TW201726549A - 多孔碳材料及其製造方法、以及過濾介質、薄片及觸媒用載體 - Google Patents
多孔碳材料及其製造方法、以及過濾介質、薄片及觸媒用載體 Download PDFInfo
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- TW201726549A TW201726549A TW106101595A TW106101595A TW201726549A TW 201726549 A TW201726549 A TW 201726549A TW 106101595 A TW106101595 A TW 106101595A TW 106101595 A TW106101595 A TW 106101595A TW 201726549 A TW201726549 A TW 201726549A
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 89
- 238000004519 manufacturing process Methods 0.000 title claims description 31
- 239000003054 catalyst Substances 0.000 title claims description 16
- 239000011148 porous material Substances 0.000 claims abstract description 38
- 230000005484 gravity Effects 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000000465 moulding Methods 0.000 claims description 15
- 238000001994 activation Methods 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000010903 husk Substances 0.000 claims description 4
- 238000004887 air purification Methods 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 241000196324 Embryophyta Species 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 238000001179 sorption measurement Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003763 carbonization Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000012530 fluid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
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- 238000003795 desorption Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
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- 239000010902 straw Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 244000062793 Sorghum vulgare Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 235000019713 millet Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
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- 238000004804 winding Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical compound C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241001474374 Blennius Species 0.000 description 1
- 241000195940 Bryophyta Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000526670 Echinochloa esculenta Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 241000985694 Polypodiopsida Species 0.000 description 1
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- 241000209056 Secale Species 0.000 description 1
- 235000007238 Secale cereale Nutrition 0.000 description 1
- 241000592342 Tracheophyta Species 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000002603 lanthanum Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
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Abstract
本發明的目的係提供一種多孔碳材料,其粒徑在10μm以上且1cm以下,其容積比重在0.20g/cm3以上,且其中孔容積在0.10cm3/g以上。
Description
本發明係關於多孔碳材料及其製造方法、以及過濾介質、薄片及觸媒用載體。
一直以來,以活性碳為代表的多孔碳材料係藉由以下方式來得到的:在高溫下,將植物性原料(例如木漿、椰子殼、穎殼等)、礦物性原料(例如煤、焦油、石油瀝青等)、及合成樹脂等作為原料之碳化物,以氣體及/或藥品處理並賦活化來形成微細孔。前述微細孔係以網狀構成於碳內部,且因為前述微細孔產生大的表面積,而使前述多孔碳材料的吸附能力優異。因此一直以來,前述多孔碳材料被廣泛地應用於去除惡臭、去除液體中不純物、溶劑蒸氣的回收以及去除等各種用途。更進一步,前述多孔碳材料還被用於載持觸媒的觸媒用載體。
就植物來源的多孔碳材料而言,舉例來說,先前技術揭示了將植物來源的材料碳化後,藉由酸或鹼的處理而得到多孔碳材料,前述多孔碳材料之氮BET法比表面積的値係10m2
/g以上,矽含量係1重量%以下,且細孔容積係0.1cm3
/g以上(參照專利文獻1)。
[先前技術文獻] [專利文獻] [專利文獻1]日本特開2008-273816號公報
[發明所欲解決之課題] 在多孔碳材料當中,對於大分子的吸附及/或高速吸附能力而言,中孔發達之碳材料係優異的。然而,因為如此之多孔碳材料空隙多且容積比重小,舉例來說,於濾心等重視單位體積下之性能的情況下,與一般來自椰子殼的活性碳相比,其僅能填充1/5~1/4的重量。 因此,雖然中孔發達之碳材料在單位重量下之吸附特性優異,但若從單位體積來看,則其無法發揮的情況很多,故其作為濾芯等時,具有很難發揮習知產品的性能以上之問題。
本發明係以解決習知的前述多個問題來達成以下目的,以作為課題。 意即,本發明之目的係提供一種中孔發達且容積比重大的多孔碳材料及其製造方法、以及使用前述多孔碳材料的過濾介質、濾芯、薄片及觸媒用載體。
[用於解決課題之手段] 作為解決前述課題的手段而言,如以下所述。意即, <1> 一種多孔碳材料,其粒徑在10μm以上且1cm以下,其容積比重在0.20g/cm3
以上,且其中孔容積在0.10cm3
