A method for preparing a carbon monoxide removal catalyst

Abstract

The present invention develops a preparation method for a carbon monoxide removal catalyst. By subjecting vermiculite powder and cordierite powder to alkali treatment to prepare an activated base material, the treatment efficiency and durability of the carbon monoxide removal catalyst can be effectively improved, and the sensitivity to water vapor can be reduced, which is beneficial to prolonging the service life and making it suitable for various occasions.

Description

Technical Field

[0001] The present invention relates to a catalyst preparation process, in particular to a method for preparing a carbon monoxide removal catalyst. Background Art

[0002] Carbon monoxide removal catalysts can effectively convert CO into CO2 and are widely needed in waste gas treatment, air purification, gas masks and other fields.

[0003] Carbon monoxide removal catalysts encompass a variety of systems, broadly categorized into precious metal catalysts and non-precious metal catalysts. Precious metal catalysts generally include gold, platinum, palladium, and rhodium, and are characterized by high efficiency but high cost. Non-precious metal catalysts, such as copper-chromium, copper-zinc, and copper-manganese systems, suffer from poor long-term effectiveness and are sensitive to water vapor. Summary of the Invention

[0004] The present invention develops a preparation method for a carbon monoxide removal catalyst. By subjecting vermiculite powder and cordierite powder to alkali treatment to prepare an activated base material, the treatment efficiency and durability of the carbon monoxide removal catalyst can be effectively improved, and the sensitivity to water vapor can be reduced, which is beneficial to prolonging the service life and making it suitable for various occasions.

[0005] The preparation method of the carbon monoxide removal catalyst is as follows:

[0006] 1. Preparation of activated base material

[0007] (1) Grind vermiculite and cordierite to a particle size of less than 10 μm, then mix them in a mass ratio of 1-2:1-2, add them to an alkaline solution 1-1.5 times the mass of the mixed powder, and boil for 30-50 min;

[0008] (2) cooling and settling, then filtering out the mixed powder, washing it 3-5 times with purified water, and drying it to obtain a dehydrated mixed powder;

[0009] (3) dissolving TiCl4 in toluene to prepare a toluene solution with a mass fraction of 1% to 2%, adding 2-3 times the mass of the dehydrated mixed powder to the toluene solution, recovering the toluene by vacuum distillation, and then continuously introducing humid air to prepare an activated base material;

[0010] 2. Preparation of loaded base material

[0011] (4) mixing organic copper and organic manganese, and then dissolving them in 30-50 times the mass of toluene to prepare a toluene solution;

[0012] (5) adding 3-5 times the mass of the activated base material to the toluene solution obtained in step (4), and recovering the toluene by vacuum distillation to obtain the loaded base material;

[0013] 3. Preparation of Carbon Monoxide Removal Catalyst

[0014] (6) Take 60-80 parts of the loading base, 2-5 parts of kaolin, 0.5-1 part of cellulose, 5-10 parts of water, and 10-15 parts of diglycerol, mix thoroughly, and prepare a blank; the above parts are all by weight;

[0015] (7) The blank is molded into a porous block or sphere and then sintered;

[0016] (8) During sintering, the temperature is first raised to 300-350°C, kept warm for 20-30 minutes, then quickly raised to 1100-1250°C, kept warm for 1-1.5 hours, and then cooled to obtain a porous block carbon monoxide removal catalyst or a spherical carbon monoxide removal catalyst.

[0017] Furthermore, the alkaline solution in step (1) is a saturated KHCO3 solution or a saturated NaHCO3 solution.

[0018] Furthermore, the drying process in step (2) is: temperature 110-120°C.

[0019] Furthermore, the reduced pressure distillation process in step (2) or step (5) is: temperature 105-110°C, vacuum degree -0.06MPa--0.09MPa.

[0020] Furthermore, the organic copper is copper acetylacetonate or copper acetylacetate.

[0021] Furthermore, the organic manganese is manganese acetylacetonate.

[0022] Furthermore, when mixing the organic copper and organic manganese in step (4), the mass ratio of the copper element: the manganese element is controlled to be 0.5-0.6:1.

[0023] Furthermore, the cellulose in step (6) is hypromellose.

[0024] Furthermore, the kaolin particle size in step (6) is 200-400 mesh.

[0025] Furthermore, the mixing method in step (6) is as follows: cellulose is first dissolved in water, and then diglycerol, a loading base material, and kaolin are added and mixed thoroughly to obtain a blank.

