Production of FAME from acid oil,a by-product of vegetable oil refining

Simple alkyl FA esters have numerous uses, including serving as biodiesel, a fuel for compression ignition (diesel) engines. The use of acid-catalyzed esterification for the synthesis of FAME from acid oil, a by-product of edible vegetable oil refining that is produced from soapstock, was investigated. Soybean acid oil contained 59.3 wt% FFA, 28.0 wt% TAG, 4.4 wt% DAG, and less than 1% MAG. Maximum esterification occurred at 65°C and 26 h reaction at a molar ratio of total FA/methanol/sulfuric acid of 1∶15∶1.5. Residual unreacted species under these conditions, as a fraction of their content in unesterified acid oil, were FFA, 6.6%; TAG, 5.8%; and DAG, 2.6%. This corresponds to estimated concentrations of FFA, 3.2%; TAG, 1.3%; and DAG, 0.2%, on a mass basis, in the ester product. In an alternative approach, the acylglycerol species in soapstock were saponified prior to acidulation. High-acid (HA) acid oil made from this saponified soapstock had an FFA content of 96.2 wt% and no detectable TAG, DAG, or MAG. Optimal esterification conditions for HA acid oil at 65°C were a mole ratio of FFA/methanol/acid of 1∶1.8∶0.17, and 14 h incubation. FAME recovery under these conditions was 89% of theoretical, and the residual unesterified FFA content was approximately 20 mg/g. This was reduced to 3.5 mg/g, below the maximum FFA level allowed for biodiesel, by washing with NaCl, NaHCO₃, and Ca(OH)₂ solutions. Alternatively, by subjecting the unwashed ester layer to a second esterification, the FFA level was reduced to less than 2 mg/g. The acid value of this material exceeded the maximum allowed for biodiesel, but was reduced to an acceptable value by a brief wash with 0.5 N NaOH.     

Optical Properties and London Dispersion Forces of Amorphous Silica Determined by Vacuum Ultraviolet Spectroscopy and Spectroscopic Ellipsometry

Precise and accurate knowledge of the optical properties of amorphous silica is important because of the increasing application of SiO₂ in optical and electrooptical devices, including photolithography masks for semiconductor fabrication, recently as a potential 157 nm mask substrate. The optical properties in the vacuum ultraviolet (VUV) region have been investigated, because they convey detailed information on the electronic structure and interatomic bonding of the material. In this work, we have combined spectroscopic ellipsometry and VUV spectroscopy to directly determine the optical functions of SiO₂ in this range, thereby reducing the uncertainty in the low-energy extrapolation of the data, essential for Kramers–Kronig analysis of VUV reflectance. We report the complex optical properties of SiO₂, over the range of 1.5 to 42 eV, showing improved agreement with theory when contrasted with earlier results. In addition to the features previously reported at 10.4, 11.6, 14.03, and 17.10 eV, new interband transitions have been observed at 21.3 eV along with O 2 s transitions at 32 eV. We found the bulk plasma peak to be 23.7 eV in the energy loss function spectrum. Based on the magnitude of these new results, the Hamaker constant for SiO₂|Vacuum|SiO₂ is 71.6 zJ, which is larger than the previously reported value of 66 zJ.     

Humanization of lepidopteran insect-cell-produced glycoproteins

The insect cell-baculovirus expression vector system, widely used for glycoprotein production, is not ideal for pharmaceutical glycoprotein production due to the characteristics of the N-glycans in the expressed products. Insect cells lack several enzymes required for mammalian-type N-glycan synthesis and contain a specific N-acetylglucosaminidase that stunts the growth of chains and a core alpha-1,3-fucosyltransferase that yields potentially allergenic glycoforms. Current knowledge on N-glycan processing in lepidopteran insect cells is summarized, and strategies to develop better glycoprotein expression systems suitable for pharmaceutical glycoprotein production are discussed.     

Tamoxifen derivatives for delivery of the antitumoral (DACH)Pt group: selective synthesis by McMurry coupling,and biochemical behaviour

The goal of our study was to potentiate the effects of the ((R,R)-trans-1,2-diaminocyclohexane)-platinum(II) fragment [(DACH)Pt], known for its cytotoxic properties, either with tamoxifen (Tam), the most widely used antiestrogen in the treatment of hormone-dependent breast cancers, or with its active metabolite hydroxytamoxifen (hydroxy-Tam). We coupled Tam or hydroxy-Tam derivatives bearing a malonato group at the para position of the beta aromatic ring with the (DACH)Pt fragment. The malonato-Tam and malonato-hydroxy-Tam compounds were prepared through McMurry coupling of the appropriate ketones. The presence of the malonate group resulted in a pronounced stereospecificity in the reaction, since malonato-Tam was obtained only as the Z isomer, while malonato-hydroxy-Tam was obtained as an 80/20 E/Z mixture. Attribution of the isomeric structures was achieved by 2D NMR spectroscopy. The platinum complexes (DACH)Pt-malonato-Tam and (DACH)Pt-malonato-hydroxy-Tam were then prepared by coupling the barium salts derived from the malonato-Tam and malonato-hydroxy-Tam with the nitrate derived from (DACH)PtCl(2). Study of the biochemical properties of these two platinum complexes showed that, while the hydroxy-Tam complex is satisfactorily recognized by the estrogen receptor (relative binding affinity, RBA=6.4 %), the Tam complex is less well recognized (RBA=0.5 %). The effects of these complexes on two hormone-dependent breast cancer cell lines (MCF7 and MVLN) were studied in vitro. Both complexes showed an antiproliferative effect on MCF7 cells, and an antiestrogenic effect on MVLN cells. The observed effects appear to be essentially antihormonal, since incorporation of the (DACH)Pt fragment into the tamoxifen skeleton did not cause an increase in the cytotoxicity of the complexes.     

