CN106732666B - 一次成型的大孔硫化型加氢催化剂的制备方法 - Google Patents
一次成型的大孔硫化型加氢催化剂的制备方法 Download PDFInfo
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- CN106732666B CN106732666B CN201510803488.6A CN201510803488A CN106732666B CN 106732666 B CN106732666 B CN 106732666B CN 201510803488 A CN201510803488 A CN 201510803488A CN 106732666 B CN106732666 B CN 106732666B
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Classifications
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/882—Molybdenum and cobalt
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
- B01J23/8885—Tungsten containing also molybdenum
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Abstract
本发明提供了一种一次成型的大孔硫化型加氢催化剂的制备方法，包括如下内容：（1）将硫化剂、硫化助剂和添加剂颗粒混合均匀，在90‑150℃条件下恒温5‑50min，然后加入含有加氢活性金属的水溶液，100‑140℃下反应5‑60min，分离除去添加剂颗粒，得到液体混合物I；（2）将胶溶剂、水和尿素混合均匀，得到液体混合物II；（3）将液体混合物I、液体混合物II和铝源混捏、挤出成型，得到湿物料；（4）将湿物料进行氨处理过程，然后进行冷冻，干燥、焙烧得到硫化型加氢催化剂。本发明通过催化剂制备和硫化过程同时完成，催化剂的孔分布更加集中，制备过程简单、提高催化剂的催化活性、降低催化剂制备成本，具有较为广阔的市场应用前景。
Description
技术领域
本发明涉及一次成型的大孔硫化型加氢催化剂的制备方法。
背景技术
加氢精制、加氢处理和加氢裂化等炼油催化加氢生产工艺过程是环境友好的炼油生产工艺，可广泛应用于生产汽油、煤油、柴油、润滑油、石蜡等清洁石油产品。随着产品质量的不断升级、环保法规的日益严格以及原油日趋劣质化、重质化，加氢技术在全世界范围内都得到广泛重视和应用，我国炼油企业的加氢装置处理能力不断增长、对加氢催化剂需求量逐年增加，而这些催化剂大多经硫化后才可获得更好的性能。加氢过程中催化剂的预硫化（活性金属从氧化物状态转化为硫化物状态）是催化剂应用的重要环节之一。因此，催化剂在与烃油接触之前必须先进行预硫化处理，以将催化剂的活性金属从氧化态转化成硫化态。
目前市场提供的加氢催化剂活性金属大多是金属氧化物，国内普遍采用的硫化方法是器内预硫化方法，即在加氢装置内通过严格控制的复杂过程将催化剂的活性金属从氧化态转化为硫化态。加氢催化剂的器内预硫化过程中需要使用和处置一些如二硫化碳CS2等的有毒有害硫化剂；装置需要配套建设仅在新鲜催化剂（或再生催化剂）在开工时才使用的造价较高的硫化系统设施；催化剂反应器内活化过程复杂，硫化剂注入速率、硫化氢浓度和升温速度等控制步骤繁多，使装置开工时间变得漫长，不仅占用了装置有效的生产运行时间，而且加氢催化剂得不到充分的预硫化，催化剂活性金属不能被充分利用，催化剂真正起活性作用的活性中心数所占有的比例不高；催化剂开工现场进行器内预硫化时存在着安全生产隐患及环境污染等问题，如在催化剂硫化期间，加氢装置处于高浓度H2S气氛下，并且在短时间内反复升降温也给炼油企业的安全生产带来隐患；此外，采用器内活化方法，催化剂装填和反应器内构件等众多因素均会严重影响催化剂的活化效果。因此，开发了器外预硫化技术，并在国内外得到广泛的研究和应用。加氢催化剂器外预硫化技术是将新鲜或再生的氧化态催化剂在装入加氢装置反应器之前，在加氢反应器之外对氧化态催化剂进行预硫化处理的工艺方法。采用特殊的工艺过程，将硫化剂提前加到催化剂上，并以硫化物的某种化学形式与催化剂的活性金属组分相结合，将氧化态催化剂制成器外预硫化催化剂，最终将氧化态催化剂转化成硫化态催化剂。
