CN112495133A - Activated carbon-based catalytic desulfurization process - Google Patents
Activated carbon-based catalytic desulfurization process Download PDFInfo
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Abstract
The invention discloses an activated carbon-based catalytic desulfurization process, which is characterized by comprising the following steps: the method comprises the following steps: collecting the discharged flue gas, and conveying the collected flue gas into the rotary joint through a pipeline, so as to facilitate the primary dust removal of a filter cylinder connected in the pipeline; the flue gas after primary dust removal enters a desulfurization box body through a rotary joint, desulfurization is carried out by using activated carbon in the desulfurization box body, the activated carbon used for desulfurization is recycled through a regeneration method, and lost activated carbon is supplemented; conveying the flue gas subjected to activated carbon desulfurization into a heat exchange cooler for cooling; and conveying the cooled flue gas into a leaching tower, and discharging the leached flue gas through a bag-type dust collector at the top of the leaching tower after the leaching tower is leached by a plurality of spraying pipelines arranged in the leaching tower. The invention can regenerate and reuse the used activated carbon, and plays the roles of reducing the cost and saving resources.
Description
Technical Field
The invention relates to an activated carbon-based catalytic desulfurization process, in particular to a preparation method of columnar activated carbon prepared by high-temperature reaming and ammonia high-temperature modification, which is used for preparing a catalyst with rich mesoporous structure and nitrogen-containing functional groups on the surfaceThe high-efficiency desulfurized columnar activated carbon of the cluster is used for desulfurizing equipment in various industries such as power generation, steel, chemical engineering and the like, and has high capacity and high activity SO2Adsorbing the activated carbon.
Background
The activated carbon is a porous carbon material with high specific surface area, developed pore structure and adjustable surface chemical property, and is widely applied to a plurality of fields such as adsorption, catalysis, electrochemistry and the like. The performance of activated carbon depends on its pore structure and surface chemistry, i.e., surface functional groups, significantly affected by heteroatoms (e.g., oxygen, nitrogen, phosphorus, and sulfur, etc.). Among these heteroatoms, the most widely studied are oxygen and nitrogen, which form oxygen-containing and nitrogen-containing functional groups, respectively, on the carbon surface. Because the nitrogen-containing functional group on the surface of the activated carbon can obviously improve the adsorption, catalysis and electrochemical properties of the activated carbon, the research for improving the pore structure and the nitrogen-containing functional group of the activated carbon draws extensive attention and attention.
The method for reaming the activated carbon by the high-temperature process is not only used in the desulfurization process, but also widely applied in the existing denitration and mercury removal links, has a good reaming effect, can obviously improve the pore structure of the activated carbon, improves the porosity and the mesoporous volume, and achieves the effect of improving the adsorption capacity of the activated carbon.
Ammonia modification of activated carbon is the most common method for introducing nitrogen-containing functional groups onto the carbon surface. The preoxidized active carbon is modified by ammonia gas at different ammonia gas treatment temperatures, and amide, lactam, imide, pyridine, pyrrole, quaternary nitrogen and other nitrogen-containing functional groups can be introduced to the surface of the active carbon SO as to greatly improve the SO adsorption of the active carbon2The adsorption rate of (c). At the high-temperature modification temperature, when the ammonia gas treatment temperature reaches above 800 ℃, the nitrogen-containing groups on the carbon surface mainly come from N-6, N-5 and quaternary nitrogen (N-Q) nitrogen-containing functional groups formed by directly combining ammonia gas and carbon atoms on the carbon surface, and have higher thermal stability and desulfurization activity than nitrogen-containing groups of nitrogen oxides (N-X) such as amide, imide, lactam and the like formed in a medium-low temperature environment (below 800 ℃).
