WO2021176462A1

WO2021176462A1 - Process for preparation of magnetite loaded sulfur oil (mlso) composite adsorbent

Info

Publication number: WO2021176462A1
Application number: PCT/IN2021/050105
Authority: WO
Inventors: S.K. Bajpai; Seema Tiwari; Aniteshma Chanpuria; Manjula Bajpai; Deepika Dubey
Original assignee: Bajpai S K; Seema Tiwari; Aniteshma Chanpuria; Manjula Bajpai; Deepika Dubey
Priority date: 2020-03-02
Filing date: 2021-02-02
Publication date: 2021-09-10

Abstract

The present invention generally relates to the field of nanomaterials composites, and in particularly relates to a process for preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent. The process includes the steps of: dissolving 40ml of slightly acidified distilled water with 10.4 grams of ferrous sulphate hepta hydrate under mild stirring and following by addition of 12 grams offerric chloride anhydrous; dissolving again 12 grams of NaOH in 40 ml of distilled water under continuous stirring; adding NaOH solution drop-wise into an aqueous solution of Fe(II)/Fe(III) under moderate stirring at 70°C for a period of 1 h; collecting magnetite nano particles after the aqueous solution gets turned into brown or black, wherein the aqueous solution gets turned into brown or black when the solution is centrifuged at a speed of 2000 rpm and kept in an electric oven at 50°C.

Description

PROCESS FOR PREPARATION OF MAGNETITE LOADED SULFUR OIL (MLSO) COMPOSITE ADSORBENT

FIELD OF THE INVENTION

5

The present invention generally relates to the field of nanomaterials composites, and in particularly relates to a process for preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent. 0 BACKGROUND OF THE INVENTION

One of the most important developments in the field of material science is that of architecture of nano materials. Nanostmctured materials are assemblies of nano-sized units that display unique, characteristic properties at a macroscopic scale. The size range of such units lies within the5 colloidal range, where the individual properties are different to both those of atoms/molecules and to those of the bulk. The properties of the nanostmctured assemblies, therefore, can be tuned by varying the colloidal properties of the constituents, mainly particle size, surface properties, inter particle interactions and inter particle distance.

The use of nanoparticles in the field of biomedical applications is a major focus of numerous0 research groups today. Nanoparticles possess several qualities that make them useful in biomedical applications, such as diagnostic bioimaging, dmg delivery, and gene therapy.

Recently, oil spill has emerged out as a serious threat to the aquatic environment as well as to human being. Oil spill can occur through natural as well as anthropogenic processes. Natural5 causes generally include the permeation of oil from the ocean deep which then pierce into the aquatic environment .A natural process involves organic matter from dead aquatic plants and animals leads to formation of cmde oil. In addition, oil can enter into water bodies through a number of ways such as leakage through tanks kept underground in fuel supply stations, mixing of oil containing effluent from edible oil mills into water bodies, discharge coming out from automobile repairing shops, etc.

In the oil spill high concentration of contaminants are released in atmosphere which effect society environmentally, economically, and socially. In general spilled oil mainly affects our

5 biodiversity , aquatic mammals when exposed to oil spills can develop inability to insulate, dissipation of digestive process, and liver functions which often leads to imbalance in metabolic process , dehydration, and in some cases when oil enters in lungs , and kidney death can also occur. One more adverse effect of oil spill is release of highly volatile chemicals like benzene, toluene, PAH ,and oxygenated PAH into the atmosphere 0

In recent past, a large number of oil absorbing materials have been reported which include manufactured resins, flocculent, lignin nanoparticle, cattail fibers, fungi, cellulose aerogel, interlinked multilayered Graphene ultra- light gel etc. 5 The major drawback, associated with the various adsorption based techniques employed for oil uptake, is the lack of any effective technique that could be employed in removal of the oil-sorbed adsorbent from the system. The reason is that oil floats over the surface of water and once it has been adsorbed by the adsorbent material, it is essential to remove it completely from water. In the case of oil spills on a large surface, it becomes very difficult to remove the adsorbent. Indeed,0 a magnetically driven adsorbent could have been a better option for overcoming aforesaid problem. Bearing this novel idea in mind, we have developed a super hydrophobic magnetite nanoparticles loaded poly (sulfur)/oil composite material that not only absorbs the oil effectively, but it can conveniently be removed from the system just using a magnet of proper strength which retains all the oil-loaded adsorbent particles on its surface. 5

