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CN119015852A - Preparation and application of a high-activity and high-specific-surface-area iron oxyhydroxide desulfurizer - Google Patents

Preparation and application of a high-activity and high-specific-surface-area iron oxyhydroxide desulfurizer Download PDF

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CN119015852A
CN119015852A CN202411419412.9A CN202411419412A CN119015852A CN 119015852 A CN119015852 A CN 119015852A CN 202411419412 A CN202411419412 A CN 202411419412A CN 119015852 A CN119015852 A CN 119015852A
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iron oxyhydroxide
iron
desulfurizer
desulfurizing agent
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凌绍文
苏春花
刘健
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Yueyang Haida Environmental Protection Technology Co ltd
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Yueyang Haida Environmental Protection Technology Co ltd
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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
    • 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
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/52—Hydrogen sulfide
    • 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
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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
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • 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
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8612—Hydrogen sulfide
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract

本发明提供一种高活性高比表面积羟基氧化铁脱硫剂的制备和应用，所述脱硫剂制备方法步骤如下：S1：取全铁、水合氧化铁、羟基氧化铁、载体材料、钙试剂、造孔剂和氧化铝于容器中研磨均匀后添加溶剂，进行成型处理；S2：对S1所得粘状混合物进行加热、加压、通入活化气体处理，得反应物；S3：将S2反应物冷却至室温后，经压制、焙烧后冷却，得到羟基氧化铁脱硫剂。本发明不仅能保持脱硫剂的高硫容，且确保了脱硫过程的高效率和有效型，适合各种无氧或低氧环境的气体精脱硫处理，特殊设计的微孔结构增强了材料的吸附效率，延长了使用寿命等。

The present invention provides a preparation and application of a high-activity and high-specific surface area iron oxyhydroxide desulfurizer, and the steps of the preparation method of the desulfurizer are as follows: S1: take all iron, hydrated iron oxide, iron oxyhydroxide, carrier material, calcium reagent, pore-forming agent and aluminum oxide in a container, grind them evenly, add solvent, and perform molding treatment; S2: heat, pressurize, and introduce activated gas into the viscous mixture obtained by S1 to obtain a reactant; S3: cool the S2 reactant to room temperature, pressurize, roast, and then cool to obtain the iron oxyhydroxide desulfurizer. The present invention can not only maintain the high sulfur capacity of the desulfurizer, but also ensure the high efficiency and effectiveness of the desulfurization process, and is suitable for various gas fine desulfurization treatments in anaerobic or low-oxygen environments. The specially designed microporous structure enhances the adsorption efficiency of the material and prolongs the service life.

Description

Preparation and application of high-activity high-specific-surface-area iron oxyhydroxide desulfurizing agent
Technical Field
The invention relates to the technical field of flue gas desulfurization, in particular to preparation and application of a high-activity high-specific-surface-area iron oxyhydroxide desulfurizing agent.
Background
Iron oxyhydroxide (FeOOH) is a material with unique crystal structure and physicochemical properties and is widely used in desulfurization processes. In the desulfurization process, the iron oxyhydroxide and sulfide react to generate an easily-processed solid product, so that the hydrogen sulfide is effectively removed. In addition, the preparation method of the iron oxyhydroxide comprises the steps of mixing Fe2+ salt solution with alkali solution, and reacting under the action of oxygen-containing gas to finally obtain the iron oxyhydroxide.
