Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
  • C10G21/12—Organic compounds only
  • C10G21/14—Hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
  • C10G19/073—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with solid alkaline material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
  • C10G29/04—Metals, or metals deposited on a carrier
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/201—Impurities
  • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/40—Characteristics of the process deviating from typical ways of processing
  • C10G2300/44—Solvents
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
  • C10G31/09—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by filtration

Definitions

• the present disclosure relates to desulphurization processes. Particularly, the disclosure relates to a process for desulphurization of petroleum heavy oils and residual petroleum oils, more particularly carbon black feed oil.
• Petroleum oils are complex mixtures of primarily hydrocarbons and other carbon containing compounds.
• the overall composition of the petroleum oil or crude oil is known to vary significantly from its origin or geographical location of the refinery.
• the elemental composition of these oils consists of about carbon (84-87%), hydrogen (12-14%) along with oxygen, nitrogen, sulfur, moisture and ash.
• the sulfur content may vary substantially from 0.2 - 8%.
• the crude oils may also contain hydrocarbons, paraffins, asphaltenes, resins and ash.
• the crude oil compositions can be differentiated into various individual fractions at different boiling ranges.
• the low boiling fractions are typically napthas, those between 180 - 250°C are kerosene and the ones boiling in the range of 250 - 350 °C are termed as gas oils.
• the fractions boiling above 350°C are generally termed as residues and are obtained after all or most of the distillable products have been removed from the petroleum oil. These residue fractions could be further distinguished as light vacuum gas oils, heavy vacuum gas oils and vacuum residues.
• Each of these different fractions has different molecular distribution of various hydrocarbon species and related compounds. In particular, one of the significant aspects is the distribution of sulfur containing species in these fractions.
• the use of the petroleum oil residues includes heating (as a fuel), and as a feedstock for the manufacture of carbon black.
• the presence of sulfur in the petroleum oil residue has a number of shortcomings. During the complete or partial combustion of the petroleum residue, sulfur gets converted to SO 2 and SO 3 . These cause major environmental issues in the form of acid rains and adversely affect health. Further, the sulfur species cause poisoning of catalyst systems used in the refineries. These are also known to be the primary cause of corrosion of equipments and exhaust. The presence of sulfur in the residue fraction has further ramifications in case of use of this as raw material for carbon black manufacturing. Apart from significant air pollution, these species remain associated with the final carbon black product which is detrimental to various applications. Furthermore, high sulfur content affects the throughput of the manufacturing process.
• Carbon black feed oil is a raw material used for manufacturing carbon black, an important material used in the tyre industry.
• Carbon black feedstock is a mixture of C 12 and higher components rich in naphthalene, methylindenes, anthracene, fluorene and other poly-aromatic components.
• CBFO is essentially procured either from oil refineries or from coal tar distillers. There are two types of CBFO viz. High BMCI type and General type. "BMCI" (Bureau of Mines Co-relation Index) effectively measures the degree yield of carbon black. Higher the BMCI, better the yield of carbon black.
• High BMCI CBFO is used as a raw material by carbon black manufacturers while the other grade is used by various consumers to manufacture rubber process oils, incense sticks etc.
• a desulphurization process is usually carried out to remove sulfur (S) from natural gas and petroleum products such as gasoline or petrol, jet fuel, kerosene, diesel fuel and fuel oils.
• the refinery feedstock contains a wide range of organic sulfur compounds, including thiols, thiophenes, organic sulfides, disulfides and many others. These organic sulfur compounds are the products of degradation of sulfur containing biological components, present during the natural formation of the fossil fuel, petroleum crude oil.
• the purpose of removing sulfur is to reduce sulfur dioxide (SO 2 ) emissions that result from using these fuels in automotive vehicles, aircrafts, railroad locomotives, ships, gas or oil burning power plants, residential and industrial furnaces, and other forms of equipment using fuel for combustion.
• the hydro-desulfurization is commonly used for this purpose. This process is based on catalytic hydrogenation of the sulfur species to convert it into H 2 S.
• the hydro-desulfurization is known to work efficiently on lower boiling fractions such as gasoline, naptha, kerosene, and the like.
• the catalyst systems generally include transition metals such as Ni, Co, Mo supported on Al 2 O 3 .
