TW201249532A - Binder-converted aluminosilicate X-type zeolite compositions with low LTA-type zeolite - Google Patents
Binder-converted aluminosilicate X-type zeolite compositions with low LTA-type zeolite Download PDFInfo
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/20—Faujasite type, e.g. type X or Y
- C01B39/22—Type X
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
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- 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
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
- B01J20/186—Chemical treatments in view of modifying the properties of the sieve, e.g. increasing the stability or the activity, also decreasing the activity
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- 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
- B01J20/28002—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 physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
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- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/067—C8H10 hydrocarbons
- C07C15/08—Xylenes
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
Abstract
Description
201249532 六、發明說明： 【發明所屬之技術領域】 本發明係關於源自於X型鋁矽酸鹽沸石之新家族的新的 經黏結劑轉換之組合物。更具體而言，此新的經黏結劑轉 換之組合物係使用具有低或無可檢測含量（如藉由X射線繞 射所測定）之LTA型沸石之X型沸石及可轉換成X型沸石之 黏結劑材料製得。 本申請案主張均於2011年04月13日申請之美國臨時申請 案第61/474,927號及61/474,923之優先權之權益。 【先前技術】 彿石係為微孔的且係自拐角共享之八1〇2及8丨〇2四面體形 成之結晶鋁矽酸鹽組合物。大量沸石（天然存在的以及以 合成方式製備的）係用於各種工業製程中。合成沸石係採 用Si、Al及諸如鹼金屬、鹼土金屬、胺或有機銨陽離子等 結構導向劑之適宜來源經由熱液合成來製得。結構導向劑 存在於沸石之孔中且係最終所形成之特定結構之主要原 因。該等種類平衡與鋁相關之骨架電荷且亦可充當空間填 充劑。沸石描述為具有尺寸均勻之孔開口、具有顯著之離 子交換容量及其吸附並可逆地脫附遍及晶體之内部空隙所 分散之吸附相的能力，而不顯著置換構成永久沸石晶體結 構之任何原子。 在各種用途中，沸石尤其可用於製造吸附劑材料。在吸 附劑材料中’沸石可分離多組份氣體混合物或液體混合物 之組份。通常瞭解，惰性或非反應性沸石（「污染物沸 163742.doc 201249532 石」）之存在經常可減弱某些沸石之吸附性能。然而，通 常一些相對較低（但仍可容許）濃度之污染物沸石之存在已 視為商業上可接受的’此乃因通常認為其在成品吸附劑性 能中造成之損《或下降不㈣。因Λ，在進一步減少污染 物/弗石3量方面’返回點逐漸減弱。因此通常認為，馨於 污染物沸石之相關吸附劑之預計性能，保留與活性沸石混 合之污染物沸石較移除或進一步減少污染物沸石更成本有 效。 因此，f 0需要具有經?文良純度之濟石，更特定而言相 比於對於進一步減少污染物沸石含量超過常規位準或將其 完全移除之程度而言所預期者可對沸石之製程性能具有更 有益影響的X型沸石。 然而’除此習用觀點以外，申請人已發現並成功製造出 具有少許至無可檢測量之特定污染物沸石（即，LTA型沸石 (在下文中「LTA沸石」）)之沸石。更具體而言，申請人已 發現並製造出具有少許或無可檢測LTA沸石之沸石χ(「含 有低LTA之X沸石」）之形 <，如藉由下文所闡述之X射線 繞射（「XRD」）方法所測定，其亦具有不大於2 7微米⑽） 之粒徑，如藉由下文所闡述之沉降圖分析所測定。申請人 亦已發現含有低LTA之X沸石係用於製造經黏結劑轉換之 沸石組合物（下文所闡述）。 一種感興趣之吸附劑應用尤其係關於在固定床製程中自 二曱笨之混合物分離對二甲苯（ρχ) ’該固定床製程經常係 模擬移動床（SMB)吸附製程。 163742.doc 201249532 在商業上’ SMB吸附製程係用於若干大規模石油化學分 離中，以自經混合二甲苯回收高純度ρΧ。本文中所使用之 「經混合二曱苯」係指a芳香族異構體之混合物，其包括 乙笨（ΕΒ)、ρΧ、間二甲苯（mX)及鄰二曱苯（〇χ)。高純度 ρΧ係用於產生聚酯纖維、樹脂及膜。通常，將ρΧ轉換成 對苯二甲酸（ΤΡΑ)或對苯二曱酸二曱酯（DMT)，然後使其 與乙二醇反應以形成聚對苯二甲酸乙二酯（PET)(大部分聚 酯之原材料）。 SMB吸附分離製程之實施中所採用之一般技術係經廣泛 闡述並實踐。通常，該製程模擬吸附劑之移動床，其中液 體給料連續逆流流經吸附劑。給料及產物以幾乎恆定組成 連續進入並離開吸附劑床。分離係藉由利用相對於其他 芳香族異構體該吸附劑對ρχ之親和力之差異來實現。 SMB吸附製程中所使用之典型吸附劑通常包括結晶銘石夕 酉文鹽ί弗石且可包含天然以及合成銘妙酸鹽β用作對ρχ具有 選擇性之吸附劑的適宜結晶鋁矽酸鹽沸石包括彼等具有銘 矽酸鹽籠結構者，在該等鋁矽酸鹽籠結構中氧化鋁及二氧 化矽四面體在開放三維結晶網絡中彼此緊密連接。藉由所 共享之氧原子使四面體交聯，其中在沸石部分或全部脫水 之前介於四面體之間之空間由水分子佔據。脫水導致交錯 有具有分子尺寸之通道的晶體。 在水合形式中，結晶鋁矽酸鹽沸石通常係由下式來表 不： M2/n〇：Al2〇3：wSi〇2：yH2〇 163742.doc 201249532 其中「Μ」係平衡四面體之電子原子價之陽離子且通常稱 為可交換陽離子位點，「nj表示陽離子之原子價，「wj表 示Si02之莫耳(m〇ie)，「y」表示水之莫耳。發現作為吸 附劑之用途之該等結晶鋁矽酸鹽沸石具備相對良好界定之 孔結構。確切類型之鋁矽酸鹽沸石通常係藉由特定二氧化 石夕：氧化紹莫耳比及籠結構之孔尺寸來鐘別。 可利用其他陽離子藉由在結晶鋁矽酸鹽之領域中熟習此 項技術者所熟知之離子交換方法代替佔據沸石吸附劑中之 可交換陽離子位點之陽離子（Μ)β已知結晶鋁矽酸鹽（例 如，在沸石内之可交換陽離子位點處具有鋇及鉀陽離子之 沸石X)選擇性吸附包含至少一種除ρΧ以外之其他C8芳香族 異構體之混合物中之pX。 通常，分離製程中所使用之沸石吸附劑含有沸石結晶材 料’該沸石肖晶材料分散於具有使液體能夠接近該結晶材 料之通道及腔之非晶形材料或無機基質中。二氧化矽、氧 化鋁或某些黏土及其混合物係該等無機基質材料之典型， 該等無機基質材料充當「黏結劑」以形成原本會包含精細 粉末之沸石結晶粒子或使其黏m，經黏聚沸石吸附 劑可呈擠出物、聚集體、鍵劑、諸如珠粒、顆粒或諸如此 類等大球體之形式。 黏結劑常常係惰性的且對吸附分離製程貢獻極小（若存 在)。改良吸附劑效力之努力通常集中於(a)降低形成吸附 劑之/弗石粒子之大小及（b)增加吸附劑内之彿石體積（即， 活刀離組伤）《· -種增加吸附劑中之沸石體積之方法係 163742.doc 201249532 在稱為「沸石化」之轉換製程中將黏結劑轉換成沸石，同 時較佳（尤其）維持或改良吸附劑材料之強度及大孔隙度。 從而’此黏結劑轉換製程獲得經黏結劑轉換之沸石組合 物’其經常稱為「黏結劑較少之」沸石吸附劑。然而， 「黏結劑較少之」的描述必然意指未將所有原始黏結劑材 料轉換成沸石材料，此乃因某一小部分之黏結劑材料（例 如’至多3 wt°/。）可未經轉換，此視諸如原始黏結劑含量、 沸石化條件等各種因素而定。儘管黏結劑轉換製程已導致 經改良吸附劑效力，但仍期望進一步提高吸附分離製程效 率。 因此，本文中更充分闡述經改良之經黏結劑轉換之沸石 吸附劑組合物，其得自具有經改良純度之χ沸石—更具體而 言，粒徑不大於2.7 μηι且含有低LTA之χ沸石_以在液相分 離製程中使用該經黏結劑轉換之沸石吸附劑自經混合二甲 苯回收高純度pX。本文中亦目述獲得粒徑不大於27㈣且 含有低lta之χ沸石的方法，以及使用此一含有mLTA2X 獲得經黏結劑轉換之沸石吸附劑的方法。 此外，根據本發明之隨後詳細說明及隨附申請專利範 圍，本發明之其他期望特性及特徵將變得顯而易見。 【發明内容】 根據本發明之一態樣，提供經黏結劑轉換之沸石組合 物，其包含： (a)，弗石X組。物纟至少具有平均直徑不大於2 7微米（如 藉由沉降圖分析所測定）之第—沸石X及第二沸石X，其中 163742.doc 201249532 第二沸石x係藉由將黏結劑材料轉換成第二沸石χ來獲 得’且黏結劑材料係在沸石X組合物之5 wt%至3〇 wt%之 範圍内，及 (b)未經轉換黏結劑材料含量，在完成至第二沸石χ之轉 換後’其係在沸石X組合物之0 wt%至3 wt%之範圍内； 其中沸石X組合物具有 (1)在1.0至1.5之範圍内之平均Si/Al骨架莫耳比，其中第 一沸石及第二沸石之Si/Al骨架莫耳比可相同或不同；及 (Π)不大於1.0之相對LTA強度，如藉由χ射線繞射（XRD)方 法所測定’該方法使用CuKa輻射之來源以獲得在5。至25。 2Θ之範圍内之xrd強度， 其中’該相對LTA強度係如下來計算：1〇〇乘以下式之商： —_該沸石X之檨品LTA XRD強疳__ 基本上由LTA沸石組成之LTA沸石參照材料之參時 XRD強度 ^ 其中， (1) 沸石X組合物之樣品LTA XRD強度係在7.27 ± 〇.160、 16.29 ± 0.34。及24.27 ± 0.50。2Θ處米勒指數（Miller indi⑷ 為（2 0 0)、（4 2 0)及（6 2 2)之每一 LTA峰之強度之和，且 (2) LTA型沸石參照材料之參照xrd強度係在7 27 ± 0.16。、16.29 ± 0.34。及 24.27 ± 0.50。2Θ處米勒指數為（2 〇 0)、（4 2 0)及（6 2 2)之每一 LTA峰之強度之和， 其中， 該樣品LTA XRD強度及該參照Xrd強度各自係 163742.doc 201249532 (a) 分別針對沸石χ組合物及LTA型沸石參照材料之Na交 換形式而獲得，且 (b) 在50%相對濕度下平衡。 【實施方式】 申睛人已製備使用具有低或無可檢測LTA沸石含量之沸 石所產生的經黏結劑轉換之沸石組合物。 沸石X製備 沸石又之結構係詳細闡述於1;8 2,882,244中。可（例如）使 用沸石晶種材料或起始劑材料製備粒徑不大於2 7 μπι(如 藉由下文所闡述之沉降圖分析所測定）且含有低LTA之X沸 石（如藉由下文所闡述之XRD方法所測定）。沸石粒徑在業 内有時稱為微晶大小，但為了 一致性本文中將使用粒徑。 了使用用於起始沸石微晶生長（有時描述為成核）之晶種 成起始劑材料來獲得較小彿石粒徑。因此，首先製備晶種 或起始劑材料，且然後以凝膠組合物對起始劑之比率將其 摻和至凝膠組合物中，以獲得在目標範圍内之沸石粒徑。 凝膠組合物對晶種或起始劑材料之比率支配成核位點之相 對數量或濃度’其進而影響沸石X之所獲得粒徑。通常， 較兩濃度之晶種或起始劑材料使粒徑減小。例如，使用以 重量汁分別在7900至1及85至1之範圍内之凝膠對晶種/起 始劑比率來製造平均直徑在2·7微米至〇 5微米之範圍内之 沸石X製劑。鑒於本揭示内容，熟習此項技術者可輕易地 改變凝膠對晶種或起始劑之重量比，以獲得不大於2.7 μιη 之任何平均沸石粒徑。 163742.doc 201249532 典型凝膠組合物包含Na2〇、Si〇2、Ah〇3及水。申請人 已發現，通常，當增加所使fflNa2〇相對於其他凝膠或起始 劑組份（即，Si〇2、八丨2〇3、Ηβ)之量時，所獲得之沸石χ 之平均直徑減小。然而，當增加凝膠或起始劑組合物中之 NaaO之量時’產生污染*LTA沸石之趨勢增加。而且，當 使用相對於Si02及Al2〇3濃度增加之Na20時，Si02對Al2〇3 之比率有效地降低，進而當使用晶種或起始劑材料製造χ 沸石時獲得沸石中較低Si/Al骨架比率。但通常，較低 Si/Al骨架比率導致較大沸石骨架單位晶胞大小（ucs)，其 進而可不利地影響沸石對某些感興趣種類之選擇性。因 此’儘管藉由增加NazO濃度來獲得較小粒徑可係有益的， 但同時其可產生其他不期望屬性，例如形成污染物LTA沸 石及較大UCS » 令人感興趣的，若不使用起始劑或晶種材料來製造沸石 X ’則最小可獲得之平均直徑係3 μιη，即使當Na20、Si02 及Al2〇3總莫耳比與彼等用於使用起始劑或晶種材料之合 成者實質上相同或類似時亦如此。 申請人已意外地發現如何產生具有減小之UCS之沸石 X ’同時在沸石X之形成中產生少許至無可檢測LTA沸石。 下文提供小粒子、含有低LTA之X沸石之主要反應物相對 於Ah〇3之總莫耳比（包括晶種或起始劑材料貢獻）。 含有起始劑範圍之小粒子、 含有低LTA之X沸石 Na20 Si02 Al2〇3 h2o 廣義值 3.94-4.05 2.96-3.34 1.00 200.1-202.8 較佳值 3.99-4.02 3.15-3.24 1.00 201.5-202.1 實例S-1及S-2 4.02 3.24 1.00 202.1 163742.doc •11· 201249532 出於比較目的’下文提供用於習用小粒子、含有高LTA 之X沸石合成之主要反應物相對於Ai2〇3之典型莫耳比（包 括晶種或起始劑材料貢獻）》 含有起始劑範圍之小粒子、 含有高LTA之X沸石 Na2〇 Si02 AI2O3 H20 遍值 3.86-3.93 2.70-2.95 1.00 198.3-200.1 實例C-1 3.93 2.95 1.00 200.1 處於比較目的，下文提供用於不使用起始劑之習用大粒 子（即，> 3 μιη平均直徑）、含有低LTA之X沸石合成之主要 反應物相對於αι2ο3的典型莫耳比。 無起始劑範圍之大粒子、 含有低LTA之X沸石 Na20 Si02 AI2O3 H20 廣義值 2.50-4.26 2.77-3.01 1.00 65-240 食例C-2 2.63 2.83 1.00 79.9 如上文所述，對於不使用起始劑或晶種材料所製得之X 沸石而言，可獲得之最小平均直徑係3 μηι。且儘管此一大 粒子沸石X往往具有低LTA含量，但若申請人最近未發現 用於製造平均直徑不大於2.7 4爪且含有低LTA之χ沸石的 製程，則其在不使用起始劑或晶種材料時不能獲得低於3 μηι之平均直徑’此必然使得產生不期望之高LTA含量。 凝膠组合物 可藉由將凝膠補充溶液與含有（例如）12重量％氧化鋁之 鋁酸鹽補充溶液組合來製備凝膠組合物。藉由以下來製備 凝膠補充溶液：混合水、苛性鹼溶液及矽酸鈉，並將混合 物冷卻至38°C (100°F)。藉由以下來製備鋁酸鹽補充溶液： 163742.doc -12· 201249532201249532 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a novel binder-converting composition derived from a new family of X-type aluminosilicate zeolites. More specifically, the new binder-switched composition uses X-type zeolite having a low or no detectable content (as determined by X-ray diffraction) and can be converted to zeolite X. Made of a binder material. The present application claims the benefit of priority to U.S. Provisional Application Nos. 61/474,927 and 61/474,923, filed on Apr. 13, 2011. [Prior Art] The buddha is microporous and is a crystalline aluminosilicate composition formed from a square of 8 〇 2 and 8 丨〇 2 tetrahedrons shared by the corners. A large number of zeolites (naturally occurring and synthetically prepared) are used in a variety of industrial processes. Synthetic zeolites are prepared by hydrothermal synthesis using Si, Al and suitable sources of structural directing agents such as alkali metals, alkaline earth metals, amines or organic ammonium cations. The structure directing agent is present in the pores of the zeolite and is the primary cause of the particular structure ultimately formed. These species balance the framework charge associated with aluminum and can also act as a space filler. Zeolites are described as having a uniform pore opening, a significant ion exchange capacity, and the ability to adsorb and reversibly desorb the dispersed phase dispersed throughout the internal voids of the crystal without significantly replacing any atoms that make up the permanent zeolite crystal structure. Zeolites are especially useful in the manufacture of adsorbent materials in a variety of applications. The zeolite can separate components of the multicomponent gas mixture or liquid mixture in the adsorbent material. It is generally understood that the presence of inert or non-reactive zeolites ("contaminant boiling 163742.doc 201249532 stone") often reduces the adsorption properties of certain zeolites. However, the presence of some relatively low (but still permissible) concentrations of contaminant zeolites has been considered commercially acceptable. This is because it is generally considered to cause damage in the performance of the finished adsorbent, or not to fall (4). Because of this, the return point gradually weakened in