Techno-economical evaluations of decarbonized hydrogen production based on direct biogas conversion using thermo-chemical looping cycles

Hydrogen production by biogas conversion represent a promising solution for reduction of fossil CO₂ emissions. In this work, a detailed techno-economic analysis was performed for decarbonized hydrogen production based on biogas conversion using calcium and chemical looping cycles. All evaluated concepts generate 100,000 Nm³/h high purity hydrogen. As reference cases, the biogas steam reforming design without decarbonization and with CO₂ capture by gas-liquid chemical absorption were also considered. The results show that iron-based chemical looping design has higher energy efficiency compared with the gas-liquid absorption case by 2.3 net percentage points as well as a superior carbon capture rate (99% vs. 65%). The calcium looping case shows a lower efficiency than chemical scrubbing, with about 2.5 net percentage points, but the carbon capture rate is higher (95% vs. 65%). The hydrogen production cost increases with decarbonization, the calcium looping shows the most favourable situation (37.14 €/MWh) compared to the non-capture steam reforming case (33 €/MWh) and MDEA and iron looping cases (about 42 €/MWh). The calcium looping case has the lowest CO₂ avoidance cost (10 €/t) followed by iron looping (20 €/t) and MDEA (31 €/t) cases.     

Extraction and characterization of hydroxyapatite-based materials from grey triggerfish skin and black scabbardfish bones

The conversion of food industry by-products to compounds with high added value is nowadays a significant topic, for social, environmental, and economic reasons. In this paper, calcium phosphate-based materials were obtained from black scabbardfish (Aphanopus carbo) bones and grey triggerfish (Balistes capriscus) skin, which are two of the most abundant fish by-products of Madeira Island. Different calcination temperatures between 400 and 1000°C were employed. Materials obtained from calcination of bones of black scabbard fish were composed by homogeneous mixtures of hydroxyapatite (Ca₁₀(PO4)₆(OH)₂, HAp) and β-tricalcium phosphate (β-Ca₃(PO₄)₂, β-TCP). Because of the high biocompatibility of HAp and the good resorbability of β-TCP, these natural biphasic materials could be very relevant in the field of biomaterials, as bone grafts. The ratio between HAp and β-TCP in the biphasic compound was dependent on the calcination temperature. Differently, the material obtained from skin of grey triggerfish contained HAp as the main phase, together with small amounts of other mineral phases, such as halite and rhenanite, which are known to enhance osteogenesis when used as bone substitutes. In both cases, the increase of calcination temperature led to an increase in the particles size with a consequent decrease in their specific surface area. These results demonstrate that from the fish by-products of the most consumed fishes in Madeira Island it is possible to obtain bioceramic materials with tunable composition and particle morphology, which could be promising materials for the biomedical field.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Structural Basis for the Function of the C-Terminal Proton Release Pathway in the Calcium Pump

The calcium pump (sarco/endoplasmic reticulum Ca²⁺-ATPase, SERCA) plays a major role in calcium homeostasis in muscle cells by clearing cytosolic Ca²⁺ during muscle relaxation. Active Ca²⁺ transport by SERCA involves the structural transition from a low-Ca²⁺ affinity E2 state toward a high-Ca²⁺ affinity E1 state of the pump. This structural transition is accompanied by the countertransport of protons to stabilize the negative charge and maintain the structural integrity of the transport sites and partially compensate for the positive charges of the two Ca²⁺ ions passing through the membrane. X-ray crystallography studies have suggested that a hydrated pore located at the C-terminal domain of SERCA serves as a conduit for proton countertransport, but the existence and function of this pathway have not yet been fully characterized. We used atomistic simulations to demonstrate that in the protonated E2 state and the absence of initially bound water molecules, the C-terminal pore becomes hydrated in the nanosecond timescale. Hydration of the C-terminal pore is accompanied by the formation of water wires that connect the transport sites with the cytosol. Water wires are known as ubiquitous proton-transport devices in biological systems, thus supporting the notion that the C-terminal domain serves as a conduit for proton release. Additional simulations showed that the release of a single proton from the transport sites induces bending of transmembrane helix M5 and the interaction between residues Arg762 and Ser915. These structural changes create a physical barrier against full hydration of the pore and prevent the formation of hydrogen-bonded water wires once proton transport has occurred through this pore. Together, these findings support the notion that the C-terminal proton release pathway is a functional element of SERCA and also provide a mechanistic model for its operation in the catalytic cycle of the pump.     

Impact of gypsum on flotation of scheelite and fluorite using sodium oleate as collector

ABSTRACT

In this study, effect of calcium and gypsum on scheelite and fluorite was investigated using sodium oleate as collector. Micro-flotation and contact angle results showed that the adsorption of calcium could inhibit the hydrophobicity of scheelite and fluorite. Moreover, sulfate could enhance the inhibition. FT-IR results showed that calcium could be priori precipitated into calcium oleate and adsorb on mineral surface. The adsorption of calcium could increase the scheelite potential to IEP, while it showed limited effect on fluorite potential. However, the interaction of calcium on scheelite and fluorite in gypsum solution was more complex than that in calcium solution.     

