CN108603127A - 在杂合反应器中通过捕获分散催化剂改善重质产物的方法 - Google Patents

在杂合反应器中通过捕获分散催化剂改善重质产物的方法 Download PDF

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CN108603127A
CN108603127A CN201680074175.4A CN201680074175A CN108603127A CN 108603127 A CN108603127 A CN 108603127A CN 201680074175 A CN201680074175 A CN 201680074175A CN 108603127 A CN108603127 A CN 108603127A
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catalyst
fixed bed
dispersed catalyst
dispersed
bed catalyst
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M.德雷亚尔
J.迈舍尔
J.马克斯
P.沙特龙-米肖
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IFP Energies Nouvelles IFPEN
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Abstract

本发明涉及一种在至少一个包含固定床催化剂的反应器中加氢处理的重油进料的方法，在该方法中将包含分散催化剂或分散催化剂前体的溶液连续引入所述反应器中，所述分散催化剂的粒度为1nm至100µm。更具体地，本发明涉及用于加氢处理方法的原位催化剂形成，所述加氢处理方法基于在固体载体上捕获分散催化剂的固定床催化剂。

Description

在杂合反应器中通过捕获分散催化剂改善重质产物的方法
发明领域
本发明涉及炼油的领域，更具体地涉及催化加氢处理油馏分的领域。
现有技术
一般而言，加氢处理在一种或多种固定床或沸腾床催化剂或通常已知为浆料的细粒分散体中的催化剂存在下进行。固定床催化剂被固体负载，而分散催化剂为分布在整个反应介质中的细粒形式。
固定床催化剂由沉积在一般由氧化铝或二氧化硅-氧化铝构成的固体载体上的活性相构成。常规地，在使用所述催化剂之前，将一般包含钼和/或钨的液体溶液非原位地浸渍至所述固体载体上。
分散催化剂一般为活性相的复合体形式，通常含有钼和/或钨，具有脂溶性有机配体。
催化剂的活性相为必要的相，一般由金属构成，由于其分子结构而可以催化反应。
一直以来以改善加氢处理催化剂的性能为目的对其进行研究。
因此，专利US 7 578 928和US 7 517 446提出胶体催化剂与固定床催化剂相结合从而构成杂合床(hybrid bed)。这种类型的杂合床能够用于处理较宽范围的进料，因为相比于胶体催化剂，固定床催化剂只能够处理不能进入固定床催化剂的载体的孔的非常大尺寸的分子的一部分，例如沥青质。胶体催化剂的前体溶液与进料紧密混合，其引起与沥青质的特定亲和力并导致获得针对胶体催化剂的小于100 nm的粒度，并因此该胶体催化剂能够位于沥青质周围。因此，借助于胶体催化剂使沥青质裂解并且不影响负载的催化剂。胶体催化剂的颗粒因此不被固定床催化剂捕获，并必定与流出的流出物分离。
Heon Jung et al. Energy & Fuels 2004, 18, 924-929的文章记载一种用于延长固定床加氢脱硫催化剂的循环时间的方法。一旦催化剂不再足够有活性，立即将可溶于油中的金属的前体全部注入。进行类似的随后注入从而再活化所述催化剂并从而延长催化剂的使用寿命。
因此，已经很深度地研究了对催化剂性能和使用寿命的改善，但对这类工作中仍然有兴趣，因为凭借新方法仍然能够获得大幅成本节约。
