A honeycomb-shaped homogeneous desulfurizer and a method for preparing the same

Abstract

The present application relates to a kind of honeycomb type homogeneous desulfurizer, which is prepared from the following raw materials in the following mass ratio: 10-50% of attapulgite clay, 1-15% of lubricant, 1-10% of pore-forming agent, 5-30% of binder, 1-20% of non-noble metal oxide and 30-70% of deionized water. The preparation method comprises the following steps: mixing the powdered attapulgite clay, lubricant, pore-forming agent, binder and deionized water according to the proposed ratio, then kneading for a certain period of time, repeatedly pugging in a vacuum pug mill to form a rubber-like clay body, then aging the clay body at room temperature in a sealed environment, extruding the aged clay body using an extruder with a honeycomb mold to obtain a honeycomb-shaped body, drying at room temperature and then calcining to obtain the final honeycomb type VOCs homogeneous desulfurizer. The present application can solve the problem that general adsorbents have strong adsorption performance for VOCs but poor desorption performance at normal temperature and pressure, and the chemical properties of the component materials are not active and non-flammable, so the present application is safe to use.

Description

Technical Field

[0001] This invention relates to a honeycomb homogeneous desulfurizing agent and its preparation method. Specifically, it relates to a homogeneous desulfurizing agent and its preparation method used for homogeneous pretreatment and desulfurization of sulfur-containing waste gas with large fluctuations in VOCs concentration, and is used in the field of waste gas treatment. Background Technology

[0002] In the treatment of VOCs-containing waste gas, situations often arise where VOCs concentrations fluctuate significantly and sulfides are present, such as exhaust gas from tank roofs in tank farms and gaseous exhaust gas from wastewater ponds. For such waste gases, it is generally necessary to first remove the sulfides, then stabilize the VOCs concentration, and finally carry out in-depth treatment.

[0003] Currently, the main technologies for controlling sulfur-containing gases researched both domestically and internationally include adsorption, biological methods, and the use of homogenization desulfurization equipment. Adsorption methods purify VOCs gases with high sulfur content by adsorbing them with adsorbents. However, the adsorption effect of treating high-sulfur VOCs gases using adsorption methods is determined by factors such as the properties of the adsorbent and the operating temperature, humidity, and pressure of the adsorption system. According to literature reports, common adsorbents include activated carbon, molecular sieves, MOFs, zeolite silica gel, and polymer adsorption resins. In practical industrial applications, activated carbon adsorption is currently the most widely used adsorption technology. However, activated carbon has disadvantages such as flammability and explosiveness during high-temperature desorption, poor safety, and competitive adsorption of high-sulfur VOCs gases, resulting in poor selectivity, easy saturation, and limited adsorption capacity for organic sulfur gases in VOCs.

[0004] In addition, as a homogenization method, a homogenizing tank is usually added at the front end of the treatment process to homogenize the concentration of VOCs in the waste gas. Homogenizing agents typically use adsorbents such as columnar activated carbon or spherical alumina. Adsorbents undergo two processes in their action on waste gas: adsorption and desorption. Generally, adsorbents are more effective at adsorbing high-concentration waste gas than low-concentration waste gas. When an adsorbent adsorbs high-concentration waste gas, its saturation is relatively high. When treating low-concentration waste gas, the adsorbent will desorb the previously adsorbed high-concentration waste gas. Homogenizing agents utilize this characteristic of adsorbents to homogenize the concentration. For an adsorbent to be used as a homogenizing agent, it not only needs a high adsorption capacity for VOCs in the waste gas, but also needs to ensure that the adsorbed VOCs are easily desorbed into the low-concentration waste gas.

[0005] In typical treatment processes, adsorption-desorption occurs solely based on the concentration of the waste gas itself, placing certain requirements on the pore structure of the adsorbent. Typically, the diameter of VOC molecules is [missing information]. such as benzene Toluene xylene ethanol Cyclohexane chloroform Micropores and mesopores with pore sizes 3 to 5 times the molecular diameter of the adsorbent can effectively adsorb VOCs. However, this pore size has an overly strong binding effect on VOCs, hindering the diffusion of adsorbed VOCs into low-concentration gases, thus making it unsuitable as a homogenizer. To meet the requirements for homogenizer use, the adsorbent should primarily employ mesopores for VOCs adsorption, with the optimal pore size being 10 to 15 times the diameter of the VOC molecules. Adsorbents with this pore structure can adsorb VOCs in high-concentration waste gas and desorb the adsorbed VOCs in low-concentration waste gas, exhibiting excellent homogenization effects.

