CN111661846A - Method for preparing activated carbon - Google Patents
Method for preparing activated carbon Download PDFInfo
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- CN111661846A CN111661846A CN202010413603.XA CN202010413603A CN111661846A CN 111661846 A CN111661846 A CN 111661846A CN 202010413603 A CN202010413603 A CN 202010413603A CN 111661846 A CN111661846 A CN 111661846A
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- C01B32/30—Active carbon
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- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- C01B32/318—Preparation characterised by the starting materials
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- C—CHEMISTRY; METALLURGY
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- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
The invention relates to a method for preparing activated carbon, which comprises the following steps: s1, uniformly mixing raw material coal and carbon powder to form a first material; s2, adding an environment-friendly solid binder into the first material, uniformly stirring, adding a liquid solvent, and uniformly mixing to form a second material; s3, preparing the second material into a molding material; s4, performing high-temperature dry distillation treatment on the molding material to obtain a carbonized material; and S5, activating the carbonized material to obtain the activated carbon. The invention realizes the comprehensive utilization of the carbon powder generated by the activated carbon dry-method flue gas desulfurization and denitrification regeneration tower, reduces the raw material cost and improves the comprehensive index of the desulfurization and denitrification activated carbon.
Description
Technical Field
The invention relates to a method for preparing activated carbon, in particular to a method for preparing activated carbon by replacing part of raw coal with recycled carbon powder.
Background
A large amount of desulfurization and denitrification active carbon is used by steel enterprises every year due to sintering flue gas purification, a large amount of active carbon powder is generated by friction between materials and equipment in the using process of the desulfurization and denitrification active carbon, and the active carbon powder is combined with flue gas dust to finally form carbon powder containing impurities. Generally, these powdered carbons are treated for heat generation after the combustion in a blast furnace, but this reduces resource utilization and causes secondary pollution. In addition, because the existing activated carbon preparation method adopts coal tar as a binder to be mixed with raw material coal as an initial material, and when the initial material is further treated in the preparation process, benzene and naphthalene pollutants are generated due to the contained coal tar, so that the harm to a human body is caused, and the pollution to the surrounding environment is larger.
Disclosure of Invention
The invention aims to provide a method for preparing activated carbon, which reasonably utilizes carbon powder generated in the sintering flue gas purification process.
To achieve the above object, the present invention provides a method for preparing activated carbon, comprising:
s1, uniformly mixing raw material coal and carbon powder to form a first material;
s2, adding an environment-friendly solid binder into the first material, uniformly stirring, adding a liquid solvent, and uniformly mixing to form a second material;
s3, preparing the second material into a molding material;
s4, performing high-temperature dry distillation treatment on the molding material to obtain a carbonized material;
and S5, activating the carbonized material to obtain the activated carbon.
According to an aspect of the present invention, in step S1, the raw coal is at least one of weakly caking coal, coking coal, semi-coke, and anthracite.
According to one aspect of the present invention, in step S1, the raw material coal is a mixture of weakly caking coal, coking coal and semi coke, and the mass ratio of the weakly caking coal is: coking coal: the semi-coke is 1-2: 3-4: 4-6.
According to an aspect of the present invention, in step S1, the weakly caking coal, the coking coal, and the semi coke are mixed by mass as follows: coking coal: semi-coke is 1:3: 6.
According to one aspect of the invention, the first material further comprises asphalt powder, and the proportion of the asphalt powder in the first material is 0-30 wt%.
According to one aspect of the invention, the proportion of the asphalt powder in the first material is 10-15 wt%.
According to an aspect of the present invention, in step S1, if the raw material coal is prepared at a ratio of X1 and the charcoal powder is prepared at a ratio of X2 in the first material, the following are satisfied: x1+ X2 is less than or equal to 1, wherein X1 is less than or equal to 70 wt% and less than or equal to 99 wt%, and X2 is less than or equal to 1 wt% and less than or equal to 30 wt%.
According to one aspect of the invention, the amount of the environmentally friendly solid binder added in step S2 is 2 wt% to 8 wt% of the mass of the first material.
According to one aspect of the invention, the fineness of the first material satisfies a sieve fraction of greater than 90% on a 325 mesh tyler standard sieve;
the fineness of the environment-friendly solid binder meets the condition that the sieving rate on a 100-mesh Taylor standard sieve is more than 90 percent.
