Techno-Economic Feasibility of Selective CO2 Capture Processes from Biogas Streams using Ionic Liquids as Physical Absorbents

Biogas from anaerobic digestion of sewage sludge is a renewable resource with high energy content, which is formed mainly of CH4 (40-75 vol.%) and CO2 (15-60 vol.%) Other components such as water (H2O, 5-10 vol.%) and trace amounts of hydrogen sulfide and siloxanes can also be present. A CH4-rich stream can be produced by removing the CO2 and other impurities so that the upgraded bio-methane can be injected into the natural gas grid or used as a vehicle fuel. The main objective of this paper is to develop a new modeling methodology to assess the technical and economic performance of biogas upgrading processes using ionic liquids which physically absorb CO2. Three different ionic liquids, namely the 1-ethyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide, 1-hexyl-3-methylimidazoliumbis[(trifluoromethyl)sulfonyl]imide and trihexyl(tetradecyl)phosphonium bis[(trifluoromethyl)sulfonyl]imide, are considered for CO2 capture in a pressure-swing regenerative absorption process. The simulation software Aspen Plus and Aspen Process Economic Analyzer is used to account for mass and energy balances as well as equipment cost. In all cases, the biogas upgrading plant consists of a multistage compressor for biogas compression, a packed absorption column for CO2 absorption, a flash evaporator for solvent regeneration, a centrifugal pump for solvent recirculation, a pre-absorber solvent cooler and a gas turbine for electricity recovery. The evaluated processes are compared in terms of energy efficiency, capital investment and bio-methane production costs. The overall plant efficiency ranges from 71-86 % whereas the bio-methane production cost ranges from £6.26-7.76 per GJ (LHV). A sensitivity analysis is also performed to determine how several technical and economic parameters affect the bio-methane production costs. The results of this study show that the simulation methodology developed can predict plant efficiencies and production costs of large scale CO2 capture processes using ionic liquids without having to rely on gas solubility experimental data.

Comparison of Chemical Absorbents Used for CO2 Capture in Coal-Fired Power Plants.

Climate change conference was hold in Copenhagen in 2009, global warming became the worldwide focus once again. China as a developing country has paid more attention for this environmental problem. In China, a large part of carbon dioxide is emitted to the atmosphere from combustion of fossil fuels in power plants. How to control emission of the greenhouse gas into atmosphere is becoming an urgent concern. Among numerous methods, CO2 capture is the hope to limit the amount of CO2 emitted into the air. The well-established method for CO2 capture is to remove CO2 by absorption into solutions in conventional equipment. Absorbents used for CO2 and H2S capture are important choice for CO2 capture technology. It is related to the cost and efficiency of plant directly and is essential to investigate the proposed CO2 and H2S absorbents.

