201028209 六、發明說明： 【發明所屬之技術領域】 本發明爲一種團聚的沸石吸附劑及其製備方法，具體 地說，是一種用於吸附分離芳烴異構物的吸附劑及其製備 方法。 【先前技術】 Φ 在具有多取代基的芳烴類化合物的生產過程中，由於 反應過程和反應熱力學平衡的限制，得到的往往是多種異 構物並存的混合產物，必須經過進一步的分離才能獲得其 中最有應用價値的異構物。然而這些異構物通常具有非常 接近的沸點，採用傳統的精餾方法很難加以分離。爲此， 工業上普遍採用選擇性吸附的方法來實現異構物之間的分 離。 吸附分離技術的原理是採用特定的吸附劑，利用其優 • 先吸附或優先不吸附目的產品的特性，並配合適當的方法 ’以從混合物料中分離、提純出目的產品。吸附劑是吸附 分離技術的基礎和核心。目前已知與鋇陽離子、鉀陽離子 ’單獨或混合，進行離子交換的X沸石具有優先吸附對位 芳烴異構物的特性。因此工業上廣泛使用Bax或BaKX作 爲吸附劑’並配合連續逆流模擬移動床技術，以從（：8芳 烴異構物中吸附分離出對二甲苯。高純度的對二甲苯係由 T歹!1方法得到：在吸附塔中，利用吸附劑優先吸附對二甲 苯的特性’經過反覆逆流質傳交換，使對二甲苯被吸附於 -5- 201028209 吸附劑中，使得對二甲苯濃度不斷增加；達到所需產品純 度後，再以解吸劑解吸出被吸附的對二甲苯；及精餾萃取 液以回收解吸劑。經由該法而生產的對二甲苯之純度可達 99.8質量％，且產率可達98質量％。此外，USP4940548 和USP 5 1 498 87還披露了此類吸附劑用於二乙基甲苯、甲 基苯酚等異構物的分離。 性能優良的吸附劑應具備以下三方面的性質··例如， 吸附能力高、吸附選擇性好、和質傳速率快。顯然，吸附 劑的吸附能力與其中的沸石含量成正比，即沸石含量越高 ，吸附劑的吸附能力越大。由於人工合成的沸石通常爲粉 末狀，需要加入一定量的黏結劑以將其聚結，才能滿足工 業應用的要求，因而導致部分吸附能力的損失。因此，減 少吸附劑中的惰性黏結劑用量，並儘量使其轉化成沸石， 成爲提高吸附劑性能的有效方法。USP 3 960 774最早公佈 了用氫氧化鈉水溶液處理含X或Y沸石和黏結劑的吸附 劑前體來提高吸附劑的結晶度，然後再與鋇和鉀陽離子進 行離子交換。 吸附劑的選擇性主要從交換離子種類和沸石性質方面 進行改善。USP3 997 620採用錁和鋇雙金屬離子交換以製 成SrBaX吸附劑，以提高對二甲苯的選擇性。USP4283587 將經過離子交換後的x或γ沸石再用烷基胺或烷基銨鹽 酸鹽處理，以提高其對位異構物的選擇性。CN 1 27 5 92 6 A 公開了 一種團聚的沸石吸附劑，其中使用Si/Al原子比爲 1〜1.15且二氧化矽含量低之X沸石爲原料製備吸附劑， -6- 201028209 並與鋇離子和鉀離子進行交換。該吸附劑中的可交換位址 被鋇離子佔據至少70%，被鉀離子佔據至多30% »所述吸 附劑採用高嶺土作爲黏結劑，且此吸附劑經鹼液處理以使 其當場結晶爲X沸石，如此以提高吸附劑的吸附能力。 爲了提高吸附劑的性能，除改善吸附劑的吸附能力和 選擇性外，還要提高吸附劑的質傳速率。CN 1 44 82 1 3A和 CN 1565718A分別採用晶粒爲0.5〜1.0微米或0.1〜0.4微 米的小晶粒X沸石爲吸附劑的活性組分，以提高吸附劑的 沸石的晶內質傳速率。 CN 1 3 5 8 5 66A公開了一種吸附劑及其製備方法，其中 藉由改善吸附劑的次級孔分佈來提高吸附劑的性能。該吸 附劑將X或Y沸石和黏結劑混合，於混合物中加入0.5〜 6.0質量％的擴孔劑，繼之混合均勻、加水模塑成型、乾 燥、活化、鹼處理、及離子交換，以製得吸附劑。所述的 黏結劑爲選自高嶺土、膨潤土、有機皂土（bent one)、矽溶 膠、鋁溶膠、和水玻璃中之一或多者。擴孔劑爲選自木質 素、纖維素鈉和田菁粉中之一或多者。 【發明內容】 本發明的目的是提供一種團聚的沸石吸附劑及其製備 方法。該吸附劑具有高吸附能力和快速的質傳速率。 本發明之團聚的沸石吸附劑包括95〜99.5質量％的X 沸石和0.5〜5 . 〇質量％的黏結劑。所述X沸石的可交換陽 離子位址爲ΠΑ族金屬和/或K所佔據。所述吸附劑採用壓 201028209 汞測孔法測定的總孔體積不小於〇·26毫升/克’其中孔徑 爲100〜500奈米的孔的體積佔總孔體積的至少60%。 根據本發明，在吸附劑製備過程中，在混合粉料中加 入成孔劑，以使轉晶後所得之團聚的沸石吸附劑富含晶間 堆積孔道，以壓汞測孔法測定的大孔比例高、孔體積大， 且具有良好的質傳性能，提高了吸附劑中沸石的利用率和 鹼處理過程中黏土的當場結晶程度，從而顯著地提高了吸 附劑的吸附能力’進而提高了單位質量吸附劑的生產能力 ，同時保持了良好的機械強度。 進行本發明之模式 須指明的是，本說明書和附隨的申請專利範圍中所用 的單數形（“一”、和“該”）均包含複數的指示對象，除非特 別指明。 根據本發明，將X沸石和可沸石化的黏土混合，其中 所述沸石NaX或NaKX與可沸石化的黏土之質量比爲88 〜95: 12〜5，且添加成型助劑，並在小球成型時加入成 孔劑，較佳爲成孔劑的水溶液，接著使成孔劑藉由煅燒分 解爲揮發性組分而去除。結果，使團聚的小球內部形成富 含孔道的系統，並使最終吸附劑以壓汞測孔法測得的孔體 積不小於0.26毫升/克，並且其中孔徑1〇〇〜500奈米的孔 的體積佔總孔體積的至少60%，而孔徑大於5 00奈米的孔 的體積佔總孔體積的5〜1 5 %，較佳是9〜1 5 %。所述吸附 劑的質傳性能良好，因而可明顯縮短達到吸附平衡的時間 201028209 ，提高吸附劑顆粒內部沸石的利用率。另外，由於團聚的 小球經過高溫煅燒，導致黏土的原有晶體結構被破壞，轉 變爲具有反應活性的無定形的矽酸鋁。在適當條件下經鹼 處理後，大部分之無定形的矽酸鋁會進一步轉化爲X沸石 ，因此可獲得包含至少95質量％ X沸石之團聚的吸附劑 顆粒。同時，鹼處理轉晶過程還使小球內部的沸石晶粒之 間形成更緊密的結合，以使吸附劑具有良好的機械強度。 φ 根據本發明，採用壓汞測孔法以測定吸附劑中具有一 定孔徑的大孔的比例和總孔體積。如壓汞測孔法所測定， 本發明之吸附劑的總孔體積較佳不小於0.28毫升/克，孔 徑爲100〜500奈米的孔的體積較佳爲總孔體積的至少 70%。 所述吸附劑中X沸石的可交換陽離子位址爲ΠΑ族金 屬及/或K所佔據，其中所述ΠΑ族金屬較佳爲鋇。當所述 的吸附劑中X沸石的陽離子爲Ba和K時，吸附劑中氧化 參 鋇與氧化鉀的莫耳比爲20〜60，較佳爲30〜50。吸附劑 中的氧化鈉含量應不大於1.0質量％，較佳不大於0.6質 量％。吸附劑的水含量以600 °C煅燒2小時後的灼燒減量 表示。一般控制吸附劑的灼燒減量不大於7.0質量％，較 佳的灼燒減量爲4.0〜6.0質量％。 爲增加吸附劑的質傳速率，本發明所述吸附劑選自小 晶粒的X沸石，其平均晶粒粒徑爲0.1〜2.0微米，較佳 爲0.2〜1.0微米。 所述吸附劑中的黏結劑爲高嶺土族礦物經當場結晶後 -9- 201028209 殘留之未晶化的基質，其中所述的高嶺土族礦物爲高嶺石 、地開石、珍珠石、埃洛石或它們的混合物。 本發明提供一種製備吸附劑的方法，其包括下列步驟 (1 )將沸石NaX或NaKX與可沸石化的黏土和成型 助劑混合製成混合粉料，其中所述沸石NaX或NaKX與可 沸石化的黏土之質量比爲88〜95: 12〜5，在該混合粉料 中加入作爲成孔劑之水溶性碳酸鹽或水溶性聚合物化合物 以使之藉由翻滾而團聚成小球，然後乾燥和煅燒； (2 )將步驟（1 )之烟燒後的小球用氫氧化鈉溶液或 氫氧化鈉與矽酸鈉的混合溶液在90〜100。(：下處理，使其 中的黏土當場結晶爲X沸石，然後乾燥和煅燒； (3)使步驟（2)所得產物與ΠΑ族金屬的可溶性鹽 溶液或者與鉀鹽和ΠΑ族金屬的可溶性鹽的混合溶液進行 陽離子交換，繼之進行活化。 所述方法中，步驟（1)係用於成型吸附劑。將NaX 或NaKX沸石與可沸石化的黏土按預定的比例混合，並加 入成型助劑，以形成混合粉料，再使得到的混合粉料進行 翻滾成型。翻滾成型所用的設備可爲轉盤、糖衣鍋或滾筒 。成型時，將混合粉料放入轉動設備中，邊翻滾邊向混合 粉料中噴灑水，使粉料逐漸黏附團聚成小球並長大。翻滾 成型至一定粒徑的小球後，將小球從成型設備中取出，然 後將其篩分，取粒徑爲0_2〜1·5毫米，較佳粒徑爲0.35〜 〇.8〇毫米的小球，乾燥和煅燒後，製得成型小球。 -10- 201028209 步驟（1)中之可沸石化的黏土較佳爲高嶺土族礦物 。所述的高嶺土族礦物較佳爲高嶺石、地開石、珍珠石、 埃洛石或它們的混合物。 所述的成型助劑較佳爲選自木質素、田菁粉、乾源粉 、羧甲基纖維素、活性炭中之一或多種化合物。加入的成 型助劑的質量與所述的沸石NaX或NaKX和黏結劑的總質 量之比爲1〜8 %，較佳爲2〜5 %。 • 步驟（1 )中的成孔劑係選自水溶性碳酸鹽或水溶性 聚合物化合物’而其在煅燒過程中以揮發性組分的形態從 吸附劑中脫除。所述的水溶性碳酸鹽較佳爲碳酸銨、碳酸 鈉或碳酸氫鈉。所述的水溶性聚合物化合物較佳爲一或多 種選自聚丙烯醯胺、聚乙烯醇和聚乙二醇之化合物。步驟 (1 )中較佳使用成孔劑的水溶液。所述成孔劑的水溶液 的濃度爲0.5〜10.0質量％，較佳爲1.〇〜8.0質量％。翻滾 成型時’較佳以由成孔劑配成的水溶液代替水向混合粉料 • 中噴灑，加入的成孔劑的水溶液爲混合粉料的總質量的10 〜4 0 %，較佳爲2 0〜3 0 %。 所述方法中，步驟（2)是將步驟（1)成型煅燒後的 小球進行鹼處理，以使其中的可沸石化的黏土當場結晶生 成X沸石。當場結晶處理時，液/固體積比爲1.2〜2.0:1 。當場結晶處理所用鹼液係選自氫氧化鈉溶液、或氫氧化 鈉與矽酸鈉的混合溶液。當鹼處理所用的鹼液爲氫氧化鈉 溶液時，其濃度較佳爲1.0〜4.0莫耳/升；當鹼處理所用 的鹼液爲氫氧化鈉與矽酸鈉的混合溶液時，該混合溶液中 -11 - 201028209 氧化鈉含量爲3.0〜8.0質量％，二氧化矽含量爲1.0〜7.0 質量％。當場結晶的處理時間較佳爲3〜1 〇小時。當場結 晶後將所得小球進行乾燥和煅燒。 步驟（1)和步驟（2)中的乾燥溫度較佳爲60〜 120°C，乾燥時間較佳爲4〜12小時。煅燒溫度較佳爲500 〜70 0 °C，煅燒時間較佳爲2〜6小時。 所述方法中，步驟（3 )是將當場結晶後的小球進行 陽離子交換，使其中的X沸石的陽離子位址轉化爲ΠΑ族 金屬和/或K。如此，以調變沸石晶體間隙內的靜電場性質 ，增大吸附選擇性。所述的陽離子交換可以在釜狀或柱狀 容器中進行，較佳爲在交換柱中以連續方式進行交換。交 換溫度較佳爲60〜160°C，更佳爲90〜100°C，交換液的體 積空間速率爲1.0〜12.0時較佳爲2.0〜6.0時·1。交換 時間爲5〜4 0小時，較佳爲1 〇〜2 0小時。交換液中的陽 離子與沸石中鈉離子之莫耳比，即交換比爲1.5〜5.0。當 所欲的是同時含有ΠΑ族金屬和鉀的吸附劑時，用鉀鹽和 EA族金屬的可溶性鹽的混合溶液進行陽離子交換。或者 ，也可先用ΠΑ族金屬的可溶性鹽溶液進行交換，再用鉀 鹽溶液進行鉀交換。經陽離子交換後的小球在活化之前需 先經洗滌以除去游離金屬離子。所述的活化較佳在流動的 空氣或氮氣中進行以脫除吸附劑中的水分。活化溫度較佳 爲180〜250 °C，時間較佳爲2〜12小時。 離子交換所用的ΠΑ族金屬的可溶性鹽較佳爲鋇的可 溶性鹽，例如硝酸鋇或氯化鋇。離子交換用於的鉀鹽較佳 -12- 201028209 爲氯化鉀或硝酸鉀。 所述吸附劑中X沸石的氧化矽-氧化鋁比，即爲沸石 中之氧化矽與氧化鋁的莫耳比，應爲較低，如此以增加吸 附劑的吸附選擇性。所用X沸石的氧化矽-氧化鋁比較佳 爲 2.0〜2.4 。 製備本發明吸附劑所用的X沸石較佳爲小晶粒的X 沸石，其平均晶粒粒徑爲0.1〜1.0微米。製備小晶粒X φ 沸石的方法有多種，例如按CN 1 4483 3 8 A和EP960854A1 的方法製備。 本發明方法製備的吸附劑適合於用以分離芳烴異構物 之液相吸附分離方法。更具體言之，該吸附劑適合於從異 構物混合物中分離出具有對位二取代基的芳烴異構物，例 如，從鄰二甲苯、間二甲苯、對二甲苯和乙苯的混合物中 吸附分離出對二甲苯。也可用於二乙基苯的異構物、或二 乙基甲苯的異構物、或甲基苯酚的異構物之吸附分離。所 φ 述液相吸附分離可採用多柱串聯方式進行操作，也可利用 由旋轉閥或電磁閥組達成的模擬移動床方式進行操作。吸 附分離的操作壓力較佳爲0.5〜1.6 MPa，溫度較佳爲120 〜200〇C。 雖然本發明之體系將由上文所述之各個體系及對應之 說明和圖式加以描述，但是決不表示限制本發明的內容於 所述之各個體系中。反之，本發明包括爲本發明之各個體 系的精神和範圍所涵蓋之所有的替代、變化、和等同體。 下面經由實例進一步說明本發明，但本發明並不僅限 -13- 201028209 於此。 【實施方式】 實例中吸附劑中X沸石的含量和評價性能資料的測定 方法爲： 吸附劑中X沸石的含量係經由測定樣品在一定條件下 對甲苯的吸附能力來計算。測定條件爲：3 5 t恆溫水浴、 常壓下，攜帶甲苯蒸汽的氮氣通過吸附劑直至吸附飽和， 其中甲苯的相對壓力爲0.5 (相對壓力指在測試溫度下甲 苯分壓與甲苯飽和蒸汽壓的比値）；並設定當甲苯吸附能 力等於0.235克/克的樣品時，X沸石的含量定爲100質量 %。 吸附劑的機械強度以抗壓破碎率來表示，其測定方法 爲：取在空氣中自然飽和之適量的吸附劑，稱重後裝入底 端封閉的不鏽鋼筒內；在吸附劑上方安放與不鏽鋼筒配合 的圓柱頂針，然後放置在顆粒強度測定儀上，加壓至2 5 0 牛頓；卸壓後取出吸附劑，用0.3毫米的篩子篩分；將未 通過篩眼的小球稱重；過篩後所得樣品減少的量與加壓前 樣品的質量百分比即定義爲被測樣品的抗壓破碎率。破碎 率越低，表示樣品的強度越好。 吸附劑樣品的孔的體積和尺寸分佈係利用美國 Micromeritics 公司 Autopore 11-9220 型壓荥儀，採用 ASTM D4382-03 方法測定。 吸附劑的內擴散的質傳速率的測定方法爲：取3〜4 -14- 201028209 克經預先脫水活化並在氮氣下乾燥冷卻的吸附劑樣品， 於帶有磁力攪拌的平衡釜中，同時加入15毫升的鄰二 苯，將釜蓋密閉，於12 (TC下靜置4小時，使吸附劑被 二甲苯充分飽和。然後開啓磁力攪拌，迅速注入15毫 對二甲苯。開始計時，並立即提取少量平衡釜中的液體 品。用氣相色譜法分析其組成，以計算混合溶液中對二 苯的初始濃度Cp然後每間隔一段時間提取少量液體樣 φ 並分析其組成，以計算對二甲苯的對應濃度ct。繼續提 樣品，直至平衡釜中液體的組成不再發生變化，即達到 擴散平衡，此時溶液中對二甲苯的濃度記爲Cco。以取 時間t爲橫坐標，以（Co — Ct ) / ( Co - c„)爲縱坐標作 ，得到圖1所示的擴散曲線。由圖1可知，對二甲苯的 擴散過程分爲快、慢兩個階段，初始擴散速率較快，接 平衡後獷散速度明顯變慢。曲線在（c〇—ct)/(c0 — )=0 · 9的附近有一轉折點。爲了比較不同吸附劑樣品 0 間的質傳速率的差異，將（C。— Ct) / (C。- Coo) = 0.9 對應的擴散時間作爲衡量吸附劑質傳速率快慢的指標， 爲內擴散質傳速率。（Co — Ct) / (Co-Cd達到0.9所 的時間越短，表示樣品的質傳性能越好。例如，由圖1 示吸附劑A和B的擴散曲線計算求得吸附劑A的內擴 質傳速率爲tA，吸附劑B的內擴散質傳速率爲tB。當 小於tB時，表示吸附劑A的質傳性能優於吸附劑B。 