Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products o...Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products obtained over different catalysts were determined by GC-PFPD.The test results showed that the diatomite-dispersed NiMoW catalyst had high hydrodesulfurization activity for FCC diesel,which could be contributed to the excellent hydrogenation performance of the said catalyst.Characterization of catalyst by TEM and XRD indicated that the diatomite-dispersed NiMoW catalyst possessed higher layer stacking,larger curvature of MoS2or WS2,and segregated Ni3S2crystals relative to the supported catalyst.This kind of structure leads to high hydrogenation activity of the diatomite-dispersed NiMoW catalyst.展开更多
The computational fluid dynamics(CFD) code, FLUENT, was used to simulate the liquid-phase FCC diesel hydrotreating tubular reactor with a ceramic membrane tube dispenser. The chemical reaction and reaction heat were a...The computational fluid dynamics(CFD) code, FLUENT, was used to simulate the liquid-phase FCC diesel hydrotreating tubular reactor with a ceramic membrane tube dispenser. The chemical reaction and reaction heat were added to the model by user-defined function(UDF), showing the distribution of temperature and content of sulfides, nitrides, bicyclic aromatics and monocyclic aromatics in different parts of the reaction bed. When the pressure was 6.5 MPa, the amount of mixing hydrogen was 0.84%(m), the space velocity was 2 h-1 and the inlet temperature was 633 K, the temperature reached a maximum at a height of 0.15 m, and the range of radial temperature reached its maximum(2.5 K) at a height of 0.15 m. It indicated that the proper ratio of height to diameter of catalyst bed in the tubular reactor was 5-6. The increase of inlet temperature, the mixing hydrogen and the decrease of space velocity led to the decrease in the content of bicyclic aromatics, sulfides and nitrides, and the increase in monocyclic aromatics content, while the high temperature increased. The results were in good agreement with experimental data, indicating to the high accuracy of the model.展开更多
According to the characteristics of FCC diesel, a technology of liquid-phase hydrodesulfurization of the diesel in tubular reactors was proposed and lab-scale experiments were carried out. A kinetic model for the hydr...According to the characteristics of FCC diesel, a technology of liquid-phase hydrodesulfurization of the diesel in tubular reactors was proposed and lab-scale experiments were carried out. A kinetic model for the hydrodesulfurization process was developed and verified. The model was utilized to predict the sulfur content of products under different operating conditions. The effects of temperature, space velocity, pressure, and hydrogen concentration on the dcsulfurization rate were investigated.展开更多
The need for cleaner fuels has resulted in a continuing worldwide trend to reduce diesel sulfur and aromatics. There are many approaches to reducing sulfur and aromatics in diesel. Most of them have a common drawback ...The need for cleaner fuels has resulted in a continuing worldwide trend to reduce diesel sulfur and aromatics. There are many approaches to reducing sulfur and aromatics in diesel. Most of them have a common drawback of high cost because of adopting two stages of hydrotreating and using noble-metal catalyst, especially for reducing aromatics. The attempt to resolve this issue has led to the recent development of the Single Stage Hydrotreating (SSHT) process by Research Institute of Petroleum Processing (RIPP), SINOPEC.The SSHT process is a single-stage hydrotreating technology for producing low sulfur and low aromatics diesel. The process uses one or two non-noble-metal catalysts system and operates at moderate pressure. When revamping an existing unit to meet low aromatics diesel specification, the only thing to do is to add a reactor or replace the existing reactor, In pilot plant tests, the SSHT technology has successfully treated SRGO (Straight Run Gas Oil), LCO (Light Cycle Oil) or the blend of them. It is shown that by using the SSHT process diesel with sulfur of 30 ppm and aromatics of 15 m% can be produced from Middle-East SRGO and diesel with aromatics content of 25 m% can be produced from cracked feed, such as FCC-LCO. High diesel yield and cetane number gain (from cracked feed stocks) give the SSHT technology a performance advantage compared to conventional hydrocracking and hydrotreating processes.The lower investment and operating cost is another advantage. The first commercial application of the SSHT technology has been in operation since September 2001.展开更多
