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CN114452966B - 一种大孔氧化铝的制备方法 - Google Patents

一种大孔氧化铝的制备方法 Download PDF

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CN114452966B
CN114452966B CN202011135395.8A CN202011135395A CN114452966B CN 114452966 B CN114452966 B CN 114452966B CN 202011135395 A CN202011135395 A CN 202011135395A CN 114452966 B CN114452966 B CN 114452966B
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alumina
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boehmite
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CN114452966A (zh
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翁延博
季洪海
袁胜华
隋宝宽
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

本发明公开了一种大孔氧化铝的制备方法。本发明的大孔氧化铝的制备方法，包括如下内容：（1）用适当浓度的氯化铵水溶液浸渍处理氧化铝前驱物；（2）将步骤（1）得到的物料进行焙烧处理，制得大孔氧化铝；其中所述的氧化铝前驱物为胶溶指数低于85%的拟薄水铝石。本发明方法操作过程简单，扩孔效果明显，可以有效提高氧化铝中10‑30nm的孔道含量，得到的大孔氧化铝可以应用于大分子的催化、吸附等领域。

Description

一种大孔氧化铝的制备方法
技术领域
本发明涉及无机材料制备领域，具体地说涉及一种大孔氧化铝的制备方法。
背景技术
活性氧化铝是一种多孔性材料，具有优异的物化特性，作为催化剂或载体被广泛应用。氧化铝载体的孔结构不仅影响着所负载活性组分的分散度还与催化剂的活性、选择性、催化剂寿命等密切相关。随着原油重质化日趋严重，传统的小孔氧化铝已无法满足生产要求，介孔和大孔活性氧化铝的研发与生产愈加重要。
CN104340997A公开一种大孔径氧化铝的制备方法，该方法将薄水铝石、拟薄水铝石或薄水铝石与拟薄水铝石按任意比例组成的混合物溶解在去离子水中，形成氢氧化铝悬浮液；分区段升温处理；将处理后的氢氧化铝悬浮液进行水热老化；老化完毕后进行干燥、焙烧处理，最终得到大孔径的氧化铝产品。
CN105600810A公开一种大孔氧化铝材料的制备方法，该方法首先将炭黑与碱液混合搅拌处理，然后配置铝盐溶液，将过滤干燥得到的炭黑与铝盐溶液混合搅拌并超声波处理后加入铵盐，然后将混合物干燥，最后依次置于氮气、氧气、氮气气氛中处理，得到氧化铝。
CN102795647A公开一种大孔氧化铝及其制备方法，该方法氧化铝采用两段老化法制备，第一段老化向氢氧化铝悬浮液中加入碱性化合物或酸性化合物调节悬浮液的pH值后进行老化，第二段老化加入脂肪醇，老化完毕后，分离出脂肪醇，将除去脂肪醇的浆液干燥、焙烧即得本发明的大孔径、大比表面、大孔体积的氧化铝。
杜明仙等（杜明仙, 翟效珍, 李源, 李林东, 朱华青, 谭长瑜. 高比表面积窄孔分布氧化铝的制备I.沉淀条件的影响. 催化学报, 2002, 23(5): 465-468.）采用pH摆动法制备了具有较高比表面积和较高大孔含量的氧化铝。
研究发现，采用以上技术可以制备具有较高大孔含量的氧化铝，但存在制备过程复杂，不易工业化生产的不足。
发明内容
针对现有技术中的不足，本发明提供了一种大孔氧化铝的制备方法。该方法采用简单的扩孔技术，可以有效提高氧化铝中10-30nm的孔道含量，同时降低10nm以下孔道含量，得到的大孔氧化铝可以应用于大分子的催化、吸附等领域。
本发明的大孔氧化铝的制备方法，包括如下内容：
（1）用适当浓度的氯化铵水溶液浸渍氧化铝前驱物，固液分离，干燥处理；
