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CN108367277B - 结晶双氨过渡金属钼钨酸盐 - Google Patents

结晶双氨过渡金属钼钨酸盐 Download PDF

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CN108367277B
CN108367277B CN201680073308.6A CN201680073308A CN108367277B CN 108367277 B CN108367277 B CN 108367277B CN 201680073308 A CN201680073308 A CN 201680073308A CN 108367277 B CN108367277 B CN 108367277B
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crystalline
transition metal
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bisammonia
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CN108367277A (zh
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S·米勒
L·柯林斯
S·C·柯斯特
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Abstract

本发明开发了独特的结晶双氨过渡金属钼钨酸盐材料。此材料可以用作加氢操作催化剂。加氢操作可以包括：加氢脱氮，加氢脱硫，加氢脱金属化，加氢脱芳构化，加氢脱硅，加氢异构化，加氢处理，加氢精制，以及加氢裂解。

Description

结晶双氨过渡金属钼钨酸盐
在先国家申请的优先权
本申请要求2015年12月15日递交的美国申请No.62/267,865的优先权，将其内容全部引入本文以供参考。
发明领域
本发明涉及新的加氢操作催化剂。更具体而言，本发明涉及独特的结晶双氨过渡金属钼钨酸盐及其作为加氢操作催化剂的用途。加氢操作可以包括加氢脱氮，加氢脱硫，加氢脱金属化，加氢脱硅，加氢脱芳构化，加氢异构化，加氢处理，加氢精制和加氢裂解。
背景技术
为了满足日益增长的对石油产品的需求，希望更多地利用含硫石油，当与在燃料中的氮和硫浓度相关的环境法规更严格时，含硫石油引起精制问题加重。在精制工艺的加氢处理期间的目的是从燃料原料去除含硫(加氢脱硫–HDS)和含氮(加氢脱氮–HDN)的化合物，此目的是通过将有机氮和硫分别转化成氨和硫化氢实现的。
从1940年开始，已经证明使用含镍(Ni)和钼(Mo)或钨(W)的催化剂能除去至多80％的硫。参见例如V.N.Ipatieff,G.S.Monroe,R.E.Schaad,Division of PetroleumChemistry,115th Meeting ACS,San Francisco,1949。数十年来，现在十分关注开发能催化深度脱硫的材料，从而将硫浓度降低到ppm水平。一些近期的突破致力于开发和使用更活泼和稳定的催化剂以生产用于超低硫燃料的原料。一些研究已经证明通过消除载体例如Al2O3改进了HDS和HDN活性。使用无载体的本体材料提供一种提高在反应器中的活性相载荷的途径，并提供另一种关于这些催化剂的化学机理。
在此领域中，较近期的研究致力于通过无载体的Ni-Mo/W“三金属”材料实现超深脱硫性能，例如参见US 6,156,695。含有钼、钨和镍的广泛无定形混合金属氧化物的受控合成明显优于常规的加氢处理催化剂。三金属混合金属氧化物材料的结构化学与水滑石类材料相似，参见详细描述层状钼酸镍材料的合成和表征的文献，其中报道了用钨部分地代替钼能获得广泛的无定形相，其在通过硫化分解时获得优异的加氢处理活性。
这些层状的类似水滑石的材料的化学性质首先由H.Pezerat,contributionàl‘étude des molybdates hydrates de zinc,cobalt et nickel,C.R.Acad.Sci.,261,5490报道，其中确认了具有理想式MMoO4.H2O、EHM2O-(MoO4)2.H2O和E2-x(H3O)xM2O(MoO4)2的一系列相，其中E可以是NH4 +、Na+或K+，并且M可以是Zn2+、Co2+或Ni2+。
Pezerat将所观察到的不同相归类为Φc、Φy或Φy，并检测Φx和Φy的晶体结构；但是由于小微晶尺寸、受限的结晶学能力和材料的复杂性质的组合，对于这些材料的结构评估质量存在疑问。在70年代中期，Clearfield等人试图更详细地分析Φx和Φy相，参见例如A.Clearfield,M.J.Sims,R.Gopal,Inorg.Chem.,15,335；A.Clearfield,R.Gopal,C.H.Saldarriaga-Molina,Inorg.Chem.,16,628。对于从水热方法得到的产物进行的单晶研究允许确认Φx结构；但是他们没有成功合成Φy，而是合成了另一个相Na-Cu(OH)(MoO4)，参见A.Clearfield,A.Moini,P.R.Rudolf,Inorg.Chem.,24,4606。
Φy的结构未得到确认，直到1996年Ying等人的研究。他们研究了室温ChimieDouce合成技术以得到层状钼酸锌铵，得到亚稳态的铝取代的红锌矿相，这通过煅烧Zn/Al层状双氢氧化物(Zn4Al2(OH)12CO3.zH2O)制得。参见例如D.Levin,S.L.Soled,J.Y.Ying,Inorg.Chem.,1996,35,4191-4197。此材料与七钼酸铵的溶液在室温下反应以制备高度结晶的化合物，其结构不能通过常规的从头开始(ab-initio)方法测定。Astier将此材料进行指标化，得到与钼酸镍铵相同的结晶学参数，参见例如M.P.Astier,G.Dji,S.Teichner,J.Ann.Chim.(Paris),1987,12,337，属于铵-胺-镍-钼氧化物类的材料与Pezerat的材料紧密相关。Astier没有公开此类材料的任何详细结构数据，所以Ying等人重新制备此材料并通过高分辨率粉末衍射进行分析，从而明确其结构。Ying等人将此类材料命名为“层状过渡金属钼酸盐”或LTM。
