CN212451324U - Dry purification device for total sulfur removal of blast furnace gas - Google Patents
Dry purification device for total sulfur removal of blast furnace gas Download PDFInfo
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- CN212451324U CN212451324U CN202021580358.3U CN202021580358U CN212451324U CN 212451324 U CN212451324 U CN 212451324U CN 202021580358 U CN202021580358 U CN 202021580358U CN 212451324 U CN212451324 U CN 212451324U
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Abstract
The utility model relates to a dry purification device for total sulfur removal of blast furnace gas, which comprises a catalytic hydrolysis tower, a desulfurizing tower, a pneumatic conveying device (19) and a gas replacement system; the blast furnace gas after dust removal and waste heat and residual pressure power generation sequentially passes through a catalytic hydrolysis tower and a desulfurization tower; carbonyl sulfide (COS) and carbon disulfide (CS)2) Organic sulfur is catalytically hydrolyzed and converted in a catalytic hydrolysis towerTo hydrogen sulfide (H)2S); supplying desulfurizer to the desulfurizing tower through a pneumatic conveying device to absorb hydrogen sulfide (H)2S), sulfur dioxide (SO)2) Hydrogen chloride (HCl) and other acid gases, realizes the removal of sulfur-containing substances in blast furnace gas, and solves sulfur dioxide (SO) from the source2) The problem of standard exceeding is solved, and the corrosion problem of the gas pipeline is controlled to a certain extent by the synergistic removal of hydrogen chloride (HCl).
Description
Technical Field
The utility model relates to a dry purification device for removing total sulfur in blast furnace gas, in particular to a dry purification device capable of realizing COS and CS in blast furnace gas2、H2S、SO2A dry purification device for removing sulfur-containing substances and removing HCl in a synergistic manner belongs to the pollutant control technology in the technical field of environmental protection engineering, and is used for realizing total sulfur removal of blast furnace gas in a set of process.
Background
The blast furnace gas is used as the combustible gas with the maximum output of the steel enterprises, and the statistical output is up to 700-. The existing blast furnace gas purification and subsequent application mainly adopts bag type dust removal to remove particulate matters, and the particulate matters are sent to user units such as a blast furnace hot blast stove, a steel rolling heating furnace, gas power generation and the like to be used as fuels after TRT residual pressure power generation, but the blast furnace gas still contains harmful substances such as sulfur, chlorine and the like. With the promulgation of the opinion about the promotion of the ultra-low emission in the steel industry, the steel industry formally enters the 'ultra-low emission' era, and users of blast furnace hot blast stoves, steel rolling heating furnaces, gas power generation and the like all require the burning of tail gas SO2The ultra-low emission limit is reached, and the prior blast furnace gas purification process can not meet the requirement of SO2And (5) controlling the requirements.
The current technical route mainly comprises source control and tail end treatment after combustion, if a tail end treatment mode is adopted, desulfurization facilities need to be arranged at multiple points, and meanwhile, the waste gas amount after gas combustion is large, and the scale of treatment facilities is enlarged; if a source control mode is adopted, centralized treatment can be realized, and the treated gas amount is only about 60% of the flue gas amount after combustion, so that the total investment is low, the total occupied area is small, the operation cost is low, and the management is convenient. Meanwhile, the source management promotes the service life and the combustion efficiency of the pipe network. The method implements the total sulfur removal of the blast furnace gas, reduces the sulfur content in the gas, can greatly reduce the pressure of the tail end treatment, and even saves tail end treatment facilities.
Blast furnace gas total sulfur removal is a new technical development direction, at present, a single organic sulfur hydrolysis technology and a dry adsorption removal technology are more, and a blast furnace gas dechlorination technology has related application examples, but no reports or engineering cases of the blast furnace gas total sulfur removal technology exist, so the blast furnace gas total sulfur removal technology still belongs to a front-edge exploration stage.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide a dry purification device that can realize the complete sulphur desorption of blast furnace gas, preferred one kind can realize COS, CS in the blast furnace gas2、H2S、SO2And the like, and a dry purification device for removing HCl in a synergistic manner, so as to solve the technical problems.
In order to solve the technical problems, the dry purification device for removing the total sulfur in the blast furnace gas is provided, and the dry purification device is preferably a dry purification device capable of realizing carbonyl sulfur (COS) and carbon disulfide (CS) in the blast furnace gas2) Hydrogen sulfide (H)2S), sulfur dioxide (SO)2) The dry purification device comprises a catalytic hydrolysis tower, a desulfurization tower, a pneumatic conveying device (19) and a gas replacement system, wherein the dry purification device is used for removing sulfur-containing substances and cooperatively removing hydrogen chloride (HCl); the catalytic hydrolysis tower is filled with a hydrolysis catalyst and is used for carrying out hydrolysis catalysis on blast furnace gas introduced into the catalytic hydrolysis tower, the catalytic hydrolysis tower is connected with a blast furnace gas inlet (20) arranged at one side of the desulfurizing tower and is used for leading the blast furnace gas after hydrolysis catalysis treatment toSending the mixture into a desulfurizing tower for treatment; the pneumatic conveying device (19) is connected with the top of the desulfurizing tower and is used for conveying a desulfurizing agent into the desulfurizing tower to carry out total sulfur removal on blast furnace gas; the other side of the desulfurizing tower is provided with a clean blast furnace gas discharge port (21) for discharging the clean blast furnace gas after the total sulfur removal through the clean blast furnace gas discharge port (21) and sending the clean blast furnace gas into a blast furnace gas pipe network; the gas replacement system is connected with a replacement gas interface of the desulfurizing tower and used for replacing coal gas in the desulfurizing tower with replacement gas before replacing the desulfurizing agent.
