CN113710359A - 一种用于从液态烃中分离有机氯化合物的吸附剂及其方法 - Google Patents

一种用于从液态烃中分离有机氯化合物的吸附剂及其方法 Download PDF

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CN113710359A
CN113710359A CN202080030533.8A CN202080030533A CN113710359A CN 113710359 A CN113710359 A CN 113710359A CN 202080030533 A CN202080030533 A CN 202080030533A CN 113710359 A CN113710359 A CN 113710359A
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adsorbent
range
silica
metal
high electronegativity
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Y·冯阿沙里亚
S·彭巴尼奇
M·查伦帕尼奇
W·顿派
T·威腾
P·伦格龙
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PTT Global Chemical PCL
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Abstract

本发明涉及用于从液态烃分离有机氯化合物的吸附剂及其方法，其中所述吸附剂是通过具有高电负性的小金属对表面性质进行改性的具有渗透结构的二氧化硅和铝硅酸盐复合材料。

Description

一种用于从液态烃中分离有机氯化合物的吸附剂及其方法
技术领域
本发明涉及化学领域，尤其涉及用于从液态烃中分离有机氯化合物的吸附剂及其方法。
背景技术
催化重整是一种用于转化石脑油(naphtha)的化学过程，石脑油是从原油精炼中获得的，具有低辛烷值至具有较高辛烷值。从催化重整过程中得到的产物称为重整产物。主要使用的催化剂是二氧化硅或硅铝复合载体上的铂或铼。所述催化剂需要氯化，以防止铂或铼聚集成更大的颗粒而导致催化剂劣化。
然而，重整过程中产生的氢气将与催化剂表面的氯化物反应，形成氯化氢。生成的氯化氢将与不饱和烃化合物反应形成有机氯化合物。氯化氢是腐蚀性很强的物质，在生产过程中会损坏设备。尽管有机氯化合物的腐蚀性不如氯化氢，但有机氯化合物可在低温下分解为氯化氢，从而导致腐蚀。
可以通过几种方法从进料流中分离氯化氢和有机氯化合物。高效且不影响进料流中其他烃化合物的方法是通过将被氯化氢和有机氯化合物污染的物流置于含有特定于所述物质的吸附剂的固定床吸附器的吸附过程。
通常，使用碱金属作为促进剂(如美国专利号5,316,988所公开)，氧化铝可从物流中去除氯化氢，以保持浓度低于1ppm。然而，有机氯化合物的去除更加困难，并且关于有机氯化合物吸附剂的数据也有限。
美国专利号3,8629,00公开了使用具有7至11埃范围内孔隙的10X和13X沸石(zeolite)去除有机氯化合物的方法。结果表明，13X沸石的效率最高。
美国专利号8,551,328B2公开了硅铝比值低于1.25的13X沸石对有机氯化合物(氯乙烯)的吸附效率优于硅铝比值为1.25的标准13X沸石。
美国专利号3,864,243公开了使用铝土矿型氧化铝吸附剂从烃化合物中吸附有机氯化合物，该吸附剂在900-1000°F温度范围内煅烧4-6小时，然后具有多孔性和高比表面积。在室温和常压(atmospheric pressure)下，含有机氯化合物的烃化合物的吸附效率为85-96％。
美国专利号5,107,061A公开了从聚异丁烯(PIB)蒸馏塔排出的烃类化合物吸附有机氯化合物，其中，所述有机氯化合物为50-100ppm的2-丁基氯和5-10ppm的叔丁基氯，所述烃类化合物包含50％的正丁烷、30％的1-丁烯、15％的2-丁烯、3％的异丁烯(iso-butylene)和2％的异丁烯(isobutene)。结果表明，氧化铝和NaX沸石两种类型吸附剂组合比单独使用NaX沸石对有机氯化合物的吸附效率更高。