In one solution, a process is described for preparation of nanocomposite particles and structures by polymerizing monomers onto a functional inorganic colloid comprising a polymerization initiation site. The polymerization process is preferably a controlled/living polymerization process, including but not limited to, atom transfer radical polymerization and stable free radical polymerization. The nanocomposite particles can self-organize in solution, on surfaces or in films forming nanocomposite stmctures. Tethered AB block nanocomposite particles bring size control, solubility control and control over micro- and macro-functionality to the particles. The process may be catalyzed by a transition metal complex which participates in a reversible redox

5 cycle with at least one of the group and a compound having a radically transferable atom or group, to form a nanocomposite particle with a tethered polymer chain. The process may be continued to form tethered copolymer chain. The particle may be silicon based including, for example, silica, silicates and poly (silsesquioxane). A nanocomposite stmcture may be formed by casting, depositing or forming the material including nanocomposite particles. 0

In one solution, method is provided for the synthesis of unagglomerated, highly dispersed, stable core/shell nanocomposite particles comprised of preparing a reverse micelle microemulsion that contains nanocomposite particles, treating the microemulsion with a silane coupling agent, breaking the microemulsion to form a suspension of the nanocomposite particles by adding an5 acid/alcohol solution to the microemulsion that maintains the suspension of nanocomposite particles at a pH of between about 6 and 7, and simultaneously washing and dispersing the suspension of nanocomposite particles, preferably with a size exclusion HPLC system modified to ensure unagglomeration of the nanocomposite particles. The primary particle size of the nanocomposite particles can range in diameter from between about 1 to 100 nm, preferably from0 between about 10 to 50 nm, more preferably about 10 to 20 nm, and most preferably about 20 nm.

In one solution, a method of making a reverse osmosis membrane, comprising: providing, on the surface of a porous membrane, a composition comprising: a polyamine and a polyfunctional acyl5 halide, the porous support membrane comprising a polymer matrix and microparticles, nanoparticles, or a combination thereof, dispersed throughout the body of the polymer matrix; and interfacially polymerizing the polyamine and polyfunctional acyl halide on the surface of the porous support membrane to form a reverse osmosis membrane comprising: the porous support membrane and a discrimination layer comprising a polyamide.

The existing systems do not provide nanoparticle composite adsorbent that could adsorb an appropriate quantity of oil and then could be removed from water with the help of a magnet of

5 appropriate strength). In addition , the existing systems do not provide the synthesis of nanocomposite for effective removal of oil and grease, which are required to be removed. Further, the existing systems do not develop a super hydrophobic magnetite nanoparticles loaded poly(sulfur)/oil composite material. Therefore, there exists a need to have a process for preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent. 0

SUMMARY OF THE INVENTION

The present invention generally relates to the field of nanomaterial composites, and in particularly relates to a process for the preparation of magnetite loaded sulfur oil (MLSO)5 composite adsorbent.

In an embodiment, a process for preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent is provided. The process includes the steps of: dissolving 40ml of slightly acidified distilled water with 10.4 gram of ferrous sulphate hepta hydrate under mild stirring and following0 by addition of 12 grams of ferric chloride anhydrous; dissolving again 12 gram of NaOH in 40 ml of distilled water under continuous stirring; adding NaOH solution drop-wise into an aqueous solution of Fe(II)/Fe(III) under moderate stirring at 700C for a period of 1 h; collecting magnetite nano particles after the aqueous solution gets turned into brown or black, wherein the aqueous solution gets turned into brown or black when the solution is centrifuged at a speed of 2000 rpm5 and and kept in an electric oven at 50°C; mixing 10ml of edible Palm oil with 10 gram of sulfur powder and magnetite nanoparticles in an air tight steel container and allowing to be heated gradually at 180°C under vigorous stirring with help of magnetic beads; forming magnetite- loaded polymer composite, wherein the formation of the magnetite loaded polymer composite is indicated as the magnetic beads stopped to rotate; and taking out MLSO composite material from the steal container and keeping in a watch glass to dry overnight in an electric oven at 50°C.

