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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha
  • C10G69/10—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha hydrocracking of higher boiling fractions into naphtha and reforming the naphtha obtained
• • 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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
• • 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
  • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
• • 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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
• • 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
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural parallel stages only
• • 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
  • C10G2300/1003—Waste materials
  • C10G2300/1007—Used oils
• • 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
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1062—Lubricating oils
• • 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
  • C10G2300/203—Naphthenic acids, TAN
• • 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
  • C10G2300/205—Metal content
• • 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
  • C10G2300/4006—Temperature
• • 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
  • C10G2300/4012—Pressure
• • 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
  • C10G2300/70—Catalyst aspects
  • C10G2300/708—Coking aspect, coke content and composition of deposits
• • 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
  • C10G2400/20—C2-C4 olefins
• • 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 synergistic co-conversion of used oils to value added products. More particularly, the present disclosure relates to a process for synergistic co-conversion of Used Lubricating Oil (ULO) and Used Cooking Oil (UCO) to value added products.
• UAO Used Lubricating Oil
• UO Used Cooking Oil
• ULO is a petroleum based spent oil and has become unsuitable for its original purpose as it is subjected to high temperature and mechanical strain during running of the vehicle for stipulated time. It is a brown to black color liquid mixture consisting of low to high molecular weight (C 16 -C 36 ) aliphatic and aromatic hydrocarbons viz polychlorinated biphenyl, chloro-dibenzofurans, alkylbenzenes, naphthalene, methylnaphthalenes, poly glycols or base oils termed as Lube Oil Base Stock (LOB S) of different grades depending on the applications, polyol esters, lubricative additives such ZDDP (zinc dialkyl thiophosphate, phosphate esters, thiophosphate esters as anti-wear, calcium based detergent additives such as calcium sulphonates, calcium phosphonates and decomposition products such as zinc thiophosphates, zinc pyro-polythiophosphates.
• UCO is leftover cooking oil containing carcinogenic substances that results from the frying process. Furthermore, UCO contains high content of unsaturated aliphatic fatty acids which indicates high Total Acid Number (TAN).
• Used lubricating oil can be from motor vehicles, combustion, engines, gear boxes; Used Cooking Oil from food industry, hotels, restaurants and conventional residue feed such as reduced crude oil, vacuum residue, slop oil etc. from refineries.
• the present disclosure relates to the development of a process for providing value addition to used oils by reducing and/or redistributing the impurity profiles and processing in delayed coking and steam cracking process units in a synergistic manner.
• ULO is reacted in a reactor vessel at an elevated temperature with fatty acids rich in UCO to mitigate the acidic content, via. formation of fatty acid glycol esters as well as redistribute the metal impurities selectively to the high boiling fraction of the obtained ULO+UCO reaction mixture.
• the mixture is fractionated into lighter fraction which is utilized in steam cracker process to produce olefins and aromatics while heavier fraction of the mixture is subjected to delayed coking process for production of value-added products.
• This process not only prevents Delayed Coking Unit (DCU) as well as steam cracker hardware from corrosion but also saves additional energy requirement in reboiler of prefractionation column by heat integrating reboiler of prefractionation column with hot Heavy Coker Gas Oil (HCGO) stream from Main Fractionator (MF) of DCU. This also prevents and/or mitigates fouling as well as deactivation in the hydrotreating based feed pretreatment catalyst(s) of steam cracker process.
• DCU Delayed Coking Unit
• HCGO Heavy Coker Gas Oil
• US005248410A describes a process comprising passing a used petroleum derived lubricating oil to a reaction zone and coking at delayed coking reaction conditions.
• the reaction product comprises coke, hydrocarbon liquids and gas.
• US 2022/0177785 A1 discloses systems and methods for producing one or more olefins using waste plastics and used lubricating oil.
• EP0259378A1 discloses a process for purifying used lubricating oil wherein used lubricating oil is refined by treating the distillate of the same with small amount of caustic in presence of specific amount of water. The resultant two phase mixture is separated from saline phase to obtain purified lubricating oil.
