A METHOD FOR PRODUCING BIOACTIVE PHOSPHATE GLASS FROM WASTE TOMATO STEM ASH THROUGH PHOSPHORIC ACID ACTIVATION.

Abstract

The invention involves the production of bioactive phosphate through the utilization of organic waste of agricultural origin. The invention relates to a manufacturing method that enables the production of glass. More specifically, the invention; phosphoric acid from ash obtained from lignocellulosic agricultural waste such as tomato stems production of phosphate-based amorphous glass by chemical activation It involves a process that makes this possible. In this method, agricultural waste ash It is purified from organic components by undergoing a pre-calcination process and It is then ground to a homogeneous particle size. The resulting ash, by reacting it with a phosphoric acid solution of a specific concentration, the ash calcium and / or magnesium oxide components present within it in situ This reaction results in the formation of phosphate compounds. A phosphate precursor is formed, and the gel phase is dried and pre-heated. The preliminary organization of the glass mesh structure is carried out through this process. The resulting intermediate product is then melted at relatively low temperatures and rapidly Amorphous phosphate glass is obtained through a cooling method. The developed method... thanks to the high purity used in traditional bioactive glass production processes The need for chemical raw materials is reduced, and the melting required for glass production is minimized. The temperature is lowered and energy consumption is significantly reduced. Furthermore... The invention enables the conversion of agricultural waste into value-added biomaterials. This is important in terms of sustainable material production and waste recycling. It offers advantages. The resulting phosphate-based bioactive glasses are used in bone tissue. engineering, dental biomaterials, biodegradable implant coatings, and the environment. It can be used in various fields, such as engineering applications.

