WO2020155856A1 - 一种钟乳石状大孔活性炭的制备方法 - Google Patents

一种钟乳石状大孔活性炭的制备方法 Download PDF

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WO2020155856A1
WO2020155856A1 PCT/CN2019/123705 CN2019123705W WO2020155856A1 WO 2020155856 A1 WO2020155856 A1 WO 2020155856A1 CN 2019123705 W CN2019123705 W CN 2019123705W WO 2020155856 A1 WO2020155856 A1 WO 2020155856A1
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Prior art keywords
activated carbon
temperature
stalactite
macroporous
activated
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French (fr)
Inventor
郭灏
唐立成
吴宁宁
陈晓涛
石斌
陈铤
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Guizhou Meiling Power Supply Co Ltd
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Guizhou Meiling Power Supply Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/342—Preparation characterised by non-gaseous activating agents
    • C01B32/348—Metallic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/354—After-treatment

Definitions

  • the invention belongs to the technical field of activated carbon materials, and particularly relates to a preparation method of stalactite-like macroporous activated carbon.
  • activated carbon has the advantages of high specific surface area, low cost, high chemical and thermal stability, and high electrical conductivity. Although conventional activated carbon has a specific surface area of more than 2000m 2 /g, the actual utilization rate is not high. The reason is that the porous activated carbon material prepared under the existing process conditions cannot avoid the formation of micropores with a pore diameter of 2nm or less, and the ideal porous carbon material The diameter of the small holes is generally greater than 2nm to effectively form an electric double layer or for material growth. Therefore, it is necessary to adopt a chemical activation method to increase the specific surface area and control the diameter of the micropores to make the diameter larger than 2 nm.
  • the traditional chemical activation process of activated carbon usually uses a tube furnace or an atmosphere furnace with nitrogen or argon protection. First, it is pre-fired at 350°C for 1.5h-3h, and then activated at 800°C or above for 1h-3h. The time required for activation is compared. Long, the entire activation process and the heating process require at least 4 hours, resulting in relatively high consumption of energy and protective gas. Therefore, how to reduce energy consumption and time cost is the key to large-scale commercial application of activated carbon with high specific area and high specific capacitance.
  • patent application CN107973296A discloses a large-pore activated carbon and its preparation method.
  • Claim 1 discloses the following steps: Step 1. Crush the activated carbon raw material and soak the raw material in ethanol In the solution, hydroxide is added as a pore expander in the ethanol solution. After ultrasonic vibration, the pretreated activated carbon is obtained by washing and drying with water; step 2. The pretreated activated carbon is added with a surfactant at a temperature of 80-100°C. Soak for 7-9h and stir at 2-3h intervals to make it evenly mixed; Step 3.
  • the mixed gas with carbon dioxide is activated at 700-800 degrees for 1-3 hours to obtain activated carbon with large pores; beneficial effects: firstly, the present invention uses physical and chemical methods to act simultaneously to expand the pores; secondly, carbon dioxide and water are used in the activation process The mixed gas of steam is physically activated, which broadens the pore size of activated carbon under the synergistic effect of the two.
  • Patent application CN107226470A discloses a method for preparing macroporous biological activated carbon with adjustable pores without a binder, including the following steps: (1) bamboo is selected as the raw material, the debris is crushed, and sieved, and the bamboo debris is 80 ⁇ 5 meshes. The moisture content is 8 ⁇ 0.5%; (2) The compression ratio is 1:5 to 1:10 for briquetting granulation, the compression ratio refers to diameter/length; (3) Carbonization treatment: carbonization temperature is 450-700°C , The carbonization time is 0.5-2.5h; (4) Activation reaction: the activation temperature is 700-1000°C, and the activation time is 1-3.5h.
  • Patent application CN107140635A includes the following steps: (1) select bamboo as raw material, crush the scraps, and sieving, take the bamboo scraps 80 ⁇ 5 mesh, and the moisture content is 8 ⁇ 0.5%; (2) add adhesive, adhesive The dosage is 5 to 35% by weight of bamboo chips, and the mixture is uniform; (3) According to the compression ratio of 1:5 to 1:10 briquetting granulation; compression ratio refers to diameter/length; (4) carbonization treatment: carbonization temperature At 450-700°C, the carbonization time is 0.5-2.5h; (5) Activation reaction: the activation temperature is 700-1000°C, and the activation time is 1-3.5h.
  • the activation reaction temperature is above 700°C
  • the activation time is 1 to 3 hours
  • the activation temperature is higher, and the time required for activation is longer, which will result in the consumption of energy and protective gas. high.
  • Patent application CN109179404A discloses a method for preparing medium and large pore activated carbon using long flame coal.
  • the selected coal type is a single long flame coal and a multi-component composite binder is used.
  • the addition amount of the raw coal is 60% to 80% based on the total weight, the addition amount of the binder is 10% to 25%, and the addition amount of water is 3% to 10%.
  • the raw materials are processed by powdering and bonding, layering granulation, carbonization and secondary carbonization, activation, etc., to obtain long-flame coal medium and large pore activated carbon.
  • Patent application CN109081344A discloses a process for preparing macroporous activated carbon.
  • the activated carbon adopts finished activated carbon, and its steps include DMF process and activation process; DMF process: finished activated carbon is immersed in DMF solution for 12 hours; activation process: dipped in DMF process The finished activated carbon is put into an activation furnace for activation, and after the temperature rises to 850°C, it stays for one hour before taking it out to obtain macroporous activity.
  • Patent application CN108963291A discloses a thin thermal battery with independent electrode system and heating system, including an electrode system and a heating system.
  • the heating system is wrapped by a thermally conductive insulating layer.
  • the heating system supplies heat to the electrode system from all around.
  • this patent application belongs to the design and composition of thermal batteries, not in the technical field of carbon materials, and is significantly different from carbon materials in terms of principle, efficacy, structure, and element composition, and this patent application cannot solve the problem of activation during the preparation of activated carbon.
  • Technical problems such as higher temperature, longer time required for activation, and higher consumption of energy and protective gas.
  • Patent application CN106587053A discloses a preparation process of activated carbon special for desulfurization, including the following steps: pressurization and pressure relief treatment; heating and freezing; explosion expansion; cold blowing; carbonization; activation. It is disclosed that magnesium powder and sodium hydroxide are mixed and mixed with raw materials to produce a puffing effect to form a larger pore size. However, this patent application still requires the carbonization furnace to provide an external high-temperature environment at the activation temperature.
