CN101544904A - 一种复合金属氧化物催化剂及制备和应用 - Google Patents
一种复合金属氧化物催化剂及制备和应用 Download PDFInfo
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
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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
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- C—CHEMISTRY; METALLURGY
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Abstract
本发明涉及柴油超深度加氢脱硫,具体地说是一种复合金属氧化物催化剂及制备和应用,它是由一种VIII族金属MI和两种VIB族金属MII和MIII形成的复合氧化物结构,其中,VIII族金属MI与VIB族金属MII+MIII的摩尔比为1∶9-9∶1;而两种VIB族金属MII和MIII的摩尔比为1∶5-5∶1。本发明的催化剂用于柴油的超深度加氢脱硫中,表现出极高的加氢脱硫活性,在同样的操作条件下,其活性是工业参比剂的7.5倍。
Description
技术领域
本发明涉及柴油超深度加氢脱硫,具体地说是一种复合金属氧化物催化剂及制备和应用,此种催化剂具有多金属氧化物复合结构的活性物种,从而表现出极高的加氢脱硫活性。
背景技术
随着日益严格的环境法规,要求液体燃料中的硫含量越来越低,但是世界范围内高硫原油逐年增多,因此开发性能良好的柴油超深度加氢脱硫催化剂,已经成为举世瞩目的新课题。燃料油中的有机硫化物经燃烧后产生的SOx不仅能导致酸雨,还能使汽车发动机尾气净化系统的三效催化剂产生不可逆中毒,因此引起人们广泛的关注。为此,各国都颁布了严格的柴油含硫量标准,我国将在2010年7月1日实行相当欧IV(<50ppm)的排放标准(北京、上海等大城市提前2年)。因此,迫切需要研制具有高加氢脱硫活性的催化剂来满足柴油超深度加氢的要求。
目前,工业上使用的加氢脱硫催化剂的基本组成都很相似,即以VIII族金属Co或Ni做催化剂助剂,以VIB族金属Mo或W做催化剂活性组分,采用活性氧化铝或硅铝氧化物做载体,还可以通过添加各种助剂(如硼、钛、磷或硅)来改善催化剂的性能。然而,传统的催化剂较难脱除液体燃料中烷基取代的多环芳香噻吩类含硫化合物,如二苯并噻吩及4,6-二甲基二苯并噻吩。此外,重质油加氢过程中,硫化钼类催化剂易于中毒失活。为了适应液体燃料超深度脱硫和重质油精加工的趋势,要求寻找和开发新的催化体系。调整工艺操作条件和使用新型反应器都需要巨额的投资费用,相比之下,研制一种能够在现有的生产装置上,按照现行的操作条件进行超深度加氢脱硫的新型催化剂,是一种更为经济,更加可行的方法。
我们知道,由于载体本身的催化效果有限,它只是通过增大反应物与载体的接触面积或载体与活性组分间的协同作用来增加催化效果,所以一般担载型催化剂的加氢脱硫活性很难再进行大幅度改进。而多金属本体催化剂,即多金属非担载型催化剂,由于其具有多种活性组分,并且活性中心数目要大大多于担载型催化剂,所以它是一种具有很高催化活性的催化剂,在近期的文献和专利报道中,显示出了极高的加氢脱硫反应活性,引起人们的广泛关注。
美国专利6299760、6156695、6783663、6712955、6758963等都报道了新型NiMoW本体催化剂合成和应用,且这种新型的催化剂的加氢脱硫活性是其他的工业参比剂的三倍左右。这种催化剂的合成过程都是以氨水为络合剂,反应生成NiMoW催化剂前体,再通过焙烧和硫化,形成NiMoW催化剂。此种合成方法的不足之处在于,合成过程中使用了浓氨水,会对环境造成污染。
