CN115676828A - Activated carbon preparation device and method - Google Patents
Activated carbon preparation device and method Download PDFInfo
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- CN115676828A CN115676828A CN202110855579.XA CN202110855579A CN115676828A CN 115676828 A CN115676828 A CN 115676828A CN 202110855579 A CN202110855579 A CN 202110855579A CN 115676828 A CN115676828 A CN 115676828A
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Abstract
The invention relates to the technical field of activated carbon preparation, in particular to an activated carbon preparation device and method. One aspect of the present invention provides an activated carbon preparation apparatus, comprising a moving bed reactor, wherein the moving bed reactor comprises an oxidant inlet, and a preheating section, a combustion section, and an activation section which are sequentially arranged along a material moving direction, wherein: a preheating section for drying, devolatilizing and low-temperature oxidizing the materials in an oxidant atmosphere to produce combustible gas and carbonized materials; the combustion section is used for carrying out oxidation reaction on combustible gas and carbonized materials in the atmosphere of an oxidant and supplying heat generated by the oxidation reaction to the preheating section and the activation section; the activation section is used for carrying out activation reaction on the carbonized material under the atmosphere of an activating agent so as to generate activated carbon and coal gas; an oxidant inlet for introducing an oxidant into the moving bed reactor; wherein the activating agent is derived from the products of the preheating section and the combustion section.
Description
Technical Field
The invention relates to the technical field of activated carbon preparation, in particular to an activated carbon preparation device and method.
Background
The active carbon is a porous carbon material prepared by taking high-carbon substances such as charcoal, wood chips, various shells, coal, petroleum coke and the like as raw materials and performing special treatment such as carbonization, activation and the like. Due to the advantages of developed pore structure, larger specific surface area, excellent adsorption performance, wide raw material source, low price and the like, the method is widely applied to refining and purifying processes in the industries of military industry, food, metallurgy, chemical industry, environmental protection, medicine and the like. With the emergence of new application fields of active carbon such as hydrogen storage, electrode materials, soil remediation, radiation protection and the like and the gradual strict national environmental protection requirements, the demand of the active carbon will be further increased.
Up to now, the preparation technology of activated carbon is numerous. The materials can be classified into a fixed bed type, a moving bed type and a fluidized bed type according to the relative motion state of the materials in the carbonization furnace and the activation furnace. In these three types of apparatus, the material will be maintained in a stationary state, in a moving state intermittently or continuously, and in a fluidized state of the particles, respectively.
The fixed bed furnace is mainly used in the early stage and is gradually eliminated due to the defects of high energy consumption, serious pollution, high labor intensity, relatively poor product quality and the like. The fluidized bed furnace also gradually loses market competitiveness due to the problems of short residence time, unfavorable continuous production and the like. At present, a rake furnace, a Slapple furnace, a rotary furnace and the like widely applied to activated carbon enterprises belong to a moving bed type, and have the advantages of high production capacity, relatively high thermal efficiency and the like. Nevertheless, under the pressure of gradual upgrade of national policy efforts such as energy conservation, consumption reduction, pollution prevention and the like, the activated carbon production devices still expose a lot of problems. Firstly, most of the preparation of the activated carbon adopts a carbonization and activation two-step method, and the high-temperature treatment process of the materials is finished in a carbonization furnace and an activation furnace respectively, so that the integration level of the whole system is lower, and the heat utilization efficiency in the preparation process of the activated carbon is insufficient. The transfer of material between the two devices brings additional operations, increasing the amount of labour. Secondly, the material heating mode of the prior art is usually indirect or direct heating through high-temperature activated gas, and the heating mode needs an external auxiliary heat source and has larger energy consumption. The indirect heating also causes the problems of long material heating period, poor heat exchange efficiency, uneven heating of the activated carbon and the like. Thirdly, in the process of preparing the activated carbon, the generation of tar is difficult to avoid, and in order to solve the tar problem, a tar treatment device is often required to be additionally arranged, so that the production cost of the activated carbon is increased. In addition, the existing activated carbon production equipment has the problems of complex structure, high equipment investment, large occupied area and the like.
Disclosure of Invention
Technical problem to be solved
In view of the above, the present invention provides an apparatus and a method for preparing activated carbon to at least partially solve the above technical problems.
(II) technical scheme
One aspect of the present invention provides an activated carbon preparation apparatus, comprising a moving bed reactor, wherein the moving bed reactor comprises an oxidant inlet, and a preheating section, a combustion section, and an activation section which are sequentially arranged along a material moving direction, wherein:
a preheating section for drying, devolatilizing and low temperature oxidizing the material in an oxidant atmosphere to produce a combustible gas and a carbonized material;
the combustion section is used for carrying out oxidation reaction on combustible gas and carbonized materials in an oxidant atmosphere and supplying heat generated by the oxidation reaction to the preheating section and the activation section;
the activation section is used for carrying out activation reaction on the carbonized material under the atmosphere of an activating agent so as to generate activated carbon and coal gas;
an oxidant inlet for introducing an oxidant into the moving bed reactor;
wherein the activating agent is derived from the products of the preheating section and the combustion section.
