CN110023459A - 用于气相氧化脱硫催化剂的添加剂 - Google Patents

用于气相氧化脱硫催化剂的添加剂 Download PDF

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Publication number
CN110023459A
CN110023459A CN201780044463.XA CN201780044463A CN110023459A CN 110023459 A CN110023459 A CN 110023459A CN 201780044463 A CN201780044463 A CN 201780044463A CN 110023459 A CN110023459 A CN 110023459A
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Prior art keywords
composition according
cuznal
composition
type zeolite
catalyst
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Inventor
奥默·里法·科塞奥格卢
金亚明
济恩费·伊斯马吉洛夫
斯韦特兰娜·亚什尼科
米哈伊尔·克尔任采夫
瓦连京·帕蒙
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Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences
Saudi Arabian Oil Co
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Boreskov Institute of Catalysis Siberian Branch of Russian Academy of Sciences
Saudi Arabian Oil Co
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Publication of CN110023459A publication Critical patent/CN110023459A/zh
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  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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Abstract

描述了用于气态烃的氧化脱硫的组合物，其包括CuZnAl‑O混合氧化物和H型沸石。混合氧化物可以包含一种或多种金属氧化物促进剂。H型沸石可以是脱硅的，且还可以包含一种或多种过渡金属。

Description

用于气相氧化脱硫催化剂的添加剂
技术领域
本发明涉及可用于气态含硫烃的氧化脱硫的催化组合物。更具体地，本发明涉及以下称为“CuZnAl”催化剂的催化剂，与H型沸石相结合以形成催化组合物。
背景技术及现有技术
含硫烃燃料的氧化脱硫是一个发展成熟的领域。参见2016年1月4日提交的待决的美国专利申请14/987,141，以及已公布的美国专利申请2013/0028822和2013/0026072，所有这些的全部内容通过引用并入。这些材料尤其公开了催化组合物，其包含10-50wt％的氧化铜、5-少于20wt％的氧化锌和20-70wt％的氧化铝，其中X射线无定形相(如下文所述)，具有化学式CuxZn1-xAl2O4，其中X的范围为从0至1，且其还包含晶体ZnO和CuO。这些催化剂可以“掺杂”一种或多种促进剂，优选地为VIB族金属氧化物，诸如Mo、W、Si、B或P的氧化物。促进剂可以以最高至组合物的20wt％的量存在。
这些催化组合物以及本发明的组合物是用于优选地在高于300℃的温度下选择性氧化气态烃中的有机硫化合物的有效催化剂。
然而，本领域中的研究已经表明，当单独使用现有技术的催化剂时，催化氧化脱硫的效果并不理想。因此，将催化剂与添加剂相结合以使其更有效地进行氧化脱硫引起了兴趣。一种方法是将沸石与催化剂结合使用。在这方面，参见例如美国专利Nos.4,673,557；6,579,347；4,405,443；和7,749,376，美国专利公布2010/0037774和2007/0131589和PCT/NL93/00282，所有这些的全部内容通过引用并入。