According to one aspect of the invention, the environment-friendly solid binder is one or a mixture of polyvinyl alcohol, starch, guar gum, xanthan gum, polyacrylamide, sodium carboxymethylcellulose, sodium alginate and urea-formaldehyde resin.
According to one aspect of the invention, in step S4, the molding material is subjected to high-temperature dry distillation treatment by a carbonization furnace, and the molding material is sequentially shifted from the region with the carbonization temperature of 400-.
According to one aspect of the invention, the content A of volatile matters in the carbon powder meets the following requirements: a is more than or equal to 3 wt%.
According to one aspect of the invention, the carbon powder is carbon powder produced in a flue gas purification process.
According to one aspect of the invention, the carbon powder is generated in a flue gas purification process by desulfurization and denitrification activated carbon.
According to one aspect of the invention, the carbon powder contains iron oxide.
According to an aspect of the present invention, in step S3, the second material is extruded into a strip-shaped molding material.
According to one aspect of the invention, in step S3, the second material is pressed under a pressure of 5 to 25MPa, and the shaped material has a particle size of 7 to 10mm and a length of 0.5 to 1.5 cm.
According to an aspect of the present invention, in the step of forming the second material after adding the liquid solvent and mixing in step S2, the liquid solvent is added when the temperature of the material reaches 50 to 60 ℃, and the material is kneaded and stirred for at least 10 min.
According to one scheme of the invention, the carbon powder produced by the steel enterprise flue gas desulfurization and denitrification regeneration tower is comprehensively utilized to a great extent, the raw material cost is reduced, and the comprehensive index of the desulfurization and denitrification activated carbon is improved.
According to one scheme of the invention, the recycled carbon powder (namely the activated carbon particle powder with the particle size of less than 1.4 mm) is mixed with the raw material coal according to the proportion, and the activated carbon powder generated in the sintering flue gas purification process is reasonably utilized, so that the carbon powder generated in the flue gas purification process is reused, and the utilization rate of the carbon powder is improved. In addition, the recycled carbon powder also contains volatile substances and a small amount of oxides, which is beneficial to improving various performance indexes of the activated carbon and enables key indexes such as the adsorption performance of the finished activated carbon to be better. In addition, the carbon powder contains a plurality of pores, and further promotes the pore development of the raw material coal.
According to the scheme of the invention, the environment-friendly solid binder is adopted to replace coal tar production, so that the use difficulty is solved, the potential safety hazard is reduced, and the management investment is reduced. Meanwhile, the difficulty of treating the carbonized tail gas caused by coal tar production is solved, the investment of tail gas treatment equipment is reduced, and the cost is saved.
According to one scheme of the invention, the environment-friendly solid adhesive does not generate gas harmful to human bodies, so that the environment-friendly solid adhesive is beneficial to ensuring the health of staff. In addition, the adhesive adopted in the scheme adopts the adhesive of the type, and the adhesive has no harm, so that the adhesive is further beneficial to ensuring the physical health of staff.
According to the scheme of the invention, the active carbon produced by the scheme has higher mesopore-micropore ratio, more developed pores and large micropore ratio, has obvious desulfurization and denitration effects on flue gas and enables the desorption speed of the active carbon to be higher.
According to one scheme of the invention, the addition amount of the environment-friendly solid binder in the first material is set to be within the range, so that the second material has good viscosity and plasticity in the subsequent material forming process, and the second material is easier to form. Meanwhile, during carbonization, the environment-friendly solid binder volatilizes along with the rise of temperature, pores are generated at the position, and favorable conditions are created for re-pore forming during activation, so that the development of the pores is promoted, the iodine value is increased, the activation time is shortened, the process cost is reduced, the addition amount of the environment-friendly solid binder is set in the range, the development of the pores in the activation process is more sufficient, and the iodine value is more excellent.
According to one scheme of the invention, under the condition that the fineness of the raw material coal and the carbon powder is reached, the carbon particles can be more tightly connected in the extrusion forming process, the molecular van der Waals force is larger, and the strength of the obtained molding material is higher. And the environment-friendly solid binder is controlled to be in the fineness, so that the carbon particles and the binder particles can be in closer contact in the forming process, and the strength of the forming material is favorable. In addition, in the present invention, the environment-friendly solid binder having a fineness of 100 mesh is directly stirred with the first material in step S2, so that the solid binder among the coal particles can be uniformly dispersed.
According to one scheme of the invention, the formed material has higher compactness, lower moisture and higher strength by applying high pressure in the extrusion process. In addition, the particle size and the length of the molding material are set in the range, so that the development of the internal pores is more favorable, the defect of uneven development of the internal pores is avoided, the adsorption performance of the finished product of the active carbon is better, and the efficiency of the carbonization and activation processes is higher.
