Bio-oil Process Research Articles

Protein molecular structure in relation to predicted biodegradation and nutrient supply of feedstocks and co-products from bio-oil processing with CNCPS system: Comparison Crusher Plants within Canada and within China as well as between Canada and China

Recently, rapid non-invasive advanced vibrational molecular spectroscopy has been developed to detect tissue inherent molecular structure. However, this advanced technique is seldom known by animal scientists and seldom used to study feed molecular structure in relation to nutrient utilization and availability in animals. The objectives of this study were to 1) detect the interactive association between the processing-induced protein molecular structure changes and biodegradation and intestinal digestion in ruminants using advanced vibrational molecular spectroscopy, and 2) develop a model to predict protein and carbohydrate degradation and digestions based on feed inherent protein molecular structure. The feed used for this study were various sources of feedstock (oil seeds) and co-products (canola meal, canola pellets) from ten different crushing plants in Canada and China with multi-source samples from each crushing plant. The predictable protein and carbohydrate degradable sub-fractions and nutrient supply of sub-fractions to dairy cows were evaluated with the updated Cornell Net Carbohydrate and Protein System (CNCPS 6.5). The protein molecular structure was revealed using advanced vibrational molecular spectroscopy (FT/IR-ATR). The molecular structure spectral analyses were carried out using uni- and multi-variate molecular spectral analyses. The model variable selection was carried out using SAS with a Stepwise option. The results showed that protein molecular structure spectral characteristics could be used to predict CNCPS protein and carbohydrate nutrient supply to dairy cows. Strong positive correlation was found in canola meal between rumen degraded PA2 and amide I area (r = 0.67, P < 0.001), amide I height (r = 0.73, P < 0.001), and α-helix height (r = 0.83, P < 0.001). RDPB2 was negatively correlated with α-helix height (r = −0.69, P < 0.001). Moreover, TRDC was negatively correlated with amide I area (r=-0.64, P < 0.001), amide I height (r = −0.65, P < 0.001), and α-helix height (r = −0.62, P < 0.001). It was concluded that protein and carbohydrate degradable and undegradable sub-fractions had interactive associations with the processing-induced protein molecular structure changes in co-products from bio-oil processing.

On a Molecular Basis, Investigate Association of Molecular Structure with Bioactive Compounds, Anti-Nutritional Factors and Chemical and Nutrient Profiles of Canola Seeds and Co-Products from Canola Processing: Comparison Crusher Plants within Canada and within China as well as between Canada and China

The objectives of this study were to: (1) Use molecular spectroscopy as a novel technique to quantify protein molecular structures in relation to its chemical profiles and bioenergy values in oil-seeds and co-products from bio-oil processing. (2) Determine and compare: (a) protein molecular structure using Fourier transform infrared (FT/IR-ATR) molecular spectroscopy technique; (b) bioactive compounds, anti-nutritional factors, and chemical composition; and (c) bioenergy values in oil seeds (canola seeds), co-products (meal or pellets) from bio-oil processing plants in Canada in comparison with China. (3) Determine the relationship between protein molecular structural features and nutrient profiles in oil-seeds and co-products from bio-oil processing. Our results showed the possibility to characterize protein molecular structure using FT/IR molecular spectroscopy. Processing induced changes between oil seeds and co-products were found in the chemical, bioenergy profiles and protein molecular structure. However, no strong correlation was found between the chemical and nutrient profiles of oil seeds (canola seeds) and their protein molecular structure. On the other hand, co-products were strongly correlated with protein molecular structure in the chemical profile and bioenergy values. Generally, comparisons of oil seeds (canola seeds) and co-products (meal or pellets) in Canada, in China, and between Canada and China indicated the presence of variations among different crusher plants and bio-oil processing products.

Co-upgrading of raw bio-oil with kitchen waste oil through fluid catalytic cracking (FCC)

Raw bio-oil was produced from fast pyrolysis of pine sawdust in a fluidized-bed boiler at 550 °C. Then the raw bio-oil is partially mixed with kitchen waste oil (100:0, 50:50, 0:100 by weight) and subsequently subjected to off line co-catalytic cracking process for upgrading over HZSM-5. The raw bio-oil mixed with kitchen waste oil test shows that the co-catalytic cracking improves the organic bio-oil yield and inhibits the coke formation. The oxygen content of organic bio-oil decreased significantly after upgrading. The reaction pathway of co-upgrading is proposed, which shows that kitchen waste oil, as a hydrogen supplier, transform hydrogen from high saturation degree to the unsaturation oxygenated compounds to form hydrocarbons. Co-catalytic cracking process of raw bio-oil and kitchen waste oil not only can be used in raw bio-oil upgrading but also can recycle kitchen waste oil with relatively low cost. Moreover, the deactivation catalysts are analyzed by TG-FTIR (Thermogravimetric-Fourier Transform Infrared spectroscopy) and SEM (Scanning Electron Microscope).