The catalytic hydrolysis tower is provided with a catalytic hydrolysis tower inlet flue, a catalytic hydrolysis tower shell (2), a catalytic hydrolysis tower outlet flue, a catalyst support net (4), a feeding port (3), a discharging port (5) and a sewage discharging port (6), the top end of the catalytic hydrolysis tower shell (2) is connected with the catalytic hydrolysis tower inlet flue and used for feeding blast furnace gas into the catalytic hydrolysis tower, the lower end of the catalytic hydrolysis tower shell (2) is connected with the catalytic hydrolysis tower outlet flue, and the catalytic hydrolysis tower outlet flue is connected with a blast furnace gas inlet (20) of a desulfurization tower and used for feeding the blast furnace gas subjected to hydrolysis catalytic treatment into the desulfurization tower for treatment; the catalyst supporting net (4) is arranged in the catalytic hydrolysis tower shell (2) and is used for supporting a hydrolysis catalyst; a sewage outlet (6) is arranged at the bottom end of the catalytic hydrolysis tower shell (2); the catalytic hydrolysis tower shell (2) is provided with a feed inlet (3) and a discharge outlet (5) for feeding and discharging hydrolysis catalyst.
Wherein, the upper part of the catalytic hydrolysis tower shell (2) is conical, the middle part is cylindrical, and the lower part is conical; the catalytic hydrolysis tower inlet flue is arranged at the top end of the upper cone, the drain outlet (6) is arranged at the bottom end of the lower cone, and the catalytic hydrolysis tower outlet flue is arranged on the lower cone and is positioned at the upper part of the drain outlet (6); the catalyst support screen (4) is disposed within the central cylinder.
Wherein the catalyst is one or more of honeycomb, rod, Raschig ring and sphere, and is used for separating carbonyl sulfide (COS) and carbon disulfide (CS) in blast furnace gas2) Catalytic conversion to H by iso-organic sulfur hydrolysis2S, the active component of the catalyst is one or more of Na, K, Fe, Cu and Ni salt, and the carrier is active alumina, active carbon and cordieriteOne or more of bluestone and hydrotalcite-like compound.
Wherein the catalyst is Raschig annular catalyst, and is randomly stacked on the catalyst support net (4) in the catalytic hydrolysis tower from large to small, and the catalyst is filled with a certain volume, so that the space velocity of the catalytic reaction is 500-4000h-1The gas flow rate is 0.5-2 m/s; preferably, 80 to 95 percent of carbonyl sulfide (COS) and carbon disulfide (CS) in volume fraction of blast furnace gas in the catalytic hydrolysis tower2) Is catalytically converted into H2S。
The desulfurizing tower is a gas-solid cross flow moving bed, the gas pressure is reduced, the desulfurizing agent is less worn, the gas-solid two phases are uniformly contacted, and the residence time adjustment elasticity of the desulfurizing agent is large. Preferably, the flow velocity of the gas in the desulfurizing tower is controlled to be 0.5-3m/s, so that the uniform air distribution is ensured; preferably, the temperature of the blast furnace gas inlet (20) is 40-90 ℃, and the temperature of the clean blast furnace gas discharge outlet (21) is kept basically unchanged.
The outlet flue of the catalytic hydrolysis tower is connected with a blast furnace gas inlet (20) of the desulfurizing tower, and a plurality of desulfurizing agent bins, preferably 4 desulfurizing agent bins, are sequentially arranged on the right side of the blast furnace gas inlet (20).
Wherein, a desulfurizer inlet (7), a first inlet shutoff valve (8), an inlet buffer bin (9), a second inlet shutoff valve (11), a reaction bin (12), a first outlet shutoff valve (14), an outlet buffer bin (16), a second outlet shutoff valve (17) and a desulfurizer outlet (18) are sequentially arranged in the single desulfurizer bin from top to bottom; the replacement gas interface is provided with a first replacement gas interface (10) and a second replacement gas interface (15), the first replacement gas interface (10) is arranged on the side surface of the inlet buffer bin (9), the second replacement gas interface (15) is arranged on the side surface of the outlet buffer bin (16), the gas replacement system is connected with the inlet buffer bin (9) through the first replacement gas interface (10), and is connected with the outlet buffer bin (16) through the second replacement gas interface (15) and used for replacing coal gas in the buffer bin with nitrogen before the desulfurizer is replaced, so that the coal gas is prevented from leaking.
The first inlet shutoff valve (8) is arranged between the desulfurizer inlet (7) and the inlet buffer bin (9) and is used for opening or closing the communication between the desulfurizer inlet (7) and the inlet buffer bin (9); the second inlet shutoff valve (11) is arranged between the inlet buffer bin (9) and the reaction bin (12) and is used for opening or closing the communication between the buffer bin (9) and the reaction bin (12); the first outlet shutoff valve (14) is arranged between the reaction bin (12) and the outlet buffer bin (16) and is used for opening or closing the communication between the reaction bin (12) and the outlet buffer bin (16); the second outlet shutoff valve (17) is arranged between the outlet buffer bin (16) and the desulfurizer outlet (18) and is used for opening or closing the communication between the outlet buffer bin (16) and the desulfurizer outlet (18).
Wherein, two sides of the inlet buffer bin (9), the reaction bin (12) and the outlet buffer bin (16) are respectively provided with a rapping motor which is used for rapping the bin wall periodically and keeping the fluidization state of the desulfurizer. Preferably, the blast furnace gas reacts with the desulfurizer in the reaction bin (12) to remove the total sulfur, and the gas inlet and outlet sides of the reaction bin (12) are provided with desulfurizer baffles (23), so that the desulfurizer is prevented from leaking and the uniform distribution of gas flow is realized. Preferably, an observation window (13) is arranged on the side surface of the reaction bin (12) and is used for observing the conditions in the reaction bin (12) in real time in the operation process.
Wherein, the desulfurizer is porous column type, the carrier is a mixture of zeolite and pumice, and the mol ratio of the pumice to the zeolite is between 0.2 and 0.5; the active ingredient is mainly one or more of ferric oxide, manganese oxide, potassium hydroxide and sodium carbonate, wherein the active ingredient accounts for 3-10% of the mass fraction of the desulfurizer.
