pre-combustion trapping, oxycombustion, and post-combustion trapping. Wherein, CO after combustion 2 Trapping means separating CO from flue gas after combustion of fuel 2 The fuel of the current power plant is mainly burnt in the air, so that the CO in the flue gas 2 Lower concentration, poor trapping effect and higher cost. Oxygen-enriched combustion CO 2 The trapping technique is to trap the fuel in an oxygen-rich (O) atmosphere 2 The concentration is higher than 95 percent), so that the CO in the flue gas can be greatly improved 2 Concentration, but this process is limited by the efficiency of cryogenic air separation and the cost of oxygen production technology. Pre-combustion capture is primarily applied in integrated coal gasification combined cycle power generation systems where syngas produced by a coal gasification unit is subjected to a water gas shift reaction to yield higher concentration CO 2 At this time, CO is carried out 2 Trapping, which can reduce energy consumption and improve process efficiency.
In CO 2 In the field of trapping, MgO belongs to the medium-temperature solid adsorption material, and has theoretical CO 2 High adsorption capacity (
Figure BDA0003062046530000011
) Low cost, no toxicity, environmental protection, high abundance of Mg element and the like, and is considered to be the most potential pre-combustion CO 2 Trapping the material. However practical lower CO limited to pure MgO 2 Adsorption capacity, slower adsorption rate and poorer adsorption-regeneration cycle stability, and the application of the MgO-based adsorption material is influencedTo a great extent. Therefore, in order to increase CO of MgO-based adsorbent 2 The adsorption performance can be reduced by introducing molten alkali metal nitrate 2+ -O 2 -]Lattice energy, promotion of CO 2 The adsorption performance or other components are doped to enhance the stability of the material.
Disclosure of Invention
The invention aims to prepare medium-temperature CO based on Ce-K CO-doped MgO 2 Adsorbent material having excellent CO 2 And (4) adsorption performance.
Ce-K codoped MgO-based medium-temperature CO 2 The adsorbing material is characterized in that the adsorbing material is prepared from a specific content of auxiliary agent NaNO 3 And a specific ratio of Ce-K co-doped MgO carrier, as shown below:
[Mg x Ce y K z ]-[Na] m
[Mg x Ce y K z ]represents a Ce-K co-doped MgO carrier, [ Na ]]Represents NaNO 3 。
x represents the mole percentage of MgO in the carrier, and x is between 80 and 90; y represents doped CeO 2 The molar percentage of y in the carrier is between 5 and 10; z represents doped KNO 3 The molar percentage of z in the carrier is between 5 and 10; the sum of x, y and z is 100;
m represents NaNO 3 M is 15-25 mol% of the carrier.
The invention also provides a preparation method of the adsorbing material, which comprises the following steps:
(1) respectively weighing a certain amount of magnesium salt, cerium salt and potassium salt, dissolving in deionized water, stirring for about 30min until the solution is transparent and clear,
wherein: the magnesium salt is one of magnesium acetate and magnesium nitrate; the cerium salt is one of cerium acetate and cerium nitrate; the potassium salt is one of potassium acetate, potassium nitrate and potassium citrate; the mole number of the magnesium salt in each 100mL of deionized water is between 0.01 and 0.02;
(2) then weighing a certain amount of citric acid and polyethylene glycol (average molecular weight is 400) and adding into the clear solution obtained in the step (1),
wherein: the molar ratio of the citric acid to magnesium ions in the solution is between 1.2 and 1.5, and the volume ratio of polyethylene glycol (average molecular weight 400) to deionized water is between 0.05 and 0.10;
(3) transferring the solution obtained in the step (2) into a flask, mechanically stirring the solution in the flask in a constant-temperature water bath at the stirring speed of 500rpm, the temperature of the constant-temperature water bath is 80 ℃, and the constant-temperature time is 4 hours;
(4) taking out the sol prepared in the step (3), placing the sol in an evaporation dish, and placing the evaporation dish in a drying oven at 150 ℃ for 5 hours to obtain fluffy gel;
(5) grinding the solid obtained in the step (4) into powder, putting the powder into a muffle furnace for calcination, heating to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, and calcining to obtain a Ce-K co-doped MgO carrier;
(6) separately weighing a certain amount of NaNO 3 Placing the mixture into a single-neck flask, adding a certain amount of anhydrous methanol, and stirring to ensure that NaNO is added 3 The mixture is completely dissolved and dissolved in the solvent,
wherein: NaNO per 100mL of anhydrous methanol 3 The mole number is between 0.005 and 0.01;
(7) weighing a certain amount of the Ce-K co-doped MgO carrier obtained in the step (5) according to the proportion, adding the carrier into the solution obtained in the step (6), and stirring for 2 hours;
(8) carrying out vacuum rotary evaporation on the suspension obtained in the step (7) at the temperature of 60 ℃, and removing the methanol solvent to obtain NaNO 3 The modified Ce-K co-doped MgO-based adsorption material.