[0006] At the same time, since the homogenizer will come into contact with extremely high concentrations of VOCs-containing waste gas, the homogenizer itself must be chemically inert, not react with VOCs, and certainly not undergo combustion.

[0007] CN202210358673.9 introduces a composite oxidizing granular filter media and its preparation method, which relates to the field of filter media technology and solves the technical shortcomings of existing filter media such as low oxidant loading capacity, easy clogging of adsorbent and granular filter media pores, and lack of adjuvants.

[0008] CN202210475817.9 introduces a waste gas treatment filter material, its preparation method and application, which relates to the field of air purification and treatment technology, and solves the technical shortcomings of existing filter materials, such as easy collapse after use, easy clogging of adsorption sites, poor filtration effect and high use cost.

[0009] The study "Research on Catalytic Combustion Degradation of Hydrocarbon-Containing Waste Gas from Petrochemical Wastewater Treatment Plants" (Modern Chemical Industry, 2005(05)) proposed using activated carbon as a homogenizer to regulate hydrocarbon-containing waste gas from petrochemical wastewater treatment plants.

[0010] CN105413446A describes a solid desulfurizing agent. This solid desulfurizing agent comprises the following components in parts by weight: 3-9 parts calcium oxide; 5-16 parts ferric oxide; 5-10 parts calcium fluoride; 1-6 parts aluminum oxide; 2-8 parts sodium bicarbonate; and 7-16 parts a neodymium-containing coordination polymer. By adding a novel neodymium-containing coordination polymer, the solid desulfurizing agent of this invention exhibits better desulfurization effect and higher sulfur capacity compared to commonly available solid desulfurizing agents. However, this desulfurizing agent does not mention its homogenizing effect on VOCs.

[0011] CN107866198A describes a method for preparing a solid desulfurizing agent. Using attapulgite as raw material, the agent undergoes alkali modification and activation treatment, followed by drying, grinding, sieving, granulation, and further calcination and activation. Finally, it is sieved into spherical attapulgite desulfurizing agent products. The attapulgite desulfurizing agent of this invention exhibits good alkali modification, with rough and hard spherical particles that are not easily broken. It has a large specific surface area, high porosity, good sulfur dioxide adsorption performance, is easy to regenerate, has a simple production process, and is low in cost. It can replace activated carbon (coke) for flue gas desulfurization, significantly reducing the operating cost of dry desulfurization methods. It can also be used in wastewater treatment and other applications. This desulfurizing agent does not mention its homogenizing effect on VOCs, and it employs physical adsorption for desulfurization. Therefore, the desulfurization effect is greatly affected by ambient temperature and gas moisture content.

[0012] The homogenizers and desulfurizers mentioned in the above reports all employ chemical methods to modify their adsorption surfaces, improving their adsorption performance and stability. However, they do not mention the control of their desorption capacity and pore size. Although these adsorbents have a good capture effect on various VOCs during the adsorption process, the adsorbed VOCs are difficult to desorb at room temperature and pressure, making them unsuitable for use as homogenizers. Moreover, none of them simultaneously possess both homogenizing and desulfurizing functions.

[0013] Therefore, there is a need for an adsorbent with excellent VOCs adsorption and desorption performance at room temperature and pressure. This adsorbent should be able to efficiently adsorb VOCs in high-concentration waste gas and promptly release adsorbed VOCs in low-concentration waste gas, forming an effective adsorption-desorption cycle that continuously changes with the VOCs concentration in the waste gas. This would act as a homogenizing pretreatment, smoothing out peaks and filling valleys in the VOCs concentration in the waste gas. Simultaneously, it should effectively remove sulfides from the waste gas. Finally, its constituent materials should be chemically inert and non-flammable. Summary of the Invention

[0014] The technical problem to be solved by this invention is that general adsorbents have poor desorption performance for VOCs at normal temperature and pressure. At the same time, it can remove sulfides from waste gas. Finally, the chemical properties of its components are inactive, non-flammable, and have high safety in use.

[0015] The honeycomb homogeneous desulfurizing agent of this invention is prepared from the following raw materials in the following mass ratio:

[0016] Attapulgite clay 10-50%, lubricant 1-15%, pore-forming agent 1-10%, binder 5-30%, non-precious metal oxides 1-20%, deionized water 30-70%.

