Hydrothermal conversion of cellulose into lactic acid with nickel catalyst

Utilization of biomass has become a major topic of research around the world. One promising aspect of utilization is production of lactic acid from carbohydrate biomass. Our previous study showed that lactic acid can be formed from glucose and cellulose by alkaline hydrothermal reactions, but the yield of lactic acid was low, particular for cellulose. In this study, an efficient method for producing lactic acid from cellulose under hydrothermal conditions with NaOH in the presence of nickel was developed. Experiments were conducted in a batch reactor at 300 °C for 1?C4 min. Results showed that nickel could promote the yield of lactic acid from cellulose. The highest yield of 34.07% was obtained by adding 0.5 mmol nickel using 2.5 M NaOH solution at 300 °C for 1 min.     

Production of acetic acid from liquid crystal display waste by use of a hydrothermal method

Because of the large quantity of liquid crystal displays (LCDs) in use, the volume of waste LCDs is ever-increasing, causing growing concern about their effective treatment. Polarizers are among the most important functional films used in LCDs and are mainly treated by incineration after being discarded. In this study, they were used to produce acetic acid under the hydrothermal conditions; this could aid development of a new environmentally sustainable process for treatment of waste polarizers. The experiment was performed in a 5.7-ml bath reactor heated by use of a salt-bath. The liquid product was analyzed by high-performance liquid chromatography. The effect of reaction temperature, reaction time, and oxidant on acetic acid production was investigated. Results showed that the yield and selectivity for acetic acid initially increased with increasing reaction temperature, reaction time, and H₂O₂ supply but then decreased within the ranges of the experiments performed. The highest acetic acid yield of 33.4 %, with selectivity of 26.7 % based on carbon, was obtained by hydrothermal treatment of waste polarizer at 350 °C for 5 min with 0.6 ml H₂O₂.     

Synthesis and catalytic performance of ZSM-5/MCM-41 composite molecular sieve from palygorskite

ZSM-5/MCM-41 composite molecular sieve has been hydrothermally synthesized through a two-step crystallization process using palygorskite (PAL) as silicon and aluminum source. The products were characterized by various means and their catalytic properties for acetalization of cyclohexanone and esterification of acetic acid and n-butanol were also investigated. In the first step ZSM-5 zeolite could be formed from the acid-treated PAL after hydrothermal treatment using tetrapropylammonium bromide as template. XRD patterns, N₂ adsorption and desorption data, and TEM images show that the composite obtained in the secondary step had a well-ordered mesoporous MCM-41 phase and a microporous ZSM-5 zeolite phase. Compared with ZSM-5, ZSM-5/MCM-41 composite possessed more total acid amount, weak acid sites and large pore structure due to the formation of MCM-41 and exhibited higher catalytic activity for the acetalization and esterification reaction.     

Preparation and utilization of perillyl acetate

Perillyl acetate is a fragrance compound that was prepared by the reaction of β-pinenoxide with acetic anhydride and using acetic acid as an acid catalyst. Several selected catalysts were tested (homogenous: phosphoric acid, boric acid, acetic acid, and citric acid; heterogeneous: zeolite USY, SSA, and montmorillonite K-10) and the reaction conditions optimized for this reaction. The yield 78.7 % of perillyl acetate was obtained. Mayol (4-isopropylcyclohexylmethanol), a valuable fragrance compound, was further obtained by a two-step synthesis from perillyl acetate. Firstly, perillyl acetate was saponified to perillyl alcohol. The yield of alcohol was 94.4 %. The last step of the entire preparation was the hydrogenation of perillyl alcohol to Mayol. The yield of the desired product of this reaction was 94.6 %.     

Homogeneous Degradation of Cellulose in Its Aqueous Solution at Mild Temperature under Atmospheric Pressure

Degradation of cellulose to chemicals is one of major routes for biomass conversion. Here, a new simple and two-step method has been developed to convert cellulose in its homogeneously alkaline solution to organic acids under atmospheric pressure at mild temperature. At first, cellulose was degraded to small molecular intermediates at 110 ℃ for 3 h under atmospheric pressure, and then it was oxidized with H₂O₂ at 50 ℃ for 4 h. Under the optimal condition, 73.5% conversion of cellulose could be achieved, and the yield of organic acids was 32.8% (formic acid), 11.6% (lactic acid), and 2.3% (oxalic acid), respectively. It is noteworthy that the new strategy reduces energy consumption in the process of reaction, unlike the hydrothermal reaction under high temperature and high pressure.     

