Low-Temperature Dilute Acid Hydrolysis of Oil Palm Frond

Oil palm frond (OPF) fiber, a lignocellulosic waste from the palm oil industry, contains high cellulose and hemicellulose content, thus it is a potential feedstock for simple sugars production. This paper describes the two-stage hydrolysis process focusing on the use of low-temperature dilute acid hydrolysis to convert the hemicellulose in OPF fiber to simple sugars (xylose, arabinose, and glucose). The objective of the present study was to evaluate the effect of operating conditions of dilute sulfuric acid hydrolysis undertaken in a 1 L self-built batch reactor on xylose production from OPF fiber. The reaction conditions were temperatures (100–140°C), acid concentrations (2–6%), and reaction times (30–240 min). The mass ratio of solid/liquid was kept at 1:30. Analysis of the three main sugars glucose, xylose, and arabinose were determined using high-pressure liquid chromatography. The optimum reaction temperature, reaction time, and acid concentration were found to be 120°C, 120 min, and 2% acid, respectively. Based on the potential amount of xylose (10.8 mg/mL), 94% conversion (10.15 mg/mL) was obtained under the optimum conditions with small amount of furfural (0.016 mg/mL). To enhance the effectiveness of dilute acid hydrolysis, the hydrolysis of OPF fiber was also performed using ultrasonic-pretreated OPF fiber. The effects of ultrasonic parameters power (40–80%) and ultrasonication times (20–60 min) were determined on sugar yields under optimum hydrolysis conditions (2% acid sulfuric, 120°C and 120 min). However, the use of ultrasonication was found to have detrimental effect on the yield of simple sugars due to the 10-fold increase in the formation of furfural.     

Modeling and optimization of dilute nitric acid hydrolysis on corn stover

BACKGROUND: Because of its high cost, nitric acid has not been widely employed as the catalyst for hydrolysis of lignocellulosic biomass to obtain fermentable sugars. However, recently more and more research results have reported that nitric acid was more effective than other acids for the hydrolysis of lignocellulose. Therefore, it is necessary to find an optimum condition for nitric acid pretreatment and a means of reducing the cost. RESULTS: In this work, low concentrations of nitric acid and short reaction times were considered to optimize the pretreatment process. The kinetic parameters of models to predict the concentrations of xylose, glucose, arabinose, acetic acid and furfural in the hydrolysates were obtained. Applying the kinetic models, the optimum conditions were: 150 °C, 0.6% HNO₃ and 1 min, which yielded a solution containing up to 22.01 g L^?1 xylose, 1.91 g L^?1 glucose, 2.90 g L^?1 arabinose, 2.42 g L^?1 acetic acid and 0.21 g L^?1 furfural, which were consistent with the predicted values. The influence of temperature was also studied using the Arrhenius equation. CONCLUSIONS: A combination of experimental data and model analysis suggested that 96% xylose yield can be achieved by using low concentration nitric acid for a short reaction time, which could greatly reduce the pretreatment cost. Therefore, dilute nitric acid could be considered a good choice for the hydrolysis of corn stover. Copyright © 2010 Society of Chemical Industry     

Pretreatment of barley husk for bioethanol production

This paper reports on the optimization of steam pretreatment of barley husk for high pentose and hexose recovery in the subsequent enzymatic hydrolysis step, as well as high ethanol yield, following simultaneous saccharification and fermentation. The parameters optimized in the steam pretreatment step were residence time (5–15 min), temperature (190–215 °C), and concentration of the acid catalyst (0 or 0.5% H₂SO₄). A microwave oven was employed for screening of the optimal conditions to obtain the highest sugar yield following combined pretreatment and enzymatic hydrolysis. The final optimization of the pretreatment prior to enzymatic hydrolysis was performed on a larger scale, in a steam pretreatment unit. Simultaneous saccharification and fermentation was carried out following steam pretreatment on 5 and 10% dry matter steam‐pretreated slurries. Fermentability tests were performed to determine the effect of by‐products (ie furfural and 5‐hydroxymethyl furfural) in the bioconversion of glucose to ethanol by baker's yeast. The maximum glucose yield, 88% of the theoretical, was obtained following steam pretreatment with 0.5% H₂SO₄ at 200 °C for 10 min. Under these conditions, a sugar to ethanol conversion of 81% was attained in simultaneous saccharification and fermentation. Copyright © 2004 Society of Chemical Industry     

Restructuring the processes for furfural and xylose production from sugarcane bagasse in a biorefinery concept for ethanol production

