Efficient Synthesis of Biodiesel Catalyzed by Chitosan-Based Catalysts

Wang, Anping; Quan, Wenxuan; Zhang, Heng

doi:https://doi.org/10.1155/2021/8971613

International Journal of Chemical Engineering

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Abstract Introduction Conclusions Data Availability Conflicts of Interest Acknowledgments References Copyright Related Articles

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Thermal Catalytic Synthesis of Biofuels and High-Value Chemicals

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Review Article | Open Access

Volume 2021 | Article ID 8971613 | https://doi.org/10.1155/2021/8971613

Efficient Synthesis of Biodiesel Catalyzed by Chitosan-Based Catalysts

Anping Wang,¹Wenxuan Quan,¹and Heng Zhang²

Academic Editor: Prem Kumar Seelam

Received09 Jul 2021

Revised16 Nov 2021

Accepted17 Nov 2021

Published29 Dec 2021

Abstract

Catalysts play an important role in the preparation of biodiesel. It is of great significance to study catalysts with high efficiency, low cost, and easy preparation. Compared with the homogeneous catalyst system, the heterogeneous catalyst is easy to separate and has a better catalytic effect. In heterogeneous catalysts, supports and preparation methods have important effects on the dispersion of active centers and the overall performance of catalysts. However, the supports of existing solid catalysts have defects in porosity, structural uniformity, stability, and specific surface area, and the preparation methods cannot stabilize covalent bonds or ionic bonds to bind catalytic sites. Considering the activity, preparation method, and cost of the catalyst, biomass-based catalyst is the best choice, but the specific surface area of the biomass-based catalyst is relatively low, the distribution of active centers is uneven, and it is easy to lose. Therefore, the hybrid carrier of biomass-based catalyst and other materials can not only improve the specific surface area but also make the distribution of active centers uniform and the catalytic activity better. Based on this, we summarized the application of chitosan hybrid material catalysts in biodiesel. The preparation, advantages and disadvantages, reaction conditions, and so on of chitosan-based catalysts were mainly concerned. At the same time, exploring the effects of different types of chitosan-based catalysts on the preparation of biodiesel and exploring the process technology with high efficiency and low consumption is the focus of this paper.

1. Introduction

In recent decades, with the accelerated development of industrialization, global fossil fuel consumption and greenhouse gas emissions have increased rapidly. Scientists predict that the total global energy consumption will increase by 28% from 2015 to 2040 [1]. However, traditional energy, which is the main source of global energy supply, is constantly consumed, leading to energy shortage. This problem has attracted the attention of researchers all over the world, who are looking for sustainable and ecofriendly alternative energy [2, 3]. Therefore, scientists try to replace fossil fuels by developing renewable green energy, among which biofuels are the most competitive. Biodiesel is the most representative liquid biofuel among biofuels. It has the advantages of green, renewable, nontoxic, and environmental protection [4]. Meanwhile, biodiesel is almost free of sulfur and aromatic substances, biodegradable, and belongs to truly renewable “green energy” [5].

First of all, the main raw materials used to prepare biodiesel are rapeseed oil, soybean oil, and other edible oils, but this has an impact on national food safety and there is a problem of competing with people for food. Later, further research showed that nonedible oils are also used as the raw materials for biodiesel production, such as Jatropha curcas, Euphorbia lathyris [6], Xanthium sibiricum [7], Firmiana platanifolia [8], and Koelreuteria integrifoliola [9]. This expands the raw material source of biodiesel and greatly reduces the cost. After that, to further reduce the cost, biodiesel was prepared from waste cooking oil and animal fat with high acid value [10]. In addition, microalgae are also used as biodiesel raw materials, which is effective to reduce the cost of biodiesel, but the cultivation of microalgae also requires additional costs. In short, the new raw materials of biodiesel are of great significance for alleviating the energy crisis, protecting the ecological environment and adjusting the agricultural structure [11–13].

Biodiesel is generally a mixture of fatty acid methyl ester or ethyl ester, mainly because the raw materials for its synthesis contain many types of triglycerides [5]. The conventional method of synthesizing biodiesel are esterification and transesterification. Generally, acids [14], bases [15], and enzymes [16] are used as catalysts for biodiesel synthesis. Heterogeneous catalysts have gradually replaced homogeneous catalysts, which is mainly because heterogeneous catalysts can be reused many times, which can effectively reduce the cost [11]. Nowadays, different kinds of heterogeneous catalysts have been used to prepare biodiesel, including carbon materials [17], SiO₂ materials [18], oxides [19], ion exchange resins [20], magnetic materials [21], and supported enzymes [22]. However, the traditional solid catalyst has the disadvantages of easy loss of active sites and poor reusability. Therefore, looking for a green, efficient, and stable heterogeneous catalyst to prepare biodiesel has become one of the research hotspots for the preparation of high-performance heterogeneous catalysts [1].

Nowadays, people realize that the development of renewable and biodegradable biomass-based catalysts is more conducive to green environmental protection [23]. The excellent performance of functionalized biomass-based catalysts has attracted much attention [24]. In terms of biomass, chitosan prepared from shrimp shells and crab shells is a high molecular polymer biomass-based material. Chitosan has a large number of active −OH and −NH₂ groups and has strong modification ability. At the same time, chitosan is a cheap polymer material, which has natural advantages as a catalyst material in industrial production. Chitin, the raw material of chitosan, is a natural polymer compound second only to cellulose in nature. It is not only rich in resources but also widely used in medicine, food, chemical industry, cosmetics, water treatment, and other fields because of its biological function, compatibility, safety, and biodegradability [25–29].

This paper focuses on the research progress of chitosan-based catalysts in biodiesel. The synthesis method, physicochemical properties, catalytic efficiency, and reaction conditions of chitosan-based catalysts were also discussed. We hope that through this paper, we can provide new ideas for the preparation of biomass-based catalysts and obtain more efficient, green, and environmentally friendly new catalysts for the industrial synthesis of biodiesel.

