Process for degrading vocs in sulfur-containing exhaust gas

Abstract

The present application belongs to the technical field of metal catalyst preparation, and particularly relates to a process for degrading VOCs in sulfur-containing waste gas. The process comprises: (1) preparing a surfactant solution and a catalyst carrier; (2) mixing phthalocyanine ring ligand, ZIF-L, central metal salt, reaction aid and the surfactant solution, and adding the catalyst carrier for one-time impregnation; continuing to add heteropoly acid and vanadium salt for two-time impregnation; (3) mixing the catalyst carrier after two-time impregnation with a nitrogen source, and carrying out a melt reaction; (4) one-time calcination by increasing temperature and passing in air, and then two-time calcination under an inert atmosphere, and then cooling to obtain a VOCs catalyst; (5) loading the VOCs catalyst into a reactor, increasing temperature, and passing in sulfur-containing waste gas to degrade VOCs in the sulfur-containing waste gas. The present application prepares a multi-metal catalyst to improve the efficiency of the existing metal catalyst for degrading VOCs and the ability to resist sulfur dioxide poisoning.

Description

Technical Field

[0001] This invention belongs to the field of metal catalyst preparation technology, specifically relating to a process for degrading VOCs in sulfur-containing waste gas. Background Technology

[0002] Volatile organic compounds (VOCs) are widely present in various fields such as petroleum processing, printing, coatings, and building materials production. These organic compounds are diverse and contribute to the formation of PM2.5 and photochemical smog in the atmosphere, polluting the environment. Furthermore, they can volatilize at room temperature, posing a threat to human health. Currently, large-scale control methods generally involve installing metal catalysts in exhaust gas systems to degrade VOCs into harmless carbon dioxide, nitrogen, and water through catalytic oxidation. However, to address the high throughput and low residence time characteristics of exhaust gases, the VOCs treatment efficiency per unit volume of catalyst is insufficient. For example, in petroleum refining and petrochemical production processes, the exhaust gas composition is complex, including non-methane hydrocarbons, aldehydes, and sometimes volatile sulfur compounds such as sulfur dioxide, which can easily lead to the deactivation of metal catalysts.

[0003] Chinese patent CN108295866A discloses a nano-spinachite CoMn2O4 catalyst for the catalytic oxidation of VOCs. The catalyst is a single-phase CoMn2O4, prepared by a sol-gel method using manganese acetate, cobalt nitrate, and oxalic acid. This patent focuses primarily on its low-temperature activity and oxygen flow properties, and as stated in the original text, the nano-spinachite is a single-phase CoMn2O4. However, its resistance to sulfur dioxide poisoning is limited, and the patented catalyst does not address other measures to combat sulfur dioxide poisoning.

[0004] Chinese patent CN119869598A discloses a VOCs catalyst and its preparation method. The VOCs catalyst comprises a modified ZSM-5 zeolite molecular sieve and supported active metals and / or active metal oxides. The preparation method involves calcining the H-ZSM-5 zeolite molecular sieve and then adding it to an organic alkaline solution for a hydrothermal reaction. After the reaction is complete, the sieve is washed, filtered, dried, and calcined to obtain alkaline-treated ZSM-5. Subsequently, the alkaline-treated ZSM-5 is added to an acid / salt solution corresponding to the active metal / metal oxide, and after removing water, it is calcined to obtain the VOCs catalyst. This patent involves multiple calcination and hydrothermal treatment steps, which is cumbersome and not conducive to industrial production. Summary of the Invention

[0005] The purpose of this invention is to provide a process for degrading VOCs in sulfur-containing waste gas, so as to improve the efficiency of existing metal catalysts in degrading VOCs and their resistance to sulfur dioxide poisoning.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0007] The process for degrading VOCs in sulfur-containing waste gas according to the present invention includes the following steps:

[0008] (1) Preparation of surfactant solution and catalyst support;

[0009] (2) The phthalocyanine ring ligand, ZIF-L, central metal salt, reaction aid and surfactant solution are mixed together, and a catalyst support is added for a first impregnation; then heteropoly acid and vanadium salt are added for a second impregnation.