In the invention patent with the application number of CN201610655211.8, a modified active carbon and a preparation method thereof are disclosedApplication ", the preparation method is as follows: graphitized activated carbon HNO3After treatment, high-temperature heat treatment is carried out in an ammonia gas atmosphere to obtain the activated carbon carrier with high mesoporous rate, the activated carbon carrier has the characteristics of larger pore volume, higher mesoporous rate (more than or equal to 97%), good conductivity and the like, and when the activated carbon carrier is used for an ammonia synthesis catalyst carrier, the dispersion degree of noble metal ruthenium can be obviously improved, and the methanation resistance, the thermal stability and the activity of the catalyst are improved. In the invention patent with the application number of CN201210381226.1, a modified activated carbon material and a preparation method thereof are disclosed, and the preparation method comprises the following steps: the method comprises the steps of taking activated carbon as a raw material, placing the activated carbon in a heating furnace, firstly introducing nitrogen, raising the temperature to 600-900 ℃, then introducing ammonia, and reacting the activated carbon in the ammonia for 10-120min to obtain the modified activated carbon material. The modified activated carbon material has high adsorption performance on perchlorate ions in water, can improve the ability of raw activated carbon to adsorb perchlorate in water by nearly 9 times, and has the characteristics of high mechanical strength, long service life cycle and low use cost. The invention provides a method for adsorbing pollutants in water by using commercial columnar activated carbon, which is mainly applied to adsorption of pollutants in water, wherein high-temperature nitrogen reaming is firstly carried out by using commercial columnar activated carbon, the mesoporous rate is improved, then high-temperature ammonia modification is carried out to enrich surface nitrogen-containing functional groups, and the SO of the activated carbon is greatly improved2The adsorption efficiency.
The invention provides that the commercial columnar activated carbon is firstly treated at high temperature of 900 plus 1100 ℃ in nitrogen atmosphere, the pore structure of the activated carbon is obviously improved, the porosity and the mesoporous rate are increased, and the adsorption capacity of the activated carbon is greatly enhanced. Secondly, the active carbon after hole expansion is modified by ammonia gas at the high temperature of 900-1100 ℃, the surface nitrogen functional group is obviously increased, the thermal stability and the activity are obviously enhanced, and SO is realized2And the large-capacity adsorption and removal are carried out.
Disclosure of Invention
Aiming at the defects of small adsorption volume, low desulfurization activity, poor thermal stability of surface nitrogen-containing functional groups and the like of the existing activated carbon, the invention designs a set of preparation process which has high adsorption volume, high thermal stability and high adsorption activity and is easy to realize an industrialized system, and the modified activated carbon is modified under the actual flue gas conditionActivated carbon to SO in flue gas2The adsorption of (1).
The invention provides an activated carbon-based catalytic desulfurization process, which is characterized by comprising the following steps: the method comprises the following steps:
s1: preliminary dust removal: collecting the discharged flue gas, and conveying the collected flue gas into the rotary joint through a pipeline, so as to facilitate the primary dust removal of a filter cylinder connected in the pipeline;
s2: activated carbon desulfurization: via step S1: the flue gas after preliminary dust removal enters a desulfurization box body through a rotary joint, desulfurization is carried out by using activated carbon in the desulfurization box body, the activated carbon used for desulfurization is recycled through a regeneration method, and lost activated carbon is supplemented;
s3: cooling flue gas: will go through step S2: conveying the flue gas subjected to activated carbon desulfurization into a heat exchange cooler for cooling;
s4: leaching and discharging: will go through step S3: and after cooling, conveying the flue gas into the leaching tower, and after leaching through a plurality of spraying pipelines arranged in the leaching tower, discharging the leached flue gas through a bag-type dust remover at the top of the leaching tower.
Further: step S2: the specific method for desulfurizing the activated carbon comprises the following steps:
A1. opening a clean flue gas outlet and an ammonia gas inlet; closing the nitrogen inlet, the sulfur-containing gas outlet, the cold air inlet, the cold air outlet, the hot air inlet and the hot air outlet;
A2. the original flue gas enters the desulfurization box body from the rotary joint, the flue gas is subjected to desulfurization reaction through the active carbon in the flue gas in the process of passing through the active carbon channel, and the clean flue gas is discharged through the clean flue gas outlet.
