Preliminary Study On Hydrogenation Of Dalian Mixed Residue

With the sustainable economic development of the society,the demand of middle distillate oil and quality are increasing.The oil resources are decreasing,and the crude oils tend to be heavy and inferior.Thus promoting heavy oil,improving the production and quality of middle distillate oil are essential.Residue hydrogenation technology has an important position in many aspects,such as the deepening of the residue processing,the improvement of oil quality,the flexibility of operation,the improvement of the comprehensive utilization of petrochemical products,and the implementation of sustainable development strategy.In this paper,Dalian mixed residue as raw material oil was studied.The effects of temperature and the ratio of catalysts were investigated.The results showed that both the increase of the reaction temperature and the ratio of the catalyst could increase the removal rate of heteroatoms,including sulfur and nitrogen of the metal nickel,and vanadium.The saturation content increased after the reaction,while the asphaltene content decreased.The coking rate of the reaction sample after hydrogenation was negatively correlated with the stability of colloidal.When the reaction temperature exceeded T,the high temperature had a great effect on the colloidal stability and the coke rate.After the reaction at T+,the pores of the catalysts were almost completely blocked,the average loss of pore capacity raised up to 81.7%,with 7.3% of coke rate.Study on the structure and distribution of sulfur-containing functional groups using XANES,the results show that the sulfur-containing functional groups in the asphaltene component are mainly thiophene,sulfoxide,sulfone and sulfuric acid ester,and the content of thiophene sulfur is the highest,and the relative content is more than 50% of the total.After the hydrogenation reaction,the relative content of thiophene sulfur increased with the increase of the reaction temperature,and the relative content of sulfone and sulfate decreased.With the increase of the oil ratio,the relative content of thiophene sulfur decreased.The sulfur content of the sulfur functional groups decreased with the increase of sulfuric acid ester and sulfone.Hydrogenation process in the process of reducing the state of the sulfone and sulfuric acid ester to the intermediate state of sulfur(sulfoxide)and oxidation(thiophene)sulfur conversion.The distribution of basic nitrogen-containing compounds in the residual oil before and after hydrogenation was studied by Fourier transform ion cyclotron resonance mass spectrometry(ESIFT-ICRMS),the results showed that the mass spectra of basic nitrogen-containing compounds in the residual oil were mainly distributed in the range of 270 ~ 600(P <0.05).The results showed that the distribution of basic nitrogen compounds in the residual oil before and after hydrogenation was studied by Fourier transform ion cyclotron resonance mass spectrometry 70~600 m/z,the mass spectrum peaks are approximately normal distribution,and the most dense mass center of mass spectrometry is about 360 m / z.The types of heteroatom compounds in the samples are mainly N1?O1?N1S1?O3?O1S1?O2?N1O1?N2.The relative abundance of N1 is the largest,followed by the abundance of O1 and N1S1,indicating that the heteroatom N,S,O type and content is higher.The polarities of oil samples were investigated before and after hydrogenation,the results show that the asphaltene dipole moment is the largest,and between 14 and 17,the gelatinic dipole moment is only about 1/3 of asphaltene.After the hydrogenation reaction,the polarity of asphaltene and colloid is obviously reduced,the decrease of asphaltene is about 20%,the decrease of glial is about 30%,the pyrolysis of glial components is relatively simple The change trend of sulfur content in asphaltene component is basically the same as that of dipole moment,and decreases with the increase of reaction temperature.Residue colloidal stabilization is not only related to composition,but also to the nature of the components.Hydrodesulfurization of the residue before the desulfurization,denitrification treatment can effectively reduce the coke rate.