TW201515993A - 多孔質碳、調濕吸附材、吸附式熱泵及燃料電池 - Google Patents
多孔質碳、調濕吸附材、吸附式熱泵及燃料電池 Download PDFInfo
- Publication number
- TW201515993A TW201515993A TW103122658A TW103122658A TW201515993A TW 201515993 A TW201515993 A TW 201515993A TW 103122658 A TW103122658 A TW 103122658A TW 103122658 A TW103122658 A TW 103122658A TW 201515993 A TW201515993 A TW 201515993A
- Authority
- TW
- Taiwan
- Prior art keywords
- water vapor
- porous carbon
- adsorption
- vapor adsorption
- benzene
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/28—Selection of materials for use as drying agents
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28088—Pore-size distribution
- B01J20/28092—Bimodal, polymodal, different types of pores or different pore size distributions in different parts of the sorbent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
- F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B30/00—Heat pumps
- F25B30/04—Heat pumps of the sorption type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/8605—Porous electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8803—Supports for the deposition of the catalytic active composition
- H01M4/8807—Gas diffusion layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/96—Carbon-based electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0234—Carbonaceous material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/31—Pore size distribution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Drying Of Gases (AREA)
- Inert Electrodes (AREA)
Abstract
本發明係以提供一種於高濕度側可充分地吸附水蒸氣之多孔質碳為目的。
本發明之多孔質碳,其特徵為具備中孔及微孔,且以下述(1)式所示之水蒸氣吸附量比率為1.8以上,特別是,以下述(1)式所示之水蒸氣吸附量比率為2.0以上者佳。此外,係以相對濕度為70%時之水蒸氣吸附量為50mg/g以上者佳。
水蒸氣吸附量比率=相對濕度為90%時之水蒸氣吸附量/相對濕度為70%時之水蒸氣吸附量‧‧‧(1)
Description
本發明係關於多孔質碳等,特別是關於於高濕度側可充分地吸附水蒸氣之多孔質碳等。
