CN114555228A - 具有使用螯合剂掺入金属的有机添加剂的加氢处理催化剂以及制备和使用此类催化剂的方法 - Google Patents
具有使用螯合剂掺入金属的有机添加剂的加氢处理催化剂以及制备和使用此类催化剂的方法 Download PDFInfo
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- CN114555228A CN114555228A CN202080071885.8A CN202080071885A CN114555228A CN 114555228 A CN114555228 A CN 114555228A CN 202080071885 A CN202080071885 A CN 202080071885A CN 114555228 A CN114555228 A CN 114555228A
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- acetate
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- -1 acetate compound Chemical class 0.000 claims description 51
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0209—Esters of carboxylic or carbonic acids
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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
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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
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- 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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—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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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
- B01J31/0238—Amines with a primary amino group
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
一种高活性加氢处理催化剂,其包含已经用金属浸渍溶液浸渍的无机氧化物载体颗粒,所述金属浸渍溶液包含络合剂和氢化金属,所述氢化金属进一步掺入有机添加剂共混物。
Description
本申请要求于2019年10月18日提交的美国临时专利申请62/923,389的权益,该临时专利申请的标题为“具有使用螯合剂掺入金属的有机添加剂的加氢处理催化剂以及制备和使用此类催化剂的方法(HYDROPROCESSING CATALYST HAVING AN ORGANIC ADDITIVEWITH METALS INCORPORATED USING CHELANT AND METHOD OF MAKING AND USING SUCHCATALYST)”,其全部内容通过引用并入本文。
技术领域
本发明涉及一种包括已经用氢化金属组分和金属络合剂的溶液浸渍并用乙酸盐化合物和不饱和脂肪胺化合物的有机添加剂共混物完成的无机载体的加氢处理催化剂组合物、制备该催化剂组合物的方法和该催化剂组合物的用途。