Synthesis and modifications of metal oxide nanostructures and their applications

Transition metal oxides are functional materials that have advanced applications in many areas, because of their diverse properties (optical, electrical, magnetic, etc.), hardness, thermal stability and chemical resistance. Novel applications of the nanostructures of these oxides are attracting significant interest as new synthesis methods are developed and new structures are reported. Hydrothermal synthesis is an effective process to prepare various delicate structures of metal oxides on the scales from a few to tens of nanometres, specifically, the highly dispersed intermediate structures which are hardly obtained through pyro-synthesis. In this thesis, a range of new metal oxide (stable and metastable titanate, niobate) nanostructures, namely nanotubes and nanofibres, were synthesised via a hydrothermal process. Further structure modifications were conducted and potential applications in catalysis, photocatalysis, adsorption and construction of ceramic membrane were studied. The morphology evolution during the hydrothermal reaction between Nb2O5 particles and concentrated NaOH was monitored. The study demonstrates that by optimising the reaction parameters (temperature, amount of reactants), one can obtain a variety of nanostructured solids, from intermediate phases niobate bars and fibres to the stable phase cubes. Trititanate (Na2Ti3O7) nanofibres and nanotubes were obtained by the hydrothermal reaction between TiO2 powders or a titanium compound (e.g. TiOSO4·xH2O) and concentrated NaOH solution by controlling the reaction temperature and NaOH concentration. The trititanate possesses a layered structure, and the Na ions that exist between the negative charged titanate layers are exchangeable with other metal ions or H+ ions. The ion-exchange has crucial influence on the phase transition of the exchanged products. The exchange of the sodium ions in the titanate with H+ ions yields protonated titanate (H-titanate) and subsequent phase transformation of the H-titanate enable various TiO2 structures with retained morphology. H-titanate, either nanofibres or tubes, can be converted to pure TiO2(B), pure anatase, mixed TiO2(B) and anatase phases by controlled calcination and by a two-step process of acid-treatment and subsequent calcination. While the controlled calcination of the sodium titanate yield new titanate structures (metastable titanate with formula Na1.5H0.5Ti3O7, with retained fibril morphology) that can be used for removal of radioactive ions and heavy metal ions from water. The structures and morphologies of the metal oxides were characterised by advanced techniques. Titania nanofibres of mixed anatase and TiO2(B) phases, pure anatase and pure TiO2(B) were obtained by calcining H-titanate nanofibres at different temperatures between 300 and 700 °C. The fibril morphology was retained after calcination, which is suitable for transmission electron microscopy (TEM) analysis. It has been found by TEM analysis that in mixed-phase structure the interfaces between anatase and TiO2(B) phases are not random contacts between the engaged crystals of the two phases, but form from the well matched lattice planes of the two phases. For instance, (101) planes in anatase and (101) planes of TiO2(B) are similar in d spaces (~0.18 nm), and they join together to form a stable interface. The interfaces between the two phases act as an one-way valve that permit the transfer of photogenerated charge from anatase to TiO2(B). This reduces the recombination of photogenerated electrons and holes in anatase, enhancing the activity for photocatalytic oxidation. Therefore, the mixed-phase nanofibres exhibited higher photocatalytic activity for degradation of sulforhodamine B (SRB) dye under ultraviolet (UV) light than the nanofibres of either pure phase alone, or the mechanical mixtures (which have no interfaces) of the two pure phase nanofibres with a similar phase composition. This verifies the theory that the difference between the conduction band edges of the two phases may result in charge transfer from one phase to the other, which results in effectively the photogenerated charge separation and thus facilitates the redox reaction involving these charges. Such an interface structure facilitates charge transfer crossing the interfaces. The knowledge acquired in this study is important not only for design of efficient TiO2 photocatalysts but also for understanding the photocatalysis process. Moreover, the fibril titania photocatalysts are of great advantage when they are separated from a liquid for reuse by filtration, sedimentation, or centrifugation, compared to nanoparticles of the same scale. The surface structure of TiO2 also plays a significant role in catalysis and photocatalysis. Four types of large surface area TiO2 nanotubes with different phase compositions (labelled as NTA, NTBA, NTMA and NTM) were synthesised from calcination and acid treatment of the H-titanate nanotubes. Using the in situ FTIR emission spectrescopy (IES), desorption and re-adsorption process of surface OH-groups on oxide surface can be trailed. In this work, the surface OH-group regeneration ability of the TiO2 nanotubes was investigated. The ability of the four samples distinctively different, having the order: NTA > NTBA > NTMA > NTM. The same order was observed for the catalytic when the samples served as photocatalysts for the decomposition of synthetic dye SRB under UV light, as the supports of gold (Au) catalysts (where gold particles were loaded by a colloid-based method) for photodecomposition of formaldehyde under visible light and for catalytic oxidation of CO at low temperatures. Therefore, the ability of TiO2 nanotubes to generate surface OH-groups is an indicator of the catalytic activity. The reason behind the correlation is that the oxygen vacancies at bridging O2- sites of TiO2 surface can generate surface OH-groups and these groups facilitate adsorption and activation of O2 molecules, which is the key step of the oxidation reactions. The structure of the oxygen vacancies at bridging O2- sites is proposed. Also a new mechanism for the photocatalytic formaldehyde decomposition with the Au-TiO2 catalysts is proposed: The visible light absorbed by the gold nanoparticles, due to surface plasmon resonance effect, induces transition of the 6sp electrons of gold to high energy levels. These energetic electrons can migrate to the conduction band of TiO2 and are seized by oxygen molecules. Meanwhile, the gold nanoparticles capture electrons from the formaldehyde molecules adsorbed on them because of gold’s high electronegativity. O2 adsorbed on the TiO2 supports surface are the major electron acceptor. The more O2 adsorbed, the higher the oxidation activity of the photocatalyst will exhibit. The last part of this thesis demonstrates two innovative applications of the titanate nanostructures. Firstly, trititanate and metastable titanate (Na1.5H0.5Ti3O7) nanofibres are used as intelligent absorbents for removal of radioactive cations and heavy metal ions, utilizing the properties of the ion exchange ability, deformable layered structure, and fibril morphology. Environmental contamination with radioactive ions and heavy metal ions can cause a serious threat to the health of a large part of the population. Treatment of the wastes is needed to produce a waste product suitable for long-term storage and disposal. The ion-exchange ability of layered titanate structure permitted adsorption of bivalence toxic cations (Sr2+, Ra2+, Pb2+) from aqueous solution. More importantly, the adsorption is irreversible, due to the deformation of the structure induced by the strong interaction between the adsorbed bivalent cations and negatively charged TiO6 octahedra, and results in permanent entrapment of the toxic bivalent cations in the fibres so that the toxic ions can be safely deposited. Compared to conventional clay and zeolite sorbents, the fibril absorbents are of great advantage as they can be readily dispersed into and separated from a liquid. Secondly, new generation membranes were constructed by using large titanate and small ã-alumina nanofibres as intermediate and top layers, respectively, on a porous alumina substrate via a spin-coating process. Compared to conventional ceramic membranes constructed by spherical particles, the ceramic membrane constructed by the fibres permits high flux because of the large porosity of their separation layers. The voids in the separation layer determine the selectivity and flux of a separation membrane. When the sizes of the voids are similar (which means a similar selectivity of the separation layer), the flux passing through the membrane increases with the volume of the voids which are filtration passages. For the ideal and simplest texture, a mesh constructed with the nanofibres 10 nm thick and having a uniform pore size of 60 nm, the porosity is greater than 73.5 %. In contrast, the porosity of the separation layer that possesses the same pore size but is constructed with metal oxide spherical particles, as in conventional ceramic membranes, is 36% or less. The membrane constructed by titanate nanofibres and a layer of randomly oriented alumina nanofibres was able to filter out 96.8% of latex spheres of 60 nm size, while maintaining a high flux rate between 600 and 900 Lm–2 h–1, more than 15 times higher than the conventional membrane reported in the most recent study.

