CN114746176A - 包封铂的沸石加氢裂化催化剂以及制备包封铂的沸石加氢裂化催化剂的方法 - Google Patents

包封铂的沸石加氢裂化催化剂以及制备包封铂的沸石加氢裂化催化剂的方法 Download PDF

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CN114746176A
CN114746176A CN202080083026.0A CN202080083026A CN114746176A CN 114746176 A CN114746176 A CN 114746176A CN 202080083026 A CN202080083026 A CN 202080083026A CN 114746176 A CN114746176 A CN 114746176A
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zeolite
platinum
hydrocracking catalyst
sodalite
catalyst
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CN114746176B (zh
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丁连辉
玛纳尔·阿尔艾德
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Saudi Arabian Oil Co
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Saudi Arabian Oil Co
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Abstract

本公开的实施例涉及加氢裂化催化剂以及制备所述加氢裂化催化剂的方法。所述加氢裂化催化剂包含包封铂的沸石，所述包封铂的沸石具有通过X射线粉末衍射分析测定的大于20％的结晶度。

Description

包封铂的沸石加氢裂化催化剂以及制备包封铂的沸石加氢裂 化催化剂的方法
技术领域
本公开总体上涉及加氢裂化技术，并且更具体地说，涉及包封铂的沸石加氢裂化催化剂以及制备这些加氢裂化催化剂的方法。
背景技术
与常规的蒸汽裂化原料，例如天然气、石脑油和柴油的窄馏分相比，全原油原料包括更多的杂质和相当大量的多环芳烃，这些物质不能通过蒸汽裂化直接转化。为了使从全原油原料中烯烃和苯、甲苯和二甲苯(BTX)生产率最大化，全原油原料需要加氢处理以去除杂质(S、N和金属)，转化多环芳烃，并将重馏分转化为较轻馏分。
多环芳烃的氢化和原油的加氢裂化是原油升级和将原油转化为清洁燃料和石化产品的关键加氢处理步骤。贵金属负载型催化剂通常用于多环芳烃氢化和加氢转化中。然而，即使在百万分之几(ppm)的H2S或硫化合物下，贵金属催化剂也非常容易发生硫中毒。沸石Y是一种用于重油加氢裂化催化剂中的广泛使用的裂化组分。如果在具有大孔径(约0.75nm)的沸石Y上负载如铂(Pt)的金属，则H2S很容易接近并毒化Pt活性位点。方钠石沸石，其常用作贵金属载体，孔径为0.30nm或更小，这防止原油中的大分子扩散进出沸石孔隙；然而，较大的分子不能有效地加氢裂化，这大大降低了反应效率。
发明内容
因此，需要具有改进的加氢裂化效率同时减少催化剂的硫中毒的加氢裂化催化剂。
