CN112206758A - Biomass charcoal-based desulfurization catalyst and preparation method and application thereof - Google Patents
Biomass charcoal-based desulfurization catalyst and preparation method and application thereof Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 81
- 230000023556 desulfurization Effects 0.000 title claims abstract description 81
- 239000002028 Biomass Substances 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 60
- 239000003610 charcoal Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 14
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 12
- 239000011630 iodine Substances 0.000 claims abstract description 12
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 230000000149 penetrating effect Effects 0.000 claims abstract description 5
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000011280 coal tar Substances 0.000 claims description 17
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 10
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 10
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 10
- 239000011425 bamboo Substances 0.000 claims description 10
- 238000001125 extrusion Methods 0.000 claims description 9
- 235000013399 edible fruits Nutrition 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003546 flue gas Substances 0.000 claims description 5
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 238000007906 compression Methods 0.000 abstract description 3
- 230000006835 compression Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- 239000002245 particle Substances 0.000 description 13
- 239000003575 carbonaceous material Substances 0.000 description 12
- 238000007873 sieving Methods 0.000 description 10
- 241001330002 Bambuseae Species 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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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
- B01D53/8609—Sulfur oxides
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention discloses a biomass charcoal-based desulfurization catalyst, and a preparation method and application thereof. The compression strength of the biomass charcoal-based desulfurization catalyst is more than or equal to 160N/cm, the penetrating sulfur capacity in the first period is more than or equal to 200mg/g, and the iodine adsorption value is more than or equal to 1000 mg/g. The preparation method comprises the following steps: (1) under the protection of inert atmosphere, the biomass raw material is thermally treated for 2-3h at the temperature of 500-600 ℃ to obtain carbon powder; (2) granulating a mixture consisting of carbon powder, a binder and a dispersing agent to obtain a first precursor; (2) under the protection of inert atmosphere, carrying out heat treatment on the first precursor at the temperature of 500-700 ℃ for 2-6h to obtain a second precursor; (3) and carrying out heat treatment on the second precursor at the temperature of 800-900 ℃ for 2-6h in the atmosphere containing activated gas to obtain the biomass carbon-based desulfurization catalyst. The biomass charcoal-based desulfurization catalyst with high desulfurization activity and high compressive strength is prepared by a special and simple process and process parameters, and has low cost and long service life, so that the biomass charcoal-based desulfurization catalyst has very high application value.
Description
Technical Field
The invention relates to the technical field of sewage and waste gas desulfurization, in particular to a biomass charcoal-based desulfurization catalyst and a preparation method and application thereof.
Background
Currently, a desulfurization method using a porous carbon material as a desulfurization catalyst for desulfurization attracts attention because a high-quality sulfuric acid by-product can be obtained, as compared with a limestone-gypsum desulfurization method. The novel desulfurization method utilizes the nano-pore structure of the porous carbon material to adsorb and catalytically oxidize sulfur dioxide into sulfur trioxide, and the porous carbon material after saturated adsorption is washed by water, washed by dilute sulfuric acid or heated, so that the catalytic activity of the porous carbon material is recovered, and the impurity content of washing liquid is low, so that the porous carbon material can be used as a sulfuric acid byproduct.
In flue gas desulfurization, porous carbon materials are generally packed in a fixed bed reactor for use, and the flue gas is desulfurized while passing through the fixed bed reactor. In order to improve the desulfurization efficiency of the porous carbon material, an effective means is to improve the degree of development of pores of the porous carbon material; meanwhile, in order to prolong the life of the porous carbon material, one effective way is to increase the compressive strength of the porous carbon material. However, the degree of development of pores and the magnitude of compressive strength tend to be inversely related, i.e., the more developed the pores, the less compressive strength although the desulfurization efficiency is improved. In order to achieve higher desulfurization efficiency, compressive strength is often sacrificed. For example, the compressive strength of the existing porous carbon material is generally less than 160N/cm, and although good desulfurization efficiency can be obtained, it needs to be frequently replaced at the time of desulfurization due to the small compressive strength.
