CN102773096A - 一种多功能催化剂添加剂组合物及其制备方法 - Google Patents
一种多功能催化剂添加剂组合物及其制备方法 Download PDFInfo
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- CN102773096A CN102773096A CN2012101449625A CN201210144962A CN102773096A CN 102773096 A CN102773096 A CN 102773096A CN 2012101449625 A CN2012101449625 A CN 2012101449625A CN 201210144962 A CN201210144962 A CN 201210144962A CN 102773096 A CN102773096 A CN 102773096A
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Abstract
本发明涉及一种多功能催化剂添加剂组合物及其制备方法。本发明涉及一种用于减少流化催化裂化过程中的一氧化碳和氮氧化物的多功能催化剂添加剂组合物,其包括无机氧化物;铝硅酸盐或沸石;贵金属;I A族金属;II A族金属;III A族金属;IV A族金属;V A族金属;稀土氧化物;至少一种VIII族金属。该组合物是耐磨损的并且合并在载体上。本发明也披露了用于制备该多功能催化剂添加剂组合物的方法。本发明还披露了包括该多功能催化剂添加剂组合物的流化裂化催化剂。
Description
技术领域
本发明提供了一种用于流化催化裂化(fluid catalytic cracking,FCC)工艺(过程,process)中的一氧化碳氧化和氮氧化合物(NOx)还原的多功能催化剂添加剂组合物(multifunctional catalyst additive composition)。本发明为提供了一种使用废弃的炼油厂催化剂(refinery catalyst)材料制备所述多功能催化剂添加剂组合物的方法。本发明进一步提供了用于在裂化工艺期间增强一氧化碳的氧化、还原NOx、有效的热量回收,以及在再生过程中利用所述多功能催化剂添加剂组合物而不产生稀释作用的方法。因此,本发明提供了用于减少FCC装置(单元,unit)的排放的方法。
背景技术
世界上普遍的商业实践是通过将更重的石油级分裂化为更轻的、更有价值的材料以生产汽油、燃料油和柴油燃料。为完成这个转化,一种主要的商业技术是通过流化催化裂化或FCC。在FCC中,石油进料(feed)部分如真空瓦斯油在高温下和约1到4大气压的中等压力下与热的、反应性催化剂的颗粒接触。催化剂的量应适当,并且在高温下汽化进料,以将石油进料升高至约480°C到590°C的裂化温度,并提供反应的吸收热。为了发生烃转化,油和催化剂一同流动。在重石油进料和中间馏出级分的FCC转化过程期间,副产物焦炭(碳)沉积在催化剂颗粒上,因此使催化剂失活。碳沉积的催化剂颗粒,在旋风分离器(cyclone)中与裂化的石油产品分离。在分馏器中回收该产品,并且将焦结的催化剂送往再生器(regenerator)。将再生的热催化剂送回到提升管(riser)以进一步反应,因而完成该循环。FCC工艺是热平衡的。再生器中焦炭的烧制(burn)提供热,以提供裂化系统所有的热需求。在裂化期间产生的焦炭的量之间存在稳定的联系,焦炭在再生期间逐渐烧尽,并且该加热的催化剂返回到该工艺的裂化方面(裂化侧,cracking side)。这种结合不是完全独立的且可控的。在给定的一系列裂化条件下其又部分地受该石油馏分的性质的影响以产生或多或少的焦炭。
解决所有效果和相反效果的平衡以便调整进料、停留时间等以实现热平衡操作,这已经是惯常FCC操作的实践。因此,在裂化方面(crackingside)调整进料类型、进料速率、进料温度、催化剂的类型、催化剂与油的比率、接触时间、反应温度等,以便在催化剂上沉积充分数量的焦炭以满足系统的同时,生产出合乎需要的产品构成(product slate)。
用热交换器来处理系统的改变,如进料或催化剂的固有焦化倾向,(在其上精炼机不受控制)。使用空气流速和/进料预热器以对特殊情形的独特需求调整操作。
总是需要精炼机,以减少一氧化碳和诸如NO、N2O(NOx)的氮氧化物从FCC再生器排放到废气中。在某些情况下,这已通过使用一氧化碳锅炉(carbon monoxide boiler)和涤气器(scrubber)完成。虽然这些做得很好,但是需要相当大的资金投入,并且造成维护与修理方面的问题。因此,当为了日常或应急修理和维护而脱机取出生产中分离的一氧化碳氧化系统时,来自FCC再生器的一氧化碳和NOx排放则将固有地增加。因此,为了在容限(tolerable system)内维持烟气(stack gas)排放标准的纯度,(人们)认为有必要具有候补的(backup)一氧化碳和NOx控制系统;或者修改整个FCC操作;抑或改变排放控制需求。
