CN117046442B - Preparation system and preparation method for co-production of flue gas activated carbon by coal staged pyrolysis combustion - Google Patents
Preparation system and preparation method for co-production of flue gas activated carbon by coal staged pyrolysis combustion Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 178
- 239000003245 coal Substances 0.000 title claims abstract description 154
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 138
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 134
- 239000003546 flue gas Substances 0.000 title claims abstract description 133
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 106
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 230000004913 activation Effects 0.000 claims abstract description 95
- 239000007789 gas Substances 0.000 claims abstract description 61
- 230000003213 activating effect Effects 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000779 smoke Substances 0.000 claims abstract description 18
- 239000012190 activator Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000000047 product Substances 0.000 claims description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 239000000446 fuel Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 230000007246 mechanism Effects 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000003034 coal gas Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000013459 approach Methods 0.000 abstract description 3
- 238000001994 activation Methods 0.000 description 81
- 238000001179 sorption measurement Methods 0.000 description 26
- 239000011148 porous material Substances 0.000 description 14
- 238000005265 energy consumption Methods 0.000 description 8
- 230000001276 controlling effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
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- 239000001257 hydrogen Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
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- 238000006477 desulfuration reaction Methods 0.000 description 3
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- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B1/00—Methods of steam generation characterised by form of heating method
- F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
- F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B33/00—Steam-generation plants, e.g. comprising steam boilers of different types in mutual association
- F22B33/18—Combinations of steam boilers with other apparatus
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22G—SUPERHEATING OF STEAM
- F22G1/00—Steam superheating characterised by heating method
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23B—METHODS OR APPARATUS FOR COMBUSTION USING ONLY SOLID FUEL
- F23B90/00—Combustion methods not related to a particular type of apparatus
- F23B90/04—Combustion methods not related to a particular type of apparatus including secondary combustion
- F23B90/06—Combustion methods not related to a particular type of apparatus including secondary combustion the primary combustion being a gasification or pyrolysis in a reductive atmosphere
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23C—METHODS OR APPARATUS FOR COMBUSTION USING FLUID FUEL OR SOLID FUEL SUSPENDED IN A CARRIER GAS OR AIR
- F23C10/00—Fluidised bed combustion apparatus
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23L—SUPPLYING AIR OR NON-COMBUSTIBLE LIQUIDS OR GASES TO COMBUSTION APPARATUS IN GENERAL ; VALVES OR DAMPERS SPECIALLY ADAPTED FOR CONTROLLING AIR SUPPLY OR DRAUGHT IN COMBUSTION APPARATUS; INDUCING DRAUGHT IN COMBUSTION APPARATUS; TOPS FOR CHIMNEYS OR VENTILATING SHAFTS; TERMINALS FOR FLUES
- F23L15/00—Heating of air supplied for combustion
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
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- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a preparation system and a preparation method for co-production of flue gas activated carbon by coal fractional pyrolysis combustion, wherein the method comprises the following steps: a pyrolysis step, wherein coal pyrolysis generates coal semicoke; a combustion step, namely burning part of coal semicoke generated in the pyrolysis step to obtain flue gas; an activation step, wherein another part of coal semicoke generated in the pyrolysis step and a part of smoke generated in the combustion step are subjected to an activation reaction to obtain activated carbon and gas-like gas, and a part of smoke is used as an activator of the activation reaction; and the gas-like gas generated in the activation step is used for participating in the combustion of the coal semicoke in the combustion step. The method has the advantages that the activated carbon is co-produced by using the staged pyrolysis combustion system, the flue gas is used as an activating agent for preparing the activated carbon, local material is obtained, the downstream utilization of the coal semicoke is widened, the economy of the system is improved, and an effective technical approach is provided for realizing the stepped efficient and clean utilization of the coal.
Description
Technical Field
The invention relates to the technical field of coal chemical industry, in particular to a preparation system and a preparation method for co-production of flue gas activated carbon by coal fractional pyrolysis combustion.
Background
The energy consumption of China is a large country, and along with the economic development, the energy consumption demand is continuously increased. At present, energy structures are continuously upgraded and converted, china still has a certain degree of dependence on coal for a period of time, and as coal is a non-renewable resource, the coal cannot be efficiently utilized to cause a great amount of resource waste, and meanwhile, the coal also causes more and more serious environmental problems. With macroscopic regulation of national production removal, the living space of traditional high pollution and high energy consumption industries such as coal industry is further compressed. The realization of efficient and clean utilization of coal is one of the important tasks of high-quality development of the economic society of China at present in the face of increasingly highlighted energy and environment contradictions.
The coal semicoke is used as an important pyrolysis product accounting for about 50-70% of the mass of raw coal, is mostly used for direct combustion in the prior art, has low utilization value and low deep processing utilization rate.