This study consisted in restructuring the processes for furfural and xylose production from sugarcane bagasse in a biorefinery concept for the residues utilization on ethanol production.The dilute acid hydrolysis conditions for furfural or xylose production were firstly established on laboratory scale and then reproduced on a 10-L bench reactor fed with direct steam. The furfural production was maximum when using a 1.25% (w/w on dry fiber) H₂SO₄ solution at 175 °C during 40 min; whereas the xylose production attained the best results when using a 1% (w/v) H₂SO₄ solution in a solid/liquid ratio of 1/4 (g/mL), and the sugarcane bagasse impregnated with the acid solution during 24 h prior to the hydrolysis reaction. Enzymatic hydrolysis of the residual solid material obtained from furfural or xylose production was performed with yields of 17.4 and 9.3 g glucose/100 g initial raw material, respectively. Subsequently, ethanol was produced from the residual solid materials obtained from furfural and xylose production with yields of 87.4% and 89.3% respectively, based on the maximum theoretical value (0.51 g ethanol per g glucose in hydrolysate). Such results demonstrated the possibility of restructuring the processes for furfural or xylose production to obtain solid residues able to be used as substrate for ethanol production by fermentation.     

Production of xylose,furfural, fermentable sugars and ethanol from agricultural residues

With the developing shortage of petroleum, reliance on biomass as a source of chemicals and fuels will increase. In the present work, bagasse and rice husk were subjected to dilute acid (H₂SO₄) hydrolysis using pressurised water to obtain furfural and fermentable sugars. Various process conditions such as particle size, solid-liquid ratio, acid concentration, reaction time and temperature have been studied to optimise yields of furfural, xylose and other fermentable sugars. The use of particle sizes smaller than 495 μm did not further increase the yield of reducing sugars. A solid-liquid ratio of 1:15 was found to be the most suitable for production of reducing sugars. Hydrolysis using 0.4% H₂SO₄ at 453 K resulted in selective yields (g per 100 g of dried agricultural residues) of xylose from bagasse (22.5%) and rice husk (21.5%). A maximum yield of furfural was obtained using 0.4% H₂SO₄ at 473 K from bagasse (11.5%) and rice husk (10.9%). It was also found that hydrolysis using 1% H₂SO₄ at 493 K resulted in maximum yields of total reducing sugar from bagasse (53.5%) and rice husk (50%). The reducing sugars obtained were fermented to ethanol after removal of furfural. The effect of furfural on the fermentation of sugars to ethanol was also studied. Based on these studies, an integrated two-step process for the production of furfural and fermentable sugars could be envisaged. In the first step, using 0.4% H₂SO₄ at 473 K, furfural could be obtained, while in the second step, the use of 1% H₂SO₄ at 493 K should result in the production of fermentable sugars.     

醋酸水解玉米芯中木聚糖的动力学

利用醋酸作为催化剂水解玉米芯中半纤维素来制备还原糖,测定了温度在160-200℃、固液质量比为1∶15、搅拌速度为500 r/min下,不同水解时间水解液中还原糖的收率以及副产物糠醛的收率.利用半纤维素高温液态水的Garrote模型拟合还原糖生成过程.实验表明,该模型能够较好地描述还原糖生成过程以及副产物糠醛的产生过程...     

Hemicellulose Removal from Hardwood Chips in the Pre-Hydrolysis Step of the Kraft-Based Dissolving Pulp Production Process

Abstract

A pre-hydrolysis step to remove hemicelluloses from mixed hardwood chips consisting of maple, aspen, and birch with a ratio of 7:2:1 has been carried out. The effects of parameters on the pre-hydrolysis such as time, temperature, acetic acid addition, and raw material species, were determined. Different sugars, acetic acid, and furfural formation in the pre-hydrolysis liquor were quantified. The results showed that the pre-hydrolysis is a dynamic process, in which the removal of hemicelluloses increased with time while the conversion of extracted hemicelluloses to monosaccharides due to acid hydrolysis increased and part of the xylose was converted to furfural. The maximum temperature was the most critical parameter for hemicelluloses extraction and conversion, and a temperature of 170°C was the optimum for hemicelluloses extraction with relatively low conversion of xylose to furfural. About 11% of the xylan (in both monomeric and oligomeric forms) was removed at 170°C. Due to the presence of a high amount of xylan, birch produced the highest amount of xylose, followed by maple, and then aspen.     

Production of furfural by acid hydrolysis of corncobs

Hydrolysis of corncobs for producing furfural was carried out in a pressurized batch reactor using superheated water and diluted sulphuric acid as catalyst. The range of experimental conditions was T=140–200°C and P=350–1550 kPa. Yields of furfural are reported as a function of reaction temperature, particle size, acid concentration and liquid/solid ratio. Attention has been focused on the solid residue remaining after the hydrolysis process, so that it can be further used as a humic fertilizer after oxiammoniation treatment.     

