Synthesis of a Zr/Sn/Al-SBA-15 catalyst for the conversion of glucose to lactic acid

Recently, much attention has been paid to the development of technologies that facilitate the conversion of biomass into platform chemicals such as 5-hydroxymethylfurfural (5-HMF). In this paper, a tin-containing silica molecular sieve (Sn-MCM-41) was found to act as a bifunctional heterogeneous catalyst for the efficient conversion of glucose into 5-HMF in ionic liquid. In the presence of [EMIM]Br, the yield of 5-HMF converted from glucose reached 70% at 110 °C after 4 h. During the reaction, the active center of the catalyst first catalyzed the isomerization of glucose into fructose and then the dehydration of fructose into 5-HMF. After the reaction, the heterogeneous catalyst Sn-MCM-41 could be easily recovered and reused without a significant loss in activity. The catalyst Sn-MCM-41 was also able to catalyze the conversion of fructose into 5-HMF at an 80% yield. Moreover, the low toxicity of the Sn-based catalyst makes the method a greener approach for the conversion of saccharides into 5-HMF.

Photocatalytic conversion of biomass is considered an effective, clean, and environmentally friendly route to obtain high-valued chemicals and hydrogen. However, the limited conversion efficiency and poor selectivity are still the main bottlenecks for photocatalytic biomass conversion. Herein, we report the highly selective photocatalytic conversion of glucose solution on holo-symmetrically spherical three-dimensionally ordered macroporous TiO₂-CdSe heterojunction photonic crystal structure (s-TCS). The obtained s-TCS photocatalysts show excellent stability and strong light harvesting, uniform mass diffusion and exchange, and efficient photogenerated electrons/holes separation and utilization. The optimized s-TCS-4 photocatalyst displays the highest photocatalytic performance for glucose oxidation and hydrogen production. The glucose conversion, lactic acid selectivity, and yield on s-TCS-4 are about 95.9%, 94.3%, and 96.4%, respectively. The photocatalytic production of lactic acid for s-TCS-4 (18.5 g/L) is 2.3 times higher than the pure spherical TiO₂ photonic crystal without CdSe (s-TiO₂, 8.1 g/L), and the hydrogen production rate of s-TCS-4 is 9.4 times that of s-TiO₂. For the first time, we reveal that the photocatalytic conversion of glucose to lactic acid is a third-order and four-electron-involved reaction. This work could shed some new light on the efficient photocatalysis conversion of biomass to highly value-added products with high selectivity and yield, and simultaneously sustainable hydrogen evolution.

MnOx was used as a vanadium-free catalyst for conversion of glucose to formic acid in water with 81% yield in which α-scission (C1–C2 bond cleavage) with arabinose being an intermediate was found to be the major conversion pathway.

In this research, I studied cellulose conversion into levulinic acid and lactic acid. Cellulose in biomass is considered as a renewable carbon source because of decreasing of fossil fuel in the world. I studied the effect of hot compressed water with carbon dioxide process on cellulose conversion into levulinic acid and I also studied the effect of metal oxides as a catalyst on cellulose conversion into lactic acid. Moreover, the optimum condition, amount of catalyst, the type of catalyst, and reusability of catalyst were investigated. The results are divided as three parts. First part, I reported that the use of hot compressed water with carbon dioxide could be directly converted cellulose to levulinic acid and that the yield of levulinic acid slightly differed when carbon dioxide is added into reaction. Thus, I concluded that the use of hot compressed water with carbon dioxide was not enough for cellulose conversion into levulinic acid. Second part, I studied the effect of metal oxides on cellulose conversion into lactic acid. The result showed that ZrO2 gave the high yield of lactic acid. I obtained 21.2% yield of lactic acid by using ZrO2 as a catalyst. The optimum condition for cellulose conversion was reaction temperature 473 K, reaction time 6 h. Many ZrO2 was characterized to understand correlation between the yield of lactic acid and properties of catalyst. I found that the amount of acid site and base site of catalyst played an important role for cellulose conversion into lactic acid. The result of reusability of catalyst showed that the yield of lactic acid slightly decreased after the first reaction. Third part, I studied the effect of mixed metal oxides on cellulose conversion into lactic acid. Various mixed metal oxide were used in reaction. The results showed that 10%ZrO2-Al2O3 gave the 25.3 % yield of lactic acid.

A series of water-tolerant Lewis acidic TiO2/Nb2O5·nH2O heterojunction catalysts with different Ti : Nb ratios have been prepared and investigated in the conversion of glucose into HMF in water.