• the high boiling fractions or resids contain sulfur species that are part of the more stable ring compounds such as substituted benzothiophenes and higher derivatives or large molecule ring compounds which are extremely difficult to desulfurize.
• Some prior art examples for treating residues by hydro-desulfurization include US2640011 , US2992182 , US4328127 and US4576710 .
• the treatment parameters are extreme i.e. use of high temperatures in excess of 400°C and pressures in excess of 1000 psig.
• the desulfurization efficiencies are low. Further, due to these difficult processing conditions hydro-desulfurization results in coke formation, leading to deactivation of the catalyst systems.
• H 2 S hydro-desulfurization process results in the formation of H 2 S; which again cannot be disposed, off due its environmental concerns.
• the common oxidizing agents used are H 2 O 2 or H 2 O 2 in combination with acetic acid and in the presence of an oxidizing catalyst system.
• tert -butyl hydroperoxide can also be used as an oxidant as it tends to be soluble in oil.
• the adsorptive processes generally use absorbents such as clay, Al 2 O 3 , bauxite, transition metal oxides systems supported on silica or alumina, zeolites, activated carbon, etc.
• Another such desulfurization process is based on the use of alkali metal, especially sodium metal as the desulfurizing agent.
• the sulfur is primarily removed as a metal sulfide instead of the removal of the entire sulfur containing molecule.
• Some typical prior art examples of this process are US1938672 , US1952616 , US2902441 , US3004912 , US3093575 , US3617530 , US3755149 , US3787315 , US4003824 , US4120779 , US4123350 , US4147612 , US4248695 , US4437980 , US6210564 , US7192516 , US7507327 , US7588680 .
• the sodium metal can be used as pure metal or in an alloy, supported on inert species, or as dissolved in solvent such as ammonia. Also, these processes use hydrogen at high pressures in combination to the sodium metal for desulfurization. In some processes, sodium-based compounds such as NaHS, NaNH 2 , and the like, are used for the desulfurization. A major product formed as a reaction of the sodium metal with the sulfur in the feed oil is sodium sulfide (Na 2 S). Some of the above-mentioned prior art documents also describe the regeneration of sodium from Na 2 S.
• GB441703 discloses a process for desulphurization of petroleum oils, comprising the following steps : transferring the petroleum oil to a reactor vessel, adding solid sodium metal to the petroleum oil in the reactor vessel with a concentration up to 20%, reacting the petroleum oil with sodium at a temperature in the range of 240-350°C under mixing, cooling the resultant mixture, decanting and filtering.
• US2007295640 discloses a composition for reducing the viscosity of heavy oils; the nature of the petroleum oil solvent: alkanes, alkenes; cyclic-alkenes; n-hexane, cyclohexane, heptane, pentene, hexene, heptene; toluene and xylene; and the concentration of the petroleum oil solvent: 5 to 50%; the separation and recovery of the solvent is performed by distillation.
• US5935421 discloses a process for desulphurization of petroleum oils, comprising a step of reacting solid sodium metal with the oil in the temperature range of 260-400°C with a hydrogen pressure of 690-4825 kPa (100-700 psi) and for the amount of treatment time 2-90 minutes.
• the known desulphurization processes are associated with a number of limitations such as low yield of desulphurized feed oil, formation of large amount of insoluble sludge, requirement of hydrogen and safety issues.
• the inherent high viscosity of heavy oils and petroleum residues makes it difficult for the processing and separation operations before and after the desulphurization process.
• the present invention is an improved process for petroleum oil desulphurization, especially carbon black feed oil (CBFO) desulfurization, which reduces the sulfur content in the oil.
• CBFO carbon black feed oil
• An object of the present disclosure is to provide a process for desulphurization of carbon black feed oil which provides improved yield and high quality of desulphurized oil.
• Another object of the present disclosure is to provide a process for desulphurization of carbon black feed oil with improved processing and handling operations.
• Yet another object of the present disclosure is to provide a process for desulphurization of carbon black feed oil without the use of hydrogen.
• Another object of the present disclosure is to provide a process for further treatment of the desulfurized oil for removal of the residual sodium content.
