Integration of Bio-refinery Concepts in Oil Refineries

In this work, the systematic integration of bio-refineries within oil refineries is considered. This is particularly relevant due to the lack of adaptation of existing refineries to diminishing oil supply. Moreover, the integration of oil and bio-refineries has a massively positive effect on the reduction of CO2 emissions. For instance, the biodiesel produced in bio-refineries could be integrated with conventional oil refinery processes to produce fuel, thusly reducing the dependence on crude oil. This represents a suitable alternative for increasing profit margins while being increasingly environmentally friendly. The identified possible routes of integration will be discussed in this contribution. For this purpose, the different proposed alternatives and their configurations were simulated and analysed. The developed models simulated key integrations e.g. a gasification unit that is fed from pyrolysis oil, biodiesel, and refinery residue, before being combined into one system involving all three. Varying forms of synthesis for these three feeds were also considered, focusing on novel techniques as well as environmentally friendly options that made use of waste products from other processes. The simulations revealed valuable gas stream rich in H2, with some CO2 and with a slight excess of CO resulting from the gasification unit. Further upgrading of these products was achieved by coupling the gasifier with a water gas shift (WGS) unit. This allowed a fine tune of the H2:CO ratio in the gas stream which can be further processed to obtain liquid hydrocarbons via Fischer-Tropsch (FT) synthesis or alternatively, clean hydrogen for fuel cells applications

Activity of immunoproteasome inhibitor ONX-0914 in acute lymphoblastic leukemia expressing MLL–AF4 fusion protein

Proteasome inhibitors bortezomib and carfilzomib are approved for the treatment of multiple myeloma and mantle cell lymphoma and have demonstrated clinical efficacy for the treatment of acute lymphoblastic leukemia (ALL). The t(4;11)(q21;q23) chromosomal translocation that leads to the expression of MLL–AF4 fusion protein and confers a poor prognosis, is the major cause of infant ALL. This translocation sensitizes tumor cells to proteasome inhibitors, but toxicities of bortezomib and carfilzomib may limit their use in pediatric patients. Many of these toxicities are caused by on-target inhibition of proteasomes in non-lymphoid tissues (e.g., heart muscle, gut, testicles). We found that MLL–AF4 cells express high levels of lymphoid tissue-specific immunoproteasomes and are sensitive to pharmacologically relevant concentrations of specific immunoproteasome inhibitor ONX-0914, even in the presence of stromal cells. Inhibition of multiple active sites of the immunoproteasomes was required to achieve cytotoxicity against ALL. ONX-0914, an inhibitor of LMP7 (ß5i) and LMP2 (ß1i) sites of the immunoproteasome, and LU-102, inhibitor of proteasome ß2 sites, exhibited synergistic cytotoxicity. Treatment with ONX-0914 significantly delayed the growth of orthotopic ALL xenograft tumors in mice. T-cell ALL lines were also sensitive to pharmacologically relevant concentrations of ONX-0914. This study provides a strong rationale for testing clinical stage immunoproteasome inhibitors KZ-616 and M3258 in ALL

Kinetic studies of CO2 methanation over a Ni/γ-Al2O3 catalyst using a batch reactor

The methanation of CO2 was investigated over a wide range of partial pressures of products and reactants using a gradientless, spinning-basket reactor operated in batch mode. The rate and selectivity of CO2 methanation, using a 12 wt% Ni/γ–Al2O3 catalyst, were explored at temperatures 453–483 K and pressures up to 20 bar. The rate was found to increase with increasing partial pressures of H2 and CO2 when the partial pressures of these reactants were low; however, the rate of reaction was found to be insensitive to changes in the partial pressures of H2 and CO2 when their partial pressures were high. A convenient method of determining the effect of H2O on the rate of reaction was also developed using the batch reactor and the inhibitory effect of H2O on CO2 methanation was quantified. The kinetic measurements were compared with a mathematical model of the reactor, in which different kinetic expressions were explored. The kinetics of the reaction were found to be consistent with a mechanism in which adsorbed CO2 dissociated to adsorbed CO and O on the surface of the catalyst with the rate-limiting step being the subsequent dissociation of adsorbed CO