  • Patent application CN103058186B discloses a method for preparing granular activated carbon from wood chips as raw materials, a. The wood chips are crushed to a certain granularity and dried for later use; b. Then the wood chips obtained in step a are phosphoric acid and the wood chips obtained in step a are Mixing, mixing and adding the co-catalyst disodium hydrogen phosphate to obtain a mixture; c. performing low-temperature immersion, plasticizing, kneading, extrusion molding, drying, carbonization, activation, recycling, rinsing, drying, and crushing of the mixture in sequence , Get the product after screening. It is disclosed that the auxiliary activator is added to reduce the activation temperature and activation time. But the overall time is still longer and the temperature is higher.
  • the four general methods are 1 colloidal crystal template and colloidal particle template method, 2 micro-float method, 3 two-step template method, 4 biological template method (CN107140635A, CN107226470A), but still
  • 4 biological template method CN107140635A, CN107226470A
  • the present invention provides a method for preparing stalactite-like macroporous activated carbon.
  • the present invention discloses for the first time a preparation method for obtaining stalactite-like macroporous activated carbon in a low temperature environment, which shortens the activation time, compresses the traditional activation time from more than 1h to several minutes to several seconds, and greatly improves the macroporous
  • the preparation efficiency of activated carbon reduces the traditional activation environment temperature from above 800°C to 120°C ⁇ 200°C.
  • a preparation method of stalactite-like macroporous activated carbon includes the following steps:
  • the mass ratio of the low-temperature combustion-supporting agent, the high-temperature self-igniting agent, the activated activated carbon precursor and the heat-conducting substrate 0.3 ⁇ 1.5:8 ⁇ 15:1:0.5 ⁇ 1.
  • the activated activated carbon precursor is activated carbon and potassium hydroxide, and the mass ratio of the activated carbon to potassium hydroxide is 1:3.1-7.9.
  • the oxidant is one or more of potassium perchlorate, lithium perchlorate, and sodium perchlorate.
  • the press pressure of the tablet is 10kpa to 2000kpa.
  • step (4) the activation time is 3 s to 2 min.
  • thermally conductive substrate is one of nickel, titanium, and platinum.
  • the diameter of the thermally conductive substrate is 18-130 mm.
  • This application uses zirconium and barium chromate with extremely high burning rates as low-temperature combustion aids, which do not spontaneously combust at room temperature to ensure safety in use, and can control combustion by adjusting the ratio of zirconium to barium chromate Speed; the iron powder in the high-temperature self-igniting agent is seriously excessive to ensure that the oxidizer and the iron powder completely react without generating excess oxygen to cause side reactions; the activated activated carbon precursor uses potassium hydroxide and activated carbon to react to generate impact gas, which guarantees the impact A sufficient source of gas will not cause side reactions with the thermally conductive substrate, and the ratio of activated carbon to potassium hydroxide ensures complete reaction of potassium hydroxide.
  • the morphology of macroporous activated carbon can be controlled by adjusting the ratio of activated carbon and potassium hydroxide.
  • the quality of the high-temperature self-igniting agent determines the ratio and quality of the high-temperature self-igniting agent; the heat-conducting substrate adopts a metal with high thermal conductivity and corrosion resistance to ensure the timely conduction of heat, so as to achieve a high-temperature local reaction temperature zone without side reactions with raw materials.
  • the selection and dosage range of the application materials make the preparation method of the present invention efficient and convenient.
  • ordinary finished activated carbon is selected as the carbon source, and the ordinary finished activated carbon has a wide source, many brands and low price.
  • Ordinary finished activated carbon is often used as a gas adsorbent, but all have a microporous structure (pore size ⁇ 2nm).
  • the finished activated carbon does not require a carbonization process, and the finished activated carbon is mixed uniformly with potassium hydroxide to become an "activated activated carbon precursor", and the preparation idea of the "deflagration method" first proposed in the present invention is adopted for solid phase activation preparation.
  • the biggest difference between the "deflagration method” and traditional equipment is that it does not need to consider the heating process and heat preservation process of the equipment.
  • the traditional "macroporous activation” is carried out under a "mild” condition, with a slow heating rate ( ⁇ 5°C/min) and a high temperature (>800°C) for more than 1h.
  • the reason for this is to protect the safety of the equipment during the high-temperature heating stage. Because the heating rate in the high-temperature stage is too fast, the temperature control of the equipment will fail, and the equipment will be damaged by "over-temperature” heating.
  • the “deflagration method” innovatively uses the “step heating method” to instantly create a "local high temperature area". Because the heating equipment is in the low temperature range ( ⁇ 200°C) as a whole, there is no need to worry about the damage to the equipment by the instant local high temperature.
  • the low-temperature combustion-supporting agent is composed of zirconium and barium chromate. Through the screening of the particle size and the adjustment of the ratio, it can reach an ultra-fast burning rate of 20cm/s ⁇ 90cm/s at a temperature exceeding 120°C, thus relying on the low-temperature combustion-supporting agent to complete the Rapid activation of high temperature self-igniting agent.
  • the invention mainly relies on the material's own energy (iron powder and oxidant) to complete the entire "macroporous activation process". Among them, the high-temperature self-igniting agent takes iron and potassium perchlorate as an example.
  • the reaction temperature can reach 1538°C, which is equivalent to the high temperature when metallic iron melts into a liquid;
  • the reaction temperature can reach 1413°C;
  • the mass ratio of iron and potassium perchlorate is 88:12, the reaction temperature can reach 1369°C.
  • the energy produced by the violent reaction of the high-temperature self-igniting agent acts on the activated carbon and potassium hydroxide, which can make it react violently in an instant, and realize the "macroporous activation" of the activated carbon by potassium hydroxide.
  • potassium salt instead of sodium salt
  • sodium has a low boiling point (762°C) and sodium has a high boiling point (883°C)
  • the high temperature reaction kinetics of potassium salt is faster.
  • potassium hydroxide is used for potassium salt because of its low molecular weight (56.1g/mol), so it is compatible with potassium carbonate (138.21g/mol), potassium bicarbonate (100.115g/mol) and potassium acetate (98.14g/mol).
  • potassium perchlorate 138.55g/mol
  • potassium permanganate 158.034g/mol
  • other potassium salts have a higher molar mass under the same mass ratio. In the actual reaction, the molar mass determines the reaction mass. It is not quality, so the use of potassium hydroxide has a larger reaction volume than other potassium salts and saves the amount of potassium used.