According to one scheme of the invention, the pores inside and outside the molding material are preliminarily formed through the step temperature change, the defect that the molding material is cracked due to the rapid temperature change is avoided under the step temperature heating, and the method is favorable for ensuring the quality and the strength of the carbonized material. In addition, through high-temperature discharging, the carbonized material can have certain activity when entering a subsequent activation process, so that the time required by the activation process is shorter, and the efficiency is higher.
According to one scheme of the invention, the proportion of the mesopores and the macropores of the carbonized material is increased, and the formation of the pores can improve the absorption speed and the desorption speed of the activated carbon in the using process, so that the activated carbon has excellent desulfurization and denitrification performances.
Drawings
Fig. 1 is a block diagram schematically illustrating steps of a method for preparing activated carbon using recycled carbon powder instead of a portion of raw coal according to an embodiment of the present invention.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
The present invention is described in detail below with reference to the drawings and the specific embodiments, which are not described in detail herein, but the embodiments of the present invention are not limited to the following embodiments.
1. Preparation process of activated carbon
As shown in fig. 1, according to an embodiment of the present invention, a method for preparing activated carbon using recycled carbon powder instead of a portion of raw coal according to the present invention includes:
s1, uniformly mixing raw material coal and recycled carbon powder to form a first material;
s2, adding an environment-friendly solid binder into the first material, uniformly stirring, adding a liquid solvent, and uniformly mixing to form a second material;
s3, preparing the second material into a molding material;
s4, performing high-temperature dry distillation treatment on the molding material to obtain a carbonized material;
and S5, activating the carbonized material to obtain the activated carbon.
According to an embodiment of the present invention, in step S1, the raw material coal is at least one of weakly caking coal, coking coal, semi-coke, and anthracite. In the present embodiment, the raw material coal is a mixture of weakly caking coal, coking coal, and semi coke. In the embodiment, the weakly caking coal, the coking coal and the semi coke are mixed according to a certain proportion, and the specific mass ratio is that the weakly caking coal: coking coal: the semi-coke is 1-2: 3-4: 4-6. Further preferably, in the present embodiment, the mass ratio of the weakly caking coal, the coking coal and the semi coke is: weakly caking coal: coking coal: semi-coke is 1:3: 6. Through the arrangement, the activated carbon generated by the raw material coal consisting of the weakly caking coal, the coking coal and the semi coke according to the preparation proportion is better in quality, and higher in strength, porosity and activity.
According to one embodiment of the invention, the first material can be added with asphalt powder, and the proportion of the asphalt powder in the first material is 0-30 wt%. Preferably, the proportion of the asphalt powder in the first material is 10-15 wt%.
According to one embodiment of the present invention, in step S1, when the blending ratio of the raw coal is X1 and the blending ratio of the recovered carbon powder is X2 in the first material, the following are satisfied: x1+ X2 is less than or equal to 1, wherein X1 is less than or equal to 70 wt% and less than or equal to 99 wt%, and X2 is less than or equal to 1 wt% and less than or equal to 30 wt%. In this embodiment, the recycled carbon powder is a solid mixed powder generated by mutual friction of activated carbon, abrasion of the activated carbon and equipment, and capture of other dust by a bag-type dust collector in a sintered flue gas desulfurization and denitrification tower in the steel industry, and the main component of the solid mixed powder is activated carbon powder and contains a part of volatile components.
According to one embodiment of the invention, the carbon powder comprises iron oxide.
Through the arrangement, the recycled carbon powder (namely the activated carbon particle powder with the particle size smaller than 1.4 mm) is mixed with the raw material coal according to the proportion, and the activated carbon powder generated in the sintering flue gas purification process is reasonably utilized, so that the carbon powder generated in the flue gas purification process is reused, and the utilization rate of the carbon powder is improved. In addition, the recycled carbon powder also contains volatile substances and a small amount of oxides, which is beneficial to improving various performance indexes of the activated carbon and enables key indexes such as the adsorption performance of the finished activated carbon to be better. In addition, the carbon powder contains a plurality of pores, and further promotes the pore development of the raw material coal.
