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chinese.click(function () { if(english.is(':hidden')) { english.show(); }else{ english.hide(); } }); }); </script> <header class="agency-01"> <div id="tp1ttpr" class="top-bar"> <div id="rpp1tpp" class="container"> <div id="p1tprpp" class="row"> <div id="tt7pt55" class="col-sm-6"> <ul class="list-unstyled list-inline"> <li><a href="mailto:info@opton-theme.com">郵箱: admin@sinohefa.com</a></li> <li><a href="tel:+49123456789">銷(xiāo)售部: 13376432136</a></li> </ul> </div> <div id="prr175r" class="col-sm-6" style="text-align: right"> <div id="15rrttp" class="top-right"> <a href="http://www.showinfantildonovan.com/" class="stock">簡(jiǎn)體中文</a> <div id="ptpt5pp" class="toggle"> <a >English</a> </div> </div> </div> </div> </div> </div> <div id="ttttrtr" class="container"> <div id="5rtpt7t" class="row"> <div id="tpr15pr" class="col-sm-2 col-xs-5"> <div id="1ptprp1" class="logo"> <a href="http://www.showinfantildonovan.com"> <img src="http://www.showinfantildonovan.com/assets/images/logo2.png" 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class="submenu"> </ul> </li> </ul> </nav> </div> </div> </div> </header> <style> .btn-btm{ border-radius: 2px; border: 1px solid #e4e4e4; display: inline-block; font-size: 11px; line-height: .5px; line-height: 2.09; color: #202020; padding: 7px 28px; font-weight: 700; } .btn-btm :hover{ background-color: rgb(43, 91, 55) !important; color: #000; } .btn-up{ position: relative; top:-20px; } </style> <div id="pt1ttrp" class="blog-posts-std-list blog-std-page blog-page-single"> <div id="t51tp1t" class="container"> <div id="rppttp1" class="row"> <div id="pttrt5t" class="col-md-9 col-sm-8"> <div id="tttt5rp" class="blog-box"> <div class="1tr51pp" id="blog-img-slider" class=""> </div> <div id="r5tptrp" class="blog-content"> <h3>疏水性沸石分子篩及其在二氧化碳控制技術(shù)中的應用</h3> <div id="rtpp1pp" class="blog-meta"> <p><span id="pprr5tt" class="meta-date">2018-07-12</span></p> </div> <p>摘　要: 介紹了疏水性沸石的疏水機理、制作方法、特性以及應用于二氧化碳控制技術(shù)中的特點(diǎn)。