A high-efficiency catalytic oxidation desulfurizer and its preparation method and application

Abstract

The present invention proposes a high-efficiency catalytic oxidation desulfurizer, a preparation method and application thereof, which loads the desulfurization active component cobalt phthalocyanine onto the surface of a molecular sieve with a rich specific surface area to achieve the desulfurization of sulfur-containing waste gas. The preparation method includes three steps: activation of the hydroxyl groups on the surface of the molecular sieve, modification of the molecular sieve with a silane coupling agent, and loading the molecular sieve with cobalt phthalocyanine, and finally obtaining a high-efficiency catalytic oxidation desulfurizer loaded with cobalt phthalocyanine. The present invention modifies the molecular sieve so that the cobalt phthalocyanine is linked to the surface of the molecular sieve in the form of a chemical bond, and adopts an ultrasonic impregnation method to disperse the desulfurization active component cobalt phthalocyanine as much as possible on the surface of the adsorption desulfurizer. The desulfurizer involved in the present invention can efficiently remove sulfides such as organic sulfur and H2S from sulfur-containing waste gas, and is applied to the selective catalytic oxidation desulfurization process of sulfur-containing gas, and can reduce the total sulfur content in the sulfur-containing waste gas to 1.0 mg / Nm 3 The desulfurizer has a relatively high air velocity (0.1s ‑1 ) and penetration sulfur capacity (200-300mg / g desulfurizer), and has a long service life, good repeatability, and can be recycled.

Description

Technical Field

[0001] The invention belongs to the technical field of adsorbents, and in particular relates to a high-efficiency catalytic oxidation desulfurization agent and a preparation method and application thereof. Background Art

[0002] Volatile sulfur compounds have serious impacts on the environment and human health. Sulfur-containing waste gas is primarily composed of H2S, but sometimes also contains a wide variety of organic sulfur compounds, including sulfides, disulfides, mercaptans, thiophene sulfides, and their derivatives. Desulfurization and purification of waste gas is currently the primary and most effective technical means of controlling pollution from volatile sulfur compounds worldwide.

[0003] Since the total sulfur content in sulfur-containing waste gas is relatively low, dry desulfurization is generally recommended. Dry desulfurization technology has the advantages of low cost, no wastewater and waste acid generation, and simple process. The solid desulfurizer is directly loaded and used, the equipment investment is small, the operation is simple, and it is widely used. However, the effect of dry desulfurization still needs to be improved, especially the desulfurizer and its process for removing organic sulfur, which still have a lot of room for improvement. At present, the dry desulfurizers that are widely studied and industrially applied at home and abroad mainly include: activated carbon-based desulfurizers, iron-based desulfurizers, zinc-based desulfurizers, copper-based desulfurizers and manganese-based desulfurizers. Among them, oxidative desulfurization (ODS) technology is a deep desulfurization technology with broad application prospects (it can remove organic sulfur). It has the advantages of mild reaction conditions, simple operation, and high desulfurization rate. It can reduce the total sulfur content from several hundred ppm to less than 50 ppm and is regarded as one of the most promising desulfurization methods in the future.

[0004] Discovered in the early 20th century, phthalocyanine is a complex with 18 π electrons, a π,π conjugated and p,π conjugated system. This large conjugated system is highly stable and facilitates electron transfer, making it suitable for catalysis. Within the phthalocyanine ring lies a cavity approximately 0.27 nm in diameter, which can accommodate transition metals such as iron, cobalt, and nickel. Metallophthalocyanines are formed when two hydrogen atoms in the metallophthalocyanine molecule are replaced by metal atoms. The most significant advantage of metallophthalocyanines as catalysts is their ability to enable oxidation reactions to proceed at low temperatures and with high efficiency. The highly planar nature of metallophthalocyanines allows catalytic reactions to occur axially within this plane. In particular, their highly selective axial coordination for organosulfides makes them highly valuable for theoretical research and promising application prospects. In the field of catalytic oxidative desulfurization (DOS), molecular sieves are considered important supports for DOS catalysts due to their superior structural characteristics, including high hydrostatic and thermal stability, wide pore shape selectivity, large specific surface area, and adjustable pore size. Pores with diameters less than 2 nanometers are called micropores, those greater than 50 nanometers are called macropores, and those between 2 and 50 nanometers are called mesoporous molecular sieves. Pure silicon mesoporous molecular sieves such as MCM-41, SBA-15, and HMS have amorphous pore walls, and the pure silicon skeleton has few lattice defects, resulting in low catalytic activity. Modifying the surface functionality of molecular sieves and introducing organic groups into the pores to prepare novel organic-inorganic composite materials has become a recent research hotspot.

[0005] Patent CN102512942A provides a low-temperature fine desulfurizer, which uses catalyst waste (the main component is alumina) as a carrier, mixed with zinc carbonate and copper carbonate, and obtained under the action of pore-forming agent and binder to obtain a fine desulfurizer, thereby improving the desulfurization accuracy and sulfur capacity of the desulfurizer; Kong Lingyan et al. dispersed Ag in TS-1 molecular sieve by equal volume impregnation method. Since Ag species has a strong adsorption capacity for sulfide, the sulfide is concentrated around the titanium active center of the catalyst, thereby increasing the sulfur concentration around the active site, but this method is relatively expensive; Zhao Lixia used the organic base tetrapropylammonium hydroxide to modify TS-1, and characterization found that the specific surface area and pore volume of TS-1 were slightly increased.

