Preparation of Hydrogen through Catalytic Steam Reforming of Bio-oil

Hydrogen was prepared via catalytic steam reforming of bio-oil which was obtained from fast pyrolysis of biomass in a fluidized bed reactor.Influential factors including temperature,weight hourly space velocity(WHSV) of bio-oil,mass ratio of steam to bio-oil(S/B) as well as catalyst type on hydrogen selectivity and other desirable gas products were investigated.Based on hydrogen in stoichiometric potential and carbon balance in gaseous phase and feed,hydrogen yield and carbon selectivity were examined.The experimental results show that higher temperature favors the hydrogen selectivity by H2 mole fraction in gaseous products stream and it plays an important role in hydrogen yield and carbon selectivity.Higher hydrogen selectivity and yield,and carbon selectivity were obtained at lower bio-oil WHSV.In catalytic steam reforming system a maximum steam concentration value exists,at which hydrogen selectivity and yield,and carbon selectivity keep constant.Through experiments,preferential operation conditions were obtained as follows:temperature 800～850℃,bio-oil WHSV below 3.0 h-1,and mass ratio of steam to bio-oil 10～12.The performance tests indicate that Ni-based catalysts are optional,especially Ni/α-Al2O3 effective in the steam reforming process.

Effects of Temperature and Catalyst to Oil Weight Ratio on the Catalytic Conversion of Heavy Oil to Propylene Using ZSM-5 and USY Catalysts

It is useful for practical operation to study the rules of production of propylene by the catalytic conversion of heavy oil in FCC （fluid catalytic cracking）. The effects of temperature and C/O ratio （catalyst to oil weight ratio） on the distribution of the product and the yield of propylene were investigated on a micro reactor unit with two model catalysts, namely ZSM-5/Al2O3 and USY/Al2O3, and Fushun vacuum gas oil （VGO） was used as the feedstock. The conversion of heavy oil over ZSM-5 catalyst can be comparable to that of USY catalyst at high temperature and high C/O ratio. The rate of conversion of heavy oil using the ZSM-5 equilibrium catalyst is lower compared with the USY equilibrium catalyst under the general FCC conditions and this can be attributed to the poor steam ability of the ZSM-5 equilibrium catalyst. The difference in pore topologies of USY and ZSM-5 is the reason why the principal products for the above two catalysts is different, namely gasoline and liquid petroleum gas （LPG）, repspectively. So the LPG selectivity, especially the propylene selectivity, may decline if USY is added into the FCC catalyst for maximizing the production of propylene. Increasing the C/O ratio is the most economical method for the increase of LPG yield than the increase of the temperature of the two model catalysts, because the loss of light oil is less in the former case. There is an inverse correlation between HTC （hydrogen transfer coefficient） and the yield of propylene, and restricting the hydrogen transfer reaction is the more important measure in increasing the yield of propylene of the ZSM-5 catalyst. The ethylene yield of ZSM-5/A1203 is higher, but the gaseous side products with low value are not enhanced when ZSM-5 catalyst is used. Moreover, for LPG and the end products, dry gas and coke, their ranges of reaction conditions to which their yields are dependent are different, and that of end products is more severe than that of LPG. So it is clear that maximizing LPG and propylene and restricting dry gas and coke can be both achieved via increasing the severity of reaction conditions among the range of reaction conditions which LPG yield is sensitive to.

Low gas-liquid ratio foam flooding for conventional heavy oil

The recovery of heavy oil by water flooding is 10% lower than that of conventional crude oil, so enhanced oil recovery （EOR） is of great significance for heavy oil. In this paper, foam flooding with a gas-liquid ratio （GLR） of 0.2：1 for the Zhuangxi heavy oil （325 mPa.s at 55 ℃） was performed on cores, sand packs and plate model. In sand pack tests, polymer enhanced foam flooding increased oil recovery by 39.8%, which was 11.4% higher than that for alkali/surfactant/polymer （ASP） flooding under the same conditions. Polymer enhanced foam flooding in plate models shows that the low GLR foam flooding increased oil recovery by about 30%, even when the extended water flooding was finished at 90% water cut. Moreover, it was discovered by microscopy that foam was more stable in heavy oil than in light oil. These results confirm that low GLR foam flooding is a promising technology for displacing conventional heavy oil.

