CN113457661A - 一种醋酸氨化合成乙腈用催化剂及其制备方法 - Google Patents
一种醋酸氨化合成乙腈用催化剂及其制备方法 Download PDFInfo
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- CN113457661A CN113457661A CN202110929087.0A CN202110929087A CN113457661A CN 113457661 A CN113457661 A CN 113457661A CN 202110929087 A CN202110929087 A CN 202110929087A CN 113457661 A CN113457661 A CN 113457661A
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Abstract
本发明提供了一种醋酸氨化合成乙腈用催化剂及其制备方法,催化剂为含有过渡金属或稀土金属氧化物的多孔球形氧化铝,氧化铝的晶型为γ型或δ型中一种或两种的混合晶相,将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石混合后与过渡金属和稀土金属盐及扩孔剂混合,使用油氨柱成球方法制得小球,活化焙烧,得到含有过渡金属和稀土金属氧化物的多孔球形氧化铝,再将得到的氧化铝进行水化处理,干燥后得到该催化剂。本发明所述的催化剂在制备过程中加入了少量过渡金属和稀土金属等助剂,使催化剂稳定性得到改善,催化反应温度大幅降低,改善催化剂结焦情况,延长催化剂寿命,催化剂活性及选择性得到提高。
Description
技术领域
本发明属于催化剂领域,尤其是涉及一种醋酸氨化合成乙腈用催化剂及其制备方法。
背景技术
乙腈亦称甲基腈,是一种重要的化工原料。由于乙腈具有特殊官能团腈基,作为溶剂,它除了具有乙醇、甲醇等溶剂所具有的特性外,还具有比醇类更好的分配比和解吸能力,同时有高的介电强度和偶极矩,因而可成为无机和有机化合物的优良溶剂。由于高纯乙腈在200nm-400nm不吸收紫外线,因此,可作为高效液相色谱HPLC的溶剂,可使分析灵敏度高达10-9级。随着这项测试技术的普及,色谱纯级高纯乙腈需求量将逐年增长。乙腈还可作为萃取蒸馏法的溶剂,从C4烃类中分离丁二烯。乙腈也用于其它烃类的分离,如从烃的馏分中分离出丙烯、异戊二烯和甲基乙炔等。乙腈还用于一些特殊的分离,如从植物油和鱼肝油中萃取分离脂肪酸,使处理过的油色淡、纯净、气味改善,而维生素含量不变。在医药、农药、纺织、塑料部门里,也广泛采用乙腈作溶剂。在医药上,乙腈用于合成维生素B1,甲硝羟乙唑、乙胺丁醇、氨苯蝶啶、腺嘌呤和敌退咳等一系列重要药物中间体;在农药上,用于合成拟除虫菊酯类杀虫剂和乙肟威等农药中间体。由于乙腈是极性较强的有机溶剂,对油脂、无机盐、有机物和高分子化合物均有很好的溶解性,可以清洗掉硅片上的油脂、蜡、指纹、腐蚀剂和助焊剂残留物等。所以开始使用高纯乙腈作半导体清洗剂。
目前,国内外乙腈的工业生产方法,主要是由生产丙烯腈的副产物中提取的,除此之外还可以通过醋酸、乙醇、乙炔等原料合成乙腈:
(1)丙烯腈副产法:丙烯气相氨氧化制取丙烯腈的过程中,副产2%左右的乙腈,反应方程式如下:2C3H6+3NH3+3O2→3CH3CN+6H2O;
(2)乙醇氨氧化法:乙醇在高温下与氨气、氧气催化剂生成乙腈,反应方程式如下:2C2H5OH+3NH3+3O2→CH3CN+8H2O+2HCN;
(3)乙醇氨化脱氢法,反应方程式如下:C2H5OH+NH3→CH3CN+2H2+H2O;
(4)乙炔氨化法,以乙炔、氨气为原料,以三氧化二铝催化剂,在500-600℃温度下,一步反应合成乙腈反应式如下:C2H2+NH3→CH3CN+H2;
(5)醋酸高温氨化脱水制乙腈是比较常见的乙腈化学合成方法,反应方程式如下:CH3COOH+NH3→CH3CN+2H2O
上述方法中,丙烯腈副产法的乙腈产量受丙烯腈产能的限制,每生产一吨丙烯腈副产约20kg乙腈;乙醇氨氧化法会产生副产物氢氰酸;乙醇氨化法会副产氢气,同时会有甲胺、二甲胺、三甲胺等副产物;乙炔法反应温度过高,能耗大。目前醋酸高温氨化脱水制乙腈是主流的乙腈合成工艺,被很多人研究。
