ADVANCED OSMOSIS MEMBRANE-SUPPORTED NEW GENERATION ELECTRO-OSMOTIC MEMBRANE BIOREACTOR

Abstract

The invention integrates wastewater treatment, water recovery, and nutrient recovery. electro-assisted advanced osmosis membrane bioreactor (MBR) that performs this function It is related to the system. The system in question is one where biological treatment is carried out. bioreactor, semi-permeable forward osmosis membrane module, electrical conduction on the membrane anode and cathode electrodes applying the field, withdrawal solution circuit, nutrient return MAP production reactor for recovery and reconcentration of withdrawal solution. It consists of a unit that enables the processing of wastewater. In this invention, wastewater is primarily processed... It is biologically treated in a bioreactor through microorganisms, then Water is drawn in by the effect of osmotic pressure difference thanks to the advanced osmosis membrane. It is transferred to the solution. The electric field applied to the membrane module Thanks to this, reverse salt flux is reduced and membrane fouling is controlled. and system performance is improved. Human urine or as a withdrawal solution. The necessary osmotic pressure is achieved by using urine-derived solutions. Moreover, it becomes possible to utilize a waste resource. The system Within this scope, nitrogen and phosphorus components found in wastewater are analyzed using MAP (magnesium phosphate) testing. It is recovered in the form of ammonium phosphate, and the resulting product is used as fertilizer. can be used or reused as a withdrawal solution within the system. can be evaluated. In addition, the diluted withdrawal solution can be reconcentrated. By doing this, the system can be operated in a closed loop. In this respect, the invention; reverse salt reducing flux, minimizing membrane fouling, and providing energy efficiency, reducing chemical use while simultaneously enabling water and nutrient recovery. It offers a sustainable and integrated treatment system.