Description

1  TARIFF Phosphoric acid activation from waste tomato stem ash. BIOACTIVE PHOSPHATE GLASS PRODUCTION METHOD  TECHNICAL FIELD The invention relates to biomaterials, glass technologies, sustainable material production, and waste. It relates to the technical fields of recycling, especially organic waste of agricultural origin. 10 in the production of bioactive phosphate glass through chemical activation of ashes It relates to a production method aimed at evaluation. The invention involves the phosphoric acid content of ash obtained from the incineration of agricultural biomass waste. chemical activation with acid, calcium and / or found in the ash Converting magnesium oxides into a phosphate network structure and thus achieving a low 1% efficiency. A production process that enables the production of amorphous bioactive phosphate glass at high temperatures. It relates to the process. The invention also applies to biomedical implant materials and bone tissue engineering. applications, dental biomaterials, biodegradable glass coatings and environmentally friendly  bioactive materials that can be used in sustainable material production technologies It is a method that involves the production of glass. PREVIOUS TECHNIQUE 3 Bioactive glasses are used particularly in bone tissue engineering, implant coatings, and dental applications. advanced biomaterials widely used in fields such as biomaterials One of them is these glasses, which interact with biological environments, forming hydroxyapatite on their surfaces. because they have the ability to form similar layers to bone They are known as materials that can form biological bonds. Today, bioactive materials are  Glass production mostly uses silicate-based glass systems. is being carried out.   In current production techniques, bioactive glasses are generally made from silicon dioxide (SiO₂), calcium carbonate (CaCO₃), sodium carbonate (Na₂CO₃) and phosphorus pentoxide (P₂O₅) mixing high-purity chemical raw materials such as these in specific proportions and It is then obtained by melting it at high temperatures. This  In these methods, the melting temperatures required for glass formation are often 1300–1500. It is in the °C range, which requires high energy consumption. High The temperature requirement also increases production costs and production It also negatively affects the environmental impacts of these processes. 10 In some studies on the production of bioactive glass, the addition of elements to the glass composition... to provide plant-derived ash or biomass derivative materials It can be used. However, in the literature, these types of biomass ashes are mostly used as additives. It appears to be evaluated as a raw material or auxiliary mineral source. This In applications, biomass ash is generally used as an auxiliary component instead of the main raw material. It is used as such, and the basic components of glass are again pure chemicals. It is obtained from raw materials. Furthermore, in current techniques, glass production is mostly done by direct melting. Since this is accomplished, the formation of the glass network structure occurs entirely during the melting phase. This occurs because there is no pre-reaction step and the glass The formation of its structure requires a high temperature. This situation, This leads to low energy efficiency in the production process. Some studies in the literature have shown that different chemical reactions occur in phosphate-based glass production. He suggested using alternative methods or sol-gel-like techniques. However, this The raw materials used in most of these methods are again commercial chemical compounds. It is obtained by using agricultural waste as a direct main mineral source. The processes in which it is used are quite limited. Furthermore, agricultural waste ash cannot be used directly. Integrated  for the conversion of phosphate to glass network via phosphoric acid activation It appears that one of the production methods is not widely known in the literature.   Problems Encountered Current bioactive glass production techniques have various technical and economic disadvantages. These disadvantages include high energy consumption and raw materials. This creates significant problems in terms of costs and environmental sustainability. It extracts.  Firstly, high-purity chemicals used in traditional glass production methods. The procurement of raw materials constitutes a significant portion of production costs. The preparation and refining of these raw materials requires additional energy and resources. Because it requires it, the production process is burdensome both economically and environmentally. It can create. Another major problem is the high cost required for the production of bioactive glass. These are melting temperatures. Temperatures above 1300 °C increase both energy consumption. both increasing production costs and making production equipment more durable and expensive. This is especially true for large-scale production facilities. This significantly increases their costs. Furthermore, most of the raw materials used in current production processes are natural. These are pure minerals or chemical reagents obtained from sources. This situation,  the depletion of natural resources and the sustainability of production processes This leads to limitations. In contrast, agricultural waste... This assessment could both reduce the environmental waste burden and create new It has the potential to minimize the use of raw materials. 3 In current techniques, the use of biomass ash in glass production is also mostly practiced. It remains limited and these ashes are generally used as an auxiliary additive rather than the main mineral source. It is used as a material. Therefore, complete biomass-derived materials are used. In essence, it is sufficient to transform them into value-added advanced materials. It cannot be accomplished. 