CN115666781A - 稳定的成型氧化铝及其生产方法 - Google Patents
稳定的成型氧化铝及其生产方法 Download PDFInfo
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- CN115666781A CN115666781A CN202180037724.1A CN202180037724A CN115666781A CN 115666781 A CN115666781 A CN 115666781A CN 202180037724 A CN202180037724 A CN 202180037724A CN 115666781 A CN115666781 A CN 115666781A
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- alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 194
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000013078 crystal Substances 0.000 claims abstract description 15
- 230000032683 aging Effects 0.000 claims abstract description 9
- 239000006185 dispersion Substances 0.000 claims description 36
- 239000011148 porous material Substances 0.000 claims description 32
- 229910001593 boehmite Inorganic materials 0.000 claims description 29
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 29
- 238000009826 distribution Methods 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 239000002019 doping agent Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 12
- 238000007493 shaping process Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000007704 transition Effects 0.000 claims description 9
- 229910052797 bismuth Inorganic materials 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910001680 bayerite Inorganic materials 0.000 claims description 2
- 229910001679 gibbsite Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003116 impacting effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- QFCVQKSWGFVMTB-UHFFFAOYSA-N trihexoxyalumane Chemical compound [Al+3].CCCCCC[O-].CCCCCC[O-].CCCCCC[O-] QFCVQKSWGFVMTB-UHFFFAOYSA-N 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum alkoxide Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 239000013618 particulate matter Substances 0.000 description 1
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- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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Abstract
本发明涉及煅烧成型氧化铝和制备煅烧成型氧化铝的方法。该方法包括将氧化铝悬浮液中的氧化铝水热老化以具有特定的晶体尺寸。这进而产生特别是在1200℃及更高的温度下呈煅烧成型氧化铝形式的高度稳定的氧化铝。
Description
技术领域
本发明涉及煅烧成型氧化铝或同义使用的“煅烧成型氧化铝载体”,以及制备煅烧成型氧化铝载体/煅烧成型氧化铝的方法。
背景技术
活性氧化铝广泛用作多种非均相催化应用的载体。一方面,这些包括固定床,也称为填充床,而另一方面,还包括移动床或流化床应用。对于固定床应用,重要的是所制备的催化剂要提供床的均匀填充以避免沟道化和温度梯度,而对于流化床或移动床应用,一个关键方面是制备稳定而牢固的催化剂,以避免催化剂颗粒因撞击反应器壁或彼此撞击而磨损或破裂。对于某些应用,对铝进行成型是有利的。特别是在固定床催化中,现有技术中提出了许多催化剂形状,以平衡所经历的催化剂活性和跨催化剂床的压降方面的困难。
如本说明书中所用,成型是指将将颗粒物聚结成更大形状(优选具有一定规则性的形状)的工艺和方法,并且成型的具有相应的含义。在这种成型之后,需要煅烧这种形状以提供强度并使形状固定。因此,本发明领域的技术人员将会理解的是,煅烧成型氧化铝/煅烧成型氧化铝载体是指,例如,优选在成形塔中成型的氧化铝球、氧化铝挤出物和氧化铝片。
US 4542113提供了一种由勃姆石氧化铝制备球状氧化铝的工艺方法。通过所公开的方法获得的球体据称具有2-3mm的直径、最高达200N/球体的抗压强度、0.45-0.75mL/g的孔体积和220-250m2/g的表面积。
对于具有特定性质,特别是特定性质的组合的改进成型催化剂载体,仍存需要。
发明内容
根据本发明的第一方面,提供了一种煅烧成型氧化铝/煅烧成型氧化铝载体,其包括以下特征a)和b):
a)30-70N,优选40-60N的抗压强度;和
b)中值孔半径为5-12nm、优选7-10nm的单分散孔半径分布。
优选所述煅烧成型氧化铝还包括一个或多个以下特征c)至f),而优选全部特征c)-f):
c)0.4-1.2cm3/g,优选0.7-1.0cm3/g的总孔体积;
d)在1200℃下煅烧3小时后,BET表面积为10-100m2/g之间,优选1200℃煅烧3小时之后,BET表面积为40-80m2/g;
e)煅烧成型氧化铝的Na、Fe和Si杂质的含量各自低于100ppm,优选各自低于50ppm;和
f)α转变温度高于1200℃,优选高于1300℃。
优选所述包括特征a)和b)的煅烧成型氧化铝至少还包括特征c)。
该煅烧成型氧化铝可以根据以下方法进行生产。
根据本发明的一个进一步的方面,提供了一种制备煅烧成型氧化铝的方法,该方法包括以下步骤:
i)制备氧化铝悬浮液,所述氧化铝悬浮液包含氧化铝和至少水;
iii)可选地干燥所述水热老化的氧化铝悬浮液以获得氧化铝粉末;
iv)可选地由所述氧化铝粉末制备氧化铝糊膏或由所述氧化铝粉末或所述水热老化的氧化铝悬浮液制备氧化铝分散体;
v)将所述氧化铝粉末或所述氧化铝糊膏或所述氧化铝分散体或所述水热老化的氧化铝悬浮液或其混合物进行成型以形成成型氧化铝;
vi)干燥所述成型氧化铝以形成干燥的成型氧化铝;和
vii)煅烧干燥的成型氧化铝以形成煅烧的成型氧化铝。
步骤iv)是可选的,因为步骤iii)的所述氧化铝粉末可以在步骤v)中直接成型。步骤iii)是可选的,因为步骤ii)的所述水热老化的氧化铝悬浮液能够直接用于步骤iv)或v)。
该煅烧成型氧化铝是煅烧成型氧化铝载体或能够用作多相催化应用的载体。
具体实施方式
该煅烧成型氧化铝可以呈优选在成形塔中成形的球状体、挤出物、片状物或其混合物的形式。该煅烧成型氧化铝优选呈球状体,即球状氧化铝。在本发明中,球状体或球形体是指球形度优选高于0.9的球状体。
在成形塔中形成球状氧化铝取决于将含氧化铝溶胶、溶液或其他混合物作为液滴引入液体中,然后将其转化为球状体。本领域技术人员已知尤其适用于将球状氧化铝颗粒成形的许多变化和改进,并且,例如,描述于US 4542113及其引用的技术中。US 4542113的公开内容通过引用结合于本文中,特别是关于通过使用成形塔的成型。
该煅烧成型氧化铝的最长尺寸为至少0.5mm(对于球体而言,最长尺寸,例如,是直径)。当该煅烧成型氧化铝呈球状氧化铝的形式时,其可以包括直径为0.5mm-3.0mm的进一步特征。
球状氧化铝的直径根据ASTM D1155标准进行测定。
根据一个实施方式,该煅烧成型氧化铝包含单分散的孔半径分布。单分散的孔半径分布是指通过汞浸入法(DIN 66133)获得的孔半径分布,其中对于1-100nm范围内的半径,仅确定一个全体最大值而没有确定局部最大值(即,孔半径分布为单峰)。这是本发明的优点之一,因为在过去的情况下,预期会有两个最大值。本发明的煅烧成型氧化铝包含5-12nm,优选7-10nm的介孔半径(median pore radius,中孔半径)。
使用标准DIN 66133(通过汞浸入法测定孔体积分布和固体比表面积)测量孔半径分布,进而测量总孔体积。
众所周知,当温度升高时,氧化铝不同相的热转化最终会导致生成α-氧化铝。通常而言,热转化的最后一步是从θ相向α相的相转化(相变,phase transition)。向α相的转化会伴随着孔隙率和表面积的损失,而通过高温煅烧生产的α-氧化铝粉末通常特征在于具有约5m2/g的低BET表面积。
根据一个实施方式,本发明的煅烧成型氧化铝的特征在于具有优异的热稳定性,即其中氧化铝抵抗向α相的相转化,并且保持处于θ相。即使在确实发生向α相的相转化的情况下,本发明的煅烧氧化铝的特征在于比对于典型α氧化铝预期的更大表面积。本文中使用的术语“热稳定性”是指对表面和/或晶相变化的热稳定性,这些变化是由温度变化引起的外部影响可能连同其他外部影响如水、化学品、压力和机械应力所引起的。例如,热稳定性可以通过根据DIN ISO 9277使用氮气的BET法测定的表面积进行表征,该表面积是样品在马弗炉中1200℃下煅烧3小时后或1300℃下煅烧3小时后(加热速率1K/min-10K/min)保持的表面积。
该煅烧成型氧化铝可以进一步包含掺杂剂。该掺杂剂优选包含稀土元素、过渡元素(元素周期表第3-11族,具体而言第4-11族的元素,具体而言元素周期表第4族(旧IUPAC编号IVb)和第5族(旧IUPAC编号Vb)的元素)以及锡和铋。掺杂剂的添加量为0-1wt%或大于0-1wt%,优选0-0.5wt%或大于0-0.5wt%,该掺杂剂的重量以元素计算,而wt%则相对于该煅烧成型氧化铝。优选该煅烧成型氧化铝掺杂过渡元素、稀土元素和元素周期表第4族(旧IUPAC编号IVb)和第5族(旧IUPAC编号Vb)的元素(更优选Sn和Bi)的有机和无机盐。最优选该煅烧成型氧化铝掺杂SnCl4或Bi(NO3)3×5H2O。
根据本发明的方法的优选实施方式进一步限定如下:
该煅烧成型氧化铝可以呈优选在成形柱中成型的球状体、挤出物、片状或其混合物的形式。该煅烧成型氧化铝的最大尺寸为至少0.5mm(对于球体,最大尺寸例如为直径)。该煅烧成型氧化铝优选是球状体,即球状氧化铝。
该氧化铝悬浮液包含氧化铝和至少水。该氧化铝悬浮液中以Al2O3计的氧化铝含量优选占该氧化铝悬浮液的2wt%-20wt%,更优选5wt%-10wt%。该氧化铝悬浮液优选通过醇盐的水解而获得。
该氧化铝悬浮液中的氧化铝可以包括勃姆石、三水铝石(gibbsite)、三羟铝石(bayerite)、过渡氧化铝(至少包括γ-氧化铝、δ-氧化铝和θ-氧化铝),并且最优选是勃姆石。例如,该勃姆石氧化铝可以通过铝醇盐在水中水解而获得。
沿(120)和(020)轴的所需晶体尺寸通过水热老化该氧化铝悬浮液而获得,其中至少该水热老化的氧化铝悬浮液包括勃姆石。该水热老化反应通常在搅拌下在60-300℃,优选80-180℃的温度下进行1-30小时,优选15-30小时。
温度和时间进行独立选择。水热老化后勃姆石沿(120)轴和(020)轴的晶体尺寸优选各自为更优选在水热老化后勃姆石具有沿(120)轴的晶体尺寸与沿(020)轴的晶体尺寸之比为0.5:1-2.0:1,优选0.9:1-1.1:1。
该氧化铝分散体包含氧化铝和至少水。该氧化铝分散体中以Al2O3测量的氧化铝含量为10wt%-40wt%,优选25wt%-35wt%。
该氧化铝分散体优选包含酸。所述可以使用的酸是有机酸或无机酸,优选硝酸、乙酸、甲酸或其混合物。该氧化铝分散体中酸的浓度可以为0.1wt%-1.5wt%,优选0.9wt%-1.2wt%。该分散体中氧化铝的粒度优选低于1μm,优选低于500nm。
此外,该氧化铝分散体可以包含沸点高于250℃的烃,具体而言是煤油。该氧化铝分散体中所含的烃,具体而言是煤油的量可以占该氧化铝分散体的大于0-10wt%,优选该氧化铝分体的大于0-5wt%。煤油是指支链和非支链烷烃的液体混合物。根据EINECS 232-384-2,典型煤油的比重为0.81-0.89g/cm3,沸点高于250℃。
在成型以形成该成型氧化铝之前,可以将掺杂剂添加到氧化铝糊膏、或氧化铝分散体、或水热老化的氧化铝悬浮液或其混合物中。该掺杂剂优选包括稀土元素、过渡元素(元素周期表的第3-11族元素,优选第4-11族元素,具体而言周期表第4族(旧IUPAC编号IVb)和第5族(旧IUPAC编号Vb)的元素)以及锡和铋。当向该氧化铝分散体中添加掺杂剂时,该氧化铝分散体优选包含0-1wt%或大于0-1wt%,优选0-0.5wt%或大于0-0.5wt%的掺杂剂,该掺杂剂的重量以元素和相对于该煅烧成型氧化铝的重量进行计算。
优选该氧化铝分散体包括稀土元素和过渡元素的有机和无机盐,特别是元素周期表第4族(旧IUPAC编号IVb)和第5族(旧的IUPAC编号Vb)的元素,更优选Sn和Bi。最优选该氧化铝分散体包含SnCl4或Bi(NO3)3×5H2O。通常包括锡和铋为了其催化作用。
该氧化铝糊膏优选包含氧化铝和酸。以Al2O3测量的氧化铝糊膏中的氧化铝含量可以为20wt%-65wt%,优选40wt%-60wt%。所述可以使用的酸是有机酸或无机酸,优选硝酸、乙酸、甲酸或其混合物。该氧化铝糊膏中酸的浓度可以为0.1wt%-4.0wt%,优选1.0wt%-2.5wt%。
优选该氧化铝分散体由氧化铝粉末进行制备。
本发明的煅烧成型氧化铝是通过使用本领域已知的各种技术对氧化铝粉末、或氧化铝糊膏、或氧化铝分散体或水热老化的氧化铝悬浮液或其混合物进行成型而获得。例如,为了制备球状体,该氧化铝分散体以液滴的形式滴入成形塔中。为了形成挤出物或片状物,使用本领域已知的技术挤出或压制所述氧化铝粉末或氧化铝糊膏。
根据本发明的一个实施方式,该成型氧化铝优选在90-150℃温度下,更优选110-130℃的温度下干燥,并且优选与其独立地通过使用静态烘箱或带式干燥器以2-24小时的停留时间进行干燥。这种干燥技术对于本发明领域的技术人员而言是已知的。
根据本发明的一个实施方式,煅烧在450-1100℃,优选550-750℃的温度下,通常在马弗炉或窑中,以10分钟-10小时,优选2-4小时的停留时间进行。温度和时间独立地进行选择。
本发明现在将参照非限制性实施例和附图进行描述,其中:
图1显示了比较实施例1和2(样品1和2)以及实施例1和6(样品3a和7)的孔半径分布;
图2显示了在不同温度下煅烧的实施例1和2的孔半径分布;
图3显示了包含不同掺杂剂的实施例4和5(样品5和6)的孔半径分布;
图4显示了比较实施例1和实施例1的DSC(差示扫描量热法)-TG(热重法)分析;和
图5是比较实施例2和实施例1在1200℃下煅烧3小时后的X-射线衍射图;
图6显示了比较实施例3的孔半径分布。
实施例
分析方法和定义
根据本发明的勃姆石的晶体尺寸使用通用Scherrer公式沿(120)和(020)轴进行确定:
晶体尺寸=(K×λ×57.3)/(β×cosθ)
其中:
K(形状系数): 0.992
λ(X-射线波长): 0.154nm
β(仪器的校正线展宽): 反射依赖(reflex dependent)
θ: 反射依赖
使用Bruker CubiX3仪器进行这些测量。勃姆石的测量参数为沿(120)轴反射的θ=14°,而沿(020)轴反射的θ=7°,两种反射的β=0.919。
本文所提供的比表面积根据DIN-ISO 9277通过使用氮气的BET法测量。
球状氧化铝的直径根据ASTM D1155测定。
根据ASTM D6175测定挤出物的压碎强度,而根据ASTM D4179测定其他形状的压碎强度。
DSC根据DIN 51007进行测定。
如ISO 13322-2(2006)中所述,球形度通过使用Retsch的Camsizer P4进行动态成像分析进行测定。球形度(SPHT3)根据所测量的周长P和颗粒投影面积A使用以下公式进行计算
所测定的值是无量纲的,并且对于理想球体为1,而对于非理想球体的球状颗粒,通常低于1。在本申请的情况下,该球形度高于0.9。
这些程序完全按照所规定的方法进行。
颗粒尺寸使用Mie理论通过激光衍射(Malvern Mastersizer 2000)进行测定。
所述水热老化的样品的制备:
样品A
己醇酸铝(Al-hexanolate)的水解在98℃下的2%碳酸氢铵水溶液中进行。在105℃下以3.2m/s的搅拌速度将所获得的具有7.5wt%Al2O3的氧化铝悬浮液(=勃姆石悬浮液)搅拌18小时。
样品B
己醇酸铝的水解在98℃下在2%碳酸氢铵水溶液中进行。将所获得的具有按Al2O3计算的7.5wt%氧化铝的氧化铝悬浮液(=勃姆石悬浮液)在100℃下以3.2m/s的搅拌速度搅拌16小时。所述老化的氧化铝悬浮液在喷雾干燥器中干燥(入口温度:120℃)。获得了沿(120)轴晶体尺寸为而沿(020)轴晶体尺寸为的勃姆石粉末。
实验
实施例1=样品3a
通过将根据样品A的勃姆石分散于酸性水中而制备氧化铝分散体。该分散体含有32.5wt%的勃姆石(以Al2O3计算)和0.03g硝酸/g勃姆石。根据US 4542113,搅拌10分钟后,将溶胶以液滴形式加入到温度为20-25℃的成形塔中,该成形塔填充了8wt%的氨溶液。在120℃下干燥从成形塔排出的生料球状体,直到获得恒重。干燥球状体在650℃下煅烧3小时。
实施例2=样品3b
按照实施例1进行实施例2,但将所述干燥的球状体在950℃下煅烧3小时。
实施例3=样品4
按照实施例1进行实施例3,但所述勃姆石起始氧化铝是样品B。
实施例4=样品5
按照实施例3进行实施例4,但除了勃姆石、水和酸之外,该分散体还含有掺杂剂SnCl4×2H2O,其对应于0.4wt%的Sn,这以SnO2计算并基于所煅烧氧化铝球体。
实施例5=样品6
按照实施例3进行实施例5,但除了勃姆石、水和酸之外,该分散体还含有掺杂剂Bi(NO3)3×5H2O,其对应于0.1wt%的Bi,这基于所述煅烧氧化铝球体以Bi2O3进行计算。
实施例6=样品7
按照实施例3进行实施例6,但除了勃姆石、水和酸之外,该分散体还含有0.1g煤油/g勃姆石。
实施例7=样品8(挤出物)
通过在高剪切混合器中将1500g样品B与1250g 4wt%乙酸混合15分钟而制成氧化铝糊膏。该糊膏通过孔盘压制,而获得直径为1.69mm的挤出物。在120℃下干燥生坯,直至恒重。所述干燥的挤出物在650℃下煅烧3小时。
实施例8=样品9(片状物)
通过本领域已知的方法使用样品B的勃姆石粉末压制成片(5.1×5.2mm),并在650℃下煅烧3小时。
比较实施例1=样品1(不含煤油)
氧化铝分散体通过将沿(120)轴晶体尺寸为而沿(020)轴晶体尺寸为的勃姆石粉末在酸性水中混合而制备,该勃姆石粉末是在没有老化步骤的情况下制备。该分散体含有32.5wt%固体和0.03g硝酸/g勃姆石。搅拌10分钟后,将溶胶以液滴形式进料至温度为20-25℃的成形塔中,其中填充有8wt%的氨溶液。在120℃下干燥从成形塔排出的生料球状体,直至恒重。所述干燥的球状体在650℃下煅烧3小时。
比较实施例2=样品2(含有煤油)
按照比较实施例1进行比较实施例2,但除了勃姆石、水和酸之外,该分散体含有0.1g煤油/g勃姆石。
实施例和比较实施例1和2的总结(包括结果)包括于下面的表1中。
图1比较了比较实施例1(样品1)、比较实施例2(样品2)和实施例1(样品3a)、实施例6(样品7)的孔半径分布。根据图1,可以清楚的是,比较实施例1的介孔半径低于本发明实施例的介孔半径。图2显示了具有相同起始材料但在不同温度下煅烧的实施例1和2的孔半径分布。图3显示了具有不同掺杂剂的实施例4和5(样品5和6)的孔半径分布。图4是DSC(差示扫描量热法)曲线,显示了根据比较实施例1(样品1)和实施例1(样品3a)的氧化铝的相转化。如图所示,比较实施例1(样品1)的特征在于在1188.6℃时相转化为α相,而根据本发明制备的实施例1(样品3a)显示在1314℃时转转化为α相。向α相的相转化伴随着表面积减少。图5显示了比较实施例2(样品2)和实施例1(样品3a)在1200℃下煅烧3小时后的比较。比较实施例2显示出α相,而实施例2仅显示出θ相。
比较实施例3(US 4542113的实施例5)
通过修改US 4542113的实施例5进行比较实施例3。使用了完全相同的实验程序。原料是两种具有以下性质的勃姆石混合物:
表2
将所得材料的性质与US 4542113的实施例5中报告的性质进行比较,所得出的结论是该修改具有代表性(见表3)。
表3:
图6显示了比较实施例3的孔半径分布。所测量的介孔尺寸为4.9nm,而该孔半径分布为双峰。
Claims (19)
