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Catalysis in Biodiesel Production - A Review PDF
Catalysis in Biodiesel Production - A Review PDF
1, 2–23
doi: 10.1093/ce/zky020
Advance Access Publication Date: 17 December 2018
Homepage: https://academic.oup.com/ce
Review Article
Catalysis in biodiesel production—a review
Baskar Thangaraj1*, Pravin Raj Solomon2, Bagavathi Muniyandi3,
Abstract
Catalysts play a significant role in transesterification of vegetable oils. Currently, chemical and biological
catalysts are being investigated, and both have their inherent merits and demerits. In large-scale applications,
these catalysts are expected to be cost effective and environmentally friendly. If the catalyst is homogeneous
in its physical form it is more effective than is the heterogeneous catalyst, but its separation from the mixture
is a major issue. Some of the heterogeneous catalysts suffer leaching in harsh reaction conditions. Of late,
nanocatalysts that demonstrate high efficiency are being studed. Nanoparticles are used in biological catalysts
as solid carriers for lipase immobilization. Lipase immobilized on magnetic nanoparticles has proved to be a
versatile biocatalyst for biodiesel production. This article reviews the role of various catalytic systems commonly
used in the transesterification reaction of oils in biodiesel generation.
Key words: transesterification; chemical catalysts; biological catalysts; biodiesel; renewable energy
sulphur dioxide and unburned hydrocarbons compared to catalysts are effective in bringing the process to complete-
petroleum-based diesel fuel [3, 4]. One of the major issues ness, although the reaction demands high energy and a
confronting the biodiesel production path is the use of a cumbersome purification process to obtain the purified
suitable catalyst in accordance with the nature of the oil. end product [31, 32]. Among the biological catalysts, immo-
The functional efficiencies and side effects of catalysts bilized lipases are much preferred. The different catalytic
during transesterification have become a matter for dis- processes of transesterification used to produce biodiesel
cussion and thus attracted comprehensive analysis. are presented in Fig. 1. Enzymatic transesterification has
Biodiesel is now receiving attention as a fluid fuel devel- an environmental advantage over the other methods
oped as a modified vegetable oil. Biodiesel produced from [33–37]. Its major disadvantage is its prohibitive cost [35].
edible oils is currently more expensive than the conven- Table 1 explains the merits and demerits of using enzymes
tional petroleum-based fuels; in addition, it competes in the transesterification process.
with cooking oil. Hence the focus has shifted to the use of
non-edible oils as a raw material for biodiesel [5]. Popular
non-edible oils being considered for biodiesel production 1.1 Chemical catalysts
Catalytic systems
Chemical Biological
Table 1 Advantages and disadvantages of free, traditionally immobilized lipase and lipase immobilized on magnetic nanoparti-
cles [37–41]
Lipase-based
catalyst Advantages Disadvantages
Free lipase More efficient catalytic activity, highly selective, Lipase inactivation by methanol, lipase stability, re-
involves less energy consumption (mild reaction covery and reusability
conditions). Environmentally favorable.
Traditional immo- Improved lipase stability and reusability; eco- High mass-transfer resistance, lower reaction rate,
bilized lipase nomical. Provides operational flexibility, in- surface to volume ratio moderate. Centrifugation
creased thermal stability and chemical stability. and filtration required for separation. Decreased
Eliminates downstream operations like separ- enzyme activity during immobilization process.
ation and recycling. Costly fabrication.
Lipase immobil- High activity and selectivity. Less energy consump- Increased magnetic nanoparticle size by agglomer-
ized on magnetic tion, green catalysts, improved thermal stability, ation among particles. Decreased enzyme activity
nanoparticles high operational stability, easily recovered from during immobilization process. Costly fabrication
reaction mixture by an external magnetic field. process.
