CN111849566A - Blast furnace gas hydrolysis desulfurization device and method - Google Patents
Blast furnace gas hydrolysis desulfurization device and method Download PDFInfo
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- CN111849566A CN111849566A CN202010754248.2A CN202010754248A CN111849566A CN 111849566 A CN111849566 A CN 111849566A CN 202010754248 A CN202010754248 A CN 202010754248A CN 111849566 A CN111849566 A CN 111849566A
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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
- C10K1/34—Purifying combustible gases containing carbon monoxide by catalytic conversion of impurities to more readily removable materials
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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
- C10K1/002—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
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B5/00—Making pig-iron in the blast furnace
- C21B5/06—Making pig-iron in the blast furnace using top gas in the blast furnace process
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
- C21B2100/40—Gas purification of exhaust gases to be recirculated or used in other metallurgical processes
- C21B2100/42—Sulphur removal
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Abstract
The invention provides a blast furnace gas hydrolysis desulfurization device and a method, wherein the hydrolysis desulfurization device comprises a shell, a flue gas inlet pipeline of the shell is externally connected with an inlet bypass, a pretreatment catalyst layer and a catalyst layer are arranged in the shell along the flow direction of flue gas, a transition area is arranged between two adjacent catalyst layers, and a transition area is arranged between the pretreatment catalyst layer and the catalyst layer adjacent to the pretreatment catalyst layer. The hydrolysis desulfurization method comprises the following steps: under the normal working state, the blast furnace gas enters from an air inlet pipeline of the hydrolysis desulfurization device, and is discharged after catalytic hydrolysis desulfurization; when the pretreatment catalyst layer works abnormally, the blast furnace gas is switched to the inlet bypass to enter, and the pretreatment catalyst layer is replaced, so that the maintenance without stopping the vehicle is realized; the invention reduces the influence of impurities such as particles in the coal gas by arranging the pretreatment catalyst layer and the air inlet bypass, improves the utilization rate and the service life of the catalyst, has the characteristics of good adaptability to working conditions, simple structure and adjustable pressure drop, and can obviously improve the treatment efficiency of the blast furnace gas.
Description
Technical Field
The invention belongs to the technical field of blast furnace gas hydrolysis desulfurization, and relates to a blast furnace gas hydrolysis desulfurization device and a blast furnace gas hydrolysis desulfurization method.
Background
Blast furnace gas is a byproduct in the iron making process, is used as combustible gas with the largest output in iron and steel enterprises, has wide application, and is generally sent to user units such as a blast furnace hot blast stove, a steel rolling heating furnace, a gas power generation unit and the like to be used as fuel. At present, users of blast furnace hot blast stoves, steel rolling heating furnaces, gas power generation and the like all require burning 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, hydrolysis 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 large; if a source control mode is adopted, the blast furnace gas is subjected to fine hydrolysis desulfurization, the sulfur content in the fuel gas is reduced, the pressure of terminal treatment can be greatly reduced, and even terminal treatment facilities are omitted. The blast furnace gas comprises approximately 6-12% of carbon dioxide, 28-33% of carbon monoxide, 1-4% of hydrogen, 55-60% of nitrogen, 0.2-0.5% of hydrocarbons and sulfides, and the total sulfur content is 200-3Most of which are COS, H2S only occupies a small part, so that the removal of COS in the blast furnace gas is the core of the hydrolysis and desulfurization of the blast furnace gas, the existing designed hydrolysis and desulfurization device of the blast furnace gas is not perfect, and a large lifting space is provided.
CN110467944A discloses a blast furnace gas hydrolysis tower, which comprises a primary hydrolysis tower, a secondary hydrolysis tower and a connecting pipeline, wherein blast furnace gas enters from the bottom of the primary hydrolysis tower, passes through a catalyst layer in the middle of the primary hydrolysis tower, enters the bottom of the secondary hydrolysis tower through an inter-tower connecting pipeline after first hydrolysis and desulfurization treatment, passes through a catalyst layer in the middle of the secondary hydrolysis tower again, and is output from an upper blast furnace gas outlet of the secondary hydrolysis tower after second hydrolysis and desulfurization treatment, so that the problem of blast furnace gas hydrolysis and desulfurization can be effectively solved. However, the invention is formed by connecting two hydrolysis towers in series, and has the problems of large resistance and waste water generation; and when the catalyst is blocked or poisoned, the catalyst can only be stopped, which brings inconvenience to production.
CN205796890U discloses a coke oven gas hydrolysis desulphurization device, includes: a first prehydrolysis desulfurization tank, a second prehydrolysis desulfurization tank, corresponding branch pipes, an air inlet main pipe and an air outlet main pipe are arranged at the bottom of the first prehydrolysis desulfurization tank; each pipeline is provided with at least one stop valve. The first pre-hydrolysis desulfurization tank and the second pre-hydrolysis desulfurization tank are arranged in parallel, and when one hydrolysis desulfurization tank needs to replace the catalyst, the coke oven gas only passes through the other hydrolysis desulfurization tank by adjusting the stop valve, so that the catalyst replacement is completed under the condition of no shutdown. However, the invention increases the occupied area of the equipment and the investment cost by arranging two parallel hydrolysis desulfurization tanks.