實例1201028209 VI. Description of the Invention: [Technical Field] The present invention is an agglomerated zeolite adsorbent and a preparation method thereof, and more particularly, an adsorbent for adsorbing and separating an aromatic isomer and a preparation method thereof. [Prior Art] Φ In the production process of aromatic hydrocarbon compounds having multiple substituents, due to the limitation of the reaction process and the thermodynamic equilibrium of the reaction, a mixture of a plurality of isomers is often obtained, which must be further separated to obtain The most useful isomers. However, these isomers usually have very close boiling points and are difficult to separate using conventional rectification methods. For this reason, selective adsorption is commonly used in the industry to achieve separation between isomers. The principle of the adsorptive separation technique is to use a specific adsorbent, which utilizes the characteristics of the preferred adsorbent or preferentially adsorbs the product of the target, and cooperates with an appropriate method to separate and purify the desired product from the mixed material. Adsorbents are the foundation and core of adsorption separation technology. It is known that X zeolite which is ion-exchanged with ruthenium cations and potassium cations ‘alone or mixed has the property of preferentially adsorbing para-isomer isomers. Therefore, Bax or BaKX is widely used in the industry as an adsorbent' and combined with continuous countercurrent simulated moving bed technology to separate and separate para-xylene from (8-arene isomers). High-purity p-xylene is from T歹!1 The method obtains: in the adsorption tower, the adsorption characteristic of the p-xylene is preferentially adsorbed by the adsorbent. After the reverse countercurrent mass transfer, the para-xylene is adsorbed in the adsorbent of -5 - 201028209, so that the concentration of p-xylene is continuously increased; After the desired product purity, the adsorbed para-xylene is desorbed by the desorbent; and the rectification extract is used to recover the desorbent. The purity of the para-xylene produced by the method can reach 99.8% by mass, and the yield can be obtained. In addition, USP 4,940,548 and USP 5 1 498 87 disclose the use of such adsorbents for the separation of isomers such as diethyltoluene and methylphenol. The adsorbent having excellent properties should have the following three properties. · · For example, high adsorption capacity, good adsorption selectivity, and fast mass transfer rate. Obviously, the adsorption capacity of the adsorbent is proportional to the zeolite content, that is, the higher the zeolite content, the adsorption of the adsorbent The greater the ability to attach. Since the synthetic zeolite is usually in the form of a powder, it is necessary to add a certain amount of binder to coalesce it to meet the requirements of industrial applications, thus causing a loss of partial adsorption capacity. Therefore, reducing the amount of adsorbent The amount of inert binder and its conversion to zeolite is an effective method to improve the performance of the adsorbent. USP 3 960 774 first announced the treatment of adsorbent precursors containing X or Y zeolite and binder with aqueous sodium hydroxide to improve The crystallinity of the adsorbent is then ion exchanged with the lanthanum and potassium cations. The selectivity of the adsorbent is mainly improved in terms of exchange ion species and zeolite properties. USP3 997 620 uses ruthenium and osmium bimetallic ion exchange to make SrBaX adsorption. To increase the selectivity of para-xylene. USP 4283587 The ion-exchanged x or gamma zeolite is treated with an alkylamine or alkylammonium hydrochloride to increase the selectivity of its para-isomer. CN 1 27 5 92 6 A discloses an agglomerated zeolite adsorbent in which X zeolite having a Si/Al atomic ratio of 1 to 1.15 and a low ceria content is used as a raw material. Adsorbent, -6- 201028209 and exchanged with cesium and potassium ions. The exchangeable sites in the sorbent occupy at least 70% by cesium ions and up to 30% by potassium ions. »The adsorbent uses kaolin as a bond. And the adsorbent is treated with an alkali solution to crystallize it as X zeolite in the field, so as to improve the adsorption capacity of the adsorbent. In order to improve the performance of the adsorbent, in addition to improving the adsorption capacity and selectivity of the adsorbent, it is also required to be improved. The mass transfer rate of the adsorbent. CN 1 44 82 1 3A and CN 1565718A respectively use small-grain X zeolite with crystal grains of 0.5-1.0 μm or 0.1-0.4 μm as the active component of the adsorbent to enhance the zeolite of the adsorbent. The rate of intragranular mass transfer. CN 1 3 5 8 5 66A discloses an adsorbent and a process for the preparation thereof, wherein the performance of the adsorbent is improved by improving the secondary pore distribution of the adsorbent. The adsorbent mixes the X or Y zeolite and the binder, and adds 0.5 to 6.0% by mass of a pore-expanding agent to the mixture, followed by uniform mixing, water molding, drying, activation, alkali treatment, and ion exchange. Get the adsorbent. The binder is one or more selected from the group consisting of kaolin, bentonite, bent one, enamel, aluminum sol, and water glass. The pore-expanding agent is one or more selected from the group consisting of lignin, cellulose sodium and phthalocyanine powder. SUMMARY OF THE INVENTION An object of the present invention is to provide an agglomerated zeolite adsorbent and a process for the preparation thereof. The adsorbent has high adsorption capacity and fast mass transfer rate. The agglomerated zeolite adsorbent of the present invention comprises 95 to 99.5% by mass of X zeolite and 0.5 to 5% by mass of a binder. The exchangeable cation address of the X zeolite is occupied by a lanthanide metal and/or K. The adsorbent has a total pore volume of not less than 〇26 ml/g as measured by a mercury porosimetry method of 201028209. The volume of the pores having a pore diameter of 100 to 500 nm accounts for at least 60% of the total pore volume. According to the present invention, a porogen is added to the mixed powder during the preparation of the adsorbent, so that the agglomerated zeolite adsorbent obtained after the crystal transformation is rich in intergranular pores, and the macropores are determined by mercury intrusion porosimetry. High ratio, large pore volume, and good mass transfer performance, improve the utilization of zeolite in the adsorbent and the degree of on-site crystallization of clay during alkali treatment, thereby significantly improving the adsorption capacity of the adsorbent' and thus increasing the unit. The production capacity of the mass adsorbent while maintaining good mechanical strength. Modes for Carrying Out the Invention It is to be understood that the singular forms ""","," According to the invention, X zeolite and zeolitic clay are mixed, wherein