Cu/HY催化剂在乙炔氢氯化反应中的性能及其失活原因

doi:10.11944/j.issn.1000-0518.2018.12.180055

摘要/Abstract

摘要：

采用等体积浸渍法制备了以分子筛为载体的铜基无汞催化剂(Cu/HY),在固定床反应器中,考察了Cu/HY催化剂用于乙炔氢氯化反应制取氯乙烯的催化性能,并采用扫描电子显微镜(SEM)、能量散射光谱(EDS)、电感耦合等离子光谱(ICP-AES)、氮气吸脱附(BET)、热重分析(TG)、透射电子显微镜(TEM)、X射线粉末衍射(XRD)和X射线光电子能谱(XPS)表征手段对反应前后的催化剂进行了表征和分析。结果表明,反应温度为160 ℃,常压,空速为120 h^-1,V(HCl)/V(C₂H₂)=1.25,Cu的负载质量分数为15%时,Cu/HY催化剂的乙炔氢氯化性能最佳,乙炔转化率可达84%,氯乙烯选择性始终大于95%,且具有较好的稳定性;通过表征分析,认为催化剂表面形成积碳,铜活性物种的还原、团聚和流失是导致Cu/HY催化剂活性下降的主要原因。

关键词: 催化剂, 分子筛, 乙炔氢氯化, 催化, 氯乙烯

Abstract:

Zeolite supported Cu-based mercury-free catalysts(Cu/HY) were prepared by incipient-wetness impregnation, and their catalytic performance for acetylene hydrochlorination was evaluated in a fixed reactor. The structure parameters and theory properties of the fresh and used catalysts were characterized by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), inductively coupled plasma-atomic emission spectroscopy(ICP-AES), N₂ adsorption and desorption isotherms(BET), thermogravimetry(TG), transmission electron microscopy(TEM), X-ray powder diffraction(XRD) and X-ray photoelectron spectroscopy(XPS). The acetylene conversion reached 84%, the selectivity for vinyl chloride was more than 95% and a better stability was observed on Cu/HY mercury-free catalysts with 15%(mass fraction) Cu loading, under the reaction conditions of 160 ℃, 101.325 kPa, a total gas hourly space of 120 h^-1, V(HCl)/V(C₂H₂)=1.25. Besides, the characterization results show that the generation of carbon deposition, the reduction, agglomeration and loss of Cu active components are the main reasons for the decrease of the catalyst activity.

Key words: catalysts, zeolite, acetylene hydrochlorination, catalysis, vinyl chloride

相博文, 王璐, 王丰, 王吉德. Cu/HY催化剂在乙炔氢氯化反应中的性能及其失活原因[J]. 应用化学, 2018, 35(12): 1449-1456.

XIANG Bowen, WANG Lu, WANG Feng, WANG Jide. Catalytic Performance and Deactivation of Cu/HY Catalysts for Acetylene Hydrochlorination[J]. Chinese Journal of Applied Chemistry, 2018, 35(12): 1449-1456.