Therefore, there is an urgent need for a porous carbon with high compressive strength and high desulfurization activity, so as to ensure the desulfurization efficiency of the porous carbon material and have a long service life.
Disclosure of Invention
The invention mainly aims to provide a biomass charcoal-based desulfurization catalyst, and a preparation method and application thereof, so as to solve the technical problems of low desulfurization efficiency and short service life in the prior art.
In order to achieve the above object, according to a first aspect of the present invention, there is provided a biomass char-based desulfurization catalyst. The compressive strength of the biomass charcoal-based desulfurization catalyst is more than or equal to 160N/cm, the penetrating sulfur capacity in the first period is more than or equal to 200mg/g, and the iodine adsorption value is more than or equal to 1000 mg/g.
In order to achieve the above object, according to a second aspect of the present invention, there is provided a method for preparing a biomass char-based desulfurization catalyst. The compression strength of the biomass charcoal-based desulfurization catalyst is more than or equal to 160N/cm, the penetrating sulfur capacity in the first period is more than or equal to 200mg/g, and the iodine adsorption value is more than or equal to 1000mg/g, and the preparation method comprises the following steps:
(1) under the protection of inert atmosphere, the biomass raw material is thermally treated for 2-3h at the temperature of 500-600 ℃; cooling and then grinding to obtain carbon powder;
(2) granulating a mixture consisting of carbon powder, a binder and a dispersing agent to obtain a first precursor;
(2) under the protection of inert atmosphere, carrying out heat treatment on the first precursor at the temperature of 500-700 ℃ for 2-6h to obtain a second precursor;
(3) and carrying out heat treatment on the second precursor at the temperature of 800-900 ℃ for 2-6h in the atmosphere containing activated gas to obtain the biomass carbon-based desulfurization catalyst.
Furthermore, the particle size of the carbon powder is less than or equal to 75 μm.
Further, the granulation includes kneading and extrusion molding, and the obtained first precursor has a columnar shape, a diameter of a cross section of 2 to 6mm, and a length of 4 to 15 mm.
Further, the adhesive is coal tar; the dispersant is water.
Further, the mass ratio of the carbon powder, the coal tar and the water in the mixture is (2-4): 1: (0.1-2).
Further, the coal tar is high-temperature coal tar with the mass fraction of pitch being more than or equal to 50%.
Further, the biomass raw material is one or more of bamboo, straw, coconut shell, fruit shell and fruit stone.
Further, the activated gas is one or more of water vapor, flue gas, CO and air.
Further, when the activating gas is water vapor, the mass ratio of the water vapor to the second precursor is 1 to 2.
In order to achieve the above object, according to a third aspect of the present invention, there is provided a desulfurization method. The desulfurization method adopts the biomass charcoal-based desulfurization catalyst or the biomass charcoal-based desulfurization catalyst prepared by the preparation method, and the biomass charcoal-based desulfurization catalyst is filled in a fixed bed reactor when in use.
The biomass charcoal-based desulfurization catalyst with high desulfurization activity and high compressive strength is prepared by special process and process parameters, the preparation process is simple, the cost is low, the first-period sulfur penetration capacity is more than or equal to 200mg/g when the catalyst is applied to desulfurization, the compressive strength is high, the service life is long, and therefore the catalyst has very high application value.
The present invention will be further described with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The present invention will now be described more fully hereinafter. Those skilled in the art will be able to implement the invention based on these teachings. Before the present invention is explained, it is to be noted that:
the technical solutions and features provided in the present invention in the respective sections including the following description may be combined with each other without conflict.
Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
With respect to terms and units in the present invention. The terms "comprising," "having," and any variations thereof in the description and claims of this invention and the related sections are intended to cover non-exclusive inclusions.
The term "first period breakthrough sulfur capacity" refers to the capacity of sulfur dioxide that can be removed per unit volume of biomass carbon-based desulfurization catalyst when first used, and is also referred to as first sulfur capacity or first sulfur capacity.