Diffusion and Rheological Properties of Asphalt Modified by Bio-Oil Regenerant Derived from Waste Wood

To decrease the usage of energy and improve waste recovery, dynamic simulations are conducted to understand the diffusion mechanism and rheological properties of bio-oil regenerated asphalt. A new simplified model of bio-oil modified asphalt (BMA) is built to calculate diffusion coefficients, diffusion driving force, viscosity, solubility parameters, and ductility. The calculated diffusion coefficients of bio-oil, asphaltenes, saturates, and resins are 4.5×10−3 cm2/s, 3.6×10−4 cm2/s, 4.2×10−4 cm2/s, and 5.1×10−4 cm2/s at 298 K, respectively. Results indicate that the bio-oil diffuses faster than asphaltenes, saturates, and resins, and that it can increase the ductility of asphalt and improve asphalt’s elastic property. Moreover, potential energy is the key driving force of diffusion. There is no chemical reaction involved in the diffusion process of BMA and bio-oil can both reduce the viscosity of asphalt and soften it.

Potential nitrogen to energy synchronization, rumen degradation kinetics, and intestinal digestibility of blend pelleted products of new co-products from bio-fuel processing, pulse screenings and lignosulfonate compound in dairy cows

Recently, a new co-product (carinata meal) has been emerged from the bio-fuel processing industry, which nutritional value has not been yet fully understood and evaluated nor even registered as a feed for ruminants. So, it becomes an urgent need to explore the potential of this new coproduct in livestock feeds when blend with other feedstuffs. The aim of this project was to develop and test blend pelleted products based on combination of new and conventional co-products from bio-fuel (carinata meal) and bio-oil (canola meal) processing, pea screenings and lignosulfonate compound (feed additive) at different levels in order to efficiently utilize the new co-product and optimize various nutrient supply in dairy cows. The eight blend pelleted products were: BPP1: lignosulfonate 0.0% + carinata meal 50.0% + pea screenings 50.0%; BPP2: lignosulfonate 4.8% + carinata meal 47.6% + pea screenings 47.6%; BPP3: lignosulfonate 0.0% + carinata meal 75.0% + pea screenings 25.0%; BPP4: lignosulfonate 4.8% + carinata meal 71.4% + pea screenings 23.8%; BPP5: lignosulfonate 0.0% + canola meal 50.0% + pea screenings 50.0%; BPP6: lignosulfonate 4.8% + canola meal 47.6% + pea screenings 47.6%; BPP7: lignosulfonate 0.0% + canola meal 75.0% + pea screenings 25.0%; BPP8: lignosulfonate 4.8% + canola meal 71.4% + pea screenings 23.8%. All blended proportions were on dry matter (DM) basis. The results were compared between blend pelleted products based on new co-product carinata meal and conventional co-product canola meal; high and low level of inclusion of co-products (contrarily, low and high level of inclusion of pea screenings); and inclusion and no inclusion of lignosulfonate compound in terms of rumen degradation kinetics, indigestible neutral detergent fiber(NDF) at 288 h (iNDF), hourly effective rumen degradation ratios/potential nitrogen-to energy synchronization and intestinal digestion of rumen undegraded nutrients. The results showed that carinata based pelleted product BPP3 and BPP4 had higher (P < 0.05) level of rumen undegraded protein (BCPDVE: 233 and 239 g/kg DM; RUPNRC: 210 and 216 g/kg DM; respectively) than the other blend pelleted products. The BPP3 also showed higher (P < 0.05) effective degradation of NDF (EDNDF: 64 g/kg DM) than the other blend pelleted products except BPP4 and BPP7 (56 and 61 g/kg DM; respectively). The iNDF was higher in canola based pelleted product BPP7, while the values were ranged from 5.3 to 12.5% DM. Intestinal absorbable feed protein (IADP) was higher in BPP4 (168 g/kg DM) than the other pelleted products except BPP3; however, BPP3 showed higher (P < 0.05) total digestible protein (TDP: 405 g/kg DM) than the other blend pelleted products followed by BPP4 (383 g/kg DM) and BPP7 (370 g/kg DM). In addition, BPP3 showed higher (P < 0.05) total digestible NDF (TDNDF: 139 g/kg DM) than the other blend pelleted products. In summary, the new co-product (carinata meal) based pelleted products (BPP1 to BPP4) contained higher RUP (+56 g/kg DM), lower EDCP (–24 g/kg DM), higher EDNDF (+2.9%), lower iNDF (−4.2% DM), higher IADP (+55.7 g/kg DM) and higher TDP (+32 g/kg DM) than canola based pelleted products (BPP6 to BPP8). Therefore, the result of this study suggest that the Carinata meal based pelleted products BPP3 and BPP4 can be used as high quality protein supplements for dairy cows.