中国专利号103611495A公开了使用三种类型的吸附剂制备有机氯化合物吸附剂，包括：(1)硅铝比值在2-2.5范围内且与锌(Zn)进行离子交换的X或Y沸石；(2)大孔无机材料，即硅藻土；和(3)用于提高强度的粘土，即膨润土和凹凸棒土。结果表明，当与未进行离子交换和未添加无机材料的沸石相比时，在沸石中交换锌离子并添加适量无机材料可以显著提高氯乙烯的吸附效率。
Arjang等人2018年研究了起始浓度为8.5-105mg/L的有机氯化合物在具有230-400m2/g的特定比表面积、20nm平均粒径的伽马氧化铝载体上的吸附。研究发现，当有机氯化合物的起始浓度为8.5mg/L时，吸附效率高达96％。
发明内容
本发明涉及用于从液态烃分离有机氯化合物的吸附剂及其方法，其中所述吸附剂是通过具有高电负性的小金属对表面性质进行改性的具有渗透结构的二氧化硅(silica)和铝硅酸盐(aluminosilicate)复合材料(composite)。
具体实施方式
本发明涉及用于从液态烃分离有机氯化合物的吸附剂及其方法，将根据以下实施例对其进行描述。
除非另有说明，否则本文描述的任何方面还意味着包括对本发明的其他方面的应用。
除非另有说明，否则本文使用的技术术语或科学术语具有本领域普通技术人员理解的定义。
本文中命名的任何工具、设备、方法或化学品是指由本领域技术人员通常操作或使用的工具、设备、方法或化学品，除非另有说明它们是仅在本发明中特定的工具、设备、方法或化学品。
在权利要求或说明书中使用带有“包含”的单数名词或单数代词表示“一个”，并且还包括“一个或多个”、“至少一个”和“一个或超过一个”。
此后，示出了本发明的实施方式，其目的不在于限制本发明的任何范围。
本发明涉及用于从液态烃分离有机氯化合物的吸附剂，其中所述吸附剂是通过具有高电负性的小金属对表面性质进行改性的具有渗透结构的二氧化硅和铝硅酸盐复合材料。
在本发明的一个方面中，所述吸附剂为二氧化硅和铝硅酸盐复合材料，其包含约2nm至15nm范围内的小孔和约40nm至100nm范围内的大孔，其中小孔与大孔的比值为0至1。
在本发明的一个方面中，所述二氧化硅和铝硅酸盐复合材料的硅铝比值在1-20范围内，优选在2-10范围内。
在本发明的一个方面中，具有高电负性的金属选自锌(Zn)、铁(Fe)、钙(Ca)和镁(Mg)，优选锌。
在本发明的一个方面中，所述吸附剂包含在约0.1重量％至10重量％范围内、优选在约0.5重量％至5重量％范围内的具有高电负性的金属。
在本发明的一个方面中，所述吸附剂包含7重量％到15重量％范围内的钠金属。
在一个方面中，可使用诸如离子交换或浸渍等已知方法将所述金属添加到二氧化硅和铝硅酸盐复合吸附剂中。
在一个方面，所述二氧化硅和铝硅酸盐复合材料吸附剂可使用已知方法制备，并可以粉末、颗粒的形式使用，无需经过成型工艺，或使用但不限于从氧化铝(alumina)、二氧化硅(silica)、铝硅酸盐(aluminosilicate)、粘土，或它们的混合物中选择的粘合剂进行成型工艺，或在不使用粘合剂的情况下进行成型工艺。
在本发明的一个方面中，本发明涉及从液态烃中分离有机氯化合物的方法，包括将与有机氯化合物混合的液态烃与吸附剂接触以吸附所述有机氯化合物并获得具有较少量有机氯化合物的液态烃的步骤，其中，所述吸附剂是通过具有高电负性的小金属对表面性质进行改性的具有渗透结构的二氧化硅和铝硅酸盐复合材料。
在本发明的一个方面中，在根据本发明的分离方法中使用的吸附剂可从如上所述的吸附剂中选择。
在本发明的一个方面中，所述有机氯化合物选自烷基氯(alkyl chloride)、烯丙基氯(allyl chloride)，或它们的混合物。优选地，有机氯化合物选自1-氯己烷(1-chlorohexane)、1-氯-2-甲基丁烷(1-chloro-2-methylbutane)、1-氯戊烷(1-chloropentane)，或它们的混合物，最优选1-氯己烷。
在本发明的一个方面中，所述液态烃是沸点高于50℃的烃。优选地，沸点在约50℃至210℃的范围内。所述液态烃可选自甲苯(toluene)、链烷烃(paraffin)、烯烃(olefin)、环烷烃(naphthene)、芳烃(aromatic)，或它们的混合物。