[0010] (3) The catalyst support after secondary impregnation is blended with a nitrogen source and then reacted in a melt reaction;

[0011] (4) Continue heating, introduce air for a first calcination, then calcinate again under an inert atmosphere to cool down, and obtain VOCs catalyst;

[0012] (5) Take VOCs catalyst and load it into the reactor, heat it up, and introduce sulfur-containing waste gas to degrade the VOCs in the sulfur-containing waste gas.

[0013] in:

[0014] In step (1), the surfactant solution is prepared by mixing surfactant, micelle stabilizer and water in a mass ratio of (85~100):(35~50):2500. The surfactant is 1-hexadecyl-3-methylimidazolium bromide or didecyldimethylammonium bromide, and the micelle stabilizer is potassium bromide or sodium bromide.

[0015] In step (1), the preparation of the catalyst support includes the following steps: Fe-Cr-Al honeycomb metal is pretreated, heated, impregnated with support slurry, dried and calcined in sequence to obtain the catalyst support;

[0016] The pretreatment involves washing the Fe-Cr-Al honeycomb metal in toluene, then washing it in a 1.5-3 mol / L nitric acid aqueous solution, and finally rinsing it with clean water and drying it. The heating temperature is 880-900℃, and the heating time is 8-10 h. The carrier slurry is prepared by mixing γ-Al2O3 powder, boehmite, and water, adjusting the pH to 4-4.5, and stirring for 7-9 h. The carrier slurry is prepared by mixing 25-30 wt% γ-Al2O3, 5-6 wt% boehmite, and the balance water. The mass ratio of Fe-Cr-Al honeycomb metal to carrier slurry is 650:(1500-1800). The calcination temperature is 550-570℃, and the calcination time is 1-2 h.

[0017] In step (2), the phthalocyanine ring ligand is 4-sulfonated ammonium phthalate, the central metal salt is cobalt chloride hexahydrate, the reaction aid is ammonium tungstate, and the mass ratio of the phthalocyanine ring ligand, ZIF-L, central metal salt, reaction aid and surfactant solution is (250~275):(8~10):60:(40~50):(2620~2650).

[0018] In step (2), the heteropoly acid is 12-molybdenum phosphate, and the vanadium salt is ammonium metavanadate; the mass ratio of catalyst support, heteropoly acid, vanadium salt and surfactant solution is 600:(90~120):(72~90):(2620~2650).

[0019] In step (2), the first immersion time is 30-40 minutes, and the second immersion time is 18-25 minutes.

[0020] In step (3), the nitrogen source is urea, and the mass ratio of urea to catalyst support is (750~850):600.

[0021] In step (3), the melting reaction temperature is 190~200℃ and the melting reaction time is 2.5~3.5h.

[0022] In step (4), the heating rate is 10.5~13.5℃ / min and the air introduction rate is 9700~12000mL / min.

[0023] In step (4), the calcination temperature is 550~560℃ and the calcination time is 3~4h.

[0024] In step (4), the secondary calcination temperature is 550~560℃, the secondary calcination time is 0.5~1h, and the cooling rate is 6~8℃ / min.

[0025] In step (5), the reactor temperature is 260~280℃; the volume hourly space velocity of the sulfur-containing waste gas is 13000~18000 h⁻¹. -1 .

[0026] In step (5), the sulfur-containing waste gas contains VOCs, which include non-methane total hydrocarbons and non-hydrocarbon VOC components. The non-hydrocarbon VOC components are formaldehyde, acetaldehyde, and succinate. The content of non-methane total hydrocarbons is 200~3500 mg / m³. 3 The total content of non-hydrocarbon VOCs components is 50~1800 mg / m³ 3 The sulfur dioxide content is 50~780 mg / m³ 3 .

