Rawel Singh

Effective catalytic conversion of cellulose into high yields of methyl glucosides over sulfonated carbon based catalyst.

An amorphous carbon based catalyst was prepared by sulfonation of the bio-char obtained from fast pyrolysis (N(2) atm; ≈ 550°C) of biomass. The sulfonated carbon catalyst contained high acidity of 6.28 mmol/g as determined by temperature programmed desorption of ammonia of sulfonated carbon catalyst and exhibited high catalytic performance for the hydrolysis of cellulose. Amorphous carbon based catalyst containing -SO(3)H groups was successfully tested and the complete conversion of cellulose in methanol at moderate temperatures with high yields ca. ≥ 90% of α, β-methyl glucosides in short reaction times was achieved. The methyl glucosides formed in methanol are more stable for further conversion than the products formed in water. The carbon catalyst was demonstrated to be stable for five cycles with slight loss in catalytic activity. The utilization of bio-char as a sulfonated carbon catalyst provides a green and efficient process for cellulose conversion.

Hydrothermal conversion of lignin to substituted phenols and aromatic ethers

Hydrothermal liquefaction of lignin was performed using methanol and ethanol at various temperatures (200, 250 and 280°C) and residence times of 15, 30 and 45min. Maximum liquid product yield (85%) was observed at 200°C and 15min residence time using methanol. Increase in temperature was seen to decrease the liquid products yield. With increase in residence time, liquid yields first increased and then decreased. FTIR and (1)H NMR showed the presence of substituted phenols and aromatic ethers in liquid products and breakage of β-O-4 or/and α-O-4 ether bonds present in lignin during hydrothermal liquefaction was confirmed through FTIR of bio-residue. In comparison to the existing literature information, higher lignin conversion to liquid products and maximum carbon conversion (72%) was achieved in this study.

Catalytic hydrothermal liquefaction of water hyacinth.

Thermal and catalytic hydrothermal liquefaction of water hyacinth was performed at temperatures from 250 to 300 °C under various water hyacinth:H2O ratio of 1:3, 1:6 and 1:12. Reactions were also carried out under various residence times (15-60 min) as well as catalytic conditions (KOH and K2CO3). The use of alkaline catalysts significantly increased the bio-oil yield. Maximum bio-oil yield (23 wt%) comprising of bio-oil1 and bio-oil2 as well as conversion (89%) were observed with 1N KOH solution. (1)H NMR and (13)C NMR data showed that both bio-oil1 and bio-oil2 have high aliphatic carbon content. FTIR of bio-residue indicated that the usage of alkaline catalyst resulted in bio-residue samples with lesser oxygen functionality indicating that catalyst has a marked effect on nature of the bio-residue and helps to decompose biomass to a greater extent compared to thermal case.

Opportunities for utilization of non-conventional energy sources for biomass pretreatment

The increasing concerns over the depletion of fossil resources and its associated geo-political issues have driven the entire world to move toward sustainable forms of energy. Pretreatment is the first step in any biochemical conversion process for the production of valuable fuels/chemicals from lignocellulosic biomass to eliminate the lignin and produce fermentable sugars by hydrolysis. Conventional techniques have several limitations which can be addressed by using them in tandem with non-conventional methods for biomass pretreatment. Electron beam and γ (gamma)-irradiation, microwave and ultrasound energies have certain advantages over conventional source of energy and there is an opportunity that these energies can be exploited for biomass pretreatment.

Pyrolysis of agricultural biomass residues: Comparative study of corn cob, wheat straw, rice straw and rice husk

Pyrolysis studies on conventional biomass were carried out in fixed bed reactor at different temperatures 300, 350, 400 and 450°C. Agricultural residues such as corn cob, wheat straw, rice straw and rice husk showed that the optimum temperatures for these residues are 450, 400, 400 and 450°C respectively. The maximum bio-oil yield in case of corn cob, wheat straw, rice straw and rice husk are 47.3, 36.7, 28.4 and 38.1wt% respectively. The effects of pyrolysis temperature and biomass type on the yield and composition of pyrolysis products were investigated. All bio-oils contents were mainly composed of oxygenated hydrocarbons. The higher area percentages of phenolic compounds were observed in the corn cob bio-oil than other bio-oils. From FT-IR and 1H NMR spectra showed a high percentage of aliphatic functional groups for all bio-oils and distribution of products is different due to differences in the composition of agricultural biomass.

Conversion of rice straw to monomeric phenols under supercritical methanol and ethanol.

