CN115318249A - Desulfurization and denitrification active coke and preparation method thereof - Google Patents
Desulfurization and denitrification active coke and preparation method thereof Download PDFInfo
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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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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2257/40—Nitrogen compounds
Abstract
The invention provides desulfurization and denitrification active coke and a preparation method thereof, and belongs to the technical field of active coke. The method provided by the invention mixes coke, adhesive and catalytic active components and then carries out extrusion forming to obtain a formed blank; under the protection of nitrogen, sequentially carrying out carbonization treatment and activation treatment on the formed blank to obtain the desulfurization and denitrification active coke. Compared with the existing preparation method of the active coke, the preparation method of the invention has the advantages of cheap and easily obtained raw materials, low pollution in the preparation process, high strength of the obtained active coke, excellent desulfurization and denitrification performance and good application value.
Description
Technical Field
The invention relates to the technical field of activated coke, in particular to desulfurization and denitrification activated coke and a preparation method thereof.
Background
A great deal of SO discharged into the atmosphere in industrial processes such as fossil fuel combustion, metal smelting, chemical engineering and the like 2 、NO x Greenhouse gases and other harmful substances, not only pollutingIt is environmental friendly and causes waste of sulfur resources. As the environmental requirements become more stringent, NO x Greenhouse gases and other harmful substances such as heavy metal ions, metalloid ions, dioxins and hydrogen halides also require abatement. Among various flue gas purification technologies, the active coke dry method flue gas purification technology is a carbon method flue gas purification technology with the characteristics of resource utilization, wide spectrum purification, water saving, sulfur recovery and the like, and the technology can also remove NO simultaneously x 、SO 2 HCl, HF, dioxin, heavy metals and the like, and has wide development and application prospects.
At present, most flue gas desulfurization devices adopt a lime/limestone-gypsum wet flue gas desulfurization technology, and the method has the technical problems of blockage, scaling and the like and the problem of treatment of desulfurization by-product gypsum. The denitration is generally carried out by a Selective Catalytic Reduction (SCR) method and adding NH 3 As reducing agent, make NO x Is reduced to N 2 However, the conventional denitration catalyst has the problems of high price, low conversion rate, poor regeneration performance and the like. The moving bed active coke desulfurization and denitrification process needs to adopt the formed active coke with high mechanical strength, the currently industrially applied desulfurization and denitrification active coke has large internal diffusion resistance and low internal surface utilization rate, and simultaneously, the loss is caused by crushing and abrasion in the active coke conveying process to cause carbon loss.
Foreign research into activated coke began since the 60's of the last century. The technology for preparing the active coke developed by the German Bergbau-Forschung company takes coal as a raw material, firstly, the coal is crushed into coal dust with a certain granularity, then, the coal dust is oxidized, then, the coal dust is mixed with a binding agent, and finally, the active coke is prepared by carbonization and activation. The research on the active coke in China starts late, coal is generally used as a production raw material, coal tar is used as an adhesive, and the active coke is prepared by processes such as kneading, molding, carbonizing, activating and the like. Therefore, a material with low price, high carbon content, high strength and good desulfurization and denitrification performance is searched to be used as a substitute of high-quality coal and lignite to produce the active coke, the production cost of the active coke can be effectively reduced, and the active coke has good economic value.
Disclosure of Invention
The invention aims to provide desulfurization and denitrification active coke and a preparation method thereof aiming at overcoming the defects of the prior art, and aims to solve the technical problems that the desulfurization and denitrification active coke in the prior art is high in production process cost and pollutes the environment, and the active coke is low in strength and has desulfurization and denitrification activity.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of desulfurization and denitrification active coke, which comprises the following steps:
(1) Mixing coke, an adhesive and a catalytic active component, and then carrying out extrusion forming to obtain a formed blank;
(2) Under the protection of nitrogen, the formed blank is sequentially subjected to carbonization treatment and activation treatment to obtain the desulfurization and denitrification active coke.
Preferably, the mass ratio of the coke, the binder and the catalytic active component is 100:20 to 80:2 to 40.
