CN100528353C - 沸石催化剂改性方法 - Google Patents

沸石催化剂改性方法 Download PDF

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CN100528353C
CN100528353C CNB2005100696625A CN200510069662A CN100528353C CN 100528353 C CN100528353 C CN 100528353C CN B2005100696625 A CNB2005100696625 A CN B2005100696625A CN 200510069662 A CN200510069662 A CN 200510069662A CN 100528353 C CN100528353 C CN 100528353C
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CN1704167A (zh
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A·K·戈霍斯
G·朱特图
P·哈维
N·库卡尼
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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Abstract

提供一种对沸石催化剂进行改性以增加在甲苯甲基化反应中沸石催化剂的对二甲苯选择性的方法。该方法包括：形成ZSM-5型沸石和磷化合物的水溶液的淤浆；从淤浆中除去水，提供一种未经蒸汽处理的、经磷处理的ZSM-5沸石催化剂，而无需通过有机磷蒸汽沉积在催化剂上沉积磷。所得未经蒸汽处理的、经磷处理的ZSM-5沸石催化剂具有0.2ml/g或更低的孔体积，和在用于甲苯甲基化时提供按混合二甲苯计80%以上的对二甲苯选择性。

Description

沸石催化剂改性方法
技术领域
本发明一般地涉及芳香化合物烷基化和这类反应所使用的催化剂。
背景技术
对二甲苯是一种有价值的取代芳香化合物，因为为生产形成聚酯纤维和树脂的主要成分对苯二甲酸而对其具有大量需求。它能够大规模生产自石脑油的加氢处理(催化重整)，石脑油或汽油的蒸汽裂化，以及甲苯歧化。
采用甲醇进行甲苯烷基化也称为甲苯甲基化，已经在实验室研究中用于生产对二甲苯。已知甲苯甲基化发生在酸性催化剂上，特别是沸石或沸石类催化剂上。具体地说，已经将ZSM-5-型沸石、沸石β和硅铝磷酸盐(SAPO)催化剂用于该方法。一般说，自甲苯甲基化能形成邻(o)、间(m)和对(p)二甲苯的热力学平衡混合物，正如下述反应所示：
在反应温度约500℃下，邻、间和对二甲苯的热力学平衡组成可以分别为约25、50和25mol％。但是，这种甲苯甲基化反应可以发生在广范围的温度下。对二甲苯能够通过吸附和异构化的循环过程从混合的二甲苯中分离出来。诸如Ca+和其它芳香产物等副产物能够通过二甲苯产物的二次烷基化来生产。
如果催化剂具有择形性能，那么在甲苯甲基化反应中能够得到显著的较高量的对二甲苯。就改性沸石催化剂而论，择形性能能够通过改进沸石气孔孔径大小、沸石外表面钝化或者控制沸石酸性来得到。甲苯甲基化可以发生在改性ZSM-5或ZSM-5型沸石催化剂上，所得到的二甲苯产物包含的对二甲苯含量大大高于其热力有效浓度。
已经应用磷酸和其它含磷化合物改进ZSM-5沸石催化剂提供择形性能。例如，美国专利6,504,072公开了采用磷来处理ZSM-5沸石催化剂，以便在强蒸汽处理之前控制扩散性和孔体积降低提供对位选择的催化剂。美国专利4,554,394叙述了采用汽相有机磷试剂处理ZSM-5沸石提供对位选择性能。
不幸的是，对于大规模地成功地进行甲苯甲基化而言尚有许多技术障碍，因此需要进行改进。
