TWI618578B - 粉狀氧化鈦、其製備方法及其用途 - Google Patents
粉狀氧化鈦、其製備方法及其用途 Download PDFInfo
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- TWI618578B TWI618578B TW105114891A TW105114891A TWI618578B TW I618578 B TWI618578 B TW I618578B TW 105114891 A TW105114891 A TW 105114891A TW 105114891 A TW105114891 A TW 105114891A TW I618578 B TWI618578 B TW I618578B
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- titanium oxide
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 158
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 55
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- 239000000725 suspension Substances 0.000 claims description 62
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 43
- 239000004408 titanium dioxide Substances 0.000 claims description 33
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- 230000001699 photocatalysis Effects 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 7
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000012065 filter cake Substances 0.000 claims description 5
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Abstract
本發明有關一種粉狀經無機後處理的氧化鈦,其製造方法,及其於生產觸媒之用途,特別是作為光觸媒及作為精煉觸媒撐體之應用。
Description
本發明有關一種粉狀、經無機後處理的氧化鈦,其製備方法,及其於製備觸媒之用途,特別是作為光觸媒及作為精煉觸媒撐體之應用。
許多二氧化鈦、及亦TiO2-SiO2材料為相關技藝已知,且被用作觸媒及/或催化活性材料的撐體。
在光催化領域中,商業供應許多TiO2為主的光觸媒。此等一般呈銳鈦礦、銳鈦礦-金紅石混合物或摻雜的二氧化鈦形式,具有廣泛範圍應用可能性。當光催化期間暴露於UV照射時,在自由基反應或電荷載體轉移中,氣相或溶解材料轉化成二氧化鈦,最常為銳鈦礦。已知具有大表面積之二氧化鈦例如商業銷售產品「HOMBIKAT UV100」或「HOMBIKAT M211」具有良好光催化性質。然而,仍想要進一步增進光催化活性。
長期已知在製造加氫脫硫(HDS)及加氫脫氮(HDN)之氫化處理觸媒中,使用二氧化鈦作為撐體材料。例如,
US6419889B1敘述使用具有比表面積70至99m2/g及雙峰孔分布之二氧化鈦撐體,其中90%孔具有至少100nm直徑。然而,純二氧化鈦之熱穩定性對典型於400℃發生的氫化處理應用還不夠好,造成老化效果及損失催化活性。
通常已知TiO2/SiO2材料亦可在多樣化催化應用中被用作觸媒或觸媒撐體,特別是來自爐、焚化廠、氣體渦輪機、工業裝置、內部燃燒引擎的廢氣中二氧化氮還原,作為選擇催化還原之撐體,及作為V-SCR觸媒。關於此點,典型導入SiO2以增加熱穩定性。然而,當添加SiO2時,部分催化活性二氧化鈦表面被SiO2覆蓋,限制催化性質。
已知許多方法製備此種TiO2/SiO2材料。若干製造如此TiO2/SiO2材料之方法係在添加或未添加含Si溶液下,以鹼從含Ti溶液(Ti-烷氧化物、硫酸氧鈦、氧氯化鈦等)沉澱。
例如,EP668100A1敘述製備觸媒之方法,將含矽化合物之酸性溶液及溶解其中的鈦化合物加入鹼性化合物溶液,引發共沉澱。
在DE3619337A1中,敘述混合硫酸鈦水溶液與含銨、水性SiO2溶膠而製造TiO2/SiO2粉末。將沉澱物洗滌、乾燥與煅燒,並用於生產觸媒材料。
除了以上外,文獻敘述許多從鈦-有機先質階段製備奈米TiO2之溶膠-凝膠方法,一個如此實例係敘述於EP 1719737A1。
沉澱獲得之SiO2/TiO2材料及溶膠-凝膠方法製備之SiO2/TiO2材料兩者幾乎完全非晶質,即若根本由X射線繞射法,信號僅非常微弱可偵測。此等非晶質TiO2/SiO2典型具有非常拙劣催化
性質。為了創造根據先前技藝TiO2/SiO2顆粒,需要熱處理例如熱液處理及/或煅燒。此等步驟適用於增加結晶性,但其等亦減少羥基含量的比表面積。此減少不利於催化應用。
