CN101255360B - 使用担载催化剂的重质烃原料和/或煤浆料相加氢转化方法 - Google Patents
使用担载催化剂的重质烃原料和/或煤浆料相加氢转化方法 Download PDFInfo
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- CN101255360B CN101255360B CN2007101857267A CN200710185726A CN101255360B CN 101255360 B CN101255360 B CN 101255360B CN 2007101857267 A CN2007101857267 A CN 2007101857267A CN 200710185726 A CN200710185726 A CN 200710185726A CN 101255360 B CN101255360 B CN 101255360B
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- 238000007725 thermal activation Methods 0.000 description 1
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Abstract
本发明的发明名称是使用担载催化剂的重质烃原料和/或煤浆料相加氢转化方法。本发明涉及在氢气和催化剂存在下在浆料反应器中进行的重质原料转化方法,该催化剂含氧化铝担载的至少一种催化金属或第VIB族和/或第VIII族催化金属化合物,其孔结构是由多个并置的聚集体构成的,每个聚集体由多个针状片晶构成,每个聚集体的片晶彼此相对并相对于聚集体中心通常呈放射状取向,所述催化剂有不规则的非球形状,主要呈碎片形式,根据在说明书中具体描述的包括步骤a)-h)的制备方法得到。本发明的方法使用具有特定孔结构、形状和粒度的催化剂,得到改进的性能。
Description
技术领域
本发明涉及使用担载催化剂的重质烃原料和/或煤浆料相加氢转化方法。
背景技术
重质烃馏分加氢转化采用的浆料相法是一种本技术领域的技术人员已知的方法,该方法往往在可溶性催化前体存在下能够加氢精制重质原料。在专利US 3 231 488中描述了在氢气和/或H2S存在下,注入呈有机金属形式的金属,生成细分散的催化相,使得在注入这种原料后该残留物得以加氢精制。这种催化相的尺寸非常精细,随液体一起通过反应区。在US 4 244 839中,C.L.Aldridge和R.Bearden描述了一种催化相,特别用于残留物加氢转化,该催化相是由可溶于油的、可热分解的催化前体制备的,在高温与氢气和H2S存在下与含有康氏碳的原料接触。许多催化前体能够起到可热分解金属化合物的作用:有机可溶解化合物,像环烷酸钼、辛酸钼,还有水溶性化合物,像专利US 3 231 488(UOP)、US 4 637 870和US 4 637 871提到的磷钼酸,或专利US 6 043 182引用的七钼酸铵。在水溶性化合物的情况下,该催化前体一般通过乳化与该原料进行混合。
本技术领域的技术人员熟知这些金属化合物的作用:在某些条件下,优选地在硫化氢存在与高温下,这些含有第II、III、IV、V、VIB、VIIB或VIII族金属的盐、酸或化合物分解生成分散的金属硫化物,它们在加氢转化方法中的催化活性例如有利于重质烃的裂解、氢化、加氢脱硫、加氢脱氮和加氢脱金属反应。
专利US 4 376 037和US 4 389 301(Chevron)描述了在分散氢化催化剂与不含氢化化合物的多孔颗粒,优选地廉价多孔颗粒存在下,让油和氢气进行接触。多孔固体典型地是具有10-50微米粒度的废FCC催化剂。这些颗粒优选地装在封闭的床中,而不被原料夹带。这些作者提到分散催化剂与多孔颗粒之间的协同作用,它们能够减少流出液中金属和沥青质的含量。
在Intevep公司的专利US 4 937 218和US 6 384 091中,提出一种加氢转化方法,该方法使用就地(即浆料反应器本身)生成的可再生催化剂,该催化剂含有活性相和耐火载体。根据这些专利,优点是生成可再生的催化剂。在反应区中,该有机金属盐与耐火载体进行反应,以生成具有良好HDM(加氢脱金属)、HDS(加氢脱硫)和HDN(加氢脱氮)活性的多孔的担载催化剂。
最后,专利FR 2 534 828涉及粉碎催化剂的加氢转化方法,该方法主要以固定床运行。它提到在将催化剂分散于液相里的方法中使用这样的催化剂。但是,看起来该专利的催化剂没有足够的机械强度用于以工业规模运行的浆料法中。
发明内容
本申请人发现,在含有金属的重质烃原料的加氢转化的浆料操作中使用具有适当粒度和形状的担载固体催化剂,能够产生改进的流出液氢化的性能。
所述催化剂含有呈主要不规则的非球形的氧化铝基聚集体形式的载体,其特定形状是由粉碎步骤造成的,含有至少一种催化金属或一种第VIB族和/或第VIII族(新的元素周期表符号中的第8、9或10族)催化金属化合物,任选地至少一种掺杂元素,它选自磷、硼和卤素,所述催化剂基本上由多个并置的聚集体构成,每个聚集体由多个针状片晶构成,每个聚集体的片晶一般彼此相对并相对于聚集体中心取向。
令人惊奇地,本申请人发现在这些制备方法步骤中改变粉碎步骤位置时,可以得到呈主要不规则的非球形的氧化铝基聚集体形式的具有“栗子壳斗”结构的多模态催化剂,它的机械强度比采用专利申请FR 2534 828方法的有改进。这个重要优点能够期望在浆料反应器使用该催化剂,而它不适合于采用FR 2 534 828方法得到的催化剂。
有利地,该催化剂注入一部分液体转化产品中,这些产品含有在接近反应区温度与压力的温度与压力条件下溶解的硫化氢。
本发明将分散的担载催化剂使用、浆料使用和异地制备的担载催化剂使用结合起来,本发明有许多优点,即:
·尽管催化相沉积在载体上,由于小的催化剂颗粒尺寸和载体的多模态孔隙度,但它依然与大烃结构充分接触,所谓″栗子壳斗″,即有利于物质往孔内转移的孔隙度;
