CN111841296A - Desulfurizing agent for blast furnace gas and preparation method thereof - Google Patents
Desulfurizing agent for blast furnace gas and preparation method thereof Download PDFInfo
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- CN111841296A CN111841296A CN202010731667.4A CN202010731667A CN111841296A CN 111841296 A CN111841296 A CN 111841296A CN 202010731667 A CN202010731667 A CN 202010731667A CN 111841296 A CN111841296 A CN 111841296A
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- blast furnace
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- 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
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- 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
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- 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
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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
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a desulfurizer for blast furnace gas and a preparation method thereof, belonging to the technical field of atmospheric pollution treatment. The desulfurizer comprises blast furnace slag, steel slag, red mud of steel plants, red mud of aluminum plants, organic binders, pore-forming agents, peptizing agents and water. The method utilizes the solid waste of the iron and steel enterprises, adopts a simple preparation process, produces the desulfurizer with low price, high sulfur capacity and high desulfurization precision, reduces the cost of the prior blast furnace gas dry desulfurization, and solves the problem of solid waste discharge of the iron and steel enterprises.
Description
Technical Field
The invention relates to the technical field of air pollution treatment, in particular to a desulfurizer for blast furnace gas and a preparation method thereof.
Background
At present, the steel industry formally enters the 'ultra-low emission' era, and a blast furnaceThe users of hot blast stove, steel rolling heating furnace, gas power generation and the like require to burn the tail gas SO2The ultra-low emission limit is reached, and the prior blast furnace gas purification process can not meet the requirement of SO2And (5) controlling the requirements. With the increasing emphasis on environmental protection in China, the problem of overhigh content of sulfide in blast furnace gas is urgently solved.
The total sulfur content of blast furnace gas is 50-180mg/m3In between, the organic sulfur accounts for 75%, and COS is the main component. The blast furnace gas desulfurization usually adopts carbonyl sulfide hydrolysis series dry desulfurization process. Common dry desulfurization agents include activated carbon, zinc oxide, molecular sieves, and iron oxide. The active carbon desulfurizer is suitable for fine desulfurization of water gas and semi-water gas, water vapor and oxygen are needed during desulfurization, the sulfur capacity is about 20%, and the price of the active carbon desulfurizer is high. The zinc oxide desulfurizer is suitable for fine desulfurization of natural gas, oilfield associated gas and synthesis gas, the sulfur capacity is about 10% during normal-temperature desulfurization, and the desulfurizer is expensive. The molecular sieve total sulfur removing agent can absorb various organic sulfur and inorganic sulfur, the absorption capacity is 8-9 times of that of active carbon and 10-20 times of that of silica gel, but the price is high, and the water vapor in the raw material gas and the sulfide generate competitive absorption on the surface of the molecular sieve. The iron oxide desulfurizer is suitable for fine desulfurization of natural gas, oilfield associated gas, synthesis gas, water gas and semi-water gas, the sulfur capacity is about 20-50% during normal-temperature desulfurization, and the price of the desulfurizer is low. Iron oxide desulfurizer is mostly adopted to integrate desulfurization effect and economy.
Chinese patent CN98117729.8 'desulfurizing agent and preparation method thereof' provides Ca used in liquid and gaseous materials with large sulfur capacity and high desulfurizing precision2Fe2O5A method for preparing a desulfurizing agent which is an effective active component. The composite material is prepared by taking powder of ferric oxide, ferric hydroxide and ferric nitrate and powder of calcium oxide, calcium hydroxide, calcium bicarbonate and calcium carbonate as raw materials through the processes of mixing, extruding, forming, drying, roasting and the like. However, the raw materials used in the method are expensive, and the production cost of the desulfurizer is high; and the ferric nitrate can be decomposed to generate a large amount of nitrogen oxides during roasting, so that the environmental protection treatment pressure is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing a desulfurizer for blast furnace gas and a preparation method thereof.
The desulfurizer comprises blast furnace slag, steel slag, red mud of steel plants, red mud of aluminum plants, organic binder, pore-forming agent, peptizing agent and water, wherein the blast furnace slag, the steel slag, the red mud of steel plants, the red mud of aluminum plants, the organic binder and the pore-forming agent are dry materials, and the mass ratio of the blast furnace slag and the steel slag is 30-55%, the red mud of steel plants and the red mud of aluminum plants is 30-55%, the organic binder is 1-10%, the pore-forming agent is 1-5%, the peptizing agent is 0.5-5% of the total weight of the dry materials, and the water is 20-50% of the total weight of the dry materials.