The current requirements on pollutant control and treatment are more and more severe, in the adsorption field, the porous material activated carbon has various advantages, has stable structure and no secondary pollution, is easy to regenerate after adsorption saturation, and the traditional preparation method has contradiction between cost and efficiency.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation system and a preparation method for co-production of flue gas activated carbon by coal staged pyrolysis combustion, which take coal semicoke generated by coal pyrolysis as a raw material, and combine flue gas activation generated by coal semicoke combustion to prepare an activated carbon product with excellent adsorption performance, so that local materials are obtained, good economy is realized, the value of the coal semicoke is improved, the energy consumption is reduced, and the coal ladder-type efficient clean utilization is realized.
The invention provides a preparation method of co-production flue gas activated carbon by coal fractional pyrolysis combustion, which comprises the following steps:
A pyrolysis step, wherein coal pyrolysis generates coal semicoke;
a combustion step, namely burning part of coal semicoke generated in the pyrolysis step to obtain flue gas;
an activation step, wherein another part of coal semicoke generated in the pyrolysis step and a part of smoke generated in the combustion step are subjected to an activation reaction to obtain activated carbon and gas-like gas, and a part of smoke is used as an activating agent for the activation reaction; and the gas-like gas generated in the activation step is used for participating in the combustion of the coal semicoke in the combustion step.
According to the technical scheme, part of the coal semicoke obtained by pyrolysis in the pyrolysis device is directly activated, so that the production process is greatly simplified, the utilization efficiency of coal resources is improved, and the downstream utilization of semicoke by coal classification is widened. And meanwhile, part of flue gas generated by burning the coal semicoke is used as an activating agent to react with the coal semicoke, so that local materials are obtained, and the method has better economy. In addition, the gas-like gas in the scheme comprises combustible gases such as hydrogen, carbon monoxide and the like generated by activation, and the combustible gases are discharged into the atmosphere to cause pollution, and the combustible gases are introduced into a combustion step for combustion, so that the combustible gases and the combustion flue gas can be used and treated together, and the environment-friendly gas-like gas is environment-friendly; and secondly, heat can be provided for the reaction in the combustion device, so that the activated carbon is prepared with low energy consumption. Compared with the traditional single physical activation method, the method shortens the activation time, and compared with the chemical activation method, the method has the advantages of low cost, less pollution and no corrosion. Improves the economical efficiency of the system and provides an effective technical approach for realizing the efficient clean utilization of the coal ladder.
In an alternative technical scheme of the invention, in the activation step, the composition of the flue gas is as follows: 5-20% of water vapor, 5-15% of CO 2 and 3-8% of O 2; the temperature of the flue gas is 750-900 ℃, and the residence time of the flue gas is 0.5-1h.
According to the technical scheme, under the conditions of the smoke composition, the smoke concentration and the smoke residence time, the activating agent and the coal semicoke are subjected to an activation reaction, so that the structure and the performance of the activated carbon are improved.
In an alternative technical scheme of the invention, the preparation method further comprises the following steps: a water vapor supply step: the water exchanges heat with another part of flue gas generated in the combustion step to obtain superheated steam, and part of the extracted steam is used as an activating agent in the supplementary activation step; controlling the amount of water vapor extracted to adjust the amount of water vapor in the activation step; a hot air supply step: after the flue gas in the water vapor supply step exchanges heat with water, preheating air, and extracting part of the preheated air to be used as an activating agent in the supplementary activation step; controlling the amount of extraction of the preheated air to adjust the concentration of oxygen in the activation step; a fuel wind supply step: the preheated air is used as fuel wind to participate in the combustion of the coal semicoke in the combustion step.
According to the technical scheme, if the concentration of the water vapor and the oxygen in the flue gas is insufficient, part of the flue gas exchanges heat with water, the heat-exchanged flue gas exchanges heat with air, part of the water vapor and the heat-exchanged air after the heat exchange are extracted to be used as an activating agent for activating, so that the heat energy of the flue gas can be fully utilized, and the water vapor and the oxygen content in the activating process can be regulated; the water vapor has good diffusion performance, and hydrogen generated by the reaction of the water vapor and the coal semicoke is beneficial to the activation process, and the prepared activated carbon has a better pore structure and good adsorption performance; meanwhile, oxygen is favorable for increasing the pore structure of the activated carbon and improving the adsorption performance of the activated carbon; the preheated part of air is used as fuel wind to participate in the combustion of the coal semicoke, so that heat can be provided for the combustion, a combustion main body can be increased, and the recycling of resources is realized.
In an alternative embodiment of the invention, the pyrolysis temperature of the coal in the pyrolysis step is 550-800 ℃.
According to the technical scheme, under the temperature condition, the coal can be quickly heated and pyrolyzed, so that volatile components are quickly separated out, and the coal semicoke is obtained.
