CN1942560A - 制备小晶粒ssz-32的方法及其在烃转化方法的应用 - Google Patents
制备小晶粒ssz-32的方法及其在烃转化方法的应用 Download PDFInfo
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- CN1942560A CN1942560A CNA2004800349197A CN200480034919A CN1942560A CN 1942560 A CN1942560 A CN 1942560A CN A2004800349197 A CNA2004800349197 A CN A2004800349197A CN 200480034919 A CN200480034919 A CN 200480034919A CN 1942560 A CN1942560 A CN 1942560A
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 230000009183 running Effects 0.000 description 1
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- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
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- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 235000012976 tarts Nutrition 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Abstract
本发明涉及制备称为SSZ-32X的小晶粒SSZ-32沸石的方法。本催化剂适用于将包括10个或更多碳原子的直链和轻度支化链烷烃烃的进料脱蜡来生产异构化产物的方法,异构化物料收率有所提高且轻端产量有所减少。
Description
发明领域
本发明涉及制备包括小晶粒中孔径沸石、特别是SSZ-32的催化剂的方法。催化剂适用于将包括10个或更多碳原子的直链和轻度支化链烷烃的进料异构化。
发明背景
近年来采用加氢法生产II类和III类基础油的倾向不断增加。不断在寻求在异构化选择性和转化率方面有所提高的催化剂。如美国专利5282958的1-2栏所讨论,在异构化和择形脱蜡过程中使用中孔分子筛如ZSM-22、ZSM-23、ZSM-35、SSZ-32、SAPO-11、SAPO-31、SM-3、SM-6是众所周知的。其它典型的脱蜡用沸石包括ZSM-48、ZSM-57、SSZ-20、EU-I、EU-13、镁碱沸石、SUZ-4、θ-1、NU-10、NU-23、NU-87、ISI-1、ISI-4、KZ-1和KZ-2。
美国专利5252527和5053373公开-种用N-低级烷基-N’-异丙基-咪唑阳离子作为模板制备的如SSZ-32的沸石。5053373公开硅铝比为大于20到小于40,且焙烧后氢型的约束指数为13或更高。5252527没有限定约束指数为13或更高。5252527公开将金属负载于沸石上以便提供加氢-脱氢功能。典型的置换阳离子可包括氢铵离子、金属如稀土金属、IIA族和VIII族金属的阳离子以及它们的混合物。美国专利5707601公开了使用小的中性胺制备MTT型沸石如SSZ-32或ZSM-23的方法。
美国专利5397454公开了使用如小晶粒和焙烧后氢型的约束指数大于13或更高的SSZ-32的沸石进行烃转化的方法。催化剂的硅铝比大于20且小于40。美国专利5300210的目标也是使用SSZ-32进行烃转化的方法。美国专利5300210的SSZ-32不限定于小晶粒。
发明概述
本发明涉及适用于将烃进料脱蜡来生产异构化产物的小晶粒SSZ-32沸石(下文称为SSZ-32X)。本发明还涉及制备该沸石的方法和使用包括SSZ-32X的催化剂的脱蜡方法。过程进料包括10个或更多碳原子的直链和轻度支化链烷烃。在异构化条件下,于氢气存在下将进料与包括SSZ-32X的催化剂接触。本催化剂要比标准SSZ-32规定的结晶度低,氩气吸附比改变、外表面积增加且裂化活性比异构化所用的其它中孔分子筛降低。在异构化反应中使用本催化剂可使润滑产物的收率更高且气体产量更低。
附图简介
图1(a)、1(b)和1(c)示出标准SSZ-32与SSZ-32X之间X射线衍射图的对比。
图2(a)和2(b)示出异构脱蜡过程中使用SSZ-32X与使用标准SSZ-32在收率和VI特性方面的对比。
优选方案的详述
制备催化剂