[0017] The preferred mass ratio of the aforementioned raw materials is:

[0018] Attapulgite clay 25-35%, lubricant 3-5%, pore-forming agent 2-4%, binder 5-10%, non-precious metal oxides 5-10%, deionized water 40-60%.

[0019] The attapulgite clay is in powder form. The applicant has found through research that a suitable particle size range can better crosslink with the binder and non-precious metal oxides to form the required clay body. After a large number of experiments, the particle size range of the attapulgite clay was determined to be 0.1 to 100 μm, preferably 0.5 to 20 μm.

[0020] The lubricant is a machine oil or edible oil with lubricating properties, selected from one or more of glycerin, automotive engine oil, and edible oil, with glycerin being preferred.

[0021] The binder is one or more of silica sol, alumina sol, starch, hydroxymethyl cellulose, and polyvinyl alcohol, preferably one or more of silica sol, alumina sol, and hydroxymethyl cellulose. These binders can better crosslink attapulgite clay powder and non-precious metal oxides to form the desired clay model.

[0022] The pore-forming agent is one or more of glucose, polyethylene glycol, and waterborne polyurethane resin. Since glucose is easily decomposed by heat and releases a large amount of carbon dioxide, it forms pores during the drying process of the honeycomb preform and has excellent pore-forming performance. Therefore, glucose is preferred as the pore-forming agent.

[0023] The non-precious metal oxide is one or more of zinc oxide, iron oxide, copper oxide, and calcium oxide, with a particle size ranging from 0.1 to 100 μm, preferably from 0.5 to 20 μm, to better crosslink with the binder.

[0024] The preparation method of the honeycomb homogeneous desulfurizer of the present invention includes the following steps:

[0025] 1. Mix powdered attapulgite clay, lubricant, pore-forming agent, binder, non-precious metal oxide, and deionized water, and then place them in a kneader for kneading.

[0026] 2. Add the mixture obtained after kneading in step 1) into a vacuum plywood machine and knead it repeatedly until a clay model is formed.

[0027] 3. Seal the clay model obtained in step 2) at room temperature and allow it to age in an airtight environment;

[0028] 4. The aged clay model from step 3) is extruded using an extruder equipped with a honeycomb mold to obtain a honeycomb-shaped blank;

[0029] 5. The honeycomb-shaped embryo obtained in step 4) is first dried at room temperature, and then further dried.

[0030] 6. The dried honeycomb material from step 5) is calcined to obtain the integral honeycomb homogeneous desulfurizer.

[0031] To ensure the uniformity of the mud and prevent changes in composition due to excessive time, the kneading time in step 1) is 0.5 to 24 hours, preferably 2 to 6 hours; the number of times the mud is kneaded is repeated is 2 to 15 times, preferably 5 to 10 times.

[0032] The aging time in step 3) is 1 to 48 hours, preferably 6 to 12 hours.

[0033] To ensure the formation of the clay honeycomb without causing deformation due to excessive pressure, the extrusion pressure in step 4) is 0.5–20 MPa, preferably 2–5 MPa.

[0034] In step 5), the air-drying time is 1 to 48 hours, preferably 12 to 24 hours, the drying temperature is 60 to 200°C, preferably 80 to 120°C, and the drying time is 1 to 24 hours, preferably 2 to 6 hours.

[0035] The applicant found through research that if the baking temperature is too low or the baking time is too short, the strength of the honeycomb finished product will be insufficient, and if the baking temperature is too high or the baking time is too long, the honeycomb finished product will easily crack. Based on a large number of studies and experiments, the baking temperature in step 6) is limited to 400-800℃, preferably 500-600℃, and the baking time is 2-24h, preferably 4-6h.