The development of highly-efficient catalysts for conversion of glucose and fructose to 5-hydroxymethylfurfural (HMF) is of great importance. In this work, theoretical simulations form the basis for rational design and synthesis of a superhydrophobic mesoporous acid, that can completely prevent HMF hydration, giving HMF as sole product from full conversion of fructose. Interestingly, the combined superhydrophobic solid acid and superhydrophilic solid base catalysts are very efficient for one-pot conversion of glucose to HMF, giving a yield as high as 95.4 %. The excellent catalytic data in the conversion of glucose to HMF is attributed to the unique wettabilities of the solid acid and base catalysts.

Production of lactic acid from paper sludge using acid-tolerant, thermophilic Bacillus coagulan strains

The continuous production of lactic acid from deproteinized whey by immobilized single and mixed culture of L. casei and L. lactis in Ca‐alginate beads has been investigated. A coimmobilized culture system gave better results than immobilized single cultures regarding lactic acid concentration, productivity, yield, and lactose utilization. Maximum lactic acid productivity of 7 g/lh was obtained at D=0.4 h−1 with a yield of 70% lactic acid and 50% lactose utilization. At a dilution rate of 0.1 h−1, a lactic acid productivity of 2.5 g/lh was obtained with a 55.5% lactic acid yield and 90% lactose utilization. The bioreactor system was operated at a constant dilution rate of 0.1 h−1 for 20 days without loss of original activity. In this case, the average lactic acid productivity, lactic acid yield and lactose utilization were 24 g/lh, 55% and 90%, respectively.

This study investigated the exchange affinity of Fe3+, Cu2+, and Zn2+ cations in sulfuric acid-purified montmorillonite (S-MMT) to enhance Lewis acid sites and subsequently improve the catalytic conversion of glucose to lactic acid. XRD analysis suggested the successful cation exchange process, leading to structural expansion of the resultant cation exchanged-MMTs (CE-MMTs). XRF and TGA indicated that Zn2+ had the highest exchange affinity, followed by Cu2+ and then Fe3+. This finding was further supported by the results of TPD-NH3 analysis and pyridine-adsorption test, which demonstrated that Zn-MMT had the highest total acid sites (TAS) and the ratio of Lewis acid-to-Brønsted acid surface site (LA/BA). These results indicated dominant presence of Lewis acid sites in Zn-MMT due to the higher amount of exchanged Zn2+ cations. Consistently, time-dependent catalytic studies conducted at 170 °C showed that a 7 h-reaction generated the highest lactic acid yield, with the catalytic performance increasing in the order of Fe-MMT < Cu-MMT < Zn-MMT. The study also observed the impact of adding alcohols as co-solvents with water at various ratios on the conversion of glucose to lactic acid catalysed by Zn-MMT. The addition of ethanol enhanced lactic acid yield, while methanol and propanol inhibited lactic acid formation. Notably, a water-to-ethanol ratio of 30 : 70 v/v% emerged as the optimal solvent condition, resulting in ca. 35 wt% higher lactic acid yield compared to using water alone. Overall, this study provides valuable insights into the cation exchange affinity of different cations in MMT catalysts and their relevance to the conversion of glucose to lactic acid. Furthermore, the incorporation of alcohol co-solvent presents a promising way of enhancing the catalytic activity of CE-MMTs.

Biomass valorization by photoreforming approach provides a promising and alternative strategy to generate value-added chemicals and fuels. In this work, we demonstrate the selective production of lactic acid from glucose photoreforming over pristine graphitic carbon nitride (g-C3N4) photocatalyst. Control experiments screen the best condition for the highest yield of lactic acid, including modulating pH, catalyst loading, and reaction time. 100% glucose conversion is achieved along with almost 100% lactic acid yield under the optimized condition. Density functional theory (DFT) calculations reveal that the rate-determining step (RDS) of the overall reaction on g-C3N4 is the conversion of pyruvaldehyde, where an electron transfer takes place. This present work provides experimental insights and theoretical understanding for selective lactic acid production from biomass photoreforming.

A rotating fibrous-bed bioreactor (RFB) was developed for fermentation to produce L(+)-lactic acid from glucose and cornstarch by Rhizopus oryzae. Fungal mycelia were immobilized on cotton cloth in the RFB for a prolonged period to study the fermentation kinetics and process stability. The pH and dissolved oxygen concentration (DO) were found to have significant effects on lactic acid productivity and yield, with pH 6 and 90% DO being the optimal conditions. A high lactic acid yield of 90% (w/w) and productivity of 2.5 g/L.h (467 g/h.m(2)) was obtained from glucose in fed-batch fermentation. When cornstarch was used as the substrate, the lactic acid yield was close to 100% (w/w) and the productivity was 1.65 g/L.h (300 g/h.m(2)). The highest concentration of lactic acid achieved in these fed-batch fermentations was 127 g/L. The immobilized-cells fermentation in the RFB gave a virtually cell-free fermentation broth and provided many advantages over conventional fermentation processes, especially those with freely suspended fungal cells. Without immobilization with the cotton cloth, mycelia grew everywhere in the fermentor and caused serious problems in reactor control and operation and consequently the fermentation was poor in lactic acid production. Oxygen transfer in the RFB was also studied and the volumetric oxygen transfer coefficients under various aeration and agitation conditions were determined and then used to estimate the oxygen transfer rate and uptake rate during the fermentation. The results showed that the oxygen uptake rate increased with increasing DO, indicating that oxygen transfer was limited by the diffusion inside the mycelial layer.

