CN113583721A - Oxygen-free high-water-content high-furnace gas desulfurization system and process - Google Patents
Oxygen-free high-water-content high-furnace gas desulfurization system and process Download PDFInfo
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- CN113583721A CN113583721A CN202110827625.5A CN202110827625A CN113583721A CN 113583721 A CN113583721 A CN 113583721A CN 202110827625 A CN202110827625 A CN 202110827625A CN 113583721 A CN113583721 A CN 113583721A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
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- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/002—Removal of contaminants
- C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
- C10K1/004—Sulfur containing contaminants, e.g. hydrogen sulfide
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/32—Purifying combustible gases containing carbon monoxide with selectively adsorptive solids, e.g. active carbon
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Abstract
The invention discloses an oxygen-free high-water-content high-furnace-gas desulfurization system and a process, wherein the system comprises a cooler, a first heat exchanger, a hydrolysis tower and an adsorption tower, a cold air outlet of the cooler is communicated with a first heat exchange air inlet of the first heat exchanger, a first heat exchange air outlet of the first heat exchanger is communicated with a hydrolysis air inlet of the hydrolysis tower, and a hydrolysis air outlet of the hydrolysis tower is communicated with an adsorption air inlet of the adsorption tower. The invention greatly prolongs the service life of the hydrolytic agent by dehydrating the blast furnace gas before hydrolyzing the blast furnace gas; meanwhile, the invention carries out source desulphurization on the blast furnace gas by mutually matching the processes of dehydration, hydrolysis, oxygenation and adsorption, so that a user of the blast furnace gas does not need to use desulphurization equipment, the emission of sulfur is intensively treated, and the aim of directly discharging the blast furnace gas after reaching the standard after combustion is fulfilled.
Description
Technical Field
The invention relates to the technical field of atmosphere purification and environment protection, in particular to a system and a process for desulfurizing oxygen-free high-water-content high-furnace gas.
Background
Blast furnace gas has considerable combustion value, with a carbon monoxide content of about 28% by volume, a hydrogen content of about 1% by volume and a methane content of about 0.5% by volume. Blast furnace gas is usually sent to a hot blast stove, a heating furnace, a coke oven, a boiler and a gas turbine set in a fuel mode for combustion. However, in addition to the above-mentioned gases, the blast furnace gas contains COS (carbonyl sulfide) and CS2、H2S, wherein the main component of the sulfide is COS, and the total sulfur concentration generally reaches 200mgS/Nm3The above. These sulfides may be SO, if not limited2Is discharged into the air, thereby causing a large amount of acid rain to form. With the increasing awareness of environmental protection, the emission limit of sulfur is becoming more and more strict, and each terminal using blast furnace gas builds up a huge flue gas desulfurization device. The dispersed desulfurization device not only greatly wastes the limited steel mill space, but also increasingly highlights the cost and secondary pollution of flue gas desulfurization. Therefore, source desulfurization of blast furnace gas becomes an ideal method for treating sulfur species, compared to terminal desulfurization techniques.
The prior art CN 111534335A discloses a blast furnace gas dry-method fine desulfurization treatment system and a method, which comprises the following steps: the blast furnace gas firstly enters a gas cooling heat exchanger for cooling, the cooling heat exchanger reduces the temperature of the gas by 5 ℃, and partial moisture is separated out. Then the gas enters a catalytic hydrolysis tower, organic sulfur contained in the gas is converted into inorganic sulfur after passing through a hydrolysis catalyst, the hydrolyzed blast furnace gas passes through a reheater at the front end of the adsorption tower and is heated to enter a hydrogen sulfide adsorption tower, and the inorganic sulfur in the gas is removed through a catalyst in the tower. The blast furnace gas after inorganic sulfur removal can be directly conveyed to a downstream customer using end. But the temperature of blast furnace gas with larger water content is reduced by only 5 ℃, and the water in the blast furnace gas can not be effectively removed, thus seriously affecting the hydrolysis efficiency of the hydrolytic agent. In addition, when the oxygen content in the blast furnace gas is less than 0.01 vol%, the adsorption efficiency of the metal-based supported adsorbent is also seriously affected.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a system and a process for desulfurizing oxygen-free high-water-content high-furnace gas, which effectively meet the requirement of the prior blast-furnace gas desulfurization process on the water content of the blast-furnace gas by adopting low-temperature dehydration and micro-oxygenation technologies and greatly improve the desulfurization efficiency of the blast-furnace gas.