[0026] Advantages of the present invention:

[0027] 1. The present invention treats vermiculite powder and cordierite powder with alkali to dissolve part of SiO2 to form active sites, and then deposits a TiO2 layer to improve the treatment efficiency of the copper-manganese system, enhance its long-lasting effect, and reduce its sensitivity to water vapor;

[0028] 2. The present invention uses a two-step temperature-raising sintering process to cause the vermiculite powder to deform and then solidify and shape, effectively improving the processing area and processing efficiency. DETAILED DESCRIPTION

[0029] Example 1

[0030] The preparation method of the carbon monoxide removal catalyst is as follows:

[0031] 1. Preparation of activated base material

[0032] (1) Vermiculite and cordierite were ground to a particle size of 3 μm, then mixed at a mass ratio of 1:1.5, added to a saturated KHCO solution (1.1 times the mass of the mixed powder), and boiled for 30 min.

[0033] (2) cooling and settling, then filtering out the mixed powder, washing it three times with purified water, and drying it at 115° C. to obtain a dehydrated mixed powder;

[0034] (3) dissolving TiCl4 in toluene to prepare a toluene solution with a mass fraction of 1.2%, adding twice the mass of the dehydrated mixed powder to the toluene solution, recovering the toluene by vacuum distillation, and then continuously introducing humid air to prepare an activated base material;

[0035] 2. Preparation of loaded base material

[0036] (4) mixing copper acetylacetonate and manganese acetylacetonate, controlling the mass ratio of copper element:manganese element to be 0.58:1, and then dissolving in 40 times the mass of toluene to prepare a toluene solution;

[0037] (5) adding 4 times the weight of the activated base material to the toluene solution obtained in step (4), and recovering the toluene by vacuum distillation to obtain the loaded base material;

[0038] 3. Preparation of Carbon Monoxide Removal Catalyst

[0039] (6) Take 65 parts of the loading base, 4 parts of kaolin with a particle size of 250 mesh, 1 part of hypromellose, 8 parts of water, and 12 parts of diglycerol. Dissolve the hypromellose in water first, then add diglycerol, loading base, and kaolin, and mix thoroughly to prepare a blank. The above parts are all parts by mass.

[0040] (7) The blank is molded into a porous block and then sintered;

[0041] (8) During sintering, the temperature was first raised to 350°C, kept at this temperature for 30 minutes, and then rapidly raised to 1200°C, kept at this temperature for 1.5 hours, and then cooled to obtain a porous block-shaped carbon monoxide removal catalyst.

[0042] The reduced pressure distillation process in step (2) or step (5) is: temperature 110° C., vacuum degree -0.06 MPa.

[0043] Comparative Example 1

[0044] TiCl4 was replaced by 10 nm TiO2 equivalent to the Ti in Example 1, and the TiO2 was first adsorbed with the same amounts of copper acetylacetonate and manganese acetylacetonate as in Example 1. Then, the same amounts of untreated vermiculite powder as in Example 1 were mixed with cordierite powder, kaolin, hydroxypropyl methylcellulose, water, and diglycerol in the same mixing method as in Example 1 to prepare a porous block carbon monoxide removal catalyst.

[0045] Comparative Example 2

[0046] Without adding TiO2, a porous block carbon monoxide removal catalyst was prepared by directly mixing equal amounts of copper acetylacetonate, manganese acetylacetonate, and unalkaline-treated vermiculite powder with cordierite powder, kaolin, hydroxypropyl methylcellulose, water, and diglycerol as in Example 1 using the same mixing method as in Example 1.

[0047] Comparative Example 3

[0048] The vermiculite powder and cordierite powder were not subjected to the alkali treatment in step (1), and the rest of the preparation method was the same as in Example 1.

[0049] Comparative Example 4

[0050] The vermiculite powder was replaced by an equal amount of cordierite powder, and the rest of the preparation method was the same as that of Example 1.

[0051] Comparative Example 5

[0052] When copper acetylacetonate and manganese acetylacetonate were mixed, the mass ratio of copper element:manganese element was controlled to be 0.4:1. The rest of the preparation method was the same as that in Example 1.

[0053] Comparative Example 6

[0054] When copper acetylacetonate and manganese acetylacetonate were mixed, the mass ratio of copper element:manganese element was controlled to be 0.7:1. The rest of the preparation method was the same as that in Example 1.

[0055] Comparative Example 7

[0056] An equal amount of 100-mesh kaolin was used to replace the 250-mesh kaolin. The rest of the preparation method was the same as that in Example 1.

[0057] Comparative Example 8

[0058] An equal amount of water was used to replace diglycerol, and the rest of the preparation method was the same as that in Example 1.

[0059] Comparative Example 9

[0060] An equal amount of glycerol was used to replace diglycerol, and the rest of the preparation method was the same as in Example 1.

