CN112915777A - Blast furnace gas dechlorination, desulfurization and purification process - Google Patents

Blast furnace gas dechlorination, desulfurization and purification process Download PDF

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CN112915777A
CN112915777A CN201911233736.2A CN201911233736A CN112915777A CN 112915777 A CN112915777 A CN 112915777A CN 201911233736 A CN201911233736 A CN 201911233736A CN 112915777 A CN112915777 A CN 112915777A
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blast furnace
furnace gas
gas
reactor
dust removal
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张先茂
郑峰伟
王泽�
王瑜
金建涛
陈凯
周正
瞿玖
王国兴
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Wuhan Kelin Chemical Industry Group Co ltd
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D50/00Combinations of methods or devices for separating particles from gases or vapours
    • B01D50/20Combinations of devices covered by groups B01D45/00 and B01D46/00
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/48Sulfur compounds
    • B01D53/52Hydrogen sulfide
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/54Nitrogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/46Removing components of defined structure
    • B01D53/68Halogens or halogen compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77Liquid phase processes
    • B01D53/78Liquid phase processes with gas-liquid contact
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D53/00Separation 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
    • B01D53/34Chemical or biological purification of waste gases
    • B01D53/74General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86Catalytic processes
    • B01D53/8603Removing sulfur compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D2257/00Components to be removed
    • B01D2257/10Single element gases other than halogens
    • B01D2257/104Oxygen

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Abstract

The invention discloses a blast furnace gas dechlorinating, desulfurizing and purifying process. Firstly, the pipeline between the gravity dust removal and the cloth bag dust removal is used as a deacidification fluidized bed reactor to remove hydrogen chloride and cyanic acid in blast furnace gas, and then the blast furnace gas enters a deoxidation reactor to catalyze and remove O2Then the organic sulfur is hydrolyzed into H in an organic sulfur hydrolysis conversion reactor2S, finally entering a wet method for removingThe sulfur system removes sulfides. The process does not influence the dry dedusting and the residual pressure turbine power generation device to recover the residual pressure and the residual heat for power generation, can efficiently remove chloride, cyanide and sulfide in the blast furnace gas, and has the characteristics of high removal precision, simple flow, small pressure drop and temperature drop, simple equipment, less investment, low operation cost and small occupied area, and the whole technical and economic advantages are very obvious.

Description

Blast furnace gas dechlorination, desulfurization and purification process
Technical Field
The invention relates to a process for dechlorinating, desulfurizing and purifying blast furnace gas, belonging to the field of coal chemical industry.
Background
3500-4000 m blast furnace gas is generated when 1 ton of coke is consumed in the iron making process, and the reasonable and effective utilization of the blast furnace gas has important significance for circular economy, energy conservation and emission reduction. In recent years, with the widespread use of blast furnace gas dry dedusting and residual pressure turbine power generation units (TRTs), the pressure energy and heat energy of blast furnace gas are sufficiently recovered, the enterprise efficiency is improved, and the development of enterprises is promoted, but harmful substances (such as chloride, sulfide, and cyanide) in the gas are not effectively treated, SO that not only pipelines and power generation equipment are corroded, but also SO is emitted in the combustion of the lower section2And HCl causes serious environmental pollution. With the implementation of the ultralow emission standard of atmospheric pollutants in the iron and steel industry, the flue gas SO generated after the combustion of blast furnace gas is required2≤30mg/m³、NOxCarrying out fruit thinning according to 50mg/m or less, carrying out fruit thinning according to 5mg/m or less. Therefore, the comprehensive utilization and purification of blast furnace gas must be performed simultaneously.
Compared with the traditional wet dust removal method, the blast furnace gas adopts dry dust removal, can recover and utilize sensible heat of the gas, save water and electricity, reduce the occupied area of industry, and improve TRT (blast furnace top gas recovery turbine) generating capacity and dust removal rate, so that the blast furnace gas is favored by various iron and steel enterprises. The wet dust removal method can simultaneously remove harmful substances such as sulfur, chlorine and nitrogen in the gas, and the energy-saving and environment-friendly dry dust removal method needs to add purification equipment, so that the problem that the iron and steel enterprises need to solve urgently is solved by efficiently removing impurities such as cyanic acid, chlorine, sulfur and the like in the blast furnace gas and further slowing down or solving the problems of salt accumulation and corrosion of the equipment.