Wherein, the desulfurizer is filled in a certain volume, so that the desulfurization reaction airspeed is 500-5000h-1And ensures the high-efficiency removal of pollutants in blast furnace gas.
Wherein, the pneumatic conveying device (19) is connected with a desulfurizer inlet (7) at the top of the desulfurizer bin and is used for conveying the desulfurizer into the reaction bin (12) to carry out total sulfur removal on blast furnace gas.
The gas replacement system comprises a first gas replacement valve (25), a first diffusion valve (24), a first compressed air pipeline, a first nitrogen pipeline, a second compressed air pipeline, a second nitrogen pipeline, a second gas replacement valve (27) and a second diffusion valve (26); the first nitrogen pipeline and the first compressed air pipeline are connected with a first replacement gas interface (10) through a first gas replacement valve (25), the second nitrogen pipeline and the second compressed air pipeline are connected with a second replacement gas interface (15) through a second gas replacement valve (27), and a first diffusion valve (24) and a second diffusion valve (26) are arranged on the diffusion pipeline and used for controlling the diffusion of the replaced coal gas.
The utility model also relates to a dry purification process which can realize the total sulfur removal of blast furnace gas, preferably COS and CS in blast furnace gas2、H2S、SO2A dry purification process for removing sulfur-containing substances and removing HCl in a synergistic manner; which comprises the following steps:
(1) the inlet blast furnace gas (1) firstly enters a catalytic hydrolysis tower for treatment, and COS and CS in the blast furnace gas are treated by a catalyst filled in the catalytic hydrolysis tower2Catalytic conversion to H2S；
(2) Generation of H2S enters the desulfurizing tower along with the blast furnace gas, and a desulfurizing agent is sent into the desulfurizing tower through a pneumatic conveying device (19) to absorb H2S、SO2HCl and other acidic gases, thereby realizing the removal of sulfur-containing substances in the blast furnace gas; preferably, the desulfurizer is the desulfurizer transported by a truck;
(3) the blast furnace gas treated by the desulfurizing tower is discharged through a clean blast furnace gas discharge port (21) and sent into a blast furnace gas pipe network, thereby realizing the desulfurization of the blast furnace gas.
Wherein, the desulfurizing tower has a plurality of desulfurizer storehouses, and wherein 1 desulfurizer storehouse is spare, and other desulfurizer storehouses are in the running state, preferably, 4 desulfurizer storehouses, and wherein 3 are spare for 1, and a plurality of desulfurizer storehouses carry out the desulfurizer replacement according to certain time interval in turn in the operation process, guarantee desulfurization effect.
Wherein, the first inlet shutoff valve (8), the second inlet shutoff valve (11), the first outlet shutoff valve (14) and the second outlet shutoff valve (17) are all in a closed state in the normal operation process of the desulfurizing tower; if the desulfurizer needs to be replaced, firstly opening a first outlet shutoff valve (14), discharging the desulfurizer in a reaction bin (12) into an outlet buffer bin (16), then closing the first outlet shutoff valve (14), opening a second gas replacement valve (27) and a second diffusion valve (26) of a gas replacement system, introducing nitrogen into the outlet buffer bin (16), and replacing and diffusing coal gas in a discharge bin; then closing the second gas replacement valve (27) and the second diffusion valve (26), opening the second outlet shutoff valve (17), discharging the desulfurizer in the outlet buffer bin (16) through a desulfurizer outlet (18), preferably transporting the desulfurizer away by a truck, and closing the second outlet shutoff valve (17); adding the desulfurizer preferably conveyed by the truck into a desulfurizer inlet (7) through a pneumatic conveying device (19), opening a first gas replacement valve (25) and a first diffusion valve (24), introducing nitrogen into an inlet buffer bin (9), and replacing and diffusing coal gas in a discharge bin; then closing the first gas replacement valve (25) and the first diffusion valve (24), opening the first inlet shutoff valve (8), discharging the desulfurizer into the inlet buffer bin (9), closing the first inlet shutoff valve (8), opening the second inlet shutoff valve (11), discharging the desulfurizer into the reaction bin (12), closing the second inlet shutoff valve (11), and completing the desulfurizer replacement process. The blast furnace gas can not leak by adopting a buffer bin and a gas replacement mode, and the operation safety of the system is ensured. If the desulfurizing tower needs to be overhauled, after the desulfurizing agent is emptied according to the mode, the first inlet shutoff valve (8) and the second outlet shutoff valve (17) are closed, the second inlet shutoff valve (11) and the first outlet shutoff valve (14) are opened, the second gas replacement valve (27) and the second diffusion valve (26) are opened, nitrogen is introduced into the whole desulfurizing tower, coal gas in the tower is replaced and diffused, and then the whole system is blown and swept by compressed air, so that the safety of maintainers is ensured.
Preferably, the utility model relates to a dry purification device capable of realizing total sulfur removal of blast furnace gas, preferably a dry purification device capable of realizing COS and CS in the blast furnace gas2、H2S、SO2The device comprises a dry purification device for removing sulfur-containing substances and cooperatively removing HCl, wherein the dry purification device comprises a catalytic hydrolysis tower, a desulfurizing tower, a pneumatic conveying device (19) and a gas replacement system; the pneumatic conveying device (19) is connected with the desulfurizing tower and is used for conveying a desulfurizing agent into the desulfurizing tower; the catalytic hydrolysis tower is filled with a hydrolysis catalyst and is used for carrying out hydrolysis catalysis on blast furnace gas introduced from the upper part of the catalytic hydrolysis tower, the catalytic hydrolysis tower is connected with a blast furnace gas inlet (20) of the desulfurizing tower and is used for sending the blast furnace gas after hydrolysis catalysis treatment into the desulfurizing tower for treatment, and the side surface of the desulfurizing towerThe device is provided with a clean blast furnace gas discharge port (21) for discharging the blast furnace gas treated by the desulfurizing tower through the clean blast furnace gas discharge port (21) and sending the blast furnace gas into a blast furnace gas pipe network.
