Abstract

General Background: The increasing demand for sustainable energy sources has driven interest in replacing fossil fuels with biofuels. Specific Background: Second-generation bio-refining technologies utilizing lignocellulosic biomass offer a promising path toward environmentally and economically viable biofuel production. Knowledge Gap: However, efficient catalytic systems for cellulose hydrolysis under mild conditions remain limited. Aims: This study aims to synthesize and evaluate a heterogeneous catalyst, Silica-Amino methanesulfonic acid, for effective cellulose hydrolysis into glucose. Results: The catalyst, synthesized via one-pot and reflux methods, achieved up to 88% hydrolysis yield at 130 °C within 6 hours. The one-pot method yielded a 4.2 g catalyst with slightly superior activity. Optimal conditions were determined as 0.1 g catalyst mass and 130 °C. Solvent screening revealed that DMF/LiCl and Cyclohexanol/LiCl mixtures were most effective. Novelty: The direct (one-pot) synthesis method produced a catalyst with comparable or superior performance to traditional reflux methods, highlighting a more efficient and scalable approach. Implications: These findings demonstrate the potential of Silica-Amino methanesulfonic acid as a robust and reusable catalyst for bio-refining processes, contributing to the advancement of green chemistry and sustainable fuel alternatives.

Highlights:

1. Catalyst achieved 88% glucose yield from cellulose.

2. One-pot synthesis more efficient than reflux.

3. DMF/LiCl best solvent for hydrolysis process.

Keywords: Biofuels, Cellulose Hydrolysis, Heterogeneous Catalyst, Silica-Amino Methanesulfonic Acid, Lignocellulosic Biomass

Introduction

Nowadays, the entire globe suffers of two kinds of troubles, i.e., depletion of new sources and the generation of surplus waste. From economic point of view, energy requirements, as well as the environments of developing and developed countries, the best method of resolving these troubles is to incorporate these wastes in the primary current of manufacturing. As result of this recognition, every manufacturing region is attempting to increase its revenue through utilization waste as source in its products [1]. Waste recycling can be defined as a process that converts waste materials into new uses materials, which lead at last reduced accumulation of raw materials [2]. Currently farming residues are used as renewable sources important industrial applications and produce of light wall panels. For the reason it can contribute to environmental protection, and also wallboard manufacture for development of new products in light industry. Construction materials that are environmentally friendly and generate revenue for farmers in village communities which are grow economic plants by utilize substance from rice straw and corn husk as main component [3]. Rice husk (RH) was burning in the air as natural waste product and this could give ash (RHA). Annually about 701 million tons of RH residuals were generated throughout the world, production of 140 million tons of RHA from calcination all RH [4]. The reduced elimination of RH through burial in the land is a bad technique which raises environmental contamination. Currently, RH is reused only for limited implementations. RH is a bio-support substance, that has been investigated as a potential source of a sustainable and renewable energy [5]. Nevertheless, carbon and ash are the primary elements of charcoal. These two residues may be defined as RH carbon (RHC) and RHA that need handling to avoid the formation of the pollutants. The fabrication of nanoparticles based on bio char was previously reported for use in 1 Chapter one Introduction water purification [6]. Furthermore, highly porous activated carbon (AC) can be produced by stimulating RHC in the lack of oxygen atmosphere, which is the more frequent component applied in filtration and purification [7]. RHC-based AC is very useful in supporting the catalyst [8], super capacitors [9], and CO2 capture [10]. Several wastes such as fly ash have been discovered as powerful components utilized in the production of ceramics [11]. In general, many benefits were obtained from waste recycling such as reduce level of consumption of raw materials, decrease energy usage, lowering air and water pollution caused by gas emissions such as (NO2, CO2 and NO) which could occur as result of reducing the need for conventional unwanted materials [12]. Numerous studies identified tolerable solutions to improve the waste in advanced countries, including compost or biogas generation in addition organic waste buyback programs [13], Carrying out convert residue waste to energy methods and technologies [14] , conversion solid waste to potential in parallel with recycling of glass, metals, and other inert [ 15] process templates making, generation of power from biomass waste through the [16]. Among the various alternatives established until now for Petro-fuel, bio-fuels have the potential efficiency to solve the difficulties related to energy safety, ecological deterioration, foreign exchange deficit, socioeconomic growth, and rustic retardation [17]. Generation and consuming of recyclable fuels have growingly increased attractiveness in the 21st. century. Bio-fuel usually include a variety of solid, gases, and liquid fuels such as alcohols (ethanol, methanol, butanol), biodiesel, Fischer Tropic gasoline/diesel, bio-oil, bio-crude, hydrogen, methane, and bio char derivatives of bio-originated feed stocks [18]. The primary methods to generate energy from biomass are calcination, gasification, pyrolysis, liquefaction, hydro gasification, alcoholic fermentation anaerobic digestion and trans esterification. Each method has its special features, which vary according to biomass origin in addition to type of energy required [19]. Burning is the main technique is applied to generate heat and energy from biomass. It is method that has wide range of industrial and ecological interests due to, it is a low cost, environmentally friendly and renewable source of energy [20]. Through the last some ten years, biofuel construction by the conversion of organic matter of lignin and cellulose have gained rising noticed because of its minimal working condition [21]. Despite that, because the structure strong of lignocellulose biomass, preprocessing is required to cleavage cross-linkage of lignocellulose biomass in order to improve the availability and biodegradation of cellulose micro strand and hemicellulose arrays [22]. Lignocellulose biomass, which includes forestry residues, farming residue, courtyard waste, timber products, animal and human wastes are a renewable source which storage energy from sunlight in its chemical bonds. Biomass content from of cellulose, hemicellulose and lignin varies greatly, according to the kind of biomass. The cellulose composite in some sources may extent of 40%-60%, the hemicellulose composition is 15%-30%, and the lignin amount is around10-25%. Further to the three main ingredients, little part of extrication and inorganic ash too found at biomass as amorphous elements which not form the cell wall or cell layers. Agricultural and grasses biomass consist higher extractives and ash, whereas wood biomass consists significantly more quantities from the three major constituents (>90% [23]. Techno-economic analysis revealed that pyrolysis pathways for producing transportation fuel from biomass include economic benefits more than different conversion pathways, like gasification and biochemical routes [24],[25]. Biomass pyrolysis technique will bring rising interests from both academic research and industrialization, Because the great requirements toward liquid transport fuels [26]. Rice husk (RH) and sugarcane are the primary sources of biomass. The RH and rice straw have enormous potential for generating bioenergy, an alternative renewable source of power [27].

