CN113549474A - Blast furnace gas step-by-step dry deacidification system and method - Google Patents

Blast furnace gas step-by-step dry deacidification system and method Download PDF

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CN113549474A
CN113549474A CN202110892639.5A CN202110892639A CN113549474A CN 113549474 A CN113549474 A CN 113549474A CN 202110892639 A CN202110892639 A CN 202110892639A CN 113549474 A CN113549474 A CN 113549474A
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tower
gas
pipeline
hydrolysis
inorganic acid
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CN113549474B (en
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张玉文
祝凯
董辉
耿淑华
鲁雄刚
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University of Shanghai for Science and Technology
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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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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    • B01D53/26—Drying gases or vapours
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    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
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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
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    • C10K1/02—Dust removal
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    • C10K1/00—Purifying combustible gases containing carbon monoxide
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    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The invention discloses a blast furnace gas step-by-step dry deacidification method, which comprises the following steps: the clean gas generated by the raw gas generated at the top of the blast furnace after passing through a gravity dust collector and a bag-type dust collector is sent into a dehydration drying tower for dehydration through a gas input pipeline, the middle part in the dehydration drying tower is provided with a dehydration drying agent bed layer which is filled with anhydrous CaCl2A desiccant; the coal gas passing through the dehydration drying tower is sent into an inorganic acid removal tower through a pipeline to remove HCl and H2S, installing an inorganic acid adsorbent bed layer in the middle of the inorganic acid removal tower, and filling CaO adsorbent in the inorganic acid adsorbent bed layer; the gas passing through the inorganic acid removing tower is sent into an organic sulfur hydrolysis tower through a pipeline for COS hydrolysis, a hydrolysis catalyst bed layer is arranged in the middle of the organic sulfur hydrolysis tower, and a COS hydrolysis catalyst is filled in the organic sulfur hydrolysis tower; the coal gas passing through the organic sulfur hydrolysis tower is sent to a desulfurization tower through a pipeline to remove H2S, a desulfurizer bed layer is arranged in the middle of the desulfurization tower and filled with Fe2O3And the desulfurizer enters the gas output pipeline through the gas of the desulfurizing tower.

Description

Blast furnace gas step-by-step dry deacidification system and method
Technical Field
The invention relates to blast furnace gas purification, in particular to a system and a method for removing acid components including sulfur and chlorine in blast furnace gas by a dry method.
Background
The dry dedusting process of blast furnace gas and the residual pressure waste heat power generation technology are advanced technologies for promoting energy conservation, emission reduction and circular economy development of the steel industry in China. The blast furnace gas dry dedusting technology gradually replaces the traditional wet dedusting with the advantages of water saving, high dedusting efficiency, full utilization of sensible heat of gas, high residual pressure power generation capacity of gas and the like, and becomes the first choice of the blast furnace gas dedusting technology. Practice proves that compared with the traditional wet dust removal, the dry dust removal technology can save 35% of investment, 7-9 t of circulating water, 60-70% of electricity, 30% of newly increased electricity generation and a great amount of discharge of sewage and sludge. However, the blast furnace gas after dry dedusting can cause serious corrosion of gas pipelines, blades of a residual pressure turbine power generation device (TRT for short) and other accessory equipment, thereby causing the vibration of the TRT blades, gas leakage, the reduction of the heat storage efficiency of checker bricks of the hot blast stove and the like, seriously influencing the normal operation of the residual pressure waste heat recovery device and the normal smelting of the blast furnace and bringing about great potential safety production hazards. The reason for causing corrosion is that acidic corrosive components in blast furnace gas after dry dedusting cannot be taken away by liquid like wet dedusting and remain in the gas, and further form an acidic liquid environment with condensed water separated out due to the reduction of the temperature of the gas, so that the corrosion is caused to the surface of equipment.