·该催化剂用原料被连续供给与更新,从而限制催化功能失活,特别因堵塞孔产生的催化功能失活;
·该催化剂在反应段上游异地(ex-situ)制备,这样能够优化采用本技术领域技术人员已知的任何方法的催化剂的制备,在活性相元素在载体上分散性方面尤其如此,温度、压力和引起焦化的含碳分子存在因素除外;
·活性相担载形式使得该催化剂再生容易,由于所述活性相被稳定在该氧化铝上,因此不存在任何与其升华相关的问题。
发明的说明
本发明涉及在氢气存在下和在催化剂存在下在浆料反应器中进行的重质原料转化方法,该催化剂含有氧化铝担载的至少一种催化金属或第VIB族和/或第VIII族催化金属的化合物,其孔结构是由多个并置的聚集体构成的,每个聚集体由多个针状片晶形成,每个聚集体的片晶彼此相对并相对于聚集体中心通常呈放射状取向,所述催化剂具有不规则的非球形状,主要呈碎片形式,是根据包括下述步骤的制备方法得到的;
a)使用具有结晶不好的结构和/或无定形结构的活性氧化铝粉末制粒,得到珠状聚集体;
b)所述珠在60-100℃的湿润气氛中熟化,然后干燥;
c)筛分以回收所述珠的部分;
d)粉碎所述部分;
e)在温度250-900℃温度下煅烧至少一部分所述粉碎部分;
f)在80-250℃温度下进行酸浸渍和水热处理;
g)干燥,然后在500-1100℃温度下煅烧;
h)浸渍至少一种催化金属或第VIB族和/或第VIII族催化金属化合物。
这种担载催化剂或者在上游注入或者直接在该反应器中被注入并混合在原料中,并且随这种烃相在浆料反应器中循环,其浓度以重质烃原料计是0.1-20重量%,优选地0.5-10重量%。
该催化剂颗粒的平均尺寸是25-1000微米,优选地100-800微米。
该氧化铝基载体不含有成分,例如单个或混合的二氧化硅(SiO2)、二氧化硅-氧化铝、二氧化钛(TiO2)、沸石或粘土,这些成分在这些反应条件下能增加所述氧化铝基氧化物的表面酸性。这种酸性是可造成严重后果的,因为它产生大量焦化,过早堵塞催化剂的孔隙。
相反地,该氧化铝基载体可以含有不产生酸度的成分,例如稀土、碱土金属或磷,如果它被加入的含量为2重量%以下。
主要呈不规则形式的氧化铝基载体一般地具有下述特征:
-在1000℃下煅烧测定的烧失量是约1-15重量%;
-比表面是50-250m2/g;
-总孔体积(VPT)是0.5至约2.0cm3/g;
-采用Hg孔隙测定法技术(本文采用Hg的任何测定都是根据标准4284-92,润湿角140°进行的)测定的孔分布,其特征优选如下:
-平均直径小于的孔的总孔体积的%:0-10
所述催化剂的活性相含有至少一种催化金属或一种第VIB族催化金属的化合物(新周期表符号中第6族),优选钼或钨,和/或任选地至少一种催化金属或一种第VIII族催化金属化合物(新周期表符号第8、9和10族),优选镍或钴。有利地,该催化剂还可以含有至少一种选自磷、硼和卤素(第VIIA族或新周期表符号第17族)的掺杂元素,优选地是磷。优选地,该催化剂含有至少一种第VIB族金属(优选钼)和任选地至少一种第VIII族非贵重金属,优选地是镍。优选的催化剂是Ni Mo P类的。
第VIB族金属的量,以氧化物重量相对于最后催化剂重量的%表示,是1-20%,优选地2-12%。
第VIII族非贵重金属的量,以氧化物重量相对于最后催化剂重量的%表示,可以是0-10%,优选地1-4%。
磷的量,以氧化物重量相对于最后催化剂重量的%表示,可以是0.3-10%,优选地1-5%,还更优选地1.2%-4%。
硼的量,以氧化物重量相对于最后催化剂重量的%表示是6%以下,优选地2%以下。
元素磷与第VIB族元素的原子比有利地是0.3-0.75。
至少一种掺杂元素是含卤素元素(第VIIA族),卤素的量是以最后催化剂重量计5重量%以下。
该催化剂加到该原料中的浓度(总重量相对于原料的%表示)是0.1-20%,优选地0.5-10%。
载体制备
该氧化铝-基载体具有一种多孔结构,它由多个并置聚集体构成,每个聚集体由多个针状片晶构成,每个聚集体的片晶一般地彼此相对并相对于聚集体中心通常呈放射状取向,所述载体具有不规则的非球状,且主要呈现出通过粉碎氧化铝珠得到的碎片形状,并且是根据包括下述步骤的制备方法得到的:
a)使用结晶不好的结构和/或无定形结构的活性氧化铝粉末制粒,以便得到珠状聚集体;
b)所述珠在60-100℃的湿润气氛中熟化,然后干燥;
c)筛分以回收所述珠的部分;
d)粉碎所述部分;
e)在温度250-900℃温度下煅烧至少一部分所述粉碎部分;
f)在80-250℃温度下进行酸浸渍和水热处理;
g)干燥,然后在温度500-1100℃温度下煅烧。
由该方法得到的载体颗粒的平均尺寸是25-1000微米,优选地100-800微米。
a)第一步,称作“造粒”,目的在于按照如FR 1 438 497描述的方法,由具有结晶不好的结构和/或无定形结构的活性氧化铝粉末形成基本上球状的聚集体。该方法在于借助于水溶液,润湿具有结晶不好的结构和/或无定形结构的活性氧化铝,然后在造粒机或制粒机中成团。优选地,在造粒过程中添加一种或多种成孔剂。可使用的成孔剂特别地是木屑、木炭、纤维素、淀粉、萘,和一般地能通过煅烧被除去的所有有机化合物。
“结晶不好的结构的氧化铝”应理解是这样一种氧化铝,对其进行的X-射线分析得到仅具有一个或几个漫射线的图,这些线相应于低温转变氧化铝的晶体相,并基本上包括χ、ρ、η、γ和假γ相和它们的混合物。一般而言,使用的活性氧化铝是通过氢氧化铝快速脱水得到的,氢氧化铝例如是三羟铝石、水铝矿或三水铝石、新三水氧化铝或羟基氧化铝,如勃姆石和硬水铝石。这种脱水处理可以在任何适合的装置中借助于热气流进行。气体进入装置的温度一般是约400-1200℃,氢氧化物或羟基氧化物与热气体的接触时间一般是几分之一秒至4-5秒。
一般而言,通过氢氧化物或羟基氧化物快速脱水得到活性氧化铝的比表面通过BET法测定是约50-400m2/g,颗粒直径一般是0.1-300微米,优选地1-120微米。利用在1000℃煅烧测定的烧失量一般是3-15%,这相应于H2O/Al2O3摩尔比为0.17-0.85。
