Syngas production from methane reforming with CO2/H2O and O2 over NiO–MgO solid solution catalyst in fluidized bed reactors

Catalyst performance of NiO–MgO solid solution catalysts for methane reforming with CO₂ and H₂O in the presence of oxygen using fluidized and fixed bed reactors under atmospheric and pressurized conditions was investigated. Especially, methane and CO₂ conversion in the fluidized bed reactor in methane reforming with CO₂ and O₂ was higher than those in the fixed bed reactor over Ni_0.15Mg_0.85O catalyst under 1.0 MPa. In contrast, conversion levels in the fluidized and fixed bed reactor were almost the same over MgO-supported Ni and Pt catalysts. It is suggested that the promoting effect of catalyst fluidization on the activity is related to the catalyst reducibility. On a catalyst with suitable reducibility, the oxidized and deactivated catalyst can be reduced with the produced syngas and the reforming activity regenerates in the fluidized bed reactor during the catalyst fluidization. In addition, the catalyst fluidization inhibited the carbon deposition.     

催化剂形貌对沸腾床渣油加氢Ni-Mo/Al2O3催化剂活性位的影响机制

随着原油供应趋于劣质化和严格的环保法规出台,沸腾床渣油加氢技术引起了广泛关注。采用挤压成型法和STRONG沸腾床的特殊成型法分别制备了圆柱形和球形Ni-Mo/Al₂O₃催化剂,系统地研究了催化剂的颗粒形貌对活性相和渣油加氢性能的影响。采用XRD、N₂物理吸脱附、H₂-TPR、HRTEM、XPS和电子微探针分析等手段对催化剂进行了表征。结果表明,球形催化剂具有活性更强的Type Ⅱ类型活性位点、更优异的孔道结构性质和更好的流化性能,这使得其具有更高的渣油加氢活性。球形催化剂中的金属和载体之间相互作用较弱,这有利于形成更高硫化程度和堆垛层数的Ni-Mo-S Ⅱ型活性相,这种活性相在渣油加氢中具有更高的活性。此外,球形催化剂具有比圆柱形催化剂更大的孔径和孔体积,这有利于大分子杂质在孔道中的扩散和活性位点上的吸附,并且使得金属沉积物均匀分布在球形催化剂中,而不是集中分布在孔口。而且球形催化剂尺寸更小,可能更易于流化,这增强了催化剂的传质性能。     

Si含量对CO_2加氢制烃铁基催化剂的影响

以湿固相研磨法制备不同硅含量的铁基催化剂,采用X射线衍射、H2程序升温还原和傅里叶红外光谱对催化剂进行表征,在V(H_2)∶V(CO_2)∶V(N_2)=16∶8∶1、反应压力1.6 MPa、反应温度230℃、反应时间48 h和空速6 000 m L·(h·g-cat)-1条件下,在固定床反应器中考察催化剂的CO_2加氢制烃反应活性和烃类选择性。结果表明,随着Si O_2掺入量增加,催化剂的还原性能降低,结晶度呈下降趋势,CO_2转化率下降,但C5+烃类产物选择性在硅含量为10%时达到最大,为38.6%。     

活化气氛对CO2加氢制取低碳烯烃Fe-K催化剂构-效关系

CO₂加氢直接制取低碳烯烃是实现其资源化利用的重要途径。通过热分解法制备了5种不同K含量（1%、3%、5%、7%、9%）的Fe-K催化剂用于CO₂加氢反应,结果表明Fe95-K5（95% Fe-5% K,质量分数）催化剂具有最优的活性及C₂～C₄烯烃选择性;随后对Fe95-K5催化剂进行了10% H₂/Ar、10% CO/Ar及5% CO/5% H₂/Ar 3种不同气氛活化处理以及CO₂加氢反应。结果发现,10% CO/Ar活化的催化剂具有最高的C₂～C₄烯烃选择性（38.1%）及链增长能力（α=0.644）。此外,还通过X射线衍射、Raman、程序升温等表征技术揭示了催化剂在不同活化气氛下的结构演变历程。研究发现,10% CO/Ar与5% CO/5% H₂/Ar活化的催化剂会生成γ₁型碳化铁结构,而10% H₂/Ar活化的催化剂则会在反应过程中生成γ₂型碳化铁结构,两种碳化铁结构对CO₂解离均有促进作用。     

