Marwan Abdul Hakim Shaah
a,
Md. Sohrab Hossain
*a,
Faisal Aboelksim Salem Allafi
a,
Alyaa Alsaedi
a,
Norli Ismail
a,
Mohd Omar Ab Kadir
b and
Mardiana Idayu Ahmad
*a
aSchool of Industrial Technology, Universiti Sains Malaysia, 11800 USM, Penang, Malaysia. E-mail: sohrab@usm.my; mardianaidayu@usm.my; Fax: +6046533678; Tel: +6046532216 Tel: +6046532214
bPultex Sdn Bhd, Jalan Kampung Jawa, Bayan Baru, 11950 Bayan Lepas, Penang, Malaysia
First published on 19th July 2021
There is increasing concern regarding alleviating world energy demand by determining an alternative to petroleum-derived fuels due to the rapid depletion of fossil fuels, rapid population growth, and urbanization. Biodiesel can be utilized as an alternative fuel to petroleum-derived diesel for the combustion engine. At present, edible crops are the primary source of biodiesel production. However, the excessive utilization of these edible crops for large-scale biodiesel production might cause food supply depletion and economic imbalance. Moreover, the utilization of edible oil as a biodiesel feedstock increases biodiesel production costs due to the high price of edible oils. A possible solution to overcome the existing limitations of biodiesel production is to utilize non-edible crops oil as a feedstock. The present study was conducted to determine the possibility and challenges of utilizing non-edible oil as a potential feedstock for biodiesel production. Several aspects related to non-edible oil as a biodiesel feedstock such as overview of biodiesel feedstocks, non-edible oil resources, non-edible oil extraction technology, its physicochemical and fatty acid properties, biodiesel production technologies, advantages and limitation of using non-edible oil as a feedstock for biodiesel production have been reviewed in various recent publications. The finding of the present study reveals that there is a huge opportunity to utilize non-edible oil as a feedstock for biodiesel production.
Biodiesel is a liquid biofuel that can be synthesized from industrial crops, agricultural by-products, and municipal wastes.3 Studies have been performed on biodiesel production from various matrices and develop its quantitative and qualitative properties to improve its reliability and sustainability as a renowned source of green energy.1,5 Biodiesel has been produced by utilizing various agricultural crops (i.e., corn, sugarcane, and wheat) and edible oil (rapeseed, sunflower, soybean and palm) as feedstock for the first-generation biofuel.5,6 However, the utilization of agricultural crops and edible oil to produce biodiesel have raised a potential conflict of “food vs. fuel”. Besides, this increased the biodiesel production cost due to increasing feedstock price with growing market demand along with competition for food.6 Consequently, studies have been carried out on biodiesel production from non-food crops, animal fats, fungi, bacteria, and microalgae.5–8
Various technologies have been employed to produce biodiesel from non-edible oils.3,8–10 The potential advantages of producing biodiesel from non-edible oils are available in abundance, low production cost, high oil yield and above all it does not conflict with food products. Therefore, the present study was conducted to review the potential and challenges of utilizing non-edible oils as a reliable feedstock for biodiesel production. Wherein, the feasibility of non-edible oil as a feedstock was determined by reviewing various aspects of non-edible oils such as oil composition, cultivation, oil yield, land and resources availability for cultivation. Besides, biodiesel conversion technologies and the properties of produced biodiesel from various non-edible oils were also reviewed in this study. Finally, it was pointed out the best non-edible crop, conversation technology and author views to overcome limitations of using non-edible oil as a potential feedstock for biodiesel production.
Global energy consumption has increased hastily with increasing population, lifestyle, and rural development. However, the utilization of fossil fuels-based energy is significantly increasing the environmental pollution concern and threatening our ecosystem.3,5,8 Due to the rapid depletion of primary energy sources and the ecological pollution concern of using petroleum-based fuel, the world energy commission is looking for alternative energy, wherein biodiesel is highly promising. The name ‘Biodiesel’ was promoted by the National Soy Diesel Development Board, USA in 1992.14 Generally, biodiesel is a non-petroleum-based fuel consisting of mono-alkyl esters of long-chain fatty acids, derived from vegetable oils or animal fats with an added requisite of minimizing greenhouse gas emissions. Global biodiesel production was 9.2 Mtoe in 2000, which increased to 95 Mtoe in 2018.15 Global biodiesel production and consumption are currently leading by the USA and Europe. The annual consumption of biodiesel in 2005 was 3.02 MT in Europe mad 3.32 MT in the USA. These are about 0.5–1% and about 2% of total biofuels consumption in the transportation section of USA and Europe, respectively.15 Many countries in the world are encouraged to use biodiesel in the transportation sectors, which tremendously enhanced global biodiesel consumption. It was reported that the total biodiesel consumption was 26.8 MT in 2016 by 56 countries, where 58% of the total biodiesel consumed by the five countries, as shown in Fig. 1.
Many countries encourage to increase biodiesel production and utilization in the transportation sectors. Like Europe and the USA, the biodiesel production and utilization has also started experiencing in Asian countries, including China, India and Malaysia. For instance, China and India government have targeted to utilize 15% biodiesel blended with petro-diesel in 2020. The government of Malaysia has stated lunching B10 (10% biodiesel blended with petro-diesel) in 2019, which would be increased to B20 in 2020.16 The global biodiesel production is increasing rapidly due to its potential advantage in replacing petro-diesel, such as:2,3,9,17
(i) Biodiesel is derived from renewable energy sources.
(ii) Biodiesel is highly biodegradable.
(iii) Biodiesel is noncorrosive.
(iv) Minimize the dependency on fossil fuels.
(v) Reduce greenhouses gases emission and global warming.
(vi) It can be utilized as an alternative fuel for diesel in boilers or internal combustion engines with minor mechanical modifications.
(vii) Biodiesel promotes complete combustion.
(viii) Suitable to utilize in modern diesel engines with equally engine performance of petro-diesel.
(ix) Biodiesel has a higher lubricity than petroleum-derived diesel.
Biodiesel is derived from plant oils, and animal fats have similar characteristics to petroleum-derived diesel oil.21 The edible oil utilized for biodiesel production is including sunflower oil,19 soybean oil,22 rapeseed oil,23 palm oil24 and coconut oil.25 Over 95% of biodiesel are currently obtained from edible oils.15,21 Several issues have raised with the utilization of edible oils for the biodiesel production, mainly its consequences to the world food market. Large-scale biodiesel production from edible oil crops may bring global imbalance of food supply, which might enhance the global food insecurity.7,11 The argument of whether the production of feedstock is for food or fuel continues, albeit with the overstated consequences as this may result in a price hike of biodiesel and edible oils. Recently, the environmentalist has also raised concern on biodiesel production from edible oil. They argued that the large-scale production of biodiesel requires the expansion plantation of edible oil crops, which causing deforestation and destroying the ecosystem.4,6 Thus, biodiesel production from edible oil enforces the competition between food vs. fuel economy. Wherein, the production of biodiesel from edible oil is competing with the limited land area available for the food crops production. This trend is already being observed in many countries globally, where a significant amount of land has been utilized for oil crops production to mitigate the increasing demand for biodiesel production. Eventually, the implementation of edible oil biodiesel as a substitute for petroleum diesel oil may reduce the worldwide edible oil supply.