Propene and 1-Octene Hydroformylation with Silica-Supported, Ionic Liquid-Phase (SILP) Rh-Phosphine Catalysts in Continuous Fixed-Bed Mode

Supported ionic liquid-phase (SILP) catalysts were made by immobilizing Rh-monophosphine complexes of bis(m-phenylguanidinium)phenylphosphine 1 and NORBOS 2 ligands in 1-n-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF₆], on a silica support. The catalysts were active in continuous gas- and liquid-phase hydroformylation of propene and 1-octene, exhibiting TOFs up to 88 h^-1 for SILP Rh-2 catalysts, while only low selectivities up to 74% n-aldehyde (n/iso ratio of 2.8) were obtained. This is the first example of continuous fixed-bed liquid-phase hydroformylation using SILP catalysts.     

Rather the Rule than the Exception: Non-Convex Pareto Sets and their Navigation in Distillation Processes

Novel algorithms for adaptive approximation and interactive navigation of Pareto sets are applied to various homogeneous distillation processes with recycle streams within an industrial flowsheet simulator. The adaptive approximation scheme shows that the Pareto set consists of both convex and non-convex regions when the product purities are maximised while minimising the total heat duties. It is illustrated how such Pareto sets can be navigated interactively using a ray tracing technique. Our results suggest that the occurrence of non-convex regions in the Pareto sets is due to recycle streams in the flowsheets and is therefore the rule rather than the exception in multi-objective optimisation of flowsheet simulations in chemical engineering.     

AI in Process Industries – Current Status and Future Prospects

The chemical industry is one of the key industrial sectors in Germany and at the same time one of the largest consumers of energy and raw materials. A successful energy transition and the development of a circular economy can only succeed if they are actively supported and shaped by the chemical industry – through the redesign of existing production processes and the exploration and implementation of new process routes. The challenge is to realize this transformation within a very short time and for many production processes, whereby a much larger number of process routes must be explored. Digital technologies are key to master this transformation towards more sustainability, climate, and environmental protection. The KEEN project aims to explore and leverage artificial intelligence (AI) opportunities in process industry. The newly developed AI methods are tested wherever possible in real working environments and production plants to prove the economic benefit, applicability, and reliability of the methods and technologies.     

Strategien zum Schließen der Stoffkreisläufe beim Recycling von Fluorpolymeren

In fluoropolymers, a large portion or even all of the hydrogen atoms in a polymer chain are replaced by fluorine, which results in a number of special properties such as high chemical and temperature resistance. As a result of this combination of properties, these high-performance polymers are not replaceable, or only with difficulty, for some applications. The recycling of polymers and the associated closing of material loops is an essential development task for the entire polymer industry. Materials such as fluoropolymers have a special position due to their chemical composition and their low market volume, as they cannot be recycled together with other bulk polymers at the end of their life cycle. This paper discusses different processes in terms of their technical maturity and suitability to allow fluoropolymers to be fully recycled.     

Formulation for chemical EOR: Development and evaluation of an ASP formulation In customer field conditions

Alkali surfactant polymer (ASP) flooding is an enhanced oil recovery (EOR) technology with an impressive potential for increasing incremental oil production from conventional hydrocarbon bearing reservoirs. A challenge to ASP application is the complexity of determining an effective formulation, typically requiring extensive laboratory screening of nearly countless combinations of surfactants and cosolvents. This paper focuses on demonstrating the utility of the hydrophilic–lipophilic deviation (HLD) concept for EOR application to simplify surfactant formulation workstreams seeking an economically viable ASP formulation for field application. In describing work performed for EOR application of ASP under customer conditions using crude oil, the discussion covers the initial evaluation of the promising surfactant formulation (interfacial tension and solubility), the improvement upon the formulation via HLD principles, and the evaluation of the improved surfactant formulation (coreflood studies). The final ASP formulation identified consisted of a 9 to 1 mixture of alkyl propoxy sulfate sodium salt (APS) to alkyl ethoxy sulfate sodium salt (AES) totaling 2000 ppm active surfactant content, 2.0 wt% Na₂CO₃, and 3000 ppm polyacrylamide polymer (all commercially available products). This formulation had ultra-low interfacial tension and favorable mixing behavior under reservoir conditions. In coreflood studies, the final formulation reproducibly achieved cumulative oil recovery of 96.4%–98.5% of original oil in place with only 0.3 PV of ASP injection with a chase alkali polymer injection.     

Thiol-yne 3D Printable Polymeric Resins for the Efficient Removal of a Model Pollutant from Waters

A new 3D printable resin formulation is developed and optimized from commercially available thiol (pentaerythritol tetrakis(3-mercaptopropionate); PETMP) and alkyne (3-butyn-1-ol; BA) monomers. Printed objects are characterized by Fourier-transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The extraction efficiency of the printed thiol-yne device is then investigated using a model dye – malachite green (MG). The results displayed excellent dye removal efficiency with > 95% MG removed within 5 min. The 3D-printed devices are reusable and show 100% removal over six cycles after washing with deionized water and methanol. The presence of surface hydroxyl groups derived from the BA monomer is shown to enhance dye adsorption in comparison to control materials. The printing procedure and resin formulation are robust and consistent when devices from different resin batches are compared for MG dye removal. The thiol-yne 3D printed devices demonstrated excellent dye removal (> 99%) from water samples collected from a tap and a nearby river source. The successful development of this resin provides a new thiol-yne-based resin system for stereolithography (SLA) 3D printing for the removal of organic dyes from wastewater and presents a potential for broad applications in water treatment.