A study of the promoting effect of noble metal addition on niobia and niobia alumina catalysts

The catalytic activity of Nb₂O₅ and Nb₂O₅/Al₂O₃-supported metal catalysts was evaluated in the n-heptane conversion, CO hydrogenation and butadiene hydrogenation. After high temperature of reduction (HTR), the metal adsorption capacity decreases on all the samples, due to the reduction of Nb₂O₅ with subsequent blocking of metal atoms and bimetallic effect.

It was also observed that the activity decay caused by metal-support interaction was remarkably inhibited on the bimetallics with respect to the monometallics by comparing reaction rates after HTR. Thus, the addition of Rh to Co, Cu to Pd and Sn to Pt on niobia catalysts significantly altered the product distribution in Fischer–Tropsch synthesis (FTS) and in the hydrogenation and dehydrogenation of hydrocarbons, respectively. In addition, an unusual bifunctional effect was obtained in Pt/Nb₂O₅/Al₂O₃ catalyst.     

Performance characteristics of fluidized bed syngas methanation over Ni-Mg/Al2O3 catalyst

The performance characteristics of isothermal fluidized bed syngas methanation for substitute natural gas are investigated over a self-made Ni–Mg/Al2O3 catalyst. Via atmospheric methanation in a laboratory fluidized bed reactor it was clarified that the CO conversion varied in 5% when changing the space velocity in 40–120 L·g?1·h?1 but the conversion increased obviously by raising the superficial gas velocity from 4 to 12.4 cm·s?1. The temperature at 823 K is suitable for syngas methanation while obvious deposition of uneasy-oxidizing Cγoccurs on the catalyst at temperatures around 873 K. From a kinetic aspect, the lowest reaction temperature is suggested to be 750 K when the space velocity is 60 L·g?1·h?1. Raising the H2/CO ratio of the syngas increased proportionally the CO conversion and CH4 selectivity, showing that at enough high H2/CO ratios the active sites on the catalyst are sufficient for CO adsorption and in turn the reaction with H2 for forming CH4. Introducing CO2 into the syngas feed suppresses the water gas shift and Boudouard reactions and thus increased H2 consumption. The ratio of CO2/CO in syngas should be better below 0.52 because varying the ratio from 0.52 to 0.92 resulted in negligible increases in the H2 conversion and CH4 selectivity but decreased the CH4 yield. Introducing steam into the feed gas affected little the CO conversion but decreased the selectivity to CH4. The tested Ni–Mg/Al2O3 catalyst manifested good stability in structure and activity even in syngas containing water vapor.     

载体对镍基催化剂顺酐液相加氢性能的影响

分别以ZrO₂、SiO₂与Al₂O₃为载体,采用等体积浸渍法制备了Ni质量分数为15%的催化剂,考察了其催化顺酐液相加氢性能,并利用BET、XRD、H₂-TPR以及TPO-MS等表征手段对催化剂进行了详细表征。结果表明,随载体不同各催化剂的加氢活性及选择性存在较大差异,Ni/Al₂O₃催化剂的C=C键加氢活性最高,但其几乎没有C=O加氢活性,催化顺酐加氢主产物为丁二酸酐。Ni/ZrO₂催化剂具有最高的C=O加氢活性,催化顺酐加氢主产物为γ-丁内酯,在反应温度为483 K,氢气压力为5 MPa的条件下反应8 h时,Ni/ZrO₂催化剂的γ-丁内酯选择性达79.20%。催化剂的套用实验表明,Ni/ZrO₂与Ni/SiO₂催化剂具有高的使用稳定性,Ni/Al₂O₃催化剂则在套用过程中快速失活。顺酐加氢至γ-丁内酯的中间产物--丁二酸酐与催化剂间的相互作用是影响催化剂加氢选择性及使用稳定性的主要原因。     

