Surface chemical characterization of deactivated low-level mercury catalysts for acetylene hydrochlorination

Mercury-containing catalysts are widely used for acetylene hydrochlorination in China. Surface chemical characteristics of the fresh low-level mercury catalysts and spent low-level mercury catalysts were compared using multiple characterization methods. Pore blockage and active site coverage caused by chlorine-containing organics are responsible for catalyst deactivation. The reactions of chloroethylene and acetylene with chlorine free radical can generate chlorine-containing organic species. SiO₂ and functional groups on activated carbon contribute to the generation of carbon deposition. No significant reduction in the total content of mercury was observed after catalyst deactivation, while there was mercury loss locally. The irreversible loss of HgCl₂ caused by volatilization, reduction and poisoning of elements S and P also can lead to catalyst deactivation. Si, Al, Ca and Fe oxides are scattered on the activated carbon. Active components are still uniformly absorbed on activated carbon after catalyst deactivation.     

High nitrogen carbon material with rich defects as a highly efficient metal-free catalyst for excellent catalytic performance of acetylene hydrochlorination

In this work,we developed a simple strategy to synthesize a carbon material with high nitrogen and rich carbon defects.Our approach polymerized diaminopyridine(DAP) and ammonium persulfate(APS).Following a range of different temperature pyrolysis approaches,the resulting rough surface was shown to exhibit edge defects due to N-doping on graphite carbon.A series of catalysts were evaluated using a variety of characterization techniques and tested for catalytic performance.The catalytic performance of the N-doped carbon material enhanced alongside an increment in carbon defects.The NC-800 catalyst exhibited outstanding catalytic activity and stability in acetylene hydrochlorination(C_2 H_2 GHSV=30 h~(-1),at 220℃,the acetylene conversion rate was 98%),with its stability reaching up to 450 h.Due to NC-800 having a nitrogen content of up to 13.46%,it had the largest specific surface area and a high defect amount,as well as strong C_2 H_2 and HCl adsorption.NC-800 has excellent catalytic activity and stability to reflect its unlimited potential as a carbon material.     

碳纳米管表面基团对Bi基催化剂在乙炔氢氯化反应中催化性能的影响

以多壁碳纳米管(MWCNTs)、羟基碳纳米管(MWCNTs-OH)、羧基碳纳米管(MWCNTsCOOH)为催化剂载体,采用等体积浸渍法制备负载型Bi基催化剂,在固定床反应器中评价催化剂在乙炔氢氯化反应中的性能。结果表明,以MWCNTs-OH为载体的Bi基催化剂催化性能最优,乙炔转化率最高52%。BET、FT-IR、XRD、XPS、EDS、TG、TEM和H_2-TPR表征表明,碳纳米管表面基团,尤其是羟基,可以提高活性组分的分散度、抑制催化剂表面积炭生成和减少Bi物种流失。     

含氮碳材料在乙炔氢氯化反应中的研究进展

由于汞污染和汞资源匮乏的问题,研发新型、绿色、高效的乙炔氢氯化无汞催化剂是实现聚氯乙烯行业绿色可持续发展的关键.具有优异性能的含氮碳材料作为催化剂载体为乙炔氢氯化无汞催化剂的研究提供了一种新的思路,也是目前此领域的研究热点之一.该文综述了含氮碳材料在乙炔氢氯化反应中的应用现状,并展望了含氮碳材料在乙炔氢氯化反应中发展趋势.     

