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\\n\\nArtificial Intelligence, ISSN 2633-1403
\\n\\nVeterinary Medicine and Science, ISSN 2632-0517
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\n\nAfter a robust peer-review process, accepted works are published quickly, thanks to Online First, ensuring research is made available to the scientific community without delay.
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\n\nIntechOpen Book Series will also publish a program of research-driven Thematic Edited Volumes that focus on specific areas and allow for a more in-depth overview of a particular subject.
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\n\nNote: Edited in October 2021
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Sugarcane crop met ideal soil and climate conditions, and it was used by the Portuguese to establish their settlement in Brazil. With the production of sugar, alcoholic beverages were produced by alcoholic fermentation of sucrose. The first studies on ethanol, as a fuel for internal combustion vehicles, started in the 1920s [1]. The characteristics of ethanol (liquid fuel, high-energy density, and relatively safe handling) made it an important substitute for liquid fuel from petroleum in the Brazilian energetic matrix. In fact, the world overwhelming dominance of gasoline, diesel, and jet fuel for transportation clearly shows the preference for liquid fuels due to their high-energy density. Except for the ethanol, most of the liquid fuels in the world are petroleum based. As petroleum is not renewable, in the long term, it must be substituted by other kind of energy. Aside from that, the use of fossil energy results in the releasing of greenhouse gas emission, which contributes for global warming. Hence, society in general is looking for alternatives to avoid global warming and thus replace petroleum. Biomass, like the sugarcane, clearly represents a sustainable and low-cost resource that can be converted into liquid fuels on a large scale to have a meaningful impact on petroleum use.
The beginning of the development of the ethanol fuel in Brazil is related to the petroleum shortage in Brazilian territory and the worldwide oil crisis. Brazil had few oil wells in 1970s, and the country was extremely vulnerable to international oil crisis. In 1973, during the first oil crisis, prices increased by 400%, which greatly affected the Brazilian economy in this way, and the Brazilian government began to seek an alternative to reduce its international dependence on oil. At that time, anhydrous ethanol, produced from sugarcane, had already been mixed to gasoline at a ratio of 5%, since 1931. In 1975, government created the Brazilian ethanol program,
Fuel and anhydrous ethanol production; ethanol-powered car and flex fuel car sold in Brazil, and the price of the oil barrel. Source: [
At this point, it is worth defining “ethanol fuel” compared to anhydrous ethanol. “Ethanol fuel” is also known as “hydrous ethanol,” and it is basically composed of ethanol (92.5–94.6%wt) and water. Ethanol fuel is used straightly into car engines without any blend. Anhydrous ethanol consists of at most 0.7% water by weight, and it has been used mixed with gasoline in different blend levels. Figure 2 shows the fraction of anhydrous ethanol mixed with gasoline over the years. Anhydrous ethanol is also used as anti-knock agent, substituting the additive added to gasoline to avoid getting ignited early before spark occurs. Many countries still use methyl tert-butyl ether (MTBE) as a gasoline additive instead of ethanol, despite the environmental and health concerns. In the United States, MTBE has been replaced by corn ethanol since 2005 [4]. In Europe, part of the MTBE has been substituted by ethyl-tertiary-butyl-ether (ETBE) which is an additive obtained by the reaction of isobutene with ethanol [5]. In Europe, the amount of ETBE used instead of MTBE is dependent on the price of ethanol.
Fraction of anhydrous ethanol added to gasoline. Source: MME Brazilian Ministry of Mines and Energy.
In 1985, after government system changed to democracy, the congress changed the rules of public policy concerning ethanol to include stakeholders on the government decision. As a result, the government moved away from the sector and the bio-ethanol fuel development faced more challenges to overcome. Firstly, the oil price decreased and ethanol became economically noncompetitive compared to gasoline. Oil should cost more than U$ 45.00/barrel in order to let sugarcane ethanol to be competitive [6]. Then, in 1990, the government suspended the quote requirement on the mill to produce ethanol [7, 8]. In 1996, the price control on the fuel sector ended [9]. In 1999, government completely deregulated the sugarcane sector [10]. As a result, the ethanol consumption stopped rising, and the ethanol fuel sector suffered without government regulations and incentives.
Besides the end of the many subsidies, ethanol car technology had to deal with lack of consumer confidence, and so the sales of ethanol fuel-based car decreased. In 1984, ethanol car was still under development and, at that time, many problems were still unsolved such as the engine cold start. In 1989, due to the sugar price raising and the low oil price, sugarcane mills started to produce more sugar than ethanol. This resulted in a shortage of ethanol fuel, which led ethanol car users to stop using it. Besides, the ethanol engine, due to technical reasons, could not be easily converted to gasoline engine. For this reason, as shown in Figure 1, the ethanol car sales dropped from 76% to about 11% in Brazil, and 6 years later, no car manufacturer had ethanol fuel cars in its production lines. From 1995 to 2003, the ethanol demand was basically to supply fuel to the ethanol cars which had been sold before.
By 2003, due to the rising of oil price, ethanol fuel regained its competitiveness. At this time, as a consequence of the ethanol production/demand occurred after 1985, automakers started manufacturing cars using flex fuel technology and, as a result, the demand for ethanol as fuel rose again. Due to the flex technology, the customers can decide whether to fuel their cars with ethanol or gasoline. So, there were no more customers concerns about purchasing ethanol-powered cars. Hence, it became a self-regulating market; for instance, during the sugarcane crop season, the ethanol fuel price decreases, which motivates the preferential use of ethanol instead of gasoline. By analogy, when the stock of ethanol fuel is low, the price of ethanol would rise and it could be preferable for customers to use gasoline instead. This also corrected the problems related to the possibility of ethanol shortage due to climate changes that would affect the sugarcane crop and the amount of sugarcane diverted to produce sugar instead of ethanol. Consequently, the flex technology seems to have solved most of the problems related to the use of ethanol as fuel.
Flex fuel technology consists in adjusting the engine to operate using both kinds of fuel, ethanol or gasoline, and their blend in any concentration. In an Otto cycle engine, each fuel has different operation characteristics such as air/fuel ratio, compression ratio, and ignition timing [11]. The air/fuel ratio issue has been solved by measuring the oxygen content of the exhaust gas by the lambda sensor, which supplies the necessary information for optimal air/fuel mixture to the engine control unit. Electronic ignition timing controller adjusts the ignition time for maximum torque and fuel conversion efficiency [12]. However, the compression ratio, which is the ratio of the volume of the combustion chamber from its largest to its smallest capacity, cannot be easily changed in an engine. Ethanol engine requires a higher compression ratio than the gasoline one; thereby, the commercial flex fuel car has an intermediate compression ratio, which is intermediate to the ideal one for both fuels. Automakers have worked in variable compression ratio engines, which would result in an increment of engine efficiency [13].
Nowadays, most of the cars sold in Brazil are flex fuel, and ethanol is easily found in every fuel station; thus, the customers are able to choose which fuel they want to use. It is worth noting that most Brazilians customers do not choose to use ethanol because it is environmentally friendly, but due to economic reasons. A survey carried out by the Brazilian Sugarcane Industry Association (UNICA) [14] shows that Brazilian consumers in general are not willing to pay more for ethanol than for gasoline even though the majority recognizes its environmental benefits. Even when ethanol has the same cost per driving kilometers (about 70% of the price of gasoline), 55% of the consumers choose to fuel the car with gasoline due to its higher autonomy. This behavior may be explained by “The Tragedy of the Commons” [15] in which the rational man finds that his share of the cost of the CO2 he discharges into the commons is less than the cost of not releasing it individually. Consequently, the majority of the consumers choose the fuel taking into account only their own benefits. This means that ethanol can survive as an alternative fuel only if it is economically competitive when compared to gasoline or by law regulations.