[0061] Comparative Example 10

[0062] The rest of the preparation method is the same as that of Example 1. During sintering, the temperature is rapidly raised to 1200° C., kept at this temperature for 2 hours, and then cooled to obtain a porous block-shaped carbon monoxide removal catalyst.

[0063] Test method:

[0064] A porous block-shaped carbon monoxide removal catalyst of the same specifications was prepared according to the above examples and comparative examples. The catalyst was treated with the same flow rate of dry air containing 10 ppm CO at 60°C. The CO content (ppm) in the outlet air was measured in real time. The service life was defined as the end point when the CO content in the outlet air reached 0.2 ppm.

[0065] Then test with saturated humid air containing 10 ppm CO and record the service life (h).

[0066] test Dry air service life (h) Service life in humid air (h) Example 1 32.3 19.6 Comparative Example 1 14.3 2.8 Comparative Example 2 8.9 1.1 Comparative Example 3 25.1 10.5 Comparative Example 4 21.2 10.1 Comparative Example 5 22.5 12.6 Comparative Example 6 25.9 14.5 Comparative Example 7 29.4 17.2 Comparative Example 8 24.6 14.3 Comparative Example 9 29.9 17.7 Comparative Example 10 26.8 15.0

[0067] From the above test results, it can be seen that the SiO2 content in the mixed powder of vermiculite powder and cordierite powder is reduced from 46.1% to 37.5% by alkali treatment, which has a significant effect on improving the active sites.

[0068] As for the use of kaolin, the smaller the particle size, the more favorable it is for sintering. However, if the particle size is too small, it will fill the active sites obtained by the above-mentioned alkali treatment, which will have a negative impact on the processing capacity of the carbon monoxide removal catalyst.

[0069] Finally: The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing a carbon monoxide removal catalyst, characterized in that: The preparation method is specifically as follows:

1. Preparation of activated base material (1) Grind vermiculite and cordierite to a particle size of less than 10 μm, then mix them in a mass ratio of 1-2:1-2 of vermiculite powder to cordierite powder, add them to an alkaline solution 1-1.5 times the mass of the mixed powder, and boil for 30-50 minutes; (2) Cool and settle, then filter out the mixed powder, wash it with purified water 3-5 times and dry it to obtain a dehydrated mixed powder; (3) Dissolve TiCl4 in toluene to prepare a toluene solution with a mass fraction of 1%-2%, add 2-3 times the mass of the dehydrated mixed powder to the toluene solution, recover the toluene by vacuum distillation, and then continuously introduce humid air to obtain an activated base material; 2. Preparation of loaded base material (4) mixing the organic copper and the organic manganese, and then dissolving them in 30-50 times the mass of toluene to prepare a toluene solution; (5) adding 3-5 times the mass of the activated base material to the toluene solution obtained in step (4), and recovering the toluene by vacuum distillation to obtain the loaded base material; 3. Preparation of Carbon Monoxide Removal Catalyst (6) Take 60-80 parts of the loading base material, 2-5 parts of kaolin, 0.5-1 part of cellulose, 5-10 parts of water, and 10-15 parts of diglycerol, mix thoroughly, and prepare a blank; The above parts are all parts by mass; (7) The blank is molded into a porous block or sphere through a mold and then sintered; (8) During sintering, the temperature is first raised to 300-350°C, kept at this temperature for 20-30 minutes, then quickly raised to 1100-1250°C, kept at this temperature for 1-1.5 hours, and then cooled to obtain a porous block carbon monoxide removal catalyst or a spherical carbon monoxide removal catalyst.

2. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: The alkaline solution in step (1) is a saturated KHCO3 solution or a saturated NaHCO3 solution.

3. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: The drying process in step (2) is: temperature 110-120°C.

4. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: The reduced pressure distillation process in step (5) is as follows: temperature 105-110°C, vacuum degree -0.06MPa--0.09MPa.

5. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: The organic copper is copper acetylacetonate or copper acetylacetate.

6. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: The organic manganese is manganese acetylacetonate.

7. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: When mixing the organic copper and organic manganese in step (4), the mass ratio of copper element:manganese element is controlled to be 0.5-0.6:

1.

8. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: The cellulose described in step (6) is hypromellose.

9. The method for preparing the carbon monoxide removal catalyst according to claim 1, wherein: The particle size of the kaolin in step (6) is 200-400 mesh.

10. The method for preparing the carbon monoxide removal catalyst according to claim 1, characterized in that: The mixing method described in step (6) is as follows: cellulose is first dissolved in water, and then diglycerol, a loading base material, and kaolin are added and mixed thoroughly to obtain a blank.