Optimization of dilute acid and hot water pretreatment of different lignocellulosic biomass: A comparative study

Pretreatment of biomass to alter their recalcitrant structures is an essential step to obtain high yield of products via bioconversion processes. In this study, main emphasis was to compare the results evaluated in terms of total reducing sugars (TRS) yield after acid and hot water pre-treatment process performed with laboratory scale equipment using different lignocellulosic biomass. The biomass chosen for this purpose i.e. sugarcane bagasse and bamboo were collected from Guwahati, Assam and their physico-chemical characteristics were examined using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy and thermo gravimetric analysis (TGA) including proximate and ultimate analysis. Crystalinity of the biomass used was observed to be 33.15% and 31.29% for sugarcane bagasse and bamboo respectively. Hot water and dilute acid pretreatment allows selective solubility of hemicellulose which improves the accessibility of enzymes for cellulose hydrolysis. The highest yield of TRS was observed at run order 8 for both acid and hot water pretreatment (23.49 and 26.50 gL⁻¹) with respect to sugarcane bagasse. But, the pretreatment results obtained for bamboo was slightly different to that of sugarcane bagasse. The highest yield of TRS was obtained at run order 8 for acid (15.6 gL⁻¹) and run order 10 for hot water (17.98 gL⁻¹) pretreatment respectively. Irrespective of biomass type, hot water pretreatment process produced more TRS than acid pretreatment process.     

Disruption of sugarcane bagasse lignocellulosic structure by means of dilute sulfuric acid pretreatment with microwave-assisted heating

Disruption of lignocellulosic structure of biomass plays a key role in producing bioethanol from lignocelluloses. This study investigated the impact of dilute sulfuric acid pretreatment on bagasse structure using microwave heating. Three reaction temperatures of 130, 160 and 190 °C with two heating times of 5 and 10 min were considered and a number of instruments were employed to analyze the properties of the bagasse particles. On account of microwave irradiation into the solution with dielectric heating, the experiments indicated that an increase in reaction temperature destroyed the lignocellulosic structure of bagasse in a significant way. The pretreated bagasse particles were simultaneously characterized by fragmentation and swelling. When the reaction temperature was as high as 190 °C, the fragmentation of particles became fairly pronounced so that the specific surface area of the pretreated material grew substantially. Meanwhile, almost all hemicellulose was removed from bagasse and the crystalline structure of cellulose disappeared. In contrast, the feature of lignin was remained clearly. However, a comparison between the heating times of 5 and 10 min revealed that the influence of the heating time on the lignocellulosic structure was not significant, indicating that the pretreatment with 5 min was sufficiently long.     

酸预处理对生物质快速热裂解产物的影响

文章旨在通过酸预处理提高生物质热裂解过程中左旋葡聚糖的生成量,基于裂解-气相色谱/质谱联用仪(Py-GC/MS)技术,以黄松为原料,采用3种不同酸预处理条件进行了热裂解和酸预处理条件优化实验;通过测量酸预处理前后生物质中无机金属离子(Ca~(2+),Mg~(2+),K~+和Na~+)含量的变化,探讨了酸预处理对于生物质中无机金属离子含量以及热解产物的影响特性。研究结果表明:酸预处理后,生物质中无机金属离子含量显著降低;黄松裂解过程中,左旋葡聚糖产量显著提高;左旋葡萄糖酮产量显著降低。在所选3种酸预处理条件中,磷酸预处理的黄松裂解产物的左旋葡聚糖得率最高(20.5%),乙酸和2-甲氧基-4-丙基苯酚的得率最低。     

Improvement of enzymatic saccharification of Populus and switchgrass by combined pretreatment with steam and wet disk milling

To reduce the recalcitrance of lignocellulosic biomass for subsequent biological processing, we pretreated energy crop feedstocks with mild steam treatment (ST; 130 and 150 °C for 60 min) and wet disk milling (WDM). We tested two phylogenetically different, but typical energy crop feedstocks: Populus trichocarpa and switchgrass (Panicum virgatum). WDM after ST facilitated the fibrillation of both types of biomass, resulting in an increase of specific surface area, improved enzymatic saccharification yield, and decrease in cellulose crystallinity. After steam treatment at 150 °C followed by 17 cycles of WDM, enzymatic hydrolysis resulted in almost complete glucan to glucose conversion in both feedstocks.     