Hydrogen production from steam reforming of methanol over CuO/ZnO/Al2O3 catalysts: Catalytic performance and kinetic modeling

A series of CuO/ZnO/Al_2O_3, CuO/ZnO/ZrO_2/Al_2O_3 and CuO/ZnO/CeO_2/Al_2O_3 catalysts were prepared by coprecipitation and characterized by N_2 adsorption, XRD, TPR, N_2O titration and HRTEM. The catalytic performances of these catalysts for the steam reforming of methanol were evaluated in a laboratory-scale fixed-bed reactor at 0.1 MPa and temperatures between 473 and 543 K. The results showed that the catalytic activity depended greatly on the catalyst reducibility and the specific surface area of Cu. An approximate linear correlation between the catalytic activity and the Cu surface area was found for all catalysts investigated in this study.Compared to CuO/ZnO/Al_2O_3, the ZrO_2-doped CuO/ZnO/Al_2O_3 exhibited higher activity and selectivity to CO,while the CeO_2-doped catalyst displayed lower activity and selectivity. Finally, an intrinsic kinetic study was carried out over a screened CuO/ZnO/CeO_2/Al_2O_3 catalyst in the absence of internal and external mass transfer effects. A good agreement was observed between the model-derived effluent concentrations of CO(CO_2) and the experimental data. The activation energies for the reactions of methanol-steam reforming, water-gas shift and methanol decomposition over CuO/ZnO/CeO_2/Al_2O_3 were 93.1, 85.1 and 116.5 k J·mol~(-1), respectively.     

二氧化碳甲烷化催化剂的研究进展

CO₂催化加氢甲烷化反应是温室气体CO₂资源化利用的有效途径之一。本文回顾了CO₂催化加氢甲烷化催化剂的研究现状, 其中Ni基催化剂是研究最为广泛的CO₂甲烷化催化剂。重点介绍了Al₂O₃、SiO₂和La₂O₃载体及CeO₂和La₂O₃助剂等对Ni基催化剂CO₂甲烷化性能的影响, 阐述了载体的结构、电子性能、化学性能和助剂等对Ni基催化剂CO₂甲烷化性能的影响。结合几种非Ni基CO₂甲烷化催化剂的对比研究发现, 具有有序介孔结构的Co基催化剂也表现出了优越的CO₂甲烷化性能。由此表明, 催化剂新颖的结构也是影响CO₂甲烷化性能的重要因素, 通过催化剂结构、组成等的调变, 能实现CO₂低温高效甲烷化, 为CO₂甲烷化工业化进程奠定基础。     

Preparation and characterization of Ir-based catalysts on metallic supports for high-temperature steam reforming of methanol

Ir-based catalysts on heat-resisting foil supports with different washcoats were investigated for hydrogen production by high-temperature steam reforming of methanol. Al₂O₃, Ce_0.8Zr_0.2O₂–Al₂O₃, Ce_0.8Zr_0.2O₂/Al₂O₃ and Ce_0.8Zr_0.2O₂ coatings were prepared on the metallic supports and iridium was deposited on them as the active component. The samples were characterized by X-ray powder diffraction (XRD), ultrasonic vibration test, scanning electron microscope (SEM) and temperature-programmed reduction (TPR). The performance of the catalysts for steam reforming of methanol was evaluated with a fixed-bed reactor. It was found that the phase structure, the shape of the surface particles and the coating adherence were different from each other for the four kinds of coatings. The activities, selectivities and stabilities of these Ir-based catalysts on metallic supports were compared to select the optimal one for use in high-temperature methanol steam reforming. The results indicated that the Ir/Ce_0.8Zr_0.2O₂/Al₂O₃/FeCrAl catalyst showed better performance than the other catalysts, which is a promising candidate for hydrogen production via the methanol steam reforming process in Pd membrane reactors.     