[0006] Wang Guanqing et al. used the liquid phase reflux impregnation method to modify the surface of HMS molecular sieve, and used the modified molecular sieve as a carrier to load phosphotungstic acid HPW on it to prepare HPW-NH2-HMS desulfurizer; and used the ultrasonic impregnation method to metal-modify the in situ synthesized Ti-HMS molecular sieve, thereby improving the dispersion of active components on the molecular sieve surface. The activity of the catalyst loaded with metal components is in the order of Zn / Ti-HMS>Cu / Ti-HMS>Fe / Ti-HMS.

[0007] Xue Kechuang and his colleagues synthesized aluminum tetranitrophthalocyanine and studied its catalytic activity for the removal of ethanethiol. However, metal phthalocyanine compounds tend to form aggregates in solution, reducing their catalytic activity. A drawback is that catalyst recovery is difficult, and they can only remove sulfides in the liquid phase.

[0008] Ren Tengjie et al. attempted to maximize the catalytic properties of metallophthalocyanines by loading them onto corresponding molecular sieves. Using an impregnation method, they loaded metallophthalocyanines onto supports such as MCM-41 molecular sieve, bamboo charcoal, and titanium silicalite molecular sieves. They then investigated the desulfurization efficiency of these supported desulfurizers for DBT. The results showed that phthalocyanines catalyzed the removal of organic sulfur, and that the substituents on the phthalocyanine ring influenced their catalytic activity. However, this method has the disadvantage that the metallophthalocyanines are only supported on the support by weak van der Waals forces and are easily desorbed from the support, resulting in a continuous decrease in desulfurization efficiency and a short service life.

[0009] Zhang Juan et al. synthesized a titanium silicalite molecular sieve, Ti-MCM-41, and modified it by covalently loading iron phthalocyanine with various substituents onto the Ti-MCM-41. At room temperature and pressure, the Ti-MCM-41-loaded iron phthalocyanine served as a catalyst, air as an oxidant, and tetrabutylammonium bromide caprolactam as an ionic liquid as an extractant to catalyze the oxidation of dibenzothiophene. Results showed that dibenzothiophene removal rates reached as high as 95.6%. However, this method has the disadvantages of requiring light and primarily targeting dibenzothiophene removal in a liquid phase (model oil).

[0010] In order to overcome the above-mentioned problems, it is urgent to develop an efficient desulfurizer for sulfur-containing waste gas, improve the removal effect of organic sulfur, extend the service life of the desulfurizer, and reduce the desulfurization cost of sulfur-containing waste gas. Summary of the Invention

[0011] In order to solve the above problems in the prior art, the present invention proposes a high-efficiency catalytic oxidation desulfurization agent and a preparation method and application thereof.

[0012] In a first aspect, the present invention provides a high-efficiency catalytic oxidation desulfurizer, which is composed of a modified molecular sieve and an active component, cobalt phthalocyanine. Specifically, the active component, cobalt phthalocyanine, is loaded on the surface of the modified molecular sieve by chemical bonding.

[0013] As a specific embodiment of the present invention, the molecular sieve includes at least one of MCM, SBA, HMS, and ZSM, and the molecular sieve has a specific surface area of 100m 2 / g-1000m 2 / g, average crushing strength>80N / particle, bulk density of 0.60kg / L~1.05kg / L, and wear rate<1.0wt%.

[0014] As a specific embodiment of the present invention, the cobalt phthalocyanine includes one of hydroxyphthalocyanine cobalt and aminophthalocyanine cobalt. Based on the weight of the molecular sieve in the high-efficiency catalytic oxidation desulfurizer, the cobalt phthalocyanine loading is 0.2wt%-1.0wt%; and / or the amount of the silane coupling agent is 1.0wt%-1.5wt%.

[0015] As a specific embodiment of the present invention, the silane coupling agent includes at least one of a hydroxy silane coupling agent, a carboxyl silane coupling agent, and a vinyl silane coupling agent, preferably including one of 3-aminopropyltrimethoxysilane, ethanoltriethoxysilane, acetoxytrimethoxysilane, and vinyltrimethoxysilane.

[0016] As a specific embodiment of the present invention, the concentration of the silane coupling agent solution is 0.1-1.0 wt %.

[0017] As a specific embodiment of the present invention, the physical properties of the desulfurizer are as follows: specific surface area> 100m 2 / g, pore volume ≥0.2mL / g, the organic sulfur removal rate of the high-efficiency catalytic oxidation desulfurizer is >90%, and the H2S desulfurization accuracy is <1.0mg / Nm 3 , the total breakthrough sulfur capacity is 60.6-372.9mg / g desulfurizer.

[0018] According to the present invention, the calculation formula for breakthrough sulfur capacity is:

[0019]

[0020] Where Q S is the gas flow rate of the simulated gas, ml / s;

[0021] C a is the sulfur content in the simulated gas, mg / Nm 3 ;

[0022] Va is the desulfurizer loading amount, ml;

[0023] ρ is the bulk density of the desulfurizer in g / ml.