Production of formic and acetic acids from phenol by hydrothermal oxidation

Hydrothermal technology is a core environmental-protection technique which can be used for waste water treatment and biomass conversion. In this paper a novel idea, alkaline hydrothermal oxidation, is proposed for producing formic and acetic acids from wastewater containing phenolic compounds. The effects of the most important conditions??reaction temperature, reaction time, oxygen supply, and type of alkaline catalyst??on yields of formic and acetic acids were investigated. The results indicated that the optimum conditions for production of formic and acetic acids were: reaction temperature 300???C, reaction time 90?s, H₂O₂ equivalent to 60% oxygen, and NaOH concentration 1.5?mmol. Under the optimum conditions the yields of formic and acetic acids reached 4.8 and 23.5%, respectively. In addition, the effect of different alkalis on yields of formic and acetic acids was also investigated. The results showed that compared with use of NaOH addition of KOH had a more pronounced effect on improving the yield of acetic acid. This research indicated that high-value-added formic and acetic acids can be recovered as resources by hydrothermal oxidation of phenolic wastewater, and thus hydrothermal oxidation has high potential for converting phenolic compounds in wastewater into value-added products.     

Analytical determination of organic acids formed during hydrothermal and organosolv degradation of lignocellulosic biomass

Summary The present study deals with the isotachophoretic and the ion chromatographic analysis of organic acids found in hydrolysates of lignocellulosic biomass. The samples were pretreated by means of ultrafiltration to increase the reproducibility of the measurements. The qualitative and quantitative analysis of the fractions obtained during hydrothermal and organosolv degradations of wheat straw allowed a comparison of the rate and amount of organic acids formed (formic acid, glycolic acid, lactic acid, acetic acid). Isotachophoresis facilitates research on the reaction mechanisms underlying the hydrolysis of biomass.

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Analyse der durch Hydrothermolyse und Organosolv-Aufschluß von lignocellulosehaltiger Biomasse gebildeten organischen Säuren

     

Biohydrogen Production from Cheese Whey Wastewater in a Two-Step Anaerobic Process

Cheese whey-based biohydrogen production was seen in batch experiments via dark fermentation by free and immobilized Enterobacter aerogenes MTCC 2822 followed by photofermentation of VFAs (mainly acetic and butyric acid) in the spent medium by Rhodopseudomonas BHU 01 strain. E. aerogenes free cells grown on cheese whey diluted to 10 g lactose/L, had maximum lactose consumption (～79%), high production of acetic acid (1,900 mg/L), butyric acid (537.2 mg/L) and H(2) yield (2.04 mol/mol lactose; rate,1.09 mmol/L/h). The immobilized cells improved lactose consumption (84%), production of acetic acid (2,100 mg/L), butyric acid (718 mg/L) and also H(2) yield (3.50 mol/mol lactose; rate, 1.91 mmol/L/h). E. aerogenes spent medium (10 g lactose/L) when subjected to photofermentation by free Rhodopseudomonas BHU 01 cells, the H(2) yield reached 1.63 mol/mol acetic acid (rate, 0.49 mmol/L/h). By contrast, immobilized Rhodopseudomonas cells improved H(2) yield to 2.69 mol/mol acetic acid (rate, 1.87 mmol/L/h). The cumulative H(2) yield for free and immobilized bacterial cells was 3.40 and 5.88 mol/mol lactose, respectively. Bacterial cells entrapped in alginate, had a sluggish start of H(2) production but outperformed the free cells subsequently. Also, the concomitant COD reduction for free cells (29.5%) could be raised to 36.08% by immobilized cells. The data suggest that two-step fermentative H(2) production from cheese whey involving immobilized bacterial cells, offers greater substrate to- hydrogen conversion efficiency, and the effective removal of organic load from the wastewater in the long-term.     

