A foamed metal loaded bismuth oxide, its preparation method and air capture applications
By preparing foam metal-supported mesoporous nano-Bi2O3, the problem of high desorption temperature in DAC technology was solved, achieving low-energy and high-efficiency CO2 capture, which is suitable for direct air capture.
Patent Information
- Application Number
- CN202511338244.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-18
- Publication Date
- 2025-11-25
- Estimated Expiration
- 2045-09-18
AI Technical Summary
In existing DAC technologies, the desorption temperature of oxide adsorbents is relatively high, resulting in high energy consumption and easy material deactivation, making it difficult to achieve efficient and low-cost CO2 capture.
Mesoporous Bi2O3 nanoparticles were prepared by using foam metal-supported bismuth oxide, which was pretreated with hydrochloric acid to form a microporous structure. The desorption temperature was reduced to 220℃ by combining hydrothermal reaction and calcination.
It achieves efficient adsorption and desorption of CO2 at room temperature and pressure, reduces energy consumption, improves the material's recycling performance and CO2 capture capacity, and reduces by-products and environmental pollution.
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Figure CN120838351B_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of carbon dioxide capture, in particular to a foamed metal loaded bismuth oxide and a preparation method and air capture application thereof. BACKGROUND
[0002] Under the aggravation of global warming, carbon capture, storage and utilization (CCUS) technology has become a key support, among which direct air capture (DAC) technology can capture CO2 for dispersed emission sources, and becomes an important supplement to achieve carbon neutralization.
[0003] DAC technology includes alkaline hydroxide solution DAC technology, amine solution DAC technology, amino acid solution / BIGs technology, solid amine adsorbent DAC technology, MOFs material DAC technology, and variable humidity adsorption technology. The DAC technology widely used in industry at present is mainly alkaline hydroxide DAC technology, which converts Na2CO3 after absorbing CO2 by KOH or NaOH, and then adds Ca(OH)2 to generate precipitate CaCO3, and finally decomposes at high temperature to produce CO2 and CaO, and the adsorbent can be recycled in the whole DAC technology.
[0004] However, DAC technology has defects in CO2 desorption temperature. The desorption temperature of the adsorbent of the existing DAC technology metal oxide is high, as shown in Table 1. Calcium oxide has the largest desorption amount as an adsorbent, but the material is extremely easy to sinter after high-temperature decomposition for many times, thereby causing material deactivation. Magnesium oxide also has a high desorption amount, but its adsorption kinetics and specific surface area are low. Lithium zirconate / silicate has a high desorption amount, but the cost of Li is high, and it also has a high desorption temperature. Therefore, reducing the desorption temperature of the material can greatly reduce the energy consumption of DAC, thereby greatly saving the cost.
[0005] SUMMARY
[0006] To solve the above problems, the present application provides a foamed metal loaded bismuth oxide and a preparation method and air capture application thereof. The core of the foamed metal loaded bismuth oxide is a composite structure of a foamed metal carrier pretreated by hydrochloric acid and a mesoporous nano Bi2O3 active component, which solves the high energy consumption problem of the existing DAC technology with a desorption temperature higher than 300 DEG C. The foamed metal loaded bismuth oxide can adsorb CO2 at room temperature and normal pressure, and the desorption temperature is only 220 DEG C. The preparation process is simple, the by-products are few, and it meets the green concept. The CO2 capture amount reaches 2.2 mmol / g, and the cycle performance is excellent, which can be effectively applied to direct air capture.
[0007] The technical scheme of the present application is as follows:
[0008] The first aspect of the present application provides a foamed metal loaded bismuth oxide, which is composed of a carrier and an active component.
[0009] The carrier is a foamed metal pretreated by hydrochloric acid, and a microporous structure is formed on the surface of the pretreated foamed metal.
[0010] The active component is mesoporous nano Bi2O3, which is prepared by dissolving bismuth nitrate pentahydrate in ethylene glycol, dispersing with polyvinylpyrrolidone, mixing with a phosphate buffer solution, and then performing hydrothermal reaction and calcination.