An inhibitor of proteasome beta 2 sites sensitizes myeloma cells to immunoproteasome inhibitors

Bio-organic Synthesi

The influence of catalytic additives on kinetics of coal gasification process

Catalytic coal gasification is a process that has the potential to become one of the efficient industrial technology of energy production. For this reason, the subject of this study was to analyze the kinetics of catalytic gasification of ‘Janina’ coal with steam. Isothermal measurements were performed at 800 °C, 900 °C, 950 °C and 1000 °C at a pressure of 1 MPa using cations of sodium, potassium and calcium as catalysts. During examination the thermovolumetric method was used. This method allows to determine the formation rates of a gaseous product such as carbon monoxide, hydrogen, methane and carbon dioxide as well as their contribution to the resulting gas. Moreover, the influence of catalysts on the kinetics of CO and H2 formation at various temperatures was determined and the kinetics parameters were calculated with the use of isoconversional model, Random Pore Model and Grain Model. The obtained results confirmed the positive effect of catalysts on the coal gasification process. The catalytic measurements were characterized by higher reaction rate and shorter duration of the process, and the calculated values of the kinetic parameters were lower than for the gasification process without the addition of catalysts

Reasonable potential for GHG savings by anaerobic biomethane in Germany and UK derived from economic and ecological analyses

This study introduces a new approach to estimate biomethane market potential by analysing biogas markets and their relative environmental and economic advantages. This potential is then combined with greenhouse gas emission values for different feedstock shares (farm-fed and waste-fed systems) and different application share to determine the possible contribution of biomethane to national greenhouse gas emission saving goals. Markets that are considered are Germany and the UK being the biggest emitters of CO2eq in the European Union. The current use was compared with the scenarios (i) market projection, derived from literature study and (ii) reasonable potential, derived from environmental and economic calculations. The current market status is presented to show the past market development until the present date and associated greenhouse gas savings. Additionally the potential of biomethane to contribute to greenhouse gas emission savings is extensively described. Results indicate that the share of application in Germany is more environmental beneficial than the one in the UK achieving higher greenhouse gas savings at comparable feed-in level. In contrast, the UK has a higher share of waste-fed systems to produce biomethane. The use of biomethane in CHP plants achieves the highest GHG emission savings and if organic waste is used as feedstock the possible savings are even higher. With an increase of biomethane used in CHP plants and a decrease of biomethane used for direct heating the savings in the UK could increase up to 52%. Current savings of 2446 kt CO2eq (Germany) and 606 kt CO2eq (UK) can be extended to 4483 kt CO2eq (Germany) and 1443 kt CO2eq (UK) respectively. Scenario results were determined based on the environmental and economic advantageousness development of the existing biogas market. In this way positive future market development as well as improved shares of feedstock and application can contribute to further greenhouse gas emission savings of Germany and the UK

Thermodynamic analysis of methanation of palm empty fruit bunch (PEFB) pyrolysis oil with and without in situ CO2 sorption

Thermodynamic equilibrium analysis for conversion of palm empty fruit bunch (PEFB) bio-oil to methane using low-temperature steam reforming (LTSR) process was conducted by assuming either isothermal or adiabatic condition, with and without sorption enhancement (SE-LTSR), with CaO(S) or Ca(OH)2(S) as CO2 sorbent. Temperatures of 300-800 K, molar steam to carbon (S/C) ratios of 0.3-7.0, pressures of 1-30 atm and molar calcium to carbon ratios (Ca:C) of 0.3-1.0 were simulated. For reasons of process simplicity, the best conditions for CH4 production were observed for the adiabatic LTSR process without sorption at S/C between 2.5 and 3 (compared to the stoichiometric S/C of 0.375), inlet temperature above 450 K, resulting in reformer temperature of 582 K, where close to the theoretical maximum CH4 yield of 38 wt % of the simulated dry PEFB oil was obtained, resulting in a reformate consisting of 44.5 vol % CH4, 42.7 vol % CO2 and 12.7 vol % H2 and requiring only moderate heating mainly to partially preheat the reactants. Temperatures and S/C below these resulted in high risk of carbon by-product