Citation: Daniel A. Barone, Ana C. Krieger. The Function of Sleep[J]. AIMS Neuroscience, 2015, 2(2): 71-90. doi: 10.3934/Neuroscience.2015.2.71
[1] | Vo Thanh Phuoc, Kunio Yoshikawa . Effect of the storage condition of microalgae on hydrochar lipids and direct esterification-transesterification of hydrochar lipids for biodiesel production. AIMS Energy, 2017, 5(1): 39-53. doi: 10.3934/energy.2017.1.39 |
[2] | Bárbara Gonçalves Rocha, Alice Lopes Macedo, Bárbara Rodrigues Freitas, Priscylla Caires de Almeida, Vany P. Ferraz, Luis Carlos Duarte Cavalcante, José Domingos Fabris, José Domingos Ardisson . Magnetic fraction from phosphate mining tailings as heterogeneous catalyst for biodiesel production through transesterification reaction of triacylglycerols in bio-oil. AIMS Energy, 2017, 5(5): 864-872. doi: 10.3934/energy.2017.5.864 |
[3] | Maria del Pilar Rodriguez, Ryszard Brzezinski, Nathalie Faucheux, Michèle Heitz . Enzymatic transesterification of lipids from microalgae into biodiesel: a review. AIMS Energy, 2016, 4(6): 817-855. doi: 10.3934/energy.2016.6.817 |
[4] | Dejene Beyene, Dejene Bekele, Bezu Abera . Biodiesel from blended microalgae and waste cooking oils: Optimization, characterization, and fuel quality studies. AIMS Energy, 2024, 12(2): 408-438. doi: 10.3934/energy.2024019 |
[5] | Douglas Queiroz Santos, Ana Paula de Lima, Maíra Martins Franco, David Maikel Fernandes, Waldomiro Borges Neto, José Domingos Fabris . Evaluation and Characterization of Biodiesels Obtained Through Ethylic or Methylic Transesterification of Tryacylglicerides in Corn Oil. AIMS Energy, 2014, 2(2): 183-192. doi: 10.3934/energy.2014.2.183 |
[6] | Douglas Faria, Fernando Santos, Grazielle Machado, Rogério Lourega, Paulo Eichler, Guilherme de Souza, Jeane Lima . Extraction of radish seed oil (Raphanus sativus L.) and evaluation of its potential in biodiesel production. AIMS Energy, 2018, 6(4): 551-565. doi: 10.3934/energy.2018.4.551 |
[7] | Vo Thanh Phuoc, Kunio Yoshikawa . Comparison between direct transesterification of microalgae and hydrochar. AIMS Energy, 2017, 5(4): 652-666. doi: 10.3934/energy.2017.4.652 |
[8] | Edith Martinez-Guerra, Veera Gnaneswar Gude . Energy aspects of microalgal biodiesel production. AIMS Energy, 2016, 4(2): 347-362. doi: 10.3934/energy.2016.2.347 |
[9] | Ee Sann Tan, Kumaran Palanisamy, Teuku Meurah Indra Mahlia, Kunio Yoshikawa . Performance and emission study on waste cooking oil biodiesel and distillate blends for microturbine application. AIMS Energy, 2015, 3(4): 798-809. doi: 10.3934/energy.2015.4.798 |
[10] | Aman Santoso, Titania Nur Kusumah, Sumari Sumari, Anugrah Ricky Wijaya, Rini Retnosari, Ihsan Budi Rachman, Siti Marfuah, Muhammad Roy Asrori . Synthesis of biodiesel from waste cooking oil using heterogeneous catalyst of Na2O/γ-Al2O3 assisted by ultrasonic wave. AIMS Energy, 2022, 10(5): 1059-1073. doi: 10.3934/energy.2022049 |
ASTM | American Society for Testing and Materials |
FAME | Fatty Acid Methyl Ester |
FFA | Free Fatty Acid |
GHG | Green House Gas |
IEA | International Energy Agency |
IUPAC | International Union of Pure and Applied Chemistry |
OECD | Organization for Economic Co-operation and Development |
The U.S Energy Information Administration, in its International Energy Outlook 2016 report, indicated that the world total energy consumption is significantly increasing. In this report, the worldwide energy consumption is projected over the 28 year period from 2012 to 2040 as shown in Figure 1.
This projection specified that much of the growth in energy consumption is expected from non-OECD countries, where strong economic growth and expanding populations lead the increase in world energy use.
As countries develop and living standards improve, energy demand grows rapidly. For instance, in nations experiencing fast-paced economic growth, their life style changed and more economic activities emerge demanding more and more energy.
Crude oil, coal and gas are the main dominant resources for world energy supply [2]. However, most argue that demand for renewables would increase owing to limited reserve of the conventional fuels, which jeopardize the energy security issue, as well as for the environmental benefit of using renewables as alternative energy supplies.
According to the IEA Medium Term Renewable Energy Report 2015, the renewable energy share in the total world energy consumption is expected to have at least 26% increment by 2020 [3]. And the International Energy Agency, world energy outlook 2013 [4], particularly showed that, for the next two decades, world fuel oil demand is concentrated in transport sector and in which, diesel fuel demand is expected to dominate by 5.5 million barrel per day as shown in Figure 2.
As it can be seen from Figure 2, diesel fuel use is expected to be the main to get the highest score in increment in oil demand for the years to come. This indicates there is more practical opportunity in working towards substituting the conventional diesel fuel with biodiesel so that attaining the required demand without causing negative consequence to our environment.
In accordance with this, the awareness of energy issues and environmental problems associated with burning fossil fuels has globally encouraged many researchers to investigate the possibility of using alternative sources of energy instead of oil and its derivatives. Among them, biodiesel seems very interesting for several reasons.
The invention of the vegetable oil fueled engine by Sir Rudolf Diesel dated back in the 1900s, however, full exploration of biodiesel only came into light in the 1980s as a result of renewed interest in renewable energy sources for reducing greenhouse gas (GHG) emissions, and alleviating the depletion of fossil fuel reserves. Biodiesel is defined as mono-alkyl esters of long chain fatty acids derived from vegetable oils or animal fats and alcohol with or without a catalyst [5,6,7,8,9].
Biodiesel is highly biodegradable and has minimal toxicity. It has almost zero emissions of aromatic compounds and other chemical substances that are destructive to the environment. It has a small net contribution of carbon dioxide (CO2) when the whole life-cycle is considered (including cultivation, production of oil and conversion of oil to biodiesel); and its production can be decentralized so that it could have significant potential for improvement of rural economy [5,10].
Compared to diesel fuel, biodiesel produces no sulfur, less carbon monoxide, less particulate matters, less smoke and hydrocarbons emission and more oxygen. More free oxygen leads to the complete combustion and reduced emission [11,12].
Vegetable oil and/or animal fat can be converted to fuel for diesel engine through four major possible ways: direct use or blending of oils, micro-emulsion, thermal cracking or pyrolysis and transesterification reaction. Among these methods, the most preferred one is transesterification reaction. Transesterification reactions enables the use of diverse feedstock types to produce a fuel highly resemble to conventional diesel in quality. Through this method, oils and fats (triglycerides) are converted to their alkyl esters with viscosity similar to diesel fuel.
Transesterification reaction can be catalyzed or non-catalyzed. The catalysis of transesterification is usually either chemically like base catalyzed transesterification and acid catalyzed transesterification, or using enzyme catalysts like lipase-catalyzed transesterification. However, there are also some less investigated but efficient ways to produce biodiesel through esterification of oils and fats such as those using Nano catalysts and ionic liquid catalysts. The non-catalyzed transesterification is carried out without any catalyst only by using an alcohol at supercritical conditions where the alcohol, usually methanol, is at a temperature and pressure above its critical point, where distinct liquid and gas phases do not exist [13,14,15]. In the supercritical state, the dielectric constant of alcohol is decreased so that two-phase formation of vegetable oil/alcohol mixture is not encountered and only a single phase is found favoring the reaction [16].
Each transesterification technique requires different feedstock character. For example, some can handle feedstock with high FFA content where as others are very sensitive to even small amount. Some esterification techniques are more advantages than the others at least with respect to cost of production, or minimum waste generation, or high productivity and the like. In addition, there are some very important reaction conditions, which should always be optimized for efficient production of biodiesel. Among them the very commonly studied are: molar ratio of alcohol to oil, type and amount of catalyst, reaction temperature, reaction time, reaction medium, type and relative amount of solvents.
Accordingly, in this paper, more emphasis is given on reviewing the effect of the main reaction conditions for an efficient production of biodiesel from different feedstock types as well as on summarizing the advantages and disadvantages of these major transesterification techniques.
The dominant technologies, which enable us to use oil and fat feedstock types as fuel in diesel engines, are usually described as direct use or blending of oils, micro-emulsion, pyrolysis and transesterification. Transesterification being currently mentioned by various researchers as the most preferable due to better quality of fuel produced [17,18,19].
Pyrolysis refers to a chemical change caused by the application of thermal energy in the absence of air or oxygen, or by the application of heat in the presence of a catalyst, which results in cleavage of bonds and formation of a variety of small molecules. Pyrolysis is conducted at temperature range of 400–600 ℃. The process produces gases, bio-oil, and a char depending on the rate of pyrolysis. Based on the operating conditions, the pyrolysis process can be divided into three subclasses: conventional pyrolysis, fast pyrolysis and flash pyrolysis [20] as shown in Table 1. Fast pyrolysis is the one used for production of bio-oil.
Method | Temperature (℃) | Residence Time | Heating rate (℃/s) | Major products |
Conventional/slow pyrolysis | Med-high (400–500) | Long 5–30 min | Low 10 | Gases Char Bio-oil (tar) |
Fast pyrolysis | Med-high (400–650) | Short 0.5–2 s | High 100 | Bio-oil (thinner) Gases Char |
Ultra-fast/flash pyrolysis | High (700–1000) | Very short < 0.5 s | Low 10 | Gases Bio-oil |
This liquid fraction of the thermally decomposed vegetable oil, bio-oil, is likely to approach diesel fuel properties and characteristics. Ma et al. [21] mentioned that the chemical compositions (heavy hydrocarbons) of the diesel fractions produced by catalytic cracking of copra oil and palm oil stearin were similar to fossil fuels. The process was simple and effective compared with other cracking processes according to them.
According to Ma et al. [21] pyrolytic chemistry is difficult to characterize because of the variety of reaction paths and the variety of reaction products that may be obtained from the reactions that occur. The pyrolyzed material can be vegetable oils, animal fats, natural fatty acids and methyl esters of fatty acids.
In another study, Mahanta et al. [22] mentioned that pyrolyzate (product of pyrolysis) from any feedstock type has lower viscosity, flash point, and pour point than petroleum diesel fuel and equivalent calorific values. In addition, the cetane number of the pyrolyzate is lower. According to them, the pyrolyzed vegetable oils contain acceptable amounts of sulfur, water and sediments and give acceptable copper corrosion values but unacceptable quantities of ash, carbon residual and pour point.
Abbaszaadeh et al. [23] also reported that biodiesel fuel produced through a pyrolysis process or known as bio-oil is suitable for diesel engines; however, low-value materials are produced due to the elimination of oxygen during the process. Undesirable properties that sometimes restrict the application of biodiesel produced through this process are low heating value, incomplete volatility, and instability [24]. But, in another view, Singh and Singh [25], mentioned that thermal pyrolysis of triglycerides has several advantages such as lower processing cost, simplicity, less waste, and no pollution.
Another disadvantage of pyrolysis is the need for distillation equipment for separation of the various fractions. Also the product obtained is similar to gasoline containing sulphur which makes it less ecofriendly [26].
The equipment for thermal cracking and pyrolysis is expensive for modest throughputs. In addition, while the products are chemically similar to petroleum-derived gasoline and diesel fuel, the removal of oxygen during the thermal processing also removes any environmental benefits of using an oxygenated fuel. It produces some low value materials and, sometimes, more gasoline than diesel fuel [21].
Among the physical properties of raw vegetable oil, which makes it to be not directly used as fuel, is its viscosity. Ma et al. [21] pointed out that, the formation of micro-emulsion is one of the potential solutions for solving the problem of vegetable oil viscosity.
According to IUPAC definition, micro-emulsion is dispersion made of water, oil, and surfactant (s) that is an isotropic and thermodynamically stable system with dispersed domain diameter varying approximately from 1 to 100 nm, usually 10 to 50 nm [27].
The components of a biodiesel micro-emulsion include diesel fuel, vegetable oil, alcohol, and surfactant and cetane improver in suitable proportions. Alcohols such as methanol and ethanol are used as viscosity lowering additives, higher alcohols are used as surfactants and alkyl nitrates are used as cetane improvers [28].
Mahanta et al. [22] reported that micro-emulsion can be made of vegetable oils with an ester and dispersant (co-solvent), or of vegetable oils, and alcohol and a surfactant and a cetane improver, with or without diesel fuels. All micro-emulsions with butanol, hexanol and octanol met the maximum viscosity requirement for diesel fuel. The 2-octanol is an effective amphiphile in the micellar solubilization of methanol in triolein and soybean oil [29].
Micro-emulsions can improve spray properties by explosive vaporization of the low boiling constituents in the micelles. Micro-emulsion results in reduction in viscosity, increase in cetane number and good spray characters in the biodiesel. According to Srivastava and Prasad [30], short term performances of both ionic and non-ionic micro-emulsions of aqueous ethanol in soybean oil was nearly as good as that of NO. 2 diesel fuel, in spite of the lower cetane number and energy content. NO. 2 diesel fuel is a fuel with distillation temperature of 640 degrees Fahrenheit at the 90% recovery point and meets the specifications defined in ASTM Specification D 975 [31].
However, as indicted by Parawira [32], continuous use of micro-emulsified diesel in engines causes problems like injector needle sticking, carbon deposit formation and incomplete combustion.
Direct uses of vegetable oils have generally been considered not satisfactory and impractical for both direct and indirect diesel engines. The high viscosity, acid composition, free fatty acid content, as well as gum formation due to oxidation and polymerization during storage and combustion, carbon deposits and lubricating oil thickening are obvious problems. In another view, Ma et al. [21], pointed out that oil deterioration and incomplete combustion are the two severe problems associated with the direct use of vegetable oils as fuels.
In such cases, it is helpful to dilute vegetable oils with such materials as diesel fuels, solvent or ethanol. Dilution results in reduction of viscosity and density of vegetable oils. Bilgin et al. [33] indicated that the addition of 4% ethanol to diesel fuel increases the brake thermal efficiency, brake torque and brake power, while decreasing the brake specific fuel consumption. They also argued that since the boiling point of ethanol is less than that of diesel fuel, it could assist the development of the combustion process through an unburned blend spray.
In their review of biodiesel production methods, Ma et al. [21] mentioned that, the viscosities of 50/50 (winter rapeseed oil and diesel) and 70/30 (whole winter rapeseed oil and diesel) blends were much higher (6–18 times) than NO. 2 diesel. According to them, a blend of 70/30 winter rapeseed oil and NO. 1 diesel fuel (A light distillate fuel oil that has distillation temperatures of 550 degrees Fahrenheit at the 90% recovery point and meets the specifications defined in ASTM Specification D 975 [31]) was used successfully to power a small single-cylinder diesel engine for 850 h. No adverse wear and no effects on lubricating oil or power output were noted.
Transesterification is the main convenient method to produce biodiesel from oil and fat feedstock types, which chemically resembles petroleum diesel. Through this method, oils and fats (triglycerides) are converted to their alkyl esters with reduced viscosity to near diesel fuel levels. This product is thus a fuel with properties similar to petroleum based diesel fuel, which enable it be used in existing petroleum diesel engines without modifications. Generally, transesterification is a reversible reaction, which simply proceeds essentially by mixing the reactants usually under heat and/or pressure. However, if some kind of catalyst is added to the reaction, it will be accelerated. The simplest chemical reaction for transesterification of triglycerides is presented in Figure 3.
There are a number of ways to produce biodiesel through transesterification. The general schematics diagram for these possible ways is shown in Figure 4.
All of the catalytic transesterification processes involve the reaction of a triglyceride (fat or oil) with an alcohol in the presence of some catalyst to form esters and glycerol. A triglyceride has a glycerin molecule as its base with three long chain fatty acids attached. The characteristics of the oil/fat are determined by the nature of the fatty acids attached to the glycerin. The nature of the fatty acids can in turn affect the characteristics of the biodiesel [34].
A successful transesterification reaction for efficient biodiesel production is signified by easy and effective separation of the ester and glycerol layer after the reaction time. The heavier, co-product, glycerol can be purified for use in other industries, e.g. the pharmaceutical, cosmetics etc.
Acid catalyzed transesterification was the first method ever in history to produce biodiesel (ethyl ester) from palm oil using ethanol and Sulfuric acid [35].
The acid catalyzed process is due to the reaction of a triglyceride (fat/oil) with an alcohol in the presence of acid catalyst to form esters (biodiesel) and glycerol. Specially, this method is convenient and economically viable in producing biodiesel from oil or fat resources with high free fatty acid content. However, the acid catalyzed reaction requires a longer reaction time and a higher temperature than the alkali catalyzed reaction [36].
Acid catalyzed transesterification starts by mixing the oil directly with the acidified alcohol, so that separation and transesterification occur in single step, with the alcohol acting both as a solvent and as esterification reagent [23].
The acid catalyzed transesterification should be carried out in the absence of water, in order to avoid the competitive formation of carboxylic acids which reduce the yields of alkyl esters [22]. Park et al. [37] did an investigation of the effect of water on transesterification of oleic acid with methanol in the presence of sulfuric acid as a catalyst. In their work, the yield of fatty acid methyl ester (FAME) was studied at oil to methanol molar ratios of 1:3 and 1:6 and reaction temperatures of 60 ℃ and 80 ℃. According to the result of their study, the rate of esterification of oleic acid significantly decreased as the initial water content increased to 20% of the oil [37].
Since transesterification is an equilibrium reaction, there should always be more alcohol than the oil to favor the forward reaction for complete conversion of the oil to alkyl ester. It is also known that the temperature and the amount of acid catalyst affect the transesterification rate and the yield of alkyl ester. However, more alcohol beyond the optimum will also cause some extra cost on separation of more produced glycerol from the alkyl ester and that is why there should always be an optimization of the ratio for efficient production. Different studies have been conducted to investigate how the molar ratio of oil to alcohol to acid as well as how temperature ranges affect the transesterification and thus the alkyl ester yield.
Zheng et al. [38] showed that, with convenient molar ratios and temperature ranges, methyl ester conversion of waste cooking oil in acid catalyzed transesterification can reach up to 99%. By their study, they concluded that, the oil: methanol: acid molar ratios and the temperature were the most significant factors affecting the yield of fatty acid methyl ester (FAME). According to their study result, at 70 ℃ with oil: methanol: acid molar ratios of 1:245:3.8, and at 80 ℃ with oil: methanol: acid molar ratios in the range 1:74:1.9–1:245:3.8, the transesterification was essentially a pseudo-first-order reaction as a result of the large excess of methanol which drove the reaction to completion (99 ± 1%) at 4 hours. In the presence of the large excess of methanol, free fatty acids present in the waste oil were very rapidly converted to methyl esters in the first few minutes under the above conditions [38].
Sulphuric acid, sulfonic acid, and hydrochloric acid are the usual acid catalysts but the most commonly used is sulphuric acid. There are also various studies done to see the yield effect of using alternative acids.
Soriano et al. [39] demonstrated that AlCl3 could be used to catalyze the esterification of stearic acid suggesting that it is a potential alternative catalyst for biodiesel preparation using cheaper vegetable oil containing high amount of FFA. In their study, optimum conditions to afford 98% conversion of canola oil to FAME is with the use of methanol to oil molar ratio of 24:1 and reaction time of 18 h at 100 ℃ in the presence of 5% AlCl3 as catalyst [39].
Marchetti et al. [40] mentioned that one of the drawbacks of producing biodiesel using acid catalyzed transesterification is having more amount of free glycerol in the biodiesel higher than the maximum value allowed to satisfy the international standard ASTM. However, they also mentioned in their study that this could be improved either by adding equipment for purification of the product stream or by modifying some of the process variable such as residence time in the reactor [40].
The use of co-solvents to overcome the mass transfer resistance due to immiscibility of alcohol with oil as well as the use of different acids usually help to get different alternatives for efficient production of biodiesel from low value feedstock. In this regard, Miao et al. [41] studied the effectiveness of trifluoroacetic acid catalyzed transesterification of soybean oil to produce biodiesel. The results from their study showed that the oil could be converted to biodiesel directly by one-step trifluoroacetic acid catalyzed process without extreme temperature and pressure conditions. The optimum process combination was 2.0 M (M is for Molarity, which is defined as the number of moles of solute dissolved per liter of solution) catalyst concentration with 20:1 molar ratio of methanol to oil at temperature of 120 ℃ [41]. According to the authors this procedure represents a simple and mild method for biodiesel production with short reaction time and with high conversion rate, which would offer potential for an industrial process[41].
Despite its relatively slow reaction rate, the acid-catalyzed process offers benefits with respect to its independence from free fatty acid content and the consequent absence of a pretreatment step. These advantages favor the use of the acid-catalyzed process when using feedstock types like waste cooking oil as well as most non-edible plant oil, which are usually associated with higher content of fatty acid [42]. Table 2 indicates some selected research results about the effect of process variables on acid catalyzed transesterification of different feedstock types.