[45]. Sulphuric acid catalyzed the transesterification used at the 5% level in series. This esterification reaction
reaction of Zanthoxylum bungeanum seed oil with metha- gave a biodiesel yield of >90% with different alcohols such
nol recovered >94% in 12 h [22]. Tin tetrachloride (SnCl4) as methanol, ethanol and butanol [51]. The double-stage
catalyzed the esterification of Z. bungeanum seed oil and process has become a successful practice in different oils
achieved >96% output in optimum reaction conditions [47]. having high FFA content. Crude rubber seed oil has ~17%
The acid catalyst offers high yield but the reaction rate is FFA, which was reduced to <2% by a sulphuric acid (H2SO4)
too slow, requires a higher oil/alcohol molar ratio and and esterification process and was followed by an alkali (NaOH)
an extended reaction duration (>1 day) [48, 49]. transesterification process [10]. Two-step methods were
If the oil has a high FFA content, it is treated first also followed for transesterification of crude rubber seed
with p-toluene-4-sulphonic acid and then with potas- oil, which brought a recovery of 96.8% [10, 15, 16, 52–54].
sium hydroxide (KOH) [50]. The biodiesel thus obtained H2SO4 was found to reduce the FFA by 88.8% in waste oil,
is refined by washing repeatedly with hot distilled water and subsequently with alkali (KOH) catalysis a 94% bio-
and neutralized using sulphuric acid. This product is again diesel yield was obtained at 50°C [55].
washed and freed from moisture by a suitable dehydrant The effect of the type of alcohol being used on the
[6]. To extract the ester from vegetable refinery waste, the transesterification process indicated that methanol is best
heterogeneous acid catalyst Amberlyst-35 sulphonic resin suited, with a faster reaction and good ester isolation. The
and homogeneous catalyst p-toluenesulphonic acid were reaction speed is relatively low in ethanol use, and the
Thangaraj et al. | 5
ester recovery also is low [56]. The effect of different alco- CaO, MgO/KOH and Na/NaOH/λ–Al2O3 are efficient hetero-
hols on biodiesel production from different vegetable oils geneous catalysts for transesterification reaction [4, 67].
has also been investigated. Methanol is a better reactant Solid acid catalysts favour both esterification and transes-
with vegetable oils than other alcohols (ethanol, 2-pro- terification simultaneously for biodiesel production from
panol and 1-butanol). Biodiesel production using metha- oils with high FFA content [61]. NaY zeolite-supported
nol as compared with ethanol is recommended because La2O3 catalysts prepared by a physical mixing method for
the ethanol purity is less than that of methanol. Ethanol the transesterification of castor oil achieved a biodiesel
procurement is relatively difficult and expensive. Long- yield of 84.6% under optimized reaction conditions [70].
chain alcohols such as 2-propanol and 1-butanol are also Air-stable and water-tolerant zirconocene perfluorooc-
recommended for biodiesel production, especially when a tanesulphonate Lewis acid catalyst was used in the direct
high oil/alcohol (1:70) ratio is employed. 2-Propanol may esterification of FFAs and transesterification of triglyc-
not give a high yield of biodiesel in a shorter reaction time erides. In addition, this catalyst behaves as a reaction-
because of its branched chain and it also needs a high tem- induced self-separating agent, because during the course
perature to dissolve the alkaline catalyst. 1-Butanol also of reaction it transforms from homogeneous to heteroge-
producing highly cost-effective catalysts [83]. A solid base Amberlyst are solid-acid catalysts for esterification reac-
catalyst of CaO nanocatalyst achieved 93% biodiesel con- tion of fatty acids through its organosulfonic groups [95–
version in jatropha oil [84]. A CaO/KF (or KF/CaU) solid-base 97]. MCM-41 (Mobil Composition of Matter No. 41) coated
catalyst is prepared by loading CaO on KF, which exhibits with different organic and inorganic compounds shapes
high catalytic activity [85]. Even though CaO showed high the properties of catalysts by its nanostructured surface
catalytic activity in transesterification, this catalyst leached with flexible pore sizes [97]. The Fe3O4/MCM-41 composite
out the calcium (Ca2+) ions that influence the quality of the catalyst has extraordinary catalytic activities in transester-
product. The leaching of Ca2+ ions is due to the presence of ification of soybean oil, with a biodiesel yield of 99.2%. The
moisture that hydrolyzes the calcium diglyceride (derived solid catalyst showed a strong magnetic response as Fe3O4
by the instability of CaO with the by-product glycerol). The is a superparamagnetic material [98].