乙炔氢氯化反应用无汞催化剂的研究进展

综述了国内外乙炔氢氯化反应用无汞催化剂的研究情况，介绍了目前实验室中无汞催化剂的开发进展，展望了无汞催化剂的发展前景。     

乙炔氢氯化低汞催化剂的表征方法

介绍了乙炔氢氯化低汞催化剂表征中用到的4种分析方法,包括BET比表面积法、扫描电子显微镜、热分析技术和原子吸收光谱法。     

乙炔氢氯化低汞催化剂的研究进展

综述了国内外乙炔氢氯化低汞催化剂的研究方向及成果,简介实验室目前对低汞催化剂的开发进展,并展望乙炔氢氯化催化剂的发展前景。     

乙炔氢氯化制氯乙烯Pt/C催化剂的性能

以PtCl₄和PtCl₂为活性组分,活性炭为载体,采用浸渍法制备Pt/C催化剂,考察Pt/C催化剂用于乙炔氢氯化制取氯乙烯的催化性能,并采用热重分析、N₂等温吸附-脱附和H₂-TPR等方法对Pt/C催化剂进行表征。结果表明, 加入少量Pt(Ⅱ)（质量分数20%）有利于提高催化剂的初始活性,但加剧了催化剂失活。而活性组分被还原是催化剂失活的主要原因,反应过程中积炭堵塞微孔结构也是导致催化剂失活的原因。     

乙炔氢氯化反应无汞催化剂的研究进展

概括评述了前人对乙炔氢氯化反应无汞催化剂结构性能与催化活性关系的研究,并根据金属离子络合能力的差别,分析总结出了碱金属和碱土金属以及其它金属离子可能的催化反应机理。同时从非均相反应体系和均相反应体系两方面综述了国内外无汞催化剂催化乙炔氢氯化反应的研究情况,特别是对金基催化剂的研究,从催化剂的组分、催化机理、失活和再生等方面做了详细概述,对有机溶剂和离子液体做溶剂的均相体系进行了简要评述,并从组分、溶剂、载体等方面对各种无汞催化反应体系将来的开发方向进行了展望。     

乙炔氢氯化反应非汞催化剂研究进展

综述了非汞金属催化剂催化乙炔氢氯化反应制备氯乙烯的研究进展,探讨了非汞催化剂的种类、结构与性能的关系,分析了该反应的机理和非汞催化剂失活的原因,并展望了今后的研发趋势。     

Process monitoring of the Au-S bond conversion in acetylene hydrochlorination

The continuous expansion of vinyl chloride production increases environmental pollution caused by mercury catalysts, which is an issue that urgently needs to be solved. Green and stable catalysts should be researched to alleviate this issue. In this research, Thiolactic acid acts as a ligand where sulfhydryl groups form a stable complex with Au on the surface of a spherical activated carbon (SAC). An Au-thiolactic acid/SAC catalyst was designed with a Au theoretical loading of 0.5% (mass) to overcome the disadvantages of traditional Au-based catalysts, such as a low conversion rate and poor life cycle. The ratio of Au to ligand was screened, and the activity was best when Au/S = 1:8. The formation of the Au-S bond was proven by FT-IR and UV–vis. The longevity test of the Au1S8 /SAC catalyst was carried out at 1200 h^-1 for 50 h. Samples with reaction times of 0 h, 5 h, 10 h, 20 h, and 50 h were taken to monitor the catalyst status. The XPS and TPR tests proved that the Au-S bond broke as the acetylene hydrochlorination reaction proceeded. The DFT calculation proved that the Au-S bond is the active site, and the sulfur atom promotes the adsorption of C₂H₂ by the catalyst.     

乙炔氢氯化反应无汞贵金属催化剂的研究进展

受“水俣公约”和环境保护政策约束,研究和开发新型无汞催化剂是保障我国乙炔法制备聚氯乙烯未来发展的核心环节。无汞催化剂包括贵金属催化剂、非贵金属催化剂和非金属催化剂,其中贵金属催化剂被认为是最具有工业化应用前景的催化剂。本文概述了近年来国内外乙炔氢氯化贵金属Au、Ru、Pd和Pt催化剂的研究进展,重点综述了不同催化剂的活性组分、催化机理及催化剂的改性方法等方面的研究,分析了不同改性方法的作用机制及不同催化剂改性的研究方向。研究表明,添加助剂或多金属复配、配体和离子液体的使用及载体改性均使贵金属催化剂的催化活性和稳定性得到一定程度提高,从而进一步增加了贵金属催化剂工业化应用的可能性。     

