A review on biomass-derived levulinic acid for application in drug synthesis.

Levulinic acid (LEV) has been identified as a key building block chemical produced entirely from biomass. Its derivatives can be used to synthesize a variety of value-added chemicals, such as 2-butanone, 2-methyltetrahydrofuran, and so on. LEV has carbonyl and carboxyl functional groups, which makes it flexible, diverse, and unique during drug synthesis. It also reduces the cost of drug synthesis and makes the reaction cleaner and, not the least, has untapped potential in the field of medicine. This article reviews the application of LEV in cancer treatment, medical materials, and other medical fields. Overall, LEV can be used in the following ways: (1) Used as a raw material to directly synthesize drugs; (2) Used to synthesize related derivatives, which can be more specifically used in drug synthesis, and derivatives can achieve the corresponding release of drugs, such as paclitaxel (PTX)- LEV, polymer-betulinic acid (BA)-LEV after amidation; (3) It can modify chemical reagents or act as linkers to connect pharmaceutical reagents with carriers to form pharmaceutical intermediates, a pharmaceutical intermediate skeleton, and so on. (4) It can acylate and esterify to form: acetylpropionate and levulinyl, the indole, pyridazine, and other medicinally active functional groups can be synthesized by a long chain, which can reduce the cost of drug synthesis and simplify the tedious synthesis steps. (5) To form the protective group of levulinic acid, the hydroxyl or carboxyl position is first protected, and then the protective group is removed after the corresponding reaction, in order to participate in drug synthesis.

Comparative study on the hydrogenolysis performance of solid residues from different bamboo pretreatments.

Both alkaline organosolv and formaldehyde stabilization pretreatment can yield high-quality lignin by preventing condensation. For the hydrogenolysis of the pretreated solid residues, the highest yield of C2-C4 chemicals was 66.8% under alkaline organosolv pretreatment for 60 min. Specifically, the crimped fibers and residual lignin and hemicellulose increased the surface roughness of the residue by 40.6%, the crystallinity index decreased to 44.4%, and the crystal size was reduced to 2.15 nm, which in turn promoted hydrogenolysis of the residue. However, the increase of crystallinity and crystal size and the decrease in surface roughness of the formaldehyde stabilization pretreatment residue greatly hindered the conversion of polysaccharides. In addition, residual formaldehyde on the residue may also inhibit catalyst activity. Overall, this study provides novel perspectives on the full utilization of biomass, as well as new insights into the conversion of polysaccharides.

Tungsten oxide decorated silica-supported iridium catalysts combined with HZSM-5 toward the selective conversion of cellulose to C6 alkanes.

Herein, WOx-decorated Ir/SiO2 (W/Ir = 0.06) and HZSM-5 were coupled to selectively convert microcrystalline cellulose (MCC) into C6 alkanes. A 92.8% yield of liquid alkanes including an 85.3% yield of C6 alkanes was produced at 210 °C. Cellulose hydrolysis, glucose hydrogenation and sorbitol hydrodeoxygenation were integrated to produce alkanes via a sorbitol route. Ir-WOx/SiO2 showed high performance for hydrogenation and hydrodeoxygenation reactions after hydrolysis catalyzed by HZSM-5. The intimate contact between WOx and Ir enhanced the synergistic interaction through the electron transfer from Ir to WOx. The interaction strengthened the reduction capability of Ir for hydrogenations, as well as improved the adsorption and activation of C-O bonds on reduced WOx for deoxygenations. The monotungstate WOx species provided moderate Lewis acids to cooperate with Ir to accelerate hydrodeoxygenations with alleviated retro-aldol condensation to yield more C6 alkanes.

Could preoxidation always promote the subsequent hydroconversion of lignin? Two counterexamples catalyzed by Cu/CuMgAlOx in supercritical ethanol.

In this study, two counterexamples of lignin preoxidation-hydroconversion were reported. First, two lignin feedstocks were preoxidized with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) in acetonitrile with various dosages (15%, 30%, and 60%). Then, these preoxidized lignins (HELOs and MWLOs) were hydroconverted in supercritical ethanol catalyzed by Cu/CuMgAlOx. Total yields from HELOs were all higher than those from HEL, indicating the good promotion of DDQ preoxidation on the subsequent hydroconversion of HELOs, especially with the DDQ dosage of 15%. Differently, the promotion effect of DDQ preoxidation on the hydroconversion of MWLOs depended on the DDQ dosage as well as the reaction time. Through the comparison of two counterexamples, this work bursted the myth that preoxidation can always promote the subsequent hydroconversion of lignin, revealed the influence of lignin property, preoxidation degree, and reaction conditions on the subsequent hydroconversion of preoxidized lignin, and presented the new insight into the preoxidation-hydroconversion strategy for lignin.