（2）将步骤（1）得到的固相物料，进行焙烧处理，得到大孔氧化铝粉末或大孔氧化铝成型载体。
本发明方法中，步骤（1）所述的氧化铝前驱物为胶溶指数低于85%的拟薄水铝石粉末或由上述粉末制备的成型物，优选胶溶指数低于80%。
本发明方法中，步骤（1）所述的成型物制具体指以胶溶指数低于85%的拟薄水铝石粉末为原料经混捏、成型、干燥后的物料。所述的混捏、成型为本领域共知技术，混捏、成型过程为将适量拟薄水铝石与适量田菁粉混合均匀，然后加入适量浓度的胶溶剂水溶液，所述的胶溶剂水溶液为硝酸、盐酸、柠檬酸、醋酸、草酸中的一种或几种混合的水溶液，溶液的质量浓度为1%-3%，加入量视成型效果而定。所述的干燥温度为80-160℃，干燥时间为1-10小时。
本发明方法中，步骤（1）所述的氯化铵溶液浓度为2-7.5mol/L，优选3-6mol/L，溶液的用量为使拟薄水铝石粉末或拟薄水铝石成型物完全浸没，浸渍时间为0.5-3小时，优选2-3小时。
本发明方法中，步骤（1）所述的固液分离一般采用过滤、离心等方式，分离得到的液相可以经浓度调整后循环使用。
本发明方法中，步骤（1）所述的干燥条件为：干燥温度为80-200℃，优选100-160℃，干燥时间为1-10小时，优选4-8小时。
本发明方法中，步骤（2）所述的焙烧条件为：焙烧温度为500-850℃，优选650-800℃，焙烧时间为1-10小时，优选4-8小时。焙烧过程对焙烧气氛无特殊要求，一般在空气气氛下焙烧即可，也可以在惰性气氛下和/或氧气气氛进行。
本发明同时提供一种加氢催化剂，该催化剂包含上述方法制备的大孔氧化铝成型载体或大孔氧化铝粉末制备得到的氧化铝载体。
本发明的加氢催化剂在重质油加氢工艺中的应用，特别适用于重质油的加氢脱金属、脱硫和脱氮等加氢工艺。
与现有技术相比，本发明具有以下优点：
（1）本发明使用氯化铵水溶液浸渍拟薄水铝石，浸渍后的拟薄水铝石经干燥、焙烧制得氧化铝。浸渍时氯离子、铵根离子及水分子等物质均匀分布于拟薄水铝石晶粒表面及片层结构中。浸渍后的拟薄水铝石高温焙烧时氯化铵溶液受热分解，产生氨气、氯化氢和水蒸气，产生的气体一方面可以起到冲孔作用；另一方面，由于氧化铝为两性氧化物，产生的氨气和氯化氢气体可与氧化铝晶粒作用，改变晶粒尺寸及堆积形态，进而改善氧化铝材料的孔道结构，提高载体中的大孔含量。
（2）该方法过程简单，原料易得，易于工业化生产。
具体实施方式
下面结合实施例来进一步说明本发明的技术方案和技术效果，但并不局限于以下实施例。
BET法：应用N2物理吸-脱附表征实施例与对比例载体孔结构，具体操作如下：采用ASAP-2420型N2物理吸-脱附仪对样品孔结构进行表征。取少量样品在300℃下真空处理3-4小时，最后将产品置于液氮低温（-200℃）条件下进行氮气吸-脱附测试。其中比表面积根据BET方程得到，孔容和孔直径在100nm以下的分布率根据BJH模型得到。
本发明方法中拟薄水铝石的胶溶指数DI的测定方法按照以下方法测定：称取5g筛分小于200目的拟薄水铝石（干基）置于250mL锥形瓶中，加入适量蒸馏水，开动电磁搅拌，加入适量盐酸，继续搅拌一定时间后静置沉降24h，倒掉上层悬浊液后，干燥，焙烧，称量剩余样品质量为w，DI=(5-w)/5×100%。
本发明方法中使用的拟薄水铝石A1的胶溶指数DI为82%，拟薄水铝石A2的胶溶指数DI为78%。
实施例1
称取适量拟薄水铝石A1，然后加入适量摩尔浓度为4.5mol/L的氯化铵溶液使拟薄水铝石完全被浸没，浸没后的物料浸渍2小时后经液固分离，固体物料于120℃干燥6小时，干燥后物料置于马弗炉中于700℃，空气气氛下焙烧6小时，制得氧化铝S1，载体性质见表1。
实施例2
称取适量拟薄水铝石A2，然后加入适量摩尔浓度为3.5mol/L的氯化铵溶液使拟薄水铝石完全被浸没，浸没后的物料浸渍2小时后经液固分离，固体物料于140℃干燥5小时，干燥后物料置于马弗炉中于750℃，氮气气氛下焙烧4小时，制得氧化铝S2，载体性质见表1。
实施例3
称取适量拟薄水铝石A1，然后加入适量摩尔浓度为2.5mol/L的氯化铵溶液使拟薄水铝石完全被浸没，浸没后的物料浸渍2小时后经液固分离，固体物料于160℃干燥4小时，干燥后物料置于马弗炉中于800℃，氧气气氛下焙烧6小时制得氧化铝S3，载体性质见表1。
实施例4