The invention prepares the monodisperse granular MgO-based adsorbing material by a sol-gel method and a deposition method, and the material is fused with NaNO 3 And a doping component CeO 2 /KNO 3 Shows excellent CO under the promotion effect of 2 And (4) adsorption performance. The adsorption material has the characteristics of high adsorption capacity, high adsorption rate, simple and convenient preparation method and the like, and has practical application prospect; secondly, the adsorption material has a unique monodisperse granular structure. At moderate temperature CO 2 The structure can allow the NaNO to melt in the adsorption process 3 Is evenly dividedCloth on the surface, thereby promoting CO 2 Adsorption performance; thirdly, doping component CeO in the adsorbing material 2 Can provide a certain amount of oxygen vacancy, thereby forming lattice defects in the MgO and facilitating the carbonation reaction of the MgO; and doped KNO 3 Can be dissolved in molten NaNO 3 In the presence of a eutectic compound, thereby reducing [ Mg 2+ -O 2 -]Lattice energy, CO of the promoted material 2 And (4) adsorption performance.
Drawings
FIG. 1 shows [ Mg ] in example 1 of the present invention 85 Ce 5 K 10 ]-[Na] 20 Scanning electron microscope image of
FIG. 2 is XRD patterns of example 1, comparative example 1 and comparative example 2 of the present invention
FIG. 3 compares the adsorption rates of example 1, example 2, comparative example 1, comparative example 2 and comparative example 3 of the present invention
Adsorption conditions: 325 ℃, 40 vol.% CO 2 ，60min
FIG. 4 compares the adsorption-regeneration cycle performance of example 1 of the present invention with that of comparative example 1
Adsorption conditions: 325 ℃, 40 vol.% CO 2 30 min; regeneration conditions are as follows: 400 ℃, 100 vol.% N 2 ，5min
FIG. 5 shows [ Mg ] in example 2 of the present invention 80 Ce 10 K 10 ]-[Na] 20 Adsorption/regeneration cycle performance diagram of
The adsorption conditions are as follows: 325 ℃, 40 vol.% CO 2 30 min; regeneration conditions are as follows: 400 ℃, 100 vol.% N 2 ，5min
FIG. 6 shows [ Mg ] in example 3 of the present invention 90 Ce 5 K 5 ]-[Na] 20 Adsorption/regeneration cycle performance diagram of
Adsorption conditions: 325 ℃, 40 vol.% CO 2 30 min; regeneration conditions are as follows: 400 ℃, 100 vol.% N 2 ，5min
FIG. 7 shows [ Mg ] in example 4 of the present invention 85 Ce 5 K 10 ]-[Na] 25 Adsorption/regeneration cycle performance diagram of
Adsorption conditions: 325 ℃, 40 vol.% CO 2 30 min; regeneration conditions：400℃，100vol.％N 2 ，5min
Detailed Description
The present invention is described in more detail below with reference to specific embodiments, but the invention is not limited thereto.
