A carbon-modified alumina support, catalyst, preparation method thereof, and method for deep removal of trace amounts of CO

Abstract

This invention provides a carbon-modified alumina support, a catalyst, its preparation method, and a method for deep removal of trace amounts of CO. The specific surface area of ​​the alumina support is ≥300 m². 2 / g, pore volume 1.0~3.5m 3 / g. The preparation method includes: first, preparing a sodium aluminate solution from sodium hydroxide and sodium aluminate, adding it to an aluminum sulfate solution to obtain a boehmite precursor, crystallizing it to obtain boehmite, then adding it to a nitrogen-containing polymer solution, impregnating it, and reacting it. The resulting reaction product is calcined under a protective atmosphere to obtain the carbon-modified alumina support; contacting it with an impregnation solution containing active components, removing the impregnated carbon-modified alumina support, and then subjecting it to a second calcination under a protective atmosphere to obtain the catalyst; and then reacting the CO-containing material with the obtained catalyst to remove CO. The catalyst prepared by this invention has a large specific surface area of ​​support, resulting in a large catalyst loading and high dispersion of active metals.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and more specifically, to a carbon-modified alumina support, a catalyst, a method for preparing the same, and a method for deep removal of trace amounts of CO. Background Technology

[0002] Alumina-supported catalysts are widely used in petrochemical plants. Supports in catalysts increase mechanical strength, reduce wear, increase specific surface area, facilitate good dispersion of active components, and can also act as co-catalysts. Activated alumina is a porous, highly dispersible solid material with high resistance to breakage, moderate specific surface area, adjustable pore size and porosity, good adsorption performance, a wide crystal temperature range, and acidic surface properties. It has become one of the most widely used catalysts or catalyst supports in the chemical and petroleum industries, playing a crucial role in reactions such as petroleum component cracking, hydrorefining, hydrodesulfurization, hydrocarbon reforming for hydrogen production, and automobile exhaust purification. Structure is one of the important properties of catalyst supports; key measures describing the pore structure include specific surface area, pore volume, average pore size, and pore distribution. Catalytic reactions occur on the catalyst surface, and specific surface area plays a crucial role in the dispersion of active components, which in turn is closely related to catalytic activity. Pore volume is the sum of the volumes of all micropores per unit mass of catalyst and is closely related to catalyst stability and lifetime. Pore ​​size and pore shape affect the internal diffusion rate of reactants and products, thus influencing the activity and selectivity of the catalyst. As a catalyst support, a high specific surface area and abundant pore structure provide active sites and pathways for the reaction, essential for improving reaction efficiency. The specific surface area and total pore volume, as well as pore size and its distribution, significantly impact catalyst performance. Large pore volume facilitates the diffusion of macromolecular compounds into the catalyst particles, enabling the hydrogenation conversion of macromolecules. High specific surface area promotes the diffusion of active metals, thereby increasing the performance of the catalytic catalyst. Large pore structures can improve reaction selectivity, maximizing the utilization of active sites within the pores and enhancing catalyst activity. Furthermore, large pore structures can inhibit coking on the catalyst surface, extending catalyst lifetime.

[0003] There are few alumina supports with large specific surface area in the existing technology, and they are difficult to prepare. It is necessary to study an alumina support with a large specific surface area so that the catalyst loading is large and the dispersion of active metals is high. Summary of the Invention

[0004] To address the technical problems existing in the prior art, the present invention provides a carbon-modified alumina support, a catalyst, a method for preparing the same, and a method for deep removal of trace amounts of CO.

[0005] Compared with the impregnation method, the traditional preparation method produces larger active metal particles; however, the impregnation method results in a lower carrier loading. This invention solves the problem of low carrier loading in traditional alumina.

[0006] This invention first prepares a large specific surface area alumina support, then contacts the large specific surface area alumina support with a nitrogen-containing polymer solution, and then calcines the contact product under an inert atmosphere to obtain the support. Finally, the active component is loaded onto the support to obtain the catalyst. The carbon-modified large specific surface area alumina-supported catalyst prepared by this invention has a large specific surface area of ​​support, which allows for a large catalyst loading and high dispersion of active metals.

