Comparison of ethanol production from corn cobs and switchgrass following a pyrolysis-based biorefinery approach

Background One of the main obstacles in lignocellulosic ethanol production is the necessity of pretreatment and fractionation of the biomass feedstocks to produce sufficiently pure fermentable carbohydrates. In addition, the by-products (hemicellulose and lignin fraction) are of low value, when compared to dried distillers grains (DDG), the main by-product of corn ethanol. Fast pyrolysis is an alternative thermal conversion technology for processing biomass. It has recently been optimized to produce a stream rich in levoglucosan, a fermentable glucose precursor for biofuel production. Additional product streams might be of value to the petrochemical industry. However, biomass heterogeneity is known to impact the composition of pyrolytic product streams, as a complex mixture of aromatic compounds is recovered with the sugars, interfering with subsequent fermentation. The present study investigates the feasibility of fast pyrolysis to produce fermentable pyrolytic glucose from two abundant lignocellulosic biomass sources in Ontario, switchgrass (potential energy crop) and corn cobs (by-product of corn industry). Results Demineralization of biomass removes catalytic centers and increases the levoglucosan yield during pyrolysis. The ash content of biomass was significantly decreased by 82–90% in corn cobs when demineralized with acetic or nitric acid, respectively. In switchgrass, a reduction of only 50% for both acids could be achieved. Conversely, levoglucosan production increased 9- and 14-fold in corn cobs when rinsed with acetic and nitric acid, respectively, and increased 11-fold in switchgrass regardless of the acid used. After pyrolysis, different configurations for upgrading the pyrolytic sugars were assessed and the presence of potentially inhibitory compounds was approximated at each step as double integral of the UV spectrum signal of an HPLC assay. The results showed that water extraction followed by acid hydrolysis and solvent extraction was the best upgrading strategy. Ethanol yields achieved based on initial cellulose fraction were 27.8% in switchgrass and 27.0% in corn cobs. Conclusions This study demonstrates that ethanol production from switchgrass and corn cobs is possible following a combined thermochemical and fermentative biorefinery approach, with ethanol yields comparable to results in conventional pretreatments and fermentation processes. The feedstock-independent fermentation ability can easily be assessed with a simple assa

Application of cost effective and real-time resistivity sensor to study early age concrete

Concrete is a widely used construction material, demanding strict quality control to maintain its integrity. The durability and lifespan of concrete structures rely heavily, amongst other factors, on the characteristics of fresh and early age concrete, which are strongly dependent on the curing process. To ensure long-term durability, it is crucial to assess concrete properties throughout construction and verify compliance with design specifications. Currently, electrical resistivity-based sensors are available and used for quality control and monitoring, however, these sensors tend to be costly or only measure at a single location within the concrete cover. This study introduces a printed circuit board (PCB)-based array of electrodes capable of measuring concrete resistivity profiles across the concrete cover, from its fresh state to early age development. In this work, the feasibility of such resistivity PCB-sensors, novel for concrete, is evaluated under laboratory conditions. The sensors exhibit a promising performance in monitoring the efficiency of concrete curing under various conditions. Additionally, they successfully evaluate the effectiveness of internal curing (in our study, promoted by superabsorbent polymers) during the initial stages of hardening. This sensor array provides a valuable tool for monitoring the curing of concrete at early age, and showcases a preliminary solution that could be further developed to ensure long-term performance of concrete infrastructure

Combined organic acid leaching and torrefaction as pine wood pretreatment before fast pyrolysis

Reducing pine wood particle size is beneficial for acid leaching (shorter leaching time, smaller equipment size) and also for pyrolysis (low pyrolysis time, high oil and sugar yields). Torrefaction helps to improve the energy efficiency of grinding. However, it is not well established whether alkali and alkaline earth metals can still be removed effectively, after torrefaction, by leaching with an acetic acid solution, while keeping high oil and sugar yields. To investigate this, an experimental study was carried out combining torrefaction (290 °C, 20 minutes) and subsequently acid leaching of pine wood as pretreatment step before fast pyrolysis of the feedstock at 530 °C. The oil, char, gas, water, pyrolytic lignin, light oxygenates and levoglucosan yields were compared with the results obtained from fast pyrolysis of untreated pine wood and acid leached pine wood at 530 °C. In addition, pyrolysis vapors were condensed step-wise into two distinguished fractions (condensation T = 80 oC) to increase the levoglucosan concentration up to 45 wt. % with or without applying torrefaction as pretreatment. Intra-particle reactions during torrefaction are more profound in the presence of alkali and alkaline earth metals. Cellulose and lignin derived products (e.g. levolucosan (~0.2 kg/kg pine wood) and pyrolytic lignin (~0.11 kg/kg pine wood) were not affected by the torrefaction pre-treatment of acid leached pine wood. In general, torrefaction of acid leached pine wood followed by fast pyrolysis showed similar total organics, char, gas, light oxygenates and produced water yields compared to fast pyrolysis of acid leached pine wood. Contrary, when acid leaching is applied after torrefaction the organics (dry bio-oil) and light oxygenates yields are quite comparable to the results of untreated pine wood fast pyrolysis