Example 1
0.017mol of magnesium nitrate hexahydrate, 0.001mol of cerium nitrate hexahydrate and 0.002mol of potassium acetate were weighed, dissolved in 100mL of deionized water, and stirred for about 30min until the solution was transparent and clear. 0.022mol of citric acid and 5mL of polyethylene glycol (average molecular weight 400) were weighed into the resulting clear solution. The resulting solution was transferred to a 250mL single-neck flask, and the solution in the flask was mechanically stirred in a constant temperature water bath at a stirring speed of 500rpm, a temperature of 80 ℃ and a constant temperature time of 4 hours. And taking out the prepared sol, placing the sol in an evaporating dish, and placing the evaporating dish in an oven at 150 ℃ for 5 hours to obtain a fluffy gel structure. Then grinding the mixture into powder, putting the powder into a muffle furnace for calcination, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 3 hours, and obtaining a Ce-K co-doped MgO carrier after calcination; 0.01mol of sodium nitrate was weighed into a 250mL single-neck flask, 150mL of anhydrous methanol was added, and the alkali metal salt was completely dissolved by stirring. Weighing 2.33g of Ce-K co-doped MgO carrier, adding the carrier into the solution, magnetically stirring for 2 hours, performing vacuum rotary evaporation at 60 ℃, and removing the methanol solvent to obtain NaNO 3 Modified Ce-K co-doped MgO-based adsorption Material, i.e. [ Mg ] 85 Ce 5 K 10 ]-[Na] 20 . The scanning electron micrograph is shown in figure 1, the XRD spectrogram is shown in figure 2, the result shows that the material mainly consists of monodisperse MgO particles with the average particle size of 153.1nm, and the XRD analysis shows that MgO and CeO exist in the material 2 、NaNO 3 With KNO 3 The phase of (1).
Isothermal CO 2 The method for testing the adsorption performance comprises the following steps:
the invention adopts a thermogravimetric analyzer to test the adsorption isotherm of the material. About 5mg of sample was loaded in the thermogravimetric analyzer in N 2 The temperature was raised to 325 ℃ at 10 ℃/min under atmosphere, followed by 40 vol.% CO 2 Adsorbing with 20mL CO 2 And 30mL of N 2 The adsorption time was 60 min. Experiment ofThe results are shown in FIG. 3, which shows that the material was treated at 325 deg.C, 40 vol.% CO 2 And the adsorption time is 60min, the carbon dioxide adsorption capacity is
Figure BDA0003062046530000052
Calculating the carbon dioxide adsorption amount of the material according to the mass change data of the material recorded in the experimental process, wherein the carbon dioxide adsorption amount is defined as follows:
Figure BDA0003062046530000051
the adsorption-regeneration cycle performance test method comprises the following steps:
the invention adopts a thermogravimetric analyzer to test the carbon dioxide adsorption quantity of the material adsorption-regeneration cycle. The conditions for thermogravimetric analysis were: (1) the thermobalance was charged with about 5mg of sample in N 2 Heating to 325 deg.C at 10 deg.C/min under atmosphere, and then 40 vol.% CO 2 Adsorbing for 30 min; (2) after adsorption, raising the temperature to 400 ℃ (25 ℃/min) for material regeneration for 5 min; (3) after regeneration is completed, the furnace temperature is reduced to 325 ℃ at the rate of 25 ℃/min, and the cycle stability of the material can be tested by repeating the steps, and the example is performed for 10 cycles. The experimental result is shown in figure 4, and the result shows that after 10 adsorption-regeneration cycles, the carbon dioxide adsorption amount of the material is stabilized
Figure BDA0003062046530000053
Example 2