[0027] The beneficial effects of this invention are as follows:

[0028] In the melting reaction stage of this invention, urea melts at 190~200℃ to form a homogeneous molten medium with good fluidity. Compared with liquid phase reaction, this invention reduces the complex post-treatment process of liquid phase reaction and breaks the mass transfer limitation of direct solid phase reaction. At the same time, urea decomposes upon heating to release ammonia, maintaining the weakly alkaline reaction atmosphere of the system. In addition to serving as precursors for the active sites of VOCs catalysts, ammonium metavanadate and other substances can also serve as catalysts, providing favorable reaction conditions for the reaction of 4-sulfonated ammonium phthalate, cobalt chloride, urea, etc., to generate metal phthalocyanine compounds.

[0029] Under acidic conditions, boehmite undergoes peptidation to form a positively charged alumina sol, which forms a stable slurry with γ-Al2O3 powder through electrostatic interaction. After calcination, boehmite decomposes into γ-Al2O3, which sintersects with the original powder to form a continuous, high-specific-surface-area porous γ-Al2O3 coating. The porous γ-Al2O3 coating is a weakly acidic surface, and its adsorption capacity for acidic sulfide molecules is weaker than that of alkaline carriers. 1-Hexadecyl-3-methylimidazolium bromide or didecyldimethylammonium bromide, as cationic surfactants, can form micellar soft templates in aqueous solutions. These templates can interact with anionic precursors (sulfonated phthalate, molybdenum phosphate, tungstate, vanadate) in the system to achieve molecular-level uniform dispersion of Co, W, Mo, and V multimetallic precursors, avoiding agglomeration of active components during subsequent calcination. The highly dispersed active sites themselves have stronger anti-poisoning redundancy, reducing the probability of complete sulfide coverage and deactivation.

[0030] During the two impregnations of the catalyst support, ZIF-L plays a role in confinement and nitrogen source pre-loading. The pores of ZIF-L can confine metal precursor ions, preventing migration and aggregation. Simultaneously, 4-sulfonated ammonium phthalate, influenced by the tendency to minimize surface energy, forms metal phthalocyanine compounds with metal ions and free Co ions on ZIF-L during the melt reaction. These metal phthalocyanine compounds form π-π stacking through a macrocyclic structure, promoting anchorage of the metal phthalocyanine compounds on the ZIF-L surface, preventing the formation of crystalline phases and maximizing the exposure of metal active sites. Conversely, the metal phthalocyanine compounds also ensure the pre-assembly effect of ZIF-L. Furthermore, 12-molybdenum phosphate can be embedded in the pre-assembled network formed by ZIF-L and the metal phthalocyanine compounds. 12-molybdenum phosphate has excellent sulfur resistance and will not be deactivated by SO2 sulfidation, serving as a long-lasting acidic site and auxiliary active center.

[0031] By forming a pre-assembled network, it is beneficial to form uniform and well-dispersed MNC (M refers to W, Mo, V, etc., which are auxiliary Co metal active centers) anti-sulfur active sites during subsequent calcination. That is, using the nitrogen-doped carbon structure as a bridge, W, Mo, V multi-metals and Co (and Co metal oxides) are combined to form a multi-metal composite catalyst, which is the key to improving the sulfur poisoning resistance of VOCs catalysts.

[0032] The high oxidation state of W, Mo, and V can freely regulate the electronic structure of the Co center, reducing the binding force between the active metal centers such as Co and volatile sulfides. At the same time, through pre-coordination, the nitrogen-carbon doped structure formed during calcination serves as an electron transport channel, which can be uniformly embedded between the Co, W, Mo, and V sites. Through physical barrier, it can effectively reduce the probability of multiple sulfide molecules binding at the same time without affecting the catalytic activity of the metal active center. Detailed Implementation

[0033] The present invention will now be described and illustrated in detail with reference to the embodiments.

[0034] The raw materials used in the following examples and comparative examples are all commercially available products, of which ZIF-L was provided by Xi'an Ruixi Biotechnology Co., Ltd.

