EP0514549A1 - Procede pour raffiner du petrole brut - Google Patents

Procede pour raffiner du petrole brut Download PDF

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Publication number
EP0514549A1
EP0514549A1 EP91917699A EP91917699A EP0514549A1 EP 0514549 A1 EP0514549 A1 EP 0514549A1 EP 91917699 A EP91917699 A EP 91917699A EP 91917699 A EP91917699 A EP 91917699A EP 0514549 A1 EP0514549 A1 EP 0514549A1
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EP
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Prior art keywords
fraction
crude oil
oil
distillation
residual
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EP91917699A
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German (de)
English (en)
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EP0514549B1 (fr
EP0514549A4 (en
Inventor
Meishi Tanaka
Shuji Sugiyama
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Priority claimed from JP40619290A external-priority patent/JPH04209696A/ja
Priority claimed from JP41406490A external-priority patent/JP2863326B2/ja
Priority claimed from JP41406390A external-priority patent/JP2863325B2/ja
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Publication of EP0514549A1 publication Critical patent/EP0514549A1/fr
Publication of EP0514549A4 publication Critical patent/EP0514549A4/en
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    • 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
    • C10G69/04—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 catalytic 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps

Definitions

  • the present invention relates to a novel method of refining crude oil. More particularly, the present invention relates to a novel method of refining crude oil with higher efficiency by simplified unit.
  • crude oil is made into products of various fractions by distillation of the crude oil at the atmospheric pressure. Each product is then treated to a quality level of refining suited for the purpose of the individual products by appropriate methods such as hydrogenation and the like.
  • the number of the units utilized for the refining is necessarily increased and, at the same time, the units are complicated because the treatments for the refining are made separately for each of the fractions after the crude oil is separated into the fractions.
  • Yields of individual products and the content of sulfur are varied depending on the kind of crude oil utilized.
  • the same unit is utilized for desulfurization of both of kerosene and gas oil. Because of these reasons, it has been the general practice that intermediate tanks are installed between the units for various processes and fractions are temporarily stored in these intermediate tanks. This practice requires additional expenditures as well as additional spaces to install them. The fractions are cooled down during the storage in the intermediate tanks and energy is not utilized efficiently in these systems of units.
  • the object described above can be attained by a method comprising separation of a naphtha fraction from crude oil, desulfurization of the residual fraction and, then, separation of the desulfurized fraction into further fractions by distillation or by a method comprising separation of a naphtha fraction from crude oil and distillation of the residual fraction after the treatment of the residual fraction for refining by well arranged introduction of hydrotreating, separation under high pressure and fluid catalytic cracking of the heavy residual oil.
  • the present invention was completed on the basis of the discovery.
  • the present invention provides a method of refining crude oil by distillation and desulfurization for preparation of petroleum products which comprises separating a naphtha fraction from crude oil by distillation, hydrodesulfurizing the residual fraction which remains after the naphtha fraction has been removed from the crude oil and separating the hydrodesulfurized fraction into further fractions by distillation (Invention 1).
  • the present invention also provides a method of refining crude oil by distillation and desulfurization for preparation of petroleum products which comprises separating a naphtha fraction from crude oil by distillation, hydrodesulfurizing the residual fraction which remains after the naphtha fraction has been removed from the crude oil, hydrotreating the hydrodesulfurized fraction and separating the hydrotreated fraction into further fractions by distillation (Invention 2).
  • the present invention further provides a method of refining crude oil by distillation and desulfurization for preparation of petroleum products which comprises separating a naphtha fraction from crude oil by distillation, hydrodesulfurizing the residual fraction which remains after the naphtha fraction has been removed from the crude oil, separating the hydrodesulfurized fraction into a light fraction and a heavy residual oil in a high pressure separator and hydrotreating the light fraction (Invention 3).
  • the present invention still further provides a method of refining crude oil by distillation and desulfurization for preparation of petroleum products which comprises separating a naphtha fraction from crude oil by distillation, hydrodesulfurizing the residual fraction which remains after the naphtha fraction has been removed from the crude oil, separating the hydrodesulfurized fraction into a light fraction and a residual heavy oil in a high pressure separator, cracking the residual heavy oil by fluid catalytic cracking, fractionating the cracked residual heavy oil by distillation, combining a cracked gas oil obtained by the fractionation by distillation with the light fraction separated in the high pressure separator and hydrotreating the combined fraction (Invention 4).
  • Figure 1 ⁇ Figure 4 are schematic flow diagrams of examples of the basic constitutions of units to perform the present invention.
  • Figure 5 shows the storage stability of the light fractions obtained in Examples 2 and 3.
  • Figure 6 shows the storage stability of the light fractions obtained in Example 4 and Comparative example 2.
  • Figure 7 shows the storage stability of the light fractions obtained in Example 5, Comparative examples 3 and 4.
  • Figure 1 is a schematic flow diagram of an example of a basic constitution of units to perform Invention 1 of the present invention.
