Numerical Investigation of Gas-Liquid Reacting Flow in a Jet-Type Singlet Oxygen Generator

A numerical simulation was carried out to investigate the process of gas-liquid reaction in a jet-type singlet oxygen generator by using volume-of-fluid coupled with large eddy simulation. The coupled hydrodynamic and reaction simulations provide detailed information about the reacting flow. Results reveal that the reaction aggravates the jet instability and affects the jet structure significantly due to the differential pressure around the liquid jet. The effects of gas velocity on chlorine conversion and the yield of singlet oxygen were investigated. The key is the increasing of the interface area rather than the convection. This numerical simulation study is convenient for the design of singlet oxygen reactors and the research of gas-liquid two-phase flow with reaction.     

Design and Properties of Porphyrin-based Singlet Oxygen Generator

In this review, we address recent studies of porphyrin-based molecular systems for efficient singlet oxygen (¹O₂) generation. Porphyrins have a highly conjugated, delocalized 18-π electron system (for the shortest cyclic path) that is responsible for the strong absorption and emission characteristics in the visible region. Singlet oxygen is useful for applications in photodynamic cancer therapy (PDT), photooxidation of toxic molecules, and photoproduction of important intermediates for various chemicals owing to its high oxidation ability. Porphyrin and its analogues have been investigated as photosensitizers for ¹O₂ generation. The production of ¹O₂ is successfully regulated by photophysical parameters, such as intersystem crossing, triplet state (T₁) lifetime, and photosensitizer to ³O₂ energy transfer in molecular systems. Introduction of substituents with heavy atoms (halogen, metal) and radicals onto the photosensitizer (PS) exerts a strongly positive impact on intersystem crossing of the singlet excited state of the PS, promoting generation of the triplet excited state. Environmental conditions, such as solvent and pH, may also influence ¹O₂ generation. As a means to limit cellular photodamage, two-photon absorption and DNA switches for ¹O₂ generation have been proposed and developed. Achieving control of singlet oxygen generation is pertinent to many arenas at the cutting edge of modern science, ranging from the chemical industry to biomedical applications.     

Modeling of High‐Pressure Ethene Homo‐ and Copolymerization

While reaction engineering of low‐molecular weight compounds mainly focuses on equilibria and selectivities, polymer properties are tremendously influenced by molecular weight distribution as well as branching structure. In order to determine the branching structure of low‐density polyethylene (LDPE) copolymers in dependence on chosen process conditions, a Monte‐Carlo approach was developed. By modeling the topology as well as the comonomer distribution in the polymer chains a deeper insight in the process‐microstructure‐properties relationship is gained.     

Influence of Membrane Intrusion on Permeate‐Sided Pressure Drop During High‐Pressure Reverse Osmosis

By replacing thermal concentration processes, high‐pressure reverse osmosis has the potential to contribute to cost and energy savings regarding concepts for industrial water reuse. To provide a better understanding of the spiral‐wound element behavior during high‐pressure operation, this study focusses on the investigation of their performance by scrutinizing the crucial effect of the permeate‐sided pressure drop induced by membrane‐spacer interactions. The experiments show a considerable influence of membrane intrusion on the element performance with a strong dependence on the feed pressure.     

Deoxygenation of Methanol over ZSM‐5 in a High‐Pressure Catalytic Pyroprobe

Deoxygenation is a critical step in making hydrocarbon‐rich biofuels from biomass constituents. Although the thermal effects of oxygenate aromatization have been widely reported, the effect of pressure on this critical reaction has not yet been closely investigated, one primary reason being the unavailability of a reactor that can pyrolyze oxygenates, especially those in solid form, under pressurized conditions. Here, the first of a series of studies on how oxygenates behave when catalytically pyrolyzed under elevated pressure and temperature conditions is reported. Methanol, the simplest alcohol, was selected as the candidate to study the chemical phenomena that occur under pressurized catalytic pyrolysis. The reactions were carried out over the shape‐selective catalyst ZSM‐5 (SiO₂/Al₂O₃ = 30) under varying pressure (0 to 2.0684 MPa (300 psi) in 0.3447 MPa (50 psi) increments) and temperature (500 to 800 °C in 50 °C increments) conditions. Benzene, toluene, ethyl benzene, and xylenes (BTEX) were analyzed as the deoxygenated products of the reaction. The results indicate that the reactor pressure significantly affects deoxygenated product composition.     

