Low temperature sulfur tolerant co tail gas treatment using a temperature rise catalyst

Abstract

The application provides a low-temperature sulfur-resistant CO tail gas treatment utilization temperature-rising catalyst, which comprises a catalyst carrier and a catalyst coating, wherein the catalyst coating comprises X i ZrOSO 4a Sn b Zr m -nAl2O3, i:a:b:m:n=(1-5):(25-35):(10-20):(13-18):(45-55), a rare earth additive, Pd, Pt, a precipitator, a binder and cellulose, X i ZrOSO 4a Sn b Zr m -nAl2O3, and the oxide content of the -nAl2O3 is 25-40%, X i ZrOSO 4a Sn b Zr m -nAl2O3, and the specific surface area of the -nAl2O3 is greater than or equal to 140 m 2 / g, and the pore volume is greater than or equal to 0.7 ml / g; the design of high specific surface area and high pore volume makes the catalyst have higher reaction activity and better adsorption, and the catalyst can more effectively treat the sulfur-containing CO tail gas. The catalyst has excellent low-temperature sulfur resistance, can effectively treat the sulfur-containing CO tail gas in a low-temperature environment, helps to reduce environmental pollution, and also has high-temperature hydrothermal resistance.

Description

Technical Field

[0001] This invention relates to a temperature-rising catalyst for tail gas treatment, and more specifically to a low-temperature sulfur-resistant CO tail gas treatment catalyst for temperature-rising catalyst. Background Technology

[0002] With rapid industrialization, emissions from industries such as steel smelting have become increasingly serious, placing enormous pressure on the environment and resources. The treatment and utilization of CO exhaust gas is particularly crucial in heavy industries like steel. This field is unique in that it requires achieving high catalyst activity under low-temperature, high-sulfur conditions while simultaneously reducing energy consumption to meet national energy and environmental protection requirements.

[0003] In existing technologies, CO tail gas treatment typically involves recovering and utilizing the gas through catalytic oxidation, generating heat to provide a heat source for the denitrification process. This method is mainly used for treating industrial tail gas emissions such as those from steel smelting, exhibiting good low-temperature sulfur resistance below 230°C. However, existing technologies for treating CO tail gas require raising the catalyst temperature to above 250°C using electric or gas heating methods to achieve effective treatment and provide a heat source for denitrification. This method has the following problems:

[0004] (1) High energy consumption: Heating the catalyst requires a large amount of electrical energy and gas resources, resulting in high energy consumption throughout the process;

[0005] (2) Poor sulfur resistance of catalyst: Under high temperature conditions, the existing catalyst has poor sulfur resistance and is easily deactivated, which affects the effect of the entire treatment process.

[0006] (3) High operating costs: Due to the poor sulfur resistance of the catalyst, it needs to be replaced frequently, resulting in high operating costs.

[0007] Currently, there are no effective solutions to these problems using existing technologies. Large-scale steel and other smelting plants in China have large equipment volumes and consume significant amounts of electricity and natural gas. Using existing technologies to treat CO exhaust gas is not only energy-intensive but also detrimental to the country's efforts to address energy shortages. Furthermore, existing technologies cannot meet the country's requirements for carbon emission recovery and utilization.

[0008] In summary, there is an urgent need to study a low-temperature sulfur-resistant CO tail gas treatment catalyst that utilizes temperature rise. Summary of the Invention

[0009] To address the problems of high energy consumption, poor sulfur resistance of catalysts, and high operating costs in existing technologies, this invention provides a low-temperature sulfur-resistant CO tail gas treatment method utilizing a temperature-rise catalyst, as detailed below:

[0010] A low-temperature sulfur-resistant CO tail gas treatment catalyst, the catalyst comprising a catalyst support and a catalyst coating, the catalyst coating comprising X i ZrOSO 4a Sn b Zr m -nAl2O3, i:a:b:m:n=(1~5):(25~35):(10~20):(13~18):(45~55), rare earth additives, Pd, Pt, precipitants, binders and cellulose, X i ZrOSO 4a Sn b Zr m The oxide content of -nAl2O3 is 25-40%.

[0011] Furthermore, X i ZrOSO 4a Sn b Zr m The specific surface area of ​​-nAl2O3 is ≥140m². 2 / g, pore volume ≥0.7ml / g.

[0012] Furthermore, the mass percentages of each component in the catalyst coating are shown below:

[0013] X i ZrOSO 4a Sn b Zr m -nAl2O3 80~90%;

[0014] Rare earth additives 1-3%;

[0015] Pt 0.1-1%;

[0016] Pd 0.1–0.5%;

[0017] Precipitant 5-10%;

[0018] Adhesive 10-15%;

[0019] Cellulose 0.1-0.5%.

