CN111001411A - 一种渣油加氢处理催化剂及其制备方法 - Google Patents
一种渣油加氢处理催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开的是一种渣油加氢处理催化剂及其制备方法,催化剂介孔孔径集中分布且均一,同时具有大孔的双峰孔催化剂,其中10~30nm介孔的分布在50%以上,且集中分布,大孔分布在25%以上,制备方法:配制铝盐溶液,采用pH摆动法进行溶胶的混合,加入有机扩孔剂,导加入成胶罐中成胶,经老化、干燥、成型、焙烧,获得氧化铝载体;将氧化铝载体浸渍在浸渍液,干燥、焙烧,得到加氢脱金属催化剂,本发明催化剂具有良好的扩散性能和优异的脱金属性能,能够满足含Ni、V重金属化合物扩散的孔道,显著提高了催化剂的脱镍、脱钒性能,提升了催化剂的脱金属活性、容金属能力及活性稳定性,制备工艺简单,易操作。
Description
技术领域
本发明涉及一种催化剂及其制备方法,更具体一点说,涉及一种渣油加氢处理催化剂及其制备方法,属于石油化工领域。
背景技术
随着世界范围内原油日趋重质化、劣质化,炼厂的渣油产量日益增多,减压渣油的加工成为了炼厂设计的核心。而石油产品需求趋于轻质化、清洁化,因此最大限度的将渣油转化为轻质油品及高附加值产品,改善产品质量,提高原油的综合利用,成为炼厂提高经济效益的关键。
渣油作为炼油过程中的“桶底油”,其特点是富含原油中大多数的硫、氮、重金属(Ni、V为主)等杂质,且分子量大、黏度高,反应过程受内扩散影响显著,可加工性能差。固定床渣油加氢处理以其过程清洁化、杂质脱除率高、产品液收高等优势,成为改善渣油可加工性能,实现渣油高效绿色转化的核心工艺路线。固定床渣油加氢处理的核心是渣油加氢处理催化剂。
但现有加氢处理的关键问题是重油中金属化合物易于在脱金属催化剂孔道及表面沉积,导致催化剂的床层压降增大、催化剂使用寿命低、需要及时更换催化剂,加氢处理操作成本高。
开发高活性与稳定性的渣油加氢处理催化剂,需要对重油加氢脱金属的扩散、反应及沉积规律进行深入的认识,形成催化剂开发的理论指导,如不同金属化合物扩散、反应对孔道尺寸的要求、对表面酸性的要求,沥青质对金属沉积的影响等。因此,具有较大孔容与最佳孔径的载体是高活性加氢脱金属催化剂制备的基础,适宜酸性与匹配加氢活性则是催化剂制备的关键。
目前,一般的加氢脱金属催化剂的开发多是围绕扩大载体的孔径这一基础而展开,即在载体的制备过程中,通过加入扩孔剂等手段得到大孔氧化铝载体。研究表明,脱金属催化剂需要较大的孔容和孔径,才能保证催化剂容金属能力,进而提高催化剂的使用寿命,延长装置的运转周期。另一方面,催化剂的大孔能够为大分子反应物料提供适宜的扩散孔道,使得大分子物质更易到达催化剂的内部表面,有效改善大分子反应物的扩散效应,并能够促进催化剂内部金属沉积,提高催化剂的利用率。更确切的研究结果表明,>100nm孔径更有利于大分子的扩散;介孔是催化剂脱金属的最佳孔径区间,可为反应提供高比表面积,提高活性金属分散度,促进杂质的脱除与沉积,更确切的,10~30nm孔径是脱金属的最佳孔道。因此,催化剂的介孔孔径(10~30nm)集中分布且均一,同时兼具大孔(>100nm)的双峰孔催化剂是最佳的高活性与稳定性的渣油加氢脱金属催化剂。
CN 106914250A公布了一种渣油加氢处理催化剂及其制备方法,将成型并预焙烧的氧化铝前驱体,用浓度逐渐增加的酸性溶液进行处理得到大孔载体;大孔载体经浸渍金属后进行预干燥和水洗处理,最后经干燥和焙烧后得到催化剂。该法需对氧化铝前驱体进行均匀喷洒浓度连续的酸或酸性溶液,难以实现载体大孔的均匀分布;且制备过程采取多次干燥、焙烧操作,造成催化剂机械强度下降,整体制备流程过于复杂。
