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14 декабря, 2021
Wet oxidation
Wet oxidation is an oxidative pre-treatment method which employs oxygen or air as catalyst, and can be operated at relatively low temperatures and short reaction times [182]. It is an exothermic process, therefore self-supporting with respect to heat while the reaction is started [183]. Wet oxidation of the hemicellulose fraction is a balance between solubilisation and degradation. Wet oxidation has been proven to be an efficient method for separating the cellulosic fraction from lignin and hemicellulose [184], and also been widely used for ethanol production followed by SSF [185]. Wet oxidation pre-treatment mainly causes the formation of acids from hydrolytic processes, as well as oxidative reactions. The hemicelluloses are extensively cleaved to monomer sugars, cellulose is partly degraded, and the lignins undergo both cleavage and oxidation in wet oxidation pre-treatment. Therefore lignin produced by wet oxidation cannot be used as a fuel [186]. In general, low formation of inhibitors and efficient removal of lignin can be achieved with wet oxidation pre-treatment.
Ozonolysis
Ozone is a powerful oxidant that shows high delignification efficiency [106]. This method can effectively degrade lignin and part of hemicellulose. The pre-treatment is usually carried out at room temperature, and does not lead to inhibitory compounds [187]. It is usually performed at room temperature and normal pressure and does not lead to the formation of inhibitory compounds that can affect the subsequent hydrolysis and fermentation. However, ozonolysis might be expensive since a large amount of ozone is required, which can make the process economically unviable [106].
Although there are a great number of insects feeding on willows, three main species are of concerns for willow short rotation coppice in Quebec. The first is the willow leaf beetle (Plagiodera versicolora Laicharteg.), one of the most common insects found on willows. The willow leaf beetle is a small (4 — 6 mm long), metallic-blue beetle widely distributed around the world. In Quebec, adults emerge from their overwintering quarters under the loose bark and feed on young willow foliage in spring. Egg laying begins in mid-June. Females lay yellow eggs grouped on the undersides of the leaves. The young larvae emerge a few days later and begin feeding on both sides of the leaves and eating the tissue between the veins, thus skeletonizing the leaves and, depending on the extent of the attack, in all probability leading to a reduction of plant growth. In Quebec, this insect has been frequently observed feeding on leaves of clones of Salix viminalis and to a much lesser extent on most common commercial varieties of S. miyaheana (SX64 and SX67) and S. sachalinensis (SX61). To date, the reported threshold of damage caused by this insect has never been high enough to justify any type of control. However, in case of severe attack, non-toxic products based on Bacillus thuringiensis, shown to be effective in eliminating this pathogen, can be used [60].
The other predominant insects found feeding on willow trees and shrubs are two aphid species: the giant willow aphid, Tuherolachnus salignus (Gmelin) and the black willow aphid, Pterocomma salicis (L) [61].
The giant willow aphid. is one of the largest aphids ever recorded, measuring up to 5.8 mm in length [62]. It feeds almost exclusively on willow, but has very occasionally been recorded on poplar (Populus spp.). The species is strongly aggregative, forming vast colonies on infested trees. These colonies can cover a significant portion of the 1-3 year old stem surface of a willow tree. Laboratory experiments with willows grown in soil and in hydroponic culture have revealed that this species can reduce the above-ground yield of biomass willows, have severe negative effects on the roots and reduce the survival of both newly planted and established trees [63]. Other preliminary studies carried out in the UK have shown that this insect’s feeding behavior is affected by chemical cues from the host. Researchers found that one of its most preferred willows was S. viminalis [64]. Although large colonies of this insect have recently been found on several willow varieties in Quebec, it is not yet possible to estimate its threat to willow plantations in this region (Figure 5).
Figure 5. Giant aphids feeding on willow. This insect is often found forming large colonies at base of the stem.
The black willow aphid, Pterocomma salicis (L) may actually pose a threat only if severe, frequent attacks occur. Several studies have shown that this species is less damaging than the giant willow aphid, with a less persistent negative impact on willow growth. In Quebec, high density populations of this species have recently been found at the end of June on a willow plantation in the upper St. Lawrence River valley (Huntingdon), mainly on S. miyabeana (SX67 and SX64); it did not seem to feed on S. viminalis.