According to an embodiment of the present invention, the moving bed reactor further comprises a guide section and a fuel section arranged in sequence along the material moving direction, wherein:
the flow guide section is used for guiding the material;
the fuel section is used for loading materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section;
wherein, the oxidant inlet is communicated with the inlet of the flow guide section;
wherein, the height ratio of the preheating section to the burning section is more than 2: 1, the height of the burning section is more than or equal to 0.5m, and the height of the activating section is more than 2m.
According to an embodiment of the invention, the apparatus further comprises a feeding device, a cooling device, wherein:
the feeding device is communicated with the inlet of the flow guide section and is used for feeding materials into the moving bed reaction furnace;
and the cooling device is communicated with an outlet of the activation section and is used for generating cooled activated carbon and second temperature water after the heat exchange is carried out on the first temperature water and the activated carbon in the cooling device, wherein the temperature of the second temperature water is higher than that of the first temperature water.
According to an embodiment of the invention, the apparatus further comprises:
the combustor is used for combusting the coal gas to generate first-temperature flue gas;
and the tube bundle heat exchanger is arranged in the activation section and is communicated with a first temperature flue gas outlet of the combustor so as to provide heat of the first temperature flue gas for the activation reaction of the carbonized material in the activation section through the tube bundle heat exchanger and then generate second temperature flue gas, wherein the temperature of the second temperature flue gas is lower than that of the first temperature flue gas.
According to an embodiment of the invention, the apparatus further comprises:
the flue gas heat exchanger is communicated with the second temperature flue gas outlet of the tube bundle heat exchanger and is used for generating saturated steam after heat exchange is carried out between the second temperature flue gas and the second temperature water in the flue gas heat exchanger;
the combustion section heat exchanger is arranged in the fuel section and used for heating saturated steam into superheated steam by utilizing heat generated by oxidation reaction of the combustion section;
and the steam spray pipe is arranged in the activation section and used for feeding superheated steam serving as a supplementary activating agent into the activation section.
According to an embodiment of the present invention, the moving bed reactor further comprises a diversion section and a fuel section arranged in sequence along the moving direction of the material, wherein:
the flow guide section is used for guiding the material;
the fuel section is used for loading materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section;
wherein the oxidant inlet is in direct communication with the combustion section.
According to an embodiment of the invention, wherein: and auxiliary airflow is introduced into an inlet of the flow guide section and is used for providing a back pressure environment for the space above the fuel section of the moving bed reaction furnace.
The invention also provides an activated carbon preparation method by utilizing the activated carbon preparation device, which comprises the following steps:
introducing an oxidant into the moving bed reaction furnace through an oxidant inlet of the moving bed reaction furnace;
feeding the material into a moving bed reactor so that the oxidant and the material react in sequence in a preheating section, a combustion section and an activation section of the moving bed reactor, wherein:
in a preheating section, the materials are dried, devolatilized and oxidized at low temperature in the atmosphere of an oxidant to generate combustible gas and carbonized materials;
in the combustion section, the combustible gas and the carbonized material are subjected to oxidation reaction in the oxidant atmosphere, and the oxidation reaction in the combustion section generates heat so as to provide the heat to the preheating section and the activation section;
in the activation section, the carbonized material is subjected to activation reaction in the atmosphere of an activating agent to generate activated carbon and coal gas;
wherein the activating agent is derived from the products of the preheating section and the combustion section.
According to an embodiment of the invention, wherein:
the method comprises the following steps that materials sequentially pass through a flow guide section and a fuel section of the moving bed reaction furnace before being sent into a preheating section of the moving bed reaction furnace, wherein the flow guide section is used for guiding the materials; the fuel section is used for loading materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section;
the oxidant is introduced into the diversion section of the moving bed reactor;
the method further comprises the following steps:
discharging the activated carbon and the coal gas out of the moving bed reaction furnace;
by adjusting the discharge rate of the activated carbon, the oxidizing agentParameters such that the reaction in the moving bed reactor satisfies stable operating conditions, wherein the stable operating conditions are: downward moving speed v of material AC Equal to the ignition front upward propagation velocity vf, where the parameters of the oxidizer include the flow rate of the oxidizer, or the oxygen concentration in the oxidizer.
According to an embodiment of the invention, wherein:
the method comprises the following steps that materials sequentially pass through a flow guide section and a fuel section of a moving bed reaction furnace before being sent into a preheating section of the moving bed reaction furnace, wherein the flow guide section is used for guiding the materials; the fuel section is used for loading materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section;
the oxidant is introduced into the combustion section of the moving bed reactor;
the method further comprises the following steps:
discharging the activated carbon and the coal gas out of the moving bed reaction furnace;
the reaction in the moving bed reaction furnace meets the stable operation conditions by adjusting the discharge rate of the activated carbon and the parameters of the oxidant, wherein the stable operation conditions are as follows: downward moving speed v of material AC Not greater than upward propagation velocity v of the ignition front f ；
In the combustion section, the oxidation reaction comprises homogeneous phase oxidation reaction of combustible gas and heterogeneous phase oxidation reaction of carbonized materials;
the method further comprises the following steps:
the oxygen concentration in the oxidant is adjusted to be more than 50 percent so as to strengthen the homogeneous oxidation reaction and weaken the heterogeneous oxidation reaction.