Description

1 TARIFF ADVANCED OSMOSIS MEMBRANE-SUPPORTED NEW GENERATION ELECTRO-OSMOTIC MEMBRANE BIOREACTOR TECHNICAL FIELD The invention relates to wastewater treatment, membrane separation technologies, and advanced osmosis (FO) processes. Osmotic membrane bioreactor (OsMBR) systems, electrochemical processes, and It is located at the intersection of technical fields of food recovery technologies. 10 The invention relates to water treatment and simultaneous nitrogen extraction using electric field-assisted membrane systems. Sustainable and circular economy based on processes that enable phosphorus recovery. It is geared towards the development of integrated systems. PREVIOUS TECHNIQUE 15 Today, the most widely used systems in wastewater treatment are... Membrane bioreactor (MBR) technologies are emerging. These systems are used in biological treatment. by combining membrane filtration, high-quality effluent water is obtained. However, the high ventilation requirement in these systems necessitates increased transmembrane 20 The high pressure and energy consumption are significant disadvantages. In addition... the formation of fouling and dissolved microbial products on the membrane surface (SMP) and extracellular polymeric substances (EPS) accumulation in the system This reduces its performance and necessitates frequent chemical cleaning. In addition, these systems recover valuable nutrients such as nitrogen and phosphorus. It cannot be recovered and is mostly lost in the waste sludge phase. Advanced osmosis (FO) systems have become prominent in recent years due to their advantage of low energy consumption. This has come to the forefront. In these systems, water is transported by osmotic pressure difference, therefore high pressure. The need for pressure is eliminated. However, the most important 30 of FO systems... One of the problems is known as reverse salt flux. [Tensions / Reduction] The diffusion of ions present in the solution back into the bioreactor environment, in the system 2 This leads to increased conductivity and causes inhibition of microorganisms. In addition, commercial chemicals used as extraction solutions high cost and the need for reconcentration after the process, This makes the system economically disadvantageous. Osmotic membrane bioreactor (OsMBR) systems enable biological treatment with FO. Although developed as a combination, current systems use reverse salt flux and ion deposition. And membrane biofouling problems have still not been effectively solved. Long During prolonged operation, a drop in flux occurs, and system stability is compromised. Furthermore... Providing suitable, sustainable and low-cost tensile solutions is a major problem. 10 It continues as such. On the other hand, in the literature, magnesium ammonium phosphate (MAP, Nutrient recovery can be achieved through the production of struvite (a type of struvite). However, these processes... They are usually carried out in separate reactors and integrated with water treatment systems. 15 It is not used. The MAP produced is mostly used only as fertilizer. is being evaluated, and a holistic approach towards reuse within the process is being considered. no approach exists. When current techniques are evaluated in general; 20  Water recovery and nutrient recovery are not integrated,  The reverse salt flux cannot be effectively controlled,  Membrane fouling is a significant operational problem,  Electric field-assisted OsMBR systems have not been developed,  The costs of the extraction solution are high and unsustainable, 25  It appears that a closed-loop system approach is not available. This situation necessitates the development of new, more efficient, economical, and sustainable systems. This makes it necessary. Consequently, the aforementioned negative consequences and Due to these shortcomings, the need for an innovation in the relevant technical field has arisen. 30 3 THE PURPOSE OF THE INVENTION The overall purpose of the invention is to create a complete system that meets the requirements mentioned above. especially wastewater, which eliminates disadvantages and brings some additional advantages. water purification, membrane separation technologies, advanced osmosis (FO) processes, osmotic 5 Membrane bioreactor (OsMBR) systems, electrochemical processes and nutrient recovery It is related to acquisition technologies. Due to the drawbacks of the previous technique, the invention, as described above, It aims to resolve the negative aspects. 10 The primary purpose of this invention is to explore advanced osmosis, osmotic membrane bioreactors, and electric fields. application and nutrient recovery processes within a single integrated system. combining the production of high-quality water and valuable nutrients simultaneously from wastewater. The goal is to ensure its recovery. 15 Another aim of the invention is to address the reverse salt flux problem encountered in existing OsMBR systems. a controlled electric field to the membrane module to reduce the problem by minimizing ion back diffusion, thus bioreactor The aim is to prevent the negative impact on the activity of microorganisms within it. This 20 This increases system stability and treatment efficiency. The invention also aims to reduce membrane fouling. Electric field effect. By creating an electrostatic repulsive force on the membrane surface, pollutants are removed. The adhesion to the membrane is made more difficult, and in addition, 25 modified with nanomaterials. Thanks to its engineered membrane structure, resistance to fouling is increased. Another important objective is to eliminate the cost of the tensile solution used in the system. as a direct extraction solution of human urine for the purpose of removal This approach both utilizes waste as a resource and also generates 30 Dependence on commercial chemicals is eliminated. 4 Another aim of the invention is to convert nitrogen and phosphorus obtained from urine into magnesium. recovery in the form of ammonium phosphate (MAP) and the use of this product as both fertilizer and... by enabling its reuse as an osmotic puller, it creates a closed loop. It is about creating a system. In this way, resource efficiency is increased and circular A structure consistent with economic principles is obtained. 5 Furthermore, the invention is environmentally friendly, sustainable, and operates with low energy consumption. The aim is to develop a wastewater treatment system that can be implemented on an industrial scale. The system has a modular structure that can be integrated into existing treatment plants, and both It aims to achieve superiority both economically and technically. 