[0007] One of the objectives of this invention is to provide a carbon-modified alumina support.

[0008] The specific surface area of ​​the alumina carrier is ≥300m². 2 / g, preferably 320-550m 2 / g, more preferably 400-480m 2 / g; pore volume is 1.0~3.5cm³ 3 / g, preferably 1.5–3.0cm 3 / g.

[0009] The alumina carrier of this invention has a water absorption rate of 110-160%, wherein the test method for the water absorption rate is as follows:

[0010] Weigh a fixed mass of alumina carrier m1, place it in deionized water, and after 10 minutes, use absorbent paper to absorb the water stains on the surface and weigh it as m2. The water absorption rate is equal to (m2-m1) / m1.

[0011] A second objective of this invention is to provide a method for preparing a carbon-modified alumina support, comprising the following steps:

[0012] (1) Sodium hydroxide and sodium aluminate were prepared into a sodium aluminate solution, which was then added to an aluminum sulfate solution and mixed to obtain a boehmite precursor.

[0013] (2) The boehmite precursor obtained in step (1) is crystallized to obtain boehmite;

[0014] (3) The boehmite obtained in step (2) is post-treated and added to a nitrogen-containing polymer solution. After impregnation, the reaction product is calcined in a protective atmosphere to obtain the carbon-modified alumina support.

[0015] In a preferred embodiment of the present invention,

[0016] Step (1),

[0017] The concentration of aluminum ions in the sodium aluminate solution is 0.1–0.9 mol / L, preferably 0.3–0.9 mol / L; the sodium-aluminum molar ratio in the sodium aluminate solution is (2–6):1, preferably (2–5):1;

[0018] The method of addition is dropwise addition;

[0019] The concentration of the aluminum sulfate solution is 0.1–0.9 mol / L, preferably 0.3–0.6 mol / L;

[0020] The amount of sodium aluminate solution added is until the pH value is 8-11;

[0021] The mixing temperature is 10–35℃, the mixing time is 10–60 min, and the mixing method is stirring. Preferably, the stirring speed is 200–800 rpm.

[0022] In a preferred embodiment of the present invention,

[0023] Step (2),

[0024] The crystallization temperature is 50–120℃, preferably 70–120℃;

[0025] The crystallization time is 2–24 hours; preferably 5–20 hours.

[0026] The crystallization is preferably carried out using hydrothermal crystallization.

[0027] In a preferred embodiment of the present invention,

[0028] Step (3),

[0029] The post-processing includes filtration, washing, and drying; filtration can be performed using existing general methods, such as vacuum filtration; washing can be performed using existing general methods, such as washing with deionized water 3 to 5 times; drying can be performed using existing general methods, such as drying in an oven, preferably with a drying temperature of 100 to 140°C and a drying time of 2 to 8 hours.

[0030] The nitrogen-containing polymer is at least one of polyvinylimidazolium, polyvinylpyrrolidone, and polyvinylpyridine;

[0031] The solvent in the nitrogen-containing polymer solution is at least one of methanol and ethanol;

[0032] The mass ratio of the boehmite to the nitrogen-containing polymer is (1-100):1, preferably (5-100):1, and more preferably (10-100):1;

[0033] The reaction temperature is 80–150℃, preferably 100–120℃;

[0034] The reaction time is 4 to 10 hours, preferably 5 to 10 hours;

[0035] The concentration of the nitrogen-containing polymer solution is 0.1–2 wt%, preferably 0.6–1.8 wt%.

[0036] The protective gas is nitrogen or an inert gas;

[0037] The immersion temperature is 10–35℃, and the immersion time is 0.5–2 hours.

[0038] The roasting temperature is 400-600℃, and the roasting time is 3-10h.

[0039] A third objective of this invention is to provide a carbon-modified alumina support obtained by the above preparation method.