Preferably, the binder comprises one or more of coal tar pitch, petroleum asphalt and thermoplastic phenolic resin; the coke comprises semicoke and/or petroleum coke.
Preferably, the catalytic active component comprises one or more of chromium slag, aluminum plant waste slag, pyrite cinder, alkali plant white mud, desulfurization ash and carbide slag.
Preferably, the extrusion molding temperature is 20 to 40 ℃, and the extrusion molding pressure is 1 to 10MPa.
Preferably, the carbonization treatment is carried out at 2 to 4 ℃ per minute -1 The temperature is raised to 550-650 ℃ at the temperature raising rate, and the carbonization is carried out for 40-80 min.
Preferably, in the carbonization treatment, the flow rate of nitrogen is 250 to 350 mL/min -1 。
Preferably, the activation treatment is carried out at 4 to 6 ℃ per minute under the condition of introducing steam -1 The temperature is raised to 750-975 ℃ at the temperature raising rate, and the activation is carried out for 30-240 min; the flow rate of the water vapor is 0.2-1.2 mL/min -1 ·g -1 。
Preferably, in the activation treatment, the flow rate of nitrogen gas is 50 to 80 mL/min -1 。
The invention also provides the desulfurization and denitrification active coke prepared by the preparation method.
The invention has the beneficial effects that:
the invention adopts coal pitch or petroleum pitch or thermoplastic phenolic resin as an adhesive, then the adhesive, coke and active components are ground, kneaded and molded, and then carbonized and activated to prepare the desulfurization and denitrification active coke. Compared with the existing preparation method of the active coke, the preparation method of the invention has the advantages of cheap and easily obtained raw materials, low pollution in the preparation process, high strength of the obtained active coke, and excellent desulfurization and denitrification performances.
Detailed Description
The invention provides a preparation method of desulfurization and denitrification active coke, which comprises the following steps:
(1) Mixing coke, an adhesive and a catalytic active component, and then carrying out extrusion forming to obtain a formed blank;
(2) Under the protection of nitrogen, sequentially carrying out carbonization treatment and activation treatment on the formed blank to obtain the desulfurization and denitrification active coke.
In the invention, the mass ratio of the coke, the adhesive and the catalytic active components is 100:20 to 80:2 to 40, preferably 100:30 to 70:5 to 35, more preferably 100: 40-60: 10 to 30.
In the invention, the binder comprises one or more of coal tar pitch, petroleum pitch and thermoplastic phenolic resin, and preferably the coal tar pitch.
In the present invention, the coke comprises semicoke and/or petroleum coke, preferably semicoke.
In the invention, the catalytic active component comprises one or more of chromium slag, aluminum plant waste slag, pyrite cinder, alkali plant white mud, desulfurization ash and carbide slag, preferably one or more of aluminum plant waste slag, pyrite cinder and desulfurization ash.
In the invention, the extrusion forming temperature is 20-40 ℃, preferably 23-38 ℃, and more preferably 25-35 ℃; the pressure for extrusion molding is 1 to 10MPa, preferably 3 to 8MPa, and more preferably 4 to 7MPa.
In the invention, in the step (1), the coke, the adhesive and the catalytic active component are independently ground and crushed, and are mixed after being screened by a sieve of 150-250 meshes.
In the present invention, the particle sizes of the coke, the binder and the catalytically active component are preferably 160 to 240 mesh, and more preferably 180 to 220 mesh, independently.
In the invention, the extrusion molding process is to knead and extrude the strips on a strip extruding machine; the molding blank is a columnar blank with the diameter of 1.5-3 mm, preferably 1.8-2.8 mm, and more preferably 2.0-2.5 mm.
In the invention, the formed blank obtained in the step (1) is naturally dried.
In the invention, the temperature of the natural airing treatment is 20-30 ℃, preferably 22-28 ℃, and more preferably 23-25 ℃; the time for the natural drying treatment is 36 to 60 hours, preferably 40 to 55 hours, and more preferably 45 to 50 hours.