本公开的实施例满足了对改进的加氢裂化催化剂的这种需要。具体地说，本发明的加氢裂化催化剂包含包封在方钠石沸石笼中的铂(Pt/SOD)。方钠石沸石笼的孔隙开口足够小，以排除最小的含硫分子(H2S，0.36nm)，同时允许氢分子(0.28nm)扩散进出方钠石笼并在Pt簇上反应以有效地形成解离的氢原子。这些解离的氢原子可能会溢出到相邻的氢化或酸位点，如氧化铝、沸石Y、NiMo和NiW金属，在那里可以对较大的烃分子进行氢化和裂化。因此，将包封Pt的方钠石与较大孔径的沸石Y混合可以大大增强原油的加氢裂化。
根据本公开的一个实施例，提供了制备加氢裂化催化剂的方法。所述方法包含：将氢氧化钠、铝化合物、具有阴离子和阳离子的盐和硅化合物添加到水溶液中以形成水性混合物；搅拌水性混合物；将铂化合物添加到水性混合物中以形成预催化剂混合物；将预催化剂混合物在80℃至200℃下加热至少24小时，从而使预催化剂混合物结晶以形成包含包封铂的沸石的加氢裂化催化剂。
根据本公开的另一个实施例，提供了加氢裂化催化剂。加氢裂化催化剂可以包含包封铂的沸石，包封铂的沸石具有通过X射线粉末衍射分析测定的大于20％的结晶度。
附图说明
图1是根据本公开的一个或多个实施例的加氢裂化催化剂以及加氢裂化反应的示意图。
图2是根据本公开的一个或多个实施例的加氢裂化催化剂以及加氢裂化和氢化反应的示意图。
具体实施方式
本公开的实施例涉及加氢裂化催化剂和制备方法，并且具体地说涉及包含包封Pt的沸石的加氢裂化催化剂。另外的实施例涉及包含这些加氢裂化催化剂、如沸石Y的附加沸石以及氢化催化剂(例如NiMo或NiW)的加氢裂化催化剂。
如贯穿本公开所使用的，“全原油”、“原油”或“全原油原料”是指未精炼的石油原油，以及在加氢裂化之前已经进行了一些预处理的原油。如本公开中所使用的，“预处理”包括水-油分离、气-油分离、脱盐、稳定化或这些的组合；然而，它不包括在加氢裂化之前进行蒸馏(例如，真空蒸馏或常压蒸馏)的原油。原油的美国石油学会(API)比重(°)可以为10°至50°。
如贯穿本公开所使用的，术语“加氢裂化”涉及将原油中的重烃分子催化裂化为较小的烯烃和芳烃，裂化在至少一种催化剂和氢气的存在下执行。“加氢裂化”还包括氢化，所述氢化涉及将氢添加到如烯烃和芳烃的不饱和烃中，以稳定石油产品和还原芳烃。具体地说，氢化将烯烃和芳烃转化为链烷烃和环烷烃。此外，“加氢处理”包括加氢裂化和附加反应机制，例如，加氢脱芳烃、加氢脱氮、加氢脱硫或这些的组合。
下文提供了用于制备加氢裂化催化剂的实施例。根据一个实施例，通过以下来生产加氢裂化催化剂：将氢氧化钠、铝化合物、具有阴离子和阳离子的盐和硅化合物添加到水溶液中以形成水性混合物；搅拌水性混合物；将铂化合物添加到水性混合物中以形成预催化剂混合物；将预催化剂混合物在80℃至200℃下加热至少24小时，从而使预催化剂混合物结晶以形成包含包封铂的沸石的加氢裂化催化剂。如将在随后的段落中进一步详细描述的，包封铂的沸石可以包含方钠石。
各种化合物被认为适合于铝化合物，例如，铝金属粉末、氢氧化铝(Al(OH)3))、铝酸钠(NaAlO2)或其组合。在一个实施例中，铝化合物包含氢氧化铝。
在一个或多个实施例中，硅化合物可以包含二氧化硅、硅酸钠、胶态二氧化硅、热解法二氧化硅或其组合。在一些实施例中，硅化合物包含胶态二氧化硅。
盐可以包含氯化钠、重铬酸钾、氯化钙、硫酸氢钠、硫酸铜或其组合。在一个实施例中，盐包含氯化钠。
此外，各种化合物被认为适合于铂化合物，如铂盐。铂盐可以包含Pt(NH3)Cl2、PtCl2、PtCl4、(NH4)2PtCl6、(NH4)2Pt(NO3)2、Na2PtCl6.6H2O、H2PtCl6.6H2O、Na2PtCl4.4H2O、(NH4)2PtCl4或其组合。在一个实施例中，铂化合物包含(NH4)2PtCl4。
基于上述不同组分的可能性，经考虑，预催化剂混合物或预催化剂浆料可以包括许多不同组分混合物。在多个实施例中的一个中，预催化剂混合物包含xNaOH:1Al2O3:2SiO2:yNaCl:z(NH4)2PtCl4:wH2O，其中x＝10-30，y＝0-10，z＝0.02-0.5，并且w＝100-500。
