CN104066819B - 用于fcc工艺的改进的金属钝化剂/捕获剂 - Google Patents
用于fcc工艺的改进的金属钝化剂/捕获剂 Download PDFInfo
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- CN104066819B CN104066819B CN201180076265.4A CN201180076265A CN104066819B CN 104066819 B CN104066819 B CN 104066819B CN 201180076265 A CN201180076265 A CN 201180076265A CN 104066819 B CN104066819 B CN 104066819B
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- kaolin
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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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Abstract
本发明提供了包含FCC催化剂和金属钝化剂/捕获剂的催化剂混合物,及其在烃原料的催化裂化过程中捕获金属污染物的用途。
Description
技术领域
本发明提供了金属钝化剂/捕获剂和减轻金属对烃原料的催化裂化的有害作用的方法。通过使用混合金属添加剂作为金属污染物的钝化剂和捕获剂,实现这一目的。
背景技术
催化裂化是商业上大规模应用的石油炼制工艺。美国大约50%的炼油厂汽油调合池由这种工艺生产,几乎所有都使用流化催化裂化(FCC)工艺生产。在FCC工艺中,重烃馏分通过在高温下在催化剂存在下发生的反应转化成较轻产物,其中大部分转化或裂化在气相中进行。FCC烃原料(原料)由此转化成汽油和其它液态裂化产物以及每分子四个或更少碳原子的较轻气态裂化产物。这些液态和气态产物由饱和和不饱和烃构成。
在FCC工艺中,将原料注入FCC反应器的提升管段,在此原料在与从催化剂再生器循环至提升管反应器的热催化剂接触时裂化成更轻更有价值的产物。随着发生吸热裂化反应,碳沉积到催化剂上。这种碳(被称作焦炭)降低了催化剂活性,且催化剂必须再生以恢复其活性。催化剂和烃蒸气沿提升管上升至FCC反应器的分离段,在此它们分离。随后催化剂流入汽提段,在此通过蒸汽喷射汽提随催化剂夹带的烃蒸气。在从废裂化催化剂中除去夹带的催化剂后,汽提过的催化剂流经废催化剂立管并进入催化剂再生器。
通常,通过将空气引入再生器并烧除焦炭以恢复催化剂活性,再生催化剂。这些焦炭燃烧反应高度放热,因此加热催化剂。热的再活化的催化剂经再生催化剂立管流回提升管以完成催化剂周期。焦炭燃烧废气流升至 再生器顶部并经由再生器烟道离开再生器。该废气通常含有氮氧化物(NOx)、硫氧化物(SOx)、一氧化碳(CO)、氧气(O2)、HCN或氨、氮和二氧化碳(CO2)。
因此可以区分裂化催化剂经受的FCC工艺的三个特有步骤:1)裂化步骤,其中将原料转化成较轻产物,2)汽提步骤,以除去吸附在催化剂上的烃,和3)再生步骤,以烧除沉积在催化剂上的焦炭。再生的催化剂然后再用于裂化步骤。在60年代早期。随着分子筛或沸石的引入,迎来FCC催化剂中的主要突破。这些材料并入构成当时的FCC催化剂的非晶和/或非晶/高岭土材料中。含有在二氧化硅、氧化铝、二氧化硅-氧化铝、高岭土、粘土等的非晶或非晶/高岭土基质中的结晶硅铝酸盐沸石的这些新型沸石催化剂在烃裂化方面的活性比早期的含有二氧化硅-氧化铝催化剂的非晶或非晶/高岭土高至少1,000-10,000倍。沸石裂化催化剂的这种引入彻底革新了催化裂化工艺。开发出了应对这些高活性的新工艺,例如提升管裂化、缩短的接触时间、新再生工艺、新的改进的沸石催化剂发展等。
新的催化剂发展以下述内容为中心:各种沸石(例如合成X和Y型和天然存在的八面沸石)的发展;通过经离子交换技术加入稀土离子或铵离子而提高沸石的热-蒸汽(水热)稳定性;和用于负载沸石的更耐磨基质的发展。沸石催化剂发展使得石油工业能在使用相同装置而不扩张并且不需要新的装置构造的同时在提高的转化率和选择性下大大提高原料处理量。
在引入含沸石的催化剂后,伴随着对辛烷值不断提高的汽油的需求日益增长,石油工业开始受困于原油的量和品质的可得性。全球原油供应状况在60年代末70年代初急剧改变。供应状况从过剩的轻质低硫原油变成紧缩供应,而重质原油,如具有较高硫含量的石油渣油的量不断增长。