在以汽車用吸附式冷凍機為首之熱泵等中,係要求溶劑吸附量多、吸脫附速度快、相對於施加壓力之反應性高。此外,由於暴露在高溫下,故亦要求一定程度的化學穩定性。然而,如下述非專利文獻1~3所示般,在被評估作為一般的吸附材之活性碳或二氧化矽凝膠等中,其並非可充分地滿足目前所需之吸附性能(吸附量、吸脫附速度)之材料。特別是,並無可於高濕度側充分地吸附水蒸氣之材料。
此外,係有人提出一種調濕用碳材,其係於650~800℃乾餾石油焦炭所得之調濕用碳材,其特徵為:於20的容量%以上30的容量%以下的範圍內具有氣孔(下述專利文獻1)。
[專利文獻1]日本特開2007-209844號公報
[非專利文獻1]Denso Technical Review Vol.11 No.1 2006
[非專利文獻2]Adsorption News Vol.10, NO.3, p.12-16(July 1996)(日本吸附學會)
[非專利文獻3]化學工學論文集15(1), p38-43
然而,即使使用上述專利文獻1所示之調濕用碳材,仍有於高濕度側無法充分地吸附水蒸氣之課題。
因此,本發明係以提供一種於高濕度側可充分地吸附水蒸氣之多孔質碳等為目的。
為了達成上述目的,本發明之多孔質碳,其特徵為:具備中孔及微孔,且以下述(1)式所示之水蒸氣吸附量比率為1.8以上。
水蒸氣吸附量比率=相對濕度為90%時之水蒸氣吸附量/相對濕度為70%時之水蒸氣吸附量‧‧‧(1)
根據本發明,係達到可提供一種於高濕度側可充分地吸附水蒸氣之多孔質碳等之優異效果。
1‧‧‧聚醯胺酸樹脂
2‧‧‧氧化鎂
3‧‧‧碳質壁
4‧‧‧細孔
5‧‧‧多孔質碳
第1圖係顯示本發明之製造步驟之圖,第1圖(a)顯示混合聚醯胺酸樹脂與氧化鎂之狀態之說明圖,第1圖(b)顯示對混合物進行熱處理之狀態之說明圖,第1圖(c)顯示多孔質碳之說明圖。
第2圖係顯示碳A1~A3、Z1~Z5中之相對濕度與水蒸氣吸附量的關係之圖表。
為了達成上述目的,本發明之多孔質碳,其特徵為:具備中孔及微孔,且以下述(1)式所示之水蒸氣吸附量比率為1.8以上。
水蒸氣吸附量比率=相對濕度為90%時之水蒸氣吸附量/相對濕度為70%時之水蒸氣吸附量‧‧‧(1)
當上述水蒸氣吸附量比率未達1.8時,於相對濕度為70%之時點,乃成為幾乎不具有多孔質碳的水蒸氣吸附餘力之狀態(具體而言,水大致充滿多孔質碳的細孔之狀態)。因此,當相對濕度超過70%時,幾乎無法吸附更多
的水蒸氣,難以控制水蒸氣吸附量。相對於此,當上述水蒸氣吸附量比率為1.8以上時,於相對濕度為70%之時點,係成為多孔質碳的水蒸氣吸附餘力充分之狀態(具體而言,水仍未充滿多孔質碳的細孔之狀態)。因此,即使相對濕度超過70%,仍可吸附更多的水蒸氣,可充分地控制水蒸氣吸附量。
以上述水蒸氣吸附量比率為2.0以上者佳。
當水蒸氣吸附量比率為2.0以上時,於高濕度氛圍中可進一步吸附水蒸氣,所以更能夠發揮作為吸附材的機能。
以上述相對濕度為70%時之水蒸氣吸附量為50mg/g以上者佳。
當相對濕度為70%時之水蒸氣吸附量未達50mg/g時,可吸附之水蒸氣量變少。因此無法發揮作為吸附材的機能,可應用之領域有時會受限。
以上述相對濕度為90%時之水蒸氣吸附量為300mg/g以上700mg/g以下者佳。
當相對濕度為90%時之水蒸氣吸附量未達300mg/g時,作為吸附材的機能低,可應用之領域有時會受限。另一方面,當相對濕度為90%時之水蒸氣吸附量超過700mg/g時,乃成為主要產生吸附現象之微孔的絕大部分由水蒸氣所填滿之狀態,有時難以控制吸附動作。
如上述般,主要產生水蒸氣的吸附現象者是微孔,但高濕度側之水蒸氣的吸附量則受到中孔的容量的影響。
以上述中孔的孔徑為3nm以上50nm以下,上述中孔的容量為0.9ml/g以上2.0ml/g以下者佳,特別是,以上述中孔的孔徑為4.5nm以上50nm以下者佳。
將上述中孔的孔徑限制在3nm以上(特別是4.5nm以上)者,是由於有時難以製作出較此更小孔徑者。此外,將中孔的容量限制在0.9ml/g以上2.0ml/g以下者,係依據以下所示之理由。當中孔的容量未達0.9ml/g時,比表面積小,有時於高濕度側無法充分地吸附水蒸氣。另一方面,當中孔的容量超過2.0ml/g時,全細孔中之微孔的容量(比率)極小,有時無法確保用以吸附水蒸氣之充分的比表面積。
全細孔的容量與微孔的容量與中孔的容量之關係如下述(2)式所示。
微孔的容量=全細孔的容量-中孔的容量‧‧‧(2)
以上述微孔的容量為0.3ml/g以上0.7ml/g以下者佳。
