CN114887583A - Mesoporous alumina loaded Cu 2 Preparation method of O adsorbent - Google Patents

Mesoporous alumina loaded Cu 2 Preparation method of O adsorbent Download PDF

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CN114887583A
CN114887583A CN202210454170.1A CN202210454170A CN114887583A CN 114887583 A CN114887583 A CN 114887583A CN 202210454170 A CN202210454170 A CN 202210454170A CN 114887583 A CN114887583 A CN 114887583A
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mesoporous alumina
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CN114887583B (en
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吴昊阳
王倩玉
秦明礼
李子宜
贾宝瑞
曲选辉
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University of Science and Technology Beijing USTB
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    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
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Abstract

Mesoporous alumina loaded Cu 2 A preparation method of an O adsorbent belongs to the technical field of gas purification. The raw materials are as follows: aluminum nitrate, cupric salt and fuel, wherein the molar ratio of the aluminum nitrate to the cupric salt is 1: (2.5-12): (1.7-14.9) in the ratio, and decomposing the aluminum nitrate into gamma-Al by Solution Combustion Synthesis (SCS) and subsequent calcination at 300-600 DEG C 2 O 3 Decomposing the cupric salt into CuO, and finally, directly self-reducing the CuO into Cu by high-temperature heat treatment under the conditions of stable nitrogen flow and 600-700 DEG C 2 O to obtain Cu with high specific surface area, large pore volume 2 Uniform O loading on gamma-Al 2 O 3 The composite adsorbent of (1). The adsorbent is passed through gamma-Al 2 O 3 The synergistic effect of the physical adsorption and the pi complex chemical adsorption of Cu (I) is used for adsorbing and purifying CO, and the excellent CO adsorption capacity is shown. The invention provides a simple and extensible synthesis method for developing the CO adsorbent with large working capacity and high selectivity, and the production process is environment-friendly and pollution-free, the operation cost is low, the economic benefit is high, and the method has a good industrial application prospect.

