CN111704132B - Active coke and preparation method and application thereof - Google Patents
Active coke and preparation method and application thereof Download PDFInfo
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- CN111704132B CN111704132B CN202010592429.XA CN202010592429A CN111704132B CN 111704132 B CN111704132 B CN 111704132B CN 202010592429 A CN202010592429 A CN 202010592429A CN 111704132 B CN111704132 B CN 111704132B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/336—Preparation characterised by gaseous activating agents
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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
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/33—Preparation characterised by the starting materials from distillation residues of coal or petroleum; from petroleum acid sludge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention provides active coke and a preparation method and application thereof. The preparation method of the active coke comprises the following steps: mixing a coke-making raw material, metal salt and a binder, granulating and drying to obtain a pre-sintered substance; and heating the presintered matter in an inert gas atmosphere for carbonization, introducing water vapor into the system for activation, and finally cooling in the inert gas atmosphere to obtain the active coke. The active coke is prepared by the preparation method. The application of the activated coke is used for flue gas desulfurization and denitration. The activated coke prepared by the preparation method of the activated coke provided by the application has the advantages of high wear-resistant and compressive strength, less moisture, ash and volatile matters, simple synthesis method, low cost, very excellent sulfur denitration performance and good industrial application prospect.
Description
Technical Field
The invention relates to the field of steelmaking, in particular to active coke and a preparation method and application thereof.
Background
The active coke flue gas desulfurization and denitrification technology is a flue gas purification technology with a wide-spectrum purification function, and no secondary pollution such as waste water, waste residue and waste gas is discharged because water is basically not used in the pollution removal process, and the desulfurized byproducts can be changed into valuables.
In the active coke desulfurization and denitrification technology, the active coke needs to be regenerated, so that the requirements on the mechanical strength, the wear resistance and the pressure resistance of the active coke are high. According to statistics, the consumption of the active coke accounts for more than 50-70% of the total cost of the active coke flue gas desulfurization and denitrification process technology, and is a key factor influencing the economic performance of the process technology. The quality of the active coke is closely related to the consumption of the active coke, and the main way for reducing the flue gas desulfurization and denitration technology cost of the active coke at present is to improve the performance of the active coke and reduce the consumption and production cost of the active coke.
The desulfurization and denitrification performance, the mechanical strength, the wear resistance and the compression resistance of the active coke prepared by the existing method are improved to a limited extent.
In view of this, the present application is specifically made.
Disclosure of Invention
The invention aims to provide active coke, a preparation method and application thereof, so as to solve the problems.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of activated coke comprises the following steps:
mixing a coke-making raw material, metal salt and a binder, granulating and drying to obtain a pre-sintered substance;
and heating the presintered matter in an inert gas atmosphere for carbonization, introducing water vapor into the system for activation, and finally cooling in the inert gas atmosphere to obtain the active coke.
The metal salt participates in the reaction process in the coke making process, changes the groups on the surface of the active coke, and improves the adsorption performance of the active coke, particularly the desulfurization and denitrification performance; the binder is beneficial to forming the active coke, is beneficial to increasing internal micropores of the active coke in the coke making process, and can further improve the desulfurization and denitrification performance; the carbonization is carried out under the inert gas atmosphere, so as to replace oxygen in the system, ensure the proceeding of the carbonization pyrolysis process, avoid oxidation reaction and combustion as much as possible and ensure the carbonization effect; the steam activation is a process of generating micropores by the reaction of steam and carbon; finally, the purpose of using the inert gas is to replace the gases such as water vapor, carbon monoxide and residual oxygen, and the like, and maintain the microporous structure of the active coke, so that the desulfurization and denitrification performance is improved.
The inert gas referred to herein is a gas that does not chemically react with the system substance under the reaction temperature conditions, and is, for example, nitrogen gas, a rare gas, or the like. From the viewpoint of cost, nitrogen is preferable.
Preferably, the coking raw materials comprise anthracite, bituminous coal, coking coal and asphalt;
preferably, the mass ratio of the anthracite coal, the bituminous coal, the coking coal and the asphalt is (3-5): (2-4): (2-4): (1-3).
The selection of the raw materials for preparing the coke is the basis for ensuring the performance of the active coke, and is beneficial to reducing the cost and optimizing the resource allocation.
Alternatively, the mass ratio of the anthracite coal, the bituminous coal, the coking coal and the pitch may be 3: 2: 2: 1. 3: 4: 2: 1. 3: 4: 4: 1. 4: 3: 3: 2. 5: 4: 4: 3 and (3-5): (2-4): (2-4): (1-3).
