CN111876206A - Blast furnace gas fine desulfurization combined process method - Google Patents
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- CN111876206A CN111876206A CN202010787553.1A CN202010787553A CN111876206A CN 111876206 A CN111876206 A CN 111876206A CN 202010787553 A CN202010787553 A CN 202010787553A CN 111876206 A CN111876206 A CN 111876206A
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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
- 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
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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
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/22—Apparatus, e.g. dry box purifiers
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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
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
- C10K1/26—Regeneration of the purifying material contains also apparatus for the regeneration of the purifying material
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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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Abstract
The invention provides a blast furnace gas fine desulfurization combined process method, belonging to the technical field of atmospheric pollution treatment. The process comprises the steps of firstly enabling blast furnace gas to pass through a deoxidation unit after bag-type dust removal, then enabling the blast furnace gas to enter a carbonyl sulfide hydrolysis system, enabling the hydrolyzed gas to enter a residual pressure turbine power generation device, then enabling the hydrolyzed gas to enter a dry desulfurization system, enabling the desulfurization system to be provided with two towers for one use, starting a standby tower after a working desulfurization tower is saturated in adsorption, and simultaneously starting a regeneration system to regenerate the desulfurizer saturated in adsorption. The invention can protect the rear-end hydrolytic agent, has no solid waste and waste water, and has safety, environmental protection and economy.
Description
Technical Field
The invention relates to the technical field of air pollution treatment, in particular to a blast furnace gas fine desulfurization combined process method.
Background
Blast furnace gas is one of the main fuels of the whole iron and steel company, and is often used as a hot blast stove of a power plant blast furnace and a steel rolling mill,The fuel of the heating furnace of the iron works is used. SO in flue gas discharged by blast furnace gas2The content of SO in the flue gas which is normally discharged can not meet the national ultra-clean discharge requirement2The content is more than 50mg/m3Even up to 200mg/m3The above.
The blast furnace gas mainly comprises CO and CO2、N2And also contains a small amount of O2、COS、H2S, dust and the like. Aiming at the requirements of source treatment, the COS and H in the blast furnace gas need to be removed2And S, dust. The patent CN110643395A adopts a cloth bag to remove dust, and then enters the hydrolysis tower from the top to contact with a honeycomb carbonyl sulfide hydrolysis catalyst in the tower, so as to convert organic sulfur into hydrogen sulfide. And (3) generating power by a turbine, and removing sulfides in the hydrolyzed blast furnace gas containing hydrogen sulfide by countercurrent contact of alkali liquor in an absorption tower. And the purified blast furnace gas is separated from the top of the absorption tower by a demister, and then enters a gas pipe network. The method has small pressure loss and small influence on TRT power generation, but the hydrolysis reaction temperature of the process is higher than 80 ℃, and the process is carried out in the presence of O2Hydrolysis tests show that the hydrolytic agent is easy to sulfate, and the active components of the hydrolytic agent generate sulfate, so that the hydrolysis efficiency is reduced, and the service life of the hydrolytic agent is shortened; in addition, the agent adopts an alkali liquor absorption method to remove hydrogen sulfide, and a large amount of waste water is generated.
Therefore, at the present stage, the case of falling to the ground is less for the control of the blast furnace gas source. The blast furnace gas mainly comprises CO and CO2Small amount of H2、O2And a harmful component COS of carbonyl sulfide and inorganic sulfur H2And S. The source treatment needs to convert the COS into the H by the action of the COS hydrolyzing agent2And desulfurizing after S. Because the raw material gas contains oxygen, the carbonyl sulfide hydrolytic agent is easy to be sulfated under the condition of oxygen, the hydrolysis efficiency is reduced, the service life of the hydrolytic agent is shortened, and the hydrolysis of the carbonyl sulfide is incomplete. In addition, carbonyl sulfide is hydrolyzed to become inorganic sulfur hydrogen sulfide, and the hydrogen sulfide is absorbed by an alkaline liquor method generally because the raw material gas contains a large amount of CO2Therefore, the method consumes much alkali and produces a large amount of desulfurization waste water which is difficult to treat.
Therefore, aiming at the current situation, the invention develops a novel combined process which can remove oxygen in blast furnace gas, protect the service life of carbonyl sulfide hydrolytic agent, adopts dry method recyclable desulfurizing agent, solves the problems of waste water, solid waste and the like and has excellent economical efficiency.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a blast furnace gas fine desulfurization combined process method.
