CN105384182B - 一种氧化铝微球的制备方法 - Google Patents
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
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- B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
本发明涉及一种氧化铝微球的制备方法，其特征在于：将氧化铝前驱体加入到65‑90℃的结冷胶溶液中，形成氧化铝前驱体‑结冷胶悬浮液；将上述悬浮液加入80‑100℃油相中进行高速搅拌，冷却后加入阳离子溶液继续搅拌可得到凝胶微球，将凝胶微球洗涤、干燥、焙烧可得到氧化铝微球。该法具有成型速度快，制备过程无污染，生产成本低等优势，而且操作步骤简单，易于实现工业化生产，产品磨耗较低，颗粒尺寸满足多种反应器要求。
Description
技术领域
本发明属于催化剂载体领域，涉及一种氧化铝微球的制备方法，尤其是一种利用结冷胶与金属离子溶液形成凝胶的特性制备氧化铝微球。
技术背景
γ-氧化铝具有较大的比表面，可调控的孔结构及良好的热稳定性能、吸附性能，广泛用于催化剂载体及其吸附剂。目前球形氧化铝的制备方法主要有：喷雾造粒，滚动成型、油(氨)柱成型及水柱成型。其中喷雾干燥制备氧化铝微球的粒径为几十微米到几百微米，但此法制备的产品粒度分布不均匀，且存在较多的粉尘，环境污染严重。滚动成型难以制备微米级的颗粒。油(氨)柱成型及水柱成型产品的颗粒尺寸均大于几百微米。当球形氧化铝应用于流化床中时，要求的颗粒粒径在几十微米至几千微米，且样品的耐磨性能要求较高。
中国专利201210376310.4中，以脲醛树脂微球作为模板吸附铝离子，然后在环氧丙烷的开环作用下使铝离子发生羟联反应和阳联反应，制备氧化铝微球。此法所用原料模板的成本较高，交联时间需要4-5小时，生产效率较低。
中国专利201310057670.2中，利用静电纺丝技术制备氧化铝微球，粒径在0.1-1μm。但此工艺的生产效率较低，控制因素(电压、电流、纺丝距离、湿度、温度等)较多，设备的输出电压为20-30KV且成本较高，苛刻的实验条件及较高的生产成本难以实现工业化生产。
结冷胶是一种阴离子型线性多糖，具有平行的双螺旋结构，胶体链为4个基本单元重复聚合组成，基本单元由一份子的鼠李糖和葡萄糖全算及两分子的葡萄糖构成，并可与金属阳离子的溶液形成凝胶。
发明内容
本发明的目的是提供一种新型的制备氧化铝微球的方法，以解决技术背景中所述的工艺复杂、生产成本高及难以实现工业化生产等问题，同时产品的磨耗较低，粒度相对较为集中，满足多种反应器要求。
本发明的技术方案概述如下：
一种氧化铝微球的制备方法，包括以下步骤：
将氧化铝前驱体、结冷胶分散于去离子水中，然后加热至65～90℃，使结冷胶充分溶解，形成混悬液；将上述混悬液加入到80～100℃油相中进行高速搅拌10～30min，然后在搅拌作用下将体系冷却至10-30℃后，加入阳离子溶液继续搅拌形成凝胶微球；将凝胶微球取出进行洗涤、干燥、焙烧得到氧化铝微球；所述氧化铝前驱体在浆液中的固含量为5-30wt％，结冷胶含量为0.1-5wt％。
所述氧化铝前驱体为拟薄水铝石、薄水铝石、氧化铝水凝胶或者纳米氧化铝溶胶中的一种或多种。
所述油相为煤油、石蜡油中的一种或者多种，混悬液与油相的体积比为1:1～10。
所述搅拌速度为500-1000rpm。
所述阳离子溶液为钾、钠或铝离子的盐溶液，阳离子总浓度为0.1-0.5mol/L。。
本发明方法与现有技术相比，其有益效果如下：
