TWI579485B - 具有單塊碳吸附劑之氣體儲存及配送系統 - Google Patents

具有單塊碳吸附劑之氣體儲存及配送系統 Download PDF

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TWI579485B
TWI579485B TW102102674A TW102102674A TWI579485B TW I579485 B TWI579485 B TW I579485B TW 102102674 A TW102102674 A TW 102102674A TW 102102674 A TW102102674 A TW 102102674A TW I579485 B TWI579485 B TW I579485B
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唐諾卡路瑟斯
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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Description

具有單塊碳吸附劑之氣體儲存及配送系統
本發明大致係關於氣體儲存及配送系統,及尤其係關於利用單塊碳吸附劑作為氣體儲存介質之此種類型的系統。
Tom等人之美國專利5,518,528中所揭示之以物理吸附劑為基礎之氣體儲存及配送系統係完全改變在半導體工業中之有害氣體的輸送、供給及使用。此系統包括容納對儲存於容器中及自其中選擇性配送之氣體具有吸附親和力之物理吸附劑介質,諸如分子篩或活性碳之容器。相對於容納在「游離」(未吸附)狀態之相當量之氣體,該氣體之相對的空(指吸附劑)容器在減壓下以在吸附劑介質上之吸附狀態收容於容器中。
藉由此種減壓儲存,由於相對於習知之高壓氣體儲存鋼瓶,任何洩漏導致氣體逸入至周遭環境中之速率係非常低,因而氣體儲存及配送操作之安全性可實質上地獲得改良。此外,由於減壓降低在系統組件諸如閥、流量控制器、聯結器、接頭等等上之應力及磨損,因而以吸附劑為基礎之 系統之低壓操作使此種氣體洩漏事件的可能性較低。
在此種以吸附劑為基礎之氣體儲存及配送系統中,物理吸附劑介質之工作容量係為操作限制。工作容量係可儲存(「負載」)於吸附劑介質上,及自此種吸附劑介質脫附移除供使用之氣體量。工作容量係含吸附劑介質之氣體儲存容器中之氣體之儲存壓力、及脫附氣體之配送條件(例如,當使用壓差於達成脫附時為脫附氣體之配送壓力,及當使用氣體之熱脫附作為配送形式時為各別儲存及配送條件之溫度值)、及吸附劑介質本身之類型和特性(例如,包括諸如吸附劑介質大小、形狀、孔隙度、孔隙大小分佈、及內部孔隙通道之曲折之參數)之函數。
技藝中仍持續尋求以物理吸附劑為基礎之氣體儲存及配送系統之工作容量的改良。
本發明係關於以物理吸附劑為基礎之氣體儲存及配送系統,及關於改良工作容量之此種類型的系統。
在一態樣中,本發明係關於一種流體儲存及配送裝置,其包括一具有內部體積之流體儲存及配送容器,其中內部體積包含將流體吸附滯留於其上,且流體可自其脫附以自容器配送之物理吸附劑,及連結至容器,以自容器配送脫附流體之配送組件,其中物理吸附劑包括單塊碳物理吸附劑,其特徵在於以下特徵之至少一者:(a)在25℃及650托爾(torr)壓力下對胂氣體測量為每公升吸附劑大於400克胂之填充密度; (b)該吸附劑之整體孔隙度的至少30%,包括尺寸在自約0.3至約0.72奈米之範圍內之狹縫形孔隙,及整體孔隙度之至少20%包括直徑<2奈米之微孔隙;及(c)在低於1000℃之溫度下經由熱解及非必需之活化形成,且具有每立方公分自約0.80至約2.0克之體密度(bulk density)。
本發明之另一態樣係關於一種形成使用於氣體儲存及配送系統中之單塊吸附劑之方法,該方法包括:將可熱解材料成型成單塊形狀;及將可熱解材料在熱解條件下熱解,而產生特徵在於以下特徵之至少一者之單塊吸附劑:(a)在25℃及650托爾壓力下對胂氣體測量為每公升吸附劑大於400克胂之填充密度;(b)該吸附劑之整體孔隙度的至少30%,包括尺寸在自約0.3至約0.72奈米之範圍內之狹縫形孔隙,及整體孔隙度之至少20%包括直徑<2奈米之微孔隙;及(c)每立方公分自約0.80至約2.0克之體密度,其中前述之熱解條件包括低於1000℃之溫度。