當上述微孔的容量未達0.3ml/g時,難以確保比表面積,有時無法充分地吸附水蒸氣。另一方面,當上述微孔的容量超過0.7ml/g時,由於微孔的容量對水蒸氣往微孔的擴散速度造成影響者所起因,有時會使作為吸附材的反應速度(吸附速度)降低。
係以將上述多孔質碳使用作為調濕吸附材的吸附材者為特徵。此外,係以將上述多孔質碳使用作為吸
附式熱泵的吸附材者為特徵。再者,係以將上述多孔質碳使用作為燃料電池用電極的碳系擔體者為特徵。
以下係說明具體的實施形態。
上述多孔質碳,例如可以下列方式製作。首先,本發明之多孔質碳,係在溶液或粉末狀態下,濕式或乾式混合含有有機質樹脂之流動性材料與氧化物(鑄模粒子)而製作出混合物。接著在非氧化氛圍或減壓氛圍下,例如在500℃以上的溫度使該混合物碳化。最後進行洗淨處理而去除鑄模粒子,藉此可製作出多孔質碳。如此製作之多孔質碳,具有多數個細孔(中孔及微孔)。惟細孔的配置並非具規則性,而是呈隨機配置之構造。
在此,藉由改變鑄模粒子的直徑或有機質樹脂的種類,可調整細孔徑、多孔質碳的細孔分布、及碳質壁的厚度。因此,藉由適當地選擇鑄模粒子的直徑或有機質樹脂的種類,亦可製作出具有更大的細孔容量之多孔質碳。
具體而言,上述有機質樹脂,係以使用於單位結構中含有至少一個以上的氮或氟原子之聚醯亞胺。該聚醯亞胺可藉由酸成分與二胺成分之聚縮合而得。惟此時於酸成分與二胺成分中任一者或兩者中必須具有一個以上的氮原子或氟原子。
具體而言,可藉由使聚醯亞胺的前驅物之聚醯胺酸成膜,並加熱去除溶劑而得到聚醯胺酸膜。接著在200℃以上使所得之聚醯胺酸膜進行熱醯亞胺化,藉此可製造出聚
醯亞胺。
前述二胺,可例示出2,2-雙(4-胺苯基)六氟丙烷[2,2-Bis(4-aminophenyl)hexafluoropropane]、2,2-雙(三氟甲基)-聯苯胺[2,2'-bis(trifluoromethyl)-benzidine]、4,4'-二胺基八氟聯苯、或3,3'-二氟-4,4'-二胺基二苯基甲烷、3,3'-二氟-4,4'-二胺基二苯基醚、3,3'-二(三氟甲基)-4,4'-二胺基二苯基醚、3,3'-二氟-4,4'-二胺基二苯基丙烷、3,3'-二氟-4,4'-二胺基二苯基六氟丙烷、3,3'-二氟-4,4'-二胺基二苯基酮、3,3',5,5'-四氟-4,4'-二胺基二苯基甲烷、3,3',5,5'-四(三氟甲基)-4,4'-二胺基二苯基甲烷、3,3',5,5'-四氟-4,4'-二胺基二苯基丙烷、3,3',5,5'-四(三氟甲基)-4,4'-二胺基二苯基丙烷、3,3',5,5'-四氟-4,4'-二胺基二苯基六氟丙烷、1,3-二胺基-5-(全氟壬烯氧基)苯、1,3-二胺基-4-甲基-5-(全氟壬烯氧基)苯、1,3-二胺基-4-甲氧基-5-(全氟壬烯氧基)苯、1,3-二胺基-2,4,6-三氟-5-(全氟壬烯氧基)苯、1,3-二胺基-4-氯-5-(全氟壬烯氧基)苯、1,3-二胺基-4-溴-5-(全氟壬烯氧基)苯、1,2-二胺基-4-(全氟壬烯氧基)苯、1,2-二胺基-4-甲基-5-(全氟壬烯氧基)苯、1,2-二胺基-4-甲氧基-5-(全氟壬烯氧基)苯、1,2-二胺基-3,4,6-三氟-5-(全氟壬烯氧基)苯、1,2-二胺基-4-氯-5-(全氟壬烯氧基)苯、1,2-二胺基-4-溴-5-(全氟壬烯氧基)苯、1,4-二胺基-3-(全氟壬烯氧基)苯、1,4-二胺基-2-甲基-5-(全氟壬烯氧基)苯、1,4-二胺基-2-甲氧基-5-(全氟壬烯氧基)苯、1,4-二胺基-2,3,6-三氟-5-(全氟壬烯氧基)苯、1,4-二胺基-2-氯-5-(全氟壬烯氧基)
苯、1,4-二胺基-2-溴-5-(全氟壬烯氧基)苯、1,3-二胺基-5-(全氟己烯氧基)苯、1,3-二胺基-4-甲基-5-(全氟己烯氧基)苯、1,3-二胺基-4-甲氧基-5-(全氟己烯氧基)苯、1,3-二胺基-2,4,6-三氟-5-(全氟己烯氧基)苯、1,3-二胺基-4-氯-5-(全氟己烯氧基)苯、1,3-二胺基-4-溴-5-(全氟己烯氧基)苯、1,2-二胺基-4-(全氟己烯氧基)苯、1,2-二胺基-4-甲基-5-(全氟己烯氧基)苯、1,2-二胺基-4-甲氧基-5-(全氟己烯氧基)苯、1,2-二胺基-3,4,6-三氟-5-(全氟己烯氧基)苯、1,2-二胺基-4-氯-5-(全氟己烯氧基)苯、1,2-二胺基-4-溴-5-(全氟己烯氧基)苯、1,4-二胺基-3-(全氟己烯氧基)苯、1,4-二胺基-2-甲基-5-(全氟己烯氧基)苯、1,4-二胺基-2-甲氧基-5-(全氟己烯氧基)苯、1,4-二胺基-2,3,6-三氟-5-(全氟己烯氧基)苯、1,4-二胺基-2-氯-5-(全氟己烯氧基)苯、1,4-二胺基-2-溴-5-(全氟己烯氧基)苯、或是不含氟原子之對苯二胺(PPD:p-Phenylene Diamine)、二氧基二苯胺等之芳香族二胺。此外,上述二胺成分可組合2種以上之上述各芳香族二胺而使用。