Fatty acid composition and oxidation of lipids in Korean catfish

This study determined the lipid content and FA composition of muscle and a mixture of muscle and viscera from Korean catfish as well as lipid oxidation and hydrolysis. Lipid content and FA compositions in Korean catfish, which were purchased every month or two during September 1999–July 2000, were analyzed. Lipid oxidation and hydrolysis were determined as PV, thiobarbituric acid value, and FFA in the muscle and the mixture during storage at 2°C for 12 d and −14°C for 9 wk. Lipid contents of the muscle and the mixture were 3.2 (w/w) and 5.4%, respectively. Oleic acid was the most abundant FA in the catfish lipids, constituting 28.0% (w/w) of total FA in the muscle and 25.6% in the mixture, followed by palmitic acid and linoleic acid, amounting to 20.2 and 12.2%, respectively, in the muscle and 20.2 and 12.5% in the mixture. EPA and DHA were 3.2 and 6.8%, respectively, in the muscle and 3.5 and 8.1% in the mixture. Seasonal variation in lipid contents and FA composition was minimal in catfish. Lipids in minced catfish oxidized and hydrolyzed readily at 2°C. Inclusion of viscera into the muscle increased lipid oxidation and hydrolysis. Frozen storage at −14°C and addition of ascorbic acid both reduced lipid oxidation. Frozen storage retarded lipid hydrolysis in catfish.     

Hydrolysis of sugar cane bagasse with hydrochloric acid: Separation of the acid by pervaporation. Evaluation of the bergius process

Polyester reinforced PTFE membranes with a nominal pore size of 0.02 μm are very effective in pervaporating HCl gas from hydrochloric acid solutions and cellulose hydrolysates. The efficiency of such membranes, which may be as high as 1.8x10^?2 mmol HCl min^?1 cm^?2 at 40°C, is almost independent of the flow rate and the static pressure of the acidic solution but depends strongly on the acid concentration. At an acid concentration of 26% (w/v) the pervaporation of HCl is negligible at 40°C, but can be accelerated by increasing the temperature. A slow increase of temperature during the pervaporation process is proposed, as this promotes post-hydrolysis of the sugars. Lithium chloride induces structural changes in the membrane which increase efficiency without compromising performance. The use of this new technology in conjunction with the original Bergius process could improve the performance of the latter and reduce its overall costs. The use of the improved process for the hydrolysis of sugar cane bagasse could double the yields of sugar or alcohol per hectare of planted sugar cane.     

Hydrolysis of sugar cane bagasse with hydrochloric acid,promoted by metallic cations

Lithium chloride, in combination with commercial grade hydrochloric acid, is very effective in the hydrolysis of prehydrolysed sugar cane bagasse. After 10 min at 50°C the holocellulosic portion is completely dissolved and after 20 min most of the sugar oligomers are hydrolysed to monomers, making the time-and energy-consuming post-hydrolysis unnecessary. With longer reaction times the sugars start to reoligomerise and decompose. Zinc chloride is a milder promoter, requiring post-hydrolysis even after reaction for 30 min at 50°C. On the other hand, it does not decompose the sugars giving the highest sugar yields after prolonged reaction time and post-hydrolysis. Ferric chloride is mostly ineffective in the hydrolysis of cellulose but is a good promoter of the hydrolysis of the sugar oligomers, under the reaction conditions.     

Kinetic studies of hemicellulose hydrolysis of corn stover at atmospheric pressure

The object of this work was to study the xylose production by hydrolysis of corn stover with diluted sulfuric acid at 100 °C. Several concentrations of H₂SO₄ (2%, 4% and 6% w/w) and reaction time (0–300 min) were evaluated. Kinetic parameters of mathematical models for predicting the concentrations of xylose, glucose and furfural in the hydrolysates were found. Optimal conditions for hydrolysis were 5.5% H₂SO₄ at 100 °C for 60 min; under these conditions, 86.7% of xylose yield and 2.82 g/g selectivity were attained, leading to liquors containing up to 18.73 g/l xylose, 6.64 g/l glucose and 0.63 g/l furfural. The models could be successfully used to predict the concentrations of xylose, glucose and furfural within 0–300 min under experimental acid concentrations. Furthermore, the hydrolysis process of corn stover using dilute acid could be conceived as the first stage of an integrated strategy for corn stover utilization.     

