WO2019047155A1 - 一种氨气活化制备含氮活性炭的方法 - Google Patents

一种氨气活化制备含氮活性炭的方法 Download PDF

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Publication number
WO2019047155A1
WO2019047155A1 PCT/CN2017/101025 CN2017101025W WO2019047155A1 WO 2019047155 A1 WO2019047155 A1 WO 2019047155A1 CN 2017101025 W CN2017101025 W CN 2017101025W WO 2019047155 A1 WO2019047155 A1 WO 2019047155A1
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activation
nitrogen
temperature
activated carbon
atmosphere
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PCT/CN2017/101025
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English (en)
French (fr)
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左宋林
张文彬
王永芳
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南京林业大学
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Priority to US16/308,750 priority Critical patent/US20200299140A1/en
Priority to CN201780002479.4A priority patent/CN108064215A/zh
Priority to PCT/CN2017/101025 priority patent/WO2019047155A1/zh
Publication of WO2019047155A1 publication Critical patent/WO2019047155A1/zh

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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
    • C01B32/318—Preparation characterised by the starting materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/336—Preparation characterised by gaseous activating agents

Definitions

  • the invention relates to the field of activated carbon technology, in particular to a method for preparing nitrogen-containing activated carbon by activation of ammonia gas.
  • Activated carbon is a porous carbonaceous material with well-developed pore structure. It has excellent thermal stability and chemical stability and is widely used in environmental protection, electronics, energy, chemical, food and pharmaceutical fields. From the basic properties of activated carbon, its application properties mainly depend on its pore structure and surface chemistry, and its surface chemistry depends on a small number of constituent elements other than carbon and its combination with carbon. According to the main types of small amounts of elements contained in activated carbon, activated carbon can be classified into oxygen-containing activated carbon and nitrogen-containing activated carbon.
  • Nitrogen-containing activated carbon not only has similar energy storage and energy conversion capabilities as advanced nano-carbon materials, but also has rich electronic and alkaline properties due to nitrogen-containing groups such as pyridine, pyrrole and quaternary nitrogen in carbon structures. Nitrogen-containing activated carbon exhibits unique catalytic ability and excellent ability to selectively adsorb acidic components such as CO 2 .
  • the method for preparing nitrogen-containing activated carbon in the prior art mainly uses plasma treatment, impregnation of nitrogen-containing compounds, etc. to surface-modify the activated carbon to achieve the purpose of introducing nitrogen.
  • the use of surface modification requires the use of modified reagents and more complex modification processes, which are more complicated to operate and greatly increase the preparation cost.
  • the present invention provides a method for preparing a nitrogen-containing activated carbon by activating ammonia gas.
  • the present invention directly activates a carbonaceous raw material under an activator atmosphere to obtain a nitrogen-containing activated carbon, which is extremely simple and easy to operate. Implemented and at a lower cost.
  • the technical solution adopted by the present invention is:
  • a method for preparing nitrogen-containing activated carbon by activation of ammonia gas comprises the following steps:
  • the carbonaceous raw material is heated to a switching temperature under a protective atmosphere, the protective atmosphere being provided by one or more of nitrogen, argon and ammonia; the switching temperature is greater than or equal to 700 ° C and less than or equal to the activation temperature ;
  • the carbonaceous raw material is subjected to an activation reaction at an activation temperature to obtain a nitrogen-containing activated carbon.
  • the activator atmosphere further comprises an inert gas.
  • the volume content of ammonia in the activator atmosphere is ⁇ 50%.
  • the activation temperature is from 800 to 1100 °C.
  • the activation reaction time is 0.5 to 5 hours.
  • the carbonaceous raw material is one or more of biomass carbon, nitrogen-free activated carbon, coal and polymer material carbonized material.
  • the biomass carbon is one or more of charcoal, bamboo charcoal, nutshell charcoal and straw charcoal.
  • the polymer material is one or more of rubber, phenolic resin, epoxy resin and polyurethane.
  • the carbonaceous raw material has a particle size of ⁇ 80 mesh.
  • the temperature increase rate at which the carbonaceous raw material is heated to the switching temperature is 1 to 10 ° C/min.
  • the temperature increase rate from the switching temperature to the activation temperature is 1 to 10 ° C / min.