CN209702678U discloses a blast furnace gas dry hydrolysis desulfurization device, which comprises: the system comprises a blast furnace gas temperature cooler, a blast furnace gas dry hydrolysis desulfurization tower, a blast furnace gas bypass regulating valve and a blast furnace gas hydrolysis desulfurization tower inlet pipe; the inlet pipe of the blast furnace gas hydrolysis desulfurization tower is connected with a blast furnace gas bypass regulating valve, and the gas bypass regulating valve is put into use when reaching the use condition, so that the normal and safe production of the device is ensured. However, when the concentration of sulfide changes, the coal gas is directly discharged to the outlet through the bypass, and the effect of continuous hydrolysis desulfurization is not achieved.
The existing blast furnace gas hydrolysis desulfurization device can not solve the problems of complex structure, large running resistance, adjustable pressure drop and no-parking maintenance. Therefore, how to guarantee the hydrolysis desulfurization device with good hydrolysis desulfurization effect and simple structure, small running resistance and good working condition performance, becomes the problem to be solved urgently at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a blast furnace gas hydrolysis desulfurization device and a blast furnace gas hydrolysis desulfurization method, wherein by arranging a pretreatment catalyst layer and an air inlet bypass, under the normal working state, the blast furnace gas enters from an air inlet pipeline of the hydrolysis desulfurization device, sequentially passes through the pretreatment catalyst layer and at least one catalyst layer, and is discharged after catalytic hydrolysis desulfurization; when the pretreatment catalyst layer works abnormally, blast furnace gas is switched to an air inlet bypass to enter, and after the pretreatment catalyst layer is replaced quickly, the blast furnace gas recovers to work normally, so that maintenance without stopping the vehicle is realized. The section of the pretreated catalyst layer is different from that of the catalyst layer, and when the working condition pressure fluctuates or the pressure change of the subsequent working section is large, the section can be changed by a bypass to replace compensation, so that the purpose is achieved, the invention adopts the following technical scheme:
in a first aspect, the invention provides a blast furnace gas hydrolysis desulfurization device, which comprises a shell, wherein a pretreatment catalyst layer and at least one catalyst layer are arranged in the shell at intervals along the flow direction of flue gas, a transition region is arranged between two adjacent catalyst layers, and a conversion region is arranged between the pretreatment catalyst layer and the catalyst layer adjacent to the pretreatment catalyst layer;
an air inlet bypass is externally connected to the smoke inlet pipeline of the shell, the outlet end of the air inlet bypass is connected into the conversion area, and smoke flows into the conversion area through the air inlet bypass.
According to the invention, by arranging the air inlet bypass, when the pretreatment catalyst layer works abnormally, the blast furnace gas is switched to the air inlet bypass to enter, and after the pretreatment catalyst layer is rapidly replaced, the blast furnace gas recovers to work normally, so that the maintenance without stopping the vehicle is realized.
As a preferred technical solution of the present invention, the pretreated catalyst layer and the catalyst layer are disposed inside the housing in a modular manner.
It should be noted that the modular arrangement referred to in the present invention means that the pretreatment catalyst layer and the catalyst layer are integrally arranged, and the specific implementation form may be: the catalyst is arranged in the net cage to form a whole body which is convenient to replace.
Preferably, the shape of the catalyst filled in the pretreatment catalyst layer comprises one or a combination of at least two of honeycomb, granule or sphere.
Preferably, the shape of the catalyst filled in the catalyst layer comprises one or a combination of at least two of honeycomb, granular or spherical.
Preferably, the shape of the catalyst filled in the pretreated catalyst layer is the same as or different from the shape of the catalyst filled in the catalyst layer.
Preferably, the kind of the catalyst filled in the pretreatment catalyst layer is the same as or different from that of the catalyst filled in the catalyst layer.
Preferably, the catalyst filled in the catalyst layer is an alumina-based hydrolysis catalyst, a titania-based hydrolysis catalyst, an iron oxide-based desulfurizing agent or a microcrystalline catalyst.
Preferably, the catalyst filled in the pretreatment catalyst layer is an alumina-based hydrolysis catalyst.
The kind of the catalyst in the present invention is not particularly limited and is not particularly limited, and examples thereof include an alumina-based hydrolysis catalyst, a titania-based hydrolysis catalyst, an iron oxide-based desulfurizing agent and a microcrystalline catalyst.
As a preferred technical scheme of the invention, the height of the transition zone is recorded as H1Height of the single catalyst layer is denoted as H2，H1≤H2。
Preferably, the volume space velocity of the pretreatment catalyst layer and the catalyst layer is 1500--1For example, it may be 1500h-1、2000h-1、2500h-1、3000h-1、3500h-1、4000h-1、4500h-1Or 5000h-1However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
Preferably, H1Is H20.2 to 0.5 times of (e.g. H)1Is H20.2 times, 0.3 times, 0.4 times or 0.5 times of the total amount of the components, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, H10.3 to 0.6m, for example, 0.3m, 0.35m, 0.4m, 0.45m, 0.5m, 0.55m or 0.6m, but not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable, and further preferably, H is added1Is 0.5 m.
