Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.T...Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.展开更多
Abstract： In order to study the flammability and explosion property of gases during the propane oxidation to acrylic acid process, the explosion limits and the safety oxygen content of gases at the recycle gas compre...Abstract： In order to study the flammability and explosion property of gases during the propane oxidation to acrylic acid process, the explosion limits and the safety oxygen content of gases at the recycle gas compressor outlet, the reactor inlet, and the reactor outlet were theoretically calculated and experimentally tested. Finally, the inert limit was also determined. It showed that gases at the recycle gas compressor outlet and the reactor outlet were nonflammable based on three indicators： the explosion limits, the safety oxygen content and the inert limit. The C3H6 and O2 contents were higher at the reactor inlet, which made the mixed gases easily ignitable. However, the large amount of inert gases suppressed the possibility of explo- sion effectively. As a consequence, no explosion phenomenon would happen in all three locations. But gases at the reactor inlet are most dangerous, where more supervision on the concentration of gases and more strict control on the temperature and pressure should be implemented. Besides this, open flame, hot surfaces and other sources of ignition are prohibited in working spaces. The experimental results can be applied to similar process for oxidation of propane.展开更多
The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic aci...The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio （Mo1V0.31Te0.23Nb0.12）. The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H8 ：O2 ： H2O ： N2 = 4.4： 12.8 ： 15.3 ： 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.展开更多
The effects of chemical composition and preparation conditions,especially calcination atmosphere and water content on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of p...The effects of chemical composition and preparation conditions,especially calcination atmosphere and water content on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid were investigated.Among the catalysts studied,Mo_(1.0)V_(0.3)Te_(0.23)Nb_(0.12)O_(x) catalyst calcined in inert atmosphere at 600℃shows the best performance in terms of propane conversion and selectivity to acrylic acid.The results reveal that proper chemical composition, calcination atmosphere and water content affect greatly the catalysts in many ways including structure,chemical composition,which are related to their catalytic performances;and 51.0%propane conversion and 30.5%one-pass yield to acrylic acid can be achieved at the same time.展开更多
Selective oxidation of propane by lattice oxygen of vanadium-phosphorus oxide(VPO) catalysts was investigated with a pulse reactor in which the oxidation of propane and there-oxidation of catalyst were implemented alt...Selective oxidation of propane by lattice oxygen of vanadium-phosphorus oxide(VPO) catalysts was investigated with a pulse reactor in which the oxidation of propane and there-oxidation of catalyst were implemented alternately in the presence of water vapor. The principalproducts are acrylic acid (AA), acetic acid (HAc), and carbon oxides. In addition, small amounts ofC_1 and C_2 hydrocarbons were also found, molar ratio of AA to HAc is 1.4-2.2. The active oxygenspecies are those adsorbed on catalyst surface firmly and/or bound to catalyst lattice, i.e. latticeoxygen; the selective oxidation of propane on VPO catalysts can be carried out in a circulatingfluidized bed (CFB) riser reactor. For propane oxidation over VPO catalysts, the effects of reactiontemperature in a pulse reactor were found almost the same as in a steady-state flow reactor. Thatis, as the reaction temperature increases, propane conversion and the amount of C_1+C_2 hydrocarbonsin the product increase steadily, while selectivity to acrylic acid and to acetic acid increaseprior to 350℃ then begin to drop at temperatures higher than 350℃, and yields of acrylic acid andof acetic acid attained maximum at about 400℃. The maximum yields of acrylic acid and of aceticacid for a single-pass are 7.50% and 4.59% respectively, with 38.2% propane conversion. When theamount of propane pulsed decreases or the amount of catalyst loaded increases, the conversionincreases but the selectivity decreases. Increasing the flow rate of carrier gases causes theconversion pass through a minimum but selectivity and yields pass through a maximum. In a fixed bedreactor, it is hard to obtain high selectivity at a high reaction conversion due to the furtherdegradation of acrylic acid and acetic acid even though propane was oxidized by the lattice oxygen.The catalytic performance can be improved in the presence of excess propane. Propylene can beoxidized by lattice oxygen of VPO catalyst at 250℃, nevertheless, selectivity to AA and to HAc areeven lower, much more acetic acid was produced (molar ratio of AA to HAc is 0.19:1-0.83:1) thoughthe oxidation products are the same as from propane.展开更多
The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic re...The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity （GHSV） and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts.展开更多