在现有技术中将元素硫引入催化剂的方式一般包括升华吸附、熔化浸渍、分散在有机溶液中浸渍、直接用固体元素硫粉末混合等。CN200510046429.5公开了一种加氢催化剂组合物及其制备方法。该方法通过引入有机氮化合物与硫、有机溶剂共同作用下，可以进一步提高催化剂在活化时的持硫率，减缓集中放热，降低催化剂床层的温升，并且可以提高催化剂活性。但是，无论采用器内预硫化技术还是器外预硫化技术，催化剂在实际应用之前都必须经历催化剂的载体制备（载体的挤条成型、干燥、焙烧），催化剂活性金属物质的添加，活性金属物质转化为氧化态（催化剂的挤条成型、干燥、焙烧）、活性金属物质由氧化态转化为硫化态的过程（催化剂的器内预硫化或器外预硫化），因此，上述过程复杂，生产过程的影响因素多、催化剂产品的制造成本高。另外，由于经历了多个步骤最终完成催化剂的硫化，使得催化剂的活性金属只能处于催化剂最外表面的能够得到利用，而内层或与催化剂载体形成较强相互作用的部分不能得到充分硫化，从而影响催化剂活性的发挥。
CN201210442769.X公开了一种硫化型加氢催化剂的制备方法，该方法中的方式一：采用载体前驱物与元素硫、辅助剂混捏，成型，干燥，负载加氢活性金属组分，然后进行热处理，得到硫化型加氢催化剂；方式二：将活性金属在制备载体时引入，可混捏加入活性金属盐溶液，也可与活性金属盐与载体前驱物、元素硫、辅助剂、成型助剂混合，成型后干燥和热处理。然后再高温处理。其中，方式一制备的催化剂存在元素硫与加氢活性金属组分是分步加入的，即元素硫和载体前驱物辅及助剂先混合，然后在经过一定的热处理后才与活性金属组分相互作用，因此，元素硫先与载体物质作用，与活性金属组分很难很好地相互作用，不利于活性金属组分的硫化反应，从而影响活性金属的利用率，降低催化剂活性；方式二制备催化剂时是直接将活性金属组分与载体前驱物、元素硫、辅助剂、成型助剂混合，同样存在活性金属组分与元素硫混合的相互作用效果不好的问题。
发明内容
针对现有技术的不足，本发明提供了一种一次成型的大孔硫化型加氢催化剂的制备方法。本发明通过催化剂制备和硫化过程同时完成，得到适宜孔结构和催化性能，制备过程简单、提高催化剂的催化活性、降低催化剂制备成本，有效地解决催化剂硫化反应的集中放热问题和初始温度低的问题，而且本发明方法制备的催化剂可以获得较大的孔容，而且催化剂的孔分布更加集中，切合了当前国内炼油企业的现实需求，具有较为广阔的市场应用前景。
本发明的一次成型的大孔硫化型加氢催化剂的制备方法，包括如下内容：（1）将硫化剂、硫化助剂和添加剂颗粒混合均匀，在90-150℃条件下恒温5-50min，然后加入含有加氢活性金属的水溶液，100-140℃下反应5-60min，分离除去添加剂颗粒，得到液体混合物I；（2）将胶溶剂、水和尿素混合均匀，得到液体混合物II；（3）将液体混合物I、液体混合物II和铝源混捏、挤出成型，得到湿物料；（4）将湿物料进行氨处理过程，然后进行冷冻，干燥、焙烧得到硫化型加氢催化剂。
本发明方法中，步骤（1）所述的硫化剂为二硫化碳（CS2）、二甲基二硫化物（DMDS）、叔壬基多硫（TNPS）、硫脲、正丁基硫醇（NBM）、乙基硫醇（EM）、环丁砜和二甲亚砜等中的一种或几种。
本发明方法中，步骤（1）所述的硫化助剂为植物油、动物油、汽油、煤油、柴油、白油、润滑油等中的一种或几种，所述的植物油可以为菜子油、豆油、花生油、玉米油、亚麻油、蓖麻油、棉籽油、葵花籽油、茶籽油和椰子油等植物油，所述的动物油为猪油、牛油和羊油等。
本发明方法中，步骤（1）所述的添加剂为加氢领域中常用的加氢精制催化剂和/或用于加氢裂化的加氢裂化催化剂，所述的加氢精制催化剂如加氢脱硫或加氢脱氮的催化剂，可以是商用的或自行研发制备的。如用于如中国石油化工股份有限公司抚顺石油化工研究院研制开发的催化剂FH-40B、FH-40C、UDS-5、UDS-6、FF-36、FF-46、FC-12、FC-32和FC-50等，以及上述这些氧化态催化剂经过器外预硫化处理的器外预硫化催化剂等中的一种或几种。如中国石油化工股份有限公司抚顺石油化工研究院研制开发的FH-40B催化剂进行器外预硫化处理，预硫化处理过程为本领域技术人员熟知，优选采用如下方式：FH-40B催化剂：单质硫：煤油：菜子油质量比为1：0.02-0.20：0.001-0.05：0.10-0.50，进行混合10-40min，在50-200℃条件下经过器外预硫化处理后，得到FH-40B器外预硫化催化剂。
本发明方法中，步骤（1）所述的添加剂的颗粒直径范围为0.1-100mm，较好范围为0.5-50mm，最好范围在3-10mm。本发明对于催化剂的颗粒大小无特别限制，只是当催化剂的颗粒直径>3.0mm时方便催化剂与溶液的分离。