the mass ratio of the zeolite NaX or NaKX to the zeolitic clay is 88 to 95: 12 to 5, and a molding aid is added and the pellet is added A pore former, preferably an aqueous solution of a pore former, is added during molding, and then the pore former is removed by calcination to a volatile component. As a result, a system rich in pores is formed inside the agglomerated pellets, and the pore volume of the final adsorbent measured by mercury intrusion porosimetry is not less than 0.26 ml/g, and pores having a pore diameter of 1 〇〇 500 500 nm. The volume accounts for at least 60% of the total pore volume, and the pores having a pore diameter of more than 500 nm account for 5 to 15%, preferably 9 to 15%, of the total pore volume. The mass transfer performance of the adsorbent is good, so that the time to reach the adsorption equilibrium can be significantly shortened 201028209, and the utilization rate of the zeolite inside the adsorbent particles is improved. In addition, since the agglomerated pellets are calcined at a high temperature, the original crystal structure of the clay is destroyed and converted into a reactive amorphous aluminum niobate. After alkali treatment under appropriate conditions, most of the amorphous aluminum ruthenate is further converted into X zeolite, and thus agglomerated sorbent particles containing at least 95% by mass of X zeolite can be obtained. At the same time, the alkali treatment of the crystallizing process also forms a tighter bond between the zeolite grains inside the pellets, so that the adsorbent has good mechanical strength. φ According to the present invention, a mercury intrusion porosimetry method is employed to determine the ratio of the large pores having a certain pore diameter in the adsorbent and the total pore volume. The total pore volume of the adsorbent of the present invention is preferably not less than 0.28 ml/g as measured by mercury intrusion porosimetry, and the volume of pores having a pore diameter of from 100 to 500 nm is preferably at least 70% of the total pore volume. The exchangeable cation site of the X zeolite in the adsorbent is occupied by a lanthanum metal and/or K, wherein the lanthanum metal is preferably ruthenium. When the cation of the X zeolite in the adsorbent is Ba and K, the molar ratio of the oxidized cerium to the potassium oxide in the adsorbent is 20 to 60, preferably 30 to 50. The content of sodium oxide in the adsorbent should be not more than 1.0% by mass, preferably not more than 0.6% by mass. The water content of the adsorbent is expressed by the ignition loss after calcination at 600 °C for 2 hours. Generally, the ignition loss of the adsorbent is controlled to be not more than 7.0% by mass, and the preferable ignition loss is 4.0 to 6.0% by mass. In order to increase the mass transfer rate of the adsorbent, the adsorbent of the present invention is selected from the group consisting of small-grain X zeolite having an average crystal grain size of 0.1 to 2.0 μm, preferably 0.2 to 1.0 μm. The binder in the adsorbent is an uncrystallized matrix remaining after the kaolinite mineral is crystallized on the spot, -9-201028209, wherein the kaolinite mineral is kaolinite, dickite, pearlite, halloysite or a mixture of them. The present invention provides a process for preparing an adsorbent comprising the steps of (1) mixing zeolite NaX or NaKX with a zyzable clay and a forming aid to form a mixed powder, wherein the zeolite NaX or NaKX is zeolifiable The mass ratio of the clay is 88 to 95: 12 to 5, and a water-soluble carbonate or water-soluble polymer compound as a pore former is added to the mixed powder to be agglomerated into small balls by tumbling, and then dried. And calcination; (2) The pellet of the calcined step (1) is prepared by using a sodium hydroxide solution or a mixed solution of sodium hydroxide and sodium citrate at 90 to 100. (: treatment under the condition that the clay therein is crystallized as X zeolite in the field, and then dried and calcined; (3) the soluble salt solution of the product obtained in the step (2) and the lanthanum metal or the soluble salt of the potassium salt and the lanthanum metal The mixed solution is subjected to cation exchange, followed by activation. In the method, the step (1) is used to form the adsorbent. The NaX or NaKX zeolite is mixed with the zeparable clay in a predetermined ratio, and a molding aid is added. In order to form a mixed powder, the obtained mixed powder is subjected to roll forming. The equipment used for the roll forming may be a turntable, a sugar-coated pan or a drum. When molding, the mixed powder is placed in a rotating device, and the mixed powder is turned to the mixed powder. The water is sprayed in the material to gradually agglomerate the powder into small balls and grow up. After rolling to form a small ball of a certain particle size, the small ball is taken out from the molding equipment, and then sieved to obtain a particle size of 0_2~1. · 5 mm, preferably a pellet having a particle diameter of 0.35 to 〇.8 mm, after drying and calcining, to obtain a shaped pellet. -10- 201028209 The zeolitic clay in the step (1) is preferably kaolin. Family minerals. The kaolinite mineral is preferably kaolinite, dickite, perlite, halloysite or a mixture thereof. The forming aid is preferably selected from the group consisting of lignin, tianjing powder, dry source powder, and carboxymethyl. One or more compounds of the base cellulose and the activated carbon. The ratio of the mass of the forming aid to be added to the total mass of the zeolite NaX or NaKX and the binder is from 1 to 8%, preferably from 2 to 5%. The pore former in the step (1) is selected from a water-soluble carbonate or a water-soluble polymer compound' which is removed from the adsorbent in the form of a volatile component during calcination. Preferably, it is ammonium carbonate, sodium carbonate or sodium hydrogencarbonate. The water-soluble polymer compound is preferably one or more compounds selected from the group consisting of polyacrylamide, polyvinyl alcohol and polyethylene glycol. Preferably, the aqueous solution of the pore former is used. The concentration of the aqueous solution of the pore former is from 0.5 to 10.0% by mass, preferably from 1. to 8.0% by mass, and preferably in the form of a pore former. Instead of water, spray into the mixed powder. • Add water to the porogen. The liquid is 10 to 40%, preferably 20 to 30%, of the total mass of the mixed powder. In the method, the step (2) is to alkali treat the pellet after the step (1) is calcined. In order to crystallize the zeolitic clay in the field to form X zeolite. The liquid/solid ratio is 1.2~2.0:1 in the field crystallization treatment. The lye used in the field crystallization treatment is