Preferably, the metal salt comprises one or more of iron salt, cerium salt and vanadium salt;
preferably, the metal salt comprises one or more of iron nitrate, cerium nitrate and vanadium nitrate;
preferably, the metal salt is ferric nitrate;
preferably, the metal salt is configured into a metal salt solution with the concentration of 0.05-0.5 mol/L;
preferably, the concentration of the ferric nitrate solution is 0.25 mol/L;
preferably, the mass ratio of the coking raw material to the metal salt solution is (8-14): 1.
the iron salt, cerium salt and vanadium salt have a large effect of improving the performance of the activated coke, the iron salt is the most preferable, and the comprehensive conditions of the improvement effect, the cost and the like of 0.25mol/L iron salt are the best.
Alternatively, the concentration of the metal salt solution may be any value between 0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L, and 0.05-0.5 mol/L.
Preferably, the binder comprises one or more of coal tar, pitch, cellulose and starch;
preferably, the binder is a mixture of cellulose and coal tar;
preferably, the mass ratio of the cellulose to the coal tar in the mixture is 1: 1;
preferably, the mass ratio of the coking raw material to the binder is (5-7): 1.
Through the optimization of the binder, the function of the binder in the aspect of increasing micropores can be further improved, and the wear resistance and the compression resistance of the activated coke are also improved.
Optionally, the mass ratio of the coking raw material to the binder may be 5: 1. 6: 1. 7: 1 and (5-7) 1.
Preferably, water is further added when the coke making raw material, the metal salt and the binder are mixed;
preferably, the mass ratio of the coke making raw material to the water is (3-5): 1.
The water is added to ensure the molding effect of the pre-sintered material (raw material). The amount of water to be added may be increased by adjusting the concentration of the metal salt solution, but it is preferable to add water separately when the concentration of the metal salt solution is controlled.
Optionally, the mass ratio of the coking raw material to the water may be 3: 1. 4: 1. 5: 1 and (3-5) 1.
Preferably, the carbonizing comprises:
preserving heat for 10-30min at the temperature of 250-350 ℃, and then raising the temperature to 600-700 ℃ and preserving heat for 20-50 min;
preferably, the heating rate from 250-350 ℃ to 600-700 ℃ is 10-20 ℃/min;
preferably, the introduction of the inert gas into the system is stopped when the steam is introduced.
The initial temperature is controlled to be 250-350 ℃, because the presintered substance can be quickly crushed and cannot be molded under the condition of low temperature; the temperature rise to 600-700 ℃ and the heat preservation stage are carbonization processes, mainly carbonization occurs, and volatile components are volatilized at the same time, and the stage is an important time period for determining the strength performance of the activated coke. The control of the heating rate is to ensure that the reaction of each stage is carried out under the ordered and controllable condition, which is beneficial to improving the performance of the active coke.
Optionally, the temperature during the carbonization process may be controlled within the range of 350 ℃ for 250-; the temperature range of 600-700 deg.C may be, for example, any value between 600 deg.C, 610 deg.C, 620 deg.C, 630 deg.C, 640 deg.C, 650 deg.C, 660 deg.C, 670 deg.C, 680 deg.C, 690 deg.C, 700 deg.C and 600-700 deg.C, and the heat-preserving time may be any value between 20min, 25min, 30min, 35min, 40min, 45min, 50min and 20-50 min. The temperature rise rate from 350 ℃ at 250 ℃ to 700 ℃ at 600 ℃ can be any value between 10 ℃/min, 15 ℃/min, 20 ℃/min and 10-20 ℃/min.
Preferably, the activation comprises:
raising the temperature of the system to 750-800 ℃, keeping the temperature for 10-30min after the water vapor is introduced, and then raising the temperature of the system to 850-900 ℃ and keeping the temperature for 20-50 min;
preferably, the heating rate from 600-800 ℃ to 750-800 ℃ is 5-20 ℃/min, and the heating rate from 750-800 ℃ to 850-900 ℃ is 5-20 ℃/min.
The reaction of water vapor and carbon is mainly carried out in the temperature range of 750-900 ℃ to generate micropores, and the optimization of the process is greatly helpful for improving the desulfurization and denitrification performance. This stage is divided into two parts, again to control the process of creating the micropores.