To overcome from this distressing phenomenon, numerous researches have been conducted worldwide to determine alternative and renewable feedstocks for biodiesel production.3,8,9,18 Biodiesel derived from non-edible oil is considered 2nd generation biofuel. Jatropha, rubber seed, jojoba, tobacco seed, sea mango, neem, candlenut, mahua, karanja, yellow oleander are examples of non-edible plant sources which make up the 2nd generation feedstock.18 Moreover, animal fats sources like poultry fat, pork lard, and beef tallow can be utilized as a source for producing biodiesel.18,26 In recent years, waste edible oils such as yellow grease and waste cooking oils have also been utilized as possible sources of biodiesel production.16,20 Biodiesel can also derive from algal biomass.17 Algae can be divided into two major groups, such as unicellular (microalgae) and multicellular (macroalgae or seaweeds).27 Microalgae as a source of liquid fuel was initiated during the 1980s,17 which has sparked the study of various kinds of microalgae species to produce biodiesel in different growth environments. Generally, the high lipids content of algae (about 70%) makes it considerable source for biodiesel production. Therefore, a large amount of biodiesel can be produced a relatively small amount of algal biomass. Besides, its high photosynthetic efficiency impacts in controlling global warming. Thus, algal biomass could be applied as a leading feedstock for the production of biodiesel. However, the conversion of biodiesel from algal biomass requires advanced technology for the algal oil extraction and removal of the fermentable sugar from algal biomass.28 Besides, the algal biomass has potential applications in food, pharmaceuticals, and cosmetics industries.27 Table 1 represents the comparisons among first, second and third-generation feedstock for biodiesel production.3,6,18,29
Biofuels | Feedstock source | Advantages | Disadvantages |
---|---|---|---|
1st generation | Edible oil | - Simple conversation process | - Relative low oil yield |
- Food vs. biofuel debate | |||
- Causes deforestation and destroying ecosystem | |||
2nd generation | Non-edible oil | - Abundance availability number of non-edible crops worldwide | - Intractable structure of the feedstock |
- No debate between food vs. fuel economy | |||
3rd generation | Algal biomass | - High lipids content | - It requires advance technology for biodiesel conversion |
- High growth rate | - It has other application in food, pharmaceutical and cosmetics industries | ||
- Its cultivation reduces global warming |
Table 2 shows the list of non-edible oil crops, their annual production per hector land per year (kg per ht per year) and percentage oil yield (wt%). The raw materials price is the main obstacle to produce biodiesel. It is being reported that the raw material price for biodiesel production is an account of 70–90% of the total biodiesel production.29,32 Non-edible oil crops such as such as Jatropha (2500 kg per ht per year),33 candlenut (1600 kg per ht per year),35 neem (2670 kg per ht per year),40 karanja (900–9000 kg per ht per year),41 yellow oleander (5200 kg per ht per year),46 sea mango (1900–2500 kg per ht per year)47 grow in plenty. These plants can grow almost anywhere with minimal cultivation efforts, even in sandy and saline soils, which are not suitable for food crops production.33,39,44 Thus, the utilization of the non-edible oil as a feedstock would minimize the biodiesel production cost due to the cheaper raw materials source. Generally, the plantation cost for non-edible oil crops is much cheaper than edible crops. This is because the cultivation of the edible crop requires high soil nutrition, a good irrigation system, and incentive care to maintain soil nutrients and moisture.33 Another important fact for determining the suitability of using non-edible oil as an alternative feedstock for biodiesel production is the percentage of oil content (wt%). The percentage oil content in Jatropha seed (40–60 wt%),33 rubber seed (40–50 wt%),36 see mango seed (40–50 wt%),47 candlenut (60–65 wt%),35 polanga (60–70 wt%)43 and yellow oleander (60–65 wt%)46 are much higher than edible oil crops such as rapeseed (37–50 wt%),23 soybean (20 wt%)22 and palm (20 wt%).24
Non-edible oil crops | Scientific name | Plant type | Major crop | Yield (kg per ha per year) | Oil content (wt%) | References |
---|---|---|---|---|---|---|
Jatropha | Jatropha curcas | Tree | Seed | 2500 | 40–60 | 33 |
Mahua | Madhuca longifolia | Tree | Seed | 20–200 | 35–50 | 34 |
Candlenut | Aleurites moluccanus | Tree | Seed | 16000 | 60–65 | 35 |
Rubber | Hevea brasiliensis | Tree | Seed | 100–150 | 40–50 | 36 |
Soapnut | Sapindus mukorossi | Tree | Seed | — | 23–30 | 33 and 37 |
Jojoba | Simmondsia chinensis | Shrub | Seed | 500–5000 | 40–50 | 38 |
Tobacco | Nicotiana tabacum | Herb | Seed | 1170 | 35–49 | 39 |
Neem | Azadirachta indica | Tree | Seed | 2670 | 25–45 | 40 |
Karanja | Millettia pinnata | Tree | Seed | 900–9000 | 30–50 | 41 |
Castor | Ricinus communis | Tree/shrub | Seed | 450 | 45–50 | 42 |
Polanga | Calophyllum inophyllum L. | Tree | Seed | 3700 | 65–75 | 43 |
Cotton | Gossypium | Tree | Seed | 649 | 17–23 | 44 |
Kusum | Carthamus tinctorius | Tree | Seed | — | 51–62 | 45 |
Yellow oleander | Cascabela thevetia | Tree | Seed | 52000 | 60–65 | 46 |
Sea mango | Cerbera odollam | Tree | Seed | 1900–2500 | 40–50 | 47 |
Tung | Vernicia fordii | Tree | Seed | 450–600 | 30–40 | 33 |
Bottle tree | Brachychiton rupestris | Tree | Seed | 250–300 | 50–60 | 48 |
Mahua (Madhuca indica) tree is a medium-sized tree with a height of up to 20 m. It generally grows mostly in India, Pakistan, Bangladesh, and Malaysia.34,50 It is a fast-growing evergreen or semi-green tree, and it can be planted in hot and wet regions. The potential production of mahua seed is about 60 MT per annum in India.34 The oilseeds and oil yield in the mahua crops vary with the maturity of the mahua tree. Generally, total oilseed yield per annum from the mature mahua tree ranges from 20 to 200 kg ha−1, wherein the total oil yield per annum is about 2.7 tonnes per ha. The calorific value of mahua seed oil is reported to be 38.5 kJ kg−1, which is lower by 14% than the mineral diesel's calorific value (42 kJ kg−1).50 Candlenut (Aleurites moluccana L.) is a flowering tree and the height of a mature candlenut tree about 20 m. It is also known as kemiri in Bahasa Indonesia and kukui nut in Hawaii.51 The candlenut tree is a domesticated multipurpose tree, mainly growing in the Indo-Malaysia region.35 The annual production of the candlenut seed about 16 ton per ha and the yearly oil yield is around 3200 kg ha−1.51 Candlenut seed contains approximately 30–60% of candlenut oil, and the oil can be obtained from the candlenut seeds using several extraction techniques. Candlenut oil has a high iodine number (≥125) and a lower pour point.
