CN108187709A - 一种深度加氢脱硫催化剂的制备方法及该催化剂的应用 - Google Patents
一种深度加氢脱硫催化剂的制备方法及该催化剂的应用 Download PDFInfo
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- CN108187709A CN108187709A CN201711400168.1A CN201711400168A CN108187709A CN 108187709 A CN108187709 A CN 108187709A CN 201711400168 A CN201711400168 A CN 201711400168A CN 108187709 A CN108187709 A CN 108187709A
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- catalyst
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- deep hydrodesulfurizationof
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- deep
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 20
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
本发明公开一种深度加氢脱硫催化剂的制备方法,其将拟薄水铝石、固体铝溶胶、活性α氧化铝粉、粘结剂、扩孔剂在混料机中混合均匀后,加入磷酸和乙酸混合水溶液,将粉料揉合成泥,再通过混捏、挤压成型、干燥、断条和焙烧,得到催化剂载体;然后采用浸渍法负载金属W,Mo,Co,Ni和P,经干燥和焙烧,得到深度加氢脱硫催化剂。本发明制备所得的催化剂具有高吸水性,孔容和比表面积大,金属分散度高,边沿活性中心位多,加氢脱氮、芳烃饱和活性及超深度加氢脱硫活性好,机械强度高,金属含量低的特点。
Description
技术领域
本发明属于加氢脱硫技术领域,尤其是涉及一种深度加氢脱硫催化剂的制备方法及该催化剂的应用。
背景技术
原油的重质化、劣质化导致原油高硫化趋势在进一步扩大,据报道,目前世界上低硫原油仅占17wt%,含硫>2wt%的高硫原油高达58wt%。柴油中的硫、氮及芳烃等在燃烧过程中排放出的SOx、NOx、CH及碳烟等会导致形成酸雨、光化学烟雾、致癌物等,对环境造成严重污染,对居民健康造成严重危害,基于此各国政府对大气清洁越来越关注,对车用柴油规格的要求也越来越严格。未来清洁柴油规格正向着无硫化、低芳烃、低密度、高十六烷值的方向发展。
柴油加氢精制原料大多是直柴、焦柴、催柴等中的一种或两种以上的混合油。近年炼厂大量加工中东等地区的高含硫原油,使直溜柴油中的硫含量大幅度提高,催化裂化掺炼渣油、蜡油比例的上升使催化柴油中的一些高沸点大分子硫化物、氮化物及多环芳烃等聚集,实际柴油加氢精制原料的反应性能进一步降低,加工难度大大增加。
一般而言,相对于重质馏分油,汽油馏分中所含的硫容易通过加氢精制脱除。但是,由于支链化程度较低的烯烃在此过程中极易加氢饱和成低辛烷值的烷烃,这不仅会使汽油辛烷值的大幅下降,同时造成大量无谓的氢耗,因此,采用加氢方法对汽油馏分油进行脱硫的主要问题是如何在保证脱硫的同时减少烯烃加氢饱和,提高加氢反应的选择性。
CN1133723公开了一种馏分油加氢精制催化剂及其制备方法,以含二氧化硅5~15wt%的氧化铝小球为载体,含MoO321~28wt%,NiO22~8wt%,CoO 0.03~2.0wt%,采用两段喷浸。所述的催化剂同时具有较高的加氢脱硫和加氢脱氮活性,适用于同时含硫氮较多的劣质馏分油加氢精制。