[0011] The mesoporous nano Bi2O3 has a mesoporous pore size of 29-30 nm and a specific surface area of 0.4-0.6 m 2 / g; and the mesoporous nano Bi2O3 is uniformly loaded on the surface and micropores of the foamed metal.
[0012] Further, the foamed metal loaded bismuth oxide has a CO2 desorption temperature of not less than 220℃.
[0013] Further, the foamed metal is at least one of foamed zinc, foamed nickel, foamed nickel-molybdenum, foamed titanium, and foamed molybdenum.
[0014] Further, the hydrochloric acid pretreatment specifically includes:
[0015] The foamed metal is placed in a 1-2 mol / L hydrochloric acid solution for 2-4 min and ultrasonicated for 10-15 min, and then washed with ethanol and ultrapure water alternately for 3-5 times, and dried to complete the pretreatment.
[0016] Further, the phosphate buffer solution is an aqueous solution of potassium dihydrogen phosphate and sodium hydrogen phosphate, and the mass ratio of potassium dihydrogen phosphate to sodium hydrogen phosphate is (1-2) : (1-5); and the pH value of the phosphate buffer solution is 6-8.
[0017] Further, the concentration of the bismuth nitrate pentahydrate after being dissolved in ethylene glycol is 0.8-1.1 g / mL.
[0018] The second aspect of the present application provides a preparation method of the foamed metal loaded bismuth oxide according to any one of the first aspect, based on the same inventive concept, which comprises the following steps:
[0019] S1. Dissolve bismuth nitrate pentahydrate in ethylene glycol, add polyvinylpyrrolidone, and ultrasonicate for 10-15 min to obtain a mixed solution;
[0020] S2. The mixed solution is mixed with a phosphate buffer solution, the hydrofoamed metal pre-processed with hydrochloric acid is added, and the mixture is placed in an autoclave, and hydrothermal growth is performed at a hydrothermal temperature of 150-160 DEG C and a temperature rising rate of 10 DEG C / min for 5-7 h. After completion, the mixture is taken out, washed, dried, calcined at 380-420 DEG C, and a temperature rising rate of 10 DEG C / min, and calcination is performed for 30-40 min to obtain the hydrofoamed metal loaded bismuth oxide.
[0021] Further, the volume ratio of the phosphate buffer solution to the mixed solution is 1:3-4, and the stirring speed is 200-300 r / min, and the stirring time is 30-40 min.
[0022] In a third aspect based on the same inventive concept, the present application provides a use of the hydrofoamed metal loaded bismuth oxide of any one of the first aspect or the hydrofoamed metal loaded bismuth oxide prepared by the method of any one of the second aspect in direct air capture of CO2.
[0023] Further, the direct air capture of CO2 includes the following steps:
[0024] The hydrofoamed metal loaded bismuth oxide is placed in a capture device, air is introduced at a flow rate of 100 mL / min, and adsorption is stopped when the CO2 concentration at the air outlet is consistent with that of the air. Ar gas is introduced into the capture device until the CO2 concentration at the air outlet is 0. Desorption is performed by heating to 220 DEG C, and 50 mL / min of argon gas is introduced. When the CO2 concentration at the air outlet is 0, the desorption is completed, and the cycle is used. The CO2 capture capacity of the hydrofoamed metal loaded bismuth oxide is 2.2 mmol / g.
[0025] Compared with the prior art, the embodiments of the present application have at least the following advantages or beneficial effects:
[0026] 1. Compared with the product bismuth oxide carbonate after adsorption of bismuth oxide, the hydrofoamed metal loaded bismuth oxide of the present application can significantly reduce the desorption temperature of the adsorption product.
[0027] 2. The present application uses hydrofoamed metal loaded bismuth oxide to directly capture CO2 from air. Compared with other capture technologies, the capture process of the present application can be performed at normal temperature and pressure, and has the advantages of no pollution, no solvent loss, no corrosion to equipment, high desorption capacity, excellent cycle capture performance, etc.