[0024] t b is the running time of the desulfurization agent evaluation experiment, h.

[0025] In a second aspect, the present invention provides a method for preparing the high-efficiency catalytic oxidation desulfurizer, comprising loading the active component cobalt phthalocyanine on the surface of a modified molecular sieve carrier;

[0026] The modification of the molecular sieve is modification with a silane coupling agent, and the silane coupling agent includes at least one of a hydroxy silane coupling agent, a carboxyl silane coupling agent, and a vinyl silane coupling agent.

[0027] As a specific embodiment of the present invention, the preparation method comprises the following steps:

[0028] S1: activating the surface of the molecular sieve with hydroxyl groups to obtain an activated molecular sieve;

[0029] S2: Modifying the activated molecular sieve obtained in step S1 with a silane coupling agent to obtain a modified molecular sieve;

[0030] S3: mixing the modified molecular sieve obtained in step S2 with cobalt phthalocyanine, filtering, washing, and low-temperature calcining to obtain the high-efficiency catalytic oxidation desulfurization agent loaded with cobalt phthalocyanine.

[0031] As a specific embodiment of the present invention, in step S1, the hydroxyl activation treatment includes soaking the molecular sieve in a NaOH aqueous solution.

[0032] The soaking time is 5 hours to 24 hours, and the concentration of the NaOH aqueous solution is 0.05 mol / L to 0.5 mol / L, preferably 0.1 mol / L.

[0033] As a specific embodiment of the present invention, in step S2, the silane coupling agent modification treatment includes immersing the activated molecular sieve in a silane coupling agent solution, adjusting the solution pH to 3.5-5.5, continuously stirring at 100° C. in a N2 atmosphere, and then cooling, washing with deionized water, and drying;

[0034] The silane coupling agent includes one of 3-aminopropyltrimethoxysilane, ethanoltriethoxysilane, acetoxytrimethoxysilane and vinyltrimethoxysilane.

[0035] The solvent in the silane coupling agent solution includes one of pure water, ethanol, benzene and toluene.

[0036] The concentration of the silane coupling agent solution is 0.1 wt%-1.0 wt%.

[0037] The amount of the silane coupling agent used is 1.0 wt%-1.5 wt%.

[0038] As a specific embodiment of the present invention, in step S3, the phthalocyanine is a cobalt phthalocyanine solution, and the solubility of the cobalt phthalocyanine solution is 1 mmol / L-100 mmol / L; the mixing method adopts an ultrasonic impregnation method to impregnate the modified molecular sieve into the cobalt phthalocyanine solution; preferably, the ultrasonic frequency range is 2×10 4 ~10 10HZ, the reaction temperature is 30-120° C., the stirring rate is 100 r / min-1000 r / min, and the reaction time is 0.1 h-1 h; the solvent in the cobalt phthalocyanine solution is one of DMF, DMSO, dichloromethane, acetone or sulfolane.

[0039] As a specific embodiment of the present invention, the specific surface area of the obtained high-efficiency catalytic oxidation desulfurization agent is greater than 100m 2 / g, pore volume ≥0.2mL / g, organic penetrating sulfur capacity>50mg / g desulfurizer, total penetrating sulfur capacity is between 200-372.9mg / g desulfurizer.

[0040] In a third aspect, the present invention provides application of the high-efficiency catalytic oxidation desulfurizer in the field of desulfurization of sulfur-containing waste gas.

[0041] As a specific embodiment of the present invention, the high-efficiency catalytic oxidation desulfurizer can remove sulfides containing organic sulfur and H2S in sulfur-containing waste gas.

[0042] As a specific embodiment of the present invention, the equivalent diameter of the desulfurizer is in the range of 1.0mm-10.0mm according to the desulfurization process requirements; the volume space velocity of the desulfurizer is not greater than 0.1s -1 , the residence time is not less than 10s; the desulfurizer is regenerated by 200-350 ℃ steam purge, the purge gas can enter the sulfur recovery unit to recover sulfur, the entire desulfurization process does not produce three wastes.

[0043] The above raw materials in the present invention can be prepared in-house or purchased commercially, and the present invention is not particularly limited thereto.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] 1. The high-efficiency catalytic oxidation desulfurizer of the present invention has high activity, which can not only remove H2S, but also has a good removal effect on organic sulfur, and can purify the total sulfur content in sulfur-containing waste gas to 1.0 mg / Nm 3 Within.

[0046] 2. The preparation method of the high-efficiency catalytic oxidation desulfurizer of the present invention is easy to operate, has low energy consumption, can disperse the desulfurization active components on the surface of the adsorption desulfurizer, and the desulfurizer has a high sulfur penetration capacity and a long service life. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 Schematic diagram of the surface silanolization of the molecular sieve of the present invention;

[0048] Figure 2 Schematic diagram of the modification of the molecular sieve of the present invention by a silane coupling agent;

[0049] Wherein, R is an alkyl group; X is a methoxy group, an ethoxy group, a chloro group, etc.; Y is an organic reactive group (vinyl group, epoxy group, amino group, hydroxyl group, carboxyl group, etc.);

[0050] Figure 3 This is a schematic diagram of a desulfurizing agent evaluation device according to the present invention;

[0051] Figure 4 This is the test result of test case 1;

[0052] Figure 5 This is the test result of test case 2.