从已有报道工作不难发现,现有的本体催化剂的合成方法存如下不足的地方:(1)使用的原料对环境不友好;(2)催化剂制备成本较高;(3)催化剂粒子较大,活性还有待进一步提高。
发明内容
本发明的目的是提供一种高活性的复合金属氧化物催化剂及制备和应用。
为实现上述目的,本发明采用的技术方案为:
一种复合金属氧化物催化剂,其粒径为10-100nm,并且具有多金属氧化物复合结构的活性物种,由一种VIII族金属和两种VIB族金属组成;其中,VIII族金属与VIB族金属的摩尔比为1:9-9:1,优选的摩尔比为1:6-6:1,推荐的摩尔比为1:4-4:1;而两种VIB族金属的摩尔比为1:5-5:1,优选的摩尔比为1:3-3:1,推荐的摩尔比为1:2-2:1。
通过氢气程序升温还原以及紫外可见漫反射光谱分析测试,可以发现MI-MII-O,MI-MIII-O和MI-MII-MIII-O类型结构的活性物种,说明了在本发明合成的催化剂中形成了具有多金属氧化物复合结构的活性物种。
所述催化剂的制备方法,其步骤为:
a)将VIII族金属的碱式碳酸盐加入水中,形成碱式碳酸盐浓度为0.1~0.9mol/l的悬浊液;
b)将VIB族的两种金属元素的盐溶于水中,形成金属离子浓度为0.03~0.3mol/l,并加入表面活性剂、使表面活性剂于溶液中的浓度为1~5wt%,搅拌加热至50-250℃;
c)将步骤a)的悬浊液加入步骤b)溶液中,于50-250℃下回流反应4-25小时,反应时间优选8-25小时,推荐16-25小时;
步骤b)和步骤c)中的温度优选50-200℃,推荐50-120℃;
d)将步骤c)得到的产物过滤、洗涤、干燥,得到目标产物;
所述的表面活性剂为:十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十八烷基三甲基溴化铵或十八烷基三甲基氯化铵,优选十六烷基三甲基溴化铵或十六烷基三甲基氯化铵,推荐十六烷基三甲基氯化铵。
所述的制备方法,其中,VIB族金属盐包括:钼酸铵、钨酸铵、偏钨酸铵、钼酸钠或钨酸钠,推荐钼酸铵、钨酸铵或偏钨酸铵。
本发明所合成的多金属本体催化剂,通过氢气程序升温还原以及紫外可见漫反射光谱分析测试,可以发现类似Ni(Co)WO4,Ni(Co)MoO4和Ni(Co)-Mo-W-O结构的活性物种,说明在本发明合成的催化剂中形成了具有多金属氧化物复合结构的活性物种。
本发明提供的多金属本体催化剂,可以应用在柴油超深度加氢脱硫反应中,其反应温度280-400℃,氢气压力1-20MPa,氢油体积比为50-1000,物料的体积空速0.1-10h-1。
本发明催化剂在进行柴油加氢脱硫反应前应作如下预处理:
(i)在空气气氛中,于350-550℃焙烧;
(ii)研磨、混捏、成型;
(iii)在加氢脱硫固定反应床上,于300-450℃下以含硫有机物与氢气的混合物进行原位硫化,含硫有机物在混合气体中的体积含量为10%,这些含硫有机物可以是硫化氢、二硫化碳或二甲基硫。
本发明的多金属本体催化剂和公知技术相比,具有如下优点:
1、本发明中合成催化剂的原料简单廉价,合成过程易于操作,对于环境友好,催化剂可以工业化生产。
2、本发明合成的催化剂具有纳米尺度大小,较高的分散程度、较均匀的粒径大小分布等特点;而且最终的产物可能保持了碱式碳酸盐层状结构;在本发明合成的催化剂中形成了具有多金属氧化物复合结构的活性物种,从而增加了催化剂的活性。
3、该催化剂用于柴油的超深度加氢脱硫之中,表现出极高的加氢脱硫活性,在同样的操作条件下,其活性是工业参比剂的7.5倍。通过对催化剂的H2-TPR和紫外可见漫反射光谱的分析测试,可以发现NiWO4,NiMoO4和Ni-Mo-W-O多金属复合结构的活性物种,进一步发现在本发明合成的催化剂在中形成了具有多金属氧化物复合结构的活性物种,从而决定了此催化剂具有极高的加氢脱硫活性。
附图说明
图1是NiMoW类催化剂前躯体的紫外可见漫反射光谱图。在谱图上,我们可以看到催化剂氧化物前躯体在600nm-800nm之间,只在720nm左右存在宽峰,而在650nm左右没有明显的峰存在,说明催化剂中以四面体配位的Ni2+离子存在的Ni金属很少,它主要以八面体配位的形式存在,与Mo和W形成了NiWO4,NiMoO4和Ni-Mo-W-O类型的活性物种。