Optionally, the temperature control during the activation process may be any value between 750-800 ℃, for example, 750 ℃, 760 ℃, 770 ℃, 780 ℃, 790 ℃, 800 ℃ and 750-800 ℃, and the heat preservation time may be any value between 10min, 15min, 20min, 25min, 30min and 10-30 min; the temperature range of 850-. The heating rate from 600-800 ℃ to 750-800 ℃ and the heating rate from 750-800 ℃ to 850-900 ℃ can be any value of 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min and 5-20 ℃/min.
Preferably, the system temperature is reduced to 450-500 ℃ before the "temperature reduction under the inert gas atmosphere".
The cooling process is divided into two stages, so as to ensure the structure of the micropores and avoid the situations of closure, collapse and the like.
Alternatively, the system temperature may be reduced to any value between 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃ and 450-500 ℃ before being reduced in the inert gas atmosphere.
An active coke, prepared by the preparation method;
preferably, the length of the active coke is 1-1.5cm, and the diameter is 0.7-0.9 cm.
Alternatively, the length of the active coke may be any value between 1cm, 1.1cm, 1.2cm, 1.3cm, 1.4cm, 1.5cm and 1-1.5cm, and the diameter may be any value between 0.7cm, 0.8cm, 0.9cm and 0.7-0.9 cm.
An application of active coke in desulfurization and denitrification of flue gas.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the active coke, the properties of desulfurization and denitrification, mechanical strength, wear resistance and compression resistance and the like of the obtained active coke are greatly improved by adding the metal salt, carbonizing in an inert gas atmosphere, introducing steam for activation and cooling in the inert gas atmosphere; the preparation method is relatively simple and has good industrial application prospect.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present invention, and therefore should not be considered as limiting the scope of the present invention.
FIG. 1 is an ammonia adsorption infrared spectrum of active coke modified by adding ferric nitrate with different concentrations;
FIG. 2 is the infrared spectrum of the active coke modified by different metal salts.
Detailed Description
The terms as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
Embodiments of the present invention will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Example 1
Grinding a certain amount of anthracite, bituminous coal, coking coal and asphalt into powder, and uniformly mixing, wherein the ratio of the anthracite, the bituminous coal, the coking coal and the asphalt in the coke making raw materials is 1000 g: 750 g: 750 g: 200 g. Then 300g of 0.25mol/L ferric nitrate solution is added, and the mixture is stirred vigorously for more than 20min to be mixed evenly. Then 200g of cellulose and 200g of coal tar are added into the mixture and stirred to be uniformly mixed; 600mL of water was then added to the mixture and stirring was continued until the mixture was viscous and not loose. The above mixture was slowly poured into a pelletizer to form a rod-shaped activated coke having a length of about 7cm and a diameter of about 0.7 cm. Placing the granulated columnar active coke in a well-ventilated area for airing, wherein the airing time is not less than 20 h; it was then cut to an active coke length of 1 cm. The tubular furnace used for carbonization and activation is preheated to 300 ℃ from room temperature, and then the cut active coke is immediately placed in the tubular furnace, nitrogen is introduced, and the temperature is kept for 10min at 300 ℃. Then the temperature is raised to 700 ℃ at a heating rate of 10 ℃/min and kept for 10min, and then raised to 780 ℃ at a heating rate of 5 ℃/min, and water vapor is introduced and kept for 10 min. And then, increasing the temperature to 870 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 20min, then, beginning to cool, closing the water vapor when the temperature is reduced to 500 ℃, switching to a nitrogen atmosphere to continue cooling, and obtaining a sample which is the final active coke after the temperature is reduced to room temperature.
Example 2
Grinding a certain amount of anthracite, bituminous coal, coking coal and asphalt into powder, and uniformly mixing, wherein the ratio of the anthracite, the bituminous coal, the coking coal and the asphalt in the coke making raw materials is 1000 g: 750 g: 750 g: 200 g. Then 200g of 0.5mol/L ferric nitrate solution is added, and the mixture is stirred vigorously for more than 20min to be mixed evenly. Then 200g of starch and 200g of coal tar are added into the mixture and stirred to be uniformly mixed; 900mL of water was then added to the mixture and stirring was continued until the mixture was viscous and not loose. The above mixture was slowly poured into a pelletizer to form a rod-shaped activated coke having a length of about 7cm and a diameter of about 0.7 cm. Placing the granulated columnar active coke in a well-ventilated area for airing, wherein the airing time is not less than 20 h; it was then cut to an active coke length of 1 cm. The tubular furnace used for carbonization and activation is preheated to 300 ℃ from room temperature, and then the cut active coke is immediately placed in the tubular furnace, nitrogen is introduced, and the temperature is kept for 10min at 300 ℃. Then the temperature is raised to 700 ℃ at a heating rate of 10 ℃/min and kept for 10min, and then raised to 780 ℃ at a heating rate of 5 ℃/min, and water vapor is introduced and kept for 10 min. And then, increasing the temperature to 870 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 20min, then, beginning to cool, closing the water vapor when the temperature is reduced to 500 ℃, switching to a nitrogen atmosphere to continue cooling, and obtaining a sample which is the final active coke after the temperature is reduced to room temperature.