乙炔氢氯化反应贵金属无汞催化剂研究进展

概述近年来国内外乙炔氢氯化反应贵金属无汞催化剂的研究进展,主要探讨了催化剂的活性组分、载体及其对催化活性的影响,简要介绍催化剂失活原因与再生手段.多种贵金属的协同催化、载体处理方法的多样化、制备过程的条件优化是贵金属无汞催化剂未来的发展方向.     

乙炔氢氯化反应非贵金属无汞催化剂的研究进展

由于具有较好的催化活性和环境友好性,用于乙炔氢氯化反应的无汞催化剂日益受到人们的重视。本文概述了近年来国内外乙炔氢氯化反应无汞催化剂的研究进展,综述了改善非贵金属催化剂性质的主要方法,探讨了催化剂的活性组分、载体及制备过程对催化活性的影响,简要介绍了气固相催化体系和液相催化体系的催化机理与催化活性之间的关系,分析了高活性、长寿命的乙炔氢氯化反应非贵金属无汞催化剂所应具备的必要条件。研究表明,多种非贵金属的协同催化、载体处理方法的多样化、制备过程的优选组合及离子液体的应用将是今后乙炔氢氯化反应催化剂的发展趋势。     

乙炔氢氯化金基无汞催化剂的研究进展

乙炔氢氯化无汞催化剂对我国煤基聚氯乙烯（PVC）工业实现绿色可持续发展具有重要意义,金基催化剂因其优良的催化性能而受到广泛的关注。本文从金基催化剂产业化应用存在成本高、稳定性差等问题出发,全面阐述了金基催化剂的反应和失活机理。从活性组分、载体等因素对催化性能的影响出发,概述了多年来金基催化剂的研究进展,重点总结了研究者们从改进活性组分和载体方面入手,使催化剂性能不断提升至工业化应用所做的工作。最后展望了金基催化剂的发展前景,并提出应深入研究内在反应机理,以简化制备及再生过程,探索低成本高效无汞催化剂及其工程化问题是该领域的研究重点。     

乙炔氢氯化制氯乙烯无汞催化剂研究进展

氯乙烯是重要的化工原料,乙炔氢氯化是制取氯乙烯主要方法之一,工业上普遍采用汞催化剂,对环境污染严重,且危害人体健康。对汞资源的过度消耗和依赖是聚氯乙烯行业发展面临的巨大障碍,开发无毒环保的非汞催化剂已成为首要解决的问题。综述近年来乙炔氢氯化无汞催化剂的研究现状,主要包括以Au为代表的贵金属催化剂、以Cu、Sn和Ni等为代表的非贵金属催化剂以及以新兴的C-N材料为代表的非金属催化剂。Au用作催化剂价格昂贵,不利于工业化应用。碳氮材料具有较大的比表面积,对氯化氢具有优异的吸附性能,用于乙炔氢氯化反应具有较高活性,并具有较大的工业应用潜力,以碳氮材料为代表的非金属催化剂成为新的研究热点。     

HY型分子筛负载Pd催化剂用于乙炔氢氯化反应制氯乙烯的催化性能

以水热法合成HY分子筛为载体,等体积浸渍法制备HY型分子筛负载Pd催化剂(Pd/HY)。在反应温度160℃、空速120 h-1和V(HCl)∶V(C2H2)=1.1∶1条件下,考察催化剂用于乙炔氢氯化反应制氯乙烯的催化性能及载体中硅铝比对催化剂催化性能的影响。用XRD、FI-IR、SEM和BET对Pd/HY催化剂的物化性质进行表征,结果表明,Pd/HY(HY分子筛的Si/Al=8)催化剂表现出较好的催化活性,乙炔转化率为97.67%,氯乙烯选择性为98.44%。与工业HY型分子筛为载体的催化剂相比,乙炔转化率提高29%,寿命较长,稳定性良好。     

