1.

INTRODUCTION
It is well-known that sulphur compounds are undesirable in the fuels. Elemental sulphur is not toxic, but many simple sulphur derivates are very toxic, such as sulphur dioxide (SO2) and hydrogen sulphide. Combustion of sulphur-containing compounds in fossil fuels emits sulphur oxides, which can cause adverse effects on health, environment and economy. Globally sulphuric substances can have the following effects on human health: Disturbance of blood circulation, Heart damage, Effects on eyes and eyesight, Reproductive failure, Damage to immune systems, Stomach and gastrointestinal disorder, Damage to liver and kidney functions, Hearing defects, Disturbance of the hormonal metabolism, Dermatological effects, Suffocation and lung embolism and, Neurological effects and behavioural changes Need for Desulfurization: Presence of sulphur in crudes is a menace because it causes many difficulties like-corrosion of metals, in processing of oils, and also environmental pollution as a result of burning of high sulphur fuels that are processed from crudes having high sulphur content. In brief, presence of sulphur in crudes causes [1]: 1. Problems of corrosion and odour 2. Pollution problems 3. Cost of waste treatment is a punitive for all refiners with high- sulphur crudes 4. Sulphur containing residums when cracked leaves cross-linked structures that resemble the phenomenon of vulcanization of rubber and offer perennial problems 5. It desists the effects of additives
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6. Its presence in different fractions complicates the refining and treatment methods Types of sulphur compounds in various fuels Table 1.1 below gives us an idea of the type of sulphur compounds that are present in various fuels. Although sulphur concentrations in gasoline and diesel fuel are moving to progressively lower levels, additional steps to remove the remaining sulphur are still required. Table 1.1 Type of sulphur compound BOILING RANGE SULPHUR COMPOUNDS GASOLINE 25 225 *C Mercaptans, disulphides, and its sulphides, thiophene alkylated

derivatives, Benzothiophene JET FUEL/ KEROSENE 130-300 *C Mercaptans, benzothiophene, alkylated Benzothiophene DIESEL 160-380*C Alkylated benzothiophene, benzothiophene, alkylated dibenzothiophene di-