  • the entire activation reaction follows the following reaction equation:
  • the carbon dioxide produced by the finished activated carbon is basically transformed into carbonate in the form of reaction equation (4), that is, the carbon consumed in the activation process mainly generates potassium carbonate, so that the finished activated carbon is completed in the form of activated activated carbon precursor
  • the macroporous activated carbon with similar stalactite morphology in the present invention is obtained.
  • the morphology of the stalactite in the present invention is related to the mechanism of the present invention.
  • the use of potassium hydroxide to open the activated carbon The process can be seen as the process of accelerated water erosion of rocks.
  • the instantaneous high temperature region provided by the present invention makes potassium hydroxide and the finished activated carbon react violently at the contact interface, and finally obtains the SEM test images of the stalactite-like macroporous activated carbon as shown in Figs. 2-5.
  • the present invention discloses for the first time a preparation method for obtaining stalactite-like macroporous activated carbon in a low temperature environment, shortening the activation time, and compressing the traditional activation time from more than 1 hour to several minutes to several seconds, greatly improving Improved the production efficiency of macroporous activated carbon, and reduced the traditional activation environment temperature from above 800°C to 120°C ⁇ 200°C. It pioneered the transitional local high-temperature heating method, creating a stepped rapid heating method, and realizing activated carbon in a very short time. Porosity; equipment power consumption is greatly reduced.
  • the safety in the production process is also greatly improved, and it has the characteristics of simple production, fast reaction speed, and low environmental temperature required for reaction.
  • the time required from the preparation of raw materials to obtaining the finished stalactite-like macroporous activated carbon can be controlled within 1h at the fastest, which can greatly improve the preparation efficiency of macroporous activated carbon. It has the advantages of high efficiency, high safety, low energy consumption, and good activated carbon appearance. , Has extremely high engineering application value.
  • This application uses zirconium and barium chromate to generate a strong oxidation-reduction reaction in the lower temperature range of 120°C to 200°C.
  • Zirconium and barium chromate can generate a high temperature of thousands of degrees Celsius at the moment of combustion, so that iron powder and The high-temperature self-igniting agent composed of strong oxidant reacts more violently, keeping the impact temperature above 1000°C in a short period of time, so that the potassium ions in the activated activated carbon precursor form potassium vapor, which diffuses into the carbon framework and reacts to produce carbon dioxide, Carbon monoxide, a small amount of hydrogen and other gases violently impact the microscopic surface of the activated carbon material, which has a significant impact on its specific surface and pore structure, resulting in stalactite-like macroporous activated carbon; moreover, there is a serious excess of iron powder in the high-temperature self-igniting agent, so as to fully contact the strong oxidant The reaction avoids the production of excess oxygen and the
  • the zirconium and barium chromate used in the present invention are used as the combustion-supporting agent.
  • the working temperature of the combustion-supporting agent is significantly higher than room temperature, does not cause spontaneous combustion at room temperature, has good safety, and is significantly lower than the traditional activated carbon above 800°C
  • the activation temperature greatly reduces the activation energy consumption.
  • the material itself can maintain a high temperature exceeding 1000°C in a short period of time, shortening the traditional activation time from 1h to several minutes. Within ten seconds, the activation efficiency is greatly improved.
  • This application is the first to create a transitional local high temperature heating method, creating a stepped rapid heating method to realize the macroporosity of activated carbon in a very short period of time; it breaks through "under the same other conditions, within a certain range, the activation time increases It is helpful to improve the activation effect, that is, shorten the activation time and the activation effect will become worse.” It can activate in a short time and ensure the activation effect.
  • the present invention Since there is no need to carry out the carbonization process, and the finished activated carbon is directly used for "macroporation" activation treatment, the present invention has no special requirements on the original microscopic morphology of the finished activated carbon used, and any morphology of activated carbon can be used.
  • the invention carries out fast, low energy consumption and simple macroporous processing.
  • Figure 1 is a schematic diagram of a sandwich structure made of stalactite-like macroporous activated carbon of the present invention
  • Figure 2 is an SEM image of stalactite-like macroporous activated carbon prepared in Example 1 of the present invention
  • Example 3 is an SEM image of stalactite-like macroporous activated carbon prepared in Example 2 of the present invention
  • Example 4 is an SEM image of stalactite-like macroporous activated carbon prepared in Example 3 of the present invention
  • Figure 5 is an SEM image of stalactite-like macroporous activated carbon prepared in Example 4 of the present invention.
  • a preparation method of stalactite-like macroporous activated carbon includes the following steps:
  • the activated carbon precursor on the thermally conductive substrate has a local temperature above 1000°C, and then completes activation.
  • the activation time is 3s to 2min. After cooling to room temperature, stalactite-like macroporous activated carbon is obtained on the thermally conductive substrate.
  • the mass ratio of the low-temperature combustion-supporting agent, the high-temperature self-igniting agent, the activated activated carbon precursor and the heat-conducting substrate 0.5:10:1:1; in steps (1), (2) and (3), the The press pressure for pressing into tablets is 10kpa-2000kpa; the heat-conducting substrate is nickel; the diameter of the heat-conducting substrate is 18-130mm.
  • the micro morphology of the stalactite-like macroporous activated carbon in this example is shown in FIG. 2.
  • a preparation method of stalactite-like macroporous activated carbon includes the following steps:
  • the mass ratio of the low-temperature combustion-supporting agent, the high-temperature self-igniting agent, the activated activated carbon precursor and the heat-conducting substrate 0.5:10:1:1; in steps (1), (2) and (3), the The press pressure for pressing into tablets is 10kpa-2000kpa; the heat-conducting substrate is titanium; the diameter of the heat-conducting substrate is 18-130mm.
  • the microscopic morphology of the stalactite-like macroporous activated carbon in this example is shown in FIG. 3.
  • a preparation method of stalactite-like macroporous activated carbon includes the following steps:
  • the mass ratio of the low-temperature combustion-supporting agent, the high-temperature self-igniting agent, the activated activated carbon precursor and the heat-conducting substrate 0.5:15:1:1; in steps (1), (2) and (3), the The press pressure for pressing into tablets is 10kpa-2000kpa; the heat-conducting substrate is one of nickel, titanium, and platinum; and the diameter of the heat-conducting substrate is 18-130mm.
  • the micro morphology of the stalactite-like macroporous activated carbon in this example is shown in FIG. 4.