[0036] The technical effects of this invention are as follows:

[0037] This invention provides a homogenizer with excellent VOCs adsorption and desorption performance at room temperature and pressure. It can efficiently adsorb VOCs in high-concentration waste gas and promptly release adsorbed VOCs in low-concentration waste gas, forming an effective adsorption-desorption cycle that continuously changes with the VOCs concentration in the waste gas. This homogenization pretreatment effectively "smooths out peaks and fills valleys" in the VOCs concentration of the waste gas. Simultaneously, it can effectively remove sulfides from the waste gas. Finally, its component materials are chemically inert and non-flammable. Attached Figure Description

[0038] Figure 1 This is a pore size distribution diagram of Embodiment 1 of the present invention;

[0039] Figure 2 This is a pore size distribution diagram of Embodiment 2 of the present invention;

[0040] Figure 3 This is a pore size distribution diagram of Embodiment 3 of the present invention;

[0041] Figure 4 This is a pore size distribution diagram of Embodiment 4 of the present invention;

[0042] Figure 5 This is a pore size distribution diagram of Embodiment 5 of the present invention;

[0043] Figure 6 This is a pore size distribution diagram of Embodiment 6 of the present invention;

[0044] Figure 7 This is a pore size distribution diagram of Embodiment 7 of the present invention;

[0045] Figure 8 This is a pore size distribution diagram of Embodiment 8 of the present invention;

[0046] Figure 9 This is a pore size distribution diagram of Embodiment 9 of the present invention;

[0047] Figure 10 This is a pore size distribution diagram of Embodiment 10 of the present invention;

[0048] Figure 11 This is a diagram showing the aperture distribution of Comparative Example 1;

[0049] Figure 12 This is a diagram showing the aperture distribution of Comparative Example 2. Detailed Implementation

[0050] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are only for illustrating the present invention and should not be regarded as limiting the scope of the present invention.

[0051] The present invention will be further described in detail below with reference to the embodiments, but the present invention is not limited to these embodiments.

[0052] Example 1

[0053] 1. Mix 35g (35% wt) powdered attapulgite clay (particle size range 2-10 μm), 5g (5% wt) glycerol, 4g (4% wt) glucose, 3g (3% wt) aluminum sol, 3g (3% wt) silica sol, 4g (4% wt) hydroxymethyl cellulose, 2g (2% wt) zinc oxide, 2g iron oxide (2% wt), 1g copper oxide (1% wt), 1g calcium oxide (1% wt), and 40g (40% wt) deionized water and knead in a kneader for 4 hours.

[0054] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 8 times to form a clay-like model;

[0055] 3. The prepared clay model is aged in a sealed container at room temperature for 9 hours in an airtight environment;

[0056] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 4 MPa to obtain a honeycomb-shaped preform.

[0057] As long as the required extrusion pressure can be achieved, other types of extruders can also be used, and the extrusion direction can also be transverse.

[0058] 5. Dry at room temperature for 12 hours, then dry at 150℃ for 4 hours;

[0059] 6. The dried honeycomb material was calcined at 500℃ for 5 hours to finally obtain the integral honeycomb homogeneous desulfurizer, numbered 1-1.

[0060] Example 2

[0061] 1. Mix 30g (30% wt) powdered attapulgite clay (particle size range 2-10 μm), 3g (3% wt) glycerol, 2g (2% wt) glucose, 2g (2% wt) aluminum sol, 2g (2% wt) silica sol, 1g (1% wt) hydroxymethyl cellulose, 2.5g (2.5% wt) zinc oxide, 2.5g iron oxide (2.5% wt), 2.5g copper oxide (2.5% wt), 2.5g calcium oxide (2.5% wt), and 50g (50% wt) deionized water and knead in a kneader for 4 hours.

[0062] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 8 times to form a clay-like model;

[0063] 3. The prepared clay model is aged in a sealed container at room temperature for 9 hours in an airtight environment;

[0064] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 4 MPa to obtain a honeycomb-shaped preform.

[0065] 5. Dry at room temperature for 12 hours, then dry at 150℃ for 4 hours;

[0066] 6. The dried honeycomb material was calcined at 500℃ for 5 hours to finally obtain the integral honeycomb homogeneous desulfurizer, numbered 1-2.

[0067] Example 3

[0068] 1. Mix 30g (30% wt) powdered attapulgite clay (particle size range 2-10 μm), 4g (4% wt) glycerol, 3g (3% wt) glucose, 2g (2% wt) aluminum sol, 2g (2% wt) silica sol, 2g (2% wt) hydroxymethyl cellulose, 2g (2% wt) zinc oxide, 2g iron oxide (2% wt), 2g copper oxide (2% wt), 1g calcium oxide (1% wt), and 50g (50% wt) deionized water and knead in a kneader for 4 hours.