/g以上。 <2> 如前述<1>所述之多孔碳,其中,前述多孔碳材料係由植物來源的材料而成。 <3> 如前述<2>所述之多孔碳,其中,前述植物來源的材料係穎殼。 <4> 一種過濾介質,其係包含前述<1>~<3>中任一者所述之多孔碳材料。 <5> 如前述<4>所述之過濾介質,其係淨水用。 <6> 如前述<4>所述之過濾介質,其係空氣淨化用。 <7> 一種濾芯,其係包含如前述<4>~<6>中任一者所述之過濾介質。 <8> 一種薄片,其係包含如前述<1>~<3>中任一者所述之多孔碳材料。 <9> 一種觸媒用載體,其係包含如前述<1>~<3>中任一者所述之多孔碳材料。 <10> 一種多孔碳材料的製造方法,其係製造如前述<1>~<3>中任一者所述之多孔碳材料的製造方法,其係包含:成型物製作製程,將植物來源的材料加壓成型,並得到成型物;碳化物製作製程,將前述成型物碳化,並得到碳化物;及賦活製程,賦活前述碳化物。 <11> 如前述<10>所述之多孔碳材料的製造方法,其中,前述植物來源的材料係穎殼。 <12> 如前述<10>或<11>所述之多孔碳材料的製造方法,其中,前述成型物製作製程係將含水率3質量%以上且30質量%以下之前述植物來源的材料加壓成型之製程。
[發明的效果] 根據本發明,能解決習知的前述多個問題,達成前述目的,能提供一種中孔發達且容積比重大的多孔碳材料及其製造方法、以及使用前述多孔碳材料的過濾介質、濾芯、薄片及觸媒用載體。
(多孔碳材料) 本發明的多孔碳材料係滿足以下(1)~(3)。 (1) 粒徑在10μm以上且1cm以下。 (2) 容積比重在0.20g/cm3
以上。 (3) 中孔容積在0.1cm3
/g以上。
<粒徑> 前述粒徑小於10μm之多孔碳材料的容積比重係很難變大(例如0.2g/cm3
以上)。前述粒徑超過1cm之多孔碳材料,其酸處理或鹼處理之去除灰分的所需時間容易變長,製造效率下降。
前述粒徑係例如使用雷射繞射/散射式粒徑分布測定裝置LA-950(HORIBA公司製)來求得。使用LA-950並藉由濕式法,在粒徑0.01μm~3,000μm的範圍下測定粒徑分布。前述粒徑係指,在橫軸為粒徑且縱軸為個數頻率所描繪之粒徑分布中,對應於分布中央值的粒徑(中位徑)。
<容積比重> 前述多孔碳材料的容積比重係0.20g/cm3
以上,較佳係0.20g/cm3
以上且0.40g/cm3
以下,更佳係0.20g/cm3
以上且0.35g/cm3
以下。 一般來說,中孔發達(即中孔容積在0.1cm3
/g以上)之多孔碳材料的容積比重係0.10g/cm3
左右。因此,若從單位體積來看,並無法發揮對於大分子的吸附及/或高速吸附能力優異之優異性。另一方面,若容積比重在0.20g/cm3
以上,則從單位體積來看或從單位重量來看,皆能發揮對於大分子的吸附及/或高速吸附能力優異之優異性。
容積比重係指,於一定容積的容器中使粉末自然落下並充填等,而將成為特定形狀之粉末的質量除以此時的體積來求得之比重(每單位體積的質量),容積比重越小則體積越大。
<中孔容積> 前述多孔碳材料的中孔容積係0.1cm3
/g以上,較佳係0.1cm3
/g以上且0.3cm3
/g以下,更佳係0.1cm3
/g以上且0.2cm3
/g以下。若前述中孔容積小於0.1cm3
/g,則不可謂中孔發達,無法得到對於大分子的吸附及/或高速吸附能力優異之優異性。另一方面,若前述中孔容積過大,則難以得到大的容積比重。
前述多孔碳材料具有很多細孔(Pore)。細孔係可分成中孔、微孔、大孔。此處,中孔係指孔徑2nm~50nm的細孔,微孔係指孔徑小於2nm的細孔,大孔係指孔徑大於50nm的細孔。
舉例來說,前述中孔容積係能夠使用以下裝置進行測定。 使用Micromeritics日本有限責任公司製的3FLEX來測定氮吸附等溫線,並能夠使用BJH法來算出。 前述BJH法係作為細孔分布解析法而被廣泛使用的方法。基於BJH法來解析細孔分布的情況下,首先,藉由將氮作為吸附分子而於吸附劑(多孔碳材料)吸附脫附,來求得脫附等溫線。接著,基於求得之脫附等溫線,求得從細孔填滿吸附分子(例如氮)的狀態至吸附分子階段性地脫附時之吸附層的厚度、以及此時所產生之孔的內徑(核半徑的兩倍),並基於式(1)來算出細孔半徑rp
,再基於式(2)來算出細孔容積。然後,藉由從細孔半徑與細孔容積來繪製相對於細孔徑(2rp
)的細孔容積變化率(dVp
/drp
),得到細孔分布曲線(參照日本BEL股份有限公司製的BELSORP-mini與BELSORP解析軟體使用手冊的第85頁~第88頁)。
rp
= t+rk
(1) Vpn
= Rn
・dVn
-Rn
・dtn
・c・ΣApj
(2) 且,Rn
= rpn 2
/(rkn-1
+dtn
)2
(3)
此處, rp
:細孔半徑 rk
:於細孔半徑rp
的細孔內壁吸附有於其壓力下之厚度t吸附層時的核半徑(內徑/2) Vpn
:產生第n次氮脫附時的細孔容積 dVn
:此時的變化量 dtn
:產生第n次氮脫附時吸附層厚度tn
的變化量 rkn
