A La-modified Al2O3 catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts c...A La-modified Al2O3 catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts calcined at different temperatures were characterized using NH3-TPD, pyridine-FTIR, X-ray diffraction, and Raman techniques. It was found that the calcination process could not only change the structure of these catalysts but also modify the amount of surface acidity on the catalysts. The catalyst calcined at 400 ℃ exhibited the highest conversion of acetylene （94.6%） and highest selectivity to vinyl fluoride （83.4%） and lower coke deposition selectivity （0.72%）. The highest activity was related to the largest amount of surface acidity on the catalyst, and the coke deposition was also related to the total amount of surface acidic sites.展开更多
Ag3PO4/Ag/Ag2Mo2O7 composite photocatalyst was successfully prepared via an in situ precipitation method. The as-prepared Ag3PO4/Ag/Ag2Mo2O7 nanocomposite included Ag3PO4 nanoparticles （NPs） as well as Ag NPs assemb...Ag3PO4/Ag/Ag2Mo2O7 composite photocatalyst was successfully prepared via an in situ precipitation method. The as-prepared Ag3PO4/Ag/Ag2Mo2O7 nanocomposite included Ag3PO4 nanoparticles （NPs） as well as Ag NPs assembling on the surface of Ag2Mo2O7 nanowires. Under visible light irradiation （λ〉420 nm）, the Ag3PO4/Ag/Ag2Mo2O7 com- posite degraded rhodamine B （Rh B） efficiently and showed much higher photocatalytic efficiency than pure AgaPO4, Ag2Mo2O7, or Ag3PO4/Ag2Mo2O7. It was elucidated that the excellent photocatalytic performance of Ag3PO4/Ag/Ag2Mo2O7 for the degradation of Rh B under visible light could be ascribed to the high specific surface area, the extended absorption in the visible light region resulting from the Ag3PO4/Ag loading, and the effi- cient separation of photogenerated electrons and holes through the ternary heterostrucure composed of Ag3PO4, Ag and Ag2Mo2O7.展开更多
The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonizatio...The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.展开更多
A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-co...A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.展开更多
The V/O5-WO3-MoOy＇TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction （XRD）, scanning electron micrograph （SEM...The V/O5-WO3-MoOy＇TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction （XRD）, scanning electron micrograph （SEM） and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass per- centage of V ： W ： Mo ： TiO2 ： fiber glass = 1 ： 4.5 ： 4.5 ： 72 ： 18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to ruffle by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3. The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615 1640 mg.m-3. Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.展开更多
Aluminum recovery is a key issue for the overall recycling of valuable metals from spent catalysts. This paper focuses on the recovery and regeneration of alumina with high additional value from the spent hydrodesulfu...Aluminum recovery is a key issue for the overall recycling of valuable metals from spent catalysts. This paper focuses on the recovery and regeneration of alumina with high additional value from the spent hydrodesulfurization catalyst CoMo/Al_2O_3. The results indicate that 98.13% alumina is successfully leached from the treated spent catalysts by an alkaline leaching process under the conditions of 5 mol·L^(-1) sodium hydroxide,a liquid/solid ratio of 20 ml·g^(-1),a temperature of 160 0 C and a reaction time of 4 h. In the leaching residue, no difficult leaching compound is found and cobalt and nickel are enriched,both of which are conducive to the subsequent metal recovery step. The reaction order of aluminum leaching is 0.99. This reaction fits well with the interfacial chemical reaction model, and its apparent activation energy is calculated as 45.50 kJ mol^(-1). Subsequently, y-Al_2O_3 with a high specific surface area of 278.3 m^2·g^(-1), a mean size of 2.2 μm and an average pore size of 3.10 nm is then regenerated from the lixivium, indicating its suitability for use as a catalyst carrier. The recovery and regeneration of alumina from spent catalysts can not only significantly contribute to the total recycling of such hazardous spent catalysts but also provide a new approach for the preparation of y-Al_2O_3 with a high specific surface area using spent catalysts as the aluminum sources.展开更多