Preferably, the outlet flue of the catalytic hydrolysis tower is connected with a blast furnace gas inlet (20) of the desulfurization tower, 4 desulfurizer bins are sequentially arranged on the right side of the gas inlet of the desulfurization tower, and a desulfurizer inlet (7), a first inlet shutoff valve (8), an inlet buffer bin (9), a second inlet shutoff valve (11), a reaction bin (12), a first outlet shutoff valve (14), an outlet buffer bin (16), an outlet shutoff valve (17) and a desulfurizer outlet (18) are sequentially arranged from top to bottom in a single desulfurizer bin; and the side surfaces of the inlet buffer bin (9) and the outlet buffer bin (16) are respectively provided with a replacement gas interface (10) and a replacement gas interface (15) which are used for replacing the coal gas in the buffer bins with nitrogen before the desulfurizer is replaced, so that the coal gas is prevented from leaking.
Preferably, 4 desulfurizer bins 3 in the desulfurizing tower are used for 1, and 4 desulfurizer bins are alternately replaced according to a certain time interval in the operation process, so that the desulfurizing effect is ensured. In the normal operation process, the first inlet shutoff valve (8), the second inlet shutoff valve (11), the first outlet shutoff valve (14) and the second outlet shutoff valve (17) are all in a closed state. If the desulfurizer needs to be replaced, firstly opening a first outlet shutoff valve (14), discharging the desulfurizer in the reaction bin into an outlet buffer bin (16), then closing the first outlet shutoff valve (14), opening a second gas replacement valve (27) and a second diffusion valve (26), introducing nitrogen into the outlet buffer bin (16), and replacing and diffusing coal gas in the outlet bin; then closing the second gas replacement valve (27) and the second relief valve (26), opening the second outlet shutoff valve (17), discharging the desulfurizer in the outlet buffer bin (16) through a desulfurizer outlet (18), transporting away the desulfurizer by a truck, and closing the second outlet shutoff valve (17); next, adding the desulfurizer conveyed by the truck into a desulfurizer inlet (7) through a pneumatic conveying device (19), opening a first gas replacement valve (25) and a first diffusion valve (24), introducing nitrogen into an inlet buffer bin (9), and replacing and diffusing coal gas in a discharge bin; then closing the first gas replacement valve (25) and the first diffusion valve (24), opening the first inlet shutoff valve (8), discharging the desulfurizer into the inlet buffer bin (9), closing the first inlet shutoff valve (8), opening the second inlet shutoff valve (11), discharging the desulfurizer into the reaction bin (12), closing the second inlet shutoff valve (11), and completing the desulfurizer replacement process. The blast furnace gas can not leak by adopting a buffer bin and a gas replacement mode, and the operation safety of the system is ensured. If the desulfurizing tower needs to be overhauled, after the desulfurizing agent is emptied according to the mode, the first inlet shutoff valve (8) and the second outlet shutoff valve (17) are closed, the second inlet shutoff valve (11) and the first outlet shutoff valve (14) are opened, the second gas replacement valve (27) and the second diffusion valve (26) are opened, nitrogen is introduced into the whole desulfurizing tower, coal gas in the tower is replaced and diffused, and then the whole system is blown and swept by compressed air, so that the safety of maintainers is ensured.
The principle of the utility model is COS and CS in blast furnace gas2Is catalytically converted into H in a catalytic hydrolysis tower2S; the desulfurizer in the desulfurizing tower absorbs H in the coal gas2S、SO2Acid gases such as HCl; and discharging the treated clean coal gas from the desulfurizing tower and merging the treated clean coal gas into a pipe network. The process realizes the removal of sulfur-containing substances in the blast furnace gas and solves the problem of SO from the source2The problem of exceeding standard is solved, and meanwhile, the corrosion problem of the gas pipeline is controlled to a certain extent by the synergistic removal of HCl.
The utility model provides a technical process is simple, the cost is low, the reliability is good, especially can be in 40-90 ℃ temperature interval, realize H among the blast furnace gas2S、SO2And HCl and other acidic gases.
The utility model has the advantages that: the utility model provides a realize H in blast furnace gas simultaneously2S、SO2And HCl and other acidic gases. The purification process of the utility model firstly uses COS and CS2Isoorganosulfur catalytic conversion to H2S, then absorbing H in the coal gas by a desulfurizer in a desulfurizing tower2S、SO2And acid gases such as HCl. The process can provide accurate process layout scheme and operation parameters for controlling the sulfur pollutants in the blast furnace gas for steel mills and environmental protection companies, and solve the problem of SO from the source2The problem of standard exceeding is solved, meanwhile, the problem of corrosion of the gas pipeline is controlled to a certain extent by the synergistic removal of HCl, the process is simple, and the method can be used forGood reliability and stable operation, and reduces the pollutant control cost.
Drawings
FIG. 1 is a process flow diagram of a dry scrubbing unit for the desulfurization of blast furnace gas;
FIG. 2 is a layout of a dry cleaning plant for the desulfurization of blast furnace gas;
FIG. 3 is a side view of a dry scrubbing apparatus for the desulfurization of blast furnace gas;
FIG. 4 is a detail view of the desulfurizer baffle
Fig. 5 is a diagram of a process for the removal of sulfur contaminants.
The labels in the figure are: 1-inlet blast furnace gas, 2-catalytic hydrolysis tower shell, 3-catalytic hydrolysis tower charging port, 4-catalyst supporting net, 5-catalytic hydrolysis tower discharging port, 6-catalytic hydrolysis tower discharging port, 7-desulfurizer inlet, 8-first inlet shutoff valve, 9-inlet buffer bin, 10-first replacement gas interface, 11-second inlet shutoff valve, 12-reaction bin, 13-observation window, 14-first outlet shutoff valve, 15-second replacement gas interface, 16-outlet buffer bin, 17-second outlet shutoff valve, 18-desulfurizer outlet, 19-pneumatic conveying device, 20-blast furnace gas inlet, 21-blast furnace gas discharging port, 22-rapping motor, 23-desulfurizer baffle, 24-first bleeding valve, 25-first gas displacement valve, 26-second bleed valve, 27-second gas displacement valve.