  • the units for refining in Invention 1 comprise preliminary distillation tower 1 for separation of a naphtha fraction in the crude oil by distillation, a unit for desulfurization of the residual fraction which remains after the naphtha fraction has been removed, such as the hydrodesulfurization unit 2 for desulfurizing the residual fraction by the contact with a desulfurizing catalyst in the presence of hydrogen, an atmospheric distillation tower 3 for fractionation of the residual fraction treated by the desulfurization process into fractions, such as kerosene, gas oil, heavy gas oil and the residual oil, an hydrodesulfurization unit 4 for desulfurizing the naphtha fraction separated from the crude oil in the preliminary distillation tower 1 and a heat exchanger 5 for recovery of heat.
  • a unit for desulfurization of the residual fraction which remains after the naphtha fraction has been removed such as the hydrodesulfurization unit 2 for desulfurizing the residual fraction by the contact with a desulfurizing catalyst in the presence of hydrogen
  • an atmospheric distillation tower 3 for fractionation of the
  • the naphtha fraction (C5 ⁇ 157°C) in the crude oil is, at first, separated from the crude oil by distillation.
  • the optimum condition of the distillation is suitably adopted according to the composition and the properties of the crude oil and the constitution and the stage number of the distillation tower.
  • the generally adopted condition is a pressure in the range from the atmospheric pressure to 10 kg/cm2G and a temperature in the range from 145 to 200°C. It is preferable that the naphtha fraction in the crude oil is separated at a pressure around 1.5 kg/cm2G and at a temperature in the range described above.
  • the naphtha fraction separated in the preliminary distillation tower 1 is desulfurized in the hydrodesulfurization unit 4 by utilizing a conventional method.
  • the content of sulfur in the naphtha fraction can be made 1 weight ppm or less by the desulfurization by utilizing a Co-Mo catalyst, at the temperature in the range from 280 to 340°C, at the pressure in the range from 18 to 40 kg/cm2G, at the liquid hourly space velocity (LHSV) in the range from 3 to 10 hr ⁇ 1 and at the amount of hydrogen in the range from 50 to 100 Nm3/kl.
  • the separation of the naphtha fraction is preferably made by distillation but other methods such as flashing operation may be utilized.
  • the heavy fraction comprising the kerosene fraction and other heavier fractions which is the residual fraction in the preliminary distillation tower 1 is introduced into the hydrodesulfurization unit 2 without separating into its components. It is desirable that the hydrodesulfurization unit 2 is operated so that the content of sulfur in the final residual oil is controlled within a specified range of amount.
  • a catalyst for hydrodesulfurization such as a catalyst which comprises one or more than one kinds of metals of the VIth group or the VIIIth group of the Periodic Table, like Mo, W, Co and Ni, preferably Co-Mo and Ni-Mo, supported on a support, like alumina, silica, zeolite,
  • the temperature in the range from 370 to 420°C, the pressure in the range from 100 to 200 kg/cm2G, LHSV in the range from 0.2 to 2.0 hr ⁇ 1 and the amount of hydrogen in the range from 800 to 2,000 Nm3/kl are more preferable. Sulfur contained in other fractions than the residual fraction can be sufficiently removed by this method.
  • the fraction desulfurized by the above process is introduced to the atmospheric distillation tower and separated into the individual fractions.
  • the fraction is separated into the kerosene fraction, the gas oil fraction, the heavy gas oil fraction and the residual oil fraction by setting the cutting temperatures at the atmospheric pressure at the range from C5 to 157°C for the naphtha fraction, at the range from 157 to 239°C for the kerosene fraction, at the range from 239 to 371°C for the gas oil fraction, at the range from 371 to 472°C for the heavy gas oil fraction and at the range from 472°C to higher temperatures for the residual oil fraction.
  • the fractions ranging from the kerosene fraction to the residual oil fraction which come out from the main distillation tower 3 can, after the heat is recovered by utilizing the heat exchanger 5 with the crude oil, be sent for storage directly to the storage tanks of the corresponding products or delivered directly to customers because the fractions have already been finished with the treatment of desulfurization.
  • the desulfurization is made after the removal of the naphtha fraction and the fractions such as the kerosene fraction and the other fractions having higher boiling points are separated after the desulfurization, the units necessary for refining the crude oil are simplified to a great extent while the properties of the products are maintained at the same level or better than conventional products. Energy losses accompanied with the charging and discharging of materials to the intermediate tanks can be eliminated by removing the intermediate tanks. Because the process of desulfurization is performed on the combined fractions at the same time, the control of operation is made more easily and it is further possible that the cost of investment for control instruments is reduced and the number of operator is reduced.
  • unstable substances which may be formed during the desulfurization process can be separated and removed during distillation in the atmospheric distillation tower.
  • the stability of the gas oil fraction as the intermediate fraction can be improved.
  • Figure 2 is the schematic flow diagram of the basic constitution of the units to perform the method of Invention 2.
  • the units for refining to perform Invention 2 comprise the preliminary distillation tower 1 to separate the naphtha fraction in the crude oil by distillation, the desulfurization unit to desulfurize the residual fraction after the naphtha fraction has been removed, for example the hydrodesulfurization unit 2 to desulfurize the residual fraction by contact with a desulfurization catalyst in the presence of hydrogen, the hydrotreating unit 6 to remove nitrogen-containing compounds and other impurities from the fraction after the desulfurization and the atmospheric distillation tower 3 to fractionate the purified fraction by distillation into individual fractions, such as kerosene, gas oil, heavy gas oil and the residual oil.