[0040] A fourth objective of this invention is to provide a catalyst comprising a carbon-modified alumina support, wherein the catalyst further comprises an active component, and preferably an auxiliary component; more preferably,

[0041] The active component includes Cu;

[0042] The auxiliary component is at least one selected from Zn, Mg, Ni, Co, Mn, and Co.

[0043] More preferably,

[0044] With a total catalyst mass of 100%, the catalyst comprises:

[0045] The carbon-modified alumina support comprises 30-90%; preferably 55-70%.

[0046] The active ingredient comprises 10-60%; preferably 25-40%.

[0047] The auxiliary component comprises 0-10%; preferably 0-6%.

[0048] The fifth objective of this invention is to provide a method for preparing a catalyst supported on carbon-modified alumina, comprising:

[0049] The carbon-modified alumina support is contacted with a solution or mixture containing active components, preferably the solution or mixture also containing auxiliary components. After contact, the carbon-modified alumina support is removed and then subjected to a second calcination under a protective gas atmosphere to obtain the catalyst of the carbon-modified alumina support.

[0050] In a preferred embodiment of the present invention,

[0051] The mixture containing the active component is a mixture of a solution containing the active component and a solution containing the auxiliary component; more preferably, the water-soluble salt of the active component in the solution containing the active component has a mass percentage of 30-60 wt%; the water-soluble salt of the auxiliary component in the solution containing the auxiliary component has a mass percentage of 1-8 wt%, preferably 4-6 wt%.

[0052] The temperature at which the solution or mixture containing the active component contacts the carbon-modified alumina support is 15–40°C and the time is 10–60 min.

[0053] The solution or mixture containing the active component comes into contact with the carbon-modified alumina carrier by at least one of impregnation or spraying.

[0054] The carbon-modified alumina support is contacted with a solution or mixture containing active components, and the product is then subjected to a second drying followed by a second calcination; preferably, the temperature of the second drying is 100-130°C and the time is 8-15 hours.

[0055] The protective gas is at least one of nitrogen and an inert gas; the inert gas is preferably at least one of argon and helium.

[0056] The second roasting temperature is 400-800℃, and the time is 2-10h.

[0057] The sixth objective of this invention is to provide a catalyst obtained by the above preparation method.

[0058] The seventh objective of this invention is to provide a method for deep removal of trace amounts of CO, comprising:

[0059] The CO-containing material is brought into contact with the catalyst to react and remove CO.

[0060] In a preferred embodiment of the present invention,

[0061] The CO content in the CO-containing material is 0.01 ppm to 200 ppm, preferably 0.01 to 100 ppm, more preferably 0.01 to 10 ppm, and most preferably 0.1 to 5 ppm;

[0062] The reaction temperature is 0–150℃, preferably 20–120℃;

[0063] The reaction pressure is 0.1–5 MPa, preferably 0.1–3 MPa;

[0064] The volume hourly space velocity (VHSV) for gas-phase reactions is 1000–10000 h⁻¹ -1 ;

[0065] The volume hourly space velocity (VHSV) for liquid-phase reactions is 1–150 h⁻¹.-1 .

[0066] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0067] (1) The catalyst supported on carbon-modified alumina with a large specific surface area has a higher surface area, higher water absorption rate, larger adsorption of metals, and higher loading.

[0068] (2) The catalyst prepared by the impregnation method has higher metal dispersion and higher reaction activity, and can remove CO at a lower reaction temperature.

[0069] (3) Carbon-modified supports can change the acidity or alkalinity of the catalyst surface, resulting in high catalyst stability. Detailed Implementation

[0070] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are only used to further illustrate the present invention and should not be construed as limiting the scope of protection of the present invention. Some non-essential improvements and adjustments made by those skilled in the art based on the content of the present invention are still within the scope of protection of the present invention.

[0071] All raw materials used in the examples are commercially available.

[0072] Test method:

[0073] Measurement of water absorption rate: Weigh a fixed mass of alumina carrier m1, place it in deionized water, and after 10 minutes, use absorbent paper to absorb the water stains on the surface and weigh it as m2. The water absorption rate is equal to (m2-m1) / m1.