已经针对修改FCC工艺的操作而做出实质性进展,以便通过减少或消除对下游一氧化碳氧化设施的需求,来减少再生器废气中的一氧化碳和NOx。这通过向再生器增加空气进料或利用多功能(multifunctional)催化剂添加剂完成。在再生器中烧制一氧化碳,往往会增加再生器中的热量。这对一些FCC操作具有一些有利的影响,因为它减少再生催化剂上的残余碳,可能允许催化剂总量(inventory)的减少(reduction);和/或更低的催化剂与油的比率;和/或更高的裂化温度。它也可允许裂化进料原料(stock)构成较少量的焦炭,其固有地产生低量焦炭,这是由于自始至终将更少的焦炭充分烧制成二氧化碳可能产生足够的热。
FCC过程在再生器中释放一氧化碳、NOx等。因此,具有关于精炼机的环境规定,以从FCC再生器烟气中减少一氧化碳和NOx的排放,并且安全地处理用过的催化剂。某些情况下一氧化碳的减少已经通过使用焚化炉(incinerator)或一氧化碳锅炉实现。氮氧化物减少(还原,reduction)已通过注入氨实现。焚化炉或锅炉的使用涉及大量的资本投入。一氧化碳锅炉也造成维护与修理问题。无论何时因种种理由取出一氧化碳氧化系统,从FCC再生器中排放的一氧化碳增加。通过许多方式处理使用过的催化剂,如降解该材料和用于其它用途或将该材料为送去金属回收和填埋。
因此,为了在允许限制(allowable limit)内维持烟气中有害气体的排放,(人们)认为有必要具备载体(support)一氧化碳控制系统或者使用外部试剂修正FCC的整个操作以减少FCC再生器烟气中的一氧化碳和NOx的排放。也必需有效地利用在一氧化碳氧化过程中产生的热。
美国专利4064039披露包括铂(Pt)或铼(Re)的催化剂,其改进了在再生器密相床(dense bed)中一氧化碳的烧制。这个专利描述利用贵金属改进的FCC催化剂的使用。然而,这个专利没有讨论关于废弃的炼油厂催化剂的使用。
美国专利4915035和4915037教导,使用包括硅石(二氧化硅)、氧化铝、硅石/氧化铝、高岭土以及包括Pt、铑、锇的混合物的低表面积多孔载体(具有大于50m2/g的表面积)。平均粒径在400-1200微米范围内。这些专利披露Pt的浓度范围为0.01到100ppm,但是也透露如Rh、钯(Pd)和锇(Os)的其他金属。这些文献中没有揭露实际载体或载体材料的组合物。除此之外,这些文献中揭露的粒度,在较高的方面(higher side),可能在反应器和再生器的流化中造成不均一性。在这两篇文献中揭露的多孔载体用于流化床锅炉(fluid bed boiler)。这些专利没有使用炼油厂废弃的材料,并且最终用途不同。
美国专利4350615教导,少量的包括Pd和钌(Ru)的助催化剂(promoter)在没有显著增加NOx排放的情况下增强一氧化碳的氧化。在没有引起氮氧化物过量的情况下,在FCC的再生区域内,通过使用合适的吸附剂,Pd-Ru助催化剂也提高了硫氧化物的捕获。这个专利没有讨论关于炼油厂用尽或废弃的材料的再循环。
美国专利4544645披露了裂化含硫烃的工艺和将SO2转化成SO3的经改进的氧化助催化剂,其包括Pd和至少一种选自包含钯、锇(Os)、铱(Ir)、Re和Rh的组中的其他金属的紧密结合(intimate association)。该文献没有披露一氧化碳和NOx的反应。
美国专利4300997教导,少量的Pd和Ru增强一氧化碳的转化而不过度影响FCC再生器中NOx的水平。Pd与Ru的金属比从0.1到10的重量百分比变化。在没有过量NOx生成的情况下这也具有脱除SOx的额外优势。然而,该发明没有使用炼油厂废弃的材料。
美国专利6902665描述包括含有酸载体、碱金属和/或碱土金属、具备储氧能力的过渡金属氧化物和Pd金属的组分的组合物。酸性氧化物载体优选包括硅石-氧化铝(silica alumina)。该文献描述特定类型的组合物非常有效地促进CO氧化,同时使NOx减到最少。在该文献中,二氧化铈必要地以按重量百分比2到50份的浓度用作载体的构成部分。然而,这个发明没有使用炼油厂废弃的材料。
