Based on the mechanism of resid hydrotreating reaction by coordinating the catalyst activity and stability, the diffusion mechanism and catalyst reactivity, the cost and catalyst performance, and the production and ap...Based on the mechanism of resid hydrotreating reaction by coordinating the catalyst activity and stability, the diffusion mechanism and catalyst reactivity, the cost and catalyst performance, and the production and application requirements, the third-generation series catalysts for residue hydrotreating have been developed by Research Institute of Petroleum Processing, SINOPEC. The new series RHT catalysts possess higher activity for HDS, HDM and HDCCR performance as well as longer run length. The commercial results for application of these catalysts have demonstrated that the new catalyst system performs better than the reference ones.展开更多
This article has summarized the optimized measures relating to the loading of catalyst,and the sixth operating cycle of the residue hydrotreating unit at SINOPEC's Maoming Branch Company,and made a detailed compar...This article has summarized the optimized measures relating to the loading of catalyst,and the sixth operating cycle of the residue hydrotreating unit at SINOPEC's Maoming Branch Company,and made a detailed comparison on the impurities removal rate,hydrogen consumption and energy consumption of the sixth operating cycle with those achieved by the previous five cycles.Test results have revealed that the second-generation RHT series novel residue hydrotreating catalysts featured high activity,good stability,and long operating cycle and could remarkably reduce the hydrogen consumption and energy consumption of process unit.The hydrotreated AR product,having low Conradson carbon residue,low sulfur content,low metal content,high content of saturated hydrocarbons,and low content of asphaltenes and resins,is an excellent FCC feed.Judging from their overall property the second-generation RHT series of residue hydrotreating catalysts used in the sixth operating cycle have commanded a leading position among other catalysts used in previous operating cycles.展开更多
This article refers to the first commercial application of upflow residuum hydrotreating serial catalyst, developed by Fushun Research Institute of Petroleum and Petrochemicals (FRIPP), in the residuum hydrotreating u...This article refers to the first commercial application of upflow residuum hydrotreating serial catalyst, developed by Fushun Research Institute of Petroleum and Petrochemicals (FRIPP), in the residuum hydrotreating unit at Shengli refinery of Qilu Petrochemical Company. This catalyst features large pore volume and large pore diameter. The production practice for more than one year has revealed that the domestic upflow residuum hydrotreating catalyst has shown good performance and stability over the whole period of operation despite its high activity at the start of run, and has basically reached the level of similar imported catalyst.展开更多
In order to extend the operating cycle of the upflow reactor for resid hydrotreating, the Re- search Institute of Petroleum Processing taking into account the specifics of resid hydrotreating upflow reactor has develo...In order to extend the operating cycle of the upflow reactor for resid hydrotreating, the Re- search Institute of Petroleum Processing taking into account the specifics of resid hydrotreating upflow reactor has developed the high-performance RUF series of catalysts suitable for operation in the upflow reactor. The results of commercial application of catalysts revealed that this RUF series of catalysts loaded after optimized grading could effectively remove metals, sulfur and carbon residue from the re-siduum to provide improved oil for the following fixed-bed reactor. In the meantime, the RUF series of catalysts have excellent stability to reach an operating cycle of 1.5 years, resulting in minimization of losses caused by refinery downtime.展开更多
A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in...A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in liquid phases to Fe2 P and Fe P.It was found that the iron sulfides(Fe0.96 S and Fe_3S_4) exhibited the low activity for the hydrodesulfurization(HDS) reactions.The HDS activity was also low on the Fe(metal)/Al_2O_3 and Fe_2 P/Al_2O_3 catalysts since they were converted into Fe0.96 S and Fe_3S_4 during the HDS reactions.In contrast,the FeP/Al_2O_3 was found to be stable and active for the HDS reactions.In particular,Fe P/Al_2O_3 possessed significantly smaller Fe P particles than Fe P/C,leading to the significant higher HDS activity of FeP/Al_2O_3 than Fe P/C.展开更多
X-ray absorption fine structure (XAFS) and other techniques have been used to characterize Ni-Mo/Al2O3 supported catalysts. The analysis of Mo K-edge spetrum shows that the active species over sulfide catalysts are ...X-ray absorption fine structure (XAFS) and other techniques have been used to characterize Ni-Mo/Al2O3 supported catalysts. The analysis of Mo K-edge spetrum shows that the active species over sulfide catalysts are MoS2-alike and the dispersion of Mo is high at the level of nanometer particles. There may exist some distortion of the local environment of MoS2, which has an influence on the hydrotreating activities of catalysts. Ni K-edge analysis shows that the coordination effects of Ni-Mo favor the dispersion state of active phase and imply a close relationship with catalyst activities.展开更多
