CN114425354B - 一种重质油加氢催化剂制备方法及所制备的催化剂和应用 - Google Patents
一种重质油加氢催化剂制备方法及所制备的催化剂和应用 Download PDFInfo
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- CN114425354B CN114425354B CN202011185917.5A CN202011185917A CN114425354B CN 114425354 B CN114425354 B CN 114425354B CN 202011185917 A CN202011185917 A CN 202011185917A CN 114425354 B CN114425354 B CN 114425354B
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- 238000007598 dipping method Methods 0.000 claims description 27
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- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
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- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000463 material Substances 0.000 abstract description 3
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- 238000006243 chemical reaction Methods 0.000 description 7
- 229910000480 nickel oxide Inorganic materials 0.000 description 7
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 7
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- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 2
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- 239000000376 reactant Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
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- 238000001354 calcination Methods 0.000 description 1
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
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- 239000001257 hydrogen Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/883—Molybdenum and nickel
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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- B01J27/20—Carbon compounds
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- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J37/02—Impregnation, coating or precipitation
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
本发明提供一种重质油加氢催化剂的制备方法及所制备的催化剂和应用。制备方法包括：配制一种含有机酸、含磷化合物、胺类化合物、表面活性剂以及至少一种活性金属的水溶液作为浸渍液。浸渍液浸渍载体以负载活性金属组分，浸渍液喷淋量达到理论值90%~98%时，用液体油脂喷淋余量。经养生处理、低温干燥、高温焙烧后获得重质油加氢处理催化剂。本发明具有催化剂耐金属能力高，活性金属和催化剂利用率高的特点，并且物料用量少，工艺操作简单。
Description
技术领域
本发明涉及一种重质油加氢催化剂制备方法及所制备的催化剂和应用，尤其是涉及一种用于提高重质油加氢催化剂的脱硫及脱金属能力的催化剂制备方法及由此所制备的催化剂和应用。
背景技术
加氢反应通常是一种存在气液固的多相反应，大多数催化剂采用负载型，将活性金属配制为稳定溶液后按照等体积浸渍或过饱和浸渍的方法与载体充分接触，经过干燥、焙烧过程后得到催化剂成品。催化剂的物化性质根据所加工的原料不同而不同。包括外观形状、孔结构、活性金属组成等。为了能够充分发挥催化剂活性组分的作用，研究人员通常会根据反应的实际需要对活性组分分布方式进行设计，包括均匀型、蛋壳型、蛋黄型等。在一些扩散步骤为控制步骤的反应中，提高活性金属利用率是很重要的。尤其对于重质油加工过程而言，反应物性质劣质化程度较为严重，分子尺寸大、组成复杂、粘度大、杂质含量高是其主要特征，从而导致反应物分子的扩散阻力大，反应效率相对低。渣油加氢反应过程中重金属等倾向于在催化剂颗粒表面和近表面反应并沉积。随着运行时间的推移，过多的金属沉积导致催化剂孔口堵塞。因此，有针对性的设计出活性金属在催化剂颗粒上为外少里多的不均匀分布，有利于渣油大分子向孔道内部扩散并发生反应，使脱除的金属和积炭等杂质更多的沉积在催化剂颗粒的内部，有利于提高催化剂的容金属量，并能够在一定程度上缓解催化剂表面结焦的问题，避免催化剂床层板结，减缓床层压降升高速度，从而延长催化剂使用寿命。
CN101927176A公开了一种活性金属和酸性助剂浓度呈梯度增加分布的加氢催化剂制备方法。该方法通过配制较稀的活性金属溶液和酸性助剂溶液和去离子水，在喷渍过程中，逐步添加较浓的活性金属溶液和酸性助剂溶液的方法饱和喷渍载体；或通过配制不同浓度的活性金属溶液和酸性助剂溶液，按活性金属浸渍液和酸性助剂溶液浓度从低到高顺序浸渍在载体上；或用酸性助剂浓度较低的溶液和去离子水浸渍，浸渍过程中逐步添加酸性助剂浓度较高的溶液至浸渍液中；干燥焙烧；再用活性金属浓度较低溶液和去离子水浸渍，浸渍过程中逐步添加活性金属浓度较高的溶液至浸渍液中，最终实现金属组分梯度分布。其工艺过程较为繁琐，浸渍过程较难控制。
CN109833890A公开了一种渣油加氢催化剂及其制备，该方法是用含司班表面活性剂的有机溶剂喷浸渣油加氢脱金属催化剂载体，然后干燥；再用含有聚丙烯酸根的活性金属溶液浸渍干燥后的载体，然后干燥、焙烧制得催化剂。该方法制备的渣油加氢催化剂具有高活性金属利用率、高金属分散度、高活性等优点。该方法工艺过程繁琐，二次浸渍操作时存在控制难度加大的风险。
综上，现有技术手段制备催化剂的工艺过程繁杂，不易控制，因此开发一种工艺可控、易操作，具有较强脱硫及脱金属能力的催化剂具有十分重要的意义。
发明内容
针对现有技术的不足，本发明目的在于提供一种适用于重质油加氢处理催化剂的制备方法及其所制备的催化剂及应用。以期提高活性金属利用率、降低物料用量，并且简化制备步骤。本发明另一目的在于提供一种加氢催化剂，以提高脱硫及脱金属性能。
本发明第一方面在于提供一种重质油加氢处理催化剂的制备方法，主要包括以下步骤：