In the invention, the carbonization treatment is carried out at 2-4 ℃ per minute -1 The temperature is raised to 550-650 ℃ at the temperature raising rate, the carbonization is carried out for 40-80 min, preferably 2.5-3.5 ℃ min -1 The temperature is raised to 570-640 ℃ at the temperature raising rate, and the carbonization is carried out for 30-70 min, and the temperature is further preferably 3 ℃ min -1 The temperature is raised to 580-620 ℃ at the temperature raising rate, and the carbonization is carried out for 40-60 min.
In the present invention, the flow rate of nitrogen gas in the carbonization treatment is 250 to 350 mL/min -1 Preferably 270 to 330 mL/min -1 More preferably 290 to 310 mL/min -1 。
In the invention, the activation treatment is carried out at 4-6 ℃ per minute under the condition of introducing water vapor -1 The temperature rising rate is increased to 750-975 ℃, the activation is carried out for 30-240 min, and the temperature rising rate is preferably 4.5-5.5 ℃ min under the condition of introducing water vapor -1 The temperature rise rate is increased to 780-950 ℃, the activation is carried out for 50-220 min, and the temperature rise rate is preferably 5 ℃ min under the condition of introducing water vapor -1 Heating rate of up to 800E to EActivating at 930 deg.c for 90-180 min.
In the present invention, the flow rate of the steam is 0.2 to 1.2 mL/min -1 ·g -1 Preferably 0.3 to 1.0 mL/min -1 ·g -1 More preferably 0.5 to 0.7 mL/min -1 ·g -1 。
In the present invention, the flow rate of nitrogen gas in the activation treatment is 50 to 80 mL/min -1 Preferably 55 to 75 mL/min -1 More preferably 58 to 72 mL/min -1 。
The invention also provides the desulfurization and denitrification active coke prepared by the preparation method.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
1. Performance characterization
(1) Activated coke Strength test
The invention provides an active coke strength testing method according to HG/T2783-1996 molecular sieve crushing resistance testing method, and the DLIV intelligent particle strength tester is used for measuring the compression strength of the active coke. The specific test process is as follows: intercepting a cylindrical active coke sample with the length of 1cm, vertically placing the cylindrical active coke sample in the center of a 1cm mould of a tester, setting the tester as a radial test mode of the cylindrical sample, then starting to test, continuously increasing the pressure applied to the active coke sample by the tester until the sample is broken, recording the display pressure of the tester at the moment, repeating the measurement for 5 times, and taking the average value of the displayed pressure, namely the strength of the sample with the unit of N.
(2) Determination of active iodine adsorption value
The invention determines the iodine adsorption value of the active coke according to GB/T12496.8-1999 test method of wooden active carbon-determination of iodine adsorption value.
(3)N 2 Physical adsorption
The invention adopts a specific surface and porosity analyzer of ASAP 2020PLUS HD88 model of American Micromeritics company to carry out N on an active coke sample 2 And (4) performing physical adsorption testing. The degassing temperature was 573K and the analysis temperature 77K. Proportion tableThe area is analyzed by the BET method and the pore size distribution is analyzed by the t-plot method.
(4) Evaluation of desulfurization and denitrification capabilities of activated coke
The invention utilizes an evaluation device consisting of a fixed bed reactor and a KM9206 type flue gas analyzer produced by Kane company in England to measure the desulfurization and denitrification capacities of the active coke. The specific evaluation process of the desulfurization and denitrification capability of the activated coke is as follows: firstly, crushing an active coke sample, sieving to obtain 10-16-mesh granular active coke, and drying in an oven at 120 ℃ for 12 hours for later use. Then accurately measuring 10mL of the treated active coke sample and filling the sample into a constant temperature section in the middle of the reaction tube; and (3) starting a heating device of the fixed bed reactor, opening a flue gas analyzer after the temperature is raised to the set temperature and is constant for 30min, introducing simulated flue gas, and starting to perform desulfurization capacity test.
The desulfurization reaction conditions are as follows: the flow rate of flue gas is 161.3mL/min, the reaction temperature is 120 ℃, and the air inlet space velocity is 1000h -1 Simulating the composition of the flue gas mixture: SO 2 0.1％，O 2 5％，H 2 O10%, the remainder being N 2 And (4) supplementing.