CN 103864124A公布了一种结合软硬双模板法制备介孔-大孔梯度孔结构氧化铝载体的方法,该方法首先采用无乳化剂聚合的方法制备粒径均匀的聚丙烯酸甲酯(PMMA)微球,并通过离心的方法组装成PMMA硬模板,然后将PMMA硬模板浸润在含有九水硝酸铝和表面活性剂F127乙醇溶液中,最后通过抽滤、干燥、焙烧得到三维有序大孔氧化铝。但该法生产的载体孔径梯度分布,最有效的介孔(10-30nm)分布较少,难题提高催化剂的脱金属活性。
CN 1135518A公布了一种加氢处理催化剂及其制备方法,该法利用PH摆动法制备得到氧化铝载体。虽然该法工艺流程简单,但所得的氧化铝载体的大孔孔径分布较少,不利于大分子反应物向内部孔隙扩散,易于结焦堵塞孔道,催化剂的容金属能力明显不足。
综上所述,基于渣油中重金属Ni、V等化合物在催化剂内部扩散与反应特性,构筑具有介孔孔径集中分布且均一,同时兼具大孔的双峰孔催化剂,才能满足大分子金属化合物在催化剂内部孔道的扩散需求,减少金属在催化剂孔口堵塞,同时在最佳的介孔孔道中进行脱金属反应,提高脱金属催化剂的活性与稳定性。
发明内容
本发明的目的是针对现有技术的不足,提供一种渣油加氢处理催化剂及其制备方法,该法获得的催化剂具有介孔孔径分布集中且均一、同时兼具大孔的双峰孔分布结构,可作为劣质重油尤其是渣油加氢处理催化剂使用。
本方法的关键技术是采用PH摆动法制备均一的氧化铝载体过程中加入有机扩孔剂。PH摆动法制备的氢氧化铝凝胶,因PH的有序摆动而生成不同粒径胶团的氢氧化铝凝胶,有利于载体生成均一的介孔。在PH摆动中加入有机扩孔剂,有机扩孔剂能够更加均匀的分散到氢氧化铝凝胶中,通过调控加入扩孔剂的量,可以精确的调控载体中介孔和大孔的比例。通过该方法焙烧后制备的载体具有介孔孔径分布集中且均一、同时兼具大孔的双峰孔分布结构,可作为劣质重油尤其是渣油加氢处理催化剂使用。
为了实现上述目的,本发明是通过以下技术方案实现的:
一种渣油加氢处理催化剂,其特征在于:所述催化剂以10~30nm孔径集中分布且均一,同时具有>100nm的大孔分布的氧化铝为载体,通过特定金属担载的方法使介孔表面更多的负载VIII族和VIB族催化剂活性金属,催化剂载体的孔容为0.9~1.2ml/g、比表面积200~350m2/g,10~30nm介孔的孔容占载体总孔容的40~80%,>100nm大孔的孔容占载体总孔容的10~40%,制备催化剂含有MoO3或者WO3为6.0~14.0w%,优选为6.5~12.0w%,CoO或者NiO为1.0~5.0w%,优选为1.5~3.5w%(以氧化物含量计)。
优选的,上述任意一种渣油加氢处理催化剂载体的比表面积为220~330m2/g。
优选的,上述任意一种渣油加氢处理催化剂载体的孔容为0.95~1.2ml/g。
优选的,上述任意一种渣油加氢处理催化剂载体的10~30nm介孔的孔容占载体总孔容的50~70%,>100nm大孔的孔容占载体总孔容的15~40%。
本发明制备的加氢脱金属催化剂可以用于各种重质馏分油及渣油的加氢脱金属过程,特别适合于脱沥青油及渣油的加氢脱金属过程。
本发明提出的催化剂制备过程如下:
(1)制备载体:配制铝盐溶液,采用PH摆动法进行溶胶的混合,在混合过程中加入有机扩孔剂,导加入成胶罐中,于60~90℃成胶,成胶结束后,经老化、干燥、成型、焙烧,即氧化铝载体;其中,所述pH调节剂的用量以最终反应体系的pH值为8~10为准;
(2)由(1)所得的氧化铝载体,等体积浸渍一定量的Mo/W和/或Co/Ni溶液(MoO3/WO3的总质量占催化剂质量的5.0~14.0%,NiO/CoO的总质量占催化剂质量的1.0~5.0%),然后在90~150℃温度条件下干燥2~8小时,再在600~800℃下,焙烧1~5小时,得到加氢脱金属催化剂。
其中,步骤(1)中所述的有机扩孔剂为聚苯乙烯球或聚甲基丙烯酸甲酯球中的一种或者几种,其直径为30~300nm。
步骤(1)中聚苯乙烯球或聚甲基丙烯酸甲酯球的用量,以焙烧后的氧化铝为基准计算,10~30%。
步骤(1)中所述载体的焙烧温度为550℃~1100℃。
步骤(2)中的浸渍液选自Mo~Ni、Mo~Co、W~Co溶液中的一或者几种。