  • a preparation method of stalactite-like macroporous activated carbon includes the following steps:
  • the mass ratio of the low-temperature combustion-supporting agent, the high-temperature self-igniting agent, the activated activated carbon precursor and the heat-conducting substrate 0.5:12:1:1; in steps (1), (2) and (3), the The press pressure for pressing into tablets is 10kpa-2000kpa; the heat-conducting substrate is one of nickel, titanium, and platinum; and the diameter of the heat-conducting substrate is 18-130mm.
  • the microscopic morphology of the stalactite-like macroporous activated carbon in this example is shown in FIG. 5.
  • Example 4 200°C 10s Comparative example 1 700°C ⁇ 1000°C 1h ⁇ 3.5h Comparative example 2 700°C ⁇ 1000°C 1h ⁇ 3.5h Comparative example 3 800°C ⁇ 950°C 2h ⁇ 3h Comparative example 4 850°C 1h Comparative example 5 1850°C 1h Comparative example 6 700°C ⁇ 800°C 1h ⁇ 3h Comparative example 7 600 ⁇ 800°C 1h Comparative example 8 900°C 2h
  • the activated carbon preparation method of the present application has a shorter activation time and requires a lower activation environment temperature.
  • the present invention can obtain stalactite-like macroporous activated carbon in a low temperature environment, shorten the activation time, compress the traditional activation time from more than 1h to several minutes to several seconds, and change the traditional activation environment temperature from 800°C
  • the above is reduced to 120°C ⁇ 200°C, the first transitional local high temperature heating method, creating a step-shaped rapid heating method, realizing activated carbon macroporosity in a very short time; equipment power consumption is greatly reduced, the reaction speed is fast, and the reaction requires the environment
  • the low temperature can greatly improve the preparation efficiency of macroporous activated carbon. It has the advantages of high efficiency, high safety, low energy consumption, and good activated carbon morphology, and has extremely high engineering application value.

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Abstract

一种钟乳石状大孔活性炭的制备方法，包括以下步骤：将活化活性炭前驱体球磨15min～2h，压制成片状，在其两侧设置导热基底，使其处于两片导热基底之间；将高温自引燃剂压制成片状后，置于上述导热基底无活化活性炭前驱体的侧面上；将低温助燃剂压制成片状后，置于上述高温自引燃剂的外侧面上，活化活性炭前驱体、高温自引燃剂、低温助燃剂与导热基底制成夹心结构；将上述夹心结构置于密闭的氩气、氮气或真空氛围中加热至120℃～200℃，冷却至室温后得到钟乳石状大孔活性炭。上述制备方法将传统的活化环境温度从800℃以上降低至120℃～200℃，缩短了活化时间，具有效率高、安全性高、能耗低、活性炭形貌好的优点。

Description

一种钟乳石状大孔活性炭的制备方法 技术领域
本发明属于活性炭材料技术领域，尤其涉及一种钟乳石状大孔活性炭的制备方法。
背景技术
由于活性炭具有高比表面积、低成本、化学稳定性和热稳定性高以及电导率较高等优点。虽然常规活性炭具有超过2000m 2/g的比表面积，但实际利用率并不高，原因在于现有的工艺条件制备的多孔活性炭材料无法避免孔径为2nm以下微孔的形成，而理想的多孔炭材料的小孔直径一般要大于2nm才可有效的形成双电层或用于材料生长。因此，需要采用化学活化的方法提高比表面积并控制微孔直径，使其直径大于2nm。