根据一个特别的实施方式,优选地来自Bayer水合物(水铝矿)快速脱水得到的活性氧化铝,Bayer水合物是工业氢氧化铝,它易于得到,且特别便宜。本技术领域的技术人员熟知上述活性氧化铝,FR1 108 011中特别地描述了它的制备方法。
采用的活性氧化铝可以原样使用,或者经过处理使以Na2O表示的苏打含量低于1000ppm(重量)后进行使用。采用的活性氧化铝可以经过研磨或未经研磨。
b)得到的球形聚集体然后在不高的温度,优选地60-约100℃,潮湿气氛下进行熟化,接着在100-120℃下进行干燥。
c)在该步骤,基本上呈珠状的聚集体具有足够的机械强度以接受筛分,以便根据期望的最终颗粒粒度选择适合的颗粒粒度范围。因此,例如,为了得到20-1000微米粒度范围内的最终氧化物,将进行筛分并选择1000-2000微米范围内的一部分珠。
d)接着,对所选粒度范围内的这部分珠进行研磨。在本技术领域的技术人员已知的任何类型的破碎机中进行这一操作,优选地在具有球磨的破碎机中。其持续时间是5-60分钟,优选地10-30分钟。
在粉碎步骤之后,氧化铝颗粒主要呈非常不规则的非球形的碎片状。为了更好地限定得到的形状,可以规定这些碎片可以呈粉碎后的珠状,而不具有非常明显的断口面,或者呈固体状,其最接近的几何形状可能是不规则多面体,一定不能具有平面。术语“主要”表示至少50重量%,优选地至少60重量%的珠状聚集体已在粉碎过程中有效地改变其形状,其余部分表示保持完整的珠形聚集体。事实上,人们熟知由于粉碎是一种低效率的简单操作,通常很大部分的颗粒未经粉碎。
e)粉碎后,至少一部分碎片在约250-900℃下,优选地500-850℃下经过煅烧。未经煅烧的部分一般相应于“超规格”细粉。优选地,全部粉碎部分进行煅烧。
f)然后进行酸浸渍,接着根据US 4 552 650描述的方法(其全文应用于本方法中)进行水热处理,即:
-在含有,优选由至少一种酸和至少一种化合物的混合物组成的含水介质中处理这些粉碎聚集体,该酸能溶解氧化物的至少一部分氧化铝,该化合物带有能与溶液中的铝离子化合的阴离子,后一种化合物是与前述酸截然不同的化学个体,
-这样处理的粉碎聚集体同时或者随后接受水热处理(或高压蒸气处理)。
“能使至少部分的氧化物的氧化铝溶解的酸”应该理解是任何酸,它与以上定义的活性氧化铝聚集体接触,使至少一部分铝离子进入到溶液中。酸溶解至少0.5重量%和至多15重量%聚集体的氧化铝。它在含水处理介质中的浓度是低于20重量%,优选地1-15重量%。
优选地使用如硝酸、盐酸、高氯酸或硫酸的强酸,或者使用如乙酸的弱酸,它们以使其水溶液的pH低于约4的浓度进行使用。
“带有能与溶液中铝离子化合的阴离子的化合物”应该理解是能在溶液中释放A(-n)阴离子的任何化合物,该阴离子能与Al(3+)阳离子生成产物,其中n(A/Al)原子比小于或等于3。
这些化合物的一个特别的情况可以通过具有通式Al2(OH)xAy的碱性盐举例说明;其中0<x<6,ny<6,n代表阴离子A的电荷数。
该化合物在含水处理介质中的浓度是低于50重量%,优选地3%-30%。
优选地使用能在溶液中释放阴离子的化合物,这些阴离子选自硝酸根、氯离子、硫酸根、高氯酸根、氯乙酸根、二氯乙酸根、三氯乙酸根、溴乙酸根、二溴乙酸根阴离子和具有通式RCOO(-)的阴离子,其中R代表选自H、CH3、C2H5、CH3CH2和(CH3)2CH的基团。
能在溶液中释放A(-n)阴离子的化合物可以或者直接释放,例如利用离解,或者间接释放,例如利用水解。这些化合物可以特别地选自有机或无机酸、酸酐、有机或无机盐、酯。在这些无机盐中,可以列举可溶于含水介质的碱金属盐或碱土金属盐,像钠盐、钾盐、镁盐或钙盐、铵盐、铝盐和稀土盐。
或者利用聚集体的干浸渍,或者利用聚集体在酸性水溶液中浸渍,可进行该第一项处理。“干浸渍”应该理解是使氧化铝聚集体与一定体积的溶液接触,这个体积小于或等于被处理聚集体的总孔体积。
根据一个特别优选的实施方式,使用硝酸或乙酸或硝酸和甲酸的混合物作为含水介质。
水热处理在约80-250℃温度下进行约5分钟至约36小时。
这种水热处理不会造成氧化铝损失。
优选地使用温度120-220℃,时间为15分钟到18小时。
这种处理构成活性氧化铝聚集体的水热处理,水热处理使至少部分聚集体转化成勃姆石。或者在饱和蒸汽压力下,或者在相应于处理温度的饱和蒸汽压力的至少70%的水蒸汽分压下,可以进行这种水热处理(高压蒸气处理)。
能溶解至少一部分氧化铝的酸与能在水热处理中生成上述产物阴离子的结合导致生成特别的勃姆石,即本发明氧化物的针状片晶前体,其生长由结晶晶种开始以放射方式进行。
此外,处理混合物中酸和化合物的浓度和采用水热处理条件使得不会有氧化铝损失。因此,处理后孔隙度增加是由于处理过程中聚集体膨胀,而不是由于氧化铝损失。
g)最后,一般在约100-200℃下,粉碎的聚集体然后任选地进行干燥一段时间,该时间足以去除没有被化学结合的水。然后聚集体在约500-1100℃下接受热活化,活化时间约15分钟到24小时。
得到的活性氧化铝主要呈不规则非球状,一般具有下述特征:通过在1000℃煅烧测定的烧失量约1-15重量%,比表面约80-300m2/g,其总孔体积约0.45-1.5cm3/g。
此外,得到活性氧化铝粉碎聚集体优选地具有下述特征:
-比表面75-250m2/g;
-夯实密度约0.25-0.65g/cm3;
-总孔体积(VPT)为0.5到约2.0cm3/g;
-采用Hg孔隙度测定技术测定的孔分布优选地有如下特征:
-平均直径的孔的总孔体积的%:40-80;
-平均直径的孔的总孔体积的%:5-60,优选地8-35;
-平均直径的孔的总孔体积的%:3-50,优选地5-30;
h)活性相沉积(金属或催化金属化合物)
优选地,采用本技术领域的技术人员熟知的所谓″干″浸渍方法,在粉碎氧化铝聚集体上进行活性相,即至少一种金属或第VIB族和/或第VIII族的催化金属化合物,和一种或多种掺杂元素的沉积。非常优选地使用含有所有最后催化剂组成元素的溶液(共-浸渍)采用单步骤进行这种浸渍,为了得到这种催化剂可以采用其它的浸渍顺序。