0.016mol of magnesium acetate tetrahydrate, 0.002mol of cerium acetate and 0.002mol of potassium nitrate were weighed, dissolved in 100mL of deionized water, and stirred for about 30min until the solution was clear. To the resulting clear solution was weighed 0.024mol citric acid and 8mL polyethylene glycol (average molecular weight 400). The resulting solution was transferred to a 250mL single-neck flask, and the solution in the flask was mechanically stirred in a constant temperature water bath at a stirring speed of 500rpm, a temperature of 80 ℃ and a constant temperature time of 4 hours. Will make intoTaking out the obtained sol, placing the sol in an evaporating dish, and placing the evaporating dish in a drying oven at 150 ℃ for 5 hours to obtain a fluffy gel structure. Then grinding the mixture into powder, putting the powder into a muffle furnace for calcination, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 3 hours, and obtaining a Ce-K co-doped MgO carrier after calcination; 0.01mol of sodium nitrate was weighed into a 250mL single-neck flask, 150mL of anhydrous methanol was added, and the alkali metal salt was completely dissolved by stirring. Weighing 2.66g of Ce-K co-doped MgO carrier, adding the carrier into the solution, magnetically stirring for 2 hours, performing vacuum rotary evaporation at 60 ℃, and removing the methanol solvent to obtain NaNO 3 Modified Ce-K co-doped MgO-based adsorption Material, i.e. [ Mg ] 80 Ce 10 K 10 ]-[Na] 20 。
Adsorption-regeneration cycle performance testing: performing adsorption-regeneration cycle experiment on the prepared adsorbing material on a thermogravimetric analyzer, recording the carbon dioxide adsorption capacity in 10 cycles, wherein the adsorption temperature is 325 ℃, the time is 30min, and the atmosphere is 40 vol.% CO 2 (ii) a The regeneration temperature is 400 ℃, the time is 5min, and the atmosphere is N 2 . The experimental result is shown in figure 5, and the result shows that after 10 adsorption-regeneration cycles, the carbon dioxide adsorption amount of the material is stabilized
Figure BDA0003062046530000061
Example 3
0.018mol of magnesium nitrate hexahydrate, 0.001mol of cerium acetate and 0.001mol of potassium citrate were weighed, dissolved in 100mL of deionized water, and stirred for about 30min until the solution was clear. 0.022mol of citric acid and 8mL of polyethylene glycol (average molecular weight 400) were weighed into the resulting clear solution. The resulting solution was transferred to a 250mL single-neck flask, and the solution in the flask was mechanically stirred in a constant temperature water bath at a stirring speed of 500rpm, a temperature of 80 ℃ and a constant temperature time of 4 hours. And taking out the prepared sol, placing the sol in an evaporation dish, and placing the sol in an oven at 150 ℃ for 5 hours to obtain a fluffy gel structure. Then grinding the mixture into powder, putting the powder into a muffle furnace for calcination, heating to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, and calcining to obtain a Ce-K co-doped MgO carrier; weigh 0.008mol of nitreSodium salt was placed in a 250mL single-neck flask, 150mL of anhydrous methanol was added, and the alkali metal salt was completely dissolved by stirring. Weighing 1.86g of Ce-K co-doped MgO carrier, adding the carrier into the solution, magnetically stirring for 2 hours, performing vacuum rotary evaporation at 60 ℃, and removing the methanol solvent to obtain NaNO 3 Modified Ce-K co-doped MgO-based adsorption Material, i.e. [ Mg ] 90 Ce 5 K 5 ]-[Na] 20 。
Adsorption-regeneration cycle performance testing: performing adsorption-regeneration cycle experiment on the prepared adsorbing material on a thermogravimetric analyzer, recording the carbon dioxide adsorption capacity in 10 cycles, wherein the adsorption temperature is 325 ℃, the time is 30min, and the atmosphere is 40 vol.% CO 2 (ii) a The regeneration temperature is 400 ℃, the time is 5min, and the atmosphere is N 2 . The experimental result is shown in figure 6, and the result shows that after 10 adsorption-regeneration cycles, the carbon dioxide adsorption amount of the material is stabilized
Figure BDA0003062046530000062
Example 4