本發明之再一態樣係關於一種儲存及配送氣體之方法,包括:製造氣體儲存及配送容器;將對該氣體具吸附親和力之物理吸附劑設置於容器中;將該氣體裝填至該容器,以吸附於物理吸附劑上;利用包含可引動閥之閥頭密封容器,以封住物理吸附劑及吸附氣體,及使其與容器之外部環境隔離;使吸附氣體自物理吸附劑脫附,及引動閥頭中之可引動閥,以使氣體自容器流經可引動閥,而進行氣體配送, 其中物理吸附劑之特徵在於以下特徵之至少一者:(a)在25℃及650托爾壓力下對胂氣體測量為每公升吸附劑大於400克胂之填充密度;(b)該吸附劑之整體孔隙度的至少30%,包括尺寸在自約0.3至約0.72奈米之範圍內之狹縫形孔隙,及整體孔隙度之至少20%包括直徑<2奈米之微孔隙;及(c)每立方公分自約0.80至約2.0克之體密度,其中該熱解條件包括低於1000℃之溫度。
本發明之其他態樣、特徵及具體例將可由隨後之揭示內容及隨附之申請專利範圍而更加明白。
200‧‧‧儲存及配送系統
204‧‧‧儲存及配送容器
205‧‧‧單塊吸附劑本體
206‧‧‧閥頭
208‧‧‧手動引動器
210‧‧‧聯結器
212‧‧‧配送導管
214‧‧‧壓力轉換器
216‧‧‧惰性沖洗單元
220‧‧‧質量流量控制器
222‧‧‧過濾器
224‧‧‧聯結器
310‧‧‧流體儲存及配送容器
312‧‧‧管閥連接閥頭
314‧‧‧手柄
圖1係Kureha 578-66-6珠粒活性碳(以實心菱形記號標示之數據點)、Takachiho ABF 14-03顆粒活性碳(以實心方形記號標示之數據點)及由聚偏二氯乙烯聚合物(Saran A,Dow Chemical Co.)形成之碳(以空心三角形記號標示之數據點)之每公升碳所吸附之膦(PH3)之以克為單位之重量成以托爾為單位之壓力值之函數的圖。
圖2係Kureha 578-66-6珠粒活性碳(以實心菱形記號標示之數據點)及由聚偏二氯乙烯聚合物(Saran A,Dow Chemical Co.)形成之碳(以空心三角形記號標示之數據點)之每公升碳所吸附之胂(AsH3)之以立方公分為單位之體積成以托爾為單位之壓力值之函數的圖。
圖3係根據本發明之一具體例之利用單塊吸附劑之儲存及傳送系統的概略圖式。
圖4係根據本發明之另一具體例之利用單塊吸附劑之長方體流體儲存及配送容器之透視圖。
圖5係Kureha 578-66-6珠粒活性碳(以實心菱形記號標示之數據點)及由聚偏二氯乙烯聚合物(Saran A,Dow Chemical Co.)形成之碳(以實心方形記號標示之數據點)之每公升碳所吸附之三氟化硼(BF3)之以克為單位之吸附重量成以托爾為單位之壓力值之函數的圖。
本發明係基於發現可利用其中具有單塊碳吸附劑材料之流體儲存及配送容器製造以物理吸附劑為基礎之流體儲存及配送裝置而完成,其有關於在吸附劑上吸附及脫附之氣體之性質及程度,容器中之物理吸附劑介質所可達到之填充密度,及包括此種容器之流體儲存及配送裝置對於半導體製造操作之效用之驚人且在意料之外的優點。
本發明因此於技藝中獲致較諸如說明於Tom等人之美國專利第5,518,528號中之類型之以吸附劑為基礎之氣體儲存及配送系統(其迄今為止使用呈微細分割形態之物理吸附劑介質,諸如所謂的珠粒活性碳)的實質進步。根據本發明,當活性碳並非以珠粒或顆粒形態,而係以特定特性之單塊形態提供時,氣體儲存及配送系統之工作容量可顯著地獲得改良。
可經由使用單塊形態活性碳所達到之相對於先前技藝中所使用之微細分割形態的改良程度係高度地在意料之外,且當氣體儲存及配送容器係為配合吸附劑單塊之形狀時,其可再獲得更驚人的改良。
舉例來說,當容器係為與於2002年12月以Dennis Brestovansky、Michael J.Wodjenski、Jose I.Arno及J.D.Carruthers之名義提出申請之共同提出申請之美國專利申請案第_[ATMI-566]號,「長方體形流體儲存及配送系統(Rectangular Parallelepiped Fluid Storage and Dispensing System)」之揭示內容一致之較佳的立方體或其他長方體形狀時,使用形狀可配合之單塊可使以物理吸附劑為基礎之氣體儲存及配送系統之工作容量相對於使用經填裝珠粒活性碳之相同「足跡(footprint)」及容器內部體積之氣體儲存鋼瓶之先前技藝系統提高至少85%。
經由說明本發明之單塊物理吸附劑於以物理吸附劑為基礎之流體儲存及配送裝置中之長方體構形容器中之較佳填裝之意料外之優點的背景,將長方體構形使用於以物理吸附劑為基礎之流體儲存及配送系統之一開始的考量由於下列因素而似乎相當不利:(i)長方體容器具有六個面,如容器之各面為個別物件,則將需製作12個熔接線(相對地,可自管狀捲繞鋼原料形成沒有接縫的圓柱形容器);(ii)與(i)一致地,預期矩形構形容器之製造成本實質上將較相對的圓柱形容器高;(iii)長方體構形包括在相鄰垂直取向壁之接面的「尖銳」角落,其提供在接線處形成空隙的可能,其中吸附劑床將不會相對於相對的圓柱形體容器(其沒有此種角落,反之其係包圍容器之內部體積中之物理吸附劑材料床的最小截面積形狀)「填充」於角落;及(iv)兩垂直壁彼此的相交產生相對於「無接縫」圓柱形容器易受作用於上之壓力或力破壞之接點。
