CN101296746A - 用于制备成形的本体催化剂的方法 - Google Patents
用于制备成形的本体催化剂的方法 Download PDFInfo
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- CN101296746A CN101296746A CNA2006800399212A CN200680039921A CN101296746A CN 101296746 A CN101296746 A CN 101296746A CN A2006800399212 A CNA2006800399212 A CN A2006800399212A CN 200680039921 A CN200680039921 A CN 200680039921A CN 101296746 A CN101296746 A CN 101296746A
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- Prior art keywords
- catalyst
- metal oxide
- group vib
- oxide particle
- metal
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 154
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 claims abstract description 102
- 239000002184 metal Substances 0.000 claims abstract description 102
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 74
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 74
- 150000002739 metals Chemical class 0.000 claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000007493 shaping process Methods 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims description 22
- 238000005987 sulfurization reaction Methods 0.000 claims description 21
- 229910052721 tungsten Inorganic materials 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 16
- 239000010937 tungsten Substances 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 239000000853 adhesive Substances 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910003294 NiMo Inorganic materials 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000005336 cracking Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 238000001694 spray drying Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000007701 flash-distillation Methods 0.000 claims 1
- -1 VIB metals Chemical class 0.000 abstract 3
- 238000012360 testing method Methods 0.000 description 16
- 239000012065 filter cake Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 229910003296 Ni-Mo Inorganic materials 0.000 description 9
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- OFQCQIGMURIECL-UHFFFAOYSA-N 2-[2-(diethylamino)ethyl]-2',6'-dimethylspiro[isoquinoline-4,4'-oxane]-1,3-dione;phosphoric acid Chemical compound OP(O)(O)=O.O=C1N(CCN(CC)CC)C(=O)C2=CC=CC=C2C21CC(C)OC(C)C2 OFQCQIGMURIECL-UHFFFAOYSA-N 0.000 description 1
- 101100255944 Arabidopsis thaliana RWA1 gene Proteins 0.000 description 1
- 101100255945 Arabidopsis thaliana RWA2 gene Proteins 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000000498 stratum granulosum Anatomy 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