背景技术
加氢处理催化剂用于从烃原料中除去有机硫和氮化合物的工艺中,该烃原料通常源自原油蒸馏。在这些工艺中,有机硫和氮化合物在氢存在下分别催化转化成硫化氢和氨,然后后续从加氢处理的原料中除去。
典型的加氢处理催化剂包括其上沉积有VIB族金属(例如钼和钨)和VIII族金属(例如镍和钴)的载体。磷也可以存在于加氢处理催化剂中。一种制备加氢处理催化剂的方法包括用氢化金属组分浸渍载体,随后煅烧浸渍的载体以将金属组分转化成氧化物。然后将经煅烧的催化剂进行硫化处理以将金属氧化物转化成金属硫化物。
现有技术中存在许多不同的催化剂组合物,其可用于烃原料的加氢处理。例如,US9,156,029(Gabrielov等人)公开了一种加氢处理催化剂,其具有负载有活性金属前驱体、胺组分和不含胺的极性添加剂的载体。该催化剂通过将金属组分掺入载体材料中以得到负载金属的载体,随后用胺化合物和不含胺的极性添加剂浸渍来制备。然后用氢和硫化合物处理浸渍的组合物,并且用于烃原料的加氢处理。
在US 8,262,905(Gabrielov等人)中公开了发现可用于烃原料的加氢处理的另一种催化剂。该催化剂通过将金属组分掺入载体材料中以提供负载有金属的载体材料,随后用烃油和极性添加剂浸渍来制备。然后用氢和硫化合物处理浸渍的组合物,并且用于烃原料的加氢处理。
US 9,211,536(Gabrielov等人)公开了一种加氢处理催化剂,其具有优异的加氢脱硫和加氢脱氮活性和良好的催化稳定性。该催化剂包括由无机氧化物粉末和催化剂细粉的混合物形成的成型载体。将螯合剂、至少一种催化金属和极性添加剂掺入到已经干燥和煅烧的成型载体中。将极性添加剂浸渍到经掺入金属的载体处理的干燥螯合剂中。然后用氢和硫化合物处理该组合物,并用于烃原料的加氢处理。
US 9,376,637(Gabrielov等人)公开了另一种优异的加氢处理催化剂。该催化剂包含具有金属溶液的成型载体,其中螯合剂通过一步浸渍掺入到成型载体中。将极性添加剂掺入到该干燥的掺入金属的载体中,随后用氢气和硫处理以提供催化剂组合物。这种活化添加剂浸渍的组合物可以适当地用于馏出物原料的加氢处理。
需要不断寻找具有增强催化特性的新的和改进的加氢处理催化剂。工业上一直在寻找更好的加氢处理催化剂组合物,当用于处理具有高浓度硫和氮的石油衍生烃工艺物流时,该组合物具有高活性和稳定性。
发明内容
因此,本发明的目的是提供一种在烃原料的催化加氢处理中有用并且具有高活性的组合物以及此类组合物的制备方法。
因此,提供了一种加氢处理催化剂,其包含用金属浸渍溶液浸渍的无机氧化物载体颗粒,所述金属浸渍溶液包括金属络合剂和钴或镍中的一者或两者,以及钼,并且进一步在其中掺入了包含乙酸盐化合物和不饱和脂肪胺化合物的有机添加剂共混物。
加氢处理催化剂通过用包含至少一种氢化金属组分和金属络合剂的金属浸渍溶液浸渍无机氧化物载体颗粒,以提供金属浸渍的颗粒来制备。将金属浸渍的颗粒干燥以提供用有机添加剂共混物浸渍的干燥颗粒,该有机添加剂共混物包含乙酸盐化合物和不饱和脂肪胺化合物。
本发明的加氢处理催化剂和通过本发明方法制备的催化剂组合物可用于通过在加氢处理条件下使原料与催化剂接触来处理烃原料以产生经处理的烃流出物。
具体实施方式
本发明的组合物特别适用于涉及石油衍生原料的催化加氢处理的应用,例如常压馏出物、瓦斯油和残渣以及真空瓦斯油和残渣的加氢处理。
本发明的催化剂组合物包含已经用金属浸渍溶液浸渍的无机氧化物载体颗粒,该金属浸渍溶液包括金属络合剂和钴或镍中的一者或两者,以及钼,在其上掺入包含乙酸盐化合物和不饱和脂肪胺的有机添加剂共混物。
与对比催化剂组合物相比,本发明的组合物表现出改进的加氢脱硫(HDS)和加氢脱氮(HDN)活性。这种催化性能的改进归因于将金属络合剂作为用于产生金属浸渍颗粒的金属浸渍溶液的组分与随后用特定有机添加剂共混物或混合物浸渍金属浸渍颗粒的组合应用。换句话说,本发明的金属络合剂与无机氧化物载体颗粒的金属浸渍和有机添加剂共混物的掺入的结合使用提供了具有增强的催化特性的本发明的加氢处理催化剂。
