A catalyst resistant to sulfur poisoning, and a preparation method and application thereof
The sulfur poisoning resistant catalyst prepared by the impregnation method utilizes oxalic acid as a vanadium source to support platinum and vanadium, which solves the problems of low activity and easy poisoning of existing catalysts, and achieves high efficiency in catalytic carbon monoxide oxidation and improved sulfur resistance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- INST OF URBAN ENVIRONMENT CHINESE ACAD OF SCI
- Filing Date
- 2024-09-11
- Publication Date
- 2026-05-26
AI Technical Summary
Existing anti-sulfur poisoning catalysts have low activity and are difficult to effectively degrade carbon monoxide in flue gas from the steel industry, while also posing a problem of sulfur dioxide poisoning.
A sulfur poisoning resistant catalyst was prepared by impregnation. Oxalic acid was used as a vanadium source to simultaneously load platinum and vanadium onto the surface of an alumina support. Vanadium acted as a sacrificial agent to adsorb sulfur oxides and protect the active sites of platinum. The one-step impregnation method eliminated the molding step, resulting in a clean and low-cost production process.
The prepared catalyst has excellent sulfur resistance and high activity, and can effectively catalyze the oxidation of carbon monoxide, while maintaining high efficiency after sulfidation.
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Figure CN118976488B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of catalyst technology, and in particular to an anti-sulfur poisoning catalyst, its preparation method, and its application. Background Technology
[0002] Carbon monoxide (CMon) is a common air pollutant, and the steel industry is one of the main sources of CMon emissions. The sintering process alone accounts for 40% of the total CMon emissions from the steel industry, necessitating focused control. Currently, the mainstream technology for CMon emission control is catalytic oxidation, which uses a catalyst to lower the reaction energy barrier of CMon, converting it into non-toxic carbon dioxide under relatively mild conditions. The core of this technology is the development of high-performance CMon oxidation catalysts. Stationary source flue gas compositions are complex; for example, flue gas from the steel industry often includes sulfur dioxide. The presence of sulfur dioxide reacts with the active components on the catalyst surface to form inert sulfates, causing catalyst deactivation.
[0003] Currently, the sulfur poisoning resistant catalysts prepared by existing technologies have low activity. Therefore, there is an urgent need to develop carbon monoxide oxidation catalysts that combine high activity and high sulfur resistance. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides an anti-sulfur poisoning catalyst, its preparation method, and its application. The anti-sulfur poisoning catalyst prepared by this invention exhibits excellent sulfur resistance and high activity. Through the sacrificial action of vanadium, it adsorbs sulfur oxides, thereby protecting the platinum active sites. This invention employs an impregnation method, utilizing oxalic acid as a co-solubilizing vanadium source; the production process is clean, low-cost, and shows promising application prospects.
[0005] To achieve this objective, the present invention adopts the following technical solution:
[0006] In a first aspect, the present invention provides a method for preparing an anti-sulfur poisoning catalyst, the method comprising:
[0007] Under stirring conditions, a platinum source, a vanadium source, oxalic acid, aluminum oxide, and a solvent are mixed to obtain a suspension; the suspension is dried and sintered to obtain the sulfur poisoning resistance catalyst.
[0008] This invention employs an impregnation method, utilizing oxalic acid as a vanadium source co-solubilizer. Capillary pressure generated by surface tension allows the mixed solvent to penetrate into the solid alumina, eliminating the need for catalyst forming. Furthermore, this application utilizes a one-step impregnation method to directly load both platinum and vanadium sources onto the surface of an alumina support, resulting in a clean, low-cost production process with broad application prospects.
[0009] Preferably, the platinum source comprises platinum tetraamminenitrate.
[0010] Preferably, the platinum source accounts for 0.1-0.5% of the mass of the aluminum oxide, for example, it can be 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45% or 0.5%, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0011] Preferably, the vanadium source includes ammonium metavanadate.
[0012] Preferably, the vanadium source accounts for 1-25% of the mass of the aluminum oxide, for example, it can be 1%, 3%, 5%, 7%, 9%, 11%, 15%, 17%, 20% or 25%, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0013] This invention can further improve the catalytic activity of carbon monoxide by controlling the amount of vanadium source, while also exhibiting excellent resistance to sulfur poisoning.
[0014] Preferably, the solvent includes deionized water.
[0015] Preferably, the mixing temperature is 30-40°C, for example, 30°C, 32°C, 34°C, 36°C, 37°C, 39°C or 40°C, but not limited to the listed values. Other unlisted values within the range are also applicable.
[0016] Preferably, the mixing order is as follows: first mix the solvent and platinum source, then mix the vanadium source and oxalic acid, and finally mix aluminum oxide.
