CN106914249B - 渣油加氢脱金属催化剂及其制备方法 - Google Patents
渣油加氢脱金属催化剂及其制备方法 Download PDFInfo
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- CN106914249B CN106914249B CN201510984716.4A CN201510984716A CN106914249B CN 106914249 B CN106914249 B CN 106914249B CN 201510984716 A CN201510984716 A CN 201510984716A CN 106914249 B CN106914249 B CN 106914249B
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 16
- 229910052796 boron Inorganic materials 0.000 claims description 16
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- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 15
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
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- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 1
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- UFMBFIIJKCBBHN-MEKJRKEKSA-N myelin peptide amide-16 Chemical compound C([C@@H](C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](C)C(=O)N[C@@H](CO)C(=O)N[C@@H](C)C(N)=O)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CO)NC(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](CO)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCNC(N)=N)NC(=O)[C@H](CCCCN)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@H](C)NC(=O)[C@H](C)NC(C)=O)C1=CC=C(O)C=C1 UFMBFIIJKCBBHN-MEKJRKEKSA-N 0.000 description 1
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Classifications
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
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Abstract
一种渣油加氢脱金属催化剂及其制备方法。本发明催化剂孔容为0.2~1.2mL/g;比表面积为40~200m2/g;孔直径在500nm以上的孔所对应的孔容占总孔容的比例为5%~30%,孔直径在1000nm以上的孔所对应的孔容占总孔容的比例为5%~15%;以氧化铝为载体,催化剂中含有占催化剂总重量4~12%的钼和/或钨和0.4~4%的钴和/或镍的氧化物;同时具备双峰孔结构和活性金属梯度减少分布特性。本发明的方法是将水合氧化铝与非酸性粘合剂、复合扩孔剂混合并成型,对所得载体进行金属浸渍、预干燥和水洗处理,最后经干燥和焙烧得到催化剂。本发明提供催化剂具有高的脱金属活性和稳定性。