可以利用各种加工条件来生产包封铂的沸石。例如，可以将预催化剂混合物加热至少12小时、至少24小时、至少48小时或至少72小时。此外，在形成包封铂的沸石之后，还考虑了如冲洗的附加步骤。例如，包封铂的沸石可以通过以下方式冲洗：将第二水溶液(例如，去离子水)添加到包封铂的沸石中；搅拌第二水溶液(例如去离子水)内的包封铂的沸石；以及将第二水溶液内的包封铂的沸石离心以从第二水溶液中分离出包封铂的沸石。在从第二水溶液中分离出包封铂的沸石之后，此冲洗步骤可以反复地进行直到第二水溶液包含小于1ppm的阴离子。
此外，所述过程可以包括包含将包封铂的沸石干燥至少2小时、或至少4小时、或至少8小时。除了干燥持续时间以外，各种干燥温度都是合适的。例如，干燥温度可以为90℃至150℃，或100℃至120℃。
在另外的实施例中，包封铂的沸石可以与如沸石、氧化铝和附加基于金属的催化剂的其他组分共混。在一个实施例中，将包封铂的方钠石沸石与沸石Y共混。在一个具体实施例中沸石Y包含超稳沸石(USY)。此外，如镍、钼、钨或其组合的基于金属的催化剂可以与沸石Y和包封铂的沸石共混。这些基于金属的催化剂的添加可以包括混合或浸渍到沸石Y、包封铂的沸石或其组合中。如本领域技术人员所熟悉的，沸石Y、氧化铝、包封铂的沸石和基于金属的催化剂(例如Ni)可以与粘结剂组合地共混。
为了说明而非限制，提供了生产加氢裂化催化剂的示例性实施例。作为初始步骤，水热合成法用于生产包封Pt的方钠石。凝胶组成为xNaOH:1Al2O3:2SiO2:yNaCl:zPt盐:wH2O，其中x＝10-30，y＝0-10，z＝0.02-0.5，并且w＝100-500。典型的合成方法列出如下：
(1)将NaOH溶解在去离子H2O中。
(2)向从步骤(1)获得的溶液中添加Al(OH)3并在搅拌下平缓地加热，直到Al完全溶解以形成澄清溶液。在此步骤期间弥补了加热期间的水损失。
(3)将胶态SiO2和NaCl添加到来自(2)的澄清溶液中，剧烈搅拌30-60分钟形成浆料。
(4)添加(NH4)2PtCl4(或PtCl2或Na2PtCl6)，搅拌，直到完全溶解。
将来自(4)的浆料转移到聚丙烯瓶中，密封，并且然后放入80℃-200℃的烘箱中24-72小时。
在结晶之后，将固体产物转移到聚丙烯烧杯中，添加水，在60℃下搅拌30分钟，并且然后离心以分离固体产物。这可以重复，直到溶液中检测不到Cl-(用0.1M AgNO3溶液测试)。
然后将固体产物在100℃-120℃下干燥过夜。采用前述Y沸石和Pt-方钠石，通过混合或浸渍方法制备加氢裂化催化剂。
除了制备方法以外，附加实施例涉及由制备方法生产的加氢裂化催化剂。如先前所陈述，加氢裂化催化剂可以包含包封铂的沸石，所述包封铂的沸石具有通过X射线粉末衍射分析测定的大于20％的结晶度。
在一个或实施例中，沸石可以是含有立方晶体结构的方钠石(Na8(Al6Si6O24)Cl2)沸石。在一个实施例中，方钠石的Si/Al摩尔比为0.8至1.2，或1。方钠石具有六元氧孔，孔直径很窄。只有如氢气
Figure BDA0003669077060000044
氦气
Figure BDA0003669077060000042
氨
Figure BDA0003669077060000043
和水
Figure BDA0003669077060000045
的非常小的分子可以接近并进入空隙，使方钠石成为分离这些较小分子的合适候选物。方钠石的这种立方晶体结构，也称为方钠石笼，包封铂。参考图1和2，方钠石笼的孔径的范围可以在H2和H2S的动力学直径之间。因此，H2S被排除进入方钠石笼，而氢气分子可以进入方钠石笼中以被吸附在方钠石所包封的Pt簇上并在其上反应。因此，氢气可以容易且有效地解离为H原子，所述H原子对于多环芳烃氢化和较大分子的裂化具有很高的活性。由于方钠石的孔径，方钠石内部的Pt不会被H2S和其他硫化合物毒化。