理论上,金属络合剂的应用以与有机添加剂的掺入协同的方式有助于本发明添加剂浸渍的催化剂特性的增强。它通过与掺入到催化剂的无机载体中的金属形成金属螯合络合物来实现。当随后将有机添加剂掺入到无机载体中时,金属螯合络合物的形成帮助金属的分散。这是因为螯合反应将金属从无机载体的表面拉出或防止金属牢固地结合到无机载体的表面,当金属浸渍的颗粒进一步用本发明的有机添加剂共混物浸渍时,这提供了改进的金属分散。
可以使用任何合适的方法制备本发明组合物的载体颗粒。在一种方法中,将无机氧化物与水混合以形成混合物。混合物应具有允许其形成颗粒如聚集体、球、挤出物和丸粒的特性。该混合物优选为可挤出的混合物或糊状物,使得它可以被挤出并形成挤出物。如果需要,可以将一种或多种添加剂例如胶溶剂和挤出助剂与无机氧化物和水混合。胶溶剂可以是提供无机氧化物胶溶的任何材料。可能的胶溶剂的实例选自无机酸,例如硝酸、盐酸和硫酸。将形成的载体颗粒干燥并煅烧以提供用于制备本发明催化剂的载体颗粒。
在载体颗粒的制备中使用的无机多孔耐火氧化物可以是适合允许掺入金属加氢组分和接收加氢处理催化剂的有机添加剂共混物的任何材料。载体颗粒的无机多孔耐火氧化物应具有允许进一步用金属浸渍溶液填充和在干燥后用本发明的有机添加剂共混物填充的孔隙。
载体颗粒的可能合适的无机多孔耐火氧化物的实例包括二氧化硅、氧化铝、二氧化钛、氧化锆、二氧化硅-氧化铝、二氧化硅-二氧化钛、二氧化硅-氧化锆、二氧化钛-氧化铝、氧化锆-氧化铝、二氧化硅-二氧化钛及其两种或更多种的组合。用于制备本发明组合物的载体的优选多孔耐火氧化物是选自由氧化铝、二氧化硅和二氧化硅-氧化铝组成的组中的一种。其中,最优选的多孔耐火氧化物是氧化铝。
多孔耐火氧化物一般可以具有约50埃至约200埃范围内的平均孔径。通过标准压汞孔率法测量的多孔耐火氧化物的总孔体积在约0.2cc/克至约2cc/克的范围内。
通过B.E.T.测量的多孔耐火氧化物的表面积一般超过约100m2/克,并且其通常在约100m2/克至约500m2/克的范围内,或在125至400m2/克的范围内。
在载体颗粒的制备中,将其在标准干燥条件下干燥,该标准干燥条件可包括50℃至200℃,优选75℃至175℃,并且更优选90℃至150℃范围内的干燥温度。干燥后,在标准煅烧条件下煅烧载体颗粒,该标准煅烧条件包括250℃至900℃,优选300℃至800℃,并且最优选350℃至600℃范围内的煅烧温度。
载体颗粒应具有允许其用包含氢化金属组分和金属络合剂的浸渍溶液浸渍的表面积和孔体积,随后用本发明的有机添加剂共混物浸渍。载体颗粒可以具有50m2/g至450m2/g,优选75m2/g至400m2/g,并且最优选100m2/g至350m2/g范围内的表面积(通过采用N2的BET方法、ASTM测试方法D3037测定)。
载体颗粒的孔体积应超过0.55cc/g,并且通常在0.5cc/g至1.1cc/g的范围内。更通常是,孔体积在0.6cc/g至1.0cc/g,最通常是0.7至0.9cc/g的范围内。
本文提及的载体颗粒的孔径分布和孔体积是通过压汞法、ASTM测试方法D 4284测定的性质。载体颗粒的孔径分布的测量是通过任何合适的测量仪器,使用140°的接触角和在25℃下474dyne/cm的汞表面张力进行的。
为了提供本发明的金属浸渍的颗粒,用金属浸渍溶液浸渍载体颗粒。浸渍溶液包含至少一种氢化金属组分和金属络合剂。用一定量的一种或多种氢化金属组分浸渍载体颗粒,以在最终催化剂中提供具有有效催化剂所需浓度范围内的金属含量。金属浸渍溶液中金属络合剂的浓度应在本发明的有机添加剂共混物浸渍后提供具有增强的催化特性的最终催化剂。
使用一种或多种含有至少一种金属盐的水溶液,在一个或多个浸渍步骤中用至少一种金属组分浸渍载体颗粒,其中金属盐溶液的金属化合物是活性金属或活性金属前驱体。金属元素是选自IUPAC元素周期表的第6族(例如,铬(Cr)、钼(Mo)和钨(W))和IUPAC元素周期表的第9和10族(例如,钴(Co)和镍(Ni))的那些。磷(P)也是所需的金属组分。
