EP3950891A1 - Composition d'huile combustible - Google Patents

Composition d'huile combustible Download PDF

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Publication number
EP3950891A1
EP3950891A1 EP20779052.8A EP20779052A EP3950891A1 EP 3950891 A1 EP3950891 A1 EP 3950891A1 EP 20779052 A EP20779052 A EP 20779052A EP 3950891 A1 EP3950891 A1 EP 3950891A1
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EP
European Patent Office
Prior art keywords
fuel oil
mass
calcium
calcium salicylate
diluted product
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP20779052.8A
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German (de)
English (en)
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EP3950891A4 (fr
Inventor
Keiichi Odagiri
Taro SUMI
Eiji KATSUNO
Ryou HANAMURA
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Adeka Corp
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Adeka Corp
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Publication of EP3950891A1 publication Critical patent/EP3950891A1/fr
Publication of EP3950891A4 publication Critical patent/EP3950891A4/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/189—Carboxylic acids; metal salts thereof having at least one carboxyl group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
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    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
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    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/223—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond having at least one amino group bound to an aromatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2425—Thiocarbonic acids and derivatives thereof, e.g. xanthates; Thiocarbamic acids or derivatives thereof, e.g. dithio-carbamates; Thiurams
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2443—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds
    • C10L1/2456—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds sulfur with oxygen and/or nitrogen in the ring, e.g. thiazoles
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2608—Organic compounds containing phosphorus containing a phosphorus-carbon bond
    • C10L1/2616—Organic compounds containing phosphorus containing a phosphorus-carbon bond sulfur containing
    • C—CHEMISTRY; METALLURGY
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    • C10L1/00—Liquid carbonaceous fuels
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    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
    • C—CHEMISTRY; METALLURGY
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0213—Group II metals: Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Hg
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    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

  • the present invention relates to a fuel oil composition that is suppressed from causing deposition of sludge at the time of its storage or at the time of its use.
  • an object of the present invention is to provide a fuel oil composition that can effectively suppress the deposition of sludge at the time of its storage or at the time of its use.
  • a fuel oil composition including a specific fuel oil base oil and a specific sludge dispersant is excellent in suppression of the deposition of sludge at the time of its storage or at the time of its use.
  • a fuel oil composition comprising: a fuel oil base oil having a sulfur element content of from 0.01 mass% to 0.50 mass%; and a calcium salicylate having a total base number of from 100 mgKOH/g to 1,200 mgKOH/g.
  • the fuel oil composition that can suppress the deposition of sludge at the time of its storage or at the time of its use.
  • a fuel oil base oil to be used in the present invention is a fuel oil base oil having a sulfur element content of from 0.01 mass% to 0.50 mass%.
  • Such fuel oil base oil is not particularly limited as long as its sulfur element content is from 0.01 mass% to 0.50 mass%, and a liquid fuel oil that may be used as a fuel oil is appropriately selected in accordance with use purposes and conditions.
  • a fuel oil having an adjusted sulfur element content such as gasoline, light oil, heavy oil, kerosene, or a biofuel, may be used.
  • Specific examples of such fuel oil include JIS Special No. 1 light oil, JIS No. 1 light oil, JIS No. 2 light oil, JIS No. 3 light oil, JIS Special No.
  • JIS A-type heavy oil JIS B-type heavy oil, JIS C-type heavy oil, JIS No. 1 kerosene, JIS No. 2 kerosene, a marine gas oil (MGO), a marine diesel oil (MDO), a very low sulfur fuel oil (VLSFO), an ultra low sulfur fuel oil (ULSFO), palm oil, coconut oil, rapeseed oil, soybean oil, sunflower oil, corn oil, sesame oil, tall oil, bone oil, and whale oil.
  • Those fuel oils may be used alone or in combination thereof.