[0035] Example 1

[0036] 96g of 1-hexadecyl-3-methylimidazolium bromide was dissolved in 2500g of deionized water, and 42g of potassium bromide was added and mixed. After vacuum degassing, a surfactant solution was prepared. 650g of Fe-Cr-Al honeycomb metal (material type 1Cr13Al4, a type of metal honeycomb carrier) was washed in toluene until it was clean and free of stains. It was then acid-washed in 2L of 2mol / L dilute nitric acid for 20min, rinsed with water and dried. It was then placed in a muffle furnace and kept at 900℃ for 8h. After cooling to room temperature, it was taken out for use. 1600g of suspension was prepared by mixing γ-Al2O3 powder, boehmite and water, wherein the solid content of γ-Al2O3 was 28.5% and the solid content of boehmite was 5.3%. The pH was adjusted to 4~4.5 and stirred for 7h to obtain a carrier slurry. The prepared Fe-Cr-Al honeycomb metal was immersed in the carrier slurry and repeatedly extracted for 10min. It was then taken out, dried and calcined at 550℃ for 2h to obtain a catalyst carrier.

[0037] At room temperature, 250g of ammonium 4-sulfonated phthalate, 5g of ZIF-L, 60g of cobalt chloride hexahydrate and 40g of ammonium tungstate were added to a surfactant solution, followed by the addition of 600g of catalyst support for impregnation. After ultrasonic dispersion for 40min, 90g of 12-molybdic acid and 90g of ammonium metavanadate were added, and ultrasonic dispersion was carried out for 22min. The catalyst support after impregnation was then obtained.

[0038] The impregnated catalyst support was transferred to a reactor, 750 g of urea was added, and the mixture was sealed and melted at 200 °C for 2.5 h. After cooling to room temperature, the catalyst was removed and dried to constant weight, then transferred to a tube furnace and heated to 560 °C at a rate of 13.5 °C / min. Air was then introduced at a rate of 9700 mL / min and calcined for 3 h. The catalyst was then calcined for another 1 h in a nitrogen atmosphere. After cooling to room temperature at a rate of 7 °C / min, the catalyst was removed to obtain the VOCs catalyst.

[0039] VOCs catalyst was loaded into the reactor, which was preheated to 260℃ for 10 minutes. Then, sulfur-containing waste gas was introduced, with the volume hourly space velocity (VHSV) controlled at 15000 h⁻¹. -1 The sulfur-containing waste gas contains VOCs, including non-methane total hydrocarbons and non-hydrocarbon VOC components such as formaldehyde, acetaldehyde, and succinate. The content of non-methane total hydrocarbons is 200 mg / m³. 3 The total content of non-hydrocarbon VOCs components is 50 mg / m³. 3 The sulfur dioxide content is 50 mg / m³. 3 After 90 hours of stable operation, samples were taken from the reactor outlet every 15 hours for testing, and the VOCs removal rate remained above 99.3%. Finally, sulfur dioxide was removed through desulfurization to obtain elemental sulfur, thus completing the treatment of sulfur-containing waste gas.

[0040] Example 2

[0041] Dissolve 85g of didecyldimethylammonium bromide in 2500g of deionized water, add 35g of potassium bromide and mix well. Degas under vacuum to obtain a surfactant solution. Wash 650g of Fe-Cr-Al honeycomb metal (material type 1Cr13Al4, a type of metal honeycomb carrier) in toluene until it is clean and free of stains. Acid wash with 2L of 1.5mol / L dilute nitric acid for 20min, rinse with water and dry. Then place it in a muffle furnace and keep it at 890℃ for 9.5h. Cool to room temperature and remove for later use. Prepare a 1500g suspension of γ-Al2O3 powder, boehmite and water, wherein the solid content of γ-Al2O3 is 30% and the solid content of boehmite is 5%. Adjust the pH to 4~4.5 and continue stirring for 8h to obtain a carrier slurry. Immerse the prepared Fe-Cr-Al honeycomb metal in the carrier slurry and repeatedly extract for 10min. Remove, dry and calcine at 560℃ for 1h to obtain a catalyst carrier.

