CN113930264A - Improved organic sulfur desulfurizer and use method thereof for blast furnace gas desulfurization - Google Patents

Improved organic sulfur desulfurizer and use method thereof for blast furnace gas desulfurization Download PDF

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Publication number
CN113930264A
CN113930264A CN202111114858.7A CN202111114858A CN113930264A CN 113930264 A CN113930264 A CN 113930264A CN 202111114858 A CN202111114858 A CN 202111114858A CN 113930264 A CN113930264 A CN 113930264A
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blast furnace
oxide
furnace gas
desulfurizer
organic sulfur
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CN202111114858.7A
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田黎霞
何俊良
刘建英
徐成华
杨皓
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Chengdu University of Information Technology
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Chengdu University of Information 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
    • C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
    • C10K1/205—Methods and apparatus for treating the purifying masses without their regeneration
    • 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
    • B01D53/14—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 absorption
    • B01D53/1456—Removing acid components
    • B01D53/1468—Removing hydrogen sulfide
    • 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
    • B01D53/14—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 absorption
    • B01D53/1493—Selection of liquid materials for use as absorbents
    • 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
    • B01D53/26—Drying gases or vapours
    • 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
    • B01D53/50—Sulfur oxides
    • B01D53/508—Sulfur oxides by treating the gases with solids
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B01D53/82—Solid phase processes with stationary reactants
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/204—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/306—Alkali metal compounds of potassium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20738—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/30—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/808—Hydrolytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/304—Hydrogen sulfide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/308—Carbonoxysulfide COS

Abstract

The patent relates to an improved organic sulfur desulfurizer and a use method thereof for blast furnace gas desulfurization, belonging to the field of energy conservation and environmental protection. The desulfurizer adopts ferric oxide and silicon dioxide hydrogel raw materials to prepare a silicon-oxygen-iron framework structure, sodium oxide-potassium oxide with the molar ratio of 0.1-5% is loaded on the surface of the silicon-oxygen-iron framework, the desulfurizer is heated to 150-280 ℃, the desulfurizer is used as a reducing agent after being dehydrated by blast furnace gas, carbon monoxide reduces ferric oxide into ferrous oxide, the concentration of carbon monoxide at an inlet and an outlet in the blast furnace gas is basically unchanged, and activation is completed; the desulfurizing agent is cooled and used for organic sulfur conversion and absorption of blast furnace gas at 100-150 ℃, sodium oxide-potassium oxide is used as an organic sulfur hydrolysis conversion active center, and ferrous oxide is used as a hydrogen sulfide absorbent.

