TW202216284A - 一種間二甲苯吸附劑及其製備方法 - Google Patents
一種間二甲苯吸附劑及其製備方法 Download PDFInfo
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- TW202216284A TW202216284A TW110137928A TW110137928A TW202216284A TW 202216284 A TW202216284 A TW 202216284A TW 110137928 A TW110137928 A TW 110137928A TW 110137928 A TW110137928 A TW 110137928A TW 202216284 A TW202216284 A TW 202216284A
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Abstract
一種間二甲苯吸附劑,包括94~99.9質量%的Y分子篩和0.1~6質量%的基質,所述Y分子篩由非轉晶Y分子篩和轉晶生成的Y分子篩組成,所述非轉晶Y分子篩為介孔奈米Y分子篩,所述介孔奈米Y分子篩晶粒粒徑為20~450奈米,含有兩種介孔孔道,最可能孔直徑分別為5~20奈米和25~50奈米。該吸附劑用於從混合碳八芳烴中吸附分離間二甲苯,具有良好的質傳性能以及較高的間二甲苯吸附選擇性和吸附容量。
Description
本發明為分子篩吸附劑及其製備方法,具體地說,是一種間二甲苯吸附劑及其製備方法。
間二甲苯(MX)是重要的基本有機化工原料,廣泛應用於合成樹脂、農藥、醫藥、塗料和染料等領域。工業上,高純度的間二甲苯通常是採用吸附分離技術從含有乙苯、對二甲苯、間二甲苯和鄰二甲苯的混合碳八芳烴中分離獲得。
吸附劑是吸附分離技術的基礎和核心,其活性組元多為沸石材料。CN1136549A和US6137024分別報導了以Silicalite-1和氫型β沸石為活性組元的吸附劑,但是Silicalite-1、β沸石的吸附容量較低,使其應用受到限制。相比而言,Y分子篩的吸附容量較高,具有更為廣闊的應用前景。
US4306107公開了一種從混合碳八芳烴中分離間二甲苯和乙苯的方法。該方法採用NaY沸石為吸附劑的活性組元,以甲苯為解吸劑,利用NaY沸石對間二甲苯的吸附能力最強、對二甲苯和鄰二甲苯居中、乙苯最弱的特點,將混合碳八芳烴通入模擬移動床進行逆流操作,在模擬移動床的不同位置分別得到間二甲苯、對二甲苯和鄰二甲苯、乙苯。
US4326092公開了一種從混合碳八芳烴中分離間二甲苯的方法,採用氧化矽與氧化鋁莫耳比為4.5~5.0的NaY沸石製備吸附劑,可以獲得更高的間二甲苯選擇性。
US5900523報導以氧化矽與氧化鋁莫耳比為4.0~6.0的NaY沸石為活性組元的吸附劑,水含量以500℃灼減量計為1.5~2.5質量%,以二氫化茚為解吸劑,在100~150℃進行液相吸附分離間二甲苯,取得了好的分離效果。
CN1939883A公開了一種從碳八芳烴異構體中分離間二甲苯的方法,採用氧化矽與氧化鋁莫耳比為5~6的NaY沸石製備吸附劑,該沸石含水0~8質量%,吸附溫度25~250℃,解吸劑選自四氫化萘及其烷基化衍生物。
本發明的目的是提供一種間二甲苯吸附劑及其製備方法,該吸附劑用於從混合碳八芳烴中吸附分離間二甲苯,具有良好的質傳性能以及較高的間二甲苯吸附選擇性和吸附容量。
本發明提供的間二甲苯吸附劑包括94~99.9質量%的Y分子篩和0.1~6質量%的基質,所述Y分子篩由非轉晶Y分子篩和轉晶生成的Y分子篩組成,所述非轉晶Y分子篩為介孔奈米Y分子篩,所述介孔奈米Y分子篩的晶粒粒徑為20~450奈米,含有兩種介孔孔道,最可能孔直徑分別為5~20奈米和25~50奈米。。
本發明吸附劑活性組份Y分子篩中的非轉晶Y分子篩為介孔奈米Y分子篩,所述介孔奈米Y分子篩為奈米級Y分子篩晶粒自聚集而成的自聚體,且包含兩種介孔孔道。該吸附劑用於吸附分離混合碳八芳烴中的間二甲苯,具有較高的間二甲苯吸附選擇性,以及較高的吸附容量和質傳速率,可顯著提高吸附劑對吸附分離原料的處理能力。
本發明吸附劑中的活性組份Y分子篩由非轉晶Y分子篩和轉晶生成的Y分子篩組成,其中的非轉晶Y分子篩為奈米級Y分子篩晶粒自聚集形成的自聚體,自聚體粒徑相對較大,所述的奈米級Y分子篩有利於改善質傳性能,較大的自聚體粒徑可以較好地解決分子篩合成時,因產生奈米級分子篩晶粒而引起的固液分離困難的問題。此外,該奈米Y分子篩自聚體包含兩種介孔孔道,進一步賦予了其良好的質傳性能,而質傳性能的改善又能提高介孔奈米Y分子篩對間二甲苯的吸附選擇性。
本發明將介孔奈米Y分子篩(非轉晶Y分子篩)與作為黏合劑的高嶺土礦物、成型助劑和矽源混合後滾球成型,在高溫下焙燒,使其中的高嶺土礦物轉化為偏高嶺土,然後再通過鹼處理,使偏高嶺土原位晶化轉化成Y分子篩,然後乾燥、焙燒得到吸附劑。
優選地,本發明所述的吸附劑包括98~99.9質量%的Y分子篩和0.1~2質量%的基質。