(III) advantageous effects
The activated carbon preparation device provided by the invention has the following advantages:
a. the heat required by the preparation of the activated carbon is released only by the combustion of a small amount of raw materials, the heat utilization rate is high, a high-power auxiliary heat source is not required to be provided, and the energy consumption is low;
b. the raw materials are self-heated by combustion of part of the raw materials, and the in-situ utilization of the heat released by combustion is realized, so that the self-heating mode has high heat utilization rate, high heating rate and uniform heating of the materials;
c. based on the bed layer partition conversion characteristic, tar is generated in a preheating section and is subjected to high-temperature oxidation in a combustion section and activated carbon catalysis in an activation section to be cracked, no tar is contained in tail gas, and the method is clean and environment-friendly and does not need tar treatment equipment;
d. raw material combustion in the reaction furnace only needs to provide 0.01-0.1 m/s of oxidant, the oxidant consumption is small, the flow rate is low, high-power gas supply equipment is not needed, and the oxidant cost is low;
e. part of activating agent is CO generated in preheating and burning stage in preparation process of activated carbon 2 And H 2 O, fully utilizing effective components in the raw materials, showing a certain self-activation property and saving the using amount of an activating agent;
f. the raw materials are integrally carbonized and activated in the reaction furnace, so that a plurality of devices are prevented from being used simultaneously, and the system integration level is high;
g. the continuous production of the activated carbon can be realized, the production efficiency is high, and the single machine productivity is high;
h. the device is simple, easy to process and construct and low in equipment investment cost.
Drawings
Fig. 1 is a schematic structural diagram of an activated carbon preparation apparatus according to an embodiment of the present invention;
fig. 2 is a schematic structural diagram of an activated carbon preparation apparatus according to another embodiment of the present invention;
fig. 3 is a schematic structural diagram of an activated carbon preparation apparatus according to another embodiment of the present invention.
Description of the reference numerals:
1-a feeding device; 2-moving bed reaction furnace, 21-diversion section; 22-a fuel section; 23-a preheating section; 24-a combustion section; 25-an activation section; 26-an ignition device; 3-a cooling device; 4-a combustion section heat exchanger; 5-a steam nozzle; 6-a tube bundle heat exchanger; 7-a burner; 8-flue gas heat exchanger.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments. It should be understood that these descriptions are illustrative only and are not intended to limit the scope of the present disclosure. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the disclosure. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The terms "comprises," "comprising," and the like, as used herein, specify the presence of stated features, steps, operations, and/or components, but do not preclude the presence or addition of one or more other features, steps, operations, or components.
All terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. It is noted that the terms used herein should be interpreted as having a meaning that is consistent with the context of this specification and should not be interpreted in an idealized or overly formal sense.
In those instances where a convention analogous to "at least one of A, B, and C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, and C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.). Where a convention analogous to "at least one of A, B, or C, etc." is used, in general such a construction is intended in the sense one having skill in the art would understand the convention (e.g., "a system having at least one of A, B, or C" would include but not be limited to systems that have A alone, B alone, C alone, A and B together, A and C together, B and C together, and/or A, B, and C together, etc.).
The invention provides an active carbon preparation device which comprises a moving bed reaction furnace, wherein the moving bed reaction furnace comprises an oxidant inlet, a preheating section, a combustion section and an activation section, wherein the preheating section, the combustion section and the activation section are sequentially arranged along the moving direction of materials, the lower part of the preheating section is connected with the upper part of the combustion section, and the lower part of the combustion section is connected with the upper part of the activation section. Wherein:
a preheating section for drying, devolatilizing and low temperature oxidizing the material in an oxidant atmosphere to produce a combustible gas and a carbonized material;
the combustion section is used for carrying out oxidation reaction on combustible gas and carbonized materials in the atmosphere of an oxidant and supplying heat generated by the oxidation reaction to the preheating section and the activation section;
the activation section is used for carrying out activation reaction on the carbonized material under the atmosphere of an activating agent so as to generate activated carbon and coal gas;
an oxidant inlet for introducing an oxidant into the moving bed reactor; wherein the activating agent is derived from the products of the preheating section and the combustion section.
According to an embodiment of the present invention, the moving bed reactor further comprises a guide section and a fuel section arranged in sequence along the material moving direction, wherein: the flow guide section is used for guiding the material; the fuel section is used for loading materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section; wherein the oxidant inlet is communicated with the inlet of the flow guide section.
According to the embodiment of the invention, according to the partition characteristic of the material bed layer, in order to avoid that the preheating section is too short and the fuel is pyrolyzed in advance due to too large influence of the combustion section, the height ratio of the preheating section to the combustion section is set to be more than 2: 1, the height of the combustion section is more than or equal to 0.5m, and the height of the activation section is more than 2m in order to ensure the activation residence time of the carbonized material in the furnace.