除了如上述混合含Ti溶液與含Si溶液且然後引發沉澱之選擇外,先前技藝亦包含沉澱Si化合物於微粒二氧化鈦上之方法敘述。
因此,US6956006有關一種含有矽與二氧化鈦之複合材料,其中孔結構展現較大的熱與熱液抗性。獲得複合材料可從含有硫酸鹽與脲的水溶液沉澱氫氧化鈦,接著在母液中熱液處理,然後使沉澱物與鹼性膠態矽石反應。
WO0114054A1進一步敘述製備粉末形式的中孔TiO2/SiO2材料之方法,其中首現沉澱出呈氫氧化鈦形式之二氧化鈦,然後添加SiO2組分。
US 7125536B2敘述製備具高熱穩定性的奈米結構顆粒之方法,以鹼沉澱鋯或鈦鹽,添加例如發煙矽石的穩定劑,熱液老化,洗滌,乾燥及煅燒。
在根據US8545796B2方法中,將二氧化鈦懸浮液與Si源混合,然後調整pH值至<8.5,以致SiO2沉澱於TiO2顆粒上。以此方式製備之產物具有比表面積<400m2/g及孔體積<0.4cm3/g。
在以上引用的沉澱SiO2於微粒二氧化鈦之方法中,發現添加SiO2具有覆蓋部分催化活性二氧化鈦表面之效果,削弱催化性質。
先前技藝未知組合良好熱穩定性與非常大比表面積、高孔體積與顯著結晶性,且所以甚至於升高應用溫度下具有優
異性質作為觸媒或先質材料之二氧化鈦。
發明人現已發現根據發明經無機後處理的粉狀氧化鈦具有顯著增進的催化性質以及良好熱穩定性,因而克服先前技藝缺點。
發明產物之經無機後處理的粉狀氧化鈦,其特徵尤其在於下列性質:- 至少90重量%的組合含量之具有通式TiO(2-x)(OH)2x之水合氧化鈦〔其中0<x≦1、特別是0.1<x≦1(以TiO2計算)〕及包含其水合先質形式之二氧化矽(以SiO2計算),其中TiO2/SiO2重量比(TiO2與SiO2如方法敘述各自測定)係至少3、較好至少5且小於30、較好小於25,重量%係相對於105℃已乾燥至少2小時後的觸媒材料總重;其中餘料達100重量%由以下解釋的化學結合水及痕量副元素組成;- 乾燥產物之比表面積係>300m2/g、特別好>350m2/g;- 等電點係pH範圍4.0至7.0、較好4.5至5.9、特別好4.7至5.9。
當材料於105℃乾燥至少2小時,直接製備、經無機後處理、粉狀氧化鈦作為根據發明產物經歷重量損失高達10%,其中多數重量損失由水說明。除了在之前已乾燥的經無機後處理、粉狀氧化鈦中當時仍化學結合的水外,其可說明高達7重量%產物於105℃乾燥且僅可於更高溫度約200至800℃被引離,可含有痕量副元素例如Na、K、Ca、Mg、Cl、硫酸鹽、硝酸鹽、Nb、Zr、Fe、Cr、V、Li、Al作為產物構成要素呈組合總量不超過3%。因而,在直接製備
經無機後處理、粉狀氧化鈦作為產物中TiO2加SiO2總含量係如所述於105℃乾燥後至少90重量%。不管乾燥程度,根據發明經無機後處理、粉狀氧化鈦之TiO2/SiO2重量比係介於3至30,其亦未受其他組分影響。
因此,根據發明經無機後處理的氧化鈦亦可被敘述為粉狀觸媒材料,其含有通式TiO(2-x)(OH)2x之氧化鈦(0<x≦1、特別是0.1<x≦1)及包含其先質形式之二氧化矽,TiO2/SiO2重量比至少3、較好至少5且小於30、較好小於25,具有比表面積>300m2/g等電點範圍4.0至7.0,其中在直接製備的粉狀、經無機後處理氧化中,TiO2加SiO2總含量係至少80重量%,剩餘高達100重量%係由化學結合水及先前所述源自製造方法與起始物材料(例如鈦鐵礦)之痕量副元素組成。
關於此點,粉狀、經無機後處理氧化鈦亦可有利具有至少一個以下性質:●由篩選分類之粒徑不超過1mm;●在常態大氣中於500℃熱處理1小時後,產物比表面積仍至少80m2/g、特別是至少100m2/g、較好大於150m2/g;●根據方法章節所述方法測量,由氯仿分解率測量之光催化活性大於0.3mmol/(h*m2)、特別是大於0.5mmol/(h*m2)、最特別是大於0.6mmol/(h*m2)、特別好大於0.7mmol/(h*m2);●孔體積(N2脫附,總計)>0.3cm3/g、較好>0.5cm3/g、特別好>0.7cm3/g;●銳鈦礦相具微晶尺寸5至15nm;●孔分布具最大範圍10至35nm、特別是範圍10至30、較好20至
30nm。
提及根據本發明氧化鈦或氧化鈦懸浮液時,欲了解根據發明鈦-氧化合物意指具式TiO(2-x)(OH)2x(0<x≦1),及亦呈二氧化鈦水合物,其亦可一起敘述為TiO2與TiO(OH)2或其水性懸浮液。
與電解質接觸的氧化物由於解離過程,在其等表面上發展電荷,此等電荷於某些pH值的規模與極性係關心氧化物的特徵。表面未攜帶電荷之pH值稱為等電點(IEP)。以高於IEP之pH值,表面永遠荷負電,低於IEP,其永遠荷正電。純二氧化鈦或氧化鈦水合物之等電點係約pH 6。SiO2之等電點係pH=2至3。因此,此「等電點」(IEP)可用作測量二氧化鈦顆粒表面積被SiO2覆蓋之程度。二氧化鈦/氧化鈦水合物表面積被SiO2之覆蓋域造成等電點範圍從pH 5轉移至2,取決於被SiO2覆蓋之二氧化鈦表面積百分率。當100%二氧化鈦表面積被SiO2覆蓋時,SiO2/TiO2的IEP係約pH=3至2。由於用SiO2處理二氧化鈦表面積,IEP越少轉移向pH=2,已用SiO2覆蓋之表面積百分率越低。相反地,此增加由二氧化鈦組成之顆粒表面積百分率,依序導致催化活性增加。同時,被SiO2覆蓋之二氧化鈦表面積百分率不僅取決於SiO2含量,而且視Si處理方法而定。由此推斷催化性能不僅由結構性質(5點BET,孔體積)及絕對SiO2含量決定,而且由SiO2遍布於TiO2表面之方法決定。