Other less damaging insects have been found on willow plantations in Quebec. Calligrapha multipunctata bigsbyana adults and larvae may feed on willow leaves without destroying leaf veins, with consequences quite similar to those of Plagiodera versicolora. Willow flea beetles of the genus Crepidodera (C. nana and C. decoraalso feed on Salicaceae leaves [65], and are easy to recognize by their brilliant metallic and bicoloured upper surface; blue or green head and pronotum tinged with strong bronze, copper or violet; and unicolorous blue or green elytra. This beetle feeds on either the upper or lower leaf surface, consuming the epidermis and tissue below, but not on the opposite side. After desiccating, the tissue falls out, resulting in a leaf with a bullet-hole appearance. Varieties of willows developed in Europe, based on pedigrees with Salix viminalis or S. viminalis x S. schwerinii, are susceptible to potato leafhopper (Empoasca fabae Harris), which causes serious damage to this species and its cultivars or hybrids. Willow shoot sawfly (Janus abbreviates Say) larvae have recently been found in Quebec, carving deep tunnels on young willow S. miyabeana SX64 shoots where they cause wilting, change of colour (brown or black) and eventually drooping of shoot tips. It has been observed that in some cases 30% of individuals of SX64 in Huntingdon showed at least one shoot affected by this insect. However, only repeated and severe attacks in young willow plantations may adversely affect tree growth.
Willow can be injured by several diseases [66]. Willow leaves may be sensitive to Alternaria spp., Melamsora spp. and Venturia spp., whereas Cryptodiaporthe spp., Glomerella spp. and Valsa spp. are found to affect stems and branches and Armillaria spp., Fusarium spp. and Verticilium spp. roots [67]. However, the most widespread, frequent and damaging disease in willow plantations is leaf rust, caused by Melampsora spp. In northern Europe, leaf rust is considered a major factor limiting growth of short-rotation coppice willow [68]. It can cause premature defoliation, poor cold acclimation, premature leaf senescence, and a predisposition to abiotic stress (e. g., competition and drought) in host trees, along with secondary disease organisms, and it may reduce yields by as much as 40% [69]. One of the main alternative solutions to spraying fungicides proposed in northern Europe is growing willow in inter — and intra-species mixtures [70]. If a variety dies out of a mixture due to disease, competition or some other factor, the remaining varieties can compensate for the loss [71]. In some willow plantations in Quebec, severe attacks of Melamsora spp. have been detected mainly on a specific commercial clone S301 (S. interior 62 x S. eriocepala 276), which seemed to be more vulnerable to rust than any other clone studied in the area [29]. Few rust attacks have been reported for most commercial clones, however, chemical or biological disease control is generally not required.
Zeolites are crystalline aluminosilicates, three-dimensional, microporous, based on framework structure with a rigid anion, with well-defined channels and cavities. These cavities contain exchangeable metal cations (Na+, K+, etc.) And can also retain removable and replaceable guest molecules (water in natural zeolites). To date about 40 have been characterized structures of natural zeolites and have developed more than 130 synthetic structures. The most important natural zeolites are analcime, chabazite, clinoptilolite, erionite, ferrierite, heulandite, laumontite, and phillipsite mordonita [58].
Zeolites are composed of aluminum, silicon, sodium, hydrogen and oxygen. The crystal structure is based on the three network addresses with SiO4 tetrahedral shaped with four oxygens shared with adjacent tetrahedra. The physical properties unique aspects provide for a wide variety of practical applications. Figure 4 shows the basic structure of the zeolite tetrahedral [63].
Figure 4. Basic tetrahedral structure of the zeolites. |
The physical properties of the zeolite are that they possess features bright, hardness and wear resistance. Applications of natural zeolites make use of one or more of its chemical properties, usually including adsorption, ion exchange and catalysis. These properties are a function of the crystal structure of each species, cationic structure and composition [63].
Clinoptilolite is from the zeolite minerals are best known for its uses and applications. It is a natural zeolite formed from volcanic ash in lakes and marine waters millions of years ago. Clinoptilolite, is the most studied and is considered more useful, since it is known as an adsorbent of certain toxic gases such as hydrogen sulfide and sulfur dioxide. In fact few countries that have had deposits in operation, including: Japan, Italy, USA, Russia, Hungary, Bulgaria, Cuba, Yugoslavia and Mexico [39]. Recognizes the capacity of the zeolites natural adsorb heavy metals and other contaminants from water. In certain cases, it requires a pretreatment of the zeolite to modify or improve its adsorption properties [62].
This chapter has provided the results of research of aerobic and anaerobic biomass in the batch and continuous system using a support for the biomass: silica, polyacrylamide gel, polyurethane, calcium alginate, glutaraldehyde, charcoal and zeolites. The use of support for the biomass increases the development of the microorganisms. Also describes the affecting parameters: time, pH, temperature, HRT, toxicity and stirring speed. Also in this chapter describe the techniques for determination of parameters for anaerobic such as, chemical oxygen demand (COD), alkalinity, methane production, total solids (TSS), volatile solids (VSS), volatile fatty acids (VFA) concentrations, and for the aerobics, the biomass concentration using % of transmittance, McFarland nephelometer, isolation, macroscopic and microscopic characterization, growth kinetics, in batch and continuous system.