The invention provides a preparation system for co-production of flue gas activated carbon by coal staged pyrolysis combustion, which comprises the following steps:
the pyrolysis device is provided with a coal semicoke discharge hole and is used for providing a coal pyrolysis reaction place to generate coal semicoke;
the combustion device is used for providing a reaction place for combustion of the coal semicoke and comprises a coal semicoke feeding port, a coal gas-like inlet and a combustion device flue gas outlet, wherein the coal semicoke feeding port is communicated with a coal semicoke discharging port, and flue gas at the combustion device flue gas outlet is used as an activating agent for activating the coal semicoke;
The activation device provides an activation place of the coal semicoke and comprises an activation device flue gas inlet, a coal semicoke feeding port, a coal-like gas outlet and an activated carbon outlet, wherein the activation device flue gas inlet is communicated with a combustion device flue gas outlet, the coal-like gas outlet is communicated with the coal-like gas inlet, and the coal semicoke feeding port is communicated with a coal semicoke discharging port.
In an alternative technical scheme of the invention, the preparation system further comprises an evaporator and a water supply mechanism, wherein the evaporator is communicated with a flue gas outlet of the combustion device and an outlet of the water supply mechanism, the evaporator is used for generating heat exchange between water and flue gas so as to generate superheated steam, and a steam outlet of the evaporator is communicated with a flue gas inlet of the activation device;
The evaporator also comprises an evaporator flue gas outlet; the preparation system also comprises an air preheater and a flue gas purifier, wherein the air preheater is provided with a preheater flue gas inlet, a preheater flue gas outlet, a first air outlet and a second air outlet, the preheater flue gas inlet is communicated with the evaporator flue gas outlet, the preheater flue gas outlet is communicated with the flue gas purifier, the first air outlet is communicated with the combustion device, and the second air outlet is communicated with the activation device.
According to the technical scheme, the evaporator is communicated with the combustion device, and the rest of the flue gas generated by the combustion device is subjected to heat exchange with water in the evaporator except for the part serving as the activation part, so that superheated steam is generated; the air preheater is connected with the evaporator, and the flue gas subjected to heat exchange by the evaporator exchanges heat with normal-temperature air which is introduced into the air preheater from the outside to generate high-temperature air which is used as fuel wind of the combustion device. Part of steam can be extracted, and the air after the heat exchange of the air preheater is extracted part of the steam is introduced into the activation device for adjusting the concentration of water vapor and/or oxygen in the flue gas activator.
In an alternative technical scheme of the invention, the pyrolysis device further comprises a gas inlet and a pyrolysis product outlet, wherein the pyrolysis product outlet is communicated with the gas inlet, and gas generated by pyrolysis of the coal enters the gas inlet through the pyrolysis product outlet.
According to the technical scheme, the gas is supplemented into the pyrolysis device, so that the recycling of the pyrolysis gas is realized, heat is provided for pyrolysis, and the energy utilization rate is improved.
In the alternative technical scheme of the invention, solid products at the outlet of the combustion device can be put into the combustion device again through the coal semicoke feeding hole for combustion and utilization.
According to the technical scheme, the full utilization of coal resources is facilitated, and the utilization rate of the resources is improved.
In an alternative embodiment of the present invention, the activation device is an activation oven.
According to the technical scheme, the activation furnace is adopted for activation, so that the full activation of the coal semicoke can be ensured, the productivity of the activated carbon is improved, the production cost is saved, and the method is suitable for large-scale production of the activated carbon.
In an alternative embodiment of the present invention, the combustion device is a fluidized bed combustion furnace.
According to the technical scheme, the fluidized bed combustion furnace has the advantages of large heat capacity, high burning strength, full contact between fuel and air, high combustion speed, complete combustion and small residual carbon content, and is suitable for large-scale production of activated carbon.
Drawings
Fig. 1 is a schematic structural diagram of a system for preparing activated carbon for co-production of flue gas by coal staged pyrolysis combustion in an embodiment of the invention.
Fig. 2 is a schematic diagram of a preparation flow of co-production of flue gas activated carbon by coal staged pyrolysis combustion in an embodiment of the invention.
Fig. 3 is a schematic structural diagram of a system for preparing activated carbon for co-production of flue gas by coal staged pyrolysis combustion in an embodiment of the invention.
Fig. 4 is a schematic flow diagram of media in a system for preparing activated carbon from flue gas by coal staged pyrolysis combustion in accordance with an embodiment of the present invention.
FIG. 5 is a scanning electron microscope image of the activated carbon sample of example 1 in an embodiment of the present invention.
Fig. 6 is an infrared spectrum of the activated carbon samples of example 1 and example 2 according to the embodiment of the present invention.
FIG. 7 is a scanning electron microscope image of the activated carbon sample of example 2 in an embodiment of the present invention.