An object of the present invention is to develop a super hydrophobic magnetite nanoparticles

5 loaded poly(sulfur)/oil composite material.

Another object of the present invention is to provide a nanocomposite could be removed from the adsorption system using a magnet of proper strength which retains all the oil-loaded adsorbent particles on its surface from water supply. 0 Another object of the present invention is to provide a process for preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent.

Another object of the present invention the synthesis of nanocomposite for effective removal of oil and grease. 5

To further clarify advantages and features of the present invention, a more particular description of the invention will be rendered by reference to specific embodiments thereof, which is illustrated in the appended drawings. It is appreciated that these drawings depict only typical embodiments of the invention and are therefore not to be considered limiting of its scope. The0 invention will be described and explained with additional specificity and detail with the accompanying drawings.

BRIEF DESCRIPTION OF FIGURES 5 These and other features, aspects, and advantages of the present invention will become better understood when the following detailed description is read with reference to the accompanying drawings in which like characters represent like parts throughout the drawings, wherein:

Figure 1 shows a flowchart for a process for preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent;

Figure 2 shows TEM images of magnetite nanoparticles with (a) 50 nm and (b) 20 nm bar length;(c) SAED pattern and (d) Particle size distribution of magnetite nanoparticles in accordance with an embodiment of the present invention;

5 Figure 3 shows XRD patterns of (a) magnetite nanoparticles, (b) SO( sulfur/oil) and (c) MLSO composite materials in accordance with an embodiment of the present invention;

Figure 4 shows FTIR spectra of (a) magnetite, (b) SO and (c) MLSO composite materials in accordance with an embodiment of the present invention;

Figure 5 shows TGA/DTA analysis of (a) magnetite, (b) SO and (c) MLSO composite materials in0 accordance with an embodiment of the present invention;

Figure 6 shows SEM images with 5000X and 10,000X magnifications (a) ,(b) of SO and (C),(d) of MLSO composite materials in accordance with an embodiment of the present invention;

Figure 7 shows graph plots obtained between Relative Pressure (P/Po) and volume of gas at STP for (a) SO and (b) MLSO composite particles in accordance with an embodiment of the present5 invention; and

Figure 8 shows data showing (a) percent oil removal (PRO) and (b) x/m for different quantities of adsorbent MLSO composite particles in accordance with an embodiment of the present invention.

Further, skilled artisans will appreciate that elements in the drawings are illustrated for simplicity0 and may not have been necessarily been drawn to scale. For example, the flow charts illustrate the method in terms of the most prominent steps involved to help to improve understanding of aspects of the present invention. Furthermore, in terms of the constmction of the device, one or more components of the device may have been represented in the drawings by conventional symbols, and the drawings may show only those specific details that are pertinent to5 understanding the embodiments of the present invention so as not to obscure the drawings with details that will be readily apparent to those of ordinary skill in the art having benefit of the description herein.

DETAILED DESCRIPTION: For the purpose of promoting an understanding of the principles of the invention, reference will now be made to the embodiment illustrated in the drawings and specific language will be used to describe the same. It will nevertheless be understood that no limitation of the scope of the

5 invention is thereby intended, such alterations and further modifications in the illustrated system, and such further applications of the principles of the invention as illustrated therein being contemplated as would normally occur to one skilled in the art to which the invention relates.

It will be understood by those skilled in the art that the foregoing general description and the0 following detailed description are exemplary and explanatory of the invention and are not intended to be restrictive thereof.