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2. LITERATURE REVIEW
Li et al[1] in 2008 had worked on desulphurization of fuel using CuNaY zeolites that were prepared by microwave irradiation and also studied about the influence of aromatics on thiophene adsorption. The zeolites are prepared by Solid phase ion exchange (SPIE) or liquid phase ion exchange (LPIE). LPIE is quite common. In contrast to the usual process of heating the exchange suspension through an oil or water bath, microwave irradiation is used. On analysing the X-Ray powder Diffraction patterns of Na-Y and Cu-ion exchanged zeolite samples, recorded at 2 values between 5 and 60, Li showed that the irradiation technique is a better option because the characteristic peaks for Cu ion-exchanged zeolite samples are similar to those of Na-Y and no shift in the peak positions and no significant diffraction lines assigned to any new phase were observed. They observed the effects of the microwave irradiating power, duration time and the copper ion concentration in aqueous solutions on the ion exchange level and the structure of copper ion-exchanged zeolite samples with the help of atomic absorption spectrophotometer, X-ray powder diffraction, N2 adsorption and scanning electron microscope and X-ray photoelectron spectroscopy and showed that microwave irradiation was a more attractive zeolite preparation method. Xiao et al [2] in 2008 worked on the adsorption of benzo-thiophene (BT) and di-benzo-thiophene (DBT) on transition metal ion impregnated activated carbons and ion exchanged Y- zeolites. A total of 10 samples were prepared where 5 of them were transition-metal ions (Ag+, Ni2+, Cu2+, Zn2+, and Fe3+) separately loaded on the ACs by the impregnation method and the other five included Y-type zeolites separately containing Ag+, Ni2+, Cu2+, Zn2+, and Fe3+, prepared by the liquid ion-exchange method. They compared the Isotherms of BT and DBT on original activated carbon, with, the effects of different ions on isotherms of BT and DBT, and concluded that the adsorbing capacity depended on the concentration of BT, where, at high concentration of BT, activated
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carbon was a better sorbent and at low concentration, Y-zeolite was a good adsorbent. It was observed that the pore surfaces of the ACs have stronger interactions with adsorbate DBT compared to BT because the size of DBT is larger than that of BT. This was the reason why, there was no adsorption of DBT on Na(I)/Y zeolites. They showed that (1) the adsorption of BT by Ag(I)/Y was the highest, while that by Na/Y was the lowest and (2) the Ag (I)/AC was the highest, while that on Fe (III)/AC was the lowest. David L. King et al [3], worked on removal of sulfur components from low sulfur gasoline using copper exchanged zeolite Y at ambient temperature. Copper-exchanged zeolite Y has been shown to be an effective material for removal of a variety of sulfur species from hydrocarbon streams, and both monovalent (Cu(I)) and divalent (Cu(II)Y) materials have been claimed to be effective. In their work, they discussed about experiments aimed at providing a direct performance comparison between the two copper-containing materials. Cu(I)Y zeolite is somewhat more effective than Cu(II)Y in removing thiophene from various fuel blends. Capacity of both materials for thiophene diminishes markedly when aromatics and/or olefins are present, and Cu(I)Y immediately turns dark on exposure to such feeds. Both materials demonstrate ability to convert thiols to disulfides at ambient temperature. AnkurSrivastav et al [4], there study shows that the alumina could be used as adsorbent for the desulfurization of liquid fuels. There studies were performed to understand the mechanism of DBT adsorption onto alumina. Presence of DBT on the surface of alumina was confirmed by comparing EDX of DBT loaded alumina. Equilibrium between the DBT in the solution and on the alumina surface was practically achieved in 24 h. The adsorption processes was well described by his amulti-stage diffusion model. The DBT up take was found to be controlled by external mass transfer at earlier stages and by intraparticle diffusion at later stages The adsorption of DBT onto alumina was found
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to be endothermic in nature with the heat of adsorption being 19.5 kJ/mol. His experiments best represents the equilibrium adsorption data at all temperatures. Babich et al [5] ,they discussed about the technologies of sulfur removal from refinery streams leads to a better research topic. There several topics have the character of demonstration better removal of sulfur. Some of the integrated approachs are catalyst selection, reactor design, process configuration will lead to efficient desulfurization processes that will produce fuels with zero sulfur emission. There other approaches to sulfur removal, such as extractive desulfurization, look less attractive since the involvement of an additional phase leads to large plants and limited efficiency. The same applies for oxidative extraction, in which in addition to the solvent an oxidant is required in addition to the solvent, although recycling might reduce the amounts consumed. Blanco-Brieva et al [6],worked to improve the adsorption capacity and sorbent regeneration in areas such as increasing specific desulfurization activity, hydrocarbon phase tolerance, sulfur removal at higher temperature, and development of new porous substrates for desulfurization of a broader range of sulphur compounds. There work comprehensively describes the adsorption of organo-sulfur compounds present in liquid fuels on metal-organic framework (MOF) compounds. They has been demonstrated that the extent of dibenzothiophene (DBT) adsorption at temperatures close to ambient (304 K) is much higher on MOF systems than on the benchmarked Y-type zeolite and activated carbons. In addition, the DBT adsorption capacity depends strongly on the MOF type as they illustrated by the much higher extent of adsorption observed on the Cu-(C300) and Al-containing (A100) MOF systems than on the Fe-containing (F300) MOF.

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Chetan Borkar et al [7], worked on several experiments on adsorption of VOC, namely, dichloromethane,on activated carbon by a flow-through gravimetric technique using a thermo-gravimetric analyser. They took the measurements which were performed at three different temperatures, namely, (303.15, 318.15, and 353.15) K. They compared the results to already available data for the adsorption of dicholoro-methane on activated carbon.Although higher partial pressures can readily be obtained, he measured the isothermsup to partial pressures of about 1 kPa; higher partial pressureswould be rarely encountered in industry. The isotherms werefit using virial and Langmuir models. It was observed that thebest description of experimental data is obtained using a virialisotherm across all of the temperatures. The limiting enthalpyof adsorption obtained using the virial model was -41 kJ mol-1. I.HilalGbbk et al [8],conducted several experiments on synthesis, characterization, and sorption properties of silica gel-immobilized Schiff base derivative. Theyderivatized the Silica gel from benzophenone 4-