Thermodynamic study for hydrogen production from bio-oil via sorption-enhanced steam reforming: Comparison with conventional steam reforming

The thermodynamic analysis of the sorption-enhanced steam reforming (SESR) process of bio-oil for hydrogen production was investigated in terms of equilibrium compositions, energy consumption, with the comparison with the conventional steam reforming (CSR) process. Compared to CSR process, the SESR process could obtain higher H2 yield and concentration at lower temperature and S/C ratio, with both of the yield and concentration reaching over 90%. For decreasing the energy consumption, the sensible heat of the hot output streams from the two processes was recovered, with the recovered heat calculated by pinch analysis. To produce the same amount H2, the total energy demand of the SESR process was obviously lower the CSR process, especially under low temperature zone. Finally, the parameters of the two processes were optimized with a matrix analysis method. For SESR process, the optimal SR conditions were the temperature of 500 °C–600 °C, the S/C ratio of 3.0, under which the consumptions of bio-oil and energy were about 20% and about 30% lower than those under the optimal conditions of CSR process, respectively.

Optimization of bio-asphalt using bio-oil and distilled water

The objective of this research is to improve the high temperature performances and anti-aging properties of bio-asphalt. In this paper, the bio-asphalt was prepared using bio-oil to modify petroleum asphalt, and the contents of bio-oil were 10%, 15%, 20%, 25% and 30%. The gas chromatograph-mass spectrometer (GC-MS) test was applied to characterize the chemical compounds in bio-oil. The Fourier transform infrared spectroscopy (FTIR) test was utilized to determine whether some compounds were removed from bio-oil based on the functional groups present. Then the rotating thin film oven (RTFO) test was used to verify whether the high temperature performance and anti-aging properties of bio-asphalt improved. Furthermore, the orthogonal experimental design and dynamic shear rheometer (DSR) test were employed to study the effect of optimization process parameters on high temperature performances. It was found that a large amount of polar light weighted components can be removed from bio-oil using distilled water. During the treatment process of bio-oil, the water-oil mass ratio had a significant influence on the high temperature of bio-asphalt while stirring time and stirring temperature were not significant factors. Additionally, the anti-rutting properties of bio-asphalt had an increasing trend when the water-oil mass ratio varied from 1:1 to 2:1 and reached a maximum when the water-oil mass ratio was 2:1.The bio-oil optimization process involved stirring the water-oil mix for 10 min at 50 °C with a water-oil mass ratio of 2:1. Using bio-oil and distilled water is reliable in optimizing bio-asphalt as the high temperature performance and anti-aging performance of bio-asphalt were improved after bio-oil was treated with distilled water.

On a molecular basis pelleting-induced changes on carbohydrate structure of co-products from bio-oil production revealed with vibrational molecular spectroscopy plus chemometrics: Sensitivity and response to conditioning temperature and time