公开号为CN104447404B的专利公开一种使用锆钨介孔分子筛催化剂制备乙腈的方法,醋酸和氨在摩尔比1:2.5-7混合进入装有催化剂的固定床反应器,反应温度360-450℃,气体经水吸收得到乙腈产品;
公开号为CN101856608A的专利一种乙腈合成催化剂制备方法,该催化剂是由氧化铝、K2MoO4、固体酸等混合而成,反应温度350℃,醋酸和氨在摩尔比1:1.5;
公开号为CN104529819B的专利公开了醋酸氨化法制备乙腈的方法,将醋酸和氨气混合预热后进入装有脱水催化剂的固定床反应器,反应温度360-450℃,反应得到乙腈产品,催化剂为氢型分子筛,转化率接近100%,乙腈收率大于99%;
公开号为CN107108475B的专利公开了一种乙腈的制备方法,使用具有氧八元环细孔结构的沸石分子筛为催化剂如SAPO34、SSZ-13、ALPO-34进行反应,得到的乙腈中杂质甲苯的含量低于1ppm。
但上述专利所使用的反应条件一般都在350℃以上,反应温度较高,且氨气用量较大,提高了后续氨气回收成本,且部分专利并没有对该反应的杂质进行详细描述。
发明内容
有鉴于此,本发明旨在提出一种醋酸氨化合成乙腈用催化剂及其制备方法,以在较低温度和较少的氨用量下,得到较高的醋酸转化率及乙腈收率,同时得到较低的副产物收率。
为达到上述目的,本发明的技术方案是这样实现的:
一种醋酸氨化合成乙腈用催化剂,所述催化剂为含有过渡金属或稀土金属氧化物的多孔球形氧化铝,氧化铝的晶型为γ型或δ型中一种或两种的混合晶相。
进一步地,所述催化剂的比表面积为300-400m2/g,堆密度为0.1-1g/ml,孔容为0.1-1cc/g,孔径分布10-100nm,最可几孔径分布为5-20nm,催化剂抗压强度大于50N/颗。
进一步地,所述过渡金属为Cr、Zn、Mn、Cu、Fe、Co、Ni、Zr、Nb、Mo中至少一种金属,所述稀土金属为La、Ce、Sm、Pr、Nd中至少一种金属,催化剂中氧化铝与过渡金属及稀土金属氧化物的质量比为100:1-10:1-10。
如上所述的催化剂的制备方法,包括以下步骤:
(1)将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石混合制胶,然后将其与一定量的过渡金属和稀土金属盐及扩孔剂混合均匀,然后使用油氨柱成球方法制得小球,将小球在空气气氛下活化焙烧,得到含有过渡金属和稀土金属氧化物的多孔球形氧化铝;
(2)将步骤(1)中得到的氧化铝进行水化处理,干燥后得到催化剂成品。
进一步地,步骤(1)中的扩孔剂为聚乙烯醇、聚乙二醇、田箐粉、聚丙烯酰胺、甲基纤维素中的一种,催化剂中氧化铝与扩孔剂的质量比为100:5-20。
进一步地,步骤(1)中硫酸铝和偏铝酸钠中和反应中硫酸铝和偏铝酸钠的物质的量的比为1:6-6.5,中和反应的温度为60-80℃。
进一步地,步骤(1)中硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石的质量比为70-90:30-10。
进一步地,步骤(1)中制得的小球的直径为2-3mm。
进一步地,步骤(1)中的焙烧温度为300-800℃,焙烧时间为2-10h;优选地,焙烧温度为300-600℃,焙烧时间为3-8h。
进一步地,步骤(2)中水化处理温度为50-100℃,处理时间为2-10h,干燥温度为100-300℃,干燥时间为2-5h;优选地,水化处理温度为70-90℃。
相对于现有技术,本发明所述的醋酸氨化合成乙腈用催化剂及其制备方法具有以下优势:
本发明所述的催化剂在制备过程中加入了少量过渡金属和稀土金属等助剂,使催化剂稳定性得到改善,催化反应温度大幅降低,改善催化剂结焦情况,延长催化剂寿命,催化剂活性及选择性得到提高,经检测使用本发明中的催化剂进行催化反应的温度小于340℃,醋酸转化率大于99.9%,乙腈选择性大于98%,丙酮选择性小于1.5%,乙酰胺选择性小于0.5%,微量杂质总选择性小于0.5%。
具体实施方式