The selective catalytic hydrogenation of naphthalene to high-value tetralin was systematically investigated.A series of Al2O3 catalysts containing different active metals(Co,Mo,Ni,W)were prepared by incipient wetness ...The selective catalytic hydrogenation of naphthalene to high-value tetralin was systematically investigated.A series of Al2O3 catalysts containing different active metals(Co,Mo,Ni,W)were prepared by incipient wetness impregnation.The effects of different active metals forms(oxidation,reduction,sulfuration)and reaction conditions on naphthalene hydrogenation were investigated and the catalysts were characterized by XRD,XPS,BET,NH3-TPD and SEM.Especially,Ni-Mo/Al2O3 was first used in this reactive system.The results show that the oxidative4%Ni O-20%MoO3/Al2O3 is the best catalyst for the preparation of tetralin.The conversion of naphthalene and the selectivity of tetralin can reach 95.62%and 99.75%respectively at 200℃,8 h and 6 MPa.Compared with reduced and sulfureted 4%Ni O-20%MoO3/Al2O3 catalysts,oxidative 4%Ni O-20%MoO3/Al2O3 has a well dispersed and uniform monolayer of the active metals,larger pore volume and size,and larger total acidity.NiO-MoO3/Al2O3 has a synergistic effect between NiO activity and MoO3 selectivity.展开更多
Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption,...Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS）. The Pd-only three-way catalysts （Pd-TWC） supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3＋ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.展开更多
1-Decene was oligomerized over the supported AlCl3/γ-Al2O3 catalyst in a fixed-bed reactor. The effects of temperature and LHSV on oligomerization of 1-decene were investigated and the synthetic PAO was characterized...1-Decene was oligomerized over the supported AlCl3/γ-Al2O3 catalyst in a fixed-bed reactor. The effects of temperature and LHSV on oligomerization of 1-decene were investigated and the synthetic PAO was characterized with GC technique. Furthermore, the life of immobilized catalyst was tested and the mechanism of catalyst deactivation was discussed. The results showed that with an increasing temperature, the PAO yield increased and the kinematic viscosity of oil decreased. The GC results indicated that the synthesized PAO was a mixture consisting of dimers, trimers, tetramers and pentamers. The results of chloride content measurements and BET tests showed that catalyst deactivation could be mainly attributed to the loss of active components.展开更多
Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in d...Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.展开更多
Processes based on non-thermal plasma（NTP） for indoor air treatment inevitably lead to the formation of toxic by-products such as ozone（O3） and nitrogen oxides（NOx）. Adding a step of heterogeneous catalysis in s...Processes based on non-thermal plasma（NTP） for indoor air treatment inevitably lead to the formation of toxic by-products such as ozone（O3） and nitrogen oxides（NOx）. Adding a step of heterogeneous catalysis in series with NTP could allow for the decomposition of the by-products. Therefore, different catalysts were developed based on transition metal oxides, such as NiOx, CoOxand MnOxwith different weight percentage 1, 5 and 10 wt.%,deposited on a γ-Al2O3 support. The O3 removal efficiency（ORE） and the NOxremoval efficiency（NRE） were very encouraging in dry air： about 65% and 80%, respectively, by using2 g 5 wt.% MnOx/Al2O3 catalyst under the experimental conditions. However, strongly negative effects of relative humidity（RH） on the catalytic decomposition performance were observed. To overcome this limitation, the catalyst surface was modified to make it hydrophobic using a cost-effective chemical grafting method. This treatment consisted in impregnating the 5 wt.% MnOx/Al2O3 catalyst with different trichloro（alkyl）silanes（TCAS）.The effects of different linker lengths and amounts of TCAS for the hydrophobicity and the decomposition performance of surface-modified catalysts under humid conditions were investigated. Our results show that the surface-modified catalyst with the shortest linker and 0.25 mmol/gcatof modifying agent represents the best catalytic decomposition performance for O3. Its ORE is 41% at 60% RH, which is twice that of the non-modified catalyst.展开更多
A series of 3.0Mo/MCM-22-Al2O3 catalysts with γ-Al2O3 contents in the range of 0-100 wt% were prepared and applied in the metathesis reaction of ethene and butene-2. Addition of γ-Al2O3did not affect the structure o...A series of 3.0Mo/MCM-22-Al2O3 catalysts with γ-Al2O3 contents in the range of 0-100 wt% were prepared and applied in the metathesis reaction of ethene and butene-2. Addition of γ-Al2O3did not affect the structure of MCM-22 zeolite as evidenced by XRD and N2 adsorption measurements. It was deduced from TPR experiments that γ-Al2O3 phase favored the formation of polymolybdate or multilayered Mo oxide, while more Al2（MoO4）3 species were generated over MCM-22 zeolites. Alumina content in the support was directly related to the metathesis activity of ethene and butene-2 to propene. Mo species with higher valence （Mo6＋or Mo5＋） contributed more to the excellent performance of catalyst than metallic Mo. The best catalyst activity and stability was obtained over 3.0Mo/（MCM-22-30%Al2O3） under the reaction condition of 1.0 MPa and 125℃ using N2 as the pretreatment gas.展开更多
Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst...Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst(T-202) were studied in a continuous flow fixed bed reactor under pressures of 1.6-2.8 MPa, space time of 1.32-3.55 s and temperatures of 240-360 °C. Though the COG contains about 0.6 mol/mol H2, hydrogenation of CO and CO2 is not significant on this catalyst. The conversions of unsaturated hydrocarbons depend on their molecular structures. Diolefins and alkynes can be completely hydrogenated even at relatively low temperature and pressure. Olefins, in contrast, can only be progressively hydrogenated with increasing temperature and pressure. The hydrodesulfurization(HDS) of CS2 on this catalyst is easy. Complete conversion of CS2 was observed in the whole range of the conditions used in this work. The original COS in the COG can also be easily converted to a low level. However, its complete HDS is difficult due to the relatively high concentration of CO in the COG and due to the limitation of thermodynamics. H2 S can react with unsaturated hydrocarbons to form ethyl mercaptan and thiophene, which are then progressively hydrodesulfurized with increasing temperature and pressure. Based on the experimental observations, reaction kinetic models for the conversion of ethylene and sulfur-containing compounds were proposed; the values of the parameters in the models were obtained by regression of the experimental data.展开更多
Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal lo...Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal loading amount of Fe2O3 on Ce0.67Zr0.33 O2-Al2O3 in our experimental condition for catalytic combustion of methane was 8% （ mass fraction）. The prepared catalysts were characterized by BET, TPR, XRD analyses, and their catalytic activity was investigated after being calcined at 873 K and after being aged in water gas at 1273 K. When the loading amount of Fe203 was 8% （ mass fraction）, the catalyst held the highest activity, and the best temperature speciality and thermal stability. The complete-conversion temperature of methane for fresh and aged sample was 788 and 838 K, respectively. The range between the light-off temperature and the complete-conversion temperature was only 15 K. The characterization results of XRD indicated that Fe2O3 was well dispersed on the Ce0.67Zr0.33O2-Al2O3 matrix. The results of BET and TPR were in good harmony with the catalytic activity results.展开更多
Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the s...Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the surface acid-base properties of catalysts by introduction of alkali metal （Na, K） oxides inhibits the carbonization and as a result, improves the operational stability of these catalysts. An effect of promotion of nickel-alumina based composite doped by lanthanum oxide is found. This effect, caused by an additional route for the CO2 activation on Ni-La2O3/Al2O3/cordierite catalyst, is displayed in increase of methane conversion under conditions of an oxidant excess.展开更多
The surface nature of fresh Mo2N/Al2O3, Mo2C/Al2O3 and/MoP/Al2O3 catalysts, which were synthesized directly in the IR cell to avoid passivation, were characterized by in situ IR spectroscopy with CO as a probe molecul...The surface nature of fresh Mo2N/Al2O3, Mo2C/Al2O3 and/MoP/Al2O3 catalysts, which were synthesized directly in the IR cell to avoid passivation, were characterized by in situ IR spectroscopy with CO as a probe molecule. CO adsorbed on fresh catalysts showed characteristic IR bands at 2045 cm-1 for Mo2N/Al2O3 catalyst, 2054 cm-1 for MozC/Al2O3 catalyst and 2037 cm-1 for MoP/Al2O3 catalyst, respectively. A strong band at 2200 cm-1 for Mo2N/Al2O3 catalyst, which could be ascribed to NCO species formed when CO reacted upon surface active nitrogen atoms, and a weak band at 2196 cm-1 for Mo2C/Al2O3 catalyst, which could be attributed to CCO species, were also detected. CO adsorbed on fresh Mo2N/Al2O3 catalyst, Mo2C/Al2O3 catalyst and MoP/Al2O3 catalyst, showed strong molecular adsorption, just like noble metals. Our experimental results are bolstered by direct IR evidence demonstrating the similarity in surface electronic property between the fresh Mo2N/Al2O3, Mo2C/Al2O3 and MoP/Al2O3 catalysts and noble metals.展开更多
基金ACKNOWLEDGMENT This work was supported by the National Natural Science Foundation of China （No.20873125）,
文摘A La-modified Al2O3 catalyst was prepared with deposition-precipitation method. The effect of calcination temperature on the reactivity for vapor phase hydrofluorination of acetylene to vinyl fluoride. The catalysts calcined at different temperatures were characterized using NH3-TPD, pyridine-FTIR, X-ray diffraction, and Raman techniques. It was found that the calcination process could not only change the structure of these catalysts but also modify the amount of surface acidity on the catalysts. The catalyst calcined at 400 ℃ exhibited the highest conversion of acetylene （94.6%） and highest selectivity to vinyl fluoride （83.4%） and lower coke deposition selectivity （0.72%）. The highest activity was related to the largest amount of surface acidity on the catalyst, and the coke deposition was also related to the total amount of surface acidic sites.