The main component of the blast furnace top gas is 0.5-2.5% of H2、2～4％CmHn、18～24％CO、16～22％CO2And 56 to 63% N2And other components comprise: COS and H2S、NOxAnd HCl, etc., and further contains a certain amount of furnace dust and water vapor. The blast furnace gas condensate water after dry dedusting is analyzed, and the blast furnace gas pipe network condensate water medium has the pH value of 1-2 and belongs to a strong acid solution; and the solution is a high salt water with a salt content of up to 32623mg/L and Cl-The content of SO is up to 26548mg/L, accounting for 85 percent of the total salt content4 2-The content is 611mg/L, so that the strong acidic components such as Cl and S contained in the blast furnace gas are the main cause of the corrosion problem. The HCl and H mainly exist in the form of gas in the blast furnace gas and contain strong acidic components such as Cl and S2S, and COS, wherein HCl, H2S is inorganic acid and can be removed by a conventional alkaline adsorbent, and COS which is taken as organic sulfur is difficult to remove by a conventional method and needs to be removed after being hydrolyzed and converted by a catalyst. To completely solve the problem of acid corrosion caused by blast furnace gas, HCl and H need to be added2And removing the S and COS components.
Therefore, those skilled in the art are devoted to developing a system and a method for removing acidic components from blast furnace gas by a dry method.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention provides a system and a method for removing acidic components from blast furnace gas by a dry method.
In order to realize the aim, the invention firstly provides a step-by-step dry deacidification system for blast furnace gas, and the dedusted blast furnace clean gas is supplied to a subsystem, a dehydration drying tower dehydration subsystem and an inorganic acid removal tower to remove HCl and H2S subsystem, organic sulfur hydrolysis tower hydrolysis COS subsystem, desulfurizing tower H removal2The system comprises an S subsystem and a deacidification agent replacing subsystem, wherein the blast furnace clean gas supply subsystem sends the clean gas generated by the top of the blast furnace after the raw gas passes through a gravity dust collector and a bag-type dust collector into a dehydration subsystem of a dehydration drying tower through a gas input pipeline; the middle part in a dehydration drying tower of a dehydration subsystem of the dehydration drying tower is provided with a dehydration drying agent bed layer which is filled with anhydrous CaCl2A desiccant; the coal gas passing through the dehydration subsystem of the dehydration drying tower is sent to an inorganic acid removal tower through a pipeline to remove HCl and H2In the S subsystem, an inorganic acid adsorbent bed layer is arranged in the middle of the inorganic acid removal tower and is filled with a CaO adsorbent; removing HCl and H by an inorganic acid removing tower2The coal gas of the S subsystem is sent into a COS (sulfur carbonyl) hydrolysis subsystem of an organic sulfur hydrolysis tower through a pipeline, a hydrolysis catalyst bed layer is arranged in the middle of the organic sulfur hydrolysis tower, and a COS hydrolysis catalyst is filled in the hydrolysis catalyst bed layer; the coal gas of the COS subsystem hydrolyzed by the organic sulfur hydrolysis tower is sent to the desulfurization tower through a pipeline to remove H2In the S subsystem, a desulfurizer bed layer is arranged in the middle of the desulfurization tower and filled with Fe2O3A desulfurizing agent; removal of H by a desulfurization column2And the coal gas of the S subsystem enters a coal gas output pipeline.
Furthermore, the joint of the upper end of the dehydration drying tower and the pipeline is in flange connection, and a tower cover of the upper half part of the dehydration drying tower is in flange connection with the tower body; the lower end of the dehydration drying tower is connected with the pipeline through a flange, and the bottom of the dehydration drying tower is connected with the tower body through a flange.
Furthermore, the joint of the upper end of the inorganic acid removal tower and the pipeline is in flange connection, and the tower cover of the upper half part of the inorganic acid removal tower is in flange connection with the tower body; the lower end of the inorganic acid removing tower is connected with a pipeline through a flange, and the bottom of the inorganic acid removing tower is connected with the tower body through a flange.
Furthermore, the joint of the upper end of the organic sulfur hydrolysis tower and the pipeline is in flange connection, and a tower cover of the upper half part of the organic sulfur hydrolysis tower is in flange connection with the tower body; the lower end of the organic sulfur hydrolysis tower is connected with a pipeline through a flange, and the bottom of the lower half part of the organic sulfur hydrolysis tower is connected with a tower body through a flange.
Furthermore, the joint of the upper end of the desulfurizing tower and the pipeline is in flange connection, and the tower cover of the upper half part of the desulfurizing tower is in flange connection with the tower body; the lower end of the desulfurizing tower is connected with the pipeline through a flange, and the bottom of the desulfurizing tower is connected with the tower body through a flange.