Molecular structure changes are closely related to nutrient utilization and availability. However, so far little research was found to determine the processing induced changes on carbohydrate structure in co-products from bio-oil processing. The objectives of this study were to investigate synergistic effects of conditioning temperature (70, 80 and 90°C) and time (50 and 75 s) during the pelleting process on carbohydrate structure profile of the co-products from bio-oil processing (canola meal). The vibrational molecular spectroscopy (ATR-VMS) with chemometrics was used to determine the impact of pelleting at different conditions on the inherent molecular structure changes. The molecular spectral analyses, Univariate and Multivariate spectral analyses, were used in this study. Multivariate spectral analyses included cluster analysis and principal analysis. The chemical functional groups mainly associated with carbohydrate structure profile in this lipid-free co-products (or with very little lipid) included cellulosic compounds (CEL, ranged at ca. 1302-1186 cm −1 ), structural CHO (SCHO, ranged at ca. 1488- 1186 cm −1 ) and total CHO (TCHO, ranged at ca. 1193-879 cm −1 ). The results showed that the pelleting process was able to alter inherent structures of CHO functional groups in the co-products from bio-oil processing. The univariate molecular analysis indicated that spectral intensities of CHO functional groups in the co-products were significantly affected by the pelleting process in the current study ( P< 0.05). Altering processing conditions resulted changes in molecular structure features of CHO functional groups except TCHO. The results of multivariate spectral analysis of CHO indicated that inherent CHO structural characteristics of all functional groups were not fully distinguished. This study demonstrated that the pelleting process under the conditions investigated caused partial changes in carbohydrate structures in terms of the spectral features of specific functional groups. These changes were not sufficient enough to make the entire spectral region of CHO functional groups become fully distinguishable. Future research is needed to investigate the interactive relationships between the absorption intensities of carbohydrate functional groups (TCHO, SCHO, CEL) and biodegradation and digestion of the co-products in order to reveal how carbohydrate molecular structure changes induced by processing affect nutritive availability.

Evaluation of hydrodeoxygenation reactivity of pyrolysis bio-oil with various Ni-based catalysts for improvement of fuel properties

To improve bio-oil quality, deoxygenation degree and energy efficiency of the process, Ni/C, Ni/SBA-15 and Ni/Al-SBA-15 were synthesized and subjected to hydrodeoxgygenative upgrading process of bio-oil.

Treatment of Bio-Oil Refinery Storm Water by a Simulated Constructed Wetland: A Sustainable Management Alternative

Abstract Contaminated storm-water discharge is a growing concern in the United States owing to a steady increase of harmful pollutants entering freshwater sources. This study remediated contaminated storm-water runoff from a bio-oil conversion facility through a simulated constructed wetland. A six-phase series of constructed wetlands was contaminated with varying dilution levels of bio-oil process water. The study concluded that there was a significant decrease in biological oxygen demand (BOD) and microtoxicity over a 10-day remediation cycle within the constructed wetlands for the lower levels of contaminated storm water. The higher levels of contamination changed very little in total volume of pollution. A comparative screening of the bacterial community within the wetlands during the contamination process showed a similar trend in species richness and composition for the first three phases of contamination. There was a shift in richness and diversity for the final three phases of contamination after 10 days. The constructed wetlands were successful at lowering BOD and toxicity levels and achieving permissible pH levels at dilutions higher than 500 times. When the concentrations of contaminated water were lower than 830 mL of contaminated bio-oil wastewater for every 240 liters of rainwater, the constructed wetlands were successful only at achieving permissible pH discharge levels. Better results for high-level contamination may be achievable with longer residence time in the wetlands.

Combustion characteristics of bio-oil from swine manure/crude glycerol co-liquefaction by thermogravimetric analysis technology

ABSTRACTThe thermal analysis and kinetics of bio-oils derived from swine manure/crude glycerol co-liquefaction were studied by thermogravimetric analysis (TGA) in the air. It was found that the combustion processes of bio-oils can be divided into three stages, with most of the materials decomposing between 330 and 370°C. In kinetic calculations, oxidation of the bio-oils was determined using the Coats–Redfern method, considering that bio-oil combustion occurs in three consecutive steps. Four models including more than 12 alpha functions were tested to fit the study’s experimental results. The calculation shows that the diffusion models are the best fit for describing the bio-oil combustion process in the air.