Environmental and social concerns also have a beneficial impact on the fuel ethanol program: pressures from nongovernmental organization (NGO) and the United Nations (UN) about reduction of greenhouse gas emissions (GHGs), and some civil society organizations about the social impact of ethanol supply chain on the society. One action taken to support the claim for reducing GHG was the creation of a tax on the nonrenewable fuel [16], which aims to support environmental programs and natural disasters caused by GHG. This is based on the “beneficiary pays principle,” whereby when purchasing fossil fuel, the beneficiaries should pay the bear costs on the environment, which are believed to contribute to climate change. This seems suitable; however, it is very difficult to precisely evaluate the impact on the environment. Moreover, in 2018, the Brazilian government created the
Besides its use as fuel, ethanol is used as a raw material to produce biopolyethylene. Polyethylene is one of the most popular plastics in the world. It is a polymer of ethylene and consists of a carbon backbone chain with pendant hydrogen atoms. Biopolyethylene is a polyethylene made from ethanol. The process consists in dehydrating ethanol to obtain ethylene prior to polymerization. The properties of this bioplastic are identical to the fossil-fuel based polymer. The main advantage of the polyethylene made from ethanol is that it captures and fixes CO2 from the atmosphere.
Through this brief ethanol history, it is possible to infer that biofuel ethanol has undergone two different expansion phases: the first one is the
Since the beginning of the ethanol fuel program in Brazil, an improvement in all production chain has been observed. With the emerging technologies, new improvements are expected. Hence, in this section, the recent enhancements in productivity and efficiency of the sector and what is expected in a near future are analyzed.
During the last decade, the principal change in crop management was the mechanization. One of the main reason for mechanizing the sugarcane crop is concerned environment protection. The traditional harvest was done manually and the sugarcane leaves had to be burned in the field. The consequence was high particle and CO2 emissions, which led the Brazilian legislation to prohibit the burning of sugarcane leaves in the field [20]. This provided an opportunity to the sector to use this leaves (straw) as an additional feedstock to the ethanol process, producing electricity or second-generation ethanol. Yet this has also increased the amount of pesticides needed to control sugarcane bugs and diseases [21, 22] that are kept in the field for the next crop. It is important to mention that sugarcane is a semi-perennial crop, which means that the same plant may be harvested (without uprooting the plant) and re-grown for up to 5 years. In addition, mechanical harvest and crop have reduced the production cost; however, the amount of dirt brought with the cane to the refinery has increased, thus affecting the industrial process [23].
The productivity in Brazil is uneven concerning the region of the country, for example, in the 2016/2017 crop, the average productivity in the south, southeast, and central regions was 75.3 tonne/ha while in the north and northeast it was 48.6 tonne/ha [24]. In addition, some regions in Brazil, such as the southeast, can reach an avarange production yield higher than 100 tonne/ha [25]. Nowadays, in a good climate condition scenario, a national average productivity of at least 80 tonne/ha is expected [26]. The average sugarcane productivity and planted area have increased since 1980. There was a rapid acceleration in productivity growth in the 1980s, which is mainly due to the investments from the
Productivity of sugarcane and planted area. Source: UNICA União da Indústria de Cana de Açúcar.
Transportation plays a crucial role in the cost of sugarcane production, owing to the multiple transport facilities and time-consuming activities involved in the delivery process. For instance, the total average cost of sugarcane production in São Paulo, in 2016/2017, was R$ 49.56 (U$ 14.57) per tonne of sugarcane [28]. In order to evaluate how much the delivery represents on the total cost, Françoso et al. [29] studied two cities in the same state and in the same crop season, and the cost of cutting, loading, and transportation of sugarcane from the farm to the mill gate 25-km away varied from R$ 26.77 (U$ 7.87) to R$ 37.25 (U$ 10.96) which represents 54–75% of the total production cost, respectively. The great variation in the transportation costs of sugarcane is due to the region topography, quality of roads, and technology employed in the transportation. So, the role of sugarcane transportation on the cost of bio-ethanol cannot be overlooked.
The most economical way of transporting sugarcane from field to the industry is the two semi-trailers attached to a tractor unit. The distance from the farm to the sugar mill is about 25 km. Different ways to transport sugar have been tested, from railroad, rivers, and road [30]. Until 2017, the largest truck licensed was nine axles with the total length of 30 m and a load of 74 tonne, which was the most economical way of bringing sugarcane from the field to the industry [31]. This kind of transport allows drivers to disconnect the tractor from the full trailer on arrival in the mill and then connect to an empty trailer and get back to the field without waiting to unload. As from 2017, the department responsible for monitoring the road traffic has authorized 11 axles, two semi-trailers attached to a tractor unit with the same length, and a total load of 91 tonne [32]. To the best of our knowledge, there are no studies on the viability of this transport mode; however, this might be the most efficient transport mode since this is a claim made by sugarcane producers.
The farmers are rewarded according to the quality of the sugarcane supplied to the industry. When the sugarcane arrives at the mill by a truck, it is weighed, and then the load is drilled in order to collect a sample. The quality of the sugarcane undergoes standardized analysis of the sample. The responsible for the standard is
An appropriate sampling method is fundamental to correctly evaluate the shipment. The collection of samples is usually done by drilling the shipment with mechanical oblique probe samplers. This kind of sampler was introduced in 2007 and has undoubted advantages over the method formerly used because it allows the sample to be taken from the top to the bottom of the truck load. Before the oblique probe, sugarcane was sampled using a horizontal probe or randomly samples were taken at three different points of the shipments.
Mechanization has increased the level of dirt brought with the sugarcane to the industrial process, so a cleaning process has become necessary. When sugarcane was harvested manually, it was possible to wash it before its being forward to an industrial-cutting shredder and milling process. However, because of mechanization, sugarcane arrived at the industry in small stalks since the harvester already cut the sugarcane. Sugarcane in small pieces cannot be washed due to the fact that a lot of sugar would be lost by the stalk-cutting edge. For this reason, a dry-cleaning technology has been adopted by many industries to avoid dirt from entering the industrial process. Increasing 1 kg of dirt per 100 kg of sugarcane is expected to a decrease in the sugar recovery at the industrial process by 0.1% [23]. The loss of sugar occurs with bagasse and filter cake during the sugar juice treatment step. However, the dry-cleaning system consumes about 0.5–1.0 kW per tonne of cane. Because electricity and sugar are products sold by the refinery, there is a feasible balance between profit and loss, that is, the cost of the electricity used to clean the sugarcane should be lower than the cost of the sugar lost due to the dirt. In fact, as shown by some suppliers [34], the dry cleaning system would be feasible when the sugarcane leaves (straw) are intentionally brought with the sugarcane to be burnt in the boiler. In this case, straw is easily collected with cane by lowering the speed of the harvester clean blower. Thus, the dry-cleaning process would separate straw from stalks before the extraction process and then would mix the straw and bagasse after milling. In fact, this is not a consolidated technology, since some industries prefer to harvest the straw on the field and bring it separately. Thus, the implementation of the sugarcane dry cleaner method will depend on the manner of straw handling.
The next process applied to the sugarcane is the extraction, which is done by the mill or diffuser. The aim is to separate fiber, a solid stream, from sugar in a liquid stream. In this process, sugarcane is first reduced into small pieces and the sugar-bearing cells are ruptured to facilitate the subsequent extraction process. This is basically a mechanical process whereby size reduction is generally achieved through the use of rotating knives and swing hammer shredder in the cane-conveying system. In the case of billeted cane, mechanically harvested, it can be fed directly into a shredder without any additional cutting. For cane juice extraction, there are many studies comparing milling and diffuser [30, 35, 36]. The main advantage of a diffuser over mill is the greater extraction of sugar; however, a diffuser uses more imbibition water and steam than a mill. As a result, there is a dilemma to the industrials: to increase sugar extraction, more thermal energy is spent. In Brazil, the preference has been for the use of mills, which consists of a set of four to six mill units. A new extraction technology called “Hydrodynamic Extraction” or “Rivière Juice Extractor” is under development and aims to achieve the same level of diffuser extraction using less imbibition water with a lower cost of installation and maintenance when compared to both technologies [37]; however, to the best of our knowledge, there is no commercial plant using this technology.
