Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
  • C10G21/06—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents characterised by the solvent used
  • C10G21/12—Organic compounds only
  • C10G21/16—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
  • C10G21/02—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents with two or more solvents, which are introduced or withdrawn separately
• • 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
  • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
• • 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
  • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
  • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
  • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
  • C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
• • 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
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/302—Viscosity
• • 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
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/308—Gravity, density, e.g. API
• • 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
  • C10G2300/4025—Yield
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/80—Additives
  • C10G2300/802—Diluents
• • 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
  • C10G2400/18—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

• This Invention relates to a process for producing process oil by means of reextraction of distillate aromatic extract (DAE) at lubricant oil processing. More specifically, the present invention relates to liquid-liquid extraction process from DAE feed which resulted treated distillate aromatic extract (TDAE) that have low content of polyaromatic hydrocarbon (PAHs) and content of polycyclic aromatic (PCA) less than 3%.
• DAE distillate aromatic extract
• PAHs polyaromatic hydrocarbon
• PCA polycyclic aromatic
• process oil The world ' s demand of process oil is estimated around 1,000,000 ton per year, including the European that consumed about 250,000 ton.
• This process oil consists of various types, such as. DAE, residual aromatic extract (RAE) , mild extraction solvate (MES) , and naphthenic oil.
• the limit of 8 Grimmers PAH are assumed equivalent to polycyclic aromatic (PCA) content less than 3% weight. This regulation is effective on 1 January 2010.
• the eight (8) substances of PAH referred are Benzo (a) pyrene (BaP) , Benzo (e) pyrene (BeP), Benzo (a) antracene (BaA) , Chrysene (CHR) , Benzo (b) fluoranthene (BbFA) , Benzo ( ) fluoranthene (Bj FA) , Benzo ( k) fluoranthene (BkFA) and Dibenzo (a, h) antracene (DBAhA) .
• the Measurement of 8 Grimmer PAH content can be conducted by means of Gas Chromatography Mass Spectrometer Isotope dilution method (GCMS-SIM) , while PCA content can be analysed gravimetricaly according to IP-346 method.
• GCMS-SIM Gas Chromatography Mass Spectrometer Isotope dilution method
• the IP-346 analysis method can only measure the amount of PCA compound as a group of aromatic compound, though the group of PAH compound that contained in the group of aromatic (PCA) must be analyzed, as well.
• GCMS Gas Chromatography Mass Spectrometer
• component of aromatic compounds content in the second extract product is minimum 20 % weight, whereas in the present invention the component of aromatic compound is larger than 25 % weight, even can reach as much of 30 to 37% weight.
• initial feeds that is DAE-1, DAE-2 and DAE-3
• DAE feeds that consist of mixing two DAE Feed or three DAE Feed at once.
• Determination of component of the formula of DAE Feed is defined base on the kinematic viscosity at temperature of 100 °C of the three DAEs, that is, DAE-1 : 14 - 17 cSt, DAE- 2: 19 - 35 cSt dan DAES: 52 - 67 cSt, respectively.
• the mixing of these three type of DAE will produce DAE Feed that have kinematic viscosity at temperature of 100 °C as high as 24 - 57 cSt with density 0,99 - 1,20 kg/liter.
• This present invention discloses a process of DAE production conducted through steps as follow; mixing the DAE Feed obtained from the above mixing process with a diluent in-line or off-line to give rise to flow of Mixture of DAE Feed at density of 0, 75 - 0, 85 kg/liter; guiding the flow direction of Mixture of DAE Feed toward the extractors that have isothermic temperature conditions; contacting the feed flow with certain solvent, such as furfural, N-methyl pyrrolidone (NMP) , and dimethylsulfoxide (DMSO) to carry out a counter current liquid-liquid extraction at the appropriate isothermic temperature , that is, 22 to 35 °C.
• solvent such as furfural, N-methyl pyrrolidone (NMP) , and dimethylsulfoxide (DMSO)
• TDAE TDAE- I dan TDAE.
• TDAE-1 contains PCA less than 3% weight
• TDAE-2 contains .
• HACE high aromatic concentrated extract
• Figure 1 is diagram flow of process on Blending of DAE Feed, Mixture of DAE Feed and TDAE-1 and TDAE-2 productions.
• Figure 1 explains the flow diagram of TDAE-1 and TDAE-2 production.
• Flows (1, 2, and 3) illustrate the mixing process of one, two or three types of DAE to yield the DAE Feed (4).
• the mixing process are conducted at the kinematic viscosity desired, at temperature of 100°C, that is, 24 - 67 cSt and density 0, 98 - 1, 20 kg/liter.
• the formula determinations are based on the kinematic viscosities at temperature of 100°C for each component of DAE-1, DAE-2 and DAE-3, respectively.