aminobenzoylhydrazone (BAH), a Schiff base derivative, after silanization of silica by 3-chloropropyltrimethoxysilane (CPTS) by using a reported method. The mean sorption energy (E) of benzophenone 4-aminobenzoylhydrazone (BAH) immobilization onto silica gel was calculated from DR isotherms, indicating a chemical sorption mode for four cations. He also calculated the thermodynamic parameters, like _G, _S, and _H for the system. They observed _H values were found to be endothermic: 27.0, 22.7, 32.6, and 34.6 kJmol1 for Cu(II), Ni(II), Co(II), and Zn(II) metal ions, respectively and _S values were calculated to be positive for thesorption of the same sequence of divalent cations onto sorbent. They observed negativeG-values, which indicate that the sorption process for these three metal ions onto immobilized silica gel is spontaneous.This study indicated that the immobilized silica gel surface using BAH after CPTS, as precursor silylating agent, could be used as effective adsorbent material for the purification of water. The sorption of four metal ions,
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from aqueous solution onto an immobilized silica gel, was studied in his work. The order of sorption capacities order was Zn >Cu >Co >Ni. Immobilized silica gel may be used as an inexpensive, effective, and alternative sorbent for removal of four metal ions from aqueous solutions. Chunshan Song et al [9], worked on deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel. It was clear that deep reduction of gasoline sulfur (from 330 to 30 ppm) must be made without decreasing octane number or losing gasoline yield. The problem is complicated by the high olefins contents of FCC naphtha which contributes to octane number enhancement but can be saturated under HDS conditions. Deep reduction of diesel sulfur (from 500 to <15 ppm sulfur) is dictated largely by 4,6-dimethyldibenzothiophene, which represents the least reactive sulfur compounds that have substitutions on both 4and 6-positions. The deep HDS problem of diesel streams is exacerbated by the inhibiting effects of co-existing polyaromatics and nitrogen compounds in the feed as well as H2S in the product. The approaches to deep desulfurization include catalysts and process developments for hydro-desulfurization (HDS), and adsorbents or reagents and methods for non-HDS-type processing schemes. His research on Desulfurization should also take into consideration of the fuelcell fuel processing needs, which will have a more stringent requirement on desulfurization (e.g., <1 ppm sulfur) than IC engines. Kyu-Sung Kim et al [10], have worked on removal of sulphur compounds in FCC raw C4 using activated carbon impregnated with CuCl and PdCl2 . They studied on several activated carbon(AC) based were of to develop a more efficient during the adsorbent FCC for

adsorbents removal

mercaptans

and sulfides

refinery

process. The

adsorbents were prepared

by impregnating AC with

CuCl and PdCl2 .Kyu-Sung Kim evaluate the degree of metal halide impregnation
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into the activated carbon support, and each adsorbent

was characterized by N2 adsorption, elemental analysis (EA) and XRF.

After repeating

the experminent several times he stated

the sulfur

adsorption capacities of adsorbents decreased in the following order : AC impregnated PdCl2, AC impregnated CuCl and non-impregnated

AC (NIAC). The saturated adsorbents were regenerated by toluene treatmentand reactivated at 130 C under a vacuum. Hisham S. Bamuflehet al [11], conducted several experiments on single and binary sulfur removal components from model diesel fuel using granular activated carbon. Sulfur compounds in diesel comprise mainly of alkylated benzothiophene (BT), dibenzothiophene (DBT) and its derivatives. They conducted several studies to desulfurize diesel fuel and opted

Hydrodesulfurization process (HDS) at high temperature (320380 8C) and high pressure (37 MPa) over CoMo or NiMo catalysts is which is currently a major process in petroleum refineries to reduce the sulfur in diesel fuel. Activated carbon surface structure and properties can be controllable to propose better adsorbents. They chose activated carbon was for refractory compounds desulfurization of liquid fuels such as fuel oil straight run gas oil and it showed high adsorptive capacity and selected the refractory sulfur compounds such as 4,6-DMDBT. Selective adsorption of 4,6-DMDBT using activated