According to one embodiment of the invention, the content A of volatile matters in the carbon powder meets the following requirements: a is more than or equal to 3 wt%. Preferably, the content A of the volatile components in the carbon powder meets the following requirements: a is more than or equal to 10 wt%. Through the arrangement, the volatile matters in the carbon powder are ensured to be in the range, and the content of the activated carbon prepared from the carbon powder with high volatile matter content is further ensuredThe volatile matter refers to volatile matter which is absorbed by the recycled activated carbon powder in the desulfurization and denitrification process and is easy to generate gaseous matter to volatilize from the carbon powder after being heated and decomposed, and the volatile gaseous matter accounts for the total mass of the activated carbon sample and is called as volatile matter, for example, SO2NOx, VOCs and other sulfur containing species, and the like.
According to one embodiment of the invention, the environmentally friendly solid binder is added in an amount of 2 wt% to 8 wt% based on the mass of the first material. In this embodiment, the amount of the environmentally friendly solid binder added does not account for the total mass of the first material. In this embodiment, the environment-friendly solid binder is one or a mixture of polyvinyl alcohol, starch, guar gum, xanthan gum, polyacrylamide, sodium carboxymethylcellulose, sodium alginate, and urea-formaldehyde resin. In the embodiment, the environment-friendly solid binder adopts guar gum, xanthan gum and starch mixture.
Through the arrangement, the addition amount of the environment-friendly solid binder (such as guar gum, xanthan gum and starch mixture) in the first material is set within the range, so that the second material has good viscosity and plasticity in the subsequent material forming process, and the second material is easier to form. Meanwhile, during carbonization, the environment-friendly solid binder volatilizes along with the rise of temperature, pores are generated at the position, and favorable conditions are created for facilitating the molecules of the activating agent to enter the pores during activation and carrying out activation reaction with the surfaces of the carbon particles for pore forming again, so that the development of the pores is promoted, the iodine value is increased, the activation time is shortened, the process cost is reduced, the addition amount of the environment-friendly solid binder is set in the range, the development of the pores in the activation process is more sufficient, and the iodine value is more excellent.
According to one embodiment of the invention, the fineness of the first material is such that the sieve fraction on a 325 mesh tyler standard sieve is greater than 90%; the fineness of the environment-friendly solid binder meets the condition that the sieving rate on a 100-mesh Taylor standard sieve is more than 90 percent. Through the arrangement, under the condition that the raw material coal and the carbon powder respectively reach the fineness, the raw material coal particles and the carbon powder particles can be fully and uniformly mixed, the raw material coal particles and the carbon powder particles can be connected more tightly in the process of high-pressure forming of the material, the van der Waals force of molecules is larger, and the strength of the obtained formed material is higher. Under the condition of controlling the fineness of the environment-friendly solid binder, the raw material coal particles, the carbon powder particles and the binder particles can be uniformly dispersed and closely contacted in the forming process, and the environment-friendly solid binder is also favorable for improving the strength of a formed material. In the invention, the fineness of the environment-friendly solid binder is 100 meshes, and the environment-friendly solid binder is directly stirred with the raw coal in the step S2, so that the solid binder among coal particles can be uniformly dispersed.
According to one embodiment of the invention, the liquid solvent added to the first mass is primary water. By adopting the primary water, the purity requirement of the activated carbon production can be met, and the cost is low and the acquisition is convenient.
It should be noted that primary water refers to water directly delivered from underground and municipal water delivery lines, which is defined as clean water that is not used by chemical enterprises.
According to one embodiment of the present invention, in the step of extruding the second material into the shaped material in the form of a strand, the second material is pressed under a pressure of 5 to 25MPa, and the shaped material has a particle diameter of 7 to 10mm and a length of 0.5 to 1.5 cm. By applying high pressure in the extrusion process, the formed material has higher compactness, low moisture and high strength. In addition, the particle size and the length of the molding material are set in the range, so that the development of the internal pores is more favorable, the defect of uneven development of the internal pores is avoided, the adsorption performance of the finished product of the active carbon is better, and the efficiency of the carbonization and activation processes is higher.
According to one embodiment of the invention, in the step of performing high-temperature dry distillation treatment on the molding material to obtain the carbonized material, the molding material is subjected to high-temperature dry distillation treatment by a carbonization furnace, and the molding material is sequentially shifted from a region with a carbonization temperature of 400-. Through the change of the step temperature, the pores inside and outside the molding material are preliminarily formed, the defect that the molding material is cracked due to the rapid change of the temperature is avoided under the heating of the step temperature, and the carbonization material is ensured to have favorable quality and strength.