传统的活性炭的化学活化过程通常使用管式炉或气氛炉，通氮气或氩气保护，先进行350℃预烧1.5h～3h，然后在800℃以上活化1h～3h，活化所需的时间比较长，整个活化过程与升温过程，至少需要的时间为4h，导致能源及保护气体的消耗比较高。因此，如何降低能耗及时间成本，是高比面积、高比电容活性炭大规模商业应用的关键。
目前，关于活性炭制备的专利有一些，例如：专利申请CN107973296A，公开了一种大孔径活性炭及其制备方法，权力要求1公开了一下步骤：步骤1、粉碎活性炭原料，将所述原料浸泡于乙醇溶液中，所述乙醇溶液中还加入氢氧化物为扩孔剂，经过超声波振荡后，水洗涤烘干得预处理活性炭；步骤2、所述预处理活性炭加入表面活性剂在80-100℃温度下浸渍7-9h，间隔2-3h搅拌，使其混合均匀；步骤3、在氮气保护下加热2-4小时，加热温度为300-500度，得预 处理活性炭，后将氮气切换成水蒸气和二氧化碳的混合气体，在700-800度活化时间1-3小时，得到大孔径活性炭；有益效果：首先，本发明采用物理和化学方法同时作用进行扩孔；其次，活化过程中采用二氧化碳和水蒸气的混合气体进行物理活化，在二者的协同作用下拓宽了活性炭的孔径。
专利申请CN107226470A，公开了一种无粘接剂孔隙可调的大孔生物活性炭制备方法，包括如下步骤：(1)原材料选取竹子，碎屑粉碎，并筛分，取竹屑80±5目，含水率在8±0.5％；(2)按照压缩比在1:5至1:10压块造粒，所述压缩比是指直径/长度；(3)炭化处理：炭化温度在450-700℃，炭化时间为0.5-2.5h；(4)活化反应：活化温度在700-1000℃，活化时间为1-3.5h。
专利申请CN107140635A，包括以下步骤：(1)原材料选取竹子，碎屑粉碎，并筛分，取竹屑80±5目，含水率在8±0.5％；(2)添加粘接剂，粘接剂用量为竹屑5-35％(重量)，混合均匀；(3)按照压缩比在1:5至1:10压块造粒；压缩比是指直径/长度；(4)炭化处理：炭化温度在450-700℃，炭化时间为0.5-2.5h；(5)活化反应：活化温度在700-1000℃，活化时间为1-3.5h。
但是，上述公开的关于活性炭制备方法中，活化反应温度均在700℃以上，活化时间为1～3h，活化温度较高，活化所需的时间较长，这会导致能源及保护气体的消耗比较高。
另外，也有专利申请CN102442665A，公开了一种热处理活性炭及其制备方法，将经过高温处理后的活性炭与扩孔剂混合均匀，于300-1000℃扩孔处理0.1-48小时得中孔和大孔率高的热处理活性炭。但是，该专利申请是依靠极高的环境温度对材料进行漫长的前处理后再降低温度制备(所有实施例均提到了需将“商业活性炭置于氩气中1850℃处理1小时后”)，所需的温度远远超过本申请的环境温度，且所需的能耗也是比较高的，该专利申请本质上依旧是过渡依赖较高的环境温度，不符合低温、低能耗的需求。
专利申请CN109179404A，公开了一种利用长焰煤制备中大孔活性炭的方法，所选煤种为单一长焰煤，采用多元复合型粘合剂。所述原料煤添加量按照总 重量计为60％～80％，粘合剂添加量为10％～25％，水添加量为3％～10％。原料经制粉粘合、压条造粒、炭化与二次炭化、活化等处理，制得长焰煤中大孔活性炭。
专利申请CN109081344A，公开一种大孔活性炭制备工艺，活性炭采用成品活性炭，其步骤包含有DMF工序和活化工序；DMF工序：成品活性炭浸渍于的DMF溶液中12小时；活化工序：将DMF工序中浸渍完成的成品活性炭放入活化炉中进行活化，在温度升至850℃后停留一小时后取出，得到大孔活性。
专利申请CN108963291A，公开了一种电极系统与加热系统独立的薄型热电池，包括电极系统和加热系统，加热系统由导热绝缘层包裹，加热系统从四周给电极系统供热。但是，该专利申请属于热电池的设计构成，不属于碳材料技术领域，且从原理、功效、结构、元素组成上来看热电池和碳材料显著不同，且该专利申请不能解决活性炭制备过程中活化温度较高、活化所需的时间较长、能源及保护气体的消耗比较高的技术问题。
专利申请CN106587053A，公开了一种脱硫专用活性炭的制备工艺，包括以下步骤：加压、泄压处理；加热、冷冻；喷爆膨化；冷吹；炭化；活化。公开了采用镁粉和氢氧化钠混合后与原料混合，产生膨化效果形成较大孔径。但是该专利申请在活化温度上还是需要碳化炉提供外界高温环境。
专利申请CN103058186B，公开了一种以木屑为原料制备颗粒活性炭的方法，a.将木屑破碎至一定颗粒度，烘干备用；b.然后以磷酸与步骤a得到的所述木屑按照一定的磷木比进行混合，混合同时加入助催化剂磷酸氢二钠得到混合物；c.对所述混合物依次进行低温浸渍、塑化、捏合、挤压成型、干燥、炭化、活化、回收、漂洗、烘干、破碎、筛分后得到产品。公开了添加助活化剂，从而在降低活化温度和活化时间。但是整体的时间还是较长、温度也较高。
目前，在整个大孔材料领域，通用的四大方法为①胶体晶体模板和胶体粒子模板法，②微浮液法，③两步模板法，④生物模板法(CN107140635A、CN107226470A)，但是，还没有任何公开的现有技术是主要依靠材料自身能量而非环境供能的方式来进行活性炭微观大孔化改性。因此，研发出一种便捷的、低能耗、且快速制备大孔活性炭的制备方法尤为重要。
发明内容
本发明为了解决上述技术问题，提供了一种钟乳石状大孔活性炭的制备方法。本发明首次公开了一种可在低温环境内获得钟乳石状大孔活性炭的制备方法，缩短了活化时间，将传统的活化时间在1h以上压缩到数分钟至几秒内，极大提高了大孔活性炭的制备效率，并将传统的活化环境温度从800℃以上降低至120℃～200℃。
为了能够达到上述所述目的，本发明采用以下技术方案：
一种钟乳石状大孔活性炭的制备方法，包括以下步骤：
(1)称取活化活性炭前驱体，置于转速为200r/min～1200r/min的球磨罐中球磨15min～2h，然后将球磨后的活化活性炭前驱体压制成片状，在其两侧设置导热基底，使其处于两片导热基底之间；
(2)称取高温自引燃剂压制成片状后，置于上述导热基底无活化活性炭前驱体的外侧面上；
(3)称取低温助燃剂压制成片状后，置于上述高温自引燃剂的外侧面上，使得原料从外向内依次形成低温助燃剂→高温自引燃剂→导热基底→活化活性炭前驱体的夹心结构；
(4)将上述夹心结构置于密闭的氩气、氮气或真空氛围中加热至120℃～200℃，利用环境温度引燃低温助燃剂，令低温助燃剂瞬间产生上千摄氏度的温度引燃高温自引燃剂，使得在导热基底上的活化活性炭前驱体局部温度处于1000℃以上，完成活化，冷却至室温后在导热基底上得到钟乳石状大孔活性炭。