:此時的核半徑 c:固定値 rpn
:產生第n次氮脫附時的細孔半徑 同時,ΣApj
係表示從j = 1至j = n-1為止,細孔壁面之面積的累加値。
[具體的測定方法] 準備多孔碳材料30mg,並能夠使用設定了測定條件為相對壓力(P/P0)係0.0000001至0.995的範圍之3FLEX,來測定中孔容積。
<多孔碳材料的原料> 前述多孔碳材料的原料係較佳為植物來源的材料。若為植物來源,則容易將中孔容積値調整至上述所欲的値。同時,就減少環境負荷的觀點來看,使用植物來源亦有其優點。
就前述植物由來的材料而言,並未特別限制,能因應目的適當選擇,舉例來說,能夠例如為米(稻)、大麥、小麥、黑麥、日本雜穀(Japanese barnyard millet)、粟(小米)等的穎殼或秸稈,或者,蘆葦、海帶芽梗部。更甚者,例如植被於陸上的維管束植物、蕨類植物、苔蘚植物、藻類、海草。再者,此等材料係可單獨作為原料使用,亦可混合複數種來使用。同時,植物來源的材料之形狀或形態並未特別限定,可例如為穎殼或秸稈其本身,或者亦可為乾燥處理品。進一步,亦可使用經過在啤酒或洋酒等飲食品加工中的發酵處理、焙煎處理、萃取處理等之物品。特別是,從冀求將產業廢棄物資源化的觀點來看,較佳係使用經過脫粒等加工後的秸稈或穎殼。此等加工後的秸稈或穎殼係能夠從例如農業合作社及酒類製造公司、食品公司大量且容易地得到。
就前述多孔碳材料的製造方法而言,雖未特別限制,能因應目的適當選擇,但較佳係後述之多孔碳材料的製造方法。
(多孔碳材料的製造方法) 本發明多孔碳材料的製造方法係包含成型物製作製程、碳化物製作製程、賦活製程,較佳係包含脫灰分製程,且因應必要,包含其他製程。 前述製造多孔碳材料的方法,是用於製造本發明的多孔碳材料的方法
<成型物製作製程> 就前述成型物製作製程而言,只要是將植物來源的材料加壓成型,並得到成型物之製程,則並未特別限制,能因應目的適當選擇。
就前述植物來源的材料而言,並未特別限制,能因應目的適當選擇,舉例來說,例如在前述多孔碳材料的說明中所示例之前述植物來源的材料。此等當中,就容易製造所欲之多孔碳材料的觀點而言,較佳係穎殼。
就前述成型物的形狀而言,並未特別限制,能因應目的適當選擇。
於前述加壓成型中,舉例來說,使用於生物質(biomass)成型泛用之造粒機來進行,使其含水率成為3質量%以上且30質量%以下,較佳係5質量%以上且20質量%以下,加入水分並將搗碎後之穎殼成型。因為此時的壓力係根據成型機通過時之模具與穎殼的摩擦阻力來決定,故期望根據成型物的尺寸來調整水分的量。 同時,於前述加壓成型中,雖然因為摩擦而產生熱,但較佳係藉由加熱裝置來加熱。 藉由適度調整水分、壓力與熱,吾人推定能夠萃取含於前述植物來源的材料中之水溶性成分,並將其與粉體們連接而得到成型物。
藉由將前述植物來源的材料加壓成型,與未進行加壓成型的情況相比,能夠得到中孔發達且容積比重大的多孔碳材料。
<碳化物製作製程> 就前述碳化物製作製程而言,只要是將前述成型物碳化,且得到碳化物(碳材質物質)的製程,並未特別限制,能因應目的適當選擇。 前述碳化一般係指將有機物(於本發明係指植物來源的材料)熱處理並變換成碳材質物質(例如,參照JIS M0104-1984)。再者,作為用於碳化的氛圍,能夠舉出遮斷氧的氛圍,具體而言,真空氛圍、氮氣、氬氣等惰性氣體、或使前述成型物成為一種蒸燒狀態的氛圍。作為到達碳化溫度為止的升溫速度,於相關氛圍下,能夠例如1℃/分以上,較佳係3℃/分以上,更佳係5℃/分以上。同時,作為碳化時間的上限,雖然可例如10小時,較佳係7小時,更佳係5小時,但並不限於此。碳化時間的下限較佳係能夠確實地將前述成型物碳化的時間。
就前述熱處理的溫度而言,舉例來說,例如300℃~1,000℃等。
<賦活製程> 就前述賦活製程而言,只要是將前述碳化物賦活的製程,並未特別限制,能因應目的適當選擇,舉例來說,例如氣體賦活法、藥品賦活法等。 此處,賦活係指,使碳材料的細孔構造發達,並附加細孔。
前述氣體賦活法係使用作為賦活劑之氧、水蒸氣、二氧化碳、空氣等,且在氣體氛圍下,舉例來說,藉由於700℃~1,000℃,數十分鐘~數小時下,將前述碳化物加熱,再藉由前述碳化物中的揮發成分或碳分子,來使微細構造發達之方法。再者,雖然加熱溫度係基於植物來源材料的種類、氣體的種類、濃度等來適宜選擇,但較佳係800℃~950℃。 作為氣體賦活法中所用之氧或水蒸氣的替代,前述藥品賦活法係使用氯化鋅、氯化鐵、磷酸鈣、氫氧化鈣、碳酸鎂、碳酸鉀、硫酸等來賦活,並使用鹽酸洗淨,再使用鹼性水溶液調整pH,並使其乾燥的方法。