• WO 2008/036696 A2 discloses a process for recovering used lubricating oil using clay and centrifugation wherein used lubricating oil is mixed with clay in a reactor at temp of 80-200°C and is pumped through filter in order to recover oil free of contaminants.
• WO 2019/116122 A1 describes the co-processing of used lubricating oil with conventional coker feedstock at Delayed Coker conditions to produce gas, liquid and coke which is of anode grade quality.
• the present invention describes a process wherein ULO is reacted at an elevated temperature with fatty acids rich UCO to mitigate the acidic content, via. formation of fatty acid glycol esters as well as redistribute the metal impurities selectively to the high boiling fraction of the obtained ULO+UCO reaction mixture.
• the reaction mixture is fractionated into heavier fraction and lighter fraction, wherein the heavier fraction is subjected to delayed coking process for production of value-added products.
• the metals present in the reaction mixture will further be reduced due to deposition of the same on the coke produced from Delayed Coker producing liquid products with low metal contents.
• the lighter fraction of ULO+UCO reaction mixture is fed to steam cracker unit for production of high value petrochemicals such as light olefins and aromatics.
• the method of the present disclosure is advantageous as it takes care of contaminants of used oils by synergistic combination of UCO & ULO and also produces value added fuels along with petrochemicals.
• US 2022/0177785 A1 describes about system and method wherein used lubricating oil is blended with waste plastic pyrolysis oil obtained from plastic pyrolysis process and resultant mixture is fractionated into lighter cut which is routed to steam cracker for olefins production while heavy cut is vacuum distilled to obtain lighter stream which is routed to hydro-processing for naphtha generation and naphtha again is fed to steam cracker while heavy par from vacuum column is recycled back to plastic pyrolysis process.
• the present invention utilizes used lubricating oil and used cooking oil using steam cracker and delayed coking processes. It does not involve vacuum distillation and hydro-processing processes for generation of naphtha.
• the invention takes care of contaminants of used oils unlike the prior art by synergistic combination of UCO & ULO and also produces value added fuels along with petrochemicals.
• EP0259378A1 discloses process for purifying used lubricating oil wherein used lubricating oil is refined by treating the distillate of the same with small amount of caustic in presence of specific amount of water. The resultant two phase mixture is separated from saline phase to obtain purified lubricating oil.
• the present invention discloses a process where contaminants present in the UCO are neutralized by reacting it with ULO to produce low acid and low metal content mixture. The invention not only takes care of contaminants of used oils by synergistic combination of UCO & ULO but also produces value added fuels along with petrochemicals.
• WO2008/036696 A2 discloses a process for recovering used lubricating oil using clay and centrifugation wherein used lubricating oil is mixed with clay in a reactor at temp of 80-200°C and is pumped through filter in order to recover oil free of contaminants.
• the present invention discloses a process where contaminants present in the UCO are neutralized by reacting it with ULO to produce low acid and low metal content mixture. The invention not only takes care of contaminants of used oils by synergistic combination of UCO & ULO but also produces value added fuels along with petrochemicals.
• the present disclosure provides a process wherein ULO containing metal impurities is reacted in a reactor vessel at an elevated temperature with fatty acids rich UCO to mitigate the acidic content, via. formation of fatty acid glycol esters as well as redistribute the metal impurities selectively to the high boiling fraction of the obtained ULO+UCO reaction mixture thereby making it suitable for subjecting to synergistic processing in delayed coking and steam cracking process in an integrated manner for production of value-added products.
• ULO and UCO undergo esterification reaction to form fatty acid glycol esters neutralizing the fatty acids of UCO making the ULO+UCO reaction mixture suitable for processing it in Delayed Coker and Steam Cracker process hardware.
• the inventors have also discovered that there is an effect of capture of the metals into the heavier boiling molecules from the metal and phosphorous containing moieties in the ULO by reaction with the heavier molecules of UCO.
• the process also involves heat integration of HCGO stream with reboiler of prefractionation column thereby saving additional energy requirement.