对于第9族和第10族金属,用于制备浸渍溶液的金属盐包括第9或10族金属的乙酸盐、甲酸盐、柠檬酸盐、氧化物、氢氧化物、碳酸盐、硝酸盐、硫酸盐及其两种或更多种。优选的金属盐是金属硝酸盐,例如镍或钴的硝酸盐,或两者。对于第6族金属,金属盐包括第6族金属氧化物或硫化物。优选含有第6族金属和铵离子的盐,例如七钼酸铵和二钼酸铵。
考虑到浸渍水溶液的载体颗粒的孔体积,选择金属浸渍溶液中金属化合物的浓度以在本发明的最终组合物中提供期望的金属含量。本发明最终组合物中的金属浓度如本文所述。通常,浸渍溶液中金属化合物的浓度在0.01至100摩尔金属/升溶液的范围内。
选择金属浸渍溶液中金属络合剂的浓度以提供与其金属组分的足够部分的反应,以在用有机添加剂共混物浸渍载体颗粒后产生具有增强的催化特性的最终催化剂组合物。金属浸渍溶液中的金属络合剂(也称为螯合剂)的量应在金属浸渍溶液的总重量的0.5重量%(wt.%)至15重量%的范围内。它更具体地在金属浸渍溶液的总重量的1重量%至13重量%,并且最具体地2重量%至12重量%的范围内。
已经发现,使用如本文所述的本发明的螯合剂与用本发明的有机添加剂共混物浸渍干燥的金属浸渍的颗粒或干燥颗粒组合具有协同效应。本发明的螯合剂理想地是糖醇或含有至少两个羧基部分的化合物或这些化合物的组合。
优选糖醇选自由每分子具有4至7个碳原子的糖醇组成的组。这些糖醇的实例包括赤藓糖醇(C4)、苏糖醇(C4)、阿糖醇(C5)、木糖醇(C5)、核糖醇(C5)、甘露醇(C6)、山梨糖醇(C6)、半乳糖醇(C6)、岩藻糖醇(C6)、艾杜糖醇(C6)、肌醇(C6)和庚七醇(C7)。更优选的糖醇是每分子具有5或6个碳原子的那些。其中,这些更优选的糖醇是木糖醇和山梨糖醇。
作为本发明合适螯合剂的含有两个或更多个羧基官能团的化合物包括二羧酸化合物和三羧酸化合物。二羧酸化合物可以选自每分子具有4至6个碳原子的化合物。三羧酸化合物可以选自具有5至7个碳原子的化合物。优选的二羧酸化合物是苹果酸(C4H6O5)。优选的三羧酸化合物是柠檬酸(C6H8O7)。
螯合剂的量相对于金属浸渍溶液中含有的金属组分的量是重要的,因为需要形成金属配位络合物以提供具有改进特性的最终催化剂组合物。基于螯合剂的总重量/作为元素的金属总重量的比率,例如镍和钼的总重量,或钴和钼的总重量、或钴、镍和钼的总重量,螯合剂的浓度相对于金属浸渍溶液中的总金属浓度应在0.01:1至20:1的范围内。
期望金属浸渍溶液中螯合剂与总金属组分的重量比为至少0.025:1,并且更期望金属浸渍溶液中螯合剂与总金属组分的重量比为至少0.05:1、或至少0.1:1。金属浸渍溶液中螯合剂与总金属组分的重量比的期望上限是小于15:1,更期望的上限是小于10:1。
金属浸渍的载体颗粒中金属的量可以取决于本发明的最终组合物的应用。一般地,对于加氢处理应用,第9和10族金属组分(即钴或镍)可以以在0.5重量%至20重量%,优选1重量%至15重量%,并且最优选2重量%至12重量%范围内的量存在于载体颗粒中以提供其中掺入有金属组分的金属浸渍的载体颗粒。这些重量百分比值是按干燥金属浸渍的载体颗粒和元素形式的金属组分的重量计,而不管其在组合物中的实际形式,例如氧化物形式或硫化物形式。
第6族金属组分(即钼或钨),优选钼,以在5重量%至50重量%,优选8重量%至40重量%,并且最优选12重量%至30重量%范围内的量掺入载体颗粒中。这些重量百分比值是按干燥金属浸渍的载体颗粒和元素形式的金属组分的重量计,而不管其在组合物中的实际形式,例如氧化物形式或硫化物形式。
在制备或制造本发明的催化剂组合物的创造性方法中,金属浸渍溶液可以是包含至少一种如上所述的具有氢化功能的氢化金属组分和金属络合剂的水溶液。金属浸渍溶液的至少一种氢化金属组分可以包括例如选自由镍、钴、钼、钨及其两种或更多种的任何组合组成的组中的金属,并且掺入载体颗粒中,从而提供金属浸渍的载体颗粒。