Description

Mesoporous alumina loaded Cu 2 Preparation method of O adsorbent
Technical Field
The invention belongs to the technical field of gas purification, and particularly relates to mesoporous alumina loaded Cu 2 O adsorbent and its preparation method.
Background
Carbon monoxide (CO) is a widely distributed pollutant in the atmosphere and is easily produced due to incomplete combustion of carbonaceous materials in coal furnaces, gas water heaters, automobile engines and cigarettes. In many cases, CO is not easily noticed due to its colorless, odorless properties, and poses many hazards to the ecological environment and human health. The rapid combination of CO and hemoglobin reduces the oxygen content in blood, thus resulting in hypoxia and being highly toxic to human body. It is reported that at least 15200 people in the united states require hospitalization for CO poisoning each year. In addition, CO is widely used in the chemical industry as a valuable raw material for the production of various chemicals such as methanol, phosgene, formic acid, acetic acid, ethylene glycol, and polyurethane foam. However, although the source of CO is extensive, it is usually associated with CO 2 、H 2 O、N 2 、CH 4 And H 2 And the like exist as mixed gases, and these CO-containing gases cannot be directly used for the synthesis of chemicals. Therefore, the selective capture of CO from various gas mixtures is of vital importance for environmental health as well as economic impact. Currently, mature techniques for separating CO rely primarily on cryogenic distillation, absorption and adsorption processes. Among them, the adsorption method has received much attention because of its high efficiency operation and low energy cost, but the success of the adsorption technology depends on the development of high efficiency adsorption materials. However, the adsorption performance of widely studied CO adsorption materials, such as Activated Carbon (AC), zeolites, molecular sieves, metal oxides and metal organic frameworks, is not ideal. Therefore, it remains very challenging to develop materials with high CO selectivity, large CO working capacity, and high stability.
Physical adsorption is a weak adsorption process carried out by van der waals force, and has the main advantages of energy-saving operation and regeneration, but the adsorption capacity of physical adsorption is limited and relatively low, and the requirement of adsorbing CO in practical application cannot be met. Chemisorption is a strong adsorption process in which chemical reactions occur between the adsorbent and the adsorbate due to the action of chemical bonds, and the adsorption capacity of chemisorption is much higher than that of physical adsorption. Therefore, the introduction of chemisorption into the adsorbent can further enhance the CO adsorption performance of the adsorbent material. Cu (I) on a porous carrier is reported to be strongly combined with CO molecules through pi complexation, and Cu (I) is low in price, environment-friendly and stable in performance and is considered as the first transition metal ion for preparing CO adsorbent. Mesoporous alumina (gamma-Al) 2 O 3 ) It has been widely used as a CO gas adsorbent for research because of its outstanding characteristics of high specific surface area, large pore volume, abundant porosity, uniform pore size distribution, stability over a wide temperature range, durability, catalytic activity, etc. Thus, in gamma-Al 2 O 3 Introduction of Cu on a support 2 The O active adsorption site is a CO adsorption material with a very promising prospect. But conventional Cu 2 The preparation method of the O-based adsorbent is rather complicated, and CuO is reduced to Cu 2 The yield of O is far from satisfactory.
In the invention, a simple solution combustion synthesis assisted CuO self-reduction method is developed for the first time to prepare Cu with improved pore structure, high specific surface area and high Cu (I) dispersion in a carrier material 2 O@γ-Al 2 O 3 The composite adsorbent is then used for adsorptive CO separation. Compared with the traditional method, the yield of Cu (I) is obviously improved by using our strategy, and the gamma-Al can be accurately adjusted according to the actual application requirement 2 O 3 Pore structure of, and Cu 2 Degree of O Dispersion and Cu 2 O loading to improve CO adsorption capacity, selective adsorption and regenerability, and has the advantages of cost-effectiveness, wide application and easy scale-up.
Disclosure of Invention
The invention aims at the problems of low removal efficiency and unsatisfactory adsorption selectivity of the existing CO adsorbent,the method designs a new idea for preparing the cuprous oxide loaded mesoporous alumina powder material by adopting a solution combustion synthesis method, and the mesoporous alumina matrix of the material has high stability, relatively higher specific surface area and pore volume and in-situ loaded Cu 2 The O particle size distribution is uniform, and the bonding property with the matrix is good. The adsorbent has the characteristics of high efficiency of removing CO in gas, simple preparation method, environmental-friendly and pollution-free production process, simple and convenient operation, suitability for large-scale production and the like.
The invention comprises the following specific steps:
(1) the preparation process comprises the steps of taking aluminum nitrate, cupric salt and fuel as raw materials, proportioning according to a certain molar ratio, dissolving in deionized water, performing magnetic stirring until the materials are fully dissolved to form a homogeneous transparent solution, heating the solution on an electric furnace at 100 ℃ to form gel, and performing combustion reaction in an oxygen-rich environment to obtain fluffy precursor powder.