The process method comprises the steps of firstly enabling blast furnace gas to pass through a deoxidation unit after bag-type dust removal, then enabling the blast furnace gas to enter a carbonyl sulfide hydrolysis system, enabling the hydrolyzed gas to enter a residual pressure turbine power generation device, then enabling the hydrolyzed gas to enter a dry-method desulfurization system, enabling the desulfurization system to be provided with two towers, one tower for use and one standby tower for use, starting the standby tower after a working desulfurization tower is saturated in adsorption, and simultaneously starting a regeneration system to regenerate the desulfurizer saturated in adsorption.
The method specifically comprises the following steps:
(1) dedusting blast furnace gas by a cloth bag;
(2) passing through a deoxidizing unit and then entering a carbonyl sulfide hydrolysis system;
(3) the hydrolyzed coal gas enters a residual pressure turbine power generation device;
(4) and (4) entering a dry desulfurization system, starting the standby tower after the working desulfurization tower is saturated in adsorption, and simultaneously starting a desulfurizer regeneration system to regenerate the desulfurization tower saturated in adsorption.
Wherein, a deoxidizing agent layer is arranged in the deoxidizing unit in the step (2), the bottom of the deoxidizing agent layer is provided with a discharge opening and a charging opening, and the deoxidizing agent adopts a commercially available sulfur-tolerant deoxidizing catalyst. The reaction temperature in the deoxidation unit is 100-150 ℃, the deoxidation catalyst is filled according to the gas quantity of the raw material gas, and the air speed of the deoxidizer is 3000-6000h-1。
The carbonyl sulfide hydrolysis system device in the step (2) comprises a hydrolysis reactor and a sound wave soot blowing system; the hydrolysis conditions are that the temperature is 80-200 ℃, the pressure is 50-300kPa, the carbonyl sulfide hydrolysis catalyst is filled in the hydrolysis reactor according to the gas quantity of the raw material gas, and the air speed of the hydrolysis catalyst is 4000--1。
The dry desulfurization system device in the step (4) comprises a desulfurizer bed layer, the bottom of the desulfurizer bed layer is provided with a discharge opening and a feed opening, the desulfurizer adopts an iron system desulfurizer, and the main active component is Fe2O3The desulfurizer generates Fe after absorbing hydrogen sulfide2S3The oxidation is recycled, the using temperature of the dry desulfurizing agent is 25-100 ℃, and the air speed of the desulfurizing agent is 1000--1。
And (4) the desulfurizer regeneration system comprises a high-speed pulping tank, an oxidation tank, a flotation tank, a deodorization induced draft fan, an oxidation air compressor, a plate-and-frame filter and forming equipment.
And (3) after the blast furnace gas passes through the turbine power generation device, reducing the temperature to 60-120 ℃.
The technical scheme of the invention has the following beneficial effects:
the invention protects the carbonyl sulfide hydrolyzing agent and ensures the hydrolysis efficiency of the carbonyl sulfide by adopting a combined process of deoxidation, carbonyl sulfide hydrolysis, dry desulphurization and desulfurizer regeneration; the dry desulfurization process is adopted to realize deep purification of the blast furnace gas of the iron and steel enterprises before the blast furnace gas enters downstream users for use, and the problem of standard exceeding of the flue gas emission of the blast furnace gas downstream users in the industry is solved; the desulfurizing agent capable of being regenerated and circulated is adopted, so that the problem of a large amount of waste water caused by alkali liquor desulfurization is solved, solid waste is avoided through regeneration and circulation, and the combined process has the advantages of economy, environmental protection, safety and the like.
Drawings
FIG. 1 is a flow chart of a blast furnace gas desulfurization process of the present invention;
FIG. 2 is a flow chart of the desulfurizing agent regeneration process of the present invention.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a blast furnace gas fine desulfurization combined process method.
As shown in figure 1, in the process, firstly, blast furnace gas passes through a deoxidation unit after being subjected to bag dust removal and then enters a carbonyl sulfide hydrolysis system, the hydrolyzed gas enters a residual pressure turbine power generation device and then enters a dry desulfurization system, the desulfurization system is provided with two towers, one tower is used, the standby tower is started after the working desulfurization tower is saturated in adsorption, and meanwhile, a regeneration system is started to regenerate the desulfurizer saturated in adsorption.
The method specifically comprises the following steps:
(1) dedusting blast furnace gas by a cloth bag;
(2) passing through a deoxidizing unit and then entering a carbonyl sulfide hydrolysis system;
(3) the hydrolyzed coal gas enters a residual pressure turbine power generation device;
(4) and (4) entering a dry desulfurization system, starting the standby tower after the working desulfurization tower is saturated in adsorption, and simultaneously starting a desulfurizer regeneration system to regenerate the desulfurization tower saturated in adsorption.