Evaluation of the effects of operational parameters in the pretreatment of sugarcane bagasse with diluted sulfuric acid using analysis of variance

The pretreatment of lignocellulosic residues has been extensively studied as a method to disrupt the cellulose–hemicelluloses–lignin complex in biomass to access the sugars in their respective components. In this work, we carried out a study using sulfuric acid pretreatment of sugarcane bagasse by varying the following operational parameters: solid loading (10–30% of bagasse relative to the volume of the sulfuric acid solution), sulfuric acid concentration (0.5–2.5% relative to the dry mass of bagasse), reaction time (5–25?min), and temperature (135–195°C). The obtained solids from each pretreatment condition were submitted to enzymatic hydrolysis under the same process conditions: 0.232?g of Celluclast 1.5?L and 0.052?g of Novozym 188 per g of pretreated sugarcane bagasse, 72?h of hydrolysis, and 200?rpm of agitation at 50°C. Using central composite rotational design configuration in the experiments and analysis of variance, the results indicate that the conditions that produced larger quantities of glucose by enzymatic hydrolysis (0.35?g glucose/g pulp) with minimum amounts of degradation products were as follows: 20% solids loading, 15?min of reaction time, 1.5% sulfuric acid, and a minimum temperature of reaction of 170°C.     

蔗渣预水解液酸催化制备糠醛及其萃取分离（急）

以蔗渣为原料,在高温低酸浓度（H2SO4添加量占蔗渣绝干质量的0.176%）条件下预水解得到富含木糖的预水解糖液,再进一步深度酸解得到糠醛,并以混合有机溶剂实现了糠醛从水相中高效萃取分离。对蔗渣预水解条件、糠醛的有机溶剂萃取条件进行了探索,并采用FT-IR、XRD、SEM、TGA对蔗渣及预水解渣的形貌和结构进行了表征,利用紫外分光光度计对预水解过程中的木糖及深度酸解过程中的糠醛进行了定量检测。结果表明,在160 °C,液固比6：1,浓硫酸/蔗渣绝干质量为0.176%条件下,预水解液中木糖浓度最高（41.72 g/L）;该预水解液直接在170 °C条件下深度酸解90 min,溶液中糠醛浓度最高可达15.91 g/L,糠醛摩尔得率最高为59.60%。以v(1,2-二氯乙烷):v(正丁醇) = 9:1的比例混合有机溶剂对水溶液中糠醛进行萃取,萃取相体积比为v(有机相):v(水相) = 2:1,糠醛的萃取率可达93.53%。     

Influence of pretreatment conditions on composition of liquid hydrolysate and subsequent enzymatic saccharification of remaining solids

In the present work, the effect of dilute acid pretreatment was studied on the composition of liquid hydrolysate obtained after pretreatment by employing different combinations of process variables (temperature, time and acid concentration). The effect of pretreatment was also studied on subsequent enzymatic saccharification of remaining solids to obtain maximum yield of sugars. The efficiency of pretreatment was measured in terms of high‐xylose and low‐glucose yields, which was found most suitable at pretreatment conditions of 120°C, 120 min and 2% (v/v) acid concentration. With increased severity of pretreatment, xylose yield decreased with concomitant increase in glucose yield. The decrease in xylose yield was attributed to conversion into degradation products such as 5‐hydroxylmethyl furfural (HMF) and acetic acid. The percentage of enzymatic saccharification increased with increased pretreatment severity. Saccharification of biomass pretreated at 180°C, 7 min and 0.5% (v/v) acid concentration produced the maximum glucose yield of saccharification of 352 g/kg dry matter, compared to just 97 g glucose/kg dry matter in the case of untreated biomass. The same pretreatment conditions resulted in maximum total sugar yield of pretreatment and saccharification of 459 g/kg dry matter, which was more than 67% of the total potential sugars in biomass. © 2012 Canadian Society for Chemical Engineering     

Switchgrass pretreatment and hydrolysis using low concentrations of formic acid

BACKGROUND: Acid hydrolysis using organic acids is a promising approach for liquefying biomass without introducing any additional inorganic salt species into the reaction media. Formic acid may be a very useful acid catalyst for biomass pre‐treatment because (i) it is an effective, strong acid catalyst, (ii) it is no more corrosive than sulfuric acid, (iii) it is an organic acid, so it adds noinorganic salt species that might negatively impact downstream catalysis, and (iv) it can be produced from biomass, making ita green reagent. RESULTS: At pH_{25 °C} = 1.65, formic acid yielded high dissolution of switchgrass (52 wt%) at a high temperature (200 °C), comparable with the dissolution yield achieved using sulfuric acid. When treated 9/1 wt/wt with an 8 wt% aqueous solution of formic acid at 150 °C for 1 h, 44 wt% of switchgrass was dissolved, yielding 63 wt% of the carbohydrates from switchgrass. CONCLUSIONS: The efficiency of formic acid for the hydrolysis and dissolution of the carbohydrate fraction of switchgrass was proved and compared with other organic and mineral acids. The liquid product of pretreatment of switchgrass using formic acid at both 150 °C and 200 °C showed that 24 wt% and 28 wt%, respectively, of soluble monosaccharides after enzymatic hydrolysis consisted of glucose. Copyright © 2011 Society of Chemical Industry     

