CN111565841A - 具有提高的中孔率的fcc催化剂、其制备和用途 - Google Patents

具有提高的中孔率的fcc催化剂、其制备和用途 Download PDF

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Publication number
CN111565841A
CN111565841A CN201980008084.4A CN201980008084A CN111565841A CN 111565841 A CN111565841 A CN 111565841A CN 201980008084 A CN201980008084 A CN 201980008084A CN 111565841 A CN111565841 A CN 111565841A
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catalyst
rare earth
silica
zeolite
slurry
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Inventor
A·萨巴希
E·伊亚姆佩鲁马尔
N·G·瓦加斯
W·诺尔斯
A·J·勒布尔
J·A·弗兰西斯
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Albemarle Corp
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Albemarle Corp
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Publication of CN111565841A publication Critical patent/CN111565841A/zh
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Abstract

本文提供了用于制备催化剂的方法和包括提高的中孔率的催化剂。因此，在一个实施方案中，提供了一种颗粒状FCC催化剂，其包含约2至约50重量％的一种或多种超稳定的高SiO2/Al2O3比的大孔八面沸石或含稀土的USY，0至约50重量％的一种或多种稀土交换的大孔八面沸石，0至约30重量％的中小孔径沸石，约5至约45重量％的准结晶勃姆石，约0至约35重量％的微晶勃姆石，0至约25重量％的第一二氧化硅，约2至约30重量％的第二二氧化硅，约0.1至约10重量％的一种或多种稀土组分，其显示出提高的在6‑40nm范围内的中孔率，所述二氧化硅的编号对应于其在制备方法中的引入顺序。

Description

具有提高的中孔率的FCC催化剂、其制备和用途
技术领域
本发明涉及一种具有更好的物理性质和性能的催化剂组合物及其在用于裂化或转化由烃(例如像从原油加工获得的那些烃)组成的进料的方法中的用途。
背景技术
在非均相催化剂的设计和生产中的常见挑战是在活性位点的有效性和/或可及性与固定基质在赋予催化剂颗粒足够的物理强度(即耐磨损性)方面的有效性之间寻找良好的折衷。此外，需要开发具有更好的焦炭选择性的催化剂或催化体系。
在一些现有技术文献中公开了耐磨损催化剂的制备。US 4,086,187公开了通过喷雾干燥水性浆液来制备耐磨损催化剂的方法，所述水性浆液通过将(i)钠含量小于5重量％的八面沸石与(ii)高岭土、(iii)胶溶的假勃姆石和(iv)聚硅酸铵混合而制备。根据US 4,206,085的耐磨损催化剂通过喷雾干燥浆液来制备，所述浆液通过混合两种类型的酸化假勃姆石、沸石、氧化铝、粘土和聚硅酸铵或硅溶胶而制备。
WO 02/098563公开了一种制备具有高耐磨损性和高可及性的FCC催化剂的方法。催化剂通过以下来制备：将沸石、粘土和勃姆石浆化，将浆液进料到成形设备中，并使混合物成形以形成颗粒，其特征在于就在成形步骤之前使混合物去稳定。这种去稳定化是通过例如温度升高、pH升高、pH降低或加入凝胶诱导剂(诸如盐、磷酸盐、硫酸盐和(部分)胶凝的二氧化硅)来实现的。在去稳定化之前，浆液中存在的任何可胶溶化合物必须已被充分胶溶。
WO 06/067154描述了FCC催化剂、其制备和用途。它公开了一种用于制备具有高耐磨损性和高可及性的FCC催化剂的方法。催化剂通过以下来制备：将粘土、沸石、无钠二氧化硅源、准结晶勃姆石和微晶勃姆石浆化，条件是所述浆液不包含胶溶的准结晶勃姆石，b)向浆液中加入一价酸，c)将浆液的pH调节至大于3的值，和d)使浆液成形以形成颗粒。
WO2015057841公开了一种中孔催化剂，其通过将用多磷酸盐处理的基质前体与用阳离子电解质处理的金属氧化物组合而形成。即使形成的FCC催化剂的中孔体积与大孔体积的比率增加，用多磷酸盐和阳离子聚电解质进行的组合处理也在耐磨损性方面产生出人意料的改进，同时保持高的总孔体积。