carbonactivated prepared by ZnCl2 activator and prepared at differentconditions from dates stone is feasible, promising and worthfurther studying. The studies of dynamics desulfurizationby adsorption of DBT and 4,6-DMDBT from model andcommercial diesel in fixed bed adsorbers of activated carbon. Rosaset al [12], have done several experiments on desulfurization of low sulfur diesel by adsorption using activated carbon by adsorption isotherms .Diesel fuels with ultralow sulfur content (15 ppmw) can be contaminated when they are transported. Experiment conducted desulfurization of diesel fuel with 72 ppmw of sulfur in a batch system using four activated carbons at 303.15 K, atmospheric pressure, and magnetic stirring during 18 h was performed. Theycorrelates better the experimental behavior of this adsorbent. For sulfur
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removal of diesel from a total sulfur concentration of 72-15 ppmw, and recommended to process less than 4.2 g-D/g-A with the used activated carbons. Also, Celia Marin-Rosas recommended to make additional test to study the selectivity and competitively between the sulfur compounds and the rest of the organic compounds present into diesel fuel, such asaromatics, paraffins, isoparaffins, naphthenes, and olefins. Yang et al [13], have worked on Desulfurization of Liquid Fuels by Adsorption via Complexation with Cu(I)-Y and Ag-Y Zeolites. Fixed-bed adsorption using different -complexation adsorbents for desulfurization of liquid fuels was investigated. Cu(I)-Y (autoreduced Cu(II)-Y), Ag-Y, H-Y, and Na-Y zeolites were used to separate low-concentration thiophene from mixtures including benzene and/or n-octane, all at room temperature and atmospheric pressure. Sulfur-free (i.e., below the detection limit of 4 ppmw sulfur) fuels were obtained with Cu(I)-Y, Ag-Y, and H-Y but not Na-Y. Breakthrough and saturation adsorption capacities obtained for an influent concentration of 760 ppmw sulphur (or 2000 ppmwthiophene) in n-octane follow the order Cu(I)-Y > Ag-Y > H-Y > Na-Y and Cu(I)-Y > H-Y > Na-Y > Ag-Y, respectively.

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3. THEORY
3.1 Adsorption and types of adsorption:
Adsorption is a process that occurs when a gas or liquid solute accumulates on the surface of a solid or a liquid (adsorbent), forming a molecular or atomic film (the adsorbate). It is different from absorption, in which a substance diffuses into a liquid or solid to form a solution. The term sorption encompasses both processes, while desorption is the reverse process. Adsorption is operative in most natural physical, biological, and chemical systems, and is widely used in industrial applications such as activated charcoal, synthetic resins and water purification. Similar to surface tension, adsorption is a consequence of surface energy. In a bulk material, all the bonding requirements (be they ionic, covalent or metallic) of the constituent atoms of the material are filled. But atoms on the (clean) surface experience a bond deficiency, because they are not wholly surrounded by other atoms. Thus it is energetically favourable for them to bond with whatever happens to be available. The exact nature of the bonding depends on the details of the species involved, but the adsorbed material is generally classified as exhibiting physisorption or chemisorption. Physisorption or physical adsorption is a type of adsorption in which the adsorbate adheres to the surface only through Vander Waals (weak intermolecular) interactions, which are also responsible for the non-ideal behaviour of real gases. Chemisorption is a type of adsorption whereby a molecule adheres to a surface through the formation of a chemical bond, as opposed to the Van der Waals forces which cause physisorption.

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Adsorption is usually described through isotherms, that is, functions which connect the amount of adsorbate on the adsorbent, with its pressure (if gas) or concentration (if liquid). One can find in literature several models describing process of adsorption, namely: Freundlich isotherm, Langmuir isotherm, BET isotherm, etc. Table 3.1 Comparison between Physisorption and Chemisorption Physisorption Chemisorption

Low heat of adsorption usually in the High heat of adsorption in the range range of 20-40 kJ mol-1 of 40-400 kJ mol-1

Force of attraction are Van der Waal's Forces of attraction are chemical forces It usually takes place at low temperature and decreases with increasing It takes place at high temperature bond forces

temperature It is reversible It is irreversible

It is related to the ease of liquefaction of The extent of adsorption is generally the gas It is not very specific It forms multi-molecular layers It does not require any activation energy not related to liquefaction of the gas It is highly specific It forms monomolecular layers It requires activation energy

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Factors affecting adsorption: The extent of adsorption depends upon the following factors: Nature of adsorbate and adsorbent. The surface area of adsorbent. Activation of adsorbent. Experimental conditions. E.g., temperature, pressure, etc.

3.2 Applications of adsorption:

The principle of adsorption is employed, 1. In heterogeneous catalysis. 2. In gas masks where activated charcoal adsorbs poisonous gases. 3. In the refining of petroleum and decolouring cane juice. 4. In creating vacuum by adsorbing gases on activated charcoal. 5. In chromatography to separate the constituents' of a mixture. 6. To control humidity by the adsorption of moisture on silica gel.