Description

Improved organic sulfur desulfurizer and use method thereof for blast furnace gas desulfurization
Technical Field
The invention relates to the field of energy conservation and environmental protection, and discloses a method for solving the problems that the existing desulfurizer is low in sulfur capacity, high in production cost and capable of discharging waste water and waste residues in the production process.
Background
The blast furnace gas is a byproduct containing CO and CO in the iron-making process of iron and steel enterprises2、N2、H2Of low calorific value combustible gas. Raw blast furnace gas also contains a large amount of dust and sulfides, which are mainly divided into organic sulfur and inorganic sulfur, and the organic sulfur accounts for a higher proportion than the inorganic sulfur. The main components of the organic sulfur comprise carbonyl sulfide, carbon disulfide, thioether mercaptan, thiophene and the like, and the carbonyl sulfide is taken as the main component; the inorganic sulfur mainly contains hydrogen sulfide, sulfur dioxide, etc. The emission of sulfur dioxide in flue gas of blast furnace gas after untreated combustion exceeds the standard. Therefore, the blast furnace gas needs to be purified to remove dust and sulfides carried in the gas before combustion and power generation.
In the existing blast furnace gas purification process, the dust removal link is a dry dust removal process which replaces the traditional wet process. In the aspect of sulfide removal, a wet scrubbing device is arranged behind a TRT device in the mature method at present. The method can effectively remove inorganic sulfur such as H in blast furnace gas2S，SO2，SO3But the organic sulfur in the blast furnace gas can not be removed, resulting in SO in the flue gas after combustion2The discharge is not up to standard, and the moisture carried by the wet desulphurization can enter subsequent pipeline equipment to cause corrosion. The removal of organic sulfur, especially COS, is an important link of blast furnace gas fine desulfurization, and the currently effective solution is to convert COS into H through catalytic hydrolysis2And removing the S.
CN111334341A of Maguangwei and the like of Shandong Zhongzhou blue environmental protection science and technology Limited company announces a desulfurization method of blast furnace gas, and mainly solves the technical problems that in the prior art, sulfide and dust in blast furnace gas purification cannot be completely removed, so that a gas pipeline is easy to corrode, and sulfur dioxide emission after the blast furnace gas is combusted exceeds the standard. The method comprises the following steps: a. blast furnace gas from a blast furnace enters a dry dedusting unit, and a material flow I is formed after dedusting; b. the material flow I enters an organic sulfur conversion device filled with a medium-temperature hydrolysis catalyst, the catalyst is a microcrystalline material catalyst, and the material flow I is subjected to catalytic conversion to form a material flow II; c. the material flow II enters a TRT power generation unit to generate power to form a material flow III; d. the material flow III enters a desulfurizing tower and forms a material flow IV after being absorbed by active carbon or an iron oxide fine desulfurizing agent; e. the material flow IV enters a subsequent blast furnace gas use workshop section, so that the problem is better solved, and the method can be used for industrial production of blast furnace gas purification. The method adopts medium-temperature hydrolysis for organic sulfur, and the hydrolysis agent is easy to inactivate, short in service life and high in price.
CN112940795A of Lixianwei et al, Hubei Huateler purification science and technology, Inc., Baoshan iron and Steel, Inc., announced an iron-based desulfurizer for blast furnace gas, wherein the desulfurizer comprises the following main raw materials: 30-50wt% of ferrous sulfate, 20-30wt% of calcium hydroxide, 10-40wt% of carbide slag, 5-15wt% of fly ash and 5-15wt% of sawdust. The solid reacts in the kneading and forming process to generate a desulfurizer precursor, and then the desulfurizer precursor is naturally oxidized into a finished desulfurizer product. The desulfurizer prepared by the method has high sulfur capacity, working sulfur capacity of 35-45wt%, saturated sulfur capacity of 60-70wt%, simple preparation process, no waste water and waste residue in the production process, low production cost and suitability for large-scale production. The process has no significant conversion to organic sulfur.
CN1102619648A of Jianellong, Fuzhou university, and the like, announces a copper-cobalt-based catalyst for organic sulfur hydrolysis removal and a preparation method thereof, wherein the copper-doped cobaltosic oxide catalyst is prepared by combining a hydrothermal auxiliary coprecipitation synthesis method with high-temperature roasting. The prepared copper-cobalt-based catalyst has high crystallinity, is nano-flaky, mainly takes mesopores, has high ion diffusion rate and has high catalytic hydrolysis performance on carbonyl sulfide. When the reaction temperature is 70 ℃, the conversion rate of COS reaches up to 100 percent, and the method is suitable for low-temperature catalytic hydrolysis desulfurization of carbonyl sulfide-containing gases such as blast furnace gas, natural gas and the like. The method adopts low-temperature hydrolysis for organic sulfur, and the working temperature of the hydrolysis agent is higher than 100 ℃, so that the method is easy to inactivate, short in service life and high in price.
At present, the desulfurization of blast furnace gas generally adopts organic sulfur hydrolytic agent to convert COS into H2S, then using a desulfurizing agent to react H2And (4) S absorption. Blast furnace gas de-H2S is usually activated carbon desulfurizer or ferric oxide desulfurizer. The biggest problems of the method are that the hydrolysis catalyst is high in manufacturing cost and is quickly deactivated because the hydrolysis catalyst is easy to block pores and deactivate. The original skeleton structure can not be regenerated and reused.
Disclosure of Invention
The improved organic sulfur desulfurizer is used in blast furnace gas desulfurization and is prepared with ferric oxide and silica hydrogel as material and through a Si-O-Fe skeleton structure. Loading sodium oxide-potassium oxide with a molar ratio of 0.1-5% on the surface of a silicon-oxygen-iron framework, heating a desulfurizer to 150-280 ℃ for dehydration, using the dehydrated blast furnace gas as a reducing agent, reducing iron oxide by carbon monoxide to obtain ferrous oxide until the concentration of carbon monoxide at an inlet and an outlet in the blast furnace gas is basically unchanged, and completing activation; cooling the desulfurizer, and using the cooled desulfurizer for conversion and absorption of organic sulfur in blast furnace gas at 100-150 ℃, wherein sodium oxide-potassium oxide is used as an organic sulfur hydrolysis conversion active center, and ferrous oxide is used as a hydrogen sulfide absorbent. The desulfurizer has the capabilities of hydrolysis conversion and hydrogen sulfide absorption, is low in cost, can be directly used for sintering the ferrosilicon pellets after being absorbed and saturated by the desulfurizer, is suitable for being used as a ferrosilicon pellet sintering raw material, is combined with calcium carbonate, potassium oxide and sodium to be solidified, and does not generate dangerous waste.
Detailed Description
Example 1:
the desulfurizer adopts ferric oxide and silicon dioxide hydrogel raw materials to prepare a silicon-oxygen-iron framework structure. Sodium oxide-potassium oxide with the molar ratio of 0.1% is loaded on the surface of the silicon-oxygen-iron framework, the desulfurizer is heated to 150 ℃, the desulfurizer is used as a reducing agent after being dehydrated by blast furnace gas, carbon monoxide reduces iron oxide into ferrous oxide until the concentration of carbon monoxide at an inlet and an outlet in the blast furnace gas is basically unchanged, and activation is completed; cooling the desulfurizing agent, and using the cooling agent for conversion and absorption of organic sulfur in blast furnace gas at 120 ℃, wherein sodium oxide-potassium oxide is used as an organic sulfur hydrolysis conversion active center, and ferrous oxide is used as a hydrogen sulfide absorbent.
Example 2:
the desulfurizer adopts ferric oxide and silicon dioxide hydrogel raw materials to prepare a silicon-oxygen-iron framework structure. Loading sodium oxide-potassium oxide with a molar ratio of 3% on the surface of a silicon-oxygen-iron framework, heating a desulfurizer to 200 ℃, using the dehydrated blast furnace gas as a reducing agent, reducing iron oxide into ferrous oxide by carbon monoxide until the concentration of carbon monoxide at an inlet and an outlet in the blast furnace gas is basically unchanged, and completing activation; cooling the desulfurizing agent, and using the cooling agent for conversion and absorption of organic sulfur in blast furnace gas at 120 ℃, wherein sodium oxide-potassium oxide is used as an organic sulfur hydrolysis conversion active center, and ferrous oxide is used as a hydrogen sulfide absorbent.
Example 3:
the desulfurizer adopts ferric oxide and silicon dioxide hydrogel raw materials to prepare a silicon-oxygen-iron framework structure. Loading sodium oxide-potassium oxide with a molar ratio of 5% on the surface of a silicon-oxygen-iron framework, heating a desulfurizer to 280 ℃, using the dehydrated blast furnace gas as a reducing agent, reducing iron oxide into ferrous oxide by carbon monoxide until the concentration of carbon monoxide at an inlet and an outlet in the blast furnace gas is basically unchanged, and completing activation; cooling the desulfurizing agent, and using the cooling agent for conversion and absorption of organic sulfur in blast furnace gas at 120 ℃, wherein sodium oxide-potassium oxide is used as an organic sulfur hydrolysis conversion active center, and ferrous oxide is used as a hydrogen sulfide absorbent.
The invention combines the current blast furnace gas desulfurization process flow in the steel industry to invent an improved organic sulfur desulfurizer, the desulfurizer has the capabilities of hydrolysis conversion and hydrogen sulfide absorption, the desulfurizer is cheap, can be directly used for sintering ferrosilicon pellets after being absorbed and saturated, and does not generate dangerous waste.