发明概述
本发明制备了独特的结晶双氨过渡金属钼钨酸盐材料，并任选地进行硫化，从而得到活性加氢操作催化剂。结晶双氨过渡金属钼钨酸盐材料具有独特的x-射线粉末衍射图案，其中在7.33、5.06和
Figure BDA0001695788810000032
处显示强峰。结晶双氨过渡金属钼钨酸盐材料具有下式：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值；所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure BDA0001695788810000031
另一个实施方案涉及制备具有下式的结晶双氨过渡金属钼钨酸盐材料的方法，
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值；所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure BDA0001695788810000041
此方法包括：形成含有NH4OH、H2O以及M、W和Mo的源物质的反应混合物；将反应混合物的pH调节到8.5-10的pH；并回收结晶双氨金属钼酸盐材料。
再一个实施方案涉及一种转化方法，包括使进料与催化剂在转化条件下接触以得到至少一种产物，所述催化剂包含：具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值；所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure BDA0001695788810000051
本发明的其它特征和优点将从本发明的下文描述、附图和权利要求显现出来。
附图简述：
图1是如实施例1-3中所述通过沸腾结晶制备的结晶双氨过渡金属钼钨酸盐的x-射线粉末衍射图案。
本发明的详细描述
本发明涉及结晶双氨过渡金属钼钨酸盐组合物，制备此组合物的方法，以及使用此组合物作为催化剂的转化方法。此组合物被指定为UPM-6。此组合物具有经验式：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值。
本发明的结晶组合物的特征在于具有M-O-M的扩展网络，其中M表示上述金属，或上述金属的组合。结构单元本身重复成为至少两个相邻的单元，且没有键接的终止。此组合物可以具有一维网络，例如直链。
结晶双氨过渡金属钼钨酸盐组合物进一步的特征在于具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure BDA0001695788810000061
本发明的结晶双氨过渡金属钼钨酸盐具有如图1所示的x-射线粉末衍射图案。
结晶双氨过渡金属钼钨酸盐是通过反应混合物的溶剂加热结晶制备的，所述反应混合物通常是通过将反应性的钼源和钨源和合适金属‘M’的源物质和溶剂以及氨源混合制得的。可用于本发明中的钼源的具体例子包括、但不限于三氧化钼，二钼酸铵，硫代钼酸铵，以及七钼酸铵。可用于本发明中的钨源的具体例子包括、但不限于三氧化钨、二钨酸铵、硫代钨酸铵和偏钨酸铵。其它金属“M”的源物质包括、但不限于相应的卤化物、乙酸盐，硝酸盐、碳酸盐、硫醇和氢氧化物盐。具体例子包括：氯化镍，氯化钴，溴化镍，溴化钴，氯化镁，氯化锌，硝酸镍，硝酸钴，硝酸铁，硝酸锰，硝酸锌，乙酸镍，乙酸钴，乙酸铁，碳酸镍，碳酸钴，氢氧化锌，氢氧化镍和氢氧化钴。
氨源可以包括、但不限于：氢氧化铵，碳酸铵，碳酸氢铵，氯化铵，氟化铵，或其混合物。
通常，用于制备本发明组合物的工艺涉及形成反应混合物，其中所有组分例如Ni、Mo、W、NH4OH和H2O在溶液中一起混合。例如，反应混合物可以按照由下式表示的氧化物摩尔比率形成：
AMOx：BMoOy：CWOz：D(NH3)：H2O
其中‘M’是选自铁、钴、镍、锰、铜、锌及其混合物；‘A’表示‘M’的摩尔比率，并且可以在0.1-3的范围内，或是0.75-2，或是1-1.5；‘x’是满足M价键的数值；‘B’表示‘Mo’的摩尔比率，并且可以在0.1-3的范围内，或是0.75-2，或1-1.5；‘y’是满足Mo价键的数值；‘C’表示‘W’的摩尔比率，并且可以在0.01-2的范围内，或是0.05-1，或0.2-0.75；‘z’是满足W价键的数值；‘D’表示NH3的摩尔比率，并且可以在0.5-15的范围内，或是1-10，或是3-7；H2O的摩尔比率是在0.1-1000的范围内，或是1-300，或是1-100。
必要的是将反应混合物的pH调节到8.5-10的pH。混合物的pH可以通过加入碱来控制，例如NH4OH、季铵氢氧化物、胺等。
一旦形成反应混合物，反应混合物在60-250℃的温度下反应30分钟至约14天的时间。在一个实施方案中，反应温度的范围是70-180℃；在另一个实施方案中的温度范围是80-140℃。在一个实施方案中，反应时间是1-48小时；在另一个实施方案中，反应时间是2-12小时。此反应是在大气压下或在密封容器中在自生压力下进行。在一个实施方案中，合成可以在开放容器中在回流条件下进行。结晶双氨过渡金属钼钨酸盐的特征在于其独特的x-射线粉末衍射图案，如上表A和图1中所示。
在形成后，可以向结晶双氨过渡金属钼钨酸盐组合物中引入粘合剂，其中选择的粘合剂包括但不限于：阴离子性和阳离子性粘土，例如水滑石，鳞镁铁矿-水镁铁石-水滑石，蒙脱土和相关的粘土，高岭土，海泡石，二氧化硅，氧化铝例如(假)勃姆石，三水铝石，快速煅烧的三水铝石，η-氧化铝，氧化锆，氧化钛，氧化铝涂布的氧化钛，二氧化硅-氧化铝，二氧化硅涂布的氧化铝，氧化铝涂布的二氧化硅，以及它们的混合物，或通常称为颗粒粘合剂的用于保持颗粒完整性的其它材料。这些粘合剂可以在胶溶或不胶溶的情况下施用。可以将粘合剂加入本体结晶双氨过渡金属钼钨酸盐组合物中，并且粘合剂的量可以是最终催化剂的1-30重量％，或是最终催化剂的5-26重量％。粘合剂可以与结晶双氨过渡金属钼钨酸盐化学连接，或者作为与结晶双氨过渡金属钼钨酸盐的物理混合物存在。
