CN104114275B - 制备加氢裂化催化剂的方法 - Google Patents
制备加氢裂化催化剂的方法 Download PDFInfo
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- CN104114275B CN104114275B CN201280069622.9A CN201280069622A CN104114275B CN 104114275 B CN104114275 B CN 104114275B CN 201280069622 A CN201280069622 A CN 201280069622A CN 104114275 B CN104114275 B CN 104114275B
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 15
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
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- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- 150000002739 metals Chemical class 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
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- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical class CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
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- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
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- 238000002441 X-ray diffraction Methods 0.000 description 1
- YDHWWBZFRZWVHO-UHFFFAOYSA-H [oxido-[oxido(phosphonatooxy)phosphoryl]oxyphosphoryl] phosphate Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O YDHWWBZFRZWVHO-UHFFFAOYSA-H 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
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- BYHYXWHABSWXTJ-UHFFFAOYSA-N aluminum oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4].[O-2].[Al+3] BYHYXWHABSWXTJ-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
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- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
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- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
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- 238000002459 porosimetry Methods 0.000 description 1
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- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
制备硫化的加氢裂化催化剂的方法,其包括下列步骤:(a)用一种或多种VIB族金属组分、一种或多种VIII族金属组分和C3‑C12多羟基化合物处理无定形的二氧化硅‑氧化铝载体,(b)在最高200℃的温度下干燥所述处理的催化剂载体以形成浸渍的载体,和(c)硫化所述浸渍的载体以获得硫化的催化剂。
Description
技术领域
本发明涉及一种制备加氢裂化催化剂的方法,以及使用所述催化剂的加氢裂化方法。
发明背景
包括在催化剂的存在下用氢处理原油和其他石油进料的方法是已知的。一种这样的方法是加氢裂化,其中在催化剂的存在下,重质馏分烃在氢气压力下转换成较低分子量的产物。加氢裂化被用于石油工业以制备范围广泛的材料,范围从C3/C4的生产到润滑油的制造。
加氢裂化和加氢处理的不同之处在于,加氢处理旨在去除含硫化合物且使碳-碳键断裂最小,而加氢裂化依赖于重质油分子的分解。在商业实践中,加氢裂化和加氢处理催化剂之间有明显的区别,因为加氢裂化催化剂被污染物失活,所述污染物是加氢处理催化剂的主要目标。在目标上的差异使得加氢处理和加氢裂化催化剂在组成和制造方法上有所不同。
加氢裂化可以作为单阶段或多阶段方法进行操作。多阶段加氢裂化通常包括第一阶段,其主要是加氢处理阶段,其中杂质和不饱和化合物在具有高度加氢功能的第一催化剂的存在下被加氢,和第二阶段,其中大部分裂化发生在具有强的裂化功能的第二催化剂的存在下。在单阶段加氢裂化中,处理和裂化步骤发生在一个反应器中,并且可以使用单一催化剂或使用若干顺序的催化剂床来执行,所述催化剂床通常是在一个反应器中串联的两个床,即作为堆叠床。同样,在多阶段加氢裂化中,每个阶段可以使用单一催化剂或多种催化剂(通常为两种)的堆叠床。
加氢裂化中采用的催化剂通常由在其上沉积有催化活性金属的载体材料制得,所述催化活性金属选自镍、钴、钼、钨、钯和铂。
加氢裂化催化剂的活性越高,转化就越高效。特别地,活性更大的催化剂可以在比活性较小的催化剂更低的温度下操作而实现相同程度的转化。这是有利的,因为较低的操作温度延长催化剂寿命并且降低操作成本。因此,一直存在改善催化剂活性的需要。
有时在催化剂制造过程中加入络合剂,以便稳定含金属溶液和/或抑制沉积在载体上的活性金属聚结。
若干种有机添加剂被描述为对基于氧化铝的加氢处理催化剂有利。实例为烃油和极性添加剂,例如二甲基甲酰胺(US2010/236988)、不饱和二元醇(US2008/087577)、邻苯二甲酸酯(US2007/037695)、有机含氮化合物(US2007/155618)、羟基羧酸(EP 482817)或糖衍生物(WO 2004/018097)。
发明概述
本发明现在提供一种制备硫化的加氢裂化催化剂的方法,其包括下列步骤:
(a)用一种或多种VIB族金属组分、一种或多种VIII族金属组分和C3-C12多羟基化合物处理无定形的二氧化硅-氧化铝载体,
(b)在最高200℃的温度下干燥处理后的催化剂载体以形成浸渍的载体,和
(c)硫化所述浸渍的载体以获得硫化的催化剂。
发明详述
本发明的催化剂采用无定形的二氧化硅-氧化铝材料作为载体。术语“无定形”是指在载体材料中缺少晶体结构,如X射线衍射所限定的,但可能存在一些短程有序。
适用于制备催化剂载体的无定形二氧化硅-氧化铝是可商购的。或者,所述二氧化硅-氧化铝可以通过如本领域熟知的共凝胶方法或接枝方法制备。所述无定形二氧化硅-氧化铝优选以基于载体单独计算(即基于总载体)25至95重量%范围内的量含有二氧化硅。更优选地,在载体中的二氧化硅的量大于35重量%,最优选至少40重量%。一种非常适用于制备所述催化剂载体的无定形二氧化硅-氧化铝产品包含45重量%的二氧化硅和55重量%的氧化铝,并且是可商购的(来自Criterion Catalysts and Technologies,美国)。
任选地,所述载体中可以包含沸石。所述沸石可以是提议用于加氢裂化催化剂中的任何沸石。然而,在使用八面沸石、特别是沸石Y时发现具有良好的结果。所述沸石Y有用地是具有在24.10至范围内的单胞尺寸和在4至100范围内的本体或总体二氧化硅-氧化铝比(SAR)的稳定化的沸石Y。优选地,所述沸石Y具有的SAR范围是从20到100,尤其是从25到90。这样的沸石Y材料是容易地例如从Zeolyst International商购的。