[0069] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 8 times to form a clay-like model;

[0070] 3. The prepared clay model is aged in a sealed container at room temperature for 9 hours in an airtight environment;

[0071] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 4 MPa to obtain a honeycomb-shaped preform.

[0072] 5. Dry at room temperature for 12 hours, then dry at 150℃ for 4 hours;

[0073] 6. The dried honeycomb material was calcined at 500℃ for 5 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-3.

[0074] Example 4

[0075] 1. Mix 30g (30% wt) powdered attapulgite clay (particle size range 2-10 μm), 4g (4% wt) glycerol, 3g (3% wt) glucose, 3g (3% wt) aluminum sol, 3g (3% wt) silica sol, 3g (3% wt) zinc oxide, 2g iron oxide (2% wt), 2g copper oxide (2% wt), and 50g (50% wt) deionized water and knead in a kneader for 4 hours.

[0076] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 8 times to form a clay-like model;

[0077] 3. The prepared clay model is aged in a sealed container at room temperature for 9 hours in an airtight environment;

[0078] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 4 MPa to obtain a honeycomb-shaped preform.

[0079] 5. Dry at room temperature for 12 hours, then dry at 150℃ for 4 hours;

[0080] 6. The dried honeycomb material was calcined at 500℃ for 5 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-4.

[0081] Example 5

[0082] 1. Mix 30g (30% wt) powdered attapulgite clay (particle size range 2-10 μm), 4g (4% wt) glycerol, 3g (3% wt) glucose, 6g (6% wt) aluminum sol, 7g (7% wt) zinc oxide, and 50g (50% wt) deionized water in a kneader and knead for 4 hours.

[0083] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 8 times to form a clay-like model;

[0084] 3. The prepared clay model is aged in a sealed container at room temperature for 9 hours in an airtight environment;

[0085] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 4 MPa to obtain a honeycomb-shaped preform.

[0086] 5. Dry at room temperature for 12 hours, then dry at 150℃ for 4 hours;

[0087] 6. The dried honeycomb material was calcined at 500℃ for 5 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-5.

[0088] Example 6

[0089] 1. Combine 10g (10% wt) powdered attapulgite clay (particle size range 20–100 μm), 0.5g (0.5% wt) glycerin, 0.25g (0.25% wt) Mobil 5W-30 engine oil, 0.25g (0.25% wt) rapeseed oil, 0.5g (0.5% wt) glucose, 0.25g (0.25% wt) polyethylene glycol, and 0.25g (0.25% wt) water-based... Polyurethane resin, 1g (1% wt) silica sol, 1g (1% wt) aluminum sol, 1g (1% wt) starch, 1g (1% wt) hydroxymethyl cellulose, 1g (1% wt) polyvinyl alcohol, 5g zinc oxide (5% wt), 3g iron oxide (3% wt), 3g copper oxide (3% wt), 2g calcium oxide (2% wt), and 70g (70% wt) deionized water were mixed and kneaded in a kneader for 0.5h.

[0090] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process twice to form a clay-like model;

[0091] 3. The prepared clay model is aged in a sealed container at room temperature for 1 hour in the absence of air;

[0092] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 0.5 MPa to obtain a honeycomb-shaped preform;

[0093] 5. Dry at room temperature for 48 hours, then dry at 60℃ for 24 hours;

[0094] 6. The dried honeycomb material was calcined at 400℃ for 24 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-6.

[0095] Example 7

[0096] 1. Combine 50g (50% wt) powdered attapulgite clay (particle size range 20–100 μm), 1g (1% wt) glycerin, 1g (1% wt) Mobil 5W-30 engine oil, 1g (1% wt) rapeseed oil, 5g (3% wt) glucose, 2.5g (2.5% wt) polyethylene glycol, 2.5g (2.5% wt) waterborne polyurethane resin, 1g (1% wt) silica sol, and 1g (1% wt) [unclear text - possibly a typo]. 1g (wt) aluminum sol, 1g (1%wt) starch, 1g (1%wt) hydroxymethyl cellulose, 1g (1%wt) polyvinyl alcohol, 0.25g zinc oxide (0.25%wt), 0.25g iron oxide (0.25%wt), 0.25g copper oxide (0.25%wt), 0.25g calcium oxide (0.25%wt), and 30g (30%wt) deionized water were mixed and kneaded in a kneader for 24 hours.