Onofre Monge Amaya, Maria Teresa Certucha Barragan and Francisco Javier Almendariz Tapia
University of Sonora, Department of Chemistry and Metallurgy. Hermosillo, Sonora. Mexico
This work was made possible through support provided by the University of Sonora, through the Department of Chemical Engineering and Metallurgy, and Engineering Division. The authors would like to thank: The National Council for Science and Technology (CONACyT), well as students Gisel Figueroa, Gonzalo Figueroa, Guadalupe Lopez, Karla Hernandez, Hiram Banuelos, Carlos Jaramillo, Luis Carlos Platt, Axel Valenzuela, Glenda Duarte.
Sender (2008) studied the long term changes of the macrophytes structure in the Lake Moszne located in the Poleski National Park in Poland. Lake Moszne is a relatively small (17.5 ha), distrophic and shallow (1 m) water body. The lake is not connected with the size, nor with the depth of the reservoir, thus depending on the climatic conditions as well as on the economic and recreational activities, and on the hydro-technical changes imposed to the lake (Sender 2008). As a result, a distinct decrease of the plant association variety was observed, as well as changes in their qualitative composition. In fact, changes in qualitative and quantitative structure of lake Moszne macrophytes were probably caused by both abiotic and biotic factors. The macrophytes structure was subject to fluctuation, the changes indicating notable growth of water trophy. The biomass of macrophytes also showed an increase tendency. Nowadays, the structure of vegetation of the lake does not show the typical features for distrophic lakes.
It is well known that algal populations are often present in considerable and varying densities within shallow lakes, as both planktonic and benthic components (Talling & Parker 2002), and that shallow lakes have become the archetypical example of ecosystems with alternative stable states (Scheffer & van Nes 2007). Moreover, that shallow lakes may switch from a state dominated by submersed macrophytes to a phytoplankton-dominated state when a critical nutrient is exceeded (Kosten et al. 2011). Last authors explored how climate change affected that critical nutrient concentration by linking a graphical model to data from 83 lakes along a large climate gradient in South America. Their data indicated that in warmer climates, submersed macrophytes may tolerate more underwater shade than in cooler lakes, although the relationship between phytoplankton biomass and nutrient concentrations did not change consistently along the climate gradient. According to Kosten et al. (2011), in several lakes in the warm and intermediate regions, submersed macrophytes were found until relatively greater depths than in the cool regions, taking the available light at the sediments surface into account.
Rip et al. (2007) is an excellent case-study of how temporal pattern of precipitation and flow from land to water, may give a coherent, quantitative explanation of the observed dynamics in P, phytoplankton, turbidity and charophytes. Studying the external P load to a wetland with two shallow lakes in the Botshol Nature Reserve, The Netherlands the above authors observed that P load reduction resulted in a rapid decrease of phytoplankton biomass and turbidity, and after four years in an explosive charophyte growth. Such a clear water state, however, was unstable and the ecosystem alternated between clear, high-vegetation and turbid, low-vegetation states. Rip et al. (2007) used a water quality processes’ model in conjunction with a 14-year nutrient budget for Botshol to determine if fluctuations in precipitation and nutrient load effectively caused the ecosystem instability. Their results indicated that during wet winters when groundwater level rose above surface water level, P from runoff was stored in the lake sediments and banks (Figure 3). Stored P was released the following spring and summer under anaerobic sediments conditions, thus resulting in an increase of phytoplankton density and light attenuation in the water column. Also, in years with high net precipitation, flow from land to surface water also transported humic acids, further increasing light attenuation. Conversely, in years with dry winters, P and humic acid loads to surface water were reduced, and growth of submersed macrophytes enhanced by clear water. Rip et al. (2007) concluded by stating that global warming caused winters in the Netherlands to become warmer and wetter during the last 50 years, consequently increasing flow from land to water of humic acids and P and, ultimately, enhancing instability of charophyte populations. Finally, in the first half of the 20th Century interannual variation in precipitation was not sufficient to cause large changes in the internal P flux in Botshol, and submersed macrophytes population were stable.
