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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/049—The hydrotreatment being a hydrocracking
• • 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step 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
  • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
  • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
  • C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
  • C10G67/0454—Solvent desasphalting
  • C10G67/0463—The hydrotreatment being a hydrorefining
• • 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

Definitions

• the present invention relates to a refining method for heavy oil that can efficiently remove impurities derived from a crude oil by a solvent extraction process and a hydrorefining process, and in particular, to a method that can obtain a refined oil that is suitable as a feedstock for light olefin production from a heavy oil that could not be conventionally used as feedstock for light olefin production.
• distillate that is, distillated oils drawn off from a tower by distillation
• these impurities can be removed by a simple refining process.
• they can be used s for automobile fuel, gas turbine fuel, petrochemical feedstock, or the like, which are high quality oil products from which impurities have be removed to a high degree.
• One use of high quality refined oil is as a petrochemical feedstock.
• Light olefins such as ethylene, propylene, and the like, which are key materials in the petrochemical field, are produced by thermal cracking using light oils such as ethane and naphtha as the main feedstock, but a part of the heavy fraction, such as gas oil and vacuum gas oil, are also used as feedstock.
• ethylene plants that use ethane as feedstock are common, while in Japan, Asia, and Europe, where naphtha is inexpensive, in most cases naphtha is used as the feedstock.
• Vacuum gas oil whose molecular weight is higher than naphtha and contains much sulfur, is used as a feedstock for an ethylene plant, and is considered to be the limit for commercial operation.
• the invention provides a refining method for heavy oil that can economically recover refined oil suitable as a feedstock for light olefin production by carrying out a refining process using a simple and reliable method on heavy oil such as an atmospheric residue that is not conventionally suitable as a feedstock for light olefins.
• the inventors have discovered that impurities in heavy oil can be efficiently removed to obtain a high quality refined oil having impurities removed to a high degree by using as a feedstock a heavy oil having a hydrogen content of 12 wt % or less, processing the heavy oil so that the hydrogen content is increased by a certain amount or greater by using a solvent extraction, and then processing the obtained deasphalted oil so that the hydrogen content is increased by a certain amount or greater by using a hydrorefining process.
• a refined oil is obtained by processing that includes a solvent extraction process that obtains an extracted oil by subjecting a feed oil to a solvent extraction process and a hydrorefining process that obtains a refined oil by subjecting the obtained extracted oil to a hydrogenation process in the presence of hydrogen and a catalyst.
• This feed oil is a heavy oil having a hydrogen content of 12 wt % or less.
• a deasphalted oil (DAO) is obtained as an extracted oil by subjecting the feed oil to a solvent extraction process such that the hydrogen content is increased by 0.2 wt. % or greater over that of the feed oil.
• a refined oil is obtained by hydrorefining the deasphalted oil such that the hydrogen content is increased by 0.5 wt % or greater over that of the deasphalted oil.
• a high quality refined oil can be reliably obtained that has impurities reduced to a high degree that cannot be anticipated by using either of the refining processes alone because impurities that are difficult to remove by downstream hydrorefining are processed in advance under conditions in which the hydrogen content is increased by a certain amount or greater by using a solvent extraction, and subsequently being processed under conditions in which the hydrogen content increases by a certain amount or greater by using a hydrorefining process.
• the hydrogen content of the obtained refined oil is 11.5 wt % or greater, and most preferably, 12.0 wt % or greater.
• a commercial operation becomes possible in which the generation of coking and fouling can be repressed even during a thermal cracking reaction by application to a feedstock for light olefin production, which is a petrochemical feedstock. Therefore, the present invention can obtain a refined oil having a high added value reliably and efficiently, and is economically superior.
• the present invention uses as a feedstock a heavy oil having a hydrogen content of 12 wt % or less, and preferably 10 to 12 wt %, and in a solvent extraction process and a hydrorefining process, the heavy oil is processed under conditions in which respective predetermined degrees of refinement are attained.
• the heavy oil having a hydrogen content of 12 wt % or less used in the present invention generally includes residues such as atmospheric residue, ultra heavy oil, and the like, whose uses are limited because of their high impurity concentrations.