[0097] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 15 times to form a clay-like model;

[0098] 3. The prepared clay model is aged in a sealed container at room temperature for 48 hours in an airtight environment;

[0099] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 20 MPa to obtain a honeycomb-shaped preform;

[0100] 5. Dry at room temperature for 48 hours, then dry at 200℃ for 1 hour;

[0101] 6. The dried honeycomb material was calcined at 800℃ for 2 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-7.

[0102] Example 8

[0103] 1. Mix 10g (10% wt) powdered attapulgite clay (particle size range 20-100 μm), 5g (5% wt) glycerol, 5g (5% wt) glucose, 6g (6% wt) silica sol, 6g (6% wt) aluminum sol, 6g (6% wt) starch, 6g (6% wt) hydroxymethyl cellulose, 6g (6% wt) polyvinyl alcohol, 5g zinc oxide (5% wt), 5g iron oxide (5% wt), 5g copper oxide (5% wt), 5g calcium oxide (5% wt), and 30g (30% wt) deionized water and knead in a kneader for 2 hours.

[0104] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 5 times to form a clay-like model;

[0105] 3. The prepared clay model is aged in a sealed container at room temperature for 6 hours in an airtight environment;

[0106] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 2 MPa to obtain a honeycomb-shaped preform;

[0107] 5. Dry at room temperature for 12 hours, then dry at 80℃ for 6 hours;

[0108] 6. The dried honeycomb material was calcined at 500℃ for 4 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-8.

[0109] Example 9

[0110] 1. Mix 10g (10% wt) powdered attapulgite clay (particle size range 20-100 μm), 15g (15% wt) glycerol, 10g (10% wt) glucose, 5g (5% wt) silica sol, 2.5g (2.5% wt) aluminum sol, 2.5g (2.5% wt) hydroxymethyl cellulose, 15g zinc oxide (15% wt), and 40g (40% wt) deionized water and knead in a kneader for 6 hours.

[0111] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 10 times to form a clay-like model;

[0112] 3. The prepared clay model is aged in a sealed container at room temperature for 12 hours in an airtight environment;

[0113] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 5 MPa to obtain a honeycomb-shaped preform.

[0114] 5. Dry at room temperature for 24 hours, then dry at 200℃ for 2 hours;

[0115] 6. The dried honeycomb material was calcined at 600℃ for 4 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-9.

[0116] Example 10

[0117] 1. Mix 25g (25% wt) powdered attapulgite clay (particle size range 2-10 μm), 3g (3% wt) glycerol, 2g (2% wt) glucose, 2g (2% wt) aluminum sol, 2g (2% wt) silica sol, 1g (1% wt) hydroxymethyl cellulose, 2g (2% wt) zinc oxide, 1g iron oxide (1% wt), 1g copper oxide (1% wt), 1g calcium oxide (1% wt), and 60g (60% wt) deionized water and knead in a kneader for 4 hours.

[0118] 2. Then add the mixture to a vacuum plywood machine and repeat the plywood process 8 times to form a clay-like model;

[0119] 3. The prepared clay model is aged in a sealed container at room temperature for 9 hours in an airtight environment;

[0120] 4. The aged clay model is extruded using a hydraulic vertical extruder with a honeycomb mold at a pressure of 4 MPa to obtain a honeycomb-shaped preform.

[0121] 5. Dry at room temperature for 12 hours, then dry at 150℃ for 4 hours;

[0122] 6. The dried honeycomb material was calcined at 500℃ for 5 hours to finally obtain the integral honeycomb homogeneous desulfurizing agent, numbered 1-10.

[0123] Comparative Example 1

[0124] The method in Example 2 uses activated carbon powder instead of attapulgite clay, with the other steps remaining unchanged. This is Comparative Example 1, numbered 2-1.

[0125] Comparative Example 2

[0126] The method in Example 2 is followed without adding a pore-forming agent, and the remaining steps remain unchanged. This is Comparative Example 2, numbered 2-2.

[0127] This invention provides a homogenizer with excellent VOCs adsorption and desorption performance at room temperature and pressure. It can efficiently adsorb VOCs in high-concentration waste gas and promptly release adsorbed VOCs in low-concentration waste gas, forming an effective adsorption-desorption cycle that continuously changes with the VOCs concentration in the waste gas. This homogenization pretreatment effectively "smooths out peaks and fills valleys" in the VOCs concentration of the waste gas. Simultaneously, it can effectively remove sulfides from the waste gas. Finally, its component materials are chemically inert and non-flammable.