This article refers to the commercial application assessment of the novel S-RHT catalysts.The application outcome has shown that the catalysts loading was reduced with its performance kept at the original level at the...This article refers to the commercial application assessment of the novel S-RHT catalysts.The application outcome has shown that the catalysts loading was reduced with its performance kept at the original level at the initial and middle stages of operation. The performance of catalysts at the end of operation was analyzed, and factors affecting the performance of the novel catalysts at the end of run were identified to facilitate further improvement of the said catalysts.展开更多
PASCA, ESR and Microreactor, have been used to study the states and properties of coking deposits on catalyst. The results indicate that the C exists as three types of states on catalyst surface. The first and second ...PASCA, ESR and Microreactor, have been used to study the states and properties of coking deposits on catalyst. The results indicate that the C exists as three types of states on catalyst surface. The first and second types of carbon are the main reason of the catalyst deactivation, but the third type has a promoting role in n-C_7 hydrocracking reaction. The S_s-C interacts strongly with catalyst, forming metal-carbon-support interaction (MCSI).展开更多
The RHT technology and the second generation RHT catalysts were applied in design of an 1.7Mt/a VRDS unit at the SINOPEC Changling Branch Co. The commercial application result demonstrated that the RHT catalysts showe...The RHT technology and the second generation RHT catalysts were applied in design of an 1.7Mt/a VRDS unit at the SINOPEC Changling Branch Co. The commercial application result demonstrated that the RHT catalysts showed good activity and stability in processing low-sulfur and high-nitrogen residue. The first long period run of unit for processing high Fe and high Ca content residue was achieved. The reasons for excessive pressure drop of R-101 were ascribed to Fe and Ca deposition as well as coke formation.展开更多
The development and application of ex-situ presulfurization(EPRES)technology for hydrotreating catalysts has been reviewed in the present article.The studies in laboratory scale and commercial practice indicated that ...The development and application of ex-situ presulfurization(EPRES)technology for hydrotreating catalysts has been reviewed in the present article.The studies in laboratory scale and commercial practice indicated that the adoption of the EPRES catalyst in industrial application can significantly enhance the degree of presulfurization of metal oxide components,shorten the start-up period,and effectively reduce the environmental impact as well as the danger of start-up procedure in industrial hydrotreating unit.This catalyst has been proved to be versatile for different types of hydrogenation reactions.Different types of active site models are also discussed for better understanding the nature of presulfur-ized catalysts.展开更多
The SHIFT-G technology of inverse catalyst loading is used to optimize the catalyst grading in the residue hydrotreating unit. The results, taken from pilot tests and commercial units, have showed that the optimized c...The SHIFT-G technology of inverse catalyst loading is used to optimize the catalyst grading in the residue hydrotreating unit. The results, taken from pilot tests and commercial units, have showed that the optimized catalyst grading system can reasonably distribute the reaction load, effectively improve the prop- erties of hydrotreated products, prolong the operating cycle and promote economic benefits.展开更多
Based on the reaction mechanism of resid hydrodemetallization, a new catalyst carrier was designed and prepared. As compared with the similar type of catalyst carrier, the said new carrier featured a higher pore volum...Based on the reaction mechanism of resid hydrodemetallization, a new catalyst carrier was designed and prepared. As compared with the similar type of catalyst carrier, the said new carrier featured a higher pore volume, a larger pore diameter and a weaker surface acidity, which could improve the diffusion performance and stable reaction performance of the catalyst. The active metal components were loaded on the said carrier by a new technique for better metal dispersion, thus the impurity removal rate of the new catalyst, RDM-3, was improved significantly. The commercial test of the RDM-3 catalyst showed that the process of catalyst preparation was stable, the catalyst performance was slightly better than the catalyst prepared in the lab, therefore, the catalyst could be manufactured in commercial scale.展开更多