Feedstock | Alcohol | Process variables | Yield % achieved | Ref. | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time | Stirring speed | Acid Catalyst | Catalyst concentration | ||||
Mixed oil b | Methanol | 6:1 | 60 | - | 300 rpm | H2SO4 | 2.5% | 96.6% | [43] |
Soybean oil | Methanol | 20:1 | 120 | 5 h | - | trifluoroacetic acid | 2.0 M | 98.4% | [41] |
Canola oil | Methanol with terahydrofuran as Co-solvent | 24:1 | 110 | 18 h | AlCl3 | 5% | 98% | [39] | |
Corn oil | Methanol with dimethyl ether as Co-solvent | 6:1 | 80 | 2 h | - | p-toluenesulfonic acid | 4 wt.% | 100% | [44] |
Canola oil up to 20% FFA | Methanol | 9:1 | 200 | - | - | 12-Tungstophosphoric acid | 3 wt.% | 90 wt.% | [45] |
b mixed oil-50% sunflower and 50% soybean oil |
The alkaline catalyzed transesterification process is the reaction of a triglyceride (fat/oil) with an alcohol in the presence of alkaline catalysts such as alkaline metal alkoxides and hydroxides as well as sodium or potassium carbonates to form esters (biodiesel) and glycerol. Alkali catalyzed transesterification is much faster than acid catalyzed transesterification and is less corrosive to industrial equipment and therefore is the most often used commercially [26,46]. However, presence of water and high amount of free fatty acid in a feedstock gives rise to saponification of oil and therefore, incomplete reaction during alkaline transesterification process with subsequent formation of emulsion and difficulty in separation of glycerol [32]. The saponification reaction is represented by the equation shown below:
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The main disadvantage resulted due to saponification reaction is the consumption of catalyst and increased difficulty in separation process, which leads to high production cost. In addition to that, formation of water in the product will also inhibit the reaction. In this case, water generated either from vegetable oil (due to its high water content) or formed during saponification reaction will hydrolyze triglyceride to form more free fatty acid as shown in the equation below.
Generally, base catalyst manifest much higher catalytic activity than acid catalysts in the transesterification reaction, but are selectively suitable for deriving biodiesel only from refined oils having low content of free fatty acids (FFA) usually less than 0.5% [48]. This makes base catalyzed transesterification confined to use only best quality refined oil like vegetable cooking oil for input, which in turn makes it expensive way to produce biodiesel while creating food versus energy controversy. Here we can consider esterification as additional step to decrease the free fatty acid content of feedstock with greater than 0.5% FFA. This will enable us to choose among different feedstock types with higher FFA content. However, this additional process usually makes it more complex in the instrumentation (because of the addition of esterification unit) than the sole alkaline-catalyzed process, thereby resulting in an increase in equipment and operating costs.
The efficient production of biodiesel using base catalyzed transesterification is not only dependent on the quality of the feedstock, it is also dependent on the crucial reaction operation variables such as alcohol to oil molar ratio, reaction temperature, rate of mixing, reaction time, type and concertation of catalyst and also on the type of alcohol used [19,25,49].
Even though in theory, the stoichiometric ratio of alcohol (usually methanol) to oil is 3:1, in order to assist the forward reaction so that to get more conversion, the concentration of the methanol has to be increased. This is because; lower amount of methanol means slower forward reaction and less percentage of yield. In contrary, high methanol amount beyond the optimum, interfere with the separation of glycerin because of an increase in solubility; the glycerin remaining in the solution drives the equilibrium back to the left side of reaction, resulting in the lower yield of esters. This is due to the fact that methanol, with one polar hydroxyl group, can act as an emulsifier that enhances emulsions [19].
Sodium hydroxide, potassium hydroxide and sodium methoxide are catalysts usually used in base catalyzed transesterification. Sodium hydroxide is mostly preferable owing to its intermediate catalytic activity and a much lower cost [50]. Lueng et al. [51] evaluated the effect of catalyst on transesterification by comparing the maximum ester content and yield percentage attained using three base catalysts while other determinant variables were kept the same for all conditions during the base catalyzed transesterification processes. The result of their study is shown in Table 3.
Catalyst | Concentration of the catalyst (wt.%, by weight of crude oil) | Ester content (wt.%) | Product yield (wt.%) |
NaOH | 1.1 | 94.0 | 85.3 |
KOH | 1.5 | 92.5 | 86.0 |
CH3ONa | 1.3 | 92.8 | 89.0 |
This study revealed that sodium hydroxide is better in attaining purity percentage (ester content) than the others whereas sodium methoxide is good in providing higher yield percentage.
The relative concentration of catalysts required for maximum production is dependent on the type of feedstock used. Dias et al. [52] compared the performance of three alkali catalysts for transesterification of virgin and waste soybean and sunflower oil and they reported that, the optimum conditions which ensured that the attainment of the final product being in agreement with the European biodiesel standard were: 0.6 (wt.%) CH3ONa for both virgin oils; 0.6 (wt.%) NaOH for sunflower oil and 0.8 (wt.%) for soybean oil and; 0.8 (wt.%) using both sodium based catalysts for waste frying oils. They also reported that under these optimum conditions, a purity of 99.4 (wt.%) could be obtained.
In the study carried out by Hossain and Boyce [53] in spite of higher yield, using NaOH as catalyst during biodiesel synthesis from waste sunflower cooking oil, causes more emulsion than KOH and makes separation of biodiesel from glycerin complicated, as they reported. The solution of alkaline catalyst in methanol is recommended to be prepared freshly in order to avoid the moisture absorbance and to maintain the catalytic activity [54].
Leung et al. [51] reported that the conversion of waste cooking oil using sodium hydroxide catalysts was approximately 86%. As presented in Table 4, Ojolo et al. [55], explained that the increase of the catalyst concentration influences the ester yield in a positive manner up to 0.80% NaOH for Jatropha oil and then after that it decreases.
Catalyst (gm) |
Oil (gm) |
Methanol (gm) |
Reaction Time (hr) |
Reaction Temp. (℃) |
Biodiesel (%) |
Glycerin (%) |
1.2 | 100 | 20 | 1 | 65 | 87.20 | 30.80 |
1.0 | 100 | 20 | 1 | 65 | 92.40 | 27.35 |
0.8 | 100 | 20 | 1 | 65 | 95.33 | 24.22 |
0.6 | 100 | 20 | 1 | 65 | 74.45 | 45.37 |
Parawira [32] reported that, the alkaline catalyst concentration in the range of 0.5–1% by weight yield 94–99% conversion of most vegetable oils into esters. There are several disadvantages in using an alkaline catalysis process although it gives high conversion levels of triglycerides to their corresponding methyl esters in short reaction times. According to Parawira [32], the process is energy intensive, recovery of glycerol is difficult, the alkaline catalyst has to be removed from the product, alkaline wastewater generated requires treatment and the level of free fatty acids and water greatly interfere with the reaction. The risk of free fatty acid or water contamination results in soap formation that makes the separation process difficult [56].
Table 5 summarizes the results of some researches done to study the effect of different process variables on base catalyzed transesterification of different feedstock types.
Feedstock | Alcohol | Process variables | Yield % achieved | Ref. | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time | Stirring speed | Catalyst type | Cat. Concentration | ||||
Rice bran oil | methanol | 1:09 | 55 | 60 minute | - | NaOH | 0.75% (w/w) | Optimum | [57] |
Sunflower cooking oil | methanol | 6:01 | 40 | - | 320 rpm | KOH | 1% | 99.50% | [53] |
refined cooking vegetable oils | methanol | 6:01 | 65 | 60 minute | - | KOH | 1.2 wt.% | 97.50% | [58] |
Waste cooking vegetable oils | methanol | 6:01 | 65 | 60 minute | - | KOH | 1.2 wt.% | 93.20% | [58] |
Jatropha oil | methanol | 5:01 | 65 | 60 minute | - | NaOH | 0.80% | 95.5%. | [59] |
Soybean oil | methanol | 6:01 | 60 ± 1 | 60 minute | - | NaOH | 1% | 90% | [60] |
Cottonseed oils | methanol | 6:01 | 60 ± 1 | 60 minute | - | NaOH | 1% | 98.50% | [60] |
Waste frying oils | methanol | 7.5:1 | 50 | 30 minute | - | NaOH | 0.50% | 96% | [61] |
Karanja oil | methanol | 6:01 | 65 | 15 minute | 360 rpm | KOH | 1% | > 85% | [54] |
Karanja oil | methanol | 12:01 | 65 | 60 minute | 360 rpm | KOH | 1% | 98% | [54] |
Duck tallow | methanol | 6:01 | 65 | 180 minute | - | KOH | 1 wt.% | 97% | [62] |
Silurus triostegus Heckel fish oil (STFO) | methanol | 6:01 | 32 | 60 minute | - | KOH | 0.50% w/w | 96% | [49] |
Waste cooking oil | methanol | 6:01 | microwave power of 750 W | 3 minute | - | CH3ONa | 0.75 wt.% | 97.90% | [63] |
soybean oil-assisted by low-frequency ultrasound (20 kHz) | Ethanol | 6:01 | 60 | 6 minute | 600 rpm | KOH | 1% (m/m) | 98% | [64] |
Waste frying oils | methanol | 12:01 | 65 | 150 minute | - | Tetramethylguanidine | 3 wt.% | > 90% | [65] |
The use of homogeneous catalysts, especially base catalysts, are associated with some amount of difficulty in purification of by-product glycerol as well as in the requirement of wastewater treatment. To alleviate these problems, the use of heterogeneous catalysts usually solid base catalyst is recommended. Solid base catalysts have many advantages, such as having mild reaction condition, easy separation, and high activity and less contaminant [66].
Many researchers argued that the use of heterogeneous catalysts both in acid and base form brought about the advantage of having easy and less costly separation as well as possibility of reusing the catalyst. Parawira [32] mentioned that, the heterogeneous catalyst eliminates the additional cost associated with the homogeneous sodium hydroxide to remove the catalyst after transesterification. In addition, the heterogeneous catalyst offers a wide option for the catalytic selection because of its high selectivity and reusability characteristics [67]. Dell'Anna et al. [68] investigated transesterification of polyunsaturated compounds catalyzed by a recyclable polymer supported palladium catalyst. They found out that the heterogeneous solid catalyst, palladium exhibited a remarkable activity and was reusable for eight consecutive cycles.
Heterogeneous solid catalysts are usually categorized as acid solids capable to catalyze free fatty acids esterification reaction; base solids, which are able to catalyze triglycerides transesterification reaction; and bifunctional solids (acid-base character) which show ability to simultaneously catalyze esterification and transesterification reaction [69].
There are various efforts made to find effective solid catalysts in both acid and basic form for heterogeneous catalyzed process. Bournay and Casanave [70] investigated the use of new solid catalyst for continuous transesterification process. They mentioned that this new solid catalyst consists of a mixed oxide of zinc and aluminum, which promotes the transesterification reaction without catalyst loss. Actually using this new catalyst, the reaction has to be performed at higher temperature and pressure than homogeneous catalysis processes, with an excess of methanol, which can finally be removed by vaporization and recycled to the process [70]. In contrary, however, there are some solid metal oxides, such as oxides of tin, magnesium, and zinc, which are well known as catalysts, and perform like homogeneous catalysis and end up as metal soaps or metal glycerates [70].
Bournay and Casanave [70] claimed also that, while using this new solid catalyst, neither catalyst recovery nor aqueous treatment steps are required. The purification steps of products could then be much more simplified so that very high yields of methyl esters, close to the theoretical value, could be obtained. In addition, the glycerin can directly be produced with high purity levels (at least 98%) without any salt contaminants.
Heterogeneous catalysts such as amorphous zirconia, titanium and potassium zirconias have also been used for catalyzing the transesterification of vegetable oils. Furuta et al. [71] evaluated amorphous zirconia catalysts, titanium-, aluminum-, and potassium-doped zirconias, in the transesterification of soybean oil with methanol at 250 ℃, and the esterification of n-octanoic acid with methanol at 175–200 ℃. They reported that, titanium-and aluminum-doped zirconias are promising solid catalysts for the production of biodiesel fuels from soybean oil because of their high performance, with over 95% conversion in both of the reactions.
In another study, Huaping et al. [72] demonstrated the potential of preparing biodiesel from Jatropha curcas oil catalyzed by solid super base of calcium oxide. When treated with ammonium carbonate solution and calcinated at high temperature, calcium oxide becomes a solid super base, which shows high catalytic activity in transesterification. They reported that, under the optimum conditions, the conversion of Jatropha curcas oil can reach 93%.
Sánchez et al. [73] studied the influence of the reaction temperature, the alcohol:oil ratio and the catalyst percent on the methanolysis of Jojoba oil using CaO as a catalyst, which was particularly derived from mussel shells. According to their study, the variables which had the higher positive effect on the methanolysis of Jojoba oil, in a pressurized environment (with approximate 10 bars in Parr reactor), are the methanol:oil ratio and the temperature, whereas the catalyst percent had a slight negative impact on the process. They reported that, using this catalyst, the reaction time could be reduced by half, from 10 to 5 hours and the Jojoba oil conversion reached a maximum of 96.3% with a pressurized environment in the reactor.
Avhad et al. [74] investigated the catalytic activity of glycerol-enriched calcium oxide for ethanolysis of avocado oil. The calcium oxide catalyst was derived from Mytilus Galloprovincialis shells through thermal and glycerol (with glycerol dosage of 10% with respect to catalyst weight) treatment before using for the ethanolysis reaction. This shell is simply a waste generated from the fish industry. In this study, they examined the influence of temperature, ethanol-to-oil molar ratio, and the catalyst amount on the variation in the concentration of triacylglycerols and biodiesel with reaction time. They also determined the interaction between the reaction variables (ethanol-to-oil molar ratio and catalyst amount), their influence on the ethanolysis process, and the optimum variables affecting the process through the response surface methodology. According to their conclusion, both catalyst amount and ethanol-to-oil molar ratio significantly affected the described ethanolysis process. They also reported that, temperature of 75 ℃, ethanol-to-oil molar ratio of 9:1, and 7 wt.% catalyst amount was taken to be suitable for the studied glycerol-enriched CaO assisted avocado oil ethanolysis process.
The sensitivity of the base catalyzed transesterification to the FFA and water content of the feedstock still persist as the main problem in case of heterogeneous base catalyzed transesterification reaction too. Again, to solve such feedstock quality problem, solid acid catalyst for simultaneous esterification of FFAs and transesterification of triglycerides can be good alternative for biodiesel production from feedstock with higher FFA and water content. Moreover, Melero et al. [75] mentioned that a heterogeneous acid catalyst if incorporated into a packed bed continuous flow reactor, can simplify product separation and purification and reducing waste generation. Solid acid catalyst can be recycled, easily removed and can simultaneously catalyze esterification and transesterification [76].
Peng et al. [76] characterized and studied the activity of a solid acid catalyst comprising SO42−/TiO2–SiO2 for the production of biodiesel from several low cost feedstocks with high FFAs. They studied the influence of reaction parameters and found out that optimum yield could be attained at reaction temperature of 200 ℃, molar ratio of methanol to oil 9:1 and catalyst concentration of 3wt.%. They finally concluded that, the solid acid catalyst SO42−/TiO2–SiO2 is inexpensive and environment friendly, has high catalytic activity, and is stable for biodiesel production from cheap raw feedstocks with high FFAs.
In another study, Juan et al. [77] carried out transesterification of refined and crude vegetable oils with a sulfonic acid-modified mesostructured catalyst. According to them the catalyst could enable to yield fatty acid methyl ester (FAME) with purity over 95 wt.% and oil conversion close to 100% under best reaction conditions of temperature 180 ℃, methanol/oil molar ratio 10, and catalyst loading 6 wt. %. They reported that, regardless of the presence of free fatty acids, the sulfonic acid-modified mesostructured catalyst showed high activity towards simultaneous esterification and transesterification.
The other way of transesterification of oils and fats for biodiesel production is using enzymes in which there is no problem of saponification, purification, washing and neutralization so that it is always a preferred method from these perspectives. Enzymatic catalysts can also be applied on a feedstock with high FFA and can convert more of the oil into biodiesel. However, the problems associated with enzyme catalysts are their higher cost and longer reaction time [19]. Usually because of these two drawbacks, enzyme catalyzed transesterification method is not very frequently used.
In another view, it is more frequently pointed out that enzymatic transesterification has currently attracted much attention for biodiesel production as it produces high purity product (esters) and enables easy separation from the by-product, glycerol [26,78]. The enzymes that are usually found to be capable of catalyzing transesterification are the lipases.
The lipase catalyzed transesterification process is the reaction of a triglyceride (fat/oil) with an alcohol in the presence of lipase enzyme as a catalyst to form esters (biodiesel) and glycerol. Mahanta et al. [22] mentioned that, in a lipase catalyzed process no complex operations are needed not only for the recovery of glycerol but also in the elimination of catalyst and soap. This is an environmentally more attractive option to the conventional process. However, Mahanta et al. [22] again argued that the reaction yields as well as the reaction times are still unfavorable compared to the alkaline catalyzed reaction systems.
Lipases for their transesterification activity on different oils can be found from different sources. Ability to utilize all mono, di, and triglycerides as well as the free fatty acids, low product inhibition, high activity and yield in non-aqueous media, low reaction time, reusability of immobilized enzyme, temperature and alcohol resistance are the most desirable characteristics of lipases for transesterification of oils for biodiesel production [79].
Some also argue that, biocompatibility, biodegradability and environmental acceptability of the biotechnological procedure when using lipase as a catalyst are the desired properties in this alternative biodiesel production method [46,78]. However, the use of extracellular lipase as a catalyst requires complicated recovery, purification and immobilization processes for industrial application [80]. Consequently, the direct use of whole cell biocatalyst of intracellular lipases has received considerable research efforts [78]. For the industrial transesterification of fats and oils, Pseudomonas species immobilized with sodium alginate gel can be used directly as a whole cell bio-catalyst [78].
Devanesan et al. [78] reported maximum yield (72%) of biodiesel from transesterification of Jatropha oil and short chain alcohol (methanol on hexane) using Pseudomonas fluorescens immobilized with sodium alginate gel at the optimum conditions of 40 ℃, pH 7.0, molar ratio of 1:4, amount of beads of 3 g and reaction time of 48 h.
According to Parawira [32], in all the work in literature on lipases, the enzymes or whole cells are immobilized when used for catalysis. It is usually mentioned that, the advantage of immobilization is that the enzyme can be reused without separation. In addition, the operating temperature of the process is low (50 ℃) compared to other techniques which operate at harsh conditions. However, the cost of enzymes remains a barrier for its industrial implementation [81].
Most of the time, in order to tackle this cost barrier of the process, the enzyme (both intracellular and extracellular) should be reused by immobilizing in a suitable support particle, which is usually associated with considerable increase in efficiency.
Enzymes are usually immobilized for better enzyme loading, activity and stability. Selecting and designing the support matrix are important in enzyme immobilization [82]. With this respect, there are a number ways to immobilize enzymes. These include cross-linked enzyme aggregates, microwave-assisted immobilization, click chemistry technology, mesoporous supports and most recently nanoparticle-based immobilization of enzymes [83]. Recently, the use of nanoparticles has emerged as a versatile tool for generating excellent supports for enzyme stabilization due to their small size and large surface area [82], which results in better stability and activity of enzymes immobilized on such materials. In addition, Nanoparticles strongly influence the mechanical properties of the material like stiffness and elasticity and provide biocompatible environments for enzyme immobilization [82].
However, during transesterification, the activity of immobilized enzyme is inhibited by methanol and glycerol which are always present in the reacting mixture. The use of tert-butanol as solvent, continuous removal of glycerol, stepwise addition of methanol are some of the ways to reduce the inhibitory effects thereby increasing the cost effectiveness of the process [26].
Guang Jin et al. [81] examined the use of whole-cell biocatalysts to produce biodiesel at room temperature (25 ℃). They used Rhizopus oryzae (ATCC® 10260TM) to catalyze the conversion of virgin and waste oils (triglycerides) into biodiesel fuel in the presence of 15% water. Their research results indicated that the whole-cell biocatalyst could produce about a 90% yield of fatty acid methyl ester from virgin oil, and nearly complete conversion of the remaining oil into free fatty acid, using a 96-hour reaction at room temperature (25 ℃). They also reported that, in a 72 hour reaction, fatty acid methyl ester yields were about 75% for virgin oil, 80% for waste vegetable oil, and 55% for brown (trap) grease [81], which implies, whole-cell biocatalysts may be an effective way to trans esterify waste oils or greases that are high in FFA and difficult to dewater [81].
Du et al. [84] developed methyl acetate, a novel acyl acceptor, for biodiesel production and carried out a comparative study on Novozym 435 catalyzed transesterification of soybean oil for biodiesel production with different acyl acceptors. They reported that methanol has a serious negative effect on enzymatic activity as for example a molar ratio of methanol to oil of above 1:1 leads to serious inactivation of the enzyme. In their study, they used methyl acetate as the acyl acceptor, and reported that, a yield of 92% of methyl ester could be obtained with a molar ratio of methyl acetate to oil of 12:1, and methyl acetate showed no negative effect on enzymatic activity. They also mentioned that, with crude soybean oil as the oil source and methanol as acyl acceptor, a much lower methyl ester yield was obtained than that with refined soybean oil, while with methyl acetate as acyl acceptor, an equally high yield of methyl ester (92%) was achieved for both soybean oils. Lipase loses its activity very rapidly during repeated experiments with methanol as the acyl acceptor, however, according to their report, there was almost no detected loss in lipase activity, even after being continuously used for 100 batches, when methyl acetate was used for biodiesel production [84].
During enzymatic transesterification for biodiesel production, it has been demonstrated that excessive methanol present in the reaction medium would cause significant deactivation of the lipase. However, effective methanolysis using extracellular lipase has been reported to improve by stepwise addition of methanol (usually, a three-step addition of methanol in solvent-free medium) through which, according to Watanabea, 90–95% conversion can be achieved even after 50 and 100 cycles of repeated operation [85].
In another study, Li et al. [86] used tert-Butanol, as a novel reaction medium, for lipase-catalyzed transesterification of rapeseed oil for biodiesel production, with which, they claimed, both the negative effects caused by excessive methanol and by-product glycerol could be eliminated. They reported the highest biodiesel yield of 95% achieved under the optimum conditions of tert-butanol/oil volume ratio 1:1; methanol/oil molar ratio 4:1; 3% Lipozyme TL IM and 1% Novozym 435 based on the oil weight; temperature 35 ℃; 130 rpm, and 12 hours. According to them, there was no obvious loss in lipase activity even after being repeatedly used for 200 cycles with tert-butanol as the reaction medium [86].
