CN113275032A - 用于甲苯甲醇侧链烷基化的分子筛催化剂及其制备方法和应用 - Google Patents
用于甲苯甲醇侧链烷基化的分子筛催化剂及其制备方法和应用 Download PDFInfo
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 23
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- BKBMACKZOSMMGT-UHFFFAOYSA-N methanol;toluene Chemical group OC.CC1=CC=CC=C1 BKBMACKZOSMMGT-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910000397 disodium phosphate Inorganic materials 0.000 claims abstract description 12
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
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- 238000003756 stirring Methods 0.000 claims description 5
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- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 4
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- 125000003944 tolyl group Chemical group 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
本发明公开了一种用于甲苯甲醇侧链烷基化的分子筛催化剂，包括NaX型分子筛和负载在其上的Na3PO4或Na2HPO4。本发明提供的分子筛催化剂可有效催化甲苯甲醇侧链烷基化反应。本发明还提供了一种用于甲苯甲醇侧链烷基化的分子筛催化剂的制备方法，该方法简便易行，且成本低廉。
Description
技术领域
本发明涉及甲苯甲醇侧链烷基化生产苯乙烯的技术领域，更具体而言，涉及一种用于甲苯甲醇侧链烷基化的分子筛催化剂。此外，本发明还涉及该催化剂的制备方法和应用。
背景技术
苯乙烯是工业上重要的单体，可用于生产许多聚合物，例如，橡胶和塑料。当前，苯乙烯的生产方法主要需要两个步骤：首先是用乙烯进行苯烷基化生产乙苯，然后将乙苯脱氢为苯乙烯，该工艺过程通常在高温(高于600℃)下进行，吸热、能耗大且热力学受限。此外，这种由乙苯生产苯乙烯的方法还存在一些主要的环境问题，例如，排放有害的温室气体。
甲苯甲醇侧链烷基化是一项在温和条件下实现一步法生产苯乙烯的前瞻性技术。这种生产苯乙烯的方法减少了温室气体的排放，并且相对节能。
到目前为止，许多研究人员已经使用不同的分子筛催化剂进行了甲苯甲醇侧链烷基化，特别是CsX分子筛催化剂，然而，这些催化剂的生产成本很是昂贵。NaX型分子筛便宜得多，因此，人们期望可以使用NaX型分子筛来进行甲苯甲醇侧链烷基化。
CN 109395767 A中公开了一种K3PO4/NaX催化剂，其制备方法是：a)将NaX型分子筛和K3PO4溶液按比例混合，在80℃水浴下搅拌2h，抽滤，得到固体I；b)将步骤a)所得的固体I按比例加入K3PO4溶液混合，在80℃水浴下搅拌2h，抽滤，得到固体II；c)将步骤b)所得的固体II按比例加入K3PO4溶液混合，在80℃水浴下搅拌2h，抽滤，得到固体III；在80℃条件下，将固体III干燥12h，焙烧3h。
该方法要求将NaX型分子筛与K3PO4溶液交换三次并洗涤三次来制备K3PO4/NaX催化剂，步骤复杂。
发明内容