  • a straight-run light oil fraction, a vacuum light oil fraction, a desulfurized light oil fraction, a cracked base oil fraction, a directly desulfurized light oil fraction, an atmospheric distillation residual oil, a vacuum distillation residual oil, directly desulfurized heavy oil, cracked heavy oil, or the like may be used as light oil or heavy oil out of those fuel oils.
  • such fuel oils as described above may be subjected to hydrogenation treatment before their use.
  • the fuel oil base oil to be used in the present invention is excellent in sludge deposition-suppressing property when its sulfur element content falls within the range of from 0.01 mass% to 0.50 mass%.
  • the sulfur element content in the fuel oil base oil is preferably from 0.03 mass% to 0.48 mass%, more preferably from 0.10 mass% to 0.45 mass%.
  • sulfur element content in the fuel oil base oil refers to a sulfur element content derived only from the fuel oil base oil, and a sulfur element derived from an additive is not included in the calculation of the content.
  • the sulfur element content is measured by an ultraviolet fluorescence method described in JIS K 2541-6 (2003).
  • a method of adjusting the sulfur element content of the fuel oil base oil is not particularly limited, and the sulfur element content only needs to be adjusted to from 0.01 mass% to 0.50 mass% by a known method.
  • the sulfur element content of a fuel oil containing more than 0.50 mass% of a sulfur element may be set to from 0.01 mass% to 0.50 mass% by subjecting the fuel oil to direct desulfurization treatment, indirect desulfurization treatment, or the like.
  • the following adjustment may be performed: a fuel oil containing more than 0.50 mass% of a sulfur element and a fuel oil containing less than 0.50 mass% of a sulfur element are mixed to provide a fuel oil base oil having a sulfur element content of from 0.01 mass% to 0.50 mass%.
  • its kinematic viscosity at 40°C is preferably from 1 mm 2 /s to 600 mm 2 /s, more preferably from 2 mm 2 /s to 500 mm 2 /s, still more preferably from 2 mm 2 /s to 400 mm 2 /s, still more preferably from 2 mm 2 /s to 250 mm 2 /s.
  • the kinematic viscosity is measured by a method described in JIS K 2283 (2000).
  • a fuel oil base oil containing at least one selected from light oil (including light oil special grade 1, light oil grade 1, light oil grade 2, light oil grade 3, light oil special grade 3, and a MGO) and heavy oil (including heavy oil A, heavy oil B, heavy oil C, a MDO, a VLSFO, and an ULSFO) is preferably used.
  • the total content of the light oil and the heavy oil in the fuel oil base oil is not particularly limited, but from the viewpoint of the effect of the present invention, the total amount of the light oil and the heavy oil is preferably from 10 mass% to 100 mass%, more preferably from 40 mass% to 100 mass%, still more preferably from 80 mass% to 100 mass% with respect to the total amount of the fuel oil base oil.
  • a fuel oil base oil in which a content ratio between the light oil and the heavy oil is from 0:100 to 90:10 in terms of mass ratio is preferred.
  • a fuel oil base oil containing at least one selected from the MGO and the heavy oil is particularly preferably used as the fuel oil base oil.
  • the total content of the MGO and the heavy oil in a fuel oil base oil is not particularly limited, but from the viewpoint of the effect of the present invention, the total amount of the MGO and the heavy oil is preferably from 10 mass% to 100 mass%, more preferably from 40 mass% to 100 mass%, still more preferably from 80 mass% to 100 mass%, particularly preferably 100 mass% with respect to the total amount of the fuel oil base oil.
  • a content ratio between the MGO and the heavy oil when the total amount of the MGO and the heavy oil in the fuel oil base oil is 100 mass% is not particularly limited.
  • the content ratio between the MGO and the heavy oil may be set to from 0:100 to 100:0 in terms of mass ratio, and is preferably set to from 0:100 to 90:10.
  • a calcium salicylate to be used in the present invention is a calcium salicylate having a total base number of from 100 mgKOH/g to 1,200 mgKOH/g.
  • the total base number is a value measured in conformity with ASTM D2896.