Detailed Description
As shown in fig. 1, 2, 3 and 4, a dry purification device for total sulfur removal of blast furnace gas is provided, preferably a dry purification device capable of realizing carbonyl sulfide (COS) and carbon disulfide (CS) in blast furnace gas2) Hydrogen sulfide (H)2S), sulfur dioxide (SO)2) The dry purification device comprises a catalytic hydrolysis tower, a desulfurization tower, a pneumatic conveying device 19 and a gas replacement system; the catalytic hydrolysis tower is filled with a hydrolysis catalyst and is used for carrying out hydrolysis catalysis on blast furnace gas introduced into the catalytic hydrolysis tower, and the catalytic hydrolysis tower is connected with a blast furnace gas inlet 20 arranged at one side of the desulfurization tower and is used for feeding the blast furnace gas subjected to hydrolysis catalysis treatment into the desulfurization tower for treatment; the pneumatic conveying device 19 is connected with the top of the desulfurizing towerThe part is used for sending the desulfurizer into a desulfurizing tower to carry out total sulfur removal on blast furnace gas; the other side of the desulfurizing tower is provided with a clean blast furnace gas discharge port 21 for discharging the clean blast furnace gas after the total sulfur removal through the clean blast furnace gas discharge port 21 and sending the clean blast furnace gas into a blast furnace gas pipe network; the gas replacement system is connected with replacement gas interfaces 10 and 15 of the desulfurizing tower and is used for replacing coal gas in the desulfurizing tower with replacement gas before replacing the desulfurizing agent.
As shown in fig. 2, the catalytic hydrolysis tower is provided with a catalytic hydrolysis tower inlet flue, a catalytic hydrolysis tower shell 2, a catalytic hydrolysis tower outlet flue, a catalyst support net 4, a feeding port 3, a discharging port 5 and a sewage discharging port 6, wherein the top end of the catalytic hydrolysis tower shell is connected with the catalytic hydrolysis tower inlet flue and is used for feeding blast furnace gas into the catalytic hydrolysis tower, the lower end of the catalytic hydrolysis tower shell is connected with the catalytic hydrolysis tower outlet flue, and the catalytic hydrolysis tower outlet flue is connected with a desulfurization tower blast furnace gas inlet 20 and is used for feeding the blast furnace gas subjected to hydrolysis catalytic treatment into the desulfurization tower for treatment; the catalyst supporting net 4 is arranged in the catalytic hydrolysis tower shell 2 and is used for supporting a hydrolysis catalyst; a sewage outlet 6 is arranged at the bottom end of the catalytic hydrolysis tower shell; the shell of the catalytic hydrolysis tower is provided with a feed inlet 3 and a discharge outlet 5 for feeding and discharging the hydrolysis catalyst. The upper part of the catalytic hydrolysis tower shell is conical, the middle part of the catalytic hydrolysis tower shell is cylindrical, and the lower part of the catalytic hydrolysis tower shell is conical; the catalytic hydrolysis tower inlet flue is arranged at the top end of the upper conical part, the drain outlet 6 is arranged at the bottom end of the lower conical part, and the catalytic hydrolysis tower outlet flue is arranged on the lower conical part and is positioned at the upper part of the drain outlet 6; the catalyst support screen 4 is disposed on the intermediate cylinder. The catalyst is one or more of honeycomb, rod, Raschig ring and sphere, and is used for treating COS and CS in the blast furnace gas2Catalytic conversion to H by iso-organic sulfur hydrolysis2S, the active component of the catalyst is one or more of Na, K, Fe, Cu and Ni salt, and the carrier is one or more of activated alumina, activated carbon, cordierite and hydrotalcite-like compound. The catalyst configuration is preferably Raschig annular catalyst, the catalyst is scattered and stacked from large to small on the catalyst support net 4 in the catalytic hydrolysis tower, and the catalyst is filled in a certain volume, so that the space velocity of the catalytic reaction is 500-4000-h-1The gas flow rate is 0.5-2 m/s; preferably, the volume fraction of COS and CS in the catalytic hydrolysis tower is 80-95 percent2Is catalytically converted into H2S。
As shown in figures 1, 2, 3 and 4, the desulfurizing tower is in a gas-solid cross flow moving bed form, the gas pressure is reduced, the desulfurizing agent is less worn, the gas-solid two phases are uniformly contacted, and the residence time adjustment elasticity of the desulfurizing agent is large. The flow velocity of gas in the desulfurizing tower is controlled to be 0.5-3m/s, so that the uniform air distribution is ensured; preferably, the blast furnace gas inlet temperature is 40-90 ℃ and the outlet temperature is kept substantially constant. The outlet flue of the catalytic hydrolysis tower is connected with a desulfurizing tower blast furnace gas inlet 20, 4 desulfurizing agent bins are sequentially arranged on the right side of the desulfurizing tower gas inlet, and a desulfurizing agent inlet 7, a first inlet shutoff valve 8, an inlet buffer bin 9, a second inlet shutoff valve 11, a reaction bin 12, a first outlet shutoff valve 14, an outlet buffer bin 16, a second outlet shutoff valve 17 and a desulfurizing agent outlet 18 are sequentially arranged on a single desulfurizing agent bin from top to bottom; the side surfaces of the inlet buffer bin 9 and the outlet buffer bin 16 are respectively provided with a replacement gas interface 10 and a replacement gas interface 15 which are used for replacing the coal gas in the buffer bins with nitrogen before the desulfurizer is replaced, so that the coal gas is prevented from leaking. Rapping motors 22 are arranged on two side surfaces of the inlet buffer bin 9, the reaction bin 12 and the outlet buffer bin 16 of the desulfurizing tower, and rapping is carried out on the bin wall regularly to keep the fluidizing state of the desulfurizing agent. The gas inlet and outlet sides of the reaction bin 12 are provided with desulfurizer baffles 23, which ensure that the desulfurizer does not leak and simultaneously play a role of uniform distribution of gas flow. An observation window 13 is arranged on the side surface of the reaction bin 12, and the condition in the bin is observed in real time in the operation process. Preferably, the desulfurizer is directly placed in the desulfurization tower and divided into four modules, and the four modules are separated by a desulfurizer baffle plate 23, so that the desulfurizer in each module can be replaced independently. The desulfurizer retainer 23 is shown in fig. 4, and the desulfurizer retainer 23 has holes so that the desulfurizer can be retained but the gas can pass through. Preferably, the blast furnace gas inlet 20 is a hole formed in the reaction chamber 12 and is an interface of the reaction chamber. The gas enters the desulfurization tower directly through inlet 20. All the reaction bins are arranged in the desulfurizing tower and are separated by a desulfurizing agent baffle plate 23.