在本发明的一个方面中，根据本发明的分离方法在30℃至50℃的温度和大气压(atmospheric pressure)至10巴的压力下操作。
在本发明的一个方面中，根据本发明的方法能分离液态烃中的有机氯化合物，其中在与吸附剂接触前，有机氯化合物的浓度在2ppm至200ppm的范围内。与吸附剂接触后，产生具有较少量有机氯化合物的液态烃，有机氯化合物的浓度小于0.2ppm。
在本发明的一个方面中，所述含有机氯化合物的液态烃与吸附剂的接触可分批或连续操作，其中所述吸附剂可用在固定床系统、移动床系统或流化床系统中，并可连续顺序或并行使用。
以下实施例用于演示本发明的实施方式，而不是以任何方式限制本发明的范围。
为了研究吸附剂对从液态烃分离有机氯化合物的效率的影响，使用甲苯中的1-氯己烷作为液态烃中有机氯化合物的实施例，而不以任何方式限制本发明的范围。
吸附剂的制备
二氧化硅和铝硅酸盐复合材料的制备
制备具有渗透结构的二氧化硅和铝硅酸盐复合材料的步骤是通过将硅酸钠溶液或加热时产生硅氧化物和氢氧化铝的溶液或加热时产生铝氧化物的溶液在约30-70℃的温度下的水中混合来完成的。硅与铝的不同比值如表1所示。然后，将pH值调整至5.5-8.5，并将混合物再搅拌1小时或更长时间。之后，将pH值调整至9-11，并将混合物再搅拌3-24小时。洗涤所得凝胶，在约100-120℃的温度下干燥，并在约500-700℃的温度下煅烧。
钠(Na)浸出处理
将根据上述方法制备的约1g二氧化硅和铝硅酸盐复合材料分散于约200mL去离子水中，并在约80℃的温度下搅拌约30min。可如上所述重复此操作以获得所需的钠含量。然后，将混合物离心。将所得固体在约100℃的温度下干燥约12小时。之后，在约630℃的大气环境下煅烧约3小时，去除剩余的有机物。
高电负性金属处理
具有渗透结构的二氧化硅和铝硅酸盐复合材料或用上述方法制备的钠浸出处理过的二氧化硅和铝硅酸盐复合材料用具有高电负性的金属进行表面性质的改性(在这种情况下，锌)，以表1所示的不同样品的重量百分比为设计量，使用从硝酸锌、氯化锌或醋酸锌中选择的金属盐溶液进行浸渍的方法。然后，将混合物在约100℃的温度下干燥约12小时。之后，在高温下煅烧混合物以去除有机物，在约400℃至550℃的温度下煅烧约2-4小时。
通过N2-物理吸附技术对上述方法获得的吸附剂进行分析，以确定比表面积(surface area)和孔径。结果如表2所示。
表1:不同样品的吸附剂
Figure BDA0003311981930000061
Figure BDA0003311981930000071
表2：总比表面积、孔径、总孔体积、小孔的孔体积、大孔的孔体积以及小孔与大孔的比值
Figure BDA0003311981930000072
吸附剂吸附效率的测试
在使用前，将吸附剂在烘箱中在约110℃的温度下干燥，以除去水分。然后，使用1-氯己烷的浓度为2至200ppm的含1-氯己烷的甲苯与约1g吸附剂接触约2小时。通过配备电子捕获检测器(electron capture detector，ECD)的气相色谱法分析液相，以确定剩余的1-氯己烷。然后，将所得结果用于计算，以根据以下方程式确定吸附效率和吸附1-氯己烷的量。结果如表3所示。
Figure BDA0003311981930000081
Figure BDA0003311981930000082
表3：从甲苯中在不同起始浓度的1-氯己烷的吸附效率
Figure BDA0003311981930000083
Figure BDA0003311981930000091
吸附能力表示为每种吸附剂的吸附等温线，通过朗缪尔等温线方程(Langmuirisotherm equation)计算最大吸附量。结果如表4所示。
表4：1-氯己烷的最大吸附量
Figure BDA0003311981930000092
综上所述，可以说，如本发明的目的所述，根据本发明的吸附剂可以有效地从液态烃中分离有机氯化合物。
本发明的最佳模式或优选实施方式
本发明的最佳模式或优选实施方式如本发明的描述中所提供。