如先前所陈述，方钠石的孔径需要足以排除最小的含硫分子，同时允许氢气分子扩散进出方钠石笼。在一个或多个实施例中，当使用布鲁诺尔-艾米特-泰勒(Brunauer-Emmett-Teller，BET)技术计算时，方钠石的孔径可以为0.10nm至0.30nm、0.15nm至0.30nm、0.25nm至0.30nm，或0.30nm。方钠石的表面积可以为0.05至0.20m2/g、0.05至0.20m2/g、0.10至0.15m2/g，或0.12m2/g。方钠石的孔体积可以为0.05至0.20ml/g、0.05至0.20ml/g、0.10至0.15ml/g，或0.13ml/g。
在另外的实施例中，包封铂的沸石(例如，Pt-方钠石)包含大于35％的结晶度，或大于50％的结晶度，或大于75％的结晶度，或大于95％的结晶度。在另外的实施例中，加氢裂化催化剂可以包含如根据X射线粉末衍射分析测量的25％至50％、30％至45％或30％至40％的结晶度。
如先前所述并在图1和2中示出，包封铂的方钠石可以解离H原子，所述H原子溢出到相邻的氢化位点或酸位点，以帮助裂化和氢化。因此，加氢裂化催化剂的另外的实施例可以包括如沸石Y的附加沸石。另外的实施例还可以包括氧化铝。在一个实施例中，沸石Y包含超稳沸石Y(USY)。当包封铂的方钠石与沸石Y共混时，经考虑，方钠石笼与沸石Y骨架相邻或安置在沸石Y骨架内。
沸石Y可以由各种特性定义。例如，沸石Y的SiO2/Al2O3摩尔比可以为5至80、10至60、20至60或30-50。另外，沸石Y的表面积可以大于700m2/g。在另一个实施例中，沸石Y的表面积可以为700至750m2/g。如先前所提到，沸石Y将具有比方钠石笼大的孔径，例如，约0.70至0.80nm，或0.74至0.76nm。
此外，加氢裂化催化剂可以包括氢化催化剂，其通常包含基于金属的材料。这些基于金属的材料可以包括金属元素、金属氧化物、金属氢氧化物、合金及其组合。在一个或多个实施例中，这些基于金属的材料可以包含包含镍、钼、钨或其组合。在结构上，基于金属的材料可以浸渍在沸石Y、包封铂的沸石、氧化铝或其组合内。此外，基于金属的材料可以安置在沸石Y、包封铂的沸石、氧化铝或其组合的表面上。在操作中，通过与从由包封Pt的方钠石执行的加氢裂化中产生的解离的离子组合的氢化催化剂，可以对大的烃分子进行氢化和裂化。虽然目前的讨论将如镍负载型沸石Y的催化剂归类为氢化催化剂，但还考虑并预期了如加氢裂化的同时发生的反应。
在一个实施例中，加氢裂化催化剂可以包含NiMo催化剂。在一个或实施例中，加氢裂化催化剂可以包含5wt％至50wt％、10wt％至40wt％或10至20wt％的NiMo催化剂。NiMo催化剂可以包含基于金属的材料的组合，例如MoO3和NiO。在一个或多个实施例中，加氢裂化催化剂可以包含10至20wt％或14至16wt％的MoO3和另外1至10wt％或4至6wt％的NiO。
在另一个实施例中，加氢裂化催化剂可以包含NiW催化剂。在一个或实施例中，加氢裂化催化剂可以包含5wt％至50wt％、10wt％至40wt％或20至30wt％的NiW催化剂。NiW催化剂可以包含基于金属的材料的组合，例如WO3和NiO。在一个或多个实施例中，加氢裂化催化剂可以包含20至30wt％或20至26wt％的WO3和另外1至10wt％或4至6wt％的NiO。
