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.     

Hydropyrolysis of Light Hydrocarbons in H2/Ar Plasma Jet

The hydropyrolysis of light hydrocarbons were carried out in H₂/Ar plasma jet at atmosphere pressure and average temperature between 1500K and 3000K. The raw material was Liquefied Petroleum Gas. The experimental results show that among all the pyrolysis products, major product is acetylene. Carbon black is the byproduct. The yield and selectivity of acetylene can reach 74%, 80%, respectively. Carbon black is characterized with XRD, TEM, and adsorption-and-desorption of liquid nitrogen, respectively.     

Thermogravimetric study on the pressurized hydropyrolysis kinetics of a lignite coal

Hydropyrolysis of coal is considered to be a third coal conversion technology between the coal liquification and gasification technologies. It is also the primary process for coal hydrogasification (CHG). However, the detailed kinetic characteristics of coal hydropyrolysis (CHP) are still rarely studied, which is adverse to the further development of the CHP and CHG technologies. In this work, the hydropyrolysis kinetics of a lignite coal is studied in a pressurized thermogravimetric analyzer (P-TGA). The non-isothermal thermogravimetric method is used and the effect of pressure on the pyrolysis kinetics of the lignite coal is detected. Finally, some useful results are found from the analyses for the lignite hydropyrolysis under P-TGA. With the increment of the pyrolysis pressure, the initial pyrolysis temperature increases when the pressure is higher than 1 MPa; the temperature span of the pyrolysis process shrinks; the weight loss peak value position of the derivative thermogravimetric (DTG) curve shifts rightwards when the pressure is lower than 1 MPa, while it shifts leftwards when the pyrolysis pressure is higher than 1 MPa; the reaction process will be restrained when the pressure is lower than 2 MPa. In addition, the kinetic triplets including the pre-exponential factor, the activation energy and the kinetic mechanism function are defined for the hydropyrolysis process under different pressures.     

Hydrodeoxygenation of oils from cellulose in single and two-stage hydropyrolysis

To investigate the removal of oxygen (hydrodeoxygenation) during the hydropyrolysis of cellulose, single and two-stage experiments on pure cellulose have been carried out using hydrogen pressures up to 10 MPa and temperatures over the range 300–520°C. Carbon, oxygen and aromaticity balances have been determined from the product yields and compositions. For the two-stage tests, the primary oils were passed through a bed of commercial Ni/Mo γ-alumina-supported catalyst (Criterion 424, presulphided) at 400°C. Raising the hydrogen pressure from atmospheric to 10 MPa increased the carbon conversion by 10 mole % which was roughly equally divided between the oil and hydrocarbon gases. The oxygen content of the primary oil was reduced by over 10% to below 20% w/w. The addition of a dispersed iron sulphide catalyst further increased the oil yield at 10 MPa and reduces the oxygen content of the oil by a further 10%. The effect of hydrogen pressure on oil yields was most pronounced at low flow rates where it is beneficial in helping to overcome diffusional resistances. Unlike the dispersed iron sulphide in the first stage, the use of the Ni-Mo catalyst in the second stage reduced both the oxygen content and aromaticity of the oils.     

Hydropyrolysis of Light Hydrocarbons in H2/Ar Plasma Jet

Abstract

The hydropyrolysis of light hydrocarbons were carried out in H₂/Ar plasma jet at atmosphere pressure and average temperature between 1500K and 3000K. The raw material was Liquefied Petroleum Gas. The experimental results show that among all the pyrolysis products, major product is acetylene. Carbon black is the byproduct. The yield and selectivity of acetylene can reach 74%, 80%, respectively. Carbon black is characterized with XRD, TEM, and adsorption-and-desorption of liquid nitrogen, respectively.     

Hydropyrolysis of Alberta coal and petroleum residue using calcium oxide catalyst and toluene additive

Hydropyrolysis of a mixture of Alberta coal and Athabasca bitumen was carried out in a batch reactor using calcium oxide as an alternate catalyst and the results were compared with those of widely used iron oxide and well-known NiMo/Al₂O₃ catalysts. Most of the reactions were done at temperatures of 500–540°C, residence time of 1 min and hydrogen pressure of 3.4 MPa. Maximum distillable oil (below 523°C) yield of 55 wt% and pitch conversion of 62 wt% were obtained in the presence of CaO or Fe₂O₃ and these values were higher than those without catalyst, although NiMo/Al₂O₃ catalyst gave much higher oil yield and pitch conversion. Catalyst concentration (above 2 wt%) has no consequence upon the distribution of various product fractions.

In another study, addition of 15% toluene to the feed in the absence of catalyst led to higher distillable oil yield (68 wt%) and pitch conversion (72 wt%) in the hydroconversion of coal and bitumen mixture. Increase in toluene concentration from 15 to 50 wt% had no positive effect on the product yields.     

The study of different methods of bio-liquids production from wood biomass and from biomass/polyolefine mixtures

The different methods of wood biomass thermal liquefaction at atmospheric and elevated pressures were investigated in order to select the more effective one. Wood biomass liquefaction by melted formate/alkali mixtures and with the use of metallic iron/Na₂CO₃ system is carried out at low pressures. But these methods give only moderate yield of bio-liquids. The highest yield of bio-liquid was obtained in the process of biomass dissolvation in methanol media in the presence of Zn–Cr–Fe catalyst at 20 MPa. Co-pyrolysis and co-hydropyrolysis of biomass/polyolefine mixtures makes it possible to obtain the rather high yield of bio-liquid at the moderate pressures (3 MPa).     

High pressure hydropyrolysis of coals by using a continuous free-fall reactor

Rapid hydropyrolysis of coal was carried out at temperatures ranging from 923 to 1123 K and H₂ pressures up to 7 MPa by using a continuous free-fall pyrolyzer. The effects of the reaction conditions on product yields were investigated. Carbon mass balance was fairly good. It was revealed that a large amount of methane was produced due to the hydrogenolysis of higher hydrocarbons and the hydrogasification of char. The influence of pyrolysis temperature was significant on both reactions while H₂ pressure mainly affected the latter. A considerable amount of reactive carbon was formed during hydropyrolysis of coal. It was converted to methane at high temperatures and high H₂ pressures, while the hydrogasification of reactive carbon takes place relatively slowly at low temperatures and low H₂ pressures, resulting in a low overall carbon conversion. The coal conversions observed in the present study were much higher than those obtained with using reactors where the contact between coal particles and H₂ is insufficient.     

两种灰岩的生气特征比较研究

依据较纯灰岩和泥灰岩的加水热模拟实验结果,探讨了二者的生气特征。认为二者生气特征存在差异主要与有机质类型和岩石矿物成分有关。泥灰岩比纯灰岩所产气体中含有更多的甲烷、乙烷、异丁烷和异戊烷。在中、低温度段,泥灰岩所产气体的C1/ΣC+1、C2/C3值和所产氢气、氮气的量高于纯灰岩。氢气主要形成于较高和较低温度段,氮气主要形成于中、低温度段。二氧化碳含量与碳酸盐含量有关。在中、低温度段,纯灰岩的总气体、总烃气产率高于泥灰岩,当温度更高时,烃气产率大小则相反。