The denitration reaction conditions are as follows: the flow rate of flue gas is 161.3mL/min, the reaction temperature is 120 ℃, and the air inlet space velocity is 1000h -1 Simulating the composition of the flue gas mixture: NO 0.04%, NH 3 0.04％，O 2 5％，H 2 O (g) 10%, the remainder being composed of N 2 And (4) supplementing.
The main evaluation index of the desulfurization ability of activated coke is SO 2 The removal rate, the penetration time, the sulfur adsorption capacity and the like. Breakthrough time in the context of the present invention means the time during which the removal rate is above 50%, and outlet SO is described 2 Concentration as a function of adsorption time. The absorption of sulfur capacity means that the removal rate is kept above 50 percent and the SO absorbed by the active coke is accumulated 2 The quality of (c). Active coke pair SO 2 The formula for calculating the removal rate is as follows:
in the formula: eta SO2 Represents SO as active coke 2 The removal rate of (1);
C 0 represents SO at the inlet 2 Molar concentration of (c), mol. M -3 ；
C n Representing SO at the outlet 2 Molar concentration of (1), mol. M -3 。
The calculation formula of the sulfur adsorption capacity of the activated coke is as follows:
in the formula: s is the sulfur capacity of the active coke in mg g -1 ；
t n The concentration reaches C at any time n Time, h;
m is the mass of the active coke in the reactor, g;
q is the flow of the simulated flue gas, L/h;
C n at any time, the SO is discharged 2 Concentration of (1), mol. M -3 ；
C 0 Is SO at the inlet of the reactor 2 Concentration of (b), mol. M -3 ；
M is the molar mass of sulfur dioxide, and 64g/mol is taken;
V m 22.4L/mol is taken as the gas molar volume.
The main evaluation indexes of the denitration capability of the activated coke include the removal rate of NO, the penetration time, the denitration adsorption amount and the like. Breakthrough time in the present invention refers to the time at which the removal rate lasts above 34%, describing the change in outlet NO concentration with adsorption time. The denitration adsorption amount means the mass of NO adsorbed by the active coke cumulatively while the removal rate is maintained at 34% or more. The formula for calculating the NO removal rate of the activated coke is as follows:
the removal rate of active coke NO was calculated as follows:
in the formula: eta NO Is an active coke pairRemoval rate of NO,%;
C 0 mol. M concentration of NO at the reactor inlet -3 ；
C n Is the concentration of NO at the outlet of the reactor, mol. M -3 ；
The calculation formula of the denitration adsorption amount of the activated coke is as follows:
in the formula: q is the denitration adsorption quantity of the active coke in a period of time, mg.g -1 ；
n is the total number of measurements;
m is the mass of the active coke in the reactor, g;
i is the number of measurements of the outlet NO;
q is the flow of the simulated flue gas, L/min;
m is the molar mass of NO, and 30g/mol is taken;
C i at the i-th measurement, the NO concentration at the outlet, mol. M -3 ；
C 0 Mol. M concentration of NO at the reactor inlet -3 ；
t i ，t (i-1) Denitration time min at the ith and (i-1) th measurement;
example 1
Grinding and crushing the semicoke, the petroleum asphalt and the pyrite cinder respectively, sieving by a 200-mesh sieve, and mixing the materials according to a mass ratio of 100:20:2, putting the mixture into a kneading machine, uniformly kneading, carrying out extrusion forming at the temperature of 20 ℃ and the pressure of 1MPa, and standing at the temperature of 25 ℃ for 40 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace and nitrogen gas was introduced at a flow rate of 250 mL/min -1 And heating to 600 ℃ at the heating rate of 3 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen gas is 60 mL/min -1 Introducing columnar carbon at the flow rate of 0.2 mL/min -1 ·g -1 Continuously heating to 750 deg.C at a heating rate of 4 deg.C/min under water vapor condition, and activating for 60min to obtain active coke. The BET specific surface area of the obtained active coke is 328m 2 Iodine value of 413mg/g, compressive strength of 127N 2 The adsorption capacity is 86mg/g, and the denitration adsorption capacity is 15mg/g.