And further: step S2: the regeneration method in the desulfurization of the activated carbon comprises the following steps:
B1. when the adsorption of the activated carbon in the activated carbon channel is saturated, closing the original flue gas inlet, the purified flue gas outlet and the ammonia gas inlet; sequentially opening a nitrogen inlet, a sulfur-containing gas outlet, a hot air inlet and a hot air outlet;
B2. introducing 380-550 ℃ hot air to start heating the activated carbon in the activated carbon flue gas desulfurization and regeneration device, so that sulfur dioxide adsorbed by the activated carbon is gradually released and enters a sulfur dioxide utilization system along with nitrogen through a sulfur-containing gas outlet;
B3. closing the hot air inlet and the hot air outlet after the release of the sulfur dioxide is finished; opening a cold air inlet and a cold air outlet;
B4. and (3) cooling the activated carbon to below 150 ℃ by introducing cold air, then closing the cold air inlet, the cold air outlet, the nitrogen inlet and the sulfur-containing gas outlet, and finishing the activated carbon regeneration process.
And further: the preparation method of the active carbon comprises the following steps:
c1: washing the commercial columnar activated carbon with deionized water for 30-40 times, removing surface dust, and drying in a drying oven at 105 ℃ for 12-24h, wherein the specific steps are as follows:
c2: taking out the activated carbon prepared in the step (C1), and setting the N2Carrying out temperature programming under the condition of continuous introduction, setting the temperature rise rate of 10-20 ℃/min, and calcining for 2.5-4h in the temperature range of 900-;
c3: taking the activated carbon prepared in the step (C2) out, and placing the activated carbon in a tube furnace for high-temperature NH3Modifying, firstly weighing a certain amount of active carbon in a tube furnace, firstly, N2Raising the temperature to 300 ℃ at a certain temperature raising rate under the atmosphere, and then switching to NH3Under the atmosphere, continuously heating to 900-1100 ℃, and carrying out high-temperature modification at the temperature for 2-3 h;
c4: modifying the activated carbon in the step (C3) to high NH3And cooling to room temperature under the flow condition to obtain the required sample.
And further: in step C1, commercial columnar activated carbon with diameter of 4-6mm, length of 5-10mm, and specific surface area greater than 750m is selected2(g), ash content is less than 8%, and strength is more than 98%.
And further: in step C2, N is injected2The flow rate of the gas is always kept at 70-80mL/min, the temperature of the calcining furnace is kept at 900-1100 ℃, and the calcining time is kept for 2.5-4 h.
And further: in step C3, NH for modification3Purity of 99.99%, N2The flow rate is 70-80mL/min, the heating rate is 10 ℃/min, and NH is added3The flow rate is 1-2ml/min, and the modification time is 2-3 h.
And further: in step C4, NH is added after the modification is completed3The flow rate was increased from 1-2ml/min to 60ml/min, and the introduction was continued until cooling to room temperature.
And further: the desulfurization box body is fixed at the top of the mounting table, the bottom of the mounting table is provided with a rotary joint, four pipelines are connected around the rotary joint, the four pipelines are communicated with a flue gas inlet at the bottom of the desulfurization box body through the rotary joint, each pipeline is provided with a butterfly valve, a plurality of activated carbon channels 7 are arranged in the desulfurization box body, a grid support plate is further arranged in the desulfurization box body below the activated carbon channels, activated carbon in the activated carbon channels is limited in the activated carbon channels through the grid support plate, the side wall of the desulfurization box body above the activated carbon channels is provided with a clean flue gas outlet, a sulfur-containing gas outlet, a cold air inlet and a hot air inlet, the side wall of the desulfurization box body below the activated carbon channels is provided with an ammonia inlet, a nitrogen inlet, a cold air outlet and a hot air outlet, the desulfurization box body is connected with a heat exchange cooler through the clean flue gas outlet, the heat exchange cooler be linked together with the drip washing tower of one side again, the gas vent department at drip washing tower top still be provided with the sack cleaner, the top of desulfurization box still be provided with the activated carbon storehouse, the inside airborne of the desulfurization box of activated carbon storehouse through hopper and activated carbon passageway top be linked together, activated carbon in the activated carbon storehouse is discharged into the activated carbon passageway through the hopper and is replenished.