According to an embodiment of the invention, the device further comprises a feeding device and a cooling device, wherein:
the feeding device is communicated with the inlet of the flow guide section and is used for feeding materials into the moving bed reaction furnace;
and the cooling device is communicated with an outlet of the activation section and is used for generating cooled activated carbon and second temperature water after the heat exchange of the first temperature water and the activated carbon is carried out in the cooling device, wherein the temperature of the second temperature water is higher than that of the first temperature water.
According to the embodiment of the invention, through the device, the preheating, combustion and activation of the materials are carried out in the same moving bed reaction furnace, so that the self-heating is realized, namely, the heat generated by the oxidation reaction is provided for the preheating section and the activation section by means of the combustion of part of the raw materials in the combustion section, the self-heating of the materials is realized, the in-situ utilization of the heat released by combustion is realized, and the self-heating mode has the advantages of high heat utilization rate, high heating rate and uniform material heating. And because of high energy utilization rate, the heat required by the preparation of the activated carbon is released only by the combustion of a small amount of raw materials, the heat utilization rate is high, a high-power auxiliary heat source is not required to be provided, and the energy consumption is low.
According to the embodiment of the invention, the partial activating agent is used as CO generated in the preheating and combustion stage in the preparation process of the activated carbon by the device 2 And H 2 And O, the active ingredients in the raw materials are fully utilized, a certain self-activation property is shown, and the using amount of an activating agent is saved.
According to the embodiment of the invention, by the device, based on the bed layer partition conversion characteristic, tar is generated in the preheating section and is subjected to high-temperature oxidation in the combustion section and cracking by activated carbon catalysis in the activation section, and the tail gas is free of tar, clean and environment-friendly, and does not need tar treatment equipment.
According to the embodiment of the invention, by the device, the raw materials are integrally carbonized and activated in the reaction furnace, so that a plurality of devices are prevented from being used simultaneously, and the system integration level is high; the continuous production of the activated carbon can be realized, the production efficiency is high, and the single machine productivity is high; and the device is simple, easy to process and construct and low in equipment investment cost.
Example one
Fig. 1 is a schematic structural diagram of an activated carbon preparation apparatus according to an embodiment of the present invention. As shown in fig. 1, the apparatus includes a feeding device 1, a moving bed reactor 2, and a cooling device 3.
Wherein, the moving bed reactor 1 consists of a diversion section 21, a fuel section 22, a preheating section 23, a combustion section 24 and an activation section 25. The flow guide section 21 is positioned at the top of the moving bed reactor 2, the upper part of the flow guide section 21 is connected with the feeding device 1 and the oxidant gas source, the lower part of the flow guide section 21 is connected with the upper part of the fuel section 22, the lower part of the fuel section 22 is connected with the upper part of the preheating section 23, the lower part of the preheating section 23 is connected with the upper part of the combustion section 24, and the lower part of the combustion section 24 is connected with the upper part of the activation section 25. Wherein, a flow guide body can be arranged in the flow guide section 21, so that the materials can fall uniformly; a level gauge may be disposed within the fuel section 22 for monitoring the level to maintain the level within the fuel section 22; the lower part of the activation section 25 is conical, and an ignition device is arranged at the necking part and is used for starting the furnace and igniting; a plurality of temperature measuring points are arranged along the height of the moving bed reactor 2 for monitoring the process of preparing activated carbon in the reactor, in particular for limiting the position of the ignition front in the reactor within the combustion section 22 by monitoring.
The feeding device 1 and the oxidant inlet are connected with the inlet at the top of the moving bed reaction furnace 2 and are directly communicated with the diversion section 21, and the raw material for preparing the active carbon and the oxidant are added into the moving bed reaction furnace 2 in the same direction. After the raw materials are subjected to a carbon activation process in the moving bed reaction furnace 2, the raw materials and the generated coal gas are discharged out of the reaction furnace together by means of gravity, and then gas-solid separation is carried out. Cooling the high-temperature activated carbon in a cooling device 3 to obtain an activated carbon product; the separated high-temperature coal gas is a byproduct in the preparation process of the activated carbon and can be directly used as gaseous fuel.
According to the partition characteristic of the material bed layer, the ratio of the minimum height of the preheating section to the minimum height of the combustion section is more than 2: 1, and the height of the combustion section is not less than 0.5m. In order to ensure the activation residence time of the carbonized material in the furnace, the height of the activation section should be higher than 2m.
Example two
Fig. 2 is a schematic structural diagram of an activated carbon preparation apparatus according to another embodiment of the present invention. As shown in fig. 2, the structure of the device in this embodiment is substantially the same as that of the device in the embodiment of fig. 1, except that:
wherein the oxidant inlet is directly communicated with the combustion section; and the inlet of the flow guide section is introduced with auxiliary airflow, and the auxiliary airflow is used for providing a back pressure environment for the space above the fuel section of the moving bed reaction furnace.
As shown in fig. 2, the top of the reaction furnace is connected with an auxiliary gas flow, the upper part of the combustion section of the reaction furnace is connected with an oxidant gas source, and the oxidant inlet is arranged in a mode of realizing uniform air distribution in the furnace. At the moment, the majority of the gas introduced into the reaction furnace is oxidant; the auxiliary gas flow accounts for a very small part, and the flow control of the auxiliary gas flow is based on the principle that the flow is not higher than the minimum oxygen flow required by the self-sustaining combustion of the raw materials.
