CN111116224A - Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof - Google Patents
Desulfurizer using red mud waste residue as active raw material, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a desulfurizer taking red mud waste residue as an active raw material and a preparation method and application thereof. The porous ceramic-based desulfurizer with green high sulfur capacity and low cost is prepared from red mud waste residues, walnut shell powder, straw fibers, zinc oxide powder and a forming agent solution by the processes of crushing, proportioning, granulating, forming, calcining and the like. The desulfurizer of the invention can realize resource utilization of red mud, walnut shells and straw fiber, and thoroughly solve heavy gold in red mud waste residuesIs polluted and absorbs and removes low-concentration H2The S has high precision, high efficiency, wide application range and wide market application prospect.
Description
Technical Field
The invention provides a porous ceramic-based desulfurizer taking red mud waste residues as active raw materials and a preparation method thereof, belonging to the field of waste product resource utilization and new environmental materials.
Background
China, as the first major alumina producing country in the world, discharges up to billions of tons of red mud every year. The open-air stacking of the red mud is taken as a main disposal mode of the current alumina production enterprises, the disposal cost of the red mud accounts for about 5 percent of the production value of alumina products, and the red mud is not effectively utilized. The red mud mainly contains chemical elements of calcium, silicon, aluminum, iron, sodium and titanium, a small amount of magnesium, potassium and sulfur, and trace heavy metal elements of manganese, zinc, copper, chromium and lead, and can form precipitates, suspended matters and soluble matters when leaking into underground water, surface water and other water bodies in the piling process, thereby causing heavy metal pollution, pH value rise of the water bodies and other adverse ecological influences. At present, the economic and environmental problems caused by the red mud with continuously increasing stacking quantity make the comprehensive utilization of the red mud become a difficult problem to be solved urgently in the development process of the aluminum industry. The patent CN201810204108.0 discloses that red mud is used as a mineral raw material and is applied to the fields of sand stratum grouting reinforcement and the like. Although the treatment mode can solve the problem of batch application of the red mud, the economic value is low, and the problem that the grouting material is polluted by heavy metal permeating when meeting water cannot be solved. Patent CN201310407079.5 discloses a method for preparing a red mud-based polymer photocatalyst by using red mud as a raw material, and performing photocatalytic decomposition on water to prepare hydrogen. Although the complete utilization of the red mud raw material can be solved, the catalyst needs to be separated again after each use, and the hydrogen production rate is low. Patent CN201510802366.5 discloses a red mud-based iron catalyst prepared from red mud, and the catalyst is applied to methane cracking to prepare hydrogen. Although the method can fully utilize the mineral composition with catalysis and catalysis assisting functions in the red mud, the red mud needs to be subjected to acid dissolution treatment during the preparation of the catalyst, secondary pollution is caused, and the problem of large-scale application of the red mud cannot be solved. Therefore, the disposal of the red mud waste residue not only needs to improve the economic value of large-scale utilization, but also needs to consider the heavy metal pollution in the red mud waste residue and the secondary pollution problem in the preparation of the catalyst.
Meanwhile, as a big agricultural country, China can generate more than 7 hundred million tons of straws every year, so that the straws become wastes which are not used much but need to be treated, and the crop straws belong to a valuable biomass energy resource in an agricultural ecological system. Therefore, the improvement of the comprehensive development and utilization of the straws of the crops such as rice, wheat and the like and the utilization rate thereof have important significance for promoting the income increase of farmers, environmental protection, resource saving and sustainable development of agricultural economy. In addition, the walnut shell powder is used as a water quality purification filtering material and is widely applied to industrial sewage treatment in oil fields, chemical industry, leather making and the like and urban water supply and drainage engineering at present. However, the walnut shell powder is used as a filter material for a limited number of times, and a large amount of solid waste can still be generated after the filtration performance of the walnut shell powder is reduced. Therefore, the method has important research significance for improving the resource utilization value of the walnut shell powder and thoroughly solving the solid waste pollution.