Example 2
Respectively grinding and crushing petroleum coke, coal tar and waste residues of an aluminum plant, sieving with a 220-mesh sieve, and mixing the materials according to a mass ratio of 100:50:10, putting the mixture into a kneading machine, uniformly kneading, carrying out extrusion forming at the temperature of 40 ℃ and the pressure of 10MPa, and standing at the temperature of 26 ℃ for 40 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace, and nitrogen gas was introduced at a flow rate of 260 mL/min -1 And heating to 550 ℃ at the heating rate of 3 ℃/min, and carbonizing for 70min to obtain the columnar carbon. The flow rate of nitrogen gas is 60 mL/min -1 Introducing columnar carbon at the flow rate of 0.8 mL/min -1 ·g -1 And continuously heating to 860 ℃ at the heating rate of 5 ℃/min under the condition of water vapor, and performing activation treatment for 120min to obtain the active coke. The BET specific surface area of the obtained active coke is 423m 2 Iodine value of 479mg/g, compressive strength of 178N 2 The adsorption capacity is 103mg/g, and the denitration adsorption capacity is 15.37mg/g.
Example 3
Respectively grinding and crushing petroleum coke, thermoplastic phenolic resin and chromium slag, sieving by a 200-mesh sieve, and mixing the petroleum coke, the thermoplastic phenolic resin and the chromium slag according to a mass ratio of 100:50:15 putting the mixture into a kneading machine, uniformly kneading the mixture, carrying out extrusion forming at the temperature of 35 ℃ and the pressure of 9MPa, and standing the mixture at the temperature of 30 ℃ for 58 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace, and nitrogen gas was introduced at a flow rate of 300 mL/min -1 And heating to 600 ℃ at the heating rate of 4 ℃/min, and carbonizing for 50min to obtain the columnar carbon. The flow of nitrogen is introduced at 55 mL/min -1 Introducing columnar carbon at the flow rate of 0.8 mL/min -1 ·g -1 Continuously heating to 900 ℃ at the heating rate of 5 ℃/min under the condition of water vapor, and carrying out activation treatment for 90min to obtain the active coke. The BET specific surface area of the obtained activated coke is 487m 2 Iodine value of 536mg/g, compression strength 192N 2 The adsorption capacity is 132mg/g, and the denitration adsorption capacity is 18.11mg/g.
Example 4
Mixing semicoke and coal pitchAnd respectively grinding and crushing the desulfurization ash, sieving by a 230-mesh sieve, and mixing the materials according to the mass ratio of 100:60:25, putting the mixture into a kneading machine, uniformly kneading, carrying out extrusion forming at the temperature of 23 ℃ and the pressure of 5MPa, and standing for 45 hours at the temperature of 30 ℃ to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tube-type resistance furnace, and a nitrogen flow of 310 mL/min was introduced -1 And heating to 570 ℃ at the heating rate of 3.5 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen gas is 50 mL/min -1 Introducing columnar carbon at a flow rate of 1.0 mL/min -1 ·g -1 Continuously heating to 780 ℃ at the heating rate of 5.5 ℃/min under the condition of water vapor, and carrying out activation treatment for 240min to obtain the active coke. The BET specific surface area of the obtained active coke is 405m 2 (ii) iodine value of 466mg/g, compressive strength of 268N 2 The adsorption capacity is 88mg/g, and the denitration adsorption capacity is 9.7mg/g.
Example 5
Grinding and crushing the semicoke, the thermoplastic phenolic resin and the carbide slag respectively, sieving the powder with a 250-mesh sieve, and mixing the powder with the coke, the thermoplastic phenolic resin and the carbide slag according to a mass ratio of 100:80:40, putting the mixture into a kneading machine, uniformly kneading, performing extrusion forming at the temperature of 25 ℃ and the pressure of 7MPa, and standing for 51 hours at the temperature of 28 ℃ to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace and nitrogen gas was introduced at a flow rate of 270 mL/min -1 And heating to 650 ℃ at the heating rate of 3 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow of nitrogen is 80 mL/min -1 Introducing columnar carbon at a flow rate of 1.2 mL/min -1 ·g -1 And continuously heating to 880 ℃ at the heating rate of 6 ℃/min under the condition of water vapor, and performing activation treatment for 130min to obtain the active coke. The BET specific surface area of the obtained active coke is 439m 2 Iodine value of 507mg/g, compressive strength of 305N 2 The adsorption capacity is 128mg/g, and the denitration adsorption capacity is 14.66mg/g.