[0128] Evaluation and Comparison Test

[0129] (I) Basic Performance Testing

[0130] The specific surface area and pore volume of each homogenizer were measured using an ASAP 2020HD88 fully automatic gas adsorption instrument, and the strength of each homogenizing desulfurizer was determined using a KD3 particle strength analyzer. The results are shown in Table 1.

[0131] Table 1. Measurement results of homogenizer strength, specific surface area, and pore volume.

[0132] Protective agent number Initial strength, N / cm Specific surface area, m2 / g Pore ​​volume, cm3 / g 1-1 269 244 0.65 1-2 259 245 0.66 1-3 266 244 0.63 1-4 263 243 0.64 1-5 266 239 0.67 1-6 241 203 0.65 1-7 255 176 0.58 1-8 235 199 0.6 1-9 232 188 0.59 1-10 266 220 0.59 2-1 252 630 0.37 2-2 269 114 0.24

[0133] The homogeneous desulfurizers 1-1 to 1-10 prepared by the present invention are comparable in strength to the homogeneous desulfurizer 2-1 used for comparison. 2-1 has a significant advantage in specific surface area. However, 1-1 to 1-10 has a much larger pore volume than 2-1, indicating that the homogeneous desulfurizers prepared by the present invention are mainly mesoporous, while 2-1 is mainly microporous.

[0134] The homogeneous desulfurizing agents 1-1 to 1-10 prepared using the present invention are superior to the comparative homogeneous agent 2-2 in terms of specific surface area and strength, and the pore volume of 1-1 to 1-10 is much greater than that of 2-2.

[0135] The homogeneous desulfurizing agents 1-1 to 1-10 prepared using this invention are comparable in strength to the homogeneous desulfurizing agent 2-1 used for comparison. While 2-1 shows a significant advantage in specific surface area, the pore volume of 1-1 to 1-10 is much larger than that of 2-1. This indicates that the homogeneous agents prepared by the method of this patent are predominantly mesoporous, while 2-1 is predominantly microporous. This difference is evident from… Figures 1-10 The pore size distribution characterization shows that the homogenizer prepared by the method of this patent has a pore size of... The 2-1 pore size distribution used for comparison is mostly in... the following.

[0136] The homogeneous desulfurizing agents 1-1 to 1-10 prepared using this invention have comparable strength to the comparative homogeneous desulfurizing agent 2-2. However, the specific surface area and pore volume of 1-1 to 1-10 are significantly greater than those of 2-2. This indicates that the homogeneous agents prepared by the method of this patent are mainly mesoporous, while 2-2 does not contain any pore-forming agent. This difference is evident from... Figures 1-12 The pore size distribution characterization shows that the homogenizer prepared by the method of this patent has a pore size of... The 2-2 pore size distribution used for comparison is mostly in... the following.

[0137] (II) Stability Performance Test

[0138] The changes in the strength, pore volume, and specific surface area of ​​the homogenizer were investigated by a high-temperature (air-ventilated) stability test at 600℃. The results are shown in Table 2.

[0139] Test conditions: A certain amount of homogenizer was placed in a muffle furnace, and a certain amount of air was introduced into the muffle furnace. The test time was 12 hours. After cooling to room temperature, the changes in the homogenizer strength, specific surface area and pore volume were measured.

[0140] Table 2. Comparison of the stability of homogeneous desulfurizers

[0141]

[0142]

[0143] As can be seen from Table 2, the homogeneous desulfurizer prepared by this method has better stability than comparative examples 2-1 and 2-2.

[0144] (III) Desulfurization effect test

[0145] The desulfurization effect of homogeneous desulfurizing agents 1-1 to 1-5, 2-1, and 2-2 was tested. (See attached...) Figure 1 In the test procedure shown, the air in the cylinder is divided into two paths. One path enters the bubbling tank, which carries the methanethiol into the mixing tank and mixes it with the air that has not passed through the bubbling tank. The mixed gas passes through the homogenizing desulfurizer and then enters the chromatograph to measure the content of methanethiol.

[0146] The test conditions were: ambient temperature and pressure, air velocity 1000 h⁻¹. -1 The concentration of methanethiol in the gas mixture is 500 mg / m³. 3 The test results are shown in Table 3.