A deoxidizing agent layer is arranged in the deoxidizing unit, a discharge opening and a charging opening are formed in the bottom of the deoxidizing agent layer, and a commercially available sulfur-resistant deoxidizing agent is adopted as the deoxidizing agent;
the organic sulfur hydrolysis system device mainly comprises a hydrolysis reactor and a sound wave soot blowing system.
The dry desulfurization system device mainly comprises a desulfurizer bed layer, wherein the bottom of the desulfurizer bed layer is provided with a discharge opening and a feed opening, the desulfurizer adopts an iron system desulfurizer, and the main active component is Fe2O3The desulfurizer generates Fe after absorbing hydrogen sulfide2S3And can be regenerated in an oxidation cycle.
As shown in fig. 2, the desulfurizer regeneration system mainly comprises a high-speed pulping tank, an oxidation tank, a flotation tank, a deodorization induced draft fan, an oxidation air compressor, a plate-frame filter and a forming device.
The blast furnace gas after cloth bag dust removal firstly enters a deoxidation unit, and oxygen with low concentration in the feed gas and CO or H are reacted under the action of a deoxidation catalyst2The reaction is carried out, thus achieving the purpose of removing oxygen. And the deoxidized feed gas enters from the top of the hydrolysis tower and contacts with a hydrolysis catalyst in the tower, and carbonyl sulfide in the blast furnace gas converts organic sulfur into hydrogen sulfide under the action of a hydrolysis agent (the temperature is 80-200 ℃, and the pressure is 50-300 kPa). Meanwhile, in order to prevent the catalyst of the hydrolysis system from being blocked, the sound wave soot blowing system is added to periodically blow, so that the phenomenon that the pore passages of the hydrolysis agent are blocked by fly ash to reduce the hydrolysis efficiency is avoided.
The temperature of blast furnace gas after turbine power generation is reduced to 60-120 ℃, the blast furnace gas enters a dry desulphurization system and enters from the lower part of a desulphurization tower, the blast furnace gas containing hydrogen sulfide and a desulfurizer in a reactor perform chemical adsorption reaction to remove the hydrogen sulfide, and the purified blast furnace gas enters a gas pipe network.
When the desulfurizer is adsorbed and saturated, the hydrogen sulfide can not be removed to become a waste desulfurizer, and the waste desulfurizer is Fe2S3The novel desulfurizer is obtained by the production processes of crushing, pulping, oxidation regeneration, plate-frame filtration, molding and drying.
The following description is given with reference to specific examples.
Example 1
After the blast furnace gas is subjected to cloth bag dust removal, the temperature is 120 ℃, the pressure is 100-300 kPa, and the COS concentration is 120mg/m3，H2The S concentration is 40mg/m3. The raw material gas firstly passes through a deoxidation unit, the deoxidation efficiency is 92 percent, the oxygen concentration is reduced from 0.4 percent to 320ppm, then the raw material gas enters a carbonyl sulfide hydrolysis system, the hydrolysis efficiency is 95 percent, and the COS concentration of the hydrolyzed gas is less than 10mg/m3，H2The S concentration is 102mg/m3And the hydrolyzed raw material gas enters a residual pressure turbine power generation device.
The blast furnace gas after power generation enters a dry desulphurization system, the desulphurization system is provided with a working reactor and a spare reactor, the blast furnace gas enters a working reactor, and an inlet H2The S concentration is 102mg/m3After passing through the desulfurization bed layer, the hydrogen sulfide is removed by chemical adsorption reaction with the desulfurizing agent, and an outlet H is monitored2S concentration is less than 5mg/m3And the sulfur capacity is measured to be 15% after the working desulfurizing tower gradually absorbs and is saturated. When the working desulfurizing tower is saturated in adsorption, the raw material gas is switched to the standby reactor, the reactor saturated in adsorption is subjected to unloading regeneration, and the sulfur capacity of the regenerated desulfurizing agent is reduced to about 12%.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (8)
1. A blast furnace gas fine desulfurization combined process method is characterized in that: firstly, blast furnace gas passes through a deoxidation unit after being subjected to bag dust removal and then enters a carbonyl sulfide hydrolysis system, the hydrolyzed gas enters a residual pressure turbine power generation device and then enters a dry desulfurization system, the desulfurization system is provided with two towers, one tower is used, when a working desulfurization tower is saturated in adsorption, the standby tower is opened, and meanwhile, a regeneration system is started to regenerate the desulfurizer saturated in adsorption.