Description
技术领域
本发明是关于一种渣油加氢脱金属催化剂及其制备方法,更具体的说是关于一种同时具有双峰孔结构和金属组分梯度减少分布特征的渣油加氢脱金属催化剂及其制备方法。本发明催化剂用于劣质重油特别是渣油的加氢处理过程。
背景技术
劣质重油如渣油等含有较高的Ni、V等金属杂质,通常需要经过加氢处理进行脱除,以便经过后续的加工(如催化裂化),生产出清洁的汽、柴油等油品和化工原料。研究表明,渣油中金属杂质主要存在于胶质和沥青质,这部分物质分子量大、结构复杂,扩散困难,因此要求催化剂具有优良的孔道结构和良好的活性金属分散特性,促进大分子反应物质向催化剂颗粒内部扩散、反应和沉积,从而获得高的脱杂质活性和稳定性。
一种提高催化剂扩散性能的有效途径是采用双峰孔结构载体,即催化剂同时存在直径在10-30nm的孔道结构和直径在100nm以上的孔道结构。在反应过程中,孔直径在100nm以上的大孔为大分子反应物质的扩散提供通道,促进杂质向催化剂的内部孔道扩散和反应;而孔直径在10-30nm的孔道则为杂质提供反应表面和沉积场所。两类孔道协同作用,从而使催化剂具有高的脱金属活性和高的容杂质能力。
CN1103009A公开了一种具有双重孔氧化铝载体的制备方法,该方法由两种孔径分布不同的氧化铝或其前身物与炭黑粉、表面活性剂、胶溶剂和水混合成型,经干燥和焙烧制成。当采用炭黑粉作为扩孔剂时,扩孔效果较差,且载体强度较低,同时,胶溶剂的加入会降低载体的孔容和孔径。
CN1647857A公开了一种大孔氧化铝载体的制备方法,该方法将含有机物扩孔剂的拟薄水铝石组合物进行成型和焙烧,得到具有双峰孔结构的氧化铝载体。该方法需先将有机扩孔剂和拟薄水铝石打浆并喷雾干燥,制备过程较为复杂。
上述方法的一个共同缺点是,所制备载体中大孔孔径多集中在500nm以下,500nm以上以及1000nm以上孔道较少,不能最大程度的改善催化剂的扩散性能。
另外,通过优化催化剂的活性金属分散特性,即采用非均匀分布的方式,使催化剂中活性金属的含量从颗粒中心至外表面逐渐降低,降低催化剂外表面处的加氢活性,从而在反应过程中促进渣油原料中金属杂质更多的向催化剂颗粒内部沉积,避免催化剂发生孔口堵塞,以此提高催化剂容金属能力和活性金属利用效率,进而提高催化剂使用寿命,确保装置的长周期运转。
欧洲专利EP0204314提供了一种具有不均匀活性金属组分分布的加氢处理催化剂,该催化剂采用了一种分步、多次浸渍的方法担载活性金属组分,即先把载体浸入到含有部分活性金属组分的A溶液中,取出后经水洗、干燥和焙烧,再浸入含有其它活性组分的B溶液中,取出后经水洗、干燥和焙烧得到催化剂。由于该方法需要多次、分步浸渍、水洗和焙烧,制备过程过于复杂。
专利CN101927196公开了一种活性金属组分溶液呈梯度减少分布的加氢催化剂,其制备方法是在喷浸活性金属溶液的过程中逐渐降低溶液中金属组分浓度或先后喷浸浓度由高到低的不同溶液。这种方法虽然具有理论可行性,但操作难度较大,喷浸时难以保证溶液均匀喷洒至不同的载体颗粒上,所得催化剂上不同颗粒间金属组分的梯度分布均一性较差;加之不同金属组分其在载体孔道内的吸附及扩散特性存在差异,易导致同一催化剂颗粒内不同区域的金属组分配比存在差异,从而影响其催化性能。
此外,现有氧化铝载体制备技术中,在氧化铝成型时均需加入诸如硝酸、醋酸、硝酸铝等酸性物质作为胶溶剂,而酸性物质的加入会破坏氧化铝的粒子结构,降低载体的孔容和孔径。降低酸性胶溶剂对氧化铝孔结构的破坏是制备大孔氧化铝载体的一种有效技术路线,如CN1154668和CN1611578均在氧化铝混捏成型过程中加入一定的氨对胶溶酸进行部分中和,从而达到增大载体孔容孔径的目的,但此种方法不能彻底消除酸性物质对载体孔结构的不利影响,效果有限。