[0053] Among them, 1-sulfur-containing waste gas source; 2-pressure reducing valve; 3-desulfurization inlet pressure gauge; 4-desulfurization inlet valve; 5-gas volume flow meter; 6-distributor and upper filler; 7-desulfurizer bed; 8-lower filler; 9-desulfurization outlet valve; 10-desulfurization outlet back pressure valve. DETAILED DESCRIPTION

[0054] The present invention will be further described below with reference to specific examples, but they do not constitute any limitation to the present invention.

[0055] The desulfurizer evaluation device, gas chromatograph, specific surface area and pore size analyzer, electric constant temperature blast drying oven (including inert gas system), filter paper, beaker, flask with reflux, loaded reactor, muffle furnace, electronic balance, series of cobalt phthalocyanine and its corresponding solvents DMF, dimethyl sulfoxide (DMSO), dichloromethane, acetone or cyclopentane, etc. and NaOH (analytical grade), molecular sieves, nitrogen, silane coupling agent (3-aminopropyltrimethoxysilane, ethanoltriethoxysilane, acetoxytrimethoxysilane, vinyltrimethoxysilane) and its corresponding solvent pure water, ethanol, benzene, toluene, etc. and other related terms involved in each embodiment of the present invention do not limit the present invention. They are only for the purpose of describing specific embodiments and are not intended to limit the present invention. They should not be understood as being limited to the embodiments described herein.

[0056] Example 1

[0057] This embodiment provides a high-efficiency catalytic oxidation desulfurization agent and a preparation method thereof, the specific details of which are as follows:

[0058] S1: Activation of hydroxyl groups on the molecular sieve surface: Weigh 100 ml of MCM-41 molecular sieve (bulk density 0.6, specific surface area 1000 m 2 / g), the molecular sieve was soaked in a 0.05 mol / L NaOH aqueous solution at room temperature and pressure for 5 h, and then rinsed with deionized water to obtain;

[0059] S2: Silane coupling agent modification of molecular sieve: Weigh 600 mg of 3-hydroxy-propyltrimethoxysilane into a three-necked flask and add 119.4 g of deionized water (solvent) to prepare a 0.5% dilute solution. Use liquid phase reflux impregnation method to treat MCM-41 molecular sieve, immerse MCM-41 molecular sieve in the solution, adjust the solution pH to 3.5, stir continuously in N2 atmosphere, heat reflux at 100°C for 5 hours, then cool, wash with deionized water, and then dry at 50°C for 3 hours in an electric constant temperature blast drying oven under inert gas protection;

[0060] S3: Cobalt phthalocyanine loading: Weigh 6g of cobalt tetrahydroxyphthalocyanine (635.46) and add 100ml of N,N-dimethylformamide (DMF) to prepare a solution of approximately 100mmol / L. The DMF solution of cobalt tetrahydroxyphthalocyanine and 3-hydroxypropyltrimethoxysilane-modified MCM-41 molecular sieve were placed in a loading reactor and treated by ultrasonic immersion. The loading reaction conditions were: ultrasonic frequency of 2×10 4 HZ, reaction temperature is 30 ° C, stirring rate is 100 r / min, reaction time is 1 h, loading amount is 1.0 wt%; after the reaction is completed, it is filtered, washed and calcined in a muffle furnace at 300 ° C for 5 h to obtain CoPc-MCM-41 desulfurizer loaded with cobalt phthalocyanine.

[0061] The bulk density of the highly efficient catalytic oxidation desulfurizer CoPc-MCM-41 obtained in Example 1 is 0.68 g / cm 3 ;Specific surface area is 800m 2 / g, and the pore volume is 0.55mL / g.

[0062] Example 2

[0063] This embodiment provides a high-efficiency catalytic oxidation desulfurization agent and a preparation method thereof, the specific details of which are as follows:

[0064] S1: Activation of hydroxyl groups on the molecular sieve surface: Weigh 100 ml of SBA-15 molecular sieve (bulk density 0.8, specific surface area 500 m 2 / g), the molecular sieve was soaked in 0.1 mol / L NaOH aqueous solution at room temperature and pressure for 10 h, and then rinsed with deionized water;

[0065] S2: Silane coupling agent modification of molecular sieve: Weigh 800 mg of ethanol triethoxysilane into a three-necked flask and add 799.2 g of ethanol (solvent) to prepare a 0.1% dilute solution. Use liquid phase reflux impregnation method to treat SBA-15 molecular sieve, immerse SBA-15 molecular sieve in the solution, adjust the solution pH to 4.5, stir continuously in N2 atmosphere, heat reflux at 100°C for 5 hours, then cool, wash with deionized water, and then dry at 50°C for 3 hours in an electric constant temperature blast drying oven under inert gas protection;