Figure 3. Calculated Chara biomass as model results and field surveys at subarea I of the Botshol Natural Reserve for 1989-2002 (Rip et al. 2007). |
Recently, Salmaso et al. (2012) studied the combined effects of nutrient availability and temperature on phytoplankton in large and deep lakes of the Alps, lakes Garda, Iseo, Como, Lugano and Maggiore. A significant effect of temperature fluctuations and trophic status on the development of the main groups of cyanobacteria and eukaryotic phytoplankton was observed. However, high positive relationships of nutrient availability with temperature were found only in a few algal groups including charophytes, chlorophytes, dinophytes and, partly, cyanobacteria. Their results have implications in the evaluation of the impact of different climatic scenarios in lakes of different trophic status, suggesting a net increase of only selected eutrophic — or eurytrophic sensitive groups with increasing water temperature in more enriched systems.
provide the necessary information about the features of the chosen bioprocessing system; (c) it synthesizes the characteristics of the specified living cells’ evolution and hence, it is the best technique to predict the process efficiency.
The models show the complex biosystems attributes; so they must be as possible as extensive and non-speculative. Moreover the models are an acceptable compromise between the presentation of processes in detail, with considerable number of parameters, and the use of few parameters, easy to apply and estimate.
Most important properties of a biological mathematical model were defined in the Edwards and Wilke’ postulates [2]: (a) it is capable to represent all the culture phases; (b) it is flexible enough to approximate different data types without the insertion of significant distortions; (c) it must be continuously derivable; (d) it must be easy to operate, once the parameters evaluated; (e) each model parameter is to have a physic significance and must be easy to evaluate.
The attempts to realize high global models were not successful: firstly, due to the impossibility to measure on-line the great number of bioprocess parameters, and secondly, due to the high degree of complexity. Finally several types of models can represent the evolution of the aerobic bioprocess. The most important categories will be presented further on.
1. The unstructured global models are in use nowadays as the main tool for both the bioprocess modeling, but also for being applied in overall computer control [2]. Their limit is they are a simplified representation of the bioprocess behavior: conforming to this concept the bioprocess evolution depends directly and only on the macroscopic variables representing the working conditions in the bioreactor. Therefore the unstructured models are essentially kinetic equations that describe the variation of substrate or product concentrations and of a unique biological state variable-the cell concentration, and can also express the influences of some important process variables (pH, pO2, temperature, and others), and only sometimes they are balance equations.
1 dX
Generally speaking [9], one considers that the specific growth rate (ц =———— ) is the key
X dt
variable for cell growth, substrate consumption and product formation. The specific growth rate is time dependent and dependent on different physical, chemical and/or biological parameters (substrate concentration-S, cell concentration-X, product concentration-P, pH, temperature-T, dissolved oxygen concentration-C, and different inhibitors-I).
Conforming to the literature assumptions [10], the specific growth rate dependence upon different process parameters can be considered as follows:
ц = f (S, X, P, pH, C, I,….,t) (1)
a. p=p(S) Kinetic models with growth limitation through substrate concentration (without inhibition) Main model equations [2, 11] are presented in Table 1.
Model equation |
Constants |
Authors |
Comments |
U(S) = U4 (2) KS + S |
pmax=max specific growth rate [1/h] KS = saturation constant [g/L] |
Monod equation (1942, 1949) |
Empirically derived from the Michaelis & Menten equation |
u(S) = UmaxS (3) Ks + S" |
Moser equation (1988) |
Analogy with a Hill kinetic (n>0) |
|
S u(S) = Umax KS + KD + s ^4) |
KD=diffusion constant |
Powell equation (1958) |
Influence of cell permeability, substrate diffusion and cell dimensions through KD parameter |
Table 1. Models u=u(S) |
There are also some models, which utilize the substrate concentration in more complex structures. Nyholm (1976) introduces a dual function for substrate utilization: consumption (including assimilation and dissimilation in the liquid phase) and growth (substrate utilization for growth):
Se is the substrate for growth and Sa the substrate used for consumption. The growth rate is linked to the intracellular concentration of limiting substrate (Snt/X) and to preserved substrates (i. e. inorganic ions or vitamins, not decomposed through cell metabolism) with application in wastewater bio treatment:
b. U=u(X, S) The influence of cell and substrate concentrations upon the specific growth
rate2′ 11
Model equation |
Constants |
Authors |
Comments |
UY) = Umax(1 — KY (7) |
kX=kinetic constant |
Verhulst (1845) |
It is known as growth logistic model |
So — X U(X, S) = Umax——— YY (8) Ks + So — Y |
So=substrate initial concentration Y=substrate/cell yield. |
Meyrath (1973) |
It is based on Monod kinetics. |
N — N0 exp(Pmaxt) No¥zxeMu’Lj) (9) pax + mxN0(eMprnJ) — 1) |
N=population density m=limiting size of the population (the carrying capacity) |
Verhulst — Pearl kinetics |
Logistic growth: combination between the population trend to growth according to a geometric progression and the environment tendency to limit the excessively high densities of the population |
KxX +S (M) |
KX=kinetic constant |
Contois (Contois — Fujimoto) equation (1959): |
If S = constant, the only dependence remains p = f(X). |
Table 2. Modelsp =p(X, S) |
c. Growth kinetics with substrate inhibition
In most cases, the kinetic model equations are derived (like the Monod model) from the inhibition theory of enzymatic reactions. Consequently they are not generally valid and can be applied in connection with experimental acceptability [2, 11].
