性能优异的Pd-[DBU][Cl]/AC无汞催化剂在乙炔氢氯化中的应用

doi:10.1016/S1872-2067(22)64204-9

催化学报 ›› 2023, Vol. 46: 137-147.DOI: 10.1016/S1872-2067(22)64204-9

性能优异的Pd-[DBU][Cl]/AC无汞催化剂在乙炔氢氯化中的应用

董兴宗^a^,^b, 刘广业^a, 陈兆安^a, 张权^a^,^b, 徐云鹏^a^,^*(), 刘中民^a^,^b

^a中国科学院大连化学物理研究所, 大连洁净能源国家实验室, 低碳催化技术国家工程研究中心, 辽宁大连 116023
^b中国科学院大学, 化学工程学院, 北京 100049

收稿日期:2022-10-14 接受日期:2022-12-05 出版日期:2023-03-18 发布日期:2023-02-21
通讯作者: *电子邮箱: xuyunpeng@dicp.ac.cn (徐云鹏)
基金资助:
国家重点研发计划(2016YFB0301603); 辽宁振兴人才计划(XLYC1905017)

Enhanced performance of Pd-[DBU][Cl]/AC mercury-free catalysts in acetylene hydrochlorination

Xingzong Dong^a^,^b, Guangye Liu^a, Zhaoan Chen^a, Quan Zhang^a^,^b, Yunpeng Xu^a^,^*(), Zhongmin Liu^a^,^b

^aNational Engineering Research Center of Lower-Carbon Catalysis Technology, Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
^bSchool of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2022-10-14 Accepted:2022-12-05 Online:2023-03-18 Published:2023-02-21
Contact: *E-mail: xuyunpeng@dicp.ac.cn (Y. Xu)
Supported by:
Key Technologies Research and Development Program(2016YFB0301603);The Liaoning Revitalization Talents Program(XLYC1905017)

摘要/Abstract

摘要：

氯乙烯单体(VCM)作为重要的有机化工原料, 主要用于聚氯乙烯(PVC)生产, 在煤炭资源丰富的国家和地区氯乙烯单体的制备很大程度上依赖乙炔氢氯化反应. 目前工业乙炔氢氯化过程仍然使用传统的活性炭负载氯化汞(HgCl₂/AC)作为反应的催化剂, 但该催化剂的易挥发性和高毒性对人类健康和生态环境造成了极大的危害, 因此探索和发展性能优异且环境友好的无汞催化剂尤为重要. Pd基催化剂展现出较好的乙炔氢氯化活性, 但较差的化学稳定性限制了其工业应用. 因此, 通过调节Pd(II)活性中心的电子结构、配位状态和微环境去提升Pd基催化剂的化学稳定性是当前的研究热点和挑战. 相关的文献结果表明, Pd基催化剂的快速失活主要归因于Pd(II)被乙炔分子还原成Pd(0), 导致催化剂表面大量积碳的形成以及活性Pd物种流失, 根本原因是催化剂活性位点对乙炔的吸附较强而对氯化氢的吸附较弱, 这种不匹配的吸附会造成吸附态的乙炔无法与氯化氢发生有效碰撞生成产物氯乙烯, 因此如何促进氯化氢的高效吸附和活化是阻止催化剂失活的关键因素. 基于我们前期的工作(Mol. Catal., 2022, 525, 112366)和相关文献调研发现, 1,8-二氮杂二环十一碳-7-烯氯盐([DBU][Cl])对氯化氢分子有较强的吸附和活化能力, 而且[DBU][Cl]作为配体能与Pd(II)金属中心配位构建一个稳定的活性位点.