Furthermore, the gas-liquid separator further comprises a bypass pipeline, wherein the bypass pipeline is connected with the gas outlet pipeline and the gas inlet pipeline, and a one-way return valve and a booster fan are arranged on the bypass pipeline.
Further, a gas pressure detection device is arranged above the reaction bed layers of the dehydration drying tower, the inorganic acid removal tower, the organic sulfur hydrolysis tower and the desulfurization tower.
The invention secondly provides a blast furnace gas step-by-step dry deacidification method, which comprises the following steps:
the clean gas generated by the raw gas generated at the top of the blast furnace after passing through a gravity dust collector and a bag-type dust collector is sent into a dehydration drying tower for dehydration through a gas input pipeline, the middle part in the dehydration drying tower is provided with a dehydration drying agent bed layer which is filled with anhydrous CaCl2A desiccant; the coal gas passing through the dehydration drying tower is sent into an inorganic acid removal tower through a pipeline to remove HCl and H2S, installing an inorganic acid adsorbent bed layer in the middle of the inorganic acid removal tower, and filling CaO adsorbent in the inorganic acid adsorbent bed layer; the gas passing through the inorganic acid removing tower is sent into an organic sulfur hydrolysis tower through a pipeline for COS hydrolysis, a hydrolysis catalyst bed layer is arranged in the middle of the organic sulfur hydrolysis tower, and a COS hydrolysis catalyst is filled in the organic sulfur hydrolysis tower; the coal gas passing through the organic sulfur hydrolysis tower is sent to a desulfurization tower through a pipeline to remove H2S, a desulfurizer bed layer is arranged in the middle of the desulfurization tower and filled with Fe2O3And the desulfurizer enters the gas output pipeline through the gas of the desulfurizing tower.
Further, the method also comprises the following steps: when the dehydration drying towerWithout water in CaCl2After the drying agent is invalid, the flange connection is disassembled, the invalid anhydrous drying agent in the dehydration drying tower is emptied, and new anhydrous CaCl is filled2A desiccant; when the CaO adsorbent in the inorganic acid removal tower fails, the failed CaO adsorbent in the inorganic acid removal tower is emptied by disassembling the flange connection, and a new CaO adsorbent is loaded; when the COS hydrolysis catalyst in the organic sulfur hydrolysis tower fails, the COS hydrolysis catalyst which fails in the organic sulfur hydrolysis tower is emptied through dismounting flange connection, and a new COS hydrolysis catalyst is loaded; when Fe is in the desulfurizing tower2O3After the desulfurizer fails, the flange connection is disassembled to empty the failed Fe in the desulfurizing tower2O3Desulfurizing agent, charging new Fe2O3A desulfurizing agent.
Further, the method also comprises the following steps: and adjusting the opening degree of a one-way backflow valve on a bypass pipeline connecting the gas inlet pipeline and the gas outlet pipeline and the rotating speed of the booster fan to enable part of the gas in the gas outlet pipeline to flow back to the gas inlet pipeline and be mixed with the gas in the gas inlet pipeline so as to obtain the required reactant concentration and pressure.
The invention utilizes the step-by-step process to remove HCl and H2S inorganic acid in the blast furnace gas and the hydrolysis conversion of organic sulfur COS, and makes up the defect that the traditional industry can only remove HCl or sulfur-containing components in the blast furnace gas in a single way; and according to the coal gas after partial reaction of the pressurization circulation of the bypass pipeline, a dehydration drying process and an inorganic acid removal process before organic sulfur hydrolysis are set according to the optimal reaction condition in the deacidification process.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a schematic view of a blast furnace gas step-by-step dry deacidification system in a preferred embodiment of the present invention;
FIG. 2 is a schematic view of a blast furnace gas step dry deacidification system in a further embodiment of the present invention;
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Referring to fig. 1, the blast furnace gas stepwise dry deacidification system according to the present invention includes:
the dust-removed blast furnace clean gas supply subsystem, the dehydration drying tower dehydration subsystem and the inorganic acid removal tower remove HCl and H2S subsystem, organic sulfur hydrolysis tower hydrolysis COS subsystem, desulfurizing tower H removal2S subsystem, deacidification agent change subsystem.