因此，申请人已经开发了一种新型加氢处理方法，其使用由仅包含少量活性相的固定床催化剂与原位浸渍所述固定床催化剂的固体载体的分散催化剂的组合构成的催化剂。
发明目的
因此，本发明涉及一种加氢处理重油进料的方法，其在至少一个反应器中进行，该反应器包含固定床催化剂，其中将包含分散催化剂或分散催化剂前体的溶液连续引入所述反应器中，所述分散催化剂的粒度为1 nm至100 µm。
更具体地，本发明涉及加氢处理方法的催化剂的原位形成，该方法从在固体载体上捕获分散催化剂的固定床催化剂起始。
本发明的一个优点为获得时间稳定性和催化剂使用寿命的延长。
本发明的另一个优点是无需分散催化剂的再处理步骤，因为其活性相被固定床催化剂捕获。
本发明的另一个优点为通过限制为了补偿催化剂失活所需要的温度的升高而提高或维持加氢处理方法的性能。
发明的详细描述
根据本发明的方法中处理的进料典型地选自在炼油厂中生产的烃级分和重油进料。
术语“重油进料”是指包含单独的或作为混合物的如下物质的油：其中至少80重量%具有高于300℃的沸点的烃、常压渣油或减压渣油、由加氢处理、加氢裂解或加氢转化获得的常压渣油或减压渣油、新鲜的或精炼的减压馏出物和由脱沥青单元获得的脱沥青油。
优选地，本发明上下文中处理的进料由从粗油或从粗油的常压蒸馏或从粗油的减压蒸馏获得的烃级分构成，所述进料包含至少80重量%的分子具有至少300℃，优选至少350℃和更优选至少375℃的沸点的级分，并更优选沸点为至少450℃，优选至少500℃并更优选至少540℃的减压渣油。
有利地，所述进料包含单独的或作为混合物的由煤的直接液化获得的渣油级分、由煤的直接液化获得的减压馏出物，或实际上由木质纤维素生物质的直接液化获得的渣油级分。
这些进料可以包含杂质，例如金属、硫、氮、康氏残碳和不溶于庚烷的化合物（称为C7沥青质）。这些类型的进料实际上一般富含杂质，其中金属含量一般大于20 ppm并甚至大于100 ppm。硫含量一般大于0.5重量%，并甚至可以大于2重量%。
C7沥青质为由于它们的如下性质而被已知的化合物：通过它们的形成重烃残渣（一般称为焦炭）的能力和通过它们的产生基本上限制加氢处理单元操作性能的沉积物的倾向而抑制加氢处理催化剂。
根据本发明，在至少一个反应器中加氢处理所述重油进料。有利地，所述反应器为三相反应器。
所述加氢处理方法在2 MPa至38 MPa，优选5 MPa至25 MPa并更优选8 MPa至20MPa的绝对压力下在300℃至550℃，优选350℃至500℃并更优选360℃至440℃的温度下进行。
进料体积相对于催化剂体积的小时空速(HSV)为0.05 h-1至10 h-1，优选0.1 h-1至5 h-1并更优选0.15 h-1至2 h-1。
与所述进料混合的氢气的量优选为50至5000标准立方米(Nm3)/立方米(m3)液体进料，优选100 Nm3/m3至2000 Nm3/m3并更优选200 Nm3/m3至1000 Nm3/m3。
根据本发明，所述反应器包含固定床催化剂。所述固定床催化剂包含沉积在固体载体上的来自元素周期表第4至12族的一种或多种元素。有利地，所述固体载体选自无定形固体，并优选选自二氧化硅、氧化铝、二氧化硅-氧化铝、二氧化钛和沸石，单独地或作为混合物地。优选地，所述固体载体为氧化铝。
术语“总孔体积”是指通过压汞法(mercury porosimetry)测量并根据ASTM标准D4284-83以4000 bar的最大压力使用484 达因/厘米的表面张力和140°的接触角通过压汞法(mercury intrusion porosimetry)测定的体积。根据Jean Charpin和Bernard Rasneur编著的题目为"Techniques de l'ingénieur, traité analyse et caractérisation[Engineering techniques, analysis and characterization], P 1050-5的作品中的推介，假设润湿角为140°。
