Adsorbing material for gas desulfurization and preparation method thereof

Abstract

According to the adsorption material for gas desulfurization and the preparation method thereof, waste carbon powder and a carbon-containing enhancer are mixed and ground in advance, so that the balling performance of the waste carbon powder is improved, meanwhile, the use amount of an adhesive is reduced, the situation that the adsorption performance of a carbon-based adsorption material is affected by excessive adhesive proportion is avoided, and then high-value utilization of the waste carbon powder is achieved. Furthermore, ammonia gas is adopted to modify the thermal-state material, and abundant nitrogen-containing functional groups are introduced into the carbon-based material by accurately regulating and controlling the modification process, so that the surface adsorption sites of the carbon-based adsorption material are enhanced, and the sulfur selectivity and adsorbability of the carbon-based adsorption material are improved. The method has the advantages of easily available raw materials, short and easily controllable process, and easy industrial application. The obtained product is stable in quality, remarkable in adsorption and removal effect on hydrogen sulfide in gas, and remarkable in economic benefit, environmental benefit and social benefit.

Description

Technical Field

[0001] The present invention relates to gas purification materials, in particular to an adsorption material for gas desulfurization and a preparation method thereof, belonging to the technical field of carbon-based adsorption materials for gas desulfurization. Background Art

[0002] The "Opinions on Promoting the Implementation of Ultra-Low Emissions in the Steel Industry" jointly issued by the Ministry of Ecology and Environment and five other ministries and commissions clearly proposed that steel companies should strengthen source control and implement fine desulfurization of blast furnace gas. That is, the main sulfur-containing gases (COS and H2S) in blast furnace gas need to be treated at the source to ensure that the sulfur content in blast furnace gas is effectively controlled and the end-of-pipe desulfurization cost is reduced to meet the energy conservation, emission reduction and low-carbon consumption reduction needs of steel companies.

[0003] Carbon-based adsorbent materials, due to their high specific surface area and rich pore structure, have excellent adsorption and removal properties for H2S gas. Currently, commercially available carbon-based hydrogen sulfide adsorbents primarily use raw coal as their raw material and undergo a series of processes, including grinding, forming, carbonization, activation, impregnation, and drying. Using raw coal directly as the raw material results in relatively high production costs, and the impregnation process is often extensive, making product performance difficult to control. The purification of industrial waste gas and wastewater generates a large amount of waste carbon powder for desulfurization and denitrification, or VOCs adsorption. Due to their poor pelletizing properties, these waste carbon powders can often only be incorporated into raw coal in small amounts to replace a portion of the raw coal for pelletizing. This results in low carbon powder utilization efficiency, with the majority of the carbon powder being used as fuel or directly incinerated, resulting in a relatively low utilization value. Furthermore, due to the large proportion of raw coal in carbon-based adsorbent materials containing a small amount of carbon powder, their desulfurization performance is not significantly improved compared to that of all-coal-based adsorbent materials. If the carbon powder is pelletized independently, a large amount of binder needs to be added, which is costly. In addition, the desulfurization performance of the resulting carbon-based adsorption material is relatively low due to the high proportion of binder in the material. Summary of the Invention

[0004] In response to the problems of low carbon powder utilization efficiency and low desulfurization performance of all-carbon powder-based adsorption materials in the prior art, the present invention provides an adsorption material for gas desulfurization and a preparation method thereof. By pre-grinding waste carbon powder with a carbon-containing enhancer, the pelletizing performance of the waste carbon powder is improved, while the amount of binder used is reduced to avoid excessive binder proportion affecting the adsorption performance of the carbon-based adsorption material, thereby achieving high-value utilization of waste carbon powder. Furthermore, ammonia is used to modify the hot material, thereby introducing rich nitrogen-containing functional groups into the carbon-based material, enhancing the surface adsorption sites of the carbon-based adsorption material, and improving the sulfur selectivity and adsorption of the carbon-based adsorption material. At the same time, by precisely controlling the modification process, the performance indicators of the carbon-based adsorption material are directionally controlled, significantly improving the overall performance of the product.

[0005] In order to achieve the above technical objectives, the technical solutions adopted by the present invention are specifically described as follows:

[0006] According to a first embodiment of the present invention, there is provided a method for preparing an adsorbent material for gas desulfurization:

[0007] A method for preparing an adsorption material for gas desulfurization, the method comprising the following steps:

[0008] 1) Ingredients: Grind the carbon powder and the carbon-containing reinforcing agent, and then mix them with a binder and water to obtain a mixture.

[0009] 2) Granulation: The mixture is kneaded, formed and dried to obtain raw granules.

[0010] 3) Heat treatment: The raw pellets are carbonized and / or activated to obtain hot materials.

[0011] 4) Modification: The hot material is brought into contact with the ammonia-containing mixed gas for modification. The introduction state of the ammonia-containing mixed gas is controlled according to the quality of the hot material and the target performance requirements of the adsorption material, thereby obtaining an adsorption material that meets the working conditions.