selected from sodium hydroxide solution or sodium hydroxide. a mixed solution with sodium citrate. When the alkali solution used for the alkali treatment is a sodium hydroxide solution, the concentration thereof is preferably 1.0 to 4.0 mol/liter; when the alkali solution is used, the alkali solution is sodium hydroxide and sodium citrate. In the mixed solution, the mixed solution has a sodium oxide content of 3.0 to 8.0% by mass and a ceria content of 1.0 to 7.0% by mass. The treatment time for the crystallization on the spot is preferably 3 to 1 hr. The resulting pellets were dried and calcined after crystallization on the spot. The drying temperature in the step (1) and the step (2) is preferably from 60 to 120 ° C, and the drying time is preferably from 4 to 12 hours. The calcination temperature is preferably from 500 to 70 ° C, and the calcination time is preferably from 2 to 6 hours. In the method, the step (3) is to carry out cation exchange of the crystallization balls on the spot, and convert the cation sites of the X zeolite therein into lanthanum metals and/or K. Thus, the adsorption field selectivity is increased by modulating the electrostatic field properties in the intercrystalline zeolite crystal gap. The cation exchange can be carried out in a kettle or column vessel, preferably in a continuous manner in an exchange column. The exchange temperature is preferably from 60 to 160 ° C, more preferably from 90 to 100 ° C, and the volume ratio of the exchange liquid is from 1.0 to 12.0, preferably from 2.0 to 6.0 hr. The exchange time is 5 to 40 hours, preferably 1 to 2 hours. The molar ratio of the cation in the exchange liquid to the sodium ion in the zeolite, i.e., the exchange ratio is 1.5 to 5.0. When an adsorbent containing both a lanthanide metal and potassium is desired, cation exchange is carried out using a mixed solution of a potassium salt and a soluble salt of an EA metal. Alternatively, it may be exchanged with a soluble salt solution of a lanthanum metal, followed by potassium exchange with a potassium salt solution. The cation exchanged pellets are washed prior to activation to remove free metal ions. The activation is preferably carried out in flowing air or nitrogen to remove moisture from the adsorbent. The activation temperature is preferably from 180 to 250 ° C, and the time is preferably from 2 to 12 hours. The soluble salt of the lanthanum metal used for ion exchange is preferably a soluble salt of cerium, such as cerium nitrate or cerium chloride. The potassium salt used for ion exchange is preferably -12- 201028209 is potassium chloride or potassium nitrate. The cerium oxide-alumina ratio of X zeolite in the adsorbent, i.e., the molar ratio of cerium oxide to alumina in the zeolite, should be low to increase the adsorption selectivity of the adsorbent. The cerium oxide-alumina of the X zeolite used is preferably 2.0 to 2.4. The X zeolite used in the preparation of the adsorbent of the present invention is preferably a small crystallite X zeolite having an average crystal grain size of 0.1 to 1.0 μm. There are various methods for preparing small-grain X φ zeolite, for example, according to the methods of CN 1 4483 3 8 A and EP 960854 A1. The adsorbent prepared by the process of the present invention is suitable for a liquid phase adsorption separation process for separating aromatic isomers. More specifically, the adsorbent is suitable for separating an aromatic isomer having a paradisubstituted group from a mixture of isomers, for example, from a mixture of o-xylene, m-xylene, p-xylene, and ethylbenzene. Adsorption separation of p-xylene. It can also be used for the adsorption separation of an isomer of diethylbenzene or an isomer of diethyltoluene or an isomer of methylphenol. The liquid phase adsorption separation of φ can be operated by a multi-column series method, or by a simulated moving bed method by a rotary valve or a solenoid valve group. The operating pressure for the adsorption separation is preferably from 0.5 to 1.6 MPa, and the temperature is preferably from 120 to 200 〇C. Although the system of the present invention will be described in terms of the various systems described above and the corresponding description and drawings, it is not intended to limit the scope of the invention in the various systems described. Rather, the invention is to cover all alternatives, modifications, and equivalents of the embodiments of the invention. The invention is further illustrated by the following examples, but the invention is not limited thereto -13-201028209. [Embodiment] The content of X zeolite in the adsorbent and the evaluation property data in the examples are as follows: The content of X zeolite in the adsorbent is calculated by measuring the adsorption capacity of the sample to toluene under certain conditions. The measurement conditions are as follows: 3 5 t constant temperature water bath, under normal pressure, the nitrogen carrying toluene vapor passes through the adsorbent until the adsorption is saturated, wherein the relative pressure of toluene is 0.5 (relative pressure refers to the partial pressure of toluene and the saturated vapor pressure of toluene at the test temperature) When the sample having a toluene adsorption capacity equal to 0.235 g/g was set, the content of the X zeolite was set to 100% by mass. The mechanical strength of the adsorbent is expressed by the crushing resistance of the crushing agent. The measuring method is as follows: taking an appropriate amount of adsorbent naturally saturated in the air, weighing it into a stainless steel cylinder closed at the bottom end; placing the stainless steel above the adsorbent The cylindrical thimble with the barrel is placed on the particle strength tester and pressurized to 250 ton; after the pressure is released, the adsorbent is taken out and sieved with a 0.3 mm sieve; the small ball that has not passed through the mesh is weighed; The amount of reduction of the sample obtained after sieving and the mass percentage of the sample before pressurization are defined as the crush breaking rate of the sample to be tested. The lower the breaking rate, the better the strength of the sample. The volume and size distribution of the pores of the adsorbent sample was determined by the American Micromeritics Autopore Model 11-9220 pressure gauge using the ASTM D4382-03 method. The mass transfer rate of the internal diffusion of the adsorbent is determined by taking 3~4 -14-201028209 grams of the adsorbent sample which is pre-dehydrated and dried under nitrogen, and is cooled in a balanced kettle with magnetic stirring. 