Example 3
Grinding a certain amount of anthracite, bituminous coal, coking coal and asphalt into powder, and uniformly mixing, wherein the ratio of the anthracite, the bituminous coal, the coking coal and the asphalt in the coke making raw materials is 1000 g: 750 g: 750 g: 200 g. Then 250g of 0.25mol/L ferric nitrate solution is added, and the mixture is stirred vigorously for more than 20min to be mixed evenly. Then 200g of pitch and 200g of coal tar are added into the mixture and stirred to be uniformly mixed; 800mL of water were then added to the mixture and stirring was continued until the mixture was viscous and not loose. The above mixture was slowly poured into a pelletizer to form a rod-shaped activated coke having a length of about 7cm and a diameter of about 0.7 cm. Placing the granulated columnar active coke in a well-ventilated area for airing, wherein the airing time is not less than 20 h; it was then cut to an active coke length of 1 cm. The tubular furnace used for carbonization and activation is preheated to 300 ℃ from room temperature, and then the cut active coke is immediately placed in the tubular furnace, and water vapor is introduced into the tubular furnace and kept at 300 ℃ for 10 min. Then the temperature is raised to 700 ℃ at a heating rate of 10 ℃/min and kept for 10min, and then raised to 780 ℃ at a heating rate of 5 ℃/min, and water vapor is introduced and kept for 10 min. And then, increasing the temperature to 870 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 20min, then, beginning to cool, closing the water vapor when the temperature is reduced to 500 ℃, switching to a nitrogen atmosphere to continue cooling, and obtaining a sample which is the final active coke after the temperature is reduced to room temperature.
Example 4
Grinding a certain amount of anthracite, bituminous coal, coking coal and asphalt into powder, and uniformly mixing, wherein the ratio of the anthracite, the bituminous coal, the coking coal and the asphalt in the coke making raw materials is 1000 g: 750 g: 750 g: 200 g. Then 200-300mL of 0.2mol/L ferric nitrate solution is added and stirred vigorously for more than 20min to mix evenly. Then, 320g of cellulose and 80g of coal tar are added into the mixture and stirred to be uniformly mixed; 700mL of water was then added to the mixture and stirring was continued until the mixture was viscous and not loose. The above mixture was slowly poured into a pelletizer to form a rod-shaped activated coke having a length of about 7cm and a diameter of about 0.7 cm. Placing the granulated columnar active coke in a well-ventilated area for airing, wherein the airing time is not less than 20 h; it was then cut to an active coke length of 1 cm. The tubular furnace used for carbonization and activation is preheated to 300 ℃ from room temperature, and then the cut active coke is immediately placed in the tubular furnace, nitrogen is introduced, and the temperature is kept for 10min at 300 ℃. Then the temperature is raised to 700 ℃ at a heating rate of 10 ℃/min and kept for 10min, and then raised to 780 ℃ at a heating rate of 5 ℃/min, and water vapor is introduced and kept for 10 min. And then, increasing the temperature to 870 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 20min, then, beginning to cool, closing the water vapor when the temperature is reduced to 500 ℃, switching to a nitrogen atmosphere to continue cooling, and obtaining a sample which is the final active coke after the temperature is reduced to room temperature.
Comparative example 1
Grinding a certain amount of anthracite, bituminous coal, coking coal and asphalt into powder, and uniformly mixing, wherein the ratio of the anthracite, the bituminous coal, the coking coal and the asphalt in the coke making raw materials is 1000 g: 750 g: 750 g: 200 g. Then 200g of pitch and 200g of coal tar are added into the mixture and stirred to be uniformly mixed; 600mL of water was then added to the mixture and stirring was continued until the mixture was viscous and not loose. The above mixture was slowly poured into a pelletizer to form a rod-shaped activated coke having a length of about 7cm and a diameter of about 0.7 cm. Placing the granulated columnar active coke in a well-ventilated area for airing, wherein the airing time is not less than 20 h; it was then cut to an active coke length of 1 cm. The tubular furnace used for carbonization and activation is preheated to 300 ℃ from room temperature, and then the cut active coke is immediately placed in the tubular furnace, nitrogen is introduced, and the temperature is kept for 10min at 300 ℃. Then the temperature is raised to 700 ℃ at a heating rate of 10 ℃/min and kept for 10min, and then raised to 780 ℃ at a heating rate of 5 ℃/min, and water vapor is introduced and kept for 10 min. Then the temperature is increased to 870 ℃ at the heating rate of 10 ℃/min and is kept for 20min, then the temperature is reduced, and when the temperature is reduced to 500 ℃, the water vapor is closed without the protection of nitrogen. And cooling to room temperature to obtain the final active coke.