[0012] Preferably, in step 1), the carbon powder is one or more of desulfurization and denitrification waste carbon powder, VOCs adsorption waste carbon powder, and waste carbon powder generated during the production and transportation of activated carbon, preferably desulfurization and denitrification waste carbon powder and / or VOCs adsorption waste carbon powder.

[0013] Preferably, in step 1), the amount of the carbon powder is 55-85% of the total mass of the mixture, preferably 60-80%, more preferably 65-75%.

[0014] Preferably, in step 1), the carbon-containing enhancer is asphalt, coal-to-liquid liquefaction residue, or a mixture thereof. Preferably, the asphalt is one or more of coal tar pitch, petroleum pitch, and natural asphalt. The coal-to-liquid liquefaction residue is direct coal liquefaction residue (CLR), which is composed of unconverted coal organic matter, asphaltenes, pre-asphaltenes, inorganic minerals, and residual liquefaction catalyst from the coal-to-liquid process.

[0015] Preferably, in step 1), the amount of the carbon-containing reinforcing agent is 3-15% of the total mass of the mixture, preferably 5-12%, and more preferably 8-10%.

[0016] Preferably, in step 1), the binder is one or more of coal tar, carboxymethyl cellulose, polyvinyl alcohol, sesbania powder, starch, and resin, preferably starch.

[0017] Preferably, in step 1), the amount of the binder is 1-15% of the total mass of the mixture, preferably 2-12%, and more preferably 3-10%.

[0018] Preferably, in step 1), the amount of water used is 12-30% of the total mass of the mixture, preferably 14-28%, and more preferably 15-25%.

[0019] Preferably, in step 1), the particle size of the material after the carbon powder and the carbon-containing reinforcing agent are mixed and ground is such that more than 80% of the particle size passes through 200 mesh or more than 60% of the particle size passes through 325 mesh.

[0020] Preferably, in step 2), the raw pellets are in the form of spheres, cylinders, blocks, or honeycombs. The average particle size of the raw pellets is 3 to 15 mm, preferably 5 to 12 mm.

[0021] Preferably, in step 2), the drying temperature is 50-90° C., preferably 60-80° C. The drying time is such that the moisture content of the raw pellets is less than 10%, preferably less than 8%.

[0022] Preferably, in step 3), the carbonization is carried out at a temperature of 200-1000° C. (preferably 300-900° C.) for 15-180 min (preferably 30-150 min), and the final carbonization temperature is 600-900° C.

[0023] Preferably, in step 3), the activation is carried out at a temperature of 800-1000° C. (preferably 850-950° C.) for 30-1500 min (preferably 60-1200 min), and the activation medium is water vapor.

[0024] Preferably, in step 4), the ammonia-containing mixed gas is a mixed gas consisting of ammonia and a protective gas, wherein the protective gas is one or more of nitrogen, helium, neon, argon, xenon, and carbon dioxide.

[0025] Preferably, in step 4), the concentration of ammonia in the ammonia-containing mixed gas is 30-75 mg / L, preferably 40-70 mg / L, and more preferably 50-65 mg / L.

[0026] Preferably, in step 4), controlling the state of the ammonia-containing mixed gas according to the mass of the hot material and the target performance requirements of the adsorption material specifically includes controlling the amount of the ammonia-containing mixed gas according to the mass of the hot material and the target ammonia content of the adsorption material. The mass of the hot material, the target ammonia content of the adsorption material, and the amount of the ammonia-containing mixed gas satisfy the following formula:

[0027] (1);

[0028] In formula (1), Q is the target ammonia content of the adsorbent material, which is 1-4%, preferably 2-3% (of the mass ratio of the adsorbent material). a is the modification correction coefficient, which is 0.85-1.15. k is the adsorption constant of ammonia adsorbed by the carbon-based material, which is 0.01-0.1, L / mg. C0 is the initial ammonia concentration of the ammonia-containing mixed gas, mg / L. C1 is the real-time concentration of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material, mg / L. V is the amount of ammonia-containing mixed gas required to be introduced into the modification inlet, L (continuous introduction). m is the mass of the hot material, mg. T1 is the real-time temperature of the carbon-based material before modification, °C. T2 is the temperature of the carbon-based material after modification, °C. T3 is the temperature of the mixed gas before modification, °C. T4 is the temperature of the mixed gas after modification, °C.

[0029] Preferably, the adsorption material obtained in step 4) is cooled and sieved to obtain large-particle adsorption material, and the small-particle activated carbon obtained after cooling and sieving is returned to step 1) for reuse as carbon powder.

[0030] According to a second embodiment of the present invention, there is provided an adsorption material for gas desulfurization:

[0031] An adsorption material for gas desulfurization is prepared according to the method described in the first embodiment.

