Scale‐down des Strahlzonen‐Schlaufenreaktors: Entwicklung eines Screening‐Tools für transportlimitierte chemische Reaktionen

The jet zone loop reactor (JZR) is a high performance loop reactor in which it was shown on different reactions that the use of multiscale transport phenomena leads to a significant increase in the space‐time yield and selectivity. As the use of a JZR in a semi‐industrial scale means a high effort, the development of a comparable screening tool in a laboratory scale is the logical step in which the new technology can be estimated easily and quickly. Experimental hydrodynamic studies of the laboratory reactor showed that significant integral and local parameters are similar to the reactor in semi‐industrial scale, so that the reactor could be used to study a consecutive fast chlorination.     

Potenzial des IR Micro‐Imaging zur In‐situ‐Untersuchung chemischer Reaktionen in nanoporösen Katalysatoren

The in‐situ study of chemical reactions is an intensively studied research topic. A suitable method for this investigation is the IR micro‐imaging technique, which allows to record space‐ and time‐resolved IR spectra. The preparation of a suitable model system with a 3D pore system for the in‐situ recording of concentration profiles using IR micro‐imaging is described, enabling the space‐ and time‐resolved monitoring of catalytic reactions in nanoporous catalysts for the first time. The model system consists of a nanoporous glass monolith with gas‐tight sealed outer surface, therefore, enabling the recording of concentration profiles of cyclohexane and cyclohexane‐benzene mixtures as a function of time.     

Degradation of 1‐amino‐4‐bromoanthraquinone‐2‐sulfonic acid using combined airlift bioreactor and TiO2‐photocatalytic ozonation

BACKGROUND: Traditional treatment systems failed to achieve efficient degradation of anthraquinone dye intermediates at high loading. Thus, an airlift internal loop reactor (AILR) in combination with the TiO₂‐photocatalytic ozonation (TiO₂/UV/O₃) process was investigated for the degradaton of 1‐amino‐ 4‐bromoanthraquinone‐2‐ sulfonic acid (ABAS). RESULTS: The AILR using Sphingomonas xenophaga as inoculum and granular activated carbon (GAC) as biocarrier, could run steadily for 4 months at 1000 mg L^?1 of the influent ABAS. The efficiencies of ABAS decolorization and chemical oxygen demand (COD) removal in AILR reached about 90% and 50% in 12 h, respectively. However, when the influent ABAS concentration was further increased, a yellow intermediate with maximum absorbance at 447 nm appeared in AILR, resulting in the decrease of the decolorization and COD removal efficiencies. Advanced treatment of AILR effluent indicated that TiO₂/UV/O₃ process more significantly improved the mineralization rate of ABAS bio‐decolorization products with over 90% TOC removal efficiency, compared with O₃, TiO₂/UV and UV/O₃ processes. Furthermore, the release efficiencies of Br^? and SO₄^2? could reach 84.5% and 80.2% during TiO₂/UV/O₃ treatment, respectively, when 91.5% TOC removal was achieved in 2 h. CONCLUSION: The combination of AILR and TiO₂/UV/O₃ was an economic and efficient system for the treatment of ABAS wastewater. © 2012 Society of Chemical Industry     

Oxidative degradation of 4‐nitrophenol in UV‐illuminated titania suspension

An internally‐irradiated annular photoreactor has been used to investigate the oxidative degradation of aqueous 4‐nitrophenol with titania as the photocatalyst. Reaction runs were performed over a 3‐h period and in practically all cases, complete degradation was possible within about 2 h. The kinetics was determined as a function of nitrophenol concentration, oxygen partial pressure, catalyst loading, pH, temperature and light intensity. The reaction was characterised by a relatively low activation energy of 7.83 kJ mol^?1 although transport intrusions were negligible. Rate decreased almost exponentially with pH while a quadratic (maximum) behaviour with respect to both oxygen pressure and nitrophenol concentration is symptomatic of self‐inhibition possibly due to the formation of intermediates which competitively adsorb on similar sites to the reactants. Increased catalyst dosage also improved the reaction rate although the possible effects of light scattering and solution opacity caused a drop at loadings higher than about 1.20 g dm^?3. Rate, however, has a linear dependency on light intensity, suggesting that hole–electron recombination processes were negligible at the conditions investigated. © 2001 Society of Chemical Industry     

