The integrated catalytic hydrogenation and catalytic cracking process has been gradually adopted by refineries to satisfy the requirements for manufacture of light and clean petroleum products. To explore the reaction...The integrated catalytic hydrogenation and catalytic cracking process has been gradually adopted by refineries to satisfy the requirements for manufacture of light and clean petroleum products. To explore the reaction laws of hydrogenated aromatics in hydrotreated oil, the catalytic cracking reaction laws of hydrogenated aromatics have been reviewed by taking tetralin and decalin as examples of different degrees of hydrogenated aromatics. Moreover, the reaction mechanism of tetralin and decalin has been analyzed emphatically. The effects of zeolite pore structure, acid properties and process parameters on reaction laws have been analyzed carefully. It is considered that the catalytic cracking performance of hydrogenated aromatics with different hydrogen saturation degrees is quite different. It is necessary to control the hydrogenation depth, optimize the hydrocarbon composition of catalytic cracking feed materials for maximizing the yield of target products.展开更多
Catalytic pyrolysis process(CPP)producing ethylene and propylene from paraffin base atmospheric residue was developed by RIPP and its first in the world unit was put into commercial operation successfully.The results ...Catalytic pyrolysis process(CPP)producing ethylene and propylene from paraffin base atmospheric residue was developed by RIPP and its first in the world unit was put into commercial operation successfully.The results of performance test showed that the yield of ethylene and propylene reached 14.84% and 22.21% ,respectively,at a reaction temperature of610℃by using Daqing atmospheric residue as the feedstock under an operation mode of producing ethylene and propylene at the same time,and the aromatic content of cracked naphtha reached 82.46% .The successful operation of this unit has opened a novel route for producing light olefins and aromatics from heavy oil,which is also a good example symbolizing the integration of refining technology with petrochemical process.展开更多
The emerging FCC-based technologies are applied in an attempt to shift to the production of designated light olefins(including mainly ethylene and propylene) as well as light aromatics(including benzene, toluene, and ...The emerging FCC-based technologies are applied in an attempt to shift to the production of designated light olefins(including mainly ethylene and propylene) as well as light aromatics(including benzene, toluene, and xylene)developed by the Research Institute of Petroleum Processing(RIPP), SINOPEC. The RIPP's proprietary technologies covering the Deep Catalytic Cracking(DCC), the Enhanced Deep Catalytic Cracking(DCC-PLUS), and the Maximizing Catalytic Propylene(MCP) have been playing decisive roles in the processing of crude aimed at closer integration of petroleum refining and petrochemical production both inside and outside of China since 1990. Three cases of commercial applications in five refineries, including Case Ⅰ— the closer integration between the steam cracker and the DCC/DCC-PLUS unit, Case Ⅱ— the petrochemical refinery provided with a DCC-PLUS unit, and Case Ⅲ— the integrated petrochemical/fuels refinery provided with a MCP unit, have highlighted their far-reaching effects on global petrochemicals production.展开更多
Over the past decades SINOPEC has been uninterruptedly engaging in the development and upgrading of deep catalytic cracking （DCC） technology for manufacturing propylene from heavy oil. Recently SINOPEC after having ...Over the past decades SINOPEC has been uninterruptedly engaging in the development and upgrading of deep catalytic cracking （DCC） technology for manufacturing propylene from heavy oil. Recently SINOPEC after having made a lot of progress in the area of oil refining at the molecular level has developed a new generation DMMC-1 type catalyst designed for the DCC process. The laboratory evaluation tests have shown that compared to the existing MMC-2 type catalyst that features the best comprehensive performance, the DMMC-1 type catalyst has increased the propylene yield by 2.2% with the propylene selectivity increased by 10%. The said catalyst has improved its ability for heavy oil cracking and coke selectivity along with reduction of olefin content in gasoline to achieve a better product distribution and improve the product quality. The results of application of the said catalyst in a 650-kt/a commercial DCC unit at SINOPEC Anqing Branch Company have revealed that the DMMC- 1 catalyst demonstrated an enhanced capability for heavy oil cracking and could increase the total liquid yield to 84.56 m% from 83.92 m%, the LPG yield to 38.90 m % from 34.60 m %, the propylene yield to 17.80 m% from 15.37 m% and the propylene concentration to 45.91 m% from 44.91 m%, and reduce the coke yield from 7.61 m% to 7.05 m% and the olefin content in gasoline from 42.3 v% to 37.5 v%, resulting in an incremental profit amounting to 52.19 million RMB a year. This technology has further upgraded and developed the DCC technology which has been commanding a leading position among the industry peers.展开更多