石油渣油是石油原油在大气压下(常压渣油)或在减压下(减压渣油)的蒸馏后留下的重馏分。渣油具有高分子量并通常含有多环芳烃(PAH's)。这些分子具有多于3-4个芳环并最大限制渣油转化成所需产物。这是因为它们的高稳定性和在环结构中缺乏足够的氢以致无法转化成更小更有用的分子。此外,所需产物,例如运输燃料仅限于烷基化单一芳环。无论采用哪种类型的渣油转化工艺,相当大比例的渣油分子具有可以在运输燃料和真空油沸程中裂化成液体(或气体)的片段。在FCC裂化条件下无法裂化芳核(为了也除去这些物类,必须考虑加氢裂化)。因此,不应尝试过度转化渣油,因此选择性随之会移向热力学上有利但价值较低的产物:焦炭和气态烃。因此,在渣油FCC加工中汽油产率较低。这些重质和高硫原油和渣油为炼油商带来加工问题,即这些重质原油始终还含有重得多的金属,伴随着显著提高的沥青含量。典型的污染金属是镍、钒和铁。
长期已知的是,具有高污染金属含量的拔顶原油、渣油和拔顶油存在严重问题,例如降低对有价值的运输燃料的选择性和在相对较高的金属浓度(例如5,000-10,000ppm)以及升高的再生器温度下使FCC催化剂失活。还特别认识到,当在含结晶沸石的催化剂上加工具有高钒和镍含量的含拔顶油的进料时,尤其是在该催化剂上具有高钒含量时,发生沸石的快速失活。这种失活实质表现为结晶沸石结构的损失。在1,000ppm或更低的钒含量下已观察到这种损失。随着钒含量提高,结晶沸石结构的损失变得更快更严重,在大约5,000ppm的钒含量下,特别是在接近10,000ppm的含量下,可能发生沸石结构的完全破坏。通过提高原始催化剂的添加速率,可以降低在小于10,000ppm的钒含量下的钒失活效应,但这样做在经济上昂贵。如上所述,钒毒化裂化催化剂并降低其活性。这一领域中的文献已报道,原料中存在的钒化合物并入沉积在裂化催化剂上的焦炭中,其随后在再生器中在烧除焦炭时氧化成五氧化钒(M.Xu等人.J.Catal.V.207(2),237-246)。在空气和蒸汽存在下在700-830℃下,V将以酸性形式呈表面活动状态。这种V物类与阳离子钠反应,以促进其从Y交换位点释放。由此形成的偏钒酸钠在蒸汽中水解形成NaOH和偏钒酸,其再与Na+阳离子反应。V由此催化破坏性的NaOH的形成。
另一方面,铁和镍不活动。含镍的烃沉积在催化剂上并在再生器中形成氧化镍。在提升管段中,其可能还原成金属镍,其类似于金属铁,催化烃脱氢形成不想要的氢和焦炭。高的氢产率是不合意的,因为其造成FCC下游操作中的限制(湿气压缩机的体积有限)。另外,高焦炭量会造成再 生器鼓风机限制,这可能导致降低的进料处理量。
由于含有钒和其它金属的化合物通常不容易作为挥发性化合物从裂化单元中除去,常见方法是在裂化工艺过程中遇到的条件下捕获和/或钝化这些化合物。捕获或钝化可能涉及将添加剂掺入裂化催化剂中或与裂化催化剂一起加入单独的添加剂粒子。这些添加剂与金属组合并因此充当活动V物类的“捕获剂(traps)”或“下降剂(sinks)”,以保护裂化催化剂的活性组分,或充当不活动的Ni和Fe的钝化剂。然后与在正常运行过程中从该系统中取出的催化剂一起除去金属污染物,并与补充催化剂一起加入新鲜金属捕获剂,以实现在运行过程中连续除去有害的金属污染物。根据原料中的有害金属含量,可以相对于补充催化剂改变添加剂的量以实现所需的金属捕获和/或钝化程度。
已知在FCC催化剂粒子中掺入各种类型的氧化铝以捕获钒和镍。其实例可见于共同转让的美国专利Nos.6,716,338和6,673,235,它们将可分散的勃姆石添加到裂化催化剂中。在煅烧时,勃姆石转化成过渡氧化铝相,该过渡氧化铝相已被发现可用于烃原料中的镍和钒污染物的钝化。同时,高表面积氧化铝也可用于捕获钒,以保护沸石,但不是钝化钒,以致污染物氢和焦炭的含量仍然高。
也可以使用含碱土金属的捕获剂(Ca、Mg、Ba)和/或稀土基捕获剂捕获并有效钝化钒,参见共同转让并共同待审的申请12/572,777;美国专利Nos.4,465779;4549,548;5300,496;7,361,264;WO82/00105;GB 218314;EP A020151和EP A0189267。但是,这些捕获剂对硫敏感,硫可能堵塞用于钒捕获的活性位点以致它们效率变低。
锑和锑化合物作为钝化剂的应用也是专利文献中公知的,包括美国专利Nos.3,711,422;4,025,458;4,031,002;4,111,845;4,148,714;4,153,536;4,166,806;4,190,552;4,198,317;4,238,362和4,255,287。据报道,锑与镍反应形成NiSb合金,其在提升管条件下难还原,由此使用于催化氢和焦炭形成的镍失活。这一过程常被称作钝化。