The pretreatment catalysisThe cross-sectional area of the housing in which the agent layer is located is denoted as S1And the sectional area of the case in which the catalyst layer adjacent to the pretreated catalyst layer is located is denoted as S2，S1＜S2。
Preferably, S1And S2In a ratio of (0.45-0.9) to 1, e.g. S1And S2Is 0.45:1, 0.6:1, 0.75:1 or 0.9:1, but is not limited to the recited values, and other values not recited within the numerical range are equally applicable.
According to the invention, by setting the difference of the windward areas of the pretreatment catalyst layer and the catalyst layer, when the working condition pressure fluctuates or the pressure change of the subsequent working section is large, the cross section can be changed by the bypass for compensation, so that the effect of adjusting the pressure drop is achieved.
As a preferred technical scheme of the invention, both ends of the shell are respectively provided with an air outlet area and an ash deposition area, the ash deposition area is positioned at one end of the shell of the flue gas inlet pipeline, and the flue gas passes through the air outlet area and is discharged by an air outlet pipeline of the hydrolysis desulfurization device.
As a preferred technical solution of the present invention, the switching zone is provided with a valve for isolating the pretreatment catalyst layer from the switching zone.
Preferably, the valve of the switching zone is a sealing gate valve.
As a preferable technical solution of the present invention, the intake bypass is provided with a sealing valve.
Preferably, a sealing valve is arranged on the air inlet pipeline of the hydrolysis desulfurization device.
As a preferable technical scheme of the invention, the shell is a cuboid, a positive polygon or a cylinder.
According to the invention, by arranging the pretreatment catalyst layer and the air inlet bypass, when the pretreatment catalyst layer works abnormally, the blast furnace gas is switched to the air inlet bypass to enter, and after the pretreatment catalyst layer is rapidly replaced, the blast furnace gas recovers to work normally, so that the maintenance without stopping the vehicle is realized. And the sections of the pretreatment catalyst layer and the catalyst layer are different, and when the working condition pressure fluctuates or the pressure change of the subsequent working section is large, the section can be changed by a bypass to replace compensation.
In a second aspect, the present invention provides a hydrolytic desulfurization method using the blast furnace gas hydrolytic desulfurization apparatus according to the first aspect, the hydrolytic desulfurization method including:
under the normal working state, the blast furnace gas enters from an air inlet pipeline of the hydrolysis desulfurization device, sequentially passes through the pretreatment catalyst layer and at least one catalyst layer, and is discharged after catalytic hydrolysis desulfurization; when the pretreatment catalyst layer works abnormally, the blast furnace gas is switched to the inlet bypass to enter.
The hydrolysis desulfurization method specifically comprises the following steps:
in a normal working state, opening a valve of a conversion area and a sealing valve on an air inlet pipeline, closing the sealing valve on an air inlet bypass, and discharging blast furnace gas which enters from the air inlet pipeline, sequentially passes through a pretreatment catalyst layer and at least one catalyst layer, and is desulfurized through catalytic hydrolysis;
(II) when the pretreatment catalyst layer works abnormally, closing a valve of the conversion area and a sealing valve on the air inlet pipeline, opening a sealing valve on the air inlet bypass, allowing blast furnace gas to enter the conversion area through the air inlet bypass, sequentially passing through at least one catalyst layer, and discharging the gas after catalytic hydrolysis desulfurization;
and (III) replacing the pretreatment catalysis layer in the process of the step (II), and recovering the normal working state after the replacement is finished.
In a preferred embodiment of the present invention, in step (i), the blast furnace gas includes sulfide.
Preferably, the sulfide includes COS and H2S。
Preferably, the total sulfur content of the sulfide is 200-300mg/m3For example, the total sulfur content of the sulfide is 200mg/m3、220mg/m3、240mg/m3、260mg/m3、280mg/m3Or 300mg/m3However, the numerical values recited are not intended to be limiting, and other numerical values not recited within the numerical range may be equally applicable.
Preferably, in step (I), the temperature of the catalytic hydrolysis desulfurization is 40 to 120 ℃, and may be, for example, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃ or 120 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, in step (I), the catalytic hydrolysis desulfurization is carried out at a pressure of 20 to 1000kPa, for example, 20kPa, 100kPa, 200kPa, 300kPa, 400kPa, 500kPa, 600kPa, 700kPa, 800kPa, 900kPa, or 1000kPa, but not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, in step (I), the gas inlet amount of the blast furnace gas is 1000-3H, for example, may be 1000Nm3/h、10000Nm3/h、50000Nm3/h、100000Nm3/h、150000Nm3/h、200000Nm3/h、250000Nm3H or 300000Nm3And/h, but not limited to, the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the abnormal operation state in the step (II) is plugging of the pretreatment catalyst layer, catalyst deactivation or pressure fluctuation of the working condition.
Preferably, the working condition resistance fluctuation means that the resistance is 50-80% larger than the normal working resistance, for example, 50%, 55%, 60%, 65%, 70%, 75% or 80%, but not limited to the recited values, and other values in the range of the recited values are also applicable.
