CN113617361A - 非贵金属芳烃加氢精制催化剂的制备方法 - Google Patents
非贵金属芳烃加氢精制催化剂的制备方法 Download PDFInfo
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Abstract
本发明公开了一种非贵金属芳烃加氢精制催化剂的制备方法，涉及加氢催化剂的技术领域，本发明通过在载体中添加镍盐和钨盐,在加以烘干和煅烧的手段,制备出一种开发低成本、高活性的非贵金属芳烃加氢精制催化剂。
Description
技术领域
本发明涉及加氢催化剂的技术领域，具体是一种非贵金属芳烃加氢精制催化剂的制备方法。
背景技术
随着环保要求的逐渐提高，燃料油规范也日趋严格。其中汽、柴油中不仅对硫、氮含量的要求越来越低，也对芳烃含量进行了严格限制，加氢精制则是深度改善汽、柴油加氢工艺中油品质量的最有效方法，该技术不仅具有较高的目标产品收率，而且生产出的油品质量较高，同时深度加氢造成的油品损失较小，且没有废渣处理等问题，具有很好的社会和经济效益。
高品质的汽、柴油生产需要深度饱和芳烃，因而不仅要使稠环芳烃加氢，还要使单环芳烃加氢。
目前，汽、柴油芳烃加氢精制工艺的难点主要是加氢催化剂的开发，相比于早期加氢催化剂，现汽、柴油加氢催化剂不仅要求具有较高的加氢脱氮和脱硫能力，汽、柴油产品的低芳化还要求加氢催化剂要具有较高的加氢脱芳烃能力。总之，汽、柴油生产工艺瓶颈的突破就在于高芳烃加氢饱和率催化剂的开发。在总体生产工艺已较为成熟的前提下，优质高效的芳烃加氢饱和催化剂已成为生产高氧化安定性汽、柴油基础油的关键所在。
汽、柴油芳烃选加氢精制催化剂的发展趋势主要集中在寻求新的金属组分替代贵金属、进行新型载体开发和研制、降低催化剂的生产成本、提高芳烃饱和性能等。因此，开发低成本、高活性的非贵金属芳烃加氢精制催化剂，生产高品质汽、柴油具有重要意义。
发明内容
本发明提出了一种非贵金属芳烃加氢精制催化剂的制备方法，其包括以下步骤：
包括以下步骤：
S1、制备硫酸铝溶液和稀水玻璃溶液的混合溶液，并调节所述混合溶液的PH值；得到胶体溶液；
S2、用真空过滤器过滤所述胶体溶液得到湿滤饼，将所述湿滤饼依次经水洗、打浆、过滤、烘干、粉碎以及过筛后得到第一中间产物；
S3、将偏钨酸铵水溶液加入第一中间产物中，进行浸渍后得到第二中间产物；
S4、将第二中间产物进行干燥处理，然后在氩气气氛中煅烧，得到第三中间产物；
S5、将硝酸镍溶液加入到第三中间产物中，进行浸渍后得到第四中间产物；
S6、将第四中间产物进行干燥处理，然后在氩气气氛中煅烧，得到最终产物。
本发明的进一步设置为：所述混合溶液PH值为7.0-9.0；所述混合溶液的PH值的调节时间控制在30min-2h。
本发明的进一步设置为：所述S2中的烘干温度为90-120℃。
本发明的进一步设置为：所述S4中的干燥温度为90-120℃，烘干时间为2-3h，煅烧温度为400-500℃，煅烧时间为1-2h。
本发明的进一步设置为：所述S6的干燥温度为90-120℃、干燥时间为 2-3h、煅烧温度为800-900℃、煅烧时间为1-2h。
本发明的进一步设置为：所述S4中的加热温度为60-90℃，加热时间为10-40min。
本发明的有益技术效果为：
1、通过本制备方法所制备的催化剂具有较高的比表面积、孔容以及平均孔径。一方面使催化剂不易结焦堵孔；另一方面不仅有利于馏分油反应分子的扩散，还有利于提高装置单程运转周期，延长催化剂的使用寿命。
2、以芳烃加氢活性较高的W-Ni作为催化剂的活性组分，使该催化剂既有较强的芳烃加氢饱和性能，又不会因为酸性强而发生裂化反应，从而保证产品的高品质、高液收。
3、本发明的制备方法采用具有较弱酸性和大量中孔分布的无定型硅铝和氧化铝为载体的主要成分，W-Ni为活性组分，采用特殊浸渍工艺，镍钨金属组分能够比较均匀的分散于相应的载体上，并且没有金属聚集现象。
附图说明
图1是本发明中Al2O3含量对载体的比表面的影响的数据图；
图2是本发明中Al2O3含量对载体的孔容的影响的数据图；
图3是本发明中Al2O3含量对载体的平均孔径的影响的数据图。
具体实施方式