[0074] The method for testing metal content was as follows: X-ray fluorescence spectroscopy (XRF) was performed using an X-ray photoelectron spectrometer from PA Nalytical BV, Netherlands. The elemental composition and relative content of the sample surface were analyzed after vacuuming.

[0075] Example 1

[0076] (1) Weigh 22.56g NaOH and 17.5g sodium aluminate and dissolve them in 250ml deionized water to prepare a sodium aluminate solution. Weigh 88.4g aluminum sulfate and dissolve it in 500ml deionized water to prepare an aluminum sulfate solution. Add the prepared sodium aluminate solution dropwise to the prepared aluminum sulfate solution until the pH is 9.0. Stir at room temperature for 30min at a stirring speed of 600 rpm to obtain boehmite precursor.

[0077] (2) The obtained boehmite precursor was crystallized at 120℃ for 20h to obtain boehmite with a large specific surface area.

[0078] (3) The obtained boehmite with a large specific surface area was filtered with deionized water at room temperature and washed five times with deionized water. After drying in an oven at 120°C for 6 hours, dry boehmite with a large specific surface area was obtained. 100g of the obtained boehmite was immersed in 100g of an ethanol solution of 1wt% polyvinyl imidazole (containing 1g of polyvinyl imidazole) at room temperature for 0.5 hours. Then, it was transferred to a hydrothermal reactor and reacted at 100°C for 10 hours. After cooling and filtration, it was dried at 80°C for 4 hours and then calcined at 400°C for 10 hours under a nitrogen atmosphere to obtain a carbon-modified alumina support. The specific surface area of ​​the alumina support was 448m². 2 / g, pore volume 2.45cm³ 3 / g, and its water absorption capacity was tested to be 150%.

[0079] (4) 20g of support was placed in a 43wt% copper nitrate aqueous solution (the amount of copper nitrate used was 9.9g based on the metal element copper) for an equal volume impregnation. After impregnation at room temperature for 20min, the support was removed, drained, dried at 120℃ for 12h, and calcined at 400℃ for 3h in a nitrogen atmosphere to obtain the catalyst. The copper loading in the catalyst was 33wt% as characterized by XRF.

[0080] Example 2

[0081] (1) Dissolve NaOH and sodium aluminate in deionized water to prepare a 0.4 mol / L sodium aluminate solution with a sodium-aluminum molar ratio of 5:1. Dissolve aluminum sulfate in deionized water to prepare a 0.4 mol / L aluminum sulfate solution. Add the prepared 0.4 mol / L sodium aluminate solution dropwise to the prepared 0.4 mol / L aluminum sulfate solution until the pH reaches 10. Stir at room temperature for 50 min at a stirring speed of 400 rpm to obtain boehmite precursor.

[0082] (2) The obtained boehmite precursor was crystallized at 80℃ for 8h to obtain boehmite with a large specific surface area.

[0083] (3) The obtained boehmite with a large specific surface area was filtered with deionized water at room temperature and washed five times with deionized water. After drying in an oven at 120°C for 6 hours, a dry boehmite with a large specific surface area was obtained. 100g of the obtained boehmite was immersed in 625g of an ethanol solution of 1.6wt% polyvinyl imidazole (containing 10g of polyvinyl imidazole) at room temperature for 1 hour. Then, it was transferred to a hydrothermal reactor and reacted at 120°C for 6 hours. After cooling and filtration, it was dried at 80°C for 4 hours and then calcined at 600°C for 4 hours under a nitrogen atmosphere to obtain a carbon-modified alumina support. The specific surface area of ​​the alumina support was 469m². 2 / g, pore volume 2.51cm 3 / g, and its water absorption capacity was tested to be 152%.