Reference numerals:
A pyrolysis device 1; a coal semicoke discharge port 11; a gas inlet 12; a pyrolysis product outlet 13; a combustion device 2; a coal semicoke feed inlet 21; a gas-like inlet 22; a combustion device flue gas outlet 23; an activation device 3; an activation device flue gas inlet 31; a coal semicoke feed inlet 32; a gas-like outlet 33; an activated carbon outlet 34; an evaporator 4; an evaporator flue gas outlet 41; a turbine group 5; an air preheater 6; a preheater flue gas inlet 61; a preheater flue gas outlet 62; a first air outlet 63; a second air outlet 64; a flue gas cleaner 7; a generator 8; and a blower 9.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, the invention provides a preparation method for co-producing flue gas activated carbon by coal staged pyrolysis combustion, which comprises the following steps:
A pyrolysis step, wherein coal pyrolysis generates coal semicoke;
a combustion step, namely burning part of coal semicoke generated in the pyrolysis step to obtain flue gas;
An activation step, wherein another part of the coal semicoke generated in the pyrolysis step and the smoke generated in the combustion step are subjected to an activation reaction to obtain activated carbon and gas-like gas, and part of the smoke is used as an activating agent for the activation reaction; the gas-like gas generated in the activation step is used for participating in the combustion of the coal semicoke in the combustion step; the gas-like gas is a mixed gas of gas obtained after activation and residual flue gas, and is introduced into a combustion device for combustion, and preferably, the gas obtained after activation comprises combustible gas such as hydrogen, carbon monoxide and the like;
By the method, part of the coal semicoke obtained by pyrolysis in the pyrolysis device is directly activated, so that the production process is greatly simplified, the utilization efficiency of coal resources is improved, and the downstream utilization of semicoke by coal classification is widened. And meanwhile, part of flue gas generated by burning the coal semicoke is used as an activating agent to react with the coal semicoke, so that local materials are obtained, and the method has better economy. In addition, the gas-like gas in the scheme comprises combustible gases such as hydrogen, carbon monoxide and the like generated by activation, and the combustible gases are discharged into the atmosphere to cause pollution, and the combustible gases are introduced into a combustion step for combustion, so that the combustible gases and the combustion flue gas can be used and treated together, and the environment-friendly gas-like gas is environment-friendly; and secondly, heat can be provided for the reaction in the combustion device, so that the activated carbon is prepared with low energy consumption. Compared with the traditional single physical activation method, the method shortens the activation time, and compared with the chemical activation method, the method has the advantages of low cost, less pollution and no corrosion. Improves the economical efficiency of the system and provides an effective technical approach for realizing the efficient clean utilization of the coal ladder.
In a preferred embodiment of the invention, in the activation step, the composition of the flue gas is: 5-20% of water vapor, 5-15% of CO 2 and 3-8% of O 2; the temperature of the flue gas is 750-900 ℃, and the residence time of the flue gas is 0.5-1h. Under the conditions of the smoke composition, the smoke concentration and the smoke residence time, the activating agent and the coal semicoke are subjected to an activating reaction, so that the structure and the performance of the activated carbon are improved. Further preferably, in the activation step, the activation process includes preheating, activating and cooling, and the air is isolated entirely.
In a preferred embodiment of the present invention, as shown in fig. 2, the preparation method further comprises:
A water vapor supply step: the water exchanges heat with another part of flue gas generated in the combustion step to obtain superheated steam, and part of the extracted steam is used as an activating agent in the supplementary activation step; controlling the amount of water vapor extracted to adjust the amount of water vapor in the activation step;
a hot air supply step: after the flue gas in the water vapor supply step exchanges heat with water, preheating air, and extracting part of the preheated air to be used as an activating agent in the supplementary activation step; controlling the amount of extraction of the preheated air to adjust the concentration of oxygen in the activation step;
a fuel wind supply step: the preheated air is used as fuel wind to participate in the combustion of the coal semicoke in the combustion step.
Oxygen is the key of pore formation in the initial stage of activation, good diffusivity of water vapor and hydrogen generated by reaction with carbon are beneficial to the activation process, and the prepared active carbon has a better pore structure and good adsorption performance by controlling the concentration of oxygen and water vapor in the flue gas activator to be in a specified range. If the concentration of the water vapor and the oxygen in the flue gas is insufficient, namely the concentration of the water vapor and the oxygen in the flue gas does not reach the specified range, the heat exchange is carried out on part of the flue gas and the water, the heat exchange is carried out on the flue gas after the heat exchange and the air, and the part of the water vapor and the air after the heat exchange are extracted to be used as an activating agent for activating, so that the heat energy of the flue gas can be fully utilized, the content or the concentration of the water vapor and the oxygen in the flue gas in the activating process can be regulated, the concentration of the oxygen and the water vapor in the flue gas reaches the specified range, and the activated carbon has a better pore structure and good adsorption performance; the generated superheated steam can be used for steam power generation, so that the utilization rate of heat energy is improved; in addition, the preheated air is used as fuel wind to participate in the combustion of the coal semicoke, so that heat can be provided for the combustion, a combustion main body can be increased, and the recycling of resources is realized.