The dust-removed blast furnace clean gas supply subsystem comprises the following steps: the subsystem is characterized in that clean gas generated by raw gas generated at the top of a blast furnace after passing through a gravity dust collector and a bag-type dust collector enters a dehydration drying tower 2 through a gas pipeline 1, and is discharged through a gas pipeline 9 after being dehydrated, subjected to inorganic acid removal, hydrolyzed organic sulfur and desulfurized by a subsequent subsystem to enter a next TRT and a pressure reducing valve bank;
(II) a dehydration subsystem of a dehydration drying tower: the subsystem is connected behind a gas pipeline 1, a dehydration drying agent bed layer 2a is arranged in the middle of a dehydration drying tower, and anhydrous CaCl is filled in the dehydration drying tower2A desiccant; the joint of the upper end of the dehydration drying tower and the pipeline 1 is in flange connection 2b, and the tower cover of the upper half part of the dehydration drying tower is in flange connection 2d with the tower body; the joint of the lower end of the dehydration drying tower and the pipeline 6 is in flange connection 2c, and the bottom of the lower half part of the dehydration drying tower is in flange connection 2e with the tower body.
(III) removing HCl and H by using an inorganic acid removing tower2S subsystem: the subsystem is connected behind a gas pipeline 6, an inorganic acid adsorbent bed layer 3a is arranged in the middle of the inorganic acid removal tower, and a CaO adsorbent is filled in the inorganic acid adsorbent bed layer; the joint of the upper end of the inorganic acid removal tower and the pipeline 6 is in flange connection 3b, and the tower cover and the tower body of the upper half part of the inorganic acid removal tower are in flange connection 3 d; the joint of the lower end of the inorganic acid removing tower and the pipeline 7 is in flange connection 3c, and the bottom of the lower half part of the inorganic acid removing tower is in flange connection 3e with the tower body.
(IV) the organic sulfur hydrolysis tower hydrolysis COS subsystem: the subsystem is connected behind a gas pipeline 7, a hydrolysis catalyst bed layer 4a is arranged in the middle of the organic sulfur hydrolysis tower, and a COS hydrolysis catalyst is filled in the hydrolysis catalyst bed layer; the joint of the upper end of the organic sulfur hydrolysis tower and the pipeline 7 is in flange connection 4b, and the tower cover of the upper half part of the organic sulfur hydrolysis tower is in flange connection 4d with the tower body; the joint of the lower end of the organic sulfur hydrolysis tower and the pipeline 8 is in flange connection 4c, and the bottom of the lower half part of the organic sulfur hydrolysis tower is in flange connection 4e with the tower body.
(V) desulfurizing tower for removing H2S subsystem: the subsystem is connected behind a gas pipeline 8, a desulfurizer bed layer 5a is arranged in the middle of the desulfurization tower, and Fe is filled in the desulfurization tower2O3A desulfurizing agent; the joint of the upper end of the desulfurizing tower and the pipeline 8 is flanged 5b, and the tower cover of the upper half part of the desulfurizing tower is flanged 5d with the tower body; the joint of the lower end of the desulfurizing tower and the pipeline 9 is flanged 5c, and the bottom of the lower half part of the desulfurizing tower is flanged 4e with the tower body.
(VI) deacidification agent replacing subsystem: the subsystem comprises sixteen flange connections at 2b, 2c, 2d, 2e, 3b, 3c, 3d, 3e, 4b, 4c, 4d, 4e, 5b, 5c, 5d and 5e, and the dehydration drying agent, the inorganic acid removal adsorbent, the organic sulfur hydrolysis catalyst and the desulfurizing agent are replaced through detachable flange connections after being out of service.