Sugarcane milling did not change much during the last two decades, except for the driving system. Two driving systems are the mostly used in Brazil: steam turbine and electric motor. Even when an electric motor is used, the electricity is produced using a steam turbo-generator, that is, in both cases, the primary energy to drive the extraction process is the bagasse, which is burned in a boiler to produce steam. The driving system with steam turbine is the most widely used, mainly in old industries. This system consists of a low-efficiency steam turbine working around 22 bar and 350°C admission, and 2.5 bar exhaust, so, in this system, steam energy is converted into a mechanical energy to the mill. The electric drive system consist of an electric motor attached to each roll of the mill unit. Even with the double transformation of energy, the overall efficiency of the electric drive is higher than the work done by a single-stage turbine. These become an issue for the sugar mill, since the surplus electricity becomes a profitable product for the mills. As from 2002 when the government has regulated the commercialization of electricity by the private sector using biomass [38], many sugar mills have invested in higher-pressure boilers (65–100 bar) and high-efficiency cogeneration systems.
After being milled, the juice contains several impurities, which must be removed prior to fermentation or concentration. These impurities are removed using a set of unit operations, which basically consist of heating, adjusting the pH, settling the precipitate formed in the body juice, and filtering.
Only small changes on these processes were adopted during the last decades. In the heating, most industries prefer vertical shell-and-tube steam heaters. Despite the higher overall heat transfer coefficient in the horizontal one, the vertical one is easier to clean. The extracted sugarcane juice has a pH of about 5.3, and needs to be adjusted to 7 before clarification. For this, lime Ca(OH) is added, which is the most widespread process used. For refineries that produce sugar in addition to ethanol, processes such as sulfitation, phosphatation, and carbonation [36] are also used, aiming to lower the color and turbidity. After the pH adjustment, the juice is sent to a clarifier to settle the insoluble part of the juice. Before the use of chemical products (flocculants and polymer) and instruments to control the flow and dosing, the most popular installation used multi-tray clarifiers. The main disadvantage of multi-tray is the retention time of about 3 h. Single-tray clarifiers, known as “rapid clarifiers,” became possible with the development of chemicals that promotes the mud coagulation and settling. The retention time in this case is about 1 h. The main advantages of the rapid clarifiers over the multi-tray ones are the lower installation costs, and the small retention time, which reduces the degradation of sugars [30]. There are not many research works carried out recently about juice treatment, and consequently, great changes in this process are not expected in a near future.
Ethanol can be produced in an autonomous distillery, producing only ethanol, or in an attached distillery, which produces sugar and ethanol. In the second case, ethanol can be produced only from molasses, a residue from the sugar production process, or a mixture of molasses and juice, depending on the amount of juice diverted to produce ethanol. When sugar is produced, the juice destined to the sugar process must be concentrated to achieve a suitable brix to start the crystallization process at about 60% sucrose by weight. This concentration is obtained using multiple-effect evaporators (MEVs), which reduces the required steam to concentrate the juice, since each effect produces lower-pressure steam, which is used in the next effect to evaporate more water and so on. In this way, only the first-effect evaporator uses the exhaust steam from turbines. Saving the exhaust steam is crucial for industries that have condensation turbine installed or for refineries that want to save bagasse for other purposes, such as second-generation ethanol or just selling bagasse as a product.
When sugar and ethanol are produced in a refinery, there is a synergistic effect that reduces the total consumption of steam. Since large amount of water must be taken off from the juice in order to concentrate it in the crystallization process, this water is withdrawn as steam in an MEV. This steam from MEV is used in the ethanol process. In this manner, steam from MEV replaces the necessity of using exhaust steam. Combining ethanol and sugar production, results in an energy efficient refinery.
Alcoholic fermentation is a biological process, which converts sugars such as glucose, fructose, and sucrose into cellular energy, producing ethanol and carbon dioxide as a side effect. The overall chemical reaction for alcoholic fermentation is as follows:
Sucrose is a dimer of glucose and fructose molecules. In the first step of alcoholic fermentation, the enzyme invertase cleaves the glycolic linkage between the glucose and fructose molecules. When the fermentation finishes, the fermented liquor is centrifuged to remove east (
There are two types of process for alcoholic fermentation commonly used to produce ethanol. The majority of the sugar mills use a fed-batch fermentation process. Continuous process is also used by some industries; however, despite the lower installation cost, continuous fermentation results in lower efficiency in the production of ethanol. The lower efficiency is a result of bacterial contamination since, in a continuous process, the fermenter cannot be as frequently cleaned as in a fed batch, in which cleaning can be carried out after each batch.
The main disadvantage of the fed-batch process is related to the large size of the fermenters. Many technologies are under development to reduce this size. There are many problems in the operation of such large equipment: high cost of installation, difficulty to control parameters, such as contamination, mixing, and temperature, which can cause temperature gradients and dead zones inside the fermenter. To reduce these problems, the total volume of broth under process must be reduced. Therefore, the proposed technologies aim to increase the concentration of reactants and products. Removing ethanol during the fermentation process is one possibility, since a high concentration of ethanol is toxic to yeast. There are some studies of pervaporation [39] and stripping [40] to take ethanol off the fermentation broth during the ethanol fermentation. The high cost of pervaporation membranes and the difficulty in recovering ethanol from CO2 make this technology unfeasible nowadays. Reducing the temperature of the fermentation broth using a chiller is also an option under development, and there are some commercial-scale units [41]. At a lower temperature, yeast would resist a higher concentration of ethanol, but reducing the temperature would also reduce the reaction rate. By now, the best available technology continues to be the fed batch cooled by cooling towers.
The recent development in downstream process did not aim to improve the ethanol recovery efficiency but to save the energy demand by the process. Downstream consists of the separation of ethanol from the other components in the fermented wine; the first step is the centrifugation of wine, which recovers yeast to the next fermentation fed batch. There are two main components at the centrifuged wine: water and ethanol. Fuel ethanol also called “hydrous ethanol” (ethanol 92.5–94.6 wt%) is obtained by distillation. Due to the azeotropic point in the mixture ethanol-water, anhydrous ethanol cannot be obtained using a common distillation process. Anhydrous ethanol (99.3 wt%) must be produced in order to be used in a mixture with gasoline. There are two common dehydration systems used in Brazil: azeotropic distillation with cyclohexane or monoethyleneglycol, and, more recently, absorption on molecular sieves. The main advantage of using molecular sieves is that steam consumption is about one-third of those in the azeotropic distillation. Pervaporation is a process that could significantly reduce the energy demand; however, the high cost of membranes makes it unfeasible to be used in a commercial scale.
Vinasse is the final by-product of the ethanol distillation and is the main effluent of the ethanol process. About 12 liters of vinasse are produced per liter of hydrous ethanol. Most industries use the vinasse without any treatment as a fertilizer and, it is simultaneous used for irrigation due to its high amount of water (fertirrigation). The vinasse produced in a distillery is a stream composed basically of water, organic matter, and inorganic salts. Therefore, there are many possibilities to utilize this vinasse: as biogas obtained by conversion of the organic matter into gas, and as fertilizer through using the inorganic salts (phosphorus, potassium, and nitrogen) to partially replace synthetic fertilizers derived from the petroleum industry.
Biogas has a great potential opportunity for using the vinasse. Many studies have been carried out about the bio-digestion of vinasse [42–44]. Biogas is an easy to handle fuel since it can be transported in high-pressure cylinders, or by pipeline, and can fuel farm machinery and trucks to partially replace diesel [45]. Biogas can also be obtained from sugarcane trash (bagasse and straw) [46] in a bio-digester blended with vinasse. This is also an opportunity to the use of bagasse, that is, bagasse, as well as straw, can be converted into biogas instead of producing electricity or 2G ethanol. There are also many sugar mills close to the gas pipeline network in Brazil, which would raise the feasibility of implementing a biogas facility. Besides the high cost of installation, a great challenge to implementing biogas facilities is to deal with an unstable vinasse supply. Vinasse is not produced continuously, since industry interrupts its operation relatively frequently due to the rain, which stops the harvest, or due to the maintenance or the braking of equipment.
Another possibility is to concentrate vinasse and to recover water to be used in the process. In this case, the concentrated vinasse can be transported to longer distances to be used as liquid fertilizer. Concentrated vinasse can also be burned into the boiler; in this case, the higher the concentration, the higher its net calorific value. The main disadvantage in this process is the steam demand to concentrate vinasse.