The first inlet shutoff valve 8 is arranged between the desulfurizer inlet 7 and the inlet buffer bin 9 and is used for opening or closing the communication between the desulfurizer inlet 7 and the inlet buffer bin 9; the second inlet shutoff valve 11 is arranged between the inlet buffer bin 9 and the reaction bin 12 and is used for opening or closing the communication between the buffer bin 9 and the reaction bin 12; the first outlet shutoff valve 14 is arranged between the reaction bin 12 and the outlet buffer bin 16 and is used for opening or closing the communication between the reaction bin 12 and the outlet buffer bin 16; the second outlet shutoff valve 17 is disposed between the outlet surge bin 16 and the desulfurizing agent outlet 18, and is used for opening or closing communication between the outlet surge bin 16 and the desulfurizing agent outlet 18. Wherein, the pneumatic conveying device 19 is connected with a desulfurizer inlet 7 at the top of the desulfurizer bin and is used for conveying the desulfurizer into the reaction bin 12 to carry out total sulfur removal on the blast furnace gas. The gas replacement system comprises a first gas replacement valve 25, a first diffusion valve 24, a first compressed air pipeline, a first nitrogen pipeline, a second compressed air pipeline, a second nitrogen pipeline, a second gas replacement valve 27 and a second diffusion valve 26; the first nitrogen pipeline and the first compressed air pipeline are connected with the first replacement gas interface 10 through a first gas replacement valve 25, the second nitrogen pipeline and the second compressed air pipeline are connected with the second replacement gas interface 15 through a second gas replacement valve 27, and a first diffusion valve 24 and a second diffusion valve 26 are arranged on the diffusion pipeline and used for controlling the diffusion of the replaced coal gas.
As shown in fig. 2, 4 desulfurizing agent bins 3 in the desulfurizing tower are used for 1, and the 4 desulfurizing agent bins are alternately replaced by desulfurizing agents at certain time intervals in the operation process, so that the desulfurizing effect is ensured. During normal operation the first inlet shut-off valve 8, the second inlet shut-off valve 11, the first outlet shut-off valve 14 and the second outlet shut-off valve 17 are all in a closed state. If the desulfurizer needs to be replaced, the first outlet shutoff valve 14 is opened firstly, the desulfurizer in the reaction bin is discharged into the outlet buffer bin 16, then the first outlet shutoff valve 14 is closed, the second gas replacement valve 27 and the second diffusion valve 26 are opened, nitrogen is introduced into the outlet buffer bin 16, and the coal gas in the outlet buffer bin is replaced and diffused; then closing the second gas replacement valve 27 and the second blow-off valve 26, opening the second outlet shutoff valve 17, discharging the desulfurizer in the outlet buffer bin 16 through the desulfurizer outlet 18, transporting away by a truck, and closing the second outlet shutoff valve 17; next, adding the desulfurizer conveyed by the truck into a desulfurizer inlet 7 through a pneumatic conveying device 19, opening a first gas replacement valve 25 and a first blow-off valve 24, introducing nitrogen into an inlet buffer bin 9, and replacing and blowing off coal gas in the outlet bin; then, the first gas replacement valve 25 and the first blow-off valve 24 are closed, the first inlet shutoff valve 8 is opened, the desulfurizing agent is discharged into the inlet buffer bin 9, the first inlet shutoff valve 8 is closed, the second inlet shutoff valve 11 is opened, the desulfurizing agent is discharged into the reaction bin 12, and the second inlet shutoff valve 11 is closed, thereby completing the desulfurizing agent replacement process. The blast furnace gas can not leak by adopting a buffer bin and a gas replacement mode, and the operation safety of the system is ensured. If the desulfurizing tower needs to be overhauled, after the desulfurizing agent is emptied according to the mode, the first inlet shutoff valve 8 and the second outlet shutoff valve 17 are closed, the second inlet shutoff valve 11 and the first outlet shutoff valve 14 are opened, the second gas replacement valve 27 and the second diffusion valve 26 are opened, nitrogen is introduced into the whole desulfurizing tower, the coal gas in the tower is replaced and diffused, and then the whole system is purged by compressed air to ensure the safety of maintainers.
As shown in figure 2, the desulfurizer is in a porous column shape, the carrier is a mixture of zeolite and pumice, and the mole ratio of the pumice to the zeolite is between 0.2 and 0.5; the active ingredient is mainly one or more of ferric oxide, manganese oxide, potassium hydroxide and sodium carbonate, wherein the active ingredient accounts for 3-10% of the mass fraction of the desulfurizer. The desulfurizer is filled in a certain volume, so that the desulfurization reaction airspeed is 500-5000h-1And ensures the high-efficiency removal of pollutants in blast furnace gas.