稀硫酸预处理玉米秸秆条件的优化研究

对稀硫酸预处理玉米秸秆优化工艺条件进行了试验研究,在考察温度、时间、稀硫酸质量分数、固液质量比和玉米秸秆粒度5个单因素对预处理效果影响的基础上,采用响应面分析法对预处理条件进行优化,建立了以戊糖得率为响应值的二次回归方程模型,得到最佳预处理条件为水解温度120℃,水解时间75 min,稀硫酸质量分数1.0%,固液质量比1∶15,玉米秸秆颗粒为40目。此条件下,理论预测戊糖得率为65.018%,试验验证戊糖得率为64.37%,与预测值接近,说明预测模型可靠性较高,可应用于稀酸预处理条件的优化。     

Impact of dilute acid pretreatment on the structure of bagasse for bioethanol production

Dilute acid pretreatment is a commonly used pretreatment method in the course of producing bioethanol from lignocellulosics and the structure variation of the lignocellulosics is highly related to the pretreatment process. To understand the impact of dilute acid pretreatment on the structure of bagasse, four different pretreatment conditions by varying heating time are considered where the bagasse and the pretreated materials are examined using a variety of analysis methods. The obtained results indicate that the thermogravimetric analysis (TGA) is able to provide a useful insight into the recognition of lignocellulosic structure. Specifically, the peak of the TGA of the pretreated materials moves toward the low temperature region, revealing that the lignocellulosic structure is loosened. However, the characteristic of crystal structure of cellulose remains in the pretreated materials. Increasing heating time enhances the pretreatment procedure; as a result, the average particle size of the investigated materials increases with heating time. This swelling behavior may be attributed to the enlarged holes inside the particles in that the surface area decreases with increasing heating time. In addition, when the heating time is increased to a certain extent (e.g. 15 min), some fragments are found at the surface and they tend to peel off from the surface. It follows that the dilute acid pretreatments have a significant effect on the bagasse structure. Copyright © 2009 John Wiley & Sons, Ltd.     

Nitrogen explosion pretreatment of lignocellulosic material for bioethanol production

A novel method for the pretreatment of lignocellulosic material is investigated in this work, using floodplain meadow hay as a feedstock for bioethanol production. Pressurized nitrogen (N₂) pretreatment is combined with explosive decompression to achieve high glucose yields with simple technology and low energy input. Results show that N₂ explosion yields hydrolysis efficiencies up to 71.8%. The highest hydrolysis efficiency was achieved at a temperature of 210°C with a cellulose to glucose conversion rate of 195.1 g kg^?1 of biomass.     

木质纤维素生物质生产乙醇的预处理技术

木质纤维素生物质经过预处理后，原料的内孔面积增大，纤维素的结晶性降低，并且半纤维素和木质素被去除．预处理后的生物质容易进行酶水解生产燃料乙醇。总结了近些年来的预处理技术，如物理法、化学法和生物法。     

Hydrothermal pretreatment of switchgrass and corn stover for production of ethanol and carbon microspheres

Pretreatment of biomass is viewed as a critical step to make the cellulose accessible to enzymes and for an adequate yield of fermentable sugars in ethanol production. Recently, hydrothermal pretreatment methods have attracted a great deal of attention because it uses water which is a inherently present in green biomass, non-toxic, environmentally benign, and inexpensive medium. Hydrothermal pretreatment of switchgrass and corn stover was conducted in a flow through reactor to enhance and optimize the enzymatic digestibility. More than 80% of glucan digestibility was achieved by pretreatment at 190 °C. Addition of a small amount of K₂CO₃ (0.45-0.9 wt.%) can enhance the pretreatment and allow use of lower temperatures. Switchgrass pretreated at 190 °C only with water had higher internal surface area than that pretreated in the presence of K₂CO₃, but both the substrates showed similar glucan digestibility. In comparison to switchgrass, corn stover required milder pretreatment conditions. The liquid hydrolyzate generated during pretreatment was converted into carbon microspheres by hydrothermal carbonization, providing a value-added byproduct. The carbonization process was further examined by GC-MS analysis to understand the mechanism of microsphere formation.     