本發明所述吸附劑中含兩種Y分子篩,一種是非轉晶Y分子篩,為介孔奈米Y分子篩,具有兩種介孔孔道,另一種是吸附劑成型過程中使用的黏合劑,一般為高嶺土礦物與成型過程加入的矽源原位晶化後形成的Y分子篩。優選地,所述吸附劑包括84~93質量%的非轉晶Y分子篩、1~15.9質量%的轉晶生成的Y分子篩和0.1~6質量%的基質;更優選地,所述吸附劑包括84~93質量%的非轉晶Y分子篩、5~15.9質量%的轉晶生成的Y分子篩和0.1~2質量%的基質。
本發明所述介孔奈米Y分子篩優選為奈米級Y分子篩晶粒自聚體,自聚體粒徑優選0.5~1.5微米,自聚體中奈米級Y分子篩的晶粒粒徑優選20~400奈米、更優選50~300奈米。所述奈米Y分子篩自聚體包含兩種介孔孔道,最可能孔直徑分別為5~20奈米和25~50奈米、優選分別為10~20奈米和30~50奈米。
所述介孔奈米Y分子篩的SiO
2/Al
2O
3莫耳比優選為4.0~5.5。
所述介孔奈米Y分子篩的比表面積優選為740~1000 m
2/g、更優選750~900 m
2/g,總孔體積優選為0.40~0.65 cm
3/g、更優選0.40~0.55 cm
3/g,介孔孔體積優選為0.08~0.35 cm
3/g、更優選0.10~0.25 cm
3/g。
吸附劑中所述的基質為高嶺土礦物經原位晶化轉晶後的剩餘物。所述的高嶺土礦物優選選自高嶺石、地開石、珍珠石、耐火石和埃洛石中的至少一種。
本發明所述的吸附劑優選為小球狀,小球的粒徑優選300~850微米。
本發明所述吸附劑的製備方法,包括如下步驟:
(1)將非轉晶NaY分子篩、高嶺土礦物、矽源和成型助劑混合均勻,滾球成型製成小球,乾燥後於530~600℃焙燒,所述非轉晶NaY分子篩與高嶺土礦物的質量比為85~94:6~15,加入的矽源中所含二氧化矽與高嶺土礦物的質量比為0.1~3.6;
(2)將(1)步焙燒後所得小球用氫氧化鈉或氫氧化鈉與水玻璃的混合溶液於85~100℃進行原位晶化處理,使其中的高嶺土礦物原位晶化為Y分子篩,然後水洗、乾燥。
上述方法(1)步是將非轉晶NaY分子篩、高嶺土礦物、矽源與成型助劑混合後滾球成型,所述的高嶺土礦物中含有的晶化物質優選選自高嶺石、地開石、珍珠石、耐火石、埃洛石或它們的混合物。所述高嶺土礦物中晶化物質的質量百分數至少為90%。
(1)步所述的矽源優選選自正矽酸乙酯、矽溶膠、水玻璃、矽酸鈉、矽膠和白碳黑中的一種或幾種。優選地,加入的矽源中所含二氧化矽與高嶺土礦物的質量比為0.2~3.0。所述的成型助劑優選選自木質素、田菁粉、乾澱粉、羧甲基纖維素和活性碳中的至少一種。成型助劑加量優選為固體粉料總量的1~6質量%。
(1)步所述的成型方法優選為滾球成型或噴霧成型。對於滾球成型方法,所用的設備可為轉盤、糖衣鍋或滾筒。滾球成型時,將混合均勻的固體粉料放入轉動設備中,邊滾動邊噴水使固體粉料黏附團聚成小球。滾球時水用量優選為固體總質量的6~30%,更優選6~20%。當加入的矽源為固體時,可與非轉晶NaY分子篩、高嶺土礦物混合;當加入的矽源為液體時,可與非轉晶NaY分子篩、高嶺土礦物混合,也可加入滾球成型所用的水中,或者既在固體粉料中加入矽源,又在水中加入矽源。
(1)步滾動成球後的小球,經過篩分,取一定範圍粒徑的小球,優選取粒徑為300~850微米的小球,將其乾燥、焙燒。所述乾燥溫度優選60~110℃,時間優選2~12小時,焙燒溫度優選530~700℃,時間優選1~6小時。經過焙燒後,小球內的高嶺土礦物轉化為偏高嶺土,以便於(2)步轉晶為NaY分子篩。
上述方法(2)步為成型後小球的原位晶化,所述原位晶化可在氫氧化鈉溶液或氫氧化鈉與水玻璃的混合溶液中進行,原位晶化處理時的液/固比優選1.5~5.0升/千克,原位晶化處理溫度優選90~100℃,時間優選0.5~8小時。
(2)步原位晶化處理使用氫氧化鈉溶液時,所用的氫氧化鈉溶液中氫氧根離子的濃度優選為0.1~3.0莫耳/升,更優選0.5~1.5莫耳/升;當原位晶化處理使用氫氧化鈉和水玻璃混合溶液時,其中氧化鈉含量優選2~10質量%,二氧化矽含量優選1~6質量%。將原位晶化後的吸附劑水洗、乾燥後即得球形吸附劑。所述的乾燥溫度優選70~110℃,乾燥時間優選2~20小時。
本發明方法(1)步所述的非轉晶NaY分子篩的製備方法,包括如下步驟:
(Ⅰ)取0~5℃的矽源、鋁源,加入氫氧化鈉、水混合均勻形成分子篩合成系統,其中各物料的莫耳比為:SiO
2/Al
2O
3=5.5~9.5、Na
2O/SiO
2=0.1~0.3、H
2O/SiO
2=5~25,合成系統的溫度為1~8℃,
(Ⅱ)將(Ⅰ)步的分子篩合成系統於20~40℃靜態老化10~48小時,再於90~150℃靜態晶化2~10小時,攪拌2~10分鐘,繼續靜態晶化11~20小時,將所得固體洗滌、乾燥。
上述方法(Ⅰ)步為在低溫下製備分子篩合成系統,取0~5℃、優選0~4℃的矽源、鋁源,再加入氫氧化鈉和水製成分子篩合成系統,所述分子篩合成系統中各物料的莫耳比優選為:SiO
2/Al
2O
3=7~9、Na
2O/SiO
2=0.1~0.25、H
2O/SiO
2=8~20。合成系統的溫度優選為1~5℃。
