US20140014557A1 - Process for desulphurization of petroleum oil - Google Patents

Process for desulphurization of petroleum oil Download PDF

Info

Publication number
US20140014557A1
US20140014557A1 US14/006,803 US201214006803A US2014014557A1 US 20140014557 A1 US20140014557 A1 US 20140014557A1 US 201214006803 A US201214006803 A US 201214006803A US 2014014557 A1 US2014014557 A1 US 2014014557A1
Authority
US
United States
Prior art keywords
oil
sodium
organic solvent
pat
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US14/006,803
Other languages
English (en)
Inventor
Sandeep Vasant Chavan
Harshad Ravindra Kini
Bir Kapoor
Ranjan Ghosal
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Aditya Birla Science and Technology Co Ltd
Original Assignee
Aditya Birla Science and Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Aditya Birla Science and Technology Co Ltd filed Critical Aditya Birla Science and Technology Co Ltd
Publication of US20140014557A1 publication Critical patent/US20140014557A1/en
Priority to US15/882,350 priority Critical patent/US20180251687A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G21/00Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
    • C10G21/06Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
    • C10G21/12Organic compounds only
    • C10G21/14Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G19/00Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/073Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with solid alkaline material
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G29/00Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04Metals, or metals deposited on a carrier
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining 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
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/201Impurities
    • C10G2300/202Heteroatoms content, i.e. S, N, O, P
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40Characteristics of the process deviating from typical ways of processing
    • C10G2300/44Solvents
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G31/00Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/09Refining 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 .
  • 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.
  • 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 U.S. Pat. No. 1,938,672, U.S. Pat. No. 1,952,616, U.S. Pat. No. 2,902,441, U.S. Pat. No. 3,004,912, U.S. Pat. No. 3,093,575, U.S. Pat. No. 3,617,530, U.S. Pat. No. 3,755,149, U.S. Pat. No. 3,787,315, U.S. Pat. No.
  • these processes use hydrogen at high pressures in combination to the sodium metal for desulfurization.
  • 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).
  • Na 2 S sodium sulfide
  • Some of the above-mentioned prior art documents also describe the regeneration of sodium from Na 2 S.
  • These processes report the effectiveness of desulfurization of recalcitrant sulfur especially from that of high boiling resid oils.
  • these sodium-based desulfurization processes are associated with limitations such as low yield of desulphurized feed oil, formation of large amount of insoluble sludge, requirement of hydrogen and safety concerns.
  • 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.
  • a large amount of valuable residual feed oil remains associated to the precipitated sulfur residue or unreacted sodium in the form of a highly viscous sludge.
  • the sludge is extremely difficult to filter and separate due to its inherent viscosity and sticky nature. There is a substantial loss of feed during the process, especially during filtration or separation. Further, it was observed that the sodium-based desulfurization processes result in retention of sodium metal in the oil.
  • 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 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 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 organic solvent is selected from alkanes, alkenes, cyclic alkenes, alkynes and alcohol. More preferably, the organic solvent is xylene.
  • 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 solvent concentration used is in the range of 0.1-70%, preferably in the range of 0.1-50%, more preferably in the range of 1-30%, in the mixture of CBFO and solvent.
  • 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. Further, 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. Further, the improvement in the feed oil viscosity enhances the processing of the feed oils required in applications such as manufacturing of carbon black product.
  • Asphaltenes are considered as the n-heptane insoluble, toulene 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 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. 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 0-500 psig, preferably in the range of 0-300 psig, and more preferably in the range of 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 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 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 is carried out in the presence of hydrogen, there may be a reduction in the aromatic content of the feed due to hydrogenation (reduced C:H ratio), resulting in lower yield of the 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 cP at ambient conditions. Addition of organic solvent prior to desulphurization reduces its viscosity to a substantial extent (less than 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 . Thus, there is a tendency for the sodium to remain floating at the top of CBFO surface.
  • 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 was then pressurized up to 300 psi 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 4 h.
  • 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).
  • 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).
  • the results with respect to these different compositions are tabulated in TABLE 1.
  • the CBFO, xylene and sodium content used is also tabulated below, along with the desulfurization efficiency for each of the different CBFS:Xylene ratios.
  • 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 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.
  • 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 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
US14/006,803 2011-03-23 2012-03-20 Process for desulphurization of petroleum oil Abandoned US20140014557A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/882,350 US20180251687A1 (en) 2011-03-23 2018-01-29 Process for the desulfurization of petroleum oil

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN845MU2011 2011-03-23
PCT/IN2012/000188 WO2012127504A2 (en) 2011-03-23 2012-03-20 A process for desulphurization of petroleum oil

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2012/000188 A-371-Of-International WO2012127504A2 (en) 2011-03-23 2012-03-20 A process for desulphurization of petroleum oil

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/882,350 Continuation US20180251687A1 (en) 2011-03-23 2018-01-29 Process for the desulfurization of petroleum oil

Publications (1)

Publication Number Publication Date
US20140014557A1 true US20140014557A1 (en) 2014-01-16