然而，这些文献中没有一篇公开了H型沸石与上文所述类型的催化剂相结合。这种类型的沸石在例如美国专利Nos.3,875,290；3,948,760；和4,346,067中公开，所有这些都通过引用并入。
发明内容
本发明涉及包括氧化脱硫催化剂与作为添加剂的H型沸石相结合的催化组合物。示例性但非限制性的这类H型沸石有HZSM-5、HY、HX、H-丝光沸石、H-β和其他沸石拓扑结构，诸如MFI、FAU、BEA、MOR、FER的H型以及其脱硅型。催化组合物的沸石部分任选地用一种或多种过渡金属取代。此外，本发明的特征是用于制造这些催化剂的工艺，以及它们在氧化脱硫气态含硫烃中的用途。
下面优选实施方式的详细描述对本发明的各种实施方式进行了详细说明。
附图说明
图1示出了根据本发明对各种催化剂进行测试的结果。这些测试涉及使用甲苯中DBT的测试样品测量硫去除和S到SO2的转化。
图2示出了使用本发明的催化组合物在柴油燃料上进行测试的结果。
优选实施方式的具体描述
实施例1
通过例如在已公布的美国专利申请2013/0026072中所述的沉淀法来合成CuZnAl氧化物组合物，其全部内容通过引用并入。
简单地说，将Cu(NO3)2(0.2摩尔)、Zn(NO3)2(0.07摩尔)和Al(NO3)3(0.235摩尔)溶解于500ml的蒸馏水中，以形成以下被称为“溶液A”的溶液。溶液的pH为2.3。
类似地，将19.08g的Na2CO3(0.18摩尔)和48g的NaOH(1.2摩尔)溶解于600ml的蒸馏水中，以产生“溶液B”，其具有的pH为13。
将溶液A加热至65℃，并以约5ml/分钟的速度向溶液A中加入溶液B，不断搅拌，直到加入了所有的溶液B。得到的混合物具有的pH为11.0。将得到的沉淀在65℃、pH 11下老化6小时。将溶液冷却至室温，并用布氏漏斗过滤。用蒸馏水反复洗涤沉淀。分析表明，几乎全部的Cu、Zn和Al从溶液中沉淀析出(99％)直至PH为中性。
然后，在室温下干燥沉淀，在110℃下12小时，在500℃下煅烧4小时，并研磨成细粉。
实施例2
然后，通过众所周知的初湿浸渍法，对实施例1中制备的组合物进行处理以在其中掺入氧化钼(MoO3)。详细来说，将在实施例1中制备的干燥后的CuZnAl组合物放置在浸渍滚筒中，并在其旋转期间向滚筒中进料包含(NH4)6Mo7O24(0.22mol/L)和H3BO3(0.5mol/L)的浸渍溶液。溶液的体积由CuZnAl组合物的容水量并增加10％来计算。将浸渍后的样品再放置在旋转滚筒中20-30分钟，以使整个样品中的水分分布均匀。
然后，将样品在110℃下干燥12小时，并进一步在500℃下煅烧4小时。
干燥后的材料是深棕色的颜色。煅烧后的产物包含34-37W％的元素Cu、14-14.8W％的元素Zn、12-13.5W％的元素Al、3-8W％的元素Mo、0.4-1.5W％的元素％B和0.08-0.14W％的元素Na。(在以下所有实施例中，重量百分比是按照纯元素而不是氧化物给出的)。各组分的原子比Cu:Zn:Al为(2.5-3):1:(2.5-3)。改性催化剂具有的比表面积为35-70m2/g，孔体积为0.15-0.35cm3/g，且占主导的孔径等于10-20nm。
样品包含痕量的高度分散的CuO、ZnO和MoO3，具有X射线无定形氧化物相。如本文所用的“X射线无定形氧化物相”是指当通过高分辨率透射电子显微镜(“HRTEM”)观察时，观察到的晶体颗粒的范围为2-10nm，且通常为2-5nm。晶格常数与尖晶石的晶格常数非常接近，因此从EDX数据推导出的化学组成为Cu0.3Zn0.7Al2O4。
通过钼和硼的氧化物改性后的CuZnAl组合物的性质在表1中示出。催化组合物可以通过任何已知的方法进行造粒。也可以通过例如压制对它们进行挤出或压片。
实施例3
此实施例描述了沸石添加剂的制备。
使用硅酸盐模数(Si/Al原子比)等于30的商购批次的H型ZSM-5沸石作为之前实施例中所述的催化剂组合物的沸石添加剂。沸石的性质与其他代表性沸石的性质一起在表2中示出。“La”和“Y”是指过渡金属镧和钇，而“DeSi”意为沸石为脱硅形式。硅酸盐模数可在15-90W％的范围内变化。所有这些组合物均在下文描述。
