CN112844416A - 一种加氢催化剂及其制备方法 - Google Patents

一种加氢催化剂及其制备方法 Download PDF

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Publication number
CN112844416A
CN112844416A CN201911020915.8A CN201911020915A CN112844416A CN 112844416 A CN112844416 A CN 112844416A CN 201911020915 A CN201911020915 A CN 201911020915A CN 112844416 A CN112844416 A CN 112844416A
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China
Prior art keywords
hydrogenation catalyst
group metal
catalyst
vib
hydrogenation
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CN201911020915.8A
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Inventor
姚运海
刘丽
杨成敏
段为宇
李扬
郭蓉
周勇
孙进
郑步梅
丁莉
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201911020915.8A priority Critical patent/CN112844416A/zh
Priority to KR1020227017682A priority patent/KR20220086670A/ko
Priority to EP20878466.0A priority patent/EP4035770A4/en
Priority to US17/755,231 priority patent/US20220362751A1/en
Priority to TW109136952A priority patent/TW202124045A/zh
Priority to CA3155697A priority patent/CA3155697A1/en
Priority to PCT/CN2020/123395 priority patent/WO2021078282A1/zh
Publication of CN112844416A publication Critical patent/CN112844416A/zh
Pending legal-status Critical Current

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Abstract

本发明公开了一种加氢催化剂及其制备方法。加氢催化剂包括加氢催化剂载体和加氢活性组分，以所述催化剂的总重量为基准，第VIB族金属硫化物为2.2wt%‑33wt%，优选10wt%‑20wt%，第VIII族金属氧化物计为0.2wt%‑12wt%，优选3wt%‑6wt%。制备方法如下：（1）用含第VIB族金属的浸渍液浸渍加氢催化剂载体，然后干燥处理，干燥后的物料进行硫化处理；（2）用含第

Description

一种加氢催化剂及其制备方法
技术领域
本发明涉及到油品加氢技术领域，具体涉及到一种加氢催化剂及其制备方法。
背景技术
柴油所含硫化合物主要包括脂肪族硫化物、硫醚、二苯并噻吩(DBT)、烷基苯并噻吩和烷基二苯并噻吩等。油品的脱硫技术分为非加氢脱硫和加氢脱硫(HDS)，其中非加氢脱硫技术主要包括吸附脱硫、氧化脱硫、萃取脱硫和生物脱硫等。非加氢脱硫技术进展虽大，尤其以氧化脱硫最具应用前景，但是存在操作费用高、油品损耗高、资金和设备投入高等缺点，且油品后续处理有一定难度，故很难在较短时间内工业化。HDS技术就是采用脱硫催化剂，在高温高压条件下反应，让硫化物转化成H2S进行分离的过程。相对于其他脱硫技术，HDS技术较成熟。对于高含硫油品，该技术可大幅度降低硫含量。同时，HDS技术操作灵活，精制油收率高，色泽佳，能有效地脱除如噻吩类等难以脱除的硫化物。随着柴油的清洁化要求日益严格，HDS技术显得越来越重要，已成为炼油企业改善产品质量的重要手段，国内外对此都做了大量研究工作。