美国专利4608357披露促进CO氧化的新型催化剂制剂(formulation)。该文献主要包括Pd和通过用苛性碱溶液从煅烧粘土的成型颗粒滤去(leach)充足的二氧化硅以赋予该颗粒多孔性而获得的多孔硅铝氧化物载体上的至少一种其他贵金属。载体颗粒优选具有范围为1.58到1.64的Al2O3/SiO2摩尔比;0.15cc/g的总孔体积;20-60m2/g范围内的表面积;范围内的孔结构;到范围内的孔隙直径;50-600ppm范围内的贵金属Pd和300到500ppm范围内的贵金属Re。所述专利仅仅涉及CO氧化活性而不涉及NO的减少(还原)。该专利也没有使用炼油厂废弃的材料。
美国专利7045056描述在FCC过程中控制CO和NOx排放的组合物,其包括酸性氧化物载体、铈氧化物、除了二氧化铈之外的镧系元素氧化物如镨氧化物,可选的来自Ib、IIb如铜、银、锌以及Pt或Pd的组的金属的氧化物。使用Al2O3、铜改性(modified)的Al2O3、二氧化铈改性的氧化铝制备不同的制剂。通过使用100%蒸汽在1500F蒸发4小时使制备的样品失活。使用从50到1500ppm的贵金属Pt和Pd的混合物;进料浓度为0.1wt%的氮。该文献使用镧系元素即铈、镨氧化物中的至少一种氧化物。即使稀土金属的使用提高了该工艺的效率,然而该发明没有使用炼油厂废弃的材料。
不能经受先有技术可用材料的量,仍然需要重复利用废弃的炼油厂催化剂材料或使用新的优良载体,在没有稀释作用(dilution effect)的情况下,使新型多功能催化剂添加剂具有更好的物理性质使CO和NOx减少。
发明内容
本发明的主要目的是提供比现有技术中提到的更好的多功能催化剂添加剂组合物(multifunctional catalyst additive composition)。
本发明另一目的是提供用于FCC中的具有改善的氧化水平的一氧化碳氧化和NOx还原催化剂组合物。
本发明的又一个目的是提供多功能催化剂添加剂组合物,该组合物可包括新(未用过的,fresh)载体、或使用废的炼油厂催化剂的再配制(再形成,re-formulated)材料。
本发明的另一个目的是提供用于制备所述多功能催化剂添加剂组合物的方法。
本发明的另一目的是提供多功能催化剂组合物,其可提供对控制废催化剂上的焦炭(coke);减少一氧化碳和NOx的形成;FCC催化剂再生期间的有效热回收和利用的改进。
本发明的又一个目的是提供多功能催化剂组合物,其对于一氧化碳氧化和NOx还原是具有活性的,并且具有与现有技术中已知的那些相当或更好的优良磨损强度(attrition strength)。
本发明提供用于减少流化催化裂化工艺中一氧化碳和氮氧化物的多功能催化剂添加剂组合物,包括(i)无机氧化物;(ii)至少1%的铝硅酸盐(alumino silicate)或沸石;(iii)按重量计至少0.001%的贵金属;(iv)按重量计至少0.01%的I A族金属;(v)按重量计至少0.01%的II A族金属;(vi)按重量计至少0.45%的III A族金属;(vii)按重量计至少0.3%的IVA族元素;(viii)按重量计至少0.01%的至少一种VA族金属;(ix)按重量计至少0.05%的稀土氧化物;(x)按重量计至少0.02%的至少一种VIII族金属;其中,该组合物是耐磨损的(attrition resistant),并且合并(结合)到载体上,其还赋予对裂化的更多优势。
根据本发明的另一实施方式,该多功能催化剂添加剂组合物中的载体,是新载体或来自裂化石油工艺的废弃的炼油厂催化剂。
根据本发明的另一个实施方式,该新载体包括呈单峰孔分布,孔隙范围为20°A到300°A优选地在20到100°A范围内,更优选地在20到60°A范围内,表面积的范围为300-400m2/g,ABD 0.8以及APS在50-60微米范围内。
根据本发明的又一个实施方式,废弃的炼油厂催化剂包括双峰孔分布,孔隙范围在20°A到50°A和80°A到100°A;粒度分布在20-120微米范围内、平均粒度在70到85微米范围、表面积在117到200m2/g范围内、基质表面积(matrix surface area)在30到35m2/g范围内、微孔体积为0.03到0.04ml/g、体积密度(bulk density)在0.8到0.9g/mL范围内,磨损指数(attrition index)按重量计在2到5%范围内。
根据本发明另一个实施方式,在多功能催化剂添加剂组合物中,贵金属是按重量计在0.001%到1%范围内的钯,并且是均匀分布在该催化剂组合物中的元素形式(单质形式,elemental form)。
根据本发明的另一个实施方式,在多功能催化剂添加剂组合物中,IA族金属是按重量计在0.01%到0.25%范围内的钠;IIA族金属是按重量计在0.01到0.25%范围内的镁;IIIA族金属是按重量计在0.45到1.0%范围内的铝;IVA族元素是按重量计在0.30到1.0%范围内的碳;V族金属是按重量计在0.01到0.25%范围内的钒或按重量计在0.1到0.7%范围内的磷;稀土氧化物按重量计在0.05%到1.2%的范围内;VIII族金属是按重量计在0.02到0.07%范围内的镍或按重量计在0.1到0.45%范围内的铁;铝硅酸盐或沸石按重量计在1到56%范围内;无机氧化物在1-50wt%范围内。