因此，本发明的目的在于克服现有技术中的缺陷，提供一种制备方法简单、成本低廉且可有效催化甲苯甲醇侧链烷基化生产苯乙烯的分子筛催化剂。
本发明的第一方面涉及一种用于甲苯甲醇侧链烷基化的分子筛催化剂，具体而言，涉及用Na3PO4或Na2HPO4改性的NaX型分子筛催化剂，被称为Na3PO4(或Na2HPO4)/NaX。
本发明的分子筛催化剂包括NaX型分子筛和负载在其上的Na3PO4或Na2HPO4。
在一些实施例中，所述NaX型分子筛的Si/Al比约为1-10，比表面积约为40m2/g～600m2/g。在优选实施例中，所述NaX型分子筛的Si/Al比约为1.24，比表面积约为527m2/g。
在优选实施例中，所述分子筛催化剂的目数为40～60目。
本发明的第二方面涉及一种用于甲苯甲醇侧链烷基化的分子筛催化剂的制备方法，包括以下步骤：
(1)将NaX型分子筛浸渍于Na3PO4或Na2HPO4的水溶液中，于60～90℃下搅拌2h，然后冷却至室温；
(2)将冷却后溶液入60～90℃烘箱，蒸发掉全部液体；
(3)将步骤(2)所得固体在空气中于400～600℃下煅烧3h，加热速率为3K/min。
在一些实施例中，所述NaX型分子筛的Si/Al比约为1-10，比表面积约为40m2/g～600m2/g。在优选实施例中，所述NaX型分子筛的Si/Al比约为1.24，比表面积约为527m2/g。
在一些实施例中，步骤(1)中，Na3PO4或Na2HPO4的浓度为0.01M～0.1M。在优选实施例中，步骤(1)中，Na3PO4或Na2HPO4的浓度为0.05M～0.075M；对于甲苯甲醇侧链烷基化制苯乙烯的催化反应，在此浓度范围下制备的Na3PO4/NaX或Na2HPO4/NaX分子筛催化剂可使产物乙苯和苯乙烯的总选择性和总收率分别高达60％以上，并且可提供比K3PO4/NaX催化剂高约91％以上的苯乙烯收率。
在优选实施例中，步骤(1)中的温度为80℃。
在优选实施例中，在步骤(2)中，将冷却后溶液入60～90℃烘箱蒸发16～18h。
在优选实施例中，步骤(3)中的煅烧温度为500℃。
在优选实施例中，上述方法还包括对煅烧后固体进行粉碎、压制和筛分，筛选出40-60目颗粒的分子筛催化剂。
本发明提供的用于甲苯甲醇侧链烷基化的分子筛催化剂使用廉价的NaX型分子筛，并且负载的改性成分仅为Na3PO4或Na2HPO4，而且，制备方法简单易行，由此导致催化剂原料成本、生产成本低廉。
不同于CN 109395767A中公开的须交换三次并洗涤三次来进行制备的K3PO4/NaX催化剂，本发明提供的Na3PO4(或Na2HPO4)/NaX分子筛催化剂的制备方法更简单，只涉及一次浸渍，一次蒸干。
另外，研究发现，本发明提供的Na3PO4(或Na2HPO4)/NaX分子筛催化剂的寿命长于K3PO4/NaX。
具体实施方式
下面参照具体实施例对本发明的用于甲苯甲醇侧链烷基化的分子筛催化剂及其制备方法进行描述，应当理解，该些实施例仅是示例性的，并不用于限制本发明的范围。
实施例1
将10gNaX型分子筛(南开大学催化剂厂，Si/Al＝1.24，比表面积为527m2/g)浸渍于100mLNa3PO4·12H2O(0.01M)的水溶液中。于80℃下搅拌2h，然后静置冷却至室温。冷却后溶液无需过滤，直接入80℃烘箱约17h，蒸发掉全部液体。然后，将所得固体在空气中于500℃下煅烧3h，加热速率为3K/min。对煅烧后固体进行粉碎、压制和筛分处理，筛选出40-60目颗粒。
实施例2-5
实施例2-5与实施例1基本相同，区别仅在于所用Na3PO4水溶液的浓度不同，实施例2-5所用Na3PO4水溶液的浓度分别为0.025M、0.05M、0.075M和0.1M。
实施例6
在大气压下，于固定床反应器中测试以上实施例1-5制备的催化剂对甲苯甲醇侧链烷基化反应的催化性能。
将1.2g催化剂置于内径为7mm的不锈钢管的中间，并在反应管出口用石英砂对催化剂进行支撑，且在反应管中间用石英棉隔开。氮气用作载气，流速为10.0ml/min，甲苯与甲醇的摩尔比为5:1，质量空速为1.0h-1。首先在大气氮气氛下于450℃下对催化剂活化2h，然后，将温度降到425℃对催化剂进行性能评估。为防止反应气体冷凝，自反应器至六通阀用加热带包裹以将温度保持在200℃左右，此外，还配有辅助炉，以将自六通阀至色谱进样器的温度保持在200℃左右。