美国专利号6,022,471公开了具有改进的焦炭选择性的FCC催化剂和用于将烃原料转化为较低沸点产物的FCC方法。所述催化剂包括结晶铝硅酸盐沸石、三水铝石、稀土金属化合物以及由通过离子交换法制得的二氧化硅溶胶和通过混合硅酸钠、酸和酸的铝盐制得的酸性二氧化硅溶胶中的至少一种制备的二氧化硅基质。基质材料是中孔的，其孔径在约100与
Figure BDA0002579028140000021
之间，并且可以含有两种不同类型的二氧化硅溶胶，并且优选地含有粘土组分。第一种类型的二氧化硅溶胶是通过离子交换法而制得的。第二种类型的二氧化硅溶胶是通过使硅酸钠与无机酸反应，然后加入铝盐而制得的。
发明内容
本发明涉及一种FCC催化剂，其意在用于在特定催化剂组合物上裂化烃进料以产生分子量低于进料烃的转化产物烃化合物(例如包含高汽油馏分的产物)的方法。
因此，在一个实施方案中，提供了一种颗粒状FCC催化剂，其包含约2至约50重量％的一种或多种超稳定的高SiO2/Al2O3比的大孔八面沸石(骨架SiO2/Al2O3比大于约6.5)或含稀土的USY(骨架SiO2/Al2O3比大于约6.5)，0至约50重量％的一种或多种稀土交换的大孔八面沸石，0至约30重量％的中小孔径沸石，约5至约45重量％的准结晶勃姆石(QCB)，约0至约35重量％的微晶勃姆石(MCB)，0至约25重量％的第一二氧化硅，约2至约30重量％的来自酸性胶态二氧化硅或氨稳定的胶态二氧化硅或低钠稳定的胶态二氧化硅或聚硅酸的第二二氧化硅，约0.1至约10重量％的一种或多种稀土组分和余量的粘土，其在工业上公认的失活后表现出6-40nm范围内的提高的中孔率。
在另一个实施方案中，提供了一种制造FCC催化剂的方法，其中所述方法包括：
(a)加入粘土、一种或多种勃姆石和钠稳定的胶态二氧化硅以形成浆液；
(b)用单质子酸消化浆液至pH小于4；
(c)向浆液中加入稀土交换沸石；
(d)制成超稳定沸石、酸性胶态二氧化硅和稀土组分的混合物；
(e)将此第二浆液加入第一浆液中；
(f)混合浆液，然后通过将pH提高至4.0以上使浆液去稳定；
(g)成形并收集所得的FCC催化剂；
(h)任选地，随后是根据需要的煅烧步骤和后洗涤步骤以除去过量的钠。
在另一个实施方案中，提供了一种制造FCC催化剂的方法，其中所述方法包括：
(a)加入粘土、勃姆石、钠稳定的胶态二氧化硅以形成浆液；
(b)用单质子酸消化浆液至pH小于4；
(c)向浆液中加入一种或多种沸石；
(d)在步骤(a)之后或步骤(b)之后，将稀土组分加入浆液中并混合；
(e)在上述步骤a-e的任何位置，在线加入低钠或无钠的聚硅酸或加入酸性胶态二氧化硅或氨稳定的或低钠稳定的胶体；
(f)通过将pH提高至4.0以上使浆液去稳定；
(g)成形并收集所得的FCC催化剂；
(h)任选地，随后是根据需要的煅烧和后洗涤步骤以除去过量的钠。
在另一个实施方案中，提供了一种制造FCC催化剂的方法，其中所述方法包括：
(a)加入粘土、勃姆石、胶态二氧化硅以形成浆液；
(b)用单质子酸消化浆液至pH小于4；
(c)向浆液中加入来自超稳定的Y沸石、稀土交换的超稳定的高SiO2/Al2O3Y沸石、稀土交换的Y沸石、具有Pentasil和β结构的沸石的组中的一种或多种沸石；
(d)任选地将稀土氧化物组分加入浆液中并混合；
(e)用单质子酸调节浆液pH至小于4；
(f)在上述步骤a-e的任何位置，在线加入低钠或无钠的聚硅酸或加入酸性胶态二氧化硅或氨稳定的或低钠稳定的胶体；
(g)通过将pH提高至4.0以上使浆液去稳定；
(h)成形并收集所得的FCC催化剂；
(i)任选地，随后是根据需要的煅烧和后洗涤步骤以除去过量的钠。
在又一实施方案中，提供了一种制造FCC催化剂的方法，其中所述方法包括：
(a)加入粘土、勃姆石、钠稳定的胶态二氧化硅以形成浆液；
(b)用单质子酸消化浆液至pH小于4；
(c)向浆液中加入来自超稳定的高SiO2/Al2O3Y沸石、稀土交换的USY、稀土交换的Y沸石、具有Pentasil和β结构的沸石的组中的一种或多种沸石；
(d)在步骤(a)之后或步骤(c)之后，将稀土组分加入浆液中并混合；
(e)用单质子酸调节浆液pH至小于4；
(f)在上述步骤a-e的任何位置，在线加入低钠或无钠的聚硅酸或加入酸性胶态二氧化硅或氨稳定的或低钠稳定的胶体；
(g)通过将pH提高至4.0以上使浆液去稳定；
(h)成形并收集所得的FCC催化剂；
(i)任选地，随后是根据需要的煅烧和后洗涤步骤以除去过量的钠。
与现有技术相比，所得的催化剂显示出改进的益处。例如，改进的催化剂表现出改进的磨损和更高的ABD和可及性。此外，改进的催化剂造成在恒定转化率下更好的焦炭选择性以及更高的塔底物改质。
在再一实施方案中，提供了一种用于裂化石油馏分原料的方法，所述方法包括以下步骤：
a)提供一种FCC催化剂组合物，其包含约2至约50重量％的一种或多种超稳定的高SiO2/Al2O3比的大孔八面沸石或含稀土的USY，0至约50重量％的一种或多种稀土交换的大孔八面沸石，0至约30重量％的中小孔径沸石(Pentasil、β等)，约5至约45重量％的准结晶勃姆石，约0至约35重量％的微晶勃姆石，约0至约20重量％的来自钠稳定的胶态二氧化硅的二氧化硅，约2至约30重量％的来自酸性胶态二氧化硅或氨稳定的胶态二氧化硅或低钠稳定的胶态二氧化硅或聚硅酸的二氧化硅，约0.1至约10重量％的作为氧化物的稀土组分，和余量的粘土；