附图说明
为了更完整地理解本发明，请参阅如下描述并结合附图，其中
图1是H3PO4改性不同ZSM-5沸石催化剂的BET表面面积作为在改性中磷用量的函数的曲线图；
图2是H3PO4改性的不同ZSM-5沸石催化剂的总孔体积作为在改性中磷用量的函数的曲线图；
图3表示(a)SiO2/Al2O3摩尔比为280的NH4-ZSM-5的和(b)磷改性ZSM-5沸石催化剂两者的27Al MAS-NMR谱图。
图4是(对于自在起始SiO2/Al2O3摩尔比为30的H3PO4改性ZSM-5沸石催化剂上进行的甲苯甲基化得到的产物液流而言，总二甲苯wt％总二甲苯选择性、对二甲苯选择性作为在改性中磷用量的函数的曲线图；
图5是(对于自在起始SiO2/Al2O3摩尔比为280的H3PO4改性ZSM-5沸石催化剂上进行的甲苯甲基化得到的产物液流而言，总二甲苯wt％总二甲苯选择性、对二甲苯选择性作为在改性中磷用量的函数的曲线图。
发明内容
本文所用措词“ZSM-5-型”意指在结构上与ZSM-5沸石相同的那些沸石。另外，措词“ZSM-5”和“ZSM-5-型”在本文中可以互换应用彼此包含，并且不应该以任何限制的意义解释。ZSM-5沸石催化剂及其制备叙述在美国专利3,702,886中，在此引入该专利作为参考。
本文所用的催化活性能够定义为，以在给定甲苯甲基化反应条件下得到的产物液流中总二甲苯的wt％计量的总二甲苯生产率。本文所用的总二甲苯选择性能够定义为：
％总二甲苯选择性＝(Xtx/Xtap)×100        (2)
其中，Xtx是产物液液中总二甲苯的wt％，Xtap是产物液流中总芳族产物的wt％。本文所用的对二甲苯选择性可以表示为：
％对二甲苯选择性＝(Xp/Xtx)×100          (3)
其中，Xp是在产物液流中对二甲苯的wt％。
通过采用含磷化合物改进ZSM-5沸石催化剂以提供所选择的孔体积，可以获得增加的对位选择性而不需要对催化剂进行以后的蒸汽处理或另外的处理。另外，在采用特定ZSM-5沸石催化剂进行甲苯甲基化期间可以得到增加催化剂活性和总二甲苯选择性，同时仍然提供高的对二甲苯选择性。
起始ZSM-5沸石可以是NH4-或H-形式的沸石，其可以是粉末形式或任何其它形式。在本发明中，ZSM-5沸石催化剂可以包括在用含磷化合物改性前二氧化硅/氧化铝摩尔比大于25者。正如下文所讨论的，初始ZSM-5沸石催化剂的二氧化硅/氧化铝比，可以对随后处理的催化剂在甲苯甲基化中的催化剂活性和二甲苯选择性有影响。在某些例子中，起始ZSM-5的SiO2/Al2O3摩尔比可以为从250、280、300至1000或更多，从而得到较高的活性以及增加的对二甲苯选择性。
磷化合物可以是含磷的酸，例如磷酸(H3PO4)和亚磷酸(H3PO3)。对于含磷的酸而言，所用的酸的浓度可以为50wt％以上。磷化合物也可以包括其它非酸含磷化合物，例如磷酸氢铵[(NH4)2HPO4]。所用的磷的量可以为处理过的催化剂提供的磷含量为0.04g P/g沸石或更多。在某些应用中，掺入催化剂的磷的量可以为0.09g P/g沸石或更多，在这些应用中适宜的是约0.09g P/g沸石至约0.15g P/g沸石。
可以将磷掺入催化剂的方法包括：制备沸石和磷化合物水溶液的淤浆。将淤浆加热可以用来促进沸石催化剂的处理以及液体蒸发。在大多数情况下，适宜的是将淤浆加热至70℃～约100℃。在该步骤中也可以搅动或搅拌淤浆从而保证处理得均匀。
磷改性沸石催化剂使用时可以不进行粘结或者采用粘合剂粘结。适宜粘合剂的例子包括氧化铝、粘土和二氧化硅等材料。本领域众所周知制备粘合催化剂所使用的那些工艺。可以在400℃～570℃下，于含氧，典型地含空气，的环境中，煅烧粘合的或未粘合的催化剂。
处理过的ZSM-5沸石催化剂应该提供约0.2ml/g或更低的总孔体积。更具体地说，总孔体积可以为约0.18ml/g～约0.07ml/g。ZSM-5沸石催化剂的BET表面积可以为300m2/g以下至约10m2/g。