Qilu Petrochemical Company in order to synchronize the replacement of catalysts in the upflow reactor (UFR) and fixed-bed reactors and achieve the 1.5-year operating cycle of the residue hydrotreating unit has revampe...Qilu Petrochemical Company in order to synchronize the replacement of catalysts in the upflow reactor (UFR) and fixed-bed reactors and achieve the 1.5-year operating cycle of the residue hydrotreating unit has revamped the UFR and optimized catalysts grading. Commercial operation results have revealed that the series of catalysts for residue hydrotreating after optimized grading achieved an operating cycle of 1.5 years with the quality of hydrotreated oil products meeting the requirements for FCC feedstock.展开更多
The RHT technology is developed by Research Institute of Petroleum Processing (RIPP) for residuum hydrotreating in order to produce good quality RFCC feed. The advantages of the RHT series catalysts are presented in t...The RHT technology is developed by Research Institute of Petroleum Processing (RIPP) for residuum hydrotreating in order to produce good quality RFCC feed. The advantages of the RHT series catalysts are presented in this article, based on the results of activity tests and a 9500 hours service life test in pilot plants and the assessment on a commercial application.展开更多
The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which c...The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which could delay th aggregation and coke formation from asphaltenes on the catalyst, and make heavy components transformed into light oi The residue conversion in the presence of this additive increased by 1.94%, and the yield of light oil increased by 1.53%when the reaction time was 90 min. The surface properties of the catalyst in the presence of this additive were better tha that of the blank test within a very short time(30 min) and deteriorated rapidly after a longer reaction time due to highe conversion and coke deposition. Compared with the blank test, the case using the said additive had shown that the structur of hydrotreated asphaltene units was smaller and the condensation degrees were higher. The test results indicated that th additive could improve the hydrotreating reactivity of residue via permeation and depolymerization, the heavier componen could be transformed into light oil more easily, and the light oil yield and residue conversion were higher for the case usin the said additive in residue hydrotreating process.展开更多
The S-RHT technology is developed by FRIPP for residue hydrotreating in the fixed bed in order to process the high sulfur crude and increase the yield of light distillates. The technology can be used for treating vari...The S-RHT technology is developed by FRIPP for residue hydrotreating in the fixed bed in order to process the high sulfur crude and increase the yield of light distillates. The technology can be used for treating various kinds of atmospheric residues (AR) or vacuum residues (VR) with a total metal content less than 150 ppm under the operating conditions of a temperature ranging from 360-410℃, a hydrogen partial pressure of 14-15 MPa, a LHSV of 0.20-0.30h-1 and a hydrogen to oil ratio of 700-1000. A certain amount of light products can be obtained and the hydrotreated atmospheric residue can fully meet the needs for the feedstock to RFCC or a blending feedstock to FCC. Based on the S-RHT technology, a 2 Mt/a residue hydrotreating unit has been constructed and successfully started up at Maoming Petrochemical Company by the end of 1999.展开更多
文摘Based on the mechanism of resid hydrotreating reaction by coordinating the catalyst activity and stability, the diffusion mechanism and catalyst reactivity, the cost and catalyst performance, and the production and application requirements, the third-generation series catalysts for residue hydrotreating have been developed by Research Institute of Petroleum Processing, SINOPEC. The new series RHT catalysts possess higher activity for HDS, HDM and HDCCR performance as well as longer run length. The commercial results for application of these catalysts have demonstrated that the new catalyst system performs better than the reference ones.
文摘This article has summarized the optimized measures relating to the loading of catalyst,and the sixth operating cycle of the residue hydrotreating unit at SINOPEC's Maoming Branch Company,and made a detailed comparison on the impurities removal rate,hydrogen consumption and energy consumption of the sixth operating cycle with those achieved by the previous five cycles.Test results have revealed that the second-generation RHT series novel residue hydrotreating catalysts featured high activity,good stability,and long operating cycle and could remarkably reduce the hydrogen consumption and energy consumption of process unit.The hydrotreated AR product,having low Conradson carbon residue,low sulfur content,low metal content,high content of saturated hydrocarbons,and low content of asphaltenes and resins,is an excellent FCC feed.Judging from their overall property the second-generation RHT series of residue hydrotreating catalysts used in the sixth operating cycle have commanded a leading position among other catalysts used in previous operating cycles.
