CN111420711A - 一种氧化铝载体及其制备方法 - Google Patents

一种氧化铝载体及其制备方法 Download PDF

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CN111420711A
CN111420711A CN202010358448.6A CN202010358448A CN111420711A CN 111420711 A CN111420711 A CN 111420711A CN 202010358448 A CN202010358448 A CN 202010358448A CN 111420711 A CN111420711 A CN 111420711A
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alumina carrier
alumina
pore
pore volume
boehmite
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马博文
吴艳
李文博
陈贵锋
毛学锋
刘敏
胡发亭
钟金龙
王吉坤
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China Coal Research Institute CCRI
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Abstract

本发明公开了一种煤焦油加氢催化剂的氧化铝载体及其制备方法。所述载体的孔容为1.0～1.5mL/g，比表面积200～300m2/g，最可几孔径为15～30nm，20～30nm以上大孔的孔体积占总孔容的45～70％。本发明提供的氧化铝载体具有大孔容大孔径，扩散性能优异，适合作为处理胶质、沥青质含量高的重油的加氢催化剂载体。

Description

一种氧化铝载体及其制备方法
技术领域
本发明是关于一种氧化铝载体及其制备方法，更具体地说是一种大孔径大孔容的氧化铝载体及其制备方法。
背景技术
煤焦油是煤在热解和气化过程中获得的一种宝贵化工原料。随着低阶煤热解技术的迅速发展，中低温煤焦油产量的大幅提升。中低温煤焦油含有较多的烷烃、环烷烃和较少的稠环芳烃，适宜通过加氢的方式生产清洁燃料油和高附加值化学品。
渣油属于石油基重油中最难加工的原料，含有大量胶质和沥青质，这部分物质分子量大、结构复杂，扩散困难，因此要求催化剂具有优良的孔道结构。与渣油相比较，煤焦油中所含的沥青质远大于渣油中的含量，由于沥青质分子直径大，含有大量杂原子和金属，在加氢过程中易于缩聚形成焦炭和发生金属沉积，堵塞催化剂孔道使其失活，从而对煤焦油加氢催化剂提出更高的要求。
氧化铝载体的孔结构是催化剂十分重要的性质。煤焦油中的沥青质分子及金属杂原子化合物直径都较大，煤焦油加氢属于扩散控制过程，需要催化剂具有较大的孔径以使重质组分大分子能够进入催化剂孔道，进而与催化剂表面活性位作用，同时需要大孔容容纳脱除的金属杂质，因此氧化铝载体的孔结构对催化剂的反应效果有很大影响。
CN107303484A公开了一种含硅大孔氧化铝载体的制备方法，利用多元醇和/或糖类物质的水溶液浸渍拟薄水铝石并进行水热处理，加入用含硅溶液浸渍的炭黑粉，与助挤剂、胶溶剂混捏，制得含硅的氧化铝载体。
CN104646005A公开了一种重油脱金属催化剂制备方法，称取拟薄水铝石，加入胶溶剂、助挤剂和扩孔剂，混捏、干燥、焙烧后喷淋酸性溶液，干燥后制得一种氧化铝载体，其孔容为0.71～0.85，平均孔直径19～30nm。
上述方法所制备氧化铝载体的孔容多在0.9mL/g以下，20～30nm以上大孔的孔体积占总孔容低于45％，不能避免较小的孔道发生孔口堵塞，不能最大程度改善催化剂的扩散性能。
发明内容
针对现有技术的不足，本发明提供一种氧化铝载体及其制备方法，本方法制备的氧化铝载体20～30nm以上大孔的孔体积占总孔容的45～70％，扩散性能好，有效解决煤焦油或渣油中大量沥青质大分子物质向催化剂内部扩散和加氢转化的问题。本方法制备的氧化铝载体孔容更大，可以容纳更多的金属和积炭，延长加氢装置开工周期。本发明提供的方法在载体制备过程中无需添加酸性胶溶剂，降低了酸对水合氧化铝粒子结构的破坏，有效保护氧化铝载体的孔道结构，使上大孔结构尽可能得以保存；本发明提供的的拟薄水铝石胶溶性能好，在载体制备过程中无需添加粘结剂，大幅降低焙烧能耗并提高产品强度；使用含硼化合物与聚氧乙烯醚复合扩孔比两者单独使用，所得孔径孔容更大，同时扩孔剂加入量低，降低生产成本并提高载体强度。本发明制备的氧化铝载体可做为加氢催化剂载体特别是加氢保护剂、加氢脱金属剂和沥青质转化催化剂载体使用。
具体而言，本发明提供一种氧化铝载体，其中，
孔容为1.0～1.5mL/g；
比表面积为200～300m2/g；
最可几孔径为15～30nm；
20～30nm以上大孔的孔体积占总孔容的45～70％。
本发明同时提供一种加氢催化剂氧化铝载体的制备方法，包括如下步骤：
A、拟薄水铝石的制备
(1)将偏铝酸钠溶于去离子水中，得到偏铝酸钠溶液；
(2)将偏铝酸钠溶液在搅拌条件下加入到硫酸铝溶液中；
(3)将步骤(2)所得产物在陈化条件下陈化；
(4)将步骤(3)所得陈化产物过滤，洗涤、干燥，得到拟薄水铝石M；
B、氧化铝载体的制备
(1)将拟薄水铝石M与复合扩孔剂和助挤剂混合并成型、干燥；
(2)对(1)中所得的颗粒物在600～1000℃下焙烧1～6小时。
制得的拟薄水铝石M孔容为1.1～2.2mL/g，比表面积为130～500m2/g，最可几孔径为15～35nm。
本发明所述的氧化铝载体的制备方法，其中，所述的复合扩孔剂为含硼化合物和聚氧乙烯醚。
本发明所述的氧化铝载体的制备方法，其中，所述的含硼化合物优选硼酸、氧化硼和硼酸盐中的一种或几种。