含有或不含粘合剂的结晶双氨过渡金属钼钨酸盐可以然后在各种硫化条件下进行硫化或预硫化，这些包括通过结晶双氨过渡金属钼钨酸盐与含硫进料接触以及使用H2S/H2的气态混合物。结晶双氨过渡金属钼钨酸盐的硫化是在升高的温度下进行，通常是50-600℃，或150-500℃，或250-450℃。
本发明的无载体的结晶双氨过渡金属钼钨酸盐材料可以在各种烃转化方法中用作催化剂或催化剂载体。加氢操作方法是一种烃转化方法，其中结晶双氨过渡金属钼钨酸盐材料用作催化剂。加氢操作方法的具体例子是本领域公知的，包括加氢处理或加氢精制，氢化，加氢脱芳构化，加氢脱金属化，加氢脱硅，加氢裂解，加氢脱氮，和加氢脱硫。
上述加氢操作方法的操作条件通常包括反应压力为2.5-17.2MPa或5.5-17.2MPa，反应温度为245-440℃或285-425℃。进料与活性催化剂接触的时间由液体小时空速(LHSV)表示，应当在0.1h-1至10h-1的范围内，或是2.0h-1至8.0h-1。可以根据所用的进料使用这些范围的具体子范围。例如当对典型的柴油进料进行加氢处理时，操作条件可以包括3.5-8.6MPa、315-410℃、0.25-5/h，以及84-850Nm3H2/m3进料。其它进料可以包括汽油、石脑油、煤油、瓦斯油、馏出物和重整油。
下文提供实施例以更完全地描述本发明。这些实施例仅仅用于说明目的，不应理解为限制本发明权利要求的宽范围。
在以下实施例中所示的图案是使用标准x-射线粉末衍射技术得到的。辐照源是高强度的x-射线管，其在45kV和35mA下操作。来自铜K-α辐照的衍射图案是通过合适的基于计算机的技术得到的。将粉末样品以扁平方式压成平板，并连续地从3°至70°(2θ)扫描。从由θ表示的衍射峰位置得到晶面间距(d)，其单位为埃，其中θ是从数字化数据观察得到的布拉格角。强度是从减去背景之后的衍射峰积分面积测定的，其中“IO”是最强线或峰的强度，“I”是每个其它峰的强度。如本领域技术人员理解的那样，参数2θ的检测存在人为和机械误差，这些误差的组合导致每个2θ报告数值的不确定度为±0.4°。这种不确定度也可以解读成d-间距的报告数值，此报告数值是从2θ数值计算的。在报告的一些x-射线图案中，d-间距的相对强度是由符号vs、s、m和w表示的，它们分别表示非常强、强、中等和弱。按照100(I/I0)计，上述符号定义为：
w＝0-15，m＝15-60，s＝60-80，和vs＝80-100。
在一些情况下，合成产物的纯度可以参照其x-射线粉末衍射图案来评价。因此，例如如果样品被描述为是纯的，则这仅仅表示样品的x-射线图案不含归属于结晶杂质的线，并不表示不存在无定形物质。本领域技术人员将能理解不同的不良结晶材料可以在相同的位置产生峰。如果材料是由多种不良结晶材料组成的，则对于每种不良结晶材料观察到的峰位置将在所得的汇总衍射图案中观察到。同样，可以在不同的单相结晶材料中在相同位置具有一些峰，这可以简单地表示在这些材料内的相似距离，并不表示这些材料具有相同的结构。
实施例1
在陶瓷盘中，将15.21g碳酸镍(0.15摩尔Ni)、13.24g七钼酸铵(0.075摩尔Mo)和18.20g偏钨酸铵(0.075摩尔W)加入25ml的浓缩氢氧化铵溶液中。在定期混合的情况下将此溶液于150℃干燥18小时。经干燥的残余物通过上述x-射线衍射进行分析，X-射线粉末衍射图案如图1所示。
实施例2
溶液A：在3L烧瓶中，将35.61g碳酸镍(0.3摩尔Ni)和28.79g三氧化钼(0.2摩尔Mo)加入300ml水中以形成浆液。溶液B：在500ml烧瓶中，将13.05g偏钨酸铵(0.05摩尔W)加入90ml的浓缩NH4OH溶液中。将溶液B加入溶液A中，然后于100℃回流。在加热期间，沉淀物溶解以在形成石灰绿色沉淀物之前得到清澈的深蓝色溶液。在2小时后，观察到绿色沉淀物悬浮在蓝色的pH 9溶液中。此沉淀物被冷却到室温，过滤，用90ml的90℃水洗涤，然后于100℃干燥。经干燥的沉淀物的x-射线衍射图案符合如图1所示的X-射线粉末衍射图案。
实施例3
溶液A：在3L烧瓶中，将35.61g碳酸镍(0.3摩尔Ni)和28.79g三氧化钼(0.2摩尔Mo)加入300ml水中以形成浆液。溶液B：在500ml烧瓶中，将26.1g偏钨酸铵(0.1摩尔W)加入90ml的浓缩NH4OH溶液中。将溶液B加入溶液A中，然后于100℃回流。在加热期间，沉淀物溶解以在形成石灰绿色沉淀物之前得到清澈的深蓝色溶液。在3小时后，观察到绿色沉淀物悬浮在蓝色的pH 9溶液中。此沉淀物被冷却到室温，过滤，用90ml的90℃水洗涤，然后于100℃干燥。经干燥的沉淀物的x-射线衍射图案符合如图1所示的X-射线粉末衍射图案。
本发明的实施方案：
实施方案1是具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure BDA0001695788810000111
实施方案1的结晶双氨过渡金属钼钨酸盐材料可以作为与至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂。
实施方案1的结晶双氨过渡金属钼钨酸盐材料可以作为与至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂，其中粘合剂是选自二氧化硅、氧化铝和二氧化硅-氧化铝。
实施方案1的结晶双氨过渡金属钼钨酸盐材料，其中M是镍或钴。
实施方案1的结晶双氨过渡金属钼钨酸盐材料，其中M是镍。
实施方案1的结晶双氨过渡金属钼钨酸盐材料，其中此材料是被硫化的。
实施方案2是制备具有下式的结晶双氨过渡金属钼钨酸盐材料的方法，
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure BDA0001695788810000121
此方法包括：形成含有M、Mo和W的源物质的反应混合物；将反应混合物的pH调节到8.5-10的pH；将反应混合物加热到85-100℃，直到所得的pH是8.5-9.5；然后回收结晶双氨过渡金属钼钨酸盐材料。
实施方案2的方法，其中所述回收可以通过过滤或离心进行。
实施方案2的方法，其中还包括将粘合剂加入所回收的结晶双氨过渡金属钼钨酸盐材料中。