[0017] Preferably, the stirring speed is 200-400 rpm, for example, it can be 200 rpm, 250 rpm, 300 rpm, 350 rpm or 400 rpm, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0018] Preferably, the stirring time is 2-4 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours, but not limited to the listed values. Other unlisted values within the range are also applicable.
[0019] Preferably, the drying step includes removing moisture followed by drying.
[0020] Preferably, the drying temperature is 100-120℃, for example, it can be 100℃, 102℃, 104℃, 106℃, 108℃, 110℃, 112℃, 114℃, 116℃, 118℃ or 120℃, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0021] Preferably, the drying time is 8-16 hours, for example, it can be 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or 16 hours, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0022] Preferably, the sintering temperature is 400-600℃, for example, it can be 400℃, 420℃, 440℃, 460℃, 480℃, 500℃, 520℃, 540℃, 560℃, 580℃ or 600℃, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0023] Preferably, the sintering time is 2-4 hours, for example, 2 hours, 2.5 hours, 3 hours, 3.5 hours or 4 hours, but not limited to the listed values. Other unlisted values within the range are also applicable.
[0024] As a preferred technical solution of the present invention, the preparation method includes the following steps:
[0025] Dissolve the platinum source in deionized water at 30-40℃, then add the vanadium source and oxalic acid. After all the solution is dissolved, add aluminum oxide and stir to obtain a suspension.
[0026] The suspension is dehydrated and dried at 100-120℃ for 8-16 hours to obtain the dried material.
[0027] The dried material is sintered at 400-600℃ for 2-4 hours to obtain the anti-sulfur poisoning catalyst.
[0028] In a second aspect, the present invention provides a sulfur poisoning resistant catalyst prepared by the preparation method described in the first aspect, wherein the sulfur poisoning resistant catalyst uses aluminum oxide as a support and supports platinum and vanadium.
[0029] The sulfur poisoning resistant catalyst prepared by this invention uses platinum as the main active component, with vanadium acting as a sacrificial agent to adsorb sulfur oxides, thereby protecting the platinum active sites and ensuring high catalyst activity. Therefore, the catalyst prepared by this invention exhibits excellent sulfur resistance and high activity.
[0030] Preferably, the molar ratio of platinum to vanadium is 1:(0.25-40), for example, it can be 1:0.5, 1:1, 1:2, 1:3, 1:3.5, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:12, 1:13, 1:14, 1:15, 1:20, 1:30 or 1:40, but is not limited to the listed values. Other unlisted values within the range are also applicable, preferably 1:(0.25-15).
[0031] Preferably, the molar ratio of vanadium to aluminum oxide is (1-10):1, for example, it can be 1:1, 1:3, 1:5, 1:7, 1:9, 1:10, but is not limited to the listed values. Other unlisted values within the range are also applicable. More preferably, it is (1-9):1.
[0032] Thirdly, the present invention provides an application of the sulfur poisoning resistant catalyst as described in the second aspect, wherein the sulfur poisoning resistant catalyst is applied to the catalytic oxidation of carbon monoxide.
[0033] Compared with the prior art, the present invention has at least the following beneficial effects:
[0034] (1) This invention uses an impregnation method, which generates capillary pressure through surface tension, allowing the mixed solvent to penetrate into the solid alumina, eliminating the need for catalyst forming. Furthermore, this application utilizes a one-step impregnation method with oxalic acid as a co-solubilizing vanadium source to directly load both platinum and vanadium sources onto the surface of the alumina support. This process is clean, low-cost, and has broad application prospects.
[0035] (2) In the sulfur poisoning resistant catalyst prepared by this invention, vanadium is the sacrificial agent and platinum is the active component of the catalyst. Vanadium adsorbs sulfur oxides, thereby protecting the platinum active sites and ensuring the high activity of the catalyst. Therefore, the catalyst prepared by this invention has excellent sulfur resistance and high activity. Attached Figure Description
[0036] Figure 1 This is a graph showing the catalytic activity of the anti-sulfur poisoning catalysts prepared in Examples 1, 4-7 and Comparative Example 1 for oxidizing carbon monoxide before presulfurization.
[0037] Figure 2 This is a graph showing the catalytic activity of the sulfur-resistant catalysts prepared in Examples 1, 4-7 and Comparative Example 1 after presulfurization for carbon monoxide oxidation. Detailed Implementation
[0038] The technical solution of the present invention will be further described below with reference to the accompanying drawings and specific embodiments. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention is determined by the claims.