30   In addition, in traditional glass production methods, the glass mesh structure is only Since it occurs during the melting process, it is a pre-reaction that can lower the melting temperature. or pre-organizational mechanisms are generally absent. This situation This emerges as a limiting factor in energy efficiency in the production process.  Consequently, due to the aforementioned drawbacks and shortcomings, the relevant The need for an innovation in the technical field has arisen. 10   THE PURPOSE OF THE INVENTION The overall purpose of the invention is to create a complete system that meets the requirements mentioned above. especially those that eliminate disadvantages and bring additional advantages; biomaterials, glass technologies, sustainable material production and waste recycling its recovery relates to technical fields, particularly organic waste of agricultural origin. bioactive phosphate glass production through chemical activation of ash It relates to a production method aimed at evaluation. Due to the drawbacks of the previous technique, the invention, as described above, It aims to resolve the negative aspects. The main purpose of this invention is to add value to organic waste ash of agricultural origin. An innovative bioactive phosphate glass production process that enables its conversion into biomaterials. The aim is to develop a method. In this context, the invention involves agricultural waste as only an additive. not only as a material, but also as the main mineral source of glass structure. It aims to offer a production approach that enables its use. Another aim of the invention is to utilize pure chemicals in the production of bioactive glass. The aim is to reduce dependence on raw materials. Agricultural waste ash contains  Evaluation of naturally occurring calcium and magnesium oxides Thanks to this, a significant portion of the calcium sources required for glass production are available. The aim is to produce it from raw materials derived from waste. The invention also solves the problem of high energy consumption encountered in glass production processes. It aims to reduce [the effects of ash]. The method developed for this purpose uses ash. A gel-phase phosphate precursor is formed as a result of the chemical reaction between phosphoric acid and... the formation of the glass mesh structure, thus partially melting it beforehand. This approach ensures that glass formation is organized. required melting temperature is lower than in traditional methods  It becomes possible to realize it.   Another aim of the invention is to facilitate the production of phosphate-based glass structures and to create an in- A novel chemical reaction pathway based on the in situ phosphate formation mechanism. The aim is to improve it. Thanks to this method, the calcium and Magnesium oxide components are directly converted into a phosphate bond structure in glass. It contributes to the formation of the network. In addition, the invention is significant in terms of environmental sustainability and waste recycling. It aims to offer an important solution. This arises as a result of agricultural activities. By utilizing the resulting biomass waste, both environmental waste is reduced. both reducing the amount and transforming these wastes into high value-added biomaterials. The aim is to transform it. Finally, the invention has implications for bone tissue engineering, dental biomaterials, and biodegradable materials. Phosphates with bioactive properties that can be used in areas such as implant coatings. to ensure that glass can be produced in an economical and sustainable way 1 It aims to... To fulfill all the purposes stated above and those that can be derived from the detailed explanation. The invention aims to bring about the activation of phosphoric acid from waste tomato stem ash. It is related to the bioactive phosphate glass production method.    DESCRIPTION OF THE FIGURES Figure 1; SEM images of DSK-CaO, the subject of the invention. Figure 2; FTIR spectra of DSK-CaO, the subject of the invention. Figure 3; EDX spectra of DSK-CaO, the subject of the invention. Figure 4 shows the XRD patterns of DSK-CaO, the subject of this invention. 10   DETAILED DESCRIPTION OF THE INVENTION The overall purpose of the invention is to create a complete system that meets the requirements mentioned above. especially those that eliminate disadvantages and bring additional advantages; biomaterials, glass technologies, sustainable material production and waste recycling its recovery relates to technical fields, particularly organic waste of agricultural origin. bioactive phosphate glass production through chemical activation of ash It relates to a production method aimed at evaluation. Due to the drawbacks of the previous technique, the invention, as described above, It aims to resolve the negative aspects. Figure 1 shows SEM images of DSK-CaO, the subject of the invention. Figure 2 shows the FTIR spectra of DSK-CaO, the subject of the invention. Figure 3 shows the EDX spectra of DSK-CaO, which is the subject of this invention. Figure 4 shows the XRD patterns of DSK-CaO, which is the subject of this invention.  Process Steps A) Ash Preparation Pre-calcination at 500–700 °C <75 µm grinding 3 B) Chemical Activation 60–85% H₃PO₄ solution Solid / Liquid ratio: 1:1 – 1:3 70–90 °C 30 Mixing for 1-3 hours. At this stage:   CaO + H₃PO₄ → Ca-phosphate gel matrix C) Drying 110–150 °C 12–24 hours D) Pre-calcination 400–600 °C Phosphate network formation is initiated. 10 E) Low Temperature Melting 850–1050 °C 1 hour F) Rapid Cooling 1 Metal plate or water quench Surface morphology of tomato stem ash (TSK) is shown in SEM in Figure 1. The images were examined using half of a DSK-CaO molecule of approximately the same size. It has been observed that they consist of clusters of spheres. These clusters are homogeneous. It has dispersed. FTIR spectra of DSK-CaO samples were obtained using KBr pellets at ranges of 400–4000 cm-1. The range was determined as follows (Figure 2). The peak between 500 cm-1 and 370 cm-1 indicates the Ca-O bond. It demonstrates its existence. Regions below 600 cm−1 are attributed to SS stress.  