基金supported by the National Natural Science Foundation of China(No.21407059,No.21576112,No.21407064,and No.21607051)the Science Development Project of Jiangsu Province(BK20140527)+1 种基金the Science and Technology Research Project of the Department of Education of Jilin Province(No.2015220)the Open Subject of the State Key Laboratory of Rare Earth Resource Utilization(RERU2017011)
文摘Ag3PO4/Ag/Ag2Mo2O7 composite photocatalyst was successfully prepared via an in situ precipitation method. The as-prepared Ag3PO4/Ag/Ag2Mo2O7 nanocomposite included Ag3PO4 nanoparticles （NPs） as well as Ag NPs assembling on the surface of Ag2Mo2O7 nanowires. Under visible light irradiation （λ〉420 nm）, the Ag3PO4/Ag/Ag2Mo2O7 com- posite degraded rhodamine B （Rh B） efficiently and showed much higher photocatalytic efficiency than pure AgaPO4, Ag2Mo2O7, or Ag3PO4/Ag2Mo2O7. It was elucidated that the excellent photocatalytic performance of Ag3PO4/Ag/Ag2Mo2O7 for the degradation of Rh B under visible light could be ascribed to the high specific surface area, the extended absorption in the visible light region resulting from the Ag3PO4/Ag loading, and the effi- cient separation of photogenerated electrons and holes through the ternary heterostrucure composed of Ag3PO4, Ag and Ag2Mo2O7.
基金supported by the National Natural Science Foundation of China(Nos.22276060 and 21976059)Guangdong Basic and Applied Basic Research Foundation(No.2024A1515012636)China Scholarship Council Scholarship(No.201906155006)。
文摘The reduction of carbon emissions in the steel industry is a significant challenge,and utilizing CO_(2) from carbon intensive steel industry off-gases for methanol production is a promising strategy for decarbonization.However,steelwork off-gases typically contain various impurities,including H_(2)S,which can deactivate commercial methanol synthesis catalysts,Cu/ZnO/Al_(2)O_(3)(CZA).Reverse water-gas shift(RWGS)reaction is the predominant side reaction in CO_(2) hydrogenation to methanol which can occur at ambient pressure,enabling the decouple of RWGS from methanol production at high pressure.Then,a series of activated CZA catalysts has been in-situ pretreated in 400 ppm H_(2)S/Ar at 250℃and tested for both RWGS reaction at ambient pressure and CO_(2) hydrogenation to methanol at high pressure.An innovative decoupling strategy was employed to isolate the RWGS reaction from the methanol synthesis process,enabling the investigation of the evolution of active site structures and the poisoning mechanism through elemental analysis,X-ray Diffraction,X-ray Photoelectron Spectroscopy,Fourier Transform Infrared Spectroscopy,Temperature Programmed Reduction and CO_(2) Temperature Programmed Desorption.The results indicate that there are different dynamic migration behaviors of ZnO_(x) in the two reaction systems,leading to different poisoning mechanisms.These interesting findings are beneficial to develop sulfur resistant and durable highly efficient catalysts for CO_(2) hydrogenation to methanol,promoting the carbon emission reduction in steel industry.
基金financially supported by the National Natural Science Foundation of China(21173195)~~
文摘A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.