除有定义外,以下实施例中所用的技术术语具有与本发明所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明,均为常规生化试剂;所述实验方法,如无特殊说明,均为常规方法。
下面结合实施例来详细说明本发明。
本发明中醋酸氨化合成乙腈用催化剂的制备方法如下:
(1)将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为70-90:30-10混合制胶,然后将其与一定量的过渡金属和稀土金属盐及扩孔剂混合均匀,然后使用油氨柱成球方法制得直径为小球,将小球在300-800℃空气气氛下活化焙烧2-10h,,得到含有过渡金属和稀土金属氧化物的多孔球形氧化铝,其中,硫酸铝和偏铝酸钠中和反应中硫酸铝和偏铝酸钠的物质的量之比为1:6-6.5,中和反应的温度为60-80℃;
(2)将上述氧化铝进行水化处理,水化处理温度为50-100℃,处理时间为2-10h,处理完毕后在100-300℃下干燥2-5h,得到催化剂成品。
其中,步骤(1)中过渡金属为Cr、Zn、Mn、Cu、Fe、Co、Ni、Zr、Nb、Mo中至少一种金属,稀土金属为La、Ce、Sm、Pr、Nd中至少一种金属,催化剂中氧化铝与过渡金属和稀土金属氧化物的质量比为100:1-10:1-10。其中,扩孔剂为聚乙烯醇、聚乙二醇、田箐粉、聚丙烯酰胺、甲基纤维素中的一种,催化剂中氧化铝和扩孔剂质量比为:100:5-20。偏铝酸钠和硫酸铝的中和反应中,两者的物质的量的比为6-6.5:1,中和反应温度在60-80℃。
步骤(2)制得的催化剂比表面积为300-400m2/g,堆密度为0.1-1g/ml,孔容为0.1-1cc/g,孔径分布10-100nm,最可几孔径分布为5-20nm,催化剂抗压强度大于50N/颗,氧化铝晶型为γ型或δ型混合晶相。经检测上述催化剂的进行催化反应的条件如下:反应温度<340℃,反应压力1bar,醋酸和氨气摩尔比1:1-1.1,醋酸转化率>99.9%,乙腈选择性>98%,丙酮选择性<1.5%,乙酰胺选择性<0.5%,微量杂质总选择性<0.5%。
本发明制备的催化剂的评价方法如下:将300g催化剂装入固定床反应器中,反应器为DN40长度为1m的不锈钢管,反应管外有导热油夹套,反应器由高温导热油系统供热。冰醋酸由计量泵输送和氨气在汽化器中混合预热至300℃,进入装有催化剂的反应器中,反应温度控制在320℃,反应压力为1bar,醋酸和氨气摩尔比为1:1.05。反应产物经冷凝器冷凝进入气液分离罐分离气液两相,对液相进行收集并进行气相色谱分析。
气相色谱分析条件如下:
设备:色谱:安捷伦8860;
色谱柱:安捷伦,HP-INNOWAX,30m×530um×1um;
检测器:温度300℃,空气流量400sccm,氢气流量30sccm;
进样口:温度300℃,压力15psi;
柱箱温度:50℃(升温速度25℃/min)→150℃(保持5min)→150℃(升温速度25℃/min)→250℃(保持5min)。
实施例1
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为80:20混合制胶,然后将其与一定量的硝酸锌和硝酸镧及田箐粉混合均匀,然后使用油氨柱成球方法制得直径为3mm小球,将小球在400℃的空气气氛下活化焙烧8小时,得到含有氧化锌和氧化镧的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为70℃,处理时间为10h,处理完毕后在200℃下干燥5h,得到催化剂成品。其中氧化铝与氧化锌和氧化镧的质量比为100:5:5,氧化铝与田箐粉的质量比为100:10。所得催化剂比表面积为310m2/g,堆密度为0.6g/ml,孔容为0.65cc/g,孔径分布10-50nm,最可几孔径分布为16.5nm,催化剂抗压强度为98N/颗,氧化铝晶型为γ型。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.91%,乙腈选择性为98.4%,丙酮选择性为1.25%,乙酰胺选择性为0.163%,丙腈选择性为0.066%,丁酮选择性为0.028%,丙啶选择性为0.035%,丁烯腈选择性为0.047%。