In the present study, the use of Sn-Beta zeolite to facilitate the conversion of lignocellulosic biomass-derived glucose and xylose into lactic and levulinic acid was explored. The reactions were carried out in a batch reactor using water as the solvent. Water is the preferred solvent over methanol as it reduces downstream product acid recovery and purification complexity. Optimization experiments were performed for reaction temperature and residence time. Under optimized reaction conditions, the Sn-Beta facilitated reaction of a pure sugar solution resulted in lactic acid yields of 13 and 19 wt% of inlet carbon of glucose and xylose, respectively, plus levulinic acid yields of 18 and 0.8 wt%, respectively. When actual biomass-derived sugar solutions were tested, the yields of lactic acid were significantly higher than those from the optimized model solution experiments with lactic acid yields of 34 wt%. These biomass-derived sugar solutions contained residual levels of CaSO4 from the neutralization step of the hydrolysis process. Further experiments were performed to examine the potential effects from CaSO4 contributing to this increase. It was found that the sulfate ions increased the Brønsted basicity and the calcium increased the Lewis acidity of the reaction solution, and that the combination of both effects increased the conversion of the original sugars into lactic acid. These effects were verified by testing other organic bases to isolate the Brønsted acid neutralization effect and the Lewis acid enhancement effect. The addition of CaSO4 resulted in attractive lactic acid yields, 68 wt% and 50 wt% of inlet carbon from pure glucose and xylose solutions, respectively. Increasing the actual corn stover and forage sorghum derived sugars concentration (in water) allowed lactic acids yields of greater than 60 wt% to be achieved. When the optimized Sn-Beta reaction system was applied to corn stover and forage sorghum mixtures, it was found that the ratio of lactic-to-levulinic acid generated was inversely dependent upon the glucose-to-xylose ratio in the recovered sugar mixture.

The lespedeza stalks with steam pretreatment were fermented to lactic acid by simultaneous saccharification and fermentation (SSF) in this study. Orthogonal design methodology was used to evaluate the optimum SSF conditions that give maximum lactic acid yield. We have investigated the following relative factors, such as temperature, loading of cellulase, calcium carbonate and concentration of substrate. The optimum operating conditions were found to be temperature of 43 °C, cellulase loading of 30 FPU/g substrate, calcium carbonate of 3 % and substrate of 6 %. Comparisons of different steam pretreated conditions on lactic acid yield from lespedeza stalks were also made. The results showed that lactic acid yields from lespedeza stalks with 4 min pretreatment at pressure of 1.0, 1.25, 1.5 and 2.0 Mpa were 41.8 %, 42.5 %, 50.6 % and 64.0 % of the theoretical, respectively. The lactic acid yield from steam pretreated lespedeza stalks was much higher than that of lespedeza stalks without pretreatment (23.9 %). It can be concluded that the lactic acid yield was remarkably improved by steam pretreatment. The yield of lactic acid from steam pretreated lespedeza stalks was 1.68 times higher than that of untreated ones. Additionally, the lactic acid yield could be further promoted from 64.0 % to 89.4 % by washing pretreated stalks with water, which suggested that water processing is a promising method to remove inhibitors in broth to improve lactic acid yield.

Highly robust Zr-based MOF-808, featuring Lewis acid Zr sites and coordinate hydroxide ions upon the removal of the monocarboxylate capping reagent, emerges as an efficient catalyst for the hydrothermal conversion of glucose into lactic acid. A remarkable 99% glucose conversion with an impressive 76.6% yield of lactic acid can be achieved. The large pore window of MOF-808 facilitates the diffusion of glucose to the active sites within the framework. The single-site attribute of the catalytic center enables a high selectivity of lactic acid over the competitive product, 5-(hydroxymethyl)furfural, under hydrothermal reaction conditions.

Highly selective catalytic conversion of raw sugar and sugarcane bagasse to lactic acid over YbCl3, ErCl3, and CeCl3 Lewis acid catalysts without alkaline in a hot-compressed water reaction system