在發展本發明方法及根據該方法製備的粉狀經無機後處理氧化鈦時,發明人已使用此發現。因此,發明人已製備主要有銳鈦礦改質的定義晶形區之如此粉狀、經無機後處理氧化鈦,其中部分表面積係以SiO2或水合先質階段或其混合物覆蓋,其中產物全體稱為含Si化合物,因而能夠在乾燥後提供材料增加的熱穩定
性,同時其催化活性實際上未改變。根據發明人發現,可獲得此等性質,由於沉澱於具通式TiO(2-x)(OH)2x(0<x≦1)個別氧化鈦顆粒上之SiO2與其水合先質在乾燥期間保持個別TiO2顆粒「分開」之事實,以致個別TiO2晶形區無法聚結,造成保存具充分催化活性表面積的結果。
根據發明,獲得經無機後處理、粉狀氧化鈦因而係用一或多種懸浮液之含Si化合物處理具有式TiO(2-x)(OH)2x(0<x≦1)之氧化鈦顆粒懸浮液,以致該氧化鈦顆粒表面積與此塗布。
因此,根據發明方法係一種製備以粉末形式氧化鈦為基礎的觸媒材料之方法,其中:a.藉由加強攪拌及/或分散,將適中尺寸顆粒20至500nm具有通式TiO(2-x)(OH)2x(其中0<x≦1、特別是0.1<x≦1)的氧化鈦水合物顆粒及/或水合氧化鈦或其混合物之水性懸浮液(以下稱為「氧化鈦懸浮液」)與含Si化合物溶液混合,較好同時維持pH於pH值pH=3至9、特別是4至7,b.若需要,視情況調整pH值範圍介於4至7,c.過濾獲得的懸浮液,d.視情況用水洗滌獲得的濾餅,直到濾液具有導電性不超過500μS/cm,且e.乾燥獲得的產物。
在添加含Si溶液前,由添加酸或鹼溶液,氧化鈦懸浮液之pH值可被調整達pH值3.0至9.0、特別是4.0至8.5、較好4.0至7.5、特別好4.0至7.0。當添加含Si溶液時,可在先前設立的pH值維持pH值。
關於此點,選擇含氧化鈦懸浮液及含Si化合物溶液之數量,以致如上述於105℃乾燥至少2小時後,根據發明產物具有總含量至少90重量%TiO2加SiO2。
在具體化中,具有式TiO(2-x)(OH)2x(其中0<x≦1)的氧化鈦顆粒之懸浮液可為具式TiO(OH)2的偏鈦酸,其在用於製備二氧化鈦之硫酸鹽方法中沉澱為中間產物。
在其他生產方法中,雖然具式TiO(2-x)(OH)2x(其中0<x≦1)的氧化鈦顆粒較好由硫酸鹽方法獲得,但具式TiO(2-x)(OH)2x(其中0<x≦1)的氧化鈦顆粒之懸浮液亦可由沉澱、水解或溶膠-凝膠方法從含Ti溶液獲得,特別是從可水解化合物例如含TiOSO4或TiOCl2溶液。
此所用「氧化鈦懸浮液」-表示此具通式TiO(2-x)(OH)2x(其中0<x≦1、特別是0.1<x≦1)的氧化鈦水合物及/或水合氧化鈦顆粒或其混合物之懸浮液-較好具有以下性質:- 呈二氧化鈦計算之Ti含量50至400g TiO2/l,- 平均粒徑20nm至1000nm、較好20nm至500nm、特別好50nm至200nm,最特別好50nm至150nm,- 顆粒比表面積200至500m2/g、較好200至400m2/g、特別好300至400m2/g(在105℃乾燥至少120分鐘後,由N2孔隙測定計、5點BET測量),- 顆粒總孔體積>0.3cm3/g、較好>0.5cm3/g、特別好>0.7cm3/g(在105℃乾燥至少120分鐘後,由N2孔隙測定計、5點BET測量),- 在105℃乾燥至少120分鐘後,多數顆粒晶相呈銳鈦礦相存在,即
扣除直線次表面(linear subsurface)後,銳鈦礦結構的最強烈反射高度(反射(101))與金紅石結構的最強烈反射高度(反射(110))之比率係至少5:1、較好至少10:1。根據此文件「方法」章節敘述進行之XRD分析較好僅涉及銳鈦礦結構的反射。
所用偏鈦酸含有鈦-氧化合物,亦可含有自由與結合硫酸,其中鈦-氧化合物的晶形分率係如早先提及呈銳鈦礦改質存在,且具有典型微晶尺寸約5至15nm。鈦-氧化合物可以通式TiO(2-x)(OH)2x(其中0<x≦1)敘述。根據硫酸鹽方法製備TiO2時,偏鈦酸係沉澱為中間產物。在硫酸鹽方法中,鈦鐵礦及/或熔渣與90%H2SO4崩解,將如此獲得的崩解餅溶於水,令溶液沉降。添加廢鐵,將三價溶解鐵轉化成其二價形式,因為Fe3+會與偏鈦酸一起沉澱,然後被吸收,其並不想要。取決於溶液之Fe含量,在溶液冷卻並從系統移除後,沉澱出FeSO4 x 7 H2O。在隨後水解期間,TiOSO4轉化成偏鈦酸。其他水合形式例如原鈦酸轉化成偏鈦酸,並釋放H2O。
根據發明,(硫酸)偏鈦酸可特別用鹼性溶液中和,較好選自NaOH、氨、碳酸鈣、氫氧化鈣、或亦Ba(OH)2,特別好用NaOH。
從而獲得的中和偏鈦酸較好用水洗滌,直到其於濾液中達到導電性不大於500μS/cm,然後將洗滌的崩解餅置入懸浮液或分散,較好用攪拌器,特別好用溶解器。
較好借助渦輪攪拌器、溶解器、環形粉碎機、粉碎機泵、梯度泵、分批珠式粉碎機或轉子-定子分散機(如由IKA生產之ULTRA-TURRAX),進行加強攪拌或分散「氧化鈦懸浮液」。
此敘述給予之重量百分率數字根據發明涉及根據發明在105℃已乾燥至少120分鐘之粉狀、經無機後處理氧化鈦的總重,一起添加時等於100重量%材料總重,其中包含任選組分。
根據發明材料之氧化鈦顆粒係不規則形狀,且可約略敘述為球形。材料並非為管形、桿形或小板形。