上述方法(Ⅱ)步為將分子篩合成系統進行晶化製備分子篩,優選地,將分子篩合成系統於20~40℃靜態老化15~30小時,再於90~120℃靜態晶化4~9小時,攪拌2~10分鐘,繼續靜態晶化11~15小時。晶化後所得固體經洗滌、乾燥,得到介孔奈米Y分子篩。所述乾燥溫度優選70~100℃、更優選75~90℃,乾燥時間優選2~20小時、更優選8~16小時。
上述方法(Ⅰ)步所述的鋁源優選選自低鹼度偏鋁酸鈉溶液、氧化鋁、氫氧化鋁、硫酸鋁溶液、氯化鋁、硝酸鋁和鋁酸鈉中的一種或幾種,更優選低鹼度偏鋁酸鈉溶液和/或硫酸鋁溶液。所述低鹼度偏鋁酸鈉溶液中Al
2O
3含量優選17~28質量%,Na
2O含量優選19~30質量%,該低鹼度偏鋁酸鈉溶液中所含Na
2O與Al
2O
3的莫耳比優選1.7~2.5、更優選1.7~2.2。當所述的鋁源選自低鹼度偏鋁酸鈉溶液和硫酸鋁溶液時,硫酸鋁溶液與低鹼度偏鋁酸鈉溶液的質量比為1~6:1,硫酸鋁溶液中所含的鋁以Al
2O
3計,其中Al
2O
3的含量優選為5~15質量%。
(Ⅰ)步所述的矽源優選矽溶膠或水玻璃。所述水玻璃中SiO
2含量優選為25~38質量%,Na
2O含量優選為9~15質量%。
本發明所述的吸附劑適用於從混合碳八芳烴中吸附分離間二甲苯。
吸附選擇性和對吸附目的組份的吸附、解吸速率是評價吸附劑性能的重要指標。選擇性為吸附平衡時,吸附相中兩組份濃度的比值與非吸附相中該兩組份濃度的比值之比。所述吸附平衡是指混合碳八芳烴與吸附劑接觸後,吸附相和非吸附相之間不發生組份淨轉移時的狀態。吸附選擇性的計算公式如下:
其中,C和D表示欲進行分離的兩種組份,A
C和A
D分別表示吸附平衡時吸附相中C、D兩種組份的濃度,U
C和U
D分別表示吸附平衡時非吸附相中C、D兩種組份的濃度。當兩種組份的選擇性β≈1.0時,表明吸附劑對兩種組份的吸附能力相當,不存在被優先吸附的組份。當β大於或小於1.0時,表明一種組份被優先吸附。具體地說,當β>1.0時,吸附劑優先吸附C組份;當β<1.0時,吸附劑優先吸附D組份。從分離的難易程度講,β值越大,吸附分離越容易進行。較快的吸附、解吸速率,有利於減少吸附劑和解吸劑的用量,提高產品產率,降低吸附分離裝置的操作費用。
本發明使用一種動態脈衝實驗裝置測定吸附選擇性和間二甲苯的吸附、解吸速率。該裝置由進料系統、吸附柱、加熱爐、壓力控制閥等組成。吸附柱為Ф6×1800毫米的不銹鋼管,吸附劑裝量為50毫升。吸附柱下端入口與進料和氮氣系統相連,上端出口接壓力控制閥,再與流出物收集器連接。實驗所用解吸劑組成為30體積%的甲苯(T)和70體積%的正庚烷(NC
7),脈衝液組成為各佔5體積%的乙苯(EB)、對二甲苯(PX)、間二甲苯(MX)、鄰二甲苯(OX)、正壬烷(NC
9)和75體積%的上述解吸劑。
吸附選擇性的測定方法為:將稱量好的吸附劑裝入吸附柱震盪填實,在氮氣流中於160~280℃脫水活化。然後通入解吸劑排除系統中的氣體,將壓力升至0.8MPa,溫度升至145℃,停止通入解吸劑,按1.0小時
-1的體積空速通入8毫升的脈衝進料液,然後停止通入脈衝液,並以同樣的空速通入解吸劑進行脫附,每2分鐘取3滴脫附液樣品,用氣相層析分析組成。以脫附用解吸劑進料體積為橫坐標,NC
9和EB、PX、MX、OX各組份濃度為縱坐標,繪製上述各組份的脫附曲線。作為示蹤劑的NC
9不被吸附,首先出峰,它給出了吸附系統的死體積。將示蹤劑半峰寬的中點作為零點,測定EB、PX、MX、OX各組份半峰寬中點到零點的解吸劑進料體積,即淨保留體積V
R。兩組份淨保留體積之比即為吸附選擇性β。如MX的淨保留體積與EB的淨保留體積之比即為MX相對於EB的吸附選擇性,記為β
MX/EB。
為了實現吸附劑的循環連續使用,提取組份與解吸劑之間選擇性也是一個重要的性能指標,可以通過對脈衝試驗提取組份脫附曲線的進一步解析來確定。將MX的脈衝脫附曲線前沿流出液中MX濃度從10%上升到90%時所需的解吸劑體積定義為吸附速率[S
A]
10-90,將脫附曲線後沿MX濃度從90%下降到10%時所需的解吸劑體積定義為解吸速率[S
D]
90-10。二者的比值[S
D]
90-10/[S
A]
10-90即可表徵為MX與解吸劑(T)之間的吸附選擇性β
MX/T。若β
MX/T遠小於1.0,表示吸附劑對解吸劑的吸附能力太強,這對吸附過程是不利的,若β
MX/T遠大於1.0,則表示對解吸劑的吸附能力太弱,將會使脫附過程變得困難,理想的狀況是β
MX/T約等於1.0。
下面通過實例進一步說明本發明,但本發明並不限於此。
實例和對照例中,吸附劑的物性參數測定方法如下:
吸附劑抗壓強度由一定壓力下小球吸附劑的破碎率表示,破碎率越低,抗壓強度越高。吸附劑抗壓強度測定方法:採用DL-II型顆粒強度測定儀(大連化工研究設計院生產)測定,吸附劑小球過300微米的篩後,在不銹鋼筒體中裝入約1.5毫升吸附劑。測定時安裝一個與不銹鋼筒體過盈配合的頂針,在預先設定好的壓力下壓一次後倒出吸附劑,再過300微米的篩稱重,吸附劑加壓測試前後質量減少量為在設定壓力下吸附劑的破碎率。