此外，加氢裂化催化剂可以包含10至80wt％的包封铂的方钠石和沸石Y，或10至60wt％的包封铂的方钠石和沸石Y，或20至60wt％的包封铂的方钠石和沸石Y，或30至60wt％的包封铂的方钠石和沸石Y，或40至60wt％的包封铂的方钠石和沸石Y。加氢裂化催化剂可以包含1至30wt％的包封铂的方钠石，或1至20wt％的包封铂的方钠石，或1至10wt％的包封铂的方钠石。此外，加氢裂化催化剂可以包含10至60wt％的沸石Y，或20至50wt％的沸石Y，或30至50wt％的沸石Y。
在一个或多个实施例中，按加氢裂化催化剂的总重量计，加氢裂化催化剂包含小于20wt％的铂，或小于15wt％的铂，或小于小于5wt％的铂。
任选地，加氢裂化催化剂可以包含与其他组分混合的氧化铝(Al2O3)。考虑了各种量，例如，10至80wt％、20至80wt％、10至70wt％、10至50wt％、20至40wt％或25至35wt％的Al2O3。氧化铝可以由各种特性来定义；然而，氧化铝将具有比方钠石大的孔径。例如，氧化铝的孔径可以大于10nm，并且表面积大于150m2/g。
在另一个实施例中，NiMo催化剂可以包含10至20wt％的MoO3、1至10wt％的NiO、20至80wt％的Al2O3和10至60wt％的包封铂的方钠石和沸石Y。在又一个实施例中，NiW加氢裂化催化剂包含20至30wt％的WO3、1至10wt％的NiO、20至80wt％的Al2O3以及10至60wt％的包封铂的方钠石和沸石Y。
测试方法
BET技术
针对从Quantachrome Autosorb iQ仪器获取的数据，使用BET技术，通过物理吸附，对包括表面积、孔体积、孔径和孔径分布的样品质地特性进行表征。在吸附之前，将样品在873K下煅烧4小时。将大约30-40mg粉末样品在样品制备站中在473K和1.33E-3Pa下脱气15小时，然后切换到分析站，用于在77K的液氮下进行吸附和解吸，平衡时间为2分钟。表面积用多点BET方程计算，线性区域在0.05至0.35的P/Po范围中。根据P/Po＝0.99时氮的最大吸附量计算孔体积。
XRD粉末衍射分析
使用带有铜X射线管的Rigaku Ultima IV多用途衍射仪，通过粉末X射线衍射(XRD)测量固体产物的结晶度和相纯度。扫描范围设置在2°到50°之间，以2θ布拉格角为单位，步长为0.04°，并且总计数时间为每分钟1°。结晶度百分比由PANalytical High ScorePlus软件通过比较最强衍射峰下的面积与参考沸石(没有包封Pt的方钠石)的图案的面积来计算。参考(比较)沸石的结晶度为100％。
实例
以PtCl2和(NH4)2PtCl4作为Pt源，进行了Pt-方钠石的水热合成，凝胶组成和合成条件总结在表1中。结果表明，在所有条件下，均可形成Pt-方钠石。随着Pt含量的增加，相对结晶度急剧下降。
表1.使用不同Pt源和量的Pt/方钠石水热合成
样品名称 SZ-5 SZ-6 SZ-7
凝胶摩尔比
PtCl<sub>2</sub> 1.0
NaOH 20 20 15
Al<sub>2</sub>O<sub>3</sub> 1 1 1
SiO<sub>2</sub> 1 1 1
(NH<sub>4</sub>)<sub>2</sub>PtCl<sub>4</sub> 2 0.05 0
H<sub>2</sub>O 300 300 300
水热条件
温度 140 140 140
时间，小时 72 168 48
干固体产量，g 4.58 3.13 0.53
XRD结果 方钠石 方钠石 方钠石
结晶度，％ 20 100 38
Pt，wt％ 59 2.8 14.54