Patent CN106435077B discloses a dry purification method and system for blast furnace gas, the method comprises a chemical looping combustion reactor and two adsorption towers, carrier gas is heated by heat release of the chemical looping combustion reaction, high-temperature carrier gas is used for desorbing and regenerating adsorbent, and desorbed NH is3Introducing the gas into a chemical looping combustion reactor to perform reduction reaction with the oxidation state oxygen carrier, introducing air into the chemical looping combustion reactor to perform an oxidation regeneration process of the reduction state oxygen carrier after the desorption of the adsorbent in the adsorption tower is completed, and purifying the blast furnace gas by adopting the alternate adsorption and regeneration of two parallel adsorption towers. The process adopts a chemical adsorption method to adsorb acid gas, carbonyl sulfide, carbon disulfide and the like are not treated, and pollutants can still enter a gas combustion unit along with blast furnace gas, so that harmful substances in the discharged tail gas are still not solved.
Patent CN109609202A discloses a method for desulfurizing and purifying blast furnace gas, comprising the steps of: s1, the blast furnace gas enters an organic sulfur conversion device after being dedusted by a dry cloth bag dedusting device, and the organic sulfur is converted into H2S; s2, then, the mixed gas enters a residual pressure turbine power generation device to recover pressure energy and heat energy; and S3, the cooled blast furnace gas enters a wet desulphurization device to remove hydrogen sulfide, and then the blast furnace gas goes to each user device. The method can effectively remove sulfides in the coal gas, but oxygen in the blast furnace gas is not removed, and the oxygen can not only cause sulfation of the organic sulfur hydrolysis catalyst, but also easily react with desulfurization rich liquid in a wet desulfurization tower to separate out elemental sulfur, thereby causing pipeline blockage; in addition, the dechlorination of the invention needs to be separately provided with a dechlorination tower, thus increasing the cost input.
Disclosure of Invention
The invention aims to meet higher environmental protection requirements and demands, and develops a complete blast furnace gas purification process with high dechlorination and desulfurization efficiency and low construction or reconstruction cost aiming at the defects of the existing blast furnace gas purification process.
To realizeThe technical scheme of the invention is as follows: firstly, the pipeline between the gravity dust removal and the cloth bag dust removal is used as a deacidification fluidized bed reactor to remove hydrogen chloride and cyanic acid in blast furnace gas, and then the blast furnace gas enters a deoxidation reactor to catalyze and remove O2Then the organic sulfur is hydrolyzed into H in an organic sulfur hydrolysis conversion reactor2S, finally, entering a wet desulphurization system to remove sulfide, and specifically comprising the following steps:
a. the blast furnace gas firstly enters gravity dust removal, then enters cloth bag dust removal to filter dust in the gas, deacidification powder adsorbent is sprayed into a pipeline between the gravity dust removal and the cloth bag dust removal, hydrogen chloride and cyanic acid in the gas react with active components to be removed under certain conditions, deacidification saturated powder adsorbent is collected by the cloth bag dust removal, and the chlorine of the deacidified gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3
b. B, the blast furnace gas treated in the step a enters a deoxidation reactor, and under certain reaction conditions and the action of a deoxidation catalyst, O in the gas2And H2Or CO is reacted to H2O or CO2Removing oxygen, oxygen-removing reactor, and removing O2The content is less than 80mg/m3
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device to recover residual pressure and generate power by waste heat, then enters an organic sulfur hydrolysis conversion reactor, and carbonyl sulfide, carbon disulfide and water vapor in the blast furnace gas are subjected to hydrolysis reaction under certain conditions and under the action of an organic sulfur hydrolysis catalyst to be converted into H which is easy to remove2S, the hydrolysis conversion rate is more than 95 percent;
d. the blast furnace gas after hydrolysis conversion enters a wet desulphurization system for desulphurization, firstly, desulphurization absorption liquid is sprayed into a pipeline between an organic sulfur hydrolysis reactor and a desulphurization absorption tower, the blast furnace gas is cooled and coarsely desulfurized, then the cooled blast furnace gas is in countercurrent contact with the desulphurization absorption liquid in the desulphurization absorption tower for fine desulphurization, gas-liquid separation is carried out in the absorption tower, and the total sulfur content after purification is less than 10mg/Nm3The blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption rich solution reacts with air in a regeneration tank to be separated out and separate sulfur foam to obtain regeneration liquid, and the regeneration liquid is circularly absorbedAnd (6) recovering and desulfurizing.