发明内容
针对现有技术的不足,本发明提供一种同时具有双峰孔结构和金属组分梯度减少分布特征的加氢催化剂及其制备方法,本发明方法制备的催化剂扩散性能优异,具有反应活性高、容杂质能力强、使用寿命长的优点,可作为重质油加氢催化剂特别是渣油加氢脱金属催化剂使用。
本发明提供一种渣油加氢脱金属催化剂,其中,
孔容为0.2~1.2mL/g;
比表面积为40~200m2/g;
孔直径在500nm以上的孔所对应的孔容占总孔容的比例为5%~30%,孔直径在1000nm以上的孔所对应的孔容占总孔容的比例为5%~15%;
以氧化铝为载体,催化剂中含有占催化剂总重量4~12%的钼和/或钨和0.4~4%的钴和/或镍的氧化物;
催化剂颗粒中金属组分浓度从颗粒中心至外面表逐渐减少;催化剂颗粒外表面与中心处金属重量之比为0.05~0.60,0.66R处与中心处金属重量之比为0.40~0.80,0.33R处与中心处金属重量之比为0.60~0.95,R为以催化剂颗粒中心为初始点的催化剂的颗粒半径。
本发明还提供一种渣油加氢脱金属催化剂的制备方法,其是上述渣油加氢脱金属催化剂的制备方法,包括如下步骤:
(1)在拟薄水铝石干胶粉中加入非酸性粘合剂、复合扩孔剂和水,充分混捏、成型并干燥和焙烧,得载体;
(2)配制含有钼和/或钨和镍和/或钴的金属溶液,并对(1)中所得载体以饱和浸渍的方式负载金属;
(3)采用振动流化床干燥设备对(2)中所得的颗粒物进行预干燥,热风温度控制在40~100℃,催化剂最终水含量控制在20~60%;
(4)将(3)中所得物料浸于净水中,浸入时间1~60分钟,净水温度20~80℃;
(5)步骤(4)中水洗后的物料在80~150℃下经振动流化床干燥,控制水含量小于8%,然后在400~650℃下焙烧2~6小时,催化剂中含有占催化剂总重量4~12%的钼和/或钨和0.4~4%的钴和/或镍的氧化物。
本发明所述的渣油加氢脱金属催化剂的制备方法,其中,所述非酸性粘合剂优选为甲基纤维素、乙基纤维素、羟丙基甲基纤维素和羟乙基甲基纤维素中的一种或几种。
本发明所述的渣油加氢脱金属催化剂的制备方法,其中,所述非酸性粘合剂的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的1~5%。
本发明所述的渣油加氢脱金属催化剂的制备方法,其中,所述复合扩孔剂优选为含硼化合物和聚乙烯醇。
本发明所述的渣油加氢脱金属催化剂的制备方法,其中,所述含硼化合物优选为硼酸、氧化硼和硼酸盐中的一种或几种。
本发明所述的渣油加氢脱金属催化剂的制备方法,其中,以硼计,所述含硼化合物的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的1~4%。
本发明所述的渣油加氢脱金属催化剂的制备方法,其中,所述聚乙烯醇优选为聚乙烯醇溶液或聚乙烯醇粉末。
本发明所述的渣油加氢脱金属催化剂的制备方法,其中,所述聚乙烯醇的加入量优选为拟薄水铝石干胶粉中对应的氧化铝重量的5~20%。
本发明还可详述如下:
本发明的加氢催化剂,孔容为0.2~1.2mL/g,比表面积为40~200m2/g,孔直径在500nm以上的孔所对应的孔容占总孔容的比例为5%~30%,孔直径在1000nm以上的孔所对应的孔容占总孔容的比例为5%~15%;催化剂中含有催化剂总重量4-12%的钼和/或钨和0.4-4%的钴和/或镍的氧化物;催化剂颗粒中金属组分浓度从颗粒中心至外面表逐渐减少;催化剂颗粒外表面与中心处金属重量之比为0.05-0.60,0.66R处与中心处金属重量之比为0.40-0.80,0.33R处与中心处金属重量之比为0.60-0.95。R为以催化剂颗粒中心为初始点的催化剂的颗粒半径。