<脫灰分製程> 就前述脫灰分製程而言,只要是將前述碳化物中的灰分去除的製程,並未特別限制,能因應目的適當選擇,舉例來說,將前述碳化物浸漬於酸水溶液或鹼水溶液的方法等。 較佳係於前述脫灰分製程前,粉碎前述碳化物,並使前述碳化物成為易浸透於酸水溶液或鹼水溶液的尺寸。
以下係顯示前述多孔碳材料製造方法的一例。 藉由於氮氣流中,將穎殼加壓成型後之物體以500℃加熱5小時,並得到碳化碳化物。之後,將該碳化物10g置入鋁製的坩鍋,於氮氣流中(10升/分)使用5℃/分的升溫速度升溫至1,000℃。接著,在1,000℃下碳化5小時,並變換成碳材料物質(多孔碳材料前驅物)後,冷卻至室溫。然後,於碳化及冷卻中持續流入氮氣。接著,將碳材料物質粗粉碎至易進行鹼處理之1cm以下的尺寸,並使用1mol%的氫氧化鈉水溶液來去除材料內的灰分。之後,將材料洗淨並除去材料表面的鹼,進一步洗淨。之後,在水蒸氣氛圍下以950℃對材料進行熱處理,而得到容積比重高之植物來源的多孔碳材料。
(薄片) 本發明的薄片係含有本發明的前述多孔碳材料,更因應必要,含有其他材料。
前述薄片係例如藉由將含有前述多孔碳材料之粉末以濕式抄紙來得到的。舉例來說,較佳係藉由使用碎漿機、打漿機、磨漿機等裝置,將含有前述多孔碳材料之粉末混合、切斷且製作均勻分散的漿體,再以特定的流量將得到之漿體朝線上流動並脫水,而調整至任意之紙基本重量(basis weight)。之後,較佳係通過按壓部分(press part)並使用乾燥部分(dryer part)將薄片乾燥,且使用壓延部分(calendar part)使薄片平滑化後再使用捲軸(reel)並以纏捲等公知技術來製造。
(過濾介質) 本發明的過濾介質係包含本發明的前述多孔碳材料,更因應必要,包含其他材料。 前述過濾介質係例如作為淨水用過濾介質、空氣淨化用過濾介質等使用。
前述過濾介質係例如由將前述薄片成型而得。 就為了得到前述過濾介質的成型法而言,舉例來說,雖然可舉出捲繞本發明的前述薄片並進行熱處理而成為圓柱狀或圓筒狀的過濾介質之方法,或者使薄片層積而沖壓出任意形狀的過濾介質之方法,但並不限於此。
(濾芯) 本發明的濾芯係至少包含本發明的前述過濾介質,更因應必要,包含殼體等其他成分。
前述過濾介質係例如被收容於前述殼體。 前述殼體係例如包含殼體本體、流體流入部與流體流出部。 前述流體流入部係設置於前述殼體本體,使待過濾流體能夠流入。 前述流體流出部係設置於前述殼體本體,使過濾後之流體能夠流出。
(觸媒用載體) 本發明的觸媒用載體係包含本發明的前述多孔碳材料,更因應必要,包含其他材料。 舉例來說,前述觸媒用載體係前述多孔碳材料本身。 前述觸媒用載體係能夠保持多量之貴金屬等觸媒。因此,於前述觸媒用載體載持觸媒的觸媒載持體係能夠促進各種化學反應,並提升產率。
同時,除了上述以外,本發明的前述多孔碳材料還能夠用於電容器的電極材料、各種吸附劑、口罩、吸附薄片等。
[實施例] 以下雖然說明本發明的實施例,但本發明並不限於該等實施例。
於本實施例中,使用前述方法測定粒徑、容積比重、中孔容積。 殘留氯去除性能係藉由以下的通水試驗測定。
<通水試驗及殘留氯測定> 於實施例與比較例中,皆是將通過10mesh篩子且未通過32mesh篩子的試料填充至管柱,在入口殘留氯濃度0.5±0.1mg/L下輸送液體,並在空間速度SV=2000/h下進行通水試驗。 使用435nm發色的分光光度計並藉由鄰聯甲苯胺法測定,且將通過管柱後液體中的遊離殘留氯定量。
(實施例1) 使用穎殼(Chaff)作為原料。使用新興工機股份有限公司製S-5型平模(Flat die)式造粒機使粉碎後之穎殼成型為直徑6mm、長度數mm~數十m並得到成型物。將成型時的含水率、成型物的容積比重、成型物的狀態顯示於表1。 再者,成型時的含水率係藉由使用噴霧器將水噴霧至原料之步驟、以及此時的噴霧量來調整。
[表1]
含水率(質量%)係含於原料的水分之量,並藉由加熱乾燥式水分計測定。具體而言,使用A&D公司的ML-50,將試料1g在150℃下乾燥20分鐘,並根據乾燥前後的重量變化來測定含水率。舉例來說,在試料1.0g乾燥後變成0.9g的情況下,含水率係10質量%。
接著,將製作之含水率16質量%的成型物在氮氣下,以600℃加熱3小時並得到碳化物。 接著,將碳化物粗粉碎成2mm左右尺寸之後,浸漬於1mol%的氫氧化鈉水溶液,且在去除灰分後洗淨。 接著,在水蒸氣氛圍下,以950℃加熱3.5小時並進行賦活化,而得到多孔碳材料。
