Production and properties assessment of biochars from rapeseed and poplar waste biomass for environmental applications in Romania.

Biochar obtained by pyrolysis is receiving great research interest as it is perceived to be a renewable resource available for agronomic and environmental applications. Since biochar is a highly heterogeneous material with chemical composition that varies widely depending on feedstock and pyrolysis conditions, this study compares the characteristics of biochar produced by pyrolysis at six temperature levels ranging between 300 and 800 °C of two types of biomass, i.e. rapeseed straw (RS)-agriculture waste and poplar tree shavings (PP)-forest waste from furniture making. Twelve biochars were generated via pyrolysis under low oxygen conditions of the selected biomasses in an electrically heated batch reactor. To determine how pyrolysis temperature affects the properties of biochars and consequently their possible utilization, physical, chemical, thermal, porosity and EDX analysis were measured for all biochars and for the corresponding feedstocks. SEM images of the biochar revealed that an increase in temperature led to a higher number of pores for PP biochar compared to RS biochar, and that PP biochar pores tended to shrink with temperature. The elemental composition and the pH of biochars were also compared. Based on the experimental results a utilization matrix was designed as to offer indications concerning possible applications of RS and PP biochars in substitution to fossil derived products for soil remediation (e.g., agriculture fertilizers) and in environmental applications (e.g., removal of pollutants).

Novel Design Integrating a Microwave Applicator into a Crystallizer for Rapid Temperature Cycling. A Direct Nucleation Control Study.

The control of nucleation in crystallization processes is a challenging task due to the often lacking knowledge on the process kinetics. Inflexible (predetermined) control strategies fail to grow the nucleated crystals to the desired quality because of the variability in the process conditions, disturbances, and the stochastic nature of crystal nucleation. Previously, the concept of microwave assisted direct nucleation control (DNC) was demonstrated in a laboratory setup to control the crystal size distribution in a batch crystallization process by manipulating the number of particles in the system. Rapid temperature cycling was used to manipulate the super(under)saturation and hence the number of crystals. The rapid heating response achieved with the microwave heating improved the DNC control efficiency, resulting in halving of the batch time. As an extension, this work presents a novel design in which the microwave applicator is integrated in the crystallizer, hence avoiding the external loop though the microwaves oven. DNC implemented in the 4 L unseeded crystallizer, at various count set points, resulted in strong efficiency enhancement of DNC, when compared to the performance with a slow responding system. The demonstrated crystallizer design is a basis for extending the enhanced process control opportunity to other applications.

Subtle Microwave-Induced Overheating Effects in an Industrial Demethylation Reaction and Their Direct Use in the Development of an Innovative Microwave Reactor.

A systematic study of the conventional and microwave (MW) kinetics of an industrially relevant demethylation reaction is presented. In using industrially relevant reaction conditions the dominant influence of the solvent on the MW energy dissipation is avoided. Below the boiling point, the effect of MWs on the activation energy Ea and k0 is found nonexistent. Interestingly, under reflux conditions, the microwave-heated (MWH) reaction displays very pronounced zero-order kinetics, displaying a much higher reaction rate than observed for the conventionally thermal-heated (CTH) reaction. This is related to a different gas product (methyl bromide, MeBr) removal mechanism, changing from classic nucleation into gaseous bubbles to a facilitated removal through escaping gases/vapors. Additionally, the use of MWs compensates better for the strong heat losses in this reaction, associated with the boiling of HBr/water and the loss of MeBr, than under CTH. Through modeling, MWH was shown to occur inhomogeneously around gas/liquid interfaces, resulting in localized overheating in the very near vicinity of the bubbles, overall increasing the average heating rate in the bubble vicinity vis-à-vis the bulk of the liquid. Based on these observations and findings, a novel continuous reactor concept is proposed in which the escaping MeBr and the generated HBr/water vapors are the main driving forces for circulation. This reactor concept is generic in that it offers a viable and low cost option for the use of very strong acids and the managed removal/quenching of gaseous byproducts.