The invention adopts the following technical scheme:
the utility model provides an anaerobic high moisture content high furnace gas desulfurization system, the system includes cooler, first heat exchanger, hydrolyzes tower and adsorption tower, the one end of cooler is equipped with blast furnace gas air inlet, and the other end is equipped with air conditioning gas outlet and comdenstion water export, be equipped with first heat transfer air inlet and first heat transfer gas outlet on the first heat exchanger, be equipped with the gas inlet of hydrolysising and hydrolysising the gas outlet on the tower of hydrolysising, be equipped with on the adsorption tower and adsorb the gas outlet, the air conditioning gas outlet with first heat transfer air inlet intercommunication, first heat transfer gas outlet with the gas inlet intercommunication of hydrolysising, the gas outlet of hydrolysising with adsorb the gas inlet intercommunication.
The cooler is also provided with a refrigerant inlet and a refrigerant outlet, and the refrigerant inlet and the refrigerant outlet are used as a communicated pair and are used for cooling and dehydrating the blast furnace gas entering the cooler through the blast furnace gas inlet; the first heat exchanger is also provided with a hot flue gas inlet and a hot flue gas outlet, and the hot flue gas inlet and the hot flue gas outlet are used as a communicated pair and used for heating blast furnace gas cooled and dehydrated by the cooler.
The system also comprises a first fan and a mixer, wherein a hydrolysis gas outlet of the hydrolysis tower and a gas outlet of the first fan are respectively communicated with a gas inlet of the mixer, a gas outlet of the mixer is communicated with an adsorption gas inlet of the adsorption tower, and blast furnace gas hydrolyzed by the hydrolysis tower and air introduced from the first fan are mixed by the mixer and then enter the adsorption tower through the adsorption gas inlet for adsorption desulfurization.
The hydrolysis tower and the adsorption tower are both of layered tower body structures, the layered tower body is sequentially provided with an upper air pressure buffer area, a packing layer and a lower air pressure buffer area from top to bottom, the hydrolysis air inlet and the adsorption air inlet are respectively arranged on one side wall of the upper air pressure buffer area of the layered tower body where the hydrolysis air inlet and the adsorption air inlet are arranged, and the hydrolysis air outlet and the adsorption air outlet are respectively arranged on the other side wall of the lower air pressure buffer area of the layered tower body where the hydrolysis air outlet and the adsorption air outlet are arranged; the filler layer in the hydrolysis tower is used for filling a hydrolysis agent; the filler layer of the adsorption tower is used for filling an adsorbent.
The volume ratio of the upper air pressure buffer area to the packing layer to the lower air pressure buffer area is 1 (1-2) to 1.
The hydrolysis tower and the adsorption tower respectively comprise at least two layered tower bodies which are stacked up and down and arranged in parallel, and a heat insulation layer is arranged between every two adjacent layered tower bodies.
Preferably, the hydrolysis tower comprises 3 layered tower bodies which are stacked up and down and arranged in parallel; the adsorption tower comprises 4 layered tower bodies which are overlapped up and down and arranged in parallel, wherein 3 layered tower bodies are used for carrying out adsorption treatment on blast furnace gas, and the other layered tower body is standby or used for regenerating an adsorbent.
The system also comprises a second heat exchanger, wherein a second heat exchange air inlet and a second heat exchange air outlet are arranged on the second heat exchanger, the second heat exchange air inlet is respectively communicated with the 4 adsorption air inlets of the adsorption tower, the 4 adsorption air outlets of the adsorption tower are converged and then divided into two paths, one path is used for recovering the purified blast furnace gas, the other path is communicated with the second heat exchange air inlet through a regeneration air inlet pipeline through a second fan, and part of the purified blast furnace gas enters the adsorption tower after being heated by the second heat exchanger and is used for regenerating the adsorbent saturated in the adsorption tower.