Model equation |
Constants definition |
Authors name |
Comments |
p — p 1 = S 1 (11) P Pmax1 + Ks + S Ks + S 1 + S_ s К k |
Ki = inhibition constant |
Andrews model (1968) |
Substrate inhibition in a chemostat |
s S(1+¥) p — p Ks (12) r* rmax c2 S + k^s¥t kS |
Ksl= inhibition constant |
Webb model (1963) |
|
P-Pmax К s (13) 1+—+У(—І s Yk ¥ |
Ki, S= inhibition constant |
Yano model (1966) |
|
S p — p —S—e K’,s (14) P Pmax ks + S |
Aiba model (1965) |
Table 3. Growth kinetics with substrate inhibition |
d. p = f(S, P) Growth kinetic with product inhibition [2, 11]
Hinshelwood (1946) detected product inhibition influences upon the specific growth rate: linear decrease, exponential decrease, growth sudden stop, and linear/exponential decrease
in comparison with a threshold value of P. The first type (Hinshelwood — Dagley model):
P) =ftmax (1 — kP) (15)
KS + S
where: k = inhibition constant (considering the product concentration influence).
Table 4. Models^ = f(S, P) |
e. The influence of dissolved oxygen (as a second substrate) upon the specific growth rate
In some cases it is needed to consider the dissolved oxygen as a second substrate. The most used equation is the kinetic model with double growth limitation, p(S, C) [2, 11]
i. Olsson model:
where: KC = oxygen saturation constant.
ii. Williams’ model, which also quantifies the P influence (Kp=P saturation constant; Kt, K2, K3, K4=modeling constants):
f. |i(St, S2) Kinetic models based on different substrates
Besides the case when the dissolved oxygen is considered as a second substrate, there are many cases when two or more carbon sources are taken into consideration. There are two typical situations: (1) the cells grow through the sequential (consecutive) substrate consumption (diauxic growth), where a simple Monod model can be applied; (2) the cells grow through the simultaneous consumption of substrates (e. g. wastewater treatment); in this case, the mathematical modeling is more complex.
Biogranules are known for their outstanding features of excellent stability and high removal efficiency making biogranulation an innovative modern technology for wastewater treatment. The size of the biogranules is an important aspect that may influence the stability and performance of the reactor system. Biogranules with bigger sizes can easily be defragmented under high shear force resulting in high biomass washout. Meanwhile, if the size is too small, the biogranules cannot develop good settling properties, resulting in higher suspended substances in the effluent. Bigger biogranules with loose structure will be developed in an SBR system supplied with low superficial air velocity. Smaller biogranules but with high strength structures are observed being formed in systems aerated at higher superficial air velocity (Chen et al., 2007). Granular sizes range from 0.3 mm to 8.8 mm in diameter possessing different granular characteristics (Dangcong et al., 1999; Zheng et al., 2005).
The hydrodynamic shear force imposed through the aeration rate of the reactor system will control the development of biogranules (Chisti, 1999). The size of biogranules is the net result of the balance between the growth and the hydrodynamic shear force imposed by superficial air velocity (Yang et al., 2004). For the optimal performance and economic purposes, the operational diameter range for effective aerobic SBR granular sludge should be in the range of 1.0-3.0 mm (Toh et al., 2003)
The usual structure of an aerobic granule is normally spherical in shape with smooth surface areas, which can be influenced by the concentration and type of substrate used in the media compositions (Zhu and Wilderer, 2003; Adav and Lee, 2008). Based on electron microscope (SEM) observations, glucose-fed granules appear with fluffy outer surface due to the predominance growth of filamentous bacteria. On the other hand, the acetate-fed granules show a more compact microstructure with smooth surface. The non-filamentous and rodlike bacteria were observed dominating the acetate-fed granules that are tightly linked together (Tay et al., 2001).