And further: the filter cartridge is characterized in that a flange plate is arranged at one end, far away from the rotary joint, of the pipeline, the flange plate is connected with the filter cartridge into a whole, the filter cartridge extends into the pipeline, external threads are arranged on the outer wall of the filter cartridge, and internal threads are arranged on the inner wall of the pipeline, corresponding to the external threads.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the hole expansion treatment of the activated carbon is realized by adopting the high-temperature hole expansion under the nitrogen atmosphere of 900-1100 ℃, and through the volatilization and other effects of organic matters, the pore structure of the activated carbon is greatly improved, the number of mesopores is increased, and the adsorption capacity of the activated carbon is improved;
(2) according to the invention, a mode of 'nitrogen heating up to 300 ℃ → ammonia heating up to 900 → 1100 ℃ → residence modification to 2-3h → ammonia cooling' is adopted, so that nitrogen-containing functional groups with strong thermal stability such as N-6, N-5 and quaternary nitrogen (N-Q) and the like are formed on the surface of the activated carbon, and the high-temperature stability and the adsorption activity of the activated carbon are improved.
Description of the drawings:
FIG. 1 is a structural diagram corresponding to the desulfurization process of the present invention.
Fig. 2 is an internal structure view of the pipe.
The specific implementation mode is as follows:
the invention provides an activated carbon-based catalytic desulfurization process, which comprises the following steps:
s1: preliminary dust removal: collecting the discharged flue gas, and conveying the collected flue gas into the rotary joint through a pipeline, so as to facilitate the primary dust removal of a filter cylinder connected in the pipeline;
s2: activated carbon desulfurization: via step S1: the flue gas after preliminary dust removal enters a desulfurization box body through a rotary joint, desulfurization is carried out by using activated carbon in the desulfurization box body, the activated carbon used for desulfurization is recycled through a regeneration method, and lost activated carbon is supplemented;
s3: cooling flue gas: will go through step S2: conveying the flue gas subjected to activated carbon desulfurization into a heat exchange cooler for cooling;
s4: leaching and discharging: will go through step S3: and after cooling, conveying the flue gas into the leaching tower, and after leaching through a plurality of spraying pipelines arranged in the leaching tower, discharging the leached flue gas through a bag-type dust remover at the top of the leaching tower.
The above step S2: the specific method for desulfurizing the activated carbon comprises the following steps:
A1. opening a clean flue gas outlet 1-1 and an ammonia gas inlet 10; closing a nitrogen inlet 11, a sulfur-containing gas outlet 1-3, a cold air inlet 1-2, a cold air outlet 1-6, a hot air inlet 1-4 and a hot air outlet 1-5;
A2. the original flue gas enters the desulfurization box body from the rotary joint, the flue gas is subjected to desulfurization reaction through the active carbon in the flue gas in the process of passing through the active carbon channel 7, and the clean flue gas is discharged through the clean flue gas outlet 11.
The above step S2: the regeneration method in the desulfurization of the activated carbon comprises the following steps:
B1. when the adsorption of the activated carbon in the activated carbon channel is saturated, closing the original flue gas inlet, the purified flue gas outlet and the ammonia gas inlet; sequentially opening a nitrogen inlet, a sulfur-containing gas outlet, a hot air inlet and a hot air outlet;
B2. introducing 380-550 ℃ hot air to start heating the activated carbon in the activated carbon flue gas desulfurization and regeneration device, so that sulfur dioxide adsorbed by the activated carbon is gradually released and enters a sulfur dioxide utilization system along with nitrogen through a sulfur-containing gas outlet;
B3. closing the hot air inlet and the hot air outlet after the release of the sulfur dioxide is finished; opening a cold air inlet and a cold air outlet;
B4. and (3) cooling the activated carbon to below 150 ℃ by introducing cold air, then closing the cold air inlet, the cold air outlet, the nitrogen inlet and the sulfur-containing gas outlet, and finishing the activated carbon regeneration process.