In addition, in the process of step temperature rise, besides providing the continuous growth of the basic pore structure of the carbon particles for coal pyrolysis and carbonization, the oxides of metals such as Fe and the like in the carbon powder can play a catalytic role in the carbonization process, and the oxides cooperate with each other to accelerate the coal pyrolysis, promote the rapid decomposition of tar-like substances generated in the pyrolysis process, and promote the gasification activation reaction of water molecules, carbon dioxide and other activator molecules formed in the carbonization process on the surfaces of the carbon particles, so that the development type pore structure is more favorably formed among the coal particles, that is, compared with the traditional activated carbon prepared by using raw coal without adding the recycled carbon powder, the activated carbon prepared by adding the recycled activated carbon powder into the raw coal not only accelerates the carbonization process, but also completes the partial activation of the carbon particles formed in the carbonization process by the raw coal. In addition, through high-temperature discharging, the carbonized material can have certain activation conditions when entering a subsequent activation process, and meanwhile, oxides such as Fe in the recovered carbon powder can catalyze and accelerate the activation reaction between the carbon particles and the gasifying agent in the subsequent activation process, so that the time required by the activation process of the carbonized material is shorter, and the efficiency is higher.
According to one embodiment of the invention, the carbonized material is subjected to an activation reaction with water vapor in an activation furnace at the temperature of 900-950 ℃ to obtain the activated carbon. Through the arrangement, the proportion of the mesopores and the macropores of the carbonized material is improved, the formation of the pores can improve the adsorption speed and the desorption speed of the activated carbon in the using process, so that the activated carbon has excellent desulfurization and denitrification performances.
2. Examples of the embodiments
To further illustrate the invention, a number of examples are shown below in Table 1. In Table 1, the iodine value mg/g is determined by taking the national standard GB/T7702.15-1987 as a standard, the abrasion resistance percent is determined by taking the national standard GB/T30202.3-2013 as a standard, the compressive strength is determined by taking the national standard GB/T30202.3-2013 as a standard, the ash is determined by taking the national standard GB/T7702.15-2008 as a standard, the desulfurization value is determined by taking the national standard GB/T30202.4-2013 as a standard, and the denitrification rate is determined by taking the national standard GB/T35254-2017 as a standard.
TABLE 1
Example 1
Referring to table 1, in example 1 of the present embodiment, weakly caking coal, coking coal and semi-coke (the ratio of weakly caking coal, coking coal and semi-coke is 1:3:6) are respectively crushed and ground into raw material coal, and the fineness of the raw material coal meets the requirement that the sieving rate on a 325-mesh taylor standard sieve is more than 90%; the carbon powder can be directly ground without being crushed, and the fineness of the carbon powder meets the requirement that the sieving rate on a 325-mesh Taylor standard sieve is more than 90 percent; the environment-friendly solid binder (adopting the mixture of guar gum, xanthan gum and starch) needs to meet the requirement that the sieving rate on a 100-mesh Taylor standard sieve is more than 90 percent.
In the embodiment, raw coal, carbon powder and an environment-friendly solid binder are weighed and placed into kneading equipment. The ratio of weakly caking coal, coking coal and semi coke in the raw coal is unchanged, the ratio accounts for 99 wt% of the first material, the carbon powder accounts for 1 wt% of the first material, the environment-friendly solid binder accounts for 3 wt% of the first material (not accounting for the total weight of the first material), the mass of the first material and the environment-friendly solid binder is from large to small (such a feeding mode has the advantage that the material with small mass can be more quickly dispersed in the material with large mass during stirring and can be more quickly and uniformly stirred), the first material and the environment-friendly solid binder are placed into kneading equipment, the kneading equipment can be heated, the constant temperature is 80 ℃, the stirring time is 30min, and the first material and the environment-friendly solid binder can be fully and uniformly mixed within the stirring time. And when the temperature of the materials reaches 50-60 ℃, weighing 13 wt% of water of the first material by mass, adding the water into kneading equipment, kneading and stirring the materials for 10min, fully playing the role of a binder under the conditions of the kneading and stirring time and the temperature of the materials, preparing for bonding the formed coal particles together in the next step, and obtaining the kneaded materials after the kneading and stirring are completed.
In the embodiment, the kneaded material is subjected to compression molding by a four-column hydraulic press to obtain a strip-shaped material, and then granulation is performed to obtain a molded material, wherein the carbon strip has a particle size of 7.8mm, a length of 1-1.5cm, and a molding pressure of 20 MPa.