磷改性催化剂，在沸石骨架中，含有大量四面体/结构Al，在约50ppm处显示弱27Al-NMR峰，但是在沸石孔内部催化剂含有“碎片”或超骨架铝(EFAl)，其在-14ppm处显示强27Al-NMR峰。对于处理过的沸石催化剂来说，骨架铝与超骨架铝之比可以为约0.12～0.25。
处理过的催化剂可以在甲苯甲基化中用作未经蒸气处理的催化剂。本文所用的“未经蒸汽处理”，就沸石催化剂来说，意指包括下述的沸石催化剂，该催化剂没有被处理或经受高温蒸流(即950℃)的处理以实现其在用于任何烷基化或甲基化反应之前的结构变化。
改性催化剂可以在甲基化反应条件下与适宜甲苯和甲醇进料接触进行甲苯甲基化反应。也可以采用氢共进料。氢的用量可以为每摩尔甲苯/甲醇进料至少0.1mol。
水或蒸汽也可以作为共进料与甲苯/甲醇进料一起引入反应器中。用于甲基化反应的水或蒸汽可以在甲基化反应起动期间，采用或不采用氢共进料，与烃进料一起引入反应器中；或者其可以在所述反应初始起动之后加入。在任一情况下，液态水可以在其与氢共进料(如果有的话)和烃进料混合之前加入和汽化。
甲苯甲基化或其它芳族烷基化的反应器压力可以变化，但是一般为约10～约1000Psig。反应器温度可以为400～700℃。
所述反应可以在各种一般用于进行芳族烷基化反应的各种反应器中进行。单个或者串联的和/或并联的多个反应器均适于进行甲苯甲基化。
改性的催化剂用于从甲苯和甲醇进料制备二甲苯产物的甲苯甲基化反应，该反应具有增加的对二甲苯选择性。具体地说，当将所述催化剂用于甲苯甲基化中时，其可以提供比80％、85％和90％大的对二甲苯选择性，另外，在某些情况下，可以得到90％以上总二甲苯选择性。
具体实施方式
以下实施例进一步说明本发明。
实施例
催化剂制备
催化剂A-H
起始材料是SiO2/Al2O3摩尔比为30的NH4-ZSM-5沸石粉末。在400ml烧杯中制备含有11.63g NH4-ZSM-5沸石和50ml去离子水的水淤浆。将烧杯置于热板上并用电磁搅拌棒搅拌沸石悬浮体。悬浮体温度维持在约90℃。将1.08g磷酸(85wt％，在水中)滴加到烧杯中。继续加热直至全部液体蒸发。磷酸改性沸石在90℃～120℃下干燥至少4hr，在340℃～360℃下干燥3hr，然后在510℃～530℃下在空气中煅烧10hr。然后粉碎煅烧过的沸石，再采用20目和40目的筛子分级。通过相对起始NH4-ZSM-5粉末的量改变磷酸的量，制备一系列的催化剂A-H(见表1)。催化剂A-H的BET表面积和总孔体积(采用N2吸附测定)示于表1以及图1和2。
表1
Figure C20051006966200081
a在制备中使用的磷酸(85％，在水中)或磷的总量
正如自表1及图1和2所能见到的，发现，采用SiO2/Al2O3摩尔比为30的NH4-ZSM-5制备的沸石催化剂A-H的BET表面积(SA)和总孔体积(PV)，随着磷酸或P的量的增加，而大幅度下降。
催化剂J-N
起始物料是SiO2/Al2O3摩尔比为280的NH4-ZSM-5沸石粉末。在400ml烧杯中制备含有12.09gNH4-ZSM-5沸石和50ml去离子水的淤浆。将烧杯置于热板上并用电磁搅拌棒搅拌沸石悬浮体。悬浮体温度维持在约90℃。将1.08g磷酸(85wt％，在水中)滴加到烧杯中。继续加热直至全部液体蒸发。磷酸改性沸石在90℃～120℃下干燥至少4hr，在340℃～360℃下干燥3hr，然后在510℃～530℃下在空气中煅烧10hr。然后粉碎煅烧过的沸石，再采用20目和40目的筛子分级。通过相对起始NH4-ZSM-5粉末的量改变磷酸的量，制备一系列的催化剂J-N(见表2)。催化剂J-N的BET表面积和总孔体积(采用N2吸附测定)示于表2以及图1和2。采用SiO2/Al2O3摩尔比为280的起始NH4-ZSM-5制备的催化剂，与采用SiO2/Al2O3摩尔比为30的起始NH4-ZSM-5制备的催化剂A-J比较，前者的SA和PA没有象后者的SA和PA那样显著下降。