  • the invention provides a method for preparing nitrogen-containing activated carbon by activating ammonia: heating a carbonaceous raw material to a switching temperature under a protective atmosphere; switching the protective atmosphere to an activator atmosphere at a switching temperature, and then raising the temperature to an activation temperature; The activation reaction is carried out at a temperature to obtain a nitrogen-containing activated carbon; the protective atmosphere is one or more of nitrogen, argon and ammonia; and the activator atmosphere contains ammonia.
  • the invention directly activates the carbonaceous raw material in an activator atmosphere, and the nitrogen in the ammonia gas and the carbon in the raw material are activated and reacted to obtain a nitrogen-containing activated carbon, which is extremely simple in operation, easy to implement and low in cost.
  • the nitrogen-containing activated carbon obtained by the invention contains nitrogen-containing groups such as pyridine, pyrrole and quaternary nitrogen, and has high specific surface area, high total pore volume and high nitrogen content. Specifically, the specific surface area can reach 2321 m 2 /g. The total pore volume can reach 1.476cm 3 /g, and the nitrogen content can reach 7.17%.
  • nitrogen-containing groups such as pyridine, pyrrole and quaternary nitrogen
  • the invention provides a method for preparing nitrogen-containing activated carbon by activation of ammonia gas, comprising the following steps:
  • the carbonaceous raw material is heated to a switching temperature under a protective atmosphere, the protective atmosphere being provided by one or more of nitrogen, argon and ammonia; the switching temperature is greater than or equal to 700 ° C and less than or equal to the activation temperature ;
  • the carbonaceous raw material is subjected to an activation reaction at an activation temperature to obtain a nitrogen-containing activated carbon.
  • the present invention heats the carbonaceous raw material to a switching temperature under a protective atmosphere.
  • the carbonaceous raw material is preferably one or more of biomass carbon, nitrogen-free activated carbon, coal, and a carbonaceous material of a polymer material.
  • the biomass charcoal is preferably one or more of charcoal, bamboo charcoal, nutshell charcoal and straw charcoal.
  • the polymer material carbonized material refers to carbon obtained by carbonization of a polymer material; the polymer material is preferably one or more of rubber, phenol resin, epoxy resin and polyurethane.
  • the carbonization operation of the present invention may be carried out by a carbonization operation well known to those skilled in the art.
  • each of the substances is preferably mixed in equal mass.
  • the particle size of the carbonaceous raw material is preferably ⁇ 80 mesh (0.178 mm), more preferably ⁇ 60 mesh (0.425 mm), and most preferably ⁇ 40 mesh (0.250 mm).
  • the present invention does not have any special requirements for the source of the carbonaceous raw material, and it is sufficient to use the above-mentioned specific materials which are well known to those skilled in the art.
  • the carbonaceous raw material is a nitrogen-free activated carbon raw material
  • the commercially available conventional nitrogen-free activated carbon raw material obtained by the method of the present application has a nitrogen-containing activated carbon containing nitrogen and having a more pore structure.
  • the carbonaceous raw material is placed in an activation device in which the atmosphere is protected and the carbonaceous raw material is heated in a protective atmosphere.
  • the activation means are preferably commercially available fixed bed activation furnaces, activation converters, multi-tube furnaces or fluidization furnaces well known to those skilled in the art.
  • the protective atmosphere is one or more of nitrogen, argon and ammonia; and when the protective atmosphere is preferably two or three of nitrogen, argon and ammonia, the mixing The gas is preferably a mixture of ammonia and other gases.
  • the inert atmosphere when the protective atmosphere is nitrogen and/or argon, the inert atmosphere can protect the carbonaceous raw material from any reaction during the temperature rising phase; when the protective atmosphere is ammonia gas, or is nitrogen and argon When one or two kinds of gas are mixed with ammonia gas, the atmosphere replacement step at the subsequent activation can be reduced, and the operation can be simplified.
  • the present invention does not have any special requirements for the manner of temperature rise, and may be carried out by a temperature rising method well known to those skilled in the art.
  • the temperature increase rate of the temperature rise is preferably from 1 to 10 ° C/min, more preferably from 5 ° C/min.
