天然气年产4万吨甲醇联产年产2.5万吨合成氨代替重油设计

利用现生产重油制氨的1000m~3(V_n)(O_2)/h空分,建设天然气并联换热蒸汽转化串纯氧部分氧化制甲醇和氨两用合成气,成为4万吨/年甲醇联产2.5万吨/年氨的生产单元组合,既节能节气、降低投资和生产消耗及成本,又充分利用现有设备发挥生产能力,同时还可增加产品和产量。     

Investigation of CH4 Reforming with CO2 on Meso-Porous Al2O3-Supported Ni Catalyst

Meso-porous Al₂O₃-supported Ni catalysts exhibited the highest activity, stability and excellent coke-resistance ability for CH₄ reforming with CO₂ among several oxide-supported Ni catalysts (meso-porous Al₂O₃ (Yas1-2, Yas3-8), -Al₂O₃, -Al₂O₃, SiO₂, MgO, La₂O₃, CeO₂ and ZrO₂). The properties of deposited carbons depended on the properties of the supports, and on the meso-porous Al₂O₃-supported Ni catalyst, only the intermediate carbon of the reforming reaction formed. XRD and H₂-TPR analysis found that mainly spinel NiAl₂O₄ formed in meso-porous Al₂O₃ and -Al₂O₃-supported catalysts, while only NiO was detected in -Al₂O₃, SiO₂, CeO₂, La₂O₃ and ZrO₂ supports. The strong interaction between Ni and meso-porous Al₂O₃ improved the dispersion of Ni, retarded its sintering and improved the activated adsorption of CO₂. The coking reaction via CH₄ temperature-programed decomposition indicated that meso-porous Al₂O₃-supported Ni catalysts were less active for carbon formation by CH₄ decomposition than Ni/-Al₂O₃ and Ni/-Al₂O₃.     

B113-2型低汽气比CO高温变换催化剂的研制

介绍了B113-2型低汽气比CO高温变换催化剂的研制方法及其特点。实验室测试表明,B113-2型催化剂具有堆密度低、运行强度高、选择性好、抗沸水性能优、本体含硫低及低温活性好等优点。     

Comparison of two IT DIR-SOFC models: Impact of variable thermodynamic, physical, and flow properties. Steady-state and dynamic analysis

This paper compares two dynamic, one-dimensional models of a planar anode-supported intermediate temperature (IT) direct internal reforming (DIR) solid oxide fuel cell (SOFC): one where the flow properties (pressure, gas stream densities, heat capacities, thermal conductivities, and viscosity) and gas velocities are taken as constant throughout the system, based on inlet conditions, and one where this assumption is removed to focus on the effect of considering the variation of local flow properties on the prediction of the fuel cell performance. The refined model consists of mass, energy, and momentum balances, and of an electrochemical model that relates the fuel and air gas compositions and temperatures to voltage, current density, and other relevant fuel cell variables. Simulations for steady-state and dynamic conditions have been carried out and the results obtained from the two models compared. For a co-flow SOFC operating on a 10% pre-reformed methane fuel mixture, with 75% fuel utilisation, inlet fuel and air temperatures of 1023 K, average current density of , and an air ratio of 8.5, the results show that, although the error incurred in the prediction of the flow properties in the first model is significant, there is good agreement between both models in terms of the overall cell performance: the maximum difference in the local temperature values is about 7 K and the cell efficiency differs by less than 1%. However, the discrepancies between the two models increase, especially in the fuel channel, when higher current density values are assigned to the cell.     

Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles

A microkinetic model for methanol decomposition on platinum is presented. The model incorporates competitive decomposition pathways, beginning with both O–H and C–H bond scission in methanol, and uses results from density functional theory (DFT) calculations [Greeley and Mavrikakis, J. Am. Chem. Soc. 124 (2002) 7193, Greeley and Mavrikakis, J. Am. Chem. Soc. 126 (2004) 3910]. Results from reaction kinetics experiments show that the rate of H₂ production increases with increasing temperature and methanol concentration in the feed and is only nominally affected by the presence of CO or H₂ with methanol. The model, based on the values of binding energies, pre-exponential factors and activation energy barriers derived from first principles calculations, accurately predicts experimental reaction rates and orders. The model also gives insight into the most favorable reaction pathway, the rate-limiting step, the apparent activation energy, coverages, and the effects of pressure. It is found that the pathway beginning with the C–H bond scission (CH₃OH→H₂COH→HCOH→CO) is dominant compared with the path beginning with O–H bond scission. The cleavage of the first C–H bond in methanol is the rate-controlling step. The surface is highly poisoned by CO, whereas COH appears to be a spectator species.     