0.017mol of magnesium acetate tetrahydrate, 0.002mol of cerium acetate and 0.002mol of potassium citrate are weighed, dissolved in 100mL of deionized water, and stirred for about 30min until the solution is transparent and clear. 0.022mol of citric acid and 5mL of polyethylene glycol (average molecular weight 400) were weighed into the resulting clear solution. The resulting solution was transferred to a 250mL single-neck flask, and the solution in the flask was mechanically stirred in a constant temperature water bath at a stirring speed of 500rpm, a temperature of 80 ℃ for 4 hours. And taking out the prepared sol, placing the sol in an evaporation dish, and placing the sol in an oven at 150 ℃ for 5 hours to obtain a fluffy gel structure. Then grinding the mixture into powder, putting the powder into a muffle furnace for calcination, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 3 hours, and obtaining a Ce-K co-doped MgO carrier after calcination; 0.008mol of sodium nitrate was weighed into a 250mL single-neck flask, 150mL of anhydrous methanol was added, and the mixture was stirred to completely dissolve the alkali metal salt. Weighing 1.49g of Ce-K co-doped MgO carrier, adding the Ce-K co-doped MgO carrier into the solution, magnetically stirring the solution for 2 hours, performing vacuum rotary evaporation at the temperature of 60 ℃, and removing a methanol solvent to obtain NaNO 3 ModifiedCe-K codoped MgO-based adsorption Material, [ Mg ] 85 Ce 5 K 10 ]-[Na] 25 。
Adsorption-regeneration cycle performance testing: and performing an adsorption-regeneration cycle experiment on the prepared adsorbing material on a thermogravimetric analyzer, and recording the carbon dioxide adsorption amount in the 10-cycle process. The adsorption temperature is 325 ℃, the time is 30min, and the atmosphere is 40 vol.% CO 2 (ii) a The regeneration temperature is 400 ℃, the time is 5min, and the atmosphere is N 2 . The experimental result is shown in figure 7, and the result shows that after 10 adsorption-regeneration cycles, the carbon dioxide adsorption amount of the material is stabilized
Figure BDA0003062046530000071
Comparative example 1
0.02mol of magnesium nitrate hexahydrate is weighed, dissolved in 100mL of deionized water and stirred for about 30min until the solution is clear. 0.024mol of citric acid and 5mL of polyethylene glycol (average molecular weight 400) were weighed into the resulting clear solution. The resulting solution was transferred to a 250mL single-neck flask, and the solution in the flask was mechanically stirred in a constant temperature water bath at a stirring speed of 500rpm, a temperature of 80 ℃ for 4 hours. And taking out the prepared sol, placing the sol in an evaporating dish, and placing the evaporating dish in an oven at 150 ℃ for 5 hours to obtain a fluffy gel structure. Then grinding the powder into powder and putting the powder into a muffle furnace for calcination, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 3 hours, and obtaining an MgO carrier after calcination; 0.01mol of sodium nitrate was weighed into a 250mL single-neck flask, 150mL of anhydrous methanol was added, and the alkali metal salt was completely dissolved by stirring. Weighing 2.0g MgO carrier, adding into the above solution, magnetically stirring for 2h, vacuum rotary evaporating at 60 deg.C, removing methanol solvent to obtain NaNO 3 Modified MgO adsorbent materials, i.e. [ Mg ] 100 ]-[Na] 20 。
And (3) performance testing: para [ Mg ] on thermogravimetric Analyzer 100 ]-[Na] 20 Carrying out isothermal CO 2 Adsorption experiment, adsorption temperature 325 ℃, time 60min, atmosphere 40 vol.% CO 2 The results are shown in FIG. 3. Experimental adsorption-regeneration cycleProvided that the adsorption temperature was 325 ℃, the time was 30min, and the atmosphere was 40 vol.% CO 2 (ii) a The regeneration temperature is 400 ℃, the time is 5min, and the atmosphere is N 2 . The experimental result is shown in figure 4, and the result shows that after 10 adsorption-regeneration cycles, the carbon dioxide adsorption amount of the material is
Figure BDA0003062046530000081