可以通过本领域技术人员已知的任何合适的手段或方法将金属浸渍溶液掺入载体颗粒中。此类方法可以包括通过初始润湿的标准浸渍或甚至用比在干浸渍或初始润湿中使用的过量的金属浸渍溶液浸泡载体颗粒。
然而,不管用于将金属浸渍溶液掺入到载体颗粒的实际手段或方法如何,所得金属浸渍的载体颗粒的孔都用金属浸渍溶液填充。因此,孔不能保留或填充额外体积的液体或其它材料,例如本发明的有机添加剂共混物。
因此,掺入金属的载体颗粒经历干燥步骤,通过该干燥步骤,至少一部分挥发物含量被从金属浸渍的载体颗粒驱除,但将金属留在载体颗粒的表面上。提供了具有可用孔体积的干燥颗粒,其可以用本发明的有机添加剂共混物填充。因此,干燥颗粒是已经用金属浸渍溶液浸渍的载体颗粒,其提供金属浸渍的载体颗粒。然后干燥金属浸渍的载体颗粒,得到干燥颗粒。
然后在包括低于煅烧温度的干燥温度的干燥条件下干燥金属浸渍的载体颗粒。这确实是本发明方法的重要特征,即在不超过煅烧温度的干燥温度下干燥金属浸渍的载体颗粒。
然后干燥温度不应超过400℃,并且优选地,金属浸渍的载体颗粒干燥时的干燥温度不超过300℃,并且最优选地,干燥温度不超过250℃。应当理解,该干燥步骤一般在比上述温度低的温度下进行。通常,干燥温度将在60℃至150℃范围内的温度下进行。该干燥步骤提供了可以用本发明的有机添加剂共混物填充的干燥颗粒。
优选以提供在期望范围内挥发物含量的所得干燥颗粒的方式控制金属浸渍的载体颗粒的干燥。应控制干燥颗粒的挥发物含量,使其不超过20重量%LOI。优选干燥颗粒的LOI在1重量%至20重量%LOI,并且最优选3重量%至15重量%LOI的范围内。
LOI或烧失量定义为材料在482℃的温度下暴露于空气2小时后的重量损失百分比。LOI可用下式表示:(暴露前的样品重量减去暴露后的样品重量)乘以100并除以(暴露前的样品重量)。
将本发明的加氢处理催化剂的有机添加剂共混物组分浸渍到通过干燥金属浸渍的载体颗粒提供的干燥颗粒的孔的可用孔体积中。这是通过将有机添加剂共混物掺入干燥颗粒中以通过应用任何合适的方法或手段以用有机添加剂共混物浸渍干燥颗粒以提供添加剂浸渍的干燥颗粒来完成。
用有机添加剂共混物浸渍干燥颗粒的优选方法可以是任何标准的已知的孔填充方法,由此通过利用毛细管作用将液体吸入干燥颗粒的孔中来填充孔体积。用有机添加剂共混物填充的干燥颗粒的孔体积的百分比在干燥颗粒的可用孔体积的25%至100%的范围内。优选地,干燥颗粒的可用孔体积的至少50%填充有有机共混物,并且更优选地,至少70%填充有有机添加剂共混物。优选用有机添加剂共混物填充干燥颗粒的至多100%的可用孔体积,但添加剂浸渍的干燥颗粒的孔可以具有用有机添加剂共混物填充的至多95%或甚至至多90%的可用孔体积。用有机添加剂共混物填充干燥颗粒提供了最终组合物,其在活化时表现出优异的加氢处理催化特性。
使用用氢化金属和金属络合剂两者浸渍的、进一步用有机添加剂共混物浸渍的载体颗粒的组合特征提供了具有增强的加氢处理活性的本发明组合物。本发明催化剂的有机添加剂共混物组分包含乙酸盐化合物和不饱和脂肪胺。有机添加剂共混物应包括其各个组分,不饱和脂肪胺化合物与乙酸盐化合物的重量比在0.1:1至10:1的范围内。优选有机添加剂共混物中不饱和脂肪胺与乙酸盐具有在0.2:1至8:1,并且更优选0.3:1至2:1范围内的重量比。最优选地,不饱和脂肪胺与乙酸盐的重量比在30/70至15/10的范围内。
用于制备本发明的催化剂组合物的有机添加剂共混物的乙酸盐化合物组分可以是任何合适的具有乙酸盐部分并且有助于增强本发明最终催化剂组合物的催化特性的分子化合物。此类乙酸盐化合物在催化剂制备的温度条件下(通常在0℃至40℃的温度范围内)必须是液体并且可与本发明催化剂组合物的有机添加剂共混物的不饱和脂肪胺组分混溶。
有机添加剂共混物的乙酸盐化合物可以选自由乙酸烷基酯、乙酸乙氧基烷基酯、乙酸甲氧基烷基酯和乙酸烷氧基烷氧基烷基酯组成的组中的合适的乙酸盐化合物。
从中选择乙酸盐化合物的乙酸烷基酯可以由下式表示:CH3C(O)ORn,其中R表示烷基并且n=1至20的整数,表示R中的碳原子数。
