Adsorbent for efficient removal of trace co and preparation and application thereof

Abstract

The present application relates to a kind of micro CO efficient removal adsorbent and its preparation and application, the preparation method includes the following steps: (1) active carbon powder, active component A, inorganic clay and dispersing agent are placed in ball mill and are uniformly ground, and mixture material is obtained;(2) active component B and the water solution of reducing agent are atomized and sprayed into the mixture material, then glue is added, and wet material is obtained;(3) wet material is extruded into shape by template, after heat reduction, after drying, calcination, CO removal adsorbent is obtained, i.e. target product;Active component A is monovalent copper salt, and active component B is the mixture of lanthanum chloride and at least one of cerium chloride or yttrium chloride.The strength and adsorption capacity of the CO removal adsorbent of the present application are increased by more than 30% and 25% respectively, the strength is ≥40N / cm, the wear is ≤1.5wt%, the CO adsorption capacity is ≥35ml / g (40℃), the removal precision can reach below 0.01ppm, suitable for the efficient purification of trace CO in hydrogen, nitrogen and other raw gas.

Description

Technical Field

[0001] This invention belongs to the field of adsorbent preparation technology, and relates to a high-efficiency adsorbent for the removal of trace amounts of CO, its preparation and application. Background Technology

[0002] Hydrogen and nitrogen, commonly used raw materials in chemical production, typically contain trace amounts of CO. The presence of this CO not only severely affects the activity of downstream catalysts but also poses a significant environmental hazard, thus requiring purification and removal. Currently, commonly used purification methods include pressure swing adsorption (PSA) and temperature swing adsorption (PST), with Cu-supported adsorbents being the most frequently used. + Molecular sieves or Cu-supported + Activated carbon. Compared to molecular sieve-based adsorbents, activated carbon-based adsorbents have a higher CO adsorption capacity and more thorough regeneration and desorption, making them more suitable for industrial applications.

[0003] Literature Cu + - The preparation and CO adsorption performance of activated carbon adsorbents were reported. A CO removal adsorbent was prepared by loading CuCl2 onto an activated carbon support using an impregnation method, followed by reduction with a reducing gas. Patent CN1050403A reported an adsorbent for separating carbon monoxide and ethylene using pressure swing adsorption. This patent describes a process where, under vacuum or air atmosphere conditions, the activated carbon support is first impregnated in a CuCl2 solution, followed by dehydration and reduction with ammonia or an inert ammonia gas at 150-300℃, and then cooled under inert gas protection to obtain the CuCl / activated carbon adsorbent. Patent CN1085114C reports a catalyst for purifying carbon monoxide in nitrogen-containing gas and its application. The patent first impregnates activated carbon powder in a mixed solution of copper chloride and rare earth chloride. After separation, washing, and drying, activated carbon powder loaded with copper chloride and rare earth chloride is obtained. Then, the activated carbon powder loaded with copper chloride and rare earth chloride is mixed with attapulgite, extruded and calcined in a nitrogen atmosphere to obtain an adsorbent intermediate. Finally, the adsorbent intermediate is reduced in a reducing atmosphere containing hydrogen or carbon monoxide at 140-300℃ to obtain a CO removal adsorbent.

[0004] Although the aforementioned patents and literature have reported CO removal adsorbents and their preparation methods, these methods still have many problems and shortcomings. Firstly, all of these preparation methods involve a reducing gas process to thermally reduce the adsorbent. This thermal reduction process places high demands on the equipment, is complex to operate, consumes a lot of energy, and poses safety hazards. Secondly, the CO removal adsorbent preparation methods reported in the patents and literature all employ impregnation methods, and the Cu raw materials used are mostly soluble copper salts. When insoluble copper salts are used as raw materials, the dissolution process requires a large amount of hydrochloric acid and auxiliary heating, making the operation extremely inconvenient. When granular activated carbon is used as a carrier to impregnate and load the active components, there are problems such as low active component loading and uneven active component loading, which leads to low CO adsorption capacity and removal accuracy of the prepared CO removal adsorbent. When using powdered activated carbon as a carrier, although the impregnation process can improve the uniformity of the active component loading, the problem of low active component loading still exists. Furthermore, the separation and drying of the powder increases the complexity of the process, not only raising operating costs but also creating environmental pressure due to wastewater. In addition, the CO removal adsorbents prepared in the aforementioned patents and literature have low strength and high abrasion; during long-term repeated regeneration, severe powder loss occurs, adsorption performance decreases significantly, service life is greatly shortened, and downstream pipeline blockage occurs. Summary of the Invention