（1）制备浸渍液；
（2）用步骤（1）中浸渍液浸渍载体；
（3）用液体油脂喷淋步骤（2）所得的载体；
（4）将步骤（3）所得的产物养生处理、干燥、焙烧后获得重质油加氢处理催化剂。
进一步，步骤（2）中浸渍液浸渍载体时浸渍液的用量为载体饱和浸渍理论值的90%~98%，优选为92%~96%。步骤（3）中液体油脂喷淋载体时液体油脂的量为步骤（2）浸渍液浸渍载体后载体饱和浸渍理论值的余量。
其中，步骤（1）制备浸渍液的方法包括如下步骤：
（a）配制活性金属、有机酸、含磷化合物的水溶液；
（b）向步骤（a）的水溶液中加入胺类化合物和表面活性剂，得到所述浸渍液。
步骤（a）中所述活性金属为包括至少一种选自第VIII族的金属和至少一种选自VIB族的金属。所述第VIII族金属优选为镍和/或钴。所述第VIB族金属优选为钼和/或钨，最优选为钼。浸渍溶液中活性金属含量以氧化物计，其中第VIB族金属优选为三氧化钼，含量为100~400g/L，优选120~250g/L；第VIII族金属优选氧化镍和/或氧化钴，含量为20~150g/L，优选25~60g/L。所述三氧化钼原料为工业级三氧化钼、钼酸盐、仲钼酸盐中的一种或几种，优选三氧化钼；所述氧化镍原料为工业级硝酸镍、醋酸镍、碱式碳酸镍、氯化镍中的一种或几种，优选碱式碳酸镍；氧化钴原料为硝酸钴、醋酸钴、碱式碳酸钴、氯化钴中的一种或几种，优选碱式碳酸钴。
所述含磷化合物优选为磷酸。所述磷酸的原料为工业级磷酸。在浸渍液中，磷酸的含量以磷计为10~90g/L，优选20~70g/L。
所述有机酸为富马酸、己二酸、酒石酸、柠檬酸、草酸、醋酸、水杨酸、苹果酸中的一种或多种。优选柠檬酸，有机酸类化合物在浸渍液中的含量为2~120g/L，优选4~50g/L。
步骤（a）中所述浸渍液配制方法包括：将活性金属、含磷化合物按照需要量投入到去离子水中，在常温下开始反应15~50分钟，优选20~35分钟，再加入需要量的有机酸继续反应10~60分钟，优选20~40分钟，然后开始升温加热沸腾至原料全部溶解；恒温30~120分钟，优选40~80分钟，然后降温至室温。
步骤（b）中所述溶液配制方法包括：在搅拌状态下向步骤（a）所得水溶液中缓慢加入胺类化合物和表面活性剂。
步骤（b）中所述胺类化合物为六次甲基四胺、乙二胺、辛胺、甲醇胺、二甲醇胺、三甲醇胺、丙醇胺、二丙醇胺、三丙醇胺、多聚醇胺、乙醇胺、二乙醇胺、三乙醇胺中的一种或多种；胺类化合物在浸渍液中的含量为80g/L ~280g/L，优选100g/L ~210g/L。
步骤（b）中所述表面活性剂为吐温-20、吐温-30、吐温-40、吐温-60、吐温-80、吐温-85中一种或多种，优选吐温-60和/或吐温-80；表面活性剂在浸渍液中含量为2~80g/L，优选5~60g/L。
步骤（2）中所述载体为氧化铝载体，可以为市售氧化铝载体，也可以采用任何现有技术来制备，颗粒形状可以为各种形状，优选为条形、圆柱形、三叶草形、四叶草形；氧化铝载体的性质如下：平均孔径超过13nm、颗粒粒径超过1.0mm、吸液率在0.85~1.20范围内。所述浸渍可采用常规的浸渍方法，优选为喷浸法。
步骤（3）中所述液体油脂为花生油、豆油、玉米油、亚麻油、蓖麻油、菜籽油中的一种或多种，优选玉米油和/或蓖麻油。
步骤（4）中，浸渍后样品在常温封闭的条件下放置0.5~12小时。干燥条件为60~160℃下恒定1~3小时。干燥后样品焙烧条件是400~650℃，恒温1~6小时，优选450~600℃下恒温1.5~3.0小时。
本发明第二方面在于提供一种前述方法所制备的重质油加氢处理催化剂。
本发明第三方面在于提供一种前述方法所制备催化剂在重质油加氢过程中的应用。
与现有技术相比，本发明的重质油加氢处理催化剂制备方法具有如下优点：
（1）本发明采用浸渍液和液体油脂分步浸渍载体。浸渍液浸渍90%~98%，液体油脂浸渍余量。由于含活性金属的水溶液已经充满或大部分充满载体孔内空间，液体油脂附着在颗粒表面和部分近表面形成一层油膜，对于浸渍液中金属组分向孔口处的迁移具有一定抑制作用。而且本发明浸渍液的组成及含量更有利于其与液体油脂间的配合作用。使得所制备的催化剂可以抑制金属向孔口迁移趋势，降低孔口金属组分沉积，解决沉积的金属带来的孔口堵塞问题。延长催化剂的使用寿命。
（2）本发明制备过程简单，环保安全，且无需改变现有其他操作。可以提高活性金属利用率及催化剂颗粒利用率，提高催化剂耐金属能力。
（3）本发明的原料液体油脂在使用时单独喷淋至物料上，用量少，制作成本低。
附图说明
图1 为实施例1与对比例1及对比例2催化剂活性金属钼在催化剂横截面的分布趋势图。
具体实施方式
下面结合具体实施方式对本发明内容进行详细阐述。实施例仅为示例性展示发明内容，本发明保护范围不受具体实施方式的限制。
实施例及对比例中金属分布采用日本JEOL公司JSM7500F场发射扫描电子显微镜（分辨率1.0nm）测试。催化剂酸强度分布及酸类型采用吡啶吸附-红外光谱法测得。催化剂孔结构采用美国麦克仪器公司ASAP2420 型物理吸附仪测得。样品经过 300°C抽真空预处理4h，然后在 77K 温度下进行等温N2吸附-脱附实验。
实施例1
称取一种三叶草形市售氧化铝载体100g，编号为A-0，测量其吸水率η为1.05。氧化铝颗粒粒径为1.1mm，平均孔径为14.3nm。称取三氧化钼（含氧化钼99wt%）18.5g，碱式碳酸镍（含氧化镍52wt%）7.2g，磷酸液（含磷26.7wt%）7.6g，加入去离子水。常温下溶解30分钟后，加入柠檬酸1.0g，继续溶解30分钟后开始升温加热沸腾至原料全部溶解。恒温60分钟后降温至室温。在搅拌状态下缓慢加入10g三乙醇胺，再缓慢加入3g吐温-60，待溶液澄清后定容100mL待用。采用喷淋方式将上述浸渍液浸渍在载体A-0上，保持转鼓转动匀化10分钟后，将5mL玉米油喷淋颗粒上并保持转鼓转动匀化30分钟，得到A-1。将A-1在室温封闭容器中下放置5.0小时后在130℃下干燥2小时，最后在580℃下焙烧3小时制得催化剂AC-1。
实施例2
称取一种三叶草形市售氧化铝载体100g，编号为A-0，测量其吸水率η为1.05。氧化铝颗粒粒径为1.1mm，平均孔径为14.3nm。称取三氧化钼（含氧化钼99wt%）18.5g，碱式碳酸镍（含氧化镍52wt%）7.5g，磷酸液（含磷26.7wt%）8.0g，加入去离子水。常温下溶解25分钟后，加入柠檬酸2.0g，继续溶解20分钟后开始升温加热沸腾至原料全部溶解。恒温40分钟后降温至室温。在搅拌状态下缓慢加入12g二丙醇胺，再缓慢加入4g吐温-80，待溶液澄清后定容95mL待用。采用喷淋方式将上述浸渍液浸渍在载体A-0上，保持转鼓转动匀化15分钟后，将10mL蓖麻油喷淋颗粒上并保持转鼓转动匀化30分钟，得到A-2。将A-2在室温封闭容器中下放置4.0小时后在130℃下干燥2小时，最后在560℃下焙烧3小时制得催化剂AC-2。
实施例3
称取一种三叶草形市售氧化铝载体100g，编号为A-0，测量其吸水率η为1.05。氧化铝颗粒粒径为1.1mm，平均孔径为14.3nm。称取三氧化钼（含氧化钼99wt%）18.5g，碱式碳酸镍（含氧化镍52wt%）7.0g，磷酸液（含磷26.7wt%）10.0g，加入去离子水。常温下溶解35分钟后，加入柠檬酸2.6g，继续溶解30分钟后开始升温加热沸腾至原料全部溶解。恒温70分钟后降温至室温。在搅拌状态下缓慢加入14g二乙醇胺，再缓慢加入6g吐温-60，待溶液澄清后定容101mL待用。采用喷淋方式将上述浸渍液浸渍在载体A-0上，保持转鼓转动匀化15分钟后，将4mL亚麻油喷淋颗粒上并保持转鼓转动匀化40分钟，得到A-3。将A-3在室温封闭容器中下放置6小时后在120℃下干燥3小时，最后在570℃下焙烧3小时制得催化剂AC-3。
实施例4
称取一种三叶草形市售氧化铝载体100g，编号为A-0，测量其吸水率η为1.05。氧化铝颗粒粒径为1.1mm，平均孔径为14.3nm。称取三氧化钼（含氧化钼99wt%）24.0g，碱式碳酸镍（含氧化镍52wt%）9.5g，磷酸液（含磷26.7wt%）8.0g，加入去离子水。常温下溶解40分钟后，加入柠檬酸2g，继续溶解20分钟后开始升温加热沸腾至原料全部溶解。恒温80分钟后降温至室温。在搅拌状态下缓慢加入12g乙二胺，再缓慢加入2g吐温-80，待溶液澄清后定容98mL待用。采用喷淋方式将上述浸渍液浸渍在载体A-0上，保持转鼓转动匀化15分钟后，将7mL豆油喷淋颗粒上并保持转鼓转动匀化30分钟，得到A-4。将A-4在室温封闭容器中下放置5小时后在120℃下干2.5小时，最后在560℃下焙烧3小时制得催化剂AC-4。
实施例5
同实施例1，区别在于催化剂制备过程中未加入柠檬酸，制得催化剂AC-5。
实施例6
同实施例1，区别在于催化剂制备过程中未加入三乙醇胺，制得催化剂AC-6。
对比例1
称取一种三叶草形市售氧化铝载体100g，编号为A-0，测量其吸水率η为1.05。氧化铝颗粒粒径为1.1mm，平均孔径为14.3nm。称取三氧化钼（含氧化钼99wt%）18.5g，碱式碳酸镍（含氧化镍52wt%）7.5g，磷酸液（含磷26.7wt%）8.0g，加入去离子水溶解常温下溶解30分钟后加入柠檬酸2.5g，继续溶解30分钟后开始升温加热沸腾至原料全部溶解。恒温60分钟后降温至室温并定容取105mL待用。采用喷淋方式将上述浸渍液浸渍在载体A-0上得到A-5。将A-5在室温封闭容器中下放置4.0小时后在120℃下干燥3小时，最后在560℃下焙烧3小时制得催化剂AC-7。
即同实施例1，区别在于取浸渍液105mL浸渍载体，不加玉米油，制得催化剂AC-7。
对比例2
同实施例1，区别在于待溶液澄清后定容90mL待用。采用喷淋方式将上述浸渍液浸渍在载体A-0上，保持转鼓转动匀化10分钟后，将15mL玉米油喷淋颗粒上并保持转鼓转动匀化30分钟，得到A-6。将A-6在室温封闭容器中下放置5.0小时后在130℃下干燥2小时，最后在580℃下焙烧3小时制得催化剂AC-8。
对实施例及对比例中催化剂的性质进行测试，分别见图1及表1-表3。
表1实施例与对比例中催化剂红外酸性质比较
| 项 目 | 160℃ | 250℃ | 350℃ | 450℃ |
| AC-1 | ||||
| 总酸量，mmol/g | 0.362 | 0.238 | 0.129 | 0.101 |
| B酸，mmol/g | 0.073 | 0.041 | 0.018 | 0.007 |
| L酸，mmol/g | 0.289 | 0.197 | 0.111 | 0.094 |
| AC-2 | ||||
| 总酸量，mmol/g | 0.359 | 0.245 | 0.123 | 0.094 |
| B酸，mmol/g | 0.068 | 0.040 | 0.018 | 0.005 |
| L酸，mmol/g | 0.291 | 0.205 | 0.105 | 0.089 |
| AC-3 | ||||
| 总酸量，mmol/g | 0.367 | 0.252 | 0.130 | 0.083 |
| B酸，mmol/g | 0.071 | 0.057 | 0.011 | 0.002 |
| L酸，mmol/g | 0.296 | 0.195 | 0.119 | 0.081 |
| AC-4 | ||||
| 总酸量，mmol/g | 0.408 | 0.283 | 0.156 | 0.108 |
| B酸，mmol/g | 0.086 | 0.053 | 0.025 | 0.009 |
| L酸，mmol/g | 0.322 | 0.23 | 0.131 | 0.099 |
| AC-5 | ||||
| 总酸量，mmol/g | 0.358 | 0.231 | 0.108 | 0.077 |
| B酸，mmol/g | 0.057 | 0.032 | 0.013 | 0.002 |
| L酸，mmol/g | 0.301 | 0.199 | 0.095 | 0.075 |
| AC-6 | ||||
| 总酸量，mmol/g | 0.356 | 0.229 | 0.109 | 0.073 |
| B酸，mmol/g | 0.050 | 0.027 | 0.009 | - |
| L酸，mmol/g | 0.306 | 0.202 | 0.100 | 0.073 |
| AC-7 | ||||
| 总酸量，mmol/g | 0.347 | 0.226 | 0.113 | 0.078 |
| B酸，mmol/g | 0.061 | 0.036 | 0.010 | - |
| L酸，mmol/g | 0.286 | 0.190 | 0.103 | 0.078 |
| AC-8 | ||||
| 总酸量，mmol/g | 0.361 | 0.249 | 0.126 | 0.081 |
| B酸，mmol/g | 0.068 | 0.055 | 0.012 | 0.004 |
| L酸，mmol/g | 0.293 | 0.194 | 0.114 | 0.077 |
表2 实施例和对比例中催化剂的组成和性质
| 项 目 | AC-1 | AC-2 | AC-3 | AC-4 | AC-5 | AC-6 | AC-7 | AC-8 |
| MoO3，wt% | 14.3 | 14.6 | 14.4 | 17.8 | 14.4 | 14.5 | 14.5 | 14.3 |
| NiO，wt% | 2.9 | 2.8 | 2.8 | 3.6 | 2.7 | 2.8 | 2.7 | 2.7 |
| 比表面积，m2/g | 191 | 187 | 190 | 176 | 188 | 185 | 186 | 186 |
| 孔容，cm3/g | 0.488 | 0.491 | 0.485 | 0.472 | 0.483 | 0.481 | 0.481 | 0.483 |
表3 实施例与对比例的催化剂加氢脱硫性能比较
| 项目 | AC-1 | AC-2 | AC-3 | AC-4 | AC-5 | AC-6 | AC-7 | AC-8 |
| 原料油 | 渣油 | 渣油 | 渣油 | 渣油 | 渣油 | 渣油 | 渣油 | 渣油 |
| S/µg·g-1 | 2.6 | 2.6 | 2.6 | 2.6 | 2.6 | 2.6 | 2.6 | 2.6 |
| Ni+V/µg·g-1 | 71 | 71 | 71 | 71 | 71 | 71 | 71 | 71 |
| 反应条件 | ||||||||
| 反应压力，MPa | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 | 15.7 |
| 反应温度，℃ | 388 | 388 | 388 | 388 | 388 | 388 | 388 | 388 |
| 体积空速，h-1 | 0.32 | 0.32 | 0.32 | 0.32 | 0.32 | 0.32 | 0.32 | 0.32 |
| 氢油比，V/V | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 |
| 相对活性，wt% | ||||||||
| 脱硫 | 116 | 115 | 113 | 129 | 110 | 108 | 100 | 105 |
| 脱金属 | 113 | 112 | 109 | 121 | 108 | 106 | 100 | 104 |
如图1所示，实施例催化剂颗粒表面和近表面活性金属分布相对少，催化剂孔口堵塞效应弱，有利于渣油大分子扩散至催化剂孔道内部并与活性中心接触并发生加氢反应。因此其加氢脱硫和脱金属能力更强。实施例的酸性质中，总酸量和B酸量均高于其他对比例催化剂。从催化剂的活性评价结果来看，采用本发明提供的方法制备的催化剂的脱硫和脱金属性能较佳，对比例1-2中的催化剂脱硫和脱金属性能差于实施例催化剂。
Claims (19)
1.一种重质油加氢处理催化剂的制备方法，其特征在于，包括以下步骤：
（1）制备浸渍液；
（2）用步骤（1）中浸渍液浸渍载体；
（3）用液体油脂喷淋步骤（2）所得的载体；
（4）将步骤（3）所得的产物养生处理、低温干燥、高温焙烧后获得重质油加氢处理催化剂；
所述步骤（1）中制备浸渍液的方法如下：
（a）配制活性金属、有机酸、含磷化合物的水溶液；
（b）向步骤（a）的水溶液中加入胺类化合物和表面活性剂，得到所述浸渍液；
步骤（2）中浸渍液浸渍载体时浸渍液的用量为载体饱和浸渍理论值的90%~98%；步骤（3）中液体油脂喷淋载体时液体油脂的量为步骤（2）浸渍液浸渍载体后载体饱和浸渍理论值的余量；步骤（3）中所述液体油脂为花生油、豆油、玉米油、亚麻油、蓖麻油、菜籽油中的一种或多种；
步骤（a）中所述活性金属为包括至少一种选自第VIII族的金属和至少一种选自VIB族的金属；所述第VIII族金属为镍和/或钴；所述第VIB族金属为钼和/或钨；
步骤（2）中所述载体为氧化铝载体。
2.根据权利要求1所述的制备方法，其特征在于，步骤（2）中浸渍液浸渍载体时浸渍液的用量为载体饱和浸渍理论值的92%~96%；步骤（3）中液体油脂喷淋载体时液体油脂的量为步骤（2）浸渍液浸渍载体后载体饱和浸渍理论值的余量。
3.根据权利要求1所述的制备方法，其特征在于，所述第VIB族金属为钼。
4.根据权利要求3所述的制备方法，其特征在于，浸渍液中活性金属含量以氧化物计，其中第VIB族金属含量为100~400g/L；第VIII族金属含量为20~150g/L。
5.根据权利要求4所述的制备方法，其特征在于，浸渍液中活性金属含量以氧化物计，其中第VIB族金属含量为120~250g/L；第VIII族金属含量为25~60g/L。
6.根据权利要求1所述的制备方法，其特征在于，步骤（a）中所述含磷化合物为磷酸，在浸渍液中，磷酸的含量以磷计为10~90g/L。
7.根据权利要求1所述的制备方法，其特征在于，步骤（a）中所述含磷化合物为磷酸，在浸渍液中，磷酸的含量以磷计为20~70g/L。
8.根据权利要求1所述的制备方法，其特征在于，步骤（a）中所述有机酸为富马酸、己二酸、酒石酸、柠檬酸、草酸、醋酸、水杨酸、苹果酸中的一种或多种；有机酸在浸渍液中的含量为2~120g/L。
9.根据权利要求8所述的制备方法，其特征在于，步骤（a）中所述有机酸为柠檬酸。
10.根据权利要求8所述的制备方法，其特征在于，步骤（a）中，有机酸在浸渍液中的含量为4~50g/L。
11.根据权利要求1所述的制备方法，其特征在于，步骤（b）中所述胺类化合物为六次甲基四胺、乙二胺、辛胺、甲醇胺、二甲醇胺、三甲醇胺、丙醇胺、二丙醇胺、三丙醇胺、多聚醇胺、乙醇胺、二乙醇胺、三乙醇胺中的一种或多种；胺类化合物在浸渍液中的含量为80g/L ~280g/L。
12.根据权利要求11所述的制备方法，其特征在于，步骤（b）中，胺类化合物在浸渍液中的含量为100g/L ~210g/L。
13.根据权利要求1所述的制备方法，其特征在于，步骤（b）中所述表面活性剂为吐温-20、吐温-30、吐温-40、吐温-60、吐温-80、吐温-85中一种或多种；表面活性剂在浸渍液中浓度为2~80g/L。
14.根据权利要求13所述的制备方法，其特征在于，步骤（b）中所述表面活性剂为吐温-60和/或吐温-80。
15.根据权利要求13所述的制备方法，其特征在于，步骤（b）中，表面活性剂在浸渍液中浓度为5~60g/L。
16.根据权利要求1所述的制备方法，其特征在于，步骤（3）中所述液体油脂为玉米油和/或蓖麻油。
17.根据权利要求1所述的制备方法，其特征在于，步骤（2）中，所述氧化铝载体的性质如下：平均孔径超过13nm、颗粒粒径超过1.0mm、吸液率在0.85~1.20范围内。
18.一种权利要求1~17任一项所述制备方法所制备的重质油加氢处理催化剂。
19.一种权利要求1~17任一项所述制备方法所制备的重质油加氢处理催化剂在重质油加氢过程中的应用。
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