Solvent effects on improvement of fuel properties during hydrodeoxygenation process of bio-oil in the presence of Pt/C

Bio-oil was subjected to hydrodeoxygenation (HDO) reactions with polar protic (ethanol), polar aprotic (acetone), and nonpolar (ether) solvents in the presence of Pt/C catalyst. Mass balances (gas, light oil, heavy oil and char) of products were influenced by the solvent used. Subjecting the oil to HDO yielded improvement in the following heavy oil properties: water content, heating value, viscosity, acidity, and oxygen level. Especially, the viscosity was reduced from 29.6 cSt of the bio-oil to 2.2–4.4 cSt when ethanol was used, to 3.0–4.2 cSt when acetone was used, and to 6.5–6.7 cSt when ether was used. The initially acidic bio-oil was neutralized by HDO. Furthermore, HDO decreased the water and oxygen content of heavy oil, thereby improving its higher heating value (HHV). Because the polar protic solvent was able to react with bio-oil as a co-reactant during HDO, acid-type components in the bio-oil were converted into acid or ester forms, which were found in the light oil. In terms of carbon recovery from bio-oil to the heavy oil fraction, acetone was the most effective solvent, yielding 72.8% recovery, followed by ether (64.7%) and ethanol (55.3%).

Analysis of coke precursor on deactivated catalyst in bio-oil upgrading process

ABSTRACTCharacterization of coke precursor on deactivated catalyst in bio-oil upgrading under CO atmosphere was analyzed with thermogravimetry, X-ray diffraction, infrared analysis, scanning electron microscopy, and nuclear magnetic resonance. The results showed that the deposition of coke precursor on a catalyst surface was mainly low-boiling point of saturated hydrocarbon compounds and the coke precursor of internal channels of deactivated catalyst were major aromatic hydrocarbon compounds. The coke precursor was in an amorphous state, which was highly dispersed on the catalyst surface or into the catalyst micropore. In addition, the catalyst deactivation mechanism was speculated that the small molecule aromatic compounds entered the internal channels of a catalyst and formed macromolecular aromatic hydrocarbons by aromatization gradually, further condensed to form coke and obstructed the channels of the catalyst.

Study of X-ray photoelectron spectroscopy on coke deposited on Ni/HZSM-5 in bio-oil hydrodeoxygenation

The coke deposited on the surfaces of Ni/HZSM-5 catalyst in bio-oil hydrodeoxygenation (HDO) was characterized by using a technique of X-ray photoelectron spectroscopy. The results show that the compounds with carbon related oxygen are the main constituent of the coke on the Ni/HZSM-5 catalysts. The amount of carbon compounds with two oxygen atoms is decreased with increasing reaction temperature due to their splitting by activated H2 during HDO processing of bio-oil. Carbon compounds with one oxygen atom are changed during the HDO of bio-oil processing, where soluble carbon compounds were converted to insoluble ones, with increasing reaction temperature leading to increase in hard carbon compounds. Graphite appeared on the surface of the Ni/HZSM-5 catalysts in the HDO of bio-oil at the highest temperature in the experiments. The related mechanism is presented in the paper.

Autothermal reforming of palm empty fruit bunch bio-oil: thermodynamic modelling

This work focuses on thermodynamic analysis of the autothermal reforming of palm empty fruit bunch (PEFB) bio-oil for the production of hydrogen and syngas. PEFB bio-oil composition was simulated using bio-oil surrogates generated from a mixture of acetic acid, phenol, levoglucosan, palmitic acid and furfural. A sensitivity analysis revealed that the hydrogen and syngas yields were not sensitive to actual bio-oil composition, but were determined by a good match of molar elemental composition between real bio-oil and surrogate mixture. The maximum hydrogen yield obtained under constant reaction enthalpy and pressure was about 12 wt% at S/C = 1 and increased to about 18 wt% at S/C = 4; both yields occurring at equivalence ratio Φ of 0.31. The possibility of generating syngas with varying H2 and CO content using autothermal reforming was analysed and application of this process to fuel cells and Fischer-Tropsch synthesis is discussed. Using a novel simple modelling methodology, reaction mechanisms were proposed which were able to account for equilibrium product distribution. It was evident that different combinations of reactions could be used to obtain the same equilibrium product concentrations. One proposed reaction mechanism, referred to as the ‘partial oxidation based mechanism’ involved the partial oxidation reaction of the bio-oil to produce hydrogen, with the extent of steam reforming and water gas shift reactions varying depending on the amount of oxygen used. Another proposed mechanism, referred to as the ‘complete oxidation based mechanism’ was represented by thermal decomposition of about 30% of bio-oil and hydrogen production obtained by decomposition, steam reforming, water gas shift and carbon gasification reactions. The importance of these mechanisms in assisting in the eventual choice of catalyst to be used in a real ATR of PEFB bio-oil process was discussed.