2. Chitosan Derivatives

Because chitosan is easy to be modified, there are many derivatives of chitosan, which makes it possible to prepare a variety of chitosan-based catalysts, with more and more applications for the production of biodiesel.

Zhao et al. [30] prepared CoFe₂O₄-CS-SO₃H chitosan solid magnetic sulfonic acid catalyst for the synthesis of compounds. The preparation process of the catalyst is simple, and the obtained catalyst has strong magnetism (Figure 1).

Chitosan is a kind of polysaccharide that is easy to graft. Some researchers have tried to graft sulfonic groups onto chitosan monomers and synthesized several chitosan sulfate membranes. This makes the catalyst contain the sulfonic group and amino functional group, which further improves the activity of the catalyst [31]. Gu et al. [32] prepared chitosan-doped polyvinyl alcohol films by the blending heating method. The surfaces of these membranes are usually wrinkled and have excellent separation performance. They can be used for pervaporation to separate methanol-biodiesel mixtures. Gupta and Jabrail [33] used the glutaraldehyde crosslinking method to prepare chitosan microspheres (in Figure 2). Usually, glutaraldehyde condenses with the amino group of chitosan ammonia to form a network polymer, and the formed chemical bond crosslinks and solidifies the microspheres. In this process, the loaded particles can be wrapped in the microspheres or adsorbed on the surface of the microspheres. This is conducive to the encapsulation of internal magnetic particles and the adsorption of external catalyst particles.

Liu et al. [34] introduced a simple method for preparing magnetic chitosan Fe₃O₄ nanoparticles. Immobilized lipase was prepared by a glutaraldehyde crosslinking reaction under a 0.45 T static magnetic field. The results show that there is no significant difference in the structure of nanoparticles, the morphology of nanoparticles changes from spherical to a rod, and the magnetic properties change significantly.

Li et al. [35] prepared a series of chitosan hybrids based on polyoxometalates by anion exchange of a novel cross-linked chitosan ionic polymer with H₃PW₁₂O₄₀. Bodmeier et al. [36] first proposed the preparation of chitosan microspheres by the ionic gel method (in Figure 3). The polyanion of sodium tripolyphosphate is used as a crosslinking agent, which is combined with the positively charged amino group after the protonation of the chitosan molecular chain. Through the electrostatic interaction, the physical crosslinking of the molecules can be reversible, intramolecular or intramolecular, so that the chitosan can be gelated into spherical particles.

Huang et al. [37] prepared N-doped carbon prepared by chitosan with a large specific surface area. Chitosan is dissolved in acetic acid and carbonized to form porous carbon. After KOH activation, its specific surface area can reach 3532 m²/g. The carbon-based catalyst is relatively stable and has a large specific surface area.

A new type of sustainable catalytic material was prepared from biological waste (chitosan) and rare earth–rich cobalt salt (in Figure 4). Through the chelation of chitosan with Co, the carbonized catalyst has a carbon shell containing N and encapsulates Co and Co₃O₄, which can improve the performance of the catalyst and effectively reduce the loss of active components. The catalyst has been reused many times, and the efficiency has not changed significantly [38].

Roosen et al. [39] prepared SiO₂ chitosan composite mesoporous material with a specific surface area of 219 m²/g, pore volume of 1.036 cm³/g, and pore size of 9.5 nm, which belongs to mesoporous structure and is more suitable as a catalyst support material. Sana et al. [40] prepared chitosan microspheres supported a Pd catalyst, including the direct complexation of Pd²⁺ with the amino group on chitosan and the complexation of chitosan modified by glutaraldehyde with Pd²⁺, and the complexation of chitosan modified by glutaraldehyde with Pd²⁺. γ-Thiobutyrolactone-modified chitosan has three kinds of catalysts: sulfhydryl group and Pd²⁺. The specific surface areas of the three catalysts are 239, 239, and 302 m²/g, respectively. γ-Thiobutyrolactone-modified chitosan microspheres have a higher specific surface area. Also, the catalyst is used in the mixed solution of water and ethanol, so it has strong hydrophobicity. It is expected that the modified biodiesel can be used in the preparation of water-containing biodiesel.

3. Chitosan Gel and Chelating Metal Catalysts

3.1. Chitosan Gel

To reduce the production cost of biodiesel, more and more kitchen waste oil, non-edible vegetable oil, and microalgae oil are used as raw materials of biodiesel. However, these raw materials contain a large amount of free fatty acids (FFA). The key to the synthesis of biodiesel is to find heterogeneous catalysts that can simultaneously catalyze esterification and transesterification. Kayser and Pienkoß [41] evaluated the transesterification with chitosan and frozen gel as catalysts for different oils and methanol. As a green waste and a catalyst for biofuel production, chitosan can increase new possibilities for local value. Chitosan freeze-gel successfully catalyzed transesterification of three oleic glycerin and soybean oil with methanol and achieved a yield of 90% of biodiesel at 8 to 32 hours at 100–150°C. The chitosan beads were washed with tertbutyl alcohol and methanol, and the fat and glycerin were desorbed. To achieve practical use, further research and development opportunities can be identified at the catalyst design level, and new catalysts based on chitosan, such as aerogels, layers, and chitosan derivatives can be used to achieve more efficient catalytic activity and will show a greater degree of recyclable results.

3.2. Chitosan Chelating Metal Catalysts

Da Silva et al. [42] used chitosan-adsorbed Cu (II) and Co (II) catalysts for transesterification of soybean and babassu oil. The maximum adsorption capacities of copper and cobalt ions were 1.584 and 1.260 mg, respectively, while the oil conversion of biodiesel was higher when using chitosan-adsorbed Co (II) as a catalyst.

