To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation betwe...To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation between the surface characteristics of four different alumina and the existing Mo species states was established.It was found that the Mo equilibrium adsorption capacity can be used as a specific descriptor to quantitatively evaluate the changes in surface characteristics of different alumina.A lower Mo equilibrium adsorption capacity for alumina means weaker metal-support interaction and the loaded Mo species are easier to transform into MoS2.However,the Mo-O-Al bonds still exist at the metal-support interface.The introduction of cationic surfactant hecadecyl trimethyl ammonium bromide(CTAB)can further improve Mo species dispersion through electrostatic attraction with Mo anions and interaction of its alkyl chain with the alumina surface;meanwhile,the introduction of ethylenediamine tetraacetic acid(EDTA)can complex with Ni ions to enhance the Ni-promoting effect on Mo.Therefore,the NiMo catalyst designed using alumina with lower Mo equilibrium adsorption capacity and the simultaneous addition of EDTA and CTAB exhibits the highest hydrodesulfurization activity for 4,6-dimethyl dibenzothiophene because of its proper metal-support interaction and more well-dispersed Ni-Mo-S active phases.展开更多
The FCC naphtha selective hydrodesulfurization technology(RSDS-II)has been tested with different feedstocks in pilot scale.The results show that RSDS-II technology is viable in terms of its adaptability to different f...The FCC naphtha selective hydrodesulfurization technology(RSDS-II)has been tested with different feedstocks in pilot scale.The results show that RSDS-II technology is viable in terms of its adaptability to different feedstocks.To produce gasoline with a sulfur content of less than 50μg/g by the RSDS-II technology,the gasoline RON loss is less than 1.8,0.9and 0.2 units,respectively,upon processing the conventional high-sulfur and high-olefin FCC naphtha,the high-sulfur MIP naphtha,and the medium-sulfur or low-sulfur MIP naphtha.Upon using the naphtha produced from pre-hydrotreated FCC feedstock as the RSDS-II feedstock to manufacture gasoline with a sulfur content of lower than 10μg/g,the RON loss does not exceed 1.0 unit.The RSDS-II technology has been commercialized successfully at many refineries.The result of operating commercial RSDS-II unit at the Shanghai Petrochemical Company has revealed that upon processing a feedstock containing 38.7 v% —43.3 v% of olefins and 250—470 mg/g of sulfur,the sulfur content in the treated gasoline ranges from 33μg/g to 46μg/g and the RON loss is equal to only 0.3—0.6 units.Till now this RSDS-II unit has been operating smoothly over 30 months.Thanks to its high HDS activity and good selectivity,the RSDS-II technology can meet the refinery’s needs for adequate upgrading of gasoline.展开更多
To adapt to the change in the demand of the oil refining market,two hydrocracking catalysts,RHC-1 and RHC-5,were developed to improve the quality of tail oil.The catalysts were designed based on the theory of selectiv...To adapt to the change in the demand of the oil refining market,two hydrocracking catalysts,RHC-1 and RHC-5,were developed to improve the quality of tail oil.The catalysts were designed based on the theory of selective ring-opening.By selecting more acidic molecular sieves,the problem of poor selectivity of conventional materials can be solved to properly match up to the hydrogenation performance of catalysts.Compared with the performance of previous catalysts,the quality of the tail oil achieved by the said catalysts is better,and the BMCI is reduced by 1—2 units.In the long cycle operation of the petroleum industry,the good quality of the tail oil has been verified and the adaptability of the process conditions is good.When the RHC-1 catalyst is used to process heavy feed under medium pressure,a BMCI value of about12 can be obtained along with a nearly 60%yield of tail oil.The total yield of chemical raw material(steaming cracking feed+catalytic reforming feed)can exceed 80%,and the hydrogen consumption has dropped by nearly 50%as compared to the conventional hydrocracking conversion rate.When processing a mixed CGO and VGO feed with the full conversion mode under a hydrogen pressure of 13.0 MPa,the RHC-5 catalyst can yield about 68.4%of heavy naphtha with a potential aromatic content of up to 50.6,while the total yield of chemical raw materials can reach more than 98%.The results of industrial application of these catalysts show that more than 30%of high quality tail oil can be obtained via processing of inferior quality feed,and its BMCI value can reach 10.7.The total yield of chemical raw materials can reach more than65%.The industrial operation process has implemented two operating cycles totaling 8 years.展开更多