然而,經測定長方體構形產生在鄰接於相鄰壁交點之接縫,係具有較不緊密填充之吸附劑床區域的容器,但其並非缺點,此種較低密度之吸附劑床區域,事實上由於可使間隙的脫附或未吸附氣體流出吸附劑床之整體體積有較高的氣體流動傳導路徑而有利。
此外,確切而言由於圓柱形容器係最小截面積的構形,其具有包圍壁面積之最小周圍程度,因而對圓柱形容器之壁所「呈現」的吸附劑量為最大。反過來思考,包圍(鄰接於)截面中之吸附劑床之壁的周邊範圍在長方體構形中較在圓柱形容器中為大。由於包圍吸附劑床之壁表面為非吸附性,且其在矩形構形容器中在吸附劑床之外圍較於圓柱形容器中成比例地較高,因而長方體構形可使較自相對尺寸之圓柱形容器大之體積之氣體自容器離開。結果,在壁區域之脫附氣體於其之自吸附劑介質之起始脫附釋放後,將較在吸附劑床內部部分中之脫附氣體不易再被吸附。
基於此等理由,長方體容器構形對於容納本發明之單塊形態之物理吸附劑具有特殊之效用。
此處所使用之「單塊」係指吸附劑介質係為單一或塊狀的形態,例如,呈塊、磚、碟、鑲嵌物(boules)等等之形態,其係對比於一般利用於包括大量習知之微細分割形態,諸如珠粒、顆粒、細粒、圓球等等床形態中之此種珠粒、顆粒、細粒、圓球等等。因此,在大量微細分割物理吸附劑元件之床形態中,活性吸附劑之空隙體積的特性主要為間隙或顆粒間,其係根據吸附劑顆粒之尺寸、形狀及填裝密度而異。 相對地,在單塊形態中,活性吸附劑之空隙體積係為吸附劑材料之本質之孔隙度及可能係在其之加工過程中形成於整體吸附劑本體中之空隙的形態。
本發明之一態樣係關於一種流體儲存及配送裝置,其包括一具有內部體積之流體儲存及配送容器,其中內部體積包含將流體吸附滯留於其上,且流體可自其脫附以自容器配送之物理吸附劑,及連結至容器,以自容器配送脫附流體之配送組件,其中物理吸附劑包括單塊碳物理吸附劑,其特徵在於以下特徵之至少一者:(a)在25℃及650托爾壓力下對胂氣體測量為每公升吸附劑大於400克胂之填充密度;(b)該吸附劑之整體孔隙度的至少30%,包括尺寸在自約0.3至約0.72奈米之範圍內之狹縫形孔隙,及整體孔隙度之至少20%包括直徑<2奈米之微孔隙;及(c)在低於1000℃之溫度下經由熱解及非必需之活化形成,且具有每立方公分自約0.80至約2.0克之體密度。
單塊吸附劑可為單一單塊吸附劑物件或多數單塊吸附劑物件之形態。吸附劑可經適當成形成配合於其所設置之容器之內部體積,及其以佔據容器之內部體積之至少60%,例如,此內部體積之75至95%較佳。雖然本發明就將單塊吸附劑容納於較佳之長方體形容器中而更完整論述於下,但當明瞭本發明並不因此受限,而係可利用其他的容器形狀及構形,例如,圓柱形容器、桶形容器、截頂圓錐形容器等等。
單塊吸附劑可經形成為有機樹脂之熱解產物,及更 一般而言,其可自任何適當的可熱解材料,諸如,比方說,聚偏二氯乙烯、酚-甲醛樹脂、聚呋喃甲醇、椰子殼、花生殼、桃子核、橄欖核、聚丙烯腈、及聚丙烯醯胺形成。吸附劑可於將要儲存流體供後續配送用之流體儲存及配送容器中,即於原位形成,或可先形成吸附劑,然後再將其引入至流體儲存及配送容器中。在一具體例中,吸附劑具有其孔隙中之孔隙度之至少20%具低於2奈米之直徑。
吸附劑可以多數聚集構成吸附劑物質之單塊吸附劑物件提供於流體儲存及配送容器中。在此種多數單塊物件之配置中,多數個別單塊吸附劑物件之各者可具有在容器內部體積之高度之0.3及1.0倍之間的長度,及在容器之矩形截面積之0.1及0.5倍之間的截面積。多數個別單塊物件之各者可具有長方體形狀或圓柱形或其他適當的形狀。在流體儲存及配送容器之內部體積中,個別的單塊物件可橫向及/或縱向緊靠,而與相鄰的單塊元件表面接觸。在一具體例中,多數個別單塊物件之各者具有自約2至約20,例如,在自約4至約15之範圍內之長度對截面尺寸比L/D,其中L係單塊碳吸附劑物件之長度或主軸尺寸,及D係橫向或次軸尺寸。在另一具體例中,單塊吸附劑物件可具有高度對直徑比H/D係自約0.10至約0.80之碟形。
吸附滯留於吸附劑上,及於適當脫附條件下脫附以進行流體配送之流體儲存及配送容器中之流體可為任何適當類型之流體,例如,具有在半導體製造中之效用之流體,諸如氫化物、鹵化物及有機金屬氣態試劑,例如,矽烷、鍺烷、 胂、膦、光氣、二硼烷、鍺烷、氨、、硫化氫、硒化氫、碲化氫、一氧化二氮、氰化氫、環氧乙烷、氘化氫化物、鹵化物(氯、溴、氟及碘)化合物及有機金屬化合物。
容器中之流體可儲存於任何適當的大氣壓力、低於大氣壓力或超過大氣壓力下,例如,低於2500托爾之壓力,諸如在自約20托爾至約1200托爾之範圍內,或對供離子植入或其他低於大氣壓力應用之氣體之低於大氣壓力供給在自約20托爾至約750托爾之範圍內之壓力。
