CN116273154B - 兼具噻吩烷基化与硫醇醚化双功能催化剂及其制备方法 - Google Patents
兼具噻吩烷基化与硫醇醚化双功能催化剂及其制备方法 Download PDFInfo
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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Abstract
本发明公开一种兼具噻吩烷基化与硫醇醚化双功能催化剂及其制备方法，制备过程包括以下步骤：首先将高岭土在高温下焙烧活化得到偏高岭土，然后采用磷酸溶液对偏高岭土进行脱铝处理，最后向偏高岭土的磷酸浆液中加入合成SAPO‑11分子筛所用的硅源、铝源和模板剂并进行晶化，经过滤、洗涤和干燥得到梯级孔SAPO‑11@高岭土酸性载体材料。负载活性金属Ni‑Mo后得到兼具硫醇醚化和噻吩烷基化功能的催化剂。以噻吩和乙硫醚为模型化合物进行反应性能测试，噻吩烷基化和硫醇醚化转化率可高达95%以上。
Description
技术领域
本发明涉及一种兼具噻吩烷基化与硫醇醚化功能的催化剂及其制备，属于炼油催化剂领域。
背景技术
催化裂化(FCC)汽油具有硫含量和烯烃含量高的特点，在我国汽油池中90%以上的硫化物来源于 FCC汽油，因此，我国汽油清洁化的关键在于降低 FCC汽油中硫和烯烃含量，并尽可能的降低辛烷值损失。选择性加氢脱硫技术具有操作简单和技术成熟的优点，被广泛的应用于汽油清洁化生产过程，其工艺原理是将催化裂化汽油中的低沸点、小分子硫醇经过醚化反应转化为高沸点硫醚，或者将沸点更高的噻吩经过烷基化反应转化为更高沸点的烷基取代噻吩，最后经过切割工艺将全馏分汽油切割为轻汽油和重汽油，从而实现轻汽油中的烯烃不被加氢饱和成为低辛烷值烷烃的目的。因此，兼具硫醇醚化和噻吩烷基化功能催化剂的开发是汽油清洁化技术开发的重点。
CN 201611056044.1公开了一种低温硫醇醚化催化剂的制备方法，通过添加碱性金属助剂氧化物制备的Ni-Mo催化剂，在缓和的条件下具有反应活性高、脱硫醇效率好的特点，可用于汽油和液化气脱硫工艺。2000年，BP公司提出将汽油中的噻吩与烯烃发生烷基化反应的设计思路之后，噻吩烷基化催化剂被广泛的研究。201019114007.5公开了一种汽油醚化、烷基化脱硫的方法，催化剂是以SiO2-Al2O3或SiO2-ZrO2为载体，磷酸或多聚磷酸为活性组分，制备的催化剂硫醇和噻吩的转移率达90%以上，但这一催化剂用于工业生产中存在流失的问题。美国专利US 2563087和US5171916公开了噻吩与烯烃发生烷基化反应的催化剂，以AlCl3等为酸性载体材料制备而成，在工业生产中存在设备腐蚀等问题，不利于工业化生产。CN200710010741.8公开了一种汽油烷基化脱硫催化剂及其制备方法，采用介孔MCM-22分子筛为酸性载体材料制备的催化剂可将汽油中60%以上的硫化物转化脱除，效果比较理想。
本发明以脱铝高岭土为原料，采用球磨晶化的方法合成出SAPO-11@高岭土酸性载体材料，并负载活性金属Ni-Mo制备成兼具硫醇醚化和噻吩烷基化功能的催化剂，噻吩烷基化和硫醇醚化转化率高达95%以上，表现出了较好的硫化物转移和脱除活性。
发明内容
本发明提供一种兼具噻吩烷基化和硫醇醚化功能催化剂及其制备方法，制备过程包括以下步骤：
（1）高岭土活化脱铝：将高岭土在一定温度下焙烧得到偏高岭土，然后再将磷酸溶液加入到偏高岭土中加热搅拌进行脱铝处理，结束后得到脱铝后的高岭土浆液；
（2）SAPO-11@高岭土的合成：向步骤(1)的浆液中加入模板剂、硅源、铝源，然后在球磨机中球磨得到凝胶前驱体，将凝胶前驱体转移至带聚四氟乙烯内衬的反应釜中，并在旋转烘箱中水热晶化、过滤、洗涤得到SAPO-11@高岭土；
（3）催化剂制备：将SAPO-11@高岭土挤条成型，550-600oC干燥得到酸性载体，然后将硝酸镍和钼酸铵溶解于去离子水中等体积浸渍到SAPO-11@高岭土酸性载体表面，120℃烘箱中干燥 4 h，马弗炉520℃焙烧4 h，焙烧结束得到Ni-Mo/(SAPO-11@高岭土)催化剂，即为所述的兼具噻吩烷基化与硫醇醚化双功能催化剂。
