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WO2021258667A1 - Coke activé, son procédé de préparation et son application - Google Patents

Coke activé, son procédé de préparation et son application Download PDF

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Publication number
WO2021258667A1
WO2021258667A1 PCT/CN2020/136090 CN2020136090W WO2021258667A1 WO 2021258667 A1 WO2021258667 A1 WO 2021258667A1 CN 2020136090 W CN2020136090 W CN 2020136090W WO 2021258667 A1 WO2021258667 A1 WO 2021258667A1
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Prior art keywords
activated coke
preparation
temperature
coke
metal salt
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English (en)
Chinese (zh)
Inventor
熊敬超
宋自新
邵雁
向浩
代伟有
刘子豪
郭华军
刘颖
杨振
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China City Environment Protection Engineering Ltd
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China City Environment Protection Engineering Ltd
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Publication of WO2021258667A1 publication Critical patent/WO2021258667A1/fr
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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

Definitions

  • the invention relates to the field of steelmaking, in particular to an activated coke and a preparation method and application thereof.
  • Activated coke flue gas desulfurization and denitrification technology is a flue gas purification technology with a wide-spectrum purification function. Since water is basically not used in the pollution removal process, there is no secondary pollution such as waste water, waste residue, and exhaust gas. Later by-products can be turned into treasures.
  • the mechanical strength, wear resistance and compression performance of activated coke have high requirements.
  • the consumption of activated coke accounts for more than 50% to 70% of the total cost of the activated coke flue gas desulfurization and denitrification process technology, which is a key factor affecting the technical and economic performance of the process.
  • the quality of activated coke is closely related to the consumption of activated coke.
  • the main way to reduce the cost of activated coke flue gas desulfurization and denitrification technology is to improve the performance of activated coke and reduce the consumption and production cost of activated coke.
  • the activated coke prepared by the existing method has limited improvements in desulfurization and denitration performance, mechanical strength, wear resistance and compression resistance.
  • the purpose of the present invention is to provide an activated coke and its preparation method and application to solve the above-mentioned problems.
  • a preparation method of activated coke includes:
  • the pre-fired product is heated in an inert gas atmosphere for carbonization, then water vapor is introduced into the system for activation, and finally the activated coke is obtained by lowering the temperature in the inert gas atmosphere.
  • Metal salt participates in the reaction process in the coking process, changing the groups on the surface of the activated coke, and improving the adsorption performance of the activated coke, especially the desulfurization and denitration performance; the binder is beneficial to the formation of the activated coke, and at the same time, it is beneficial to increase the activated coke during the coking process.
  • the internal micropores can also further improve the desulfurization and denitrification performance;
  • the carbonization in an inactive gas atmosphere is to replace the oxygen in the system, to ensure the progress of the carbonization pyrolysis process, and to avoid oxidation and combustion as much as possible to ensure the effect of the carbonization;
  • Water vapor activation is a process in which water vapor reacts with carbon to generate micropores; the purpose of using inactive gas is to replace water vapor, carbon monoxide, residual oxygen and other gases, maintain the micropore structure of activated coke, and improve desulfurization and denitration. performance.
  • the inactive gas referred to here refers to a gas that does not chemically react with system substances under the reaction temperature condition, such as nitrogen, rare gas, etc. From a cost point of view, nitrogen is preferred.
  • the raw materials for coking include anthracite, bituminous coal, coking coal and pitch;
  • the mass ratio of the anthracite, the bituminous coal, the coking coal and the pitch is (3-5): (2-4): (2-4): (1-3).
  • the selection of coke-making raw materials is the basis for the performance of activated coke, and at the same time helps to reduce costs and optimize resource allocation.
  • the mass ratio of the anthracite, 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 any value between (3-5):(2-4):(2-4):(1-3).
  • the metal salt includes one or more of iron salt, cerium salt, and vanadium salt;
  • the metal salt includes one or more of iron nitrate, cerium nitrate, and vanadium nitrate;
  • the metal salt is iron nitrate
  • the metal salt is configured as a metal salt solution with a concentration of 0.05-0.5 mol/L;
  • the concentration of the ferric nitrate solution is 0.25 mol/L;
  • the mass ratio of the coking raw material to the metal salt solution is (8-14):1.
  • Iron salt, cerium salt, and vanadium salt have a greater effect on improving the performance of activated coke, and iron salt is the most preferred. Among them, 0.25 mol/L of iron salt has the best overall situation of improving effect and cost.