优选地，所述固体载体的总孔体积为0.5 mL/g至3.0 mL/g，优选0.5 mL/g至2.0mL/g，更优选0.5 mL/g至1.5 mL/g。
在根据本发明的方法中使用的固定床催化剂的所述固体载体具有包括大孔和中孔的孔分布。根据ASTM标准D4284-83以4000 bar的最大压力使用484达因/厘米的表面张力和140°的接触角通过压汞法测量大孔和中孔的体积。
术语“大孔”是指具有大于50 nm的开口的孔。
优选地，用于所述固定床催化剂的固体载体的大孔体积占总孔体积的0至80%，优选占总孔体积的5%至70%并更优选占总孔体积的10%至60%。
所述用于固定床催化剂的固体载体的大孔体积定义为在0.2 MPa至30 MPa的压力下引入的汞的累积体积，对应于在具有大于50 nm的视直径的孔中容纳的容积。
所述用于固定床催化剂的固体载体的所述大孔体积有利地为0.0 mL/g至2.4 mL/g，优选0.1 mL/g至2.0 mL/g并更优选0.3 mL/g至1.5 mL/g。
此外，所述载体的大孔的中值直径（Dp，以nm计）定义为使得具有低于某一直径的尺寸的全部孔占总大孔体积的50%的该直径，其通过压汞法测量。
所述固定床催化剂的固体载体的大孔的所述中值直径有利地为100 nm至5000 nm并优选150 nm至3000 nm，优选200 nm至2000 nm并还更优选300 nm至1000 nm。
术语“中孔”是指具有范围为2 nm至50 nm（包括边界值）的开口的孔。
优选地，所述固定床催化剂的固体载体的中孔体积占总孔体积的20%至100%，优选占总孔体积的30%至95%，并更优选占总孔体积的40%至90%。
所述固定床催化剂的固体载体的中孔体积定义为在30 MPa至400 MPa的压力下引入的汞的累积体积，对应于具有在2至50 nm范围内的视直径的孔中容纳的体积。
所述固定床催化剂的固体载体的所述中孔体积有利地为0.1 mL/g至3.0 mL/g，优选0.3 mL/g至2.0 mL/g，并更优选0.5 mL/g至1.5 mL/g。
所述载体的中孔的中值直径（Dp，以nm计）定义为使得具有低于某一直径的尺寸的全部中孔占总中孔体积的50%的该直径，其通过压汞法测量。
所述固定床催化剂的固体载体的中孔的所述中值直径有利地为10 nm至40 nm，优选15 nm至30 nm并更优选18 nm至25 nm。
所述固定床催化剂的固体载体有利地具有大于75 m2/g，优选大于100 m2/g并更优选大于125 m2/g的比表面积。
术语“比表面积”是指根据在周刊"The Journal of the American ChemicalSociety", 60, 309, (1938)中记载的BRUNAUER-EMMETT-TELLER方法形成的ASTM标准D3663-78通过氮吸附法测定的BET比表面积。
有利地，所述固定床催化剂包含至少一种来自第VIB族的金属。优选地，所述来自第VIB族的金属选自钼和钨。高度优选地，所述来自第VIB族的金属为钼。
有利地，所述来自第VIB族的金属与至少一种来自第VIII族的金属结合使用。优选地，所述来自第VIII族的金属选自镍和钴。高度优选地，所述来自第VIII族的金属为镍。
优选地，所述固定床催化剂包含镍和钼，更优选地，所述固定床催化剂包含镍、钴和钼。
在其中所述固定床催化剂包含钼的情况下，以三氧化钼(MoO3)的重量表达的钼含量有利地为0.5重量%至30重量%，优选1重量%至15重量%。
在其中所述固定床催化剂包含镍的情况下，以氧化镍(NiO)的重量表达的镍含量有利地低于10重量%，优选低于6重量%。
有利地，所述固定床催化剂进一步以10重量%或更少，优选5重量%或更少的量包含磷和/或氟。
所述固定床催化剂有利地为挤出物或珠粒形式。所述固定床催化剂的尺寸为0.1mm至10 mm，优选0.5 mm至7 mm并更优选0.5 mm至5 mm。