The rubber tree is also known as the para rubber, and it derives from the amazon rain forest in Brazil. The rubber tree is distributed in Malaysia, Indonesia, India, Thailand, Sri Lanka, and Liberia. The height of a rubber tree up to 34 m and rubber seeds' weight ranging from 2–4 g.33 A typical plantation has about 350–500 trees per ha and yields about 100 to 150 kg ha−1 rubber seeds annually.52 The rubber seeds oil is brown, and the oil content in rubber seeds and kernel accounts for 40–60 wt%.33 The fatty acid content in rubber seed oil is about 17%, higher than vegetable oils. The major fatty acid compositions in rubber seeds oil are stearic acid, oleic acid, palmitic acid, linoleic acid, and linolenic acid.53
Soapnut tree is generally growing in tropical and subtropical climates.54 The soapnut tree can grow in leached and deep loamy soils; therefore, the cultivation of the soapnut tree in leached and deep loamy soils would minimize soil erosion.33 The seeds contain 23–51.8 wt% oil, the oil contains about 92% is triglycerides.37 Jojoba tree grows in Mexico, Mojave, and the Sonoran Deserts.38 Jojoba tree is 0.7–1.0 m high, and the jojoba fruits look like dark brown nutlike fruit. The seeds of the jojoba contain about 45 to 55 wt% lipid.55 The characteristics of jojoba oil differ fundamentally from edible oil. The chemical structure of the jojoba seeds oil contains long straight-chain ester, and the oil contains about 97% of waxed ester and 3% of FFAs.56 Jojoba oil is non-toxic, biodegradable, high viscosity, low volatility, high flash points, and relatively stable with a high dielectric constant.55 The high oil content and the wild nature of jojoba plants make it one of the best non-edible crops to be used as a potential feedstock for biodiesel production.
Tobacco is one of the most common non-edible crops in the world, with enormous social and economic importance. It is an annually grown herbaceous plant widespread in South and North America, Russia, India, and Macedonia.39 Tobacco seed contains 35–49 wt% of tobacco oil, and the oil does not contain nicotine.33 The primary fatty acids in tobacco seed oil are palmitic acid, linoleic acid, stearic acid, and oleic acid.57 Neem is a fast-growing tree with a height of 25 m.40 Generally, the neem tree can tolerate high temperatures and grow in non-fertile and degraded soil. The tree is originated from the Indian subcontinent but becomes a very established tree in many countries around the world, including Africa, central and south America, Bangladesh, Burma, Malaysia, Pakistan, and Sri Lanka.33 The fruiting of the neem tree starts at 3–5 years, but the maximum productivity of neem seeds begins after 15 years of plantation. The neem fruit has a shape that varies from oval to round, with a diameter of 1.0–1.5 cm and length 1.4–2.8 cm.58 Neem seeds have 45 wt% oil, and it mainly contains oleic, palmitic, and stearic acids.40
Karanja is a fast-growing and medium-sized leguminous tree. It can grow in various agro-climatic conditions, including clayey soil, stony soil, and sandy soil.59 The height of the karanja is about 25 m. The harvesting of the karanja seeds can carry out after 4–6 years of plantation. The yield of karanja seeds of 0.9 to 9.0 tonnes per ha.41 The fresh seeds contain approximately 30–35 wt% thick yellow-orange to brown oil.59 The karanja oil is considered a non-edible oil due to having karanjin and toxic di-ketone pongamol.41 The major fatty acids in karanja oil are palmitic, linoleic, oleic acid, and stearic acids.59 Castor plant grows in tropical regions worldwide, and it grows well in dry subtropical areas to wet tropics within the temperature range from 20–25 °C.60 The plant is drought and pest-resistant and can be grown practically anywhere land is available. It grows well from the. Castor seeds are poisonous to humans and animals due to the presence of ricin and other toxic compounds. The oil content in castor seeds is 46–55 wt%.42 Polanga is a medium to large evergreen and non-edible oilseed tree with an average length 8–20 m. It grows on exposed sea sands or in deep soil with a 750–5000 mm per year rainfall requirement. The tree begins yield after 4–5 years of plantation. The fruit bears a seed inside a corky shell covering and size of the seeds is 10–20 mm. The oil yield from polanga plantation is about 2000 kg per ha per annum. Polanga seeds have a high oil content (65–75%) that contains various saturated and unsaturated fatty acid.43 The polanga seeds oil is greenish with thick, woodsy or nutty-smelling.61
Kusum tree is a medium to large-sized tree with 35 to 45 feet in height. The oil content in kusum seeds is 51–62%.45 The oil contains toxic cyanogenic compounds and therefore, the kusum oil is not considered as edible oil. The fatty acid profile in kusum oil shows about 40% unsaturated fatty acid, and 53% saturated fatty acid.62 Yellow oleander is a drought-resistant, and non-edible shrub.46 The Yellow oleander plant is native to tropics and subtropics countries and is inherent to Central and South America. The height of the yellow oleander tree is about 10–18 feet. The annual production of yellow oleander seeds is about 52 tonnes per ha, and the seeds contain 60–65 wt% oil.29 Tung tree grows in native China and other countries below an altitude of 1600 m. The average height of the tung trees is about 20 m.63 The fruit's oil content is between 14–20%, seed's oil content between 30–40% and the kernel oil content between 53–60%. The average oil yield is 450–600 kg per ha per annum.33,64 Tung oil contains unsaturated fatty acids, α-eleostearic acid, β-eleostearic acid, and high conjugated triene fatty acid.63 Moringa oleifera is a fast-growing and widely cultivated plant. Generally, the moringa plants grow in tropical and subtropical areas with a required rainfall between 250 and 2000 mm. It can grow in tolerates poor soil and dry sandy soil.65,66 The moringa seed contains 38–40% of oil, and the oil contains high-quality fatty acid (oleic acid > 70%).66
Although non-edible oil crops oil is considered as an alternative feedstock for biodiesel production, the low oil yield of some non-edible crops, high FFAs, high polyunsaturated fatty acids, and low unsaturated fatty acids content in oil is the major barrier for the commercial-scale biodiesel production.18,29,63 Better quality biodiesel contains a higher amount of mono-unsaturated fatty acids, the lesser amount of saturated and polyunsaturated fatty acids. To overcome these limitations, scientists and plant biotechnologists have implemented genetic engineering technology.67 The purpose of genetically modified plants is to enhance seed oil yield in crops and improve oil quality by changing the fatty acids compositions in plant seed oil. For instance, Roesler et al.68 obtained an increase 5% rapeseed seed oil by modifying rapeseed chloroplast using a cytosolic version of acetyl-CoA carboxylase enzymes. Vigeolas and Geigenberger69 increased about 40% seed oil content in rapeseed with increasing glycerol-3-phosphate levels in seeds by overexpression of a yeast cytosolic glycerol-3-phosphate dehydrogenase. Pollard et al.70 found that the accumulation of 90% short and medium-chain fatty acids in cuphea (Cuphea hookeriana) seeds by inserting of chain length specific acyl-ACP thioesterases in seeds.