[0005] The purpose of this invention is to provide a high-efficiency adsorbent for removing trace amounts of CO, its preparation and application, which has the advantages of high strength, low wear, high CO adsorption capacity and removal accuracy.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] One of the technical solutions of the present invention provides a method for preparing a high-efficiency adsorbent for the removal of trace amounts of CO, comprising the following steps:

[0008] (1) Place activated carbon powder, active component A, inorganic clay and dispersant in a ball mill and grind and mix them evenly to obtain a mixture;

[0009] (2) Atomize and spray the aqueous solution of active component B and reducing agent into the obtained mixture, and then add glue to obtain wet material;

[0010] (3) The wet material is extruded through a template, thermally reduced, dried and calcined to obtain the CO adsorbent, which is the target product;

[0011] The active component A is a monovalent copper salt, and the active component B is a mixture of lanthanum chloride and at least one of cerium chloride or yttrium chloride.

[0012] Furthermore, in step (1), the amount of each material used, based on dry weight, is as follows: 50-80 parts of activated carbon powder, 10-30 parts of active component A, 10-30 parts of inorganic clay, and 0.1-1.0 parts of dispersant.

[0013] Furthermore, in step (1), the activated carbon powder is selected from coconut shell activated carbon, with a specific surface area ≥1000 m². 2 / g, pore volume ≥0.75cm 3 / g.

[0014] Furthermore, the inorganic clay is a mixture of kaolin, diatomaceous earth or bentonite and attapulgite, and the dry basis mass ratio of kaolin, diatomaceous earth or bentonite to attapulgite is 1:1-5.

[0015] Furthermore, the dispersant is one or a mixture of several of sodium stearate, calcium stearate, potassium stearate, etc.

[0016] Furthermore, in step (1), the active component A is one or a mixture of several of cuprous chloride, cuprous formate, cuprous acetate, cuprous sulfate, and cuprous bromide.

[0017] Furthermore, in step (2), the mass ratio of active component B to active component A is (0.1-2.0):(10-30) on a dry basis, and in active component B, cerium chloride or yttrium chloride accounts for 1-5 wt% of the mass of lanthanum chloride.

[0018] Furthermore, in step (2), the reducing agent is one or a combination of several of urea, sucrose, oxalic acid, formic acid, ammonium citrate, and sodium sulfite, and the mass ratio of the reducing agent to active component B is (0.1-5):1. Specifically, the concentration of the reducing agent in the aqueous solution is 0.1-3.0 wt%.

[0019] Furthermore, in step (2), the adhesive is a sodium pyrophosphate solution, silica sol, or sodium water glass (i.e., sodium silicate) solution, and the amount of adhesive added is such that the total moisture content of the wet material reaches 60-70%. Specifically, the concentrations of sodium pyrophosphate, silica, and sodium silicate in the adhesive are 0.1-3.0 wt%.

[0020] Furthermore, in step (2), the heat reduction process is as follows: the wet strip extruded through the template is heated to 50-100℃ in a sealed environment and kept at that temperature for 1-12 hours.

[0021] Furthermore, the drying process is as follows: air dry at room temperature for 12-36 hours.

[0022] Furthermore, the calcination process is carried out under inert gas protection, with a calcination temperature of 250-450℃ and a calcination time of 2-8 hours.

[0023] A second technical solution of the present invention provides a high-efficiency micro-CO removal adsorbent, which is prepared by any of the preparation methods described above. This adsorbent possesses high crushing strength and low abrasion loss, with crushing strength increased by more than 30% and abrasion loss reduced by more than 50%. Specifically, the crushing strength of this CO removal adsorbent is ≥40 N / cm, and the abrasion loss is ≤1.5 wt%.