本发明所述的氧化铝载体的制备方法，其中，以硼计，所述的含硼化合物的加入量优选为拟薄水铝石M中对应的氧化铝重量的0.5～5％。
本发明所述的煤焦油加氢预处理催化剂的制备方法，其中，所述的聚氧乙烯醚为烷基酚聚氧乙烯醚、蓖麻油聚氧乙烯醚、脂肪胺聚氧乙烯醚、脂肪酸聚氧乙烯脂其中的一种或几种。
本发明所述的氧化铝载体的制备方法，其中，所述的聚氧乙烯醚的加入量优选为拟薄水铝石M中对应的氧化铝重量的0.5～3％。
本发明所述的氧化铝载体的制备方法，其中，所述的助挤剂优选为田菁粉或淀粉。
本发明所述的氧化铝载体的制备方法，其中，所述的助挤剂的加入量优选为拟薄水铝石M中对应的氧化铝重量的1～3％。
本发明氧化铝载体的形状可以根据不同的要求进行改变。
与现有技术相比，本发明的优点在于：
针对现有技术的不足，本发明提供一种氧化铝载体及其制备方法，本发明提供的氧化铝载体本方法制备的氧化铝载体20～30nm以上大孔的孔体积占总孔容的45～70％，扩散性能更好，有效解决煤焦油或渣油中大量沥青质大分子物质向催化剂内部扩散和加氢转化的问题；本方法制备的氧化铝载体孔容更大，可以容纳更多的金属和积炭，延长加氢装置开工周期；本发明提供的方法在载体制备过程中无需添加酸性胶溶剂，降低了酸对水合氧化铝粒子结构的破坏，有效保护氧化铝载体的孔道结构，使上大孔结构尽可能得以保存；本发明提供的的拟薄水铝石胶溶性能好，在载体制备过程中无需添加粘结剂，大幅降低焙烧能耗并提高产品强度；使用含硼化合物与聚氧乙烯醚复合扩孔比两者单独使用，所得孔径孔容更大，同时扩孔剂加入量低，降低生产成本并提高载体强度。
本发明制备的氧化铝载体可做为加氢催化剂载体特别是加氢保护剂、加氢脱金属剂和沥青质转化催化剂载体使用。
本发明提供的氧化铝载体的最可几孔径为15～30nm，20～30nm以上大孔的孔体积占总孔容的45～70％，可做为固定床加氢催化剂氧化铝载体使用，特别是作为氧化铝载体制备重油加工用的加氢保护剂、脱金属催化剂和脱沥青质催化剂等加氢催化剂。
具体实施方式
以下对本发明的实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和过程，但本发明的保护范围不限于下述实施例，下列实施例中未注明具体条件的实验方法，通常按照常规条件。
实施例1
制备拟薄水铝石M。用氮气吸附法测定拟薄水铝石的比表面积和孔体积，M的比表面积为245m2/g，孔体积1.4mL/g，最可几孔径为20.8nm。
称取上述拟薄水铝石M100g(干基)，加入田菁粉3g，将1.2g硼酸和0.6g聚氧乙烯醚溶解于110g去离子水中，加入前述物料中，混捏后在单螺杆挤条机上挤成直径2.5mm的圆柱形，105℃干燥4小时，再800℃焙烧4小时，得到氧化铝载体A，其性质见表1。
实施例2
制备拟薄水铝石M。用氮气吸附法测定拟薄水铝石的比表面积和孔体积，M的比表面积为224m2/g，孔体积1.5mL/g，最可几孔径为19.6nm。
称取上述拟薄水铝石M100g(干基)，加入田菁粉3g和1.0g氧化硼，将1.7g聚氧乙烯醚溶解于107g去离子水中，加入前述物料中，混捏后在单螺杆挤条机上挤成直径3.0mm的三叶草形，120℃干燥3小时，再600℃焙烧5小时，得到氧化铝载体B，其性质见表1。
实施例3
制备拟薄水铝石M。用氮气吸附法测定拟薄水铝石的比表面积和孔体积，M的比表面积为230m2/g，孔体积1.5mL/g，最可几孔径为19.5nm。
称取上述拟薄水铝石M100g(干基)，加入田菁粉3g，将1.6g硼酸和0.8g聚氧乙烯醚溶解于110g去离子水中，加入前述物料中，混捏后在单螺杆挤条机上挤成直径3.0mm的四叶草形，110℃干燥4小时，再750℃焙烧4小时，得到氧化铝载体C，其性质见表1。
实施例4
制备拟薄水铝石M。用氮气吸附法测定拟薄水铝石的比表面积和孔体积，M1的比表面积为240m2/g，孔体积1.5mL/g，最可几孔径为21.2nm。
称取上述拟薄水铝石M100g(干基)，加入田菁粉3g，将1.8g氧化硼和1.2g聚氧乙烯醚溶解于110g去离子水中，加入前述物料中，混捏后在单螺杆挤条机上挤成直径2.0mm的圆柱形，60℃干燥10小时，再800℃焙烧4小时，得到氧化铝载体D，其性质见表1。
比较例1
称取商用的大孔拟薄铝石干胶粉(干基含量71.5wt％)100g，加入2.1g田菁粉和4.2g硼酸，混合均匀；将3.6g乙酸溶解于86g去离子水中，加入前述物料，混捏后在单螺杆挤条机上挤成直径3.0mm的三叶草形。在100℃干燥5小时，再于750℃焙烧4小时，得到氧化铝载体E，其性质见表1。
比较例2
将34.1g氢氧化铝干胶粉(含氧化铝75％的烷基铝水解产物)和硫酸铝法制得的氢氧化铝39.3g混合后加入聚氧乙烯醚3.5g和2.1g醋酸、66mL水混捏，在单螺杆挤条机上挤成直径2.5mm的圆柱形。在80℃干燥8小时，再于600℃焙烧4小时，得到氧化铝载体F，其性质见表1。
采用BET对上述实施例和对比例制备得到的氧化铝载体进行分析，结果见表1。
表1氧化铝载体物化性质
项目 A B C D E F
比表面积，m<sup>2</sup>/g 229 220 218 214 154 171
孔体积，mL/g 1.05 1.07 1.10 1.20 0.68 0.64
最可几孔径，nm 21.1 23.4 23.4 21.6 11.5 10.7
20～30nm孔分布，％ 50.3 53.5 56.8 64.8 8.2 4.3
强度，N/mm 23.4 21.8 19.2 15.0 12.7 10.1
表1的结果表明，与比较例相比较，本发明方法制备的氧化铝载体孔容、孔径更大，最可几孔径为15～30nm，20～30nm以上大孔的孔体积占总孔容的45～70％；含硼化合物和聚氧乙烯醚的复合扩孔作用更好，孔径孔容更大；本发明方法制备的氧化铝载体，强度更高，满足工业应用要求。