国外比较成熟的HDS技术多是以新开发的高活性催化剂为核心，如美国雅宝公司的STARS和 NEBULA系列催化剂、美国标准公司的CENTINEL系列催化剂、丹麦托普索公司的TK系列催化剂和法国石油研究院的HR系列催化剂等。STARS催化剂技术(Ⅱ类活性反应中心)适用于生产硫质量分数小于50μg/g的低硫或超低硫清洁燃料，已工业化应用的主要有以Mo-Co为活性金属组分的KF-757和以Mo-Ni为活性金属组分的KF-848催化剂，KF-757和KF-848催化剂在不同操作条件下显示出很高的加氢脱硫活性。KF-757适于在中、低压条件下生产硫质量分数小于50μg/g的产品，KF-848适于在中、高压条件下生产硫质量分数小于10μg/g的清洁燃料。
通常的II类活性中心催化剂制备方法是在加氢精制催化剂的制备过程中引入螯合剂，螯合剂具有减弱活性组分与载体之间相互作用、提高活性组分在载体上的分散度、延迟助剂金属（Co、Ni）硫化等作用，可以促进高活性TypeⅡCo-Mo-S相的生成。
CN102465005A公开了一种II类活性中心催化剂的开工方法。该方案要求在135°C引入硫化油，有利于催化剂生成更多的II类活性中心。CN102443412A公开了一种器外预硫化II类活性中心加氢催化剂的开工方法。该方案引入活化油时的温度较低，活化过程恒温的温度较低，具有形成更多II类活性中心的优点。CN201010222027.7公开一种二类活性中心加氢催化剂开工硫化方法，该发明硫化方法工艺简单，操作便捷，硫化效果较常规方法更为理想，从而有利于提高二类活性中心数量，进而提高催化剂的活性。以上专利提高催化剂二类活性中心数的方法主要是采用改变硫化过程的方法来提高催化剂的活性。
发明内容
针对现有技术的不足，本发明提供了一种加氢催化剂及其制备方法。本发明催化剂具有较高的硫化度及高的II类活性中心数，本发明的催化剂可以应用在馏分油、渣油等油品加氢处理过程。
本发明的加氢催化剂，包括加氢催化剂载体和加氢活性组分，加氢活性组分为第VIB族金属硫化物和第VIII族金属氧化物，其中第VIB族金属优选Mo和/或W，第VIII族金属优选Co和/或Ni。
以所述催化剂的总重量为基准，第VIB族金属硫化物为2.2wt%-33wt%，优选10wt%-20wt%，第VIII族金属氧化物计为0.2wt%-12wt%，优选3wt%-6wt%。所述催化剂采用XPS能谱分析，其中+4价态的第VIB族金属含量占总的VIB族金属含量摩尔比例为60%-90%。
所述催化剂经过硫化后采用XPS能谱分析，其中+4价态的第VIB族金属含量占总第VIB族金属含量摩尔比例为65%-100%，第VIII族金属与第VIB族金属相互作用的物种含量摩尔占第VIII族金属总含量比例为60%-100%。硫化处理处理条件为：采用干法硫化或湿法硫化，干法硫化剂为硫化氢，湿法硫化剂为二硫化碳、二甲基二硫醚、甲基硫醚、正丁基硫醚中的一种或多种；硫化压力为3.2-6.4MPa，硫化温度为250-400℃，硫化时间为4-12h。
所述的加氢催化剂载体为多孔性无机耐熔氧化物选自元素周期表中第II族、第III族、第IV族和第IVB族元素的氧化物中的一种或多种，更优选选自二氧化硅、氧化铝、氧化镁、氧化锆、氧化钛、氧化硅铝、氧化硅镁和氧化铝镁中的一种或多种，进一步优选氧化铝。所述的加氢催化剂载体可以根据需要进行改性处理，如采用B、P、F等改性元素进行改性，以改性后的加氢催化剂载体重量为基准，改性元素重量百分含量为0.5wt%-10wt%。
本发明的加氢催化剂的制备方法，包括以下内容：
（1）用含第VIB族金属的浸渍液浸渍加氢催化剂载体，然后干燥处理，干燥后的物料进行硫化处理；
（2）用含第
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族金属的浸渍液浸渍到步骤（1）硫化后的的物料，然后在惰性气氛下，进行干燥和焙烧，得到加氢催化剂。