2. The blast furnace gas fine desulfurization combined process method according to claim 1, characterized in that: the method specifically comprises the following steps:
(1) dedusting blast furnace gas by a cloth bag;
(2) the blast furnace gas after dust removal enters a carbonyl sulfide hydrolysis system through a deoxidation unit;
(3) the hydrolyzed coal gas enters a residual pressure turbine power generation device;
(4) and (4) enabling the coal gas treated in the step (3) to enter a dry-method desulfurization system, starting a standby tower after the working desulfurization tower is saturated in adsorption, and simultaneously starting a desulfurizer regeneration system to regenerate the desulfurization tower saturated in adsorption.
3. The blast furnace gas fine desulfurization combined process method according to claim 2, characterized in that: and (3) arranging a deoxidizing agent layer in the deoxidizing unit in the step (2), wherein the bottom of the deoxidizing agent layer is provided with a discharge opening and a charging opening, and the deoxidizing agent adopts a commercially available sulfur-tolerant deoxidizing catalyst.
4. The blast furnace gas fine desulfurization combined process method according to claim 2, characterized in that: the reaction temperature in the deoxidation unit in the step (2) is 100--1。
5. The blast furnace gas fine desulfurization combined process method according to claim 2, characterized in that: the carbonyl sulfide hydrolysis system device in the step (2) comprises a hydrolysis reactor and a sound wave soot blowing system; the hydrolysis condition is temperature of 80-The temperature is 200 ℃, the pressure is 50-300kPa, the carbonyl sulfide hydrolysis catalyst is filled in the hydrolysis reactor according to the gas quantity of the raw material gas, and the air speed of the hydrolysis catalyst is 4000--1。
6. The blast furnace gas fine desulfurization combined process method according to claim 2, characterized in that: the dry desulfurization system device in the step (4) comprises a desulfurizer bed layer, the bottom of the desulfurizer bed layer is provided with a discharge opening and a feed opening, the desulfurizer adopts an iron system desulfurizer, and the desulfurizer generates Fe after absorbing hydrogen sulfide2S3The oxidation is recycled, the using temperature of the dry desulfurizing agent is 25-100 ℃, and the air speed of the desulfurizing agent is 1000--1。
7. The blast furnace gas fine desulfurization combined process method according to claim 2, characterized in that: and (4) the desulfurizer regeneration system comprises a high-speed pulping tank, an oxidation tank, a flotation tank, a deodorization induced draft fan, an oxidation air compressor, a plate-frame filter and forming equipment.
8. The blast furnace gas fine desulfurization combined process method according to claim 2, characterized in that: and (4) after the blast furnace gas passes through the turbine power generation device in the step (3), reducing the temperature to 60-120 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583721A (en) * | 2021-07-21 | 2021-11-02 | 福州大学 | Oxygen-free high-water-content high-furnace gas desulfurization system and process |
| CN113813756A (en) * | 2021-10-20 | 2021-12-21 | 国家能源集团重庆恒泰发电有限公司 | Flue gas purification system of coal-fired unit |
| 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 |
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| CN108479827A (en) * | 2018-04-03 | 2018-09-04 | 太原理工大学 | Medium temperature hydrolyzation converts carbonyl sulfur and the difunctional coupled catalyst of deoxidation and preparation method |
| CN109609202A (en) * | 2019-01-17 | 2019-04-12 | 武汉禾谷环保有限公司 | A kind of blast furnace gas desulfurizing and purifying method |
| CN111334339A (en) * | 2020-03-16 | 2020-06-26 | 山东洲蓝环保科技有限公司 | Fine desulfurization method for blast furnace gas |
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2020
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705108A (en) * | 2009-12-11 | 2010-05-12 | 郝天臻 | Liquid hydrocarbon mercaptan removal technique capable of deeply removing total sulfur |
| CN108479827A (en) * | 2018-04-03 | 2018-09-04 | 太原理工大学 | Medium temperature hydrolyzation converts carbonyl sulfur and the difunctional coupled catalyst of deoxidation and preparation method |
| CN109609202A (en) * | 2019-01-17 | 2019-04-12 | 武汉禾谷环保有限公司 | A kind of blast furnace gas desulfurizing and purifying method |
| CN111334339A (en) * | 2020-03-16 | 2020-06-26 | 山东洲蓝环保科技有限公司 | Fine desulfurization method for blast furnace gas |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113583721A (en) * | 2021-07-21 | 2021-11-02 | 福州大学 | Oxygen-free high-water-content high-furnace gas desulfurization system and process |
| CN113583721B (en) * | 2021-07-21 | 2022-10-18 | 中琉科技有限公司 | Oxygen-free high-water-content high-furnace gas desulfurization system and process |
| CN113813756A (en) * | 2021-10-20 | 2021-12-21 | 国家能源集团重庆恒泰发电有限公司 | Flue gas purification system of coal-fired unit |
| 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 |
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Application publication date: 20201103 |