另一方面,酸成分可列舉出包含氟原子之4,4-六氟異亞丙基二鄰苯二甲酸酐(6FDA:4,4-Hexafluoroisopropylidene Diphthalic Anhydride)、及不含氟原子之3,4,3',4'-聯苯四羧酸二酐(BPDA:3,4,3',4'-Biphenyltetracarboxylic Dianhydride)、焦蜜石酸二酐(PMDA:Pyromellitic Dianhydride)等。
此外,用作為聚醯亞胺前驅物的溶劑之有機溶劑,可
列舉出N-甲基-2-吡咯啶酮、二甲基甲醯胺等。
醯亞胺化的手法,如一般所知的方法[例如參考高分子學會編「新高分子實驗學」共同出版、1996年3月28日、第3卷高分子的合成及反應(2)158頁]所示般,可依循加熱或化學醯亞胺化中任一方法,本發明並不受該醯亞胺化的方法左右。
再者,聚醯亞胺以外的樹脂,可使用石油焦分瀝青、丙烯酸樹脂等。
另一方面,使用作為上述氧化物之原料,除了鹼土類金屬氧化物(氧化鎂、氧化鈣)之外,亦可使用藉由熱處理,在熱分解過程中該狀態轉變為氧化鎂之金屬有機酸(檸檬酸鎂、草酸鎂、檸檬酸鈣、草酸鈣等)、氯化物、硝酸鹽、硫酸鹽。
此外,去除氧化物之洗淨液,係使用鹽酸、硫酸、硝酸、檸檬酸、乙酸、甲酸等之一般的無機酸,以使用2mol/l以下的稀薄酸者佳。此外,亦可使用80℃以上的熱水。
再者,前述混合物的碳化,係在非氧化氛圍或減壓氛圍下,在500℃以上,以在1500℃以下的溫度中進行者佳。由於高碳產率的樹脂為高分子,所以在未達500℃時,有時碳化不足而使細孔的發達不足,另一方面,超過1500℃時,收縮增大使氧化物燒結而粗大化,導致細孔的大小縮小而使比表面積降低。非氧化氛圍,是指氬氣氛圍或氮氣氛圍,減壓氛圍,是指133Pa(1torr)以
下的氛圍。
上述多孔質碳的總體密度,以0.1g/cc以上1.0g/cc以下者佳。當總體密度未達0.1g/cc時,難以確保比表面積,變得無法保持碳質壁的形狀,另一方面,當總體密度超過1.0g/cc時,難以形成三維網目構造,有時會使細孔的形成不足。
首先如第1圖(a)所示,以3:2的重量比混合作為鑄模粒子的氧化鎂粉末(MgO,平均粒徑為5nm)2與作為碳前驅物的有機物樹脂(聚乙烯醇)1。接著如第1圖(b)所示,將此混合物於惰性氛圍中,在900℃進行2小時的熱處理,使聚乙烯醇熱分解,藉此得到具備碳質壁3之燒結物。然後如第1圖(c)所示,藉由以1mol/l的比率所添加之硫酸溶液洗淨所得之燒結物,使MgO完全溶出。藉此得到具有多數個細孔4之非晶質的多孔質碳5。
以下,將如此製作之多孔質碳材料稱為材料A1。
除了使用平均粒徑為20nm的氧化鎂粉末作為鑄模粒子之外,其他與上述實施例1相同而製作出多孔質碳。
以下,將如此製作之多孔質碳材料稱為材料A2。
除了使用鎂鹽(乙酸鎂)作為鑄模粒子,並使用作為碳前驅物的有機物樹脂(聚乙烯醇)之外,其他與上述實施例1相同而製作出多孔質碳。
以下,將如此製作之多孔質碳材料稱為材料A3。
使用市售的活性碳(和光純藥工業股份有限公司製 活性碳(製品編號037-02115))。
以下,將如此製作之活性碳稱為材料Z1。
在氮氣氛圍中,在900℃對由聚醯亞胺所構成之薄膜進行熱處理,而製作出碳材料。
以下,將如此製作之材料稱為材料Z2。
使用市售的合成沸石系吸附材(和光純藥工業股份有限公司製 合成沸石A-3(製品編號269-00555))。
以下,將如此製作之材料稱為材料Z3。
使用市售的合成沸石系吸附材(和光純藥工業股份有
限公司製 合成沸石F-9(製品編號261-00635))。
以下,將如此製作之材料稱為材料Z4。
使用市售的二氧化矽(Sigma-Aldrich公司製 MCM-41 type 643645)。
以下,將如此製作之材料稱為材料Z5。
對於上述材料A1~A3、Z1~Z5中的BET比表面積等,藉由下列方法進行調查,此等結果如第1表所示。