  • the refining units for performing Invention 2 also comprise the hydrodesulfurization unit 4 to desulfurize the naphtha fraction separated in the preliminary distillation tower 1.
  • the naphtha fraction (C5 ⁇ 157°C) in crude oil is, at first, separated from the crude oil by distillation from the crude oil in the preliminary distillation tower 1.
  • the condition of distillation is similar to the condition described in performing Invention 1.
  • the content of residual sulfur in the naphtha fraction can be made 1 weight ppm or less by the distillation process.
  • the separation of the naphtha fraction is preferably made by distillation but other methods such as flashing operation may be utilized.
  • the heavy fraction comprising the kerosene fraction and other heavier fractions which is the residual fraction in the preliminary distillation tower 1 is introduced into the apparatus for hydrodesulfurization 2 without separating into its components. It is desirable that the apparatus for desulfurization 2 is operated so that the content of sulfur in the final residual oil is controlled within a specified range of amount.
  • the condition of operation is similar to the condition described in performing Invention 1.
  • the fraction desulfurized in the process described above is then introduced into the hydrotreating unit 6 without separating into the component fractions. It is desirable that the operation of the hydrotreating unit 6 is controlled so that the content of sulfur in the final residual oil is controlled within the specified range of amount and, at the same time, other impurities such as nitrogen-containing impurities are removed.
  • a catalyst comprising a metal
  • the temperature in the range from 320 to 360°C, the pressure in the range from 100 to 200 kg/cm2G, the LHSV in the range from 0.2 to 2.0 hr ⁇ 1 and the amount of hydrogen in the range from 800 to 2,000 Nm3/kl are more preferred as the condition of operation, though the preferable condition may different depending on the situation.
  • the fraction hydrotreated by the above process is introduced into the atmospheric distillation tower 3 and fractionated into further fractions.
  • the condition of the atmospheric distillation is similar to the condition described in performing Invention 1.
  • the fractions ranging from the kerosene fraction to the residual oil fraction which come out of the atmospheric distillation tower 3 are already hydrodesulfurized and hydrotreated, they can, after the heat is recovered by utilizing the heat exchanger with the crude oil according to necessity, be sent for storage directly to the storage tanks of the corresponding products or delivered directly to customers.
  • the naphtha fraction can be desulfurized by the hydrodesulfurization unit 4 together with the naphtha separated from the crude oil according to necessity.
  • the desulfurization is made after the removal of the naphtha fraction and the fractions such as the kerosene fraction and the other fractions having higher boiling points are separated after the desulfurization, the units necessary for refining the crude oil are simplified to a great extent while the properties of the products are maintained at the same level or better than conventional products. Energy losses accompanied with the charging and discharging of materials to the intermediate tanks can be eliminated by removing the intermediate tanks. Because the process of desulfurization and the process of hydrotreating are performed on the combined fractions at the same time, the control of operation is made more easily and it is further possible that the cost of investment for control instruments is reduced and the number of operator is reduced.
  • unstable substances which may be formed during the desulfurization process can be separated and removed during distillation in the main distillation tower.
  • the desulfurization so as to reduce the content of sulfur in the residual oil fraction to the value below the specified level, the content of sulfur in the lighter fractions can be reduced to the value below the level of conventional products.
  • Stability of the gas oil fraction can be improved by the process of Invention 2 because impurities such as nitrogen-containing compounds in lighter fractions can be removed by hydrotreating.
  • Figure 3 is the schematic flow diagram of an example of the basic constitution of the units to perform the method of Invention 3.
  • the units for refining to perform Invention 3 comprise the preliminary distillation tower 1 to separate the naphtha fraction in the crude oil by distillation, the desulfurization unit to desulfurize the residual fraction after the naphtha fraction has been removed, for example the hydrodesulfurization unit 2 to desulfurize the residual fraction by contact with a desulfurization catalyst in the presence of hydrogen, the high pressure separator 7 to separate fractions at a high pressure after the desulfurization, the hydrotreating unit 6 to refine the lighter fractions separated in the high pressure separator and the atmospheric distillation tower 3 to fractionate the refined fraction by distillation into individual fractions, such as naphtha, kerosene and gas oil.
  • the refining units for performing Invention 3 also comprise the hydrodesulfurization unit 4 to desulfurize the naphtha fraction separated in the preliminary distillation tower 1.
  • the naphtha fraction (C5 ⁇ 157°C) in crude oil is, at first, separated from the crude oil by distillation in the preliminary distillation tower 1.
  • the condition of distillation is similar to the condition described in performing Invention 1.
  • the heavy fraction comprising the kerosene fraction and other heavier fractions which is the residual fraction in the preliminary distillation tower 1 is introduced into the hydrodesulfurization unit 2 without separating into its components. It is desirable that the hydrodesulfurization unit 2 is operated so that the content of sulfur in the residual oil is controlled within a specified range of amount.
  • the operation conditions are similar to the conditions described previously.
  • the fraction desulfurized in the above process is introduced into the high pressure separator 7 without preliminary separation into its components and then separated into the lighter fraction and the heavy residual fraction.