在所述催化剂中可以存在不止一种沸石,并且这种额外的沸石可以是被发现展现出有用的加氢裂化活性的任何合适的沸石,尤其当少量用于加氢裂化催化剂中时。合适的额外的沸石可以选自β沸石、ZSM-5沸石、和具有不同于本发明的催化剂中首要使用的单胞尺寸和/或SAR的沸石Y。
如果存在,本发明催化剂中的总沸石量的范围有用地是基于载体总重量的1至40重量%,优选的范围是从1至20,尤其是1至10重量%。
所述方法进一步包括用一种或多种VIII族金属组分和一种或多种VIB族金属组分处理载体,所述金属在CRC Handbook of Chemistry and Physics,68th Edition,1985,CRC Press,INC中公布的周期表中给出。
优选地,VIII族金属选自镍、钴及其混合物;而VIB族金属优选选自钼和钨及其混合物。在优选的实施方案中,VIII族金属是镍,并且VIB族金属是钼和/或钨,优选钼。
VIII族金属和VIB族金属在催化剂中的量可以根据金属类型和所述催化剂的预期目的而变化,然而,基于催化剂的总重量,VIII族金属的量将优选在0.5至10重量%的范围内,而VIB族金属的量将优选在3至30重量%的范围内,所述量作为金属进行测定。根据本发明所述的优选催化剂包含镍的量的范围是1至6重量%,更优选3至6重量%;和钼的量的范围是6至19重量%,优选10至16重量%,或钨的量的范围是10至25重量%,优选15至22重量%。
加氢裂化催化剂的制造进一步包括用C3-C12多羟基化合物进行的处理。发现使用C3-C12多羟基化合物提供了显示增强的加氢裂化活性的更稳定的催化剂,尤其是在第一阶段加氢裂化底床的应用中。不受理论的约束,据信C3-C12多羟基化合物的加入有利于在干燥时形成金属溶解(并因此分散)的玻璃状浸渍态。这样处理的催化剂载体进行干燥和硫化,而不进行间歇性的煅烧。在这些具体的情况下,认为它们导致硫化状态金属的分散增强。
所述C3-C12多羟基化合物优选是糖、糖醇和/或糖酸。更优选地,它是C6或C12糖、糖醇和/或糖酸。尤其优选的化合物是蔗糖和/或葡萄糖酸。
所述C3-C12多羟基化合物以对应于基于催化剂总重量的3-30重量%,优选5-20重量%的量存在于干燥且处理过的催化剂中。
所述催化剂中可以包括磷酸。可使用偏磷酸、焦磷酸、正磷酸、三磷酸和四磷酸中的任何一个作为磷酸。也可以使用所述酸的可溶性盐如磷酸镍。在干燥且处理过的催化剂中的量通常是0.1-10重量%。
氟化合物也可以包括在所述催化剂中以提高催化剂的活性,如US3,6713,108中所描述的那样。这可以通过在浸渍溶液中包括水溶性化合物,如氢氟酸、三氟乙酸或六氟磷酸,或其适合的盐来实现。在催化剂中的氟水平优选的范围是0.1至6.0重量%。氟在操作过程中逐渐从催化剂中损失。其水平可以通过向进料中加入烃溶性氟化合物来维持,如US3,6713,108中所描述的那样。合适的氟化合物的实例包括1,1-二氟乙烷或邻氟甲苯。
催化剂的总表面积优选大于100m2/g和更优选在200~300m2/g范围内,通过根据ASTM测试D3663-03的BET法测定。总孔隙体积优选大于0.4ml/g。所需的最小表面积决定了可应用的最大孔隙体积。优选5至40体积%范围内的总孔隙体积以直径大于的孔隙存在。孔隙体积使用通过压汞法测定催化剂的孔隙体积分布的标准测试方法(StandardTest Method for Determining Pore Volume Distribution of Catalysts by MercuryIntrusion Porosimetry)ASTM D 4284-88来测定。
本文描述的催化剂可以通过本领域已知的任何合适的制备技术来制备。优选地,使用单步浸渍方法。包含无定形的二氧化硅-氧化铝的载体用包含VIII族金属、VIB族金属、和C3-C12多羟基化合物、以及任何其他添加剂(磷酸、氟)的溶液浸渍,并且所生成的催化剂在最高200℃的温度下干燥。
任选地包括沸石的无定形的二氧化硅-氧化铝载体可以通过本领域已知的任何合适的载体制备技术来制备。制备所述载体的优选方法包括研磨无定形二氧化硅-氧化铝、任选的所述沸石和合适的液体的混合物,挤出所述混合物和加热所生成的挤出物。