优选地，所述固定床催化剂使用常规方法例如共混合或浸渍然后进行一个或多个热处理制备。
所述固定床催化剂有利地在其经历通过硫化或通过还原而活化的步骤之后使用。
根据本发明，将包含分散催化剂或分散催化剂前体的溶液连续引入所述反应器。所述分散催化剂可以有利地原位地、在反应器内、在用于加氢处理步骤的反应条件下、从所述分散催化剂的前体起始，或非原位地在反应器外部形成。优选地，所述分散催化剂原位地从所述分散催化剂前体形成。
根据本发明，所述分散催化剂具有1 nm至100 µm的尺寸。优选地，所述分散催化剂具有10 nm至75 µm的尺寸，并更优选具有100 nm至50 µm的尺寸。
有利地，将包含所述分散催化剂或所述分散催化剂前体的所述溶液与所述进料或与输送流体(conveying fluid)一起连续引入，所述分散催化剂没有沉积在固体载体上。
在所述溶液与输送流体一起引入的情况下，所述流体选自单独的或作为混合物的芳烃和减压馏出物。
将所述溶液通过至少一个反应器入口连续地引入，所述入口位于反应器中的不同高度，在反应器的底部、在反应器的顶部或在反应器的底部和顶部之间的任何点。
在溶解之前，所述分散催化剂或所述分散催化剂前体为固体形式或为液体形式。
在所述分散催化剂或所述分散催化剂前体为固体形式的情况下，其有利地选自黄铁矿和硫化钼。
在其中所述分散催化剂或所述分散催化剂前体为液体形式的情况下，其有利地选自在有机或水性介质中的可溶性金属的前体，并优选选自环烷酸钼、环烷酸镍、环烷酸钒、磷钼酸、钼酸铵、辛酸钼，特别是2-乙基己酸钼、辛酸镍、辛酸钒和五羰基铁。
所述分散催化剂原位地或非原位地，通过在氢气中还原或通过硫化进行活化。
相对于进料，在一个或多个反应器中的分散催化剂的量为1 ppm按重量计至10000ppm按重量计，并优选为10 ppm按重量计至300 ppm按重量计。
所述分散催化剂沉积在固定床催化剂上，这意味着活性相能够保留在载体上，即使所述固定床催化剂总是部分被焦化。此外，沉积分散催化剂在固定床催化剂上意味着能够无需与最终流出物分离的步骤。
附图的简要描述
图1为表示根据现有技术和根据本发明的为了补偿催化剂失活而需要的温度升高曲线的图。
实施例
实施例N°1:
实施例1：固定床加氢处理（并非根据本发明）
实施例1为并非根据本发明的，其既不是分散催化剂，也不是注入的分散催化剂前体。
在15 MPa的压力和0.8 h-1的HSV下在氢气存在下加氢处理含4重量%硫和90 ppm按重量计的金属的具有0.99的D 15/4密度的常压蒸馏渣油。为补偿催化剂活性的降低，随时间升高反应器的温度。
所使用的催化剂的活性相包含4%的钼。所述活性相沉积在具有1 mL/g的孔体积的氧化铝类型的载体上。大孔体积为总孔体积的40%，其中中值大孔直径为1000 nm。
通过加氢处理产生的流出物具有0.95的D 15/4密度和30 ppm按重量计的金属含量。
图1中的实线示出为了补偿反应介质失活的该反应介质的温度升高的曲线。所使用的最初温度为T基线。在相对于T基线升高温度70℃之后，该温度对于加氢处理以能够产生高品质产品而言过高。在反应5800 h之后达到T基线 + 70℃。
实施例2：采用连续引入分散催化剂的固定床加氢处理（根据本发明）
在实施例2中进行的方法类似于实施例1中进行的方法，但伴随常压蒸馏渣油另外连续注入钼在瓦斯油中的溶液。
将钼前体、2-乙基己酸钼与减压馏出物混合从而在反应器中获得相对于进料10ppm按重量计的量的分散催化剂。
通过加氢处理产生的流出物具有0.95的D 15/4密度和30 ppm按重量计的金属含量。
图1中的虚线示出为了补偿反应介质失活而该反应介质温度升高的曲线。在反应7900 h之后达到温度T基线 + 70℃，高于该温度时加氢处理不再能进行从而获得高品质的产物。
图1示出在根据本发明的方法中温度升高较缓慢。因此，根据本发明的方法可以用于显著地提高循环时间2100 h，即约36%。

