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WO2006120898A1 - Procédé de fabrication de composition d’essence sans plomb et de base d’essence craquée à faible teneur en soufre - Google Patents

Procédé de fabrication de composition d’essence sans plomb et de base d’essence craquée à faible teneur en soufre Download PDF

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Publication number
WO2006120898A1
WO2006120898A1 PCT/JP2006/308696 JP2006308696W WO2006120898A1 WO 2006120898 A1 WO2006120898 A1 WO 2006120898A1 JP 2006308696 W JP2006308696 W JP 2006308696W WO 2006120898 A1 WO2006120898 A1 WO 2006120898A1
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WIPO (PCT)
Prior art keywords
gasoline
sulfur
cracked gasoline
cracked
fraction
Prior art date
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PCT/JP2006/308696
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English (en)
Japanese (ja)
Inventor
Yasuhiro Araki
Katsuaki Ishida
Original Assignee
Japan Energy Corporation
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Filing date
Publication date
Application filed by Japan Energy Corporation filed Critical Japan Energy Corporation
Priority to JP2007528215A priority Critical patent/JP5219247B2/ja
Publication of WO2006120898A1 publication Critical patent/WO2006120898A1/fr

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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
    • 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
    • C10G45/04—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 characterised by the catalyst used
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/02—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material
    • C10G25/03—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with ion-exchange material with crystalline alumino-silicates, e.g. molecular sieves
    • C10G25/05—Removal of non-hydrocarbon compounds, e.g. sulfur 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
    • 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
    • C10G45/04—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 characterised by the catalyst used
    • C10G45/06—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • 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
    • C10G45/04—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 characterised by the catalyst used
    • C10G45/06—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G67/06—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 a sorption process as the refining step in the absence of hydrogen

Definitions

  • the present invention relates to a method for producing a low-sulfur cracking gasoline base material with reduced environmental impact, and an unleaded gasoline composition.
  • the sulfur content in the cracked gasoline fraction can be easily reduced by a known technique in which the cracked gasoline fraction is hydrotreated in the presence of high-pressure hydrogen and a catalyst.
  • the olefin component which is contained in the cracked gasoline fraction and is relatively hydrogenated, is hydrogenated to lower the RON of the base material.
  • the unleaded gasoline composition blended with oil as a base material has the problem that sufficient driving performance cannot be obtained.
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-277768
  • the present invention uses a method for producing a low-sulfur cracked gasoline base material with reduced sulfur content while ensuring sufficient operating performance, and using the low-sulfur cracked gasoline base material. The challenge is to provide an unleaded gasoline composition.
  • the present inventors have conducted a process of fractionating cracked gasoline and contacting each fraction with a catalyst containing molybdenum or tungsten in the presence of hydrogen.
  • the present inventors found that the sulfur content of the cracked gasoline base material can be reduced while minimizing the loss of octane number by desulfurization by appropriately combining the treatment with a desulfurization agent containing nickel and zinc in the presence of hydrogen. It was.
  • the present invention provides:
  • step B in which the heavy cracked gasoline fraction obtained in step A is contacted with a catalyst containing molybdenum and Z or tungsten in the presence of hydrogen to reduce the sulfur content (step B); All or part of the light cracked gasoline fraction obtained in Step A and the heavy cracked gasoline fraction with reduced sulfur content obtained in Z or Step B contains nickel and zinc in the presence of hydrogen.
  • a porous desulfurizing agent to reduce and remove sulfur to 5 mass ppm or less.
  • step D Mixing step of mixing the cracked gasoline fraction obtained in steps A to C to obtain a low sulfur cracked gasoline base material having a sulfur content of 12 mass ppm or less and a research octane number of 85.0 or more (step D)
  • the preliminary desulfurization control coefficient ⁇ expressed by the following formula (1) is 12 to 30
  • LW is the fraction of light cracked gasoline fractionated in process A (volume%)
  • LS is the sulfur content in the light cracked gasoline obtained in process A (mass ppm)
  • HW is in process A.
  • the fraction (volume%) of the heavy cracked gasoline fractionated in this manner and HS represents the sulfur content (mass ppm) in the heavy cracked gasoline obtained in Step B).
  • the ratio of supplying to the process C and treating with respect to the total amount of cracked gasoline supplied to the process A is 20% by volume or more and 90% by volume or less. It is preferable.
  • Step B or Step C the whole or part of the cracked gasoline fraction is brought into contact with a catalyst containing at least one metal selected from Group 8 element force in the periodic table in the presence of hydrogen. It is preferable to include a Gen reduction processing step (Process E) that performs Gen reduction processing. Further, it is preferable to include a pretreatment step (step F) that increases the molecular weight of the sulfur-containing compound contained in the cracked gasoline fraction before step A or at the same time as the fractionation step of step A.
  • a Gen reduction processing step Process E
  • step F pretreatment step that increases the molecular weight of the sulfur-containing compound contained in the cracked gasoline fraction before step A or at the same time as the fractionation step of step A.
  • the present invention contains 30% by volume or more of the low sulfur cracking gasoline base material produced by the above method, the research octane number is 89 or more, the sulfur content is 10 mass ppm or less, and the doctor test is negative. It is a lead-free gasoline composition that has a corrosive power of silver plate or less.