Reference throughout this specification to “an aspect”, “another aspect” or similar language means that a particular feature, stmcture, or characteristic described in connection with the5 embodiment is included in at least one embodiment of the present invention. Thus, appearances of the phrase “in an embodiment”, “in another embodiment” and similar language throughout this specification may, but do not necessarily, all refer to the same embodiment.

The terms "comprises", "comprising", or any other variations thereof, are intended to cover a0 non-exclusive inclusion, such that a process or method that comprises a list of steps does not include only those steps but may include other steps not expressly listed or inherent to such process or method. Similarly, one or more devices or sub-systems or elements or stmctures or components proceeded by "comprises...a" does not, without more constraints, preclude the existence of other devices or other sub-systems or other elements or other stmctures or other5 components or additional devices or additional sub- systems or additional elements or additional stmctures or additional components.

Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The system, methods, and examples provided herein are illustrative only and not intended to be limiting.

Embodiments of the present invention will be described below in detail with reference to the

5 accompanying drawings.

The present invention generally relates to the field of nano materials composites, and in particularly relates to a process for preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent. 0

Figure 1 illustrates a flowchart for a process of preparation of magnetite loaded sulfur oil (MLSO) composite adsorbent. The process 100 includes the steps of: Step 102 of dissolving 40ml of slightly acidified distilled water with 10.4 grams of ferrous sulphate hepta hydrate under mild stirring and following by addition of 12 grams offerric chloride anhydrous; Step 1045 of dissolving again 12 grams of NaOH in 40 ml of distilled water under continuous stirring; Step 106 of adding NaOH solution drop-wise into an aqueous solution of Fe(II)/Fe(III) under moderate stirring at 700C for a period of 1 h; Step 108 of collecting magnetite nano particles after the aqueous solution gets turned into brown or black, wherein the aqueous solution gets turned into brown or black when the solution is centrifuged at a speed of 2000 rpm and and kept0 in an electric oven at 50°C; Step 110 of mixing 10ml of edible Palm oil with 10 gram of sulfur powder and magnetite nanoparticles in an air tight steel container and allowing to be heated gradually at 1800° C under vigorous stirring with help of magnetic beads; Step 112 of forming magnetite -loaded polymer composite, wherein the formation of the magnetite loaded polymer composite is indicated as the magnetic beads stopped to rotate; and Step 114 of taking out MLSO5 composite material from the steal container and keeping in a watch glass to dry overnight in an electric oven at 350°C.

In an embodiment, co-precipitation of Fe(II) and Fe(III) are formed in the presence of strong alkaline solution results in formation of magnetite nanoparticles. In an embodiment, thermo gravimetric analysis and differential thermal analysis of magnetite nanoparticles, and MLSO composite materials are performed to investigate their thermal stability.

5

In an embodiment, FTIR spectmm of sulphur oil (SO) composite polymer shows a peak at 2920.5 cm ¹ which belongs to olefinic hydrogen of soyabean oil.

In an embodiment, surface area of SO and MLSO are calculated by BET analysis using the0 adsorption and desorption plots obtained between Relative Pressure (P/Po) and volume of gas.

In an embodiment, the MLSO composite material is intended to be used as a super oil adsorbent by introducing a bar magnet of appropriate strength. 5 In an embodiment, definite concentration of oil water mixture is taken and varying quantities of adsorbent MLSO composite is mixed and shaken gently for a period of 15 min, wherein MLSO composite adsorbs oil and gets settled down at the bottom.

In an embodiment, quantity of 100 mg of adsorbent is effective to remove 3.8 g of oil per g of0 adsorbent material.

In an embodiment, Lerrous sulphate hepta- hydrate extra pure (LeS0₄.7H20) molar mass 278.02 g/mol, Lerric chloride anhydrous (FeCL), molar mass 162.21g/mol, Sodium hydroxide and Sulfur Powder (S) atomic weight-32.05, n-heptane( C₇H₁₆) molar mass 100.21g/mol and acetic5 acid are used to carry out the process.