4. Acidic Modified Chitosan Catalysts

4.1. Sulfonic Acid

Based on the fact that chitosan is easy to crosslink, a new type of acidic chitosan membrane (ACM) was formed by crosslinking chitosan with sulfosuccinic acid (SSA). The esterification reaction of oleic acid and methanol was carried out to test the catalytic effect (in Figure 5). The acid density of ACM was 4.62 mmol/g, which was only slightly lower than that of Amberlyst-15 (4.76 mmol/g). Under the same conditions, the catalytic efficiency of Amberlyst-15 was only 44.30%, while that of ACM was 98.76%. The reaction conditions were optimized by combining a single factor test with the response surface method. The catalytic activity of ACM for esterification of fatty acids with alcohols was studied. In addition, the reusability of ACM is also studied [43]. In conclusion, the active sites are more exposed after chitosan crosslinking, which is beneficial to the catalytic reaction, which is also the reason why ACM has higher catalytic efficiency.

Caetano et al. [44] studied the esterification of palmitic acid with methanol at 60°C. The sulfonic group was introduced into chitosan (CT) by crosslinking with sulfosuccinic acid (SSA). With the increase of sulfonic group content in chitosan, the catalytic activity increased. However, with the increase of sulfonic group content, the catalytic activity decreased. This kind of behavior can be explained by the factors of limiting diffusion. The catalytic stability of CT4 (2.08 mmol sulfonic group/g) was evaluated by using the same catalyst samples for continuous batch operation. After the second batch reaction, the catalytic activity tends to be stable. CT4 catalyst is also used for esterification of oleic acid and stearic acid with methanol. CT4 has good catalytic activity for different substrates used in esterification. It is confirmed that chitosan is a kind of biopolymer rich in the sulfonic group, and it is an efficient and environmentally friendly heterogeneous catalyst.

Wang et al. [45] prepared a chitosan sulfonic acid catalyst by a relatively simple method. The specific method is to disperse chitosan with dichloromethane as the solvent and then sulfonate chitosan with chlorosulfonic acid to obtain a biomass-based catalyst with an acid density up to 3.81 mmol/g. SEM results show that CS-SO₃H is spherical with a diameter of about 10 μm. After four times of reuse, the yield of the catalyst can still reach 85.7%, which indicates that this kind of sulfonic acid catalyst has a good application prospect.

4.2. Heteropoly Acid

Tong et al. [46] used H₃PW₁₂O₄₀, chitosan, and Ti⁴⁺ as carriers to prepare water-insoluble multifunctional active sites and H₃PW₁₂O₄₀/Ti/chitosan hybrid materials (in Figure 6). Due to the presence of B acid from H₃PW₁₂O₄₀, Lewis acid from Ti⁴⁺, and base from −NH₂ group of chitosan, the catalyst showed high activity in the esterification reaction, all of which was due to the pore formation in chitosan by introducing Ti ions. Moreover, H₃PW₁₂O₄₀/Ti/chitosan can be reused at least 6 times as a heterogeneous catalyst; the activity reduction is not obvious, and only a small amount of Ti⁴⁺ and H₃PW₁₂O₄₀ are leached from the carrier chitosan.

Han et al. [47] prepared organic-inorganic hybrid catalysts by glycine (Gly) and phosphotungstic acid (TPA), namely [Gl_yH]_xH_3-xPW₁₂O₄₀ (x = 1.0−3.0), and studied the catalytic performance of various Gly-TPA catalysts in the esterification of palmitic acid with methanol to produce methyl palmitate. Under the optimum conditions, the yield of biodiesel can reach 93.3%.

4.3. Chitosan Magnetic Acid

Wang and his colleagues [48] synthesized a new magnetic mesoporous solid acid catalyst (FCHC-SO₃H) (in Figure 7). The catalyst was prepared from biodegradable chitosan with a double-shell hollow structure, which increased the active sites, and the synthesis process was mild and environmentally friendly. More importantly, the catalyst has good catalytic performance for the esterification of oleic acid and methanol to biodiesel, which can be reused 5 times without a significant decrease in activity and can be easily separated by an external magnetic field.

5. Basic-Modified Chitosan Catalysts

5.1. Inorganic Base

Used waste cooking oil (WCO) or frying oil is considered to be a rich source of economic raw materials for biodiesel production. Zeolite/chitosan/KOH composite was used as a solid heterogeneous catalyst for transesterification of WCO to methyl ester (biodiesel) (in Figure 8). The results show that the treatment of natural zeolite (clinoptilolite) with KOH can significantly reduce the silicon content and increase its K⁺. The content is determined by the formation of hydroxy calcium carbonate. Electrolysis (EM) is used as a suitable technology for energy and resource recovery in waste treatment. In theory, EM can convert any biodegradable waste into H₂, O₂, biofuel, glycerol, and other byproducts. However, the effectiveness of the system may vary greatly in different situations. In the presence of water, the conversion of biodiesel from WCO was obtained with 93% yield within 3 hours with 1% catalyst concentration and 1 : 70 alcohol/oil ratio (at 40 V) and 2% of the total solution. The best conversion process can be achieved by using acetone as the cosolvent [49].

Correia et al. [50] think that chitosan can be used as a structural agent by inserting calcium oxide and as a catalyst in transesterification. These calcium-doped chitosan spheres were calcined to obtain porous calcium catalyst without organic matter. The materials were characterized by X-ray diffraction, thermogravimetric analysis, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, temperature-programmed CO₂ desorption, scanning electron microscopy, and specific surface area analysis. Then, the calcined calcium/chitosan spheres were used for the transesterification of sunflower oil with methanol. Sunflower seed oil was converted to methyl ester (FAME) under the optimal reaction conditions: 3 wt%; time, 4 h; temperature, 60°C; magnetic stirring (1000 rpm) was 56.12 ± 32% by weight. These results indicate that chitosan can be used as a precursor for the formation of calcium/chitosan spheres to produce porous calcium oxide (with a high surface area) which can be used as an alkaline catalyst for biodiesel production.

