TW202241807A - Method for producing porous carbon - Google Patents
Method for producing porous carbon Download PDFInfo
- Publication number
- TW202241807A TW202241807A TW110114336A TW110114336A TW202241807A TW 202241807 A TW202241807 A TW 202241807A TW 110114336 A TW110114336 A TW 110114336A TW 110114336 A TW110114336 A TW 110114336A TW 202241807 A TW202241807 A TW 202241807A
- Authority
- TW
- Taiwan
- Prior art keywords
- activation
- carbon
- porous carbon
- treatment
- carbonization
- Prior art date
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
Description
本發明係有關於一種可以增加比表面積之活性碳製程方法。The invention relates to an activated carbon process method capable of increasing the specific surface area.
一般的活性碳需要經過活化處理，才能產生具有高孔隙與高比表面積的活性碳，並能夠利用其強力的吸附能力將物質吸附。而活化處理可區分為物理活化法與化學活化法。物理活化法是利用二氧化碳或是水蒸氣做為活化劑，將系統加熱到高溫，使碳材中的碳變為二氧化碳逸散，而在表面留下孔洞，惟此種活化方法會造成大量碳材損失使產率降低。又化學活化法則是利用氫氧化鉀、氫氧化鈉、氯化鋅、磷酸等化學藥劑，使碳材直接和化學藥劑進行反應，原料經過膨脹、脫水、侵蝕後產生許多孔隙，但所使用的化學藥劑會有污染環境的缺點產生。General activated carbon needs to be activated to produce activated carbon with high porosity and high specific surface area, and can use its strong adsorption capacity to adsorb substances. The activation treatment can be divided into physical activation method and chemical activation method. The physical activation method is to use carbon dioxide or water vapor as an activator to heat the system to a high temperature, so that the carbon in the carbon material becomes carbon dioxide and escapes, leaving holes on the surface. However, this activation method will cause a large amount of carbon Losses reduce productivity. The chemical activation method is to use chemical agents such as potassium hydroxide, sodium hydroxide, zinc chloride, phosphoric acid, etc. to make the carbon material directly react with the chemical agent. The raw material will produce many pores after expansion, dehydration, and erosion, but the chemical used Medicines have the disadvantage of polluting the environment.
因此有中華民國109年3月11日所公告之發明第I687371號「用於電極材料的活性碳製造方法」專利案，主要係包含：將活化的碳材料在包括含氯氣體的環境中進行熱處理的步驟，其中，在所述進行熱處理的步驟之後的活化的碳材料中，金屬雜質的含量為0.1ppm至20ppm以下。並對與活化劑混合的碳化的碳材料進行該活化的步驟能夠在500℃以上；500℃至1200℃；500℃至1000℃；或者600℃至800℃的活化溫度中執行。當包括在該溫度範圍時，能夠提供比表面積大，微孔等的形成好，避免因活性碳凝結導致的粒子大小增加問題，以及結晶度優秀的活性碳。惟該專利前案由於需要使用高溫活化，會造成能源的耗損。Therefore, there is the patent case of Invention No. I687371 "Activated Carbon Manufacturing Method for Electrode Materials" announced on March 11, 2019, which mainly includes: heat-treating activated carbon materials in an environment containing chlorine gas The step, wherein, in the activated carbon material after the step of performing heat treatment, the content of metal impurities is 0.1 ppm to 20 ppm or less. And the step of activating the carbonized carbon material mixed with an activator can be performed at an activation temperature above 500°C; 500°C to 1200°C; 500°C to 1000°C; or 600°C to 800°C. When included in this temperature range, it is possible to provide activated carbon having a large specific surface area, good formation of micropores, etc., avoiding the problem of particle size increase due to coagulation of activated carbon, and excellent crystallinity. However, due to the need to use high temperature activation in this patent, it will cause energy consumption.
又有2020年4月30日所公開的論文「Mesopore-dominated hollow carbon nanoparticles prepared by simple air oxidation of carbon black for high mass loading supercapacitors」。該篇論文雖然揭露有使用低於550度的溫度，利用空氣空燒碳的技術。但是其僅揭露利用碳黑做為碳材的原料，並未揭露其他的材料做為碳材的原料。而且所製成的活性碳僅能達到比表面積為750m 2/g左右，並無法達到3000m 2/g，因此與本發明的技術特徵明顯不同。 There is also a paper "Mesopore-dominated hollow carbon nanoparticles prepared by simple air oxidation of carbon black for high mass loading supercapacitors" published on April 30, 2020. Although the paper discloses the technology of using air to burn carbon at a temperature lower than 550 degrees. However, it only discloses the use of carbon black as the raw material of the carbon material, and does not disclose other materials as the raw material of the carbon material. Moreover, the activated carbon can only reach a specific surface area of about 750m 2 /g, but cannot reach 3000m 2 /g, so it is obviously different from the technical characteristics of the present invention.