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- 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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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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- 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
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- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
本发明涉及一种用于制备成形的本体催化剂的方法,所述成形的本体催化剂包括含有一种或多种VIII族金属和两种或更多种VIB族金属的金属氧化物颗粒,该方法包括步骤:提供包括一种或多种第一VIII族金属和一种或多种第一VIB族金属的第一金属氧化物颗粒;提供分别制备的第二金属氧化物颗粒,其包括一种或多种第二VIII族金属和一种或多种第二VIB族金属,其中,在第一和第二金属氧化物颗粒中的VIB族和VIII族金属的组成不同;在成形之前和/或期间将第一和第二金属氧化物颗粒混合;以及使混合的第一和第二金属氧化物颗粒成形,以形成成形的本体催化剂。本发明进一步涉及用该方法所获得的硫化或非硫化形式的成形本体催化剂及其在加氢操作中的应用。
Description
本发明涉及一种用于制备成形的本体催化剂的方法,所述成形的本体催化剂包括含有一种或更多种VIII族金属和两种或更多种VIB族金属的金属氧化物颗粒。本发明进一步涉及用该方法可获得的、以硫化或非硫化形式的成形本体催化剂及其在加氢操作中的应用。
关于本体催化剂意思是指包括至少60wt%的金属氧化物颗粒(基于金属氧化物相对于本体催化剂的总重量计算的wt%)的催化剂,其区别于含有沉积在载体材料上明显小于60wt%的金属氧化物的负载型催化剂。本体催化剂通常为成形颗粒的形式,例如通过挤出包括金属氧化物颗粒和0~40wt%的附加材料,特别是粘合剂材料的组合物来生产的。本体催化剂在加氢操作中通常具有非常高的活性。
在本文中的术语“加氢操作或加氢处理”包括在升高的温度和升高的压力下烃类进料与氢反应的所有方法,包括诸如氢化、加氢脱硫、加氢脱氮、加氢脱金属、加氢脱芳烃(hydrodearomatization)、加氢异构化、加氢脱蜡、加氢裂解以及在缓和压力条件下的加氢裂解,这通常被称作为缓和加氢裂解。除非另有说明,在下文中,当提及本发明的本体催化剂的高活性时,特别意指加氢脱硫活性。
WO 00/41810描述了包括含至少一种VIII族金属和至少两种VIB族金属的本体催化剂颗粒的本体催化剂(下文称作为三金属本体催化剂),特别是镍/钼/钨基催化剂。比较例还描述了实质上包括仅一种VIB族金属和一种VIII族金属的本体催化剂(下文称作为双金属本体催化剂)。三金属本体催化剂表现出高于双金属本体催化剂的催化活性。在以下方法中制备三金属本体催化剂,其中,将包括一种或更多种VIII族金属和两种或更多种VIB族金属的金属化合物在存在质子性液体的条件下进行混合,并且其中一种或更多金属化合物在整个方法期间至少部分保持为固态。其中至少一种所述金属化合物至少部分保持为固态且至少一种化合物为溶解物状态的方法被称作为固体-溶解物方法。
其中所有VIB族和VIII族金属化合物至少部分保持为固态的方法被称作为固-固方法。
WO 00/41811描述了三金属本体加氢操作催化剂及其制备方法,该方法包括步骤:使溶液中的至少一种VIII族金属化合物与溶液中的至少两种VIB族金属化合物在反应混合物中混合和反应以获得沉淀物。此方法被称作溶解物-溶解物方法。比较例还描述了包括仅一种VIB族金属和仅一种VIII族金属的双金属本体催化剂。三金属本体催化剂具有明显高于双金属本体催化剂的催化活性。
不同的加氢处理条件、不同的加氢处理进料或者不同的设备条件可能需要不同组成的三金属本体催化剂组合物。不论所用的生产方法的类型,从化学的观点来看,生产包括两种或更多种VIB族金属的三金属本体催化剂组合物显然比生产双金属催化剂更困难。所希望的本体催化剂的组成上的变化不能总是直接转化为起始金属化合物的组成的变化和/或方法条件的变化。除此之外,在现有技术方法中,从一种本体催化剂组合物切换到另一种时,在生产运转之间存在有相当多的停机时间,导致生产能力降低。此外,当从一种本体催化剂组合物切换到另一种时,与单一生产运转相比产生更多的废弃物,导致更大的环境负担和贵金属损失。
本发明的目的是提供一种用于制造三金属本体催化剂组合物的方法,其不具有上述缺点。
根据本发明,提供一种用于制备成形的本体催化剂的方法,该方法包括步骤:
i)提供第一金属氧化物颗粒,其包括一种或多种第一VIII族金属和一种或多种第一VIB族金属的;
ii)提供分别制备的第二金属氧化物颗粒,其包括一种或多种第二VIII族金属和一种或多种第二VIB族金属,其中在第一和第二金属氧化物颗粒中的VIB族和VIII族金属的组成是不同的;
iii)在成形之前和/或期间,将所述第一和第二金属氧化物颗粒混合,以形成本体催化剂组合物;以及
iv)使混合的第一和第二金属氧化物颗粒成形,以形成成形的本体催化剂。
从化学的观点来看,发现根据本发明的方法较简单,并且在改变为不同的本体催化剂组合物方面具有最佳的适应性。在独立地优化的标准生产运转中生产第一和第二金属氧化物颗粒,赋予所获得的金属氧化物本体催化剂颗粒优化的高质量和优化的高生产能力,而且在改变为不同组成的本体催化剂组合物时,不必产生停机时间和额外的废弃物。令人惊奇地发现,本发明的成形的本体催化剂的活性可以与组成完全相同的现有技术三金属催化剂的活性相比,或者甚至更高。这对于本发明工艺的优选模式是特别令人惊奇的,其中第一和第二金属氧化物颗粒中的一种或两者是包括仅一种VIB族金属的双金属氧化物颗粒,因为根据现有技术,双金属本体催化剂具有明显较低的催化活性。