[0039] Example 1
[0040] This embodiment provides a method for preparing an anti-sulfur poisoning catalyst, the preparation method being as follows:
[0041] (1) Dissolve 0.03g of tetraammineplatinum nitrate in 150mL of deionized water at 37℃, then add 0.41g of ammonium metavanadate and 6.2g of oxalic acid. After the tetraammineplatinum nitrate, ammonium metavanadate and oxalic acid are completely dissolved, add 6g of Al2O3 and stir at 37℃ and 300rpm for 3h to obtain a suspension.
[0042] (2) The suspension obtained in step (1) is placed in a rotary evaporator to remove moisture, and then dried in an oven at 110°C for 10 hours to obtain dried material;
[0043] (3) The dried material described in step (2) is placed in a muffle furnace and sintered at 500°C for 3 hours to obtain the anti-sulfur poisoning catalyst.
[0044] The catalyst prepared in this embodiment is named F-Pt. 0.25 V3Al2O3.
[0045] Example 2
[0046] This embodiment provides a method for preparing an anti-sulfur poisoning catalyst, the preparation method being as follows:
[0047] (1) Dissolve 0.006g of tetraammine nitrate platinum in 100mL of deionized water at 40℃, then add 0.06g of ammonium metavanadate and 6g of oxalic acid. After the tetraammine nitrate platinum, ammonium metavanadate and oxalic acid are completely dissolved, add 6g of Al2O3 and stir at 40℃ and 400rpm for 2h to obtain a suspension.
[0048] (2) The suspension obtained in step (1) is placed in a rotary evaporator to remove moisture, and then dried in an oven at 120°C for 8 hours to obtain dried material;
[0049] (3) The dried material described in step (2) is placed in a muffle furnace and sintered at 400°C for 4 hours to obtain the anti-sulfur poisoning catalyst.
[0050] The catalyst prepared in this embodiment is named F2-Pt. 0.05 V 0.4 Al2O3.
[0051] Example 3
[0052] This embodiment provides a method for preparing an anti-sulfur poisoning catalyst, the preparation method being as follows:
[0053] (1) Dissolve 0.03g of tetraammineplatinum nitrate in 100mL of deionized water at 30℃, then add 1.38g of ammonium metavanadate and 6g of oxalic acid. After the tetraammineplatinum nitrate, ammonium metavanadate and oxalic acid are completely dissolved, add 6g of Al2O3 and stir at 30℃ and 200rpm for 4h to obtain a suspension.
[0054] (2) The suspension obtained in step (1) is placed in a rotary evaporator to remove moisture, and then dried in an oven at 100°C for 16 hours to obtain dried material;
[0055] (3) The dried material described in step (2) is placed in a muffle furnace and sintered at 600°C for 2 hours to obtain the anti-sulfur poisoning catalyst.
[0056] The catalyst prepared in this embodiment is named F3-Pt. 0.25 V 10 Al2O3.
[0057] Example 4
[0058] The only difference between this embodiment and embodiment 1 is that, except for the addition of 0.14g of ammonium metavanadate in step (1), everything else is the same as in embodiment 1.
[0059] The catalyst prepared in this embodiment is named F-Pt. 0.25 V1Al2O3.
[0060] Example 5
[0061] The only difference between this embodiment and Embodiment 1 is that, except for the addition of 0.69g of ammonium metavanadate in step (1), everything else is the same as in Embodiment 1.
[0062] The catalyst prepared in this embodiment is named F-Pt. 0.25 V5Al2O3.
[0063] Example 6
[0064] The only difference between this embodiment and Embodiment 1 is that, except for the addition of 0.96g of ammonium metavanadate in step (1), everything else is the same as in Embodiment 1.
[0065] The catalyst prepared in this embodiment is named F-Pt. 0.25 V7Al2O3.
[0066] Example 7
[0067] The only difference between this embodiment and Embodiment 1 is that, except for the addition of 1.38g of ammonium metavanadate in step (1), everything else is the same as in Embodiment 1.
[0068] The catalyst prepared in this embodiment is named F-Pt. 0.25 V 10 Al2O3.
[0069] Example 8
[0070] The only difference between this embodiment and embodiment 1 is that, except that the sintering temperature in step (3) is 700°C, everything else is the same as in embodiment 1.
[0071] The catalyst prepared in this embodiment is named F4-Pt. 0.25 V3Al2O3.
[0072] Example 9
[0073] The only difference between this embodiment and embodiment 1 is that, except that the sintering temperature in step (3) is 300°C, everything else is the same as in embodiment 1.
[0074] The catalyst prepared in this embodiment is named F5-Pt. 0.25 V3Al2O3.
[0075] Comparative Example 1
[0076] The only difference between this comparative example and Example 1 is that, except that ammonium metavanadate is not added in step (1), everything else is the same as in Example 1.