(1)首先將材料A1~A3、Z1~Z5配置在密閉之吸附測定用玻璃光槽內後,於真空中,在300℃進行2小時的脫氣處理。
(2)使用氮氣作為吸附氣體,在77K(-196℃)進行測定並求取氮吸附等溫線。該測定係使用BEL Japan股份有限公司製的自動氣體/蒸氣吸附量測定裝置BELSORP-18。BET比表面積,係從相對壓(P/P0)=0.05~2.20之範圍的測定點中算出。
全細孔的容量,係從相對壓(P/P0)0.95時的吸附量中求取,微孔的容量,係藉由Dubinin-Radushkevitch(DR)法求取。此外,中孔的容量,係從上述全細孔的容量及微孔的容量之差所求取。
(3)中孔徑及微孔徑的導出
中孔徑係以BJH(Berret-Joyner-Halenda)法求取,微孔徑係以HK(Horvath-Kawazoe)法求取。
(4)水蒸氣吸附測定
水蒸氣吸附測定,係使用BEL Japan股份有限公司製的自動氣體/蒸氣吸附量測定裝置BELSORP-18來進行。測定條件,係將吸附溫度設為25℃,並在相對壓(P/P0)為0~0.9的範圍內進行。此外,成為吸附質之水,係使用重複進行4~5次的凍結及脫泡處理而達到高純度化之蒸餾水。所得之吸附等溫線,係以橫軸為水蒸氣相對壓(P/P0),縱軸為試樣每1g所吸附之水蒸氣的量(mg/g)而描繪出。該結果如第2圖所示。
從第2圖中,調查25℃時的水蒸氣相對壓P/P0為0.70(意味著相對濕度為70%,以下有時稱為RH70)時之水蒸氣吸附量,以及P/P0為0.90(意味著相對濕度為90%,以下有時稱為RH90)時之水蒸氣吸附量,算出下述(1)式所示之水蒸氣吸附量比率。
水蒸氣吸附量比率=RH90時之水蒸氣吸附量/RH70時之水蒸氣吸附量‧‧‧(1)
從第1表及第2圖中,可得知於材料Z1~Z5中,RH90時之水蒸氣吸附量/RH70時之水蒸氣吸附量(以下有時稱為RH90/RH70)之值為1.0~1.7,相對於此,於材料A1~A3中,RH90/RH70之值為2.3~7.8。從該結果中,可得知材料A1~A3與材料Z1~Z5相比,其RH90/RH70之值較大。因此,於材料Z1~Z5中,於RH70之時點,乃成為幾乎不具有多孔質碳的水蒸氣吸附餘力之狀態,所以在成為RH90時,幾乎無法吸附水蒸氣。相對於此,於材料A1~A3中,於RH70之時點,係成為多孔質碳的水蒸氣吸附餘力充分之狀態,因此,即使成為RH90時,仍可充分地吸附水蒸氣。
成為該結果者,可考量為高濕度下的水蒸氣吸附量係與中孔的容量相依之故。亦即,於材料A1~A3中,中孔的容量為0.834~1.861ml/g之非常大之值,相對於此,於材料Z1~Z5中,不存在中孔,或即使存在,其容量也僅為0.024~0.455ml/g之非常小之值。因此,其可考量為導致上述實驗結果者。
本發明可使用作為調濕吸附材、吸附式熱泵、燃料電池用電極擔體等。
Claims (10)
- 一種多孔質碳,其特徵為:具備中孔及微孔,且以下述(1)式所示之水蒸氣吸附量比率為1.8以上,水蒸氣吸附量比率=相對濕度為90%時之水蒸氣吸附量/相對濕度為70%時之水蒸氣吸附量‧‧‧(1)。
- 如請求項1之多孔質碳,其中上述水蒸氣吸附量比率為2.0以上。
- 如請求項1或2之多孔質碳,其中上述相對濕度為70%時之水蒸氣吸附量為50mg/g以上。
- 如請求項1~3中任一項之多孔質碳,其中上述相對濕度為90%時之水蒸氣吸附量為300mg/g以上700mg/g以下。
- 如請求項1~4中任一項之多孔質碳,其中上述中孔的孔徑為3nm以上50nm以下,上述中孔的容量為0.9ml/g以上2.0ml/g以下。
- 如請求項5之多孔質碳,其中上述中孔的孔徑為4.5nm以上50nm以下。
- 如請求項1~6中任一項之多孔質碳,其中上述微孔的容量為0.3ml/g以上0.7ml/g以下。
- 一種調濕吸附材,其特徵為:使用如請求項1~7中任一項之多孔質碳作為吸附材。
- 一種吸附式熱泵,其特徵為:使用如請求項1~7中任一項之多孔質碳作為吸附材。
- 一種燃料電池,其特徵為:使用如請求項1~7中任一項之多孔質碳作為電極的碳系擔體。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013-184729 | 2013-09-06 | ||