实施例4
对实施例2的CuZnAl组合物和实施例3的ZSM-5进行称重并按85％至15％的重量比例混合。将混合物充分研磨10分钟，压制并细分，无需热处理。
所得材料的主要物理化学性质与本文所述的其他组合物的物理化学性质一起在表3中示出。
表3.有添加剂(15W％)的改性0.5B-10MoO2/Cu-Zn-Al2O3(B-Mo/CuZnAl)催化剂(85W％)的结构性质
1所有催化剂均通过将添加剂(15％)与85％的B-Mo/CuZnAl催化剂物理混合来制备，通过压制3次，随后在500℃下煅烧来制备。B-Mo/CuZnAl和添加剂的化学性质和XRD-相性质分别在表1和表2中示出。
实施例5
此实施例描述了由MoO3、B和包含La的沸石添加剂修饰的CuZnAl组合物的制备：0.5B-10MoO3/Cu-Zn-Al2O3+15％La/H-ZSM-5
该组合物的制备方式与实施例4的组合物相同，唯一不同的是沸石添加剂的组成，即为由镧改性的有ZSM-5结构的沸石(La/H-ZSM-5)。可以通过本文所使用的途径以外的已知途径将La和Y引入ZSM-5中，诸如离子交换模式，通过使用La和Y盐的水溶液。La和Y含量可以在0.1％至5W％的范围内变化。
为了合成这种沸石添加剂，将如上文所述的硅酸盐模数等于30的H型H-ZSM-5样品用硝酸镧La(NO3)3的水溶液进行初湿浸渍。用于浸渍的溶液的体积由沸石粉(VH2O＝0.6ml/g)的容水量增加10％来计算。La(NO3)3在溶液中的浓度为0.65mol/L。
然后，将样品在110℃下干燥4小时，并在500℃下煅烧4h。
镧在La/H-ZSM-5中的含量为4.75wt.％。它的一些性质如上文表2中所示。
由Mo、B和La/H ZSM-5改性的CuZnAl催化剂的组成和一些性质在上文表3中示出。
实施例6
此实施例描述了由MoO3、B和包含Y的沸石添加剂改性的CuZnAl组合物的制备：0.5B-10MoO3/Cu-Zn-Al2O3+15Y％La/H-ZSM-5。可以通过本文所使用的途径以外的途径将La和Y引入ZSM-5中，诸如离子交换，使用La或Y盐的水溶液。La和Y含量可以在0.1至5W％内变化。
所使用的制备方法遵照上文实施例4，但使用由钇改性的有ZSM-5结构的沸石(Y/H-ZSM-5)。
为了合成Y/H-ZSM-5，将如上文所述的硅酸盐模数等于30的H型ZSM-5样品用硝酸钇Y(NO3)3的水溶液进行初湿浸渍。用于浸渍的溶液的体积由沸石粉(VH2O＝0.6ml/g)的容水量增加10％来计算。Y(NO3)3在溶液中的浓度为1mol/L。
然后，将样品在110℃下干燥4小时，并在500℃下煅烧4h。
钇在Y/H-ZSM-5中的含量为4.75wt.％。其主要性质在上文表2中示出。
由Mo、B和Y/H ZSM-5改性的CuZnAl催化剂的组成和主要性质在上文表3中示出。
实施例7
描述了由MoO3、B和脱硅的ZSM-5结构(H-DeSi-ZSM-5)改性的CuZnAl组合物—0.5B-10MoO2/Cu-Zn-Al2O3+15％H-DeSi-ZSM-5的制备。
同样，遵照实施例4制备，但使用脱硅的ZSM-5结构(H-DeSi-ZSM-5)。
为了合成H-DeSi-ZSM-5，将可商购的硅酸盐模数等于30的H型H-ZSM-5样品置于有水夹套的反应器中，并在0.2M NaOH溶液中于80℃下进行脱硅2h。沸石质量(g)与溶液体积(ml)的比率等于30。然后对样品进行过滤，并用5倍体积的水洗涤。
洗涤之后，通过用0.5M NH4NO3在60℃下进行1小时的离子交换过程来从样品中移除钠阳离子。脱硅沸石质量(g)与溶液体积(ml)的比率等于30。然后，对样品进行过滤并用水洗涤至洗涤水的pH达到中性。
将所得到的材料在110℃下干燥4h，并在500℃下煅烧4h。
H-DeSi-ZSM-5的主要性质在上文表2中示出。
由Mo、B和H-DeSi-ZSM-5改性的CuZnAl催化剂的组成和主要性质在上文表3中示出。
实施例8
本文描述了由MoO3、B和脱硅的Na-Y结构(Na-DeSi-Y)改性的CuZnAl组合物——0.5B-10MoO3/Cu-Zn-Al2O3+15％的制备。
同样，遵照实施例4，使用有H-Y结构的脱硅沸石。
制备有H-Y结构的脱硅沸石的条件与用于制备有HZSM-5结构的脱硅沸石的条件类似。在用NaOH处理之后，样品被指定为Na-DeSi-Y，且其不再进行离子交换。脱硅沸石添加剂Na-DeSi-Y和通过加入Mo、B和Na-DeSi-Y而改性的CuZnAl催化剂的性质在上文表2和表3中示出。