  • Various methods can be utilized for the separation in the high pressure separator. For example, when hydrogen is introduced from the bottom of the separator, the fraction charged into the separator can be efficiently separated into the lighter fraction and the heavy residual fraction and, at the same time, hydrogen necessary for the subsequent hydrotreating is sufficiently provided.
  • the lighter fraction separated in the high pressure separator 7 is introduced into the hydrotreating unit 6. It is desirable that the operation of the hydrotreating unit 6 is controlled so that the content of sulfur in the gas oil is controlled within the specified range of amount and, at the same time, other impurities such as nitrogen-containing impurities are removed.
  • the operation conditions are similar to the corresponding conditions described previously. It is preferable that the pressure in the hydrotreating unit, in the hydrodesulfurization unit 2 and in the high pressure separator 7 are substantially the same.
  • the fraction hydrotreated by the above process is introduced into the atmospheric distillation tower 3 singly or as a mixture with the heavy residual oil fraction separated in the high pressure separator and fractionated into the naphtha fraction, the kerosene fraction, the gas oil fraction and the heavy residual fuel oil fraction. Whether the hydrotreated fraction is distilled singly or as a mixture with the heavy residual oil fraction can be decided according to separation conditions between the lighter fraction and the heavy residual oil fraction in the high pressure separator.
  • the kerosene fraction and the gas oil fraction can be made by atmospheric distillation wherein the naphtha fraction, the kerosene fraction, the gas oil fraction, the heavy gas oil fraction and the residual oil fraction are obtained by setting the cut temperatures at the range from C5 to 157°C, at the range from 157 to 239°C, at the range from 239 to 371°C, at the range from 371 to 472°C and at the range from 472°C to higher temperatures, respectively.
  • the fractions ranging from the kerosene fraction to the residual oil fraction which come out of the atmospheric distillation tower 3 are already hydrodesulfurized and hydrotreated, they can, after the heat is recovered by utilizing the heat exchanger with the crude oil according to necessity, be sent for storage directly to the storage tanks of the corresponding products or delivered directly to customers.
  • the naphtha fraction can be desulfurized by the hydrodesulfurization unit 4 together with the naphtha separated from the crude oil according to necessity.
  • unstable substances which may be formed during the desulfurization process can be separated and removed during distillation in the main distillation tower.
  • the desulfurization so as to reduce the content of sulfur in the residual oil fraction to the value below the specified level, the content of sulfur in the lighter fractions can be reduced to the value below the level of conventional products.
  • Stability and quality of the gas oil fraction can be improved by the process of Invention 3 because impurities such as nitrogen-containing compounds and metals in lighter fractions can be removed by the high pressure separation and the hydrotreating.
  • Figure 4 is the schematic diagram of an example of the basic constitution of the units to perform the method of Invention 4.
  • the units for refining to perform the method of refining of Invention 4 comprise the preliminary distillation tower 1 to separate the naphtha fraction in the crude oil by distillation, the unit for desulfurization to desulfurize the residual fraction after the naphtha fraction has been removed, for example the hydrodesulfurization unit 2 to desulfurize the residual fraction by contact with a desulfurization catalyst in the presence of hydrogen, the high pressure separator 7 to separate fractions after the desulfurization at a high pressure, the fluid catalytic cracking unit 8 to crack the heavy residual oil fraction separated in the high pressure separator 7, the hydrotreating unit 6 to refine the lighter fraction separated by the high pressure separator 7 and the lighter fraction formed by the cracking in the fluid catalytic cracking unit 8 and the atmospheric distillation tower 3 to fractionate the fractions by distillation into individual fractions, such as kerosene, gas oil, heavy gas oil and the residual oil.
  • the refining units for performing Invention 4 also comprise the hydrodesulfurization unit 4 to desulfurize the nap
  • the naphtha fraction (C5 ⁇ 157°C) in crude oil is, at first, separated from the crude oil by distillation from the crude oil in the preliminary distillation tower 1.
  • the condition of distillation is similar to the condition described in performing Invention 1.
  • the heavy fraction comprising the kerosene fraction and other heavier fractions which is the residual fraction in the preliminary distillation tower 1 is introduced into the hydrodesulfurization unit 2 without separating into its components. It is desirable that the desulfurization unit 2 is operated so that the content of sulfur in the final residual oil is controlled within a specified range of amount.
  • the condition of operation is similar to the condition described in performing Invention 1.
  • the fraction desulfurized in the above process is introduced into the high pressure separator 7 without preliminary separation into its components and then separated into the lighter fraction and the heavy residual fraction.
  • Various methods can be utilized for the separation in the high pressure separator. For example, when hydrogen is introduced from the bottom of the separator, the fraction charged into the separator can be efficiently separated into the lighter fraction and the heavy residual fraction and, at the same time, hydrogen necessary for the subsequent hydrotreating is sufficiently provided.
  • the heavy residual fraction still amounts to almost 50 weight % of the initial crude oil and is not advantageous for utilization. Therefore, in the method of Invention 4, the residual heavy fraction is catalytically cracked by the fluid catalytic cracking unit 8 and cracked gas oil and gasoline are obtained in the amount from 8 to 18 weight % based on the amount of the crude oil.