N2 explosive decompression pretreatment of biomass for lignocellulosic ethanol production

This paper presents a novel biomass pretreatment method that uses high pressured N₂ and temperature to break the hemicellulose and lignin seal around the cellulose macro fibrils in the cell walls of the lignocellulosic biomass in order to open up the biomass structure for more efficient enzymatic hydrolysis. In this method the biomass is exposed to a high pressure using N₂ gas, and temperature. Under pressure, cells of the lignocellulosic biomass are filled with a solution saturated with nitrogen. When the pressure is then suddenly released, the feedstock is exposed to an explosive decompression and the dissolved nitrogen is released from the solution. Sudden change in the volume breaks the cell walls and opens the biomass structure resulting in increased surface area of the substrate for enzymatic hydrolysis. No catalysts or chemicals were added in the process thereby, making it economically and environmentally attractive. In this research, a range of different pressures (1–60 bar) and temperatures (25–175 °C) were applied to barley straw to evaluate the efficiency of the pretreatment. The pretreatment was followed by enzymatic hydrolysis and fermentation. Resulting glucose and ethanol concentrations were measured and the yields were considered as an estimate for the most suitable set of pretreatment conditions. The results indicate that the highest glucose yield and hydrolysis efficiency were gained at 150 °C and 10–30 bars. The fermentation efficiency was lower at higher temperatures. Nonetheless, the highest ethanol yield was still gained at the same conditions.     

Statistical optimization of dilute acid pretreatment of pinus needles to be used as substrate for biofuel production

In this study response surface methodology (RSM) was applied to study the effect of H₂SO₄ concentration, temperature, and time on the production of reducing sugars, total sugars, and total phenolic compounds from pine needles. Three variables with three levels showed that maximum release of total phenolic compounds (31.20 ± 0.002 mM) was observed at 1% H₂SO₄ concentration, 130°C temperature for 75 min of residence time. Under these conditions, the predicted value of total phenolic compounds was 31.27 mM, which indicated that the model is valid, having negligible variation in observed and predicted values. These results suggested that this substrate could be potentially used as substrate for bioethanol production.     

Biohydrogen production from pure and natural lignocellulosic feedstock with chemical pretreatment and bacterial hydrolysis

Pretreatment and saccharification of lignocellulosic materials is the key technology affecting the efficiency of cellulosic biohydrogen production. In this work, two pure cellulosic materials (i.e., carboxymethyl-cellulose (CMC) and xylan) were directly hydrolyzed (without pretreatment) by a cellulolytic isolate Cellulomonas uda E3-01 able to release extracellular cellulolytic enzymes. Natural cellulosic feedstock (i.e., sugarcane bagasse) was chemically pretreated prior to the bacterial hydrolysis.A temperature-shift strategy (35 °C for cellulolytic enzymes production and 45 °C for hydrolysis reaction) was used to increase the production of reducing sugars during the bacterial hydrolysis. The hydrolysates of CMC, xylan, and bagasse were efficiently converted to H₂ via dark fermentation with Clostridium butyricum CGS5. The maximum hydrogen yield was 8.80 mmol H₂/g reducing sugar (i.e., 1.58 mol H₂/mol hexose) for CMC, 6.03 mmol H₂/g reducing sugar (i.e., 0.91 mol H₂/mol pentose) for xylan, and 6.01 mmol H₂/g reducing sugar for bagasse.     

Optimisation of dilute alkaline pretreatment for enzymatic saccharification of wheat straw

Physico-chemical pretreatment of lignocellulosic biomass is critical in removing substrate-specific barriers to cellulolytic enzyme attack. Alkaline pretreatment successfully delignifies biomass by disrupting the ester bonds cross-linking lignin and xylan, resulting in cellulose and hemicellulose enriched fractions. Here we report the use of dilute alkaline (NaOH) pretreatment followed by enzyme saccharifications of wheat straw to produce fermentable sugars. Specifically, we have assessed the impacts of varying pretreatment parameters (temperature, time and alkalinity) on enzymatic digestion of residual solid materials. Following pretreatment, recoverable solids and lignin contents were found to be inversely proportional to the severity of the pretreatment process. Elevating temperature and alkaline strengths maximised hemicellulose and lignin solubilisation and enhanced enzymatic saccharifications. Pretreating wheat straw with 2% NaOH for 30 min at 121 °C improved enzyme saccharification 6.3-fold when compared to control samples. Similarly, a 4.9-fold increase in total sugar yields from samples treated with 2% NaOH at 60 °C for 90min, confirmed the importance of alkali inclusion. A combination of three commercial enzyme preparations (cellulase, ??-glucosidase and xylanase) was found to maximise monomeric sugar release, particularly for substrates with higher xylan contents. In essence, the combined enzyme activities increased total sugar release 1.65-fold and effectively reduced cellulase enzyme loadings 3-fold. Prehydrolysate liquors contained 4-fold more total phenolics compared to enzyme saccharification mixtures. Harsher pretreatment conditions provide saccharified hydrolysates with reduced phenolic content and greater fermentation potential.     