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Important Adsorbents and their Uses: Silica Gel: Drying of gases, refrigerants, organic solvents, transformer oils Desiccant in packings and double glazing Dew point control of natural gas Activated Alumina: Drying of gases, organic solvents, transformer oils Removal of HCl from hydrogen Removal of fluorine in alkylation process Carbons: Nitrogen from air Hydrogen from syngas Ethene from methane and hydrogen Clean-up of nuclear off-gases Water purification Zeolites: Oxygen from air Drying of gasses Removing water from azeotropes Sweetening sour gases and liquids Purification of hydrogen Separation of xylenes and ethyl benzene Polymers and Resins: Water purification Recovery and purification of steroids, amino acids Separation of fatty acids from water and toluene

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3. 3. Methods for Desulfurization

Hydrodesulphurization process (HDS) at high temperature (320380 8C) and high pressure (37 MPa) over CoMo or NiMo catalysts was a major process in petroleum refineries to reduce the sulphur in diesel fuel. The major sulphur compounds existing in current commercial diesel are the alkyl dibenzothiophenes (DBTs) with one or more alkyl groups at 4 or/and 6 positions which have been considered to be refractory sulphur compounds in the fuel due to the steric hindrance of the alkyl groups in HDS. This process is highly efficient for the removal of thiols, sulfides, and disulfides.However, it is difficult to reduce sulphur levels to an ultra low level using the HDS process because of the very low reactivity of the HDS catalysts towards sulphur compounds and also towards refractory sulphur-containing compounds such as dibenzothiophene and its derivatives especially 4,6-dimethydibenzothiophene (4,6-DMDBT). An increase in the reactor size and hydrogen consumption is required to achieve high levels of desulphurization. Other methods, such as oxidative desulphurization and bio-

desulphurization, have shown good potential for removing refractory sulphur under mild conditions. This process is based on the well known propensity of organic sulphur compounds to be oxidized; it consists of an oxidation followed by the extraction of the oxidized products. The greatest advantage of oxidative desulphurization and bio-desulphurization, compared with the conventional HDS technology, is that they can be carried out in the liquid phase under very mild conditions near room temperature and under atmospheric pressure. The advantage of BDS is that it can be operated in conditions that require less energy and hydrogen. BDS operates at ambient temperature and pressure with high selectivity, resulting in decreased energy costs, low emission, and no generation of undesirable side products. Over the last two decades several

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research groups have attempted to isolate bacteria capable of efficient desulphurization of oil fractions. ODS offers several advantages compared with HDS. For example, the refractory-substituted dibenzothiophenes (DBTs) are easily oxidized under low temp and pressure conditions so expensive hydrogen is not required and, therefore, the capital requirement for an ODS unit is significantly less than that for a deep HDS unit.Currently, the main obstacles to the industrial application of ODS are (1) their low-oxidation activity and their low selectivity for the sulfides present in fuel oils, (2) the difficulties in separation and recovery of the catalysts after the reactions, (3) the low utilization efficiency of H2O2, and (4) the introduction of other components to the oxidation systems. Desulphurization of commercial fuels by selective adsorption has been reported as an alternative technology for the current HDS method. Yang and coworkers reported using zeolites for selective adsorption under ambient conditions for the desulphurization of commercial fuels [6-10]. Metal ionexchange Y zeolites have also been shown to effectively remove sulphur compounds under ambient conditions. However, the sulphur adsorption capacity depends on the composition of the fuel. Adsorptive removal of sulphur compounds from liquid commercial fuels has been widely investigated using various different adsorbents. Ag-Y and Cu-Y zeolites have been shown to have a particularly high adsorption capacity and selectivity for thiophene and its derivatives. The advantages of using absorbents, such as the low-energy demands of the process, potential to regenerate the spent adsorbent, and broad availability of adsorbents, have made adsorption processes an attractive area of research.

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Methods available for De-sulfurization

decompostion of sulphur compounds with hydrocarbon return
conventional HDS HDS with octane recovery selective oxidation reactive adsorption bio-desulfurization

seperation of Scompounds without S elimination

alkylation extraction oxidation to sulfones precipitation adsorption

combination combinationseperation +decomposition

catalytic distillation

Figure 3.1 .1 Methods for Desulfurization

3.4 Gas Chromatograph Chromatography:

Gas chromatography is used to identify and quantitate individual components in a mixture. Quantitation uses chromatographic data to determine the amount of a given component in a mixture and the data can be in the form of either peak height or peak area which is obtained from an integrated chromatogram.