The iron oxyhydroxide is used as a desulfurizing agent, the main component of the iron oxyhydroxide is FeOOH, and the iron oxyhydroxide can react with sulfides in the desulfurizing process to generate a solid product which is easy to process, so that the hydrogen sulfide is effectively removed. The method is not only efficient, but also low in cost and pollution, and is an ideal hydrogen sulfide treatment method. For example, prior patent CN101584962a discloses a high strength iron oxyhydroxide desulfurizer consisting of 50-95 wt% amorphous iron oxyhydroxide FeOOH, 0-45 wt% carrier, 5-50 wt% organic binder; wherein the carrier is one or more of aluminum oxide, diatomite, natural zeolite and catalytic cracking waste catalyst; the organic binder is one or more of methyl cellulose sodium salt, sesbania powder and cellulose powder. CN101585556a relates to a process for the preparation of amorphous iron oxyhydroxide, comprising the steps of: (a) Mixing solid soluble ferrous salt and solid hydroxide according to the mole ratio of iron to hydroxide of 1:2-1:3; (b) The mixed material obtained in the step (a) is subjected to kneading to complete the reaction, and the temperature of the material is controlled to be not more than 70 ℃ in the kneading process; (c) Airing the reaction product obtained in the step (b) in air; (d) washing the material obtained in the step (c) with water and filtering; (e) And (3) naturally drying or oven drying the solid obtained in the step (d). CN103182236a relates to a high-strength water-resistant high-sulfur-capacity desulfurizing agent, which is prepared from the following raw materials in parts by weight: 90-98 parts of iron oxyhydroxide; 2-4 parts of sodium carboxymethyl cellulose or sodium hydroxypropyl methyl cellulose; starch 0.2-2 parts. The above-described technique still has disadvantages in preparing a desulfurizing agent having a high sulfur capacity and a microporous structure.
Therefore, preparing a desulfurizing agent with a high sulfur capacity and a microporous structure, ensuring high efficiency and effectiveness in the desulfurization process remains a challenge, and problems such as how to further improve the adsorption efficiency of the material and prolong the service life are all urgently needed to be solved.
Disclosure of Invention
In order to achieve the aim of the invention, the invention provides the preparation and the application of the high-activity high-specific-surface-area iron oxyhydroxide desulfurizer, which not only can keep the high sulfur capacity of the desulfurizer, but also ensures the high efficiency and the effectiveness of the desulfurization process, is suitable for the gas fine desulfurization treatment in various anaerobic or low-oxygen environments, and has simple operation in the whole process, the adsorption efficiency of materials is enhanced by the specially designed micropore structure, the service life is prolonged, and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
On one hand, the invention provides a high-activity high-specific surface area iron oxyhydroxide desulfurizer which is prepared from the following components: whole iron, hydrated iron oxide, iron oxyhydroxide, a carrier material, a calcium reagent, a pore-forming agent, and alumina.
Further, the iron oxyhydroxide desulfurizer is prepared from the following components in parts by weight: 20-40 parts of total iron, 30-60 parts of hydrated ferric oxide, 30-60 parts of hydroxyl ferric oxide, 10-40 parts of carrier material, 1-10 parts of calcium reagent, 0.1-5 parts of pore-forming agent and 1-10 parts of alumina.
Further, the iron oxyhydroxide desulfurizer is prepared from the following components in parts by weight: 30 parts of total iron, 50 parts of hydrated ferric oxide, 60 parts of hydroxyl ferric oxide, 10 parts of carrier material, 4.5 parts of calcium reagent, 1.5 parts of pore-forming agent and 4 parts of alumina.
Further, the hydrous iron oxide exists in a variety of forms in the desulfurizing agent, including at least one of α-Fe2O3、α-Fe2O3·H2O、β-Fe2O3、β-Fe2O3·H2O、γ-Fe2O3、γ-Fe2O3·H2O and amorphous Fe 2O3.
Further, the particle size number of the iron oxyhydroxide is 20-40 mesh.
Further, the carrier material comprises at least one of diatomite carrier, activated carbon and kaolin.
Further, the calcium reagent comprises one or more of quicklime, slaked lime, calcium oxide and calcium chloride.
Further, the pore-forming agent comprises one of starch, corn starch, sucrose, lactose, sodium carbonate and sodium bicarbonate.
On the one hand, the invention provides a preparation method of a high-activity high-specific surface area iron oxyhydroxide desulfurizer, which comprises the following specific steps:
S1: taking total iron, hydrated ferric oxide, hydroxyl ferric oxide, a carrier material, a calcium reagent, a pore-forming agent and aluminum oxide according to the weight ratio, uniformly grinding in a container, adding a solvent, preparing into a viscous mixture, and performing molding treatment;
s2: heating and pressurizing the viscous mixture obtained in the step S1, and introducing activating gas into the reactant under stirring to obtain an activated reactant;
s3: and cooling the activated reactant to room temperature, pressing into particles or blocks, roasting, and cooling to obtain the iron oxyhydroxide desulfurizer.
