A porous copper oxide catalyst, a preparation method and application thereof

Abstract

The present application provides a porous copper oxide catalyst, a preparation method and application thereof. The porous copper oxide catalyst has a porous structure, a density of 0.5-1.5 g / cm 3 , and a specific surface area of 60-180 m 2 / g. The preparation method comprises: uniformly mixing a metal salt and a solidified system of carbonizable organic matter, and then solidifying to obtain a catalyst precursor; the metal comprises copper; and carbonizing the catalyst precursor at high temperature under the protection of a protective gas to obtain the porous copper oxide catalyst. The catalyst prepared by the present application has a low density, a higher utilization rate of catalyst metal oxides, and a lower cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalysts, and further relates to a porous copper oxide catalyst, a preparation method and application thereof. BACKGROUND

[0002] In various industrial fields, the presence of trace CO is often harmful to the reaction system or the safety of the system, and needs to be removed as an impurity. In the electronic industry and the polyolefin industry, the content of carbon monoxide and oxygen in the material flow is even in the ppb order of magnitude. With the development of the ethylene industry, the purity of ethylene entering the polymerization refining section is getting higher and higher. Many manufacturers have proposed process parameters in which the inlet CO is even less than 1 ppm, and even less than 0.5 ppm. The existing technology for removing trace CO mainly uses copper oxide catalyst prepared by coprecipitation, which is in the form of cylindrical particles. The copper oxide in the interior of the particles actually only plays a supporting role and cannot catalyze the oxidation reaction with CO. That is to say, only a small amount of CuO in the catalyst plays a catalytic role, and a large amount of CuO only plays a supporting role, and the utilization rate of CuO is very low. That is to say, the activity of copper in unit mass of catalyst is not high. Due to the low utilization rate of CuO, many existing catalysts cannot meet the requirements of the process. In addition, the catalyst prepared by the tablet method has a relatively high density due to the preparation process. In industrial catalytic reactions, the demand for catalysts is in units of volume, so reducing the density of the catalyst can effectively reduce the mass of the catalyst. That is to say, under the premise of the same removal capacity, reducing the density of the catalyst can not only effectively improve the catalytic activity of unit mass of catalyst, but also effectively reduce the cost. Beijing Chemical Research Institute has developed a composite copper oxide catalyst. The catalyst is obtained by compounding Raney copper with porous carbon and then oxidizing. Compared with the industrialized copper oxide catalyst, the composite copper oxide catalyst improves the utilization rate of copper, but the copper-aluminum alloy in the central part only plays a supporting role, and the improvement in reducing the density of the catalyst is not obvious.

[0003] Therefore, it is necessary to develop a porous copper oxide catalyst with lower density, which can improve the utilization rate of the catalyst and effectively reduce the cost of the catalyst. SUMMARY

[0004] In order to solve the technical problems in the prior art, the present application provides a porous copper oxide catalyst, a preparation method and application thereof.

[0005] The present application uses metal salt as raw material, and the metal salt is decomposed into smaller particles after calcination, which has smaller particle size and lower density compared with alloy particles as raw material; meanwhile, the gas generated in the process of metal salt decomposition foams in the carbonizable organic matrix, which can make the carbonized organic material more loose and form a porous structure, thereby further reducing the density of the catalyst.

[0006] Compared with the porous composite copper oxide catalyst of the prior art, the preparation method of the catalyst of the present application further simplifies the operation process. The catalyst after high-temperature decomposition has no center and only supports the inactive components, and the whole catalyst has catalytic activity, and the method effectively reduces the density of the catalyst.

[0007] The porous alumina prepared by the traditional method is mainly prepared by tabletting method, and the catalyst obtained has small specific surface area and large density. The catalyst prepared by the present application has low density, and the same catalyst activity is achieved with lower metal content, and the same volume of catalyst has less metal content, which improves the utilization rate of the catalyst and reduces the cost of the catalyst, overcomes the problem of low utilization rate of CuO catalyst obtained by tabletting method in the prior art, and can remove trace CO.

[0008] One of the purposes of the present application is to provide a porous copper oxide catalyst.