本发明方法中，步骤（1）所述的加氢活性金属为第VIB族、第VIII族金属中的一种或几种，第VIB族金属为Mo和/或W，第VIII族金属为Ni和/或Co；含有加氢活性金属的水溶液浓度以氧化物计：WO3和/或MoO3为5-200g/100ml，优选为10-180g/100ml，更优选为20-100g/100ml，NiO和/或CoO 为1-80g/100ml，优选为5-50g/100ml；例如Mo-Ni-P水溶液浓度为：MoO3 20-100g/100ml，NiO 5-40g/100ml。又如Mo-Co水溶液浓度为MoO3 20-100g/100ml，CoO5-40g/100ml。如W-Ni-P水溶液浓度为WO3 20-100g/100ml，NiO 5-40g/100ml。含有加氢活性金属的水溶液的配制方式为本领技术技术人员熟知，一般采用含有活性金属的盐类等原料进行配制，如硝酸镍、碳酸镍、柠檬酸镍、三氧化钼、七钼酸铵、二钼酸铵、钼酸铵、（偏）钨酸铵、（碱式）碳酸钴、硝酸钴、柠檬酸钴等。
本发明方法中，步骤（1）所述液体混合物I各组分的质量百分比为：硫化剂0.2%~30%，硫化助剂0.8%~69%，加氢活性金属水溶液1%~99%；液体混合物I各组分质量百分比较好为：硫化剂1%~25%，硫化助剂4%~55%，加氢活性金属水溶液20%~95%；液体混合物I各组分质量百分比最好为：硫化剂2%~15%，硫化助剂8%~35%，加氢活性金属水溶液50%~90%。
本发明方法中，步骤（1）所述的添加剂与液体混合物I中的硫化剂与质量比为：1:0.001-50，优选为1:0.01-5.0，更优选为1:0.04-1.6。
本发明方法中，步骤（2）所述的胶溶剂为无机酸和/或有机酸，其中无机酸选自硝酸、磷酸等。使用的有机酸可以是含有2~25个碳原子的有机羧酸，优选含有4~18个碳原子的有机羧酸，可以是一元酸也可以是二元酸、三元酸等，如草酸、柠檬酸、月桂酸、乳酸、苹果酸、酒石酸、琥珀酸、乙酸、乙二酸、乙二胺四乙酸、壬酸、水杨酸、醋酸乙烯、丁二烯酸、葡萄酸、麦芽酸、油酸、亚油酸、硬脂酸、软脂酸、12-羟基硬脂酸、3,4,5-三甲氧基苯甲酸等中的一种或几种。
本发明方法中，步骤（2）所述的液体混合物II各组分的质量百分比为：
所述的胶溶剂0.1%~30%，尿素0.1%~50%，水20%~99.8%；所述的液体混合物II各组分的质量百分比较好为：胶溶剂1%~25%，尿素1%~35%，水40%~98%；所述的液体混合物II各组分的质量百分比最好为：胶溶剂3%~14%，尿素2%~16%，水70%~95%。
本发明方法中，步骤（2）所述的胶溶剂优选无机酸和有机酸两种，其中无机酸:有机酸的质量比为：1:0.1-25，较好为1:0.5-12.5，最好为1:1-2.5。
本发明方法中，步骤（3）所述的铝源为拟薄水铝石、氢氧化铝、氧化铝、氧化铝干胶、高醇铝、铝片、硝酸铝、分子筛或蒙脱土中的一种或几种。
本发明方法中，步骤（3）所述的除了铝源之外，还可以加入硅、钛、锆等助剂。其中，硅源为硅溶胶、水玻璃、 硅酸、二氧化硅、四氟硅酸铵、硅酸钠、正硅酸乙酯、分子筛、白碳黑和蒙脱土中的一种或几种。钛源为二氧化钛、三氯化钛、四氯化钛、硝酸钛和硫酸钛的一种或几种。锆源为二氧化锆、氧氯化锆、氯化锆、硝酸锆和硫酸锆的一种或几种。助剂的加入方式可以在步骤（1）、步骤（2）和步骤（3）任意的步骤中加入，如果助剂以液态的形式加入，则加入液体混合物I、液体混合物II之中；如果助剂以固态物质加入，则可以在步骤（3）的混捏过程中加入。助剂的加入量以铝源: 助剂质量比为：1:0.001-0.8，较好为1:0.05-0.5，最好为1:0.01-0.15。
本发明方法中，步骤（3）所述的铝源:液体混合物I:液体混合物II质量比为：1:0.1-33:0.1-155，较好为1:0.1-16:0.2-78，最好为1:0.1-3.3:0.3-15.5。
本发明方法中，步骤（3）所述的干燥条件为：60-240℃下干燥2-8h；所述的焙烧条件为：350-600℃下焙烧2-8h。
本发明方法中，步骤（4）所述的氨处理过程为：将挤条后的湿物料浸渍稀氨水溶液或含铵类化合物和/或有机胺的稀氨水溶液；其中有机胺和/或铵类化合物与稀氨水溶液（未加入铵类化合物和/或有机胺的稀氨水溶液）的质量比为：0.001~0.5:1，较好为0.01~0.15:1，最好为0.02~0.1:1。
氨处理条件为常温常压；浸渍的液固体积比为0.5-20：1，较好为1-10：1，最好为1-3：1；氨处理时间为0.01-40 h，较好为0.5-20 h，最好为2-10 h；其中稀氨水溶液的浓度为0.05-40%，较好为2-20%，最好为5-15%。