A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene andpropylene from heavy oil feedstock has been developed. The catalyst CEP was specially designedfor this process, which has bi-functional c...A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene andpropylene from heavy oil feedstock has been developed. The catalyst CEP was specially designedfor this process, which has bi-functional catalytic activities for both carbonium ion reaction andfree radical reaction, so as to maximize the yields of ethylene and propylene. The commercial trialshowed that the yield of ethylene and propylene was 20.37% and 18.23% respectively inmaximum ethylene operation with Daqing AR as feedstock, and the yield of ethylene and propylenewas 9.77% and 24.60% respectively in maximum propylene operation by using the same feedstock.Compared with steam cracker, the feed cost of CPP is much lower for producing ethylene andpropylene.展开更多
Two series of molybdenum-containing MCM-41 catalysts were prepared for oxidative desulfurization ofdibenzothiophene （DBT） using t-butylhydroperoxide （TBHP） as the oxidant. The electronic properties, pore dimension...Two series of molybdenum-containing MCM-41 catalysts were prepared for oxidative desulfurization ofdibenzothiophene （DBT） using t-butylhydroperoxide （TBHP） as the oxidant. The electronic properties, pore dimension and hydrophilic properties of the catalysts were studied by XRD, BET, and 1R spectrometry. The Mo-Al2O3 catalyst and TiMCM-3% were also studied for comparison. The two series of MCM-41 zeolite with MoO3 in the framework or impregnated on the surface exhibited considerable activities at low MoO3 content and both were faxbetter than the Mo-Al2O3 catalyst, but had lower activities as compared to the TiMCM-3% catalyst. The catalysts with the highest activity were evaluated in a fixed-bed reactor. The concentration of DBT in model diesel upon oxidative desulfurization was successfully reduced from 5000 ppm to less than 150 ppm, but the catalysts were deactivated very fast. The probable reason was the high affinity of DBTO2 to the MCM-41 skeleton, especially to MoO3. The catalysts could restore most of its original activity by treating with alcohol.展开更多
The influence of operating parameters on ethylene content in dry gas obtained during catalytic cracking of gasoline was investigated in a pilot fixed fluidized bed reactor in the presence of the MMC-2 catalyst. The re...The influence of operating parameters on ethylene content in dry gas obtained during catalytic cracking of gasoline was investigated in a pilot fixed fluidized bed reactor in the presence of the MMC-2 catalyst. The results have shown that the majority of dry gas was formed during the catalytic cracking reaction of gasoline, with a small proportion of dry gas being formed through the thermal cracking reaction of gasoline. The ethylene content in dry gas formed during the catalytic cracking reaction was higher than that in dry gas formed during the thermal cracking reaction. The ethylene content in dry gas formed during catalytic cracking of gasoline with a higher olefin content was higher than that in dry gas formed during catalytic cracking of gasoline with a lower olefin content, which meant that the higher the amount of carbonium ions was produced during the reaction, the higher the ethylene content in the dry gas would be. An increasing reaction temperature could increase the percentage of dry gas formed during thermal cracking reaction in total dry gas products, leading to decreased ethylene content in the dry gas. An increasing catalyst/oil ratio could be conducive to the catalytic cracking reactions taking place inside the zeolite Y, leading to a decreased ethylene content in the dry gas. A decreasing space velocity could be conducive to the catalytic cracking reactions taking place inside the shape-selective zeolite, leading to increased ethylene content in the dry gas.展开更多
The structure and energy of the carbonium ions formed upon protonation of butane were studied by the DFT methods. Four stable structures are identified for the protonated form of n-butane, the energy increases in the ...The structure and energy of the carbonium ions formed upon protonation of butane were studied by the DFT methods. Four stable structures are identified for the protonated form of n-butane, the energy increases in the following order： C2HC3〈C1HC2〈C2HH〈C1HH, and the stability decreases in the following order C2HC3〉C1HC2〉C2HH〉C1HH. The stability of the penta-coordinated carbonium ions may be explained by the electron distribution in the three-center-two-electron bonds. The delocalization of the penta-coordinated carbonium ion CHC with three-center-two-electron bonds on positive charges was stronger than that of the penta-coordinated earbonium ion CHH with three-center-two-electron bonds and its stability was higher than that of the penta-coordinated carbonium ion CHH with three-center-two-electron bonds.展开更多