The deacidification powder adsorbent in the step a comprises magnesium oxide as a main active ingredient, calcium oxide, manganese oxide and iron oxide as auxiliary agents, and the critical fluidization speed of the powder is 0.012 m.S-1
The step a of spraying the deacidification powder adsorbent into the pipeline between the gravity dust removal and the cloth bag dust removal utilizes the pipeline as a deacidification fluidized bed reactor; the certain conditions are that the temperature is 110-250 ℃, and the blast furnace gas flow velocity is greater than the critical fluidization velocity of the powder adsorbent.
The chlorine and the cyanogen in the blast furnace gas treated by the step a are less than 0.1mg/m3(ii) a The decyanation and dechlorination can protect the deoxidation catalyst and the organic sulfur hydrolysis catalyst from poisoning.
The deoxygenation reactor in the step b and the organic sulfur hydrolysis conversion reactor in the step c both adopt radial flow reactors, so that the pressure drop of gas passing through the reactors is reduced, and the resistance of a single reactor is less than 3 kPa.
The deoxygenation reactor in the step b is filled with a deoxygenation catalyst, the catalyst takes at least one of a large-hole spherical A-type molecular sieve and cloverleaf-shaped mordenite as a carrier, takes Cu, Mn, Ti, Ce and Mo as active components and takes lanthanide metal as an auxiliary agent.
The certain reaction condition of the step b is that the space velocity is 3750-10000 h-1The temperature is 100-230 ℃.
And c, filling an organic sulfur hydrolysis conversion reactor with an organic sulfur hydrolysis catalyst, wherein the catalyst takes at least one of cloverleaf strip-shaped X-type molecular sieves or Y-type molecular sieves as a carrier, and takes multiple elements of Na, Mg, Ca, Fe, Co, Ti, Mo and W as active components.
The certain reaction condition in the step c is that the airspeed is 4000-10000 h-1The temperature is 50-120 ℃.
The wet desulphurization system in the step d adopts any one of a PDS method, a tannin extract method and an iron complexing method; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3
The blast furnace gas purification process has the following beneficial effects: (1) the pipeline between the gravity dust removal and the cloth bag dust removal is fully utilized as a deacidification fluidized bed reactor, so that the investment cost is saved; the problem of corrosion of the whole purification system can be relieved by removing chlorine before cloth bag dust removal; (2) the deoxidation reactor and the organic sulfur hydrolysis conversion reactor both adopt radial flow reactors, so that the pressure drop of gas passing through the reactors can be effectively reduced, and the resistance of a single reactor is less than 3 kPa; (3) the pipeline between the organic sulfur hydrolysis reactor and the wet desulphurization system is fully utilized as the desulphurization absorption reactor, so that the design capacity of the desulphurization absorption tower can be reduced, the temperature of coal gas can be reduced as much as possible in the pipeline, and the cost investment of a cooling tower or heat exchange equipment is reduced; (4) the oxygen in the coal gas is removed, so that the phenomenon that the pipeline is blocked due to elemental sulfur separated out by the reaction of the desulfurization rich solution in the pipeline or the absorption tower and the oxygen can be avoided; (5) the desulfurization powder adsorbent, the deoxidation catalyst and the organic sulfur hydrolysis catalyst have wide application temperature range, and can be directly used without changing the temperature of blast furnace gas by heat exchange. In conclusion, the process can simultaneously remove sulfides, chlorides, cyanic acid and the like in the blast furnace gas, has the characteristics of high removal precision, simple flow, small pressure drop and temperature drop, simple equipment, less investment, low operation cost and small occupied area, and has obvious advantages of the whole technology and economy.
Drawings
FIG. 1 is a process flow diagram of the dechlorination, desulfurization and purification process of blast furnace gas.
In fig. 1, 1 is gravity dust removal, 2 is bag dust removal, 3 is a deoxidation reactor, 4 is a residual pressure turbine power generation device (TRT), 5 is an organic sulfur hydrolysis conversion reactor, 6 is a desulfurization absorption tower, 7 is a regeneration tank, and 8 is a sulfur foam collecting tank.