Further, putting all the components in the step S1 into a mortar for uniform mixing, then putting into a ball mill, setting the ball milling rotating speed to be 100-400r/min, grinding for 2-6h, taking out for standby, putting the ground powder into a 200-mesh sieve for sieving, and obtaining the powder with the granularity of 100-200 meshes after ball milling.
Further, the solvent is one or more of water, ethanol, methanol and ethanol water solution.
Further, the molding treatment means that the sticky mixture enters a plodder for strip extrusion molding, and the strip extrusion pressure of the plodder is more than or equal to 15MPa. Further, the extruded strip is one of a cylinder, a Raschig ring and a special-shaped strip, and the diameter of the extruded strip is 1-5 mm.
Further, the heating and pressurizing treatment process is as follows: heating the obtained viscous mixture to 300 ℃ within 5-10 min, and keeping the temperature at 10MPa for 20-30 min; heating to 400-600 ℃ within 5-10 min, and keeping the temperature for 20-100 min under 10 MPa.
Further, the activating gas is introduced at a speed of 1-5 m 3/h for 10-60min, and heating treatment is kept in the introduction process. The activated gas enters the carrier through the pore channel to react, so that the carrier with large pore volume, large specific surface and strong adsorption capacity can be obtained while the activation time is shortened.
Further, the activating gas is one of hydrogen, ammonia and carbon monoxide.
Further, the pressure during the pressing of the granules or blocks is maintained between 15MPa and 180MPa.
Further, the roasting is performed under an inert atmosphere, wherein the inert atmosphere is one of nitrogen, helium, neon and argon; the roasting process is that the roasting is carried out for 2-8 hours at 450-500 ℃, 3-5 hours at 550-650 ℃, 2-4 hours at 250-350 ℃, and 1-4 hours at 50-100 ℃.
On one hand, the invention provides an application of a high-activity high-specific surface area iron oxyhydroxide desulfurizer, which comprises the following specific processes:
The sulfur-containing gas is passed through a reactor filled with a high-activity high-specific surface area iron oxyhydroxide desulfurizing agent, the reaction temperature of normal pressure and 30 ℃ is set, and the sulfur content of the outlet gas is measured by a microsulfide analyzer, so that the penetrating sulfur capacity is ensured to reach 16.
The invention has the beneficial effects that:
The invention adopts different types of iron preparations, ensures high efficiency, high activity and stability in the desulfurization process, optimizes desulfurization reaction and improves the overall performance of the desulfurizing agent.
In the preparation process of the desulfurizer, activated gas enters the carrier through the pore canal to react, so that the high-activity high-specific-surface-area iron oxyhydroxide desulfurizer with large pore volume, large specific surface and strong adsorption capacity can be obtained while the activation time is shortened.
Through the roasting process, the particles or the blocks form rich pore channels, and simultaneously the materials are carbonized and contracted, so that the components are firmly and tightly combined together, the desulfurizing agent has higher strength, and the performance of iron metal can be exerted in the catalysis process;
The desulfurizer with high strength prepared by the invention is not easy to generate broken and pulverized in the filling and using process, does not increase the resistance of a bed layer, and does not cause bias flow of gas in the application process.
The desulfurizing agent prepared by the invention has enough water resistance through heating, pressurizing treatment, activating treatment and roasting treatment. The waste water vapor content in the application process of the desulfurizing agent prepared by the invention is relatively large, and the conditions of hardening, bias flow and the like of the desulfurizing agent are avoided.
Under the anoxic environment, the high-activity high-specific surface area iron oxyhydroxide desulfurizer (HD-3 desulfurizer) prepared by the invention can still maintain high sulfur capacity, ensures high efficiency and effectiveness of the desulfurization process, and is suitable for gas fine desulfurization treatment in various anaerobic or low-oxygen environments; in the preparation process, the oxygen supplementing operation is omitted, the whole desulfurization process flow is simplified, the operation complexity and the investment cost are reduced, and the safety and the reliability of the system are improved; by adopting the active ferric oxide with different forms, the high efficiency and stability of the desulfurization process are ensured, the desulfurization reaction is optimized, and the overall performance of the desulfurizing agent is improved; by introducing the activated gas, the specially designed microporous structure enhances the adsorption efficiency of the material, prolongs the service life and improves the economical efficiency and the overall desulfurization efficiency of the desulfurizing agent.