实施例9
此实施例描述了由MoO3、B和有H-Y结构的脱硅沸石(H-DeSi-Y)改性的CuZnAl组合物——0.5B-10MoO2/Cu-Zn-Al2O3+15％的制备。
同样，遵照实施例4，使用有H-Y结构的脱硅沸石。基础沸石是可商购的。
制备有H-Y结构的脱硅沸石的条件与用于制备有HZSM-5结构的脱硅沸石的条件类似。在用NaOH处理之后，用硝酸铵溶液对样品进行离子交换。该产物被指定为H-DeSi-Y。
脱硅沸石添加剂H-DeSi-Y和通过加入Mo、B和H-DeSi-Y改性的CuZnAl催化剂的性质在上文表2和表3中示出。
实施例10
对根据本发明制备的催化组合物进行测试，以确定其氧化脱硫烃的能力。在此实施例中，将DBT溶解在甲苯中，以生成包含1％硫的测试混合物。测试了如上文所述的催化组合物，即：
0.5B+10Mo/CuZnAl
ZSM-5/0.5B+10Mo/CuZnAl
La-ZSM-5/0.5B+10Mo/CuZnAl
Y-ZSM-5/0.5B+10Mo/CuZnAl
DeSi–ZSM-/0.5B+10Mo/CuZnAl
NaDeSi-Y/0.5B+10Mo/CuZnAl
HDeSi-Y/0.5B+10Mo/CuZnAl。
在测试中，将本文所述的测试混合物与所列的每种催化组合物合并并加热。测量了硫至SO2的转化和硫去除的百分比，并描绘在图1中。在所测试温度(240-440℃)下，测试混合物处于气相。
对这些数字的综述表明，在使用沸石时的最大催化活性明显高于不使用沸石时的。
实施例11
然后，测试了上文所述的催化组合物催化对残余燃料油的氧化脱硫的能力。测试材料(残余燃料油)的性质为：
测试所用条件在下文列出的表4中示出。注意使用本发明的组合物的脱硫量与现有技术相比(56.6对37.1)有所增加。
表4在由B、Mo改性的CuZnAl催化剂和由B、Mo和Y-沸石改性的催化剂上与残余燃料油的ODS反应的研究结果
催化剂 添加剂 温度 进料S O<sub>2</sub>/S GHSV WHSV CO<sub>2</sub> SO<sub>2</sub> H<sub>2</sub>S COS DSLP<sup>1</sup>
℃ W％ h<sup>-1</sup> h<sup>-1</sup> V％ V％ V％ V％ W％
1B-5MoO<sub>3</sub>/CuZnAl - 485 2.6027 25 7850 6 21.812 0.315 0.006 0 -
1B-5MoO<sub>3</sub>/CuZnAl - 500 2.6027 25 7850 6 27.021 0.525 0.016 0 46.8
0.5B-10MoO<sub>3</sub>/CuZnAl Y沸石 400 2.6027 25 7855 6 20.903 0.679 0.001 0 57.6
1.DSLP—基于液体分析，液相中的元素硫的脱硫量
实施例12
对柴油和残余燃料的混合物进行类似的实验。相关性质为：
密度： 0.906g/cc
硫(wt％) 1.30
MCR(wt％) 1.8
下面的表5示出了工作的条件和结果。注意脱硫量从57.4增加至71.1。
实施例13
测试了催化组合物Y-沸石/0.5B-10 MoO3CuZn从柴油燃料中去除硫的能力。测试在400℃下进行，GHSV＝7860h-1，WHSV h-1。硫含量为0.97wt％。图2示出了不同O2/S比率下的硫去除、硫至SO2的转化和氧消耗。
上述公开列出了本发明的特征，包括催化组合物及其用途。催化组合物包括CuZnAl-O混合氧化物，其中氧化物的重量百分比为：
10-50CuO
5->20ZnO
20–70Al2O3
这些混合氧化物(复合氧化物)还包含高度分散的尖晶石氧化物相，其中该相具有化学式
CuxZn1-xAl2O4
x的范围为从0至1，优选地为.1至.6，且最优选地为从.2至.5。任选地，混合氧化物可以包含至少一种氧化物促进剂，诸如Mo、W、Si、B或P的一种或多种氧化物。
组合物还包括至少一种H型沸石，诸如HZSM-5、HY、HX、H-丝光沸石、H-β、MFI、FAU、BEA、MOR或FER。这些H型可以是脱硅的，和/或包含一种或多种过渡金属，诸如La或Y。