  • the total base number of the calcium salicylate is preferably from 200 mgKOH/g to 1,000 mgKOH/g, more preferably from 300 mgKOH/g to 900 mgKOH/g, still more preferably from 370 mgKOH/g to 800 mgKOH/g.
  • calcium salicylate having a total base number of from 100 mgKOH/g to 1,200 mgKOH/g means that the total base number of the calcium salicylate itself is from 100 mgKOH/g to 1,200 mgKOH/g, and when the fuel oil composition of the present invention uses two or more kinds of calcium salicylates, the total base number means the total base number of a mixture formed of the calcium salicylates.
  • a commercial product and a product produced by a known method may each be used as the calcium salicylate to be used in the present invention, and examples thereof include calcium salicylates obtained by: a method including causing an alkyl phenol, which is obtained by alkylating phenol with an olefin having 4 to 32 carbon atoms, to react with an alkali metal hydroxide to provide an alkyl phenoxide, then causing the alkyl phenoxide to react with a carbon dioxide gas to carboxylate the phenoxide, and then causing the carboxylated product to react with a calcium compound; and a method including causing salicylic acid and an olefin having 4 to 32 carbon atoms to react with each other through use of an alkylating agent to provide an alkylsalicylic acid, and then causing the alkylsalicylic acid to react with a calcium compound.
  • the calcium salicylate to be used in the present invention may be specifically, for example, a calcium salt of an alkylsalicylic acid represented by the following general formula (1) or general formula (2).
  • R 1 represents a hydrocarbon group having 4 to 32 carbon atoms.
  • examples of such group include: a linear alkyl group having 4 to 32 carbon atoms; a branched alkyl group having 4 to 32 carbon atoms; a linear alkenyl group having 4 to 32 carbon atoms; a branched alkenyl group having 4 to 32 carbon atoms; an alicyclic hydrocarbon group having 4 to 32 carbon atoms; and an aromatic hydrocarbon group having 6 to 32 carbon atoms.
  • R 1 represents preferably a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 12 to 28 carbon atoms out of those groups.
  • R 2 represents a hydrocarbon group having 4 to 32 carbon atoms.
  • examples of such group include: a linear alkyl group having 4 to 32 carbon atoms; a branched alkyl group having 4 to 32 carbon atoms; a linear alkenyl group having 4 to 32 carbon atoms; a branched alkenyl group having 4 to 32 carbon atoms; an alicyclic hydrocarbon group having 4 to 32 carbon atoms; and an aromatic hydrocarbon group having 6 to 32 carbon atoms.
  • R 2 represents preferably a hydrocarbon group having 6 to 30 carbon atoms, more preferably a hydrocarbon group having 12 to 28 carbon atoms out of those groups.
  • One or more kinds of calcium salts of alkylsalicylic acids each represented by the general formula (1) described above may be used as the calcium salicylate to be used in the present invention, one or more kinds of calcium salts of alkylsalicylic acids each represented by the general formula (2) may be used, or the one or more kinds of calcium salts of alkylsalicylic acids each represented by the general formula (1) and the one or more kinds of calcium salts of alkylsalicylic acids each represented by the general formula (2) may be used in combination.
  • a calcium salt obtained by treating an alkylsalicylic acid represented by the general formula (1) or the general formula (2) with a calcium compound, such as calcium hydroxide, calcium carbonate, calcium borate, calcium chloride, or heavy calcium carbonate, may be used.
  • the calcium salicylate to be used in the present invention preferably contains at least one of calcium salt of an alkylsalicylic acid represented by the general formula (1) or the general formula (2), and is more preferably a mixture of a calcium salt of an alkylsalicylic acid represented by the general formula (1) and a calcium salt of an alkylsalicylic acid represented by the general formula (2).
  • a content ratio between the respective alkylsalicylic acids is not particularly limited.