Family

ID=46879832

Family Applications (2)

Application Number Title Priority Date Filing Date
US14/006,803 Abandoned US20140014557A1 (en) 2011-03-23 2012-03-20 Process for desulphurization of petroleum oil
US15/882,350 Abandoned US20180251687A1 (en) 2011-03-23 2018-01-29 Process for the desulfurization of petroleum oil

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/882,350 Abandoned US20180251687A1 (en) 2011-03-23 2018-01-29 Process for the desulfurization of petroleum oil

Country Status (12)

Country Link
US (2) US20140014557A1 (ko)
EP (1) EP2688984B1 (ko)
JP (1) JP5841229B2 (ko)
KR (1) KR101946791B1 (ko)
CN (1) CN103534337B (ko)
BR (1) BR112013024269B1 (ko)
CA (1) CA2830881C (ko)
ES (1) ES2687687T3 (ko)
HU (1) HUE044215T2 (ko)
MX (1) MX362134B (ko)
RU (1) RU2561725C2 (ko)
WO (1) WO2012127504A2 (ko)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410042B2 (en) 2012-03-30 2016-08-09 Aditya Birla Science And Technology Company Ltd. Process for obtaining carbon black powder with reduced sulfur content
US9873797B2 (en) 2011-10-24 2018-01-23 Aditya Birla Nuvo Limited Process for the production of carbon black
US11828531B2 (en) 2021-09-24 2023-11-28 Bsh Home Appliances Corporation User interface module with adjustable mount for domestic appliance

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6386812B2 (ja) * 2014-06-26 2018-09-05 旭カーボン株式会社 蛍光x線元素分析用の試料作製方法
CN111363588B (zh) * 2018-12-25 2023-08-15 中国石油化工股份有限公司 生产低硫石油焦的方法和反应系统
EP4334027A1 (en) * 2021-05-06 2024-03-13 King Abdullah University Of Science And Technology Reactor configuration for ultrasonically induced cavitation with optimal bubbles distribution
AU2022270439A1 (en) * 2021-05-06 2023-12-07 King Abdullah University Of Science And Technology System for oxidative desulfurization enhanced by ultrasonically induced cavitation

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787315A (en) * 1972-06-01 1974-01-22 Exxon Research Engineering Co Alkali metal desulfurization process for petroleum oil stocks using low pressure hydrogen
US4119528A (en) * 1977-08-01 1978-10-10 Exxon Research & Engineering Co. Hydroconversion of residua with potassium sulfide
US20050040078A1 (en) * 2003-08-20 2005-02-24 Zinnen Herman A. Process for the desulfurization of hydrocarbonacecus oil
US20070227951A1 (en) * 2004-05-31 2007-10-04 Jeyagorwy Thirugnanasampanthar Novel Process for Removing Sulfur from Fuels
US7588680B1 (en) * 2003-04-17 2009-09-15 Trans Ionics Corporation Desulphurization of petroleum streams using metallic sodium
US20100264067A1 (en) * 2009-04-16 2010-10-21 General Electric Company Method for removing impurities from hydrocarbon oils

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1938672A (en) * 1929-07-05 1933-12-12 Standard Oil Co Desulphurizing hydrocarbon oils
GB441703A (en) * 1934-04-19 1936-01-20 Justin Fed Wait Improvements in or relating to methods of and apparatus for treating petroleum hydrocarbon oils and spirits
JPS5014649B1 (ko) * 1969-06-03 1975-05-29
US3755149A (en) * 1971-06-09 1973-08-28 Sun Oil Co Pennsylvania Process for desulfurizing petroleum resids
JPS5640197B2 (ko) * 1974-05-31 1981-09-18
GB1478490A (en) * 1974-09-04 1977-06-29 Haskett F Process for desulphurizing hydrocarbon especially petroleum fractions
DE2558505A1 (de) * 1975-04-28 1976-11-18 Exxon Research Engineering Co Verfahren zur entschwefelung und hydrierung von kohlenwasserstoffen
US4076613A (en) * 1975-04-28 1978-02-28 Exxon Research & Engineering Co. Combined disulfurization and conversion with alkali metals
US5935421A (en) * 1995-05-02 1999-08-10 Exxon Research And Engineering Company Continuous in-situ combination process for upgrading heavy oil
US6210564B1 (en) * 1996-06-04 2001-04-03 Exxon Research And Engineering Company Process for desulfurization of petroleum feeds utilizing sodium metal
US7192516B2 (en) * 2003-04-17 2007-03-20 Trans Ionics Corporation Desulfurization of petroleum streams using metallic sodium
JP2005307103A (ja) * 2004-04-26 2005-11-04 Idemitsu Kosan Co Ltd 重質油の水素化精製方法
CA2531262A1 (en) * 2005-12-21 2007-06-21 Imperial Oil Resources Limited Very low sulfur heavy crude oil and process for the production thereof
US7691788B2 (en) * 2006-06-26 2010-04-06 Schlumberger Technology Corporation Compositions and methods of using same in producing heavy oil and bitumen
CN101139530B (zh) * 2006-09-05 2010-07-28 中国石油天然气集团公司 一种柴油油品还原脱硫的方法
JP4897434B2 (ja) * 2006-11-07 2012-03-14 Jx日鉱日石エネルギー株式会社 灯油用脱硫剤、脱硫方法およびそれを用いた燃料電池システム
CN102197115B (zh) * 2008-09-18 2014-09-10 雪佛龙美国公司 用于生产粗产品的系统和方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3787315A (en) * 1972-06-01 1974-01-22 Exxon Research Engineering Co Alkali metal desulfurization process for petroleum oil stocks using low pressure hydrogen
US4119528A (en) * 1977-08-01 1978-10-10 Exxon Research & Engineering Co. Hydroconversion of residua with potassium sulfide
US7588680B1 (en) * 2003-04-17 2009-09-15 Trans Ionics Corporation Desulphurization of petroleum streams using metallic sodium
US20050040078A1 (en) * 2003-08-20 2005-02-24 Zinnen Herman A. Process for the desulfurization of hydrocarbonacecus oil
US20070227951A1 (en) * 2004-05-31 2007-10-04 Jeyagorwy Thirugnanasampanthar Novel Process for Removing Sulfur from Fuels
US20100264067A1 (en) * 2009-04-16 2010-10-21 General Electric Company Method for removing impurities from hydrocarbon oils