新型SSZ-32沸石适合由含下列来源的水溶液制备:碱金属氧化物或氢氧化物、烷基胺(如异丁胺)、N-低级烷基-N’-异丙基-咪唑(优选N,N’-二异丙基-咪唑阳离子或N-甲基-N’-异丙基咪唑阳离子)(随后经离子交换成羟型)、铝的氧化物(优选其中的氧化铝源提供能以共价形式分散于氧化硅上的氧化铝)和另外的硅氧化物。反应混合物具有下列摩尔比范围的组成:
表1摩尔比组成
宽 | 优选 | |
SiO2/Al2O3 | 20-小于40 | 30-35 |
OH-/SiO2 | 0.10-1.0 | 0.20-0.40 |
Q/SiO2 | 0.05-0.50 | 0.10-0.25 |
M+/SiO2 | 0.05-0.30 | 0.15-0.30 |
H2O/SiO2 | 20-300 | 25-60 |
Q/Q+M+ | 0.25-0.75 | 0.33-0.67 |
其中Q是Qa和Qb的总和。
Qa是N-低级烷基-N’-异丙基-咪唑阳离子(优选N,N’-二异丙基-咪唑阳离子或N-甲基-N’-异丙基咪唑阳离子)。Qb是胺。适宜Qb的实例是异丁基胺、新戊基胺或一乙基胺,尽管也可用其它胺。Qb必须大于咪唑化合物Qa的摩尔浓度。通常Qb的摩尔浓度为从2到约9倍的Qa摩尔浓度范围。美国专利5785947(并入本文作为参考)描述了用两种有机源来合成沸石的方法,其中一种有机源是含1-8个碳原子的胺,该方法比仅用季铵离子源(如咪唑)作为有机组分源的方法能显著节省成本。将两种有机氮源组合使用的方法可让主模板(用量很少)形成所期望沸石结构的核,然后胺则有助于以稳定方式在晶体生长过程中填充孔洞。高氧化硅沸石的空孔在合成条件下很容易再溶解。胺还有助于维持合成过程的高碱度。
M是碱金属离子,优选钠或钾。所用的起季铵离子源作用的有机阳离子化合物可提供氢氧离子。
结晶混合物的阳离子组分Qa优选衍生自下式化合物:
其中R是包含1-5个碳原子的低级烷基且优选是-CH3或异丙基,且阴离子(Aθ)对沸石的形成无不利影响。代表性的阴离子包括卤素如氟、氯、溴和碘,氢氧根、乙酸根、硫酸根、羧酸根等。氢氧根是最优选的阴离子。
采用标准沸石制备技术来制成反应混合物。反应混合物中铝氧化物的典型来源包括铝酸盐、氧化铝和铝化合物,如涂铝硅胶(优选Nalco 1056溶胶,尽管也可使用其它品牌)Al2(SO4)3和其它沸石。
在一个优选的制备沸石SSZ-32X的方法中,我们发现为沸石合成混合物提供能将铝氧化物以共价形式分散于氧化硅上的铝氧化物源可使结晶的沸石具有更高的铝含量。铝含量增加将促进异构化反应。在另一途径中,可使用高硅五元环型结构和低氧化硅/氧化铝比(约10)的沸石作为沸石SSZ-32X合成的铝氧化物源或原料。在上述有机源Qa和Qb存在下,这些沸石可重结晶成新的SSZ-32X沸石。
发光沸石和镁碱沸石是两类适合此用途的铝氧化物或原料来源。后一类沸石也可用于ZSM-5和ZSM-11的结晶(美国专利4503024)。
在铝氧化物以共价形式分散于氧化硅的另一优选途径中,使用一种涂铝氧化硅溶胶如Nalco化学公司生产的商品名为1056溶胶(氧化硅26%,氧化铝4%)的产品。使用该溶胶除能提供具有高铝含量的新型SSZ-32X外,还能生成具有出人意料高异构化能力的小于1000A(沿主轴方向)的晶体。
实际上,SSZ-32X(氢型)在裂化能力方面的催化性能可由约束指数值(如J.Catalysis 67第218页所定义)为13或更高且优选为13-22来显示。美国专利4481177中也公开了约束指数的测定方法。一般来说,降低沸石的晶体尺寸会导致择形性下降。在J.Catalysis99,327(1986)所示的涉及芳族化合物的ZSM-5反应已显示了这一点。此外,已发现沸石ZSM-22(美国专利4481177)与ZSM-23密切相关(J.Chem.Soc.Chem.Comm.1985第1117页)。在上面ZSM-22的参考文献中显示将所生产的晶体进行球磨处理能生成约束指数为2.6的催化剂。对这种材料来说这是一个令人意外的低值,另外的研究表明它是一种高选择性的10环道高硅五元环型(Proc.of 7th Intl.ZeoliteConf.Tokyo,1986,23页)。大概球磨处理生成了更小的晶体,导致选择性降低而催化活性提高。令人意外处也就在此,在SSZ-32X的情况下,更小的晶体能维持高选择性。
典型的硅氧化物源包括硅酸盐、氧化硅水凝胶、硅酸、胶质氧化硅、水蒸汽法二氧化硅、四烷基正硅酸盐和氢氧化氧化硅。可将盐特别是碱金属卤化物如氯化钠加入或形成于反应混合物中。据文献披露它们的作用是帮助沸石结晶同时避免氧化硅吸留于网格内。
将反应混合物维持在一个升温条件下直到沸石晶体形成。水热结晶步骤的温度一般维持在约140-200℃、优选约160-180℃且最优选约170-180℃。结晶周期一般大于1天且优选约4-10天。
水热结晶步骤在加压条件下实施,且通常是在高压釜内进行,这样反应混合物自动产生压力。在加入各组分及结晶时可将反应混合物搅拌。