The secondary gas stream may be a low oxygen concentration gas, e.g. air, CO 2 Inert gas, or a mixed gas thereof; the oxidant may be air or oxygen-enriched gas.
In this embodiment, the auxiliary air flow functions as: the reaction furnace has the advantages that certain back pressure is provided for the space above the reaction furnace, smooth feeding is guaranteed, upward and reverse channeling of gas in the furnace is avoided, and the reaction furnace is favorable for carrying steam and pyrolysis gas generated in the preheating section to the downstream reaction section (the combustion section and the activation section). The function of the oxidant is as follows: the oxygen required for the combustion reaction taking place in the combustion section is provided.
In the device of the embodiment shown in fig. 1, in order to maintain stable preparation of the activated carbon, the ignition front position needs to be strictly limited in the combustion section, and stable operation needs to be ensured: downward moving speed v of material AC Equal to the upward propagation velocity v of the ignition front f 。
In this oxidant arrangement shown in FIG. 2, even though the reactor is at v f ＞v AC Can still strictly limit the ignition front position in the combustion section, particularly the oxidant nozzle. Therefore, the temperature in the furnace can be increased by increasing the parameters of the oxidant, and the activation of the subsequent carbonized materials is further strengthened without influencing the stable operation of the reaction furnace. Under the condition, the discharging speed of the activated carbon can be even reduced, the activation retention time of the activated carbon in the furnace is further prolonged, and the operating condition range for preparing the activated carbon is widened. In this case, the reaction in the moving bed reactor satisfies the stable operation conditions by adjusting the discharge rate of the activated carbon and the parameters of the oxidizing agent, wherein the stable operation conditions are as follows: downward moving speed v of the material AC Not greater than upward propagation velocity v of the ignition front f 。
EXAMPLE III
Fig. 3 is a schematic structural diagram of an activated carbon preparation apparatus according to another embodiment of the present invention. The device structure in this embodiment is substantially the same as that shown in the embodiment of fig. 1, except that:
the device also comprises a combustor 7, a tube bundle heat exchanger 6, a flue gas heat exchanger 8, a combustion section heat exchanger 4 and a steam spray pipe 5.
The burner 7 is used for burning coal gas to generate first-temperature flue gas.
And the tube bundle heat exchanger 6 is arranged in the activation section, is communicated with a first temperature flue gas outlet of the combustor, and is used for providing heat of the first temperature flue gas for activation reaction of the carbonized material in the activation section through the tube bundle heat exchanger to generate second temperature flue gas, wherein the temperature of the second temperature flue gas is lower than that of the first temperature flue gas.
In this embodiment, the cooling device 3 is configured to generate cooled activated carbon and water with the second temperature after the heat exchange is performed between the water with the first temperature and the activated carbon in the cooling device.
And the flue gas heat exchanger 8 is communicated with the second temperature flue gas outlet of the tube bundle heat exchanger and is used for generating saturated water vapor after the heat exchange is carried out between the second temperature flue gas and the second temperature water in the flue gas heat exchanger.
And the combustion section heat exchanger 4 is arranged in the fuel section and used for heating saturated steam into superheated steam by utilizing heat generated by oxidation reaction of the combustion section.
And the steam spray pipe 5 is arranged in the activation section and is used for feeding superheated steam serving as a supplementary activating agent into the activation section.
In the device shown in fig. 3, water with a first temperature at normal temperature is heated by a cooling device, a flue gas heat exchanger and a combustion section heat exchanger in sequence, is converted into superheated steam at 600-800 ℃, and is introduced into an activation furnace through a steam spray pipe.
In this embodiment, the above apparatus can enhance the activated carbon preparation process, specifically: 1) Except for active gases generated by the raw materials in the preheating section and the combustion section, water vapor is additionally introduced into the activation section of the reaction furnace to be used as an auxiliary activating agent for activating the carbonized materials, so that the concentration of the activating agent in the activation section is greatly improved, and the forward progress of the activation reaction of the carbonized materials is promoted; 2) In the preparation process of the activated carbon, high-temperature flue gas at 1000-1300 ℃ generated by burning byproduct gas in a burner is used for maintaining the temperature of an activation section at 800-950 ℃ through a tube bundle heat exchanger and maintaining the temperature condition required by activation of carbonized materials at the middle lower part of the activation section.
In addition, the flow of the oxidant can be increased, or the oxygen concentration of the oxidant can be increased, the combustion strength in the combustion section is enhanced, on one hand, the temperature of the carbonized material is increased to ensure the efficient activation of the subsequent carbonized material, on the other hand, the water vapor can be further heated to a state of directly participating in the activation reaction through the heat exchanger of the combustion section, and the energy utilization rate is increased.
According to the embodiment of the invention, by adopting the device, the heat generated in the preparation process of the activated carbon is fully utilized, and the overall temperature of the activation section of the reaction furnace is maintained in a higher interval. Meanwhile, the concentration of the activating agent in the reaction furnace is greatly improved, and the activation reaction is favorably carried out. Under the measures, the length of the activation section of the reaction furnace can be properly prolonged so as to increase the retention time of materials in the furnace and realize the preparation of the activated carbon with higher specific surface area.