在共同转让的U.S.7,678,735中,描述了将氨氧化催化剂添加到FCC 再生器,以降低FCC催化剂再生过程中的NOx和NOx前体排放。特别有用的氨氧化催化剂是铁锑和另一金属(例如Mg、Mn、Mo、Ni、Sn、V或Cu)的混合氧化物。在该专利中没有提到氨氧化催化剂在渣油裂化中、特别是在可毒化和/或钝化沸石裂化催化剂的镍和钒污染物的捕获和/或钝化中的特定效用。
发明概述
本发明涉及改进的金属钝化剂/捕获剂,其包含锑、至少一种氧化还原元素和任选地助催化剂的混合金属氧化物,及其在烃原料的催化裂化过程中捕获金属污染物的用途。
附图简述
为了更充分理解本发明的性质和优点,应该参考联系附图阅读的下列详述。
图1图解由含有铁/锑添加剂和被3000ppm Ni金属化的的FCC催化剂在各种转化率下带来的以重量%计的H2产率的降低。
图2图解由含有铁/锑添加剂和被3000ppm V金属化的的FCC催化剂在各种转化率下带来的以重量%计的H2产率的降低。
图3图解随着作为金属钝化剂/捕获剂与被3000ppm Ni和3000ppmV污染的FCC催化剂一起使用的铁/锑添加剂的量提高,以重量%计的H2产率的降低。
发明详述
本发明涉及改进的金属钝化剂/捕获剂,及其与FCC催化剂一起用于催化含有显著量的金属污染物(即Ni和/或V)的石油进料的用途。具体而言,该金属钝化剂/捕获剂包含金属氧化物的混合物,以固定钒和镍,以降低烃油进料中的金属污染物对FCC催化剂的减活化作用和/或提高对运输燃料的选择性(FCC操作中使用的所有类型)。本发明特别可用于在现代流化催化裂化单元中加工全原油、拔顶原油、渣油和拔顶油进料中存在的碳-金属(carbo-metallic)油组分。
本发明的方法包括使用催化剂混合物的烃质原料的催化裂化,所述催化剂混合物包含第一组分——其是优选包含在基质材料内的裂化催化剂,和第二组分——其包含具有金属钝化和金属捕获效力的如上所述的混合金属氧化物合金。本发明的改进在于甚至在原料含有高量金属时该催化剂体系也正常运作的能力。
必须指出,“钝化剂”和“捕获剂”不可互换使用,且本发明的金属氧化物的混合物含有钝化或者捕获金属污染物的组分。“钝化剂”是指降低不想要的金属(即镍和钒)在FCC工艺过程中产生污染物H2和焦炭的活性的组合物。而“捕获剂”是固定污染物金属(即V和Na)的组合物,不然,所述污染物金属在FCC催化剂混合物中的微球内或之间自由迁移。钝化剂可能不一定固定V,而捕获剂当然可能不钝化V。
裂化催化剂
本发明的方法中所用的裂化催化剂组分可以是具有显著活性的任何所需类型的任何裂化催化剂。优选地,本发明所用的催化剂是下述催化剂:其含有结晶的硅铝酸盐,优选为铵交换的和至少部分被稀土金属阳离子交换的,且有时被称作“稀土交换的结晶硅铝酸盐”,即REY、CREY或REUSY;或稳定化的铵或氢沸石之一。
本发明中用作催化裂化催化剂的具有裂化活性的典型沸石或分子筛是本领域中公知的。合成的沸石最初为碱金属硅铝酸盐形式。通常使碱金属离子与稀土金属和/或铵离子交换以赋予该沸石裂化特征。该沸石是含有通过较小的相对均匀空穴或通道互连的大量均匀开孔或空腔的结晶三维稳定结构。合成沸石的有效孔径合适地为6至直径,但不限于此。
本发明中可用的沸石包括天然和合成沸石。这些沸石包括钠菱沸石、菱沸石、环晶石、斜发沸石、八面沸石、片沸石、方沸石、插晶菱沸石、毛沸石、方钠石、钙霞石、霞石、青金石、钙沸石、钠沸石、菱钾铝矿、 中沸石、发光沸石、锶沸石、镁碱沸石等。八面沸石是优选的。可根据本发明处理的合适的合成沸石包括沸石X,Y,包括化学或水热脱铝的高硅/铝Y、A、L、ZK-4、β、ZSM类型或pentasil、boralite和ω。本发明所用的术语“沸石”不仅涉及硅铝酸盐,还涉及铝被镓或硼替代的物质和硅被锗替代的物质。用于本发明的优选沸石是Y和X类型的合成八面沸石或其混合物。或者,来自BASF Corporation的被称作的催化剂也可用。用于本发明的催化剂的量为该催化剂混合物的大约30至大约95重量%。大约50%至大约90%的量也是有用的。
为了获得良好的裂化活性,沸石必须为适当的形式,在大多数情况下这涉及将沸石的碱金属含量降至尽可能低的水平。此外,高碱金属含量降低热结构稳定性,并因此损害催化剂的有效寿命。除去碱金属并使沸石呈适当形式的程序是本领域中公知的,例如如美国专利No.3,537,816中所述。
该沸石可被并入基质中。合适的基质材料包括天然存在的粘土,例如高岭土、埃洛石和蒙脱石,和包含非晶催化无机氧化物,例如二氧化硅、二氧化硅-氧化铝、二氧化硅-氧化锆、二氧化硅-氧化镁、氧化铝-氧化硼、氧化铝-二氧化钛等及其混合物的无机氧化物凝胶。该无机氧化物凝胶优选是含二氧化硅的凝胶,该无机氧化物凝胶更优选是非晶二氧化硅-氧化铝组分,例如传统的二氧化硅-氧化铝裂化催化剂,其中几种类型和组合物可购得。这些材料通常作为二氧化硅和氧化铝的共凝胶、共沉淀的二氧化硅-氧化铝或作为沉淀在预形成并预老化的水凝胶上的氧化铝制备。通常,二氧化硅作为主要组分存在于此类凝胶中存在的催化固体中,以大约55至100重量%的量存在。但是,最通常,活性商业FCC催化剂基质衍生自拟薄水铝石、勃姆石和颗粒状水合或可再水合的氧化铝,例如三羟铝石、三水铝石和快速煅烧的三水铝石,并与可胶溶的拟薄水铝石和/或胶态二氧化硅或与羟基氯化铝(aluminum chlorohydrol)结合。基质组分可以合适地以FCC催化剂的大约25至大约92重量%、优选大约30至大约80重量%的量存在于本发明的催化剂中。