[0009] The porous copper oxide catalyst has a porous structure, and the density is 0.5-1.5 g / cm 3 , preferably 0.5-1.0 g / cm 3 , and more preferably 0.5-0.8 g / cm 3 , the specific surface area is 60-180 m 2 / g, preferably 120-180 m 2 / g.

[0010] In a preferred embodiment of the present application,

[0011] The porous copper oxide catalyst is regenerated by air oxidation after the activity is reduced or deactivated; preferably,

[0012] The oxidation temperature is 60-120℃; and / or,

[0013] The heating time is 3-48 hours, preferably 10-24 hours.

[0014] The second purpose of the present application is to provide a preparation method of a porous copper oxide catalyst, comprising the following steps:

[0015] (1) uniformly mixing metal salt and solidification system of carbonizable organic matter, and then solidifying to obtain catalyst precursor; the metal includes copper;

[0016] (2) Under the protection of protective gas, the catalyst precursor obtained in step (1) is carbonized at high temperature to obtain the porous copper oxide catalyst.

[0017] In a preferred embodiment of the present invention,

[0018] Step (1),

[0019] The mass ratio of the metal salt to the carbonizable organic matter in the curing system is (0.1-5):1, preferably (0.2-2):1, and more preferably (0.2-0.6):1;

[0020] The solidification system of the carbonizable organic matter comprises the carbonizable organic matter and an additive.

[0021] In a preferred embodiment of the present invention,

[0022] The metal salt is at least one of nitrate, carbonate, and bicarbonate;

[0023] The metal further comprises at least one of zinc, manganese and magnesium;

[0024] The mass of copper accounts for no less than 50% of the total mass of the metal, preferably no less than 60%.

[0025] In a preferred embodiment of the present invention,

[0026] The carbonizable organic matter refers to an organic matter that is treated under certain temperature and atmospheric conditions, whereby hydrogen, oxygen, nitrogen, sulfur, etc. in the organic matter are completely or partially volatilized, thereby obtaining a synthetic material with a high carbon content. The obtained carbon material has properties such as high temperature resistance, high strength, high modulus, and porosity. The carbonizable organic matter is an organic polymer compound, preferably at least one of epoxy resin, phenolic resin, furan resin, polystyrene, polyacrylonitrile, starch, viscose fiber, lignin, cellulose, styrene-butadiene rubber, and polyurethane rubber.

[0027] The additives include a curing agent, and preferably also include at least one of a curing accelerator, a dye, a colorant, an antioxidant, a stabilizer, a plasticizer, a lubricant, a flow modifier, a flame retardant, an anti-drip agent, an anti-caking agent, an adhesion promoter, a conductive agent, an impact modifier, a demoulding aid, and a nucleating agent; the additives can specifically adopt the additives commonly used in the field, and a suitable curing agent and an optional curing accelerator can be selected according to the different carbonizable organic matter. The amount of the additives also adopts the amount commonly used in the field and is adjusted according to the actual requirements.

[0028] Mixing can be carried out by a common mixing method in the art, such as stirring;

[0029] The curing conditions also adopt the conventional curing conditions in the art, such as curing at 100-200° C., normal pressure-10 MPa, and 5-240 min.

[0030] After carbonization, the oxide particles are distributed within the carbon voids. The porous carbon structure effectively disperses the metal oxide particles, minimizing sintering during the high-temperature reaction and effectively extending the catalyst's service life. Furthermore, the carbonized organic polymer decomposes during the carbonization and sintering process, creating pores and a fluffy, ultra-light structure. The metal salt also produces a large amount of gas during decomposition, further expanding the pores of the composite catalyst.

[0031] In a preferred embodiment of the present invention,

[0032] Step (2),

[0033] The protective gas is at least one of nitrogen and an inert gas; the inert gas is preferably argon; and / or,

[0034] The carbonization temperature is 400 to 1200°C; preferably 400 to 700°C, more preferably 550 to 700°C; and / or,

[0035] The carbonization time is 1 to 10 hours, preferably 2 to 6 hours, and more preferably 2 to 4 hours.

[0036] The third object of the present invention is to provide a porous copper oxide catalyst obtained by the above preparation method.

[0037] A fourth object of the present invention is to provide an application of a porous copper oxide catalyst in the removal of trace CO.

