CN114073947A - 一种二氧化碳氧化乙烷催化剂的制备方法 - Google Patents

一种二氧化碳氧化乙烷催化剂的制备方法 Download PDF

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CN114073947A
CN114073947A CN202010828950.9A CN202010828950A CN114073947A CN 114073947 A CN114073947 A CN 114073947A CN 202010828950 A CN202010828950 A CN 202010828950A CN 114073947 A CN114073947 A CN 114073947A
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贺健
殷惠琴
田先国
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Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Abstract

本发明属于化工催化剂技术领域,具体涉及一种二氧化碳氧化乙烷催化剂的制备方法。其特征是将硅酸钠和硝酸铬的混合溶液中放置于超声波中,而后加入碳酸铵溶液形成凝胶,经成型、老化、干燥、焙烧等工序制得催化剂。采用本发明方法制备的催化剂物理性能良好,热稳定性高,成本低廉,用于二氧化碳氧化乙烷反应中,乙烷转化率大于35%,乙烯选择性大于65%。

Description

一种二氧化碳氧化乙烷催化剂的制备方法
技术领域
本发明属于化工催化剂技术领域,具体涉及一种二氧化碳氧化乙烷催化剂的制备方法。
技术背景
乙烯产量是衡量一个国家石油化工发展水平的重要标志之一,其生产目前主要来源于石脑油或者轻油的解裂过程。随着石油资源日趋紧张,利用来源丰富且廉价的乙烷脱氢来制取乙烯越来越引起人们的关注。
乙烷脱氢制乙烯虽然已经实现了工业化,但是由于受热力学平衡转化率的限制,反应温度基本在850℃以上,能耗特别高。因此在反应体系中引入温和氧化剂二氧化碳成为一种可行的实验方案,它不发生乙烷深度氧化,可以保证产物乙烯的选择性;同时为脱氢吸热反应提供部分能源,降低反应温度,符合当今环保需求。
目前用于二氧化碳氧化乙烷制乙烯的催化剂虽具有较好的活性好选择性,但是催化剂的稳定性却非常差;如果提高稳定性又会牺牲活性,成本也大幅提升。因此价格低廉的高效催化剂是目前二氧化碳氧化乙烷脱氢制备乙烯领域的重要研究方向。
发明内容
本发明的目的是提供二氧化碳氧化乙烷催化剂的制备方法,获得活性高、稳定性好的二氧化碳氧化乙烷催化剂。
本发明提出的一种二氧化碳氧化乙烷催化剂的制备方法,是将硅酸钠和硝酸铬的混合溶液置于超声波环境中,而后加入碳酸铵溶液形成凝胶,经成型、老化、干燥、焙烧等工序制得催化剂。
在本发明的催化剂制备方法中,原料硅酸钠模数为2.5-3.0. 硅酸钠与硝酸铬摩尔比为20-30.
本催化剂制备方法采用超声波,超声波频率为25-30Hz,超声时间为1-3h。
在本发明的催化剂制备方法中,凝胶老化时间为15-30h,干燥温度为105-120℃,焙烧温度为600-700℃。
采用本发明方法制备的催化剂孔容为0.65-0.85mL/g,比表面积为180-300m2/g,平均孔径为8-10nm。
将本发明方法制备的催化剂用在二氧化碳氧化乙烷反应中,在温度700℃,压力0.4MPa,空速1500h-1的条件下,乙烷转化率为40%-50%,乙烯选择性为50%-70%。
本发明的有益效果:
1)采用本发明方法制备的催化剂大大降低了乙烷制备乙烯反应温度,降低了反应能耗;
2)催化剂制备方法简单,稳定性强,在二氧化碳氧化乙烷制乙烯反应中具有较高的乙烷转化率和乙烯选择性。
具体实施方式
下面结合实施例对本发明做进一步说明,但本发明的保护范围不限于此。
实施例1
称取模数为2.5的硅酸钠配置成1mol/L溶液,量取100ml该硅酸钠溶液和50ml 0.1mol/L的硝酸铬,将其混合搅拌后放置于25Hz超声波反应器中,而后滴加碳酸铵溶液反应1h形成凝胶,老化15h后在105℃干燥以及600℃焙烧后制得催化剂A1。
实施例2
称取模数为2.5的硅酸钠配置成1mol/L溶液,量取100ml该硅酸钠溶液将放置于25Hz超声波反应器中,而后滴加碳酸铵溶液反应1h形成凝胶,老化15h后在105℃干燥以及600℃焙烧后制得催化剂B1。
实施例3
称取模数为3的硅酸钠配置成1mol/L溶液,量取150ml该硅酸钠溶液和50ml 0.1mol/L的硝酸铬,将其混合搅拌后放置于30Hz超声波反应器中,而后滴加碳酸铵溶液反应3h形成凝胶,老化30h后在120℃干燥以及700℃焙烧后制得催化剂A2。
实施例4
称取模数为3的硅酸钠配置成1mol/L溶液,量取150ml该硅酸钠溶液,将其放置于30Hz超声波反应器中,而后滴加碳酸铵溶液反应3h形成凝胶,老化30h后在120℃干燥以及700℃焙烧后制得催化剂B2。
实施例5
称取模数为2.8的硅酸钠配置成1mol/L溶液,量取120ml该硅酸钠溶液和50ml 0.1mol/L的硝酸铬,将其混合搅拌后放置于28Hz超声波反应器中,而后滴加碳酸铵溶液反应2h形成凝胶,老化20h后在110℃干燥以及650℃焙烧后制得催化剂A3。
实施例6
称取模数为2.8的硅酸钠配置成1mol/L溶液,量取120ml该硅酸钠溶液,将其放置于28Hz超声波反应器中,而后滴加碳酸铵溶液反应2h形成凝胶,老化20h后在110℃干燥以及650℃焙烧后制得催化剂B3。
实施例7
用全自动多功能气体吸附仪测试催化剂物理性质如下:
催化剂 孔容mL/g 比表面积m<sup>2</sup>/g 孔径nm
A1 0.66 185 9.7
B1 0.71 198 9.4
A2 0.78 273 8.3
B2 0.82 301 9.5
A3 0.71 213 8.9
B3 0.75 240 9.1
实施例8
在温度700℃,压力0.4MPa,空速1500h-1的条件下,测试催化剂在二氧化碳氧化乙烷反应中转化率和选择性,其结果如下:
Figure 535366DEST_PATH_IMAGE002