根据本发明的方法的第一实施方式,在成形之前和/或成形期间,将第一和第二金属氧化物颗粒混合,以形成成形的混合本体催化剂颗粒。将第一和第二金属氧化物颗粒混合,还包括含第一和第二金属氧化物颗粒的组合物的混合。例如,在混合和成形之前,可以用粘合剂材料加工助剂将第一和/或第二金属氧化物颗粒复合。成形工艺的细节描述如下。在此实施方式中,优选均匀地混合第一和第二金属氧化物颗粒,使得所有的成形颗粒具有基本上完全相同的三金属组成。
第一和第二氧化物本体颗粒以基于催化剂的设计最终应用的相对量来混合,优选本体催化剂组合物中的钼与钨的摩尔比在1∶9和9∶1之间。
关于“不同组成”,主要意指第一金属氧化物颗粒中的VIB族和/或VIII族金属不同于第二金属氧化物颗粒中的VIB族和/或VIII族金属。优选的是,在方法中第一金属氧化物颗粒中的VIB族金属不同于第二金属氧化物颗粒中的VIB族金属。进一步优选的是,第一金属氧化物颗粒中的VIII族金属与第二金属氧化物颗粒中的VIII族金属相同。在本发明的方法中,优选第一金属氧化物颗粒包括钼作为主要VIB族金属,第二金属氧化物颗粒包括钨作为主要VIB族金属。更优选地,第一和第二金属氧化物颗粒中的VIII族金属相同,优选为镍或钴,并且第一氧化物本体催化剂中的VIB族金属实质上只有钼,第二氧化本体催化剂中的VIB族金属实质上只有钨。“实质上只有”暗指催化剂优选没有其它的VIB族或VIII族金属,但可以含有非实质量的另外VIB族或VIII族金属,优选小于5摩尔%,更优选小于3摩尔%,最优选小于1摩尔%(相对于VIB族或VIII族金属的总量)。最优选地,第一和第二金属氧化物颗粒实质上分别为双金属NiMo和NiW氧化物颗粒。在另一实施方式中,第一金属氧化物颗粒包括两种或更多种VIB族金属和一种或更多种VIII族金属,并且其中第二氧化物颗粒实质上包括仅有一种VIB金属和一种或多种VIII族金属。在此实施方式中,第一金属氧化物颗粒是三金属NiMoW颗粒,第二金属氧化物颗粒实质上是双金属NiW和/或NiMo金属氧化物颗粒。
成形的本体催化剂优选包括仅一种VIII族金属,优选非贵金属钴、镍或铁,但是,任选地可以包括额外的VIII金属。尽管较不优选,催化剂可以包含少量的其它金属。本体催化剂可以任选地进一步包括优选小于10%,更优选小于9%,甚至更优选小于7%,最优选低于5%(相对于总的VIB族金属的摩尔%)的额外的其它金属,特别是V族金属,优选为铌。
在本发明方法的最重要的实施方式中,第一和第二氧化物本体颗粒都是新制备的。然而,可设想的是,可能使用用用于改变先前制备的成品本体催化剂的催化性能的本发明方法,以根据不同的需要改变性能。例如,还可以将该方法用于制备以下的本体催化剂组合物,其中,至少部分以失效的、用过的、不合格的或再生的失效氧化物颗粒或者本体催化剂的形式提供第一氧化物本体颗粒,而第二金属氧化物颗粒是新制备的。可能有必要使失效的、不合格的或再生的失效氧化物颗粒或者本体催化剂处于合适的形式,例如通过研磨,使得它能够与新制备的金属氧化物颗粒一起方便地组合和成形。可以将失效的、用过的或再生的失效本体催化剂升级,以满足用于特定加氢处理条件的需要。
可以按照现有技术中所描述的各种不同方法制备第一和第二金属氧化物颗粒。从所获得的催化剂的高催化活性和高产率来考虑,优选在下述方法中分别制备第一和/或第二氧化物本体颗粒,该方法包括:在存在质子性液体的条件下制备包括一种或多种第一化合物和一种或多种第二化合物的反应混合物,所述第一化合物包含一种或多种VIII族金属,优选为Ni或Co,所述第二化合物包含一种或多种VIB族金属,优选为钼或钨;使第一和第二化合物反应,其中,在整个反应过程中第二金属化合物至少部分保持为固态。
尽管热处理或煅烧是优选的,但它不是必要的。必要的是,在本体催化剂组合物,特别是本体催化剂组合物中的金属氧化物颗粒的热处理期间的温度低于发生向非活性结构转化的温度。在本体催化剂的生产方法中,这适用于任意及所有的热处理步骤。本领域技术人员可以确定所给定的催化剂组合物的最大热处理温度。这同样特别适用于成形的本体催化剂颗粒在复合和成形之后的热处理。优选地,在低于450℃,更优选低于400℃,甚至更优选低于375℃且最优选低于350℃下热处理所述本体催化剂。
该方法可以进一步包括一个或多个如下方法步骤:
i)在使金属化合物混合和/或反应之前、期间或之后,将金属氧化物颗粒与0~40wt%的选自以下组的一种或多种材料复合:粘合剂材料、常规加氢处理催化剂、酸性促进剂或它们的混合物;
ii)喷雾干燥、(快速)干燥、研磨、捏合、浆料混合、干式或湿式混合或它们的组合;
iii)成形;
iv)干燥和/或热处理;以及
v)硫化。
在现有技术,具体在WO 00/41810或WO 00/41811中描述了用于制备第一和第二金属氧化物颗粒的方法步骤的详细情况,通过参考引入本申请文件中。
本体催化剂包括至少60wt%的金属氧化物颗粒(基于金属氧化物相对于本体催化剂的总重量来计算的wt%),其区别于含有沉积在载体材料上远小于60wt%金属氧化物的负载型催化剂。从获得高催化活性考虑,优选的是,根据本发明的本体催化剂包括至少70wt%,更优选至少75wt%,甚至更优选至少80wt%,最优选至少85wt%的金属氧化物颗粒。其余量0~40wt%可以是选自以下组的一种或多种材料:粘合剂材料、常规加氢处理催化剂、酸性促进剂和裂解组分。
通常,用粘合剂将金属氧化物颗粒复合,然后成形,优选被挤出,以形成成形的本体催化剂颗粒。在成形的本体催化剂中,优选的是,用粘合剂材料结合金属氧化物颗粒,以提高成形颗粒的侧面压碎强度。适合的成形方法是挤出、制成球、制成颗粒,还有喷雾干燥(任选地在存在粘合剂的条件下)和研磨或团聚(任选地与过筛至特定的窄粒度分布相结合)。