Methods

2.1 Raw materials

Sigma-Aldrich provided us with 98% pure amino methanesulfonic acid, 99% pure lithium chloric acid, and 99% pure toluene. System provided us with 99% pure sodium hydroxide and 99.5% pure dimethylformamide DMF. BDH delivered 99% pure Dinitrosalycilic acid (DNS). Riedle-De Haen provided 99% pure cyclohexanol, while Fluka supplied 98% pure butanol. No purifying process was carried out on any of the aforementioned chemicals.

2.3 Preparation of in one pot synthesis

The sodium silicate was combined with 2.0 gram and 6.0 mL of CPTES. As the pH changed and the reaction was being monitored to the finish, a titration of the combination agents (3.0 M) HNO3 acid was carried out. At pH 9, the white gel had started to take shape. After stopping the titration at pH 3, the gel was set aside and covered to be kept at room temperature until the next day. The material was washed with distilled water and centrifuged seven times at 4000 rpm for fifteen minutes to achieve the separation. The previous wash was done using acetone. Following that, the product was dried for 48 hours at 110°C. There were 4.2 grams of catalyst in total.

2.4 Preparation of reflux method

The was made by dissolving 2.0 g of RHACCl in 25 mL of dry toluene and adding 1.5 g of to the solution. For 24 hours, the reaction mixture was refluxed at 120 °C. After that, distilled water was used to filter and rinse the solid phase. For twenty-four hours, the solid sample (1.4 gram) was dried at 110°C.

Result and Discussion

3.0 FT-IR spectral analysis

The broad band seen about 3400 cm-1 is usually ascribed to SiO-H O-H and 3400 of NH vibrations. Silica- Amino methanesulfonic acid detects the aromatic C-H stretching vibration at 3090 cm-1. These bands were not visible in RHA stretching modes. The CH2 group's bending modes, which included both symmetric and asymmetric vibrations, emerged at 1460 cm-1. The shoulder at 1640 cm-1 was the result of the H2O groupings.

Figure 1.The FT-IR spectra of Silica- Amino methanesulfonic acid.

3.1 Electron Microscopy (TEM and SEM)

Figure2- A shows silica-amino methanesulfonic acid. The TEM micrograph was given shape B from silica-amino methanesulfonic acid, which has big molecules grouped in different ways. The rough porous surface was observed with large particles.

3.3 X-ray Diffraction (XRD)

The X-ray powder diffraction pattern for Silica- Amino methanesulfonic acid.is displayed in Fig3. Since only a broad pattern was seen at a 2 θ angle of about 23.5o, it seems that the samples are amorphous.