  • the present invention switches the protective atmosphere to the activator gas at the switching temperature.
  • the activator atmosphere preferably contains ammonia gas, and more preferably further contains an inert gas.
  • the inert atmosphere is preferably argon and/or nitrogen.
  • the volume content of ammonia gas in the activator atmosphere is preferably ⁇ 50%, more preferably ⁇ 70%, and most preferably ⁇ 90%. .
  • the present invention does not have any special requirements for the embodiment of the atmosphere switching, and may be carried out in a manner commonly used by those skilled in the art.
  • the present invention preferably drives all of the protective atmosphere in the activation device out by means of an activation atmosphere. After the atmosphere is switched, if the switching temperature is lower than the activation temperature, the present invention immediately starts the next stage of the temperature rising operation until the temperature is raised to the activation temperature, and the temperature of the switching temperature does not need to be maintained; if the switching temperature is equal to the activation temperature, The present invention can be directly subjected to an activation reaction without further performing a temperature rising operation.
  • the activation temperature is preferably 800 to 1100 ° C, more preferably 850 to 1000 ° C, and most preferably 900 ° C.
  • the present invention does not have any special requirements for the temperature rise mode when the temperature is switched from the switching temperature to the activation temperature, and may be carried out by a temperature rising method well known to those skilled in the art.
  • the temperature increase rate of the temperature increase in this step is preferably from 1 to 10 ° C / min, more preferably 5 ° C / min.
  • the present invention performs an activation reaction at an activation temperature to obtain a nitrogen-containing activated carbon.
  • the activation reaction time is preferably from 0.5 to 5 hours, more preferably from 1 to 4 hours, and most preferably from 2 to 3 hours.
  • the present invention can take out the nitrogen-containing activated carbon product by lowering the activation device to room temperature; for cost consideration, the present invention can take out the nitrogen-containing activated carbon product after cooling the activation device to below 500 ° C, and then continue to activate The unit performs atmosphere replacement and feeding operations for the next batch production.
  • the nitrogen-containing activated carbon obtained by the invention has the characteristics of high specific surface area, high total pore volume and high nitrogen content. Specifically, the specific surface area can reach 2321 m 2 /g, the total pore volume can reach 1.476 cm 3 /g, and the nitrogen content can be Up to 7.17%.
  • AC 40-60 mesh coconut shell activated carbon
  • the carbonaceous raw material is placed in a fixed bed activation furnace, nitrogen gas is introduced, and the temperature is switched to the switching temperature at 5 ° C / min, and the gas is switched to ammonia. Gas, after the temperature is continuously raised to a predetermined activation temperature, the activation reaction is carried out by holding for 1 hour. After completion, the nitrogen-containing activated carbon was taken out to below 500 ° C, and the yield of ammonia activation was calculated from the ratio of the mass of the nitrogen-containing activated carbon obtained to the mass of the raw material.
  • the prepared sample was named AC-X and X represents the activation temperature.
  • the content of C, H, N, O in nitrogen-containing activated carbon samples was determined by the Vario EL cube elemental analyzer from Elementar, Germany. The O content was determined by analysis in oxygen mode.
  • the adsorption-desorption isotherm of activated carbon was tested using a Quantachrome Autosorb-iQ2 automatic adsorber.
  • the mesoporous pore volume (V mes ) is obtained by subtracting the pore volume from the total pore volume.
  • the carbonaceous raw material is placed in a fixed bed activation furnace, nitrogen gas is introduced, and the temperature is raised to 700 ° C at 5 ° C / min, and ammonia gas is introduced, when the temperature rises.
  • the activation reaction was carried out by holding for 1 hour.
  • the nitrogen-containing activated carbon was taken out to below 500 ° C, and the yield of ammonia activation was calculated from the ratio of the mass of the nitrogen-containing activated carbon obtained to the mass of the raw material.
  • the prepared sample was named WC-X and X represents the activation temperature.
  • ammonia gas can significantly activate charcoal to produce nitrogen-containing activated carbon with highly developed pore structure, and its nitrogen content can reach between 3 and 7%.
  • specific surface area of 1000 °C activated by ammonia can be prepared to achieve a specific surface area of more than 2300m 2 ⁇ g -1 high specific surface area of a nitrogen-containing activated carbon.
