CN1097483C - 新型无铬铁系一氧化碳高温变换催化剂及其制备 - Google Patents

新型无铬铁系一氧化碳高温变换催化剂及其制备 Download PDF

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CN1097483C
CN1097483C CN00105435A CN00105435A CN1097483C CN 1097483 C CN1097483 C CN 1097483C CN 00105435 A CN00105435 A CN 00105435A CN 00105435 A CN00105435 A CN 00105435A CN 1097483 C CN1097483 C CN 1097483C
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魏可镁
郑起
徐建本
林性怡
魏明灯
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CHEMICAL FERTILIZER CATALYST STATE ENGINEERING RESEARCH CENTER FUZHOU UNIV
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Abstract

本发明公开了一种用于合成氨及制氨工业中一氧化碳加水蒸气变换反应制取氢气的新型无铬铁系一氧化碳高温变换催化剂及其制备方法。它由氧化铁、铝铁硅复合氧化物或铝硅胶、钒氧化物、镁氧化物、镍氧化物、氧化钾等化学组份组成，分别采用混沉淀和混碾法两种工艺制备方法，制得该种无铬高变催化剂产品。

Description

新型无铬铁系一氧化碳高温变换催化剂及其制备
所述技术领域
本发明涉及一种用于合成氨及制氢工业中一氧化碳加水蒸汽变换反应制取氢气的催化剂及其制备方法，具体地说是一种新型无铬铁系一氧化碳高温变换催化剂。
背景技术
传统的一氧化碳高变催化剂为铁铬系变换催化剂，铬是该催化剂重要的助剂，它可大幅度提高催化剂的活性、耐热性和使用寿命。但它又是一种很强的致癌物质，在催化剂制造、使用过程及废弃后都给人体和环境带来严重的危害。因此，无铬铁系高变催化剂的研制，已引起国内外学者的极大关注。
自七十年代以来，世界各国开展无铬高变催化剂研究工作的有：
前苏联伊凡诺夫化工研究所研制的CTK-＞KC型铁铅系高变催化剂，含PbO10％～14％，引入了新的污染物铅。
英国ICI公司开发无铬71-1和71-2型催化剂，其主要成份为CaO、CeO2、ZrO2或HfO2等。但制造困难，价格昂贵。
日本日产公司采用Fe2O3、Al2O3、CuO、K2O及Pt组份制备无铬催化剂。
中国内蒙古工业大学申请的专利《铁系无铬型高(中)温变换催化剂及其生产方法》(申请号：95121834.4)是采用Fe2O3、CeO2、Al2O3、K2O组份开展NBC型无铬催化剂的研制。
上述研究工作不同程度存在着制造困难、成本高、产生新污染源等问题，致使研究进展缓慢。
发明内容
为了克服现有催化剂污染等问题，本发明的目的是制造一种能彻底消除铬的污染，且不增加新的污染源，原料易得，制备工艺简单，可在现行高变催化剂生产线上实现规模生产的，由氧化铁、铝铁硅复合氧化物或铝硅胶、钒氧化物、镁氧化物、镍氧化物、氧化钾等化学组份组成的新型无铬铁系一氧化碳高温变换催化剂。
本发明解决其技术问题采用的技术方案是：一种新型无铬铁系一氧化碳高温变换催化剂及其制备，其催化剂的特征在于无铬组份，有效组份由重量百分含量为65％～90％的氧化铁，1％～10％的铝铁硅复合氧化物或铝硅胶，0.5％～2.0％的钒氧化物，0.5％～3.0％的镁氧化物，0.5％～5.0％的镍氧化物，0.1％～0.6％的氧化钾组成。
催化剂的制备方法：用30℃～50℃的热水溶解固体硫酸亚铁FeSO4.7H2O，其浓度以氧化铁计为130～180g/l，将固体碳酸氢铵溶化为溶液并通液氨调节使碳酸铵溶液中(NH4)2CO3浓度为180g/L～280g/L，NH4OH浓度20g/L～100g/L。将上述的硫酸亚铁液和碳酸铵液在中和罐中并流中和沉淀，中和温度为65℃～75℃，pH值为6.5～7.5，时间180min，沉淀液经90℃～95℃热煮60min后，用40℃～60℃清水洗涤4-6次，澄清液用10％的BaCl2溶液滴定，无白色沉淀，为洗涤完成。洗涤后的料浆由下面两种工艺流程完成催化剂制备：