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Figure 3.2 Schematic Layout of GC

Quantitative Methods
The most common methods used are Area percent, Single point external standard,Multiplepoint external standard, Single point internal standard and multiple point internal standards. Among those:

Area Percent Method: This method provides a rough estimate of the amounts
of analytes present and for calculating area percent take the area of an analyte and divide it by the sum of areas for all peaks. This value represents the percentage of an analyte in the sample.

Single Point External Standard: Analyze a sample containing a known

amount of analyte or analytes and record the peak area. Then calculate a response factor.

Response factor = (Peak area / sample amount)

after getting the response factor we can calculate the amount of unknown analyte of the sample

Amount of analyte=(Peak area / response factor)

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Procedure:
When a sample is injected into the correct column, a carrier gas sweeps the sample through the column. If necessary, an oven heats the system to vapourize the sample and speed its passage through the column. The different components of the sample will be separated by the column because each of the components sticks to the liquid coating that on the column packing differently. The greater the stickiness the longer it takes for a substance to pass through the column. When a substance leaves the column, it is sensed by a detector. The detector generates a voltage that is proportional to the amount of the substance. The signal from the detector is then displayed by a chart recorder and/or fed into a computer. Modern gas chromatographs are connected to a computer which displays the peaks of all the substances in the sample. This is called the chromatogram. The time that it takes a substance topass through the instruments from injection to detection is called retention time. The retention time is measured from the injection point topeak height. The amount of substance in a sample is proportional to the area under the peak of that substance and that proportionality constant is different for each substance and detector. Chromatography(GC) is a method of separating volatile compounds so that they may detected individually in complex mixtures. Compounds are separated based on differences in their vapour pressures and their attraction to solid materials inside the instruments. Because the vapour pressure of a given compound is a function of intermolecular forces between molecules, GC takes advantages in differences in at least one of the properties of matter In GC, the sample is injected into the instrument using a small syringe. The sample is swept into the instrument using a carrier gas where the sample is separated into its individual chemical components, called analytes. Separation is
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achieved by both attraction to the stationary phase and differences in vapour pressure. Because vapour pressure varies with temperature, the temperature of the instrument is often adjusted during the chromotoraphic run. A detector, which is designed to sense analyte molecules as they exit the GC, is at the exit of the column. Because the analyte molecules bind differently to the stationary phase, they travel through the GC column at different rates. That is, they have different retention times on the column. As an analyte appears in the detector, its presence is signaled by a peak. Thus, a gas chromatogram consists of a series of peaks,one for each of the components of the sample. The chromatogram is displayed on a chart recorder or computer screen. Gas chromatography is an instrumental method for the separation and identification of chemical compounds. Chromatography involves a sample being dissolved in a mobile phase. The mobile phase is then forced through an immobile, immiscible stationary phase. The phases are chosen such that components of the sample have differing solubilites in each phase. A component that is quite solute in the stationary phase will take longer to travel through it than a component that is not very soluble in the stationary phase but very soluble in the mobile phase. As a result of these differences in mobilities, sample components will become separated from each other as they travel through the stationary phase. After the separation of the compounds, Flame Ionization Detector(FID) is used to identify each of them and determine their mass. The effluent from the column is mixed with hydrogen and air, and ignited. Organic compounds burning in the flame produce ions and electrons that can conduct electricity through the flame. A large electrical potential is applied at the burner tip, and a collector electrode is located above the flame. The current resulting from the pyrolysis of any organic compounds is measured. FID s are
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mass sensitive rather than concentration sensitive; this gives the advantage that changes in mobile phase flow rate do not affect the detectors response. The FID is a useful general detector for the analysis of organic compounds; it has high sensitivity, a large linear response range, and low noise. It is also robust and easy to use, but it destroys the injected sample. After detection, a signal is sent to the recording device. Each analyte in a sample will have different retention time. The time taken for the mobile phase to pass through the column is called tM. A GC can separate the compounds, but cannot identify them itself. By calibrating GC you can find out at what time various organic compounds are being detected. The area under the curve may be expressed in terms of concentration of the pollutant, by running some calibration standards at known concentration.

Calculating the Area: The area of a peak is proportional to the amount of the
compound that is present. The area can be approximated by treating the peak as a triangle. The area of a triangle is calculated by multiplying the height of peak times its width at half height.