还可能的是,在制备载体过程中,特别在制粒步骤期间加入这些金属的一部分和一部分这种或这些掺杂元素,甚至全部。
可以使用的第VIB族元素源是本技术领域的技术人员熟知的。例如,在这些钼和钨源中,有利地可使用这些氧化物、氢氧化物、钼酸和钨酸及其盐,特别地铵盐,例如钼酸铵、七钼酸铵、钨酸铵、磷钼酸和磷钨酸及其盐,乙酰基丙酮酸盐、黄原酸盐、氟化物,氯化物,溴化物、碘化物、氟氧化物,氯氧化物,溴氧化物、碘氧化物、羰基配合物、硫代钼酸盐和羧酸盐。优选地,使用氧化物和铵盐,例如钼酸铵、七钼酸铵或钨酸铵。
可以使用的第VIII族元素源是已知的且例如是硝酸盐、硫酸盐、磷酸盐、卤化物、羧酸盐,像乙酸盐,或碳酸盐、氢氧化物和氧化物。
优选磷源是正磷酸,但其盐和酯,像碱金属磷酸盐、磷酸铵、磷酸镓或磷酸烷基酯也是合适的。有利地,还可以使用磷的酸,例如次磷酸、磷钼酸及其盐,磷钨酸及其盐。这种磷例如可以以磷酸和含有氮的碱性有机化合物的混合物形式加入,这种有机化合物例如是氨、伯和仲胺、环胺、吡啶和喹啉类化合物以及吡咯类化合物。
硼源可以是硼酸,优选地是原硼酸H3BO3、二硼酸铵或五硼酸铵、硼氧化物或硼酸酯。例如通过硼酸在水/醇混合物中或水/乙醇胺混合物中的溶液加入硼。
可以使用的第VIIA族元素(卤素)源是本技术领域的技术人员熟知的。例如氟阴离子可以氢氟酸或其盐形式加入。这些盐是用碱金属、铵或有机化合物生成的。在其后一种情况下,这种盐有利地是在该反应混合物中通过该有机化合物与氢氟酸的反应生成的。例如用氢氟酸或氟化铵水溶液浸渍可以加入氟。
有利地,在所述载体浸渍后,制备本发明催化剂的方法包括下述步骤:
·湿固体在潮湿气氛下在温度10℃-80℃熟化12-36小时;
·在温度60℃-150℃干燥所得到的湿固体;
·任选地,在温度150℃-800℃下煅烧在干燥后得到的固体。
在浸渍溶液不含有抑制硫化作用的元素氮的化合物的情况下,煅烧就不是必需的。
催化剂的特征
采用Hg孔隙度测定技术测定的催化剂孔分布如下:
-平均直径小于的孔的总孔体积的%:0-10
采用Hg孔隙度测定本发明催化剂的总孔体积是0.4-1.8cm3/g。
采用BET法测定的所述催化剂比表面是50-250m2/g。
根据ASTM D 5757-00的方法,在空气流中通过摩擦测定该催化剂的机械稳定性。对于所述的催化剂,在进行所采用的试验时,产生细粉(其尺寸小于24微米)是5重量%以下。
催化剂的使用
该担载催化剂或者在上游,或者直接在该反应器中被注入并与原料混合,再以浓度0.1-20重量%,优选地0.5-10重量%随该烃相在浆料反应器中进行循环。
优选地,在原料中使用溶解的硫化氢在催化剂达到反应区之前使该催化剂硫化。
根据本发明特别优选的实施方式,在接近反应区温度与压力的温度与压力条件下,将该催化剂注入至少一部分含有溶解硫化氢的液体转化产品中。有利地,这种注入是在所述转化产品的循环回路中进行的。
一般而言,在浆料反应器中有利于加氢转化的条件如下:
·总压力1-50MPa,优选地2-30MPa;
·氢分压1-50MPa,优选地2-30MPa;
·温度300℃-600℃,优选地350℃-500℃;
·液体烃在反应区中的停留时间5分钟至20小时,优选地1-10小时。
采用本发明方法处理的重质原料是例如来自石油真空蒸馏的馏出物或残留物的重质烃原料。它还可以是以悬浮状加入到液体石油馏分中的炭或焦炭。
更一般地,该方法特别适合于处理石油馏分,例如常压蒸馏在塔底得到的常压残留物或这些残留物的一部分,或来自真空蒸馏的残留物(塔底)。一般地,对于至少80重量%的初始沸点高于300℃的原料化合物,这些馏分的特征在于其沸点高于540℃。它们(新原料)在100℃的粘度小于40000cSt,优选地在100℃小于20000cSt,金属Ni+V含量高于1ppm(重量),而在庚烷中沉淀的沥青质含量高于0.1重量%。
根据一个有利实施方式,一部分转化流出物可以被循环到进行加氢转化单元的上游。这些循环流出物含有一部分也被循环的催化组合物。
催化剂再生
一般地,该催化剂再生后再全部或部分被循环到浆料反应器中。
根据一个本发明优选方式,在反应器出口,采用本技术领域的技术人员已知的任何方法,例如蒸馏、过滤或溶剂提取,将该催化剂与这些产物分离,然后使用溶解最大量有机分子的溶剂进行洗涤。
然后可以进行再生,这种再生在于通过在氧化性气氛中在450℃-600℃热处理所述的催化剂,将吸附在该催化剂表面和孔中的焦炭燃烧掉。
根据一个还更优选方式,在热处理步骤前后,优选地使用酸溶液进行化学侵蚀,以便提取大部分金属(镍和钒),这些金属开始存在于原料中,并且在加氢转化和加氢脱金属作用时沉积在该催化剂上。
这些操作能够得到再生催化剂,其活性接近于新催化剂的活性。另外,令人惊奇地,再生后还保持这种多孔的栗子壳斗状结构。
如果想循环大量的催化剂,它们的粒度分布应该是足够稳定的。不同步骤(产物分离、化学侵蚀、再生)因此不应该造成太多催化剂磨损,这样涉及提供在耐磨损方面具有足够机械强度的催化剂。
根据ASTM D5757-00方法,通过在空气流中磨损评价该催化剂的机械强度。本申请人认为,对于该催化剂是可再生的时,它在磨损试验中不应该产生5重量%以上的细粉。
具体实施方式
实施例1:制备具有栗子壳斗状孔结构的氧化铝载体(根据本发明)
原料是在热空气流(T=1000℃)中非常快速分解三水铝石得到的氧化铝。得到的产物是由转变氧化铝混合物组成的:(χ)和(ρ)氧化铝。这种产物的比表面是300m2/g,烧失量(PAF)是5%。
该氧化铝(磨碎后)呈粉状,其平均颗粒直径是7微米。
这种氧化铝与作为成孔剂的木屑混合(15重量%),然后在造粒机或制粒机中成型一段时间,调整成期望的颗粒粒度。对得到的聚集体通过100℃水蒸汽达24小时进行熟化步骤,然后进行干燥。接着对它进行筛分,然后粉碎,最终进行煅烧。