Hydrolysis - Hydrogenation of soybean oil and tallow

Hydrolysis reactions are of major importance to the oleochemical industry in the production of fatty acid and their derivates. Hydrolysis of triglyceride from vegetable oil has been studied under various parameters such as: heterogeneous catalyst, temperature, reaction time and agitation speed. During the hydrolysis of soybean oil and tallow using nickel catalysts on alumina support was verified that the glycerol produced worked as hydrogen donor, allowing the hydrogenation of unsaturated fatty acids produced. Maximum conversion was achieved in 3 hours, catalysts 25% NiO/Al2O3, temperature of 250oC and 270oC and 250 rpm.

Aqueous-phase catalytic hydrogenation of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts:Model reaction for upgrading of bio-oil

A series of Cu-Mg-Al hydrotalcites derived oxides with a(Cu+Mg)/Al mole ratio of 3 and varied Cu/Mg mole ratio(from 0.07 to 0.30) were prepared by co-precipitation and calcination methods, then they were introduced to the hydrogenation of furfural in aqueous-phase. Effects of Cu/Mg mole ratio, reaction temperature, initial hydrogen pressure, reaction time and catalyst amount on the conversion rate of furfural as well as the selectivity toward desired product cyclopentanol were systematically investigated. The conversion of furfural over calcined hydrotalcite catalyst with a Cu/Mg mole ratio of 0.2 was up to 98.5% when the reaction was carried out under 140 ?C and the initial hydrogen pressure of 4 MPa for 10 h, while the selectivity toward cyclopentanol was up to 94.8%. The catalysts were characterized by XRD and SEM. XRD diffraction of all the samples showed characteristic pattern of hydrotalcite with varied peak intensity as a result of different Cu content. The catalytic activity was improved gradually with the increase of Cu component in the hydrotalcite.

Hydrogen production via steam reforming of bio-oil model compounds over supported nickel catalysts

The steam reforming of four bio-oil model compounds（acetic acid,ethanol,acetone and phenol） was investigated over Ni-based catalysts supported on Al2O3 modified by Mg,Ce or Co in this paper.The activation process can improve the catalytic activity with the change of high-valence Ni（Ni2O3,NiO） to low-valence Ni（Ni,NiO）.Among these catalysts after activation,the Ce-Ni/Co catalyst showed the best catalytic activity for the steam reforming of all the four model compounds.After long-term experiment at 700°C and the S/C ratio of 9,the Ce-Ni/Co catalyst still maintained excellent stability for the steam reforming of the simulated bio-oil（mixed by the four compounds with the equal masses）.With CaO calcinated from calcium acetate as CO2 sorbent,the catalytic steam reforming experiment combined with continuous in situ CO2 adsorption was performed.With the comparison of the case without the adding of CO2 sorbent,the hydrogen concentration was dramatically improved from 74.8% to 92.3%,with the CO2 concentration obviously decreased from 19.90% to 1.88%.

Hydrogenation of Pyrolysis Oil from Loblolly Pine Residue

Loblolly pine residue prepared with and without zeolite ZSM-5 was pyrolyzed at 600℃ and the pyrolysis oil was hydrogenated using formic acid as a hydrogen source, in the presence of a Ru/activated carbon catalyst. As indicated by the pyrolysis yield, addition of the zeolite ZSM-5 increased the yield of light oil but decreased the yield of heavy oil. The pyrolysis oils were analyzed by 13C-,31P-,19F-nuclear magnetic resonance(NMR), and heteronuclear single quantum coherence or heteronuclear single quantum correlation nuclear magnetic resonance(HSQC-NMR), demonstrating that the zeolite ZSM-5 can efficiently induce decarboxylation reactions and decrease the content of aliphatic hydroxyl groups in the heavy oil by 57%.After hydrogenation of the pyrolysis oil, the aromatic carbon content decreased by 78%, with a significant increase in the aliphatic carbon content.