Example 6
Respectively grinding and crushing petroleum coke, petroleum asphalt and desulfurized ash, sieving by a 200-mesh sieve, and mixing the petroleum coke, the petroleum asphalt and the desulfurized ash according to a mass ratio of 100:60:25, putting the mixture into a kneading machine, uniformly kneading, carrying out extrusion forming at the temperature of 27 ℃ and the pressure of 4MPa, and standing at the temperature of 23 ℃ for 52 hours to obtain a formed blank with the diameter of 2 mm; will obtainThe formed blank is put into a tubular resistance furnace, and nitrogen flow is introduced at 280 mL/min -1 And raising the temperature to 610 ℃ at the temperature rise rate of 3 ℃/min, and carbonizing for 40min to obtain the columnar carbon. The flow of nitrogen is 75 mL/min -1 Introducing columnar carbon at a flow rate of 1.0 mL/min -1 ·g -1 Continuously heating to 780 ℃ at the heating rate of 5.5 ℃/min under the condition of water vapor, and carrying out activation treatment for 240min to obtain the active coke. The BET specific surface area of the obtained activated coke is 405m 2 (ii) iodine value of 466mg/g, compressive strength of 268N 2 The adsorption capacity is 115mg/g, and the denitration adsorption capacity is 9.66mg/g.
Example 7
Respectively grinding and crushing petroleum coke, coal pitch, white mud of an alkali factory and carbide slag, sieving by a 200-mesh sieve, and mixing the petroleum coke, the coal pitch, the alkali factory white mud and the carbide slag according to a mass ratio of 100:80:15:5, putting the mixture into a kneading machine, uniformly kneading the mixture, carrying out extrusion forming at the temperature of 31 ℃ and the pressure of 8MPa, and standing the mixture at the temperature of 21 ℃ for 50 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace, and nitrogen gas was introduced at a flow rate of 300 mL/min -1 And heating to 620 ℃ at the heating rate of 3 ℃/min, and carbonizing for 80min to obtain the columnar carbon. The flow rate of nitrogen introduced is 65 mL/min -1 Introducing columnar carbon at a flow rate of 1.2 mL/min -1 ·g -1 Continuously heating to 880 ℃ at the heating rate of 6 ℃/min under the condition of water vapor, and performing activation treatment for 90min to obtain the active coke. The BET specific surface area of the obtained active coke is 509m 2 Iodine value of 548mg/g, compressive strength of 231N 2 The adsorption capacity is 150mg/g, and the denitration adsorption capacity is 25.13mg/g.
Example 8
Respectively grinding and crushing petroleum coke, thermoplastic phenolic resin, chromium slag and carbide slag, sieving with a 230-mesh sieve, and mixing the petroleum coke, the thermoplastic phenolic resin, the chromium slag and the carbide slag according to a mass ratio of 100:65:30:5, putting the mixture into a kneading machine, uniformly kneading the mixture, performing extrusion forming at the temperature of 33 ℃ and the pressure of 6MPa, and standing the mixture at the temperature of 25 ℃ for 48 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace and a nitrogen flow of 340 mL/min was introduced -1 And raising the temperature to 600 ℃ at the temperature rise rate of 3.5 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen gas is 50 mL/min -1 Mixing the columnar carbonAt an inlet flow rate of 0.7 mL/min -1 ·g -1 And continuously heating to 825 deg.C at a heating rate of 4.5 deg.C/min under the condition of water vapor, and activating for 180min to obtain active coke. The BET specific surface area of the obtained active coke is 600m 2 Iodine value of 700mg/g, compressive strength of 380N 2 The adsorption capacity is 160mg/g, and the denitration adsorption capacity is 30mg/g.