terms of further reducing the amount of pollutants/fuss. It is therefore generally accepted that the expected performance of the adsorbent associated with the contaminated zeolite, retaining the contaminating zeolite mixed with the active zeolite, is more cost effective than removing or further reducing the contaminating zeolite. Therefore, f 0 needs to have a good purity of the jade stone, more specifically than to further reduce the extent to which the contaminant zeolite content exceeds the conventional level or completely removes it. X-type zeolite with more beneficial effects on performance. However, in addition to this conventional viewpoint, Applicants have discovered and succeeded in producing a zeolite having a specific contaminant zeolite (i.e., LTA type zeolite (hereinafter "LTA zeolite") having a slight to no detectable amount. More specifically, Applicants have discovered and produced zeolites ("X zeolites containing low LTA") with little or no detectable LTA zeolite, as described by X-ray diffraction as explained below ( The "XRD" method also has a particle size of not more than 27 μm (10)) as determined by the sedimentation pattern analysis described below. Applicants have also discovered that zeolite X containing low LTA is used in the manufacture of a binder-converted zeolite composition (described below). One type of adsorbent application of interest is in particular the separation of paraxylene (ρχ) from a mixture of two in a fixed bed process. This fixed bed process is often a simulated moving bed (SMB) adsorption process. 163742.doc 201249532 Commercially, the 'SMB adsorption process is used in several large-scale petrochemical separations to recover high purity rhodium from mixed xylenes. As used herein, "mixed diphenylbenzene" means a mixture of a aromatic isomers including phenyl, phex, m-xylene and o-diphenylbenzene. High purity ρΧ is used to produce polyester fibers, resins and films. Typically, ρ Χ is converted to terephthalic acid (ΤΡΑ) or diterpene terephthalate (DMT), which is then reacted with ethylene glycol to form polyethylene terephthalate (PET) (most Raw materials for polyester). The general techniques employed in the implementation of the SMB adsorption separation process are extensively described and practiced. Typically, the process simulates a moving bed of adsorbent wherein the liquid feed continuously flows countercurrently through the adsorbent. The feedstock and product enter and exit the adsorbent bed in an almost constant composition. Separation is achieved by utilizing the difference in affinity of the adsorbent for ρχ relative to other aromatic isomers. Typical adsorbents used in the SMB adsorption process typically include the crystalline crystalline sulphate salt and can contain natural and synthetic salts of the salt as a suitable crystalline aluminate zeolite for the selective adsorption of ρχ. Including those having a strontium cage structure in which alumina and cerium oxide tetrahedrons are closely connected to each other in an open three-dimensional crystalline network. The tetrahedron is crosslinked by the shared oxygen atoms, wherein the space between the tetrahedra is occupied by water molecules before the partial or total dehydration of the zeolite. Dehydration results in the interlacing of crystals having channels of molecular size. In the hydrated form, the crystalline aluminosilicate zeolite is usually represented by the following formula: M2/n〇: Al2〇3: wSi〇2: yH2〇163742.doc 201249532 where “Μ” is an electron atom of a balanced tetrahedron The cation of the valence and is often referred to as the exchangeable cation site, "nj represents the valence of the cation, "wj represents the moth of SiO2, and "y" represents the moiré of water. These crystalline aluminosilicate zeolites have been found to have relatively well defined pore structures for use as adsorbents. The exact type of aluminosilicate zeolite is usually distinguished by the specific dioxide dioxide: oxidation of the Sommer ratio and the pore size of the cage structure. Other cations may be utilized to replace the cation (Μ) β, which is known to those skilled in the art, in the field of crystalline aluminosilicates, which is known to be an exchangeable cationic site in the zeolite adsorbent. The salt (e.g., zeolite X having a ruthenium and potassium cation at the exchangeable cation sites in the zeolite) selectively adsorbs pX in a mixture comprising at least one other C8 aromatic isomer other than ρ 。. Typically, the zeolite adsorbent used in the separation process contains zeolite crystalline material. The zeolite crystallite material is dispersed in an amorphous or inorganic matrix having channels and cavities that allow liquid to access the crystalline material. Cerium oxide, aluminum oxide or certain clays and mixtures thereof are typical of such inorganic matrix materials, which act as "bonding agents" to form zeolite crystal particles which would otherwise contain fine powders or to make them m. The cosmic zeolite adsorbent can be in the form of extrudates, aggregates, bonds, large spheres such as beads, granules or the like. Adhesives are often inert and contribute very little to the adsorption separation process, if any. Efforts to improve the effectiveness of adsorbents are generally focused on (a) reducing the size of the adsorbent/fossil particles and (b) increasing the volume of the fossils within the adsorbent (ie, the biopsy off-group injury). The method for the volume of zeolite in the agent is 163742.doc 201249532 The conversion of the binder into zeolite is carried out in a conversion process known as "zeolilation", while it is preferred (especially) to maintain or improve the strength and macroporosity of the adsorbent material. Thus, the binder conversion process results in a binder-converted zeolite composition which is often referred to as a "less binder" zeolite adsorbent. However, the description of "less binder" necessarily means that all of the original binder material is not converted to zeolitic material because a small portion of the binder material (eg, 'up to 3 wt ° /.) may not be Conversion, depending on various factors such as the original binder content, zeolitic conditions, and the like. Although the binder conversion process has resulted in improved sorbent efficacy, it is desirable to further increase the efficiency of the adsorptive separation process. Accordingly, the improved binder-converted zeolite adsorbent composition is more fully described herein, which is derived from a zeolite having improved purity, more specifically, a zeolite having a particle size of not more than 2.7 μηι and containing a low LTA. The high purity pX is recovered from the mixed xylene using the binder-converted zeolite adsorbent in a liquid phase separation process. Also described herein are methods for obtaining a zeolite having a particle size of not more than 27 (d) and containing a low lta, and a method of obtaining a zeolite-adsorbed zeolite adsorbent using the mLTA2X. In addition, other desirable features and characteristics of the present invention will become apparent from the Detailed Description of the invention. SUMMARY OF THE INVENTION According to one aspect of the invention, a binder-converted zeolite composition is provided comprising: (a) a group of vermiculite X. The substance has at least a first zeolite X and a second zeolite X having an average diameter of not more than 27 μm (as determined by sedimentation analysis), wherein 163742.doc 201249532 second zeolite x is converted into a binder material by The second zeolite is obtained to obtain 'and the binder material is in the range of 5 wt% to 3 wt% of the zeolite X composition, and (b) the unconverted binder material content is completed to the second zeolite After conversion, it is in the range of 0 wt% to 3 wt% of the zeolite X composition; wherein the zeolite X composition has (1) an average Si/Al skeleton molar ratio in the range of 1.0 to 1.5, wherein The Si/Al framework molar ratio of a zeolite and a second zeolite may be the same or different; and (Π) the relative LTA intensity of not more than 1.0, as determined by a χ ray diffraction (XRD) method, which uses CuKa radiation. The source is obtained at 5. To 25. The xrd strength in the range of 2Θ, where 'the relative LTA strength is calculated as follows: 1〇〇 multiplied by the following formula: —_The zeolite X is a product of LTA XRD 疳__ LTA consisting essentially of LTA zeolite The time-dependent XRD intensity of the zeolite reference material ^ (1) The sample LTA XRD strength of the zeolite X composition was 7.27 ± 160.160, 16.29 ± 0.34. And 24.27 ± 0.50. 