Preform impregnation to optimize the properties and microstructure of RB-SiC prepared with laser sintering and reactive melt infiltration

Indirect selective laser sintering (SLS) was combined with reactive melt infiltration (RMI) to fabricate RB-SiC, and the effects of preform impregnation with different carbon source on the carbonized sample and final RB-SiC were investigated. Results show that the impregnation treatment led to increased bulk density and mechanical strength of samples at all stages. The pore size dwindled and the porosity decreased significantly for the carbonized sample, and the content of Si reduced for the final RB-SiC. The impregnation with PF resin containing 30 % nano carbon black (PFnanoC) seems more promising for the comprehensive properties improvement, the final RB-SiC had a relatively fewer amount of residual pore and carbon and showed superior mechanical properties compared with those of sample impregnated with only PF resin. Kinetics analysis indicates a slower pore-clogging rate under the PFnanoC impregnation condition, which avoided or hindered a too-early infiltration cease during the RMI process.     

还原氧化石墨烯/粘胶基钒酸铋光催化材料的制备及其性能

针对钒酸铋(BiVO₄)光催化效率低、难回收的缺点,利用硅烷偶联剂KH-560和氧化石墨烯(GO)依次对粘胶非织造布改性,再利用搅拌水热法在其表面生长BiVO₄制备还原氧化石墨烯(RGO)/粘胶基BiVO₄光催化材料。采用扫描电子显微镜、X射线衍射、X射线光电子能谱和紫外-可见吸收光谱对材料进行了表征,并研究了RGO/粘胶基BiVO₄材料的光催化活性、重复使用性能和光催化机制。结果表明:BiVO₄成功负载在RGO/粘胶非织造布表面,得到了RGO/粘胶基BiVO₄光催化材料;在1 kW氙灯照射下,90 min内对活性黑5脱色率达到95%以上,重复5次后仍达到92%以上;自由基捕捉实验表明,光生空穴、超氧自由基和羟基自由基参与了光化学反应,其中羟基自由基的作用最大。     

Heat-integrated reactive distillation process for synthesis of fatty esters

Catalytic reactive distillation (RD) offers novel opportunities for manufacturing fatty acid alkyl esters involved in specialty chemicals and at a larger scale in biodiesel. The integration of reaction and separation into one RD unit, corroborated with the use of a heterogeneous catalyst, provides major benefits such as low capital investment and operating costs. This work presents a novel heat-integrated process based on reactive distillation that aims to reduce furthermore the energy requirements for biodiesel production, leading to competitive operating costs. Despite the high degree of integration, the process is well controllable using an efficient control structure proposed in this work. Rigorous simulations embedding experimental results were performed using computer aided process engineering tools, such as AspenTech Aspen Plus and Aspen Dynamics. The RD column was simulated using the rigorous RADFRAC unit with RateSep (rate-based) model, and explicitly considering three phase balances. Steady-state and dynamic simulation results are given for a plant producing 10 ktpy fatty acid methyl esters (FAME) from methanol and waste vegetable oil with high free fatty acids (FFA) content, using sulfated zirconia as green catalyst. The heat-integrated RD process eliminates all conventional catalyst related operations, efficiently uses the raw materials and the reactor volume offering complete conversion of the fatty acids and allowing significant energy savings. Remarkably, compared to previously reported RD processes, the energy requirements of this process are about 45% lower - only 108.8 kW h/ton biodiesel - while the capital investment cost remains the same as no additional equipment is required.     

Reactive sintering process and thermoelectric properties of boron rich boron carbides

Dense boron rich boron carbides were reactive sintered by hot pressing at 2050 °C using elementary boroncarbon compositions with carbon contents of 9.1, 11.1, 13.3 and 18.8 at.%. The following material characteristics are presented: relative density, SEM images, EDX, X-ray diffraction and corresponding lattice parameters, Seebeck coefficient, electrical conductivity and thermoelectric power factor. Significant grain growth has been obtained with increasing boron content. A deeper understanding of the boron and carbon reaction and the overall sintering process is gained by thermal and chemical analysis in combination with X-ray diffraction. Additionally a thermal experiment with boron and carbon layers illustrates the solid state diffusion behaviour. The found results of boron carbide properties of this paper correspond with results by other authors. The aim is to correlate technological aspects of sintering procedure with material properties. This should help to improve the thermoelectric efficiency of boron carbide based materials.     

Production of ethyltert-butyl ether fromtert-butyl alcohol and ethanol catalyzed byβ-zeolite in reactive distillation

The synthesis of ethyl tert-butyl ether (ETBE) from a liquid phase reaction between tert-butyl alcohol (TBA) and ethanol (EtOH) in reactive distillation has been studied.β-Zeolite catalysts with three compositions (Si/Al ratio=13, 36 and 55) were compared by testing the reaction in a semi-batch reactor. Although they showed almost the same performance, the one with Si/Al ratio of 55 was selected for the kinetic and reactive distillation studies because it is commercially available and present in a ready-to-use form. The kinetic parameters of the reaction determined by fitting parameters with the experimental results at temperature in the range of 343–363 K were used in an ASPEN PLUS simulator. Experimental results of the reactive distillation at a standard condition were used to validate a rigorous reactive distillation model of the ASPEN PLUS used in a simulation study. The effects of various operating parameters such as condenser temperature, feed molar flow rate, reflux ratio, heat duty and mole ratio of H₂O : EtOH on the reactive distillation performance were then investigated via simulation using the ASPEN PLUS program. The results were compared between two reactive distillation columns: one packed withβ-zeolite and the other with conventional Amberlyst-15. It was found that the effect of various operating parameters for both types of catalysts follows the same trend; however, the column packed withΒ-zeolite outperforms that with Amberlyst-15 catalyst due to the higher selectivity of the catalyst.     

The utility of coal molecular models

There are a large number (> 125) of molecular representations for coals that span the rank range over seven decades. However, their utility has mostly been in representing chemical structural features, rather than in probing physical structure or exploring the structure-behavior relationship. This paper examines the utility of coal models and reviews the existing and emerging opportunities for coal models to contribute to coals effective utilization via demystification of the structure-behavior relationship. Coal models have been used to explore the coalification pathway, including contraction with water removal. Physical evaluations have probed the density of models as a check on their accuracy. Pore size distribution and sorption have been explored in simple pores and more recent work with carbon dioxide, water and methane sorption within the porous structure of large-scale (< 20,000 atoms) model. Pair distribution frequency and small angle X-ray scattering simulations have also been compared with experimental observations and offer an additional check on the constitution of the model structure. Simulated HRTEM and simulated (calculated) NMR spectra also exist. Models have been disassembled in efforts to represent the pyrolysis process, char formation, and char reactivity (including the role of ion-exchangable ions). Similar to the pyrolysis models, direct liquefaction has been explored with a pyrolysis style approach. Coal-solvent swelling, and coal-solvent solubility have also been explored. While considerable progress has accompanied improvements in computational power and software advances, it is the generation of the model that is the most significant barrier to the meaningful utility of these models. The ability to generate large-scale models (incorporation of molecular weight diversity and structural diversity) with new automation approaches, coupled with new dynamic force-fields that can simulate reactive events in complicated materials like coals, offers a new hope for the utility of coal or char molecular models to probe our understanding and aid in the scientific method rather than our current informed trial and error approach.     

