The pyrolysis dechlorination of PVC (polyvinyl chloride) has been carried out by batch operation under atmospheric pressure. The kinetics involved in the PVC thermal decomposition was studied by using thermogravimetri...The pyrolysis dechlorination of PVC (polyvinyl chloride) has been carried out by batch operation under atmospheric pressure. The kinetics involved in the PVC thermal decomposition was studied by using thermogravimetric technique. Several tests were carried out at the heating rate of 5-10℃/min, the yields of products and the distribution of chlorine were also studied. The kinetic parameters such as activation energies, reaction orders and preexponential factors under nitrogen atmosphere were calculated by applying Friedman’s method. The results showed that the PVC thermal degradation is substantially a two-step process. The first step mainly involves dechlorination of the polymers. HCI is the main volatile product and this reaction can be seen as a first-order reaction. A kinetic model for the thermal dechlorination of PVC has been developed.展开更多
Commercial production of vinyl chloride from acetylene relies on the use of HgCla as the catalyst, which has caused severe environmental problem and threats to human health because of its toxicity. Therefore, it is vi...Commercial production of vinyl chloride from acetylene relies on the use of HgCla as the catalyst, which has caused severe environmental problem and threats to human health because of its toxicity. Therefore, it is vital to explore alternative catalysts without mercury. We report here that N-doped carbon can catalyze directly transformation of acetylene to vinyl chloride. Particularly, N-doped high surface area mesoporous carbon exhibits a rather high activity with the acetylene conversion reaching 77% and vinyl chloride selectivity above 98% at a space velocity of 1.0 mL.min-l.g-1 and 200 ~C. It delivers a stable performa℃nce within a test period of 100h and no obvious deactivation is observed, demonstrating potentials to substitute the notoriously toxic mercuric chloride catalyst.展开更多
Commercialization of acetylene hydrochlorination using AuCl3 catalysts has been impeded by its poor stability. We have been studying that nitrogen-modified Au/NAC catalyst delivered a stable performance which can impr...Commercialization of acetylene hydrochlorination using AuCl3 catalysts has been impeded by its poor stability. We have been studying that nitrogen-modified Au/NAC catalyst delivered a stable performance which can improve acetylene hydrochlorination activity and has resistance to catalytic deactivation. Here we show that nitrogen and sulfur co-doped activated carbon supported AuCl3 catalyst worked as efficient catalysts for the hydrochlorination of acetylene to vinyl chloride. Au/NSAC catalyst demonstrated high activity comparative to Au/AC catalyst. Furthermore, it also delivered stable performance within the selectivity of acetylene, reaching more than 99.5%, and there was only a 3.3% C2H2 conversion loss after running for 12 h under the reaction conditions of a temperature of 180 C and a C2H2 hourly space velocity of 1480 h 1. The presence of the sulfur atoms may serve to immobilize/ anchor the Au and also help prevent reduction and sintering of the Au and hence improve the catalytic activity and stability. The excellent catalytic performance of the Au/NSAC catalyst demonstrated its potential as an alternative to mercury chloride catalysts for acetylene hydrochlorination.展开更多
Catalyst supports have very important effects on catalyst performance.A novel expanded multilayered vermiculite（EML-VMT） is successfully used as the catalyst support for the acetylene hydrochlorination.By mixing car...Catalyst supports have very important effects on catalyst performance.A novel expanded multilayered vermiculite（EML-VMT） is successfully used as the catalyst support for the acetylene hydrochlorination.By mixing carbon on the surface of EML-VMT[i.e.,EML-VMT-C）,the HgCl2/EML-VMT-C achieved a high acetylene conversion of 97.3%,a vinyl chloride selectivity of 100%and a turn over frequency（TOF） value of 8.83 × 10^-3s^-1 at a temperature of 140 C,an acetylene gas hourly space velocity（GHSV） of 108 h^-1,and a feed volume ratio V（HC1）/V（C2H2） of 1.15.Moreover,the HgCl2/EML-VMT-C shows good stability.The EML-VMT also shows potential in the preparation of other EML-VMT-supported catalysts.展开更多
AuCl3 loaded structured catalysts were prepared on SiC foam supported with pre-coated activated carbon layers. The catalytic properties of the structured catalysts towards hydrochlorination of acetylene were tested in...AuCl3 loaded structured catalysts were prepared on SiC foam supported with pre-coated activated carbon layers. The catalytic properties of the structured catalysts towards hydrochlorination of acetylene were tested in a fixed- bed reactor with the AuCl3 loaded on activated carbon pellets as a reference. For isopyknic catalysts, the structured catalyst with only one fifth of the Au amount as that was used on the reference catalyst exhibited even a little higher acetylene conversion and much better stability than the latter no matter what the gas hourly space velocities of acetylene were used. The results indicated that the more homogeneous distribution of AuCl3 particles and better heat transfer along the fixed-bed reactor originated from the low pressure drop and high thermal conductivity of the SiC foam supported structured catalysts might be able to account for their improved efficiency and stability. It is befieved that these novel structured C/Au catalysts can be potentially applied in VCM industrialization in view of their greatly reduced cost and much prolonged life.展开更多
文摘The pyrolysis dechlorination of PVC (polyvinyl chloride) has been carried out by batch operation under atmospheric pressure. The kinetics involved in the PVC thermal decomposition was studied by using thermogravimetric technique. Several tests were carried out at the heating rate of 5-10℃/min, the yields of products and the distribution of chlorine were also studied. The kinetic parameters such as activation energies, reaction orders and preexponential factors under nitrogen atmosphere were calculated by applying Friedman’s method. The results showed that the PVC thermal degradation is substantially a two-step process. The first step mainly involves dechlorination of the polymers. HCI is the main volatile product and this reaction can be seen as a first-order reaction. A kinetic model for the thermal dechlorination of PVC has been developed.