Shah et al. [87] also worked on three different lipases (Chromobacterium viscosum, Candida rugosa, and Porcine pancreas) for a transesterification reaction of Jatropha oil in a solvent-free system to produce biodiesel. They reported that, only lipase from Chromobacterium viscosum was found to give appreciable yield. Immobilization of lipase (Chromobacterium viscosum) on Celite-545 enhanced the biodiesel yield to 71% from 62% yield obtained by using free tuned enzyme preparation with a process time of 8h at 40 ℃. Further addition of water to the free (1%, w/v) and immobilized (0.5%, w/v) enzyme preparations enhanced the yields to 73% and 92%, respectively. They mentioned also that, immobilized Chromobacterium viscosum lipase can be used for ethanolysis of oil. According to their conclusion immobilization of lipases and optimization of transesterification conditions resulted in adequate yield of biodiesel in the case of the enzyme-based process.
Some authors also argued that using convenient reaction medium would help increase conversion of oil to biodiesel in lipase-catalyzed transesterification reactions. In this respect, Ha et al. [88] demonstrated production of biodiesel through immobilized Candida antarctica lipase-catalyzed methanolysis of soybean oil in 23 different ionic liquids. They reported that, the highest fatty acid methyl esters (FAMEs) production after 12 h at 50 ℃ was achieved in EmimTfO (1-Ethyl-3-methylimidazolium trifluoromethanesulfonate). They also pointed out that around 15% higher free fatty acid production could be achieved using this ionic fluid as a reaction medium than the production system using tert-butanol as an additive. Table 6 summarizes results of some selected researches done to optimize production of biodiesel through lipase-catalyzed transesterification of different feedstock types.
Feedstock | Alcohol | Alcohol to oil Ratios | Enzymes | wt.% of Enzyme | Temp. (℃) | Stirring | Reaction time | Yield % | Remarks | Ref. |
Rapeseed oil | methanol with tert-butanol as a solvent | methanol/oil molar ratio 4:1 | Lipozyme TL IM | 3 wt.% | 35 | 130 rpm | 12 h | 95% | No loss in lipase activity after being repeatedly used for 200 cycles with tert-butanol | [86] |
Tert butanol/oil volume ratio 1:1 | Novozym 435 | as the reaction medium | ||||||||
Soybean oil | methanol | 1:1 | lipozyme TL | 0.04 | 40 | 150 rpm | - | 66% | - | [89] |
Soybean oil | methanol | 1:1 | silica gel | 0.06 | 40 | 150 rpm | - | 90% | Silica gel combined with lipozyme TL and three-step addition of methanol | [89] |
lipozyme TL | ||||||||||
Soyabean oil in ionic fluid-EmimTfO | methanol | 4:1 | Novozym 435 Pseudomonas cepacia immobilized on celite | 2 wt.% 0.1 | 50 | 250 rpm | 12 h | 80% | High production yield in ionic liquids show that ionic liquids are potential reaction media for biodiesel production | [88] |
Jatropha oil | ethanol | 4:1 | 50 | 200 rpm | 8 h | 98% | With presence of 4–5% (w/w) water | [90] |
According to Marchetti et al. [46], the use of lipase is a great viable method for production of ester from different sources of oil or grease even though, research on this topic is still in progress due to the enzyme flexibility and adaptability to new process.
However, when we compare enzymatic production of biodiesel with conventional chemical processes, the major obstacles repeatedly mentioned are the cost of lipases, the relatively slower reaction rate and lipases inactivation caused by methanol and glycerol. Some main advantages and disadvantages of using lipases as catalyst are summarized in Table 7.
The advantages of using lipases |
✔ Biocompatible, biodegradable and environmental acceptability ✔ Possibility of regeneration and reuse of the immobilized residue, because it can be left in the reactor if one keep the reactive flow ✔ Use of enzymes in reactors allows use of high concentration of them and that makes for a longer activation of the lipases ✔ Immobilization of lipase could protect it from the solvent that could be used in the reaction and that will prevent all enzyme particles getting together ✔ Separation of product will be easier using this catalyst, producing product of very high purity with less or no downstream operations |
Some disadvantages |
✔ Loss of some initial activity due to volume of the oil molecule ✔ Number of support enzyme is not uniform ✔ More expensive |
In general, process optimization in lipase-catalyzed transesterification, can be done at least in the following: screening of various commercial lipase preparations; pH tuning; immobilization; adjusting water content in the reaction media; adjusting amount of enzyme used; and adjusting temperature of the reaction [90].
There a number of recent developments in catalytic conversion of oils and fats to biodiesel. Among them biodiesel production using Nano catalyst and Ionic liquid catalysts are more promising in terms of few advantages over the conventional acid/base catalysts.
Nano catalysis involves the use of nanomaterials as catalysts for a variety of homogeneous and heterogeneous catalysis applications. Nanoscale catalysts have high specific surface area and surface energy resulting in high catalytic activity. Generally, Nano catalysts improve the selectivity of the reactions by allowing reaction at a lower temperature, reducing the occurrence of side reactions, higher recycling rates and recovery of energy consumption [91]. With this respect, Nano catalysts are promising alternatives for efficient production of biodiesel from oils and fats as they have high specific surface area and high catalysis activities eliminating the specific problem of mass transfer resistance associated with conventional catalysts.
Wen et al. [92] studied that the solid base Nano catalyst KF/CaO can be used for biodiesel production with yield of more than 96%. This catalyst can efficiently be used to convert the oil with higher acid value into biodiesel [92,93]. It is porous with particle sizes of 30–100 nm. Wen et al. [92] could show, using X-ray powder diffraction analysis, that the Nano catalyst KF/CaO has new crystal KCaF3, which increases catalytic activity and stability. The high specific surface area and large pore size are favorable for contact between catalyst and substrates, which effectively improve efficiency of transesterification [93].
Few have studied on the possible optimum conditions for production of biodiesel from different oil inputs using different Nano catalysts. Sidra et al. [94] investigated the production of biodiesel from Jatropha oil through transesterification process by using CaO-Al2O3 Nano catalyst. According to them, the optimization results for production of biodiesel from the transesterification of Jatropha curcas oil catalyzed by CaO-Al2O3 nanoparticles showed maximum yield of 82.3% at 5:1 methanol to oil molar ratio [94]. Similarly, Sivakumar et al. [95] did comprehensive study of smoke deposited Nano sized MgO as a catalyst for biodiesel production. They studied the transesterification reaction to determine the optimum conditions for different parameters like catalyst quantity, methanol oil molar ratio, reaction temperature and reaction time. A maximum conversion of 98.7% was obtained at 1.5 wt.% catalyst; 5:1 methanol oil molar ratio at 55 ℃, achieved after 45 min. The conversion was three to five times higher than those reported for laboratory MgO in literature [95]. According to this study, the higher conversion was mainly due to the enhancement of surface area of the catalyst. The other advantage is that the catalyst can be easily recovered and reused up to eight times with easy regeneration steps [95]. Table 8 shows some of optimization studies on biodiesel production using Nano catalysts.
Feedstock | Alcohol | Alcohol to oil Ratios | Nano catalyst | wt.% of catalyst | Temp. (℃) | Reaction time | Yield % | Remarks | Ref. |
Waste mixed vegetable oil | Methanol | 5:1 | smoke deposited nano sized MgO | 1.5 | 55 | 45 min | 98.7 | The transesterification reaction was studied under constant ultrasonic mixing for different parameters | [95] |
Stillingia oil | Methanol | 12:1 | KF/CaO–Fe3O4 (Calcinated at 600 ℃) | 4 | 65 | 3 h | 95 | The catalyst is able to be reused up to 14 times without much deterioration in its activity | [99] |
Chinese tallow seed oil | Methanol | 12:1 | KF/CaO | 4 | 65 | 2.5 h | 96.8 | - | [92] |
Waste cooking oil | 7:1 | Nano CaO | 1.5 | 75 | 6 h | 94.37 | - | [100] | |
Waste cooking oil | 7:1 | Mixture of Nano CaO and Nano MgO | 3 | 75 | 6 h | 98.95 | The optimum mass proportion for CaO to MgO is 0.7:0.5 | [100] | |
Soybean oil | 12:1 | Nanoparticle of CaO from calcium Nitrate (CaO/CaN) | 8 | 65 | 6 h | 93 | - | [98] | |
Soybean oil | 12:1 | Nanoparticle of CaO from Snail shell (CaO/SS) | 8 | 65 | 6 h | 96 | - | [98] |
In another two separate studies Mookan et al. [96,97] conducted an investigation on the fuel quality of biodiesel produced from castor oil as well as Pongamia pinnata oil with methanol using iron nanoparticles as catalyst. The fuels properties that they investigated are specific gravity, kinematic viscosity, flash point, cloud point, water content, carbon residue, refractive index, copper corrosion and calorific value. They pointed out that, these properties of resulting biodiesel both from castor oil and Pongamia pinnata oil agree well with the specifications of biodiesel standards ASTM D6751 except for specific gravity and kinematic viscosity. According to them, most of the physico-chemical properties of castor oil biodiesel match well with the normal diesel. They also concluded that the use of iron nanoparticles as catalyst showed more advantages than the conventional acid/base catalyst for the production of biodiesel in terms of shorter reaction time as well as less amount and reusability of the catalyst.
More recently, Gupta et al. [98] did a research on the preparation and characterization of CaO nanoparticle for biodiesel production from Soybean oil. They synthesized Nanoparticle of CaO from calcium Nitrate (CaO/CaN) and Snail shell (CaO/SS) so as to investigate the performance of the catalysts in terms of biodiesel yield. According to their conclusion, the Nano catalyst from snail shell exhibits excellent catalytic activity and stability for the transesterification reaction, which suggested that this catalyst would be potentially used as a solid base Nano catalyst for biodiesel production [98].
The catalytic activity of such Nano catalysts are usually affected by calcination temperature during catalyst preparation with calcination. This is because in the preparation process of the catalyst, calcination treatment of catalyst at high temperature is favorable for the interaction between support and active ingredient, which generates new active sites for the catalyst [99]. With this respect Hu et al. [99], did an investigation on the optimum calcination temperature for the preparation of three Nano catalysts, KF/CaO–Fe3O4, KF/SrO–Fe3O4 and KF/MgO–Fe3O4. And they found out that the fatty acid methayl ester yield reaches the maximum value at calcination temperature of 600 ℃, 600 ℃, and 500 ℃ for KF/CaO–Fe3O4, KF/SrO–Fe3O4 and KF/MgO–Fe3O4, respectively [99]. Thus, calcination temperature can be taken as additional parameter to optimize biodiesel production using Nano catalysts prepared through calcination.
Ionic liquids are organic salts comprising of anions and cations that are liquid at room temperature. The cations are responsible for the physical properties of ionic liquids (such as melting point, viscosity and density), while the anion controls its chemical properties and reactivity [101]. Their unique advantage is that while synthesized, they can be moderated to suit required reaction conditions.
Another great advantage of using Ionic Liquids specifically to catalyze transesterification for biodiesel production is the formation of a biphasic system at the end of the reaction. This biphasic system occurs because the ionic liquid, insoluble in the organic phase, remains in the aqueous phase along with alcohol, the catalyst used and glycerol produced during the reaction [102]. This makes it very easy to separate the final products, because most of the top phase is biodiesel with very little amount of methanol. Pure biodiesel can then be isolated by simple vacuum evacuating of this very little amount of methanol [103]. The bottom phase contains methanol, glycerol and Ionic Liquids. This bottom phase can then be rinsed with water for 3 to 4 cycles to separate glycerol with high purity [104], or pure glycerol can be obtained simply by distillation [103], which leaves the pure Ionic Liquid behind for further direct use for another reaction.
Among the different possible types of ionic liquids for catalysis of transesterification reaction for biodiesel production, Ionic liquids composed of the 1-n-butyl-3-methylimidazolium cation are the most widely studied and discussed compounds [105].
Very few researches are done to investigate the optimum reaction conditions for ionic liquid catalyzed transesterification with respect to temperature, molar ratio, catalyst amount, etc. Guo et al. [106] did a research to find out such optimum conditions for ionic liquid catalyzed transesterification of soybean oil with methanol by using ultrasound (24 kHz, 80 W). They found out that, at 60 ℃ under ultrasonic irradiation and a molar ratio of 14:1 methanol to oil, a biodiesel yield in excess of 96% can be achieved in a remarkably short time duration of 20 minutes or less in comparison to 5h or more using conventional method. They concluded that ionic liquid catalyzed transesterification is proved to be efficient and time saving for the preparation of biodiesel from soybean oil. They also mentioned the ionic liquid had a good reusability and can be easily separated from the biodiesel by simple decantation [106].
In another study, Ren et al. [103] investigated the influence of some reaction conditions, such as the amount of morpholine alkaline basic ionic liquid 1-butyl-3-methyl morpholine hydroxide ([Hnmm]OH) as a catalyst, the molar ratio of methanol to soybean oil, reaction temperature and time. The optimum reaction conditions to get the maximum biodiesel yield (97.0%) were found as 4% (mass fraction) of [Hnmm]OH, the methanol to soybean oil molar ratio of 8, temperature of 70 ℃ and reaction time of 1.5 hours. They pointed out that, the reaction exhibited high stability upon recycling, and the biodiesel yield remained more than 90% even after being reused for five times [103]. Table 9 shows the results of some few researches done on optimized reaction conditions for ionic liquid catalyzed transesterification.
Feedstock | Alcohol | Alcohol to oil Ratios | Ionic liquid catalyst | Wt.% of catalyst | Temp. (℃) | Reaction time | Yield % | Remarks | Ref. |
Soybean oil | Methanol | 8:1 | Basic Ionic Liquids [Hnmm]OH | 4 | 70 | 1.5 h | 97 | The catalytic activity was affected by its alkalinity | [103] |
Cottonseed Oil | Methanol | 12:1 | 1-(4-Sulfonic acid) butylpyridinium hydrogen sulfate | 0.057 a | 170 | 5 h | 92 | The catalytic activity of the ionic liquid is dependent on its Brønsted acidic strength. | [107] |
Rapeseed oil | Methanol | 10:1 | 1-propyl-3-methyl imidazolium hydrogen sulfate ([PrMIM][HSO4]) | 10 | 140 | 5 h | 19.74 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-propylsulfonate-3methyl imidazolium hydrogen sulfate ([PrSO3HMIM][HSO4]) | 10 | 130 | 5 h | 94.91 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]) | 10 | 110 | 5 h | 8.89 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-butylsulfonate-3-methyl imidazolium hydrogen sulfate ([BSO3HMIM][HSO4]) | 10 | 130 | 5 h | 100 | - | [108] |
a molar ratio of ionic liquid to oil |
One of the approaches to overcome problems associated with poor immiscibility between the reactants and at the same time, technical problems caused by catalysts is to use supercritical method. Supercritical alcohol transesterification reaction takes place under extremely high temperature and pressure. When a gas or liquid is under high pressure and temperature beyond its critical point, unusual phenomena are exhibited on its properties. In this case, liquid and vapor phase are no longer confined under these conditions and single supercritical fluid phase is generated [19]. In the supercritical transesterification method, methanol and oil, which are immiscible liquids at room temperature, will form a homogenous fluid. This is due to the sharp drop in the solubility of methanol and reduction in dielectric constant, which makes methanol a non-polar substance [19]. In this case, the reaction will be accelerated, as there is no mass transfer limitation under such conditions.
When we consider specific application of the mothed for biodiesel production, super critical methanol is usually used to speed up the transesterification reaction. Using this technique, the conversion of vegetable oils into biodiesel is done in about 4 min but extremely high pressure and temperature is required for this method, which makes it highly sensitive and costly [9]. A lot of energy is required to build such a high pressure and temperature. Some authors recommend use of co-solvent to improve the conversion efficiency.
The simple chemical catalyzed transesterification processes mentioned above (Acid catalyzed and Base catalyzed) are confronted with two problems, i.e. the processes are relatively time consuming and need separation of the catalyst and saponified impurities from the biodiesel. The first problem is due to the phase separation of the oil/alcohol mixture, which can be alleviated by vigorous stirring. These problems are totally mislaid in the supercritical method of transesterification. This is perhaps due to the fact that the tendency of two phase formation of vegetable oil/alcohol mixture is not encountered and a single phase is found due to decrease in the dielectric constant of alcohol in the supercritical state [9]. In general, the supercritical methanol process, which is non-catalytic, is simpler in purification, takes lower reaction time and lower energy use than the common commercial process[16,51].
It is argued that supercritical transesterification, as an alternative technology, satisfies all the requirements to produce biodiesel suitable to be used on normal engines. In addition, it produces more than a kilo of fuel per kilo of oils used [40]. According to a study done by Marchetti et al. [109], the techno-economic analysis of the supercritical process shows that, although the supercritical alternative appears as a good technical possibility to produce biodiesel, today, it is not an economic alternative due to its high operating cost. However, there is still a possibility in reducing the operating cost and making the method more economically advantageous too. Kasteren and Nisworo [110] have proved this by using one reaction step in the process as well as propane as a co-solvent in supercritical biodiesel production plant so as to decrease operating cost.
In another view, Atabania et al. [111] pointed out that, supercritical methanol method uses lower energy and completes in a very short time (2–4 minutes) compared to catalytic transesterification. According to them, since no catalyst is used, the purification of biodiesel and the recovery of glycerol are much easier, trouble free and environment friendly. However, the method has a high cost in reactor and operation (due to high pressures and high temperatures), and high methanol consumption (e.g., high methanol/crude-oil molar ratio of 40/1) [9].
Similarly, Marulanda [13] carried out a lab scale experiment on biodiesel production process by supercritical transesterification in a continuous reactor working at a 9:1 methanol to triglycerides molar ratio and 400 ℃. The results of this study showed that for a specified biodiesel production plant capacity set at 10, 000 tons/year the total energy consumption of this specific process (573 kW) was considerably lower than another supercritical process working at a 42:1 molar ratio and 300 ℃ (2407 kW), and the conventional base catalyzed process (2326 kW).
Different studies done on investigation of optimum condition for supercritical transesterification process agree that among the determinant variables temperature has the highest impact on yields, followed by reaction time and pressure. Kiss et al. [112] have done a series of experiments with ethyl alcohol to the effect of temperature, time and pressure. They found that, by increasing the reaction time at 350 ℃ and 12 MPa, yield increases during the whole range (from 63.36% to 93.22%). After reduction of pressure at 350 ℃ temperature, the maximum yield (80.1%) was reached within 30 min. They concluded that, in general, lowering the pressure would result in yield decrease. By reducing the reaction temperature (350–250 ℃), the yield decreases which can in general be compensated with prolonging the duration of reaction. They attained lowest yield at a minimum temperature, minimum pressure and short reaction time (250 ℃, 8 MPa, 7 min; the yield is 14.8%) [112]. Table 8 summarizes the results of some selected researches done on optimization of reaction conditions for supercritical transesterification of different feedstock types.
Feedstock | Alcohol | Process variables | Methyl ester % | Ref | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time (min) | Stirring speed (rpm) | Pressure (MPa) | |||||
Refined lard | Methanol | 45:1 | 335 | 15 | 500 | 20 | 89.91% | [14] | |
Rapeseed oil | Methanol | 45:1 | 350 | 4 | - | 14 | 95% | [113] | |
Coconut oil | Methanol | 42:1 | 350 | 7 | - | 19 | 95% | [114] | |
Palm kernel oil | Methanol | 42:1 | 350 | 7 | - | 19 | 96% | [114] | |
Rapeseed oil | Methanol | 42:1 | 350 | 15 | - | 12 | 93% | [115] | |
Rapeseed oil | Ethanol | 42:1 | 350 | 20 | - | 12 | 91.9% | [115] | |
Rapeseed oil | 1-propanol | 42:1 | 350 | 25 | - | 12 | 91.1% | [115] | |
Jatropha oil | Methanol | 43:1 | 320 | 4 | - | 8.4 | 100% | [116] | |
Sunflower seed oil | Methanol | 41:1 | 252 | 20 | - | 24 | 95% | [117] | |
Sunflower seed oil | Methanol with 0.3% CaO | 41:1 | 252 | 17 | - | 24 | 95% | [117] | |
Sunflower seed oil | Methanol with 5% CaO | 41:1 | 252 | 13 | - | 24 | 100% | [117] | |
RBDaPalm oil | Methanol | 45:1 | 350 | 5 | - | 40 | 95% | [118] | |
Vegetable oil | Ethanol with C2O Co-solvent | 25:1 | 200 | 6 | - | 20 | 80% | [119] | |
a Refined, Bleached and Deodorized |
As it has been tried to clearly put in the different research works reviewed in this paper, the different transesterification techniques do have their own advantages and disadvantages. These advantages and disadvantages can be seen with respect to cost of input material, degree of waste generation, cost of production, product purity, yield percentage, environmental and health hazard and the like. Table 9 shows a summary on advantages and disadvantages of these major transesterification techniques as well as required character of suitable feedstock for each method.