含Si化合物可特別為Na2SiO3溶液,具SiO2濃度50至500g SiO2/l、特別是100至500g SiO2/l、較好200至400g SiO2/l。較好如下添加含Si化合物:在分散期間,於pH值3至9、較好pH 4至8.5、特別是4至7.5、特別好pH=4至7,將含Si溶液(如具濃度SiO2=50至500g SiO2/l形式)添加至具有式TiO(2-x)(OH)2x(其中0<x≦1)的氧化鈦懸浮液,獲得TiO2/SiO2重量比率至少3。
從而獲得根據發明粉狀氧化鈦-SiO2觸媒材料可根據發明以下列方法用於生產根據發明成形體:1.從以下製備水性氧化鈦-SiO2糊漿:- 根據發明塗布有一或多種擠壓助劑之粉狀氧化鈦-SiO2觸媒材料,- 解膠劑,較好為鹽酸、硫酸、硝酸、乙酸、草酸,- 水,較好為去礦質水,及以下作為視情況構成要素i.塑化劑例如纖維素、黏土、聚乙烯醇、聚乙二醇,較好為纖維素,特別好為泰勒粉(tylose)ii.黏合劑例如TiO2溶膠、TiOSO4溶液、氧化鋁、SiO2溶膠或黏土,較好為TiO2溶膠、TiOSO4溶液或AlO(OH)(水鋁石或假水鋁石)iii.鹼,較好為氨或含胺化合物
iv.潤滑劑例如甘油v.孔洞產生器例如澱粉或碳黑關於此點,糊漿中水含量係較好選擇糊漿,以致於壓力1至100巴或若需要高達200巴,糊漿可由擠壓機(雙螺旋鑽)推進穿過具出口截面1至5mm之噴嘴;2.在如雙z捏合機中,捏合從而獲得的糊漿,典型30至60分鐘;3.成形,如擠壓糊漿以製造成形體,例如具有直徑如1至5mm及長度典型10至25mm之繩索;4.乾燥例如擠出物之成形體,最初於20至30℃、特別是25℃乾燥大於1小時、特別是大於6小時、相當特別大於12小時,然後於80至120℃、特別於90℃乾燥60至120分鐘,然後於300至600℃、特別是350至600℃、特別好350℃至450℃、特別是400℃煅燒1至4小時。
可使用一或多種塗布TiO2-SiO2顆粒表面之化合物作輔助成形劑,在溫度低於銳鈦礦成金紅石之轉化溫度(915℃)、較好低於600℃、特別好低於400℃,較好無殘渣下,化合物蒸發、昇華或分解。擠壓助劑支持成形且可被遺留介於及/或在粉狀觸媒材料顆粒上,在捏合步驟期間具有有利效果,較好幫助保持粉狀觸媒材料之顆粒分開。以此方式,可添加物質作為擠壓助劑,首先於捏合期間促進塑性塊形成,然後於成形時亦支持模製體的機械穩定性。此等擠壓助劑於煅燒期間移除,完全移除為較佳。
擠壓助劑可較好為有機烴化合物,其可含有至少一個選自羥基、羧基、胺基、亞胺基、醯胺基、酯基、磺醯基、酮基、及其硫類似物或從該組群數種不同物質之官能基,且在溫度低於銳
鈦礦轉化成金紅石之溫度(915℃)、較好低於600℃、特別好低於400℃下,例如在製造根據發明二氧化鈦成形體期間,其蒸發、分解或昇華。較好係具至少一個官能基且含有一或多個氧原子(例如羥基、羧基)之低分子有機烴化合物。為了本發明目的,欲了解低分子有機烴化合物係具有1至12個碳原子且具有選自羥基、羧基、胺基、亞胺基、醯胺基、醯亞胺基、酯基、磺醯基、酮基、及其硫類似物(特別是羥基及羧基)取代基之一的烴化合物。
因此,擠壓助劑可係在溫度低於銳鈦礦轉化成金紅石之溫度(915℃)、較好低於600℃、特別好低於400℃下,煅燒根據發明二氧化鈦成形體期間,蒸發、分解或昇華之酸、鹼、烷醇胺或若干其他物質。
擠壓助劑較好為有機酸,特別好為羧酸,特別是具有1至6個碳原子、包含二-與三羧酸,特別好乙酸、草酸、酒石酸、順丁烯二酸或檸檬酸,特別是草酸。硝酸、氨、烷醇胺或釋氨化合物亦可較好被用作擠壓助劑。同樣地,醣例如纖維素、纖維素醚、泰勒粉、葡萄糖、聚丙烯酸胺、聚乙烯醇、硬脂酸、聚乙二醇或其混合物亦可被用作擠壓助劑。蒸發、昇華或分解擠壓助劑後,根據發明成形體具有剩餘碳含量小於2重量%、較好小於1重量%,相對於煅燒後成形體重量。
從根據發明觸媒材料製造之成形體典型具有以下性質:- 壓碎強度>5N/mm、特別是>8N/mm、較好>10N/mm、特別好>15N/mm、最特別好>25N/mm;- 比表面積>80m2/g、特別是>100m2/g、較好>120m2/g、特別好
>150m2/g、最特別好>200m2/g;- N2孔體積>0.2cm3/g、較好>0.3cm3/g、特別好>0.6cm3/g;- 每體積的總比表面積大於100,000m2/l、較好大於120,000m2/l。
從根據發明觸媒材料製造之根據發明成形體可根據發明被用作以下應用領域中催化活性金屬(例如V、W、Co、Mo、Ni、Fe、Cu、Cr、Ru、Pd、Pt、Ag、Zn)之觸媒或觸媒撐體- 光催化- 克勞司(Claus)催化- 克勞司尾部氣體處理- SCR、氫化處理、氣體對液體、費雪-闕布希方法等。
如此負載的根據發明含氧化鈦成形體典型具有含量10至35重量%Mo、0至6重量%Co及/或Ni〔各呈金屬氧化物(MoO3、CoO及NiO)計算〕,及具有通式TiO(2-x)(OH)2x之氧化鈦(具0<x≦1、特別是0.1<x≦1)與SiO2含量高達100重量%,且比表面積至少80m2/g、特別是至少100m2/g及孔體積大於0.25cm3/g、較好大於0.27cm3/g,其中重量百分率係相對負載的含氧化鈦成形體總重。如此負載的根據發明含氧化鈦成形體之MoO3含量可特別為18至30重量%。如此負載的根據發明含氧化鈦成形體之平均孔徑可為7至15nm。