• reaction between ULO and UCO would result in reduction of phosphorus, zinc and calcium content in ULO+UCO lighter fraction (boiling range below 200°C) which otherwise is a poison for hydrotreating catalyst.
• the lighter fraction (boiling range below 200°C) of ULO+UCO reaction mixture is fed to a steam cracker for petrochemicals production.
• the middle fraction (200-370°C) of ULO is utilized as alternative for conventional quench oil.
• the heavier cut (boiling range above 200°C) is fed along with residue feed to DCU for production of value-added fuels.
• synergistic combination involving reaction of UCO and ULO lowers the impurity content and makes the reaction mixture suitable for processing in DCU.
• heat integration of prefractionation column reboiler with HCGO from MF of DCU is
• the primary object of the present disclosure is to develop a process wherein UCO & ULO is utilized in Delayed Coker and steam cracker processes for production of value-added fuels along with petrochemicals. Moreover, delayed coking of mixture in the process of the present disclosure causes further reduction in metal content as the metal gets deposited on the solid coke produced during delayed coking.
• Another object of the present disclosure is to provide a process wherein contaminants are reduced by synergistic combination of used oils at a particular proportion to produce low metal and low acid mixture.
• Still another objective of the present disclosure is to provide a process for direct processing of used oils after treatment in secondary conversion units such as DCU is cost effective route compared to conventional methods.
• Another object of the present disclosure is to provide a process wherein processing of used oils along with residue feedstock is carried out hence, it indirectly reduces overall crude consumption for same throughput and thus, reduces overall crude oil import dependency.
• the process of the present disclosure is advantageous as it provides a suitable pathway for proper utilization of the used oils such as used lubricating oil and used cooking oil in refineries instead of disposing in the environment. It reduces high levels of impurities in terms of phosphorus, metals in ULO, TAN content in UCO which otherwise is difficult to process directly in refineries. Hence, the claimed process is a cost-effective process for re-refining ULO/UCO and reduces dependence on crude oil import by providing alternative feedstock.
• the present disclosure relates to a process for synergistic co-conversion of Used Lubricating Oil (ULO) and Used Cooking Oil (UCO) to value added products.
• UEO Used Lubricating Oil
• UO Used Cooking Oil
• the reactor can be selected either from continuous stirred tank reactor or plug flow reactor or batch reactor or fluidized bed reactor.
• reaction mixture (4, 46) has lower Total Acid Number value compared to base mixture of ULO and UCO.
• stream cracker unit is operated at a temperature in the range of 750-950°C, pressure in the range of 0.5-2.0 bar, residence time in the range of 0.1-1.0 second, the steam to feed ratio is in the range of 0.2-1.4.
• a process for synergistic co-conversion of used oils to value added products as described herein wherein the plurality of coke drums is operated in parallel to complete a coking cycle one after another, and the coke drum effluents is systematically passed into each of the plurality of coke drums through a switch valve to facilitate the coking cycle in each of the plurality of coke drums.
• the present disclosure relates to a process for synergistic co-conversion of Used Lubricating Oil (ULO) and Used Cooking Oil (UCO) to value added products.
• UAO Used Lubricating Oil
• UO Used Cooking Oil
• the present disclosure provides a process for synergistic co-conversion of Used Lubricating Oil (ULO) and Used Cooking Oil (UCO) to value added products.
• Used Lubricating Oil (1) containing metal and phosphorus impurities is synergistically combined with Used Cooking Oil (2) containing acid impurities in a reactor vessel (3) to obtain a ULO+UCO reaction mixture (4) wherein ULO is reacted at an elevated temperature with fatty acids rich UCO to mitigate the acidic content via formation of fatty acid glycol esters as well as redistribute the metal impurities selectively to the high boiling fraction of the obtained ULO+UCO reaction mixture (4).
• the reaction mixture (4) is fed to the pre-fractionator column (5) wherein it is fractionated into two fractions namely lighter fraction (6) and heavier fraction (7).
• the lighter fraction (6) along with straight run naphtha stream (34) from conventional Atmospheric Distillation Unit (ADU) is then routed to hydrotreating unit (35) for removal of sulfur impurities to obtain a low sulfur stream (36) suitable for Steam cracker unit.