图2是NiMoW类催化剂氧化物前躯体的氢气程序升温还原谱图,通过查阅文献,从H2-TPR的谱图中找到了各个还原峰的归属,其中,对于Cat-F催化剂,在420℃左右的肩峰可以归属为Ni2+物种的还原峰,在450℃的强峰可以归属为Ni2+或聚合八面体Mo物种的还原峰,475℃的强峰归属为类NiMoO4物种或聚合八面体Mo物种的还原峰,在480℃-600℃的肩峰可以归属为聚合八面体Mo物种的还原峰,高于800℃的强峰可以归属为W物种的还原峰。同样,对于NiMoW-B催化剂,也有相似的归属,在600℃和700℃左右的肩峰分别归属为八面体配位Ni2+物种和四面体配位Mo物种的还原峰。对于NiMoW-F催化剂,我们可以看到其主要存在的是归属为NiMoO4类型物种的还原峰。另外,在催化剂氧化物前躯体中,其W物种的还原峰向高温移动,说明其与Ni和Mo之间发生了相互作用。因此,通过表征结果我们可以说明,本发明合成的催化剂其三种活性金属间形成了某种NiWO4,NiMoO4和Ni-Mo-W-O复合结构的活性物种。
图3是NiMoW催化剂硫化后的SEM及TEM表征:(a)硫化后的NiMoW催化剂的扫描电子显微镜照片;(b)硫化后的NiMoW催化剂的透射电子显微镜照片。通过透射电子显微镜测试可以观察到催化剂是由大小均一,高度分散的粒子组成,且具有纳米尺寸;进一步通过透射电子显微镜的测试还可以观察到明显的归属于相应金属硫化物的晶面间距条纹,且经过本发明合成的催化剂于文献中报道的催化剂相比具有更短的条纹和更少的晶面条纹堆积,由此可以推测本发明合成的催化剂具有更高的活性。
具体实施方式
为了进一步说明本发明,列举以下实施实例,但它并不限制各附加权利要求所定义的发明范围。比如,本发明根据实验结果提出可以制备一种VIII族金属和两种VIB族金属的具有纳米尺寸的多金属本体催化剂,这种VIII族金属可以是Co、Ni、Fe等,而VIB族金属则可以是Cr、Mo、W等;
实施例1
本发明中NiMoW本体催化剂的制备:
a、分别称取的钼酸铵和偏钨酸铵,其中Mo6+0.01mol,W6+0.01mol,将它们溶于350ml水和5ml十六烷基三甲基氯化铵组成的混合溶剂中,形成溶液,并将此溶液加热至120℃,不断搅拌,形成无色透明溶液;随后称取自制碱式碳酸镍,含Ni2+0.03mol,将其加入50ml的水中,配成悬浊液,并加热至120℃;将此反应悬浊液慢慢地加入无色透明溶液中,形成浅绿色反应液,在150℃反应温度下回流反应20小时;将反应得到的黄绿色粉末过滤、洗涤,并在120℃烘干,得到NiMoW催化剂前体。
此实施例中合成的催化剂用Cat-A来表示,其透射电子显微镜、扫描电子显微镜照片列于图3中,可以观察到催化剂是由大小均一,高度分散的粒子组成,具有纳米尺寸,其粒径为10-100nm。
b、然后将此催化剂的前体进行焙烧,条件为空气气氛中400℃烧2个小时,得到NiMoW催化剂氧化物前体。在进行加氢脱硫和一些表征之前,在对此催化剂前体进行硫化,硫化条件为在体积含量10%H2S/H2气氛中,在400℃下反应2个小时,其中H2S/H2混合气体的流速为60毫升/分钟。
实施例2
同实施例1,只是步骤a中使用了350ml水和5ml十六烷基三甲基溴化铵组成的混合溶剂溶解0.01mol Mo6+和0.01mol W6+形成溶液,合成的催化剂产物用Cat-B来表示。
实施例3
同实施例1,只是步骤a中使用了350ml水和5ml十八烷基三甲基溴化铵组成的混合溶剂溶解0.01mol Mo6+和0.01mol W6+形成溶液,合成的催化剂产物用Cat-C来表示。
实施例4
同实施例1,只是步骤a中催化剂合成反应温度为50℃,合成的催化剂用Cat-D来表示。
实施例5
同实施例1,只是步骤a中催化剂合成反应温度为250℃,合成的催化剂用Cat-E来表示。