实施方案2的方法，其中还包括将粘合剂加入所回收的结晶双氨过渡金属钼钨酸盐材料中，其中粘合剂可以选自氧化铝、二氧化硅和氧化铝-二氧化硅。
实施方案2的方法，其中还包括使所回收的结晶双氨过渡金属钼钨酸盐材料进行硫化。
实施方案3是一种转化方法，此方法包括使进料与催化剂在转化条件下接触以得到至少一种产物，所述催化剂包含：具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内，或是0.6-1.3，或是0.8-1.2；‘y’在0.01-0.25的范围内，或是0.1-0.2；(x+y)的总和必须≤1.501或≤1.2；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure BDA0001695788810000131
实施方案3的方法，其中转化方法是加氢操作。
实施方案3的方法，其中转化方法是选自加氢脱氮，加氢脱硫，加氢脱金属化，加氢脱芳构化，加氢异构化，加氢脱硅，加氢处理，加氢精制，以及加氢裂解。
实施方案3的方法，其中结晶双氨过渡金属钼钨酸盐材料作为与至少一种粘合剂的混合物存在，和其中此混合物含有至多25重量％的粘合剂。
实施方案3的方法，其中结晶双氨过渡金属钼钨酸盐材料是被硫化的。

Claims (11)

1.具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内；‘y’在0.01-0.25的范围内；(x+y)的总和必须≤1.501；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure FDA0002946880170000011
2.权利要求1的结晶双氨过渡金属钼钨酸盐材料，其中结晶双氨过渡金属钼钨酸盐材料是作为与选自二氧化硅、氧化铝和二氧化硅-氧化铝的至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂。
3.权利要求1的结晶双氨过渡金属钼钨酸盐材料，其中结晶双氨过渡金属钼钨酸盐材料是被硫化的。
4.一种制备具有下式的结晶双氨过渡金属钼钨酸盐材料的方法，
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内；‘y’在0.01-0.25的范围内；(x+y)的总和必须≤1.501；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure FDA0002946880170000021
此方法包括：
(a)形成含有M、W和Mo的源物质的反应混合物；
(b)将反应混合物的pH调节到8.5-10的pH，其中混合物的pH通过加入碱来控制，碱选自NH4OH、季铵氢氧化物和胺；
(c)将反应混合物加热到85-100℃，直到所得的pH是8.5-9.5；和
(d)回收结晶双氨过渡金属钼钨酸盐材料。
5.权利要求4的方法，还包括将选自氧化铝、二氧化硅和氧化铝-二氧化硅的粘合剂加入所回收的结晶双氨过渡金属钼钨酸盐材料中。
6.权利要求4的方法，还包括使所回收的结晶双氨过渡金属钼钨酸盐材料进行硫化。
7.一种转化方法，包括使进料与催化剂在转化条件下接触以得到至少一种产物，所述催化剂包含：具有下式的结晶双氨过渡金属钼钨酸盐材料：
(NH3)2-nM(OH2)nMoxWyOz
其中‘n’在0.1-2.0的范围内；‘M’表示选自Mg、Mn、Fe、Co、Ni、Cu、Zn及其混合物的金属；‘x’在0.5-1.5的范围内；‘y’在0.01-0.25的范围内；(x+y)的总和必须≤1.501；‘z’是满足M、Mo和W的价键总和的数值，所述材料具有独特的x-射线粉末衍射图案，其中显示在表A所列出的d-间距处的峰：
表A
Figure FDA0002946880170000031
8.权利要求7的方法，其中转化方法是加氢操作方法，和其中加氢操作方法是选自加氢脱金属化，加氢脱芳构化，加氢异构化，加氢脱硅，加氢精制，以及加氢裂解。
9.权利要求8的方法，其中加氢精制选自加氢脱氮和加氢脱硫。
10.权利要求7的方法，其中结晶双氨过渡金属钼钨酸盐材料是作为与至少一种粘合剂的混合物存在，并且其中此混合物含有至多25重量％的粘合剂。
11.权利要求7的方法，其中结晶双氨过渡金属钼钨酸盐材料是被硫化的。
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Families Citing this family (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10882030B2 (en) 2017-08-25 2021-01-05 Uop Llc Crystalline transition metal tungstate
US10773245B2 (en) 2017-08-25 2020-09-15 Uop Llc Crystalline transition metal molybdotungstate
US10843176B2 (en) * 2017-12-20 2020-11-24 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US10875013B2 (en) 2017-12-20 2020-12-29 Uop Llc Crystalline oxy-hydroxide transition metal molybdotungstate
US11078088B2 (en) 2017-12-20 2021-08-03 Uop Llc Highly active multimetallic materials using short-chain alkyl quaternary ammonium compounds
US11007515B2 (en) 2017-12-20 2021-05-18 Uop Llc Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds
US10995013B2 (en) 2017-12-20 2021-05-04 Uop Llc Mixed transition metal tungstate