Claims (9)

1.一种二氧化碳氧化乙烷催化剂的制备方法,其特征在于,将硅酸钠和硝酸铬的混合溶液置于超声波环境中,而后加入碳酸铵溶液形成凝胶,经成型、老化、干燥、焙烧等工序制得催化剂。
2.如权利要求1所述催化剂制备方法,其特征在于所述硅酸钠模数为2.5-3.0。
3.如权利要求1所述催化剂制备方法,其特征在于所述硅酸钠与硝酸铬摩尔比为20-30。
4.如权利要求1所述催化剂制备方法,其特征在于所述超声波频率为25-30Hz。
5.如权利要求1所述催化剂制备方法,其特征在于所述超声时间为1-3h。
6.如权利要求1所述催化剂制备方法,其特征在于所述老化时间为15-30h。
7.如权利要求1所述催化剂制备方法,其特征在于所述干燥温度为105-120℃。
8.如权利要求1所述催化剂制备方法,其特征在于所述焙烧温度为600-700℃。
9.如权利要求1所述催化剂制备方法,其特征在于所制备的催化剂孔容为0.65-0.85mL/g,比表面积为180-300m2/g,平均孔径为8-10nm。
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05170673A (ja) * 1991-12-25 1993-07-09 Tosoh Corp エタンによる二酸化炭素の変換方法
CN106563489A (zh) * 2016-10-28 2017-04-19 复旦大学 用于二氧化碳气氛下乙烷脱氢制乙烯的催化剂及其制备方法
CN110586094A (zh) * 2019-08-27 2019-12-20 天津大学 碳酸乙烯酯加氢生产甲醇和乙二醇的铜基纳米花催化剂及其制备方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05170673A (ja) * 1991-12-25 1993-07-09 Tosoh Corp エタンによる二酸化炭素の変換方法
CN106563489A (zh) * 2016-10-28 2017-04-19 复旦大学 用于二氧化碳气氛下乙烷脱氢制乙烯的催化剂及其制备方法
CN110586094A (zh) * 2019-08-27 2019-12-20 天津大学 碳酸乙烯酯加氢生产甲醇和乙二醇的铜基纳米花催化剂及其制备方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
魏可;和晓才;陈家辉;施辉献: "沉淀法和沉淀二氧化硅微粒" *

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