• the hydrogen content of these heavy oils is generally 9 to 12.5 wt %, and many are 9 to 11.5 wt %, and conventionally the heavy oils have been considered to be unsuitable as a petrochemical feedstock for light olefins or the like because their impurities could not be removed even by refining, and thus have not been used.
• the present invention carries out solvent extraction processing as a first process using heavy oil having a hydrogen content of 12 wt % or less as a feed oil, and recovers a deasphalted oil, which is an extracted oil having the hydrogen content increased by 0.2 wt. % or greater.
• the asphaltene component having a low hydrogen content is selectively removed.
• This asphaltene component has a micelle structure comprising compounds having a low hydrogen content such as condensed polycyclic aromatics and cycloparaffin rings, and it is known that among these, residual carbon and metallic porphyrin compounds such as V and Ni are incorporated, and thus impurities are concentrated. It is known that the asphaltene component severely inhibits the hydrorefining reaction, and promotes degradation of the catalyst.
• the solvent extraction process is carried out under conditions in which the hydrogen content increases by 0.2 wt % or greater, and as a result, a predetermined amount of asphaltene is selectively removed.
• a conventionally known solvent deasphalting process can be applied, and by bringing the heavy oil into contact in countercurrent with the C3 to C5 solvents in a solvent extraction tower, the deasphalted oil and the asphaltene, in which the former has a high hydrogen content and diluted metals and residual carbon, the latter has a low hydrogen content and concentrated metals and residual carbon, are drawn off.
• the extraction processing conditions are controlled so that the hydrogen content is increased by 0.2 wt % or greater, and the extracted oil of the present invention can be obtained.
• C3 to C5 solvents preferably at least one selected from propane, butane, or pentane is used.
• the deasphalted oil is recovered as an extracted liquid along with the solvent from the top of the extraction tower, and can be obtained by subjecting the solvent in the extracted liquid to separation and removal under supercritical conditions.
• the asphaltene is recovered as a raffinate along with a portion of the solvent from the bottom of the tower, and the solvent in the raffinate is recovered by vaporization.
• the hydrogen content of the deasphalted oil obtained by this type of solvent extraction process is increased by 0.2 wt % or greater than the hydrogen content of the feedstock heavy oil. Furthermore, an increase by 0.2 to 1.5 wt % is preferable, and an increase by 0.2 to 1.2 wt % is most preferable.
• the increased amount of the hydrogen con in the solvent extraction process changes depending on the value of the hydrogen content in the feedstock heavy oil. That is, in the case that the hydrogen content of the feed oil is 11 wt % or greater, in the solvent extraction process, the extraction process conditions are controlled such that the increase in the hydrogen content is preferably by 0.2 to 1.0 wt %, or most preferably, 0.2 to 0.5 wt % of the feed oil. If the hydrogen content is less than 11.0 wt %, an amount of increase is preferably in a range of 0.5 to 1.5 wt %, and most preferably, 0.8 to 1.3 wt %.
• the deasphalted oil subjected to a solvent extraction process such that the hydrogen content increases by 0.2 wt % or greater in the solvent extraction process described above is next subject to a hydrorefining process as a second process.
• hydrorefining process of the present invention processing is carried out under the condition that the hydrogen content is increased by 0.5 wt % or greater.
• This hydrorefining process is a representative refining process in which hydrocarbons are processed at high temperature and high pressure in the presence of hydrogen and a catalyst, and can include all the reactions such as hydrocracking, hydrodesulfurization, hydrodemetalization, and hydrodenitrogenation.
• hydrocracking which obtains a low molecular weight refined oil from the feedstock heavy oil
• hydrodesulfurization which reacts the sulfur compounds in the hydrocarbons with hydrogen to produce and separate out hydrogen sulfide, and obtain a refined oil with a low sulfur concentration from a feed oil
• hydrodemetalization in which a metallic compound in the hydrocarbon is hydrolyzed at high temperature and high pressure in the presence of hydrogen, made into elemental metals, and precipitated on the catalyst to obtain a refined oil having a low metal concentration
• hydrodenitrogenation in which the nitrogen compounds in the hydrocarbons are reacted with hydrogen at high temperature and high pressure in the presence of hydrogen to produce and separate out ammonia and obtain a refined oil that has a low nitrogen concentration from the feed oil.