本发明还涉及根据本发明的方法可获得的成形的本体催化剂,其包括含一种或多种VIII族金属和两种或更多种VIB族金属的金属氧化物颗粒。本发明还涉及已经硫化的上述成形的本体催化剂,成形的本体催化剂或硫化的本体催化剂在加氢处理包括含硫和氮的有机化合物的烃类进料中的应用;并且还涉及用于加氢处理烃进料的方法,其包括在催化转化条件下和在有催化有效量的本发明的成形本体催化剂或硫化的本体催化剂的条件下使所述进料与氢接触。
发现富含钨的所述催化剂在加氢脱硫中特别活泼。本发明进一步涉及根据本发明的成形的本体催化剂或硫化的本体催化剂及其在烃进料的加氢处理中作为加氢脱硫催化剂的应用,其中所述催化剂包括至少50%的钨,优选大于60%、65或甚至70%(相对于VIB族金属总量的摩尔%)的钨。进一步发现在高压下其活性明显更高。因此,压力优选大于20巴,优选大于40巴,甚至更优选大于50巴。可选择地,本发明涉及成形的本体催化剂或硫化的本体催化剂及其在烃进料的加氢处理中作为加氢脱氮催化剂的应用,其中,所述催化剂包括至少50%,优选大于60%、65%或者甚至70%的钼(相对于VIB族金属总量的摩尔%)。发现与相应的钼含量较低的三金属催化剂相比,所述催化剂在加氢脱氮中更活泼。
通过下述的实施例和比较试验进一步说明本发明。用下述内燃机测试程序D1(Diesel test procedure D1)测试了催化剂,其采用表2中所述的两种不同温度和压力测试条件1和2以及表1中所述的汽油进料。后缀1或2(例如RWA1和RWA2中)分别指测试条件1和2。将内燃机测试程序D1中的参照催化剂C1的RWA/RVA值定义为100。相对于此参照催化剂计算所有其它RWA/RVA值。
内燃机测试程序D1
在下流管式反应器中测试了催化剂。每个反应管包含10ml催化剂,该催化剂与等量的SiC颗粒混合且夹在SiC颗粒层之间。在测试前,采用已经用二甲基二硫化物掺杂至总硫含量为3.7wt%的表1所述的进料,通过液相预硫化将所述催化剂进行预硫化。然后,在具有表1所示性能的内燃机进料的加氢处理中测试所述预硫化的催化剂:
表1
汽油进料 | |
硫含量(%wt) | 1.24 |
氮含量(ppmwt) | 86 |
单芳香族化合物(%wt) | 16.5 |
二芳香族化合物(%wt) | 10.8 |
二+芳香族化合物(%wt) | 0.8 |
总的芳香族化合物(%wt) | 28.1 |
模拟的蒸馏ASTM-D86 | |
初始沸点(℃) | 184 |
5%体积(℃) | 218.6 |
10%体积(℃) | 231.1 |
20%体积(℃) | 250.9 |
30%体积(℃) | 264.8 |
40%体积(℃) | 276.4 |
50%体积(℃) | 286.8 |
60%体积(℃) | 298.1 |
70%体积(℃) | 309.7 |
80%体积(℃) | 324.7 |
90%体积(℃) | 345.3 |
95%体积(℃) | 360.3 |
最终沸点(℃) | 373.8 |
在表2所示的两种条件下测试所述催化剂。
表2
预硫化 | 条件1 | 条件2 | |
温度(℃) | 315 | 320 | 340 |
压力(巴) | 30 | 40 | 20 |
H2与油的比(Nl/l) | 200 | 300 | 300 |
LHSV(l/h) | 3.0 | 2.0 | 1.5 |
表3中给出了测试结果,其中RWA是基于反应器中所装载的总催化剂量的相对重量活性。HDN是加氢脱氮,以及HDS是加氢脱硫。CBD意指催化剂的压实体积密度。R3表示固-固反应方法,其中第一和第二金属化合物在反应期间至少部分为固体。
比较例1(C1:Ni1.5Mo0.5W0.5R3)
在6400mL的水中将115.2g的MoO3(0.8摩尔Mo,福斯公司(ex.Aldrich))和200g的H2WO4(0.8摩尔W,ex.Aldrich)浆料化(悬浮液A),并且加热至90℃。将282.4g的碱式碳酸镍2NiCO3·3Ni(OH)2·4H2O(2.4摩尔Ni,ex.Aldrich)悬浮在1600ml水中(悬浮液B),并且加热至90℃。在这个及其它实施例中所使用的碱式碳酸镍具有239m2/g的BET比表面积。在10分钟内将悬浮液B添加到悬浮液A中,在持续搅拌下将所得混合物在90℃保持16小时(整夜)。在此时间结束时,过滤该悬浮液。产率大于98%(基于所有金属成分已转化为它们的氧化物的计算重量)。将得到的滤饼与2.5wt%的粘合剂(基于催化剂组合物的总重)湿混合。为了获得可挤出的混合物,调节混合物中的水含量,随后将混合物挤出。所得固体在120℃干燥16小时(整夜),并且在300℃煅烧1小时。
将催化剂硫化,并且用内燃机测试程序1的程序进行测试,其转化结果汇总在表3中。
比较例2(C2:由未反应的氧化物制成的Ni1.5W0.5Mo0.5)
通过将VIB族和VIII族金属组分的未反应氧化物湿混合,制备催化剂:采用185.6g的WO3(0.8摩尔W,ex.Aldrich)、115.2g的MoO3(0.8摩尔Mo,ex.Aldrich)和180g的NiO(2.4摩尔Ni,ex.Aldrich)制备催化剂。将该湿氧化物混合物与基于所述催化剂组合物的总重为2.5wt%的粘合剂进行混合。将金属氧化物颗粒挤出、干燥、煅烧和硫化,随后按照C1中所述的进行测试。其转化结果汇总在表3中。差活性的结果表明,在混合之前使VIB族和VIII族氧化金属化合物反应是必要的。
实施例1(E1:混合R3催化剂湿饼的Ni1.5W0.25Mo0.75)
如在C1中所述的方式,制备Ni-W湿滤饼,除了仅用一种VIB族组分钨之外:采用400g的钨酸(1.6摩尔W,ex.Aldrich)和180g的NiO(2.4摩尔Ni)制备催化剂。产率约99%。此外,如C1中所述制备的Ni-Mo湿滤饼,除了仅用一种VIB族组分钼之外:采用230.4g的三氧化钼(1.6摩尔Mo,ex.Aldrich)和282.4g的碱式碳酸镍(2.4摩尔Ni)制备催化剂。其产率约85%。