参考文献

[1]	Zhu M Y,Wang Q Q,Chen K,et al. Development of a Heterogeneous Non-Mercury Catalyst for Acetylene Hydrochlorination[J]. ACS Catal,2015,5(9):5306-5316.
[2]	Chao S L,Guan Q X,Li W.Study of the Active Site for Acetylene Hydrochlorination in AuCl3/C Catalysts[J]. J Catal,2015,330:273-279.
[3]	Zhou K,Jia J C,Li C H,et al. Low Content Au-Based Catalyst for Hydrochlorination of C2H2 and Its Industrial Scale-Up for Future PVC Process[J]. Green Chem,2014,17(1):356-364.
[4]	Zhao W L,Zhu M Y,Dai B.The Preparation of Cu-g-C3N4/AC Catalyst for Acetylene Hydrochlorination[J]. Catalysts,2016,6(12):193-203.
[5]	Zhang J L,He Z H,Li W,et al. Deactivation Mechanism of AuCl3 Catalyst in Acetylene Hydrochlorination Reaction:A DFT Study[J]. RSC Adv,2012,2(11):4814-4821.
[6]	Song Q L,Wang S J,Shen B X,et al. Palladium-Based Catalysts for the Hydrochlorination of Acetylene:Reasons for Deactivation and Its Regeneration[J]. Liq Fuels Technol,2010,28(18):1825-1833.
[7]	Pu Y F,Zhang J L,Li Y,et al. Active Ruthenium Species in Acetylene Hydrochlorination[J]. Appl Catal,A,2014,488:28-36.
[8]	Mitchenko S A,Krasnyakova T V,Mitchenko R S,et al. Acetylene Catalytic Hydrochlorination over Powder Catalyst Prepared by Pre-milling of K2PtCl4 Salt[J]. J Mol Catal A:Chem,2007,275(1):101-108.
[9]	Li H,Wang F M,Cai W F,et al. Hydrochlorination of Acetylene Using Supported Phosphorus-doped Cu-based Catalysts[J]. Catal Sci Technol,2015,5(12):5174-5184.
[10]	Hu D,Wang F,Wang J D.Bi/AC Modified with Phosphoric Acid as Catalyst in the Hydrochlorination of Acetylene[J]. RSC Adv,2017,7(13):7567-7575.
[11]	GUO Yanyan,LIU Ying,HU Ruisheng,et al. Preparation and Optimization of SnCl2-ZnCl2/C Mercury-free Catalyst for Acetylene Hydrochlorination[J]. Chinese J Appl Chem,2014,31(5):624-626(in Chinese). 郭燕燕,刘鹰,胡瑞生,等. SnCl2-ZnCl2/C无汞乙炔氢氯化催化剂的制备与优化[J]. 应用化学,2014,31(5):624-626.
[12]	Zhou K,Si J K,Jia J C,et al. Reactivity Enhancement of N-CNTs in Green Catalysis of C2H2 Hydrochlorination by a Cu Catalyst[J]. RSC Adv,2014,4(15):7766-7769.
[13]	Zhang J L,Liu N,Li W,et al. Progress on Cleaner Production of Vinyl Chloride Monomers over Non-mercury Catalysts[J]. Front Chem Sci Eng,2011,5(4):514-520.
[14]	Wang L,Wang F,Wang J D,et al. Hydrochlorination of Acetylene to Vinyl Chloride over Pd Supported on Zeolite Y[J]. React Kinet Mech Catal,2013,110(1):187-194.
[15]	Zhao J G,Zeng J J,Cheng X G,et al. An Au-Cu Bimetal for Acetylene Hydrochlorination with Renewableb γ-Al2O3 as the Support[J]. RSC Adv,2015,5(22):16727-16734.
[16]	Abudawood R H,Alotaibi F M,Garforth A A.Hydroisomerization of n-Heptane over Pt-Loaded USY Zeolites. Effect of Steaming, Dealumination, and the Resulting Structure on Catalytic Properties[J]. Ind Eng Chem Res,2011,50(17):9918-9924.
[17]	Agudelo J L,Mezari B,Hensen E J M,et al.On the Effect of EDTA Treatment on the Acidic Properties of USY Zeolite and Its Performance in Vacuum Gas Oil Hydrocracking[J]. Appl Catal,A,2014,488(3):219-230.
[18]	Song Z J,Liu G Y,He D W,et al. Acetylene Hydrochlorination Over 13X Zeolite Catalyst at High Temperature[J]. Green Chem,2016,18:5994-5998.
[19]	SONG Zhijia,LIU Shaofeng,HE Dawei,et al. Performance of CuCl2/13X Catalyst in Acetylene Hydrochlorination[J]. Sci Sin Chim,2018,48(2):186-295(in Chinese). 宋智甲,刘少峰,贺大威,等. CuCl2/13X催化剂在乙炔氢氯化反应中的应用[J]. 中国科学:化学,2018,48(2): 186-295.
[20]	WANG Lu.Preparation and Performance of Zeolite-supported on Supported Palladium Catalysts for Acetylene Hydrochlorination[D]. Urumqi:Xinjiang University,2013(in Chinese). 王璐. 乙炔氢氯化分子筛负载型钯催化剂的制备及性能研究[D]. 乌鲁木齐: 新疆大学,2013.
[21]	WANG Shengjie,SHEN Benxian,ZHAO Jigang,et al. Deactivation of PdCl2/C Catalyst in Hydrochlorination of Acetylene[J]. Petrochem Technol,2009,38(3):249-253(in Chinese). 王声洁,沈本贤,赵基钢,等. 乙炔氢氯化PdCl2/C催化剂失活原因分析[J]. 石油化工,2009,38(3):249-253.
[22]	Zhao J,Zhang T T,Di X X,et al. Activated Carbon Supported Ternary Gold-Cesium(Ⅰ)-Indium(Ⅲ) Catalyst for the Hydrochlorination of Acetylene[J]. Catal Sci Technol,2015,5(11):4973-4984.
[23]	Wang L,Wang F,Wang J D.Effect of K Promoter on the Stability of Pd/NFY Catalysts for Acetylene Hydrochlorination[J]. Catal Commun,2016,83:9-13.
[24]	Xu H,Zhou K,Si J K,et al. A Ligand Coordination Approach for High Reaction Stability of an Au-Cu Bimetallic Carbon-based Catalyst in the Acetylene Hydrochlorination Process[J]. Catal Sci Technol,2015,6(5):1357-1366.
[25]	Biesinger M C,Lau L W M,Gerson A R,et al. Resolving Surface Chemical States in XPS Analysis of First Row Transition Metals, Oxides and Hydroxides:Sc, Ti, V, Cu and Zn[J]. Appl Surf Sci,2010,257(3):887-898.