Figure 2 shows Transmission electron microscopy(TEM) images of magnetite nanoparticles with (a) 50 nm and (b) 20 nm bar length;(c) Selective area diffraction pattem(SAED) pattern and (d) Particle size distribution of magnetite nanoparticles in accordance with an embodiment of the present invention. The results of TEM analysis are shown in Lig. 2(a) and (b) with 50 and 20 nm bar length respectively. It can be seen that particles are not spherical but cubic shaped with a size range of 10 to 20 nm. In this way a very narrow size range of magnetite nanoparticles has been obtained.

5 The formation of relatively smaller nanoparticles could be attributed to the fact that higher stirring rate of reaction mixture. As a result of higher stirring speed, energy transferred to the suspension medium is also increased and the reaction solution can be dispersed into smaller droplets and the size is reduced. The SEAD pattern, shown in Fig. 2(c), reveals a number of bright concentric circles thus indicating polycrystalline nature of the material. 0

The d-values, obtained for various circles, are 1.61, 1.72, 2.10, 2.53, and 2.97 Ao , thus indexing the planes (511), (422), (400) , (311) and (220) respectively. Almost similar values have also been reported elsewhere. 5 Finally, the particle size distribution curve is obtained by selecting a large number of particles in a random manner from images obtained at various magnifications and determining their diameters (see Fig. 2(d)). It may be noticed that the distribution curve is almost binomial with around 68 percent of particles within the size range of 5-10 nm. 0 Figure 3 shows XRD patterns of (a) magnetite nanoparticles, (b) SO and (c) MFSO composite materials in accordance with an embodiment of the present invention. Sharp peaks observed in Fig. 3(a) at 32°, 34.5°, 45°, 53°, 56°, 62.8°, 74° correspond to the reflections through the planes (220), (311), (400), (422), (511) , (440) and (622) respectively. These peaks are very consistent with the standard pattern. Almost similar patterns have also been reported by others for magnetite 5 nanoparticles.

The XRD pattern of SO composite exhibits sharp , but low intensity, 20 peaks at 23, 25 , 28, 31, 35, 43, 47, and 51 are attributed to the crystal planes of sulfur at 222, 040, 313, 044, 422, 319, 515, and 266 respectively All these peaks are in close resemblance with JCPDS no. 08-0247. Almost similar results have also been reported in XRD pattern of sulfurnanoparticles.

Finally, the XRD pattern of MLSO composite material, shown in Fig. 3(b), shows a number of peaks along the whole XRD pattern with an amorphous type structure. It is worth mentioning

5 that the various peaks observed are due to presence of magnetite as well as SO composite material.

Finally, in order to test the purity of magnetite nanoparticles and to confirm their composition, the energy dispersive X-ray spectroscopy analysis is carried out as shown in Fig. 3(c). The0 weight percent of iron and oxygen are 64.93 and 35.07 respectively. On the basis of atomic masses of Fe and O, the formula of compound formed is confirmed as Fe304. This also confirms its purity.

Figure 4 shows FTIR spectra of (a) magnetite, (b) SO and (c) MLSO composite materials in5 accordance with an embodiment of the present invention. FTIR spectrum of magnetite nanoparticles is shown in Fig.4(a) . A band at 1626.8 cm-1 and broad band centered at 3346.3 cm ¹ are related to the presence of hydroxyl groups and attributed to OH-bending and OH- stretching vibrations. A peak at 545 cm -1 is attributed to the stretching vibration mode associated to the metal oxygen bond. 0

FTIR spectmm of sulfur/oil(SO)composite polymer, depicted in Fig. 4(b), shows a peak at 2920.5 cm 'which belongs to olefinic hydrogen of soyabean oil. A sharp stretching peak of carbonyl is obtained at 1739.54 cm ¹. A significant peak at 716.14 cm ¹ shows presence of C-S group. 5

Finally, Fig.4(c) shows FTIR spectmm of magnetite loaded sulfur- oil (MLSO) composite polymer. A wide band between 3100 cm-1 and 3600 cm-1 shows presence of OH vibrations of absorbed water of magnetite which is also present spectrum of pure magnetite nanoparticle. In this way, presence of magnetite particles in MLSO composite material is confirmed by spectroscopy.