本发明提供方法的要点包括:1)将水合氧化铝与非酸性粘合剂、复合扩孔剂和水等混合、成型、干燥和焙烧,得到载体;2)配制含有钼和/或钨和镍和/或钴的金属溶液,并对所得载体以饱和浸渍的方式负载金属;3)采用振动流化床干燥设备对2)中所得的颗粒物进行预干燥,热风温度控制在40-100℃,催化剂最终水含量控制在20-60%;4)将3)中所得物料浸于净水中,浸入时间1-60分钟,净水温度20-80℃;5)水洗后的物料在80-150℃下经振动流化床干燥,控制水含量小于8%,然后在400-650℃下焙烧2-6小时,催化剂中含有催化剂总重量4-12%的钼和/或钨和0.4-4%的钴和/或镍的氧化物。
所述非酸性粘合剂选自甲基纤维素、乙基纤维素、羟丙基甲基纤维素、羟乙基甲基纤维素中的一种或几种,加入量为氧化铝重量的1-5%。
所述复合扩孔剂为含硼化合物和聚乙烯醇。所述含硼化合物选自硼酸、氧化硼、硼酸盐中的一种或几种,以单质硼计,所述含硼化合物的加入量为氧化铝重量的1-4%。所述聚乙烯醇为各种规格的聚乙烯醇溶液或聚乙烯醇粉末,加入量为氧化铝重量的5-20%。
本发明催化剂制备方法可在载体成型过程中根据需要加入P、Ti、Si、Zr等不同助剂和田菁粉、淀粉等助挤剂。
本发明催化剂的形状可以根据不同的要求进行改变。
与现有技术相比,本发明催化剂同时具有双峰孔结构和金属组分梯度减少分布特征,催化剂反应活性、容杂质能力和使用寿命更优。本发明提供方法在载体成型过程中不使用酸性胶溶剂,降低了酸对水合氧化铝粒子结构的破坏,因而载体孔容和孔径均较大;使用含硼化合物与聚乙烯醇复合扩孔,所得大孔孔径更大,大孔比例更高;对浸渍金属溶液后的催化剂先低温预干燥再进行水洗处理,金属组分分布梯度性好,操作性较强,不同催化剂颗粒间金属梯度分布均一性较好,同一催化剂颗粒内不同部位金属配比均一性较好。
本方法中采用含硼化合物与聚乙烯醇复合扩孔,扩孔效果更好,这是因为聚乙烯醇遇到含硼化合物时会发生“凝胶化”反应,使处于溶解或分散状态的聚乙烯醇物质产生一定程度的缩合和交联,在高温焙烧时通过碳化和分解,更易形成贯通的孔道结构,且孔径更大。
本方法中采用振动流化床干燥设备对催化剂进行预干燥或干燥,具有干燥效果均匀、干燥温度低、干燥速度快的优点,以振动流化床对浸渍后的催化剂先低温预干燥,然后再水洗和振动流化干燥,可以减少因金属组分扩散造成的分布梯度降低,同时颗粒间梯度分布均一性较好。
本发明加氢催化剂,可作为重油加氢处理催化剂、特别是渣油加氢脱金属催化剂使用。
由本发明提供方法制备的氧化铝载体具有典型的双峰孔结构和金属组分梯度减少分布特征。例如,按照本发明提供方法制备的催化剂经500℃焙烧3小时,孔容为0.76cm3/g,比表面积为145m2/g,孔直径在500纳米以上的孔所对应孔容占总孔容的24.1%,孔直径在1000纳米以上的孔所对应孔容占总孔容的12.4%;催化剂含有占其总重量8.1%MoO3和1.0%的NiO;催化剂颗粒外表面与中心处金属重量之比为0.32,0.66R处与中心处金属重量之比为0.55,0.33R处与中心处金属重量之比为0.78。
附图说明
图1:实施例1催化剂压汞孔径分布示意图;
图2:实施例1催化剂金属组分分布示意图。
具体实施方式
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
实施例1
称取烟台恒辉化工有限公司生产的大孔拟薄水铝石干胶粉(干基含量71.5wt%)500g,加入粘度为15万mPa·s(指2%水溶液的粘度)的羟丙基甲基纤维素10.7g、规格为17-88的聚乙烯醇粉末53.6g,混合均匀;将40.9g硼酸溶解于570g净水中,缓慢加入前述物料中,混捏成可塑体,然后在单螺杆挤条机上挤成直径为1.6mm的三叶草形。120℃干燥2.0小时,再置入焙烧炉中,850℃恒温3小时,得到载体。配制含有(10.7g MoO3+1.3g NiO)/100mL的稳定金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍;浸渍所得物料在振动流化床中进行预干燥,热风温度70℃,控制催化剂水含量为50%;预干燥后的催化剂置于温度为40℃的净水中,浸泡20分钟;水洗后的催化剂于振动流化床中干燥,热风温度120℃,干燥后水含量为6%;焙烧炉中500℃恒温3小时,得催化剂A。催化剂物性见表1。