Liang et al. [51] prepared a new polymer-based alkaline biodiesel catalyst from epichlorohydrin (ECH)-crosslinked n-[(2-hydroxy-3-trimethylammonium) propyl] chitosan chloride (HTCC) and sodium silicate (Na₂SiO₃). The structure and properties of the catalyst were studied by Fourier-transform infrared spectroscopy, thermogravimetry-mass spectrometry, and transmission electron microscopy. The effects of various factors on the preparation of biodiesel by transesterification of soybean oil were studied. The results show that Na₂SiO₃ is bridged on the HTCC chain by ECH and dispersed in the HTCC matrix in nanoscale. Under the optimum reaction conditions (6/1 methanol/oil mole ratio and 4 wt% catalyst dosage at 55°C for 1 h), a high biodiesel yield of 97.0% was obtained. After the second reaction, the catalyst activity remained stable, which was conducive to the stability and dispersion of Na₂SiO₃ in the catalyst.

Fu et al. [52] used chitosan as a new substrate for immobilization of CaO. Biodiesel was produced by transesterification of soybean oil with methanol, and Cao immobilized on chitosan beads was used as a heterogeneous catalyst. To obtain a stable immobilized catalyst, chitosan beads with immobilized CaO were crosslinked with glutaraldehyde. Two crosslinking parameters, crosslinking time and glutaraldehyde concentration were studied to reveal the optimal immobilization conditions, which were 30 min and 0.22 mol/L⁻¹, respectively. Under those conditions, the immobilized catalyst with a very low CaO leaching rate can be obtained. The immobilized CaO catalyst was prepared by transesterification of soybean oil with methanol. The transesterification rate was studied by response surface methodology, which was affected by catalyst loading, methanol-oil molar ratio, and temperature. The maximum reaction rate was 0.6 H⁻¹, the molar ratio of methanol to oil was 13.4 at 60°C, and the catalyst loading was 13.78 wt%. Under these conditions, the equilibrium conversion of soybean oil was 97% after 3 hours. In addition, the fixed catalyst can be reused at least five times. This study developed a simple and energy-saving method to prepare chitosan-based immobilized CaO catalyst, which is expected to be used in potential applications including biodiesel production.

5.2. Organic Base

He et al. [53] synthesized guanidine chitosan (GCS) as the heterogeneous basic catalyst for transesterification of soybean oil with methanol using amino methylene sulfonic acid as a graft (in Figure 9). The structure and properties of GCS films were studied by Fourier-transform infrared spectroscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. Under the conditions of catalyst dosage of 20%, methanol-oil ratio of 2.5 : 1, reaction temperature of 60°C, and reaction time of 6 h, the conversion of soybean oil reached 98.8% for the first time, and 96.6% for the fifth time. The results showed that the transesterification mainly occurred on the surface of the catalytic membrane. The kinetics of transesterification was studied by a pseudohomogeneous model. The reaction was a first-order reaction with an activation energy of 76.95 kJ/mol and a pre-exponential factor of 7.94 × 10⁹ min⁻¹.

6. Modified Chitosan/Enzyme Catalysts

The unique structure of chitosan is not considered an excellent carrier for immobilized lipase, which promotes the production of a variety of chitosan-loaded lipases. Its advantages include low reaction temperature, repeated use, and high reaction activity. This makes chitosan-loaded lipase widely used in the production of biodiesel.

Rhizopus lipase was immobilized on magnetic chitosan microspheres (MCMs), and biodiesel was prepared from soybean oil and methanol. The maximum content of methyl ester in the reaction mixture reached 91.3 (w/v) at the flow rate of 25 mL/min and the magnetic field strength of 150 Oe. In addition, MCMs-immobilized lipase in the reactor has excellent reusability, and it still maintains 82% productivity even after 6 batches, which is far better than that in a traditional fluidized bed reactor. These results show that MCMs-immobilized lipase is a promising biodiesel production method [54].

The preparation of biodiesel from rapeseed soap residue methanol catalyzed by chitosan-immobilized Candida lipase (CRL) was studied by response surface methodology (RSM). Methanol-substrate molar ratio, enzyme dosage, water content, and reaction temperature are four important parameters. RSM analysis shows that the experimental values are in good agreement with the predicted values. The results show that the most effective parameter is water content, which is in good agreement with the experimental values. The coefficient of determination (R2) of the model is 92.86%, with a probability value of . The optimal conditions for biodiesel production by immobilized lipase were as follows: the molar ratio of methanol to the substrate was 4 : 1, the amount of lipase was 8%, the water content was 6%, and the reaction temperature was 45°C. After molecular distillation, the content of methyl ester is more than 95% [55].

Magnetic whole-cell biocatalyst (MWCB) was prepared using chitosan Fe₃O₄ microspheres as a carrier (in Figure 10). The yield of biodiesel was 87.32% after 48 h. After 10 cycles, the yield of biodiesel was 83.57%, which was higher than that of whole-cell biocatalyst without Fe₃O₄ (74.06%). It can be seen that the introduction of magnetic particles not only makes the catalyst easy to separate but also effectively immobilizes the active enzyme to avoid the loss of yield. Interestingly, in previous studies, it was not realized that the introduction of magnetic particles can also increase the yield [56].