通過(guò)與空間站環(huán)控生保系統中傳統的四床分子篩二氧化碳控制技術(shù)的對比, 對以疏水性沸石為核心的兩床分子篩系統的特性進(jìn)行了分析, 探討了這一技術(shù)的發(fā)展前景與研究方向。關(guān)鍵詞: 沸石分子篩; 疏水性; 二氧化碳去除; 空間站中圖分類(lèi)號: R 852. 82 　　文獻標識碼: A　　文章編號: 1671-3206( 2002) 03-0012-04<br/></p><p>　　常用的沸石分子篩是一種人工合成的不溶性鋁硅酸鹽,它的晶體結構屬立方晶系,由 SiO4 和 AlO4 四面體結構單元所組成[ 1] 。這類(lèi)鋁硅酸鹽中硅氧比為 1∶ 2 ,符合于最簡(jiǎn)單式 SiO2 。由于在格架中有 Al3+離子代替了 Si4+離子,格架就帶負電荷, 為平衡AlO4 四面體的負電荷,在格架的空隙中必須存在補償電荷的陽(yáng)離子存在,這些陽(yáng)離子便成為極性點(diǎn), 使沸石分子篩具有親水特性。</p><p>圖 1　沸石的 SiO2/Al2O3 的摩爾比與吸水特性的關(guān)系</p><p>要提高沸石分子篩的疏水性,就要降低結晶中鋁的含量,提高 SiO2/Al2O3 的比例。圖 1 是 SiO2/ Al2O3 的摩爾比與吸水特性的關(guān)系,圖 1 中的關(guān)系清楚表明,吸水量隨結晶中鋁的含量的減少而顯著(zhù) 減少。疏水沸石結晶骨架中,沒(méi)有鋁原子,只有硅與氧原子。硅與氧原子的鍵距為 1. 6 ?,離子半徑各為 0. 40 及 1. 40,因此,吸附微孔被氧原子所包圍。這種 Si-O -Si 鍵中的氧原子并不呈堿性,也不形成氫鍵。從而微孔表面無(wú)極性,表現出疏水特性。本文對疏水性沸石的制作方法、特性以及在航天環(huán)控生保中的應用研究進(jìn)行介紹。 1　疏水性沸石分子篩的制法[ 2,3 ]</p><p>可通過(guò)直接合成法或以高硅沸石分子篩為材料,采用各種方法降低其鋁的含量。 1. 1　直接合成法這一方法的要點(diǎn)在沸石的水熱合成時(shí)添加有機礦化劑。在一般的沸石合成中,SiO2/Al2O3、OH/ SiO2 、H2O/SiO2 及無(wú)機堿的種類(lèi)與比例決定水熱合成的組成,但在疏水性沸石的合成中所用的堿,不僅是無(wú)機鹽,而且有如銨鹽那樣的有機堿礦化劑,在沸石的生成過(guò)程中,起到了模板的作用。制得的疏水性沸石的結晶中含有這種有機礦化劑, 但加熱到</p><p>第 31 卷第 3 期 2002年 6月</p><p>　　　　　　　　　　　　　　　　應　用　化　工 Applied Chemical Industry</p><p>　　　　　　　　　　　　　　　　Vol. 31 No. 3 Jun 2002</p><p>500 ℃以上就能分解除去。 1. 2　水熱生成與酸萃取組合法水熱燒成法是在蒸汽共存的情況下,將銨離子型或陽(yáng)離子型沸石在 500 ℃以上燒制的一種方法。在水熱燒制中,鋁原子從結晶骨架上脫落,同時(shí)由其它部分的硅原子置換, 從而提高 SiO2/Al2O3 的比例。但是從結晶骨架脫落下來(lái)的鋁原子,殘留在微孔中,必須將其除去。為此利用鹽酸將殘留在微孔中的鋁溶解下來(lái)。結晶骨架的 SiO2/Al2O3 比例的提高是依靠其它部分硅的補充,因此,產(chǎn)生缺限晶格 (空隙晶格) ,在結晶內存在空隙。L 型及 Ψ型沸石都能采用水熱燒成法穩定生產(chǎn)。</p><p>1. 3　六氟硅酸銨法銨型的沸石生料中加入六氟硅酸銨水溶液,沸石結晶骨架中的鋁原子直接由硅原子置換。由此結晶內的缺限極少,這一方法具有在低溫、液相中進(jìn)行的特點(diǎn)。反應如下:</p><p>O Al</p><p>NH+ 4</p><p>+(NH4) 2SiF6 O Si O O</p><p>+(NH4) 3AlF6</p><p>1. 4　四氯化硅法在 400 ℃以上的高溫下,將無(wú)水沸石與四氯化硅氣體反應,從而實(shí)現將結晶中的鋁原子與硅原子的置換。Y 型( SiO2/Al2O3 的摩爾比大于 4)沸石與四氯化硅蒸汽在常壓、450 ℃～ 550 ℃下,反應 2 h , SiO2/Al2O3 的比例可提高到 40～ 100。進(jìn)一步用鹽酸處理,SiO2/Al2O3 的比例可達 550。這一方法所制得的 Y 型沸石無(wú)缺限晶格。</p><p>O Al</p><p>NH+ 4</p><p>+SiCl4 O Si O O</p><p>+NH4Cl+AlCl3</p><p>2　疏水性沸石的特性</p><p>2. 