Supercritical carbon dioxide-assisted reactive extrusion for preparation long-chain branching polypropylene and its rheology

An environmental benign process, which uses supercritical carbon dioxide (ScCO₂) as a processing aid, is developed in this work to prepare long chain branching polypropylene (LCB-PP). Results from the oscillatory shear rheology, melt elongational behavior and Fourier transformed infrared spectroscopy (FTIR) show that long chains have been linked as branches to the original linear PP chains using scCO₂-assisted reactive extrusion in the presence of cumene hydroperoxide and 1,6-hexanediol diacrylate. Compared to the initial linear PP, the branched samples show higher storage modulus (G′) at low frequency, distinct strain hardening of elongational viscosity, lower melt flow rate, increased crystallization temperature and improvement of the melt strength. ScCO₂ can improve the branching efficiency of modified PPs. The elastic response, melt strength and strain hardening parameter of the modified PPs increase with increasing scCO₂ concentration, which is ascribed to scCO₂ acting as a plasticizer for reducing PP viscosity and a carrier for active chemical species.     

Reactive pressure swing batch distillation by a new double column system

Ethyl-acetate is generally produced by the esterification reaction of ethanol with acetic-acid. Since the reaction is equilibrium-limited, the use of reactive distillation is an attractive option. A new double-column system is suggested for ethyl-acetate production by applying reactive pressure swing batch distillation. The system was investigated by a feasibility study based on the analysis of reactive and non-reactive residue curve maps. Two different process options were found to be feasible. In the first option, the reactive column operates at the lower pressure (1.01 bar), and the non-reactive column that removes ethyl-acetate from the system operates at the higher pressure (10 bar). The second option allows the reactive column to operate at the higher pressure (10 bar), and the non-reactive column removes water at the lower pressure (1.01 bar). The first process option was studied by rigorous simulation based on less simplifying assumptions using a professional dynamic simulator. The influence of the most important operation parameters was also studied.     

Photo-degradation of methylene blue in the presence of 2-anthraquinone sulfonate and cyclohexanol

Hydroxyl radical is a highly reactive oxygen species and can be used to oxidize many pollutants and toxic organic compounds. 2-Anthraquinone sulfonate (2-AQS) was found capable of producing hydroxyl radicals under UVA exposure. In this study, the photo-induced oxidative degradation of methylene blue (MB) by 2-anthraquinone sulfonate was investigated. Results indicated that 2-anthraquinone sulfonate was able to photo-degrade methylene blue. Addition of some chemical such as cyclohexanol could significantly increase the photo-degradation of methylene blue by 2-anthraquinone sulfonate. The degradation process was investigated by using LC-MS. Potential photochemical reaction mechanism of 2-anthraquinone sulfonate was proposed in this paper. Influence of solution pH value and different ratios of 2-AQS, cyclohexanol and MB mixture on the degradation of methylene blue were also studied.     

Pilot plant study of post-combustion carbon dioxide capture by reactive absorption: Methodology, comparison of different structured packings, and comprehensive results for monoethanolamine

Post-combustion carbon capture (PCC) from fossil fuel power plants by reactive absorption can substantially contribute to reduce emissions of the greenhouse gas CO₂. To test new solvents for this purpose small pilot plants are used. The present paper describes results of comprehensive studies of the standard PCC solvent MEA (0.3 g/g monoethanolamine in water) in a pilot plant in which the closed cycle of absorption/desorption process is continuously operated (column diameters: 0.125 m, absorber/desorber packing height: 4.25/2.55 m, packing type: Sulzer BX 500, flue gas flow: 30-110 kg/h, CO₂ partial pressure: 35-135 mbar). The data establish a base line for comparisons with new solvents tested in the pilot plant and can be used for a validation of models of the PCC process with MEA. The ratio of the solvent to the flue gas mass flow is systematically varied at constant CO₂ removal rate, and CO₂ partial pressure in the flue gas. Optimal operating points are determined. In the present study the structured packing Sulzer BX 500 is used. The experiments with the removal rate variation are carried out so that the results can directly be compared to those from a previous study in the same plant that was carried out using Sulzer Mellapak 250.Y. A strategy for identifying the influence of absorption kinetics on the results is proposed, which is based on a variation of the gas load at a constant L/G ratio and provides valuable insight on the transferability of pilot plant results.