[0032] In the present invention, it is found through research that the desulfurization and denitrification waste carbon powder or VOCs adsorption waste carbon powder has undergone multiple pollutant adsorption and thermal regeneration, that is, multiple cycles of high temperature and acidic environment treatment, which leads to an increase in the number of functional groups and specific surface area inside the activated carbon. The corresponding waste activated carbon powder produced has surface functional groups and pore structure characteristics that are more superior than those of fresh carbon-based materials, and thus the adsorption catalytic performance is enhanced. In other words, the waste carbon powder itself has a relatively developed pore structure, a large specific surface area and a rich variety of surface functional groups, and already has a certain effect of adsorbing hydrogen sulfide gas. Therefore, using desulfurization and denitrification waste carbon powder or VOCs adsorption waste carbon powder as raw material can significantly reduce the raw material cost and turn waste into treasure compared to directly using raw coal as raw material. On the other hand, it can also make the resulting carbon-based adsorption material have relatively better morphological characteristics, and thus have better adsorption catalytic performance.

[0033] In the present invention, research has found that by adding a certain amount of carbon-containing strengthening agent (such as asphalt and / or coal-to-liquid liquefaction residue) to waste carbon powder and then grinding it, the waste carbon powder and the carbon-containing strengthening agent are uniformly mixed. The carbon-containing strengthening agent's wrapping and adhesion properties can significantly improve the pelletization of the waste carbon powder. Moreover, because the carbon-containing strengthening agent itself contains a large amount of carbon, it can also reduce the proportion of non-carbon elements compared to ordinary binders, thereby ensuring the strength of the carbon-based material and the uniform distribution of micro- and fine pores during subsequent heat treatment, thereby obtaining a carbon-based adsorbent with excellent adsorption properties. Using too much or too little carbon-containing strengthening agent is not conducive to forming a carbon-based adsorbent with the required morphological characteristics. When the amount of carbon-containing reinforcing agent is too low, the proportion of waste carbon powder in the mixture formed by it and waste carbon powder is too high, which leads to low ball-forming properties of the mixture. It is difficult to directly mix and knead the mixture into a shape, or the strength of the molded material obtained after forced molding is low, and it is easy to explode during heat treatment. Therefore, it is necessary to increase the amount of non-carbon binder used, which increases the cost and makes it difficult to obtain a larger proportion of micro- and fine pores after heat treatment. When the amount of carbon-containing reinforcing agent is too high, the proportion of waste carbon powder with better surface functional groups and pore structure characteristics will decrease, while the proportion of ordinary carbon elements will increase, which is not conducive to subsequent molding and granulation, nor is it conducive to ensuring the adsorption performance of the subsequent finished carbon-based adsorption material.

[0034] In the present invention, the materials (carbon powder, carbon-containing reinforcement, binder, water, etc.) are mixed using a high-pressure mixer, such as a vertical, horizontal, or angled mixer equipped with stirring blades. The high-pressure mixer offers better mixing efficiency and continuity than existing batch mixers and roller mixing and kneading equipment, resulting in a more uniform distribution of the mixed material components. The mixing and kneading of the solid waste carbon powder mixture (carbon powder + carbon-containing reinforcement), binder, and liquid water are more evenly mixed, further ensuring stable product performance. The ground mixed powder (carbon powder + carbon-containing reinforcement) and binder can be fed directly into the mixer separately or mixed together before simultaneously. Water can be added to the mixer by spraying or atomizing.

[0035] In the present invention, depending on the purpose of the carbon-based adsorbent material, the kneaded material is pressurized to form a carbon-based molding material of a certain shape. The molding material of a certain shape mentioned here refers to the appearance of the molding material, which can be spherical, cylindrical, block, honeycomb, etc., preferably cylindrical. For example, the size of a cylindrical molding material is generally 3~15mm (preferably 5~12mm). It should be noted that the molding material has a high moisture content and is relatively soft overall. During the carbonization process, it will affect the porosity and strength of the activated carbon, making the performance of the carbon-based material fail to meet the requirements. That is, the extruded molding material needs to be dried to a certain strength and a certain moisture content before heat treatment. For example, after the kneading molding process, the molding material needs to be further dried at 50~90℃ (preferably 60~80℃) to a moisture content of less than 10% (preferably less than 8%) to obtain a raw pellet that can be directly heat-treated.

[0036] In the present invention, the raw pellets are subjected to high-temperature heat treatment to achieve a melt-polycondensation reaction between the waste carbon powder and the carbon-containing strengthening agent at high temperature, forming a carbon-based material with a certain strength and a certain pore structure. It should be noted that the heat treatment process can be carbonization only, activation only, or a combination of carbonization and activation. If carbonization only is used, carbonization can be performed in a rotary carbonization furnace or a horizontal, translational, and electric-driven furnace. The carbonization process is controlled to have a temperature of 200-1000°C, a final carbonization temperature of 600-900°C (preferably 650-800°C), and a carbonization time of 15-180 minutes. If carbonization combined with activation is used, carbonization can be performed in a rotary carbonization furnace or a horizontal, translational, and electric-driven furnace. The carbonization process is controlled to have a temperature of 200-900°C, a final carbonization temperature of 600-850°C, and a carbonization time of 15-180 minutes. The activation process can be carried out in a vertical Slep furnace or a horizontal sliding pusher electric heating furnace. The activation process is controlled at an activation temperature of 800-1000°C, an activation time of 30-1440 minutes, and the activation medium is steam.