  • the concentration of the metal salt solution can be between 0.05 mol/L, 0.1 mol/L, 0.2 mol/L, 0.3 mol/L, 0.4 mol/L, 0.5 mol/L and 0.05-0.5 mol/L. Any value.
  • the binder includes one or more of coal tar, pitch, cellulose, and starch;
  • the binder is a mixture of cellulose and coal tar
  • the mass ratio of the cellulose and the coal tar in the mixture is 1:1;
  • the mass ratio of the coke-making raw material to the binder is (5-7):1.
  • the effect of the binder in increasing the micropores can be further improved, and the wear resistance and compression resistance of the activated coke can also be improved.
  • the mass ratio of the coke-making raw material to the binder may be any value between 5:1, 6:1, 7:1, and (5-7):1.
  • water is also added when the coke-making raw material, the metal salt and the binder are mixed;
  • the mass ratio of the coking raw material to the water is (3-5):1.
  • Water is added to ensure the molding effect of the pre-fired material (raw meal). It should be noted that the amount of water added can also 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.
  • the mass ratio of the coke-making raw material to the water may be any value between 3:1, 4:1, 5:1, and (3-5):1.
  • the carbonization includes:
  • the heating rate from 250-350°C to 600-700°C is 10-20°C/min;
  • the introduction of inactive gas into the system is stopped.
  • the starting temperature is controlled to 250-350°C, because the pre-fired material will quickly break and cannot be formed when the temperature is too low; the temperature rise to 600-700°C and the heat preservation stage are the carbonization process, mainly carbonization occurs, and at the same time The volatile matter evaporates.
  • This stage is an important time period for determining the strength and performance of activated coke.
  • the control of the heating rate is to ensure that the reaction of each stage is carried out in an orderly and controllable condition, which is beneficial to improve the performance of the activated coke.
  • the temperature control during the carbonization process can be 250-350°C, for example, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C , 350°C and any value between 250-350°C
  • the holding time can be any value between 10min, 15min, 20min, 25min, 30min and 10-30min; for the 600-700°C interval, for example, it can be 600 °C, 610°C, 620°C, 630°C, 640°C, 650°C, 660°C, 670°C, 680°C, 690°C, 700°C and any value between 600-700°C
  • the holding time can be 20min, 25min , 30min, 35min, 40min, 45min, 50min and any value between 20-50min.
  • the heating rate from 250-350°C to 600-700°C can be any value between 10°C/min, 15°C/
  • the activation includes:
  • the heating rate from 600-700°C to 750-800°C is 5-20°C/min
  • the heating rate from 750-800°C to 850-900°C is 5-20°C/min.
  • the temperature control during the activation process can be any value between 750°C, 760°C, 770°C, 780°C, 790°C, 800°C, and 750-800°C for the range of 750-800°C.
  • the holding time can be any value between 10min, 15min, 20min, 25min, 30min and 10-30min; for the interval of 850-900°C, for example, it can be 850°C, 860°C, 870°C, 880°C, 890°C,
  • the holding time can be any value between 20min, 25min, 30min, 35min, 40min, 45min, 50min and 20-50min.
  • the heating rate from 600-700°C to 750-800°C and the heating rate from 750-800°C to 850-900°C can be independently 5°C/min, 10°C/min, 15°C/min, 20 Any value between °C/min and 5-20°C/min.
  • the temperature of the system is lowered to 450-500° C. before the “temperature is lowered in the inert gas atmosphere”.
  • the cooling process is divided into two stages in order to ensure the structure of the micropores and avoid closure and collapse.
  • the temperature of the system can be lowered to any value between 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, and 450-500°C.
  • a kind of activated coke which is prepared by using the described preparation method
  • the length of the activated coke is 1-1.5 cm, and the diameter is 0.7-0.9 cm.
  • the length of the active coke can be any value between 1cm, 1.1cm, 1.2cm, 1.3cm, 1.4cm, 1.5cm and 1-1.5cm, and the diameter can be 0.7cm, 0.8cm, 0.9cm. cm and any value between 0.7-0.9cm.
  • the beneficial effects of the present invention include:
  • the preparation method of activated coke provided in the present application by adding a metal salt, carbonization in an inert gas atmosphere, activation by water vapor, and cooling in an inert gas atmosphere, the obtained activated coke is excellent in desulfurization, denitrification, mechanical strength, and resistance.