Strong bands in the range of 1100–1000 cm−1 are characteristic peaks of polysaccharides. It originates from the C–O group. Ionic carboxyl groups (–COO−) Symmetrical stretching vibration produces a peak at 1409.71 cm−1. 3700–2600 cm−1 The gap can be attributed to the stretching vibration band of acidic OH groups in DSK-CaO. A peak showing CH stretching bonds was observed at 2987.20 cm-1.  10  The SEM-EDX results of DSK-CaO ash are shown in Figure 3. The EDX results indicate that... According to the EDX spectrum of DSK-CaO, C (8.88% w / w), O (45.27% w / w), Mg Peaks corresponding to (%1.63 w / w), Si (%1.21 w / w) and Ca (%43.02 w / w) This indicates its presence. EDX peaks support the XRF result.  The XRD peaks of the DSK-CaO material are detailed in Figure 4. XRD The sharp peaks in the model clearly show the CaO content in the (hkl) plane. 32.20 (1-1-1), 37.35 (0-0-2), 53.85 (0-2-2), 64.15 (1-1-3) and 67.37 (2-2-2) angular The peaks identified at these positions represent the sizes of the CaO particles. In addition to CaO, the DSK-CaO material contains a high concentration of 10. The compound apatite-(CaOH) (C1.5H1.97Ca9Na0.5O24.47P4.5) has been identified. The tomato stalks remaining after the fruit harvest were collected and cleaned. Two The elements in the material, both in their raw form and after the burning process. It was then determined by XRF analysis. The XRF results are given in Table 1. XRF 1 According to the results, there were significant differences in the ratios of silicon dioxide (SiO2) and Fe2O3 compounds. No change was observed. Magnesium oxide (MgO) after combustion. A significant increase in quantity has been observed. This increase is due to the sintering of MgO at 900°C. This indicates the formation of MgO in the material. This situation in the material... Magnesium hydroxide (Mg(OH)2) transforms into MgO with increasing temperature. This can be explained. According to the findings, the sulfur trioxide in the composition of raw tomato stems... The amount of (SO3) increased after being kept at high temperatures. This situation indicates that the raw material... high levels of sulfur-containing molecules (e.g., SO2) in the structure of the substance This may be due to its conversion to SO3 at higher temperatures. 3 Table 1. XRF results of DSK-CaO and DS. Material: Raw tomato stem (DS) DSK-CaO Element Component (%) Component (%) Na2O 0.11 0.60 MgO 1.55 7.65 P2O5 0.42 1.66 SiO2 0.35 0.39 11  SO3 0.85 2.66 Fe2O3 0.39 0.20 CaO 26.94 67.93 XRF analysis of raw tomato stems (DS) revealed 26.94% CaO. compounds were detected. After the tomato stem was burned in an oven at 900°C, DSK's The ratio to CaO compound increased significantly, reaching 67.93%. DSK production In this stage, the conversion of CaCO3 to CaO was achieved at 900°C and  This has been supported by characterization analyses. How the Invention Works This invention involves the chemical treatment of agricultural organic waste ash with phosphoric acid. It is a method for producing phosphate-based amorphous glass as a result of activation. The process, Unlike traditional silicate-based glass production, phosphate mesh is used at low temperatures. It is based on its formation. The production method consists of the following stages: 15  In the first stage, organic waste of agricultural origin (e.g., lignocellulosic biomass) (waste) is subjected to controlled burning or calcination to obtain ash. The resulting ash is subjected to pre-calcination at a temperature range of 450–750 °C. By retaining it, organic residues are removed and inorganic oxide phases are stabilized. is then processed. Afterwards, the ash is ground to a homogeneous particle size.   In the second stage, the ash is mixed with a phosphoric acid solution of a specific concentration (50–85%). It is mixed in a controlled manner. At this stage, the calcium found in the ash... oxide (CaO) and / or magnesium oxide (MgO) components react with acid It enters and forms in-situ calcium / magnesium phosphate intermediates.  The reaction is carried out at a controlled temperature (60–100 °C) and the mixture is in the gel phase. Phosphate is converted into a precursor. This gel formation is a precursor to the glass network structure. By organizing it, it allows for a lower melting temperature. 12   In the third stage, the resulting gel phase is dried at a temperature of 100–200 °C to release it. Water is removed. The dried material undergoes preheat treatment in the range of 350–650 °C. It is subjected to this process. During this process, partial polymerization occurs in the phosphate network structure. It happens.   In the final stage, the intermediate product is melted at a temperature range of 800–1100 °C. Gel pre- Thanks to its reaction, it can be used at lower temperatures compared to traditional glass production temperatures. A homogeneous molten phase is obtained at low temperatures. The resulting melt is metal. rapid casting onto a plate or by sudden immersion in a liquid medium. By cooling, amorphous phosphate glass is obtained. 10 The amorphous structure of the produced glass is confirmed by XRD analysis, and the presence of crystalline elements in the structure is also noted. No peak is observed. The resulting product is phosphate-based and may exhibit bioactive properties. It has a glass structure. 1) The basic working principle of this method is based on the natural properties found in agricultural waste ash. calcium and magnesium oxides without the use of an external calcium source It is based on the direct conversion of phosphate into a glass network structure. Gel phase formation. Thanks to this, melting time is reduced and energy consumption decreases.  