从中选择乙酸盐化合物的乙酸乙氧基烷基酯可以由下式表示:CH3CH2ORnO(O)CCH3,其中R表示在n=1至10的整数范围内的碳数。
从中选择乙酸盐化合物的乙酸甲氧基烷基酯可以由下式表示:CH3ORnO(O)CCH3,其中R表示在n=1至10的整数范围内的碳数。
从中选择乙酸盐化合物的乙酸烷氧基烷氧基烷基酯可以由下式表示:R1OR2OR3O(O)CCH3,其中R1表示1至4范围内的碳数,R2表示1至4范围内的碳数,R3表示1至4范围内的碳数,R4表示1至4范围内的碳数。
用作有机添加剂共混物组分的最优选的乙酸盐化合物是乙酸丁基卡必醇酯(乙酸丁氧基乙氧基乙酯)。
用于制备本发明的有机添加剂共混物的不饱和脂肪胺化合物组分可以是有助于本发明的最终催化剂组合物的增强特性的任何合适的分子化合物。合适的不饱和脂肪胺是可与用于制备有机添加剂共混物的乙酸盐化合物混溶的那些。
不饱和脂肪胺化合物可以选自由每分子具有8至22个碳原子的不饱和脂肪胺组成的组中的合适的不饱和脂肪胺化合物。有机添加剂共混物的不饱和脂肪胺包括连接到8个或更多个碳原子长至22个碳原子的烃链的胺部分,其中至少一个碳-碳双键在烃链内。
用作有机添加剂共混物的组分的最优选的不饱和胺化合物是油胺(C18H35NH2,在第九个(9th)碳上具有双键)。
用有机添加剂共混物浸渍干燥颗粒提供了包含载体颗粒、至少一种氢化金属和有机添加剂共混物的组合物。如上所述,浸渍到干燥颗粒中的有机添加剂共混物的量提供了干燥颗粒的孔体积填充,其中有机添加剂共混物占可用孔体积的25%至100%。干燥颗粒的孔体积可通过本领域技术人员已知的任何合适的方法或手段测量。一种合适的方法是通过水滴定或通过用水填充干燥颗粒并且测量干燥颗粒和填充水的颗粒之间的重量差以测定吸附水的体积来测量干燥颗粒的水孔体积。
最终的或有机添加剂共混物浸渍的组合物可以在非原位或原位用氢和用硫化合物处理,并且实际上,本发明的有益特征之一是它允许将未硫化的组合物运输和递送到反应器中,在该反应器中可通过氢处理步骤和随后的硫化步骤将其原位活化。该组合物可首先进行氢处理,然后用硫化合物处理。
氢处理包括将组合物暴露于温度高达250℃的含氢气体环境中。优选地,浸渍的组合物在100℃至225℃范围内的氢处理温度下暴露于氢气,并且最优选地,氢处理温度在125℃至200℃范围内。
在氢处理步骤中使用的气态气氛的氢分压通常可以在1巴至70巴,优选1.5巴至55巴,最优选2巴至35巴的范围内。浸渍的组合物在上述温度和压力条件下与气体环境接触0.1小时至100小时范围内的氢处理时间,并且优选氢处理时间在1小时至50小时,并且最优选2小时至30小时的范围内。
用氢处理后的组合物的硫化可使用本领域技术人员已知的任何常规方法进行。因此,经氢处理的组合物可在本发明的接触条件下与含硫化合物接触,该含硫化合物可为硫化氢或可分解为硫化氢的化合物。这种可分解化合物的实例包括硫醇,CS2,噻吩,二甲基硫醚(DMS)和二甲基二硫醚(DMDS)。此外,优选地,通过在合适的硫化处理条件下使氢处理的组合物与含有一定浓度的硫化合物的烃原料接触来实现硫化。烃原料的硫化合物可以是有机硫化合物,特别是通常包含在通过加氢脱硫方法加工的石油馏出物中的有机硫化合物。
合适的硫化处理条件是提供将经氢处理的组合物的活性金属组分转化为其硫化形式的那些条件。通常,经氢处理的组合物与硫化合物接触的硫化温度在150℃至450℃,优选175℃至425℃,并且最优选200℃至400℃的范围内。
当使用烃原料硫化经氢处理的组合物时,硫化条件可与进行加氢处理的工艺条件相同。经氢处理的组合物硫化时的硫化压力一般可在1巴至70巴,优选1.5巴至55巴,并且最优选2巴至35巴的范围内。
应认识到,本发明的最终或添加剂浸渍的组合物,在其用氢和硫处理后,是用于烃原料加氢处理的高效催化剂。该催化剂在涉及烃原料的加氢脱硫(HDS)或加氢脱氮(HDN)或两者的应用中特别有用,并且尤其是,已经发现它是用于瓦斯油原料的HDS和HDN中的优异催化剂。