Evaluation of pretreatment potential and hydrogen recovery from lignocellulosic biomass in an anoxic double-staged bioelectrochemical system

The possible impact of bio and electrochemical reactions during pretreatment of rice straw using solvents, sulphuric acid (SA), ammonia (AM), sodium hydroxide (NA), and distilled water (W) was investigated. The total volatile fatty acids (tVFAs) of 163.48 ± 10.49 mM in the electrochemical pre-treatment in the presence of sodium hydroxide (ENA) followed by sulfate-reducing bacteria (EBA) (140.88 ± 0.07 mM) indicating the involvement of electrolytic breakdown of lignocellulosic biomass. The hydrogen production of 0.224 ± 0.05 and 0.218 ± 0.10 mM/g of the substrate was found in the ENA and anoxic sodium hydroxide pre-treatment (CNA) respectively. There was no detectable gasification in SA and AM electrochemical pre-treatments. The major advantage of the electrochemical process is the formation of acetic acid at a lower temperature, whereas processes like autohydrolysis form it at high temperatures during stream explosion pretreatment. The hydrogen production of 1.26 mM/g was found from anoxic hydrolysate pretreated (ECP) rice straw. The SEM and FTIR analysis show distortion of outer layers of biomass in the electrochemical pretreatment (ECP) system, which improved its accessibility towards enzymes for value-added product recovery.     

Catalytic effects observed during the co-gasification of coal and switchgrass

We are investigating catalytic gasification of coal char using biomass-derived potassium salts. Alkali metal salts, especially those containing potassium, are excellent promoters of gasification reactions but are generally considered too expensive for commercial use. Fast-growing biomass, which contains large quantities of potassium, may prove to be an excellent source of inexpensive gasification catalyst. A series of CO₂-char gasification tests were performed in a thermogravimetric analyzer (TGA) to evaluate the catalytic activity of alkali-rich biomass-derived materials. Both switchgrass char and switchgrass ash displayed catalytic activity in mixtures with coal char produced from Illinois No. 6 coal. The results obtained with switchgrass ash were especially impressive, with an almost eight-fold increase in coal char gasification rate at 895°C in a 10:90 mixture of coal char and switchgrass ash. These results give encouragement that biomass could be the source of inexpensive, coal gasification catalysts.     

微波辅助NaOH预处理提高油菜秸秆酶解效率的研究

为提高油菜秸秆的酶解效率,试验借助于常压微波加热技术辅助NaOH预处理,并对处理条件进行了优化。结果表明,与未处理比较,经微波预处理的油菜秸秆致密结构明显破坏,利于被纤维素酶水解。微波辅助预处理的最优化条件:微波功率600 W,时间5 min,NaOH 0.1 mol/L,温度80℃,经预处理后的油菜秸秆酶解率可达28.09%,较未处理前增加2.75倍,显著提高了酶解效果。     

Insights into biological delignification of rice straw by Trametes hirsuta and Myrothecium roridum and comparison of saccharification yields with dilute acid pretreatment