Claims (25)

1.一种吸附剂，所述吸附剂用于从液态烃中分离有机氯化合物，其中所述吸附剂是通过具有高电负性的小金属对表面性质进行改性的具有渗透结构的二氧化硅和铝硅酸盐复合材料。
2.根据权利要求1所述的吸附剂，其中所述二氧化硅和铝硅酸盐复合材料包括2nm至15nm范围内的小孔和40nm至100nm范围内的大孔，其中所述小孔与所述大孔的比值为0至1。
3.根据权利要求1所述的吸附剂，其中所述二氧化硅和铝硅酸盐复合材料具有在1-20范围内的硅铝比值。
4.根据权利要求3所述的吸附剂，其中所述二氧化硅和铝硅酸盐复合材料具有在2-10范围内的硅铝比值。
5.根据权利要求1所述的吸附剂，其中所述具有高电负性的金属选自锌(Zn)、铁(Fe)、钙(Ca)和镁(Mg)。
6.根据权利要求5所述的吸附剂，其中所述具有高电负性的金属是锌。
7.根据权利要求1、5或6中任一项所述的吸附剂，其中所述吸附剂包含0.1重量％至10重量％范围内的具有高电负性的金属。
8.根据权利要求7所述的吸附剂，其中所述吸附剂包含0.5重量％至5重量％范围内的具有高电负性的金属。
9.根据权利要求1所述的吸附剂，其中所述吸附剂包含在7重量％到15重量％范围内的钠金属。
10.一种从液态烃分离有机氯化合物的方法，所述方法包括将与有机氯化合物混合的液态烃与吸附剂接触以吸附所述有机氯化合物并获得具有较少量有机氯化合物的液态烃的步骤，其中，所述吸附剂是通过具有高电负性的小金属对表面性质进行改性的具有渗透结构的二氧化硅和铝硅酸盐复合材料。
11.根据权利要求10所述的方法，其中所述二氧化硅和铝硅酸盐复合材料包括2nm至15nm范围内的小孔和40nm至100nm范围内的大孔，其中所述小孔与所述大孔的比值为0至1。
12.根据权利要求10所述的方法，其中所述二氧化硅和铝硅酸盐复合材料具有在1-20范围内的硅铝比值。
13.根据权利要求12所述的方法，其中所述二氧化硅和铝硅酸盐复合材料具有在2-10范围内的硅铝比值。
14.根据权利要求10所述的方法，其中所述具有高电负性的金属选自锌(Zn)、铁(Fe)、钙(Ca)和镁(Mg)。
15.根据权利要求14的方法，其中所述具有高电负性的金属是锌。
16.根据权利要求10的方法，其中所述吸附剂包含0.1重量％至10重量％范围内的具有高电负性的金属。
17.根据权利要求16的方法，其中所述吸附剂包含0.5重量％至5重量％范围内的具有高电负性的金属。
18.根据权利要求10所述的方法，其中所述吸附剂包含7重量％至15重量％范围内的钠金属。
19.根据权利要求10所述的方法，其中所述有机氯化合物选自烷基氯、烯丙基氯，或它们的混合物。
20.根据权利要求19所述的方法，其中所述有机氯化合物选自1-氯己烷、1-氯-2-甲基丁烷、1-氯戊烷，或它们的混合物。
21.根据权利要求20所述的方法，其中所述有机氯化合物为1-氯己烷。
22.根据权利要求10所述的方法，其中所述液态烃是具有在50℃至210℃范围内沸点的烃。
23.根据权利要求22所述的方法，其中所述液态烃选自甲苯、链烷烃、烯烃、环烷烃、芳烃，或它们的混合物。
24.根据权利要求10至23中任一项所述的方法，其中所述方法在30℃至50℃的温度和大气压至10巴的压力下操作。
25.根据权利要求10所述的方法，其中所述具有较少量有机氯化合物的液态烃具有小于0.2ppm的有机氯化合物。
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