将如上所述方式制备的湿Ni-W滤饼与如上所述的湿Ni-Mo滤饼混合。调节各滤饼的量,以获得Ni∶Mo∶W摩尔比为1.5∶0.25∶0.75(512g(干重)的Ni-W饼+128g的Ni-Mo饼(干重))。将金属氧化物颗粒挤出、干燥、煅烧和硫化,随后如C1中所述的进行测试。其转化结果汇总在表3中。令人惊奇地HDS活性,特别是在第一测试条件下明显优于三金属的参照催化剂C1。
实施例2(E2:混合R3催化剂湿饼的Ni1.5W0.5Mo0.5)
如E1中的方式制备催化剂,除了调节各滤饼的量,以获得Ni∶Mo∶W摩尔比为1.5∶0.5∶0.5(341.6g(干重)的Ni-W饼+256g的Ni-Mo饼(干重))。将金属氧化物颗粒挤出、干燥、煅烧和硫化,随后如C1中所述的进行测试。其转化结果汇总在表3中。
实施例3(E3:混合R3催化剂湿饼的Ni1.5W0.75Mo0.25)
如E1中的方式制备催化剂,除了调节各滤饼的量,以获得Ni∶Mo∶W摩尔比为1.5∶0.75∶0.25(170.4g(干重)Ni-W饼+384.8g的Ni-Mo饼(干重))。将金属氧化物颗粒挤出、干燥、煅烧和硫化,随后如C1中所述的进行测试。其转化结果汇总在表3中。
实施例3(E3:混合R3催化剂干饼的Nil.5W0.5Mo0.5)
如C3中所述的方式制备Ni-W滤饼,随后在120℃干燥16小时,将Ni-W滤饼与Ni-Mo滤饼混合,所述Ni-Mo滤饼如C4中所述的方式制备,随后在120℃干燥16小时。调节各滤饼的量,以获得Ni∶Mo∶W摩尔比为1.5∶0.5∶0.5(341.6g(干重)的Ni-W饼+256g的Ni-Mo饼(干重))。将金属氧化物颗粒混合物挤出、干燥、煅烧和硫化,随后,如C1中所述的进行测试。其转化结果汇总在表3中。
实施例E1到E3表明,增大的W∶Mo的比例获得逐渐升高的HDS1活性;而在另一方面,降低的W∶Mo的比例获得逐渐升高的HDN1活性。具有超过50%的Mo(相对于W和Mo总量的摩尔%)的催化剂优选用作HDN催化剂;而具有超过50%的W的催化剂优选用作HDS催化剂。通过按照获得设想的最终应用所希望的成形本体催化剂的全部组成所需要的相对量来混合第一和第二氧化物颗粒,采用同样的Ni-W和Ni-Mo三金属金属氧化物颗粒,能够容易地制备这两种所述催化剂。
表3.活性测试结果
样品 | 组成 | 方法 | 测试 | RWA | RWA | RWA | RWA |
挤出物 | HDS1 | HDS2 | HDN1 | HDN2 | |||
C1 | Ni1.5Mo0.5W0.5 | R3 | D1 | 100 | 100 | 100 | 100 |
C2 | 由未反应氧化物制成的Ni1.5Mo0.5W0.5 | 共混 | D1 | 14 | 27 | 33 | 30 |
E1 | 混合湿饼的Ni1.5Mo0.25W0.75 | R3 | D1 | 121 | 86 | 119 | 90 |
E2 | 混合湿饼的Ni1.5Mo0.5W0.5 | R3 | D1 | 118 | 89 | 127 | 100 |
E3 | 混合湿饼的Ni1.5Mo0.75W0.25 | R3 | D1 | 86 | 86 | 151 | 102 |
E4 | 混合干饼的Ni1.5Mo0.5W0.5 | R3 | D1 | 115 | 87 | 132 | 96 |
Claims (25)
1.一种用于制备成形的本体催化剂的方法,所述成形的本体催化剂包括含有一种或多种VIII族金属和两种或更多种VIB族金属的金属氧化物颗粒,该工艺包括步骤:
i)提供第一金属氧化物颗粒,其包括一种或多种第一VIII族金属和一种或多种第一VIB族金属;
ii)提供分别制备的第二金属氧化物颗粒,其包括一种或多种第二VIII族金属和一种或多种第二VIB族金属,其中,在第一和第二金属氧化物颗粒中的VIB族和VIII族金属的组成不同;
iii)在成形之前和/或成形期间,将所述第一和第二金属氧化物颗粒混合,以形成本体催化剂组合物;以及
iv)将混合的第一和第二金属氧化物颗粒成形,以形成成形的本体催化剂。
2.根据权利要求1所述的方法,其中,在第一金属氧化物颗粒中的所述一种或多种第一VIB族金属和/或VIII族金属不同于所述一种或多种第二VIB族金属和/或VIII族金属。
3.根据权利要求1所述的方法,其中,在第一金属氧化物颗粒中的VIB族金属不同于在第二金属氧化物颗粒中的VIB族金属。
4.根据权利要求3所述的方法,其中,所述第一金属氧化物颗粒包括VIB族金属钼,第二金属氧化物颗粒包括VIB族金属钨。
5.根据权利要求1所述的方法,其中,在第一金属氧化物颗粒中的所述一种或多种VIII族金属与在第二金属氧化物颗粒中的所述一种或多种VIII族金属相同。
6.根据权利要求5所述的方法,其中,在第一和第二金属氧化物颗粒中的所述一种或多种VIII族金属是相同的,优选为镍或钴;并且在第一氧化物本体催化剂中的VIB族金属实质上只有钼,在第二氧化物本体催化剂中实质上只有钨。
7.根据权利要求6所述的方法,其中,所述第一和第二金属氧化物颗粒分别是NiMo和/或NiW氧化物颗粒。
8.根据权利要求1所述的方法,其中,所述第一金属氧化物颗粒包括2种或更多种VIB族金属和一种或多种VIII族金属,所述第二氧化物颗粒实质上仅包含一种VIB族金属和一种或多种VIII族金属。
9.根据权利要求8所述的方法,其中,所述第一金属氧化物颗粒是NiMoW颗粒,所述第二金属氧化物颗粒是NiW和/或NiMo氧化物颗粒。
10.根据权利要求1~7所述的方法,其中,将所述第一和第二氧化物本体颗粒以这样的相对量混合,使得在所述成形的本体催化剂组合物中的钼与钨的摩尔比在1∶9和9∶1之间。
11.根据权利要求1所述的方法,其中,所述第一和第二氧化物本体颗粒都是新制备的。
12.根据权利要求1所述的方法,其中,以再生的失效或不合格的金属氧化物颗粒或本体催化剂的形式提供所述第一或第二氧化物本体颗粒中的一种,所述第一或第二氧化物本体颗粒中的另一种是新制备的。