  • a content molar ratio between the alkylsalicylic acid represented by the general formula (1) and the alkylsalicylic acid represented by the general formula (2) is preferably from 10:1 to 0.1:1, more preferably from 8.0:1 to 0.5:1, still more preferably from 5.0:1 to 1.0:1, particularly preferably from 4.0:1 to 1.5:1.
  • R 1 and R 2 each preferably represent an alkyl group having 14 to 18 carbon atoms.
  • R 1 and R 2 each preferably represent an alkyl group having 16 to 18 carbon atoms.
  • R 1 and R 2 each preferably represent an alkyl group having 20 to 28 carbon atoms.
  • R 1 and R 2 each preferably represent an alkyl group having 16 carbon atoms.
  • R 1 and R 2 each preferably represent an alkyl group having 14 to 28 carbon atoms.
  • a metal ratio with respect to the calcium salicylate to be used in the present invention is not particularly limited, from the viewpoint of the effect of the present invention, the ratio is preferably from 0.2 to 10, more preferably from 0.5 to 8.0, still more preferably from 1.0 to 5.0.
  • the metal ratio with respect to the calcium salicylate can be adjusted by adjusting a ratio between the calcium element content and the alkylsalicylic acid content (adjusting a raw material ratio at the time of the treatment of the alkylsalicylic acid with the calcium compound).
  • the metal ratio may be increased by, for example, treating the alkylsalicylic acid with an excess amount of the calcium compound.
  • the metal ratio can be set to less than 1.0 by reducing the ratio of the calcium compound.
  • a calcium element ratio with respect to the calcium salicylate to be used in the present invention is not particularly limited, from the viewpoint of the effect of the present invention, the ratio may be set to, for example, from 1.0 mass% to 35 mass%, and is preferably from 1.0 mass% to 30 mass%, more preferably from 5.0 mass% to 30 mass%, still more preferably from 10 mass% to 28 mass%.
  • the calcium salicylate to be used in the present invention may be treated as follows before its use: before the preparation of the fuel oil composition, the calcium salicylate is diluted with a fuel oil base oil in advance to be turned into a calcium salicylate-diluted product.
  • the content of the calcium salicylate in the calcium salicylate-diluted product can be appropriately adjusted in accordance with purposes.
  • the content ratio of the calcium salicylate may be set to from 10 mass% to 99 mass% with respect to the total amount of the calcium salicylate-diluted product.
  • the fuel oil base oil for diluting the calcium salicylate may be the same fuel oil base oil as the fuel oil base oil to be used in the fuel oil composition of the present invention, or may be a fuel oil base oil different therefrom.
  • the total base number of the calcium salicylate-diluted product that may be used in the present invention is not particularly limited, for example, the total base number is preferably from 30 mgKOH/g to 400 mgKOH/g, more preferably from 60 mgKOH/g to 360 mgKOH/g, still more preferably from 100 mgKOH/g to 300 mgKOH/g, particularly preferably from 150 mgKOH/g to 260 mgKOH/g.
  • a calcium element ratio with respect to the calcium salicylate in the calcium salicylate-diluted product that may be used in the present invention is not particularly limited, from the viewpoint of the effect of the present invention, the ratio may be set to, for example, from 1.0 mass% to 35 mass%, and is preferably from 1.0 mass% to 30 mass%, more preferably from 2.0 mass% to 20 mass%, still more preferably from 10 mass% to 28 mass%, still more preferably from 5.0 mass% to 12.0 mass%, particularly preferably from 6.0 mass% to 9.0 mass%.
  • the content of the calcium salicylate in the fuel oil composition of the present invention is preferably from 0.001 mass% to 5.0 mass%, more preferably from 0.005 mass% to 3.0 mass%, still more preferably from 0.01 mass% to 2.0 mass% with respect to the total amount of the fuel oil composition.