After biodigestion, water can be withdrawn from vinasse using commercial technologies such as evaporator or ultra-filtration membrane. Reducing the use of water has a positive environmental impact, but the cost of these processes may be higher than the intake of water from natural sources (mainly rivers). So, only few refineries in Brazil are withdrawn water from vinasse to be used in the process.
What makes ethanol from sugarcane superior to that from other feedstocks (e.g., corn) is the bagasse that comes with the sugarcane. First-generation ethanol processes from sugarcane have a positive energetic balance, which means that it is not only self-sufficient on energy, but it can export the surplus energy usually as electricity. Using the combined heat and power (CHP) process is the most efficient way to produce electricity. In the CHP, high-pressure steam (between 65 and 100 bar) is expanded in turbines coupled with electric generators, and the exhaust steam from the turbines is used as thermal energy for the process. A high-efficient process, that is, a process which consumes small amount of thermal energy, results in surplus bagasse that can be used as feedstock to another process, such as second-generation ethanol, or to produce surplus steam—the steam produced by the boiler and not condensed in the process. The surplus steam can be expanded in condensation steam turbines to allow maximizing the electricity production.
The condensation turbine used to produce electricity with the steam competes with the cellulosic ethanol. The condensation turbine cannot be classified as CHP, since only power is produced and the exhaust steam is condensed by cooling water, that is, heat is not used in the process. Despite the fact that it maximizes the production of electricity, an energetic analysis shows that the larger enthalpy jump occurs in the condenser and not in the turbo-generator expansion. Thus, the energy to condense the steam is released to the surrounding cooling tower.
Sugarcane bagasse has become a valuable product for sugarcane refineries, and it is really an important source of energy for the Brazilian economy. Before the possibility of exporting electricity to the grid [38], most sugarcane mills had low pressure and inefficient boiler and turbo-generator (about 22 bar 350°C). This allows the refinery to be self-sufficient in electricity, however, without the possibility to export to the grid. Some sugarcane mills are still running using this old technology. High-pressure and high-efficiency boiler and turbines allow the refinery to export electricity. For instance, in a scenario in which a refinery has a higher-efficiency boiler, counter-pressure and condensation turbine, and electrified mill, it is possible to export about 79.7 kW·h per tonne of sugarcane. The parameter and efficiency of this scenario are shown in Table 1. To verify the potential of the bagasse in Brazil, in 2016, the country produced 666.8 million tonne of sugarcane [47] and in the same year produced 35,236 GW·h of electricity from sugarcane bagasse [48]. If every sugar mill was prepared to export electricity as described in this scenario, this number could have been 53,135 GW·h. Further, considering the possibility of bringing 50% of the sugarcane straw (leaves and tips) which yields about 140 kg per tonne of sugarcane (15% humidity) [49], it would be possible to export 135,470 GW·h per year. For an idea of the order of magnitude, Itaipu, the biggest hydroelectric power plant in Brazil, in the same year, produced 103,098 GW·h.
Bagasse produced per kg of sugarcane | 0.276 kg |
Bagasse losses due to degradation and boiler startup | 5% |
Net calorific value of bagasse | 7300 kJ/kg |
Boiler temperature | 520°C |
Boiler pressure | 68 bar |
Boiler efficiency | 85% |
Counter-pressure turbo-generator efficiency | 83.5% |
Condensation-pressure turbo-generator efficiency | 78.3% |
Steam consumption in the first-generation process per kg of sugarcane | 0.4 kg |
Electricity consumption per tonne of sugarcane | 32 kW |
Sugarcane straw brought with sugarcane per kg of sugarcane | 0.140 kg |
Net calorific value of sugarcane straw | 12,900 kJ/kg |
Parameters used to obtain the electricity production from sugarcane bagasse.
The conventional ethanol production utilizes a fermentation process to convert sugars, such as starch, sucrose, glucose, and fructose, into ethanol. Second-generation biofuels, also commonly known as advanced biofuels, utilize agricultural residues or other feedstock that cannot be straightly used as food for humans. Cellulose is an important structural material for plants (along with lignin), and it is made up of many repeating sugar units. These repeating sugar units can be broken down by various processes into the component sugars, which can finely be fermented into ethanol.
Many investments on the development of ethanol from cellulosic material have been made, and some industrial-scale plants have been built; however, it has been taken longer than expected for cellulosic ethanol to succeed. In the United States, for instance, there are at least four commercial plants (DuPont Cellulosic Ethanol, Poet Project Liberty, Abengoa Bioenergy Biomass, Alliance Bio-Products INEOS) with an installed capacity of 121, 88, 110, and 35 million liters per year, respectively. In Brazil, there are two commercial plants, Granbio and Raizen, with an installed capacity of 82 and 40 million liters per year, respectively. In addition, in Italy, the first cellulosic plant, Crescentino, a Mossi & Ghisolfi group company, has an installed capacity of 31 million liters per year. Most of them started their operation in 2014, but not all has been well: in 2017, DuPont decided to close its plant and announced that it will sell the company’s ethanol facility in Nevada, Iowa. Abengoa announced bankruptcy and financial restructuring in 2016 and, in the same year, the cellulosic biofuel plant was bought by Sinatra-Bio. In the end of 2017, Crescentino also applied for
Surplus bagasse can be used to produce more electricity or second-generation ethanol. Both fuels can be used in light vehicles. For instance, take two commercial cars where car “A” being sold in the USA and uses electricity and car “B” being sold in Brazil and using a flex fuel engine (it can use ethanol or gasoline). Knowing that surplus bagasse can be converted into electricity or second-generation ethanol, it is possible to draw two hypothetical scenarios where scenario 1 consists in a refinery processing 1 tonne of sugarcane to produce ethanol in the first-generation process and electricity using a condensation turbine as described in Table 1, and scenario 2, in which the same 1 tonne of sugarcane is used to produce second-generation ethanol from surplus bagasse besides first-generation ethanol. The parameters and efficiency adopted for second-generation ethanol is described in Table 2. Table 3 compares both scenarios side by side to obtain the distance driven in each scenario.
Parameter and efficiency adopted | Second-generation ethanol plant |
---|---|
Steam consumed per tonne of bagasse at second-generation process. | 451 kg [52] |
Electricity consumed per tonne of bagasse at second-generation process. | 155 kW·h [52] |
Lignin per kg of bagasse (dry basis). | 0.264 kg [53] |
Glucan group per kg of bagasse (dry basis). | 0.405 kg [53] |
Xylan group per kg of bagasse (dry basis). | 0.197 kg [53] |
Net calorific value of lignin (35% moisture). | 12671.8 kJ/kg [54] |
Pretreatment efficiency. | 90% |
Sucrose and glucose fermentation efficiency. | 90% |
Xylose fermentation efficiency. | 80% |
Distillation efficiency. | 97% |
Parameters used to obtain the consumption rating of two vehicles.
Parameter | Scenario | |
---|---|---|
First scenario | Second scenario | |
Surplus electricity | 79.7 kW·h | 38 kW·h |
Ethanol | 90 L | 104.3 L |
City consumption ratings car “A” | 6.20 km/kW·h | |
Highway consumption ratings car “A” | 4.90 km/kW·h | |
City consumption ratings car “B” | 8.34 km/L | |
Highway consumption ratings car “B” | 9.9 km/L | |
Distance driven in a city using car “A” | 494 km | 237 km |
Distance driven in a highway using car “A” | 390 km | 186 km |
Distance driven in a city using car “B” | 750 km | 870 km |
Distance driven in a highway using car “B” | 891 km | 1072 km |
Total distance driven in a city | 1245 km | 1107 km |
Total distance driven in a highway | 1281 km | 1258 km |
Parameters used to obtain the consumption rating of two vehicles.
Looking through these results, it would be possible to infer that, considering these parameters and efficiency, it is better to produce electricity instead of ethanol since the distance driven in scenario 1 is higher than in scenario 2. However, this is not a conclusive result since to reach a reliable best scenario, studies such as live cycle analysis, return on investment, energy storage method, concentrated versus dispersed emissions, autonomy, and the preferable fuel by customers are needed.