有益效果:具有良好的扩散性能和优异的脱金属性能,大孔能够满足含Ni、V重金属化合物扩散的孔道,而集中分布的介孔孔道显著提高了催化剂的脱镍、脱钒性能,提升了催化剂的脱金属活性、容金属能力及活性稳定性,本发明催化剂适用于劣质重油,如减压渣油、减压馏分油、脱沥青油的加氢处理过程;本申请采用PH摆动法制备均一的氧化铝载体过程中加入有机扩孔剂。PH摆动法制备的氢氧化铝凝胶,因PH的有序摆动而生成不同粒径胶团的氢氧化铝凝胶,有利于载体生成均一的介孔。在PH摆动中加入有机扩孔剂,有机扩孔剂能够更加均匀的分散到氢氧化铝凝胶中,通过调控加入扩孔剂的量,可以精确的调控载体中介孔和大孔的比例。通过该方法焙烧后制备的载体具有介孔孔径分布集中且均一、同时兼具大孔的双峰孔分布结构,可作为劣质重油尤其是渣油加氢处理催化剂使用。
具体实施方式
以通过具体的实施例对本发明作进一步说明,但本发明并不局限于以下实施例。
一种渣油加氢处理催化剂,所述催化剂包括催化剂载体以及负载在催化剂载体上催化剂主体,所述催化剂主体上具有介孔,所述介孔集中分布且大小均一,且介孔的孔径范围为10~30nm,所述催化剂载体具有大于100nm的大孔;
所述催化剂载体的总孔容为0.9~1.2ml/g,比表面积200~350m2/g,介孔的孔容占催化剂载体总孔容的40~80%,大孔的孔容占催化剂载体总孔容的10~40%;以氧化物为基准所述催化剂含有6.0~14.0w%的MoO3或WO3,1.0~5.0w%的CoO或NiO。
作为一种改进的实施例方式,所述催化剂含有6.5~12.0w%的MoO3或WO3以及1.5~3.5w%的CoO或NiO。
作为一种改进的实施例方式,所述催化剂载体比表面积为220~330m2/g。
作为一种改进的实施例方式,所述催化剂载体总孔容为0.95~1.1ml/g。
作为一种改进的实施例方式,所述催化剂载体为氧化铝。
作为一种改进的实施例方式,所述介孔的孔容占催化剂载体总孔容的50~70%,所述大孔的孔容占催化剂载体总孔容的15~40%。
本发明一种渣油加氢处理催化剂的制备方法,该制备方法包括如下步骤:
步骤1):制备载体:配制铝盐溶液(三氯化铝溶液),采用pH摆动法进行溶胶的混合,在混合过程中加入有机扩孔剂,导加入成胶罐中,于60~90℃成胶,成胶结束后,经老化、干燥、成型,然后在550℃~1100℃条件下焙烧,获得氧化铝载体;PH摆动范围为4~10,最终反应体系的pH值为8~10为准;
步骤2):将氧化铝载体等体积浸渍在Mo或W以及Co或Ni的浸渍液,然后在90~150℃温度条件下干燥2~8小时,再在600~800℃下,焙烧1~5小时,得到加氢脱金属催化剂;
所述加氢脱金属催化剂中含有MoO3或WO3以及NiO或CoO,所述MoO3或WO3的总质量占催化剂质量的5.0~14.0%,所述NiO或CoO的总质量占催化剂质量的1.0~5.0%。
作为一种改进的实施例方式,步骤1)中所述有机扩孔剂为聚苯乙烯球、聚甲基丙烯酸甲酯球中的一种或者两种,所述有机扩孔剂的直径为30~300nm。
作为一种改进的实施例方式,以焙烧后的氧化铝为基准计算,所述聚苯乙烯球和/或聚甲基丙烯酸甲酯球的用量占10~50%。
作为一种改进的实施例方式,步骤2)中的浸渍液为Mo-Ni、Mo-Co、W-Co、W-Ni溶液中的一种。
本申请在载体制备的过程中,采用PH摆动法引入到溶胶中的扩孔剂可以均匀地分散在载体中,引入有机扩孔剂是制备技术的关键,扩孔剂在溶胶凝胶生产的过程中,可以均匀地分散在载体中。
催化剂载体以及催化剂主体的孔结构性质采用美国康塔公司的Poremater Macro压汞仪进行测定,催化剂抗压碎强度采用BR17~GCS催化剂颗粒抗压测试仪进行,油品中金属含量的测定是利用原子发射光谱仪进行测定。
在滴流床加氢微型反应装置上,以某减压渣油原料进行加氢脱金属催化剂的反应活性评价,在100ml固定床反应器上评价催化剂。加氢脱金属反应300小时后取样进行金属镍、钒含量的测定。采用等离子发射光谱(AES/ICP)方法测定生成油中的镍和钒的含量,并计算脱金属率。