本發明將以下列包含根據發明製造實例及比較例之實驗章節,更大幅詳細解釋。
為了決定具有通式TiO(2-x)(OH)2x之氧化鈦(其中0<x≦1)的平均粒徑,將水性「氧化鈦懸浮液」首先稀釋於1g calgon/l去離子水的溶液,獲得濃度大約0.4g TiO2於60ml溶液。然後分散以此方式稀釋的「氧化鈦懸浮液」係於超音波浴(如Sonorex Super RK106,Bandelin生產)攪拌5分鐘,然後用超音波探針(Sonifier W-450,Branson生產,具波幅放大的含金升壓器及3/4吋高效能共振器)分散5分鐘。使用光子相關光譜計,以Malvern生產之Zetasizer高級軟體(如Zetasizer 1000HSa)決定粒徑分布。在測量溫度25℃採用具多模計算之測量。體積分布d50值,符合考慮密度之質量分布係給予為平均粒徑d50。
記錄X射線繞射圖,決定結晶改質(相鑑定)。對此,在結晶晶格面,根據布拉格定律繞射之X射線束的強度係對繞射角2θ測量。X射線繞射圖案典型係針對相。
借助目的撐體,將欲調查的材料伸展於製備撐體上。使用JCPDS粉末繞射測定資料庫評估粉末繞射測定數據。相於測量繞射圖與儲存線圖相配時被辨識。
測量條件典型係:2θ=100至700,2θ增值=0.020,每停止測量時間:1.2s。
根據下式,使用謝樂方法,在2θ 25.30,從銳鈦礦反射之半高峰寬決定微晶尺寸:
D微晶=K*I/(S*cosθ)
其中:
D微晶:微晶尺寸〔nm〕
K:成形常數=0.9
θ:測量反射2θ/2之角位置
S:測量反射半高處之峰寬
I:所用X射線束波長
秤重及以硫酸/硫酸銨蛻變材料,隨後用蒸餾水稀釋,過濾及用硫酸洗滌。然後煅燒濾器且重量決定SiO2含量。
以硫酸/硫酸銨或硫酸鉀蛻變材料。以Al還原成Ti3+。以硫酸銨鐵(III)滴定(指示劑:NH4SCN)。
樣品中呈TiO2及SiO2計算之Ti及Si濃度係如上述決定。然後決定TiO2/SiO2比率係將計算的TiO2含量除以計算的SiO2含量。
使用Quantachrome GmbH生產之Autosorb 6或6B設備,由N2孔隙測定計計算比表面積及孔結構(孔體積及孔直徑)。根據DIN ISO 9277決定BET(Brunnauer、Emmet及Teller)表面積,根據DIN 66134測量孔分布。
將秤入測量槽的樣品於烘乾站真空預乾燥16小時。然後於真空加熱高至180℃約30分鐘。然後仍於真空維持溫度1小時。當除氣器記錄平穩壓力20至30毫托,且真空泵已拆接後真空顯示器的針保持穩定約2分鐘時,考慮樣品充分除氣。
使用20個吸附點及25個脫附點測量全部N2等溫線。評估測量如下:
比表面積(多點BET)
5個測量點於評估範圍0.1至0.3p/p0
評估總孔體積
根據Gurvich規則決定孔體積
(使用最後吸附點決定)
根據DIN 66134,以Gurvich規則為基礎,決定總孔體積。根據Gurvich規則,在吸附測量期間,從最後壓力點決定樣品之
總孔體積:
p.吸附劑的壓力
p0.吸附劑的飽和蒸汽壓
Vp.根據Gurvich規則之比孔體積(在p/P0=0.99之總孔體積)。實際上在測量期間達到最後吸收壓力點。
評估平均孔直徑(液壓孔直徑)
對此計算,使用關係4Vp/ABET,符合「平均孔直徑」。ABET比表面積根據ISO 9277。
從光催化分解氣相有機物質(例如甲醇或氯仿)可決定光活性,決定光活性係對示範目的於90mm直徑盤皿進行。藉由超音波攪拌,在燒杯中將50mg粉末樣品及100mg硫酸鋇(鋇白)XR-HN(Sachtleben Chemie GmbH生產之商業產品)分散於40ml純化水,立刻將所有倒入培養皿。在50℃真空中,蒸發懸浮液達完全乾燥。乾燥後,必須保持粉末均勻分布層。以此方式製備的粉末樣品於UV光下用輻射照度值約10W/m2調理10小時。
為了決定光催化活性,將粉末樣品置入氣體光催化組件之氣體反應器(如由Ansyco),具UV燈(E=5至40W/m2)及連接的氣體層析儀(具分流/不分流注射及FID與PDD偵檢器、控制組件及放大器,例如「Trace GC Ultra」)。照明強度預先已設定為7W/m2,使用UV測量儀器(如PCE-UV34)檢查。已安置樣品後,設定超壓為0.6巴,系統用合成空氣(50%相對溼度)沖洗10分鐘。沖洗後,設定氣流100l/h,超壓降低至0巴,在此設定静置系統5分
鐘以穩定化。後來,將1.0μl氯仿(等值於12.4μmol)注射穿過隔片。每7分鐘進行層析圖測量。照射未立即開始,使試驗氣體達到吸附/脫附平衡,亦即對四個連續測量試驗氣體含量偏離平均不大於0.2μmol。已建立此平衡後,開始UV燈照射。然後,每7分鐘採取GC測量反應器之氯仿含量。預先對氯仿校正GC。
根據0及7分鐘數據,借助線性回歸,決定比光催化分解率呈mmol/(h*m2)。比分解率係計算如下:
顆粒的等電點定義係ζ電位為零之pH值。關於此點,ζ電位係移除懸浮液中顆粒界面層處之電位(亦稱為Coulomb電位)。在具滴定組件之「PA Field ESA設備」中測量電泳移動性。當靜電顆粒暴露於頻率範圍約0.8至1.2MHz的交流電場時,測量創造的超音波壓力振福。
以下方程式相關聯:ESA=c Φ △ρ μ
其中:
ESA=電動聲學振福(信號壓力振福)
c=溶液的音速