Transesterification method | Suitable feedstock character | Advantages | Disadvantages | Ref |
Homogeneous Acid catalyzed | Any type of oil/fat feedstock including those with high free fatty acid. | ✔ Gives relatively high yield ✔ Insensitive to FFA content in feedstock, thus preferred-method if low-grade feedstock is used ✔ Esterification and transesterification occur simultaneously ✔ Less energy intensive |
✖ Corrosiveness of acids damage equipment ✖ More amount of free glycerol in the biodiesel ✖ Requires higher temperature operation but less than supercritical ✖ Relatively difficult to separation of catalyst from product. ✖ Has slower rate of production (relatively takes longer time) |
[22,40,43,44,120] |
Homogeneous Base catalyzed | Oil/fat feedstock with FFA content less than 0.5% by weight of the oil | ✔ Faster reaction rate than acid catalyzed transesterification ✔ Reaction can occur at mild reaction condition and less energy intensive ✔ Common catalysts such as NaOH and KOH are relatively cheap and widely available ✔ less corrosive |
✖ Sensitive to FFA content in the oil ✖ Saponification of oil is the main problem due to quality of feedstock ✖ Recovery of glycerol is difficult, ✖ Alkaline wastewater ✖ generated requires treatment |
[19,32,46,48,52,120] |
Heterogeneous Base Catalysis | Oil/fat feedstock with FFA content less than 0.5% by weight of the oil | ✔ Improved selectivity ✔ Easy to separate catalyst from reaction mixture ✔ Reduced process stages and wastes ✔ Enable to regenerate and reuse the catalyst ✔ Reaction can occur at mild reaction condition and less energy intensive |
✖ Catalyst might be poisoned when exposed to ambient air ✖ Sensitive to FFA content in the oil so selective to feedstock type ✖ Soap will be formed if there is high FFA content ✖ Soap formation associated with reduced biodiesel yield and problem in product purification ✖ Leaching of catalyst active sites may result to product contamination |
[32,66,69,71,120] |
Heterogeneous Acid Catalysis | Any type of oil/fat feedstock including those with high free fatty acid. | ✔ Catalyst separation from reaction mixture is easy ✔ Has reduced process stages and wastes ✔ Insensitive to feedstocks' FFA content. ✔ Preferred-method if low-grade oil is used ✔ Esterification and transesterification occur simultaneously ✔ Solid acid catalyst can be easily removed recycled |
✖ Complicated catalyst synthesis procedures lead to higher cost ✖ Requires high reaction temperature, high alcohol to oil molar ratio and long reaction time. ✖ Relatively energy intensive |
[69,75,76,120] |
Lipase catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content. | ✔ Insensitive to FFA and water content in the oil, thus preferred when low grade feedstock is used ✔ It is carried out at low reaction temperature ✔ Purification requires simple step, by enabling easy separation from the by-product, glycerol ✔ Gives high purity product (esters) ✔ Enables to reuse immobilized enzyme |
✖ The cost of enzyme is usually very high ✖ Gives relatively low yield ✖ It takes high reaction time ✖ The problem of lipases inactivation caused by methanol and glycerol |
[19,22,26,46,78,79,120] |
Nano catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content | ✔ Relatively with shorter reaction time ✔ Less amount of catalyst can be enough since has high specific surface area ✔ Catalyst can be reused many times ✔ Wide range of catalyst choice |
✖ Requires relatively more alcohol for effective yield ✖ In some cases preparation of appropriate catalysts costs more |
[91,92,93,94,95,96,97] |
Ionic liquid catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content but dependent on which type of ionic liquid is used (Acidic/basic) | ✔ Easy to separate final products due to formation of biphasic. ✔ Efficient and time saving ✔ While preparing catalysts their properties can be designed to suit a particular need ✔ Catalyst can be easily separated and reused many times ✔ High catalytic activity, excellent stability |
✖ High cost of ionic liquid production ✖ Requires relatively more alcohol for effective yield |
[101,102,103,104,105,106] |
Supercritical transesterification | Any oil and fat with greater range and water content and high FFA content (in particular, used cooking oil) | ✔ It takes very less time to complete ✔ Insensitive to greater water content of the feedstocks ✔ Produces more than a kilo of fuel per kilo of feedstock ✔ No need of washing the product as there is no catalyst used ✔ It is more easier to design as a continuous process |
✖ Requires higher temperature and pressure ✖ It is not an economic alternative due to its high operating cost, due to high pressures and high ✖ temperatures ✖ Relatively there is high methanol consumption (e.g., high methanol/crude-oil molar ratio of 40/1) |
[9,40,111,112,115,118,119] |
Even though biodiesel is a good alternative over petroleum diesel in various aspects, it is always jeopardized by the high cost of feedstock and absence of economically and technically viable technology for its efficient production from any feedstock type.
Different researchers recommend different methods of biodiesel production, which are usually dependent on properties of the feedstock. Among the methods to change fat and oil to biodiesel, the most convenient one is the transesterification or also called alcoholysis reaction. There are a number of techniques used to carry out transesterification of fat/oil for biodiesel production, each of which requiring specific feedstock property and optimum operating condition for efficient production of biodiesel.
From the review of different works, it can be concluded that:
(1) Homogenous acid catalyzed transesterification is relatively insensitive to FFA content of the feedstock, is relatively less energy intensive but requires higher temperature operation and the biodiesel produced usually has more amount of free glycerol (low purity percentage).
(2) Homogeneous base catalyzed transesterification is very sensitive to FFA and water content and thus is very selective in feedstock type. The reaction is fast, the catalysts are relatively cheap, and thus it is usually applied at industrial scale for biodiesel production.
(3) Heterogeneous acid catalyzed transesterification avoids the problem of product separation and purification and enable reuse of the catalyst. However, it relatively requires high alcohol to oil molar ratio and long reaction time.
(4) Heterogeneous base catalyzed transesterification reduces process stages and wastes, and enables easy catalyst separation and reuse. However, catalyst might possibly be poisoned when exposed to ambient air so that not environmentally friendly.
(5) Lipase catalyzed transesterification is insensitive to FFA and water content, carried out at low temperature, and convert more amount of the feedstock to biodiesel. Nevertheless, it is costly due to expensiveness of the enzymes and takes longer time to have good yield.
(6) Nano catalyzed transesterification is insensitive to FFA and water content, carried out relatively at low temperature and takes short time. The catalyst can be reused many times providing cost benefits. However, it requires more alcohol for effective yield and in some cases preparation of appropriate catalysts is expensive.
(7) Ionic Liquids catalyzed transesterification enables easy separation of final products due to formation of biphasic thus reducing process cost and be efficient and time saving. In addition, it enables modulating desired properties of catalysts while preparing them. Catalysts have high catalytic activity, excellent stability and can also be easily separated and reused many times. However it requires relatively more alcohol for effective yield and usually expensive to have ionic liquids.
(8) Supercritical transesterification is insensitive to FFA and water content of feedstock and thus enable to use wider feedstock types, usually takes shorter time and produces more fuel amount per feedstock mass. However, it requires higher temperature and pressure and consumes more methanol so that it is not economically profitable due to its high operating cost.
The authors would like to thank Norwegian University of Life Sciences, NORAD and NORHED for their financial support.
All authors declare no conflicts of interest in this paper.
[1] | Banks S, Dinges DF (2007) Behavioral and physiological consequences of sleep restriction. J Clin Sleep Med 3: 519-528. |
[2] | Van Dongen HP, Maislin G, Mullington JM, et al. (2003) The cumulative cost of additional wakefulness: dose-response effects on neurobehavioral functions and sleep physiology from chronic sleep restriction and total sleep deprivation. Sleep 26: 117-126. |
[3] |
Knutson KL, Spiegel K, Penev P, et al. (2007) The metabolic consequences of sleep deprivation. Sleep Med Rev 11: 163-178. doi: 10.1016/j.smrv.2007.01.002
![]() |
[4] |
Dixit A, Mittal T (2015) Executive Functions are not Affected by 24 Hours of Sleep Deprivation: A Color-Word Stroop Task Study. Indian J Psychol Med 37: 165-168. doi: 10.4103/0253-7176.155615
![]() |
[5] |
Mignot E (2008) Why we sleep: the temporal organization of recovery. PLoS Biol 6: e106. doi: 10.1371/journal.pbio.0060106
![]() |
[6] |
McCormick DA, Bal T (1997) Sleep and arousal: thalamocortical mechanisms. Annu Rev Neurosci 20: 185-215. doi: 10.1146/annurev.neuro.20.1.185
![]() |
[7] |
Pace-Schott EF, Hobson JA (2002) The neurobiology of sleep: genetics, cellular physiology and subcortical networks. Nat Rev Neurosci 3: 591-605. doi: 10.1038/nrn895
![]() |
[8] |
Villablanca JR (2004) Counterpointing the functional role of the forebrain and of the brainstem in the control of the sleep-waking system. J Sleep Res 13: 179-208. doi: 10.1111/j.1365-2869.2004.00412.x
![]() |
[9] | Krueger J CL, Rector D (2009) Cytokines and other neuromodulators. Stickgold R, Walker M (eds) The neuroscience of sleep. |
[10] | Porkka-Heiskanen T (2011) Methylxanthines and sleep. Fredholm BB (ed) Methylxanthines, handbook of experimental pharmacology 331-348. |
[11] |
Krueger JM, Rector DM, Roy S, et al. (2008) Sleep as a fundamental property of neuronal assemblies. Nat Rev Neurosci 9: 910-919. doi: 10.1038/nrn2521
![]() |
[12] |
Vyazovskiy VV, Olcese U, Hanlon EC, et al. (2011) Local sleep in awake rats. Nature 472: 443-447. doi: 10.1038/nature10009
![]() |
[13] |
Llinas RR, Steriade M (2006) Bursting of thalamic neurons and states of vigilance. J Neurophysiol 95: 3297-3308. doi: 10.1152/jn.00166.2006
![]() |
[14] |
Coulon P, Budde T, Pape HC (2012) The sleep relay--the role of the thalamus in central and decentral sleep regulation. Pflugers Arch 463: 53-71. doi: 10.1007/s00424-011-1014-6
![]() |
[15] | Steriade M MR (1990) Brainstem control of wakefulness and sleep. Plenum, New York. |
[16] |
Haas HL L, JS (2012) Waking with the hypothalamus. Pflugers Arch 463: 31-42. doi: 10.1007/s00424-011-0996-4
![]() |
[17] |
Basheer R SR, Thakkar MM, McCarley RW (2004) Adenosine and sleep-wake regulation. Progr Neurobiol 73: 379-396. doi: 10.1016/j.pneurobio.2004.06.004
![]() |
[18] |
Obal F, Jr., Krueger JM (2003) Biochemical regulation of non-rapid-eye-movement sleep. Front Biosci 8: d520-550. doi: 10.2741/1033
![]() |
[19] |
De Sarro G, Gareri P, Sinopoli VA, et al. (1997) Comparative, behavioural and electrocortical effects of tumor necrosis factor-alpha and interleukin-1 microinjected into the locus coeruleus of rat. Life Sci 60: 555-564. doi: 10.1016/S0024-3205(96)00692-3
![]() |
[20] |
Manfridi A, Brambilla D, Bianchi S, et al. (2003) Interleukin-1beta enhances non-rapid eye movement sleep when microinjected into the dorsal raphe nucleus and inhibits serotonergic neurons in vitro. Eur J Neurosci 18: 1041-1049. doi: 10.1046/j.1460-9568.2003.02836.x
![]() |
[21] |
De A, Churchill L, Obal F, Jr., et al. (2002) GHRH and IL1beta increase cytoplasmic Ca(2+) levels in cultured hypothalamic GABAergic neurons. Brain Res 949: 209-212. doi: 10.1016/S0006-8993(02)03157-8
![]() |
[22] | Huber R, Tononi G, Cirelli C (2007) Exploratory behavior, cortical BDNF expression, and sleep homeostasis. Sleep 30: 129-139. |
[23] |
Porkka-Heiskanen T, Alanko L, Kalinchuk A, et al. (2002) Adenosine and sleep. Sleep Med Rev 6: 321-332. doi: 10.1053/smrv.2001.0201
![]() |
[24] |
Oishi Y, Huang ZL, Fredholm BB, et al. (2008) Adenosine in the tuberomammillary nucleus inhibits the histaminergic system via A1 receptors and promotes non-rapid eye movement sleep. Proc Natl Acad Sci U S A 105: 19992-19997. doi: 10.1073/pnas.0810926105
![]() |
[25] | Rosenberg PA, Li Y, Le M, et al. (2000) Nitric oxide-stimulated increase in extracellular adenosine accumulation in rat forebrain neurons in culture is associated with ATP hydrolysis and inhibition of adenosine kinase activity. J Neurosci 20: 6294-6301. |
[26] |
MM H (2011) Thalamocortical dynamics of sleep: roles of purinergic neuromodulation. Semin Cell Dev Biol 22: 245-251. doi: 10.1016/j.semcdb.2011.02.008
![]() |
[27] |
Steriade M, McCormick DA, Sejnowski TJ (1993) Thalamocortical oscillations in the sleeping and aroused brain. Science 262: 679-685. doi: 10.1126/science.8235588
![]() |
[28] |
Brown RE, Basheer R, McKenna JT, et al. (2012) Control of sleep and wakefulness. Physiol Rev 92: 1087-1187. doi: 10.1152/physrev.00032.2011
![]() |
[29] | Rechtschaffen A KA (1968) A manual of Standardized Terminology, Techniques and Scoring System for Sleep Stages of Human Subjects. National Institue of Health Publication Washington, DC: NIH US Goverment Printing Office |
[30] |
Jeanneret PR, Webb WB (1963) Strength of grip on arousal from full night's sleep. Percept Mot Skills 17: 759-761. doi: 10.2466/pms.1963.17.3.759
![]() |
[31] |
Tassi P, Muzet A (2000) Sleep inertia. Sleep Med Rev 4: 341-353. doi: 10.1053/smrv.2000.0098
![]() |
[32] | Klemm WR (2011) Why does rem sleep occur? A wake-up hypothesis. Front Syst Neurosci 5: 73. |
[33] |
Roffwarg HP, Muzio JN, Dement WC (1966) Ontogenetic development of the human sleep-dream cycle. Science 152: 604-619. doi: 10.1126/science.152.3722.604
![]() |
[34] | Endo T, Roth C, Landolt HP, et al. (1998) Selective REM sleep deprivation in humans: effects on sleep and sleep EEG. Am J Physiol 274: R1186-1194. |
[35] | Barone DA, Krieger AC (2014) Muscle Tone Control of REM Sleep. REM Sleep: Characteristics, Disorders, and Physiological Effects / Editor: Chelsea L Saylor |
[36] |
Kamphuis J, Lancel M, Koolhaas JM, et al. (2015) Deep sleep after social stress: NREM sleep slow-wave activity is enhanced in both winners and losers of a conflict. Brain Behav Immun 47:149-54. doi: 10.1016/j.bbi.2014.12.022
![]() |
[37] |
Benington JH, Heller HC (1995) Restoration of brain energy metabolism as the function of sleep. Prog Neurobiol 45: 347-360. doi: 10.1016/0301-0082(94)00057-O
![]() |
[38] | H. Blake RWG (1937) Brain potentials during sleep. Am J Physiol 119 692-703. |
[39] | Friedman L, Bergmann BM, Rechtschaffen A (1979) Effects of sleep deprivation on sleepiness, sleep intensity, and subsequent sleep in the rat. Sleep 1: 369-391. |
[40] |
Tobler I, Borbely AA (1986) Sleep EEG in the rat as a function of prior waking. Electroencephalogr Clin Neurophysiol 64: 74-76. doi: 10.1016/0013-4694(86)90044-1
![]() |
[41] |
Dijk DJ, Beersma DG, Daan S (1987) EEG power density during nap sleep: reflection of an hourglass measuring the duration of prior wakefulness. J Biol Rhythms 2: 207-219. doi: 10.1177/074873048700200304
![]() |
[42] |
Franken P, Tobler I, Borbely AA (1991) Sleep homeostasis in the rat: simulation of the time course of EEG slow-wave activity. Neurosci Lett 130: 141-144. doi: 10.1016/0304-3940(91)90382-4
![]() |
[43] |
Lancel M, van Riezen H, Glatt A (1992) The time course of sigma activity and slow-wave activity during NREMS in cortical and thalamic EEG of the cat during baseline and after 12 hours of wakefulness. Brain Res 596: 285-295. doi: 10.1016/0006-8993(92)91559-W
![]() |
[44] |
Huber R, Deboer T, Tobler I (2000) Effects of sleep deprivation on sleep and sleep EEG in three mouse strains: empirical data and simulations. Brain Res 857: 8-19. doi: 10.1016/S0006-8993(99)02248-9
![]() |
[45] | Sanchez-Vives MV, Mattia M (2014) Slow wave activity as the default mode of the cerebral cortex. Arch Ital Biol 152: 147-155. |
[46] |
Meerlo P, Pragt BJ, Daan S (1997) Social stress induces high intensity sleep in rats. Neurosci Lett 225: 41-44. doi: 10.1016/S0304-3940(97)00180-8
![]() |
[47] |
Meerlo P, de Bruin EA, Strijkstra AM, et al. (2001) A social conflict increases EEG slow-wave activity during subsequent sleep. Physiol Behav 73: 331-335. doi: 10.1016/S0031-9384(01)00451-6
![]() |
[48] |
Berger RJ, Phillips NH (1995) Energy conservation and sleep. Behav Brain Res 69: 65-73. doi: 10.1016/0166-4328(95)00002-B
![]() |
[49] |
Berger RJ (1984) Slow wave sleep, shallow torpor and hibernation: homologous states of diminished metabolism and body temperature. Biol Psychol 19: 305-326. doi: 10.1016/0301-0511(84)90045-0
![]() |
[50] |
Siegel JM (2009) Sleep viewed as a state of adaptive inactivity. Nat Rev Neurosci 10: 747-753. doi: 10.1038/nrn2697
![]() |
[51] |
Rechtschaffen A (1998) Current perspectives on the function of sleep. Perspect Biol Med 41: 359-390. doi: 10.1353/pbm.1998.0051
![]() |
[52] |
Zepelin H, Rechtschaffen A (1974) Mammalian sleep, longevity, and energy metabolism. Brain Behav Evol 10: 425-470. doi: 10.1159/000124330
![]() |
[53] | Horne J (2002) Why sleep? Biologist (London) 49: 213-216. |
[54] | Schmidt MH (2014) The energy allocation function of sleep: A unifying theory of sleep, torpor, and continuous wakefulness. Neurosci Biobehav Rev 47c: 122-153. |
[55] |
Adam K (1980) Sleep as a restorative process and a theory to explain why. Prog Brain Res 53: 289-305. doi: 10.1016/S0079-6123(08)60070-9
![]() |
[56] |
Oswald I (1980) Sleep as restorative process: human clues. Prog Brain Res 53: 279-288. doi: 10.1016/S0079-6123(08)60069-2
![]() |
[57] |
Landgraf D, Shostak A, Oster H (2012) Clock genes and sleep. Pflugers Arch 463: 3-14. doi: 10.1007/s00424-011-1003-9
![]() |
[58] |
Wisor JP (2012) A metabolic-transcriptional network links sleep and cellular energetics in the brain. Pflugers Arch 463: 15-22. doi: 10.1007/s00424-011-1030-6
![]() |
[59] |
Cirelli C, Gutierrez CM, Tononi G (2004) Extensive and divergent effects of sleep and wakefulness on brain gene expression. Neuron 41: 35-43. doi: 10.1016/S0896-6273(03)00814-6
![]() |
[60] |
Mackiewicz M, Shockley KR, Romer MA, et al. (2007) Macromolecule biosynthesis: a key function of sleep. Physiol Genomics 31: 441-457. doi: 10.1152/physiolgenomics.00275.2006
![]() |
[61] |
Cirelli C (2006) Cellular consequences of sleep deprivation in the brain. Sleep Med Rev 10: 307-321. doi: 10.1016/j.smrv.2006.04.001
![]() |
[62] | Clugston GA, Garlick PJ (1982) The response of protein and energy metabolism to food intake in lean and obese man. Hum Nutr Clin Nutr 36c: 57-70. |
[63] | Clugston GA, Garlick PJ (1982) The response of whole-body protein turnover to feeding in obese subjects given a protein-free, low-energy diet for three weeks. Hum Nutr Clin Nutr 36: 391-397. |