实例中所用的试剂,除特别说明的以外,均为化学纯试剂。
实施例1
(1)制备载体:配制0.98M的三氯化铝溶液,在搅拌条件下,将上述三氯化铝溶液与氨水采用PH摆动法并流加入至成胶罐中,三氯化铝流速为2.0ml/min,控制成胶罐中温度70℃,PH摆动范围为4~10,最终反应体系的pH值为8~10,同时加入聚苯乙烯球扩孔剂溶液2.0ml/min,扩孔剂总加入量为焙烧后氧化铝质量的30%,成胶结束后,老化0.5h,真空条件下于50℃干燥60h,挤条成型后,700℃焙烧6h,即得氧化铝载体γ~Al2O3;
(2)浸渍活性金属:按照最终催化剂中MoO3的含量7.0wt%,NiO的含量2.0%计,称取适量的七钼酸铵和硝酸镍配制成水溶液,采用等体积浸渍法浸渍载体,于70℃浸渍2h,然后在120℃条件下真空干燥2h,650℃下焙烧4h,得到催化剂MoO3-NiO/γ~Al2O3催化剂A1。
实施例2
(1)制备载体:配制0.98M的三氯化铝溶液,在搅拌条件下,将上述三氯化铝溶液与氨水采用PH摆动法并流加入至成胶罐中,三氯化铝流速为2.0ml/min,控制成胶罐中温度70℃,PH摆动范围为4~10,最终反应体系的pH值为8~10,同时加入聚苯乙烯球扩孔剂溶液2.0ml/min,扩孔剂总加入量为焙烧后氧化铝质量的35%,成胶结束后,老化0.5h,真空条件下于50℃干燥60h,挤条成型后,700℃焙烧6h,即得氧化铝载体γ~Al2O3;
(2)浸渍活性金属:按照最终催化剂中MoO3的含量7.0wt%,NiO的含量2.0%计,称取适量的七钼酸铵和硝酸镍配制成水溶液,采用等体积浸渍法浸渍载体,于70℃浸渍2h,然后在120℃条件下真空干燥2h,650℃下焙烧4h,得到催化剂MoO3-NiO/γ~Al2O3催化剂A2。
实施例3
(1)制备载体:配制1.1M的三氯化铝溶液,在搅拌条件下,将上述三氯化铝溶液与氨水采用PH摆动法并流加入至成胶罐中,三氯化铝流速为2.0ml/min,控制成胶罐中温度70℃,PH摆动范围为4~10,最终反应体系的pH值为8~10,同时加入聚苯乙烯球扩孔剂溶液2.0ml/min,扩孔剂总加入量为焙烧后氧化铝质量的40%,成胶结束后,老化0.5h,真空条件下于50℃干燥60h,挤条成型后,700℃焙烧6h,即得氧化铝载体γ~Al2O3;
(2)浸渍活性金属:按照最终催化剂中MoO3的含量7.0wt%,NiO的含量2.0%计,称取适量的七钼酸铵和硝酸镍配制成水溶液,采用等体积浸渍法浸渍载体,于70℃浸渍2h,然后在120℃条件下真空干燥2h,650℃下焙烧4h,得到催化剂MoO3-NiO/γ~Al2O3催化剂A3。
对比例1
按照实施例1的方法,但是不加入有机扩孔剂聚苯乙烯球,制备的催化剂为对比催化剂D1。
各个催化剂载体的性质列于表1中。
表1各个载体的性质
A1 | A2 | A3 | 对比例1 | |
比表面积/m<sup>2</sup>/g | 265 | 239 | 223 | 273 |
孔容/ml/g | 0.95 | 1.01 | 1.15 | 0.60 |
平均孔径/nm | 29.5 | 34.3 | 36.7 | 6.8 |
<10nm | 5.20% | 4.50% | 4.10% | 86.44% |
10~30nm | 58.43% | 54.60% | 52.70% | 6.43% |
30~100nm | 11.24% | 9.70% | 9.40% | 1.48% |
>100nm | 25.13% | 31.20% | 33.80% | 5.65% |
MoO<sub>3</sub> | 7.0% | 7.0% | 7.0% | 7.0% |
NiO | 2.0% | 2.0% | 2.0% | 2.0% |