• the hydrocarbon organic solvent is selected from a group consisting of n-hexane, cyclohexane, heptane, pentene, hexene, heptene, octene, toluene and xylene.
• the process includes the step of purging the reactor vessel with hydrogen gas at a pressure in the range of 101 - 3550 kPa (0 - 500 psig).
• the process includes the step of separating the organic solvent from desulfurized petroleum oil by distillation.
• the process includes the step of mixing sodium with the oil-solvent mixture in the reactor vessel by using high shear mixing by means of a mixer selected from an inline mixer, a mechanical mixer, a pump around loop and an ultrasonic mixer.
• a mixer selected from an inline mixer, a mechanical mixer, a pump around loop and an ultrasonic mixer.
• a process for removing residual sodium metal including the steps of: treating the desulfurized petroleum oil with 0.1 - 10 % carboxylic acid in an organic solvent, on a volume basis, at a temperature in the range of 50 - 150°C for 30 minutes to 90 minutes under vigorous stirring; and filtering the resultant mixture to obtain desulfurized petroleum oil having sodium content between 10 - 50 ppm.
• the carboxylic acid is selected from acetic acid, formic acid and propionic acid.
• the carboxylic acid organic solvent is selected from alkanes, alkenes, cyclic alkenes, alkynes and alcohol. More preferably, the carboxylic acid organic solvent is xylene.
• a process for removing residual sodium metal by purging the desulfurized petroleum oil with air at a temperature in the range of 30 - 150°C.
• the present disclosure relates to a process for desulphurization of carbon black feed oil (CBFO).
• the feed oil (CBFO) has high viscosity at ambient conditions.
• the process comprises diluting the feed oil with a suitable organic solvent, prior to the desulphurization reaction.
• the organic solvent can be selected from the group of hydrocarbon solvents consisting of alkanes, alkenes, cyclic alkenes and alkynes.
• other oils such as petrol, kerosene, crude oil, and the like, can also be used for diluting the feed oil.
• the organic solvent is particularly selected from the group consisting of n-hexane, cyclohexane, heptane, pentene, hexene, heptene, octene, toluene and xylene, preferably the solvent is xylene.
• the ratio of the organic solvent to petroleum oil in the oil-solvent mixture is in the range of 50:50 - 20:80, on the basis of the weight in g of petroleum oil and the volume in ml of the hydrocarbon organic solvent in the mixture.
• the feed to the process of the present disclosure is carbon black feed oil having a sulfur content in the range of 0.1 % - 20 %.
• the process of the present disclosure can also be used for petroleum oils of various boiling fractions.
• the process of the present disclosure can be used to desulphurize coal tar, shale oil or other organic sulfur bearing compounds.
• the organic solvent is removed after the desulphurization process.
• the present process results in a desulphurized stream (after xylene removal) with a substantial viscosity reduction.
• the formation of insoluble sludge (unusable material) due to polymerization reactions of the desulphurized species is reduced due to improvement in the feed oil viscosity.
• the improvement in the feed oil viscosity enhances the processing of the feed oils required in applications such as manufacturing of carbon black product.
• the process results in improvement of feed oil quality by means of reducing the asphaltene content in the feed oil.
• Asphaltenes are considered as the n-heptane insoluble, toluene soluble components of a carbonaceous material such as crude oil, bitumen or coal. Asphaltenes are high molecular weight hetero-atom species that are generally considered detrimental to the quality of the processed carbon black product.
• the process of the present disclosure is carried out in the absence of hydrogen at a pressure in the range of 101 - 3550 kPa (0 - 500 psig), this results in an higher C:H ratio of the processed oil as compared to processes carried in the presence of high pressure hydrogen. This is beneficial for converting most of the processed oil into carbon black, as the hydrogen leaves the process in the form of water vapor without contributing to the formation of product.
• the process removes moisture present in the CBFO.
• the CBFO generally contains about ⁇ 1% moisture.
• Na metal is known to have strong affinity to water and thereby react with moisture.
• the present process uses sodium metal in a concentration between 0.1 - 20 % of the CBFO oil concentration, on a weight basis. Thus, moisture present in the CBFO is completely removed.
• the process is carried out in the presence of hydrogen.