称取适量拟薄水铝石A1，然后加入适量摩尔浓度为5.5mol/L的氯化铵溶液使拟薄水铝石完全被浸没，浸没后的物料浸渍2小时后经液固分离，固体物料于100℃干燥7小时，干燥后物料置于马弗炉中于650℃，空气气氛下焙烧7小时制得氧化铝S4，载体性质见表1。
实施例5
称取适量拟薄水铝石A1，然后加入适量摩尔浓度为2.5mol/L的氯化铵溶液使拟薄水铝石完全被浸没，浸没后的物料浸渍2小时后经液固分离，固体物料于180℃干燥3小时，干燥后物料置于马弗炉中于700℃，空气气氛下焙烧6小时，制得氧化铝S5，载体性质见表1。
实施例6
称取适量拟薄水铝石A1，加入适量田菁粉，控制田菁粉质量为拟薄水铝石A1质量的1%，将上述物料混合均匀，然后加入适量质量浓度为1%的硝酸水溶液混捏均匀，挤条成型，成型后的条形物料于120℃干燥6小时制得拟薄水铝石成型物。
称取适量上述拟薄水铝石成型物，然后加入适量摩尔浓度为4.5mol/L的氯化铵溶液使拟薄水铝石成型物完全被浸没，浸没后的物料浸渍2小时后经液固分离，固体物料于120℃干燥6小时，干燥后物料置于马弗炉中于700℃，空气气氛下焙烧6小时，制得氧化铝载体S6，载体性质见表1。
实施例7
称取适量拟薄水铝石A2，加入适量田菁粉，控制田菁粉质量为拟薄水铝石A1质量的1%，将上述物料混合均匀，然后加入适量质量浓度为1%的硝酸水溶液混捏均匀，挤条成型，成型后的条形物料于120℃干燥6小时制得拟薄水铝石成型物。
称取适量上述拟薄水铝石成型物，然后加入适量摩尔浓度为4.5mol/L的氯化铵溶液使拟薄水铝石成型物完全被浸没，浸没后的物料浸渍2小时后经液固分离，固体物料于120℃干燥6小时，干燥后物料置于马弗炉中于700℃，空气气氛下焙烧6小时，制得氧化铝载体S7，载体性质见表1。
对比例1
同实施例1，只是拟薄水铝石A1中未加入氯化铵，而是将拟薄水铝石直接焙烧制得对比氧化铝S8，载体性质见表1。
对比例2
同实施例1，只是拟薄水铝石A2中未加入氯化铵，而是将拟薄水铝石直接焙烧制得对比氧化铝S9，载体性质见表1。
对比例3
同实施例1，只是将氯化铵换成相同摩尔浓度的氟化铵制得对比氧化铝S10，载体性质见表1。
对比例4
同实施例1，只是将氯化铵换成相同摩尔浓度的柠檬酸铵制得对比氧化铝S11，载体性质见表1。
对比例5
同实施例6，只是拟薄水铝石成型物未经氯化铵溶液浸渍处理，而是将拟薄水铝石成型物制备焙烧制得对比氧化铝载体S12，载体性质见表1。
对比例6
同实施例6，只是将氯化铵换成相同摩尔浓度的氟化铵制得对比氧化铝载体S13，载体性质见表1。
对比例7
同实施例7，只是拟薄水铝石成型物未经氯化铵溶液浸渍处理，而是将拟薄水铝石成型物制备焙烧制得对比氧化铝载体S14，载体性质见表1。
表1氧化铝性质。
实施例1 实施例2 实施例3 实施例4 实施例5 实施例6 实施例7
氧化铝载体 S1 S2 S3 S4 S5 S6 S7
比表面积，m2/g 212 230 204 221 213 181 209
孔容，mL/g 0.80 0.86 0.79 0.79 0.81 0.73 0.83
孔分布，v%
<10nm，% 34.8 32.4 36.2 35.7 38.5 41.1 37.8
10-30nm，% 56.4 62.8 55.7 55.3 53.6 54.6 58.6
>30nm，% 8.8 4.8 8.1 8.0 7.9 4.3 3.6
表1（续）氧化铝性质。
对比例1 对比例2 对比例3 对比例4 对比例5 对比例6 对比例7
氧化铝载体 S8 S9 S10 S11 S12 S13 S14
比表面积，m2/g 217 241 146 228 183 151 215
孔容，mL/g 0.81 0.86 0.61 0.81 0.72 0.60 0.82
孔分布，v%
<10nm，% 45.7 41.2 39.6 50.1 48.3 44.2 45.8
10-30nm，% 48.6 55.6 52.5 45.8 47.6 50.1 51.6
>30nm，% 5.7 3.2 7.9 4.1 4.1 5.7 2.6
从表1可以看出，采用本发明方法对拟薄水铝石进行氯化铵溶液浸渍处理后制得的氧化铝与未处理的氧化铝相比小于10nm的孔道含量降低，而10-30nm及大于30nm的孔道含量增加，这说明该处理方法具有提高氧化铝孔径的作用。而加入氟化铵溶液时，对载体的孔容和比表面积破坏较严重。加入柠檬酸铵溶液后使载体的孔径降低。

