CuZnTiO2/SAPO-34双功能催化剂的设计、制备及其用于CO2加氢制烯烃性能

doi:10.16085/j.issn.1000-6613.2019-0544

摘要/Abstract

摘要：

CO₂加氢经甲醇（含氧中间体）制低碳烯烃工艺路线，可实现成醇、脱水两步反应串联协同进行，打破费托合成产物Anderson-Schulz-Flory（ASF）分布限制，高选择性地制取低碳烯烃。传统甲醇合成Cu基催化剂加氢能力较强，在两步反应中产物以CH₄、低碳烷烃为主。实验设计、制备了CuZnTiO₂/(Zn-)SAPO-34复合催化剂，实现了CO₂加氢在Cu基复合催化剂上高选择性合成C₂～C₄烯烃（约60%）。研究表明，两步反应过程中甲醇体积分数较低（＜6%），且高温下逆水煤气变换反应严重，导致催化剂酸性变化对产物分布的影响较大。调变两类活性位点比例发现，CH₄的产生与串联反应存在竞争关系，SAPO-34酸量的增加抑制了CH₄的生成，促进串联反应正向进行；合适的酸性有助于生成C₂～C₄烯烃。控制成醇、脱水两类活性位点接触距离可调变烯烃的二次反应，降低加氢能力，改善产物分布。

关键词: 二氧化碳, 加氢, 分子筛, 低碳烯烃, 接触距离

Abstract:

CO₂ hydrogenation to light olefins bymethanol synthesis or oxide intermediates, is accomplished through two successive reactions of activation of CO₂ to methanol and methanol conversion to olefins. This route can break the product distribution limitation of Anderson-Schulz-Flory (ASF) via Fischer-Tropsch synthesis and produce light olefins with high selectivity. It is reported that the products from traditional Cu-based composite catalysts mainly include methane and alkanes due to their strong hydrogenation ability during CO₂ hydrogenation. Herein, we report the design and preparation of CuZnTiO₂/(Zn-)SAPO-34 composite catalyst that shows high selectivity for C₂—C₄ olefins (around 60%). The study demonstrates that the acidity of the catalyst has great influence on product distribution, due to the low methanol concentration (＜6%) and high activity of the reverse water gas shift reaction (RWGS) at high temperature during the two-step reaction process. There exists competition between the formation of methane and the tandem reaction with the change of the content of two active components. The increase of the acid content of SAPO-34 can inhibit the formation of methane and promote the tandem reaction. Reduction in acidity of SAPO-34 by Zn promotion also contributes to the formation of light olefins. It is favorable to suppress the secondary hydrogenation reaction of light olefins, by controlling the distance between the two active components.

Key words: carbon dioxide, hydrogenation, molecular sieves, light olefins, contact distance

中图分类号:

O643

陈静宇,张建红,盛浩,吴大凯,高新华,马清祥,张建利,范素兵,赵天生. CuZnTiO₂/SAPO-34双功能催化剂的设计、制备及其用于CO₂加氢制烯烃性能[J]. 化工进展, 2020, 39(2): 567-576.

Jingyu CHEN,Jianhong ZHANG,Hao SHENG,Dakai WU,Xinhua GAO,Qingxiang MA,Jianli ZHANG,Subing FAN,Tiansheng ZHAO. Design and preparation of CuZnTiO₂/SAPO-34 bifunctional catalyst and its catalytic performance in CO₂ hydrogenation to light olefins[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 567-576.

