CN100586560C - 坡缕石负载镍基生物质焦油重整制氢催化剂及其制备方法 - Google Patents
坡缕石负载镍基生物质焦油重整制氢催化剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种以坡缕石为载体的镍基催化剂及其制备方法，按重量百分比计，氧化镍在催化剂中的含量为1-40%，氧化铁为5-20%，氧化钾为1-10%。采用共沉淀吸附的方式将镍、铁负载到坡缕石表面，催化剂经过滤、成型、干燥、煅烧制得成品催化剂。在常压、反应温度为480～650℃的操作条件下，固定床反应器中，热解焦油的产气量和裂解率都大大提高，制得的催化剂与商业轻油蒸汽转化制氢催化剂相比具有成本低、低温活性好、易还原、抗积碳能力强的特点。广泛适用于化学、化工领域的各类烷烃的水蒸气重整制氢反应。
Description
技术领域
本发明属于能源化工领域，涉及能适用于生物质气化过程中下游焦油催化重整过程或生物质油直接水蒸气重整制氢过程的催化剂和制备技术，特别是以坡缕石为载体的镍基生物质焦油水蒸气重整制氢催化剂及其制备方法。
背景技术
随着化石能源的日益枯竭和全球环境恶化，生物质作为可再生能源越来越受到人们的广泛关注。其中，生物质气化制氢技术因为结合了可再生能源和清洁能源载体(氢能)的优点而成为一种十分有发展前景的技术。然而，在气化过程中不可避免的伴随着焦油的产生。焦油因在低温下冷凝、聚集而导致设备腐蚀、堵塞和能量的损失，如何高效去除焦油、净化产气成为生物质气化技术能够广泛应用的瓶颈。在众多的焦油的去除技术中，以催化水蒸气重整焦油最为有效。相关催化剂如白云石、碱金属和镍基催化剂等已得到广泛研究。结果表明，催化剂的积碳是导致催化剂失活的主要原因。此外，催化温度也不宜太高，在下游固定床中最适宜的反应温度为500～600℃，因为这几乎不需额外的热量加入，使得该项技术更具有经济上的可行性。因此，开发能在低温下具有良好的活性和抗积碳能力的镍基催化剂变得十分必要。目前世界上以ICI公司开发的ICI46-1和齐鲁石化开发的Z409石脑油烃类蒸汽转化制氢催化剂研究较为广泛。但现有催化剂存在低温活性低、易积碳和价格较昂贵的缺点。
发明内容
本发明克服现有技术中不足之处，提供一种生产成本低廉、低温活性好、抗积碳能力强的以坡缕石为载体的镍基生物质焦油水蒸气重整制氢催化剂及其制备方法。
本发明的技术方案是：以坡缕石为载体的镍基生物质焦油水蒸气重整制氢催化剂，该催化剂的载体为坡缕石，其中NiO的重量百分比为1-40％，Fe2O3的重量百分比为5-20％，K2O的重量百分比为1-10％，坡缕石的重量白分比为50-95％。
以坡缕石为载体的镍基生物质焦油水蒸气重整制氢催化剂的制备方法，该制备方法由下列步骤组成：
(1)坡缕石的预处理：
首先，将250-350目的精制坡缕石用1-2倍体积的稀盐酸溶液浸泡8-12小时，后用蒸馏水反复洗涤至呈中性备用；
(2)共沉淀：
将含结晶水的商品化Ni(NO3)2·6H2O和Fe(NO3)3·9H2O配制成混合金属盐水溶液备用，将商品化的KOH配制成水溶液作为沉淀剂，在装有一定量的蒸馏水的容器中，在连续强力搅拌的条件下，缓慢地将上述配好的金属盐溶液和沉淀剂溶液并流连续滴加到反应容器中，并控制溶液的PH值在9-10，滴加完毕后形成一种浅黄褐色的絮状悬浮液；
(3)吸附和老化：
将步骤(1)制备的盐酸处理过的坡缕石和煮沸淀粉溶液作为造孔剂加入到上述悬浮液中，继续搅拌2-4小时，静止老化8-12小时；
(4)将步骤(3)所得的下层沉淀溶液直接在压滤机中压滤，得浅黄褐色的滤饼。
(5)将步骤(4)得到的滤饼在80-90℃下干燥除去水分，最后在550-650℃下煅烧3-8小时，即为本发明的成型镍基催化剂。