Technology | Advantages | Limitation | References |
---|---|---|---|
Mechanical press | - Higher yield | - High maintain cost | 72–74 |
- Easy to operate | - Requires moisture reduction in oil seeds | ||
- Requires further oil refining and degumming processes | |||
- Not suitable for non-edible seed oil extraction | |||
Soxhlet extraction | - Low cost | - Utilize volatile organic solvent | 75–79 |
- Easy to operate | - Long operating time | ||
- Higher yield | - High operating temperature | ||
- Requires solvent separation process | |||
- Requires refining process | |||
Microwave extraction | - Enhance oil extraction yield | - Operating temperature vary with solvent boiling temperature | 80–84 |
- Minimize solvent uses | - Generally utilized as a pretreatment for solvent extraction | ||
- Shorter extraction time than solvent extraction | |||
Enzymatic oil extraction | - Organic solvent free technology | - Requires prolonged extraction time | 85 and 86 |
- Environmentally friendly | |||
scCO2 extraction | - Green technology | - High cost of the equipment | 87–89 |
- Does not require toxic organic solvent | |||
- Does not require any refining and oil separation technology | |||
- Low temperature technology | |||
- Higher selectivity and diffusivity to fatty acids |
Mechanical press, also known as screw press or hydraulic press, is the most common method used in extracting oils from natural materials. This technique is the most conventional oil extraction method. This method is widely used on seeds with high oil content, such as olive, Jatropha, and candlenut.71–73 The mechanical pressing extraction technique operates using a rotating worm shaft to increase the pressure up 174 to 100 MPa by reducing the space and volume on the extraction chamber to squeeze out the oil from the materials.51,72 The mechanical press has a relatively simple operation process, giving a high yield of oil extraction. However, tedious pre-treatments are required on the material before the press method, such as drying, dehulling, particle size reduction, and cooking, to increase the extraction method.51,74 Uquiche et al.74 utilized microwave radiation as a substrate pre-treatment to extract hazelnut oil using mechanical extraction. The study reported that the hazelnut nut oil yield increased with the pre-treatment. Rodrigues et al.8 reported that moisture content plays an influential role in the extraction of Jatropha seed oil subjected to mechanical extraction. The disadvantage of applying mechanical extraction technology in non-edible extraction is that the extracted oil requires further oil purification of filtration and degumming processes.69 The mechanical extraction of non-edible seed oil depends on moisture content, percentage of oil containing in the seeds, and pre-treatment process of seeds.51,71 However, the mechanical extractor designs have been made for some oilseeds. Therefore, the extraction yields influence when the extractor design is utilized in other seed oil extraction.
Soxhlet extraction is commonly used for the extraction of oil using an organic solvent, where hexane is the most used solvent.74,75 Other solvents used in Soxhlet extraction for non-edible oil extraction are methanol, ethanol, diethyl ether, acetone, and chloroform.74,77 Several parameters control the performance of Soxhlet extraction, which are the type of solvent, operating temperature, and particle size of a sample. A mixture of solvents can also apply during the extraction of lipids, which have different types of polarities.77 Particle size is one of the most influential parameters in Soxhlet extraction, as the smaller particle size has a greater interfacial area between the solvent and solid matrices.76 Temperature potentially influences the extraction rate because an increase of temperate increases the solubility of the solid matrices.75 Karthikeyan et al.76 extracted non-edible oil from Catharanthus roseus seed oil using the Soxhlet extraction method with several organic solvents, including methanol, diethyl ether, acetone, and chloroform. The study reported that the highest oil yield of 31.50% was obtained using methanol as solvent at 65 °C for 3 h. Jamil et al.78 determined the influence of Soxhlet extraction process parameters such as time, temperature and solvent to seed ratio for the extraction of date pit oil. The highest yield of date pits oil was gained of 16.5 wt% at a solvent to seed ratio of 4:1, temperature 65 °C and time 7 h.78 Mueanmas et al.79 extracted non-edible oil from waste coffee grounds for being a feedstock for biodiesel production.
The implementation of microwave heating as a pre-treatment process in solvent extraction has recently attracted interest to the researcher as it increases the extraction efficiency of trace organic pollutants from foods and non-food materials. Studies have been conducted the determine the efficiency of the combination of microwave heating and solvent extraction method to extract several compounds from various matrices, including pectin,80 essential oils,81 pesticides,82 and polychlorobiphenyls.83 It was found that the combination of microwave heating and solvent extraction method offering many advantages, such as less solvent usage, shorter extraction time, higher extraction rate, and high quality of extract.80,82 Ibrahim et al.84 utilized microwave heating as pre-treatment during the extraction of non-edible sandbox seed oil using hexane as a solvent. The study reported that the application of microwave heating enhances the oil yield and minimizes the FFA content in solvent-extracted sandbox seed oil. The enzymatic technique has been viewed as a promising extraction method for non-edible oil extraction as an organic solvent-free extraction technology.85 The main advantage of the enzymatic oil extraction technology is that it is environmentally friendly and does not require any volatile organic solvent.86 However, the enzymatic oil extraction method requires prolonged extraction time compared to the other available technology for edible and non-edible oil extraction.
In recent years, there is an increasing interest in utilizing supercritical carbon dioxide (scCO2) technology to extract separation edible and non-edible oil due to the environmental pollution concern with the organic solvents used in conventional solvent extraction.87–89 The organic solvents used in solvent extraction are toxic and volatile, those can pose various environmental pollution concerns including atmospheric and soil toxicity.89 The scCO2 is viewed as an attractive alternative solvent to organic solvents because it is neither toxic nor volatile. Although CO2 is a greenhouse gas, the CO2 utilized in the supercritical extraction system is withdrawn from the environment and return to the environment after extraction. Therefore, the scCO2 does not contribute to greenhouse effects.90 The scCO2 extraction is viewed as the most promising technology in extraction separation of edible and non-edible oil due to the several distinct advantages over other existing technology, including higher solubility, higher selectivity, mass transfer rates, and does not require further refining process to separate the extracted oil.84,89 The component selectivity depends on the density of the supercritical fluid, which could be altered by varying the process pressure and temperature.87 Furthermore, the scCO2 extraction method can efficiently extract several compounds such as essential oil, caffeine, pesticide, lipids, and fatty acids, as reported elsewhere.87,89,91,92 The extraction is carried out by the scCO2 in the extraction vessel. Subsequently, the extracted oil is collected from the separation vessel, while the fiber retains in the extraction chamber.