Surface modification of alumina nanofibres for the selective adsorption of alachlor and imazaquin herbicides

The effective removal of pollutants using a thermally and chemically stable substrate that has controllable absorption properties is a goal of water treatment. In this study, the surfaces of thin alumina (γ-Al2O3) nanofibres were modified by the grafting either of two organosilane agents, 3-chloro-propyl-triethoxysilane (CPTES) and octyl-triethoxysilane (OTES). These modified materials were then trialed as absorbents for the removal of two herbicides, alachlor and imazaquin from water. The formation of organic groups during the functionalisation process established super hydrophobic sites on the surfaces of the nanofibres. This super hydrophobic group is a kind of protruding adsorption site which facilitates the intimate contact with the pollutants. OTES grafted substrate were shown to be more selective for alachlor while imazaquin selectivity is shown by the CPTES grafted substrate. Kinetics studies revealed that imazaquin was rapidly adsorbed on CPTES-modified surfaces. However, the adsorption of alachlor by OTES grafted surface was achieved more slowly.

Charge-controlled switchable CO2 capture on boron nitride nanomaterials

Increasing concerns about the atmospheric CO2 concentration and its impact on the environment are motivating researchers to discover new materials and technologies for efficient CO2 capture and conversion. Here, we report a study of the adsorption of CO2, CH4, and H2 on boron nitride (BN) nanosheets and nanotubes (NTs) with different charge states. The results show that the process of CO2 capture/release can be simply controlled by switching on/off the charges carried by BN nanomaterials. CO2 molecules form weak interactions with uncharged BN nanomaterials and are weakly adsorbed. When extra electrons are introduced to these nanomaterials (i.e., when they are negatively charged), CO2 molecules become tightly bound and strongly adsorbed. Once the electrons are removed, CO2 molecules spontaneously desorb from BN absorbents. In addition, these negatively charged BN nanosorbents show high selectivity for separating CO2 from its mixtures with CH4 and/or H2. Our study demonstrates that BN nanomaterials are excellent absorbents for controllable, highly selective, and reversible capture and release of CO2. In addition, the charge density applied in this study is of the order of 1013 cm–2 of BN nanomaterials and can be easily realized experimentally.

Effect of an Ethylene Absorbent on Quality of Tomato Slices

Ethylene production is stimulated during the slicing of fresh cut tomato slices. Experiments were conducted to investigate whether the inclusion of ethylene absorbents in packaging affects the quality of tomato slices cv. Revolution during storage at 5OC. ‘Pink’ maturity stage tomatoes were cut into 7mm thick slices and vertically stacked in closed glass containers for 12 days with or without Purafil® to remove ethylene. The ethylene removal treatment resulted in reduced ethylene, less CO2 accumulation, and firmer slices.

Photoresponse of double-stacked graphene to Infrared radiation

We report the photoresponse of stacked graphene layers towards infrared radiation. Graphene is stacked in two configurations, namely, crossed and parallel layers. Raman analysis demonstrated a strong interaction among the stacked graphene layers. Graphene in the crossed configuration exhibited the presence of both negative and positive conductivities; however, other configurations of graphene exhibited positive conductivity only. The presence of negative photoconductivity is proposed to be due to oxygen or oxygen-related functional group absorbents that are trapped in between two monolayers of graphene and act as scattering centers for free carriers. An interesting trend is reported in differential conductivity when stacked layers are compared with multilayers and parallel-stacked graphene layers.