容納其上經吸附流體之吸附劑的容器可由任何適當的容器構造材料,諸如金屬(例如,鋼、不銹鋼、鋁、銅、黃銅、青銅及其合金)、玻璃、陶瓷、玻化材料、聚合物、及複合材料形成。
容器可為適合於特定流體儲存及配送應用之任何適當的形狀及尺寸。例如,容器可為具方形截面之細長垂直豎立形態之長方體形狀,或容器可為具圓形截面之圓柱形,或任何其他適當的形狀、尺寸及形態。
在一具體例中,本發明在界定一封閉內部體積,且具有與使氣體自容器選擇性排出之氣體配送組件連結之口的長方體容器中利用單塊形態之物理吸附劑。本發明之單塊形態之吸附劑介質提供使吸附質氣體以期望量吸附滯留的足夠容量,氣體在脫附條件下之良好的脫附釋放,及具良好底部(heels)行為之良好的工作容量(即起始吸附氣體之高的脫附程度),且對相關氣體具有適當的吸附親和力,以致在將氣體儲存於其中之過程中於容器之內部體積中維持低氣體壓力。
根據本發明之物理吸附劑可為任何適當的單塊形態,例如,塊、磚、鑲嵌物之形態或大小與流體儲存及配送容器相稱之類似的吸附劑材料形態,以致容器包含一個或少數,例如,低於75個,以低於20個更佳之個別的單塊物件。在再一較佳態樣中,容器包含不多於8個此種個別的單塊物件,不多於4個此種物件再更佳,及容器包含單一的單塊物理吸附劑物件最佳。
配置於流體儲存及配送容器中之單塊物件提供尺寸及形狀配合於流體儲存及配送容器之內部體積,以致單塊物件之吸附劑物質佔據容器內部體積之至少60%較佳,以在此種容器之內部體積之自約75%至約95%之範圍內較佳的聚集吸附劑物質。
如以單一的單塊吸附劑物件提供,則吸附劑介質可對此種用途在容器中於原位形成,例如,經由使呈液態或其他可流動形態之有機樹脂熱解,在於容器中將其熱解之前,將其於容器中填充至期望程度。
或者,如以多個單塊物件之形態提供,則此種物件之各者可具有在容器內部體積之高度之0.3及1.0倍之間的長度,及在容器之矩形截面積之0.1及0.5倍之間的截面積。當容器為長方體形狀時,各單塊元件可具有長方體形狀,以使容器內部體積之體積利用率最大化,其中各單塊元件可橫向及/或縱向緊靠,而與容器內部體積中之相鄰的單塊元件表面接觸。或者,在一些情況中,可能希望吸附劑單塊元件係為實心圓柱之形態,其中各別的圓柱形元件係經裝入至內部 體積中,使其沿其之面對側面彼此相切緊靠,及至少在其之圓形截面端面彼此面對面地部分接觸緊靠。除立方體或其他長方體形狀外之形狀的流體儲存及配送容器中,可相對地形成配合容器內部體積之形狀的單塊吸附劑物件。舉例來說,流體儲存及配送容器可為圓柱形狀,而其中之單塊吸附劑物件包括吸附劑之碟形本體的垂直堆疊,其各具有使其之周邊順應於容器形狀,與容器之面對內壁表面緊鄰的直徑。
由於物理吸附劑材料一般係以其可供吸附滯留工作氣體(吸附質)用之表面積分類,因此具其之高表面對體積比之顆粒形態一直被視為優於具較低視表面對體積比之整體形態諸如塊及磚(即單塊形態),因而伴隨使用單塊形態之活性碳而來之較諸先前技藝之微細分割顆粒形態的改良程度係在意料之外。因此,直覺上將會預期單塊形態之吸附劑將係具降低吸附容量及工作容量之低效率形態。
然而,經發現可形成具有與相對之珠粒碳類似之微孔隙體積,但具實質上較高之密度,例如,在較相對之珠粒碳之密實密度高自約25%至約80%之範圍內之密度的碳單塊,且當將此種高密度單塊使用於以物理吸附劑為基礎之氣體儲存及配送系統中時,其可相較於珠粒碳之床而提供每單位體積之吸附劑所吸附之氣體質量的驚人改良。
有用於本發明之廣義實行的碳單塊包括粗磚、塊及錠形態作為整體形態,其以具有三維(x,y,z)特性較佳,其中各此種尺寸係大於1.5公分,及以大於2公分較佳。舉例來說,碳單塊可為由聚合木炭諸如聚偏二氯乙烯(PVDC)或其他適當 聚合物所製得之單塊煤磚的形態,其具有高體密度(將空隙測量在內),例如,在每立方公分自約0.80至約2.0克左右,具高工作容量(高微孔隙度及低底部)及夠低而可確保容易及快速之吸附及脫附之孔隙曲折。
在一具體例中,本發明之單塊碳吸附劑包括在活性碳上之摻雜劑,以使吸附質流體在長期儲存過程中之分解減至最小。可有用於本發明之廣義實行之摻雜劑的說明例為硼酸(H3BO3)、四硼酸鈉(Na2B4O7)、矽酸鈉(Na2SiO3)及磷酸氫二鈉(Na2HPO4)。
在另一態樣中之單塊碳吸附劑物件可具有自約2至約20,及自約4至約15更佳之長度對截面尺寸比L/D,其中L係單塊碳吸附劑物件之長度或主軸尺寸,及D係橫向或次軸尺寸。在一特定具體例中,單塊碳吸附劑係以高度大約6英吋之1英吋×1英吋方形截面PVDC木炭單塊煤磚的形態提供。
一較佳的單塊碳吸附劑包括Saran A、Saran MC-10S或Saran XPR-1367-D-01452-050 PVDC均聚物或共聚物之熱解產物,由於超微孔隙性碳具有高比例之小尺寸,例如,在自約0.3至約0.75奈米之範圍內之狹縫形孔隙。