表2
Figure C20051006966200091
a在制备中使用的磷酸(85％，在水中)或磷的总量
催化剂P-S
起始物料是SiO2/Al2O3摩尔比为280的NH4-ZSM-5沸石粉末。在400ml烧杯中制备含有51.66g NH4-ZSM-5沸石和200ml去离子水的淤浆。将烧杯置于热板上并用电磁搅拌棒搅拌沸石悬浮体。悬浮体的温度维持在约90℃。将9.07g磷酸氢铵，(NH4)2HPO4，溶解在50ml水中，然后将该盐溶液滴加到烧杯中。继续加热直至全部液体蒸发。磷酸氢铵改性沸石在90℃～120℃下干燥至少4hr，在340℃～360℃下干燥3hr，然后在510℃～530℃下在空气中煅烧10hr。然后粉碎煅烧过的沸石，再采用20目和40目的筛子分级。通过相对于起始NH4-ZSM-5粉末的量改变磷酸氢铵的量，制备一系列催化剂P-S(见表3)。催化剂P-S的BET表面积和总孔体积(采用N2吸附测定)示于表3。
表3
Figure C20051006966200101
a在制备中使用的磷酸(85％，在水中)或磷的总量
在给定磷量下采用磷酸制备的催化剂系列J-N和采用磷酸氢铵制备的催化剂系列P-S的表面面积和孔体积几乎没有差异或没有差异。因此，应用磷酸或磷酸氢铵作含磷化合物来制备对二甲苯选择催化剂并没有显著差别。
对比催化剂I&O
为了进行比较制备不含磷的ZSM-5沸石催化剂。起始物料或者是SiO2/Al2O3摩尔比为30的NH4-ZSM-5沸石粉末或者是SiO2/Al2O3摩尔比为280的NH4-ZSM-5沸石粉末。沸石粉末在340℃～360℃下干燥3hr，然后在510℃～530℃下在空气中煅烧10hr。然后将煅烧过的样品压碎，再用20目和40目筛子分级，以便用于进行甲苯甲基化反应的反应器中。催化剂I和O的性能分别列于表1和2中。
27Al MAS-NMR
对SiO2/Al2O3摩尔比为280的起始NH4-ZSM-5沸石和磷改性催化剂样品进行幻角自旋(MAS)固态NMR研究。测定采用400MHz分光计(27Al，在104.5MHz下)，室温，氮化硅转子(Si3N4)，13～14KHz样品自旋(约800000rpm)，10度末端以避免饱和和4000～10000扫描信号平均次数。不使用质子去偶。所有波谱均参考在化学位移标度0.0ppm处氯化铝六水合物(在管中独立试验)。这样得到关于氮化铝(在氮化硅转子中的少量杂质)的内标104.85ppm。
起始NH4-ZSM-5沸石样品在约55ppm处显示强27Al MAS-NMR峰，认为这是骨架四面体(4配位)铝所造成的(波谱a，图3)。共振锐度和对称性表明，沸石相对地是具有很少晶格缺陷的结晶。骨架Al决定沸石的酸性和起始沸石样品显示强酸性。磷改性样品在55～50ppm区域显示弱峰，这归因于结构四面体铝(波谱b，图3)。四面体铝峰严重畸变，说明在除去一些骨架铝之后在结构中存在由孔引起的多巢硅烷醇。邻近峰(30～40ppm)归因于严重畸变但仍然可能与氧3配位或5配位形式存在于骨架中的铝原子。波谱中-14ppm处最大峰得自八面体配位铝原子，这些铝原子在通过如上文所述磷酸盐改性方法从沸石骨架除去四面体配位的骨架铝时形成。
实施例1～19
在上文和表1～3中所述催化剂A-I，J-O和P-S均用于甲苯甲基化反应。所述反应均在固定床、连续流动型反应器中进行。在每种情况下，催化剂均通过在氢(H2)气流下缓慢升高催化剂床温度(约5℃/min)至200℃历时至少1hr进行干燥。将预混合的甲苯和甲醇进料(摩尔比2/1)加入到200℃反应器中并使催化剂床入口温度增加到约500℃。液体时空速度(LHSV)(以甲苯/甲醇进料为基准)保持在约31hr-1，进料入H2气共进料并维持H2/HC摩尔比约0.1。将水加到烃(HC)进料中，其在进入反应器之前汽化。H2O/HC摩尔比为约0.65，反应器压力为约20Psig。在运转时间为约3～4hr时，收集液体产物并进行分析。其结果列于下表4～6中。图4是催化剂A-I的对二甲苯选择性和总二甲苯选择性曲线图。图5是催化剂J-O的对二甲苯选择性和总二甲苯选择性曲线图。