採用甲苯氣相吸附實驗測定分子篩或吸附劑的吸附容量,具體操作方法為:在35℃下,使攜帶甲苯的氮氣(甲苯分壓為0.05 MPa)與一定質量的吸附劑接觸,直到甲苯達到吸附平衡。根據甲苯吸附前後吸附劑的質量差由下式計算出被測吸附劑的吸附容量。
其中,C為吸附容量,單位為毫克/克;m
1為吸附甲苯前被測吸附劑的質量,單位為克;m
2為吸附甲苯後被測吸附劑的質量,單位為克。
吸附劑的灼基堆密度的測定方法:在100 mL量筒中加入50 mL吸附劑,在振實密度儀(遼寧儀錶研究所有限責任公司生產)上振動5分鐘,再加入50 mL吸附劑並振動5分鐘,量筒中吸附劑質量與體積之比為吸附劑堆密度;取一定質量的吸附劑於600℃灼燒2小時,並置於乾燥器中冷卻至室溫,灼燒後與灼燒前吸附劑質量之比為灼基,灼基與吸附劑堆密度之積為灼基堆密度。
分子篩的比表面積、總孔體積、微孔孔體積和介孔孔體積按照ASTMD4365-95(2008)測定。
實例1
(1)製備鋁源
將200 kg氫氧化鋁、181.52 kg氫氧化鈉和214.84 kg去離子水加入反應釜中,加熱至100℃,攪拌6小時,形成澄清透明的低鹼度偏鋁酸鈉溶液,作為鋁源1。所述鋁源1中Al
2O
3含量為21.58質量%,Na
2O含量為23.59質量%,Na
2O與Al
2O
3的莫耳比為1.80。將87.89 kg十八水合硫酸鋁溶於112.11 kg水中,攪拌1小時,得到澄清透明的硫酸鋁溶液,作為鋁源2。所述鋁源2中Al
2O
3含量為6.73質量%。
(2)原料預處理
分別將水玻璃(SiO
2含量為37.17質量%,Na
2O含量為11.65質量%)和(1)步製備的鋁源降溫至0℃。
(3)製備Y分子篩
在攪拌條件下,取(2)步降溫處理的89.68 kg的0℃的水玻璃、49.79 kg的0℃的硫酸鋁溶液、18.14 kg的0℃的低鹼度偏鋁酸鈉溶液,和5.61 kg去離子水加入反應釜中,得到Y分子篩合成系統,其中各物料的莫耳比為SiO
2/Al
2O
3=7.8,Na
2O/SiO
2=0.25,H
2O/SiO
2=10。合成系統的溫度為3℃。
將上述分子篩合成系統轉移到密閉反應釜中,於30℃靜態老化24小時,再升溫至100℃靜態晶化8小時,攪拌5分鐘,繼續靜態晶化12小時,過濾,所得固體用去離子水洗滌至濾液pH為8~9,80℃乾燥12小時,得到奈米Y分子篩a,其SiO
2/Al
2O
3莫耳比為4.6(採用X射線螢光光譜分析,下同),XRD圖譜見圖1,SEM照片見圖2,孔徑分佈曲線見圖3。由圖2可知,奈米級Y分子篩晶粒自聚形成自聚體,自聚體粒徑為0.6微米,奈米級Y分子篩的晶粒粒徑為60~150奈米。圖3顯示,奈米Y分子篩a的最可能孔直徑分別為10奈米和37奈米,其比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
實例2
按實例1的方法製備Y分子篩,不同的是(3)步中,在攪拌條件下,取(2)步降溫處理的89.68 kg的0℃的水玻璃、53.29 kg的0℃的硫酸鋁溶液、17.04 kg的0℃的低鹼度偏鋁酸鈉溶液,和3.50 kg去離子水加入反應釜中,得到Y分子篩合成系統,其中各物料的莫耳比為SiO
2/Al
2O
3=7.8,Na
2O/SiO
2=0.23,H
2O/SiO
2=10。合成系統的溫度為4℃。將上述分子篩合成系統轉移到密閉反應釜中,經靜態老化、中間有攪拌的兩段靜態晶化,所得固體用去離子水洗滌、乾燥後得到奈米Y分子篩b,其SiO
2/Al
2O
3莫耳比為4.8,由奈米級Y分子篩晶粒形成的自聚體粒徑為0.8微米,奈米級Y分子篩的晶粒粒徑為80~180奈米,孔徑分佈曲線見圖4,最可能孔直徑分別為12奈米和40奈米,比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
實例3
按實例1的方法製備Y分子篩,不同的是(3)步中,在攪拌條件下,取(2)步降溫處理的89.68 kg的0℃的水玻璃、58.56 kg的0℃的硫酸鋁溶液和15.04 kg的0℃的低鹼度偏鋁酸鈉溶液,和0.32 kg去離子水加入反應釜中,得到Y分子篩合成系統,其中各物料的莫耳比為SiO
2/Al
2O
3=7.8、Na
2O/SiO
2=0.20、H
2O/SiO
2=10。合成系統的溫度為5℃。將上述分子篩合成系統轉移到密閉反應釜中,經靜態老化、中間有攪拌的兩段靜態晶化,所得固體用去離子水洗滌、乾燥後得到奈米Y分子篩c,其SiO
2/Al
2O
3莫耳比為4.9,由奈米級Y分子篩晶粒形成的自聚體粒徑為1.0微米,奈米級Y分子篩的晶粒粒徑為90~200奈米,孔徑分佈曲線見圖5,最可能孔直徑分別為15奈米和42奈米,比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
實例4
按實例1的方法製備Y分子篩,不同的是(3)步中,在攪拌條件下,取(2)步降溫處理的59.79 kg的0℃的水玻璃、39.05 kg的0℃的硫酸鋁溶液、10.27 kg的0℃的低鹼度偏鋁酸鈉溶液,和33.54 kg去離子水加入反應釜中,得到Y分子篩合成系統,其中各物料的莫耳比為SiO