本发明方法中，步骤（1）所述的第VIB族金属的浸渍液的配制方法为本领域技术人员熟知，如一般采用磷酸盐或铵盐溶液等，所述的浸渍液的质量浓度为0.1g/mL~2.0g/mL，可以采用等体积浸渍的方式。所述的第VIB族金属优选Mo和/或W。
本发明方法中，步骤（1）所述的干燥条件为：干燥温度90-200℃，干燥时间3-6小时。
本发明方法中，步骤（1）所述的硫化处理为本领域技术人员熟知，通常采用干法硫化或湿法硫化，干法硫化剂为硫化氢，湿法硫化剂为二硫化碳、二甲基二硫醚、甲基硫醚、正丁基硫醚中的一种或两种；硫化压力为3.2-6.4MPa，硫化温度为250-400℃，硫化时间为4-12h。
本发明方法中，步骤（2）所述的第
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族金属的浸渍液的配制方法为本领域技术人员熟知，如一般采用硝酸盐、醋酸盐、硫酸盐溶液等，所述的浸渍液的质量浓度为0.1g/mL~1.0g/mL，可以采用等体积浸渍的方式，所述的第
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族金属为Ni和/或Co。
本发明方法中，步骤（2）所述的惰性气氛为N2和惰性气体中的一种或多种；所述的干燥温度为20-90℃，干燥时间为4-16小时；所述的焙烧温度为200-500℃，焙烧时间为2-5小时。
本发明的加氢催化剂在馏分油、渣油等油品加氢处理过程中的应用。
本发明的加氢催化剂在应用前需要进行硫化处理，一般的硫化处理条件为：采用干法硫化或湿法硫化，干法硫化剂为硫化氢，湿法硫化剂为二硫化碳、二甲基二硫醚、甲基硫醚、正丁基硫醚中的一种或多种；硫化压力为3.2-6.4MPa，硫化温度为250-400℃，硫化时间为4-12h。
由于催化剂在硫化前是以氧化态的形式存在，而VIB族金属较难硫化VIII族金属容易硫化，易造成硫化态VIII族金属被硫化态VIB族金属包裹的现象，造成VIII族金属无法充分发挥其助剂作用，不易生成II类活性中心，造成催化剂活性的降低。发明人另辟蹊径，通过不同活性金属分步浸渍和硫化的方式，先在载体上浸渍第VIB族金属，然后预先硫化，然后在硫化物上浸渍第
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族金属，能够使第
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族金属覆盖在硫化态的第VIB族金属表面上，充分发挥
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族金属助剂作用，创造二者之间的相互作用的条件，促进II类活性中心的生成，进而提高催化剂的活性。
具体实施方式
下面通过实施例进一步说明本发明方案及效果，但并不构成对本发明的限制。本发明提供的催化剂组成可以通过电感耦合等离子体ICP和XPS能谱结合起来表征，首先通过ICP表征出催化剂中第VIB族金属的总含量和第
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族金属的总含量，然后通过XPS谱仪定量表征催化剂中不同价态金属元素的含量。本发明提供的催化剂的金属硫化度，用Mo4+或W4 +含量表示催化剂的金属硫化度。采用在320℃下用30mL/min的H2S硫化2h，XPS谱仪表征样品表面的金属价态，采用XPSPEAK Version4.0分别对Mo3d、W4f、Co2p、Ni2p能谱进行拟合分峰，根据峰面积计算得到金属硫化度和Co-Mo-S、Ni-Mo-S、Co-W-S、Ni-W-S的比例。
实施例1
将17.6g的(NH4)6Mo7O24•4H2O，用氨水调解至钼酸铵完全溶解，用100mL容量瓶定容，然后等体积浸渍到氧化铝载体，经过120℃干燥3h。然后采用含有1.5%H2S的氢气进行硫化处理，硫化温度为350℃，硫化压力为4.0MPa，硫化时间为8h，然后在N2气氛中降至室温，得到MoS2/Al2O3。将9.31g的Co(NO3)2•6H2O溶解到50mL的去离子水中，在N2气氛中等体积浸渍到MoS2/Al2O3中，然后在N2气氛下，90℃干燥4h，300℃焙烧3h，得到MoS2-CoO/Al2O3催化剂C-1。