Hydrothermal pretreatment conditions to enhance ethanol production from poplar biomass

Pretreatment has been recognized as a key step in enzyme-based conversion processes of lignocellulose biomass to ethanol. The aim of this study is to evaluate two hydrothermal pretreatments (steam explosion and liquid hot water) to enhance ethanol production from poplar (Populus nigra) biomass by a simultaneous saccharification and fermentation (SSF) process. The composition of liquid and solid fractions obtained after pretreatment, enzymatic digestibility, and ethanol production of poplar biomass pretreated at different experimental conditions was analyzed. The best results were obtained in steam explosion pretreatment at 210°C and 4 min, taking into account cellulose recovery above 95%, enzymatic hydrolysis yield of about 60%, SSF yield of 60% of theoretical, and 41% xylose recovery in the liquid fraction. Large particles can be used for poplar biomass in both pretreatments, since no significant effect of particle size on enzymatic hydrolysis and SSF was obtained.     

中枢神经兴奋药物莫达非尼的合成新方法

提出了两步法合成中枢神经兴奋药物莫达非尼的新路线。合成路线简捷,得到的产品易纯化,缩短了反应时间,适合于工业化生产,莫达非尼总产率高达97.5%。第一步,二苯甲醇∶硫脲∶氢溴酸∶氢氧化钠∶氯乙酰胺的摩尔比为1.0∶1.2∶2.0∶3.5∶1.8,水为溶剂,温度恒定70℃;第二步,温度40℃,用过氧化氢氧化。     

Effect of ethyl acetate on carbohydrate components and crystalline structure of pulp produced in aqueous acetic acid pulping

The aim of this study was to investigate the changes in carbohydrate components and the crystalline structure in hemp bast fibers by adding ethyl acetate to acetic acid/water pulping processes. It was found that ethyl acetate added to acetic acid/water process had a positive effect on yield, viscosity and carbohydrate components in pulp. It was assumed that the delignification ratio increased by adding ethyl acetate to aqueous acetic acid pulping. Xylose content in hemp bast fibers was affected more negatively in the ethyl acetate/acetic acid/water process than in the acetic acid/water one. Crystallinity and crystallite size were higher in pulp sample obtained by the acetic acid/water process without ethyl acetate.     

Separate and Concentrate Lactic Acid Using Combination of Nanofiltration and Reverse Osmosis Membranes

The processes of lactic acid production include two key stages, which are (a) fermentation and (b) product recovery. In this study, free cell of Bifidobacterium longum was used to produce lactic acid from cheese whey. The produced lactic acid was then separated and purified from the fermentation broth using combination of nanofiltration and reverse osmosis membranes. Nanofiltration membrane with a molecular weight cutoff of 100–400 Da was used to separate lactic acid from lactose and cells in the cheese whey fermentation broth in the first step. The obtained permeate from the above nanofiltration is mainly composed of lactic acid and water, which was then concentrated with a reverse osmosis membrane in the second step. Among the tested nanofiltration membranes, HL membrane from GE Osmonics has the highest lactose retention (97 ± 1%). In the reverse osmosis process, the ADF membrane could retain 100% of lactic acid to obtain permeate with water only. The effect of membrane and pressure on permeate flux and retention of lactose/lactic acid was also reported in this paper.     

介孔Ni/MgO催化剂催化水蒸气重整生物质油制氢

采用水热法制备了介孔MgO作为催化剂的载体,并制备了介孔Ni/MgO催化剂。利用N_2吸附-脱附、XRD、H_2-TPR等对样品进行表征,并考察了介孔Ni/MgO催化水蒸气重整糠醛、生物质油模型物和两种商用生物质油制氢的活性。结果表明,在介孔Ni/MgO催化剂催化水蒸气重整糠醛制氢反应中,随着反应温度的提高,水蒸气重整糠醛中糠醛的转化率、氢气的产率和氢气的选择性,都呈现递增的趋势。在反应温度提高到600℃时,糠醛的转化率和氢气的产率分别达到94.9%和83.2%。Ni/MgO催化水蒸气重整二组分模拟生物质油,糠醛/乙酸、糠醛/羟基丙酮制氢的反应中,氢气的产率分别达到87.3%和86.8%,均高于水蒸气重整糠醛反应中氢气的产率。由此表明,乙酸或羟基丙酮的存在,提高了模拟生物质油中主要有机物组分糠醛的转化率,并相应地提高了氢气的产率。在水蒸气重整商用生物质油制氢反应中,随着反应物水碳比(S/C(molar ratio)=5、10、15、20、25)的提高,主要有机物的转化率、氢气的产率和选择性呈现出增加的趋势。在水碳比为20时,两种生物质油的主要有机物组分(糠醛、乙酸和羟基丙酮)的转化率均可达90%以上,氢气的产率也达到81.0%以上。由此可知,Ni催化剂对于水蒸气重整商用生物质油也具有较高的催化活性。     