Geranylgeranyl diphosphate synthase (GGPPS) plays a key role in the biosynthesis of antioxidative ca-rotenoid from the extremely radioresistant bacterium Deinococcus radiodurans. In this work, the recombinant GGPPS ex...Geranylgeranyl diphosphate synthase (GGPPS) plays a key role in the biosynthesis of antioxidative ca-rotenoid from the extremely radioresistant bacterium Deinococcus radiodurans. In this work, the recombinant GGPPS expressed in Escherichia coli by cloning and transforming the gene dr1395 of D. radiodurans was isolated rapidly by an immobilized metal affinity supermacroporous cryogel, i.e., Cu2+-iminodiacetic acid (IDA)-cryogel. The properties of the Cu2+-IDA-cryogel were characterized using capillary-based mathematical model and experi-mental measurements. The obtained protein samples were analyzed by the sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). The porosity of the present Cu2+-IDA-cryogel is 90.4% and the water permeabil-ity is 5.04×10-12 m2. From the capillary-based model, this cryogel presents a slightly wide normal pore (capillary) size distribution with the mean diameter of 55.2 μm, the standard deviation of 28.0 μm and the half of skeleton wall thickness of 2.8 μm. The pore size distribute from about 10 to 141 μm and the effective tortuosity of these capillary pores increases from 2.60 to 9.05. The isolation of the GGPPS from cell homogenate can be achieved at the flow velocity of 3.40×10-4 m·s-1 by the Cu2+-IDA-cryogel bed. High-purity GGPPS (about 91.4%) is obtained according to the SDS-PAGE analysis of the elution samples, indicating that the present method is a promising, simple and ef-fective approach to isolate GGPPS from cell homogenate of engineering strains.展开更多
基金funding of the National Key Research and Development Plan(Grant 2017YFB0306600)the Project of SINOPEC(NO.117006).
文摘To prepare a highly efficient NiMo/Al_(2)O_(3) hydrodesulfurization catalyst,the combined effects of specific organic functional groups and alumina surface characteristics were investigated.First,the correlation between the surface characteristics of four different alumina and the existing Mo species states was established.It was found that the Mo equilibrium adsorption capacity can be used as a specific descriptor to quantitatively evaluate the changes in surface characteristics of different alumina.A lower Mo equilibrium adsorption capacity for alumina means weaker metal-support interaction and the loaded Mo species are easier to transform into MoS2.However,the Mo-O-Al bonds still exist at the metal-support interface.The introduction of cationic surfactant hecadecyl trimethyl ammonium bromide(CTAB)can further improve Mo species dispersion through electrostatic attraction with Mo anions and interaction of its alkyl chain with the alumina surface;meanwhile,the introduction of ethylenediamine tetraacetic acid(EDTA)can complex with Ni ions to enhance the Ni-promoting effect on Mo.Therefore,the NiMo catalyst designed using alumina with lower Mo equilibrium adsorption capacity and the simultaneous addition of EDTA and CTAB exhibits the highest hydrodesulfurization activity for 4,6-dimethyl dibenzothiophene because of its proper metal-support interaction and more well-dispersed Ni-Mo-S active phases.
基金financially supported bu the Nationol Key Technology R&D Program of China(2007BAE43B01)and SINOPEC Corporation(contact No.106076)
文摘The FCC naphtha selective hydrodesulfurization technology(RSDS-II)has been tested with different feedstocks in pilot scale.The results show that RSDS-II technology is viable in terms of its adaptability to different feedstocks.To produce gasoline with a sulfur content of less than 50μg/g by the RSDS-II technology,the gasoline RON loss is less than 1.8,0.9and 0.2 units,respectively,upon processing the conventional high-sulfur and high-olefin FCC naphtha,the high-sulfur MIP naphtha,and the medium-sulfur or low-sulfur MIP naphtha.Upon using the naphtha produced from pre-hydrotreated FCC feedstock as the RSDS-II feedstock to manufacture gasoline with a sulfur content of lower than 10μg/g,the RON loss does not exceed 1.0 unit.The RSDS-II technology has been commercialized successfully at many refineries.The result of operating commercial RSDS-II unit at the Shanghai Petrochemical Company has revealed that upon processing a feedstock containing 38.7 v% —43.3 v% of olefins and 250—470 mg/g of sulfur,the sulfur content in the treated gasoline ranges from 33μg/g to 46μg/g and the RON loss is equal to only 0.3—0.6 units.Till now this RSDS-II unit has been operating smoothly over 30 months.Thanks to its high HDS activity and good selectivity,the RSDS-II technology can meet the refinery’s needs for adequate upgrading of gasoline.