Another aspect of the present invention also provides a method for preparing activated carbon using the above apparatus for preparing activated carbon, which can be understood with reference to the apparatus structure shown in fig. 1, the method comprising:
s1: introducing an oxidant into the moving bed reaction furnace through an oxidant inlet of the moving bed reaction furnace;
s2: feeding the material into a moving bed reactor so that the oxidant and the material react in sequence in a preheating section, a combustion section and an activation section of the moving bed reactor, wherein:
in a preheating section, the materials are dried, devolatilized and oxidized at low temperature in the atmosphere of an oxidant to generate combustible gas and carbonized materials;
in the combustion section, the combustible gas and the carbonized materials are subjected to oxidation reaction in the oxidant atmosphere, and the oxidation reaction in the combustion section generates heat so as to provide the heat to the preheating section and the activation section;
in the activation section, the carbonized material is subjected to activation reaction in the atmosphere of an activating agent to generate activated carbon and coal gas;
wherein the activating agent is derived from the products of the preheating section and the combustion section.
S3: and discharging the activated carbon and the coal gas out of the moving bed reaction furnace.
According to an embodiment of the invention, wherein: the method comprises the following steps that materials sequentially pass through a flow guide section and a fuel section of the moving bed reaction furnace before being sent into a preheating section of the moving bed reaction furnace, wherein the flow guide section is used for guiding the materials; and the fuel section is used for loading materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section.
According to the embodiment of the invention, the specific operation flow for preparing the activated carbon is as follows: (1) adding materials into the reaction furnace to enable the height of the materials to be positioned in the fuel section; (2) starting an oxidant gas source, starting an ignition device, and starting ignition; (3) in this mode of ventilation, the sign of successful ignition is the formation of a stable upward propagating ignition front inside the furnace; (4) after ignition is successful, the ignition device is closed, and the position of an ignition front is monitored according to temperature change; (5) when the ignition front is transmitted to the combustion section, the downward moving speed of the materials in the reaction furnace is controlled by adjusting the discharging speed of the activated carbon, and the position of the ignition front is strictly limited in the combustion section; (6) when the upward propagation speed of the ignition front is equal to the downward moving speed of the materials in the furnace, entering an active carbon stable preparation stage; (7) in the whole process, the height of the material layer in the furnace is monitored in real time, corresponding feeding operation is carried out, and the material level in the furnace is maintained in the fuel section.
In the apparatus according to the embodiment shown in fig. 1, according to an embodiment of the present invention, the oxidant is introduced into the guide section of the moving bed reactor; in order to maintain the stable preparation of the activated carbon, the ignition front position needs to be strictly limited in the combustion section, and the stable operation needs to be ensured: downward moving speed v of material AC Equal to the upward propagation velocity v of the ignition front f 。
Specifically, in the stable operation stage, the reaction in the moving bed reactor can meet the stable operation conditions, namely, the following conditions can be met by adjusting the discharge rate of the activated carbon and the parameters of the oxidant: downward moving speed v of material AC Equal to the upward propagation velocity v of the ignition front f Wherein the parameter of the oxidant comprises a flow rate of the oxidant, or a concentration of oxygen in the oxidant. I.e. when the flow rate of the oxidizing agent is increased, orWhen the oxygen concentration in the oxidant, the oxidation process is accelerated, the discharging speed is also accelerated, and in order to limit the ignition frontal surface position in the combustion section, the discharging speed needs to be correspondingly accelerated.
In order to realize the purpose, the supply quantity of the oxidant introduced into the furnace is kept at a low level, the apparent flow velocity of the oxidant is controlled to be 0.01-0.1 m/s magnitude, and the oxygen flux is in an oxygen control or extreme oxygen control state relative to the feeding quantity of the raw materials as a whole, and the method comprises the following steps: the equivalence ratio between the oxygen amount needed by the theoretical combustion of the fuel skipped by the ignition front and the actual oxygen amount introduced into the reaction furnace should not be less than 10. The oxidant can be air, oxygen-enriched gas (O) 2 /N 2 、O 2 /CO 2 、O 2 /N 2 /CO 2 ) And the like. In the process of stable operation of the reaction furnace, the materials in the reaction furnace move downwards by gravity and move downwards at a speed (v) AC ) Equal to the upward propagation velocity (v) of the ignition front f Taking the start-up stage as an example, v is f And = delta d/delta t, wherein delta d is the distance between two specific thermocouples on the reaction furnace, delta t is the time interval when the two thermocouples reach the highest temperature in the furnace starting stage), and the ignition front position is in the combustion section.
According to an embodiment of the invention, wherein:
in the combustion section, the oxidation reaction comprises homogeneous phase oxidation reaction of combustible gas and heterogeneous phase oxidation reaction of carbonized materials; the method further comprises the following steps: the oxygen concentration in the oxidant is adjusted to be more than 50 percent so as to strengthen the homogeneous oxidation reaction and weaken the heterogeneous oxidation reaction.
