Page 155 - 《精细化工》2023年第9期

第 40 卷第 9 期 精 细 化 工 Vol.40, No.9
20 23 年 9 月 FINE CHEMICALS Sept. 2023

催化与分离提纯技术
用于合成气制高值产物的 InZrO 制备及性能
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郭玉静 ，郑和平 ，肖大强 ，任 宇 ，冉龙腾 ，唐建华
（1. 四川大学 化学工程学院，四川 成都 610065；2. 四川煤炭产业集团有限责任公司，四川 成都
610091；3. 攀煤联合焦化有限责任公司，四川 攀枝花 617000）
摘要：以四水合硝酸铟和五水合硝酸锆为原料，通过共沉淀法和水热法制备了 InZrO x ，并在最佳制备方法下探
究煅烧温度对合成 InZrO x 晶体结构和催化效果的影响。与 SAPO-34 分子筛结合为双功能催化剂用于合成气催化
转化制高值产物。采用 XRD、SEM-EDS、HRTEM、XPS 和 BET 对 InZrO x 的织构性质、晶体结构、形貌特征
及表面元素进行了表征与测试，并在固定床反应器中研究了空速、原料气 H 2 /CO 物质的量比（简称氢碳比）、
InZrO x 与分子筛质量比、反应温度及反应压力对催化效果的影响规律。结果表明，共沉淀法得到的 InZrO x 在各
方面表现均优于水热法，最佳煅烧温度为 550 ℃。在空速为 2000 mL/(g cat ·h)、原料气氢碳比为 3∶1、m(InZrO x )∶
m(SAPO-34)=1∶1、400 ℃、3 MPa 的反应条件下，得到了较高的 CO 转化率（67.58%）、高值产物选择性〔低
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碳烯烃（C 2~4 ）选择性为 37.74%、液体燃料（C 5+ ）烃类选择性为 33.07%〕和 C 2~4 收率（23.98%），副产物 CO 2
选择性仅为 5.99%。
关键词：合成气；轻烯烃；双功能催化剂；水热法；共沉淀法；催化技术
中图分类号：O643.36；TQ133.53 文献标识码：A 文章编号：1003-5214 (2023) 09-2003-10

Preparation and performance of InZrO x on conversion

of syngas to high-value products

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GUO Yujing , ZHENG Heping , XIAO Daqiang , REN Yu , RAN Longteng , TANG Jianhua
（1. College of Chemical Engineering, Sichuan University, Chengdu 610065, Sichuan, China; 2. Sichuan Coal Industry
Group Limited Liability Company, Chengdu 610091, Sichuan, China; 3. Panzhihua Coal United Coking Limited
Liability Company, Panzhihua 617000, Sichuan, China）
Abstract: InZrO x was prepared from co-precipitation and hydrothermal reaction of indium nitrate
tetrahydrate and zirconium nitrate pentahydrate respectively, and the effect of calcination temperature on
the crystal structure and catalytic performance of the synthesized InZrO x was investigated under the optimal
preparation method. The InZrO x obtained was then combined with SAPO-34 molecular sieve to form a
bifunctional catalyst, which was applied in the catalytic conversion of syngas to high-value products. The
texture properties, crystal structure, morphology features, and surface elements of the InZrO x were
characterized by XRD, SEM-EDS, HRTEM, XPS and BET. And the catalytic performance influencing
factors, including space velocity, mole ratio of H 2 to CO in feed gas (hydrogen carbon ratio), mass ratio of
InZrO x to molecular sieve, reaction temperature, and reaction pressure, were analyzed in a fixed bed reactor.
The results showed that the InZrO x obtained by co-precipitation method exhibited better performance in all
aspects in comparison to that from hydrothermal reaction, with the optimum calcination temperature of
550 ℃. Under the conditions of space velocity 2000 mL/(g cat ·h), hydrogen carbon ratio 3∶1, m(InZrO x)∶
m(SAPO-34)=1∶1, 400 ℃, and 3 MPa, the catalytic reaction displayed high CO conversion rate (67.58%),
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high-value product selectivity [(The selectivity of light olefins (C 2~4) and liquid fuels (C 5+) were 37.74%
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and 33.07%)] and C 2~4 yield (23.98%), and by-product CO 2 selectivity of 5.99%.
Key words: syngas; light olefins; bifunctional catalysts; hydrothermal method; co-precipitation method;
catalysis technology

收稿日期：2022-11-24; 定用日期：2023-03-22; DOI: 10.13550/j.jxhg.20221078
基金项目：国家自然科学基金（22178236，21878194）；横向项目二氧化碳耦合瓦斯气催化制乙烯技术开发（22H0551）
作者简介：郭玉静（1999—），女，硕士生，E-mail：guoyujing990127@163.com。联系人：郑和平（1970—），男，博士，高级工程师，
E-mail：zhpcd@sina.com。