Figure 5 shows TGA/DTA analysis of (a)magnetite,(b) SO and (c) MLSO composite materials in accordance with an embodiment of the present invention. The thermo gravimetric analysis and

5 differential thermal analysis of magnetite nanoparticles , SO and MLSO composite materials are performed to investigate their thermal stability. The TGA/DTA analysis of magnetite nanoparticles, as depicted in Fig. 5(a) , shows that initially, there is marginal weight loss up to 150°C , attributable to the loss of moisture present on the surface of magnetite nanoparticles. As the temperature is further raised, the sample appears to be quite stable up to 850°C,0 suffering an approximate weight loss of 18% only. This indicates that magnetite nanoparticles are fairly stable against heat. Differential thermal analysis (DTA) of magnetite nanoparticle shows the first endothermic peak at 120°C . An exothermic peak at 780°C shows phase transition of substance. 5 The TGA/DTA of SO composite, shown in Fig.5(b), reveals some interesting facts. The sample is fairly stable up to 180°C, suffering almost no weigh loss. This is quite expected because SO composite is highly hydrophobic in nature and does not have any moisture on its surface. However, as the temperature is further increased, the sample begins to suffer an appreciable weight loss of around 95% up to 620°C.Thgis may probably be due to de- carboxylation and0 decomposition of sulfur chains. Differential thermal analysis of sample sulfur-oil-composite polymer shows the first endothermic peak at 166°C°C and initial thermal transition area is between 166°C and 225 °C. An exothermic peak near 620°C shows phase transition of substance. The results of TGA/DT analysis of sample MLSO composite polymer, as depicted in Fig.5(c) show an intermediate trend. Initially, the polymer is fairly stable up to 200°C, probably due to5 hydrophobicity rendered due to presence of S/O polymer matrix. Later on, the polymer suffers a weight loss of 61 % when heated up to 5400C, which is attributable to the decomposition of sulfur and de -carboxylation coupled with breaking of chains. Differential Thermal analysis shows the first endothermic peak at 153°C . An exothermic peak near 585°Cshows phase transition of substance and 70.5°C weight loss at 587.41°C Figure 6 shows SEM images with 5000X and IO,OOOC magnifications (a) ,(b) of SO and (C),(d) of MLSO composite materials in accordance with an embodiment of the present invention. The surface of the sample SO, as shown in Fig.6(a) and (b) , appears quite rough, uneven with

5 heterogeneous texture and having pores of different sizes . Indeed, the polymer does not appear to be highly porous. The surface of MLSO composite material, displayed in Fig.6 (c) and (d), is also very rough and uneven. Moreover, there can be observed a large number of magnetite particles throughout the surface. However, the particles are aggregated also. 0 Figure 7 shows graph plots obtained between Relative Pressure (P/Po) and volume of gas at STP for (a) SO and (b) MLSO composite particles in accordance with an embodiment of the present invention. Surface area of samples SO and MLSO are calculated by BET analysis using the adsorption and desorption plots obtained between Relative Pressure (P/Po) and volume of gas at STP as shown in Fig. 7(a) and (b) respectively. 5

As per data shown, surface area of samples SO and MLSO are found to be 4.063 m²/g and 2.770 m²/g respectively. It may be noticed that surface area of composite MLSO is less than that of the sample SO. This may probably be due to the fact that magnetite nanoparticles well occupy the pores present in the plain composite SO and therefore the pores volume of composite MLSO is0 less than that of the sample SO.