Based on the relative motion relationship among the flame front, the material and the oxidant, the oxidant and the material can change as follows in the downward movement process: in the diversion section and the fuel section (room temperature), the oxidant and the materials are basically maintained in the original state; in a preheating section (lower than 500 ℃), the materials are subjected to transformation such as drying, devolatilization, low-temperature oxidation and the like in sequence, unitary solid fuel is gradually transformed into combustible gas and carbonized material binary mixed fuel, and a small amount of oxygen in an oxidant is consumed; in the combustion section (500-1000 deg.C), only a small amount of binary mixed fuel is oxidized due to oxygen control, and in this region, the rest oxygen is completely removedConsumption; in the activation section (700-1000 deg.C), mainly carbonized material and CO are produced 2 And an endothermic activation reaction between active gases (generated in the preheating section and the combustion section) such as water vapor, to sufficiently activate the carbonized material.
In the above-mentioned material conversion process, the oxidation reaction in the combustion section involves homogeneous oxidation of the volatile components and heterogeneous oxidation of the carbonized material. In the combustion section, the principle of strengthening homogeneous phase oxidation and weakening heterogeneous phase oxidation should be adhered to, and the principle can be realized by increasing the flow rate and the oxygen concentration of the oxidant. Generally, the oxygen consumption ratio of homogeneous oxidation is higher than 50%, and for the oxygen-rich working condition, the homogeneous oxidation ratio is even as high as more than 80%. In the preheating section and the combustion section, the combustion share of the fuel is lower than 10 percent, and even lower than 5 percent under the oxygen-rich working condition. The heat released by combustion in the combustion section provides all heat sources for the whole preparation process of the activated carbon: the preheating section is heated in a heat conduction and radiation mode, so that materials are promoted to be dried, devolatilized and transformed; the carbonized material and the combustible gas are heated to a high-temperature state in the combustion section, and the sensible heat of the gas and the solid provides heat for the activation reaction of the carbonized material in the activation section.
In the device and the method for preparing the activated carbon, provided by the embodiment of the invention, granular activated carbon can be used as a material, and the granular activated carbon comprises broken carbon and formed carbon, and the particle size is generally larger than 3mm.
According to the examples of the present invention, the yield of activated carbon was m under the above-mentioned operating conditions AC ＝(Δd/Δt)·S·ρ AC Wherein S is the cross-sectional area of the reaction furnace, rho AC Is the bulk density of the activated carbon product. The yield of activated carbon is proportional to the diameter of the reactor at a specific ignition front propagation velocity. For a reaction furnace with the inner diameter of 1m, the yield of the activated carbon can reach 1-5 t/h.
According to the embodiment of the invention, by adopting the preparation method of the activated carbon, the heat required by the preparation of the activated carbon only depends on the combustion heat release of a small amount of raw materials, the heat utilization rate is high, a high-power auxiliary heat source is not required to be provided, and the energy consumption is low; the raw materials are self-heated by means of combustion of part of the raw materials, and in-situ utilization of combustion heat release is realized, so that the self-heating mode is high in heat utilization rate, high in heating speed and uniform in material heating; based on bed layer partition conversionThe tar is generated in the preheating section and is subjected to high-temperature oxidation in the combustion section and catalytic cracking by activated carbon in the activation section, the tail gas is free of tar, and the method is clean and environment-friendly and does not need tar treatment equipment; part of activating agent is CO generated in preheating and burning stage in preparation process of activated carbon 2 And H 2 And O, the active ingredients in the raw materials are fully utilized, a certain self-activation property is shown, and the using amount of an activating agent is saved.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (15)
1. An activated carbon preparation device comprises a moving bed reaction furnace, wherein the moving bed reaction furnace comprises an oxidant inlet, a preheating section, a combustion section and an activation section which are sequentially arranged along the material moving direction, wherein:
the preheating section is used for drying, devolatilizing and low-temperature oxidizing the materials in an oxidant atmosphere so as to generate combustible gas and carbonized materials;
the combustion section is used for carrying out oxidation reaction on the combustible gas and the carbonized materials under the atmosphere of oxidant and supplying heat generated by the oxidation reaction to the preheating section and the activation section;
the activation section is used for performing activation reaction on the carbonized material in the atmosphere of an activating agent to generate activated carbon and coal gas;
the oxidant inlet is used for introducing the oxidant into the moving bed reaction furnace;
wherein the activator is derived from the products of the pre-heating stage and the combustion stage.
2. The apparatus of claim 1, wherein the moving bed reactor further comprises a guide section and a fuel section arranged in sequence along a moving direction of the material, wherein:
the flow guide section is used for guiding the material;
the fuel section is used for loading the materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section;
wherein the oxidant inlet is in communication with an inlet of the inducer.
3. The apparatus of claim 2, wherein:
the height ratio of the preheating section to the combustion section is more than 2: 1, the height of the combustion section is more than or equal to 0.5m, and the height of the activation section is more than 2m.
4. The apparatus of claim 2, further comprising a feed device, a cooling device, wherein:
the feeding device is communicated with the inlet of the diversion section and is used for supplying the materials into the moving bed reaction furnace;
the cooling device is communicated with an outlet of the activation section and is used for generating cooled activated carbon and second temperature water after the heat exchange is carried out on the activated carbon in the cooling device, wherein the temperature of the second temperature water is higher than that of the first temperature water.