Organic matter transformation ratio, hydrocarbon expulsion efficiency and shale oil enrichment type in Chang 7_(3) shale of Upper Triassic Yanchang Formation in Ordos Basin, NW China

The major enrichment type of shale oil in the Chang 7_(3) shale of Upper Triassic Yanchang Formation in the Ordos Basin is unknown.This paper analyzes the organic matter transformation ratio,hydrocarbon expulsion efficiency and roof/floor sealing conditions of the Chang 7_(3) shale,and evaluates the major enrichment type of shale oil in this interval.The average organic matter transformation ratio of the Chang 7_(3) shale is about 45%;in other words,more than 50%of the organic matters have not transformed to hydrocarbons,and the lower the maturity,the greater the proportion of untransformed organic matters.The cumulative hydrocarbon expulsion efficiency of the transformed hydrocarbon is 27.5% on average,and the total proportion of untransformed organic matters plus retained hydrocarbons is greater than 70%.The relative hydrocarbon expulsion efficiency of the Chang 7_(3) shale is 60%on average,that is,about 40% of hydrocarbons retain in the shale.The Chang 7_(3) shale corresponds to Chang 7_(1+2) and Chang 8 sandstones as the roof and floor,respectively,and is further overlaid by Chang 6 shale,where extensive low porosity and low permeability–tight oil reservoirs have formed in the parts with relatively good porosity and permeability.Moreover,the Chang 7_(3) shale is tested to be in a negative pressure system(the pressure coefficient of 0.80–0.85).Therefore,the roof/floor sealing conditions of the Chang 7_(3) shale are poor.The retained hydrocarbons appear mostly in absorbed status,with low mobility.It is concluded that the medium–high mature shale oil is not the major enrichment type of shale oil in the Chang 7_(3) shale,but there may be enrichment opportunity for shale oil with good mobility in the areas where the sealing conditions are good without faults and fractures and oil reservoirs are formed off Chang 7_(1+2),Chang 6 and Chang 8.Furthermore,low–medium mature shale oil is believed to have great potential and is the major enrichment type of shale oil in the Chang 7_(3) shale.It is recommended to prepare relevant in-situ conversion technologies by pilot test and figure out the resource availability and distribution.

Influences of stoichiometric ratio B/A on structures and electrochemical behaviors of La_(0.75)Mg_(0.25)Ni_(3.5)M_x (M=Ni,Co;x=0-0.6) hydrogen storage alloys

In order to investigate the influences of the stoichiometric ratio of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structures and electrochemical performances of the AB3.5-4.1-type electrode alloys, the La-Mg-Ni-Co system La0.75Mg0.25Ni3.5Mx (M=Ni, Co; x= 0, 0.2, 0.4, 0.6) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The results show that the structures and electrochemical performances of the alloys are closely relevant to the B/A ratio. All the alloys exhibit a multiphase structure, including two major phases, (La, Mg)2Ni7 and LaNi5, and a residual phase LaNi2, and with rising ratio B/A, the (La,Mg)2Ni7 phase decreases and the LaNi5 phase increases significantly. When ratio B/A=3.7, the alloys obtain the maximum discharge capacities. The high rate discharge(HRD) capability of the alloy (M=Ni) monotonously rises with growing B/A ratio, but that of the alloy (M=Co) first mounts up then declines. The cycle stability of the alloy (M=Co) monotonously increases with rising B/A ratio, but it first decreases slightly then increases for the alloy (M=Ni). The discharge potential of the alloy (M=Ni) declines with increasing B/A ratio (x>0.2), but for the alloy (M=Co), the result is contrary. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed ratio B/A=3.7, the Co substitution enhances the discharge capacity from 365.7 to 401.8 mA·h/g, the capacity retention ratio (S100) after 100 charging-discharging cycles from 50.32% to 53.26% and the HRD from 88.65% to 90.69%.