[0037] In the present invention, the carbon-based material in the initial cooling section after heat treatment generally still has a relatively high temperature and residual heat. During this process, an ammonia-containing mixed gas can be introduced to fully contact the carbon-based material, allowing the carbon-based material and ammonia to undergo a surface activation reaction at a relatively high temperature and introduce specific nitrogen-containing functional groups, thereby further enhancing the surface alkalinity of the carbon-based material and improving its selectivity for sulfur-containing gases. Research has found that during the modification process, when the amount of ammonia adsorbed in the carbon-based adsorbent material causes the nitrogen-containing functional groups to overload, the excess nitrogen-containing functional groups will occupy the micropore entrances or the interior of the pores, hindering the diffusion of gas molecules. At the same time, excessive alkalinity will reduce the adsorption efficiency of acidic gases (such as SO2). Excessive amino groups (-NH2) make the surface strongly alkaline, reacting rapidly with SO2 to form ammonium sulfate salts, but salt deposition blocks pores and inhibits subsequent reactions. In addition, the carbon skeleton structure on the surface of the over-modified carbon-based adsorbent material becomes fragile, and wear resistance may decrease. However, if the nitrogen functional group loading of carbon-based adsorption materials is too low, the adsorption capacity for polar or acidic gases (such as NOx and H2S) will be low, and efficient selective reaction for sulfur-containing gases will not be achieved.

[0038] In the present invention, when performing ammonia modification, it is necessary to control the state of the ammonia-containing mixed gas introduced according to the mass of the hot material and the target performance requirements of the adsorbent material, thereby obtaining an adsorbent material that meets the working conditions. Specifically, the amount of the ammonia-containing mixed gas introduced is controlled according to the mass of the hot material and the target ammonia content of the adsorbent material. The mass of the hot material, the target ammonia content of the adsorbent material, and the amount of the ammonia-containing mixed gas introduced satisfy the following formula:

[0039] (1)

[0040] In formula (1), Q is the target ammonia content of the adsorbent material, which is 1-4%, preferably 2-3% (based on the mass ratio of the adsorbent material). a is the modification correction coefficient, which is 0.85-1.15%. k is the adsorption constant of ammonia adsorbed by the carbon-based material, which is 0.01-0.1 L / mg. C0 is the initial ammonia concentration of the ammonia-containing mixed gas, mg / L. C1 is the real-time concentration of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material, mg / L; V is the amount of ammonia-containing mixed gas required to be introduced into the modification inlet, L. m is the mass of the hot material, mg. T1 is the real-time temperature of the carbon-based material before modification, which needs to be measured, °C. T2 is the temperature of the carbon-based material after modification, which needs to be measured, °C. T3 is the temperature of the mixed gas before modification, which needs to be measured, °C. T4 is the temperature of the mixed gas after modification, which needs to be measured, °C. That is, the amount of ammonia-containing mixed gas introduced under given working conditions is calculated according to formula (1) so that the ammonia content of the obtained adsorption material meets the working condition requirements.

[0041] It should be noted that all formulas in the present invention are obtained by fitting by the inventors based on experiments and engineering applications, and all calculations are numerical values ​​converted according to prescribed units, and are obtained by substituting the converted numerical values ​​into the formulas (after converting the units, only the numerical values ​​are substituted into the formulas for calculation, without substituting the units; the units are only used to adjust the size of the numerical values).

[0042] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0043] 1: The present invention significantly improves the pelletizing performance of the waste carbon powder by compounding the waste carbon powder with a carbon-containing strengthener, so that the waste carbon powder can replace raw coal in large quantities or even completely as a carbon-based raw material for preparing carbon-based adsorption materials. The raw material source is wide and the price is low, which can not only effectively reduce the investment cost, but also realize the high-value utilization of the waste carbon powder, and at the same time help to further improve the adsorption performance of the carbon-based adsorption material.

[0044] 2: The present invention can precisely control the thermal reaction modification of the hot carbon-based material after heat treatment with ammonia, and can directionally regulate the introduction of appropriate nitrogen-containing functional group content into the product, effectively enhance the surface adsorption sites of the carbon-based adsorption material, improve the sulfur selectivity and adsorption of the carbon-based adsorption material, and ensure the stability of the comprehensive performance of the carbon-based adsorption material.

