PhD Student,
Urgench State University after named Abu Rayhan Beruni,
Uzbekistan, Urgench
E-mail: nazokat.matrasulova@urdu.uz
BLEACHING OF COTTONSEED OIL USING A FIBROUS SORBENT DERIVED FROM SILK FIBER WASTE
УДК: 547.962.94
Abstract
Various sorbents, mainly soil-based sorbents, are used in the purification of vegetable oils. We obtained a multifunctional sorbent from silk fiber waste by various methods of purification of vegetable oils. Silk factories produce a large amount of fibrous waste from natural silk at different stages. A fibroin-based sorbent from silk waste was obtained by alkaline hydrolysis and activation under the influence of ultrahigh-frequency rays, and the sorbent was used to purify cottonseed oil. As a result of purifying cottonseed oil using sorbent samples from silk fiber waste, we were able to reduce the peroxide value from 10.58 mmol/L to 5.81 mmol/L. Reducing the peroxide value of vegetable oils increases the shelf life of vegetable oils. The sorbent does not affect the oil composition, even if it is in an oil environment for a long time. In addition, the obtained fibrous sorbent sample reduces the acid number of the oil to 0.15 mmol/L KOH. The sorbent derived from silk fiber waste that we recommend is also important because it reduces waste from silk factories and is easy to separate from oil.
Аннотация
Для очистки растительных масел используются различные сорбенты, в основном почвенные. Мы получили многофункциональный сорбент из отходов шелкового волокна различными методами очистки растительных масел. Шелковые фабрики производят большое количество волокнистых отходов натурального шелка на разных этапах. Сорбент на основе фиброина из отходов шелка был получен путем щелочного гидролиза и активации под воздействием ультравысокочастотных лучей, и этот сорбент был использован для очистки хлопкового масла. В результате очистки хлопкового масла с использованием образцов сорбента из отходов шелкового волокна нам удалось снизить перекисное число с 10,58 ммоль/л до 5,81 ммоль/л. Снижение перекисного числа растительных масел увеличивает срок их хранения. Сорбент не влияет на состав масла, даже если он находится в масляной среде в течение длительного времени. Кроме того, полученный образец волокнистого сорбента снижает кислотное число масла до 0,15 ммоль/л KOH. Рекомендуемый нами сорбент, полученный из отходов шелкового волокна, также важен, поскольку он уменьшает количество отходов шелковых фабрик и легко отделяется от масла.
Ключевые слова: фиброин шелка, ультравысокочастотное излучение, хлопковое масло, перекисное число, кислотное число.
Keywords: Silk fibroin, ultra high frequency radiation, cottonseed oil, peroxide value, acid number.
Introduction
One of the most important sectors of the food industry is the vegetable oil sector. A large part of the food produced worldwide comes from the vegetable oil sector. Cottonseed, linseed, sunflower, soybean oil , etc., are the main products of the industry. The production of competitive, high-quality, and environmentally responsible products is the main goal of the vegetable oil industry. Vegetable oils are currently purified using various adsorbents, mainly silicates and clays[1,2]. They consume a lot of money and energy to purify vegetable oils. Bentonites are activated with acids at high temperatures (250–300ºC) to purify vegetable oils. However, if the oil remains with the adsorbent for a longer period of time, it oxidizes and releases a vegetable odor, which changes the structure of the oil . Sorbents used in the cottonseed oil refining process mainly need to bind impurities such as phospholipids, free fatty acids, pigments, various oxidation products, and gossypol. In modern refining processes, the capacity of sorbents is not only determined by adsorption capacity, but also by selectivity, regeneration, and food safety requirements [2,3]. Solving this problem is one of the most urgent problems. To solve this problem, we used sorbents obtained from silk fiber waste.
It is very important to study the mechanical, physical and chemical properties and applications of natural silk fibroin. Currently, various preparations based on natural silk fibroin have been created and are used in many areas [4–8]. Based on the research, the sorption processes of heavy metals in silk fibroin, the adsorption conditions, and the mechanism of various dyes were studied[9,10], and the high sorption capacity of silk fibroin was once again demonstrated. The sorbent properties of natural silk fibroin have been studied. Hydrolyzed fibroin ("HF") from waste natural silk fibers can be used to refine vegetable oils, prepare food products, and study medicines.
Up to ten to twenty-eight percent of silk fibers extracted from the cocoon become waste. Depending on the production capacity of the business, one silk spinning factory in Uzbekistan produces an average of 60 tons of silk waste annually. The separation of waste fibers from additives and silk fibers requires a large amount of energy. Finding ways to reuse this fiber waste is one of the most pressing problems. Silk fiber waste is considered unsuitable for the textile industry due to its mechanical and qualitative properties.