根据本发明又一个实施方式,提供一种流化裂化催化剂(fluid crackingcatalyst),包括如上描述的多功能催化剂添加剂组合物。
根据另一种实施方式,本发明提供了用于制备用于减少流化催化裂化工艺中一氧化碳和氮氧化物的多功能催化剂添加剂组合物的方法,包括以下步骤:i)通过加热干燥该载体;ii)向经干燥的载体上合并(结合)贵金属;iii)干燥和煅烧并入金属的载体。
根据另一个实施方式,本发明提供用于制备多功能催化剂添加剂组合物的方法,其中该载体是新载体,平均粒度为约60-80微米。通过顺次浸渍(连续浸渍、分步浸渍,sequential impregnation)或共浸渍(coimpregnation)或平衡吸附(equilibrium adsorption)合并(结合、并入,incorporate)如Ni、V、Na、Fe、Mg、稀土金属的金属。然后干燥并煅烧该载体。这种经煅烧的材料用作合并贵金属的载体并且经受干燥和煅烧步骤。
根据又一个实施方式,本发明提供用于制备多功能催化剂添加剂组合物的方法,其中载体材料的干燥步骤由以下构成:(i)500°C下于空气中在玻璃反应器中加热4小时;ii)在室温或稍高于室温优选低于40°C下,通过平衡吸附或湿浸渍法向干燥的载体中合并贵金属钯;iii)在110°C到120°C下干燥该金属沉积材料8到16小时,之后在450°C到500°C下煅烧3到4小时。
根据本发明的另一实施方式,废弃的炼油厂催化剂包括在0.3-1.0wt%范围内的碳,并且如上所述在合并其他金属之前或之后烧制该碳。
根据本发明的另一个实施方式,废弃的炼油厂催化剂在氧气或空气优选1%氧气其余诸如氮或氦的惰性气体的存在下烧制,并且温度以2°C每分钟的步阶上升。
根据本发明的又一个实施方式,贵金属钯在碳脱除(carbon removal)之前或之后合并到该干燥的载体上。
根据本发明的另一个实施方式,经烧制的焦炭和沉积在废弃的催化剂载体中的钯经受高温,其中,所述高温是在空气或诸如氮的惰性气氛中以2°C每分钟升高到400°C至600°C。
根据另一实施方式,本发明提供一种用于制备用于减少流化催化裂化工艺中的一氧化碳和氮氧化物的多功能催化剂添加剂组合物的方法,包括步骤:i)通过在500°C下于空气中在玻璃反应器中加热4小时以干燥载体,其中所述载体是新载体或来自裂化石油工艺的废弃的炼油厂催化剂。载体平均粒度为约60-80微米,且所述废弃的炼油厂催化剂包含在0.3-1.0wt%范围内的碳;ii)在室温或稍高于室温优选低于40°C下,通过平衡吸附或湿浸渍法向干燥的载体中合并贵金属钯;iii)在110°C到120°C下干燥该载体8到16小时;iv)在450°C到500°C下煅烧该载体3到4小时;v)通过顺次浸渍或共浸渍或平衡吸附合并金属如Ni、V、Na、Fe、Mg、稀土金属。然后干燥和煅烧该载体。这种经煅烧的材料用作合并贵金属的载体并且经受干燥和煅烧步骤。
根据另一个实施方式,本发明提供一种流化裂化催化剂,其包括通过以上描述的方法制备的多功能催化剂添加剂组合物,其中所述催化剂是耐磨损的,对裂化没有稀释作用,且减少流化催化裂化工艺中的一氧化碳及氮氧化物。
附图说明
图1:用于制备多功能添加剂的载体的孔径分布(孔隙大小分布,poresize distribution)比较。在图1中,a、b、c是用于制备催化剂添加剂的不同载体。
具体实施方式
在已经概述本发明之后,现在将在下文中参考下列描述和非限制性实施例进行详细描述。
来自再生区域(regeneration zone)的催化剂的焦炭沉积物的烧制可简化为碳的氧化和NO的还原,其可通过下列化学方程式表示。
(1)C+O2→CO2
(2)2C+O2→2CO
(3)2CO+O2→2CO2
(4)CO+2NO→N2+CO2
反应(1)和(2)都在典型的催化剂再生条件下发生,其中该催化剂温度可能为约500至700°C,并当在这个范围的温度下再生催化剂时其为示例性的气固化学相互作用。温度的任何升高的效果反映在碳氧化的增长率以及从催化剂颗粒更完全地脱除焦炭中。气相反应(3)也通过升高的温度和更高的压力加速,尤其是在存在过量的氧时。在采用添加的多功能催化剂添加剂的情况下,可采用稍低的温度。在再生器中NO浓度较大时,反应(4)是最优选的。它有助于减少NO和CO二者。助催化剂可合并到该催化剂中,或者单独引入再生区域。此外,对于涉及由碳形成一氧化碳的上述反应,在焦炭中也会由氢形成水。