Example 9
Grinding and crushing the semicoke, the petroleum asphalt, the waste slag of an aluminum plant and the carbide slag respectively, sieving with a 220-mesh sieve, and mixing the materials according to the mass ratio of 100:40:20:8, putting the mixture into a kneading machine, uniformly kneading, carrying out extrusion forming at the temperature of 38 ℃ and the pressure of 3MPa, and standing at the temperature of 20 ℃ for 49 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace and a nitrogen flow of 330 mL/min was introduced -1 And heating to 580 ℃ at the heating rate of 2 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen gas is 80 mL/min -1 Introducing columnar carbon at the flow rate of 0.8 mL/min -1 ·g -1 And continuously heating to 900 ℃ at the heating rate of 4.5 ℃/min under the condition of water vapor, and carrying out activation treatment for 30min to obtain the active coke. The BET specific surface area of the obtained active coke is 437m 2 Iodine value of 480mg/g, compressive strength of 210N 2 The adsorption capacity is 107mg/g, and the denitration adsorption capacity is 13.36mg/g.
Example 10
Grinding and crushing the semicoke, coal pitch, white mud of an alkali factory and desulfurized ash respectively, sieving with a 250-mesh sieve, and mixing the materials according to a mass ratio of 100:80:16:10, putting the mixture into a kneading machine, uniformly kneading the mixture, carrying out extrusion forming at the temperature of 35 ℃ and the pressure of 8MPa, and standing the mixture at the temperature of 21 ℃ for 55 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank is placed in a tubular resistance furnace, and nitrogen flow is introduced at 350 mL/min -1 And heating to 640 ℃ at the heating rate of 4 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen introduced is 55 mL/min -1 Introducing columnar carbon at the flow rate of 1.1 mL/min -1 ·g -1 And continuously heating to 780 ℃ at the heating rate of 5.8 ℃/min under the condition of water vapor, and carrying out activation treatment for 200min to obtain the active coke. The BET specific surface area of the obtained active coke is 397m 2 Iodine value/g459mg/g, compressive strength 206N 2 The adsorption capacity is 86mg/g, and the denitration adsorption capacity is 5.88mg/g.
Example 11
Respectively grinding and crushing petroleum coke, thermoplastic phenolic resin and waste residues of aluminum plants, sieving by a 230-mesh sieve, and mixing the petroleum coke, the thermoplastic phenolic resin and the waste residues in the aluminum plant according to a mass ratio of 100:50:9, putting the mixture into a kneading machine, uniformly kneading the mixture, carrying out extrusion forming at the temperature of 28 ℃ and the pressure of 9MPa, and standing the mixture at the temperature of 28 ℃ for 36 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace and nitrogen gas was introduced at a flow rate of 300 mL/min -1 And heating to 600 ℃ at the heating rate of 3 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen gas is 60 mL/min -1 Introducing columnar carbon at the flow rate of 1.2 mL/min -1 ·g -1 And continuously heating to 800 ℃ at the heating rate of 6 ℃/min under the condition of water vapor, and performing activation treatment for 210min to obtain the active coke. The BET specific surface area of the obtained active coke is 371m 2 Iodine value of 476mg/g, compressive strength of 195N 2 The adsorption capacity is 71.32mg/g, and the denitration adsorption quantity is 6.21mg/g.
Example 12
Grinding and crushing the semicoke, the petroleum asphalt and the desulfurized ash respectively, sieving by a 200-mesh sieve, and mixing the materials according to a mass ratio of 100:50:40, putting the mixture into a kneading machine, uniformly kneading, carrying out extrusion forming at the temperature of 20 ℃ and the pressure of 2MPa, and standing at the temperature of 25 ℃ for 40 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank is placed in a tubular resistance furnace, and nitrogen flow is introduced at 250 mL/min -1 And heating to 600 ℃ at the heating rate of 3 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen introduced is 65 mL/min -1 Introducing columnar carbon at the flow rate of 0.2 mL/min -1 ·g -1 And continuously heating to 750 ℃ at the heating rate of 4 ℃/min under the condition of water vapor, and performing activation treatment for 60min to obtain the active coke. The BET specific surface area of the obtained active coke is 402m 2 Iodine number 491mg/g, compressive strength 201N, SO 2 The adsorption capacity is 68mg/g, and the denitration adsorption capacity is 4.31mg/g.