The first fan is an air blower, and the second fan is an induced draft fan.
A desulfurization process for oxygen-free high-water-content blast furnace gas comprises the following steps:
s1, introducing the blast furnace gas with high water content and no oxygen into a cooler, and cooling to 5-15 ℃ for dehydration treatment to obtain first feed gas with low water content;
s2, heating the dehydrated first raw material gas to 70-100 ℃ through a first heat exchanger, introducing the first raw material gas into a hydrolysis tower, carrying out organic sulfur hydrolysis treatment on the first raw material gas through a hydrolytic agent, and converting organic sulfur into inorganic sulfur to obtain a hydrolyzed second raw material gas;
and S3, introducing the second raw material gas into an adsorption tower, and performing adsorption desulfurization treatment by using an adsorbent to obtain the purified blast furnace gas.
Before the second raw material gas is introduced into the adsorption tower in the step S3, adding air into the second raw material gas so that the volume ratio of the air to the second raw material gas is 1: (1000-3000), the oxygen content in the mixed gas is 0.03-0.1 vol%, and the mixed gas are introduced into an adsorption tower.
The method also comprises the step of regenerating the adsorbent in the adsorption tower:
and S4, heating part of the blast furnace gas desulfurized and purified in the step S3 to 180-200 ℃ by a second heat exchanger, introducing the heated blast furnace gas into a layered tower body of the adsorbent to be regenerated of the adsorption tower, and regenerating the adsorbent by utilizing the reducing atmosphere in the purified blast furnace gas.
In the step S1, the water content in the blast furnace gas before dehydration is greater than 30%, and the water content in the blast furnace gas after dehydration is less than 7%.
The technical scheme of the invention has the following advantages:
A. the oxygen-free high-water-content high-furnace gas desulfurization system greatly prolongs the service life of the hydrolytic agent by dehydrating the blast furnace gas before the blast furnace gas is hydrolyzed; meanwhile, the invention carries out source desulphurization on the blast furnace gas by mutually matching the processes of dehydration, hydrolysis, oxygenation and adsorption, so that a user of the blast furnace gas does not need to use desulphurization equipment, the emission of sulfur is intensively treated, and the aim of directly discharging the blast furnace gas after reaching the standard after combustion is fulfilled.
B. According to the oxygen-free high-water-content high-furnace gas desulfurization system provided by the invention, each layered tower body structure in the hydrolysis tower and the adsorption tower comprises the upper air pressure buffer area of the packing layer, the packing layer and the lower air pressure buffer area positioned below the packing layer, so that the thickness of the packing layer is reduced, and the pretreatment gas is discharged from top to bottom, so that the resistance drop of the packing layer can be effectively reduced (the resistance drop of the blast furnace gas passing through the hydrolysis tower and the adsorption tower is less than 500Pa), the pressure requirement of the desulfurization system on the blast furnace gas is reduced, and the effective treatment capacity of the blast furnace gas is improved.
C. According to the invention, the layered tower body structures in the hydrolysis tower and the adsorption tower are vertically arranged, so that the floor area of the system is greatly reduced, and land resources are saved.
Drawings
In order to more clearly illustrate the embodiments of the present invention, the drawings which are needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained from the drawings without inventive labor to those skilled in the art.
FIG. 1 is a schematic view of the overall structure of an oxygen-free high water content high furnace gas desulfurization system of the present invention;
FIG. 2 is a schematic view of a layered tower structure of a hydrolysis tower according to the present invention;
FIG. 3 is a schematic view of a layered tower structure of an adsorption tower of the present invention.