爰此，有鑑於目前活性碳在活化處理時具有上述的缺點。故本發明提供一種多孔碳製造方法，包含有：將一碳材原料進行一碳化處理，係將該碳材原料進置入一碳化空間內進行碳化處理；將該碳材原料置入於一活化空間內進行一活化處理，並添加一活化氣體，該活化氣體的添加量係為0.3至1920公升，進行該活化處理時的活化溫度係為400至550℃，活化時間係為30至960分鐘，藉以製成一多孔碳材。Therefore, in view of the current activated carbon has the above-mentioned shortcomings in the activation treatment. Therefore, the present invention provides a method for producing porous carbon, which includes: carrying out a carbonization treatment on a carbon material raw material, which is to put the carbon material raw material into a carbonization space for carbonization treatment; place the carbon material raw material in an activation An activation treatment is carried out in the space, and an activation gas is added. The amount of the activation gas added is 0.3 to 1920 liters, the activation temperature is 400 to 550°C, and the activation time is 30 to 960 minutes. In order to make a porous carbon material.
上述碳材原料的來源係為廢輪胎碳、廢塑膠、生質物質、木屑、咖啡渣、稻稈、甘蔗渣、瀝青、碳黑、石墨、石墨烯、碳管其中之一或其任意組合。The sources of the above-mentioned carbon materials are waste tire carbon, waste plastics, biomass, wood chips, coffee grounds, rice straw, bagasse, pitch, carbon black, graphite, graphene, carbon tubes, or any combination thereof.
上述碳材原料係採用廢輪胎碳、木屑、咖啡渣、稻稈或甘蔗渣，需要先進行一純化處理，該純化處理係以0.5至6M的酸性溶液或0.5至6M的鹼性溶液進行處理，其處理溫度為25至100℃，處理時間為0.5至16小時。The above-mentioned carbon materials are made of waste tire carbon, sawdust, coffee grounds, rice straw or bagasse, and need to be purified first. The purification process is treated with an acidic solution of 0.5 to 6M or an alkaline solution of 0.5 to 6M. The treatment temperature is 25 to 100° C., and the treatment time is 0.5 to 16 hours.
上述酸性溶液的成分係為鹽酸、硫酸或硝酸，該鹼性溶液的成分係為氫氧化鉀或氫氧化鈉。The components of the above-mentioned acidic solution are hydrochloric acid, sulfuric acid or nitric acid, and the components of the alkaline solution are potassium hydroxide or sodium hydroxide.
上述碳化空間係為一碳化爐，該活化空間係為一活化爐。The above-mentioned carbonization space is a carbonization furnace, and the activation space is an activation furnace.
上述活化氣體係為氧氣及/或空氣，該氧氣的添加量係為0.3至1920公升，該空氣的添加量係為0.3至1920公升，活化溫度係為450至550℃，活化時間係為90至300分鐘。The above-mentioned activation gas system is oxygen and/or air, the addition amount of the oxygen is 0.3 to 1920 liters, the addition amount of the air is 0.3 to 1920 liters, the activation temperature is 450 to 550 ° C, and the activation time is 90 to 90 liters. 300 minutes.
上述活化處理選用該氧氣或該空氣時，需再添加一活化輔助氣體，該活化輔助氣體的輸入量係為0.3至1920公升，該活化輔助氣體的輸入流速為10至2000ml/min。When the above-mentioned activation process uses the oxygen or the air, it is necessary to add an activated auxiliary gas. The input volume of the activated auxiliary gas is 0.3 to 1920 liters, and the input flow rate of the activated auxiliary gas is 10 to 2000 ml/min.
上述活化輔助氣體係為氧化氮、二氧化氮、一氧化碳、二氧化碳或水蒸氣。The above activated auxiliary gas system is nitrogen oxide, nitrogen dioxide, carbon monoxide, carbon dioxide or water vapor.
上述多孔碳材的比表面積係為500至3000m 2/g。 The specific surface area of the above-mentioned porous carbon material is 500 to 3000 m 2 /g.
上述碳化處理的碳化溫度係為250至800℃，碳化時間係為0.5至16小時。The carbonization temperature of the above carbonization treatment is 250 to 800° C., and the carbonization time is 0.5 to 16 hours.