  • the amount of the residual fuel oil can be finally reduced to the amount from 2 to 5 weight % based on amount of the crude oil by this method.
  • the fluid catalytic cracking is performed in the presence of a zeolite cracking catalyst comprising rare earth elements in the amount of 5 weight % or less, preferably in the range from 0.5 to 2 weight %, and zeolite in the amount in the range from 20 to 60 weight %, preferably in the range from 30 to 40 weight %, in the condition of the weight ratio of the catalyst to the oil in the range from 5 to 15, preferably in the range from 8 to 10, at the temperature in the range from 450 to 560°C, preferably in the range from 510 to 540°C, and at the pressure in the range from 1.0 to 3.0 kg/cm2G.
  • a zeolite cracking catalyst comprising rare earth elements in the amount of 5 weight % or less, preferably in the range from 0.5 to 2 weight %, and zeolite in the amount in the range from 20 to 60 weight
  • the lighter fraction separated in the high pressure separator 7 and the cracked gas oil obtained in the fluid catalytic cracking unit 8 are introduced into the hydrotreating unit 6. It is desirable that the operation of the hydrotreating unit 6 is controlled so that the content of sulfur in the final gas oil is controlled within the specified range of amount and, at the same time, other impurities such as nitrogen-containing impurities are removed.
  • the operation condition is similar to the corresponding condition in Invention 1.
  • the fraction hydrotreated by the above process is introduced into the atmospheric distillation tower 3, further fractionated and separated into individual fractions.
  • the condition of the fractionation is similar to the corresponding condition in Invention 1.
  • the fractions such as the kerosene fraction and the light fraction which come out of the atmospheric distillation tower 3 are already treated with the hydrodesulfurization and the hydrotreating, they can, after the heat is recovered by utilizing the heat exchanger with the crude oil according to necessity, be sent for storage directly to the storage tanks of the corresponding products or delivered directly to customers.
  • the naphtha fraction can be desulfurized by the hydrodesulfurization unit 4 together with the naphtha separated from the crude oil.
  • the operation of the fluid catalytic cracking unit is added to a series of the operations of the desulfurization and the hydrotreating and, then, the refined fraction is fractionated, the unit necessary for the refining of the crude oil is simplified to a great extent while the properties of the products are maintained at the level equal to or higher than conventional products. Energy losses accompanied with the charging and discharging of materials to intermediate tanks can be eliminated by removing the intermediate tanks. Because the process of desulfurization and the process of hydrotreating are performed on the combined fractions at the same time, the control of operation is made more easily and it is further possible that the cost of investment for control instruments is reduced and the number of operator is reduced.
  • unstable substances which may be formed during the desulfurization process can be separated and removed during distillation in the main distillation tower.
  • the desulfurization so as to reduce the content of sulfur in the residual oil fraction to the value below the specified level
  • the content of sulfur in the lighter fractions can be reduced to the value below the level of conventional products.
  • Stability of the lighter fractions can be improved and the yields of the lighter fractions can be increased by the process of invention 4 because impurities in the lighter fractions including the cracking gas oil, such as nitrogen-containing compounds, can be removed by the high pressure separation, the fluid catalytic cracking and the hydrotreating.
  • a crude oil having the following composition and properties was utilized and the naphtha fraction was separated at 157°C by a preliminary distillation unit operated at the pressure of 1.5 kg/cm2G. density(15°C) 0.9101 g/cm3 sulfur content 2.78 weight % nitrogen content 0.14 weight % vanadium 41 weight ppm nickel 14 weight ppm naphtha fraction (C5 ⁇ 157°C) 20.0 weight % kerosene fraction (157°C ⁇ 239°C) 13.0 weight % gas oil fraction (239 ⁇ 371°C) 19.2 weight % heavy gas oil fraction (371 ⁇ 472°C) 7.7 weight % heavy residual oil (above 472°C) 40.1 weight %
  • the crude oil from which the naphtha fraction had been removed was introduced into a hydrodesulfurization unit loaded with a Co-Mo catalyst (CoO: 1.2 weight %, Mo2O3: 10.5 weight %, support: alumina/silica, surface area: 225 m2/g, volume of pores: 0.62 cc/g) and desulfurized at the pressure of 135 kg/cm2G, at the temperature of 390°C and at the LHSV of 0.5 hr ⁇ 1.
  • the amount of hydrogen consumption was 76 Nm3/kl.
  • the oil hydrodesulfurized in the above was fractionated by an atmospheric distillation unit and separated into individual fractions. Properties of the fractions thus obtained are shown in Table 2.
  • Example 2 The same crude oil as that utilized in Example 1 was refined by utilizing a conventional method.
  • the conditions of the atmospheric distillation were: a stage number of tray: 45 stages, the pressure of the operation: 0.5 kg/cm2G and the temperature at the inlet of the distillation tower: 370°C.
  • the crude oil was separated into individual fractions and the fractions were, after being temporarily stored in individual intermediate tanks, hydrodesulfurized individually.
  • the conditions of hydrodesulfurization for the individual fractions are shown in Table 1.
  • the same catalyst as that in Example 1 was utilized. Properties of the fractions thus prepared are shown in Table 2.