Detailed Description
The invention will be further illustrated with reference to fig. 1 and the examples, but the invention is not limited to the examples.
The technological process of dechlorination, desulfurization and purification of blast furnace gas disclosed by the invention is shown in figure 1 and comprises the following steps:
a. blast furnace gas firstly enters a gravity dust removal device 1 and then enters a cloth bag dust removal device 2 to passFiltering dust in the coal gas; a pipeline A between the gravity dust removal 1 and the cloth bag dust removal 2 is used as a deacidification fluidized bed reactor, and a deacidification powder adsorbent is sprayed into the pipeline A; the gas flow velocity of the blast furnace is 0.012 m.S higher than the critical fluidization velocity of the powder adsorbent at the temperature of 110-250 DEG C-1Under the condition, hydrogen chloride and cyanic acid in the coal gas react with active components to be removed, and a cloth bag dust removal 2 is utilized to collect deacidification saturated powder adsorbent; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3
b. B, allowing the blast furnace gas treated in the step a to enter a radial flow deoxygenation reactor 3, wherein the pressure drop of a bed layer is less than 3 kPa; at the airspeed of 3750-10000 h-1At a temperature of 100 to 230 ℃ and O2And H2Or CO is reacted to H2O or CO2Removing oxygen; after passing through a deoxygenation reactor, O2The content is less than 80mg/m3
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device 4 to recover residual pressure and generate power by waste heat, and then enters an organic sulfur hydrolysis conversion reactor 5 at the airspeed of 4000-10000 h-1Under the conditions of 50-120 ℃ and the catalytic action of the organic sulfur hydrolysis catalyst, carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas are subjected to hydrolysis reaction and converted into H which is easy to remove2S。
d. The blast furnace gas after hydrolysis and conversion enters a wet desulphurization system; firstly, spraying desulfurization absorption liquid into a pipeline B between an organic sulfur hydrolysis reactor 5 and a desulfurization absorption tower 6 to carry out temperature reduction and primary desulfurization on blast furnace gas; the cooled blast furnace gas is in countercurrent contact with desulfurization absorption liquid in a desulfurization absorption tower 6 for fine desulfurization, and gas-liquid separation is carried out in the absorption tower; the purified blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption pregnant solution reacts with air in the regeneration tank 7 to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization.
Example 1
The dechlorinating, desulfurizing and purifying process of blast furnace gas in certain steel and iron works in Shanxi is shown in attached figure 1. The gas amount of the raw material gas is 400000Nm3The temperature is 130-250 ℃, and the components, harmful substances and the content of the harmful substances are shown in table 1.
TABLE 1 composition of feed gases and harmful substances and their contents
Components content/V% Hazardous substances content/mg/Nm3
CO 24 HCN 17
H2 4.1 HCl 36.4
CO2 13.8 H2S 15.3
N2 57.5 COS 122.6
O2 0.6 CS2 19.8
H2O Saturated steam
The specific purification steps are as follows:
a. the blast furnace gas firstly enters a gravity dust removal device 1 and then enters a cloth bag dust removal device 2 to filter dust in the gas; a pipeline A between the gravity dust removal 1 and the cloth bag dust removal 2 is used as a deacidification fluidized bed reactor, and a deacidification powder adsorbent is sprayed into the pipeline A; the deacidification powder adsorbent comprises magnesium oxide as a main active component and calcium oxide, manganese oxide and iron oxide as auxiliaries; the gas flow velocity of the blast furnace is 0.012 m.S higher than the critical fluidization velocity of the powder adsorbent at the temperature of 130-250 DEG C-1Under the condition, hydrogen chloride and cyanic acid in the coal gas react with active components to be removed, and a cloth bag dust removal 2 is utilized to collect deacidification saturated powder adsorbent; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3(ii) a And the temperature of the blast furnace gas after the dry dedusting 2 is 120-230 ℃.
b. B, allowing the blast furnace gas treated in the step a to enter a radial flow deoxidation reactor 3, wherein the pressure drop of a bed layer is less than 3kPa, the reactor is filled with 40m deoxidation catalyst which takes a macroporous spherical A-type molecular sieve and cloverleaf strip-shaped mordenite as carriers, Cu, Mn, Ti, Ce and Mo as active components and lanthanide metal as an auxiliary agent3(ii) a At airspeed of 10000h-1The temperature is 120-230 ℃ and the O in the coal gas is under the catalytic action of a deoxidation catalyst2And H2Or CO is reacted to H2O or CO2Removing oxygen; after passing through a deoxidation reactor, blast furnace gas O2The content is less than 80mg/m3(ii) a Deoxidation belongs to exothermic reaction, and the outlet temperature of the deoxidation reactor 3 is maintained at 120-230 ℃.