一旦形成沸石晶体,则采用标准机械分离技术如过滤或离心分离技术将固体产物从反应混合物中分离出来。将晶体水洗后例如在90-150℃下干燥8-24小时,得到合成好的沸石晶体。干燥步骤可在大气压下或低于大气压力下操作。
水热结晶步骤中,可使晶体从混合物中自发成核。反应混合物也可用SSZ-32做晶种来导引并加速结晶,以及使不期望的铝硅酸盐杂质最少化。
SSZ-32X可合成后直接使用或是进行热处理(焙烧)。通常最好是通过离子交换法将碱金属阳离子移出并置换成氢、铵或任何期望的金属离子。将沸石用螯合剂如EDTA沥滤或用酸溶液稀释来增加氧化硅氧化铝摩尔比。也可将SSZ-32X汽蒸处理,汽蒸处理有助于晶体网格受酸攻击时能够稳定。
SSZ-32X常常与那些期望有加氢脱氢功能用途的加氢组分紧密联用。典型的置换组分包括氢、铵、金属如稀土、IIA族和VII族金属阳离子以及它们的混合物。优选的加氢组分包括钨、钒、钼、铼、镍、钴、锰、铂、钯(或其它贵金属)
添加用来影响催化剂整体功能(包括增强异构化和降低裂化活性)的金属包括镁、镧(和其它稀土金属)、钡、钠、镨、锶、钾和钕。也可用来改进催化剂活性的其它金属包括锌、镉、钛、铝、锡和铁。
氢、铵以及金属组分可被交换入SSZ-32X。也可将沸石用金属浸渍,或者用本领域已知的标准方法将金属与SSZ-32X直接物理混合。并且通过在制备SSZ-32所用的混合物中已有所期望金属以离子形式存在的方法可使该金属吸留于晶体网格内。
典型的离子交换技术包括将SSZ-32X与含所期望的置换阳离子或阳离子的溶液进行接触。尽管有很多盐可用,但特别优选氯化物或其它卤化物、硝酸盐和硫酸盐。代表性的阳离子交换技术公开于很多专利,包括美国专利3140249、3140251和3140253。离子交换步骤可在SSZ-32X焙烧前或后进行。
与所期望的置换阳离子盐溶液进行接触后,一般是将SSZ-32X用水洗涤并在65℃-约315℃范围的温度下干燥。洗涤后,可在空气或惰性气氛中于约200-820℃范围的温度下将SSZ-32X焙烧1-48小时或更长时间,制成特别适用于烃转化过程的催化活性产物。
将上述SSZ-32X沸石转化为酸型并与难熔无机氧化物载体的前体和水溶液混合来形成一个混合物,水溶液优选是酸性的。溶液起胶溶剂的作用。载体(又称为底物或粘结剂)可选用来耐受有机转化过程所用温度和其它条件。这类底物材料包括活性或非活性材料和合成或天然存在沸石以及无机材料如粘土、氧化硅和金属氧化物。后者可是天然存在的或是凝胶状沉淀、溶胶或凝胶体形式。在某些有机转化过程中将活性材料与SSZ-32X联用即并用往往能提高转化率和催化剂选择性。
SSZ-32X通常是与多孔性底物材料和混合底物材料如氧化硅、氧化铝、氧化钛、氧化镁、氧化硅-氧化铝、氧化硅-氧化镁、氧化硅-氧化锆、氧化硅-氧化钍、氧化硅-氧化铍、氧化硅-氧化钛、氧化钛-氧化锆、及三元复合物如氧化硅-氧化铝-氧化钍、氧化硅-氧化铝-氧化锆、氧化硅-氧化铝-氧化镁和氧化硅-氧化镁-氧化钍组合。底物可以是共凝胶形式。本发明中,优选的底物材料是氧化铝和氧化硅。在实际合成SSZ-32X的过程中以及催化剂制备后几步中可加入金属来增强催化剂的性能。制备方法包括可通过热手段实现的固态离子交换法,金属盐溶液喷雾干燥法和制备盐溶液的淤浆法。可过滤淤浆液来回收已负载金属的SSZ-32X。
非活性材料适合起稀释剂作用,用来在指定过程中控制转化量,以便能经济地获得产物,无需采用其它控制反应速度的手段。通常,沸石材料已并入天然存在的粘土如膨润土和高岭土。这些材料如粘土、氧化物等部分起催化剂粘结剂作用。最好是提供具有良好压碎强度的催化剂,因为在石油炼制过程中,催化剂经常会受到粗暴操作,这往往会使催化剂破碎成粉末,造成加工过程出现问题。
可与本发明的合成SSZ-32X组合的天然存在粘土包括蒙脱石和高岭土系列,包括次膨润土和常称为Dixie、McNamee、Georgia和Florida粘土的高岭土或是其中主要矿石构成为叙永石、高岭石、地开石、珍珠陶土和蠕陶土的其它材料。纤维状粘土如海泡石和绿坡缕石也可用作载体。这些粘土可以开采时的原始状态使用,或者先经焙烧、酸处理和化学改性后使用。
SSZ-32X与粘结剂的混合物可成型为各种物理形状。一般来说,混合物可成型为粉末状、颗粒和模制产物,如粒径足以通过2.5目(Tyler)筛网且保留在48目(Tyler)筛网上的挤出物。在催化剂为模制的情况中,如与有机粘结剂一起挤出的情况中,混合物可在干燥前挤出,或者干燥或部分干燥后挤出。SSZ-32X也可经汽蒸处理。汽蒸处理有助于晶体网格受酸攻击时能够稳定。然后采用焙烧法将干燥的挤出物热处理。
焙烧温度范围为390-1100。焙烧进行时间在0.5-5小时范围或更长时间,生成特别适用于烃转化过程的催化活性产物。