Cubides-Roman et al. [57] used magnetic chitosan-immobilized Pseudomonas fluorescens lipase as a biocatalyst to study the enzymatic synthesis of ethyl ester from coconut oil and ethanol in an electromagnetic field-assisted bioreactor. The results show that under the conditions of 30°C, 45°C, and 60°C, oil alcohol molar ratios of 1 : 6, 1 : 9, and 1 : 12, and magnetic induction intensity of 6.5, the maximum conversion is about 12%. In the differential reactor, the molar ratio of oil to alcohol was 1 : 11.25, and the reaction time was 12 h In this unconventional bioreactor, under the assistance of a magnetic field, the synthesis of esters is positively affected by the molar ratio and temperature, and magnetic induction is very important for the establishment of a magnetically stabilized bed. In addition, magnetic biocatalysts are retained/separated for further use. Although this interesting device did not obtain a large yield, the application of the new device proved that this model can be used for transesterification to synthesize biodiesel, which added a new method for the preparation of biodiesel.

At present, the efficiency of biomass-based materials is further improved, and the application of immobilized enzymes in biodiesel synthesis is expanded. Batista et al. [58] reported a new biodegradable membrane catalyst, which is composed of chitosan, lipase, and polyvinyl alcohol. The thicknesses of PVA/chitosan and PVA/chitosan/lipase membranes were 70.4 and 79 μm, respectively. The SEM images showed the formation of continuous films without holes or cracks. It is estimated that the lipase rejection efficiency is 92%. The membrane can be reused for 25 hydrolysis cycles and can maintain 62% of the initial activity. These results show that PVA/chitosan/lipase is a promising material for biodiesel production. Similarly, Xie and Wang [25] used magnetic chitosan microspheres to immobilize lipase to study the transesterification of soybean oil. Using glutaraldehyde as a crosslinking agent, magnetic chitosan microspheres lipase was prepared by the chemical coprecipitation method. Using immobilized lipase, the yield of converted soybean oil fatty acid methyl ester reached 87% at an alcohol-oil ratio of 4 : 1, 35°C, and 30 h. the catalyst was reused 4 times without significant reduction inactivity.

Undoubtedly, lipase can efficiently catalyze transesterification at low temperatures, which is considered to be the greatest advantage of lipase in biodiesel synthesis. However, the high cost of lipase is considered to be the main obstacle to the commercialization of enzymatic transesterification. Karimi synthesized superparamagnetic iron oxide nanoparticles (SPIONs), coated them on silica, and then grafted aldehyde groups to immobilize Bacillus capacity lipase, which is a promising method to improve the economy of enzymatic transesterification. The results show that the average particle size of SPIONs is about 20 nm. The nanoparticles linked to lipase showed almost superparamagnetism. Under the conditions of methanol to oil molar ratio of 6 : 1, immobilized lipase concentration of 25%, n-hexane content of 10%, the water content of 10%, reaction temperature at 35°C, and reaction time of 35 h, the conversion rate of WCO to biodiesel reached 91%. The immobilized lipase is easy to recover and reuse, and the enzyme activity has hardly decreased [59].

Chitosan was tried to be used as a perfect carrier for lipase immobilization by adsorption and crosslinking. The immobilization efficiency of the crosslinking method was 99.1%, and the reusability was 12 cycles. The esterification of oleic acid and transesterification of olive oil showed that the partially purified enzyme proved its ability to catalyze the formation of methyl oleate. The partially purified and immobilized lipase of Rhizopus oryzae R1 has excellent efficiency and reusability and plays an important role in biodiesel production [60].

7. Conclusions

This paper reviews the application of heterogeneous catalysts supported on biomass-based chitosan in the synthesis of biodiesel. Chitosan has the greatest advantage of having a large number of active amino and hydroxyl groups, easy to modify and graft, and easy to chelate metal ions. At the same time, it can be compounded with a variety of materials to obtain multifunctional catalytic materials, which will undoubtedly improve the catalytic efficiency. At present, it is common to prepare chitosan-based catalysts rich in acid, alkali, metal ions, or enzyme active sites. However, these catalysts with different forms still have the problems of low catalyst surface area, easy loss of active centers, and difficult separation, and there is still a need for further improvement.

Therefore, we need to further develop new chitosan-based materials to make this kind of catalyst not only to have good catalytic efficiency but also biodegradable, green, and nontoxic and can be used many times. At present, the number of chitosan-based biodiesel synthesis materials reported is limited. It is hoped that more chitosan-based catalysts with excellent performance can be developed and applied to the large-scale production of biodiesel based on laboratory research.

Data Availability

No data were used in the study.

Conflicts of Interest

The authors declare no conflicts of interest.

Acknowledgments

This study was financially supported by the Guizhou Science and Technology Foundation ([2021]075) and Guizhou Provincial Characteristic Key Laboratory (QJHKY [2021]002).