Comparative example 2
0.019mol of magnesium nitrate hexahydrate and 0.001mol of cerium nitrate hexahydrate are weighed, dissolved in 100mL of deionized water, and stirred for about 30min until the solution is clear and clear. To the resulting clear solution was weighed 0.024mol citric acid and 5mL polyethylene glycol (average molecular weight 400). The resulting solution was transferred to a 250mL single-neck flask, and the solution in the flask was mechanically stirred in a constant temperature water bath at a stirring speed of 500rpm, a temperature of 80 ℃ and a constant temperature time of 4 hours. And taking out the prepared sol, placing the sol in an evaporation dish, and placing the sol in an oven at 150 ℃ for 5 hours to obtain a fluffy gel structure. Then grinding the mixture into powder, putting the powder into a muffle furnace for calcination, heating to 500 ℃ at a heating rate of 5 ℃/min, keeping the temperature for 3 hours, and calcining to obtain an MgO carrier; 0.01mol of sodium nitrate was weighed into a 250mL single-neck flask, 150mL of anhydrous methanol was added, and the alkali metal salt was completely dissolved by stirring. Weighing 2.33g MgO carrier, adding into the above solution, magnetically stirring for 2h, vacuum rotary evaporating at 60 deg.C, removing methanol solvent to obtain NaNO 3 Modified MgO adsorbent materials, i.e. [ Mg ] 95 Ce 5 ]-[Na] 20 。
And (3) performance testing: para [ Mg ] on thermogravimetric Analyzer 95 Ce 5 ]-[Na] 20 Carrying out isothermal CO 2 The results of the adsorption experiments are shown in FIG. 3. Adsorption temperature 325 ℃, time 60min, atmosphere 40 vol.% CO 2 . The carbon dioxide adsorption amount of the material in the adsorption time of 60min is
Figure BDA0003062046530000082
Comparative example 3
0.02mol of magnesium nitrate hexahydrate is weighed, dissolved in 100mL of deionized water and stirred for about 30min until the solution is clear. To the resulting clear solution was weighed 0.024mol citric acid and 5mL polyethylene glycol (average molecular weight 400). The resulting solution was transferred to a 250mL single-neck flask, and the solution in the flask was mechanically stirred in a constant temperature water bath at a stirring speed of 500rpm, a temperature of 80 ℃ and a constant temperature time of 4 hours. And taking out the prepared sol, placing the sol in an evaporation dish, and placing the sol in an oven at 150 ℃ for 5 hours to obtain a fluffy gel structure. Then grinding the mixture into powder and putting the powder into a muffle furnace for calcination, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min, keeping the temperature for 3 hours, and obtaining an MgO carrier, namely [ Mg ] after calcination 100 ]。
And (3) performance testing: para [ Mg ] on thermogravimetric Analyzer 100 ]Carrying out isothermal CO 2 The results of the adsorption experiments are shown in FIG. 3. Adsorption temperature 325 ℃, time 60min, atmosphere 40 vol.% CO 2 . The carbon dioxide adsorption amount of the material in the adsorption time of 60min is
Figure BDA0003062046530000083
As can be seen from the above figures and examples, in contrast to NaNO 3 Modified MgO adsorbent (comparative example 1) in which CeO was doped 2 (comparative example 2) can provide a certain amount of oxygen vacancy to form lattice defect on the MgO surface, thereby facilitating adsorption of CO by MgO 2 (ii) a And for NaNO 3 Modified Ce-K Co-doped MgO adsorption Material (example 1), doped KNO 3 Can be dissolved in molten NaNO 3 In the presence of a eutectic compound, thereby reducing [ Mg 2+ -O 2- ]Lattice energy, promotion of CO 2 The adsorption performance is that after 10 adsorption-regeneration cycles, the carbon dioxide adsorption quantity of the material is stabilized
Figure BDA0003062046530000091
Therefore, the Ce-K CO-doped MgO base medium-temperature CO provided by the invention 2 The adsorbing material has the characteristics of high adsorption capacity, high adsorption rate and the like, and shows practical application prospects.