藉由石磨機將得到之多孔碳材料粉碎,並藉由篩子分級。 針對分級後的多孔碳材料,求得粒徑與容積比重的關係,並顯示於圖1。 同時,將分級後之多孔碳材料的比表面積、中孔容積顯示於表2。
[表2]
再者,就繪製於圖1之各粒徑的全部試樣而言,其等的比表面積相同且中孔容積相同。
(比較例1) 使用穎殼作為原料。 接著,在氮氣氛圍下,以600℃加熱3小時並得到碳化物。 接著,將碳化物浸漬於1mol%的氫氧化鈉水溶液,且在去除灰分後洗淨。 接著,在水蒸氣氛圍下,以950℃加熱3小時並進行賦活化,而得到多孔碳材料。
藉由石磨機將得到之多孔碳材料粉碎,並藉由篩子分級。 針對分級後的多孔碳材料,求得粒徑與容積比重的關係,並顯示於圖1。 同時,將分級後之多孔碳材料的比表面積、中孔容積顯示於表3。
[表3]
再者,就繪製於圖1之各粒徑的全部試樣而言,其等的比表面積相同且中孔容積相同。
從圖1得知,相對於比較例1的多孔碳材料(既有的多孔碳材料),其容積比重係0.10g/cm3
且與粒徑無關,實施例1的多孔碳材料在粒徑10μm以上的區域,其容積比重相較於既有的多孔碳材料係明顯變大。 特別是在粒徑100μm以上的區域,容積比重係變成比較例的3倍左右。因為容積比重變成3倍左右,充填於同一容器內的重量亦變大,舉例來說,在用於淨水用過濾介質的情況下,淨水性能大幅提升。 同時,在前述的方法中,將調查了在同一體積下殘留氯去除性能之結果顯示於圖2。 藉由改善容積比重,吸附容量提升。因此,舉例來說,在比較例1中,去除率下降至80%以下之單位材料體積的通水量係27L/mL。相對於此,在實施例1中,即使單位材料體積的通水量係超過100L/mL,其去除率亦超過80%。此係顯示作為殘留氯去除過濾介質的壽命變長為4倍左右。
(實施例2) 除了將實施例1中的賦活化時間從3.5小時變更成3小時以外,與實施例1相同地,製作多孔碳材料。將得到之多孔碳材料的比表面積以及中孔容積顯示於表4。 再者,實施例2中粒徑與容積比重的値係與實施例1(圖1)相同。
(比較例2) 除了將比較例1中的賦活化時間從3.5小時變更成2.5小時以外,與比較例1相同地,製作多孔碳材料。將得到之多孔碳材料的比表面積以及中孔容積顯示於表4。 再者,比較例2中粒徑與容積比重的値係與比較例1(圖1)相同。
同時,針對在實施例2與比較例2所得到之多孔碳材料而言,同時,將於前述方法中在同一體積下所調查之殘留氯去除性能的結果顯示於圖3。 即使於比表面積、以及中孔容積相異的實施例2與比較例2中,也得到與實施例1、以及比較例1相同的結果。
[表4]
[產業利用性] 因為本發明的多孔碳材料中孔發達且容積比重大,故能使用在電容器的電極材料、各種吸附劑、口罩、吸附薄片、觸媒用載體等。
無。
[圖1] 圖1係顯示實施例1及比較例1之粒徑與容積比重的關係之圖。 [圖2] 圖2係顯示實施例1及比較例1之殘留氯去除性能之圖。 [圖3] 圖3係顯示實施例2及比較例2之殘留氯去除性能之圖。
無。
Claims (12)
- 一種多孔碳材料,其粒徑在10μm以上且1cm以下,其容積比重在0.20g/cm3 以上,且其中孔容積在0.10cm3 /g以上。
- 如請求項1所述之多孔碳材料,其中,前述多孔碳材料係由植物來源的材料而成。
- 如請求項2所述之多孔碳,其中,前述植物來源的材料係穎殼。
- 一種過濾介質,其係包含如請求項1~3中任一項所述之多孔碳材料。
- 如請求項4所述之過濾介質,其係淨水用。
- 如請求項4所述之過濾介質,其係空氣淨化用。
- 一種濾芯,其係包含如請求項4所述之過濾介質。
- 一種薄片,其係包含如請求項1~3中任一項所述之多孔碳材料。
- 一種觸媒用載體,其係包含如請求項1~3中任一項所述之多孔碳材料。
- 一種多孔碳材料的製造方法,其係製造如請求項1~3中任一項所述之多孔碳材料的製造方法,其係包含: 成型物製作製程,將植物來源的材料加壓成型,並得到成型物; 碳化物製作製程,將前述成型物碳化,並得到碳化物;及 賦活製程,賦活前述碳化物。
- 如請求項10所述之多孔碳材料的製造方法,其中,前述植物來源的材料係穎殼。
- 如請求項10所述之多孔碳材料的製造方法,其中,前述成型物製作製程係將含水率3質量%以上且30質量%以下之前述植物來源的材料加壓成型之製程。
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