The preparation method of the activated carbon comprises the following steps:
c1: washing the commercial columnar activated carbon with deionized water for 30-40 times, removing surface dust, and drying in a drying oven at 105 ℃ for 12-24h, wherein the specific steps are as follows:
c2: taking out the activated carbon prepared in the step (C1), and setting the N2Carrying out temperature programming under the condition of continuous introduction, setting the temperature rise rate of 10-20 ℃/min, and calcining for 2.5-4h in the temperature range of 900-;
c3: taking the activated carbon prepared in the step (C2) out, and placing the activated carbon in a tube furnace for high-temperature NH3Modifying, firstly weighing a certain amount of active carbon in a tube furnace, firstly, N2Raising the temperature to 300 ℃ at a certain temperature raising rate under the atmosphere, and then switching to NH3Under the atmosphere, continuously heating to 900-1100 ℃, and carrying out high-temperature modification at the temperature for 2-3 h;
c4: modifying the activated carbon in the step (C3) to high NH3And cooling to room temperature under the flow condition to obtain the required sample.
In the step C1, commercial columnar activated carbon with diameter of 4-6mm, length of 5-10mm and specific surface area greater than 750m is selected2(g), ash content is less than 8%, and strength is more than 98%.
In the above step C2, N is injected2The flow rate of the gas is always kept at 70-80mL/min, the temperature of the calcining furnace is kept at 900-1100 ℃, and the calcining time is kept for 2.5-4 h.
NH for modification in the above step C33Purity of 99.99%, N2The flow rate is 70-80mL/min, the heating rate is 10 ℃/min, and NH is added3The flow rate is 1-2ml/min, and the modification time is 2-3 h.
In the step C4, NH is added after the modification is completed3The flow rate was increased from 1-2ml/min to 60ml/min, and the introduction was continued until cooling to room temperature.
The desulfurization box body 1 shown in the figure 1 is fixed at the top of a mounting table 2, the bottom of the mounting table is provided with a rotary joint 3, four pipelines 4 are connected around the rotary joint and communicated with a flue gas inlet at the bottom of the desulfurization box body through the rotary joint, each pipeline is provided with a butterfly valve 5, a plurality of activated carbon channels 7 are arranged in the desulfurization box body, a grid supporting plate 9 is further arranged in the desulfurization box body below the activated carbon channels, activated carbon in the activated carbon channels is limited in the activated carbon channels through the grid supporting plate, the side wall of the desulfurization box body above the activated carbon channels is provided with a clean flue gas outlet 1-1, a sulfur-containing gas outlet 1-3, a cold air inlet 1-2 and a hot air inlet 1-4, the side wall of the desulfurization box body below the activated carbon channels is provided with an ammonia inlet 10, a sulfur-containing, Nitrogen gas entry 11, cold wind export 1-6, hot air exitus 1-5, the desulfurization box pass through clean flue gas export and heat transfer cooler 13 and link to each other, the heat transfer cooler be linked together with the drip washing tower of one side again, the exhaust port department at drip washing tower top still be provided with the sack cleaner, the top of desulfurization box still be provided with activated carbon storehouse 8, the inside airborne of desulfurization box that passes through hopper 12 and activated carbon passageway top in the activated carbon storehouse be linked together, activated carbon in the activated carbon storehouse is discharged into the activated carbon passageway through the hopper and is supplemented.