所述的有机胺是含有1~15个碳原子的有机胺化合物，优选含有2~10个碳原子的有机胺化合物，如烃基胺类物质、醇胺类物质、氨基酸类物质、酰胺类物质等中的一种或几种，具体物质如乙二胺、乙醇胺、二乙醇胺、三乙醇胺、二异丙醇胺、三乙胺、2－环己二胺、1,3－丙二胺、三乙烯二胺、三乙烯四胺、叔丁胺、十二胺、三辛胺、三异丙酸铵、N,N-二乙基乙醇胺、氨基壬酸、氨基乙酸、次氨基三乙酸、N,N-二乙基羟胺、N-甲基二乙醇胺、六亚甲基四胺、N,N-二异丙基乙醇胺、碳酰胺、乙酰苯胺、N,N-二羟乙基苯胺、尿素、硫脲、乙二胺四乙酸、氨基脲、谷氨酸、硫氰化铵或氢氧化四甲胺，以及与上述物质结构相近的其它物质中的一种或几种。优选同时含有两个或多个胺基基团的有机物，如乙二胺、尿素、硫脲和乙二胺四乙酸；所述的铵化合物为有机铵或无机铵，其中有机铵是含有1~15个碳原子的有机铵化合物，优选含有2~10个碳原子的有机铵化合物；所述的铵类化合物选自碳酸乙二酸铵、二甲氨基二硫代甲酸铵、硫氰化铵、碳酸铵、碳酸氢铵、磷酸铵、磷酸氢铵、磷酸二氢铵、硫化铵、硝酸铵或氯化铵等，以及与上述物质结构相近的其它物质中的一种或几种，优选碳酸铵、碳酸氢铵、磷酸氢铵或磷酸二氢铵。有机胺化合物可以和铵类化合物同时使用，也可以单独使用，混合比例没有限制。同时使用时，也可以将有机胺化合物和/或铵类化合物在水溶液中加入，也可以在油相中加入。
本发明方法中，步骤（4）所述湿物料的冷冻条件：冷冻温度为-40℃～0℃，较好为-18℃～0℃，最好为-8℃～-1℃；冷冻时间为0.5-72 h，较好为3-20 h，最好为6-16 h。
本发明方法中，还可以在步骤（1）、步骤（2）或步骤（3）中加入扩孔剂，如聚环氧乙烷、环氧树脂、聚乙二醇（PET）、聚乙烯醇、丙二醇、甘油、三甘醇、聚丙酰胺、田菁粉、淀粉、纤维素、季铵盐。扩孔剂在步骤（3）中加入时，铝源: 扩孔剂质量比为：1:0.001-0.5，较好为1:0.005-0.2，最好为1:0.02-0.10。扩孔剂在步骤（1）中加入时，扩孔剂:液体混合物I质量为1:0.1-800，较好为1:1-400，最好为1:2-88。扩孔剂在步骤（2）中加入时，扩孔剂:液体混合物II质量比为1:0.1-2000，较好为1:0.2-1000，最好为1:1-410。
本发明方法中，上述所加入的活性金属、铝源、助剂、扩孔剂等物质可以采用多样加入方式。如果这些物质是可溶解与水中的物质、或是可以水相和（/或）与油相溶的液态物质，则可以在液态的形式加入液体混合物I、液体混合物II之中；如果这些物质是固态物质，则可以加入固体混合物之中。
本发明催化剂应用于柴油加氢脱硫反应和加氢脱氮反应时，以混合柴油为原料油，在反应压力4.0-8.0MPa、氢油体积比200-500、体积空速1-4h-1、反应温度340-360℃的工艺条件下。
本发明与现有技术相比具有如下优点：
（1）本发明人在研究中发现，无论是活性金属的金属氧化物、硫化剂与氧化铝前身物这种混捏方式，还是完全硫化后的金属硫化物再与氧化铝前身物混捏，即使存在助挤剂、胶溶剂的情况下，物料之间的结合度并不是很好，物料之间很容易发生松散，而通过控制金属与硫的硫化程度，使二者之间交联缩合反应时，硫处于双键的交联键合之中，此时这种活性半硫化金属硫化物（没有完全硫化生成金属硫化物）与氢氧化铝很容易结合在一起，混捏之后，得到的催化剂的强度大大提高，同时活性组分分布更加均匀；本发明在制备过程中加入氧化型催化剂或器外预硫化催化剂等添加剂，促进了活性金属的金属氧化物与硫化剂形成活性半硫化金属硫化物。
（2）本发明通过预先氨处理和冷冻方法制备的催化剂可以获得较大的孔容，而且催化剂的孔分布更加集中。本发明利用湿物料（湿载体或湿催化剂）中含水在冰冻的温度条件下，利用水的冷冻时的融胀作用使得催化剂孔容增大，并同时将催化剂孔壁压实，增大催化剂孔容的同时提高催化剂的强度。通过控制低温或冷冻的时间，来调节载体或催化剂的孔的大小和比例，从而可以满足不同反应类型和不同反应物对于催化剂不同大小孔的需要。如有利于4，6-二甲基苯并噻吩等大分子化合物进行加氢脱硫反应和加氢加氢脱氮反应。本发明催化剂用于重油以及渣油的加氢脱硫和加氢脱氮反应，具有更好的催化活性。
（3）本发明在制备过程中加入的尿素，通过调节尿素与胶溶剂的比例，使活性金属逐步均匀沉淀，同时与氢氧化铝结合，促进了活性金属硫化物的均匀分布，避免产生活性金属团聚的现象，然后经过干燥与焙烧过程时，尿素或是水解反应生成NH3和CO2，或是缩合反应生成缩二脲，这两种反应最终都有利于催化剂孔道的生成；在挤条过程中，保存下来的孔促使在催化剂自然断裂开，形成催化剂的自然断条；
（4）本发明在制备过程中稀氨水溶液的处理过程使得催化剂具有更大孔容的同时具有更集中的孔分布，有利于提高催化剂活性。而且稀氨水溶液或铵类化合物和/或有机胺的加入有利于催化剂的固孔作用，使得催化剂具有更好的强度。
（5）本发明催化剂具有多级孔道，有利于催化剂的加氢脱硫和加氢脱氮反应的进行，有利于加氢反应过程中反应物在催化剂孔道内的扩散，提高催化剂的活性。而且，硫化剂同时作为扩孔剂，可以使得催化剂的制备催化剂的孔刚好形成于催化剂表面活性金属所在处，有利于反应物扩散在此反应，因而提高了催化剂的加氢活性，同时提高催化剂的活性金属利用率。