Effects of conditioning temperature and time during the pelleting process on feed molecular structure, pellet durability index, and metabolic features of co-products from bio-oil processing in dairy cows

The objectives of this study were to systematically determine effects of conditioning temperature (70, 80, and 90°C), time (50 and 75 s), and interaction (temperature × time) during the pelleting process on co-products from bio-oil processing (canola meal) in terms of processing-induced changes on (1) protein molecular structure, (2) pellet durability index, (3) detailed chemical profile, (4) metabolic features and fractions of protein and carbohydrate, (5) total digestible nutrients and energy values, and (6) rumen degradable and undegradable content. Pellet durability was increased with increasing conditioning time. Chemical and carbohydrate profiles of co-products were not altered by pelleting process under different conditioning temperatures and times. With regard to protein fraction profiles, pellets conditioned for 50 s had higher soluble crude protein (SCP) and lower neutral detergent insoluble crude protein (NDICP) contents than those conditioned for 75 s (21.7 vs. 20.1% SCP, 16.0 vs. 16.5% NDICP, respectively). Total digestible nutrients and energy values were not altered by processing. Samples conditioned for 50 s had a higher content of rapidly degradable protein fraction (PA2) than those conditioned for 75 s (21.7 vs. 21.1% crude protein). In addition, the slowly degradable true protein fraction (PB2) was affected by the interaction of conditioning temperature and time. However, carbohydrate fractions did not differ with different conditioning temperatures and time. Different temperatures and time of conditioning during pelleting process greatly affect protein profiles without altering carbohydrate profiles. Molecular structure analyses also showed that pelleting altered inherent protein molecular structures of the co-products from bio-oil processing. Future study is needed to detect how molecular structure changes affect nutrient availability in dairy cattle.

Corrosion Considerations for Thermochemical Biomass Liquefaction Process Systems in Biofuel Production

Thermochemical liquefaction processing of biomass to produce bio-derived fuels (e.g., gasoline, jet fuel, diesel, home heating oil, etc.) is of great recent interest as a renewable energy source. Approaches under investigation include direct liquefaction, hydrothermal liquefaction, hydropyrolysis, fast pyrolysis, etc., to produce energy dense liquids that can be utilized as produced or further processed to provide products of higher value. An issue with bio-oils is that they tend to contain significant concentrations of organic oxygenates, including acids, which make the bio-oil a potential source of corrosion issues in transport, storage, and use. Efforts devoted to modified/further processing of bio-oils to make them less corrosive are currently being widely pursued. Another issue that must also be addressed in bio-oil liquefaction is potential corrosion issues in the process equipment. Depending on the specific process, bio-oil liquefaction production temperatures are typically in the 300–600°C range, and the process environment can contain aggressive sulfur and halide species from both the biomass used and/or process additives. Detailed knowledge of the corrosion resistance of candidate process equipment alloys in these bio-oil production environments is currently lacking. This paper summarizes recent, ongoing efforts to assess the extent of corrosion of bio-oil process equipment, with the ultimate goal of providing a basis for the selection of the lowest cost alloy grades capable of providing the long-term corrosion resistance needed for future bio-oil production plants.

Hydrodeoxygenation of anisole as bio-oil model compound over supported Ni and Co catalysts: Effect of metal and support properties

Hydrodeoxygenation (HDO) is considered one of the most promising routes to convert the pyrolysis bio-oils produced from lignocellulose into biofuels very similar to those derived from petroleum. This work reports results obtained in the catalytic HDO of anisole over non-conventional hydrotreating catalysts based on metallic Ni and Co supported on micro-mesoporous carriers of different acidity. Anisole has been chosen as representative of those compounds, containing a methoxy-phenyl group, which are abundant in lignocellulose pyrolysis bio-oils. The effect of both metal phase and support properties on their performance as HDO catalysts has been studied. With this aim, three supports with different textural and acidic properties have been employed: hierarchical ZSM-5, mesostructured pure silica SBA-15 and mesostructured Al-SBA-15. The reactions have been carried out in a stainless steel high pressure batch reactor at 220°C and with 50bar of pure hydrogen.The interaction of the metallic species (Ni or Co) with the porous supports, as well as their dispersion, is strongly affected by the support nature and the presence of Al. Thus, it has been found a synergetic effect between the acid sites of the supports and the metallic active phases, which favors and enhances the HDO of anisole. In the case of the acidic supports, Ni-based catalysts (Ni/Al-SBA-15 and Ni/h-ZSM-5) show larger anisole conversions compared to Co-based materials. The strong interaction with the acidic supports of the latter hinders the total Co reduction prior to the reaction, being probably the major reason of their lower activity. Hydrodeoxygenation, hydrodearomatization and isomerization reactions take place extensively over Ni/h-ZSM-5, revealing it is a promising catalyst for bio-oil processing in order to attain high quality fuel production.