Vanadium phosphorus oxide (VPO) catalyst samples with different P/V molar ratios were prepared in mixture of isobutanol and benzyl alcohol, and their catalytic performance for selective oxidation of propane to acrylic...Vanadium phosphorus oxide (VPO) catalyst samples with different P/V molar ratios were prepared in mixture of isobutanol and benzyl alcohol, and their catalytic performance for selective oxidation of propane to acrylic acid (AA) and acetic acid (HAc) by lattice oxygen was investigated in a pulse reactor. The results showed that the AA and HAc only formed over the catalyst samples with n (P)/ n (V)>1 0. The proper n (P)/ n (V) is about 1 1, with which the catalyst samples have the best catalytic performance and maximum reversible oxygen storage capacity. It was also found that the ratio of n (AA)/ n (HAc) increased with the increasing of both the reaction temperature and the n (P)/ n (V) in the catalyst. The XRD results indicated that the title reaction is sensitive to the crystal structure and the active phase is (VO) 2P 2O 7.展开更多
Both the partially reduced and non-reduced multi-component heteropoly compound catalysts with Keggin structure were prepared and used for the selective oxidation of propane. The catalysts were characterized by IR, H...Both the partially reduced and non-reduced multi-component heteropoly compound catalysts with Keggin structure were prepared and used for the selective oxidation of propane. The catalysts were characterized by IR, H2-TPR, NH3-TPD, SEM and XRD. The addition of Cs increased the selectivity of acrylic acid and acetic acid. The selective oxidation performance was greatly improved with the addition of As. Among all of the tested catalysts, the catalytic performance of the Cs1.8Fe0.16HxPVAs0.4Mo11O40 (non-reduced) was the best and the maximum yield of acrylic acid reached 16.42%.展开更多
文摘Alkaline earth metal （Mg,Ca,Sr and Ba）-doped Mo-V-Sb-O x catalysts,prepared by a dry-up method,have been investigated for their catalytic performance in the oxidation of propane under different reaction conditions.The catalysts have been characterized by N2 adsorption-desorption,temperature-programmed desorption （TPD） of NH3,SEM and XRD.Influence of water vapor on the catalytic performance,particularly on the selectivities to acetic acid and acrylic acid,has also been studied.The selectivity to acrylic acid was improved significantly by the doping of alkaline earth metals to Mo-V-Sb-O x catalysts.The surface acidic sites of the catalyst decreased with the doping of the catalyst with alkaline earth metals,which ultimately was found to be beneficial for obtaining high selectivity to acrylic acid.The catalytic activity and product selectivities were found to be influenced by the reaction temperature,C3H8/O2 ratio and space velocity.A significant improvement in the selectivity to acrylic acid has also been observed by the addition of water vapor in the feed of propane and oxygen in the oxidation of propane.
基金financially supported by the National Science and Technology Support Program of China(2012BAK13B01)
文摘Abstract： In order to study the flammability and explosion property of gases during the propane oxidation to acrylic acid process, the explosion limits and the safety oxygen content of gases at the recycle gas compressor outlet, the reactor inlet, and the reactor outlet were theoretically calculated and experimentally tested. Finally, the inert limit was also determined. It showed that gases at the recycle gas compressor outlet and the reactor outlet were nonflammable based on three indicators： the explosion limits, the safety oxygen content and the inert limit. The C3H6 and O2 contents were higher at the reactor inlet, which made the mixed gases easily ignitable. However, the large amount of inert gases suppressed the possibility of explo- sion effectively. As a consequence, no explosion phenomenon would happen in all three locations. But gases at the reactor inlet are most dangerous, where more supervision on the concentration of gases and more strict control on the temperature and pressure should be implemented. Besides this, open flame, hot surfaces and other sources of ignition are prohibited in working spaces. The experimental results can be applied to similar process for oxidation of propane.
文摘The effects of metal atomic ratio, water content, oxygen content, and calcination temperature on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid have been investigated and discussed. Among the catalysts studied, it was found that the MoVTeNbO catalyst calcined at a temperature of 600 ℃ showed the best performance in terms of propane conversion and selectivity for acrylic acid under an atmosphere of nitrogen. An effective MoVTeNbO oxide catalyst for propane selective oxidation to acrylic acid was obtained with a combination of a preferred metal atomic ratio （Mo1V0.31Te0.23Nb0.12）. The optimum reaction condition for the selective oxidation of propane was the molar ratio of C3H8 ：O2 ： H2O ： N2 = 4.4： 12.8 ： 15.3 ： 36.9. Under such conditions, the conversion of propane and the maximum yield of acrylic acid reached about 50% and 21%, respectively.
文摘The effects of chemical composition and preparation conditions,especially calcination atmosphere and water content on the catalytic performances of MoVTeNbO mixed oxide catalyst system for the selective oxidation of propane to acrylic acid were investigated.Among the catalysts studied,Mo_(1.0)V_(0.3)Te_(0.23)Nb_(0.12)O_(x) catalyst calcined in inert atmosphere at 600℃shows the best performance in terms of propane conversion and selectivity to acrylic acid.The results reveal that proper chemical composition, calcination atmosphere and water content affect greatly the catalysts in many ways including structure,chemical composition,which are related to their catalytic performances;and 51.0%propane conversion and 30.5%one-pass yield to acrylic acid can be achieved at the same time.