2/Al
2O
3=7.8、Na
2O/SiO
2=0.20、H
2O/SiO
2=15。合成系統的溫度為4℃。將上述分子篩合成系統轉移到密閉反應釜中,經靜態老化、中間有攪拌的兩段靜態晶化,所得固體用去離子水洗滌、乾燥後得到奈米Y分子篩d,其SiO
2/Al
2O
3莫耳比為4.9,由奈米級Y分子篩晶粒形成的自聚體粒徑為1.1微米,奈米級Y分子篩的晶粒粒徑為90~220奈米,孔徑分佈曲線見圖6,最可能孔直徑分別為17奈米和43奈米,比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
實例5
按實例1的方法製備Y分子篩,不同的是(3)步中,在攪拌條件下,取(2)步降溫處理的44.84 kg的0℃的水玻璃、29.29 kg的0℃的硫酸鋁溶液、7.7 kg的0℃的低鹼度偏鋁酸鈉溶液,和50.16 kg去離子水加入反應釜中,得到Y分子篩合成系統,其中各物料的莫耳比為SiO
2/Al
2O
3=7.8、Na
2O/SiO
2=0.20、H
2O/SiO
2=20。合成系統的溫度為5℃。將上述分子篩合成系統轉移到密閉反應釜中,經靜態老化、中間有攪拌的兩段靜態晶化,所得固體用去離子水洗滌、乾燥後得到奈米Y分子篩e,其SiO
2/Al
2O
3莫耳比為5.0,由奈米級Y分子篩晶粒形成的自聚體粒徑為1.2微米,奈米級Y分子篩的晶粒粒徑為100~240奈米,孔徑分佈曲線見圖7,最可能孔直徑分別為19奈米和46奈米,比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
對照例1
(1)製備鋁源
將200 kg氫氧化鋁、232.15 kg氫氧化鈉和652.33 kg去離子水加入反應釜中,加熱至100℃,攪拌6小時,形成澄清透明的低鹼度偏鋁酸鈉溶液,作為鋁源。所述鋁源中Al
2O
3含量為11.87質量%,Na
2O含量為16.59質量%,Na
2O與Al
2O
3的莫耳比為2.3。
(2)製備導向劑
在攪拌條件下,將3.81 kg氫氧化鈉、8.86 kg去離子水、4.48 kg(1)步製備的鋁源和23.24 kg的水玻璃(水玻璃中SiO
2含量為20.17質量%,Na
2O含量為6.32質量%)加入反應釜中,其各物料的莫耳比為SiO
2/Al
2O
3=15、Na
2O/SiO
2=1.07、H
2O/SiO
2=21,於35℃靜置16小時得到導向劑。
(3)製備Y分子篩
在攪拌條件下,將50.74 kg的水玻璃、42.51 kg去離子水、7.56 kg(2)步製備的導向劑、8.66 kg實例1(1)步所述的硫酸鋁溶液和11.01 kg(1)步製備的低鹼度偏鋁酸鈉溶液加入反應釜中,得到Y分子篩合成系統,其中各物料的莫耳比為SiO
2/Al
2O
3=9.5,Na
2O/SiO
2=0.43,H
2O/SiO
2=30,導向劑中所含Al
2O
3與Y分子篩合成系統中所含Al
2O
3的莫耳比為5%,合成系統的溫度為35℃。
將上述分子篩合成系統轉移到密閉反應釜中,升溫至100℃水熱晶化28小時,過濾,所得固體用去離子水洗滌至濾液pH=8~9,80℃乾燥12小時,得到Y分子篩f,其SiO
2/Al
2O
3莫耳比為4.8,XRD圖譜見圖8,SEM照片見圖9,Y分子篩晶粒粒徑為0.9微米,孔徑分佈曲線見圖10,顯示無明顯介孔,其比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
對照例2
按傳統不用導向劑的方法製備Y分子篩
將5.0 kg鋁酸鈉(含30質量%Na
2O,44.1質量%Al
2O
3,25.9質量%H
2O)和27.3 kg氫氧化鈉溶於219 kg水中,攪拌1小時,得到澄清溶液,在攪拌條件下加入124.2 kg矽溶膠(含29.5質量%SiO
2),繼續攪拌0.5小時得到混合均勻的合成系統,其中各物料的莫耳比為SiO
2/Al
2O
3=28.2,Na
2O/SiO
2=0.6,H
2O/SiO
2=28.7。將上述合成系統轉移至密閉反應釜中,升溫至120℃水熱晶化3小時,過濾,所得固體用去離子水洗滌至濾液pH=8~9,80℃乾燥12小時,製得Y分子篩g,其SiO
2/Al
2O
3莫耳比為3.8,比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
對照例3
按照CN109692656A實例1的方法製備單一介孔NaY分子篩
取10.9千克偏鋁酸鈉溶液(其中含Al
2O
317.3質量%,Na
2O 21.0質量%)、48.3千克去離子水和13.1千克氫氧化鈉,攪拌使固體鹼完全溶解,然後加入66.8千克水玻璃(其中含SiO
228.3質量%,Na
2O 8.8質量%),攪拌至混合均勻,25℃靜置老化20小時製得導向劑,其中各物料莫耳比為:SiO
2/Al
2O
3=17,Na
2O/SiO
2=0.95,H
2O/SiO
2=17.6。