方法一：按配料比配入铝铁硅复合氧化物、镁氧化物、钒氧化物、镍氧化物，打浆30min，打浆后的物料将经压滤得到滤饼，滤饼经烘干后按配料比配入KOH，在碾磨机中碾压60min，碾压后的物料经造粒、300℃～350℃焙烧90～120min后，再配入0.5％～1.0％石墨粉进行打片，即得圆柱状无铬催化剂产品。
方法二：洗涤后的料浆经压滤、烘干后按配料比配入所有助剂，在碾压机中碾压1小时。碾压后的物料经造粒、300℃～350℃焙烧90～120min，再配入0.5％～1.0％的石墨粉进行打片，即得圆柱状产品。
本发明的有益效果是通过深入的基础理论研究和大量性能测定、表征，发现铬在高变催化剂中不仅起结构助剂作用，而且还起电子助剂作用。在此理论指导下，经过大量的配方筛选，工艺改革，应用特殊工艺加工形成铝铁硅复合氧化物或铝硅胶，通过制造、还原进入Fe3O4晶格，使晶粒度变小，比表面增大，取代氧化铬的骨架助剂作用提高了催化剂的稳定性；加入钒氧化物在反应体系中以V4+存在于Fe3O4的A位(正四面体位)代替Cr6+起电子助剂作用，从XPS和穆斯堡尔谱证实了这点；镍氧化物的加入提高了催化剂表面富集OH基团的能力，使催化剂在水碳比为1.85下仍具有高活性和高抗硫能力。为此，本发明无铬铁系高变催化剂的性能达到传统铁铬系催化剂的水平。
附图说明
图1是本发明方法1的工艺流程图。
图2是本发明方法2的工艺流程图。
具体实施方式
图1中将固体硫酸亚铁溶解为硫酸亚铁溶液，将固体碳酸氢铵溶解为溶液并通入氨调节得到所需的铵液。硫酸亚铁液和铵液在中和罐中并流中和沉淀，沉淀经热煮、洗涤后按配料比加入助剂进行打浆，打浆后物料经压滤后得到滤饼。滤饼经烘干、加入KOH碾压、造粒、加石墨混合、打片，即得成品。
图2中将固体硫酸亚铁溶解为硫酸亚铁液，将固体碳酸氢铵溶解为溶液并通入氨调节得到所需的铵液。硫酸亚铁液和铵液在中和罐中并流中和沉淀，沉淀经热煮、洗涤、压滤、烘干、按配料比加入各种助剂碾压、造粒、加石墨混合、打片，即得成品。
实例1：
以生产1000kg催化剂为基准，需90％的七水合硫酸亚铁3100kg，碳酸氢铵1200kg，液氨200kg，铝铁硅复合氧化物60kg，钒氧化物15kg，镁氧化物20kg，镍氧化物45kg，氢氧化钾5kg，石墨8kg。
将FeSO4.7H2O溶于30℃～50℃的热水中，得到以氧化铁浓度为130～180g/l的硫酸亚铁溶液，将固体碳酸氢铵溶解为溶液并通液氨调节使铵液中(NH4)2CO3浓度为180g/L～280g/L，NH4OH浓度20g/L～100g/L。当反应罐的底水温度达60℃时，将上述的硫酸亚铁液和铵液并流加入反应罐起中和反应，起始小流量，逐渐加大。中和温度65℃～75℃，pH控制在6.5～7.5，时间约为180min。中和结束前半小时，溶液进行返酸处理，调节流量使pH控制在6.5，维持15min返碱，pH调至7.2搅拌15min后，结束中和。中和后沉淀物料提温至90℃～95℃热煮60min.沉淀物料用40℃～60℃清水洗涤4～6次，洗涤液用10％的BaCl2溶液滴定，无白色沉淀，为洗涤完成，得到氧化铁料浆。
在氧化铁料浆中按配料比配入铝铁硅复合氧化物、镁氧化物、钒氧化物、镍氧化物，打浆30min，打浆后的料浆经压滤得到滤饼，滤饼经烘干后按配料比配入氢氧化钾溶液，在碾磨机中碾压60min，碾压后的物料经造粒、300℃～350℃焙烧90～120min后，再配入0.5％～1.0％石墨粉进行打片，即得Φ9mmχ(6～8)mm圆柱状无铬催化剂产品。
该成品按ZBG74001-89标准检测，耐热后CO转化率为55.7％，平均颗粒径向抗压碎强度275N/cm，低强度百分率2.5％，磨耗率3.6％，烧失重2.5％。
实例2：
氧化铁料浆的制备方法同实例1，洗涤合格后的氧化铁料浆经压滤、烘干后按配料比配入所有助剂，在碾压机中碾压1小时。碾压后的物料经造粒、300℃～350℃焙烧90～120min，再配入0.5％～1.0％的石墨粉进行打片，即得成品。
该成品按ZBG74001-89标准检测条件进行检测，耐热后CO转化率为52.3％，平均颗粒径向抗压碎强度325N/cm，低强度百分率0％，磨耗率3.3％，烧失重5.1％。
该批样在工业试用，效果良好，寿命达3年以上。
实例3：
以生产1000kg催化剂为基准，需90％的七水合硫酸亚铁3100kg，碳酸氢铵1200kg，液氨200kg，铝硅胶(含硅铝40％，硅铝比2∶8)100kg，钒氧化物15kg，镁氧化物20kg，镍氧化物45kg，氢氧化钾5kg，石墨8kg。生产方法同实例2。
该成品按ZBG74001-89标准检测条件进行检测，耐热后CO转化率为49.3％，平均颗粒径向抗压碎强度360N/cm，低强度百分率0％，磨耗率4.5％，烧失重6.1％。