Comparative example 2
Grinding a certain amount of anthracite, bituminous coal, coking coal and asphalt into powder, and uniformly mixing, wherein the ratio of the anthracite, the bituminous coal, the coking coal and the asphalt in the coke making raw materials is 1000 g: 750 g: 750 g: 200 g. Then 200g of cellulose and 200g of coal tar are added into the mixture and stirred to be uniformly mixed; 600mL of water was then added to the mixture and stirring was continued until the mixture was viscous and not loose. The above mixture was slowly poured into a pelletizer to form a rod-shaped activated coke having a length of about 7cm and a diameter of about 0.7 cm. Placing the granulated columnar active coke in a well-ventilated area for airing, wherein the airing time is not less than 20 h; it was then cut to an active coke length of 1 cm. The tubular furnace used for carbonization and activation is preheated to 300 ℃ from room temperature, and then the cut active coke is immediately placed in the tubular furnace, nitrogen is introduced, and the temperature is kept for 10min at 300 ℃. Then the temperature is raised to 700 ℃ at a heating rate of 10 ℃/min and kept for 10min, and then raised to 780 ℃ at a heating rate of 5 ℃/min, and water vapor is introduced and kept for 10 min. And then, increasing the temperature to 870 ℃ at a heating rate of 10 ℃/min, keeping the temperature for 20min, then, beginning to cool, closing the water vapor when the temperature is reduced to 500 ℃, switching to a nitrogen atmosphere to continue cooling, and obtaining a sample which is the final active coke after the temperature is reduced to room temperature.
Comparative example 3
Grinding a certain amount of anthracite, bituminous coal, coking coal and asphalt into powder, and uniformly mixing, wherein the ratio of the anthracite, the bituminous coal, the coking coal and the asphalt in the coke making raw materials is 1000 g: 750 g: 750 g: 200 g. Then 300g of 0.25mol/L ferric nitrate solution is added, and the mixture is stirred vigorously for more than 20min to be mixed evenly. Then 200g of cellulose and 200g of coal tar are added into the mixture and stirred to be uniformly mixed; 600mL of water was then added to the mixture and stirring was continued until the mixture was viscous and not loose. The above mixture was slowly poured into a pelletizer to form a rod-shaped activated coke having a length of about 7cm and a diameter of about 0.7 cm. Placing the granulated columnar active coke in a well-ventilated area for airing, wherein the airing time is not less than 20 h; it was then cut to an active coke length of 1 cm. The tubular furnace used for carbonization and activation is preheated to 300 ℃ from room temperature, and then the cut active coke is immediately placed in the tubular furnace, nitrogen is introduced, and the temperature is kept for 10min at 300 ℃. Then the temperature is raised to 700 ℃ at a heating rate of 10 ℃/min and kept for 10min, and then raised to 780 ℃ at a heating rate of 5 ℃/min, and water vapor is introduced and kept for 10 min. And then, the temperature is increased to 870 ℃ at the heating rate of 10 ℃/min and is kept for 20min, then the temperature is reduced, when the temperature is reduced to 500 ℃, the water vapor is closed, nitrogen protection is not used, and the obtained sample is the final active coke after the temperature is reduced to the room temperature.
The following description of the related testing method specifically includes the following steps:
the method for testing the wear resistance and the compression resistance of the active coke comprises the following steps:
weighing 50g of the active coke finished product cut to about 2.5cm, respectively loading into rotary drums at two sides of an intensity tester, tightly closing drum covers, opening the tester, and operating for 20 min. And after the steps are completed, opening the drum cover, placing the active coke on a vibrating screen machine for screening for 180s, collecting the sample remained on the screen layer, weighing, and calculating the mass ratio of the remained active coke to the originally used active coke to obtain the wear resistance. And (3) measuring the compressive strength, namely randomly extracting not less than 20 particles of finished active coke with a smooth surface, testing on a compressive strength instrument, and recording the pressure value at the moment of crushing the sample, namely the compressive strength.
