CN113856736B - 用于催化氧化柴油中噻吩的催化剂及其制备方法和应用 - Google Patents
用于催化氧化柴油中噻吩的催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明属于催化剂领域，具体提供了一种用于催化氧化柴油中噻吩的催化剂及其制备方法和应用，先使用原位合成法制备了HTC‑Al2O3，在组成上的灵活性为开发新的催化剂、催化剂前体或催化剂载体提供了一个良好的机会，该催化剂具有量身定制的结构设计，可控制催化位点和活性的可行性。再通过沉淀法负载量双金属氧化物，催化剂活性中心稳定，具有比表面积大，活性高，将柴油通过氧化脱硫，将噻吩氧化为亚砜，亚砜极其不稳定，再氧化为砜类，砜类极性增加，容易通过吸附/萃取方法。在柴油中，噻吩转化率可以达到96％，噻吩砜选择性可以达到98％，收率在95％以上。
Description
技术领域
本发明属于催化剂领域，特别涉及一种用于催化氧化柴油中噻吩的催化剂及其制备方法和应用。
背景技术
炼油厂产品由75-80％的柴油、汽油和非运输燃料组成，均经过脱硫处理。在过去的几十年里，炼油厂和研究机构开发了选择性和高效的工艺，并升级了现有的生产极低含硫量燃料的技术，以满足更严格的新环境法规的要求。此外，在21世纪初，亚洲地区如韩国、中国、孟加拉国、日本、印度、老挝、缅甸、朝鲜和泰国出现了大量的硫氮化合物沉积。2017年，美国环保局规定超低硫柴油和联邦汽油的含硫量分别为15和10ppm此外，欧盟(EU)法规将柴油和汽油的总硫含量限制在10ppm以下。菲律宾2016年欧IV标准将柴油总硫含量限制在50ppm以下。燃料油中所含的含硫化合物被认为在精炼过程和商业使用中是有害的。石油加工过程中的催化剂失活和管道、泵送和炼油设备的腐蚀问题是炼油过程中硫化物造成的固有问题。在燃料燃烧中，颗粒物和硫酸盐的形成有助于空气污染和酸雨的形成。此外，含硫化合物的废气对用于悬浮颗粒物和氮氧化物的排放控制技术造成损害。
发明内容
为了解决背景技术中存在的技术问题，本发明提供了一种用于催化氧化柴油中噻吩的催化剂及其制备方法和应用。
本发明先使用原位合成法制备了HTC-Al2O3，在组成上的灵活性为开发新的催化剂、催化剂前体或催化剂载体提供了一个良好的机会，该催化剂具有量身定制的结构设计，可控制催化位点和活性的可行性。再通过沉淀法负载量双金属氧化物，催化剂活性中心稳定，具有比表面积大，活性高，将柴油中的噻吩氧化为亚砜，亚砜极其不稳定，再氧化为砜类，砜类极性增加，容易通过吸附/萃取方法。
为了实现本发明目的，所采用的技术方案为：一种用于催化氧化柴油中噻吩的催化剂的制备方法，包括如下步骤：
(1)将γ-氧化铝均匀分散在尿素水溶液中，然后加入到特氟龙不锈高压釜中，在80-120℃下加热12-36h，然后冷却至室温，其中γ-氧化铝和尿素的质量比为1-10：8-15，尿素水溶液的浓度为0.4-1.25g/ml。
进一步说明，在Al2O3浸渍的水溶液中分解尿素，原位合成LDHs。层状双氢氧化物(LDHs)，也被称为类水滑石材料，是一类阴离子粘土，其结构是基于水镁石(Mg(OH)2)类层，其中一些二价阳离子被三价离子取代，形成带正电荷的薄片。
(2)向步骤(1)冷却至室温后的体系中加入Mg(NO3)2 6H2O，充分溶解并均匀分散后，在特氟龙不锈钢高压釜中，在120-150℃下加热12-36h，然后在马弗炉中400-600℃煅烧4-8h，得水滑石修饰得氧化铝(简称HTC-Al2O3)，Mg(NO3)2 6H2O与γ-氧化铝的质量比为10-20：1-10。
(3)将步骤(2)制备的HTC-Al2O3分散在去离子水、无水乙醇、乙二醇中搅拌2-8h，然后加入硝酸铈溶液，充分分散后通过氨水和氢氧化钠调节PH在8-9之间，再在80-100℃回流2-8h，沉淀物过滤，洗涤，在100-130℃烘箱干燥。进一步说明，去离子水、无水乙醇、乙二醇体积比为(7-9):(3-6):1，乙二醇的作用是连接剂，硝酸铈与HTC-Al2O3质量比(0.10-0.30):1。
(4)将步骤(3)干燥好的物质分散在去离子水、无水乙醇和乙二醇混合溶剂中，加入硝酸铁溶液，通过氨水和氢氧化钠调节PH为8-9，在80-100℃回流2-8h，沉淀物过滤、洗涤，然后在100-130℃烘箱中干燥，然后在马弗炉中300-450℃煅烧3-6h，得用于催化氧化柴油中噻吩的催化剂(简称CeO2-Fe2O3/HTC-Al2O3)。