CN1101454公开了一种馏分油加氢脱硫催化剂及制备方法,催化剂以氧化铝或含硅氧化铝为载体,以Mo-Ni为活性组分,添加磷助剂,通过采用碱性的 Mo-Ni-P共浸液分段共浸载体,使得催化剂上的金属分布更均匀,催化剂的活性,特别是馏分油加氢脱硫活性得以提高。
CN1472283公开了一种用于含烯烃石脑油选择性加氢脱硫的催化剂及其制备方法,所述催化剂主要通过采用单层分散法制备而成,其成分配比为: CoO+MoO3:6~20wt%;MgO:8~20wt%;Al2O3:40~86wt%,所述CoO 和MoO3的混合物中的Mo/Co原子比为1~6:1。
U.S.Pat.No.5525211公开了一种选择性加氢脱硫催化剂,该催化剂含有 0.1~40重量%的选自第VIB族的钼和/或钨,0.1~15重量的选自第VIII族的镍和钴,0.01~20重量%的选自第IA族碱金属,碱土金属,Sc,Y和镧系元素,载体为具有尖晶石结构的MgAl2O4,ZnAl2O4,CaAl2O4,NiAl2O4,CoAl2O4或 BaAl2O4。
WO2007084438公开了一种选择性加氢脱硫催化剂,该催化剂含有8~30 重量%的选自第VIB族的钼,2~8重量的选自第VIII族的钴,及适当量的有机物作为络合剂负载在硅载体上。使用该催化剂处理催化裂化汽油原料,烯烃饱和率低。
发明内容
为解决上述问题,本发明的目的是提供一种双峰孔径、大比表面积、大孔容、高吸水率、酸性中心分布合理的深度加氢脱硫催化剂的制备方法,其制备得到的催化剂具有成本低、加氢活性和选择性高的特点;还公开上述深度加氢脱硫催化剂的应用。
为实现上述发明目的,本发明采用如下技术方案:
一种深度加氢脱硫催化剂的制备方法,其包括以下步骤:
步骤a、催化剂载体制备:
将拟薄水铝石、固体铝溶胶、活性α氧化铝粉、粘结剂、扩孔剂在混料机中混合均匀后,加入磷酸和乙酸混合水溶液,将粉料揉合成泥,再通过混捏、挤压成型、干燥、断条和焙烧,得到催化剂载体;其中,拟薄水铝石、固体铝溶胶、活性α氧化铝粉的质量比为70~90:30~5:0~10,外加的粘结剂用量为上述粉料总重量1~20%,扩孔剂用量为上述粉料总重量1~30%;
步骤b、将金属化合物溶于去离子水或蒸馏水中,配置成金属水溶液;
步骤c、采用浸渍法在步骤a的催化剂载体上负载活性元素W、Mo、Co、 Ni、P,经干燥和焙烧,得到深度加氢脱硫催化剂。
进一步地,以催化剂的重量为基准,上述的步骤a中的拟薄水铝石含量为 40wt%~90wt%,优选为60wt%~90wt%。
进一步地,上述的步骤a中,在催化剂载体制备过程中加入有磷酸和乙酸混合水溶液,以增加催化剂载体的机械强度,磷酸和乙酸的外加含量为0.10wt%~ 10wt%,优选为1wt%~5wt%。
进一步地,上述的步骤a中,粘结剂为甲基纤维素、羧甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素、杨梅树胶、田菁胶中的一种或几种混合。
进一步地,上述的步骤a中,扩孔剂为一水柠檬酸、淀粉醚、淀粉中的一种或几种混合。
进一步地,上述的步骤a中,在成型过程中还加入有成型助剂,成型助剂包括胶溶酸和助挤剂,胶溶酸为硝酸,助挤剂为甘油、硬脂酸或油酸。
进一步地,上述的步骤a中,焙烧温度为650~900℃,优选为700~800℃。
进一步地,上述的深度加氢脱硫催化剂的制备方法中,其活性元素W、Mo、 Co、Ni、P的来源物分别为偏钨酸铵、七钼酸铵、六水硝酸钴、六水硝酸镍、磷酸。