然后,这些珠在浸渍滚筒中用溶液进行干浸渍,该溶液在水相中含有例如硝酸和乙酸的混合物。一旦经过浸渍,它们就在210℃温度与20.5巴压力下被加到高压釜中约2小时。
在高压釜出口得到粉碎的氧化铝聚集体,然后在100℃下干燥4小时,在650℃煅烧2小时。
这些聚集体的尺寸是200-500微米。它们的孔体积等于0.95cm3/g。载体比表面是130m2/g。
采用Hg孔隙度测定技术测定的孔分布特征如下:
-平均直径的孔的总孔体积的%:75;
实施例2:制备由磨碎氧化铝氧化物组成的载体(非本发明)
原料是由勃姆石或La Roche公司以商品名Versal 250销售的氧化铝凝胶组成的基质。这种凝胶与含有52.7%硝酸的水溶液进行混合(每克干凝胶为1重量%酸),然后在具有Z形搅拌臂的混合器中进行混合20分钟。然后,这种糊剂在同一混合器中与含有20.3%氨的水溶液进行混合5分钟(每克酸为40摩尔%氨)。这种混合结束后,让得到的糊剂通过在活塞式挤出机上的具有直径等于或小于1.0mm的圆柱形孔的拉丝模。这些挤出物在120℃干燥一夜,在含有200g水/kg干燥空气的湿空气流中在750℃煅烧两小时,最后被粉碎得到粒度200-500微米的碎片。
而且氧化铝的这种氧化物的比表面是190m2/g,总孔体积0.95cm3/g,双模态孔分布。采用Hg孔隙度测定技术测定的孔分布的特征如下:
实施例3:制备具有栗子壳斗状孔结构的氧化铝载体(非本发明)
采用实施例1的操作方式制备呈珠状的载体,只是在高压釜步骤后进行粉碎步骤除外。
于是,在干燥(4h,100℃)和煅烧(2h,650℃)步骤后的高压釜出口,这些珠被粉碎、筛分得到尺寸200-500微米的部分。
实施例4:使用实施例1、2和3载体制备催化剂A、B和C
实施例1、2和3的载体使用含有钼和镍盐与磷酸的水溶液进行干浸渍。钼前体是钼氧化物MoO3,镍的前体是碳酸镍Ni(CO3)。在室温在用水饱和的气氛下熟化后,浸渍载体在120℃干燥一夜,然后在干燥空气中在500℃煅烧2小时。三氧化钼的最后含量是成品催化剂的9.4重量%。氧化镍NiO最后含量是成品催化剂的2重量%。氧化磷P2O5最后含量是成品催化剂的2重量%。
分别由实施例1、2和3载体得到催化剂A、B和C的结构和物理化学特征列于表1中。
表1
一般而言,本发明方法使用催化剂的孔分布与该载体的几乎相同。
实施例5:催化剂A、B、C机械强度比较
采用ASTM D5757-00空气流磨损方法,称为“″FCC磨损法″测定催化剂A、B和C的机械强度。
下表2列出催化剂A、B、C磨损得到的结果。
表2
催化剂 | A(非本发明) | B | C |
%产生<24微米细粉 | 2% | 3% | 6% |
对于催化剂C,采用这种方法产生的细粉百分数与其在浆料和再生中的应用是不相相容的。
实施例6:在间断反应器中以浆料方式加氢转化残留物中催化剂A、
B、C的性能比较
催化剂A、B和C以浓度1重量%与原料一起加到间断反应器中。保持搅拌。
使用原料是富含金属的RA Zuata,其具有下述特征:
原料 | RA Zuata |
比重 | 1.045 |
硫(重量%) | 4.35 |
氮(ppm,以重量计) | 9000 |
粘度(cSt) | 900 |
粘度温度(℃) | 125 |
康氏C(重量%) | 19.95 |
沥青质,C7(重量%) | 13 |
Ni(ppm,以重量计) | 134 |
V(ppm,以重量计) | 660 |
DS:PI,℃ | 295 |
DS:5体积%,℃ | 375 |
DS:10体积%,℃ | 419.5 |
DS:30体积%,℃ | 540 |
DS:48体积%,℃ | 613.5 |
D1160:60体积%,℃ | - |
高压釜试验分两步进行:
1)硫化步骤:在氢气压力100巴下,在DMDS(二甲基二硫醚)存在下,让该催化剂与RA原料混合。该混合物被加热到350℃持续1小时内:这个温度能使DMDS分解,于是产生H2S分压力,模拟工业单元循环回路中的H2S分压。这个步骤能使沉积在该催化剂上的钼硫化;
2)然后,将该反应器冷却直到低于100℃的温度,并用氮气汽提H2S和氢气。
然后,在下述条件下启动加氢转化步骤:
·温度:410℃;
·H2压力:150巴;
·停留时间:1小时30分钟
试验结束时,采用热过滤从液相中分离出固体相;分析滤液中的金属和沥青质(不溶C7),以测定%HDM(加氢脱金属作用)和HDAsphC7(加氢脱沥青)。
催化剂 | 转化(重量%) | HDM(重量%) | HDAsphC7 |
A | 52 | 77 | 60 |
B | 50 | 72 | 57 |
C | 52 | 76 | 59 |
因此,催化剂A(本发明)在HDM和HDAsphC7方面相对于催化剂B(非本发明)的上述方面具有明显改善的催化性能,催化剂B没有″栗子壳斗″类型的孔结构。另外一方面,它们也稍微优于催化剂C,催化剂C有″栗子壳斗″类型的孔结构,但没有足以用于浆料反应器中的机械强度。
Claims (19)
1.在氢气存在下与在催化剂存在下在浆料反应器中进行的重质原料转化方法,该催化剂含有在氧化铝上担载的至少一种催化金属或第VIB族和/或第VIII族催化金属化合物,其孔结构是由多个并置的聚集体构成的,每个聚集体由多个针状片晶构成,每个聚集体的片晶彼此相对并相对于聚集体中心通常呈放射状取向,所述催化剂具有不规则的非球形状,主要呈碎片形式,是根据包括下述步骤的制备方法得到的:
a)使用具有结晶不好的结构和/或无定形结构的活性氧化铝粉末制粒,得到珠状聚集体;
b)所述珠在60-100℃的湿润气氛中熟化,然后干燥;
c)筛分以回收所述珠的部分;
d)粉碎所述部分;
e)在温度250-900℃下煅烧至少一部分的所述粉碎部分;
f)在温度80-250℃下进行酸浸渍和水热处理;
g)干燥,然后在温度500-1100℃温度下煅烧;
h)浸渍至少一种催化金属或第VIB族和/或第VIII族催化金属化合物。
2.根据权利要求1所述的方法,其中根据ASTM D5757-00标准测定的所述担载的催化剂磨损损失小于5重量%。