[0066] S3: Cobalt phthalocyanine loading: Weigh 4g of aminophthalocyanine cobalt (631.46) and add 126ml of N,N-dimethylformamide (DMF) to prepare a solution of approximately 50mmol / L. The DMF solution of aminophthalocyanine cobalt and ethanol-triethoxysilane-modified SBA-15 molecular sieve were placed in a loading reactor and treated by ultrasonic immersion. Loading reaction conditions: Ultrasonic frequency of 10×10 4 HZ, the reaction temperature is 40 ° C, the stirring rate is 200 r / min, the reaction time is 0.5 h, and the loading amount is 0.5 wt%; after the reaction is completed, it is filtered, washed and calcined in a muffle furnace at 300 ° C for 5 h to obtain a CoPc-SBA-15 desulfurizer loaded with cobalt phthalocyanine.

[0067] The bulk density of the highly efficient catalytic oxidation desulfurizer CoPc-SBA-15 obtained in Example 2 is 0.85 g / cm 3 ;Specific surface area is 710m 2 / g, and the pore volume is 0.45mL / g.

[0068] Example 3

[0069] This embodiment provides a high-efficiency catalytic oxidation desulfurization agent and a preparation method thereof, the specific details of which are as follows:

[0070] S1: Activation of hydroxyl groups on the surface of molecular sieve: Weigh 100 ml of ZSM-5 molecular sieve (bulk density 0.68, specific surface area 100 m 2 / g), the molecular sieve was soaked in 0.3 mol / L NaOH aqueous solution at room temperature and pressure for 24 h, and then rinsed with deionized water;

[0071] S2: Silane coupling agent modification of molecular sieve: Weigh 1050 mg of vinyltrimethoxysilane into a three-necked flask and add 418.9 g of toluene (solvent) to prepare a dilute solution with a concentration of 0.25%. Use liquid phase reflux impregnation method to treat ZSM-5 molecular sieve, immerse ZSM-5 molecular sieve in the solution, adjust the solution pH to 3.5, stir continuously in N2 atmosphere, heat reflux at 100 ° C for 5 hours, then cool, wash with deionized water, and then dry at 50 ° C for 3 hours in an electric constant temperature blast drying oven under inert gas protection;

[0072] S3: Cobalt phthalocyanine loading: Weigh 2.5g of aminophthalocyanine cobalt (631.46) and add 79.8ml of N,N-dimethylformamide (DMF) to prepare a solution of approximately 50mmol / L. The aminophthalocyanine cobalt DMF solution and vinyltrimethoxysilane-modified ZSM-5 molecular sieve were placed in a loading reactor and treated by ultrasonic immersion. Loading reaction conditions: Ultrasonic frequency of 1000×10 4 HZ, the reaction temperature is 60 ° C, the stirring rate is 300 r / min, the reaction time is 0.7 h, and the loading amount is 0.2 wt%; after the reaction is completed, it is filtered, washed and calcined in a muffle furnace at 300 ° C for 5 h to obtain a CoPc-ZSM-5 desulfurizer loaded with cobalt phthalocyanine.

[0073] The bulk density of the highly efficient catalytic oxidation desulfurizer CoPc-ZSM-5 obtained in Example 3 is 0.72 g / cm 3 Specific surface area: 178m 2 / g, and the pore volume is 0.20mL / g.

[0074] Example 4

[0075] This embodiment provides a high-efficiency catalytic oxidation desulfurization agent and a preparation method thereof, the specific details of which are as follows:

[0076] S1: Activation of hydroxyl groups on the molecular sieve surface: Weigh 100 ml of HMS molecular sieve (bulk density 1.0, specific surface area 300 m 2 / g), the molecular sieve was soaked in 0.5 mol / L NaOH aqueous solution at room temperature and pressure for 15 h, and then rinsed with deionized water;

[0077] S2: Silane coupling agent modification of molecular sieve: Weigh 1000 mg of acetoxytrimethoxysilane into a three-necked flask, add 132.3 g of benzene (solvent) to make a dilute solution with a concentration of 0.75%. Use liquid phase reflux impregnation method to treat HMS molecular sieve, immerse HMS molecular sieve in the solution, adjust the solution pH to 5.5, stir continuously in N2 atmosphere, heat reflux at 100 ° C for 5 hours, then cool, wash with deionized water, and then dry at 50 ° C for 3 hours in an electric constant temperature blast drying oven under inert gas protection;

[0078] S3: Cobalt phthalocyanine loading: Weigh 5g of cobalt tetrahydroxyphthalocyanine (635.46) and add 157.4ml of N,N-dimethylformamide (DMF) to prepare a solution of approximately 50mmol / L. Place the DMF solution of cobalt tetrahydroxyphthalocyanine and the HMS molecular sieve modified with acetoxytrimethoxysilane in a loading reactor and treat with ultrasonic immersion. Loading reaction conditions: Ultrasonic frequency of 100×10 4 HZ, the reaction temperature is 50 ° C, the stirring rate is 300 r / min, the reaction time is 0.6 h, and the loading amount is 0.75 wt%; after the reaction is completed, it is filtered, washed and calcined in a muffle furnace at 300 ° C for 5 h to obtain a CoPc-HMS desulfurizer loaded with cobalt phthalocyanine.