• the hydrogen added could be in the range of 101 - 3550 kPa (0 - 500 psig), preferably in the range of 101 - 2170 kPa (0 - 300 psig), and more preferably in the range of 101 - 791 kPa (0-100 psig).
• the hydrogen may not be present in the form of closed system i.e. under no hydrogen pressure or a pressureless system. Thus, it could be added in a continuous or a semi continuous flow of hydrogen gas.
• the process of desulphurization of the present disclosure gives crystalline sodium sulfide as the by-product.
• the by-product so formed is easier to separate and filter and thus results in a better recovery of the desulfurized oil as well as better separation and processing efficiency of the desulfurized oil.
• An important aspect of the present disclosure is that it provides a process for reducing the size of dispersed sodium - as solid particles or molten form as droplets. Finer dispersion of sodium metal increases the efficiency of the desulphurization process.
• the by-product, sodium sulfide tends to cover the surface of sodium metal thereby reducing the efficiency of the process. Therefore, mixing, preferably high shear mixing, for a duration in the range of 15 minutes - 4 hours at a temperature in the range of 240 - 350°C is provided; high shear mixing causes the breaking of sodium sulfide and thereby provides new sodium surfaces for enhancing the reaction. Any form of mixing may be used, such as an inline mixer, a pump around loop, a mechanical mixer, or an ultrasonic mixer, that provides the required amount of dispersion to the sodium metal.
• the pure CBFO has a high viscosity of above 1500 mPa.s (1500 cP) at ambient conditions.
• the process of the present disclosure results in a desulfurized stream (after xylene/solvent removal) having a substantial viscosity reduction to the range of 100 - 150 mPa.s (100 - 150 cP) at ambient conditions.
• the overall effect is that the desulphurization process is carried out in the absence of hydrogen and results in lower loss of feed oil caused by insoluble sludge formation as well as improvement in the feed oil viscosity which is further expected to enhance the characteristics of the processed carbon black product.
• the process of the present disclosure can also be extended by means of carrying the desulphurization with Na and organic solvent, along with hydrogen. These results with simultaneous presence of organic solvent and hydrogen before desulphurization also show benefits in terms of product quality and yield, wherein the desulfurized feed oil yield is greater by 15 - 20 % as against the known processes. The scope of our process could thus be further extended as an improved desulphurization process involving simultaneous use of organic solvent and hydrogen, however, in an optimized combination (or absence) of each of the reactants.
• Another aspect of the process of the present disclosure is the by-product formation and processing after the desulphurization reaction.
• the desulphurization of feed oil using Na metal results in the formation of Na 2 S as the by-product.
• a large amount of valuable residual CBFO is lost as it remains associated to this Na 2 S residue or unreacted sodium in the form of a highly viscous sludge.
• the presence of organic solvent in the feed oil prior to the desulphurization reaction results in the formation of a crystalline and pure by-product. This product is easier to separate and filter as there is substantially less CBFO loss. This results in a better recovery of the desulphurized oil as well as a better separation and processing efficiency post the desulphurization reaction.
• the present disclosure uses high shear mixing apparatus aimed at reducing the size of dispersed sodium - as solid particles or molten form as droplets. This gives finer dispersion of sodium metal in the feed oil which increases the desulphurization efficiency of the process. Secondly, during the desulphurization process, the by-product formed tends to cover the surface of sodium metal thereby reducing the efficiency.
• the high shear mixing helps in breaking these surfaces and bringing new sodium surfaces for enhancing the reaction. Any form of mixing may be used, such as an inline mixer, a pump around loop, a mechanical mixer, or an ultrasonic mixer, that provides the required amount of dispersion to the sodium metal.
• the carbon black feed oil is highly viscous with a viscosity of above 1500 mPa.s (1500 cP) at ambient conditions. Addition of organic solvent prior to desulphurization reduces its viscosity to a substantial extent (less than 50 mPa.s (50 cP) at ambient conditions, depending upon the amount of solvent added), making it simpler to transfer and handle as well as facilitate better mixing and contact with other reactants.
• the density of CBFO is also high, typically between 1.01 - 1.08 g/cm 3 .
• the density of sodium solid at 30 °C is about 0.96 g/cm 3 and that of molten sodium is about 0.927 g/cm 3 .