  • the 40-60 mesh coconut shell carbonized material (YC) is used as the carbonaceous raw material, and the carbonaceous raw material is placed in a fixed bed activation furnace, nitrogen gas is introduced, and the temperature is raised to 700 ° C at 5 ° C / min, and ammonia gas is introduced. After the temperature is raised to 1000 ° C, the activation reaction is carried out for a predetermined time (activation time). End After cooling to 500 ° C or less, the nitrogen-containing activated carbon was taken out, and the yield of ammonia activation was calculated according to the ratio of the mass of the nitrogen-containing activated carbon obtained to the mass of the raw material.
  • the prepared sample was named YC-X, and X represents the activation time (minutes).
  • the nitrogen-containing activated carbon having a specific surface area of 2300 m 2 ⁇ g -1 can be prepared by activating the coconut shell carbon raw material at 1000 ° C, and the nitrogen content thereof can reach 3.5% or more.
  • the activation time has a significant effect on the activation of ammonia. With the extension of time, the yield of activated carbon is significantly reduced, and the pore structure becomes more developed. However, too long activation time, ie excessive ablation, is not conducive to the development of pores.
  • the activated raw material is placed in a fixed bed activation furnace, nitrogen gas is introduced, and the temperature is raised to 700 ° C at 5 ° C / min, then ammonia gas is introduced, and when the temperature is raised to 1000 ° C Thereafter, the activation reaction is carried out for a predetermined time (activation time) of the incubation. After completion, the nitrogen-containing activated carbon was taken out to below 500 ° C, and the yield of ammonia activation was calculated from the ratio of the mass of the nitrogen-containing activated carbon obtained to the mass of the raw material.