Claims (4)

1.一种新型无铬铁系一氧化碳高温变换催化剂其特征在于无铬组份，有效组份由重量百分含量为65％～90％的氧化铁，1％～10％的铝铁硅复合氧化物或铝硅胶，0.5％～2.0％的钒氧化物，0.5％～3.0％的镁氧化物，0.5％～5.0％的镍氧化物，0.1％～0.6％的氧化钾组成。
2.根据权利要求1所述的催化剂的制备方法，其特征是制备方法1将固体FeSO4.7H2O溶化为硫酸亚铁溶液，并将固体碳酸氢铵溶化为溶液并通液氨调节为碳铵溶液，硫酸亚铁液和碳酸铵液在中和罐中并流中和沉淀，沉淀液经热煮、洗涤后得到氧化铁料浆，按配料比配入铝铁硅复合氧化物、镁氧化物、钒氧化物、镍氧化物，打浆经压滤得到滤饼，滤饼经烘干后按配料比配入KOH，再经碾压、造粒、焙烧、打片，即得圆柱状无铬催化剂产品；其特征是制备方法2将固体FeSO4.7H2O溶化为硫酸亚铁溶液，并将固体碳酸氢铵溶化为溶液并通液氨调节为碳铵溶液，硫酸亚铁液和碳酸铵液在中和罐中并流中和沉淀，沉淀液经热煮、洗涤、过滤、烘干后，按配料比配入所有助剂，经碾压、造粒、焙烧、打片，即得圆柱状无铬催化剂产品。
3.根据权利要求2所述的催化剂的制备方法，其中氧化铁料浆的制备特征是将固体硫酸亚铁FeSO4.7H2O在30℃～50℃下溶化为硫酸亚铁溶液，其浓度以氧化铁计为130～180g/l，将固体碳酸氢铵溶化为溶液并通液氨调节为碳铵溶液，其中(NH4)2CO3浓度为180g/L～280g/L，NH4OH浓度20g/L～100g/L；硫酸亚铁液和碳酸铵液在中和罐中并流中和沉淀，控制中和温度为65℃～75℃，pH值为6.5～7.5，中和反应时间为180min，沉淀液经90℃～95℃热煮60min后，用40℃～60℃清水洗涤4-6次，澄清液用10％的BaCl2溶液滴定，无白色沉淀，为洗涤完成，得到氧化铁料浆。
4.根据权利要求2所述的催化剂的制备方法，其特征是打浆时间为30min，碾压时间为60min。
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