1)本发明利用浆液加入油相中，在高速搅拌作用下可形成球形的小液滴，该法操作简便，再利用结冷胶与阳离子形成凝胶，进一步固化，得到凝胶微球。
2)该法通过控制混悬液与油相的体积比，可控制形成的氧化铝微球颗粒的尺寸在50μm-1000μm可调，且颗粒尺寸相对集中，磨耗较低。
3)原料及过程绿色、无污染，是一种低成本制备高性能氧化铝微球的方法，易于实现工业化生产。
具体实施方式
下面结合具体实施例对本发明一种氧化铝微球的制备方法作进一步说明，但并不因此而限制本发明。
实施例1
(1)将100g拟薄水铝石样品加入到70℃的300ml结冷胶水溶液(浓度2％)中，拟薄水铝石在浆液中的固含量为25％，形成拟薄水铝石-结冷胶悬浮液。
(2)将上述混悬液加入到90℃煤油中，且煤油的体积为300ml，开启搅拌速度500rpm，搅拌时间15min，将体系冷却到25℃。
(3)加入铝离子溶液继续搅拌，铝离子总浓度为0.1mol/L，可以得到凝胶微球。
(4)将凝胶颗粒洗涤后，在100℃下干燥10h，550℃焙烧4h，得到的氧化铝微球的性质见表1。
实施例2
按照实施例1中的步骤制备氧化铝微球，不同的是加入的铝源为氧化铝水凝胶，且在浆液中的固含量为10％，得到的微球性质见表1。
实施例3
按照实施例1中的步骤制备氧化铝微球，不同的是加入的油相为石蜡油，得到的微球的性质见表1。
实施例4
按照实施例1中的步骤制备氧化铝微球，混悬液与油相的体积比变为1:5，得到的微球的性质见表1。
实施例5
按照实施例1中的步骤制备氧化铝微球，混悬液与油相的体积比变为1:10，得到的微球的性质见表1。
实施例6
按照实施例1中的步骤制备氧化铝微球，不同的是加入的阳离子为钾离子，得到的微球的性质见表1。
实施例7
按照实施例1中的步骤制备氧化铝微球，不同的是阳离子铝离子在浆液中的浓度为0.4mol/L,得到的微球的性质见表1。
表1氧化铝微球物性结果
| 实施例 | 粒径(μm) | 磨耗(％) |
| 1 | 730-820 | 0.2 |
| 2 | 290-400 | 0.31 |
| 3 | 720-850 | 0.23 |
| 4 | 450-550 | 0.28 |
| 5 | 50-160 | 0.35 |
| 6 | 690-810 | 0.44 |
| 7 | 580-690 | 0.05 |
Claims (5)
1.一种氧化铝微球的制备方法，其特征在于，按照以下的工艺步骤进行：将氧化铝前驱体、结冷胶分散于去离子水中，然后加热至65～90℃，使结冷胶充分溶解，形成混悬液；将上述混悬液加入到80～100℃油相中进行高速搅拌10～30min，然后在搅拌作用下将体系冷却至10-30℃后，加入金属阳离子溶液继续搅拌形成凝胶微球；将凝胶微球取出进行洗涤、干燥、焙烧得到氧化铝微球；所述氧化铝前驱体在所述混悬液中的固含量为5-30wt％，结冷胶在所述混悬液中的含量为0.1-5wt％。
2.按照权利要求1所述方法，其特征在于，所述的氧化铝前驱体为拟薄水铝石、薄水铝石、氧化铝水凝胶或者纳米氧化铝溶胶中的一种或多种。
3.按照权利要求1所述方法，其特征在于，所述的油相为煤油、石蜡油中的一种或者多种，所述混悬液与所述油相的体积比为1:1～10。
4.按照权利要求1所述方法，其特征在于，所述的搅拌速度为500-1000rpm。
5.按照权利要求1所述方法，其特征在于，所述阳离子溶液为钾、钠或铝离子的盐溶液，阳离子总浓度为0.1-0.5mol/L。
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