High performance of Mo-promoted Ir/SiO2 catalysts combined with HZSM-5 toward the conversion of cellulose to C5/C6 alkanes.

In this study, the Mo-promoted Ir/SiO2 (Ir-MoOx/SiO2) catalysts combined with the zeolite HZSM-5 were used for the direct conversion of microcrystalline cellulose (MCC) to liquid fuel (C5/C6 alkanes) in n-dodecane/H2O system. A synergistic effect was formed between the partially reduced MoOx species and the Ir particles, which effectively promoted the catalytic activity of Ir/SiO2 catalyst. When the Mo/Ir molar ratio was 0.5, a high yield of C5/C6 alkanes (91.7%) was achieved at 210 â„ƒ for 12 h. In addition, the main component of C5/C6 alkanes was n-hexane, which was proven to be obtained by the hydrogenolysis of the key intermediate, sorbitol, formed from the hydrolysis and hydrogenation of MCC.

Efficient depolymerization of Kraft lignin to liquid fuels over an amorphous titanium-zirconium mixed oxide supported partially reduced nickel-cobalt catalyst.

A series of non-precious metal/metal oxide nickel-cobalt catalysts was prepared for a highly efficient depolymerization of Kraft lignin (KL) into liquid fuels using amorphous TiZr-oxide (Ti1-yZryO2) as a carrier. The effects of Ni-NiOx, Co-CoOx, NiCo-NiCoOx, NiCoOx and NiCo catalysts supported on amorphous TiZr-oxide carrier on KL depolymerization were investigated. It was found that the NiCo-NiCoOx/Ti1-yZryO2 catalyst is optimal for converting KL to petroleum ether (PE)-soluble product (mainly composed of monomers and dimers) in an 80.2% high yield at 320 °C for 24 h, with excellent reusability and a low formation of char. Under these conditions, the higher heating value (HHV) increased from 25.11 to 33.89 MJ/kg. A meticulous study on NiCo-NiCoOx/Ti1-yZryO2 catalysts revealed that the synergistic effect among Lewis acid sites, basic sites and metal active sites played an important role in obtaining high yields of monomers and low rates of char formation during lignin conversion.

Catalytic depolymerization of the hydrolyzed lignin over mesoporous catalysts.

In this work, the mesoporous SBA-15 and a series of modified catalysts based on it, such as Al-SBA-15 and Ni/Al-SBA-15, were synthesized and used for eliminating the char formation during the depolymerization of hydrolyzed lignin. The temperature, time and solvent effects on the lignin depolymerization were also investigated. Results showed that the repolymerization was effectively suppressed over SBA-15 due to its well-ordered pore structure and large pore size. The addition of Al and Ni elements in SBA-15 could improve the lignin depolymerization performance and saturate the instable intermediates. Ethanol was found to be more effective in suppressing repolymerization than other solvents. 81.4% liquefaction degree and 21.90wt% monomer yield was achieved, and no obvious char was observed after the depolymerization of hydrolyzed lignin in ethanol solvent at 300°C for 4h over Ni/Al-SBA-15(20) catalyst.

A two-stage pretreatment process using dilute hydrochloric acid followed by Fenton oxidation to improve sugar recovery from corn stover.

A two-stage pretreatment process is proposed in this research in order to improve sugar recovery from corn stover. In the proposed process, corn stover is hydrolyzed by dilute hydrochloric acid to recover xylose, which is followed by a Fenton reagent oxidation to remove lignin. 0.7wt% dilute hydrochloric acid is applied in the first stage pretreatment at 120°C for 40min, resulting in 81.0% xylose removal. Fenton reagent oxidation (1g/L FeSO4·7H2O and 30g/L H2O2) is performed at room temperature (about 20°C) for 12 has a second stage which resulted in 32.9% lignin removal. The glucose yield in the subsequent enzymatic hydrolysis was 71.3% with a very low cellulase dosage (3FPU/g). This two-stage pretreatment is effective due to the hydrolysis of hemicelluloses in the first stage and the removal of lignin in the second stage, resulting in a very high sugar recovery with a low enzyme loading.

Insight into the solvent, temperature and time effects on the hydrogenolysis of hydrolyzed lignin.