The recitation of numerical ranges herein includes not only the above-recited numerical values, but also any numerical values between non-recited numerical ranges, and is not intended to be exhaustive or to limit the invention to the precise numerical values encompassed within the range for brevity and clarity.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention provides a blast furnace gas hydrolysis desulfurization device, which can greatly reduce the influence of impurities such as particles in gas by arranging a pretreatment catalyst layer in a shell, has the characteristics of high catalyst utilization rate, small resistance, adjustable pressure drop, good adaptability to working conditions, simple device structure and high operation rate, greatly prolongs the service life, can obviously improve the treatment efficiency of blast furnace gas and has considerable economic benefit.
2. Through having the bypass of admitting air at flue gas intake pipe external on the road, the exit end access switching district of the bypass of admitting air, when pretreatment catalyst layer work is unusual, the blast furnace gas switches over to the bypass of admitting air and gets into, and after the quick replacement pretreatment catalyst layer, normal work resumes, realizes not stopping the maintenance.
Drawings
Fig. 1 is a schematic structural diagram of a blast furnace gas hydrolysis and desulfurization device according to an embodiment of the present invention.
The catalyst comprises a catalyst layer, a transition zone, a conversion zone, a pretreatment catalyst layer, a gas inlet zone, a catalyst layer and a catalyst layer, wherein the catalyst layer comprises 1-a gas outlet zone, 2-a catalyst layer, 3-a transition zone, 4-a conversion zone.
Detailed Description
It is to be understood that in the description of the present invention, the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and 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 taken as limiting the present invention. Furthermore, the terms "first", "second", etc. are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
It should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "disposed," "connected" and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; 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 meaning of the above terms in the present invention can be understood by those of ordinary skill in the art through specific situations.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In one embodiment, the present invention provides a blast furnace gas hydrolysis desulfurization device, as shown in fig. 1, comprising a housing which may be in the form of a rectangular parallelepiped, a regular polygonal body, or a cylinder; a layer of pretreatment catalyst layer 5 and at least one layer of catalyst layer 2 are arranged in the shell at intervals along the flow direction of flue gas; an air inlet bypass 10 is externally connected to a flue gas inlet pipeline 8 of the shell, sealing valves are arranged on the flue gas inlet pipeline 8 and the air inlet bypass 10, the outlet end of the air inlet bypass 10 is connected to the conversion area 4, flue gas flows into the conversion area 4 through the air inlet bypass 10, and the conversion area 4 is provided with a sealing gate valve 11 for separating the pretreatment catalyst layer 5 and the conversion area 4; the two ends of the shell are respectively provided with an air outlet area 1 and an ash deposition area 7, the ash deposition area 7 is positioned at one end of the shell of the flue gas inlet pipeline 8, and the flue gas is discharged from an air outlet pipeline 9 of the hydrolysis desulfurization device through the air outlet area 1.
Wherein the transition zone 3 has a height H1Is a single layer of catalyst layer 2 height H20.2 to 0.5 times of (A), a transition zone 3 and a height H10.3 to 0.6 m. The pretreatment catalyst layer 5 and the catalyst layer 2 are arranged in a modularized mode, the ratio of the sectional area of the pretreatment catalyst layer 5 to the sectional area of the catalyst layer 2 adjacent to the pretreatment catalyst layer 5 is (0.45-0.9): 1, the shape of the catalyst filled in the pretreatment catalyst layer 5 and the catalyst layer 2 comprises one or the combination of at least two of honeycomb shape, granular shape or spherical shape, and the shape and the type of the catalyst filled in the pretreatment catalyst layer 5 and the catalyst layer 2 can be the same or different.
In another embodiment, the present invention provides a hydrolytic desulfurization method using the blast furnace gas hydrolytic desulfurization apparatus, wherein the hydrolytic desulfurization method specifically comprises:
in the normal working state, opening a sealing gate valve 11 of a conversion area 4 and a sealing valve 13 of an air inlet pipeline 8, closing a sealing valve 12 of the air inlet bypass on an air inlet bypass 10, enabling blast furnace gas to enter an air inlet area 6 from the air inlet pipeline 8, wherein the volume concentration of carbon dioxide in the blast furnace gas is 6-12%, the volume concentration of carbon monoxide is 28-33%, the volume concentration of hydrogen is 1-4%, the volume concentration of nitrogen is 55-60%, the volume concentration of hydrocarbons is 0.2-0.5%, and the total sulfur content of sulfide is 200-3(ii) a The blast furnace gas sequentially passes through the pretreatment catalyst layer 5 and at least one catalyst layer 2, is discharged after catalytic hydrolysis desulfurization, the temperature of the catalytic hydrolysis desulfurization is 40-120 ℃, the working pressure of the catalytic hydrolysis desulfurization is 20-1000kPa, and the gas inlet quantity of the blast furnace gas of the catalytic hydrolysis desulfurization is 1000-300000Nm3/h；；
(II) when the catalyst layer blockage, catalyst inactivation or working condition pressure fluctuation is pretreated, the sealing gate valve 11 of the conversion region 4 and the air inlet pipeline sealing valve 13 on the air inlet pipeline 8 are closed, the air inlet bypass sealing valve 12 on the air inlet bypass 10 is opened, blast furnace gas enters the conversion region through the air inlet bypass 10, sequentially passes through at least one catalyst layer 2, and is discharged after the catalytic hydrolysis desulfurization;
and (III) replacing the pretreatment catalysis layer in the process of the step (II), and recovering the normal working state after the replacement is finished.