[0024] The third technical solution of this invention provides an application of a high-efficiency CO removal adsorbent for the deep removal of CO (0.3 ppm-10%) from hydrogen, nitrogen, or other nitrogen-containing feed gases. Preferably, it is used in PSA and PST processes for the efficient purification of trace amounts of CO from hydrogen, nitrogen, or other nitrogen-containing feed gases. Exemplarily, its CO adsorption capacity can be increased by more than 25% and it possesses higher removal accuracy. Specifically, the CO adsorbent has a CO adsorption capacity ≥35 ml / g (40°C) and a CO removal accuracy below 0.01 ppm.

[0025] Compared with the prior art, the present invention has the following advantages:

[0026] 1) Compared with existing activated carbon-based CO removal adsorbent preparation technologies, this invention uses a solid-phase mixing method to prepare the CO removal adsorbent, avoiding the use of large amounts of hydrochloric acid in the impregnation method, and also avoiding the operation of dissolving copper salts by heating acid solution. This allows for the preparation of CO removal adsorbents with higher active component content. The use of ball milling mixing process, the introduction of dispersant, and the combination of atomization spraying method solve the problem of mixing uniformity among activated carbon powder, active components, and inorganic clay. The uniform mixing of raw materials results in a lower intensity distribution dispersion and higher utilization rate of active components in the prepared CO removal adsorbent.

[0027] 2) Compared with existing activated carbon-based CO removal adsorbent preparation technologies, this invention adopts a method of synergistic molding of composite clay and sintering aids, which significantly improves the strength of the CO removal adsorbent and greatly reduces its wear, effectively ensuring the structural stability of the CO removal adsorbent during long-term use and avoiding powder shedding that could block downstream pipelines or equipment.

[0028] 3) Compared with existing activated carbon-based CO removal adsorbent preparation technologies, this invention introduces rare earth dichlorides, with lanthanum chloride as the main component, in addition to copper chloride salt as the main active component. The introduction of cerium chloride or yttrium chloride improves the monolayer dispersion of copper chloride salt and lanthanum chloride in the adsorbent. The improved monolayer dispersion of copper chloride salt and lanthanum chloride increases the utilization rate of the active component, thereby significantly increasing the CO adsorption capacity of the CO removal adsorbent.

[0029] 4) Compared with existing activated carbon-based CO adsorbent preparation technologies, this invention directly uses monovalent copper as a raw material, significantly reducing the use of reducing agents. Furthermore, a liquid-phase reducing agent is introduced into the material by spraying an aqueous solution; further closed-loop, low-temperature, humidified reduction can remove the small amount of Cu generated during the preparation process. 2+ Reducing to Cu + No additional reducing gas thermal reduction process or liquid phase reducing agent impregnation reduction process is required.

[0030] 5) Compared with existing activated carbon-based CO removal adsorbents, the activated carbon-based CO removal adsorbent prepared by this invention has higher crushing strength, lower wear, higher CO adsorption capacity, and higher removal accuracy. It also has a longer service life when used to purify CO from hydrogen, nitrogen, or nitrogen-containing feed gases, and is suitable for the higher hydrogen purity requirements of downstream high-end hydrogenation catalysts. Furthermore, for the same packing volume, the CO removal adsorbent prepared by this invention has a longer regeneration cycle, lower regeneration switching frequency, and lower operating costs.

[0031] 6) The preparation method of the activated carbon-based CO adsorbent proposed in this invention does not require the introduction of acid, generates no wastewater, and has a simple, safe, low-energy-consumption, and stable product performance, making it suitable and easy for industrial production. Attached Figure Description

[0032] Figure 1 The XRD pattern of the CO removal adsorbent prepared in Example 1 is shown below.

[0033] Figure 2 The XRD pattern of the CO removal adsorbent prepared in Example 2 is shown below.