  • the content of the calcium salicylate in the fuel oil composition of the present invention is preferably from 1 ppm by mass to 2,000 ppm by mass, more preferably from 5 ppm by mass to 1,500 ppm by mass, still more preferably from 10 ppm by mass to 1,000 ppm by mass with respect to the total amount of the fuel oil composition in terms of calcium element content.
  • a ratio between the sulfur element content in the fuel oil base oil and a calcium element content derived from the calcium salicylate is preferably from 1,000:1 to 0.5:1, more preferably from 800:1 to 1:1, still more preferably from 500:1 to 2:1 in terms of mass ratio.
  • the fuel oil composition of the present invention can be produced through the mixing of the fuel oil base oil having a sulfur element content of from 0.01 mass% to 0.50 mass% and the calcium salicylate or the calcium salicylate-diluted product by a known method.
  • the composition may be produced by, for example, adding the total amount of the calcium salicylate or the calcium salicylate-diluted product to the fuel oil base oil in one stroke, or adding the calcium salicylate or the calcium salicylate-diluted product thereto in a plurality of baches, under an environment at from normal temperature to 100°C, and stirring and mixing the materials at from normal temperature to 150°C.
  • the composition preferably further includes a sorbitan ester.
  • the sorbitan ester that may be used in the present invention is not particularly limited as long as the sorbitan ester is a compound obtained by esterifying the entirety or part of the hydroxy groups of sorbitol or anhydrous sorbitol.
  • Examples thereof include a sorbitan monofatty acid ester, a sorbitan difatty acid ester, a sorbitan trifatty acid ester, a sorbitan sesquifatty acid ester, and a polyoxyalkylene-condensed sorbitan fatty acid ester.
  • a sorbitan ester whose fatty acid is any one of lauric acid, stearic acid, and oleic acid is preferably used.
  • the HLB of the sorbitan ester is not particularly limited, the HLB is preferably from 1.2 to 12.0, more preferably from 1.5 to 11.0, still more preferably from 1.8 to 10.0.
  • the HLB is described in detail in, for example, WO 2019/245024 A1 as described below.
  • the hydrophilic-lipophilic balance represents the ratio of the molecular weight of a hydrophilic group moiety to the total molecular weight of a surfactant, and the HLB of a nonionic surfactant is determined from Griffin's equation.
  • the HLB of a mixed surfactant including two or more kinds of nonionic surfactants is determined as described below.
  • the HLB of the mixed surfactant is obtained by arithmetically averaging the HLB values of the respective nonionic surfactants on the basis of their blending ratios:
  • Mixed HLB ⁇ HLBx ⁇ Wx / ⁇ Wx
  • the content of the sorbitan ester if the fuel oil composition of the present invention includes the sorbitan ester is not particularly limited, from the viewpoint of the effect of the present invention, the content of the sorbitan ester is preferably from 0.001 mass% to 5.0 mass%, more preferably from 0.005 mass% to 3.0 mass%, still more preferably from 0.01 mass% to 2.0 mass% with respect to the total amount of the fuel oil composition.
  • a ratio between the calcium element content derived from the calcium salicylate and the content of the sorbitan ester in the fuel oil composition is not particularly limited.
  • the ratio between the calcium element content derived from the calcium salicylate and the content of the sorbitan ester in the fuel oil composition may be set to, for example, from 1:1 to 1:10,000 in terms of mass ratio, and is set to preferably from 1:1 to 1:1,000, more preferably from 1:2 to 1:500.
  • the fuel oil composition of the present invention When the fuel oil composition of the present invention is formed as described above, there can be easily produced a fuel oil composition, which can suppress the deposition of sludge at the time of its storage or at the time of its use, and has various characteristics, such as combustibility, storage stability, low-temperature fluidity, and handleability.
  • the fuel oil composition of the present invention may further include any other additive in accordance with purposes such as improvements in combustibility, storage stability, oxidation stability, wear resistance, uniformity, safety, environmental compatibility, startability, low-temperature fluidity, and handleability.