13.根据权利要求1所述的方法,其中,所述第一和/或第二氧化物本体颗粒是在包括以下步骤的方法中制备的:
i)在存在质子性液体的情况下,制备包括一种或多种第一化合物和一种或多种第二化合物的反应混合物,所述第一化合物包含一种或多种VIII族金属,优选为Ni或Co,所述第二化合物包含一种或多种VIB族金属,优选为钼或钨;
ii)使所述第一和第二化合物反应,其中,在整个反应期间,所述第一和/或第二金属化合物至少部分保持为固态。
14.根据权利要求13所述的方法,其中,所述第一和第二金属化合物都不含氮原子,并且与反应后的金属氧化物颗粒分离的质子性液体被重新用于制备反应混合物。
15.根据权利要求1~14所述的方法,其中,在低于400℃的温度下煅烧所述成形的氧化物本体催化剂。
16.根据权利要求1~15所述的用于制造本体催化剂的方法,进一步包括一个或多个下列方法步骤:
i)在将金属化合物混合和/或反应之前、期间或之后,将金属氧化物颗粒与0~40wt%的选自以下组的一种或多种材料复合:粘合剂材料、常规加氢处理催化剂、裂解化合物、酸性促进剂或它们的混合物;
ii)喷雾干燥、(闪蒸)干燥、研磨、捏合、浆料混合、干式或湿式混合或它们的组合;
iii)成形;
iv)干燥和/或热处理;以及
v)硫化。
17.一种成形的本体催化剂,包括含一种或多种VIII族金属和两种或更多种VIB族金属的金属氧化物颗粒,可以通过权利要求1~16所述的方法获得。
18.一种硫化的本体催化剂组合物,其包括已经硫化的权利要求17所述的成形的本体催化剂。
19.权利要求17或18所述的成形的本体催化剂或硫化的本体催化剂用于加氢处理包括含硫和氮的有机化合物的烃类进料的应用。
20.权利要求17或18所述的成形的本体催化剂或硫化的本体催化剂的应用,其中,所述催化剂包含至少50%(相对于VIB族金属总量的摩尔%)的钨,作为在烃类进料的加氢处理中的加氢脱硫催化剂。
21.权利要求17或18所述的成形的本体催化剂或硫化的本体催化剂的应用,其中,所述催化剂包含至少50%(相对于VIB族金属总量的摩尔%)的钼,作为在烃类进料的加氢处理中的加氢脱氮催化剂。
22.用于加氢处理烃类进料的方法,包括在存在催化有效量的权利要求17或18所述的成形的本体催化剂或硫化的本体催化剂的情况下和在催化转化条件下,使所述进料与氢接触。
23.根据权利要求22所述的加氢处理方法,使用权利要求17或18所述的成形的本体催化剂或硫化的本体催化剂作为加氢脱硫催化剂,所述成形的本体催化剂或硫化的本体催化剂含有至少50%的钨,优选大于60%、65%或70%的钨(相对于VIB族金属总量的摩尔%)。
24.根据权利要求23的加氢处理方法,其中,在至少20巴,优选至少40巴的压力下进行所述加氢处理。
25.根据权利要求22所述的加氢处理方法,使用权利要求17或18所述的成形的本体催化剂或硫化的本体催化剂作为加氢脱氮催化剂,所述成形的本体催化剂或硫化的本体催化剂含有至少50%的钼,优选大于60%、65%或70%的钼(相对于VIB族金属总量的摩尔%)。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101890379B (zh) * | 2009-05-19 | 2012-09-12 | 中国石油化工股份有限公司 | 一种体相催化剂及其制备方法 |
CN107774296A (zh) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | 一种加氢裂化催化剂的制备方法 |
CN107790143A (zh) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | 加氢处理催化剂的制备方法 |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BRPI0717817B1 (pt) * | 2006-09-14 | 2015-09-08 | Albemarle Netherlands Bv | processo para recuperar um ou mais metais do grupo vib a partir de um catalisador que tem um ou mais metais do grupo vib e um ou mais metais do grupo viii; composto metálico sólido; processo para a fabricação de um catalisador fresco |
AU2008318836B2 (en) * | 2007-10-31 | 2013-04-04 | Chevron U.S.A. Inc. | Hydroconversion processes employing multi-metallic catalysts and method for making thereof |
JP5543361B2 (ja) | 2007-12-04 | 2014-07-09 | アルベマール・ネーザーランズ・ベー・ブイ | バルク金属酸化物粒子を調製するためのプロセス |
US20090271306A1 (en) * | 2008-04-29 | 2009-10-29 | Iovation Inc. | System and Method to Facilitate Secure Payment of Digital Transactions |
EP2196260A1 (en) * | 2008-12-02 | 2010-06-16 | Research Institute of Petroleum Industry (RIPI) | Hydrodesulphurization nanocatalyst, its use and a process for its production |