Claims (1)

1. Ce-K CO-doped MgO-based medium-temperature CO 2 The adsorbing material is characterized by comprising a Ce-K co-doped monodisperse granular MgO carrier and an auxiliary agent NaNO loaded on the carrier in a specific proportion 3 The composition, expressed as follows:
[Mg x Ce y K z ]-[Na] m
[Mg x Ce y K z ]represents a Ce-K co-doped MgO carrier, [ Na ]]Represents NaNO 3，
x represents the mole percentage of MgO in the carrier, and x is between 80 and 90; y represents doped CeO 2 The molar percentage of y in the carrier is between 5 and 10; z represents doped KNO 3 The molar percentage of z in the carrier is between 5 and 10; the sum of x, y and z is 10,
m represents NaNO 3 M is 15-25 mol percent of the carrier;
the Ce-K CO-doped MgO base medium temperature CO 2 The adsorbent material is prepared by a method comprising the steps of:
(1) respectively weighing a certain amount of magnesium salt, cerium salt and potassium salt, dissolving in deionized water, stirring for 30min until the solution is transparent and clear,
wherein: the magnesium salt is one of magnesium acetate and magnesium nitrate; the cerium salt is one of cerium acetate and cerium nitrate; the potassium salt is one of potassium acetate, potassium nitrate and potassium citrate; the mole number of the magnesium salt in each 100mL of deionized water is between 0.01 and 0.02;
(2) then weighing a certain amount of citric acid and polyethylene glycol with the average molecular weight of 400, and adding the citric acid and the polyethylene glycol into the clear solution obtained in the step (1);
wherein: the molar ratio of the citric acid to magnesium ions in the solution is between 1.2 and 1.5, and the volume ratio of polyethylene glycol with the average molecular weight of 400 to deionized water is between 0.05 and 0.10;
(3) transferring the solution obtained in the step (2) into a single-mouth flask, mechanically stirring the solution in the flask in a constant-temperature water bath at the stirring speed of 500rpm, the temperature of the constant-temperature water bath is 80 ℃, and the constant-temperature time is 4 hours;
(4) taking out the sol prepared in the step (3), placing the sol in an evaporating dish, and placing the evaporating dish in a drying oven at the temperature of 150 ℃ for 5 hours to obtain fluffy gel;
(5) grinding the solid obtained in the step (4) into powder, putting the powder into a muffle furnace for calcination, heating to 500 ℃ at a heating rate of 5 ℃ per minute, keeping the temperature for 3 hours, and calcining to obtain a Ce-K co-doped MgO carrier;
(6) separately weighing a predetermined amount of NaNO 3 Placing the mixture into a single-neck flask, adding a certain amount of anhydrous methanol, and stirring to ensure that NaNO is added 3 The mixture is completely dissolved and dissolved in the solvent,
wherein: NaNO per 100mL of anhydrous methanol 3 The mole number is between 0.005 and 0.01;
(7) weighing a certain amount of the Ce-K co-doped MgO carrier obtained in the step (5) in proportion, adding the weighed Ce-K co-doped MgO carrier into the solution obtained in the step (6), and stirring for 2 hours;
(8) carrying out vacuum rotary evaporation on the suspension obtained in the step (7) at the temperature of 60 ℃, and removing a methanol solvent to obtain NaNO 3 The modified Ce-K co-doped MgO-based adsorption material.
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