  • a crude oil having the following composition and properties was utilized and the naphtha fraction was separated at 157°C by a preliminary distillation unit operated at the pressure of 1.5 kg/cm2G. density(15°C) 0.9040 g/cm3 sulfur content 2.60 weight % nitrogen content 0.15 weight % vanadium 50 weight ppm nickel 15 weight ppm naphtha fraction (C5 ⁇ 157°C) 14.5 weight % kerosene fraction (157°C ⁇ 239°C) 11.7 weight % gas oil fraction (239 ⁇ 370°C) 20.9 weight % heavy residual oil (above 370°C) 52.9 weight %
  • the crude oil from which the naphtha fraction had been removed was introduced into a hydrodesulfurization unit loaded with a Co-Mo catalyst and desulfurized at the pressure of 135 kg/cm2G, at the temperature of 390°C and at the LHSV of 0.8 hr ⁇ 1.
  • Properties of the catalyst utilized in the desulfurization is shown in Table 3.
  • the oil hydrodesulfurized in the above was introduced into a hydrotreating unit without fractionation and hydrotreated.
  • the refined oil thus prepared was fractionated into the naphtha fraction of C5 ⁇ 157°C, the kerosene fraction of 157 ⁇ 239°C, the gas oil fraction of 239 ⁇ 370°C and the heavy residual oil fraction of above 370°C.
  • the results of the analysis of the fractions obtained are shown in Table 4.
  • the hydrotreating was operated by using a Ni-Mo catalyst (hydrogenation catalyst (A) shown in Table 3) at the pressure of 135 kg/cm3G, at the temperature of 360°C and at the LHSV of 1.25 hr ⁇ 1.
  • Example 3 The same crude oil as that in Example 2 was treated by the same processes as those in Example 2 except that another Ni-Mo catalyst (hydrogenation catalyst (B) shown in Table 3) was utilized for the hydrotreating.
  • the hydrodesulfurized oil was introduced into a hydrotreating unit without fractionation and treated in the same way as in Example 2.
  • the results of the analysis of the fractions obtained are shown in Table 4.
  • Storage stability of the gas oil fractions obtained in Example 2 and Example 3 was evaluated by the following method.
  • a 500 ml glass vessel having a vent containing 400 ml of the gas oil fraction obtained above was stored at a dark place kept at 43°C.
  • a sample was taken out at a time of a specified interval and the absorbance at 470 nm was measured. The results of the measurement are shown in Figure 5 and Table 5.
  • the storage stability was evaluated according to the method of ASTM D4625-86. Result of evaluation of a commercial gas oil is also shown as the reference in Table 5.
  • the absorbance level of the storage stability test of commercial gas oil is generally in the range from 0.12 to 0.40 after the storage for 30 days. This range is shown in the Figure 5 by the shaded area.
  • Example 2 0.11 0.25 none
  • a crude oil having the following composition and properties was utilized and the naphtha fraction was separated at 157°C by a preliminary distillation unit operated at the pressure of 1.5 kg/cm2G. density (15°C) 0.9040 g/cm3 sulfur content 2.60 weight % nitrogen content 0.15 weight % vanadium 50 weight ppm nickel 15 weight ppm naphtha fraction (C5 ⁇ 157°C) 14.5 weight % kerosene fraction (157°C ⁇ 239°C) 11.7 weight % gas oil fraction (239 ⁇ 370°C) 20.9 weight % heavy residual oil (above 370°C) 52.9 weight %
  • the crude oil from which the naphtha fraction had been removed was introduced into a hydrodesulfurization unit loaded with a Co-Mo catalyst (CoO: 1.2 weight %, Mo2O3: 10.5 weight %, support: alumina/silica) and desulfurized in the condition to make the sulfur content of the heavy residual oil fraction 0.5 weight %: at the pressure of 135 kg/cm2G, at the temperature of 380°C, at the LHSV of 0.6 hr ⁇ 1 and by utilizing hydrogen in the amount of 1,000 Nm3/kl.
  • Co-Mo catalyst CoO: 1.2 weight %, Mo2O3: 10.5 weight %, support: alumina/silica
  • the oil thus desulfurized was transferred to a high pressure separator without reducing the pressure of the system and the lighter fraction was separated by introducing hydrogen from the bottom of the separator.
  • the lighter fraction was introduced into a hydrotreating unit with an adequate amount of hydrogen and hydrotreated.
  • the hydrotreated oil thus obtained was fractionated by the atmospheric distillation into a naphtha fraction of C5 ⁇ 157°C, a kerosene fraction of 157 ⁇ 239°C and a gas oil fraction of 239 ⁇ 370°C.
  • the hydrotreating was operated by using a Ni-Mo catalyst (NiO2: 4.0 weight %, Mo2O3: 25.0 weight % and support: alumina) at the pressure of 135 kg/cm3G, at the temperature of 320°C, by utilizing hydrogen in the amount of 1,000 Nm3/kl and at the LHSV of 2.0 hr ⁇ 1.