The blast furnace gas step-by-step dry deacidification method comprises the following steps:
the blast furnace clean gas at 150 ℃ discharged from the bag-type dust collector enters a dehydration drying tower 2 through a gas pipeline 1, and the gas passes through anhydrous CaCl2H in the gas at the time of drying agent bed 2a2O is absorbed by the drying agent to remove H in the coal gas2The O enters the next tower through a pipeline 6;
the coal gas from the dehydration drying tower 2 enters an inorganic acid removal tower 3 through a coal gas pipeline 6, and HCl and H in the coal gas pass through a CaO adsorbent bed layer 3a2S respectively chemically reacts with CaO adsorbent to form CaCl2CaS, removing HCl and H in the blast furnace gas after the blast furnace gas passes through a CaO adsorbent bed layer 3a2S, then entering the next tower through a pipeline 7;
from inorganicThe gas from the acid removing tower 3 enters an organic sulfur hydrolysis tower 4 through a gas pipeline 7, and when the gas passes through a COS hydrolysis catalyst bed layer 4a, COS and H in the gas2O is subjected to hydrolysis reaction under the promotion of a hydrolysis catalyst and is converted into inorganic sulfur H2S, after the blast furnace gas passes through a COS hydrolysis catalyst bed layer 4a, the COS is converted into H2S, then entering the next tower through a pipeline 8;
the coal gas from the organic sulfur hydrolysis tower 4 enters a desulfurizing tower 5 through a coal gas pipeline 8, and the coal gas passes through Fe2O3H converted from COS in the desulfurizing agent bed layer 5a2S and Fe2O3The desulfurizing agent is subjected to chemical reaction to form Fe2S3Blast furnace gas passing through Fe2O3H in the coal gas is removed after a desulfurizer bed layer 5a2S, then enters a TRT and a pressure reducing valve bank through a pipeline 9;
anhydrous CaCl in dehydration drying tower 22After the drying agent is invalid, the anhydrous CaCl which is invalid in the emptying dehydration drying tower 2 is detached through the flange connection of 2c and 2e2The drying agent is detachably filled with new anhydrous CaCl through 2b and 2d flange connection2A desiccant;
after the CaO adsorbent in the inorganic acid removal tower 3 is invalid, the invalid CaO adsorbent in the inorganic acid removal tower 3 is emptied through flange connection and disassembly of 3c and 3e, and new CaO adsorbent is loaded through flange connection and disassembly of 3b and 3 d;
after the COS hydrolysis catalyst in the organic sulfur hydrolysis tower 4 is invalid, the invalid COS hydrolysis catalyst in the organic sulfur hydrolysis tower 4 is emptied through flange connection and disassembly of 4c and 4e, and a new COS hydrolysis catalyst is loaded through flange connection and disassembly of 4b and 4 d;
fe in desulfurizing tower 52O3After the desulfurizer is invalid, the invalid Fe in the emptying desulfurizing tower 5 is detached through the flange connection of 5c and 5e2O3Desulfurizing agent, detachable and filled with new Fe through 5b and 5d flange connection2O3A desulfurizing agent;
according to the blast furnace gas acidic component stepwise removal principle of the invention:
1. using anhydrous CaCl2Drying agent for absorbing water in blast furnace gas and dehydratingBasic principle of drying
The purified gas obtained after the blast furnace gas is subjected to gravity dust removal and cloth bag dust removal enters a dehydration drying tower to remove H in the gas2The principle of O is that anhydrous CaCl is arranged on a fixed bed layer of a dehydration drying tower2Desiccant for absorbing H in coal gas2And O, achieving the dehydration of the blast furnace gas. The chemical reaction equation that takes place during drying is as follows:
CaCl2+2H2O——→CaCl2·2H2O (1)
the reason for carrying out the drying treatment before the removal of the acid components of the blast furnace gas is as follows: research has shown that trace amounts of H in gases2O can promote or even promote the hydrolysis reaction of COS, and excessive H2O inhibits H2S removal and COS hydrolysis reaction, wherein a dehydration drying tower is arranged at the position for the H in the blast furnace gas in order to ensure that the subsequent deacidification reaction achieves the best effect2And removing the O.