Benefits of the Invention The invention describes a method for the utilization and reduction of agricultural waste. At these temperatures, bioactive phosphate glass production becomes possible, and the current production... Significant technical, economic and environmental benefits compared to other methods  It provides benefits which are explained in detail below. Primarily, the invention involves transforming agricultural waste into value-added advanced materials. Contributing to sustainable material production by enabling its transformation. It provides. Large quantities are produced as a result of agricultural activities. Biomass waste is often disposed of by incineration or by using low-value materials. It is used in various applications. Thanks to this invention, these wastes can only be processed in these applications. It is transformed from a byproduct that needs to be disposed of into a biomedical product. 13  In the production of high value-added bioactive glasses that can be used in applications. It can be used as a raw material. Thus, it contributes to waste management. and a production model in line with the circular economy approach is provided. It is being presented.  Another important benefit of the invention is the use of pure chemicals in glass production. The goal is to reduce the need for raw materials. Traditional bioactive glass production. In these processes, calcium and other metal oxide sources are generally commercial chemical products. It is obtained from compounds. Within the scope of the invention, agricultural waste ash is used. Naturally occurring calcium oxide and magnesium oxide components directly 10 It can be used in the formation of glass mesh structures. This means that additional elements can be added to the production process. By reducing the use of chemical raw materials, it provides both a cost advantage and... It also contributes to the more efficient use of natural resources. The invention also contributes to lowering the melting temperature required in glass production. It provides opportunities. In traditional silicate-based bioactive glass production methods Melting temperatures generally occur above 1300 °C. In the production method developed within the scope of the invention, phosphoric acid is used. Through chemical activation and gel-phase precursor formation, glass is produced. The network structure is partially organized before melting. This allows the glass to be  The temperature range required for melting is significantly reduced, and the production process This can be achieved at approximately 800–1100 °C. This situation provides energy. making production processes more economical and efficient by reducing consumption It provides. 3 Another technical advantage of the invention is its in-situ phosphate formation mechanism. The goal is to obtain a homogeneous glass network structure. This is achieved using phosphoric acid. calcium and magnesium oxides present in the ash during the chemical reaction. The components are directly converted into phosphate compounds. This conversion process affects the glass. By enabling the pre-formation of the network structure, a more homogeneous and stable phosphate glass  This contributes to the achievement of its structural integrity. This situation affects the structural integrity of the produced glass. 14  It enhances its integrity and exhibits more controlled dissolution properties in biological environments. It allows him to demonstrate this. The invention also offers significant advantages in terms of energy efficiency. High-temperature furnaces used in glass production have a very high energy consumption. It is high and constitutes a significant portion of production costs. Invention Production thanks to the low-temperature melting method developed within the scope of this project. The amount of energy consumed in this process can be significantly reduced. This situation both reducing production costs and decreasing the carbon footprint of production processes It contributes to its reduction. 10 Another important benefit of the invention is its potential for use in biomedical applications. The goal is to produce glasses with bioactive properties. Phosphate-based glass structures. thanks to its ability to interact with biological environments and its controlled dissolution properties It can be used in bone tissue engineering and implant coating technologies. 15 The glasses produced as part of this invention also interact with biological environments in a similar way. by entering the potential to support bone tissue regeneration This is especially true for bone grafts, biodegradable implant crowns, and This provides a significant advantage in terms of dental applications.  The invention also makes significant contributions to environmental sustainability. By utilizing agricultural waste, both the environmental impact associated with waste disposal is reduced. This reduces the burden and also saves natural resources needed for the production of new raw materials. consumption is restricted. In addition, it is carried out at low temperatures. Reduction in energy consumption thanks to the production process, environmental benefits of production processes  It helps to minimize their effects. Finally, the invention enables flexible production that can be applied in many different sectors. It presents a method. The developed method is limited to tomato stem ash only. not only, but also different agricultural biomass wastes with similar chemical compositions  This allows for evaluation. This situation makes the method widely applicable. 1)  to ensure that it has its own area and agricultural waste located in different geographies It allows for the economic utilization of resources. In these respects, the invention excels in both technical performance and economic and environmental aspects. Significantly better compared to existing bioactive glass production methods in terms of sustainability. It provides advantages. To fulfill all the purposes stated above and those that can be derived from the detailed explanation. The invention aims to bring about the activation of phosphoric acid from waste tomato stem ash. This relates to the bioactive phosphate glass production method. 10