本发明的组合物也可以用于制备硫浓度小于15ppmw,优选小于10ppmw,并且最优选小于8ppmw的超低硫馏出物产物。而且,如所指出的,本发明的组合物可以用于处理较重质烃原料,例如瓦斯油。在瓦斯油的加氢处理中,经处理的产物的氮含量通常小于1000ppmw,或小于800ppmw,并且甚至小于600ppmw。经处理的产物的硫含量通常小于500ppmw,或小于400ppmw,并且甚至小于300ppmw。
在加氢处理应用中,该组合物优选用于延迟进料引入程序或以其它方式用氢和硫处理,如上所述。在该程序中,组合物在合适的加氢脱硫条件下与通常具有硫浓度的烃原料接触。这提供了组合物的硫化。
可以使用本发明的组合物加工的一种烃原料是在大气压下具有在140℃至410℃范围内的沸腾温度的石油中间馏出物馏分。这些温度接近中间馏出物的初始和沸腾温度。打算包括在中间馏分油含义内的炼油厂物流的实例包括在所述沸程内沸腾的直馏馏分燃料,例如煤油,喷气燃料,轻质柴油,加热油,重质柴油和裂化馏分,例如FCC循环油,焦化瓦斯油和加氢裂化器馏分。优选馏出物原料是在约140℃至400℃的柴油沸程内沸腾的中间馏出物。
瓦斯油也可以使用本发明的组合物进行加工。这些瓦斯油可以包括常压瓦斯油、轻质真空瓦斯油和重真空瓦斯油。进一步预期的是,本发明的组合物也可以用于渣油原料的处理。
中间馏分油原料的硫浓度可以是高浓度,例如,基于元素硫的重量和包括硫化合物在内的馏分油原料的总重量,在馏分油原料的至多约2重量%的范围内。然而,馏出物原料通常具有0.01重量%(100ppmw)至1.8重量%(18,000)范围的硫浓度。但是,更典型地,硫浓度为0.1wt%(1000ppmw)-1.6wt%(16,000ppmw),和最典型地0.18wt%(1800ppmw)-1.1wt%(11,000ppmw)。应理解,本文提及的馏出物原料的硫含量是指通常在馏出物原料或加氢脱硫馏出物产物中发现的那些化合物,并且是含有硫原子且通常包括有机硫化合物的化合物。
本发明的组合物可以用作任何合适的反应器***的一部分,所述反应器***提供使其或其衍生物与馏出物原料在合适的加氢脱硫条件下接触,该条件可以包括氢气的存在和升高的总压力和温度。这种合适的反应***可包括固定催化剂床***,沸腾催化剂床***,浆化催化剂***和流化催化剂床***。优选的反应器***包括包含在反应器容器内的本发明催化剂的固定床,所述反应器容器配备有用于将馏出物原料引入反应器容器的反应器进料入口装置如进料喷嘴,和用于从反应器容器取出反应器流出物或处理过的烃产物或超低硫馏出物产物的反应器流出物出口装置如流出物出口喷嘴。
加氢处理工艺一般在689.5kPa(100psig)至13,789kPa(2000psig),优选1896kPa(275psig)至10,342kPa(1500psig),并且更优选2068.5kPa(300psig)至8619kPa(1250psig)范围内的加氢处理反应压力下操作。
加氢处理反应温度一般在200℃(392℉)至420℃(788℉),优选260℃(500℉)至400℃(752℉),并且最优选320℃(608℉)至380℃(716℉)范围内。
应认识到,使用本发明组合物的一个意想不到的特征是,它表现出比某些其它替代的催化剂组合物更高的催化活性,并且因此,对于给定量的脱硫或脱氮或两者,它一般提供相对较低的所需工艺温度。
将烃原料加入本发明工艺的反应区的流速一般提供0.01hr-1至10hr-1范围内的液时空速(LHSV)。如本文所用,术语“液时空速”是指以每小时体积计的将烃原料加入本发明工艺的反应区的速率除以烃原料加入的反应区中所含催化剂体积的数值比。优选LHSV在0.05hr-1至5hr-1,更优选0.1hr-1至3hr-1,并且最优选0.2hr-1至2hr-1范围内。
