CN106513049A - 一种具有超高抑焦性能的重油加氢纳米催化剂及其制备方法和应用 - Google Patents
一种具有超高抑焦性能的重油加氢纳米催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种具有超高抑焦性能的重油加氢纳米催化剂及其制备方法和应用，该催化剂为采用具有R1—C2H5—R2—R3结构的修饰配体分子在一定条件下对过渡金属硫化物纳米颗粒进行表面修饰得到的，其中修饰配体分子含量在1～25m％之间。所制备的具有超高抑焦性能的重油加氢纳米催化剂在修饰配体分子的作用下，在劣质重油、渣油沥青质上吸附的浓度高于其在劣质重油、渣油中的平均浓度。本发明提供的具有超高抑焦性能的重油加氢纳米催化剂具有抑焦性能极高、在原料油中分散度高、制备工艺简单等优点，在原油、常压渣油、减压渣油、煤焦油、脱沥青油、油砂沥青、沥青、煤焦油沥青中的一种或几种混合物的悬浮床加氢反应中表现了极高的催化加氢活性和超高的抑焦性能。
Description
技术领域
本发明涉及一种具有超高抑焦性能的重油加氢纳米催化剂及其制备方法，以及其在劣质重油、渣油悬浮床加氢过程中的应用，属于纳米材料的合成及催化应用领域。
背景技术
随着优质原油不断消耗，原油品质重质化、高硫化和高酸化的趋势愈来愈明显。此外，石油炼制过程中还产生了大量渣油，约占原油的30～50wt％。如何对大量的劣质原油和炼化渣油进行有效加工利用是石化行业目前面临的难题之一。悬浮床加氢工艺是使用劣质原油、页岩油、油砂沥青、炼化渣油制备液体燃料油的先进工艺技术。悬浮床加氢工艺最为突出的特点是使用非负载的分散型催化剂，分散型催化剂在原料油中高度分散，一次通过反应器后不回收。因此，用于悬浮床加氢工艺的分散型催化剂要求具有活性高、分散性好、稳定性高、用量小、成本低等特点。重油悬浮床加氢反应使用的分散型催化剂包括固体粉末催化剂、水溶性催化剂和油溶性催化剂等。近年来，研究人员又开发了纳米催化剂用于重油悬浮床加氢反应。
美国专利4125455使用C7-C12的脂肪酸钼或钨溶解于渣油原料中，加入量以金属计为500～1000μg/g，在430℃，13.7MPa反应条件下进行加氢裂化反应，当用辛酸钼作催化剂，加入量为590μg/g(以金属计)，反应8小时后454℃转化率可达80m％。
CN200710013466.5公开了一种用于劣质重油、渣油悬浮床加氢裂化的液溶胶催化剂，该液溶胶催化剂由粒径为0.1μm～100μm之间的过渡金属Fe、Co、Ni、Cr、Cu、Mn、Mo、W硫化物颗粒均匀分散在水相中构成，金属活性组分含量为2～25％。该催化剂是将过渡金属可溶性盐在水相中与单齿配体或有机多齿配体形成配合物，然后进行硫化反应得到的。
中国专利CN02109399.7将MoS2、WS2粉末与溶剂混合，向混合物中加入分散剂和稳定剂，氢气气氛中于一定温度下搅拌得到催化剂的胶体油剂，其中MoS2、WS2的平均粒径低于500nm。采用该催化剂对劣质重、渣油进行悬浮床加氢裂化，反应温度435～440℃，反应压力10～14MPa，催化剂加入量≤400μg/g(以金属计)，反应5h后＜500℃液体产品收率达80m％以上，脱硫率超过60m％，脱氮率在40m％以上。上述催化剂均存在悬浮床加氢原料中分散效果差、加氢活性低、加入量大、成本高等缺点。
中国专利CN201110167627.2公开了一种由α-FeO(OH)或者针铁矿和油溶性有机钼组成的重质油加氢催化剂，其中油溶性有机钼中的钼原子与催化剂中的铁原子的摩尔比为1-1720:170。该催化剂用于煤系或者油系重质馏分进行加氢裂化，可得到低硫的轻质馏分油。但该催化剂的用量较大，催化抑焦性能较差。