As shown in figures 1 and 2, a dry purification process capable of realizing total sulfur removal of blast furnace gas, preferably a dry purification process capable of realizing COS and CS in the blast furnace gas2、H2S、SO2The dry purification process for removing sulfur-containing substances and removing HCl in a synergistic manner, preferably, the dry purification process is the dry purification process which can realize the total sulfur removal of blast furnace gas and is shown in the figures 1 and 2; the method is characterized by comprising the following steps:
(1) the inlet blast furnace gas 1 firstly enters a catalytic hydrolysis tower for treatment, and COS and CS in the blast furnace gas are treated by a catalyst filled in the catalytic hydrolysis tower2Catalytic conversion to H2S；
(2) Generation of H2S enters the desulfurizing tower along with the blast furnace gas, and the desulfurizing agent conveyed by the truck is conveyed into the desulfurizing tower through a pneumatic conveying system to absorb H2S、SO2HCl and other acidic gases, thereby realizing the removal of sulfur-containing substances in the blast furnace gas;
(3) the blast furnace gas treated by the desulfurizing tower is discharged through the clean blast furnace gas discharge port 21 and sent into a blast furnace gas pipe network, thereby realizing the desulfurization of the blast furnace gas.
According to H in outlet gas in the running process2The concentration of S adjusts the replacement frequency of the desulfurizer, realizes the removal of sulfur-containing substances in blast furnace gas, and solves the problem of SO from the source2The problem of exceeding standard is solved, and meanwhile, the corrosion problem of the gas pipeline is controlled to a certain extent by the synergistic removal of HCl.
The technical process of the utility model is as follows: combustible gas (containing nitrogen (N)) as byproduct in blast furnace iron-making production process2) Carbon monoxide (CO) and carbon dioxide (CO)2) Hydrogen (H)2) Hydrocarbons, a small amount of sulfur-containing compounds and dust) through gravity dust removal, bag dust removal, and a residual pressure turbine power generation unit (TRT), just as the inlet blast furnace gas 1 of the purification process. Blast furnace gas passes through a catalytic hydrolysis tower filled with a catalyst. The catalyst takes one or more of active alumina, active carbon, cordierite and hydrotalcite-like compound as a carrier, one or more of Na, K, Fe, Cu and Ni salts as an active component, and the configuration of the catalyst is a Raschig annular catalyst. The catalyst is filled in a certain volume, so that the space velocity of the catalytic reaction is 500-4000h-1The gas flow rate is 0.5-2m/s, so that 80-95% of COS and CS in the blast furnace gas in the catalytic hydrolysis tower are in volume fraction2Is catalytically converted into H2And S. And then enters the desulfurization tower of fig. 2. A desulfurizing agent is filled in the desulfurizing tower, the desulfurizing agent is in a porous column shape, the carrier is a mixture of zeolite and pumice, and the molar ratio of the pumice to the zeolite is between 0.2 and 0.5; the active ingredient is mainly one or more of ferric oxide, manganese oxide, potassium hydroxide and sodium carbonate, wherein the active ingredient accounts for 3-10% of the mass fraction of the desulfurizer. The desulfurizing agent is filled in a volume such thatThe desulfurization reaction space velocity is 500-5000h-1And ensures the high-efficiency removal of pollutants in blast furnace gas.
As shown in fig. 5, in the catalytic hydrolysis tower, the blast furnace gas and the moisture react with the catalyst as follows:
COS+H20＝CO2+H2S；
CS2+H20＝COS+H2S；
CS2+2H2O＝2H2S+CO2。
h produced by subsequent reaction2S and small amount of HCl and SO in blast furnace gas2And (3) reacting the acid gas with a desulfurizing agent as follows:
Fe2O3.H2O+3H2S＝Fe2S3.H2O+3H2O
MnO+H2S＝MnO+H2O
H2S+2KOH＝K2S+2H2O，SO2+2KOH＝K2SO3+H2O，HCl+KOH＝KCl+H2O
H2S+2Na2CO3＝Na2S+2NaHCO3，SO2+2Na2CO3+H2O＝2NaHCO3+Na2SO3，HCl+Na2CO3＝NaCl+NaHCO3
O2when present, Na2SO3Can be oxidized to Na2SO4。
Example (b):
the blast furnace gas of a certain steel mill adopts the device and the process of the utility model, the temperature of the inlet gas of the catalytic hydrolysis tower is 90 ℃, COS and CS2The content is 120mg/Nm3，H2S content of 50mg/Nm3The inlet gas flow rate is 5000Nm3H, 2.5m is filled in the catalytic hydrolysis tower3The cross-sectional area of the catalyst perpendicular to the flow direction of the flue gas is 1.5m2The flow velocity of flue gas in the catalytic hydrolysis tower is 1m/s, and the flow velocity isOver-catalytic hydrolysis column, COS and CS2Catalytic conversion to H2The proportion of S was 91%. Blast furnace gas enters the desulfurizing tower through a gas inlet on the side surface of the desulfurizing tower, a gas channel of the desulfurizing tower is square, the side length is 1.2m, and the apparent flow velocity of the gas is 0.9 m/s. 4 desulfurizing agent bins are arranged in total, 3 uses 1 device, and the volume of a single desulfurizing agent bin is 4m3The outlet gas temperature was 85 ℃. After the purification process of the drying method, COS and CS2Conversion efficiency is greater than 90%, and outlet H2S concentration lower than 15mg/Nm3。
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutes or changes made by the technical personnel in the technical field on the basis of the utility model are all within the protection scope of the utility model. The protection scope of the present invention is subject to the claims.