进一步地，所述低温助燃剂、高温自引燃剂、活化活性炭前驱体和导热基底的质量比＝0.3～1.5:8～15:1:0.5～1。
进一步地，在步骤(1)，所述活化活性炭前驱体为活性炭和氢氧化钾，且所述活性炭与氢氧化钾的质量比为1:3.1～7.9。
进一步地，在步骤(2)，所述高温自引燃剂为铁粉和氧化剂，且所述铁粉和氧化剂的质量比＝70～88:12～30。
进一步地，所述氧化剂为高氯酸钾、高氯酸锂、高氯酸钠中的一种或一种以上。
进一步地，在步骤(3)，所述低温助燃剂为锆和铬酸钡，且所述锆和铬酸钡的质量比＝3～4:6～7。
进一步地，在步骤(1)、(2)及(3)，所述压制成片的压机压力为10kpa～2000kpa。
进一步地，在步骤(4)，所述活化的时间为3s～2min。
进一步地，所述导热基底为镍、钛、铂中的一种。
进一步地，所述导热基底的直径为18～130mm。
本申请的原理：本申请采用具有极高燃速的锆与铬酸钡作为低温助燃剂，其在室温下不自燃以保障使用安全性，并且可以通过调控锆与铬酸钡的比例来控制燃速；高温自引燃剂中铁粉严重过量，以保证氧化剂与铁粉完全反应而不产生多余氧气发生副反应；活化活性炭前驱体中采用氢氧化钾与活性炭反应来产生冲击气体，既保障了冲击气体的充足来源也不会与导热基底发生副反应，且活性炭与氢氧化钾的比例保证氢氧化钾完全反应完毕，通过调控活性炭和氢氧化钾的比例可控制大孔活性炭的形貌，且它们的质量决定了高温自引燃剂的配比及质量；导热基底采用热导率高且耐腐蚀的金属来保障热量的及时传导，以实现高温局部反应温区，且不与原材料发生副反应。本申请材料的选择及用量范围使得本发明的制备方式高效便捷。
本发明选用市售普通成品活性炭作为碳源，普通成品活性炭来源广，品牌多，价格低。普通成品活性炭常用作气体吸附剂，但均为微孔结构(孔径＜2nm)。采用成品活性炭不需要进行炭化过程，直接将成品活性炭与氢氧化钾混合均匀后变为“活化活性炭前驱体”，采用本发明首次提出的“爆燃法”制备思路进行固相活化制备。“爆燃法”与传统设备相比最大的差别在于不用考虑设备升温过程和保温过程。传统“大孔化活化”在一种“温和”的条件进行，升温速率慢(＜5℃/min)并保持高温(＞800℃)1h以上。这样做的原因在于保护设备在高温加热阶段的安全性，因在高温阶段升温速率过快会导致设备温控失效，出现“超温”加热损坏设备。而“爆燃法”创新地采用利用“阶梯升温法”来瞬间创造“局部高温区域”，因加热设备整体处于处于低温段(≤200℃)，所以不用担心瞬间局部高温对设备的损坏。低温助燃剂由锆与铬酸钡组成，通过对粒径的筛选和配比调控，在超过120℃下其能达到20cm/s～90cm/s的超快燃速，从而依靠低温助燃剂完成对高温自引燃剂的快速激活。本发明主要依靠材料自身能量(铁粉和氧化剂)完成整个“大孔化活化过程”。这其中，高温自引燃剂以铁与高氯酸钾为例，当铁和高氯酸钾的质量比＝80:20时，其反应温度可以达到1538℃，相当于金属铁熔化成液体时的高温；当铁和高氯酸钾的质量比＝86:14时，其反应温度可以达到1413℃；当铁和高氯酸钾的质量比＝88:12时，其反应温度可以达到1369℃。高温自引燃剂剧烈反应所产生的能量作用于活性炭和氢氧化钾，即可令其瞬间进行剧烈反应，实现氢氧化钾对活性炭的“大孔化活化”。
采用钾盐而不选用钠盐的原因在于，钾的沸点低(762℃)，而钠的沸点高(883℃)，因而钾盐的高温反应动力学更快。本发明中钾盐仅选用氢氧化钾是因其分子量低(56.1g/mol)，因而与碳酸钾(138.21g/mol)，碳酸氢钾(100.115g/mol)，醋酸钾(98.14g/mol)，高氯酸钾(138.55g/mol)、高锰酸钾(158.034g/mol)等其他钾盐相比，在同样质量占比下其摩尔量更高，实际反应中是摩尔量决定反应量而不是质量，故采用氢氧化钾与其它钾盐相比拥有更大的反应量，并节约钾盐的使用量。整个活化反应遵循如下反应方程式：
2KOH→K 2O+H 2O      (1)
C+H 2O→H 2+CO       (2)
CO+H 2O→H 2+CO 2     (3)
K 2O+CO 2→K 2CO 3     (4)
K 2O+H 2→2K+H 2O     (5)
K 2O+C→2K+CO       (6)
活化过程中成品活性炭产生的二氧化碳基本都以反应方程式(4)的形式变成碳酸盐，即活化过程中消耗掉的炭主要生成了碳酸钾，从而使成品活性炭以活化活性炭前驱体的形式完成了大孔化处理，得到了本发明中具有类似钟乳石形貌的大孔活性炭。本发明中钟乳石的形貌与本发明的机理有关，因爆燃法的高温反应动力学极快(在瞬间超过1000℃并在短期内维持高温)，所以在采用氢氧化钾对活性炭的进行开孔过程可以看做加速的水对岩石的侵蚀过程。采用本发明提供的瞬时高温区域令氢氧化钾与成品活性炭在接触界面上剧烈反应，最终获得如图2～图5所示的钟乳石状大孔活性炭的SEM测试图。
由于本发明采用了以上技术方案，具有以下有益效果：
(1)本发明首次公开了一种可在低温环境内获得钟乳石状大孔活性炭的制备方法，缩短了活化时间，将传统的活化时间在1h以上压缩到数分钟至几秒内，极大提高了大孔活性炭制备效率，并将传统的活化环境温度从800℃以上降低至120℃～200℃，首创跃迁式局部高温加热方法，创造阶梯形的快速升温方式，实现活性炭在极短时间内大孔化；设备功耗大幅降低，此外，由于活化环境温度的降低，也极大的提高了生产过程中的安全性，且具有制作简易，反应速度快，反应所需环境温度低等特点，从原材料准备到获得钟乳石状大孔活性炭成品所需时间最快可控制在1h内，可以极大提高大孔活性炭的制备效率，具有效率高、安全性高、能耗低、活性炭形貌好的优点，具有极高的工程应用价值。
(2)本申请利用锆与铬酸钡在120℃～200℃的较低温度区间内发生强氧化还原反应，锆与铬酸钡在燃烧瞬间可产生上千摄氏度的高温，从而令铁粉与强氧 化剂组成的高温自引燃剂发生更剧烈的反应，令冲击温度在短期内维持在1000℃以上，令活化活性炭前驱体中钾离子形成钾蒸汽，扩散到碳骨架中，发生反应生成二氧化碳、一氧化碳、少量氢气等气体剧烈冲击活性炭材料微观表面，对其比表面和孔结构产生显著影响，得到钟乳石状大孔活性炭；而且，在高温自引燃剂中铁粉严重过量，以便与强氧化剂充分接触反应，避免产生多余氧气与活性炭接触发生副反应生成二氧化碳导致原材料受损，此外，通过调配强氧化剂占比来控制质量比发热量，从而达到控制反应时间的目的。