[0020] Furthermore, X can be any one of La, Ce, or Y.

[0021] Furthermore, the precipitant is Ce-Zr composite alumina, and the rare earth additive is one or a mixture of several of La, Ce, or Y.

[0022] Furthermore, the preparation method includes the following steps:

[0023] S1: Weigh the materials according to their mass percentage;

[0024] S2: Weigh out the Pt solution and dilute it. Weigh out the rare earth additive and add it to the Pt solution. After it is completely dissolved, take 1 / 5 of the amount and add it to the bucket. Weigh out the Pd solution and dilute it. Weigh out the additive and add it to the Pd solution. After it is completely dissolved, add it to the bucket. Stir well and then add the remaining Pt solution.

[0025] S3: Add precipitant and stir, then add binder;

[0026] S4: Finally, add cellulose and stir until the appropriate viscosity is achieved;

[0027] S5: Coating is performed on the catalyst support.

[0028] Beneficial effects:

[0029] This invention provides a low-temperature sulfur-resistant CO tail gas treatment catalyst utilizing temperature rise, which has the following advantages:

[0030] (1) This patent provides a novel low-temperature sulfur-resistant CO tail gas treatment catalyst, the main component of which is X. i ZrOSO 4a Sn b Zr m -nAl2O3, specific surface area ≥140m² 2 With a pore volume ≥0.7 ml / g, this high specific surface area and high pore volume design gives the catalyst higher reactivity and better adsorption, enabling more effective treatment of sulfur-containing CO tail gas. The catalyst exhibits excellent low-temperature sulfur resistance, effectively treating sulfur-containing CO tail gas at low temperatures, helping to reduce environmental pollution, while also possessing high-temperature hydrothermal resistance. The catalyst coating includes rare earth additives, Pd, Pt, precipitants, binders, and cellulose. This composite structure design results in higher catalytic efficiency and a longer service life, thereby improving the catalyst's economic benefits.

[0031] (2) The precipitant in the catalyst coating is Ce-Zr composite alumina, which has excellent oxygen storage capacity and can improve the catalytic efficiency of the catalyst. Attached Figure Description

[0032] Figure 1 The image shows the ignition temperature characteristic curve of the catalyst prepared in the example. Detailed Implementation

[0033] To enhance understanding of the present invention, the present invention will be further described in detail below with reference to embodiments and accompanying drawings. These embodiments are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0034] Example 1:

[0035] A low-temperature sulfur-resistant CO tail gas treatment catalyst utilizing temperature rise, comprising a catalyst support and a catalyst coating, wherein the catalyst coating comprises the following components in weight percentage:

[0036] X i ZrOSO 4a Sn b Zr m -nAl2O3 (80%)

[0037] Rare earth additive: La (2%)

[0038] Pt (0.5%)

[0039] Pd (0.3%)

[0040] Precipitant: Ce-Zr composite alumina (8%)

[0041] Adhesive (10%)

[0042] Cellulose (0.2%)

[0043] Among them, i:a:b:m:n=(1~5):(25~35):(10~20):(13~18):(45~55)

[0044] A method for preparing a low-temperature sulfur-resistant CO tail gas treatment catalyst utilizing temperature rise includes the following steps:

[0045] S1: Weigh the materials according to the above mass percentage.

[0046] S2: Weigh out the Pt solution and dilute it. Weigh out the La and add it to the Pt solution. After it is completely dissolved, take 1 / 5 of the amount and add it to the container. Weigh out the Pd solution, dilute it, add it to the La solution, and after it is completely dissolved, add it to the container. Stir well and then add the remaining Pt solution.

[0047] S3: Add Ce-Zr composite alumina precipitant and stir, then add binder.

[0048] S4: Finally, add cellulose and stir until the desired viscosity is reached.

[0049] S5: Coating is performed on the catalyst support.

[0050] Example 2:

[0051] A low-temperature sulfur-resistant CO tail gas treatment catalyst utilizing temperature rise, comprising a catalyst support and a catalyst coating, wherein the catalyst coating comprises the following components in weight percentage:

[0052] -X i ZrOSO 4a Sn b Zr m-nAl2O3 (85%)

[0053] - Rare earth additive: Ce (3%)

[0054] -Pt(0.8%)

[0055] -Pd(0.4%)

[0056] - Precipitant: Ce-Zr composite alumina (7%)

[0057] - Adhesive (12%)

[0058] - Cellulose (0.3%)

[0059] Among them, i:a:b:m:n=(1~5):(25~35):(10~20):(13~18):(45~55)

[0060] The preparation method is the same as in Example 1.