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4. EXPERIMENTAL PROCEDURE
Adsorbent properties: 1. cbv-3020 (H-ZSM-5) Si/Al Pore size Pore Volume = 33 = 0.54 mm = 0.19 ml/gm

2. cbv 20A: (Hmodermite-c) Si/Al Surface Area =20 =420 m2/gm

Nominal Cation form = H2

Ag-Y Zeolite Adsorbent Preparation:

As Na in Na-Y zeolite is less active towards sulphur, it is better to replace the Na with Cu or Ag(which are more active towards sulphur). To prepare 0.2M Ag-Y Zeolite adsorbent , take 60ml distilled water in a 250ml conical flask and add 2gms of Na-Y zeolite and 2gms of AgNO3(Silver Nitrate). Keep this solution away from sunlight by keeping in a dark room for 48 hours. After 48 hours filtrate the solution by using filter papers and dry it. Later wash the dried filtrate with distilled water. Again filter the solution and dry it. The required Ag-Y Zeolite is prepared[9].

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Procedure:
Take 3 conical flasks of 50 ml volume. Fill these conical flasks with 10 ml toluene in each with the help of burette. To make a 500 ppm of sulphur content, add 5 milligrams of Thiophene in each flask. Measure the Thiophene peaks of each flask with the help of Gas Chromatography Equipment for one of the adsorbent. And then add available adsorbents like zeolites, activated carbon etc. Before adding the adsorbents, they have to be activated at 110 C in heater. After activating the adsorbents, add 1gm of each adsorbent in each conical flask. After adding adsorbents, keep these flasks in shaker for 24hours. After 24 hours of shaking, filtrate the solutions and measure the sulphur content in each flask with the help of Gas Chromatography Equipment. The percentage of suphur removal and the amount of sulfur adsorbed onto the adsorbent were measured using the expressions Percentage sulfur removal = 100*(C0Cf)/C0 Amount of adsorbed sulfur per gram of solid =(C0Cf)/m where, C0 is the initial sulfur concentration (mg/l), Cf is final sulfur concentration (mg/l) and mis the adsorbent dose in grams per litre of solution

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Table 4.1 Gas Chromatography Operating Conditions:

COLUMN USED INJECTION TEMPERATURE COLUMN TEMPERATURE FID TEMPERATURE SPLIT RATIO ZB WAX PLUS 250C 120C 250C 100

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5. RESULTS AND DISCUSSION

Table 5.1: Percentage of sulphur removal

Adsorbent

INITIAL CONC

FINAL CONC

% REMOVED

cbv-3020

500

97

80

cbv-720

500

337.2

33.56

H-zeolite

500

207.3

58.5

Ag-Y

500

148.5

70.3

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6.0

5.0

Amount of sulfur adsorbed mmol/gm

4.0

3.0

2.0

1.0

0.0 Cbv 3020 zeolite Hbeta zeolite Cbv 720 zeolite Ag-y zeolite

Figure 5.1: The amount of sulphur adsorbed in mmol/gm on different adsorbents

90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 Cbv 3020 zeolite Hbeta zeolite Cbv 720 zeolite Ag-y zeolite % sulfur removed

Figure 5.2: The percentage of sulphur removal on four adsorbents.

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Table 5.1shows the initial and final concentrations of the thiophene-toluene solutions onto the different zeolites. Figure 5.1 shows the amount of sulphur adsorbed in mmol by the various adsorbents for 1gm of sample solution taken.While Figure 5.2 shows the percentage of sulfur removed by various adsorbents and all the experiments were carried out at normal atmospheric conditions ie., room temperature. The amount of thiophene adsorbed onto the cbv-3020 is 4.78 mmol/gm and it can be seen that the cbv-3020 zeolite is a very efficient zeolite for desulfurization. Whereas Xiao et al suggested that Ag-Y zeolite interaction towards thiophene is more compared to Na-Y zeolite. So in our laboratory we attempted to synthesize the modified Zeolite ie.,replacing the Na+ metal ion in Na-Y zeolite with Ag+ metal, and we observed the amount of thiophene adsorption is higher than the Na-Y zeolite. On interpreting the results we find that the cbv-3020 zeolite is having higher adsorption, due to its large surface area and pore size. The pore size of cbv-3020 zeolite adsorbent is 0.54mm which is higher than the other adsorbents and allowing more thiophene molecules to accommodate in its pores. Whereas H zeolite, due to its low surface area and pore size cannot adsorb sulphur efficiently.

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6. CONCLUSION
Conventional HDS process is highly efficient for the removal of thiols, sulfides, and disulfides. However, it is difficult to reduce sulphur levels to an ultra- low level because of the very low reactivity of the HDS catalysts towards sulphur compounds and also towards refractory sulphur-containing compounds such as di-benzothiophene and its derivatives. Adsorption is also another method available for the removal of sulfur at ambient temperature and pressure and this process can be worked out without using hydrogen. The reactivity order of sulfur components is Thiophene > Benzothiophene > Dibenzothiophene.