（6）本发明催化剂开工时可以直接活化，不需要再硫化，节省加氢装置的开工时间，提高炼油厂的经济效益。
具体实施方式
下面结合实施例进一步说明本发明的制备过程，但并不因此限制本发明。
实施例1
1. 配制Mo-Ni-P溶液：首先在配制容器内加入净水50ml，启动搅拌器，缓慢加入氧化钼57.2 g、碱式碳酸镍22.4g，最后缓慢加入磷酸1.27g，避免碱式碳酸盐加热分解出二氧化碳突沸，物料加完盖紧盖，然后加热升温至＞100℃，恒温1～2hr，至氧化钼和碱式碳酸镍全部溶解，制备得到Mo-Ni -P溶液。Mo-Ni -P溶液浓度为MoO3， 57.1g/100ml；NiO，9.8 g/100ml；P，4.0 g/100ml；
2. 取单质硫10.9 g、煤油2g、菜子油22g进行混合15min；加入Mo-Ni 型EPRES器外预硫化催化剂UDS-6（Φ3.0）5g，升温至100-120℃，恒温5-15min；然后，加入上述Mo-Ni -P溶液64ml，并在120℃恒温25min，然后，冷却并分离除掉器外预硫化催化剂UDS-6，得到液体混合物I；
3. 取水50ml，加入浓硝酸4.6ml稀释后得到稀硝酸；然后，再加入柠檬酸5g和尿素4g，然后，加入甘油2g，搅拌混匀，得到液体混合物II；
4.将液体混合物I 、液体混合物II 、将醇铝法制备的拟薄水铝石66.7g、硫酸铝法制备的氢氧化铝71.4g和田菁粉3g加入混捏机中，混合20min；然后将混合物料加入碾压机中进行碾压30min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ0.9mm-3.0mm），得到催化剂的前驱物；
5. 取10%稀氨水200ml，加入氨基乙酸0.5g和碳酸铵2g，搅拌混匀，催化剂的前驱物在上述的稀氨水中浸泡10min，取出催化剂浸氨湿料；
6. 催化剂浸氨湿料在-18℃冷冻5.0h；
7. 催化剂物料在120℃烘干4h；
8. 烘干物在500焙烧3h，得到催化剂A，该催化剂内活性金属组分的含量为MoO324.0%，NiO 4.15%。
实施例2
1. 首先在配制容器内加入净水25ml，启动搅拌器，缓慢加入碱式碳酸钴9.8g，柠檬酸14g，然后加热升温至＞100℃，恒温10～20min，自然冷却至室温，得到Co-柠檬酸溶液。溶液浓度为CoO，14.5 g/100ml；
2. 取单质硫10.9g、柴油2g、豆油22g、甘油3g进行混合5min；加入Co-Mo型EPRES器外预硫化催化剂FH-40B（Φ3.0）5g，升温至100-120℃，恒温25min；然后，加入上述Co-柠檬酸溶液65ml，并在120℃恒温25min。然后，冷却并分离除掉器外预硫化催化剂FH-40B，得到液体混合物I；
3. 取水50ml，加入浓硝酸4.6ml稀释后得到稀硝酸；然后，再加入柠檬酸5g和尿素4g，然后，再加入硅溶胶20g，搅拌混匀，得到液体混合物II；
4.将液体混合物I 、液体混合物II 、醇铝法制备的拟薄水铝石67.8g、硫酸铝法制备的氢氧化铝72.5g、淀粉3.5g、三氧化钼42.6g加入混捏机中，混合20min；II然后将混合物料加入碾压机中进行碾压30min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ 0.9mm），得到催化剂的前驱物；
5. 将100ml浓度为2.5%稀氨水中加入乙二胺0.15g，搅拌均匀，催化剂前驱物在上述的稀氨水中浸泡25min；
6. 催化剂浸氨湿料在-4℃冷冻6.0h，催化剂冷冻物料常温放置3h；
7. 催化剂物料在120℃烘干4h；
8. 烘干物在480℃焙烧3hr，得到催化剂B。该催化剂内活性金属组分的含量为MoO3 42.0%，CoO 3.70%。
实施例3
1. 首先在配制容器内加入净水25ml，启动搅拌器，缓慢加入碱式碳酸钴9.8g，柠檬酸14g，然后加热升温至＞100℃，恒温10～20min，自然冷却至室温，溶液体积35ml。制备得到Co-柠檬酸溶液。然后加入七钼酸铵18.2g，再加入氨水(比重0.94g/ml)50ml，配制得到Co-Mo柠檬酸溶液浓度为MoO3， 21.1g/100ml；CoO，3.90g/100ml；
2. 取单质硫12.9 g、白油2.2g、猪油24g进行混合15min；加入氧化态Co-Mo催化剂UDS-5（Φ3.0）5.0g，升温至100-120℃，恒温5-15min；然后，加入上述Co-Mo柠檬酸溶液66ml，并在120℃恒温25min，然后，冷却并分离除掉催化剂UDS-5，得到液体混合物I；
3. 取水52ml，加入浓硝酸4.7ml稀释后得到稀硝酸；然后，再加入柠檬酸5g和尿素4g，搅拌混匀，得到液体混合物II；