目前，重油悬浮床加氢使用的分散型催化剂还普遍存在催化抑焦性能较差、分散度较低、用量大等问题，影响了悬浮床加氢工艺的应用和推广。
发明内容
本发明的目的在于提供一种具有超高抑焦性能的重油加氢纳米催化剂及其制备方法，以及其在劣质重油、渣油悬浮床加氢过程中的应用。本发明所述的具有超高抑焦性能的重油加氢纳米催化剂具有抑焦性能极高、在原料油中分散度高、制备工艺简单等优点，用于劣质重油、渣油悬浮床加氢反应中表现出极高的催化加氢活性和超高的抑焦性能。
为实现上述目的，本发明采用的技术方案是：
一种具有超高抑焦性能的重油加氢纳米催化剂，其特征在于所述催化剂为采用修饰配体分子修饰后的过渡金属硫化物纳米颗粒，其中修饰配体分子含量在1～25m％之间。当修饰配体分子含量低于1m％时，少量的修饰配体分子不能产生足够的作用力使重油加氢纳米催化剂向重油中的沥青质定向扩散与吸附；当修饰配体分子含量高于25m％时，过多的修饰配体分子占据重油加氢纳米催化剂的催化活性点位，不利于氢气在催化剂表面的活化；因此，修饰配体分子含量低于1m％或高于25m％均会降低重油加氢纳米催化剂的抑焦性能。
上述具有超高抑焦性能的重油加氢纳米催化剂中，所述的修饰配体分子选自由下式(1)表示的化合物中的至少一种，
R1—C2H5—R2—R3 (1)
其中R1表示具有1～4个芳香环的基团，并且所述芳香环为渺位缩合或迫位缩合，其中至多有一个芳香环为杂环芳香环；R2表示具有1～12个碳原子的烷基或链烯基，并且所述链烯基可以为直链状、支链状或环状中的任一种；R3表示巯基或羧基。
上述具有超高抑焦性能的重油加氢纳米催化剂中，所述的过渡金属硫化物为Cr、Mn、Fe、Co、Ni、Cu、Mo、Pd、Cd、W的硫化物。
上述具有超高抑焦性能的重油加氢纳米催化剂中，所述的过渡金属硫化物纳米颗粒的粒径为1～400nm。
上述具有超高抑焦性能的重油加氢纳米催化剂是通过以下方法制备得到的，将过渡金属硫化物纳米颗粒和修饰配体分子按质量比为1:0.2～50分散于油性介质中，在氮气气氛中于40～150℃下搅拌反应2～100h，然后离心、洗涤、干燥后得到具有超高抑焦性能的重油加氢纳米催化剂。经过上述反应过程，修饰配体分子通过牢固的化学键吸附在过渡金属硫化物纳米颗粒表面，从而对纳米催化剂在重油加氢反应中的扩散、分布、吸附状态、催化活性和抑焦性能等产生影响。
本发明制备的具有超高抑焦性能的重油加氢纳米催化剂，用于劣质重油、渣油悬浮床加氢反应，反应温度430～445℃、氢压12～18MPa、空速0.6～1.5h-1、具有超高抑焦性能的重油加氢纳米催化剂的浓度≤160ppm。
根据上述具有超高抑焦性能的重油加氢纳米催化剂在劣质重油、渣油悬浮床加氢反应中的应用，所述纳米催化剂在劣质重油、渣油沥青质上吸附的浓度高于其在劣质重油、渣油中的平均浓度。这是由于在修饰配体分子与重油沥青质的强相互作用下，所制得的具有超高抑焦性能的重油加氢纳米催化剂将向沥青质定向扩散并吸附，实现在沥青质这一生焦前驱物附近的局部高浓度，从而高效的抑制焦炭(甲苯不溶物)的生成。
根据上述具有超高抑焦性能的重油加氢纳米催化剂在劣质重油、渣油悬浮床加氢反应中的应用，所述劣质重油、渣油包括原油、常压渣油、减压渣油、煤焦油、脱沥青油、油砂沥青、沥青、煤焦油沥青中的一种或几种。
附图说明
图1是本发明制得的具有超高抑焦性能的硫化镍纳米催化剂TEM照片。
图2是本发明制得的具有超高抑焦性能的二硫化钼纳米催化剂TEM照片。
图3是本发明制得的具有超高抑焦性能的二硫化钨纳米催化剂TEM照片。