The method for testing the moisture, ash content and volatile components of the activated coke comprises the following steps:
and (3) measuring moisture: grinding the prepared active coke finished product into powder, weighing 3g of the powder and putting the powder into a pre-dried weighing bottle with a cover. The weighing bottle with the sample is opened, and placed in a constant temperature oven at 150 ℃ for 2 h. Taking out the weighing bottle, covering the cover, putting the bottle into a dryer, cooling to room temperature and weighing. After drying for 30min, weighing again until the mass change is not more than 0.0010 g. Note that a set of parallel samples was made. The moisture is calculated as the ratio of the mass lost from the activated coke before and after weighing to the original mass.
And (3) determination of ash content: and (3) placing the cupel into a muffle furnace, burning for 1h at 800 ℃, taking out, placing into a dryer, and cooling to room temperature. 1g of active coke is weighed and evenly distributed in a cupel. Placing the cupel in a muffle furnace at 300 ℃, closing the furnace door, opening the ventilation opening, raising the temperature to 500 ℃ within not less than 30min, keeping the temperature for 30min, continuously raising the temperature to 800 ℃, and burning for 1h at the temperature. And taking out the cupel from the furnace, placing the cupel on a heat-resistant asbestos plate for cooling for 5min, then transferring the cupel to a dryer for cooling to room temperature, and weighing the cupel once every 20min of burning until the mass change does not exceed 0.0010 g. The ash is calculated as the ratio of the mass remaining after complete combustion to the original mass.
Determination of volatile matter: and (3) placing the cupel into a muffle furnace, burning for 1h at 800 ℃, taking out, placing into a dryer, and cooling to room temperature. 1g of active coke is weighed and evenly distributed in a cupel. Placing the cupel in a muffle furnace at 300 ℃, closing the furnace door, continuously heating to 920 ℃, and burning for 8min at the temperature. And taking out the cupel from the furnace, placing the cupel on a heat-resistant asbestos plate for cooling for 5min, then transferring the cupel to a dryer for cooling to room temperature, and weighing the cupel once every 20min of burning until the mass change does not exceed 0.0010 g. The volatile component is calculated as the ratio of the loss of mass of the sample to the mass of the original sample.
Method for testing active iodine value:
firstly, preparing a hydrochloric acid solution with the mass fraction of 5% (measuring 70mL of hydrochloric acid, slowly injecting the hydrochloric acid into 550mL of water, and uniformly mixing); then 0.1000M was prepared (24.820 g sodium thiosulfate in about 75mL fresh boiled distilled water. 0.10g sodium carbonate was added to minimize bacterial decomposition of the solution. the mixture was transferred in full volume to a 1L volumetric flask and diluted to mark. before calibration, it had to stand for at least 4 days. the solution should be stored in an amber glass bottle); then preparing a standard iodine solution: putting 12.700g of iodine and 19.100g of potassium iodide into a beaker, mixing the iodine and the potassium iodide, adding 2-5mL of water into the beaker, and uniformly stirring; water was added continuously-portionwise-portions during stirring (about 5mL each time) until the total amount reached 50-60 mL; the solution was left for at least 4h to ensure that all crystals were dissolved; during the 4h period, stirring is required to be carried out at all times to assist dissolution; the total amount of the mixture was transferred to a volumetric flask of l L and marked with additional distilled water. For iodine solutions, it is most important to control the weight ratio of potassium iodide to iodine to be between 1.5-l. Storing the solution in an amber glass bottle; followed by the preparation of a potassium iodate solution (0.1000mol/L) (4 g or more of a primary standard potassium iodate was dried at 110 ℃ for 2 hours and cooled to room temperature in a desiccator 3.5667mg of dried potassium iodate was dissolved in about 100mL of distilled water, the whole amount was transferred to a L L volumetric flask, supplemented with distilled water for labeling, well mixed and stored in a stoppered glass bottle, finally the starch solution preparation (1.0 g of starch was mixed with 5-19mL of cold water to form a paste, 25mL of water was added to the starch paste with stirring; the starch mixture was poured into L L boiling water with stirring and boiled for 4-5min, the solution had to be ready to use every day.) after the above solution had been prepared, the sodium thiosulfate solution was calibrated (25.0 mL of the prepared potassium iodate solution was pipetted and transferred to a 250mL flask; 2.00g of potassium iodide was titrated, the titration flask was shaken to dissolve the potassium iodide crystals. 