[0079] The bulk density of the highly efficient catalytic oxidation desulfurizer CoPc-HMS obtained in Example 4 is 1.06 g / cm 3 ;Specific surface area is 400m 2 / g, and the pore volume is 0.26mL / g.

[0080] Test Case

[0081] like Figure 3 As shown, it is a desulfurizer evaluation device commonly used in this technical field, wherein the sulfur-containing waste gas source 1, the desulfurizer evaluation experiment replaces the sulfur-containing waste gas with simulated gas, H2S is inorganic sulfur, and methyl mercaptan, ethyl mercaptan, and DMDS replace organic sulfur; the desulfurizer evaluation test of the present invention is to fill 50ml of desulfurizer in the desulfurizer bed 7; adjust the pressure reducing valve 2 to a suitable gas source, and the desulfurization inlet pressure gauge 3 generally displays 100kPa-1000kPa, indicating the desulfurizer bed inlet pressure; adjust the gas volume flowmeter 5 to a gas flow rate of 2.0ml / s-5.0ml / s to control the space velocity of the desulfurizer; the sulfur-containing waste gas passes through the distributor and the upper filler 6, the desulfurizer bed 7, and the lower filler 8 in sequence, and the desulfurization temperature is room temperature, generally 20℃-50℃. The gas after desulfurization passes through the desulfurizer bed 7 and the desulfurization outlet valve 9 to analyze and detect the desulfurization effect; the desulfurization outlet back pressure valve 10 is used to control the desulfurization reaction pressure.

[0082] Test Example 1

[0083] The desulfurization agent CoPc-MCM-41 in Example 1 was loaded into the desulfurization agent bed 7 of the desulfurization agent evaluation device, wherein the gas source composition is shown in Table 1. The desulfurization process was evaluated according to Table 2. The desulfurization outlet gas was chromatographically analyzed every 72 hours to monitor the total sulfur content. Figure 4 As shown; when the total sulfur content at the outlet is greater than 1.0 mg / Nm 3 The sulfur capacity, desulfurization accuracy, and organic sulfur removal rate of the desulfurizer were calculated. The results are shown in Table 9.

[0084] Table 1

[0085]

[0086] Table 2

[0087] project Numerical Gas flow ml / s 2 Desulfurization temperature ℃ 20 Desulfurization pressure kPa 100 <![CDATA[Hourly space velocity -1 > 144 Desulfurizer particle size (mm) 1.6 Desulfurizer filling amount ml 50 <![CDATA[Density g / cm 3 > 0.68

[0088] Test Example 2

[0089] The desulfurizer CoPc-SBA-15 in Example 2 was loaded into the desulfurizer bed 7 of the desulfurizer evaluation device, wherein the gas source composition is shown in Table 3. The desulfurization process was evaluated according to Table 4. The desulfurization outlet gas was chromatographically analyzed every 72 hours to monitor the total sulfur content. When the outlet total sulfur content was greater than 1.0 mg / Nm 3 The sulfur capacity, desulfurization accuracy, and organic sulfur removal rate of the desulfurizer were calculated. The results are shown in Table 9.

[0090] Table 3

[0091]

[0092] Table 4

[0093] project Numerical Gas flow ml / s 5 Desulfurization temperature ℃ 40 Desulfurization pressure kPa 200 <![CDATA[Hourly space velocity -1 > 360 Desulfurizer particle size (mm) 1.6 Desulfurizer filling amount ml 50 <![CDATA[Density g / cm 3 > 0.85

[0094] Test Example 3

[0095] The desulfurization agent CoPc-ZSM-5 in Example 3 was loaded into the desulfurization agent bed 7 of the desulfurization agent evaluation device, wherein the gas source was the sulfur-containing waste gas generated in the process of treating a certain alkali slag, the composition of which is shown in Table 5. The desulfurization process was evaluated according to Table 6. The desulfurization outlet gas was chromatographically analyzed every 72 hours to monitor the total sulfur content. When the outlet total sulfur content was greater than 10.0 mg / Nm 3 The sulfur capacity, desulfurization accuracy, and organic sulfur removal rate of the desulfurizer were calculated. The results are shown in Table 9.

[0096] Table 5

[0097]

[0098]

[0099] Table 6

[0100] project Numerical Gas flow ml / s 3 Desulfurization temperature ℃ 40 Desulfurization pressure kPa 500 <![CDATA[Hourly space velocity -1 > 216 Desulfurizer particle size (mm) 1.6 Desulfurizer filling amount ml 50 <![CDATA[Density g / cm 3 > 0.72

[0101] Test Example 4

[0102] The desulfurizer CoPc-HMS in Example 4 was loaded into the desulfurizer bed 7 of the desulfurizer evaluation device, wherein the gas source was the sulfur-containing waste gas from the waste oil tank, the composition of which is shown in Table 7. The desulfurization process was evaluated according to Table 8. The outlet gas was chromatographically analyzed every 72 hours to monitor the total sulfur content. When the outlet total sulfur content was greater than 1.0 mg / Nm 3 The sulfur capacity, desulfurization accuracy, and organic sulfur removal rate of the desulfurizer were calculated. The results are shown in Table 9.