实施例2
称取前述拟薄水铝石500g,加入粘度为15万mPa·s(指2%水溶液的粘度)的羟丙基甲基纤维素3.6g、规格为17-99的的聚乙烯醇粉末28.6g,混合均匀;将20.5克硼酸溶解于570g净水中,按照前述方法进行成型和干燥,在焙烧炉中以900℃恒温2小时,得到载体。配制含有(16.0g WO3+0.6g NiO)/100mL的稳定金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍;浸渍所得物料在振动流化床中进行预干燥,热风温度40℃,控制催化剂水含量为60%;预干燥后的催化剂置于温度为80℃的净水中,浸泡1分钟;水洗后的催化剂于振动流化床中干燥,热风温度150℃,干燥后水含量为4%;焙烧炉中400℃恒温6小时,得催化剂B。催化剂物性见表1。
实施例3
称取前述拟薄水铝石500g,加入粘度为10万mPa·s(指2%水溶液的粘度)的羟乙基甲基纤维素17.9g、氧化硼28.6g混合均匀;将31.0克硼酸和规格为17-88的聚乙烯醇粉末17.9g溶解于570g净水中,按照前述方法进行成型和干燥,在焙烧炉中以700℃恒温4小时,得到载体。配制含有(6.7g WO3+5.3gMoO3+1.3g NiO+1.3g Co2O3)/100mL的稳定金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍;浸渍所得物料在振动流化床中进行预干燥,热风温度100℃,控制催化剂水含量为20%;预干燥后的催化剂置于温度为20℃的净水中,浸泡60分钟;水洗后的催化剂于振动流化床中干燥,热风温度80℃,干燥后水含量为7%;焙烧炉中650℃恒温2小时,得催化剂C。催化剂物性见表1。
实施例4
称取前述拟薄水铝石500g,加入粘度为15万mPa·s(指2%水溶液的粘度)的羟丙基甲基纤维素6.7g和粘度为10万mPa·s(指2%水溶液的粘度)的甲基纤维素4.0g、氧化硼28.6g,混合均匀;规格为24-88的聚乙烯醇粉末71.5g溶解于570g净水中,按照前述方法进行成型和干燥,在焙烧炉中以800℃恒温3小时,得到载体。配制含有(5.3g MO3+5.3g NiO)/100mL的稳定金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍;浸渍所得物料在振动流化床中进行预干燥,热风温度80℃,控制催化剂水含量为40%;预干燥后的催化剂置于温度为60℃的净水中,浸泡15分钟;水洗后的催化剂于振动流化床中干燥,热风温度110℃,干燥后水含量为5%;焙烧炉中500℃恒温3小时,得催化剂D。催化剂物性见表1。
比较例1-2说明现有方法和由现有方法制备的催化剂。
比较例1
本比较例中载体按照CN1103009A所描述的方法制得,常规方法负载金属。
将34.1克氢氧化铝干胶粉(含氧化铝75%的烷基铝水解产物)和硫酸铝法制得的氢氧化铝粉39.3克混合后加入高耐磨炭黑4.7克及表面活性剂SA-203.5克和2.1克硝酸铝、66毫升水充分碾混,在单螺杆挤条机上挤成直径1.6毫米三叶草形,120℃烘干,800℃焙烧4小时,得到载体。配制含有(8.9g MoO3+1.1g NiO)/100mL的稳定金属浸渍液,以饱和浸渍的方法对所得载体进行浸渍,鼓风干燥箱中120℃干燥3小时,焙烧炉中500℃恒温3小时,得催化剂E。催化剂物性见表1。
比较例2
本比较例中载体按照常规方法制得,金属负载按照CN101927196方法进行。