Experimental study of crystal anisotropy based on ultra-precision cylindrical turning of single-crystal calcium fluoride

To realize ultimately efficient signal processing, it is necessary to replace electrical signal processing circuits with optical ones. The optical micro-resonator, which localizes light at a certain spot, is an essential component in optical signal processing. Single-crystal calcium fluoride (CaF₂) is the most suitable material for a highly efficient optical micro-resonator. The CaF₂ resonator can only be manufactured by ultra-precision machining processes, because its crystal anisotropy does not allow the application of chemical etching. However, the optical micro-resonator's performance depends definitely on the surface integrity.This study investigated the relationship between surface quality after ultra-precision machining and crystal anisotropy. Firstly, crack initiation was investigated on the (1 0 0), (1 1 0), and (1 1 1) planes using the micro-Vickers hardness test. Secondly, brittle-ductile transition was investigated by orthogonal cutting tests. Finally, cutting performance of cylindrical turning was evaluated, which could be a suitable method for manufacturing the CaF₂ resonator. The most difficult point in cylindrical turning of CaF₂ is that the crystalline plane and cutting direction vary continuously. In order to manufacture the CaF₂ optical micro-resonator more efficiently, analysis was conducted on crack initiation and surface quality of all crystallographic orientations from the perspective of slip system and cleavage.     

Synergistic antimicrobial effect of lactocin AL705 and nisin combined with organic acid salts against Listeria innocua 7 in broth and a hard cheese

The effectiveness of antimicrobial mixtures against Listeria innocua 7, used as a L. monocytogenes surrogate, was investigated in broth and a food system. Synergistic effects were found for nisin (Nis), potassium sorbate (PS), calcium propionate (CP) and sodium lactate (SL), Nis + PS being the most effective binary mixture that exhibited listericidal activity in broth. To assess the effect of adding lactocin AL705 (AL705) to Nis + organic acid salt combinations, tridimensional isobolograms were generated. Sub-MIC combinations of the antimicrobials exerted bactericidal activity against L. innocua 7 after AL705 addition to the binary mixtures. However, when applied on Sardo cheese contaminated with L. innocua 7 (initial inoculum 4.45 ± 0.06 CFU g⁻¹), only Nis + PS + AL705 produced count reductions respect to the control, reaching 3.04 ± 0.35 CFU g⁻¹ counts after 15 days at 15 °C. Ternary combinations containing AL705 showed potential to reduce antimicrobial usages for L. innocua 7 inhibition.     

MPTA型原油脱金属剂的工业应用

在对高金属含量原油进行初步评价的基础上，利用SH—Ⅰ型电脱盐试验仪对自主开发的MPTA型原油脱金属剂进行了原油脱金属的实验室研究。结果表明，当MPTA型脱金属剂加入量为250μg／g时，钙的脱除率可达97．4％，并且对其它金属元素，如镍、铁、钠、锰、铝和钒也有明显的脱除效果。该剂在山东恒源石油化工股份有限公司重交沥青车间500kt／a的电脱盐装置上进行原油脱金属工业试验的结果表明，经过二级电脱盐处理后，钙的脱除率达到99．1％，钠的脱除率为94．6％，铁的脱除率为82．9％，并可在一定程度上降低原油中镍和铜的含量。使用MPTA型原油脱金属剂显著降低了一、二级电脱盐装置的电场电流，有利于炼油厂的节能降耗。     

Continuous precipitation of calcium sulfate dihydrate from waste sulfuric acid and lime

Precipitation of calcium sulfate dihydrate, gypsum, from (i) a pure sulfuric acid/lime suspension and (ii) a waste sulfuric acid/lime suspension in a continuous pilot plant in the temperature range from 40 °C to 80 °C was studied. It was observed that in the case of waste sulfuric acid with a high content of Mg²⁺ and Fe²⁺ ions, several hours after the beginning of the precipitation, partial dissolution of the product and modification of the crystals from needle‐ and plate‐like to agglomerated structures occurred. It is suggested that the secondary changes occur due to the increased concentration of Mg²⁺ and Fe²⁺ ions in the reactor. Below 60 °C, and above 70 °C plate‐like and needle‐like single crystals respectively were formed. The mean size (d₅₀) of the crystals was found to increase with increasing temperature and decrease with the initial concentration of lime. Gypsum produced between 70 °C and 80 °C is suitable for further processing for construction plaster. In a precipitation process with pure sulfuric acid only single perfect needle‐like crystals occurred. Copyright © 2005 Society of Chemical Industry     

探讨电石法PVC烟气治理方法

分析了电石法PVC生产链中电石炉烟气及电厂烟气二氧化硫的排放情况,指出利用电石炉烟气中的CO合成氨、再将合成氨用于燃煤电厂烟气的"氨法"脱硫是具有较大应用潜力的循环经济产业链。