Agriculture crop residues as a source for the production of nanofibrillated cellulose with low energy demand

Nanofibrillated cellulose (NFC) from three agricultural crop (rice straw, corn and rapeseed stalk) residues was isolated with high-yield production using either high pressure homogenisation or a high speed blender. The fibres were extracted from the neat biomass via an NaClO₂/acetic acid and alkali pulping process. TEMPO-mediated oxidation pretreatment at pH 7 and 10 was accomplished to facilitate the release of the cellulose microfibrils. The fibrillation yield, transparency degree and morphological characteristics of the ensuing NFC were analysed using the centrifugation method, transmittance measurement and SEM observation. The energy consumption during the disintegration process was also accessed. It was shown that the mode of lignin removal and the fibre pretreatment notably affected the nanofibrillation efficiency and energy demand. A successful production of NFC with yield exceeding 90 %, using a simple Waring blender, was achieved when the NaClO₂/acetic acid delignification followed by a TEMPO-NaBr–NaClO oxidation at pH 10 was adopted.     

Corn steep liquor as a cost-effective nutrition adjunct in high-performanceZymomonas ethanol fermentations

The economics of large-scale production of fuel ethanol from biomass and wastes requires the efficient utilization of all the sugars derived from the hydrolysis of the heteropolymeric hemicellulose component of lignocellulosic feedstocks. Glucuronic and 4-0-methyl-glucuronic acids are major side chains in xylans of the grasses and hardwoods that have been targeted as potential feedstocks for the production of cellulosic ethanol. The amount of these acids is similar to that of arabinose, which is now being viewed as another potential substrate in the production of biomass-derived ethanol. This study compared the end-product distribution associated with the fermentation of D-glucose (Glc) and D-glucuronic acid (GlcUA) (as sole carbon and energy sources) byEscherichia coli B (ATCC 11303) and two different ethanologenic recombinants—a strain in whichpet expression was via a multicopy plasmid (pLOI297) and a chromosomally integrated construct, strain KO11. pH-stat batch fermentations were conducted using a modified LB medium with 2% (w/v) Glc or GlcUA with the set-point for pH control at either 6.3 or 7.0. The nontransformed host culture produced only lactic acid from glucose, but fermentation of GlcUA yielded a mixture of ethanol, acetic, and lactic acids, with acetic acid being the predominant end-product. The ethanol yield associated with GlcUA fermentation by both recombinants was similar, but acetic acid was a significant by-product. Increasing the pH from 6.3 to 7.0 increased the rate of glucuronate fermentation, but it also decreased the ethanol mass yield from 0.22 to 0.19 g/g primarily because of an increase in acetic acid production. In all fermentations there was good closure of the carbon mass balance, the exception being the recombinant bearing plasmid pLOI297 that produced an unidentified product from GlcUA. The metabolism of GlcUA by this metabolically engineered construct remains unresolved. The results offered insights into metabolic fluxes and the regulation of pyruvate catabolism in the wild-type and engineered strains. End-product distribution for metabolism of glucuronic acid by the nontransformed, wild-typeE. coli B and recombinant strain KO11 suggests that the enzyme pyruvate-formate lyase is not solely responsible for the production of acetylCoA from pyruvate and that derepressed pyruvate dehydrogenase may play a significant role in the metabolism of GlcUA.     

Monitoring of substrate and product concentrations in acetic fermentation processes for onion vinegar production by NIR spectroscopy: value addition to worthless onions