[0084] (4) 20g of the support was placed in a 56wt% copper nitrate aqueous solution (the amount of copper nitrate, calculated as copper metal, was 12.8g) and impregnated by an equal volume. After impregnation for 40min at room temperature, the support was removed, drained, dried at 120℃ for 12h, and calcined at 700℃ for 8h in a nitrogen atmosphere to obtain the catalyst.

[0085] XRF characterization showed that the copper loading in the catalyst was 39 wt%.

[0086] Example 3

[0087] Steps (1) to (3) are the same as in Example 1.

[0088] (4) 20 g of the support was placed in a mixed solution consisting of 51 wt% copper nitrate aqueous solution and 5 wt% magnesium nitrate solution (where the amount of copper nitrate, calculated as elemental copper, was 10.7 g, and the amount of magnesium nitrate, calculated as elemental magnesium, was 1.8 g). After immersion at room temperature for 20 min, the support was removed, drained, dried at 120 °C for 12 h, and calcined at 400 °C for 3 h in a nitrogen atmosphere to obtain the catalyst. XRF characterization showed that the copper loading in the catalyst was 33 wt% and the magnesium loading was 5.5 wt%.

[0089] Example 4

[0090] The difference from Example 3 is that the mixed solution is a 54 wt% copper nitrate aqueous solution (of which the amount of copper nitrate, calculated as the metallic element copper, is 11.0 g) and a 5 wt% zinc nitrate aqueous solution (of which the amount of zinc nitrate, calculated as the metallic element zinc, is 1.3 g).

[0091] Apart from the differences mentioned above, all other conditions in Example 4 were the same as in Example 3, and a catalyst was obtained.

[0092] XRF characterization showed that the catalyst contained 34 wt% copper and 4.0 wt% zinc.

[0093] Comparative Example 1

[0094] The difference from Example 1 is that commercially available alumina is used as the carrier instead of the modified alumina carrier;

[0095] The specific surface area of ​​commercially available alumina carriers is 236 m². 2 / g, pore volume 1.0cm 3 / g;

[0096] Apart from the differences mentioned above, all other conditions in Comparative Example 1 were the same as in Example 1, and a catalyst was obtained.

[0097] XRF characterization showed that the copper loading in the catalyst was 33 wt%.

[0098] Comparative Example 2

[0099] The difference from Example 3 is that commercially available alumina is used as the carrier instead of the modified alumina carrier;

[0100] The specific surface area of ​​commercially available alumina carriers is 236 m². 2 / g, pore volume 1.0cm 3 / g;

[0101] Apart from the differences mentioned above, all other conditions in Comparative Example 2 were the same as in Example 3, and a catalyst was obtained.

[0102] XRF characterization showed that the catalyst contained 25 wt% copper and 5.5 wt% magnesium.

[0103] Comparative Example 3

[0104] The difference from Example 4 is that commercially available alumina is used as the carrier instead of the modified alumina carrier;

[0105] The specific surface area of ​​commercially available alumina carriers is 236 m². 2 / g, pore volume 1.0cm 3 / g;

[0106] Apart from the differences mentioned above, all other conditions in Comparative Example 3 were the same as in Example 4, and a catalyst was obtained.

[0107] XRF characterization showed that the catalyst contained 25 wt% copper and 4 wt% zinc.

[0108] The catalysts prepared in Examples 1-4 and Comparative Examples 1-3 were used to conduct carbon monoxide removal tests and continuous reaction tests, as detailed below:

[0109] Carbon monoxide removal test:

[0110] The catalyst was evaluated 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 h.

[0111] The material was a mixed gas containing 2.2 ppm CO, the reaction pressure was 3.5 MPa, the reaction temperature was 50℃ and 90℃, and the space velocity was 3000 hr. -1 4500hr -1 10000hr -1 .

[0112] Raw materials and products were detected using an Agilent 7890 gas chromatograph with a nickel methanation converter, thermal conductivity detector, and flame hydrogen detector, with a limit of detection of 0.1 ppm for carbon monoxide, and an AMETEK trace carbon monoxide analyzer with a limit of detection of 1 ppb for carbon monoxide.