[0034] Figure 3 The image shows the XRD pattern of the CO removal adsorbent prepared in Example 3. Detailed Implementation

[0035] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0036] The raw materials used in the following examples were purchased from Fujian Xingsen Activated Carbon Co., Ltd., cuprous chloride from Suzhou Jinrui Environmental Protection Resources Comprehensive Utilization Co., Ltd., kaolin, attapulgite, diatomite and bentonite from Lingshou Aotai Mining Co., Ltd., sodium stearate, calcium stearate, potassium stearate, lanthanum chloride, cerium chloride, yttrium chloride, urea, sucrose, oxalic acid, formic acid, ammonium citrate and sodium sulfite from Sinopharm Chemical Reagent Co., Ltd., sucrose from Anhui Mukang Food Co., Ltd., sodium pyrophosphate from Wujiang Xincheng Fine Chemical Co., Ltd., cuprous chloride, cuprous formate, cuprous acetate, cuprous sulfate and cuprous bromide from Shanghai Zhanyun Chemical Co., Ltd., and silica sol and sodium water glass from Shanghai Silicon Edge Materials Technology Co., Ltd.

[0037] Example 1

[0038] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (Changsha Yonglekang Instrument Equipment Co., Ltd., YKT-04, grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain the mixture.

[0039] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0040] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0041] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 46.5 N / cm and its abrasion loss was 0.7 wt%. The XRD pattern is shown below. Figure 1 As shown.

[0042] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 36.8 ml / g, and the CO content at the outlet could be as low as 0.01 ppm. Compared with the commercially available CO removal adsorbent (Nanjing Huahua Chemical Co., Ltd.), the strength, wear, CO adsorption capacity, and removal accuracy of the CO removal adsorbent prepared in this example were significantly improved. The results are shown in Table 1.

[0043] Comparative Example 1

[0044] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a conical mixer (Zhengzhou Qingyuan Machinery Co., Ltd., QY-SY5, speed 30r / min, mixing time 2h), and then mixed evenly to obtain the mixture.

[0045] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0046] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0047] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 37.1 N / cm and its abrasion loss was 2.0 wt%.

[0048] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of the CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of the CO removal adsorbent was 31.9 ml / g.

[0049] It is evident that the CO removal adsorbent prepared by ball milling has higher crushing strength and greater adsorption capacity, which is because the ball milling process improves the mixing uniformity between different materials.

[0050] Example 2

[0051] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0052] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then adjust the material to a total moisture content of 60-70% with a 1.0 wt% sodium pyrophosphate solution to obtain the clay blank.

[0053] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at 80°C for 8 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 24 hours, and finally calcined at 380°C for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0054] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 45.9 N / cm and its abrasion loss was 0.8 wt%.

[0055] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 38.3 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0056] Compared with commercially available CO adsorbents (Nanjing Huahua), the CO adsorption strength, wear, CO adsorption capacity and removal accuracy prepared in this embodiment are significantly improved, as shown in Table 1.

[0057] Comparative Example 2

[0058] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0059] 2) Kneading: Transfer the evenly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts of lanthanum chloride onto the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1.0 wt% sodium pyrophosphate solution to obtain the clay blank.

[0060] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at 80°C for 8 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 24 hours, and finally calcined at 380°C for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0061] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 44.5 N / cm and its abrasion loss was 1.0 wt%.

[0062] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO adsorbent was 32.5 ml / g.

[0063] It is evident that the CO adsorbent prepared by introducing cerium chloride has a larger CO adsorption capacity. This is because cerium chloride improves the monolayer dispersion of copper chloride salt and lanthanum chloride in the adsorbent, increases the utilization rate of the active components copper chloride salt and lanthanum chloride, and thus significantly increases the CO adsorption capacity of the CO adsorbent.

[0064] Example 3

[0065] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of diatomaceous earth, 20 parts of attapulgite and 0.5 parts of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0066] 2) Kneading: Transfer the evenly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a suitable dryness and moisture content with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0067] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at 100℃ for 1 hour for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 12 hours, and finally calcined at 450℃ for 2 hours under nitrogen protection to obtain the finished CO adsorbent.