JP2013184729A JP5695147B2 (ja) | 2013-09-06 | 2013-09-06 | 多孔質炭素、調湿吸着材、吸着式ヒートポンプ、及び燃料電池 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201515993A true TW201515993A (zh) | 2015-05-01 |
TWI638771B TWI638771B (zh) | 2018-10-21 |
Family
ID=52628132
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103122658A TWI638771B (zh) | 2013-09-06 | 2014-07-01 | Porous carbon, humidity-control adsorption material, adsorption heat pump and fuel cell |
Country Status (9)
Country | Link |
---|---|
US (1) | US10137405B2 (zh) |
EP (1) | EP3042877B1 (zh) |
JP (1) | JP5695147B2 (zh) |
KR (1) | KR102328148B1 (zh) |
CN (1) | CN105531224B (zh) |
CA (1) | CA2922942C (zh) |
MX (1) | MX2016001521A (zh) |
TW (1) | TWI638771B (zh) |
WO (1) | WO2015033643A1 (zh) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6391808B2 (ja) * | 2015-03-26 | 2018-09-19 | 新日鐵住金株式会社 | 固体高分子形燃料電池用の担体炭素材料及び触媒 |
JP6671719B2 (ja) * | 2015-11-16 | 2020-03-25 | アイシン精機株式会社 | バイオ燃料電池用のガス拡散電極材、及び、ガス拡散電極材の作製方法、ガス拡散電極材を備えるバイオ燃料電池 |
TWI647175B (zh) * | 2017-10-25 | 2019-01-11 | 台灣中油股份有限公司 | 生質油製作多重孔洞碳材之方法 |
JP7125892B2 (ja) * | 2018-11-20 | 2022-08-25 | 株式会社クレハ | アミロイドβ除去器具、生体由来液浄化システム、アミロイドβ除去方法およびアミロイドβ除去用吸着材 |
WO2021059932A1 (ja) * | 2019-09-27 | 2021-04-01 | パナソニックIpマネジメント株式会社 | 触媒、触媒層、膜/電極接合体、電気化学デバイス、触媒の製造方法 |
JPWO2022071320A1 (zh) | 2020-09-29 | 2022-04-07 | ||
EP4223415A1 (en) | 2020-09-29 | 2023-08-09 | N.E. Chemcat Corporation | Catalyst for electrodes, composition for forming gas diffusion electrode, gas diffusion electrode, membrane electrode assembly, and fuel cell stack |
FR3122585A1 (fr) * | 2021-05-04 | 2022-11-11 | Universite Claude Bernard Lyon 1 | Solide mésoporeux pour réguler l’humidité dans les espaces clos |
CN118715636A (zh) * | 2022-10-21 | 2024-09-27 | 宁德时代新能源科技股份有限公司 | 碳质材料及其制备方法、以及含有其的二次电池和用电装置 |