  • Ni-Mo catalyst NiO2: 4.0 weight %, Mo2O3: 25.0 weight % and support: alumina
  • Example 4 The same crude oil as that utilized in Example 4 was distilled at the atmospheric pressure by a conventional method and fractionated into a kerosene fraction, a gas oil fraction and a heavy residual oil fraction. The fractions were hydrodesulfurized individually. The conditions for the hydrodesulfurization are shown in Table 6.
  • the absorbance level of the storage stability test of the commercial gas oil is generally in the range from 0.12 to 0.40 after the storage for 30 days.
  • Table 8 (Change of color) before the storage test (absorbance) after the storage test of 30 days (absorbance) formation of sludge
  • Example 4 0.01 0.03 none Comparative example 2 0.06 0.14 none
  • a crude oil having the following composition and properties was utilized and the naphtha fraction was separated at 157°C by a preliminary distillation unit operated at the pressure of 1.5 kg/cm2G. density (15°C) 0.9040 g/cm3 sulfur content 2.60 weight % nitrogen content 0.15 weight % vanadium 50 weight ppm nickel 15 weight ppm naphtha fraction (C5 ⁇ 157°C) 14.5 weight % kerosene fraction (157°C ⁇ 239°C) 11.7 weight % gas oil fraction (239 ⁇ 370°C) 20.9 weight % heavy residual oil (above 370°C) 52.9 weight %
  • the crude oil from which the naphtha fraction had been removed was introduced into a hydrodesulfurization unit loaded with a Co-Mo catalyst (CoO: 1.2 weight %, Mo2O3: 10.5 weight %, support: alumina/silica) and desulfurized at the pressure of 135 kg/cm2G, at the temperature of 380°C, at the LHSV of 0.6 hr ⁇ 1 and by utilizing 1,000 Nm3 of hydrogen per kiloliter of feed.
  • Co-Mo catalyst CoO: 1.2 weight %, Mo2O3: 10.5 weight %, support: alumina/silica
  • the oil thus hydrodesulfurized was transferred to a high pressure separator without reducing the pressure of the system and the lighter fraction was separated by introducing hydrogen from the bottom of the separator.
  • the heavy residual oil was then transferred to the fluid catalytic cracking apparatus for the residual oil and cracked to the fractions of gas, LPG, gasoline, cracked gas oil and heavy oil.
  • the cracking was operated in the presence of a commercial catalyst for the fluid catalytic cracking (kaolin/alumina of USY type containing 40 weight % of zeolite and 0.5 weight % of rare earth elements) at the weight ratio of the catalyst to the oil of 7, at the temperature of 520°C and at the pressure of 1.5 kg/cm.
  • the cracked gas oil obtained here was utilized in Comparative example 3.
  • the properties of the cracked gas oil are shown in Table 9.
  • the yield of the cracked gas oil was 9.6 weight % based on the crude oil.
  • the cracked gas oil thus obtained was pressured, mixed with the lighter fraction obtained before, introduced into a hydrotreating unit and hydrotreated.
  • the refined oil was fractionated by the atmospheric distillation tower into a naphtha fraction of C5 ⁇ 157°C, a kerosene fraction of 157 ⁇ 239°C and a gas oil fraction of 239 ⁇ 370°C.
  • the result of the analysis of the gas oil fraction thus obtained is shown as Example 5 in Table 9.
  • the yield of the gas oil fraction was 35.1 weight % based on the crude oil.
  • the hydrotreating was operated in the presence of a Ni-Mo catalyst (Ni: 4 weight %, Mo: 25 weight % and support: alumina) at the pressure of 135 kg/cm3G, at the temperature of 340°C, by utilizing 1,000 Nm3 of hydrogen per kiloliter of feed and at the LHSV of 1.0 hr ⁇ 1.
  • Ni-Mo catalyst Ni: 4 weight %, Mo: 25 weight % and support: alumina
  • Example 5 The same crude oil as that utilized in Example 5 was distilled at the atmospheric pressure by a conventional method and fractionated into a kerosene fraction, a gas oil fraction and a heavy residual oil fraction. The fractions were hydrodesulfurized individually. The conditions for the hydrodesulfurization are shown in Table 10. The desulfurized heavy residual oil obtained by desulfurizing the heavy residual oil fraction obtained above was then introduced into the fluid catalytic cracking unit and cracked to the fractions of gas, LPG, gasoline, cracked gas oil and heavy oil. The condition of the cracking is the same as that in Example 5. Properties of the cracked gas oil are shown in Table 9.
  • Storage stability of the gas oil fractions obtained in Example 5 and Comparative examples 3 and 4 was evaluated by the following method.
  • a 500 ml glass vessel having a vent containing 400 ml of the gas oil fraction obtained above was stored at a dark place kept at 43°C.
  • a sample was taken out at a time of a specified interval and the absorption at 470 nm was measured. The results of the measurement are shown in Figure 7 and Table 9.
  • the storage stability was evaluated according to the method of ASTM D4625-86.
  • the absorbance level of the storage stability test of commercial gas oil is generally in the range from 0.12 to 0.40 after the storage for 30 days.
  • cost for unit can be reduced to a large extent by the elimination of intermediate tanks and the unification of the desulfurization units.
  • Running cost can also be reduced by efficient utilization of energy because the decrease of temperature during the temporary storage in the intermediate tanks can be avoided.