The unit of compressive strength is N/cm, and the compressive strength means that a single-particle biomass charcoal-based catalyst is axially placed between two platforms, and load is uniformly applied to the single-particle biomass charcoal-based catalyst until the particles of the single-particle biomass charcoal-based catalyst are crushed. The number of the particles is more than or equal to 50 in the general compression strength test, and the average value is taken.
The term "iodine adsorption value" refers to the developed degree of micropores larger than 1.0nm in the pores of the biomass charcoal-based desulfurization catalyst, and the higher the iodine adsorption value is, the stronger the adsorption capacity of the biomass charcoal-based desulfurization catalyst on small molecular impurities is.
In order to prepare the biomass charcoal-based desulfurization catalyst which has the compressive strength of more than or equal to 160N/cm, the penetrating sulfur capacity of a first period of more than or equal to 200mg/g, the iodine adsorption value of more than or equal to 1000mg/g and is filled in a fixed bed reactor for desulfurization, the preparation method of the biomass charcoal-based desulfurization catalyst provided by the invention comprises the following steps:
(1) under the protection of inert atmosphere, the biomass raw material is thermally treated for 2-3h at the temperature of 500-600 ℃ to obtain biochar; wherein the biomass raw material is one or more of bamboo, straw, coconut shell, fruit shell and fruit stone.
(2) The carbon powder with the granularity less than or equal to 75 mu m is obtained by grinding and sieving by a screen.
(3) Kneading and extruding a mixture consisting of carbon powder, a binder and a dispersing agent to obtain a first precursor; wherein:
the adhesive is high-temperature coal tar with the mass fraction of pitch being more than or equal to 50%, the dispersing agent is water, and the mass ratio of the carbon powder, the coal tar and the water in the mixture is (2-4): 1: 0.5; the first precursor obtained by extrusion molding is columnar, the diameter of the cross section of the first precursor is 2-6mm, and the length of the first precursor is 4-15 mm;
within the above numerical range, the shape of the first precursor has relatively little influence on the desulfurization efficiency and compressive strength, but it is still different that it is verified that the optimum desulfurization efficiency can be obtained when the first precursor is stacked in the fixed bed reactor when the first precursor has a cross-sectional diameter of 4mm and a length of 8 mm.
(4) And under the protection of inert atmosphere, carrying out heat treatment on the first precursor at the temperature of 500-700 ℃ for 2-6h to obtain a second precursor.
(5) In the presence of steam, flue gas, CO2And in one or more of air, carrying out heat treatment on the second precursor at the temperature of 800-900 ℃ for 2-6h to obtain the biomass carbon-based desulfurization catalyst.
The beneficial effects of the present invention will be further illustrated by the following examples and comparative examples using the above method but with different process parameters.
The process parameters for examples 1-5 and comparative examples 1-2 were as follows:
in the step (1), bamboo is used as a biomass raw material, and the technological parameters of heat treatment are shown in table 1.
In the step (2), the carbon powder with the granularity less than or equal to 75 mu m is obtained by sieving the ground carbon powder by a 200-mesh sieve.
In the step (3), the mass ratio of the carbon powder, the coal tar and the water in the mixture is 3: 1: 0.5; the first precursor obtained by extrusion molding was columnar in shape, with a cross section of 4mm in diameter and 8mm in length.
In the step (4), the first precursor is subjected to heat treatment at 700 ℃ for 2h under the protection of inert atmosphere to obtain a second precursor.
In the step (5), in the atmosphere containing water vapor, the mass ratio of the water vapor to the second precursor is 1.5, and the second precursor is thermally treated at 900 ℃ for 2h to obtain the biomass charcoal-based desulfurization catalyst.
The results of the performance tests of the biomass char-based desulfurization catalysts of examples 1-5 and comparative examples 1-2 are shown in Table 1.