美国专利No.4,493,902——其教导内容通过交叉引用并入本文——公 开了包含含有大于大约40%、优选50-70重量%Y八面沸石的耐磨、高沸石含量的催化活性微球的新型流化裂化催化剂,和通过使大于大约40%钠Y沸石在由两种不同形式的化学反应性煅烧粘土——即偏高岭土(煅烧以发生与脱羟基相关联的强吸热反应的高岭土)和在比用于将高岭土转化成偏高岭土的那些条件更剧烈的条件下煅烧的高岭粘土,即煅烧以发生特有的高岭土放热反应的高岭粘土,有时被称作尖晶石形式的煅烧高岭土——的混合物构成的多孔微球中结晶来制造此类催化剂的方法在一个优选实施方案中,将含有这两种形式的煅烧高岭土的微球浸在碱性硅酸钠溶液中,将其加热,优选直至在该微球中结晶最大可获得量的Y八面沸石。
在'902技术的实践中,在其中结晶该沸石的多孔微球优选如下制备:形成粉状粗制(水合)高岭土(Al2O3:2SiO2:2H2O)和已经与次要量的硅酸钠(其充当该浆料的流化剂)一起发生放热的粉状煅烧高岭土的含水浆料,将其装入喷雾干燥器以形成微球,然后用于为喷雾干燥的微球的组分提供物理完整性。然后将含有水合高岭土和煅烧至发生放热的高岭土的混合物的喷雾干燥的微球在比使高岭土发生放热所需的条件温和的受控条件下煅烧,以使该微球的水合高岭土部分脱水并使其转化成偏高岭土,这产生含有偏高岭土、煅烧至发生放热的高岭土和硅酸钠粘合剂的所需混合物的微球。在'902专利的示例性实施例中,大约等重量的水合粘土和尖晶石存在于喷雾干燥器进料中,所得煅烧微球含有略多于偏高岭土的已发生放热的粘土。'902专利教导了该煅烧微球包含大约30-60重量%偏高岭土和大约40-70重量%以其特有的放热为特征的高岭土。该专利中描述的较不优选的方法涉及将含有预先煅烧偏高岭土条件的高岭土和煅烧至发生放热的高岭土的混合物的浆料喷雾干燥,但在该浆料中不包括任何水合高岭土,由此直接提供含有偏高岭土和煅烧至发生放热的高岭土的微球,而不将水合高岭土煅烧转化成偏高岭土。
在实施'902专利中描述的发明时,由煅烧至发生放热的高岭土和偏高岭土构成的微球在结晶引发剂(晶种)存在下与富含碱的硅酸钠溶液反应以将微球中的二氧化硅和氧化铝转化成合成钠八面沸石(沸石Y)。将微 球与硅酸钠母液分离,与稀土离子、铵离子或两者离子交换以形成稀土形式或各种已知的稳定化形式的催化剂。'902专利的技术提供了实现高沸石含量与高活性、良好选择性和热稳定性以及耐磨性的合意和独特组合的方式。
金属钝化剂/捕获剂
本发明的金属钝化剂/捕获剂减轻在瓦斯油和渣油的FCC裂化过程中裂化催化剂的钒侵袭和镍脱氢。
本发明中用于钝化/捕获的成功的混合金属氧化物催化剂由被称作RSbM的混合物构成,其中R是选自Fe2+/3+、Ce3+/4+、Cr2+/3+、U5+/6+、Sn或Mn的至少一种氧化还原元素,其作用是由O2制造晶格氧,然后用这种晶格氧补充Sb3+/5+活性位点,它们各自可通过添加选自Na、Zn、W、Te、Ca、Ba、Mo、Mg、Mn、Sn或Cu的氧化物的至少一种任选助催化剂M进一步改进。
特别地,本发明涉及使用在载体上的铁-锑(FeSb)钝化和/或捕获Ni和V,其中在提升管的还原性气氛中发生与镍的反应,同时在再生器的氧化性气氛中发生钒的吸收。下列方程式阐述这一反应:
Fe2Sb2O8+NiO+V2O5→2FeVO4+NiSb2O6
尽管铁已知是催化剂毒物并导致形成氢和焦炭,但出乎意料地发现,Fe和Sb的组合降低了氢和焦炭的产率。
制备具有低表面积的FeSb以限制H2形成。Sb是活动的以使Sb可以找到和钝化催化剂上的Ni。由于Sb和V在化学上类似(V也是活动的),FeOx可以与V反应形成FeVOx。FeVOx适合作为含有SOx的再生器气体中的非硫化钒酸盐。不希望受制于任何操作理论,但我们相信,FeSb结构促进V进入或交换到氧化铁结构中。
R:Sb:M比率对催化结果也重要。R:Sb:M的原子比可以为0.1-10比0.1-10比0-10,优选0.5-3比0.5-3比0-5。
该金属钝化剂/捕获剂可以在引入FCC单元之前与单独的沸石催化剂 粒子掺合。或者,可以将该钝化剂/捕获剂粒子单独装入裂化单元中的循环催化剂存货中。金属钝化粒子通常以该催化剂混合物的1至50重量%,优选2至30重量%,最优选5至25重量%范围内的量存在。当用量不足时,钒和镍钝化的改进不足。当过量使用时,可能损害裂化活性和/或选择性,且该操作变昂贵。最佳比例随油进料内的金属污染物含量而变。