A new era with a clean worldwide energy matrix is expected nowadays. Ethanol has been shown to be a fuel with great potential to meet this world’s aspiration. In this new phase, the fuel needs to be recognized by its environmental benefits and not only by the energy that it contains. Consequently, it has to be rewarded according to the benefits it brings to the society. For this in recent years, the sugarcane industry has positioned itself not only as a food industry but also as an energy industry. Having a look into the sugarcane feedstock, bringing a different viewpoint, one could say that it produces three different kinds of energy: sugar—energy for human beings; ethanol—energy for transportation; and electricity—energy for a variety of uses. As an energy company, the process itself cannot be energetically wasteful. So, recent improvements in the process have aimed to maximize its efficiency; meaning that using less energy in the process itself results in more energy left to be sold as a product. However, many questions, such as the destination of the use of straw, bagasse, and vinasse, are still unanswered and will depend on the next technology improvement. This new era will result in increasing the demand for ethanol, which must be met not only by the increase in the production but also in the productivity and efficiency. Nevertheless, many technologies, with notorious performances, are not applied to the production of ethanol nowadays because of their low feasibility. They would become feasible, however, if ethanol was rewarded for its environmental benefits.
The authors kindly acknowledge FAPESP (Fundação de Amparo à Pesquisa do Estado de São Paulo) process number 2015/50684-9 for its financial support.
Currently, water pollution is becoming one of the most serious challenges confronting human beings due to steady increase in population, advancements in industrial activities, and urbanization [1]. Contamination of water bodies through discharge of organic pollutants such as dyes, heavy metals, and petroleum are posing a significant danger to humans as well as the aquatic ecosystem [2]. The effects of these pollutants differ and depend on the source and type; for example, organic dyes and heavy metals have been recognized as carcinogens while cosmetics and pharmaceutical waste products have been identified as endocrine disruptive agents [3]. These agents impede hormonal processes, thereby disturbing regular homeostatic reproduction, advancement, or behavior [4]. Furthermore, presence of dyes in the water bodies blocks sun from penetrating into the water bodies and lessens dissolved oxygen, therefore, causing death to photosynthetic organisms that live in the aquatic system [5].
To mitigate the impact of water pollution, scientists are making efforts to develop approaches to treat wastewaters before being discharged into rivers, streams, and underground water. Approaches such as chlorination, aerobic treatment, aeration, and filtration have been used to treat waste. However, greater attention has been given to treatment processes that involve the use of nanomaterials. Inorganic metal oxides nanoparticles (NPs) have benefits such as no secondary pollution, cost, and energy efficiency and are easily operated [6, 7]. Metal-oxide NPs have been studied for potential degradation of contaminants [8, 9, 10], heavy metals [11, 12], and inactivation of bacteria [13, 14, 15]. Many other compounds such as metal halides [16], metal nitrides [17], and metal chalcogenides [18, 19] have also been evaluated for photocatalytic applications. Among which, perovskite nanomaterial has drawn so much attention because of its wide variety of properties. Perovskite nanomaterial has indicated a broad range of electro-optical effects, piezo, ferro, and pyro-electrical properties that enable them to exhibit outstanding performances as structural, electronic, and magnetic material [20]. In addition, because of their crystalline structure, perovskites have unique chemical properties that contain a spectrum of cations to generate surface defects, which can balance unstable oxidation states [21].
Titanate-based perovskite material is among the most commonly studied perovskites for photocatalytic applications under visible light. This is because their optical band-gaps energy is easily modified and quite stable for a long period throughout a photocatalytic reaction [22]. A good number of titanium-based perovskites such as SrTiO3, MnTiO3, BaTiO3, ZnTi3, MgTiO3, and CaTiO3 have optical band-gaps energy above 3 eV [23, 24, 25], thereby allowing photocatalytic activities only under UV source. On the other hand, TBP, such as CoTiO3 and NiTiO3, have band-gap energy lower than 3 eV but their CB is below the oxidation potential [26, 27], which also limits their chances for photocatalytic applications.
Excellent photocatalyst semiconductor (SC) is expected to have excellent charge carrier mobility and charge separation to prevent recombination of electron (e) and hole (h) generated in the system [28]. Efforts have been made by scientists to enhance photocatalytic activities of SC photocatalyst through various means by modification of physiochemical properties of the nanomaterial. The modification can be done via doping (with metals, nonmetals, and salts), defect engineering, heterostructure, and cocatalysts [29, 30, 31]. Research has shown that doping greatly affects the electronic structure of SC nanomaterial [32]. Like TBP, the majority of SC photocatalysts have wide band-gaps energy, which makes it difficult for them to have photocatalytic activation with a visible light source [33, 34]. To improve the efficiency and quantum yield of SC photocatalysts such as TBP, their optical band-gap energy should be altered to respond to visible light sources. Another parameter that affects the photocatalytic activities of this material is presence of defects. Defects seen in a material can be artificial or natural specific structure. Surface defects alter geometric structure, as well as the chemical environment of the host material [35]. It can also serve as charge carrier traps and adsorption sites; the induced electrons can be transferred to the sites and, therefore, prevent recombination of photogenerated e—h+ pairs.
This chapter highlighted fundamental principles and mechanisms of SC photocatalysis and recent synthesis techniques that have been deployed in preparing TBP nanomaterial. The influence of reaction conditions and approaches such as doping, codoping, composites, temperature, pH, precursor type, surface area, and morphology on surface defects and optical band-gap energy of TBP nanomaterial was noted. Ultimately, impact of surface defects and optical properties of TBP on its photocatalytic activities against organic pollutants was discussed. Considering progress recorded so far in this area, some perspectives on how to advance and improve degradation efficiency of TBP against organic pollutants were proposed.
Generally, photocatalysis is initiated when a SC photocatalyst absorbs photons with energy equal to or higher than its optical band-gap energy. Consequently, electrons in the valence band (VB) are excited into the conduction band (CB) leaving holes in the VB. This excitation produces a potential difference midway CB and VB bands, creating reductive and oxidative entities at the CB and VB, respectively. These photo-activated charge carriers can react with H2O or dissolved oxygen to generate free radicals such as OH and O−2 that can degrade pollutants into smaller molecules [36] as shown in Eqs. (1)–(6). It is fundamental that the minimum material CB is located at a higher negative potential compared to the reduction potential for H+ to H2, at the same time, it is also essential that the highest VB is located at a higher positive potential compared to the oxidation potential for H2O to O2 [22]. Figure 1 describes the indirect organic pollutant degradation process by SC photocatalyst.
Pictorial description of indirect organic pollutant degradation process by SC photocatalyst. Adapted with permission [
Perovskite material is generally referred to as material whose crystal structure is described by the formula ABO3, A and B are ions that often have different sizes and O is an ion that is bonded to A and B. It has a cubic structure that contains B cations in a 6-fold orientation encircled by an octahedral of anion while the A cation in a 12-fold cuboctahedral orientation [38]. Figure 2a
(a and b) Crystal structure of a perovskite. Adapted from [
Various synthesis methods have been successfully deployed in the formulation of TBP nanomaterial. Surface defects and optical band-gap energy of TBP can be manipulated by deploying appropriate synthesis methods, which include the temperature, pH of the reaction, types of precursor, and solvents. In this section, we summarized recent methods deployed in synthesizes of TBP in Table 1 including the precursors used, reaction conditions, and pollutant/application.