c. Blast furnace gas entry residue after deoxidationThe pressure turbine power generation device 4 recovers residual pressure and generates power by using the residual pressure, and the temperature of blast furnace gas at a TRT outlet is 50-120 ℃; then the organic sulfur hydrolysis conversion catalyst enters a radial flow organic sulfur hydrolysis conversion reactor 5, the pressure drop of a bed layer is less than 3kPa, the reactor is filled with 100m organic sulfur hydrolysis catalyst which takes cloverleaf strip-shaped X-type molecular sieves and Y-type molecular sieves as carriers and takes Na, Mg, Co, Ti, Mo and W elements as active components3(ii) a At the airspeed of 4000h-1Under the condition that the temperature is 50-120 ℃, the organic sulfur hydrolysis catalyst catalyzes carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas to perform hydrolysis reaction, and the carbonyl sulfide, the carbon disulfide and the water vapor are converted into H which is easy to remove2S; the conversion rate of carbonyl sulfide and carbon disulfide into inorganic sulfur through catalytic hydrolysis is more than 95%.
d. The blast furnace gas after hydrolytic conversion enters a complex iron wet desulphurization system, firstly, a desulphurization absorption liquid is sprayed into a pipeline B between an organic sulfur hydrolysis reactor 5 and a desulphurization absorption tower 6, and the blast furnace gas is cooled and subjected to coarse desulphurization to ensure that the temperature of the blast furnace gas is lower than 80 ℃; the cooled blast furnace gas is in countercurrent contact with desulfurization absorption liquid in a desulfurization absorption tower 6 for fine desulfurization, and gas-liquid separation is carried out in the absorption tower; the purified blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption pregnant solution reacts with air in a regeneration tank 7 to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3
Example 2
After the blast furnace gas of a certain steel plant in Hebei exceeds the standard after being combusted, the purification process is reconstructed on the basis of the original wet desulphurization, TRT power generation equipment is added to increase the attached economic benefit, and the existing dechlorination desulphurization purification process is shown as the attached drawing 1. The gas amount of the raw material gas is 300000Nm3The temperature is 110-230 ℃, and the components, harmful substances and the content thereof are shown in Table 2.
TABLE 2 composition of feed gas and harmful substances and their contents
Components content/V% Hazardous substances content/mg/Nm3
CO 24.2 HCN 13.2
H2 5.9 HCl 29.9
CO2 16.8 H2S 11.4
N2 52.8 COS 154.7
O2 0.3 CS2 38.3
H2O Saturated steam
The specific purification steps are as follows:
a. the blast furnace gas firstly enters a gravity dust removal device 1 and then enters a cloth bag dust removal device 2 to filter dust in the gas; a pipeline A between the gravity dust removal 1 and the cloth bag dust removal 2 is used as a deacidification fluidized bed reactor, and a deacidification powder adsorbent which takes magnesium oxide as an active ingredient and calcium oxide, manganese oxide and iron oxide as auxiliaries is sprayed into the pipeline A; the gas flow velocity of the blast furnace coal gas is 0.012 m.S higher than the critical fluidization velocity of the powder adsorbent at the temperature of 110-230 DEG C-1Under the condition, hydrogen chloride and cyanic acid in the coal gas react with active components to be removed, and a cloth bag dust removal 2 is utilized to collect deacidification saturated powder adsorbent; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3(ii) a And the temperature of the blast furnace gas after the dry dedusting 2 is 100-215 ℃.
b. B, allowing the blast furnace gas treated in the step a to enter a radial flow deoxidation reactor 3, wherein the pressure drop of a bed layer is less than 3kPa, the reactor is filled with a deoxidation catalyst 80m which takes a macroporous spherical A-type molecular sieve and cloverleaf strip-shaped mordenite as carriers, Cu, Mn, Ti, Ce and Mo as active components and lanthanide metal as an auxiliary agent3(ii) a At the space velocity of 3750h-1At the temperature of 100-215 ℃, the deoxidation catalyst catalyzes O in the coal gas2And H2Or CO is reacted to H2O or CO2Removing oxygen; after passing through a deoxidation reactor, blast furnace gas O2The content is less than 50mg/m3(ii) a Deoxidation belongs to exothermic reaction, and the outlet temperature of the deoxidation reactor 3 is maintained at 100-215 ℃.