通过配备有HP-FFAP柱(0.53mm×50m)的海欣GC950气相色谱仪在线定量分析反应产物，并通过氢火焰离子化检测器(FID)检测反应产物。色谱仪的具体参数设置如下：柱炉温度为70℃，检测器温度为220℃，气化室温度为200℃，空气分压为0.05MPa，氢气分压为0.12MPa，载气流速为35ml/min，注气量为0.1ml/h。产物组成用面积校正归一化法计算。由于反应体系中使用的甲苯过量，因此，转化率、产物选择性和收率都基于甲醇进行计算。
下面的表1给出了实施例6的测试结果，具体而言，给出了在实施例1-5制备的催化剂的催化作用下，摩尔比为5:1的甲苯和甲醇组合物进料在1.0h-1的质量空速、10ml/min的氮气流速及425℃的反应温度下的甲醇转化率、乙苯和苯乙烯的选择性和收率的结果。
表1催化剂性能
由表1结果可知，本发明实施例的Na3PO4/NaX催化剂可有效催化甲苯甲醇侧链烷基化反应，特别是利用0.05M～0.075M Na3PO4溶液制得的Na3PO4/NaX催化剂可使产物乙苯和苯乙烯的总选择性和总收率高达60％以上。此外，利用0.05M～0.075M Na3PO4溶液制得的Na3PO4/NaX催化剂可使苯乙烯的收率明显高于CN 109395767A中公开的K3PO4/NaX催化剂，苯乙烯收率提高了约91％以上。
另外，发明人发现，使用0.01M～0.1M Na2HPO4溶液制备的Na2HPO4/NaX催化剂应用于甲苯甲醇侧链烷基化反应时，可获得与上面Na3PO4/NaX催化剂类似的结果。
以上参照优选实施例对本发明作了进一步说明，然而，在不脱离所附权利要求书限定的范围的情况下，可以对该些实施例作出许多变化或修改。
Claims (10)
1.用于甲苯甲醇侧链烷基化的分子筛催化剂，其特征在于，所述分子筛催化剂包括NaX型分子筛和负载在其上的Na3PO4或Na2HPO4。
2.根据权利要求1所述的分子筛催化剂，其特征在于，所述NaX型分子筛的Si/Al比为1-10，比表面积为40m2/g～600m2/g，优选的，所述NaX型分子筛的Si/Al比为1.24，比表面积为527m2/g。
3.根据前述任一权利要求所述的分子筛催化剂，其特征在于，所述分子筛催化剂的目数为40～60目。
4.用于甲苯甲醇侧链烷基化的分子筛催化剂的制备方法，其特征在于，所述方法包括以下步骤：
a.将NaX型分子筛浸渍于Na3PO4或Na2HPO4的水溶液中，于60～90℃下搅拌2h，然后静置冷却至室温；
b.将冷却后溶液入60～90℃烘箱，蒸发掉全部液体；
c.将步骤b所得固体在空气中于400～600℃下煅烧3h，加热速率为3K/min。
5.根据权利要求4所述的方法，其特征在于，所述NaX型分子筛的Si/Al比为1-10，比表面积为40m2/g～600m2/g，优选的，所述NaX型分子筛的Si/Al比为1.24，比表面积为527m2/g。
6.根据权利要求4-5任一项所述的方法，其特征在于，步骤a中，Na3PO4或Na2HPO4的浓度为0.01M～0.1M，优选的，Na3PO4或Na2HPO4的浓度为0.05M～0.075M。
7.根据权利要求4所述的方法，其特征在于，步骤a中的温度为80℃，在步骤b中，将冷却后溶液入60～90℃烘箱蒸发16～18h，步骤c中的煅烧温度为500℃。
8.根据权利要求4所述的方法，其特征在于，所述方法还包括对步骤c所得的煅烧后固体进行粉碎、压制和筛分，筛选出40-60目颗粒的分子筛催化剂。
9.权利要求5-13任一项所述的方法制备的用于甲苯甲醇侧链烷基化的分子筛催化剂。
10.权利要求1-4任一项所述的分子筛催化剂或权利要求5-13任一项所述的方法制备的分子筛催化剂在甲苯甲醇侧链烷基化中的应用。
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