  • the surface ignition inhibitor examples include: organic phosphorus-based compounds, such as tributyl phosphite, trimethyl phosphite, tricresyl phosphate, tricyclohexyl phosphate, cresyl diphenyl phosphate, trimethyl phosphate, and methyl phenyl phosphate; and organic boron-based compounds, such as 2-ethylhexyl boronate and butyl diisobutyl boronate. Those inhibitors may be used alone or in combination thereof.
  • the content of the surface ignition inhibitor is not particularly limited, the content is preferably, for example, from 0.001 mass% to 10 mass% with respect to the total amount of the fuel oil composition.
  • octane number improver examples include methanol, ethanol, butanol, butyl acetate, methyl-tert-butyl ether, ethyl-tert-butyl ether, methyl-tert-amyl ether, N-methylaniline, methylcyclopentadienyl manganese tricarbonyl, and tetraethyllead. Those improvers may be used alone or in combination thereof.
  • the content of the octane number improver is not particularly limited, the content is preferably, for example, from 0.001 mass% to 10 mass% with respect to the total amount of the fuel oil composition.
  • cetane number improver examples include: aliphatic nitrates, such as ethyl nitrate, methoxyethyl nitrate, isopropyl nitrate, amyl nitrate, hexyl nitrate, heptyl nitrate, octyl nitrate, 2-ethylhexyl nitrate, and cyclohexyl nitrate; and peroxides such as di-tert-butyl peroxide. Those improvers may be used alone or in combination thereof.
  • the content of the cetane number improver is not particularly limited, the content is preferably, for example, from 0.001 mass% to 10 mass% with respect to the total amount of the fuel oil composition.
  • antimicrobial or microbicidal agent examples include: inorganic microbicidal agents, such as silver sulfate, silver nitrate, zinc sulfate, zinc nitrate, copper sulfate, and copper ethylenediaminetetraacetate; organic nitrogen-based antimicrobial agents, such as hexahydro-1,3,5-tris(2-hydroxyethyl)-triazine; organic bromine-based antimicrobial agents, such as 2,2-dibromo-3-nitrilopropionamide, 1,4-bis(bromoacetoxy)-2-ethane, and bistribromomethylsulfone; and isothiazoline-based antimicrobial agents, such as 2-methyl-4-isothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-octylisothiazolin-3-one
  • the rust inhibitor examples include an aliphatic amine and a salt thereof, an organic phosphoric acid ester, and an organic sulfonic acid salt. Those inhibitors may be used alone or in combination thereof.
  • the content of the rust inhibitor is not particularly limited, the content is preferably, for example, from 0.001 mass% to 10 mass% with respect to the total amount of the fuel oil composition.
  • Examples of the deposit improver include tricresyl phosphate, trimethyl phosphate, tris(chloroethyl) phosphate, polypropylene, polybutene, polyisobutylene amine, polyether amine, polyalkylamine, polyoxyalkyleneamine, polyalkylphenoxyaminoalkane, and polyalkylene succinimide. Those improvers may be used alone or in combination thereof. Although the content of the deposit improver is not particularly limited, the content is preferably, for example, from 0.001 mass% to 10 mass% with respect to the total amount of the fuel oil composition.