Figure 8 shows data showing (a) percent oil removal (PRO) and (b) x/m for different quantities of adsorbent MLSO composite particles in accordance with an embodiment of the present invention. The proposed MLSO composite material is intended to be used as a super oil5 adsorbent with an additional advantage that it could simply be removed from the system by introducing a bar magnet of appropriate strength. To investigate the oil removal efficiency of MLSO composite, a definite concentration of oil /water mixture is taken and varying quantities of adsorbent MLSO composite is mixed and shaken gently for a period of 15 min. The polymer adsorbs oil and is settled down at the bottom. Now a bar magnet is introduced in the solution, which attracts all the oil- containing adsorbent. Now the magnet is taken out. The oil-sorbed MLSO sorbent is successfully removed from the adsorption system using a bar magnet. It is clear that as the amount of MLSO material increases, x/m decreases. This may be attributable to the fact that once the all active sites are occupied, further increase in quantity also

5 of adsorbent does not cause any further uptake of oil. It is also noteworthy that a quantity of 100 mg of adsorbent is effective to remove 3.8 g of oil per g of adsorbent material.

In an embodiment, the present invention concludes that introduction of magnetite nanoparticles into the sulfur/oil composite material imparts it magnetic properties and the adsorbent can be0 successfully removed by using magnet of moderate strength. Such adsorbent eliminates the practical problems that are usually encountered while removing the adsorbent after the adsorption process is over. It is also worth mentioning that the adsorbent prepared is having proper magnetic strength and so it will be successfully removed from the adsorption system without any failure. 5

In an exemplary embodiment, magnetite powder, composites SO and MLSO are analyzed by Fourier Transform Infrared (FTIR) spectroscopy with FTIR spectrophotometer (Shimadzu, 8400, Japan) using KBr. The powdered sample is mixed with KBr .The scans recorded are the average of 100 scans and the selected spectral range between 400 to 4000 cm ¹. Detailed morphological0 information of the synthesized MLSO composite material is collected by carrying out SEM (Scanning Electron Microscope) analysis. The size of the magnetite nanoparticles synthesized is determined by Transmission electron microscopy. Thermal stability of magnetite nanoparticle, SO and MLSO composites is investigated by TG analysis in the temperature range of ambient to 800°C under heating rate of 10°C per min with a nitrogen flow of 20 mL per5 min.The identification and quantification of In order to determine the crystalline nature of magnetite nanoparticles, composites SO and MLSO, XRD analysis is carried out. The various peaks are also verified to confirm the formation and presence of magnetite nanoparticles in composite material. The X-ray diffraction (XRD) method is used to measure the crystalline nature films. These measurements are carried out on a Rikagu Diffractometer (Cu radiation = 0.1546 nm) running at 40 kV and 40 mA. The diffractogram is recorded in the range of 2 from 3 to 500 at the speed rate of 4 degree/ min. Finally, the surface area of plain composite SO and magnetite loaded sample MLSO is determined using BET equation. Automated gas sorption data are obtained by Quanta chrome Instruments version 3.0 .Nitrogen gas is used as an adsorbate at

5 bath temperature 77.350 K.

In order to investigate the effectiveness of MLSO composite in removing oil from synthetic oil- contaminated water, varying quantities of adsorbent MLSO composite are added in to synthetic oil-contaminated water samples, with an oil concentration of 1.814 g/liter and allowed to0 equilibrate under mild stirring for a period of 30 min, which is found to be sufficient time for the attainment of equilibrium. The adsorbent is removed from the adsorption system by introducing a bar magnet and the remaining oil is separated carefully with the help of a separating funnel and is made up to a definite volume by addition of heptane. The absorbance of the solution is measured spectrophotometrically and is transformed into concentration using Lambert-Beers law5 obtained for a series of solutions of oil in heptane with varying concentrations. The percent oil removal (POR) is determined using the following expression:

In an implementation, The co-precipitation of Fe(II) and Fe(III) in the presence of strong alkaline0 solution results in formation of magnetite nanoparticles. The reaction temperature is maintained at 70°C and pH of the solution is around 12. The chemical reaction involved is shown below:

Fe²⁺ + 2 Fe³⁺ + 8 OH Fe₃0₄ +4H₂0

Preparation of MLSO composite adsorbent 5

In this study, perhaps for the first time, we have synthesized poly (sulfur)/oil composite material in the presence of uniformly distributed magnetite nanoparticles. When magnetite nano particles are mixed in to sulfur powder containing edible oil under high stirring, magnetite particles are well distributed in the oil phase .As the temperature of the reaction mixture is increased beyond 110°C, sulfur particles melt and form a homogeneous phase with oil and suspended nanoparticles. After the temperature reaches 180oC, liquid Ss undergoes de -polymerization and attacks the p bond of triglycerides present in oil. During the course of the reaction, magnetite nanoparticles remain well homogenously distributed and finally amagnetic composite polymer is formed.