The effect of crystal size of USY zeolite on the performance of hydro-upgrading catalysts for treating catalytically cracked(FCC) LCO(light cycle oil) was studied.Three W-Ni catalysts supported on USY zeolites with di...The effect of crystal size of USY zeolite on the performance of hydro-upgrading catalysts for treating catalytically cracked(FCC) LCO(light cycle oil) was studied.Three W-Ni catalysts supported on USY zeolites with different crystal sizes and Al2O3 were prepared by impregnation method.The catalysts were characterized by XRD and BET methods,and evaluated in a micro-reactor using tetralin as the model compound and in an 100-mL hydrogenation test unit using FCC LCO as the feedstock.By contrast,catalyst made from smaller crystal-size USY zeolite had higher external surface area and shorter pore length,having more hydrogenation activity sites and short contact time of reactant molecules with acidity sites.The evaluation results showed that the catalyst prepared on the basis of small crystal-size USY zeolite had higher tetralin conversion and better hydro-upgrading performance for treating FCC LCO.展开更多
Modification and characterization of natural zeolite under some various methods for hydrocracking catalyst of waste lubricant to gasoline and diesel fractions have been conducted. Natural zeolite from Klaten was activ...Modification and characterization of natural zeolite under some various methods for hydrocracking catalyst of waste lubricant to gasoline and diesel fractions have been conducted. Natural zeolite from Klaten was activated using hydrothermal treatment at temperature 500 ℃ for 6 h (produced ZAAHd), the ZA sample was treated with hydrothermal followed by Microwave (produced ZAAHdM), the ZA sample was treated with HCI 3 N at temperature of 90 ℃ for 30 min (produced ZAAH), the ZAAH sample was heated in to microwave (produced ZAAHM), the ZAAHM was treated hydrothermal (produced ZAAHMHd), the ZAAHMHd sample was heated in to microwave (produced ZAAHMHdM), soaking of natural zeolit activated by HCl-microwave-hydrothermal-microwave in NH4NO3 1 N which was stirred using stirer at room temperature for 24 h (produced ZAAHMHdMN) and the ZAAHMHdMN sample was heated into microwave (ZAAHMHdMNM). The heating process by microwave was conducted at 550 watt for 15 rain. Catalyst characterization involved determination of the number of total acid sites using gravimetric method with vapour adsorption of NH3 and pyridine, catalyst crystallinity by XRD (X-ray diffraction) and TO4 (T= Si and AI) site by infra red spectrophotometer (IR). Hydrocracking of waste lubricants oil was performed in a fixed bed reactor of stainless steel at temperature of 450 ℃, H2 flow rate of 15 mL/min., feed/catalyst ratio of 5. Liquid products of the hydrocracking were analyzed using GC (gas chromatography). The characterization results showed that various modification of natural zeolite increased acidity and dealumination degree of the catalysts. Products of the hydrocracking were liquid, coke, and gas fractions. Liquid products consisted of gasoline fraction (C5-C12), diesel fraction (C12-C20), and heavy oil fraction (〉 C20).Thc conversion of liquid products was increased with the increase of catalyst acidity. The greatest liquid product conversion was produced by the ZAAHMHdMNM catalyst, i.e., 56.80%, with selectivity towards gasoline, diesel, and heavy oil fractions was 88.37%, 8.61% and 3.02%, respectively. The increase of catalyst acidity increased the selectivity of gasoline fraction.展开更多
基金support of National Natural Science Foundation of China(Grant No.21306106)the Specialized Research Fund for the Doctoral Program of Higher Education of China(Grant No.2012371812012)China Postdoctoral Science Foundation(Grant No.2012M541941)
文摘Diatomite-dispersed NiMoW catalyst was prepared and characterized,and the activity of catalyst samples was tested during the HDS reaction of FCC diesel.Sulfur compounds in the feedstock and the hydrogenated products obtained over different catalysts were determined by GC-PFPD.The test results showed that the diatomite-dispersed NiMoW catalyst had high hydrodesulfurization activity for FCC diesel,which could be contributed to the excellent hydrogenation performance of the said catalyst.Characterization of catalyst by TEM and XRD indicated that the diatomite-dispersed NiMoW catalyst possessed higher layer stacking,larger curvature of MoS2or WS2,and segregated Ni3S2crystals relative to the supported catalyst.This kind of structure leads to high hydrogenation activity of the diatomite-dispersed NiMoW catalyst.
文摘The computational fluid dynamics(CFD) code, FLUENT, was used to simulate the liquid-phase FCC diesel hydrotreating tubular reactor with a ceramic membrane tube dispenser. The chemical reaction and reaction heat were added to the model by user-defined function(UDF), showing the distribution of temperature and content of sulfides, nitrides, bicyclic aromatics and monocyclic aromatics in different parts of the reaction bed. When the pressure was 6.5 MPa, the amount of mixing hydrogen was 0.84%(m), the space velocity was 2 h-1 and the inlet temperature was 633 K, the temperature reached a maximum at a height of 0.15 m, and the range of radial temperature reached its maximum(2.5 K) at a height of 0.15 m. It indicated that the proper ratio of height to diameter of catalyst bed in the tubular reactor was 5-6. The increase of inlet temperature, the mixing hydrogen and the decrease of space velocity led to the decrease in the content of bicyclic aromatics, sulfides and nitrides, and the increase in monocyclic aromatics content, while the high temperature increased. The results were in good agreement with experimental data, indicating to the high accuracy of the model.