It is understood that processes or substitutions and variations of conventional data provided by embodiments of the present invention are within the scope and disclosure of the present invention.
Example 1
The embodiment provides a blast furnace gas hydrolysis desulphurization device, which comprises a cuboid shell; a layer of pretreatment catalyst layer 5 and a layer of catalyst layer 2 are arranged in the shell at intervals along the flow direction of the flue gas; an air inlet bypass 10 is externally connected to a flue gas inlet pipeline 8 of the shell, sealing valves are arranged on the flue gas inlet pipeline 8 and the air inlet bypass 10, the outlet end of the air inlet bypass 10 is connected to the conversion area 4, flue gas flows into the conversion area 4 through the air inlet bypass 10, and the conversion area 4 is provided with a sealing gate valve 11 for separating the pretreatment catalyst layer 5 and the conversion area 4; the two ends of the shell are respectively provided with an air outlet area 1 and an ash deposition area 7, the ash deposition area 7 is positioned at one end of the shell of the flue gas inlet pipeline 8, and the flue gas is discharged from an air outlet pipeline 9 of the hydrolysis desulfurization device through the air outlet area 1.
Wherein the transition zone 3 has a height H1Is a single layer of catalyst layer 2 height H20.2 times of the height H of the single catalyst layer 221.5m, transition zone 3 height H1Is 0.3 m. The pretreatment catalyst layer 5 and the catalyst layer 2 are arranged in a modular manner, and the ratio of the sectional area of the pretreatment catalyst layer 5 to the sectional area of the catalyst layer 2 adjacent to the pretreatment catalyst layer 5 is 0.9: 1. The shape of the catalyst filled in the pretreatment catalyst layer 5 is honeycomb-shaped, the shape of the catalyst filled in the catalyst layer 2 is spherical, and the catalyst filled in the pretreatment catalyst layer 5 and the catalyst layer 2 is alumina-based hydrolysis catalyst.
The embodiment also provides a method for performing hydrolysis desulfurization on blast furnace gas by using the hydrolysis desulfurization device, and the hydrolysis desulfurization method specifically comprises the following steps:
in the normal working state, opening a sealing gate valve 11 of a conversion area 4 and a sealing valve 13 of an air inlet pipeline on an air inlet pipeline 8, closing a sealing valve 12 of the air inlet bypass on an air inlet bypass 10, and enabling blast furnace gas to enter the air inlet area 6 from the air inlet pipeline 8, wherein the volume concentration of carbon dioxide in the blast furnace gas is 6%, the volume concentration of carbon monoxide is 29%, the volume concentration of hydrogen is 4%, the volume concentration of nitrogen is 60%, the volume concentration of hydrocarbons is 0.2%, and the total sulfur content of sulfides is 200mg/m3(ii) a The blast furnace gas sequentially passes through the pretreatment catalyst layer 5 and the catalyst layer 2, is discharged after catalytic hydrolysis desulfurization, the temperature of the catalytic hydrolysis desulfurization is 110 ℃, the working pressure of the catalytic hydrolysis desulfurization is 200kPa, and the gas inlet amount of the blast furnace gas subjected to the catalytic hydrolysis desulfurization is 30000Nm3/h；
(II) when the blockage of the catalyst layer, the inactivation of the catalyst or the pressure fluctuation of the working condition are pretreated, the sealing gate valve 11 of the conversion region 4 and the sealing valve 13 of the air inlet pipeline 8 are closed, the sealing valve 12 of the air inlet bypass on the air inlet bypass 10 is opened, the blast furnace gas enters the conversion region through the air inlet bypass 10, passes through the catalyst layer 2, is desulfurized through catalytic hydrolysis, and is discharged;
and (III) replacing the pretreatment catalysis layer in the process of the step (II), and recovering the normal working state after the replacement is finished.
By the hydrolysis desulfurization method, the hydrolysis desulfurization efficiency reaches 99.3 percent.
Example 2
The embodiment provides a blast furnace gas hydrolysis desulfurization device, which comprises a shell which can be a positive polygon body, as shown in fig. 1; a layer of pretreatment catalyst layer 5 and two layers of catalyst layers 2 are arranged in the shell at intervals along the flow direction of flue gas; an air inlet bypass 10 is externally connected to a flue gas inlet pipeline 8 of the shell, sealing valves are arranged on the flue gas inlet pipeline 8 and the air inlet bypass 10, the outlet end of the air inlet bypass 10 is connected to the conversion area 4, flue gas flows into the conversion area 4 through the air inlet bypass 10, and the conversion area 4 is provided with a sealing gate valve 11 for separating the pretreatment catalyst layer 5 and the conversion area 4; the two ends of the shell are respectively provided with an air outlet area 1 and an ash deposition area 7, the ash deposition area 7 is positioned at one end of the shell of the flue gas inlet pipeline 8, and the flue gas is discharged from an air outlet pipeline 9 of the hydrolysis desulfurization device through the air outlet area 1.