Nevertheless, silk waste and silk fibers have the same physicochemical properties and the same chemical composition. This allows the production of hydrolyzed fibroin from waste silk fibers with strong sorption properties and solves some problems in its practical application [11]. The amount of fibroin and sericin proteins in silk depends on the nutrition and living conditions of the silkworms. Our research has shown that silkworm cocoons grown in the Khorezm region of Uzbekistan contain 67.5% fibroin, 32.5% sericin, and other chemicals. During the production process, 28% is converted into fiber residues. It is very important to study the sorbent properties of fibrous waste
Materials and methods
Required materials and equipment. Fibrous waste of silk (Cleaned of additives. Urganch Bahmal, LLC, Urgench, Uzbekistan), Sodium carbonate (purity 99,9%), KOH (purity 99,9%) was purchased from Chimreaktivinvest (Uzbekistan), unrefined oil obtained from cotton Seeds. Bidistilled water is obtained from the “GFL 2104 Double distillation water still” device (Germany). Optical microscope ("Optika_B-150 DBR"), Lovibond® Tintometer Model F. Ultra-high frequency radiation was performed on a ME81ARW (Samsung) device at a frequency of 2450 MHz. ATR-IR Fourier spectroscopy analyses were performed on a “FTIR 4600 JASCO” (Japan) spectrophotometer.
Obtaining fibroin fiber from fibrous wastes of natural silk . Studies have focused on the use of silkworm waste as a sorbent in the purification of vegetable oils. The fibrous waste of silk was found to contain up to 88% fibroin, up to 12% sericin, and other substances. Conditions were selected for the obtaining of fibroin from the fibrous waste of silk: sericin was dissolved in a NaHCO3 solution at 90ºC for 40 minutes [12]. Fibroin fibers were obtained from the solution and washed with distilled water.
Obtaining “HF” from silk fibroin. Further studies were conducted on the hydrolysis of fibroin fibers from silk fibers and their sorbent properties. Silk fiber fibroin was hydrolyzed under alkaline conditions and with ultrahigh-frequency radiation (510 W) to obtain “HF” in the form of fibers[13]. The extraction of “HF” in an alkaline medium was carried out by immersion in a 3% KOH solution. In this case, it took 60 minutes to obtain “HF” in a 3% KOH solution. The formation of cracks and pores on the surface of “HF” fibers was studied. The fact that “HF” has ampholytic properties and the presence of polyfunctional groups allow it to be used in various environmental conditions. To further increase the cracks and porosity in “HF” particles, “HF” powder was exposed to ultrahigh-frequency radiation for 5 minutes after immersion in an alkaline medium and in a wet state. After the procedure, the sample was neutralized and washed with hot distilled water until the salt remained. As the cracks and pores in the "HF" increase, its sorption properties also increase.
Purification of cottonseed oil with “HF” . Cottonseed oil was purified to test the sorption properties of the obtained "HF" samples.100 g of purified vegetable oil was poured into numbered flasks and immersed in a water bath. When the temperature reached 70ºC, 1.0 g of hydrolyzed fibroin ("HF") sample was added to the flask and mixed at a speed of 250 rpm. Continue mixing for 30 minutes, bringing the oil temperature to 90ºC. At the end of the process, the oil was filtered. The color level of the filtered oil was measured on a Lovibond device. The peroxide value and acid content were measured by the method of [14].
Result and discussion
The surface and sizes of GF samples obtained from silk fiber waste were studied using optical microscopy. Optical images of the samples were obtained using a digital - “Optika_B-150 DBR” -USB optical microscope [15]. The length values of HF 52 particles were determined using an optical microscope, and the average fiber length was calculated based on this. Among the particles, the smallest particle was 20 μm and the largest particle was 193 μm. The average fiber length is 100 μm (Table 1).
Table 1. Length of KOH-treated HF fibers
|
HF particle sizes, μm |
||
|
smallest particle |
largest particle |
average particle size
|
|
20 |
193 |
100 |
/Matrasulova.files/image002.jpg)
1-A. Image of HF particles 1-B. Image of cracks formed on
treated with KOH (100x) the surface of the hydrolized fiber
under the influence of UHF rays
Figure 1. Image of hydrolized fibroin particles
The reduction in fiber size of silk fibroin, its conversion to the “HF” state through alkaline gyrolysis, leads to an increase in the number of active polyfunctional micro- and nano-sized pores on the surface of the “HF” particles.The effect of high-frequency radiation further increases the efficiency of this process. Due to the presence of active polyfunctional porosity, “HF” can be used as a polyampholyte sorbent in the differeneces processes.
FTIR spectra analysis of silk fibroin and alkaline hydrolyzed fibroin.ATR-IR Fourier spectroscopy analyses were performed on a “FTIR 4600 JASCO” spectrophotometer and studied in the range of 4000-400 cm-1 [16]. In this, samples of silk fibroin waste fiber washed with sericin and fiber hydrolyzed in alkaline medium were analyzed.