图4是本发明制得的具有超高抑焦性能的硫化钴纳米催化剂TEM照片。
具体实施方式
下面结合实施例和附图对本发明做进一步详细说明，但本发明并不局限于以下的实施例。
实施例1
将1.0g粒径3～6nm的硫化镍纳米颗粒与12.0g式(2)所述的修饰配体分子(简称：A)分散于50ml环己烷中，在氮气气氛中于120℃下搅拌反应20h，然后离心、洗涤、干燥后得到具有超高抑焦性能的硫化镍纳米催化剂，其中修饰配体分子A的含量为8.7m％。图1是制得的具有超高抑焦性能的硫化镍纳米催化剂的TEM照片，显示硫化镍纳米催化剂在制备过程中没有发生团聚现象，仍以原来的粒径均匀分散。取本实施例制备的具有超高抑焦性能的硫化镍纳米催化剂以1000ppm的浓度(以镍含量计算)分散于克拉玛依超稠油减压渣油中，在氮气气氛下，在100℃下以500rpm的速率搅拌1h，然后迅速分离出沥青质，采用原子吸收光谱法测定沥青质中镍的含量为1415ppm，高于在克拉玛依超稠油减压渣油中的平均浓度。
实施例2
将1.5g粒径80～200nm的二硫化钼纳米颗粒与60.0g式(3)所述的修饰配体分子(简称：B)分散于200ml液体石蜡中，在氮气气氛中于55℃下搅拌反应88h，然后离心、洗涤、干燥后得到具有超高抑焦性能的二硫化钼纳米催化剂，其中修饰配体分子B的含量为23.9m％。图2为制得的具有超高抑焦性能的二硫化钼纳米催化剂的TEM照片。取本实施例制备的具有超高抑焦性能的二硫化钼纳米催化剂以1000ppm的浓度(以钼含量计算)分散于克拉玛依超稠油减压渣油中，在氮气气氛下，在100℃下以500rpm的速率搅拌1h，然后迅速分离出沥青质，采用原子吸收光谱法测定沥青质中钼的含量为1468ppm，高于在克拉玛依超稠油减压渣油中的平均浓度。
实施例3
将3.8g粒径100～320nm的二硫化钨纳米颗粒与2.5g式(4)所述的修饰配体分子(简称：C)分散于40ml甲苯中，在氮气气氛中于90℃下搅拌反应2h，然后离心、洗涤、干燥后得到具有超高抑焦性能的二硫化钨纳米催化剂，其中修饰配体分子C的含量为5.6m％。图3是制得的具有超高抑焦性能的二硫化钨纳米催化剂TEM照片。取本实施例制备的具有超高抑焦性能的二硫化钨纳米催化剂以1000ppm的浓度(以钨含量计算)分散于克拉玛依超稠油减压渣油中，在氮气气氛下，在100℃下以500rpm的速率搅拌1h，然后迅速分离出沥青质，采用原子吸收光谱法测定沥青质中钨的含量为1522ppm，高于在克拉玛依超稠油减压渣油中的平均浓度。
实施例4
将2.0g粒径3～10nm的硫化钴纳米颗粒与16.0g式(5)所述的修饰配体分子(简称：D)分散于50ml石脑油中，在氮气气氛中于60℃下搅拌反应55h，然后离心、洗涤、干燥后得到具有超高抑焦性能的硫化钴纳米催化剂，其中修饰配体分子D的含量为16.3m％。图4是制得的具有超高抑焦性能的硫化钴纳米催化剂TEM照片。取本实施例制备的具有超高抑焦性能的硫化钴纳米催化剂以1000ppm的浓度(以钴含量计算)分散于克拉玛依超稠油减压渣油中，在氮气气氛下，在100℃下以500rpm的速率搅拌1h，然后迅速分离出沥青质，采用原子吸收光谱法测定沥青质中钴的含量为1598ppm，高于在克拉玛依超稠油减压渣油中的平均浓度。
实施例5-12
以下实施例使用的重油原料为克拉玛依超稠油减压渣油(KLVR)和Athabasca油砂沥青(AOS)，具体组成与性质见表1。实施例5-8采用悬浮床加氢工艺，以克拉玛依超稠油减压渣油、Athabasca油砂沥青或二者1:1混合原料油为原料，分别测试了实施例1-4所制备具有超高抑焦性能的重油加氢纳米催化剂的催化活性和抑焦性能，测试结果见表2。实施例9-12则采用悬浮床加氢工艺，在相同条件下，分别测试了对应的未修饰的过渡金属硫化物纳米催化剂的催化活性和抑焦性能，测试结果见表2。