文摘This article refers to the first commercial application of upflow residuum hydrotreating serial catalyst, developed by Fushun Research Institute of Petroleum and Petrochemicals (FRIPP), in the residuum hydrotreating unit at Shengli refinery of Qilu Petrochemical Company. This catalyst features large pore volume and large pore diameter. The production practice for more than one year has revealed that the domestic upflow residuum hydrotreating catalyst has shown good performance and stability over the whole period of operation despite its high activity at the start of run, and has basically reached the level of similar imported catalyst.
文摘In order to extend the operating cycle of the upflow reactor for resid hydrotreating, the Re- search Institute of Petroleum Processing taking into account the specifics of resid hydrotreating upflow reactor has developed the high-performance RUF series of catalysts suitable for operation in the upflow reactor. The results of commercial application of catalysts revealed that this RUF series of catalysts loaded after optimized grading could effectively remove metals, sulfur and carbon residue from the re-siduum to provide improved oil for the following fixed-bed reactor. In the meantime, the RUF series of catalysts have excellent stability to reach an operating cycle of 1.5 years, resulting in minimization of losses caused by refinery downtime.
基金Financial supports from the NSFC-DFG (21761132006),NSFC (21773108)fundamental research funds for central universities are acknowledged
文摘A 60%Fe/Al_2O_3 catalyst was prepared by the co-precipitation method.It was reduced by H_2 to produce metallic Fe,which was then sulfided by CS_2 to Fe_(0.96) S and Fe_3S_4 or phosphided by triphenylphosphine(PPh3) in liquid phases to Fe2 P and Fe P.It was found that the iron sulfides(Fe0.96 S and Fe_3S_4) exhibited the low activity for the hydrodesulfurization(HDS) reactions.The HDS activity was also low on the Fe(metal)/Al_2O_3 and Fe_2 P/Al_2O_3 catalysts since they were converted into Fe0.96 S and Fe_3S_4 during the HDS reactions.In contrast,the FeP/Al_2O_3 was found to be stable and active for the HDS reactions.In particular,Fe P/Al_2O_3 possessed significantly smaller Fe P particles than Fe P/C,leading to the significant higher HDS activity of FeP/Al_2O_3 than Fe P/C.
文摘X-ray absorption fine structure (XAFS) and other techniques have been used to characterize Ni-Mo/Al2O3 supported catalysts. The analysis of Mo K-edge spetrum shows that the active species over sulfide catalysts are MoS2-alike and the dispersion of Mo is high at the level of nanometer particles. There may exist some distortion of the local environment of MoS2, which has an influence on the hydrotreating activities of catalysts. Ni K-edge analysis shows that the coordination effects of Ni-Mo favor the dispersion state of active phase and imply a close relationship with catalyst activities.
文摘This article refers to the commercial application assessment of the novel S-RHT catalysts.The application outcome has shown that the catalysts loading was reduced with its performance kept at the original level at the initial and middle stages of operation. The performance of catalysts at the end of operation was analyzed, and factors affecting the performance of the novel catalysts at the end of run were identified to facilitate further improvement of the said catalysts.
文摘PASCA, ESR and Microreactor, have been used to study the states and properties of coking deposits on catalyst. The results indicate that the C exists as three types of states on catalyst surface. The first and second types of carbon are the main reason of the catalyst deactivation, but the third type has a promoting role in n-C_7 hydrocracking reaction. The S_s-C interacts strongly with catalyst, forming metal-carbon-support interaction (MCSI).
基金support from the SINOPEC Research Program(No.111145)
文摘The RHT technology and the second generation RHT catalysts were applied in design of an 1.7Mt/a VRDS unit at the SINOPEC Changling Branch Co. The commercial application result demonstrated that the RHT catalysts showed good activity and stability in processing low-sulfur and high-nitrogen residue. The first long period run of unit for processing high Fe and high Ca content residue was achieved. The reasons for excessive pressure drop of R-101 were ascribed to Fe and Ca deposition as well as coke formation.