• the stream (36) is then routed to Steam Cracker Unit (37) for production of high value petrochemicals such as ethylene, propylene, butylenes and aromatics (38).
• the heavier fraction (7) is then mixed with residue feed (8) in a surge drum (9) to obtain feed mixture (10) which is pumped using surge drum pump (11) to the bottom of Main Fractionator (MF) (13) as primary feed stream (12).
• the secondary feed stream (14) which is obtained from mixing of primary feed stream (12) & an internal recycle in main fractionator, is then pumped through coker furnace (16) using fractionator bottom pump (15). Heating of the secondary feed stream (14) to obtain coker furnace effluent (17). In other words, the secondary feed stream (14) is heated in coker furnace up to desired coking temperatures to obtain coker furnace effluent (17).
• the coker furnace effluent (17) is then diverted to a plurality of coke drums (19, 20) using switch valve (18).
• the coke drums (19, 20) provide sufficient residence time for the thermal cracking of coker furnace effluent (17) to take place till the completion of coking reaction.
• the Gas Oils are used as quenching stream for quenching the coke drum effluent (21) which is routed to the MF (13) for product fractionation and solid petroleum coke which is removed after completion of coking cycle.
• Two coke drums (19, 20) are operated in parallel in order to ensure smooth functioning of coking cycle.
• coke drum (19) When coke drum (19) is full of coke, the coking cycle ends and the furnace outlet flow is then transferred from coke drum (19) to a parallel coke drum (20) to initiate its coking cycle, while coke removal process is initiated in the filled drum (19) which comprises of steaming, water cooling, coke cutting, and vapor heating and draining.
• the wash liquid (22) from the drums is discharged into a blow down section.
• the coke drum effluents (21) after quenching are again sent to Main fractionator (13), where it is separated and recovered.
• Heavy coker gas oil (HCGO) (23), Light coker gas oil (LCGO) (24) and Kerosene (25) are drawn off the fractionator at desired boiling temperature ranges using side strippers.
• HCGO pump around stream (31) from the main fractionator is then utilized as a heat integrating stream to reboiler (32) of Pre-fractionator column (5) to provide sufficient heat for ULO+UCO reaction mixture re-boiling while the cooled HCGO stream (33) is again routed back to MF.
• the wet gas (26) coming out of fractionator top goes to three phase separator (27) where gaseous hydrocarbons (39), water as aqueous phase (28) and un-stabilized naphtha as liquid phase (29) are separated with reflux (30) to the fractionator (13).
• the Used Lubricating Oil (40) is fed to the Pre-fractionator column (41) wherein it is fractionated into two fractions namely lighter fraction (42) and heavier fraction (43).
• the lighter fraction (42) along with straight run naphtha stream (73) from conventional Atmospheric Distillation Unit (ADU) is then routed to hydrotreating unit (74) for removal of sulfur impurities to obtain a low sulfur stream (75) suitable for Steam cracker unit.
• ADU Atmospheric Distillation Unit
• the stream (75) is then routed to Steam cracker Unit (76) for production of high value petrochemicals (77) such as ethylene, propylene, butylenes and aromatics.
• high value petrochemicals such as ethylene, propylene, butylenes and aromatics.
• the heavier fraction (43) from Pre-fractionator column (41) is synergistically combined with Used Cooking Oil (44) in a reactor vessel (45) wherein heavier fraction (43) is reacted at an elevated temperature with fatty acids rich UCO (44) to mitigate the acidic content via formation of fatty acid glycol esters to obtain the reaction mixture (46).
• the reaction mixture (46) is then mixed with residue feed (47) in a surge drum (48) to obtain feed mixture (49) which is pumped using surge drum pump (50) to the bottom of Main Fractionator (MF) (52) as primary feed stream (51).
• the secondary feed stream (53) is heated in coker furnace upto desired coking temperatures to obtain coker furnace effluent (56).
• the coker furnace effluent is then diverted to a plurality of coke drums (58, 59) using switch valve (57).