取187.2千克水玻璃、464.5千克去離子水和16.3千克氫氧化鈉,25℃充分攪拌混合,並在攪拌下加入90.6千克偏鋁酸鈉,然後加入0.9千克導向劑,攪拌均勻,加入8.2千克濃度為20質量%的聚二烯丙基二甲基氯化銨(R)水溶液為模板劑溶液,聚二烯丙基二甲基氯化銨分子量為100000~200000,繼續攪拌至混合均勻,得到合成系統,其中各物料莫耳比為:SiO
2/Al
2O
3=5.8,Na
2O/SiO
2=0.88,H
2O/SiO
2=31,R/SiO
2的質量比為0.03,導向劑的加量以其中的SiO
2計為合成系統SiO
2質量的0.2%。
將上述合成系統升溫至100℃,在靜止條件下水熱晶化8小時。將晶化產物用去離子水洗滌至洗滌液pH值小於10,所得固體於80℃乾燥12小時,空氣氣氛中於200℃進行一段焙燒1小時,380℃進行二段焙燒1小時,540℃進行三段焙燒4小時,得到介孔NaY分子篩h,其SiO
2/Al
2O
3莫耳比為5.1,晶粒粒徑為1.3微米,孔徑分佈曲線見圖11,顯示為單一介孔,其比表面積、總孔體積、微孔孔體積和介孔孔體積以及甲苯吸附容量見表1。
實例6
製備本發明吸附劑並測試吸附性能。
(1)滾球成型:將92千克(灼基質量,下同)實例1製備的奈米NaY分子篩a與8千克高嶺土(含90質量%的高嶺石)、3千克白碳黑、3千克田菁粉混合均勻,放入轉盤中邊滾動邊噴入適量的去離子水,使固體粉料聚集成小球,滾球時噴入的水量為固體粉料的8質量%,白碳黑所含二氧化矽與高嶺土的質量比為0.3。經篩分,取粒徑為300~850µm的小球,80℃乾燥10小時、540℃焙燒4小時。
(2)原位晶化:將64千克(1)步焙燒後的小球置於200升氫氧化鈉與水玻璃(水玻璃中SiO
2含量為20.17質量%,Na
2O含量為6.32質量%)混合溶液中對焙燒後小球進行原位晶化處理,混合溶液中氧化鈉含量為5質量%,二氧化矽含量為3質量%,於95℃原位晶化處理4小時,取晶化後固體水洗至洗滌液pH小於10,80℃乾燥10小時,製得吸附劑A,吸附劑A中含89.3質量%的Y分子篩a、9.3質量%的轉晶生成的Y分子篩,1.4質量%的基質,採用脈衝實驗測得的吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
實例7
按實例6的方法製備吸附劑,不同的是(1)步使用實例2製備的奈米NaY分子篩b與高嶺土、白碳黑和田菁粉混合後滾球成型,經原位晶化製得吸附劑B,其中含89.3質量%的Y分子篩b、9.6質量%的轉晶生成的Y分子篩,1.1質量%的基質,吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
實例8
按實例6的方法製備吸附劑,不同的是(1)步使用實例3製備的奈米NaY分子篩c與高嶺土、白碳黑和田菁粉混合後滾球成型,經原位晶化製得吸附劑C,其中含89.3質量%的Y分子篩c、9.8質量%的轉晶生成的Y分子篩,0.9質量%的基質,吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
實例9
按實例6的方法製備吸附劑,不同的是(1)步使用實例4製備的奈米NaY分子篩d與高嶺土、白碳黑和田菁粉混合後滾球成型,經原位晶化製得吸附劑D,其中含89.3質量%的Y分子篩d、9.5質量%的轉晶生成的Y分子篩,1.2質量%的基質,吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
實例10
按實例6的方法製備吸附劑,不同的是(1)步使用實例5製備的奈米NaY分子篩e與高嶺土、白碳黑和田菁粉混合後滾球成型,經原位晶化製得吸附劑E,其中含89.3質量%的Y分子篩e、10.0質量%的轉晶生成的Y分子篩,0.7質量%的基質,吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
對照例4
按實例6的方法製備吸附劑,不同的是(1)步使用對照例1製備的NaY分子篩f與高嶺土、白碳黑和田菁粉混合後滾球成型,經原位晶化製得吸附劑F,其中含97.2質量%的Y分子篩,2.8質量%的基質,吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
對照例5
按實例6的方法製備吸附劑,不同的是(1)步使用對照例2製備的NaY分子篩g與高嶺土、白碳黑和田菁粉混合後滾球成型,經原位晶化製得吸附劑G,其中含97.6質量%的Y分子篩,2.4質量%的基質,吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
對照例6
按實例6的方法製備吸附劑,不同的是(1)步使用對照例3製備的NaY分子篩h與高嶺土、白碳黑和田菁粉混合後滾球成型,經原位晶化製得吸附劑H,其中含97.6質量%的Y分子篩,2.4質量%的基質,吸附選擇性、吸附容量、不同壓力下的破碎率和灼基堆密度見表2。
實例11
在連續逆流的小型模擬移動床裝置上用吸附劑A進行吸附分離間二甲苯的實驗。