Rice straw is the most abundant agricultural residue on a global scale and is widely available as feedstock for cellulosic fuel production. However, it is highly recalcitrant to biochemical deconstruction and also generates inhibitors that affect enzymatic saccharification. Rice straw from eastern Arkansas was subjected to dilute acid pretreatment (160 °C, 48 min and 1.0% sulfuric acid) and solid-state fermentation with two lignocellulolytic fungi, Trametes hirsuta and Myrothecium roridum, and their saccharification efficacies were compared. T. hirsuta and M. roridum were tested separately; pretreatment of rice straw with either strain for seven days resulted in 19 and 70% enrichment of its holocellulose content, respectively. However, liquid chromatography analysis of the alkali extracts showed significant differences in cell wall degradation by T. hirsuta and M. roridum. T. hirsuta removed 15% more phenolic compounds and 38% more glucan than M. roridum, while M. roridum removed 77% more xylan than T. hirsuta. Fungal and dilute acid pretreated biomass was then hydrolyzed using Accellerase^® 1500, a saccharification cocktail. Saccharification efficiency of M. roridum was 37% higher than that of dilute acid pretreatment of rice straw, requiring 8% lower enzyme loading and 50% shorter enzymatic hydrolysis duration. Alkali extraction of fungal pretreated biomass also yielded 10–15 g kg⁻¹ of acid precipitable polymeric lignin (APPL), which is a valuable co-product for biorefineries. In comparison to dilute acid pretreatment, fungal pretreatment could be a cost-effective alternative for the degradation of recalcitrant biomass, such as rice straw.     

Chemical composition and response to dilute-acid pretreatment and enzymatic saccharification of alfalfa,reed canarygrass,and switchgrass

Alfalfa stems, reed canarygrass, and switchgrass; perennial herbaceous species that have potential as biomass energy crops in temperate regions; were evaluated for their bioconversion potential as energy crops. Each forage species was harvested at two or three maturity stages and analyzed for carbohydrates, lignin, protein, lipid, organic acids, and mineral composition. The biomass samples were also evaluated for sugar yields following pretreatment with dilute sulfuric followed by enzymatic saccharification using a commercial cellulase preparation. Total carbohydrate content of the plants varied from 518 to 655 g kg⁻¹ dry matter (DM) and cellulose concentration from 209 to 322 g kg⁻¹ DM. Carbohydrate and lignin contents were lower for samples from early maturity samples compared to samples from late maturity harvests. Several important trends were observed in regards to the efficiency of sugar recovery following treatments with dilute acid and cellulase. First, a significant amount of the available carbohydrates were in the form of soluble sugars and storage carbohydrates (4.3–16.3% wt/wt). Recovery of soluble sugars following dilute acid pretreatment was problematic, especially that of fructose. Fructose was found to be extremely labile to the dilute acid pretreatments. Second, the efficiency at which available glucose was recovered was inversely correlated to maturity and lignin content. However, total glucose yields were higher for the later maturities because of higher cellulose contents compared to the earlier maturity samples. Finally, cell wall polysaccharides, as determined by the widely applied detergent fiber system were found to be inaccurate. The detergent fiber method consistently over-estimated cellulose and hemicellulose and underestimated lignin by substantial amounts.     

稀酸处理对秸秆厌氧发酵产氢的影响

以稻草秸秆为纤维素原料,先利用稀硫酸对其进行预处理,再利用活性污泥进行厌氧发酵产氢。试验研究了压力、温度、硫酸浓度、加压时间、固液比以及原料粒度对预处理结果的影响,并根据产氢量优化了预处理条件。试验结果表明:在硫酸浓度为0.7%、处理压力为0.1MPa、加压时间为60min、固液比为1∶12,秸秆原料过60目筛的情况下预处理效果最好,此时每克秸秆产氢量为113ml,秸秆中半纤维素、纤维素的利用率为87.47%,秸秆的有效利用率为52.38%。     

Influence of heating source on the efficacy of lignocellulosic pretreatment - A cellulosic ethanol perspective

Three different heating devices (Hot plate (HP), Autoclave (AC) & Microwave (MW)) were tested for their efficiency to pretreat garden biomass (GB), a lignocellulosic substrate. Effectiveness of different modes of heat on pretreatment was assessed taking into consideration the yield of reducing sugar (RS), recovery of cellulose after pretreatment, conversion of hemicellulose into reducing sugar, changes in the ultra structure of GB tissues, changes in the crystallinity of GB etc. The results indicated that all three heating devices are useful for pretreatment, however, the efficacy of MW on GB was found be better than AC and HP. A maximum of 53.95% of cellulose recovery was obtained in case of MW heating along with 46.97% of reducing sugar yield. This when compared to AC and HP is significantly higher (more than 10% increase) and time saving (only 15 min reaction time) as well.