As shown in fig. 2, a flange 6 is arranged at one end of the pipeline far away from the rotary joint, the flange is connected with the filter cylinder into a whole, the filter cylinder extends into the pipe, external threads are arranged on the outer wall of the filter cylinder, and internal threads are arranged on the inner wall of the pipeline at positions corresponding to the external threads
Example 1:
selecting commercial columnar activated carbon with diameter of 4mm, length of 5mm and specific surface area of 800m3(iv)/g, strength 98.5%, ash content 8%; washing commercial columnar activated carbon with deionized water for 30 times, cleaning and drying, and then placing the columnar activated carbon in a drying oven for drying at 105 ℃ for 12 hours; taking out the activated carbon prepared in the step (C2), and setting the N2Carrying out temperature programming under the condition of continuously introducing air flow speed of 75mL/min, setting the temperature range of 900 ℃ at the temperature rise rate of 15 ℃/min, calcining for 2.5h, further expanding the surface pore structure of the carrier activated carbon, and realizing hole expansion; taking the activated carbon prepared in the step (C3) out, and placing the activated carbon in a tube furnace for high-temperature NH3Modifying, firstly weighing a certain amount of active carbon in a tube furnace, firstly, N2Continuously introducing the gas with the gas flow rate of 75mL/min, heating to 300 ℃ at the heating rate of 10 ℃/min, and then switching to NH3Under the atmosphere, keeping NH3Continuously heating to 900 ℃ under the condition of 2ml/min of airflow, and performing high-temperature modification at the temperature for 3 h; after the activated carbon in the step (C4) is modified, NH is added3The flow rate is increased to 60ml/min, and the introduction is continued until the temperature is cooled to the room temperature, thus preparing the required sample.
15g of the product, namely activated carbon, was taken and subjected to desulfurization adsorption test on a fixed bed apparatus. The components of the smoke are as follows: space velocity 2374h-1，SO2:1000ppm,O 210% and the balance of N2The total gas flow is 2L/min, and the reaction shows that SO2The adsorption efficiency reaches 95 percent, and the duration is 4.5 h. The pore structure on the surface is analyzed by BET, and S is foundBETUp to 954m2/g，VmesUp to 0.025cm3The content of nitrogen-containing functional groups on the surface was 0.81 mmol/g.
Example 2:
selecting commercial columnar activated carbon with diameter of 5mm, length of 5mm and specific surface area of 850m3(ii)/g, strength 99%, ash content 7.5%; washing commercial columnar activated carbon with deionized water for 30 times, cleaning and drying, and then placing the columnar activated carbon in a drying oven for drying at 105 ℃ for 12 hours; taking out the activated carbon prepared in the step (C2), and setting the N2Carrying out temperature programming under the condition of continuously introducing air flow speed of 75mL/min, setting the temperature range of 1000 ℃ at the temperature rising rate of 10 ℃/min, calcining for 3h, further expanding the surface pore structure of the carrier activated carbon, and realizing hole expansion; taking out the activated carbon prepared in the step (C3), and putting the activated carbon into a quartz tube furnace for high-temperature NH3Modifying, firstly weighing a certain amount of active carbon in a tube furnace, firstly, N2Continuously introducing the gas with the gas flow rate of 75mL/min, heating to 300 ℃ at the heating rate of 10 ℃/min, and then switching to NH3Under the atmosphere, keeping NH3The temperature is continuously raised to 1000 ℃ under the condition of airflow of 1.5ml/min, and high-temperature modification is carried out at the temperature for 3 h. After the activated carbon in the step (C4) is modified, NH is added3The flow rate is increased to 60ml/min, and the introduction is continued until the temperature is cooled to the room temperature, thus preparing the required sample.
15g of the product, namely activated carbon, was taken and subjected to desulfurization adsorption test on a fixed bed apparatus. The components of the smoke are as follows: space velocity 2374h-1，SO2:1000ppm,O 210% and the balance of N2Total gas flow 2L/min, test verification SO2The adsorption efficiency reaches 97.06 percent, and the duration is 5 h. The pore structure on the surface is analyzed by BET, and S is foundBETReach 1025m2/g，VmesUp to 0.032cm3The content of nitrogen-containing functional groups on the surface was 0.86mmol/g.