[0028] 3. The hydrofoamed metal loaded bismuth oxide prepared by the present application has simple and convenient cycle conditions and is easy to operate.
[0029] 4. In the preparation of the hydrofoamed metal loaded bismuth oxide, the by-products and waste produced are less and easy to handle, which can reduce the pollution to the environment and meet the development trend of green chemistry. BRIEF DESCRIPTION OF DRAWINGS
[0030] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the embodiments. It should be understood that the following drawings only show some of the embodiments of the present application, and therefore should not be considered as limiting the scope. For those skilled in the art, other related drawings can also be obtained without creative labor on the basis of these drawings.
[0031] Figure 1 X-ray diffraction analysis spectrum of the product of example 1 after adsorption;
[0032] Figure 2 SEM spectrum of the adsorption process of the product of example 1, wherein a is the SEM spectrum of the product of example 1 before adsorption; b is the SEM spectrum during adsorption; c is the SEM spectrum after adsorption; d is the SEM spectrum of bismuth oxide prepared in comparative example 1;
[0033] Figure 3 TG spectrum of the direct air capture and desorption process of the product of example 1;
[0034] Figure 4 TG spectrum of the direct air capture and desorption process of the product of comparative example 1;
[0035] Figure 5 TPD spectrum of the direct air capture and desorption process of the product of example 1;
[0036] Figure 6 TPD spectrum of the direct air capture and desorption process of the product of comparative example 1. DETAILED DESCRIPTION
[0037] In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be described clearly and completely below. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of the present application.
[0038] Unless otherwise specifically indicated, all the various raw materials, reagents, instruments and equipment used in the present application can be purchased from the market or can be prepared by the existing methods.
[0039] The present application will be further described below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present application and not used to limit the scope of the present application. The experimental methods not specified in the following examples are generally determined according to the national standards. If there is no corresponding national standard, the international standard, the conventional condition, or the condition suggested by the manufacturer is used.
[0040] Example 1
[0041] The present example provides a foam metal loaded bismuth oxide, and the preparation method comprises the following processes:
[0042] 1.37 g of disodium hydrogen phosphate powder and 1.2 g of sodium dihydrogen phosphate were added into 10 ml of deionized water, and magnetic stirring was performed for 10 min to obtain a phosphate buffer solution; 4.583 g of bismuth nitrate pentahydrate was dissolved in 30 ml of ethylene glycol, and ultrasonic treatment was performed for 10 min to prepare a mixed solution with a concentration of 1.1 g / ml; the foam zinc was placed in a 1 mol / L hydrochloric acid solution, and was allowed to stand for 2 min and was subjected to ultrasonic treatment for 10 min, and then the foam zinc was taken out and washed with anhydrous ethanol and deionized water for 3-5 times to obtain hydrochloric acid treated foam zinc; the phosphate buffer solution was mixed with the mixed solution and stirred for 30 min at a rotation speed of 300 r / min; the hydrochloric acid treated foam zinc was added and placed in an autoclave, and was heated to 150°C at a heating rate of 10°C / min, and was kept for 6 h, and then was taken out, washed and dried to obtain a solid mixture; the solid mixture was placed in a muffle furnace and heated to 400°C at a heating rate of 10°C / min, and was kept for 30 min, and then was naturally cooled to obtain the foam metal loaded bismuth oxide.