Wherein the mass ratio of the blast furnace slag to the steel slag is 1: 0.25-4, wherein the mass ratio of the red mud in the steel plant to the red mud in the aluminum plant is 1: 0.25 to 4.
The organic binder is one or more of starch, sesbania powder and carboxymethyl cellulose.
The pore-forming agent is wood dust.
The peptizing agent is one or more of glacial acetic acid, oxalic acid and citric acid.
The preparation method of the desulfurizer comprises the following steps:
s1: sieving blast furnace slag, steel slag, red mud of steel plants and red mud of aluminum plants, and taking undersize products as raw materials of a desulfurizer;
s2: mixing blast furnace slag, steel slag, red mud of steel plants, red mud of aluminum plants, organic binder and pore-forming agent;
s3: adding a peptizing agent and water into the mixed material in the S2 for kneading;
s4: extruding and molding the kneaded material of S3;
s5: and drying and roasting the molded material S4 to obtain the desulfurizer with the active component being calcium ferrite.
Wherein the mesh number of the S1 sieve is 60 meshes; the mixing time of the materials in the S2 is 10-300 min; the kneading time of the materials in the S3 is 10-120 min; the drying temperature of the material in the S5 is 30-120 ℃, and the drying time is 1-12 h; the roasting condition of the material is 650-950 ℃ in an oxidizing atmosphere for 0.5-24 h.
The technical scheme of the invention has the following beneficial effects:
the raw materials of the invention are solid wastes, the produced desulfurizer has low price and high sulfur capacity, solves the problem of solid waste discharge of steel enterprises, reduces the cost of the prior blast furnace gas dry desulphurization, solves the problem of solid waste discharge of the steel enterprises, changes waste into valuable, has obvious economic benefit and environmental benefit, and meets the policy requirements of national circular economy.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved by the present invention clearer, the following detailed description is given with reference to specific embodiments.
The invention provides a desulfurizing agent for blast furnace gas and a preparation method thereof.
(1) Sieving blast furnace slag, steel slag, red mud of steel plants and red mud of aluminum plants, and taking undersize products as raw materials of a desulfurizer;
(2) mixing blast furnace slag and steel slag with red mud of a steel plant and red mud of an aluminum plant, an organic binder and a pore-forming agent, wherein the blast furnace slag and the steel slag account for 30-55 parts, the red mud of the steel plant and the red mud of the aluminum plant account for 30-55 parts, the organic binder is one or more of starch, sesbania powder and carboxymethyl cellulose, the organic binder accounts for 1-10 parts, the pore-forming agent is wood dust and the pore-forming agent accounts for 1-5 parts;
(3) adding water into the mixed material obtained in the step (2) for kneading, wherein the peptizing agent is one or more of glacial acetic acid, oxalic acid and citric acid, the adding amount of the peptizing agent is 0.5-5% of the weight of the dry material, and the adding amount of the water is 20-50% of the weight of the dry material;
(4) molding the kneaded material in the step (3);
(5) drying the formed material in the step (4) at 30-120 ℃ for 1-12h, and then roasting at 650-950 ℃ for 0.5-24h in an oxidizing atmosphere to obtain the active component calcium ferrite (Ca)2Fe2O5) The desulfurizing agent of (1).
In the specific application, the process is as follows:
1) 25 parts of blast furnace slag, 30 parts of steel slag, 10 parts of steel mill red mud, 30 parts of aluminum mill red mud, 3 parts of starch and 2 parts of wood dust are mixed for 30 min.
2) Adding glacial acetic acid accounting for 2% of the weight of the dry materials and water accounting for 30% of the weight of the dry materials into the mixed materials in the step 1) and kneading for 40 min;
3) extruding and molding the kneaded material in the step 2);
4) drying the formed material in the step 3) at 80 ℃ for 6 h, and then roasting the dried material at 800 ℃ for 6 h in an oxidizing atmosphere to obtain the calcium ferrite (Ca) serving as an active component2Fe2O5) The desulfurizing agent of (1).
The bulk density of the obtained calcium ferrite desulfurizer is 1.08 kg/L, the radial crushing strength is 128N/cm, and the penetrating sulfur capacity is 28 wt%.
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 desulfurizing agent for blast furnace gas is characterized in that: the red mud material comprises, by mass, 30-55% of blast furnace slag, 30-55% of steel mill red mud and aluminum mill red mud, 1-10% of organic binder, 1-5% of pore-forming agent, 0.5-5% of peptizing agent and 20-50% of water.