A novel catalytic cracking process named the MIP process was developed by the Research Institute of Petroleum Processing(RIPP),SINOPEC,to manufacture clean gasoline with lower olefin contents. The MIP pro-cess feature...A novel catalytic cracking process named the MIP process was developed by the Research Institute of Petroleum Processing(RIPP),SINOPEC,to manufacture clean gasoline with lower olefin contents. The MIP pro-cess features a unique riser consisting of two sequential reaction zones with different radii,in which different kinds of chemical reactions are intensified respectively to achieve better product slates and product properties. In order to fully implement the MIP potentials,a proprietary catalyst RMI tailored to the needs of the MIP process was devel-oped by adopting an AIRY zeolite having improved accessibility to active sites,which could result in better heavy oil cracking,coke selectivity and olefin reduction performance compared with the conventional REUSY zeolite. Its commercial application showed that the RMI catalyst could further reduce the olefin content in gasoline and raise the gasoline octane number while increasing the total liquid yield. On the basis of the MIP process,the MIP-CGP process was also developed to significantly reduce the olefin content in FCC naphtha and to enhance the propylene yield simultaneously. As far as the MIP-CGP process itself is concerned,both the MIP-CGP process and the MIP process have the similar reactor configuration but with different reactor size and operating parameters. The proprietary catalyst CGP-1 is also proposed to tailor for the MIP-CGP process. The specific features of the CGP-1 catalyst cover the new matrix,which possesses excellent capability to accommodate coke formation in the first reaction zone;the modified Y zeolite,which exhibits high hydrogen transfer activity in the second reaction zone;and the MFI zeolite,which has good gasoline olefin cracking activity. The commercial test results of MIP-CGP process applied along with the CGP-1 catalyst showed that the olefin content of gasoline was less than 18 v% and the propylene yield was more than 8 m%. Furthermore,as compared with the conventional FCC process,the gasoline properties were improved greatly and a higher total liquid yield was obtained. The advantages and characteristics of the MIP-CGP process were fully exploited by using the CGP-1 catalyst.展开更多
The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was ...The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was studied in a small- scale fixed fluid catalytic cracking unit. Test results have revealed that compared to the USY zeolite and Beta zeolite, the catalytic pyrolysis of n-heptane in the presence of the ZRP zeolite catalyst can result in higher yield and selectivity of ethyl- ene and propylene, while a higher reaction temperature and a higher catalyst/oil ratio can promote the formation of ethylene and propylene during catalytic pyrolysis of n-heptane. The ethylene formation reaction is more sensitive to the changes in reaction temperature, whereas the changes in catalyst/oil ratio are more influential to the propylene formation reaction. This paper has made a preliminary exploration into the different reaction pathways for formation of ethylene and propylene on zeolites with different structures.展开更多
文摘The integrated catalytic hydrogenation and catalytic cracking process has been gradually adopted by refineries to satisfy the requirements for manufacture of light and clean petroleum products. To explore the reaction laws of hydrogenated aromatics in hydrotreated oil, the catalytic cracking reaction laws of hydrogenated aromatics have been reviewed by taking tetralin and decalin as examples of different degrees of hydrogenated aromatics. Moreover, the reaction mechanism of tetralin and decalin has been analyzed emphatically. The effects of zeolite pore structure, acid properties and process parameters on reaction laws have been analyzed carefully. It is considered that the catalytic cracking performance of hydrogenated aromatics with different hydrogen saturation degrees is quite different. It is necessary to control the hydrogenation depth, optimize the hydrocarbon composition of catalytic cracking feed materials for maximizing the yield of target products.
文摘Catalytic pyrolysis process(CPP)producing ethylene and propylene from paraffin base atmospheric residue was developed by RIPP and its first in the world unit was put into commercial operation successfully.The results of performance test showed that the yield of ethylene and propylene reached 14.84% and 22.21% ,respectively,at a reaction temperature of610℃by using Daqing atmospheric residue as the feedstock under an operation mode of producing ethylene and propylene at the same time,and the aromatic content of cracked naphtha reached 82.46% .The successful operation of this unit has opened a novel route for producing light olefins and aromatics from heavy oil,which is also a good example symbolizing the integration of refining technology with petrochemical process.