The ligand coordination approach for improving the stability of low-mercury catalyst in the hydrochlorination of acetylene

Mercuric chloride supported on activated carbon (HgCl2/AC) is used as an industrial catalyst for the hydrochlorination of acetylene.Loss of HgCl2 by sublimating from the surface of activated carbon causes the irreversible deactivation of mercury catalyst and environmental pollution.In this work,a ligand coordination approach based on the Principle of Hard and Soft Acids and Bases (HSAB) was employed to design more stable lowmercury catalyst.The low-mercury catalysts (4％ HgCl2 loading) were prepared by using HgCl2 and potassium halides (KX,X =Cl,I) as precursors.The HgCl2-4KI/AC catalyst showed best catalytic stability than HgCl2/AC and HgCl2-4KCl/AC in the hydrochloriantion of acetylene.HgCl2 could form more stable complex with KI,K2HgI4 as the main active component of the HgCl2-4KI/AC catalyst.The characterizations of XRD and EDX analysis illustrated that the active component of HgCl2-4KI/AC was highly dispersed on the surface of activated carbon.The sublimation rates of HgCl2 from the catalysts verified that the active component with larger stability constant had better thermal stability.Using Hg(Ⅱ) complexes with high stability constant as the active component may be the research direction of developing highly stable low-mercury catalyst for the hydrochlorination of acetylene.     

乙炔法合成氯乙烯用无汞催化剂的失活原因与再生

对近几十年乙炔氢氯化合成氯乙烯用非均相无汞催化剂失活的原因和再生方法进行总结。乙炔法合成氯乙烯催化机理分先吸附乙炔和先吸附氯化氢两类。催化剂活性组分锡、铋和钯流失,氧化态铂和金被乙炔分子还原至低价或金属态,活性组分分散不均和晶粒长大均容易导致催化活性下降。先通入乙炔或乙炔进料过量、表面短链类聚乙烯或聚乙炔过渡态化合物难脱附、不同的载体及其表面性质均会诱导生成积炭物质。制备复合催化剂、添加碱土或稀土金属助剂有助于协同催化和自行还原再生。表面改性能改变吸附顺序,在线通入适量NO以及时去除积炭,可提高催化剂的稳定性。离线有氧烧炭再生含碳载体效果较差,而硝酸加热处理或王水处理失活的贵金属催化剂能恢复初始或接近初始催化活性。并对乙炔氢氯化无汞催化剂的发展进行展望。     

非金属氮掺杂活性炭催化剂制备及其催化CH4-CO2重整反应

采用硝酸和尿素联合对活性炭进行改性,制备了富含氮元素的氮掺杂活性炭,考察了孔结构、氮含量和氮种类（吡啶氮、吡咯氮和石墨氮）对CH₄-CO₂重整反应催化性能的影响。采用BET、SEM、EA、FTIR、XPS、CO₂-TPD和TG表征手段对反应前后催化剂的物理化学性质进行了表征,对引入活性炭表面的含氮官能团的种类及其在重整过程中所起的作用进行了分析。相比于未改性的原活性炭,硝酸和尿素同时改性制备的氮掺杂活性炭（AC-U.NA）引入了更多的羟基官能团和含氮官能团。特别是通过两者共同改性后,所制备的氮掺杂活性炭引入的吡啶氮官能团比例明显提高,为CH₄-CO₂重整反应提供了更多的活性位点,初始CH₄和CO₂转化率达到55.94%和66.46%。同时经过两者联合改性后,所制备的AC-U.NA材料表面具有极性,不仅有利于酸性CO₂分子的吸附和活化,而且有利于CO₂消碳反应,减少了积炭的生成,对所制备的非金属重整催化剂的活性和抗积炭性具有重要的意义。