CN109621970B - 一种用于费托合成低分子直链烷烃异构化的催化剂 - Google Patents
一种用于费托合成低分子直链烷烃异构化的催化剂 Download PDFInfo
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Abstract
一种费托合成低分子直链烷烃(nC5‑nC8)异构化催化剂、制备方法及其应用,用于解决现有费托合成低分子直链烷烃异构化催化剂活性低、稳定性差和转化率低的问题。本发明采用共沉淀法制备Al2O3‑ZrO2复合氧化物载体,加入镧盐以提高氧化锆四方相的比例,调控Al2O3含量以保持催化剂酸性,再采用等体积浸渍法制备Ni‑WO3/Al2O3‑ZrO2催化剂,得到以Al2O3‑ZrO2为载体,活性金属组分为Ni,W,La的用于费托合成低分子直链烷烃异构化的催化剂。三种活性组分的含量分别为1~5wt%的Ni,10~15wt%的W和0.5~2.5wt%的La。该催化剂具有较高的异构化活性和选择性,重复性和催化稳定性好,并且反应温度低,在高温下能够保持低分子直链烷烃的异构化活性。
Description
技术领域
本发明属于催化剂制备技术领域,具体涉及一种用于费托合成低分子直链烷烃异构化催化剂、制备方法及其应用。
背景技术
随着环保的要求越来越高,对汽油进行加氢脱硫和降烯烃,可将硫含量降至10μg/g以下,烯烃含量降至24v%以下。虽然汽油中的烯烃、芳烃含量逐步降低,但其辛烷值也被大大降低。若要在不损失或很少损失辛烷值的情况下降低硫、烯烃含量,则需要进行选择性加氢裂化或异构化。加氢异构对于提高汽油辛烷值显得尤为重要。异构烷烃的RON比相同碳数的正构烷烃高很多。例如,nC6的RON为24.8,而2,2-二甲基C4为91.8;nC7为0,三甲基C4为112.1,二甲基C5为81~93。因此将小分子量的正构烷烃转化成异构烷烃来提高轻油馏分的辛烷值,从而改善汽油的辛烷值具有十分重要的意义。
ZrO2具有熔点高、强度好及耐磨损等优点,是唯一一种同时具有酸性、碱性氧化性和还原性的化合物,因此作为催化剂或催化剂载体目前已经得到了广泛的应用。然而纯二氧化锆存在比表面积小、表面酸度弱等缺点,不适合应用于工业生产中,一些研究者选择在氧化锆中掺杂含有p或d轨道的金属原子(如Ti,Ce,Al,Si等),不同金属原子的引入会对ZrO2的性质造成不同的改变,如引入金属原子Ti会增加复合氧化物载体的比表面积,从而提高催化剂的催化活性;引入稀土金属原子如Ce等会提高载体的热稳定性和储氧能力;引入含有酸性位的金属原子如Al等会使复合氧化物载体的吸附能力和表面酸性增大。掺杂这些金属原子的锆基复合氧化物具有较高的织构性能和催化性能。
发明内容
本发明所要解决的技术问题在于针对上述现有技术中的不足,提供一种用于费托合成的低分子直链烷烃异构化催化剂,该催化就采用共沉淀法制备Al2O3-ZrO2复合氧化物载体,加入镧盐以提高氧化锆四方相的比例,调控Al2O3含量以保持催化剂酸性,再采用等体积浸渍法制备Ni-WO3/Al2O3-ZrO2催化剂,得到以Al2O3-ZrO2为载体,活性金属组分为Ni,W,La的用于费托合成低分子直链烷烃异构化的催化剂。三种活性组分的含量分别为1~5wt%的Ni,10~15wt%的W和0.5~2.5wt%的La。所述载体的比表面为100~150m2/g,其孔容为0.05~0.1ml/g,NH3-TPD总酸度为0.6~1.5mmol/g,产物辛烷值在78~80该催化剂具有较高的异构化活性和选择性,重复性和催化稳定性好,并且反应温度低,在高温下能够保持低分子直链烷烃的异构化活性。
合成方法主要包含如下步骤:
(1)将计算量的Al(NO3)3·9H2O,锆盐(锆铝比1:1),镧盐(0.5~2.5wt%La)溶解于去离子水,调节pH值8~9;
(2)将混合物加入水热釜于110-200℃进行12-48小时的水热反应,用水洗涤至无Cl-且为中性为止;
(3)对洗涤得到的滤饼于80-180℃进行干燥处理,得到四方相Al2O3-ZrO2载体。
(4)将步骤(3)制备的锆基复合氧化物载体溶解于偏钨酸铵水溶液中,经搅拌、老化、干燥焙烧后得到WO3/Al2O3-ZrO2粉末;
(5)将步骤(4)中得到的WO3/Al2O3-ZrO2粉末分散于硝酸镍的水溶液中,继续搅拌、老化、干燥和焙烧,得到Ni-WO3/Al2O3-ZrO2催化剂;
具体实施方式
以下结合具体实施例进一步阐释本发明的技术方案,但不作为对本发明保护范围的限制。
实施例1