[0068] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 43.6 N / cm and its abrasion loss was 1.1 wt%. The XRD pattern is shown below. Figure 2 As shown.

[0069] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 37.1 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0070] Compared with commercially available CO adsorbents (Nanjing Huahua), the CO adsorption strength, wear, CO adsorption capacity and removal accuracy prepared in this embodiment are significantly improved, as shown in Table 1.

[0071] Comparative Example 3

[0072] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of diatomaceous earth, 20 parts of attapulgite and 0.5 parts of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0073] 2) Kneading: Transfer the well-mixed material into the drum of a high-speed mixer. While stirring at high speed, pour a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1.0 wt% sodium pyrophosphate solution to obtain the clay blank.

[0074] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at 100℃ for 1 hour for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 12 hours, and finally calcined at 450℃ for 2 hours under nitrogen protection to obtain the finished CO adsorbent.

[0075] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 39.1 N / cm and its abrasion loss was 1.8 wt%.

[0076] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 33.7 ml / g.

[0077] It is evident that the CO removal adsorbent prepared by atomized spraying has higher crushing strength and greater CO adsorption capacity. This is because atomized spraying improves the dispersion uniformity of lanthanum chloride, cerium chloride, and adhesive in the material, thereby increasing the crushing strength and CO adsorption capacity of the CO removal adsorbent.

[0078] Example 4

[0079] 1) Mixing: Weigh 80 parts of material with a specific surface area of ​​1050 m² 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 10 parts of cuprous chloride, 5 parts of kaolin, 5 parts of attapulgite and 0.8 parts of potassium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0080] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, a 3.0 wt% formic acid solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride is atomized and sprayed onto the above mixture. Then, a 1.0 wt% sodium pyrophosphate solution is used to adjust the material to a total moisture content of 60-70% to obtain the clay blank.

[0081] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 60℃ for 6 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 24 hours, and finally calcined at 300℃ for 6 hours under nitrogen protection to obtain the finished CO adsorbent.

[0082] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 42.7 N / cm and its abrasion loss was 1.3 wt%.

[0083] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 36.6 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0084] Compared with commercially available CO adsorbents (Nanjing Huahua), the CO adsorption strength, wear, CO adsorption capacity and removal accuracy prepared in this embodiment are significantly improved, as shown in Table 1.

[0085] Comparative Example 4

[0086] 1) Mixing: Weigh 80 parts of material with a specific surface area of ​​1050 m² 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 10 parts of cuprous chloride, 5 parts of kaolin and 5 parts of attapulgite are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0087] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, a 3.0 wt% formic acid solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride is atomized and sprayed onto the above mixture. Then, a 1.0 wt% sodium pyrophosphate solution is used to adjust the material to a total moisture content of 60-70% to obtain the clay blank.

[0088] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 60℃ for 6 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 24 hours, and finally calcined at 300℃ for 6 hours under nitrogen protection to obtain the finished CO adsorbent.

[0089] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 40.5 N / cm and its abrasion loss was 1.6 wt%.

[0090] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 32.8 ml / g.

[0091] It is evident that the CO adsorbent prepared by introducing a dispersant has higher crushing strength and greater CO adsorption capacity. This is because the dispersant improves the mixing uniformity between different materials, thereby increasing the crushing strength and CO adsorption capacity of the CO adsorbent.

[0092] Table 1. Comparison of CO removal adsorbents prepared in each embodiment and comparative example with commercially available similar products.

[0093]

[0094]

[0095] Example 5

[0096] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0097] 2) Kneading: Transfer the evenly mixed material into the drum of a high-speed mixer. Under high-speed stirring, a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts yttrium chloride is atomized and sprayed onto the above mixture. Then, the material is adjusted to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0098] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0099] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 47.1 N / cm and its abrasion loss was 0.6 wt%.

[0100] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 36.4 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0101] Example 6

[0102] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of bentonite, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0103] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0104] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0105] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 45.5 N / cm and its abrasion loss was 0.8 wt%.

[0106] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 37.3 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0107] Example 7

[0108] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of diatomaceous earth, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain the mixture.