In the embodiment, the molding material is sent into a carbonization furnace for carbonization and dry distillation treatment to obtain a carbonized material, wherein the molding material is shifted from a carbonization temperature of 400 ℃ to a carbonization temperature of 550 ℃ in the carbonization furnace and then shifted to a carbonization temperature of 700 ℃, and then is discharged from a discharge bin of the carbonization furnace to obtain the carbonized material, and the carbonization time is 40 min.
In the embodiment, the carbonized material is fed into an activation furnace for activation treatment to obtain activated carbon, wherein the activation treatment conditions are as follows: the method takes water vapor as an activating medium, and when the temperature of the furnace body is raised to 800 ℃, the water vapor is introduced, so that the carbonized material has a water vapor atmosphere when being activated; when the temperature of the furnace body is raised to 950 ℃, the activation furnace runs for 15min at constant temperature, and the method can stabilize the temperature of the furnace to 950 +/-1 ℃; and (3) feeding the carbonized material into an activation furnace for activation reaction, wherein the activation time is 15min, and obtaining the activated carbon. The indexes of the prepared active carbon are as follows: the abrasion resistance is 98.42 percent, the compression strength is 47.8kgf, the iodine value is 337mg/g, the ash content is 12.70 percent, the desulfurization value is 15.31mg/g, and the denitration rate is 53.78 percent. Compared with indexes GB/T30201-2013 coal granular activated carbon for desulfurization and denitrification, the invention obtains the qualified activated carbon product with excellent wear resistance and compressive strength.
It should be noted that, in this embodiment, the raw coal, the environment-friendly solid binder, and the like are changed so that the production process is identical to the above process, and the details are not repeated herein.
Examples 2 to 12
As is clear from Table 1, examples 2 to 11 differ from example 1 in the content of carbon powder added to the raw material, while example 12 differs from example 1 in the case where no carbon powder is added to the raw material. Further, as can be seen from table 1, the corresponding indexes of the final activated carbon products obtained in the different embodiments were also changed.
As can be seen from table 1, the content of the recycled carbon powder is set to 1 wt% to 30 wt%, the recycled carbon powder can be recycled to the greatest extent, and the index of the activated carbon prepared from the recycled carbon powder is greater than or equal to 330mg/g in iodine value, greater than or equal to 97% in abrasion resistance, greater than or equal to 40kgf in compressive strength, greater than or equal to 15.3mg/g in desulfurization value, and greater than or equal to 53.7% in denitration rate. In contrast, in example 12, in the case where no carbon powder was used, the iodine value, desulfurization value and denitration rate were all decreased, that is, the iodine value, desulfurization value and denitration rate of activated carbon prepared by mixing raw material coal with recovered carbon powder as one of the raw materials of activated carbon were better, which was related to the fact that the recovered carbon powder itself had a porous structure and that the carbon powder contained oxides of metals such as Fe, which were capable of catalyzing and accelerating the carbonization of raw material coal and the activation reaction of carbon particles. The porous structure of the recovered carbon powder and the attached metal oxides such as Fe are cooperated with each other in the coal carbonization pyrolysis and carbon particle activation processes, so that the development of the porous structure in the activated carbon is promoted, the specific surface area and the desulfurization and denitrification performance of the activated carbon are greatly improved, as shown in examples 1 to 11, the iodine value, the desulfurization value and the denitrification rate are gradually improved along with the increase of the specific gravity of the recovered carbon powder in the first material, and when the carbon powder accounts for 16 wt%, the high-grade activated carbon can be obtained. Therefore, the first material in the invention adopts the recycled carbon powder to replace part of the raw material coal, thereby not only saving the cost of the raw material and producing the activated carbon with qualified index, but also having higher desulfurization and denitrification performance. In the invention, the content of the carbon powder can be seen from the index condition, so that the content of the carbon powder is not only 1 wt% -30 wt%, but also can be more than 30 wt%.