b)使FCC催化剂与所述石油馏分原料在400℃至650℃范围内的温度下接触，停留时间在0.5至12秒的范围内。
根据以下包括所附权利要求的详细描述，本发明的这些以及其他实施方案、优点和特征将变得更加明显。
具体实施方式
除非另有说明，否则本文所用的重量百分比(___重量％)是基于指定物质或物质形式为其成分或组分的产品的总干基重，物质的指定形式的干基重百分比。应当进一步理解，当在本文中以某种方式将步骤或组分或元素描述为优选时，它们在本公开的初始日期是优选的，并且这些优选当然可以根据给定的情况或本领域的未来发展而变化。
一般程序
制造改进的催化剂的方法的第一步骤是将粘土源与胶态二氧化硅以及一种或多种氧化铝(勃姆石)源混合。如以下将讨论的，可以向此浆液中或在随后的步骤中任选地加入酸性胶态二氧化硅或氨稳定的或低钠稳定的胶体的第二二氧化硅源。可以将粘土、沸石、QCB、MCB、胶态二氧化硅和任选的其他组分作为干燥固体加入水中而浆化。或者，将包含单独材料的浆液混合以形成浆液。也可以将某些材料作为浆液加入，而另一些材料作为干燥固体加入。任选地，可以加入其他组分，例如水合氯化铝、硝酸铝、Al2O3、Al(OH)3、阴离子粘土(例如水滑石)、蒙脱石、海泡石、钛酸钡、钛酸钙、硅酸钙、硅酸镁、钛酸镁、混合金属氧化物、层状羟基盐、其他沸石、氧化镁、碱或盐和/或金属添加剂，诸如含有碱土金属(例如Mg、Ca和Ba)、IIIA族过渡金属、IVA族过渡金属(例如Ti、Zr)、VA族过渡金属(例如V、Nb)、VIA族过渡金属(例如Cr、Mo、W)、VIIA族过渡金属(例如Mn)、VIIIA族过渡金属(例如，Fe、Co、Ni、Ru、Rh、Pd、Pt)、IB族过渡金属(例如，Cu)、IIB族过渡金属(例如，Zn)、镧系元素(例如，La、Ce)或其混合物的化合物。可以使用这些化合物的任何添加顺序。也可以同时组合所有这些化合物。
术语“勃姆石”在工业中用于描述表现出接近于氧化铝-氢氧化物[AlO(OH)]的X射线衍射(XRD)图案的氧化铝水合物。此外，术语勃姆石通常用于描述各种氧化铝水合物，其包含不同量的水合水，具有不同的表面积、孔体积、比密度并且在热处理时表现出不同的热特性。然而，尽管它们表现出特征性勃姆石[AlO(OH)]峰，但它们的XRD图案通常在其宽度上有所变化，并且在其位置上也会发生偏移。XRD峰的尖锐度及其位置已用于指示结晶度、晶体尺寸和缺陷量。
广义上，勃姆石氧化铝有两类：准结晶勃姆石(QCB)和微晶勃姆石(MCB)。在现有技术中，准结晶勃姆石也被称为假勃姆石和凝胶状勃姆石。通常，与MCB相比，这些QCB具有更高的表面积、更大的孔和孔体积以及更低的比密度。它们容易分散在水或酸中，晶体尺寸比MCB更小，并且含有更大量的水合水分子。QCB的水合程度可具有宽范围的值，例如每摩尔Al约1.4直至约2摩尔水，通常有序地或以其他方式插在八面体层之间。一些典型的可商购获得的QCB是
Figure BDA0002579028140000081
和
Figure BDA0002579028140000082
产品。
微晶勃姆石与QCB的区别在于它们的高结晶度、相对较大的晶体尺寸、非常低的表面积和高密度。与QCB相反，MCB显示的XRD图案具有较高的峰强度和非常窄的半宽度。这是由于它们的插入的水分子的数量相对较少，晶体尺寸大，块状材料的结晶度较高以及晶体缺陷量较小。通常，插入的水分子的量可以在每摩尔Al约1直至约1.4的范围内变化。
第一二氧化硅源通常是低钠二氧化硅源，并且通常被加入初始浆液中。此类二氧化硅源的实例包括但不限于硅酸钾、硅酸钠、硅酸锂、硅酸钙、硅酸镁、硅酸钡、硅酸锶、硅酸锌、硅酸磷和硅酸钡。合适的有机硅酸盐的实例是硅酮(聚有机硅氧烷，诸如聚甲基苯基硅氧烷和聚二甲基硅氧烷)和其他包含Si-O-C-O-Si结构的化合物及其前体，诸如甲基氯硅烷、二甲基氯硅烷、三甲基氯硅烷及其混合物。优选的低钠二氧化硅源是钠稳定的胶态二氧化硅。基于最终催化剂的重量，浆液还包含约0至约25重量％、更优选约0至约20重量％的来自无钠硅源的二氧化硅。
第二二氧化硅源通常是酸性或低钠或无钠的胶态二氧化硅或者聚硅酸或者氨稳定的或其他低钠稳定的胶态二氧化硅。作为第二二氧化硅源加入的合适的硅源包括(聚)硅酸、硅酸钠、无钠硅源和有机硅源。一种此类第二二氧化硅源是钠稳定的或无钠的聚硅酸，其是通过混合适量的硫酸和水玻璃的方法在线制成的。酸性胶态二氧化硅是分散在水或任何合适的溶剂中的酸稳定的无钠或低钠的无定形胶态二氧化硅颗粒。也可以使用氨(pH＝8-10.5，PSD＝5-85nm)或低钠稳定的胶态二氧化硅(pH＝5-8，PSD＝5-85nm)代替酸性胶态二氧化硅。基于最终催化剂的重量，此第二次加入二氧化硅通常以约5至25重量％、优选约5至约20％的量加入。
第二二氧化硅源的选择可影响将材料加入上述浆液中的时间。如果使用酸性胶态二氧化硅，则可以在pH调节步骤之前的任何步骤加入二氧化硅。然而，如果第二二氧化硅源是钠稳定的或无钠的聚硅酸或者氨稳定的或低钠稳定的胶体，则应在沸石加入之后就在pH调节步骤之前加入二氧化硅。另外，由于聚硅酸的钠含量，可能需要洗涤最终催化剂以除去过量的钠。可能还需要煅烧最终催化剂。