  • the properties such as wear resistance and compression have been greatly improved; the preparation method is relatively simple, and has good industrial application prospects.
  • Figure 1 shows the ammonia adsorption infrared spectrum of activated coke modified with different concentrations of ferric nitrate
  • Figure 2 shows the infrared spectra of activated coke modified by different metal salts.
  • compositions, step, method, product, or device containing the listed elements is not necessarily limited to those elements, but may include other elements not explicitly listed or inherent in such a composition, step, method, product, or device Elements.
  • Parts by mass refers to the basic measurement unit that represents the mass ratio relationship of multiple components.
  • 1 part can represent any unit mass, such as 1g, or 2.689g. If we say that the parts by mass of component A is a part, and the parts by mass of component B are part b, it means the ratio of the mass of component A to the mass of component B is a:b. Or, it means that the mass of component A is aK, and the mass of component B is bK (K is an arbitrary number and represents a multiple factor). It should not be misunderstood that, unlike the number of parts by mass, the sum of parts by mass of all components is not limited to 100 parts.
  • a and/or B includes (A and B) and (A or B).
  • a certain amount of anthracite, bituminous coal, coking coal, and pitch are ground and mixed uniformly, and the ratio of anthracite, bituminous coal, coking coal, and pitch in the coking raw materials is 1000g: 750g: 750g: 200g.
  • 300 g of ferric nitrate solution with a concentration of 0.25 mol/L and stir vigorously for more than 20 minutes to make it evenly mixed.
  • 200 g of cellulose and 200 g of coal tar to the above mixture and stir to mix evenly; then add 600 mL of water to the above mixture and continue stirring until the mixture is viscous and not loose.
  • the above mixture is slowly poured into a granulator to form a rod-shaped activated coke with a length of about 7 cm and a diameter of about 0.7 cm.
  • the columnar activated coke after granulation is placed in a well-ventilated area to dry for no less than 20h; then it is cut into activated coke with a length of 1 cm.
  • the tube furnace used for carbonization activation was preheated from room temperature to 300°C, and then the cut activated coke was immediately placed in the tube furnace, and nitrogen gas was introduced and kept at 300°C for 10 minutes.
  • the temperature was increased to 700°C at a temperature increase rate of 10°C/min and maintained for 10 minutes, and then the temperature was increased to 780°C at a rate of 5°C/min, and steam was introduced and maintained for 10 minutes.
  • the temperature was increased to 870°C at a heating rate of 10°C/min and kept for 20 minutes, and then the temperature began to drop.
  • the temperature dropped to 500°C the water vapor was turned off and the temperature was continued to be switched to a nitrogen atmosphere.
  • the sample obtained after the temperature dropped to room temperature was The final activated coke.
  • a certain amount of anthracite, bituminous coal, coking coal, and pitch are ground and mixed uniformly, and the ratio of anthracite, bituminous coal, coking coal, and pitch in the coking raw materials is 1000g: 750g: 750g: 200g.
  • 200 g of ferric nitrate solution with a concentration of 0.5 mol/L and stir vigorously for more than 20 minutes to make it evenly mixed.
  • 200 g of starch and 200 g of coal tar to the above mixture and stir to mix evenly; then add 900 mL of water to the above mixture and continue stirring until the mixture is viscous and not loose.
  • the above mixture is slowly poured into a granulator to form a rod-shaped activated coke with a length of about 7 cm and a diameter of about 0.7 cm.
  • the columnar activated coke after granulation is placed in a well-ventilated area to dry for no less than 20h; then it is cut into activated coke with a length of 1 cm.
  • the tube furnace used for carbonization activation was preheated from room temperature to 300°C, and then the cut activated coke was immediately placed in the tube furnace, and nitrogen gas was introduced and kept at 300°C for 10 minutes.
  • the temperature was increased to 700°C at a temperature increase rate of 10°C/min and maintained for 10 minutes, and then the temperature was increased to 780°C at a rate of 5°C/min, and steam was introduced and maintained for 10 minutes.
  • the temperature was increased to 870°C at a heating rate of 10°C/min and kept for 20 minutes, and then the temperature began to drop.
  • the temperature dropped to 500°C the water vapor was turned off and the temperature was continued to be switched to a nitrogen atmosphere.