所述挤出物可以具有本领域已知的任何合适的形式,例如圆柱形、中空圆柱形、多叶形或扭曲多叶形。催化剂颗粒的优选形状是多叶形,例如三叶形。典型地,所述挤出物具有0.5至5mm,优选1至3mm的标称直径。
在挤出后,将挤出物干燥。干燥可以在升高的温度下、优选最高300℃下、更优选最高200℃下进行。干燥的周期通常最长5小时,优选在30分钟至3小时范围内。优选地,然后将所述挤出物在干燥之后在极高温度下、优选在400至1000℃之间进一步加热(煅烧),通常周期最长5小时,优选在30分钟至4小时范围内。
VIII族和VIB族金属可以使用本领域已知的任何合适的方法沉积在载体上,例如通过离子交换、竞争性离子交换或浸渍。当使用浸渍时,这优选与所述C3-C12多羟基化合物、和其他添加剂(如果包括的话)一起进行。当浸渍与所述C3-C12多羟基化合物一起进行时,应该在不超过200℃、优选不超过170℃、更优选不超过120℃的温度下进行干燥。
可替代地,用冷冻干燥法干燥处理过的催化剂载体,所述冷冻干燥法包括冷冻处理的催化剂载体和降低环境压力,以使得冻结的水从固相直接升华至气相。以这种方式制备的催化剂被发现在加氢裂化中尤其有活性,因为所述方法可以在减压下进行和/或得到的产物具有减少的硫和/或氮含量。
将所述加氢裂化催化剂在用于加氢裂化方法之前硫化。所述催化剂可以使用本领域已知的任何技术,例如非原位或原位硫化来方便地硫化。例如,硫化可以通过使所述催化剂接触含硫气体,如氢和硫化氢的混合物、氢和二硫化碳的混合物或氢和硫醇(如丁硫醇)的混合物来进行。可替代地,硫化可以通过使所述催化剂接触氢和含硫烃油,如含硫煤油或蜡油来进行。所述硫还可以通过添加合适的含硫化合物,例如,例如二甲基二硫化物或叔壬基多硫化物而引入所述烃油中。
使用本发明催化剂的加氢裂化方法包括在氢和加氢裂化催化剂的存在下使烃给料加氢裂化。如本领域技术人员将理解的那样,所述加氢裂化方法采用的条件可以变化,然而,通常转化温度优选在250至500℃、更优选300至450℃、和最优选350至450℃的范围内。此外,所述加氢裂化方法中的总压力将优选在5×106帕(50巴)至3×107帕(300巴)、更优选在7.5×106帕(75巴)至2.5×107帕(250巴)、和甚至更优选1×107帕(100巴)至2×107帕(200巴)的范围内;同时氢气分压将优选在2.5×106帕(25巴)至2.5×107帕(250巴)、更优选5×106帕(50巴)至2×107帕(200巴)、和仍然更优选6×106帕(60巴)至1.8×107帕(180巴)的范围内。此外,按照每升催化剂每小时的kg新鲜给料(kg.l-1.h-1)计的给料空速将优选在0.1至10、更优选0.2至8、和甚至更优选0.5至5的范围内;同时总气体速率(气体/进料比)将优选在100至5000Nl/kg,更优选250至2500Nl/kg的范围内。
范围广泛的烃给料可以用于加氢裂化方法中。可以方便地采用的给料的实例包括蜡油、焦化蜡油、减压蜡油、脱沥青油、使用Fischer-Tropsch合成方法制备的馏分(如蜡油和蜡馏分)、常压渣油、催化裂化循环油、热或催化裂化蜡油、和合成原油,任选地源于焦油砂、页岩油、残渣升级方法或生物质。也可以采用各种烃油的组合。给料通常将使得至少50重量%具有高于370℃的沸点。烃给料中的氮或硫含量不是关键的,并且给料可以具有高达5000ppmw(按重量计百万分之一)的氮含量和高达6重量%的硫含量。典型地,氮含量可以在250至2000ppmw的范围内而硫含量在0.2至5重量%的范围内。
由本发明方法制备的催化剂可以用于多阶段加氢裂化中的有利作用,特别是作为多个催化剂床的堆叠中的底床催化剂,其中基于无定形的二氧化硅-氧化铝的催化剂被显示为展现出比基于氧化铝的预处理催化剂更佳且更稳定的加氢脱氮活性和更高的加氢裂化活性。这样的堆叠可以例如由基于氧化铝的催化剂的顶床和基于二氧化硅-氧化铝的催化剂的底床以从1:1到4:1的基于氧化铝的催化剂对基于二氧化硅-氧化铝的催化剂的体积比构成。
本发明的催化剂还可以用于单阶段加氢裂化中的有利作用,其中它在甚至暴露于包含氮和含硫污染物的给料时也给出了良好的转化效率