[0038] In a preferred embodiment of the present invention,

[0039] The CO content in the material is 0.01 to 1000 ppm, preferably 0.01 to 100 ppm, more preferably 0.01 to 10 ppm, and most preferably 0.1 to 5 ppm;

[0040] Reaction temperature 0-150°C, preferably 20-120°C;

[0041] The reaction pressure is 0.1 to 5 MPa, preferably 0.1 to 3.5 MPa;

[0042] The volume space velocity during gas phase reaction is 100~10000h -1 ;

[0043] The volume space velocity during liquid phase reaction is 0.5~100h -1 ;

[0044] When removing trace amounts of CO, the CO content in the material flow after removal is less than 0.1 ppm, preferably less than 60 ppb, and more preferably less than 20 ppb. When the CO content in the material is relatively high, the method of the present invention is also suitable for removal. However, when the CO content in the material is relatively high, the CO concentration in the material flow after removal will be slightly higher accordingly.

[0045] In a preferred embodiment of the present invention,

[0046] The material is at least one of α-olefins, saturated hydrocarbons, styrene, and other materials; the other material is preferably at least one of hydrogen, nitrogen, oxygen, air, and inert gas; the material is preferably at least one of liquid materials of propylene, 1,3-butadiene, 1-butene, and 2-butene, or at least one of gaseous ethylene, gaseous propylene, hydrogen, nitrogen, oxygen, air, and inert gas.

[0047] In view of the fact that the removal of trace amounts of S, O2, As and Cl releases very little heat, elemental copper catalysts are often also used for the removal of these impurities. The catalyst disclosed in the present invention can also be applied in these fields.

[0048] The contents involved in the present invention, such as %, ppm and ppb, are all based on weight.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] (1) The present invention uses metal salts as raw materials. After calcination, the metal salts decompose into smaller particles. Compared with alloy particles, the particles are smaller and have a lower density. Furthermore, the gases generated during the decomposition of the metal salts foam within the carbonizable organic matrix, causing the carbonized organic matter to become looser and form a porous structure, which can further reduce the density of the catalyst. Therefore, the catalyst prepared by the present invention has a low density, and the catalyst mass per unit volume is about 2 / 3 of the mass of catalysts prepared by traditional tableting methods.

[0051] (2) The catalyst prepared by the present invention has a low density. While achieving the same catalyst activity, the metal content is lower. The metal content of the catalyst of the same volume is even less, which improves the utilization rate of the catalyst while reducing the cost of the catalyst. Compared with the porous alumina prepared by the tableting method of the prior art, the utilization rate of the catalyst metal oxide is higher.

[0052] (3) The preparation method of the present invention allows carbon to isolate the copper oxide active component, preventing the excessive growth of copper oxide nanoparticles and reducing the CO removal ability, thereby effectively extending the life of the catalyst.

[0053] (4) The catalyst of the present invention has a low reaction temperature, a simple preparation process, and is easy to load and unload. DETAILED DESCRIPTION

[0054] The application will be described in detail below with reference to specific examples. It is necessary to point out that the following examples are only used to further illustrate the application and cannot be understood as limiting the protection scope of the application. Some non-essential improvements and adjustments of the application made by those skilled in the art according to the content of the application still fall within the protection scope of the application.

[0055] The raw materials used in the examples are all conventional commercially available raw materials.

[0056] Test method:

[0057] Density: The laboratory determination method is the bulk specific gravity, and 100 mL of the catalyst is weighed by a measuring cylinder.

[0058] Pore volume and specific surface area: Determined by a BET adsorption instrument.

[0059] Metal oxide content in the catalyst: X-ray fluorescence spectroscopy (XRF) is performed by using an X-ray photoelectron spectrometer of PA Nalytical BV Company, Netherlands. The element composition and relative content on the surface of the sample are analyzed after vacuum extraction.

[0060] Example 1

[0061] (1) 100 parts by mass of liquid epoxy resin (Balin Petrochemical, CYD-128), 85 parts by mass of curing agent methyltetrahydrophthalic anhydride (MeTHPA) (Guangdong Shengsidaketrade Co., Ltd.), and 1.5 parts by mass of curing accelerator triethanolamine (TEA) (Tianjin Chemical Reagent Factory No. 1) are stirred uniformly.