[0113] After the reaction stabilized for about 10 to 20 hours, the test data were collected and are listed in Tables 1 and 2.

[0114] Continuous reaction test:

[0115] The large specific surface area alumina supported catalyst from Example 1 was used in a reaction at a pressure of 3.5 MPa, a temperature of 90 °C, and a space velocity of 3000 hr. -1 The reaction was carried out continuously for 200 hours.

[0116] Raw materials and products were detected using an Agilent 7890 gas chromatograph with a nickel methanation converter, thermal conductivity detector, and flame hydrogen detector, with a limit of detection of 0.1 ppm for carbon monoxide, and an AMETEK trace carbon monoxide analyzer with a limit of detection of 1 ppb for carbon monoxide.

[0117] The test data is listed in Table 3.

[0118] Table 1

[0119]

[0120] Table 2

[0121]

[0122] Table 3

[0123]

[0124] Comparative Examples 1-3 used commercially available alumina supports to prepare catalysts. The specific surface area of ​​the commercially available alumina supports was small (236 m²). 2 / g), with low water absorption, and with low copper content under the same catalyst preparation conditions as in Examples 1, 3, and 4, the ability of Examples 1 to 4 and Comparative Example 1 to deeply remove trace amounts of CO was tested, and the test data are listed in Tables 1 to 3.

[0125] Table 1 shows that at 90℃ for 3000 hours... -1 4500hr -1 10000hr -1 hour:

[0126] The outlet CO concentrations in Example 1 were 18 ppb, 17 ppb, and 20 ppb, while the outlet CO concentrations in Comparative Example 1 were 50 ppb, 52 ppb, and 89 ppb.

[0127] The outlet CO concentrations in Example 3 were 17 ppb, 13 ppb, and 13 ppb, while the outlet CO concentrations in Comparative Example 2 were 53 ppb, 51 ppb, and 78 ppb.

[0128] The outlet CO concentrations in Example 4 were 13 ppb, 13 ppb, and 15 ppb, while the outlet CO concentrations in Comparative Example 3 were 36 ppb, 45 ppb, and 68 ppb.

[0129] Table 2 shows that at 50℃ for 3000 hours... -1 4500hr -1 10000hr -1 hour:

[0130] The outlet CO concentrations in Example 1 were 30 ppb, 45 ppb, and 65 ppb, while the outlet CO concentrations in Comparative Example 1 were 100 ppb, 120 ppb, and 180 ppb.

[0131] The outlet CO concentrations in Example 3 were 25 ppb, 36 ppb, and 47 ppb, while the outlet CO concentrations in Comparative Example 2 were 103 ppb, 131 ppb, and 140 ppb.

[0132] The outlet CO concentrations in Example 4 were 23 ppb, 34 ppb, and 45 ppb, while the outlet CO concentrations in Comparative Example 3 were 110 ppb, 145 ppb, and 168 ppb.

[0133] Comparing the above data, it can be seen that, compared with catalysts prepared using commercially available alumina supports under the same conditions, the catalyst prepared using carbon-modified alumina supports of the present invention has an improved ability to remove trace amounts of CO by about 3 to 5 times.

[0134] As can be seen from the data in Table 3 after 200 hours of continuous reaction, the catalyst prepared in this invention has good stability.

[0135] The carbon-modified alumina supports prepared in Examples 1-4 of this invention have a specific surface area of ​​448-469 m². 2 / g. Compared with the alumina supports of the prior art, the carbon-modified alumina supports prepared in Examples 1-4 have a higher external surface area, higher water absorption rate, larger adsorption metal amount, and higher loading capacity. Therefore, the catalysts prepared by the impregnation method have higher metal dispersion, higher reactivity, and better stability.