WO2024202884A1 (ja) * | 2023-03-31 | 2024-10-03 | 日鉄ケミカル&マテリアル株式会社 | 固体高分子型燃料電池の触媒担体用炭素材料、固体高分子型燃料電池用触媒層、燃料電池、及び固体高分子型燃料電池の触媒担体用炭素材料の製造方法 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02187127A (ja) * | 1989-01-14 | 1990-07-23 | Osaka Gas Co Ltd | 除湿材 |
JP2000072426A (ja) * | 1998-08-21 | 2000-03-07 | Daikyo Kensetsu Kk | 活性炭製造方法、調湿用活性炭及び調湿用建材 |
JP2002080213A (ja) * | 2000-09-07 | 2002-03-19 | Mitsubishi Chemicals Corp | 炭素質多孔材 |
JP4245522B2 (ja) * | 2003-07-07 | 2009-03-25 | 東洋炭素株式会社 | 炭素化物及びその製造方法 |
GB0506278D0 (en) | 2005-03-29 | 2005-05-04 | British American Tobacco Co | Porous carbon materials and smoking articles and smoke filters therefor incorporating such materials |
JP4571883B2 (ja) * | 2005-04-25 | 2010-10-27 | 株式会社タクマ | 含塩有機物を用いた蒸気吸放出材料 |
JP2007099612A (ja) * | 2005-09-06 | 2007-04-19 | National Institute Of Advanced Industrial & Technology | 均一な粒子径を有するメソ多孔性炭素ビーズ、その製造方法および製造装置、ならびに該メソ多孔性炭素ビーズを担体とする水処理用触媒、該触媒の性能評価装置と、該触媒を用いた実廃水処理装置 |
JP5057671B2 (ja) * | 2006-02-07 | 2012-10-24 | Jx日鉱日石エネルギー株式会社 | 調湿用炭素材およびその製造方法 |
JP5013503B2 (ja) * | 2006-02-16 | 2012-08-29 | 国立大学法人埼玉大学 | 疎水性活性炭の製造方法 |
JP4875562B2 (ja) * | 2007-07-20 | 2012-02-15 | クラレケミカル株式会社 | スピーカ装置用材料およびこれを用いたスピーカ装置 |
US20110315922A1 (en) | 2008-11-04 | 2011-12-29 | Donaldson Company Inc. | Custom water adsorption material |
JP2010208887A (ja) * | 2009-03-10 | 2010-09-24 | Toyo Tanso Kk | 多孔質炭素及びその製造方法 |
GB0904196D0 (en) | 2009-03-11 | 2009-04-22 | British American Tobacco Co | Methods for increasing mesopores in adsorbents |
JP5344473B2 (ja) * | 2009-04-07 | 2013-11-20 | 独立行政法人産業技術総合研究所 | 親水性炭素微細孔体およびその製造方法 |
JP5485734B2 (ja) * | 2010-02-05 | 2014-05-07 | 株式会社実践環境研究所 | 活性炭の製造方法及び活性炭 |
GB201007667D0 (en) * | 2010-05-07 | 2010-06-23 | British American Tobacco Co | Method of preparing porous carbon |
JP5935039B2 (ja) * | 2012-02-23 | 2016-06-15 | 地方独立行政法人青森県産業技術センター | 活性炭製造方法 |
-
2013
- 2013-09-06 JP JP2013184729A patent/JP5695147B2/ja active Active