H2S gas is one of main atmospheric pollutants, and has the characteristics of wide pollution range, great harm and the like. H contained in industrial exhaust gas2S gas can not only cause the poisoning of pipelines and catalysts, cause the deterioration of process conditions and the corrosion of equipment, but also cause serious environmental pollution problems and even harm to the safety and health of human beings. Currently, for H2The treatment scheme of S includes a dry method and a wet method. The dry desulfurization method is widely applied in the fields of high precision, simple process and convenient operation and maintenance, and is particularly suitable for occasions with low concentration and large air quantity. The dry desulfurization techniques commonly used in the market at present include an iron oxide method, a zinc oxide method, a manganese ore method, a molecular sieve method and the like. Patent CN201711321654.4 uses diatomite to dip copper nitrate solution and calcines to prepare a CuO diatomite desulfurizer which can remove Hg and H in coal flue gas simultaneously2And S. The catalyst has simple process and low cost, but H2The S removal rate of 95 percent can only reach the crude desulfurization standard, and the application range is limited. Patent CN201811446537.5 discloses a molecular sieve catalyst obtained by high-temperature activation, alkali liquor treatment and ion replacement, which can convert H2The concentration of S is controlled below 1ppm to realize H2And (4) removing the S with high precision. But the breakthrough sulfur capacity is only 6.34%, which limits the use space of the catalyst.
Disclosure of Invention
In view of the domestic existence of a large amount of red mud waste residues, straws and walnut shell powder, and the lack of advanced safe disposal and high value-added resourcesThe invention discloses a porous ceramic-based desulfurizer prepared by using walnut shell powder, straw fiber, zinc oxide powder, forming agent solution and red mud waste residue, which solves the problem of disposal of large quantities of red mud waste residue, straw and walnut shell powder fundamentally and realizes high value-added resource utilization. The main basis is as follows: most of the oxides in the red mud waste residue can react with H2S is combined to form metal sulfide, the metal sulfide has a good desulfurization effect, and proper amount of zinc oxide powder is added to improve the performance of the desulfurizer by utilizing the synergistic effect of active components in the red mud waste residue and the zinc oxide. After the red mud waste residue is prepared into the porous ceramic, heavy metal ions can be fixed in the ceramic desulfurizer, the problem of heavy metal secondary pollution can not be caused in the using process, meanwhile, straw fibers and walnut shell powder are added to improve the pore structure in the porous ceramic, the porosity of the ceramic is improved, and H is promoted2S and porous ceramic desulfurizer. The successful application of the invention can not only thoroughly solve the problem of safe disposal of the red mud waste residue, the straw and the walnut shell powder, but also solve the problem of H as a desulfurizer2S pollution, thereby bringing great economic, environmental protection and social benefits.
The purpose of the invention can be realized by the following technical scheme:
a desulfurizer which takes red mud waste residue as an active raw material is characterized in that walnut shell powder, straw fiber, zinc oxide powder, forming agent solution and red mud waste residue are used as a catalyst to prepare a porous ceramic-based desulfurizer;
wherein: red mud waste residue: walnut shell powder: straw fiber: zinc oxide powder: the mass ratio of the forming agent solution is 55-65: 15-20: 5-10: 5-10: 5 to 15.
The technical scheme of the invention is as follows: the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 5-15%; the red mud waste residue is polluted red mud discharged when aluminum oxide is extracted in the aluminum production industry, and the granularity is 0.106-0.150 mm.
The technical scheme of the invention is as follows: the granularity of the walnut shell powder is 0.250-0.425 mm; the granularity of the zinc oxide powder is 0.106-0.150 mm; the straw fiber is rice or wheat straw and has a length of less than 5 mm.
The technical scheme of the invention is as follows: the desulfurizer is prepared by the following method:
(4) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing straws of rice or wheat by a crusher to obtain straw fibers with the length of less than 5 mm;
(5) proportioning and granulating
According to the raw material formula of the porous ceramic-based desulfurizer, the raw material powder sieved in the step (1) is weighed in sequence and stirred uniformly, then the forming agent solution and the deionized water are weighed, mixed, ground and granulated, wherein the mass ratio of the forming agent solution to the deionized water is 1: 0.1 to 3;
(6) shaping and calcining
And extruding and molding the granulated pug to obtain a ceramic blank, and then placing the ceramic blank into a muffle furnace for calcining to obtain the porous ceramic-based desulfurizer.