A supercritical condition can be defined as a state that has a pressure and temperature greater than its critical point where vapour and liquid reach equilibrium in this phase.87,92 In the supercritical condition, the fluid has a liquid-like density and gas-like viscosities, where its diffusivity is higher than liquid solvents, making it capable of performing better mass transfer (such as extraction) and reaction rates.91 Carbon dioxide reaches supercritical conditions at a critical temperature above 31.1 °C and critical pressure above 7.39 MPa.86 Cheng et al.93 extracted lipids from microalgae using solvent extraction and scCO2 extraction methods for 241 biodiesel synthesis. The study reported that the scCO2 technology effectively produces higher selectivity lipid extraction for biodiesel synthesis. Chen et al.94 produced biodiesel from scCO2-extracted Jatropha oil using a supercritical methylation process. The study reported that the scCO2 is a superior technology for the extraction of lipids for biodiesel syntheses, since this technology does degrade triglycerides in the extracted lipids. Subroto et al.87 reported that the candlenut oil is susceptible to oxidation with temperature due to containing a high amount of unsaturated fatty acids, including the linoleic acids, accounting for 65% of the total oil. Thus, it urges a low-temperature extraction method to maintain the fatty acids content and avoid FFA production, wherein the scCO2 extraction method is highly promising.
Plant seed oil | Viscosity at 40 °C | Flash point (°C) | Cloud point (°C) | Moisture content (%) | Iodine number (mg g−1) | Acid value (mg KOH per g oil) | FFA (%) | Color | References |
---|---|---|---|---|---|---|---|---|---|
Jatropha | 36 | 292 | 2 | 0.02 | 135 | 1.50 | 1.05 | Golden yellow | 95 |
Castor | 222 | 294 | 14 | 0.30 | 84 | 2.41 | 1.41 | Yellow | 96 |
Jojoba | 24 | 295 | 8 | 0.02 | 86 | 0.71 | NA | Golden yellow | 56 |
Candlenut | 26 | NA | NA | 0.26 | 137 | 1.59 | 7 | Golden yellow | 51 |
Karanja | 40 | 225 | 3.5 | 0.2 | 87 | 5.70 | 5 | Yellowish red | 97 |
Mahua | 25 | 232 | 15 | NA | 71 | 36 | 18 | Yellow | 34 |
Kusum | 25 | 268 | 12 | 0.25 | 215 | 21 | 11 | Yellowish | 98 |
Cotton | 29 | 255 | −3.5 | 0.02 | 69 | 0.24 | 1.07 | Yellow | 99 |
Neem | 44 | 167 | 19 | 0.25 | 85 | 18 | 17 | Reddish brown | 100 |
Polanga | 58 | 239 | 8 | NA | 94 | 0.34 | 22 | Dark brown | 43 |
Rubber | 76 | 198 | −9 | 0.1 | 135 | 0.52 | 17 | Dark | 101 |
The presence of viscosity in non-edible oil reveals the presence of FFAs in the oil. Acid value is another factor to decide the suitability of alkaline transesterification of non-edible oil for biodiesel synthesis. The non-edible oil contains below 2 mgKOH g−1 acid value can proceed with the conventional alkaline transesterification for biodiesel conversion.43 However, the acid value over 2 mgKOH g−1 in non-edible requires a pretreatment to reduce the acid value in non-edible oil prior to biodiesel conversion. As can see in Table 4, non-edible oil derived from castor (2.41 mgKOH g−1), karanja (5.70 mgKOH g−1), mahua (36 mgKOH g−1) and kusum (21 mgKOH g−1) contains acid value over 2 mgKOH g−1, which reveals that alkaline transesterification is not a suitable technology for biodiesel conversion from these non-edible oils. The iodine number (mg g−1) refers to the presence of unsaturated fatty acids in the oil. The higher the iodine number, the higher the unsaturated fatty acids content and thus, the lower the oxidative stability of the biodiesel.57 It is found that non-edible oil contains a high iodine number (Table 4), which reveals the oxidative stability of the non-edible oil.
Fatty acid compositions are the crucial parameter for a biodiesel feedstock to evaluate biodiesel conversion efficiency. Generally, biodiesel conversion technology does not affect the fatty acids compositions present in the feedstocks. However, the types of fatty acids and their percentage compositions in non-edible oils vary with plant species, plant growth conditions and technology utilize to extract the oil.57,87 Table 5 shows the types of fatty acids present in the Soxhlet extracted non-edible oils. The most common fatty acids present in non-edible oil are C16 and C18 acids. The fatty acids are generally aliphatic carboxylic acids. The fatty acids is the major components of biodiesel. Generally, biodiesel contains various fatty acids, such as palmitic acid (C16:0), linoleic acid (C18:2), oleic acid (C18:1), stearic acid (C18:0), and linolenic acid (C18:3).106–108 Similar fatty acids in non-edible oil reveal that the non-edible oil could be utilized as feedstock for biodiesel production.