10 In conclusion, this invention leads to water recovery, nutrient recovery, energy efficiency, and an innovative wastewater treatment technology that simultaneously meets sustainability criteria It aims to improve. To fulfill all the purposes stated above and those that can be derived from the detailed explanation. The invention aims to bring about a new generation of electro-osmotic systems supported by advanced osmosis membranes. It is related to membrane bioreactors. DESCRIPTION OF THE FIGURES Figure 1; The subject of the invention is the surface modification of a CTA membrane with nanosilica. Figure 2; 5 photographs taken at different magnifications of MAP obtained from urine, which is the subject of the invention. SEM images (A: 10 µm; B: 4 µm; C: 1 µm; D: 500 nm), Figure 3; EDX spectrum of the MAP obtained from urine, which is the subject of the invention. Figure 4; XRD peaks of the MAP, which is the subject of the invention, 10 Figure 5; The subject of the invention is the flux when the effect of the electric field is determined. time graph, Figure 6; Subject of the invention, (a) top surface (×50,000) and (b) cross 15 of the pure CTA membrane. Cross-sectional (×500) SEM image, Figure 7; EDX image of the pure CTA membrane, which is the subject of the invention. Figure 8; Contact angle of the pure CTA membrane, which is the subject of the invention, 20° Figure 9; SEM images of the nanosilicate, which is the subject of the invention (A: ×100,000 and B: ×200,000) Figure 10; EDX image of the nanosilicate, the subject of the invention, 25 Figure 11; XRD image of the nanosilicate, which is the subject of the invention. Figure 12; Subject of the invention, Epoxy-functionalized CTA membrane (a) 0.25% (b) Top surface of membrane containing nanosilica (×20,000), 30% containing nanosilica. Membrane top surface (×20,000), (c) Membrane top containing 1.0% nanosilica 6 surface (×20,000) and (d) top surface (×20,000) of membrane containing 2.5% nanosilica SEM images, Figure 13; Subject of the invention, Epoxy-functionalized CTA membrane (a) 0.25% (b) containing nanosilica, (c) containing 1.0% nanosilica and (d) 5 SEM-EDX images of a membrane containing 2.5% nanosilica, Figure 14; Subject of the invention, Epoxy-functionalized CTA membrane (a) 0.25% (b) containing nanosilica, (c) containing 0.5% nanosilica, (d) containing 1.0% nanosilica The contact angle of the membrane containing 2.5% nanosilica is 10°. Figure 15; The subject of the invention is the powder of an epoxy-functionalized CTA membrane. When an electric field is applied to a CTA membrane modified with nanosilica There is a flow-time graph. 7 DETAILED DESCRIPTION OF THE INVENTION The invention integrates wastewater treatment, water recovery, and nutrient recovery. electro-assisted advanced osmosis membrane bioreactor (MBR) that performs this function It is related to the system. The system in question is a 5 where biological treatment is carried out. bioreactor, semi-permeable forward osmosis membrane module, electrical conduction on the membrane anode and cathode electrodes applying the field, withdrawal solution circuit, nutrient return MAP production reactor for recovery and reconcentration of withdrawal solution. It consists of a unit that enables the processing of wastewater. In this invention, wastewater is primarily processed... It is biologically treated in a bioreactor through microorganisms, then 10 Water is drawn in by the effect of osmotic pressure difference thanks to the advanced osmosis membrane. It is transferred to the solution. The electric field applied to the membrane module Thanks to this, reverse salt flux is reduced and membrane fouling is controlled. and system performance is improved. Human urine or as a withdrawal solution. The use of urine-derived solutions provides the necessary osmotic pressure. 15 Moreover, it becomes possible to utilize a waste resource. The system Within this scope, nitrogen and phosphorus components found in wastewater are analyzed using MAP (magnesium phosphate) testing. It is recovered in the form of ammonium phosphate, and the resulting product is used as fertilizer. can be used or reused as a withdrawal solution within the system. It can be evaluated. In addition, the diluted withdrawal solution is reconcentrated 20 By doing this, the system can be operated in a closed loop. In this respect, the invention; reverse salt reducing flux, minimizing membrane fouling, and providing energy efficiency, reducing chemical use while simultaneously enabling water and nutrient recovery. It offers a sustainable and integrated treatment system. The overall purpose of the invention is to create a complete system that meets the requirements mentioned above. especially wastewater, which eliminates disadvantages and brings some additional advantages. water treatment, membrane separation technologies, advanced osmosis (FO) processes, osmotic Membrane bioreactor (OsMBR) systems, electrochemical processes and nutrient recovery It is related to acquisition technologies. 30 8 Due to the drawbacks of the previous technique, the invention, as described above, It aims to resolve the negative aspects. The primary purpose of this invention is to explore advanced osmosis, osmotic membrane bioreactors, and electric fields. application and nutrient recovery processes in a single integrated system 5 combining the production of high-quality water and valuable nutrients simultaneously from wastewater. The goal is to ensure its recovery. How the Invention Works or Production Technique The invention integrates an electric field-assisted osmotic membrane bioreactor system with 10 It is a treatment system that performs nutrient recovery in the same structure. The system; biological treatment, advanced osmosis membrane separation, electric field application and It consists of a magnesium ammonium phosphate production unit. I. Basic Components of the System 15 The system consists of the following main units: • Bioreactor tank • Forward osmosis (FO) membrane module • Electric field application unit (anode, cathode and DC power supply) • Draw solution tank 20 • MAP production reactor • Reconcentration (RO or equivalent) unit II. How the System Works 1. Biological Treatment Stage 25 • Wastewater is fed into the bioreactor. Activated sludge is placed inside the reactor. Microorganisms break down organic matter. • COD and BOD removal occurs. • Ammonium and phosphate remain in the solution. 2. Advanced Osmosis (FO) Membrane Separation 9 • Semi-permeable FO membrane between the bioreactor and the withdrawal solution. It is found. • Water molecules are drawn into the solution due to osmotic pressure difference. It passes. • Pollutants are captured in the bioreactor. 5 • However, in order to reduce the reverse salt flux observed in classical systems The system is operated under an electric field. 3. Electric Field Assisted Operation Electrodes are placed on both sides of the membrane module and a low-voltage DC current of 10 is applied. It is applied. Thanks to the electric field: • An electrostatic repulsive force is generated on the negatively charged membrane surface. • Ion backdiffusion from the withdrawal solution to the bioreactor is reduced. • Reverse salt flux is minimized. 15 • Biofouling on the membrane surface is reduced. • Flux stability increases. 4. Use of Urine as an Withdrawal Solution Urine or urine-derived solutions are used as the withdrawal solution in the system. 20 In urine: • Ammonium • Phosphate • Potassium • Dissolved salts create high osmotic pressure, hindering water passage. provides. This approach eliminates the need for commercially available traction solutions. 