[64] | Golden MH, Waterlow JC (1977) Total protein synthesis in elderly people: a comparison of results with [15N]glycine and [14C]leucine. Clin Sci Mol Med 53: 277-288. |
[65] |
Horne JA (1980) Sleep and body restitution. Experientia 36: 11-13. doi: 10.1007/BF02003942
![]() |
[66] |
Meddis R (1975) On the function of sleep. Anim Behav 23: 676-691. doi: 10.1016/0003-3472(75)90144-X
![]() |
[67] |
Rial RV, Nicolau MC, Gamundi A, et al. (2007) The trivial function of sleep. Sleep Med Rev 11: 311-325. doi: 10.1016/j.smrv.2007.03.001
![]() |
[68] |
Webb WB (1974) Sleep as an adaptive response. Percept Mot Skills 38: 1023-1027. doi: 10.2466/pms.1974.38.3c.1023
![]() |
[69] | Villafuerte G, Miguel-Puga A, Rodriguez EM, et al. (2015) Sleep deprivation and oxidative stress in animal models: a systematic review. Oxid Med Cell Longev 2015: 234952. |
[70] |
Komoda Y, Honda K, Inoue S (1990) SPS-B, a physiological sleep regulator, from the brainstems of sleep-deprived rats, identified as oxidized glutathione. Chem Pharm Bull (Tokyo) 38: 2057-2059. doi: 10.1248/cpb.38.2057
![]() |
[71] |
Honda K, Komoda Y, Inoue S (1994) Oxidized glutathione regulates physiological sleep in unrestrained rats. Brain Res 636: 253-258. doi: 10.1016/0006-8993(94)91024-3
![]() |
[72] |
Kimura M, Kapas L, Krueger JM (1998) Oxidized glutathione promotes sleep in rabbits. Brain Res Bull 45: 545-548. doi: 10.1016/S0361-9230(97)00441-3
![]() |
[73] |
Krueger JM, Obal F, Jr., Fang J (1999) Why we sleep: a theoretical view of sleep function. Sleep Med Rev 3: 119-129. doi: 10.1016/S1087-0792(99)90019-9
![]() |
[74] |
Basner M, Rao H, Goel N, et al. (2013) Sleep deprivation and neurobehavioral dynamics. Curr Opin Neurobiol 23: 854-863. doi: 10.1016/j.conb.2013.02.008
![]() |
[75] |
Hennevin E, Huetz C, Edeline JM (2007) Neural representations during sleep: from sensory processing to memory traces. Neurobiol Learn Mem 87: 416-440. doi: 10.1016/j.nlm.2006.10.006
![]() |
[76] |
Tononi G, Cirelli C (2014) Sleep and the price of plasticity: from synaptic and cellular homeostasis to memory consolidation and integration. Neuron 81: 12-34. doi: 10.1016/j.neuron.2013.12.025
![]() |
[77] |
Xie L, Kang H, Xu Q, et al. (2013) Sleep drives metabolite clearance from the adult brain. Science 342: 373-377. doi: 10.1126/science.1241224
![]() |
[78] |
Mendelsohn AR, Larrick JW (2013) Sleep facilitates clearance of metabolites from the brain: glymphatic function in aging and neurodegenerative diseases. Rejuvenation Res 16: 518-523. doi: 10.1089/rej.2013.1530
![]() |
[79] | Spira AP, Gamaldo AA, An Y, et al. (2013) Self-reported sleep and beta-amyloid deposition in community-dwelling older adults. JAMA Neurol 70: 1537-1543. |
[80] |
Hahn EA, Wang HX, Andel R, et al. (2014) A change in sleep pattern may predict Alzheimer disease. Am J Geriatr Psychiatry 22: 1262-1271. doi: 10.1016/j.jagp.2013.04.015
![]() |
[81] |
Lim AS, Yu L, Kowgier M, et al. (2013) Modification of the relationship of the apolipoprotein E epsilon4 allele to the risk of Alzheimer disease and neurofibrillary tangle density by sleep. JAMA Neurol 70: 1544-1551. doi: 10.1001/jamaneurol.2013.4215
![]() |
[82] |
Ambrosini MV, Giuditta A (2001) Learning and sleep: the sequential hypothesis. Sleep Med Rev 5: 477-490. doi: 10.1053/smrv.2001.0180
![]() |
[83] | Ribeiro S, Mello CV, Velho T, et al. (2002) Induction of hippocampal long-term potentiation during waking leads to increased extrahippocampal zif-268 expression during ensuing rapid-eye-movement sleep. J Neurosci 22: 10914-10923. |
[84] |
Ribeiro S, Gervasoni D, Soares ES, et al. (2004) Long-lasting novelty-induced neuronal reverberation during slow-wave sleep in multiple forebrain areas. PLoS Biol 2: E24. doi: 10.1371/journal.pbio.0020024
![]() |
[85] |
Huber R, Ghilardi MF, Massimini M, et al. (2004) Local sleep and learning. Nature 430: 78-81. doi: 10.1038/nature02663
![]() |
[86] |
Walker MP, Stickgold R (2004) Sleep-dependent learning and memory consolidation. Neuron 44: 121-133. doi: 10.1016/j.neuron.2004.08.031
![]() |
[87] |
Stickgold R, Walker MP (2005) Memory consolidation and reconsolidation: what is the role of sleep? Trends Neurosci 28: 408-415. doi: 10.1016/j.tins.2005.06.004
![]() |
[88] | Maquet P, Schwartz S, Passingham R, et al. (2003) Sleep-related consolidation of a visuomotor skill: brain mechanisms as assessed by functional magnetic resonance imaging. J Neurosci 23: 1432-1440. |
[89] |
Tononi G, Cirelli C (2006) Sleep function and synaptic homeostasis. Sleep Med Rev 10: 49-62. doi: 10.1016/j.smrv.2005.05.002
![]() |
[90] |
Kavanau JL (1997) Memory, sleep and the evolution of mechanisms of synaptic efficacy maintenance. Neuroscience 79: 7-44. doi: 10.1016/S0306-4522(96)00610-0
![]() |
[91] |
Stickgold R (2006) Neuroscience: a memory boost while you sleep. Nature 444: 559-560. doi: 10.1038/nature05309
![]() |
[92] |
Eichenbaum H (2007) To sleep, perchance to integrate. Proc Natl Acad Sci U S A 104: 7317-7318. doi: 10.1073/pnas.0702503104
![]() |
[93] |
Fenn KM, Nusbaum HC, Margoliash D (2003) Consolidation during sleep of perceptual learning of spoken language. Nature 425: 614-616. doi: 10.1038/nature01951
![]() |
[94] |
Ferrara M, Iaria G, De Gennaro L, et al. (2006) The role of sleep in the consolidation of route learning in humans: a behavioural study. Brain Res Bull 71: 4-9. doi: 10.1016/j.brainresbull.2006.07.015
![]() |
[95] |
Peigneux P, Laureys S, Fuchs S, et al. (2004) Are spatial memories strengthened in the human hippocampus during slow wave sleep? Neuron 44: 535-545. doi: 10.1016/j.neuron.2004.10.007
![]() |
[96] |
Gottselig JM, Hofer-Tinguely G, Borbely AA, et al. (2004) Sleep and rest facilitate auditory learning. Neuroscience 127: 557-561. doi: 10.1016/j.neuroscience.2004.05.053
![]() |
[97] |
Peters KR, Smith V, Smith CT (2007) Changes in sleep architecture following motor learning depend on initial skill level. J Cogn Neurosci 19: 817-829. doi: 10.1162/jocn.2007.19.5.817
![]() |
[98] |
Ellenbogen JM, Payne JD, Stickgold R (2006) The role of sleep in declarative memory consolidation: passive, permissive, active or none? Curr Opin Neurobiol 16: 716-722. doi: 10.1016/j.conb.2006.10.006
![]() |
[99] |
Ellenbogen JM, Hulbert JC, Stickgold R, et al. (2006) Interfering with theories of sleep and memory: sleep, declarative memory, and associative interference. Curr Biol 16: 1290-1294. doi: 10.1016/j.cub.2006.05.024
![]() |
[100] |
Roth TC, 2nd, Rattenborg NC, Pravosudov VV (2010) The ecological relevance of sleep: the trade-off between sleep, memory and energy conservation. Philos Trans R Soc Lond B Biol Sci 365: 945-959. doi: 10.1098/rstb.2009.0209
![]() |
[101] | Fogel SMS, C. T. (2006) Declarative learningdependent changes in theta power during REM sleep. Sleep: A375-A375. |
[102] |
Born J, Rasch B, Gais S (2006) Sleep to remember. Neuroscientist 12: 410-424. doi: 10.1177/1073858406292647
![]() |
[103] |
Wyatt RJ, Fram DH, Kupfer DJ, et al. (1971) Total prolonged drug-induced REM sleep suppression in anxious-depressed patients. Arch Gen Psychiatry 24: 145-155. doi: 10.1001/archpsyc.1971.01750080049007
![]() |
[104] |
Siegel JM (2001) The REM sleep-memory consolidation hypothesis. Science 294: 1058-1063. doi: 10.1126/science.1063049
![]() |
[105] |
Rasch B, Pommer J, Diekelmann S, et al. (2009) Pharmacological REM sleep suppression paradoxically improves rather than impairs skill memory. Nat Neurosci 12: 396-397. doi: 10.1038/nn.2206
![]() |
[106] |
Irwin MR (2015) Why sleep is important for health: a psychoneuroimmunology perspective. Annu Rev Psychol 66: 143-172. doi: 10.1146/annurev-psych-010213-115205
![]() |
[107] |
Baglioni C, Battagliese G, Feige B, et al. (2011) Insomnia as a predictor of depression: a meta-analytic evaluation of longitudinal epidemiological studies. J Affect Disord 135: 10-19. doi: 10.1016/j.jad.2011.01.011
![]() |
[108] |
Dryman A, Eaton WW (1991) Affective symptoms associated with the onset of major depression in the community: findings from the US National Institute of Mental Health Epidemiologic Catchment Area Program. Acta Psychiatr Scand 84: 1-5. doi: 10.1111/j.1600-0447.1991.tb01410.x
![]() |
[109] | Lee E, Cho HJ, Olmstead R, et al. (2013) Persistent sleep disturbance: a risk factor for recurrent depression in community-dwelling older adults. Sleep 36: 1685-1691. |
[110] |
Cho HJ, Lavretsky H, Olmstead R, et al. (2008) Sleep disturbance and depression recurrence in community-dwelling older adults: a prospective study. Am J Psychiatry 165: 1543-1550. doi: 10.1176/appi.ajp.2008.07121882
![]() |
[111] | Jaussent I, Bouyer J, Ancelin ML, et al. (2011) Insomnia and daytime sleepiness are risk factors for depressive symptoms in the elderly. Sleep 34: 1103-1110. |
[112] | Manber R, Edinger JD, Gress JL, et al. (2008) Cognitive behavioral therapy for insomnia enhances depression outcome in patients with comorbid major depressive disorder and insomnia. Sleep 31: 489-495. |
[113] |
Giedke H, Schwarzler F (2002) Therapeutic use of sleep deprivation in depression. Sleep Med Rev 6: 361-377. doi: 10.1016/S1087-0792(02)90235-2
![]() |
[114] |
Grozinger M, Kogel P, Roschke J (2002) Effects of REM sleep awakenings and related wakening paradigms on the ultradian sleep cycle and the symptoms in depression. J Psychiatr Res 36: 299-308. doi: 10.1016/S0022-3956(02)00022-5
![]() |
[115] |
Killgore WD, Kamimori GH, Balkin TJ (2011) Caffeine protects against increased risk-taking propensity during severe sleep deprivation. J Sleep Res 20: 395-403. doi: 10.1111/j.1365-2869.2010.00893.x
![]() |
[116] |
McKenna BS, Dickinson DL, Orff HJ, et al. (2007) The effects of one night of sleep deprivation on known-risk and ambiguous-risk decisions. J Sleep Res 16: 245-252. doi: 10.1111/j.1365-2869.2007.00591.x
![]() |
[117] | Venkatraman V, Chuah YM, Huettel SA, et al. (2007) Sleep deprivation elevates expectation of gains and attenuates response to losses following risky decisions. Sleep 30: 603-609. |
[118] | Killgore WD, Killgore DB, Day LM, et al. (2007) The effects of 53 hours of sleep deprivation on moral judgment. Sleep 30: 345-352. |
[119] |
Trinder J, Waloszek J, Woods MJ, et al. (2012) Sleep and cardiovascular regulation. Pflugers Arch 463: 161-168. doi: 10.1007/s00424-011-1041-3
![]() |
[120] |
Barone DA, Krieger AC (2013) Stroke and obstructive sleep apnea: a review. Curr Atheroscler Rep 15: 334. doi: 10.1007/s11883-013-0334-8
![]() |
[121] |
Mullington JM, Haack M, Toth M, et al. (2009) Cardiovascular, inflammatory, and metabolic consequences of sleep deprivation. Prog Cardiovasc Dis 51: 294-302. doi: 10.1016/j.pcad.2008.10.003
![]() |
[122] |
Vgontzas AN, Fernandez-Mendoza J, Liao D, et al. (2013) Insomnia with objective short sleep duration: the most biologically severe phenotype of the disorder. Sleep Med Rev 17: 241-254. doi: 10.1016/j.smrv.2012.09.005
![]() |
[123] |
Meng L, Zheng Y, Hui R (2013) The relationship of sleep duration and insomnia to risk of hypertension incidence: a meta-analysis of prospective cohort studies. Hypertens Res 36: 985-995. doi: 10.1038/hr.2013.70
![]() |
[124] |
Palagini L, Bruno RM, Gemignani A, et al. (2013) Sleep loss and hypertension: a systematic review. Curr Pharm Des 19: 2409-2419. doi: 10.2174/1381612811319130009
![]() |
[125] |
Suka M, Yoshida K, Sugimori H (2003) Persistent insomnia is a predictor of hypertension in Japanese male workers. J Occup Health 45: 344-350. doi: 10.1539/joh.45.344
![]() |
[126] | Vgontzas AN, Liao D, Bixler EO, et al. (2009) Insomnia with objective short sleep duration is associated with a high risk for hypertension. Sleep 32: 491-497. |
[127] |
Fernandez-Mendoza J, Vgontzas AN, Liao D, et al. (2012) Insomnia with objective short sleep duration and incident hypertension: the Penn State Cohort. Hypertension 60: 929-935. doi: 10.1161/HYPERTENSIONAHA.112.193268
![]() |
[128] | Chung WS, Lin CL, Chen YF, et al. (2013) Sleep disorders and increased risk of subsequent acute coronary syndrome in individuals without sleep apnea: a nationwide population-based cohort study. Sleep 36: 1963-1968. |
[129] |
Vozoris NT (2013) The relationship between insomnia symptoms and hypertension using United States population-level data. J Hypertens 31: 663-671. doi: 10.1097/HJH.0b013e32835ed5d0
![]() |
[130] | Phillips B, Buzkova P, Enright P (2009) Insomnia did not predict incident hypertension in older adults in the cardiovascular health study. Sleep 32: 65-72. |
[131] | Phillips B, Mannino DM (2007) Do insomnia complaints cause hypertension or cardiovascular disease? J Clin Sleep Med 3: 489-494. |
[132] |
Ayas NT, White DP, Manson JE, et al. (2003) A prospective study of sleep duration and coronary heart disease in women. Arch Intern Med 163: 205-209. doi: 10.1001/archinte.163.2.205
![]() |
[133] | Hoevenaar-Blom MP, Spijkerman AM, Kromhout D, et al. (2011) Sleep duration and sleep quality in relation to 12-year cardiovascular disease incidence: the MORGEN study. Sleep 34: 1487-1492. |
[134] |
Mallon L, Broman JE, Hetta J (2002) Sleep complaints predict coronary artery disease mortality in males: a 12-year follow-up study of a middle-aged Swedish population. J Intern Med 251: 207-216. doi: 10.1046/j.1365-2796.2002.00941.x
![]() |
[135] |
Wang Q, Xi B, Liu M, et al. (2012) Short sleep duration is associated with hypertension risk among adults: a systematic review and meta-analysis. Hypertens Res 35: 1012-1018. doi: 10.1038/hr.2012.91
![]() |
[136] |
Cappuccio FP, Cooper D, D'Elia L, et al. (2011) Sleep duration predicts cardiovascular outcomes: a systematic review and meta-analysis of prospective studies. Eur Heart J 32: 1484-1492. doi: 10.1093/eurheartj/ehr007
![]() |
[137] | Sabanayagam C, Shankar A, Buchwald D, et al. (2011) Insomnia symptoms and cardiovascular disease among older American Indians: the Native Elder Care Study. J Environ Public Health 2011: 964617. |
[138] |
Heslop P, Smith GD, Metcalfe C, et al. (2002) Sleep duration and mortality: The effect of short or long sleep duration on cardiovascular and all-cause mortality in working men and women. Sleep Med 3: 305-314. doi: 10.1016/S1389-9457(02)00016-3
![]() |
[139] |
Kronholm E, Laatikainen T, Peltonen M, et al. (2011) Self-reported sleep duration, all-cause mortality, cardiovascular mortality and morbidity in Finland. Sleep Med 12: 215-221. doi: 10.1016/j.sleep.2010.07.021
![]() |
[140] | Ikehara S, Iso H, Date C, et al. (2009) Association of sleep duration with mortality from cardiovascular disease and other causes for Japanese men and women: the JACC study. Sleep 32: 295-301. |
[141] |
Suzuki E, Yorifuji T, Ueshima K, et al. (2009) Sleep duration, sleep quality and cardiovascular disease mortality among the elderly: a population-based cohort study. Prev Med 49: 135-141. doi: 10.1016/j.ypmed.2009.06.016
![]() |
[142] |
Dew MA, Hoch CC, Buysse DJ, et al. (2003) Healthy older adults' sleep predicts all-cause mortality at 4 to 19 years of follow-up. Psychosom Med 65: 63-73. doi: 10.1097/01.PSY.0000039756.23250.7C
![]() |
[143] |
Kripke DF, Garfinkel L, Wingard DL, et al. (2002) Mortality associated with sleep duration and insomnia. Arch Gen Psychiatry 59: 131-136. doi: 10.1001/archpsyc.59.2.131
![]() |
[144] | LeBlanc M, Merette C, Savard J, et al. (2009) Incidence and risk factors of insomnia in a population-based sample. Sleep 32: 1027-1037. |
[145] |
Morin CM, LeBlanc M, Daley M, et al. (2006) Epidemiology of insomnia: prevalence, self-help treatments, consultations, and determinants of help-seeking behaviors. Sleep Med 7: 123-130. doi: 10.1016/j.sleep.2005.08.008
![]() |
[146] | Ohayon M (1996) Epidemiological study on insomnia in the general population. Sleep 19: S7-15. |
[147] |
Ohayon MM (2002) Epidemiology of insomnia: what we know and what we still need to learn. Sleep Med Rev 6: 97-111. doi: 10.1053/smrv.2002.0186
![]() |
[148] | Buysse DJ (2014) Sleep health: can we define it? Does it matter? Sleep 37: 9-17. |
[149] |
Besedovsky L, Lange T, Born J (2012) Sleep and immune function. Pflugers Arch 463: 121-137. doi: 10.1007/s00424-011-1044-0
![]() |
[150] | Redwine L, Hauger RL, Gillin JC, et al. (2000) Effects of sleep and sleep deprivation on interleukin-6, growth hormone, cortisol, and melatonin levels in humans. J Clin Endocrinol Metab 85: 3597-3603. |
[151] |
Meier-Ewert HK, Ridker PM, Rifai N, et al. (2004) Effect of sleep loss on C-reactive protein, an inflammatory marker of cardiovascular risk. J Am Coll Cardiol 43: 678-683. doi: 10.1016/j.jacc.2003.07.050
![]() |
[152] | Haack M, Sanchez E, Mullington JM (2007) Elevated inflammatory markers in response to prolonged sleep restriction are associated with increased pain experience in healthy volunteers. Sleep 30: 1145-1152. |
[153] |
Vgontzas AN, Zoumakis E, Bixler EO, et al. (2004) Adverse effects of modest sleep restriction on sleepiness, performance, and inflammatory cytokines. J Clin Endocrinol Metab 89: 2119-2126. doi: 10.1210/jc.2003-031562
![]() |
[154] |
van Leeuwen WM, Lehto M, Karisola P, et al. (2009) Sleep restriction increases the risk of developing cardiovascular diseases by augmenting proinflammatory responses through IL-17 and CRP. PLoS One 4: e4589. doi: 10.1371/journal.pone.0004589
![]() |
[155] |
Abedelmalek S, Chtourou H, Aloui A, et al. (2013) Effect of time of day and partial sleep deprivation on plasma concentrations of IL-6 during a short-term maximal performance. Eur J Appl Physiol 113: 241-248. doi: 10.1007/s00421-012-2432-7
![]() |
[156] | Schmid SM, Hallschmid M, Jauch-Chara K, et al. (2011) Disturbed glucoregulatory response to food intake after moderate sleep restriction. Sleep 34: 371-377. |
[157] |
Stamatakis KA, Punjabi NM (2010) Effects of sleep fragmentation on glucose metabolism in normal subjects. Chest 137: 95-101. doi: 10.1378/chest.09-0791
![]() |
[158] |
Faraut B, Boudjeltia KZ, Dyzma M, et al. (2011) Benefits of napping and an extended duration of recovery sleep on alertness and immune cells after acute sleep restriction. Brain Behav Immun 25: 16-24. doi: 10.1016/j.bbi.2010.08.001
![]() |
[159] |
Shearer WT, Reuben JM, Mullington JM, et al. (2001) Soluble TNF-alpha receptor 1 and IL-6 plasma levels in humans subjected to the sleep deprivation model of spaceflight. J Allergy Clin Immunol 107: 165-170. doi: 10.1067/mai.2001.112270
![]() |
[160] |
Irwin M, Rinetti G, Redwine L, et al. (2004) Nocturnal proinflammatory cytokine-associated sleep disturbances in abstinent African American alcoholics. Brain Behav Immun 18: 349-360. doi: 10.1016/j.bbi.2004.02.001
![]() |
[161] |
Irwin M, Mascovich A, Gillin JC, et al. (1994) Partial sleep deprivation reduces natural killer cell activity in humans. Psychosom Med 56: 493-498. doi: 10.1097/00006842-199411000-00004
![]() |
[162] | Irwin M, McClintick J, Costlow C, et al. (1996) Partial night sleep deprivation reduces natural killer and cellular immune responses in humans. Faseb j 10: 643-653. |