2 Miller Miller index (Miller indi (4) is the sum of the intensity of each LTA peak of (2 0 0), (4 2 0) and (6 2 2), and (2) LTA type zeolite reference material The reference xrd intensity is 7 27 ± 0.16, 16.29 ± 0.34, and 24.27 ± 0.50. The Miller index is the intensity of each LTA peak of (2 〇 0), (4 2 0), and (6 2 2). And, wherein the sample LTA XRD intensity and the reference Xrd intensity are respectively 163742.doc 201249532 (a) obtained for the Na exchange form of the zeolite ruthenium composition and the LTA type zeolite reference material, respectively, and (b) at 50% relative Balanced under humidity. [Embodiment] The present invention has prepared a binder-converted zeolite composition produced by using a zeolite having a low or no detectable LTA zeolite content. The zeolite X preparation zeolite is further described in detail in 1; 8 2,882,244. X zeolites having a particle size of not more than 27 μπι (as determined by sedimentation plot analysis as set forth below) and containing low LTA can be prepared, for example, using zeolite seed material or starter material (eg, borrowed As determined by the XRD method described below.) Zeolite particle size in the industry The time is called the crystallite size, but for the sake of consistency, the particle size will be used here. The seed crystals used to initiate the zeolite crystallite growth (sometimes described as nucleation) are used as initiator materials to obtain smaller fossils. Particle size. Thus, a seed or starter material is first prepared and then blended into the gel composition at a ratio of gel composition to starter to achieve a zeolite particle size within the target range. The ratio of the gel composition to the seed crystal or the starter material governs the relative amount or concentration of the nucleation sites, which in turn affects the particle size obtained for zeolite X. Typically, the seed crystal or the starter material is more than two concentrations. The particle size is reduced. For example, using a gel to seed/starter ratio in the range of 7900 to 1 and 85 to 1 with a weight juice to produce an average diameter in the range of 2·7 μm to 〇 5 μm. Zeolite X formulation. In view of the present disclosure, those skilled in the art can readily vary the weight ratio of gel to seed or starter to achieve any average zeolite particle size of no greater than 2.7 μη. 163742.doc 201249532 Typical The gel composition comprises Na2〇, Si〇2, Ah 3 and water. Applicants have found that, generally, when increasing the amount of fflNa2 〇 relative to other gel or starter components (ie, Si〇2, 丨2〇3, Ηβ), The average diameter of the zeolite 减小 is reduced. However, when the amount of NaaO in the gel or starter composition is increased, the tendency to generate contamination*LTA zeolite is increased. Moreover, when the concentration is increased relative to SiO 2 and Al 2 〇 3 At Na20, the ratio of SiO 2 to Al 2 〇 3 is effectively lowered, and the lower Si/Al skeleton ratio in the zeolite is obtained when the cerium zeolite is produced using the seed crystal or the initiator material. Generally, however, lower Si/Al framework ratios result in larger zeolite framework unit cell sizes (ucs), which in turn can adversely affect the selectivity of the zeolite for certain classes of interest. Thus 'although it may be beneficial to obtain a smaller particle size by increasing the NazO concentration, but at the same time it may produce other undesirable properties, such as the formation of contaminant LTA zeolite and larger UCS » Interesting, if not used The starting agent or seed material to make zeolite X 'the smallest available average diameter is 3 μηη, even when the total molar ratio of Na20, SiO 2 and Al 2 〇 3 is used in combination with the initiator or seed material. The same is true when the persons are substantially the same or similar. Applicants have unexpectedly discovered how to produce zeolite X' with reduced UCS while producing a little to no detectable LTA zeolite in the formation of zeolite X. The total molar ratio (including seed or initiator material contribution) of the primary reactant of the small particles, X zeolite containing low LTA, relative to Ah 〇 3 is provided below. Small particles containing a range of initiators, X zeolite containing low LTA Na20 Si02 Al2〇3 h2o Generalized value 3.94-4.05 2.96-3.34 1.00 200.1-202.8 Preferred value 3.99-4.02 3.15-3.24 1.00 201.5-202.1 Example S-1 And S-2 4.02 3.24 1.00 202.1 163742.doc •11· 201249532 For comparison purposes, the following provides a typical molar ratio of the main reactants for the synthesis of small particles, X zeolite containing high LTA, relative to Ai2〇3 ( Including seed or initiator material contribution) Small particles containing starter range, X zeolite containing high LTA Na2〇SiO 2 AI2O3 H20 Pass value 3.86-3.93 2.70-2.95 1.00 198.3-200.1 Example C-1 3.93 2.95 1.00 200.1 For comparison purposes, the following provides typical molar ratios of the primary reactants for the synthesis of large particles (i.e., > 3 μιη average diameter) without the use of an initiator, and the synthesis of zeolite X containing low LTA relative to αι2ο3. Large particles without initiator range, X zeolite containing low LTA Na20 Si02 AI2O3 H20 Generalized value 2.50-4.26 2.77-3.01 1.00 65-240 Case C-2 2.63 2.83 1.00 79.9 As mentioned above, for no start For the X zeolite prepared from the agent or seed material, the smallest average diameter available is 3 μηι. And although this large particle zeolite X tends to have a low LTA content, if the applicant has not recently found a process for producing a cerium zeolite having an average diameter of not more than 2.7 4 paws and containing a low LTA, it does not use an initiator or An average diameter of less than 3 μηι cannot be obtained for the seed material', which inevitably results in an undesirably high LTA content. Gel Composition A gel composition can be prepared by combining a gel replenishing solution with an aluminate replenishing solution containing, for example, 12% by weight of alumina. A gel replenishing solution was prepared by mixing water, a caustic solution, and sodium citrate, and cooling the mixture to 38 ° C (100 ° F). The aluminate replenishing solution was prepared by the following: 163742.doc -12· 201249532
加需要量之晶種。Add the required amount of seed crystals.
將三水合氧化銘溶解於苛性鹼溶液中(同時視需要加熱用 於溶解）’隨後冷卻並在3 8 M 晶種材料製備Dissolve the trihydrate oxidized in a caustic solution (while heating as needed for dissolution)' followed by cooling and preparation at 3 8 M seed material
々叭农镝晶種。因此，典型晶種 2、Ah。3及水。對於每一莫耳之 組合物亦包含Na20、Si02、々 镝 镝 镝 镝 。. Therefore, the typical seed crystal 2, Ah. 3 and water. For each mole composition, Na20, SiO2,
Ah〇3而言，可使用10莫耳至2〇莫耳之Na2ag^i〇2及i5〇至 5〇〇莫耳之水。用於製備晶種之鋁酸鹽溶液可含有（例如y 8 重量％氧化鋁。在組合凝膠組合物與晶種之後，加熱混合 物同時維持擾動，且然後在撥動條件及251 (75卞）至 150eC(300°F)之溫度下老化5小時至50小時之時間，以自晶 種核形成期望微晶。然後可過濾、洗滌並乾燥所得固體材 料，以獲得小粒徑沸石X。沸石X之粒徑係藉由沉降圖分 析來測定，如在下文表徵實例部分中更充分地闡述。 黏結劑 然後藉由將第一「所製備J或先前所製得之沸石X與沸 石X前體組合來將沸石X用於合成經黏結劑轉換之組合 物。較佳沸石X前體包括黏土，該等黏土將獲得在丨至i 5 之範圍内之Si/Al骨架比率且較佳地與原始的含有低LTA之 X沸石在黏土轉換之前在1.15至1.35之範圍内之較佳以/以 比率實質上一致的Si/Al骨架比率。更佳地，滞石X前體係 諸如高嶺土（kaolin)、高嶺石（kaolinite)及多水高嶺土等黏 163742.doc -13- 201249532 土。使用沸石x前體來製造經黏結劑轉換之組合物中之第 —彿石X。 較佳地，黏結劑材料之平均粒子直徑係在04 4〇1至46 μπι之範圍内。 成形程序涉及將沸石X前體（由高嶺土黏土所例示）與所 製備之第一沸石X之沸石X粉末及視情況諸如孔生成材料 (例如，提供大孔隙度之玉米澱粉）等其他添加劑及根據需 要之水組合以獲得適當之成型稠度。成型或成形成較大珠 粒、球體、丸粒等可使用包括諸如Nauta混合、翻轉或圓 筒翻滾等珠粒成形製程之習用方法以製備較大粒子（例 如，在16至60標準美國網目大小之範圍内）來實施。然後 在通常在50(TC至70(TC (930卞至13〇〇卞）之範圍内之溫度下 使包含所製備之第一沸石X及沸石χ前體之所成形粒子活 化。在包含尚嶺土黏土之沸石X前體之情形下，活化使得 此材料經受吸熱脫羥基，藉此形成無序偏高嶺土相。 在活化之後，然後所成形粒子之苛性消化（例如，使用 氫氧化鈉）將經活化沸石χ前體轉換成第二沸石χ，從而導 致了包3具有低或無可檢測LTA沸石含量之沸石χ或基本 上由其組成的經黏結劑轉換之組合物。 沸石X之所轉換部分2Si/A1骨架比率以及此材料在最終 調配物中之貢獻可根據納入所成形粒子中之沸石χ前體之 類型及量而改變。通常，在轉換成沸石χ之後將實質上保 持沸石X前體之Si/A丨比率。因此，Si/Ai比率在：川至丨」之 範圍内之典型高嶺土黏土將轉換成沸石骨架比率在此範圍 163742.doc •14· 201249532 内之沸石x部分。因此，可製備沸石x之第一（所製備）與第 二（所轉換）部分之Si/Al比率不同的經黏結劑轉換之組合 物。 然而，將沸石X之Si/Al骨架比率自ιοί hl之範圍增加 至1.05至1.35之範圍可導致pX之吸附分離中之脫附劑強度 增加（例如，使用對二乙苯（pDEB)脫附劑）β當用Si/Ai骨架 比率為1.0之沸石X代替吸附劑調配物中之較高比率沸石X 時，pDEB脫附劑強度大大降低（即，脫附劑相對強度之倒 數之值升高）。脫附劑強度之此降低影響脫附劑將期望 產物置換至提取物流中之能力，在（特定而言）用於以模擬 移動床模式操作之ρχ吸附分離之商業製程中獲得具有高純 度及回收率之ρΧ方面可具有不利後果。 該等結果闡釋因使用經黏結劑轉換之組合物可得到之製 程效率，在該等組合物中沸石Χ之所轉換部分具有在1〇5 至1.35之範圍内之以/八丨骨架比率，此“/八丨骨架比率可與沸 石X之所製備部分之則骨架比率相同或實質上相同。然 而’諸如高嶺土黏土等沸石χ前體經常具有較低Si，"比 率，例如1.0,且因此通常不轉換成期望之較高比率彿石 X。 义然而，可修改經黏結劑轉換之組合物之合成中將沸石x 刖體轉換成沸石χ之程序’以增加沸石χ之所轉換部分中 一氧化矽對氧化鋁之莫耳比。此可藉助添加諸如以下等二 氧化#來源來達成：膠質二氧切溶膠、料、石夕酸納、 石夕膠或反應性微粒二氧化妙（例如，梦藻土、亂如等卜 163742.doc •15· 201249532 可在吸附劑粒子成形步驟或苛性消化步驟或兩者期間添加 二氧化矽來源。所添加二氧化矽之量使得沸石χ前體（例 如，偏尚嶺土）及二氧化矽來源之整體反應混合物受到控 制，以使反應組合物在以下範圍内：Na2〇/Si〇2 = 〇 8至 1.5 ’ Si02/A1203=2.5至 5，H20/Na20=25至 60。 因此，二氧化矽之單獨來源之使用可允許製備經黏結劑 轉換之組合物，在該組合物中沸石χ之所製備及所轉換部 分兩者之Si/Al比率係經密切匹配（例如，均係在i 〇至i 5且 通常1.05至1.35之範圍内），從而克服上文所論述關於在ρχ 之吸附分離中使用較低比率沸石χ之缺點。有利地，沸石 X之所轉換部分中二氧化矽對氧化鋁之莫耳比增加亦可改 良所得經黏結劑轉換之組合物之熱液穩定性。 經黏結劑轉換之組合物中沸石χ之第一所製備及第二所 轉換部分之相對量可有所改變。根據一些實施例，用於製 備所成形粒子之沸石χ前體之量將係在5重量％至4〇重量0/〇 且較佳10重量％至3 〇重量％之範圍内。因此，該等範圍亦 對應於本文中所闡述之代表性經黏結劑轉換之組合物中所 存在之所轉換沸石χ的量。 較佳地’黏結劑材料含量在轉換成第二沸石之後係在〇 wt%至3 wt0/〇之範圍内。在實例性經黏結劑轉換之組合物 中’非沸石材料係實質上缺乏的（例如，通常係以小於2重 量0/。、常常小於1重量。/。且經常小於〇. 5重量。/。之量存在於該 組合物中）。非沸石或非晶形材料之缺乏或實質上缺乏可 藉由使用X射線繞射及/或高解析度掃描電子顯微鏡（HR_ I63742.doc -16 - 201249532 SEM)分析經黏結劑轉換之組合物以檢驗晶體結構來確 認、°大孔及微孔結構及分佈可使用汞孔隙度測定法或液氡 吸附法來描述並確認。 藉由XRD測定沸石X中之LTA沸石含量 . 