5. MAP (Struvite) Production • Add urine or concentrated nitrogen-phosphorus to the flow MAP reactor at 30°C. is directed. • Magnesium is added to the reactor and crystallization is carried out. • The compound produced: • Magnesium Ammonium Phosphate (MgNH₄PO₄·6H₂O) • The resulting MAP: • It separates as a solid phase. • Can be used as fertilizer 5 • If desired, it can be dissolved and reused in the preparation of the extraction solution. can be given to the system • This enables closed-loop nutrient recovery. III. Membrane Manufacturing Technique 10 The membrane is modified as follows: 1. Basic Membrane Cellulose triacetate (CTA) or polyamide based FO membrane is used. 2. Surface Modification The membrane surface is modified using a nanomaterial coating method. Materials used: 3. Coating Method 20 • Dip coating • Spray coating • Vacuum filtration • In situ polymerization • After coating: 25 • Negative surface charge increases • Hydrophilicity increases • The reverse salt diffusion coefficient decreases. • Fouling resistance increases IV. Reconcentration Phase 11 • The diluted withdrawal solution after FO is fed into the reverse osmosis (RO) unit. is directed. • Pure water is obtained. • The extraction solution is reconcentrated. • The system operates in a closed loop. 5 V. Technical Impact of the System • Thanks to this working principle: • Reverse salt flux is brought under control. • Membrane fouling is reduced. 10 • Energy consumption decreases. • The need for chemical extraction solutions is eliminated. • Nitrogen and phosphorus are converted into economically valuable products. • Water and nutrient recovery are carried out in the same system. VI. The Innovative Aspect of the System System; • Electric field-assisted OsMBR concept • Use of urine as a direct withdrawal solution • Dual-function evaluation of MAP 20 • Using nanomaterial modified FO membranes offers the same properties. in terms of bringing them together in an integrated structure, compared to the existing technology They are leaving. Table 1. General information on tensile solutions 25 Pull solution Chemical formula Molar mass Resolution (in the water) Intensity Conductivity (mS / cm) Osmotic pressure (Posm) (MPa) Fresh urine liquid - - Soluble 1.005- 1.030 g / cm3 20.79 2.5 12 day kept waiting urine - - Soluble 1.002- 1.020 g / cm3 10.22 1.2 KOI content reduced urine liquid - - Soluble 1.005- 1.030 g / cm3 18.07 1.5 MAP NH4MgPO4· 6H2O 137.3 g / mol Low soluble 1.711 g / cm3 24.80 2.9 Sea water -- Soluble 1.024 g / cm3 39.30 3.5 Calcium acetate C₄H₆CaO₄ 158.1 g / mol 34.7 g / 100 mL (20 °C) 1.509 g / cm3 35.10 3.2 Magnesium um acetate Mg(CH₃CO O)₂ 142.4 g / mol 14.75 g / 100 ml (25 °C) 1,450 g / cm³ 29.70 3.0 Glucose C₆H₁₂O₆ 180.2 g / mol 47.0 g / 100 mL (20 °C) 1,560 g / cm³ 1.86 2.5 Sucrose C12H22O11 342.3 g / mol 211.4 g / 100 mL (25 °C) 1,587 g / cm3 0.63 2.2 Modification with Nanosilica As is known, NF and RO membranes have a negative surface charge (pH˃3). Wastewater Many pollutants and microorganisms in it cause the pH of domestic wastewater to be 6-9. It has a negative surface charge in the range of 5. Thus, it has an electrical repulsive force. Therefore, the membranes become fouled more slowly. However, in a bioreactor... dissolved microbial resulting from the vital activities of microorganisms products (SMP) and extracellular polymeric materials (EPS) on the membrane surface It begins to accumulate. Within the scope of the study, the membrane surface has a strong negative surface. modified with silica nanoparticles (zeta potential: -45 mV at pH: 7) by achieving a stronger effect on the CTA membrane surface (zeta potential: -23 mV at pH 7). 13 By creating an electrostatic repulsive force (approximately 2 times), both biofouling and It is envisioned that reverse salt flux should be minimized or prevented. For this purpose... Modification was carried out using 4 different methods. For membrane modification... A dip coating device was used. In-situ modification Silica nanoparticles, ranging from 10 to 500 nm, possess a variety of shapes and physicochemical properties. SiNPs can be synthesized using a series of protocols that yield nanoparticles in a specific size range. The most commonly used method for its synthesis is the Stober process. Stober The method was first used in 1968 with monodisperse silica 10 in the sub-micrometer range. It was introduced for the synthesis of particles (Stöber et al. 1968). In this method, ethanol and hydrolyzed in the presence of ammonium hydroxide (NH2OH) and then emitted at a speed of less than 200 nm to produce smaller, non-porous silica particles tetraethyl orthosilicate, a silica precursor following a polycondensation reaction. (TEOS) is used. 15 According to this synthesis protocol, the first step involves 360 mL of ethanol, 36 mL of pure water, and To a solution containing 4 mL of ammonia, different percentages (0.25%, 0.5%, 1.0% and 2.5%) are added. TEOS was added and mixed. CTA was added immediately after the addition of TEOS. The membrane was immersed in the liquid solution at a speed of 10 mm / sec for 30 minutes. silica was left to stand and then withdrawn from the solution at the same rate. Nanoparticles were formed in situ on the membrane surface. The process took 24 hours. It has continued. Modification with powdered nanosilica 25 The first step in obtaining powdered nanosilica involves mixing 90 mL of ethanol, 9 mL of pure water, and 1 mL of... 4.5 mL of TEOS was added to an ammonia-containing solution and stirred for 8 hours. The mixture was then centrifuged to obtain the solid precipitate. The resulting solid... The precipitates were dried at 40°C for 8 hours, thus forming SiO nanoparticles. It was produced. Different percentages (0.25%, 0.5%, 30%) of SiO nanoparticles were produced. CTA membrane fluid solution is prepared immediately after preparation of the 1.0% and 2.5% solutions. immersed in at a speed of 10 mm / sec, left for 30 minutes, and then the same 14 silica nanoparticles are rapidly withdrawn from the solution and transferred to the membrane surface. The coating process was completed. The operation lasted 24 hours. In-situ modification of epoxy-functionalized membrane (3-glycidyloxypropyl)trimethoxysilane (GOPTS) 5, which has an epoxy functional group. The chemical was treated with a CTA membrane covering an area of ​​25 cm2. This In this step, a 1% GOPTS solution was prepared (pH 10) and membrane CTA was added to it. The membrane was added and shaken for 2 hours. As a result of the reaction, silica was formed. nanoparticles chemically bonded to the membrane surface and coated The next stage has been reached. A 10-liter tank containing 360 mL of ethanol, 36 mL of pure water, and 4 mL of ammonia has been prepared. TEOS was added to the solution in different percentages (0.25%, 0.5%, 1.0% and 2.5%). It was mixed. Immediately after the addition of TEOS, an epoxy group appeared on its surface. The formed CTA membrane was immersed in the liquid solution at a speed of 10 mm / sec, silica was left for a few minutes and then withdrawn from the solution at the same rate. Nanoparticles were formed in situ on the membrane surface. The process took 24 hours and 15 minutes. It has continued. Powder nanosilica modification of epoxy-functionalized membrane (3-glycidyloxypropyl)trimethoxysilane (GOPTS) with epoxy functional group A 1% solution of the chemical treated a 25 cm2 area CTA membrane. It has been done. The epoxy functional group of GOPTS and the hydroxyl group of the CTA membrane silica groups as a result of interfacial chemical bonding reactions Nanoparticles are chemically bonded to the membrane surface. Epoxy groups Because they tend to react at high pH conditions, the reaction is at pH 11- This was carried out in the 12 range. During the bonding process, 25% of the epoxy compound was used. Ring opening occurs in epoxy groups to form a β-hydroxyl group. These molecules form secondary ether bonds when combined with hydroxyl groups. The