EFFECTS OF STOICHIOMETRIC RATIO ON STRUCTURE AND ELECTRODE PERFORMANCE OF HYDROGEN STORAGE ALLOYS

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Towards the insights into the deactivation behavior of acetylene hydrogenation catalyst

A series of model catalysts were obtained by treating commercial fresh and spent catalysts unloaded from the factory with different methods, including green oil dipping, extraction and high-temperature regeneration;finally, the deactivation behavior of the commercial catalyst for acetylene hydrogenation were studied. The influence of various possible deactivation factors on the catalytic performance was elucidated via detailed structural characterization, surface composition analysis, and activity evaluation.The results showed that green oil, carbon deposit and sintering of active metal were the main reasons for deactivation, among which green oil and carbon deposit led to rapid deactivation, while the activity could be recovered after regeneration by high-temperature calcination. The sintering of active metal components was attributed to the high-temperature regeneration in hydrothermal conditions, which was slow but irreversible and accounted for permanent deactivation. Thus, optimizing the regeneration is expected to extend the service life of the commercial catalyst.

Production of Cocoa Butter Replacer by Dry Fractionation, Partial Hydrogenation, Chemical and Enzymatic Interesterification of Tea Seed Oil

Production of cocoa butter replacer (CBR) from tea seed oil through common modification methods of oils (dry fractionation, partial hydrogenation, chemical and enzymatic interesterification) was evaluated. Some physico-chemical properties (iodine, saponification, acid and peroxide values) and fatty acid composition (FAC) of modified samples were analyzed and compared with a reference cocoa butter (CB). Solid and liquid fractions for large amounts of unsaturated fatty acids (approx. 80%) and thereby lower iodine values (81 - 85 gI2/100g) than that of CB (37% and 34 gI2/100 g, respectively), are not suitable as CBR. Among all ratios of chemically and enzaymatically interesterified oil blends (20%, 25% and 30% of hydrogenated tea seed oil with 80%, 75% and 70% of tea seed oil/liquid fraction/solid fraction), the samples with ratio of 30:70 from both chemical and enzymatic interesterification had FAC and iodine value closer to that of CB. A comparision between chemically and enzymatically interesterified samples (CISs and EISs, respectively), in terms of solid fat content (SFC) indicated that although the SFC values in EIS were much lower than that of CB, but the thermal behavior of this sample is comprable to CB at 20℃- 30℃ (sharp melting point of CB).

Effects of ratio of hydrogen flow on microstructure of hydrogenated microcrystalline silicon films deposited by magnetron sputtering at 100 ℃

Hydrogenated microcrystalline silicon(μc-Si:H)films were prepared on glass and silicon substrates by radio frequency magnetron sputtering at 100°C using a mixture of argon(Ar)and hydrogen(H2)gasses as precursor gas.The effects of the ratio of hydrogen flow(H2/(Ar+H2)%)on the microstructure were evaluated.Results show that the microstructure,bonding structure,and surface morphology of theμc-Si:H films can be tailored based on the ratio of hydrogen flow.An amorphous to crystalline phase transition occurred when the ratio of hydrogen flow increased up to 50%.The crystallinity increased and tended to stabilize with the increase in ratio of hydrogen flow from 40%to 70%.The surface roughness of thin films increased,and total hydrogen content decreased as the ratio of hydrogen flow increased.Allμc-Si:H films have a preferred(111)orientation,independent of the ratio of hydrogen flow.And theμc-Si:H films had a dense structure,which shows their excellent resistance to post-oxidation.

RNA/DNA Ratio and LPL and MyoD mRNA Expressions in Muscle of Oreochromis niloticus Fed with Elevated Levels of Palm Oil