• Mixing process are conducted in in-line or off-line and completed with stirring in a container.
• the mixture of raffinate phase and mixture of extract phase then are guided to the Recovery Unit (10 and 13), respectively, to yield TDAE-1 and TDAE-2 and HACE (14) products, at the same time recovering all the solvent and diluents for continues reutilization .
• the process for TDAE-1 and TDAE-2 production in the present invention is started with DAE feed making by mixing the components of DAE-1, DAE-2 and DAE-3; or using a single type of DAE.
• the mixing manner can be applied to two or three types of the DAE.
• the formula determination is based on the kinematic viscosities at temperature of 100°C for each component of DAE-1, DAE-2 and DAE-3 so that they yield " DAE Feed with the kinematic' viscosity at 100°C, between 24 to 67 with density of 0,98 - 1,20 kg/liter.
• the mixing process are conducted in-line or off-line and completed with stirring them in a container.
• the next process is mixing the DAE feed and diluent of alkane compound/paraffin that have chain of carbon atom range C5 - C8.
• the ratio of the mixing between the diluent and the DAE Feed is 0.3 - 3.0, preferably at 1.0. This is done using an equipment that can control and that arrange the amount of diluent flow into the flow of DAE Feed, so that yield Mixture of DAE Feed with density between 0.75 to 0.80 kg/liter.
• This flow of Mixture of DAE Feed then become next feed at liquid-liquid extraction process in the extracttor (7).
• this extractor consist of some compartments, wherein each compartment provided with one static disc and one turbine agitator which is revolvable in accordance with the desired operation condition.
• the turbine agitator function to disperse each of flow to become droplet so that a perfect extraction process may take place at a minimum density difference of 0.05 kg/liter.
• the extraction process of Mixture of DAE feed in the extractor is carried out using certain solvent, such as furfural, NMP and DMSO as polar solvent.
• the operation condition is arranged in a manner such that the isothermic temperature at upper and lower extractor are at 22-35°C achieved, with rotational speed of agitator 75 - 100 RPM, and the ratios of certain solvent such as furfural, NMP and DMSO and the DAE mixture feed range 0.5 - 2.0.
• the ratio of polar solvent to DAE mixture feed ranges 1.7 - 2.0 a TDAE-1 containing PAH less than 10 mg/kg and BaP less than 1 mg/kg with PCA less than ,3% weight will be yielded.
• the ratio of. - polar solvent to __DAE mixture feed ranges 0.5 - 1.7 a TDAE-2 containing PAH less than 10 mg/kg and BaP less than 1 mg/kg with PCA less than 3% weight will be yielded.
• the extraction process requires 15-30 minute time for retention of Mixture of DAE Feed so that the layers of mixture of raffinate and mixture of extract are formed. During this process no pseudo raffinate is present such that occurs in the other regular extraction processes.
• the interface layer of the two mixtures can be set through a control equipment disposed at the lower portion of the extractor. The placement of the equipment at the lower portion is to prevent the undesirables extract flow (entrainment) from entering the flow of raffinate which may lower the quality of the raffinate.
• the mixture of raffinate is led into the solvent recovery unit for separation of raffinate from its certain solvent components, like furfural, NMP and DMSO and diluent.
• TDAE-1 or TDAE-2 which have the kinematic viscosities at temperature of 100°C (ASTM D445-06) above 16 cSt, the aromatic component analysed using the method of ASTM D 2140- 97 ranges 25-38 % weight, specific gravity at 15.6°C ranges 0,966 - 0,988 , aniline point ranges 43, 0 - 75, 0 °C, refractive index at 20°C ranges 1,5379 - 1,5546.
• the mixture of extract is led into the recovery unit for extract separation process from its certain solvent component, like furfural, NMP and DMSO. From this process an end product, that is, HACE will be obtained.
• Flo.w of certain solvents like furfural, NMP and DMSO and the . diluent from solvent recovery unit are collected at one particular decanter * (container) henceforth, conducted separation process between diluent and the certain solvent, like furfural, NMP and DMSO. Both of the flow is returned back into the extraction process that run continuously.
• the TDAE-1 and TDAE-2 being produced will be utilized as process oil in the tyre manufacturing and in the printing ink replacing the DAE that will be totally eliminated from its application due to its poor health effects due to the content of carcinogen substances. ⁇ Examples>>
• the extract of DAE-1 , DAE-2 , and DAE-3 are prepared according to their properties as can be seen in the Table 1, respectively.
• the mixing process of the two or three DAE are conducted at the kinematic viscosity desired, that is, at temperature of 100°C, is 24 to 60 cSt.
• the formula determination is based on the kinematic viscosities of each component of DAE-1, DAE-2 and DAE-3, respectively, so that they can yield the desired.