[0043] Example 2
[0044] The present example provides a foam metal loaded bismuth oxide, and the preparation method comprises the following processes:
[0045] 1.37 g of disodium hydrogen phosphate powder and 1.2 g of sodium dihydrogen phosphate were added into 10 ml of deionized water, and magnetic stirring was performed for 10 min to obtain a phosphate buffer solution; 4.583 g of bismuth nitrate pentahydrate was dissolved in 30 ml of ethylene glycol, and ultrasonic treatment was performed for 10 min to prepare a mixed solution with a concentration of 1.1 g / ml; the foam zinc was placed in a 1 mol / L hydrochloric acid solution, and was allowed to stand for 2 min and was subjected to ultrasonic treatment for 10 min, and then the foam zinc was taken out and washed with anhydrous ethanol and deionized water for 3-5 times to obtain hydrochloric acid treated foam zinc; the phosphate buffer solution was mixed with the mixed solution and stirred for 30 min at a rotation speed of 300 r / min; the hydrochloric acid treated foam zinc was added and placed in an autoclave, and was heated to 150°C at a heating rate of 10°C / min, and was kept for 6 h, and then was taken out, washed and dried to obtain a solid mixture; the solid mixture was placed in a muffle furnace and heated to 400°C at a heating rate of 10°C / min, and was kept for 30 min, and then was naturally cooled to obtain the foam metal loaded bismuth oxide.
[0046] Example 3
[0047] The present example provides a foam metal loaded bismuth oxide, and the preparation method comprises the following processes:
[0048] 1.37 g of disodium hydrogen phosphate powder and 1.2 g of sodium dihydrogen phosphate were added into 10 ml of deionized water, and magnetic stirring was performed for 10 min to obtain a phosphate buffer solution; 4.583 g of bismuth nitrate pentahydrate was dissolved in 30 ml of ethylene glycol, and ultrasonic treatment was performed for 10 min to prepare a mixed solution with a concentration of 1.1 g / ml; the foamed nickel was placed in a 1 mol / L hydrochloric acid solution, and was allowed to stand for 2 min and was subjected to ultrasonic treatment for 10 min, and then the foamed nickel was taken out and was washed with anhydrous ethanol and deionized water for 3-5 times to obtain foamed nickel treated with hydrochloric acid; the phosphate buffer solution was mixed with the mixed solution, and stirring was performed at a speed of 300 r / min for 30 min; the foamed nickel treated with hydrochloric acid was added and was placed in an autoclave, and was heated to 150°C at a heating rate of 10°C / min, and was allowed to stand for 6 h, and then was taken out and was washed and dried to obtain a solid mixture; the solid mixture was placed in a muffle furnace, and was heated to 400°C at a heating rate of 10°C / min, and was allowed to stand for 30 min, and then was naturally cooled to obtain foamed metal loaded with bismuth oxide.
[0049] Comparative Example 1
[0050] The present comparative example provides a pure bismuth oxide which is not loaded with metal, and the preparation method is as follows:
[0051] 1) 0.1 mol of bismuth acetate powder was added into 1 L of deionized water, and 6 mL of 0.5 mol / L citric acid was added to form a mixed solution, and magnetic stirring was performed for 1 h, and ultrasonic oscillation was performed for 1 h;
[0052] 2) 0.1 mol / L sodium hydroxide was added to the solution in step 1, and magnetic stirring was performed for 1 h, and standing was performed for 24 h. The volume ratio of the bismuth acetate solution to the sodium hydroxide was 1:1;
[0053] 3) The mixed solution in step 2 was stirred at 200 rpm for 1 h, and then was allowed to stand for 24 h and was filtered, and the obtained precipitate was repeatedly washed with deionized water, and was dried at 60°C for 1 h;
[0054] 4) The precipitate in step 3 was placed in a high-temperature decomposition furnace, and was calcined at 380°C for 1 h to obtain yellow solid bismuth oxide.
[0055] Comparative Example 2
[0056] The present comparative example is a commercially available calcium oxide product, which is used as a comparison of the desorption temperature of the product of the present application and the existing DAC technology.
[0057] Comparative Example 3
[0058] The present comparative example is a commercially available magnesium oxide product, which is used as a comparison of the desorption temperature of the product of the present application and the existing DAC technology.
[0059] In order to better understand the present application, the following tests were conducted on the products prepared in the examples and comparative examples.
[0060] Test Example 1
[0061] This test example used the products prepared in the above examples and comparative examples to collect CO2 in direct air, and the specific implementation steps were as follows:
[0062] 1). 1 g of the product prepared in the examples and comparative examples was taken into the trapping device.