粘土优选具有低钠含量(小于0.1重量％的Na2O)，或不含钠。合适的粘土包括高岭土、膨润土、皂石、海泡石、绿坡缕石、合成锂皂石、锂蒙脱石、英国粘土、阴离子粘土诸如水滑石和热处理或化学处理的粘土诸如偏高岭土。浆液优选包含约0至约70重量％、更优选约10至约60重量％、并且最优选约10至约50重量％的粘土。
在下一步骤中，将一价酸加入悬浮液中，引起消化。可以使用有机和无机一价酸，或其混合物。合适的一价酸的实例是甲酸、乙酸、丙酸、硝酸和盐酸。将酸以足以获得低于7、更优选在1与4之间的pH值的量加入浆液中。
然后可以加入一种或多种沸石。用于根据本发明的方法的沸石优选具有低钠含量(小于1.5重量％的Na2O)，或者不含钠。待加入的合适的沸石包括用于应用的典型沸石，诸如Y-沸石，包括HY、USY、脱铝的Y、RE-Y和RE-USY沸石β、ZSM-5、磷活化的ZSM-5、离子交换的ZSM-5、MCM-22和MCM-36、金属交换的沸石、ITQ、SAPO、ALPO及其混合物。特别地，使用一种或多种超稳定的高SiO2/Al2O3比的大孔八面沸石(骨架SiO2/Al2O3比高于约6.5)或含稀土的USY(骨架SiO2/Al2O3比高于约6.5)。特别地，在催化剂中使用约2至约50重量％的一种或多种超稳定的高Y沸石或RE-USY。另外，可以将约0至约50重量％的一种或多种稀土交换的Y沸石加入一种或多种超稳定的高Y沸石或RE-USY中。
任选地，此时可以将中小孔径的沸石加入混合物中。通常，加入量为约0至约30重量％的量。可以使用任何合适的中孔沸石。此类合适的中孔沸石包括但不限于ZSM-5、ZSM-11、ZSM-22、β或镁碱沸石。
基于氧化物形式，以盐或溶液的形式向混合物中加入约0.1至约10重量％的量的稀土组分。合适的稀土元素的实例包括但不限于镧、钇和铈。稀土通常以氢氧化物、氯化物、氧化物、硝酸盐、硫酸盐、氯氧化物、乙酸盐或碳酸盐的形式添加。优选地，基于氧化物形式，以盐或溶液形式加入约0.1至约10重量％的量硝酸镧。如上所述，可以在氧化铝的胶溶(或消化)之前或之后加入稀土组分。
然后，使上述合并的浆液通过高剪切混合器，在其中通过增加pH值使其去稳定。随后将浆液的pH调节至3以上、更优选3.5以上、甚至更优选4以上的值。浆液的pH优选不高于7，因为具有较高pH的浆液可能难以处理。可以通过向浆液中加入碱(例如，NaOH或NH4OH)来调节pH。pH调节与成形步骤之间的时间段优选为30分钟或更短，更优选小于5分钟，并且最优选小于3分钟。在此步骤中，浆液的固体含量优选为约10至约45重量％，更优选约15至约40重量％，并且最优选约25至约35重量％。
然后使浆液成形。合适的成形方法包括喷雾干燥、脉冲干燥、造粒、挤出(任选地与捏合组合)、成珠或在催化剂和吸收剂领域中使用的任何其他常规成形方法或其组合。优选的成形方法是喷雾干燥。如果通过喷雾干燥使催化剂成形，则喷雾干燥器的入口温度优选在300℃至600℃范围内，并且出口温度优选在105℃至200℃范围内。
所得的催化剂
如此获得的催化剂具有特别好的耐磨损性和可及性。因此，本发明还涉及可通过根据本发明的方法获得的催化剂。所述催化剂通常是FCC催化剂，其包含约2至约50重量％的一种或多种超稳定的高SiO2/Al2O3比的Y沸石或RE-USY，0至约50重量％的一种或多种稀土交换的Y沸石，0至约30重量％的中小孔径沸石，约5至约35重量％的准结晶勃姆石，约0至约50重量％的微晶勃姆石，约0至约20重量％的来自钠稳定的胶态二氧化硅的二氧化硅，约2至约30重量％的来自酸性胶态二氧化硅或聚硅酸或氨稳定的胶态二氧化硅或低钠胶态二氧化硅的二氧化硅，约0.1至约10重量％的通过其氧化物测量的稀土组分和余量的粘土。
所得的催化剂的关键特征是中孔率比先前的催化剂增加。图中显示了在工业上公认的在Ni/V和蒸汽存在下的循环失活之后，由本发明催化剂以及标准基础催化剂的N2物理吸附测量得出的BJH孔径分布。这表明与标准基础催化剂相比，本发明的催化剂具有增加的在6-40nm范围内的中孔。从给出的表中可以清楚地看出，在约2.0至6nm的孔径处具有峰值的孔径分布占总孔体积的约20-30％，并且直径6至40nm的孔的孔体积占总孔体积的约55％-70％，更优选60％-70％。而基础催化剂显示具有上述孔径范围的孔的孔体积的几乎相等的结果。结果表明，本发明的催化剂将大量直径约2.0至6nm的孔移动至6至40nm的中孔。据信，中孔率的增加改进了本发明催化剂在使用渣油进料的FCC测试中的性能。据信，增加的中孔可能有利于更具选择性的裂化，特别是对于导致更少的焦炭和更高的塔底物改质的较大分子。