References

R. V. Quah, Q. Yie, H. Tan et al., “An overview of biodiesel production using recyclable biomass and nonbiomass derived magnetic catalysts,” Journal of Environmental Chemical Engineering, vol. 7, no. 4, Article ID 103219, 2019.
View at: Publisher Site | Google Scholar
H. Zhang, H. Li, C. C. Xu, and S. Yang, “Heterogeneously chemo/enzyme-functionalized porous polymeric catalysts of high-performance for efficient biodiesel production,” ACS Catalysis, vol. 9, no. 12, pp. 10990–11029, 2019.
View at: Publisher Site | Google Scholar
M. R. Avhad and J. M. Marchetti, “Innovation in solid heterogeneous catalysis for the generation of economically viable and eco-friendly biodiesel: a review,” Catalysis Reviews, vol. 58, no. 2, pp. 157–208, 2016.
View at: Publisher Site | Google Scholar
Z.-E. Tang, S. Lim, Y.-L. Pang, H.-C. Ong, and K.-T. Lee, “Synthesis of biomass as heterogeneous catalyst for application in biodiesel production: state of the art and fundamental review,” Renewable and Sustainable Energy Reviews, vol. 92, pp. 235–253, 2018.
View at: Publisher Site | Google Scholar
N. Mansir, Y. H. Taufiq-Yap, U. Rashid, and I. M. Lokman, “Investigation of heterogeneous solid acid catalyst performance on low-grade feedstocks for biodiesel production: a review,” Energy Conversion and Management, vol. 141, pp. 171–182, 2017.
View at: Publisher Site | Google Scholar
R. Wang, M. A. Hanna, W.-W. Zhou et al., “Production and selected fuel properties of biodiesel from promising non-edible oils: Euphorbia lathyris L., Sapium sebiferum L. and Jatropha curcas L,” Bioresource Technology, vol. 102, no. 2, pp. 1194–1199, 2011.
View at: Publisher Site | Google Scholar
F. Chang, M. A. Hanna, D.-J. Zhang et al., “Production of biodiesel from non-edible herbaceous vegetable oil: Xanthium Sibiricum patr,” Bioresource Technology, vol. 140, pp. 435–438, 2013.
View at: Publisher Site | Google Scholar
H. Zhang, H. Li, H. Pan et al., “Efficient production of biodiesel with promising fuel properties from Koelreuteria integrifoliola oil using a magnetically recyclable acidic ionic liquid,” Energy Conversion and Management, vol. 138, pp. 45–53, 2017.
View at: Publisher Site | Google Scholar
H. Zhang, Q. Zhou, F. Chang et al., “Production and fuel properties of biodiesel from Firmiana platanifolia L.f. as a potential non-food oil source,” Industrial Crops and Products, vol. 76, pp. 768–771, 2015.
View at: Publisher Site | Google Scholar
M. Kirubakaran and V. Arul Mozhi Selvan, “A comprehensive review of low cost biodiesel production from waste chicken fat,” Renewable and Sustainable Energy Reviews, vol. 82, pp. 390–401, 2018.
View at: Publisher Site | Google Scholar
A. F. Lee, J. A. Bennett, J. C. Manayil, and K. Wilson, “Heterogeneous catalysis for sustainable biodiesel productionviaesterification and transesterification,” Chemical Society Reviews, vol. 43, no. 22, pp. 7887–7916, 2014.
View at: Publisher Site | Google Scholar
N. Narkhede, S. Singh, and A. Patel, “Recent progress on supported polyoxometalates for biodiesel synthesis via esterification and transesterification,” Green Chemistry, vol. 17, no. 1, pp. 89–107, 2015.
View at: Publisher Site | Google Scholar
B. S. Sazzad, M. A. Fazal, A. S. M. A. Haseeb, and H. H. Masjuki, “Retardation of oxidation and material degradation in biodiesel: a review,” RSC Advances, vol. 6, no. 65, pp. 60244–60263, 2016.
View at: Publisher Site | Google Scholar
I. M. Atadashi, M. K. Aroua, A. R. A. Aziz, and N. M. N. Sulaiman, “Production of biodiesel using high free fatty acid feedstocks,” Renewable & Sustainable Energy Reviews, vol. 16, no. 5, pp. 3275–3285, 2018.
View at: Google Scholar
A. Marwaha, A. Dhir, S. K. Mahla, and S. K. Mohapatra, “An overview of solid base heterogeneous catalysts for biodiesel production,” Catalysis Reviews, vol. 60, no. 4, pp. 594–628, 2018.
View at: Publisher Site | Google Scholar
A. Guldhe, B. Singh, T. Mutanda, K. Permaul, and F. Bux, “Advances in the synthesis of biodiesel via enzyme catalysis: novel and sustainable approaches,” Renewable and Sustainable Energy Reviews, vol. 41, pp. 1447–1464, 2015.
View at: Publisher Site | Google Scholar
F. Zhang, X.-H. Wu, M. Yao, Z. Fang, and Y.-T. Wang, “Production of biodiesel and hydrogen from plant oil catalyzed by magnetic carbon-supported nickel and sodium silicate,” Green Chemistry, vol. 18, no. 11, pp. 3302–3314, 2016.
View at: Publisher Site | Google Scholar
B. Yang, L. Leclercq, J.-M. Clacens, and V. Nardello-Rataj, “Acidic/amphiphilic silica nanoparticles: new eco-friendly pickering interfacial catalysis for biodiesel production,” Green Chemistry, vol. 19, no. 19, pp. 4552–4562, 2017.
View at: Publisher Site | Google Scholar
A. Wang, H. Li, H. Zhang, H. Pan, and S. Yang, “Efficient catalytic production of biodiesel with acid-base bifunctional rod-like Ca-B oxides by the sol-gel approach,” Materials, vol. 12, no. 1, p. 83, 2019.
View at: Google Scholar
A. Hykkerud and J. M. Marchetti, “Esterification of oleic acid with ethanol in the presence of Amberlyst 15,” Biomass and Bioenergy, vol. 95, pp. 340–343, 2016.
View at: Publisher Site | Google Scholar
H. Zhang, L.-L. Zhang, X. Tan, H. Li, and S. Yang, “Catalytic high-yield biodiesel production from fatty acids and non-food oils over a magnetically separable acid nanosphere,” Industrial Crops and Products, vol. 173, Article ID 114126, 2021.