本发明的有益效果是：本发明的催化剂的载体选择为坡缕石。坡缕石(又名凹凸棒石粘土)是一种层链状结构的含水富镁铝硅酸盐粘土矿物，它具有来源广泛、价格低廉、高比表面积、良好的吸附、脱色和粘结的性能。在催化剂的组成中，坡缕石起到为活性组分提供大的比表面、催化剂粘接成型、吸附水和焦油分子的作用；氧化镍作为活性组分起到催化焦油、甲烷等水蒸气重整作用；氧化铁起到促进焦油裂解、水煤气反应和增加催化剂强度的作用；氧化钾起到抗积碳的作用。淀粉在成型时起到造孔剂的作用。
附图说明
下面结合附图和实施例对本发明作进一步说明。
图1是本发明的500℃下产气量随时间的变化图
图2是本发明的600℃下产气量随时间的变化图
图3是本发明的制备流程图
具体实施方式：
实例1
实验室制备15克催化剂(35wt％，NiO)配方：
| 原料种类 | 坡缕石 | 盐酸 | 硝酸镍 | 硝酸铁 | 氢氧化钾 |
| 重量(克) | 10 | 10ml | 13.91 | 4.02 | 9.71 |
实例2
部分成型催化剂(12wt％，NiO)配方：
| 原料种类 | 坡缕石 | 硝酸镍 | 硝酸铁 | 氢氧化钾 | 淀粉 |
| 重量(克) | 125 | 48.68 | 70.26 | 52.86 | 5 |
以固定床杏核热解焦油水蒸气重整为催化剂活性评价实验，并与商业轻油蒸汽转化制氢催化剂Z409进行比较。比较结果表明：500℃下自制Ni-Fe/坡缕石催化剂催化效果明显好于商业Z409催化剂，而600℃下虽初始活性相同但自制催化剂的抗积碳失活能力要明显好于Z409催化剂。
评价条件及结果：
焦油进量：1.1ml/h；N2：44ml/min；催化剂：2.0g；水碳比(摩尔比)：4.3。
表1：两种催化剂组成对比(质量分数)
表二：反应60分钟时取样分析结果
| 催化剂 | Ni-Fe/坡缕石 | Z409 |
| 反应温度(℃) | 500 600 | 500 600 |
| 产气量(ml/min) | 43.5 44.3 | 34.9 44.5 |
| 产气组成(mol％)H<sub>2</sub>CH<sub>4</sub>COCO<sub>2</sub> | 69.1 68.10.5 0.73.5 5.226.8 26.0 | 70.9 68.21.4 0.35.5 3.222.1 28.4 |
| 碳转化率 | 92.1 97.1 | 67.1 97.5 |
Claims (2)
1、坡缕石负载镍基生物质焦油重整制氢催化剂，其特征在于，该催化剂的载体为坡缕石，其中NiO的重量百分比为1-40％，Fe2O3的重量百分比为5-20％，K2O的重量百分比为1-10％，坡缕石的重量白分比为50-95％。
2、坡缕石负载镍基生物质焦油重整制氢催化剂的制备方法，其特征在于，该制备方法由下列步骤组成：
(1)坡缕石的预处理：
首先，将250-350目的精制坡缕石用1-2倍体积的稀盐酸溶液浸泡8-12小时，后用蒸馏水反复洗涤至呈中性备用；
(2)共沉淀：
将含结晶水的商品化Ni(NO3)2·6H2O和Fe(NO3)3·9H2O配制成混合金属盐水溶液备用，将商品化的KOH配制成水溶液作为沉淀剂，在装有一定量的蒸馏水的容器中，在连续强力搅拌的条件下，缓慢地将上述配好的金属盐溶液和沉淀剂溶液并流连续滴加到反应容器中，并控制溶液的PH值在9-10，滴加完毕后形成一种浅黄褐色的絮状悬浮液；
(3)吸附和老化：
将步骤(1)制备的盐酸处理过的坡缕石和煮沸淀粉溶液作为造孔剂加入到上述悬浮液中，继续搅拌2-4小时，静止老化8-12小时；
(4)将步骤(3)所得的下层沉淀溶液直接在压滤机中压滤，得浅黄褐色的滤饼；
(5)将步骤(4)得到的滤饼在80-90℃下干燥除去水分，最后在550-650℃下煅烧3-8小时，即为本发明的成型镍基催化剂。
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