Claims (8)

1.一种大孔氧化铝的制备方法，其特征在于：包括如下内容：(1)用浓度为2-7.5mol/L的氯化铵水溶液浸渍氧化铝前驱物，固液分离，进行干燥处理；(2)将步骤(1)得到的固相物料，进行焙烧处理，得到大孔氧化铝粉末或大孔氧化铝成型载体；所述的氧化铝前驱物为胶溶指数78％的拟薄水铝石粉末或由上述粉末制备的成型物；步骤(1)所述的氯化铵溶液的用量为使拟薄水铝石粉末或拟薄水铝石成型物完全浸没，浸渍时间为0.5-3小时。
2.根据权利要求1所述的方法，其特征在于：步骤(1)所述的成型物具体指以胶溶指数78％的拟薄水铝石粉末为原料经混捏、成型、干燥后的物料。
3.根据权利要求1所述的方法，其特征在于：步骤(1)所述的氯化铵溶液浓度为3-6mol/L。
4.根据权利要求1所述的方法，其特征在于：步骤(1)所述的干燥条件为：干燥温度为80-200℃，干燥时间为1-10小时。
5.根据权利要求1所述的方法，其特征在于：步骤(2)所述的焙烧条件为：焙烧温度为500-850℃，焙烧时间为1-10小时。
6.根据权利要求1所述的方法，其特征在于：步骤(2)所述的焙烧条件为：焙烧温度为650-800℃，焙烧时间为4-8小时。
7.一种加氢催化剂，其特征在于：该催化剂包含权利要求1-6任一方法制备的大孔氧化铝成型载体或大孔氧化铝粉末。
8.一种权利要求7所述的加氢催化剂在重质油加氢工艺中的应用。
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