基金supported by the Natural Science Foundation of China(No.11079005 and 21033009)the Ministry of Science and Technology of China(2011CBA00503 and 2012CB720302)
文摘Commercial production of vinyl chloride from acetylene relies on the use of HgCla as the catalyst, which has caused severe environmental problem and threats to human health because of its toxicity. Therefore, it is vital to explore alternative catalysts without mercury. We report here that N-doped carbon can catalyze directly transformation of acetylene to vinyl chloride. Particularly, N-doped high surface area mesoporous carbon exhibits a rather high activity with the acetylene conversion reaching 77% and vinyl chloride selectivity above 98% at a space velocity of 1.0 mL.min-l.g-1 and 200 ~C. It delivers a stable performa℃nce within a test period of 100h and no obvious deactivation is observed, demonstrating potentials to substitute the notoriously toxic mercuric chloride catalyst.
文摘Commercialization of acetylene hydrochlorination using AuCl3 catalysts has been impeded by its poor stability. We have been studying that nitrogen-modified Au/NAC catalyst delivered a stable performance which can improve acetylene hydrochlorination activity and has resistance to catalytic deactivation. Here we show that nitrogen and sulfur co-doped activated carbon supported AuCl3 catalyst worked as efficient catalysts for the hydrochlorination of acetylene to vinyl chloride. Au/NSAC catalyst demonstrated high activity comparative to Au/AC catalyst. Furthermore, it also delivered stable performance within the selectivity of acetylene, reaching more than 99.5%, and there was only a 3.3% C2H2 conversion loss after running for 12 h under the reaction conditions of a temperature of 180 C and a C2H2 hourly space velocity of 1480 h 1. The presence of the sulfur atoms may serve to immobilize/ anchor the Au and also help prevent reduction and sintering of the Au and hence improve the catalytic activity and stability. The excellent catalytic performance of the Au/NSAC catalyst demonstrated its potential as an alternative to mercury chloride catalysts for acetylene hydrochlorination.
基金financially supported by National Natural Science Foundation of China(Nos.21163015,21366027)the Doctor Foundation of Bingtuan(No.2014BB004)+2 种基金the National Basic Research Program of China(973Program,No. 2012CB720300)the Program for Changjiang Scholars,Innovative Research Team in University(No.IRT1161)the Program of Science and Technology Innovation Team in Bingtuan(No.2011CC001)
文摘Catalyst supports have very important effects on catalyst performance.A novel expanded multilayered vermiculite（EML-VMT） is successfully used as the catalyst support for the acetylene hydrochlorination.By mixing carbon on the surface of EML-VMT[i.e.,EML-VMT-C）,the HgCl2/EML-VMT-C achieved a high acetylene conversion of 97.3%,a vinyl chloride selectivity of 100%and a turn over frequency（TOF） value of 8.83 × 10^-3s^-1 at a temperature of 140 C,an acetylene gas hourly space velocity（GHSV） of 108 h^-1,and a feed volume ratio V（HC1）/V（C2H2） of 1.15.Moreover,the HgCl2/EML-VMT-C shows good stability.The EML-VMT also shows potential in the preparation of other EML-VMT-supported catalysts.
基金supported by the National Key Technology R&D Program of China with Grant No.2011BAE03B07
文摘AuCl3 loaded structured catalysts were prepared on SiC foam supported with pre-coated activated carbon layers. The catalytic properties of the structured catalysts towards hydrochlorination of acetylene were tested in a fixed- bed reactor with the AuCl3 loaded on activated carbon pellets as a reference. For isopyknic catalysts, the structured catalyst with only one fifth of the Au amount as that was used on the reference catalyst exhibited even a little higher acetylene conversion and much better stability than the latter no matter what the gas hourly space velocities of acetylene were used. The results indicated that the more homogeneous distribution of AuCl3 particles and better heat transfer along the fixed-bed reactor originated from the low pressure drop and high thermal conductivity of the SiC foam supported structured catalysts might be able to account for their improved efficiency and stability. It is befieved that these novel structured C/Au catalysts can be potentially applied in VCM industrialization in view of their greatly reduced cost and much prolonged life.