5. The apparatus of claim 4, further comprising:
a burner for burning the gas to generate a first temperature flue gas;
and the tube bundle heat exchanger is arranged in the activation section and is communicated with a first temperature flue gas outlet of the combustor so as to provide the heat of the first temperature flue gas for the activation reaction of the carbonized material in the activation section through the tube bundle heat exchanger to generate a second temperature flue gas, wherein the temperature of the second temperature flue gas is lower than that of the first temperature flue gas.
6. The apparatus of claim 5, further comprising:
the flue gas heat exchanger is communicated with a second temperature flue gas outlet of the tube bundle heat exchanger and is used for generating saturated steam after heat exchange is carried out on the second temperature flue gas and the second temperature water in the flue gas heat exchanger;
and the combustion section heat exchanger is arranged in the fuel section and used for heating the saturated steam into superheated steam by utilizing heat generated by the oxidation reaction of the combustion section.
7. The apparatus of claim 6, further comprising:
a steam lance disposed in the activation section for feeding the superheated steam as a supplemental activator into the activation section.
8. The apparatus of claim 1, wherein the moving bed reactor further comprises a guide section and a fuel section arranged in sequence along the moving direction of the material, wherein:
the flow guide section is used for guiding the material;
the fuel section is used for loading the materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section;
wherein the oxidant inlet is in direct communication with the combustion section.
9. The apparatus of claim 8, wherein:
and auxiliary airflow is introduced into an inlet of the flow guide section and is used for providing a back pressure environment for the space above the fuel section of the moving bed reaction furnace.
10. A method for preparing activated carbon using the activated carbon preparation apparatus of any one of claims 1 to 9, comprising:
introducing an oxidant into the moving bed reactor through an oxidant inlet of the moving bed reactor;
feeding the material into the moving bed reactor so that the oxidant and the material react in a preheating section, a combustion section and an activation section of the moving bed reactor in sequence, wherein:
in the preheating section, the materials are dried, devolatilized and oxidized at low temperature in the atmosphere of oxidant to generate combustible gas and carbonized materials;
in the combustion section, the combustible gas and the carbonized material are subjected to an oxidation reaction under an oxidant atmosphere, and in the combustion section, the oxidation reaction generates heat so as to provide the heat to the preheating section and the activation section;
in the activation section, the carbonized material is subjected to activation reaction in the atmosphere of an activating agent to generate activated carbon and coal gas;
wherein the activating agent is derived from the products of the pre-heating stage and the combustion stage.
11. The method of claim 10, wherein:
the material sequentially passes through a diversion section and a fuel section of the moving bed reaction furnace before being sent to a preheating section of the moving bed reaction furnace, wherein the diversion section is used for conducting diversion on the material; the fuel section is used for loading the materials, wherein the downstream end of the fuel section in the material moving direction is adjacent to the preheating section.
12. The method of claim 11, wherein:
the oxidant is introduced into the flow guide section of the moving bed reactor;
the method further comprises the following steps:
discharging the activated carbon and the coal gas out of the moving bed reaction furnace;
and (2) enabling the reaction in the moving bed reaction furnace to meet stable operation conditions by adjusting the discharge rate of the activated carbon and the parameters of the oxidant, wherein the stable operation conditions are as follows: the downward moving speed v of the material AC Equal to the upward propagation velocity v of the ignition front f Wherein the parameters of the oxidizing agent include at least one of: the oxidizing agentFlow rate, oxygen concentration in the oxidant.
13. The method of claim 12, wherein adjusting the parameters of the activated carbon draw rate, the oxidant, and the like comprises:
under the condition of improving the parameters of the oxidant, the discharging speed of the activated carbon is improved; and
and under the condition of reducing the parameters of the oxidizing agent, reducing the discharge rate of the activated carbon.
14. The method of claim 10, wherein:
said oxidant is passed into said combustion section of said moving bed reactor;
the method further comprises the following steps:
discharging the activated carbon and the coal gas out of the moving bed reaction furnace;
and (2) enabling the reaction in the moving bed reaction furnace to meet stable operation conditions by adjusting the discharge rate of the activated carbon and the parameters of the oxidant, wherein the stable operation conditions are as follows: downward moving speed v of the material AC No greater than upward propagation velocity v of ignition front f 。
15. The method of claim 10, wherein:
in the combustion section, the oxidation reaction comprises a homogeneous phase oxidation reaction of the combustible gas and a heterogeneous phase oxidation reaction of the carbonized material;
the method further comprises the following steps: adjusting the oxygen concentration in the oxidant to above 50% so as to intensify the homogeneous oxidation reaction while weakening the heterogeneous oxidation reaction.
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| JPH05345605A (en) * | 1992-06-16 | 1993-12-27 | Katsufumi Akizuki | Activated carbon production unit |
| CN204824185U (en) * | 2015-08-06 | 2015-12-02 | 西安科技大学 | Integrated device of pyrolysis of coal and active carbon production |
| CN105905894A (en) * | 2016-01-28 | 2016-08-31 | 赵英杰 | Carbonization and activation device for active coke production |
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