The preparation method comprises the following steps: and (4) calcining at 900-1000 ℃ for 4-6 h.
The technical scheme of the invention is as follows: the desulfurizing agent is at low concentration H2S removal; preferably: the low concentration is 100-1000 ppm.
The desulfurization reaction conditions and results of the present invention: 7mL of desulfurizer (phi 3mm, L7mm) is filled into a U-shaped tube, and two sides of the desulfurizer are kept flat in the U-shaped tube (the tube diameter is 10mm, and the height is 250 mm). The U-tube was transferred to a box furnace and maintained at 220 ℃. 500ppm of H and 80mL/min of H are introduced2And S, recording the concentration of the tail gas. The breakthrough point was marked when the tail gas concentration rose to 25 ppm.
Breakthrough sulfur capacity (amount of gas × concentration of hydrogen sulfide × time)/volume of catalyst × 100%
The desulfurizer of the invention can work continuously for more than 3400min, and the penetration sulfur capacity is higher than 19.4%.
Has the advantages that:
the leaching rates of lead, zinc and chromium of the porous ceramic-based desulfurizer prepared by the invention are far lower than those of GB25466-2010
The limit value requirements of each element content (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the emission standards of lead and zinc industrial pollutants thoroughly and effectively solve the secondary pollution and high added value resource utilization of the red mud waste residue. Simultaneously utilizes the synergistic effect of active components in the red mud and the zinc oxide to remove H2S, increasing the sulfur capacity of desulfurizer to solve H2S, the problem of environmental pollution. The porous ceramic-based desulfurizer of the invention adsorbs and removes low-concentration H2The S has high precision, high efficiency, wide application range and wide market application prospect.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
example 1
(1) Raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing rice straws by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing 55g of red mud waste residue powder, 15g of walnut shell powder, 10g of rice straw fiber and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and calcining the ceramic blank in a muffle furnace at 900 ℃ for 4 hours in an air atmosphere to obtain a porous ceramic-based desulfurizer;
(4) testing of desulfurizing agent Performance
7mL of desulfurizer (phi 3mm, L7mm) is filled into a U-shaped tube, and two sides of the desulfurizer are kept flat in the U-shaped tube (the tube diameter is 10mm, and the height is 250 mm). The U-tube was transferred to a box furnace and maintained at 220 ℃. 500ppm of H and 80mL/min of H are introduced2And S, recording the concentration of the tail gas. When the tail gas is richThe increase in the degree to 25ppm marks the breakdown point. At this time, the desulfurizer can continuously work for 3518min, and the penetrating sulfur capacity is 20.1%.
(5) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
(6) The application range is as follows: the desulfurizer prepared by the method is suitable for low-concentration H2And (4) removing the S.
Example 2:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing rice straws by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing 65g of red mud waste residue powder, 15g of walnut shell powder, 5g of rice straw fiber and 5g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and calcining the ceramic blank in a muffle furnace for 6 hours at 1000 ℃ in an air atmosphere to obtain a porous ceramic-based desulfurizer;
(4) testing of desulfurizing agent Performance
7mL of desulfurizer (phi 3mm, L7mm) is filled into a U-shaped tube, and two sides of the desulfurizer are kept flat in the U-shaped tube (the tube diameter is 10mm, and the height is 250 mm). The U-tube was transferred to a box furnace and maintained at 220 ℃. 500ppm of H and 80mL/min of H are introduced2And S, recording the concentration of the tail gas. The breakthrough point was marked when the tail gas concentration rose to 25 ppm. At this time, the desulfurizer can continuously work for 3400min, and the penetrating sulfur capacity is 19.4%.
(5) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
(6) The application range is as follows: the desulfurizer prepared by the method is suitable for low-concentration H2And (4) removing the S.