在滴流床加氢微型反应装置上,以减压渣油原料进行加氢脱金属催化剂的反应活性评价,在100ml固定床反应器上评价催化剂。采用的硫化及反应条件如表2所示,加氢脱金属反应300小时后取样进行金属镍、钒含量的测定。采用等离子发射光谱(AES/ICP)方法测定生成油中的镍和钒的含量,并计算脱金属率,结果列于表3中。
表2催化剂加氢脱金属反应活性评价工艺条件
表3催化剂加氢脱金属性能数据
A1 | A2 | A3 | 对比例1 | |
HDNi/% | 61.9 | 64.5 | 60.2 | 35.2 |
HDV/% | 80.9 | 83.7 | 81.5 | 54.5 |
通过表3中的加氢脱金属性能数据发现,采用本发明方法制备的加氢脱金属催化剂具有较高的脱镍性能和脱钒性能,本发明催化剂脱镍、钒的百分比远远高于对比例1中催化剂脱镍、钒百分比,表明了催化剂介孔孔径集中分布且均一,同时具有大孔的双峰孔催化剂有助于提高催化剂的脱镍与脱钒活性,尤其是脱镍活性得到更大幅度的提高。
最后,需要注意的是,本发明不限于以上实施例,还可以有很多变形。本领域的普通技术人员能从本发明公开的内容中直接导出或联想到的所有变形,均应认为是本发明的保护范围。
Claims (10)
1.一种渣油加氢处理催化剂,其特征在于:所述催化剂包括催化剂载体以及负载在催化剂载体上催化剂主体,所述催化剂主体上具有介孔,所述介孔集中分布且大小均一,且介孔的孔径范围为10~30nm,所述催化剂载体具有大于100nm的大孔;
所述催化剂载体的总孔容为0.9~1.2ml/g,比表面积200~350m2/g,介孔的孔容占催化剂载体总孔容的40~80%,大孔的孔容占催化剂载体总孔容的10~40%;
以氧化物为基准所述催化剂含有6.0~14.0w%的MoO3或WO3,1.0~5.0w%的CoO或NiO。
2.根据权利要求1所述的一种渣油加氢处理催化剂,其特征在于:所述催化剂含有6.5~12.0w%的MoO3或WO3以及1.5~3.5w%的CoO或NiO。
3.根据权利要求1或2所述的一种渣油加氢处理催化剂,其特征在于:所述催化剂载体比表面积为220~330m2/g。
4.根据权利要求1或2所述的一种渣油加氢处理催化剂,其特征在于:所述催化剂载体总孔容为0.95~1.2ml/g。
5.根据权利要求1所述的一种渣油加氢处理催化剂,其特征在于:所述催化剂载体为氧化铝。
6.根据权利要求1所述的一种渣油加氢处理催化剂,其特征在于:所述介孔的孔容占催化剂载体总孔容的50~70%,所述大孔的孔容占催化剂载体总孔容的15~40%。
7.一种渣油加氢处理催化剂的制备方法,其特征在于该制备方法包括如下步骤:
步骤1):制备载体:配制铝盐溶液,采用pH摆动法进行溶胶的混合,在混合过程中加入有机扩孔剂,导加入成胶罐中,于60℃~90℃成胶,成胶结束后,经老化、干燥、成型,然后在550℃~1100℃条件下焙烧,获得氧化铝载体;pH摆动范围为4~10,最终反应体系的pH值为8~10;
步骤2):将氧化铝载体等体积浸渍Mo或W以及Co或Ni的浸渍液,然后在90~150℃温度条件下干燥2~8小时,再在600~800℃下,焙烧1~5小时,得到加氢脱金属催化剂;
所述加氢脱金属催化剂中含有MoO3或WO3以及NiO或CoO,所述MoO3或WO3的总质量占催化剂质量的5.0~14.0%,所述NiO或CoO的总质量占催化剂质量的1.0~5.0%。
8.根据权利要求7所述的一种渣油加氢处理催化剂的制备方法,其特征在于:步骤1)中所述有机扩孔剂为聚苯乙烯球、聚甲基丙烯酸甲酯球中的一种或者两种,所述有机扩孔剂的直径为30~300nm。
9.根据权利要求8所述的一种渣油加氢处理催化剂的制备方法,其特征在于:以焙烧后的氧化铝为基准计算,所述聚苯乙烯球和/或聚甲基丙烯酸甲酯球的用量占10~50%。
10.根据权利要求1所述的一种渣油加氢处理催化剂的制备方法,其特征在于:步骤2)中的浸渍液为Mo-Ni、Mo-Co、W-Co、W-Ni溶液中的一种。
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