然后采用如浸渍的技术将挤出物或颗粒用VIII族金属负载来增强加氢功能。最好是按美国专利4094821所公开内容,一次性将改性金属与VIII族金属共浸渍。VIII族金属优选是铂、钯或二者的混合物。负载后,可将材料在空气或惰性气体中于500-900温度下进行焙烧。
进料
本发明可用来将范围从较轻的蒸馏馏分如煤油和航空燃料到高沸点油料如全部粗石油、常压重油、真空蒸馏塔渣油、循环油、合成原油(如页岩油、沥青和焦油等)、瓦斯油、真空瓦斯油、油脚、费-托过程衍生的蜡和其它重油的原料进行脱蜡。本文有时会将16个或更多碳原子的直链正构链烷烃单独或与仅轻度支链的链烷烃一起称为蜡。原料通常是C10+原料,一般沸点要高于约350,因为更轻的油所含蜡组分的量通常不很显著。但是,本方法特别适用于含蜡馏分油料如中间馏分油料,包括瓦斯油、煤油和航空燃料、润滑油、民用燃料油和其它倾点和粘度必须维持在某一规定限定值内的蒸馏馏分。润滑油油料的沸点通常高于230℃(450)、更常常是高于315℃(600)。加氢处理的油料还有其它蒸馏馏分就是这类很方便的油料源,因为它们一般都含有大量的蜡质正构链烷烃。本方法的原料一般可以是含链烷烃、烯烃、环烷烃、芳烃和杂环化合物的C10+原料,且主要部分是对原料蜡性质负有责任的较高分子量正构链烷烃和轻度支化链烷烃。在加氢处理过程中,正构链烷烃和轻度支化链烷烃进行一些裂化和加氢裂化反应来形成对低粘产物有利的液体范围物质。但是,要对裂化进行的程度有所限制,以减少沸点低于原料的产物产率,从而保持原料的经济价值。
典型的原料包括加氢处理和加氢裂化瓦斯油,加氢处理润滑油提余油、光亮油、润滑油料、合成有、油脚、费-托合成油、高倾点聚烯烃、正构α-烯烃蜡、软蜡、脱油蜡和微晶蜡。
条件
本发明异构化/脱蜡方法的实施条件通常包括温度在约392-800范围,压力约为15-3000psig。更优选压力约为100-2500psig。接触过程中液时空速通常约为0.1-20、更优选约0.1-5。优选在氢气存在下进行接触。氢气与烃的比例优选在约2000-10000标准立方英尺H2/桶烃范围、更优选约为2500-5000标准立方英尺H2/桶烃。
本发明的产物可进一步进行处理如加氢精制。加氢精制常规是在金属加氢催化剂如氧化铝担载的铂存在下进行的。加氢精制可在约374-644的温度和约400-3000psig的压力下实施。例如美国专利3852207(并入本文作为参考)中描述了按此方式的加氢精制方法。
实施例
合成宽峰(broadline)SSZ-32X沸石(参看X射线衍射图)的真正意思就是结晶出很小晶体的沸石样品。随着晶体尺寸减小,x射线衍射峰变宽。一般对于MTT结构沸石体系如标准SSZ-32及SSZ-32X体系来说,随着SiO2/Al2O3比降低(沸石产物中wt%Al较高),晶体尺寸也减小。
图1(a)将SSZ-32X的峰位置和相对强度与标准SSZ-32进行比较。相对强度是将强度值除以参比强度并乘100%得到的,或表示为100×I/I0。
图1(b)和(c)是将SSZ-32X图叠合到标准SSZ-32图上,可清楚地看到主峰的相配性。图1(c)示出图1(b)的更细节部分。表2(a)示出标准SSZ-32的峰列表和各峰的相对强度。表2(b)放大了峰宽以便能很容易地比较SSZ-32X和标准SSZ-32。
表2(a)-标准SSZ-32的峰列表
2θ | d-晶面间距() | 相对强度(%)(I/I0)×100 |
7.9 | 11.2 | 19 |
8.2 | 10.8 | 24 |
8.9 | 10.0 | 11 |
11.4 | 7.8 | 20 |
14.7 | 6.05 | 2 |
15.9 | 5.59 | 5 |
11.4 | 5.41 | 4 |
18.2 | 4.88 | 12 |
19.6 | 4.52 | 69 |
20.1 | 4.43 | 11 |
20.9 | 4.25 | 70 |
21.4 | 4.15 | 9 |
22.8 | 3.90 | 100 |
23.9 | 3.73 | 53 |
24.0 | 3.70 | 58 |
24.7 | 3.61 | 50 |
25.2 | 3.53 | 36 |
26.0 | 3.43 | 42 |
28.2 | 3.16 | 11 |
29.4 | 3.03 | 7 |
31.6 | 2.83 | 13 |
表2(b)-所制备的SSZ-32X的各峰
2θ | d-晶面间距() | 相对强度(%)(I/I0)×100 |
8.03 | 11.0 | 33 |
8.83 | 10.0 | 6 |
11.30 | 7.83 | 20 |
15.71 | 5.64 | 3 |
16.34 | 5.42 | 3 |
18.09 | 4.90 | 7 |
19.54 | 4.54 | 33 |
19.67 | 4.51 | 20 |
20.81 | 4.27 | 31 |
21.21 | 4.18 | 14 |
22.74 | 3.91 | 63 |