如上文所論述，本發明需要X沸石具有不大於2.7 μπι之For Ah〇3, it is possible to use Na2ag^i〇2 and i5〇 from 10 to 2 moles to 5 inches of water. The aluminate solution used to prepare the seed crystals may contain (e.g., y 8 wt% alumina. After combining the gel composition with the seed crystals, the mixture is heated while maintaining the perturbation, and then in the toggle condition and 251 (75 卞) The desired crystallites are formed from the seed crystal nucleus by aging for 5 hours to 50 hours at a temperature of 150 eC (300 °F). The resulting solid material can then be filtered, washed and dried to obtain a small particle size zeolite X. Zeolite X The particle size is determined by sedimentation analysis as more fully illustrated in the characterization section below. The binder is then combined by first "prepared J or previously prepared zeolite X with zeolite X precursor" Zeolite X is used to synthesize a binder-converted composition. Preferably, the zeolite X precursor comprises clay which will achieve a Si/Al framework ratio in the range of 丨 to i 5 and preferably with the original The zeolite X containing low LTA preferably has a Si/Al framework ratio which is substantially uniform in the range of 1.15 to 1.35 before the clay conversion. More preferably, the stagnation X pre-system such as kaolin, kaolin Stone (kaolinite) and watery kaolin Sticky 163742.doc -13- 201249532 soil. The zeolite x precursor is used to make the first-fossil X in the composition of the binder-converted composition. Preferably, the average particle diameter of the binder material is between 04 4〇1 In the range of 46 μm. The forming procedure involves the zeolite X precursor (exemplified by kaolin clay) and the prepared zeolite X powder of the first zeolite X and, if appropriate, pore-forming materials (for example, corn starch providing large porosity) And other additives and water combination as needed to obtain a suitable molding consistency. Forming or forming large beads, spheres, pellets, etc. may be used in a bead forming process including, for example, Nauta mixing, turning or cylindrical tumbling The method is carried out to prepare larger particles (for example, in the range of 16 to 60 standard US mesh sizes) and then at temperatures typically in the range of 50 (TC to 70 (TC (930 卞 to 13 〇〇卞)) The shaped particles comprising the prepared first zeolite X and the zeolite cerium precursor are activated. In the case of a zeolite X precursor comprising a clay clay, the activation causes the material to undergo endothermic dehydroxylation, thereby forming disorder Kaolin phase. After activation, the caustic digestion of the shaped particles (eg, using sodium hydroxide) converts the activated zeolite cerium precursor to a second zeolite cerium, resulting in packet 3 having low or no detectable LTA zeolite content. a zeolite χ or a composition consisting essentially of a binder-converted composition. The ratio of the converted 2Si/A1 framework of zeolite X and the contribution of this material in the final formulation can be based on the zeolite enthalpy incorporated into the shaped particles. The type and amount of the body vary. Generally, the Si/A ratio of the zeolite X precursor is substantially maintained after conversion to zeolite ruthenium. Therefore, a typical kaolin clay having a Si/Ai ratio in the range of: Sichuan to 丨" The zeolite x fraction will be converted to a zeolite framework ratio in this range 163742.doc •14·201249532. Thus, a binder-converted composition having a different Si/Al ratio of the first (prepared) to the second (converted) portion of zeolite x can be prepared. However, increasing the Si/Al framework ratio of zeolite X from the range of ιοί hl to a range of 1.05 to 1.35 may result in an increase in the strength of the desorbent in the adsorption separation of pX (for example, the use of p-diethylbenzene (pDEB) desorbent). β When the zeolite X in the Si/Ai framework ratio of 1.0 is substituted for the higher ratio of zeolite X in the adsorbent formulation, the strength of the pDEB desorbent is greatly reduced (ie, the reciprocal value of the relative strength of the desorbent is increased) . This reduction in the strength of the desorbent affects the ability of the desorbent to displace the desired product into the extraction stream, obtaining high purity and recovery in a commercial process (specifically) for the adsorption separation of the plutonium in a simulated moving bed mode. The rate of ρ can have adverse consequences. These results illustrate the process efficiencies achievable by the use of a composition converted by a binder in which the converted portion of the zeolite ruthenium has a /octagonal framework ratio in the range of from 1 〇 5 to 1.35. The "/octane skeleton ratio may be the same or substantially the same as the framework ratio of the portion prepared for zeolite X. However, zeolite precursors such as kaolin clay often have a lower Si, " ratio, such as 1.0, and thus are generally Not converted to the desired higher ratio of Fossil X. However, the procedure for converting zeolite x steroids to zeolite oxime in the synthesis of the composition converted by the binder can be modified to increase the oxidization of the converted portion of the zeolite ruthenium The molar ratio of lanthanum to aluminum oxide. This can be achieved by adding a source of oxidation such as: colloidal dimethyl sol, material, sodium sulphate, sulphate or reactive microparticles (for example, dreams) Algae, chaos, etc. 163742.doc •15· 201249532 The source of cerium oxide may be added during the sorbent particle forming step or the caustic digestion step or both. The amount of cerium added is such that the cerium lanthanum precursor ( For example, the overall reaction mixture of the source of cerium oxide and cerium oxide is controlled so that the reaction composition is in the range of Na2〇/Si〇2 = 〇8 to 1.5 'SiO 2 /A1203 = 2.5 to 5, H20 /Na20 = 25 to 60. Thus, the use of a separate source of cerium oxide may allow for the preparation of a binder-converted composition in which the Si/Al ratio of both the prepared and converted portions of the zeolite is Closely matched (e.g., both in the range of i 〇 to i 5 and typically in the range of 1.05 to 1.35), thereby overcoming the above-discussed disadvantages of using a lower ratio of zeolite hydrazine in the adsorption separation of ρ 。. Advantageously, the zeolite The increase in the molar ratio of cerium oxide to aluminum oxide in the converted portion of X can also improve the hydrothermal stability of the resulting binder-converted composition. The first preparation of zeolite ruthenium in a composition converted by a binder The relative amount of the second converted portion may vary. According to some embodiments, the amount of the zeolite ruthenium precursor used to prepare the shaped particles will range from 5% by weight to 4% by weight 0/〇 and preferably 10% by weight. Up to 3 〇% by weight. Therefore These ranges also correspond to the amount of converted zeolite cerium present in the representative binder-switched composition set forth herein. Preferably, the binder material content is after the conversion to the second zeolite. In the range of wt% to 3 wt0 / 。. In the example binder-converted composition, the 'non-zeolitic material is substantially deficient (for example, usually less than 2 weight 0 /., often less than 1 weight. / And often less than 〇. 5 重量. The amount is present in the composition. The lack or substantial lack of non-zeolitic or amorphous materials can be achieved by using X-ray diffraction and / or high-resolution scanning electron microscopy (HR_ I63742.doc -16 - 201249532 SEM) Analysis of the composition converted by the binder to verify the crystal structure to confirm that the macroporous and microporous structure and distribution can be described by mercury porosimetry or liquid helium adsorption. confirm. Determination of LTA Zeolite Content in Zeolite X by XRD. As discussed above, the present invention requires X zeolite to have a size of no greater than 2.7 μm
. 平均直徑。另外，本發明亦需要含有低LTA之X沸石。LTA. The average diameter. In addition, the present invention also requires X zeolites containing low LTA. LTA