(3)本发明采用的锆和铬酸钡作为助燃剂，该助燃剂工作温度显著高于室温，不会出现室温自燃现象，具备良好的安全性，又显著低于传统的800℃以上的活性炭活化温度，极大的降低了活化能耗，在120℃～200℃低温环境内的局部区域中依靠材料自身能量短期内维持超过1000℃的高温，将传统活化时间从1h以上缩短到几分钟至十几秒内，大大提高了活化效率。
(4)本申请开创了“爆燃法”，该方法在大孔材料的制备领域应用提供了一个开端，具有极高的创新价值和工业生产价值，制得的大孔活性炭形貌好，速度快，能耗低，简易制备，产量高，具有现有技术所不具备的巨大优势。
(5)本申请首创跃迁式局部高温加热方法，创造阶梯形的快速升温方式，实现活性炭在极短时间内大孔化；突破了“在其他条件相同时，在一定范围内，活化时间的增加有助于提高活化效果，即缩短活化时间活化效果也会变差”的常规思想误区，能够在短时间内活化并保证活化效果。
(6)由于不用进行炭化过程，而直接采用成品活性炭进行“大孔化”活化处理，因而本发明对所采用的成品活性炭的原始微观形貌没有特殊要求，任何形貌的活性炭均可采用本发明进行快速、低能耗、简便的大孔化处理。
附图说明
为了更清楚地说明本发明实例或现有技术中的技术方案，下面将对实施实例或现有技术描述中所需要的附图做简单地介绍，显而易见地，下面描述中的附图 仅仅是本发明的一些实例，对于本领域普通技术人员来说，在不付出创造性的前提下，还可以根据这些附图获得其他的附图：
图1为本发明钟乳石状大孔活性炭制得的夹心结构示意图；
图2为本发明实施例1制得的钟乳石状大孔活性炭的SEM图；
图3为本发明实施例2制得的钟乳石状大孔活性炭的SEM图；
图4为本发明实施例3制得的钟乳石状大孔活性炭的SEM图；
图5为本发明实施例4制得的钟乳石状大孔活性炭的SEM图。
具体实施方式
下面对本发明的具体实施方式作进一步详细的说明，但本发明并不局限于这些实施方式，任何在本实施例基本精神上的改进或代替，仍属于本发明权利要求所要求保护的范围。
实施例1
一种钟乳石状大孔活性炭的制备方法，包括以下步骤：
(1)按照质量比为1:5称取总质量为180g的活性炭与氢氧化钾作为活化活性炭前驱体，置于转速为200r/min～1200r/min的球磨罐中球磨15min～2h混合均匀，平均分成10份，每份18g，然后将球磨后的活化活性炭前驱体压制成片状，在其两侧设置导热基底，使其处于两片导热基底之间；
(2)按照质量比为83:17称取铁粉和高氯酸钾作为高温自引燃剂，压制成片状后，置于上述导热基底无活化活性炭前驱体的外侧面上；所述高氯酸钾作为氧化剂；
(3)按照质量比为1:2称取锆与铬酸钡作为低温助燃剂，压制成片状后，置于上述高温自引燃剂的外侧面上，使得原料从外向内依次形成低温助燃剂→高温自引燃剂→导热基底→活化活性炭前驱体的夹心结构；
(4)将10个上述夹心结构置于密闭的氮气氛围中加热至120℃～200℃，利用环境温度引燃低温助燃剂，令低温助燃剂瞬间产生上千摄氏度的温度引燃高温自引燃剂，使得在导热基底上的活化活性炭前驱体局部温度处于1000℃以上，然后完成活化，活化的时间为3s～2min，冷却至室温后在导热基底上得到钟乳石状大孔活性炭。
进一步地，所述低温助燃剂、高温自引燃剂、活化活性炭前驱体和导热基底的质量比＝0.5:10:1:1；在步骤(1)、(2)及(3)，所述压制成片的压机压力为10kpa～2000kpa；所述导热基底为镍；所述导热基底的直径为18～130mm。本实施例钟乳石状大孔活性炭的微观形貌如图2所示。
实施例2
一种钟乳石状大孔活性炭的制备方法，包括以下步骤：
(1)按照质量比为1:5称取总质量为180g活性炭和氢氧化钾作为活化活性炭前驱体，置于转速为200r/min～1200r/min的球磨罐中球磨15min～2h混合均匀，平均分成10份，每份18g，然后将球磨后的活化活性炭前驱体压制成片状，在其两侧设置导热基底，使其处于两片导热基底之间；
(2)按照质量比为83:17称取铁粉和高氯酸钾作为高温自引燃剂，压制成片状后，置于上述导热基底无活化活性炭前驱体的外侧面上；所述高氯酸钾作为氧化剂；
(3)按照质量比为1:2称取锆和铬酸钡作为低温助燃剂，压制成片状后，置于上述高温自引燃剂的外侧面上，使得原料从外向内依次形成低温助燃剂→高温自引燃剂→导热基底→活化活性炭前驱体的夹心结构；
(4)将10个上述夹心结构置于密闭的氩气、氮气或真空氛围中加热至120℃～200℃，利用环境温度引燃低温助燃剂，令低温助燃剂瞬间产生上千摄氏度的温度引燃高温自引燃剂，使得在导热基底上的活化活性炭前驱体局部温度处 于1000℃以上，然后完成活化，活化的时间为3s～2min，冷却至室温后在导热基底上得到钟乳石状大孔活性炭。
进一步地，所述低温助燃剂、高温自引燃剂、活化活性炭前驱体和导热基底的质量比＝0.5:10:1:1；在步骤(1)、(2)及(3)，所述压制成片的压机压力为10kpa～2000kpa；所述导热基底为钛；所述导热基底的直径为18～130mm。本实施例钟乳石状大孔活性炭的微观形貌如图3所示。
实施例3
一种钟乳石状大孔活性炭的制备方法，包括以下步骤：
(1)按照质量比为1:4称取总质量为180g活性炭和氢氧化钾作为活化活性炭前驱体，置于转速为200r/min～1200r/min的球磨罐中球磨15min～2h混合均匀，平均分成10份，每份18g，然后将球磨后的活化活性炭前驱体压制成片状，在其两侧设置导热基底，使其处于两片导热基底之间；
(2)按照质量比为83:17称取铁粉和高氯酸钠作为高温自引燃剂，压制成片状后，置于上述导热基底无活化活性炭前驱体的外侧面上；所述高氯酸钠作为氧化剂；
(3)按照质量比为1:2称取锆和铬酸钡作为低温助燃剂，压制成片状后，置于上述高温自引燃剂的外侧面上，使得原料从外向内依次形成低温助燃剂→高温自引燃剂→导热基底→活化活性炭前驱体的夹心结构；
(4)将10个上述夹心结构置于密闭的氩气氛围中加热至120℃～200℃，利用环境温度引燃低温助燃剂，令低温助燃剂瞬间产生上千摄氏度的温度引燃高温自引燃剂，使得在导热基底上的活化活性炭前驱体局部温度处于1000℃以上，然后完成活化，活化的时间为3s～2min，冷却至室温后在导热基底上得到钟乳石状大孔活性炭。
进一步地，所述低温助燃剂、高温自引燃剂、活化活性炭前驱体和导热基底的质量比＝0.5:15:1:1；在步骤(1)、(2)及(3)，所述压制成片的压机压力 为10kpa～2000kpa；所述导热基底为镍、钛、铂中的一种；所述导热基底的直径为18～130mm。本实施例钟乳石状大孔活性炭的微观形貌如图4所示。