15 ml of o-diphenyl, the lid was sealed, and allowed to stand at 12 (TC for 4 hours) to fully saturate the adsorbent by xylene. Then magnetic stirring was started, and 15 milli-xylene was quickly injected. The timing was started and immediately extracted. A small amount of liquid in the equilibrium tank. The composition was analyzed by gas chromatography to calculate the initial concentration of p-diphenyl in the mixed solution Cp and then a small amount of liquid sample φ was taken at intervals and the composition was analyzed to calculate the paraxylene. Corresponding to the concentration ct. Continue to take the sample until the composition of the liquid in the equilibrium tank no longer changes, that is, reach the diffusion equilibrium. At this time, the concentration of p-xylene in the solution is recorded as Cco. Take the time t as the abscissa to (Co- Ct) / (Co - c„) is plotted on the ordinate to obtain the diffusion curve shown in Figure 1. As can be seen from Figure 1, the diffusion process of para-xylene is divided into two stages, fast and slow, and the initial diffusion rate is faster. After the equilibrium, the dispersing speed is obviously slower. The curve has a turning point near (c〇-ct)/(c0 — )=0 · 9. In order to compare the difference in mass transfer rate between different adsorbent samples, (C —Ct) / (C.- Coo) = 0.9 The corresponding diffusion time is used as an index to measure the rate of mass transfer of the adsorbent, which is the rate of endogenous mass transfer. (Co — Ct) / (Co-Cd reaches 0.9 time) The shorter, the better the mass transfer performance of the sample. For example, the diffusion rate of adsorbent A is calculated from the diffusion curves of adsorbents A and B in Figure 1 to determine the internal diffusion rate of adsorbent A as tA, and the internal diffusion mass transfer rate of adsorbent B. It is tB. When it is less than tB, it means that the mass transfer performance of adsorbent A is better than that of adsorbent B. Example 1
置 甲 鄰 升 樣 甲 品 取 了 樣 圖 內 近 之 之 稱 需 所 散 t A 15- 201028209 製備本發明吸附劑並測試其吸附性能。 (1 )小晶粒X沸石之製備： 在100公升合成釜中加入16.4公斤偏鋁酸鈉溶液（ 其中Al2〇3的含量爲17.3質量％，Na20的含量爲21.0質 量％) 、11.0公斤去離子水和2.9公斤氫氧化鈉。攪拌使 固體鹼完全溶解，然後加入11.8公斤矽酸鈉溶液（其中 Si〇2的含量爲28.3質量％，Na20的含量爲8.8質量％ )。 攪拌混合物至均勻，並在2 5 °C下靜置使老化20小時，得 導向劑（guiding agent)。 在25°C下，於2000公升釜中加入25 5公斤矽酸鈉溶 液、1001公斤去離子水、和37公斤氫氧化鈉，攪拌使之 充分混合。並在攪拌下加入227公斤偏鋁酸鈉，然後加入 B公斤的導向劑。繼續攪拌至得均勻混合物。升溫至 1 〇〇°C，靜置使結晶4小時。產物經水洗至洗滌液的pH値 小於10。過濾產物，接著在8(TC下乾燥12小時，得到 NaX沸石。由單位晶胞常數計算得到該沸石的Si02/Al203 莫耳比爲2.19,以掃描式電子顯微鏡觀測得其平均晶粒粒 徑爲0.7微米。 (2 )翻滾成型·· 將88公斤（以乾重爲基準，以下同）步驟（1)中製 備的NaX沸石與9公斤高嶺土（高嶺石的含量爲90質量 %’中國山西臨汾產）和3.4公斤田菁粉混合均勻形成混 -16- 201028209 合粉料。將混合粉料放入轉盤中。邊翻滾邊將適量之濃度 爲5·〇質量％的碳酸鈉水溶液噴灑在混合粉料上，以使固 體混合粉料黏附團聚成小球。翻滾時噴灑的碳酸鈉水溶液 的量爲固體混合粉料的25質量％。篩取粒徑爲0.35〜0.80 毫米的小球，在8〇t：下乾燥1〇小時，在54(TC空氣流中煅 燒4小時。 • ( 3 )當場結晶： 將上述煅燒後的小球按液/固體積比2.0 : 1的比例， 用1.5 m〇L/L的氫氧化鈉溶液處理，並在96°C下靜置4.0 小時’以使其中的高嶺土當場結晶成X沸石。當場結晶後 所得的小球用去離子水洗滌至洗滌液pH値爲9.0。在 80 °C下乾燥12小時，並在500 °C下煅燒2小時，其甲苯吸 附能力爲0.225克/克，相當於團聚的小球中之X沸石的 含量爲95.7質量％。 (4)離子交換： 取當場結晶並煅燒後的小球，用慣用的交換柱連續進 行離子交換，交換液爲0.18 moL/L的硝酸鋇溶液。在 92 °C和常壓下進行鋇離子交換10小時，交換液的體積空 間速率4.0時〃。所用硝酸鋇溶液與小球的體積比爲40 : 1 。交換完成後，用1 〇倍於小球體積的去離子水洗滌小球 ，在220°C氮氣流中乾燥6小時，製得吸附劑A-1。600°C 煅燒2小時後，測定其灼燒減量爲4.3質量％，吸附劑的 -17- 201028209 組成、由壓汞測孔法測得的孔的體積和尺寸分佈、及其匕 物理性質示於表1。 實例2 按實例1的方法製備吸附劑’不同的是··步驟（2) 之翻滾成型中，5.0質量％的碳酸銨水溶液的噴灑量爲固 體混合粉料的28質量％ ;於步驟（3 )中’將煅燒後小球 用氫氧化鈉和矽酸鈉的混合溶液處理以進行當場結晶’其 中該混合溶液包含4.3質量％的Na20和2.1質量％的Si〇2 ，當場結晶後所得團聚的小球之甲苯吸附能力爲〇.230克/ 克，相當於團聚的小球中之X沸石的含量爲9 7.9質量％。 離子交換並活化後得到的吸附劑A-2，在600 °C煅燒2小 時後的灼燒減量爲4.5質量％。吸附劑的組成、由壓汞測 孔法測得的孔的體積和尺寸分佈、及其它物理性質示於表 實例3 按實例1的方法製備吸附劑，不同的是：步驟（2) 中，將63公斤實例1製備的NaX沸石與5.4公斤高嶺土 和2.7公斤羧甲基纖維素（購自中國山東青州清泉纖維素 廠）混合均句。將混合物放入轉盤中，邊翻滾邊噴灑適量 之濃度爲2_0質量％的聚丙烯醯胺（購自中國上海恆暗創 新醯胺有限公司）的水溶液’以使固體混合粉料黏附團聚 成小球。翻<滾時噴灑的聚丙烯醯胺水溶液的量爲固體混合 -18- 201028209 粉料的20質量％。然後按照實例丨所述的後續步驟進行乾 燥、煅燒、及當場結晶。測定當場結晶後所得小球的甲苯 吸附能力爲0.226克/克，相當於團聚小球中之X沸石的 含量爲96_2質量％。 將當場結晶後的小球按實例1步驟（4 )的方法用硝 酸鋇溶液進行離子交換，不同的是：離子交換後經水洗的 小球在200 °C氮氣流中乾燥6小時，製得吸附劑A-3，測 定其在600°C煅燒2小時後的灼燒減量爲5.6質量％。吸附 劑的組成、由壓汞測孔法測得的孔的體積和尺寸分佈 '及 其它物理性質示於表1。 實例4 按實例1的方法製備吸附劑，不同的是：步驟（2) 中，將63公斤實例1製備的NaX沸石與5.4公斤高嶺土 和2.7公斤羧甲基纖維素混合均句。將混合物放入轉盤中 ’邊翻滾邊噴灑適量之濃度爲2.0質量％的聚乙烯醇（購 自上海邵榮貿易有限公司）的水溶液，以使固體混合粉料 黏附團聚成小球。翻滾時噴灑的聚乙烯醇水溶液的量爲固 體混合粉料的22質量％。然後按照實例1所述的後續步驟 進行乾燥、煅燒、及當場結晶。測定當場結晶後所得小球 的甲苯吸附能力爲0.224克/克，相當於團聚小球中之X 沸石的含量爲95.3質量％。 將當場結晶後的小球按實例1步驟（4 )的方法用硝 酸鋇溶液進行離子交換，不同的是：離子交換後經水洗的 -19- 201028209 小球在20(TC氮氣流中乾燥6小時，製得吸附劑A-4，測 定其在600°C煅燒2小時後的灼燒減量爲5.3質量％。吸附 劑的組成、由壓汞測孔法測得的孔的體積和尺寸分佈、及 其它物理性質示於表1。 實例5 按EP 0960854A1所述的方法製備NaKX沸石。在100 公升合成釜中加入5.5公斤偏鋁酸鈉溶液（其中Al2〇3的 含量爲17.3質量％，Na20的含量爲21.0質量％) 、12.6 公斤去離子水和7.4公斤氫氧化鈉。攪拌使固體鹼完全溶 解，然後加入19.6公斤矽酸鈉溶液（其中Si02的含量爲 28.3質量％，Na20的含量爲8.8質量％)。攪拌混合物至 均句。混合物在40°C下靜置使老化1.0小時，製得導向劑 。40 °C下，在.2 000公升釜中加入198公斤矽酸鈉溶液、 660公斤去離子水、90公斤氫氧化鈉和105公斤氫氧化鉀 ，攪拌使之充分混合。並在攪拌下加入288公斤偏鋁酸鈉 ，然後加入3公斤的導向劑》繼續攪拌至得均勻混合物。 混合物在40°C下以250 U/分鐘攪拌老化4小時。接著使混 合物升溫至70 °C，靜置使結晶4小時。產物經水洗至洗滌 液pH値小於1 0。過濾產物，在7 0 °C下乾燥12小時，得 到NaKX沸石。由晶胞常數計算沸石的Si02/Al203莫耳比 爲2.03，以掃描式電子顯微鏡觀測得其平均晶粒粒徑爲 〇.4微米。 將75公斤NaKX沸石、8.3公斤高嶺土和3.0公斤羧 201028209 甲基纖維素混合均勻製成混合粉料。將混合粉料放入轉盤 中，邊翻滾邊噴灑濃度爲5.0質量％的碳酸錢水溶液，以 使固體混合粉料黏附團聚成小球。翻滾時噴灑的碳酸銨水 溶液的量爲固體混合粉料的27質量％。然後按照實例1所 述的後續步驟進行乾燥、煅燒、和當場結晶。測定當場結 晶後所得小球的甲苯吸附能力爲0.228克/克，相當於團聚 小球中之X沸石的含量爲9 7 · 0質量％。 Φ 將當場結晶後的小球按實例1步驟（4)的方法用硝 酸鋇溶液進行離子交換，不同的是··離子交換後經水洗的 小球在2 3 0 °C氮氣流中乾燥4小時，製得吸附劑a-5，測 定其在600 °C煅燒2小時後的灼燒減量爲4.2質量％。吸附 劑的組成、由壓汞測孔法測得的孔的體積和尺寸分佈、及 其它物理性質示於表1。 實例6 φ 按實例5的方法製備吸附劑，不同的是：當場結晶後 得到的小球用氯化鉀和硝酸鋇的混合溶液作爲交換液以進 行離子交換，其中K+離子濃度爲〇.1莫耳/升，Ba2 +離子 濃度爲0.20莫耳/升。離子交換時，所消耗的交換液與固 體小球的體積比爲40 : 1。製得的吸附劑A-6中之氧化鉀 的含量爲〇· 75質量％，氧化鋇的含量爲45質量％。吸附劑 A-6中之氧化鋇與氧化鉀的莫耳比爲36.8。吸附劑A-6在 6 0 01：煅燒2小時後測得的灼燒減量爲4.8質量％。吸附劑 的組成、由壓汞測孔法測得的孔的體積和尺寸分佈、及其 -21 - 201028209 它物理性質示於表1。 比較例1 將7〇公斤實例1製備的NaX沸石與7公斤高嶺土混 合均勻。將混合物放入轉盤中，邊翻滾邊噴灑適量的去離 子水，以使固體粉料黏附團聚成小球。翻滾時噴灑的水量 爲固體粉料的30質量％。篩取0.35〜0.80毫米的小球’ 使這些小球於8 0 °C下乾燥1 〇小時，在5 4 0。(：空氣流中煅燒 4小時。再將煅燒後小球用氫氧化鈉和矽酸鈉的混合溶液 處理以進行當場結晶，其中該混合溶液包含4.3質量°/。的 Na20和2.1質量％的Si02。當場結晶後，所得的小球用去 離子水洗滌至洗滌液pH値爲9.0。接著小球於80°C下乾 燥12小時，於500°C下煅燒2小時。得到的團聚小球之甲 苯吸附能力爲0.219克/克，相當於團聚小球中之X沸石 的含量爲93.2質量％。 將當場結晶處理後得到的團聚小球按實例1步驟（4 )的方法進行離子交換和乾燥脫水，得比較吸附劑B-1。 測定其在6 0 0 °C煅燒2小時後的灼燒減量爲4.7質量％。吸 附劑的組成、由壓汞測孔法測得的孔的體積和尺寸分佈、 及其它物理性質示於表1。 比較例2 將70公斤實例1製備的NaX沸石與7公斤高嶺土和 2.8公斤羧甲基纖維素混合均勻製成混合粉料。將混合粉 -22- 201028209 料放入轉盤中，邊翻滾邊噴灑適量的去離子水’使固體粉 料黏附團聚成小球。翻滾時噴灑的水量爲固體混合粉料的 32質量％。篩取0.35〜0.80毫米的小球。使這些小球於 下乾燥10小時，然後在540°C空氣流中煅燒4小時° 再將煅燒後小球用氫氧化鈉和矽酸鈉的混合溶液處理以進 行當場結晶，其中該混合溶液包含4.3質量％的NaaO和 2.1質量％的Si02。當場結晶後，所得的小球用去離子水 φ 洗滌至pH値爲9.0。小球於80°C下乾燥12小時’及於 5 0 0 °C下煅燒2小時。得到的團聚小球的甲苯吸附能力爲 0.223克/克，相當於團聚小球中之X沸石的含量爲95.7 質量％。 將當場結晶處理後得到的團聚的小球按實例1步驟（ 4 )的方法進行離子交換和乾燥脫水，得比較吸附劑B-2 ’ 測定其在600 °C锻燒2小時後的灼燒減量爲5 · 1質量％。吸 附劑的組成、由壓汞測孔法測得的孔的體積和尺寸分佈、 φ 及其它物理性質示於表1。 實例7 在連續逆流的小型模擬移動床上用吸附劑A-2進行吸 附分離對二甲苯的實驗。 所述小型模擬移動床包括24根串聯的吸附柱’其中 每根柱長195毫米’內徑30毫米。吸附劑的總裝塡量爲 3300毫升。如圖2所示，在串聯的24根吸附柱中之第— 根吸附柱和最後一根吸附柱係以循環泵連接而構成封閉的 -23 - 201028209 環路。圖2中，以輸入或輸出的四股物料，即吸附原料、 解吸劑、提取液、和提餘液’將24根吸附柱分成四個區 段。即，吸附原料（柱15)和提餘液（柱21)之間的7 根吸附柱爲吸附區；提取液（柱6)和吸附原料（柱14) 之間的9根吸附柱爲提純區；解吸劑（柱1)和提取液（ 柱5)之間的5根吸附柱爲解吸區；及提餘液（柱22)和 解吸劑（柱24 )之間的3根吸附柱爲緩衝區。整個吸附系 統的溫度控制在177 °C，壓力控制在〇.8 MPa。 操作過程中，分別將流速1420毫升/時的解吸劑對二 乙苯和流速1190毫升/時的吸附原料連續地注入上述模擬 移動床中，並以710毫升/時的流速將提取液自裝置中取出 ，及以1 900毫升/時的流速將提餘液自裝置中取出。