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
• • 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
  • C10G21/16—Oxygen-containing compounds
• • 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
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
  • C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of 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
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
  • C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of solvents
  • C10G73/08—Organic compounds
  • C10G73/10—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
  • C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
  • C10G73/02—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils
  • C10G73/06—Recovery of petroleum waxes from hydrocarbon oils; Dewaxing of hydrocarbon oils with the use of solvents
  • C10G73/08—Organic compounds
  • C10G73/12—Oxygen-containing compounds
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1096—Aromatics or polyaromatics
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/30—Aromatics

Definitions

• the present disclosure relates to a process for producing raffinate with improved aromaticity.
• FCC fluid catalytic cracking
• aromaticity used in the specification means chemical property in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibit a stabilization stronger than would be expected by the stabilization of conjugation alone.
• raffinate as used in the specification means paraffin extracted clarified slurry oil.
• BMCI Bureau of Mines Correlation Index.
• Carbon black feed stock is a heavy hydrocarbon mix (C 20 to C 50 ) which is the key raw material in manufacturing carbon black. Carbon black finds extensive use in the rubber industry as a reinforcing agent in rubber products such as tyres, tubes, conveyer belts, cables and other mechanical rubber goods. CBFS is also used as heating fuel oil in several industrial units. Carbon black is obtained by the partial combustion and thermal decomposition of highly aromatic hydrocarbon oils under controlled conditions. Some of the most important feedstocks used for producing carbon black include: clarified slurry oil (CSO) obtained from fluid catalytic cracking of gas oils, ethylene cracker residue from naphtha steam cracking and coal tar oils.
• CSO clarified slurry oil
• paraffins in heavy aromatic hydrocarbon fractions substantially reduces their suitability for certain applications such as production of carbon black, anode coke, needle coke, and asphaltene stabilization in delayed coker feedstock. Therefore, lower the amount of paraffins in the heavy aromatic hydrocarbon fractions higher is the value of such feedstocks for the above mentioned applications.
• Another important characteristic is the Bureau of Mines Correlation Index (BMCI), wherein, carbon black feedstock must have a high BMCI to be able to offer a high yield of carbon black; therefore, heavy aromatic hydrocarbon feedstock used to obtain the CBFS should have a high BMCI.
• the BMCI is indicative of the aromaticity in aromatic hydrocarbons.
• Feedstocks having a high BMCI give a higher yield of carbon black with minimum heat input hence reducing the cost of manufacturing. Also, the feedstock for carbon black should have low sulfur content, as sulfur adversely affects the product quality, leads to lower yield and corrodes the equipment.
• the BMCI value for CBFS should be more than 132; whereas, BMCI value of CSO obtained at FCC plant is in the range of 110 - 130, typically less than 126, depending on the conversion in the FCC unit. Higher conversion leads to higher BMCI. Therefore, there is felt a need to increase the BMCI value of CSO above 132 before CSO can be used as a CBFS feedstock for manufacturing Carbon Black. Further, there is also felt a need to reduce the paraffin content of CSO to enhance the applicability of the feedstock.
• Vacuum distillation of CSO separates light cycle oil (LCO) range components from CSO.
• LCO light cycle oil
• the process involves removing asphaltic material from clarified slurry oil (CSO) through the extractive or precipitant action of solvents.
• CSO clarified slurry oil
• US2002005374 discloses a process for upgrading a non-hydrotreated feedstream which comprises solvent deasphalting the feedstream to obtain a first product stream comprising deasphalted oil and a second product stream comprising an asphalt product; slurry hydroprocessing the asphalt product to obtain a hydroprocessed product; and separating an upgraded oil from the hydroprocessed product and unconverted asphaltene bottoms.
• US20090166253 disclose systems and methods for processing one or more hydrocarbons for selectively separating to provide one or more light deasphalted oils (DAO) which can be cracked to provide hydrocarbon products.
• the method comprises: combining the feedstock comprising heavy oils, light oils, and asphaltenes with one or more solvents to provide a first mixture; separating the asphaltenes from the first mixture to provide a second mixture comprising solvent, heavy deasphalted oils, and light deasphalted oils; selectively separating the heavy deasphalted oils from the second mixture to provide a third mixture comprising the solvent and light deasphalted oils; and selectively separating the solvent from the third mixture to give light deasphalted oils.
• DAO light deasphalted oils
• US2010243518 discloses integrated slurry hydrocracking (SHC) and solvent de- asphalting (SDA) methods for making slurry hydrocracking (SHC) distillates.
• the method involves subjecting SHC gas oil to the SDA process to obtain de-asphalted oil (DAO) and an SDA pitch, wherein, at least a portion of the DAO is recycled to the SHC reaction zone.
• DAO de-asphalted oil
• US20090166266 discloses a method for dewatering and deasphalting a crude oil that comprises hydrocarbons, asphaltenes and water with one or more solvents.
• the feed as employed in the presently known deasphalting processes is usually a vacuum residue or atmospheric residue or crude oil with an asphaltene content in excess of 5wt %. It is known that the presently known deasphalting process cannot be carried out if the asphaltene content in the input stream is lower than 5 wt %.
