Bimetal oxide catalyst and preparation method thereof

Abstract

The invention discloses a bimetallic oxide catalyst and a preparation method thereof. The preparation method comprises the following steps: selecting 80-90-mesh gamma-Al2O3 as a carrier; the preparation method comprises the following steps: taking a certain amount of H2IrCl6. NHO2 and RuCl3. NHO2, and diluting to form an aqueous solution for dipping gamma-Al2O3; adding propyl alcohol, stirring for N hours, filtering and drying; adding ethanol, reducing for 18 hours at the hydrogen pressure of 4.0 Mpa and the temperature of 140 DEG C, and then filtering and drying to obtain the bimetallic catalyst Ru-Ir / gamma-Al2O3; according to the invention, Ir has the characteristic of good activity, but an azo compound is easily formed by hydrogenation, Ru has good selectivity and low catalytic activity, the Ir and the Ru are combined, the Ru with low price is used as a main component, a small amount of Ir is used for adjusting the performance of the catalyst, the performance of the Ru and the Ir is fully exerted under mild adjustment, the catalytic activity of the Ru is improved, and the catalytic activity of the Ru is improved. Meanwhile, azo compounds of Ir are inhibited.

Description

Technical Field

[0001] The present invention relates to the technical field related to metal catalysts, and in particular to a bimetallic oxide catalyst and a preparation method thereof. Background Art

[0002] Catalysis is the mainstay of modern chemistry and a vital field in modern chemistry and chemical engineering. 85% of chemical industrial reactions in the world are carried out under the action of catalysts. Highly active, highly selective and long-life catalysts have made significant contributions to reducing raw material and energy consumption, improving production economy and preventing environmental pollution. In order to obtain supported metal catalysts that meet actual production needs, methods for modifying the morphology, size and carrier of metal particles have been developed. However, catalysts with a single metal component are still difficult to meet the increasing demand for catalytic applications. The use of a second metal to form a bimetallic structure can effectively improve the performance of the catalyst through the synergistic effect between the two metals. Therefore, bimetallic catalysts have attracted extensive research in the field of catalysis. The preparation of bimetallic catalysts generally has the disadvantages of low catalyst activity, low utilization of active metals, high cost, and is not conducive to large-scale production promotion and application. Summary of the invention

[0003] In order to solve the defects of the prior art in the preparation of bimetallic catalysts, such as low catalyst activity, low utilization rate of active metals, high cost, and disadvantages of large-scale production promotion and application, the present invention provides a bimetallic oxide catalyst and a preparation method thereof.

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions:

[0005] The present invention provides a bimetallic oxide catalyst and a preparation method thereof, comprising the following steps:

[0006] Step 1: Select 80-90 mesh γ-Al 2 O 3 For the carrier;

[0007] Step 2: Take a certain amount of H 2 IrCl 6 ·nHO 2 and RuCl 3 ·nHO 2 Dilute to form an aqueous solution to treat γ-Al 2 O 3 Perform impregnation;

[0008] Step 3, then add propanol and stir for N hours, then filter and dry;

[0009] Step 4: Add ethanol to the reduction kettle for hydrogenation reduction and reduce for 18 hours at a hydrogen pressure of 4.0 MPa and a temperature of 140 degrees, then filter and dry to obtain the bimetallic catalyst Ru-Ir / γ-Al 2 O 3 ;

[0010] The reduction kettle comprises a kettle body, and a kettle cover is provided on the kettle body, and a magnetic stirrer for stirring materials is provided in the kettle body, a thermometer for detecting the internal temperature of the kettle body is also provided on the cover, and a pressure gauge for detecting the internal pressure of the kettle body is also provided on the kettle body, and an automatic sampling mechanism for sampling the internal materials is also provided on the kettle body; and a feed pipe and a hydrogen filling pipe are provided on the kettle cover.

[0011] As a preferred technical solution of the present invention, H in step 2 2 IrCl 6 ·nHO 2 and RuCl 3 ·nHO 2 The amount taken is such that the molar ratio of Ir to Ru is 1:4.

[0012] As a preferred technical solution of the present invention, after adding propanol and stirring for N hours in step 3, filtering and drying are performed by drying with an infrared lamp.

[0013] As a preferred technical solution of the present invention, the automatic sampling mechanism includes a sampling tube arranged in the kettle body and vertically downward, and a spiral upward conveying auger is provided in the sampling tube, an inclined material guide tube is provided between the upper end of the sampling tube and the kettle body, and the outer end of the material guide tube extends out of the kettle body, and the material guide tube is provided with a filter at one end located inside the kettle body, and a buffer barrel is provided at the bottom end of the material guide tube, a first solenoid valve is provided between the pipelines of the material guide tube and the buffer barrel, and the bottom of the buffer barrel is connected to a collecting cylinder via a conduit, and a second solenoid valve is provided on the conduit.