[0147] Table 3 Comparison of desulfurization effects of homogeneous desulfurizing agents

[0148]

[0149] As can be seen from Table 3, the homogeneous desulfurizer prepared by this method has a good effect on the removal of sulfides and can maintain long-term desulfurization stability, while comparative examples 2-1 and 2-2 cannot maintain long-term desulfurization performance.

Claims

1. A honeycomb homogeneous desulfurizing agent, characterized in that... It is prepared from the following raw materials in the following mass ratio: Attapulgite clay 10-50%, lubricant 1-15%, pore-forming agent 1-10%, binder 5-30%, non-precious metal oxides 1-20%, deionized water 30-70%.

2. The honeycomb homogeneous desulfurizer as described in claim 1, characterized in that... The mass ratio of each raw material is as follows: Attapulgite clay 25-35%, lubricant 3-5%, pore-forming agent 2-4%, binder 5-10%, non-precious metal oxides 5-10%, deionized water 40-60%.

3. The honeycomb homogeneous desulfurizer as described in claim 1 or 2, characterized in that... Attapulgite clay is in powder form, with a particle size range of 0.1–100 μm, preferably 0.5–20 μm.

4. The honeycomb homogeneous desulfurizer as described in claim 1 or 2, characterized in that... The lubricant is a machine oil or edible oil with lubricating properties, selected from one or more of glycerin, automotive engine oil, and edible oil, with glycerin being preferred.

5. The honeycomb homogeneous desulfurizer as described in claim 1 or 2, characterized in that... The binder is one or more of silica sol, aluminum sol, starch, hydroxymethyl cellulose, and polyvinyl alcohol, preferably one or more of silica sol, aluminum sol, and hydroxymethyl cellulose.

6. The honeycomb homogeneous desulfurizer as described in claim 1 or 2, characterized in that... The pore-forming agent is one or more of glucose, polyethylene glycol, and water-based polyurethane resin, with glucose being preferred.

7. The honeycomb homogeneous desulfurizer as described in claim 1 or 2, characterized in that... The non-precious metal oxide is one or more of zinc oxide, iron oxide, copper oxide and calcium oxide, with a particle size range of 0.1 to 100 μm, preferably 0.5 to 20 μm.

8. The method for preparing the honeycomb homogeneous desulfurizing agent according to any one of claims 1 to 7, characterized in that... The preparation steps include the following: 1) Mix powdered attapulgite clay, lubricant, pore-forming agent, binder, non-precious metal oxide and deionized water and place them in a kneader for kneading. 2) Add the mixture obtained after kneading in step 1) into a vacuum plywood machine and knead it repeatedly until a clay-like model is formed; 3) Seal the clay model obtained in step 2) at room temperature to allow it to age in an airtight environment; 4) The aged clay model from step 3) is extruded using an extruder with a honeycomb mold to obtain a honeycomb-shaped embryo. 5) The honeycomb-shaped embryo obtained in step 4) is first air-dried at room temperature, and then dried. 6) The dried honeycomb preform from step 5) is calcined to obtain a honeycomb homogeneous desulfurizer.

9. The preparation method of the honeycomb homogeneous desulfurizing agent as described in claim 8, characterized in that... The kneading process in step 1) takes 0.5 to 24 hours, preferably 2 to 6 hours.

10. The preparation method of the honeycomb homogeneous desulfurizing agent as described in claim 8, characterized in that... In step 2), the number of times the mud is kneaded is repeated is 2 to 15 times, preferably 5 to 10 times.

11. The preparation method of the honeycomb homogeneous desulfurizing agent as described in claim 8, characterized in that... The aging time in step 3) is 1 to 48 hours, preferably 6 to 12 hours.

12. The method for preparing the honeycomb homogeneous desulfurizing agent as described in claim 8, characterized in that... The extrusion pressure in step 4) is 0.5 to 20 MPa, preferably 2 to 5 MPa.

13. The preparation method of the honeycomb homogeneous desulfurizing agent as described in claim 8, characterized in that... In step 5), the air-drying time is 1 to 48 hours, preferably 12 to 24 hours, the drying temperature is 60 to 200°C, preferably 80 to 120°C, and the drying time is 1 to 24 hours, preferably 2 to 6 hours.

14. The method for preparing the honeycomb homogeneous desulfurizing agent as described in claim 1, characterized in that... In step 6), the roasting temperature is 400–800℃, preferably 500–600℃, and the roasting time is 2–24h, preferably 4–6h.

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