实施例6
同实施例1,只是步骤a中使用了商业碱式碳酸镍,合成的催化剂产物用Cat-F来表示。
实施例7
同实施例1,只是步骤a中使用钼酸铵和钨酸铵(其中含有0.01mol Mo6+和0.01mol W6+)为原料,合成催化剂产物用Cat-G来表示。
实施例8
同实施例1,只是步骤a中使用钼酸钠和钨酸钠(其中含有0.01mol Mo6+和0.01mol W6+)为原料,合成催化剂产物用Cat-H来表示。
实施例9
同实施例1,只是步骤a中的投料比为Ni:Mo:W=1:1:2,合成催化剂产物用Cat-I来表示。
实施例10
同实施例1,只是步骤a中的投料比为Ni:Mo:W=6:2:1,合成催化剂产物用Cat-J来表示。
实施例11
同实施例1,只是步骤b中使用的硫化混合气体是体积含量为10%CS2/H2,合成催化剂产物用Cat-K来表示。
实施例12
同实施例1,只是步骤b中使用硫化混合气体是体积含量为10%二甲基硫/氢气混合气,合成催化剂产物用Cat-L来表示。
实施例13
同实施例1,只是步骤b中催化剂焙烧温度为350℃,合成的催化剂用Cat-M来表示。
实施例14
同实施例1,只是步骤b中催化剂焙烧温度为550℃,合成的催化剂用Cat-N来表示。
实施例15
同实施例1,只是步骤a中催化剂合成反应时间为4小时,合成的催化剂用Cat-O来表示。
实施例16
同实施例1,只是步骤b中催化剂硫化温度为300℃,合成的催化剂用Cat-P来表示。
实施例17
对Cat-B,Cat-F,Cat-G进行氢气程序升温还原以及紫外可见漫反射光谱分析测试,见图1和图2,可以发现MI-MII-O,MI-MIII-O和MI-MII-MIII-O类型结构的活性物种,说明了在本发明合成的催化剂中形成了具有多金属氧化物复合结构的活性物种。
实施例18
本发明中CoMoW本体催化剂的制备:
a、分别称取钼酸铵和偏钨酸铵,其中Mo6+0.01mol,W6+0.01mol,将它们溶于350ml水和十六烷基三甲基氯化铵混合溶剂中,形成溶液,并将此溶液加热至120℃,不断搅拌;随后称取碱式碳酸钴,含Co2+0.03mol,将其溶于少量的水中,配成悬浊液,并加热至120℃;将此反应悬浊液慢慢地加入无色透明溶液中,形成浅绿色反应液,在150℃反应温度下回流反应20小时;将反应得到的黄绿色粉末过滤洗涤,并在120℃烘干,得到CoMoW催化剂前体。
b、然后将此催化剂的前体进行焙烧,条件为空气气氛中400℃烧2个小时,得到CoMoW催化剂氧化物前体。在进行加氢脱硫和一些表征之前,在对此催化剂前体进行硫化,硫化条件为在体积含量10%H2S/H2气氛中,在400℃下反应2个小时,其中10% H2S/H2的流速为60毫升/分钟。
合成的催化剂用Cat-Q来表示。
催化剂在加氢脱硫反应中性能的研究
以含硫量为1200ppm的真实柴油来考察催化剂在加氢脱硫反应中的性能,反应在固定床反应器中进行。反应条件为:催化剂质量1g,反应温度在300℃,氢气压力3.5Mpa,氢油比为600Nm3/m3,体积空速6h-1。对于样品中含硫量的测试采用的是微库仑滴定仪。
性能实验测试比较了Cat-A、Cat-B、Cat-C、Cat-D、Cat-E、Cat-F、Cat-G、Cat-H、Cat-I、Cat-J以及工业参比剂的活性,反应活性结果列于表1中。
本发明制备催化剂的活性用相对活性表示,即以参比剂运转200小时的活性为100,本发明催化剂与之比较所得的活性表示发明催化剂的相对活性。相对脱硫活性按下列公式计算:
相对脱硫活性=100×[(1/Sp)0.65-(1/Sf)0.65]/[(1/Spr)0.65-(1/Sfr)0.65]式中Sfr、Spr分别表示参比剂所用原料油和经参比剂加氢处理后产物的含硫浓度,Sf、Sp分别表示发明催化剂所用原料油和经发明催化剂加氢处理后的产物含硫浓度。
表1、几种NiMoW催化剂与工业参比剂加氢脱硫活性的比较
催化剂 | 相对脱硫活性 | 催化剂 | 相对脱硫活性 |