  • Sarako research method octane number 92 or more, sulfur content 10 mass ppm or less, doctor test A lead-free gasoline composition which is negative and has a silver plate corrosive power ⁇ or less is preferred.
  • Various cracked gasoline fractions such as catalytically cracked gasoline fractions and pyrolyzed gasoline fractions are rich in high octane olefins.
  • hydrodesulfurization using a catalyst containing molybdenum or tungsten and an appropriate combination of treatment with a porous desulfurization agent containing nickel and zinc in the presence of hydrogen can be used for decomposition while minimizing olefin loss. It is possible to reduce the sulfur content of gasoline.
  • the cracked gasoline fraction in the method for producing a low sulfur cracked gasoline base material of the present invention is a petroleum fraction, a refined process oil, a petrochemical process oil, a coal liquefied oil, an oil sand, an oil shale, a polyolefin, a plastic,
  • Typical processes for obtaining cracked gasoline fractions include catalytic cracking processes and thermal cracking processes.
  • a catalytic cracked gasoline fraction can be preferably used as the cracked gasoline fraction in the method for producing a low sulfur cracked gasoline base material of the present invention.
  • the process for producing the catalytic cracking gasoline fraction can employ any known production process that does not specifically limit the catalytic cracking equipment, feedstock, and operating conditions.
  • Catalytic cracking equipment includes amorphous silica alumina, zeolite, etc.
  • the catalytic cracking of diesel fuel oil obtained from heavy oil indirect desulfurization equipment, direct desulfurization oil obtained from heavy oil direct desulfurization equipment, and atmospheric residual oil This is a device for obtaining a high octane gasoline base material.
  • the catalytic cracking feed oil preferably has a sulfur content of 8000 ppm by mass or less, particularly preferably 4000 ppm by mass or less, more preferably ⁇ or 2000 ppm by mass, or more, or 1000 ppm by mass or less. Use fractions reduced to 500 mass ppm or less by hydrorefining.
  • Specific catalytic cracking methods include, for example, UOP catalytic cracking method, flexi cracking method, ultra-orthoflow method, fluid catalytic cracking method such as Texaco fluid catalytic cracking method, residual oil fluid catalytic cracking such as RCC method and HOC method. (The Petroleum Institute of Japan, Petroleum Refining Process, P. 125, Kodansha Scientific Fukui (1998)).
  • a heavy oil pyrolysis gasoline fraction can also be used as the cracked gasoline fraction preferably used in the method for producing a low sulfur cracking gasoline base material of the present invention.
  • Heavy oil pyrolysis A gasoline fraction is a fraction with a carbon number of approximately 4 or more and a boiling point of 250 ° C or less obtained by applying a heat reaction to a heavy oil fraction and mainly a radical reaction. For example, a fraction obtained by a delayed coking method, a visbreaking method or a fluid coking method.
  • the light cracked gasoline fraction obtained in this way does not need to be subjected to a hydrodesulfurization step in which it is brought into contact with a hydrodesulfurization catalyst in the presence of high-pressure hydrogen as in step B described later. Since the olefinic compound is not hydrogenated, a decrease in RON of the light cracked gasoline fraction can be avoided.
  • the cracked gasoline fraction may be fractionated into three or more fractions. Then, the hydrodesulfurization step (step B) described later is performed on the heavy cracked gasoline fraction containing a relatively large amount of sulfur. As a result, the load on the collection / removal sulfur process (process C) described later can be reduced, and desulfurization can be carried out economically.
  • the preferred properties of the fractionated light cracked gasoline fraction are: 5% distillation temperature 35-55 ° C, especially 40-50 ° C, 95% distillation temperature 65-125 ° C, especially is seventy-five to one hundred fifteen ° C, sulfur content L ⁇ 50ppm, particularly 5 to 20 ppm, Orefin content 30-70 volume 0/0, especially from 40-60% by volume.
  • the heavy cracked gasoline fraction is heavier than the light cracked gasoline fraction, and usually has a higher sulfur content and lower olefin content than the light cracked gasoline fraction.
  • Preferred properties of the fractionated heavy cracked gasoline fraction 5% distillation temperature of 80 to 170 ° C, particularly 95 ⁇ 160 o C, 95 0/0 distillation temperature strength S175 ⁇ 215. C, especially ⁇ or 190-220. Is C, sulfur force ⁇ 20 ⁇ 500ppm, particularly ⁇ or 50 ⁇ 300ppm, old olefin component force 1-35 capacity 0/0, is particularly ⁇ or 5-25% by volume.
  • the fractionation step fractionates the cracked gasoline fraction obtained from a cracking process such as a catalytic cracking process, but the light cracking gasoline fraction directly from the fractionation step included in the final stage of the cracking process. And heavy cracked gasoline fractions can also be obtained.