[0014] As a preferred technical solution of the present invention, the bottom end of the sampling tube is a closed end, and a feed port is provided on the side wall of the sampling tube.

[0015] As a preferred technical solution of the present invention, a material circulation mechanism is provided on the kettle body, and the material circulation mechanism includes a discharge pipe arranged at the bottom of the kettle body, and a three-way valve is provided on the discharge pipe, and an inlet pipe is provided at the upper end of the kettle body, a circulation pump is provided between the inlet pipe and one end of the three-way valve, and a discharge pipe is provided at the last end of the three-way valve.

[0016] As a preferred technical solution of the present invention, the buffer barrel is provided with a hydrogen release pipe, and the hydrogen release pipe is provided with a switch valve, and the end of the hydrogen release pipe is connected to a collection tank for collecting hydrogen.

[0017] As a preferred technical solution of the present invention, the buffer barrel is made of transparent material.

[0018] The beneficial effects of the present invention are:

[0019] 1. Preparation method of the supported bimetallic catalyst Bimetallic catalyst Ru-Ir / γ-Al 2 O 3 Among them, Ir has the characteristics of good activity, but it is easy to form azo compounds after hydrogenation. Ru has good selectivity but low catalytic activity. The two are combined, in which cheap Ru is used as the main catalyst and a small amount of Ir is used to adjust the performance of the catalyst. Under mild regulation, the performance of Ru and Ir is fully exerted, the catalytic activity of Ru is improved, and the azo compounds of Ir are inhibited.

[0020] 2. In the preparation method of this supported bimetallic catalyst, a specific reduction kettle is set up to carry out reduction, wherein the reduction kettle is provided with an automatic sampling mechanism for sampling the internal material, which can automatically sample to monitor the reduction process and then make corresponding adjustments and analyses on the reduction work.

[0021] 3. In the preparation method of the supported bimetallic catalyst, a material circulation mechanism is provided and a circulation pump is used to provide power so that the material circulates in the kettle, thereby enabling the material to fully undergo a reduction reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The accompanying drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation of the present invention. In the accompanying drawings:

[0023] Figure 1 It is a schematic flow diagram of a bimetallic oxide catalyst and a preparation method thereof of the present invention;

[0024] Figure 2 It is a schematic structural diagram of a reduction kettle of a bimetallic oxide catalyst and a preparation method thereof of the present invention;

[0025] Figure 3 It is a structural schematic diagram of an automatic sampling mechanism of a bimetallic oxide catalyst and a preparation method thereof of the present invention;

[0026] Figure 4 It is a structural schematic diagram of a feed port of a bimetallic oxide catalyst and a preparation method thereof of the present invention.

[0027] In the figure: 1. reduction kettle; 2. kettle body; 3. agitator; 4. thermometer; 5. pressure gauge; 6. automatic sampling mechanism; 7. sampling tube; 8. conveying auger; 9. material guide pipe; 10. filter screen; 11. buffer barrel; 12. first solenoid valve; 13. conduit; 14. second solenoid valve; 15. feed port; 16. material circulation mechanism; 17. discharge pipe; 18. three-way valve; 20. circulation pump; 21. discharge pipe; 22. feed pipe; 23. hydrogen filling pipe; 24. hydrogen release pipe; 25. switch valve; 26. collecting tank. DETAILED DESCRIPTION

[0028] The preferred embodiments of the present invention are described below in conjunction with the accompanying drawings. It should be understood that the preferred embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0029] Example: Figure 1 As shown, the present invention provides a bimetallic oxide catalyst and a preparation method thereof, comprising the following steps:

[0030] Step 1: Select 80-90 mesh γ-Al 2 O 3 For the carrier;

[0031] Step 2: Take a certain amount of H 2 IrCl 6 ·nHO 2 and RuCl 3 ·nHO 2 Dilute to form an aqueous solution to treat γ-Al 2 O 3 Perform impregnation;

[0032] Step 3, then add propanol and stir for N hours, then filter and dry;

[0033] Step 4: Then add ethanol and reduce for 18 hours at a hydrogen pressure of 4.0 MPa and a temperature of 140 degrees, and then filter and dry to obtain a bimetallic catalyst Ru-Ir / γ-Al 2 O 3 .