Example 3:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing rice straws by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing 55g of red mud waste residue powder, 20g of walnut shell powder, 5g of rice straw fiber and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and calcining the ceramic blank in a muffle furnace at 900 ℃ for 6 hours in an air atmosphere to obtain a porous ceramic-based desulfurizer;
(4) testing of desulfurizing agent Performance
7mL of desulfurizer (phi 3mm, L7mm) is filled into a U-shaped tube, and two sides of the desulfurizer are kept flat in the U-shaped tube (the tube diameter is 10mm, and the height is 250 mm). The U-tube was transferred to a box furnace and maintained at 220 ℃. 500ppm of H and 80mL/min of H are introduced2And S, recording the concentration of the tail gas. The breakthrough point was marked when the tail gas concentration rose to 25 ppm. At the moment, the desulfurizer can continuously work for 3483min, and the penetrating sulfur capacity is 19.9%.
(5) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
(6) The application range is as follows: the desulfurizer prepared by the method is suitable for low-concentration H2And (4) removing the S.
Comparative example 1
Weighing 7mL of commercial ZnO desulfurizer (phi 3mm, L7mm) and filling the ZnO desulfurizer into a U-shaped tube to ensure that two sides of the catalyst in the U-shaped tube are level. The U-tube was transferred to a box furnace and held at 220 ℃. 500ppm of H with a flow rate of 80ml/min was introduced2And S, recording the concentration of the tail gas. When the tail gas concentration rises to 25ppm and is marked as a breakthrough point, the desulfurizer continuously works for 1200min at the moment, and the breakthrough sulfur capacity is 6.86 percent.
The contrast effect is as follows: compared with example 1, the commercial ZnO desulfurizer has performance inferior to that of the desulfurizer of the invention, and the breakthrough sulfur capacity is only 34% of that of example 1.
Comparative example 2
(1) Raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use;
(2) proportioning and granulating
Weighing 80g of red mud waste residue powder and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and calcining the ceramic blank in a muffle furnace at 900 ℃ for 6 hours in an air atmosphere to obtain a porous ceramic-based desulfurizer;
(4) testing of desulfurizing agent Performance
7mL of desulfurizer (phi 3mm, L7mm) is filled into a U-shaped tube, and two sides of the desulfurizer are kept flat in the U-shaped tube (the tube diameter is 10mm, and the height is 250 mm). The U-tube was transferred to a box furnace and maintained at 220 ℃. 500ppm of H and 80mL/min of H are introduced2And S, recording the concentration of the tail gas. The breakthrough point was marked when the tail gas concentration rose to 25 ppm. At this time, the desulfurizer can continuously work for 1795min, and the penetrating sulfur capacity is 10.3%.
(5) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
(6) The contrast effect is as follows: compared with the examples 1-3, the penetration sulfur capacity is obviously reduced when the walnut shell powder and the straw powder are not added during the preparation of the desulfurizer.
Comparative example 3
(1) Raw material crushing
Crushing the red mud waste residue by a ball mill, and homogenizing by a standard sieve (0.106-0.150mm) of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing rice straws by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing 65g of red mud waste residue powder, 15g of walnut shell powder and 10g of rice straw fibers, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and calcining the ceramic blank in a muffle furnace for 6 hours at 1000 ℃ in an air atmosphere to obtain a porous ceramic-based desulfurizer;
(4) testing of desulfurizing agent Performance
7mL of desulfurizer (phi 3mm, L7mm) is filled into a U-shaped tube, and two sides of the desulfurizer are kept flat in the U-shaped tube (the tube diameter is 10mm, and the height is 250 mm). The U-tube was transferred to a box furnace and maintained at 220 ℃. 500ppm of H and 80mL/min of H are introduced2And S, recording the concentration of the tail gas. The breakthrough point was marked when the tail gas concentration rose to 25 ppm. At this time, the desulfurizer can continuously work for 2315min, and the penetrating sulfur capacity is 13.22%.
(5) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) are far lower than the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant emission standard)
(6) The contrast effect is as follows: compared with the examples 1-3, the penetrating sulfur capacity of the desulfurizer is obviously reduced when no zinc oxide powder is added during preparation.