所述小型模擬移動床裝置包括24根串聯的吸附柱,每根柱長195毫米,柱內直徑30毫米,吸附劑的總裝填量為3300毫升,裝填吸附劑A。在串聯的24根柱子首尾兩端用循環泵連接構成一個封閉的環路,如圖12所示。吸附原料、解吸劑、提取液、提餘液四股進、出物料將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根吸附柱為吸附區,提取液(柱6)和吸附原料(柱14)之間的9根吸附柱為提純區,解吸劑(柱1)和提取液(柱5)之間的5根吸附柱為解吸區,提餘液(柱22)和解吸劑(柱24)之間的3根吸附柱為緩衝區。吸附分離的溫度控制為145℃,壓力為0.8 MPa。
操作過程中,分別按1600毫升/時和500毫升/時的流量連續地向上述模擬移動床裝置中注入解吸劑甲苯和吸附原料,並以761毫升/時的流量將提取液抽出裝置,1339毫升/時的流量將提餘液抽出裝置。所述吸附原料的組成為乙苯14.99質量%、對二甲苯20.14質量%、間二甲苯42.25質量%、鄰二甲苯21.75質量%、非芳烴組份0.87質量%。設定循環泵流量3960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(圖12中,從實線至虛線位置,以此類推)。在穩定操作狀態下得到的間二甲苯純度為99.58質量%,產率為97.15質量%。
實例12
在小型模擬移動床裝置上裝填吸附劑B,按實例11的方法進行吸附分離間二甲苯實驗,穩定操作狀態下獲得的間二甲苯的純度為99.62質量%,產率為97.29質量%。
對照例7
在小型模擬移動床裝置上裝填對照吸附劑F,按實例11的方法進行吸附分離間二甲苯實驗,穩定操作狀態下得到的間二甲苯的純度為99.51質量%,產率為91.53質量%。
對照例8
在小型模擬移動床裝置上裝填對照吸附劑H,按實例11的方法進行吸附分離間二甲苯實驗,穩定操作狀態下得到的間二甲苯的純度為99.52質量%,產率為89.77質量%。
表1
實例號 | Y分子篩編號 | 比表面積,m 2/g | 總孔體積,cm 3/g | 微孔孔體積,cm 3/g | 介孔孔體積,cm 3/g | 甲苯吸附容量,毫克/克 |
1 | a | 871 | 0.52 | 0.33 | 0.19 | 254 |
2 | b | 860 | 0.51 | 0.33 | 0.18 | 250 |
3 | c | 846 | 0.50 | 0.33 | 0.17 | 247 |
4 | d | 820 | 0.48 | 0.32 | 0.16 | 245 |
5 | e | 792 | 0.46 | 0.32 | 0.14 | 242 |
對照例1 | f | 705 | 0.33 | 0.32 | 0.01 | 236 |
對照例2 | g | 701 | 0.32 | 0.31 | 0.01 | 235 |
對照例3 | h | 745 | 0.81 | 0.30 | 0.51 | 233 |
表2
項 目 | 吸附劑編號 | |||||||||
A | B | C | D | E | F | G | H | |||
甲苯吸附容量,毫克/克 | 248.8 | 245.9 | 243.7 | 241.2 | 239.8 | 229.4 | 229.4 | 227.4 | ||
吸附選擇性 | β MX/EB | 4.87 | 4.93 | 4.83 | 4.75 | 4.53 | 4.32 | 4.10 | 4.08 | |
β MX/PX | 2.27 | 2.31 | 2.23 | 2.21 | 2.10 | 2.02 | 1.86 | 2.01 | ||
β MX/OX | 2.25 | 2.28 | 2.22 | 2.20 | 2.07 | 2.00 | 1.86 | 1.92 | ||
β MX/T | 1.00 | 1.00 | 1.00 | 1.00 | 1.00 | 1.01 | 1.00 | 1.00 | ||
[S A] 10-90,毫升 | 14.01 | 14.40 | 14.86 | 15.08 | 15.40 | 16.60 | 17.80 | 16.16 | ||
[S D] 90-10,毫升 | 14.05 | 14.43 | 14.88 | 15.11 | 15.46 | 16.76 | 17.86 | 16.20 | ||
破碎率,質量% | 130牛頓 | 0.20 | 0.21 | 0.23 | 0.20 | 0.18 | 0.49 | 0.52 | 0.56 | |
250牛頓 | 2.59 | 3.02 | 3.16 | 2.72 | 2.35 | 5.83 | 6.17 | 6.75 | ||
灼基堆密度,克/毫升 | 0.64 | 0.64 | 0.64 | 0.65 | 0.65 | 0.65 | 0.65 | 0.61 | ||
無
圖1為本發明實例1製備的介孔奈米Y分子篩的X射線繞射(XRD)圖譜。
圖2為本發明實例1製備的介孔奈米Y分子篩的掃描電子顯微鏡(SEM)照片。
圖3為本發明實例1製備的介孔奈米Y分子篩的孔徑分佈曲線。
圖4為本發明實例2製備的介孔奈米Y分子篩的孔徑分佈曲線。