[0034] The bimetallic catalyst Ru-Ir / γ-Al prepared by the method 2 O 3Among them, Ir has the characteristics of good activity, but it is easy to form azo compounds after hydrogenation. Ru has good selectivity but low catalytic activity. The two are combined, in which cheap Ru is used as the main catalyst and a small amount of Ir is used to adjust the performance of the catalyst. Under mild regulation, the performance of Ru and Ir is fully exerted, the catalytic activity of Ru is improved, and the azo compounds of Ir are inhibited.

[0035] Wherein, H in step 2 2 IrCl 6 ·nHO 2 and RuCl 3 ·nHO 2 The amount taken is such that the molar ratio of Ir to Ru is 1:4.

[0036] Wherein, after adding propanol and stirring for N hours in step 3, filtering and drying are performed, and the drying method is to use an infrared lamp for drying.

[0037] Among them, Figure 2 , Figure 3 and Figure 4 As shown, it also includes a reduction kettle 1 for hydrogenation reduction in step 4, and the reduction kettle 1 includes a kettle body 2, and the kettle body 2 is provided with a kettle cover 27, and the kettle body is provided with a stirrer 3 for stirring the material, and the cover is also provided with a thermometer 4 for detecting the internal temperature of the kettle body 2, and the kettle body 2 is also provided with a pressure gauge 5 for detecting the internal pressure of the kettle body 2, and the kettle body 2 is also provided with an automatic sampling mechanism 6 for sampling the internal material; and the kettle cover is provided with a feed pipe 22 and a hydrogen gas filling pipe 23. Reduction is performed by setting a specific reduction kettle, wherein the reduction kettle is provided with an automatic sampling mechanism for sampling the internal material, which can perform automatic sampling to monitor the reduction process, and then adjust and analyze the reduction work accordingly.

[0038] The automatic sampling mechanism 6 includes a sampling tube 7 arranged in the kettle body 2 and vertically downward, and a spiral upward conveying auger 8 is arranged in the sampling tube 7, an inclined guide tube 9 is arranged between the upper end of the sampling tube 7 and the kettle body 2, and the outer end of the guide tube 9 extends out of the kettle body 2, and the guide tube 9 is provided with a filter screen 10 at one end located inside the kettle body 2, and a buffer barrel 11 is arranged at the bottom end of the guide tube 9, and a first solenoid valve 12 is arranged between the guide tube 9 and the buffer barrel 11, and the bottom of the buffer barrel 11 is connected to a collecting barrel 14 through a conduit 13, and a second solenoid valve 28 is arranged on the conduit 13. Under the action of the conveying auger, the material in the reduction process in the kettle body is sent into the sampling tube, and flows from the guide tube 9 into the buffer barrel 11, and is buffered in the buffer barrel, and then the material in the buffer barrel is discharged into the mobile phone barrel by controlling the first solenoid valve and the second solenoid valve, thereby completing the sampling work.

[0039] The bottom end of the sampling tube 7 is a closed end, and a feed port 15 is provided on the side wall of the sampling tube 7 .

[0040] The kettle body 2 is provided with a material circulation mechanism 16, and the material circulation mechanism 16 includes a discharge pipe 17 arranged at the bottom of the kettle body 2, and a three-way valve 18 is arranged on the discharge pipe 17, and an inlet pipe 19 is arranged at the upper end of the kettle body 2, and a circulation pump 20 is arranged between the inlet pipe 19 and one end of the three-way valve 18, and a discharge pipe 21 is arranged at the last end of the three-way valve. By setting up the material circulation mechanism and using the circulation pump to provide power, the material circulates in the kettle body, so that the material can fully undergo a reduction reaction.

[0041] The buffer barrel 11 is provided with a hydrogen release pipe 24, and a switch valve 25 is provided on the hydrogen release pipe 24, and a collection tank 26 for collecting hydrogen is connected to the end of the hydrogen release pipe 24. It is convenient to discharge hydrogen into the collection pipe for collection, so that it will not be discharged into the external environment, which may cause fire and explosion.

[0042] The buffer bucket 11 is made of a transparent material 27, which is convenient for viewing during the sampling process.

[0043] The preparation method of the supported bimetallic catalyst has the following specific preparation process:

[0044] Step 1: Select 80-90 mesh γ-Al 2 O 3 For the carrier;

[0045] Step 2: Take a certain amount of H 2 IrCl 6 ·nHO 2 and RuCl 3 ·nHO2 Dilute to form an aqueous solution to treat γ-Al 2 O 3 Perform impregnation;

[0046] Step 3, then add propanol and stir for N hours, then filter and dry;

[0047] Step 4: Then add ethanol and reduce for 18 hours at a hydrogen pressure of 4.0 MPa and a temperature of 140 degrees, and then filter and dry to obtain a bimetallic catalyst Ru-Ir / γ-Al 2 O 3 .