基金The work is supported by The Department of Education of Heilongjiang Province.
文摘Selective oxidation of propane by lattice oxygen of vanadium-phosphorus oxide(VPO) catalysts was investigated with a pulse reactor in which the oxidation of propane and there-oxidation of catalyst were implemented alternately in the presence of water vapor. The principalproducts are acrylic acid (AA), acetic acid (HAc), and carbon oxides. In addition, small amounts ofC_1 and C_2 hydrocarbons were also found, molar ratio of AA to HAc is 1.4-2.2. The active oxygenspecies are those adsorbed on catalyst surface firmly and/or bound to catalyst lattice, i.e. latticeoxygen; the selective oxidation of propane on VPO catalysts can be carried out in a circulatingfluidized bed (CFB) riser reactor. For propane oxidation over VPO catalysts, the effects of reactiontemperature in a pulse reactor were found almost the same as in a steady-state flow reactor. Thatis, as the reaction temperature increases, propane conversion and the amount of C_1+C_2 hydrocarbonsin the product increase steadily, while selectivity to acrylic acid and to acetic acid increaseprior to 350℃ then begin to drop at temperatures higher than 350℃, and yields of acrylic acid andof acetic acid attained maximum at about 400℃. The maximum yields of acrylic acid and of aceticacid for a single-pass are 7.50% and 4.59% respectively, with 38.2% propane conversion. When theamount of propane pulsed decreases or the amount of catalyst loaded increases, the conversionincreases but the selectivity decreases. Increasing the flow rate of carrier gases causes theconversion pass through a minimum but selectivity and yields pass through a maximum. In a fixed bedreactor, it is hard to obtain high selectivity at a high reaction conversion due to the furtherdegradation of acrylic acid and acetic acid even though propane was oxidized by the lattice oxygen.The catalytic performance can be improved in the presence of excess propane. Propylene can beoxidized by lattice oxygen of VPO catalyst at 250℃, nevertheless, selectivity to AA and to HAc areeven lower, much more acetic acid was produced (molar ratio of AA to HAc is 0.19:1-0.83:1) thoughthe oxidation products are the same as from propane.
基金Ministry of Science Technology and Innovation (MOSTI),Malaysia,project number:IRPA RM8 SR33-02-03-3010.
文摘The selective oxidation of propane to acrylic acid over an MoVTeNb mixed oxide catalyst, dried and calcined before reaction has been studied using high-throughput instrumentation, which is called nanoflow catalytic reactor. The effects of catalyst dilution on the catalytic performance of the MoVTeNb mixed oxide catalyst in selective oxidation of propane to acrylic acid were also investigated. The effects of some reaction parameters, such as gas hourly space velocity （GHSV） and reaction temperature, for selective oxidation of propane to acrylic acid over diluted MoVTeNb catalyst have also been studied. The configuration of the nanoflow is shown to be suitable for screen catalytic performance, and its operating conditions were mimicked closely to conventional laboratory as well as to industrial conditions. The results obtained provided very good reproducibility and it showed that preparation methods as well as reaction parameters can play significant roles in catalytic performance of these catalysts.
文摘Vanadium phosphorus oxide (VPO) catalyst samples with different P/V molar ratios were prepared in mixture of isobutanol and benzyl alcohol, and their catalytic performance for selective oxidation of propane to acrylic acid (AA) and acetic acid (HAc) by lattice oxygen was investigated in a pulse reactor. The results showed that the AA and HAc only formed over the catalyst samples with n (P)/ n (V)>1 0. The proper n (P)/ n (V) is about 1 1, with which the catalyst samples have the best catalytic performance and maximum reversible oxygen storage capacity. It was also found that the ratio of n (AA)/ n (HAc) increased with the increasing of both the reaction temperature and the n (P)/ n (V) in the catalyst. The XRD results indicated that the title reaction is sensitive to the crystal structure and the active phase is (VO) 2P 2O 7.
基金Project supported by the Scientific Research Foundation of Hunan Provincial Education Department and Hunan Provincial Natural Science Founda-tion of China.
文摘Both the partially reduced and non-reduced multi-component heteropoly compound catalysts with Keggin structure were prepared and used for the selective oxidation of propane. The catalysts were characterized by IR, H2-TPR, NH3-TPD, SEM and XRD. The addition of Cs increased the selectivity of acrylic acid and acetic acid. The selective oxidation performance was greatly improved with the addition of As. Among all of the tested catalysts, the catalytic performance of the Cs1.8Fe0.16HxPVAs0.4Mo11O40 (non-reduced) was the best and the maximum yield of acrylic acid reached 16.42%.