In a preferred embodiment of the invention, in the pyrolysis step, coal is heated in the pyrolysis device 1 to be pyrolyzed to produce pyrolysis gas, coal tar and coal semicoke. The pyrolysis temperature of the coal is 550-800 ℃. Under the temperature condition, the coal can be quickly heated and pyrolyzed, so that volatile components are quickly separated out, and the coal semicoke is obtained. Wherein, the kind of coal is not limited, and bituminous coal, lignite and the like can be selected as reaction raw materials; the pyrolysis atmosphere may be an inert atmosphere or an active atmosphere, and preferably, the pyrolysis atmosphere may be a circulating pyrolysis gas generated in the pyrolysis apparatus 1. Further preferably, the reaction temperature of pyrolysis is 550 ℃ to 700 ℃.
In a preferred embodiment of the present invention, the method further comprises the step of post-treatment: the active carbon is subjected to acid washing, drying and screening treatment to obtain the finished granular active carbon. Specifically, the acid used in the pickling process is not limited in kind, and hydrochloric acid, nitric acid, phosphoric acid and the like can be selected; the drying process is to remove the water brought by the acid washing of the activated carbon by using a drying device to obtain the dried activated carbon; the screening process refers to the step of utilizing a screening device to sort the activated carbon according to the size of the activated carbon particle powder, and finally obtaining the finished product of the granular activated carbon which can be directly used as an adsorbent.
Based on the above method, as shown in fig. 3 and 4, the invention provides a preparation system for co-producing flue gas activated carbon by coal staged pyrolysis combustion, which comprises:
A pyrolysis device 1 for providing a pyrolysis reaction place of coal to generate coal semicoke, wherein the pyrolysis device 1 is provided with a coal semicoke discharge hole 11;
the combustion device 2 is used for providing a reaction place for combustion of the coal semicoke, the combustion device 2 comprises a coal semicoke feeding port 21, a coal gas-like inlet 22 and a combustion device flue gas outlet 23, the coal semicoke feeding port 21 is communicated with the coal semicoke discharging port 11, and flue gas of the combustion device flue gas outlet 23 is used as an activating agent for activating the coal semicoke;
The activation device 3 provides an activation place of the coal semicoke, the activation device 3 comprises an activation device flue gas inlet 31, a coal semicoke feeding port 32, a coal-like gas outlet 33 and an activated carbon outlet 34, the activation device flue gas inlet 31 is communicated with the combustion device flue gas outlet 23, the coal-like gas outlet 33 is communicated with the coal-like gas inlet 22, and the coal semicoke feeding port 32 is communicated with the coal semicoke discharging port 11.
In a preferred embodiment of the present invention, the device further comprises an evaporator 4 and a water supply mechanism, wherein the evaporator 4 is communicated with a flue gas outlet 23 of the combustion device and an outlet of the water supply mechanism (not shown in the figure), and is used for generating heat exchange between water and flue gas so as to generate superheated steam;
Further, the system also comprises a turbine unit 5, wherein the inlet of the turbine unit 5 is communicated with the steam outlet of the evaporator 4, the outlet of the turbine unit 5 is communicated with the flue gas inlet 31 of the activating device, and the turbine unit 5 can be connected with a generator 8 for generating electricity, so that the heat energy utilization rate of superheated steam is improved; the steam at the outlet of the turbine unit 5 is used as an activator for activating the coal semicoke, and the concentration of the steam in the activation device 3 is regulated by controlling the steam entering the activation device 3.
In a preferred embodiment of the invention, the evaporator 4 further comprises an evaporator flue gas outlet 41; the preparation system further comprises an air preheater 6 and a flue gas purifier 7, wherein the air preheater 6 is provided with a preheater flue gas inlet 61, a preheater flue gas outlet 62, a first air outlet 63 and a second air outlet 64, the preheater flue gas inlet 61 is communicated with the evaporator flue gas outlet 41, the preheater flue gas outlet 62 is communicated with the flue gas purifier 7, the first air outlet 63 is communicated with the combustion device 2, and the second air outlet 64 is communicated with the activation device 3; the hot air entering the combustion device 2 serves as fuel wind for the combustion device 2, and the hot air entering the activation device 3 serves to adjust the oxygen concentration in the activation device 3. Preferably, to reduce the number of openings of the evaporator 4, one or more of the preheater flue gas outlet 62, the first air outlet 63 and the second air outlet 64 may be the same outlet, and air may also enter through the preheater flue gas inlet.
