CN1368937A - 含有添加剂的准晶体勃姆石 - Google Patents

含有添加剂的准晶体勃姆石 Download PDF

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CN1368937A
CN1368937A CN00811389A CN00811389A CN1368937A CN 1368937 A CN1368937 A CN 1368937A CN 00811389 A CN00811389 A CN 00811389A CN 00811389 A CN00811389 A CN 00811389A CN 1368937 A CN1368937 A CN 1368937A
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additive
crystalline boehmites
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D·斯塔米里斯
P·奥康纳
G·皮尔森
W·琼斯
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Albemarle Netherlands BV
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Abstract

本发明涉及一种含有均匀分散的添加剂的准晶体勃姆石。适合的添加剂为含有选自碱土金属、碱金属、过渡金属、锕系元素、硅、镓、硼、钛和磷的元素的化合物。所述的本发明的QCB可以按照几种方式制备。通常,将准晶体勃姆石前体和添加剂转化成含有均匀分散的添加剂的准晶体勃姆石。本申请还涉及含有准晶体勃姆石的成型颗粒及催化剂,以及可以由这类准晶体勃姆石得到的过渡型氧化铝,以及含有这类过渡型氧化铝的催化剂组合物。

Description

含有添加剂的准晶体勃姆石
本发明涉及含有添加剂的准晶体勃姆石。氧化铝、α-一水合物或勃姆石及其脱水和或烧结形式是一些应用最广泛的氧化铝-氢氧化铝材料。一些主要的工业应用如陶瓷、研磨材料、阻燃剂、吸附剂、复合材料中的催化剂填料等等,均涉及这些材料中的一种或多种。另外,大部分工业勃姆石氧化铝均用于催化用途,如精制催化剂、加氢处理烃类进料的催化剂、重整催化剂、控制污染的催化剂、裂解催化剂。本文中术语“加氢处理”包括在升温、升压下烃类进料与氢反应的所有过程。这些过程包括加氢脱硫、加氢脱氮、加氢脱金属、加氢脱芳、加氢异构化、加氢脱蜡、加氢裂解及在温和压力条件下的加氢裂解,通常称之为温和加氢裂解。这类氧化铝也用作特定化学过程的催化剂,如环氧乙烷的制备及甲醇的合成。相对而言勃姆石类氧化铝或其改进形式更为近期的工业应用包括转化对环境不友好的化学组分如氯氟代烃(CFCs)及其它不希望的污染物。勃姆石类氧化铝还用作燃气轮机还原氮氧化物的催化剂材料。
这些材料在如此众多的工业应用中具有广泛和多样的成功应用的主要原因是它的灵活性,这使得它们能够制作成具有广泛的物化及机械性能的产品。
决定其工业应用包括气固相的相互作用,例如催化剂与吸附剂适用性的一些主要性能有孔体积、孔径分布、孔结构、比密度、表面积、密度及活性中心的类型、碱度和酸度、挤压强度、磨损性能、热和水热陈化性能(烧结性能)以及其长期的稳定性。
大体上,通过选择和用心控制一些参数可以获得所要求的氧化铝产品的性能。这些参数通常包括:原料、杂质、沉淀或转化过程的条件、陈化条件以及后续的热处理(煅烧/汽蒸),以及机械处理。
然而,尽管已知这项专门技术的如此广泛和多样的范围,该技术仍处于发展阶段,并且对生产者和最终的应用者来说,进一步开发这种以氧化铝为基础的材料,存在着无限的科学和技术挑战。