/Matrasulova.files/image003.png)
Figure 2. FTIR spectra of silk fibroin and alkaline hydrolyzed fibroin
The FTIR spectra of silk fibroin (IF) fiber and silk fibroin (SF-KOH-UHF irradiation) samples were studied, which were immersed in a 3% KOH solution and then treated with ultrahigh-frequency radiation, to determine the changes in their chemical structure.A broad absorption band was observed in the region of 3281–3285 cm-1 in both samples. These bands correspond to the N-H stretching vibrations of the peptide bonds in the fibroin molecule and the O-H vibrations of the hydroxyl groups. After treatment with ultrahigh-frequency radiation of IF immersed in a KOH solution, the change in intensity in this band indicates the reorganization of the hydrogen bonding system.The strong absorption band located around 1624 cm-1 corresponds to the Amide I region of fibroin and is mainly associated with the stretching vibrations of the carbonyl group (C=O) in the peptide bond. The absence of a significant shift in this range indicates that the main polypeptide chain of fibroin is preserved. However, changes in the shape and intensity of the peak may indicate a change in the ratio of β-sheet and amorphous phases.
The absorption band observed in the range of 1514–1519 cm⁻¹ belongs to the Amide II region, which is formed as a result of N–H deformation and C–N stretching vibrations. A slight decrease in the intensity of this peak in the KOH-treated sample indicates a partial disruption of hydrogen bonds around the peptide bonds.The absorption observed at 1443–1445 cm-1 corresponds to the deformation vibrations of the -CH2- groups. The preservation of this peak indicates that the main chain skeleton of the fibroin molecule is not damaged even after treatment with ultrahigh-frequency rays.The absorption band in the range of 1229–1231 cm-1 corresponds to the Amide III band and is associated with C–N stretching and N–H deformation vibrations. In the literature, this band is considered an important parameter in assessing the secondary structure of fibroin, especially the β-sheet structure. Changes in this band after treatment with KOH and ultrahigh-frequency radiation indicate a partial reorientation of the fibroin macromolecules.
The low-frequency absorption bands in the range of 550–630 cm⁻¹ can be attributed to deformation vibrations of the amide groups and skeletal vibrations of the molecule. In addition, the absorption observed at about 2930 cm⁻¹ in the original silk fibroin sample corresponds to stretching vibrations of the -CH- and -CH2- groups.
The decrease of this peak in the sample treated with ultrahigh frequency radiation in SF immersed in KOH solution indicates that some degree of change in molecular conformation has occurred as a result of the alkaline environment and the effects of ultrahigh frequency radiation.
Results of using HF sorbent in oil bleaching. Hydrolyzed fibroin ("HF" - obtained under alkaline conditions under very high frequency rays) sample are used in the purification of cottonseed oil. As a result of the cleaning process, the red color unit of the fat was reduced from 19 to 10. The acid number decreased from 0.43 mmol/L to 0.21 mmol/L. There was also a significant decrease in the peroxide number, which decreased from 10.55 mmol/L to 5.22 mmol/L. The table below shows the cottonseed oil purification performance of the sample.
Table 2. Parameters of cottonseed oil
|
Parameters |
Unrefined oil Indicators |
Oil refined with sample HF |
|
Color level |
Yellow unit:35 Red: 19 |
Yellow unit:35 Red: 10 |
|
The amount of Acid (mmol/kg) |
0.41 |
0.23 |
|
Peroxide value (mmol/kg) |
10,55 |
5.22 |
FTIR spectra analysis of oil samples
FTIR analysis of unbleached crude cottonseed oil and cottonseed oil bleached with HF sorbent ATR-IR Fourier spectroscopy analyses were performed on a “FTIR 4600 JASCO” spectrophotometer and studied in the range of 4000-400 cm-1 [16].
The results of the FTIR spectra show that the basic composition of the two oil samples is almost unchanged, with the crude and bleached cottonseed oil samples retaining the aliphatic C–H vibrations in the range of 2925–2854 cm⁻¹, the ether carbonyl (C=O) at 1747 cm⁻¹, and the C–O vibrations at 1165 cm⁻¹(Picture 3,4). This indicates that the basic triglyceride structure of the oil is preserved during the bleaching process, only the amount of additives in the oil is reduced.
Figure 3. FTIR spectra of bleached cottonseed oil
/Matrasulova.files/image005.jpg)
Figure 4. FTIR spectra of bleached cottonseed oil
Conclusion
During the hydrolysis of silk fiber waste in an alkaline environment and activation under the influence of ultra-high frequency rays, the formation of cracks and pores on the surface of “HF” fibers was studied, the average particle size is 100 μm. As the cracks and pores in “HF” increase, its sorption properties also increase. The resulting sorbent (HF) is suitable for oil purification due to its properties and does not react chemically with oil even when mixed with oil for a long time. It was found that it reduces the peroxide value of cottonseed oil to 5.81 mmol/L, the acid value to 0.15 mmol/L KOH, without changing the taste of the oil. In particular, reducing the peroxide value in the oil with the “HF” sorbent extends the shelf life of cottonseed oil.
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