[0063] 2). The air compression device was opened, the flow rate of the flow meter was set to 500 mL / min, air was introduced into the trapping device, the gas entered from the bottom of the trapping device, and a perforated stainless steel screen was present at the bottom of the device to disperse the air and increase its contact area with the product, and the CO2 concentration in the air after adsorption was detected at the gas outlet, and the adsorption was stopped when the CO2 at the gas outlet was consistent with the air.
[0064] 3). After the adsorption was completed, the Ar gas cylinder was opened, the air in the reaction chamber was discharged, and the CO2 was detected at the gas outlet using an infrared CO2 analyzer.
[0065] 4). When the concentration at the gas outlet was zero, the temperature of the device was increased to 220°C, 50 mL / min of argon was introduced, and the CO2 was detected at the gas outlet using an infrared CO2 analyzer, and when the CO2 concentration at the outlet was 0, the desorption was completed and the next cycle was performed.
[0066] The adsorption and desorption amounts of the material were calculated according to specific formulas, which were shown as follows:
[0067] Desorption amount calculation formula
[0068]
[0069] In the formula, q s is the CO2 desorption amount, mmol / g; Q is the air flow rate, mL / min; C is the outlet gas concentration, vol%; m is the adsorbent mass, g; V m is the gas molar volume, 22.4 L / mol; T0 is the temperature under standard conditions, 273 K; T is the desorption temperature, K.
[0070] The results are shown in Table 2:
[0071] From Table 2, it can be seen that the desorption amount of Examples 1-3 all exist at 220℃, and the adsorbent of Comparative Example 1 has no desorption amount, wherein the desorption amount of Example 1 can reach 2.2 mmol / g at 220℃, which indicates that it has better desorption amount at low temperature, and the pure bismuth oxide of Comparative Example 1 starts to desorb at 260℃, and the desorption amount cannot reach the desorption amount of Example 1 at 300℃, which proves that the metal loading can significantly reduce the desorption temperature, and the calcium oxide of Comparative Example 2 cannot desorb at the test temperature due to its high desorption temperature, which cannot meet the desorption temperature. The magnesium oxide of Comparative Example 3 does not desorb below 300℃, and desorption occurs at 300℃, but the desorption amount is only 1 mmol / g, which proves that the desorption temperature of magnesium oxide is the lowest and cannot be lower than 300℃, but this is also significantly different from the lowest temperature of the examples of the present application, and the examples of the present application have a significant effect on reducing the desorption temperature.
[0072] In order to better understand the present application, the foam metal loaded bismuth oxide prepared in Example 1 is further tested.
[0073] The test method is the same as that of Test Example 1, and after the experimental steps are completed, the SEM of the product after adsorption is as shown in Figure 2 , and it can be known from Figure 1 that with the progress of the reaction, the blocky bismuth oxide gradually converts into a flaky product, and at the same time, the XRD shows that the phase of bismuth carbonate initially appears.
[0074] The TG and TPD of the desorption process of Comparative Example 1 and Test Example 1 are as shown in Figures 3-6 , and it can be found that the desorption temperature of the loaded adsorption product is much lower than that of pure bismuth oxide.
[0075] From the results, it can be seen that the carbon dioxide capture process of the present example 1 is to complete adsorption after air is introduced at room temperature, and after decomposition, the product gas CO2 capture amount is 2.2 mmol g -1 , and it is proved by TG and TPD that the desorption temperature is significantly reduced compared with the prior art, which can greatly reduce the energy consumption of the DAC process.
[0076] Various embodiments of the present application can take on a variety of scopes; it should be understood that a scope in the form of a range is described merely for the sake of convenience and brevity, and should not be construed as a rigid limitation of the scope of the present application; therefore, it should be considered that the range described has specifically disclosed all possible sub-ranges and single values within that range. For example, it should be considered that a range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any cited number (fractional or integral) within the indicated range.