基金Financial supports from the SINOPEC Research program (S111088, S105086, and S193046)
文摘The emerging FCC-based technologies are applied in an attempt to shift to the production of designated light olefins(including mainly ethylene and propylene) as well as light aromatics(including benzene, toluene, and xylene)developed by the Research Institute of Petroleum Processing(RIPP), SINOPEC. The RIPP's proprietary technologies covering the Deep Catalytic Cracking(DCC), the Enhanced Deep Catalytic Cracking(DCC-PLUS), and the Maximizing Catalytic Propylene(MCP) have been playing decisive roles in the processing of crude aimed at closer integration of petroleum refining and petrochemical production both inside and outside of China since 1990. Three cases of commercial applications in five refineries, including Case Ⅰ— the closer integration between the steam cracker and the DCC/DCC-PLUS unit, Case Ⅱ— the petrochemical refinery provided with a DCC-PLUS unit, and Case Ⅲ— the integrated petrochemical/fuels refinery provided with a MCP unit, have highlighted their far-reaching effects on global petrochemicals production.
文摘Over the past decades SINOPEC has been uninterruptedly engaging in the development and upgrading of deep catalytic cracking （DCC） technology for manufacturing propylene from heavy oil. Recently SINOPEC after having made a lot of progress in the area of oil refining at the molecular level has developed a new generation DMMC-1 type catalyst designed for the DCC process. The laboratory evaluation tests have shown that compared to the existing MMC-2 type catalyst that features the best comprehensive performance, the DMMC-1 type catalyst has increased the propylene yield by 2.2% with the propylene selectivity increased by 10%. The said catalyst has improved its ability for heavy oil cracking and coke selectivity along with reduction of olefin content in gasoline to achieve a better product distribution and improve the product quality. The results of application of the said catalyst in a 650-kt/a commercial DCC unit at SINOPEC Anqing Branch Company have revealed that the DMMC- 1 catalyst demonstrated an enhanced capability for heavy oil cracking and could increase the total liquid yield to 84.56 m% from 83.92 m%, the LPG yield to 38.90 m % from 34.60 m %, the propylene yield to 17.80 m% from 15.37 m% and the propylene concentration to 45.91 m% from 44.91 m%, and reduce the coke yield from 7.61 m% to 7.05 m% and the olefin content in gasoline from 42.3 v% to 37.5 v%, resulting in an incremental profit amounting to 52.19 million RMB a year. This technology has further upgraded and developed the DCC technology which has been commanding a leading position among the industry peers.
文摘A new process named CPP (Catalytic Pyrolysis Process) for producing ethylene andpropylene from heavy oil feedstock has been developed. The catalyst CEP was specially designedfor this process, which has bi-functional catalytic activities for both carbonium ion reaction andfree radical reaction, so as to maximize the yields of ethylene and propylene. The commercial trialshowed that the yield of ethylene and propylene was 20.37% and 18.23% respectively inmaximum ethylene operation with Daqing AR as feedstock, and the yield of ethylene and propylenewas 9.77% and 24.60% respectively in maximum propylene operation by using the same feedstock.Compared with steam cracker, the feed cost of CPP is much lower for producing ethylene andpropylene.
文摘Two series of molybdenum-containing MCM-41 catalysts were prepared for oxidative desulfurization ofdibenzothiophene （DBT） using t-butylhydroperoxide （TBHP） as the oxidant. The electronic properties, pore dimension and hydrophilic properties of the catalysts were studied by XRD, BET, and 1R spectrometry. The Mo-Al2O3 catalyst and TiMCM-3% were also studied for comparison. The two series of MCM-41 zeolite with MoO3 in the framework or impregnated on the surface exhibited considerable activities at low MoO3 content and both were faxbetter than the Mo-Al2O3 catalyst, but had lower activities as compared to the TiMCM-3% catalyst. The catalysts with the highest activity were evaluated in a fixed-bed reactor. The concentration of DBT in model diesel upon oxidative desulfurization was successfully reduced from 5000 ppm to less than 150 ppm, but the catalysts were deactivated very fast. The probable reason was the high affinity of DBTO2 to the MCM-41 skeleton, especially to MoO3. The catalysts could restore most of its original activity by treating with alcohol.