23.91 | 3.72 | 100 |
24.54 | 3.62 | 24 |
25.09 | 3.55 | 34 |
25.87 | 3.44 | 31 |
26.91 | 3.31 | 5 |
28.10 | 3.17 | 4 |
29.34 | 3.04 | 5 |
31.46 | 2.84 | 8 |
31.94 | 2.80 | 3 |
34.02 | 2.63 | 1 |
35.22 | 2.55 | 17 |
36.29 | 2.47 | 16 |
实施例1合成SSZ-32X
所期望材料的制备按下述步骤合成:一个Hastelloy C衬层的5加仑高压釜单元用于混合各反应试剂和随后进行热处理。在1500RPM下并历时1/2小时,按所述顺序加入下列各组分并混合。将300克1M的N,N’-二异丙基咪唑氢氧化物溶液混入4500克水中。按US4483835实施例8制成碘盐,随后用BioRad AG1-X8交换树脂进行离子交换成羟型。加入2400克1N的KOH。加入1524克LudoxAS-30(30wt%SiO2)。加入1080克Nalco的1056溶胶(26wt%SiO2和4wt%Al2O3)。最后将181克异丁胺搅拌入混合物。通常,胺Qb的摩尔浓度必须超过咪唑化合物Qa的摩尔浓度。
搅拌完成后,关闭高压釜盖,将反应经8小时升温到170℃。系统以150RPM的速度搅拌。加热106小时后,停止反应,收集产物。过滤收集固体(进行的很慢,少量晶体为指示)。随后洗涤数次并干燥。材料用x射线衍射法进行分析,衍射图示于表3。与表2(a)所列的更标准的SSZ-32的数据进行比较,可以看出实施例1的新产物基本上与SSZ-32相符,但衍射线条大大增宽。
表3
2θ | d-晶面间距() | 强度 | 相对强度(%)(I/I0)×100 |
8.00 | 11.05 | 15 | 26 |
8.80 | 10.05 | 6 | 10 |
11.30 | 7.83 | 10 | 17 |
14.50 | 6.11 | 1 | 2 |
15.75 | 5.63 | 3 | 5 |
16.50 | 5.37 | 3 | 5 |
18.10 | 4.901 | 7 | 12 |
19.53 | 4.545 | 41 | 71 |
20.05 | 4.428 | 6肩峰 | 10肩峰 |
20.77 | 4.277 | 41 | 71 |
21.30 | 4.171 | 7 | 12 |
22.71 | 3.915 | 58 | 100 |
23.88 | 3.726 | 57 | 98 |
24.57 | 3.623 | 30 | 52 |
25.08 | 3.551 | 25 | 43 |
25.88 | 3.443 | 27 | 47 |
26.88 | 3.317 | 5 | 9 |
28.11 | 3.174 | 6 | 10 |
就所关注的产物可能是小晶体与可观的无定形材料的混合物问题,进行TEM(透射电镜)分析。电镜照片显示实施例1的产物是相当均一的SSZ-32小晶体(产物为SSZ-32X),只有极少无定形材料的迹象。晶粒的特征为分散的200-400范围内小而宽的板状(lathe-like)组分。此产物的SiO2/Al2O3比为29。
实施例2
在空气中,将实施例1的产物以1℃/分钟(1.8/分钟)的速率升温至1100进行焙烧并在250下恒温3小时、1000下恒温3小时和1100下恒温3小时。焙烧后的材料维持其x射线结晶度。按前面提及的美国专利5252527所述,于200下将焙烧后的沸石进行两次离子交换(使用NH4NO3)。离子交换后的材料再焙烧,然后用5252527所述的实验方法测定孔隙度。新产物SSZ-32X与传统的SSZ-32相比有出人意料的差异。
SSZ-32X的Ar吸附比(于87K和0.001到0.1间相对压力下的Ar吸附)/(相对压力0.1以下的全部Ar吸附)大于0.5且优选在0.55-0.70范围。传统的SSZ-32则相反,Ar吸附比小于0.5,一般在0.35-0.45之间。实施例1和2的SSZ-32X显示氩吸附分数为0.62。晶粒外表面积从约50m2/g(SSZ-32)跃升到150m2/g(SSZ-32X),表明因晶体很小故外表面积很可观。
同时,SSZ-32X的孔体积相比标准SSZ-32的约0.06cc/g下降到约0.035cc/g。
实施例3
采用约束指数试验来测试离子交换后SSZ-32X的裂化活性。该试验值是一个能显示沸石SSZ-32X专一选择性的重要参数。美国专利5252527实施例9描述了该试验。采用该试验条件,标准SSZ-32所提供的50%转化率和800下约束指数典型为13-22。本发明的实施例2产物在按相同方法进行试验时,所得转化率大大降低,约为12%,同时维持择形特性。
表4-标准SSZ-32与SSZ-32X之间的特性比较
标准SSZ-32 | SSZ-32X | |