单阶段加氢裂化的一个应用是产生中间馏分级分。中间馏分级分是具有150至370℃范围内沸点的液体级分,并包括产物如煤油(150至250℃)和蜡油(250至370℃)。对中间馏分产物存在不断增长的需求,并因此也一直需要对于中间馏分展现出强选择性并使气态(C1-C4)物质的形成最小化的加氢裂化方法,即方法的产物含有低量的气态物质和大量的中间馏分。在这一点上,本发明的加氢裂化方法已被证明对于转化重质馏分给料,例如将重质蜡油或脱沥青油转化为中间馏分级分极其具有选择性。
实施例
用于实施例中的无定形的二氧化硅-氧化铝载体是具有0.78ml/g水孔体积的1.3mm三叶形的无定形二氧化硅-氧化铝挤出物。
实施例1
煅烧催化剂的制备(非根据本发明)
将5.55g一水柠檬酸溶于10ml脱矿质水中。加入3.90g碳酸镍(39.80重量%的Ni)并将混合物加热直至得到绿色澄清溶液。随后,加入9.19g偏钨酸铵(70.9重量%的W)并加入脱矿质水,直至生成的澄清溶液的总体积达到16.2ml。然后将该溶液用于浸渍20.8g的无定形二氧化硅-氧化铝载体。然后将催化剂在通风炉中在120℃下干燥2小时,随后在450℃下煅烧2小时。催化剂的载量以基于干重的质量%计,是5.0%的Ni和21.0%的W。(以“A”表示)
实施例2
根据本发明制备的催化剂
将32.63g MoO3、6.52g NiO、60g H2O和12.18g H3PO4(85%)进行合并并煮沸约45分钟直至得到绿色澄清溶液。冷却后,加入25.0g葡萄糖酸溶液(50%的水溶液)以产生带蓝色的深绿色溶液,其经短暂煮沸而导致颜色进一步变为带绿色的深蓝色。所生成的溶液的总质量为105.7g。该溶液的五分之一(21.4g)被稀释至所需要的体积(24.3g,15.6ml)并用于浸渍20.0g的无定形二氧化硅-氧化铝载体。随后将催化剂在真空炉中在70℃下干燥。催化剂的载量以基于干重的质量%计,是3.5%的Ni、15.0%的Mo、2.2%的P,和8.53%的葡萄糖酸。(以“B”表示)
实施例3
根据本发明制备的催化剂
将16.2g MoO3、3.25g NiO、30.0g H2O和5.94g H3PO4(85%)进行合并并煮沸约45分钟,允许一定的水分蒸发,直至得到总质量为46.5g的绿色澄清溶液。将其冷却并分为23.25g的两个等份。在其中一份中加入3.13g蔗糖以产生带蓝色的深绿色溶液,其经短暂煮沸而导致颜色进一步变为深蓝色。该溶液被稀释至所需要的体积(29.0g,19.0ml)并用于浸渍25.0g的无定形二氧化硅-氧化铝载体。然后将催化剂在IPA/CO2浴中冷却并冷冻干燥过夜。催化剂的载量以基于干重的质量%计,是3.5%的Ni、15.0%的Mo、2.2%的P,和8.53%的蔗糖。(以“C”表示)
实施例4
催化剂的测试
在第一阶段加氢裂化模拟测试中,使用具有下表所示性质的重质蜡油给料测试了催化剂“A”-“C”的加氢裂化、加氢脱硫和加氢脱氮活性:
给料性质 | ||
在15/4℃下的密度 | g/ml | 0.9198 |
在70/4℃下的密度 | g/ml | 0.8856 |
在100℃下的动力粘度 | cSt | 6.995 |
碳含量 | 重量% | 85.28 |
氢含量 | 重量% | 12.07 |
硫含量 | 重量% | 2.65 |
总氮含量 | ppmw | 780 |
芳族化合物含量 | 重量% | 15.1 |
最初沸点 | ℃ | 281 |
10重量%沸点 | ℃ | 369 |
50重量%沸点 | ℃ | 441 |
90重量%沸点 | ℃ | 516 |
最终沸点 | ℃ | 580 |
在低于370℃下沸腾的级分 | 重量% | 10.3 |
在高于540℃下沸腾的级分 | 重量% | 3.6 |
本测试在负载有催化剂床的单程微流设备中进行,所述催化剂床包含15mlCriterion DN-3300催化剂(1.3mm三叶形,用等体积的0.05mm碳化硅颗粒稀释)的顶床,和5ml待测试的催化剂(同样用等体积的0.05mm碳化硅颗粒稀释)的底床。
在本测试之前,使用蜡油进料与氢和硫化氢的混合物在112巴的压力和从环境温度(22℃)上升至345℃的最终温度的温度分布下将催化剂进行液相预硫化。
为了测定加氢裂化,加氢脱硫和加氢脱氮活性,使重质蜡油给料在1.36kg重质蜡油/升催化剂/小时(kg/l/h)的重时空速、900Nl/kg的氢气/重质蜡油比、和112巴(11.2MPa)的总压力下的单程操作中与所述催化剂床接触。根据具有370℃或更高沸点的给料组分向在低于370℃下沸腾的物质的转化,通过分析在380℃催化剂床温度下和运行620小时后获得的产物,对加氢裂化性能进行评估。