The labels in the figure are as follows:
1-a cooler, 11-a blast furnace gas inlet, 12-a cold air outlet, 13-a condensed water outlet, 14-a refrigerant inlet and 15-a refrigerant outlet; 2-a first heat exchanger, 21-a first heat exchange air inlet, 22-a first heat exchange air outlet, 23-a hot flue gas inlet and 24-a hot flue gas outlet; 3-hydrolysis tower, 31-hydrolysis air inlet, 32-hydrolysis air outlet; 4-adsorption tower, 41-adsorption air inlet, 42-adsorption air outlet; 5-a first fan; 6-a mixer; 7-a second fan; 8-a second heat exchanger, 81-a second heat exchange air inlet and 82-a second heat exchange air outlet; 9-regeneration air inlet pipeline; 10-adsorption regeneration gas outlet pipeline;
a-an upper air pressure buffer zone; b-a filler layer; c-a lower air pressure buffer zone; d-heat insulation layer.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", etc., indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and "third" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, e.g., as meaning either a fixed connection, a removable connection, or an integral connection; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
As shown in fig. 1-3, the present invention provides an oxygen-free high water content high-furnace gas desulfurization system, which comprises a cooler 1, a first heat exchanger 2, a hydrolysis tower 3 and an adsorption tower 4, wherein one end of the cooler 1 is provided with a blast furnace gas inlet 11, the other end is provided with a cold air outlet 12 and a condensed water outlet 13, the first heat exchanger 2 is provided with a first heat exchange gas inlet 21 and a first heat exchange gas outlet 22, the hydrolysis tower 3 is provided with a hydrolysis gas inlet 31 and a hydrolysis gas outlet 32, the adsorption tower 4 is provided with an adsorption gas inlet 41 and an adsorption gas outlet 42, the cold air outlet 12 is communicated with the first heat exchange gas inlet 21, the first heat exchange gas outlet 22 is communicated with the hydrolysis gas inlet 31, and the hydrolysis gas outlet 32 is communicated with the adsorption gas inlet 41. The cooler 1 is also provided with a refrigerant inlet 14 and a refrigerant outlet 15, and the refrigerant inlet 14 and the refrigerant outlet 15 are a communicated pair and used for cooling and dehydrating the blast furnace gas entering the cooler 1 through the blast furnace gas inlet 11; the first heat exchanger 2 is also provided with a hot flue gas inlet 23 and a hot flue gas outlet 24, and the hot flue gas inlet 23 and the hot flue gas outlet 24 are used as a communicated pair and used for heating blast furnace gas cooled and dehydrated by the cooler 1.
The system further comprises a first fan 5 and a mixer 6, the hydrolysis gas outlet 32 of the hydrolysis tower 3 and the gas outlet of the first fan 5 are respectively communicated with the gas inlet of the mixer 6, the gas outlet of the mixer 6 is communicated with the adsorption gas inlet 41 of the adsorption tower 4, and blast furnace gas hydrolyzed by the hydrolysis tower 3 and air introduced from the first fan 5 are mixed by the mixer 6 and then enter the adsorption tower 4 through the adsorption gas inlet 41 for adsorption desulfurization. The oxygen-free high-water-content high-furnace gas desulfurization system greatly prolongs the service life of the hydrolytic agent by dehydrating the blast furnace gas before the blast furnace gas is hydrolyzed; meanwhile, the invention carries out source desulphurization on the blast furnace gas by mutually matching the processes of dehydration, hydrolysis, oxygenation and adsorption, so that a user of the blast furnace gas does not need to use desulphurization equipment, the emission of sulfur is intensively treated, and the aim of directly discharging the blast furnace gas after reaching the standard after combustion is fulfilled.
Furthermore, the hydrolysis tower 3 and the adsorption tower 4 are both of layered tower structures, each layered tower body is sequentially provided with an upper air pressure buffer area a, a packing layer b and a lower air pressure buffer area c from top to bottom, the hydrolysis air inlet 31 and the adsorption air inlet 41 are respectively arranged on one side wall of the upper air pressure buffer area a of the layered tower body where the hydrolysis air inlet is located, and the hydrolysis air outlet 32 and the adsorption air outlet 42 are respectively arranged on the other side wall of the lower air pressure buffer area c of the layered tower body where the hydrolysis air inlet is located. The volume ratio of the upper air pressure buffer area a to the packing layer b to the lower air pressure buffer area c is 1 (1-2) to 1, preferably 1:1.5: 1.