Palm oil is of great potential as one of the sustainable alternatives to fish oil(FO) in aquafeeds.In this present study,five isonitrogenous diets(32% crude protein) with elevated palm oil levels of 0%,2%,4%,6% and 8% were used during an 8-week feeding trial to evaluate its effects on RNA/DNA ratio and lipoprotein lipase(LPL) and Myo D m RNA expressions in muscle of Oreochromis niloticus.The results showed that RNA,DNA content as well as ratio of RNA to DNA were significantly affected(P < 0.05),in each case the highest was recorded in fish group subjected to 6% palm oil level.There was a strong positive correlation between nucleic acid concentration(RNA concentration and RNA:DNA ratio) and specific growth rate(SGR),protein efficiency ratio(PER),while a negative correlation existed between nucleic acid concentration(RNA concentration and RNA:DNA ratio) and feed conversion ratio(FCR).The m RNA expressions of LPL and Myo D in muscle were not significantly affected by the different palm oil levels,although the highest expression was observed in fish fed with 6% palm oil level.There also existed a strong positive correlation between the m RNA expression of LPL,Myo D and SGR,PER,while their correlation with FCR was negative.In conclusion,elevated palm oil affected the RNA,DNA concentration as well as RNA/DNA ratio significantly,although the m RNA expression of LPL and Myo D were not affected significantly by elevated palm oil levels.

Effects of Use and Re-Use of Selected Vegetable Oils on the Proximate, Minerals, Mineral Ratios and Mineral Safety Index of Raw and Fried Plantain Chips: Note I

Raw and fried plantain chips obtained from the use and re-use of olive, refined palm olein and coconut oils were investigated for the proximate, mineral compositions, computed mineral ratios and the mineral safety index using standard analytical methods. For the selected oils (both use and re-use): first and second re-use and the fresh plantain chips (unprocessed plantain chips;UPC) had the following range results: proximate composition (%) (moisture: 8.20 - 12.3, crude protein: 9.70 - 8.60, fat: 7.40 - 12.9, fibre: 3.50 - 4.90, ash: 2.80 - 3.80 and carbohydrates: 63.5 - 64.8), % energy contributions (PEC: 63.4 - 70.8, PEF: 20.2 - 28.6, PEP: 8.03 - 9.66, UEDP: 4.49 - 5.08). The mineral composition (mg/100g) of the samples had the following greater than 80.0: Ca, Mg, K and P;Fe, Cu, Mn and Zn recorded values ranging between 1.00 and 4.00;Co, Se and Ni had their concentrations between 0.00 and 0.0363 whereas Pb and Cd recorded levels lower than 0.0006. In the mineral ratios, only K/(Ca + Mg) values fell within the acceptable ideal range. No MSI aberration was observed for the minerals from all the samples obtained from the various oils. The chi-square analysis showed that on parameter wise comparisons, there were no significant differences among the levels as treated based on the various oils except gross energy, Mg, K, P, Ca/P, Fe/Pb and K/Co. Also on pairwise comparison from linear correlation and regression, all these parameters were significantly different at r = 0.01 between the unprocessed and fried plantain samples: proximate, percentage energy distribution, mineral and mineral ratios. Generally, the first (day) frying showed fairly high nutrient concentration than the first and second re-use oils products. Therefore, for optimum nutrient preservation from fried plantain chips re-use of oil for frying should be sparingly allowed. However, olive showed highest level of nutrients in terms of proximate and mineral compositions.

Comparison of ASBR and CSTR reactor for hydrogen production from palm oil mill effluent under thermophilic condition

Hydrogen production from palm oil mill effluent (POME) by Thermoanaerobacterium thermosaccharolyticum PSU-2 was investigated both in batch and continuous reactors using anaerobic sequencing batch reactor (ASBR) and continuous stirred tank reactor (CSTR). The hydrogen production determined from batch experiment of POME at an inoculum size of 0%, 10%, 20% and 30% (v/v) was 161, 201, 246 and 296 mL H2/g-COD with COD removal efficiency of 21%, 23%, 23% and 23%, respectively. Continuous hydrogen production was start-up with 30% (v/v) inoculum in both ASBR and CSTR reactors and more than 30% COD removal could be obtained at HRT of 4 days, corresponding to OLR of 11.3 g COD/ L·day. Similar hydrogen production rates of 2.05 and2.16 LH2/L. day were obtained from ASBR and CSTR, respectively. COD removal efficiency of ASBR was 37.7%, while it was 44.8% for CSTR. However, ASBR was stable in term of alkalinity, while the CSTR was stable in term of hydrogen production, soluble metabolites concentration and alkalinity. Therefore, the CSTR was found to be more stable in hydrogen production than ASBR under the same OLR.