实施例2
将17.6g的(NH4)6Mo7O24•4H2O，用氨水调解至钼酸铵完全溶解，用100mL容量瓶定容，然后等体积浸渍到氧化铝载体，经过120℃干燥3h。然后采用含有1.5%H2S的氢气进行硫化处理，硫化温度为350℃，硫化压力为4.0MPa，硫化时间为8h，然后在N2气氛中降至室温，得到MoS2/Al2O3。将9.31g的Ni(NO3)2•6H2O溶解到50mL的去离子水中，在N2气氛中等体积浸渍到MoS2/Al2O3中，然后在N2气氛下，90℃干燥4h，300℃焙烧3h，得到MoS2-NiO/Al2O3催化剂C-2。
实施例3
将17.6g的(NH4)6Mo7O24•4H2O，用氨水调解至钼酸铵完全溶解，用100mL容量瓶定容，然后等体积浸渍到氧化铝载体，经过120℃干燥3h。然后采用含有1.5%H2S的氢气进行硫化处理，硫化温度为350℃，硫化压力为4.0MPa，硫化时间为8h，然后在N2气氛中降至室温，得到MoS2/Al2O3。将5.11g的Ni(NO3)2•6H2O和4.25Co(NO3)2•6H2O溶解到50mL的去离子水中，在N2气氛中等体积浸渍到MoS2/Al2O3中，然后在N2气氛下，90℃干燥4h，300℃焙烧3h，得到MoS2-NiO-CoO/Al2O3催化剂C-3。
实施例4
将17.6g的(NH4)6Mo7O24•4H2O，用氨水调解至钼酸铵完全溶解，用100mL容量瓶定容，然后等体积浸渍到氧化硅修饰的氧化铝载体，经过120℃干燥3h。然后采用含有1.5%H2S的氢气进行硫化处理，硫化温度为350℃，硫化压力为4.0MPa，硫化时间为8h，然后在N2气氛中降至室温，得到MoS2/Al2O3。将9.31g的Co(NO3)2•6H2O溶解到50mL的去离子水中，在N2气氛中等体积浸渍到MoS2/Al2O3中，然后在N2气氛下，90℃干燥4h，300℃焙烧3h，得到MoS2-CoO/SiO2-Al2O3催化剂C-4。
实施例5
将12.6g的(NH4)6Mo7O24•4H2O，用氨水调解至钼酸铵完全溶解，然后加入10.2g的偏钨酸铵，完全溶解后，用100mL容量瓶定容，然后等体积浸渍到氧化硅修饰的氧化铝载体，经过120℃干燥3h。然后采用3wt%CS2的航煤进行硫化处理，以空速1.0h-1，氢油体积比500:1，在5.0MPa的操作压力下，硫化处理8h，然后在N2气氛中降至室温，得到MoS2/Al2O3。将9.31g的Co(NO3)2•6H2O溶解到50mL的去离子水中，在N2气氛中等体积浸渍到MoS2/Al2O3中，然后在N2气氛下，90℃干燥4h，300℃焙烧3h，得到MoS2-WS2-CoO/Al2O3催化剂C-5。
对比例1
将17.6g的(NH4)6Mo7O24•4H2O，用氨水调解至钼酸铵完全溶解，用100mL容量瓶定容，然后等体积浸渍到氧化铝载体，经过120℃干燥3h，400℃焙烧3h，得到MoO3/Al2O3。然后将9.31g的Co(NO3)2•6H2O溶解到50mL的去离子水中，等体积浸渍到MoO3/Al2O3中，然后在90℃干燥4h，300℃焙烧3h，得到MoO3-CoO/Al2O3催化剂DC-1。
对比例2
将17.6g的(NH4)6Mo7O24•4H2O，用磷酸调解至钼酸铵完全溶解，然后添加9.31g的Co(NO3)2•6H2O，完全溶液后，用100mL容量瓶定容，然后等体积浸渍到氧化铝载体，经过120℃干燥3h，400℃焙烧3h，得到MoO3-CoO/Al2O3催化剂DC-2
实施例6
本实例说明本发明提供的催化剂对于柴油的加氢脱硫反应性能。
采用的评价原料油是由中石化某炼厂提供的混合柴油。
采用200mL的固定床液相循环加氢装置分别对催化剂C-1至C-5、对比例DC-1至DC-2进行加氢反应性能评价。
催化剂的预硫化条件：使用含4wt%CS2的航煤，以空速1.0h-1，氢油体积比550:1，在5.0MPa的操作压力下，对催化剂进行预硫化。
预硫化过程如下所示：在120℃下进预硫化油，进油2h后，恒温硫化2h，以15℃/h升温至150℃，恒温硫化4h，以6℃/h升温至230℃，恒温硫化10h，以6℃/h升温至290℃，恒温硫化6h，以12℃/h升温至330℃，恒温硫化6h，最后自然降温至200℃，预硫化结束。