Wastes and by-products of the onion-processing industry pose an increasing disposal and environmental problem and represent a loss of valuable sources of nutrients. The present study focused on the production of vinegar from worthless onions as a potential valorisation route which could provide a viable solution to multiple disposal and environmental problems, simultaneously offering the possibility of converting waste materials into a useful food-grade product and of exploiting the unique properties and health benefits of onions. This study deals specifically with the second and definitive step of the onion vinegar production process: the efficient production of vinegar from onion waste by transforming onion ethanol, previously produced by alcoholic fermentation, into acetic acid via acetic fermentation. Near-infrared spectroscopy (NIRS), coupled with multivariate calibration methods, has been used to monitor the concentrations of both substrates and products in acetic fermentation. Separate partial least squares (PLS) regression models, correlating NIR spectral data of fermentation samples with each kinetic parameter studied, were developed. Wavelength selection was also performed applying the iterative predictor weighting–PLS (IPW-PLS) method in order to only consider significant spectral features in each model development to improve the quality of the final models constructed. Biomass, substrate (ethanol) and product (acetic acid) concentration were predicted in the acetic fermentation of onion alcohol with high accuracy using IPW-PLS models with a root-mean-square error of the residuals in external prediction (RMSEP) lower than 2.5% for both ethanol and acetic acid, and an RMSEP of 6.1% for total biomass concentration (a very satisfactory result considering the relatively low precision and accuracy associated with the reference method used for determining the latter). Thus, the simple and reliable calibration models proposed in this study suggest that they could be implemented in routine applications to monitor and predict the key species involved in the acetic fermentation of onion alcohol, allowing the onion vinegar production process to be controlled in real time.     

Production of lactic acid from pulp mill solid waste and xylose using Lactobacillus delbrueckii (NRRL B445)

Using the simultaneoussaccharification and fermentation (SSF) technique, pulp mill solid waste cellulose was converted into glucose using cellulase enzyme and glucose into lacticacid using NRRL B445. SSF experiments were conducted at various pH levels, temperatures, and nutrient concentrations, and the lactic acid yield ranged from 86 to 97%. The depletion of xylose in SSF was further investigated by inoculating NRRL B445 into a xylose-only medium. On prolonged incubation, depletion of xylose with lactic acid production was observed. An experimental procedure with a nonglucose medium was developed to eliminate the lag phase. From xylose fermentation, Lactobacillus delbrueckii yielded 88–92% lactic acid and 2–12% acetic acid.     

Efficient Non-sterilized Fermentation of Biomass-Derived Xylose to Lactic Acid by a Thermotolerant Bacillus coagulans NL01

Xylose is the major pentose and the second most abundant sugar in lignocellulosic feedstock. Its efficient utilization is regarded as a technical barrier to the commercial production of bulk chemicals from lignocellulosic biomass. This work aimed at evaluating the lactic acid production from the biomass-derived xylose using non-sterilized fermentation by Bacillus coagulans NL01. A maximum lactic acid concentration of about 75 g/L was achieved from xylose of 100 g/L after 72 h batch fermentation. Acetic acid and levulinic acid were identified as important inhibitors in xylose fermentation, which markedly reduced lactic acid productivity at 15 and 1.0 g/L, respectively. But low concentrations of formic acid (<2 g/L) exerted a stimulating effect on the lactic acid production. When prehydrolysate containing total 25.45 g/L monosaccharide was fermented with B. coagulans NL01, the same preference for glucose, xylose, and arabinose was observed and18.2 g/L lactic acid was obtained after 48 h fermentation. These results proved that B. coagulans NL01 was potentially well-suited for producing lactic acid from underutilized xylose-rich prehydrolysates.     

豆类秸秆两级热解特性研究

利用热裂解仪-气相色谱/质谱联用仪(Py-GC/MS)对黄豆秆进行了两级热解。结果表明,随着第一级热解温度(t1)的升高,第一级热解产物总峰面积逐渐增大,第二级热解产物总峰面积逐渐减小;在第一级热解产物中,酸类、酮类和呋喃类等源于纤维素和半纤维素的产物含量在t1为400和450℃时较高;在t1为450和500℃的条件下,第二级热解产物中烃类产物的含量高达20%以上。两级热解可以在第一级和第二级热解中分别获取不同的高含量产物,如乙酸、糠醛、愈创木酚、甲苯和苯等,实现生物质的选择性热解。     

Influence of the pH Value on the Hydrothermal Degradation of Fructose

The hydrothermal treatment of sugars features a promising technology for the production of fine and platform chemicals from renewable resources. In this work the hydrothermal decomposition of fructose was studied in a buffered medium at a pH range between 2.2 and 8.0. It is demonstrated that at lower pH values mainly 5-hydroxymethylfurfural (HMF), levulinic acid and humin are generated, while lactic acid and acetic acid are produced at higher pH values. The work shows that the use of moderate acidic conditions may have advantages for the hydrothermal HMF production over the use of strongly acidic conditions, as especially the degradation into levulinic acid is suppressed. Besides, this study deals with a rather complex reaction network, hence limitations and need for adaption of the kinetic model are discussed.