-
2014
- 2014-06-16 MX MX2016001521A patent/MX2016001521A/es unknown
- 2014-06-16 CA CA2922942A patent/CA2922942C/en active Active
- 2014-06-16 CN CN201480046082.1A patent/CN105531224B/zh active Active
- 2014-06-16 KR KR1020167008945A patent/KR102328148B1/ko active IP Right Grant
- 2014-06-16 US US14/911,593 patent/US10137405B2/en active Active
- 2014-06-16 EP EP14842926.9A patent/EP3042877B1/en active Active
- 2014-06-16 WO PCT/JP2014/065925 patent/WO2015033643A1/ja active Application Filing
- 2014-07-01 TW TW103122658A patent/TWI638771B/zh not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
TWI638771B (zh) | 2018-10-21 |
EP3042877B1 (en) | 2021-02-17 |
JP5695147B2 (ja) | 2015-04-01 |
KR20160051879A (ko) | 2016-05-11 |
JP2015051891A (ja) | 2015-03-19 |
US10137405B2 (en) | 2018-11-27 |
KR102328148B1 (ko) | 2021-11-18 |
US20160199809A1 (en) | 2016-07-14 |
EP3042877A4 (en) | 2017-05-10 |
WO2015033643A1 (ja) | 2015-03-12 |
CN105531224B (zh) | 2018-10-16 |
CA2922942A1 (en) | 2015-03-12 |
EP3042877A1 (en) | 2016-07-13 |
MX2016001521A (es) | 2017-01-11 |
CN105531224A (zh) | 2016-04-27 |
CA2922942C (en) | 2022-09-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI638771B (zh) | Porous carbon, humidity-control adsorption material, adsorption heat pump and fuel cell | |
US9156694B2 (en) | Porous carbon and method of manufacturing same | |
TWI542537B (zh) | Porous carbon and a method for producing the same | |
JP5860600B2 (ja) | 多孔質炭素 | |
JP5860602B2 (ja) | 多孔質炭素 | |
JP6350918B2 (ja) | 吸着/脱離剤 | |
JP5860601B2 (ja) | 多孔質炭素 | |
JP2012218999A (ja) | 多孔質炭素及びその製造方法 | |
JP6216359B2 (ja) | 多孔質炭素 | |
JP6426582B2 (ja) | 多孔質炭素 | |
TW201601995A (zh) | 多孔質碳、其製造方法、及使用多孔質碳的吸附/分離裝置 | |
WO2015137107A1 (ja) | 多孔質炭素シート |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Annulment or lapse of patent due to non-payment of fees |