hydroxyl group on the CTA membrane and the epoxy groups on the GOPTS membrane. To activate it, 0.1 N sodium hydroxide (NaOH) is added to the membrane at pH 10. The membranes were shaken in the solution for approximately 2 hours. Then the membranes were rinsed with pure 30 solution. It was washed three times with water and its performance was modified by testing it on E-OsMBR. It was compared with an unprocessed membrane. The pore size of the CTA membrane is 0.37 In contrast, the hydrated diameters of Na+ and Cl- ions are 0.18 nm and nm, respectively. It is 0.19 nm. Consequently, it has a high ion concentration over time. from the withdrawal solution to the bioreactor with low ion concentration. Ion migration will occur. To prevent or delay ion migration in the system... A strong 5-bit effect is achieved on the CTA membrane surface with nanosilica, which has a high negative charge. An electrostatic repulsive field has been created. The surface of the CTA membrane is coated with nanosilica. The modification is shown in Figure 1. Figure 1; The subject of the invention is the surface modification of a CTA membrane with nanosilica. Nanoasilica was synthesized using the Stöber method. This method involves the synthesis of tetra-alkyl silicate. It is based on the hydrolysis of ammonium in an alcohol medium, using ammonium as a catalyst. Tetra-ethyl orthosilicate (2.25 mL, TEOS), ethanol (42.5 mL), purified water (4.5 mL), and Ammonium hydroxide (0.75 mL) was mixed at 25°C at 250 rpm for 24 hours. SiO2 The nanoparticles were centrifuged and washed once with ethanol and twice with pure water. 15 It was then dried in an oven at 50°C for 24 hours. (Stöber method) SiO2 nanoparticles synthesized according to the formula are 0.25%, 0.5%, 1.0% and 2.5%. Used in concentrations. Reverse salt flux with SiO2 nanoparticles. The relationship between them has been investigated. Here, the active side of the modified CTA membrane is examined. It has been tested both in the withdrawal solution and on the bioreactor side. 20 Characterization of the generated MAP. In this study, the surface morphology of MAP crystals under optimum conditions was investigated. This was determined using the acquired SEM images (Figure 2). From the SEM images As can be seen, MAP shows bar 25, similar to the findings of other researchers. It has similar irregularly shaped octahedral crystals (Kemacheevakul et al. 2015). Figure 2; Photographs of the MAP obtained from urine, which is the subject of the invention, taken at different magnifications. SEM images (A: 10 µm; B: 4 µm; C: 1 µm; D: 500 nm), 16 EDX analysis of the MAP produced under ideal conditions, along with SEM images, By showing the presence of Mg+2, NH4+ and PO4-3, the crystals have a MAP composition. This has been confirmed (Figure 3). Figure 3; EDX spectrum of MAP obtained from urine, which is the subject of the invention, 5 The crystal structure of MAP was qualitatively determined by XRD analysis (Figure 4). Reference powder diffraction for MAP crystals produced under optimum experimental conditions. Density and locations of XRD patterns matching file (PDF 00-015-0762) The formation of MAP has been confirmed and the results are consistent with the literature. This has been observed (Shaddel et al. 2019). Figure 4; XRD peaks of the MAP, which is the subject of the invention. As a result of tensile solution studies, the best flux in terms of flux was obtained with 1.0 M MAP, 15. Since the results were obtained, MAP solution was used in E-OsMBR studies. The resulting flux-time graph is shown in Figure 5. Initial flux is 5.53 LMH. When the electric field of the MAP is not applied, the equilibrium flux is up to 3.89 LMH. It has decreased when 2.5, 5.0, 10, and 20 V electric fields are applied to the OsMBR system. Initial and equilibrium fluxes were 7.32, 9.24, 9.58, 10.21 LMH and 4.44, 4.92, 20 LMH, respectively. It was measured as 6.42, 6.42 LMH. As clearly seen from the results. The initial flux increased by approximately 85% when an electric field was applied. Since the flux values ​​of 20V and 3V are close to each other, the modified membrane A current of 10 V was chosen for the studies. Figure 5; The subject of the invention is the flux when the effect of the electric field is determined. time graph, Findings from modified membrane studies. The two main problems of the OsMBR process are 30 steps from the withdrawal solution to the bioreactor. The resulting problem is reverse salt flux and membrane fouling. Both membrane biofouling... and also to reduce reverse salt flux, CTA membrane is chemically treated. 17 It will be modified. Although new membranes related to FO have been developed in the literature. Intensive research is still underway to reduce reverse salt flux in OsMBRs. Within the scope of the study, the CTA membrane was chemically modified. and one with low reverse salt flux, high flux, and high biofouling resistance. The aim was to obtain a membrane. CTA membrane nanosilica, GO and BNNT 5 It has been modified. The CTA membrane was modified but not subsequently modified. Surface analysis of membranes was performed using SEM, EDX, AFM, and contact angle analyses. Their properties have been compared. All these analyses were also performed on the membranes used. It was made. CTA membrane without electric field and under 10 V electric field. It has been tested and detailed descriptions of its modification are given below. 10 Characterization of pure CTA membrane SEM, EDX, AFM, and contact angle analyses were performed on pure CTA membrane. It was compared with modified membranes. The pure CTA membrane was tested on both its top surface. SEM images were also obtained from its cross-section (Figure 6). CTA membrane 15 Based on the surface image, it appears to have a non-porous and smooth structure. (Figure 6A). Fiber according to SEM image taken from a cross-section of the CTA membrane. the active membrane surface is located on a support layer in the form of as seen (Figure 6B). Figure 6; The subject of the invention, (a) top surface (×50,000) and (b) cross-section of the pure CTA membrane. Cross-sectional (×500) SEM image, According to EDX analysis results, the structure of pure CTA membrane consists of C (49.82%) and O. It is seen that it consists of (50.18%) (Figure 7). 25 Figure 7; EDX image of the pure CTA membrane, which is the subject of the invention. The contact angles of the pure CTA membrane over time are shown in Figure 8. The membrane has a contact angle of 56.3° and is hydrophilic. 30 18 Figure 8; Contact angle of the pure CTA membrane, which is the subject of the invention. Modification with nanosilica Four different methods were used in modification with nanosilica, and these were in-situ. modification, modification with powdered nanosilica, epoxy-functionalized 5 In-situ modification of the membrane and powder of the epoxy-functionalized membrane. It is a nanosilica modification. SEM images of the synthesized nanosilica are shown in Figure. It is located in section 9 and the nanoparticle sizes were found to be below 100 nm. It has been done. Figure 9; SEM images of the nanosilicate, which is the subject of the invention (A: ×100,000 and B: ×200,000) According to EDX analysis results, the synthesized nanosilicon structure consists of C (23.43%), O It is observed that it consists of 47.33% and Si (29.24%) (Figure 10). 