上述的深度加氢脱硫催化剂的制备方法,其制备所得的深度加氢脱硫催化剂性质如下:比表面积为100~300m2/g,优选为150~270m2/g;孔径为5~40nm,优选为20~35nm;孔容为0.3~1.2ml/g,优选为0.5~1.1ml/g;吸水率为105~ 170%,优选为115~150%;堆比重为0.35~0.9g/ml,优选为0.45~0.8g/ml;红外酸量为0.3~1.0mmol/g,优选为0.4~0.8mmol/g;B酸/L酸的比值为1.5~2.0,优选为1.6~1.9。
本发明的深度加氢脱硫催化剂用于轻质柴油的加氢过程,尤其是较高硫含量的轻质柴油生产超低硫含量白油的过程。
本发明的深度加氢脱硫催化剂在对轻质柴油进行加工时,需要采用干法硫化方式预先硫化,使活性物质由氧化态置换成硫化态以提高催化剂的活性和稳定性。
本发明的深度加氢脱硫催化剂在对轻质柴油进行加工时,反应条件为在氢气存在条件下,反应压力为6~20MPa,氢油体积比500~3000,液时体积空速 0.3~3.0h-1,反应温度280~420℃。
由于采用如上所述的技术方案,本发明具有如下优越性:
本发明深度加氢脱硫催化剂的制备方法,其在催化剂载体制备过程中选用去离子水或蒸馏水,能够减少自来水中钙、镁离子对催化剂金属的负面影响,使金属液更好地的分散在催化剂载体上。
本发明制备所得的深度加氢脱硫催化剂为孔径双峰值型催化剂,具体为大孔容,且孔直径分布在3~15nm和3~25um范围的两个尖锐的峰值催化剂,其中 3~25um孔主要由扩孔剂生成,生成原理为:先将扩孔剂混合于步骤a粉料中,制成泥坯,后经泥坯500℃~900℃温度焙烧制成催化剂载体,在催化剂载体焙烧过程中同时也将泥坯中扩孔剂灼烧掉,使扩孔剂原先在泥坯中占有的体积腾出来了,形成了镂空,大量的镂空能明显增加催化剂载体的单位质量内孔容量,能使催化剂载体在后续负载金属时候,增加了负载空间,即扩孔剂使催化剂载体增加了更多的“房间”,更多的面积来容纳催化剂活性金属物质,提高了催化剂活性金属在载体中的中的分布能力,提高了活性,同时,其大量的“房间”还增加了催化剂载体材料孔隙率和孔通道,有利于反应物和反应产物的快速交换和逸出,避免聚合反应产生“飞温”现象;3~15nm的孔径主要负责催化剂主体反应,提高反应效率。
本发明深度加氢脱硫催化剂的制备方法,其工艺过程简单,操作方便,成本低,易于操作,适合工业生产;制备所得的催化剂适于轻质柴油的加氢脱硫过程,特别适合于较高硫含量的轻质柴油的加氢脱硫脱芳反应。
本发明深度加氢脱硫催化剂的制备方法,其制备所得的催化剂具有高吸水性,孔容和比表面积大,金属分散度高,边沿活性中心位多,加氢脱氮、芳烃饱和活性及超深度加氢脱硫活性好,机械强度高,金属含量低的特点。
具体实施方式
参照以下实施例可以对本发明作进一步详细说明;但是,以下实施例仅仅是例证,本发明并不局限于这些实施例。
本发明制备所得的深度加氢脱硫催化剂的比表面积和孔容采用低温液氮吸附法测定,酸量和酸性质采用红外光谱仪测得,所使用吸附剂为吡啶,wt%为质量分数。
一、催化剂载体的制备步骤为:
1、原料预混,将拟薄水铝石、固体铝溶胶、活性α氧化铝粉按70~90:30~5: 0~10的净重配比,并外加其重量1~20%的粘结剂和1%~30%扩孔剂,投入混料机,干混10~60分钟,取出粉料过20~60目的筛网以去除粗颗粒;
2、制备制泥溶液:以步骤1中的粉料总重为基础,称取其重量0.5~10%的磷酸和乙酸溶解在粉料总重60~150%的去离子水中;
3、将粉料投入制泥机内,加入步骤2中得到的制泥溶液溶液,密封混料5~30 分钟,使粉料变成泥料;
4、将步骤3中得到的泥料送入练泥机,将泥料练成密实的泥段以备后续成型用;
5、通过挤出机和模具将步骤4中得到的泥段成型成具有外形结构的泥坯;
6、步骤5中得到的泥坯采用室温~130℃温度干燥,干燥时间视实际情况而定,一般为0.5~24小时,直至坯体含水率10%以下;