[0045] 3. The method of the present invention has readily available raw materials, a simple and easy-to-control process, and is readily applicable industrially. The resulting product has stable quality and is highly effective in removing hydrogen sulfide from gases, resulting in significant economic, environmental, and social benefits. BRIEF DESCRIPTION OF THE DRAWINGS

[0046] Figure 1 The process flow chart of the method of the present invention is shown in FIG. DETAILED DESCRIPTION

[0047] The technical solutions of the present invention are illustrated below with examples, and the scope of protection requested by the present invention includes but is not limited to the following embodiments.

[0048] Example 1

[0049] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0050] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 1.01, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.036 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 30 mg / L, the real-time temperature T1 of the carbon-based material before modification is 572°C, the temperature T2 of the carbon-based material after modification is 352°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 80°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 10,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 200 min). After the modification treatment under the above operating conditions, the adsorption material was obtained. After testing, the actual ammonia content of the adsorption material was approximately 2.93%.

[0051] The adsorption material with an ammonia content of about 2.93% is used to absorb hydrogen sulfide with a content of about 50 mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 60.6%.

[0052] Example 2

[0053] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 2.4 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0054] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 1.03, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.038 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 28.8 mg / L, the real-time temperature T1 of the carbon-based material before modification is 565°C, the temperature T2 of the carbon-based material after modification is 346°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 76°C. According to formula (1), the total amount of ammonia-containing mixed gas under the current modification operating conditions is calculated to be approximately 10,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 200 min). After the modification treatment under the above operating conditions, the adsorption material is obtained. After testing, the actual ammonia content of the adsorption material is approximately 2.84%.

[0055] The adsorption material with an ammonia content of about 2.84% is used to absorb the hydrogen sulfide content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 58.2%.

[0056] Example 3

[0057] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 3.0 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0058] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 1.04, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.039 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 26.5 mg / L, the real-time temperature T1 of the carbon-based material before modification is 562°C, the temperature T2 of the carbon-based material after modification is 341°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 74°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 10,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 200 min). After the modification treatment under the above operating conditions, the adsorption material is obtained. After testing, the actual ammonia content of the adsorption material is approximately 2.75%.

[0059] The adsorption material with an ammonia content of about 2.75% is used to absorb hydrogen sulfide with a content of about 50 mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 56.3%.

[0060] Example 4

[0061] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 0.9 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0062] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 1.01, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.036 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 28.7 mg / L, the real-time temperature T1 of the carbon-based material before modification is 571°C, the temperature T2 of the carbon-based material after modification is 352°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 78°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 10,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 200 min). After the modification treatment under the above operating conditions, the adsorption material was obtained. After testing, the actual ammonia content of the adsorption material was approximately 2.69%.

[0063] The adsorption material with an ammonia content of about 2.69% is used to absorb the hydrogen sulfide content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 55.4%.

[0064] Example 5

[0065] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 0.6 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0066] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 0.98, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.034 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 30 mg / L, the real-time temperature T1 of the carbon-based material before modification is 581°C, the temperature T2 of the carbon-based material after modification is 363°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 82°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification conditions is approximately 10,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 200 min). After the modification treatment under the above operating conditions, the adsorption material was obtained. After testing, the actual ammonia content of the adsorption material was approximately 2.65%.

[0067] The adsorption material containing about 2.65% ammonia is used to absorb hydrogen sulfide with a content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 54.5%.

[0068] Example 6

[0069] Example 1 was repeated, except that ammonia and nitrogen were first mixed to obtain an ammonia-containing mixed gas with an ammonia concentration of approximately 30 mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Testing revealed that the actual ammonia content of the resulting adsorbent material was approximately 1.03%.

[0070] The adsorption material containing about 1.03% ammonia is used to absorb hydrogen sulfide with a content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 39.6%.

[0071] Example 7

[0072] Example 1 was repeated, except that ammonia and nitrogen were first mixed to obtain an ammonia-containing mixed gas with an ammonia concentration of approximately 40 mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Testing revealed that the actual ammonia content of the resulting adsorbent material was approximately 1.65%.

[0073] The adsorption material containing about 1.03% ammonia is used to absorb hydrogen sulfide with a content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 48.2%.

[0074] Example 8

[0075] Example 1 was repeated, except that ammonia and nitrogen were first mixed to obtain an ammonia-containing mixed gas with an ammonia concentration of approximately 50 mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Testing revealed that the actual ammonia content of the resulting adsorbent material was approximately 2.36%.

[0076] The adsorption material containing about 1.03% ammonia is used to absorb hydrogen sulfide with a content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption material for adsorption purification. The carbon-based adsorption material adsorbs part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 51.9%.

[0077] Example 9

[0078] Example 1 was repeated, except that ammonia and nitrogen were first mixed to obtain an ammonia-containing mixed gas with an ammonia concentration of approximately 65 mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Testing revealed that the actual ammonia content of the resulting adsorbent material was approximately 3.26%.

[0079] The adsorption material containing about 1.03% ammonia is used to absorb hydrogen sulfide with a content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 62.8%.