6.根据权利要求1或2所述的方法,其中采用Hg孔隙度测定技术测定的担载催化剂总孔体积是0.4-1.8cm3/g,采用B.E.T法测定的比表面是50-250m2/g。
7.根据权利要求1或2所述的方法,其中所述催化剂含有的第VIB族金属是钼或钨。
8.根据权利要求1或2所述的方法,其中所述催化剂含有的第VIII族金属是镍或钴。
9.根据权利要求1或2所述的方法,其中所述催化剂含有至少一种选自磷、硼和卤素的掺杂元素。
10.根据权利要求9所述的方法,其中所述催化剂的掺杂元素是磷。
11.根据权利要求1或2所述的方法,其中所述催化剂是NiMoP类的。
12.根据权利要求1或2所述的方法,其中所述催化剂的颗粒平均尺寸是25-1000微米。
13.根据权利要求12所述的方法,其中所述催化剂的平均颗粒尺寸是100-800微米。
14.根据权利要求1或2所述的方法,其中所述催化剂注入至少部分所述液体转化产品中,它们含有在接近于浆液反应器操作温度和压力的温度和压力条件下溶解的硫化氢。
15.根据权利要求1或2所述的方法,其中所述催化剂以浓度0.1-20重量%添加到这种原料中。
16.根据权利要求15所述的方法,其中所述催化剂以浓度0.5-10重量%添加到这种原料中。
17.根据权利要求1或2所述的方法,其中对这种浆料反应器供给一种原料,其中对于至少80重量%的初始沸点高于300℃的原料化合物,原料的沸点高于540℃,并在下述条件下进行:
●总压力1-50MPa;
●氢分压1-50MPa;
●温度300℃-600℃;
●烃停留时间5分钟至20小时。
18.根据权利要求1或2所述的方法,其中所述催化剂通过实施下述步骤进行再生:
●在反应器出口从这些产物中分离该催化剂;
●使用可溶解性溶剂洗涤;
●在氧化性气氛中在450℃-600℃下热处理催化剂。
19.根据权利要求18所述的方法,其中在热处理步骤前或后进行化学侵蚀。
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Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101767375B1 (ko) | 2009-04-21 | 2017-08-11 | 알베마를 유럽 에스피알엘 | 인 및 붕소를 함유하는 수소처리 촉매 |
FR2958657B1 (fr) * | 2010-04-13 | 2012-05-11 | Inst Francais Du Petrole | Procede d'hydroconversion de charges petrolieres via une technologie en slurry permettant la recuperation des metaux du catalyseur et de la charge mettant en oeuvre une etape de cokefaction. |
CA2772170C (fr) | 2009-10-08 | 2018-03-06 | IFP Energies Nouvelles | Procede d'hydroconversion de charges lourdes carbonees integrant une technologie a lit bouillonnant et une technologie en slurry |
FR2958658B1 (fr) * | 2010-04-13 | 2012-03-30 | Inst Francais Du Petrole | Procede d'hydroconversion de charges petrolieres via une technologie en slurry permettant la recuperation des metaux du catalyseur et de la charge mettant en oeuvre une etape de lixiviation. |
FR2958656B1 (fr) * | 2010-04-13 | 2012-05-11 | Inst Francais Du Petrole | Procede d'hydroconversion de charges petrolieres via une technologie en slurry permettant la recuperation des metaux du catalyseur et de la charge mettant en oeuvre une etape d'extraction. |
GB2478332A (en) | 2010-03-04 | 2011-09-07 | Grimley Smith Associates | Method of metals recovery from refinery residues |
US8608945B2 (en) | 2010-06-10 | 2013-12-17 | Uop Llc | Process for using supported molybdenum catalyst for slurry hydrocracking |
US8617386B2 (en) | 2010-06-10 | 2013-12-31 | Uop Llc | Process for using supported molybdenum catalyst for slurry hydrocracking |
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 |
US8802587B2 (en) * | 2010-12-30 | 2014-08-12 | Chevron U.S.A. Inc. | Hydroprocessing catalysts and methods for making thereof |