Hydrothermal liquefaction of rice straw has been carried out using various organic solvents (CH3OH, C2H5OH) at different temperatures (250, 280 and 300 °C) and residence times (15, 30 and 60 min) to understand the effect of solvent and various reaction parameters on product distribution. Maximum liquid product yield (47.52 wt%) was observed using ethanol at 300 °C and 15 min reaction time. FTIR and NMR ((1)H and (13)C) of liquid product indicate that lignin in rice straw was converted to various monomeric phenols. GC-MS of the liquid product showed the presence of various phenol and guaiacol derivatives. Main compounds observed in liquid product were phenol, 4-ethylphenol, 4-ethyl-2-methoxyphenol (4-ethylguaiacol), 2,6-dimethoxyphenol (syringol), 2-isopropyl-5-methylphenol (thymol). Powder XRD and SEM of bio-residue showed that rice straw was decomposed to low molecular weight monomeric phenols.

Value addition to rice straw through pyrolysis in hydrogen and nitrogen environments

Pyrolysis of rice straw has been carried out under hydrogen atmosphere at 300, 350, 400 and 450 °C and pressures of 1, 10, 20, 30 and 40 bar and in nitrogen atmosphere, experiments have been carried out at the same temperatures. It has been observed that the optimum process conditions for hydropyrolysis are 400 °C and 30 bar pressure and for slow pyrolysis, the optimum temperature is 400 °C. The bio-oil has been characterised using GC-MS, (1)H NMR and FT-IR and bio-char using FT-IR, SEM and XRD. The bio-oil yield under hydrogen pressure was observed to be 12.8 wt.% (400 °C and 30 bar) and yield under nitrogen atmosphere was found to be 31 wt.% (400 °C). From the product characterisation, it was found that the distribution of products is different for hydrogen and nitrogen environments due to differences in the decomposition reaction mechanism.

Catalytic hydrothermal upgradation of wheat husk.

Catalytic hydrothermal upgradation of wheat husk was performed at 280°C for 15 min in the presence of alkaline catalysts (KOH and K2CO3). The effect of alkaline catalysts on the yield of bio-oil products and composition of bio-oils obtained were discussed. Total bio-oil yield (31%) comprising of bio-oil1 (ether fraction) and bio-oil2 (acetone fraction) was maximum with K2CO3 solution. Powder XRD (X-ray diffraction) analysis of wheat husk as well as bio-residue samples show that the peaks due to cellulose, hemicellulose and lignin become weak in bio-residue samples which suggest that these components have undergone hydrolytic cleavage/decomposition. The FTIR spectra of bio-oils indicate that the lignin in the wheat husk samples was decomposed to low molecular weight phenolic compounds. (1)H Nuclear Magnetic Resonance (NMR) spectrum of bio-oil1 shows more than 50% of the protons resonate in the up field region from 0.5 ppm to 3.0 ppm.

Effects of temperature and solvent on hydrothermal liquefaction of Sargassum tenerrimum algae

The influence of various solvents (H2O, CH3OH, and C2H5OH) on product distribution and nature of products during hydrothermal liquefaction of sargassum tenerrimum algae has been examined. Hydrothermal liquefaction was performed using H2O (260, 280 and 300°C) and organic solvents CH3OH and C2H5OH (280°C) for 15min. The use of organic solvents significantly increased the yield of bio-oil. In the case of liquefaction with CH3OH and C2H5OH, the bio-oil yield was 22.8 and 23.8wt.% respectively whereas the bio-oil yield was 16.33wt.% with H2O. GC-MS analysis of the liquid products indicated the presence of various organic compounds including aromatics, nitrogenated and oxygenated compounds and higher selectivity amount of ester compounds were observed in the presence of alcoholic solvents. NMR and FT-IR showed that present of solvents have an effect on the decomposition of sargassum tenerrimum algae.

Slow pyrolysis of prot, alkali and dealkaline lignins for production of chemicals

Effect of different lignins were studied during slow pyrolysis. Maximum bio-oil yield of 31.2, 34.1, and 29.5wt.% was obtained at 350, 450 and 350°C for prot lignin, alkali lignin and dealkaline lignin respectively. Maximum yield of phenolic compounds 78%, 80% and 92% from prot lignin, alkali and dealkaline lignin at 350, 450 and 350°C. The differences in the pyrolysis products indicated the source of lignins such as soft and hard wood lignins. The biochar characterisation revealed that the various ether linkages were broken during pyrolysis and lignin was converted into monomeric substituted phenols. Bio-oil showed that the relative contents of each phenolic compound changes significantly with pyrolysis temperature and also the relative contents of each compound changes with different samples.