Example 3:
selecting commercial columnar activated carbon with diameter of 6mm, length of 5mm and specific surface area of 900m3(ii)/g, strength 99%, ash content 7.5%; washing commercial columnar activated carbon with deionized water for 30 times, cleaning and drying, and then placing the columnar activated carbon in a drying oven for drying at 105 ℃ for 24 hours; taking out the activated carbon prepared in the step (C2), and setting the N2Continuously introducing the gas at a gas flow rate of 75mL/minThe temperature is programmed to rise, and the calcination is carried out for 4 hours within the temperature range of 1100 ℃ at the temperature rise rate of 20 ℃/min, so as to further expand the surface pore structure of the carrier activated carbon and realize hole expansion; taking out the activated carbon prepared in the step (C3), and putting the activated carbon into a quartz tube furnace for high-temperature NH3Modifying, firstly weighing a certain amount of active carbon in a tube furnace, firstly, N2Continuously introducing the gas with the gas flow rate of 75mL/min, heating to 300 ℃ at the heating rate of 10 ℃/min, and then switching to NH3Under the atmosphere, keeping NH3And continuously heating to 1100 ℃ under the condition of airflow of 1ml/min, and carrying out high-temperature modification at the temperature for 3 h. After the activated carbon in the step (C4) is modified, NH is added3The flow rate is increased to 60ml/min, and the introduction is continued until the temperature is cooled to the room temperature, thus preparing the required sample.
15g of the product activated carbon was taken and subjected to desulfurization adsorption test on a fixed bed apparatus. The components of the smoke are as follows: space velocity 2374h-1，SO2:1000ppm,O 210% and the balance of N2Total gas flow 2L/min, test verification SO2The adsorption efficiency reaches 99.13 percent, and the duration is 6 hours. The pore structure on the surface is analyzed by BET, and S is foundBETReach 1056m2/g，VmesUp to 0.036cm3The content of nitrogen-containing functional groups on the surface was 0.94 mmol/g.
Claims (10)
1. An activated carbon-based catalytic desulfurization process is characterized in that: the method comprises the following steps:
s1: preliminary dust removal: collecting the discharged flue gas, and conveying the collected flue gas into the rotary joint through a pipeline, so as to facilitate the primary dust removal of a filter cylinder connected in the pipeline;
s2: activated carbon desulfurization: via step S1: the flue gas after preliminary dust removal enters a desulfurization box body through a rotary joint, desulfurization is carried out by using activated carbon in the desulfurization box body, the activated carbon used for desulfurization is recycled through a regeneration method, and lost activated carbon is supplemented;
s3: cooling flue gas: will go through step S2: conveying the flue gas subjected to activated carbon desulfurization into a heat exchange cooler for cooling;
s4: leaching and discharging: will go through step S3: and after cooling, conveying the flue gas into the leaching tower, and after leaching through a plurality of spraying pipelines arranged in the leaching tower, discharging the leached flue gas through a bag-type dust remover at the top of the leaching tower.
2. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: step S2: the specific method for desulfurizing the activated carbon comprises the following steps:
A1. opening a clean flue gas outlet (1-1) and an ammonia gas inlet (10); closing a nitrogen inlet (11), a sulfur-containing gas outlet (1-3), a cold air inlet (1-2), a cold air outlet (1-6), a hot air inlet (1-4) and a hot air outlet (1-5);
A2. the original flue gas enters the desulfurization box body from the rotary joint, the flue gas is subjected to desulfurization reaction through the active carbon in the flue gas in the process of passing through the active carbon channel 7, and the clean flue gas is discharged through the clean flue gas outlet (11).
3. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: step S2: the regeneration method in the desulfurization of the activated carbon comprises the following steps:
B1. when the adsorption of the activated carbon in the activated carbon channel is saturated, closing the original flue gas inlet, the purified flue gas outlet and the ammonia gas inlet; sequentially opening a nitrogen inlet, a sulfur-containing gas outlet, a hot air inlet and a hot air outlet;
B2. introducing 380-550 ℃ hot air to start heating the activated carbon in the activated carbon flue gas desulfurization and regeneration device, so that sulfur dioxide adsorbed by the activated carbon is gradually released and enters a sulfur dioxide utilization system along with nitrogen through a sulfur-containing gas outlet;
B3. closing the hot air inlet and the hot air outlet after the release of the sulfur dioxide is finished; opening a cold air inlet and a cold air outlet;
B4. and (3) cooling the activated carbon to below 150 ℃ by introducing cold air, then closing the cold air inlet, the cold air outlet, the nitrogen inlet and the sulfur-containing gas outlet, and finishing the activated carbon regeneration process.