沸；5含量必須係非可檢測的或否則具有不大於〇 35之相對 強度’如藉由在下文表徵實例中所闡述之XRD方法所測 定°如下文所更充分論述，樣品之LTA沸石之相對強度（相 對「LTA強度」）係自在 7.27 ± 〇.160、16.29 ± 0.34。及 24.27 ± 0.50。2Θ處米勒指數為（2 〇 〇)、（4 2 0)及（6 2 2)之 3 組 LTA 型}弗石峰下方之積分面積之和相對於高度結晶標準NaA沸 石之相同峰之和來測定。 除該3組峰以外’在LTA型沸石之xrd掃描中存在其他 峰。然而，在7.27 ± 0.16〇、16.29 ± 0.34〇 及 24.27 ± 0.50〇 2Θ處米勒指數為（2 〇 〇)、（4 2 〇)及（6 2 2)之該3組峰往往具 有最小重疊或來自其他非LTA型沸石材料之最小干擾，且 仍為來自Na交換LTA沸石掃描之3個峰強度之和提供有意 • 義的總強度。此外，沸石X樣品之對其LTA沸石含量之 XRD表徵必須分別使用沸石乂及LTA沸石參照材料之鈉交 換形式（即，NaA沸石）來獲得。 因此，相對LTA強度係如下來計算·· ι〇〇乘以下式之商： 163742.doc 201249532 --品 LTA XRD $ 疮 基本上由LTA沸；5如^ -y τ -γα ^ ~:--- 彿石參照材料之參照 其中彿石X之樣品LTA XRD強度係在7 27 ± 〇 16。、16 29 士 〇.34° 及 24.27 土 G.5G° 2Θ 處米勒指數為（2 G G)、（4 2 0)及（6 2 2)之3組LTA彿石峰下方之積分面積之和，且lta沸石參 ”’、材料之參照XRD強度係在具有相同米勒指數及相關“值 之3組LTA沸石峰下方之積分面積之和。 如自圖1可看到，參照材料"3交換沸石A)(標示為掃描 A)提供3組具有其上文所指定之各別米勒指數及⑼值之乙丁八 沸石峰，其可用於測定諸如（在此情形中）沸石χ等不同樣 品材料之LTA沸石含量。依照下文所闡述之合成實例（c i) 製備但在XRD分析之前進行完全Na交換之比較材料的掃描 B指示可檢測LTA沸石在平均直徑不大於2·7 μιη之沸石χ中 之存在，而含有低LTA之X沸石之掃描C指示無可檢測^丁八 沸石’其亦在XRD分析之前進行完全Na交換。 圖2圖解說明圖1之相同比較掃描’但其中未顯示Na交換 沸石A參照掃描且係在1 〇χ放大率下，因此更易觀測到最佳 指示LTA沸石（若存在）之存在之3組LTA沸石峰。 對於與比較實例C-1相關之掃描Β而言，在7.27 ± 0.16〇、16.29 ± 0.34。及 24.27 ± 0.50。2Θ 處米勒指數為（2 〇 〇)、（4 2 0)及（6 2 2)之3組LTA沸石峰下方之積分面積係 5.9、2.3及5.1。因此’該3個指定峰面積之和係ΐ3·3。對於 與Na交換沸石Α參照材料相關之掃描Α而言，在其在7.27 士 163742.doc •18- 201249532 0.16。、16.29 ± 0.34。及24 27 ± 〇 5〇〇 2Θ處米勒指數為〇 0)、(4 2 0)及(6 2 2)之峰下方之積分面積係⑷5、μ ^及 607.4。因此，該3個指定峰面積之和係1492。因此，該樣 品之相對 LTA 強度係（13 3/1492) χ 1()〇 = 〇 離子交換 經黏結劑轉換之組合物中之第一所製備沸石乂及第二所 轉換沸石X之部分最初可呈其鈉形式，且鈉陽離子可使用 已知技術由諸如鋇、鉀、锶及/或鈣等不同陽離子部分或 全部交換。例如，在可實現鈉離子經鋇及/或鉀離子之離 子交換或代替之時間及溫度（例如，〇 5小時至丨〇小時在 20C至125C下）的條件下，可將使用其至少一些離子可交 換位點係呈鈉離子形式之沸石χ所合成的經黏結劑轉換之 組合物浸潰於含有鋇離子之溶液或含有鋇及鉀離子之溶液 中。亦可根據已知技術（例如，藉由將經預加熱氯化鋇/氣 化鉀溶液泵送穿過吸附劑粒子之管柱，以完全置換沸石χ 之納陽離子）以管柱操作實施離子交換。可重複過濾經黏 結劑轉換之組合物、自該溶液移除及重新浸潰於新鮮溶液 (例如’具有相同或不同比率之陽離子或其他類型之陽離 子）中’直至達成具有期望類型及比率之陽離子之期望交 換程度為止。 有利地，經黏結劑轉換之組合物將有至少95%或實質上 所有（例如，至少99%)之沸石X離子可交換位點經鋇或鋇及 卸之組合交換。通常，沒有其他金屬離子以有效改變該組 合物之吸附性質之量佔據第一所製備沸石χ或第二所轉換 163742.doc -19- 201249532 沸石x之各部分之離子可交換位點。在一實施例中，經黏 結劑轉換之組合物之沸石X將有其60%至1 〇〇%之離子可交 換位點經鋇交換及其〇%至40%之離子可交換位點經鉀交 換。 當沸石X之整體Si/Al莫耳比增加時’離子可交換位點之 數量降低。可藉由改變第一所製備沸石χ及第二所轉換沸 石X部分中之任一者或兩者之比率來影響整體比率。而 且，當單價陽離子（例如，κ+)經二價陽離子（例如，Ba+2) 代替時，每單位晶胞之陽離子之總數量降低。在沸石χ晶 體結構内，存在許多離子可交換位點位置，一些該等位置 係在超蘢外面。總體而言，沸石晶體結構中陽離子之數量 及位置將取決於所存在陽離子之大小及數量以及沸石之 Si/Al莫耳比。 對二甲苯分離 PX之分離係藉由使pX與至少_種其他C8烧基芳香族煙 之混合物與吸附劑接觸來實施。例如，可使包含C8烷基芳 香族烴之混合物之給料物流與吸附劑之床接觸，以在吸附 相中優先於鄰二甲苯⑽）、間二甲苯㈣)及乙苯（eb)選擇 性吸附Px。給料物流之該等其他基芳香族組份可作為 非吸附相選擇性穿過吸附區。 ‘ 包含c8燒基芳香族烴之混合物之給料物流可自各種精 廠製程物流（例如，重組油）分離且亦可含有其他化合物 例如C9烷基芳香族烴。在一種類型之分離製程中， 吸附劑之吸附容量之後’停止至吸附劑之給料物 在達到 流入Ο 163742.doc •20· 201249532 流，且然後沖洗吸附區以移除最初圍繞吸附劑之非吸附 相，使其不與吸附劑接觸。其後，可藉由用脫附劑處理吸 附劑使富含期望pX之吸附相自吸附劑孔脫附，該脫附劑通 常包含環烴（例如，含有芳香族環之烴），例如甲苯、苯、 二氫茚、對二乙基苯、1，4-二異丙基苯或其混合物。通常 使用同一脫附劑來（i)將非吸附相沖洗至包含脫附劑之萃 餘物物流中並（ii)將吸附相脫附至提取物流（亦包含脫附 劑）中。當基於不含脫附劑來考慮時，相對於給料物流， 由於提取物流含有富含pX之吸附相，故提取物流亦將富含 pX。 吸附劑自C8炫《基芳香烴之混合物（例如，二曱苯（〇χ、 mX及pX)與ΕΒ之混合物）吸附特定體積之ρχ之容量係重要 特徵’此乃因容量增加使得可減少對於給料之特定裝載速 率而言分離pX所需之吸附劑之量。因此，對ρχ之吸附劑 容量增加可使分離製程更有效，限制條件係在某一經濟上 期望之壽命期間’在吸附分離製程中之實際使用期間，應 維持對提取組份（在此情形中為ΡΧ)之良好初始容量以及總 吸附劑容量。 pX與脫附劑之交換速率通常可藉由半強度處峰值包絡 (peak envelope)之寬度來描述，該寬度係藉由繪製在脈衝 測試期間獲得之不同種類在吸附區流出物中之組成對時間 之曲線來獲得。峰寬度愈窄’脫附速率愈快。脫附速率亦 可以介於示蹤劑峰值包絡之中心與剛脫附之提取組份之消 失之間的距離來描述。此距離係時間相關的且從而係對在 163742.doc •21 · 201249532 此時間間隔期間所用脫附劑之體積的量度。示蹤劑通常係 較欲分離之材料更快穿過吸附劑管柱之相對非吸附化合 物。 相對於萃餘物組份對px之選擇性（β)可以介於ρΧ峰值包 絡之中心與示蹤劑峰值包絡（或其他參照點）之間之距離與 介於萃餘物組份峰值包絡之中心與示蹤劑峰值包絡（或參 照點）之間之相應距離的比率來描述。選擇性係對應於在 平衡條件下吸附相中之兩個組份之比率除以非吸附相中之 兩個相同組份之比率。因此，選擇性可自以下計算： 選擇性=(體積％ CA/體積％ DA)/(體積％ cu/體積％ DU) 其中C及D係以重量百分數表示之給料混合物之兩個組份 且下標Α及U分別表示吸附相及非吸附相。當給料經過吸 附劑之床不改變组合物時，換言之，當在非吸附相與吸附 相之間不存在材料之淨轉移時，確定平衡條件。在上文等 式中’大於1 ·0之選擇性指示對吸附劑内組份C之優先吸 附。相反地，小於丨.0之選擇性將指示優先吸附組，使 得非吸附相富含組份c且吸附相富含組份D。 對於兩個組份之選擇性接近丨〇而言，吸附劑對一組份 不存在相對於另一組份之優先吸附（即，相對於彼此，其 兩者均以相同程度經吸附）。當選擇性偏離1.0時，吸附劑 對一組份存在相對於另一組份之愈來愈優先之吸附。選擇 fi不僅可經表達用於一給料物流化合物相對於另一給料物 流化合物（例如，ρχ相對於mX之選擇性），但亦可經表達 用於任何給料物流化合物與脫附劑之間（例如，ρχ相對於 163742.doc •22· 201249532 對二乙苯之選擇性）。 儘管當相對於萃餘物組份吸附劑對P x之選擇性僅略微大 於1時，提取組份自萃餘物組份之分離在理論上係可能 的，但出於製程經濟考慮，此選擇性較佳為至少2。通 常，選擇性愈高，實施吸附分離愈容易。較高選擇性允許 使用較小量之吸附劑來獲得相同產生率（例如，ρχ回收 率），其中吸附劑對呈混合物形式之同一組份（例如，來自 〇X、mX及ΕΒ之ΡΧ)具有相對較低選擇性。 必須慎重選擇用於吸附分離製程之脫附劑以滿足若干標 準。脫附劑應理想地具有足夠強度（即，足夠強有力地經 吸附）以合理質量流動速率自吸附劑置換卩又，而不會如此 強有力地經吸附以致阻止ρΧ在下一吸附循環中置換脫附 劑。在選擇性方面，相對於萃餘物組份吸附劑對ρχ之選擇 性較佳比相對於萃餘物組份其對脫附劑之選擇性更高。 因此’對於脫附劑而言欲考慮之性能參數係其對給料中 ρΧ之交換速率’換言之，ρχ之相對脫附速率。此參數與 吸附分離製程中所必須使用以自吸附劑脫附ρχ之脫附劑之 量直接相關。較快交換速率減少所需脫附劑之量，且從而 提高含有脫附劑之較大製程物流之操作效率，包括脫附劑 自該等物流之分離及再循環。關於提取組份之為1或略微 較低之脫附劑選擇性有助於確保以脫附劑之合理流動速率 脫附所有ρΧ ’且亦確保提取組份可在隨後吸附步驟中置換 脫附劑。量測選擇性之一方式可係藉由下文所闡述之「脈 衝測試J。 163742.doc -23- 201249532 實例 結合以下實例進一步詳細闡述本發明，該等實例闡釋或 模擬本發明實踐中所涉及之各個方面。應理解，期望屬於 本發明精神範圍内之所有變化均受到保護，且因此本發明 不應理解為受限於該等實例。 合成實例 實例s-i -種晶 藉由混合755 g氫氧化鈉（50% NaOH)、425 g三水合氧化 銘及320 g水來製備鋁酸鹽溶液。將混合物加熱至23〇卞並 保持15分鐘，然後冷卻至12〇卞》 將225 g鋁酸鹽溶液與1035 g水、643 g氫氧化鈉（5〇% NaOH)及1298 g矽酸鈉混合。混合之後’將該批次老化72 小時以產生沸石種晶。Boiling; 5 content must be non-detectable or otherwise have a relative strength no greater than 〇35' as determined by the XRD method set forth in the characterization examples below. As discussed more fully below, the relative LTA zeolite of the sample is as follows. The strength (relative to "LTA strength") is 7.27 ± 〇.160, 16.29 ± 0.34. And the sum of the integral areas under the 24.27 ± 0.50. 2 Miller Miller index of (2 〇〇), (4 2 0) and (6 2 2) of the three groups of LTA-type feldspars relative to the highly crystalline standard NaA zeolite The sum of the same peaks is measured. In addition to the three sets of peaks, there are other peaks in the xrd scan of the LTA type zeolite. However, the three sets of peaks with a Miller index of (2 〇〇), (4 2 〇) and (6 2 2) at 7.27 ± 0.16 〇, 16.29 ± 0.34 〇 and 24.27 ± 0.50 〇 2 往往 tend to have minimal overlap or The minimum interference from other non-LTA type zeolite materials, and still provides the intentional total intensity for the sum of the three peak intensities from the Na-exchanged LTA zeolite scan. In addition, the XRD characterization of the zeolite X sample for its LTA zeolite content must be obtained using the sodium exchange form of the zeolite ruthenium and the LTA zeolite reference material, i.e., NaA zeolite, respectively. Therefore, the relative LTA intensity is calculated as follows: ι〇〇 multiplied by the following formula: 163742.doc 201249532 --Product LTA XRD $ The sore is basically boiled by LTA; 5 such as ^ -y τ -γα ^ ~:-- - Reference to the Fossil reference material. The LTA XRD strength of the sample of Fo Shi X is 7 27 ± 〇16. , 16 29 g〇.34° and 24.27 soil G.5G° 2Θ The sum of the integral areas under the three groups of LTA Fossil peaks with the Miller index of (2 GG), (4 2 0) and (6 2 2) And the reference XRD intensity of the lta zeolite ginseng' is the sum of the integrated areas below the three sets of LTA zeolite peaks having the same Miller index and associated "values." As can be seen from Figure 1, the reference material "3 exchange zeolite A) (labeled as scan A) provides three sets of butyl octadecyl peaks with their respective Miller indices and (9) values specified above, which are available For determining the LTA zeolite content of different sample materials such as, in this case, zeolite ruthenium. Scan B of a comparative material prepared according to the synthesis example (ci) set forth below but subjected to complete Na exchange prior to XRD analysis indicates that the LTA zeolite can be detected in the presence of zeolites having an average diameter of not more than 2·7 μηη, while containing low Scan C of the X zeolite of LTA indicates no detectable octadecyl sulphate' which also undergoes complete Na exchange prior to XRD analysis. Figure 2 illustrates the same comparative scan of Figure 1 but in which the Na-exchanged zeolite A reference scan is not shown and is at 1 〇χ magnification, so it is easier to observe the three sets of LTAs that best indicate the presence of LTA zeolite (if present). Zeolite peak. For the scanning enthalpy associated with Comparative Example C-1, it was 7.27 ± 0.16 〇 and 16.29 ± 0.34. And 24.27 ± 0.50. 2Θ The integral area under the LTA zeolite peaks of the three groups of (2 〇 〇), (4 2 0) and (6 2 2) is 5.9, 2.3 and 5.1. Therefore, the sum of the three specified peak areas is ΐ3·3. For scanning cesium associated with the exchange of zeolite ruthenium reference materials with Na, it is at 7.27 士 163742.doc • 18- 201249532 0.16. , 16.29 ± 0.34. And 24 27 ± 〇 5〇〇 2Θ The Miller index is the integral area under the peaks of 〇 0), (4 2 0) and (6 2 2) (4) 5, μ ^ and 607.4. Therefore, the sum of the three designated peak areas is 1492. Therefore, the relative LTA strength of the sample (13 3/1492) χ 1 () 〇 = 〇 ion exchange through the binder conversion composition of the first prepared zeolite 乂 and the second converted zeolite X may initially It is in its sodium form, and the sodium cation can be exchanged partially or completely from different cations such as cesium, potassium, rubidium and/or calcium using known techniques. For example, at least some of the ions may be used under conditions that allow sodium ions to undergo ion exchange or substitution of ions and/or potassium ions (for example, 〇5 hours to 丨〇 hours at 20C to 125C). The exchangeable site is a binder-converted composition synthesized from a zeolite ion in the form of sodium ions, which is impregnated into a solution containing barium ions or a solution containing barium and potassium ions. Ion exchange can also be carried out in a column operation according to known techniques (for example, by pumping a preheated cesium chloride/potassium sulphate solution through a column of sorbent particles to completely replace the cations of the zeolite ruthenium) . The binder-switched composition can be repeatedly filtered, removed from the solution, and re-impregnated into a fresh solution (eg, 'the same or a different ratio of cations or other types of cations' until a desired type and ratio of cations are achieved The degree of exchange is expected. Advantageously, the binder-switched composition will have at least 95% or substantially all (e.g., at least 99%) of the zeolite X ion exchangeable sites exchanged by a combination of hydrazine or hydrazine. Typically, no other metal ions occupy the ion exchange sites of the first prepared zeolite or the second converted 163742.doc -19-201249532 zeolite x in an amount effective to modify the adsorption properties of the composition. In one embodiment, the zeolite X of the binder-switched composition will have 60% to 1% of its ion exchangeable sites exchanged via hydrazine and its 〇% to 40% of the ion exchangeable sites via potassium. exchange. As