[0103] Table 7

[0104]

[0105] Table 8

[0106]

[0107]

[0108] In order to more clearly illustrate that the high-efficiency catalytic oxidation desulfurizer prepared by the present invention has excellent organic sulfur removal rate, desulfurization accuracy and breakthrough sulfur capacity, the following comparative examples 1, 2, 3 and 4 were conducted.

[0109] Comparative Example 1

[0110] In the preparation process of the catalytic oxidation desulfurizer in Example 1, step S2 was omitted, and the other steps remained unchanged. Tetrahydroxy cobalt phthalocyanine was directly loaded on the MCM-41 molecular sieve to obtain the cobalt phthalocyanine loaded desulfurizer CoPc-MCM-41-A. The breakthrough sulfur capacity and desulfurization accuracy of the desulfurizer CoPc-MCM-41-A were tested on the desulfurizer evaluation device according to the gas source composition in Table 1 and the evaluation conditions in Table 2, wherein the space velocity was 144h -1 The evaluation results are shown in Table 9.

[0111] Comparative Example 2

[0112] In the catalytic oxidation desulfurizer preparation process of Example 1, the tetrahydroxyphthalocyanine cobalt was replaced with cobalt nitrate in step S3, and the other steps remained unchanged. The cobalt nitrate was loaded onto the MCM-41 molecular sieve using deionized water as the dispersion medium to obtain the cobalt oxide loaded desulfurizer CoO-MCM-41. The breakthrough sulfur capacity and desulfurization accuracy of the desulfurizer CoO-MCM-41 were tested on the desulfurizer evaluation device according to the gas source composition in Table 1 and the evaluation conditions in Table 2, wherein the space velocity was 144h -1 The evaluation results are shown in Table 9.

[0113] Comparative Example 3

[0114] The low-temperature desulfurizer in patent CN 102512942 A was used to investigate the breakthrough sulfur capacity and desulfurization accuracy of the control desulfurizer on the desulfurizer evaluation device according to the gas source composition in Table 1 and the evaluation conditions in Table 2. The air velocity was 144h -1 The evaluation results are shown in Table 9.

[0115] Comparative Example 4

[0116] The low-temperature desulfurizer in patent CN 102512942 A was used to examine the breakthrough sulfur capacity, organic sulfur removal rate, and desulfurization accuracy of the control desulfurizer on the desulfurizer evaluation device according to the gas source composition in Table 3 and the evaluation conditions in Table 4. The air velocity was 360h -1 The evaluation results are shown in Table 9.

[0117] Table 9

[0118]

[0119] As shown in Table 9, by comparing test examples 1 and 3 with control examples 3 and 4, it can be seen that under the same desulfurization conditions and desulfurization accuracy requirements, the high-efficiency catalytic oxidation desulfurizer obtained by the present invention has a higher penetration sulfur capacity than the desulfurizer of the control example, and the total sulfur capacity and organic sulfur capacity are increased by 13% and 282% respectively; by comparing test example 1 and control example 2, it can be seen that the desulfurization effect of the cobalt phthalocyanine desulfurization active component involved in the present invention is better than that of the ordinary cobalt oxide desulfurization active component; by comparing test example 1 and control example 1, it can be seen that the coupling agent modification method of the molecular sieve involved in the present invention can effectively load the cobalt phthalocyanine desulfurization active component on the surface of the molecular sieve carrier. And the high-efficiency catalytic oxidation desulfurizer obtained by the present invention has the ability of recycling and regeneration, and does not produce hazardous waste; the high-efficiency catalytic oxidation desulfurizer obtained by the present invention has good organic sulfur removal ability, and when the desulfurization accuracy is ≯10mg / Nm 3 Under the conditions of , the organic sulfur removal rate can reach 80%. When the high-efficiency catalytic oxidation desulfurizer obtained by the present invention is applied to the desulfurization of sulfur-containing waste gas generated in the alkali slag treatment process and sulfur-containing waste gas from the waste oil tank, it still has a high sulfur capacity and organic sulfur removal capacity, which can meet the requirements of sulfur-containing waste gas purification treatment.

[0120] Any numerical value mentioned in the present invention includes all values that increase by one unit each time from the lowest value to the highest value if there is only a gap of two units between any minimum value and any maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, time, etc. is stated to be 50-90, it is meant in this specification to specifically list values such as 51-89, 52-88... and 69-71 and 70-71. For non-integer values, it is appropriate to consider units of 0.1, 0.01, 0.001 or 0.0001. These are just some special examples. In this application, in a similar manner, all possible combinations of numerical values between the listed lowest value and the listed highest value are considered to have been disclosed.