[0061] Example 3:

[0062] A low-temperature sulfur-resistant CO tail gas treatment catalyst utilizing temperature rise, comprising a catalyst support and a catalyst coating, wherein the catalyst coating comprises the following components in weight percentage:

[0063] -X i ZrOSO 4a Sn b Zr m -nAl2O3 (90%)

[0064] -Rare earth additives: Y (1%)

[0065] -Pt(0.2%)

[0066] -Pd(0.1%)

[0067] - Precipitant: Ce-Zr composite alumina (5%)

[0068] - Adhesive (14%)

[0069] - Cellulose (0.4%)

[0070] Among them, i:a:b:m:n=(1~5):(25~35):(10~20):(13~18):(45~55)

[0071] The preparation method is the same as in Example 1.

[0072] Example 4:

[0073] A low-temperature sulfur-resistant CO tail gas treatment catalyst utilizing temperature rise, comprising a catalyst support and a catalyst coating, wherein the catalyst coating comprises the following components in weight percentage:

[0074] -X i ZrOSO 4a Sn b Zr m -nAl2O3 (82%)

[0075] - Rare earth additives: a mixture of La and Ce (2.5%)

[0076] -Pt(0.6%)

[0077] -Pd(0.2%)

[0078] - Precipitant: Ce-Zr composite alumina (9%)

[0079] - Adhesive (11%)

[0080] - Cellulose (0.1%)

[0081] Among them, i:a:b:m:n=(1~5):(25~35):(10~20):(13~18):(45~55)

[0082] The preparation method is the same as in Example 1.

[0083] Example 5:

[0084] A low-temperature sulfur-resistant CO tail gas treatment catalyst utilizing temperature rise, comprising a catalyst support and a catalyst coating, wherein the catalyst coating comprises the following components in weight percentage:

[0085] -X i ZrOSO 4a Sn b Zr m -nAl2O3 (88%)

[0086] - Rare earth additives: a mixture of La and Y (2%)

[0087] -Pt(0.4%)

[0088] -Pd(0.3%)

[0089] - Precipitant: Ce-Zr composite alumina (6%)

[0090] - Adhesive (13%)

[0091] - Cellulose (0.5%)

[0092] Among them, i:a:b:m:n=(1~5):(25~35):(10~20):(13~18):(45~55).

[0093] The preparation method is the same as in Example 1.

[0094] The performance of the catalysts prepared in the examples was tested under three conditions:

[0095] ① Freshness

[0096] ② Sulfur aging: S250H30: 250℃ 100ppm SO2

[0097] ③ Hydrothermal aging: A550H100: 550℃ 10% H2O

[0098] The obtained ignition temperature characteristic curve is shown in the figure below. Figure 1 As shown in the figure, the catalyst obtained by this technical solution can achieve low-temperature sulfur resistance and high-temperature hydrothermal resistance.

[0099] As a further improvement, 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 within the protection scope of the present invention.

Claims

1. A low temperature sulfur tolerant CO off-gas treatment catalyst characterized by, The catalyst includes a catalyst carrier and a catalyst coating including X i ZrOSO 4a Sn b Zr m -nAl2O3, i: a: b: m: n = (1~5): (25~35): (10~20): (13~18): (45~55), a rare earth additive, Pd, Pt, a precipitator, a binder, and cellulose, X i ZrOSO 4a Sn b Zr m The oxide content of -nAl2O3 is 25~40%. X i ZrOSO 4a Sn b Zr m - the specific surface area of -nAl2O3 is > 140 m 2 / g, the pore volume is > 0.7 ml / g; The mass percentage of each component of the catalyst coating is as follows: X i ZrOSO 4a Sn b Zr m -nAl2O380~90% Rare earth additive 1-3%; Pt 0.1-1%; Pd 0.1-0.5%; Precipitant 5-10%; Binder 10-15%; Cellulose 0.1-0.5%; X is any one of La, Ce or Y; The precipitant is Ce-Zr composite alumina; The catalyst preparation method comprises the following steps: S1: weighing the materials according to the mass percentage of each material; S2: weighing the Pt solution for dilution, weighing the rare earth additive and adding it into the Pt solution, after complete dissolution, taking 1 / 5 of the amount and adding it into the barrel; after dilution of the Pd solution, adding it into the above solution containing the rare earth additive, after complete dissolution, adding it into the barrel, and after uniform stirring, adding the remaining Pt solution; S3: adding the precipitant and stirring, and then adding the binder; S4: finally adding the cellulose and stirring to the appropriate viscosity; S5: coating on the catalyst carrier.

2. The low temperature sulfur tolerant CO off-gas treatment catalyst according to claim 1, wherein, The rare earth additive is one or a mixture of several of La, Ce or Y.

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