称取烟台恒辉化工有限公司生产的大孔拟薄水铝石干胶粉(干基含量71.5wt%)500g,加入10.7克田菁粉,混合均匀;将17.9克乙酸溶解于430g净水中,缓慢加入前述物料中,混捏成可塑体,然后在单螺杆挤条机上挤成直径为1.6mm的三叶草形。在120℃干燥2.0小时,再置入焙烧炉中,于900℃恒温3小时,得到载体。先后以含有(10.7g MoO3+1.3gNiO)/100mL的金属溶液和含有(7.4g MoO3+0.9g NiO)/100mL的金属溶液对载体进行喷浸,直至饱和。鼓风干燥箱中120℃干燥3小时,焙烧炉中500℃恒温3小时,得催化剂F。催化剂物性见表1。
实施例5
本例为以上各例催化剂的理化性质和活性评价结果。
采用BET,压汞,SEM-EDX,XRF等分析方法对催化剂物性进行分析,结果见表1。
表1催化剂物化性质
表1的结果表明,与比较例相比较,本发明方法制备的催化剂同时具备双峰孔结构特征和活性金属梯度分布特征,孔容、孔径更大,具有相当比例的500nm以上及1000nm以上孔道结构,金属分布梯度更优异。
对表1催化剂进行活性稳定性评价,评价条件见表2,评价结果见表3。
表2催化剂评价条件
原料油性质 | 中东渣油 |
密度(20℃)/g·cm<sup>-3</sup> | 0.99 |
(Ni+V),μg.g<sup>-1</sup> | 103 |
工艺条件 | |
反应温度,℃ | 385 |
氢分压,MPa | 16 |
体积空速,h<sup>-1</sup> | 0.85 |
氢/油比 | 750 |
表3催化剂金属脱除率(HD(Ni+V))
由表3评价结果知,本发明催化剂具有更高的脱金属活性和更优的活性稳定性。
Claims (7)
1.一种渣油加氢脱金属催化剂,其特征在于,
孔容为0.2~1.2 mL/g;
比表面积为40~200 m2/g;
孔直径在500nm以上的孔所对应的孔容占总孔容的比例为5%~30%,孔直径在1000nm以上的孔所对应的孔容占总孔容的比例为5%~15%;
以氧化铝为载体,催化剂中含有占催化剂总重量4~12%的钼和/或钨的氧化物和0.4~4%的钴和/或镍的氧化物;
催化剂颗粒中金属组分浓度从颗粒中心至外表面逐渐减少;催化剂颗粒外表面与中心处金属重量之比为0.05~0.60,0.66R处与中心处金属重量之比为0.40~0.80,0.33R处与中心处金属重量之比为0.60~0.95,R为以催化剂颗粒中心为初始点的催化剂的颗粒半径;
所述催化剂的制备包括如下步骤:
(1)在拟薄水铝石干胶粉中加入非酸性粘合剂、复合扩孔剂和水,充分混捏、成型并干燥和焙烧,得载体,所述复合扩孔剂为含硼化合物和聚乙烯醇;
(2) 配制含有钼和/或钨和镍和/或钴的金属溶液,并对(1)中所得载体以饱和浸渍的方式负载金属;
(3) 采用振动流化床干燥设备对(2)中所得的颗粒物进行预干燥,热风温度控制在40~100℃,催化剂最终水含量控制在20~60%;
(4) 将(3)中所得物料浸于净水中,浸入时间1~60分钟,净水温度20~80℃;
(5)步骤(4)中水洗后的物料在80~150℃下经振动流化床干燥,控制水含量小于8%,然后在400~650℃下焙烧2~6小时。
2.根据权利要求1所述的渣油加氢脱金属催化剂,其特征在于,所述非酸性粘合剂为甲基纤维素、乙基纤维素、羟丙基甲基纤维素和羟乙基甲基纤维素中的一种或几种。
3.根据权利要求1或2所述的渣油加氢脱金属催化剂,其特征在于,所述非酸性粘合剂的加入量为拟薄水铝石干胶粉中对应的氧化铝重量的1~5%。
4.根据权利要求1所述的渣油加氢脱金属催化剂,其特征在于,所述含硼化合物为硼酸、氧化硼和硼酸盐中的一种或几种。
5.根据权利要求4所述的渣油加氢脱金属催化剂,其特征在于,以硼计,所述含硼化合物的加入量为拟薄水铝石干胶粉中对应的氧化铝重量的1~4%。
6.根据权利要求1所述的渣油加氢脱金属催化剂,其特征在于,所述聚乙烯醇为聚乙烯醇溶液或聚乙烯醇粉末。
7.根据权利要求1所述的渣油加氢脱金属催化剂,其特征在于,所述聚乙烯醇的加入量为拟薄水铝石干胶粉中对应的氧化铝重量的5~20%。
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