实施例2
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为70:30混合制胶,然后将其与一定量的硝酸锰和硝酸亚铁及聚乙二醇混合均匀,然后使用油氨柱成球方法制得直径为3mm小球,将小球在450℃的空气气氛下活化焙烧6小时,得到含有氧化锰和氧化亚铁的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为50℃,处理时间为2h,处理完毕后在300℃下干燥2h,得到催化剂成品。其中氧化铝与氧化锰和氧化亚铁的质量比为100:1:10,氧化铝与聚乙二醇的质量比为100:5。所得催化剂比表面积为350m2/g,堆密度为0.55g/ml,孔容为0.56cc/g,孔径分布2-50nm,最可几孔径分布为17.2nm,催化剂抗压强度为110N/颗,氧化铝晶型为γ型。
评价方法如前所述,经评价装置评价后,醋酸转化率为100%,乙腈选择性为98.55%,丙酮选择性为1.25%,乙酰胺选择性为0.015%,丙腈选择性为0.071%,丁酮选择性为0.028%,丙啶选择性为0.035%,丁烯腈选择性为0.051%。
实施例3
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为90:10混合制胶,然后将其与一定量的硝酸铬和硝酸铈及聚乙烯醇混合均匀,然后使用油氨柱成球方法制得直径为2mm小球,将小球在500℃的空气气氛下活化焙烧2小时,得到含有氧化铬和氧化铈的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为70℃,处理时间为10h,处理完毕后在200℃下干燥5h,得到催化剂成品。其中氧化铝与氧化锌和氧化镧的质量比为100:2:8,氧化铝与聚乙烯醇的质量比为100:7。所得催化剂比表面积为380m2/g,堆密度为0.5g/ml,孔容为0.76cc/g,孔径分布10-50nm,最可几孔径分布为16.3nm,催化剂抗压强度为120N/颗,氧化铝晶型为γ型和δ型混合晶相。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.98%,乙腈选择性为98.45%,丙酮选择性为1.18%,乙酰胺选择性为0.027%,丙腈选择性为0.058%,丁酮选择性为0.05%,丙啶选择性为0.063%,丁烯腈选择性为0.169%。
实施例4
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为75:25混合制胶,然后将其与一定量的硝酸锆和硝酸钐及甲基纤维素混合均匀,然后使用油氨柱成球方法制得直径为2mm小球,将小球在300℃的空气气氛下活化焙烧2小时,得到含有氧化锆和氧化钐的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为50℃,处理时间为2h,处理完毕后在100℃下干燥2h,得到催化剂成品。其中氧化铝与氧化锌和氧化镧的质量比为100:1:9,氧化铝与田箐粉的质量比为100:1。所得催化剂比表面积为300m2/g,堆密度为0.65g/ml,孔容为0.59cc/g,孔径分布10-50nm,最可几孔径分布为15.3nm,催化剂抗压强度为90N/颗,氧化铝晶型为γ型。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.98%,乙腈选择性为98.19%,丙酮选择性为1.249%,乙酰胺选择性为0.217%,丙腈选择性为0.08%,丁酮选择性为0.053%,丙啶选择性为0.067%,丁烯腈选择性为0.141%。
实施例5