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device 4 to recover residual pressure and generate power by using residual heat, and the temperature of the blast furnace gas at the TRT outlet is 50-100 ℃; then the organic sulfur enters a radial flow organic sulfur hydrolysis conversion reactor 5, the pressure drop of a bed layer is less than 3kPa, and 30m of organic sulfur hydrolysis catalyst which takes clover strip-shaped X-type molecular sieve as a carrier and takes Na, Mg, Ca, Fe, Co and Ti as active components is filled in the reactor3(ii) a In the skyThe speed is 10000h-1Under the condition that the temperature is 50-100 ℃, the organic sulfur hydrolysis catalyst catalyzes carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas to perform hydrolysis reaction, and the carbonyl sulfide, the carbon disulfide and the water vapor are converted into H which is easy to remove2S; the conversion rate of carbonyl sulfide and carbon disulfide into inorganic sulfur through catalytic hydrolysis is more than 97%.
d. The blast furnace gas after hydrolysis conversion enters a PDS wet desulphurization system; firstly, spraying desulfurization absorption liquid into a pipeline B between an organic sulfur hydrolysis reactor 5 and a desulfurization absorption tower 6, and carrying out temperature reduction and coarse desulfurization on blast furnace gas to enable the temperature to be lower than 70 ℃; the cooled blast furnace gas is in countercurrent contact with desulfurization absorption liquid in a desulfurization absorption tower 6 for fine desulfurization, and gas-liquid separation is carried out in the absorption tower; the purified blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption pregnant solution reacts with air in a regeneration tank 7 to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3

Claims (10)

1. A blast furnace gas dechlorination, desulfurization and purification process is characterized by comprising the following steps:
a. the blast furnace gas firstly enters gravity dust removal, then enters a cloth bag dust removal to filter dust in the gas, deacidification powder adsorbent is sprayed into a pipeline between the gravity dust removal and the cloth bag dust removal, hydrogen chloride and cyanic acid in the gas react with active components under a certain condition to be removed, and deacidification saturated powder adsorbent is collected by the cloth bag dust removal; the deacidified chlorine in the gas is less than 0.1mg/m3Cyanic acid less than 0.1mg/m3
b. B, the blast furnace gas treated in the step a enters a deoxidation reactor, and under certain reaction conditions and the action of a deoxidation catalyst, O in the gas2And H2Or CO is reacted to H2O or CO2Removing oxygen, oxygen-removing reactor, and removing O2The content is less than 80mg/m3
c. The deoxidized blast furnace gas enters a residual pressure turbine power generation device to recover residual pressure and generate power by waste heat, then enters an organic sulfur hydrolysis conversion reactor, and is subjected to reaction under certain conditionsUnder the action of organic sulfur hydrolysis catalyst, carbonyl sulfide, carbon disulfide and water vapor in blast furnace gas are subjected to hydrolysis reaction and converted into H easy to remove2S, the hydrolysis conversion rate is more than 95 percent;
d. the blast furnace gas after hydrolysis conversion enters a wet desulphurization system for desulphurization, firstly, desulphurization absorption liquid is sprayed into a pipeline between an organic sulfur hydrolysis reactor and a desulphurization absorption tower, the blast furnace gas is cooled and coarsely desulfurized, then the cooled blast furnace gas is in countercurrent contact with the desulphurization absorption liquid in the desulphurization absorption tower for fine desulphurization, gas-liquid separation is carried out in the absorption tower, and the total sulfur content after purification is less than 10mg/Nm3The blast furnace gas is sent to a buffer gas holder or a gas user, the desulfurization absorption rich solution reacts with air in a regeneration tank to be separated out and sulfur foam is separated to obtain a regeneration solution, and the regeneration solution circularly absorbs desulfurization.
2. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the deacidification powder adsorbent in the step a comprises magnesium oxide as a main active ingredient, calcium oxide, manganese oxide and iron oxide as auxiliary agents, and the critical fluidization speed of the powder is 0.012 m.S-1
3. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the step a of spraying the deacidification powder adsorbent into the pipeline between the gravity dust removal and the cloth bag dust removal utilizes the pipeline as a deacidification fluidized bed reactor; the certain conditions are that the temperature is 110-250 ℃, and the blast furnace gas flow velocity is greater than the critical fluidization velocity of the powder adsorbent.
4. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the chlorine and the cyanogen in the blast furnace gas treated by the step a are less than 0.1mg/m3(ii) a The decyanation and dechlorination can protect the deoxidation catalyst and the organic sulfur hydrolysis catalyst from poisoning.
5. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the deoxygenation reactor in the step b and the organic sulfur hydrolysis conversion reactor in the step c both adopt radial flow reactors, so that the pressure drop of gas passing through the reactors is reduced, and the resistance of a single reactor is less than 3 kPa.
6. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the deoxygenation reactor in the step b is filled with a deoxygenation catalyst, the catalyst takes at least one of a large-hole spherical A-type molecular sieve and cloverleaf-shaped mordenite as a carrier, takes Cu, Mn, Ti, Ce and Mo as active components and takes lanthanide metal as an auxiliary agent.
7. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the certain reaction condition of the step b is that the space velocity is 3750-10000 h-1The temperature is 100-230 ℃.
8. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: and c, filling an organic sulfur hydrolysis conversion reactor with an organic sulfur hydrolysis catalyst, wherein the catalyst takes at least one of cloverleaf strip-shaped X-type molecular sieves or Y-type molecular sieves as a carrier, and takes multiple elements of Na, Mg, Ca, Fe, Co, Ti, Mo and W as active components.
9. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the certain reaction condition in the step c is that the airspeed is 4000-10000 h-1The temperature is 50-120 ℃.
10. The process of claim 1, wherein the blast furnace gas is dechlorinated, desulfurized and purified, and is characterized in that: the wet desulphurization system in the step d adopts any one of a PDS method, a tannin extract method and an iron complexing method; the total sulfur content in the blast furnace gas after wet desulphurization is less than 10mg/Nm3
CN201911233736.2A 2019-12-05 2019-12-05 Blast furnace gas dechlorination, desulfurization and purification process Pending CN112915777A (en)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113372965A (en) * 2021-06-28 2021-09-10 中晶环境科技股份有限公司 Blast furnace gas desulfurization process
CN113549474A (en) * 2021-08-04 2021-10-26 上海大学 Blast furnace gas step-by-step dry deacidification system and method
CN113584241A (en) * 2021-08-04 2021-11-02 上海大学 Dry-method simultaneous desulfurization and dechlorination system and method for blast furnace gas
CN113604255A (en) * 2021-08-12 2021-11-05 上海展恒环保科技有限公司 Blast furnace gas sulfur resource utilization device
CN114196448A (en) * 2022-02-16 2022-03-18 北京中航天业科技有限公司 Full-flow dry type blast furnace gas fine desulfurization system and method
CN114191929A (en) * 2021-12-24 2022-03-18 常州化工设计院有限公司 Chemical tail gas treatment process
CN114392643A (en) * 2021-12-30 2022-04-26 北京北科环境工程有限公司 Preparation method of dechlorinating agent for blast furnace gas
CN114591765A (en) * 2022-03-08 2022-06-07 河北中科朗博环保科技有限公司 Blast furnace gas fine desulfurization device and fine desulfurization method