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9873797B2 (en) 2011-10-24 2018-01-23 Aditya Birla Nuvo Limited Process for the production of carbon black
US9410042B2 (en) 2012-03-30 2016-08-09 Aditya Birla Science And Technology Company Ltd. Process for obtaining carbon black powder with reduced sulfur content
US11828531B2 (en) 2021-09-24 2023-11-28 Bsh Home Appliances Corporation User interface module with adjustable mount for domestic appliance

Also Published As

Publication number Publication date
CA2830881A1 (en) 2012-09-27
CA2830881C (en) 2016-10-11
JP5841229B2 (ja) 2016-01-13
JP2014508846A (ja) 2014-04-10
CN103534337B (zh) 2016-08-31
MX2013010786A (es) 2014-02-27
RU2013147201A (ru) 2015-04-27
KR101946791B1 (ko) 2019-02-13
EP2688984A4 (en) 2014-09-03
CN103534337A (zh) 2014-01-22
EP2688984B1 (en) 2018-05-02
RU2561725C2 (ru) 2015-09-10
BR112013024269A2 (pt) 2018-06-26
BR112013024269B1 (pt) 2019-12-17
ES2687687T3 (es) 2018-10-26
US20180251687A1 (en) 2018-09-06
KR20140048866A (ko) 2014-04-24
EP2688984A2 (en) 2014-01-29
HUE044215T2 (hu) 2019-10-28
MX362134B (es) 2019-01-07
WO2012127504A2 (en) 2012-09-27
WO2012127504A3 (en) 2012-12-27

Similar Documents

Publication Publication Date Title
US20180251687A1 (en) Process for the desulfurization of petroleum oil
US4076613A (en) Combined disulfurization and conversion with alkali metals
US9410042B2 (en) Process for obtaining carbon black powder with reduced sulfur content
EP2670820B1 (en) Hydrocarbon treatment process
CA2745424C (en) Process for producing a high stability desulfurized heavy oils stream
CN109890944B (zh) 从液体烃中分离含碱金属盐的颗粒的方法
EP3692114B1 (en) Integrated process for activating hydroprocessing catalysts with in-situ produced sulfides and mercaptans
US4007111A (en) Residua desulfurization and hydroconversion with sodamide and hydrogen
Makarevich et al. Study of the Composition of the Mining Industry Rubber Waste Pyrolyzates
CN113583708B (zh) 一种油品超深度脱硫方法
MXPA04008358A (es) Eliminacion de compuestos con contenido de azufre de corrientes de hidrocarburos liquidos.
TASHEVA ADSORPTION PROCESS OF SULPHUR REMOVAL FROM MIDDLE DISTILLATE FRACTIONS USING SORBENT MATERIAL.
Lazorko et al. Investigation of straight-run diesel oil fractions with sulphur high content oxidative desulphurization
EP3707222A1 (en) Process for preparing a sweetened hydrocarbon liquid composition with reduced tendency to form gums, a scavenger composition for use in said process, and the sweetened hydrocarbon liquid composition with reduced tendency to form gums so prepared
WO2019093890A1 (en) Process for preparing a sweetened hydrocarbon liquid composition with reduced tendency to form gums, a scavenger composition for use in said process, and the sweetened hydrocarbon liquid composition with reduced tendency to form gums so prepared
JP5420843B2 (ja) 炭化水素の硫黄分低減方法
Nagham et al. Article Open Access
US20090139903A1 (en) Desulfurization of petroleum streams utilizing a multi-ring aromatic alkali metal complex

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION