CN112469667B - 具有高纯度和高相对密度的α氧化铝、其生产方法及其用途 - Google Patents

具有高纯度和高相对密度的α氧化铝、其生产方法及其用途 Download PDF

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CN112469667B
CN112469667B CN201980049676.0A CN201980049676A CN112469667B CN 112469667 B CN112469667 B CN 112469667B CN 201980049676 A CN201980049676 A CN 201980049676A CN 112469667 B CN112469667 B CN 112469667B
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赖纳·格勒克勒
霍尔格·米策尔
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Abstract

本发明涉及一种具有高纯度、高密度和低表面积的α氧化铝，并且特别涉及一种生产这种α氧化铝的方法以及该α氧化铝在蓝宝石生产中或在复合体和陶瓷体生产中的用途。

Description

具有高纯度和高相对密度的α氧化铝、其生产方法及其用途
技术领域
本发明涉及生产α氧化铝的方法，特别涉及生产具有高纯度、高密度和低BET表面积的α氧化铝的方法。本发明进一步扩展到根据本发明的方法生产的氧化铝以及α氧化铝在蓝宝石生产或复合体和陶瓷体生产中的用途。
背景技术
在超高纯氧化铝的技术领域，重点是生产高纯度、高密度和低BET表面积的氧化铝。在EP 2070873 B1中，描述了纯度至少为99.99％且相对密度为55至90％的α氧化铝粉末。该粉末通过在α氧化铝晶种存在下煅烧无定形氢氧化铝(通过在室温下以两步法用化学计量的水来水解烷氧铝得到)来制备。
需要在不使用α氧化铝晶种的情况下生产高纯度和高密度的氧化铝，即需要简化工艺。
发明内容
根据本发明的第一方面，提供了生产α氧化铝，特别是高纯度α氧化铝的方法，至少包括以下步骤：
i)提供包含勃姆石的勃姆石浆料；其中，勃姆石浆料的勃姆石的晶体尺寸独立地在沿120轴的3.0至6.5nm和沿020轴的3.0至6.0nm的范围内；
ii)老化勃姆石浆料以得到老化的勃姆石浆料，其包含具有(120)轴和(020)轴的改变晶体尺寸的勃姆石颗粒(boehmite particles with a modified crystallite sizehaving a(120)axis and a(020)axis)，其中老化在30至240℃的温度下进行0.5至170小时的时间段，直到勃姆石颗粒：
a)具有小于1nm的沿(120)轴的长度与沿(020)轴的长度之间的差值，或
b)(120)轴大于30nm，或
c)a)和b)均适用；
iii)干燥老化的勃姆石浆料以形成干燥的勃姆石，和
iv)将干燥的勃姆石在1200至1600℃的温度下煅烧1至5小时的煅烧时间以产生α氧化铝。
差值是指沿(120)轴的长度减去沿(020)轴的长度。因此，该差值也可以具有负值。
沿(120)轴的长度与沿(020)轴的长度之间的差值优选地大于0nm且小于1nm，更优选地大于0.05nm且小于1nm，甚至更优选地大于0.1nm且小于1nm，并且最优选地大于0.5nm且小于1nm。
还优选a)和b)的组合，即其中a)包括上述优选范围，并且同时其中(120)轴大于30nm。
进一步要求保护的是根据上述方法生产的α氧化铝以及该α氧化铝用于蓝宝石生产或用于陶瓷体或复合体生产的用途，特别是通过施加压力和/或烧结。
具体实施方式
根据本发明，通过确保老化的勃姆石浆料生产具有沿(120)轴和(020)轴小于1nm，优选大于0nm且小于1nm，更优选地大于0.05nm且小于1nm，甚至更优选地大于0.1nm且小于1nm，并且最优选大于0.5nm且小于1nm的晶体尺寸差值或沿(120)轴小于30nm，优选地大于40nm的晶体尺寸的勃姆石颗粒，则能够在不使用氧化铝晶种的情况下得到相对密度大于90％的纯氧化铝。清楚地说，根据本发明，需要遵循步骤ii)的选项a)或步骤ii)的选项b)。可替代地，选项a)和选项b)都可以遵循。
对于选项a)，勃姆石颗粒沿(120)轴的长度(这意味着在施加步骤ii)的老化之后)优选为至少7nm，更优选地至少10nm，并且最优选地至少13nm。
可以通过本发明领域中已知的方法得到勃姆石浆料，例如通过如US3394990中描述的烷醇铝(aluminium alkoxide，醇铝)的水解。由烷醇铝的水解生产的商业勃姆石产品的实例包括和/>
根据用于水解的烷醇铝的纯度，勃姆石的纯度在99.8000至99.9999％，优选地在99.9900至99.9997％之间。这是超高纯氧化铝领域所需的纯度。
优选地在95至160℃的温度下老化勃姆石浆料25至40小时的时间段。老化可以在搅拌下进行。搅拌可以设置0.5至4m/s，优选地1至3m/s的圆周速度的桨式搅拌器，特别是对于选项a)。
使用众所周知的谢乐公式(Scherrer formula)(1)在(120)和(020)反射上确定根据本发明的勃姆石颗粒的晶体尺寸：
晶体尺寸＝(K×λ×57.3)/(β×cosθ)； (1)
其中
K(形状因数)：0.992
λ(x射线波长)：0.154nm
β(校正的设备线宽)：依赖于反射
θ：依赖于反射
本领域技术人员知道，在勃姆石的X射线衍射图中，(120)反射(沿120轴的反射)位于2θ＝28.2°，(020)反射(沿020轴的反射)位于2θ＝14.5°。使用这些值，可以根据等式(1)由等式(2)计算出的校正后的线宽来计算出每个反射的相应晶体尺寸。
β＝样品的半宽度-标准品的半宽度 (2)
关于选项b)，沿(120)轴的老化的勃姆石颗粒的晶体尺寸优选地在大于30和100nm之间，更优选地在大于30和50nm之间或大于40和60nm之间。
干燥步骤可以在喷雾干燥器中进行。典型的温度包括300至500℃，优选地320至400℃的入口温度和100至150℃，优选地110至120℃的出口温度。
干燥的勃姆石的煅烧优选地在1300至1400℃的温度下，更优选在1350至1360℃的温度下进行。煅烧时间优选地是3至4小时。煅烧炉的升温速率优选地是2至8℃/min，更优选地4至8℃/min。可以彼此独立选择温度、煅烧时间和升温速率。
本发明的方法生产出具有高于90％的相对密度，优选地高于94％的相对密度，和小于10m2/g的BET表面积的α氧化铝。
因此，根据本发明的第二方面，提供了根据本发明的方法生产的α氧化铝。
根据本发明的方法生产的α氧化铝可以具有高于99.99％的纯度和高于90％的相对密度，优选地高于94％的相对密度，和小于10m2/g的BET表面积。
根据本发明的第三方面，提供了具有至少99.99％的纯度和大于90％的相对密度，优选地大于94％的相对密度，和小于10m2/g的BET表面积的α氧化铝。
在本发明的另一个优选的实施方式中，本发明的α氧化铝用作生产蓝宝石的粉末形式的原料。例如，可以通过将α氧化铝粉末装入坩埚中，加热并熔化α氧化铝粉末来生产蓝宝石。α氧化铝粉末可以以高的堆密度被装入坩埚中，并且适合于生产具有较少空隙的蓝宝石。
根据本发明的另一个优选的实施方式，本发明的α氧化铝可以与其他原料一起用作生产陶瓷或复合体的原料，所述陶瓷或复合体通常是通过施加热和/或压力在模具中生产的。
现在将参考以下非限制性实施例描述本发明。
实施例
根据上述谢乐方程式测量晶体尺寸。
通过ICP原子发射法测量高纯度α氧化铝的纯度，即在使用微波加热的PSS进行溶解后通过ICP原子发射光谱仪测量Ca、Fe、Na、Si和Ti的含量。
根据等式(3)计算纯度：
以％计的纯度＝100[1-(以ppm计的杂质总量)/106] (3)
％是指相对于组合物中所含金属的wt.％。
此外，硫酸盐、氯化物和磷酸盐的含量总计小于200ppm。
使用等式(4)-(6)由颗粒密度计算相对密度：
封闭孔体积(cm3/g)＝(1/颗粒密度)-(1/3.98) (4)
烧结密度(g/cm3)＝
1/[(1/3,98)+孔体积+封闭孔体积] (5)
相对密度(％)＝(烧结密度/3.98)x 100 (6)
使用ULTRA PYCNOMETER 1000 T(Quantachrome)确定颗粒密度(等式4)。
使用Philips XRD X’pert设备进行XRD测量。
根据DIN 66133通过汞渗透方法在1.8至1000nm的孔半径范围内确定孔体积(等式5)。
BET表面积涉及通过N2吸附测定比表面积的Brunauer-Emmett-Teller方法。在液氮温度下使用典型的体积设备，如来自Quantachrome的Quadrasorb。使用DIN ISO 9277:2003-05确定表面积。
比较例1(与本发明方法的步骤ii)的选项a)有关)
将在水中的500g悬浮液(10.5wt.％的Al2O3，pH＝9)加入加热至110℃(1℃/min)的高压釜中。调节反应条件后，使用以1.6m/s的圆周速度运行的标准搅拌器使浆料在110℃下老化24小时，该圆周速度对应于搅拌器速度为500r.p.m。冷却至室温后，将老化的浆料喷雾干燥(入口温度：350℃，出口温度：110℃)。晶体尺寸为沿120轴14.1nm，沿(020)轴10.6nm。然后将颗粒在1350℃下煅烧4小时(加热速率1℃/分钟)。得到纯度为99.9990％的纯α氧化铝，相对密度为59.6％。BET表面积为16m2/g。
比较例2(与步骤ii)的选项b)有关
将在水中的500g悬浮液(7.5wt.％的Al2O3)加入加热至140℃(1℃/min)的高压釜中。自生压力是5巴。调节反应条件后，使用以3.0m/s的圆周速度运行的标准搅拌器使浆料在140℃下老化30小时，该圆周速度对应于搅拌器速度为265r.p.m。冷却至室温后，将老化的浆料喷雾干燥(入口温度：350℃，出口温度：110℃)。晶体尺寸为沿120轴24.7nm。然后将颗粒在1350℃下煅烧4小时(加热速率1℃/分钟)。得到纯度为99.9992％的纯α氧化铝，相对密度为85.2％。BET表面积为11m2/g。
实施例1(与本发明方法的步骤ii)的选项a)有关)
将在水中的500g悬浮液(10.5wt.％的Al2O3，pH＝9)加入加热至98℃(1℃/min)的烧杯中。调节反应条件后，使用以1.6m/s的圆周速度运行的标准搅拌器使浆料在98℃下老化30小时，该圆周速度对应于搅拌器速度为500r.p.m。冷却至室温后，将老化的浆料喷雾干燥(入口温度：350℃，出口温度：110℃)。晶体尺寸为沿120轴13.8nm和沿020轴13.1nm。然后将颗粒在1350℃下煅烧4小时(加热速率1℃/分钟)。得到纯度为99.9996％的纯α氧化铝，相对密度为97.9％。BET表面积为4m2/g。
实施例2(与本发明方法的步骤ii)的选项b)有关)
将在水中的500g悬浮液(7.5wt.％的Al2O3)加入加热至160℃(1℃/min)的高压釜中。自生压力是10巴。调节反应条件后，使用以3m/s的圆周速度运行的标准搅拌器使浆料在160℃下老化30小时，该圆周速度对应于搅拌器速度为265r.p.m。冷却至室温后，将老化的浆料喷雾干燥(入口温度：350℃，出口温度：110℃)。晶体尺寸为沿120轴35.8nm。然后将颗粒在1350℃下煅烧4小时(加热速率1℃/分钟)。得到纯度为99.9994％的纯α氧化铝，相对密度为94.1％。BET表面积为8m2/g。
实施例3(与本发明方法的步骤ii)的选项b)有关)
将在水中的500g悬浮液(7.5wt.％的Al2O3)加入加热至180℃(1℃/min)的高压釜中。自生压力是15巴。调节反应条件后，使用以1.6m/s的圆周速度运行的标准搅拌器使浆料在180℃下老化30小时，该圆周速度对应于搅拌器速度为500r.p.m。冷却至室温后，将老化的浆料喷雾干燥(入口温度：350℃，出口温度：110℃)。晶体尺寸为沿120轴41.8nm。然后将颗粒在1350℃下煅烧4小时(加热速率1℃/分钟)。得到纯度为99.9996％的纯α氧化铝，相对密度为97.4％。BET表面积为7m2/g。
实验结果概述在下表中：
表1-本发明方法的步骤ii)的选项a)：
表2-本发明方法的步骤ii)的选项b)：
如通过当与比较例相比时的实施例可以看出，本发明的方法生产了具有大于99.99％的纯度和大于90％的相对密度，优选地大于94％的相对密度，和小于10m2/g的BET表面积的α氧化铝。