7、将步骤6中得到的干燥好的泥坯通过断条机断成1~30mm长的半成品;
8、通过窑炉将步骤7中得到的半成品坯体在650~900℃温度下,氧化气氛焙烧4~15小时,得到催化剂载体。
二、催化剂载体负载金属的步骤如下:
本发明所涉及的金属和非金属物质为钨(W),镍(Ni),钴(Co),钼(Mo),磷(P),将前驱物按催化剂中按照W的含量为10~20wt%,Ni的含量为0.5~10 wt%,Co的含量为1~10%,Mo的含量为5~25wt%,P的含量为0.5~15%,计算出前驱物配比溶液,采用真空浸渍的方法将溶液负载在载体上,浸渍溶液后,在60~200℃温度环境下抽真空脱水至坯体含水率低于10%为止,最后将负载化合物的载体送入窑炉进行过氧焙烧5~15小时,直至上述金属盐变成氧化态物质,得到深度加氢脱硫催化剂。
三、塔外硫化,采用干法硫化方式将深度加氢脱硫催化剂预先硫化,使活性物质的氧化态通过硫化装置变成硫化态,以提高催化剂高活性和稳定性。
下面结合实施例对本发明作进一步详细描述。
实施例1
a、将5.9kg拟薄水铝石、3.6kg固体铝溶胶、0.5kg活性α氧化铝粉、0.2kg 田菁胶、淀粉2kg投入至锥形混料机内,混料15分钟后取出投入至制泥机内;
b、然后将0.5kg一水柠檬酸、0.32kg磷酸、0.2kg乙酸溶解于8.8kg去离子水中,最后将水溶液通过喷雾的形式加入制泥机内,制泥8分钟,泥料成块状后取出;
c、在步骤b所得的催化剂载体上负载金属:将金属盐偏钨酸铵、七钼酸铵、六水硝酸钴、六水硝酸镍和磷酸共40克溶解在105克水中,没有沉淀且具有较长时间的稳定性后,将催化剂载体在金属溶液内充分浸渍后进行干燥和焙烧,干燥和焙烧的条件如下:在55℃的烘箱内干燥13小时,在750℃温度下,氧化气氛环境下焙烧7小时。
制得的催化剂样品比表面积:149m2/g,孔容:0.46ml/g,平均孔径:12.3nm,径向压碎强度:16N/mm,堆比重:0.55g/ml。
催化剂化学组成:Al2O3:59.3%,NiO:2.9%,CoO:3.1%,MoO3:12.5%, WO3:16.7%,P2O5:4.3%,其它总量为1.2%。
实施例2
a、将6.7kg拟薄水铝石、2.8kg固体铝溶胶、0.5kg活性α氧化铝粉、0.2kg 田菁胶、淀粉2kg投入至锥形混料机内,混料15分钟后取出投入至制泥机内;
b、然后将0.5kg一水柠檬酸、0.5kg磷酸、0.35kg乙酸溶解于8.8kg去离子水中,最后将水溶液通过喷雾的形式加入制泥机内,制泥8分钟,泥料成块状后取出;
c、将步骤b所得的载体上负载金属:将金属盐和磷酸共40克溶解在105 克水中,没有沉淀且具有较长时间的稳定性后,将载体在金属溶液内充分浸渍后进行干燥和焙烧,干燥和焙烧的条件如下:在55℃的烘箱内干燥13小时,在750℃温度下,氧化气氛环境下焙烧7小时;
制得的催化剂样品比表面积:179m2/g,孔容:0.58ml/g,平均孔径:13.7nm,径向压碎强度:11N/mm,堆比重:0.41g/ml。
催化剂化学组成:Al2O3:59.7%,NiO:2.9%,CoO:3.1%,MoO3:12.5%, WO3:16.7%,P2O5:4.3%,其它总量为0.8%。
实施例3
采用实例1的载体,改变催化剂内活性金属的含量对催化剂性能的影响。
a、将5.9kg拟薄水铝石、3.6kg固体铝溶胶、0.5kg活性α氧化铝粉、0.2kg 田菁胶、淀粉2kg投入至锥形混料机内,混料15分钟后取出投入至制泥机内;
b、然后将0.6kg一水柠檬酸、0.48kg磷酸、0.5kg乙酸溶解于8.8kg去离子水中,最后将水溶液通过喷雾的形式加入制泥机内,制泥8分钟,泥料成块状后取出;