Evaluation of a New High‐Pressure Dispersion Unit (HPN) for Emulsification

Emulsification plays an important role in the formulation of lipophilic pharmaceutical agents. These substances are often included in the disperse phase of an oil‐in‐water emulsion. To reach a high bioavailability and a good long‐term stability, drop sizes much less than 1 micron are required. For the generation of such emulsions, energy densities of a quality which can only be reached in high‐pressure systems, are necessary. Actually available apparatus, such as high‐pressure homogenizers fitted with valves, microfluidizer or jet disperser, reach particle sizes of about 0.2 micron in continuous processes. It is indispensable to produce emulsions with smaller globules in order to receive a maximum of diversity in application. Therefore, dispersion units with a higher efficiency in drop breakup are needed. Especially in the case of parenterally administered medicament formulations an average particle size between 0.04 and 0.1 microns is requested which is up to now not reachable by continuous emulsification. In this study the drop breakup behavior of a new high‐pressure nozzle is investigated with the example of oil‐in‐water emulsions and compared to the breakup behavior of a state‐of‐the‐art nozzle and to available data published.     

变压吸附空分制氧的技术进展

介绍了近年来变压吸附空分制氧的技术进展情况,分别从空分制氧的工艺和吸附剂的改进状况进行了详细论述,并简单的描述了空分制氧的发展前景。     

Impact of Thermo‐Physical Data on the Modeling of High‐Pressure Polymerizations

Modeling the high‐pressure polymerization of ethene is of vital importance in order to avoid costly high‐pressure experiments when it comes to process optimization and product design. However, closing the heat balance when modeling high‐pressure tubular reactors with a counter‐current jacket cooling is still difficult. In this contribution the influence of thermo‐physical properties – namely viscosity and heat capacity – on the simulation results was investigated. Various literature sources were evaluated and a variety of simulations were conducted, showing that both properties influence the resulting temperature profiles and conversions visibly, while the molecular weight distribution was not affected. Uncertainties of the heat capacity of 5 % could be compensated by varying initiator efficiency and fouling layer thickness within physically reasonable boundaries.     

电化学制氧机中的炭电极研制

简介了电化学制氧机中炭电极的制备,测试了膜片的性能,同时研制了用该膜片作阴极的制氧机,并与其它文献报道的同类制氧机进行性能对比,结果表明自制的制氧机性能最佳.     

变压吸附制氮机均压方式的研究

简述了变压吸附制氮装置工艺流程、工作过程和均压方式。介绍了对变压吸附制氮装置等势平衡均压、不等势平衡均压、等势不平衡均压、不等势不平衡均压方式的实验结果,着重介绍了等势不平衡均压方式的特点。     

Isoprenoid Alcohols are Susceptible to Oxidation with Singlet Oxygen and Hydroxyl Radicals

Isoprenoids, as common constituents of all living cells, are exposed to oxidative agents—reactive oxygen species, for example, singlet oxygen or hydroxyl radicals. Despite this fact, products of oxidation of polyisoprenoids have never been characterized. In this study, chemical oxidation of isoprenoid alcohols (Prenol‐2 and ‐10) was performed using singlet oxygen (generated in the presence of hydrogen peroxide/molybdate or upon photochemical reaction in the presence of porphyrin), oxygen (formed upon hydrogen peroxide dismutation) or hydroxyl radical (generated by the hydrogen peroxide/sonication, UV/titanium dioxide or UV/hydrogen peroxide) systems. The structure of the obtained products, hydroxy‐, peroxy‐ and heterocyclic derivatives, was studied with the aid of mass spectrometry (MS) and nuclear magnetic resonance (NMR) methods. Furthermore, mass spectrometry with electrospray ionization appeared to be a useful analytical tool to detect the products of oxidation of isoprenoids (ESI–MS analysis), as well as to establish their structure on the basis of the fragmentation spectra of selected ions (ESI–MS/MS analysis). Taken together, susceptibility of polyisoprenoid alcohols to various oxidizing agents was shown for the first time.     