formation of soluble Ca2+ also directly dissociates CaO dur- The sulphonic-acid–modified mesostructured cata-
ing the reaction with methanol. The leached calcium ions lyst is used in the transesterification reaction, achieving
react with FFA of oil, which leads to saponification and a conversion as high as 100%. However, the high concen-
deactivates the effective function of the catalyst. Therefore tration of methanol has been found to be detrimental to
actively involved in diminishing the overall activity of the than transesterification and hydrolysis reactions [130].
catalysts. In such situation, researchers are required to Guanidine-functionalized Fe3O4 and Fe3O4@SiO2 magnetic
develop a catalyst system that not only shows high cata- nanoparticles (MNPs) have been used as basic recyclable
lytic activity and selectivity but also retains the catalyst catalysts for biodiesel production. Fe3O4–TBD (1,5,7-tri-
separation and regeneration. This may be achieved by azabicyclo[4,4,0]dec-5-ene) also exhibited high catalytic
grafting through covalent binding and adsorption [36] and performance in the first cycle and achieved 96% biodiesel
also by the use of nanostructured catalysts. A nanocatalyst conversion [131]. A nano-solid base catalyst, K2O/γ–Al2O3,
acts as a junction between homogeneous and heterogene- achieved 94% conversion in rapeseed oil [132]. KOH impreg-
ous catalysts so as to have the desirable characteristic of nated with alumina and calcium aluminate has also been
both systems. used in the transesterification reaction [133]. The solid
base nanocatalyst of zirconia-loaded potassium bitartrate
1.1.3 Heterogeneous nanocatalysts was also used in biodiesel production [134].
Research on nanocatalysts to produce a catalyst with Transesterification was carried out in microwave, auto-
exceedingly high activity, selectivity and high stability clave or ultrasound using nanostructured MgO. A higher
at 75°C for 3 h) in which a 91.7% yield was obtained via developed by a noncatalytic supercritical method in which
concurrent esterification and transesterification in crude the yield was 96% in 10 min [30]. A co-solvent-supported
Euphorbia lathyris seed oil [145]. The magnetically recov- supercritical methanol system can improve the yield of
erable catalyst of MgO-supported MgFe2O4 was used as a biodiesel. Hexane and supercritical CO2 act as excellent
heterogeneous nanocatalyst in transesterification of sun- solvents for vegetable oil [155]. Transesterification of soy-
flower oil. The spinel ferrite catalyst of MgFe2O4 has unique bean oil in supercritical methanol has been carried out in
and tunable magnetic, electronic and structural properties. the presence of propane and achieved a FAME efficiency of
The catalyst produced a biodiesel yield of 91.2% and main- 98% with optimum reaction conditions such as tempera-
tained its catalytic activity up to five cycles with a steady ture, methanol to oil molar ratio, duration and reaction
conversion [146]. Ni0.5Zn0.5Fe2O4 was an effective nanocata- pressure (280°C, 24:1, 10 min and 12.8 MPa). Supercritical
lyst in methyl and ethyl esterification with 99.54% recov- CO2 is applied in enzymatic reactions because the enzyme
ery [147]. In situ decorated TiO2 on reduced graphene oxide can be separated easily by reducing the pressure. As the
nanocomposite via the hydrothermal route on transesteri- enzyme and the product cannot dissolve in carbon dioxide
fication of waste cooking oil gave a yield of 98% [148]. at atmospheric conditions, they can be easily regenerated.