Examples 13 to 15
In addition, to further illustrate the advantages of the activated carbon prepared according to the present invention, experimental statistics were performed on the performance of the activated carbon prepared under the same conditions as in example 1, using the undersize waste (unqualified material, containing trace amounts of residual volatiles and trace amounts of metal oxide impurities) of the fresh activated carbon in example 12 of the present invention as a raw material, using coal tar as a binder, and using other preparation processes and control parameters, as follows in table 2:
TABLE 2
From the above table, it can be seen that the activated carbon prepared by using the crushed material of the activated carbon sieve as the raw material can obtain the activated carbon with a high iodine value, but the wear resistance and compressive strength of the activated carbon are obviously lower than those of the activated carbon generated in the present invention, the surface of the activated carbon has obvious cracks, the compressive strength is low, and the desulfurization value is not high, and the activated carbon belongs to an unqualified product compared with the national standard GB/T30201-2013 coal-quality granular activated carbon for desulfurization and denitrification. Indicating that the porous structure of the crushed material under the active carbon sieve can not generate synergistic action due to the lack of the raw material coal, and therefore, the performance index of the obtained active carbon product can not be improved.
Examples 16 to 20
In addition, to further illustrate the advantages of the activated carbon prepared according to the present invention, experimental statistics were performed on the properties of the activated carbon prepared under the same conditions as in example 1, using the undersize waste (off-spec material, containing trace amounts of residual volatiles and metal oxide impurities) of the fresh activated carbon and the raw coal as the raw materials, the coal tar as the binder, and other preparation processes and control parameters in example 12 of the present invention, as shown in table 3 below:
as can be seen from the above table, the iodine value, desulfurization value and denitration rate of the activated carbon prepared by using the crushed material of the activated carbon sieve and the raw material coal as the raw materials are still lower than the corresponding indexes of the activated carbon prepared by using the embodiments 1 to 11 of the present embodiment. It is demonstrated that even if the activated carbon is prepared by using the crushed material of the activated carbon sieve and the raw material coal, the performance index of the obtained activated carbon product is still insufficient.
Based on the comparison, in each example, the crushed material of the activated carbon sieve and the carbon powder generated by the flue gas purification adopted in the invention have different influences on the performance of the prepared activated carbon finished product. Through statistics of measured values of components in the crushed materials (fresh material waste carbon powder) screened by the activated carbon and the carbon powder generated by the flue gas purification adopted by the invention, the measured values of the iron oxide are most obviously different.
As in table 4 below:
| fresh material waste carbon powder | Carbon powder produced by flue gas purification | |
| Iron oxide (%) | 1.35 | 10.7 |
Therefore, the carbon powder generated by the flue gas purification adopted in the invention has a large content of ferric oxide, so that the pores of the activated carbon prepared by the carbon powder are effectively increased, and the effects of improving the iodine value and the desulfurization and denitrification performances are further achieved.
Examples 21 to 23
In addition, to further illustrate the advantages of the activated carbon prepared according to the present invention, experimental statistics were performed on the properties of the activated carbon prepared under the same conditions as in example 1, using only carbon powder generated in the flue gas purification process as a raw material, coal tar as a binder, and other preparation processes and control parameters, as shown in table 5 below:
as can be seen from table 5, compared with the activated carbon produced in the present invention, the activated carbon produced only from the carbon powder produced in the flue gas purification process can obtain activated carbon with high iodine value, but the wear resistance and compressive strength are significantly low, which easily causes significant cracks in the activated carbon, and the desulfurization value is also not high, and thus the activated carbon belongs to an unqualified product. The lack of raw material coal indicates that even the carbon powder produced in the flue gas purification process provides a porous structure and metal oxides, the synergistic effect cannot be exerted, and therefore, the performance index of the obtained activated carbon product cannot be improved.
In addition, the iodine value of the carbon powder generated in the flue gas purification process adopted by the invention is within the range of 250-500mg/g, the ash content is within the range of 12-20%, the volatile matter is within the range of 10-20%, and the indexes obtained after sampling detection are shown in the following table 6:
TABLE 6 carbon powder index generated during flue gas purification
To further illustrate the advantages of the carbon powder used in the present invention for preparing activated carbon, the activated carbon preparation time and the activated carbon index performance were experimentally counted according to the different addition amounts of the carbon powder, as shown in table 7 below:
TABLE 7 comparison of different activation times for indexes of activated carbon containing carbon powder
As can be seen from Table 7, the iodine value is similar in group c compared with group a, and the activation time is shortened by half, while the activated carbon performance is better on the basis that the activation time is reduced to half of the original time with the increase of the carbon powder content in group e and group g.
In the scheme of the invention, the carbon powder with the index shown in the table 6 contains a large amount of porous structures formed by mesopores and micropores, and in addition, the recovered carbon powder contains oxides such as Fe metal and the like, which can be cooperated with coal macromolecules in raw material coal to promote pyrolysis of the raw material coal, accelerate decomposition of generated coal tar, catalyze activation reaction of carbon particles, promote development of the porous structures in the activated carbon, and greatly improve the specific surface area and desulfurization and denitrification performance of the activated carbon, so that the carbon powder adopted in the invention can improve the iodine value of products and shorten the activation time.