  • the sample obtained after the temperature dropped to room temperature was The final activated coke.
  • a certain amount of anthracite, bituminous coal, coking coal, and pitch are ground and mixed uniformly, and the ratio of anthracite, bituminous coal, coking coal, and pitch in the coking raw materials is 1000g: 750g: 750g: 200g.
  • 250 g of ferric nitrate solution with a concentration of 0.25 mol/L and stir vigorously for more than 20 minutes to make it evenly mixed.
  • 200 g of pitch and 200 g of coal tar to the above mixture and stir to make it uniformly mixed; then add 800 mL of water to the above mixture and continue stirring until the mixture is viscous and not loose.
  • the above mixture is slowly poured into a granulator to form a rod-shaped activated coke with a length of about 7 cm and a diameter of about 0.7 cm.
  • the columnar activated coke after granulation is placed in a well-ventilated area to dry for no less than 20h; then it is cut into activated coke with a length of 1 cm.
  • the tube furnace used for carbonization activation was preheated from room temperature to 300°C, and then the cut activated coke was immediately placed in the tube furnace, and steam was introduced and kept at 300°C for 10 minutes.
  • the temperature was increased to 700°C at a temperature increase rate of 10°C/min and maintained for 10 minutes, and then the temperature was increased to 780°C at a rate of 5°C/min, and steam was introduced and maintained for 10 minutes.
  • the temperature was increased to 870°C at a heating rate of 10°C/min and kept for 20 minutes, and then the temperature began to drop.
  • the temperature dropped to 500°C the water vapor was turned off and the temperature was continued to be switched to a nitrogen atmosphere.
  • the sample obtained after the temperature dropped to room temperature was The final activated coke.
  • a certain amount of anthracite, bituminous coal, coking coal, and pitch are ground and mixed uniformly, and the ratio of anthracite, bituminous coal, coking coal, and pitch in the coking raw materials is 1000g: 750g: 750g: 200g.
  • 200-300mL ferric nitrate solution with a concentration of 0.2mol/L and stir vigorously for more than 20min to make it evenly mixed.
  • 320 g of cellulose and 80 g of coal tar were added to the above mixture and stirred to make it uniformly mixed; then 700 mL of water was added to the above mixture, and stirring was continued until the mixture was viscous and not loose.
  • the above mixture is slowly poured into a granulator to form a rod-shaped activated coke with a length of about 7 cm and a diameter of about 0.7 cm.
  • the columnar activated coke after granulation is placed in a well-ventilated area to dry for no less than 20h; then it is cut into activated coke with a length of 1 cm.
  • the tube furnace used for carbonization activation was preheated from room temperature to 300°C, and then the cut activated coke was immediately placed in the tube furnace, and nitrogen gas was introduced and kept at 300°C for 10 minutes.
  • the temperature was increased to 700°C at a temperature increase rate of 10°C/min and maintained for 10 minutes, and then the temperature was increased to 780°C at a rate of 5°C/min, and steam was introduced and maintained for 10 minutes.
  • the temperature was increased to 870°C at a heating rate of 10°C/min and kept for 20 minutes, and then the temperature began to drop.
  • the temperature dropped to 500°C the water vapor was turned off and the temperature was continued to be switched to a nitrogen atmosphere.
  • the sample obtained after the temperature dropped to room temperature was The final activated coke.
  • a certain amount of anthracite, bituminous coal, coking coal, and pitch are ground and mixed uniformly, and the ratio of anthracite, bituminous coal, coking coal, and pitch in the coking raw materials is 1000g: 750g: 750g: 200g.
  • 200 g of pitch and 200 g of coal tar are added to the above mixture and stir to make it uniformly mixed; then add 600 mL of water to the above mixture and continue stirring until the mixture is viscous and not loose.
  • the above mixture is slowly poured into a granulator to form a rod-shaped activated coke with a length of about 7 cm and a diameter of about 0.7 cm.
  • the columnar activated coke after granulation is placed in a well-ventilated area to dry for no less than 20h; then it is cut into activated coke with a length of 1 cm.
  • the tube furnace used for carbonization activation was preheated from room temperature to 300°C, and then the cut activated coke was immediately placed in the tube furnace, and nitrogen gas was introduced and kept at 300°C for 10 minutes. Subsequently, the temperature was increased to 700°C at a temperature increase rate of 10°C/min and maintained for 10 minutes, and then the temperature was increased to 780°C at a rate of 5°C/min, and steam was introduced and maintained for 10 minutes.