• DAE Feed Mixing process are conducted in-line or off-line and completed with stirring them in a container.
• PAH is the sum of all individual polyaromatic hydrocarbon compounds .
• ** ⁇ EC is the sum of 8 types of individual polyaromatic hydrocarbon compound (8 Grimmer PAH) that are . restricted, according to European Legislation No ⁇ . 2005/69/EC.
• the amount of 8 Grimmer PAH content disclosed at Table 3 is 106, 890 mg/kg.
• TDAE product can be lowered to 10 mg/kg, including the Benzo (a) pyrene with the amount of less than 1 mg/kg.
• Example 2 Preparation of the Mixture of Feeds >
• DAE Feed is mixed with a non polar aliphatic diluent with the chain of carbon from C5 to C8 and with ratio of diluent to the DAE Feed between 0.3 to 3.0.
• the process of feed mixing is executed at temperature of 25 to 70 °C.
• the data on the density after the mixing process is shown at Table 4.
• DAE Feed Mixture 1 resulted from mixing DAE Feed 1 with n-hexane at a ratio of 1 resulted density of 0,81 kg/liter.
• the process of liquid-liquid extraction to produce process oil is conducted using counter current method in an extraction column at temperature of 22 to 50 °C.
• Phenantrene 0,016 . 0, 082 0, 012 . 0, 015 0, 017 0, 102
• Benzo (c) phenantrene ;.: ' - ⁇ o , oo i ⁇ 0, 001 ⁇ 0, 001 0, 002 0, 001 0,040
• Tripenilena/ chrysene 0, 001 0,005 ⁇ 0, 001 0,011 0, 001 0,083
• Table 6 discloses the amount of 8 Grimmer PAH content is 0.001 - 0.273 mg/kg, which is considered far below the limit of PAH allowed by the European legislation (10 mg/kg) , whereas it is found that the highest content of Benzo (a) pyrene is 0.033 mg/kg which is still below the allowable limit of the European Legislation (1 mg/kg) .
• TDAE product can fulfill the PAHs allowable limit of the European Legislation at the same time met the PCA limit of less than 3% weight.
• the TDAE can meet the same PAH limit although the PCA content is higher than 3% weight, even as high as 13.2% weight.
• the mutagenity test was conducted using AMES Test based on OECD Guidelines for Testing of Chemicals No. 471 (1997).
• Salmonella typhimurium TA 1535 was used as microbe material which was very sensitive to mutagenic compound.
• the number of colony which grew was an indicator of mutagenic activity of the PAH. compound in the DAE Feed, TDAE-1 and TDAE-2, respectively.
• Table 8 Based on the AMES Test as shown in Table 8, the following conclusions are drawn:
• TDAE-1 and TDAE-2 The number of bacteria colony in the TDAE-1 and TDAE-2 was similar 1 to that in the control (spontaneous reversion of the colony) . This indicates that TDAE-1 and TDAE-2 products can be classified as mutagenic or carcinogenic compound.
• Liquid- liquid extraction is a technological process which based on method of operation of mass transfer to a feed that is contacted with a solvent for extracting dissolvable substances (solute) from feed materials.
• Feed materials which . consist of carrier and solute must have a property, that is, cannot be mixed (immiscible) or can be mixed partially (miscible) with the solvent, so that only solute that have higher solvability than the diluents can move into the solvent.
• “Diluent” is an alkane compound that used to lower the density of feed materials.
• Extractor is a type of agitation column extractor used in the experiments of the present invention, hereinafter referred to as extractor.
• the main part of this extractor is a turbine agitator which can be operated on the hydrodynamic conditions and serves as a stirrer to generate droplets spread.
• PCA or Polycyclic Aromatic is organic compound that consist of 3 or more rings of aromatic compound with or without branch chain, where in the PCA are contained PAH (Polycyclic Aromatic Hydrocarbon) compound and organic compound that contain hetero-atom like Nitrogen (N) , Sulphur (S) and Oxygen (0) . Not all compound that grouped as PAH have the property of carcinogenic.
• PAH or Polycyclic Aromatic Hydrocarbon is chemical compound that consist of aromatic ring bonding and does not contain hetero-atom or other substituent, consist of carbon and hydrogen molecules.
• PAH or Polycyclic Aromatic Hydrocarbon There are 23 types individual PAH compounds in DAE Feed where 8 types of them stated as carcinogenic substances or called 8 Grimmer PAH.
• Process Oil is oil which is rich in aromatic compound, used as solvent in the tire making or may also be used as a solvent at the printing ink industry.
• IP 346 is the standard method to determine PCA in lubricating oil or petroleum fraction that does not contain asphaltene .

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