In the invention, each layered tower body structure in the hydrolysis tower and the adsorption tower comprises an upper air pressure buffer area of the packing layer, the packing layer and a lower air pressure buffer area of the packing layer, so that the thickness of the packing layer is reduced, and the pretreated gas adopts an up-in and down-out mode, so that the resistance drop of the packing layer can be effectively reduced, the pressure requirement of a desulfurization system on blast furnace gas is reduced, and the effective treatment capacity of the blast furnace gas is improved.
The packing layer b in the hydrolysis tower 3 is used for filling a hydrolytic agent, the hydrolytic agent is a supported hydrolytic agent, the active component of the supported hydrolytic agent is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium oxalate, potassium oxalate, sodium sulfate and potassium sulfate, and the carrier is selected from one or more of carbon nitride, alumina, silica, magnesia, titania, zirconia and ceria. The packing layer b of the adsorption tower 4 is used for filling an adsorbent, the adsorbent is a load type adsorbent, the active component of the load type adsorbent is selected from one or more of iron oxide, cobalt oxide, nickel oxide and copper oxide, and the carrier is selected from one or more of modified bauxite, carbon nitride, alumina, silicon oxide, magnesium oxide, titanium oxide, zirconium oxide and cerium oxide.
The hydrolysis tower 3 comprises 3 vertically superposed layered tower bodies which are arranged in parallel; the adsorption tower 4 is internally provided with 4 vertical layered tower bodies which are stacked and arranged in parallel, wherein 3 layered tower bodies are used for carrying out adsorption treatment on blast furnace gas, and the other layered tower body is standby or used for regenerating an adsorbent. And a heat insulation layer d is arranged between every two adjacent layered tower bodies.
The system further comprises a second heat exchanger 8, a second heat exchange air inlet 81 and a second heat exchange air outlet 82 are arranged on the second heat exchanger 8, the second heat exchange air inlet 81 is respectively communicated with the 4 adsorption air inlets 41 of the adsorption tower 4, the 4 adsorption air outlets 42 of the adsorption tower 4 are converged and then divided into two paths, one path is used for recovering purified blast furnace gas, the other path is communicated with the second heat exchange air inlet 81 through a regeneration air inlet pipeline 9 through a second fan 7, part of purified blast furnace gas is heated through the second heat exchanger 8 and then enters the adsorption tower 4, and when the hydrogen sulfide adsorbed by the adsorbent in the adsorption tower 4 is saturated, the adsorbent in the adsorption tower 4 can be regenerated. In the invention, the first fan 5 is an air blower, and the second fan 7 is an induced draft fan.
The invention also provides an oxygen-free high-water-content high-furnace gas desulfurization process, which comprises the following steps of:
s1, introducing the high-water-content oxygen-free blast furnace gas into the cooler 1 through the blast furnace gas inlet 11, cooling to 5-15 ℃ for dehydration to obtain a first raw material gas with low water content, wherein the water content in the blast furnace gas before dehydration is more than 30%, and the water content in the blast furnace gas after dehydration is less than 7%.
S2, heating the dehydrated first feed gas to 70-100 ℃ through the first heat exchanger 2, introducing the first feed gas into a hydrolysis tower 3 through a hydrolysis gas inlet 31, hydrolyzing in the hydrolysis tower 3, and Converting Organic Sulfur (COS) in the blast furnace gas into hydrogen sulfide to obtain a hydrolyzed second feed gas;
s3, adding air into the second raw material gas, wherein the volume ratio of the air to the second raw material gas is 1: (1000-3000), the oxygen content in the mixed gas is 0.03-0.1 vol%, the mixed gas and the mixed gas are introduced into an adsorption tower 4, and the hydrogen sulfide is adsorbed by an adsorbent to obtain the purified blast furnace gas.