Ru催化加氢选择性脱除F-T合成水相中的含氧化合物

采用催化加氢技术脱除F-T合成水相中羧酸、醛、醇、酮、酯含氧化合物,考察了Ru/ZrO₂、Ru/TiO₂、Ru/SiO₂和Ru/Al₂O₃ 4种Ru催化剂的反应性能.相对于酸、醇,水中的醛、酮、酯更易被转化.其中Ru/ZrO₂和Ru/TiO₂具有良好的加氢脱羰活性,在200℃、9.8 MPa、3.0 h^-1空速下,酸、醛、醇、酮、酯均转化为C₁～C₆的烷烃,总转化率达92%.同条件下,虽然Ru/Al₂O₃对酸、醛、酮、酯的转化活性较高(>87%),但对醇的转化不到30%,具有选择性转化特点.H₂-TPR和NH₃-TPD结果表明,Ru/Al₂O₃催化剂的金属活性位与载体酸性位的协同作用有利于羧酸的加氢反应,能抑制醇的加氢脱羰活性;而金属-载体相互作用较弱和酸度较低的催化剂有利于羧酸、醇发生加氢脱羰反应.Ru/Al₂O₃催化剂运行500 h后失活,XRD、SEM和N₂-物理吸附表明,载体结构物相和织构性质的改变以及活性组分的流失是导致催化剂失活的主要因素.     

一种新γ相氧化铝负载的铁铝双金属催化剂用于反向水煤气转化反应(英文)

In reverse water gas shift (RWGS) reaction CO₂ is converted to CO which in turn can be used to produce beneficial chemicals such as methanol. In the present study, Mo/Al₂O₃, Fe/Al₂O₃ and Fe-Mo/Al₂O₃ catalysts were synthesised using impregnation method. The structures of catalysts were studied using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) method, inductively coupled plasma atomic emission spectrometer (ICP-AES), temperature programmed reduction (H₂-TPR), CO chemisorption, energy dispersive X-ray (EDX) and scanning electron microscopy (SEM) techniques. Kinetic properties of all catalysts were investigated in a batch reactor for RWGS reaction. The results indicated that Mo existence in structure of Fe-Mo/Al₂O₃ catalyst enhances its activity as compared to Fe/Al₂O₃. This enhancement is probably due to better Fe dispersion and smaller particle size of Fe species. Stability test of Fe-Mo/Al₂O₃ catalyst was carried out in a fixed bed reactor and a high CO yield for 60 h of time on stream was demonstrated. Fe₂(MoO₄)₃ phase was found in the structures of fresh and used catalysts. TPR results also indicate that Fe₂(MoO₄)₃ phase has low reducibility, therefore the Fe₂(MoO₄)₃ phase signifificantly inhibits the reduction of the remaining Fe oxides in the catalyst, resulted in high stability of Fe-Mo/Al₂O₃ catalyst. Overall, this study introduces Fe-Mo/Al₂O₃ as a novel catalyst with high CO yield, almost no by-products and fairly stable for RWGS reaction.     

铈锆固溶体担载的镍催化剂对CO2甲烷化性能研究

采用共沉淀法制备了Ce_xZr_1-xO₂固溶体作为催化剂载体,采用柠檬酸络合法将镍负载于Ce_xZr_1-xO₂载体上得到Ni/Ce_xZr_1-xO₂催化剂,利用X射线衍射（XRD）、N₂吸附-脱附（N₂-BET）、程序升温脱附（TPD）、程序升温还原（TPR）等技术对催化剂进行表征,在常压微型固定床反应器上测试了CO₂甲烷化的性能,考察了n（Ce）/n（Zr）、镍含量对催化性能的影响。研究发现制备的催化剂具有优异的活性,在常压和空速15 000 mL·g^-1·h^-1条件下,反应温度200℃时,12% Ni/Ce_0.25Zr_0.75O₂催化剂（负载量为质量分数,下同）CO₂的转化率达74%,CH₄选择性为100%。12% Ni/Ce_0.25Zr_0.75O₂催化剂300 h的稳定性测试结果显示其具有较高的抗烧结性能。催化剂的优异活性归因于采用了新的负载方法--柠檬酸络合法负载活性组分镍,该法实现了镍的高分散和催化剂的大的比表面积。     