相应地,由于金属捕获组分充当活动金属污染物的清除剂以防止此类污染物到达催化活性组分的裂化中心,可以调节该钝化剂/捕获剂在该催化剂混合物中的浓度以保持所需的催化剂活性和转化率,优选至少55%的转化率。本发明的钝化剂/捕获剂特别可用于裂化含有大约0.1ppm镍和/或0.1ppm钒浓度的金属污染物(即Ni和/或V)至大约200ppm的包含镍、钒和/或其混合物的金属污染物的油进料。但是,必须指出,在FCC裂化过程中,积聚在FCC催化剂上的金属污染物的量可以为少至300ppm至高达40,000ppm的包含镍、钒和/或其混合物的金属污染物。
载体
惰性载体材料可用于负载该金属钝化剂/捕获剂。该载体材料选自,但不限于:(i)含原位FCC的沸石,(ii)煅烧的高岭土,(iii)氧化铝或(iv)二氧化硅。如果使用二氧化硅,可以添加锆以提供热稳定性。氧化铝(例如Sasol生产的)是可用的。微球形式的煅烧高岭土是优选的。制造用于本发明的载体的方法可见于共同转让的美国专利No.7,678,735,其经此引用并入本文。所用载体的量为该催化剂混合物的大约1重量%至99重量%,优选5重量%至95重量%。该载体优选具有大约5至200平方米/克的表面积。
本发明的组合物的制备(浸渍)
该RSbM金属钝化剂/捕获剂通常如下制备:1)用锑溶液浸渍载体;2)用氧化还原元素的溶液浸渍来自1)的加工过的载体,以便仅填充载体微球的一部分孔隙体积,和3)用浓氢氧化铵溶液填充剩余部分的孔隙体积。 相应地,可以使用氯化锑或三氧化锑制备锑溶液。
所用铵的量通常等于硝酸盐+氯化物的当量。这提供中性pH,且溶解的金属在初湿体积下沉淀在微球内。如果干燥,夹带的硝酸铵盐会是爆炸性的。因此,应该使浸渍的微球反应大约30分钟,然后用去离子水制浆,过滤并洗涤以除去盐,以使RSbM水凝胶留在微球中。然后煅烧该氢氧化物混合物。如果使用助催化剂(M),该助催化剂可以与第二浸渍中的氧化还原元素或第三浸渍中的氨溶液结合,以使各溶液保持完全溶解并调节总体当量以在浸渍酸性和碱性溶液后提供中性。
或者,可以在浸渍到惰性载体上之前将氧化还原元素直接添加到锑中。特别地,在第二合成步骤中通过添加氧化还原元素的一种或多种金属盐(即硝酸盐、氯化物或乙酸盐)使金属阳离子并入锑结构中:
Fe(OAc)2+2Sb+5(OH)3O+2H2O--->Fe+2[Sb+5(OH)4O]2+2HOAc
在没有载体的情况下,也可以通过在制造过程中(高岭土的喷雾干燥、然后煅烧)引入金属盐或通过Fe和Sb盐的共沉淀制备该钝化剂/捕获剂,参见Allen等人.,Appl.Catal.A.Gen.,217(2001),31。
用途
根据上述方法的反应温度为至少大约900°F(482℃)。上限可以为大约1100°F(593.3℃)或更高。优选温度范围为大约950°F至大约1050°F(510℃至565.6℃)。反应总压力可以广泛变化,并可以为例如大约5至大约50psig(0.34至3.4大气压)或优选大约20至大约30psig(1.36至2.04大气压)。最大提升管停留时间为大约5秒,对大多数进料而言,停留时间为大约1.0至大约2.5秒或更短。对富含芳烃的高分子量进料而言,大约0.5至大约1.5秒的停留时间适合裂化单-和二-芳烃和环烷,它们是最容易裂化并产生最高汽油产率的芳烃,但在发生多环芳烃的显著裂化之前终止运行,因为这些材料产生高产率的焦炭和C2和较轻气体。反应器的长径比可以广泛变化,但该反应器应该细长以提供高线性速度,如大约25至大约75英尺/秒;为此,高于大约20至大约25的长径比是合适的。该 反应器可具有均一直径或可具有连续锥度或直径沿反应路径逐步提高以保持沿流径的几乎恒定速度。
改变催化剂与进料中的烃的重量比以影响反应器温度的变化。此外,再生催化剂的温度越高,实现给定反应温度所需的催化剂越少。因此,高再生催化剂温度允许下文阐述的极低反应器密度水平并由此有助于避免反应器中的回混。通常,催化剂再生可以在大约1250°F(676.6℃)或更高的升高的温度下进行。再生催化剂的催化剂上的碳从大约0.6至大约1.5,降至大约0.3重量%的水平。在常见的催化剂/油比率下,催化剂的量绰绰有余以实现所需催化作用,因此如果催化剂的温度高,可以安全地降低该比率而不损害转化。由于沸石催化剂例如对催化剂上的碳含量特别敏感,再生有利地在升高的温度下进行以将催化剂上的碳含量降至指定范围或更低。此外,由于催化剂的主要功能是向反应器供热,在任何给定的所需反应器温度下,催化剂进料的温度越高,需要的催化剂越少。催化剂进料速率越低,反应器中的材料密度越低。如所述,低反应器密度有助于避免回混。