Drawings
FIG. 1 is a schematic diagram of a desulfurizing agent prepared in example 1;
FIG. 2 is an electron microscopic view of the desulfurizing agent of example 1.
Detailed Description
The invention will be further illustrated with reference to specific examples. These examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1
The high-activity high-specific-surface-area iron oxyhydroxide desulfurizer is prepared from the following components in parts by weight: 30 parts of total iron, 50 parts of hydrated ferric oxide, 60 parts of hydroxyl ferric oxide, 10 parts of carrier material, 4.5 parts of calcium reagent, 1.5 parts of pore-forming agent and 4 parts of alumina.
Wherein the hydrated iron oxide exists in a variety of forms in the desulfurizing agent, including α-Fe2O3、α-Fe2O3·H2O、β-Fe2O3、β-Fe2O3·H2O、γ-Fe2O3、γ-Fe2O3·H2O and amorphous Fe 2O3.
The granularity mesh number of the iron oxyhydroxide is 30 meshes;
the carrier material comprises diatomite carrier and kaolin;
The calcium reagent comprises calcium oxide;
The pore-forming agent comprises starch.
The preparation method of the high-activity high-specific-surface-area iron oxyhydroxide desulfurizer comprises the following specific steps:
S1: taking total iron, hydrated ferric oxide, ferric hydroxide, carrier material, a calcium reagent, a pore-forming agent and alumina according to the weight ratio, putting the mixture into a mortar for uniform mixing, then putting the mortar into a ball mill, setting the ball mill rotation speed to 300r/min, grinding for 4 hours, taking out for standby, putting the ground powder into a 200-mesh sieve for sieving to obtain powder with the granularity of 100-200 meshes after ball milling, adding solvent water, preparing into a sticky mixture, and carrying out molding treatment; feeding the sticky mixture into a plodder, and extruding strips to form, wherein the extruding pressure of the plodder is more than or equal to 15MPa; the extruded strip is cylindrical and has a diameter of 1-1.5 mm;
S2: heating the viscous mixture obtained in the step S1 to 300 ℃ within 10min, and keeping the viscous mixture for 30min under the pressure of 10 MPa; heating to 600 ℃ within 5min, maintaining for 80min under the pressure of 10MPa, introducing activated gas hydrogen into the reactant under stirring, and introducing activated gas at the speed of 2.5m 3/h for 60min to obtain an activated reactant; maintaining the heating treatment of the obtained viscous mixture in the feeding process;
S3: cooling the activated reactant to room temperature, pressing the reactant into particles or blocks under the pressure of 100MPa, roasting the particles or blocks in an inert atmosphere, and cooling the roasted particles or blocks to obtain the iron oxyhydroxide desulfurizer; the roasting process is that the material is roasted for 5 hours at 500 ℃,3 hours at 550 ℃,2 hours at 300 ℃, and 4 hours at 100 ℃.
Example 2
The high-activity high-specific-surface-area iron oxyhydroxide desulfurizer is prepared from the following components in parts by weight: 40 parts of total iron, 30 parts of hydrated ferric oxide, 30 parts of hydroxyl ferric oxide, 10 parts of carrier material, 1 part of calcium reagent, 0.1 part of pore-forming agent and 1 part of alumina.
The hydrous iron oxide exists in a variety of forms in the desulfurizing agent, including α -Fe 2O3·H2O、γ-Fe2O3·H2 O and amorphous Fe 2O3.
The granularity mesh number of the iron oxyhydroxide is 40 meshes. The carrier material comprises active carbon and kaolin. The calcium reagent comprises quicklime. The pore-forming agent comprises sodium bicarbonate.