  • Process IV is a process in which the heavy cracked gasoline fraction obtained in Process IV and the hydrodesulfurization catalyst are brought into contact with each other in the presence of high-pressure hydrogen to separate the sulfur as hydrogen sulfide and hydrodesulfurize it. . Since heavy cracked gasoline fractions contain relatively large amounts of sulfur, all heavy cracked gasoline fractions are usually hydrodesulfurized to supply low sulfur gasoline, but most of them. Specifically, it is preferable to hydrodesulfurize 80% by volume or more, particularly 90% by volume or more. Through the hydrodesulfurization process, the sulfur content of the heavy cracked gasoline fraction can be 5-50 ppm, preferably 10-30 ppm.
  • the hydrodesulfurization catalyst contains molybdenum and Z or tungsten, and is preferably one in which molybdenum or tungsten is supported on an inorganic porous carrier such as alumina.
  • the hydrodesulfurization catalyst has a total content of molybdenum and tungsten of 2 to 20% by mass, especially Is preferably 5 to 15% by mass. The content is defined by mass% of the metal element contained in the catalyst.
  • component elements other than molybdenum or tungsten contained in the catalyst include cobalt, phosphorus, potassium, carbon, nitrogen, and the like.
  • the cobalt content is from 0.5 to 10 mass 0/0, especially 1 to 5 wt%, the content of phosphorus 0.1. 2 to: LO wt%, particularly is 5-5 wt% 0.1 Is preferred.
  • the catalyst is used after sulfiding.
  • Preferred reaction conditions include a reaction temperature of 150 to 350 ° C, the reaction pressure 0.1 ⁇ 4.0MPa, liquid hourly space velocity (LHSV) 1.0 ⁇ 10h _1, is hydrogen Z oil ratio 50 ⁇ 1000NLZL.
  • Particularly preferred reaction conditions include a reaction temperature of 200 to 300 [° C, the reaction pressure 0.5 ⁇ 2.5MPa, LHSV2.0 ⁇ 6.0h _1, is hydrogen Z oil ratio 100 ⁇ 600NLZL.
  • the reaction pressure in this specification is indicated by gauge pressure.
  • the heavy cracked gasoline fraction does not contain a relatively high amount of olefinic compounds with high RON. However, when hydrogenated, the olefinic compounds may be saturated and RON may be reduced. However, operation under conditions where the olefin content is reduced by 20% or more, further 10% or more, particularly 3% or more is not preferable.
  • Step B hydrogen sulfide produced by hydrodesulfurization reacts with olefins that are usually contained in cracked gasoline to produce thiols, but if gasoline contains thiols, corrosion of gasoline car parts will occur. Cause unpleasant odor.
  • the thiols in the cracked gasoline that has undergone Step B are preferably removed after going through Step C, which will be described later. Although this removal method is not particularly limited, it is preferable to remove thiols by a method of converting thiols typified by acid-sweet jung to disulfide.
  • thiols contained in heavy cracked gasoline usually have about 5 to 10 carbon atoms, and it is preferable to apply an oxidized sweet-jung process that can remove even thiols having a large carbon number.
  • Specific examples include the MERICAT-II process described in NPRA 2000 Annual Meeting AM-00-54. The details of such sweetening will be described later as a method for increasing the molecular weight of the sulfur compound.
  • As another removal method it is preferable to reduce the thiols in the gasoline base material in advance so that the sulfur content of the thiols in the unleaded gasoline composition is 2 mass ppm or less, and further 1 mass ppm or less. . [0022] [Removal and removal sulfur process (Process C)]
  • Step A after performing Step A and Step B, in the coexistence of hydrogen, a desulfurization agent containing nickel and zinc and various cracked gasoline fractions obtained in Step A and Step B, that is, Step A
  • the obtained light cracked gasoline fraction and the heavy cracked gasoline fraction and the heavy cracked gasoline fraction obtained in step B are brought into contact with each or all or a part thereof to reduce the sulfur content.
  • the preliminary desulfurization control coefficient ⁇ represented by the following formula (1) is preferably 12-30, more preferably 13-20.
  • LW is the fraction (volume%) of the light cracked gasoline fraction fractionated in step A
  • LS is the sulfur content (mass ppm) in the light cracked gasoline fraction obtained in step A
  • HW Indicates the fraction (volume%) of the heavy cracked gasoline fraction fractionated in step A
  • HS indicates the sulfur content (mass ppm) in the heavy cracked gasoline fraction obtained in step B.
  • the ratio of the light cracked gasoline fraction and the ratio of the heavy cracked gasoline fraction are the ratio to the capacity of 100% by volume of cracked gasoline fractionated in the process A.
  • the ratio HW of the heavy cracked gasoline fractionated in step A is preferably 10 to 80% by volume, particularly 25 to 60% by volume.
  • Hydrocracking a cracked gasoline fraction in the presence of a hydrodesulfurization catalyst and hydrogen to desulfurize it to a sulfur content of 5 mass ppm or less means that the RON of the gasoline base material obtained by hydrogenating olefin is Decreasing and not preferable. Furthermore, since hydrogen sulfide produced by hydrodesulfurization reacts with olefin to regenerate thiols, it is not preferable because it cannot be sufficiently desulfurized. When a porous desulfurization agent containing nickel and zinc is used in the presence of hydrogen, sulfur removed from the organic sulfur compound is fixed on the desulfurization agent and does not generate hydrogen sulfide. React with fins to regenerate thiols.