4. The activated carbon-based catalytic desulfurization process according to any one of claims 1 to 3, characterized in that: the preparation method of the active carbon comprises the following steps:
c1: washing the commercial columnar activated carbon with deionized water for 30-40 times, removing surface dust, and drying in a drying oven at 105 ℃ for 12-24h, wherein the specific steps are as follows:
c2: taking out the activated carbon prepared in the step (C1), and setting the N2Carrying out temperature programming under the condition of continuous introduction, setting the temperature rise rate of 10-20 ℃/min, and calcining for 2.5-4h in the temperature range of 900-;
c3: taking the activated carbon prepared in the step (C2) out, and placing the activated carbon in a tube furnace for high-temperature NH3Modifying, firstly weighing a certain amount of active carbon in a tube furnace, firstly, N2Raising the temperature to 300 ℃ at a certain temperature raising rate under the atmosphere, and then switching to NH3Under the atmosphere, continuously heating to 900-1100 ℃, and carrying out high-temperature modification at the temperature for 2-3 h;
c4: modifying the activated carbon in the step (C3) to high NH3And cooling to room temperature under the flow condition to obtain the required sample.
5. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: in step C1, commercial columnar activated carbon with diameter of 4-6mm, length of 5-10mm, and specific surface area greater than 750m is selected2(g), ash content is less than 8%, and strength is more than 98%.
6. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: in step C2, N is injected2The flow rate of the gas is always kept at 70-80mL/min, the temperature of the calcining furnace is kept at 900-1100 ℃, and the calcining time is kept for 2.5-4 h.
7. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: in step C3, NH for modification3Purity of 99.99%, N2The flow rate is 70-80mL/min, and the heating rate is 10 DEG C/min，NH3The flow rate is 1-2ml/min, and the modification time is 2-3 h.
8. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: in step C4, NH is added after the modification is completed3The flow rate was increased from 1-2ml/min to 60ml/min, and the introduction was continued until cooling to room temperature.
9. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: desulfurization box 1 fix at the top of mount table 2, the bottom of mount table install rotary joint 3, rotary joint be connected with four pipelines 4 all around, four pipelines are linked together through rotary joint and desulfurization bottom of the box's flue gas import, all install butterfly valve 5 on every pipeline, the desulfurization box in be provided with a plurality of active carbon passageway 7, the desulfurization box of active carbon passageway below in still be provided with grid backup pad 9, the active carbon in the active carbon passageway passes through the grid backup pad restriction in the active carbon passageway, the desulfurization box's of active carbon passageway top lateral wall on seted up clean flue gas export (1-1), contain sulfur gas export (1-3), cold wind entry (1-2) and hot-blast entry (1-4), the desulfurization box's of active carbon passageway below lateral wall on seted up ammonia entry (10), Nitrogen gas entry 11, cold wind export (1-6), hot air exitus (1-5), the desulfurization box link to each other with heat transfer cooler 13 through clean flue gas export, heat transfer cooler be linked together with the drip washing tower of one side again, the exhaust port department at drip washing tower top still be provided with the sack cleaner, the top of desulfurization box still be provided with activated carbon storehouse 8, the inside airborne of desulfurization box that activated carbon storehouse passes through hopper 12 and activated carbon passageway top be linked together, activated carbon in the activated carbon storehouse is discharged into the activated carbon passageway through the hopper and is supplemented.
10. The activated carbon-based catalytic desulfurization process according to claim 1, characterized in that: the pipeline is characterized in that a flange plate 6 is arranged at one end, away from the rotary joint, of the pipeline, the flange plate is connected with the filter cylinder into a whole, the filter cylinder extends into the pipeline, external threads are arranged on the outer wall of the filter cylinder, and internal threads are arranged on the inner wall of the pipeline, corresponding to the external threads.
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