JP2013521103A (ja) * | 2009-03-06 | 2013-06-10 | アルベマール・ユーロプ・エスピーアールエル | 塊状硫化混合金属触媒ならびに合成ガスからアルコールへの変換におけるその製造および使用のための方法 |
US8383543B2 (en) | 2009-04-29 | 2013-02-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964526B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7931799B2 (en) * | 2009-04-29 | 2011-04-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8058203B2 (en) * | 2009-04-29 | 2011-11-15 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8080492B2 (en) * | 2009-04-29 | 2011-12-20 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964525B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964524B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
EP2450103A1 (en) * | 2010-11-03 | 2012-05-09 | Centre National de la Recherche Scientifique (CNRS) | Novel bulk catalyst precursors and method for obtaining such bulk catalyst precursors |
RU2473387C1 (ru) * | 2011-10-06 | 2013-01-27 | Учреждение Российской академии наук Институт проблем переработки углеводородов Сибирского отделения РАН (ИППУ СО РАН) | Способ получения массивного катализатора гидропереработки тяжелых нефтяных фракций |
CA2883517C (en) | 2012-09-05 | 2021-03-09 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalysts and method for making thereof |
RU2695617C1 (ru) * | 2019-05-24 | 2019-07-24 | Акционерное общество "Техметалл-2002" | Способ получения катализатора окисления метанола до формальдегида |
BR102020006833A2 (pt) * | 2020-04-03 | 2021-10-19 | Petróleo Brasileiro S.A. - Petrobras | Catalisador para geração de hidrogênio e/ou gás de síntese, seu método de obtenção e uso em processo de reforma a vapor |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB626742A (en) * | 1947-02-14 | 1949-07-20 | Standard Oil Dev Co | Improvements in or relating to the catalytic synthesis of hydrocarbons |
DD130793B1 (de) * | 1977-03-28 | 1981-09-30 | Manfred Weber | Verfahren zur rejuvenierung gebrauchter hydrospaltkatalysatoren |
US5122258A (en) | 1991-05-16 | 1992-06-16 | Exxon Research And Engineering Company | Increasing VI of lube oil by hydrotreating using bulk Ni/Mn/Mo or Ni/Cr/Mo sulfide catalysts prepared from ligated metal complexes |
FR2758278B1 (fr) * | 1997-01-15 | 1999-02-19 | Inst Francais Du Petrole | Catalyseur comprenant un sulfure mixte et utilisation en hydroraffinage et hydroconversion d'hydrocarbures |
US6162350A (en) * | 1997-07-15 | 2000-12-19 | Exxon Research And Engineering Company | Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901) |