  • Better control of operation can be realized by integration of the functions of units ranging from the preliminary distillation apparatus to the final fractionation unit into a unified system of the units as well as by the elimination of the intermediate tanks and by the unification of the desulfurization units. Hence, instruments and expenses necessary for the control of the units can be reduced and number of the operator can also be decreased.
  • the unit cost can be reduced by about 10% and the running cost can be reduced by about 20% when the refining units have the capacity of 100,000 barrels per day.
  • the cost of refining of petroleum can be reduced to a great extent and various kinds of inexpensive petroleum products and inexpensive raw materials in the field of petroleum chemistry can be provided.
  • Storage stability of the products can be improved by elimination of impurities such as sulfur and nitrogen by treatment with hydrotreating.
  • the kerosene fraction prepared by the method of the invention has a smoke point of 30 or more and the gas oil fraction prepared by the method of the invention has a cetane number of 60 or more.
  • the both fractions have a low sulfur content, a low nitrogen content and a high content of saturated components and are not colored after the storage stability test but remained in the colorless and transparent condition to exhibit the quite high quality of the products.
  • the life of the catalyst utilized in the process is increased because deactivation of the catalyst is prevented by the process that the hydrotreating is operated after the heavy residual oil is separated in advance.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Est décrit un procédé de raffinage de pétrole brut, qui permet de réduire les coûts d'installation et de fonctionnement et assure un fonctionnement stable moyennant un contrôle simple. Le procédé est caractérisé en ce que, après distillation et séparation de la fraction naphta dans le pétrole brut, les fractions restant après élimination de la fraction naphta sont désulfurées par mise en contact avec un catalyseur de désulfuration puis distillées pour être séparées en fractions respectives. Lors du raffinage des fractions restant après élimination de ladite fraction naphta, le lancement judicieux du traitement de raffinage par hydrogénation, le traitement de séparation haute pression, ou bien le traitement de craquage catalytique fluide des huiles lourdes résiduelles permettent d'obtenir des fractions de kérosène ou de gazole de haute qualité et d'accroître le rendement des fractions intermédiaires desdites huiles.
EP91917699A 1990-12-07 1991-10-09 Procede pour raffiner du petrole brut Expired - Lifetime EP0514549B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
JP40619290A JPH04209696A (ja) 1990-12-07 1990-12-07 原油の精製方法
JP406192/90 1990-12-07
JP414064/90 1990-12-26
JP41406490A JP2863326B2 (ja) 1990-12-26 1990-12-26 原油の精製法
JP414063/90 1990-12-26
JP41406390A JP2863325B2 (ja) 1990-12-26 1990-12-26 原油の精製方法
PCT/JP1991/001377 WO1992010557A1 (fr) 1990-12-07 1991-10-09 Procede pour raffiner du petrole brut

Publications (3)

Publication Number Publication Date
EP0514549A1 true EP0514549A1 (fr) 1992-11-25
EP0514549A4 EP0514549A4 (en) 1993-05-05
EP0514549B1 EP0514549B1 (fr) 1996-03-13

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752460A1 (fr) * 1994-03-29 1997-01-08 Idemitsu Kosan Company Limited Procede d'hydrotraitement de composition d'hydrocarbure et de combustible liquide

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3098029A (en) * 1959-07-22 1963-07-16 Socony Mobil Oil Co Inc Combination catalytic crackinghydroprocessing operation
US3671419A (en) * 1970-02-27 1972-06-20 Mobil Oil Corp Upgrading of crude oil by combination processing
US3730879A (en) * 1970-11-19 1973-05-01 Gulf Research Development Co Two-bed catalyst arrangement for hydrodesulrurization of crude oil
US3775290A (en) * 1971-06-28 1973-11-27 Marathon Oil Co Integrated hydrotreating and catalytic cracking system for refining sour crude
JPS5037043B2 (fr) * 1972-05-27 1975-11-29
US4212729A (en) * 1978-07-26 1980-07-15 Standard Oil Company (Indiana) Process for demetallation and desulfurization of heavy hydrocarbons

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9210557A1 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0752460A1 (fr) * 1994-03-29 1997-01-08 Idemitsu Kosan Company Limited Procede d'hydrotraitement de composition d'hydrocarbure et de combustible liquide
EP0752460A4 (fr) * 1994-03-29 1998-12-30 Idemitsu Kosan Co Procede d'hydrotraitement de composition d'hydrocarbure et de combustible liquide
US6328880B1 (en) 1994-03-29 2001-12-11 Idemitsu Kosan Co., Ltd. Process for hydrotreating hydrocarbon oil
EP1734099A2 (fr) * 1994-03-29 2006-12-20 Idemitsu Kosan Company Limited Procédé d'hydrotraitement de composition d'hydrocarbures et composition de carburants
EP1734099A3 (fr) * 1994-03-29 2007-04-18 Idemitsu Kosan Company Limited Procédé d'hydrotraitement de composition d'hydrocarbures et composition de carburants

Also Published As

Publication number Publication date
EP0514549B1 (fr) 1996-03-13
DE69117937D1 (de) 1996-04-18
EP0514549A4 (en) 1993-05-05
WO1992010557A1 (fr) 1992-06-25

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