• the impurities in heavy oil include sulfur components, metals, and the like, but because the removal of these impurities in advance using only a hydrorefining process in an upstream solvent extraction process is for removing troublesome impurities, the impurities can be efficiently reduced to a very low concentration, without severe conditions.
• the hydrorefining process of the present invention preferably at least two types of catalyst are used in a combination selected from a hydrodemetalization catalyst, a hydrodesulfurization catalyst, a hydrodesulfurization and hydrodemetalization catalyst, or a hydrocracking catalyst.
• the catalyst used in hydrorefining is Co/Mo, Ni/Co/Mo, or Ni/Mo.
• the conditions for the hydrorefining reaction are not particularly limited, but preferably the ranges of the hydrorefining reaction conditions are those that are generally employed.
• the hydrogen partial pressure is 60 to 150 kg/cm 2 , and most preferably 80 to 130 kg/cm 2 .
• the hydrogen to oil ratio is preferably 400 to 1200 Nm 3 /kl, and most preferably 600 to 1000 Nm 3 /kl.
• the LHSV is preferably 0.1 to 1.0/hr, and most preferably 0.2 to 0.8/hr.
• the reaction temperature is preferably 340 to 440° C., and most preferably 350 to 420° C.
• Such conditions are the general conditions for hydrorefining, and in the present invention, if the hydrorefining process is carried out after the upstream solvent extraction process under conditions that increase the hydrogen content by 0.5 wt % or greater, the impurities in the final refined oil can be efficiently reduced.
• the hydrogen content of the refined oil obtained by the hydrorefining process with respect to the deasphalted oil is preferably increased by 0.5 to 1.0 wt %, and most preferably by 0.5 to 0.9 wt %.
• the hydrogen content of the refined oil obtained by the hydrorefining process with respect to the deasphalted oil is increased by preferably 0.6 to 1.5 wt %, and most preferably 0.8 to 1.3 wt %.
• the hydrogen content in the hydrorefining process of the present invention is preferably increased by 0.5 to 1.0 wt % if the hydrogen content of the deasphalted oil obtained by the upstream solvent extraction process is 11.5 wt % or greater, and preferably by 0.6 to 1.5 wt % if it is less than 11.5 wt %.
• the Conradson carbon residue and metal components such as Ni and V which are present in the asphaltene in a state that is concentrated and difficult to remove, can be selectively removed by solvent extraction, and then in a hydrorefining process, the impurities such as sulfur and metals such as Ni and V, which are present in an easily removable state, can be thoroughly removed.
• an refined oil that is processed so as to satisfy the conditions described above will be effective as a refined oil in the present invention, and in particular, in the case that it is used as a feedstock for light olefin production, the hydrogen content must be 11.5 wt % or greater, and preferably 12.0 wt. % or greater.
• the hydrogen content of the refined oil obtained by the solvent extraction and hydrorefining, two-stage refining of heavy oil must increase by 0.7 wt % or greater than the feedstock heavy oil, and preferably by 0.8 to 2.7 wt %, and most preferably, 1.0 to 2.2 wt %.
• the hydrogen content of the final refined oil is preferably 11.5 wt % or greater, and most preferably 12.0 to 13.5 wt %.
• the extraction operation was carried out under conditions wherein the hydrogen content of this feed oil is increased by 0.2 wt % or greater, but the Ni and V metals are included in tens to thousands of wtppm in the residue and the ultra heavy oil. This is because they are concentrated in the asphaltene, and in order to selectively remove the asphaltene in the solvent extraction process, the concentration of the Ni and V metals in the deasphalted oil, which is the refined oil whose content in the deasphalted oil has been extracted by the solvent extraction process, is 70 wtppm or less, and most preferably 50 wtppm or less.