Oxygen and hydrogen isotope ratios of chert from the Sixtymile Formation in Grand Canyon National Park,USA：a warm palaeoclimate,freshwater deposit

New oxygen and hydrogen isotope ratios of chert from middle, intraformational breccias, and upper breccia members of the Sixtymile Formation（SMF） in eastern Grand Canyon National Park（AZ） yield palaeoclimate estimates between 27 and 33℃. The isotopic compositions of cherts define a domain approximately parallel to the meteoric water line when plotted on a δD–δ-（18）O diagram; these data indicate that meteoric water was involved during formation of the chert. In thin section, the absence of interlocking mega quartz（〉35 lm） and silicafilled fractures and veins, along with preserved micromorphological silica fabrics, suggest that the chert has not been permeated by later hydrothermal fluids. Petrographic observations in thin section such as cyclic silica precipitation phases and glaebular micromorphologic fabrics lend support to the interpretation that meteoric waters were involved during chert precipitation. The post 742 Ma SMF has been correlated with diamictite（transition） beds of the Kingston Peak Formation（CA）, which in turn have been interpreted to have been deposited during the Sturtian Ice Age（-750–700 Ma）. Absence of facetted and striated clasts and other diagnostic glaciogenic features in the SMF,an unconformable contact with the stratigraphically older Chuar Group, coupled with warm palaeotemperature data inferred from stable isotope values of chert, tentatively suggest that deposition of sediment in the SMF likely did not take place during the Sturtian Ice Age.

Biohydrogen Production from Synthetic Waste Co-digested with Liquid Dairy Cow Manure： Effect of Temperature and Mixing Ratio

Biohydrogen production from synthetic waste, SW （model organic fraction of municipal solid waste） co-digested with liquid dairy manure （M） was tested in batch reactions to assess the effect of temperature and mixing ratio of the substrates. A 5 × 2 factorial design experiment was conducted. Synthetic waste： manure mixtures of 1：1, 2：1, 3：1, 1：0, 0：1 （volatile solids, VS, basis） were tested at 37 （T37） and 55 ℃ （T55） using thirty 1 L laboratory scale digesters. Total VS of each mixture was 50 g/L except SW：M 0：I treatment, where total VS was 27.4 g/L. Gas samples were taken daily to determine hydrogen production, and slurry samples taken before and after experimentation, were analyzed for volatile fatty acid （VFA） concentration, volatile solid （VS） degradation, ammonium nitrogen （NH4＋-N） and pH. Hydrogen production （mL/g-VS fed） showed a significant two-factor interaction between incubation temperature and SW：M ratio （P 〈 0.001）. Maximum production of 15.8 mL/g-VS （fed） was achieved in SW：M ratio of 3：1 at 55 ℃. Generally, hydrogen productions at thermophilic temperature （T55） were significantly higher than at mesophilic （T37） temperature for all treatments （P 〈 0.001） except for SW：M 1：0 and SW：M 0：1 treatments （P 〉 0.05）. This study indicates that hydrogen production from co-digestion of synthetic waste and manure is dependent on incubation temperature and relative contribution of wastes in the mixture.

Evaluation of diagnostic ratios of medium and serious weathered oils from five different oil sources

Laboratory experiments were conducted to simulate oil weathering process, a medium to long term weathering process for 210-d, using samples collected from five different oil resources. Based on relative deviation and repeatability limit analysis about indexes of these samples, the results show there had been significant changes in diagnostic ratios among the initial and weathered samples of different oils during this process. Changes of selected n-alkane diagnostic ratios of all oil samples displayed more obviously than diagnostic ratios of terpanes,steranes and PAHs in this process. Almost all selected diagnostic ratios of terpanes, steranes and PAHs can be efficiently used in tracking sources of hydrocarbon pollution, differentiating from the n-alkane diagnostic ratios.In these efficient diagnostic ratios, only four ratios maintained good stability in the weathering processes and are more suitable because their relative deviation（RSD） are lower than 5%.