基金Supported by the Science and Technology Development Planning of Shandong Province(2011GSF11716)China Scholarship Council for Researching in University of Birmingham
文摘The V/O5-WO3-MoOy＇TiO2 honeycomb catalyst was prepared with industrial grade chemicals. The structural and physico-chemical properties were analyzed with X-ray diffraction （XRD）, scanning electron micrograph （SEM） and mercury porosimetry. The NOx conversion and durability were investigated on a pilot plant test set under the actual operational conditions of a coal fired boiler. The catalyst monolith had good formability with mass per- centage of V ： W ： Mo ： TiO2 ： fiber glass = 1 ： 4.5 ： 4.5 ： 72 ： 18. Vanadium, tungsten and molybdenum species were highly dispersed on anatase TiO2 without causing the transformation of anatase TiO2 to ruffle by calcining under a current of air at 450℃ for 4.5 h, but there were some degrees of crystal distortion. The catalyst particle sizes were almost uniform with close pile-up and the pore structure was regular with complete macro-pore formation and large specific surface area. The NOx conversion was sensitive to temperature but nearly insensitive to NH3. The catalyst showed strong adaptability to NOx concentration with activity above 80% in the range of 615 1640 mg.m-3. Within the range of 720-8640 h continuous operation, the NOx conversion dropped at a rate of about 1% reduction per 600 h.
基金financially supported by the National Natural Science Commission-Yunnan Joint Fund Project (No.U1402274)
文摘Aluminum recovery is a key issue for the overall recycling of valuable metals from spent catalysts. This paper focuses on the recovery and regeneration of alumina with high additional value from the spent hydrodesulfurization catalyst CoMo/Al_2O_3. The results indicate that 98.13% alumina is successfully leached from the treated spent catalysts by an alkaline leaching process under the conditions of 5 mol·L^(-1) sodium hydroxide,a liquid/solid ratio of 20 ml·g^(-1),a temperature of 160 0 C and a reaction time of 4 h. In the leaching residue, no difficult leaching compound is found and cobalt and nickel are enriched,both of which are conducive to the subsequent metal recovery step. The reaction order of aluminum leaching is 0.99. This reaction fits well with the interfacial chemical reaction model, and its apparent activation energy is calculated as 45.50 kJ mol^(-1). Subsequently, y-Al_2O_3 with a high specific surface area of 278.3 m^2·g^(-1), a mean size of 2.2 μm and an average pore size of 3.10 nm is then regenerated from the lixivium, indicating its suitability for use as a catalyst carrier. The recovery and regeneration of alumina from spent catalysts can not only significantly contribute to the total recycling of such hazardous spent catalysts but also provide a new approach for the preparation of y-Al_2O_3 with a high specific surface area using spent catalysts as the aluminum sources.
基金supported by the Joint Funds of National Key R&D Program of China(2018YFB0604603)the National Natural Science Foundation of China(21536009,21776229)+2 种基金Science and Technology Plan Projects of Shaanxi Province(2017ZDCXL-GY-10-03,2018ZDXMGY-167)The Young Science and Technology Star Project of Shaanxi Province(2017KJXX-62)Science and Technology Program of Yulin(2018-2-22)。
文摘The selective catalytic hydrogenation of naphthalene to high-value tetralin was systematically investigated.A series of Al2O3 catalysts containing different active metals(Co,Mo,Ni,W)were prepared by incipient wetness impregnation.The effects of different active metals forms(oxidation,reduction,sulfuration)and reaction conditions on naphthalene hydrogenation were investigated and the catalysts were characterized by XRD,XPS,BET,NH3-TPD and SEM.Especially,Ni-Mo/Al2O3 was first used in this reactive system.The results show that the oxidative4%Ni O-20%MoO3/Al2O3 is the best catalyst for the preparation of tetralin.The conversion of naphthalene and the selectivity of tetralin can reach 95.62%and 99.75%respectively at 200℃,8 h and 6 MPa.Compared with reduced and sulfureted 4%Ni O-20%MoO3/Al2O3 catalysts,oxidative 4%Ni O-20%MoO3/Al2O3 has a well dispersed and uniform monolayer of the active metals,larger pore volume and size,and larger total acidity.NiO-MoO3/Al2O3 has a synergistic effect between NiO activity and MoO3 selectivity.