TABLE 1
In general, the more developed the pores of the biochar-based desulfurization catalyst and the higher the specific surface area, the higher the first cycle breakthrough sulfur capacity and iodine adsorption value, but the lower the compressive strength. However, as can be seen from table 1, the biomass charcoal-based desulfurization catalysts in examples 1 to 5 not only have very high first-cycle breakthrough sulfur capacity and iodine adsorption value, but also have compressive strength of more than 160N/cm, thereby solving the pain point that the desulfurization efficiency and the service life of the desulfurization material are difficult to match. On the contrary, the comparative example 1 shows that the compressive strength, the first-cycle breakthrough sulfur capacity and the iodine adsorption value are very low when the conventional low-temperature heat treatment temperature is used, and thus it is difficult to use them as a desulfurization catalyst. Meanwhile, when the heat treatment temperature was further raised (comparative example 2), the first cycle breakthrough sulfur capacity and iodine adsorption value were further lowered.
The process parameters for examples 6-8 and comparative example 3 were as follows:
in the step (1), bamboo is used as a biomass raw material, and the biomass raw material is subjected to heat treatment at 550 ℃ for 2.5 hours under the protection of inert atmosphere to obtain carbon powder.
In the step (2), the mesh number of the screen mesh adopted after grinding is shown in table 2, wherein the particle size of the carbon powder obtained by sieving with a 100-mesh screen mesh is less than or equal to 150 μm, the particle size of the carbon powder obtained by sieving with a 300-mesh screen mesh is less than or equal to 48 μm, the particle size of the carbon powder obtained by sieving with a 400-mesh screen mesh is less than or equal to 38 μm, and the particle size of the carbon powder obtained by sieving with a 500-mesh screen mesh is less than or equal to 25 μ.
In the step (3), the mass ratio of the carbon powder, the coal tar and the water in the mixture is 3: 1: 0.5; the first precursor obtained by extrusion molding was columnar in shape, with a cross section of 4mm in diameter and 8mm in length.
In the step (4), the first precursor is subjected to heat treatment at 700 ℃ for 2h under the protection of inert atmosphere to obtain a second precursor.
In the step (5), in the atmosphere containing water vapor, the mass ratio of the water vapor to the second precursor is 1.5, and the second precursor is thermally treated at 900 ℃ for 2h to obtain the biomass charcoal-based desulfurization catalyst.
The results of the performance tests of the biomass char-based desulfurization catalysts of examples 6 to 8 and comparative example 3 are shown in Table 2.
TABLE 2
As can be seen from Table 2, the combination of properties of example 3 and examples 6-8 is significantly better than that of comparative example 3. With the reduction of the particle size of the carbon powder, the penetration sulfur capacity, the iodine adsorption value and the compressive strength of the first period are all improved. Therefore, it is preferable to sieve the particles with a 200-300 mesh sieve in consideration of the cost (smaller particle size, higher production cost), desulfurization efficiency and service life.
The process parameters for examples 9-12 and comparative examples 4-5 are as follows:
in the step (1), bamboo is used as a biomass raw material, and the biomass raw material is subjected to heat treatment at 550 ℃ for 2.5 hours under the protection of inert atmosphere to obtain carbon powder.
In the step (2), the carbon powder with the granularity less than or equal to 75 mu m is obtained by sieving the ground carbon powder by a 200-mesh sieve.
In the step (3), the mass ratio of the carbon powder, the coal tar and the water in the mixture is shown in a table 3; the first precursor obtained by extrusion molding was columnar in shape, with a cross section of 6mm in diameter and 8mm in length.
In the step (4), the first precursor is subjected to heat treatment at 700 ℃ for 2h under the protection of inert atmosphere to obtain a second precursor.
In the step (5), in the atmosphere containing water vapor, the mass ratio of the water vapor to the second precursor is 1.5, and the second precursor is thermally treated at 900 ℃ for 2h to obtain the biomass charcoal-based desulfurization catalyst.
The results of the performance tests of the biochar-based desulfurization catalysts of examples 9-12 and comparative examples 4-5 are shown in Table 3.