US11117811B2 (en) 2017-12-20 2021-09-14 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US10822247B2 (en) 2017-12-20 2020-11-03 Uop Llc Highly active trimetallic materials using short-chain alkyl quaternary ammonium compounds
US11034591B2 (en) 2017-12-20 2021-06-15 Uop Llc Highly active quaternary metallic materials using short-chain alkyl quaternary ammonium compounds
US10737249B2 (en) 2018-06-26 2020-08-11 Uop Llc Crystalline transition metal molybdotungstate
US10688479B2 (en) 2018-06-26 2020-06-23 Uop Llc Crystalline transition metal tungstate
US11033883B2 (en) * 2018-06-26 2021-06-15 Uop Llc Transition metal molybdotungstate material
US10682632B2 (en) * 2018-06-26 2020-06-16 Uop Llc Transition metal tungstate material
US10737248B2 (en) 2018-06-26 2020-08-11 Uop Llc Crystalline transition metal tungstate
US10737246B2 (en) 2018-06-29 2020-08-11 Uop Llc Poorly crystalline transition metal tungstate
US10981151B2 (en) 2018-06-29 2021-04-20 Uop Llc Poorly crystalline transition metal molybdotungstate
US11213803B2 (en) 2018-12-13 2022-01-04 Uop Llc Ammonia-free synthesis for Al or Si based multimetallic materials
US10933407B2 (en) 2018-12-13 2021-03-02 Uop Llc Ammonia-free synthesis for Al or Si based multimetallic materials
US11426711B2 (en) 2019-05-22 2022-08-30 Uop Llc Method of making highly active metal oxide and metal sulfide materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6758963B1 (en) * 1997-07-15 2004-07-06 Exxonmobil Research And Engineering Company Hydroprocessing using bulk group VIII/group vib catalysts
EP1941944A1 (en) * 2005-08-31 2008-07-09 Instituto Mexicano Del Petroleo Method of preparing a catalytic composition for the hydroprocessing of petroleum fractions
CN101439882B (zh) * 2008-12-17 2010-09-01 中国石油天然气集团公司 一种用尿素作为沉淀剂合成介孔钼酸镍铵的方法
WO2010126689A2 (en) * 2009-04-29 2010-11-04 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof

Family Cites Families (73)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4820677A (en) 1984-04-02 1989-04-11 Jacobson Allan J Amorphous, iron promoted Mo and W sulfide hydroprocessing catalysts and process for their preparation
US4904634A (en) 1986-12-29 1990-02-27 Aluminum Company Of America Active material useful as adsorbent comprising metal oxide/hydroxide surfaces reacted with one or more phosphorous-containing materials having selected organic radicals attached thereto
US5278121A (en) 1990-10-01 1994-01-11 Exxon Research & Engineering Company Multimetallic sulfide catalyst containing noble metals for hydrodenitrogenation
JP3802106B2 (ja) 1995-06-08 2006-07-26 日本ケッチェン株式会社 炭化水素油の水素化処理触媒とその製造方法およびその活性化方法