Hydrogenation of carbon dioxide over copper-pyrochlore/zeolite composite catalysts

The hydrogenation of CO₂ was studied over composite catalysts obtained by mixing Cu-based methanol synthesis catalyst and HY zeolite. A mechanism associating methanol synthesis and MTG (methanol to gasoline) reaction allowed the formation of C₁-C₄ hydrocarbons. It was found that the catalytic behaviors of the composite catalysts were favorably influenced by the characteristics of the methanol synthesis catalysts. The Cu-La₂Zr₂O₇ catalyst we recently developed associated with HY zeolite exhibited interesting performances in hydrocarbon synthesis. The addition of ZrO₂ to Cu---La₂Zr₂O₇/HY enhanced the ability to produce hydrocarbons. Comparing composite catalyst systems prepared with different Cu-based methanol synthesis catalysts, the effect of Na contamination on methanol and hydrocarbon formation over composite catalysts were also discussed.     

Catalytic performance of supported Ni catalysts in partial oxidation and steam reforming of tar derived from the pyrolysis of wood biomass

Activity test of Ni/Al₂O₃, Ni/ZrO₂, Ni/TiO₂, Ni/CeO₂ and Ni/MgO catalysts in the partial oxidation (POT) and steam reforming of tar (SRT) derived from the pyrolysis of cedar wood was performed. In these activity tests, the order of the performance in both reactions was similar. Catalyst characterization was also carried out by means of H₂ adsorption, TPR and XRD. From the combination of catalyst characterization with the results of the activity tests, it is suggested that the conversion of tar in POT and SRT is mainly controlled by the number of surface Ni metal. In addition, Ni/CeO₂ showed smaller amount of coke than other catalysts in the POT and SRT. From the TGA profiles of active carbon mixed with catalysts, it is found that Ni/CeO₂ promoted the reaction of active carbon with O₂ and steam. The function of the fluidized bed reactor in the POT with respect to coke and tar amount was discussed.     

NiO/Al_2O_3基催化剂的TPR特性研究

NiO/Al_2O_3基催化剂用于替代贵金属催化剂,被广泛应用于石油和石化领域生产过程的加氢、脱硫和脱氮。采用TPR方法,研究不同Ni含量NiO/Al_2O_3及不同载体的催化剂还原特性。结果表明,NiO/Al_2O_3催化剂在10%H_2-Ar气氛下,还原温度范围较宽,为(300~800)℃,其中,(500~600)℃还原速率最大;随着NiO含量的增加,起始还原温度降低,还原耗氢量按比例增加;以MgO为载体的NiO催化剂还原呈现双峰特征,以SiO2和TiO2为载体的NiO催化剂的初始还原温度比NiO/Al_2O_3催化剂降低(100~200)℃。     

Total oxidation of propene and propane over gold–copper oxide on alumina catalysts: Comparison with Pt/Al2O3

Oxidation of propene and propane to CO₂ and H₂O has been studied over Au/Al₂O₃ and two different Au/CuO/Al₂O₃ (4 wt.% Au and 7.4 wt.% Au) catalysts and compared with the catalytic behaviour of Au/Co₃O₄/Al₂O₃ (4.1 wt.% Au) and Pt/Al₂O₃ (4.8 wt.% Pt) catalysts. The various characterization techniques employed (XRD, HRTEM, TPR and DR-UV–vis) revealed the presence of metallic gold, along with a highly dispersed CuO (6 wt.% CuO), or more crystalline CuO phase (12 wt.% CuO).

