Hydrogen Production from Catalytic Steam Reforming of Bio-Oils: A Critical Review

In the future, hydrogen will be an important energy carrier and industrial raw material. Catalytic steam reforming of bio-oils is a promising and economically viable technology for hydrogen production. However, during the reforming process, the catalysts are rapidly deactivated due to coke formation and sintering. Thus, maintaining the activity and stability of catalysts is the key issue in this process. Optimized operation conditions could extend the catalyst lifetime by affecting the coke morphology or promoting coke gasification. This article summarizes the recent developments in the field of catalytic steam reforming of bio-oils, focusing on the operation conditions, the properties of the catalysts, and the effects of the catalyst supports. The expected insights into the catalytic steam reforming of bio-oils will provide further guidance for hydrogen production from bio-oils.     

Comparison of the generation of oil by the extraction and the hydropyrolysis of biomass

This paper discusses the maximisation of the yields of useful bio-oils generated from seeds and nut-shells both by extraction and by hydropyrolysis. The formation and the composition of the bio-oils are also discussed.Powdered (<0.25 mm diameter) Rapeseed, Linseed and Safflower seed and Hazel nut and Walnut shells, that is, fresh precursors of liptinite, have been characterised by their elemental analyses, infra-red and NMR spectra. Bio-oils obtained both by extraction and by slow hydropyrolysis to 520 °C at moderate pressure in the presence of ammonium dioxydithiomolybdate have been compared by the same analyses and by gas chromatography. Consistent with previous work [Hardy JA. A greener future with biodiesel. Green Chem 2001 G56-G57], extraction of the seeds with organic solvents, including Diesel oil, gave yields of up to 40% together with an uninteresting residue. However, subsequent saponification of the residues gave further yields of oil. Hydropyrolysis removed oxygen from the seeds as water and as oxides of carbon to generate bio-oil in yields of up to 75%. Whereas little oil could be extracted from the nut-shells, hydropyrolysis gave oil yields of ∼40%. Some char was also formed, suggesting that optimisation of the hydropyrolysis might give even larger yields of oil.     

Effects of particle sizes on performances of the multi-zone steam generator using waste heat in a bio-oil steam reforming hydrogen production system

Hydrogen production by bio-oil steam reforming is an advanced production technology. It is a good method of coupling waste heat utilization with bio-oil steam reforming to produce hydrogen, which increases the cleaning ability of the bio-oil steam reforming system. A multi-zone steam generator using waste heat has been proposed, which can produce the heat source and steam source of the hydrogen system. The DEM model of the multi-zone steam generator was set up. The model has been used to investigate the effects of particle sizes (40 mm–80 mm). With increasing particle size, the flow index and the flow uniformity gradually decrease, the vertical velocity gradient increases in the area on both side with the zone steam generator, and the vertical velocity fluctuation amplitude gradually increases. So, the hydrogen production decreases from the particle size increasing.     

Catalytic hydrotreating of pyro-oil derived from green microalgae spirulina the (Arthrospira) plantensis over NiMo catalysts impregnated over a novel hybrid support

Upgrading of pyrolysis bio-oil by a novel catalytic hydrotreating process, including hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) was found as an effective technical method for the improvement of biofuel characteristics. In this study, for the first time, the performance of a novel meso-microporous composite material, HMS-ZSM-5, as a support on the catalytic activity of NiMo-based catalysts in the bio-oil hydrotreating was evaluated. The experiments were carried out in a flow fixed-bed reactor at the temperature range of 300–360 °C, 30 bar pressure, and LHSV = 4 h-1. Also, the results were and compared with those of HMS, ZSM-5, and γ-Al2O3 supports. For all catalysts, the increase in temperature resulted in the enhancement of HDO and HDN reactions efficiency. NiMo/HMS-ZSM-5 possessed a high acid property which contributed to the removal of oxygen and nitrogen from bio-oil, with the conversion of 84.10% and 69.60%, respectively. Therefore, the novel catalyst of this study represented much superior upgrading performances compared with those of stand-alone NiMo/HMS and NiMo/ZSM-5 catalysts and also the conventional catalyst of NiMo/γ-Al2O3.     

A review of bio-oils from waste biomass: Focus on fish processing waste

Biofuels are derived from biomass using biochemical, thermochemical, and physical and chemical extraction processes. Waste oils from animal and vegetable sources continue to be important biomass feedstock due to the potential benefits over petroleum and some of the virgin vegetable oil based fuels. In this paper, the chemical, thermal, and physical properties of biofuels derived from virgin and waste sources are reviewed. In addition, the processes used for recovering bio-oils from animal fats (beef tallow, lard, and poultry waste) and greases, and purification and refining of bio-oils are discussed as well as the resulting performance as a fuel. Particular focus will be on production of biofuels from fish waste. The potential for biofuel from fish waste is a function of the location and size of the processing plant, type of fuel requirements, and characteristics of the fish waste.     