當單塊碳吸附劑具有直徑低於約2奈米之孔隙時,單塊碳吸附劑可在高於其之臨界溫度吸附氣體,例如,三氟化硼,至與吸附劑材料之微孔隙體積成比例的程度。供此種用途用之較佳的單塊碳吸附劑材料具有高比例之孔隙,例如,至少50%之孔隙度,在小微孔隙,例如,超微孔隙之大 小範圍內。此效應可經由參照圖5而得見,其係(i)Kureha珠粒活性碳(以實心菱形記號標示之數據點)及(ii)由聚偏二氯乙烯聚合物(Saran A,Dow Chemical Co.)形成之碳(以實心方形記號標示之數據點)之每公升碳所吸附之三氟化硼(BF3)之以克為單位之重量成以托爾為單位之壓力值之函數的圖。
雖然微孔隙體積係選擇使用於本發明之單塊碳吸附劑系統中之碳的重要標準,且希望使微孔隙體積最大化,但以每公升吸附劑之體積的基準適當地比較儲存於固定體積容器中之氣體。在此種情況中,吸附劑填充密度變得極度重要。為此,單塊碳可消除其所使用之流體儲存及配送容器中之空隙體積。
在一較佳具體例中,根據本發明之流體儲存及配送容器中之空隙體積不超過容器之總內部體積之約40%,及儘可能地低更佳。希望單塊碳吸附劑之填充密度儘可能地高,其具有以每單位體積吸附劑之體積為基準之最大微孔隙體積,且有高比例之孔隙體積係為超微孔隙。微孔隙之構形亦重要,希望孔隙係狹縫形狀以提供高吸附值,但不會過小,以致狹縫構形會干擾在脫附條件下之氣體的容易釋放,例如,在40托爾左右之壓力值下之脫附。
在碳活化形成活性碳之期間,孔隙在非氧化氣體諸如氮之存在下在高溫下加寬,隨後再暴露至氧化氣體諸如氧或蒸氣短期間,然後再於非氧化大氣中冷卻。在此種活化中,由於高度的燒盡(burn-off)會導致孔隙之加寬,而提高微孔隙體積及伴隨顆粒密度之下降,因而要小心控制材料之燒盡程 度。
本發明之單塊碳吸附劑可以任何適當的方式適當地形成。在一具體例中,單塊碳係自聚合材料諸如購自The Dow Chemical Company(Midland,MI)之Saran A或Saran MC-10S聚合物之聚偏二氯乙烯聚合物,在適當的壓力,例如,在自約每平方英吋10仟磅至約每平方英吋20仟磅之範圍內之壓力下壓力成型,然後再於氮氣流中在自約600℃至約900℃,例如,在約700℃左右之溫度下熱解而形成。此方法產生具大大增加之填充密度(即每公升碳所吸附之例如,以克為單位之氣體重量)的碳吸附劑材料,如示於圖1及2之圖中。
本發明之單塊碳吸附劑顯著不同於利用微細分割顆粒,諸如具0.1-1.0公分之顆粒直徑,及更典型為0.25-2.0毫米之顆粒直徑之珠粒活性碳,或在整體微孔隙性碳材料之情況中(參見2002年2月21日公告之Wojtowicz等人之美國專利申請案公告US2002/0020292 A1),利用高溫,例如,>1000℃及以>1100℃較佳,於引發高石墨化程度,並結合包括經進行多達76次之重複化學吸附/脫附步驟之活化(參見Quinn等人之美國專利5,071,820)於獲致適當的微孔隙體積、表面積及每單位體積之碳吸附劑之微孔隙體積(其係製得供高壓氣體儲存應用用之適當吸附劑材料之耗時且昂貴的方法)的先前技藝實務(Wojtowicz等人之美國專利申請案公告US2002/0020292 A1揭示吸附質氣體之最佳的儲存容量需將氣體「在自約500 psi至約3500 psi之範圍內之壓力下引入至儲存容器中」,第2頁,段落[0013],最後一句)。
相對於此等先前技藝之方法,本發明之單塊碳吸附劑係由適當的聚合材料,例如,選自聚偏二氯乙烯、酚-甲醛樹脂、聚呋喃甲醇、椰子殼、花生殼、桃子核、橄欖核、聚丙烯腈、聚丙烯醯胺等等之聚合物形成,其可在例如,至多約20,000 psi或更高之成型壓力下壓力成型,而產生經壓力成型之「生樹脂(green resin)」本體,其可在低於1000℃,以不超過約900℃較佳,例如,在自約500℃至約900℃之範圍內,及在自約600℃至約900℃之範圍內更佳之溫度下熱解,而產生具有供預期氣體儲存及配送應用之適當高值之填充密度的單塊碳材料。有用於實施本發明之單塊碳吸附劑包括具有對胂氣體在25℃及650托爾壓力下測量為每公升碳吸附劑超過400克胂,及以每公升碳吸附劑大於450克胂較佳之填充密度的碳吸附劑。
可將熱解產物就此使用作為根據本發明之單塊吸附劑本體,但將此種熱解產物以可產生具高比例,例如,狹縫形孔隙之至少30%之孔隙度,及以至少60%之孔隙度較佳,具有在自約0.3至約0.72奈米之範圍內之大小,及有顯著的孔隙度,例如,整體孔隙度之至少20%,及以至少30%較佳,包括直徑<2奈米之微孔隙之具超微孔隙度之單塊碳吸附劑產物的方式活化較佳。活化程序可包括用於增進材料對相關吸附質氣體之吸附親和力,或者改良吸附劑介質對吸附/脫附工作之特性的任何適當加工步驟。舉例來說,活化程序可包括在非氧化大氣,例如,氮、氬、氦或其他非氧化氣體中加熱,隨後再在轉變為非氧化大氣及冷卻至環境溫度(例如,室 溫)之前先將大氣轉變為氧化大氣,諸如二氧化碳或蒸氣短期間。活化程序之明確條件,例如,溫度值及連續步驟之期間,可經由簡單地改變各別的程序條件及分析測定所得之吸附劑性能,諸如填充密度、多孔計定性等等,而於技藝技能內無需過多的實驗容易地決定。