二异丙基咪唑/氧化硅 | 0.00 | 0.05 |
产物的氧化硅/氧化铝比 | 35 | 28-30 |
产物的Ar吸附分数 | (0.35-0.45) | (0.55-0.70) |
约束指数 转化试验 | 50% | 12% |
晶体尺寸,微米 | 0.17 | 0.01-0.04 |
*Ar吸附比(于87K和0.001到0.1间相对压力下的Ar吸附)/(相对压力0.1以下的全部Ar吸附)。
实施例4
本材料下一个令人非常惊讶之处来自于用正十六烷为进料和Pd负载于本发明实施例2产物所进行的异构化能力试验。按前面提及的美国专利5282958实施例1所述方法进行Pd离子交换。采用美国专利5282958实施例1所述方法测试催化剂。新催化剂和SiO2/Al2O3比相当的标准SSZ-32粉末都给出了545下n-C16转化率约96%,不同之处在于本发明的实施例2新材料所给出的异构化选择性为75.8%,而按美国专利5282958实施例1所述,标准SSZ-32的该值为64%。因此尽管实施例3中显示沸石的裂化活性降低不少,但烃转化的活性等于标准SSZ-32且选择性要好很多。两个催化剂间的主要区别之一是标准SSZ-32生成约13%的C6和更低物料,而新催化剂则使该值降低到7%,液体区域增加但轻端产量减少。
实施例5
按实施例4进行实验,但本例是用Pt而不是Pd。Pt催化剂于550℃下焙烧3小时。筛分出8cc的催化剂碎片(24-42目尺寸)并在空气中500下干燥过夜后装填入一个不锈钢反应器内。500下,在2300psig的H2流中将催化剂还原1小时。金属还原后,催化剂用来将API为38.9、蜡含量33%且倾点为38℃的含蜡轻质中性加氢裂化油进料异构化。从反应器出来的全部液体产物在汽提塔内分成两股馏分,塔底产物目标是-15℃倾点。再制备标准SSZ-32催化剂并按类似方式处理。下表5的数据示出了使用新SSZ-32X作为异构化催化剂所获得的改进之处。又一个主要优点是看出轻质气体产量减少,这可能与新材料的总固有酸度较低有关。
表5
沸石 | Wt%700+ | 产物VI为4.1厘沲 | C1-C4wt% | C5-250 | 250-550 |
标准SSZ-32 | 70.2 | 127 | 5.2 | 9.3 | 10 |
SSZ-32X | 75.4 | 129 | 2.4 | 6 | 8.3 |
实施例6
用SSZ-32X粉末制备粘结型催化剂,使用氧化铝粘结剂,挤出,基础物干燥和焙烧,先湿法Pt浸渍,最后将挤出物干燥并焙烧。总Pt负载量为0.32wt%。按类似上一个实施例的负载和活化步骤后,通过加入200微摩尔氮(如三丁基胺)/g催化剂的方法进行滴定步骤操作。然后将该催化剂对一个含10%蜡和倾点为+32℃的含蜡150N加氢裂化油进料进行测试。所用工艺条件为LHSV为1.0小时-1,气油比为4000scf/bbl且总压为2300psig。图2(a)和2(b)中,当塔底产物(650+cut)与包括SSZ-32X的催化剂接触时所观察到的收率和所得VI值与当进料和标准SSZ-32沸石制成的类似粘结型催化剂接触时得到的值相当。在-5到25℃产物倾点范围内可看到收率和VI值有所改进。
Claims (37)
1.氧化硅与氧化铝摩尔比大于约20∶1到小于40∶1的沸石,其晶粒含200-400范围的小而宽板状组分且有表1所示的x射线衍射线。
2.权利要求1的沸石,该沸石的Ar吸附比(定义为于87K和0.001到0.1间相对压力下的Ar吸附分数)/(相对压力0.1以下的全部Ar吸附)大于0.5,沸石的最小微孔体积为0.02cc/g。
3.权利要求2的沸石,其中Ar吸附比在0.55-0.75范围。
4.权利要求1的沸石,其外表面积在80-300m2/g范围。
5.制备适用于将烃进料脱蜡来生产异构化产物过程的脱蜡催化剂的方法,所述催化剂比异构化用的其它中孔径分子筛所规定的结晶度低,微孔体积减小、表面积增加且裂化活性降低,该进料包括10个或更多碳原子的直链和轻度支化链烷烃,该制备方法包括如下步骤:
(a)通过采用下述步骤来合成氧化硅与氧化铝摩尔比大于约20∶1到小于40∶1的沸石,其晶粒含200-400范围的小而宽板状组分且有表1所示的x射线衍射线:
(i)将下列试剂按指定量混合形成混合物:
(1)5份N-低级烷基-N-甲基-N’-异丙基-咪唑阳离子,其已离子交换为氢氧化物型;
(2)20份碱金属氢氧化物;
(3)100份SiO2比3.5份Al2O3;
(4)20份烷基胺,
(ii)在高压釜内,将步骤(i)的混合物于自生压力、500-1500rpm下搅拌0-5小时;
(iii)将混合物在升温条件下维持40-120小时时间来形成沸石晶体;
(iv)通过过滤或离心分离收集沸石晶体;
(v)将晶体焙烧和离子交换处理;
(b)将步骤(a)合成的沸石与难熔无机氧化物载体的前体和水溶液混合形成混合物,所述混合物的分子筛含量约10-90wt%;