Claims (1)

1. An improved organic sulfur desulfurizer and a use method thereof for blast furnace gas desulfurization, wherein the desulfurizer adopts ferric oxide and silicon dioxide hydrogel raw materials to prepare a silicon-oxygen-iron framework structure, sodium oxide-potassium oxide with a molar ratio of 0.1-5% is loaded on the surface of the silicon-oxygen-iron framework, the desulfurizer is heated to 150-280 ℃, the desulfurizer is used as a reducing agent after being dehydrated by blast furnace gas, carbon monoxide reduces ferric oxide into ferrous oxide, and activation is completed until the concentration of carbon monoxide at an inlet and an outlet in the blast furnace gas is basically unchanged; the desulfurizing agent is cooled and used for organic sulfur conversion and absorption of blast furnace gas at 100-150 ℃, sodium oxide-potassium oxide is used as an organic sulfur hydrolysis conversion active center, and ferrous oxide is used as a hydrogen sulfide absorbent.
CN202111114858.7A 2021-09-23 2021-09-23 Improved organic sulfur desulfurizer and use method thereof for blast furnace gas desulfurization Pending CN113930264A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115738599A (en) * 2022-11-23 2023-03-07 攀钢集团攀枝花钢铁研究院有限公司 Simultaneous absorption of NO x And preparation method of CO complexing denitration liquid

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115738599A (en) * 2022-11-23 2023-03-07 攀钢集团攀枝花钢铁研究院有限公司 Simultaneous absorption of NO x And preparation method of CO complexing denitration liquid

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