c、将步骤b所得的载体上负载金属:将金属盐和磷酸共50克溶解在120 克水中,没有沉淀且具有较长时间的稳定性后,将载体在金属溶液内充分浸渍后进行干燥和焙烧,干燥和焙烧的条件如下:在55℃的烘箱内干燥13小时,在750℃温度下,氧化气氛环境下焙烧7小时;
制得的催化剂样品比表面积:149m2/g,孔容:0.46ml/g,平均孔径:12.3nm,径向压碎强度:16N/mm,堆比重:0.55g/ml。
催化剂化学组成:Al2O3:66.8%,NiO:2.9%,CoO:2.7%,MoO3:8.7%, WO3:13.4%,P2O5:4.3%,其它总量为1.2%。
制备所得的深度加氢脱硫催化剂在对轻质柴油进行加氢精制反应时,能够得到超低硫含量的白油产品,其原料、反应条件及产品性质如下:
表1 原料性质
表2 产品性质
Claims (10)
1.一种深度加氢脱硫催化剂的制备方法,其特征是:其包括以下步骤:
步骤a、催化剂载体制备:
将拟薄水铝石、固体铝溶胶、活性α氧化铝粉、粘结剂、扩孔剂在混料机中混合均匀后,加入磷酸和乙酸混合水溶液,将粉料揉合成泥,再通过混捏、挤压成型、干燥、断条和焙烧,得到催化剂载体;其中,拟薄水铝石、固体铝溶胶、活性α氧化铝粉的质量比为70~90:30~5:0~10,外加的粘结剂用量为上述粉料总重量1~20%,扩孔剂用量为上述粉料总重量1~30%;
步骤b、将金属化合物溶于去离子水或蒸馏水中,配置成金属水溶液;
步骤c、采用浸渍法在步骤a的催化剂载体上负载活性元素W、Mo、Co、Ni、P,经干燥和焙烧,得到深度加氢脱硫催化剂。
2.根据权利要求1所述的深度加氢脱硫催化剂的制备方法,其特征是:以催化剂的重量为基准,上述的步骤a中的拟薄水铝石含量为40wt%~90wt%。
3.根据权利要求1所述的深度加氢脱硫催化剂的制备方法,其特征是:其步骤a中,在催化剂载体制备过程中加入有磷酸和乙酸混合水溶液,磷酸和乙酸的外加含量为0.10~10wt%。
4.根据权利要求1所述的深度加氢脱硫催化剂的制备方法,其特征是:其步骤a中,粘结剂为甲基纤维素、羧甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素、杨梅树胶、田菁胶中的一种或几种混合。
5.根据权利要求1所述的深度加氢脱硫催化剂的制备方法,其特征是:其步骤a中,扩孔剂为一水柠檬酸、淀粉醚、淀粉中的一种或几种混合。
6.根据权利要求1所述的深度加氢脱硫催化剂的制备方法,其特征是:其步骤a中,焙烧温度为650~900℃。
7.根据权利要求1所述的深度加氢脱硫催化剂的制备方法,其特征是:其活性元素W、Mo、Co、Ni、P的来源物分别为偏钨酸铵、七钼酸铵、六水硝酸钴、六水硝酸镍、磷酸。
8.一种权利要求1~7中任一权利要求所述的制备方法,其特征是:其制备所得的深度加氢脱硫催化剂性质如下:比表面积为100~300m2/g;孔径为5~40nm;孔容为0.3~1.2ml/g;吸水率为105~170%;堆比重为0.35~0.9g/ml;红外酸量为0.3~1.0mmol/g;B酸/L酸的比值为1.5~2.0。
9.根据权利要求8所述的深度加氢脱硫催化剂的制备方法,其特征是:其制备所得的深度加氢脱硫催化剂性质如下:比表面积为150~270m2/g;孔径为20~35nm;孔容为0.5~1.1ml/g;吸水率为115~150%;堆比重为0.45~0.8 g/ml;红外酸量为0.4~0.8mmol/g;B酸/L酸的比值为1.6~1.9。
10.一种深度加氢脱硫催化剂的制备方法,其制备所得的深度加氢脱硫催化剂用于较高硫含量的轻质柴油生产超低硫含量白油的过程。
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