圖1係Kureha 578-66-6珠粒活性碳(以實心菱形記號標示之數據點)、Takachiho ABF 14-03顆粒活性碳(Takachiho Kabushiku Kogyo,Ltd.,日本東京)(以實心方形記號標示之數據點)、及由聚偏二氯乙烯聚合物(Saran A,Dow Chemical Co.)形成之單塊碳(以空心三角形記號標示之數據點)之每公升碳所吸附之膦(PH3)之以克為單位之重量成以托爾為單位之壓力值之函數的圖。
圖1中之數據顯示由PVDC聚合物形成之單塊碳具有較珠粒活性碳吸附劑或Takachiho顆粒活性碳吸附劑實質上更高之每公升碳的吸附膦重量,其在自0托爾至750托爾之壓力範圍內一般有多於兩倍的膦吸附載入量。
圖2係Kureha 578-66-6珠粒活性碳(以實心菱形記號標示之數據點)及由聚偏二氯乙烯聚合物(Saran A,Dow Chemical Co.)形成之碳(以空心三角形記號標示之數據點)之每公升碳所吸附之胂(AsH3)之以立方公分為單位之體積成以托爾為單位之壓力值之函數的圖。
圖2證實單塊碳吸附劑較諸珠粒活性碳對於胂載入的優越性。在0托爾至770托爾之壓力範圍內,單塊碳吸附劑之以每公升碳之立方公分計之胂的體積載入量高 50-100%+。
下表1記述胂在關於圖1論述於上之三類型之吸附劑材料,包括Kureha 578-66-6珠粒活性碳、Takachiho ABF 14-03顆粒活性碳、及PVDC木炭單塊吸附劑上之填充密度值。在650托爾之胂壓力下對各材料評估兩樣品。填充密度係以每克吸附劑之吸附胂之克數之重量基準,以及以每公升吸附劑之吸附胂之克數之體積基準測定。
表1中之結果顯示雖然單塊碳吸附劑之以重量基準計之填充密度大約較非單塊活性碳吸附劑低15-20%,但以體積基準計之單塊碳吸附劑之填充密度則較相對之非單塊活性碳吸附劑之填充密度高超過50%。
下表2係膦在關於圖1論述於上之三類型之吸附劑材料,包括Kureha 578-66-6珠粒活性碳、Takachiho ABF 14-03顆粒活性碳及PVDC木炭單塊吸附劑上之填充密度值之相對的填充密度列表。
表2中之結果顯示單塊碳吸附劑(PVDC木炭)具有高於非單塊形態之活性碳吸附劑之以重量及體積計之填充密度,以體積基準計之填充密度較膦在非單塊形態之活性碳上之體積填充密度高100%左右。
在本發明之廣義實行中滯留於單塊碳吸附劑上之吸附質流體可為任何適當類型,包括,例如,氫化物氣體(諸如胂、膦、鍺烷、矽烷、經單-、二-、及三-取代之矽烷,例如,此種類型之烷基矽烷)、鹵化物氣體(諸如三氟化硼、三氯化硼、經鹵素取代之矽烷等等)及氣態有機金屬組成物。
可在實施本發明時有用地儲存及配送之說明性的吸附質氣體種類包括矽烷、鍺烷、胂、膦、光氣、二硼烷、鍺烷、氨、、硫化氫、硒化氫、碲化氫、一氧化二氮、氰化氫、環氧乙烷、氘化氫化物、鹵化物(氯、溴、氟及碘)化合物,包括諸如F2、SiF4、Cl2、ClF3、GeF4、SiF4、鹵化硼等等之化合物,及金屬諸如鋁、鋇、鍶、鎵、銦、鎢、銻、銀、金、鈀、釓等等之有機金屬化合物。
吸附質氣體儲存於容器中之壓力可為任何適用於使用本發明之氣體儲存及配送系統之應用的適當壓力。一般有用於實施本發明之說明性的壓力值包括不超過約2500托爾之 壓力,不超過2000托爾更佳,例如,在自約20托爾至約1800托爾之範圍內之壓力,或更限制性地自約20托爾至約1200托爾。對於諸如離子植入之應用,氣體儲存及配送容器中之氣體壓力典型上不超過約800托爾,且儲存氣體可在低於大氣壓力下,例如,在自約20托爾至約750托爾之範圍內之壓力。
圖3係根據本發明之一具體例之儲存及傳送系統的概略圖式。
如圖所示,儲存及配送系統200包括儲存及配送容器204,其於其之上部結合至閥頭206,其包括包含在鋼瓶上配合閥頭用之手動引動器208之配送組件的部分。容器可由任何適當的構造材料形成,例如,包括諸如金屬、玻璃、陶瓷、玻化材料、聚合物及複合材料之材料。供此種用途用之說明性的金屬包括鋼、不銹鋼、鋁、銅、黃銅、青銅及其合金。閥頭藉由聯結器210結合至其中設置壓力轉換器214之配送導管212,用於以惰性氣體沖洗配送組件之惰性沖洗單元216,在配送操作中維持通過配送導管212之恒定流率的質量流量控制器220,及在配送氣體自配送組件排出之前將顆粒自配送氣體移除之過濾器222。
配送組件進一步包括聯結器224,以可配合地將配送組件與下游管件、閥件、或其他與使用脫附流體之軌跡相關之結構,例如,包括半導體製造設備諸如使用配送氣體作為植入物種之離子植入工具結合。