[0080] Example 10

[0081] Example 1 was repeated, except that ammonia and nitrogen were first mixed to obtain an ammonia-containing mixed gas with an ammonia concentration of approximately 75 mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Testing revealed that the actual ammonia content of the resulting adsorbent material was approximately 3.50%.

[0082] The adsorption material containing about 1.03% ammonia is used to absorb hydrogen sulfide with a content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 63.2%.

[0083] Example 11

[0084] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0085] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 1.5%, the modification correction coefficient a is 0.99, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.033 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 24.6 mg / L, the real-time temperature T1 of the carbon-based material before modification is 565°C, the temperature T2 of the carbon-based material after modification is 365°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 75°C. According to formula (1), the total amount of ammonia-containing mixed gas under the current modification operating conditions is calculated to be approximately 5000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 100 min). After the modification treatment under the above operating conditions, the adsorption material is obtained. After testing, the actual ammonia content of the adsorption material is approximately 1.48%.

[0086] The adsorption material containing about 1.48% ammonia is used to absorb hydrogen sulfide with a content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 43.5%.

[0087] Example 12

[0088] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0089] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 0.6%, the modification correction coefficient a is 0.97, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.031 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 35.5 mg / L, the real-time temperature T1 of the carbon-based material before modification is 561°C, the temperature T2 of the carbon-based material after modification is 392°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 77°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 2000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 40 min). After the modification treatment under the above operating conditions, the adsorption material is obtained. After testing, the actual ammonia content of the adsorption material is approximately 0.57%.

[0090] The adsorption material with an ammonia content of about 0.57% is used to absorb the hydrogen sulfide content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption material for adsorption purification. The carbon-based adsorption material adsorbs part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material is finally detected to be about 36.5%.

[0091] Example 13

[0092] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0093] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 2.3%, the modification correction coefficient a is 1.04, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.036 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 33.3 mg / L, the real-time temperature T1 of the carbon-based material before modification is 562°C, the temperature T2 of the carbon-based material after modification is 359°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 78°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 7600 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 152 min). After the modification treatment under the above operating conditions, the adsorption material is obtained. After testing, the actual ammonia content of the adsorption material is approximately 2.25%.

[0094] The adsorption material with an ammonia content of about 2.25% is used to absorb hydrogen sulfide with a content of about 50 mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with the flue gas is passed through a fixed device equipped with a carbon-based adsorption material for adsorption purification. The carbon-based adsorption material adsorbs part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 51.7%.

[0095] Example 14

[0096] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0097] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 2.8%, the modification correction coefficient a is 1.04, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.037 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 26.6 mg / L, the real-time temperature T1 of the carbon-based material before modification is 569°C, the temperature T2 of the carbon-based material after modification is 346°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 76°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 9300 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 186 min). After the modification treatment under the above operating conditions, the adsorption material is obtained. After testing, the actual ammonia content of the adsorption material is approximately 2.69%.

[0098] The adsorption material with an ammonia content of about 2.69% is used to absorb the hydrogen sulfide content of about 50mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 55.2%.

[0099] Example 15

[0100] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0101] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 1.03, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.038 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 32 mg / L, the real-time temperature T1 of the carbon-based material before modification is 566°C, the temperature T2 of the carbon-based material after modification is 345°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 75°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 11,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 220 min). After the modification treatment under the above operating conditions, the adsorption material was obtained. After testing, the actual ammonia content of the adsorption material was approximately 2.95%.

[0102] The adsorption material with an ammonia content of about 2.95% is used to absorb hydrogen sulfide with a content of about 50 mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 57.7%.

[0103] Example 16

[0104] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0105] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 1.04, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.039 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 25 mg / L, the real-time temperature T1 of the carbon-based material before modification is 573°C, the temperature T2 of the carbon-based material after modification is 369°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 74°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 9000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 180 min). After the modification treatment under the above operating conditions, the adsorption material was obtained. After testing, the actual ammonia content of the adsorption material was approximately 2.88%.

[0106] The adsorption material with an ammonia content of about 2.88% is used to absorb hydrogen sulfide with a content of about 50 mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 55.6%.

[0107] Example 17

[0108] Example 1 was repeated except that the coal tar pitch was replaced by natural asphalt.

[0109] Example 18

[0110] Example 1 was repeated except that the coal tar pitch was replaced by petroleum pitch.

[0111] Example 19

[0112] Example 1 was repeated except that the starch was replaced by coal tar.

[0113] Example 20

[0114] Example 1 was repeated except that the starch was replaced by carboxymethyl cellulose.

[0115] Example 21

[0116] Example 1 was repeated except that the starch was replaced by polyvinyl alcohol.

[0117] Example 22

[0118] Example 1 was repeated except that the starch was replaced with sesbania powder.

[0119] Comparative Example 1

[0120] First, 13.2 kg of desulfurization and denitrification waste carbon powder was added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 2.0 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then fed into a molding machine for granulation to obtain cylindrical molding materials with a particle size of approximately 8 mm. The molding materials were then dried at 70°C until a moisture content of 7% was obtained.