RU2098181C1 (ru) 1996-04-23 1997-12-10 Завод по производству катализаторов Акционерного общества "Куйбышевнефтеоргсинтез" Способ приготовления катализатора для гидроочистки нефтяных фракций
US6620313B1 (en) 1997-07-15 2003-09-16 Exxonmobil Research And Engineering Company Hydroconversion process using bulk group VIII/Group VIB catalysts
US6156695A (en) * 1997-07-15 2000-12-05 Exxon Research And Engineering Company Nickel molybdotungstate hydrotreating catalysts
US6783663B1 (en) 1997-07-15 2004-08-31 Exxonmobil Research And Engineering Company Hydrotreating using bulk multimetallic catalysts
US7229548B2 (en) 1997-07-15 2007-06-12 Exxonmobil Research And Engineering Company Process for upgrading naphtha
US6863803B1 (en) 1997-07-15 2005-03-08 Exxonmobil Research And Engineering Company Production of low sulfur/low nitrogen hydrocrackates
US6582590B1 (en) 1997-07-15 2003-06-24 Exxonmobil Research And Engineering Company Multistage hydroprocessing using bulk multimetallic catalyst
US7232515B1 (en) 1997-07-15 2007-06-19 Exxonmobil Research And Engineering Company Hydrofining process using bulk group VIII/Group VIB catalysts
US6635599B1 (en) 1997-07-15 2003-10-21 Exxonmobil Research & Engineering Company Mixed metal catalyst, its preparation by co-precipitation, and its use
US6929738B1 (en) 1997-07-15 2005-08-16 Exxonmobil Research And Engineering Company Two stage process for hydrodesulfurizing distillates using bulk multimetallic catalyst
US6712955B1 (en) 1997-07-15 2004-03-30 Exxonmobil Research And Engineering Company Slurry hydroprocessing using bulk multimetallic catalysts
US7288182B1 (en) 1997-07-15 2007-10-30 Exxonmobil Research And Engineering Company Hydroprocessing using bulk Group VIII/Group VIB catalysts
US6162350A (en) 1997-07-15 2000-12-19 Exxon Research And Engineering Company Hydroprocessing using bulk Group VIII/Group VIB catalysts (HEN-9901)
US7513989B1 (en) 1997-07-15 2009-04-07 Exxonmobil Research And Engineering Company Hydrocracking process using bulk group VIII/Group VIB catalysts
JP4174887B2 (ja) 1998-05-21 2008-11-05 堺化学工業株式会社 ニッケル、コバルト又は銅の炭酸塩又は水酸化物の微細な球状の粒子の製造方法
US6534437B2 (en) 1999-01-15 2003-03-18 Akzo Nobel N.V. Process for preparing a mixed metal catalyst composition
AU761109B2 (en) * 1999-01-15 2003-05-29 Albemarle Netherlands B.V. A mixed metal catalyst composition, its preparation and use
US6299760B1 (en) 1999-08-12 2001-10-09 Exxon Research And Engineering Company Nickel molybodtungstate hydrotreating catalysts (law444)
AR043243A1 (es) 2003-02-24 2005-07-20 Shell Int Research Composicion de catalizador ,su preparacion y uso
TW200425950A (en) 2003-02-24 2004-12-01 Shell Int Research Catalyst composition preparation and use