流體儲存及配送容器204經部分剖開展示,以顯示 內部的單塊吸附劑本體205。
圖4係根據本發明之另一及較佳態樣之使用長方體流體儲存及配送容器310之流體儲存及配送裝置之透視圖。長方體流體儲存及配送容器310設有管閥連接閥頭312及熔接至容器之頂面的手柄314。在一特定具體例中之容器310係經形成為沿容器之垂直(縱向)軸具有方形截面之熔接鋼壁構造。容器之壁為0.100英吋厚之碳鋼,及容器之內部體積為3.62公升。手柄314為¼英吋之桿原料,其經形成為如圖所示之形狀,並於各別端熔接至容器310。
管閥連接閥頭312之配送閥係藉由1½英吋管螺紋連接而與容器310經螺紋結合。閥頭可具有任何適當數目的口,例如,單口閥頭、雙口閥頭、三口閥頭等等。
長方體流體儲存及配送容器310於其之內部體積中包括單塊碳吸附劑,其中單塊物質可包括一或多個單塊碳本體,其各者之形狀為長方體,以配合容器之內部體積的形狀,如先前所說明較佳。
當明瞭本發明之組成物及方法可與文中之廣義揭示內容一致地以各種不同方式實行。因此,雖然本發明已參照特定的特徵、態樣及具體例說明於文中,但當明瞭本發明並不因此受限,反之其可以其他的變化、修改及具體例實行。因此,應將本發明廣義地解釋為包括在於後文提出專利申請之發明範圍內之所有此種其他的變化、修改及具體例。
200‧‧‧儲存及配送系統
204‧‧‧儲存及配送容器
205‧‧‧單塊吸附劑本體
206‧‧‧閥頭
208‧‧‧主動引動器
210‧‧‧聯結器
212‧‧‧配送導管
214‧‧‧壓力轉換器
216‧‧‧惰性沖洗單元
220‧‧‧質量流量控制器
222‧‧‧過濾器
224‧‧‧聯結器

Claims (53)

  1. 一種碳單塊(carbon monolith),該碳單塊是透過一方法所製備,該方法包含:將一可熱解材料成型成一單塊形狀;及將該可熱解材料在熱解條件下熱解,藉此產生一碳單塊,特徵在於以下特徵之至少一者:(a)在25℃及650托爾壓力下對胂氣體測量之填充密度為每公升碳單塊大於400克胂;以及(b)該碳單塊之整體孔隙度的至少30%包括尺寸在自約0.3奈米至約0.72奈米之範圍內之狹縫形孔隙,且整體孔隙度之至少20%包括直徑<2奈米之微孔隙。
  2. 如請求項1所述之碳單塊,具有在25℃及650托爾壓力下對胂氣體測量之填充密度,該填充密度為每公升碳單塊大於400克胂。
  3. 如請求項1所述之碳單塊,其中該碳單塊之整體孔隙度的至少30%包括尺寸在自約0.3奈米至約0.72奈米之範圍內之狹縫形孔隙,且整體孔隙度之至少20%包括直徑<2奈米之微孔隙。
  4. 如請求項1所述之碳單塊,其中該熱解條件包含低於1000℃的溫度,且該碳單塊具有約0.80至約2.0克/立方公分之一體密度(bulk density)。
  5. 如請求項1所述之碳單塊,具有一形態,該形態選自由塊(block)、磚(brick)、與鑲嵌物(boule)所組成的群組。
  6. 如請求項1所述之碳單塊,其中該方法進一步包含一活化步驟。
  7. 如請求項6所述之碳單塊,其中該活化步驟包含以下步驟:將該單塊暴露至一非氧化的高溫環境,之後將該單塊暴露至一氧化環境。
  8. 如請求項7所述之碳單塊,其中該非氧化環境包含氮氣。
  9. 如請求項7所述之碳單塊,其中該氧化環境包含二氧化碳。
  10. 如請求項7所述之碳單塊,其中該氧化環境包含蒸氣。
  11. 如請求項7所述之碳單塊,其中在將該單塊暴露至該氧化環境之後,在一非氧化環境中冷卻該單塊。
  12. 如請求項1所述之碳單塊,其配置於一氣體儲存及配送容器中。
  13. 如請求項12所述之碳單塊,將該碳單塊配置於該氣體儲存及配送容器中是透過一程序,該程序包含以下步驟:將一流體裝填至該容器,該單塊對該流體有吸附親和力;將該流體吸附在該單塊上;密封該容器,以將該單塊封在該容器的一內部體積中,該單塊收容(hold)吸附在該單塊上的流體;以及將該容器連接至一配送組件,以從該容器配送脫附的流體。
  14. 如請求項13所述之碳單塊,其在尺寸與形狀上順應該容器的該內部體積。
  15. 如請求項13所述之碳單塊,佔據該容器的至少60%的該內部體積。
  16. 如請求項13所述之碳單塊,佔據該容器的約75%至約95%的該內部體積。
  17. 如請求項13所述之碳單塊,包含多個個別的物件(discrete articles)。
  18. 如請求項17所述之碳單塊,其中該等個別的物件的每一物件的長度為該容器之該內部體積的高度的0.3倍至 1.0倍之間,且該等個別的物件的每一物件的截面積為該容器之該內部體積的截面積的0.1倍至0.5倍之間