And S4, heating part of the blast furnace gas desulfurized and purified in the step S3 to 180-200 ℃ through a second heat exchanger 8, then introducing the heated blast furnace gas into a layered tower body of the adsorbent to be regenerated of the adsorption tower 4, and regenerating the adsorbent by utilizing the reducing atmosphere in the purified blast furnace gas.
Experimental example 1
60000Nm3COS concentration of 80mg/m at 80 deg.C3The blast furnace gas enters from a blast furnace gas inlet 11 of the cooler 1, and is dehydrated at the low temperature of 5 ℃, and the water discharge is about 6 t/h; the dehydrated first raw material gas is heated to 70 ℃ by a first heat exchanger 2 and then enters a hydrolysis tower 3, and is filled with 7 percent Na of COS hydrolysis catalyst with the height-diameter ratio of 0.12CO3/Al2O3Post-hydrolysis to obtain COS with concentration lower than 1mg/m3A second feed gas of (a); to the second raw materialAir is added into the air in 500Nm3Mixing the raw material gas with oxygen content of about 0.1vol% and Fe with height-diameter ratio of 0.12O3/Al2O3-C3N4A layered tower body of an adsorption tower 4 of the adsorbent, and H in blast furnace gas desulfurized by the adsorption tower 42The concentration of S is less than 0.5mg/m3. A small part of clean oxygen-free and sulfur-free blast furnace gas is heated to 190 ℃ by the second heat exchanger 8, and the adsorbent is regenerated. After regeneration is completed, when the temperature is reduced to be lower than 80 ℃, the valve is switched to be alternately used with the layered tower bodies of the other three adsorption towers 4.
After the adsorption and regeneration cycle test is carried out for 10 times in the steps, H in the blast furnace gas2The concentration of S is less than 2mg/m3。
Experimental example 2
100000Nm3COS concentration of 60mg/m at 70 ℃3The blast furnace gas enters from a blast furnace gas inlet 11 of the cooler 1, and is dehydrated at low temperature of 12 ℃, and the water discharge is about 10 t/h; the dehydrated first raw material gas is heated to 100 ℃ by a first heat exchanger 2 and then enters a hydrolysis tower 3, and is filled with 6 percent Na of COS hydrolysis catalyst with the height-diameter ratio of 0.12CO3/Ti-Al2O3Post-hydrolysis to obtain COS with concentration lower than 1mg/m3A second feed gas of (a); adding 800Nm of air into the second raw material gas3Mixing the raw materials in the first step for H to ensure that the oxygen content of the raw material gas is about 0.1vol%, entering a layered tower body of an adsorption tower 4 filled with a Cu/magnesium modified bauxite adsorbent with the height-diameter ratio of 0.1, and desulfurizing the blast furnace gas H in the adsorption tower 42The concentration of S is less than 0.5mg/m3. A small part of clean oxygen-free and sulfur-free blast furnace gas is heated to 180 ℃ by the second heat exchanger 8, and the adsorbent is regenerated. After regeneration is completed, when the temperature is reduced to be lower than 80 ℃, the valve is switched to be alternately used with the layered tower bodies of the other three adsorption towers 4.
After the adsorption and regeneration cycle test is carried out for 10 times in the steps, H in the blast furnace gas2The concentration of S is less than 2.8mg/m3。
Experimental example 3
120000Nm3At 70 deg.C, COS concentration of 90mgm3The blast furnace gas enters from a blast furnace gas inlet 11 of the cooler 1, and is dehydrated at the low temperature of 15 ℃, and the water discharge is about 13 t/h; the dehydrated first feed gas is heated to 90 ℃ by a first heat exchanger 2 and then enters a hydrolysis tower 3, and 6 percent K of COS hydrolysis catalyst with the height-diameter ratio of 0.1 is filled in the material2CO3/MgAl2O3Post-hydrolysis to obtain COS with concentration lower than 1mg/m3A second feed gas of (a); adding 1000Nm of air into the second raw material gas3H, mixing to ensure that the oxygen content of the raw material gas is about 0.03vol%, entering a layered tower body of an adsorption tower 4 filled with a Ni/titanium modified bauxite adsorbent with the height-diameter ratio of 0.1, and desulfurizing the blast furnace gas H in the adsorption tower 42The concentration of S is less than 0.5mg/m3. A small part of clean oxygen-free and sulfur-free blast furnace gas is heated to 200 ℃ by the second heat exchanger 8, and the adsorbent is regenerated. After regeneration is completed, when the temperature is reduced to be lower than 80 ℃, the valve is switched to be alternately used with the layered tower bodies of the other three adsorption towers 4.