1.一种煅烧成型氧化铝,包括以下特征a)和b):
a)30-70N,优选40-60N的抗压强度;和
b)中值孔半径为5-12nm、优选7-10nm的单分散孔半径分布。
2.根据权利要求1所述的煅烧成型氧化铝,还包括特征c)-f)中的一个或多个,并且优选所有特征c)-f)
c)0.4-1.2cm3/g,优选0.7-1.0cm3/g的总孔体积;
d)在1200℃下煅烧3小时后,BET表面积为10-100m2/g,优选在1200℃下煅烧3小时后,BET表面积为40-80m2/g;
e)所述煅烧成型氧化铝的Na、Fe和Si杂质含量各自低于100ppm,优选各自低于50ppm;和
f)α相变温度高于1200℃,优选高于1300℃。
3.根据权利要求2所述的煅烧成型氧化铝,包括特征c)。
4.根据权利要求1-3中任一项所述的煅烧成型氧化铝,其中所述煅烧成型氧化铝呈球状体,优选在成形塔中成型的球状体、挤出物、片状物或它们的混合物的形式,且优选呈球状体。
5.根据权利要求1-4中任一项所述的煅烧成型氧化铝,其中所述煅烧成型氧化铝呈球状体的形式,并且所述球状体包括0.5mm-3.0mm的直径。
6.根据权利要求1-5中任一项所述的煅烧成型氧化铝,包含一种或多种掺杂剂,优选一种或多种选自由以下各项组成的组中的掺杂剂:锡,铋,过渡元素,优选IVb族元素和/或Vb族元素,和稀土元素。
7.一种制备煅烧成型氧化铝的方法,所述方法包括以下步骤:
i)制备氧化铝悬浮液,所述氧化铝悬浮液包含氧化铝和至少水;
iii)可选地干燥所述水热老化的氧化铝悬浮液以获得氧化铝粉末;
iv)可选地由所述氧化铝粉末制备氧化铝糊膏或由所述氧化铝粉末或所述水热老化的氧化铝悬浮液制备氧化铝分散体;
v)将所述氧化铝粉末或所述氧化铝糊膏或所述氧化铝分散体或所述水热老化的氧化铝悬浮液或它们的混合物成型以形成成型氧化铝;
vi)干燥所述成型氧化铝以形成干燥的成型氧化铝;和
vii)煅烧所述干燥的成型氧化铝以形成煅烧成型氧化铝。
8.根据权利要求7所述的方法,其中所述煅烧成型氧化铝呈球状体,优选在成形塔中成型的球状体、挤出物、片状物或它们的混合物的形式,优选呈球状体的形式。
9.根据权利要求7或8所述的方法,其中以Al2O3计算的所述氧化铝悬浮液的氧化铝含量为所述氧化铝悬浮液的2wt%-20wt%,优选5wt%-10wt%。
10.根据权利要求7-9中任一项所述的方法,其中以Al2O3计算的所述氧化铝分散体的氧化铝含量为10wt%-40wt%,优选25wt%-35wt%。
11.根据权利要求7-10中任一项所述的方法,其中所述氧化铝分散体包含酸。
12.根据权利要求7-11中任一项所述的方法,其中所述氧化铝分散体包含煤油,其中所述氧化铝分散体中的煤油的量优选为所述氧化铝分散体的在大于0wt%至10wt%之间,最优选所述氧化铝分散体的在大于0wt%至5wt%之间。
13.根据权利要求7-12中任一项所述的方法,其中在成型以形成所述成型氧化铝之前,将一种或多种掺杂剂添加到所述氧化铝糊膏或所述氧化铝分散体或所述水热老化的氧化铝悬浮液或它们的混合物中,优选一种或多种掺杂剂选自由以下各项组成的组中:锡,铋,过渡元素,特别是IVb族元素和/或Vb族元素,和稀土元素。
14.根据权利要求7-13中任一项所述的方法,其中所述氧化铝悬浮液中的氧化铝是勃姆石、三水铝石、三羟铝石和至少一种过渡氧化铝,并且优选是勃姆石。
15.根据权利要求7-14中任一项所述的方法,其中在水热老化后所述氧化铝悬浮液中的氧化铝包含勃姆石或由勃姆石组成。
16.根据权利要求14或15中任一项所述的方法,其中在水热老化后所述勃姆石具有0.5:1-2.0:1,优选0.9:1-1.1:1的沿(120)轴的晶体尺寸与沿(020)轴的晶体尺寸之比。
17.根据权利要求7-16中任一项所述的方法,其中水热老化反应在60-300℃、优选80-180℃的温度下进行,各自优选进行1-30小时,优选15-30小时。
18.根据权利要求7-17中任一项所述的方法,其中所述成型氧化铝在90-150℃的温度下,优选在110-130℃的温度下干燥2-24小时。
19.根据权利要求7-18中任一项所述的方法,其中煅烧在450-1100℃的温度下,优选在550-750℃的温度下进行,各自优选进行10分钟-10小时,优选2-4小时。
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