通过分别测定残余的硫和氮的水平,对同一产物进行加氢脱硫和加氢脱氮性能的评估。从下表显示的结果中,可以看出催化剂“B”和“C”的加氢裂化、加氢脱硫和加氢脱氮活性显著更大。
催化剂 | A | B | C |
370℃+的转化(基于进料的重量%,净重) | 17.84 | 19.74 | 19.32 |
液体产物中的硫(ppmw) | 322 | 241 | 298 |
液体产物中的氮(ppmw) | 25 | 14 | 16 |
实施例5
非根据本发明制备的催化剂
将16.55g MoO3、3.27g NiO、25g H2O和6.02g H3PO4(85%)进行合并并煮沸约45分钟,直至得到绿色澄清溶液。冷却后,溶液的总质量测定为40.25g。将一份12.08g的该溶液稀释至所需要的体积(13.2ml)并用于浸渍15.0g的无定形二氧化硅-氧化铝载体。随后将催化剂在真空炉中在70℃下干燥。催化剂的载量以基于干重的质量%计,是3.5%的Ni、15.0%的Mo和2.2%的P。(以“D”表示)
实施例6
二苯并噻吩的加氢脱硫性能测试(DBT测试)
二苯并噻吩的加氢脱硫实验在设置有六个反应器的纳米流反应器中以滴流进行。每个反应器都装载有385mg的压碎且筛分过的催化剂颗粒(30-80目),所述颗粒用惰性物质稀释以确保适当的流体动力学行为。在测试前,用十六烷和5.4重量%的二叔紫罗酮基五硫化物的混合物对催化剂进行原位预硫化,所述混合物在250ml/g进料的流速的H2下以0.75ml/min滴流式进料,以20℃/h加热至280℃然后维持该温度5h,随后以20℃/h加热至340℃并维持该温度2h。本测试的进料是5重量%的二苯并噻吩(DBT)、1.75重量%的十二烷和剩余部分十六烷的混合物,在250ml/g进料的流速的H2下以0.75ml/min滴流式进料。
结果概括于下表。
通过假定DBT转化具有一级反应动力学,计算了DBT转化的反应常数(kDBT)。从结果中可明了,催化剂B在DBT加氢脱硫中比对比催化剂A和D二者的活性显著更大。
Claims (10)
1.制备硫化的加氢裂化催化剂的方法,其包括下列步骤:
(a)用包含一种或多种VIB族金属组分、一种或多种VIII族金属组分和C3-C12多羟基化合物的溶液单步浸渍无定形的二氧化硅-氧化铝载体,
(b)在最高200℃的温度下干燥所述处理的催化剂载体以形成浸渍的载体,和
(c)硫化所述浸渍的载体以获得硫化的催化剂,
其中所述C3-C12多羟基化合物是糖、糖醇和/或糖酸,并且
其中所述方法在没有间歇性的煅烧下进行。
2.根据权利要求1所述的方法,其中所述C3-C12多羟基化合物以基于所述催化剂总重量的3-30重量%的量存在于所述硫化的催化剂中。
3.根据权利要求1所述的方法,其中所述C3-C12多羟基化合物以基于所述催化剂总重量的5-20重量%的量存在于所述硫化的催化剂中。
4.根据权利要求1-3任一项所述的方法,其中所述载体进一步包含沸石。
5.根据权利要求4所述的方法,其中所述载体包含基于所述载体总重量的1-10重量%的量的沸石。
6.根据权利要求1所述的方法,其中所述C3-C12多羟基化合物是蔗糖和/或葡萄糖酸。
7.加氢裂化烃流的方法,其包括使所述烃流在氢的存在下接触根据权利要求1-6任一项所述的方法制备的催化剂。
8.根据权利要求7所述的方法,其中所述催化剂是多种催化剂床的堆叠的一部分,其中所述堆叠中的其他催化剂是基于氧化铝的催化剂。
9.根据权利要求8所述的方法,其中根据权利要求1-6任一项所述的方法制备的所述催化剂是底床催化剂。
10.根据权利要求9所述的方法,其中底床催化剂与所述床中其他催化剂的体积比范围是1:1至4:1。
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FR2880822B1 (fr) | 2005-01-20 | 2007-05-11 | Total France Sa | Catalyseur d'hydrotraitement, son procede de preparation et son utilisation |