所述 吸附原料包括9.3質量％乙苯、18.5質量％對二甲苯、45.4 質量％間二甲苯、17.4質量％鄰二甲苯、和9.4質量％非芳 烴組分。根據模擬逆流色譜的原理，當循環泵流量設定爲 4 5 80毫升/時，每隔70秒，四股物料位置按與液體流向相 同的方向前移1根吸附柱。在穩定的操作狀態下，得到的 對二甲苯純度爲99.75質量％，回產率爲99.0質量％。由此 計算得出的對二甲苯生產率爲每立方米吸附劑每小時 0.066米3之經吸附分離的對二甲苯。 實例8 在小型移動床裝置上裝塡吸附劑A-6，按實例7的方法 進行吸附分離對二甲苯的實驗。在穩定操作狀態下，得到 • 24- 201028209 的對二甲苯純度爲99.80質量％，回產率爲98.4質量％。對 二甲苯的生產率爲每立方米吸附劑每小時0.0656米3之經吸 附分離的對二甲苯。 比較例3 在小型移動床裝置上裝塡比較吸附劑B-2，按實例7的 方法進行吸附分離對二甲苯的實驗。在穩定操作狀態下， • ㈣_ 二甲苯純度爲99.71質量％，回產率爲90.5質量％ 。對二甲苯生產率爲每立方米吸附劑每小時0.060 4米3之經 吸附分離的對二甲苯。 -25- 201028209 表1 實例編號 1 2 3 4 5 6 比較 例1 比較 例2 吸附劑 A-1 A-2 A-3 A-4 A-5 A-6 B-1 B-2 X沸石含量，質量％ 95.7 97.9 96.2 95.3 97.0 97.0 93.2 94.9 Na20含量，質量％ 0.58 0.55 0.63 0.57 0.52 0.44 0.61 0.57 抗壓破碎率，質量％ 10.2 11.0 9.5 9.2 10.7 10.8 9.8 10.0 以壓汞測孔法測得之 總孔體積，mL/g 0.276 0.315 0.270 0.268 0.293 0.297 0.195 0.227 孔徑100〜500奈米的 孔的體積，mL/g 0.180 0.228 0.178 0.181 0.219 0.222 0.107 0.131 孔徑100〜500奈米的 孔佔總孔體積的比例 ，％ 65.2 72.4 65.9 67.5 74.7 74.7 56.9 57.7 孔徑大於500奈米的 孔的體積，mL/g 0.034 0.043 0.028 0.025 0.038 0.041 0.036 0.048 孔徑大於500奈米的 孔佔總孔體積的比例 ，％ 12.3 13.7 10.4 9.3 13.0 13.8 18.5 21.1 內擴散質傳速率，分 鐘 5.1 4.0 4.9 5.0 4.5 4.3 6.9 6.2 可以對上述之體系進行許多變化和改良。所有的改良 和變化均涵蓋在本發明說明書的範圍內並爲下列申請專利 範圍所保護。 【圖式簡單說明】 圖1爲評價本發明吸附劑之質傳速率的擴散曲線示意 圖。 圖2爲本發明進行吸附分離的流程示意圖。 -26- 201028209 【主要元件符號說明】 1至24 :吸附柱The sample of the sample is taken from the sample and the sample is taken. The desired adsorbent is prepared. t A 15- 201028209 The adsorbent of the present invention is prepared and tested for its adsorption performance. (1) Preparation of small-grain X zeolite: 16.4 kg of a sodium metaaluminate solution (in which the content of Al2〇3 was 17.3% by mass, the content of Na20 was 21.0% by mass), and 11.0 kg of deionized was added to a 100-liter synthesizer. Water and 2.9 kg of sodium hydroxide. The solid base was completely dissolved by stirring, and then 11.8 kg of sodium citrate solution (in which the content of Si〇2 was 28.3% by mass and the content of Na20 was 8.8% by mass) was added. The mixture was stirred until homogeneous, and allowed to stand at 25 ° C for aging for 20 hours to obtain a guiding agent. At 25 ° C, 25 5 kg of sodium citrate solution, 1001 kg of deionized water, and 37 kg of sodium hydroxide were added to the 2000 liter kettle, and the mixture was thoroughly mixed by stirring. 227 kg of sodium metaaluminate were added with stirring, and then B kg of a directing agent was added. Stirring is continued until a homogeneous mixture is obtained. The temperature was raised to 1 〇〇 ° C, and allowed to stand for 4 hours. The product is washed with water until the pH of the wash solution is less than 10. The product was filtered, followed by drying at 8 (TC) for 12 hours to obtain NaX zeolite. The SiO2/Al203 molar ratio of the zeolite was calculated from the unit cell constant of 2.19, and the average grain size was observed by scanning electron microscopy. 0.7 μm. (2) Tumble forming ···················································································· Mixing with 3.4 kg of Tianjing powder to form a mixed mixture of -16-201028209. Put the mixed powder into the turntable. Spray an appropriate amount of sodium carbonate solution at a concentration of 5% by mass on the mixed powder. In order to adhere the solid mixed powder to a small ball, the amount of the sodium carbonate aqueous solution sprayed during the tumbling is 25% by mass of the solid mixed powder, and the small ball having a particle diameter of 0.35 to 0.80 mm is sieved at 8 〇t : Dry for 1 hour and calcine for 4 hours at 54 (TC air flow. • (3) Crystallization on the spot: The calcined pellets are ratio of liquid to solid: 2.0:1, 1.5 m〇L/ L treated with sodium hydroxide solution and allowed to stand at 96 ° C 4.0 Hours' to crystallize the kaolin in the field to form X zeolite. The pellet obtained after field crystallization is washed with deionized water until the pH of the washing solution is 9.0. It is dried at 80 °C for 12 hours and calcined at 500 °C. In hours, the toluene adsorption capacity is 0.225 g/g, which is equivalent to the content of X zeolite in the agglomerated pellets is 95.7 mass%. (4) Ion exchange: Take the pellets which are crystallized and calcined in the field, using a conventional exchange column The ion exchange was carried out continuously, and the exchange liquid was 0.18 moL/L cerium nitrate solution. The cerium ion exchange was carried out at 92 ° C and atmospheric pressure for 10 hours, and the volume space velocity of the exchange liquid was 4.0 〃. The cerium nitrate solution and the small sphere were used. The volume ratio is 40: 1. After the exchange is completed, the pellet is washed with 1 〇 times the volume of deionized water, and dried in a nitrogen stream at 220 ° C for 6 hours to obtain an adsorbent A-1. 600 ° C calcination After 2 hours, the ignition loss was determined to be 4.3% by mass, the composition of the adsorbent -17-201028209, the volume and size distribution of the pores measured by the mercury intrusion porosimetry, and the physical properties of the crucible are shown in Table 1. 2 Prepare the adsorbent according to the method of Example 1. 'The difference is ··· (2) In the roll forming, the spray amount of the 5.0% by mass aqueous ammonium carbonate solution is 28% by mass of the solid mixed powder; in the step (3), 'the calcined pellet is mixed with sodium hydroxide and sodium citrate. The solution is treated to perform on-site crystallization, wherein the mixed solution contains 4.3% by mass of Na20 and 2.1% by mass of Si〇2, and the agglomerated capacity of the agglomerated beads obtained after crystallization in the field is 230.230 g/g, which is equivalent to agglomeration. The content of the X zeolite in the pellet was 97.9 mass%. The adsorbent A-2 obtained by ion exchange and activation had a reduction in ignition of 4.5% by mass after calcination at 600 °C for 2 hours. The composition of the adsorbent, the volume and size distribution of the pores measured by mercury intrusion porosimetry, and other physical properties are shown in Table 3. The adsorbent was prepared according to the method of Example 1, except that in step (2), 63 kg of NaX zeolite prepared in Example 1 was mixed with 5.4 kg of kaolin and 2.7 kg of carboxymethylcellulose (purchased from Qingquan Cellulose Factory, Qingzhou, Shandong, China). Put the mixture into the turntable, and spray an appropriate amount of 2-0% by mass of polyacrylamide (available from Shanghai Hengdeng Innovative Phosphate Co., Ltd.) in an aqueous solution to make the solid mixed powder adhere to a small ball. . The amount of the aqueous solution of the polypropylene guanamine sprayed at the time of rolling was 20% by mass of the solid mixture -18- 201028209 powder. The subsequent steps as described in Example 进行 were then dried, calcined, and crystallized on the spot. The toluene