The preparation method of the high-activity high-specific-surface-area iron oxyhydroxide desulfurizer comprises the following specific steps:
S1: taking total iron, hydrated ferric oxide, ferric hydroxide, carrier material, a calcium reagent, a pore-forming agent and alumina according to the weight ratio, putting the materials into a mortar for uniform mixing, then putting the mortar into a ball mill, setting the ball mill rotation speed to 10000r/min, grinding for 2 hours, taking out for standby, putting the ground powder into a 200-mesh sieve for sieving to obtain powder with the granularity of 100-200 meshes after ball milling, adding a solvent of 25% ethanol aqueous solution, and preparing into a viscous mixture; feeding the sticky mixture into a plodder, and extruding strips to form, wherein the extruding pressure of the plodder is more than or equal to 15MPa; the extruded strip is shaped like a special-shaped strip with the diameter of 5mm;
S2: heating the viscous mixture obtained in the step S1 to 300 ℃ within 5min, and keeping the viscous mixture for 30min under the pressure of 10 MPa; heating to 600 ℃ within 5min, maintaining for 20min under 10MPa, heating and pressurizing, and introducing activating gas into the reactant under stirring to obtain an activated reactant; the activating gas is introduced at a speed of 5m 3/h for 10min, and heating treatment is kept during the introduction. The activating gas is ammonia gas.
S3: and cooling the activated reactant to room temperature, pressing the reactant into particles or blocks under the pressure of 80MPa, roasting the particles or blocks in an inert atmosphere, and cooling the roasted particles or blocks to obtain the iron oxyhydroxide desulfurizer. The roasting process is that the material is roasted for 4 hours at 450 ℃,3 hours at 550 ℃,4 hours at 250 ℃ and 4 hours at 50 ℃.
Example 3
The high-activity high-specific-surface-area iron oxyhydroxide desulfurizer is prepared from the following components in parts by weight: 40 parts of total iron, 60 parts of hydrated iron oxide, 60 parts of hydroxyl iron oxide, 10 parts of carrier material, 10 parts of calcium reagent, 5 parts of pore-forming agent and 10 parts of alumina.
The hydrous iron oxide exists in a variety of forms in the desulfurizing agent, including α -Fe 2O3、β-Fe2O3·H2 O, and amorphous Fe 2O3.
The granularity mesh number of the iron oxyhydroxide is 30 meshes. The support material comprises kaolin. The calcium reagent comprises slaked lime. The pore-forming agent comprises lactose.
The preparation method of the high-activity high-specific-surface-area iron oxyhydroxide desulfurizer comprises the following specific steps:
s1: taking total iron, hydrated iron oxide, ferric hydroxide, carrier material, a calcium reagent, a pore-forming agent and alumina according to the weight ratio, putting the mixture into a mortar for uniform mixing, then putting the mortar into a ball mill, setting the ball mill rotation speed to be 200r/min, grinding for 3 hours, taking out for standby, putting the ground powder into a 200-mesh sieve for sieving to obtain powder with the granularity of 100 meshes after ball milling, adding solvent water, preparing into a sticky mixture, and carrying out molding treatment; the sticky mixture enters a plodder for strip extrusion molding, the strip extrusion pressure of the plodder is more than or equal to 15MPa, the strip extrusion shape is a special-shaped strip, and the diameter is 5mm.
S2: heating the viscous mixture obtained in the step S1 to 300 ℃ within 10min, and keeping the viscous mixture for 20min under the pressure of 10 MPa; heating to 500 ℃ within 5min, maintaining for 50min under the pressure of 10MPa, heating and pressurizing, and introducing activating gas into the reactant under stirring to obtain an activated reactant; the activating gas is introduced at a speed of 3m 3/h for 30min, and heating treatment is kept during the introduction. The activating gas is carbon monoxide.
S3: and cooling the activated reactant to room temperature, pressing the reactant into particles or blocks under the pressure of 80MPa, roasting the particles or blocks in an inert atmosphere, and cooling the roasted particles or blocks to obtain the iron oxyhydroxide desulfurizer. The roasting process is that the material is roasted for 2 hours at 450 ℃,3 hours at 550 ℃,4 hours at 250 ℃ and 4 hours at 50 ℃.