CaO Calcination−hydration dehy- Catalyst ratio 0.02:1 (w/w); reaction time 95.8 9 [125]
dration of Polymesoda erosa 133.1 min; oil/ methanol molar ratio 1:5.15;
shells temperature 65°C; stirring rate 500 rpm
CaO (Nanocrystalline-1) Commercial CaO Catalyst amount 1 mmol; time 6 h; temperature 100 3 [124]
25°C; methanol 10 ml
CaO/CaN, CaO/ss Sol–gel method Catalyst 8 wt%; temperature 65°C; oil/methanol 93 (CaO/CaN) 96 5 [126]
ratio 1:12; time 6 h (CaO/ss)
Li–CaO Wet impregnation method Oil/methanol molar ratio 1:12; catalyst 5 wt%; >99 NA [127]
10 | Clean Energy, 2019, Vol. 3, No. 1
Reference
Bacillus thermoleovorans, Candida cylindracea, Candida rugosa,
[145]
[146]
[147]
[148]
[138]
[139]
[150]
Chromobacterium viscosum, Geotrichum candidum, Fusarium
heterosporum, Fusarium oxysporum, Humicola lanuginose,
Mucor miehei, Oospora lactis, Penicillium cyclopium, Penicillium
roqueforti, Pseudomonas aeruginosa, Pseudomonas cepacia,
Pseudomonas fluorescens, Pseudomonas putida, Rhizopus arrhi-
zus, Rhizopus boreas, Rhizopus thermosus, Rhizopus usamii,
Rhizopus stolonifer, Rhizopus fusiformis, Rhizopus circinans,
Cycles
3
6
4
NR 400, Rhizopus microsporus, Rhizopus nigricans, Rhizopus
niveus, Rhizopus oryzae, Rhizopus rhizopodiformis, Rhizopus
stolonifer NRRL 1478, Rhodotorula rubra and Staphylococcus
hyicus [166] for esterification of FFA or transesterification
Biodiesel effi-
95.7
84.2
93
98
98
97
hydrothermal method
sono-dispersion
Impregnation and
Co-precipitation
Sol–gel method
Sulfonated graphene
TiO2/RGO
(ly2HPW)
Cs–MgO
Entrapment
Wide
184]. The effect of temperature on lipase immobilization
Low has been examined by many researchers.
At 50 and 60°C the relative activity of free lipase
achieved a turnover of 88.46 and 75.38% , whereas the
immobilized lipase achieved 95.86 and 81.26%, respec-
confinement)
Very wide
in bulk [190].
The activity of an enzyme in a nonaqueous medium is
Covalent bonding
Selective
Applicability
Preparation
Continuous process
lyst microporous polymer matrix-supported enzyme was
Immobilized lipase
catalysts [190–193]
used to produce biodiesel from sunflower, soybean and
waste cooking oils; their yields were 97, 90.2 and 93.9%,
Not sensitive
respectively. This catalyst has retained its activity up to
Moderate
Possible
10 repeated cycles at 25°C with a reaction duration of 24 h
Higher
Easy
Easy
[39].
Low
Silica gel as a solid support for Lipozyme TL accelerates
the acyl migration and >90% biodiesel recovery is achieved
Continuous process
when 6% silica gel is combined with 4% lipase [193]. A high
Catalyst recovery
Lipase catalysts
yield (91.5%) of biodiesel was obtained from refined cot-
Not sensitive
Not possible
tonseed oil with 30% enzyme based on oil weight, 1:4 oil/
difficult
alcohol molar ratio, 50°C temperature and 7 h reaction
Difficult
Higher
duration. But the primary alcohol gave only a 72% yield
Easy
Low
[194]. Thermomyces languinosus lipase immobilized on
hydrophilic polyurethane foams gave 90% recovery and
Continuous process
the enzymatic activity continued after 10 cycles when
tertiary butanol was used [28]. The recombinant R. oryzae
Not applicable
Not sensitive
lipases (ROL) was immobilized on a macroporous resin and
[30, 152–158]
Ill-favoured
Ill-favoured
Absence of
anion exchange resin, namely MI-ROL and AI-ROL, respec-
catalysts
Medium
Higher
tively, and were used as biocatalysts for Pistacia chinensis
High
Easy
Bge seed oil biodiesel production with methanol. A yield
as high as 92 and 94% by MI-ROL and AI-ROL, respectively,
Continuous process
ing lipase in a microporous zeolite imidazolate framework,
Much cheaper
nanocatalysts
Not sensitive
alyzed the transesterification of soybean oil to biodiesel
(78.5%) in a solvent-free medium. The catalyst maintained
Possible
Higher
the catalytic activity up to six cycles with marginal loss in High
Easy
Easy
activity (78.5 to 56.0%) [195].