After the adsorption and regeneration cycle test is carried out for 10 times in the steps, H in the blast furnace gas2The concentration of S is less than 3.2mg/m3。
Nothing in this specification is said to apply to the prior art.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (13)
1. The oxygen-free high-water-content high-furnace gas desulfurization system is characterized by comprising a cooler (1), a first heat exchanger (2), a hydrolysis tower (3) and an adsorption tower (4), one end of the cooler (1) is provided with a blast furnace gas inlet (11), the other end is provided with a cold air outlet (12) and a condensed water outlet (13), a first heat exchange air inlet (21) and a first heat exchange air outlet (22) are arranged on the first heat exchanger (2), a hydrolysis air inlet (31) and a hydrolysis air outlet (32) are arranged on the hydrolysis tower (3), an adsorption air inlet (41) and an adsorption air outlet (42) are arranged on the adsorption tower (4), the cold air outlet (12) is communicated with the first heat exchange air inlet (21), the first heat exchange air outlet (22) is communicated with the hydrolysis air inlet (31), the hydrolysis gas outlet (32) is communicated with the adsorption gas inlet (41).
2. The oxygen-free high-water-content high-furnace gas desulfurization system according to claim 1, characterized in that the cooler (1) is further provided with a refrigerant inlet (14) and a refrigerant outlet (15), and the refrigerant inlet (14) and the refrigerant outlet (15) are used as a communicated pair for cooling and dehydrating the blast furnace gas entering the cooler (1) through the blast furnace gas inlet (11); the first heat exchanger (2) is also provided with a hot flue gas inlet (23) and a hot flue gas outlet (24), and the hot flue gas inlet (23) and the hot flue gas outlet (24) are used as a communicated pair and used for heating blast furnace gas cooled and dehydrated by the cooler (1).
3. The oxygen-free high-water-content high-furnace gas desulfurization system according to claim 1, characterized in that the system further comprises a first fan (5) and a mixer (6), wherein the hydrolysis gas outlet (32) of the hydrolysis tower (3) and the air outlet of the first fan (5) are respectively communicated with the gas inlet of the mixer (6), the gas outlet of the mixer (6) is communicated with the adsorption gas inlet (41) of the adsorption tower (4), and the blast furnace gas hydrolyzed by the hydrolysis tower (3) and the air introduced from the first fan (5) are mixed by the mixer (6) and then enter the adsorption tower (4) through the adsorption gas inlet (41) for adsorption desulfurization.
4. The oxygen-free high-water-content high-furnace gas desulfurization system according to claim 3, wherein the hydrolysis tower (3) and the adsorption tower (4) are both of a layered tower body structure, the layered tower body is sequentially provided with an upper air pressure buffer area (a), a packing layer (b) and a lower air pressure buffer area (c) from top to bottom, the hydrolysis gas inlet (31) and the adsorption gas inlet (41) are respectively arranged on one side wall of the upper air pressure buffer area (a) of the layered tower body where the hydrolysis gas inlet and the adsorption gas inlet are located, and the hydrolysis gas outlet (32) and the adsorption gas outlet (42) are respectively arranged on the other side wall of the lower air pressure buffer area (c) of the layered tower body where the hydrolysis gas inlet and the adsorption gas outlet are located; the filler layer (b) in the hydrolysis tower (3) is used for filling a hydrolysis agent; the filler layer (b) of the adsorption tower (4) is used for filling an adsorbent.