• An object of the present disclosure is to provide a paraffin extraction process that is suitable for a feed with low asphaltene content such as clarified slurry oil.
• Another object of the present disclosure is to provide a process for improving the aromaticity of heavy aromatic hydrocarbons.
• Still another object of the present disclosure is to provide a process which gives clarified slurry oil having Bureau of Mines Correlation Index (BMCI) greater than 132.
• BMCI Bureau of Mines Correlation Index
• a further object of the present disclosure is to provide a process for improving the aromaticity of clarified slurry oil, which gives a useful by-product such as extracted paraffin rich oil.
• the process further comprises heating the separated paraffin rich phase at a temperature ranging between 40 and 80 °C to remove solvent for recycling.
• the solvent is at least one selected from the group consisting of C 2 to C 7 hydrocarbons and C 3 to C 7 ketones.
• the solvent is at least one selected from the group consisting of C 2 to C 7 alkanes, C 2 to C 7 alkenes and C 3 to C 7 ketones.
• the proportion of the solvent to oil ranges between 4:1 and 10:1
• the heating is carried out at a pressure ranging between 10 and 50 kg/cm 2 .
• the mixing of heated oil-solvent mixture is carried out by using a static mixer or mechanical stirrer at a temperature ranging between 50 to 200 °C and at a pressure ranging between 10 and 50 kg/cm .
• the agitation of heated oil-solvent mixture is carried out at a speed ranging between 500 to 3000 rpm to ensure proper mixing.
• the pressure drops across static mixer is in the range of 1 to 10 kg/cm2(g) to ensure proper mixing.
• raffinate with aromatics content of at least 90 wt % and having a BMCI of at least 132 obtained by the process of the present disclosure.
• the present disclosure envisages a novel process for producing raffinate (paraffin extracted clarified slurry oil) with improved aromaticity by extracting paraffin from feedstock such as clarified slurry oil (CSO). Further, the present disclosure also aims at reducing the paraffin content of clarified slurry oil.
• the paraffin extracted clarified slurry oil (raffinate) so obtained has a high Bureau of Mining Correlation (BMCI), i.e. at least 132, which makes it suitable for applications like raw material for carbon black production, anode coke production, needle coke production, and as a diluent for improving asphaltene stability of delayed coker feedstock.
• BMCI Bureau of Mining Correlation
• the process of the present disclosure also provides an extract (paraffin rich oil) which comprises approximately 50-90 % of the total paraffin content of the clarified slurry oil feedstock.
• This byproduct can be used as a feed in fluid catalytic cracking (FCC) process and hydrocracking process, as a lube oil base stock and as a thermic fluid.
• FCC fluid catalytic cracking
• clarified slurry oil feedstock having a BMCI of 110 to 130 is mixed with a solvent in an apparatus to obtain an oil-solvent mixture.
• the solvent used is at least one selected from the group consisting of C 2 to C 7 hydrocarbons and C 3 to C 7 ketones.
• the solvent used is a light hydrocarbon selected from the group consisting of C 2 to C 7 alkanes and C 2 to C 7 alkenes.
• the structure of the hydrocarbon can be linear, branched (iso), and/ or cyclic.
• the clarified slurry oil is highly aromatic; thus, it is easier to separate out the paraffins from the slurry oil on the basis of its solubility in the light hydrocarbons, ketones or their mixtures.
• a suitable solvent or a mixture of solvents can be used in the process of the present disclosure for improving the aromatic content and reducing the paraffinic content.
• propylene or ethylene may be added to improve the selectivity towards the by-product i.e. paraffinic rich oil.
• the solvent to oil ratio used is typically in the range of 4:1 to 10: 1.
• the solubilization of the solvent in the slurry oil is typically carried out continuously in vessel or on-line which is maintained at a pressure in the range of 10 - 50 kg/cm 2 to obtain an oil- solvent mixture.
• the oil-solvent mixture is heated at a temperature in the range of 50 to 200 °C to obtain a heated oil-solvent mixture.
• the process temperature can be varied depending on type of the solvent and % of paraffinic oil lift required.
• the heated oil-solvent mixture is agitated vigorously for 0.5 to 2 hours while maintaining the temperature and pressure conditions in the autoclave.
• mechanical devices like static mixer can be used to ensure intimate mixing.
• the agitator speed is typically in the range of 500 to 3000 rpm.
• the obtained oil-solvent dispersion is allowed to cool and separate to obtain biphase mixture containing extract (paraffin rich phase) and raffinate phase.
• the extract i.e, paraffin rich oil and the raffinate phase comprising aromatic rich slurry oil are separated.
• the paraffin rich oil can be subsequently heated at a temperature in the range of 40 to 80 °C to remove solvent which is recycled as a solvent.
• the paraffin rich oil thus obtained comprises approximately 50 to 90 wt% of the total paraffins content of the clarified slurry oil feedstock.