（4）以正庚烷（75 wt%）、1-己烯（25 wt%）、500ppm噻吩和200 ppm 乙硫醇（硫醇为含硫化合物模型）的混合物为FCC汽油模型，测试催化剂的催化性能。
进一步的，步骤（1）所述高岭土的焙烧温度为850℃。
进一步的，步骤（1）所述磷酸溶液为磷酸与去离子水按照 1:1质量比配成，加热温度为80℃。
进一步的，步骤（1）所述的偏高岭土与磷酸溶液的固液比为 4:1 g/ml。
进一步的，步骤（1）所述的脱铝处理时间为3h。
进一步的，步骤（2）所述的模板剂为二正丙胺、硅源为正硅酸四乙酯、铝源为拟薄水铝石。
进一步的，步骤（2）中水热晶化过程为170-185oC下晶化24 -48h。
进一步的，Ni-Mo/(SAPO-11@高岭土)催化剂中，NiO和MoO3的负载比例分别为14wt%和7wt%，以催化剂的总质量为基准。
应用：所述的催化剂用于催化裂化汽油噻吩烷基化和硫醇醚化反应。
与现有的分子筛与氧化铝催化剂相比，本发明的优点在于：
合成的SAPO-11@高岭土酸性载体材料，兼具了SAPO-11的强酸性和高岭土的介孔结构，负载Ni-Mo活性金属制备的催化剂用于催化裂化汽油噻吩烷基化和硫醇醚化反应，噻吩烷基化与硫醇醚化转化率高达95%以上。
附图说明
图1为实施例1和对比例1的N2吸附-脱附等温线；
图2为实施例1和对比例1的孔径分布图；
图3为未改性高岭土与氧化铝的N2吸附-脱附等温线；
图4为实施例1和对比例1、2的NH3-TPD图；
图5为实施例1和对比例1、2的硫醇醚化数据图；
图6为实施例1和对比例1、2的噻吩烷基化数据图；
图7为对比例3、4、5的硫醇醚化数据图：
图8为对比例3、4、5的噻吩烷基化数据图。
具体实施方式
本发明涉及一种兼具噻吩烷基化与硫醇醚化催化剂的制备方法，具体实施过程如下。
实施例1
（1）高岭土活化脱铝。将高岭土在 850 ℃下焙烧 4 h，得到偏高岭土。然后将磷酸与去离子水按照 1:1 的质量比例配成溶液。按照液固质量比为 4:1 g/ml的条件将偏高岭土加入到磷酸溶液中，在80 ℃和120 r/min 的搅拌条件下酸处理 3 h，得到脱铝高岭土浆液。
（2）SAPO-11@高岭土合成。称取步骤(1)的混合浆液25.6 g，于搅拌条件下依次加入60 g水、4.6 g拟薄水铝石、2.5 g正硅酸四乙酯、5.0 g二正丙胺形成前驱体；然后将混合物加入球磨机中分别正转和反转球磨30min，最后转移至带聚四氟乙烯内衬的不锈钢反应釜中，置于旋转烘箱中185oC下晶化24 h，过滤、洗涤得到SAPO-11@高岭土。
（3）催化剂制备。取50 g SAPO-11@高岭土载体材料挤条成型，在600oC的条件下焙烧得到载体。称取5.0 g酸性载体，硝酸镍和钼酸铵（按最终催化剂中NiO和MoO3的质量占比分别为 14%和 7%加入）溶解于一定量去离子水中等体积浸渍，陈化24 h。120℃烘箱中干燥4 h，随后在马弗炉520℃焙烧4 h，焙烧得到Ni-Mo/(SAPO-11@高岭土)催化剂。
（4）反应性能的测试。以正庚烷（75 wt%）、1-己烯（25 wt%）、500 mg/kg噻吩和200mg/kg乙硫醇（硫醇为含硫化合物模型）的混合物为FCC汽油模型，测试催化剂的催化性能。试验在内径为10 mm、长度为500mm、催化剂为5.0 g（20~40目大小）的连续流动管状固定床反应器中进行。试验前，在质量空速（WHSV）2.0 h-1、总压力2.0 MPa、氢油比为300∶1，反应温度300oC的条件下用1 wt% CS2、正庚烷溶液预硫化氧化催化剂4 h。FCC模型汽油的评价实验在以下条件下进行：氢油比为10：1，总压力2.3 MPa，温度为160~200℃，WHSV 2.5 h-1。在稳定48 h后，每8 h收集一次液体反应产物，每次温度变化后稳定12 h。
实施例2
与实施例1中的合成步骤和方法相同，有所区别的是将实施例1步骤(2)中的晶化温度调整为170oC、晶化时间为48 h。
实施例3
与实施例1中的合成步骤和方法相同，有所区别的是将实施例1步骤(2)中凝胶组分的摩尔配比调整为：1Al2O3: 1.2P2O5: 0.3SiO2: 1.5DPA: 100H2O，具体添加量为：称取实施例1步骤(1)中的混合溶液14.4 g，于搅拌状态下依次加入27.35 g水、1.94g拟薄水铝石、1.26 g正硅酸四乙酯、3.06 g二正丙胺形成前驱体。