• coke drum (58) When coke drum (58) is full of coke, the coking cycle ends and the furnace outlet flow is then transferred from coke drum (58) to a parallel coke drum (59) to initiate its coking cycle, while coke removal process is initiated in the filled drum (58) which comprises of steaming, water cooling, coke cutting, and vapor heating and draining.
• the wash liquid (61) from the drums is discharged into the blow down section.
• the coke drum effluents (60) after quenching are again sent to Main fractionator (52), where it is separated and recovered.
• Heavy coker gas oil (HCGO) (62), Light coker gas oil (LCGO) (63) and Kerosene (64) are drawn off the fractionator at desired boiling temperature ranges using side strippers.
• HCGO pump around stream (70) from the main fractionator is then utilized as a heat integrating stream to reboiler (71) of Pre-fractionator column to provide sufficient heat for ULO re-boiling while the cooled HCGO stream (72) is again routed back to MF.
• the wet gas (65) coming out of Main fractionator top goes to three phase separator (66) where gaseous hydrocarbons (78), water as aqueous phase (67) and un-stabilized naphtha as liquid phase (68) are separated with reflux (69) to the Main fractionator (52).
• the reactor can be selected either from continuous stirred tank reactor or plug flow reactor or batch reactor or fluidized bed reactor.
• reaction mixture (4, 46) has lower Total Acid Number value compared to base mixture of ULO and UCO.
• stream cracker unit is operated at a temperature in the range of 750-950°C, pressure in the range of 0.5-2.0 bar, residence time in the range of 0.1-1.0 second, the steam to feed ratio is in the range of 0.2-1.4.
• a process for synergistic co-conversion of used oils to value added products as described herein wherein the plurality of coke drums is operated in parallel to complete a coking cycle one after another, and the coke drum effluents is systematically passed into each of the plurality of coke drums through a switch valve to facilitate the coking cycle in each of the plurality of coke drums.
• the Used Lubricating Oil (79) is fed to the Pre-fractionator column (80) wherein it is fractionated into three fractions namely lighter fraction (81) with boiling range below 200°C, middle fraction (112) with boiling range of 200-370°C and heavier fraction (82) with boiling range above 370°C.
• the lighter fraction (81) along with straight run naphtha stream (114) from conventional Atmospheric Distillation Unit (ADU) is then routed to hydrotreating unit (115) for removal of sulfur impurities to obtain a low sulfur stream (116) suitable for Steam cracker unit.
• the stream (116) is then routed to Steam cracker Unit (117) for production of high value petrochemicals such as ethylene, propylene, butylenes and aromatics (118).
• the heavier fraction (82) from Pre-fractionator column (80) is synergistically combined with Used Cooking Oil (83) in a reactor vessel (84) wherein heavier fraction (82) is reacted at an elevated temperature with fatty acids rich UCO (83) to mitigate the acidic content via.
• reaction mixture (85) is then mixed with residue feed (86) in a surge drum (87) to obtain feed mixture (88) which is pumped using surge drum pump (89) to the bottom of Main Fractionator (MF) (91) as primary feed stream (90).
• the secondary feed stream (92) which is obtained from mixing of primary feed stream (90) & internal recycle in main fractionator, is then pumped through coker furnace (94) using fractionator bottom pump (93), for achieving the desired coking temperature (usually between 460°C and 520°C) which also results in the partial vaporization and mild cracking of secondary feed stream (92) to obtain coker furnace effluent (95).
• HCGO Heavy coker gas oil
• LCGO Light coker gas oil
• Kerosene (103) are drawn off the fractionator at desired boiling temperature ranges using side strippers.
• HCGO pump around stream (109) from the main fractionator is then utilized as a heat integrating stream to reboiler (110) of Pre-fractionator column to provide sufficient heat for ULO re-boiling while the cooled HCGO stream (111) is again routed back to MF.
• the wet gas (104) coming out of Main fractionator top goes to three phase separator (105) where gaseous hydrocarbons (119), water as aqueous phase (106) and un-stabilized naphtha as liquid phase (107) are separated with reflux (108) to the Main fractionator (91).