参考下表2，用SZ-6Pt/方钠石，合成了加氢裂化催化剂。同时，在相同的组成和合成程序下，合成了不含SZ-6沸石的参考催化剂。将水热合成的SZ-6和/或USY沸石(来自Zeolyst的CBV-760)与大孔氧化铝(Sasol PURALOX TH100/150，孔体积0.96mL/g，比表面积201.6m2/g)、MoO3、六水合硝酸镍和粘结剂(部分酸胶溶氧化铝，SASOL，CATAPAL B)混合，挤出形成圆柱形挤出物，在383K下干燥过夜，并且然后在773K下在空气中煅烧4小时。发明催化剂和比较催化剂的组成总结在表2中。
表2：有和没有Pt/方钠石的催化剂的组成。
编号 MoNi/Pt-方钠石-USY MoNi/USY
组成，wt％
MoO<sub>3</sub> 15 15
NiO 5 5
USY 40 50
Pt/方钠石(SZ-6) 10
Al<sub>2</sub>O<sub>3</sub> 30 30
催化剂性能测试在5ml固定床微反应器(Autoclave Engineer，BTR-Jr-PC)中以连续操作模式进行。3ml的20-40目催化剂用相同体积的100目沙子稀释。在每次运行之前，催化剂在20vol％H2S/H2流中在320℃下原位预硫化2小时，再在360℃下在220psi氢气压力下原位预硫化2小时，LHSV 2.0h-1，氢气流速200ml/分钟。1-甲基萘(MN)(20wt％，在十六烷中)用作模型化合物。用HPLC泵将模型化合物馈送到系统中。通过GC-MS(SHIMADZU GCMS-QP5000)分析液体产物。评估条件：反应温度350℃，H2压力220psig，LHSV 2.0h-1，H2/MN体积比1000:1。为了测试Pt/方钠石的抗硫性，将一定量的DMDS(相当于20ppm H2S)与1-MN一起添加到反应器中用于进行一些测试。评估结果列于表3中。与MoNi/USY催化剂相比，添加包封Pt的方钠石，1-MN氢化转化率增加了约24wt％。Pt位于方钠石内部，不会被H2S毒化。因此，当引入20ppm的H2S时，1-MN转化率仅略有死亡。
表3.发明的催化剂和参考催化剂的反应性能
Figure BDA0003669077060000081
应注意的是，以下权利要求中的一项或多项权利要求利用术语“其中(where)”或“其中(in which)”作为过渡性短语。出于定义本发明技术的目的，应注意，此术语在权利要求书中作为用于引入结构的一系列特征的陈述的开放式过渡短语引入，并且应以与更常用的开放式前导术语“包含”相同的方式解释。出于定义本发明技术的目的，过渡短语“由……组成”可以在权利要求书中作为将权利要求的范围限制为陈述的组分或步骤和任何天然存在的杂质的封闭式前导术语引入。出于定义本发明技术的目的，过渡短语“基本上由……组成”可在权利要求书中引入以将一个或多个权利要求项的范围限制为陈述的要素、组分、材料或方法步骤以及不实质上影响所要求保护的主题的新颖特征的任何非陈述的要素、组分、材料或方法步骤。过渡短语“由……组成”和“基本上由……组成”可被解释为开放式过渡短语(如“包含”和“包括”)的子集，使得任意使用开放式短语来引入一系列要素、组分、材料或步骤的陈述应被解释为还使用封闭式术语“由……组成”和“基本上由……组成”公开一系列要素、组分、材料或步骤的陈述。举例来说，“包含”组分A、B和C的组合物的陈述应被解释为还公开“由组分A、B和C组成”的组合物以及“基本上由组分A、B和C组成”的组合物。在本申请中表达的任何定量值可被认为包括与过渡短语“包含”或“包括”相一致的开放式实施例以及与过渡短语“由……组成”和“基本上由……组成”相一致的封闭式或部分封闭式实施例。
如在说明书和所附权利要求书中所使用的，除非上下文另外明确指示，否则单数形式“一种(a)”、“一个(an)”和“所述”包括复数个参考。动词“包含”和其缀合形式应被解释为以非排他性方式引用要素、组分或步骤。所引用的要素、组分或步骤可与未明确引用的其他要素、组分或步骤一起存在、利用或组合。