The aim of this study is to explore the reaction mediums and conditions for producing high yield of valuable monomers from concentrated sulfuric acid hydrolyzed lignin. The solvent, temperature and time effects on the hydrogenolysis of hydrolyzed lignin were investigated under the catalysis of Pd/C and CrCl3. Supercritical methanol exhibits the best depolymerization performance, because of its unique diffusion, dissolution and acid-base properties. Afterwards, the influence of reaction temperature and time on depolymerization, repolymerization and coking during hydrogenolysis was examined in methanol. The high temperature is found to favor the depolymerization, with the ß-O-4 linkages cleaved significantly. However, the repolymerization is promoted simultaneously, and a high amount of ß-ß groups form. These reactions are in constant competition with each other and the repolymerization is preferred at excessive high temperature, producing bulk char residues, that is coking. This study will provide a beneficial reference for the maximization of lignin waste valorization.

Investigation on the structural effect of lignin during the hydrogenolysis process.

Structure has a significant effect on the lignin degradation, so the investigation of structural effect on the lignin depolymerization is important and imperative. In this study, hydrogenolysis of three typical lignins with different structures, dealkaline lignin, sodium lignosulfonate and organosolv lignin, was intensively compared over the synergistic catalyst of CrCl3 and Pd/C. The effects of reaction temperature, time, hydrogen pressure and catalyst dosage on the catalytic performance of lignin species were investigated. The structure evolution of lignins during the hydrogenolysis process was also compared. The results showed that organosolv lignin was more sensitive for hydrogenolysis than others due to its high unsaturation degree and low molecular weight. Further analysis indicated that the hydrogenolysis, hydrodeoxygenation and repolymerization reactions took place and competed intensely. Wherein, the depolymerization products with unsaturated carbonyl groups were prone to repolymerize. And the methylation was helpful to stabilize the depolymerization products and suppress the further repolymerization.

Conversion of corn stalk into furfural using a novel heterogeneous strong acid catalyst in γ-valerolactone.

A novel solid acid catalyst was prepared by the copolymerization of p-toluenesulfonic acid and paraformaldehyde and then characterized by FT-IR, TG/DTG, HRTEM and N2-BET. Furfural was successfully produced by the dehydration of xylose and xylan using the novel catalyst in γ-valerolactone. This investigation focused on effects of various reaction conditions including solvent, acid catalyst, reaction temperature, residence time, water concentration, xylose loading and catalyst dosage on the dehydration of xylose to furfural. It was found that the solid catalyst displayed extremely high activity for furfural production. 80.4% furfural yield with 98.8% xylose conversion was achieved at 170°C for 10 min. The catalyst could be recycled at least five times without significant loss of activity. Furthermore, 83.5% furfural yield and 19.5% HMF yield were obtained from raw corn stalk under more severe conditions (190°C for 100 min).

Efficient and product-controlled depolymerization of lignin oriented by metal chloride cooperated with Pd/C.

An efficient lignin depolymerization process with highly controllable product distribution was presented using metal chloride (MClx) cooperated with Pd/C. The catalytic performances of MClx were investigated. The effect of reaction conditions on the lignin depolymerization and products distribution were also studied. Results showed that more than 35.4% yield of phenolic monomer including 7.8% phenols and 1.1% guaiacols could be obtained under optimized condition. And the product distribution can be efficiently controlled by the modification of the metal cation through different pathway of Lewis acid catalysis and coordination catalysis. Furthermore, the Pd/C catalyst showed an excellent recyclability, where no significant loss of the catalytic activity was exhibited after 3 runs. Moreover, the product control mechanism was proposed.

An efficient and economical process for lignin depolymerization in biomass-derived solvent tetrahydrofuran.

The depolymerization of renewable lignin for phenolic monomer, a versatile biochemical and precursor for biofuel, has attracted increasing attention. Here, an efficient base-catalyzed depolymerization process for this natural aromatic polymer is presented with cheap industrial solid alkali MgO and biomass-derived solvent tetrahydrofuran (THF). Results showed that more than 13.2% of phenolic monomers were obtained under 250°C for 15 min, because of the excellent lignin dissolution of THF and its promotion effect on the catalytic activity of MgO. Furthermore, comparison characterization on the raw material, products and residual solid using elemental analysis, FT-IR, TG-DSC, Py-GC-MS and chemo-physical absorption and desorption demonstrated that this base-catalyzed process can inhibit char formation significantly. Whereas, the fact that thermal repolymerization of oligomer on the pore and surface of catalyst resulting in the declination of the catalytic performance is responsible for the residue formation.

Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel.

Single cell oil production from low-cost substrates: the possibility and potential of its industrialization.