15 Figure 10; EDX image of the nanosilicate, which is the subject of the invention. X-ray diffraction patterns of the prepared SiO2 samples are shown in Figure 11. Its amorphous structure has been confirmed. A broad peak indicates a completely amorphous structure. 20 Apart from a broad band centered at 22° which is characteristic of amorphous SiO2, there is no other No diffraction peak was observed. This broadband is indicative of an amorphous structure. This is considered acceptable and indicates that it does not contain a crystalline structure. The absence of a crystalline structure... This means the material does not have regular atomic arrangements in certain directions. income. The results were also compared with the JCPDS file for SiO2 and 25 for SiO2. No impurity peaks were observed. This finding indicates that the samples are of high purity and This confirms that the amorphous structure has been preserved. The JCPDS file is standard. It provides reference data, and comparisons made with this file show the material's... It is critical to determine whether it possesses the expected characteristics. (Ghani et al. 2017). The absence of impurity peaks in SiO2 samples indicates that the synthesis process is 30 The data obtained shows that it was carried out in a clean and effective manner. It is observed that SiO2 retains its amorphous characteristics and does not exhibit any crystalline structure. 19 This clearly shows that it did not occur (Tabatabaei et al. 2006; Bajpai et al. 2014). These results indicate that SiO2 was synthesized in accordance with the targeted amorphous structure, and This confirms that it is free from any contamination in terms of purity. Figure 11; XRD image of the nanosilicate, the subject of the invention. Powder nanosilica modification of epoxy-functionalized membrane Modification of epoxy-functionalized CTA membrane with powdered nanosilica. SEM images are shown in Figure 12. From the SEM images, it can be seen that the mixture is made of epoxy. The functionalized CTA membrane is homogeneously mixed with powdered nanosilica 10 It is observed that it is coated. In addition, EDX analyses show that silica is present on the membrane surface. This shows that it was received (Figure 12). Figure 12; Subject of the invention, Epoxy-functionalized CTA membrane (a) 0.25% (b) Top surface of membrane containing nanosilica (×20,000), (b) 15 containing 0.5% nanosilica Membrane top surface (×20,000), (c) Membrane top containing 1.0% nanosilica surface (×20,000) and (d) top surface (×20,000) of membrane containing 2.5% nanosilica SEM images, Figure 13; Subject of the invention, Epoxy-functionalized CTA membrane (a) 0.25 20 (b) containing nanosilica, (c) containing 0.5% nanosilica, (d) containing 1.0% nanosilica SEM-EDX images of a membrane containing 2.5% nanosilica, Contact angles of epoxy-functionalized CTA membrane over time (Figure) This is shown in section 14. Membranes containing 0.25%, 0.5%, 1.0%, and 2.5% nanosilica are shown in section 25. The contact angles are 28.9°, 29.6°, 28.3°, and 26.3° respectively, and they are hydrophilic. The membrane modified using this method is more hydrophilic than the pure CTA membrane. It appears that this is the case. Figure 14; Subject of the invention, Epoxy-functionalized CTA membrane (a) 0.25 30 (b) containing nanosilica, (c) containing 0.5% nanosilica, (d) containing 1.0% nanosilica Contact angle of a membrane containing 2.5% nanosilica, Modification of epoxy-functionalized CTA membrane with powdered nanosilica. The modified CTA membrane produces both non-electrical and electric field signals. The flux-time graph obtained when this is applied is shown in Figure 15. The initial flux was 7.57 LMH, while the equilibrium flux decreased to 4.42 LMH. OsMBR 5 Initial and balance fluxes when a 10 V electric field is applied to the system. They were measured as 11.31 and 7.52 LMH, respectively. Figure 15; The subject of the invention is the powder of an epoxy-functionalized CTA membrane. When an electric field is applied to the CTA membrane modified with nanosilica, it becomes 10 There is a flow-time graph. Working Principle of the Invention The invention relates to biological treatment, advanced osmosis membrane separation, electric field application, and An integrated treatment system that combines nutrient recovery units into a single system. 15 It is a technology. The system basically consists of a bioreactor, an advanced osmosis (FO) membrane module, electric field application unit, tensile solution circuit, MAP production reactor and It consists of a reconcentration unit. The system's operation process is multi-stage, and these stages complement each other. 20 They operate in an integrated manner. In the first stage, wastewater is fed into the bioreactor tank. The active material inside the reactor... Sludge microorganisms biologically break down organic pollutants, reducing COD and It performs BOD removal. During this process, organic matter removal is achieved, 25 The dissolved nitrogen and phosphorus components remain in the liquid phase. Thus, the nutrients remain within the system for subsequent recovery stages. It will be protected. In the second stage, a semi-permeable forward 30 located between the bioreactor and the withdrawal solution The osmosis membrane comes into play. Thanks to this membrane, water is separated by osmotic pressure difference. It is transported from the bioreactor medium to the withdrawal solution by means of this effect. This transfer 21 dissolved pollutants, microorganisms and suspended solids during the process The water is stored in a bioreactor. This ensures the production of high-quality water. However, the reverse salt flux problem seen in classic advanced osmosis systems is not present in this system. It is controlled by the application of an electric field. In this context, membrane 5 Low voltage is achieved through anode and cathode electrodes placed on either side of the module. A high-voltage direct current is applied. Thanks to the electric field created, the membrane An electrostatic repulsive force is generated on its surface. This force is attractive. by reducing the reverse ion back diffusion occurring from the solution to the bioreactor It minimizes salt flux. At the same time, this effect results in a 10-degree difference on the membrane surface. It controls biofouling by reducing pollutant accumulation and improves flux stability. increases. Another important component of the system is the extraction solution. In this invention, the traditional Using human urine or urine-derived solutions instead of chemical solutions 15 It is used as a solution. The high concentration of urine... Ammonium, phosphate, and dissolved salts provide the necessary osmotic pressure for water. This approach makes the transition possible. This approach both reduces costs and minimizes waste. It enables the evaluation of the resource. The nitrogen and phosphorus-rich streams generated within the system are used for MAP production. It is directed to the reactor. In this reactor, crystallization occurs with the addition of magnesium. The reaction is carried out and magnesium ammonium phosphate (MAP) is formed. The resulting MAP separates as a solid phase and can be used directly as fertilizer. Alternatively... As such, the MAP is dissolved and returned to the system as a withdrawal solution. 