Claims

1. A carbon-modified alumina support, wherein the specific surface area of ​​the alumina support is ≥300 m². 2 / g; pore volume is 1.0~3.5cm 3 / g; water absorption rate 110~160%; the alumina carrier is prepared by a method including the following steps: (1) Prepare a sodium aluminate solution by mixing sodium hydroxide and sodium aluminate, add it to an aluminum sulfate solution, and then mix to obtain a boehmite precursor; (2) The boehmite precursor obtained in step (1) is crystallized to obtain boehmite; (3) The boehmite obtained in step (2) is post-treated and added to a nitrogen-containing polymer solution. After impregnation, the reaction product is calcined in a protective atmosphere to obtain the carbon-modified alumina support. The calcination temperature is 400~600℃. The nitrogen-containing polymer is at least one of polyvinylimidazolium, polyvinylpyrrolidone, and polyvinylpyridine. The mass ratio of boehmite to nitrogen-containing polymer is (1~100):

1.

2. The carbon-modified alumina support as described in claim 1, wherein the specific surface area of ​​the alumina support is 320~550 m². 2 / g; pore volume is 1.5~3.0 cm³ 3 / g.

3. The carbon-modified alumina support as described in claim 2, wherein the specific surface area of ​​the alumina support is 400~480 m². 2 / g.

4. A method for preparing a carbon-modified alumina support as described in any one of claims 1 to 3, comprising the following steps: (1) Prepare a sodium aluminate solution by mixing sodium hydroxide and sodium aluminate, add it to an aluminum sulfate solution, and then mix to obtain a boehmite precursor; (2) The boehmite precursor obtained in step (1) is crystallized to obtain boehmite; (3) The boehmite obtained in step (2) is post-treated and added to a nitrogen-containing polymer solution. After impregnation, the reaction product is calcined in a protective atmosphere to obtain the carbon-modified alumina support.

5. The method for preparing the carbon-modified alumina support as described in claim 4, characterized in that: Step (1), The concentration of aluminum ions in the sodium aluminate solution is 0.1~0.9 mol / L; and / or, The sodium-aluminate molar ratio in the sodium aluminate solution is (2~6):1; and / or, The method of addition is dropwise addition; and / or, The concentration of the aluminum sulfate solution is 0.1~0.9 mol / L; and / or, The amount of sodium aluminate solution added is until the pH value is 8-11; and / or, The mixing temperature is 10~35℃, the mixing time is 10~60min, and the mixing method is stirring.

6. The method for preparing the carbon-modified alumina support as described in claim 5, characterized in that: Step (1), The concentration of aluminum ions in the sodium aluminate solution is 0.3~0.9 mol / L; and / or, The sodium-aluminate molar ratio in the sodium aluminate solution is (2~5):1; and / or, The concentration of the aluminum sulfate solution is 0.3~0.6 mol / L; and / or, The mixing speed is 200-800 rpm.

7. The method for preparing the carbon-modified alumina support as described in claim 4, characterized in that: Step (2), The crystallization temperature is 50~120℃; and / or, The crystallization time is 2~24h.

8. The method for preparing the carbon-modified alumina support as described in claim 7, characterized in that: Step (2), The crystallization temperature is 70~120℃; and / or, The crystallization time is 5~20h.

9. The method for preparing the carbon-modified alumina support as described in claim 4, characterized in that: Step (3), The post-processing methods include filtration, washing, drying; and / or, The nitrogen-containing polymer is at least one of polyvinylimidazolium, polyvinylpyrrolidone, and polyvinylpyridine; and / or The solvent in the nitrogen-containing polymer solution is at least one of methanol and ethanol; and / or, The mass ratio of the boehmite to the nitrogen-containing polymer is (1~100):1; and / or, The reaction temperature is 80~150℃; and / or, The reaction time is 4-10 hours; and / or, The concentration of the nitrogen-containing polymer solution is 0.1~2 wt%; and / or, The protective gas is nitrogen or an inert gas; and / or, The impregnation temperature is 10~35℃, and the impregnation time is 0.5~2h; and / or, The roasting temperature is 400~600℃ and the roasting time is 3~10h.