• a process for removal of residual sodium metal from the desulphurized oil is also disclosed.
• the sodium metal gets finely dispersed in the oil.
• some sodium metal invariably remains in the system either as a suspension or bound to the molecular chain in the oil.
• the separation or removal of this sodium from the oil system is considerably difficult by means of pure mechanical processes.
• the presence of this residual sodium even in trace quantities has serious implications on the overall quality of product for the carbon black Industry.
• the process of the present disclosure uses acetic acid in the organic solvent mixture.
• the role of acetic acid is that of scavenging the sodium metal and the organic solvent promotes a better mixing between the feedstock oil and acetic acid.
• various carboxylic acids such as formic acid, propanoic acid, and mixtures thereof, can be used.
• ethanol and such alcohols can also be used for scavenging the sodium.
• the residual sodium removal was also achieved by purging the oil with air at elevated temperatures between 30 - 150°C. Such treatment is not limited to air alone and would cover other gaseous agents such as oxygen, ozone, etc.
• the reactor vessel was first purged with nitrogen to remove air, and then the vessel was purged with hydrogen gas. The reactor was then pressurized up to 2170 kPa (300 psig) with hydrogen. The reactor was subsequently heated to a temperature of 290 °C. The reaction was carried out at this temperature for a period of 4h. The entire solution was allowed to cool down to room temperature and then the CBFO was decanted. The decanted solution was filtered out and analyzed for sulfur content by XRF (X-ray Fluorescence Spectroscopy). Similarly, the desulfurization process was carried for other varying CBFO : Xylene ratios viz. 70:30, 80:20 (as shown in examples 2 and 3 in TABLE 1).
• XRF X-ray Fluorescence Spectroscopy
• Asphaltenes are found to be detrimental for the carbon black quality as well as manufacturing processes during carbon black formation.
• the asphaltene content for treated oil and untreated oil was carried by determining the n-heptane insoluble content in both the oils. It was observed that the asphaltene content of untreated oil was 10.59 %. However, the asphaltene content of the treated oil was substantially reduced to 4.65 %. This indicated that our process is capable of reducing the asphaltene content by over 50 %.
• Example 9 appropriate amounts of CBFO : Xylene (70:30) mixture was taken in the high pressure reactor. 13.5 g of Na metal was added and the reactor was pressurized with hydrogen to a pressure of about 2170 kPa (300 psig). The reactor was then heated to a temperature of 240 °C with a residence time of 1 h. The reactor was cooled and the CBFO decanted and analyzed for the sulfur content. A desulfurization efficiency of 10 % was obtained in this case suggesting that the minimum temperature where effective desulfurization can be carried out was 240°C.
• the minimum temperature required for the desulfurization reaction was about 250 °C. Further, a residence time of 1 h was found to be sufficient for optimum desulfurization to occur. It was also observed that the residence time could be further reduced by increasing the sodium content above stochiometric or also by means of increasing the reaction temperature to above 300°C. The effect of hydrogen partial pressure was not found to affect the desulfurization efficiency significantly.
• 210 g of CBFO and 90 ml of xylene were taken in the high pressure reactor. No hydrogen was added to the reactor.
• 210 g of CBFO and 90 ml of xylene were taken in the high pressure reactor and about 2170 kPa (300 psig) of hydrogen was added to the reactor.
• 210 g of CBFO was taken and no xylene or hydrogen was added.
• stoichiometric amount of sodium metal were added.
• the reaction temperature was kept to 290 °C for a residence time of 1h. Thus, after the reaction the samples were cooled and decanted for each of the cases.
• a process for desulphurization of carbon black feed oil has several technical advantages including but not limited to the realization of: the process does not require hydrogen; the process does not require high pressure conditions; the process reduces the loss of feed oil; the process gives a reduction in the asphaltene content of the petroleum oil by >50%; the process improves the viscosity of the desulphurized oil to ⁇ 200 mPa.s (cP); the process reduces the residual sodium content to ⁇ 10 ppm; the process enhances the processing and handling conditions of the CBFO; the process provides easy filtration and separation of the desulfurized oil and by-products thereof; and the process is safe as it lowers the density of oil in comparison with sodium metal.

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