S/no | Method | Sample | Precursors | Light source | Conditions | Pollutant/application | References |
---|---|---|---|---|---|---|---|
1. | Solid state | SrTiO3, Sr1 − xBixTi1 − xFexO3(0 ≤ x ≤ 0.4) | SrCO3 TiO2 Bi2O3 Fe2O3 | Visible | 1200°C for 20 h | H2 evolution | [40] |
2. | One-pot hydrothermal | SrTiO3-rGO composite | GO Ti(OBu)4 Sr.(NO3)2 | UV | 180°C for 24 h | H2 evolution | [41] |
3. | Sol–gel | CaTiO3 CaTi1_xCuxO3 | Ca(NO3)2 Cu(NO3)2 Ti(OBu)4 | UV | 850°C for 7 h | H2 evolution | [42] |
4. | Hydrothermal | CaTiO3 | Ca(NO3)2·4H2O TiCl4 (TTC) Ti(OC3H7)4 (TIP) Ti(OC4H9)4 (TNB) | UV | 180°C for 12 h | As(III) | [43] |
5. | Modified hydrogenation | CaTiO3 | CaCO3 TiO2 | Visible | 60°C for 12 h | H2 evolution | [44] |
6. | Solution combustion | Na + co-doped CaTiO3:Eu3+ | Ca(NO3)2·4H2O Ti(OBu)4 Eu2O3 Na2CO3 | UV | 900°C for 1 h | methylene blue (MB) | [45] |
7 | Sol–gel | CaTiO3 | (CaCl2) Ti(OC4H9)4 | Visible | 900°C for 2 h | methyl orange and rhodamine degradation | [46] |
8 | Microwave-assisted hydrothermal | CaTiO3 | TiO2 (CaCl2 ErCl3·6H2O | Visible and near-infrared | 180°C for 4 h | MB degradation | [47] |
9 | solid-state | Fe-doped CaTiO3 | CaCO3 TiO2 Fe(NO3)3 | UV–visible | 1400°C for 2 h | MB Degradation | [48] |
10 | One-pot hydrothermal reaction | CaTiO3 | [Ti(C4H9O)4] Ca(NO3)2 | Visible | 200°C for 24 h | photocatalytic hydrogen generation | [49] |
11 | Hydrothermal | Rh doped BaTiO3 | TiO2 (anatase) RhCl3 | Visible | 180°C for 20 h | MB degradation | [50] |
12 | Hydrothermal | Rh doped BaTiO3 | Ba(OH)2.8H2O Rh(NO3)3 | Visible | 160°C for 42 h | H2 evolution | [51] |
13 | Sol–gel | Ag-doped BaTiO3 | Ba(C2H3O2)2 Ti(OBu)4 AgNO3 | Visible | 800°C for 2 h | Rhodamine B degradation | [52] |
14 | Hydrothermal | PbTiO3, Ag-Fe codoped PbTiO3 | C12H28O4Ti Pb (NO3)2 AgNO3), (FeH18N3O18 | UV | 400–600°C for 2 h | MB degradation | [53] |
15 | Hydrothermal microwave-assisted and hydrothermal autoclave | mixed Bi4Ti3O12/Bi12TiO20 Bi4Ti3O12/Bi2O3 | TiO2 Bi(NO3)3·5H2O | Visible | 700–800°C for 2 h | MB degradation | [54] |
16 | Microwave-assisted hydrothermal | Bi12TiO20 | Ti(OBu)4 Bi(NO3)35H2O | Visible | 180°C for 1 h | Rhodamine B Degradation | [55] |
Recent techniques used in synthesize of TBP, samples and precursors used, the reaction conditions, and pollutant/application.
In recent times, substantial work has been done to enhance the physiochemical properties of TBP nanomaterial, more especially surface defects and band-gap energy. This is because of their role in the photocatalytic activities of this group of perovskites. Attempts have been made to modify these two parameters via reaction conditions and synthesis techniques. In this section, the role of reaction conditions on these physiochemical properties was highlighted. The impact of surface defects and band-gap energy on photocatalytic activities of TBP nanomaterial was also discussed.
Zhuang and co [43] reported three different morphologies of CaTiO3 formulated from three different Ti precursors through hydrothermal techniques for removal of As(III). After 40 mins of exposure to UV source, CaTiO3 sample with (Ti(OC3H7)4) (TIP) as a precursor showed the highest activities (98.4%) in removal of As(III). Figure 3 indicates the induced changes in the concentration of the As(III) under UV source against different morphologies of CaTiO3. The higher photocatalytic activity of CaTiO3 (TIP) was associated with its fern-like morphology and the higher specific area (108.142/g) when compared to other two.
The induced changes in the concentration of the As(III) under UV-254 nm for different morphologies of CaTiO (A) CaTiO3 TTC (B) CaTiO3 TNB (C) CaTiO3 TIP and (D) No photocatalyst. Reprinted with permission from [
Cai et al. [44] fabricated surface disordered CaTiO3 using modified hydrogenation method. The as-prepared samples were utilized as a model to study roles of surface oxygen vacancies (SOVs) on photocatalytic H2 evolution under a visible light source. They demonstrated that CaTiO3 hydrogenated at 700°C induced more SOVs with a very high photocatalytic H2 evolution rate (2.96 mmol g−1 h−1). A value that is almost 49 times greater than the value of the pristine CaTiO3 without SOVs. They suggested that the significant increase in H2 production in the hydrogenated samples was because of the induced SOVs, which lower surface recombination of photogenerated e-h pair and increase charge separation.
Portia et al. [46] studied the influence of annealing temperature on photocatalytic activity of CaTiO3 NPs under the visible light source. The samples were prepared via sol–gel method and were annealed at various temperatures of 500°C, 700°C, and 900°C. The photocatalytic activities of the samples were assessed against MO and Rhb dyes. The sample annealed at 900°C exhibited the highest degradation efficiency (DE) 88% and 78% for Mo and Rhb, respectively, while sample annealed at 500°C showed DE of 53% and 38% for Mo and Rhb, respectively. The photocatalytic activity results also correlate with the result of UV–visible diffuse reflectance spectroscopy, which indicates the absorption of the sample annealed at 500°C to be 340 nm while the sample annealed at 900°C exhibited outstanding and improved visible—absorption with its peaks at 450 nm. The kinetic fit of the samples against MO and RhB dyes were shown in Figure 4. They associated the enhancement in photocatalytic activities of the sample annealed at 900°C to a decrease in the optical band-gap energy of the CaTiO3 sample, specific surface area with porous features as well as a low recombination rate of the e—h+ pairs.
The kinetic fit of the samples against MO and RhB dyes exposed to a visible light source. Reprinted with permission [
Lazono-Sánchez et al. [47] reported influence of Eu3+ doping and heat treatment on photocatalytic activities of CaTiO3 under visible and near-infrared light sources. The results showed that samples doped with 1% Er3+ exhibited the highest degradation reaction rate against MB (4.54 × 10−5 s−1), a value, which is about 2.5 times higher than that of undoped sample 1.86 × 10−5 s−1. Furthermore, the as-prepared samples were calcined at 850°C and their photocatalytic activity against MB was also evaluated under UV–vis–NIR irradiation. They reported a significant increase in the photodegradation reaction rate of the calcined sample against MB. The author attributed improvement in the photocatalytic reaction rate of the samples to introducing a new energy state in the optical band-gap of the CaTiO3 and increased crystallinity. In another work, Yang et al. [48] reported photodegradation of MB by Fe-doped CaTiO3 under UV–visible light irradiation. They found that doping CaTiO3 with Fe enhanced its photocatalytic activity against MB. Nevertheless, the photocatalytic activities of Fe doped CaTiO3 sample calcined at a high temperature of 500°C exhibited higher activity of about 100%. Yang et al. associated enhancement in the light absorption of Fe doped CaTiO3 in the visible region with the high calcination temperature.
Recently, Chen et al. [45] reported Na + codoped CaTiO3:Eu3+ fabricated via solution combustion method using stoichiometric ratio of Ca1−xTiO3:Eu3+x (x = 0, 0.005, 0.01, 0.015, 0.02, and 0.025). The photocatalytic activity of the samples was evaluated against MB under UV light source. Figure 5(a, b, and c) indicates the Ca1-xTiO3:Eu3+x degradation of MB, kinetics plots of photocatalytic degradation, and first-order apparent rate constants (k) in photodegradation of MB. They recorded significant improvement in the photocatalytic activity of CaTiO3 after being doped with Eu3+. The CaTiO3 sample doped with 5% Eu3+ exhibited the highest DE relative to other samples, which the author attributed to the smaller optical band-gap energy of the sample relative to other samples. They also noted that Eu3+ doping led to a decrease in particle size of CaTiO3 hence enhancing its light absorption potential.
