Filtern
Erscheinungsjahr
- 2017 (6) (entfernen)
Dokumenttyp
Sprache
- Englisch (6)
Schlagworte
- Fireball (3)
- Organic peroxide (3)
- DTBP (2)
- Microemulsions (2)
- Process Analytical Technology (2)
- Simulation (2)
- Steel drum (2)
- Dispersion (1)
- EuroPACT (1)
- Hydroformylation (1)
Organic peroxides are capable to form fireballs with explosive violence. Only fireball models for liquid hydrocarbon fuels are available for the assessment of the thermal radiation properties. Because the development of such fireballs usually differ from those of organic peroxides the properties need to be characterized by modified equations. In this study liquid organic peroxide fireballs from 16 kg to 155 kg substance masses are characterized and compared to selected existing correlations. Flame characteristics and irradiances are measured with infrared cameras and heat flux sensors. All fireballs are consequences of simulated worst case scenarios where filled steel drums are engulfed by fire with varying heat impact. The differences of the given semi-empirical equations and the presented experimental work are explained. A new model is proposed for organic peroxide fireballs by modifying the constants of the known equations. The thermal radiation impact and safety distances are calculated and compared.
Single and multiple fireballs of di-tert-butyl peroxide are numerically investigated using ANSYS CFX. Calculations contain varying inlet conditions, scale-adaptive shear stress turbulence modeling and one-step combustion reaction on a three-dimensional hexahedral mesh. Time-resolved flame temperatures, sizes and thermal radiation are compared to experimental results. There, fireballs were generated by fire engulfment of steel drums containing 200 l substance. After a vigorous burning, the remaining peroxide forms single and multiple fireballs involving 10 % to 20 % of the initial amount. The comparison of all simulations and two selected experiments show the special numerical treatment required for organic peroxides. Finally, the numerical predictions of irradiance in 30 m distance to the fire show a good agreement for both experiments. This proves the use of CFD as an appropriate method for thermal hazard assessment and the prediction of safety distances for organic peroxide fireballs.
To simulate a full fire engulfment during transportation or storage a closed removable head steel drum filled with 200 l Di-tert-butyl peroxide (DTBP) is subjected to a wood fire. Due to the enormous heat flux and the exothermic self-decomposition large flames arise and finally multiple fireballs occur. The fireballs consume up to 20 % of the total mass (20 % equals to 31 kg). They are characterized by high surface emissive power and large flames associated with high thermal radiation causing spontaneous ignition of objects in the surrounding. The measured sizes of the DTBP fireballs are smaller compared to the results of the general equations for hydrocarbon fireballs. Because these equations are recommended by the Health and Safety Executive (UK) to be applicable for organic peroxides explicit comparisons of DTBP with LPG, diesel and gasoline concerning the characteristics of fireballs are carried out. Also the burning time is compared and confirms a faster combustion of the peroxide. Moreover, the development of size and emissive power for DTBP and diesel fireballs are compared in a normalized graph. The results provide the assumption that new empirical models are required to be developed for hazard assessment of organic peroxide fireballs.
Within the Collaborative Research Center InPROMPT a novel process concept for the hydroformylation of long-chained olefins is studied in a mini-plant, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro¬emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the high sensitivity of this multi-phase system with regard to changes in temperature and composition demands a continuous observation of the reaction to achieve a reliable and economic plant operation. For that purpose, we tested the potential of both online NMR and Raman spectroscopy for process control. The lab-scale experiments were supported by off-line GC-analysis as a reference method.
A fiber optic coupled probe of a process Raman spectrometer was directly integrated into the reactor. 25 mixtures with varying concentrations of olefin (1-dodecene), product (n-tridecanal), water, n-dodecane, and technical surfactant (Marlipal 24/70) were prepared according to a D-optimal design. Online NMR spectroscopy was implemented by using a flow probe equipped with 1/16” PFA tubing serving as a flow cell. This was hyphenated to the reactor within a thermostated bypass to maintain process conditions in the transfer lines.
Partial least squares regression (PLSR) models were established based on the initial spectra after activation of the reaction with syngas for the prediction of unknown concentrations of 1-dodecene and n-tridecanal over the course of the reaction in the lab-scale system. The obtained Raman spectra do not only contain information on the chemical composition but are further affected by the emulsion properties of the mixtures, which depend on the phase state and the type of micelles. Based on the spectral signature of both Raman and NMR spectra, it could be deduced that especially in reaction mixtures with high 1-dodecene content the formation of isomers as a competitive reaction was dominating. Similar trends were also observed during some of the process runs in the mini-plant. The multivariate calibration allowed for the estimation of reactants and products of the hydroformylation reaction in both laboratory setup and mini-plant.
Hydroformylation of short-chained olefins has been established as a standard industrial process for the production of C2 to C6 aldehydes. Using aqueous solutions of transition metal complexes these processes are carried out homogeneously catalyzed. A biphasic approach allows for highly efficient catalyst recovery. Regarding renewable feedstocks, the hydroformylation of long-chained alkenes (> C10) in a biphasic system, using highly selective rhodium catalysts has yet not been shown. Therefore, the Collaborative Research Center SFB/TR 63 InPROMPT develops new process concepts, involving innovative tuneable solvent systems to enable rather difficult or so far nonviable synthesis paths. One possible concept is the hydroformylation of long-chained alkenes in microemulsions. For this, a modular mixer-settler concept was proposed, combining high reaction rates and efficient catalyst recycling via the application of technical grade surfactants. The feasibility of such a concept is evaluated in a fully automated, modular mini-plant system within which the characteristics of such a multiphase system pose several obstacles for the operation. Maintaining a stable phase separation for efficient product separation and catalyst recycling is complicated by small and highly dynamic operation windows as well as poor measurability of component concentrations in the liquid phases. In this contribution, a model-based strategy is presented to enable concentration tracking and phase state control within dynamic mini-plant experiments. Raman spectroscopy is used as an advanced process analytical tool, which allows for online in-situ tracking of concentrations. Combined with optical and conductivity analysis optimal plant trajectories can be calculated via the solution of dynamic optimization problem under uncertainty. Applying these, a stable reaction yield of 40 % was achieved, combined with an oil phase purity of 99,8 % (total amount of oily components in the oil phase) and catalyst leaching below 0.1 ppm.
Reaction monitoring in disperse systems, such as emulsions, is of significant technical importance in various disciplines like biotechnological engineering, chemical industry, food science, and a growing number other technical fields. These systems pose several challenges when it comes to process analytics, such as heterogeneity of mixtures, changes in optical behavior, and low optical activity. Concerning this, online nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for process monitoring in complex reaction mixtures due to its unique direct comparison abilities, while at the same time being non-invasive and independent of optical properties of the sample. In this study the applicability of online-spectroscopic methods on the homogeneously catalyzed hydroformylation system of 1-dodecene to tridecanal is investigated, which is operated in a mini-plant scale at Technische Universität Berlin. The design of a laboratory setup for process-like calibration experiments is presented, including a 500 MHz online NMR spectrometer, a benchtop NMR device with 43 MHz proton frequency as well as two Raman probes and a flow cell assembly for an ultraviolet and visible light (UV/VIS) spectrometer. Results of high-resolution online NMR spectroscopy are shown and technical as well as process-specific problems observed during the measurements are discussed.