术语勃姆石在工业上用来描述氧化铝水合物,其XRD图形接近于氧化铝-氢氧化铝[AlO(OH)],该物质为自然存在的勃姆石或一水硬铝石。另外,通用术语勃姆石可用来描述较宽范围的氧化铝水合物,这些物质含有不同量的水合水,具有不同的表面积、孔体积及比密度,并且在热处理时表现出不同的热特性。虽然它们的XRD图形显示出特定的勃姆石[AlO(OH)]峰,但是它们的宽度通常会变化,并且也可能改变位置。XRD峰的尖锐程度及其位置均被用于表明其结晶度、晶体尺寸以及其杂质的量。
大体上有两类勃姆石氧化铝。通常第一类包括在接近100℃的温度下合成和/或陈化的、大部分时间处于环境大气压力下的勃姆石。在本说明书中,这类勃姆石被称为准-晶体勃姆石。第二类勃姆石就是所谓的微晶体勃姆石。
在现有技术中,第一类勃姆石,即准晶体勃姆石,可相互替换地称为:假勃姆石、凝胶态勃姆石或准晶体勃姆石(QCBs)。通常这些QCB氧化铝有非常高的表面积、大的孔和孔体积,以及比微晶体勃姆石更低的比密度。它们很容易分散在酸的水溶液中,具有比微晶体勃姆石更小的晶体尺寸,并且含有更大数目的水合水分子。QCB的水合程度可以具有宽的取值范围,例如每摩尔AlO,含有大约1.4到大约2摩尔的水,通常可以有序地嵌入或另外位于八面体层间。
从QCB材料中释放出来的水作为温度函数的DTG(差热分析)曲线表明,同更接近晶体的勃姆石相比,主峰出现在低得多的温度下。
QCBs的XRD图形显示了很宽的峰,其半宽值表明晶体尺寸以及晶体完美程度。
最大强度处半宽值的加宽大体上是变化的,并且对于QCBs来说通常为大约2°-6°的2θ。另外随着嵌入QCB晶体中的水量增加,XRD主反射峰(020)移到更低的2θ值,对应于更大的d间隔。一些通常在工业上可以获得的QCB为:Condea Pural、Catapal和Versal产品。
第二类勃姆石为微晶体勃姆石(MCBs),与QCBs的区别在于它们高的结晶度、相对大的晶体尺寸、很低的表面积及高的密度。与QCBs不同,MCBs所显示的XRD图形具有更高的峰强度和很窄的半峰线宽。这是由于相对少的嵌入水分子数、大的晶体尺寸、主体材料更高的结晶度以及更少量的不完美结晶的存在。通常对于每摩尔AlO,嵌入的水分子数可以从1左右变化至1.4左右。在最大强度的半峰宽处XRD的主反射峰(020)的宽度为大约1.5至大约0.1度的2-θ(2θ)。针对本发明的目的,我们定义准晶体勃姆石在020峰最大强度的半峰宽为1.5或大于1.5°。
通常工业上可以获得的MCB产品为Condea的P-200级别的氧化铝。总之在QCB和MCB两类勃姆石之间基本的特征性区别包括下列不同:三维网格序列、晶体尺寸、嵌在八面体层间的水量,以及晶体的不完美程度。
对于工业制备这些勃姆石氧化铝来说,QCBs最常用的制备过程包括:
用碱中和铝盐、酸化铝盐、水解烷氧基铝、使金属铝(汞齐化的)与水反应,以及将煅烧三水铝石得到的无定形ρ-氧化铝重新水合。通常MCB型勃姆石氧化铝可利用通常在高于150℃的温度和自身压力下通过水热过程进行工业制备。这些过程通常包括水解铝盐形成凝胶态氧化铝,然后在升温、升压下在高压釜中对其进行水热陈化。在US3,357,791中描述了这类过程。针对这一基本过程存在几种变形,包括不同的起始铝源、在陈化过程中加入酸或盐,以及较宽范围内的过程条件。
还可通过水热处理三水铝石来制备MCBs。针对这些过程的改变包括:在水热处理过程中加入酸、碱金属和盐,以及使用勃姆石晶种增大三水铝石到MCB的转化率。在Alcoa的US5,194,243、US4,117,105和US4,797,139中也描述了这类过程。
然而,无论是假-、准-或微晶体,这些勃姆石材料的特征均在于其粉末的X光衍射。ICDD包括进入勃姆石并且确定应该有对应于(020)、(021)和(041)平面的反射。对于铜射线,这些反射应出现在14、28和38度的2-θ处。各种勃姆石形式可通过反射的相对强度和宽度来区分。许多作者已经确认了针对结晶程度而言的反射的精确位置。而靠近上述位置的线会指示一种或多种勃姆石相的存在。