Settleability of a biogranular sludge shows the capacity of the biogranules to settle within a specified period of time. Such properties will allow fast and clear separation between sludge biomass and effluent. The settling velocity of aerobic granules is in the range of 30 to 70 m/h depending on the size and structure of the biogranules, which is comparable to the anaerobic granules. Settling velocity of activated sludge flocs is in the range of 8 to 10 m/h that is three times lower than to those of aerobic granules. Good settleability of sludge biomass is desirable in wastewater treatment plants to facilitate high percentage of sludge retention in a reactor system. Superior characteristics of settleability assist to maintain the stable performance, high removal efficiency and can handle high hydraulic loading of wastewater (Tay et al., 2001). Good settling property of biogranules is also shown by a low value of the SVI. The SVI of biogranules is lower than 100 mL/g (Peng et al., 1999 and Qin et al., 2004), much lower compared to the SVI of flocs (above 150 mL/g). The observed density of microbial aggregates is the consequence of balance interaction between cells (Liu and Tay, 2004). The density of the aerobic granule is reported to be in the range of 32 to 110 g VSS/L (Beun et al., 2002; Arrojo et al., 2006) and the specific gravity is in the range of 1.004 to 1.065 (Etterer and Wilderer, 2001 and Yang et al., 2004).
When biogranules grow bigger, the compactness of the granules decreases. This can be detected via a less solid and loose architectural assembly (Toh et al., 2003). Biogranules with high physical strength can withstand high abrasion and shear force. The physical strength of the biogranules is expressed as an integrity coefficient. This coefficient is an indirect quantitative measurement of the ability of the biogranules to withstand the hydrodynamic shear force (Ghangrekar et al., 2005). A good granular strength is indicated by an integrity coefficient of less than 20.
Biogranules are also characterized by high cell hydrophobicity and high EPS content. The former aspect is postulated to be the main triggering force in the initial stage of the biogranulation process and is a measure of the cell-to-cell interaction (Liu et al., 2003). The latter characteristic is postulated to be responsible for the aggregation between cells (Liu et al., 2004).
The presence of the EPS will enhance the polymeric interaction, which is one of the attractive forces that can promote the adhesion of bacterial cells. The networking between cell and EPS will assist the formation of biogranules (Zhang et al., 2007).
Figure 11 shows simple pathway of the woody biomass gasification process with Ni/BCC catalyst. The woody biomass was first pyrolysis to form gas, tar and char at 923 K. Both useful gas and tar passed through the catalyst particles. Tar was dissociatively adsorbed onto a nickel site where nickel catalyzed dehydrogenation occurs. With steam injection tar would be cracked and reformed follow the mechanism. |
The chemistry of coal (biomass) gasification is usually depicted to involve the following reactions of carbon and steam [29]. The standard enthalpy change (gram molecules) at 298 K is shown for each reaction. The most important reactions are listed in Table 1[29-31]
Process Ah!?98 (kJ/mol)
Steam reforming
a for nC7Hi6 Table 1. Synthesis gas reactions |
Figure 2 illustrates the high level technologies for producing bioethanol from these various biomass feedstocks. Typically, the common steps for biologically producing bioethanol from different feedstocks are fermentation and distillation. For the first generation (1G) bioethanol production, the sugar extracted from sugar-rich crops and that from starch digestion by amylases or acids is directly fermented to bioethanol. To convert lignocellulosic biomass into second generation (2G) bioethanol, an additional step of pre-treatment is usually required. |
A wide variety of lignocellulosic feedstocks are potentially available for bioethanol production such as wood, grass, agricultural waste and MSW (municipal solid waste). Their physical structures and chemical compositions are different; therefore technologies applied for bioethanol production can be diverse. In addition to the main product bioethanol, coproducts are also usually produced, such as heat and electricity generated by burning lignin-rich residue from fermentation and also, potentially, a wide range of high value — added chemicals like acetic acid, furfural and hemicellulose sugar syrup and the low molecular weight lignin.
General technologies required for biologically producing 2G bioethanol include (1) pretreatment, (2) enzymatic hydrolysis, (3) fermentation, and (4) distillation.
Pre-treatment is applied to enhance the accessibility of enzyme to biomass by increasing available biomass particle surface area for enzyme to attack. This can be achieved by partially removing lignin and/or hemicellulose, changing the structure of biomass fibres to decrease cellulose crystallinity and its degree of polymerization. The current available pretreatment methods can be classified as mechanical, chemical and biological. Table1 summarised some typical pre-treatment methods and their characterisations. Pre-treatment has been viewed as the most expensive step in the biologically production of bioethanol. Therefore, it is important to assess the economic feasibility of the pre-treatment method in addition to its technology performance. More information about each pre-treatment method can be found in Section 5.