Effect of temperature on the fast pyrolysis of organic-acid leached pine wood; the potential of low temperature pyrolysis

In this paper, we have evaluated the potential of organic acid (mixture of acetic, formic and propionic acid) leaching of biomass and subsequent fast pyrolysis to increase the organic oil, sugars and phenols yield by varying the fluidized bed temperature between 360 °C and 580 °C (360 °C, 430 °C, 480 °C, 530 °C, and 580 °C). The pyrolysis of acid leached pinewood resulted in more organic oil and less water and residue compared to untreated pinewood over the whole temperature range. Below 500 °C the difference was most profound; for acid leached pinewood at 360 °C the organic oil was already 650 g kg−1 pine with a sugar yield of 230 g kg−1 pine. At this low pyrolysis temperature no bed agglomeration was observed for acid leached pine whereas at the higher temperatures tested agglomerates were found, which were identified to be clusters of fluidization sand glued together by sticky pyrolysis products (melt). Low reactor temperatures also favored the production of monomeric phenols, though their absolute yields remained low for both untreated and leached pine (maximum: 23 g kg−1 pine, 80 g kg−1 lignin). GPC, GC/MS and UV-fluorescence spectroscopy showed that acid leaching did not influence significantly the yield and molecular size of the aromatic fraction in the produced pyrolysis oils. Back impregnation of the removed AAEMs into leached biomass revealed that the effects of the applied acid leaching, both with respect to the product yields and bed agglomeration, can be mainly assigned to the removal of AAEMs

Aromatics extraction from pyrolytic sugars using ionic liquid to enhance sugar fermentability

Fermentative bioethanol production from pyrolytic sugars was improved via aromatics removal by liquid–liquid extraction. As solvents, the ionic liquid (IL) trihexyltetradecylphosphonium dicyanamide (P666,14[N(CN)2]) and ethyl acetate (EA) were compared. Two pyrolytic sugar solutions were created from acid-leached and untreated pinewood, with levoglucosan contents (most abundant sugar) of 29.0% and 8.3% (w/w), respectively. In a single stage extraction, 70% of the aromatics were effectively removed by P666,14[N(CN)2] and 50% by EA, while no levoglucosan was extracted. The IL was regenerated by vacuum evaporation (100 mbar) at 220 °C, followed by extraction of aromatics from fresh pyrolytic sugar solutions. Regenerated IL extracted aromatics with similar extraction efficiency as the fresh IL, and the purified sugar fraction from pretreated pinewood was hydrolyzed to glucose and fermented to ethanol, yielding 0.46 g ethanol/(g glucose), close to the theoretical maximum yiel

Using pyrolytic acid leaching as a pretreatment step in a biomass fast pyrolysis plant: process design and economic evaluation

Removing alkali and alkaline earth metals (AAEMs) from biomass, with pyrolytic acids, before pyrolysis leads to increased organic oil and sugar yields. These pyrolytic acids are produced and concentrated within the pyrolysis process itself. The purpose of this paper was to evaluate under which conditions acid leaching of pinewood, bagasse and straw can improve the technical and economic feasibility of a pyrolysis process. Therefore, a preliminary process design for the implementation of acid leaching at a pyrolysis plant, with a biomass capacity of 5 and 50 t h−1, was made and compared with a pyrolysis plant using the untreated biomass. Target products were heating oil and/or additional pyrolytic sugars. It has been calculated that with the leaching step the heat for pyrolysis and drying of the biomass can still be supplied by the combustion of the char and gases, but insufficient excess heat is available to produce electricity for the process. Critical for the economics of the acid leaching pyrolysis process are the amount of extractives in the biomass (organics ending up in the waste water) but not its moisture content. Mechanical dewatering before thermal drying turns out to be very important. The economics of the presented approach turned out to be very sensitive to the plant scale, CAPEX and obviously to the biomass price. At the current market scenario and state of proven techniques the production of sugars and heating oil from bagasse at 50 t h−1 is the most economic option (IRR 15.4%)

Pyrolysis based bio-refinery for the production of bioethanol from demineralized ligno-cellulosic biomass

This paper evaluates a novel biorefinery approach for the conversion of lignocellulosic biomass from pinewood. A combination of thermochemical and biochemical conversion was chosen with the main product being ethanol. Fast pyrolysis of lignocellulosic biomasss with fractional condensation of the products was used as the thermochemical process to obtain a pyrolysis-oil rich in anhydro-sugars (levoglucosan) and low in inhibitors. After hydrolysis of these anhydro-sugars, glucose was obtained which was successfully fermented, after detoxification, to obtain bioethanol. Ethanol yields comparable to traditional biochemical processing were achieved (41.3% of theoretical yield based on cellulose fraction). Additional benefits of the proposed biorefinery concept comprise valuable by-products of the thermochemical conversion like bio-char, mono-phenols (production of BTX) and pyrolytic lignin as a source of aromatic rich fuel additive. The inhibitory effect of thermochemically derived fermentation substrates was quantified numerically to compare the effects of different process configurations and upgrading steps within the biorefinery approac