Ca1−xTiO3:Eu3+x samples degradation of MB under UV light. (b) Ca1−xTiO3:Eu3+x kinetics plots of photocatalytic degradation of MB (c) Ca1−xTiO3:Eu3+x first-order apparent rate constants (k) in photodegradation of MB Reprinted with permission [
Bhat et al. [50] reported the influence of Rh occupying sites in BaTiO3 electronic structure. The samples were prepared by one-pot hydrothermal method and photocatalytic activities of the samples were evaluated against MB under visible light source. In the experiment, the authors found that samples doped with Rh exhibited higher photocatalytic activities than the pristine sample; with 0.5 Rh doped BaTiO3 having the highest photodegradation against MB. They attributed enhancement noted in Rh doped sample to a decrease in band-gap energy. Figure 6(a and b) describes the photocatalytic of the sample against MB and the rate constants (K) of pristine BaTiO3 and Rh-doped BaTiO3 against MB. The DFT studies also predicted that an increase in Rh concentration causes a decrease in the optical band-gap energy of the samples, which further increases the absorption light of the sample within the visible region.
(a) The photocatalytic degradation of MB and (b) the rate constants (K) of the pristine BaTiO3 and Rh-doped BaTiO3 against MB. Reprinted with permission [
Similarly, Khan and co [52] reported effects of 1, 3, and 5% Ag doping on the optical properties and photocatalytic activities of BaTiO3 against Rhb dye under visible light illumination. The decomposition efficiency of BaTiO3, 1, 3, and 5% Ag doped BaTiO3 NPs are 41, 46, 58, and 79%, respectively, as indicated in Figure 7. The linear increase in photocatalytic activities of BaTiO3 was credited to the observed decrease in band-gap energy of BaTiO3 NPs as Ag concentration is increased as well as the decrease in the e—h+ recombination rate.
Decomposition efficiency of the as-prepared samples against Rh B dye under visible light Illumination. Reprinted with permission [
Nishioka and Maeda [51] investigated H2 evolution of Rh doped BaTiO3 nanocrystal synthesized via the hydrothermal method with different precursors. The H2 evolution was evaluated using aqueous ethanol at wavelength of >420 nm. They claimed that H2 evolution via photocatalytic reaction of the samples depends strongly on the following; preferred TiO2 and Rh precursor, precursor ratio, and postheating process. A sample that consists of anatase NPs as its main phase indicated higher photocatalytic activity than sample with rutile precursor. They attributed improved photocatalytic activities of post-treated Rh doped BaTiO3 to higher temperature treatment.
Lu et al. [40] explored the effect of optical and structural properties of SrTiO3-BiFeO3 solid solution on its photocatalytic H2 production. The as-prepared sample was prepared via solid-state method using stoichiometric ratio as Sr1−xBixTi1−xFexO3 (0 ≤ x ≤ 0.4). The photocatalytic activities of the samples were studied by investigating hydrogen production from Na2SO3 (aq) solution under visible light illumination. At wavelength (≥250 nm), an obvious increase in H2 production was noted in the solid solution relative to pristine SiTiO3. The highest activity was noted in Sr0.9Bi0.1Ti0.9Fe0.1O3 sample with mean H2 production rate of 180 mol/h. This value corresponds to apparent quantum efficiency of 2.28% while pristine SrTiO3 H2 production activity rate was 17 mol/h. The pristine SrTiO3 value is one order of magnitude lower than that of the solid solution as shown in Figure 8. The authors attributed the higher activity rate of a solid solution to the observed larger surface area, which in turn creates more surface reaction sites at the surface. In addition, SrTiO3 indicated a distinct absorption edge in the UV region while the solid solution indicated a large absorption shoulder in the visible light region, which they link to metal-to-metal charge transfer.
Photocatalytic H2 production of the samples when exposed to UV and visible light sources. Reprinted with permission [
He et al. [41] reported photocatalytic activities of SrTiO3/reduced graphene oxide (SrTiO3-RGO) composites, prepared through a one-pot hydrothermal process. The as-prepared sample SrTiO3–0.8%RGO composites exhibited a considerable increase in photocatalytic production of H2 (363.79 mmol (g h)−1) than SrTiO3 under UV light exposure. The higher H2 production rate observed in the composite sample was associated with generation of more reactive sites and low recombination rate of the e—h+ caused by a suitable amount of RGO composition in SrTiO3. Moreover, the photoelectrochemical and electrochemical impedance spectroscopy analyses as shown in Figure 9(a and b) revealed that SrTiO3–0.8%RGO had higher photocurrent and lower impedance value than SrTiO3. This is an indication of enhanced charge transport, separation of the photo-generated electrons, and holes in the composite sample.
Photocatalytic H2 production and (b) photoelectrochemical spectroscopy results of the samples. Reprinted with permission [
Pei et al. [49] formulated network-like hierarchical nanosized CaTiO3 via one-pot hydrothermal method and polyvinyl alcohol (PVA) as a structure guiding agent. The synthesized sample photocatalytic H2 evolution was evaluated under visible light illumination (>400 nm). It was noted that sample synthesized with PVA had a smaller band-gap value of 2.57 V compared to band-gap of sample synthesized without PVA at 3.55 eV, a value which is typical optical band-gap energy of perovskite CaTiO3. Under visible irradiation PVA-CaTiO3 H2 generation rate was 14.19 mol h−1 g−1 while CaTiO3 alone indicated a negligible H2 generation rate. The H2 generation rate of the samples is shown in Figure 10(i and ii). The authors ascribed the improvement in H2 generation by PVA-CaTiO3 to presence of defects such as oxygen vacancies (Vo). They found out that Vo creates an energy level at 0.95 eV below the CB, acted as e− donor, and aided charge transport and separation.
(i) Depicts the H2 generation rate of PVA-CaTiO3 and pristine CaTiO3 Reprinted with permission [
Abirami et al. [53] synthesized undoped PbTiO3 and 0.01, 0.02, and 0.03% Ag–Fe codoped PbTiO3 NPs via hydrothermal method. The photocatalytic activities of the as-prepared samples were evaluated using MB dyes under UV light source. The results showed that 0.02% Ag-Fe codoped PbTiO3 exhibited the highest photocatalytic decoloration of MB (80.4%) at pH 0f 6 within 2 h. From Figure 11, it appears that pH also played a critical role in photodegradation of MB; the higher the pH value, the better the discolorization efficiency. According to Devi et al. [56], the adsorption of dyes on SC photocatalysts relies on pH as a result of the changes in the point zero charge of a SC photocatalyst at different pH. The author’s associated improvement in the decolorization to reduction in e—h+ recombination rate caused by trapping photo-excited electrons by Ag and Fe.
The decolorization efficiency of the sample at the different pH a) at pH of 2. B) at pH of 4, and c) at pH of 6 Reprinted with permission [
Pirgholi-Givi et al. [54] studied the influence of the synthesis methods on photocatalytic activities of mixed BiTi3O12 and Bi12TiO20 NPs. The samples were formulated via microwave-assisted (S1) and hydrothermal synthesis (S2) methods. Their findings revealed that photocatalytic activity of the S1-sample was about 1.4 times higher than S2-sample at a higher pH value (12.5); S1-sample degraded 98% of MB in 28 min while S2-sample degraded 98% of MB in 40 min. The presence of Bi12Ti12O20 phase in Bi4Ti3O12 substrates elevated charge carrier span, enhanced charge separation, and photodegradation of the MB. Figure 12 shows a decline in percentage of degradation of the test dye.
Photocatalytic activities of S1- sample and S2-sample against MB. Reprinted with permission [
Use of titanante-based perovskite nanomaterial in photocatalytic application seems to be a promising and effective approach to mitigate the challenges that are associated with water pollution. However, considerable numbers of TBP have large optical band-gap energy, which allows photocatalytic reaction only with a UV source. In addition, the majority of TBP have excellent photocatalytic ability but with a high rate of recombination of the photogenerated e-h+ pair which significantly affects its efficiency. Some of these challenges made scientists explore ways to optimize and improve photocatalytic activities of TBP material.