应当理解，分配给某特性的任何两个定量值可构成所述特性的范围，并且在本公开中考虑由给定特性的所有所述定量值形成的范围的所有组合。已详细地并且通过参考特定实施例描述本公开的主题。应当理解，实施方式的组分或特征的任何详细描述不一定暗示组分或特征对于具体实施例或任何其他实施例为必要的。
对于本领域的技术人员来说显而易见的是，在不背离所要求的主题的精神和范围的情况下，可以对本文所述的实施例进行各种修改和变更。因此，旨在本说明书覆盖所描述的各个实施例的修改和变更，其条件是，这类修改和变更属于在所附权利要求书以及其等效物的范围内。除非在申请中另有说明，否则所有测试、特性和实验均在室温和大气压下进行。
应当理解，加氢裂化催化剂和制备这些加氢裂化催化剂的方法的各个方面可以与各个其他方面结合使用。
根据第一方面，提供了生产加氢裂化催化剂的方法，其中所述方法包含：将氢氧化钠、铝化合物、具有阴离子和阳离子的盐和硅化合物添加到水溶液中以形成水性混合物；搅拌水性混合物；将铂化合物添加到水性混合物中以形成预催化剂混合物；和将预催化剂混合物在80℃至200℃下加热至少24小时，从而使预催化剂混合物结晶以形成包含包封铂的沸石的加氢裂化催化剂。
根据包括第一方面的第二方面，沸石是方钠石。
根据包括第一或第二方面中任一项的第三方面，加氢裂化催化剂包含通过X射线粉末衍射分析测定的大于20％的结晶度。
根据包括第一至第三方面中任一项的第四方面，铝化合物包含铝金属粉末、氢氧化铝、铝酸钠或其组合。
根据包括第一至第四方面中任一项的第五方面，硅化合物包含二氧化硅、硅酸钠、胶态二氧化硅、热解法二氧化硅或其组合。
根据包括第一至第五方面中任一项的第六方面，盐包含氯化钠、重铬酸钾、氯化钙、硫酸氢钠、硫酸铜或其组合。
根据包括第一至第六方面中任一项的第七方面，铂化合物包含选自以下群组的铂盐：Pt(NH3)Cl2、PtCl2、PtCl4、(NH4)2PtCl6、(NH4)2Pt(NO3)2、Na2PtCl6.6H2O、H2PtCl6.6H2O、Na2PtCl4.4H2O、(NH4)2PtCl4或其组合。
根据包括第一至第七方面中任一项的第八方面，预催化剂混合物包含xNaOH:1Al2O3:2SiO2:yNaCl:z(NH4)2PtCl4:wH2O，其中x＝10-30，y＝0-10，z＝0.02-0.5，并且w＝100-500。
根据包括第一至第八方面中任一项的第九方面，该所述方法进一步包含将包封铂的沸石与沸石Y共混。
根据包括第一至第九方面中任一项的第十方面，所述方法可以进一步包含将选自镍、钼、钨或其组合的一种或多种基于金属的催化剂添加到加氢裂化催化剂中。
根据包括第一至第十方面中任一项的第十一方面，添加方法可以涉及混合或浸渍到沸石Y、包封铂的沸石或其组合中。
根据第十二方面，加氢裂化催化剂包含包封铂的沸石，包封铂的沸石具有通过X射线粉末衍射分析测定的大于20％的结晶度。
根据包括第十二方面的第十三方面，加氢裂化催化剂包含大于35％的结晶度。
根据包括第十二至第十三方面中任一项的第十四方面，沸石包含方钠石。
根据包括第十二至第十四方面中任一项的第十五方面，方钠石的孔径为1.0至3.0纳米。
根据包括第十二至第十五方面中任一项的第十六方面，加氢裂化催化剂进一步包含沸石Y和任选的氧化铝。
根据包括第十二至第十六方面中任一项的第十七方面，加氢裂化催化剂进一步包含镍、钼、钨或其组合。
根据包括第十二至第十七方面中任一项的第十八方面，加氢裂化催化剂包含10至20wt％的MoO3、1至10wt％的NiO、20至80wt％的Al2O3以及10至60wt％的包封铂的方钠石和沸石Y。
根据包括第十二至第十七方面中任一项的第十九方面，加氢裂化催化剂包含20至30wt％的WO3、1至10wt％的NiO、20至80wt％的Al2O3以及10至60wt％的包封铂的方钠石和沸石Y。