Wherein the transition zone 3 has a height H1Is a single layer of catalyst layer 2 height H20.35 times of the height H of the single catalyst layer 221m, a height H of the transition zone 31Is 0.35 m. The pretreatment catalyst layer 5 and the catalyst layer 2 are arranged in a modularized manner, the ratio of the sectional area of the pretreatment catalyst layer 5 to the sectional area of the catalyst layer 2 adjacent to the pretreatment catalyst layer 5 is 0.675:1, the shape of the catalyst filled in the pretreatment catalyst layer 5 comprises a honeycomb-shaped and granular combination, the shape of the catalyst filled in the catalyst layer 2 is a granular or spherical combination, and the catalysts filled in the pretreatment catalyst layer 5 and the catalyst layer 2 are titanium oxide-based hydrolysis catalysts.
The embodiment also provides a method for performing hydrolysis desulfurization on blast furnace gas by using the hydrolysis desulfurization device, and the hydrolysis desulfurization method specifically comprises the following steps:
in the normal working state, the switching area 4 is opened to seal the gate valve 11 and the air inlet pipeline sealing valve 13 on the air inlet pipeline 8, the air inlet bypass sealing valve 12 on the air inlet bypass 10 is closed, the blast furnace gas enters the air inlet area 6 from the air inlet pipeline 8, the volume concentration of carbon dioxide in the blast furnace gas is 7 percent, the volume concentration of carbon monoxide is 33 percent, the volume concentration of hydrogen is 3 percent, the volume concentration of nitrogen is 55 percent, the volume concentration of hydrocarbon is 0.3 percent, and the total sulfur content of sulfide is 250mg/m3(ii) a The blast furnace gas sequentially passes through the pretreatment catalyst layer 5 and the two catalyst layers 2, is discharged after catalytic hydrolysis desulfurization, the temperature of the catalytic hydrolysis desulfurization is 100 ℃, the working pressure of the catalytic hydrolysis desulfurization is 100kPa, and the gas inlet amount of the blast furnace gas subjected to the catalytic hydrolysis desulfurization is 80000Nm3/h；
(II) when the catalyst layer is blocked, the catalyst is inactivated or the working condition pressure fluctuates in the pretreatment process, the sealing gate valve 11 of the conversion region 4 and the air inlet pipeline sealing valve 13 on the air inlet pipeline 8 are closed, the air inlet bypass sealing valve 12 on the air inlet bypass 10 is opened, the blast furnace gas enters the conversion region through the air inlet bypass 10, sequentially passes through the two catalyst layers 2, and is discharged after the catalytic hydrolysis desulfurization;
and (III) replacing the pretreatment catalysis layer in the process of the step (II), and recovering the normal working state after the replacement is finished.
By the hydrolysis desulfurization method, the hydrolysis desulfurization efficiency reaches 99.5 percent.
Example 3
The embodiment provides a blast furnace gas hydrolysis desulphurization device, which comprises a cylindrical shell; a pretreatment catalyst layer 5 and three catalyst layers 2 are arranged in the shell at intervals along the flow direction of flue gas; an air inlet bypass 10 is externally connected to a flue gas inlet pipeline 8 of the shell, sealing valves are arranged on the flue gas inlet pipeline 8 and the air inlet bypass 10, the outlet end of the air inlet bypass 10 is connected to the conversion area 4, flue gas flows into the conversion area 4 through the air inlet bypass 10, and the conversion area 4 is provided with a sealing gate valve 11 for separating the pretreatment catalyst layer 5 and the conversion area 4; the two ends of the shell are respectively provided with an air outlet area 1 and an ash deposition area 7, the ash deposition area 7 is positioned at one end of the shell of the flue gas inlet pipeline 8, and the flue gas is discharged from an air outlet pipeline 9 of the hydrolysis desulfurization device through the air outlet area 1.
Wherein the transition zone 3 has a height H1Is a single layer of catalyst layer 2 height H20.5 times of the height H of the single catalyst layer 221.2m, transition zone 3 height H1Is 0.6 m. The pretreatment catalyst layer 5 and the catalyst layer 2 are arranged in a modular manner, and the ratio of the sectional area of the pretreatment catalyst layer 5 to the sectional area of the catalyst layer 2 adjacent to the pretreatment catalyst layer 5 is 0.45: 1. The shape of the catalyst packed in the pretreatment catalyst layer 5 is spherical, the shape of the catalyst packed in the catalyst layer 2 is a combination of honeycomb and spherical, and the type of the catalyst packed in the pretreatment catalyst layer 5 and the catalyst layer 2 is microcrystalline catalyst.