Claims (10)

1.一种氧化铝载体，其特征在于，所述氧化铝载体的孔容为1.00～1.50mL/g；比表面积为200～300m2/g；最可几孔径为15～30nm；20～30nm以上大孔的孔体积占总孔容的45～70％，所述氧化铝载体采用的复合扩孔剂为含硼化合物和聚氧乙烯醚。
2.一种权利要求1所述的氧化铝载体的制备方法，其特征在于，包括如下步骤：
A、拟薄水铝石的制备
(1)将偏铝酸钠溶于去离子水中，得到偏铝酸钠溶液；
(2)将偏铝酸钠溶液在搅拌条件下加入到硫酸铝溶液中；
(3)将步骤(2)所得产物在陈化条件下陈化；
(4)将步骤(3)所得陈化产物过滤，洗涤、干燥，得到拟薄水铝石M；
B、氧化铝载体的制备
(1)将拟薄水铝石M与复合扩孔剂和助挤剂混合并成型、干燥；
(2)对(1)中所得的颗粒物在600～1000℃下焙烧1～6小时；
其中，所述的复合扩孔剂为含硼化合物和聚氧乙烯醚。
3.根据权利要求2所述的氧化铝载体的制备方法，其特征在于，制得的拟薄水铝石M孔容为1.1～2.2mL/g，比表面积为130～500m2/g，最可几孔径为15～35nm。
4.根据权利要求2所述的氧化铝载体的制备方法，其特征在于，所述的含硼化合物优选硼酸、氧化硼和硼酸盐中的一种或几种。
5.根据权利要求2所述的氧化铝载体的制备方法，其特征在于，以硼计，所述的含硼化合物的加入量优选为拟薄水铝石M中对应的氧化铝重量的0.5～5％。
6.根据权利要求2所述的氧化铝载体的制备方法，其特征在于，所述的聚氧乙烯醚为烷基酚聚氧乙烯醚、蓖麻油聚氧乙烯醚、脂肪胺聚氧乙烯醚、脂肪酸聚氧乙烯脂其中的一种或几种。
7.根据权利要求2所述的氧化铝载体的制备方法，其特征在于，所述的聚氧乙烯醚的加入量优选为拟薄水铝石M中对应的氧化铝重量的0.5～3％。
8.根据权利要求2所述的氧化铝载体的制备方法，其特征在于，所述的助挤剂优选为田菁粉或淀粉。
9.根据权利要求2所述的氧化铝载体的制备方法，其特征在于，所述的助挤剂的加入量优选为拟薄水铝石M中对应的氧化铝重量的1～3％。
10.根据权利要求1所述的氧化铝载体作为加氢催化剂的应用。
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