实施例4
一种钟乳石状大孔活性炭的制备方法，包括以下步骤：
(1)按照质量比为1:4称取总质量为180g活性炭和氢氧化钾作为活化活性炭前驱体，置于转速为200r/min～1200r/min的球磨罐中球磨15min～2h混合均匀，平均分成10份，每份18g，然后将球磨后的活化活性炭前驱体压制成片状，在其两侧设置导热基底，使其处于两片导热基底之间；
(2)按照质量比为80:20称取铁粉和高氯酸锂作为高温自引燃剂，压制成片状后，置于上述导热基底无活化活性炭前驱体的外侧面上；所述高氯酸锂作为氧化剂；
(3)按照质量比为1:2称取锆和铬酸钡作为低温助燃剂，压制成片状后，置于上述高温自引燃剂的外侧面上，使得原料从外向内依次形成低温助燃剂→高温自引燃剂→导热基底→活化活性炭前驱体的夹心结构；
(4)将10个上述夹心结构置于密闭的-0.9Mpa的真空氛围中加热至120℃～200℃，利用环境温度引燃低温助燃剂，令低温助燃剂瞬间产生上千摄氏度的温度引燃高温自引燃剂，使得在导热基底上的活化活性炭前驱体局部温度处于1000℃以上，然后完成活化，活化的时间为3s～2min，冷却至室温后在导热基底上得到钟乳石状大孔活性炭。
进一步地，所述低温助燃剂、高温自引燃剂、活化活性炭前驱体和导热基底的质量比＝0.5:12:1:1；在步骤(1)、(2)及(3)，所述压制成片的压机压力为10kpa～2000kpa；所述导热基底为镍、钛、铂中的一种；所述导热基底的直径为18～130mm。本实施例钟乳石状大孔活性炭的微观形貌如图5所示。
对比例1
按照专利申请CN107226470A中的实施例进行活性炭的制备。
对比例2
按照专利申请CN107140635A中的实施例进行活性炭的制备。
对比例3
按照专利申请CN109179404A中的实施例进行活性炭的制备。
对比例4
按照专利申请CN109081344A中的实施例进行活性炭的制备。
对比例5
按照专利申请CN102442665A中的实施例进行活性炭的制备。
对比例6
按照文献Appl.Sci.2017,7,1036中的方法进行活性炭的制备。
对比例7
按照文献J.Power Sources,342(2017)363-370.中的方法进行活性炭的制备。
对比例8
按照文献J.Alloys Compd.,693(2017)1297-1304.中的方法进行活性炭的制备。
采用本申请实施例1～4和对比例1～8的方法进行活性炭的制备，记录各组活化环境温度和活化时间，实验结果如下表1所示。
表1
组别 活化环境温度 活化时间
实施例1 180℃ 20s
实施例2 150℃ 20s
实施例3 120℃ 3s
实施例4 200℃ 10s
对比例1 700℃～1000℃ 1h～3.5h
对比例2 700℃～1000℃ 1h～3.5h
对比例3 800℃～950℃ 2h～3h
对比例4 850℃ 1h
对比例5 1850℃ 1h
对比例6 700℃～800℃ 1h～3h
对比例7 600～800℃ 1h
对比例8 900℃ 2h
由表1实验数据可知，与现有技术相比，本申请活性炭的制备方法活化时间较短，所需活化环境温度较低。
综上所述，本发明可在低温环境内获得钟乳石状大孔活性炭，缩短活化时间，将传统的活化时间在1h以上压缩到数分钟至几秒内，并将传统的活化环境温度从800℃以上降低至120℃～200℃，首创跃迁式局部高温加热方法，创造阶梯形的快速升温方式，实现活性炭在极短时间内大孔化；设备功耗大幅降低，反应速度快，反应所需环境温度低，可以极大提高大孔活性炭的制备效率，具有效率高、安全性高、能耗低、活性炭形貌好的优点，具有极高的工程应用价值。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在没有背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同腰间的含义和范围内的所有变化囊括在本发明的保护范围之内。

Claims (7)

  1. 一种钟乳石状大孔活性炭的制备方法，其特征在于，包括以下步骤：
    (1)称取活化活性炭前驱体，置于转速为200r/min～1200r/min的球磨罐中球磨15min～2h，然后将球磨后的活化活性炭前驱体压制成片状，在其两侧设置导热基底，使其处于两片导热基底之间；
    (2)称取高温自引燃剂压制成片状后，置于上述导热基底无活化活性炭前驱体的外侧面上；
    (3)称取低温助燃剂压制成片状后，置于上述高温自引燃剂的外侧面上，使得原料从外向内依次形成低温助燃剂→高温自引燃剂→导热基底→活化活性炭前驱体的夹心结构；
    (4)将上述夹心结构置于密闭的氩气、氮气或真空氛围中加热至120℃～200℃，利用环境温度引燃低温助燃剂，令低温助燃剂瞬间产生上千摄氏度的温度引燃高温自引燃剂，使得在导热基底上的活化活性炭前驱体局部温度处于1000℃以上，然后完成活化，冷却至室温后在导热基底上得到钟乳石状大孔活性炭；
    在步骤(1)，所述活化活性炭前驱体为活性炭和氢氧化钾，且所述活性炭与氢氧化钾的质量比为1:3.1～7.9；
    在步骤(2)，所述高温自引燃剂为铁粉和氧化剂，且所述铁粉和氧化剂的质量比＝70～88:12～30；
    在步骤(3)，所述低温助燃剂为锆和铬酸钡，且所述锆和铬酸钡的质量比＝3～4:6～7。
  2. 根据权利要求1所述的一种钟乳石状大孔活性炭的制备方法，其特征在于：所述低温助燃剂、高温自引燃剂、活化活性炭前驱体和导热基底的质量比＝0.3～1.5:8～15:1:0.5～1。
  3. 根据权利要求1所述的一种钟乳石状大孔活性炭的制备方法，其特征在于：所述氧化剂为高氯酸钾、高氯酸锂、高氯酸钠中的一种或一种以上。
  4. 根据权利要求1所述的一种钟乳石状大孔活性炭的制备方法，其特征在于：在步骤(1)、(2)及(3)，所述压制成片的压机压力为10kpa～2000kpa。
  5. 根据权利要求1所述的一种钟乳石状大孔活性炭的制备方法，其特征在于：在步骤(4)，所述活化的时间为3s～2min。
  6. 根据权利要求1所述的一种钟乳石状大孔活性炭的制备方法，其特征在于：所述导热基底为镍、钛、铂中的一种。
  7. 根据权利要求1所述的一种钟乳石状大孔活性炭的制备方法，其特征在于：所述导热基底的直径为18～130mm。
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