[0077] The foregoing is considered as illustrative only of the principles of the application. Numerous modifications and adaptations will be apparent to those skilled in the art in view of the above descriptions of the embodiments. This specification and the embodiments are not therefore to be taken in a limiting sense, but are made within the spirit of the scope of the application, and wherein is defined as follows:
Claims
1. A foamed metal supported bismuth oxide, characterized in that, The foam metal loaded bismuth oxide is composed of a carrier and an active component; The carrier is a foam metal pretreated by hydrochloric acid, and a microporous structure is formed on the surface of the pretreated foam metal; The active component is mesoporous nano Bi2O3, which is prepared by dissolving bismuth nitrate pentahydrate in ethylene glycol, dispersing with polyvinylpyrrolidone, mixing with a phosphate buffer solution, hydrothermal reaction, and calcination; The mesoporous pore size of the mesoporous nano Bi2O3 is 29-30 nm, and the specific surface area is 0.4-0.6 m 2 / g; the mesoporous nano Bi2O3 is uniformly loaded on the surface and micropores of the foam metal.
2. The foam metal supported bismuth oxide according to claim 1, characterized in that, The desorption temperature of the foam metal loaded bismuth oxide for CO2 is not lower than 220 DEG C.
3. The foam metal supported bismuth oxide of claim 1, wherein, The foam metal is at least one of foam zinc, foam nickel, foam nickel-molybdenum, foam titanium, and foam molybdenum.
4. The foam metal supported bismuth oxide of claim 1, wherein, The hydrochloric acid pretreatment specifically includes: The foam metal is placed in a 1-2 mol / L hydrochloric acid solution for 2-4 min, and ultrasonic treatment is performed for 10-15 min, and then the foam metal is washed with ethanol and ultrapure water alternately for 3-5 times, and dried to complete the pretreatment.
5. The foam metal supported bismuth oxide of claim 1, wherein, The phosphate buffer solution is an aqueous solution of potassium dihydrogen phosphate and sodium hydrogen phosphate, and the mass ratio of the potassium dihydrogen phosphate to the sodium hydrogen phosphate is (1-2) :(1-5); the pH value of the phosphate buffer solution is 6-8.
6. The foam metal supported bismuth oxide of claim 1, wherein, The concentration of the bismuth nitrate pentahydrate after being dissolved in ethylene glycol is 0.8-1.1 g / mL.
7. A method for the production of the foamed metal-supported bismuth oxide according to any one of claims 1 to 6, characterized in that, The preparation method of the foam metal loaded bismuth oxide includes the following steps: S1. Dissolve bismuth nitrate pentahydrate in ethylene glycol, add polyvinylpyrrolidone, and ultrasonic treatment for 10-15 min to obtain a mixed solution; S2. Stir and mix the mixed solution with the phosphate buffer solution, add the foam metal pretreated by hydrochloric acid, put it into a hydrothermal kettle, hydrothermal temperature is 150-160 DEG C, heating rate is 10 DEG C / min, and hydrothermal growth is performed for 5-7 h, then wash, dry, and calcine at 380-420 DEG C to obtain the foam metal loaded bismuth oxide.
8. The method of claim 7, wherein, The volume ratio of the phosphate buffer solution to the mixed solution is 1:3-4, the stirring speed is 200-300 r / min, and the stirring time is 30-40 min.
9. The foam metal loaded bismuth oxide according to any one of claims 1-6 is used for direct air capture of CO2.
10. Use according to claim 9, characterized in that, Direct air capture of CO2 includes the following steps: The foam metal loaded bismuth oxide is placed in a capture device, air is introduced at a flow rate of 100 mL / min, and adsorption is stopped when the CO2 concentration at the gas outlet is consistent with that of air; Ar gas is introduced into the capture device until the CO2 concentration at the gas outlet is 0; desorption is performed by heating to 220 DEG C, and the desorption is completed when the CO2 concentration at the gas outlet is 0, and the foam metal loaded bismuth oxide is recycled; the CO2 capture capacity of the foam metal loaded bismuth oxide is 2.2 mmol / g.
Citation Information
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