A higher CuO loading does not significantly influence the catalytic performance of the catalyst in propene oxidation, the gold loading appears to be more important. Moreover, it was found that 7.4Au/CuO/Al₂O₃ is almost as active as Pt/Al₂O₃, whereas Au/Co₃O₄/Al₂O₃ performs less than any of the CuO-containing gold-based catalysts.

The light-off temperature for C₃H₈ oxidation is significantly higher than for C₃H₆. For this reaction the particle size effect appears to prevail over the effect of gold loading. The most active catalysts are 4Au/CuO/Al₂O₃ (gold particles less than 3 nm) and 4Au/Co₃O₄/Al₂O₃ (gold particles less than 5 nm).     

镍/氧化铝加氢催化剂的制备及性能研究

羟基新戊醛（HPA）的加氢多采用贵金属和铜系催化剂,为了更好地降低催化剂生产成本和操作成本,分别对比了共沉淀法和浸渍法制备的镍/氧化铝催化剂,并以HPA为原料,在固定床装置上考察了系列催化剂加氢合成新戊二醇（NPG）的催化性能。采用X射线衍射（XRD）、氮气物理吸附（BET）、一氧化碳脉冲吸附等方法进行表征,结果表明,浸渍法制备的20%镍/氧化铝催化剂,比表面积较大,金属分散性好,且催化剂中的镍物种易被还原,其反应性能良好。在相对较温和的反应条件下,即反应温度为103 ℃、反应压力为3 MPa、液时空速为1 h^-1、氢醛物质的量比为10时,HPA转化率为100%,NPG选择性为99.3%。在1 000 h的长周期评价过程中,该催化剂保持了较好的活性,具有更好的工业化前景。     

碱/碱土金属修饰Ni基催化剂的CO2吸附与甲烷化性能

采用分步浸渍法制备了碱/碱土金属修饰Ni基催化剂Ni-M/Al₂O₃ (M=K₂CO₃, Na₂CO₃, MgO, CaO)。探究了碱/碱土金属的添加对改性Ni基催化剂CO₂吸附和甲烷化性能的影响。研究发现,碱/碱土金属的添加提高了Ni/Al₂O₃催化剂表面的碱性活性位点密度,强化了其CO₂吸附性能。碱/碱土金属类型影响Ni-M/Al₂O₃催化剂碱性活性位点的分布、NiO物相的转化及Ni的分散度,进而影响其甲烷化性能。MgO添加使NiO物相转化为与载体呈强相互作用的β型和γ型NiO,降低了催化剂表面的强碱性活性位点比例,有利于CO₂吸附活化。Ni-MgO/Al₂O₃的CO₂吸附容量最高为0.68mmolCO₂/g,其CO₂转化率和CH₄选择性分别高达58.4%和95.4%,其在烟气CO₂捕集与原位甲烷化中极具应用前景。     

Ni/Al_2O_3催化剂的CO_2-TPD表征

Ni/Al_2O_3催化剂是甲烷二氧化碳重整反应制取合成气研究最多、最具应用潜力的一种催化剂。通过对催化剂进行CO_2-TPD研究,考察还原态Ni/Al_2O_3催化剂的CO_2脱附特性。结果表明,浸渍法制备的Ni/Al_2O_3催化剂CO_2脱附曲线呈现双峰,分别在(60~65)℃和(350~380)℃出现高低温两个活性位;高温CO_2吸附量为3.0 cm~3·g~(-1),低温CO_2吸附量为24.0 cm~3·g~(-1)。催化剂的CO_2吸附量与其Ni含量无关。考察选用不同载体的CO_2脱附行为,发现以Al_2O_3为载体的催化剂CO_2吸附量是MgO和SiO_2为载体催化剂的2~4倍,以TiO_2为载体的催化剂几乎不吸附CO_2。