Interactive association between biopolymers and biofunctions in carinata seeds as energy feedstock and their coproducts (carinata meal) from biofuel and bio-oil processing before and after biodegradation: current advanced molecular spectroscopic investigations.

Recent advances in biofuel and bio-oil processing technology require huge supplies of energy feedstocks for processing. Very recently, new carinata seeds have been developed as energy feedstocks for biofuel and bio-oil production. The processing results in a large amount of coproducts, which are carinata meal. To date, there is no systematic study on interactive association between biopolymers and biofunctions in carinata seed as energy feedstocks for biofuel and bioethanol processing and their processing coproducts (carinata meal). Molecular spectroscopy with synchrotron and globar sources is a rapid and noninvasive analytical technique and is able to investigate molecular structure conformation in relation to biopolymer functions and bioavailability. However, to date, these techniques are seldom used in biofuel and bioethanol processing in other research laboratories. This paper aims to provide research progress and updates with molecular spectroscopy on the energy feedstock (carinata seed) and coproducts (carinata meal) from biofuel and bioethanol processing and show how to use these molecular techniques to study the interactive association between biopolymers and biofunctions in the energy feedstocks and their coproducts (carinata meal) from biofuel and bio-oil processing before and after biodegradation.

Using ATR–FT/IR to detect carbohydrate-related molecular structure features of carinata meal and their in situ residues of ruminal fermentation in comparison with canola meal

There is no information on the co-products from carinata bio-fuel and bio-oil processing (carinata meal) in molecular structural profiles mainly related to carbohydrate biopolymers in relation to ruminant nutrition. Molecular analyses with Fourier transform infrared spectroscopy (FT/IR) technique with attenuated total reflectance (ATR) and chemometrics enable to detect structural features on a molecular basis. The objectives of this study were to: (1) determine carbohydrate conformation spectral features in original carinata meal, co-products from bio-fuel/bio-oil processing; and (2) investigate differences in carbohydrate molecular composition and functional group spectral intensities after in situ ruminal fermentation at 0, 12, 24 and 48h compared to canola meal as a reference. The molecular spectroscopic parameters of carbohydrate profiles detected were structural carbohydrates (STCHO, mainly associated with hemi-cellulosic and cellulosic compounds; region and baseline ca. 1483–1184cm−1), cellulosic compounds (CELC, region and baseline ca. 1304–1184cm−1), total carbohydrates (CHO, region and baseline ca. 1193–889cm−1) as well as the spectral ratios calculated based on respective spectral intensity data. The results showed that the spectral profiles of carinata meal were significantly different from that of canola meal in CHO 2nd peak area (center at ca. 1091cm−1, region: 1102–1083cm−1) and functional group peak intensity ratios such as STCHO 1st peak (ca. 1415cm−1) to 2nd peak (ca. 1374cm−1) height ratio, CHO 1st peak (ca. 1149cm−1) to 3rd peak (ca. 1032cm−1) height ratio, CELC to total CHO area ratio and STCHO to CELC area ratio, indicating that carinata meal may not in full accord with canola meal in carbohydrate utilization and availability in ruminants. Carbohydrate conformation and spectral features were changed by significant interaction of meal type and incubation time and almost all the spectral parameters were significantly decreased (P<0.05) during 48h ruminal degradation in both carinata meal and canola meal. Although carinata meal differed from canola meal in some carbohydrate spectral parameters, multivariate results from agglomerative hierarchical cluster analysis and principal component analysis showed that both original and in situ residues of two meals were not fully distinguished from each other within carbohydrate spectral regions. It was concluded that carbohydrate structural conformation could be detected in carinata meal by using ATR–FT/IR techniques and further study is needed to explore more information on molecular spectral features of other functional group such as protein structure profile and their association with potential nutrient supply and availability of carinata meal in animals.