表4
1产物液流分析
表5
Figure C20051006966200122
1产物液流分析
表6
Figure C20051006966200131
1产物液流分析
虽然仅仅以本发明的一些形式说明了本发明，但是本领域技术人员应该显而易见，本发明不受这些的限制，而且在不偏离本发明范围的条件下易于进行各种变更和改进。所以适当的是，所附权利要求得到了广泛的并且与本发明范围一致的解释。

Claims (13)

1.一种对沸石催化剂进行改进以增加在甲苯甲基化反应中沸石催化剂的对二甲苯选择性的方法，该方法包括：
形成SiO2/Al2O3摩尔比为250～1000的ZSM-5-型沸石和磷化合物水溶液的淤浆；和
从所得淤浆中除去水从而提供磷处理的ZSM-5沸石催化剂，其中所述磷处理的ZSM-5沸石催化剂未被进行蒸汽处理、未被通过有机磷蒸汽沉积在催化剂上沉积磷或者未被另外的催化剂处理，和其中所得未经蒸汽处理的、经磷处理的ZSM-5沸石催化剂具有0.2ml/g或更小的孔体积和磷含量为0.04gP/g沸石或更高，和当用于甲苯甲基化中在甲苯甲基化反应条件下提供按二甲苯产物计80％以上的对二甲苯。
2.权利要求1的方法，其中：
磷化合物是含磷的酸。
3.权利要求1的方法，其中：
处理过的沸石催化剂的孔体积为0.18ml/g以下。
4.权利要求1的方法，其中：
处理过的沸石催化剂的经27Al MAS-NMR测定的骨架铝与超骨架铝之比为0.12～0.25。
5.权利要求1的方法，其中：
处理过的沸石催化剂在用于甲苯甲基化时，提供按二甲苯产物计90％以上的对二甲苯选择性。
6.权利要求1的方法，其中：
处理过的沸石催化剂在磷处理之前具有至少250的二氧化硅与氧化铝之比，和提供90％以上的总二甲苯选择性和按二甲苯产物计85％以上的对二甲苯选择性。
7.权利要求1的方法，其中：
磷化合物包括磷酸(H3PO4)、亚磷酸(H3PO3)和磷酸氢铵[(NH4)2HPO4]中的至少一种。
8.权利要求1的方法，其中：
处理过的ZSM-5沸石催化剂的磷含量为0.09gP/g沸石以上。
9.一种制备二甲苯产物的方法，包括：
形成SiO2/Al2O3摩尔比为250～1000的ZSM-5型沸石和磷化合物水溶液的淤浆；
从所得淤浆中除去水从而提供未经蒸汽处理的、经磷处理的ZSM-5沸石催化剂，其中所述磷处理的ZSM-5沸石催化剂未被进行通过有机磷蒸汽沉积在催化剂上沉积磷或者未被另外的催化剂处理，和其中所得未经蒸汽处理的、经磷处理的ZSM-5沸石催化剂具有0.2ml/g或更低的孔体积和磷含量为0.04g P/g沸石或更高；和
在适合甲苯甲基化的反应条件下，使处理过的沸石催化剂与甲苯芳族进料和甲醇接触，提供含有按二甲苯产物计80％以上的对二甲苯的二甲苯产物。
10.权利要求9的方法，其中：
处理过的沸石催化剂具有0.18ml/g以下的孔体积。
11.权利要求9的方法，其中：
磷化合物包括磷酸(H3PO4)、亚磷酸(H3PO3)和磷酸氢铵[(NH4)2HPO4]中的至少一种。
12.权利要求9的方法，其中：
处理过的沸石催化剂在进行磷处理之前具有至少250的二氧化硅与氧化铝比，和提供90％以上的总二甲苯选择性和按二甲苯产物计85％以上的对二甲苯选择性。
13.权利要求9的方法，其中：
处理过的ZSM-5沸石催化剂的磷含量为0.09gP/g沸石以上。
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