Φ=顆粒的體積分率
△ρ=顆粒與溶液間的密度差異
μ=電泳移動性
為了製備樣品,藉由劇烈搖動於燒瓶中,將粉末首先
與去礦質水混合(2體積%粉末)。使用PA Field ESA設備測量與懸浮液pH值呈函數之懸浮顆粒ESA信號。對此,以鹽酸(c(HCl)=1mol/l)及(c(NaOH)=1mol/l)滴定懸浮液。從電泳移動性可計算ζ電位。針對水性及含溶劑系統,由「PA Field ESA軟體」完成。對pH值繪製電泳移動性。等電點符合電泳移動性等於零之pH值。
呈銳鈦礦改質之二氧化鈦,具比表面積約330m2/g,孔體積約0.3cm3/g,及硫酸鹽含量約1.5重量%TiO2。
將833mL具二氧化鈦含量300g TiO2/l之偏鈦酸(來自Sachtleben Chemie GmbH)置入21玻璃燒杯。以計量率2.0mL/min添加67.6mL水玻璃(360g SiO2/L),同時攪拌。然後,pH值被決定於4.5/21℃。令懸浮液再攪拌5分鐘且以苛性鈉中和至pH 6.5/24℃,其中於pH=5.0添加400ml部分去礦質水。使懸浮液加熱至60℃,以攪拌於此溫度成熟1小時。透過布氏漏斗過濾懸浮液並洗滌。在最後洗滌濾液中,測量導電性40μS/cm。將洗滌的濾餅以強制空氣對流於溫度150℃乾燥櫥中乾燥4小時,然後於IKA實驗室粉碎機中研磨10秒。
在5L玻璃燒杯中提供500mL部分去礦質水,以溶解器
(Dispermat LL30)及具直徑6cm的溶解器盤攪拌。為了造成沉澱,將析出物1.92L硫酸氧鈦溶液(HOMBITYL,c(TiO2)=112g/L)、108mL矽酸鈉溶液(c(SiO2)=200g/L)及2.47L氨水(w(NH3)=15%)添加於水饋料,同時於190分鐘內攪拌,令pH值於沉澱期間維持於範圍pH=5至6。以旋轉速度700rpm開始沉澱,隨著沉澱物體積上升而增加至1000rpm。沉澱結束時,於45℃沉澱懸浮液中測量pH值5.4。使懸浮液以攪拌加熱至80℃,於此溫度成熟1小時。然後令沉澱懸浮液的pH值決定於4.8/80℃,並以稀釋硫酸(20%)調整至pH 4.25/80℃。透過布氏漏斗過濾懸浮液並洗滌濾餅。洗滌後,在濾液中發現導電性342μS/cm。將洗滌的濾餅於溫度150℃乾燥櫥中乾燥隔夜,然後於IKA實驗室粉碎機中研磨10秒。
使用具平均粒徑50nm及TiO2含量50g TiO2/l之「氧化鈦懸浮液」作為原料。使用溶解器,令6l「氧化鈦懸浮液」分散15分鐘。將懸浮液pH值以稀釋苛性鈉調整至pH=6.5。然後於15分鐘內,將34ml矽酸鈉溶液(350g SiO2/l)添加於氧化鈦懸浮液,同時持續溶解器分散。將懸浮液以劇烈攪拌於60℃成熟60分鐘。然後,過濾、洗滌及噴霧乾燥懸浮液。
使用具平均粒徑50nm及TiO2含量50g TiO2/l之「氧化鈦懸浮液」作為原料。在環形粉碎機中(生產商Getzman),令6l「氧化鈦懸浮液」分散30分鐘。將懸浮液pH值以稀釋苛性鈉調整至pH=
7.5。然後於30分鐘內,將68ml矽酸鈉溶液(350g SiO2/l)添加於氧化鈦懸浮液,同時持續分散。將懸浮液以劇烈攪拌於60℃成熟60分鐘。然後,過濾、洗滌及噴霧乾燥懸浮液。
使用具平均粒徑50nm及TiO2含量50g TiO2/l之「氧化鈦懸浮液」作為原料。在轉子-定子分散組件中(由IKA的ULTRA-TURRAX),令6l「氧化鈦懸浮液」分散15分鐘。將懸浮液pH值以稀釋苛性鈉調整至pH=7.5。然後於20分鐘內,將100ml矽酸鈉溶液(350g SiO2/l)添加於氧化鈦懸浮液,同時持續分散。將懸浮液以劇烈攪拌於60℃成熟60分鐘。然後,過濾、洗滌及噴霧乾燥懸浮液。
使用具平均粒徑50nm及TiO2含量100g TiO2/l之「氧化鈦懸浮液」作為原料。使用溶解器,令1.5l「氧化鈦懸浮液」分散15分鐘。將懸浮液pH值以稀釋苛性鈉調整至pH=6.0。然後於15分鐘內,將15.9ml矽酸鈉溶液(378g SiO2/l)添加於氧化鈦懸浮液,同時持續溶解器分散。將懸浮液以劇烈攪拌於60℃成熟30分鐘。然後,過濾、洗滌及噴霧乾燥懸浮液。
使用具平均粒徑50nm及TiO2含量100g TiO2/l之「氧化鈦懸浮液」作為原料。使用溶解器,令1.5l「氧化鈦懸浮液」分散
15分鐘。將懸浮液pH值以稀釋苛性鈉調整至pH=6.0。然後於15分鐘內,將31.8ml矽酸鈉溶液(378g SiO2/l)添加於氧化鈦懸浮液,同時持續溶解器分散。將懸浮液以劇烈攪拌於60℃成熟30分鐘。然後,過濾、洗滌及噴霧乾燥懸浮液。
表1列載根據發明及比較例粉末之結構性質以及熱穩定性與光催化活性。
根據先前技藝,已知經SiO2穩定的二氧化鈦於熱老化後具有(可接受)比表面積約200m2/g(參見如比較例2及3)。然而,此等光催化活性非常低(氯仿分解率不大於0.1mmol/h*m2)。由於光催化活性二氧化鈦表面被不活性SiO2覆蓋之故,想必光催化活性差,同時伴隨相對低IEP(3.8至4.4)。
純二氧化鈦例如用於VB1的商業可得產品證明可接受的光催化分解率,但此等二氧化鈦並未熱穩定。在500℃ 1小時後,此等產品之比表面積範圍僅80至100m2/g。因此,如此材料無法被用作具升溫應用之觸媒或觸媒撐體。
僅有根據發明材料組合非常高的光催化活性(氯仿分解率>0.7mmol/h*m2)與良好熱穩定性,亦即於500℃熱處理1小時後比表面積等於或大於130m2/g。