(2) Putting the precursor powder prepared in the step (1) into a vacuum furnace for high-temperature calcination to obtain copper oxide grain-loaded mesoporous alumina (CuO @ gamma-Al) 2 O 3 ) And (3) intermediate products.
(3) Putting the powder prepared in the step (2) into a tubular furnace for high-temperature heat treatment in an inert atmosphere to obtain cuprous oxide loaded mesoporous alumina (Cu) 2 O@γ-Al 2 O 3 ) An adsorbent.
Further, the molar ratio of the aluminum nitrate, the cupric salt and the fuel in the step (1) is 1: (2.5-12): (1.7-14.9).
Further, the cupric salt in the step (1) is at least one of cupric nitrate, cupric chloride, cupric acetate and cupric sulfate.
Further, the fuel in the step (1) is at least one of glycine, urea and oxalyldiamide.
Further, the combustion reaction temperature in the step (1) is 150-250 ℃.
Further, the reaction in the step (1) is carried out in a container bottle, a rubber plug is plugged at the bottle mouth, two thin pipes are inserted into the rubber plug, one thin pipe is used as an air inlet for introducing oxygen, and the other thin pipe is used as an air outlet for creating the oxygen-enriched environment.
Further, the high-temperature calcination in the step (2) has a heating rate of 3-5 ℃/min, a reaction temperature of 300-600 ℃ and a heat preservation time of 0.5-2 h.
Further, the inert atmosphere in the step (3) is a stable nitrogen flow, and the flow rate of the gas flow is 200-300 mL/min.
Further, the high-temperature heat treatment in the step (3) has the temperature rise rate of 6-10 ℃/min, the reaction temperature of 600-700 ℃ and the heat preservation time of 6-12 h.
Further, Cu obtained in the step (3) 2 O@γ-Al 2 O 3 The adsorbent has a particle size of > 1800m 2 Total specific surface area, > 3.6cm 3 The total pore volume is per gram, and the size of cuprous oxide particles is 4-15 nm; the adsorbent has high CO saturation adsorption capacity, and the adsorption capacity is 3.6-5.7 mmol/g at 293K.
The technology of the invention has the following advantages:
(1) the invention provides a preparation method of a high-performance CO adsorbent, which is characterized in that a mesoporous template is not required to be externally synthesized and introduced, a large number of holes are formed on the surface of a material by directly utilizing gas released in the combustion process, and reaction thermodynamics and oxide nucleation and growth are influenced by adjusting conditions such as raw material content, proportion, calcination temperature and the like, so that a mesoporous alumina carrier material with high specific surface area, large pore volume, regularity and order and uniform pore size is prepared, and the preparation method provides a premise for obtaining the adsorbent with high CO adsorption capacity.
(2) The adsorbent is prepared by introducing CuO into a mesoporous alumina organic framework through SCS and high-temperature calcination at 300-600 ℃, and Cu is introduced under vacuum or inert gas flow at 600-700 DEG C 2+ Can generate self-reduction on an alumina carrier to form Cu + By reducing CuO to Cu 2 O, thereby generating a target adsorbent with cuprous sites, and because various reactions are carried out at lower temperature and the framework structure of the mesoporous alumina is well preserved, the adsorbent is a pi complex adsorption material with a good structure and has good adsorption performance on CO.
(3) The invention adopts in-situ reaction to synthesize the cuprous-based adsorbent in the mesoporous alumina carrier, improves the combination stability of the cuprous-based adsorbent and the mesoporous alumina carrier, and adopts Cu 2 O is not easy to fall off in the mesoporous alumina, and the mesoporous alumina has stable physical and chemical properties, so that the obtained composite adsorbent material has stable structure and better circulation stability.
(4) The invention controls the molar ratio of the aluminum nitrate to the cupric salt to be 1: (2.5 to 12) adding Cu 2 The distribution of O in the pore channels of the mesoporous alumina is optimized, the pore channel structure of the carrier is not blocked, and Cu is ensured 2 The loading amount of the O is optimized so as to improve the adsorption capacity and the separation capacity of the adsorbent to the CO.
(5) Cu prepared by the invention 2 O@γ-Al 2 O 3 The surface of the adsorbent has stronger hydrophobicity, so that on one hand, competitive adsorption of water vapor and CO gas can be reduced, and the adsorption efficiency is improved; on the other hand, the problem that Cu (I) is easily oxidized into Cu (II) in humid air can be effectively solved, and the stability of the adsorption performance is improved.
(6) The invention adopts a solution combustion synthesis method to prepare CuO @ Al 2 O 3 The precursor powder has the advantages that raw materials are subjected to redox reaction in an oxygen-rich environment at a low temperature, so that the uniform mixing at a molecular level is achieved, the uniform loading of CuO is facilitated, the self-reduction rate of CuO can be increased due to high dispersion of CuO, and the yield of Cu (I) is remarkably improved.
(7) Cu prepared by the invention 2 O@γ-Al 2 O 3 The adsorbent has high overall stability, and the preparation method has simple process, low requirements on environment and equipment and better industrial application prospect.