根据包括第十二至第十九方面中任一项的第二十方面，加氢裂化催化剂包含1至10wt％的组合的方钠石和铂。
已经详细地并且通过参考特定实施例描述了本公开的主题，应注意，本公开中描述的各种细节不应被视为暗示这些细节与作为本公开中所描述的各种实施例的必需组分的要素相关。此外，将显而易见的是，在不脱离本公开的范围的情况下可以进行修改和变更，包括但不限于所附权利要求中限定的实施例。

Claims (18)

1.一种生产加氢裂化催化剂的方法，其中所述方法包含：
将氢氧化钠、铝化合物、具有阴离子和阳离子的盐以及硅化合物添加到水溶液中以形成水性混合物；
搅拌所述水性混合物；
将铂化合物添加到所述水性混合物中以形成预催化剂混合物；
将所述预催化剂混合物在80℃至200℃下加热至少24小时，从而使所述预催化剂混合物结晶以形成包含包封铂的沸石的所述加氢裂化催化剂。
2.根据权利要求1所述的方法，其中所述沸石是方钠石。
3.根据前述权利要求中任一项所述的方法，其中所述加氢裂化催化剂包含通过X射线粉末衍射分析测定的大于20％的结晶度。
4.根据前述权利要求中任一项所述的方法，其中所述铝化合物包含铝金属粉末、氢氧化铝、铝酸钠或其组合。
5.根据前述权利要求中任一项所述的方法，其中所述硅化合物包含二氧化硅、硅酸钠、胶态二氧化硅、热解法二氧化硅或其组合。
6.根据前述权利要求中任一项所述的方法，其中所述盐包含氯化钠、重铬酸钾、氯化钙、硫酸氢钠、硫酸铜或其组合。
7.根据前述权利要求中任一项所述的方法，其中所述铂化合物包含选自以下群组的铂盐：Pt(NH3)Cl2、PtCl2、PtCl4、(NH4)2PtCl6、(NH4)2Pt(NO3)2、Na2PtCl6.6H2O、H2PtCl6.6H2O、Na2PtCl4.4H2O、(NH4)2PtCl4或其组合。
8.根据前述权利要求中任一项所述的方法，其进一步包含：
将所述包封铂的沸石与沸石Y共混；和
将选自镍、钼、钨或其组合的一种或多种基于金属的催化剂添加到所述加氢裂化催化剂中。
9.根据权利要求8所述的方法，其中所述添加涉及混合或浸渍到沸石Y、所述包封铂的沸石或其组合中。
10.根据前述权利要求中任一项所述的方法，其中所述预催化剂混合物包含xNaOH:1Al2O3:2SiO2:yNaCl:z(NH4)2PtCl4:wH2O，其中x＝10-30，y＝0-10，z＝0.02-0.5，并且w＝100-500。
11.一种加氢裂化催化剂，其包含：
包封铂的沸石，所述包封铂的沸石具有通过X射线粉末衍射分析测定的大于20％的结晶度。
12.根据权利要求11所述的加氢裂化催化剂，其中所述沸石包含孔径为1.0至3.0纳米的方钠石。
13.根据权利要求11或12中任一项所述的加氢裂化催化剂，其进一步包含沸石Y和任选的氧化铝。
14.根据权利要求13所述的加氢裂化催化剂，其进一步包含镍、钼、钨或其组合。
15.根据权利要求14所述的加氢裂化催化剂，其中其中所述加氢裂化催化剂包含10至20wt％的MoO3、1至10wt％的NiO、20至80wt％的Al2O3以及10至60wt％的包封铂的方钠石和沸石Y。
16.根据权利要求14所述的加氢裂化催化剂，其中其中所述加氢裂化催化剂包含20至30wt％的WO3、1至10wt％的NiO、20至80wt％的Al2O3以及10至60wt％的包封铂的方钠石和沸石Y。
17.根据权利要求12至16中任一项所述的加氢裂化催化剂，其中所述加氢裂化催化剂包含1至10wt％的组合的方钠石和铂。
18.根据权利要求11至17中任一项所述的加氢裂化催化剂，其中所述加氢裂化催化剂包含大于35％的结晶度。
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