Batch and continuous flow preparation of Hantzsch 1,4-dihydropyridines under microwave heating and simultaneous real-time monitoring by Raman spectroscopy. An exploratory study.

Dialkyl 1,4-dihydro-2,6-dimethylpyridine-3,5-dicarboxylates have been prepared in a batch mode under conventional heating as well as under continuous flow conditions in the Miniflow 200SS, Sairem's microwave-assisted batch and continuous flow equipment. Real-time monitoring of the reactions by Raman spectroscopy enabled to compare both heating modes and to determine (optimized) reaction times.

Microwave plasma removal of sulphur hexafluoride.

Sulphur hexafluoride (SF(6)) gas is a common pollutant emitted during the plasma etching of thin films and plasma cleaning chemical vapor deposition (CVD) production processes used in the semiconductor industry. In this paper a method using microwave (2.45GHz frequency) plasmas sustained at atmospheric pressure for the abatement of SF(6) is investigated experimentally for various gas mixture constituents and operating conditions, with respect to its ability to decompose SF(6) to less harmful molecules. The destruction and removal efficiencies (DRE) of plasma abatement of SF(6) at concentrations between 1.7 and 5% in nitrogen in the presence of water vapor were studied as a function of the total gas flow rate and microwave power. Water vapor proved to be an effective source of free radical species that reacts with the radicals and ions resulting from SF(6) fragmentation in the plasma and also, it proved to reduce the process by-products. It was measured that approximately 25% of the initial SF(6) is converted to SO(2). Destruction and removal efficiencies of SF(6) up to 99.9% have been achieved.

Preparation of polyelectrolytes for wastewater treatment.

Liquid-phase polymerisation of acrylamide-acrylic acid to form polyelectrolytes used in wastewater cleaning was examined using accelerated electron beam and microwave irradiation methods. Polymerisation was carried out in aqueous solutions at temperatures approximately 60 degrees C. Monomers total concentration was established at 40% (36% acrylamide and 4% acrylic acid). Only using the features of simultaneous radiation-induction and microwave heating can result in the formation of linear polymer chains with good water solubility and low residual monomer concentration. The flocculation capacity of the obtained polymers was tested using two wastewaters, one sampled from a slaughterhouse and the other from a vegetable oil plant. Quality indicators such as total suspended matters (TSM), chemical oxygen demand (COD), biological oxygen demand (BOD) and fat, oils and grease (FOG) were measured before and after the treatment with polymeric flocculants and compared with the results obtained in classical treatment with Al(2)(SO(4))(3). It was found that the combined treatment with polymers and Al(2)(SO(4))(3) increases the degree of purification of both wastewaters up to 99%.

Studies of 2.45 GHz microwave induced plasma abatement of CF4.

Microwave plasmas at 2.45 GHz frequency operated at atmospheric pressure in synthetic gas mixtures containing N2 and CF4 are investigated experimentally for various operating conditions, with respect to their ability to destroy perfluorocompounds. It was found that the destruction and removal efficiency of the process is highly dependent on the total gas flow and concentration of CF4. Destruction and removal efficiencies of CF4 up to 98% have been achieved using 1.9 kW of microwave power at 16 L/min total flow rate.

Emission control of SO2 and NOx by irradiation methods.

Microwave discharges at 2.45 GHz frequency and accelerated electron beams operated at atmospheric pressure in synthetic gas mixtures containing N(2), O(2), CO(2), SO(2), and NO(x) are investigated experimentally for various gas mixture constituents and operating conditions, with respect to their ability to purify exhaust gases. An original experimental unit easily adaptable for both separate and simultaneous irradiation with microwaves and electron beams was set up. The simultaneous treatment with accelerated electron beams and microwaves was found to increase the removal efficiency of NO(x) and SO(2) and also helped to reduce the total required dose rate with approximately 30%. Concomitant removal of NO(x) ( approximately 80%) and SO(2) (>95%) by precipitation with ammonia was achieved.