[0062] (2) 125 g of the epoxy system prepared in step (1) and 33 g of copper nitrate are weighed and fully stirred and mixed, and an appropriate amount of the mixture is added to a cylindrical mold, and the flat plate vulcanizing instrument is used to mold under the conditions of a temperature of 120℃ and a pressure of 7 MPa for 30 mins, and the flat plate vulcanizing instrument is used to mold under the conditions of a temperature of 150℃ and a pressure of 7 MPa for 90 mins, and then cooled to take out, to obtain a cylindrical catalyst precursor with a size of about 2.0 mm x 3.0 mm;

[0063] (3) 100 ml of the catalyst precursor is weighed and placed in a tubular high-temperature electric furnace, the heating rate is 10℃ / min, the carbonization temperature is 650℃, and the nitrogen flow rate is 200 mL / min, and the ultra-light copper oxide catalyst is obtained after nitrogen protection cooling, with a density of 0.56 g / cm 3 , a copper oxide content of 33.1 wt%, and a specific surface area of 152 m 2 / g.

[0064] Example 2

[0065] (1) The powdered phenolic resin and the curing agent hexamethylenetetramine were mixed well by a high-speed mixer, and the weight ratio of hexamethylenetetramine to phenolic resin was 12 / 100; 125 g of the mixture was mixed well with 33 g of copper nitrate and 9 g of zinc nitrate by a high-speed mixer;

[0066] (2) The tablet press was heated to 90°C, and the above materials were put into a mold to be molded into a 2 mm thick sheet on the tablet press; the tablet press was heated to 150°C, and the molded sheet was put into the mold again to be cured under a pressure of 5 MPa for 10 min on the tablet press; the cured 2 mm thick sheet was cut into 3-5 mm rectangular small particles to obtain a catalyst precursor;

[0067] (3) 100 mL of the small particle catalyst precursor was carbonized in a tubular high-temperature electric furnace, the heating rate was 10°C / min, the furnace temperature was 600°C, and the nitrogen flow rate was 200 mL / min; after nitrogen protection cooling, an ultra-light copper oxide catalyst was obtained, the density was 0.58 g / cm 3 , the copper oxide content was 30.8 wt%, the zinc oxide content was 6.8 wt%, and the specific surface area was 148 m 2 / g.

[0068] Example 3

[0069] (1) The powdered phenolic resin and the curing agent hexamethylenetetramine were mixed well by a high-speed mixer, and the weight ratio of hexamethylenetetramine to phenolic resin was 12 / 100; 125 g of the mixture was mixed well with 33 g of copper nitrate and 9 g of zinc nitrate by a high-speed mixer;

[0070] (2) The tablet press was heated to 90°C, and the above materials were put into a mold to be molded into a 2 mm thick sheet on the tablet press; the tablet press was heated to 150°C, and the molded sheet was put into the mold again to be cured under a pressure of 5 MPa for 10 min on the tablet press; the cured 2 mm thick sheet was cut into 3-5 mm rectangular small particles to obtain a catalyst precursor;

[0071] (3) 100 mL of the small particle catalyst precursor was carbonized in a tubular high-temperature electric furnace, the heating rate was 10°C / min, the furnace temperature was 600°C, and the nitrogen flow rate was 200 mL / min; after nitrogen protection cooling, an ultra-light copper oxide catalyst was obtained, the density was 0.58 g / cm 3 , the copper oxide content was 30.8 wt%, the zinc oxide content was 6.8 wt%, and the specific surface area was 148 m 2 / g.

[0072] Example 4

[0073] (1) Powdered phenolic resin and curing agent hexamethylenetetramine were fully mixed with a high-speed stirrer, the weight ratio of hexamethylenetetramine to phenolic resin being 12 / 100; 125 g of the mixture was fully mixed with 45 g of basic copper carbonate and 25 g of zinc carbonate mixture with a high-speed stirrer;

[0074] (2) The tablet press is heated to 90°C, the above materials are placed in a mold and molded on the tablet press to form a 2 mm thick sheet; the tablet press is heated to 150°C, the molded sheet is placed in the mold again and cured under a pressure of 5 MPa on the tablet press for 10 minutes; the cured 2 mm thick sheet is cut into 3-5 mm rectangular small particles to obtain a catalyst precursor;

[0075] (3) 100 mL of small particle catalyst precursor was measured and carbonized in a tubular high-temperature electric furnace at a heating rate of 10 °C / min and a furnace temperature of 600 °C for 3 hours under nitrogen protection at a flow rate of 200 mL / min. After cooling under nitrogen protection, an ultra-light copper oxide catalyst with a density of 0.78 g / cm 3 , copper oxide content is 30.0wt%, zinc oxide content is 29.5wt%, and specific surface area is 153m 2 / g.