Figure 2.The XRD of Silica- Amino methanesulfonic acid.

Figure 3.The TEM and SEM micrographs of the Silica- Amino methanesulfonic acid

4.0 Hydrolysis procedure

4.1 Cellulose hydrolysis

With a 100 mL circular bottom flask fitted with a water condenser and a magnetic stirrer, cellulose hydrolysis was carried out in a liquid phase using Silica-Amino methanesulfonic acid as a homogeneous catalyst. A round-bottom flask containing 0.1 gm of Silica-Amino methanesulfonic acid was filled with 25 mL of DMF, 0.18 gm of cellulose, and 0.5 gm of LiCl, each separately. A temperature of 130˚C and a reflux period of 10 hours were used to perform the hydrolyses. In a vial, 0.5 mL of the clear hydrolyze solution was added to 2.0 mL of deionized water. After adding 2.0 mL of DNS reagent and 2.0 mL of 2.0 N sodium hydroxide, the solution was heated to 90 oC for five minutes in a water bath. To determine whether glucose was present, UV-visible spectroscopy was adjusted to 540 nm.

4.2 Time protocol

The effect of hydrolysis time on silica-amino methanesulfonic acid is shown in Figure 4. The hydrolysis was performed by dissolving 0.1 gm of heterogeneity in a DMF solution at 130 °C. The hydrolysis of cellulose began after the reaction and was completed to an 88% degree after 6 hours. However, it was found that the percentage of glucose during the in-situ hydrolysis to other products decreased when the hydrolysis time was prolonged beyond 6 hours. As a result, the ideal hydrolysis time for converting cellulose to glucose was 7-hours.

Figure 4.Cellulose hydrolysis over Silica- Amino methanesulfonic acid as a function of time. The hydrolysis condition was 0.1 gm mass of catalyst, at 130 °C.

4.3 Mass effect

The hydrolysis of cellulose was carried out by varying the content of Silica-amino methanesulfonic acid (from 0.05 to 0.15 gm) while maintaining the same hydrolysis period of 10 hours and temperature of 130 °C (Figure 5). As the catalyst mass increased from 0.05 to 0.15 gm, the cellulose hydrolysis showed a noticeable improvement from 30% to 88%. The rate of glucose hydrolysis was fast for both the 0.05 and 0.15 gm catalyst masses. Despite producing good hydrolysis and degradation results, the 0.05 gm catalyst mass's hydrolysis process was noticeably slower than that of the other two masses. A catalyst mass of 0.1 gm produced the best hydrolysis and degradation results.

Figure 5.The hydrolysis of cellulose over Silica- Amino methanesulfonic acid as function to catalyst mass

4.4 Hydrolysis temperature

The results of using different temperatures during the hydrolysis of cellulose are shown in Figure 6. According to the cellulose hydrolysis profile, the glucose yield was 70% at 120 °C after six hours, and it significantly increased to 88% at 130 °C in the same time frame. By contrast. 130 °C was later determined to be the ideal temperature for hydrolysis based on experimental observations.

Figure 6.Cellulose hydrolysis over Silica- Amino methanesulfonic acid at different temperatures.

4.5 Solvents effect

Different solvents were used to measure the breakdown of glucose and cellulose. As seen in Figure 7, these solvents included 1-butanol, cyclohexanol, and DMF. It was found that each solvent's hydrolysis had advanced in the following order .

DMF > Cyclohexanol >1-Butanol.

A key component of the hydrolysis process was the solvent's ability to dissolve cellulose. LiCl-containing DMF showed the best cellulose-dissolving capabilities. When compared to other solvents, cyclohexanol and 1-butanol also showed excellent performance. All solvents could form hydrogen bonds with the initial substance.

Figure 7.Cellulose hydrolysis over Silica- Amino methanesulfonic acid at different solvents.

Figure 8.Hydrolysis of cellulose to glucose to other compounds over Silica- Amino methanesulfonic acid Ref and Direct.

Figure 9.Silica- Amino methanesulfonic acid Catalyst synthesis reflux and direct method.

Conclusion

Silica-Amino methanesulfonic acid effectively hydrolyzed cellulose to glucose, at a temperature of 130°C for 6 hours. The hydrolysis activity of the catalyst reached an impressive 88% of cellulose hydrolysis The activity of Direct was seeming to be close to the activity of Reflux, with glucose emerging as the major product. Optimal mass and temperature for the process were determined to be 0.1 gm and 130°C, respectively. The best solvents for achieving high yields of hydrolysis were found to be Cyclohexanol with LiCl and DMF with LiCl. Furthermore, glucose degradation over the catalyst occurred within 7 hours.

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