  • the feedstock used in Step C was obtained by contacting the hydrocracked catalyst in the presence of high-pressure hydrogen in Step B or in part or all of the light cracked gasoline fraction obtained in Step A. Use all or part of the heavy cracked gasoline fraction. Alternatively, use a mixture of each in an appropriate ratio.
  • the ratio of treatment in Step C to the total amount of cracked gasoline before being used in Step A is 20% by volume or more and 90% by volume or less, particularly 25% by volume or more and 70% by volume or less. LV preferred. If the rate of treatment in Step C is less than 20% by volume, a sufficient effect of suppressing the decrease in octane number cannot be obtained. If the proportion treated in Step C exceeds 90% by volume, the life of the desulfurizing agent containing nickel and zinc is shortened, which is not preferable.
  • the porous desulfurization agent of the present invention contains nickel and zinc.
  • the method for producing a porous desulfurization agent containing nickel and zinc in the present invention is not particularly limited! However, a porous carrier such as alumina is impregnated with metal components such as zinc and nickel, and fired.
  • a preferable method is a production method or a production method in which a metal component such as zinc or nickel is precipitated by filtration and washed by a coprecipitation method, followed by steps such as molding and baking.
  • other elements such as iron and copper may be included.
  • the elemental mass ratio of nickel to zinc is preferably 1 to 50% by mass, particularly preferably 2 to 35% by mass, and more preferably 5 to 30% by mass with respect to 100% by mass of the total elemental mass of zinc and nickel. is there.
  • the nickel content is preferably 33% by mass or less, more preferably 20% by mass or less, based on the total mass of the desulfurizing agent.
  • the zinc content is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 55% by mass or more with respect to the total mass of the desulfurizing agent. If the nickel content exceeds 50% by mass or the zinc content is less than 30% by mass, the life of the porous desulfurizing agent is shortened, which is not preferable.
  • the sodium content is preferably 1.0% by mass or less based on the total mass of the desulfurizing agent, more preferably 0.5% by mass or less, and further 0 2% by mass or less. If sodium is contained in an amount exceeding 1.0 mass% with respect to the total mass of the desulfurizing agent, the desulfurization performance is lowered, which is not preferable.
  • a preferable desulfurizing agent contains 30 to 85% by mass, particularly 50 to 80% by mass of a metal component such as nickel and zinc. Further, the molded and fired desulfurizing agent may be further impregnated and supported with a metal component and fired.
  • the desulfurizing agent is preferably used after being treated in a hydrogen atmosphere.
  • the specific surface area of the desulfurizing agent is preferably 30 m 2 / g or more, particularly preferably 50 to 600 m 2 Zg.
  • the porous desulfurization agent of the present invention is preferably a porous desulfurization agent having a sulfur sorption function.
  • the porous desulfurization agent having a sulfur sorption function here is to fix the sulfur atom in the organic sulfur compound to the desulfurization agent, and for hydrocarbon residues other than the sulfur atom in the organic sulfur compound.
  • hydrocarbon compounds from which sulfur atoms have been removed may give products that have undergone reactions such as hydrogenation, isomerization, and decomposition. Since sulfur is fixed to the desulfurizing agent in the detachable sulfur, it does not generate sulfur compounds such as hydrogen sulfide as a product, unlike hydrorefining. Further, since hydrogen sulfide is not generated, hydrogen sulfide is not included in the recital hydrogen or purge hydrogen, and no facility for removing hydrogen sulfide is required, so that desulfurization can be achieved economically.
  • the collection / removal sulfur treatment may be carried out by a notch type or a flow type, but the light cracked gasoline fraction or the heavy cracked gasoline fraction is placed in a fixed bed desulfurization tower filled with a desulfurizing agent. It is preferable to carry out the distribution of the fraction because the separation of the desulfurization agent and the obtained desulfurized cracked gasoline fraction can be easily performed.
  • the temperature in the desulfurization treatment is preferably 100 to 400 ° C, more preferably 200 to 350 ° C, and particularly preferably 250 to 350 ° C. If the reaction temperature is less than 100 ° C, the desulfurization rate decreases, and desulfurization cannot be efficiently performed, which is not preferable.
  • reaction temperature exceeds 400 ° C
  • the desulfurization agent is sintered, and the desulfurization capacity is lowered, which is not preferable.
  • hydrogen is allowed to coexist.
  • the reaction pressure is preferably 0 to 5. OMPa, more preferably 0 to 3. OMPa, and particularly preferably 0 to 5. 2. It is OMPa. If the reaction pressure exceeds 5. OMPa, hydrogenation of the olefins contained in the hydrocarbon oil tends to proceed and RON may decrease, which is not preferable.
  • LH SV is preferably more than 2.
  • Oh _ 1 and 50 Oh _ 1 or less, more preferably 2. is a beyond 20.
  • Oh _ 1 below Oh _1, particularly preferably 10.
  • Oh _1 from more than 2.
  • the LHSV is 2.
  • Oh _ 1 or less the oil flow rate is limited or the desulfurization reactor becomes too large, and it is not preferable because it cannot economically desulfurize.
  • the LHSV exceeds 50.
  • Oh _1 a contact time sufficient for desulfurization cannot be obtained, and the desulfurization rate decreases, which is not preferable.