2. The desulfurizing agent for blast furnace gas according to claim 1, characterized in that: the mass ratio of the blast furnace slag to the steel slag is 1: 0.25-4, wherein the mass ratio of the red mud in the steel plant to the red mud in the aluminum plant is 1: 0.25 to 4.
3. The desulfurizing agent for blast furnace gas according to claim 1, characterized in that: the organic binder is one or more of starch, sesbania powder and carboxymethyl cellulose.
4. The desulfurizing agent for blast furnace gas according to claim 1, characterized in that: the pore-forming agent is wood dust.
5. The desulfurizing agent for blast furnace gas according to claim 1, characterized in that: the peptizing agent is one or more of glacial acetic acid, oxalic acid and citric acid.
6. The method for preparing the desulfurizing agent for blast furnace gas according to claim 1, characterized in that: the method comprises the following steps:
s1: sieving blast furnace slag, steel slag, red mud of steel plants and red mud of aluminum plants, and taking undersize products as raw materials of a desulfurizer;
s2: mixing blast furnace slag, steel slag, red mud of steel plants, red mud of aluminum plants, organic binder and pore-forming agent;
s3: adding a peptizing agent and water into the mixed material in the S2 for kneading;
s4: extruding and molding the kneaded material of S3;
s5: and drying and roasting the molded material S4 to obtain the desulfurizer with the active component being calcium ferrite.
7. The method for preparing a desulfurizing agent for blast furnace gas according to claim 6, characterized in that: the screen mesh number in the S1 is 60 meshes; the mixing time of the materials in the S2 is 10-300 min; the kneading time of the material in the S3 is 10-120 min.
8. The method for preparing a desulfurizing agent for blast furnace gas according to claim 6, characterized in that: the drying temperature of the material in the S5 is 30-120 ℃, and the drying time is 1-12 h; the roasting condition of the material is 650-950 ℃ in an oxidizing atmosphere for 0.5-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202010731667.4A CN111841296A (en) | 2020-07-27 | 2020-07-27 | Desulfurizing agent for blast furnace gas and preparation method thereof |
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| CN202010731667.4A CN111841296A (en) | 2020-07-27 | 2020-07-27 | Desulfurizing agent for blast furnace gas and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403254A (en) * | 2020-11-20 | 2021-02-26 | 中国铝业股份有限公司 | Method for preparing desulfurizer by using red mud as raw material and desulfurizer prepared by method |
| CN113908797A (en) * | 2021-10-28 | 2022-01-11 | 中冶南方都市环保工程技术股份有限公司 | Adsorbent for blast furnace gas desulfurization and heavy metal capture, preparation and application thereof |
| CN114231684A (en) * | 2021-12-23 | 2022-03-25 | 上海盛宝冶金科技有限公司 | High-efficiency molten iron pretreatment desulfurizer and preparation method thereof |
| CN115368940A (en) * | 2022-10-24 | 2022-11-22 | 北京中航天业科技有限公司 | Blast furnace gas deacidification agent based on superfine steel slag, preparation method and deacidification system |
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| CN1196971A (en) * | 1998-03-18 | 1998-10-28 | 北京三聚化工技术有限公司 | Sweetening agent and its prepn. method |
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| CN106866052A (en) * | 2017-02-07 | 2017-06-20 | 郑州大学 | A kind of red mud slag geo-polymer and preparation method thereof |
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2020
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Patent Citations (5)
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112403254A (en) * | 2020-11-20 | 2021-02-26 | 中国铝业股份有限公司 | Method for preparing desulfurizer by using red mud as raw material and desulfurizer prepared by method |
| CN112403254B (en) * | 2020-11-20 | 2022-09-27 | 中国铝业股份有限公司 | Method for preparing desulfurizer by using red mud as raw material and desulfurizer prepared by method |
| CN113908797A (en) * | 2021-10-28 | 2022-01-11 | 中冶南方都市环保工程技术股份有限公司 | Adsorbent for blast furnace gas desulfurization and heavy metal capture, preparation and application thereof |
| CN113908797B (en) * | 2021-10-28 | 2023-12-22 | 中冶南方都市环保工程技术股份有限公司 | Adsorbent for desulfurizing blast furnace gas and capturing heavy metals as well as preparation and application thereof |
| CN114231684A (en) * | 2021-12-23 | 2022-03-25 | 上海盛宝冶金科技有限公司 | High-efficiency molten iron pretreatment desulfurizer and preparation method thereof |
| CN115368940A (en) * | 2022-10-24 | 2022-11-22 | 北京中航天业科技有限公司 | Blast furnace gas deacidification agent based on superfine steel slag, preparation method and deacidification system |
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Application publication date: 20201030 |