  • the temperature was increased to 870°C at a heating rate of 10°C/min and kept for 20 minutes, and then the temperature began to drop.
  • the temperature dropped to 500°C, the water vapor was turned off without nitrogen protection.
  • the sample obtained after it is cooled to room temperature is the final activated coke.
  • a certain amount of anthracite, bituminous coal, coking coal, and pitch are ground and mixed uniformly, and the ratio of anthracite, bituminous coal, coking coal, and pitch in the coking raw materials is 1000g: 750g: 750g: 200g.
  • 200 g of cellulose and 200 g of coal tar to the above mixture and stir to mix evenly; then add 600 mL of water to the above mixture and continue stirring until the mixture is viscous and not loose.
  • the above mixture is slowly poured into a granulator to form a rod-shaped activated coke with a length of about 7 cm and a diameter of about 0.7 cm.
  • the columnar activated coke after granulation is placed in a well-ventilated area to dry for no less than 20h; then it is cut into activated coke with a length of 1 cm.
  • the tube furnace used for carbonization activation was preheated from room temperature to 300°C, and then the cut activated coke was immediately placed in the tube furnace, and nitrogen gas was introduced and kept at 300°C for 10 minutes. Subsequently, the temperature was increased to 700°C at a temperature increase rate of 10°C/min and maintained for 10 minutes, and then the temperature was increased to 780°C at a rate of 5°C/min, and steam was introduced and maintained for 10 minutes.
  • the temperature was increased to 870°C at a heating rate of 10°C/min and kept for 20 minutes, and then the temperature began to drop.
  • the temperature dropped to 500°C the water vapor was turned off and the temperature was continued to be switched to a nitrogen atmosphere.
  • the sample obtained after the temperature dropped to room temperature was The final activated coke.
  • a certain amount of anthracite, bituminous coal, coking coal, and pitch are ground and mixed uniformly, and the ratio of anthracite, bituminous coal, coking coal, and pitch in the coking raw materials is 1000g: 750g: 750g: 200g.
  • 300 g of ferric nitrate solution with a concentration of 0.25 mol/L and stir vigorously for more than 20 minutes to make it evenly mixed.
  • 200 g of cellulose and 200 g of coal tar to the above mixture and stir to mix evenly; then add 600 mL of water to the above mixture and continue stirring until the mixture is viscous and not loose.
  • the above mixture is slowly poured into a granulator to form a rod-shaped activated coke with a length of about 7 cm and a diameter of about 0.7 cm.
  • the columnar activated coke after granulation is placed in a well-ventilated area to dry for no less than 20h; then it is cut into activated coke with a length of 1 cm.
  • the tube furnace used for carbonization activation was preheated from room temperature to 300°C, and then the cut activated coke was immediately placed in the tube furnace, and nitrogen gas was introduced and kept at 300°C for 10 minutes.
  • the temperature was increased to 700°C at a temperature increase rate of 10°C/min and maintained for 10 minutes, and then the temperature was increased to 780°C at a rate of 5°C/min, and steam was introduced and maintained for 10 minutes.
  • the temperature was increased to 870°C at a heating rate of 10°C/min and kept for 20 minutes, and then the temperature began to drop.
  • the temperature dropped to 500°C the water vapor was turned off and nitrogen protection was not used.
  • the sample obtained after the temperature dropped to room temperature was the final activity Coke.
  • Moisture determination Grind the prepared activated coke into powder, weigh 3g and put it into a pre-dried weighing bottle with a lid. Open the lid of the weighing bottle containing the sample and put it in a constant temperature oven at 150°C for 2 hours. Take out the weighing bottle, close the lid, put it in a desiccator, cool to room temperature and weigh. Weigh again every 30 minutes after drying until the mass change is not more than 0.0010g. Note, pay attention to making a set of parallel samples. The calculation of moisture is the ratio of the lost mass of the active coke before and after weighing to the original mass.