The properties of the desulfurizing agent prepared in example 3 of the present invention are shown in Table 1 below:
performance test 1
Measuring a certain volume of desulfurizing agent by using a measuring cylinder detection method, and detecting the bulk density of the embodiment of the application;
detecting the porosity of the desulfurizing agent by a mercury replacement method;
the structural morphology distribution in the desulfurizing agent is shown in Table 2 below
Examples Specific surface area m 2/g Kg/L ％
1 67 0.63 46
2 65 0.60 40
3 70 0.65 50
As can be seen from the data in Table 2, the desulfurizing agent prepared by the application has a specially designed micropore structure and high specific surface area, and is suitable for gas fine desulfurization treatment in various anaerobic or hypoxia environments.
Performance test 2
And (3) water resistance test:
The desulfurizing agent ① prepared by the embodiment of the application is statically soaked in water for 96 hours, and no pulverization occurs; ② The desulfurizing agent prepared by the embodiment of the application has better water resistance as the desulfurizing agent is soaked in dynamic boiling water for 24 hours and is not atomized.
Performance test 3
Determination of active iron content in iron oxyhydroxide desulfurizing agent by chemical quantitative analysis method
The method is characterized in that: the active iron oxide is easily reacted with weak acid-acetic acid and separated from other iron oxides, and for this purpose, the sample is azeotropically refluxed with glacial acetic acid, and the active iron surface is extracted from the sample of the dry desulfurizing agent to obtain a solution of iron acetate. Expressed by the equation:
Fe2O3+6CH3COOH＝2Fe(OH2COO)3+3H2O
then neutralizing the excess acetic acid with concentrated aqueous ammonia and bringing the pH of the solution to l0-12 with excess concentrated aqueous ammonia, whereupon a reddish brown amorphous ferric hydroxide precipitate precipitates:
NH3+H2O＝NH4OH
CH3COOH+NH4OH＝CH3COONH4+H2O
Fe(OHCOO)3+3NH4OH＝Fe(OH)3+3CH3COONH4
The chemical heat released by the vigorous neutralization reaction increases the temperature of the solution. The solution containing the precipitate was allowed to cool naturally to room temperature and allowed to stand for 8 hours to allow the precipitate to age. Then adding a plurality of drops of strong ammonia water into the clarified solution, confirming that the precipitation is finished, filtering by using quantitative filter paper and adopting a dip-stripping method, washing the precipitate by using dilute ammonia water, drying and ashing the precipitate and the filter paper in a quantitative crucible with constant weight, and burning the precipitate into ferric oxide:
2Fe(OH)3＝＝＝Fe2O3+3H2O
and cooling the crucible and the burning residues thereof to constant weight, thus measuring the content of active iron in the desulfurizing agent and calculating the content percentage of ferric oxide.
The results are shown in Table 3 below
Examples Sample name Inspection item Unit (B) Test results
1 Iron oxyhydroxide Active iron content ％ 76
2 Iron oxyhydroxide Active iron content ％ 75.3
3 Iron oxyhydroxide Active iron content ％ 77.2
Through a crystalline phase X-ray diffraction test and a thermomagnetic study, the structural forms of alpha-Fe 2O3·H2 O and gamma-Fe 2O3·H2 O in the desulfurizing agent prepared by the invention are more than 95 percent in total. The desulfurizing agent prepared in example 3 was characterized by a crystalline phase X-ray diffraction pattern, having 2θ diffraction peaks at positions of 35.3 °, 41.6 °, 50.7 °, 63.3 °, 67.6 °, 74.6 °, and aligned to the diffraction peak positions of standard γ -Fe 2O3·H2 O.
The content of active iron measured by Lei Moen special method is up to above 70%. Is ferric oxide with the best chemical reaction performance for removing hydrogen sulfide, has good thermal stability, and is an excellent raw material for the industrial gas dry desulfurization process.
Evaluation example of Activity
The desulfurizing agents prepared in examples 1 to 3 were evaluated at normal temperature (ambient temperature, usually-5℃to 45 ℃) and normal pressure (ambient pressure, usually 1 atm) by taking 5g of each of the desulfurizing agents prepared in examples 1 to 3, and using a standard gas containing H 2 S of 40000 ppm. Wherein, the qualitative detection can be carried out by self-preparing 1% silver nitrate solution to detect the outlet sulfur; quantitative detection can be carried out by adopting a domestic comprehensive microcoulomb instrument, and the minimum detection amount of the instrument is 0.2ppm. The mechanical strength of the desulfurizing agent prepared in the above example was measured by evaluating the measured pressure thereof, wherein the average radial crushing resistance of the pellets was measured according to HG/T2782. The detection results are shown in the following table 4.