[0109] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0110] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0111] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 46.4 N / cm and its abrasion loss was 0.7 wt%.

[0112] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 36.0 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0113] Example 8

[0114] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous formate, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0115] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0116] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0117] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 45.7 N / cm and its abrasion loss was 0.8 wt%.

[0118] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 37.4 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0119] Example 9

[0120] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous acetate, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0121] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0122] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0123] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 45.5 N / cm and its abrasion loss was 0.9 wt%.

[0124] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 36.9 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0125] Example 10

[0126] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous sulfate, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain the mixture.

[0127] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0128] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0129] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 46.2 N / cm and its abrasion loss was 0.7 wt%.

[0130] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 35.9 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0131] Example 11

[0132] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous bromide, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0133] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0134] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0135] Analysis of the prepared CO removal adsorbent showed that its crushing strength was 45.4 N / cm and its abrasion loss was 0.9 wt%.

[0136] Using a mixed gas with a nitrogen content of 24 wt%, a hydrogen content of 73 wt%, and a CO content of 3.0 wt% as the raw gas, the CO adsorption performance of this CO removal adsorbent was evaluated at a pressure of 0.7 MPa and a temperature of 40 °C. The results showed that the CO adsorption capacity of this CO removal adsorbent was 36.3 ml / g, and the accuracy of the outlet CO content could reach below 0.01 ppm.

[0137] Example 12

[0138] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0139] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% urea solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0140] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0141] Example 13

[0142] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0143] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray the oxalic acid solution with a concentration of 3.0 wt% containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then adjust the material to a total water content of 60-70% with a sodium pyrophosphate solution with a concentration of 1 wt% to obtain the clay blank.

[0144] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0145] Example 14

[0146] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0147] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% ammonium citrate solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0148] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0149] Example 15

[0150] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0151] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sodium sulfite solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0152] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0153] Example 16

[0154] 1) Mixing: Weigh 60 parts of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of bentonite, 10 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0155] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% silica sol solution to obtain the clay blank.

[0156] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0157] Example 17

[0158] 1) Mixing: Weigh 60 parts of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of diatomaceous earth, 10 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain the mixture.

[0159] 2) Kneading: Transfer the evenly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then adjust the material to a total water content of 60-70% with a 1 wt% sodium water glass solution to obtain the clay blank.

[0160] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0161] Example 18

[0162] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0163] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 1.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0164] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0165] Example 19

[0166] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 5 parts of kaolin, 25 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0167] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray a 3.0 wt% sucrose solution containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then, adjust the material to a total moisture content of 60-70% with a 1 wt% sodium pyrophosphate solution to obtain the clay blank.

[0168] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0169] Example 20

[0170] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 30 parts of cuprous chloride, 10 parts of kaolin, 10 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0171] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray the oxalic acid solution with a concentration of 3.0 wt% containing 2.0 parts lanthanum chloride and 0.1 parts cerium chloride into the above mixture. Then adjust the material to a total water content of 60-70% with a sodium pyrophosphate solution with a concentration of 1 wt% to obtain the clay blank.

[0172] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0173] Example 21

[0174] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0175] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray the oxalic acid solution with a concentration of 3.0 wt% containing 0.5 parts lanthanum chloride and 0.025 parts cerium chloride into the above mixture. Then adjust the material to a total moisture content of 60-70% with a sodium pyrophosphate solution with a concentration of 1 wt% to obtain the clay blank.

[0176] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0177] Example 22

[0178] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0179] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray the oxalic acid solution with a concentration of 3.0 wt% containing 2.0 parts lanthanum chloride and 0.02 parts cerium chloride into the above mixture. Then adjust the material to a total moisture content of 60-70% with a sodium pyrophosphate solution with a concentration of 1 wt% to obtain the clay blank.

[0180] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0181] Example 23

[0182] 1) Mixing: Weigh 50 portions of material with a specific surface area of ​​1000 m². 2 / g, pore volume 0.75cm 3 / g of coconut shell activated carbon powder, 20 parts of cuprous chloride, 10 parts of kaolin, 20 parts of attapulgite and 1.0 part of sodium stearate are placed in a grinding jar (grinding speed 300r / min, grinding time 60min), and then ground evenly to obtain a mixture.