  • the hydrogen Z oil ratio is preferably 1 to 1000 NLZL, more preferably 10 to 500 NLZL. Particularly preferred is 10 to 300 NL / L.
  • Hydrogen may contain impurities such as methane, but the hydrogen purity is preferably 50% by volume or more, more preferably 80% by volume or more, especially 95% by volume or more so that the hydrogen compressor does not become too large. preferable. If a sulfur compound such as sulfur dioxide or hydrogen is contained in hydrogen, the life of the desulfurizing agent is reduced, so that it is preferably less than a certain ratio.
  • the sulfur content in hydrogen is preferably 1000 ppm by volume or less, more preferably 100 ppm by volume or less, and particularly preferably 10 ppm by volume or less.
  • the cracked gasoline fraction is treated in Step A, Step B, and Step C, and the base materials obtained in each step are mixed to obtain a sulfur content of 12 mass ppm or less, and RON is 85.
  • the sulfur content is preferably 10 ppm by mass or less, more preferably 8 ppm by mass or less.
  • RON is preferably 89.0-93.0.
  • the various base materials obtained in Process A, Process B, and Process C have a sufficient amount of production and the amount used in Process D for preparing a low sulfur cracked gasoline base material. It is economical and preferable to use it frequently.
  • the light cracked gasoline fraction obtained in step A and treated in step C is mixed with the heavy cracked gasoline fraction obtained in step A and treated in step B, or
  • the light cracked gasoline fraction obtained in step A is mixed with the heavy cracked gasoline fraction obtained in step A, treated in step B, and further treated in the same step.
  • Cracked gasoline fraction used as raw material for process A It is preferable to mix various base materials obtained with almost the entire amount, for example, 80% by volume or more, to make a low sulfur decomposition gasoline base material. Further, the mixing in step D may be performed simultaneously with the blending step described later, which is mixing with other gasoline base materials for the preparation of the gasoline composition.
  • the whole or part of the cracked gasoline fraction in the pre-process of Step B or Step C is preferably present in the presence of hydrogen, preferably on an inorganic porous support such as alumina. It is preferable to reduce the gen value by contacting with a catalyst supporting at least one metal selected from the group 8 elements in the table. Since cracked gasoline fractions contain sulfur, catalysts with high resistance to sulfur and nickel or cobalt are preferred. There are no particular restrictions on the active component elements other than the Group 8 element contained in the catalyst, but molybdenum, tungsten, and phosphorus are listed as preferred components that may be included. Usually, the catalyst is used after the sulfur treatment. The reaction conditions need to be set so that the hydrogen of the olefins can be significantly reduced and the RON cannot be significantly reduced by reducing the gen number of the cracked gasoline fraction obtained.
  • Preferred reaction conditions are a reaction temperature of 40 to 300 ° C, a reaction pressure of 0 to 4 MPa, an LHSV of 1 to: L0h_1, and a hydrogen Z oil ratio of 1 to 500 NLZL.
  • the gen number of the cracked gasoline fraction obtained by step E is preferably 0.5 gZl00 g or less, more preferably 0.3 gZl00 g, particularly preferably 0. lgZlOOg or less. If the Gen value exceeds 0.5 gZ100 g, desulfurization performance and desulfurization agent life will be greatly impaired in Process B and Process C! /, Preferable! /.
  • the decrease in olefin content is preferably 10% by volume or less, particularly preferably 5% by volume or less, more preferably 2% by volume or less, and the decrease in RON is preferably 1 or less, more preferably. It is 0.5 or less, more preferably 0.3 or less, and particularly preferably 0.2 or less.
  • the sulfur content is not substantially reduced. Part of the sulfur content may be converted to hydrogen sulfide, which may be desulfurized in the subsequent step B or step C, and a sulfur hydrogen removal facility is installed in the Jen reduction treatment step. This is not economical.
  • the gen value as used in the present invention refers to the gen value measured by UOP326-82.
  • the gen number is obtained by bringing a catalyst and catalytically cracked gasoline into contact with each other in the presence of hydrogen and converting gen to mono-olefin or reacting with a sulfur compound coexisting with gen to convert it into sulfides. Is reduced.
  • a catalyst containing a Group 8 element By using a catalyst containing a Group 8 element and applying the above-mentioned preferred reaction conditions, hydrogenation of olefin can be almost suppressed, so that the gen number can be lowered without significantly reducing RON.
  • gen in olefin is selectively hydrorefined, and can be applied as step E in the present invention.
  • the IFP Selective Hydrogenation process and the Huies Selective Hydrogenation process are used favorably (edited by the Japan Petroleum Institute, Petroleum Refining Process, p. 62, Kodansha Scientific (199 8)).
  • the SHU process 21st JPI Petroleum Refining and onference 'Recent Progress in Petroleum Process ⁇ echnology, 37 (2002)
  • CD Hydro process NPRA 2001 Annual Meeting, AM-01- 39 (2001)
  • the pretreatment step (Step F) to increase the molecular weight of the sulfur compounds contained in the cracked gasoline fraction is used for the fractionation step in Step A, or the molecular weight of the sulfur compounds is reduced simultaneously with the fractionation step in Step A. It is preferable to do pretreatment to enlarge. By selectively increasing the molecular weight of the sulfur compound such as thiols, the boiling point of the sulfur compound is increased. Therefore, in the fractionation process, the sulfur compound is contained in the heavy cracked gasoline fraction. The sulfur content of the light cracked gasoline fraction obtained in the fractionation process can be reduced.