the overall Si/Al molar ratio of zeolite X increases, the number of ion exchange sites decreases. The overall ratio can be affected by varying the ratio of either or both of the first prepared zeolite enthalpy and the second converted zeolite X portion. Moreover, when a monovalent cation (e.g., κ+) is replaced by a divalent cation (e.g., Ba+2), the total number of cations per unit cell decreases. Within the zeolite ruthenium structure, there are many ion exchange site positions, some of which are outside the ruthenium. In general, the amount and location of the cations in the crystal structure of the zeolite will depend on the size and amount of cations present and the Si/Al molar ratio of the zeolite. Separation of p-xylene Separation of PX is carried out by contacting a mixture of pX with at least one other C8 alkyl aromatic fumes with an adsorbent. For example, a feed stream comprising a mixture of C8 alkyl aromatic hydrocarbons can be contacted with a bed of adsorbent to preferentially adsorb to o-xylene (10), meta-xylene (tetra), and ethylbenzene (eb) in the adsorption phase. Px. The other base aromatic components of the feed stream can selectively pass through the adsorption zone as a non-adsorbed phase. The feed stream comprising a mixture of c8 alkyl aromatic hydrocarbons can be separated from various refinery process streams (e.g., reconstituted oils) and can also contain other compounds such as C9 alkyl aromatic hydrocarbons. In one type of separation process, the adsorbent capacity of the adsorbent is then 'stopped until the feed of the adsorbent reaches a flow of inflow Ο 163742.doc •20· 201249532, and then the adsorption zone is flushed to remove the non-adsorbed material initially surrounding the adsorbent. The phase is such that it is not in contact with the adsorbent. Thereafter, the adsorbent phase enriched in the desired pX can be desorbed from the adsorbent pores by treating the adsorbent with a desorbent, which typically comprises a cyclic hydrocarbon (eg, a hydrocarbon containing an aromatic ring), such as toluene, Benzene, indoline, p-diethylbenzene, 1,4-diisopropylbenzene or a mixture thereof. The same desorbent is typically used to (i) flush the non-adsorbed phase into the raffinate stream containing the desorbent and (ii) desorb the adsorbed phase into the extract stream (also including the desorbent). When considered based on the absence of a desorbent, the extraction stream will also be enriched in pX relative to the feed stream, since the extract stream contains a pX-rich adsorption phase. The adsorption capacity of the adsorbent from C8 Hyun's mixture of aromatic hydrocarbons (for example, a mixture of diphenylbenzene (〇χ, mX and pX) and ruthenium) is a key feature of the adsorption of a specific volume of ρ ' 'this is due to the increase in capacity, which can be reduced The amount of adsorbent required to separate pX in terms of the specific loading rate of the feedstock. Therefore, an increase in the capacity of the adsorbent for ρχ can make the separation process more efficient, and the constraint is during an economically desired lifetime period. During the actual use in the adsorption separation process, the extraction component should be maintained (in this case It is a good initial capacity and total adsorbent capacity. The rate of exchange of pX with the desorbent can generally be described by the width of the peak envelope at half intensity, which is plotted against the composition of the different species obtained in the adsorption zone during the pulse test. The curve is obtained. The narrower the peak width, the faster the desorption rate. The rate of desorption can also be described as the distance between the center of the tracer peak envelope and the loss of the freshly desorbed extracted component. This distance is time dependent and thus a measure of the volume of desorbent used during this time interval of 163742.doc • 21 · 201249532. The tracer is typically a relatively non-adsorbing compound that passes through the column of adsorbent faster than the material to be separated. The selectivity to px relative to the raffinate component (β) may be between the center of the ρΧ peak envelope and the tracer peak envelope (or other reference point) and the peak envelope of the raffinate component. The ratio of the center to the corresponding distance between the tracer peak envelope (or reference point) is described. The selectivity corresponds to the ratio of the two components in the adsorbed phase under equilibrium conditions divided by the ratio of the two identical components in the non-adsorbed phase. Therefore, the selectivity can be calculated from: Selectivity = (% by volume CA / volume % DA) / (% by volume cu / volume % DU) where C and D are the two components of the feed mixture expressed in weight percent and under The standard and U represent the adsorbed phase and the non-adsorbed phase, respectively. The equilibrium condition is determined when the feed passes through the bed of adsorbent without altering the composition, in other words, when there is no net transfer of material between the non-adsorbed phase and the adsorbed phase. The selectivity of > greater than 1.00 in the above equation indicates preferential adsorption of component C within the adsorbent. Conversely, a selectivity of less than 丨0 will indicate a preferential adsorption group such that the non-adsorbed phase is enriched in component c and the adsorbed phase is enriched in component D. For the selectivity of the two components to be close to hydrazine, the adsorbent does not have a preferential adsorption of one component relative to the other component (i.e., both are adsorbed to the same extent relative to each other). When the selectivity deviates from 1.0, the adsorbent has an increasingly preferential adsorption of one component relative to the other component. The choice fi can be expressed not only for a feed stream compound relative to another feed stream compound (e.g., the selectivity of pH relative to mX), but can also be expressed between any feed stream compound and a desorbent (e.g. , ρχ relative to 163742.doc •22· 201249532 selectivity to diethylbenzene). Although the separation of the extract component from the raffinate component is theoretically possible when the selectivity of the adsorbent to Px relative to the raffinate component is only slightly greater than 1, this option is for process economic considerations. Preferably, the property is at least 2. Generally, the higher the selectivity, the easier it is to perform adsorption separation. Higher selectivity allows the use of smaller amounts of adsorbent to achieve the same rate of production (eg, pH recovery), where the adsorbent has the same component in the form of a mixture (eg, from 〇X, mX, and ΕΒ) Relatively low selectivity. The desorbent used in the adsorption separation process must be carefully selected to meet several criteria. The desorbent should desirably have sufficient strength (i.e., sufficiently strong to adsorb) to displace the ruthenium from the adsorbent at a reasonable mass flow rate without being so strongly adsorbed that the ρ 置换 is prevented from being displaced in the next adsorption cycle. Attachment. In terms of selectivity, the selectivity of the adsorbent to the raffinate component relative to the raffinate component is preferably higher than that of the raffinate component. Thus, the performance parameter to be considered for the desorbent is its rate of exchange of ρ 给 in the feedstock. In other words, the relative desorption rate of ρ 。 . This parameter is directly related to the amount of desorbent that must be desorbed from the adsorbent in the adsorptive separation process. The faster exchange rate reduces the amount of desorbent required and thereby increases the operating efficiency of the larger process stream containing the desorbent, including the separation and recycle of the desorbent from such streams. The selectivity of the desorbent with respect to the extracted component of 1 or slightly lower helps to ensure that all of the p' is desorbed at a reasonable flow rate of the desorbent and also ensures that the extracted component can displace the desorbent in the subsequent adsorption step. . One of the methods of measuring selectivity can be further elaborated by the following examples of the "Pulse Test J. 163742.doc -23-201249532" examples, which illustrate or simulate the practice of the present invention. It is to be understood that all changes that are within the spirit of the invention are intended to be protected, and thus the invention should not be construed as being limited to the examples. Example of Synthesis Example Si - Seeding by Mixing 755 g of Sodium Hydroxide (50% NaOH), 425 g of trihydrate oxide and 320 g of water to prepare the aluminate solution. Heat the mixture to 23 Torr for 15 minutes, then cool to 12 〇卞. 225 g of aluminate solution 1035 g water, 643 g sodium hydroxide (5 〇% NaOH) and 1298 g sodium citrate were mixed. After mixing, the batch was aged for 72 hours to produce zeolite seed crystals.