Claims (10)
1. The dry purification device for total sulfur removal of blast furnace gas is characterized by comprising a catalytic hydrolysis tower, a desulfurization tower, a pneumatic conveying device (19) and a gas replacement system; the catalytic hydrolysis tower is filled with a hydrolysis catalyst and is used for carrying out hydrolysis catalysis on blast furnace gas introduced into the catalytic hydrolysis tower, and the catalytic hydrolysis tower is connected with a blast furnace gas inlet (20) arranged at one side of the desulfurization tower and is used for feeding the blast furnace gas subjected to hydrolysis catalysis treatment into the desulfurization tower for treatment; the pneumatic conveying device (19) is connected with the top of the desulfurizing tower and is used for conveying a desulfurizing agent into the desulfurizing tower to carry out total sulfur removal on blast furnace gas; the other side of the desulfurizing tower is provided with a clean blast furnace gas discharge port (21) for discharging the clean blast furnace gas after the total sulfur removal through the clean blast furnace gas discharge port (21) and sending the clean blast furnace gas into a blast furnace gas pipe network; the gas replacement system is connected with a replacement gas interface of the desulfurizing tower and used for replacing coal gas in the desulfurizing tower with replacement gas before replacing the desulfurizing agent.
2. The dry purification device according to claim 1, wherein the catalytic hydrolysis tower is provided with a catalytic hydrolysis tower inlet flue, a catalytic hydrolysis tower shell (2), a catalytic hydrolysis tower outlet flue, a catalyst support net (4), a feed inlet (3), a discharge opening (5) and a drain outlet (6), the top end of the catalytic hydrolysis tower shell (2) is connected with the catalytic hydrolysis tower inlet flue and used for feeding blast furnace gas into the catalytic hydrolysis tower, the lower end of the catalytic hydrolysis tower shell (2) is connected with the catalytic hydrolysis tower outlet flue, and the catalytic hydrolysis tower outlet flue is connected with a blast furnace gas inlet (20) of a desulfurization tower and used for feeding the blast furnace gas subjected to hydrolysis catalytic treatment into the desulfurization tower for treatment; the catalyst supporting net (4) is arranged in the catalytic hydrolysis tower shell (2) and is used for supporting a hydrolysis catalyst; a sewage outlet (6) is arranged at the bottom end of the catalytic hydrolysis tower shell (2); the catalytic hydrolysis tower shell (2) is provided with a feed inlet (3) and a discharge outlet (5) for feeding and discharging hydrolysis catalyst.
3. The dry purification device according to claim 2, characterized in that the catalytic hydrolysis column shell (2) is conical in the upper part, cylindrical in the middle part and conical in the lower part; the catalytic hydrolysis tower inlet flue is arranged at the top end of the upper cone, the drain outlet (6) is arranged at the bottom end of the lower cone, and the catalytic hydrolysis tower outlet flue is arranged on the lower cone and is positioned at the upper part of the drain outlet (6); the catalyst support screen (4) is disposed within the central cylinder.
4. The dry purification device according to one of claims 1 to 3, characterized in that the desulfurization tower is in the form of a gas-solid cross-flow moving bed.
5. The dry purification device according to one of claims 1 to 3, wherein the outlet flue of the catalytic hydrolysis tower is connected with the blast furnace gas inlet (20) of the desulfurization tower, and a plurality of desulfurizing agent bins are sequentially arranged on the right side of the blast furnace gas inlet (20).
6. The dry purification device according to claim 5, wherein a desulfurizer inlet (7), a first inlet shutoff valve (8), an inlet buffer bin (9), a second inlet shutoff valve (11), a reaction bin (12), a first outlet shutoff valve (14), an outlet buffer bin (16), a second outlet shutoff valve (17), and a desulfurizer outlet (18) are sequentially arranged from top to bottom in a single desulfurizer bin; the replacement gas interface is provided with a first replacement gas interface (10) and a second replacement gas interface (15), the first replacement gas interface (10) is arranged on the side surface of the inlet buffer bin (9), the second replacement gas interface (15) is arranged on the side surface of the outlet buffer bin (16), the gas replacement system is connected with the inlet buffer bin (9) through the first replacement gas interface (10), and the gas replacement system is connected with the outlet buffer bin (16) through the second replacement gas interface (15) and used for replacing coal gas in the buffer bin with nitrogen before the desulfurizer is replaced.
7. The dry cleaning device according to claim 6, characterized in that a first inlet shutoff valve (8) is arranged between the desulfurizer inlet (7) and the inlet surge bin (9) for opening or closing the communication between the desulfurizer inlet (7) and the inlet surge bin (9); the second inlet shutoff valve (11) is arranged between the inlet buffer bin (9) and the reaction bin (12) and is used for opening or closing the communication between the buffer bin and the reaction bin (12); the first outlet shutoff valve (14) is arranged between the reaction bin (12) and the outlet buffer bin (16) and is used for opening or closing the communication between the reaction bin (12) and the outlet buffer bin (16); the second outlet shutoff valve (17) is arranged between the outlet buffer bin (16) and the desulfurizer outlet (18) and is used for opening or closing the communication between the outlet buffer bin (16) and the desulfurizer outlet (18).
8. The dry cleaning device according to claim 6, characterized in that rapping motors are arranged on both sides of the inlet surge bin (9), the reaction bin (12) and the outlet surge bin (16); the coal gas inlet and outlet sides of the reaction bin (12) are provided with desulfurizer baffles (23) for protecting, and the side surface of the reaction bin (12) is provided with an observation window (13).
9. The dry cleaning device according to claim 6, characterized in that the pneumatic conveying device (19) is connected with a desulfurizer inlet (7) at the top of the desulfurizer bin and used for feeding the desulfurizer into the reaction bin (12) to perform total sulfur removal on the blast furnace gas.
10. The dry cleaning device according to claim 6, characterized in that the gas replacement system comprises a first gas replacement valve (25), a first blow-off valve (24), a first compressed air line, a first nitrogen line, a second compressed air line, a second nitrogen line, a second gas replacement valve (27) and a second blow-off valve (26); the first nitrogen pipeline and the first compressed air pipeline are connected with a first replacement gas interface (10) through a first gas replacement valve (25), the second nitrogen pipeline and the second compressed air pipeline are connected with a second replacement gas interface (15) through a second gas replacement valve (27), and a first diffusion valve (24) and a second diffusion valve (26) are arranged on the diffusion pipeline and used for controlling the diffusion of the replaced coal gas.
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