• the paraffin rich oil thus obtained as a by-product of the process can be suitably used as: a feedstock for fluid catalytic cracking (FCC) with or without hydrotreating to subsequently obtain FCC products; a feedstock in hydrocracking process for obtaining high quality diesel and other derivative products; as a lubricating oil base stock; and as a thermic fluid for heat transfer applications.
• the paraffin rich oil yield can be varied in the range of 15 - 30 wt % of clarified slurry oil (CSO) feedstock by manipulating the operating temperature between 50 and 85°C and varying solvent to oil ratio.
• CSO clarified slurry oil
• the raffinate phase (fraction) of clarified slurry oil obtained by the process of the present disclosure is characterized by aromatics content of at least 90 wt %. i.e. the aromatic content of the raffinate fraction of clarified slurry oil is at least 5 - 10 wt % more than the aromatic content of the clarified slurry oil feedstock.
• the BMCI of the raffinate is found to be at least 132 which is higher than the BMCI of clarified slurry oil feedstock.
• the raffinate thus obtained is a valuable feedstock for processes including: feedstock for producing carbon black which is extensively used in the tyre and ink industry; feedstock for producing anode coke which is used in manufacturing electrodes in aluminum industries; feedstock for producing needle coke which is used in manufacturing electrodes for high temperature applications in steel industries; and as a diluent for improving the asphaltene stability of delayed coker feedstock, as higher aromaticity in coker and visbreaker feed improves the asphaltene stability and helps to reduce the coking rates in furnace tubes thus giving an improved run length of coker.
• the process of the present disclosure i.e., separation of paraffin rich oil and aromatic rich raffinate by the solvent extraction of clarified slurry oil feedstock, improves the economic benefits of both the products (raffinate) and the by-product (paraffin rich oil), by making them more suitable for a variety of industrial applications.
• CSO clarified slurry oil
• the extract and raffinate were analyzed for viscosity, density, High Temperature Simulated Distillation and SARA (Saturates, Asphaltenes, Resins and Aromatics) analysis.
• SARA Saturates, Asphaltenes, Resins and Aromatics
• TLC-FID analyzer The properties of clarified slurry oil feedstock, raffinate and extract are illustrated in TABLE 1.
• the BMCI was calculated using the following equation:
• BMCI (48640/T) + (473.7 * specific gravity) - 456.8
• the aromatic content of the raffinate was 6 wt % higher than the clarified slurry oil (CSO) feedstock. Further, the corresponding API gravity of raffinate was increased by 2 units and the BMCI value calculated by gravity and distillation method was increased from 127 to 134, in comparison with the feedstock. A higher density and lower average boiling point is desired for improving the BMCI. Still further, the propane extraction process removed more than 50 % of saturates from the feedstock, as, in the raffinate obtained. The experiment was carried out in a single-stage mixer settler lab autoclave unit. The extract yield and its saturate content are expected to improve further in a continuous multi-stage extraction process having special internals for better mixing and settling.
• CSO clarified slurry oil
• the extract obtained by the extraction process of the present disclosure has low Conradson Carbon Residue (CCR) and Asphaltenes content, which makes the extract suitable as a FCC feed with or without hydrotreating, as a hydrocracker feed, as lube oil base stock, and as thermic fluid for heat transfer applications.
• CCR Conradson Carbon Residue
• Asphaltenes content which makes the extract suitable as a FCC feed with or without hydrotreating, as a hydrocracker feed, as lube oil base stock, and as thermic fluid for heat transfer applications.
• the clarified slurry oil feedstock (CSO), raffinate and extract were analyzed in a gas chromatograph (High temperature Simdist, D7169). The analysis is illustrated in TABLE 2.
• KBC VGO-HT Kinetic model estimates showed aromatics saturation in extract from 65 % to 50 % by wt and UOPK factor improvement from 10.4 to 10.7. Extract as such shows a conversion of approximately 41 wt % (at 216 °C) and approximately 66 wt % (at 370 °C). Hydrotreating improves the conversion to approximately 47 wt % (at 216 °C) and approximately 77 wt % (at 370 °C). This shows substantial potential for upgrading the extract through VGO-HT and FCC.
• TABLE 3 illustrates yields estimates of products of extract and hydrotreated (HDT) extract in FCC by KBC Simulation Kinetic model.

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• 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)
• Working-Up Tar And Pitch (AREA)
• Pigments, Carbon Blacks, Or Wood Stains (AREA)

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• 2012
  • 2012-02-10 WO PCT/IN2012/000093 patent/WO2012120537A2/fr not_active Ceased
  • 2012-02-10 JP JP2013553072A patent/JP5875604B2/ja not_active Expired - Fee Related
  • 2012-02-10 EP EP12754609.1A patent/EP2673343A4/fr not_active Withdrawn
  • 2012-02-10 US US13/983,968 patent/US20130313159A1/en not_active Abandoned
  • 2012-02-10 SG SG10201601004YA patent/SG10201601004YA/en unknown
  • 2012-02-10 KR KR1020137021507A patent/KR20140034145A/ko not_active Ceased
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