實例S-2 -沸石X 藉由混合9*70 g氫氧化鈉（5〇% NaOH) ' 313 g三水合氧化 铭及418 g水來製備鋁酸鹽溶液。將混合物加熱至23〇卞。 將559 g鋁酸鹽溶液與根據實例s_i所製備之〇 35 §種 晶、1744 g水及439 g矽酸鈉混合》 然後將溶液老化3.5小時。將所得晶體自該溶液過遽並 乾燥。藉由XRD及ICP分析晶體且其經測定為si/Al骨架莫 耳比為1.275之彿石X。根據下文所闡述之方法，藉由沉降 圖分析，粒徑係經測定為1.7 μηι 0 實例S-3 -經黏結劑轉換之沸石X组合物 使一份860 g之根據實例S-2所製備之沸石乂與14〇 g高嶺 163742.doc •24· 201249532 土（自BASF獲得之ASP 400ΤΜ)、20 g玉米澱粉及20 g羧甲基 纖維素（自BASF獲得）及適量水黏聚在一起。然後擠出混合 物’且在乾空氣下於650°C下將擠出物乾燥並活化4小時。 然後將擠出物網篩至0.5 mm之平均大小。 然後將一份100 g之團塊浸潰於濃度為2.4%之580 g NaOH溶液中用於黏結劑轉換。黏結劑轉換溫度係8〇〇c至 100°C且持續6小時。 比較實例Example S-2 - Zeolite X An aluminate solution was prepared by mixing 9*70 g of sodium hydroxide (5% by weight NaOH) with 313 g of trihydrate oxidation and 418 g of water. The mixture was heated to 23 Torr. The 559 g aluminate solution was mixed with 〇35 § seed crystals, 1744 g water and 439 g sodium citrate prepared according to Example s_i and the solution was aged for 3.5 hours. The resulting crystals were dried from the solution and dried. The crystal was analyzed by XRD and ICP and determined to be Sisha X with a si/Al skeleton molar ratio of 1.275. According to the method described below, the particle size was determined to be 1.7 μηι 0 by the sedimentation diagram analysis. Example S-3 - The binder-converted zeolite X composition was prepared in an amount of 860 g according to Example S-2. Zeolite 黏 is entangled with 14 〇g Gaoling 163742.doc •24· 201249532 soil (ASP 400 获得 obtained from BASF), 20 g corn starch and 20 g carboxymethyl cellulose (obtained from BASF) and an appropriate amount of water. The mixture was then extruded and the extrudate was dried and activated at 650 ° C for 4 hours under dry air. The extrudate mesh was then sieved to an average size of 0.5 mm. A 100 g mass was then immersed in a 2.4% 580 g NaOH solution for binder conversion. The binder conversion temperature is 8 〇〇c to 100 ° C for 6 hours. Comparative example
實例C-1 - 比較沸石X 根據實例S-2但使用825 g矽酸鈉及根據實例S-1所製備之 〇·7 g種晶來製備比較沸石X。 藉由XRD及ICP分析晶體且其經測定為si/Al骨架莫耳比 為1.225之沸石X。根據下文所闡述之方法，藉由沉降圖分 析’粒徑係經測定為1.7 μιη 〇Example C-1 - Comparative Zeolite X Comparative Zeolite X was prepared according to Example S-2 but using 825 g of sodium citrate and 〇·7 g seed crystals prepared according to Example S-1. The crystal was analyzed by XRD and ICP and determined to be a zeolite X having a si/Al skeleton molar ratio of 1.225. According to the method described below, the particle size system was determined to be 1.7 μηη by sedimentation.
實例C-2 - 比較沸石X 首先藉由混合1058 g液體鋁酸鈉、160 g氫氧化鈉（5〇% NaOH)及432 g水來形成鋁酸鹽溶液來製備另一比較彿石 X。然後，將523 g鋁酸鹽溶液與454 g水及451 g矽酸鈉混 合0 將溶液老化2.3小時且然後結晶5小時。過濾晶體。藉由 XRD及ICP分析晶體且其經測定為si/Al骨架莫耳比為1>25 之彿石X。根據下文所闡述之方法，藉由沉降圖分析，粒 徑係經測定為3 .8 μηι 〇 合成後處理實例 163742.doc •25- 201249532 實例τ-i 使根據實例S·3所製備之樣品與12 Wt% BaCl及1 wt% KC1溶液之混合物進行離子交換。離子交換溶液與固體比 率以質量計係21:1 »在管柱中在95°C下實施離子交換2小 時。完成離子交換之後，將管柱排乾且然後用水洗滌固體 材料’直至氣化物含量低於〇·〇5 wt%為止。然後在乾空氣 流下於250°C下在Blue Μ烘箱中，將經洗滌樣品乾燥i小 時。所獲得之材料具有5.7 wt%至5.8 wt%之LOI » 在本文中用在900°C下之公認LOI測試來表達吸附劑之水 含量。LOI測試係闞述於UOP測試方法第UOP954-03號（通 過 ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken，PA，19428-2959 USA 獲得）中。 實例T-2 以與實例Τ-1相同之方式對根據實例C-1所製備之比較樣 品進行離子交換。 表徵實例 實例CH-1 用於測定LTA沸石之相對量之X射線繞射（XRD) 可藉由XRD分析測定本發明沸石中之LTA沸石之相對 量。使用標準XRD技術獲得以下實例中所呈現之X射線圖 案。 將樣品研磨至粉末（常常150目或更少），然後放置於含 有CaN03飽和溶液之53%相對濕度室中至少過夜（約15小 時）。將1克經平衡粉末樣品散佈至XRD樣品架上，並放置 163742.doc • 26· 201249532 於XRD儀器上，並使用5.〇。至25.〇。2β (〇 〇2。步階大小，ι〇 秒/步階si*數時間）之參數進行掃描。XRD儀器係以…吨 XDS2000儀器或配備有銅X射線管之功能等效物。在45让乂 及35 mA之設定下運行xrD儀器。將儀器中之濕度維持於 53%濕度下。 樣〇口中LTA;弗石之相對量係自在7.27 土 〇. “ο、16.29 土 0.34 及 24.27 ± 0.50。2Θ處米勒指數為（2 〇 〇)、（4 2 〇)及（6 2 2)之3組LTA沸石峰下方之積分面積之和相對於高度結晶 標準NaA沸石之相同峰之和來測定。米勒指數（/j & 〇指定 何種LTA型沸石峰欲包括於積分程序中，並藉由以下等式 與峰位置相關聯： λ = (2 aNaLTA sin(0hk,)) / (¾2 + k2 + l2)ul 其中λ係x射線波長（對於CuKa輻射而言為1.54059 A)， aNaLTA係取決於Si/Al比率之23.8 A至24.8 A之NaA沸石晶格 參數’且0hkl係具有米勒指數（A & /)之啥之1/2繞射角。 實例CH-2 沉降圖分析 藉由Micromedtics Sedigraph 5.120粒徑分析系統來測定 沸石粒徑。Sedigraph 5120係全自動的，且依照所提供之 操作手冊操作此單元。 首先將沸石樣品分散於去離子水中（2.8克沸石/50克D.I. 水）。然後將樣品轉移至Sedigraph單元。自此設備，基於 重置平均數獲得 >弗石粒子之粒徑分佈。例如，可獲得D5〇 或D90之粒徑分佈^ D50指示50 wt.%之粒子係低於指定直 163742.doc -27- 201249532 徑之直徑，而D90指示90 wt.%之粒子係低於指定直徑之直 徑。因此，D50亦稱為平均直徑。 實例CH-3 用於選擇性性能之脈衝測試 「脈衝測試」係用於測試吸附容量、選擇性、解析度及 交換速率。脈衝測試裝置包括體積為7〇立方公分（cc)且在 室之相對末端處具有入口及出口部分之管狀吸附劑室。該 室係經配備以允許在恆定的預定溫度及壓力下操作。可將 諸如折射計、偏振計及層析儀等定量及定性分析設備附接 至該室之出口管線，並用於定性地檢測及/或定量地測定 離開吸附劑室之流出物物流中之一或多個組份。 在脈衝測試期間，首先填充吸附劑直至藉由使特定脫附 劑穿過吸附劑室與該脫附劑平衡。小體積或脈衝之給料混 合物可用脫附劑來稀釋，其係藉由在零時間時將脫附劑流 轉換成給料樣品環路來注射。重新開始脫附劑流，且當在 液體-固體層析操作中時溶析給料混合物組份。可在運轉 中分析流出物，或者，另一選擇為，可週期性收集並單獨 分析（離線）流出物樣品，且用組份濃度與流出物之量對相 應組份峰之包絡之跡線繪製曲線。 來源於脈衝測試之資訊可用於確定吸附劑空隙體積、ΡΧ 或萃餘物組份之滞留體積、相對於另一組份對一組份之選 擇性、級時間、組份之間之解析度及ρχ經脫附劑之脫附速 率。ΡΧ或萃餘物組份之滯留體積可自介於pX或萃餘物組 伤之峰值包絡之中心與示蹤劑組份之峰值包絡或一些其他 163742.doc -28 - 201249532 已夫參β點之間的距離來確^。其係用在對應於介於峰值 包絡間之距離的間隔時間期間所泵送脫附劑之立方公分形 式體積來表達。 在PX之吸附分離中評價根據實例s_3製備並根據實例Tq 離子交換之樣品。亦評價根據實例c-〗製備並根據實例τ_2 離子交換之比較樣品。 藉由首先將吸附劑裝載於70 cm3管柱中於脫附劑對二乙 苯（PDEB)下面來實施上文所闡述之標準脈衝測試。與正壬 烷（n-CO示蹤劑一起注射含有相等量之£3及三種二甲苯異 構體中每一者之給料脈衝。在12rc至177它（25〇卞至 3 50 F)之範圍内之各個管柱溫度下實施脈衝測試，以檢驗 溫度對選擇性之影響。自該等脈衝測試中之每一者所獲得 之組份峰確定PX選擇性，且將15〇t下之結果顯示於下文 表CH-1中。 實例CH-4 容量測試 對根據實例S-3製備並根據實例Τ-丨離子交換之樣品評價 其在PX之吸附分離中之容量。亦評價根據實例cm製備並 根據實例T-2離子交換之比較樣品。 用含有oX、mX、pX及EB之樣品給料混合物裝填含有7〇 cm3最初於PDEB下面所裝載之吸附劑之管柱。在15〇。(：之 管柱溫度下實施穿透測試，以測定1^〇1=5.7°/。至5.8%下吸 附劑之容量（cm3)及PX/PDEB選擇性（如上文所闡述），且將 結果顯示於下文表CH-1中》 163742.doc -29· 201249532 表 CH-lExample C-2 - Comparative Zeolite X Another comparative Fossil X was prepared by first mixing 1058 g of liquid sodium aluminate, 160 g of sodium hydroxide (5 % NaOH) and 432 g of water to form an aluminate solution. Then, 523 g of the aluminate solution was mixed with 454 g of water and 451 g of sodium citrate. The solution was aged for 2.3 hours and then crystallized for 5 hours. Filter the crystals. The crystal was analyzed by XRD and ICP and determined to be Si Shi X with a si/Al skeleton molar ratio of 1 > According to the method described below, the particle size was determined to be 3 .8 μηι 〇 by post-resolution analysis. 163742.doc •25- 201249532 Example τ-i The sample prepared according to Example S·3 was A mixture of 12 Wt% BaCl and 1 wt% KC1 solution was ion exchanged. The ratio of ion exchange solution to solids was 21:1 by mass: ion exchange was carried out at 95 °C for 2 hours in the column. After the ion exchange is completed, the column is drained and then the solid material is washed with water ' until the vapor content is less than 〇·〇 5 wt%. The washed samples were then dried for one hour in a Blue Μ oven at 250 ° C under a dry air stream. The material obtained has an LOI of 5.7 wt% to 5.8 wt% » The water content of the adsorbent is expressed herein using a well-established LOI test at 900 °C. The LOI test system is described in UOP Test Method No. UOP954-03 (available through ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA, 19428-2959 USA). Example T-2 A comparative sample prepared according to Example C-1 was subjected to ion exchange in the same manner as Example Τ-1. Characterization Examples Example CH-1 X-ray diffraction (XRD) for determining the relative amount of LTA zeolite The relative amount of LTA zeolite in the zeolite of the present invention can be determined by XRD analysis. The X-ray pattern presented in the following examples was obtained using standard XRD techniques. The sample was ground to a powder (often 150 mesh or less) and then placed in a 53% relative humidity chamber containing a saturated solution of CaN03 for at least overnight (about 15 hours). Dispense 1 gram of the balanced powder sample onto the XRD sample holder and place 163742.doc • 26· 201249532 on the XRD instrument and use 5.〇. To 25. The parameters of 2β (〇 〇 2. step size, ι〇 second/step si* number time) are scanned. The XRD instrument is a functional equivalent of a ton XDS2000 instrument or equipped with a copper X-ray tube. Run the xrD instrument at 45 乂 and 35 mA. Maintain the humidity in the instrument at 53% humidity. LTA; the relative amount of feldspar is free from 7.27 soil. "ο, 16.29 soil 0.34 and 24.27 ± 0.50. 