[163] | Vgontzas AN, Pejovic S, Zoumakis E, et al. (2007) Daytime napping after a night of sleep loss decreases sleepiness, improves performance, and causes beneficial changes in cortisol and interleukin-6 secretion. Am J Physiol Endocrinol Metab 292: E253-261. |
[164] |
Faraut B, Nakib S, Drogou C, et al. (2015) Napping reverses the salivary interleukin-6 and urinary norepinephrine changes induced by sleep restriction. J Clin Endocrinol Metab 100: E416-426. doi: 10.1210/jc.2014-2566
![]() |
[165] | Chaput JP, Despres JP, Bouchard C, et al. (2008) The association between sleep duration and weight gain in adults: a 6-year prospective study from the Quebec Family Study. Sleep 31: 517-523. |
[166] |
Patel SR, Malhotra A, White DP, et al. (2006) Association between reduced sleep and weight gain in women. Am J Epidemiol 164: 947-954. doi: 10.1093/aje/kwj280
![]() |
[167] |
Cappuccio FP, D'Elia L, Strazzullo P, et al. (2010) Quantity and quality of sleep and incidence of type 2 diabetes: a systematic review and meta-analysis. Diabetes Care 33: 414-420. doi: 10.2337/dc09-1124
![]() |
[168] |
Cooper AJ, Westgate K, Brage S, et al. (2015) Sleep duration and cardiometabolic risk factors among individuals with type 2 diabetes. Sleep Med 16: 119-125. doi: 10.1016/j.sleep.2014.10.006
![]() |
[169] |
Lou P, Qin Y, Zhang P, et al. (2015) Association of sleep quality and quality of life in type 2 diabetes mellitus: A cross-sectional study in China. Diabetes Res Clin Pract 107: 69-76. doi: 10.1016/j.diabres.2014.09.060
![]() |
[170] |
Spiegel K, Tasali E, Penev P, et al. (2004) Brief communication: Sleep curtailment in healthy young men is associated with decreased leptin levels, elevated ghrelin levels, and increased hunger and appetite. Ann Intern Med 141: 846-850. doi: 10.7326/0003-4819-141-11-200412070-00008
![]() |
[171] |
Spiegel K, Leproult R, Van Cauter E (1999) Impact of sleep debt on metabolic and endocrine function. Lancet 354: 1435-1439. doi: 10.1016/S0140-6736(99)01376-8
![]() |
[172] |
Conlon M, Lightfoot N, Kreiger N (2007) Rotating shift work and risk of prostate cancer. Epidemiology 18: 182-183. doi: 10.1097/01.ede.0000249519.33978.31
![]() |
[173] |
Kubo T, Ozasa K, Mikami K, et al. (2006) Prospective cohort study of the risk of prostate cancer among rotating-shift workers: findings from the Japan collaborative cohort study. Am J Epidemiol 164: 549-555. doi: 10.1093/aje/kwj232
![]() |
[174] |
Kubo T, Oyama I, Nakamura T, et al. (2011) Retrospective cohort study of the risk of obesity among shift workers: findings from the Industry-based Shift Workers' Health study, Japan. Occup Environ Med 68: 327-331. doi: 10.1136/oem.2009.054445
![]() |
[175] |
Parent ME, El-Zein M, Rousseau MC, et al. (2012) Night work and the risk of cancer among men. Am J Epidemiol 176: 751-759. doi: 10.1093/aje/kws318
![]() |
[176] |
Schwartzbaum J, Ahlbom A, Feychting M (2007) Cohort study of cancer risk among male and female shift workers. Scand J Work Environ Health 33: 336-343. doi: 10.5271/sjweh.1150
![]() |
[177] |
Haus EL, Smolensky MH (2013) Shift work and cancer risk: potential mechanistic roles of circadian disruption, light at night, and sleep deprivation. Sleep Med Rev 17: 273-284. doi: 10.1016/j.smrv.2012.08.003
![]() |
[178] |
von Ruesten A, Weikert C, Fietze I, et al. (2012) Association of sleep duration with chronic diseases in the European Prospective Investigation into Cancer and Nutrition (EPIC)-Potsdam study. PLoS One 7: e30972. doi: 10.1371/journal.pone.0030972
![]() |
[179] |
Jiao L, Duan Z, Sangi-Haghpeykar H, et al. (2013) Sleep duration and incidence of colorectal cancer in postmenopausal women. Br J Cancer 108: 213-221. doi: 10.1038/bjc.2012.561
![]() |
[180] | Zhang X, Giovannucci EL, Wu K, et al. (2013) Associations of self-reported sleep duration and snoring with colorectal cancer risk in men and women. Sleep 36: 681-688. |
[181] |
Bishop D (2008) An applied research model for the sport sciences. Sports Med 38: 253-263. doi: 10.2165/00007256-200838030-00005
![]() |
[182] |
Drust B, Waterhouse J, Atkinson G, et al. (2005) Circadian rhythms in sports performance--an update. Chronobiol Int 22: 21-44. doi: 10.1081/CBI-200041039
![]() |
[183] | Fullagar HH, Skorski S, Duffield R, et al. (2015) Sleep and Athletic Performance: The Effects of Sleep Loss on Exercise Performance, and Physiological and Cognitive Responses to Exercise. Sports Med 45(2):161-86. |
[184] |
Hausswirth C, Louis J, Aubry A, et al. (2014) Evidence of disturbed sleep and increased illness in overreached endurance athletes. Med Sci Sports Exerc 46: 1036-1045. doi: 10.1249/MSS.0000000000000177
![]() |
[185] |
Gleeson M (2007) Immune function in sport and exercise. J Appl Physiol (1985) 103: 693-699. doi: 10.1152/japplphysiol.00008.2007
![]() |
[186] |
Samuels C (2008) Sleep, recovery, and performance: the new frontier in high-performance athletics. Neurol Clin 26: 169-180; ix-x. doi: 10.1016/j.ncl.2007.11.012
![]() |
[187] |
Durmer JS, Dinges DF (2005) Neurocognitive consequences of sleep deprivation. Semin Neurol 25: 117-129. doi: 10.1055/s-2005-867080
![]() |
[188] | Venter RE (2014) Perceptions of team athletes on the importance of recovery modalities. Eur J Sport Sci 14 Suppl 1: S69-76. |
[189] |
Erlacher D, Ehrlenspiel F, Adegbesan OA, et al. (2011) Sleep habits in German athletes before important competitions or games. J Sports Sci 29: 859-866. doi: 10.1080/02640414.2011.565782
![]() |
[190] |
Juliff LE, Halson SL, Peiffer JJ (2015) Understanding sleep disturbance in athletes prior to important competitions. J Sci Med Sport 18: 13-18. doi: 10.1016/j.jsams.2014.02.007
![]() |
[191] |
Hanton S, Fletcher D, Coughlan G (2005) Stress in elite sport performers: a comparative study of competitive and organizational stressors. J Sports Sci 23: 1129-1141. doi: 10.1080/02640410500131480
![]() |
[192] |
Chen JC, Brunner RL, Ren H, et al. (2008) Sleep duration and risk of ischemic stroke in postmenopausal women. Stroke 39: 3185-3192. doi: 10.1161/STROKEAHA.108.521773
![]() |
[193] | Chien KL, Chen PC, Hsu HC, et al. (2010) Habitual sleep duration and insomnia and the risk of cardiovascular events and all-cause death: report from a community-based cohort. Sleep 33: 177-184. |
[194] | Gangwisch JE, Malaspina D, Boden-Albala B, et al. (2005) Inadequate sleep as a risk factor for obesity: analyses of the NHANES I. Sleep 28: 1289-1296. |
[195] | Cappuccio FP, D'Elia L, Strazzullo P, et al. (2010) Sleep duration and all-cause mortality: a systematic review and meta-analysis of prospective studies. Sleep 33: 585-592. |
[196] | Machado RM, Koike MK (2014) Circadian rhythm, sleep pattern, and metabolic consequences: an overview on cardiovascular risk factors. Horm Mol Biol Clin Investig 18: 47-52. |
[197] | Petrov ME, Lichstein KL (2015) Differences in sleep between black and white adults: an update and future directions. Sleep Med Jan 23, in press. |
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7. | Digambar Singh, Dilip Sharma, S.L. Soni, Chandrapal Singh Inda, Sumit Sharma, Pushpendra Kumar Sharma, Amit Jhalani, A comprehensive review of physicochemical properties, production process, performance and emissions characteristics of 2nd generation biodiesel feedstock: Jatropha curcas, 2021, 285, 00162361, 119110, 10.1016/j.fuel.2020.119110 | |
8. | Adolfo Senatore, Editorial: Special Issue “Automotive Tribology”, 2020, 8, 2075-4442, 48, 10.3390/lubricants8040048 | |
9. | Fatai A. Aderibigbe, Suleiman Shiru, H. B. Saka, M. K. Amosa, Sherif Ishola Mustapha, Mohammed I Alhassan, Ayoade L. Adejumo, Morufudeen Abdulraheem, R. U. Owolabi, Heterogeneous Catalysis of Second Generation Oil for Biodiesel Production: A Review, 2021, 2196-9744, 10.1002/cben.202000035 | |
10. | M. Mofijur, Sk. Yasir Arafat Siddiki, Md. Bengir Ahmed Shuvho, F. Djavanroodi, I.M. Rizwanul Fattah, Hwai Chyuan Ong, M.A. Chowdhury, T.M.I. Mahlia, Effect of nanocatalysts on the transesterification reaction of first, second and third generation biodiesel sources- A mini-review, 2021, 270, 00456535, 128642, 10.1016/j.chemosphere.2020.128642 | |
11. | Harsh Kapadia, Hardik Brahmbhatt, Yuvrajsinh Dabhi, Sajan Chourasia, Investigation of emulsion and effect on emission in CI engine by using diesel and bio-diesel fuel: A review, 2019, 28, 11100621, 323, 10.1016/j.ejpe.2019.06.004 | |
12. | Artificial Neural Network-Based Analysis of the Tribological Behavior of Vegetable Oil–Diesel Fuel Mixtures, 2019, 7, 2075-4442, 32, 10.3390/lubricants7040032 | |
13. | Raheleh Talavari, Shokoufe Hosseini, GR Moradi, Low-cost biodiesel production using waste oil and catalyst, 2021, 39, 0734-242X, 250, 10.1177/0734242X20935174 | |
14. | Gaojian Ma, Lingmei Dai, Dehua Liu, Wei Du, A Robust Two-Step Process for the Efficient Conversion of Acidic Soybean Oil for Biodiesel Production, 2018, 8, 2073-4344, 527, 10.3390/catal8110527 | |
15. | Hossein Esmaeili, Ehsan Nourafkan, Mehdi Nakisa, Waqar Ahmed, 2021, 9780128213469, 149, 10.1016/B978-0-12-821346-9.00005-5 | |
16. | Gebresilassie Asnake Ewunie, Odd Ivar Lekang, John Morken, Zerihun Demrew Yigezu, Characterizing the potential and suitability of Ethiopian variety Jatropha curcas for biodiesel production: Variation in yield and physicochemical properties of oil across different growing areas, 2021, 7, 23524847, 439, 10.1016/j.egyr.2021.01.007 | |
17. | Justina Gaidukevič, Jurgis Barkauskas, Anna Malaika, Paulina Rechnia-Gorący, Aleksandra Możdżyńska, Vitalija Jasulaitienė, Mieczysław Kozłowski, Modified graphene-based materials as effective catalysts for transesterification of rapeseed oil to biodiesel fuel, 2018, 39, 18722067, 1633, 10.1016/S1872-2067(18)63087-6 | |
18. | Nelson R. Villarante, Chelsea H. Ibarrientos, Physicochemical Characterization of Candlenut (Aleurites moluccana)-derived Biodiesel Purified with Deed Eutectic Solvents, 2021, 70, 1345-8957, 113, 10.5650/jos.ess20152 | |
19. | Hui Suan Ng, Phei Er Kee, Hip Seng Yim, Po-Ting Chen, Yu-Hong Wei, John Chi-Wei Lan, Recent advances on the sustainable approaches for conversion and reutilization of food wastes to valuable bioproducts, 2020, 302, 09608524, 122889, 10.1016/j.biortech.2020.122889 | |
20. | Aroosh Shabbir, Hamid Mukhtar, Muhammad Waseem Mumtaz, Umer Rashid, 2020, Chapter 15, 978-3-030-44175-3, 407, 10.1007/978-3-030-44176-0_15 | |
21. | Zahra Faraji Mahyari, Zeinab Khorasanizadeh, Majid Khanali, Khadijeh Faraji Mahyari, Biodiesel production from slaughter wastes of broiler chicken: a potential survey in Iran, 2021, 3, 2523-3963, 10.1007/s42452-020-04045-7 | |
22. | Felix Ishola, Damola Adelekan, Angela Mamudu, Temitope Abodunrin, Abraham Aworinde, Obafemi Olatunji, Stephen Akinlabi, Biodiesel production from palm olein: A sustainable bioresource for Nigeria, 2020, 6, 24058440, e03725, 10.1016/j.heliyon.2020.e03725 | |
23. | Martin Gojun, Anabela Ljubić, Matea Bačić, Ana Jurinjak Tušek, Anita Šalić, Bruno Zelić, Model-to-model: Comparison of mathematical process models of lipase catalysed biodiesel production in a microreactor, 2021, 145, 00981354, 107200, 10.1016/j.compchemeng.2020.107200 | |
24. | Kinetic Parameter Estimation and Mathematical Modelling of Lipase Catalysed Biodiesel Synthesis in a Microreactor, 2019, 10, 2072-666X, 759, 10.3390/mi10110759 | |
25. | Valeria Casson Moreno, Enrico Danzi, Luca Marmo, Ernesto Salzano, Valerio Cozzani, Major accident hazard in biodiesel production processes, 2019, 113, 09257535, 490, 10.1016/j.ssci.2018.12.014 | |
26. | Muhammad Sajjad Iqbal, 2021, Chapter 25, 978-3-030-48797-3, 389, 10.1007/978-3-030-48798-0_25 | |
27. | Martin Gojun, Matea Bačić, Anabela Ljubić, Anita Šalić, Bruno Zelić, Transesterification in Microreactors—Overstepping Obstacles and Shifting Towards Biodiesel Production on a Microscale, 2020, 11, 2072-666X, 457, 10.3390/mi11050457 | |
28. | N. V. Lakina, E. M. Sulman, V. Yu. Doluda, V. G. Matveeva, Biocatalytic Transesterification of Oleic Acid Triglyceride in Supercritical Carbon Dioxide, 2020, 14, 1990-7931, 1077, 10.1134/S1990793120070106 | |
29. | Khalid I. Doudin, Quantitative and qualitative analysis of biodiesel by NMR spectroscopic methods, 2021, 284, 00162361, 119114, 10.1016/j.fuel.2020.119114 | |
30. | Shemelis N. Gebremariam, Trine Hvoslef-Eide, Meseret T. Terfa, Jorge M. Marchetti, Techno-Economic Performance of Different Technological Based Bio-Refineries for Biofuel Production, 2019, 12, 1996-1073, 3916, 10.3390/en12203916 | |
31. | Naila Ghani, Javed Iqbal, Sana Sadaf, Haq Nawaz Bhatti, Muhammad Asgher, Comparison of Photo‐Esterification Capability of Bismuth Vanadate with Reduced Graphene Oxide Bismuth Vanadate (RGO/BiVO 4 ) Composite for Biodiesel Production from High Free Fatty Acid Containing Non‐Edible Oil , 2020, 5, 2365-6549, 9245, 10.1002/slct.202001913 | |
32. | Abdul Razack Sirajunnisa, Duraiarasan Surendhiran, Thangaraj Baskar, Mani Vijay, Velayutham Vijayagopal, Subramaniyan Thiruvengadam, 2019, Chapter 15, 978-3-030-14462-3, 387, 10.1007/978-3-030-14463-0_15 | |
33. | Sergii Shamanskyi, Sergii Boichenko, Lesia Pavliukh, WASTEWATER TREATMENT WITH BIOCONVERSION FOR MOTOR FUEL PRODUCTION, 2020, 2313-8416, 66, 10.21303/2313-8416.2020.001460 | |
34. | Abolanle Saheed Adekunle, John Adekunle Oyedele Oyekunle, Adelanke Ibukun Oduwale, Yetunde Owootomo, Olaoluwa Ruth Obisesan, Saheed Eluwale Elugoke, Solomon Sunday Durodola, Sanusi Babatunde Akintunde, Oluwatobi S. Oluwafemi, Biodiesel potential of used vegetable oils transesterified with biological catalysts, 2020, 6, 23524847, 2861, 10.1016/j.egyr.2020.10.019 | |
35. | Bruno L. Andrade, Fernando C. Rangel, Rosenira S. da Cruz, 2020, 9786586768442, 319, 10.7476/9786586768442.0014 | |
36. | Ragul Govindaraju, Shiao-Shing Chen, Li-Pang Wang, Hau-Ming Chang, Mithilesh Pasawan, Significance of Membrane Applications for High-Quality Biodiesel and Byproduct (Glycerol) in Biofuel Industries—Review, 2021, 2198-6592, 10.1007/s40726-021-00182-8 | |
37. | S.N. Gebremariam, J.M. Marchetti, Process simulation and techno-economic performance evaluation of alternative technologies for biodiesel production from low value non-edible oil, 2021, 149, 09619534, 106102, 10.1016/j.biombioe.2021.106102 | |
38. | Sajad Tamjidi, Hossein Esmaeili, Bahareh Kamyab Moghadas, Performance of functionalized magnetic nanocatalysts and feedstocks on biodiesel production: A review study, 2021, 305, 09596526, 127200, 10.1016/j.jclepro.2021.127200 | |
39. | Digambar Singh, Dilip Sharma, S.L. Soni, Chandrapal Singh Inda, Sumit Sharma, Pushpendra Kumar Sharma, Amit Jhalani, A comprehensive review of biodiesel production from waste cooking oil and its use as fuel in compression ignition engines: 3rd generation cleaner feedstock, 2021, 09596526, 127299, 10.1016/j.jclepro.2021.127299 | |
40. | Abdulrahman Shakir Mahmood, Haqi I. Qatta, Saadi M. D. Al-Nuzal, Talib Kamil Abed, Abdulwahab Ahmed Hardan, The effect of compression ratio on the performance and emission characteristics of C.I. Engine fuelled with corn oil biodiesel blended with diesel fuel., 2021, 779, 1755-1307, 012062, 10.1088/1755-1315/779/1/012062 | |
41. | Martin Gojun, Anita Šalić, Bruno Zelić, Integrated microsystems for lipase-catalyzed biodiesel production and glycerol removal by extraction or ultrafiltration, 2021, 180, 09601481, 213, 10.1016/j.renene.2021.08.064 | |
42. | Deshal Yadav, Sudipta Datta, Sujan Saha, Subhalaxmi Pradhan, Shweta Kumari, Pavan Kumar Gupta, Vishal Chauhan, Shiva Kumar Saw, Gajanan Sahu, Heterogeneous Nanocatalyst for Biodiesel Synthesis, 2022, 7, 2365-6549, 10.1002/slct.202201671 | |
43. | Zekarias Zeleke Zamba, Ali Shemsedin Reshad, Synthesis of Fatty Acid Methyl Ester from Croton macrostachyus (Bisana) Kernel Oil: Parameter Optimization, Engine Performance, and Emission Characteristics for Croton macrostachyus Kernel Oil Fatty Acid Methyl Ester Blend with Mineral Diesel Fuel, 2022, 7, 2470-1343, 20619, 10.1021/acsomega.2c00682 | |
44. | Onome Ejeromedoghene, Abiodun Oladipo, Charles Obinwanne Okoye, Victor Enwemiwe, Ebube Victoria Anyaebosim, Muritala Olusola, Sheriff Adewuyi, Green biodiesel based on non-vegetable oil and catalytic ability of waste materials as heterogeneous catalyst, 2022, 44, 1556-7036, 7432, 10.1080/15567036.2022.2113935 | |
45. | Teuku Azuar Rizal, Husni Husin, Fahrizal Nasution, Hamdani Umar, The Experimental Study of Pangium Edule Biodiesel in a High-Speed Diesel Generator for Biopower Electricity, 2022, 15, 1996-1073, 5405, 10.3390/en15155405 | |
46. | Anil Kumar, Vishwender Pratap Singh, Aradhana Srivastava, Quality biodiesel via biotransesterification from inedible renewable sources, 2022, 379, 09596526, 134653, 10.1016/j.jclepro.2022.134653 | |
47. | Hossein Esmaeili, A critical review on the economic aspects and life cycle assessment of biodiesel production using heterogeneous nanocatalysts, 2022, 230, 03783820, 107224, 10.1016/j.fuproc.2022.107224 | |
48. | Yudong Meng, Nasreddine Kebir, Xiaoshuang Cai, Sebastien Leveneur, In-Depth Kinetic Modeling and Chemical Analysis for the Epoxidation of Vegetable Oils in a Liquid–Liquid–Solid System, 2023, 13, 2073-4344, 274, 10.3390/catal13020274 | |
49. | Olusegun D. Samuel, Mohammad Kaveh, Oluwayomi J. Oyejide, P.V. Elumalai, Tikendra Nath Verma, Kottakkaran Sooppy Nisar, C Ahamed Saleel, Asif Afzal, O.S.I. Fayomi, H.I. Owamah, Selçuk Sarıkoç, Christopher C. Enweremadu, Performance comparison of empirical model and Particle Swarm Optimization & its boiling point prediction models for waste sunflower oil biodiesel, 2022, 33, 2214157X, 101947, 10.1016/j.csite.2022.101947 | |
50. | Nejib Hidouri, Mawaheb Mouftahi, 2021, Impact of Various Factors on the Transesterification Reaction: Case of the biodiesel production from Waste Cooking Oil, 978-1-6654-3290-0, 1, 10.1109/IREC52758.2021.9624916 | |
51. | Mohd Yunus Khan, P. Sudhakar Rao, B.S. Pabla, Suresh Ghotekar, Innovative biodiesel production plant: Design, development, and framework for the usage of biodiesel as a sustainable EDM fluid, 2022, 34, 10183647, 102203, 10.1016/j.jksus.2022.102203 | |
52. | Hossein Esmaeili, Sajad Tamjidi, 2021, 9781119729969, 1, 10.1002/9781119729969.ch1 | |
53. | Rahul Chamola, Nitin Kumar, Siddharth Jain, 2022, Chapter 32, 978-981-16-8340-4, 395, 10.1007/978-981-16-8341-1_32 | |
54. | V. Dinesh Kumar, Vinayak B. Hemadri, M. Chinnapandian, K. M. Mrityunjayaswamy, An experimental investigation of papaya oil methyl ester (POME) blends as potential alternate fuel for CI engine application, 2023, 0143-0750, 1, 10.1080/01430750.2022.2162124 | |
55. | Martin Gojun, Davor Valinger, Anita Šalić, Bruno Zelić, Development of NIR-Based ANN Models for On-Line Monitoring of Glycerol Concentration during Biodiesel Production in a Microreactor, 2022, 13, 2072-666X, 1590, 10.3390/mi13101590 | |
56. | Abu Saleh Ahmed, Nur Adibah Abdul Rahim, Md Rezaur Rahman, Mohammad Shahril Osman, Influence of Propanol as Additive with Diesel Jatropha Biodiesel Blend Fuel for Diesel Engine, 2021, 8, 2289-7771, 986, 10.33736/jaspe.3570.2021 | |