AU2007308132B2 (en) * | 2006-10-11 | 2011-12-15 | Exxonmobil Research And Engineering Company | Hydroprocessing methods for bulk group VIII/VIB metal catalysts |
CN101553554B (zh) | 2006-10-11 | 2013-08-28 | 埃克森美孚研究工程公司 | 本体第ⅷ族/第vib族金属催化剂的加氢操作方法 |
MX2008006050A (es) * | 2008-05-09 | 2009-11-09 | Mexicano Inst Petrol | Catalizador con acidez moderada para hidroprocesamiento de crudo pesado y residuo, y su procedimiento de sintesis. |
US8518239B2 (en) * | 2008-10-03 | 2013-08-27 | Chevron U.S.A. Inc. | Hydrocracking catalyst and process using a magnesium aluminosilicate clay |
US8394255B2 (en) * | 2008-12-31 | 2013-03-12 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
US8262905B2 (en) | 2009-03-19 | 2012-09-11 | Shell Oil Company | Oil and polar additive impregnated composition useful in the catalytic hydroprocessing of hydrocarbons, a method of making such catalyst, and a process of using such catalyst |
CN105289702A (zh) | 2009-04-29 | 2016-02-03 | 国际壳牌研究有限公司 | 加氢裂化催化剂 |
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2012
- 2012-12-20 CN CN201280069622.9A patent/CN104114275B/zh active Active
- 2012-12-20 US US14/366,739 patent/US10279340B2/en active Active
- 2012-12-20 WO PCT/EP2012/076292 patent/WO2013092806A1/en active Application Filing
- 2012-12-20 RU RU2014130237A patent/RU2623429C2/ru active
- 2012-12-20 IN IN4830CHN2014 patent/IN2014CN04830A/en unknown
- 2012-12-20 EP EP12812619.0A patent/EP2794092B1/en active Active
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WO2013092806A1 (en) | 2013-06-27 |
US20150209772A1 (en) | 2015-07-30 |
RU2623429C2 (ru) | 2017-06-26 |
DK2794092T3 (da) | 2020-11-16 |
US10279340B2 (en) | 2019-05-07 |
RU2014130237A (ru) | 2016-02-20 |
CN104114275A (zh) | 2014-10-22 |
IN2014CN04830A (zh) | 2015-09-18 |
EP2794092B1 (en) | 2020-08-26 |
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