本文制备了一系列Pd-[DBU][Cl]/AC催化剂去提升Pd基催化剂在乙炔氢氯化过程中的化学稳定性, 催化剂的乙炔氢氯化活性和化学稳定性在固定床微反应器上评价. 采用N₂物理吸附、X射线光电子能谱(XPS)、电感耦合等离子体发射光谱(ICP-OES)、程序升温脱附(TPD)和热重分析(TGA)等表征方法研究了Pd基催化剂的失活原因以及Pd-[DBU][Cl]/AC催化剂稳定性增强的原因. 通过DFT理论模拟分析了乙炔、氯化氢和C₂H₃Cl在Pd活性位点上的吸附行为并提出了乙炔氢氯化反应在PdCl₂-[DBU][Cl]位点上的催化循环机理. Pd/AC和Pd-20[DBU][Cl]/AC的初始乙炔转化率分别为88.2%和99.8%, 评价24 h后的转化率分别为0.7%和96.7%, 而事实上Pd/AC在反应1 h后已经基本失活, 实验结果表明, [DBU][Cl]的存在能极大地抑制Pd基催化剂的失活, 提高其化学稳定性. 表征结果表明, 反应过程中部分的Pd(II)被还原成Pd(0), Pd活性物种的流失以及大量积碳的生成是Pd/AC催化剂迅速失活的原因. 反应前后的XPS的表征结果表明, [DBU][Cl]与Pd(II)的相互作用能降低, Pd(II)被还原成Pd(0); ICP-OES数据证实[DBU][Cl]的存在能减少Pd活性物种的损失量; N₂物理吸附和TGA的实验结果也表明[DBU][Cl]的引入可以抑制催化剂表面积碳的产生. TPD实验结果表明, PdCl₂-[DBU][Cl]相比于PdCl₂拥有更大的氯化氢吸附量以及更小的C₂H₂吸附量; DFT理论计算证实PdCl₂-[DBU][Cl]相比于PdCl₂存在更大的氯化氢吸附能以及更小的乙炔和C₂H₃Cl吸附能. 寿命实验结果表明, Pd-20[DBU][Cl]/AC催化剂展现出较好的活性和良好的稳定性, 在T = 180 °C, GHSV (C₂H₂) = 360 h^‒1和V(HCl)/V(C₂H₂) = 1.2的条件下, 乙炔的初始转化率达到99.8%且在反应60 h内的失活速率仅为0.12%/h.

关键词: 乙炔氢氯化, 无汞催化剂, Pd复合物催化剂, 提升稳定性, 吸附能

Abstract:

Compared with the rapid deactivation of the Pd/AC catalyst, an eco-friendly Pd-[DBU][Cl]/AC ([DBU][Cl], 1,8-diazabicyclo[5.4.0]undec-7-ene hydrochloride) catalyst with enhanced stability was synthesized and applied in the hydrochlorination of acetylene. The Pd-20[DBU][Cl]/AC catalyst exhibits 96.7% acetylene conversion and 98.9% selectivity of vinyl chloride within the 24 h evaluation under the conditions of T = 180 °C, GHSV(C₂H₂) = 360 h^-1 and V(HCl)/V(C₂H₂) = 1.2. The enhanced stability of the Pd-[DBU][Cl]/AC catalyst is attributed to the prevention of the reduction of Pd(II) to Pd(0), the inhibition of the formation of coke deposition on the catalyst surface, and the reduction of the loss of Pd species during the reaction. TPD characterization and DFT theoretical simulations confirmed that the PdCl₂-[DBU][Cl] complex has stronger adsorption of HCl and weaker adsorption of C₂H₂ and C₂H₃Cl compared to PdCl₂. Furthermore, the catalytic mechanism of acetylene hydrochlorination over the PdCl₂ and PdCl₂-[DBU][Cl] site was put forward based on theoretical simulations. The good activity and stability of Pd-20[DBU][Cl]/AC in the 60 h lifetime test indicates that it is likely to be a promising alternative to HgCl₂ catalysts.

Key words: Acetylene hydrochlorination, Mercury-free catalyst, Pd complex catalyst, Enhanced stabilityAdsorption energy

董兴宗, 刘广业, 陈兆安, 张权, 徐云鹏, 刘中民. 性能优异的Pd-[DBU][Cl]/AC无汞催化剂在乙炔氢氯化中的应用[J]. 催化学报, 2023, 46: 137-147.

Xingzong Dong, Guangye Liu, Zhaoan Chen, Quan Zhang, Yunpeng Xu, Zhongmin Liu. Enhanced performance of Pd-[DBU][Cl]/AC mercury-free catalysts in acetylene hydrochlorination[J]. Chinese Journal of Catalysis, 2023, 46: 137-147.

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图/表 12

Table 1 Texture parameters of catalysts.

Sample	S_BET^a (m² g^-1)		V_total^b (cm³ g^-1)
Sample	Fresh	Spent	Fresh	Spent
Pd/AC	1431	53	0.53	0.13
Pd-1[DBU][Cl]/AC	1238	29	0.42	0.09
Pd-5[DBU][Cl]/AC	1233	42	0.48	0.12
Pd-10[DBU][Cl]/AC	901	62	0.37	0.12
Pd-20[DBU][Cl]/AC	538	124	0.34	0.19
Pd-40[DBU][Cl]/AC	86	72	0.15	0.15

Fig. 1. Nitrogen adsorption-desorption isotherms (a), XRD pattern (b), XPS full spectrum (c), STEM image (d) of the Pd-20 [DBU][Cl]/AC catalyst.