文摘The development and application of ex-situ presulfurization(EPRES)technology for hydrotreating catalysts has been reviewed in the present article.The studies in laboratory scale and commercial practice indicated that the adoption of the EPRES catalyst in industrial application can significantly enhance the degree of presulfurization of metal oxide components,shorten the start-up period,and effectively reduce the environmental impact as well as the danger of start-up procedure in industrial hydrotreating unit.This catalyst has been proved to be versatile for different types of hydrogenation reactions.Different types of active site models are also discussed for better understanding the nature of presulfur-ized catalysts.
文摘The SHIFT-G technology of inverse catalyst loading is used to optimize the catalyst grading in the residue hydrotreating unit. The results, taken from pilot tests and commercial units, have showed that the optimized catalyst grading system can reasonably distribute the reaction load, effectively improve the prop- erties of hydrotreated products, prolong the operating cycle and promote economic benefits.
文摘Based on the reaction mechanism of resid hydrodemetallization, a new catalyst carrier was designed and prepared. As compared with the similar type of catalyst carrier, the said new carrier featured a higher pore volume, a larger pore diameter and a weaker surface acidity, which could improve the diffusion performance and stable reaction performance of the catalyst. The active metal components were loaded on the said carrier by a new technique for better metal dispersion, thus the impurity removal rate of the new catalyst, RDM-3, was improved significantly. The commercial test of the RDM-3 catalyst showed that the process of catalyst preparation was stable, the catalyst performance was slightly better than the catalyst prepared in the lab, therefore, the catalyst could be manufactured in commercial scale.
文摘Qilu Petrochemical Company in order to synchronize the replacement of catalysts in the upflow reactor (UFR) and fixed-bed reactors and achieve the 1.5-year operating cycle of the residue hydrotreating unit has revamped the UFR and optimized catalysts grading. Commercial operation results have revealed that the series of catalysts for residue hydrotreating after optimized grading achieved an operating cycle of 1.5 years with the quality of hydrotreated oil products meeting the requirements for FCC feedstock.
文摘The RHT technology is developed by Research Institute of Petroleum Processing (RIPP) for residuum hydrotreating in order to produce good quality RFCC feed. The advantages of the RHT series catalysts are presented in this article, based on the results of activity tests and a 9500 hours service life test in pilot plants and the assessment on a commercial application.
基金the financial support provided by the National Natural Science Foundation of China (Grant No. 21376266)the Petro China Innovation Foundation (Grant No. 2011D-5006-0405)the Fundamental Research Funds for the Central Universities (Grant No. 27R1104049A)
文摘The effect of additive—dodecylbenzene sulfonic acid(DBSA)—on residue hydrotreating was studied in the au toclave. The results showed that the additive improved stabilization of the colloid system of residue, which could delay th aggregation and coke formation from asphaltenes on the catalyst, and make heavy components transformed into light oi The residue conversion in the presence of this additive increased by 1.94%, and the yield of light oil increased by 1.53%when the reaction time was 90 min. The surface properties of the catalyst in the presence of this additive were better tha that of the blank test within a very short time(30 min) and deteriorated rapidly after a longer reaction time due to highe conversion and coke deposition. Compared with the blank test, the case using the said additive had shown that the structur of hydrotreated asphaltene units was smaller and the condensation degrees were higher. The test results indicated that th additive could improve the hydrotreating reactivity of residue via permeation and depolymerization, the heavier componen could be transformed into light oil more easily, and the light oil yield and residue conversion were higher for the case usin the said additive in residue hydrotreating process.
文摘The S-RHT technology is developed by FRIPP for residue hydrotreating in the fixed bed in order to process the high sulfur crude and increase the yield of light distillates. The technology can be used for treating various kinds of atmospheric residues (AR) or vacuum residues (VR) with a total metal content less than 150 ppm under the operating conditions of a temperature ranging from 360-410℃, a hydrogen partial pressure of 14-15 MPa, a LHSV of 0.20-0.30h-1 and a hydrogen to oil ratio of 700-1000. A certain amount of light products can be obtained and the hydrotreated atmospheric residue can fully meet the needs for the feedstock to RFCC or a blending feedstock to FCC. Based on the S-RHT technology, a 2 Mt/a residue hydrotreating unit has been constructed and successfully started up at Maoming Petrochemical Company by the end of 1999.