这些催化剂可在加氢处理催化剂、烷基化催化剂、重整催化剂、气液转化催化剂、煤转化催化剂、制氢催化剂和汽车催化剂中用作FCC催化剂或FCC添加剂。本发明的方法特别适用于流化催化裂化(FCC)。在FCC方法(其细节通常是已知的)中，催化剂通常以细颗粒状存在，其包含超过90重量％的直径在约5至约300微米范围内的颗粒。在反应器部分中，将烃原料气化并向上引导通过反应区，使得颗粒状催化剂在烃原料流中被夹带和流化。来自再生器的热催化剂与被催化剂汽化和裂化的烃进料反应。通常反应器中的温度为400℃-650℃，并且压力可以在减压、大气压或超大气压下，通常为约大气压至约5个大气压。催化方法可以是固定床、移动床或流化床，并且烃流可以与催化剂流并流或逆流。本发明的方法也适用于TCC(Thermofor催化裂化)或DCC。
实施例
在任何实验室测试之前，必须使催化剂失活以模拟精炼装置中的催化剂，这通常是用蒸汽完成的。这些样品通过在蒸汽存在下用Ni/V(其由裂化、汽提和再生步骤组成)或在较高温度下用100％蒸汽(这是工业上接受的用于FCC催化剂的失活方法)的循环失活来失活。失活步骤是本领域已知的，并且对于催化活性是必需的。在商业FCC环境中，失活会在引入催化剂后不久发生，并且不需要作为单独的步骤进行。流体微活性测试或流化床模拟测试(FST)或高级裂化评估(ACE)是本领域已知并普遍接受的用于确定催化剂的FCC裂化活性的测试。在ACE中，用一系列四个催化剂与进料比(CTO)进行测试，所述四个催化剂与进料比(CTO)通过改变注入反应器的进料的质量获得，同时对于所有运行使用相同量的催化剂。测试设备模拟已知量和组成特征的烃原料的已知量的裂化。此小型测试装置是单程装置，并且大致如ASTM 5154-10中那样操作。
根据以下实施例制备的催化剂的可及性通过将1g催化剂加入包含稀释在甲苯中的50ml真空瓦斯油的搅拌容器中来测量。溶液在容器与分光光度计之间循环，在此过程中连续测量VGO浓度。
催化剂的耐磨损性使用基本上基于用于通过空气射流测定粉末催化剂的磨损和磨耗的ASTM 5757标准测试方法的方法来测量，其结果表明，当使用上述方法测试材料时，催化剂的耐磨损性越强，观察到的所得磨损指数值越低。
根据ASTM D4641方法通过BJH方法由氮吸附等温线测量失活催化剂的孔径分布。
实施例1：使用上述方法制成四种催化剂。基础情形是商业催化剂。总沸石在基础情形中为21重量％，而在本发明的催化剂中为25重量％。制成的各种样品的组分如下所示：
Figure BDA0002579028140000131
Figure BDA0002579028140000132
基于实施例1的结果，本发明的催化剂显示出更高的表面积、更高的可及性以及至少相当的磨损性(如果没有改进的话)。
实施例2孔径分布：测试实施例1的每个样品的孔径分布。如下图所示，与基础催化剂相比，失活的催化剂显示出提高的在6至40nm范围内的中孔率。对于本发明的催化剂，在约2至6nm的孔径处具有峰值的孔径分布占总孔体积的约25％-28％，而直径6至40nm的孔的孔体积占总孔体积的约65％-68％。在基础催化剂中，直径约2至6nm的孔的孔体积贡献为约39％和44％，并且直径6至40nm的孔的孔体积贡献为49％和53％。这表明本发明的催化剂显示出提高的在6至40nm范围内的中孔，这导致改进的焦炭选择性和塔底物改质，如下表的ACE测试结果中所示。
Figure BDA0002579028140000141
Figure BDA0002579028140000142
实施例3：这些催化剂和基础催化剂在渣油进料中的ACE性能评估在下文给出。与基础对照催化剂相比，发现本发明的催化剂具有高活性。与基础催化剂相比，在恒定转化率下催化剂的焦炭选择性更好(更低的焦炭)，具有更高的塔底物改质。与基础催化剂相比，催化剂的焦炭选择率和塔底物改质的更佳性能可能与这些催化剂的中孔率增加有关。
Figure BDA0002579028140000151
实施例4：在下文给出的第二实施例中，其中通过上述方法制备本发明的催化剂。如前所述，与基础催化剂相比，本发明的本发明催化剂具有更好的结合和可及性。
Figure BDA0002579028140000152
Figure BDA0002579028140000153
同样，如下图所示，与基础催化剂相比，失活的催化剂显示出提高的在6至40nm范围内的中孔率。如前所述，对于本发明催化剂，在约2至6nm的孔径处具有峰值的孔径分布占总孔体积的约23％，而直径6至40nm的孔的孔体积占总孔体积的约69％。在基础催化剂中，直径约2至6nm的孔的孔体积贡献为约38％，并且直径6至40nm的孔的孔体积贡献为48％，这表明本发明的催化剂显示出提高的在6至40nm范围内的中孔，这导致改进的焦炭选择性和塔底物改质，如下表的ACE测试结果中所示。
Figure BDA0002579028140000161
Figure BDA0002579028140000162
Figure BDA0002579028140000171
实施例5：在下文给出的实施例中，其中通过上述方法制备本发明的催化剂。从下表可以清楚地看出，与基础情形催化剂相比，本发明的催化剂显示出更好的结合和可及性。
Figure BDA0002579028140000172
Figure BDA0002579028140000173
Figure BDA0002579028140000181