下面参照附图来描述本发明的优选实施方式。本领域技术人员应当理解的是，这些实施方式仅仅用于解释本发明的技术原理，并非旨在限制本发明的保护范围。
本发明提出了一种非贵金属芳烃加氢精制催化剂的制备方法，包括一下步骤：
S1、制备硫酸铝溶液和稀水玻璃溶液的混合溶液，并调节所述混合溶液的PH值；得到胶体溶液；
S2、用真空过滤器过滤所述胶体溶液得到湿滤饼，将所述湿滤饼依次经水洗、打浆、过滤、烘干、粉碎以及过筛后得到第一中间产物；
S3、将偏钨酸铵水溶液加入第一中间产物中，进行浸渍后得到第二中间产物；
S4、将第二中间产物进行干燥处理，然后在氩气气氛中煅烧，得到第三中间产物；
S5、将硝酸镍溶液加入到第三中间产物中，进行浸渍后得到第四中间产物；
S6、将第四中间产物进行干燥处理，然后在氩气气氛中煅烧，得到最终产物。
在S1中，混合溶液的制备过程包括以下子步骤：
S11、将硫酸铝加入到蒸馏水中，同时加热并搅拌至溶解，得到硫酸铝溶液；
S12、将蒸馏水加入到工业级的浓水玻璃中，稀释后得到稀水玻璃溶液；
S13、取反应罐，在反应罐中加入蒸馏水，搅拌并加热后，开始滴加硫酸铝溶液和稀水玻璃溶液，得到混合溶液。过程中加热的温度是60～90℃。
S14、用稀氨水调节混合溶液的PH值。
S1做完后，便可以得到胶体溶液，具体反应过程如式(1)至式(3) 所示：
3Na2SiO3+Al2(SO4)3+6H2O→2Al(OH)3↓+3Na2SO4+3H2SiO3↓ 式(1)
2Al(OH)3→2Al2O3+3H2O； 式(2)
H2SiO3→SiO2+H2O。 式(3)
当S2完成后，第二中间产物，即载体便制备完成。
在S3中，偏钨酸铵溶液的制备过程是：将(NH4)6H2W12O40·8H2O放入烧杯中，加入去离子水，然后在磁力搅拌器上进行搅拌溶解。
S3步骤的具体过程是：向第一中间产物中滴加偏钨酸铵溶液，然后将滴加后的样品放入超声波震荡仪中，进行超声处理30min，超声处理后在静止状态浸渍30min。
在S4中，干燥温度为90-120℃，烘干时间为2-3h，煅烧温度为 400-500℃，煅烧时间为1-2h。较佳的是，第二中间产物在干燥箱120℃下干燥2h，经研磨后再置于内径为80mm的石英管反应器中，使其在300 ml/min的氩气气氛下，以10℃/min的升温速率从室温升至350℃进行煅烧，并在氩气气氛中保留1h。
S4完成后，得到的第三中间产物是W/SiO2-Al2O3。
在S5步骤中，硝酸镍溶液的制备过程是：将Ni(NO3)2·6H2O放入烧杯中，加入去离子水，然后在磁力搅拌器上进行搅拌溶解。
S5步骤的具体过程是：向第三中间产物中滴加硝酸镍溶液，然后将滴加后的样品放入超声波震荡仪中，进行超声处理30min，超声处理后在静止状态浸渍30min。
在S6中，干燥温度为90-120℃、干燥时间为2-3h、煅烧温度为800-900℃、煅烧时间为1-2h。较佳的是，第四中间产物在干燥箱120℃下干燥2h，经研磨后再置于内径为80mm的石英管反应器中，使其在300 ml/min的氩气气氛下，以10℃/min的升温速率从室温升至850℃进行煅烧，当反应温度达到850℃时，立刻停止加热，然后在氩气气氛中降温至室温，取出并研磨，无需钝化处理，至此最终制得W-Ni/SiO2-Al2O3加氢精制催化剂。
S6完成后，得到的最终产物W-Ni/SiO2-Al2O3。最终产物中，WOx的质量浓度是0.5g/ml；NiOy的质量浓度是0.1g/ml。
实验结果：由于载体酸性强弱、孔径、比表面积、孔容等性质直接影响到了催化剂的反应的方向、活性以及芳烃饱和与开环能力，因而我们通过调变无定型硅铝的Si/Al比例，考察了无定型硅铝载体的的酸性以及孔结构等性质的变化，结果表明，Si/Al比例对于载体的酸性以及孔结构具有明显的影响。表1为Al2O3含量对载体酸性的影响。从表1中数据可以看出，不同Si/Al比的无定型硅铝产品在170℃～400℃附近存在中等强度的酸性中心；随着产品中氧化铝含量的升高，其酸性中心的数量呈现先升高后降低的趋势。表2为三个批次的催化剂的物性表征。通过表2可以看出，三个不同批次的催化剂各项指标接近，说明具备良好的重复性。图1-3分别是 Al2O3含量对载体的比表面的、孔容、平均孔径的影响。从图1-3可以看出，随着Al2O3含量的升高，无定型硅铝的比表面积大幅下降；孔容随着Al2O3含量的升高先缓慢下降，后来则呈急剧下降趋势；而平均孔径却随着Si/Al 比例的下降略有上升。