Detailed Description
Example 1
16.131g of aluminum nitrate, 25.972g of copper nitrate, 6.773g of glycine and 2.838g of urea were weighed out and dissolved in 40mL of deionized water, and a uniform and transparent solution was formed under magnetic stirring at 200 rpm. Next, the solution was placed on a resistance furnace and heated, and evaporated with stirring at 100 ℃ to form a gel. Subsequently, heating was performed at 150 ℃ to perform a combustion reaction. In the course of this process, the temperature of the molten steel is controlled,the gel rapidly expands in volume, releasing a large amount of gas, accompanied by a violent combustion reaction, and simultaneously releasing a large amount of heat to obtain a precursor. The precursor is put into a vacuum furnace and heated to 400 ℃ at the heating rate of 5 ℃/min for high-temperature calcination for 1.5h to obtain CuO @ gamma-Al 2 O 3 And (3) intermediate products. Finally, placing the prepared powder into a tubular furnace to carry out high-temperature heat treatment in a nitrogen atmosphere of 200mL/min, wherein the heating rate is 6 ℃/min, the reaction temperature is 670 ℃, and the heat preservation time is 8h to obtain the total specific surface area of 1847.08m 2 Per g, total pore volume of 3.96cm 3 /g、Cu 2 Cu with O particle size of 7.1nm 2 O@γ-Al 2 O 3 An adsorbent. The adsorbent has good CO adsorption performance, and the saturated adsorption capacity at 293K is 4.53 mmol/g.
Example 2
14.630g of aluminum nitrate, 34.577g of copper chloride, 13.650g of copper sulfate, 9.360g of urea and 2.061g of oxalyldiamide were weighed into 60mL of deionized water and stirred magnetically at 300rpm to form a uniform and transparent solution. Next, the solution was placed on a resistance furnace and heated, and evaporated with stirring at 100 ℃ to form a gel. Subsequently, heating was performed at 200 ℃ to perform a combustion reaction. In the process, the gel rapidly expands in volume, releasing a large amount of gas, accompanied by a vigorous combustion reaction, and simultaneously releasing a large amount of heat to obtain a precursor. The precursor is put into a vacuum furnace and heated to 550 ℃ at the heating rate of 3 ℃/min for high-temperature calcination for 2h to obtain CuO @ gamma-Al 2 O 3 And (3) intermediate products. Finally, placing the prepared powder into a tubular furnace to carry out high-temperature heat treatment in a nitrogen atmosphere of 250mL/min, wherein the heating rate is 6 ℃/min, the reaction temperature is 600 ℃, and the heat preservation time is 12h to obtain the total specific surface area of 2507.31m 2 Per g, total pore volume of 5.16cm 3 /g、Cu 2 Cu with O particle size of 4.6nm 2 O@γ-Al 2 O 3 An adsorbent. The adsorbent has good CO adsorption performance, and the saturated adsorption capacity at 293K is 5.67 mmol/g.
Example 3
21.382g of aluminum nitrate, 44.382g of copper acetate and 18.574g of oxalyldiamide were weighed out and dissolved in 60mL of deionized waterUnder magnetic stirring at 350rpm, a homogeneous and transparent solution was formed. Next, the solution was placed on a resistance furnace and heated, and evaporated with stirring at 100 ℃ to form a gel. Subsequently, heating was performed at 200 ℃ to perform a combustion reaction. In the process, the gel rapidly expands in volume, releasing a large amount of gas, accompanied by a vigorous combustion reaction, and simultaneously releasing a large amount of heat to obtain a precursor. The precursor is put into a vacuum furnace and heated to 600 ℃ at the heating rate of 4 ℃/min for high-temperature calcination for 0.5h to obtain CuO @ gamma-Al 2 O 3 And (3) intermediate products. Finally, placing the prepared powder into a tubular furnace to carry out high-temperature heat treatment in a nitrogen atmosphere of 220mL/min, wherein the heating rate is 8 ℃/min, the reaction temperature is 640 ℃, and the heat preservation time is 10 hours to obtain the total specific surface area of 2133.80m 2 Per g, total pore volume of 4.45cm 3 /g、Cu 2 Cu with O particle size of 13.4nm 2 O@γ-Al 2 O 3 An adsorbent. The adsorbent has good CO adsorption performance, and the saturated adsorption capacity of the adsorbent at 293K is 4.82 mmol/g.
Example 4
9.378g of aluminum nitrate, 39.375g of copper sulfate, 13.64g of copper chloride and 8.063g of glycine were weighed out and dissolved in 80mL of deionized water, and a uniform and transparent solution was formed under magnetic stirring at 300 rpm. Next, the solution was placed on a resistance furnace and heated, and evaporated with stirring at 100 ℃ to form a gel. Subsequently, heating was performed at 250 ℃ to perform a combustion reaction. In the process, the gel rapidly expands in volume, releasing a large amount of gas, accompanied by a vigorous combustion reaction, and simultaneously releasing a large amount of heat to obtain a precursor. The precursor is put into a vacuum furnace and heated to 500 ℃ at the heating rate of 5 ℃/min for high-temperature calcination for 1h to obtain CuO @ gamma-Al 2 O 3 And (4) intermediate products. Finally, the prepared powder is put into a tube furnace to be subjected to high-temperature heat treatment in a nitrogen atmosphere of 300mL/min, the heating rate is 10 ℃/min, the reaction temperature is 700 ℃, the heat preservation time is 6h, and the total specific surface area is 1987.43m 2 Per g, total pore volume of 4.02cm 3 /g、Cu 2 Cu with O particle size of 9.7nm 2 O@γ-Al 2 O 3 An adsorbent. The adsorbent has good CO adsorption performance and saturated adsorption capacity under 293KThe amount was 3.77 mmol/g.