• the solvent extraction process is carried out so that preferably the Conradson carbon residue content is 15 wt % or less, and most preferably 12 wt % or less. That is, the hydrogen content is increased by 0.2 wt % by the solvent extraction process, and at the same time, the concentration of the Ni and V metals is preferably 70 wtppm or less, and the Conradson carbon residue is 15 wt % or less, and thereby the conditions for the downstream hydrorefining process are not made severe, impurities are reliably removed, and a high quality refined oil can be obtained.
• the sulfur concentration of the deasphalted oil is preferably 5 wt % or less, and most preferably 4 wt % or less.
• the sulfur component in the final refined oil obtained by the next hydrorefining process can be reliably processed so as to be 0.5 wt % or less, and preferably 0.3 wt % or less.
• the Conradson carbon residue concentration is 15 wt % or less, and the sulfur concentration is 5 wt % or less
• processing can be reliably carried out such that in the final oil obtained by the subsequent hydrorefining process, the Ni and V concentration of the final refined oil obtained in the subsequent hydrorefining process will be 2 wtppm or less, and preferably 1 wtppm or less
• the Conradson carbon residue concentration will be 1 wt % or less
• the sulfur concentration will be 0.5 wt % or less, and preferably 0.3 wt % or less.
• the solvent extraction process and the hydrorefining process are carried out so that the Ni and V content in the final refined oil is 2 wtppm or less, or more preferably, 1.0 wtppm or less.
• the deasphalted oil whose Ni and V metal content is reduced to 70 wtppm or less by the solvent extraction process, is further reduced to 1 wtppm or less by hydrorefining, coking can be severely reduced, the refined oil can be obtained with a high yield, and this refined oil can be used as a thermal cracking feedstock for light olefin production.
• the maintainability of coking and fouling due to heavy oil by-products and the olefin yield determine its economy, and in particular, the target of the yield of the light olefins is 25% or more. Furthermore, looking at the light olefins in detail, the targets are an ethylene yield of 15% or greater and a propylene yield of 10% or greater.
• Periodic decoking and cleaning must be carried out in response to the coking that influences the maintainability of the thermal cracking unit and fouling due to heavy oil by-products.
• by-product heavy oil when the high-temperature cracking products cracked in a cracking vessel are quenched by a downstream heat exchanger in order to prevent severe cracking, the heat exchanger and the pipes become clogged when the amount of generated heavy oil is large, and long term continuous operation is made impossible.
• the amount of generated by-product heavy oil in the thermal cracking reaction allow aiming at commercial operation.
• the refined oil obtained by the present invention subjects to a refining process a heavy oil having a hydrogen content of 12 wt % or lower that is not conventionally used as a feedstock for light olefin production, and in the case that it is provided as a feedstock for light olefin production, the olefin yield during the thermal cracking and coking properties are favorable, and industrial production is possible.
• the feedstock is separated into distillate oil and residue, which will serve as a starting feedstock, the atmospheric distillate residue and the vacuum distillate residue, which are residues, are subject to the solvent extraction and a hydrorefining process as described above to produce a refined oil, and in the refined oil, at least one part of this hydrorefined distillate oil is mixed with this refined oil to generate a refined oil.
• a heavy oil which is a residue having an API gravity of 14.3 (a hydrogen content of 11.25 wt %; a Ni+V metal content of 65 wtppm; a Conradson carbon residue (below, abbreviated “CCR”) of 11.1 wt %; and a S content of 3.95 wt %) is charged into the solvent extraction process unit as a feed oil, and using a normal pentane solvent (a solvent/oil ratio of 8/1), a deasphalted oil (below, abbreviated “DAO”) is obtained by extraction and separation so that the extraction rate is 81 wt %, subsequently this DAO is subject to a refining process under the following hydrorefining conditions, and thereby the refined oil 1 of the present invention is obtained.
• DAO deasphalted oil
• Ni/Mo+Ni/Co/Mo catalyst (a specific volume ratio of 1/9), a hydrogen partial pressure of 90 atm; an H 2 /Oil ratio of 600 Nm 3 /kl; a temperature of 380° C.; and an LHSV of 0.5 (1/hr).
• the feed oil used in Experimental Example 1 is charged into the solvent extraction process unit, using a normal pentane solvent (a solvent/oil ratio of 8/1), the DAO is obtained by extraction and separation so as to attain an extraction rate of 84 wt %, and subsequently the DAO is subject to hydrorefining under conditions identical to those of Experimental Example 1 to obtain the refined oil 2 of the present invention.