[0076] Comparative Example 1

[0077] The CuO / ZnO catalyst was prepared according to the method in Chinese invention patent CN101642707A.

[0078] The specific preparation method is:

[0079] 226 ml of 1 mol / L Cu(NO3)2 solution and 516 mL of 1 mol / L Zn(NO3)2 solution were mixed evenly, and 1000 mL of 1 mol / L Na2CO3 solution was added dropwise to the mixed solution for precipitation at 80°C and a pH value of 9.5±0.5. The mixture was aged for 2 hours under stirring at 80°C, filtered, washed with deionized water, dried at 110°C for 12 hours, and calcined at 400°C for 6 hours before being pressed into tablets. The content of copper oxide was approximately 30.2 wt%. The content of zinc oxide was 69.8 wt%, and the density was 1.5 g / cm 3 ,, the specific surface area is 39.5m 2 / g.

[0080] Comparative Example 2

[0081] (1) 100 parts by mass of liquid epoxy resin (Baling Petrochemical, CYD-128), 85 parts by mass of curing agent methyltetrahydrophthalic anhydride (MeTHPA) (Guangdong Shengshida Science and Trade Co., Ltd.), and 1.5 parts by mass of curing accelerator triethanolamine (TEA) (Tianjin Chemical Reagent Factory No. 1) were stirred evenly.

[0082] (2) Weigh 40 g of the epoxy system prepared in step (1) and 180 g of copper-aluminum alloy powder, wherein the copper-aluminum alloy has a Cu content of 50% (by weight) and an aluminum content of 50% (by weight), and stir and mix them thoroughly. Take an appropriate amount of the mixture and add it to a cylindrical mold. Press it with a flat plate vulcanizer at a temperature of 120° C. and a pressure of 7 MPa for 30 minutes. Press it with a flat plate vulcanizer at a temperature of 150° C. and a pressure of 7 MPa for 90 minutes. Cool it and take it out to obtain a granular catalyst precursor.

[0083] (3) 100 mL of the catalyst precursor was measured and placed in a tubular high-temperature electric furnace. The temperature was raised at a rate of 10°C / min and the carbonization temperature was 600°C. The temperature was maintained for 3 hours under nitrogen protection at a nitrogen flow rate of 200 mL / min. After cooling under nitrogen protection, the carbonized catalyst precursor was obtained.

[0084] (4) Prepare 400 g of 20% NaOH aqueous solution with deionized water, add the carbonized catalyst precursor obtained in step (3), maintain the temperature at 85°C, and filter out the solution after 4 hours to obtain a composite skeleton copper precursor, wherein the copper metal content is 60% (by weight) of the composite skeleton copper precursor. Wash the composite skeleton copper precursor until it is close to neutral, then place it in a methane fluorine furnace and heat it in an air atmosphere, maintain the temperature at 90°C, and keep it warm for 12 hours. The copper oxide content is 35 wt% of the composite copper oxide catalyst and the density is 0.85 g / cm 3 The specific surface area is 89.8m 2 / g.

[0085] The catalysts prepared in Examples 1 to 4 and Comparative Examples 1 to 2 were tested for carbon monoxide removal, as follows:

[0086] Carbon monoxide removal test:

[0087] Catalyst evaluation was conducted in a fixed-bed continuous flow tubular reactor. The catalyst loading was 20 mL. After loading, the catalyst was purged with air at 120°C for 12 hours. The feed gas was a mixture of high-purity N2 and CO containing 2.2 ppm CO. The reaction pressure was 3.5 MPa, the reaction temperatures were 50°C and 90°C, and the space velocity was 5000 hr. -1 .

[0088] The raw materials and products were detected by gas chromatography Agilent 7890 with a nickel methanogen converter, a thermal conductivity detector and a hydrogen flame detector, with a minimum detection limit of carbon monoxide of 0.1 ppm and by a trace carbon monoxide analyzer from AMETEK, with a minimum detection limit of carbon monoxide of 1 ppb.