Claims (10)

1. Mesoporous alumina loaded Cu 2 The preparation method of the O adsorbent is characterized by comprising the following preparation steps:
(1) the preparation process comprises the steps of taking aluminum nitrate, cupric salt and fuel as raw materials, proportioning according to a certain molar ratio, dissolving in deionized water, performing magnetic stirring until the raw materials are fully dissolved to form a homogeneous transparent solution, heating the solution at 100 ℃ to form gel, and performing combustion reaction in an oxygen-rich environment to obtain fluffy precursor powder;
(2) putting the precursor powder prepared in the step (1) into a vacuum furnace for high-temperature calcination to obtain the copper oxide grain-loaded mesoporous alumina (CuO @ gamma-Al) 2 O 3 ) An intermediate product;
(3) putting the powder prepared in the step (2) into a tubular furnace for high-temperature heat treatment in an inert atmosphere to obtain cuprous oxide loaded mesoporous alumina (Cu) 2 O@γ-Al 2 O 3 ) An adsorbent.
2. The mesoporous alumina supported Cu as claimed in claim 1 2 The preparation method of the O adsorbent is characterized in that the molar ratio of the aluminum nitrate, the cupric salt and the fuel in the step (1) is 1: (2.5-12): (1.7-14.9).
3. The mesoporous alumina-supported Cu according to claim 1 or 2 2 The preparation method of the O adsorbent is characterized in that the cupric salt is at least one of cupric nitrate, cupric chloride, cupric acetate and cupric sulfate.
4. The mesoporous alumina-supported Cu according to claim 1 or 2 2 The preparation method of the O adsorbent is characterized in that the fuel is at least one of glycine, urea and oxalyl diamine.
5. The mesoporous alumina supported Cu as recited in claim 1 2 The preparation method of the O adsorbent is characterized in that the combustion reaction temperature in the step (1) is 150-250 ℃.
6. The mesoporous alumina supported Cu as claimed in claim 1 2 The preparation method of the O adsorbent is characterized in that the reaction in the step (1) is carried out in a container bottle, a rubber plug is plugged at the bottle opening, two thin tubes are inserted into the rubber plug, one thin tube is used as an air inlet for introducing oxygen, and the other thin tube is used as an air outlet for creating the oxygen-enriched environment.
7. The mesoporous alumina supported Cu as claimed in claim 1 2 The preparation method of the O adsorbent is characterized in that the high-temperature calcination in the step (2) is carried out, the heating rate is 3-5 ℃/min, the reaction temperature is 300-600 ℃, and the heat preservation time is 0.5-2 h.
8. The mesoporous alumina supported Cu as claimed in claim 1 2 The preparation method of the O adsorbent is characterized in that the inert atmosphere in the step (3) is stable nitrogen flow, and the flow rate of the air flow is 200-300 mL/min.
9. The mesoporous alumina supported Cu as claimed in claim 1 2 The preparation method of the O adsorbent is characterized in that the high-temperature heat treatment in the step (3) is carried out, the heating rate is 6-10 ℃/min, the reaction temperature is 600-700 ℃, and the heat preservation time is 6-12 h.
10. The mesoporous alumina supported Cu as claimed in claim 1 2 The preparation method of the O adsorbent is characterized in that the Cu prepared in the step (3) 2 O@γ-Al 2 O 3 The adsorbent has a particle size of > 1800m 2 Total specific surface area, > 3.6cm 3 The total pore volume per gram, the size of cuprous oxide particles is 4-15 nm, the adsorbent has high CO saturation adsorption capacity, and the adsorption capacity is 3.6-5.7 mmol/g at 293K.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0442809A (en) * 1990-06-08 1992-02-13 Cataler Kogyo Kk Heat-resistant fibrous alumina having high surface area and its production
CN101486941A (en) * 2009-02-17 2009-07-22 华中科技大学 Process for preparing iron based oxygen carrier
CN102658080A (en) * 2012-04-13 2012-09-12 武汉理工大学 Preparation method of highly-dispersed meso pore gamma-Al2O3 base alkali (soil) metal composite adsorbent
CN109371308A (en) * 2018-12-17 2019-02-22 湘潭大学 The method for preparing multi-principal elements alloy toughened aluminum oxide base metal-ceramic composite powder end
CN110314643A (en) * 2019-07-16 2019-10-11 南京工业大学 A kind of preparation and application of the modified mesopore oxide material of high stability monovalence copper

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0442809A (en) * 1990-06-08 1992-02-13 Cataler Kogyo Kk Heat-resistant fibrous alumina having high surface area and its production
CN101486941A (en) * 2009-02-17 2009-07-22 华中科技大学 Process for preparing iron based oxygen carrier
CN102658080A (en) * 2012-04-13 2012-09-12 武汉理工大学 Preparation method of highly-dispersed meso pore gamma-Al2O3 base alkali (soil) metal composite adsorbent
CN109371308A (en) * 2018-12-17 2019-02-22 湘潭大学 The method for preparing multi-principal elements alloy toughened aluminum oxide base metal-ceramic composite powder end
CN110314643A (en) * 2019-07-16 2019-10-11 南京工业大学 A kind of preparation and application of the modified mesopore oxide material of high stability monovalence copper

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