2. By using CaO adsorbent to react with HCl and H2Basic principle of S reaction for absorption and removal
The dried gas of the blast furnace gas after passing through the dehydration drying tower enters an inorganic acid removing tower to remove HCl and H in the gas2The principle of S is that CaO adsorbent arranged on a fixed bed layer of an inorganic acid removing tower and HCl and H in coal gas are used2S is subjected to chemical reaction to remove HCl and H in the gas2And S component, so as to achieve the effect of removing the inorganic acid in the coal gas. The reason for choosing CaO as the mineral acid adsorbent is that prior studies have shown CaO to be a function of HCl and H2S has better reaction activity. The chemical reaction equations that occur during the stripping process include:
CaO+2HCl(g)——→CaCl2+H2O(g) (2)
CaO+H2S(g)——→CaS+H2O(g) (3)
the purpose of removing the inorganic acid before removing the acid components of the blast furnace gas is due to the H existing in the blast furnace gas2S and HCl can seriously affectThe hydrolysis efficiency of COS is shown by research that the mechanism of the hydrolysis reaction of COS is that the basic center on the surface of the catalyst acts on the conversion of COS into H2S, H present in the gas itself2S and HCl can be adsorbed on the surface of the catalyst, so that the activity of the basic center is reduced, and the hydrolysis efficiency of COS is further influenced. A small amount of H is generated in the reaction for removing the inorganic acid in the inorganic acid removing tower2O, according to hydrolysis reaction COS and H2The molar ratio of O is 1:1, and thus a very small portion of H is required for hydrolyzing COS2O, and here H formed by the elimination reaction of the mineral acid2O and trace H separated out from coal gas due to temperature drop2O is enough to promote the hydrolysis reaction of COS, and most of H in the blast furnace gas is removed after the blast furnace gas passes through a dehydration drying tower2O, so that H enters a subsequent process2The O content is not so high as to inhibit the hydrolysis reaction and the inorganic sulfur removal reaction.
3. Basic principle for realizing COS hydrolysis in blast furnace gas by using catalyst
The principle that the gas of the blast furnace gas after passing through the inorganic acid removing tower enters the organic sulfur hydrolysis tower to remove the COS in the gas is that the hydrolysis reaction of the COS in the gas is promoted to be converted into H by the hydrolysis catalyst arranged on the fixed bed layer of the organic sulfur hydrolysis tower2S, thereby achieving the effect of removing COS from the coal gas. The hydrolysis catalyst adopts a commercial mature COS hydrolysis catalyst, and the COS hydrolysis reaction is mainly completed by the following reaction chemical formula:
COS(g)+H2O(g)——→H2S(g)+CO2(g) (4)
4. using Fe2O3H obtained by hydrolysis conversion of COS in coal gas2Basic principle of S reaction for absorption and removal
The blast furnace gas enters a desulfurizing tower to remove H from COS through hydrolysis conversion after passing through an organic sulfur hydrolysis tower2S, the principle is that Fe is arranged on a fixed bed layer of a desulfurizing tower2O3With H in the gas2S is subjected to chemical reaction to remove H in the coal gas2S component, thereby achieving the inorganic sulfur of the coal gasH2And (4) the effect of S removal. COS in the coal gas is hydrolyzed and converted into H2S, thereby achieving the effect of removing COS from the coal gas. Selection of Fe2O3As H2The reason for the S desulfurization agent is that it is currently used industrially for removing H2S adopts a wide range of desulfurizer as Fe2O3. The chemical reaction equation that occurs during the stripping process is as follows:
Fe2O3+3H2S(g)——→Fe2S3+3H2O(g) (5)
in order to optimize the reaction process and increase the reaction efficiency, it is desirable to control and regulate the concentration and pressure of the gaseous reactants according to the reaction kinetics, especially after passing through the multi-stage reaction column, the gas pressure loss is large. Thus, as shown in fig. 2, in another embodiment according to the present invention, a bypass pipe 10 leading to the gas input pipe 1 is provided on the gas output pipe 9, a one-way return valve 11 and a booster fan 16 are provided on the bypass pipe 10, and gas pressure detecting means 12 to 15 are provided above each reaction tower bed. By controlling the opening of the one-way return valve 11 and the rotating speed of the booster fan 16, the reacted gas in the gas output pipeline 9 partially circulates and flows back, and is mixed with the input clean gas to prepare, so that the pressure of the clean gas entering the deacidification system and the concentration of reaction components can be adjusted, and meanwhile, the deacidification system is equivalent to multi-stage circulating deacidification. In addition, when CaCl needs to be replaced2Desiccant, CaO adsorbent, COS hydrolysis catalyst, or Fe2O3When the desulfurizer is used, before the flange is disassembled, the one-way return valve 11 is closed, the atmosphere communicating valves 17 and 18 are opened, and the booster fan 16 is started to purge the reaction tower to remove residual coal gas, so that the safety of operators is ensured.