Cationic lignin nanosphere was used as a carrier for
Potentially cheaper
adsorption, enzyme adsorption, entrapment and evapora-
Continuous fixed-
Not sensitive
Moderate
catalysts
Possible
Easy
butyl butyrate under the biphasic state (50% water), in a
4-fold enzyme dosage with a reaction duration of 24 h [28].
must be neutralized leading to
Repeated washing
Not possible
Difficult
Normal
methodology
Purification of
Reaction rate
biodiesel
Processing
Water/FFA
glycerol
from the products [198]. In addition, the physical charac- reaction with higher ethanol/triolein ratios [205]. The mix-
teristics of nanoparticles such as increased diffusion and ing efficiency is an important factor influencing the effi-
particle mobility can affect the intrinsic catalytic activity ciency of lipase for biodiesel production. An optimum
of immobilized enzymes [197]. Other advantages of using stirring rate was 500–600 rpm for the transesterification
nanoparticles are thermal stability, increased surface area process. Burkholderia lipase immobilized on MNPs achieved
and irradiation resistance for their potential applications 90% conversion with low-dosage biocatalyst loading and
in photodetectors, solar cells, biosensor, nanogenera- better catalyst reusability [206]. Lipase NS81006 immobi-
tors and ceramics [199]. MNPs residing on an iron oxide lized on Fe3O4@SiO2 MNPs at a ratio of 1:0.25 used in trans-
core and silica shell have unique magnetic reactivity, low esterification provided a higher yield of methyl esters than
toxicity and a chemically modified surface. Silica-coated that of Fe3O4@SiO2 MNPs developed with a high level (1:0.5,
nanoparticles (Fe3O4@SiO2) are well adapted solid carriers 1:1 and 1:2) of TEOS (tetraethyl orthosilicate) [207]. C. rugosa
for enzyme immobilization [35]. Many studies have been lipase immobilized onto Fe3O4-decorated graphene oxide
carried out for the production of biodiesel by lipase immo- yielded 92.8% biodiesel at 40°C by three-step addition of
bilized on MNPs as biocatalysts. methanol. The catalyst maintained the catalytic activity
Activity Biodiesel
Method of Immobilization recovery conversion
Catalyst immobilization efficiency (%) w(%) Reaction conditions efficiency (%) Cycles Reference
Lipase (NS81006) immobilized on Covalent binding 97.73 (APTES); 86.08 (APTES); Temperature 45°C; 3-step add- 89 (APTES) 3 [36]
APTES and MPTMS-Fe3O4 95.39 (MPTMS) 83.7 (MPTMS) ition of methanol 1:3; catalyst 81 (MPTMS)
0.5 g; stirring rate 600 rpm;
(mechanical blender); time 12 h
Burkholeria sp. lipase Physisorption alkyl- 97 96 Oil/methanol molar ratio 1:4; stir- 92 10 [206]
immobilized on Fe3O4–SiO2 functionalized ring rate 600 rpm; water con-
magnetic tent 10 wt%; temperature 40°C;
nanoparticles time 30 h; stirring rate 600 rpm
Pseudomonas cepacia lipase Covalent binding 92.3 60 Methanol/oil ratio 5.2; water 79 3 [208]
immobilized on Fe3O4 content 12.5 wt%; catalyst 40%
(w/w oil); temperature 44.2°C;
time 24 h
Candida rugosa lipase immobilized Covalent binding 84 63 Oil/methanol ratio 1:4; 3-step 86 4 [209]
on polymer [poly(styrene-meth- addition of methanol; catalyst