[0077] The catalyst prepared in this comparative example was named F-Pt. 0.25 Al2O3.
[0078] Figure 1 The graph shows the catalytic activity of the anti-sulfur poisoning catalysts prepared in Examples 1, 4-7 and Comparative Example 1 before carbon monoxide oxidation. As can be seen from the graph, the introduction of vanadium almost always increases the activity of the catalyst in oxidizing carbon monoxide. This may be because the appropriate interaction between vanadium and platinum enhances the ability of Pt to oxidize carbon monoxide.
[0079] Figure 2 This is a graph showing the catalytic activity of the sulfur-poisoning-resistant catalysts prepared in Examples 1, 4-7, and Comparative Example 1 after presulfurization for carbon monoxide oxidation. The graphs show that the presulfurized P... 0.25 V3Al2O3 catalyst has the best catalytic activity for carbon monoxide oxidation. The introduction of low vanadium content cannot fully play the role of sacrificial agent, while the introduction of excessive vanadium content will lead to the accumulation of more sulfate on the support, thereby blocking the active sites.
[0080] Comparative Example 2
[0081] The only difference between this comparative example and Example 1 is that, except that oxalic acid is not added in step (1), everything else is the same as in Example 1.
[0082] The catalyst prepared in this comparative example was named F6-Pt. 0.25 V3Al2O3.
[0083] Comparative Example 3
[0084] The only difference between this comparative example and Example 1 is that, except for step (1) where oxalic acid is replaced with ethanol, everything else is the same as in Example 1.
[0085] The catalyst prepared in this comparative example was named F7-Pt. 0.25 V3Al2O3.
[0086] Test methods
[0087] The sulfur poisoning resistant catalysts prepared in Examples 1-9 and Comparative Examples 1-3 were pre-sulfurized in a 100 ppm SO2 / Air atmosphere for 12 h. The resulting catalysts were named S-Pt, respectively. 0.25 / Al2O3、S-Pt 0.25 V1 / Al2O3, S-Pt 0.25 V3 / Al2O3, S-Pt 0.25 V5 / Al2O3, S-Pt 0.25 V7 / Al2O3, S-Pt 0.25 V 10 / Al2O3、S2-Pt 0.05 V 0.4 / Al2O3、S3-Pt 0.25 V 10 / Al2O3、S4-Pt 0.25 V3 / Al2O3 and S5-Pt 0.25 V3 / Al2O3.
[0088] A certain amount of the above-mentioned catalyst, with a size of 40-60 mesh, was placed in a catalyst activity evaluation device. The activity evaluation was carried out in a fixed-bed reactor. The test conditions were: N2 = 400 mL / min, CO = 4000 ppm, O2 = 50 mL / min; total flow rate was 500 mL / min, and reaction space velocity was 100,000 mL / gh. -1 The test results for the catalyst and the pre-sulfurized catalyst are as follows: Figure 1 and Figure 2 As shown, the T values of the catalyst before and after pre-sulfurization are compared. 10 T 50 T 90 The temperatures are recorded in Table 1 and Table 2, respectively.
[0089] Table 1
[0090] Catalyst nomenclature <![CDATA[T 10 (℃)]]> <![CDATA[T 50 (℃)]]> <![CDATA[T 90 (℃)]]> Example 1 <![CDATA[F-Pt 0.25 V3 / Al2O3]]> 178 208 216 Example 2 <![CDATA[F2-Pt 0.25 V3 / Al2O3]]> 218 237 246 Example 3 <![CDATA[F3-Pt 0.25 V3 / Al2O3]]> 175 203 215 Example 4 <![CDATA[F-Pt 0.25 V1 / Al2O3]]> 191 223 228 Example 5 <![CDATA[F-Pt 0.25 V5 / Al2O3]]> 158 199 206 Example 6 <![CDATA[F-Pt 0.25 V7 / Al2O3]]> 173 205 210 Example 7 <![CDATA[F-Pt 0.25 V 10 / Al2O3]]> 178 207 215 Example 8 <![CDATA[F4-Pt 0.25 V3 / Al2O3]]> 167 206 220 Example 9 <![CDATA[F5-Pt 0.25 V3 / Al2O3]]> 162 206 215 Comparative Example 1 <![CDATA[F-Pt 0.25 Al2O3 192 212 216 Comparative Example 2 <![CDATA[F6-Pt 0.25 V3 / Al2O3]]> 195 226 235 Comparative Example 3 <![CDATA[F7-Pt 0.25 V3 / Al2O3]]> 189 220 227
[0091] Table 2
[0092]
[0093]
[0094] The test results show that:
[0095] (1) As can be seen from Examples 1-9 and Comparative Examples 1-3, the present invention uses a one-step impregnation method and utilizes oxalic acid as a vanadium source to directly load platinum source and vanadium source onto the surface of alumina support. By adjusting the vanadium content, the interaction between the support and the active component is controlled, and finally a catalyst with excellent CO oxidation ability is obtained.