  • a catalyst is placed in a distillation column to make the sulfur content heavy, and the heavy sulfur compound moves to the distillate component on the heavy side to reduce the sulfur content of the light fraction. be able to.
  • the CD-Hydro process described below uses this!
  • a sweet jung is performed to treat the thiols to make the product non-brominated.
  • a known method for converting thiols to disulfides by an oxidation method or an oxidation extraction method can be applied as a method for increasing the molecular weight of a sulfur compound in the present invention.
  • the Marlox method, doctor method, etc. are preferably used (Oil Refining Technology Handbook 3rd Edition, Sangyo Tosho Co., Ltd. (1981)).
  • a method of increasing the molecular weight of the sulfur compound a method of reacting a sulfur compound contained in the cracked gasoline fraction with olefins can also be suitably used.
  • SHU process and OATS process 21st JPI Petroleum Refining conference Recent Progress in Petroleum Process Technology, 37 (2002)
  • a SHU process capable of simultaneously performing a process for increasing the molecular weight of a sulfur compound and a process for reducing a gen is preferable.
  • a process capable of simultaneously increasing the molecular weight of the sulfur compound and reducing the gen while carrying out fractional distillation is more preferable, and specifically, a CD-hydro process can be mentioned as such a process.
  • gasoline base materials other than the cracked gasoline fraction mixed in the blending process include catalytic reformed gasoline base materials, alkylate gasoline base materials, straight-run naphtha.
  • Desulfurized base materials isomeric gasoline base materials, aromatic base materials such as toluene and xylene, and methyl t-butyl ether (MTBE), ethyl t-butyl ether (ETBE), tamyl ether ether (TAEE ),
  • Known gasoline base materials such as oxygen-containing gasoline base materials such as ethanol and methanol can be appropriately used.
  • ETBE has a higher octane number improvement effect per oxygen content than ethanol and MTBE, and is a preferred base material because it can increase the octane number without deteriorating volatility by mixing ETBE.
  • the other gasoline base material mixed in the blending process preferably has a sulfur content of 20 ppm by mass or less, more preferably 10 ppm by mass or less, further 3 ppm by mass or less, particularly 1 ppm by mass. It is as follows. If the sulfur content of other gasoline base materials exceeds 20 mass ppm, the blending amount in the blending process of gasoline base materials is restricted, which is not preferable.
  • Preferred blending amounts are 30 to 90% by volume of cracked gasoline fraction, especially 40 to 80% by volume, 5 to 50% by volume of catalytically reformed gasoline base, particularly 10 to 45% by volume, alkylate gasoline base 5 to 40% by volume, especially 10 to 30% by volume, and oxygen-containing gasoline base material such as ETBE is 0 to 16% by volume, particularly 1 to 7% by volume.
  • the unleaded gasoline composition of the present invention has a research octane number of 89.0 or more and a total sulfur content. 10 mass ppm or less, doctor test is negative, silver plate corrosion is 1 or less.
  • the research octane number is preferably 90.0 or more and the gen number is preferably 0.1 lg / 100 g or less. If the doctor test is positive or the silver plate corrosion exceeds 1, unpleasant odor of gasoline power is generated, and corrosion of components used in gasoline automobiles is not preferable.
  • RON is preferably 92 or more, more preferably 93 to 102. Having such a high RON is preferable because it can improve the acceleration performance and fuel consumption of a gasoline automobile.
  • the sulfur content is preferably 8 mass ppm or less, more preferably 5 mass ppm or less.
  • the lead-free gasoline composition of the present invention preferably has a Reed vapor pressure (RVP) of 93 kPa or less, more preferably 44 to 93 kPa. If it exceeds 93 kPa, the amount of gasoline vapor released into the atmosphere increases, which is preferable. If it is less than 44 kPa, the startability of a gasoline vehicle deteriorates, which is not preferable. More preferably, it is preferable to adjust the RVP according to the season to 44-65 kPa in summer and 70-93 kPa in winter! /.
  • RVP Reed vapor pressure
  • the unleaded gasoline composition of the present invention has a 50% by volume distillation temperature of 75 to 105 ° C, more preferably 75 to 100 ° C. If the 50% by volume distillation temperature is less than 75 ° C, the RVP of the unleaded gasoline composition increases, which is not preferable. If it exceeds 105 ° C, the acceleration performance of gasoline automobiles will be poor, which is not preferable.
  • the aromatic content is preferably 40% by volume or less, more preferably 30% by volume or less, and particularly preferably 20 to 30% by volume. When the aromatic content is less than 20% by volume, the blending amount of the cracked gasoline base material is limited, and the production cost of the unleaded gasoline composition becomes high, which is not preferable. If it exceeds 40% by volume, the unflammable gasoline composition has poor flammability, which is preferable.
  • the olefin content which is the ratio of the unsaturated carbon number to the total carbon number, is 45% by volume or less, more preferably 20 to 40% by volume, particularly preferably 20 to 30% by volume. is there.