1　吸附特性沸石的等溫吸附線(xiàn)是 Langmuir 型,疏水性沸石</p><p>的等溫吸附也屬于這一類(lèi)型。圖 2 是一種疏水性 Y 型沸石對 2,2,3,3 ,3-五氟丙醇的吸附曲線(xiàn),由克勞修斯-克拉貝龍公式得出其吸附熱為 49 kJ/mol 左右,是吸附質(zhì)的液化熱的 1. 2 倍,凈吸附熱約為 10 kJ/mol。從這些結果來(lái)看,疏水性沸石的吸附過(guò)程是物理吸附。</p><p>圖 2　疏水性 Y 型沸石對 2, 2,3,3,3-五氟丙醇的等溫吸附曲線(xiàn)[ 2 ] 疏水性沸石的吸附是被吸附分子填充在結晶微孔中實(shí)現的,圖 3 是沸石的結晶密度與孔隙率的關(guān) 系曲線(xiàn),圖 3 中 Vf 為孔隙率,df 為骨架密度,其單位為每 1 000 (?) 3 內所含的四面體數,虛線(xiàn)是以石英的 df=26 時(shí),Vf 為 0 以及 df =0 時(shí),Vf =1 引的一條直線(xiàn),圖 3 中各點(diǎn)分別代表各種類(lèi)型的沸石分子篩的情況。疏水性的 Y 型分子篩是由 ZSM-5 及 mordenite 制得的,但它的孔隙率有極大不同,從圖3 中可見(jiàn),它與 X 型( SiO2/Al2O3 的摩爾比為 2. 5)及 A 型沸石處于相同的位置,孔隙率是原來(lái)的 ZSM-5 及 mordenite 的 2 倍,因而它的飽和吸附量也能提高 2 倍左右。此外,在一定范圍內,這種 Y 型沸石的吸附與吸附質(zhì)的分子大小、形狀無(wú)關(guān)。 2. 2　吸水特性 [ 2, 5 ] 疏水性吸附劑是在與水共存的環(huán)境下應用,因此,對環(huán)境濕度的對抗能力是它的一個(gè)極其重要物性。圖 4 是多種疏水沸石及活性炭在不同濕度環(huán)境下的等溫吸附曲線(xiàn),從圖 4 中可見(jiàn),活性炭這種疏水性吸附材料,當相對濕度超過(guò) 60%后便開(kāi)始吸水, 疏水性沸石在相對濕度達到 80 %時(shí),都能保持幾乎不吸附水的特性。從中可見(jiàn)即使對于含水的空氣, 這種吸附材料也可選擇地吸附所需的物質(zhì),并且吸附量幾乎不受影響。</p><p>13第 3 期　　　　　　　　　　黃　燕: 疏水性沸石分子篩及其在二氧化碳控制技術(shù)中的應用　　　　　　　　　　　　　　</p><p>圖 3　沸石的結晶密度與孔隙率的關(guān)系曲線(xiàn)[ 3 ]</p><p>圖 4　多種疏水沸石及活性炭在不同濕度環(huán)境下的等溫吸附曲線(xiàn) 　　圖 5 是 Y 型疏水性沸石在對二甲苯與水分共存條件下的吸附等溫線(xiàn),從圖 5 中可見(jiàn),其吸附曲線(xiàn) 基本一致,水分的影響極少。</p><p>圖 5　Y 型疏水性沸石在對二甲苯與水分共存條件下的吸附等溫線(xiàn)</p><p>2. 3　穩定特性 [ 4 ] 沸石分子篩是通過(guò)加熱來(lái)實(shí)現再生的,因此,它的熱穩定性十分重要。將 Y 型疏水性沸石在 900 ℃下焙燒2 h ,其結晶度不變。它完全繼承了沸石那種孔徑均勻、微小的優(yōu)點(diǎn)。同時(shí)它的化學(xué)穩定性也極好,當其作為催化劑載體時(shí),它本身不具有催化特性,能保證產(chǎn)品的純度,這是其它載體所不具備的優(yōu) 點(diǎn)。圖 6 是將含有 3 000 ml/m3 丁酮的氣體以 280 ml/min 的速度分別通入到裝有 0. 7 g 疏水性沸石、纖維活性炭、粒狀活性炭的吸附柱上,在不同的溫度下所測得的丁酮濃度變化。這種疏水性沸石具有其它疏水吸附劑完全不具備的新特性。</p><p>圖 6　疏水性吸附劑的催化特性比較</p><p>3　疏水性沸石分子篩在航天環(huán)控生保系統中的應用研究</p><p>在空間站等航天器中,為了保障宇航員的生命安全,需要去除座艙環(huán)境中的二氧化碳,這種座艙環(huán) 境條件如表 1 所示?？刂七@一環(huán)境中二氧化碳濃度的成熟技術(shù)主要是分子篩,如美國的空間實(shí)驗室、俄羅斯的“和平號”空間站采用的就是四床分子篩 ( 4MB) 技術(shù),國際空間站中也是采用這一技術(shù)[ 6, 7] 。圖 7 就是這種四床分子篩的流程圖,它由兩個(gè)吸附/ 解吸和兩個(gè)干燥床組成。二氧化碳的吸附劑為 5 ? 沸石,由于5 ?沸石的親水性,在這種座艙大氣濕度下,由于水氣的存在而對二氧化碳的吸附失效。因此,在進(jìn)入吸附床前,空氣必須經(jīng)過(guò)干燥處理。干燥床的吸附材料采用硅膠或 13 X 的沸石。吸附床通過(guò)加熱或降低壓力來(lái)解吸,同時(shí)濃縮二氧化碳,干燥床的水分再由凈化氣體帶走而得以解吸。圖中虛線(xiàn)</p><p>14　　　　　　　　　　　　　　　　　　　　　　　　應用化工　　　　　　　　　　　　　　　　　　　　　　第 31 卷</p><p>圖 7　四床分子篩流程圖為凈化氣體與解吸二氧化碳所通過(guò)的路徑。表 1　座艙環(huán)境參數　　　參數數　值座艙大氣溫度/ ℃ 18～ 27 座艙大氣濕度/ % 20～ 70 座艙大氣壓力/kPa 81～ 101 座艙氧分壓/kPa 19. 5～ 23. 1 座艙 CO2 分壓/kPa 0. 4 　　研制一種吸附二氧化碳的性能遠比水好的“憎水性”分子篩,從四床分子篩的流程上去掉空氣的干燥過(guò)程,而只有兩個(gè)吸附床的工作的流程( 2MB)。其體積、質(zhì)量只占四床分子篩的一半,能耗低、操作控制簡(jiǎn)單,是替代現有空間站二氧化碳去除系統的最有力的候選技術(shù),但是它的問(wèn)題主要是缺乏疏水材料的數據。經(jīng)過(guò)對大量商用及研制的材料進(jìn)行實(shí) 驗,只有沸石分子篩與活性炭分子篩通過(guò)了靜態(tài)的二氧化碳吸附實(shí)驗,但艙內環(huán)境大氣是一種含有二氧化碳的混合氣體,由于活性炭孔徑分布范圍廣,它并不適合于選擇性的吸附,同時(shí)它工作的相對濕度不能超過(guò) 50 %,只有疏水沸石分子篩能在座艙濕度條件下順利工作。正由于座艙大氣二氧化碳的控制需要選擇性的吸附,并不是所有疏水沸石分子篩都能滿(mǎn)足要求。而Deca-dodecasil 是一種全硅的分子篩,它的結構保障了它的疏水物性,它的 3. 6 ? ×4. 4 ?的孔徑有能力吸附二氧化碳, 且阻止絕大多數痕量污染物 [ 5] 。在此基礎上,設計了全尺寸的疏水沸石分子篩二氧化碳控制系統,在表 2 所示的參數下,成功地控制艙內二氧化碳的濃度。</p><p>表 2　基本設計參數　　　參數數值空氣流量/m3 30～ 48 吸附劑質(zhì)量/kg 6 ～ 10 吸附循環(huán)周期/min 20 解吸溫度/℃ 175 　　與四床分子篩系統比較,在三人規模狀態(tài)下,其吸收劑的質(zhì)量可從 20 kg 減少到 6 kg, 僅干燥床一項系統就能減少質(zhì)量 34. 4 kg。解吸溫度從 204 ℃ 降低到 175 ℃,如果采用變溫變壓吸附的方式進(jìn)行解吸,其能耗可控制在四床分子篩的 1/2 范圍內。雖然它的吸附循環(huán)周期還較短,不到四床系統( 70 min)的 1/3,但目前所研制的疏水性分子篩的吸附容量還有很大潛力,進(jìn)一步提高這一性能不但可進(jìn) 一步提高其吸附循環(huán)周期,還可減少吸附劑的質(zhì)量。因此,這一技術(shù)在載人航天環(huán)控生保系統中應用極有競爭能力。 4　結束語(yǔ)</p><p>疏水性沸石具有至今所有的疏水吸附材料所不具有的優(yōu)良特性,對這一材料的研究、開(kāi)發(fā)利用,目前正處于方興未艾之中。這一材料在環(huán)境領(lǐng)域方面,已成功地應用在有機廢氣凈化、除臭等方面。利用這一材料的兩床分子篩是載人航天環(huán)控生保系統中的大氣控制技術(shù)中的最有前途的技術(shù),具有替代現有技術(shù)的巨大潛力,美國已將其列為替代現有技術(shù)的最優(yōu)方案。因此,積極開(kāi)展疏水性分子篩材料的研究,并解決其吸附容量的問(wèn)題,對促進(jìn)這一技術(shù) 的應用具有極為重要的作用</p><p><br/></p> </div> <div id="tttp1rt" class="blog-share-box clearfix"> <div id="tp1r7pt" class="agency"> <span> </span> </div> <div id="t1rptrp" class="share-box "> </div> </div> </div> </div> <div id="r1t1ppp" class="col-md-3 col-sm-4"> <div id="prr1rrp" class=""> <div id="pr5rrr1" class="widget-title"> <h3 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