在现有技术中,我们发现含有金属离子的QCBs可以通过水解与镧系元素共沉淀的异丙氧基铝来制备,正如J.Medena的论文J.Catalysis,Vol.37(1975),91-100,以及J.Wachowski等人,Materials Chemistry,Vol.37(1994),29-38中所描述的。其产物为包藏有一种或多种镧系金属离子的假-勃姆石型氧化铝。这些材料主要用于高温工业用途,其中在假勃姆石结构中存在这些镧系金属离子延迟了γ-氧化铝向α-氧化铝相的转化。因此实现了γ相的稳定,即在转化成耐火的、比表面积较小的α-氧化铝之前,保持较高的表面积。具体地,Wachowski等人使用1-10%wt的镧系元素离子(La,Ce,Pr,Nd,Sm),在500-1200℃的温度范围内进行煅烧。WachoWski等没有提供有关500℃以下时材料的性能和状态的信息,这是有关催化剂应用的最重要的区域。
另外,EP-A1-0 597 738描述了通过加入镧,任选与钕组合,来实现氧化铝的热稳定。这种材料是在70-110℃的温度下,在含有镧盐的浆液中陈化快速煅烧过的三水铝石,然后在100-1000℃的温度下进行热处理而制备的。
其终产物与Wachowski等人所制备的产物一样,均是高温耐火的(陶瓷)材料,这种材料由于其极高密度的主体结构、很低的表面积以及小的孔在非均相催化中的应用很有限,特别是用于烃类转化或重整的催化剂,例如FCC及加氢处理的工业应用。
另外,EP-A-0 130 835描述了一种含有载带在镧或钕-β-Al2O3载体上的催化活性金属的催化剂。所述的载体是在镧、镨或钕盐溶液存在时,利用氢氧化铵沉淀硝酸铝溶液而制备的。由于沉淀后的无定形材料是直接用水洗涤并过滤的,因此在通常条件及一定pH值、浓度及温度下,氧化铝不必花时间进行陈化,以至于结晶成勃姆石氧化铝结构。
本发明涉及准晶体勃姆石,其中一种添加剂处于均匀分散状态,并且所述的添加剂不是镧系元素。
本发明的QCB中的添加剂有助于调节QCB的物理、化学及催化性能,如比密度、表面积、孔径分布、孔体积、密度及活性中心的类型、碱度和酸度、挤压强度、磨损性能等等,这些性能决定了勃姆石用作催化或吸附材料的适用性。事实是均匀分散在QCB内部的添加剂使本发明的QCBs与利用添加剂浸渍过的QCBs区分开来,并且使这些新的QCBs极其适用于催化目的或作为制备非均相催化反应催化剂的起始原料。针对本发明的目的,如果在X光衍射图中没有添加剂的反射,则说明添加剂均匀分散在QCB中,因此添加剂不是作为分散相存在。当然,也可以将不同类型的添加剂结合到本发明的QCB中。
适合的添加剂为含有选自碱土金属、碱金属、过渡金属、锕系元素、贵金属如Pt和Pd、硅、镓、硼、钛和磷的元素的化合物。例如,硅的存在增加了勃姆石中酸位的量,过渡金属引入了催化或吸附活性,如捕集SOx、捕集NOx、加氢、加氢转化及其它的气/固相互作用的催化体系。
适合的含有所需元素的化合物为硝酸盐、硫酸盐、氯化物、甲酸盐、乙酸盐、碳酸盐、钒酸盐等等。使用带有可分解的阴离子的化合物是优选的,因为所形成的带有添加剂的QCBs可以直接干燥,不需要任何洗涤,因为催化目的所不需要的阴离子是不存在的。
当然,除了上述添加剂外,含有稀土金属的化合物也可以存在于本发明的准晶体勃姆石中。
所述的本发明的QCBs可以按照几种方式进行制备。通常将准晶体勃姆石前体与添加剂转化成含有均匀分散的添加剂的准晶体勃姆石。适合的制备方法的例子如下文所述:
方法1
可以在含有所需添加剂的化合物存在时,通过水解并陈化烷氧基铝来制备QCB。可以在水解步骤过程中加入添加剂,或者在陈化步骤结束之前加入。
方法2
可以通过水解并沉淀可溶性铝盐的氢氧化物,并且陈化形成含有添加剂的QCB,从而制备QCB。适合的铝盐例子有硫酸铝、硝酸铝、氯化铝、铝酸钠以及它们的混合物。可以在水解和共沉淀进行时或者在陈化步骤结束时加入添加剂。
方法3