Non-edible oil | Palmitic (C16:0) | Stearic (C18:0) | Oleic (C18:1) | Linoleic (C18:2) | Linolenic (C18:3) | References |
---|---|---|---|---|---|---|
Jatropha | 14.6 | 7.6 | 44.6 | 31.9 | 0.3 | 103 |
Jojoba | 1.59 | 4.14 | 42.84 | 31.52 | NA | 56 |
Candlenut | 6.23 | 2.23 | 26.26 | 39.71 | 24.86 | 87 |
Karanja | 9.8 | 6.2 | 72.2 | 11.8 | NA | 97 |
Mahua | 21.36 | 18.97 | 38.98 | 19.47 | 0.16 | 34 |
Kusum | 10.35 | 11.11 | 27.08 | 6.14 | NA | 98 |
Oleander oil | 23.28 | 7.46 | 44.23 | 21.82 | NA | 104 |
Cotton oil | 24.15 | 2.90 | 19.32 | 50.72 | 1.45 | 105 |
Neem oil | 14.9 | 14.4 | 61.9 | 7.5 | 0 | 106 |
Polanga | 12.01 | 12.95 | 34.09 | 38.26 | 0.30 | 43 |
Rubber | 10.2 | 8.7 | 24.6 | 39.6 | 16.3 | 101 |
Rice bran | 21.76 | 2.31 | 41.86 | 30.99 | NA | 107 |
Tobacco | 10.96 | 3.34 | 15.54 | 69.49 | 0.69 | 108 |
Non-edible oil | Technology | Parameter | Yield (%) | References | ||||
---|---|---|---|---|---|---|---|---|
Pressure (MPa) | Time (min) | Temperature (°C) | Alcohol:oil | Catalyst (%) | ||||
Jatropha | scMeOH transesterification | 11 | 15 | 250–290 | 3:1 | NA | 99 | 94 |
Candlenut | Transesterification | 45 | 40 | 5:1 | 1 | 99.3 | 35 | |
Castor | Catalytic transesterification | 45 | 60 | 6:1 | KOH | 97 | 60 | |
Castor | Catalytic transesterification | 30 | 60 | 9:1 | KOH | 95 | 109 | |
Castor | Catalytic transesterification | 60 | 55 | 8:1 | Ni–ZnO | 95 | 110 | |
Cotton seed oil | Catalytic transesterification | 60 | 50 | 12:1 | Egg shell | 92 | 111 | |
Cotton seed oil | Catalytic transesterification | 90 | 65 | 6:1 | CH3ONa | 97 | 112 | |
Cotton seed oil | Catalytic transesterification | 60 | 55 | 6:1 | KOH | 96 | 99 | |
Jojoba oil | Catalytic transesterification | 60 | 25 | 6:1 | KOH | 83.5 | 113 | |
Karanja | scMeOH transesterification | 43 | 90 | 300 | 43:1 | NA | 81 | 59 |
Karanja | Catalytic transesterification | NA | 65 | 6:1 | H2SO4 | 97 | 114 | |
Karanja | Transesterification | 120 | 66.8 | 10.44:1 | KOH | 91.05 | 115 | |
Kusum | Catalytic transesterification | 60 | 50 | 8:1 | KOH | 95 | 116 | |
Yellow oleander | Catalytic transesterification | 30 | 60 | 4.5:1 | KOH | 93 | 46 | |
Kusum | Catalytic transesterification | 90 | 65 | 15:1 | K2Al2O4 | 97 | 117 | |
Mahua | Catalytic transesterification | 60 | 65 | 5:1 | KOH | 91 | 118 | |
Neem | Catalytic transesterification | 23 | 60 | 0.23 | Cu–ZnO | 91 | 119 | |
Polanga | Pyrolysis | 550 | NA | NA | 46 | 120 | ||
Sea mango | Catalytic transesterification | 180 | 150 | 12:1 | SO42−/ZrO | 94 | 121 | |
Sea mango | scMeOH transesterification | 380 | 40 | 45:1 | NA | 78 | 122 | |
Soap nut | Catalytic transesterification | 180 | 60 | 15:1 | Carbon residue | 89 | 37 | |
Tobacco | Pyrolysis | NA | 350 | NA | NA | 67 | 123 | |
Tobacco | Catalytic transesterification | 30 | 60 | 6:1 | KOH | 91 | 124 | |
Tung seed oil | Catalytic transesterification | 60 | 55 | 5:1 | KOH | 93 | 63 |
The quantity and quality of the extracted biofuel depend on the types of feedstocks, oil content in the plant seeds, and the types of pyrolysis use.120,125 Various types of pyrolysis reactors have been employed in the production of biofuel, including (i) circulating fluidized bed, (ii) bubbling fluidized bed, (iii) focussed solar reactor, (iv) rotating cone, and (v) ablative. The main advantages of pyrolytic bio-oil are easy to handle, store and transport. Besides, the distinct desirable properties of pyrolytic oil such as high cetane number, low viscosity, and low quantities of sulphur could be considered for being used as an alternative fuel. However, the pyrolytic bio-oil is acidic and contains different types of hydrocarbon compounds and high moisture.123 The bio-oils derived from edible and non-edible plant seeds are denser than petroleum diesel fuel, and therefore, it requires a pre-treatment process to remove moisture and neutralize prior to use as an alternative biofuel.126
Poor quality non-edible oil requires a pre-treatment technology such as cracking, blending, and hydrodeoxygenation to minimize the viscosity and FFAs content prior to producing biodiesel. However, the micro emulsification process does not require a pre-treatment process in producing biodiesel from non-edible oil. Studies reported that the utilization of the surfactant in the emulsification process enhances the yielded emulsion's stability. The most utilized surfactant in the emulsification of the non-edible is hydrophobic span 80. However, other hydrophobic and hydrophilic surfactants were also utilized in the emulsification process. Liang et al.130 utilized micro emulsification technology to stabilize bio-oil-in diesel using Span 80/Tween 80 as surfactants. Sankumgon et al.131 produce microemulsion bio-fuel from Jatropha curcas oil in the presence of the surfactant. The properties analyses of the microemulsion oil showed kinematic viscosity, moisture content, and heating values comply with the biodiesel standards and compatible to use in a diesel engine. Besides, the emission characterization showed that the microemulsions fuel combustion exhaust less smoke than diesel. The advantages of using microemulsion fuel are that it reduces toxic pollutants emission during combustion, increases combustion performance, and minimizes the ignition delay time.126–128 Microemulsion fuel properties are similar to petro diesel, but the oxidative stability is higher than petro diesel.128 The major disadvantages of utilizing micro-emulsion fuels in combustion engines are incomplete combustion and the carbon deposition in the engine.129
Fig. 3 Transesterification reaction of triglycerides for the production of biodiesel from non-edible oil. |
An excessive amount of alcohol utilization in catalytic transesterification makes it difficult for the separation of the glycerol. Therefore, it is urged to establish an ideal alcohol/oil ratio empirically. Catalytic transesterification can be carried out by alkaline catalysts using potassium or sodium hydroxide and methoxide.59,112 Alkaline catalysts provide some distinct advantages, including low operating temperature and short reaction time.34,116 The sodium methoxide (CH3ONa) is utilized as a catalyst for biodiesel production since it offers relatively higher yields in fast reaction times with low molar concentrations.116 However, alkaline transesterification requires an absence of water and minimal FFAs in oil (≤2 wt%), making them inappropriate technology for typical industrial processes.33,94 Enzymatic transesterification is an alternative to a heterogeneous catalytic transesterification process, where the lipases isolated from different microorganisms are used as a biocatalyst.85,132 In the last decades, lipase utilization as a biocatalyst in the transesterification process has dedicated attention to its mild reaction condition, simple downstream processing, and easy separation of enzymes. Enzymatic catalytic transesterification can process low-quality biodiesel feedstock to produce biodiesel because high moisture and FFAs content in feedstocks do not affect the transesterification process biodiesel production, as the enzyme has minimal sensitivity with water and FFAs.133 Moreover, the enzymatic catalytic process, the lipase enzyme can covert FFAs and triglycerides to biodiesel in a single transesterification process.85 This process does not require subsequent purification or washing to separate enzymes. The main obstacles of the enzymatic transesterification process to produce biodiesel are the relatively slower reaction rate, cost of lipase, and the inactivation of the lipase by glycerol.133
In the conventional transesterification process in biodiesel production, the presence of FFAs and moisture in non-edible oil hinders the biodiesel conversion because of consuming more catalyst, causes soap formation, reduce catalyst effectiveness.26,94 However, these catalytic transesterification processes require relatively high reaction time and further purification technology to separate the catalyst, results in increased energy consumption and production costs.