混合氧化物组分可以是颗粒形式的，并且可以使用已知方法将组合物作为整体形成为圆柱体、球体、三叶型、四叶型或任何所需形式。当为颗粒形式时，混合氧化物颗粒具有的直径为从1mm至4mm。此外，优选地混合氧化物具有的表面积为从10m2/g至100m2/g，优选地从50m2/g至100m2/g，和/或总孔体积为从约0:1cm3/g至约0.5cm3/g。
再次引用混合氧化物组合物，优选的重量分布为：
20–45wt％CuO
10->20ZnO
20–70Al2O3
且甚至更优选地:
30–45CuO
12->20ZnO
20–40Al2O3
H型沸石可以包括从约5至约50wt％的组合物，且硅酸盐模数为从2至90。
组合物可以用于氧化脱硫气态烃或烃混合物，诸如燃料油、原油、柴油等，通过在例如从200℃至500℃，优选地从240℃至440℃的温度下，将包含硫的气态烃与所述组合物相接触。其他操作参数，诸如进料、O2/S比率、GHSV、WHSV等，是由各技术人员设定的参数。
本发明的其他特征对于熟练的技术人员来说是清楚的，且这里不需重复。
已使用的术语和表达仅用作术语的描述而非限制，并且这些术语和表达的使用不旨在将所示出的以及所描述的特征或其部分的任何等同物排除在外，应当理解，在本发明的范围内可以进行各种修改。

Claims (23)

1.一种用于气态含硫烃的氧化脱硫的组合物，(i)CuZnAl-O混合氧化物组分，包括量的范围为从10重量百分比(wt％)至50wt％的标称氧化铜、量的范围为从5wt％至少于20wt％的氧化锌和量的范围为从20wt％至70wt％的氧化铝，其中，所述催化组合物具有化学式为CuxZn1-xAl2O4的高度分散的尖晶石氧化物相，其中x的范围为从0至1，分散的晶体ZnO和CuO，以及(ii)至少一种H型沸石。
2.根据权利要求1所述的组合物，其中，所述CuZnAL-O混合氧化物组分是颗粒形式的。
3.根据权利要求1所述的组合物，形成为圆柱体、球体、三叶型或四叶型。
4.根据权利要求2所述的组合物，其中，所述CuZnAL-O混合氧化物组分的颗粒具有的直径为从1mm至4mm。
5.根据权利要求1所述的组合物，其中，所述CuZnAl-O混合氧化物组分具有的表面积为从10m2/g至100m2/g。
6.根据权利要求1所述的组合物，其中，所述CuZnAL-O混合氧化物组分的总孔体积为从约0.1cm3/g至约0.5cm3/g。
7.根据权利要求1所述的组合物，所述CuZnAl-O混合氧化物组分包括从20wt％至45wt％的CuO、从10wt％至少于20wt％的ZnO和从20wt％至70wt％的Al2O3。
8.根据权利要求7所述的组合物，所述催化剂包括从30wt％至45wt％的CuO、从12wt％至少于20wt％的ZnO和从20wt％至40wt％的Al2O3。
9.根据权利要求5所述的催化组合物，所述CuZnAl-O混合氧化物组分具有的表面积为从50m2/g至100m2/g。
10.根据权利要求1所述的组合物，其中X为从.1至.6。
11.根据权利要求10所述的组合物，其中X为从.2至.5。
12.根据权利要求1所述的组合物，其中，所述CuZnAl-O混合氧化物组分还包括氧化物促进剂。
13.根据权利要求12所述的组合物氧化物促进剂，其中，所述氧化物促进剂是Mo、W、Si、B或P的氧化物的混合物。
14.根据权利要求1所述的组合物，其中，所述H型沸石是HZSM-5、HY、HX、H-丝光沸石、H-β、MFI、FAU、BEA、MOR或FER。
15.根据权利要求1所述的组合物，其中，所述H型沸石是脱硅的。
16.根据权利要求1所述的组合物，其中，所述H型沸石包含过渡金属。
17.根据权利要求12所述的组合物，其中，所述H型沸石包含过渡金属。
18.根据权利要求16所述的组合物，其中，所述过渡金属是La或Y。
19.根据权利要求17所述的组合物，其中，所述过渡金属是La或Y。
20.根据权利要求1所述的组合物，其中，所述H型沸石占所述组合物的按重量计从约5至约50百分比。
21.根据权利要求1所述的组合物，其中，所述H型沸石具有的硅酸盐模数(硅与铝的原子比率)为从2至90。
22.根据权利要求1所述的组合物，其中，所述H型沸石具有无定形或晶体结构。
23.一种用于氧化降低气态烃原料中的硫含量的方法，包括在有利于氧化脱硫的条件下将所述气态烃原料与权利要求1的所述组合物接触。
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