View at: Publisher Site | Google Scholar
A. Wang, P. Sudarsanam, Y. Xu, H. Zhang, H. Li, and S. Yang, “Functionalized magnetic nanosized materials for efficient biodiesel synthesis via acid-base/enzyme catalysis,” Green Chemistry, vol. 22, no. 10, pp. 2977–3012, 2020.
View at: Publisher Site | Google Scholar
S. H. Y. S. Abdullah, N. H. M. Hanapi, A. Azid et al., “A review of biomass-derived heterogeneous catalyst for a sustainable biodiesel production,” Renewable and Sustainable Energy Reviews, vol. 70, pp. 1040–1051, 2017.
View at: Publisher Site | Google Scholar
Y.-K. Lin, V.-H. Nguyen, J. C.-C. Yu et al., “Biodiesel production by pervaporation-assisted esterification and pre-esterification using graphene oxide/chitosan composite membranes,” Journal of the Taiwan Institute of Chemical Engineers, vol. 79, pp. 23–30, 2017.
View at: Publisher Site | Google Scholar
W. Xie and J. Wang, “Immobilized lipase on magnetic chitosan microspheres for transesterification of soybean oil,” Biomass and Bioenergy, vol. 36, pp. 373–380, 2012.
View at: Publisher Site | Google Scholar
P. A. Russo, M. M. Antunes, P. P. Neves et al., “Mesoporous carbon–silica solid acid catalysts for producing useful bio-products within the sugar-platform of biorefineries,” Green Chemistry, vol. 16, no. 9, pp. 4292–4305, 2014.
View at: Publisher Site | Google Scholar
X. Li, K. Cui, Z. Guo et al., “Heterogeneous Fenton-like degradation of tetracyclines using porous magnetic chitosan microspheres as an efficient catalyst compared with two preparation methods,” Chemical Engineering Journal, vol. 379, Article ID 122324, 2020.
View at: Publisher Site | Google Scholar
A. Dhakshinamoorthy, M. Jacob, N. S. Vignesh, and P. Varalakshmi, “Pristine and modified chitosan as solid catalysts for catalysis and biodiesel production: a minireview,” International Journal of Biological Macromolecules, vol. 167, pp. 807–833, 2021.
View at: Publisher Site | Google Scholar
Z. Yao, C. Zhang, Q. Ping, and L. Yu, “A series of novel chitosan derivatives: synthesis, characterization and micellar solubilization of paclitaxel,” Carbohydrate Polymers, vol. 68, no. 4, pp. 781–792, 2007.
View at: Publisher Site | Google Scholar
X.-N. Zhao, G.-F. Hu, M. Tang et al., “A highly efficient and recyclable cobalt ferrite chitosan sulfonic acid magnetic nanoparticle for one-pot, four-component synthesis of 2H-indazolo[2,1-b] phthalazine -triones,” RSC Advances, vol. 4, no. 93, pp. 51089–51097, 2014.
View at: Publisher Site | Google Scholar
Y. Xiang, M. Yang, Z. Guo, and Z. Cui, “Alternatively chitosan sulfate blending membrane as methanol-blocking polymer electrolyte membrane for direct methanol fuel cell,” Journal of Membrane Science, vol. 337, no. 1-2, pp. 318–323, 2009.
View at: Publisher Site | Google Scholar
L. Gu, Z. Zhang, S. Yang et al., “Chitosan-modified polyvinyl alcohol membrane high performance in biodiesel/methanol pervaporation separation,” ChemistrySelect, vol. 6, no. 34, pp. 9052–9059, 2021.
View at: Publisher Site | Google Scholar
K. C. Gupta and F. H. Jabrail, “Glutaraldehyde cross-linked chitosan microspheres for controlled release of centchroman,” Carbohydrate Research, vol. 342, no. 15, pp. 2244–2252, 2007.
View at: Publisher Site | Google Scholar
Y. Liu, S. Jia, Q. Wu, J. Ran, W. Zhang, and S. Wu, “Studies of Fe₃O₄-chitosan nanoparticles prepared by co-precipitation under the magnetic field for lipase immobilization,” Catalysis Communications, vol. 12, no. 8, pp. 717–720, 2011.
View at: Publisher Site | Google Scholar
J. Li, C. Zhang, P. Jiang, and Y. Leng, “Cross-linked chitosan supporting polyoxometalates catalyst with adjustable redox property for H₂O₂-based oxidation reactions,” Catalysis Communications, vol. 94, pp. 13–17, 2017.
View at: Publisher Site | Google Scholar
R. Bodmeier, H. Chen, and O. Paeratakul, “Novel approach to the oral delivery of micro-or nanoparticles,” Pharmaceutical Research, vol. 6, no. 5, pp. 413–417, 1989.
View at: Publisher Site | Google Scholar
J. Huang, Y. Liang, H. Hu et al., “Ultrahigh-surface-area hierarchical porous carbon from chitosan: acetic acid mediated efficient synthesis and its application in superior supercapacitors,” Journal of Materials Chemistry A, vol. 5, no. 47, pp. 24775–24781, 2017.
View at: Publisher Site | Google Scholar
B. Sahoo, A.-E. Surkus, M.-M. Pohl et al., “A biomass-derived non-noble cobalt catalyst for selective hydrodehalogenation of alkyl and (hetero) aryl halides,” Angewandte Chemie International Edition, vol. 56, no. 37, pp. 11242–11247, 2017.
View at: Publisher Site | Google Scholar
J. Roosen, J. Spooren, and K. Binnemans, “Adsorption performance of functionalized chitosan–silica hybrid materials toward rare earths,” Journal of Materials Chemistry A, vol. 2, no. 45, pp. 19415–19426, 2014.
View at: Publisher Site | Google Scholar
F. Sana, P. Ana, and L. Mohamed, “Pd embedded in chitosan microspheres as tunable soft-materials for sonogashira cross-coupling in the water-ethanol mixture,” Green Chemistry, vol. 17, pp. 1893–1898, 2015.
View at: Google Scholar
H. Kayser, F. Pienkoß, and P. Domínguez de María, “Chitosan catalyzed biodiesel synthesis: proof-of-concept and limitations,” Fuel, vol. 116, pp. 267–272, 2014.