Claims (19)

1.一种生产α氧化铝的方法，至少包括以下步骤：
i）提供包含勃姆石的勃姆石浆料；其中，所述勃姆石浆料的勃姆石的晶体尺寸在沿120轴的3.0至6.5 nm和沿020轴的3.0至6.0 nm的范围内；
ii）老化所述勃姆石浆料以得到老化的勃姆石浆料，所述老化的勃姆石浆料包含具有120轴和020轴的改变晶体尺寸的勃姆石颗粒，其中，所述老化在30至240°C的温度下进行0.5至170小时的时间段，直到所述勃姆石颗粒：
a）具有大于0且小于1 nm的沿所述120轴的长度与沿所述020轴的长度之间的差值，或
b）所述120轴大于30 nm，或
c）a）和b）均适用；
iii）干燥所述老化的勃姆石浆料以形成干燥的勃姆石，和
iv）将所述干燥的勃姆石在1300至1400°C的温度下煅烧1至5小时的煅烧时间以产生α氧化铝。
2.根据权利要求1所述的方法，其中，通过烷醇铝的水解得到所述勃姆石浆料。
3.根据权利要求1或权利要求2所述的方法，其中，沿所述120轴的长度与沿所述020轴的长度之间的差值大于0.05 nm且小于1 nm。
4.根据权利要求3所述的方法，其中，沿所述120轴的长度与沿所述020轴的长度之间的差值大于0.1 nm且小于1 nm。
5.根据权利要求4所述的方法，其中，沿所述120轴的长度与沿所述020轴的长度之间的差值大于0.5 nm且小于1 nm。
6.根据权利要求1或权利要求2所述的方法，其中，对于选项a），沿所述120轴的长度是至少7 nm。
7.根据权利要求6所述的方法，其中，对于选项a），沿所述120轴的长度是至少10 nm。
8.根据权利要求7所述的方法，其中，对于选项a），沿所述120轴的长度是至少13 nm。
9.根据权利要求1或权利要求2所述的方法，其中，对于选项b），沿所述120轴的长度大于40 nm。
10.根据权利要求1或权利要求2所述的方法，其中，所述勃姆石的纯度在99.8000%至99.9999%的范围内。
11.根据权利要求10所述的方法，其中，所述勃姆石的纯度在99.9900%至99.9997%的范围内。
12.根据权利要求1或权利要求2所述的方法，其中，所述勃姆石浆料在95至160°C的温度下老化25至40小时的时间段。
13.根据权利要求1或权利要求2所述的方法，其中，对于所述方法的步骤ii）的选项b），老化的勃姆石颗粒沿所述120轴的晶体尺寸为30至100 nm。
14.根据权利要求13所述的方法，其中，对于所述方法的步骤ii）的选项b），老化的勃姆石颗粒沿所述120轴的晶体尺寸为30至50 nm或40至60 nm。
15.根据权利要求1或权利要求2所述的方法，其中，干燥步骤是在喷雾干燥器中进行的，所述喷雾干燥器的入口温度为300至500°C，并且出口温度为100至150°C。
16.根据权利要求15所述的方法，其中，干燥步骤是在喷雾干燥器中进行的，所述喷雾干燥器的入口温度为320至400°C。
17.根据权利要求15所述的方法，其中，干燥步骤是在喷雾干燥器中进行的，所述喷雾干燥器的出口温度为110至120°C。
18.根据权利要求1或权利要求2所述的方法，其中，煅烧在1350至1400°C的温度下发生。
19.根据权利要求18所述的方法，其中，煅烧在1350至1360°C的温度下发生。
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