Hydrothermal technologies for the production of fuels and chemicals from biomass

Biomass and non-food crop residues are seen as relatively low cost and abundant renewable sources capable of making a large contribution to the world’s future energy and chemicals supply. Signifi cant quantities of ethanol are currently produced from biomass via biochemical processes, but thermochemical conversion processes offer greater potential to utilize the entire biomass source to produce a range of products. This chapter will review thermochemical gasifi cation and pyrolysis methods with a focus on hydrothermal liquefaction processes. Hydrothermal liquefaction is the most energetically advantageous thermochemical biomass conversion process. If the target is to produce sustainable liquid fuels and chemicals and reduce the impact of global warming as a result of carbon dioxide, nitrous oxide, and methane emissions (i.e., protect the natural environment), the use of “green” solvents, biocatalysts and heterogeneous catalysts must be the main R&D initiatives. As the biocrude produced from hydrothermal liquefaction is a complex mixture which is relatively viscous, corrosive, and unstable to oxidation (due to the presence of water and oxygenated compounds), additional upgrading processes are required to produce suitable biofuels and chemicals.

Studies on self-assembly hydrothermal fabrication and thermal stability of Chromium oxyhydroxide nanomaterials synthesised from Chromium oxide colloids

Chromium oxyhydroxide nanomaterials with narrow size-distribution were synthesised through a simple hydrothermal method. Experimental conditions, such as reaction duration and pH values of the precipitation process and hydrothermal treatment played important roles in determining the nature of the final product chromium oxyhydroxide nanomaterials. The effect of these synthesis parameters were studied with the assistance of X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and thermogravimetric analyses. This research has developed a controllable synthesis of Chromium oxyhydroxide nanomaterials from Chromium oxide colloids.

A hydrogen/methane sensor based on niobium tungsten oxide nanorods synthesised by hydrothermal method

An investigation on hydrogen and methane sensing performance of hydrothermally formed niobium tungsten oxide nanorods employed in a Schottky diode structure is presented herein. By implementing tungsten into the surface of the niobium lattice, we create Nb5+ and W5+ oxide states and an abundant number of surface traps, which can collect and hold the adsorbate charge to reinforce a greater bending of the energy bands at the metal/oxide interface. We show experimentally, that extremely large voltage shifts can be achieved by these nanorods under exposure to gas at both room and high temperatures and attribute this to the strong accumulation of the dipolar charges at the interface via the surface traps. Thus, our results demonstrate that niobium tungsten oxide nanorods can be implemented for gas sensing applications, showing ultra-high sensitivities.

Hydrothermal synthesis and characterisation of Cu2ZnSnS4 light absorbers for solar cells

This project has extended the knowledge in the hydrothermal synthesis of copper zinc tin sulphide (CZTS) semiconductor material which is regarded as one of the most promising light absorbing material for PV technologies. The investigation of various reaction parameters on the controlled synthesis of CZTS compound has provided important insight into the formation mechanism as well as the crystal growth behaviour of the material. CZTS nanocrystals with different crystal structure and particle size were synthesised throughout this project. The growth mechanism of CZTS crystals through a high temperature annealing treatment was also explored.

A review of hydrothermal liquefaction bio-crude properties and prospects for upgrading to transportation fuels

Hydrothermal liquefaction (HTL) presents a viable route for converting a vast range of materials into liquid fuel, without the need for pre-drying. Currently, HTL studies produce bio-crude with properties that fall short of diesel or biodiesel standards. Upgrading bio-crude improves the physical and chemical properties to produce a fuel corresponding to diesel or biodiesel. Properties such as viscosity, density, heating value, oxygen, nitrogen and sulphur content, and chemical composition can be modified towards meeting fuel standards using strategies such as solvent extraction, distillation, hydrodeoxygenation and catalytic cracking. This article presents a review of the upgrading technologies available, and how they might be used to make HTL bio-crude into a transportation fuel that meets current fuel property standards.