TABLE 3
As can be seen from Table 3, when the mass ratio of the carbon powder, the coal tar and the water is (2-4): the combination properties of examples 9 to 12 were excellent at a ratio of 1:0.5, and the combination properties of comparative examples 4 to 5 were greatly reduced when the ratio exceeded the above numerical range.
The process parameters for examples 13 to 16 and comparative examples 6 to 7 were as follows:
in the step (1), bamboo is used as a biomass raw material, and the biomass raw material is subjected to heat treatment at 550 ℃ for 2.5 hours under the protection of inert atmosphere to obtain carbon powder.
In the step (2), the carbon powder with the granularity less than or equal to 75 mu m is obtained by sieving the ground carbon powder by a 200-mesh sieve.
In the step (3), the mass ratio of the carbon powder, the coal tar and the water in the mixture is 3: 1: 0.5; the first precursor obtained by extrusion molding was columnar in shape, with a cross section of 6mm in diameter and 8mm in length.
In step (4), the heat treatment parameters are shown in Table 4.
In the step (5), in the atmosphere containing water vapor, the mass ratio of the water vapor to the second precursor is 1.5, and the second precursor is thermally treated at 900 ℃ for 2h to obtain the biomass charcoal-based desulfurization catalyst.
The results of the performance tests of the biochar-based desulfurization catalysts of examples 13-16 and comparative examples 6-7 are shown in Table 4.
TABLE 4
As can be seen from Table 4, the combination of the properties of examples 13-16 are excellent when heat treated at 500-700 deg.C for 2-6 h. The overall performance of the comparative examples 4-5 was greatly reduced when the heat treatment parameters of the prior art were used for the treatment.
The process parameters for examples 17-20 and comparative examples 8-9 were as follows:
in the step (1), bamboo is used as a biomass raw material, and the biomass raw material is subjected to heat treatment at 550 ℃ for 2.5 hours under the protection of inert atmosphere to obtain carbon powder.
In the step (2), the carbon powder with the granularity less than or equal to 75 mu m is obtained by sieving the ground carbon powder by a 200-mesh sieve.
In the step (3), the mass ratio of the carbon powder, the coal tar and the water in the mixture is 3: 1: 0.5; the first precursor obtained by extrusion molding was columnar in shape, with a cross section of 6mm in diameter and 8mm in length.
In the step (4), the first precursor is subjected to heat treatment at 700 ℃ for 2h under the protection of inert atmosphere to obtain a second precursor.
In the step (5), in the atmosphere containing water vapor, the mass ratio of the water vapor to the second precursor is shown in table 5, and the second precursor is thermally treated at 900 ℃ for 2 hours to obtain the biomass charcoal-based desulfurization catalyst.
The results of the performance tests of the biochar-based desulfurization catalysts of examples 17-20 and comparative examples 8-9 are shown in Table 5.
TABLE 5
As can be seen from Table 5, when the mass ratio of water vapor to the second precursor is (1-2): the combination properties of examples 17 to 20 were excellent at 1, and the combination properties of comparative examples 8 to 9 were greatly lowered at values outside the above-mentioned numerical ranges.
The process parameters for examples 21 to 24 and comparative examples 10 to 11 were as follows:
in the step (1), bamboo is used as a biomass raw material, and the biomass raw material is subjected to heat treatment at 550 ℃ for 2.5 hours under the protection of inert atmosphere to obtain carbon powder.
In the step (2), the carbon powder with the granularity less than or equal to 75 mu m is obtained by sieving the ground carbon powder by a 200-mesh sieve.
In the step (3), the mass ratio of the carbon powder, the coal tar and the water in the mixture is 3: 1: 0.5; the first precursor obtained by extrusion molding was columnar in shape, with a cross section of 4mm in diameter and 8mm in length.
In the step (4), the first precursor is subjected to heat treatment at 700 ℃ for 2h under the protection of inert atmosphere to obtain a second precursor.
In the step (5), in the atmosphere containing water vapor, the mass ratio of the water vapor to the second precursor is 1.5, and the parameters of the heat treatment of the second precursor are shown in table 6, so that the biomass charcoal-based desulfurization catalyst is obtained.