The embodiment also provides a method for performing hydrolysis desulfurization on blast furnace gas by using the hydrolysis desulfurization device, and the hydrolysis desulfurization method specifically comprises the following steps:
in the normal working state, the switching area 4 sealing gate valve 11 and the air inlet pipeline sealing valve 13 on the air inlet pipeline 8 are opened, the air inlet bypass sealing valve 12 on the air inlet bypass 10 is closed, the blast furnace gas enters the air inlet area 6 from the air inlet pipeline 8, the volume concentration of carbon dioxide in the blast furnace gas is 12 percent, the volume concentration of carbon monoxide is 28 percent, the volume concentration of hydrogen is 1 percent, the volume concentration of nitrogen is 56 percent, the volume concentration of hydrocarbon is 0.5 percent, and the total sulfur content of sulfide is 300mg/m3(ii) a The blast furnace gas sequentially passes through the pretreatment catalyst layer 5 and the three catalyst layers 2, is discharged after catalytic hydrolysis desulfurization, the temperature of the catalytic hydrolysis desulfurization is 110 ℃, the working pressure of the catalytic hydrolysis desulfurization is 200kPa, and the gas inlet quantity of the blast furnace gas subjected to the catalytic hydrolysis desulfurization is 100000Nm3/h；
(II) when the catalyst layer is blocked, the catalyst is inactivated or the working condition pressure fluctuates in the pretreatment process, the sealing gate valve 11 of the conversion region 4 and the air inlet pipeline sealing valve 13 on the air inlet pipeline 8 are closed, the air inlet bypass sealing valve 12 on the air inlet bypass 10 is opened, the blast furnace gas enters the conversion region through the air inlet bypass 10, sequentially passes through the three catalyst layers 2, and is discharged after being desulfurized through catalytic hydrolysis;
and (III) replacing the pretreatment catalysis layer in the process of the step (II), and recovering the normal working state after the replacement is finished.
By the hydrolysis desulfurization method, the hydrolysis desulfurization efficiency reaches 99.7 percent.
Example 4
The embodiment provides a blast furnace gas hydrolysis desulphurization device, which comprises a shell which can be cylindrical as shown in figure 1; a pretreatment catalyst layer 5 and four catalyst layers 2 are arranged in the shell at intervals along the flow direction of flue gas; an air inlet bypass 10 is externally connected to a flue gas inlet pipeline 8 of the shell, sealing valves are arranged on the flue gas inlet pipeline 8 and the air inlet bypass 10, the outlet end of the air inlet bypass 10 is connected to the conversion area 4, flue gas flows into the conversion area 4 through the air inlet bypass 10, and the conversion area 4 is provided with a sealing gate valve 11 for separating the pretreatment catalyst layer 5 and the conversion area 4; the two ends of the shell are respectively provided with an air outlet area 1 and an ash deposition area 7, the ash deposition area 7 is positioned at one end of the shell of the flue gas inlet pipeline 8, and the flue gas is discharged from an air outlet pipeline 9 of the hydrolysis desulfurization device through the air outlet area 1.
Wherein the transition zone 3 has a height H1Is a single layer of catalyst layer 2 height H20.4 times of that of the single catalyst layer 221m, a height H of the transition zone 31Is 0.4 m. The pretreatment catalyst layer 5 and the catalyst layer 2 are arranged in a modular manner, and the ratio of the sectional area of the pretreatment catalyst layer 5 to the sectional area of the catalyst layer 2 adjacent to the pretreatment catalyst layer 5 is 0.7: 1. The shape of the catalyst filled in the pretreatment catalyst layer 5 is a combination of spherical and granular shapes, the shape of the catalyst filled in the catalyst layer 2 is a combination of honeycomb and spherical shapes, and the type of the catalyst filled in the pretreatment catalyst layer 5 and the catalyst layer 2 is an iron oxide-based desulfurizer.
The embodiment also provides a method for performing hydrolysis desulfurization on blast furnace gas by using the hydrolysis desulfurization device, and the hydrolysis desulfurization method specifically comprises the following steps:
in the normal working state, the switching area 4 is opened to seal the gate valve 11 and the air inlet pipeline sealing valve 13 on the air inlet pipeline 8, and the air inlet bypass 10 is closedA gas inlet bypass seal valve 12, wherein the blast furnace gas enters the gas inlet area 6 from the gas inlet pipeline 8, the volume concentration of carbon dioxide in the blast furnace gas is 7 percent, the volume concentration of carbon monoxide is 29 percent, the volume concentration of hydrogen is 3 percent, the volume concentration of nitrogen is 58 percent, the volume concentration of hydrocarbons is 0.5 percent, and the total sulfur content of sulfide is 300mg/m3(ii) a The blast furnace gas sequentially passes through the pretreatment catalyst layer 5 and the four catalyst layers 2, is discharged after catalytic hydrolysis desulfurization, the temperature of the catalytic hydrolysis desulfurization is 90 ℃, the working pressure of the catalytic hydrolysis desulfurization is 180kPa, and the gas inlet quantity of the blast furnace gas subjected to the catalytic hydrolysis desulfurization is 90000Nm3/h；
(II) when the catalyst layer is blocked, the catalyst is inactivated or the working condition pressure fluctuates in the pretreatment process, the sealing gate valve 11 of the conversion region 4 and the air inlet pipeline sealing valve 13 on the air inlet pipeline 8 are closed, the air inlet bypass sealing valve 12 on the air inlet bypass 10 is opened, the blast furnace gas enters the conversion region through the air inlet bypass 10, sequentially passes through the four catalyst layers 2, and is discharged after the catalytic hydrolysis desulfurization;
and (III) replacing the pretreatment catalysis layer in the process of the step (II), and recovering the normal working state after the replacement is finished.