[0089] The reaction was allowed to stabilize for about 10 to 20 hours and the test data were obtained and listed in Tables 1 and 2, where:

[0090] Table 1 shows the reaction conditions of Examples 1 to 4 and Comparative Examples 1 to 2 at a reaction temperature of 50°C, a reaction pressure of 3.5 MPa, and a space velocity of 5000 hr. -1 , the inlet is a mixed gas containing 2.2ppm of CO, and the outlet CO concentration is measured;

[0091] Table 2 shows the reaction conditions of Examples 1 to 4 and Comparative Examples 1 to 2 at a reaction temperature of 90°C, a reaction pressure of 3.5 MPa, and a space velocity of 5000 hr. -1 , the inlet is a mixed gas containing 2.2ppm of CO, and the outlet CO concentration is measured.

[0092] Table 1

[0093]

[0094] Table 2

[0095]

[0096] It can be seen from the data in Table 1 that under the reaction condition of 50°C, the catalysts prepared in Examples 1 to 4 removed CO to 35 to 55 ppb, while the catalysts prepared in Comparative Examples 1 to 2 removed CO to 956 ppb and 780 ppb, respectively, which is an order of magnitude difference.

[0097] From the data in Table 2, it can be seen that under the reaction conditions of 90°C, the catalysts prepared in Examples 1 to 4 removed CO to 5.5 to 16 ppb, all lower than 20 ppb, while the catalysts prepared in Comparative Examples 1 to 2 removed CO to 80 ppb and 24.8 ppb, respectively, which still shows a large gap.

[0098] The copper oxide contents of Examples 1-4 and Comparative Examples 1-2 are comparable, allowing their activities to be compared. As shown in Tables 1-2, the activities of Catalysts 1-4 prepared according to the present invention are significantly higher than those of the catalysts prepared according to the prior art, represented by Comparative Examples 1-2. Furthermore, even at relatively low temperatures (e.g., 50°C in Table 1), the catalysts prepared according to Examples 1-4 still exhibit good CO removal capabilities. This demonstrates that the catalysts prepared according to the present invention improve the utilization of copper oxide, allowing more copper oxide nanoparticles to participate in the catalytic oxidation of CO.

[0099] The porous copper oxide catalysts prepared in Examples 1 to 4 have a porous structure and a low density, which can reach 0.5 to 0.8 g / cm 3 , while improving the utilization rate of the catalyst, it can effectively reduce the cost of the catalyst, and the preparation method is simple and environmentally friendly.

Claims

1. A porous copper oxide catalyst with a porous structure and a density of 0.5-1.5 g / cm 3 The specific surface area of ​​the catalyst is 60~180m 2 / g; The method for preparing the porous copper oxide catalyst comprises the following steps: (1) uniformly mixing a metal salt with a solidification system of a carbonizable organic matter and then solidifying the mixture to obtain a catalyst precursor; the metal includes copper; the metal salt is at least one of nitrate, carbonate, and bicarbonate; the mass of copper accounts for no less than 50% of the total mass of the metal; the mass ratio of the metal salt to the solidification system of the carbonizable organic matter is (0.1-5):1; (2) Under the protection of protective gas, the catalyst precursor obtained in step (1) is carbonized at high temperature to obtain the porous copper oxide catalyst.

2. The porous copper oxide catalyst according to claim 1, wherein: The density of the porous copper oxide catalyst is 0.5-1.0 g / cm 3 , with a specific surface area of ​​120~180m 2 / g.

3. The porous copper oxide catalyst according to claim 2, wherein: The density of the porous copper oxide catalyst is 0.5-0.8 g / cm 3 .

4. A method for preparing the porous copper oxide catalyst according to any one of claims 1 to 3, comprising the following steps: (1) uniformly mixing the metal salt and the solidification system of the carbonizable organic matter and then solidifying them to obtain a catalyst precursor; The metal includes copper; (2) Under the protection of protective gas, the catalyst precursor obtained in step (1) is carbonized at high temperature to obtain the porous copper oxide catalyst.