• a normal pentane solvent a solvent/oil ratio of 8/1
• Ni/Mo+Ni/Co/Mo catalyst (a specific volume ratio of 1/9), a hydrogen partial pressure of 85 atm; an H 2 /Oil ratio of 600 Nm 3 /kl; a temperature of 360° C.; and an LHSV of 0.5 (1/hr).
• Ni/Mo+Ni/Co/Mo catalyst (a specific volume ratio of 1/9), a hydrogen partial pressure of 110 atm; an H 2 /Oil ratio of 800 Nm 3 /kl; a temperature of 380° C.; and an LHSV of 0.3 (1/hr).
• Ni/Mo+Co/Mo catalyst (a specific volume ratio of 1/9), a hydrogen partial pressure of 90 atm; an H 2 /Oil ratio of 600 Nm 3 /kl; a temperature of 360° C.; and an LHSV of 0.5 (1/hr).
• the DAO is obtained by extraction and separation so as to attain an extraction rate of 86 wt %, and subsequently the DAO is subject to a refining process under the following hydrorefining conditions to obtain the comparative refined oil B of the present invention.
• Ni/Mo+Co/Mo catalyst (a specific volume ratio of 1/9), a hydrogen partial pressure of 90 atm; an H 2 /Oil ratio of 600 Nm 3 /kl; a temperature of 360° C.; and an LHSV of 0.5 (1/hr).
• the DAO is obtained by extraction separation so as to attain an extraction rate of 81 wt %, and subsequently the DAO is subject to a refining process under the following hydrorefining conditions to obtain the comparative refined oil C of the present invention.
• Ni/Mo+Co/Mo catalyst (a specific volume ratio of 1/9), a hydrogen partial pressure of 90 atm; an H 2 /Oil ratio of 600 Nm 3 /kl; a temperature of 345° C.; and an LHSV of 0.6 (1/hr).
• the comparative refined oil E is obtained by a refining process under the following hydrorefining conditions.
• Ni/Mo+Co/Mo catalyst (a specific volume ratio of 1/9), a hydrogen partial pressure of 150 atm; an H 2 /Oil ratio of 1000 Nm 3 /kl; a temperature of 380° C.; and an LHSV of 0.25 (1/hr).
• Example 5 Feed Refined Refined Refined oil D Refined oil E oil DAO oil A DAO oil B DAO oil C (extraction only) (hydrogenation only) Yield (wt %) 100 88 84 86 82 81 77 45 95 Hydrogen content 11.25 11.37 11.79 11.40 12.08 11.55 11.90 11.95 12.10 (wt %) Hydrogen content — 0.15 0.42 0.15 0.68 0.30 0.35 0.70 0.85 increase (wt %) Total hydrogen — — 0.57 — 0.83 — 0.65 0.70 0.85 content increase (wt %) V + Ni(wtppm) 65.0 16.8 ⁇ 0.1 13.5 ⁇ 0.1 7.3 ⁇ 0.1 2.0 7.0 Conradson carbon 11.10 4.30 1.47 3.70 0.81 2.60 1.21 0.50 5.70 residue (wt %) S (wt %) 3.95 3.57 1.03 3.51 0.32 3.35 0.83 3.07 0.50
• Reaction vessel an HPM ethylene cracking vessel having an inner diameter of 28 mm ⁇ and a length of 1440 mm (a heating section of 1200 mm) was used.
• Reaction temperature 900° C.
• Residence time 0.5 sec.
• the yield of the obtained light olefins was found from the gas composition in the generated gas analyzed using the generated gas amount and gas chromatography.
• the generated amount of by-product heavy oil was found from the amount of the bottoms after separating the naphtha fraction from the generated oil after quenching the thermal cracking gas by evaporation.
• the determination of the continuous operability was defined as 30 wt % or less (denoted O, indicating possible) and 30 wt % (denoted by X, indicating not possible) by using the generated specific gravity of the by-product heavy oil, which was precipitated in the quenching section branching from the reaction vessel and is the cause of fouling, with respect to the feed oil.