[0042] At room temperature, 275g of ammonium 4-sulfonated phthalate, 10g of ZIF-L, 60g of cobalt chloride hexahydrate and 50g of ammonium tungstate were added to a surfactant solution, followed by the addition of 600g of catalyst support for impregnation. After ultrasonic dispersion for 35min, 100g of 12-molybdic acid and 72g of ammonium metavanadate were added, and ultrasonic dispersion was carried out for 18min. The catalyst support after impregnation was then obtained.

[0043] The impregnated catalyst support was transferred to a reactor, 820 g of urea was added, and the mixture was sealed and melted at 195 °C for 3 h. After cooling to room temperature, the catalyst was removed and dried to constant weight, then transferred to a tube furnace and heated to 556 °C at a rate of 12 °C / min. Air was then introduced at a rate of 10000 mL / min and calcined for 3.5 h. Calcination was then continued for 0.5 h in a nitrogen atmosphere. The catalyst was then cooled to room temperature at a rate of 8 °C / min and removed to obtain the VOCs catalyst.

[0044] VOCs catalyst was loaded into the reactor, which was preheated to 270℃ for 10 minutes. Then, sulfur-containing waste gas was introduced, with the volume hourly space velocity (VHSV) controlled at 13000 h⁻¹. -1 The sulfur-containing waste gas contains VOCs, including non-methane total hydrocarbons and non-hydrocarbon VOC components such as formaldehyde, acetaldehyde, and succinate. The content of non-methane total hydrocarbons is 2500 mg / m³. 3 The total content of non-hydrocarbon VOCs components was 1100 mg / m³. 3 The sulfur dioxide content is 250 mg / m³. 3 After 90 hours of stable operation, samples were taken from the reactor outlet every 15 hours for testing, and the VOCs removal rate remained above 98.9%. Finally, sulfur dioxide was removed through desulfurization to obtain elemental sulfur, thus completing the treatment of sulfur-containing waste gas.

[0045] Example 3

[0046] 100g of 1-hexadecyl-3-methylimidazolium bromide was dissolved in 2500g of deionized water, and 50g of sodium bromide was added and mixed. After vacuum degassing, a surfactant solution was prepared. 650g of Fe-Cr-Al honeycomb metal (material type 1Cr13Al4, a type of metal honeycomb carrier) was washed in toluene until it was clean and free of stains. It was then acid-washed in 2L of 3mol / L dilute nitric acid for 20min, rinsed with water and dried. It was then placed in a muffle furnace and kept at 880℃ for 10h. After cooling to room temperature, it was taken out for use. 1800g of suspension was prepared by mixing γ-Al2O3 powder, boehmite and water, wherein the solid content of γ-Al2O3 was 25% and the solid content of boehmite was 6%. The pH was adjusted to 4~4.5 and stirred for 9h to obtain a carrier slurry. The prepared Fe-Cr-Al honeycomb metal was immersed in the carrier slurry and repeatedly extracted for 10min. It was then taken out, dried and calcined at 570℃ for 1.2h to obtain a catalyst carrier.

[0047] At room temperature, 265g of ammonium 4-sulfonated phthalate, 8g of ZIF-L, 60g of cobalt chloride hexahydrate and 45g of ammonium tungstate were added to a surfactant solution, followed by the addition of 600g of catalyst support for impregnation. After ultrasonic dispersion for 30min, 120g of 12-molybdic acid and 83g of ammonium metavanadate were added, and ultrasonic dispersion was carried out for 25min. The catalyst support after impregnation was then obtained.

[0048] The impregnated catalyst support was transferred to a reactor, 850 g of urea was added, and the mixture was sealed and melted at 190 °C for 3.5 h. After cooling to room temperature, the catalyst was removed and dried to constant weight, then transferred to a tube furnace and heated to 550 °C at a rate of 10.5 °C / min. Air was then introduced at a rate of 12000 mL / min and calcined for 4 h. The catalyst was then calcined for another 0.8 h in a nitrogen atmosphere. After cooling to room temperature at a rate of 6 °C / min, the catalyst was removed to obtain the VOCs catalyst.