图/表 12

图1 催化剂装填示意图

图2 (Zn-)SAPO-34的XRD谱图和FTIR谱图，CZT、TiO2以及复合催化剂的XRD谱图

图3 不同CZT/SAPO-34比例催化剂的CO2-TPD谱图

图4 催化剂的NH3-TPD谱图

表1 不同样品的NH3-TPD酸量

催化剂	弱酸		强酸		总酸量/mmol·g^-1
催化剂	温度/℃	酸量/mmol·g^-1	温度/℃	酸量/mmol·g^-1	总酸量/mmol·g^-1
CZT	—	—	—	—	—
CZT/SAPO-34(2∶1)	168	0.02	341	0.02	0.04
CZT/SAPO-34(1∶1)	163	0.03	375	0.02	0.04
CZT/SAPO-34(1∶2)	166	0.05	396	0.09	0.14
SAPO-34	172	0.13	389	0.09	0.22
Zn-SAPO-34	174	0.27	442	0.08	0.35
CZT/Zn-SAPO-34(1∶2)	169	0.04	—	0.02	0.06

图5 催化剂的H2-TPR还原曲线

图6 催化剂N2等温吸附-脱附曲线

表2 催化剂结构性质

催化剂	比表面积/m²·g^-1	总孔体积/cm³·g^-1	孔径/nm
CZT	36.4	0.12	2.86
CZT/SAPO-34(1∶2)	64.6	0.10	2.60
CZT/Zn-SAPO-34(1∶2)	60.7	0.09	2.11
SAPO-34	492.6	0.31	0.45
Zn-SAPO-34	416.3	0.32	0.45

图7 催化剂的SEM照片

表3 催化剂催化活性数据

催化剂	CO₂转化率/%	产物选择性/%			烃类选择性/%				O/P
催化剂	CO₂转化率/%	CO	CH	CH₃OH	CH₄	$C 2 = ～ C 40$	$C 2 ～ C 40$	$C 5 +$	O/P
CZT	17.93	93.34	2.55	4.11	94.62	2.56	2.82	0	0.91
CZT/SAPO-34(2∶1)	11.7	83.94	16.06	—	54.77	26.08	19.14	0	1.36
CZT/SAPO-34(1∶1)	7.38	82.96	17.04	—	58.87	16.96	24.17	0	0.7
CZT/SAPO-34(1∶2)	9.23	86.12	13.88	—	38.98	14.28	45.51	1.23	0.31
CZT/Zn-SAPO-34(1∶2)	5.34	76.18	23.82	—	22.37	59.2	16.81	1.63	3.52

表3 催化剂催化活性数据

催化剂	CO₂转化率/%	产物选择性/%			烃类选择性/%				O/P
催化剂	CO₂转化率/%	CO	CH	CH₃OH	CH₄	$C 2 = ～ C 40$	$C 2 ～ C 40$	$C 5 +$	O/P
CZT	17.93	93.34	2.55	4.11	94.62	2.56	2.82	0	0.91
CZT/SAPO-34(2∶1)	11.7	83.94	16.06	—	54.77	26.08	19.14	0	1.36
CZT/SAPO-34(1∶1)	7.38	82.96	17.04	—	58.87	16.96	24.17	0	0.7
CZT/SAPO-34(1∶2)	9.23	86.12	13.88	—	38.98	14.28	45.51	1.23	0.31
CZT/Zn-SAPO-34(1∶2)	5.34	76.18	23.82	—	22.37	59.2	16.81	1.63	3.52

图8 复合催化剂CZT/SAPO-34质量比（2∶1）、（1∶1）、（1∶2）以及CZT/Zn-SAPO-34（1∶2）反应随时间变化性能谱图

图9 活性组分的复合方式对催化性能的影响[还原条件为30%H2+70%N2，常压，350℃/6h；反应条件为H2/CO2=3、380℃、2MPa、3000h-1；反应时间24h；(a)CZT与SAPO-34粉末以质量比1∶1研磨在一起，再压片至20～40目；(b)CZT与SAPO-34压至20～40目，然后以质量比为1∶1均匀混合；(c)CZT与SAPO-34用石英棉隔开，石英棉上层为CZT 20～40目颗粒，下层为SAPO-34 20～40目颗粒，质量比为1∶1装入反应管中]

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CuZnTiO₂/SAPO-34双功能催化剂的设计、制备及其用于CO₂加氢制烯烃性能

Design and preparation of CuZnTiO₂/SAPO-34 bifunctional catalyst and its catalytic performance in CO₂ hydrogenation to light olefins

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