Production of Xylooligosaccharides from Waste Xylan,Obtained from Viscose Fiber Processing,by Selective Hydrolysis Using Concentrated Acetic Acid

Xylooligosaccharides (XOS) were prepared by selective hydrolysis of the waste xylan, obtained from viscose fiber plants, using concentrated acetic acid. The influences of acetic acid concentration, reaction temperature, and reaction time on the yield and component profiles of XOS product were investigated. These results were further ascertained by designing orthogonal experiments. The hydrolysis of xylan residue was selective, since mainly xylooligosaccharide components were formed, with hardly any impure ingredients, except for a small amount of xylose and traces of furfural, in the hydrolyzed product. Reaction temperature was found to be the most significant factor, influencing the XOS yield. Accurate HPAEC–PAD analysis of component profiles indicated that a maximum XOS yield of 45.86% was achieved on hydrolysis of 33.77 g/L waste xylan using 20% acetic acid for 20 min at 140°C. The main XOS components obtained were xylobiose, xylotriose, and xylotetraose, which were more than xylopentaose and xylohexaose.     

Hydrochloric acid‐catalyzed levulinic acid formation from cellulose: data and kinetic model to maximize yields

In this study, the kinetics of the acid catalyzed hydrolysis of microcrystalline cellulose (Avicel PH101) to levulinic (LA) and formic (FA) acids was investigated in a batch reactor over the following range of conditions: 160–200°C, hydrochloric acid concentrations of 0.309–0.927 M (11.3–33.8 g/l), cellulose concentrations of 49.8–149 mM (8.06–24.1 g/l), and residence times of 0–50 min. The maximum LA yield of around 60% of theoretical was achieved for an initial cellulose concentration of 99.6 mM, acid concentration 0.927 M, and 180–200°C. A mathematical model and its analytical solution were developed to predict conversion of cellulose to LA and FA through glucose and hydroxymethyl‐2‐furfural based on an irreversible pseudo‐first order reaction. Rate analysis of each reaction indicated that the rate‐controlling step shifted from LA formation initially to HMF formation later. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Dilute acid hydrolysis of lignocellulosic biomass

The overall aim of this work was to establish the optimum conditions for acid hydrolysis of hemicellulosic biomass in the form of potato peel. The hydrolysis reaction was undertaken in a 1l high pressure pilot batch reactor using dilute phosphoric acid. Analysis of the decomposition rate of hemicellulosic biomass (namely Cellulose, Hemicellulose and lignin) was undertaken using HPLC of the reaction products namely, 5 and 6 carbon sugars. Process parameters investigated included, reactor temperature (from 135 °C to 200 °C) and acid concentration (from 2.5% (w/w) to 10% (w/w)). Analysis of the reactor products indicated that high conversion of cellulose to glucose was apparent although arabinose conversion was quite low due to thermally un-stability. However, an overall sugar yield is 82.5% was achieved under optimum conditions. This optimum yield was obtained at 135 °C and 10% (w/w) acid concentration. 55.2 g sugar/100 g dry potato peel is produced after a time of 8 min. The work indicates that the use of potato peel may be a feasible option as a feed material for the production of sugars for biofuel synthesis, due its low cost and high sugar yields.     

Characterisation of biocatalysts immobilised in niobium—a new inorganic solid support

A new support for enzyme immobilisation, an alloy of niobium ore and graphite, was tested with: invertase from baker's yeast and inulinase from Aspergillus niger. The efficiency of immobilisation was about 30% for invertase and 72% for inulinase. The maximum activities values were observed for both enzymes at: pH 4.5, 50°C and 500 g/L of sucrose. The hydrolysis of inulin (5% w/v) by the free inulinase and invertase presented specific productivity of reducing sugars lower after immobilisation, about 15 and 1.5 times, respectively; with the hydrolysis of sucrose (50% w/v) the reductions observed were of 14 and 3.5 times, respectively. © 2012 Canadian Society for Chemical Engineering