25 It can be fed. This allows the system to operate in a closed loop. In the final stage, the extracted solution, which has been diluted in the forward osmosis process, is reversed through osmosis. or it is reconcentrated by a similar membrane process. This process As a result, both pure water is obtained and the extraction solution becomes reusable. 30 This ensures that the system can be operated continuously and sustainably. 22 Invention Implementation Processes The system described in this invention is designed with a modular structure and is compatible with existing wastewater treatment plants. It can be integrated into the facilities. The installation process follows specific steps. is being carried out. First, a bioreactor unit is installed or integrated into the existing biological treatment system. Integration is provided. This unit is followed by the advanced osmosis membrane module. It is connected to the reactor outlet. Suitable for both sides of the membrane module. The anode and cathode electrodes are positioned and these electrodes are controlled. It is connected to a direct current power supply. 10 A withdrawal solution tank is integrated into the system. This tank contains urine or a urine-based solution. It is stored and continuously fed to the membrane module. Simultaneously, MAP Nitrogen and phosphorus recovery is achieved by incorporating a production reactor into the system. is provided. 15 Optionally, the withdrawal solution can be reversed for reconcentration. An osmosis unit is added to the system. All system components, including sensors and pump systems, are included. and is made suitable for automated operation by being supported with control equipment. Operation and Implementation Method of the Invention The system can be operated in continuous or semi-continuous flow mode. During operation While wastewater is being fed into the bioreactor, the withdrawal solution is simultaneously being prepared. The system is recirculated. Water passage through the membrane is continuously monitored. and flux values ​​are checked. 25 The electric field application is optimized depending on system performance. In systems typically operated in low voltage ranges, the electric field strength is reversed. It is adjusted to minimize salt flux and reduce membrane fouling. 23 Within the system, parameters such as conductivity, pH, flux, and pressure are measured by sensors. It is continuously monitored through this method. This ensures process control and optimum operation. The conditions are maintained. During the MAP production process, pH control and magnesium dosage are carefully adjusted. 5 Maximum crystal yield is obtained. The resulting MAP is separated as a solid phase, dried, and It is stored. The resulting product can be used as agricultural fertilizer or reintroduced into the system. It can be fed. With the reconcentration unit, the withdrawal solution is continuously recovered and 10 The system operates in a closed loop. This ensures both water and nutrients. The elements are evaluated without any loss. Benefits of the Invention The electro-assisted advanced osmosis membrane bioreactor developed within the scope of the invention is 15 The system offers numerous advantages compared to existing treatment technologies. The system combines water purification, nutrient recovery, and energy efficiency in a single platform. By combining these features, they provide significant technical advantages. First, the system addresses a significant problem in classical advanced osmosis processes: reverse salt 20 It effectively reduces the flux. The electrical current applied to the membrane module... Thanks to the space, ion return occurs from the withdrawal solution to the bioreactor. Diffusion is limited by electrostatic repulsive forces. This situation affects both It improves treatment performance and reduces salt accumulation in the bioreactor environment. By preventing this, it ensures the preservation of microbial activity. 25 Another important advantage of the invention is its effect in reducing membrane fouling. The application of an electric field removes organic and inorganic deposits that accumulate on the membrane surface. It makes it difficult for pollutants to adhere and minimizes biofilm formation. This reduces the frequency of membrane cleaning, thus extending operational continuity. This increases the lifespan of the system. At the same time, it provides more stable flux values. This results in increased process efficiency. 24 The system provides high-quality water production thanks to its advanced osmosis membrane. suspended solids, pathogens and a large proportion of dissolved pollutants High-purity water is obtained on the withdrawal solution side while being retained in the bioreactor. This is a significant issue, especially in water production for reuse purposes. It offers advantages. 5 One of the invention's notable innovations is the use of human urine or other substances as an extraction solution. One approach is the use of urine-derived solutions. This approach allows for the use of commercial chemicals. The need for extraction solutions is eliminated and costs are significantly reduced. This reduces the amount of waste. At the same time, it ensures the utilization of a waste resource. This contributes to the circular economy approach. 10 The system also offers significant benefits in terms of nitrogen and phosphorus recovery. Thanks to the MAP (magnesium ammonium phosphate) production reactor, the substances found in wastewater are removed. Nutrients are recovered in solid form and used directly as fertilizer. It can be used. This situation both reduces environmental pollution and improves agricultural 15 It constitutes a valuable resource for production. Furthermore, this recovered product... Its ability to be used as a re-withdrawal solution, the closed-loop structure of the system. It strengthens. When evaluated in terms of energy efficiency, the system is an advanced 20 operating at low pressure. Thanks to the osmosis process, it is more efficient compared to traditional pressurized membrane systems. It offers low energy consumption. Low voltage for electric field applications. Since it is carried out at these levels, the additional energy requirement is minimal. This situation reduces the overall operating costs of the system. The invention also features a modular and integrable structure. It is compatible with existing wastewater treatment systems. They can be easily integrated into facilities and are available in different capacities. It is scalable. This flexibility allows the system to be used on both small and large scales. This makes it possible to use it in scaled-scale applications. From an environmental perspective, the system reduces chemical use and waste. because it minimizes its formation and supports resource recovery It offers a sustainable solution, especially in water-scarce regions. It makes significant contributions in terms of reuse. Finally, thanks to the system's closed-loop operating principle, both water and... Nutrients are continuously recovered within the system and released externally. Dependence is reduced. This feature is part of the future of sustainable wastewater treatment technologies. This represents a significant technical impact. To fulfill all the purposes stated above and those that can be derived from the detailed explanation. The invention aims to bring about a new generation of electro-osmotic systems supported by advanced osmosis membranes. It is related to membrane bioreactors.