(1)将计算量的Al(NO3)3·9H2O,锆盐(锆铝比1:1),镧盐溶解于去离子水,(锆的浓度0.4mol/L,镧的含量2wt%)在剧烈搅拌下滴加氨水调节pH值为10;
(2)将混合物加入水热釜于180℃进行24h的水热反应,用水洗涤至无Cl-且为中性为止;
(3)对洗涤得到的滤饼于120℃进行干燥处理,得到四方相Al2O3-ZrO2载体。
(4)将步骤(3)制备的锆基复合氧化物载体溶解于偏钨酸铵水溶液,经搅拌6h、老化24h,80℃下空气干燥,800℃下焙烧4h后得到W质量分数为15%的WO3/Al2O3-ZrO2粉末;
(5)将步骤(4)中得到的WO3/Al2O3-ZrO2粉末分散于硝酸镍的水溶液中,搅拌6h、老化24、80℃下空气干燥和500℃下焙烧4h,得到Ni的质量分数为5%的Ni-WO3/Al2O3-ZrO2催化剂,命名为催化剂A。催化剂性能及产物辛烷值见表1;
实施例2
与实施例1操作步骤相同,不同的是步骤(5)中,更改将步骤(4)中得到的WO3/Al2O3-ZrO2粉末分散于硝酸镍的水溶液中,搅拌6h、老化24、80℃下空气干燥和500℃下焙烧4h,得到Ni的质量分数为4%的Ni-WO3/Al2O3-ZrO2催化剂,命名为催化剂B。催化剂性能及产物辛烷值见表1;
实施例3
与实施例1操作步骤相同,不同的是步骤(5)中,更改将步骤(4)中得到的WO3/Al2O3-ZrO2粉末分散于硝酸镍的水溶液中,搅拌6h、老化24、80℃下空气干燥和500℃下焙烧4h,得到Ni的质量分数为6%的Ni-WO3/Al2O3-ZrO2催化剂,命名为催化剂C。催化剂性能及产物辛烷值见表1;
实施例4
与实施例1操作步骤相同,不同的是步骤(1)中,将计算量的Al(NO3)3·9H2O,锆盐和镧盐溶解于去离子水,(锆的浓度0.4mol/L,镧的含量0wt%)在剧烈搅拌下滴加氨水调节pH值为10,制得催化剂D。催化剂性能及产物辛烷值见表1;
实施例5
与实施例1操作步骤相同,不同的是步骤(4)中,在步骤(3)制备的锆基复合氧化物载体后,不浸渍偏钨酸铵水溶液制得催化剂E。催化剂性能及产物辛烷值见表1;
实施例6
与实施例1操作步骤相同,不同的是步骤(1)中,不加入Al(NO3)3·9H2O制得催化剂F;催化剂性能及产物辛烷值见表1;
实施例7
与实施例1操作步骤相同,不同的是步骤(1)中,不加入Al(NO3)3·9H2O,将锆盐和镧盐溶解于去离子水,(锆的浓度0.4mol/L,镧的含量0wt%)在剧烈搅拌下滴加氨水调节pH值为10制得催化剂G。催化剂性能及产物辛烷值见表1;
表1采用实施例1~7催化剂反应后产物的性能结果
由表1数据可以看出,根据本专利制备得到的以Al2O3-ZrO2为载体,活性金属组分为Ni,W,La的用于费托合成低分子直链烷烃异构化的催化剂(三种活性组分的含量分别为1~5wt%的Ni,10~15wt%的W和0.5~2.5wt%的La),具有较高的异构化活性和选择性,重复性和催化稳定性好,并且反应温度低,在高温下能够保持低分子直链烷烃的异构化活性。
以上以具体实施例说明的方式对本发明作了描述,本领域的技术人员应当理解,本公开不限于以上描述的实施例,在不偏离本发明的范围的情况下,可以做出各种变化、改变和替换。
Claims (2)
1.一种用于低分子直链烷烃异构化催化剂的制备方法,包括以下步骤:
(1)将计算量的Al(NO3)3·9H2O,锆盐,锆铝比1:1,镧盐溶解于去离子水,其中锆的浓度0.4mol/L,镧的含量2wt%,在剧烈搅拌下滴加氨水调节pH值为10;
(2)将混合物加入水热釜于180℃进行24h的水热反应 ,用水洗涤至无Cl-且为中性为止;
(3)对洗涤得到的滤饼于120℃进行干燥处理,得到四方相Al2O3-ZrO2载体;
(4)将步骤(3)制备的锆基复合氧化物载体溶解于偏钨酸铵水溶液,经搅拌6h、老化24h,80℃下空气干燥,800℃下焙烧4h后得到W质量分数为15%的WO3/ Al2O3-ZrO2粉末;
(5)将步骤(4)中得到的WO3/ Al2O3-ZrO2粉末分散于硝酸镍的水溶液中,搅拌6h、老化24h、80℃下空气干燥和500℃下焙烧4h,得到Ni的质量分数为4%的Ni-WO3/Al2O3-ZrO2催化剂。
2.权利要求1所述的制备方法制备的低分子直链烷烃异构化催化剂的用途,用于低分子直链烷烃异构化,所述低分子直链烷烃原料为含有5~8个碳原子的正构烷烃。
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