  • the ratio of unsaturated carbon to total carbon is in such a range, it becomes easy to secure the olefin and aromatic content within the above-mentioned range.
  • fuel oil additives known in the art can be blended as required. These compounding amounts can be appropriately selected. Usually, it is preferable to maintain the total compounding amount of the additives at 0.1% by mass or less.
  • fuel oil additives that can be used in water include phenolic and amine-based antioxidants, Schiff-type compounds, metal deactivators such as thioamide-type compounds, and organophosphorus compounds.
  • Detergents such as surface ignition inhibitors, succinimides, polyalkylamines, polyetheramines, anti-icing agents such as polyhydric alcohols or ethers, alkali metal salts of organic acids or alkaline earth metals
  • auxiliary agents such as salts and sulfates of higher alcohols
  • antistatic agents such as anionic surfactants, cationic surfactants and amphoteric surfactants
  • colorants such as azo dyes.
  • JIS ⁇ 2276 Pulleum product aviation fuel oil test method 14 14. Silver plate corrosion The silver plate used in “Test method” was used for evaluation. The test temperature is 50 ° C and the test time is 3 hours. The doctor test was measured according to JIS K 2276.
  • This catalytic cracking gasoline fraction B was fractionated to obtain a light catalytic cracking gasoline fraction C and a heavy catalytic cracking gasoline fraction D.
  • the ratio of light fraction C and heavy fraction D was 68:32 (volume ratio).
  • Table 1 shows the properties of light catalytic cracking gasoline fraction C and heavy catalytic cracking gasoline fraction D. Shown in
  • a solution in which 106 g of sodium carbonate was dissolved in water was heated to 60 ° C, and 58 g of nickel nitrate hexahydrate was added to the solution in which 179 g of zinc nitrate hexahydrate was dissolved in water.
  • the food was dripped.
  • the resulting precipitate was filtered and washed with water. Thereafter, after drying at 120 ° C. for 16 hours, calcination was performed at 350 ° C. for 3 hours to obtain a desulfurizing agent Z.
  • the desulfurizing agent Z had a nickel content of 17.9% by mass, a zinc content of 58.7% by mass, a sodium content of 0.02% by mass and a specific surface area of 80 m 2 Zg.
  • Table 1 shows the properties of light catalytic cracking gasoline fractions E and F.
  • the oxidized sweet jung equipment is a MERICAT-IV process manufactured by Merichem, and the reaction temperature was 41 ° C. Drove in.
  • Table 3 shows the properties of the low-sulfur cracking gasoline base material L and the properties of the above-mentioned intermediate base material.
  • the preliminary desulfurization control coefficient ⁇ in Example 3 was 18.
  • the catalytically cracked gasoline fraction B obtained in Example 1 was fractionally distilled to a volume ratio of 47:53 to obtain a light catalytic cracked gasoline fraction M and a heavy catalytic cracked gasoline fraction N.
  • the total amount of light catalytic cracking gasoline M, the half amount of heavy catalytic cracking gasoline O and the total amount of heavy catalytic cracking gasoline P were mixed to obtain a low sulfur cracking gasoline base material Q.
  • Table 4 shows the properties of the low sulfur decomposition gasoline substrate Q and related intermediate substrates. The preliminary desulfurization control coefficient ex in Example 4 was 14.
  • the light catalytic cracking gasoline fraction C obtained in Example 1 was mixed with the entire heavy catalytic cracking gasoline R to obtain cracked gasoline base material S.
  • Table 5 shows the properties of the cracked gasoline base material 3 and the related intermediate base material.
  • Gasoline base materials obtained by known techniques other than catalytic cracking include desulfurized straight-run naphtha T, catalytically reformed medium oil U, catalytically reformed heavy oil V, alkylate gasoline W, ethyl tbutylbutyl X
  • the properties are as shown in Table 6.
  • Catalytically modified medium oil U is obtained by distilling and separating a toluene-rich fraction from catalytically modified gasoline.
  • Catalytically modified heavy oil V is obtained by distillation separation of aromatics having 9 or more carbon atoms and less than 11 from catalytically reformed gasoline.
  • Example 4 An unleaded gasoline composition CC was prepared by blending 22% by volume of the cracked gasoline base material Q described above and 25% by volume of the light catalytic cracked gasoline base material M described in Example 4. Table 7 shows the properties.
  • Undecomposed gasoline composition DD was prepared by blending 70% by volume of the cracked gasoline base S described. Table 7 shows the properties.

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Abstract

L’invention concerne une composition d’essence sans plomb de teneur en soufre réduite mais assurant des performances de conduite suffisantes ; un procédé de fabrication de la composition ; et un procédé de fabrication d’une base d’essence craquée à faible teneur en soufre convenant à l’élaboration de la composition d’essence. Le procédé de fabrication d’une base d’essence craquée à faible teneur en soufre est caractérisé en ce qu’il comprend : une phase (A) dans laquelle on obtient des fractions d’essence craquée ; une phase (B) dans laquelle une fraction d’essence craquée lourde obtenue dans la phase (A) est hydrodésulfurée ; une phase (C) dans laquelle la totalité ou bien une partie d’une fraction d’essence craquée légère obtenue dans la phase (A) et/ou la totalité ou bien une partie de la fraction d’essence craquée lourde de teneur en soufre réduite obtenue dans la phase (B) sont soumises à une désulfuration par sorption ; et une phase (D) dans laquelle on mélange les fractions d’essence craquée obtenues dans les phases (A) à (C) pour obtenir une base d’essence craquée à faible teneur en soufre, ayant une teneur en soufre spécifique et une valeur d’octane spécifique.