5.0mL of concentrated HCl was pipetted into the titration flask and the free iodine was titrated with sodium thiosulfate solution until a pale yellow color appeared in the titration flask). The sodium thiosulfate normality was determined according to the following formula: n1 ═ (PR)/S formula: n1-sodium thiosulfate equivalent concentration, N; p-volume of potassium iodate, mL; R-Potassium iodateEquivalent concentration, N; volume of S-sodium thiosulfate, mL. Titration should be repeated three times and the average taken as the normality result. When the range of each value exceeds 0.0003mol/L, additional titration should be performed. This is followed by calibration of the iodine solution: 25.0mL of the iodine solution was pipetted into a 250mL wide-mouth conical flask and titrated with a calibrated sodium thiosulfate solution until the iodine solution became light yellow. Several drops of starch indicator were added and titration continued drop-by-drop until the last drop turned the solution colorless. The normality of the iodine solution was determined according to the following formula: n is a radical of2＝(SN1) In the formula I: n-equivalent iodine concentration, N; s-volume of sodium thiosulfate, mL; n1-sodium thiosulfate equivalent concentration, N; i-volume of iodine, mL. The titration should be repeated three times so that the error does not exceed 0.003 mol/L. After the solution is calibrated, the iodine value of the prepared active coke finished product is measured. The details of the determination method are shown in GB/T7702.7-2008.
The activated cokes obtained in example 1 and comparative examples 1 to 4 were tested for their properties, and the results are shown in table 1 below:
table 1 results of performance tests of example 1 and comparative examples 1 to 4
As can be seen from the analysis in Table 1, the wear-resistant and compressive strength of the activated coke prepared by the preparation method provided by the application is improved, the moisture, ash and volatile matters are reduced to a certain extent, and the desulfurization and denitrification capabilities are greatly improved. As can be seen from the comparison of example 1 and example 3, in the selection of the binder, cellulose: coal tar 1: 1 ratio of asphalt: coal tar 1: 1 the performance of the obtained active coke is very good.
In addition, the modifier mainly comprises coal tar, pitch, cellulose and iron elements, and does not influence the main steelmaking process.
To further demonstrate the effect of the concentration of iron ions in the ferric nitrate solution on the performance of activated coke, tests were conducted with the concentration of the ferric nitrate solution as a variable, and the results are shown in table 2 below:
TABLE 2 parameter indexes of active coke modified with ferric nitrate of different concentrations
From the analysis of the results in Table 2, it is found that the iodine value is highest when 0.5mol/L ferric nitrate solution is used, but the data is not significantly improved compared with 0.25mol/L ferric nitrate solution, and from the viewpoint of cost, the selection of 0.25mol/L ferric nitrate is helpful to promote the desulfurization efficiency and cost control of the activated coke.
It should be noted that the abrasion resistance (index) in table 2 refers to data obtained by detection using the standard Q/sdnz.
FIG. 1 is an ammonia adsorption infrared spectrum of active coke modified by ferric nitrate with different concentrations in the invention. As is clear from the analysis in fig. 1, as the content of iron element in the activated coke increases, the acid sites on the surface of the activated coke move from weak acid sites to medium and strong acid sites. The increase of the iron content is beneficial to ammonia adsorption so as to improve the denitration efficiency.
In order to demonstrate the effect of different metal salts on the performance of activated coke, tests were carried out with the type of metal salt as a variable, and the results are shown in fig. 2.
As can be seen from the results in FIG. 2, the infrared absorption band of the active coke prepared by adding metal element is significantly stronger in the active coke hydroxyl peak and the aliphatic hydrocarbon peak after adding metal, and the wave number is 1800-800cm-1The absorption peaks of the graphite carbon (C-C) and the oxygen-containing functional group (C ═ O, C-O) become broad and weak. The addition of the metal elements is beneficial to enriching the functional groups on the surface of the active coke, disturbs the graphitization order degree of the active coke to a certain degree and increases the active cokeThe voids of (a).
Using Fe salt, wave number 2750-4000cm-1The range shows that the obvious peaks of O-H and C-H indicate that the use of Fe is more beneficial to the increase of O-H and C-H in the active coke, and the increase of O-H and C-H is beneficial to improving the desulfurization and denitrification performance of the active coke.
Aiming at the characteristics of steel-making enterprises, the invention selects ferric salt solution as an additive, and avoids introducing impurity metal elements in the steel-making process flow.