Example 13
Respectively grinding and crushing petroleum coke, coal tar and pyrite cinder, and sieving by a 200-mesh sieveSieving, and mixing according to the mass ratio of 100:30:20 putting the mixture into a kneading machine, uniformly kneading, carrying out extrusion forming at the temperature of 20 ℃ and the pressure of 1MPa, and standing at the temperature of 20 ℃ for 40 hours to obtain a formed blank with the diameter of 2 mm; the obtained molded blank was placed in a tubular resistance furnace and nitrogen gas was introduced at a flow rate of 250 mL/min -1 And heating to 600 ℃ at the heating rate of 3 ℃/min, and carbonizing for 1 hour to obtain the columnar carbon. The flow rate of nitrogen gas is 60 mL/min -1 Introducing columnar carbon at the flow rate of 0.2 mL/min -1 ·g -1 And continuously heating to 750 ℃ at the heating rate of 4 ℃/min under the condition of water vapor, and performing activation treatment for 60min to obtain the active coke. The BET specific surface area of the obtained active coke is 389m 2 Iodine value of 449mg/g, compressive strength of 164N 2 The adsorption capacity is 40.12mg/g, and the denitration adsorption quantity is 16.14mg/g.
From the above embodiments, the invention provides a desulfurization and denitrification active coke and a preparation method thereof. According to the experimental test data results, the strength of the desulfurization and denitrification active coke prepared by the method can reach 380N, and the iodine adsorption value can reach 700mg g -1 The specific surface area can reach 600m 2 ·g -1 The sulfur adsorption capacity can reach 160mg/g -1 The denitration adsorption capacity can reach 30mg g -1 . Therefore, the preparation method has the advantages of cheap and easily-obtained raw materials, low pollution in the preparation process, high strength of the obtained product active coke and excellent desulfurization and denitrification performances.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the desulfurization and denitrification active coke is characterized by comprising the following steps:
(1) Mixing coke, an adhesive and a catalytic active component, and then carrying out extrusion forming to obtain a formed blank;
(2) Under the protection of nitrogen, the formed blank is sequentially subjected to carbonization treatment and activation treatment to obtain the desulfurization and denitrification active coke.
2. The preparation method according to claim 1, wherein the mass ratio of the coke, the binder and the catalytic active component is 100:20 to 80:2 to 40.
3. The preparation method of claim 2, wherein the binder comprises one or more of coal pitch, petroleum pitch and thermoplastic phenolic resin; the coke comprises semicoke and/or petroleum coke.
4. The preparation method according to claim 2 or 3, wherein the catalytic active component comprises one or more of chromium slag, aluminum plant waste slag, pyrite cinder, alkali plant white mud, desulfurized ash and carbide slag.
5. The method according to claim 4, wherein the temperature of the extrusion molding is 20 to 40 ℃ and the pressure of the extrusion molding is 1 to 10MPa.
6. The method according to claim 5, wherein the carbonization treatment is performed at 2 to 4 ℃ min -1 The temperature is raised to 550-650 ℃ at the temperature raising rate, and the carbonization is carried out for 40-80 min.
7. The production method according to claim 5 or 6, wherein the flow rate of nitrogen gas in the carbonization treatment is 250 to 350 mL-min -1 。
8. The method according to claim 7, wherein the activation treatment is carried out at 4 to 6 ℃ per minute under the condition of introducing steam -1 The temperature is raised to 750-975 ℃ at the temperature raising rate, and the activation is carried out for 30-240 min; the flow rate of the water vapor is 0.2-1.2 mL/min -1 ·g -1 。
9. The method of claim 8, wherein the method comprisesIn the activation treatment, the flow rate of nitrogen is 50-80 mL/min -1 。
10. The desulfurization and denitrification activated coke obtained by the preparation method of any one of claims 1 to 9.
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