By the hydrolysis desulfurization method, the hydrolysis desulfurization efficiency reaches 99.5 percent.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The blast furnace gas hydrolysis desulphurization device is characterized by comprising a shell, wherein a pretreatment catalyst layer and at least one catalyst layer are arranged in the shell at intervals along the flow direction of flue gas, a transition area is arranged between two adjacent catalyst layers, and a conversion area is arranged between the pretreatment catalyst layer and the catalyst layer adjacent to the pretreatment catalyst layer;
an air inlet bypass is externally connected to the smoke inlet pipeline of the shell, the outlet end of the air inlet bypass is connected into the conversion area, and smoke flows into the conversion area through the air inlet bypass.
2. The hydrolysis desulfurization device of claim 1, wherein the pretreatment catalyst layer and the catalyst layer are disposed inside the housing in a modular manner;
preferably, the shape of the catalyst filled in the pretreatment catalyst layer comprises one or a combination of at least two of honeycomb, granule or sphere;
preferably, the shape of the catalyst filled in the catalyst layer comprises one or a combination of at least two of honeycomb, granular or spherical;
preferably, the shape of the catalyst filled in the pretreatment catalyst layer is the same as or different from the shape of the catalyst filled in the catalyst layer;
preferably, the catalyst filled in the catalyst layer is an alumina-based hydrolysis catalyst, a titania-based hydrolysis catalyst, an iron oxide-based desulfurizer or a microcrystalline catalyst;
preferably, the catalyst filled in the pretreatment catalyst layer is an alumina-based hydrolysis catalyst.
3. The apparatus according to claim 1 or 2, wherein the height of the transition zone is recorded as H1Height of the single catalyst layer is denoted as H2，H1≤H2；
Preferably, the volume space velocity of the pretreatment catalyst layer and the catalyst layer is 1500--1；
Preferably, H1Is H20.2 to 0.5 times of;
preferably, H10.3 to 0.6m, more preferably, H1Is 0.5 m.
The sectional area of the shell where the pretreatment catalyst layer is positioned is marked as S1And the sectional area of the case in which the catalyst layer adjacent to the pretreated catalyst layer is located is denoted as S2，S1＜S2；
Preferably, S1And S2The ratio of (0.45-0.9) to (1).
4. The hydrolysis desulfurization device according to any one of claims 1 to 3, wherein an outlet area and an ash deposition area are respectively disposed at two ends of the housing, the ash deposition area is located at one end of the housing of the flue gas inlet pipeline, and the flue gas is discharged from the outlet pipeline of the hydrolysis desulfurization device through the outlet area.
5. The hydrolysis desulfurization apparatus according to any one of claims 1 to 4, wherein the shift zone is provided with a valve for blocking the pretreatment catalyst layer from the shift zone;
preferably, the valve of the switching zone is a sealing gate valve.
6. The hydrolysis desulfurization apparatus according to any one of claims 1 to 5, wherein a sealing valve is provided on the intake bypass;
preferably, a sealing valve is arranged on the air inlet pipeline of the hydrolysis desulfurization device.
7. The hydrolysis desulfurization device of any one of claims 1 to 6, wherein the housing is a rectangular parallelepiped, a regular polygonal body, or a cylinder.
8. A blast furnace gas hydrolysis desulfurization method for hydrolysis desulfurization of blast furnace gas by using the hydrolysis desulfurization apparatus according to any one of claims 1 to 7, characterized by comprising:
under the normal working state, the blast furnace gas enters from an air inlet pipeline of the hydrolysis desulfurization device, sequentially passes through the pretreatment catalyst layer and at least one catalyst layer, and is discharged after catalytic hydrolysis desulfurization; when the pretreatment catalyst layer works abnormally, the blast furnace gas is switched to the inlet bypass to enter.
9. The hydrolytic desulfurization method according to claim 8, characterized in that the hydrolytic desulfurization method specifically comprises:
in a normal working state, opening a valve of a conversion area and a sealing valve on an air inlet pipeline, closing the sealing valve on an air inlet bypass, and discharging blast furnace gas which enters from the air inlet pipeline, sequentially passes through a pretreatment catalyst layer and at least one catalyst layer, and is desulfurized through catalytic hydrolysis;
(II) when the pretreatment catalyst layer works abnormally, closing a valve of the conversion area and a sealing valve on the air inlet pipeline, opening a sealing valve on the air inlet bypass, allowing blast furnace gas to enter the conversion area through the air inlet bypass, sequentially passing through at least one catalyst layer, and discharging the gas after catalytic hydrolysis desulfurization;
and (III) replacing the pretreatment catalysis layer in the process of the step (II), and recovering the normal working state after the replacement is finished.
10. The hydrolytic desulfurization method of claim 9, wherein, in the step (i), the blast furnace gas comprises sulfide;
preferably, the sulfide includes COS and H2S；
Preferably, the total sulfur content of the sulfide is 200-300mg/m3；
Preferably, in the step (I), the temperature of the catalytic hydrolysis desulfurization is 40-120 ℃;
preferably, in the step (I), the working pressure of the catalytic hydrolysis desulfurization is 20-1000 kPa;
preferably, in the step (I), the gas inlet amount of the blast furnace gas is 1000-300000Nm3/h；
Preferably, the abnormal working state in the step (II) is plugging of a pretreatment catalyst layer, catalyst inactivation or working condition resistance fluctuation;
preferably, the fluctuation of the working condition resistance refers to that the resistance is 50-80% larger than the normal working resistance.
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