也可以在80-130℃的温度下,优选在90-110℃的温度下,使含有热处理后的三水合铝及添加剂的浆液陈化足够长的时间形成QCBs,从而制备QCB。热处理后的三水合铝为煅烧后的三水合铝和快速煅烧后的三水合铝(CP氧化铝)。这种制备方法的优点在于除了添加剂化合物中存在的所有离子外,没有其它的离子被引入QCB中。这意味着在适当选择添加剂化合物的情况下,洗涤步骤可以减少或完全不用。例如,当使用可分解的阴离子(如碳酸根、硝酸根和甲酸根)时,可以直接干燥含有添加剂的QCB,因为并不存在催化作用所不需要的阳离子。该制备方法的另一优点是可以首先使含有热处理后的三水合铝及添加剂的浆液成型,再使成型体重新形成浆液,然后陈化成型体形成QCBs。在本说明书中,成型定义为所有能够得到具有适当尺寸及强度的用于特定目的的颗粒的方法。适当的成型方法有喷射干燥、挤出成型(任选与中间喷射干燥、滤压和/或揉制一起使用)、制成球、珠或其它任何在催化剂或吸附剂领域常用的成型方法,以及它们的组合。
方法4
也可以在80-130℃的温度下,优选在90-110℃的温度下,使含有无定形凝胶氧化铝和添加剂的浆液陈化形成QCBs,从而制备QCB。与上述方法3相似,该制备方法的优点也是除了添加剂化合物离子外,没有其它的离子被引入QCB中。这意味着在适当选择添加剂化合物的情况下,洗涤步骤可以减少或完全不用。另外也可以首先使含有无定形氧化铝凝胶和添加剂的浆液成型,再使成型体重新形成浆液,然后陈化成型体形成QCBs。在这种情况下,应该注意选择成型步骤,使其中无定形凝胶氧化铝/添加剂混合物的加热温度不超过陈化温度。
方法5
也可以在所需要的添加剂化合物存在时,通过热或水热处理陈化相对无定形的QCB形成含有均匀分散的添加剂的QCB,从而制备本发明的QCBs。结晶度增大一定的程度,但所形成的产品仍然是本发明所定义的QCB。该方法也可以在(水)热处理之前,使QCB-添加剂混合物成型。另外除了添加剂化合物的离子外,没有其它离子被引入QCB中。
方法6
也可以在所需要的添加剂化合物存在时,通过水热处理,借助于适当的勃姆石晶种,陈化三水合氧化铝如三水铝石、BOC及三羟铝石,来制备QCBs。适合的晶种是制备微晶体勃姆石已知的晶种,如工业上可以得到的勃姆石(Catapal,CondeaVersal,P-200等等)、无定形晶种、磨碎的勃姆石晶种、由铝酸钠溶液制备的勃姆石等等。另外由本申请所述的方法之一制备的准晶体勃姆石也可以适当地用作晶种。与方法3、4和5类似,除了添加剂的离子以外,没有其它离子被引入QCB中,并且该方法可以在陈化步骤之前进行成型。
尽管上述方法5和6对制备微晶体勃姆石来说是已知的,但我们发现这些方法可以通过调节所使用的晶种、pH以及水热条件也可以用于形成QCBs。
针对在水热处理转化三水合铝的过程中使用晶种的最早的出版物可以追溯到40年代后期及50年代早期。例如G.Yamaguchi和K.Sakamato(1959)清楚地证明了一个概念,即勃姆石晶种主要通过降低温度、缩短反应时间及增大三水铝石的转化率,从而改善了三水铝石水热转化成勃姆石的动力学。
另外G.Yamaguchi和H.Yamanida(1963)也清楚地证明了在升高的温度及自身压力下运行的高压釜中,在水热转化三水铝石的过程中,利用勃姆石作晶种的有益原则。
在公开的文献中,还有几篇其它的出版物,其中证明了利用勃姆石和/或碱溶液作晶种具有同样的好处。另外,生产粒度更细、更容易分散在水中的勃姆石产品要使用勃姆石晶种。在1987年12月16日申请的US4,797,139及1985年9月30日申请的US5,194,243中均描述了在三水铝石水热转化的过程中使用勃姆石晶种。
上面描述的所有方法均可以按间歇或连续方式进行,任选在连续的多步操作中进行。这些方法也可以部分连续、部分间歇地进行。
如上文所述,虽然应该注意所采用的反应条件应使前体能转化成QCB,但仍可使用多种QCB前体。所述的QCB前体混合物可以在引入添加剂之前制备,或者可以在任何其它反应阶段中加入不同类型的前体。