將先前實例與比較例製造之材料用於製備觸媒撐體,其中使用擠壓助劑執行擠壓方法。因此,獲得經塗布的粉狀觸媒材料可用擠壓助劑或數種擠壓助劑混合物於溶液或懸浮液處理根據發明顆粒之懸浮液,結果根據發明顆粒之表面積被擠壓助劑塗布,隨後擠壓經塗布的顆粒以製造成形體。
將400g Hombikat M211(二氧化鈦,Sachtleben生產之商業產品)及64g 2.5%泰勒粉水溶液置入雙z捏合機之混合槽,混合約1分鐘。然後添加60g 10重量%鹽酸及亦去礦質水,直到捏合塊具
有塑性稠度。然後捏合此混合物30分鐘。隨後,添加20g氨水(25%)及20ml去礦質水,捏合混合物30分鐘。然後於壓力40至70巴透過1.8mm模(「四葉」形)擠壓捏合塊,並切成想要長度(大約15至20mm)。以此方式製造之擠出物經空氣乾燥,然後加熱至90℃ 60分鐘,然後在數小時期間加熱至煅燒溫度400℃,並維持此溫度120分鐘,然後冷卻至室溫。
將400g實例2及64g 2.5%泰勒粉水溶液置入雙z捏合機之混合槽,捏合約1分鐘。然後添加60g 10重量%鹽酸及亦去礦質水,直到捏合塊具有塑性稠度(約70ml)。然後捏合此混合物30分鐘。隨後,添加20g氨水(25%)及20ml去礦質水,捏合混合物30分鐘。然後於壓力40至70巴透過1.8mm模(「四葉」形)擠壓捏合塊,並切成想要長度(大約15至20mm)。以此方式製造之擠出物首先經空氣乾燥,然後如實例1所述回火。
將400g EB1粉末及64g 2.5%泰勒粉水溶液置入雙z捏合機之混合槽,捏合約1分鐘。然後由添加鹽酸及亦添加去礦質水,直到捏合塊具有塑性稠度,令捏合塊pH值調整至pH=1.5。然後捏合此混合物30分鐘。隨後,添加氨水(25%),將捏合塊pH值調整至pH=5,並捏合進一步30分鐘。然後於壓力40至70巴透過1.8mm模(「四葉」形)擠壓捏合塊,並切成想要長度(大約15至20mm)。以此方式製造之擠出物首先經空氣乾燥,然後如實例1所述回火。
以上述粉末EB1(EB1-E)擠壓之相似方式,從EB2及EB3粉末進行擠出物製造。
實例中擠壓製造之擠出物意欲以活性金屬例如NiMo及CoMo浸漬。為此目的,在第一步驟中,如下製備含CoMo-及NiMo-浸漬溶液:
使用對應金屬化合物例如鹽或氧化物,於磷酸存在下,在水溶液中製備浸漬溶液,且其pH以硝酸調整。
針對浸漬,將各100g擠出物置入旋轉器皿(如旋轉蒸
發器)。使浸漬溶液緩慢(0.5ml/min)加至擠出物。計量添加浸漬溶液後,將浸漬擠出物老化24小時,然後首先於120℃乾燥,然後於350℃回火。煅燒方法後,最後加工觸媒。在氫化處理反應器中進行硫化Mo物種,作為部分「活化程序」。
使用真空製氣油(VGO)實例,在HTE建造之16室「滴流床反應器」中,試驗觸媒有關加氫脫硫(HDS)及加氫脫氮(HDN)之氫化性能。
在未減少尺寸下,呈全體擠出物試驗觸媒。為此目的,選擇具長度2至4mm之擠出物,置入具內直徑5mm之反應器中。反應器裝填各自觸媒材料後,以觸媒/SiC體積比率1/0.65添加碳化矽SiC(尺寸125至160μm)。使此裝填SiC顆粒之塊狀觸媒材料緊密。選擇觸媒量以致緊密後,各個案裝填反應器體積2ml。從觸媒振實密度(tapped bulk density,TBD),計算觸媒質量(見表3)。總計,反應器具有三個區域,更高與更低區域獨佔地裝填SiC顆粒(125至160μm),中間區域裝填SiC與上述觸媒擠出物之混合物。
使用具以下性質之真空製氣油(VGO)(和緩加氫裂化器之原料)作為原料:
硫含量:27075mg S/kg
氮含量:968mg N/kg
於15℃密度:0.9273g/ml
於70℃密度:0.8919g/ml
為了活化觸媒,使LGO饋料(輕氣油)與二硫二甲烷(DMDS)反應。結果LGO/DMDS具有以下性質:
硫含量:24418mg S/kg
氮含量:116mg N/kg
於15℃密度:0.8589g/ml
將金屬塗布之擠出物調查有關其等催化性質前,在上述試驗組件中活化。活化目的係將Mo化合物硫化成催化活性硫化鉬形式。為此目的,將裝填觸媒之反應器安裝於試驗檯上,且暴露於LGO/DMDS混合物。此方法中,使用壓力60巴及每時之液體空間速度(LHSV)2h-1。氣與油比率(H2與LGO/DMDS混合物)為200標準公升/(h l)。針對活化,使用以下溫度輪廓:
1.在約35℃以LGO潤濕:24小時
2.從35℃至150℃以梯級25℃/h溫度增加
3.從150℃至250℃以梯級15℃/h溫度增加
4. T=250℃ 14小時,直到H2S信號穩定
5.從250℃至320℃以梯級10℃/h溫度增加
6. T=320℃ 11小時,直到H2S信號穩定
為了調查觸媒之氫化性能,選擇以下試驗條件:
1.壓力:p=80巴
氣與油比率:H2/VGO:600Nl(H2)/h/l(VGO)
每時之液體空間速度(LHSV):1.0〔1/h〕
溫度:T=370℃、380℃、390℃
2.壓力:p=120巴
氣與油比率:H2/饋料:600Nl(H2)/h/l(VGO)
每時之液體空間速度(LHSV):1.0〔l/h〕
溫度:T=400℃及385℃
各種設定各保持不變至少三日。溫度改變增加量係10℃/h。
由線上氣相層析法分析揮發有機產物(C1至C7)及永久氣體(H2、H2S、TCD)。為了決定硫及氮含量以及密度,引出產物樣品並離線分析。催化試驗結果顯示於表3。