  • the prepared sample was named CC-X and X represents the activation time (minutes).

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Abstract

一种氨气活化制备含氮活性炭的方法：在保护气氛下，将碳质原料升温至切换温度，在切换温度下将保护气氛切换为活化剂气氛后升温至活化温度，在活化温度下进行活化反应，得到含氮活性炭。保护气氛为氮气、氩气和氨气中的一种或几种；活化剂气氛包含氨气。该方法直接将碳质原料在活化剂气氛下进行活化，氨气中的氮和原料中的炭发生活化反应，得到含氮活性炭，操作简便，易于实施且成本较低。

Description

一种氨气活化制备含氮活性炭的方法 技术领域
本发明涉及活性炭技术领域，尤其涉及一种氨气活化制备含氮活性炭的方法。
背景技术
活性炭是一种孔隙结构发达的多孔炭质材料，热稳定性和化学稳定性优良，广泛应用于环境保护、电子、能源、化工、食品和医药等领域。从活性炭的基本性质来看，其应用性能主要取决于它的孔隙结构与表面化学性质，而其表面化学性质取决于除碳元素以外的少量组成元素种类及其与碳元素的结合方式。按照活性炭所含有的主要少量元素种类，可以将活性炭分为含氧活性炭和含氮活性炭等。
含氮活性炭不仅具有与先进纳米碳材料近似的储能和能源转化能力，并且由于炭结构中的吡啶、吡咯和季氮型等含氮基团所具有的富电子特性与显碱性特性，使含氮活性炭表现出独特的催化能力和优良选择性吸附CO2等酸性成分的能力。
目前，现有技术中制备含氮活性炭的方法主要是采用等离子处理、浸渍含氮化合物等来对活性炭进行表面改性，达到引入氮元素的目的。然而，采用表面改性方式需要采用改性试剂和较复杂的改性工艺，操作较复杂，大大增加了制备成本。
发明内容
为了克服现有技术的上述缺点，本发明提供一种氨气活化制备含氮活性炭的方法，本发明直接将碳质原料在活化剂气氛下进行活化即可得到含氮活性炭，操作极其简便，易于实施且成本较低。
为了解决上述技术问题，本发明采用的技术方案是：
一种氨气活化制备含氮活性炭的方法，包含如下步骤：
在保护气氛下，将碳质原料升温至切换温度，所述保护气氛由氮气、氩气和氨气中的一种或几种气体提供；所述切换温度大于等于700℃，且小于等于活化温度；
在切换温度下，将保护气氛切换为活化剂气氛，所述活化剂气氛包含氨气；
在活化温度下，所述碳质原料进行活化反应，得到含氮活性炭。
优选的，所述活化剂气氛还包含惰性气体。
优选的，所述活化剂气氛中氨气的体积含量≥50％。
优选的，所述活化温度为800～1100℃。
优选的，所述活化反应的时间为0.5～5h。
优选的，所述碳质原料为生物质炭、不含氮活性炭、煤炭和高分子材料炭化料中的一种或几种。
优选的，所述生物质炭为木炭、竹炭、果壳炭和秸秆炭中的一种或几种。
优选的，所述高分子材料为橡胶、酚醛树脂、环氧树脂和聚氨酯中的一种或几种。
优选的，所述碳质原料的粒度≤80目。
优选的，将碳质原料升温至切换温度的升温速率为1～10℃/min。
优选的，从切换温度升温至活化温度的升温速率为1～10℃/min。
本发明提供了一种氨气活化制备含氮活性炭的方法：在保护气氛下，将碳质原料升温至切换温度；在切换温度下将保护气氛切换为活化剂气氛后升温至活化温度；在活化温度下进行活化反应，得到含氮活性炭；所述保护气氛为氮气、氩气和氨气中的一种或几种；所述活化剂气氛包含氨气。本发明直接将碳质原料在活化剂气氛下进行活化，氨气中的氮和原料中的炭发生活化反应，得到含氮活性炭，操作极其简便，易于实施且成本较低。
本发明得到的含氮活性炭中包含吡啶、吡咯和季氮型等含氮基团，具有高比表面积、高总孔容积和高含氮率特性，具体的，比表面积可达2321m2/g，总孔容积可达1.476cm3/g，含氮率可达7.17％。
具体实施方式
本发明提供了一种氨气活化制备含氮活性炭的方法，包含如下步骤：
在保护气氛下，将碳质原料升温至切换温度，所述保护气氛由氮气、氩气和氨气中的一种或几种气体提供；所述切换温度大于等于700℃，且小于等于活化温度；
在切换温度下，将保护气氛切换为活化剂气氛，所述活化剂气氛包含氨气；
在活化温度下，所述碳质原料进行活化反应，得到含氮活性炭。
本发明在保护气氛下，将碳质原料升温至切换温度。在本发明中，所述碳质原料优选为生物质炭、不含氮活性炭、煤炭和高分子材料炭化料中的一种或几种。在本发明中，所述生物质炭优选为木炭、竹炭、果壳炭和秸秆炭中的一种或几种。在本发明中，所述高分子材料炭化料是指由高分子材料经炭化得到的碳；所述高分子材料优选为橡胶、酚醛树脂、环氧树脂和聚氨酯中的一种或几种。本发明对所述炭化操作采用本领域技术人员所熟知的炭化操作进行即可。在本发明中，当所述碳质原料优选为上述具体选择中的多种物质的混合物时，各物质优选等质量混合。