High‐Pressure Homogenization as a Process for Emulsion Formation

Emulsions find a wide range of application in industry and daily life. In the pharmaceutical industry lipophilic active ingredients are often formulated in the disperse phase of oil‐in‐water emulsions. Milk, butter, and margarine are examples of emulsions in daily life. In the metal processing industry emulsions are used in the form of coolants. Emulsions can be produced with different systems. In the following, the process of high‐pressure homogenization is briefly compared to other common mechanical emulsification systems. To facilitate the selection of an emulsification system, the influence of the most important parameters of the emulsion formulation on the resulting mean droplet diameter in the most prevalent continuous emulsification systems is outlined. Subsequently, the most common high‐pressure homogenization systems are discussed in detail. On the basis of data from the literature and own experimental results the described high‐pressure homogenization systems will be compared regarding their attainable mean droplet diameter. It shows that homogenizers with a relatively simple geometry like the patented “combined orifice valve” (Kombi‐Blende) attain the smallest mean droplet diameters. The advantage of the “combined orifice valve” compared to other high‐pressure homogenization systems is not more efficient droplet disruption but rather more efficient droplet stabilization against coalescence immediately after the droplet breakup. The greatest research potential concerning the development of new high‐pressure homogenization systems is still to be seen in improvements of droplet stabilization, i.e., the reduction of coalescence.     

Technological Aspects of Nanoemulsion Formation of Low‐Fat Foods Enriched with Vitamin E by High‐Pressure Homogenization

Formation of a low‐fat oil‐in‐water (O/W) nanoemulsion enriched with vitamin E using the nonionic surfactant Tween 40 is studied by means of a high‐pressure homogenizer. The effect of different process variables of the emulsification process, including pressure, temperature, and concentration of the emulsifying agent, is evaluated. The relation between pressure and the obtained mean droplet diameter is derived and described by an equation which can be taken as a basis of any process design. The droplet size can be decreased by increasing the vitamin E concentration. A higher fat content slightly affects the droplet size distribution and the mean droplet diameter of the nanoemulsion, so it is recommended to use preparations of nanoemulsions with low fat contents enriched with vitamin E for dietary supplement.     

The High‐Pressure Characterization of Energetic Materials: 1,4‐Dimethyl‐5‐Aminotetrazolium 5‐Nitrotetrazolate

In‐situ high‐pressure room temperature synchrotron X‐ray diffraction and infrared microspectroscopy were used to examine the structural and vibrational properties and the equation of state of 1,4‐dimethyl‐5‐aminotetrazolium 5‐nitrotetrazolate (DMATNT). The X‐ray measurements show a smoothly varying pressure‐volume relationship to 20 GPa. However, the anisotropic ratios of the unit cell parameters reveal a discontinuity near 3.3 GPa, which can be attributed to an irreversible isostructural phase transition. A significant increase in the Infrared spectral intensity near this pressure coupled with Dayvdov splitting of the NO₂ bending and scissoring modes suggest the transition results in a skewing of the NO₂ groups and increasing asymmetry of the hydrogen bonding sublattice.     

High‐Pressure Treatment of Wood – Combination of Mechanical and Thermal Drying in the “I/D Process”

Thermal drying of materials with internal pores is always a time‐consuming and energy‐intensive step within a production process. For chemical and pharmaceutical mass products and, in particular, for wood as an important raw material it is desirable to reduce the water content before thermal treatment by mechanical operations. The wood‐processing industry, facing a rising stress of competition, is forced more than ever to offer high‐quality products at lowest prices. Today, drying of timber is mostly done by air drying or by technical drying in kiln dryers. In any case, drying is necessary to prevent deterioration in quality by shrinkage, formation of cracks, discoloration or infestation. A new process of dewatering wood by combining mechanical and thermal means has been developed at the University of Karlsruhe. Compared to conventional drying processes, short drying times and a low residual moisture content can be achieved and, thus, energy consumption and costs can be reduced. In industrial wood drying only thermal processes (e.g., convective kiln drying, vacuum drying, etc.) have been established because so far no method has been known for removing liquid by mechanical force without significant change in wood structure. With the new I/D process chances for alternatives to conventional thermal drying or for mechanothermal applications are offered.     

Analytic High‐Pressure Phase Equilibria. Part II: Gas Chromatography and Sampling Method Development

The phase equilibria of supercritical CO₂‐alkane‐alcohol mixtures were studied using online gas chromatography. Gas chromatograph design criteria and quantitative detector calibration methods are presented. An adapted manual calibration injection technique eliminated liner overload and pressure wave effects. Observation of the cell contents has proven essential for accurate vapor phase sampling. Visuals, often not visible to the naked eye, show that sampling can disrupt an equilibrated high‐pressure system even though pressure and temperature remain constant within 0.1 bar and 0.01 °C. Such disruptions may manifest in one of three phenomena: global mist formation, localized mist formation, or no‐warning droplet formation.