基金Project supported by National Natural Science Foundation of China (20773090, 20803049)the Specialized Research Fund for the Doctoral Program of Higher Education (20070610026, 200806100009)
文摘Ce-Zr-Al-Nd2O3 （CZAN） support materials were prepared by co-precipitation and impregnation methods, respectively. They were characterized by X-ray diffTaction （XRD）, low temperature nitrogen adsorption-desorption, oxygen pulsing technique, H2-temperamre programmed reduction （H2-TPR） and X-ray photoelectron spectroscopy （XPS）. The Pd-only three-way catalysts （Pd-TWC） supported on these materials were prepared by incipient wetness method and studied by activity tests. The results demonstrated that the CZAN supports obtained by the two methods showed better structural, textural and redox properties than the CZA without Nd2O3, and the addition of Nd203 improved the catalytic activity of TWC. Especially, the CZAN-i support prepared by impregnation method had better thermal stability and redox property. Meanwhile, the Pd/CZAN-i catalyst exhibited the best catalytic performance. XPS measurements indicated that the Nd-modified samples possessed more Ce3＋ and oxygen vacancies on the surface of samples, which led to a better redox property. The excellent redox property of support materials helped to improve the catalytic activity of TWC.
基金the SINOPEC Corporation for the financial support
文摘1-Decene was oligomerized over the supported AlCl3/γ-Al2O3 catalyst in a fixed-bed reactor. The effects of temperature and LHSV on oligomerization of 1-decene were investigated and the synthetic PAO was characterized with GC technique. Furthermore, the life of immobilized catalyst was tested and the mechanism of catalyst deactivation was discussed. The results showed that with an increasing temperature, the PAO yield increased and the kinematic viscosity of oil decreased. The GC results indicated that the synthesized PAO was a mixture consisting of dimers, trimers, tetramers and pentamers. The results of chloride content measurements and BET tests showed that catalyst deactivation could be mainly attributed to the loss of active components.
基金supported by the National Basic Research Program of China (No. 2011CB201404)the financial support of the State Key Laboratory for Oxo Synthesis and Selective Oxidation (OSSO) of China
文摘Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.
基金financially supported by French Ministry of Higher Education and Research (No. 2015/386)
文摘Processes based on non-thermal plasma（NTP） for indoor air treatment inevitably lead to the formation of toxic by-products such as ozone（O3） and nitrogen oxides（NOx）. Adding a step of heterogeneous catalysis in series with NTP could allow for the decomposition of the by-products. Therefore, different catalysts were developed based on transition metal oxides, such as NiOx, CoOxand MnOxwith different weight percentage 1, 5 and 10 wt.%,deposited on a γ-Al2O3 support. The O3 removal efficiency（ORE） and the NOxremoval efficiency（NRE） were very encouraging in dry air： about 65% and 80%, respectively, by using2 g 5 wt.% MnOx/Al2O3 catalyst under the experimental conditions. However, strongly negative effects of relative humidity（RH） on the catalytic decomposition performance were observed. To overcome this limitation, the catalyst surface was modified to make it hydrophobic using a cost-effective chemical grafting method. This treatment consisted in impregnating the 5 wt.% MnOx/Al2O3 catalyst with different trichloro（alkyl）silanes（TCAS）.The effects of different linker lengths and amounts of TCAS for the hydrophobicity and the decomposition performance of surface-modified catalysts under humid conditions were investigated. Our results show that the surface-modified catalyst with the shortest linker and 0.25 mmol/gcatof modifying agent represents the best catalytic decomposition performance for O3. Its ORE is 41% at 60% RH, which is twice that of the non-modified catalyst.
基金supported by the National Natural Science Foundation of China (Grant No. 20903088 and 20773120)the Ministry of Science and Technology of China through the National Key Project of Fundamental Research (Grant No.2009CB623507)
文摘A series of 3.0Mo/MCM-22-Al2O3 catalysts with γ-Al2O3 contents in the range of 0-100 wt% were prepared and applied in the metathesis reaction of ethene and butene-2. Addition of γ-Al2O3did not affect the structure of MCM-22 zeolite as evidenced by XRD and N2 adsorption measurements. It was deduced from TPR experiments that γ-Al2O3 phase favored the formation of polymolybdate or multilayered Mo oxide, while more Al2（MoO4）3 species were generated over MCM-22 zeolites. Alumina content in the support was directly related to the metathesis activity of ethene and butene-2 to propene. Mo species with higher valence （Mo6＋or Mo5＋） contributed more to the excellent performance of catalyst than metallic Mo. The best catalyst activity and stability was obtained over 3.0Mo/（MCM-22-30%Al2O3） under the reaction condition of 1.0 MPa and 125℃ using N2 as the pretreatment gas.