由于加氢精制催化剂的酸性要适当，酸性太强会发生裂化反应影响收率，太弱又会影响芳烃开环饱和性能，因而综合考虑到无定型硅铝的Si/Al 比例对酸性、孔容、比表及孔径的影响，最终定型无定型硅铝中氧化硅含量为氧化铝含量的2倍。
表1 Al2O3含量对载体酸性的影响
表2三个批次的催化剂的物性表征
虽然已经参考优选实施例对本发明进行了描述，但在不脱离本发明的范围的情况下，可以对其进行各种改进并且可以用等效物替换其中的部件，尤其是，只要不存在结构冲突，各个实施例中所提到的各项技术特征均可以任意方式组合起来。本发明并不局限于文中公开的特定实施例，而是包括落入权利要求的范围内的所有技术方案。
在本发明的描述中，术语“中心”、“上”、“下”、“左”、“右”、“竖直”、“水平”、“内”、“外”等指示方向或位置关系的术语是基于附图所示的方向或位置关系，这仅仅是为了便于描述，而不是指示或暗示所述装置或元件必须具有特定的方位、以特定的方位构造和操作，因此不能理解为对本发明的限制。此外，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
此外，还需要说明的是，在本发明的描述中，除非另有明确的规定和限定，术语“安装”、“相连”、“连接”应做广义理解，例如，可以是固定连接，也可以是可拆卸连接，或一体地连接；可以是机械连接，也可以是电连接；可以是直接相连，也可以通过中间媒介间接相连，可以是两个元件内部的连通。对于本领域技术人员而言，可根据具体情况理解上述术语在本发明中的具体含义。
术语“包括”或者任何其它类似用语旨在涵盖非排他性的包含，从而使得包括一系列要素的过程、物品或者设备/装置不仅包括那些要素，而且还包括没有明确列出的其它要素，或者还包括这些过程、物品或者设备/装置所固有的要素。
至此，已经结合附图所示的优选实施方式描述了本发明的技术方案，但是，本领域技术人员容易理解的是，本发明的保护范围显然不局限于这些具体实施方式。在不偏离本发明的原理的前提下，本领域技术人员可以对相关技术特征作出等同的更改或替换，这些更改或替换之后的技术方案都将落入本发明的保护范围之内。
Claims (6)
1.一种非贵金属芳烃加氢精制催化剂的制备方法，其特征在于：包括以下步骤：
S1、制备硫酸铝溶液和稀水玻璃溶液的混合溶液，并调节所述混合溶液的PH值；得到胶体溶液；
S2、用真空过滤器过滤所述胶体溶液得到湿滤饼，将所述湿滤饼依次经水洗、打浆、过滤、烘干、粉碎以及过筛后得到第一中间产物；
S3、将偏钨酸铵水溶液加入第一中间产物中，进行浸渍后得到第二中间产物；
S4、将第二中间产物进行干燥处理，然后在氩气气氛中煅烧，得到第三中间产物；
S5、将硝酸镍溶液加入到第三中间产物中，进行浸渍后得到第四中间产物；
S6、将第四中间产物进行干燥处理，然后在氩气气氛中煅烧，得到最终产物。
2.根据权利要求1所述的非贵金属芳烃加氢精制催化剂的制备方法，其特征在于：所述混合溶液PH值为7.0-9.0；所述混合溶液的PH值的调节时间控制在30min-2 h。
3.根据权利要求1所述的非贵金属芳烃加氢精制催化剂的制备方法，其特征在于：所述S2中的烘干温度为90-120 ℃。
4.根据权利要求1所述的非贵金属芳烃加氢精制催化剂的制备方法，其特征在于：所述S4中的干燥温度为90-120 ℃，烘干时间为2-3 h，煅烧温度为400-500 ℃，煅烧时间为1-2h。
5.根据权利要求1所述的非贵金属芳烃加氢精制催化剂的制备方法，其特征在于：所述S6的干燥温度为90-120 ℃、干燥时间为2-3 h、煅烧温度为800-900 ℃、煅烧时间为1-2 h。
6.根据权利要求1所述的非贵金属芳烃加氢精制催化剂的制备方法，其特征在于：制备所述混合溶液过程中，在进行搅拌时需进行加热处理，加热温度为60-90 ℃，加热时间为10-40 min。
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