Claims

26 REQUESTS 1. The invention relates to wastewater treatment, water recovery, and nutrient recovery. It is a system that works together, and its characteristic is; — a bioreactor in which organic pollutants are biologically removed, — between the bioreactor in question and the withdrawal solution a positioned semipermeable forward osmosis membrane module, — on both sides of the forward osmosis membrane module 10 positioned and creating an electric field on the membrane surface anode and cathode electrodes structured in this way, — human urine or urine derivatives to create an osmotic pressure difference a withdrawal solution circuit containing solutions, — designed to enable nitrogen and phosphorus recovery MAP (magnesium ammonium phosphate) production reactor, 15 — a method that allows the withdrawal solution to be reconcentrated it includes a membrane separation unit and the electric field in question by reducing reverse salt flux and membrane fouling It is characterized by being controlled.

2. The invention is a method for wastewater treatment, water and nutrient recovery, feature; — wastewater is fed into a bioreactor and subjected to biological treatment. eclipse, 25 — forward osmosis located between the bioreactor and the withdrawal solution drawing water through the membrane by the effect of osmotic pressure difference transferring to the solution, — via anode and cathode electrodes on a membrane module Reducing reverse salt flux by applying an electric field and membrane 30 controlling pollution, 27 — human urine or urine-derived solutions as withdrawal solutions usage, — the nitrogen and phosphorus present in the system are used in the MAP production reactor. recovery with magnesium supplementation, — reconcentrating the diluted withdrawal solution and adding it to the system 5 It is characterized by including the recovery process steps. is being done.

3. The invention describes a drawn filter structure designed for use in advanced osmosis processes. It is a solution, and its characteristic is; 10 — ammonium, phosphate and in a way that will provide high osmotic pressure human urine or a urine-derived solution containing dissolved salts being, — 15 obtained after nitrogen and phosphorus recovery from the solution in question by dissolving the resulting MAP compound It is characterized by...

4. The invention describes a drawn filter structure designed for use in advanced osmosis processes. It is a solution, and its characteristic is; 20 — a semi-permeable forward osmosis membrane, — anode and cathode located on either side of the membrane electrodes, — the electrodes in question create a homogeneous electrical current on the membrane surface. 25 being positioned in a way that creates space, — the electric field will reduce ion back diffusion and the membrane It is structured in a way that prevents contamination on its surface. It is characterized by... 28 5. The system according to Claim 1, and its characteristic is that the anode and cathode electrodes in question... It is characterized by being connected to a low-voltage direct current source. is being done.

6. The system is defined according to claim 1, and its characteristic is that the electric field on the membrane surface is 5 by reducing the reverse salt flux by creating an electrostatic repulsive force. It is characterized by...

7. The system according to claim 1, its characteristic is; the advanced osmosis membrane is a flat plate, It is characterized by having a spiral wound or hollow fiber structure. 10 8. The system according to claim 1, its characteristic is; circulation of the withdrawal solution circuit. It is characterized by containing a pump and a storage tank.

9. The system is defined as follows according to claim 1: pH control of the MAP production reactor. It is characterized by containing a unit and a magnesium dosing system. is being done.

10. The system is defined according to claim 1, and its characteristic is that the membrane separation unit is reverse osmosis. It is characterized by the presence of a membrane. 20 11. It is a system according to claim 1, and its characteristic is that the system components are sensors. It is characterized by being monitored and managed by an automated control system. is being done.

12. This method, according to claim 2, is characterized by the low applied electric field. It is characterized by being supplied with high-voltage direct current.

13. The method according to claim 2, its characteristic is that the electric field strength is inversely proportioned. It is characterized by being adjusted to minimize flux. 30 29 14. This method, according to claim 2, is characterized by its basic pH value in MAP production. It is characterized by being kept within the range.

15. The method according to Claim 2, its characteristic is; as a magnesium source It is characterized by the use of magnesium salts. 5 16. This method, according to Claim 2, is characterized by its solid-liquid nature of the resulting MAP product. It is characterized by separation through a separation process.

17. The method according to claim 2, its characteristic is; reverse osmosis process of the withdrawal solution 10 It is characterized by its reconcentration.

18. The method according to claim 2, its characteristic is that the system has continuous or semi-continuous flow. It is characterized by being operated in mode.

19. It is a withdrawal solution according to claim 3, and its characteristic is that the urine has been pre-treated. It is characterized by being free from suspended solids.

20. It is a drawing solution according to claim 3, and its characteristic is that the solution has a certain conductivity. and characterized by its preparation within the range of ion concentrations 20 is being done.

21. It is a withdrawal solution according to claim 3, and its characteristic is that it contains a controlled concentration of MAP compound. Characterized by the regulation of osmotic pressure through dissolution. is being done. 25 22. It is a withdrawal solution according to claim 3, and its properties are: nitrogen and phosphorus. concentration that will optimize advanced osmosis performance It is characterized by its adjustment.

23. It is a withdrawal solution according to claim 4, and its characteristic is that it is used to draw up electrode membranes. characterized by being positioned parallel to the surface and at equal distances from it. is being done.

24. It is a tensile solution according to claim 4, and its characteristic is that it prevents electrode corrosion. 5 It is characterized by being selected from durable conductive materials.

25. It is a tensile solution according to claim 4, and its characteristic is that the electric field is homogeneous. by optimizing the electrode geometry to ensure even distribution. It is characterized. 10 26. It is a withdrawal solution according to claim 4, and its characteristic is that it allows flow through the membrane module. It is characterized by its structure that includes channels.

27. It is a pull-out solution according to claim 4, and its characteristic is that the electric field is adjustable. 15 It is characterized by being controlled by a power supply.

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