To overcome these limitations, the transesterification of non-edible oil can be conducted using supercritical methanol (scMeOH). The critical temperature and pressure of the methanol are 512.6 K and 8.09 MPa, respectively.90 Above this critical pressure and critical temperature, methanol (MeOH) exhibits in a supercritical state, where there is no distinct phase between liquid and gas phases exist. The scMeOH can disperse through the materials like a gas and dissolve materials like a liquid. The properties of methanol in the supercritical state can be described as an intermediate between a liquid and gas phase of the methanol.26 The scMeOH is a simplified non-catalytic biodiesel conversion process since it is simultaneously conducting the transesterification of the triglycerides and esterification of fatty acids.94,133,134
Transesterification using methanol at a supercritical state has been extensively investigated in recent years to determine an effective alternative of conventional transesterification processes.26,135 The potential advantage of the scMeOH transesterification is that water and FFA content in the non-edible do not affect the biodiesel conversion process. Moreover, the water content in non-edible enhances the biodiesel conversion in scMeOH transesterification process.132 The utilization of catalyst is not essential in the scMeOH transesterification process, since methanol and oil produce homogenous phases in the supercritical state and minimize the mass transfer limitations.133 Another distinct advantage of the scMeOH transesterification process is the more straightforward separation process of glycerol from the biodiesel because biodiesel and glycerol are immiscible at ambient temperature.59,94 Román-Figueroa et al.136 synthesized biodiesel from crude castor oil using scMeOH as catalyst-free transesterification process with varying temperature (250–350 °C), pressure (10–43 MPa), treatment time (15–90 min), and methanol to oil molar ratio of 43.1. It was obtained 96.5 wt% of biodiesel conversion at scMeOH temperature 300 °C methanol to oil molar ratio of 43.1 for 90 min reaction time. García-Martínez et al.135 optimized the experimental conditions of the scMeOH transesterification process for biodiesel production from tobacco seed oil and obtained about 93 wt% biodiesel conversion at 303.4 C for 90 min with a fixed methanol and oil molar ratio of 43.1.131 Although the utilization of catalyst in scMeOH transesterification is not essential, a few studies have utilized catalyst to enhance transesterification rate and biodiesel yield with lower energy consumption.26,136 The limitations of utilizing in the scMeOH transesterification process for biodiesel conversation are the high capital cost investment required for setting up the high pressure and temperature technology. However, the high capital investment can be compensated with similar productivity by the rapid transesterification rate in a smaller reactor.
Non-edible oil biodiesel | Density (kg m−3) | Viscosity (mm2 s−1) | Flash point (°C) | Pour point | Cloud point (°C) | Moisture content (%) | Cetane number | Iodine number (g) (I2/100 g) | Acid value (mgKOH g−1) | Sulfated ash | Calorific value (MJ kg−1) | Oxidation stability (h) | References |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Jatropha | 879 | 4.84 | 191 | 3 | 2.8 | 0.02 | 51 | — | 0.38 | 0.013 | 38.5 | 3.37 | 137 |
Castor | 946 | 15.4 | 194 | −30 | −18 | 0.15 | 43.7 | 78.21 | 2.8 | NA | 38.34 | 4.4 | 109 |
Jojoba | 871 | 5.86 | 150 | −6 | −2 | 0.053 | NA | 74.7 | 0.22 | 0.08 | 42.82 | 3.05 | 138 |
Candlenut | 886 | 4.8 | 161 | 6 | 6.84 | 0.33 | NA | NA | 0.4 | 0.005 | 0.19 | 5.9 | 139 |
Karanja | 870 | 5.6 | 174 | 7 | 10 | 0.04 | 57.6 | 91 | 0.21 | 0.001 | 37.8 | 3.68 | 140 |
Mahua | 882 | 4.2 | 170 | 6 | 13 | NA | 57 | 71 | 0.47 | 0.01 | 37 | 8.2 | 34 |
Kusum | 860 | 4.2 | 139 | −2.5 | −10.8 | NA | 47.27 | NA | 0.45 | NA | 38.33 | NA | 141 |
Cotton | 881 | 6.81 | 173 | 5 | 7 | 0.02 | 56.06 | 125 | 0.22 | NA | 39.54 | NA | 99 |
Neem | 867 | 5.16 | 170 | 8.5 | 15 | NA | 55 | NA | 0.61 | 0.01 | 38.25 | NA | 142 |
Polanga | 869 | 3.99 | 140 | 4.3 | 13.2 | NA | 51 | NA | 0.34 | NA | 41.39 | 13.08 | 43 |
Rubber | 870 | 3.7 | 110 | −2 | −6 | 0.04 | 43 | NA | 0.07 | NA | 36.5 | 8.5 | 52 |
Tobacco | 888 | 4.22 | 165 | NA | NA | NA | 51 | 136 | 0.3 | 0.0004 | 44.6 | 8 | 143 |
Yellow oleander | 870 | 4.2 | 175 | NA | NA | NA | NA | NA | NA | NA | 43.4 | NA | 46 |
Sea mango | 880 | 4.5 | 138 | NA | NA | NA | NA | NA | NA | NA | 39.09 | NA | 122 |
Soap nut | 869 | 7.7 | 151 | 4.3 | 13.2 | NA | 57.3 | 85 | 0.76 | 0.02 | 41.39 | NA | 144 |
870–890 | 1.9–6.0 | ≥130 | −15 to −16 | −3 to −12 | ≥0.05 | ≥47 | NA | ≤0.5 | 0.02 | NA | ≥3 | ASTM D 6751 | |
860–900 | 3.5–5.0 | ≥101 | NA | NA | ≥0.05 | ≥51 | 120 | ≤0.5 | 0.02 | NA | ≥6 | EN 14214 |
From Table 7, it is found that the castor biodiesel has a higher density (946 kg m−3) than standard specifications set by ASTM 6571, EN 14214. The injection and atomization properties of biodiesel far different than vegetable oil due to the presence of lower viscosity. Generally, the viscosity of the non-edible oil sharply decreases with the biodiesel transesterification processes. The lower the viscosity of biodiesel makes it easy to pump it into an engine for atomization. High viscosity of biodiesel leads to the inefficient automatization of the fuel spray, which leads to inaccurate fuel injectors operations.13,143 It was found from Table 7 that the viscosity of castor (15 mm2 s−1), cotton (6.81 mm2 s−1), and soap nut biodiesel (7.7 mm2 s−1) is higher than prescribe viscosity of biodiesel specified by ASTM 6571 and EN 14214 standards. Flashpoint is another important property of biodiesel, which indicates the lowest temperature of the fuel to spontaneously ignite in absence of a flame or spark. It is found that the non-edible biodiesel has higher flashpoint values than the recommended values reported by ASTM 6571 and EN 14214 standards, indicates that biodiesels derived from the non-edible oils are less volatile and safe to use in diesel engine.144,145 Pour point (PP) and cloud point (CP) of biodiesel indicates the low temperature application of the biofuel. From Table 7, it is found that the higher PP and CP were in neem biodiesel (8.5 and 15 °C, respectively), wherein the lowest PP and CP were found in castor biodiesel (−30 and −8 °C, respectively). Cetane number is another critical parameter to determine the biodiesel ignition quality. Generally, the cetane number provides the biodiesel readiness information for auto-ignition upon injection to the engine for combustion.146
Fig. 4 Schematic diagram for the commercial scale biodiesel production via catalytic transesterification process. |
In some cases, it urges to conduct two steps catalytic transesterifications to provide a complete chemical reaction with minimal uses of alcohol. In the 1st stage, 80% of alcohol and catalyst are added to the oil and then removed produced glycerol. The remaining 20% of alcohol is added to the reactor at the second stage catalytic transesterification process. Special processes are required if the non-edible oil contains excessive amounts of FFAs. The FFAs present in non-edible oil will react with the alkali catalyst to produce soap and water, as shown in Fig. 5. However, the FFAs content in non-edible oil below 5% can proceed with an alkali catalyst. The soap produced will wash out during the water washing of the biodiesel.