In the above manner, the evaporator 4 is communicated with the combustion device 2, and the rest of the flue gas generated by the combustion device 2, except for the part used for activation, exchanges heat with the evaporator 4, so that superheated steam is generated; the turbine set 5 is connected with the evaporator 4, and the superheated steam generated by the evaporator 4 is introduced into the turbine set 5 and can be used for realizing power generation, refrigeration or heat supply; the air preheater 6 is connected to the evaporator 4, and the flue gas after heat exchange by the evaporator 4 exchanges heat with normal temperature air introduced into the air preheater 6 from the outside to generate high temperature air for use as fuel air for the combustion device 2, and the high temperature air and the gas-like gas can enter the combustion device 2 through the same gas inlet (gas-like inlet 22) or can enter the combustion device 1 through separate inlets, which is not limited in this embodiment. Part of the steam can be extracted from the steam turbine unit 5, and the extracted part of the air subjected to heat exchange by the air preheater 6 is introduced into the activation device 3 for adjusting the concentration of water vapor and/or oxygen in the activated flue gas.
In a preferred embodiment of the present invention, the pyrolysis device 1 further comprises a gas inlet 12 and a pyrolysis product outlet 13, the pyrolysis product outlet 13 is communicated with the gas inlet 12, gas generated by pyrolysis of the coal enters the gas inlet 12 through the pyrolysis product outlet 13, and the pyrolysis atmosphere is circulating pyrolysis gas generated in the pyrolysis device 1. Through the mode, the coal gas is supplemented into the pyrolysis device 1, so that the recycling of the pyrolysis gas is realized, heat is provided for pyrolysis, and the energy utilization rate is improved.
In a preferred embodiment of the invention, the solid product at the outlet of the combustion device 2 can be further input into the combustion device 2 through the coal semicoke feeding port 21 for re-combustion and utilization. Through the mode, full utilization of coal is facilitated, and the utilization rate of resources is improved.
In a preferred embodiment of the present invention, the activation device 3 is an activation oven. The activation furnace is adopted for activation, so that the full activation of the coal semicoke can be ensured, the productivity of the activated carbon is improved, the production cost is saved, and the method is suitable for large-scale production of the activated carbon. The specific furnace type of the activation furnace 3 is not limited, and a rotary type, a fixed type or a movable type activation furnace can be selected, preferably, a continuous atmosphere rotary furnace can be adopted, continuous production can be realized, more energy consumption is saved, the heat efficiency is high, and the degree of automation is high. The activation furnace rotates at a constant speed in the activation process, so that the raw materials can be heated more uniformly, the activator is ensured to be in uniform contact with the coal semicoke and perform sufficient reaction, and the influence on the performance of the activated carbon product due to the fact that the coal semicoke is locally excessively activated or insufficient in reaction is avoided.
In this embodiment, the smoke or other gases may be extracted by the high temperature resistant fan 9. The activation process comprises preheating, activating and cooling, and the whole activation process isolates air, so that the formation of an active carbon pore structure is prevented from being influenced by external air, and the stability of the active carbon structure is ensured.
In a preferred embodiment of the present invention, the combustion device 2 is a fluidized bed combustion furnace. The fluidized bed combustion furnace has the advantages of large heat capacity, high burning strength, full contact between fuel and air, high burning speed, complete burning and small residual carbon, and is suitable for large-scale production of active carbon.
In the embodiment, the active carbon preparation system fully utilizes the heat energy generated by the system, reduces the energy consumption of the system, enables the concentration of the flue gas to be adjusted according to the actual activation requirement, directly uses the high-temperature flue gas to react with the pyrolysis semicoke generated by the pyrolysis device 1, realizes local material taking, and obtains the low-cost and high-quality active carbon.
The following further verifies the effect of the embodiments of the present invention with specific practical parameters.
Example 1:
The raw material is low-order bituminous coal, the particle size range of the coal is 0-8 mm, the raw material is fed into a pyrolysis device 1, the operation temperature of the pyrolysis device 1 is regulated to be about 650 ℃, and pyrolysis gas, coal tar, coal semicoke and the like are produced through pyrolysis. Part of the coal semicoke generated by the pyrolysis device 1 is sent to the combustion device 2 for combustion, and the other part is sent to the activation device 3 for activation. The flue gas generated by combustion is used as an activator, and is introduced into an activating device 3 to react with coal semicoke, the operating temperature of the activating device 3 is controlled to be about 850 ℃, and the residence time is 0.5 hour. The smoke component concentration was adjusted to be maintained at a main activation component of about 8% water vapor, 12% CO 2 and 7% oxygen, and the ratio of the smoke flow rate to the feed amount to the activation device 3 was 9m 3/t. The activated gas is introduced into a combustion device 2 for combustion, the combustion temperature is about 900 ℃, and the combustion flue gas is utilized and treated together. And carrying out subsequent pickling, drying and screening treatment on the obtained activated carbon to obtain the finished granular activated carbon.