对比例1
催化剂的制备方法与实施例1中的步骤（3）基本相同，有所区别的是将实施例1步骤(3)中的SAPO-11@高岭土换成氧化铝。
对比例2
催化剂的制备方法与实施例1中的步骤（3）基本相同，有所区别的是将实施例1步骤(3)中的SAPO-11@高岭土换成ZSM-5分子筛。
对比例3
催化剂的制备方法与实施例1中的步骤（3）基本相同，有所区别的是单独以SAPO-11作为载体。
对比例4
催化剂的制备方法与实施例1中的步骤（3）基本相同，有所区别的是单独以高岭土作为载体。
对比例5
催化剂的制备方法与实施例1中的步骤（3）基本相同，有所区别的是以简单物理混合的高岭土和SAPO-11作为载体（SAPO-11+高岭土）。
表1 不同载体的织构参数
由图1和图2可知，SAPO-11@高岭土呈现出一种具有介孔结构的Ⅳ型等温线。由表1可知，SAPO-11@高岭土的介孔结构集中在11 nm左右，对比其他载体具有合适的孔道结构，而反应原料中噻吩、乙硫醇、己烯分子动力学直径分别为0.53 nm、0.6 nm和2.32nm，远远小于改性高岭土的介孔结构，因此可为硫醇醚化反应提供足够的反应空间。
由图4可知，改性后的高岭土具有合适的弱酸性并且有比氧化铝更多的酸量。在145oC附近有较强的弱酸峰，而在275oC附近处的中强酸位置。由图5至图8可知，在160~200oC范围内，随着温度的升高，噻吩转化率逐渐增大，硫醇醚化率先升高后降低，最高可将近100%，并且改性高岭土具有最优脱硫效率。
球磨晶化有利于SAPO-11的生长，这可能是由于在球磨晶化过程中，反应釜的旋转以及磨球的机械作用使得反应物之间更充分地接触，有利于Si、Al在高岭土基质表面的生长，调控复合载体的介孔结构。
以上所述仅为本发明的较佳实施例，凡依本发明申请专利范围所做的均等变化与修饰，皆应属本发明的涵盖范围。
Claims (9)
1.一种兼具噻吩烷基化与硫醇醚化双功能催化剂的制备方法，其特征在于，包括以下步骤：
（1）高岭土活化脱铝：将高岭土在一定温度下焙烧得到偏高岭土，然后再将磷酸溶液加入到偏高岭土中加热搅拌进行脱铝处理，结束后得到脱铝后的高岭土浆液；
（2）SAPO-11@高岭土的合成：向步骤(1)的浆液中加入模板剂、硅源、铝源，然后在球磨机中球磨得到凝胶前驱体，将凝胶前驱体转移至带聚四氟乙烯内衬的反应釜中，并在旋转烘箱中水热晶化、过滤、洗涤得到SAPO-11@高岭土；
（3）催化剂制备：将SAPO-11@高岭土挤条成型，550-600oC干燥得到酸性载体，然后将硝酸镍和钼酸铵溶解于去离子水中等体积浸渍到SAPO-11@高岭土酸性载体表面，120℃烘箱中干燥 4 h，马弗炉520℃焙烧4 h，焙烧结束得到Ni-Mo/(SAPO-11@高岭土)催化剂，即为所述的兼具噻吩烷基化与硫醇醚化双功能催化剂。
2.根据权利要求1所述的方法，其特征在于，步骤（1）所述高岭土的焙烧温度为850℃。
3.根据权利要求1所述的方法，其特征在于，步骤（1）所述磷酸溶液为磷酸与去离子水按照 1:1质量比配成，加热温度为80℃。
4.根据权利要求1所述的方法，其特征在于，步骤（1）所述的偏高岭土与磷酸溶液的固液比为 4:1 g/ml。
5.根据权利要求1所述的方法，其特征在于，步骤（1）所述的脱铝处理时间为3h。
6.根据权利要求1所述的方法，其特征在于，步骤（2）所述的模板剂为二正丙胺、硅源为正硅酸四乙酯、铝源为拟薄水铝石。
7.根据权利要求1所述的方法，其特征在于，步骤（2）中水热晶化过程为170-185 oC下晶化24-48 h。
8.根据权利要求1-7任一项所述的制备方法制得的兼具噻吩烷基化与硫醇醚化双功能催化剂，其特征在于，Ni-Mo/(SAPO-11@高岭土)催化剂中，NiO和MoO3的负载比例分别为14wt%和7wt%。
9.根据权利要求8所述的催化剂用于催化裂化汽油噻吩烷基化和硫醇醚化反应。
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