Enzymatic hydrolysis is carried out under mild conditions with potentially high sugar yields and relatively low maintenance costs. Nevertheless, major challenges for cost — effective commercialisation remain, such as the high cost of enzymes, the slow rate of enzymatic reaction and potential inhibition by sugar degradation products from pretreatments [48]. In enzymatic hydrolysis, cellulose is hydrolysed by a suite of enzymes, including cellulase and p-glucosidase crudely purified from lignocellulose-degrading fungi such as Trichoderma reesi, Trichoderma viride and Aspergillus niger. Cellulase refers to a class of enzymes including endocellulase breaking internal bonds of cellulose, exocellulase cleaving from the free ends of chains produced by endocellulase to form cellobiose (a dimer of glucose), and cellobiase (p-glucosidase) then hydrolysing cellobiose to produce glucose monomers. In addition, most of cellulase mixtures contain hemicellulase that facilitates hemicellulose hydrolysis to assist with the overall effectiveness of enzymatic hydrolysis.
After the enzymatic hydrolysis, sugar monomers can then be fermented to ethanol by microorganisms (e. g. Saccharomyces cerevisiae and Zymomonas mobilis). Fermentation has been commercialised in brewery and food manufacturing for centuries and itself is not a complex and expensive process. The challenges regarding fermentation for the bioethanol industry are: (1) to convert pentose (C5 sugar) which cannot be fermented by the conventional yeast efficiently, and (2) to prevent inhibition caused by sugar degradation products from pretreatments. Research has shown the feasibility of construction and application of genetically engineered yeasts capable of converting both pentose and hexose to ethanol [49]. Further potential lies in using bacteria with the metabolic pathways necessary to ferment all sugars available from lignocellulosic biomass. Z. mobilis has shown to be capable of metabolising 95% of glucose, 80% of xylose and 40% of other sugars in corn stover hydrolysate [50]. Metabolic engineered Geobacillus thermoglucosidasius has demonstrated an ethanol yield of over 90% of theoretical at temperatures in excess of 60 °C [51].
Pre treatment method |
Process and conditions |
Possible changes in biomass |
Disadvantages |
Reference |
Steam explosion |
No agent temperature:160- 260°C,20-50 bar, 2-5 minutes |
Dissolve hemicelluloses Low sugar degradation |
Partially degrade hemicellulose |
[25-27] |
Ammonia fibre explosion (AFEX) |
Ammonia as agent, 6590 °C, 0.5-3 hours |
Change biomass physical structure Enhancing hemicelluloses hydrolysis |
Limited effects on soft and hardwood |
[28, 29] |
SO2/H2SO4 explosion |
SO2 as agent, 160- 220°C, < 2 minutes |
Dissolve hemicelluloses effectively for hardwood and agricultural residues |
Degradation of hemicelluloses, less effective for softwood |
[30, 31] |
CO2 explosion |
CO2 as agent, 35°C, 56.2 bar, 10-60 minutes |
Interrupt crystalline structure of cellulose |
Inefficient for softwood and high capital cost |
[32, 33] |
Hot liquid water |
Water as agent, 190- 230°C, 45 seconds-4 minutes |
Effectively dissolve hemicelluloses Very low degradation |
Water recycling prohibitively expensive |
[34-36] |
Dilute acid |
H2SO4 as agent, over 160°C, 2-10 minutes |
Effectively dissolve hemicelluloses |
Needs neutralisation, significant formation of fermentation inhibitors |
[37-39] |
Alkaline |
NaOH/ Ca(OH)2 /Ammonia as agent, 70-120 °C, 20-60 minutes |
Removal of lignin Low hemicelluloses degradation |
Costs of reagents and wastewater treatment are high |
[40-42] |
Oxidation |
Ca(OH)2+O2/H2O2 as agent, 140 °C, 3 hours |
Removal of lignin Low hemicelluloses degradation |
Costs of reagents and wastewater treatment are high |
[43, 44] |
Organic solvent |
Ethanol as agent, 140- 200°C, 30-150 minutes |
Removal of lignin |
Cost of solvent recovery is high |
[45, 46] |
Ionic liquid |
Ionic liquid as agent, 120°C, 22 hours |
Remove of lignin and hemicellulose |
Costs of reagents and long treatment time |
[47] |
Table 1. Chemical pre-treatment methods for lignocellulosic biomass. |
Bioconversion process configurations, including Separate Hydrolysis and Fermentation (SHF), Simultaneously Saccharification and Fermentation (SSF), Simultaneously Saccharification and Co-Fermentation (SSCF), and Consolidated Bioprocessing (CBP). The SHF has many advantages, such as allowing both enzyme and micro-organisms to operate at their optimum conditions. Also, any accidental failure of enzymatic hydrolysis and fermentation would not affect the other steps. Alternatively the enzymatic hydrolysis may also be combined with fermentation and can thus be carried out simultaneously in a same reactor — this being known as the simultaneous saccharification and fermentation (SSF). During enzymatic hydrolysis, the cellulases are strongly inhibited by hydrolysis products: glucose and short cellulose chains (‘end-point’ inhibition). SSF can overcome this inhibition by fermenting the glucose to ethanol as soon as it appears in solution. However, ethanol itself inhibits the action of fermenting micro-organisms and cellulase although ethanol accumulation is less inhibitory than high concentrations of hydrolysis products [52]. Nevertheless, SSF operating at the compromised temperature (37-40 °C) has some drawbacks caused by the different optimal temperatures for the action of cellulases (45-50° C) and the growth of microorganisms (typically 28-35 °C). One method to overcome this disadvantage is the utilisation of thermo-tolerant fermenting organisms. SSCF is a promising SSF process where the micro-organism co-ferment pentose and hexose to bioethanol. CBP currently becomes the focus of most research efforts to date; it integrates cellulase production, cellulose hydrolysis and fermentation in one step by using an engineered strain [53]. Many studies have been reported in CBP technologies developments recently [54-56].