Comparative example 4
(1) Raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing rice straws by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
Weighing 55g of red mud waste residue powder, 15g of walnut shell powder, 10g of rice straw fiber and 10g of zinc oxide powder, then weighing 10g of polyvinyl alcohol solution and 10g of deionized water, mixing, grinding and granulating;
(3) shaping and calcining
Extruding and molding the granulated pug to obtain a ceramic blank, and calcining the ceramic blank in a muffle furnace for 4 hours at 500 ℃ in an air atmosphere to obtain a porous ceramic-based desulfurizer;
(4) testing of desulfurizing agent Performance
7mL of desulfurizer (phi 3mm, L7mm) is filled into a U-shaped tube, and two sides of the desulfurizer are kept flat in the U-shaped tube (the tube diameter is 10mm, and the height is 250 mm). The U-tube was transferred to a box furnace and maintained at 220 ℃. 500ppm of H and 80mL/min of H are introduced2And S, recording the concentration of the tail gas. The breakthrough point was marked when the tail gas concentration rose to 25 ppm. At this time, the desulfurizer can continuously work for 3558min, and the penetrating sulfur capacity is 20.3%.
(5) Leaching test of heavy metal elements in catalyst
The leaching rates of lead, zinc and chromium elements of a sample detected by adopting ICP (inductively coupled plasma emission spectrometry) exceed the limit requirements (0.5 mg/L, 1.5mg/L and 1.5mg/L respectively) of the content of each element of GB25466-2010 lead and zinc industrial pollutant discharge Standard)
(6) The contrast effect is as follows: compared with the examples 1-3, the calcination temperature is reduced during the preparation of the desulfurizer, and although the penetrated sulfur capacity is slightly increased, heavy metal elements cannot be fixed in the desulfurizer, and are easy to separate out to cause secondary environmental pollution.
Claims (8)
1. A desulfurizer which takes red mud waste residue as an active raw material is characterized in that: the catalyst is prepared into a porous ceramic-based desulfurizer by walnut shell powder, straw fiber, zinc oxide powder, forming agent solution and red mud waste residue;
wherein: red mud waste residue: walnut shell powder: straw fiber: zinc oxide powder: the mass ratio of the forming agent solution is 55-65: 15-20: 5-10: 5-10: 5 to 15.
2. The desulfurizing agent according to claim 1, wherein: the forming agent solution is a polyvinyl alcohol solution with the mass fraction of 5-15%; the red mud waste residue is polluted red mud discharged when aluminum oxide is extracted in the aluminum production industry, and the granularity is 0.106-0.150 mm.
3. The desulfurizing agent according to claim 1, wherein: the granularity of the walnut shell powder is 0.250-0.425 mm; the granularity of the zinc oxide powder is 0.106-0.150 mm; the straw fiber is rice or wheat straw and has a length of less than 5 mm.
4. The desulfurizing agent according to claim 1, wherein: the desulfurizer is prepared by the following method:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing straws of rice or wheat by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
According to the raw material formula of the porous ceramic-based desulfurizer, the raw material powder sieved in the step (1) is weighed in sequence and stirred uniformly, then the forming agent solution and the deionized water are weighed, mixed, ground and granulated, wherein the mass ratio of the forming agent solution to the deionized water is 1: 0.1 to 3;
(3) shaping and calcining
And extruding and molding the granulated pug to obtain a ceramic blank, and then placing the ceramic blank into a muffle furnace for calcining to obtain the porous ceramic-based desulfurizer.
5. The porous ceramic-based desulfurizing agent of claim 4, wherein: and (4) calcining at 900-1000 ℃ for 4-6 h.
6. A method for preparing the desulfurizing agent according to claim 1, characterized in that: the method comprises the following steps:
(1) raw material crushing
Respectively crushing the red mud waste residue and the zinc oxide powder material by a ball mill, and homogenizing the crushed materials by a standard sieve (0.106-0.150mm) with the size of 100-140 meshes for later use; crushing walnut shell powder by a crusher, and homogenizing the crushed walnut shell powder for later use by passing the crushed walnut shell powder through a standard sieve (0.250-0.425mm) with the mesh size of 40-60; crushing straws of rice or wheat by a crusher to obtain straw fibers with the length of less than 5 mm;
(2) proportioning and granulating
According to the raw material formula of the porous ceramic-based desulfurizer, the raw material powder sieved in the step (1) is weighed in sequence and stirred uniformly, then the forming agent solution and the deionized water are weighed, mixed, ground and granulated, wherein the mass ratio of the forming agent solution to the deionized water is 1: 0.1 to 3;
(3) shaping and calcining
And extruding and molding the granulated pug to obtain a ceramic blank, and then placing the ceramic blank into a muffle furnace for calcining to obtain the porous ceramic-based desulfurizer.