圖5為本發明實例3製備的介孔奈米Y分子篩的孔徑分佈曲線。
圖6為本發明實例4製備的介孔奈米Y分子篩的孔徑分佈曲線。
圖7為本發明實例5製備的介孔奈米Y分子篩的孔徑分佈曲線。
圖8為對照例1製備的Y分子篩的XRD圖譜。
圖9為對照例1製備的Y分子篩的SEM照片。
圖10為對照例1製備的Y分子篩的孔徑分佈曲線。
圖11為對照例3製備的Y分子篩的孔徑分佈曲線。
圖12為小型模擬移動床吸附分離示意圖。
Claims (21)
- 一種間二甲苯吸附劑,包括94~99.9質量%的Y分子篩和0.1~6質量%的基質,所述Y分子篩由非轉晶Y分子篩和轉晶生成的Y分子篩組成,所述非轉晶Y分子篩為介孔奈米Y分子篩,所述介孔奈米Y分子篩的晶粒粒徑為20~450奈米,含有兩種介孔孔道,最可能孔直徑分別為5~20奈米和25~50奈米。
- 如請求項1所述的吸附劑,包括98~99.9質量%的Y分子篩和0.1~2質量%的基質。
- 如請求項1所述的吸附劑,包括84~93質量%的非轉晶Y分子篩、1~15.9質量%的轉晶生成的Y分子篩和0.1~6質量%的基質。
- 如請求項1-3中任一項所述的吸附劑,其中所述的吸附劑包括84~93質量%的非轉晶Y分子篩、5~15.9質量%的轉晶生成的Y分子篩和0.1~2質量%的基質。
- 如請求項1-4中任一項所述的吸附劑,其中所述介孔奈米Y分子篩為奈米級Y分子篩晶粒自聚體,自聚體粒徑為0.5~1.5微米,自聚體中奈米級Y分子篩晶粒粒徑為20~400奈米。
- 如請求項1-4中任一項所述的吸附劑,其中所述介孔奈米Y分子篩的SiO 2/Al 2O 3莫耳比為4.0~5.5。
- 如請求項1-4中任一項所述的吸附劑,其中所述介孔奈米Y分子篩的比表面積為740~1000 m 2/g,總孔體積為0.40~0.65 cm 3/g,介孔孔體積為0.08~0.35 cm 3/g。
- 如請求項1-4中任一項所述的吸附劑,其中所述介孔奈米Y分子篩的最可能孔徑分別為10~20奈米和30~50奈米。
- 一種如請求項1-8中任一項所述吸附劑的製備方法,包括如下步驟: (1)將非轉晶NaY分子篩、高嶺土礦物、矽源和成型助劑混合均勻,滾球成型製成小球,乾燥後於530~600℃焙燒,所述非轉晶NaY分子篩與高嶺土礦物的質量比為85~94:6~15,加入的矽源中所含二氧化矽與高嶺土礦物的質量比為0.1~3.6; (2)將(1)步驟焙燒後所得小球用氫氧化鈉或氫氧化鈉與水玻璃的混合溶液於85~100℃進行原位晶化處理,使其中的高嶺土礦物原位晶化為Y分子篩,然後水洗、乾燥。
- 如請求項9所述的方法,其中(1)步驟所述的高嶺土礦物選自高嶺石、地開石、珍珠石、耐火石、埃洛石或它們的混合物。
- 如請求項9所述的方法,其中(1)步驟所述的成型助劑選自木質素、田菁粉、乾澱粉、羧甲基纖維素和活性碳中的至少一種。
- 如請求項9所述的方法,其中(1)步驟中所述的矽源選自正矽酸乙酯、矽溶膠、水玻璃、矽酸鈉、矽膠和白碳黑中的一種或幾種,加入的矽源中所含二氧化矽與高嶺土礦物的質量比為0.2~3.0。
- 如請求項9所述的方法,其中(2)步驟中原位晶化處理的液/固比為1.5~5.0升/千克。
- 如請求項9所述的方法,其中(2)步驟原位晶化處理使用氫氧化鈉溶液時,其中氫氧根離子的濃度為0.1~3.0莫耳/升;當原位晶化處理使用氫氧化鈉和水玻璃混合溶液時,其中氧化鈉含量為2~10質量%,二氧化矽含量為1~6質量%。
- 如請求項9所述的方法,其中(1)步驟所述的非轉晶NaY分子篩的製備方法,包括如下步驟: (Ⅰ)取0~5℃的矽源、鋁源,加入氫氧化鈉、水混合均勻形成分子篩合成系統,其中各物料的莫耳比為:SiO 2/Al 2O 3=5.5~9.5、Na 2O/SiO 2=0.1~0.3、H 2O/SiO 2=5~25,合成系統的溫度為1~8℃, (Ⅱ)將(Ⅰ)步驟的分子篩合成系統於20~40℃靜態老化10~48小時,再於90~150℃靜態晶化2~10小時,攪拌2~10分鐘,繼續靜態晶化11~20小時,將所得固體洗滌、乾燥。
- 如請求項15所述的方法,其中(Ⅰ)步驟所述分子篩合成系統中各物料的莫耳比為:SiO 2/Al 2O 3=7~9、Na 2O/SiO 2=0.1~0.25、H 2O/SiO 2=8~20。
- 如請求項15所述的方法,其中(Ⅱ)步驟將分子篩合成系統於20~40℃靜態老化15~30小時,再於90~120℃靜態晶化4~9小時,攪拌2~10分鐘,繼續靜態晶化11~15小時。
- 如請求項15所述的方法,其中(Ⅰ)步驟所述的鋁源選自低鹼度偏鋁酸鈉溶液、氧化鋁、氫氧化鋁、硫酸鋁溶液、氯化鋁、硝酸鋁和鋁酸鈉中的一種或幾種。
- 如請求項18所述的方法,其中所述的低鹼度偏鋁酸鈉溶液中Al 2O 3含量為17~28質量%,Na 2O含量為19~30質量%。
- 如請求項15所述的方法,其中所述的矽源選自矽溶膠或水玻璃。
- 如請求項20所述的方法,其中所述水玻璃中SiO 2含量為25~38質量%,Na 2O含量為9~15質量%。
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