[0121] It should be noted that the embodiments described above are only used to explain the present invention and do not constitute any limitation of the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present invention may be modified as specified within the scope of the claims of the present invention, and the present invention may be revised without departing from the scope and spirit of the present invention. Although the present invention described therein relates to specific methods, materials and embodiments, it does not mean that the present invention is limited to the specific examples disclosed therein. On the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A high-efficiency catalytic oxidation desulfurizer for sulfur-containing waste gas, characterized in that: The high-efficiency catalytic oxidation desulfurizer is composed of a molecular sieve modified with a silane coupling agent and an active component, cobalt phthalocyanine, wherein the active component, cobalt phthalocyanine, is supported on the surface of the molecular sieve modified with the silane coupling agent; the molecular sieve comprises at least one of MCM, SBA, HMS, and ZSM; the silane coupling agent is one of 3-hydroxy-propyltrimethoxysilane, ethanoltriethoxysilane, acetoxytrimethoxysilane, and vinyltrimethoxysilane; and the cobalt phthalocyanine comprises one of hydroxy cobalt phthalocyanine and amino cobalt phthalocyanine. The preparation method of the high-efficiency catalytic oxidation desulfurizer comprises the following steps: S1: activating the surface of the molecular sieve with hydroxyl groups to obtain an activated molecular sieve; S2: Modifying the activated molecular sieve obtained in step S1 with a silane coupling agent to obtain a silane coupling agent-modified molecular sieve; S3: mixing the molecular sieve modified with the silane coupling agent obtained in step S2 with cobalt phthalocyanine, filtering, washing, and calcining at low temperature to obtain the high-efficiency catalytic oxidation desulfurization agent; The cobalt phthalocyanine loading is 0.2 wt% to 1.0 wt% based on the weight of the molecular sieve in the high-efficiency catalytic oxidation desulfurization agent; the organic sulfur removal rate of the high-efficiency catalytic oxidation desulfurization agent is greater than 90%, and / or the H2S desulfurization accuracy is less than 1.0 mg / Nm 3 , and / or the total breakthrough sulfur capacity is 60.6-372.9 mg / g desulfurizer.

2. The high-efficiency catalytic oxidation desulfurizer according to claim 1, characterized in that: The specific surface area of the molecular sieve is 100-1000m 2 / g, and / or average crushing strength>80N / particle, and / or bulk density is 0.60-1.05kg / L, and / or wear rate is <1.0wt%.

3. The high-efficiency catalytic oxidation desulfurizer according to claim 1, characterized in that: The amount of the silane coupling agent is 1.0wt%-1.5wt%; And / or, the concentration of the silane coupling agent solution is 0.1-1.0 wt %.

4. A method for preparing a high-efficiency catalytic oxidation desulfurizer for sulfur-containing waste gas according to any one of claims 1 to 3, characterized in that: The preparation method comprises the steps of loading the active component cobalt phthalocyanine on the surface of a molecular sieve carrier modified with a silane coupling agent; S1: activating the surface of the molecular sieve with hydroxyl groups to obtain an activated molecular sieve; S2: Modifying the activated molecular sieve obtained in step S1 with a silane coupling agent to obtain a silane coupling agent-modified molecular sieve; S3: mixing the molecular sieve modified with the silane coupling agent obtained in step S2 with cobalt phthalocyanine, filtering, washing, and calcining at low temperature to obtain the high-efficiency catalytic oxidation desulfurization agent; The silane coupling agent is one of 3-hydroxy-propyltrimethoxysilane, ethanoltriethoxysilane, acetoxytrimethoxysilane and vinyltrimethoxysilane.

5. The preparation method according to claim 4, characterized in that In the step S1, the hydroxyl activation treatment includes soaking the molecular sieve in a NaOH aqueous solution.

6. The preparation method according to claim 5, characterized in that The soaking time is 5 h to 24 h, and / or the concentration of the NaOH aqueous solution is 0.05 to 0.5 mol / L.

7. The preparation method according to claim 4, characterized in that In step S2, the silane coupling agent modification treatment includes immersing the activated molecular sieve in a silane coupling agent solution, adjusting the solution pH to 3.5-5.5, continuously stirring at 100° C. in a N2 atmosphere, and then cooling, washing with deionized water, and drying; And / or, the solvent in the silane coupling agent solution includes one of pure water, ethanol, benzene and toluene, And / or, the concentration of the silane coupling agent solution is 0.1-1.0 wt %.

8. The preparation method according to any one of claims 4 to 7, characterized in that In the step S3, the cobalt phthalocyanine is added in the form of a cobalt phthalocyanine solution.

9. The preparation method according to claim 8, characterized in that The solubility of the cobalt phthalocyanine solution is 1 mmol / L-100 mmol / L; and / or the mixing method uses ultrasonic impregnation to impregnate the modified molecular sieve into the cobalt phthalocyanine solution.

10. The preparation method according to claim 9, characterized in that The ultrasonic frequency range is 2×10 4 ~10 10 HZ, the reaction temperature is 30-120° C., the stirring rate is 100-1000 r / min, and the reaction time is 0.1 h-1 h; and / or the solvent in the cobalt phthalocyanine solution is one of DMF, DMSO, dichloromethane, acetone or sulfolane.

11. Use of the high-efficiency catalytic oxidation desulfurizer for sulfur-containing waste gas according to any one of claims 1 to 3 or the high-efficiency catalytic oxidation desulfurizer for sulfur-containing waste gas prepared by the preparation method according to any one of claims 4 to 10 in the field of sulfur-containing waste gas desulfurization.

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