Claims (15)

1.一种加氢处理重油进料的方法，所述方法在至少一个反应器中进行，该反应器包含由沉积在固体载体上的活性相构成的固定床催化剂，其中将包含分散催化剂或分散催化剂前体的溶液连续引入所述反应器中，所述分散催化剂的粒度为1 nm至100 µm，所述固定床催化剂在其固体载体上捕获所述分散催化剂。
2.权利要求1要求保护的方法，其中所述分散催化剂的粒度为10 nm至75 µm。
3.前述权利要求任一项中要求保护的方法，其中所述进料选自由从粗油或从粗油的常压蒸馏或从粗油的减压蒸馏获得的烃级分所构成的进料，所述进料包含至少80重量%的分子具有至少300℃的沸点的级分。
4.前述权利要求任一项要求保护的方法，其中所述加氢处理方法在2 MPa至38 MPa的绝对压力下和在300℃至550℃的温度下，采用0.05 h-1至10 h-1的进料体积相对于催化剂体积的小时空速(HSV)进行。
5.前述权利要求任一项要求保护的方法，其中所述固定床催化剂包含沉积在所述固体载体上的来自元素周期表的第4至12族的一种或多种元素。
6.权利要求5要求保护的方法，其中所述固定床催化剂的固体载体选自无定形固体，其选自单独的或作为混合物的二氧化硅、氧化铝、二氧化硅-氧化铝、二氧化钛和沸石。
7.权利要求5或权利要求6要求保护的方法，其中所述固定床催化剂的固体载体的大孔体积占总孔体积的0至80%，所述固定床催化剂的固体载体的大孔的中值直径为100 nm至5000 nm，所述固定床催化剂的固体载体的比表面积为大于75 m2/g。
8.权利要求5至7任一项要求保护的方法，其中所述固定床催化剂包含至少一种来自第VIB族的金属。
9.权利要求8要求保护的方法，其中所述来自第VIB族的金属选自钼和钨。
10.权利要求8至9任一项要求保护的方法，其中所述来自第VIB族的金属与至少一种来自第VIII族的金属结合使用。
11.权利要求10中要求保护的方法，其中所述来自第VIII族的金属选自镍和钴。
12.前述权利要求任一项要求保护的方法，其中将包含所述分散催化剂或所述分散催化剂前体的所述溶液与所述进料或与输送流体一起连续引入。
13.权利要求12要求保护的方法，其中所述输送流体选自单独的或作为混合物的芳烃和减压馏出物。
14.前述权利要求任一项要求保护的方法，其中所述分散催化剂或所述分散催化剂前体选自黄铁矿和硫化钼，或选自环烷酸钼、环烷酸镍、环烷酸钒、磷钼酸、钼酸铵、辛酸钼、辛酸镍、辛酸钒和五羰基铁。
15.前述权利要求任一项要求保护的方法，其中相对于所述进料，在一个或多个反应器中的分散催化剂的量为1 ppm按重量计至10000 ppm按重量计。
CN201680074175.4A 2015-12-21 2016-12-02 在杂合反应器中通过捕获分散催化剂改善重质产物的方法 Pending CN108603127A (zh)

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PCT/EP2016/079647 WO2017108377A1 (fr) 2015-12-21 2016-12-02 Procede de valorisation de produits lourds en reacteur hybride avec captation d'un catalyseur disperse

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CN1950483A (zh) * 2004-04-28 2007-04-18 上游重油有限公司 固定床加氢处理法和系统，以及用来升级已有固定床系统的方法
CN103861627A (zh) * 2012-12-18 2014-06-18 Ifp新能源公司 包含钒的渣油加氢处理催化剂及其用途

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US7816299B2 (en) * 2003-11-10 2010-10-19 Exxonmobil Research And Engineering Company Hydrotreating catalyst system suitable for use in hydrotreating hydrocarbonaceous feedstreams
CN103228355A (zh) * 2010-12-20 2013-07-31 雪佛龙美国公司 加氢加工催化剂及其制备方法
FR3011842B1 (fr) * 2013-10-10 2015-12-18 IFP Energies Nouvelles Procede optimise de conversion de la biomasse avec ajout de catalyseur disperse

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CN103861627A (zh) * 2012-12-18 2014-06-18 Ifp新能源公司 包含钒的渣油加氢处理催化剂及其用途

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MX2018007491A (es) 2018-08-01
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WO2017108377A1 (fr) 2017-06-29

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