Oxidative pyrolysis of kraft lignin in a bubbling fluidized bed reactor with air

Fast pyrolysis of kraft lignin with partial (air) oxidation was studied in a bubbling fluidized bed reactor at reaction temperatures of 773 and 823 K. The bio-oil vapors were fractionated using a series of three condensers maintained at desired temperatures, providing a dry bio-oil with less than 1% water and over 96% of the total bio-oil energy.Oxygen feed was varied to study its effect on yield, composition, and energy recovery in the gas, char and oil products. The addition of oxygen to the pyrolysis process increased the production of gases such as CO and CO₂. It also changed the dry bio-oil properties, reducing its heating value, increasing its oxygen content, reducing its average molecular weight and tar concentration, while increasing its phenolics concentration. The lower reaction temperature of 773 K was preferred for both dry bio-oil yield and quality.Autothermal operation of the pyrolysis process was achieved with an oxygen feed of 72 or 54 g per kg of biomass at the reaction temperatures of 773 and 823 K, respectively. Autothermal operation reduced both yield and total energy content of the dry bio-oil, with relative reductions of 24 and 20% for the yield, 28 and 23% for the energy content, at 773 and 823 K.     

Upgrading the lubricity of bio-oil via homogeneous catalytic esterification under vacuum distillation conditions

In order to accelerate the application of bio-oil in the internal combustion engines, homogeneous catalytic esterification technology under vacuum distillation conditions was used to upgrade the crude bio-oil. The lubricities of the crude bio-oil (BO) and refined bio-oil with homogeneous catalytic esterification (RBO_hce) or refined bio-oil without catalyst but with distillation operation (RBO_wc) were evaluated by a high frequency reciprocating test rig according to the ASTM D 6079 standard. The basic physiochemical properties and components of the bio-oils were analyzed. The surface morphology, contents and chemical valence of active elements on the worn surfaces were investigated by scanning electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy, respectively. The results show that RBO_hce has better lubricities than those of BO, but RBO_wc has worse lubricities than those of BO. The tribological mechanisms of the bio-oils are attributed to the combined actions of lubricating films and factors that will break the film. Compared with BO, plenty of phenols in RBO_wc results in corrosion of the substrate and destroys the integrity of the lubricating films, which is responsible for its corrosive wear. However, more esters and alkanes in RBO_hce contribute to forming a complete boundary lubricating film on the rubbed surfaces which result in its excellent antifriction and antiwear properties.     

An overview of empty fruit bunch from oil palm as feedstock for bio-oil production

Empty fruit bunch (EFB) from oil palm is one of the potential biomass to produce biofuels like bio-oil due to its abundant supply and favorable physicochemical characteristics. Confirming the assertion, this paper presents an overview of EFB as a feedstock for bio-oil production. The fundamental characteristics of EFB in terms of proximate analysis, ultimate analysis and chemical composition, as well as the recent advances in EFB conversion processes for bio-oil production like pyrolysis and solvolysis are outlined and discussed. A comparison of properties in terms of proximate analysis, ultimate analysis and fuel properties between the bio-oil from EFB and petroleum fuel oil is included. The major challenges and future prospects towards the utilization of EFB as a useful resource for bio-oil production are also addressed.     

Zr02-A1203负载催化剂减压精馏催化酯化生物质裂解油

以Z102-A1203作为催化剂载体,分别制备了SO^2-4／ZrO2-Al2O3、NaOH/Zr02-Al2O3、ZrO2-Al2O33种固体催化剂,并采用酯化后3A分子筛除水和减压反应精馏两种方法精制生物质裂解油。结果表明,在分别使用SO^2-4／ZrO2-Al2O3、NaOH/Zr02-Al2O3、ZrO2-Al2O333种催化剂的条件下,酯化后3A分子筛除水的方式,可以将产品的含水率降至19．6％、18．3％和15．6％,而反应精馏可以将产品含水率分别降低至4．8％、5．4％和3．8％,较之前者效果更加明显。另外,对于3种不同性质的催化剂,结合酯化度计算式,对催化生物油酯化效果进行评价,可知其催化活性为：SO^2-4／ZrO2-Al2O3、NaOH/Zr02-Al2O3、ZrO2-Al2O33。最后,将得到的油品性质进行检测（包括黏度、pH值、密度和热值等）,各项结果表明,使用硫酸化催化剂。并采用减压反应精馏的酯化方式可以制备出一种性能优良的液体燃料。