基金the financial support from the SINOPEC(No.114016)
文摘To adapt to the change in the demand of the oil refining market,two hydrocracking catalysts,RHC-1 and RHC-5,were developed to improve the quality of tail oil.The catalysts were designed based on the theory of selective ring-opening.By selecting more acidic molecular sieves,the problem of poor selectivity of conventional materials can be solved to properly match up to the hydrogenation performance of catalysts.Compared with the performance of previous catalysts,the quality of the tail oil achieved by the said catalysts is better,and the BMCI is reduced by 1—2 units.In the long cycle operation of the petroleum industry,the good quality of the tail oil has been verified and the adaptability of the process conditions is good.When the RHC-1 catalyst is used to process heavy feed under medium pressure,a BMCI value of about12 can be obtained along with a nearly 60%yield of tail oil.The total yield of chemical raw material(steaming cracking feed+catalytic reforming feed)can exceed 80%,and the hydrogen consumption has dropped by nearly 50%as compared to the conventional hydrocracking conversion rate.When processing a mixed CGO and VGO feed with the full conversion mode under a hydrogen pressure of 13.0 MPa,the RHC-5 catalyst can yield about 68.4%of heavy naphtha with a potential aromatic content of up to 50.6,while the total yield of chemical raw materials can reach more than 98%.The results of industrial application of these catalysts show that more than 30%of high quality tail oil can be obtained via processing of inferior quality feed,and its BMCI value can reach 10.7.The total yield of chemical raw materials can reach more than65%.The industrial operation process has implemented two operating cycles totaling 8 years.
基金Supported by the National Natural Science Foundation of China （30830006, 20876145, 21036005）, the International Science ＆ Technology Cooperation Program from the Ministry of Science and Technology of China （1017）, the Special Fund for Agroscientific Research in the Public Interest （201103007）, the Fundamental Research Funds for the Central Universities and the Natural Science Foundation of Zhejiang Province （Y4080326, Y407366）.
文摘Geranylgeranyl diphosphate synthase (GGPPS) plays a key role in the biosynthesis of antioxidative ca-rotenoid from the extremely radioresistant bacterium Deinococcus radiodurans. In this work, the recombinant GGPPS expressed in Escherichia coli by cloning and transforming the gene dr1395 of D. radiodurans was isolated rapidly by an immobilized metal affinity supermacroporous cryogel, i.e., Cu2+-iminodiacetic acid (IDA)-cryogel. The properties of the Cu2+-IDA-cryogel were characterized using capillary-based mathematical model and experi-mental measurements. The obtained protein samples were analyzed by the sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). The porosity of the present Cu2+-IDA-cryogel is 90.4% and the water permeabil-ity is 5.04×10-12 m2. From the capillary-based model, this cryogel presents a slightly wide normal pore (capillary) size distribution with the mean diameter of 55.2 μm, the standard deviation of 28.0 μm and the half of skeleton wall thickness of 2.8 μm. The pore size distribute from about 10 to 141 μm and the effective tortuosity of these capillary pores increases from 2.60 to 9.05. The isolation of the GGPPS from cell homogenate can be achieved at the flow velocity of 3.40×10-4 m·s-1 by the Cu2+-IDA-cryogel bed. High-purity GGPPS (about 91.4%) is obtained according to the SDS-PAGE analysis of the elution samples, indicating that the present method is a promising, simple and ef-fective approach to isolate GGPPS from cell homogenate of engineering strains.