Fig. 5 Soap formation during alkaline catalytic transesterification of non-edible oil containing excessive amount of FFAs. |
However, the alkali transesterification process of non-edible oil containing over 5 wt% FFAs would inhibit glycerol and methyl ester separation due to the emulsion formation during waster wash. Therefore, it requires a pretreatment process to reduce FFAs in the non-edible oil by converting FFAs to methyl ester, as shown in Fig. 6.151 The treated oil can proceed with an alkaline catalytic transesterification process to convert triglycerides to methyl ester. After transesterification, the glycerol is separated using either a centrifuge or a settling tank. The glycerol separation gently occurs due to its low solubility in the ester. The presence of excess alcohol may slow the separation process, but the excess alcohol generally not removed the reaction stream until completely separated the methyl ester and glycerol.152 The transesterification is a reversible process, and therefore the glycerol may recombine with methyl ester to form monoglycerides in the absence of alcohol. The glycerol stream remaining in the separator contains alcohol, catalyst, and soap. At this stage, the glycerol has little value due to the presence of the contaminate. However, the glycerol can refine with two steps refining processes by removing soap and excess alcohol. Almost 85% of glycerol can be recovered with the paurity up to 99.7%.148
Fig. 6 Pretreatment of non-edible oil containing excessive amount of FFAs before biodiesel production. |
The separated methyl esters pass through an alcohol stripper to remove the alcohol before neutralization and water washing of the biodiesel. The produced biodiesel is neutralized by adding acid to neutralize the residual catalyst and split any soap forming during the reaction. The acids react with soap and produce FFAs and water-soluble salt.152 The salt generated will wash out during the water washing of the biodiesel. Finally, the produced biodiesel is cooled in ambient temperature and makes it ready for storage and transportation. Fig. 7 shows the commercial-scale biodiesel production from non-edible oil via the non-catalytic transesterification process. The most preferred non-catalytic transesterification process is the esterification of non-edible oil using supercritical methanol (scMeOH).150 Transesterification is also an important process in the scMeOH transesterification process of non-edible oil for biodiesel production. There is also an esterification reaction between alcohol and FFAs, a relatively much faster rate than the conventional transesterification process. scMeOH transesterification is a catalyst-free transesterification process.10 It is viewed as an eco-friendly, less energy intensive, highly efficient and superior transesterification process for converting non-edible to methyl ester. Methanol over critical pressure (8.09 MPa) and temperature (239 °C) acts as a solvent for dissolving oil uniformly during transesterification.59,150 The potential advantages of this transesterification process is that it reduces treatment time and it processes the non-edible oil that contains high FFAs, which is not possible for the conventional catalytic transesterification process.10,59 In this process, the possibility of the hydrolysis of the biodiesel is neglected due to the production of a small amount of water during biodiesel production. Various parameters potentially influence the scMEOH transesterification process, including pressure, temperature, reaction time, mixing intensity, and MeOH:oil molar ratio.10,59
Fig. 7 Schematic diagram non-catalytic transesterification process for the commercial scale biodiesel production from non-edible oil. |
Source | Type of reactor | Catalyst | Quantity (t per year) | Utility and labour cost ($ per L) | Oil price (t per $) | Total production cost (×106 $) | Cost of biodiesel ($ per L) | Biodiesel selling price ($ per L) | Reference |
---|---|---|---|---|---|---|---|---|---|
Jatropha oil | Continuous stirred tank reactor | Homogeneous base | 9900 | 0.032 | 322 | 0.394 | 0.145 | 0.75 | 150 |
Supercritical methanol | Catalyst free | 110 | 0.37 | 322 | 0.443 | 0.210 | 0.75 | ||
Low quality non-edible oil | Continuous reactor | Homogeneous base | 8000 | 0.047 | 478 | 0.458 | 0.162 | 0.70–0.80 | 153 |
Tamanu seed oil | Continuous stirred tank reactor | Heterogeneous nano-catalyst | 2400 | 0.036 | 400 | 0.421 | 0.159 | 0.70 | 154 |
Cotton oil | Continuous reactor | Homogeneous base | 5102 | 0.025 | 980 | 0.532 | 0.180 | 0.58 | 149 |
Neem oil | Batch reactor | Heterogeneous base | 3285 | 0.052 | 840 | 1.06 | 0.230 | 1.03 | 155 |
Waste cooking oil | Semi-industrial reactor | Homogeneous base | 1500 | 0.075 | 990 | 0.81 | 0.270 | 0.65 | 156 |
Based on the literature survey, the development of non-edible crops as a potential feedstock for biodiesel poses challenges towards self-reliance energy security. This is because:
(i) Non-edible crops are of forest origin, and it is therefore harvesting, collection and transportation are problematic.
(ii) Lowering fuel economy, seasonal availability of non-edible crops and improper marketing channels are the major drawbacks for setting up biodiesel production industries.
(iii) The presence of high FFAs and moisture content requires a pre-treatment to minimize FFAs and water content in the oil prior to the transesterification process.
(iv) Lack of post-harvest technologies for non-edible crops affects its oil quality.
(v) Existing technologies for oil extraction and biodiesel conversion are not cost effective since these technologies require multiple purification and separation processes.
Thus, the utilization of non-edible oil as feedstock for biodiesel possess challenges and opportunity to utilize as an alternative fuel of petro-diesel for the environment and economic benefits. These urges to conduct further research on cultivation of non-edible crops and cost-effective technology for biodiesel conversion. Since non-edible crops can grow in harsh and aired lands with low moisture requirements, thus the plantation can be carried out in the most unused lands, particularly in developing countries, such as sea sore, bank of the river, desert, and other wastelands those are not suitable for edible crops. These will allow the maximum utilization of the limited land area available for crop production. The presence of FFAs and moisture content in non-edible oil could be avoided with the implementation of advance technology, particularly with the implementation waterless extraction technology like supercritical fluids technology.
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