57. | Lilies K. Kathumbi, Patrick G. Home, James M. Raude, Benson B. Gathitu, Performance of Citric Acid as a Catalyst and Support Catalyst When Synthesized with NaOH and CaO in Transesterification of Biodiesel from Black Soldier Fly Larvae Fed on Kitchen Waste, 2022, 3, 2673-3994, 295, 10.3390/fuels3020018 | |
58. | Gabriel Baioni e Silva, Tainá Manicardi, Andreza A. Longati, Electo E. S. Lora, Thais S. Milessi, Parametric comparison of biodiesel transesterification processes using non‐edible feedstocks: Castor bean and jatropha oils , 2022, 1932-104X, 10.1002/bbb.2364 | |
59. | Dhurba Neupane, Biofuels from Renewable Sources, a Potential Option for Biodiesel Production, 2022, 10, 2306-5354, 29, 10.3390/bioengineering10010029 | |
60. | Ridha Ennetta, Hakan Serhad Soyhan, Cemil Koyunoğlu, Veli Gökhan Demir, Current Technologies and Future Trends for Biodiesel Production: A Review, 2022, 47, 2193-567X, 15133, 10.1007/s13369-022-07121-9 | |
61. | Avinash P. Ingle, Rahul Bhagat, Mangesh P. Moharil, Samuel Lalthazuala Rokhum, Shreshtha Saxena, S. R. Kalbande, 2022, 9781119771364, 167, 10.1002/9781119771364.ch9 | |
62. | Jayan Sentanuhady, Wisnu Hozaifa Hasan, Muhammad Akhsin Muflikhun, Aniello Riccio, Recent Progress on the Implementation of Renewable Biodiesel Fuel for Automotive and Power Plants: Raw Materials Perspective, 2022, 2022, 1687-8442, 1, 10.1155/2022/5452942 | |
63. | Lilies K. Kathumbi, Patrick G. Home, James M. Raude, Benson B. Gathitu, Anthony N. Gachanja, Anthony Wamalwa, Geoffrey Mibei, Influence of Transesterification Catalysts Synthesized with Citric Acid on the Quality and Oxidative Stability of Biodiesel from Black Soldier Fly Larvae, 2022, 3, 2673-3994, 533, 10.3390/fuels3030032 | |
64. | Setareh Heidari, David A. Wood, 2021, 9781119724957, 447, 10.1002/9781119724957.ch17 | |
65. | Fahimeh Esmi, Venu Babu Borugadda, Ajay K. Dalai, Heteropoly acids as supported solid acid catalysts for sustainable biodiesel production using vegetable oils: A review, 2022, 404, 09205861, 19, 10.1016/j.cattod.2022.01.019 | |
66. | Xiujuan Qian, Xinhai Zhou, Dawei Zhou, Jie Zhou, Fengxue Xin, Weiliang Dong, Wenming Zhang, Min Jiang, 2023, 9780323911931, 199, 10.1016/B978-0-323-91193-1.00007-X | |
67. | Samia A. Hanafi, Mamdouh S. Elmelawy, Hanan A. Ahmed, Solvent-free deoxygenation of low-cost fat to produce diesel-like hydrocarbons over Ni–MoS2/Al2O3–TiO2 heterogenized catalyst, 2022, 6, 2538-3604, 1, 10.1007/s42108-021-00156-y | |
68. | Kamlesh Kumar R. Shah, Gayatriben B. Patel, 2022, Chapter 27, 978-981-16-4444-3, 653, 10.1007/978-981-16-4445-0_27 | |
69. | Narjes Shahraini, Mohammad H. Entezari, Biodiesel from waste oil under mild conditions by a combination of calcium‐strontium oxide nanocatalyst and ultrasonic waves, 2022, 46, 0363-907X, 13781, 10.1002/er.8098 | |
70. | Brandon Lowe, Jabbar Gardy, Ali Hassanpour, The Role of Sulfated Materials for Biodiesel Production from Cheap Raw Materials, 2022, 12, 2073-4344, 223, 10.3390/catal12020223 | |
71. | Mona Ramadhan Sahwan, Hatem Masri, Lokesh Verma, Abdulla Alotaibi, 2022, A Feasibility Study For Biodiesel Production In Kingdom Of Bahrain, 978-1-6654-9501-1, 1327, 10.1109/DASA54658.2022.9765264 | |
72. | Timothy Tibesigwa, Peter Wilberforce Olupot, John Baptist Kirabira, The critical techno-economic aspects for production of B10 biodiesel from second generation feedstocks: a review, 2022, 41, 1478-6451, 751, 10.1080/14786451.2021.1976181 | |
73. | Trinath Biswal, Krushna Prasad Shadangi, Rupam Kataki, 2022, 9781119771364, 377, 10.1002/9781119771364.ch20 | |
74. | Omojola Awogbemi, Daramy Vandi Von Kallon, Victor Sunday Aigbodion, Trends in the development and utilization of agricultural wastes as heterogeneous catalyst for biodiesel production, 2021, 98, 17439671, 244, 10.1016/j.joei.2021.06.017 | |
75. | Omojola Awogbemi, Daramy Vandi Von Kallon, Application of Tubular Reactor Technologies for the Acceleration of Biodiesel Production, 2022, 9, 2306-5354, 347, 10.3390/bioengineering9080347 | |
76. | C. J. Ramanan, Bhaskor J. Bora, Nur Alom, Abdulrajak Buradi, Shivam Shukla, INVESTIGATION OF DEAD-END FILTRATION OF CRUDE BIODIESEL USING REVERSE OSMOSIS MEMBRANE THROUGH CFD SIMULATION , 2022, 23, 2150-3621, 49, 10.1615/InterJEnerCleanEnv.2022043253 | |
77. | Natei Ermias Benti, Abreham Berta Aneseyee, Chernet Amente Geffe, Tegenu Argaw Woldegiyorgis, Gamachis Sakata Gurmesa, Mesfin Bibiso, Ashenafi Abebe Asfaw, Abnet Woldesenbet Milki, Yedilfana Setarge Mekonnen, Biodiesel production in Ethiopia: Current status and future prospects, 2023, 19, 24682276, e01531, 10.1016/j.sciaf.2022.e01531 | |
78. | Shemelis Nigatu Gebremariam, 2021, 9781119729969, 313, 10.1002/9781119729969.ch13 | |
79. | Jorge Mario Marchetti, Optimization of the esterification reaction of free fatty acids present in waste salmon oil, 2022, 16, 1932-104X, 1297, 10.1002/bbb.2374 | |
80. | Sumari Sumari, Mega Murti, Aman Santoso, Muhammad Roy Asrori, Sono-Transesterification of Kapok Seed Oil with CaO:BaO-(x:y)/Active Natural Zeolite Catalyst, 2022, 10, 2164-6341, 3659, 10.32604/jrm.2022.022995 | |
81. | Fatai Alade Aderibigbe, Harvis Bamidele Saka, Sherif Ishola Mustapha, Mutiu Kolade Amosa, Suleiman Shiru, Idowu Abdulfatai Tijani, Esther Oluwabunmi Babatunde, Bisola Taibat Bello, Waste Cooking Oil Conversion to Biodiesel Using Solid Bifunctional Catalysts, 2023, 2196-9744, 10.1002/cben.202200036 | |
82. | Chodchanok Attaphong, Nattaya Morawan, Piampoom Sarikprueck, Ampira Charoensaeng, Sutha Khaodhiar, Phase stability, fuel properties, and diesel engine performance of palm‐oil‐based microemulsion biofuels , 2023, 1097-3958, 10.1002/jsde.12668 | |
83. | Vishal Ram, Surender Reddy Salkuti, An Overview of Major Synthetic Fuels, 2023, 16, 1996-1073, 2834, 10.3390/en16062834 | |
84. | Gajanan Sahu, Sudipta Datta, Sujan Saha, Prakash D. Chavan, Deshal Yadav, Vishal Chauhan, 2023, 9781119829324, 441, 10.1002/9781119829522.ch15 | |
85. | Shemelis Nigatu Gebremariam, Biodiesel as a transport fuel, advantages and disadvantages: review, 2023, 1932-104X, 10.1002/bbb.2503 | |
86. | Yaseen M. Tayib, Farooq Al–Sheikh, Zaidoon M. Shakor, William A. Anderson, Biodiesel production from fish oil: a review, 2023, 1759-7269, 1, 10.1080/17597269.2023.2214417 | |
87. | Manpreet Kaur, Ashish Kumar Singh, Ajay Singh, Bioconversion of food industry waste to value added products: Current technological trends and prospects, 2023, 55, 22124292, 102935, 10.1016/j.fbio.2023.102935 | |
88. | Saanyol Ityokumbul Igbax, Daniel Swartling, Ahmed ElSawy, Stephen Idem, Impact of ultrasonic mixing on virgin and waste vegetable oils for biodiesel production, 2023, 11, 2296-598X, 10.3389/fenrg.2023.1268172 | |
89. | Getachew D. Gebre, Shemelis N. Gebremariam, Yadessa G. Keneni, Jorge M. Marchetti, Valorization of tropical fruit‐processing wastes and byproducts for biofuel production, 2023, 1932-104X, 10.1002/bbb.2531 | |
90. | Mohammed Falalu Hamza, Hassan Soleimani, Shelley Lorimer, Surajudeen Sikiru, Yarima Mudassir Hassan, Amir Rostami, Hojjatollah Soleimani, Birol M.R. Demiral, Hydrothermal synthesis, response surface study, and interfacial tension evaluation of modified nanotube, 2023, 391, 01677322, 123309, 10.1016/j.molliq.2023.123309 | |
91. | Yudong Meng, Nasreddine Kebir, Sebastien Leveneur, Reactivity and structure: epoxidation of cottonseed oil and the corresponding fatty acid methyl ester, 2023, 2190-6815, 10.1007/s13399-023-04985-1 | |
92. | Renuka Garg, Rana Sabouni, Mohsen Ahmadipour, From waste to fuel: Challenging aspects in sustainable biodiesel production from lignocellulosic biomass feedstocks and role of metal organic framework as innovative heterogeneous catalysts, 2023, 206, 09266690, 117554, 10.1016/j.indcrop.2023.117554 | |
93. | Nevardo Bello Yaya, Alberto Claudio Habert, Frederico de Araujo Kronemberger, Evaluation of a hollow fiber membrane contactor reactor for reactive extraction in biodiesel production, 2023, 194, 02552701, 109574, 10.1016/j.cep.2023.109574 | |
94. | Aneta Bełdycka-Bórawska, Performance of the Polish Biofuel Industry after Accession to the European Union in the Area of Sustainable Development Concepts, 2023, 16, 1996-1073, 7541, 10.3390/en16227541 | |
95. | Chantal T. Tracey, Darya O. Shavronskaya, Jing'ai Shao, Haiping Yang, Pavel V. Krivoshapkin, Elena F. Krivoshapkina, Heterogeneous carbon dot catalysts for biodiesel production: A mini review, 2024, 362, 00162361, 130882, 10.1016/j.fuel.2024.130882 | |
96. | Farhina Ahmed, Sumita Debbarma, 2024, Chapter 25, 978-981-99-6865-7, 339, 10.1007/978-981-99-6866-4_25 | |
97. | Dinku Seyoum Zeleke, Atsedemariam Ayalew Bezabih, Impact of additives from moringa stenopetela leaf extract and ethanol on the emission characteristics and performance of soybean biodiesel for single cylinder CI engine, 2024, 24058440, e27619, 10.1016/j.heliyon.2024.e27619 | |
98. | C. Senthilkumar, C. Krishnaraj, P. Nivash, C. Chanakyan, Biodiesel Production from Brassica napus Seeds and Its Characterization in Diesel Engine with Nano Additives, 2023, 57, 0040-5795, 1585, 10.1134/S0040579523330084 | |
99. | Saad S. Almady, Ali I. Moussa, Mohammed M. Deef, Moamen F. Zayed, Saleh M. Al-Sager, Abdulwahed M. Aboukarima, Biodiesel Production through the Transesterification of Non-Edible Plant Oils Using Glycerol Separation Technique with AC High Voltage, 2024, 16, 2071-1050, 2896, 10.3390/su16072896 | |
100. | Waqas Ahmad, Ahtasham Ahsan, Hafiz Abdullah Shakir, Muhammad Khan, Shaukat Ali, Ibnu Maulana Hidayatullah, Marcelo Franco, Muhammad Irfan, 2024, Chapter 10, 978-981-97-1622-7, 237, 10.1007/978-981-97-1623-4_10 | |
101. | Zahra Salimi, Seyed Ali Hosseini, Production of Biodiesel from Waste Cooking Oil in the Presence of a K2O/BaFe2O4 Nanomagnetic Catalyst, 2024, 2837-1445, 10.1021/acssusresmgt.4c00056 | |
102. | Wan Nur Aisyah Wan Osman, Mohd Hakimi Rosli, Wan Nur Athirah Mazli, Shafirah Samsuri, Comparative review of biodiesel production and purification, 2024, 13, 27726568, 100264, 10.1016/j.ccst.2024.100264 | |
103. | 2024, 9781394258079, 259, 10.1002/9781394258109.ch16 | |
104. | Sarita Yadav, Srikanth Ponnada, Indu Kumari, Rakesh K. Sharma, 2024, Chapter 2, 978-981-97-6543-0, 17, 10.1007/978-981-97-6544-7_2 | |
105. | Pirapat Arunyanart, Lida Simasatitkul, Pachara Juyploy, Peerapat Kotluklan, Jirayu Chanbumrung, Samitthichai Seeyangnok, The prediction of biodiesel production yield from transesterification of vegetable oils with Machine learning, 2024, 25901230, 103236, 10.1016/j.rineng.2024.103236 | |
106. | Suleiman Ibrahim Shelash Mohammad, Asokan Vasudevan, K.D.V. Prasad, Inas Ridha Ali, Abhinav Kumar, Ankur Kulshreshta, Vikasdeep Singh Mann, I.B. Sapaev, Teku Kalyani, Mohammad Sina, Evaluation of Diesel Engine Performance and Emissions Using Biodiesel from Waste Oils Synthesized with Fe3O4-SiO2 Heterogeneous Nano Catalyst, 2024, 24058440, e41416, 10.1016/j.heliyon.2024.e41416 | |
107. | Khalifa Musa Muhammad, Modupe Munirat Adeyemi, Joseph Jacob, Abubakar Rabiu Koko, Kabiru Dauda, Anas Ali Tamasi, Ibrahim Yahuza, Biodiesel production in Africa from non-edible sources: Sources, Production, Properties and Policies, 2024, 29498392, 100201, 10.1016/j.scenv.2024.100201 | |
108. | Nhlapo P. Lefu, Motaung Tshwafo, 2025, Chapter 10, 978-981-96-2781-3, 123, 10.1007/978-981-96-2782-0_10 | |
109. | Rashmi Priya, Preeti Yadav, 2025, 9781394301218, 285, 10.1002/9781394301287.ch11 |
Method | Temperature (℃) | Residence Time | Heating rate (℃/s) | Major products |
Conventional/slow pyrolysis | Med-high (400–500) | Long 5–30 min | Low 10 | Gases Char Bio-oil (tar) |
Fast pyrolysis | Med-high (400–650) | Short 0.5–2 s | High 100 | Bio-oil (thinner) Gases Char |
Ultra-fast/flash pyrolysis | High (700–1000) | Very short < 0.5 s | Low 10 | Gases Bio-oil |
Feedstock | Alcohol | Process variables | Yield % achieved | Ref. | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time | Stirring speed | Acid Catalyst | Catalyst concentration | ||||
Mixed oil b | Methanol | 6:1 | 60 | - | 300 rpm | H2SO4 | 2.5% | 96.6% | [43] |
Soybean oil | Methanol | 20:1 | 120 | 5 h | - | trifluoroacetic acid | 2.0 M | 98.4% | [41] |
Canola oil | Methanol with terahydrofuran as Co-solvent | 24:1 | 110 | 18 h | AlCl3 | 5% | 98% | [39] | |
Corn oil | Methanol with dimethyl ether as Co-solvent | 6:1 | 80 | 2 h | - | p-toluenesulfonic acid | 4 wt.% | 100% | [44] |
Canola oil up to 20% FFA | Methanol | 9:1 | 200 | - | - | 12-Tungstophosphoric acid | 3 wt.% | 90 wt.% | [45] |
b mixed oil-50% sunflower and 50% soybean oil |
Catalyst | Concentration of the catalyst (wt.%, by weight of crude oil) | Ester content (wt.%) | Product yield (wt.%) |
NaOH | 1.1 | 94.0 | 85.3 |
KOH | 1.5 | 92.5 | 86.0 |
CH3ONa | 1.3 | 92.8 | 89.0 |
Catalyst (gm) |
Oil (gm) |
Methanol (gm) |
Reaction Time (hr) |
Reaction Temp. (℃) |
Biodiesel (%) |
Glycerin (%) |
1.2 | 100 | 20 | 1 | 65 | 87.20 | 30.80 |
1.0 | 100 | 20 | 1 | 65 | 92.40 | 27.35 |
0.8 | 100 | 20 | 1 | 65 | 95.33 | 24.22 |
0.6 | 100 | 20 | 1 | 65 | 74.45 | 45.37 |
Feedstock | Alcohol | Process variables | Yield % achieved | Ref. | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time | Stirring speed | Catalyst type | Cat. Concentration | ||||
Rice bran oil | methanol | 1:09 | 55 | 60 minute | - | NaOH | 0.75% (w/w) | Optimum | [57] |
Sunflower cooking oil | methanol | 6:01 | 40 | - | 320 rpm | KOH | 1% | 99.50% | [53] |
refined cooking vegetable oils | methanol | 6:01 | 65 | 60 minute | - | KOH | 1.2 wt.% | 97.50% | [58] |
Waste cooking vegetable oils | methanol | 6:01 | 65 | 60 minute | - | KOH | 1.2 wt.% | 93.20% | [58] |
Jatropha oil | methanol | 5:01 | 65 | 60 minute | - | NaOH | 0.80% | 95.5%. | [59] |
Soybean oil | methanol | 6:01 | 60 ± 1 | 60 minute | - | NaOH | 1% | 90% | [60] |
Cottonseed oils | methanol | 6:01 | 60 ± 1 | 60 minute | - | NaOH | 1% | 98.50% | [60] |
Waste frying oils | methanol | 7.5:1 | 50 | 30 minute | - | NaOH | 0.50% | 96% | [61] |
Karanja oil | methanol | 6:01 | 65 | 15 minute | 360 rpm | KOH | 1% | > 85% | [54] |
Karanja oil | methanol | 12:01 | 65 | 60 minute | 360 rpm | KOH | 1% | 98% | [54] |
Duck tallow | methanol | 6:01 | 65 | 180 minute | - | KOH | 1 wt.% | 97% | [62] |
Silurus triostegus Heckel fish oil (STFO) | methanol | 6:01 | 32 | 60 minute | - | KOH | 0.50% w/w | 96% | [49] |
Waste cooking oil | methanol | 6:01 | microwave power of 750 W | 3 minute | - | CH3ONa | 0.75 wt.% | 97.90% | [63] |
soybean oil-assisted by low-frequency ultrasound (20 kHz) | Ethanol | 6:01 | 60 | 6 minute | 600 rpm | KOH | 1% (m/m) | 98% | [64] |
Waste frying oils | methanol | 12:01 | 65 | 150 minute | - | Tetramethylguanidine | 3 wt.% | > 90% | [65] |
Feedstock | Alcohol | Alcohol to oil Ratios | Enzymes | wt.% of Enzyme | Temp. (℃) | Stirring | Reaction time | Yield % | Remarks | Ref. |
Rapeseed oil | methanol with tert-butanol as a solvent | methanol/oil molar ratio 4:1 | Lipozyme TL IM | 3 wt.% | 35 | 130 rpm | 12 h | 95% | No loss in lipase activity after being repeatedly used for 200 cycles with tert-butanol | [86] |
Tert butanol/oil volume ratio 1:1 | Novozym 435 | as the reaction medium | ||||||||
Soybean oil | methanol | 1:1 | lipozyme TL | 0.04 | 40 | 150 rpm | - | 66% | - | [89] |
Soybean oil | methanol | 1:1 | silica gel | 0.06 | 40 | 150 rpm | - | 90% | Silica gel combined with lipozyme TL and three-step addition of methanol | [89] |
lipozyme TL | ||||||||||
Soyabean oil in ionic fluid-EmimTfO | methanol | 4:1 | Novozym 435 Pseudomonas cepacia immobilized on celite | 2 wt.% 0.1 | 50 | 250 rpm | 12 h | 80% | High production yield in ionic liquids show that ionic liquids are potential reaction media for biodiesel production | [88] |
Jatropha oil | ethanol | 4:1 | 50 | 200 rpm | 8 h | 98% | With presence of 4–5% (w/w) water | [90] |
The advantages of using lipases |
✔ Biocompatible, biodegradable and environmental acceptability ✔ Possibility of regeneration and reuse of the immobilized residue, because it can be left in the reactor if one keep the reactive flow ✔ Use of enzymes in reactors allows use of high concentration of them and that makes for a longer activation of the lipases ✔ Immobilization of lipase could protect it from the solvent that could be used in the reaction and that will prevent all enzyme particles getting together ✔ Separation of product will be easier using this catalyst, producing product of very high purity with less or no downstream operations |
Some disadvantages |
✔ Loss of some initial activity due to volume of the oil molecule ✔ Number of support enzyme is not uniform ✔ More expensive |
Feedstock | Alcohol | Alcohol to oil Ratios | Nano catalyst | wt.% of catalyst | Temp. (℃) | Reaction time | Yield % | Remarks | Ref. |
Waste mixed vegetable oil | Methanol | 5:1 | smoke deposited nano sized MgO | 1.5 | 55 | 45 min | 98.7 | The transesterification reaction was studied under constant ultrasonic mixing for different parameters | [95] |
Stillingia oil | Methanol | 12:1 | KF/CaO–Fe3O4 (Calcinated at 600 ℃) | 4 | 65 | 3 h | 95 | The catalyst is able to be reused up to 14 times without much deterioration in its activity | [99] |
Chinese tallow seed oil | Methanol | 12:1 | KF/CaO | 4 | 65 | 2.5 h | 96.8 | - | [92] |
Waste cooking oil | 7:1 | Nano CaO | 1.5 | 75 | 6 h | 94.37 | - | [100] | |
Waste cooking oil | 7:1 | Mixture of Nano CaO and Nano MgO | 3 | 75 | 6 h | 98.95 | The optimum mass proportion for CaO to MgO is 0.7:0.5 | [100] | |
Soybean oil | 12:1 | Nanoparticle of CaO from calcium Nitrate (CaO/CaN) | 8 | 65 | 6 h | 93 | - | [98] | |
Soybean oil | 12:1 | Nanoparticle of CaO from Snail shell (CaO/SS) | 8 | 65 | 6 h | 96 | - | [98] |
Feedstock | Alcohol | Alcohol to oil Ratios | Ionic liquid catalyst | Wt.% of catalyst | Temp. (℃) | Reaction time | Yield % | Remarks | Ref. |
Soybean oil | Methanol | 8:1 | Basic Ionic Liquids [Hnmm]OH | 4 | 70 | 1.5 h | 97 | The catalytic activity was affected by its alkalinity | [103] |
Cottonseed Oil | Methanol | 12:1 | 1-(4-Sulfonic acid) butylpyridinium hydrogen sulfate | 0.057 a | 170 | 5 h | 92 | The catalytic activity of the ionic liquid is dependent on its Brønsted acidic strength. | [107] |
Rapeseed oil | Methanol | 10:1 | 1-propyl-3-methyl imidazolium hydrogen sulfate ([PrMIM][HSO4]) | 10 | 140 | 5 h | 19.74 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-propylsulfonate-3methyl imidazolium hydrogen sulfate ([PrSO3HMIM][HSO4]) | 10 | 130 | 5 h | 94.91 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]) | 10 | 110 | 5 h | 8.89 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-butylsulfonate-3-methyl imidazolium hydrogen sulfate ([BSO3HMIM][HSO4]) | 10 | 130 | 5 h | 100 | - | [108] |
a molar ratio of ionic liquid to oil |
Feedstock | Alcohol | Process variables | Methyl ester % | Ref | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time (min) | Stirring speed (rpm) | Pressure (MPa) | |||||
Refined lard | Methanol | 45:1 | 335 | 15 | 500 | 20 | 89.91% | [14] | |
Rapeseed oil | Methanol | 45:1 | 350 | 4 | - | 14 | 95% | [113] | |
Coconut oil | Methanol | 42:1 | 350 | 7 | - | 19 | 95% | [114] | |