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为80:20混合制胶,然后将其与一定量的硝酸铜和硝酸钕及甲基纤维素混合均匀,然后使用油氨柱成球方法制得直径为2mm小球,将小球在600℃的空气气氛下活化焙烧3小时,得到含有氧化铜和氧化钕的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为100℃,处理时间为10h,处理完毕后在300℃下干燥5h,得到催化剂成品。其中氧化铝与氧化锌和氧化镧的质量比为100:8:2,氧化铝与田箐粉的质量比为100:10。所得催化剂比表面积为381m2/g,堆密度为0.65g/ml,孔容为0.61cc/g,孔径分布10-50nm,最可几孔径分布为16.5nm,催化剂抗压强度为100N/颗,氧化铝晶型为γ型和δ型混合晶相。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.91%,乙腈选择性为98.64%,丙酮选择性为0.911%,乙酰胺选择性为0.181%,丙腈选择性为0.043%,丁酮选择性为0.039%,丙啶选择性为0.049%,丁烯腈选择性为0.133%。
实施例6
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为85:15混合制胶,然后将其与一定量的硝酸钴和硝酸铌及聚乙烯醇混合均匀,然后使用油氨柱成球方法制得直径为3mm小球,将小球在800℃的空气气氛下活化焙烧10小时,得到含有氧化钴和氧化铌的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为90℃,处理时间为8h,处理完毕后在200℃下干燥4h,得到催化剂成品。其中氧化铝与氧化锌和氧化镧的质量比为100:9:1,氧化铝与田箐粉的质量比为100:5。所得催化剂比表面积为354m2/g,堆密度为0.6g/ml,孔容为0.71cc/g,孔径分布10-50nm,最可几孔径分布为17.2nm,催化剂抗压强度为100N/颗,氧化铝晶型为δ型。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.99%,乙腈选择性为98.38%,丙酮选择性为1.043%,乙酰胺选择性为0.209%,丙腈选择性为0.08%,丁酮选择性为0.048%,丙啶选择性为0.059%,丁烯腈选择性为0.177%。
实施例7
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为85:15混合制胶,然后将其与一定量的硝酸镍及田箐粉混合均匀,然后使用油氨柱成球方法制得直径为3mm小球,将小球在600℃的空气气氛下活化焙烧5小时,得到含有氧化镍的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为90℃,处理时间为6h,处理完毕后在150℃下干燥8h,得到催化剂成品。其中氧化铝与氧化镍的质量比为100:10,氧化铝与田箐粉的质量比为100:2。所得催化剂比表面积为371m2/g,堆密度为0.55g/ml,孔容为0.71cc/g,孔径分布10-50nm,最可几孔径分布为16.1nm,催化剂抗压强度为95N/颗,氧化铝晶型为γ型。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.92%,乙腈选择性为98.17%,丙酮选择性为1.008%,乙酰胺选择性为0.5%,丙腈选择性为0.043%,丁酮选择性为0.057%,丙啶选择性为0.07%,丁烯腈选择性为0.149%。
实施例8
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为85:15混合制胶,然后将其与一定量的硝酸镍及田箐粉混合均匀,然后使用油氨柱成球方法制得直径为3mm小球,将小球在600℃的空气气氛下活化焙烧5小时,得到含有氧化镍的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为90℃,处理时间为6h,处理完毕后在150℃下干燥8h,得到催化剂成品。其中氧化铝与氧化镍的质量比为100:10,氧化铝与田箐粉的质量比为100:2。所得催化剂比表面积为371m2/g,堆密度为0.55g/ml,孔容为0.71cc/g,孔径分布10-50nm,最可几孔径分布为16.1nm,催化剂抗压强度为95N/颗,氧化铝晶型为γ型。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.92%,乙腈选择性为98.17%,丙酮选择性为1.008%,乙酰胺选择性为0.5%,丙腈选择性为0.043%,丁酮选择性为0.057%,丙啶选择性为0.07%,丁烯腈选择性为0.149%。