5. The method for preparing a porous copper oxide catalyst according to claim 4, wherein: Step (1), The mass ratio of the solidification system of the metal salt and the carbonizable organic matter is (0.1-5):1; and / or, The solidification system of the carbonizable organic matter comprises the carbonizable organic matter and an additive.

6. The method for preparing a porous copper oxide catalyst according to claim 5, wherein: The mass ratio of the metal salt to the carbonizable organic matter in the curing system is (0.2~2):

1.

7. The method for preparing a porous copper oxide catalyst according to claim 6, wherein: The mass ratio of the metal salt to the carbonizable organic matter in the curing system is (0.2-0.6):

1.

8. The method for preparing a porous copper oxide catalyst according to claim 4, wherein: Step (1), The metal salt is at least one of nitrate, carbonate, and bicarbonate; and / or, The metal further comprises at least one of zinc, manganese and magnesium; and / or, The mass of copper accounts for no less than 50% of the total mass of the metal.

9. The method for preparing a porous copper oxide catalyst according to claim 8, wherein: The mass of copper accounts for no less than 60% of the total mass of the metal.

10. The method for preparing a porous copper oxide catalyst according to claim 5, wherein: The carbonizable organic matter is at least one of epoxy resin, phenolic resin, furan resin, polystyrene, polyacrylonitrile, starch, viscose fiber, lignin, cellulose, styrene-butadiene rubber, and polyurethane rubber; and / or The additives include a curing agent.

11. The method for preparing a porous copper oxide catalyst according to claim 10, wherein: The additives also include at least one of a curing accelerator, a dye, a colorant, an antioxidant, a stabilizer, a plasticizer, a lubricant, a flow modifier, a flame retardant, an anti-drip agent, an anti-caking agent, an adhesion promoter, a conductive agent, an impact modifier, a demoulding aid, and a nucleating agent.

12. The method for preparing a porous copper oxide catalyst according to claim 4, wherein: Step (2), The protective gas is at least one of nitrogen and inert gas; and / or, The carbonization temperature is 400-1200°C; and / or, The carbonization time is 1 to 10 hours.

13. The method for preparing a porous copper oxide catalyst according to claim 12, wherein: The inert gas is argon; and / or, The carbonization temperature is 400-700°C; and / or, The carbonization time is 2 to 6 hours.

14. The method for preparing a porous copper oxide catalyst according to claim 13, wherein: The carbonization temperature is 550-700°C; and / or, The carbonization time is 2 to 4 hours.

15. A porous copper oxide catalyst obtained by the preparation method according to any one of claims 4 to 14.

16. Use of the porous copper oxide catalyst according to any one of claims 1 to 3 and 15 in a reaction for removing trace amounts of CO.

17. Use of the porous copper oxide catalyst according to claim 16 in a reaction for removing trace amounts of CO from a material, characterized in that: The CO content in the material is 0.01-1000 ppm; and / or, Reaction temperature 0~150℃; and / or, The reaction pressure is 0.1~5Mpa; and / or, The volume space velocity during gas phase reaction is 100~10000h -1 and / or, The volume space velocity during liquid phase reaction is 0.5~100 h -1 .

18. Use of the porous copper oxide catalyst according to claim 17 in a reaction for removing trace amounts of CO from a material, characterized in that: The CO content in the material is 0.01-100 ppm; and / or, The reaction temperature is 20-120°C; and / or, The reaction pressure is 0.1~3.5Mpa.

19. Use of the porous copper oxide catalyst according to claim 18 in a reaction for removing trace amounts of CO from a material, characterized in that: The CO content in the material is 0.01~10ppm.

20. Use of the porous copper oxide catalyst according to claim 19 in a reaction for removing trace amounts of CO from a material, characterized in that: The CO content in the material is 0.1~5ppm.

21. Use of the porous copper oxide catalyst according to any one of claims 17 to 20 in a reaction for removing trace amounts of CO, characterized in that: The material is , saturated hydrocarbons, and styrene.

22. Use of the porous copper oxide catalyst according to claim 21 in a reaction for removing trace amounts of CO, characterized in that: The material is at least one of liquid materials of propylene, 1,3-butadiene, 1-butene, and 2-butene, or at least one of gaseous ethylene, gaseous propylene, hydrogen, nitrogen, oxygen, and air.

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