CO2 methanation: Optimal start‐up control of a fixed‐bed reactor for power‐to‐gas applications

Utilizing volatile renewable energy sources (e.g., solar, wind) for chemical production systems requires a deeper understanding of their dynamic operation modes. Taking the example of a methanation reactor in the context of power‐to‐gas applications, a dynamic optimization approach is used to identify control trajectories for a time optimal reactor start‐up avoiding distinct hot spot formation. For the optimization, we develop a dynamic, two‐dimensional model of a fixed‐bed tube reactor for carbon dioxide methanation which is based on the reaction scheme of the underlying exothermic Sabatier reaction mechanism. While controlling dynamic hot spot formation inside the catalyst bed, we prove the applicability of our methodology and investigate the feasibility of dynamic carbon dioxide methanation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 23–31, 2017     

Hydrodynamik und Stofftransport in einem Perlschnurreaktor für Gas/Flüssig/Fest‐Reaktionen

In this work, a pellet string reactor was characterized with respect to hydrodynamics and mass transfer. The catalyst packing consists of a cylindrical channel with a diameter of 1.41 mm, which was filled with spherical catalyst particles, having an outer diameter of 0.8 mm. Under reaction conditions (liquid phase hydrogenation of α‐methylstyrene) overall (gas‐liquid‐solid) volumetric mass transfer coefficients for hydrogen between 0.8 and 5.5 s^–1 were computed. Due to high mass transfer rates and simple reactor geometry, pellet string reactors can be applied in industry as highly efficient reaction units.     

Micro‐structured Bi1.5Y0.3Sm0.2O3−δ catalysts for oxidative coupling of methane

Bi_1.5Y_0.3Sm_0.2O_3?δ (BYS), a ceramic material showing great activity and selectivity to oxidative coupling of methane (OCM), has been fabricated into catalyst rings (i.e., capillary tubes) with a plurality of self‐organized radial microchannels. The unique microchannels inside such BYS catalyst rings allow easier access of reactants, as well as increased the surface area, which potentially contributes to higher reaction efficiencies due to improved mass transfer. The micro‐structured BYS catalyst rings were investigated systematically via two types of reactors; (1) randomly packed fixed bed reactor and (2) monolithic‐like structured reactor. These two reactor designs have different flow patterns of reactants, that is, non‐ideal and ideal flows, which can significantly affect the final OCM performance. A remarkable improvement in C₂₊ yield (Y_C2+ > 20%) was obtained in the monolith‐like structured reactor, in contrast to randomly packed powder and micro‐structured rings (Y_C2+ < 15%), which proves the advantages of using a micro‐structured catalyst with an ideal flow in the feed for OCM. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3451–3458, 2015     

The β‐δ‐Phase Transition and Thermal Expansion of Octahydro‐1,3,5,7‐Tetranitro‐1,3,5,7‐Tetrazocine

Phase behavior of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocine (HMX) is investigated by X‐ray powder diffraction (XRD). The XRD patterns at elevated temperature show that there is a co‐existing temperature range of β‐ and δ‐phase during the phase transition process. Additionally, mechanical forces can catalyze the conversion from δ‐ back to β‐phase. Based on the diffraction patterns of β‐ and δ‐phase at different temperatures, we calculate the coefficients of thermal expansion by Rietveld refinement. For β‐HMX, the linear coefficients of thermal expansion of a‐axis and b‐axis are about 1.37×10⁻⁵ and 1.25×10⁻⁴ °C⁻¹. A slight decrease in c‐axis with temperature is also observed, and the value is about −0.63×10⁻⁵ °C⁻¹. The volume coefficient of thermal expansion is about 1.60×10⁻⁴ °C⁻¹, with a 2.2% change from 30 to 170 °C. For δ‐HMX, the linear coefficients of thermal expansion of a‐axis and c‐axis are found to be 5.39×10⁻⁵ and 2.38×10⁻⁵ °C⁻¹, respectively. The volume coefficient of thermal expansion is about 1.33×10⁻⁴ °C⁻¹, with a 2.6% change from 30 to 230 °C. The results indicate that β‐HMX has a similar volume coefficient of thermal expansion compared with δ‐HMX, and there is about 10.5% expansion from β‐HMX at 30 °C to δ‐HMX at 230 °C, of which about 7% may be attributed to the reconstructive transition.     