实施例9
将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石按质量比为85:15混合制胶,然后将其与一定量的硝酸钼及聚丙烯酰胺混合均匀,然后使用油氨柱成球方法制得直径为3mm小球,将小球在400℃的空气气氛下活化焙烧2小时,得到含有氧化钼的多孔球形氧化铝。将上述氧化铝进行水化处理,水化处理温度为60℃,处理时间为5h,处理完毕后在200℃下干燥6h,得到催化剂成品。其中氧化铝与氧化镍的质量比为100:8,氧化铝与田箐粉的质量比为100:8。所得催化剂比表面积为390m2/g,堆密度为0.55g/ml,孔容为0.71cc/g,孔径分布10-50nm,最可几孔径分布为16.1nm,催化剂抗压强度为1205N/颗,氧化铝晶型为γ型。
评价方法如前所述,经评价装置评价后,醋酸转化率为99.93%,乙腈选择性为98.65%,丙酮选择性为0.92%,乙酰胺选择性为0.148%,丙腈选择性为0.051%,丁酮选择性为0.042%,丙啶选择性为0.052%,丁烯腈选择性为0.133%。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
1.一种醋酸氨化合成乙腈用催化剂,其特征在于:所述催化剂为含有过渡金属或稀土金属氧化物的多孔球形氧化铝,氧化铝的晶型为γ型或δ型中一种或两种的混合晶相。
2.根据权利要求1所述的催化剂,其特征在于:所述催化剂的比表面积为300-400m2/g,堆密度为0.1-1g/ml,孔容为0.1-1cc/g,孔径分布10-100nm,最可几孔径分布为5-20nm,催化剂抗压强度大于50N/颗。
3.根据权利要求1所述的催化剂,其特征在于:所述过渡金属为Cr、Zn、Mn、Cu、Fe、Co、Ni、Zr、Nb、Mo中至少一种金属,所述稀土金属为La、Ce、Sm、Pr、Nd中至少一种金属,催化剂中氧化铝与过渡金属及稀土金属氧化物的质量比为100:1-10:1-10。
4.如权利要求1-3任一所述的催化剂的制备方法,其特征在于,包括以下步骤:
(1)将硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石混合制胶,然后将其与一定量的过渡金属和稀土金属盐及扩孔剂混合均匀,然后使用油氨柱成球方法制得小球,将小球在空气气氛下活化焙烧,得到含有过渡金属和稀土金属氧化物的多孔球形氧化铝;
(2)将步骤(1)中得到的氧化铝进行水化处理,干燥后得到催化剂成品。
5.根据权利要求4所述的制备方法,其特征在于:步骤(1)中的扩孔剂为聚乙烯醇、聚乙二醇、田箐粉、聚丙烯酰胺、甲基纤维素中的一种,催化剂中氧化铝与扩孔剂的质量比为100:5-20。
6.根据权利要求4所述的制备方法,其特征在于:步骤(1)中硫酸铝和偏铝酸钠中和反应中硫酸铝和偏铝酸钠的物质的量的比为1:6-6.5,中和反应的温度为60-80℃。
7.根据权利要求4所述的制备方法,其特征在于:步骤(1)中硫酸铝和偏铝酸钠中和制得的粉体与拟薄水铝石的质量比为70-90:30-10。
8.根据权利要求4所述的制备方法,其特征在于:步骤(1)中制得的小球的直径为2-3mm。
9.根据权利要求4所述的制备方法,其特征在于:步骤(1)中的焙烧温度为300-800℃,焙烧时间为2-10h;优选地,焙烧温度为300-600℃,焙烧时间为3-8h。
10.根据权利要求4所述的制备方法,其特征在于:步骤(2)中水化处理温度为50-100℃,处理时间为2-10h,干燥温度为100-300℃,干燥时间为2-5h;优选地,水化处理温度为70-90℃。
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