文摘Producing methanol from coke oven gas(COG) is one of the important applications of COG. Removal of sulfur from COG is a key step of this process. Conversion and reaction kinetics over a commercial Fe-Mo/Al2O3 catalyst(T-202) were studied in a continuous flow fixed bed reactor under pressures of 1.6-2.8 MPa, space time of 1.32-3.55 s and temperatures of 240-360 °C. Though the COG contains about 0.6 mol/mol H2, hydrogenation of CO and CO2 is not significant on this catalyst. The conversions of unsaturated hydrocarbons depend on their molecular structures. Diolefins and alkynes can be completely hydrogenated even at relatively low temperature and pressure. Olefins, in contrast, can only be progressively hydrogenated with increasing temperature and pressure. The hydrodesulfurization(HDS) of CS2 on this catalyst is easy. Complete conversion of CS2 was observed in the whole range of the conditions used in this work. The original COS in the COG can also be easily converted to a low level. However, its complete HDS is difficult due to the relatively high concentration of CO in the COG and due to the limitation of thermodynamics. H2 S can react with unsaturated hydrocarbons to form ethyl mercaptan and thiophene, which are then progressively hydrodesulfurized with increasing temperature and pressure. Based on the experimental observations, reaction kinetic models for the conversion of ethylene and sulfur-containing compounds were proposed; the values of the parameters in the models were obtained by regression of the experimental data.
基金Project supported by the National Natural Science Key Foundation of China (20333030)
文摘Ce0.67Zr0.33O2-Al2O3 solid solution was prepared by the co-precipitation method. Fe2O3-based catalysts supported on the solid solution were obtained by the impregnation method. The article revealed that the optimal loading amount of Fe2O3 on Ce0.67Zr0.33 O2-Al2O3 in our experimental condition for catalytic combustion of methane was 8% （ mass fraction）. The prepared catalysts were characterized by BET, TPR, XRD analyses, and their catalytic activity was investigated after being calcined at 873 K and after being aged in water gas at 1273 K. When the loading amount of Fe203 was 8% （ mass fraction）, the catalyst held the highest activity, and the best temperature speciality and thermal stability. The complete-conversion temperature of methane for fresh and aged sample was 788 and 838 K, respectively. The range between the light-off temperature and the complete-conversion temperature was only 15 K. The characterization results of XRD indicated that Fe2O3 was well dispersed on the Ce0.67Zr0.33O2-Al2O3 matrix. The results of BET and TPR were in good harmony with the catalytic activity results.
文摘Nickel-alumina catalysts supported on cordierite monoliths of honeycomb structure surpass essentially the conventional granulated ones with respect to the output in carbon dioxide reforming of methane. Adjusting the surface acid-base properties of catalysts by introduction of alkali metal （Na, K） oxides inhibits the carbonization and as a result, improves the operational stability of these catalysts. An effect of promotion of nickel-alumina based composite doped by lanthanum oxide is found. This effect, caused by an additional route for the CO2 activation on Ni-La2O3/Al2O3/cordierite catalyst, is displayed in increase of methane conversion under conditions of an oxidant excess.
基金supported by the National Nature Science Foundation of China(No.20903054).
文摘The surface nature of fresh Mo2N/Al2O3, Mo2C/Al2O3 and/MoP/Al2O3 catalysts, which were synthesized directly in the IR cell to avoid passivation, were characterized by in situ IR spectroscopy with CO as a probe molecule. CO adsorbed on fresh catalysts showed characteristic IR bands at 2045 cm-1 for Mo2N/Al2O3 catalyst, 2054 cm-1 for MozC/Al2O3 catalyst and 2037 cm-1 for MoP/Al2O3 catalyst, respectively. A strong band at 2200 cm-1 for Mo2N/Al2O3 catalyst, which could be ascribed to NCO species formed when CO reacted upon surface active nitrogen atoms, and a weak band at 2196 cm-1 for Mo2C/Al2O3 catalyst, which could be attributed to CCO species, were also detected. CO adsorbed on fresh Mo2N/Al2O3 catalyst, Mo2C/Al2O3 catalyst and MoP/Al2O3 catalyst, showed strong molecular adsorption, just like noble metals. Our experimental results are bolstered by direct IR evidence demonstrating the similarity in surface electronic property between the fresh Mo2N/Al2O3, Mo2C/Al2O3 and MoP/Al2O3 catalysts and noble metals.