  19. 如請求項17所述之碳單塊,其中該等個別的物件的每一物件具有長方體形(rectangular parallelepiped)之形狀。
  20. 如請求項17所述之碳單塊,其中在該容器的該內部體積中,該等個別的物件的每一物件在橫向及/或縱向上緊靠,而與相鄰的個別的物件表面接觸。
  21. 如請求項17所述之碳單塊,其中該等個別的物件的每一物件具有實心圓柱形態。
  22. 如請求項17所述之碳單塊,其中該等個別的物件的每一物件具有一長度對截面尺寸比(L/D),該長度對截面尺寸比為自約2至約20,其中L是該物件的長度或主軸的尺寸,且D為橫向或次軸尺寸。
  23. 如請求項17所述之碳單塊,其中該等個別的物件的每一物件具有一長度對截面尺寸比(L/D),該長度對截面尺寸比為自約4至約15,其中L是該物件的長度或主軸的尺寸,且D為橫向或次軸尺寸。
  24. 如請求項13所述之碳單塊,包含低於75個個別的單塊物件。
  25. 如請求項13所述之碳單塊,包含低於20個個別的單塊物件。
  26. 如請求項13所述之碳單塊,包含低於8個個別的單塊物件。
  27. 如請求項13所述之碳單塊,包含低於4個個別的單塊物件。
  28. 如請求項12所述之碳單塊,其中該可熱解材料於該氣體儲存與配送容器中原位熱解。
  29. 如請求項1所述之碳單塊,其中該可熱解材料包含一有機樹脂。
  30. 如請求項1所述之碳單塊,其中該可熱解材料包含選自由聚偏二氯乙烯、酚-甲醛樹脂、聚呋喃甲醇、椰子殼、花生殼、桃子核、橄欖核、聚丙烯腈、聚丙烯醯胺所組成之群組的材料。
  31. 如請求項1所述之碳單塊,其中該可熱解材料於一氣體儲存與配送容器中原位熱解。
  32. 如請求項1所述之碳單塊,其中該可熱解材料包含PVDC樹脂。
  33. 如請求項1所述之碳單塊,進一步包含一摻雜劑。
  34. 如請求項33所述之碳單塊,其中該摻雜劑包含至少一種試劑,該試劑選自由硼酸、四硼酸鈉、矽酸鈉、與磷酸氫二鈉所組成之群組。
  35. 如請求項1所述之碳單塊,其中該方法進一步包含以下步驟:將該單塊配置在一氣體儲存與配送容器中;將一流體裝填至該容器,該單塊對該流體有吸附親和力,以將該流體吸附在該單塊上;密封該容器,以將該單塊封在該容器的一內部體積中,該單塊收容吸附在該單塊上的流體;以及將該容器連接至一配送組件,以從該容器配送脫附的流體
  36. 如請求項35所述之碳單塊,其中該流體包含在半導體製造中具有效用之一氣體。
  37. 如請求項35所述之碳單塊,其中該流體包含選自由氫化物、鹵化物、與有機金屬氣態試劑所組成之群組的氣體。
  38. 如請求項35所述之碳單塊,其中該流體包含一氣體,該氣體選自由下述物質所組成之群組:矽烷、鍺烷、胂、膦、光氣、二硼烷、鍺烷、氨、、硫化氫、硒化氫、碲化氫、一氧化二氮、氰化氫、環氧乙烷、氘化氫化物、鹵化物(氯、溴、氟及碘)化合物及有機金屬化合物。
  39. 如請求項35所述之碳單塊,其中該流體具有在該內部體積中不超過約2500托爾的壓力。
  40. 如請求項35所述之碳單塊,其中該流體具有在該內部體積中不超過約2000托爾的壓力。
  41. 如請求項35所述之碳單塊,其中該流體具有在該內部體積中範圍為約20托爾至約1800托爾的壓力。
  42. 如請求項35所述之碳單塊,其中該流體具有在該內部體積中範圍為約20托爾至約1200托爾的壓力。
  43. 如請求項35所述之碳單塊,其中該流體在該內部體積中具有次大氣壓之壓力。
  44. 如請求項35所述之碳單塊,其中該流體在該內部體積中具有在約20至約750托爾之範圍內的壓力。
  45. 如請求項35所述之碳單塊,其中該容器包含構造材料,該構造材料選自由金屬、玻璃、陶瓷、玻化材料、聚合物、及複合材料所組成的群組。
  46. 如請求項35所述之碳單塊,其中該容器包含金屬的構造材料。
  47. 如請求項46所述之碳單塊,其中該金屬選自由鋼、不鏽鋼、鋁、銅、黃銅、青銅、及前述金屬之合金所組成的群組。
  48. 如請求項35所述之碳單塊,其中該單塊的孔隙度的至少20%是直徑低於2奈米的孔隙。
  49. 如請求項35所述之碳單塊,其中該流體包含三氟化硼。
  50. 如請求項35所述之碳單塊,其中該容器具有一長方體形的形狀。
  51. 如請求項35所述之碳單塊,其中該容器具有方形截面的一細長形狀。
  52. 如請求項35所述之碳單塊,其中該容器具有一圓柱形狀。
  53. 如請求項35所述之碳單塊,其中該容器具有一垂直豎立的配置形態。
TW102102674A 2002-12-10 2003-11-26 具有單塊碳吸附劑之氣體儲存及配送系統 TWI579485B (zh)

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