5

The drawings and the forgoing description give examples of embodiments. Those skilled in the art will appreciate that one or more of the described elements may well be combined into a single functional element. Alternatively, certain elements may be split into multiple functional elements. Elements from one embodiment may be added to another embodiment. For example, 0 orders of processes described herein may be changed and are not limited to the manner described herein. Moreover, the actions of any flow diagram need not be implemented in the order shown; nor do all of the acts necessarily need to be performed. Also, those acts that are not dependent on other acts may be performed in parallel with the other acts. The scope of embodiments is by no means limited by these specific examples. Numerous variations, whether explicitly given in 5 the specification or not, such as differences in structure, dimension, and use of material, are possible. The scope of embodiments is at least as broad as given by the following claims.

Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, the benefits, advantages, solutions to problems, and any0 component(s) that may cause any benefit, advantage, or solution to occur or become more pronounced are not to be construed as a critical, required, or essential feature or component of any or all the claims.

Claims

We claim:

1. A process for preparation of magnetite loaded sulfur oil (MLSO) composite

5 adsorbent, said process comprising: dissolving 40ml of slightly acidified distilled water with 10.4 grams of ferrous sulphate hepta hydrate under mild stirring and following by addition of 12 grams offerric chloride anhydrous; dissolving again 12 grams of NaOH in 40 ml of distilled water under continuous0 stirring; adding NaOH solution drop-wise into an aqueous solution of Fe(II)/Fe(III) under moderate stirring at 70°C for a period of 1 h; collecting magnetite nano particles after the aqueous solution gets turned into brown or black, wherein the aqueous solution gets turned into brown or black when the solution is5 centrifuged at a speed of 2000 rpm and and kept in an electric oven at 50°C; mixing 10ml of edible Palm oil with 10 gram of sulfur powder and magnetite nanoparticles in an air tight steel container and allowing to be heated gradually at 180°C under vigorous stirring with help of magnetic beads; forming magnetite-loaded polymer composite, wherein the formation of the magnetite0 loaded polymer composite is indicated as the magnetic beads stopped to rotate; and taking out MLSO composite material from the steal container and kepping in a watch glass to dry overnight in an electric oven at 350°C.

2. The process as claimed in claim 1, wherein co-precipitation of Fe(II) and Fe(III)5 are formed in the presence of strong alkaline solution results in formation of magnetite nanoparticles.

3. The process as claimed in claim 1, wherein thermo gravimetric analysis and differential thermal analysis of magnetite nanoparticles, and MLSO composite materials are performed to investigate their thermal stability.

4. The process as claimed in claim 1, wherein FTIR spectrum of sulphur oil (SO) composite polymer shows a peak at 2920.5 cm-1 which belongs to olefinic hydrogen of

5 soyabean oil.

5. The process as claimed in claim 1, wherein surface area of SO and MLSO are calculated by BET analysis using the adsorption and desorption plots obtained between Relative Pressure (P/Po) and volume of gas. 0

6. process as claimed in claim 1, wherein the MLSO composite material is intended to be used as a super oil adsorbent by introducing a bar magnet of appropriate strength shows the the excellent separation of impurities from oil. 5 7.The process as claimed in claim 6, wherein definite concentration of oil water mixture is taken and varying quantities of adsorbent MLSO composite is mixed and shaken gently for a period of 15 min, wherein MLSO composite adsorbs oil and gets settled down at the bottom . 0 8. The process as claimed in claim 7, wherein quantity of 100 mg of adsorbent is effective to remove 3.8 g of oil per g of adsorbent material. 5