adsorption capacity of the pellet obtained after the field crystallization was determined to be 0.226 g/g, which corresponds to the content of the X zeolite in the agglomerated pellets being 96 to 2% by mass. The pellets after crystallization on the spot were ion-exchanged with a cerium nitrate solution according to the method of the first step (4), except that the water-washed pellets were dried in a nitrogen stream at 200 ° C for 6 hours after ion exchange to obtain an adsorption. For the agent A-3, the ignition loss after calcination at 600 ° C for 2 hours was measured to be 5.6% by mass. The composition of the adsorbent, the volume and size distribution of the pores measured by the mercury intrusion porosimetry, and other physical properties are shown in Table 1. Example 4 An adsorbent was prepared in the same manner as in Example 1, except that in the step (2), 63 kg of the NaX zeolite prepared in Example 1 was mixed with 5.4 kg of kaolin and 2.7 kg of carboxymethylcellulose. The mixture was placed in a turntable and sprayed with an appropriate amount of a 2.0% by mass aqueous solution of polyvinyl alcohol (purchased from Shanghai Shaorong Trading Co., Ltd.) to adhere the solid mixed powder to a small ball. The amount of the aqueous polyvinyl alcohol solution sprayed during the tumbling was 22% by mass of the solid mixed powder. It was then dried, calcined, and crystallized on the spot following the subsequent steps described in Example 1. The toluene adsorption capacity of the pellet obtained after the on-site crystallization was determined to be 0.224 g/g, which corresponds to the content of the X zeolite in the agglomerated pellets being 95.3% by mass. The pellets after crystallization on the spot were ion-exchanged with a cerium nitrate solution according to the method of Example 1 step (4), except that the -19-201028209 pellets which were washed with water after ion exchange were dried in 20 (TC nitrogen stream for 6 hours). , the adsorbent A-4 was prepared, and the ignition loss after calcination at 600 ° C for 2 hours was determined to be 5.3% by mass. The composition of the adsorbent, the volume and size distribution of the pores measured by mercury intrusion porosimetry, and Further physical properties are shown in Table 1. Example 5 NaKX zeolite was prepared according to the method described in EP 0960854 A1. 5.5 kg of sodium metaaluminate solution was added to a 100 liter synthesizer (in which the content of Al2〇3 was 17.3% by mass, the content of Na20) 21.0% by mass), 12.6 kg of deionized water and 7.4 kg of sodium hydroxide. Stirring completely dissolves the solid base, and then adding 19.6 kg of sodium citrate solution (wherein the content of SiO 2 is 28.3% by mass and the content of Na 20 is 8.8% by mass). The mixture was stirred until the mixture was allowed to stand at 40 ° C for 1.0 hour to prepare a directing agent. At 40 ° C, 198 kg of sodium citrate solution and 660 kg of deionized solution were added to the .2 000 liter kettle. Water, 90 kg of sodium hydroxide and 1 05 kg of potassium hydroxide, stir well to mix well, and add 288 kg of sodium metaaluminate under stirring, then add 3 kg of guiding agent to continue stirring until a homogeneous mixture is obtained. The mixture is at 250 U/min at 40 °C. The mixture was aged for 4 hours with stirring. The mixture was then warmed to 70 ° C and allowed to stand for 4 hours. The product was washed with water until the pH of the washing liquid was less than 10. The product was filtered and dried at 70 ° C for 12 hours to obtain NaKX zeolite. The SiO2/Al203 molar ratio of the zeolite calculated from the unit cell constant was 2.03, and the average grain size was observed by scanning electron microscopy to be 4.4 μm. 75 kg of NaKX zeolite, 8.3 kg of kaolin and 3.0 kg of carboxy 201028209 The base cellulose is uniformly mixed to form a mixed powder. The mixed powder is placed in a turntable, and a carbonated water solution having a concentration of 5.0% by mass is sprayed while being tumbling, so that the solid mixed powder adheres and agglomerates into small balls. The amount of the aqueous ammonium carbonate solution was 27% by mass of the solid mixed powder. Then, the subsequent steps described in Example 1 were followed by drying, calcination, and crystallization on the spot. The adsorption capacity is 0.228 g / g, which is equivalent to the content of X zeolite in the agglomerated pellets is 9.7 · 0% by mass. Φ The granules after crystallization on the spot are ionized with cerium nitrate solution according to the method of the first step (4) of Example 1. Exchange, the difference is that the ion-washed pellets were dried in a nitrogen stream at 230 °C for 4 hours to obtain the adsorbent a-5, and the ignition loss after calcination at 600 °C for 2 hours was measured. The composition of the adsorbent, the volume and size distribution of the pores measured by the mercury intrusion porosimetry, and other physical properties are shown in Table 1. Example 6 φ The adsorbent was prepared according to the method of Example 5. The difference was that the pellet obtained after crystallization in the field was ion exchanged with a mixed solution of potassium chloride and cerium nitrate, wherein the K+ ion concentration was 〇.1 Mo. Ear/liter, Ba2 + ion concentration is 0.20 mol/L. In ion exchange, the volume ratio of exchange fluid to solid pellets consumed is 40:1. The content of potassium oxide in the obtained adsorbent A-6 was 〇·75 mass%, and the content of cerium oxide was 45 mass%. The molar ratio of cerium oxide to potassium oxide in adsorbent A-6 was 36.8. The ignition loss of the adsorbent A-6 measured after 6,000 calcination for 2 hours was 4.8% by mass. The composition of the adsorbent, the volume and size distribution of the pores measured by mercury intrusion porosimetry, and its physical properties are shown in Table 1. Comparative Example 1 7 kg of the NaX zeolite prepared in Example 1 was uniformly mixed with 7 kg of kaolin. Put the mixture into the turntable and roll a proper amount of deionized water while rolling to solidify the solid powder into a small ball. The amount of water sprayed during tumbling was 30% by mass of the solid powder. Sifting 0.35~0.80 mm pellets' These beads were dried at 80 °C for 1 , hours at 540 °C. (: calcination in an air stream for 4 hours. The calcined pellet was further treated with a mixed solution of sodium hydroxide and sodium citrate for on-site crystallization, wherein the mixed solution contained 4.3 mass% of Na20 and 2.1 mass% of SiO2. After crystallization on the spot, the obtained pellet was washed with deionized water until the pH of the washing solution was 9.0. The pellet was then dried at 80 ° C for 12 hours and calcined at 500 ° C for 2 hours. The obtained agglomerated