在制备本发明QCBs的方法中,可以采用多个陈化步骤,例如其中陈化温度和/或条件(热或水热、pH、时间)是变化的。
制备本发明QCBs的方法的反应产物也可以循环回到反应器中。
如果将多种添加剂结合到QCB中,则各种添加剂可以在任一反应步骤中同时加入或者相继加入。
优选在水解、沉淀和/或陈化步骤中加入酸或碱,以调节pH值。
如上文所述,制备本发明的准晶体勃姆石的某些方法可以在制备过程中成型,以得到成形体。也可以使最终的QCB成型,视情况可借助于粘结剂和/或填料。
如上文所述,本发明的QCBs极其适合作为催化剂组合物或催化剂添加剂的组分或起始材料。为了这一目的,视情况可将QCB与粘结剂、填料(例如粘土如高岭土、钛氧化物、氧化锆、二氧化硅、二氧化硅-氧化铝、膨润土等等)、催化活性材料如分子筛(如ZSM-5、沸石Y、USY沸石)、以及任何其它催化剂组分如通常用于催化剂组合物中的调孔添加剂组合起来使用。对于某些应用,在用作催化剂组分之前中和QCB可能是优选的,例如改进或生成孔体积。另外优选除去所有的钠,使其含量低于0.1wt%Na2O。因此本发明还涉及含有本发明QCB的催化剂组合物及催化剂添加剂。
在本发明的另一实施方案中,在生产吸附剂、陶瓷、耐火材料、基质及其它载体的进一步处理过程中,QCB可以与其它金属氧化物或氢氧化物、粘结剂、补充剂、活化剂、调孔添加剂等等混合。
针对催化目的,通常在200-1000℃的温度下使用勃姆石。在这些高温下,勃姆石通常转化成过渡型氧化铝。因此本发明还涉及过渡型氧化铝,这种氧化铝可通过对本发明的含有添加剂的准晶体勃姆石进行热处理得到,还涉及一种过渡型氧化铝,其中添加剂不是镧系元素,并且处于均匀分散状态。本发明还涉及一种过渡型氧化铝,其中所述添加剂为含有选自碱土金属、过渡金属、锕系元素、硅、硼和磷的元素的化合物。
利用上述过渡型氧化铝,可以制备催化剂组合物或催化剂添加剂,视情况可借助于粘结剂材料、填料等等。
下面将通过如下非限定性的实施例进一步描述本发明。
实施例
对比例1
得到Catapal A,购自Vista Chemicals的XRD谱图。见图1。
实施例2
在100℃的温度下,在pH为4时,利用硝酸锌溶液处理CP氧化铝(快速煅烧后的三水合铝)18小时。图2给出了所形成的QCB的XRD图形。
实施例3
在200℃的温度下,在pH为4时,利用硅酸钠溶液处理CP氧化铝(快速煅烧后的三水合铝)1小时。图3给出了所形成的QCB的XRD图形。
实施例4
在10wt%(按以氧化铝为基准的氧化物计算)的硝酸镍和6wt%(按以氧化铝为基准的氧化物计算)的硝酸钴存在时,在80℃下,通过硫酸铝和铝酸钠共沉淀达到最终pH值10,从而共沉淀出QCB。在80℃的温度下,使反应产物陈化48小时。用热的稀氢氧化铵洗涤所形成的浆液(pH8到9)。图4给出了所形成的QCB的XRD图形。
实施例5
在10wt%(按以氧化铝为基准的氧化物计算)的硝酸镍存在时,在80℃的温度下,通过硫酸铝和铝酸钠共沉淀达到最终pH值10,从而制备QCB。在80℃的温度下,使反应产物陈化48小时。
实施例6
在8wt%(按以氧化铝为基准的氧化物计算)的硝酸钴存在时,在80℃的温度下,通过硫酸铝和铝酸钠共沉淀达到最终pH值10,从而共沉淀出QCB。在80℃的温度下,使反应产物陈化48小时。
实施例7
在5wt%(按以氧化铝为基准的氧化物计算)的硝酸钼存在时,在80℃的温度下,通过硫酸铝和铝酸钠共沉淀达到最终pH值10,从而共沉淀出QCB。在80℃的温度下,使反应产物陈化48小时。
实施例8
在8wt%的硝酸钴和5wt%(二者均按以氧化铝为基准的氧化物计算)的硝酸钼存在时,在80℃的温度下,通过硫酸铝和铝酸钠共沉淀达到最终pH值10,从而共沉淀出QCB。在80℃的温度下,使反应产物陈化48小时。
实施例9
在9wt%的硝酸镍、8wt%的硝酸钴及6wt%的硝酸钼(均按以氧化铝为基准的氧化物计算)存在时,在80℃的温度下,通过硫酸铝和铝酸钠共沉淀达到最终pH值10,从而共沉淀出QCB。在80℃的温度下,使反应产物陈化48小时。