[0049] VOCs catalyst was loaded into the reactor, which was preheated to 280℃ for 10 minutes. Then, sulfur-containing waste gas was introduced, with the volume hourly space velocity (VHSV) controlled at 18000 h⁻¹. -1 The sulfur-containing waste gas contains VOCs, including non-methane total hydrocarbons and non-hydrocarbon VOC components such as formaldehyde, acetaldehyde, and succinate. The content of non-methane total hydrocarbons is 3500 mg / m³. 3 The total content of non-hydrocarbon VOCs components is 1800 mg / m³. 3 The sulfur dioxide content is 780 mg / m³. 3 After 90 hours of stable operation, samples were taken from the reactor outlet every 15 hours for testing, and the VOCs removal rate remained above 98.0%. Finally, sulfur dioxide was removed through desulfurization to obtain elemental sulfur, thus completing the treatment of sulfur-containing waste gas.

[0050] Comparative Example 1

[0051] The surfactant was replaced with an equal mass of deionized water, and the remaining steps were the same as in Example 1, to obtain the VOCs catalyst.

[0052] Comparative Example 2

[0053] Without adding ammonium 4-sulfonated phthalate and cobalt chloride hexahydrate, the remaining steps are the same as in Example 1 to obtain the VOCs catalyst.

[0054] Comparative Example 3

[0055] Without adding ammonium 4-sulfonated phthalate, the remaining steps are the same as in Example 1 to obtain the VOCs catalyst.

[0056] Comparative Example 4

[0057] Without adding heteropolyacids, the remaining steps are the same as in Example 1 to obtain a VOCs catalyst.

[0058] Comparative Example 5

[0059] Without adding ammonium tungstate, the remaining steps are the same as in Example 1 to obtain the VOCs catalyst.

[0060] Comparative Example 6

[0061] Without adding ammonium metavanadate, the remaining steps are the same as in Example 1 to obtain the VOCs catalyst.

[0062] Comparative Example 7

[0063] First, 12-molybdenum phosphate and ammonium metavanadate were impregnated, followed by impregnation with 4-sulfonated ammonium phthalate, ZIF-L, cobalt chloride hexahydrate and ammonium tungstate. The remaining steps were the same as in Example 1 to obtain the VOCs catalyst.

[0064] Comparative Example 8

[0065] The VOCs catalyst in Example 1 was replaced with an equal mass of commercially available Pd / γ-Al2O3 catalyst, wherein the Pd loading of the commercially available Pd / γ-Al2O3 was 0.5 wt%.

[0066] Implementation effect evaluation

[0067] Referring to the waste gas treatment operation steps in Example 3, the VOCs catalysts prepared in all examples and comparative examples were tested. 5.0 g of VOCs catalyst was loaded into the reactor; when designing the mixed gas treatment capacity, the standard volume hourly space velocity was set to 18000 h⁻¹. -1 The catalyst bed was heated to 280°C. The composition of the sulfur-containing waste gas was the same as in Example 3. The initial total VOCs concentration reading (C) was... in The total concentration of VOCs in the treated sulfur-containing waste gas (C) was measured every 15 hours.out After 90 hours, the system is shut down. The VOCs removal rate is calculated as follows: Removal rate = (C in -C out ) / C in ×100%, specific VOCs catalyst performance data are shown in Table 1.

[0068] Table 1. VOCs catalyst performance test data

[0069]

[0070] As shown in Table 1, the present invention achieves a volume hourly space velocity (VHSV) of 18000 h⁻¹. -1 Sulfur dioxide concentration 780 mg / m³ 3 Under certain conditions, a high VOCs removal rate can be maintained, and the VOCs removal rate can still be maintained above 98% after 90 hours. The VOCs catalyst prepared by this invention has excellent degradation efficiency for VOCs containing complex components and resistance to sulfur dioxide poisoning.