文摘The influence of operating parameters on ethylene content in dry gas obtained during catalytic cracking of gasoline was investigated in a pilot fixed fluidized bed reactor in the presence of the MMC-2 catalyst. The results have shown that the majority of dry gas was formed during the catalytic cracking reaction of gasoline, with a small proportion of dry gas being formed through the thermal cracking reaction of gasoline. The ethylene content in dry gas formed during the catalytic cracking reaction was higher than that in dry gas formed during the thermal cracking reaction. The ethylene content in dry gas formed during catalytic cracking of gasoline with a higher olefin content was higher than that in dry gas formed during catalytic cracking of gasoline with a lower olefin content, which meant that the higher the amount of carbonium ions was produced during the reaction, the higher the ethylene content in the dry gas would be. An increasing reaction temperature could increase the percentage of dry gas formed during thermal cracking reaction in total dry gas products, leading to decreased ethylene content in the dry gas. An increasing catalyst/oil ratio could be conducive to the catalytic cracking reactions taking place inside the zeolite Y, leading to a decreased ethylene content in the dry gas. A decreasing space velocity could be conducive to the catalytic cracking reactions taking place inside the shape-selective zeolite, leading to increased ethylene content in the dry gas.
文摘The structure and energy of the carbonium ions formed upon protonation of butane were studied by the DFT methods. Four stable structures are identified for the protonated form of n-butane, the energy increases in the following order： C2HC3〈C1HC2〈C2HH〈C1HH, and the stability decreases in the following order C2HC3〉C1HC2〉C2HH〉C1HH. The stability of the penta-coordinated carbonium ions may be explained by the electron distribution in the three-center-two-electron bonds. The delocalization of the penta-coordinated carbonium ion CHC with three-center-two-electron bonds on positive charges was stronger than that of the penta-coordinated earbonium ion CHH with three-center-two-electron bonds and its stability was higher than that of the penta-coordinated carbonium ion CHH with three-center-two-electron bonds.
文摘A novel catalytic cracking process named the MIP process was developed by the Research Institute of Petroleum Processing(RIPP),SINOPEC,to manufacture clean gasoline with lower olefin contents. The MIP pro-cess features a unique riser consisting of two sequential reaction zones with different radii,in which different kinds of chemical reactions are intensified respectively to achieve better product slates and product properties. In order to fully implement the MIP potentials,a proprietary catalyst RMI tailored to the needs of the MIP process was devel-oped by adopting an AIRY zeolite having improved accessibility to active sites,which could result in better heavy oil cracking,coke selectivity and olefin reduction performance compared with the conventional REUSY zeolite. Its commercial application showed that the RMI catalyst could further reduce the olefin content in gasoline and raise the gasoline octane number while increasing the total liquid yield. On the basis of the MIP process,the MIP-CGP process was also developed to significantly reduce the olefin content in FCC naphtha and to enhance the propylene yield simultaneously. As far as the MIP-CGP process itself is concerned,both the MIP-CGP process and the MIP process have the similar reactor configuration but with different reactor size and operating parameters. The proprietary catalyst CGP-1 is also proposed to tailor for the MIP-CGP process. The specific features of the CGP-1 catalyst cover the new matrix,which possesses excellent capability to accommodate coke formation in the first reaction zone;the modified Y zeolite,which exhibits high hydrogen transfer activity in the second reaction zone;and the MFI zeolite,which has good gasoline olefin cracking activity. The commercial test results of MIP-CGP process applied along with the CGP-1 catalyst showed that the olefin content of gasoline was less than 18 v% and the propylene yield was more than 8 m%. Furthermore,as compared with the conventional FCC process,the gasoline properties were improved greatly and a higher total liquid yield was obtained. The advantages and characteristics of the MIP-CGP process were fully exploited by using the CGP-1 catalyst.
文摘The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was studied in a small- scale fixed fluid catalytic cracking unit. Test results have revealed that compared to the USY zeolite and Beta zeolite, the catalytic pyrolysis of n-heptane in the presence of the ZRP zeolite catalyst can result in higher yield and selectivity of ethyl- ene and propylene, while a higher reaction temperature and a higher catalyst/oil ratio can promote the formation of ethylene and propylene during catalytic pyrolysis of n-heptane. The ethylene formation reaction is more sensitive to the changes in reaction temperature, whereas the changes in catalyst/oil ratio are more influential to the propylene formation reaction. This paper has made a preliminary exploration into the different reaction pathways for formation of ethylene and propylene on zeolites with different structures.