实施例10
在90℃的温度下,在pH保持为7.7时,利用5%(按氧化物计算)的硝酸钼在溶液中对CP氧化铝处理18小时。图5给出了所形成的QCB的XRD图形。
实施例11
在90℃的温度下,在pH保持为6.1时,利用10wt%(按氧化物计算)的硝酸镓在溶液中对P3氧化铝处理18小时。图6给出了所形成的QCB的XRD图形。
实施例12
在100℃的温度下,在pH为4时,利用5wt%(按氧化物计算)的硝酸钡在溶液中对CP氧化铝处理18小时。图7给出了所形成的QCB的XRD图形。

Claims (20)

1.准晶体勃姆石,其中添加剂处于均匀分散状态,所述添加剂不是镧系元素。
2.权利要求1的准晶体勃姆石,其中添加剂为含有选自碱土金属、过渡金属、锕系元素、硅、硼和磷的元素的化合物。
3.权利要求1的准晶体勃姆石,包括含有稀土金属的化合物。
4.前述权利要求中任意一项的准晶体勃姆石的制备方法,其中将准晶体勃姆石前体和添加剂转化成含有均匀分散的添加剂的准晶体勃姆石。
5.权利要求4的方法,其中使用多种准晶体勃姆石前体。
6.权利要求4或5的方法,其中将烷氧基铝水解并陈化形成含有添加剂的准晶体勃姆石。
7.权利要求4或5的方法,其中一种可溶性铝盐被水解、沉淀成氢氧化物,并被陈化形成含有添加剂的准晶体勃姆石。
8.权利要求4或5的方法,其中在添加剂存在时,在水中使热处理后的三水合铝重新水合,并且在80-130℃的温度下使所形成的浆液陈化足够长的时间,以形成准晶体勃姆石。
9.权利要求4或5的方法,其中在添加剂存在时,在水中使无定形凝胶氧化铝形成浆液,并且在80-130℃的温度下使所形成的浆液陈化足够长的时间,以形成准晶体勃姆石。
10.权利要求4或5的方法,其中在添加剂存在时,通过(水)热处理使准晶体勃姆石陈化,以形成含有均匀分散的添加剂的准晶体勃姆石。
11.权利要求4或5的方法,其中在添加剂存在时,通过(水)热处理使三水合铝陈化,以形成准晶体勃姆石。
12.前述权利要求8-11中任意一项的方法,其中在陈化步骤之前,使准晶体勃姆石前体和添加剂成型,得到含有准晶体勃姆石前体/添加剂混合物的成形体。
13.前述权利要求4-12中任意一项的方法,是以连续方式进行的。
14.前述权利要求4-13中任意一项的方法,其中反应产物循环回到反应器中。
15.前述权利要求4-14中任意一项的方法,其中应用多个陈化步骤。
16.含有前述权利要求1-3中任意一项的准晶体勃姆石的成型颗粒。
17.含有前述权利要求1-3中任意一项的准晶体勃姆石以及任选的粘结剂材料的催化剂组合物。
18.过渡型氧化铝,该氧化铝可通过热处理前述权利要求1-3中任意一项的准晶体勃姆石得到。
19.其中添加剂处于均匀分散状态的过渡型氧化铝,所述的添加剂为含有选自碱土金属、过渡金属、锕系元素、硅、硼、钛和磷的元素的化合物。
20.含有权利要求18-19中任意一项的过渡型氧化铝以及任选的粘结剂材料的催化剂组合物。
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CN101116818B (zh) * 2006-07-31 2010-12-01 中国石油化工股份有限公司 一种含金属元素的水合氧化铝及其制备方法
CN102267710A (zh) * 2010-06-03 2011-12-07 中国石油化工股份有限公司 一种含硼拟薄水铝石及由其制备的氧化铝
CN102267710B (zh) * 2010-06-03 2014-05-28 中国石油化工股份有限公司 一种含硼拟薄水铝石及由其制备的氧化铝
CN116835620A (zh) * 2023-05-30 2023-10-03 中国石油大学(华东) 一种插层-剥离勃姆石制备二维纳米片的方法

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