Formation of 4‐Hydroxy‐2‐Trans‐Nonenal,a Toxic Aldehyde,in Thermally Treated Olive and Sunflower Oils

4‐Hydroxy‐2‐trans‐nonenal (HNE) is a toxic aldehyde produced mostly in oils containing polyunsaturated fatty acid due to heat‐induced lipid peroxidation. The present study examined the effects of the heating time, the degree of unsaturation, and the antioxidant potential on the formation of HNE in two light olive oils (LOO) and two sunflower oils (one high oleic and one regular) at frying temperature. HNE concentrations in these oil samples heated for 0, 1, 3, and 5 hours at 185 °C were measured using high‐performance liquid chromatography. The fatty‐acid distribution and the antioxidant capacity of these four oils were also analyzed. The results showed that all oils had very low HNE concentrations (<0.5 μg g^?1 oil) before heating. After 5 hours of heating at 185 °C, HNE concentrations were increased to 17.98, 25.00, 12.51, and 40.00 μg g^?1 in the two LOO, high‐oleic sunflower oil (HOSO), and regular sunflower oil (RSO), respectively. Extending the heating time increased HNE formation in all oils tested. It is related to their fatty‐acid distributions and antioxidant capacities. RSO, which contained high levels of linoleic acid (59.60%), a precursor for HNE, was more susceptible to degradation and HNE formation than HOSO and LOO, which contained only 6–8% linoleic acid.     

Combined Effect of Agitation/Aeration and Fed‐Batch Strategy on Ubiquin‐ one‐10 Production by Pseudomonas diminuta

The effects of aeration rate and agitation speed on ubiquinone‐10 (CoQ10) submerged fermentation in a stirred‐tank reactor using Pseudomonas diminuta NCIM 2865 were investigated. CoQ10 production, biomass formation, glycerol utilization, and volumetric mass transfer coefficient (k_La) were affected by both aeration and agitation. An agitation speed of 400 rpm and aeration rate of 0.5 vvm supported the maximum production (38.56 mg L^–1) of CoQ10 during batch fermentation. The fermentation run supporting maximum production had an k_La of 27.07 h^–1 with the highest specific productivity and CoQ10 yield of 0.064 mg g^–1h^–1 and 0.96 mg g^–1 glycerol, respectively. Fermentation kinetics performed under optimum aeration and agitation showed the growth‐associated constant (a = 5.067 mg g^–1) to be higher than the nongrowth‐associated constant (β = 0.0242 mg g^–1h^–1). These results were successfully utilized for the development of fed‐batch fermentation, which increased the CoQ10 production from 38.56 mg L^–1 to 42.85 mg L^–1.     

Thermal and Combustion Properties of 3,4‐Bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF)

Thermal decomposition of melted 3,4‐bis(3‐nitrofurazan‐4‐yl)furoxan (DNTF) in isothermal conditions was studied. The burning rates of DNTF were measured in the pressure interval of 0.1–15 MPa. The thermal stability of DNTF was found to be close to the stability of HMX, while the burning rate of DNTF was close to the burning rate of CL‐20. The thermocouple measurements in the combustion wave of DNTF showed that combustion of DNTF was controlled by the gas‐phase mechanism. The DNTF vapor pressure was determined from thermocouple measurements and agreed well with data obtained at low temperatures under isothermal conditions.