acrylic acid])–coated Fe3O4 40% (w/w oil); temperature
35°C, time 24 h
Thermomyces Covalent binding NA NA Methanol/ oil ratio 7.6:1; catalyst 97 (CA) 11 [210]
lanuginosus lipase (TLL) & Candida 3.3% (w/w oil); temperature 98 (TL)
antarctica lipase B (CALB) immo- 30°C; time 12 h; shaking rate
bilized on Fe3O4 30 rpm
Candida antarctica (Novozym Physisorption NA NA Temperature 30°C; 98.4 50 [211]
435) immobilized on acrylic MeOH/oil 3:1; stepwise adding
resin solvent-free water <1%;
pH not controlled; catalyst 4.2%;
72 h; shaker
(Pseudomonas fluorescens & P. cepa- Physical adsorption NA NA Temperature 40°C; MeOH/oil 8:1; 58, 22 h NA [212]
cia) lipase immobilized on solvent-free water 0%; pH not 37, 51.5 h
macroporous polypropylene controlled; catalyst 6.25%;
shaker
Novozym 435 C. antarctica lipase Not available NA NA Temperature 40 °C; MeOH/oil 3:1; 85 5 [213]
immobilized on acrylic resin t-butanol 78.09%; water 0.35–
0.45%[ pH not controlled, cata-
lyst 4%; 30 h, shaker
Themomyces Covalent binding 90.4 70 Temperature 45 °C; 90 3 [214]
lanuginose(Novozymes) immobi- stepwise MeOH addition (MeOH/
lized on Fe3O4 oil, 1:1 each step); pH 7.0; 35 h;
shaker
Thangaraj et al. | 15
Lipase immobilized on MPTMS- Covalent binding 94 (1:0.25); 83 (1:0.25); Temperature 45°C, 3-step add- 91 (1:0.25) 3 [207]
Fe3O4@SiO2 (1:X, X–0.25, 0.5, 1, 86 (1:0.5); 79 (1:0.5); ition of methanol 1:3; catalyst 75 (1:0.5) 3
1.2) 85 (1:1); 76 (1:1); 0.5 g; stirring rate 600 rpm; 78 (1:1) 3
82 (1:2); 68 (1:2) (mechanical blender); 12 h 71 (1:2) 4
T. lanuginosa immobilized on Fe3O4 Covalent binding 84 70 Oil/methanol ratio 1:1 (each 90 4 [216]
step); 3-step addition of
methanol (1.05 g); catalyst 40%
(w/w oil); temperature 50°C;
time 12 h; shaker
Burkholderia lipase immobilized on Physisorption NA NA Oil/methanol ratio 1:4; catalyst 70% 6 [204]
hydrophobic Fe3O4@SiO2 300 U/ml; room temperature;
10% water content; agitation
200 rpm; time 12 h
Porcine pancreas lipase (lipase Physisorption & covalent 85.2 (L1); 95.7 (L1); Catalyst 5 mg; temperature 100% (L3) 9 [217]
L1), C. rugosa lipase (lipase L2) & binding 82.4 (L2); 70.1 (L2); 40°C; shaking 120 rpm; 1.5 ml
P. cepacia lipase (lipase L3) im- 80.3 (L3); 82.6 (L30 distilled water; oil/methanol
mobilized on Fe3O4 molar ratio 1:6
Rhizopus oryzae lipase immo- Covalent binding NA NA Oil/methanol molar ratio 1:4; 91.3 6 [218]
bilized on magnetic chitosan catalyst 25 g; temperature 35°C;
microspheres reactant flow rate 20 ml/min;
magnetic field intensity 225 Oe;
time 72 h
Lipase immobilized on APTES- Covalent Binding 79 54 Temperature 45°C; 3-step add- 76 5 [219]
Fe3O4@SiO2 (1:3) ition of methanol 1:3; catalyst
0.5 g; stirring rate 600 rpm;
time 12 h
Lipase immobilized on MPTMS- Covalent binding 77 50 Temperature 45°C; 3-step add- 72 5 [220]
Fe3O4@SiO2 (1:3) ition of methanol 1:3; catalyst
0.5 g; stirring rate 600 rpm;
time 12 h
Lipase immobilized on graphene Covalent binding 85.5 64.9 Oil 48.5 g; methanol/ oil ratio 1:4; 92.8 5 [98]
oxide–Fe3O4 biocatalyst amount 20 wt%;
temperature 40°C; time 60 h
Cathode
Anode
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