上述技術特徵具有下列之優點：The above technical features have the following advantages:
1.由於採用低溫(小於550℃)進行活化處理，與習知傳統活性碳的製程不管是化學法或是物理法均需要高溫活化的技術不同，因此相對的可以大幅節省能源。1. Since the activation treatment is performed at low temperature (less than 550°C), it is different from the traditional activated carbon process that requires high temperature activation, whether it is chemical or physical, so it can save a lot of energy.
2.由於碳材原料是來自於生活中的廢棄材料及材料，因此不需要特別製備，而且可以減少廢棄物的數量及對於環境破壞的衝擊。2. Since the raw materials of carbon materials come from waste materials and materials in daily life, no special preparation is required, and the amount of waste and the impact on environmental damage can be reduced.
3. 所製成之多孔碳可以增加比表面積，更具有高純度及高熱穩定性，並可應用於氣體儲存、儲能元件(如鋰離子電池及超級電容)等技術領域。3. The prepared porous carbon can increase the specific surface area, has high purity and high thermal stability, and can be used in technical fields such as gas storage and energy storage components (such as lithium-ion batteries and super capacitors).
4.由於製造過程的步驟相當單純簡單，如果是純碳的碳材原料，甚至於只要一個活化處理步驟即可達成，完全不需要後續的純化處理。4. Since the steps of the manufacturing process are quite simple and simple, if it is a pure carbon raw material, it only needs one activation treatment step to achieve it, and no subsequent purification treatment is required at all.
請參閱第一圖所示，本發明實施例係包含有下列步驟：Please refer to the first figure, the embodiment of the present invention includes the following steps:
A.將一碳材原料進行一碳化處理。該碳材原料的來源係可為廢輪胎碳、廢塑膠、生質物質及其廢棄物(例如木屑、咖啡渣、稻稈、甘蔗渣)、瀝青、碳黑、石墨、石墨烯、碳管其中之一或其任意組合。如該碳材原料係採用廢輪胎碳或生質材料廢棄物時，需要預先進行純化處理，主要係以0.5至6M的酸性溶液或0.5至6M的鹼性溶液進行處理，其處理溫度為25至100℃，處理時間為0.5至16小時，藉以以去除其中雜質。該酸性溶液的成分係為鹽酸(HCl)、硫酸(H 2SO 4)或硝酸(HNO 3)，該鹼性溶液的成分係為氫氧化鉀(KOH)或氫氧化鈉(NaOH)。然後將該碳材原料進置入一碳化空間內進行碳化處理，該碳化空間係為一碳化爐，碳化處理的碳化溫度係為250至800℃，碳化時間係為0.5至16小時。 A. Carry out a carbonization treatment on a carbon material raw material. The source of the carbon raw material can be waste tire carbon, waste plastic, biomass and its waste (such as wood chips, coffee grounds, rice straw, bagasse), pitch, carbon black, graphite, graphene, carbon tubes, etc. one or any combination thereof. If the carbon material raw material is waste tire carbon or biomass material waste, it needs to be purified in advance, mainly with 0.5 to 6M acidic solution or 0.5 to 6M alkaline solution, and the treatment temperature is 25 to 60 100°C, the treatment time is 0.5 to 16 hours, so as to remove the impurities. The components of the acidic solution are hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ) or nitric acid (HNO 3 ), and the components of the alkaline solution are potassium hydroxide (KOH) or sodium hydroxide (NaOH). Then put the carbon raw material into a carbonization space for carbonization treatment, the carbonization space is a carbonization furnace, the carbonization temperature of the carbonization treatment is 250-800°C, and the carbonization time is 0.5-16 hours.
B.將該碳材原料進行一活化處理，並添加一活化氣體。將該碳材原料置入於一活化空間內進行碳化處理，該活化空間係為一活化爐，並於該活化空間中加入該活化氣體，該活化氣體的添加量係為0.3至1920公升。該活化氣體係為氧氣及/或空氣，該氧氣及/或空氣的添加量係分別為0.3至1920公升。進行該活化處理時的活化溫度係為400至550℃，最佳的活化溫度則為450至550℃，活化時間係為30至960分鐘，最佳的活化時間則為90至300分鐘。B. Carrying out an activation treatment on the carbon material raw material, and adding an activation gas. The carbon material raw material is placed in an activation space for carbonization treatment. The activation space is an activation furnace, and the activation gas is added into the activation space. The amount of the activation gas is 0.3 to 1920 liters. The activated gas system is oxygen and/or air, and the addition amount of the oxygen and/or air is 0.3 to 1920 liters respectively. The activation temperature during the activation treatment is 400 to 550° C., the optimum activation temperature is 450 to 550° C., the activation time is 30 to 960 minutes, and the optimum activation time is 90 to 300 minutes.