[0121] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 0.97, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.033 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 27.4 mg / L, the real-time temperature T1 of the carbon-based material before modification is 588°C, the temperature T2 of the carbon-based material after modification is 367°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 82°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 10,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 200 min). After the modification treatment under the above operating conditions, the adsorption material is obtained. After testing, the actual ammonia content of the adsorption material is approximately 2.45%.

[0122] The adsorption material with an ammonia content of about 2.45% is used to absorb hydrogen sulfide with a content of about 50 mg / m3 The blast furnace gas is desulfurized: the blast furnace gas mixed with the flue gas is penetrated through a fixed device equipped with a carbon-based adsorption material for adsorption purification. The carbon-based adsorption material adsorbs part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 52.3%.

[0123] Comparative Example 2

[0124] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of coal tar pitch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then pelletized in a molding machine to obtain cylindrical pellets with a particle size of approximately 8 mm. The pellets were then dried at 70°C until a moisture content of 7% was obtained.

[0125] Take 20kg of raw pellets and send them into the rotary carbonization furnace for carbonization treatment (the specific carbonization heating process is to put them into the furnace from 280℃, gradually rise from the low temperature zone to the high temperature zone of 800℃ and then take them out of the furnace, and the process time is 35min). After the carbonization treatment is completed, take them out of the furnace and cool them to obtain the adsorption material.

[0126] The above adsorption material is used to absorb hydrogen sulfide with a content of about 50 mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 30.1%.

[0127] Comparative Example 3

[0128] First, 13.2 kg of desulfurization and denitrification waste carbon powder and 1.8 kg of starch were added to a mixer and ground until a mixed milled material with a 325-mesh pass rate of at least 75% was obtained. 1.6 kg of starch and 3.4 kg of water were then added to the mixed milled material, which was then stirred and kneaded in a vertical intensive mixer to obtain a kneaded material. The kneaded material was then granulated in a molding machine to obtain cylindrical molding materials with a particle size of approximately 8 mm. The molding materials were then dried at 70°C until a moisture content of 7% was obtained.

[0129] 20kg of raw pellets were fed into a rotary carbonization furnace for carbonization (the carbonization temperature was raised from 280°C into the furnace, gradually rising from the low temperature zone to the high temperature zone of 800°C before exiting the furnace; the process took 35 minutes). After carbonization, approximately 13kg of hot material at approximately 600°C was removed from the furnace. Ammonia and nitrogen were mixed to produce an ammonia-containing mixed gas with an ammonia concentration of approximately 60mg / L. This ammonia-containing mixed gas was then mixed with the hot material for modification. Under the current operating conditions, the target ammonia content Q of the adsorption material is 3%, the modification correction coefficient a is 1.01, the adsorption constant k of ammonia adsorbed by the carbon-based material is 0.035 L / mg, the real-time concentration C1 of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material is 27 mg / L, the real-time temperature T1 of the carbon-based material before modification is 576°C, the temperature T2 of the carbon-based material after modification is 365°C, the temperature T3 of the mixed gas before modification is 25°C, and the temperature T4 of the mixed gas after modification is 76°C. According to formula (1), the total amount of ammonia-containing mixed gas used under the current modification operating conditions is approximately 10,000 L (when continuously input, the input rate is approximately 50 L / min, and the input time is approximately 200 min). After the modification treatment under the above operating conditions, the adsorption material was obtained. After testing, the actual ammonia content of the adsorption material was approximately 2.56%.

[0130] The adsorption material with an ammonia content of about 2.56% is used to absorb hydrogen sulfide with a content of about 50 mg / m 3 The blast furnace gas is desulfurized: the blast furnace gas mixed with flue gas is penetrated through a fixed device equipped with carbon-based adsorption materials for adsorption purification. The carbon-based adsorption materials adsorb part of the hydrogen sulfide in the flue gas. The desulfurization rate of the adsorption material was finally detected to be about 53.2%.

[0131] In the present invention, the sources of some raw materials are as follows:

[0132] Coal tar pitch, petroleum asphalt and natural asphalt were purchased from Maoming Zhengcheng Petrochemical Co., Ltd.

[0133] Ammonia was purchased from Chengdu Taiyu Industrial Gas Co., Ltd.

[0134] Starch was purchased from Foshan Gaofeng Starch Technology Co., Ltd.

[0135] Carboxymethyl cellulose was purchased from Hebei Yufei Chemical Co., Ltd.

[0136] Polyvinyl alcohol was purchased from Langfang Feitai New Material Technology Co., Ltd.

[0137] Sesbania tinctoria powder was purchased from Henan Landing Biotechnology Co., Ltd.