[0096] (2) Through Examples 1, 4-7, and Comparative Example 1, the present invention, by controlling the molar ratio of platinum to vanadium, prepares an anti-sulfur catalyst with superior anti-sulfur performance and higher activity. By controlling the amount of vanadium used, the present invention can further improve the catalyst's resistance to sulfur poisoning and further optimize its catalytic effect. Introducing too low a vanadium content cannot fully utilize the sacrificial agent's role, while introducing too high a content will lead to the accumulation of more sulfate on the support, thus blocking the active sites.
[0097] (3) As can be seen from Examples 1 and 8-9, the anti-sulfur catalyst prepared by controlling the sintering temperature in this invention has excellent anti-sulfur performance and high activity. When the sintering temperature is high, Pt and V impregnated on Al2O3 agglomerate, resulting in a reduction of active sites, thereby reducing the anti-sulfur performance and catalytic activity; when the sintering temperature is low, it is insufficient to remove impurities contained in the platinum source and vanadium source, which may reduce the anti-sulfur performance and inhibit catalytic activity.
[0098] In summary, this invention employs an impregnation method, utilizing oxalic acid as a vanadium source for dissolution. Capillary pressure generated by surface tension allows the mixed solvent to penetrate into the solid alumina, eliminating the need for catalyst forming. Furthermore, this application utilizes a one-step impregnation method to directly load both platinum and vanadium sources onto the surface of an alumina support, resulting in a clean, low-cost production process with broad application prospects. In the prepared sulfur poisoning-resistant catalyst, platinum is the main active component, while vanadium acts as a sacrificial agent to adsorb sulfur oxides, thereby protecting the platinum active sites and ensuring high catalyst activity. Therefore, the catalyst prepared by this invention exhibits excellent sulfur resistance and high activity.
[0099] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.
Claims
1. A method for preparing a sulfur poisoning resistant catalyst, characterized in that, The preparation method includes: Under stirring conditions, a platinum source, a vanadium source, oxalic acid, aluminum oxide, and a solvent are mixed to obtain a suspension; the suspension is then dried and sintered to obtain the sulfur poisoning resistance catalyst. The mixing order is as follows: first mix the solvent and platinum source, then mix the vanadium source and oxalic acid, and finally mix aluminum oxide. The platinum source accounts for 0.2-0.5% of the mass of the aluminum oxide; The vanadium source includes ammonium metavanadate; The vanadium source accounts for 11-17% of the mass of the aluminum oxide; The sintering temperature is 400-600℃.
2. The preparation method according to claim 1, characterized in that, The platinum source includes platinum tetraamminenitrate.
3. The preparation method according to claim 1, characterized in that, The solvent includes deionized water.
4. The preparation method according to claim 1, characterized in that, The mixing temperature is 30-40℃.
5. The preparation method according to claim 1, characterized in that, The stirring speed is 200-400 rpm.
6. The preparation method according to claim 1, characterized in that, The stirring time is 2-4 hours.
7. The preparation method according to claim 1, characterized in that, The drying step includes removing moisture in a rotary evaporator followed by drying.
8. The preparation method according to claim 7, characterized in that, The drying temperature is 100-120℃.
9. The preparation method according to claim 7, characterized in that, The drying time is 8-16 hours.
10. The preparation method according to claim 1, characterized in that, The sintering time is 2-4 hours.
11. The preparation method according to claim 1, characterized in that, The preparation method includes the following steps: Dissolve the platinum source in deionized water at 30-40℃, then add the vanadium source and oxalic acid. After all the solution is dissolved, add aluminum oxide and stir to obtain a suspension. The suspension was dried in a rotary evaporator to remove moisture, and then dried at 100-120℃ for 8-16 hours to obtain the dried material. The dried material is sintered at 400-600℃ for 2-4 hours to obtain the anti-sulfur poisoning catalyst.
12. A sulfur poisoning resistant catalyst prepared by the method according to any one of claims 1-10, characterized in that, The anti-sulfur poisoning catalyst uses aluminum oxide as a support and loads platinum and vanadium.
13. The application of the anti-sulfur poisoning catalyst as described in claim 12, characterized in that, The anti-sulfur poisoning catalyst is used for the catalytic oxidation of carbon monoxide.