5. The oxygen-free high water content high furnace gas desulfurization system according to claim 4, characterized in that the internal volume ratio of the upper gas pressure buffer zone (a), the packing layer (b) and the lower gas pressure buffer zone (c) is 1 (1-2): 1.
6. The oxygen-free high-water-content high-furnace gas desulfurization system according to claim 4 or 5, characterized in that the hydrolysis tower (3) and the adsorption tower (4) each comprise at least two layered tower bodies stacked up and down and arranged in parallel, and a heat-insulating layer (d) is arranged between two adjacent layered tower bodies.
7. The oxygen-free high-water-content blast furnace gas desulfurization system according to claim 6, characterized in that the hydrolysis tower (3) comprises 3 layered tower bodies stacked up and down and arranged in parallel;
the adsorption tower (4) comprises 4 layered tower bodies which are vertically stacked and arranged in parallel, wherein 3 layered tower bodies are used for adsorbing blast furnace gas, and the other layered tower body is standby or used for regenerating an adsorbent.
8. The oxygen-free high water content blast furnace gas desulfurization system according to claim 6, the system also comprises a second heat exchanger (8), a second heat exchange air inlet (81) and a second heat exchange air outlet (82) are arranged on the second heat exchanger (8), the second heat exchange air inlet (81) is respectively communicated with 4 adsorption air inlets (41) of the adsorption tower (4), 4 adsorption gas outlets (42) of the adsorption tower (4) are converged and then divided into two paths, one path is used for recovering purified blast furnace gas, the other path is communicated with the second heat exchange gas inlet (81) through a second fan (7) through a regeneration gas inlet pipeline (9), and part of the purified blast furnace gas enters the adsorption tower (4) after being heated by the second heat exchanger (8) and is used for regenerating the adsorbent saturated in the adsorption tower (4).
9. The oxygen-free high water content blast furnace gas desulfurization system according to claim 8, characterized in that the first fan (5) is an air blower and the second fan (7) is an induced draft fan.
10. The oxygen-free high-water-content high-furnace gas desulfurization process is characterized by comprising the following steps of:
s1, introducing the blast furnace gas with high water content and no oxygen into a cooler (1), and cooling to 5-15 ℃ for dehydration treatment to obtain a first raw material gas with low water content;
s2, heating the dehydrated first raw material gas to 70-100 ℃ through a first heat exchanger (2), introducing into a hydrolysis tower (3), carrying out organic sulfur hydrolysis treatment on the first raw material gas through a hydrolytic agent, and converting organic sulfur into inorganic sulfur to obtain a hydrolyzed second raw material gas;
and S3, introducing the second raw material gas into an adsorption tower (4), and performing adsorption desulfurization treatment by using an adsorbent to obtain the purified blast furnace gas.
11. The oxygen-free high water content high furnace gas desulfurization process according to claim 10, characterized in that air is added to the second raw material gas before the second raw material gas is introduced into the adsorption tower (4) in step S3, so that the volume ratio of the air to the second raw material gas is 1: (1000-3000), the oxygen content in the mixed gas is 0.03-0.1 vol%, and the mixed gas are introduced into the adsorption tower (4).
12. The oxygen-free high water content blast furnace gas desulfurization process according to claim 11, characterized by further comprising the step of regenerating the adsorbent in the adsorption tower (4):
and S4, heating part of the blast furnace gas desulfurized and purified in the step S3 to 180-200 ℃ through a second heat exchanger (8), introducing the heated blast furnace gas into a layered tower body of the adsorbent to be regenerated of the adsorption tower (4), and regenerating the adsorbent by utilizing the reducing atmosphere in the purified blast furnace gas.
13. The oxygen-free high-water-content blast furnace gas desulfurization process of claim 11, wherein the water content in the blast furnace gas before the dehydration in step S1 is more than 30%, and the water content in the blast furnace gas after the dehydration treatment is less than 7%.
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