在流体化催化剂中使用足以烧制焦炭的理论量的氧气以使再生的催化剂上参与焦炭达到期望的低水平,通常具有不期望的效果,即在稀释催化剂相(dilute catalyst phase)产生氧气和一氧化碳的可燃混合物。这可能经受通常称为后烧制(after burning)的进一步氧化。后烧制引起稀释催化剂阶段的温度显著升高,其可能到达800°C。稀释催化剂阶段的这种高温可能引起催化剂失活,从而需要向该过程的额外的催化剂更换,以便在烃反应区维持期望的催化活性。另外,这些高温可能对再生区域的硬件部件造成损坏。
下列的实施例说明和支持本发明。这些仅仅是示例性的实施例,并不旨在以任何方式限制本发明的范围。
为了本文和/或下列实施例的目的,除非另有说明,下列术语具有这里说明的定义:
(i)“新的(未用过的,fresh)”FCC催化剂是生产商提供的复合粉末材料(composite powder material)。
(ii)“平衡催化剂(equilibrium catalyst)”(E-Cat)是在一段时间内在工艺中所产生的。
(iii)废FCC催化剂,具有可忽略的用于裂化的活性,在一段时间内在工艺中产生。
实施例1
为减少一氧化碳和NOx还原的多功能催化剂添加剂通过使用商用的多孔的、表观体积密度(apparent bulk density)为0.85g/cc、表面积为332m2/g、粒度为20-120微米以及磨损指数为10的γ-氧化铝粉末制备。载体材料包括单峰孔径分布,其大多数孔隙在20-100°A范围内。在合并贵金属钯(Pd)之前,通过在500°C下于空气中在玻璃反应器中加热4小时干燥该载体。通过使用Pd金属盐,优选硝酸钯的湿浸渍法将不同量的Pd(0.1、0.15、和0.2wt%)沉积在该载体上,从而制备三组一氧化碳和NOx减少的催化剂添加剂。在浸渍之后,该材料在110-120°C干燥10小时,并在490-500°C煅烧4小时。这些样品分别成为催化剂1、催化剂2、催化剂3。
在独立的装置中进行一氧化碳和NOx减少(reduction)活性研究,该装置由固定床玻璃反应器、冷凝器、气液分离器和在线(online)NOx转换器、CO-CO2和NOx分析仪组成。使用电炉和PID温度控制器/编程器(programmer)加热该反应器。在开始实验之前用包括CO-CO2和NOx的校准气体(calibration gas)校准分析仪。使用已知重量的炼油厂废催化剂作为基础材料(base material)而不增加任何氧化催化剂,该炼油厂废催化剂具有在工艺过程中沉积于其上的碳和含氮化合物。在每个实验中与基础材料一起使用10%重量的添加剂。在氧化反应期间利用空气形成的一氧化碳和NOx的量,作为用于测量催化剂的活性的基础。重复每个实验至少两次并计算平均值。因为形成的CO2的量足够大并且超过分析仪的限值,因此这个研究仅考虑形成的一氧化碳和NOx的量。以上描述的催化剂具有以下在表1中给出的特征和活性。
表1:实施例1的物理特性和活性
SA:表面积,AI:磨损指数,ABD:表观体积密度,APS:平均粒度
即使上述一氧化碳和NOx减少(还原)催化剂添加剂具有良好的活性,但是由于其较差的物理特性如磨损强度和APS在操作期间可能造成问题,因而不考虑将其用在工厂中。
实施例2
具有190m2/g的表面积,且单峰孔隙在的范围内的另一种商用γ-氧化铝载体,用于制备另一种更好的一氧化碳和NOx减少催化剂添加剂。在合并贵金属钯之前,载体在500°C于空气中干燥4小时。通过使用钯金属盐,优选硝酸钯的湿浸渍法将不同量的钯(0.1、0.15、0.2和0.25wt%)沉积到载体上从而制备四种催化剂。如在实施例1中所描述的干燥和煅烧经浸渍的材料。这些催化剂添加剂分别称为催化剂4、催化剂5、催化剂6和催化剂7。在实施例1中描述的类似装置中实施活性研究,通过采用基础材料中10%的添加剂。表2中给出了结果。
表2:实施例2的物理特性和活性研究
由于较差磨损强度可能在工厂中造成问题,也不认为这些催化剂添加剂是良好的。
实施例3
在另一突破性发明中,通过使用炼油厂废弃的废裂化催化剂作为载体制备用于一氧化碳和NOx减少(还原)的多功能添加剂。从处理不同类型进料和催化剂的不同条件下操作的两个不同的FCC装置中收集废弃的炼油厂废催化剂样品。基于文献(Fluid Catalytic Cracking Hand Book,RezaSadeghbeigi,Gulf publishing Company Houston出版,Texas 1995,第79-120页),据信与新的催化剂的高活性相比,催化活性已经减少的FCC废催化剂是包括氧化铝、硅石和基于天然粘土的材料的复合材料。活性的损失主要原因在于热液(hydrothermal)和裂化的系列反应。