4.将液体混合物I 、液体混合物II、醇铝法制备的拟薄水铝石98.7g、硫酸铝法制备的氢氧化铝43.4g和田菁粉3.0g加入混捏机中，混合20min；然后将混合物料加入碾压机中进行碾压30min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ 0.9mm），得到催化剂的前驱物；
5. 取10%稀氨水300ml，加入氨基乙酸2.5g和碳酸氢铵2.4g，搅拌混匀，催化剂前驱物在上述的稀氨水中浸泡15min，取出催化剂浸氨湿料；
6. 催化剂浸氨湿料在-10℃冷冻7.0h；
7. 催化剂的物料在120℃烘干4h；
8. 烘干物在500℃焙烧3hr，得到催化剂C。该催化剂内活性金属组分的含量为MoO3 18.5%，CoO3.80%。
实施例4
1. 配制Mo-Ni-P溶液：首先在配制容器内加入净水50ml，启动搅拌器，缓慢加入偏钨酸61.0g、碱式碳酸镍16.0g，最后缓慢加入磷酸1.27g，避免碱式碳酸盐加热分解出二氧化碳突沸，物料加完盖紧盖，然后加热升温至＞100℃，恒温1～2hr，至氧化钼和碱式碳酸镍全部溶解，然后，加入三氯化钛3g，制备得到Mo-Ni -P溶液。Mo-Ni -P溶液浓度为MoO3，62.1g/100ml；NiO，10.8 g/100ml；P，4.0 g/100ml；
2. 取单质硫11.3 g、煤油2.4g、花生油22.5g进行混合35min；加入Ni-Mo型催化剂UDS-6（Φ3.0）15.0g，升温至100-120℃，恒温25min；然后，加入上述Mo-Ni -P溶液65ml，并在120℃恒温25min，然后，冷却并分离除掉催化剂UDS-6，得到液体混合物I；
3. 取水50ml，加入浓硝酸4.8ml稀释后得到稀硝酸；然后，再加入柠檬酸8g和尿素7g，然后，加入甘油2g，搅拌混匀，得到液体混合物II；
4.将液体混合物I 、液体混合物II 、醇铝法制备的拟薄水铝石67.1g、硫酸铝法制备的氢氧化铝75.4g、碱式碳酸镍8.4g和田菁粉7g加入混捏机中，混合20min；然后将混合物料加入碾压机中进行碾压40min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ 0.9mm），得到催化剂的前驱物；
5. 取2%稀氨水200ml，加入乙二胺四乙酸2.5g和磷酸铵0.4g，搅拌混匀，催化剂的前驱物在上述的稀氨水中浸泡50min，取出催化剂浸氨湿料；
6. 催化剂浸氨湿料在-14℃冷冻6.0h；取出催化剂物料在-4℃冷冻6.0h；
7. 将催化剂物料在120℃烘干4h；
8. 烘干物在500℃焙烧3hr，得到催化剂D，该催化剂的活性金属组分的含量为MoO3 25.3%，NiO 4.16%。
实施例5
1. 配制W-Ni -P溶液：首先在配制容器内加入净水50ml，启动搅拌器，缓慢加入偏钨酸铵58.0g、碱式碳酸镍14.9g，搅拌1～2h，至偏钨酸铵和碱式碳酸镍全部溶解，冷却后缓慢加入硝酸镍12.2g，制备得到W-Ni -P溶液。W-Ni -P溶液浓度为WO3，67.1g/100ml；NiO，11.6 g/100ml；P，3.6 g/100ml；
2. 取单质硫10.4 g、煤油2.3g、菜子油21.5g进行混合55min；加入W-Ni 型FC-32催化剂（Φ1.5）5g，升温至100-120℃，恒温25min；然后，加入上述W-Ni -P溶液65ml，并在120℃恒温25min，然后，冷却并分离除掉催化剂FC-32，得到液体混合物I；
3. 取水50ml，加入浓硝酸4.6ml稀释后得到稀硝酸；然后，再加入柠檬酸4.5g和尿素3.5g，然后加入甘油4g，搅拌混匀，得到液体混合物II；
4. 液体混合物I 、液体混合物II 、醇铝法制备的拟薄水铝石66.2g、硫酸铝法制备的氧化铝70.9g、田菁粉7.0g加入混捏机中，混合15min；然后将混合物料加入碾压机中进行碾压35min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ 0.9mm），得到催化剂的前驱物；
5. 取0.98%稀氨水400ml，加入硫脲2.5g，搅拌混匀，催化剂前驱物在上述的稀氨水中浸泡20min，取出催化剂浸氨湿料；
6. 催化剂物料在-18℃冷冻4.0 h；
7. 催化剂的前驱物在120℃烘干4h；
8. 烘干物在500℃焙烧3hr，得到催化剂E，该催化剂内活性金属组分的含量为WO326.2%，NiO 4. 5%。
实施例6
1. 配制W-Mo-Ni -P溶液：首先在配制容器内加入净水50ml，启动搅拌器，缓慢加入氧化钼47.6 g、碱式碳酸镍22.4g，最后缓慢加入磷酸1.27g，避免碱式碳酸盐加热分解出二氧化碳突沸，物料加完盖紧盖，然后加热升温至＞100℃，恒温1～2hr，至氧化钼和碱式碳酸镍全部溶解，冷却后缓慢加入偏钨酸铵16.8g，制备得到W-Mo-Ni -P溶液。W-Mo-Ni -P溶液浓度为WO3 ，13.5%；MoO3， 42.8g/100ml；NiO，9.8 g/100ml；