2 Miller Miller index is (2 〇〇), (4 2 〇) and (6 2 2) The sum of the integrated areas under the peaks of the three sets of LTA zeolites is determined relative to the sum of the same peaks of the highly crystalline standard NaA zeolite. The Miller Index (/j & 〇 specifies which LTA type zeolite peaks are to be included in the integration procedure, and It is related to the peak position by the following equation: λ = (2 aNaLTA sin(0hk,)) / (3⁄42 + k2 + l2)ul where λ is the x-ray wavelength (1.54059 A for CuKa radiation), aNaLTA Depending on the Si/Al ratio of 23.8 A to 24.8 A of the NaA zeolite lattice parameter 'and the 0hkl line has a 1/2 diffraction angle of the Miller index (A & /). Example CH-2 Settlement analysis The zeolite particle size was determined by a Micromedtics Sedigraph 5.120 particle size analysis system. The Sedigraph 5120 was fully automated and operated in accordance with the supplied manual. The zeolite sample was first dispersed in deionized water (2.8 g zeolite / 50 g DI water) Then transfer the sample to the Sedigraph unit. Since this device, based on resetting The mean number is obtained as follows: the particle size distribution of the vermiculite particles. For example, the particle size distribution of D5〇 or D90 can be obtained. The D50 indicates that the particle size of 50 wt.% is lower than the diameter of the specified straight 163742.doc -27-201249532 diameter. D90 indicates that 90 wt.% of the particles are below the diameter of the specified diameter. Therefore, D50 is also called the average diameter. Example CH-3 Pulse test for selective performance "Pulse test" is used to test adsorption capacity, selection Saturation, resolution, and exchange rate. The pulse test apparatus includes a tubular adsorbent chamber having a volume of 7 cubic centimeters (cc) and having inlet and outlet portions at opposite ends of the chamber. The chamber is equipped to allow for constant reservations. Operating at temperature and pressure. Quantitative and qualitative analytical equipment such as refractometers, polarimeters, and chromatographs can be attached to the outlet line of the chamber and used to qualitatively detect and/or quantitatively determine the flow out of the sorbent chamber. One or more components in the stream. During the pulse test, the adsorbent is first filled until it is equilibrated with the desorbent by passing a specific desorbent through the adsorbent chamber. The small volume or pulsed feed mixture can be Dilution with a desorbent by injecting the desorbent stream into a feed sample loop at time zero. Restarting the desorbent stream and eluting the feedstock during liquid-solid chromatography operations Mixture component. The effluent can be analyzed during operation, or alternatively, the effluent sample can be collected periodically and analyzed separately (offline), and the envelope of the corresponding component peak with the component concentration and the amount of effluent The trace draws a curve. Information derived from pulse testing can be used to determine the void volume of the adsorbent, the hold-up volume of the ruthenium or raffinate component, the selectivity to the other component relative to one component, the grade time, and the resolution between the components and The rate of desorption of the desorbent by ρχ. The retention volume of the ruthenium or raffinate component may be from the peak of the peak envelope of the pX or raffinate group with the peak envelope of the tracer component or some other 163742.doc -28 - 201249532 The distance between them is indeed ^. It is expressed in cubic centimeters of volume of the desorbent pumped during the interval corresponding to the distance between the peak envelopes. Samples prepared according to Example s_3 and ion exchanged according to Example Tq were evaluated in the adsorption separation of PX. Comparative samples prepared according to Example c-I and ion exchange according to Example τ_2 were also evaluated. The standard pulse test set forth above was carried out by first loading the adsorbent in a 70 cm3 column under the desorbent p-diethylbenzene (PDEB). Feeding a feed pulse containing equal amounts of each of the £3 and three xylene isomers with n-CO tracer. It ranges from 12 rc to 177 (25 〇卞 to 3 50 F) A pulse test is performed at each column temperature to check the effect of temperature on selectivity. The component peaks obtained from each of the pulse tests determine the PX selectivity and the results at 15 〇t are displayed. In Table CH-1 below. Example CH-4 Capacity Test The capacity of the sample prepared according to Example S-3 and according to the example Τ-丨 ion exchange was evaluated for its capacity in the adsorption separation of PX. Also evaluated according to the example cm prepared and according to Example Comparative sample of T-2 ion exchange. A sample feed mixture containing oX, mX, pX and EB was used to fill a column containing 7 〇cm3 of adsorbent initially loaded under the PDEB. At 15 〇. A penetration test was performed at a temperature to determine the capacity of the adsorbent (cm3) and the PX/PDEB selectivity (as explained above) at 5.1 〇 1 = 5.7 ° / to 5.8%, and the results are shown in Table CH below. -1 中》 163742.doc -29· 201249532 Table CH-l
基於選擇性及容量結果，使用模擬移動床（SMB)模型化 分析來估算商業pX分離製程中之給料通量及脫附劑對給料 (D/F)需要。結果比較亦顯示於表匸仏1中。s_3/T_i超過c_ 1/T-2之給料速率增加係1%，而脫附劑需要降低至92%。此 表示有效操作pX分離製程所需脫附劑之量顯著減少。D/F 係基於質量流動比率《此處，吾人假定c_ 1/T 2情形係為 100之基本情形。 【圖式簡單說明】 圖1顯示3組XRD掃描，其提供3組具有其各別米勒指數 及2Θ值之LTA沸石峰，其可用於測定不同樣品材料之lTA 沸石含量，其中掃描A係參照材料（Na交換沸石A)之XRD掃 描；掃描B係比較材料之xrd掃描，該比較材料係依照合 成實例（C-1)製備但在XRD分析之前進行完全Na交換，且 掃描C係含有低LTA之X沸石之XRD掃描，其指示無可檢測 LTA彿石且亦在XRD分析之前進行完全Na交換。 圖2圖解說明圖1之相同比較掃描，但其中未顯*Na交換 沸石A參照掃描且係在1 〇χ放大率下，因此更易觀測到最佳 指示LTA沸石（若存在）之存在之3組LTA沸石峰。 163742.doc -30·Simulated moving bed (SMB) modelling analysis was used to estimate feed flux and desorbent versus feed (D/F) requirements in a commercial pX separation process based on selectivity and capacity results. A comparison of the results is also shown in Table 1. The feed rate increase of s_3/T_i over c_ 1/T-2 is 1%, and the desorbent needs to be reduced to 92%. This represents a significant reduction in the amount of desorbent required to effectively operate the pX separation process. The D/F is based on the mass flow ratio. Here, we assume that the c_ 1/T 2 case is the basic case of 100. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows three sets of XRD scans, which provide three sets of LTA zeolite peaks with their respective Miller indices and two enthalpy values, which can be used to determine the content of 1TA zeolite in different sample materials. XRD scan of material (Na-exchanged zeolite A); scan B-series comparison of xrd scans of materials prepared according to Synthesis Example (C-1) but with complete Na exchange prior to XRD analysis, and Scanning Series C containing low LTA XRD scan of X zeolite indicating no detectable LTA fossils and also complete Na exchange prior to XRD analysis. Figure 2 illustrates the same comparative scan of Figure 1, but in which the Na-exchanged zeolite A reference scan is not shown and is at 1 〇χ magnification, so it is easier to observe the three groups that best indicate the presence of LTA zeolite (if present). LTA zeolite peak. 163742.doc -30·
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| JPS63260810A (en) * | 1988-03-18 | 1988-10-27 | Kanebo Ltd | Bactericidal zeolite composition and production thereof |
| AU7802198A (en) * | 1997-05-29 | 1998-12-30 | Exxon Chemical Patents Inc. | Preparation of zeolite-bound fau structure type zeolite and use thereof |
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| RU2273602C2 (en) * | 2000-11-03 | 2006-04-10 | Юоп Ллк | Uzm-5, uzm-5p, and uzm-6: crystalline aluminosilicate zeolites and processes involving them |
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