同样，在Ni、V和蒸汽存在下的失活之后，产生在5-20nm范围内的中孔，其在基础情形催化剂中是不存在的。同样，对于本发明催化剂，在约2至6nm的孔径处具有峰值的孔径分布占总孔体积的约30％，而直径6至40nm的孔的孔体积占总孔体积的约60％，而基础情形催化剂在上述孔径范围内的孔体积贡献几乎相等。胶态二氧化硅减少50％的催化剂也显示出相当的孔体积贡献。如下表所示，在使用渣油进料的ACE性能测试中揭示了在本发明的催化剂中产生的中孔的益处。
Figure BDA0002579028140000182
Figure BDA0002579028140000191
Figure BDA0002579028140000192

Claims (23)

1.一种FCC催化剂组合物，其包含约2至约50重量％的选自一种或多种超稳定的或稀土交换的超稳定的高SiO2/Al2O3比的Y的组中的第一沸石，任选地0至约50重量％的一种或多种稀土交换的Y沸石的第二沸石，任选地0至30重量％的中小孔沸石，约5至约45重量％的准结晶勃姆石，约0至约35重量％的微晶勃姆石，约0至约20重量％的第一二氧化硅，约2至约30重量％的第二二氧化硅，约0.1至约10重量％的作为氧化物的一种或多种稀土组分，和余量的粘土。
2.如权利要求1所述的FCC催化剂，其中与标准基础催化剂相比，所述催化剂具有增加的在6-40nm范围内的中孔。
3.如权利要求1所述的FCC催化剂，其还包含在约2.0至约6nm的孔径处具有峰值的孔径分布。
4.如权利要求1所述的FCC催化剂，其具有由直径约2.0nm至约6nm的孔贡献的总孔体积的约20％至约30％，以及直径约6至40nm的孔的孔体积的约55％至约70％。
5.如权利要求1所述的FCC催化剂，其中所述第一沸石是一种或多种超稳定的高SiO2/Al2O3比的Y沸石。
6.如权利要求1所述的FCC催化剂，其中所述第一沸石是一种或多种稀土交换的超稳定的高SiO2/Al2O3比的Y。
7.如权利要求1所述的FCC催化剂，其中所述一种或多种稀土组分包括镧、钇、铈或其混合物。
8.如权利要求1所述的FCC催化剂，其中所述一种或多种稀土组分包括镧。
9.如权利要求1所述的FCC催化剂，其中将所述一种或多种稀土组分以氢氧化物、氯化物、氧化物、硝酸盐、硫酸盐、氯氧化物、乙酸盐或碳酸盐的形式加入所述催化剂中。
10.如权利要求8所述的FCC催化剂，其中所述一种或多种稀土组分包括硝酸镧。
11.如权利要求1所述的FCC催化剂，其中所述中孔沸石包括ZSM-5、ZSM-11、ZSM-22、β、镁碱沸石或其混合物。
12.如权利要求1所述的FCC催化剂，其中所述第一二氧化硅包括钠稳定的胶态二氧化硅。
13.如权利要求1所述的FCC催化剂，其中所述第二二氧化硅包括酸性胶态二氧化硅或氨稳定的胶态二氧化硅或低钠稳定的胶态二氧化硅或聚硅酸或其混合物。
14.一种用于制造本发明的催化剂组合物的方法，所述催化剂组合物通过以下制备：
a.加入粘土、勃姆石、第一二氧化硅以形成浆液；
b.用单质子酸消化所述浆液至pH小于4；
c.向所述浆液和其混合物中加入来自超稳定的高SiO2/Al2O3 Y沸石、稀土交换的USY、稀土交换的Y沸石、具有Pentasil和β结构的沸石的组中的一种或多种沸石；
d.在步骤(a)之后或步骤(c)之后，将稀土组分加入所述浆液中并混合；
e.用单质子酸调节所述浆液pH至小于4；
f.在上述步骤a-e的任何位置，加入第二二氧化硅；
g.通过将pH提高至4.0以上使所述浆液去稳定；
h.成形并收集所得的催化剂。
i.任选地，随后是根据需要的煅烧和后洗涤步骤以除去过量的钠。
15.如权利要求14所述的方法，其中所述第一二氧化硅包括钠稳定的胶态二氧化硅。
16.如权利要求14所述的方法，其中所述第二二氧化硅包括酸性胶态二氧化硅或氨稳定的胶态二氧化硅或低钠稳定的胶态二氧化硅或聚硅酸或其混合物。
17.如权利要求14所述的方法，其中将所述一种或多种稀土组分以氢氧化物、氯化物、氧化物、硝酸盐、硫酸盐、氯氧化物、乙酸盐或碳酸盐的形式加入所述催化剂中。
18.如权利要求17所述的方法，其中所述一种或多种稀土组分包括硝酸镧。
19.如权利要求14所述的方法，其中与标准基础催化剂相比，所述所得的催化剂具有增加的在6-40nm范围内的中孔。
20.如权利要求14所述的方法，其中所述所得的催化剂还包括在约2.0至约6nm的孔径处具有峰值的孔径分布。
21.如权利要求14所述的方法，其中所述所得的催化剂还包括由直径约2.0nm至约6nm的孔贡献的总孔体积的约20％至约30％，以及直径约6至40nm的总孔体积的55％至约70％。
22.一种由权利要求14所述的方法制造的FCC催化剂组合物，其包含约2至约50重量％的选自一种或多种超稳定的或稀土交换的超稳定的高SiO2/Al2O3比的Y的组中的第一沸石，任选地0至约50重量％的一种或多种稀土交换的Y沸石的第二沸石，任选地0至30重量％的中小孔沸石，约5至约45重量％的准结晶勃姆石，约0至约35重量％的微晶勃姆石，约0至约20重量％的第一二氧化硅，约2至约30重量％的第二二氧化硅，约0.1至约10重量％的作为氧化物的一种或多种稀土组分，和余量的粘土。
23.一种用于裂化石油馏分原料的方法，所述方法包括以下步骤：