2. 取单质硫16.9 g、煤油8g、花生油28g进行混合15min；加入EPRES器外预硫化催化剂FH-40C（Φ3.0）25.5g，升温至140℃，恒温15min；然后，加入上述Mo-Ni -P溶液120ml，并在120℃恒温25min, 然后，冷却并分离除掉器外预硫化催化剂FH-40C，得到液体混合物I；
3. 取水10ml，加入浓硝酸10.6ml稀释后得到稀硝酸；然后，再加入柠檬酸11g和尿素10g，搅拌混匀，得到液体混合物II；
4. 将液体混合物I 、液体混合物II、将醇铝法制备的拟薄水铝石67.0g、硫酸铝法制备的氧化铝73.0g、田菁粉9.0g，加入混捏机中，混合20min；II然后将混合物料加入碾压机中进行碾压30min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ0.9mm-3.0mm），得到催化剂的前驱物；
5. 配制 4%稀氨水100ml，催化剂前驱物在上述稀氨水中浸泡20min，取出催化剂浸氨湿料；
6. 催化剂物料在-2℃冷冻10h；
7. 催化剂的前驱物在120℃烘干4h；
8. 烘干物在500℃焙烧3hr，得到催化剂F，该催化剂内活性金属组分的含量为WO38.5%；MoO3 18.7%，NiO 4.50%。
对比例1
1. 配制Mo-Ni-P溶液：首先在配制容器内加入净水50ml，启动搅拌器，缓慢加入氧化钼57.2 g、碱式碳酸镍22.4g，最后缓慢加入磷酸1.27g，避免碱式碳酸盐加热分解出二氧化碳突沸，物料加完盖紧盖，然后加热升温至＞100℃，恒温1～2hr，至氧化钼和碱式碳酸镍全部溶解，制备得到Mo-Ni -P溶液。Mo-Ni -P溶液浓度为MoO3， 57.1g/100ml；NiO，9.8 g/100ml；P，4.0 g/100ml；
2. 取单质硫10.9 g、煤油2g、菜子油22g进行混合15min；加入Mo-Ni 型EPRES器外预硫化催化剂UDS-6（Φ3.0）5g，升温至100-120℃，恒温5-15min；然后，加入上述Mo-Ni -P溶液64ml，并在120℃恒温25min，然后，冷却并分离除掉器外预硫化催化剂UDS-6，得到液体混合物I；
3. 取水50ml，加入浓硝酸4.6ml稀释后得到稀硝酸；然后，再加入柠檬酸5g和尿素4g，然后，加入甘油2g，搅拌混匀，得到液体混合物II；
4.将液体混合物I 、液体混合物II 、将醇铝法制备的拟薄水铝石66.7g、硫酸铝法制备的氢氧化铝71.4g和田菁粉3g加入混捏机中，混合20min；然后将混合物料加入碾压机中进行碾压30min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ0.9mm-3.0mm），得到催化剂的前驱物；
5. 催化剂的前驱物在120℃烘干4h；
6. 烘干物在500焙烧3h，得到催化剂G，该催化剂内活性金属组分的含量为MoO324.1%，NiO 4.05%。
对比例2
1. 取水48ml，加入浓硝酸4.6ml稀释后得到稀硝酸；然后，再加入柠檬酸5g和尿素4g，搅拌混匀，得到液体混合物I；
2. 将液体混合物I、拟薄水铝石66.7g、硫酸铝法制备的氧化铝71.4g、田菁粉3g加入混捏机中，混合20min；然后将混合物料加入碾压机中进行碾压30min，取出混合物料，在F-26型挤条机进行挤条（挤条 模具的孔径Φ0.9mm），得到催化剂的载体湿料；
3. 载体湿料在110℃烘干4h；
4. 载体烘干物在600焙烧3h，得到载体；
5. 配制Mo-Ni -P溶液：首先在配制容器内加入净水50ml，启动搅拌器，缓慢加入氧化钼57.2 g、碱式碳酸镍22.4g，最后缓慢加入磷酸1.27g，避免碱式碳酸盐加热分解出二氧化碳突沸，物料加完盖紧盖，然后加热升温至＞100℃，恒温1～2hr，至氧化钼和碱式碳酸镍全部溶解，制备得到Mo-Ni -P溶液；
6. 取载体100g，采用饱和浸渍法进行喷淋上述Mo-Ni-P溶液80ml，得到催化剂湿料；
7. 催化剂湿料在110℃烘干4h；
8. 催化剂烘干物在600℃焙烧3hr，得到催化剂H。该催化剂活性金属组分的含量为MoO3 24.3%，NiO 4.30%。
对比例3
1. 称取拟薄水铝石(山东氧化铝厂生产，干基为73wt%)900g，田菁粉19g，柠檬酸32g，己烯54ml，硝酸(重量浓度30%)48ml，硅胶(以重量计含二氧化硅30%)159ml，硫代硫酸铵溶液250ml（含硫60g/100ml）混合均匀，在挤条机上挤成1.2mm三叶草条，在鼓风干燥箱中于120℃干燥3小时，即得载体；