在本发明中，所述碳质原料的粒度优选的≤80目(0.178mm)，更优选的≤60目(0.425mm)，最优选的≤40目(0.250mm)。
本发明对所述碳质原料的来源没有任何的特殊要求，采用本领域技术人员所熟知的市售的上述具体物质即可。在本发明中，当所述碳质原料为不含氮活性炭原料时，市售的常规不含氮活性炭原料经过本申请方法处理后得到的含氮活性炭含氮且孔隙结构更加发达。
本发明优选将所述碳质原料置于活化装置中，所述活化装置内为保护气氛，使所述碳质原料在保护气氛下进行升温。在本发明中，所述活化装置优选为本领域技术人员所熟知的市售的固定床活化炉、活化转炉、多管炉或流态化炉。在本发明中，所述保护气氛为氮气、氩气和氨气中的一种或几种；当所述保护气氛优选为氮气、氩气和氨气中的两种或三种时，该混合气体优选为氨气和其它气体的混合物。在本发明中，当所述保护气氛为氮气和/或氩气时，该惰性气氛能够保护碳质原料在升温阶段不发生任何的反应；当所述保护气氛为氨气，或者为氮气和氩气中的一种或两种与氨气的混合气体时，能够减少后续活化时的气氛置换步骤，简化操作。
本发明对所述升温的方式没有任何的特殊要求，采用本领域技术人员所熟知的升温方式进行即可。在本发明具体实施例中，所述升温的升温速率优选为1～10℃/min，更优选为5℃/min。
升温至切换温度后，本发明在切换温度下将保护气氛切换为活化剂气 氛。在本发明中，所述活化剂气氛优选包含氨气，更优选的还包含惰性气体。在本发明中，所述惰性气氛优选为氩气和/或氮气。在本发明中，当所述活化剂气氛同时包含氨气和惰性气体时，所述活化剂气氛中氨气的体积含量优选的≥50％，更优选的≥70％，最优选的≥90％。本发明对所述气氛切换的实施方式没有任何的特殊要求，采用本领域技术人员所常用的方式进行即可。在具体实施过程中，本发明优选通过通入活化气氛的方式将活化装置中的保护气氛全部赶出。将气氛切换完毕后，若切换温度小于活化温度，本发明即立刻开始进行下一阶段的升温操作，直至将温度升温至活化温度，无需再继续保持切换温度的温度；若切换温度等于活化温度，本发明无需再进行升温操作，直接进行活化反应即可。
在本发明中，所述活化温度优选为800～1100℃，更优选为850～1000℃，最优选为900℃。本发明对由切换温度升温至活化温度时的升温方式没有任何的特殊要求，采用本领域技术人员所熟知的升温方式进行即可。在本发明具体实施例中，本步骤所述升温的升温速率优选为1～10℃/min，更优选为5℃/min。
本发明在活化温度下进行活化反应，得到含氮活性炭。在本发明中，所述活化反应的时间优选为0.5～5h，更优选为1～4h，最优选为2～3h。
所述活化反应结束后，本发明将活化装置降温至室温即可取出含氮活性炭产品；出于成本考虑，本发明将活化装置降温至500℃以下即可取出含氮活性炭产品，然后继续对活化装置进行气氛替换和加料操作，进行一下批次的生产。
本发明得到的含氮活性炭具有高比表面积、高总孔容积和高含氮率特性，具体的，比表面积可达2321m2/g，总孔容积可达1.476cm3/g，含氮率可达7.17％。
下面结合实施例对本发明提供的氨气活化制备含氮活性炭的方法进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
采用40～60目的椰壳活性炭(AC)为碳质原料，将碳质原料置于固定床活化炉中，通入氮气，以5℃/min升温至切换温度后，将气体切换为氨 气，当温度持续升高到预定的活化温度后，保温1小时进行活化反应。结束后冷却至500℃以下取出含氮活性炭，根据得到的含氮活性炭质量与原料的质量之比计算氨气活化的得率。所制备的样品命名为AC-X，X表示活化温度。
采用德国Elementar公司Vario EL cube型元素分析仪测定含氮活性炭样品中C，H，N，O的含量，其中O含量在氧模式下分析测定得到。采用Quantachrome公司Autosorb-iQ2型自动吸附仪测试活性炭的吸附-脱附等温线。用BET法计算样品的比表面积(SBET)，以P/P0＝0.99点计算样品的总孔容积(VTot)，采用Du-binin-Radushkevic方程计算微孔的孔容(Vmic)，总孔容减去微孔孔容即得到中孔孔容(Vmes)。
表1采用椰壳活性炭为原料的氨气活化结果
Figure PCTCN2017101025-appb-000001
从表1可以看出，含氮活性炭的得率随氨气活化温度的升高而不断降低，同时孔隙结构不断发展，其比表面积和比孔容积显著增大，但中孔孔容发展不明显；活性炭的氮元素含量可以达到3.6％以上，表明氨气活化在活性炭中引入了丰富的含氮基团。