Initially our experiments carried out on thiophene removal on different zeolites at room temperature in order to understand the interaction of thiophene molecule with different metal ions in zeolites. The adsorption capacity increases in the order of cbv 3020>AgY>H zeolite>cbv 720. The larger adsorption is due to stronger interaction towards metal ion. The adsorbent cbv-3020 was very effective in removal of sulphur and we also observed that Ag-Y zeolite was effective in removing sulphur from toluene-thiophene solution, however, due to the presence of unavoidable impurities and experimental errors, resulted in significantlycompromised adsorption performance in our tests.

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7. REFERENCES
[1] David L. King *, Liyu Li Removal of sulfur components from low sulfur gasoline usingcopper exchanged zeolite Y at ambient temperatureCatalysis Today 116 (2006) 526529 [2] Jing Xiao, Zhong Li,* Bing Liu, Qibin Xia, and Moxin Yu Adsorption of Benzothiophene and Dibenzothiophene on Ion-Impregnated Activated Carbons and IonExchanged Y Zeolites
Energy & Fuels 2008, 22, 38583863

[3]David L. King *, Liyu Li Removal of sulfur components from low sulfur gasoline using copper exchanged zeolite Y at ambient temperatureCatalysis Today 116 (2006) 526529 [4] AnkurSrivastav, Vimal Chandra Srivastava Adsorptive desulfurization by activated aluminaJournal of Hazardous Materials 170 (2009) 11331140 [5]I.V. Babich*, J.A. Moulijn Science and technology of novel processes for deep desulfurization of oil refinery streams: a reviewFuel 82 (2003) 607631 [6] G.Blanco-Brieva, J.M.Campos-Martin, S.M.Al-Zahrani REMOVAL OF REFRACTORY ORGANIC SULFUR COMPOUNDS IN FOSSIL FUELS USING MOF SORBENTS
Global NEST Journal, Vol 12, No 3, pp 296-304, 2010

[7] ChetanBorkar, DheerajTomar, and Sasidhar Gumma* Adsorption of Dichloromethane on Activated CarbonJ. Chem. Eng. Data 2010, 55, 16401644 [8] I.HilalGbbk, RamazanGp, Mustafa Ersz Synthesis, characterization, and sorption properties of silica gel-immobilizedSchiff base derivativeJournal of Colloid and Interface Science 320
(2008) 376382

[9] ChunshanSongAn overview of new approaches to deep desulfurization forultra-clean gasoline, diesel fuel and jet fuelCatalysis Today 86 (2003) 211263 [10] Kyu-Sung Kim, Sun Hee Park, Ki Tae Park, Byung-Hee Chun, and Sung Hyun Kim Removal of sulfur compounds in FCC raw C4 using activated carbon impregnated with CuCl and PdCl2Korean J. Chem. Eng., 27(2), 624-631 (2010) [11] Hisham S. Bamufleh Single and binary sulfur removal components from model diesel fuel using granular activated carbon from dates stones activated by ZnCl2Applied Catalysis A:
General 365 (2009) 153158

[12] CeliaMarn-Rosas,*, Luis F. Ramrez-Verduzco, Florentino R. Murrieta-Guevara, Gonzalo Hernandez-Tapia, and Luis M. Rodrguez-Otal Desulfurization of Low Sulfur Diesel by Adsorption Using Activated Carbon:Adsorption IsothermsInd. Eng. Chem. Res. 2010, 49,
43724376

[13] Arturo J. Hernandez-Maldonado and Ralph T. Yang Desulfurization of Liquid Fuels by Adsorption via Complexationwith Cu(I)-Y and Ag-Y ZeolitesInd. Eng. Chem. Res. 2003, 42, 123129

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8. APPENDIX
SAMPLE1

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SAMPLE 1 (AFTER ADDING ADSORBENT :CBV-3020)

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SAMPLE: 2

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SAMPLE 2( AFTER ADDING ADSORBENT:CBV 720)

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SAMPLE 3

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SAMPLE3 (AFTER ADDING ADSORBENT :H ZEOLITE)

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SAMPLE 4:

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SAMPLE 4(AFTER ADDING ADSORBENT: AG-Y ZEOLITE)

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