CN114836247A (en) * 2022-05-06 2022-08-02 桂林理工大学 Ultralow-emission low-carbon cooperative control method for deep purification of blast furnace gas in steel industry
CN115141660A (en) * 2022-08-02 2022-10-04 江苏省环境工程技术有限公司 Blast furnace gas dry-type fine desulfurization system and fine desulfurization method
EP4170049A1 (en) * 2021-10-22 2023-04-26 Danieli Corus BV Reduction of nox emission from combusting blast furnace gas

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN205007844U (en) * 2015-08-27 2016-02-03 盾安(天津)节能系统有限公司 Two circular flue desulfurization system of single tower
CN107281869A (en) * 2016-04-01 2017-10-24 天津渤海环保工程有限公司 A kind of method handled for Cremation Machine tail gas clean-up
CN110272766A (en) * 2019-05-22 2019-09-24 湖南衡钢百达先锋能源科技有限公司 A kind of method of purification and system of blast furnace gas
CN110452744A (en) * 2019-08-08 2019-11-15 佰利天控制设备(北京)有限公司 Blast furnace coal gas comprehensive management of environmental protection system and technique
CN110484307A (en) * 2019-08-20 2019-11-22 安徽宝天新能源科技有限公司 A kind of blast furnace gas dechlorination, desulphurization system and technique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN205007844U (en) * 2015-08-27 2016-02-03 盾安(天津)节能系统有限公司 Two circular flue desulfurization system of single tower
CN107281869A (en) * 2016-04-01 2017-10-24 天津渤海环保工程有限公司 A kind of method handled for Cremation Machine tail gas clean-up
CN110272766A (en) * 2019-05-22 2019-09-24 湖南衡钢百达先锋能源科技有限公司 A kind of method of purification and system of blast furnace gas
CN110452744A (en) * 2019-08-08 2019-11-15 佰利天控制设备(北京)有限公司 Blast furnace coal gas comprehensive management of environmental protection system and technique
CN110484307A (en) * 2019-08-20 2019-11-22 安徽宝天新能源科技有限公司 A kind of blast furnace gas dechlorination, desulphurization system and technique

Non-Patent Citations (8)

* Cited by examiner, † Cited by third party
Title
(日)一色尚次等著,王也康等译: "《余热回收利用系统实用手册 上》", 31 December 1988, 北京:机械工业出版社 *
刘宝鸿主编: "《化学反应器》", 30 November 1999, 北京:化学工业出版社 *
刘麟瑞等: "《冶金炉料手册》", 28 February 1991 *
宁平等: "《含CO工业废气中有机硫深度净化关键技术》", 31 January 2014, 北京:冶金工业出版社 *
徐振刚等: "《中国洁净煤技术》", 30 April 2012 *
贵永亮等: "《高炉喷煤理论与关键技术研究》", 北京:冶金工业出版社 *
赵由才等: "《农村生活垃圾处理与资源化利用技术》", 31 January 2018, 北京:冶金工业出版社 *
辽宁省科学技术志编纂委员会编: "《超重力湿式氧化法脱除气体中硫化氢技术》", 31 December 2013, 沈阳:辽宁科学技术出版社 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113372965A (en) * 2021-06-28 2021-09-10 中晶环境科技股份有限公司 Blast furnace gas desulfurization process
CN113372965B (en) * 2021-06-28 2024-05-28 中晶环境科技股份有限公司 Desulfurization process for blast furnace gas
CN113549474A (en) * 2021-08-04 2021-10-26 上海大学 Blast furnace gas step-by-step dry deacidification system and method
CN113584241A (en) * 2021-08-04 2021-11-02 上海大学 Dry-method simultaneous desulfurization and dechlorination system and method for blast furnace gas
CN113549474B (en) * 2021-08-04 2022-08-23 上海大学 Blast furnace gas step-by-step dry deacidification system and method
CN113604255A (en) * 2021-08-12 2021-11-05 上海展恒环保科技有限公司 Blast furnace gas sulfur resource utilization device
WO2023067057A1 (en) * 2021-10-22 2023-04-27 Danieli Corus B.V. REDUCTION OF NOx EMISSION FROM COMBUSTING BLAST FURNACE GAS
EP4170049A1 (en) * 2021-10-22 2023-04-26 Danieli Corus BV Reduction of nox emission from combusting blast furnace gas
CN114191929B (en) * 2021-12-24 2022-12-06 常州化工设计院有限公司 Chemical tail gas treatment process
CN114191929A (en) * 2021-12-24 2022-03-18 常州化工设计院有限公司 Chemical tail gas treatment process
CN114392643A (en) * 2021-12-30 2022-04-26 北京北科环境工程有限公司 Preparation method of dechlorinating agent for blast furnace gas
CN114392643B (en) * 2021-12-30 2022-09-23 北京北科环境工程有限公司 Preparation method of dechlorinating agent for blast furnace gas
CN114196448A (en) * 2022-02-16 2022-03-18 北京中航天业科技有限公司 Full-flow dry type blast furnace gas fine desulfurization system and method
CN114591765A (en) * 2022-03-08 2022-06-07 河北中科朗博环保科技有限公司 Blast furnace gas fine desulfurization device and fine desulfurization method
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