Examples 1 2 3
Sulfur capacity (%) 66 59 60
Intensity (N/CM) 199 187 200
As can be seen from the test results, the sulfur capacity of the iron oxyhydroxide desulfurizer prepared by the invention can reach 66% at normal temperature and normal pressure, and the pressure measurement and fixation end can reach 200N/cm.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (8)

1. The high-activity high-specific-surface-area iron oxyhydroxide desulfurizer is characterized by being prepared from the following components in parts by weight: 20-40 parts of total iron, 30-60 parts of hydrated ferric oxide, 30-60 parts of hydroxyl ferric oxide, 10-40 parts of carrier material, 1-10 parts of calcium reagent, 0.1-5 parts of pore-forming agent and 1-10 parts of alumina;
The specific preparation steps of the desulfurizing agent are as follows:
S1: taking total iron, hydrated ferric oxide, hydroxyl ferric oxide, a carrier material, a calcium reagent, a pore-forming agent and aluminum oxide according to the weight ratio, uniformly grinding in a container, adding a solvent, preparing into a viscous mixture, and performing molding treatment;
s2: heating and pressurizing the viscous mixture obtained in the step S1, and introducing activating gas into the reactant under stirring to obtain an activated reactant;
S3: cooling the activated reactant to room temperature, pressing into particles or blocks, roasting, and cooling to obtain a ferric hydroxide desulfurizing agent;
The heating and pressurizing treatment process comprises the following steps: heating the obtained viscous mixture to 300 ℃ within 5-10 min, and keeping the temperature at 10MPa for 20-30 min; heating to 400-600 ℃ within 5-10 min, and keeping the temperature for 20-100 min under 10 MPa;
The roasting process is that the roasting is carried out for 2-8 hours at 450-500 ℃, 3-5 hours at 550-650 ℃, 2-4 hours at 250-350 ℃, and 1-4 hours at 50-100 ℃.
2. The iron oxyhydroxide desulfurizer according to claim 1, characterized by being prepared from the following components in parts by weight: 30 parts of total iron, 50 parts of hydrated ferric oxide, 60 parts of hydroxyl ferric oxide, 10 parts of carrier material, 4.5 parts of calcium reagent, 1.5 parts of pore-forming agent and 4 parts of alumina.
3. The iron oxyhydroxide desulfurizing agent according to claim 1, characterized in that,
The hydrated iron oxide exists in a plurality of forms in the desulfurizing agent, including at least one of α-Fe2O3、α-Fe2O3·H2O、β-Fe2O3、β-Fe2O3·H2O、γ-Fe2O3、γ-Fe2O3·H2O and amorphous Fe 2O3;
the granularity mesh number of the iron oxyhydroxide is 20-40 meshes;
The carrier material comprises at least one of diatomite carrier, activated carbon and kaolin;
The calcium reagent comprises one or more of quicklime, slaked lime, calcium oxide and calcium chloride;
The pore-forming agent comprises one of starch, corn starch, sucrose, lactose and sodium carbonate.
4. The iron oxyhydroxide desulfurizer according to claim 1, characterized in that all components in S1 are put into a mortar for uniform mixing, then are put into a ball mill, the ball milling rotation speed is set to be 100-400r/min, are taken out for standby after grinding for 2-6h, and are put into a 200-mesh sieve for sieving, so as to obtain powder with 100-200-mesh ball milling;
The solvent is one or more of water, ethanol, methanol and ethanol water solution.
5. The iron oxyhydroxide desulfurizer according to claim 1, characterized in that the molding treatment means that the viscous mixture enters a plodder and is extruded to form strips, the extruding pressure of the plodder is more than or equal to 15MPa, the extruding shape is one of a cylinder, a Raschig ring and a special-shaped strip, and the diameter is 1-5 mm.
6. The iron oxyhydroxide desulfurizer according to claim 1, characterized in that the activating gas is introduced at a rate of 1-5 m 3/h for 10-60min, and heat treatment is maintained during the introduction;
the activating gas is one of hydrogen, ammonia and carbon monoxide;
the pressure in the pressing process of the granules or the blocks is kept between 15MPa and 180MPa.