• the operating temperature for delayed coking drums varies from 460-520°C with pressure from 1-5 bar and minimum of 10-36 hours cycle time. Temperature of HCGO stream coming out of Main fractionator is 270-390°C.
• Steam cracker feed pretreatment hydrotreating unit for obtaining hydrotreated feed for Steam cracker unit is operated at temperature in the range of 300-360°C at a pressure of 10-25 bar.
• the obtained reaction mixture can either be treated with adsorbents or catalysts or additives to further reduce the metal/acidic impurities.
• UCO instead of UCO we can either utilize vegetable oils or palmitic acid or linoleic acid or oleic acid or other sources having reacting compounds similar to UCO or combination(s) thereof.
• ULO instead of ULO we can either utilize used industrial lubricants or used metal working fluids or used synthetic lubricants or used transformer oils or used hydraulic oils or used turbine oils or other sources having reacting compounds similar to ULO or combination(s) thereof.
• the Pre-fractionator column bottom required temperatures up to 210°C for re-boiling the ULO feed.
• the integration of DCU involves initial preheating of ULO feed up to desired boiling cut temperature using one of the product streams of DCU Main fractionator i.e., HCGO pump around which leaves the Main fractionator at around 360°C.
• HCGO coming out of the Main fractionator as a stream which will preheat the ULO feed to its desired boiling fraction temperature of above 200°C, thus the amount of energy supplied by the steam for re-boiling of ULO feed will be reduced as compared to earlier.
• Heat saving calculations were performed by taking hot HCGO (Specific Heat Capacity ⁇ 2.2 KJ/KgK) pump around of 0.228 MMTPA (considering 1 MMTPA DCU) with inlet temperature as 360°C and ULO feed (Specific Heat Capacity ⁇ 1.755 KJ/KgK) of capacity 1 MMTPA with inlet temperature as 150°C.
• Heat required for re-boiling 1 MMTPA ULO was ⁇ 2.2E+10 Kcal/year while heat which can be supplied by hot HCGO pump around for re-boiling ULO was around 1.78E+10 Kcal/year.
• the heat required will be reduced by 81% using this integration.
• the ULO and UCO as provided in Table-1 were mixed in different proportions and reactions were carried out at different operating temperatures simulating the surge drum conditions as indicated in Table-2.
• TAN of the base mixture and reaction mixture were compared, and it was found that TAN, metal content of the reaction mixture reduces. Further, from the experiments, it is observed that TAN content of reaction mixture having different compositions of ULO and UCO decreases with increase in operating temperature. It appears to be because as temperature increases, reaction between fatty acids of UCO and polyglycols of ULO increases, and furthermore, decarboxylation of aliphatic fatty acids starts above 150°C which may also be the factor reduction of TAN.
• Table-2 TAN distribution of reaction mixture at different temperature (in degree Celsius) and composition Feed ULO and UCO ULO and UCO (Base mixture) (Reaction Mixture) Composition, wt% 50 +50 50 + 50 Pressure, Kg/cm 2 g 1 1 1 1 1 1 Temperature°C 30 50 100 150 200 Residence Time, min 60 60 60 60 60 TAN 6.95 5.29 4.26 2.69 2.0 Composition, wt% 75 +25 75 + 25 Pressure, Kg/cm 2 g 1 1 1 1 1 Temperature°C 30 50 100 150 200 Residence Time, min 60 60 60 60 60 TAN 3.51 3.13 2.96 2.05 1.2 Composition, wt% 25 +75 25 + 75 Pressure, Kg/cm 2 g 1 1 1 1 Temperature°C 30 50 100 150 200 Residence Time, min 60 60 60 60 60 TAN 8.61 7.24 6.41 5.15 4.13
• Example 3 Reduction of phosphorus, metal (zinc, calcium) content in ULO lighter fraction (boiling range below 200°C)
• Example 5 Steam cracking of ULO+UCO lighter fraction (boiling range below 200°C) for light olefins and aromatics

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