进一步说明，加入去离子水乙醇、乙二醇体积比和步骤(3)相同，硝酸铁与HTC-Al2O3质量比(0.34-0.72):1。
本发明还提供了上述用于催化氧化柴油中噻吩的催化剂在柴油催化氧化脱硫中的应用。
具体应用方法包括如下步骤：
在反应器中，将柴油和H2O2与十六烷基三甲基溴化铵(CATB)和催化剂混合，在25-60℃下加热搅拌混合物，进行脱硫。
与现有技术相比，本发明取得了如下有益效果：本发明方法先使用原位合成法制备了HTC-Al2O3，再通过沉淀法负载量双金属氧化物，催化剂活性中心稳定，具有比表面积大，活性高，将柴油通过氧化脱硫，将噻吩氧化为亚砜，亚砜极其不稳定，再氧化为砜类，砜类极性增加，容易通过吸附/萃取方法，将柴油含硫物质降到最低。
具体实施方式
本发明不局限于下列具体实施方式，本领域一般技术人员根据本发明公开的内容，可以采用其他多种具体实施方式实施本发明的，或者凡是采用本发明的设计结构和思路，做简单变化或更改的，都落入本发明的保护范围。需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
本发明下面结合实施例作进一步详述：
实施例1
(1)称取4gγ-氧化铝和19.2g尿素溶于15ml去离子水，加入到特氟龙不锈高压釜中，在90℃下加热24h。
(2)向步骤(1)冷却至室温后的体系中，加入10gMg(NO3)2 6H2O在特氟龙不锈钢高压釜中，在135℃下加热24h，然后在马弗炉中450℃煅烧6h。
(3)称取7g的HTC-Al2O3分散在150ml去离子水、100ml无水乙醇和20ml乙二醇中搅拌4h，然后加入0.88g六水硝酸铈溶解在5ml去离子水中，溶液分散在混合物中，通过氨水和氢氧化钠调节PH在8-9之间，混合物在90℃回流6h。过滤，洗涤，在120℃烘箱干燥
(4)将步骤(3)干燥好的物质分散在在150ml去离子水、100ml无水乙醇和20ml乙二醇中，加入5.06g无水硝酸铁溶解在13ml水中，加入混合物中，通过氨水和氢氧化钠调节PH为8-9，在90℃回流6h。过滤洗涤，在120℃烘箱干燥。然后在马弗炉中350℃煅烧5h，得柴油燃料氧化脱硫催化剂(简称CeO2-Fe2O3/HTC-Al2O3)。
(5)催化剂CeO2-Fe2O3/HTC-Al2O3在柴油氧化脱硫的应用。
制备了初始浓度为500ppm的柴油储备液。在200ml玻璃罐反应器中，将等量的柴油和H2O2与十六烷基三甲基溴化铵(CATB)和催化剂混合，CATB与催化剂质量比为1:1，在50℃下反应2h，进行了脱硫实验。在预定的时间间隔获得一份1ml样品，并冷却。样品离心10分钟，提取有机相中所含的合成油，并使用气相色谱法进行进一步分析以及紫外荧光定硫仪检测器。
实施例2
将实施例1步骤(2)中Mg(NO3)2 6H2O的质量换成20g，其余操作与实施例1相同。
实施例3
将实施例1步骤(3)中六水硝酸铈的质量改为1.76g，其余操作与实施例1相同。
步骤4
将实施例1步骤(3)中去离子水、无水乙醇和乙二醇体积改为140ml、100ml、20ml，其余操作与实施例1相同。
步骤5
将实施例1步骤(3)中去离子水、无水乙醇和乙二醇体积改为150ml、80ml、20ml，其余操作与实施例1相同。
实施例6
将实施例1步骤(4)中无水硝酸铁的质量改为2.41g，其余操作与实施例1相同。
实施7
将实施例1步骤(5)催化剂应用中，反应温度改为40℃，其余操作与实施例1相同。
实施例8
将实施例1步骤(5)催化剂应用，反应温度改为60℃，其余操作与实施例1相同。
实施例9
将实施例1步骤(5)催化剂的应用，CATB与催化剂的质量比改为0.5：1，其余操作与实施例1相同。
实施例10
将实施例1步骤(5)催化剂的应用，CATB与催化剂的质量比改为2：1，其余操作与实施例1相同。
对比例1
将实施例1步骤(2)中不加入Mg(NO3)2 6H2O，其余操作与实施例1相同。
对比例2
将实施例1中步骤(3)中不加入六水硝酸铈，其余操作与实施例1相同。
对比例3
将实施例1中步骤(4)中不加入无水硝酸铁，其余操作与实施例1相同。
对比例4
将实施例1中步骤(5)中不加入十六烷基三甲基溴化铵(CATB)。本发明实施例和比较例实验数据见表1。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，根据本发明的技术方案及其构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (6)