7. The method of claim 6, wherein: and (4) calcining at 900-1000 ℃ for 4-6 h.
8. The desulfurization agent of claim 1 at low concentration H2S removal; preferably: the low concentration is 100-1000 ppm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958099A (en) * | 2021-03-01 | 2021-06-15 | 江苏正丹化学工业股份有限公司 | Catalyst for vinyl toluene production and preparation method and application thereof |
| CN112957927A (en) * | 2021-03-05 | 2021-06-15 | 湖北第二师范学院 | Porous ceramic oil-water separation membrane taking red mud waste residues as raw materials and preparation method thereof |
| CN113072951A (en) * | 2021-03-31 | 2021-07-06 | 郑州大学 | Composite biochar, preparation method thereof and ecological restoration method for industrial solid waste |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810682A (en) * | 1986-06-26 | 1989-03-07 | Comalco Aluminum Limited | Production of useful materials including synthetic nepheline from Bayer red mud |
| CN1312350A (en) * | 2001-03-24 | 2001-09-12 | 太原理工大学 | Coarse iron oxide desulfurizer for high temperature gas and its prepn |
| CN1317548A (en) * | 2001-03-24 | 2001-10-17 | 太原理工大学 | Desulfurizing agent of zinc ferrite for high-temp gas and its preparing process |
| CN101280227A (en) * | 2008-05-21 | 2008-10-08 | 太原理工大学 | Medium-high temperature gas desulfurizer and preparation thereof |
| CN101475844A (en) * | 2009-01-20 | 2009-07-08 | 太原理工大学 | Preparation of high temperature gas desulfurizer |
-
2019
- 2019-12-31 CN CN201911418640.3A patent/CN111116224B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4810682A (en) * | 1986-06-26 | 1989-03-07 | Comalco Aluminum Limited | Production of useful materials including synthetic nepheline from Bayer red mud |
| CN1312350A (en) * | 2001-03-24 | 2001-09-12 | 太原理工大学 | Coarse iron oxide desulfurizer for high temperature gas and its prepn |
| CN1317548A (en) * | 2001-03-24 | 2001-10-17 | 太原理工大学 | Desulfurizing agent of zinc ferrite for high-temp gas and its preparing process |
| CN101280227A (en) * | 2008-05-21 | 2008-10-08 | 太原理工大学 | Medium-high temperature gas desulfurizer and preparation thereof |
| CN101475844A (en) * | 2009-01-20 | 2009-07-08 | 太原理工大学 | Preparation of high temperature gas desulfurizer |
Non-Patent Citations (1)
| Title |
|---|
| 张宗友: "铁基脱硫剂的稳定性研究与改性", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112958099A (en) * | 2021-03-01 | 2021-06-15 | 江苏正丹化学工业股份有限公司 | Catalyst for vinyl toluene production and preparation method and application thereof |
| CN112958099B (en) * | 2021-03-01 | 2023-09-05 | 江苏正丹化学工业股份有限公司 | Catalyst for vinyl toluene production and preparation method and application thereof |
| CN112957927A (en) * | 2021-03-05 | 2021-06-15 | 湖北第二师范学院 | Porous ceramic oil-water separation membrane taking red mud waste residues as raw materials and preparation method thereof |
| CN112957927B (en) * | 2021-03-05 | 2024-04-05 | 湖北第二师范学院 | Porous ceramic oil-water separation film taking red mud waste residues as raw materials and preparation method thereof |
| CN113072951A (en) * | 2021-03-31 | 2021-07-06 | 郑州大学 | Composite biochar, preparation method thereof and ecological restoration method for industrial solid waste |
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