10. The method for preparing the carbon-modified alumina support as described in claim 4, characterized in that: Step (3), The mass ratio of the boehmite to the nitrogen-containing polymer is (5~100):1; and / or, The reaction temperature is 100~120℃; and / or, The reaction time is 5-10 hours; and / or, The concentration of the nitrogen-containing polymer solution is 0.6~1.8 wt%.

11. The method for preparing the carbon-modified alumina support as described in claim 10, characterized in that: Step (3), The mass ratio of the boehmite to the nitrogen-containing polymer is (10~100):

1.

12. A carbon-modified alumina support obtained by the preparation method according to any one of claims 4 to 11.

13. A catalyst comprising the carbon-modified alumina support as described in any one of claims 1 to 3 and 12, wherein the catalyst further comprises an active component.

14. The catalyst according to claim 13, characterized in that: The active component includes Cu.

15. The catalyst according to claim 14, characterized in that: With a total catalyst mass of 100%, the catalyst comprises: Carbon-modified alumina carrier: 30-90%; Active ingredient 10~60%.

16. The catalyst according to claim 15, characterized in that: With a total catalyst mass of 100%, the catalyst comprises: Carbon-modified alumina carrier: 55-70%; Active ingredient 25-40%.

17. A method for preparing a catalyst according to any one of claims 13 to 16, comprising: The carbon-modified alumina support is contacted with a solution or mixture containing active components. After contact, the carbon-modified alumina support is removed and then subjected to a second calcination under a protective gas atmosphere to obtain the catalyst of the carbon-modified alumina support.

18. The method for preparing the catalyst according to claim 17, characterized in that: The solution or mixture also includes auxiliary components.

19. The method for preparing the catalyst according to claim 18, characterized in that: The mixture containing the active component is a mixture of a solution containing the active component and a solution containing the auxiliary component; and / or, The contact temperature between the solution or mixture containing the active component and the carbon-modified alumina support is 15-40°C, and the contact time is 10-60 min; and / or, The solution or mixture containing the active component contacts the carbon-modified alumina support by at least one of impregnation or spraying; and / or, The carbon-modified alumina support is contacted with a solution or mixture containing active components, and the product is then subjected to a second drying followed by a second calcination. And / or, The protective gas is at least one of nitrogen and an inert gas; and / or, The second roasting temperature is 400~800℃, and the time is 2~10h.

20. The method for preparing the catalyst according to claim 19, characterized in that: The solution containing the active component has a water-soluble salt content of 30-60 wt%; the solution containing the auxiliary component has a water-soluble salt content of 1-8 wt%; and / or, The second drying temperature is 100~130℃, and the time is 8~15h; and / or, The inert gas is at least one of argon and helium.

21. The method for preparing the catalyst according to claim 20, characterized in that: The mass percentage of water-soluble salts of the auxiliary component in the solution containing the auxiliary component is 4-6 wt%.

22. A catalyst obtained by the preparation method according to any one of claims 17 to 21.

23. A method for deep removal of trace amounts of CO, comprising: The CO-containing material is reacted with the catalyst described in any one of claims 13-16 and 22 to remove CO.

24. The method for deep removal of trace amounts of CO as described in claim 23, characterized in that: The CO content in the CO-containing material is 0.01 ppm to 200 ppm; and / or, The reaction temperature is 0~150℃; and / or, The reaction pressure is 0.1~5 MPa; and / or, The volume hourly space velocity (VHSV) for gas-phase reactions is 1000–10000 h⁻¹. -1 ; and / or, The volume hourly space velocity (VHSV) for liquid-phase reactions is 1–150 h⁻¹. -1 .

25. The method for deep removal of trace amounts of CO as described in claim 24, characterized in that: The CO content in the CO-containing material is 0.01~100ppm; and / or, The reaction temperature is 20~120℃; and / or, The reaction pressure is 0.1~3MPa.

26. The method for deep removal of trace amounts of CO as described in claim 25, characterized in that: The CO content in the CO-containing material is 0.01~10ppm.

27. The method for deep removal of trace amounts of CO as described in claim 26, characterized in that: The CO content in the CO-containing material is 0.1~5 ppm.

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