基于公开的信息,相信废催化剂包括约10-45wt%的沸石组分,大多具有如"Y"或"X"类型的宽孔隙,以及20-45wt%的氧化铝组分,剩余为粘土、硅石、过渡金属和碳。废弃的废催化剂是具有平均粒度大约为60-80微米的精细粉末。这些实验中使用的商用催化剂的特定样品,取自稳态条件下运行的两个不同的商业FCC工厂的剥离器出口(stripper outlet)。废弃的催化剂的物理特性如下给出。用作载体材料的废催化剂,包括双峰孔分布,具有两种类型的孔隙,在20-50°A和80-100°A范围内(图1)。通过在纯氧/空气或它们以适当组成的混合物的存在,并且在300-550°C温度下,控制加热速率2-50°C/min进行加热,从而将废弃的催化剂上的焦炭烧制2-6小时。按照如实施例1和2中描述的同样的步骤,以贵金属0.2wt%钯的固定组成,使用这些从两个不同的FCC装置收集的经处理的废催化剂作为载体,从而制备两种催化剂添加剂。在合并贵金属之前,用作载体的经处理的废催化剂也包括其他金属,如0.1-0.45wt%铁(Fe)、0.02-0.07wt%镍(Ni)、0.02-0.06wt%钒(V)、0.01-0.25wt%钠(Na)、0.01-0.6wt%磷(P)、0.01-0.7wt%氧化镁(MgO)、0.05-1.2wt%铼氧化物(Re2O3)。在这个实施例中通过使用从两个不同的FCC装置收集的经处理的废催化剂制备的催化剂称为催化剂8和催化剂9。以与之前描述的使用10wt%催化剂添加剂与基础材料的实施例相似的方式实施活性研究。以下给出结果。
表3:实施例3的物理特性和活性研究
*在括号内显示的值表示基础材料。
这二种氧化催化剂添加剂具有更好的物理特性、良好的磨损强度和活性。即使这些催化剂添加剂与之前的实施例相比活性较小,由于其物理特性,该装置中的催化剂保持更好。因此,认为这些催化剂在所有性能上都优于其他催化剂。
实施例4
在另一个实施方式中,通过使用废弃的废(用过的,spent)裂化催化剂作为载体,制备一氧化碳,NOx减少催化剂添加剂。焦炭烧制过程类似于在实施例3中解释的那样。与其他实施例不同,除一种贵金属钯之外,还加入其他贵金属铂。分别使用硝酸钯和六氯铂酸金属盐(hexa chloroplatinic acid metal salt)通过连续的湿浸渍法,将不同量的(Pt及Pd)(0.01和0.06,0.01和0.05,0.025和0.025wt%)沉积到载体上,从而制备三组催化剂添加剂。正如实施例1中解释的,干燥和煅烧经浸渍的材料。这些样品称为催化剂10、催化剂11、催化剂12。表4给出活性结果和特性。在实施例1中引用的所有其他的辅助金属(auxiliary metal)也存在于这个实施例中。
表4:实施例4的物理特性和活性研究
*圆括号内显示的数值表示基础材料。
即使这些催化剂具有更好的物理特性,但认为不是良好的催化剂,因为与其他制剂相比活性较低。
实施例5
合成载体:为了确保使用作为载体的FCC废弃的废催化剂的适合性以制备一氧化碳和NOx减少催化剂添加剂。通过使用新氧化铝、沸石和粘土以与FCC催化剂相同的组成制备合成载体,并按照Catalysis Today,141,issue 1-2(115-119),2009中描述的步骤,通过金属和蒸汽失活模拟制备平衡催化剂(Equilibrium-catalyst),在如之前实施例3中描述的焦炭烧制之后,按照在之前实施例中描述的方法,连同0.2wt%Pd金属沉积,其用作用于制备一氧化碳和NOx减少催化剂的载体,并且研究了不同金属及其浓度对一氧化碳和NOx减少的有益及有害影响,结果在表5中给出。
表5:实施例5的物理特性和活性研究
*括号中的数值是基础情况下的数值。
上面的结果显示,在上述的范围内,即使存在如Ni、V、Na、F的金属e和稀土氧化物,也可非常有效地利用FCC废催化剂。
本发明可以有利地应用于制备一氧化碳氧化和NOx还原催化剂。根据本发明,新的FCC催化剂或优选地谨慎地限制痕量金属沉积在其上的焦炭烧制的FCC废催化剂上可用作制备CO氧化和NOx还原催化剂的优良载体。在焦炭烧制后用作载体的废弃的废催化剂也具有良好的裂化活性(表6),具有长寿命和在催化流化床装置中更好的磨损强度。(表7)。此外由于废弃的催化剂包括其他金属,该金属抑制精细分散的钯金属与通常存在于真空瓦斯油(Vacuum Gas Oil,VGO)中的硫和含氮化合物接触的可达性(accessibility),因此延长添加剂的寿命。
表6:一氧化碳氧化添加剂的裂化活性
(裂化反应在由Kayser设计的M/s Xytel USA(ACE-R)提供的固定流化床反应器中实施)反应条件是T-500°C,催化剂/油:6.5,进料注入速率:2gm/min;使用的催化剂的量:6.5克(gms)。