FR2974108B1 (fr) * | 2011-04-14 | 2014-11-28 | IFP Energies Nouvelles | Procede d'hydroconversion de biomasse integrant une technologie en lit bouillonnant et une technologie en slurry |
CN102836727A (zh) * | 2011-06-23 | 2012-12-26 | 中国石油天然气集团公司 | 一种具有高脱氮和脱芳烃活性加氢催化剂的制备方法 |
CN103285939B (zh) * | 2012-03-02 | 2015-11-25 | 中国石油化工股份有限公司 | 具有加氢催化作用的催化剂及其制备方法和应用以及加氢精制方法 |
CN103285940B (zh) * | 2012-03-02 | 2016-03-23 | 中国石油化工股份有限公司 | 具有加氢催化作用的催化剂及其制备方法和应用以及加氢精制方法 |
SG10201608662PA (en) * | 2012-04-26 | 2016-12-29 | Shell Int Research | A hydroprocessing catalyst and process for treating heavy hydrocarbon feedstocks |
US20180016505A1 (en) * | 2015-05-29 | 2018-01-18 | Jxtg Nippon Oil & Energy Corporation | Method for producing hydrotreated oil and method for producing catalytic cracked oil |
US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
US20190233741A1 (en) | 2017-02-12 | 2019-08-01 | Magēmā Technology, LLC | Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil |
US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
FR3116831B1 (fr) * | 2020-11-27 | 2023-11-03 | Ifp Energies Now | Procede d’hydrogenation selective d’une essence en presence d’un catalyseur sur support meso-macroporeux |
FR3116829B1 (fr) * | 2020-11-27 | 2023-11-03 | Ifp Energies Now | Procede d’hydrodesulfuration en presence d’un catalyseur sur support meso-macroporeux |
FR3116832B1 (fr) * | 2020-11-27 | 2023-11-03 | Ifp Energies Now | Procede d’hydrodesulfuration de finition en presence d’un catalyseur sur support meso-macroporeux |
FR3116826B1 (fr) * | 2020-11-27 | 2023-11-03 | Ifp Energies Now | Procede d’hydrodesulfuration mettant en œuvre un catalyseur comprenant un support d’alumine flash |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5300212A (en) * | 1992-10-22 | 1994-04-05 | Exxon Research & Engineering Co. | Hydroconversion process with slurry hydrotreating |
US5935418A (en) * | 1997-08-29 | 1999-08-10 | Exxon Research And Engineering Co. | Slurry hydroprocessing |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2651617A (en) * | 1949-04-16 | 1953-09-08 | Universal Oil Prod Co | Treatment of alumina containing catalytic composites |
FR2496631B1 (fr) * | 1980-12-23 | 1989-06-30 | Rhone Poulenc Ind | Procede de preparation d'agglomeres d'alumine |
US5244648A (en) * | 1980-12-23 | 1993-09-14 | Rhone-Poulenc Industries | Process for the preparation of alumina agglomerates |