基金the financial support from the SINOPEC(No.2014310031600599)
文摘According to the characteristics of FCC diesel, a technology of liquid-phase hydrodesulfurization of the diesel in tubular reactors was proposed and lab-scale experiments were carried out. A kinetic model for the hydrodesulfurization process was developed and verified. The model was utilized to predict the sulfur content of products under different operating conditions. The effects of temperature, space velocity, pressure, and hydrogen concentration on the dcsulfurization rate were investigated.
文摘The need for cleaner fuels has resulted in a continuing worldwide trend to reduce diesel sulfur and aromatics. There are many approaches to reducing sulfur and aromatics in diesel. Most of them have a common drawback of high cost because of adopting two stages of hydrotreating and using noble-metal catalyst, especially for reducing aromatics. The attempt to resolve this issue has led to the recent development of the Single Stage Hydrotreating (SSHT) process by Research Institute of Petroleum Processing (RIPP), SINOPEC.The SSHT process is a single-stage hydrotreating technology for producing low sulfur and low aromatics diesel. The process uses one or two non-noble-metal catalysts system and operates at moderate pressure. When revamping an existing unit to meet low aromatics diesel specification, the only thing to do is to add a reactor or replace the existing reactor, In pilot plant tests, the SSHT technology has successfully treated SRGO (Straight Run Gas Oil), LCO (Light Cycle Oil) or the blend of them. It is shown that by using the SSHT process diesel with sulfur of 30 ppm and aromatics of 15 m% can be produced from Middle-East SRGO and diesel with aromatics content of 25 m% can be produced from cracked feed, such as FCC-LCO. High diesel yield and cetane number gain (from cracked feed stocks) give the SSHT technology a performance advantage compared to conventional hydrocracking and hydrotreating processes.The lower investment and operating cost is another advantage. The first commercial application of the SSHT technology has been in operation since September 2001.
基金support from the China National Petroleum Corporation (CNPC) (2011B-2304-0305)
文摘The effect of crystal size of USY zeolite on the performance of hydro-upgrading catalysts for treating catalytically cracked(FCC) LCO(light cycle oil) was studied.Three W-Ni catalysts supported on USY zeolites with different crystal sizes and Al2O3 were prepared by impregnation method.The catalysts were characterized by XRD and BET methods,and evaluated in a micro-reactor using tetralin as the model compound and in an 100-mL hydrogenation test unit using FCC LCO as the feedstock.By contrast,catalyst made from smaller crystal-size USY zeolite had higher external surface area and shorter pore length,having more hydrogenation activity sites and short contact time of reactant molecules with acidity sites.The evaluation results showed that the catalyst prepared on the basis of small crystal-size USY zeolite had higher tetralin conversion and better hydro-upgrading performance for treating FCC LCO.
文摘Modification and characterization of natural zeolite under some various methods for hydrocracking catalyst of waste lubricant to gasoline and diesel fractions have been conducted. Natural zeolite from Klaten was activated using hydrothermal treatment at temperature 500 ℃ for 6 h (produced ZAAHd), the ZA sample was treated with hydrothermal followed by Microwave (produced ZAAHdM), the ZA sample was treated with HCI 3 N at temperature of 90 ℃ for 30 min (produced ZAAH), the ZAAH sample was heated in to microwave (produced ZAAHM), the ZAAHM was treated hydrothermal (produced ZAAHMHd), the ZAAHMHd sample was heated in to microwave (produced ZAAHMHdM), soaking of natural zeolit activated by HCl-microwave-hydrothermal-microwave in NH4NO3 1 N which was stirred using stirer at room temperature for 24 h (produced ZAAHMHdMN) and the ZAAHMHdMN sample was heated into microwave (ZAAHMHdMNM). The heating process by microwave was conducted at 550 watt for 15 rain. Catalyst characterization involved determination of the number of total acid sites using gravimetric method with vapour adsorption of NH3 and pyridine, catalyst crystallinity by XRD (X-ray diffraction) and TO4 (T= Si and AI) site by infra red spectrophotometer (IR). Hydrocracking of waste lubricants oil was performed in a fixed bed reactor of stainless steel at temperature of 450 ℃, H2 flow rate of 15 mL/min., feed/catalyst ratio of 5. Liquid products of the hydrocracking were analyzed using GC (gas chromatography). The characterization results showed that various modification of natural zeolite increased acidity and dealumination degree of the catalysts. Products of the hydrocracking were liquid, coke, and gas fractions. Liquid products consisted of gasoline fraction (C5-C12), diesel fraction (C12-C20), and heavy oil fraction (〉 C20).Thc conversion of liquid products was increased with the increase of catalyst acidity. The greatest liquid product conversion was produced by the ZAAHMHdMNM catalyst, i.e., 56.80%, with selectivity towards gasoline, diesel, and heavy oil fractions was 88.37%, 8.61% and 3.02%, respectively. The increase of catalyst acidity increased the selectivity of gasoline fraction.