(c)将步骤(b)的混合物挤出或成型为挤出物或成型颗粒;
(d)将步骤(c)的挤出物或成型颗粒干燥;
(e)将步骤(d)的挤出物或成型颗粒焙烧;
(f)将步骤(d)的挤出物或成型颗粒负载上加氢组分或一种或多种其它改性金属来制备催化剂前体;
(g)将步骤(f)的催化剂前体干燥;
(h)将干燥的步骤(f)的催化剂前体焙烧来形成最终的粘结型脱蜡催化剂。
6.权利要求5方法制备的脱蜡催化剂。
7.权利要求4的方法,其中沸石是SSZ-32X。
8.权利要求5(f)的方法,其中其它改性金属选自镁、镧和其它稀土金属、钡、钠、镨、锶、钾、钕和钙。
9.一种由水溶液制成的、合成后及干态组成如下所述的沸石,其氧化物的摩尔比如下:(0.05-2.0)Q2O∶(0.1-2.0)M2O∶Al2O3(20-小于40)SiO2,其中M是碱金属阳离子,Q是N-低级烷基-N’-异丙基-咪唑Qa和胺Qb的总和,该沸石具有表1的x射线衍射线条,其中Qb的摩尔浓度大于Qa的摩尔浓度。
10.权利要求9的沸石,其中Qa选自N-甲基-N’-异丙基-咪唑阳离子和N,N’-二异丙基-咪唑阳离子。
11.权利要求9的沸石,其中Qb选自异丙基胺、异丁基胺、异戊基胺、新戊基胺或一乙基胺。
12.权利要求9的沸石,其约束指数在8-30范围。
13.权利要求9的沸石,其氧化硅/氧化铝比在20-40范围。
14.权利要求9的沸石,其是通过将沸石在200℃(392)-820℃(1508)的温度下热处理来制备的。
15.权利要求9的沸石,其中是用氢、铵、稀土金属、IIA族金属或VIII族金属离子进行离子交换。
16.权利要求9的沸石,其中稀土金属、IIA族金属或VIII族金属被吸留于沸石内。
17.权利要求9的沸石,其包含选自镁、镧和其它稀土金属、钡、钠、镨、锶、钾、钕和钙的改性金属。
18.将烃进料脱蜡,由此生成收率最大化的异构化产物和收率最小化的轻端产物的方法,该进料包括10个或更多碳原子的直链和轻度支化链烷烃,所述方法包括将进料在异构化条件及氢气存在下与包括按下述步骤制备的中孔径分子筛的催化剂接触:
(a)通过采用下述步骤来合成氧化硅与氧化铝摩尔比大于约20∶1到小于40∶1的沸石,其晶粒含200-400范围的小而宽板状组分且有表1所示的x射线衍射线:
(i)将下列试剂按指定量混合形成混合物:
(1)5份N-低级烷基-N-甲基-N’-异丙基-咪唑阳离子,其已离子交换为氢氧化物型;
(2)20份碱金属氢氧化物;
(3)100份SiO2比3.5份Al2O3;
(4)20份烷基胺,
(ii)在高压釜内,将步骤(i)的混合物于自生压力、500-1500rpm下搅拌0.5-5小时;
(iii)将混合物在升温条件下维持40-120小时来形成沸石晶体;
(iv)通过过滤或离心分离收集沸石晶体;
(v)将晶体焙烧和离子交换处理;
(b)将步骤(a)合成的沸石与难熔无机氧化物载体的前体和水溶液混合来形成混合物,所述混合物的分子筛含量约10-90wt%;
(c)将步骤(b)的混合物挤出或成型为挤出物或成型颗粒;
(d)将步骤(c)的挤出物或成型颗粒干燥;
(e)将步骤(d)的挤出物或成型颗粒焙烧;
(f)将步骤(d)的挤出物或成型颗粒负载上加氢组分制备催化剂前体;
(g)将步骤(f)的催化剂前体干燥;
(h)将干燥的步骤(g)的催化剂前体焙烧来形成最终的粘结型脱蜡催化剂。
19.权利要求18的脱蜡方法,其中沸石是SSZ-32X。
20.权利要求19的脱蜡方法,使用一种由水溶液制成的、合成后及干态组成如下所述的沸石,其氧化物的摩尔比如下:(0.05-2.0)Q2O∶(0.2-2.0)M2O∶Al2O3(20-小于40)SiO2,其中M是碱金属阳离子,Q是N-低级烷基-N’-异丙基-咪唑Qa和胺Qb的总和,该沸石具有表1的x射线衍射线条,其中Qb的摩尔浓度大于Qa的摩尔浓度。
21.权利要求19的方法,其中Qa选自N-甲基-N’-异丙基-咪唑阳离子和N,N’-二异丙基-咪唑阳离子。
22.权利要求19的方法,其中Qb选自异丙基胺、异丁基胺、异戊基胺、新戊基胺或一乙基胺。
23.权利要求19的方法,其中沸石的约束指数在8-30范围。
24.权利要求19的方法,其中沸石的氧化硅/氧化铝比在20-40范围。
25.权利要求19的方法,其中沸石是通过在200℃(392)-820℃(1508)的温度下进行热处理来制备的。
26.权利要求19的方法,其中沸石用氢、铵、稀土金属、IIA族金属或VIII族金属离子进行离子交换。
27.权利要求19的方法,其中稀土金属、IIA族金属或VIII族金属被吸留于沸石内。
28.权利要求19的方法,其中所述进料选自加氢处理或加氢裂化瓦斯油,加氢处理润滑油提余油、光亮油、润滑油料、合成油、蜡下油、费-托合成油、高倾点聚烯烃、正构α-烯烃蜡、软蜡、脱油蜡和微晶蜡。