PCT/JP2006/308696 2005-05-06 2006-04-26 Procédé de fabrication de composition d’essence sans plomb et de base d’essence craquée à faible teneur en soufre WO2006120898A1 (fr)

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Cited By (9)

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JP2008127569A (ja) * 2006-11-16 2008-06-05 Ifp オクタン価の喪失が少ない分解ガソリンの深度脱硫方法
JP2008248195A (ja) * 2007-03-30 2008-10-16 Japan Energy Corp 多孔質脱硫剤及びこれを用いた炭化水素油の脱硫方法
WO2008146848A1 (fr) * 2007-05-30 2008-12-04 Japan Energy Corporation Procédé de désulfuration d'huile d'hydrocarbure
JP2008303273A (ja) * 2007-06-06 2008-12-18 Idemitsu Kosan Co Ltd 脱硫重質分解ガソリンの製造方法及び該脱硫重質分解ガソリンを含有するガソリン組成物
JP2009155498A (ja) * 2007-12-27 2009-07-16 Showa Shell Sekiyu Kk ガソリン燃料組成物
JP2010138292A (ja) * 2008-12-11 2010-06-24 Showa Shell Sekiyu Kk ガソリンエンジン用燃料組成物
JP2010138294A (ja) * 2008-12-11 2010-06-24 Showa Shell Sekiyu Kk ガソリンエンジン用燃料組成物
CN104046389A (zh) * 2013-03-11 2014-09-17 中石化洛阳工程有限公司 一种劣质汽油脱硫降烯烃的方法
WO2020052145A1 (fr) * 2018-09-11 2020-03-19 福州大学 Procédé de valorisation d'essence fcc

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US4062762A (en) * 1976-09-14 1977-12-13 Howard Kent A Process for desulfurizing and blending naphtha
JPH10102070A (ja) * 1996-09-24 1998-04-21 Inst Fr Petrole 低硫黄含有量の接触クラッキング・ガソリンの製造方法および装置
JP2003183676A (ja) * 2001-12-21 2003-07-03 Nippon Oil Corp 低硫黄分ガソリンの製造方法
JP2005068415A (ja) * 2003-08-05 2005-03-17 Japan Energy Corp 接触分解ガソリン基材の製造方法およびそれを用いた無鉛ガソリン組成物

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US4062762A (en) * 1976-09-14 1977-12-13 Howard Kent A Process for desulfurizing and blending naphtha
JPH10102070A (ja) * 1996-09-24 1998-04-21 Inst Fr Petrole 低硫黄含有量の接触クラッキング・ガソリンの製造方法および装置
JP2003183676A (ja) * 2001-12-21 2003-07-03 Nippon Oil Corp 低硫黄分ガソリンの製造方法
JP2005068415A (ja) * 2003-08-05 2005-03-17 Japan Energy Corp 接触分解ガソリン基材の製造方法およびそれを用いた無鉛ガソリン組成物

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008127569A (ja) * 2006-11-16 2008-06-05 Ifp オクタン価の喪失が少ない分解ガソリンの深度脱硫方法
JP2008248195A (ja) * 2007-03-30 2008-10-16 Japan Energy Corp 多孔質脱硫剤及びこれを用いた炭化水素油の脱硫方法
WO2008146848A1 (fr) * 2007-05-30 2008-12-04 Japan Energy Corporation Procédé de désulfuration d'huile d'hydrocarbure
JPWO2008146848A1 (ja) * 2007-05-30 2010-08-19 株式会社ジャパンエナジー 炭化水素油の脱硫方法
JP2008303273A (ja) * 2007-06-06 2008-12-18 Idemitsu Kosan Co Ltd 脱硫重質分解ガソリンの製造方法及び該脱硫重質分解ガソリンを含有するガソリン組成物
JP2009155498A (ja) * 2007-12-27 2009-07-16 Showa Shell Sekiyu Kk ガソリン燃料組成物
JP2010138292A (ja) * 2008-12-11 2010-06-24 Showa Shell Sekiyu Kk ガソリンエンジン用燃料組成物
JP2010138294A (ja) * 2008-12-11 2010-06-24 Showa Shell Sekiyu Kk ガソリンエンジン用燃料組成物
CN104046389A (zh) * 2013-03-11 2014-09-17 中石化洛阳工程有限公司 一种劣质汽油脱硫降烯烃的方法
CN104046389B (zh) * 2013-03-11 2015-11-25 中石化洛阳工程有限公司 一种劣质汽油脱硫降烯烃的方法
WO2020052145A1 (fr) * 2018-09-11 2020-03-19 福州大学 Procédé de valorisation d'essence fcc

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