US7232934B2 (en) 2003-09-19 2007-06-19 Exxonmobil Chemical Patents Inc. Hydrogenation of oxo aldehydes to oxo alcohols in the presence of a nickel-molybdenum catalyst
US7709412B2 (en) 2004-04-22 2010-05-04 Exxonmobil Research & Engineering Company Bulk metal hydrotreating catalyst used in the production of low sulfur diesel fuels
US7691257B2 (en) 2004-04-22 2010-04-06 Exxonmobil Research And Engineering Company Process to manufacture low sulfur diesel fuels
US7776205B2 (en) 2004-04-22 2010-08-17 Exxonmobil Research And Engineering Company Process to upgrade hydrocarbonaceous feedstreams
HUE026582T2 (hu) 2004-04-22 2016-06-28 Albemarle Netherlands Bv V. csoportbeli fémet tartalmazó hidrogén-kezelési katalizátor
US7780845B2 (en) 2004-04-22 2010-08-24 Exxonmobil Research And Engineering Company Process to manufacture low sulfur distillates
US7648941B2 (en) 2004-09-22 2010-01-19 Exxonmobil Research And Engineering Company Bulk bimetallic catalysts, method of making bulk bimetallic catalysts and hydroprocessing using bulk bimetallic catalysts
US7544632B2 (en) 2004-09-22 2009-06-09 Exxonmobil Research And Engineering Company Bulk Ni-Mo-W catalysts made from precursors containing an organic agent
US7591942B2 (en) 2004-09-22 2009-09-22 Exxonmobil Research And Engineering Company Bulk bi-metallic catalysts made from precursors containing an organic agent
US7538066B2 (en) 2005-09-29 2009-05-26 Exxonmobil Research And Engineering Company Method of preparing a hydrotreating catalyst on a support containing a rare earth metal
US7605107B2 (en) 2005-09-29 2009-10-20 Exxonmobil Research And Engineering Company Method of preparing a supported hydrotreating catalyst
WO2007050636A2 (en) 2005-10-26 2007-05-03 Exxonmobil Research And Engineering Company Hydroprocessing using bulk bimetallic catalysts
WO2007048600A2 (en) * 2005-10-26 2007-05-03 Albemarle Netherlands Bv A bulk catalyst comprising metal oxidic particles of group vi and viii and a process for the manufacture therof
EA013580B1 (ru) 2005-10-26 2010-06-30 Альбемарл Недерландс Бв Массивный катализатор, содержащий никельвольфрамовые металлоксидные частицы
CN101340973B (zh) 2005-10-26 2013-08-07 埃克森美孚研究工程公司 利用水热制备的体相多金属催化剂的加氢处理
CA2636177C (en) 2006-01-17 2015-10-06 Exxonmobil Research And Engineering Company Selective catalysts having silica supports for naphtha hydrodesulfurization
US7951746B2 (en) 2006-10-11 2011-05-31 Exxonmobil Research And Engineering Company Bulk group VIII/group VIB metal catalysts and method of preparing same
FR2910351B1 (fr) 2006-12-22 2009-02-27 Total France Sa Catalyseur d'hydrotraitement, son procede de preparation et son utilisation.