The prepared activated carbon sample 1 is subjected to performance characterization, and the analysis result is as follows:
table 1 shows the pore structure results of the sample 1 prepared in this embodiment, table 2 shows the adsorption performance results of the sample 1 prepared in this embodiment, fig. 5 shows the surface topography of the activated carbon sample prepared in this embodiment, and fig. 6 shows the infrared spectrogram of the sample 1 prepared in this embodiment.
TABLE 1
TABLE 2
As is clear from Table 1, the yield of the activated carbon sample 1 prepared by the preparation method and the preparation system of the present embodiment is 58.06%, the specific surface area is 798.27m 2/g, the micropore volume is 0.327cm 3/g, the microporosity is 60.11%, and the activated carbon belongs to microporous activated carbon with developed pore structure. As shown in Table 2, the iodine adsorption value of sample 1 was 1056mg/g, CCl 4 adsorption rate was 66%, and the standard of the activated carbon superior product for gas phase and liquid phase adsorption (iodine adsorption value >800mg/g, CCl 4 adsorption rate > 50%) was reached.
As can be seen from FIG. 3, the product of the embodiment is mainly micropores, has uniform and fine round holes distributed on the surface, is suitable for gas phase micromolecule adsorption, can realize a desulfurization value of 30.5mg/g, and meets the standard of high-grade coal particle activated carbon products (desulfurization value >20 mg) for desulfurization and denitrification. As can be seen from fig. 4, the surface-OH basic functional group peak intensity of the activated carbon sample of this example is stronger, and is also suitable for adsorbing acidic contaminants such as sulfur dioxide.
Example 2:
The raw material is low-order bituminous coal, the particle size range of the coal is 0-8 mm, the raw material is fed into a pyrolysis device 1, the operation temperature of the pyrolysis device 1 is regulated to be about 650 ℃, and pyrolysis gas, coal tar, coal semicoke and the like are produced through pyrolysis. Part of the coal semicoke generated by the pyrolysis device 1 is sent to the combustion device 2 for combustion, and the other part is sent to the activation device 3 for activation. The flue gas generated by combustion is used as an activator, and is introduced into an activating device 3 to react with coal semicoke, the operating temperature of the activating device 3 is controlled to be about 850 ℃, and the residence time is 1 hour. The concentration of the flue gas components was adjusted to maintain a major active ingredient of about 8% water vapor, 12% CO 2 and 5% oxygen, and the ratio of the flow rate of the activated flue gas to the feed rate to the activation device 3 was 6m 3/t. The activated gas is introduced into a combustion device 2 for combustion, the combustion temperature is about 900 ℃, and the combustion flue gas is utilized and treated together. And carrying out subsequent pickling, drying and screening treatment on the obtained activated carbon to obtain the finished granular activated carbon.
The prepared activated carbon sample 2 is subjected to performance characterization, and the analysis result is as follows:
Table 3 shows the results of the pore structure of sample 2 prepared in this embodiment, and table 4 shows the results of the adsorption performance of sample 2 prepared in this embodiment. Fig. 7 is a surface morphology graph of the activated carbon sample prepared in this example, and fig. 5, curve 2, is an infrared spectrum graph of the activated carbon sample prepared in this embodiment.
TABLE 3 Table 3
TABLE 4 Table 4
As is clear from Table 3, the yield of the activated carbon sample 2 prepared by the preparation method and the preparation system of the present embodiment is 43.83%, the specific surface area is 732.69m 2/g, the total pore volume is 0.638cm 3/g, and the pore structure is developed. As shown in Table 4, the iodine adsorption value of sample 2 was about 924mg/g, and the adsorption rate of CCl 4 was about 61%, which reached the standard of the activated carbon superior product for gas phase and liquid phase adsorption (iodine adsorption value >800mg/g, adsorption rate of CCl 4 > 50%).
As can be seen from fig. 6, under the same magnification, the surface of the activated carbon product in example 2 is distributed with uniform and fine round holes, and the average pore diameter of the activated carbon sample in the same scale is larger than that of the activated carbon sample prepared in example 1, so that the activated carbon sample is suitable for the adsorption of liquid phase molecules with larger diameters, the phenol removal rate 94.08% can be realized, and the liquid phase adsorption performance is better. As can be seen from curve 2 in fig. 4, the surface c=o acidic functional group peak intensity of the activated carbon sample of this example is stronger, and can be used as the adsorption of the basic adsorbate.