要理解的是,上述催化剂混合物可用于含金属的任何烃进料的催化裂化,但特别可用于处理高金属含量进料。典型的原料是重瓦斯油或原油的重质馏分,其中富集金属污染物。使用本发明的催化剂混合物处理的特别优选的进料包括在大气压下在大约900°F(482℃)以上沸腾的脱沥青油;在大气压下在大约600°F至大约1100°F(343℃至593℃)沸腾的重瓦斯油;在大约650°F以上沸腾的常压或减压塔底液。
该金属钝化剂/捕获剂可以经由添加剂装载机以与CO助催化剂和其它添加剂相同的方式添加到FCC单元中。或者,该金属钝化剂/捕获剂可以与供应给FCC单元的新鲜FCC催化剂预掺合。
实施例1
制备包含Fe/Sb的混合物的钝化剂/捕获剂:
1.锑溶液;
在50毫升烧杯中称出适当量的Sb2O3,用水填充烧杯至30毫升,然后将混合物加热至70℃。加入H2O2并使混合物在70℃下保持1小时。发生下列反应:
Sb2O3+2H2O2+H2O--->2Sb(OH)3O
混合和加热产生乳白色胶态溶液。
2.将Sb氧化物-氢氧化物浸渍到惰性载体上:
将煅烧的高岭土载体置于碗中并滴入大约1/3来自步骤1的溶液。搅拌(wisped)该载体并用剩余2/3来自步骤1的溶液重复该过程。将浸渍载体置于Pyrex碗中并将该载体在通风100℃烘箱中干燥整夜。
3.铁溶液:
在50毫升烧杯中称出Fe(NO3)3·9H2O,用水填充烧杯至22毫升,然后混合组分直至Fe(NO3)3·9H2O溶解。
4.使用步骤2中所列的程序,用来自步骤3的铁溶液浸渍来自步骤2的加工过的惰性载体。使浸渍载体保持在室温下以使组分反应大约30分钟,然后用去离子水制浆,过滤并洗涤以除去未并入的粒子或盐。将浸渍载体(现在含有Fe和Sb)置于Pyrex碗中并在通风100℃烘箱中干燥整夜。将该载体冷却至室温,然后在通风烘箱中在400℃下煅烧该载体3小时。
实施例2
在来自实施例1的步骤后,制造各种Fe:Sb比的钝化剂/捕获剂:
表1
表2
表3
然后将钝化剂/捕获剂合并到预金属化的FCC催化剂内。将该组合在测试之前在90%蒸汽/10%空气流中在1450°F下蒸汽处理4小时:
表4
表5
实施例3
制造包含助催化剂的金属钝化剂/捕获剂:
1.在煅烧的高岭土上浸渍2.5%Sb2O3:2.5%Fe2O3:1%MnO2:
首先将3.91克SbCl3溶解在25毫升去离子水和15毫升HCl(37%)中,然后混入12.62克Fe(NO3)3·9H2O和3.53克Mn(NO3)3·4H2O。将40毫升该混合物施用到100克煅烧的高岭土上,充分混合,将该煅烧的高岭土在100℃干燥整夜(16小时)。将该浸渍载体在400℃在空气中进一步煅烧3小时。产率%为:3.0862%Fe2O3、1.0944%MnO2和2.2779%Sb2O3。
2.在煅烧的高岭土上浸渍2.5%Sb2O3:2.5%Fe2O3:1%WO3:
首先将3.91克SbCl3溶解在10毫升HCl(37%)和20毫升去离子水 中,其次将1.52克偏钨酸铵与5毫升HCl混合,然后加入12.65克Fe(NO3)3·9H2O。将30毫升该混合物施用到100克煅烧的高岭土上,充分混合,将该煅烧的高岭土在100℃干燥整夜(16小时)。将该浸渍载体在400℃下在空气中进一步煅烧3小时。产率%为3.37%Fe2O3、1.22%WO3和2.68%Sb2O3。
3.在煅烧的高岭土上浸渍2.5%Sb2O3:2.5%Fe2O3:1%ZnO:
将3.91克SbCl3溶解在20毫升HCl(37%)和15毫升去离子水中,然后加入12.62克Fe(NO3)3·9H2O和3.62克Zn(NO3)2。将35毫升该混合物施用到100克煅烧的高岭土上,充分混合,将该煅烧的高岭土在100℃下干燥整夜(16小时)。将该浸渍载体在400℃下在空气中进一步煅烧3小时。产率%为3.18%Fe2O3、0.843%ZnO和2.63%Sb2O3。
4.在煅烧的高岭土上浸渍2.5%Sb2O3:2.5%Fe2O3:1%SnO:
首先将3.91克SbCl3溶解在10毫升HCl(37%)中,然后加入12.65克Fe(NO3)3·9H2O和1.675克SnCl2·2H2O,用20毫升去离子水配平。将30毫升该混合物施用到100克煅烧的高岭土上,充分混合,将该煅烧的高岭土在100℃下干燥整夜(16小时)。将该浸渍载体在400℃下在空气中进一步煅烧3小时。产率%为2.78%Fe2O3、0.743%SnO和2.65%Sb2O3。
5.在煅烧的高岭土上浸渍2.5%Sb2O3:2.5%Fe2O3:1%MoO3:
首先将3.91克SbCl3溶解在20毫升去离子水和10毫升HCl(37%)中,然后加入12.65克Fe(NO3)3·9H2O和1.43克(NH4)2MoO4。将30毫升该混合物施用到100克煅烧的高岭土上,充分混合,将该煅烧的高岭土在100℃下干燥整夜(16小时)。将该浸渍载体在400℃下在空气中进一步煅烧3小时。产率%为:3.03%Fe2O3、1.36%MoO3和2.59%Sb2O3。
