CN109926048B - Single-component double-active-site Cu2O-CuO nano mixed phase structure copper oxide catalyst, preparation method and application - Google Patents
Single-component double-active-site Cu2O-CuO nano mixed phase structure copper oxide catalyst, preparation method and application Download PDFInfo
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Abstract
The invention belongs to the technical field of catalytic materials, and provides single-component double-active-site Cu2An O-CuO nano mixed phase structure copper oxide catalyst, a preparation method and application. The catalyst can be used for selective catalytic oxidation reaction of ammonia. The surface reconstruction process of the cuprous particles is controlled by adjusting the pretreatment condition of the catalyst, so that the aim of regulating and controlling the formation of the surface copper oxide outer wall is fulfilled. Finally obtaining the Cu2Cu with O nano-particles as cores and CuO shells wrapped outside2The O-CuO nano mixed phase structure composite copper oxide material. The catalyst has excellent ammoxidation activity and N2Selectivity, and good reaction stability. The preparation method is simple, efficient and reliable, the raw materials are easy to obtain, and the macro preparation is easy.
Description
Technical Field
The invention belongs to the technical field of catalytic materials, and particularly relates to single-component double-active-site Cu2An O-CuO nano mixed phase structure copper oxide catalyst, a preparation method and application.
Background
In recent years, the heterogeneous catalysis technology has attracted attention in the application of treating the emission of polluted gas with the characteristics of rapidness, high efficiency, energy conservation, simple process and the like. Among them, ammonia selective catalytic oxidation method (NH)3SCO) becomes an important research object as an important process link for effectively removing the excessive ammonia gas.
In view of practical application, needles are currently usedTo NH3The research on the catalytic system in SCO is mainly based on transition metal oxide catalysts, such as Cu, Mn, Fe, Co and the like. Wherein Cu oxide is converted in ammonia and N2The expression on the generation amount is particularly outstanding, and the method is considered to have good application prospect. Chmielarz et al, using zeolite modification technology, synthesize Cu-ZSM-5 supported catalysts and apply them to NH3SCO reaction, and the result shows that the oxidation-reduction characteristic of CuO species and the provided acidic site directly influence the ammoxidation activity, ammonia can be completely converted at 380 ℃, and simultaneously N is generated2The yield reaches more than 90%, and the catalyst can maintain stable conversion rate (Microp) under high temperature.&Mat, 2017,246:193- "206). In order to improve the ammonia oxidation performance of the CuO-based catalyst, a Qu task group is doped with Ce and Zr oxide components, and a series of Cu-Ce-Zr ternary oxide composite catalysts are synthesized by different preparation methods, so that the result shows that the ternary catalyst can effectively improve the catalytic activity of CuO, can completely oxidize ammonia at 230 ℃, and ensure 90% of N2Selectivity (catal.sci.&Technol.2016,6: 4491-. However, research on the CuO catalyst is focused on the supported catalyst or the multi-element composite catalyst, a complex system generates complicated preparation steps and wastes resources, and the conversion temperature of the catalyst needs to be further reduced to match the actual application requirements.
In copper oxide research, cuprous oxide (Cu)2O) material is easily overlooked due to its instability in oxidizing atmospheres. However, with Cu2The O material is widely and intensively studied, and more researches are focused on by developing its unique physicochemical properties and applying it to various fields. To date, cuprous oxide materials have been widely used in electrochemical sensors, lithium battery electrode materials, photocatalytic degradation, modified catalysts, and organic synthesis reactions. Cu2The morphological effect and surface atomic structure of O material are key to influence the catalytic efficiency, Cu is in the oxidation reaction process2The surface atomic rearrangement occurs on the surface of the O catalyst, thereby affecting the catalytic activity. For Cu2The study of O nanomaterials and their reconstitution processes is of great importance. However, it is not limited toAt present, no Cu exists2O is at NH3Application in SCO and study of subsequent control of the reconstitution process to modulate catalyst activity.