a)约2至约50重量％的选自一种或多种超稳定的或稀土交换的超稳定的高SiO2/Al2O3比的Y的组中的第一沸石，任选地0至约50重量％的一种或多种稀土交换的Y沸石的第二沸石，任选地0至30重量％的中小孔沸石，约5至约45重量％的准结晶勃姆石，约0至约35重量％的微晶勃姆石，约0至约20重量％的第一二氧化硅，约2至约30重量％的第二二氧化硅，约0.1至约10重量％的作为氧化物的一种或多种稀土组分，和余量的粘土；
b)使所述FCC催化剂与所述石油馏分原料在400℃至650℃范围内的温度下接触，停留时间在0.5至12秒的范围内。
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Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201913501D0 (en) * 2019-09-19 2019-11-06 Johnson Matthey Plc Acylation coupling method
CN116406315A (zh) * 2020-10-30 2023-07-07 雅宝公司 具有增加的污染物耐受性的基本上不含粘土的fcc催化剂、其制备和用途
CA3204869A1 (en) 2021-01-15 2022-07-21 Daniel Evans Fcc catalyst additive with pseudo solid state crsytallized zeolite
EP4363525A1 (en) * 2021-06-30 2024-05-08 Albemarle Corporation Fcc catalyst with ultrastable zeolite and transitional alumina and its use
JP2024067001A (ja) * 2022-11-02 2024-05-16 東ソー株式会社 ゼオライト成形体

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030003035A1 (en) * 2001-05-10 2003-01-02 Dennis Stamires Continuous process and apparatus for the efficient conversion of inorganic solid particles
US20030166453A1 (en) * 2002-02-25 2003-09-04 Kuvettu Mohan Prabhu Stabilized dual zeolite single particle catalyst composition and a process thereof
CN1630553A (zh) * 2001-10-17 2005-06-22 恩格哈德公司 用于含有镍和钒的原料的fcc催化剂
WO2007006047A2 (en) * 2005-07-01 2007-01-11 Albemarle Netherlands Bv Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component
CN1964785A (zh) * 2004-06-08 2007-05-16 埃克森美孚研究工程公司 使用中孔催化剂的fcc法
CN101119802A (zh) * 2004-12-21 2008-02-06 雅宝荷兰有限责任公司 Fcc催化剂及其制备和应用
CN103703105A (zh) * 2011-07-06 2014-04-02 瑞来斯实业有限公司 催化剂/添加剂的工艺和组成物，用于降低流化床催化裂化（fcc）过程中的燃料气收率

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4086187A (en) 1976-06-17 1978-04-25 Filtrol Corporation Attrition resistant zeolitic catalyst
US4206085A (en) 1979-01-15 1980-06-03 Filtrol Corporation Balanced alumina matrix in zeolite containing catalyst
US6022471A (en) 1996-10-15 2000-02-08 Exxon Research And Engineering Company Mesoporous FCC catalyst formulated with gibbsite and rare earth oxide
US20050250642A1 (en) * 2001-05-10 2005-11-10 Dennis Stamires Continuous process and apparatus for the efficient conversion of inorganic solid particles