View at: Publisher Site | Google Scholar
R. B. da Silva, A. F. Lima Neto, L. S. Soares dos Santos et al., “Catalysts of Cu (II) and Co (II) ions adsorbed in chitosan used in transesterification of soybean and babassu oils−a new route for biodiesel syntheses,” Bioresource Technology, vol. 99, no. 15, pp. 6793–6798, 2008.
View at: Publisher Site | Google Scholar
N. Saengprachum, D. Cai, M. Li, L. Li, X. Lin, and T. Qiu, “Acidic chitosan membrane as an efficient catalyst for biodiesel production from oleic acid,” Renewable Energy, vol. 143, pp. 1488–1499, 2019.
View at: Publisher Site | Google Scholar
C. S. Caetano, M. Caiado, J. Farinha et al., “Esterification of free fatty acids over chitosan with sulfonic acid groups,” Chemical Engineering Journal, vol. 230, pp. 567–572, 2013.
View at: Publisher Site | Google Scholar
A. Wang, H. Zhang, H. Li, and S. Yang, “Efficient production of methyl oleate using a biomass-based solid polymeric catalyst with high acid density,” Advances in Polymer Technology, vol. 2019, Article ID 4041631, 11 pages, 2019.
View at: Publisher Site | Google Scholar
T. Tong, Y. Li, R. Hou, X. Wang, and S. Wang, “Decoration of chitosan microspheres with brønsted heteropolyacids and lewis ion Ti: trifunctional catalysts for esterification to biodiesel,” RSC Advances, vol. 7, no. 67, pp. 42422–42429, 2017.
View at: Publisher Site | Google Scholar
X.-X. Han, K.-K. Chen, W. Yan et al., “Amino acid-functionalized heteropolyacids as efficient and recyclable catalysts for esterification of palmitic acid to biodiesel,” Fuel, vol. 165, pp. 115–122, 2016.
View at: Publisher Site | Google Scholar
A. Wang, H. Li, H. Pan et al., “Efficient and green production of biodiesel catalyzed by recyclable biomass-derived magnetic acids,” Fuel Processing Technology, vol. 181, pp. 259–267, 2018.
View at: Publisher Site | Google Scholar
L. Fereidooni and M. Mehrpooya, “Experimental assessment of electrolysis method in the production of biodiesel from waste cooking oil using zeolite/chitosan catalyst with a focus on waste biorefinery,” Energy Conversion and Management, vol. 147, pp. 145–154, 2017.
View at: Publisher Site | Google Scholar
L. M. Correia, N. D. S. Campelo, R. D. F. Albuquerque et al., “Calcium/chitosan spheres as catalyst for biodiesel production,” Polymer International, vol. 64, no. 2, pp. 242–249, 2015.
View at: Publisher Site | Google Scholar
M. Liang, B. He, Y. Shao, J. Li, and Y. Cheng, “Preparation and catalytic performance of N-[(2-Hydroxy-3-trimethylammonium)propyl] chitosan chloride/Na₂SiO₃ polymer-based catalyst for biodiesel production,” Renewable Energy, vol. 88, pp. 51–57, 2016.
View at: Publisher Site | Google Scholar
C.-C. Fu, T.-C. Hung, C.-H. Su et al., “Immobilization of calcium oxide onto chitosan beads as a heterogeneous catalyst for biodiesel production,” Polymer International, vol. 60, no. 6, pp. 957–962, 2011.
View at: Publisher Site | Google Scholar
B. He, Y. Shao, M. Liang, J. Li, and Y. Cheng, “Biodiesel production from soybean oil by guanidinylated chitosan,” Fuel, vol. 159, pp. 33–39, 2015.
View at: Publisher Site | Google Scholar
G.-X. Zhou, G.-Y. Chen, and B.-B. Yan, “Biodiesel production in a magnetically-stabilized, fluidized bed reactor with an immobilized lipase in magnetic chitosan microspheres,” Biotechnology Letters, vol. 36, no. 1, pp. 63–68, 2014.
View at: Publisher Site | Google Scholar
P. Shao, X. Meng, J. He, and P. Sun, “Analysis of immobilized candida rugosa lipase-catalyzed preparation of biodiesel from rapeseed soapstock,” Food and Bioproducts Processing, vol. 86, no. 4, pp. 283–289, 2008.
View at: Publisher Site | Google Scholar
G. Chen, J. Liu, Y. Qi, J. Yao, and B. Yan, “Biodiesel production using magnetic whole-cell biocatalysts by immobilization of pseudomonas mendocina on Fe₃O₄-chitosan microspheres,” Biochemical Engineering Journal, vol. 113, pp. 86–92, 2016.
View at: Publisher Site | Google Scholar
D. C. Cubides-Roman, V. H. Pérez, H. F. de Castro et al., “Ethyl esters(biodiesel) production by pseudomonas fluorescens lipase immobilized on chitosan with magnetic properties in a bioreactor assisted byelectromagnetic field,” Fuel, vol. 196, pp. 481–487, 2017.
View at: Publisher Site | Google Scholar
K. A. Batista, F. M. Lopes, F. Yamashita, and K. F. Fernandes, “Lipase entrapment in PVA/chitosan biodegradable film for reactor coatings,” Materials Science and Engineering: C, vol. 33, no. 3, pp. 1696–1701, 2013.
View at: Publisher Site | Google Scholar
M. Karimi, “Immobilization of lipase onto mesoporous magnetic nanoparticles for enzymatic synthesis of biodiesel,” Biocatalysis and Agricultural Biotechnology, vol. 8, pp. 182–188, 2016.
View at: Publisher Site | Google Scholar
S. E. Helal, H. M. Abdelhady, K. A. Abou-Taleb, M. G. Hassan, and M. M. Amer, “Lipase from rhizopus oryzae R1: in-depth characterization, immobilization, and evaluation in biodiesel production,” Journal of Genetic Engineering and Biotechnology, vol. 19, no. 1, pp. 1–13, 2021.
View at: Publisher Site | Google Scholar

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Copyright © 2021 Anping Wang et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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