实施例4
通过添加适当量的镍和环己烷,将样品J和K中的Flex-Tec金属化至3000ppm镍,混合并倒在堇青石托盘上以风干,然后在315℃下烧制和在593℃下煅烧。然后将钝化剂/捕获剂并入预金属化的FCC催化剂内。将该组合在测试之前在90%蒸汽/10%空气中在1450°F下蒸汽处理4小时。
在ACE流化床烃裂化单元上使用烃油进料测量氢产率。在图1中表明,在该催化剂的各种转化率下,样品K的以重量%计的氢产率比样品J(对照样品)低15%。
通过添加适当量的钒和环己烷,将样品L和M中的Flex-Tec金属化以含有3000ppm钒,混合并倒在堇青石托盘上以风干,然后在315℃下烧制和在593℃下煅烧。然后将钝化剂/捕获剂并入预金属化的FCC催化剂内。该组合在测试之前在90%蒸汽/10%空气中在1450°F下蒸汽处理4小时。
在ACE流化床烃裂化单元上使用烃油进料测量氢产率。在图2中表明,在该催化剂的各种转化率下,样品M的以重量%计的氢产率比样品J(对照样品)低20%。
通过添加适当量的钒、镍和环己烷,将样品N、O、P、Q和R中的Flex-Tec金属化至3000ppm镍和3000ppm钒,混合并倒在堇青石托盘上以风干,然后在315℃烧制和在593℃煅烧。在ACE流化床烃裂化单元上使用烃油进料测量汽提的烃速率和烃产率。表6显示样品P和T在75%转化率下的烃产率:
表6
沸石催化剂与沸石催化剂+Fe/Sb钝化剂/捕获剂的FCC裂化的比较
可以看出,H2和焦炭显著减少(>30%),而合意产物(汽油和LPG)的产率提高。基于样品R、Q、P、O和N的70%转化率相对于以重量%计的H2收率绘制图3。在图3中表明,随着Fe/Sb钝化剂/捕获剂的量提高(样品N、O、P和Q),H2收率最终由对照物(样品R)降低大约28%。
Claims (22)
1.在FCC单元床中钝化和/或捕获来自烃油进料的至少一种金属污染物的方法,其包括:使含有所述至少一种金属污染物的所述烃油进料与催化剂混合物接触,所述催化剂混合物包含1)FCC催化剂,和2)金属钝化剂/捕获剂,该金属钝化剂/捕获剂包含R、Sb和任选地M的混合物,其中R是氧化还原元素,选自Fe2+/3+、Ce3+/4+、Cr2+/3+、U5+/6+、或Mn,且M是任选的助催化剂。
2.权利要求1的方法,其中所述烃油进料选自瓦斯油、渣油、拔顶油及其混合物。
3.权利要求1的方法,其中所述助催化剂M选自下述元素的氧化物:Na、Zn、W、Te、Mo、Ca、Ba、Mg、Mn、Sn或Cu。
4.权利要求1的方法,其中所述至少一种金属污染物选自镍、钒或其混合物。
5.权利要求1的方法,其中所述烃油进料包含渣油。
6.权利要求1的方法,其中所述金属污染物以至少0.1ppm的量存在于所述烃油进料中。
7.权利要求1的方法,其中所述金属污染物以最多达200ppm的量存在于所述烃油进料中。
8.权利要求1的方法,其中在使所述烃油进料与所述催化剂混合物接触后,所述FCC催化剂具有至少300ppm的所述金属污染物积聚量。
9.权利要求1的方法,其中在使所述烃油进料与所述催化剂混合物接触后,所述FCC催化剂具有最多达40,000ppm的所述金属污染物积聚量。
10.权利要求1的方法,其中所述R是Fe2+/3+。
11.权利要求3的方法,其中所述M是Zn、W、Mo、Mn或Sn的氧化物。
12.权利要求1的方法,其中R:Sb:M的原子比为0.1-10比0.1-10比0-10。
13.权利要求12的方法,其中R:Sb:M的所述原子比为0.1-3比0.1-3比0-5。
14.权利要求1的方法,其中所述金属钝化剂/捕获剂另外含有选自i)原位沸石、ii)煅烧的高岭土、iii)氧化铝和iv)SiO2中的一种或多种的载体。
15.权利要求14的方法,其中所述载体是煅烧的高岭土。
16.权利要求14的方法,其中所述载体以所述钝化剂/捕获剂的5至70重量%的量存在。
17.权利要求1的方法,其中所述钝化剂/捕获剂以所述催化剂混合物的1重量%至25重量%的量存在。
18.权利要求1的方法,其中所述催化剂混合物另外含有惰性载体。
19.权利要求18的方法,其中所述惰性载体选自i)原位沸石、ii)煅烧的高岭土、iii)氧化铝和iv)SiO2中的一种或多种。
20.权利要求19的方法,其中所述惰性载体是煅烧的高岭土。
21.权利要求1的方法,其中在所述FCC单元中加工所述烃油进料的同时,所述催化剂混合物保持至少55重量%的转化率。
22.权利要求1的方法,其中所述催化剂混合物与不含所述金属钝化剂/捕获剂的对照催化剂相比保持了降低至少28%的氢产率。