C.於活化處理時並添加一活化輔助氣體。又如採用上述的氧氣或空氣其中之一進行活化處理時，必須另外再輸入一活化輔助氣體，該活化輔助氣體係為氧化氮、二氧化氮、一氧化碳、二氧化碳或水蒸氣，該活化輔助氣體的輸入量係為0.3至1920公升，該活化輔助氣體的輸入流速為10至2000ml/min。C. During the activation process, add an activation auxiliary gas. Another example is when one of the above-mentioned oxygen or air is used for activation treatment, an activation auxiliary gas must be input in addition. The activation auxiliary gas system is nitrogen oxide, nitrogen dioxide, carbon monoxide, carbon dioxide or water vapor. The input volume is 0.3 to 1920 liters, and the input flow rate of the activated auxiliary gas is 10 to 2000 ml/min.
如此，該碳材原料經由上述製造方法製成後，可以製成一多孔碳材。該多孔碳材經由掃描電子顯微鏡(SEM)拍攝下的表面結構，如第二圖所示。又該多孔碳材經由透射電子顯微鏡(TEM)拍攝下的孔洞結構，如第三圖所示。並且該多孔碳材經由比表面積分析儀(BET)測量後，其比表面積係為500至3000m 2/g。 In this way, the carbon material raw material can be made into a porous carbon material after being made through the above-mentioned manufacturing method. The surface structure of the porous carbon material photographed by a scanning electron microscope (SEM) is shown in the second figure. The pore structure of the porous carbon material photographed by a transmission electron microscope (TEM) is shown in the third figure. And after the porous carbon material is measured by a specific surface area analyzer (BET), its specific surface area is 500 to 3000 m 2 /g.
該多孔碳材再進一步經由實驗測試，未經活化前碳材a及低溫活化後多孔碳材b的氮氣吸/脫附等溫線，如第四圖所示，明顯可以看出多孔碳材具有優異的吸/脫附性。如第五圖所示，係為該多孔碳材在不同的活化溫度下進行活化處理後，該多孔碳材的比表面積分布圖。由該第五圖中可以清楚看出，在活化溫度500℃時，該多孔碳材的比表面積可以達到2895m 2/g，適足以證明本發明之製造方法確實可以達到增加比表面積之功效。而且製成的該多孔碳材，更具有高純度及高熱穩定性，並可應用於氣體儲存、儲能元件〔如鋰離子電池(Lithium-ion batteries)及超級電容(Supercapacitors)〕等技術領域。 The porous carbon material was further tested experimentally. The nitrogen adsorption/desorption isotherms of carbon material a before activation and porous carbon material b after low-temperature activation are shown in the fourth figure. It can be clearly seen that the porous carbon material has Excellent adsorption/desorption properties. As shown in the fifth figure, it is a distribution diagram of the specific surface area of the porous carbon material after the activation treatment of the porous carbon material at different activation temperatures. It can be clearly seen from the fifth figure that when the activation temperature is 500°C, the specific surface area of the porous carbon material can reach 2895m 2 /g, which is enough to prove that the production method of the present invention can indeed achieve the effect of increasing the specific surface area. Moreover, the porous carbon material produced has high purity and high thermal stability, and can be applied to technical fields such as gas storage and energy storage components (such as Lithium-ion batteries and supercapacitors).
綜合上述實施例之說明，當可充分瞭解本發明之操作、使用及本發明產生之功效，惟以上所述實施例僅係為本發明之較佳實施例，當不能以此限定本發明實施之範圍，即依本發明申請專利範圍及發明說明內容所作簡單的等效變化與修飾，皆屬本發明涵蓋之範圍內。Based on the description of the above-mentioned embodiments, it is possible to fully understand the operation of the present invention, use and the effect that the present invention produces, but the above-mentioned embodiments are only preferred embodiments of the present invention, and should not be used to limit the implementation of the present invention. The scope, that is, the simple equivalent changes and modifications made according to the patent scope of the present invention and the content of the description of the invention, all fall within the scope of the present invention.
a:未經活化前碳材 b:低溫活化後多孔碳材 a: carbon material without activation b: porous carbon material after low temperature activation
[第一圖]係為本發明實施例之製造流程圖。[The first figure] is the manufacturing flow chart of the embodiment of the present invention.