Claims

1. A method for preparing an adsorbent material for gas desulfurization, the method comprising the following steps: 1) Ingredients: Grind the carbon powder and carbon-containing reinforcing agent and then mix with a binder and water to obtain a mixture; 2) Granulation: The mixture is kneaded, formed and dried to obtain raw granules; 3) Heat treatment: The raw pellets are carbonized and / or activated to obtain hot materials; 4) Modification: The hot material is brought into contact with the ammonia-containing mixed gas for modification. The introduction state of the ammonia-containing mixed gas is controlled according to the quality of the hot material and the target performance requirements of the adsorption material, thereby obtaining an adsorption material that meets the working conditions.

2. The method according to claim 1, wherein: In step 1), the carbon powder is one or more of desulfurization and denitrification waste carbon powder, VOCs adsorption waste carbon powder, and waste carbon powder generated during the production and transportation of activated carbon, preferably desulfurization and denitrification waste carbon powder and / or VOCs adsorption waste carbon powder; Preferably, the amount of the carbon powder is 55-85% of the total mass of the mixture, preferably 60-80%, more preferably 65-75%.

3. The method according to claim 1 or 2, characterized in that: In step 1), the carbon-containing strengthening agent is asphalt, coal-to-liquid liquefaction residue, or a mixture of the two; preferably, the asphalt is one or more of coal tar asphalt, petroleum asphalt, and natural asphalt; Preferably, the amount of the carbon-containing reinforcing agent is 3-15% of the total mass of the mixture, preferably 5-12%, and more preferably 8-10%.

4. The method according to any one of claims 1 to 3, characterized in that: In step 1), the binder is one or more of coal tar, carboxymethyl cellulose, polyvinyl alcohol, sesbania powder, starch, and resin, preferably starch; Preferably, the amount of the binder is 1-15% of the total mass of the mixture, preferably 2-12%, more preferably 3-10%.

5. The method according to any one of claims 1 to 4, characterized in that: In step 1), the amount of water is 12-30% of the total mass of the mixture, preferably 14-28%, more preferably 15-25%; and / or In step 1), the particle size of the material after the carbon powder and the carbon-containing reinforcing agent are mixed and ground is such that more than 80% of the particle size passes through 200 mesh or more than 60% of the particle size passes through 325 mesh.

6. The method according to any one of claims 1 to 4, characterized in that: In step 2), the raw pellets are in the form of spheres, cylinders, blocks, or honeycombs; the average particle size of the raw pellets is 3 to 15 mm, preferably 5 to 12 mm; Preferably, the drying temperature is 50-90° C., preferably 60-80° C.; the drying time is such that the moisture content of the raw pellets is less than 10%, preferably less than 8%.

7. The method according to any one of claims 1 to 6, characterized in that: In step 3), the carbonization is carried out at a temperature of 200-1000°C (preferably 300-900°C) for 15-180 minutes (preferably 30-150 minutes), and the final carbonization temperature is 600-900°C; and / or In step 3), the activation is carried out at a temperature of 800-1000° C. (preferably 850-950° C.) for 30-1500 min (preferably 60-1200 min), and the activation medium is water vapor.

8. The method according to any one of claims 1 to 7, characterized in that: In step 4), the ammonia-containing mixed gas is a mixed gas composed of ammonia and protective gas; the protective gas is one or more of nitrogen, helium, neon, argon, xenon, and carbon dioxide; Preferably, the concentration of ammonia in the ammonia-containing mixed gas is 30-75 mg / L, preferably 40-70 mg / L, and more preferably 50-65 mg / L.

9. The method according to any one of claims 1 to 8, characterized in that: In step 4), the state of the ammonia-containing mixed gas being introduced is controlled according to the mass of the hot material and the target performance requirements of the adsorption material. Specifically, the amount of the ammonia-containing mixed gas introduced is controlled according to the mass of the hot material and the target ammonia content of the adsorption material. The mass of the hot material, the target ammonia content of the adsorption material, and the amount of the ammonia-containing mixed gas introduced satisfy the following formula: （1）； In formula (1), Q is the target ammonia content of the adsorbent material, ranging from 1 to 4%, preferably 2 to 3% (based on the mass ratio of the adsorbent material); a is the modification correction coefficient, ranging from 0.85 to 1.15; k is the adsorption constant of ammonia adsorbed by the carbon-based material, ranging from 0.01 to 0.1, L / mg; C0 is the initial ammonia concentration of the ammonia-containing mixed gas, mg / L; C1 is the real-time concentration of ammonia at the outlet during the adsorption reaction between the ammonia-containing mixed gas and the carbon-based material, mg / L; V is the amount of ammonia-containing mixed gas required to be introduced into the modification inlet, L; m is the mass of the hot material, mg. T1 is the real-time temperature of the carbon-based material before modification, °C; T2 is the temperature of the carbon-based material after modification, °C; T3 is the temperature of the mixed gas before modification, °C; and T4 is the temperature of the mixed gas after modification, °C.

10. An adsorption material for gas desulfurization, characterized in that: The adsorption material for gas desulfurization is prepared according to the method according to any one of claims 1 to 9.

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