Study On Pyrolysis And Catalytic Pyrolysis Of Liushuhe Oil Shale

The gradual reduction of traditional energy resources and heavy industry development result in great pressure on energy supply. The most prominent problem facing is the oil shortage. Oil shale is an unconventional energy and can be used as a substitute of oil. The pyrolysis of oil shale is the most effective and comprehensive utilization of oil shale and has aroused widespread concern.The pyrolysis of Liushuhe oil shale under nitrogen and hydrogen atmosphere was studied in this paper. The influences of pyrolysis temperature, carrier gas flow, retention time on products yields and components during pyrolysis were investigated. It was found that the optimum conditions for Liushuhe oil shale pyrolysis were:under nitrogen atmosphere, temperature500℃, carrier gas flow rate100SCCM and retention time20min; under hydrogen atmosphere, temperature480℃, carrier gas flow rate150SCCM, retention time20min.When HZSM-5, HY zeolites were used as the catalysts, the catalytic pyrolysis experiments of Liushuhe oil shale were carried out under nitrogen and hydrogen atmosphere. The influences of catalysts types, catalysts addition and temperature on pyrolysis products yields and components were studied. The results under nitrogen atmosphere indicated that with the increase of catalysts addition, the yield of shale oil was first increasing then decreasing, and reached the maximum15.51wt%and14.78wt%at catalysts addition4%, respectively. The contents of acidic and aromatic fraction in shale oil increased. And, the content of alkaline fraction in shale oil decreased. The results under hydrogen atmosphere indicated that with the increase of catalysts addition, the yield of shale oil was first increasing then decreasing, and reached the maximum14.05wt%and13.99wt%at catalysts addition4%, respectively. The contents of acidic and aliphatic fraction in shale oil decreased.Under two pyrolysis atmospheres, the catalytic pyrolysis experiments of Liushuhe oil shale were carried out using the metal (Fe, Co, Mo) loading on HZSM-5, HY zeolites catalysts. The influences of support, types and loading of metals on oil shale pyrolysis were studied. When metal supported HZSM-5zeolite was added, the yields of shale oil under nitrogen atmosphere were first increasing then decreasing. And, the yields of shale oil under hydrogen atmosphere were gradually decreasing with increasing Fe loading, and were first increasing then decreasing with increasing Co, Mo loading. When metal supported HY zeolite was added, the yields of shale oil under nitrogen atmosphere were gradually increasing with increasing Fe loading and reached the maximum15.78wt%at loading20%. But, when the Co, Mo loading increased, the yields of shale oil were the first decreasing then increasing. The yields of shale oil under hydrogen atmosphere were first increasing then decreasing with increasing Fe loading. And, when the Co, Mo loading increased, the yields of shale oil were gradually increasing. Under hydrogen atmosphere, the content of aromatic fraction in shale oil reached a maximum when metal Mo was added, which increased36.28%comparing with the shale oil of alone pyrolysis under nitrogen atmosphere.The addition of catalysts can significantly increased the content of low-carbon hydrocarbons, decreased the content of long chain hydrocarbons, and had an significantly effect on removing the nitrogen and sulfur compounds in oil shale, the maximal decrease reached55.00wt%.