Disclosure of Invention
The invention solves the problems: overcomes the defects of complex catalytic system, unfavorable synthesis and high reaction temperature in the prior art, and provides single-component double-active-site Cu for ammonia catalytic oxidation reaction2The O-CuO nano mixed phase structure copper oxide catalyst realizes the control of the surface reconstruction process of cuprous particles by adjusting the pretreatment condition of the catalyst so as to achieve the purpose of regulating and controlling the formation of the surface copper oxide outer wall. Finally obtaining the Cu2Cu with O nano-particles as cores and CuO shells wrapped outside2O-CuO nano mixed phase structure composite material. The catalyst has excellent ammoxidation activity and N2Selectivity, and good reaction stability.
The technical scheme of the invention is as follows:
single-component double-active-site Cu2O-CuO nano mixed phase structure copper oxide catalyst, Cu2Cu with O nano-particles as cores and CuO shells wrapped outside2O-CuO nano mixed phase structure composite material.
The single-component double-active site Cu2The grain diameter of the copper oxide catalyst with the O-CuO nano mixed phase structure is 100-400 nm.
The thickness of the CuO layer is 10 nm.
Single-component double-active-site Cu2The preparation method of the O-CuO nano mixed phase structure copper oxide catalyst comprises the following steps:
(1) dissolving a copper precursor in deionized water to prepare a solution a with the concentration of 0.01mol/L, then adding citric acid into the solution a, and stirring at room temperature for 0.5-1h to obtain a solution b; wherein the mass ratio of the copper precursor to the citric acid is 1 (15-20);
(2) adding an alkaline solution into the solution b until the pH value of the solution is 11, stirring at room temperature for 20-30min, adding an ascorbic acid solution to obtain a solution c, stirring the solution c at 40 ℃ for 3h, centrifuging, washing, and drying in vacuum to obtain Cu2O; of said ascorbic acid solutionThe concentration is 0.6 mol/L; the volume ratio of the ascorbic acid solution to the solution b is 1: 10;
(3) cu prepared in the step (2)2O is at NH3、O2Carrying out calcination pretreatment in mixed gas of He and He; the total flow rate of the mixed gas is 100 ml/min; NH (NH)3The concentration is 0-5000ppm, O2The concentration is 10 vol%, and the pretreatment time is 1 h; the treatment temperature was 225 ℃ and 275 ℃.
The copper precursor is copper nitrate, copper sulfate or copper chloride.
In the step (2), the alkaline solution is sodium hydroxide or potassium hydroxide, and the concentration is 2.0 mol/L.
The concentration of the pretreated mixed gas is 1000ppm NH3(ii) a The pretreatment temperature was 250 ℃.
Single-component double-active-site Cu2The O-CuO nano mixed phase structure copper oxide catalyst is used as a catalyst for ammonia catalytic oxidation reaction, and the space velocity is 50000h-1Reaction gas concentration 1000ppm NH3，10vol％O2And He balance.
The invention has the beneficial effects that: compared with the prior CuO system supported or composite system catalyst, the invention has the following advantages: because the catalyst has single copper oxide component and double active sites Cu2The catalyst has O-CuO nanometer mixed structure and can be used for ammonia selective catalytic oxidation reaction. The control of the surface reconstruction process of the cuprous particles is realized by adjusting the pretreatment condition of the catalyst, so as to achieve the purpose of regulating and controlling the formation of the surface copper oxide outer wall. Finally obtaining the Cu2Cu with O nano-particles as cores and CuO shells wrapped outside2O-CuO nano mixed phase structure composite material. The catalyst exhibits good ammoxidation activity and high N2Selectivity and stability. The catalyst can completely convert ammonia gas at 210 ℃ and has more than 90% of N2And (4) selectivity.
The preparation process is simple, the operation is easy, and the mass production can be realized.
The catalyst system is single, which is beneficial to saving cost.
The precipitation speed of copper hydroxide is controlled by adding citric acid to control Cu2O particlesThe size of the particles.
The formation of the CuO on the outer layer can be controlled by controlling the pretreatment conditions; formation of Cu under specific conditions2The O-CuO mixed-phase structure nano-catalyst has excellent catalytic performance.