Currently, single cell oils (SCO) attract much attention because of their bi-function as a supplier of functional oils and feedstock for biodiesel production. However, high fermentation costs prevent their further application, and the possibility and potential of their industrialization is suspected. Therefore, various low-cost, hydrophilic and hydrophobic substrates were utilized for SCO production. Of these substrates, lignocellulosic biomass, which is the most available and renewable source in nature, might be an ideal raw material for SCO production. Although many reviews on SCO have been published, few have focused on SCO production from low-cost substrates or evaluated the possibility and potential of its industrialization. Therefore, this review mainly presents information on SCO and its production using low-cost substrates and mostly focuses on lignocellulosic biomass. Finally, the possibility and potential of SCO industrialization is evaluated.

Conversion of cellulose and cellobiose into sorbitol catalyzed by ruthenium supported on a polyoxometalate/metal-organic framework hybrid.

Cellulose and cellobiose were selectively converted into sorbitol over water-tolerant phosphotungstic acid (PTA)/metal- organic-framework-hybrid-supported ruthenium catalysts, Ru-PTA/MIL-100(Cr), under aqueous hydrogenation conditions. The goal was to investigate the relationship between the acid/metal balance of bifunctional catalysts Ru-PTA/MIL-100(Cr) and their performance in the catalytic conversion of cellulose and cellobiose into sugar alcohols. The control of the amount and strength of acid sites in the supported PTA/MIL-100(Cr) was achieved through the effective control of encapsulated-PTA loading in MIL-100(Cr). This design and preparation method led to an appropriately balanced Ru-PTA/MIL-100(Cr) in terms of Ru dispersion and hydrogenation capacity on the one hand, and acid site density of PTA/MIL-100(Cr) (responsible for acid-catalyzed hydrolysis) on the other hand. The ratio of acid site density to the number of Ru surface atoms (nA /nRu ) of Ru-PTA/MIL-100(Cr) was used to monitor the balance between hydrogenation and hydrolysis functions; the optimum balance between the two catalytic functions, that is, 8.84

A review of thermal-chemical conversion of lignocellulosic biomass in China.

Biomass, a renewable, sustainable and carbon dioxide neutral resource, has received widespread attention in the energy market as an alternative to fossil fuels. Thermal-chemical conversion of biomass to produce biofuels is a promising technology with many commercial applications. This paper reviewed the state-of-the-art research and development of thermal-chemical conversion of biomass in China with a special focus on gasification, pyrolysis, and catalytic transformation technologies. The advantages and disadvantages, potential of future applications, and challenges related to these technologies are discussed. Conclusively, these transformation technologies for the second-generation biofuels with using non-edible lignocellulosic biomass as feedstocks show prosperous perspective for commercial applications in near future.

Structure and pyrolysis characteristics of lignin derived from wood powder hydrolysis residues.

Physicochemical characteristics of wood powder acid hydrolysis residue (WAHR) were studied firstly in this study, and WAHL (lignin derived from WAHR) was separated successfully from WAHR based on an improved isolating method. The content of functional group such as phenolic hydroxyl group of guaiacyl, syringyl, and hydroxyl-phenyl units in WAHL were identified by (31)P-NMR and DFRC (derivatization followed by reductive cleavage) method. Thermal degradation experiments were carried out on a thermogravimetric (TG) analyzer to show pyrolysis characteristics of WAHL. The compositions of pyrolysis products of WAHL were also studied throughout a pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) analyzer. It was shown that the pyrolysis of WAHL took place in a wide temperature range and there were two obvious peaks in the differential thermogravimetric diagram. Results of Py-GC-MS analysis indicated that pyrolysis products were mainly formed through cleavage of the ß-O-4 connection and multiple pyrolysis.

Kinetic study of hydrolysis of xylan and agricultural wastes with hot liquid water.

We investigated the kinetics of hot liquid water (HLW) hydrolysis over a 60-min period using a self-designed setup. The reaction was performed within the range 160-220 degrees C, under reaction conditions of 4.0 MPa, a 1:20 solid:liquid ratio (g/mL), at 500 rpm stirring speed. Xylan was chosen as a model compound for hemicelluloses, and two kinds of agricultural wastes-rice straw and palm shell-were used as typical feedstocks representative of herbaceous and woody biomasses, respectively. The hydrolysis reactions for the three kinds of materials followed a first-order sequential kinetic model, and the hydrolysis activation energies were 65.58 kJ/mol for xylan, 68.76 kJ/mol for rice straw, and 95.19 kJ/mol for palm shell. The activation energies of sugar degradation were 147.21 kJ/mol for xylan, 47.08 kJ/mol for rice straw and 79.74 kJ/mol for palm shell. These differences may be due to differences in the composition and construction of the three kinds of materials. In order to reduce the decomposition of sugars, the hydrolysis time of biomasses such as rice straw and palm shell should be strictly controlled.