Palm kernel oil | Methanol | 42:1 | 350 | 7 | - | 19 | 96% | [114] | |
Rapeseed oil | Methanol | 42:1 | 350 | 15 | - | 12 | 93% | [115] | |
Rapeseed oil | Ethanol | 42:1 | 350 | 20 | - | 12 | 91.9% | [115] | |
Rapeseed oil | 1-propanol | 42:1 | 350 | 25 | - | 12 | 91.1% | [115] | |
Jatropha oil | Methanol | 43:1 | 320 | 4 | - | 8.4 | 100% | [116] | |
Sunflower seed oil | Methanol | 41:1 | 252 | 20 | - | 24 | 95% | [117] | |
Sunflower seed oil | Methanol with 0.3% CaO | 41:1 | 252 | 17 | - | 24 | 95% | [117] | |
Sunflower seed oil | Methanol with 5% CaO | 41:1 | 252 | 13 | - | 24 | 100% | [117] | |
RBDaPalm oil | Methanol | 45:1 | 350 | 5 | - | 40 | 95% | [118] | |
Vegetable oil | Ethanol with C2O Co-solvent | 25:1 | 200 | 6 | - | 20 | 80% | [119] | |
a Refined, Bleached and Deodorized |
Transesterification method | Suitable feedstock character | Advantages | Disadvantages | Ref |
Homogeneous Acid catalyzed | Any type of oil/fat feedstock including those with high free fatty acid. | ✔ Gives relatively high yield ✔ Insensitive to FFA content in feedstock, thus preferred-method if low-grade feedstock is used ✔ Esterification and transesterification occur simultaneously ✔ Less energy intensive |
✖ Corrosiveness of acids damage equipment ✖ More amount of free glycerol in the biodiesel ✖ Requires higher temperature operation but less than supercritical ✖ Relatively difficult to separation of catalyst from product. ✖ Has slower rate of production (relatively takes longer time) |
[22,40,43,44,120] |
Homogeneous Base catalyzed | Oil/fat feedstock with FFA content less than 0.5% by weight of the oil | ✔ Faster reaction rate than acid catalyzed transesterification ✔ Reaction can occur at mild reaction condition and less energy intensive ✔ Common catalysts such as NaOH and KOH are relatively cheap and widely available ✔ less corrosive |
✖ Sensitive to FFA content in the oil ✖ Saponification of oil is the main problem due to quality of feedstock ✖ Recovery of glycerol is difficult, ✖ Alkaline wastewater ✖ generated requires treatment |
[19,32,46,48,52,120] |
Heterogeneous Base Catalysis | Oil/fat feedstock with FFA content less than 0.5% by weight of the oil | ✔ Improved selectivity ✔ Easy to separate catalyst from reaction mixture ✔ Reduced process stages and wastes ✔ Enable to regenerate and reuse the catalyst ✔ Reaction can occur at mild reaction condition and less energy intensive |
✖ Catalyst might be poisoned when exposed to ambient air ✖ Sensitive to FFA content in the oil so selective to feedstock type ✖ Soap will be formed if there is high FFA content ✖ Soap formation associated with reduced biodiesel yield and problem in product purification ✖ Leaching of catalyst active sites may result to product contamination |
[32,66,69,71,120] |
Heterogeneous Acid Catalysis | Any type of oil/fat feedstock including those with high free fatty acid. | ✔ Catalyst separation from reaction mixture is easy ✔ Has reduced process stages and wastes ✔ Insensitive to feedstocks' FFA content. ✔ Preferred-method if low-grade oil is used ✔ Esterification and transesterification occur simultaneously ✔ Solid acid catalyst can be easily removed recycled |
✖ Complicated catalyst synthesis procedures lead to higher cost ✖ Requires high reaction temperature, high alcohol to oil molar ratio and long reaction time. ✖ Relatively energy intensive |
[69,75,76,120] |
Lipase catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content. | ✔ Insensitive to FFA and water content in the oil, thus preferred when low grade feedstock is used ✔ It is carried out at low reaction temperature ✔ Purification requires simple step, by enabling easy separation from the by-product, glycerol ✔ Gives high purity product (esters) ✔ Enables to reuse immobilized enzyme |
✖ The cost of enzyme is usually very high ✖ Gives relatively low yield ✖ It takes high reaction time ✖ The problem of lipases inactivation caused by methanol and glycerol |
[19,22,26,46,78,79,120] |
Nano catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content | ✔ Relatively with shorter reaction time ✔ Less amount of catalyst can be enough since has high specific surface area ✔ Catalyst can be reused many times ✔ Wide range of catalyst choice |
✖ Requires relatively more alcohol for effective yield ✖ In some cases preparation of appropriate catalysts costs more |
[91,92,93,94,95,96,97] |
Ionic liquid catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content but dependent on which type of ionic liquid is used (Acidic/basic) | ✔ Easy to separate final products due to formation of biphasic. ✔ Efficient and time saving ✔ While preparing catalysts their properties can be designed to suit a particular need ✔ Catalyst can be easily separated and reused many times ✔ High catalytic activity, excellent stability |
✖ High cost of ionic liquid production ✖ Requires relatively more alcohol for effective yield |
[101,102,103,104,105,106] |
Supercritical transesterification | Any oil and fat with greater range and water content and high FFA content (in particular, used cooking oil) | ✔ It takes very less time to complete ✔ Insensitive to greater water content of the feedstocks ✔ Produces more than a kilo of fuel per kilo of feedstock ✔ No need of washing the product as there is no catalyst used ✔ It is more easier to design as a continuous process |
✖ Requires higher temperature and pressure ✖ It is not an economic alternative due to its high operating cost, due to high pressures and high ✖ temperatures ✖ Relatively there is high methanol consumption (e.g., high methanol/crude-oil molar ratio of 40/1) |
[9,40,111,112,115,118,119] |
Method | Temperature (℃) | Residence Time | Heating rate (℃/s) | Major products |
Conventional/slow pyrolysis | Med-high (400–500) | Long 5–30 min | Low 10 | Gases Char Bio-oil (tar) |
Fast pyrolysis | Med-high (400–650) | Short 0.5–2 s | High 100 | Bio-oil (thinner) Gases Char |
Ultra-fast/flash pyrolysis | High (700–1000) | Very short < 0.5 s | Low 10 | Gases Bio-oil |
Feedstock | Alcohol | Process variables | Yield % achieved | Ref. | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time | Stirring speed | Acid Catalyst | Catalyst concentration | ||||
Mixed oil b | Methanol | 6:1 | 60 | - | 300 rpm | H2SO4 | 2.5% | 96.6% | [43] |
Soybean oil | Methanol | 20:1 | 120 | 5 h | - | trifluoroacetic acid | 2.0 M | 98.4% | [41] |
Canola oil | Methanol with terahydrofuran as Co-solvent | 24:1 | 110 | 18 h | AlCl3 | 5% | 98% | [39] | |
Corn oil | Methanol with dimethyl ether as Co-solvent | 6:1 | 80 | 2 h | - | p-toluenesulfonic acid | 4 wt.% | 100% | [44] |
Canola oil up to 20% FFA | Methanol | 9:1 | 200 | - | - | 12-Tungstophosphoric acid | 3 wt.% | 90 wt.% | [45] |
b mixed oil-50% sunflower and 50% soybean oil |
Catalyst | Concentration of the catalyst (wt.%, by weight of crude oil) | Ester content (wt.%) | Product yield (wt.%) |
NaOH | 1.1 | 94.0 | 85.3 |
KOH | 1.5 | 92.5 | 86.0 |
CH3ONa | 1.3 | 92.8 | 89.0 |
Catalyst (gm) |
Oil (gm) |
Methanol (gm) |
Reaction Time (hr) |
Reaction Temp. (℃) |
Biodiesel (%) |
Glycerin (%) |
1.2 | 100 | 20 | 1 | 65 | 87.20 | 30.80 |
1.0 | 100 | 20 | 1 | 65 | 92.40 | 27.35 |
0.8 | 100 | 20 | 1 | 65 | 95.33 | 24.22 |
0.6 | 100 | 20 | 1 | 65 | 74.45 | 45.37 |
Feedstock | Alcohol | Process variables | Yield % achieved | Ref. | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time | Stirring speed | Catalyst type | Cat. Concentration | ||||
Rice bran oil | methanol | 1:09 | 55 | 60 minute | - | NaOH | 0.75% (w/w) | Optimum | [57] |
Sunflower cooking oil | methanol | 6:01 | 40 | - | 320 rpm | KOH | 1% | 99.50% | [53] |
refined cooking vegetable oils | methanol | 6:01 | 65 | 60 minute | - | KOH | 1.2 wt.% | 97.50% | [58] |
Waste cooking vegetable oils | methanol | 6:01 | 65 | 60 minute | - | KOH | 1.2 wt.% | 93.20% | [58] |
Jatropha oil | methanol | 5:01 | 65 | 60 minute | - | NaOH | 0.80% | 95.5%. | [59] |
Soybean oil | methanol | 6:01 | 60 ± 1 | 60 minute | - | NaOH | 1% | 90% | [60] |
Cottonseed oils | methanol | 6:01 | 60 ± 1 | 60 minute | - | NaOH | 1% | 98.50% | [60] |
Waste frying oils | methanol | 7.5:1 | 50 | 30 minute | - | NaOH | 0.50% | 96% | [61] |
Karanja oil | methanol | 6:01 | 65 | 15 minute | 360 rpm | KOH | 1% | > 85% | [54] |
Karanja oil | methanol | 12:01 | 65 | 60 minute | 360 rpm | KOH | 1% | 98% | [54] |
Duck tallow | methanol | 6:01 | 65 | 180 minute | - | KOH | 1 wt.% | 97% | [62] |
Silurus triostegus Heckel fish oil (STFO) | methanol | 6:01 | 32 | 60 minute | - | KOH | 0.50% w/w | 96% | [49] |
Waste cooking oil | methanol | 6:01 | microwave power of 750 W | 3 minute | - | CH3ONa | 0.75 wt.% | 97.90% | [63] |
soybean oil-assisted by low-frequency ultrasound (20 kHz) | Ethanol | 6:01 | 60 | 6 minute | 600 rpm | KOH | 1% (m/m) | 98% | [64] |
Waste frying oils | methanol | 12:01 | 65 | 150 minute | - | Tetramethylguanidine | 3 wt.% | > 90% | [65] |
Feedstock | Alcohol | Alcohol to oil Ratios | Enzymes | wt.% of Enzyme | Temp. (℃) | Stirring | Reaction time | Yield % | Remarks | Ref. |
Rapeseed oil | methanol with tert-butanol as a solvent | methanol/oil molar ratio 4:1 | Lipozyme TL IM | 3 wt.% | 35 | 130 rpm | 12 h | 95% | No loss in lipase activity after being repeatedly used for 200 cycles with tert-butanol | [86] |
Tert butanol/oil volume ratio 1:1 | Novozym 435 | as the reaction medium | ||||||||
Soybean oil | methanol | 1:1 | lipozyme TL | 0.04 | 40 | 150 rpm | - | 66% | - | [89] |
Soybean oil | methanol | 1:1 | silica gel | 0.06 | 40 | 150 rpm | - | 90% | Silica gel combined with lipozyme TL and three-step addition of methanol | [89] |
lipozyme TL | ||||||||||
Soyabean oil in ionic fluid-EmimTfO | methanol | 4:1 | Novozym 435 Pseudomonas cepacia immobilized on celite | 2 wt.% 0.1 | 50 | 250 rpm | 12 h | 80% | High production yield in ionic liquids show that ionic liquids are potential reaction media for biodiesel production | [88] |
Jatropha oil | ethanol | 4:1 | 50 | 200 rpm | 8 h | 98% | With presence of 4–5% (w/w) water | [90] |
The advantages of using lipases |
✔ Biocompatible, biodegradable and environmental acceptability ✔ Possibility of regeneration and reuse of the immobilized residue, because it can be left in the reactor if one keep the reactive flow ✔ Use of enzymes in reactors allows use of high concentration of them and that makes for a longer activation of the lipases ✔ Immobilization of lipase could protect it from the solvent that could be used in the reaction and that will prevent all enzyme particles getting together ✔ Separation of product will be easier using this catalyst, producing product of very high purity with less or no downstream operations |
Some disadvantages |
✔ Loss of some initial activity due to volume of the oil molecule ✔ Number of support enzyme is not uniform ✔ More expensive |
Feedstock | Alcohol | Alcohol to oil Ratios | Nano catalyst | wt.% of catalyst | Temp. (℃) | Reaction time | Yield % | Remarks | Ref. |
Waste mixed vegetable oil | Methanol | 5:1 | smoke deposited nano sized MgO | 1.5 | 55 | 45 min | 98.7 | The transesterification reaction was studied under constant ultrasonic mixing for different parameters | [95] |
Stillingia oil | Methanol | 12:1 | KF/CaO–Fe3O4 (Calcinated at 600 ℃) | 4 | 65 | 3 h | 95 | The catalyst is able to be reused up to 14 times without much deterioration in its activity | [99] |
Chinese tallow seed oil | Methanol | 12:1 | KF/CaO | 4 | 65 | 2.5 h | 96.8 | - | [92] |
Waste cooking oil | 7:1 | Nano CaO | 1.5 | 75 | 6 h | 94.37 | - | [100] | |
Waste cooking oil | 7:1 | Mixture of Nano CaO and Nano MgO | 3 | 75 | 6 h | 98.95 | The optimum mass proportion for CaO to MgO is 0.7:0.5 | [100] | |
Soybean oil | 12:1 | Nanoparticle of CaO from calcium Nitrate (CaO/CaN) | 8 | 65 | 6 h | 93 | - | [98] | |
Soybean oil | 12:1 | Nanoparticle of CaO from Snail shell (CaO/SS) | 8 | 65 | 6 h | 96 | - | [98] |
Feedstock | Alcohol | Alcohol to oil Ratios | Ionic liquid catalyst | Wt.% of catalyst | Temp. (℃) | Reaction time | Yield % | Remarks | Ref. |
Soybean oil | Methanol | 8:1 | Basic Ionic Liquids [Hnmm]OH | 4 | 70 | 1.5 h | 97 | The catalytic activity was affected by its alkalinity | [103] |
Cottonseed Oil | Methanol | 12:1 | 1-(4-Sulfonic acid) butylpyridinium hydrogen sulfate | 0.057 a | 170 | 5 h | 92 | The catalytic activity of the ionic liquid is dependent on its Brønsted acidic strength. | [107] |
Rapeseed oil | Methanol | 10:1 | 1-propyl-3-methyl imidazolium hydrogen sulfate ([PrMIM][HSO4]) | 10 | 140 | 5 h | 19.74 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-propylsulfonate-3methyl imidazolium hydrogen sulfate ([PrSO3HMIM][HSO4]) | 10 | 130 | 5 h | 94.91 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-butyl-3-methylimidazolium hydrogen sulfate ([BMIM][HSO4]) | 10 | 110 | 5 h | 8.89 | - | [108] |
Rapeseed oil | Methanol | 10:1 | 1-butylsulfonate-3-methyl imidazolium hydrogen sulfate ([BSO3HMIM][HSO4]) | 10 | 130 | 5 h | 100 | - | [108] |
a molar ratio of ionic liquid to oil |
Feedstock | Alcohol | Process variables | Methyl ester % | Ref | |||||
Alcohol to oil ratio | Temperature (℃) | Reaction time (min) | Stirring speed (rpm) | Pressure (MPa) | |||||
Refined lard | Methanol | 45:1 | 335 | 15 | 500 | 20 | 89.91% | [14] | |
Rapeseed oil | Methanol | 45:1 | 350 | 4 | - | 14 | 95% | [113] | |
Coconut oil | Methanol | 42:1 | 350 | 7 | - | 19 | 95% | [114] | |
Palm kernel oil | Methanol | 42:1 | 350 | 7 | - | 19 | 96% | [114] | |
Rapeseed oil | Methanol | 42:1 | 350 | 15 | - | 12 | 93% | [115] | |
Rapeseed oil | Ethanol | 42:1 | 350 | 20 | - | 12 | 91.9% | [115] | |
Rapeseed oil | 1-propanol | 42:1 | 350 | 25 | - | 12 | 91.1% | [115] | |
Jatropha oil | Methanol | 43:1 | 320 | 4 | - | 8.4 | 100% | [116] | |
Sunflower seed oil | Methanol | 41:1 | 252 | 20 | - | 24 | 95% | [117] | |
Sunflower seed oil | Methanol with 0.3% CaO | 41:1 | 252 | 17 | - | 24 | 95% | [117] | |
Sunflower seed oil | Methanol with 5% CaO | 41:1 | 252 | 13 | - | 24 | 100% | [117] | |
RBDaPalm oil | Methanol | 45:1 | 350 | 5 | - | 40 | 95% | [118] | |
Vegetable oil | Ethanol with C2O Co-solvent | 25:1 | 200 | 6 | - | 20 | 80% | [119] | |
a Refined, Bleached and Deodorized |
Transesterification method | Suitable feedstock character | Advantages | Disadvantages | Ref |
Homogeneous Acid catalyzed | Any type of oil/fat feedstock including those with high free fatty acid. | ✔ Gives relatively high yield ✔ Insensitive to FFA content in feedstock, thus preferred-method if low-grade feedstock is used ✔ Esterification and transesterification occur simultaneously ✔ Less energy intensive |
✖ Corrosiveness of acids damage equipment ✖ More amount of free glycerol in the biodiesel ✖ Requires higher temperature operation but less than supercritical ✖ Relatively difficult to separation of catalyst from product. ✖ Has slower rate of production (relatively takes longer time) |
[22,40,43,44,120] |
Homogeneous Base catalyzed | Oil/fat feedstock with FFA content less than 0.5% by weight of the oil | ✔ Faster reaction rate than acid catalyzed transesterification ✔ Reaction can occur at mild reaction condition and less energy intensive ✔ Common catalysts such as NaOH and KOH are relatively cheap and widely available ✔ less corrosive |
✖ Sensitive to FFA content in the oil ✖ Saponification of oil is the main problem due to quality of feedstock ✖ Recovery of glycerol is difficult, ✖ Alkaline wastewater ✖ generated requires treatment |
[19,32,46,48,52,120] |
Heterogeneous Base Catalysis | Oil/fat feedstock with FFA content less than 0.5% by weight of the oil | ✔ Improved selectivity ✔ Easy to separate catalyst from reaction mixture ✔ Reduced process stages and wastes ✔ Enable to regenerate and reuse the catalyst ✔ Reaction can occur at mild reaction condition and less energy intensive |
✖ Catalyst might be poisoned when exposed to ambient air ✖ Sensitive to FFA content in the oil so selective to feedstock type ✖ Soap will be formed if there is high FFA content ✖ Soap formation associated with reduced biodiesel yield and problem in product purification ✖ Leaching of catalyst active sites may result to product contamination |
[32,66,69,71,120] |
Heterogeneous Acid Catalysis | Any type of oil/fat feedstock including those with high free fatty acid. | ✔ Catalyst separation from reaction mixture is easy ✔ Has reduced process stages and wastes ✔ Insensitive to feedstocks' FFA content. ✔ Preferred-method if low-grade oil is used ✔ Esterification and transesterification occur simultaneously ✔ Solid acid catalyst can be easily removed recycled |
✖ Complicated catalyst synthesis procedures lead to higher cost ✖ Requires high reaction temperature, high alcohol to oil molar ratio and long reaction time. ✖ Relatively energy intensive |
[69,75,76,120] |
Lipase catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content. | ✔ Insensitive to FFA and water content in the oil, thus preferred when low grade feedstock is used ✔ It is carried out at low reaction temperature ✔ Purification requires simple step, by enabling easy separation from the by-product, glycerol ✔ Gives high purity product (esters) ✔ Enables to reuse immobilized enzyme |
✖ The cost of enzyme is usually very high ✖ Gives relatively low yield ✖ It takes high reaction time ✖ The problem of lipases inactivation caused by methanol and glycerol |
[19,22,26,46,78,79,120] |
Nano catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content | ✔ Relatively with shorter reaction time ✔ Less amount of catalyst can be enough since has high specific surface area ✔ Catalyst can be reused many times ✔ Wide range of catalyst choice |
✖ Requires relatively more alcohol for effective yield ✖ In some cases preparation of appropriate catalysts costs more |
[91,92,93,94,95,96,97] |
Ionic liquid catalyzed transesterification | Any type of oil/fat feedstock including those with high free fatty acid and water content but dependent on which type of ionic liquid is used (Acidic/basic) | ✔ Easy to separate final products due to formation of biphasic. ✔ Efficient and time saving ✔ While preparing catalysts their properties can be designed to suit a particular need ✔ Catalyst can be easily separated and reused many times ✔ High catalytic activity, excellent stability |
✖ High cost of ionic liquid production ✖ Requires relatively more alcohol for effective yield |
[101,102,103,104,105,106] |
Supercritical transesterification | Any oil and fat with greater range and water content and high FFA content (in particular, used cooking oil) | ✔ It takes very less time to complete ✔ Insensitive to greater water content of the feedstocks ✔ Produces more than a kilo of fuel per kilo of feedstock ✔ No need of washing the product as there is no catalyst used ✔ It is more easier to design as a continuous process |
✖ Requires higher temperature and pressure ✖ It is not an economic alternative due to its high operating cost, due to high pressures and high ✖ temperatures ✖ Relatively there is high methanol consumption (e.g., high methanol/crude-oil molar ratio of 40/1) |
[9,40,111,112,115,118,119] |