[0183] 2) Kneading: Transfer the uniformly mixed material into the drum of a high-speed mixer. Under high-speed stirring, spray the oxalic acid solution with a concentration of 3.0 wt% containing 2.0 parts lanthanum chloride and 0.06 parts cerium chloride into the above mixture. Then adjust the material to a total water content of 60-70% with a sodium pyrophosphate solution with a concentration of 1 wt% to obtain the clay blank.

[0184] 3) Molding: Using a template with a pore size of 2.0 mm as the extrusion template, the above-mentioned mud blank is extruded and shaped by an extrusion machine. Then, the extruded strip is sealed in an aluminum foil bag and placed in an oven at a temperature of 50℃ for 12 hours for sealed reduction. The semi-finished strip of wet CO adsorbent after heat reduction is taken out, dried at room temperature for 36 hours, and finally calcined at 380℃ for 4 hours under nitrogen protection to obtain the finished CO adsorbent.

[0185] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a micro-amount CO efficient removal adsorbent, characterized by, The method comprises the following steps: (1) grinding and mixing active carbon powder, active component A, inorganic clay and dispersant in a ball mill to obtain a mixture; (2) spraying an aqueous solution of active component B and a reducing agent to the mixture, and then adding glue to obtain a wet material; (3) extruding the wet material into a strip through a template, and then performing thermal reduction, drying and calcination to obtain a CO removal adsorbent, i.e. the target product; The active component A is a mixture of one or more of cuprous chloride, cuprous sulfate and cuprous bromide, and the active component B is lanthanum chloride and cerium chloride; In step (1), the amounts of the materials are as follows in terms of dry weight: 50-80 parts of active carbon powder, 10-30 parts of active component A, 10-30 parts of inorganic clay and 0.1-1.0 parts of dispersant; In step (2), the mass ratio of active component B to active component A is (0.1-2.0):(10-30), and the mass fraction of cerium chloride in lanthanum chloride is 1-5 wt% in the active component B; In step (2), the reducing agent is one or a combination of urea, oxalic acid, formic acid and sodium sulfite, and the mass ratio of the reducing agent to active component B is (0.1-5):1; In step (3), the thermal reduction process is as follows: heating the wet strip extruded through the template to 50-100 ℃ in a sealed environment and keeping the temperature for 1-12 h.

2. The method for preparing a micro-amount CO efficient removal adsorbent according to claim 1, characterized in that, In step (1), the activated carbon powder is selected from coconut shell activated carbon having a specific surface area of > 1000 m 2 / g, a pore volume of > 0.75 cm 3 / g; The inorganic clay is a mixture of one of kaolin, diatomite or bentonite and attapulgite, and the dry mass ratio of the one of kaolin, diatomite or bentonite to attapulgite is 1:1-5; The dispersant is one or a mixture of several of sodium stearate, calcium stearate and potassium stearate.

3. The method of claim 1, wherein the method is characterized by: In step (2), the glue is a sodium pyrophosphate solution or a silica sol, and the amount of the glue added is such that the total water content of the wet material is 60-70%.

4. The method of claim 1, wherein the method is characterized by: In step (3), the drying process is as follows: drying at room temperature for 12-36 h; The calcination process is performed under the protection of inert gas, the calcination temperature is 250-450 ℃, and the calcination time is 2-8 h.

5. A micro-amount CO efficient removal adsorbent prepared by the preparation method of any one of claims 1-4, characterized in that, The crushing strength of the micro CO removal adsorbent is ≥40 N / cm, the abrasion is ≤1.5 wt%, and the CO adsorption capacity at 40 ℃ is ≥35 ml / g.

6. The use of a micro-adsorbent for efficient removal of CO as claimed in claim 5, wherein, The adsorbent is used for deep removal of trace CO in hydrogen, nitrogen or other raw gas containing nitrogen, and the CO removal precision is below 0.01 ppm.

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