Cat-A | 698 | Cat-I | 244 |
Cat-B | 406 | Cat-J | 396 |
Cat-C | 438 | Cat-K | 287 |
Cat-D | 452 | Cat-L | 634 |
Cat-E | 383 | Cat-M | 547 |
Cat-F | 233 | Cat-N | 274 |
Cat-G | 754 | Cat-O | 131 |
Cat-H | 301 | Cat-P | 121 |
商业催化剂 | 100 | Cat-Q | 593 |
综上所述,本发明通过调变优化制备催化剂的溶剂组成,合成了具有较高加氢脱硫活性的多金属本体催化剂,这种催化剂具有纳米尺度,较高的分散程度、较均匀的粒径大小分布等特点,显示出多金属复合结构活性物种的存在,它的活性要远远大于商业催化剂,显示出巨大的工业应用价值。
Claims (10)
1.一种复合金属氧化物催化剂,其特征在于:它是由一种VIII族金属MI和两种VIB族金属MII和MIII形成的复合氧化物结构,包括MI-MII-O,MI-MIII-O和MI-MII-MIII-O三种类型结构的活性物种,其中,VIII族金属MI与VIB族金属MII+MIII的摩尔比为1:9-9:1;而两种VIB族金属MII和MIII的摩尔比为1:5-5:1。
2.如权利要求1所述的催化剂,其特征在于:VIII族金属MI与VIB族金属MII+MIII的摩尔比为1:6-6:1,两种VIB族金属MII和MIII的摩尔比为1:3-3:1。
3.如权利要求1所述的催化剂,其特征在于:VIII族金属MI与VIB族金属MII+MIII的摩尔比为1:3-3:1,两种VIB族金属MII和MIII的摩尔比为1:2-2:1。
4.如权利要求1所述的催化剂,其特征在于:所述催化剂是由钴钼钨或镍钼钨三种金属形成的复合氧化物结构,其粒径为10-100nm。
5.一种权利要求1所述催化剂的制备方法,其步骤为:
a)将VIII族金属的碱式碳酸盐加入水中,形成碱式碳酸盐浓度为0.1~0.9mol/l的悬浊液;
b)将VIB族的两种金属元素的盐加入水中,形成金属离子浓度为0.03~0.3mol/l的溶液,并加入表面活性剂、使表面活性剂于溶液中的浓度为1~5wt%,搅拌加热至50-250℃;
c)将步骤a)的悬浊液加入步骤b)溶液中,于50-250℃下回流反应4-25小时;
d)将步骤c)得到的产物过滤、洗涤、干燥,得到目标产物。
6.如权利要求5所述的制备方法,其特征在于:所述的VIB族金属盐为可溶性的钼酸铵、钨酸铵、偏钨酸铵、钼酸钠或钨酸钠。
7.如权利要求5所述的制备方法,其特征在于:所述的表面活性剂为十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十八烷基三甲基溴化铵或十八烷基三甲基氯化铵。
8.一种权利要求1所述催化剂用于柴油加氢脱硫反应中,其特征在于:反应温度280-400℃,氢气压力1-20MPa,氢油体积比为50-1000,物料的体积空速0.1-10h-1。
9.如权利要求8所述催化剂用于柴油加氢脱硫反应中,其特征在于:催化剂在进行柴油加氢脱硫反应前应作如下预处理,
(i)在空气气氛中,于350-550℃焙烧;
(ii)研磨、混捏、成型;
(iii)在加氢脱硫固定反应床上,于300-450℃下以含硫有机物与氢气的混合气体进行原位硫化,含硫有机物在混合气体中的体积含量为10%。
10.如权利要求9所述催化剂用于柴油加氢脱硫反应中,其特征在于:所述含硫有机物为硫化氢、二硫化碳或二甲基硫。
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CN116273036A (zh) * | 2023-03-17 | 2023-06-23 | 江苏大学 | 一种rgb-nmo的制备方法及其应用 |
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