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CN109126898A (zh) * | 2018-09-26 | 2019-01-04 | 宜兴汉光高新石化有限公司 | 一种可同时钝化多种金属、提高轻油及总液收率的钝化剂及其制备方法 |
CN110339865B (zh) * | 2019-07-29 | 2020-06-02 | 华东理工大学 | 一种催化裂化抗金属增液剂及其制备方法 |
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- 2011-11-21 EP EP11876225.1A patent/EP2782980A4/en not_active Withdrawn
- 2011-11-21 JP JP2014543459A patent/JP5982496B2/ja not_active Expired - Fee Related
- 2011-11-21 WO PCT/US2011/061648 patent/WO2013077836A1/en active Application Filing
- 2011-11-21 CN CN201180076265.4A patent/CN104066819B/zh not_active Expired - Fee Related
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2014
- 2014-06-18 ZA ZA2014/04460A patent/ZA201404460B/en unknown
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US4321129A (en) * | 1978-09-12 | 1982-03-23 | Phillips Petroleum Company | Cracking process employing catalyst having combination of antimony and tin |
US4335021A (en) * | 1980-02-04 | 1982-06-15 | Phillips Petroleum Company | Catalyst regeneration |
US4576709A (en) * | 1982-09-02 | 1986-03-18 | Ashland Oil, Inc. | Catalytic upgrading of reduced crudes and residual oils with a coke selective catalyst |
EP0461851A2 (en) * | 1990-06-11 | 1991-12-18 | JOSEPH CROSFIELD & SONS LTD. | FCC processing using catalyst compositions containing metal ion-exchanged zeolites |
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CN105829504A (zh) * | 2013-12-19 | 2016-08-03 | 巴斯夫公司 | Fcc方法中的氧化硼 |
Also Published As
Publication number | Publication date |
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JP5982496B2 (ja) | 2016-08-31 |
BR112014012163A2 (pt) | 2017-05-30 |
RU2014125128A (ru) | 2015-12-27 |
ZA201404460B (en) | 2015-12-23 |
EP2782980A4 (en) | 2015-11-11 |
EP2782980A1 (en) | 2014-10-01 |
JP2015504473A (ja) | 2015-02-12 |
KR20140096134A (ko) | 2014-08-04 |
CN104066819A (zh) | 2014-09-24 |
WO2013077836A1 (en) | 2013-05-30 |
CA2856493A1 (en) | 2013-05-30 |
RU2603964C2 (ru) | 2016-12-10 |
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