Fig. 2. Acetylene conversion (a) and selectivity to VCM (b) over different samples. Reaction conditions: T = 180 °C, GHSV(C2H2) = 360 h-1 and V(HCl)/V(C2H2) = 1.2. (c) Acetylene conversion under different [DBU][Cl] loading. Reaction conditions: T = 180 °C, GHSV(C2H2) = 360 h-1 and V(HCl)/V(C2H2) = 1.2. (d) Acetylene conversion of Pd-20 [DBU][Cl]/AC at different reaction temperatures. Reaction conditions: GHSV(C2H2) = 360 h-1 and V(HCl)/V(C2H2) = 1.2.

Table 4 Pd content of catalysts.

Sample	Pd content^a (%)		Nominal loss rate (%)	Actual loss rate (%)
Sample	Fresh	Spent	Nominal loss rate (%)	Actual loss rate (%)
Pd/AC	0.219	0.136	38.1	20.3
Pd-1[DBU][Cl]/AC	0.226	0.131	42.1	28.2
Pd-5[DBU][Cl]/AC	0.214	0.144	32.7	17.6
Pd-10[DBU][Cl]/AC	0.208	0.143	31.2	22.3
Pd-20[DBU][Cl]/AC	0.177	0.145	18.1	11.4
Pd-40[DBU][Cl]/AC	0.142	0.137	3.38	1.85

Fig. 3. Pd 3d XPS spectra of Pd/AC (a) and Pd-20[DBU][Cl]/AC (b). TGA profiles of Pd/AC (c) and Pd-20[DBU][Cl]/AC (d) in air atmosphere.

Fig. 4. TPD profiles of C2H2 and HCl on the fresh catalysts. (a) C2H2-TPD; (b) HCl-TPD.

Fig. 5. The HOMO structures of PdCl2 (a) and [DBU][Cl] (c) and the LUMO structures of PdCl2 (b) and [DBU][Cl] (d).

Table 2 Relative contents of Pd species on the spent catalysts.

Sample	Relative content^a (area %)
Sample	Pd(0) (3d_5/2: 333.0eV)	Pd(II) (3d_5/2: 336.8eV)
Pd/AC-Spent	67	33
Pd-1[DBU][Cl]/AC-Spent	50	50
Pd-5[DBU][Cl]/AC-Spent	44	56
Pd-10[DBU][Cl]/AC-Spent	41	59
Pd-20[DBU][Cl]/AC-Spent	31	69
Pd-40[DBU][Cl]/AC-Spent	34	66

Table 3 Coke deposition of catalysts.

Sample	The amount of coke deposition^a (%)
Pd/AC	26.43
Pd-1[DBU][Cl]/AC	21.88
Pd-5[DBU][Cl]/AC	21.58
Pd-10[DBU][Cl]/AC	12.40
Pd-20[DBU][Cl]/AC	7.57
Pd-40[DBU][Cl]/AC	0.92

Fig. 6. (a) The adsorption energy of C2H2, HCl and C2H3Cl on PdCl2 and PdCl2-[DBU][Cl]. (b) Hirshfeld charge variations in the interaction of HCl, C2H2 and C2H3Cl with PdCl2 and PdCl2-[DBU][Cl]. Positive values represent catalysts as electron acceptors. (c) The long-term stability test of Pd-20[DBU][Cl]/AC. (d) TGA profiles of the fresh and spent Pd-20[DBU][Cl]/AC after evaluation.

Fig. 7. Reaction pathway diagram and geometric structures involved in acetylene hydrochlorination over the PdCl2-[DBU][Cl] site. H, C, N, Cl and Pd atoms are depicted in white, gray, slate-blue, green and cyan respectively. The unit of bond length and distance is ?.

Fig. 8. The catalytic cycle mechanism for acetylene hydrochlorination over PdCl2-[DBU][Cl] catalyst.

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性能优异的Pd-[DBU][Cl]/AC无汞催化剂在乙炔氢氯化中的应用

Enhanced performance of Pd-[DBU][Cl]/AC mercury-free catalysts in acetylene hydrochlorination

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