Drawings
FIG. 1 shows Cu of samples obtained in examples 1 and 22(a) NH of O-CuO miscible catalyst with catalysts prepared in comparative examples 1 and 23Catalytic activity and (b) N2And (4) a selectivity graph.
FIG. 2 shows Cu obtained in example 12Stability of the O-CuO-A sample.
FIG. 3 shows Cu of samples obtained in examples 1 and 22XRD diffraction patterns of the O-CuO mixed phase structure catalyst and the catalysts prepared in comparative examples 1 and 2.
FIG. 4 shows Cu obtained in example 12A scanning electron microscope characterization (SEM) comparison graph of the O-CuO mixed-phase structure catalyst and the catalysts prepared in the comparative examples 1 and 2; wherein (a) Cu2O，(b)Cu2O-CuO-A，(c)CuO。
Detailed Description
The present invention is further illustrated in detail by the following examples, but the scope of the claims of the present invention is not limited to these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, and do not mean that the conditions must be met for achieving the purpose.
Example 1
Method for preparing cubic structure Cu by liquid phase reduction method2O particles:
(1) copper nitrate was first dissolved in 900ml of deionized water to prepare a solution at a concentration of 0.01mol/L, while 0.09g of citric acid particles were added to the solution and stirred at room temperature for 0.5 h. Then, a 2.0mol/L sodium hydroxide solution was gradually dropped into the mixed solution until the pH became 11. After stirring for a further 0.5h at room temperature, 0.6mol/L ascorbic acid solution was added to the solution, whereupon the mixture was heated to 40 ℃ and held constant, and stirring was continued for 3 h. Cu obtained by centrifugation2O samples, washed with deionized water and alcohol. Finally, the catalyst is dried for 12 hours in a vacuum environment. Scanning electron of prepared sampleThe results, as seen in FIG. 1, show that the catalyst exhibited typical Cu2An O cubic crystal structure and a smooth surface, and a particle edge size of 100 to 400 nm.
Cu2Preparing an O-CuO mixed-phase nano catalyst:
mixing the Cu prepared in the step (1)2O is at NH3，O2Carrying out calcination pretreatment in mixed gas of He and He; the total flow rate of the mixed gas is 100 ml/min; NH (NH)3Concentration 1000ppm, O2The concentration is 10 vol%, and the pretreatment time is 1 h; the pretreatment temperature is 250 ℃, and the catalyst Cu is obtained2O-CuO-A。
Example 2
The pretreatment temperatures were changed to 225 ℃ and 275 ℃ and the other steps were the same as in example 1 to obtain catalyst Cu2O-CuO-B and Cu2O-CuO-C, the catalyst is still Cu2An O-CuO mixed structure.
Comparative example 1
The calcination pretreatment step in example 1 was omitted, and the other steps were the same as in comparative example 1 to obtain catalyst Cu2O。
Comparative example 2
The calcination pretreatment temperature in example 1 was changed to 300 ℃, and the other steps were the same as in comparative example 1 to obtain a catalyst CuO.
Example 3
Catalysts prepared in examples 1,2 and comparative examples 1,2 for NH3The catalytic oxidation performance test is carried out on a fixed bed reactor in a continuous operation mode, He is used as balance gas, and NH is adopted3On-line analysis of reacted gaseous NH by analyzer and gas chromatograph3Molecule and product N2A molecule. The reaction conditions are specifically as follows: 1000ppm NH3，10vol％O2He is used as balance gas, and the reaction space velocity is 50000h-1The mass of the catalyst was 0.15 g. Ammonia conversion As shown in FIG. 1a, Cu2The catalytic activity of O-CuO-A is optimal and reaches 100 percent of NH at 210 DEG C3Conversion while FIG. 1b, N2The selectivity reaches over 90 percent in the reaction temperature section.
Example 4
For Cu prepared in example 12O-CuO mixed phase nano-catalyst, the stability of the catalyst is considered, 1800min stability experiment is carried out under the reaction condition of the example 3, and then Cu is tested by continuous operation at 210 DEG C2The stability of the O-CuO-A catalyst, as shown in FIG. 2, substantially maintains the ammoniA conversion at 100%.