Excess H is considered in the present invention2The inhibition effect of O on the deacidification process is provided with a dehydration drying process, and HCl and H are considered2The inhibiting effect of S on the COS hydrolysis process sets an inorganic acid removal process, and the optimal removal effect of each deacidification stage is ensured. Each tower body is provided with a dehydration drying agent, an inorganic acid removal adsorbent and organic sulfur hydrolysis catalysisAnd the replacement system after the desulfurizer fails increases the practical industrial feasibility. The invention utilizes a step-by-step process to remove HCl and H in blast furnace gas2The removal of inorganic acid and the hydrolysis conversion of organic sulfur COS are involved and all removed, and the defect that the traditional industry can only remove HCl or sulfur-containing components in blast furnace gas in a single way is overcome; and a dehydration drying process and an inorganic acid removal process before organic sulfur hydrolysis are set according to the optimal reaction conditions in the deacidification process. Compared with the traditional single desulfurization process or single dechlorination process, the method has the advantages that the removal of the acid components is more comprehensive and thorough, the anticorrosion effect brought to the subsequent equipment of the blast furnace is better, and the drying agent, the hydrolysis catalyst and the desulfurizing agent adopted in the deacidification process are all cheap and common materials, so that the cost is saved.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.

Claims (10)

1. A step-by-step dry deacidification system for blast furnace gas is characterized by comprising a dedusted blast furnace clean gas supply subsystem, a dehydration drying tower dehydration subsystem and an inorganic acid removal tower for removing HCl and H2S subsystem, organic sulfur hydrolysis tower hydrolysis COS subsystem, desulfurizing tower H removal2The system comprises an S subsystem and a deacidification agent replacing subsystem, wherein the blast furnace clean gas supply subsystem sends the clean gas generated by the top of the blast furnace after the raw gas passes through a gravity dust collector and a bag-type dust collector into a dehydration subsystem of a dehydration drying tower through a gas input pipeline; the middle part in a dehydration drying tower of a dehydration subsystem of the dehydration drying tower is provided with a dehydration drying agent bed layer which is filled with anhydrous CaCl2A desiccant; the coal gas passing through the dehydration subsystem of the dehydration drying tower is sent to an inorganic acid removal tower through a pipeline to remove HCl and H2In the S subsystem, the middle part in the inorganic acid removing tower is provided with an inorganic acid adsorbent bedA layer filled with a CaO sorbent; removing HCl and H by an inorganic acid removing tower2The coal gas of the S subsystem is sent into a COS (sulfur carbonyl) hydrolysis subsystem of an organic sulfur hydrolysis tower through a pipeline, a hydrolysis catalyst bed layer is arranged in the middle of the organic sulfur hydrolysis tower, and a COS hydrolysis catalyst is filled in the hydrolysis catalyst bed layer; the coal gas of the COS subsystem hydrolyzed by the organic sulfur hydrolysis tower is sent to the desulfurization tower through a pipeline to remove H2In the S subsystem, a desulfurizer bed layer is arranged in the middle of the desulfurization tower and filled with Fe2O3A desulfurizing agent; removal of H by a desulfurization column2And the coal gas of the S subsystem enters a coal gas output pipeline.
2. The blast furnace gas step-by-step dry deacidification system as defined in claim 1, wherein the joint of the upper end of the dehydration drying tower and the pipeline is flanged, and the tower cover of the upper half part of the dehydration drying tower is flanged with the tower body; the lower end of the dehydration drying tower is connected with the pipeline through a flange, and the bottom of the dehydration drying tower is connected with the tower body through a flange.
3. The blast furnace gas fractional dry deacidification system according to claim 1, wherein the joint of the upper end of the inorganic acid removal tower and the pipeline is flanged, and the tower cover of the upper half part of the inorganic acid removal tower is flanged with the tower body; the lower end of the inorganic acid removing tower is connected with a pipeline through a flange, and the bottom of the inorganic acid removing tower is connected with the tower body through a flange.