[0048] The bimetallic catalyst Ru-Ir / γ-Al prepared by the method 2 O 3 Among them, Ir has the characteristics of good activity, but it is easy to form azo compounds after hydrogenation. Ru has good selectivity but low catalytic activity. The two are combined, in which cheap Ru is used as the main catalyst and a small amount of Ir is used to adjust the performance of the catalyst. Under mild regulation, the performance of Ru and Ir is fully exerted, the catalytic activity of Ru is improved, and the azo compounds of Ir are inhibited.

[0049] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A bimetallic oxide catalyst and a preparation method thereof, characterized in that: The following steps are involved: Step 1, select 80-90 mesh γ-Al2O3 as the carrier; Step 2: Take a certain amount of H2IrCl6·nHO2 and RuCl3·nHO2 and dilute them to form an aqueous solution to impregnate γ-Al2O3; Step 3, then add propanol and stir for N hours, then filter and dry; Step 4, then adding ethanol to the reduction kettle (1) for hydrogenation reduction and reducing for 18 hours at a hydrogen pressure of 4.0 MPa and a temperature of 140 degrees, and then filtering and drying to obtain a bimetallic catalyst Ru-Ir / γ-Al2O3; The reduction kettle (1) comprises a kettle body (2), and the kettle body (2) is provided with a kettle cover (27), and the kettle body is provided with a stirrer (3) for stirring materials, the cover is also provided with a thermometer (4) for detecting the internal temperature of the kettle body (2), the kettle body (2) is also provided with a pressure gauge (5) for detecting the internal pressure of the kettle body (2), and the kettle body (2) is also provided with an automatic sampling mechanism (6) for sampling the internal materials; and the kettle cover is provided with a feed pipe (22) and a hydrogen filling pipe (23).

2. A bimetallic oxide catalyst and a preparation method thereof according to claim 1, characterized in that: The amounts of H2IrCl6·nHO2 and RuCl3·nHO2 in step 2 are such that the molar ratio of Ir to Ru is 1:

4.

3. A bimetallic oxide catalyst and a preparation method thereof according to claim 1, characterized in that: After adding propanol in step 3 and stirring for N hours, filtering and drying are performed by drying with an infrared lamp.

4. A bimetallic oxide catalyst and a preparation method thereof according to claim 1, characterized in that: The automatic sampling mechanism (6) comprises a sampling tube (7) arranged in the kettle body (2) and extending vertically downward, and a conveying auger (8) extending spirally upward is arranged in the sampling tube (7), an inclined material guide tube (9) is arranged between the upper end of the sampling tube (7) and the kettle body (2), and the outer end of the material guide tube (9) extends out of the kettle body (2), and a filter screen (10) is arranged at one end of the material guide tube (9) located inside the kettle body (2), and a buffer barrel (11) is arranged at the bottom end of the material guide tube (9), a first electromagnetic valve (12) is arranged between the pipelines of the material guide tube (9) and the buffer barrel (11), and the bottom of the buffer barrel (11) is connected to a collecting cylinder (14) via a conduit (13), and a second electromagnetic valve (28) is arranged on the conduit (13).

5. A bimetallic oxide catalyst and a preparation method thereof according to claim 4, characterized in that: The bottom end of the sampling tube (7) is a closed end, and a feed port (15) is provided on the side wall of the sampling tube (7).

6. A bimetallic oxide catalyst and a preparation method thereof according to claim 5, characterized in that: The kettle body (2) is provided with a material circulation mechanism (16), and the material circulation mechanism (16) comprises a discharge pipe (17) arranged at the bottom of the kettle body (2), and the discharge pipe (17) is provided with a three-way valve (18), and an inlet pipe (19) is provided at the upper end of the kettle body (2), a circulation pump (20) is provided between the inlet pipe (19) and one end of the three-way valve (18), and a discharge pipe (21) is provided at the last end of the three-way valve.

7. A bimetallic oxide catalyst and a preparation method thereof according to claim 6, characterized in that: The buffer barrel (11) is provided with a hydrogen release pipe (24), and the hydrogen release pipe (24) is provided with a switch valve (25), and the end of the hydrogen release pipe (24) is connected to a collection tank (26) for collecting hydrogen.

8. A bimetallic oxide catalyst and a preparation method thereof according to claim 7, characterized in that: The buffer barrel (11) is made of a transparent material (27).

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