Example 5
The catalysts prepared in examples 1 and 2 and comparative examples 1 and 2 were characterized by XRD test, and the crystal form evolution process thereof is shown in FIG. 3. Cu2The O catalyst exists in a typical cuprous cuprite crystal form, and an initially synthesized cuprous oxide structure has a good crystal form structure and stronger lattice energy. When Cu2When the O is calcined at the temperature of 225-275 ℃, the main crystal structure is from Cu2O gradually transitions to CuO. Catalyst Cu2Cu appears in O-CuO- (A-C)2An O-CuO mixed phase structure. When the calcining temperature is increased to 300 ℃, the metal belongs to Cu2The diffraction peak of the O crystal phase almost completely disappeared and only the CuO phase existed.
Example 6
The nanocatalysts prepared in example 1 and comparative examples 1 and 2 are characterized by an electron microscope, and the morphology evolution process is shown in fig. 4 a. Cu2O exhibits a typical cubic crystal structure and has a smooth surface with a particle edge size of 100 to 400 nm. After pretreatment at 250 ℃, catalyst Cu as shown in FIG. 4b2The size of the O-CuO-A particles hardly changes and the cubic structure is still maintained. But the particles start to become rough with rounded particles less than 50nm formed on the surface. When the calcination temperature is raised to 300 ℃, as shown in fig. 4c, it can be seen that the CuO shell is continuously thickened, but still has a cubic morphology.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above examples are provided only for the purpose of describing the present invention, and are not intended to limit the scope of the present invention. The scope of the invention is defined by the appended claims. Various equivalent substitutions and modifications can be made without departing from the spirit and principles of the invention, and are intended to be within the scope of the invention.
Claims (5)
1. Single-component double-active-site Cu2The application of the O-CuO nano mixed phase structure copper oxide catalyst as the ammonia catalytic oxidation reaction is characterized in that the space velocity of the reaction is 50000h-1Reaction gas concentration 1000ppm NH3，10 vol% O2He balance;
the single-component double-active site Cu2Cu as O-CuO nano mixed phase structure copper oxide catalyst2Cu with O nano-particles as cores and CuO shells wrapped outside2O-CuO nano mixed phase structure composite material; the single-component double-active site Cu2The grain diameter of the copper oxide catalyst with the O-CuO nano mixed phase structure is 100-400 nm; the thickness of the CuO layer is 10 nm;
single-component double-active-site Cu2The preparation method of the O-CuO nano mixed phase structure copper oxide catalyst comprises the following steps:
(1) dissolving a copper precursor in deionized water to prepare a solution a with the concentration of 0.01mol/L, then adding citric acid into the solution a, and stirring at room temperature for 0.5-1h to obtain a solution b; wherein the mass ratio of the copper precursor to the citric acid is 1 (15-20);
(2) adding an alkaline solution into the solution b until the pH value of the solution is 11, stirring at room temperature for 20-30min, adding an ascorbic acid solution to obtain a solution c, stirring the solution c at 40 ℃ for 3h, centrifuging, washing, and drying in vacuum to obtain Cu2O; the concentration of the ascorbic acid solution is 0.6 mol/L; the volume ratio of the ascorbic acid solution to the solution b is 1: 10;
(3) cu prepared in the step (2)2O is at NH3、O2Carrying out calcination pretreatment in mixed gas of He and He; the total flow rate of the mixed gas is 100 ml/min; NH (NH)3The concentration is 0-5000ppm, O2The concentration is 10 vol%, and the pretreatment time is 1 h; the treatment temperature was 225 ℃ and 275 ℃.
2. Use according to claim 1, wherein the copper precursor is copper nitrate, copper sulphate or copper chloride.
3. The use according to claim 1 or 2, wherein the alkaline solution in step (2) is sodium hydroxide solution or potassium hydroxide solution with a concentration of 2.0 mol/L.
4. Use according to claim 1 or 2, wherein the pre-treatment gas mixture has a concentration of 1000ppm NH3(ii) a The pretreatment temperature was 250 ℃.
5. Use according to claim 3, wherein the pre-treatment gas mixture has a concentration of 1000ppm NH3(ii) a The pretreatment temperature was 250 ℃.
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