优选将氢气与烃原料一起加入本发明工艺的反应区。在这种情况下,氢气有时被称为氢气处理气体。氢气处理气体速率是相对于加入反应区的烃原料量的氢气量,一般在至多1781m3/m3(10,000SCF/bbl)范围内。优选处理气体速率在89m3/m3(500SCF/bbl)至1781m3/m3(10,000SCF/bbl),更优选178m3/m3(1,000SCF/bbl)至1602m3/m3(9,000SCF/bbl),并且最优选356m3/m3(2,000SCF/bbl)至1425m3/m3(8,000SCF/bbl)范围内。
相对于烃原料,由本发明工艺产生的加氢处理产物具有低或降低的硫和氮浓度。
Claims (16)
1.一种制备加氢处理催化剂的方法,所述方法包含:提供无机氧化物载体颗粒;用包含至少一种氢化金属组分和金属络合剂的金属浸渍溶液浸渍所述无机氧化物载体颗粒,以提供金属浸渍的颗粒;干燥所述金属浸渍的颗粒以提供干燥颗粒;以及用包含乙酸盐化合物和不饱和脂肪胺化合物的有机添加剂共混物浸渍所述干燥颗粒。
2.根据权利要求1所述的方法,其中所述有机添加剂共混物的不饱和脂肪胺化合物与乙酸盐化合物的重量比在30/70至90/10范围内。
3.根据权利要求1所述的方法,其中所述金属浸渍溶液包括选自由糖醇和具有至少2个羧基部分的化合物组成的组中的所述金属络合剂。
4.根据权利要求3所述的方法,其中所述糖醇选自由每分子具有4至7个碳原子的糖醇组成的组。
5.根据权利要求4所述的方法,其中所述糖醇包括木糖醇和山梨糖醇,并且具有至少2个羧基部分的所述化合物包括柠檬酸和苹果酸。
6.根据权利要求5所述的方法,其中基于元素金属的总质量/所述金属络合剂的总质量,所述金属浸渍溶液的所述金属络合剂与所述氢化金属组分的重量比在0.1至0.9范围内。
7.根据权利要求2所述的方法,其中所述乙酸盐化合物选自由乙酸烷基酯、乙酸乙氧基烷基酯和乙酸甲氧基烷基酯组成的组。
8.根据权利要求7所述的方法,其中所述不饱和脂肪胺化合物选自由每分子含有8至22个原子的不饱和脂肪胺化合物组成的组。
9.根据权利要求3所述的方法,其中所述糖醇包括木糖醇和山梨糖醇,并且具有至少2个羧基部分的所述化合物包括柠檬酸和苹果酸。
10.根据权利要求1所述的方法,其中所述乙酸盐化合物是乙酸丁基卡必醇酯,并且所述不饱和脂肪胺化合物包括油胺;其中所述干燥步骤提供具有在15至35重量%范围内的LOI的所述干燥颗粒;其中浸渍到所述干燥颗粒中的所述有机添加剂共混物的量填充其可用孔体积的至少90体积%;其中浸渍到所述干燥颗粒中的所述有机添加剂共混物与所述金属浸渍的颗粒的重量比,以干重计在1/8至1/2的范围内;并且其中用至少一种氢化金属的所述金属浸渍溶液浸渍所述无机载体颗粒,所述金属浸渍溶液包括钼和镍或钴,并且其中浸渍到所述无机氧化物载体颗粒中的镍或钴的量在所述加氢处理催化剂中提供0.5至20重量%范围内的镍或钴的量,和5至50重量%范围内的钼的量,其中重量%基于作为元素的金属,而不管其实际形式,和干燥的无机载体颗粒,并且不包括所述有机添加剂共混物。
11.一种加氢处理催化剂,其包含:无机氧化物载体颗粒;金属络合剂、钼和钴或镍中的一者或两者的混合物;以及浸渍的有机添加剂共混物,其包含乙酸盐化合物和不饱和脂肪胺。
12.根据权利要求11所述的加氢处理催化剂,其中所述有机添加剂共混物的不饱和脂肪胺化合物与乙酸盐化合物的重量比在30/70至90/10范围内;并且其中所述加氢处理催化剂包含浸渍到所述无机氧化物载体颗粒中的所述有机添加剂共混物与所述无机氧化物载体颗粒的重量比,以干重计,在1/8至1/2范围内。
13.根据权利要求12所述的加氢处理催化剂,其中所述乙酸盐化合物选自由乙酸烷基酯、乙酸乙氧基烷基酯和乙酸甲氧基烷基酯组成的组;并且其中所述不饱和脂肪胺化合物选自由每分子含有8至22个碳原子的不饱和脂肪胺化合物组成的组。
14.根据权利要求13所述的加氢处理催化剂,其中所述乙酸盐化合物是乙酸丁基卡必醇酯,并且所述不饱和脂肪胺化合物是油胺。
15.一种加氢过程,其包含:在加氢处理条件下使烃原料与权利要求11至14中任一项所述的催化剂接触。
16.一种通过权利要求1至10中任一项所述的方法制备的催化剂。
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