滴灌条件下不同保水剂在枣林坡地的应用效果研究

利用野外试验方法,在滴灌条件下研究了保水剂在坡地枣林中的使用效果。试验结果证明:施用保水剂的土壤含水量较对照提高了15.3%~39.2%,使10~70 cm土层有较高贮存水量,在年生育期平均降雨量为395 mm情况下,确定红枣整个生育期(为210 d)共灌水4次,按大约每55 d灌溉一次计算,可减少灌溉2次,节约用水264 m3/hm2;0~60 cm土壤平均容重降低0.05~0.16 g/cm3,改善了土壤的通气透水的土壤物理性质,促进了枣树的生长发育,与对照株产5.6 kg相比,四年生红枣单株最高可增产2.85 kg/株;就不同保水剂综合来说,Hs和Hm表现出良好的适宜性。

保水剂对春小麦产量和水分利用效率的影响

对辽西半干旱区褐土农田施用几种保水剂的效果进行了室内模拟和田间试验研究.观测了保水剂包衣和沟施对春小麦出苗、土壤水分含量及产量的影响，对使用保水剂的适宜浓度、效果、经济效益进行了评价，并对保水剂促进出苗的机理和田间保水机制进行了探讨.结果表明，保水剂包衣能够加快种子吸水过程，促进春小麦萌发出苗，出苗期提前1～2天，出苗率提高6.5%～11.5%，增产7.5%～12.7%，投入产出比为1：7.保水剂包衣的适宜浓度为1%，浓度过大（≥5%），保水剂层过厚，会影响种子呼吸和水分通过，不利于出苗，出苗率和产量分别提高5%和10%以上.保水剂沟施，可提高土壤持水能力，0～30cm的土壤水分含量，提高了1个百分点.保水剂沟施处理，水分利用效率可提高0.7～2.0kg·mm<'-1>·hm<'-2>，提高幅度为6.7%～18.5%.研究发现，保水剂田间保水效果，与土壤含水量有关，土壤水分低于毛管断裂含水量时，保水剂对蒸发速率影响很小.

Novel DGT method with tri-metal oxide adsorbent for in situ spatiotemporal flux measurement of fluoride in waters and sediments

Natural mineral-water interface reactions drive ecosystem/global fluoride (F−) cycling. These small-scale processes prove challenging to monitoring due to mobilization being highly localized and variable; influenced by changing climate, hydrology, dissolution chemistries and pedogenosis. These release events could be captured in situ by the passive sampling technique, diffusive gradients in thin-films (DGT), providing a cost-effective and time-integrated measurement of F− mobilization. However, attempts to develop the method for F− have been unsuccessful due to the very restrictive operational ranges that most F−-absorbents function within. A new hybrid-DGT technique for F− quantification containing a three-phase fine particle composite (Fesingle bondAlsingle bondCe, FAC) adsorbent was developed and evaluated. Sampler response was validated in laboratory and field deployments, passing solution chemistry QC within ionic strength and pH ranges of 0–200 mmol L−1 and 4.3–9.1, respectively, and exhibiting high sorption capacities (98 ± 8 μg cm−2). FAC-DGT measurements adequately predicted up to weeklong averaged in situ F− fluvial fluxes in a freshwater river and F− concentrations in a wastewater treatment flume determined by high frequency active sampling. While, millimetre-scale diffusive fluxes across the sediment-water interface were modeled for three contrasting lake bed sediments from a F−-enriched lake using the new FAC-DGT platform.

Microbial biosynthesis of biopolymers and applications in the biopharmaceutical, biomedical and food industries

Biopolymers can be produced through a variety of mechanisms. They can be derived from microbial systems, extracted from higher organisms such as plants, or synthesized chemically from basic biological building blocks. A wide range of emerging applications rely on all three of these production techniques. In recent years, considerable attention has been given to biopolymers produced by microbes. It is on the microbial level where the tools of genetic engineering can be most readily applied. A number of novel materials are now being developed or introduced into the market. Biopolymers are being developed for use as medical materials, packaging, cosmetics, food additives, clothing fabrics, water treatment chemicals, industrial plastics, absorbents, biosensors, and even data storage elements. This review identifies the possible commercial applications and describes the various methods of production of microbial biopolymers.

High internal phase emulsion (HIPE) xerogels for enhanced oil spill recovery

Oil spills cause serious damage to the aquatic ecosystem and require quick cleanup. Herein we report high internal phase emulsion (HIPE) xerogels for the first time as oil absorbents for enhanced oil spill recovery. The HIPE xerogels absorb diesel from the water-oil mixture in 20-30 seconds. The absorption capacity of the HIPE xerogels ranges from 20 to 32 times for different kinds of oils, and the oils can be recovered simply by being squeezed out, with a recovery rate around 80%. They can be reused at least 40 times without obvious deterioration in oil separation properties from 0 to 45 °C. These novel xerogels are suitable for practical use in oil spill reclamation and wastewater treatment.

Quality assessment of eggs packed under modified atmosphere

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)