2. 取含钼酸铵和硝酸镍溶液（含氧化钼30g/100ml，含氧化镍5g/100ml）浸渍载体A后于120℃干燥3小时，之后在氮气保护下进行热处理，首先升温至200℃，恒温2小时，之后再升温至280℃，恒温1小时，最后升温至450℃恒温3小时，得到催化剂I，该催化剂内活性金属组分的含量为MoO3 24.1%，NiO 4.00%。
对比例4
称取拟薄水铝石(山东氧化铝厂生产，干基为73wt%)900g，田菁粉19g，硫粉100g，柠檬酸32g，十二烯30ml，钼酸铵245g，硝酸镍127g，硝酸(重量浓度30%)48ml，硅胶(以重量计含二氧化硅30%)159ml，去离子水250ml混合均匀，在挤条机上挤成1.2mm三叶草条，在鼓风干燥箱中于120℃干燥5小时，之后在氢气保护下热处理，先在290℃恒温2小时，再在400℃恒温3小时即得催化剂J，该催化剂内活性金属组分的含量为MoO3 24.0%，NiO 4.00%。
实施例7
以重质馏分油为原料油，在反应总压8.0MPa，液时体积空速1.0h-1，氢油体积比800：1，反应温度为380℃的工艺条件下，对比评价了实施例的催化剂A~F和对比例催化剂G~J的加氢活性，其中对比例1催化剂H的开工过程涉及下列步骤：(1) 用氮进行系统的吹扫直至氧的浓度低于0.5 vol%然后在3.4 MPa压力下进行气动试验；(2) 在200℃下用氮气干燥催化剂4h；(3) 在150℃用CS2和轻柴油的混合物湿处理2h进行催化剂的预硫化；(4) 以10-25℃/h的速率持续升温至230℃，然后保持温度10h；(5) 以相同速率进一步升温至320℃并再保持10h。当H2S在循环氢气的浓度为1.0 vol%时，硫化结束；(6) 逐渐引入反应油物料并结束开工过程参比催化剂的后续活性评价在上述工艺条件下进行。
催化剂A~J的性质见表1，催化剂A~J活性对比使用的原料油性质见表2活性对比结果见表3。结果表明，本发明催化剂具有较高的加氢脱硫和加氢脱氮活性。本发明催化剂活性稳定性在一个长时间的反应中进行了考察，本发明催化剂在至少1000小时反应中具有较好活性稳定性。
表1催化剂的性质。
表2 原料油性质。
表3本发明催化剂和参比催化剂的加氢活性对比。
Claims (9)
1.一次成型的大孔硫化型加氢催化剂的制备方法，其特征在于包括如下内容：（1）将硫化剂、硫化助剂和添加剂颗粒混合均匀，在90-150℃条件下恒温5-50min，然后加入含有加氢活性金属的水溶液，100-140℃下反应5-60min，分离除去添加剂颗粒，得到液体混合物I；（2）将胶溶剂、水和尿素混合均匀，得到液体混合物II；（3）将液体混合物I、液体混合物II和铝源混捏、挤出成型，得到湿物料；（4）将湿物料进行氨处理过程，然后进行冷冻，干燥、焙烧得到硫化型加氢催化剂；步骤（1）所述的添加剂为加氢领域中常用的加氢精制催化剂和/或用于加氢裂化的加氢裂化催化剂；步骤（1）所述液体混合物I各组分的质量百分比为：硫化剂0.2%~30%，硫化助剂0.8%~69%，加氢活性金属水溶液1%~99%；步骤（1）所述的添加剂与液体混合物I中的硫化剂的质量比为：1:0.001-50；步骤（2）所述的液体混合物II各组分的质量百分比为：所述的胶溶剂0.1%~30%，尿素0.1%~50%，水20%~99.8%。
2.按照权利要求1所述的方法，其特征在于：步骤（1）所述的硫化剂为二硫化碳、二甲基二硫化物、叔壬基多硫、硫脲、正丁基硫醇、乙基硫醇、环丁砜和二甲亚砜中的一种或几种。
3.按照权利要求1所述的方法，其特征在于：步骤（1）所述的硫化助剂为植物油、动物油、汽油、煤油、柴油、白油或润滑油中的一种或几种。
4.按照权利要求1所述的方法，其特征在于：步骤（1）所述的添加剂的颗粒直径范围为0.1-100mm。
5.按照权利要求1所述的方法，其特征在于：步骤（3）所述的铝源为拟薄水铝石、氢氧化铝、氧化铝、高醇铝、铝片、硝酸铝、分子筛或蒙脱土中的一种或几种。
6.按照权利要求1所述的方法，其特征在于：步骤（3）所述的铝源:液体混合物I:液体混合物II质量比为：1:0.1-33:0.1-155。
7.按照权利要求1所述的方法，其特征在于：步骤（4）所述的氨处理过程为：将挤条后的湿物料浸渍稀氨水溶液或铵类化合物和/或有机胺的稀氨水溶液；其中有机胺和/或铵类化合物与稀氨水溶液的质量比为：0.001~0.5:1；浸渍的液固体积比为0.5-20：1，氨处理时间为0.01-40h。
8.按照权利要求7所述的方法，其特征在于：步骤（4）所述的有机胺是含有1~15个碳原子的有机胺。
9.按照权利要求1所述的方法，其特征在于：步骤（4）所述湿物料的冷冻条件：冷冻温度为-40℃～0℃，冷冻时间为0.5-72 h。
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