  • Ash determination Put the ash dish in a muffle furnace, burn it at 800°C for 1 hour, take it out, put it in a desiccator, and cool it to room temperature. Weigh 1g of activated coke and evenly distribute it in the ash dish. Place the ash dish in a muffle furnace at 300°C, close the furnace door, open the vent, raise it to 500°C in no less than 30 minutes, keep it for 30 minutes, continue to heat up to 800°C, and burn at this temperature for 1 hour. Take out the ash pan from the furnace and place it on a heat-resistant asbestos board to cool for 5 minutes, then transfer it to a desiccator to cool to room temperature, and then weigh it every 20 minutes after burning until the mass change does not exceed 0.0010g. The calculation of ash is the ratio of the mass remaining after complete combustion to the original mass.
  • Determination of volatile matter Put the ash dish in a muffle furnace, burn it at 800°C for 1 hour, take it out and put it in a desiccator, and cool it to room temperature. Weigh 1g of activated coke and evenly distribute it in the ash dish. Place the ash dish in a muffle furnace at 300°C, close the furnace door, continue to heat up to 920°C, and burn for 8 minutes at this temperature. Take out the ash pan from the furnace and place it on a heat-resistant asbestos board to cool for 5 minutes, then transfer it to a desiccator to cool to room temperature, and then weigh it every 20 minutes after burning until the mass change does not exceed 0.0010g. The calculation of volatile matter is the ratio of the mass loss of the sample to the mass of the original sample.
  • the solution should be stored in amber glass bottles Medium); Then configure the standard iodine solution: Measure 12.700g of iodine and 19.100g of potassium iodide into a beaker, mix iodine and potassium iodide, add 2-5mL of water to the beaker, and stir evenly; continue during the stirring process-small portion-small Add water in portions (about 5 mL each time) until the total amount reaches 50-60 mL; leave the solution for at least 4 hours to ensure that all crystals are dissolved; during this 4 hours, stir from time to time to aid dissolution; transfer the entire amount of the mixture to 1L Fill the volumetric flask with distilled water up to the mark.
  • the iodine solution the most important thing is to control the weight ratio of potassium iodide to iodine between 1.5-1.
  • the solution is stored in an amber glass bottle; then it is prepared with potassium iodate solution (0.1000mol/L) (4g or more than 4g of primary standard potassium iodate is dried at 110°C for 2h, and placed in a desiccator Cool to room temperature.
  • potassium iodate solution (0.1000mol/L) (4g or more than 4g of primary standard potassium iodate is dried at 110°C for 2h, and placed in a desiccator Cool to room temperature.
  • Dissolve 3.5667mg of dry potassium iodate in approximately 100mL of distilled water. Transfer the entire amount to a 1L volumetric flask, add distilled water to the mark. Mix well and store in a stoppered glass bottle.
  • starch Solution configuration mix 1.0g starch with 5-19mL cold water to form a paste, add 25mL water to the starch paste while stirring. Pour the starch mixture into 1L boiling water with stirring and boil for 4-5min. The liquid must be present every day (Prepare for current use).
  • the sodium thiosulfate solution needs to be calibrated (take 25.0 mL of the prepared potassium iodate solution with a pipette, and transfer it to a 250 mL titration flask. Add 2.00 g of potassium iodide and shake to titrate. Bottle to dissolve potassium iodide crystals.
  • N1 (PR)/S where: N1—sodium thiosulfate equivalent concentration, N; P—potassium iodate volume, mL; R—potassium iodate equivalent concentration, N; S—sodium thiosulfate volume, mL.
  • N1 sodium thiosulfate equivalent concentration, N
  • P potassium iodate volume, mL
  • R potassium iodate equivalent concentration
  • S sodium thiosulfate volume, mL.
  • N 2 (SN 1 )/I
  • N the equivalent concentration of iodine, N
  • S volume of sodium thiosulfate, mL
  • N1 thio Sodium sulfate equivalent concentration, N
  • I volume of iodine, mL.
  • Example 1 The properties of the activated coke obtained in Example 1 and Comparative Examples 1-4 were tested, and the results are shown in Table 1 below:
  • the modifier is mainly composed of coal tar, pitch, cellulose and iron elements and will not affect the main steelmaking process.
  • the iodine value is the highest when 0.5mol/L ferric nitrate solution is used, but compared with 0.25mol/L ferric nitrate solution, the data increase is not obvious.
  • the dosage concentration is selected as 0.25mol/L ferric nitrate will help promote the desulfurization efficiency and cost control of activated coke.
  • wear resistance in Table 2 refers to the data obtained by using the columnar activated coke standard Q/SDNZ.H. TL ⁇ J1-2013 for flue gas purification.