表7:示出用于制备一氧化碳和NOx减少催化剂添加剂的不同载体的物理化学性质(表征)
特性 | 1 | 2 | 3 | 4 | 5 | 6 |
SA(m2/g) | 332 | 80 | 182 | 190 | 187 | 189 |
AI(wt%) | 10 | 8 | 9 | 10 | 3 | 3 |
ABD(g/cc) | 0.8 | 0.8 | 0.8 | 0.8 | 0.9 | 0.9 |
APS(μ) | 56 | 73 | 68 | 80 | 75 | 73 |
注释:1、2、3、4-从市场获得的商用载体。
5和6-由来自炼油厂的废弃的废催化剂制备的载体。(实施例3和4)
本发明的主要优势是:
1.制备供FCC使用的一氧化碳和NOx减少催化剂的方法使用具有特殊孔隙的新载体。
2.一氧化碳氧化和NOx还原催化剂具有更好的耐磨损特性。
3.用于FCC的多功能催化剂添加剂的制备方法是成本有效的。
4.除CO和NOx减少活性(还原活性,reduction activity)之外还有裂化活性的额外优势。
Claims (23)
1.一种用于减少流化催化裂化工艺中的一氧化碳和氮氧化物的多功能催化剂添加剂组合物,包括:
(i)无机氧化物材料;
(ii)至少1%的铝硅酸盐或沸石;
(iii)按重量计至少0.001%的贵金属;
(iv)按重量计至少0.01%的I A族金属;
(v)按重量计至少0.01%的II A族金属;
(vi)按重量计至少0.45%的III A族金属;
(vii)按重量计至少0.3%的IV A族元素;
(viii)按重量计至少0.01%的至少一种V A族金属;
(ix)按重量计至少0.05%的稀土氧化物;
(x)按重量计至少0.02%的至少一种VIII族金属;
其中,所述多功能添加剂组合物沉积到载体上并且是耐磨损的。
2.根据权利要求1所述的多功能催化剂添加剂组合物,其中,所述载体是新载体、或来自裂化石油工艺的废弃的炼油厂催化剂。
3.根据权利要求2所述的多功能催化剂添加剂组合物,其中,所述新载体包括无机氧化物或沸石,具有单峰孔分布,孔隙在20°A到300°A范围内,优选在20到100°A范围内,更优选在20到60°A范围内。
4.根据权利要求2所述的组合物,其中,所述废弃的炼油厂催化剂包括双峰孔分布,孔隙在20°A到50°A以及80°A到100°A的范围内。
5.根据权利要求1所述的组合物,其中,所述贵金属是按重量计在0.001%到1%范围内的钯,其中进一步地,所述钯为均匀分布在所述催化剂组合物中的元素形式。
6.根据权利要求1所述的组合物,其中,所述IA族金属是按重量计在0.01%到0.25%范围内的钠。
7.根据权利要求1所述的组合物,其中,所述IIA族金属是按重量计在0.01到0.25%范围内的镁。
8.根据权利要求1所述的组合物,其中,所述IIIA族金属是按重量计在0.45到50%范围内的铝。
9.根据权利要求1所述的组合物,其中,所述IVA族元素是按重量计在0.01到1.0%范围内的碳。
10.根据权利要求1所述的组合物,其中,所述V族金属是钒或磷,其中,所述钒按重量计在0.01到0.25%范围内,或其中,所述磷按重量计在0.1到0.7%范围内。
11.根据权利要求1所述的组合物,其中,所述稀土氧化物按重量计在0.05%到1.2%范围内。
12.根据权利要求1所述的组合物,其中,所述VIII族金属是镍或铁,其中,所述镍按重量计在0.02到0.07%范围内,或其中,所述铁按重量计在0.1到0.45%范围内。
13.根据权利要求1所述的组合物,其中,所述铝硅酸盐或沸石按重量计在1到56%范围内。
14.根据权利要求1所述的组合物,其中,所述无机氧化物是氧化铝。
15.一种用于制备权利要求1所述的用于减少流化催化裂化工艺中的一氧化碳和氮氧化物的多功能催化剂添加剂组合物的方法,包括以下步骤:
i)通过顺次浸渍或共浸渍或平衡吸附,将选自包括Ni、V、Na、Fe、Mg或稀土金属的组的金属合并到所述载体上,其中,所述载体是新载体、或来自裂化石油工艺的废弃的炼油厂催化剂;
ii)通过加热来干燥所述载体;
iii)将贵金属合并到经干燥的载体中;
iv)干燥所述载体;
v)煅烧所述载体。
16.根据权利要求15所述的方法,其中,步骤(ii)中的所述干燥是通过在500°C下于空气中在玻璃反应器中加热4小时。
17.根据权利要求15所述的方法,其中,所述贵金属是钯,并且在室温或稍高于室温优选低于40°C下,通过平衡吸附或湿浸渍法,在碳脱除之前或之后,将其合并到经干燥的载体中。
18.根据权利要求15所述的方法,其中,步骤(iv)中的所述干燥是在110°C到120°C下8到16小时。
19.根据权利要求15所述的方法,其中,所述载体的煅烧是在450°C到500°C下3到4小时。