Reforming of methane and coalbed methane over nanocomposite Ni/ZrO2 catalyst

Nanocomposite Ni/ZrO₂-AN catalyst consisting of comparably sized Ni metal and ZrO₂ nanoparticles is studied in comparison with zirconia- and alumina-supported Ni catalysts (Ni/ZrO₂-CP and commercial Ni/Al₂O₃-C) for steam reforming of methane (SRM) and for combined steam and CO₂ reforming of methane (CSCRM). The reactions are performed under atmospheric pressure with stoichiometric amounts of H₂O and CH₄ or (H₂O + CO₂) and CH₄ at 1073 K. Under a wide range of methane space velocity (gas hourly space velocity of methane GHSV_CH4 = 12,000–96,000 ml/(h g_cat.), the nanocomposite Ni/ZrO₂-AN catalyst always shows higher activity and stability for both SRM and CSCRM reactions. The two supported Ni catalysts (Ni/ZrO₂-CP and Ni/Al₂O₃-C) exhibit fairly stable catalysis under low GHSV_CH4 but they are easily deactivated under high GHSV_CH4 and become completely inactive when they are reacted for ca.100 h at GHSV_CH4 = 48,000 ml/(h g_cat.). The CSCRM reaction is carried out with different H₂O/CO₂ ratios in the reaction feed while keeping the molar ratio (H₂O + CO₂)/CH₄ = 1.0, the results prove that the nanocomposite Ni/ZrO₂-AN catalyst can be highly promising in enabling a catalytic technology for the production of syngas with flexible H₂/CO ratios (ca. H₂/CO = 1.0–3.0) to meet the requirements of various downstream chemical syntheses.     

燃料电池氢源技术--中低温乙醇水蒸气重整制氢研究

采用浸渍-热分解法制备了一种纳米Ni/Y2O3催化剂,并应用X射线衍射、BET比表面测试分析手段对该催化剂的结构性能进行了表征,采用固定床反应器对催化剂的催化性能进行测试。结果表明:该催化剂对乙醇的水蒸气重整反应表现出较高的活性和稳定性,可作为燃料电池氢源技术中乙醇重整器的候选催化剂。     

Kinetic Study of the Steam Reforming of Isobutane Using a Pt–CeO2–Gd2O3 Catalyst

Steam reforming of isobutane on a 0.5% Pt–Ce_0.8Gd_0.2O_1.9 catalyst was carried out from 300 to 700 °C under integral conditions with a gas hourly space velocity (GHSV) of 12,000 h⁻¹. The major products were H₂, CO₂, CO and CH₄. The other products produced were ethane, ethylene, propane and propylene with a total molar composition of less than 1.5%. A complete conversion of isobutane was achieved at 700 °C, Kinetic data was obtained by changing the partial pressure of the reactants and the temperature under differential conditions with a GHSV of 55,400 h⁻¹. This was done after observing stable isobutane steam reforming for 160 h and under conditions where the mass transfer limitations were insignificant. An empirical Langmuir–Hinshelwood type model that best fit the kinetic data available was developed.     

REACTOR-MEMBRANE PERMEATOR CASCADE FOR ENHANCED PRODUCTION AND RECOVERY OF H2 AND CO2 FROM THE CATALYTIC METHANE-STEAM REFORMING REACTION

The catalytic reforming of methane by steam is an important industrial process that produces H₂, CO and CO₂, thus chemically transforming natural gas, coal gas and light hydrocarbon feedstocks to synthesis gas or hydrogen fuel. Methane-steam reforming may consist of a number of reactions depending on the reforming catalyst, operating conditions and feedstock composition, The typical industrially desirable reactions are the reverse of methanation (CH₄ + H₂O = CO + 3H₂) and the water-gas shift (CO + H₂O = CO₂ + H₂). Both reactions are equilibrium limited and the composition of the mixture that exits the reformer is in accordance with the one calculated thermodynarmically. Removal of reaction products at the reactor exit by means of selective membrane permeation can offer improved CH₄ conversions and CO₂ and H₂ yields, assuming the subsequent utilization of the reject streams by a second methane-steam reformer. We numerically investigated the feasibility of a system of two tubular methane-steam reformers, in series with an intermediate permselective polyimide membrane permeator, as means of improving the overall CH₄ conversion and the H₂, CO₂ yields over conventional methane-steam reforming equilibrium reaction-separation schemes that are currently in industrial practice. The unique feature of the permselective polyimide separator is the simultaneous removal of H₂ and CO₂ versus CH₄ and CO from the reformed streams. The utilized 6FDA-3,3', 5,5'-TMB aromatic polyimide was reportedly characterized [10] and found to exhibit superior permselective properties compared with other polyimides of the same or different dianhydride sequence. Conversion and yield of the designed reactor-membrane permeator reforming system can be maximized by optimizing the permselective properties of the membrane material and the design variables of the reactors and the permeator. Product recovery and purity in the permeate stream need to be compromised to overall enhance methane conversion and product yield. The operating variables that were varied to investigate their effect on the magnitude of conversion and yield included the inlet pressure of the first reformer, the temperature of both reformers, and the permeator dimensionless Pe' number (variation of the first two variables results to a drastic change in the composition of the reformed stream that enters into the permeator). The numerical results show that the new reformer-membrane permeator cascade process can be more effective (it can offer increased CH₄ conversions and H₂, CO₂ yields) than conventional equilibrium methane-steam reforming reaction-separation processes currently in practice.     

小型合成氨厂节气节能工艺评价 (Ⅷ)换热式转化深冷净化工艺

作者对“换热式转化深冷净化工艺”用于改造以间歇蒸汽转化工艺生产合成氨小厂的工艺流程、主要原料消耗、技术经济指标和风险性进行了研究、计算、分析和比较,为国内105家以天然气为原料的小型合成氨厂节气节能改造的方案选择提供依据。