Nevertheless, other significant efforts are also required to enable future integrated biorefinery. They include (1) promising process designs to integrate energy consumption and minimise the water footprint (2) producing a range of high value added by products, e. g. power, chemicals, and lignin-derived products etc.
The oxygenated compounds in bio-oil can lead to several problems in its direct combustion, such as instability, low heating value, and high corrosiveness. Although higher water content can improve the flow properties and reduce NOx emissions in the fuel combustion process, it causes many more problems. It not only decreases the heating value of the fuel, but also increases the corrosion of the combustor and can result in flame-out. The low pH value of bio-oil also aggravates corrosiveness problems, which may lead to higher storage and transportation costs. Many researchers have tested the combustion of bio-oil in gas boiler systems, diesel engines, and gas turbines (Czernik & Bridgwater, 2004).
Fresh bio-oil from different feedstocks can generally achieve stable combustion in a boiler system. One problem, however, is the difficulty of ignition. The high water content of bio-oil not only decreases its heating value, but also consumes a large amount of latent heat of vaporization (Bridgwater & Cottam, 1992). Thus, the direct ignition of bio-oil in a cold furnace is not easy, and an external energy source is needed for ignition and pre-heating of the furnace. The combustion of bio-oil in diesel engines is more challenging. Its long ignition delay time, short burn duration, and lower peak heat release have limited its combustion properties (Vitolo & Ghetti, 1994). Experiments employing bio-oil in gas turbines have proved largely unsuccessful. The high viscosity and high ash content of bio-oil result in severe blocking and attrition problems in the injection system. Moreover, acid in the bio-oil is harmful to the mechanical components of the gas turbine.
Even though many combustion tests of bio-oil have shown its combustion performances to be inferior to those of fossil fuels, the environmental advantages of bio-oil utilization cannot be ignored. Comparative tests have shown that the SO2 emissions from bio-oil combustion are much lower than those from fossil fuel combustion.
Bio-oil is a mixture of many organic chemicals, such as acetic acid, turpentine, methanol, etc. Many compounds in bio-oil are important chemicals, such as phenols used in the resins industry, volatile organic acids used to produce de-icers, levoglucosan, hydroxyacetaldehyde, and some agents applied in the pharmaceutical, synthetic fiber, and fertilizer industries, as well as flavoring agents for food products (Radlein, 1999). Besides, bio-oil can also be used in a process that converts traditional lime into bio-lime (Dynamotive Corporation, 1995).
The sludge volume index is defined as ‘the volume in mL occupied by 1 g of sludge after it has settled for a specified period of time’ generally ranging from 20 min to 1 or 2 hr in a 1 — or 2 L cylinder. One-half hour is most common setting time allow the mixed liquor to settle for 30 min. (larger cylinder is desirable to minimize bridging of sludge floe and war effects). SVI is 50-150 mL/mg, the sludge settle ability if good.
SVI typically is used to monitor settling characteristics of activated sludge and other biological suspension. Although SVI is not supported theoretically, experience has shown it to be useful in routine process control. The SIV determination consisted of:
1. Place in the imhoff cone of 1000 mL, 100 mL of sludge and diluted to 1000 mL with phosphate buffer.
2. Was allowed to stand for 45 minutes and then stir the contents with a glass rod.
3. The volume occupied by the mud was measured by sedimentation after 30 minutes.
4. The SIV was calculated by dividing this volume by the present VSS g in 100 mL of sludge (Sludge/gVSS) [34].