• the DAO obtained by the solvent extraction processing is extracted such that in comparison to the heavy feed oil, the hydrogen content increases by 0.2% or greater, subsequently processed so that in the hydrorefined oil the hydrogen content increases by 0.5 wt % or greater in comparison to the DAO, and as a result, the final refined oil is processed such that in comparison to the heavy feed oil, the hydrogen content increases by 0.7 wt % or greater.
• the Conradson carbon residue was 0.8 wt % or less, and the sulfur concentration was 0.3 wt % or less.
• the Conradson carbon residue was 0.8 wt % or greater and the sulfur concentration was 0.3 wt % or greater.
• a heavy oil which is a residue having an API gravity of 4.2 (a hydrogen content of 10.68 wt %; a Ni+V metal content of 246 wtppm; CCR, 25 wt %; and a S content of 5.5 wt %) is charged into the solvent extraction process unit as a feed oil, and using isobutane solvent (a solvent/oil ratio of 8/1), a DAO is obtained by extraction and separation such that the extraction rate is 63 wt %, subsequently this deasphalted oil is subject to hydrorefining under the following conditions, and the refined oil 5 of the present invention is obtained.
• isobutane solvent a solvent/oil ratio of 8/1
• Ni/Co/Mo+Co/Mo catalyst (a specific volume ratio of 2/8), a hydrogen partial pressure of 110 atm; an H 2 /Oil ratio of 800 Nm 3 /kl; a temperature of 380° C.; and an LHSV of 0.3 (1/hr).
• the DAO is obtained by extraction and separation so as to attain an extraction rate of 65 wt %, and subsequently the DAO is subject to refining under the following hydrorefining conditions to obtain the refined oil 6 of the present invention.
• Ni/Mo+Co/Mo catalyst (a specific volume ratio of 2/8), a hydrogen partial pressure of 140 atm; an H 2 /Oil ratio of 1000 Nm 3 /kl; a temperature of 375° C.; and an LHSV of 0.2 (1/hr).
• Ni/Mo+Co/Mo catalyst (a specific volume ratio of 2/8), a hydrogen partial pressure of 80 atm; an H 2 /Oil ratio of 800 Nm 3 /kl; a temperature of 340° C.; and an LHSV of 0.5 (1/hr).
• the comparative refined oil G is obtained by extraction and separation so as to attain an extraction rate of 55 wt %.
• Ni/Mo+Co/Mo catalyst (a specific volume ratio of 3/7), a hydrogen partial pressure of 140 atm; an H 2 /Oil ratio of 1000 Nm 3 /kl; a temperature of 375° C.; and an LHSV of 0.2 (1/hr).
• the Ni+V concentration was 0.1 wtppm or less
• the CCR was 1 wt % or less
• the sulfur concentration was 0.5 wt % or less
• Comparative Example 7 which was refined using only the solvent extraction process, it was understood that the recovery rate fell to 55%, and even when subject to extraction refining, the impurities could not be sufficiently removed.
• Experimental Example 6 of the present invention is compared to Comparative Example 8, which was refined only using the hydrorefining, even thought the hydrorefining was carried out under identical conditions, it was understood that there was a great difference in the removal of impurities, and after increasing the hydrogen content by a predetermined amount using a solvent extraction process in advance, by carrying out a hydrorefining process the impurities are thoroughly removed.
• the ethylene yield exceeds 15% and the propylene yield exceeds 10%, and furthermore, in view of the generation conditions of by-product heavy oil, the continuous operability is within a realizable range.
• the ethylene concentration did not exceed 15%, and furthermore, there was a large amount of generated by-product heavy oil, which is a problem for continuous operability.
• a refined oil having decreased impurities can be obtained by reliably and economically refining a heavy oil having a hydrogen content of 12 wt % or less, and thereby the conventionally limited uses of heavy oil have been greatly expanded.

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  • 2002-04-02 MX MXPA03008994A patent/MXPA03008994A/es unknown
  • 2002-04-03 PL PL02353151A patent/PL353151A1/xx not_active IP Right Cessation

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