Phase-selective hydrothermal synthesis of Cu2ZnSnS4nanocrystals: The effect of the sulphur precursor

High quality Cu2ZnSnS4 (CZTS) films with uniform thickness and smooth surface were prepared using nanocrystals synthesized by a one-step hydrothermal method. It is found that the nature of the sulphur precursor used in the hydrothermal reaction influences both the compositional purity and the crystal structure of the synthesized hydrothermal product significantly. The CZTS material consisting of both wurtzite and kesterite crystal structures was obtained when using an organic sulfur precursor such as thioacetamide and thiourea in the precursor solution of the hydrothermal reaction while the pure kesterite phase CZTS nanocrystals were made when Na2S was employed as the sulphur precursor. CZTS thin films deposited on a Mo–soda lime glass substrate with uniform thickness (1.7 μm) were made by a simple doctor-blading method. The investigation of the effect of thermal treatment on the film has indicated that the wurtzite CZTS material was completely transformed to the kesterite phase when the material was annealed at 550 °C. Large grains (around 2 μm in size) were found on the surface of the CZTS film which was annealed at 600 °C. The evaluation of the photoresponse of the CZTS thin films has showed that a higher and very stable photocurrent was generated by the film annealed at 600 °C compared to the film annealed at 550 °C.

One-step synthesis of high quality kesterite Cu2ZnSnS4nanocrystals: A hydrothermal approach

The present work demonstrates a systematic approach for the synthesis of pure kesterite-phase Cu2ZnSnS4 (CZTS) nanocrystals with a uniform size distribution by a one-step, thioglycolic acid (TGA)-assisted hydrothermal route. The formation mechanism and the role of TGA in the formation of CZTS compound were thoroughly studied. It has been found that TGA interacted with Cu2+ to form Cu+ at the initial reaction stage and controlled the crystal-growth of CZTS nanocrystals during the hydrothermal reaction. The consequence of the reduction of Cu2+ to Cu+ led to the formation Cu2−xS nuclei, which acted as the crystal framework for the formation of CZTS compound. CZTS was formed by the diffusion of Zn2+ and Sn4+ cations to the lattice of Cu2−xS during the hydrothermal reaction. The as-synthesized CZTS nanocrystals exhibited strong light absorption over the range of wavelength beyond 1000 nm. The band gap of the material was determined to be 1.51 eV, which is optimal for application in photoelectric energy conversion device.

Polyacrylic Acid Assisted Synthesis of Cu2ZnSnS4 by Hydrothermal Method

Pure phase Cu2ZnSnS4 (CZTS) nanoparticles were successfully synthesized via polyacrylic acid (PAA) assisted one-pot hydrothermal route. The morphology, crystal structure, composition and optical properties as well as the photoactivity of the as-synthesized CZTS nanoparticles were characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectrometer, UV-visible absorption spectroscopy and photoelectrochemical measurement. The influence of various synthetic conditions, such as the reaction temperature, reaction duration and the amount of PAA in the precursor solution on the formation of CZTS compound was systematically investigated. The results have shown that the crystal phase, morphology and particle size of CZTS can be tailored by controlling the reaction conditions. The formation mechanism of CZTS in the hydrothermal reaction has been proposed based on the investigation of time-dependent phase evolution of CZTS which showed that metal sulfides (e.g., Cu2S, SnS2 and ZnS) were formed firstly during the hydrothermal reaction before forming CZTS compound through nucleation. The band gap of the as-synthesized CZTS nanoparticles is 1.49 eV. The thin film electrode based on the synthesized CZTS nanoparticles in a three-electrode photoelectrochemical cell generated pronounced photocurrent under illumination provided by a red light-emitting diode (LED, 627 nm), indicating the photoactivity of the semiconductor material.

Hydrothermal liquefaction of bagasse using ethanol and black liquor as solvents

The objective of this study was to examine the hydrothermal liquefaction of sugarcane bagasse using ethanol and black liquor (BL) in a pilot scale. Combinations of co-solvents (ethanol/ water, ethanol/BL) were studied at various concentrations and reaction conditions. The maximum oil yield of 61% was achieved with a reaction temperature of 300 °C for 30 min and using pure BL as a solvent, while the highest higher heating value (HHV) was obtained from a 50:50 ethanol-BL mixture. The oils contained alcohols, esters, phenolic compounds, aromatics, and heterocyclics. The O/C and H/C ratios of the oil were comparable with traditional biodiesel and commercial diesel. Although this study showed there are some improvements to be made to improve the chemical composition, the approach has potential for large-scale production of a substitute for fossil-fuel-based diesel.

Direct precipitation of lead zirconate titanate by the hydrothermal method

Direct precipitation of fine powders of lead zirconate titanate (PZT) in the complete range of solid solution, is investigated under hydrothermal conditions, starting from lead oxide and titania/zirconia mixed gels. The perovskite phase is formed in the temperature range of 165 – 340°C. Sequence of the hydrothermal reactions is studied by identifying the intermediate phases. The initial formation of PbO: TiO2 solid solution is followed by the reaction of the same with the remaining mixed gels giving rise to X-ray amorphous PZT phase. Further, through crystallite growth, the X-ray crystalline PZT is formed. This method can be extended for the preparation of PLZT powder as well. The resulting powders are sinterable to high density ceramics.

BaSnO3 fine powders from hydrothermal preparations

Attempts to prepare BaSnO3 by the hydrothermal method starting from SnO2·xH2O gel and Ba (OH)2 solution in teflonlined autoclaves at 150–260°C invariably lead to the formation of a hydrated phase, BaSn(OH)6·3H2O. On heating in air or on releasing the pressure Image at ≈260°C, BaSN (OH)6·3H2O converts to BaSnO3 fine powder which involves the formation of an intermediate oxyhydroxide, BaSnO(OH)4. TEM studies show that particle size of the resulting BaSnO3 ranges from 0.2–0.6 μm. Solid solutions of Ba(Ti, Sn) O3 were prepared from (TiO2+SnO2)·xH2O mixed gel and Ba(OH)2 solutions. Single-phase perovskite Ba(Ti, Sn)O3 was obtained up to 35 atom % Sn. Above this composition, the hydrothermal products are mixtures of BaTiO3 (cubic) and BaSn(OH)6·3H2O which on heating at ≈260°C give rise to BaTiO3+BaSnO3. Annealing at 1000°C results in monophasic Ba(Ti, Sn)O3, in the complete range of Sn/Ti. Formation of the hydrated phase is attributed to the amphoteric nature of SnO2·xH2O gel which stabilises Sn(OH)62− anions under higher H2O-pressures and elevated temperatures. The sintering characteristics and dielectric properties of ceramics prepared from these fine powders are presented.

Optimal hydrothermal load flow: Formulation and a successive approximation solution for fixed head systems

This paper deals with the optimal load flow problem in a fixed-head hydrothermal electric power system. Equality constraints on the volume of water available for active power generation at the hydro plants as well as inequality constraints on the reactive power generation at the voltage controlled buses are imposed. Conditions for optimal load flow are derived and a successive approximation algorithm for solving the optimal generation schedule is developed. Computer implementation of the algorithm is discussed, and the results obtained from the computer solution of test systems are presented.

Hydrothermal synthesis of polycrystalline carbonates

Polycrystals of orthorhobic carbonates RCO3 (R = Sr, Ba and Pb) were synthesised for the first time using formic acid as mineraliser. The unit cell parameters of this synthetic pure carbonates are: BaCO3:a=5.309, B=8.889, C=6.401; srCO3:a=5.108, B=8.420, C=6.040; PbCO3: A=5.176, B=8.511, C=6.137.

Hydrothermal phase equilibria in Ln2O3-H2O-CO2 systems : I. The lighter lanthanides

Phase diagrams for Nd2O3-H2O-CO2 and Gd2O3-H2O-CO2 systems at 1500 atm are given along with the results of selected runs in La, Sm and Eu systems. The stable phases in systems of La and Nd, are Ln(OH)CO3-B, Ln2O2CO3-II and LnOOH, in addition to the Ln(OH)3 phase at extremely low partial pressures of CO2 in the system. The systems become more and more complex with decreasing ionic radi and the number of stable carbonate phases increases. Ln2(CO3)3 · 3H2O orthorhombic (tengerate-like phase) is stable from Sm to Gd in addition to the other phases. The Gd(OH)CO3-A (ancylite-like phase) is hydrothermally stable at XCO2 greater-or-equal, slanted 0.5 while its hexagonal polymorph, Gd(OH)CO3-B is stable at low partial pressures of CO2 in the system.