4. The blast furnace gas fractional dry deacidification system according to claim 1, wherein the connection of the upper end of the organosulfur hydrolysis tower and the pipeline is flanged, and the tower cover of the upper half of the organosulfur hydrolysis tower is flanged to the tower body; the lower end of the organic sulfur hydrolysis tower is connected with a pipeline through a flange, and the bottom of the lower half part of the organic sulfur hydrolysis tower is connected with a tower body through a flange.
5. The blast furnace gas step-by-step dry deacidification system as defined in claim 1, wherein the joint of the upper end of the desulfurization tower and the pipeline is flanged, and the tower cover of the upper half part of the desulfurization tower is flanged with the tower body; the lower end of the desulfurizing tower is connected with the pipeline through a flange, and the bottom of the desulfurizing tower is connected with the tower body through a flange.
6. The blast furnace gas step-by-step dry deacidification system as claimed in claim 1, further comprising a bypass pipeline, wherein the bypass pipeline is connected with the gas outlet pipeline and the gas inlet pipeline, the bypass pipeline is provided with a one-way return valve, a booster fan and an atmosphere communicating valve for purging residual gas in the reaction tower.
7. The blast furnace gas stepwise dry deacidification system according to claim 6, wherein a gas pressure detecting device is provided above the reaction bed layers of the dehydration drying tower, the inorganic acid removing tower, the organic sulfur hydrolysis tower and the desulfurization tower.
8. A blast furnace gas step-by-step dry deacidification method is characterized by comprising the following steps:
the clean gas generated by the raw gas generated at the top of the blast furnace after passing through a gravity dust collector and a bag-type dust collector is sent into a dehydration drying tower for dehydration through a gas input pipeline, the middle part in the dehydration drying tower is provided with a dehydration drying agent bed layer which is filled with anhydrous CaCl2A desiccant; the coal gas passing through the dehydration drying tower is sent into an inorganic acid removal tower through a pipeline to remove HCl and H2S, installing an inorganic acid adsorbent bed layer in the middle of the inorganic acid removal tower, and filling CaO adsorbent in the inorganic acid adsorbent bed layer; the gas passing through the inorganic acid removing tower is sent into an organic sulfur hydrolysis tower through a pipeline for COS hydrolysis, a hydrolysis catalyst bed layer is arranged in the middle of the organic sulfur hydrolysis tower, and a COS hydrolysis catalyst is filled in the organic sulfur hydrolysis tower; the coal gas passing through the organic sulfur hydrolysis tower is sent to a desulfurization tower through a pipeline to remove H2S, a desulfurizer bed layer is arranged in the middle of the desulfurization tower and filled with Fe2O3And the desulfurizer enters the gas output pipeline through the gas of the desulfurizing tower.
9. A blast furnace gas step and dry deacidification method according to claim 8, further comprising the steps of: and adjusting the opening degree of a one-way backflow valve on a bypass pipeline connecting the gas inlet pipeline and the gas outlet pipeline and the rotating speed of the booster fan to enable part of the gas in the gas outlet pipeline to flow back to the gas inlet pipeline and be mixed with the gas in the gas inlet pipeline so as to obtain the required reactant concentration and pressure.
10. A blast furnace gas step and dry deacidification method according to claim 9, further comprising the steps of: when no CaCl is contained in the dehydration drying tower2After the drying agent is invalid, the flange connection is disassembled, the invalid anhydrous drying agent in the dehydration drying tower is emptied, and new anhydrous CaCl is filled2A desiccant; when the CaO adsorbent in the inorganic acid removal tower fails, the failed CaO adsorbent in the inorganic acid removal tower is emptied by disassembling the flange connection, and a new CaO adsorbent is loaded; when the COS hydrolysis catalyst in the organic sulfur hydrolysis tower fails, the COS hydrolysis catalyst which fails in the organic sulfur hydrolysis tower is emptied through dismounting flange connection, and a new COS hydrolysis catalyst is loaded; when Fe is in the desulfurizing tower2O3After the desulfurizer fails, the flange connection is disassembled to empty the failed Fe in the desulfurizing tower2O3Desulfurizing agent, charging new Fe2O3A desulfurizing agent; before the flange is disassembled, the one-way return valve is closed, the atmosphere communicating valve is opened, and the booster fan is started to sweep residual gas.
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