评价反应条件为：操作压力11.0MPa，反应温度360℃，循环比3，新鲜原料体积空速是1.5h-1、三次混氢，评价结果见表1。
表1催化剂的性质及评价结果
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表3中的评价结果可以说明，本发明的催化剂的活性金属具有较高的硫化度，本发明的催化剂在用于柴油液相循环加氢反应中，在操作压力11.0MPa，反应温度360℃，循环比3，新鲜原料体积空速是1.5h-1、三次混氢的工艺条件下，达到了较高的脱硫性能。

Claims (15)

1.一种加氢催化剂，包括加氢催化剂载体和加氢活性组分，其特征在于：加氢活性组分为第VIB族金属硫化物和第VIII族金属氧化物，以所述催化剂的总重量为基准，第VIB族金属硫化物为2.2wt%-33wt%，优选10wt%-20wt%，第VIII族金属氧化物计为0.2wt%-12wt%，优选3wt%-6wt%。
2.根据权利要求1所述的加氢催化剂，其特征在于：第VIB族金属硫化物为10wt%-20wt%，第VIII族金属氧化物计为3wt%-6wt%。
3.根据权利要求1所述的加氢催化剂，其特征在于：第VIB族金属为Mo和/或W，第VIII族金属为Co和/或Ni。
4.根据权利要求1所述的加氢催化剂，其特征在于：所述催化剂采用XPS能谱分析，其中+4价态的第VIB族金属含量占总的VIB族金属含量摩尔比例为60%-90%。
5.根据权利要求1所述的加氢催化剂，其特征在于：所述催化剂经过硫化后，采用XPS能谱分析，其中+4价态的第VIB族金属含量占总第VIB族金属含量摩尔比例为65%-100%，第VIII族金属与第VIB族金属相互作用的物种含量摩尔占第VIII族金属总含量比例为60%-100%。
6.根据权利要求1所述的加氢催化剂，其特征在于：所述的加氢催化剂载体为多孔性无机耐熔氧化物，选自元素周期表中第II族、第III族、第IV族和第IVB族元素的氧化物中的一种或多种。
7.根据权利要求1所述的加氢催化剂，其特征在于：所述的加氢催化剂载体为二氧化硅、氧化铝、氧化镁、氧化锆、氧化钛、氧化硅铝、氧化硅镁和氧化铝镁中的一种或多种。
8.根据权利要求1所述的加氢催化剂，其特征在于：所述的加氢催化剂载体进行改性处理，改性元素为B、P或F中一种或多种，以改性后的加氢催化剂载体重量为基准，改性元素重量百分含量为0.5wt%-10wt%。
9.一种权利要求1~8任一权利要求所述的加氢催化剂的制备方法，其特征在于包括以下内容：（1）用含第VIB族金属的浸渍液浸渍加氢催化剂载体，然后干燥处理，干燥后的物料进行硫化处理；（2）用含第
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族金属的浸渍液浸渍到步骤（1）硫化后的的物料，然后在惰性气氛下，进行干燥和焙烧，得到加氢催化剂。
10.根据权利要求9所述的方法，其特征在于：步骤（1）所述的第VIB族金属的浸渍液的质量浓度为0.1g/mL~2.0g/mL，采用等体积浸渍的方式。
11.根据权利要求9所述的方法，其特征在于：步骤（1）所述的干燥条件为：干燥温度90-200℃，干燥时间3-6小时。
12.根据权利要求9所述的方法，其特征在于：步骤（1）所述的硫化处理条件为：硫化压力为3.2-6.4MPa，硫化温度为250-400℃，硫化时间为4-12h；硫化剂为硫化氢、二硫化碳、二甲基二硫醚、甲基硫醚、正丁基硫醚中的一种或多种。
13.根据权利要求9所述的方法，其特征在于：步骤（2）所述的第
Figure 173269DEST_PATH_IMAGE001
族金属的浸渍液的质量浓度为0.1g/mL~1.0g/mL，采用等体积浸渍的方式。
14.根据权利要求9所述的方法，其特征在于：步骤（2）所述的惰性气氛为N2和惰性气体中的一种或多种；所述的干燥温度为20-90℃，干燥时间为4-16小时；所述的焙烧温度为200-500℃，焙烧时间为2-5小时。
15.一种权利要求1~9任一所述的加氢催化剂在油品加氢处理过程中的应用。
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