In the two examples provided, the two sample activated carbon products obtained by the preparation method and the preparation system provided by the two embodiments are high-quality activated carbon for adsorption with developed and uniform pore structures, and reach the standards of high-quality activated carbon for gas-phase and liquid-phase adsorption. The activated carbon product suitable for different adsorption applications is obtained by utilizing the coal semicoke and the flue gas generated in the system and regulating and controlling the reaction conditions and the atmosphere, so that the method can realize local material taking, waste utilization, simple technological process and better economy, and is beneficial to industrial application.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. The preparation method of the co-production flue gas activated carbon by coal staged pyrolysis combustion is characterized by comprising the following steps of:
A pyrolysis step, wherein coal pyrolysis generates coal semicoke;
A combustion step of combusting a part of the coal semicoke generated in the pyrolysis step to obtain flue gas;
an activation step, wherein another part of coal semicoke generated in the pyrolysis step and part of smoke generated in the combustion step are subjected to an activation reaction to obtain activated carbon and gas-like gas, the part of smoke is used as an activator of the activation reaction, and the composition of the part of smoke comprises: 5-20% of water vapor, 5-15% of CO 2 and 3-8% of O 2; and the gas-like gas generated in the activation step is used for participating in the combustion of the coal semicoke in the combustion step.
2. The method for preparing the activated carbon by co-production of flue gas by coal staged pyrolysis combustion according to claim 1, wherein in the activation step, the temperature of the flue gas is 750-900 ℃, and the residence time of the flue gas is 0.5-1h.
3. The method for preparing the flue gas activated carbon by co-production through coal staged pyrolysis combustion according to claim 2, further comprising:
A water vapor supply step: heat exchange is carried out between the water and the other part of flue gas generated in the combustion step to obtain superheated steam, and part of the extracted steam is used as an activating agent for supplementing the activating step; controlling the amount of extraction of the water vapor to adjust the content of the water vapor in the activating step;
a hot air supply step: after the flue gas in the water vapor supply step exchanges heat with water, preheating air, and extracting part of the preheated air to be used as an activating agent for supplementing the activating step; controlling the amount of extraction of the preheated air to adjust the concentration of oxygen in the activation step;
a fuel wind supply step: the preheated air is used as fuel wind to participate in the combustion of the coal semicoke in the combustion step.
4. The method for producing flue gas activated carbon by co-production by coal staged pyrolysis combustion according to claim 1, wherein in the pyrolysis step, the pyrolysis temperature of the coal is 550-800 ℃.
5. A production system for producing flue gas activated carbon by coal staged pyrolysis combustion which runs the production method for producing flue gas activated carbon by coal staged pyrolysis combustion as claimed in any one of claims 1 to 4, characterized by comprising:
A pyrolysis device for providing a pyrolysis reaction place of coal to generate coal semicoke, wherein the pyrolysis device is provided with a coal semicoke discharge hole;
The combustion device is used for providing a reaction place for combustion of the coal semicoke and comprises a coal semicoke feeding port, a coal-like gas inlet and a combustion device flue gas outlet, wherein the coal semicoke feeding port is communicated with the coal semicoke discharging port, and flue gas at the combustion device flue gas outlet is used as an activating agent for activation of the coal semicoke;
The activation device provides the activation place of coal semicoke, the activation device includes activation device flue gas entry, coal semicoke feed inlet, class coal gas delivery outlet and active carbon export, activation device flue gas entry with burner flue gas outlet intercommunication, class coal gas delivery outlet with class coal gas entry intercommunication, coal semicoke feed inlet with coal semicoke discharge gate intercommunication.
6. The system for preparing activated carbon by co-production of flue gas by staged pyrolysis combustion of coal according to claim 5, further comprising an evaporator and a water supply mechanism, wherein the evaporator is communicated with the flue gas outlet of the combustion device and the outlet of the water supply mechanism, the evaporator is used for generating heat exchange between water and flue gas so as to generate superheated steam, and the steam outlet of the evaporator is communicated with the flue gas inlet of the activation device;
the evaporator also comprises an evaporator flue gas outlet;
The preparation system further comprises an air preheater and a flue gas purifier, wherein the air preheater is provided with a preheater flue gas inlet, a preheater flue gas outlet, a first air outlet and a second air outlet, the preheater flue gas inlet is communicated with the evaporator flue gas outlet, the preheater flue gas outlet is communicated with the flue gas purifier, the first air outlet is communicated with the combustion device, and the second air outlet is communicated with the activation device.
7. The system for preparing activated carbon by co-production of flue gas by fractional pyrolysis and combustion of coal according to claim 6, wherein the pyrolysis device further comprises a gas inlet and a pyrolysis product outlet, the pyrolysis product outlet is communicated with the gas inlet, and gas generated by pyrolysis of coal enters the gas inlet through the pyrolysis product outlet.
8. The system for preparing the flue gas activated carbon by the coal staged pyrolysis combustion co-production according to claim 6, wherein solid products at the outlet of the combustion device are re-put into the combustion device through the coal semicoke feeding hole for re-combustion and utilization.
9. The production system for co-production of flue gas activated carbon by coal staged pyrolysis combustion according to any one of claims 5 to 8, wherein the activation device is an activation furnace.
10. The production system for co-production of flue gas activated carbon by coal staged pyrolysis combustion according to any one of claims 5 to 8, wherein the combustion device is a fluidized bed combustion furnace.
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