FR2528721B1 (fr) * | 1982-06-17 | 1986-02-28 | Pro Catalyse Ste Fse Prod Cata | Catalyseur supporte presentant une resistance accrue aux poisons et son utilisation en particulier pour l'hydrotraitement de fractions petrolieres contenant des metaux |
FR2534828B1 (fr) * | 1982-10-21 | 1986-12-26 | Pro Catalyse | Catalyseurs a base d'alumine, de silice ou de silice-alumine, leur preparation et leur utilisation dans le domaine de l'hydrotraitement des huiles d'hydrocarbures |
FR2538814B1 (fr) * | 1982-12-30 | 1986-06-27 | Inst Francais Du Petrole | Procede de traitement d'une huile lourde ou d'une fraction d'huile lourde pour les convertir en fractions plus legeres |
FR2538813A1 (fr) * | 1982-12-31 | 1984-07-06 | Inst Francais Du Petrole | Procede d'hydrotraitement convertissant en au moins deux etapes une fraction lourde d'hydrocarbures contenant des impuretes soufrees et des impuretes metalliques |
JP3674227B2 (ja) * | 1997-03-14 | 2005-07-20 | 株式会社日立製作所 | 可搬メディアを収納する記憶装置 |
FR2867988B1 (fr) * | 2004-03-23 | 2007-06-22 | Inst Francais Du Petrole | Catalyseur supporte dope de forme spherique et procede d'hydrotraitement et d'hydroconversion de fractions petrolieres contenant des metaux |
US20090166260A1 (en) * | 2005-12-22 | 2009-07-02 | Stephane Kressmann | Irregularly shaped non-spherical supported catalyst, and a process for hydroconverting heavy oil fractions |
-
2006
- 2006-12-21 FR FR0611403A patent/FR2910352B1/fr not_active Expired - Fee Related
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2007
- 2007-12-17 AU AU2007249084A patent/AU2007249084B2/en not_active Ceased
- 2007-12-19 CA CA2615225A patent/CA2615225C/fr not_active Expired - Fee Related
- 2007-12-20 US US11/961,132 patent/US7807044B2/en not_active Expired - Fee Related
- 2007-12-21 CN CN2007101857267A patent/CN101255360B/zh not_active Expired - Fee Related
- 2007-12-29 SA SA07280716A patent/SA07280716B1/ar unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5300212A (en) * | 1992-10-22 | 1994-04-05 | Exxon Research & Engineering Co. | Hydroconversion process with slurry hydrotreating |
US5935418A (en) * | 1997-08-29 | 1999-08-10 | Exxon Research And Engineering Co. | Slurry hydroprocessing |
Also Published As
Publication number | Publication date |
---|---|
CA2615225C (fr) | 2015-10-27 |
AU2007249084A1 (en) | 2008-07-10 |
US20080149531A1 (en) | 2008-06-26 |
US7807044B2 (en) | 2010-10-05 |
FR2910352B1 (fr) | 2010-10-08 |
SA07280716B1 (ar) | 2011-05-04 |
CA2615225A1 (fr) | 2008-06-21 |
CN101255360A (zh) | 2008-09-03 |
AU2007249084B2 (en) | 2011-08-11 |
FR2910352A1 (fr) | 2008-06-27 |
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