The foregoing is merely exemplary of particular aspects of the present invention and devices and structures not specifically described herein are understood to be those of ordinary skill in the art and are intended to be implemented in such conventional ways.
The above description is only one embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. A method of making activated carbon, comprising:
s1, uniformly mixing raw material coal and carbon powder to form a first material;
s2, adding an environment-friendly solid binder into the first material, uniformly stirring, adding a liquid solvent, and uniformly mixing to form a second material;
s3, preparing the second material into a molding material;
s4, performing high-temperature dry distillation treatment on the molding material to obtain a carbonized material;
and S5, activating the carbonized material to obtain the activated carbon.
2. The method according to claim 1, wherein in step S1, the raw material coal is at least one of weakly caking coal, coking coal, semi-coke and anthracite.
3. The method according to claim 2, wherein in step S1, the raw material coal is a mixture of weakly caking coal, coking coal and semi coke, and the mass ratio of the weakly caking coal is as follows: coking coal: the semi-coke is 1-2: 3-4: 4-6.
4. The method according to claim 3, wherein in step S1, the weakly caking coal, the coking coal and the semi-coke are mixed by mass as follows: coking coal: semi-coke is 1:3: 6.
5. The method of claim 1, wherein the first material further comprises asphalt powder, and the proportion of the asphalt powder in the first material is 0-30 wt%.
6. The method of claim 5, wherein the proportion of the asphalt powder in the first material is 10-15 wt%.
7. The method of any one of claims 1 to 6, wherein in step S1, if the raw material coal and the carbon powder are mixed together at a ratio X1 and X2, respectively, then the following conditions are satisfied: x1+ X2 is less than or equal to 1, wherein X1 is less than or equal to 70 wt% and less than or equal to 99 wt%, and X2 is less than or equal to 1 wt% and less than or equal to 30 wt%.
8. The method according to claim 1, wherein the environmentally friendly solid binder is added in an amount of 2 wt% to 8 wt% based on the mass of the first material in step S2.
9. The method of claim 1, wherein the fineness of the first material meets a screen rating of greater than 90% on a 325 mesh taylor standard screen;
the fineness of the environment-friendly solid binder meets the condition that the sieving rate on a 100-mesh Taylor standard sieve is more than 90 percent.
10. The method according to claim 1, wherein the environmentally friendly solid binder is a mixture of one or more of polyvinyl alcohol, starch, guar gum, xanthan gum, polyacrylamide, sodium carboxymethyl cellulose, sodium alginate, urea formaldehyde resin.
11. The method as claimed in claim 1, wherein in step S4, the molding material is subjected to high temperature dry distillation treatment by a carbonization furnace, and the molding material is sequentially moved from the region of carbonization temperature 400-.
12. The method as claimed in claim 1, wherein the content A of volatile components in the carbon powder satisfies the following condition: a is more than or equal to 3 wt%.
13. The method according to claim 1, wherein the carbon powder is carbon powder generated in a flue gas purification process.
14. The method of claim 13, wherein the carbon powder is carbon powder generated in a flue gas purification process by using the desulfurization and denitrification activated carbon.
15. The method as claimed in claim 13 or 14, wherein the carbon powder contains iron oxide.
16. The method according to claim 1, wherein the second material is extruded into a strip-shaped molding material in step S3.
17. The method according to claim 16, wherein in step S3, the second material is pressed under a pressure of 5-25MPa, and the shaped material has a particle size of 7-10mm and a length of 0.5-1.5 cm.
18. The method according to claim 1, wherein in the step of forming the second material after adding the liquid solvent and mixing in step S2, when the temperature of the material reaches 50-60 ℃, the liquid solvent is added and the material is kneaded and stirred for at least 10 min.
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| CN112830487A (en) * | 2021-01-15 | 2021-05-25 | 宝武集团环境资源科技有限公司 | Desulfurization and denitrification activated carbon and preparation method and application thereof |
| CN114044515A (en) * | 2021-11-04 | 2022-02-15 | 中欣环保科技有限公司 | Preparation method of desulfurization and denitrification activated carbon |
| CN114314587A (en) * | 2021-11-11 | 2022-04-12 | 宁夏浦士达环保科技有限公司 | Preparation device and method of desulfurization activated carbon |
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