CN109529950B - 一种用于h2和co制备乙烯的催化剂 - Google Patents

一种用于h2和co制备乙烯的催化剂 Download PDF

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CN109529950B
CN109529950B CN201811480284.3A CN201811480284A CN109529950B CN 109529950 B CN109529950 B CN 109529950B CN 201811480284 A CN201811480284 A CN 201811480284A CN 109529950 B CN109529950 B CN 109529950B
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陈浩
赵岩
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Xinyi Xinnan Environmental Protection Industry Technology Research Institute Co Ltd
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Abstract

本发明公开了一种用于H2和CO制备乙烯的催化剂，所述的催化剂为Cr2O3/CuO负载X5固体催化剂。该催化剂能催化CO和H2的脱水反应制备乙烯,具有较高的产物选择性。

Description

一种用于H2和CO制备乙烯的催化剂
技术领域
本发明涉及 一种用于H2和CO制备乙烯的催化剂。
背景技术
乙烯是生产众多有机化工产品的基本原料。目前，国内外生产乙烯的工业方法主要是石脑油热裂解法。鉴于由含碳或碳氢物质(煤、天然气、有机废料等)转化为合成气(CO和H2)及由乙烯生产众多有机化学品均已是成熟的工业技术，实现CO和H2低成本制备乙烯新工艺，便为合理利用含碳资源和发展乙烯化学工业提供了一条新的通道。而实CO和H2直接合成乙烯的关键技术是实用工业固体催化剂及其催化反应工艺。目前，巨内外普遍采用的石脑油砂子炉裂解制乙烯工业技术，反应在600--800℃的高温下完成，能耗很高;反应产物复杂，乙烯选择性约30%，需要通过深冷分离，过程相当复杂，极大地增加了生产成本，急需一种用于催化一氧化碳和氢气脱水反应制取乙烯效率好的催化剂。
发明内容
本发明的目的在于提供一种用于H2和CO制备乙烯的催化剂，该催化剂能催化CO和H2的脱水反应制备乙烯,具有较高的产物选择性。
一种用于H2和CO制备乙烯的催化剂，其特征在于，所述的催化剂为Cr2O3/CuO负载X5固体催化剂。
Cr2O3/CuO负载X5固体催化剂制备方法如下：
步骤1、将市售X5树脂用甲醇浸泡10h，以除去树脂中夹杂的有机杂质和色素，过滤，再用去离子水清洗至pH=7；
步骤2、用浓度23%的盐酸溶液对树脂进行活化10h后，取出过滤，再次用去离子水进行清洗至pH=7，过滤，将树脂至于干燥箱中，80℃下烘干，取出研磨，得X5树脂粉体；
步骤4、将3.6g硝酸铬和14.4g硝酸铜溶解在280ml水中超声分散10min，然后在60℃下继续磁力搅拌4h，加入36.0g的X5树脂粉体；
步骤5、激烈搅拌下缓慢滴加碳酸铵沉淀剂，滴加至溶液PH=9.3，室温下放置陈化12h，然后过滤、去离子水洗涤至PH=7；
步骤6、洗涤完毕，置于干燥箱中110℃下干燥过夜，得Cr2O3/CuO负载X5固体催化剂
有益效果：本发明提供了 一种低成本乙烯的制备方法，采用Cr2O3/CuO负载X5固体催化剂催化一氧化碳和氢气脱水反应制取高选择性和高纯度的低成本乙烯。相比较于传统的SiO2或合金催化剂，乙烯的选择性有很大的提高，利用Cr3+和Cu2+在树脂表面的均匀负载形成密集的反应活性位，极大地提高了产物的转化率；此外生成小分子乙烯后能迅速脱离催化剂表面，避免了进一步深度反应，影响反应的活性，降低副反应发生的可能，经络合分离提纯确保乙烯的纯度，充分利用反应热和产物中水蒸气和余气带来的回收热，循环利用降低能耗，从而实现在高选择性下的低成本合成，而且整个工艺过程无毒无害，符合环保生产的要求。