EP1264635A1 (en) 2001-06-05 2002-12-11 Akzo Nobel N.V. Process for the production of catalysts with improved accessibility
JP4272868B2 (ja) * 2002-10-08 2009-06-03 日揮触媒化成株式会社 炭化水素接触分解用触媒組成物の製造方法
WO2005123252A1 (en) 2004-06-08 2005-12-29 Exxonmobil Research And Engineering Company Fcc process using mesoporous catalyst
JP5255844B2 (ja) 2004-12-21 2013-08-07 アルベマール・ネーザーランズ・ベー・ブイ 触媒、これらの製造方法およびこれらの使用
CA2539231C (en) 2006-03-10 2013-08-13 Baojian Shen Catalyst composition for treating heavy feedstocks
CN101332433B (zh) 2007-06-27 2011-07-20 中国石油化工股份有限公司 一种催化裂化催化剂及其制备和应用方法
EP2027917A1 (en) * 2007-07-31 2009-02-25 Shell Internationale Researchmaatschappij B.V. Catalyst composition, its preparation and use
CN103157507B (zh) 2011-12-15 2015-05-13 中国石油天然气股份有限公司 一种重油催化裂化催化剂及其制备方法
CN103447070A (zh) 2012-06-01 2013-12-18 湖北赛因化工有限公司 一种含硅粘结剂的fcc催化剂及其制备方法
SG11201501897RA (en) 2012-09-14 2015-04-29 China Petroleum & Chemical A catalytic cracking catalyst having a rare earth-containing y zeolite and a preparation process thereof
US20150101961A1 (en) 2013-10-15 2015-04-16 Basf Corporation Mesoporous fcc catalysts with excellent attrition resistance
CN106660034A (zh) 2014-05-22 2017-05-10 沙特阿拉伯石油公司 用于流化催化裂化的骨架取代沸石催化剂，和用于流化催化裂化的方法
CA3032811A1 (en) * 2016-08-04 2018-02-08 Albemarle Corporation Fcc catalyst with more than one silica, its preparation and use

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030003035A1 (en) * 2001-05-10 2003-01-02 Dennis Stamires Continuous process and apparatus for the efficient conversion of inorganic solid particles
CN1630553A (zh) * 2001-10-17 2005-06-22 恩格哈德公司 用于含有镍和钒的原料的fcc催化剂
US20030166453A1 (en) * 2002-02-25 2003-09-04 Kuvettu Mohan Prabhu Stabilized dual zeolite single particle catalyst composition and a process thereof
CN1964785A (zh) * 2004-06-08 2007-05-16 埃克森美孚研究工程公司 使用中孔催化剂的fcc法
CN101119802A (zh) * 2004-12-21 2008-02-06 雅宝荷兰有限责任公司 Fcc催化剂及其制备和应用
WO2007006047A2 (en) * 2005-07-01 2007-01-11 Albemarle Netherlands Bv Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component
CN103703105A (zh) * 2011-07-06 2014-04-02 瑞来斯实业有限公司 催化剂/添加剂的工艺和组成物，用于降低流化床催化裂化（fcc）过程中的燃料气收率

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