[第二圖]係為本發明實施例多孔碳材經由掃描電子顯微鏡(SEM)拍攝表面結構圖。[The second picture] is the surface structure picture taken by scanning electron microscope (SEM) of the porous carbon material of the embodiment of the present invention.
[第三圖]係為本發明實施例多孔碳材經由透射電子顯微鏡(TEM)拍攝孔洞結構圖。[Figure 3] is a pore structure picture of the porous carbon material of the embodiment of the present invention taken by a transmission electron microscope (TEM).
[第四圖]係為本發明實施例未經活化前碳材及低溫活化後多孔碳材的氮氣吸/脫附等溫線圖。[Figure 4] is the nitrogen adsorption/desorption isotherm diagram of the non-activated carbon material and the porous carbon material after low-temperature activation according to the embodiment of the present invention.
[第五圖]係為本發明實施例多孔碳材在不同活化溫度下進行活化處理後的比表面積分布圖。[FIG. 5] is the specific surface area distribution diagram of the porous carbon material of the embodiment of the present invention after activation treatment at different activation temperatures.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW110114336A TWI773263B (en) | 2021-04-21 | 2021-04-21 | Method for producing porous carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW110114336A TWI773263B (en) | 2021-04-21 | 2021-04-21 | Method for producing porous carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TWI773263B TWI773263B (en) | 2022-08-01 |
| TW202241807A true TW202241807A (en) | 2022-11-01 |
Family
ID=83806923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW110114336A TWI773263B (en) | 2021-04-21 | 2021-04-21 | Method for producing porous carbon |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI773263B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115692691A (en) * | 2022-08-22 | 2023-02-03 | 常州创明超电材料科技有限公司 | Porous carbon material for lithium battery negative electrode and preparation method thereof |
| CN115676825A (en) * | 2022-11-22 | 2023-02-03 | 浙江中宁硅业有限公司 | Porous carbon, silicon-carbon negative electrode material and preparation method of porous carbon |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111422864A (en) * | 2020-04-20 | 2020-07-17 | 东北大学 | Method for converting PET into porous carbon particles based on carbonization-activation method and application |
-
2021
- 2021-04-21 TW TW110114336A patent/TWI773263B/en active
Also Published As
| Publication number | Publication date |
|---|---|
| TWI773263B (en) | 2022-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9156694B2 (en) | Porous carbon and method of manufacturing same | |
| JP5400892B2 (en) | Method for producing porous activated carbon | |
| Wang et al. | KOH activation of carbon-based materials for energy storage | |
| JP5860600B2 (en) | Porous carbon | |
| TWI773263B (en) | Method for producing porous carbon | |
| WO2017084251A1 (en) | Mesoporous carbon material and manufacturing method therefor | |
| JPH05139712A (en) | Production of electric conductive porous carbon material | |
| Ha et al. | Fluorination methods and the properties of fluorinated carbon materials for use as lithium primary battery cathode materials | |
| JP2015051891A (en) | Porous carbon, humidification adsorbent, adsorption type heat pump and fuel battery | |
| KR101631180B1 (en) | Manufacturing method of active carbon derived from rice husks for hydrogen storage using chemical activation | |
| KR101419340B1 (en) | Preparation method of Graphite oxide and graphene nanosheet | |
| JP2015078110A (en) | Carbon porous body, production method thereof and ammonia adsorbent | |
| KR101273495B1 (en) | Tuning method of interlayer spacing in graphene oxide composites for hydrogen storage | |
| JP5860601B2 (en) | Porous carbon | |
| CN114956040B (en) | Nitrogen-oxygen doped hierarchical porous carbon material, preparation method and application | |
| US6013208A (en) | Manufacturing method for carbon material for electrical double layer capacitor | |
| JP6426582B2 (en) | Porous carbon | |
| KR101082590B1 (en) | Preparing method of Carbon nanotube for hydrogen storage | |
| CN104627995B (en) | Bubbly graphene material and preparation method thereof | |
| CN112707397A (en) | Preparation method of super-capacitor activated carbon | |
| JPH11307405A (en) | Electric double layer capacitor and electrode and activated carbon and its manufacture | |
| Tung et al. | The synthesis and characterization of high purity mixed microporous/mesoporous activated carbon from rice husk | |
| CN111533112A (en) | Graphene hollow nanospheres and preparation method thereof | |
| JP2016041656A (en) | Porous carbon | |
| KR20190073710A (en) | Method for manufacturing activated carbon for electrode material |