具体实施方式
实施例1
Cr2O3/CuO负载X5固体催化剂制备方法如下：
步骤1、将市售X5树脂用甲醇浸泡10h，以除去树脂中夹杂的有机杂质和色素，过滤，再用去离子水清洗至pH=7；
步骤2、用浓度23%的盐酸溶液对树脂进行活化10h后，取出过滤，再次用去离子水进行清洗至pH=7，过滤，将树脂至于干燥箱中，80℃下烘干，取出研磨，得X5树脂粉体；
步骤4、将3.6g硝酸铬和14.4g硝酸铜溶解在280ml水中超声分散10min，然后在60℃下继续磁力搅拌4h，加入36.0g的X5树脂粉体；
步骤5、激烈搅拌下缓慢滴加碳酸铵沉淀剂，滴加至溶液PH=9.3，室温下放置陈化12h，然后过滤、去离子水洗涤至PH=7；
步骤6、洗涤完毕，置于干燥箱中110℃下干燥过夜，得Cr2O3/CuO负载X5固体催化剂。
对照例1
与实施例1不同点在于：乙烯的合成步骤1中，用等量的氧化铜作为催化剂装填反应器，其余步骤与实施例1完全相同。
对照例2
与实施例1不同点在于：乙烯的合成步骤1中，用等量的氧化铬作为催化剂装填反应器，其余步骤与实施例1完全相同。
对照例3
与实施例1不同点在于：催化剂制备过程步骤4中，硝酸铬和硝酸铜质量比1:1，其余步骤与实施例1完全相同。
对照例4
与实施例1不同点在于：催化剂制备过程步骤4中，硝酸铬和硝酸铜质量比4:1，其余步骤与实施例1完全相同。
对照例5
与实施例1不同点在于：催化剂制备过程步骤4中，采用等量氧化铝取代X5树脂，其余步骤与实施例1完全相同。
对照例6
与实施例1不同点在于：催化剂制备过程步骤4中，采用等量双酚A树脂取代X5树脂，其余步骤与实施例1完全相同。
H2和CO制备乙烯包括以下步骤：
步骤1、将实施例和对比例的固体催化剂填充在列管式等温固定床反应器的列管内，列管间用高压高温水调控催化反应温度，控制温度为128℃；
步骤2、将精制过的原料气H2和CO按摩尔比5:4，在0.7Mpa压力下与反应后混合气换热和移出催化反应器加压高温水加热至128℃，以原料气空速3300h-1通过催化反应床进行化学反应；
步骤3、反应后混合气与原料气经过换热和空气冷却至室温过程中分离出的反应产物H2O，通过加压水加热锅炉升温至128℃后作为催化反应床的调控温度水利用；
步骤4、通过络合分离乙烯后的余气作为加压水加热炉燃料回收利用，反应后的混合干气经络合分离乙烯系统制得高纯度乙烯产品。
实施例和对照例不同条件下的反应结果如表所示
实施例1 96.4
对照例1 43.2
对照例2 47.6
对照例3 47.1
对照例4 50.3
对照例5 57.3
对照例6 61.0
实验结果表明该工艺对CO和H2的脱水反应,具有较高的产物选择性，在反应条件一定时，乙烯选择性越高，催化性能越好，反之越差，对照例1至对照例 2用等量的氧化铜和氧化铬取代催化剂，其他步骤完全相同，导致产物选择性明显降低，说明单组分的催化效果并不理想；对照例3至对照例4将硝酸铬和硝酸铜质量比，效果依然不好，说明二者的负载比例影响了催化剂的催化性能；对照例5至对照例6用等量氧化铝和双酚A树脂取代X5树脂，效果明显变差，说明X5树脂比较适合该反应体系。因此使用本发明的工艺对乙烯的合成具有优异的效果。

Claims (1)

1.一种用于H2 和CO制备乙烯的催化剂，其特征在于，所述的催化剂为Cr2 O3 /CuO负载X5固体催化剂；Cr2 O3 /CuO负载X5固体催化剂制备方法如下：
步骤1、将市售X5树脂用甲醇浸泡10h，以除去树脂中夹杂的有机杂质和色素，过滤，再用去离子水清洗至pH=7；
步骤2、用浓度23%的盐酸溶液对树脂进行活化10h后，取出过滤，再次用去离子水进行清洗至pH=7，过滤，将树脂至于干燥箱中，80℃下烘干，取出研磨，得X5树脂粉体；
步骤4、将3.6g硝酸铬和14.4g硝酸铜溶解在280ml水中超声分散10min，然后在60℃下继续磁力搅拌4h，加入36.0g的X5树脂粉体；
步骤5、激烈搅拌下缓慢滴加碳酸铵沉淀剂，滴加至溶液p H=9.3，室温下放置陈化12h，然后过滤、去离子水洗涤至p H=7；
步骤6、洗涤完毕，置于干燥箱中110℃下干燥过夜，得Cr2 O3 /CuO负载X5固体催化剂。
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