实施例2
采用20～60目的木炭(WC)为碳质原料，将碳质原料置于固定床活化炉中，通入氮气，以5℃/min升温至700℃后，通入氨气，当温度升高到预定的活化温度后，保温1小时进行活化反应。结束后冷却至500℃以下取出含氮活性炭，根据得到的含氮活性炭质量与原料的质量之比计算氨气活化的得率。所制备的样品命名为WC-X，X表示活化温度。
采用与实施例1相同的方法分析木炭与含氮活性炭的元素含量与孔隙结构。其结果见表2所示。
表2采用木炭为原料的氨气活化结果
Figure PCTCN2017101025-appb-000002
从表2可以看出，氨气能够显著活化木炭制备出孔隙结构高度发达的含氮活性炭，其氮元素含量可以达到3～7％之间。采用比表面积仅仅为124m2·g-1的木炭为原料，经1000℃的氨气活化可以制备出比表面积达到2300m2·g-1以上的高比表面积含氮活性炭。
实施例3
采用40～60目的椰壳炭化料(YC)为碳质原料，将碳质原料置于固定床活化炉中，通入氮气，以5℃/min升温至700℃后，通入氨气，当温度升高到1000℃后，保温预定的时间(活化时间)进行活化反应。结束 后冷却至500℃以下取出含氮活性炭，根据得到的含氮活性炭质量与原料的质量之比计算氨气活化的得率。所制备的样品命名为YC-X，X表示活化时间(分钟)。
采用与实施例1相同的方法分析椰壳炭与活性炭的元素含量与孔隙结构。其结果见表3所示。
表3采用椰壳炭化料为原料的氨气活化结果
Figure PCTCN2017101025-appb-000003
从表3可以看出，椰壳炭原料在1000℃下经过氨气活化可以制备出比表面积达到2300m2·g-1的含氮活性炭，其氮含量可以达到3.5％以上。活化时间对于氨气活化具有显著影响，随着时间的延长，活性炭的得率显著减少，孔隙结构变得更加发达，但太长的活化时间，即过度烧蚀，不利于孔隙的发展。
实施例4
采用40～60目的煤炭(CC)为原料，将活化原料置于固定床活化炉中，通入氮气，以5℃/min升温至700℃后，通入氨气，当温度升高到1000℃后，保温预定的时间(活化时间)进行活化反应。结束后冷却至500℃以下取出含氮活性炭，根据得到的含氮活性炭质量与原料的质量之比计算氨气活化的得率。所制备的样品命名为CC-X，X表示活化时间(分钟)。
采用与实施例1相同的方法分析煤炭与活性炭的元素含量与孔隙结构。其结果见表4所示。
表4采用煤炭为原料的氨气活化结果
Figure PCTCN2017101025-appb-000004
从表4可以看出，尽管经过1000℃的氨气活化，煤炭的孔隙结构得到较显著的发展，其比表面积达到607m2·g-1，氮含量达到2.8％。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (11)

  1. 一种氨气活化制备含氮活性炭的方法，包含如下步骤：
    在保护气氛下，将碳质原料升温至切换温度，所述保护气氛由氮气、氩气和氨气中的一种或几种气体提供；
    在切换温度下，将保护气氛切换为活化剂气氛后继续升温至活化温度，所述活化剂气氛包含氨气；
    在所述活化温度下，所述碳质原料进行活化反应，得到含氮活性炭。
  2. 根据权利要求1所述的方法，其特征在于，所述活化剂气氛还包含惰性气体。
  3. 根据权利要求2所述的方法，其特征在于，所述活化剂气氛中氨气的体积含量≥50％。
  4. 根据权利要求1～3任意一项所述的方法，其特征在于，所述活化温度为800～1100℃。
  5. 根据权利要求4所述的方法，其特征在于，所述活化反应的时间为0.5～5h。
  6. 根据权利要求1所述的方法，其特征在于，所述碳质原料为生物质炭、不含氮活性炭、煤炭和高分子材料炭化料中的一种或几种。
  7. 根据权利要求6所述的方法，其特征在于，所述生物质炭为木炭、竹炭、果壳炭和秸秆炭中的一种或几种。
  8. 根据权利要求6所述的方法，其特征在于，所述高分子材料为橡胶、酚醛树脂、环氧树脂和聚氨酯中的一种或几种。
  9. 根据权利要求6～8任意一项所述的方法，其特征在于，所述碳质原料的粒度≤80目。
  10. 根据权利要求1所述的方法，其特征在于，将碳质原料升温至切换温度的升温速率为1～10℃/min。
  11. 根据权利要求1或10所述的方法，其特征在于，从切换温度升温至活化温度的升温速率为1～10℃/min。
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