Claims

  REQUESTS 1. The invention; amorphous bioactive compounds based on phosphate from agricultural organic waste ash. It is a glass production method, and its characteristic feature is;  — incineration or calcination of organic waste of agricultural origin The resulting ash is pre-treated in the temperature range of 500–700 °C. subjected to calcination, — The ash obtained after pre-calcination is ground to a size of less than 150 µm. reducing to a small particle size, 10 — phosphoric acid with a concentration of 60–85% in the ash in question Mixing with (H₃PO₄) solution in a solid / liquid ratio of 1:1–1:3, — The resulting mixture is kept at a temperature range of 70–90 °C for 1–3 hours. as a result of being subjected to a reaction for a period of time, calcium and / or Formation of a gel-phase precursor containing magnesium phosphate, 1 — drying the resulting gel phase at a temperature range of 110–150 °C, — preheating of the dried material in the temperature range of 400–600 °C being processed, — melting the resulting intermediate product at a temperature range of 850–1050 °C, — The resulting molten phase is rapidly cooled to obtain amorphous phosphate. It is characterized by including the process steps involved in obtaining glass. is being done.

2. The invention; phosphate-based amorphous bioactive from agricultural organic waste ash. It is an amorphous bioactive phosphate glass produced by the glass manufacturing method,  characteristic; by weight; — 40–60% P₂O₅, — 20–40% CaO, — Characterized by containing 1–20% MgO and / or alkali oxides  is being done.   3. Production method according to Claim 1, characterized by: — the agricultural organic waste in question includes tomato stalks, corn stalks, etc. such as stalks, rice husks, sunflower stalks or wheat straw by obtaining it from lignocellulosic biomass sources  It is characteristic.

4. It is a production method according to Claim 1, and its characteristic is; — 60–80% by weight of the ash used is calcium oxide (CaO) 10 It is characterized by its inclusion.

5. The production method according to Claim 1, its characteristic is; — magnesium oxide (MgO) at a rate of 1–15% by weight of the ash used. It is characterized by its inclusion.

6. It is a production method according to Claim 1, and its characteristic is; — during the reaction carried out with phosphoric acid,  in the ash In-situ transfer of CaO and / or MgO components to phosphate compounds. It is characterized by the formation of a gel-phase precursor as a result of its transformation.

7. It is a production method according to Claim 1, and its characteristic is; 3 — melting process in traditional silicate-based bioactive glass production their maximum temperature will be 1050 °C, which will be lower than their normal temperature. It is characterized by being carried out at a certain temperature.  14  8. It is a production method according to Claim 1, and its characteristic is; — rapid cooling process involves pouring the molten phase onto the metal surface or It is characterized by being performed by sudden immersion in a liquid medium.  9. It is a production method according to Claim 1, and its characteristic is; — external calcium carbonate, calcium oxide or during the production process The main calcium of the ash without the addition of silica raw material. It is characterized by its use as a source. 10 10. It is glass according to claim 2, and its properties are: — X-ray diffraction (XRD) analysis of the amorphous structure of glass reveals crystalline structure. It is characterized by the absence of peaks. 15 11. It is glass according to claim 2, and its properties are: — alkali and alkaline earth metals in the ash of the glass network structure  formed by oxides acting as network modifiers It is characteristic.

12. According to claim 2, it is glass and its properties are: — bone tissue engineering, dental biomaterials, biodegradable  implant coatings or heavy metal immobilization Configuring it for use in applications It is characteristic.

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