To further demonstrate the effect of different binder formulations on activated coke performance, tests were run with binder as a variable and the results are shown in table 3 below:
TABLE 3 Effect of Binders on activated Coke Performance parameters
As can be seen from the above table 3, the addition of cellulose and starch has obvious improvement on the desulfurization and denitrification performance of the active coke, and the influence on the wear resistance is small. From iodine value alone, cellulose: coal tar 4: 1 is the best mixture ratio, but the wear-resistant data is the worst at the moment, and the cellulose: coal tar 1: 1 as the best proportion of the binder.
The active coke prepared by the preparation method of the active coke provided by the application has rich pore structure and surface groups, strong wear-resistant compressive strength, excellent flue gas desulfurization and denitrification performance and lower moisture, ash content and volatile matter. Its compression resistance can be up to 886N, its wear resistance can be up to 98.42% (national standard test), and its water content, ash content and volatile component can be respectively reduced to 0.18%, 11.1% and 2.81%. The sulfur capacity is improved to 23.43mg/g from 8.42mg/g of the comparative example, the sulfur capacity is improved to 178.3 percent, and the denitration efficiency is improved to 73.5 percent from 43.17 percent and is improved to 70.3 percent of the comparative example.
The activated coke provided by the application has excellent desulfurization and denitrification performances and good industrial application prospects.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Furthermore, those skilled in the art will appreciate that while some embodiments herein include some features included in other embodiments, rather than other features, combinations of features of different embodiments are meant to be within the scope of the invention and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
Claims (15)
1. A method for preparing activated coke is characterized by comprising the following steps:
mixing a coke-making raw material, metal salt, a binder and water, granulating and drying to obtain a pre-sintered substance; the coking raw materials comprise anthracite, bituminous coal, coking coal and asphalt, the metal salt comprises one or more of ferric salt, cerium salt and vanadium salt, the binder is a mixture of cellulose and coal tar, and the mass ratio of the cellulose to the coal tar in the mixture is 1: 1;
heating the presintered substance in an inert gas atmosphere for carbonization, introducing water vapor into the system for activation, cooling the system to 500 ℃ at 450 ℃, and finally cooling in the inert gas atmosphere to obtain the active coke; the carbonization comprises the following steps: preserving heat for 10-30min at the temperature of 250-350 ℃, and then raising the temperature to 600-700 ℃ and preserving heat for 20-50 min; the activation comprises: the system temperature is raised to 750-800 ℃ and kept for 10-30min after the water vapor is introduced, and then the system temperature is raised to 850-900 ℃ and kept for 20-50 min.
2. The production method according to claim 1, wherein the mass ratio of the anthracite coal, the bituminous coal, the coking coal and the asphalt is (3-5): (2-4): (2-4): (1-3).
3. The method of claim 1, wherein the metal salt comprises one or more of iron nitrate, cerium nitrate, and vanadium nitrate.
4. The method of claim 3, wherein the metal salt is ferric nitrate.
5. The method according to claim 3, wherein the metal salt is prepared as a metal salt solution having a concentration of 0.05 to 0.5 mol/L.
6. The method according to claim 5, wherein the concentration of the ferric nitrate solution is 0.25 mol/L.
7. The preparation method according to claim 5, wherein the mass ratio of the raw coke-making material to the metal salt solution is (8-14): 1.
8. the production method according to claim 1, wherein the mass ratio of the coke-making raw material to the binder is (5-7): 1.
9. The preparation method according to claim 1, wherein the mass ratio of the coke-making raw material to the water is (3-5): 1.
10. The method as claimed in claim 1, wherein the temperature increase rate from 350 ℃ at 250 ℃ to 700 ℃ at 600 ℃ is 10-20 ℃/min.
11. The method according to claim 1, wherein the introduction of the inert gas into the system is stopped when the water vapor is introduced.
12. The method as claimed in claim 1, wherein the temperature rising rate from 600-700 ℃ to 750-800 ℃ is 5-20 ℃/min, and the temperature rising rate from 750-800 ℃ to 850-900 ℃ is 5-20 ℃/min.
13. An activated coke produced by the production method according to any one of claims 1 to 12.
14. The activated coke of claim 13, wherein the activated coke has a length of 1-1.5cm and a diameter of 0.7-0.9 cm.
15. Use of the activated coke of claim 13 or 14 for flue gas desulfurization and denitration.
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| CN112142050A (en) * | 2020-09-29 | 2020-12-29 | 上海应用技术大学 | Method for preparing active coke by adopting antibiotic bacterium residue composite anthracite |
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