7. The iron oxyhydroxide desulfurizer according to claim 1, wherein the calcination is performed under an inert atmosphere, the inert atmosphere being one of nitrogen, helium, neon, and argon.
8. The use of the high activity high specific surface area iron oxyhydroxide desulfurizing agent of claim 1, comprising the following steps:
The sulfur-containing gas is passed through a reactor filled with a high-activity high-specific surface area iron oxyhydroxide desulfurizing agent, the reaction temperature of normal pressure and 30 ℃ is set, and the sulfur content of the outlet gas is measured by a microsulfide analyzer, so that the penetrating sulfur capacity is ensured.
CN202411419412.9A 2024-10-12 2024-10-12 Preparation and application of a high-activity and high-specific-surface-area iron oxyhydroxide desulfurizer Pending CN119015852A (en)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5334564A (en) * 1990-07-16 1994-08-02 Board Of Trustees Operating Michigan State University Method for the preparation of highly reactive clay composites for the removal of SOx from flue gas streams
US20090028770A1 (en) * 2005-02-16 2009-01-29 Japan Science And Technology Agency Method for producing iron oxyhydroxide and adsorbing material comprising iron oxyhydroxide
US20100210449A1 (en) * 2006-08-28 2010-08-19 Bejing Sanju Environmental Protection and New Material Co., Ltd. Composition of amorphous iron oxide hydroxide, desulfurizer comprising the same, and methods for preparing and regenerating the desulfurizer
US20110256039A1 (en) * 2008-12-30 2011-10-20 Beijing Sanju Environmental Protection and New Material Co., Ltd. Method for regenerating amorphous iron oxide hydroxide and desulfurizer containing amorphous iron oxide hydroxide as active component
US20130004394A1 (en) * 2011-05-11 2013-01-03 Maohong Fan Catalytic CO2 Desorption on the Interface between NaHCO3 and Multifunctional Nanoporous TiO(OH)2
CN105582791A (en) * 2014-10-21 2016-05-18 青岛百键城环保科技有限公司 Desulfurizer making method
CN118356790A (en) * 2024-05-10 2024-07-19 山东海嘉石油化工有限公司 Iron oxyhydroxide desulfurizing agent and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5334564A (en) * 1990-07-16 1994-08-02 Board Of Trustees Operating Michigan State University Method for the preparation of highly reactive clay composites for the removal of SOx from flue gas streams
US20090028770A1 (en) * 2005-02-16 2009-01-29 Japan Science And Technology Agency Method for producing iron oxyhydroxide and adsorbing material comprising iron oxyhydroxide
US20100210449A1 (en) * 2006-08-28 2010-08-19 Bejing Sanju Environmental Protection and New Material Co., Ltd. Composition of amorphous iron oxide hydroxide, desulfurizer comprising the same, and methods for preparing and regenerating the desulfurizer
US20110256039A1 (en) * 2008-12-30 2011-10-20 Beijing Sanju Environmental Protection and New Material Co., Ltd. Method for regenerating amorphous iron oxide hydroxide and desulfurizer containing amorphous iron oxide hydroxide as active component
US20130004394A1 (en) * 2011-05-11 2013-01-03 Maohong Fan Catalytic CO2 Desorption on the Interface between NaHCO3 and Multifunctional Nanoporous TiO(OH)2
CN105582791A (en) * 2014-10-21 2016-05-18 青岛百键城环保科技有限公司 Desulfurizer making method
CN118356790A (en) * 2024-05-10 2024-07-19 山东海嘉石油化工有限公司 Iron oxyhydroxide desulfurizing agent and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
何则晃等编著: "《录像机与电视产品》", 31 October 1987, 科学技术文献出版社, pages: 23 *
刘武军著: "《生物质废弃物污染控制与清洁转化》", 31 March 2022, 中国科学技术大学出版社, pages: 188 *
吴国光等主编: "《煤炭气化工艺学》", 31 October 2015, 中国矿业大学出版社, pages: 241 *
陈志和主编: "《电厂化学设备及系统》", 31 March 2006, 中国电力出版社, pages: 269 *

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