  • Figure 1 is the ammonia adsorption infrared spectrum of activated coke modified with different concentrations of ferric nitrate in the present invention. It can be seen from the analysis of Figure 1 that as the content of iron in the activated coke increases, the acidic sites on the surface of the activated coke move from weak acid sites to medium and strong acid sites. It shows that the increase of iron content is conducive to the adsorption of ammonia gas and thus the denitrification efficiency.
  • the OH and CH have obvious peaks in the range of wave number 2750-4000cm -1 , indicating that the use of Fe is more conducive to the increase of OH and CH in the activated coke, and the increase of OH and CH is conducive to the improvement.
  • the desulfurization and denitration performance of activated coke When Fe salt is used , the OH and CH have obvious peaks in the range of wave number 2750-4000cm -1 , indicating that the use of Fe is more conducive to the increase of OH and CH in the activated coke, and the increase of OH and CH is conducive to the improvement.
  • the desulfurization and denitration performance of activated coke are shown in the range of wave number 2750-4000cm -1 , indicating that the use of Fe is more conducive to the increase of OH and CH in the activated coke, and the increase of OH and CH is conducive to the improvement.
  • the desulfurization and denitration performance of activated coke When Fe salt is used
  • the present invention preferably uses iron salt solution as an additive to avoid introducing impurity metal elements in the steel-making process.
  • the activated coke prepared by the method for preparing activated coke provided in this application has abundant pore structure and surface groups, strong abrasion and compressive strength, excellent flue gas desulfurization and denitrification performance, and low moisture, ash, and volatility point. Its compressive strength can reach 886N, abrasion resistance can reach 98.42% (national standard test), and the moisture, ash, and volatile content can be as low as 0.18%, 11.1%, and 2.81%, respectively.
  • the sulfur capacity was increased from 8.42 mg/g in the comparative example to 23.43 mg/g, an increase of 178.3%, and the denitrification efficiency was increased from 43.17% in the comparative example to 73.5%, an increase of 70.3%.
  • the activated coke provided by this application has excellent desulfurization and denitration performance, and has good industrial application prospects.

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Abstract

L'invention concerne un coke activé, son procédé de préparation et son application. Le procédé de préparation d'un coke activé consiste à : mélanger une matière première pour la préparation de coke, un sel métallique et un liant, et effectuer une granulation et un séchage pour obtenir une substance de pré-frittage ; chauffer la substance de pré-frittage dans une atmosphère de gaz inerte pour la carbonisation, puis faire passer la vapeur d'eau dans le système d'activation ; et enfin, refroidir celle-ci dans l'atmosphère de gaz inerte pour obtenir le coke activé. Le coke activé est préparé à l'aide du procédé de préparation. Le coke activé est appliqué à la désulfuration et à la dénitrification de gaz de combustion. Le coke activé préparé présente une résistance à l'usure et une résistance à la compression élevées et moins d'humidité, de cendres et de matière volatile, est simple dans le procédé de synthèse et de faible coût, et présente d'excellentes performances de désulfuration et de dénitrification et une bonne perspective d'application industrielle.
PCT/CN2020/136090 2020-06-24 2020-12-14 Coke activé, son procédé de préparation et son application Ceased WO2021258667A1 (fr)

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CN116081620A (zh) * 2022-12-07 2023-05-09 山西大学 一种利用焦化废水浓盐水制备脱硫脱硝活性炭的方法
CN116099498A (zh) * 2023-01-16 2023-05-12 煤炭科学技术研究院有限公司 一种利用气化渣分选精炭制备脱硫炭的方法
CN117142468A (zh) * 2023-07-12 2023-12-01 西安热工研究院有限公司 一种分级孔不定型活性焦及其制备方法和应用

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CN114602532B (zh) * 2022-05-05 2024-07-16 山东万达环保科技有限公司 一种脱硫脱硝活性焦催化剂的制备方法及其在烟气脱硫脱硝中的应用
CN115010226B (zh) * 2022-08-09 2022-11-22 河北科技大学 一种膜电解处理高氯有机废水装置

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CN116099498A (zh) * 2023-01-16 2023-05-12 煤炭科学技术研究院有限公司 一种利用气化渣分选精炭制备脱硫炭的方法
CN117142468A (zh) * 2023-07-12 2023-12-01 西安热工研究院有限公司 一种分级孔不定型活性焦及其制备方法和应用

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