In this chapter, we made efforts to avail the overview of basic principles and mechanisms of an SC photocatalyst and recent synthesis techniques that have been deployed in preparing TBP nanomaterial. Special effort was made to highlight the influence of reaction conditions and approaches such as doping, codoping, composites, temperature, and pH on the surface defects and optical properties of TBP nanomaterial. Particularly, how surface effects and optical properties of these materials impact their photocatalytic activities were also discussed. Finally, the future perspective of TBP was proposed in the chapter.
Deploying appropriate synthesis methods and precursors is quite essential as it creates room to control the particle size, crystal structure, shapes, and morphology of a TBP photocatalyst. These physiochemical parameters play a vital role in modification of the electronic bandgap and surface defects of TBP photocatalysts. Much effort should be made to adopt appropriate methods and control over physiochemical properties of these group SC photocatalysts. Attention should also be given to reaction conditions such as temperature and pH of the system during synthesis. Regulating pH and annealing temperature have shown improved crystallinity of TBP, which in turn aids its photocatalytic activities under visible light irradiation. Other strategies that have been efficient in improving photocatalytic activities of TBP material include doping, codoping, and composites with nonmetal, metals, and perovskites material. These strategies have shown to increase charge carrier span, reactive sites, surface oxygen vacancies, decrease in bandgaps, and recombination rate of photogenerated e−- h+ pair, improve charge separation, and photocatalytic absorption in the visible light region.
In spite of the progress made in recent times in understanding reaction processes and path involved in degradation of organic wastes and the role of doping TBP with other elements or TBP composite plays in altering its optical band-gap. Nevertheless, the sturdiness of these materials over time and their catalytic active cores require more detailed explanation. Hence there is a need to advance more accurate density-functional models to help optimize the photocatalytic configurations of these materials. In addition, more work should be done to optimize the reaction conditions of TBP nanomaterial, especially pH and temperature selection. Appropriate control to both parameters can enhance its photocatalytic activities as demonstrated by few authors. More work should be done to study photocorrosion of titanate-based perovskite nanomaterial.
We thank Engr. Emeka Okwuosa for the generous sponsorship of April 2014, July 2016, July 2018, and July 2021 conferences/workshops on applications of nanotechnology to Energy, Health and Environment, and for providing some research facilities.
The authors declare that they have no conflict of interest.
This research did not receive any specific grant from funding agencies in the public, commercial, or not-for-profit sectors.
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Aalborg University has Two Satellite Campuses, one in Copenhagen (Aalborg University Copenhagen) and the other in Esbjerg (Aalborg University Esbjerg).\n· He is a member of prestigious IEEE (Institute of Electrical and Electronics Engineers), and IAENG (International Association of Engineers) organizations. \n· He is the chief Editor of the Journal of Software Engineering.\n· He is the member of the Editorial Board of International Journal of Computer Science and Software Technology (IJCSST) and International Journal of Computer Engineering and Information Technology. \n· He is also the Editor of Communication in Computer and Information Science CCIS-20 by Springer.\n· Reviewer For Many Conferences\nHe is the lead person in making collaboration agreements between Aalborg University and many universities of Pakistan, for which the MOU’s (Memorandum of Understanding) have been signed.\nProfessor Akbar is working in Academia since 1990, he started his career as a Lab demonstrator/TA at the University of Sussex. After finishing his P. hD degree in 1992, he served in the Industry as a Scientific Officer and continued his academic career as a visiting scholar for a number of educational institutions. In 1996 he joined National University of Science & Technology Pakistan (NUST) as an Associate Professor; NUST is one of the top few universities in Pakistan. In 1999 he joined an International Company Lineo Inc, Canada as Manager Compiler Group, where he headed the group for developing Compiler Tool Chain and Porting of Operating Systems for the BLACKfin processor. The processor development was a joint venture by Intel and Analog Devices. In 2002 Lineo Inc., was taken over by another company, so he joined Aalborg University Denmark as an Assistant Professor.\nProfessor Akbar has truly a multi-disciplined career and he continued his legacy and making progress in many areas of his interests both in teaching and research. 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He is a full professor of signal processing and pattern recognition and is head of the Signals and Communications Department at ULPGC, teaching from 2001 on subjects on signal processing and learning theory. His research lines are biometrics, biomedical signals and images, data mining, classification system, signal and image processing, machine learning, and environmental intelligence. He has researched in 52 international and Spanish research projects, some of them as head researcher. He is co-author of 4 books, co-editor of 27 proceedings books, guest editor for 8 JCR-ISI international journals, and up to 24 book chapters. He has over 450 papers published in international journals and conferences (81 of them indexed on JCR – ISI - Web of Science). He has published seven patents in the Spanish Patent and Trademark Office. He has been a supervisor on 8 Ph.D. theses (11 more are under supervision), and 130 master theses. 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He has been a member of the IASTED Technical Committee on Image Processing from 2007 and a member of the IASTED Technical Committee on Artificial Intelligence and Expert Systems from 2011. \n\nHe has held the general chair position for the following: ACM-APPIS (2020, 2021), IEEE-IWOBI (2019, 2020 and 2020), A PPIS (2018, 2019), IEEE-IWOBI (2014, 2015, 2017, 2018), InnoEducaTIC (2014, 2017), IEEE-INES (2013), NoLISP (2011), JRBP (2012), and IEEE-ICCST (2005)\n\nHe is an associate editor of the Computational Intelligence and Neuroscience Journal (Hindawi – Q2 JCR-ISI). He was vice dean from 2004 to 2010 in the Higher Technical School of Telecommunication Engineers at ULPGC and the vice dean of Graduate and Postgraduate Studies from March 2013 to November 2017. 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His research interests include computer/machine vision, machine learning, pattern recognition, computational intelligence. \nDr. Papakostas served as a reviewer in numerous journals, as a program\ncommittee member in international conferences and he is a member of the IAENG, MIR Labs, EUCogIII, INSTICC and the Technical Chamber of Greece (TEE).",institutionString:null,institution:{name:"International Hellenic University",institutionURL:null,country:{name:"Greece"}}},editorTwo:null,editorThree:null},{id:"25",title:"Evolutionary Computation",coverUrl:"https://cdn.intechopen.com/series_topics/covers/25.jpg",isOpenForSubmission:!0,editor:{id:"136112",title:"Dr.",name:"Sebastian",middleName:null,surname:"Ventura Soto",slug:"sebastian-ventura-soto",fullName:"Sebastian Ventura Soto",profilePictureURL:"https://mts.intechopen.com/storage/users/136112/images/system/136112.png",biography:"Sebastian Ventura is a Spanish researcher, a full professor with the Department of Computer Science and Numerical Analysis, University of Córdoba. 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He obtained both his M.Sc. and Ph.D. from the University of Liverpool, England, in the field of Intelligent Systems. He is a full professor at the Universidad Autonoma de Queretaro, Mexico, and a member of the National System of Researchers (SNI) since 2009. Dr. Aceves Fernandez has published more than 80 research papers as well as a number of book chapters and congress papers. He has contributed in more than 20 funded research projects, both academic and industrial, in the area of artificial intelligence, ranging from environmental, biomedical, automotive, aviation, consumer, and robotics to other applications. He is also a honorary president at the National Association of Embedded Systems (AMESE), a senior member of the IEEE, and a board member of many institutions. 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Dr. Aydin is currently a Fellow of Higher Education Academy, UK, a member of EPSRC College, a senior member of IEEE and a senior member of ACM. In addition to being a member of advisory committees of many international conferences, he is an Editorial Board Member of various peer-reviewed international journals. He has served as guest editor for a number of special issues of peer-reviewed international journals.",institutionString:null,institution:{name:"University of the West of England",institutionURL:null,country:{name:"United Kingdom"}}},editorTwo:null,editorThree:null}]},overviewPageOFChapters:{paginationCount:20,paginationItems:[{id:"82526",title:"Deep Multiagent Reinforcement Learning Methods Addressing the Scalability Challenge",doi:"10.5772/intechopen.105627",signatures:"Theocharis Kravaris and George A. 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