1.一种用于催化氧化柴油中噻吩的催化剂的制备方法，其特征在于：包括如下步骤：
（1）将γ-氧化铝均匀分散在尿素水溶液中，然后加入到特氟龙不锈高压釜中，在80-120℃下加热12-36h，然后冷却至室温，其中γ-氧化铝和尿素的质量比为1-10：8-15，尿素水溶液的浓度为0.4-1.25g/mL；
（2）向步骤（1）冷却至室温后的体系中加入Mg(NO3)2 6H2O，充分溶解并均匀分散后，在特氟龙不锈钢高压釜中，在120-150℃下加热12-36h，然后在马弗炉中400-600℃煅烧4-8h，得HTC- Al2O3，Mg(NO3)2 6H2O与γ-氧化铝的质量比为(10-20):(1-10)；
（3）将步骤（2）制备的HTC-Al2O3分散在去离子水、无水乙醇和乙二醇的混合溶剂中搅拌2-8h，然后加入硝酸铈溶液，充分分散后通过氨水和氢氧化钠调节pH在8-9之间，再在80-100℃回流2-8h，沉淀物过滤，洗涤，在100-130℃烘箱干燥；
（4）将步骤（3）干燥好的物质分散在去离子水、无水乙醇和乙二醇混合溶剂中，加入硝酸铁溶液，通过氨水和氢氧化钠调节pH为8-9，在80-100℃回流2-8h，沉淀物过滤、洗涤，然后在100-130℃烘箱中干燥，然后在马弗炉中300-450℃煅烧3-6h，得所述用于催化氧化柴油中噻吩的催化剂。
2.根据权利要求1所述的用于催化氧化柴油中噻吩的催化剂的制备方法，其特征在于：步骤（3）混合溶剂中的去离子水、无水乙醇及乙二醇的体积比为7-9:3-6:1，硝酸铈与HTC-Al2O3质量比为0.10-0.30:1。
3.根据权利要求1所述的用于催化氧化柴油中噻吩的催化剂的制备方法，其特征在于：步骤（4）混合溶剂中的去离子水、乙醇及乙二醇体积比和步骤(3)相同，硝酸铁与HTC-Al2O3质量比为0.34-0.72:1。
4.如权利要求1至3中任一项所述的用于催化氧化柴油中噻吩的催化剂的制备方法所制得的催化剂。
5.如权利要求4所述的用于催化氧化柴油中噻吩的催化剂的应用，其特征在于：用于柴油催化氧化脱硫。
6.根据权利要求5所述的用于催化氧化柴油中噻吩的催化剂的应用，其特征在于：包括如下步骤：
在反应器中，将柴油和H2O2与十六烷基三甲基溴化铵和催化剂混合，在25-60℃下加热搅拌混合物，进行脱硫。
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| CN1275435A (zh) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | 一种烟气净化催化剂 |
| KR20040014454A (ko) * | 2001-02-09 | 2004-02-14 | 아크조 노벨 엔.브이. | 제자리에 형성된 음이온 클레이-함유 성형체 |
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| CN109722302A (zh) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | 一种裂化脱硫联合方法和装置以及催化裂化和吸附脱硫的组合工艺 |
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| CN1275435A (zh) * | 1999-05-28 | 2000-12-06 | 中国石油化工集团公司 | 一种烟气净化催化剂 |
| KR20040014454A (ko) * | 2001-02-09 | 2004-02-14 | 아크조 노벨 엔.브이. | 제자리에 형성된 음이온 클레이-함유 성형체 |
| CN101905117A (zh) * | 2010-06-29 | 2010-12-08 | 北京化工大学 | 一种催化裂化烟气硫转移剂活性组元的制备方法 |
| CN109722302A (zh) * | 2017-10-31 | 2019-05-07 | 中国石油化工股份有限公司 | 一种裂化脱硫联合方法和装置以及催化裂化和吸附脱硫的组合工艺 |
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