pellet toluene was obtained. The adsorption capacity is 0.219 g/g, which is equivalent to the content of X zeolite in the agglomerated pellets is 93.2% by mass. The agglomerated beads obtained after the on-site crystallization treatment are subjected to ion exchange and dry dehydration according to the method of the first step (4). The adsorbent B-1 was compared. The ignition loss after calcination at 600 ° C for 2 hours was determined to be 4.7% by mass. The composition of the adsorbent, the volume and size distribution of the pores measured by mercury intrusion porosimetry, And other physical properties are shown in Table 1. Comparative Example 2 70 kg of NaX zeolite prepared in Example 1 was mixed with 7 kg of kaolin and 2.8 kg of carboxymethylcellulose to form a mixed powder. The mixed powder-22-201028209 was placed. Into the turntable, spray while rolling The deionized water 'adhesively agglomerates the solid powder into small balls. The amount of water sprayed during the tumbling is 32% by mass of the solid mixed powder. The small balls of 0.35 to 0.80 mm are sieved. The beads are dried for 10 hours. Then, it was calcined in a 540 ° C air stream for 4 hours. The calcined pellet was treated with a mixed solution of sodium hydroxide and sodium citrate for on-site crystallization, wherein the mixed solution contained 4.3% by mass of NaaO and 2.1% by mass. Si02. After crystallization in the field, the obtained pellet was washed with deionized water φ to a pH of 9.0. The pellet was dried at 80 ° C for 12 hours ' and calcined at 500 ° C for 2 hours. The obtained agglomerated pellets The toluene adsorption capacity is 0.223 g/g, which is equivalent to the content of X zeolite in the agglomerated pellets is 95.7 mass%. The agglomerated pellet obtained after the on-site crystallization treatment is ion-exchanged according to the method of the first step (4). Dry dehydration, compare the adsorbent B-2 ' to determine its burning loss after calcination at 600 °C for 2 hours is 5.1% by mass. The composition of the adsorbent, the volume of the pore measured by mercury intrusion porosimetry And size distribution, φ and other physical properties are shown in 1. Example 7 Adsorption adsorption of p-xylene with adsorbent A-2 on a small counter-flowing simulated moving bed. The small simulated moving bed consists of 24 columns of adsorption columns 'each of which is 195 mm long'. The diameter of the adsorbent is 3,300 ml. As shown in Fig. 2, the first adsorption column and the last adsorption column of the 24 adsorption columns in series are connected by a circulation pump to form a closed- 23 - 201028209 Loop. In Figure 2, 24 columns of adsorption columns are divided into four sections with four materials input or output, namely adsorbent material, desorbent, extract, and raffinate. That is, the seven adsorption columns between the adsorption raw material (column 15) and the raffinate (column 21) are adsorption zones; the nine adsorption columns between the extraction liquid (column 6) and the adsorption raw material (column 14) are purification zones. The five adsorption columns between the desorbent (column 1) and the extract (column 5) are the desorption zone; and the three adsorption columns between the raffinate (column 22) and the desorbent (column 24) are buffer zones. . The temperature of the entire adsorption system was controlled at 177 °C and the pressure was controlled at 88 MPa. During the operation, the desorbent to the diethylbenzene and the flow rate of 1190 ml/hr of the adsorbent at a flow rate of 1420 ml/hr were continuously injected into the above simulated moving bed, and the extract was taken from the apparatus at a flow rate of 710 ml/hr. Remove and remove the raffinate from the unit at a flow rate of 1 900 ml/hr. The adsorbent raw material includes 9.3 mass% ethylbenzene, 18.5 mass% para-xylene, 45.4 mass% meta-xylene, 17.4 mass% o-xylene, and 9.4 mass% of a non-aromatic component. According to the principle of simulated countercurrent chromatography, when the circulation pump flow rate is set to 4 5 80 ml / hr, every 70 seconds, the four material positions are moved forward by one adsorption column in the same direction as the liquid flow direction. In a stable operating state, the obtained p-xylene had a purity of 99.75 mass% and a recovery yield of 99.0 mass%. The calculated para-xylene productivity thus obtained was 0.066 m3 of adsorbed separated p-xylene per cubic meter of adsorbent per hour. Example 8 An adsorbent A-6 was placed on a small moving bed apparatus, and an experiment for adsorbing and separating p-xylene was carried out in the same manner as in Example 7. Under stable operation, the purity of p-xylene obtained from • 24-201028209 was 99.80 mass%, and the yield was 98.4 mass%. The productivity of para-xylene is 0.0656 m3 per cubic metre of adsorbent separated p-xylene. Comparative Example 3 A comparative adsorbent B-2 was placed on a small moving bed apparatus, and an experiment of adsorbing and separating p-xylene was carried out in the same manner as in Example 7. Under stable operating conditions, • (4) _ xylene has a purity of 99.71 mass% and a recovery yield of 90.5 mass%. The para-xylene productivity is 0.060 4 m3 per cubic meter of adsorbent separated p-xylene. -25- 201028209 Table 1 Example No. 1 2 3 4 5 6 Comparative Example 1 Comparative Example 2 Adsorbent A-1 A-2 A-3 A-4 A-5 A-6 B-1 B-2 X Zeolite content, Mass% 95.7 97.9 96.2 95.3 97.0 97.0 93.2 94.9 Na20 content, mass% 0.58 0.55 0.63 0.57 0.52 0.44 0.61 0.57 Compressive crushing rate, mass% 10.2 11.0 9.5 9.2 10.7 10.8 9.8 10.0 Total pore volume measured by mercury intrusion porosimetry , mL / g 0.276 0.315 0.270 0.268 0.293 0.297 0.195 0.227 pore volume of pores 100 ~ 500 nm, mL / g 0.180 0.228 0.178 0.181 0.219 0.222 0.107 0.131 pore diameter of 100 ~ 500 nm of the proportion of the total pore volume, % 65.2 72.4 65.9 67.5 74.7 74.7 56.9 57.7 Volume of pores with a pore diameter greater than 500 nm, mL/g 0.034 0.043 0.028 0.025 0.038 0.041 0.036 0.048 Proportion of pores with a pore diameter greater than 500 nm to the total pore volume, % 12.3 13.7 10.4 9.3 13.0 13.8 18.5 21.1 Internal diffusion mass transfer rate, minutes 5.1 4.0 4.9 5.0 4.5 4.3 6.9 6.2 Many changes and modifications can be made to the above system. All modifications and variations are encompassed within the scope of the present invention and are protected by the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the diffusion curve for evaluating the mass transfer rate of the adsorbent of the present invention. 2 is a schematic view showing the flow of adsorption separation in the present invention. -26- 201028209 [Explanation of main component symbols] 1 to 24: adsorption column
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