29.权利要求27的方法,其中VIII族金属选自铂和钯,和/或其混合物。
30.权利要求19的方法,其中所述接触步骤在约450-800范围的温度,和约15-3000psig的压力下进行。
31.权利要求30的方法,其中所述压力在约100-2500psig范围。
32.权利要求21的方法,其中接触过程中液时空速为约0.1-20。
33.权利要求32的方法,其中液时空速为约0.5-5。
34.权利要求19的方法,其中烃进料在异构化之前要在325-800的温度下进行加氢处理。
35.权利要求19的方法,异构化之后进一步包括加氢精制步骤。
36.权利要求35的方法,进一步包括将异构化产物进行加氢精制。
37.权利要求36的方法,其中加氢精制在约325-590范围的温度和约400-3000psig范围的压力下进行。
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI494161B (zh) * | 2008-12-16 | 2015-08-01 | Exxonmobil Res & Eng Co | 高活性mtt架構型分子篩及其製造方法 |
CN103153860A (zh) * | 2010-11-05 | 2013-06-12 | 雪佛龙美国公司 | 制备小晶粒ssz-32的方法 |
CN106458616A (zh) * | 2014-05-21 | 2017-02-22 | 雪佛龙美国公司 | 分子筛ssz‑95 |
CN106458615A (zh) * | 2014-05-21 | 2017-02-22 | 雪佛龙美国公司 | 使用分子筛ssz‑95的方法 |
CN106458616B (zh) * | 2014-05-21 | 2019-05-14 | 雪佛龙美国公司 | 分子筛ssz-95 |
CN106458615B (zh) * | 2014-05-21 | 2019-05-14 | 雪佛龙美国公司 | 使用分子筛ssz-95的方法 |
CN107848820B (zh) * | 2015-09-11 | 2020-08-14 | 雪佛龙美国公司 | 制备沸石ssz-98的方法 |
CN105645428A (zh) * | 2016-02-29 | 2016-06-08 | 中国科学院山西煤炭化学研究所 | 具有介孔-微孔分等级结构的ssz-32分子筛的制备方法 |
CN106745029A (zh) * | 2017-01-22 | 2017-05-31 | 天津大学 | 一种无模板剂快速合成ssz‑32分子筛的方法 |
Also Published As
Publication number | Publication date |
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US20070041898A1 (en) | 2007-02-22 |
EA200600883A1 (ru) | 2007-02-27 |
WO2005042144A2 (en) | 2005-05-12 |
ZA200603295B (en) | 2007-10-31 |
BRPI0415948A (pt) | 2007-01-02 |
SG148146A1 (en) | 2008-12-31 |
US7390763B2 (en) | 2008-06-24 |
US7468126B2 (en) | 2008-12-23 |
SG148145A1 (en) | 2008-12-31 |
CA2543283C (en) | 2011-09-13 |
JP4671967B2 (ja) | 2011-04-20 |
SG148147A1 (en) | 2008-12-31 |
WO2005042144A3 (en) | 2006-10-19 |
CN100587035C (zh) | 2010-02-03 |
KR100804732B1 (ko) | 2008-02-19 |
US7569507B2 (en) | 2009-08-04 |
CA2543283A1 (en) | 2005-05-12 |
US20050092651A1 (en) | 2005-05-05 |
JP2007511457A (ja) | 2007-05-10 |
EP1684897A4 (en) | 2011-03-30 |
EA010635B1 (ru) | 2008-10-30 |
KR20060076323A (ko) | 2006-07-04 |
EP1684897A2 (en) | 2006-08-02 |
US20070048214A1 (en) | 2007-03-01 |
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