The results of the performance tests of the biochar-based desulfurization catalysts of examples 21-24 and comparative examples 10-11 are shown in Table 6.
TABLE 6
As can be seen from Table 6, the comprehensive properties of examples 21 to 24 were excellent when heat-treated at 800-.
Examples 25 to 28 differ in that the biomass feedstock is different and the remaining process parameters are the same as in example 3. The specific biomass selection and the results of the performance testing of the resulting biomass char-based desulfurization catalyst are shown in table 7.
TABLE 7
As can be seen from Table 7, the preparation method of the invention is suitable for various biomass raw materials, and when the biomass raw materials are one or more of bamboo, straw, coconut shell and walnut shell, the obtained biomass charcoal-based desulfurization catalyst has better comprehensive performance.
The contents of the present invention have been explained above. Those skilled in the art will be able to implement the invention based on these teachings. All other embodiments, which can be derived by a person skilled in the art from the above description without inventive step, shall fall within the scope of protection of the present invention.
Claims (10)
1. The biomass charcoal-based desulfurization catalyst is characterized in that: the compressive strength of the biomass charcoal-based desulfurization catalyst is more than or equal to 160N/cm, the penetrating sulfur capacity in the first period is more than or equal to 200mg/g, and the iodine adsorption value is more than or equal to 1000 mg/g.
2. The preparation method of the biomass charcoal-based desulfurization catalyst comprises the following steps of:
(1) under the protection of inert atmosphere, the biomass raw material is thermally treated for 2-3h at the temperature of 500-600 ℃; cooling and then grinding to obtain carbon powder;
(2) granulating a mixture consisting of carbon powder, a binder and a dispersing agent to obtain a first precursor;
(2) under the protection of inert atmosphere, carrying out heat treatment on the first precursor at the temperature of 500-700 ℃ for 2-6h to obtain a second precursor;
(3) and carrying out heat treatment on the second precursor at the temperature of 800-900 ℃ for 2-6h in the atmosphere containing activated gas to obtain the biomass carbon-based desulfurization catalyst.
3. The method for preparing the biomass charcoal-based desulfurization catalyst according to claim 2, characterized in that: the granularity of the carbon powder is less than or equal to 75 mu m.
4. The method for preparing the biomass charcoal-based desulfurization catalyst according to claim 2, characterized in that: the granulation comprises kneading and extrusion, and the obtained first precursor is cylindrical in shape, with a cross-section of 2-6mm in diameter and 4-15mm in length.
5. The method for preparing the biomass charcoal-based desulfurization catalyst according to claim 2, characterized in that: the adhesive is coal tar; the dispersant is water.
6. The method for preparing the biomass charcoal-based desulfurization catalyst according to claim 5, characterized in that: the mass ratio of the carbon powder, the coal tar and the water in the mixture is (2-4): 1: (0.1-2).
7. The method for preparing the biomass charcoal-based desulfurization catalyst according to claim 5, characterized in that: the coal tar is high-temperature coal tar with the mass fraction of pitch more than or equal to 50%.
8. The method for preparing the biomass charcoal-based desulfurization catalyst according to claim 2, characterized in that: the biomass raw material is one or more of bamboo, straw, coconut shell, fruit shell and fruit stone; the activated gas is one or more of water vapor, flue gas, CO and air.
9. The method for preparing a biomass charcoal-based desulfurization catalyst according to claim 8, characterized in that: when the activating gas is water vapor, the mass ratio of the water vapor to the second precursor is 1 to 2.
10. The desulfurization method is characterized in that: the biomass charcoal-based desulfurization catalyst according to claim 1, or the biomass charcoal-based desulfurization catalyst prepared by the preparation method according to any one of claims 2 to 9, which is used while being packed in a fixed bed reactor.
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| CN117531484A (en) * | 2024-01-08 | 2024-02-09 | 成都达奇科技股份有限公司 | Active carbon film material and preparation method and application thereof |
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