表1克拉玛依超稠油减压渣油和Athabasca油砂沥青的组成与性质
表2中评价结果可以看出，本发明提供的具有超高抑焦性能的重油加氢纳米催化剂在劣质重油、渣油悬浮床加氢反应中具有极高的催化加氢活性和超高的抑焦性能。在反应温度430～445℃、氢压12～18MPa、空速0.6～1.5h-1、具有超高抑焦性能的重油加氢纳米催化剂的浓度≤160ppm的情况下，劣质重油、渣油的转化率大于86m％，产物中轻油收率不低于75m％，甲苯不溶物收率低于0.1m％。
表2中评价结果可以看出，使用对应的未修饰的过渡金属硫化物纳米催化剂在劣质重油、渣油悬浮床加氢反应中催化加氢活性和抑焦性能，在相同的反应条件下，产物中甲苯不溶物收率为1.2～2.1m％。说明本发明通过采用具有一定结构的修饰配体分子对纳米催化剂进行处理，实现了纳米催化剂在劣质重油、渣油沥青质上吸附的浓度高于其在劣质重油、渣油中的平均浓度，进一步有效提高了纳米催化剂的抑焦性能，实现了甲苯不溶物的完全不生成或极低收率。
表2重油悬浮床加氢测试评价结果
Claims (9)
1.一种具有超高抑焦性能的重油加氢纳米催化剂，其特征在于所述催化剂为采用修饰配体分子修饰后的过渡金属硫化物纳米颗粒，其中修饰配体分子含量在1～25m％之间。
2.根据权利要求1所述的一种具有超高抑焦性能的重油加氢纳米催化剂，其特征在于所述的修饰配体分子选自由下式(1)表示的化合物中的至少一种，
R1—C2H5—R2—R3 (1)
其中R1表示具有1～4个芳香环的基团，并且所述芳香环为渺位缩合或迫位缩合，其中至多有一个芳香环为杂环芳香环；R2表示具有1～12个碳原子的烷基或链烯基，并且所述链烯基可以为直链状、支链状或环状中的任一种；R3表示巯基或羧基。
3.根据权利要求1或2所述的一种具有超高抑焦性能的重油加氢纳米催化剂，其特征在于所述的过渡金属硫化物为Cr、Mn、Fe、Co、Ni、Cu、Mo、Pd、Cd、W的硫化物。
4.根据权利要求3所述的一种具有超高抑焦性能的重油加氢纳米催化剂，其特征在于所述的过渡金属硫化物纳米颗粒的粒径为1～400nm。
5.一种根据权利要求1～4中任一项所述重油加氢纳米催化剂的制备方法，其特征在于将过渡金属硫化物纳米颗粒和修饰配体分子按质量比为1:0.2～50分散于油性介质中，在氮气气氛中于40～150℃下搅拌反应2～100h，然后离心、洗涤、干燥后得到具有超高抑焦性能的重油加氢纳米催化剂。
6.权利要求1～4中任一项所述的具有超高抑焦性能的重油加氢纳米催化剂在劣质重油、渣油悬浮床加氢反应的应用。
7.根据权利要求6所述的具有超高抑焦性能的重油加氢纳米催化剂在劣质重油、渣油悬浮床加氢反应的应用，其特征在于反应温度430～445℃、氢压12～18MPa、空速0.6～1.5h-1、具有超高抑焦性能的重油加氢纳米催化剂的浓度≤160ppm。
8.根据权利要求6所述的具有超高抑焦性能的重油加氢纳米催化剂在劣质重油、渣油悬浮床加氢反应的应用，其特征在于所述催化剂在劣质重油、渣油沥青质上吸附的浓度高于其在劣质重油、渣油中的平均浓度。
9.根据权利要求6所述的具有超高抑焦性能的重油加氢纳米催化剂在劣质重油、渣油悬浮床加氢反应中的应用，所述劣质重油、渣油包括原油、常压渣油、减压渣油、煤焦油、脱沥青油、油砂沥青、沥青、煤焦油沥青中的一种或几种。
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