US6620313B1 (en) * | 1997-07-15 | 2003-09-16 | Exxonmobil Research And Engineering Company | Hydroconversion process using bulk group VIII/Group VIB catalysts |
CZ298704B6 (cs) * | 1999-01-15 | 2007-12-27 | Albemarle Netherlands B.V. | Katalyzátor, zpusob jeho výroby a jeho použití |
CN1309476C (zh) * | 1999-01-15 | 2007-04-11 | 阿尔伯麦尔荷兰公司 | 新型混合金属催化剂及其用途 |
US6534437B2 (en) * | 1999-01-15 | 2003-03-18 | Akzo Nobel N.V. | Process for preparing a mixed metal catalyst composition |
JP4473393B2 (ja) * | 2000-01-13 | 2010-06-02 | 出光興産株式会社 | 脱メタル触媒及びそれを用いた重質油の水素化処理方法 |
FR2846574B1 (fr) * | 2002-10-30 | 2006-05-26 | Inst Francais Du Petrole | Catalyseur et procede d'hydrocraquage de charges hydrocarbonees |
AR043242A1 (es) * | 2003-02-24 | 2005-07-20 | Shell Int Research | Preparacion y uso de una composicion de catalizador |
TW200521219A (en) * | 2003-07-08 | 2005-07-01 | Shell Int Research | Process to prepare a base oil |
FR2859923B1 (fr) * | 2003-09-19 | 2006-10-13 | Inst Francais Du Petrole | Catalyseur d'hydroraffinage et/ou d'hydroconversion comprenant une nouvelle phase active sous forme de solution solide sulfure |
US7232934B2 (en) * | 2003-09-19 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Hydrogenation of oxo aldehydes to oxo alcohols in the presence of a nickel-molybdenum catalyst |
EP1694799A2 (en) * | 2003-10-02 | 2006-08-30 | ExxonMobil Research and Engineering Company | Process for upgrading naphtha |
DK1680486T3 (da) * | 2003-10-03 | 2022-08-22 | Albemarle Netherlands Bv | Fremgangsmåde til at aktivere en hydrogenbehandlende katalysator |
US7597795B2 (en) * | 2003-11-10 | 2009-10-06 | Exxonmobil Research And Engineering Company | Process for making lube oil basestocks |
US7648941B2 (en) * | 2004-09-22 | 2010-01-19 | Exxonmobil Research And Engineering Company | Bulk bimetallic catalysts, method of making bulk bimetallic catalysts and hydroprocessing using bulk bimetallic catalysts |
JP4934134B2 (ja) * | 2005-07-22 | 2012-05-16 | ビーエーエスエフ ソシエタス・ヨーロピア | 二次触媒材料を含有する、炭化水素の脱水素または水素化触媒 |
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Cited By (5)
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CN101890379B (zh) * | 2009-05-19 | 2012-09-12 | 中国石油化工股份有限公司 | 一种体相催化剂及其制备方法 |
CN107774296A (zh) * | 2016-08-29 | 2018-03-09 | 中国石油化工股份有限公司 | 一种加氢裂化催化剂的制备方法 |
CN107790143A (zh) * | 2016-08-29 | 2018-03-13 | 中国石油化工股份有限公司 | 加氢处理催化剂的制备方法 |
CN107790143B (zh) * | 2016-08-29 | 2020-03-17 | 中国石油化工股份有限公司 | 加氢处理催化剂的制备方法 |
CN107774296B (zh) * | 2016-08-29 | 2020-07-07 | 中国石油化工股份有限公司 | 一种加氢裂化催化剂的制备方法 |
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