Claims

1. A process for degrading VOCs in sulfur-containing waste gas, characterized in that, Includes the following steps: (1) Preparation of surfactant solution and catalyst support; The surfactant solution is prepared by surfactant, micelle stabilizer and water, wherein the surfactant is 1-hexadecyl-3-methylimidazolium bromide or didecyldimethylammonium bromide, and the micelle stabilizer is potassium bromide or sodium bromide; The catalyst support is prepared by pretreating Fe-Cr-Al honeycomb metal, heating, impregnating it with a support slurry, drying it, and calcining it. The pretreatment involves adding Fe-Cr-Al honeycomb metal to toluene for cleaning, then adding it to a nitric acid aqueous solution for cleaning, and finally rinsing with clean water and drying. The heating temperature is 880~900℃. The carrier slurry is prepared by mixing γ-Al2O3 powder, boehmite and water, adjusting the pH to 4~4.5 and continuing to stir. (2) The phthalocyanine ring ligand, ZIF-L, central metal salt, reaction aid and surfactant solution are mixed together, and a catalyst support is added for a first impregnation; heteropoly acid and vanadium salt are added for a second impregnation; the phthalocyanine ring ligand is 4-sulfonated ammonium phthalate, the central metal salt is cobalt chloride hexahydrate, the reaction aid is ammonium tungstate; the heteropoly acid is 12-molybdenum phosphate, and the vanadium salt is ammonium metavanadate; (3) The catalyst support after secondary impregnation is mixed with a nitrogen source and melted; the nitrogen source is urea, and the mass ratio of urea to catalyst support is (750~850):600; the melting reaction temperature is 190~200℃, and the melting reaction time is 2.5~3.5h; (4) Continue heating, introduce air for a first calcination, then calcinate again under an inert atmosphere, cool down, and obtain VOCs catalyst; (5) Take VOCs catalyst and load it into the reactor, heat it up, and introduce sulfur-containing waste gas to degrade the VOCs in the sulfur-containing waste gas.

2. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (1), the surfactant, micelle stabilizer and water are prepared in a mass ratio of (85~100):(35~50):2500.

3. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (1), the concentration of nitric acid aqueous solution is 1.5~3 mol / L; the heating time is 8~10 h; the stirring time is 7~9 h; γ-Al2O3 accounts for 25~30 wt% of the carrier slurry, boehmite accounts for 5~6 wt%, and the balance is water; the mass ratio of Fe-Cr-Al honeycomb metal to carrier slurry is 650:(1500~1800); the calcination temperature is 550~570℃, and the calcination time is 1~2 h.

4. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (2), the mass ratio of phthalocyanine ring ligand, ZIF-L, central metal salt, reaction aid and surfactant solution is (250~275):(8~10):60:(40~50):(2620~2650).

5. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (2), the mass ratio of catalyst support, heteropoly acid, vanadium salt and surfactant solution is 600:(90~120):(72~90):(2620~2650); the first impregnation time is 30~40 min and the second impregnation time is 18~25 min.

6. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (4), the heating rate is 10.5~13.5℃ / min and the air introduction rate is 9700~12000mL / min.

7. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (4), the first calcination temperature is 550~560℃ and the first calcination time is 3~4h; the second calcination temperature is 550~560℃ and the second calcination time is 0.5~1h; the cooling rate is 6~8℃ / min.

8. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (5), the reactor temperature is 260~280℃; the volume hourly space velocity of the sulfur-containing waste gas is 13000~18000 h⁻¹. -1 .

9. The process for degrading VOCs in sulfur-containing waste gas according to claim 1, characterized in that, In step (5), the sulfur-containing waste gas contains VOCs, which include non-methane total hydrocarbons and non-hydrocarbon VOC components. The non-hydrocarbon VOC components are formaldehyde, acetaldehyde, and succinate; the content of non-methane total hydrocarbons is 200~3500 mg / m³. 3 The total content of non-hydrocarbon VOCs components is 50~1800 mg / m³ 3 The sulfur dioxide content is 50~780 mg / m³ 3 .

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