US7838696B2 (en) 2007-10-31 2010-11-23 Chevron U. S. A. Inc. Hydroconversion process employing multi-metallic catalysts and method for making thereof
US20090114566A1 (en) 2007-10-31 2009-05-07 Chevron U.S.A. Inc. Method of upgrading heavy hydrocarbon streams to jet products
AU2007361300B2 (en) 2007-11-09 2012-07-12 Exxonmobil Research And Engineering Company Preparation of bulk metallic Group VIII/Group VIB metal catalysts
AU2008331798B2 (en) 2007-12-04 2012-11-01 Exxonmobil Research And Engineering Company Hydrocarbon hydroprocessing using bulk catalyst composition
JP5543361B2 (ja) 2007-12-04 2014-07-09 アルベマール・ネーザーランズ・ベー・ブイ バルク金属酸化物粒子を調製するためのプロセス
EP2103347A1 (en) 2008-03-17 2009-09-23 ExxonMobil Research and Engineering Company Hydrocarbon hydroprocessing using bulk catalyst composition
CN101544904B (zh) 2008-03-28 2012-11-14 中国科学院大连化学物理研究所 一种复合金属氧化物催化剂及制备和应用
TW200950880A (en) 2008-04-09 2009-12-16 Basf Se Coated catalysts comprising a multimetal oxide comprising molybdenum, bismuth and iron
US8383543B2 (en) 2009-04-29 2013-02-26 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
US7964526B2 (en) * 2009-04-29 2011-06-21 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
US8080492B2 (en) 2009-04-29 2011-12-20 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
US8058203B2 (en) * 2009-04-29 2011-11-15 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
CN102049265B (zh) 2009-10-27 2013-01-09 中国石油化工股份有限公司 一种加氢处理催化剂及其制备方法
US8636967B2 (en) 2010-01-21 2014-01-28 Intevep, S.A. Metal recovery from hydroconverted heavy effluent
US8586500B2 (en) 2010-11-11 2013-11-19 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
US8658558B2 (en) 2010-11-11 2014-02-25 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
EA024283B1 (ru) 2010-11-11 2016-09-30 Шеврон Ю.Эс.Эй. Инк. Мультиметаллический катализатор гидропереработки и способ его получения
EA201390997A1 (ru) 2010-12-30 2014-03-31 Шеврон Ю.Эс.Эй. Инк. Катализаторы гидропереработки и способы их получения
US10507458B2 (en) 2012-08-29 2019-12-17 Indian Oil Corporation Limited Hydrotreating catalyst and process for preparing the same
US9435043B2 (en) 2014-04-14 2016-09-06 California Institute Of Technology Oxygen evolution reaction catalysis
US10400181B2 (en) * 2015-12-15 2019-09-03 Uop Llc Crystalline bis-ammonia metal molybdate
US10046315B2 (en) 2015-12-15 2018-08-14 Uop Llc Crystalline transition metal molybdotungstate
US10232357B2 (en) 2015-12-15 2019-03-19 Uop Llc Crystalline ammonia transition metal molybdate
US10052614B2 (en) 2015-12-15 2018-08-21 Uop Llc Mixed metal oxides
US10399063B2 (en) 2015-12-15 2019-09-03 Uop Llc Mixed metal oxides
US10233398B2 (en) * 2015-12-15 2019-03-19 Uop Llc Crystalline transition metal oxy-hydroxide molybdotungstate
US10399065B2 (en) 2015-12-15 2019-09-03 Uop Llc Crystalline transition metal tungstate
US10053637B2 (en) 2015-12-15 2018-08-21 Uop Llc Transition metal tungsten oxy-hydroxide
US10052616B2 (en) 2015-12-15 2018-08-21 Uop Llc Crystalline ammonia transition metal molybdotungstate
US10005812B2 (en) 2015-12-15 2018-06-26 Uop Llc Transition metal molybdotungsten oxy-hydroxide
EP3408023B1 (en) 2016-01-29 2024-03-20 TotalEnergies OneTech Homogeneously dispersed multimetal oxy-hydroxide catalysts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6758963B1 (en) * 1997-07-15 2004-07-06 Exxonmobil Research And Engineering Company Hydroprocessing using bulk group VIII/group vib catalysts
EP1941944A1 (en) * 2005-08-31 2008-07-09 Instituto Mexicano Del Petroleo Method of preparing a catalytic composition for the hydroprocessing of petroleum fractions
CN101439882B (zh) * 2008-12-17 2010-09-01 中国石油天然气集团公司 一种用尿素作为沉淀剂合成介孔钼酸镍铵的方法
WO2010126689A2 (en) * 2009-04-29 2010-11-04 Chevron U.S.A. Inc. Hydroconversion multi-metallic catalyst and method for making thereof
CN102413933A (zh) * 2009-04-29 2012-04-11 雪佛龙美国公司 加氢转化多金属催化剂及其制备方法

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