表3所示結果顯示發明觸媒於經處理的真空製氣油中造成顯著更低的硫含量。因此證明根據發明觸媒材料及用其助劑製造以活性金屬塗布的撐體及因而亦根據發明CoMo-及NiMo觸媒,就HDS-及HDN活性而言,較先前技藝展現顯著改良的催化性能。
Claims (17)
- 一種以氧化鈦為基礎之粉狀觸媒材料,具有至少90重量%的組合含量之具有通式TiO(2-x)(OH)2x之水合氧化鈦〔具0<x≦1(以TiO2計算)〕及包含其水合先質形式之二氧化矽(以SiO2計算),其具有比表面積>300m2/g及等電點範圍4.0至7.0,其中TiO2/SiO2重量比(對TiO2與SiO2分別測定)係至少3,重量百分率係相對於105℃已乾燥至少2小時後的觸媒材料總重。
- 根據申請專利範圍第1項之以氧化鈦為基礎之粉狀觸媒材料,其中材料具有光催化氯仿分解率大於0.3mmol/(h*m2)。
- 根據申請專利範圍第1或2項之以氧化鈦為基礎之粉狀觸媒材料,其具有之孔總體積(N2脫附)為至少0.3cm3/g。
- 根據申請專利範圍第1或2項之以氧化鈦為基礎之粉狀觸媒材料,其在常態大氣中於500℃熱處理1小時後,具有比表面積至少80m2/g。
- 根據申請專利範圍第1或2項之以氧化鈦為基礎之粉狀觸媒材料,其中等電點範圍係4.5至5.9。
- 根據申請專利範圍第1或2項之以氧化鈦為基礎之粉狀觸媒材料,其中扣除直線次表面後,銳鈦礦結構的最強烈反射高度(反射(101))與金紅石結構的最強烈反射高度(反射(110))之比率係至少5:1。
- 一種製備根據申請專利範圍第1至6項中任一項之以氧化鈦為基礎之粉狀觸媒材料之方法,其中:a.將平均粒徑20至500nm具有通式TiO(2-x)(OH)2x(具0<x≦1)的氧化鈦水合物顆粒之水性懸浮液與含Si化合物溶液反應, 同時強烈地攪拌,其中藉由視情況添加酸或鹼性溶液可維持pH值範圍pH=3至9,b.若需要,視情況調整pH值範圍介於4至7,c.過濾獲得的懸浮液,且d.用水洗滌獲得的濾餅,直到濾液具有導電性不大於500μS/cm。
- 根據申請專利範圍第7項之方法,其中係使用具SiO2濃度100至500g SiO2/l之Na2SiO3溶液做為含Si化合物。
- 根據申請專利範圍第7或8項之方法,其中在添加含Si溶液前,可藉由視情況添加酸或鹼溶液,將氧化鈦懸浮液之pH值調整達pH值4.0至8.5。
- 一種根據申請專利範圍第1至6項中任一項之粉狀觸媒材料之用途,其係用於製備成形體。
- 一種以二氧化鈦為基礎之成形體,其具有根據申請專利範圍第1至6項中任一項之粉狀觸媒材料含量,其具比表面積>80m2/g。
- 根據申請專利範圍第11項之成形體,其具孔體積(N2,總計)大於0.2cm3/g。
- 根據申請專利範圍第11項之成形體,其具每體積的總比表面積係大於100,000m2/l。
- 一種根據申請專利範圍第11至13項任一項之含氧化鈦成形體之用途,其係作為觸媒或催化活性金屬之撐體,應用於催化領域。
- 根據申請專利範圍第11至13項中任一項之成形體,其具有含量10至35重量%Mo、0至6重量%Co及/或Ni〔以金屬氧化物(MoO3、CoO及NiO)計算〕,及具通式TiO(2-x)(OH)2x之氧化鈦(其中0 <x≦1)與SiO2,含量至高達100重量%,且其具有比表面積至少80m2/g及孔體積大於0.25cm3/g,其中重量百分率係相對裝載的含氧化鈦成形體總重。
- 根據申請專利範圍第15項之成形體,其中MoO3含量係18至30重量%。
- 根據申請專利範圍第15項之成形體,其中平均孔徑係7至15nm。
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ES2836701T3 (es) | 2021-06-28 |
DK3294449T3 (da) | 2020-12-07 |
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KR20180008690A (ko) | 2018-01-24 |
RU2713205C2 (ru) | 2020-02-04 |
UA122226C2 (uk) | 2020-10-12 |
JP6824250B2 (ja) | 2021-02-03 |
TW201703858A (zh) | 2017-02-01 |
CN107530681A (zh) | 2018-01-02 |
EP3294449B1 (de) | 2020-09-09 |
KR102557332B1 (ko) | 2023-07-18 |
CA2985154C (en) | 2023-09-26 |
CN107530681B (zh) | 2021-09-10 |
AU2016265058B2 (en) | 2020-03-12 |
MX2017014043A (es) | 2018-09-07 |
CA2985154A1 (en) | 2016-11-24 |
MY184045A (en) | 2021-03-17 |
SG11201709414XA (en) | 2017-12-28 |
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