20.根据权利要求15所述的方法,其中,所述废弃的炼油厂催化剂包括在0.3-1.0wt%范围内的碳,其在合并金属之前或之后,优选地在氧气或空气优选1%氧气的存在下,在受控的气氛中,以2°C每分钟的速率加热而进行烧制。
21.根据权利要求15到20中任一项所述的方法,其中,所述经烧制的焦炭和沉积在所述废弃的催化剂载体中的钯经受高温,其中所述高温是在空气中或惰性气氛如氮气中以2°C每分钟升高至400°-600°C。
22.根据权利要求15所述的方法,包括以下步骤:
i)通过顺次浸渍或共浸渍或平衡吸附,将选自包括Ni、V、Na、Fe、Mg或稀土金属的组的金属合并到所述载体中;
ii)通过在500°C下于空气中在玻璃反应器中加热4小时来干燥所述载体,其中,所述载体是新载体、或来自裂化石油工艺的废弃的炼油厂废催化剂,平均粒度为约60-80微米并且所述废弃的炼油厂废催化剂包括在0.3-1.0wt%范围内的碳;
iii)在室温或稍高于室温优选低于40°C下,通过平衡吸附或湿浸渍法将所述贵金属钯合并到经干燥的载体中;
iv)在110°C到120°C干燥所述载体8到16小时;
v)在450°C到500°C煅烧所述载体3到4小时。
23.一种流化裂化催化剂,包含权利要求1到14中任一项所述的且优选通过权利要求15到22中任一项所述的方法而制备的多功能催化剂添加剂组合物,其中,所述催化剂是耐磨损的,对于裂化没有稀释作用,且减少在流化催化裂化工艺中的一氧化碳和氮氧化物。
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- 2012-05-02 AU AU2012202584A patent/AU2012202584B2/en not_active Ceased
- 2012-05-03 SG SG2012032561A patent/SG185882A1/en unknown
- 2012-05-07 JP JP2012105916A patent/JP5584252B2/ja not_active Expired - Fee Related
- 2012-05-07 US US13/465,704 patent/US9227180B2/en not_active Expired - Fee Related
- 2012-05-10 CN CN201210144962.5A patent/CN102773096B/zh not_active Expired - Fee Related
- 2012-05-11 EP EP12167768.6A patent/EP2522423B1/en active Active
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US20040072675A1 (en) * | 2002-10-10 | 2004-04-15 | C. P. Kelkar | CO oxidation promoters for use in FCC processes |
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CN109575978A (zh) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | 一种生物油脂的加工方法 |
CN109575978B (zh) * | 2017-09-28 | 2021-01-08 | 中国石油化工股份有限公司 | 一种生物油脂的加工方法 |
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EP2522423A2 (en) | 2012-11-14 |
EP2522423A3 (en) | 2013-01-23 |
US9227180B2 (en) | 2016-01-05 |
US20130130888A1 (en) | 2013-05-23 |
EP2522423B1 (en) | 2020-12-02 |
AU2012202584B2 (en) | 2013-10-17 |
CN102773096B (zh) | 2016-08-24 |
JP2012236191A (ja) | 2012-12-06 |
AU2012202584A1 (en) | 2012-11-29 |
JP5584252B2 (ja) | 2014-09-03 |
SG185882A1 (en) | 2012-12-28 |
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