  • antioxidants examples include: amine-based antioxidants, such as N,N'-diisopropyl-p-phenylenediamine, N,N'-dibutyl-p-phenylenediamine, N,N'-dioctyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-ditolyl-p-phenylenediamine, and N-tolyl-N'-xylenyl-p-phenylenediamine; phenol-based antioxidants, such as 2-t-butylphenol, 2,6-ditertiarybutylphenol, 2,6-ditertiarybutyl-4-methylphenol, 2,4-dimethyl-6-tertiarybutylphenol, and 2,4,6-tri-t-butylphenol; and sulfur-based antioxidants, such as dilauryl 3,3'-thiodipropionate, distearyl 3,3'-
  • the metal deactivator examples include: amino compounds, such as ethylenediamine; salicylidene-based compounds, such as N,N'-disalicylidene-1,2-diaminopropane, N,N'-disalicylidene-2-cyclohexanediamine, N,N'-disalicylidene ethylenediamine, N,N'-bis(dimethylsalicylidene)ethylenediamine, N,N'-bis(dimethylsalicylidene)ethylenetetramine, and salicylaldoxime; triazole-based compounds, such as 1-[bis(2-ethylhexyl)aminomethyl]-1,2,4-triazole, 1-(1-butoxyethyl)-1,2,4-triazole, 4,4'-methylenebis(2-undecyl-5-methylimidazole), and bis[(N-methyl)imidazol-2-yl]carbinol octyl
  • antiwear agent examples include: sulfur-based antiwear agents, such as sulfurized fats and oils, an olefin polysulfide, a sulfurized olefin, dibenzyl sulfide, ethyl-3-[[bis(1-methylethoxy)phosphinothioyl]thio]propionate, a tris-[(2 or 4)-isoalkylphenol]thiophosphate, 3-(di-isobutoxy-thiophosphorylsulfanyl)-2-methyl-propionic acid, triphenyl phosphorothionate, ⁇ -dithiophosphorylated propionic acid, methylenebis(dibutyldithiocarbamate), O,O-diisopropyl-dithiophosphorylethyl propionate, 2,5-bis(n-nonyldithio)-1,3,4-thiadiazole, 2,5-bis(1,1,3,3-tetramethylbutan
  • the detergent or the dispersant examples include a phosphoric amide, an aminoalkane, an alkylamine phosphoric acid ester, polyether amine, polybutenylamine, an alkenyl succinimide, an alkenyl succinic acid ester, a salicylic acid metal salt (excluding a calcium salicylate), a sulfonic acid metal salt, a carboxylic acid metal salt, and a phosphonic acid metal salt.
  • Those detergents and dispersants may be used alone or in combination thereof.
  • the content of the detergent or the dispersant is not particularly limited, the content is preferably, for example, from 0.001 mass% to 10 mass% with respect to the total amount of the fuel oil composition.
  • the fluidity improver examples include a polymethacrylate-based polymer, a polyacrylate-based polymer, an olefinically unsaturated polymer, an ethylene-vinyl acetate-based copolymer, a polyolefin-substituted phenol-based polymer, an alkenyl succinamide, a fatty acid ester of an alkylene oxide adduct of an alkane polyol, and a fatty acid ester of an alkylene oxide adduct of an alkanolamine.
  • Those improvers may be used alone or in combination thereof.
  • the content of the fluidity improver is not particularly limited, the content is preferably, for example, from 0.001 mass% to 10 mass% with respect to the total amount of the fuel oil composition.
  • the calculated carbon aromaticity index (CCAI) of the fuel oil composition of the present invention is not particularly limited, from the viewpoints of various characteristics of the fuel oil composition, the CCAI is preferably 780 or more and 900 or less, more preferably 800 or more and 860 or less. In the present invention, the CCAI of the fuel oil composition is calculated on the basis of ISO 8217.
  • the flash point of the fuel oil composition of the present invention is not particularly limited, from the viewpoints of various characteristics of the fuel oil composition, the flash point is preferably 40°C or more and 120°C or less.
  • the flash point of the fuel oil composition is measured by a Pensky-Martens closed cup method described in JIS K 2265-3 (2007).
  • the pour point of the fuel oil composition of the present invention is not particularly limited, from the viewpoints of various characteristics of the fuel oil composition, the pour point is preferably -40°C or more and 30°C or less.
  • the pour point of the fuel oil composition is measured by a method described in JIS K 2269 (1987).
  • the kinematic viscosity of the fuel oil composition of the present invention is not particularly limited, from the viewpoints of various characteristics of the fuel oil composition, the kinematic viscosity thereof at 40°C is preferably from 1 mm 2 /s to 400 mm 2 /s, more preferably from 2 mm 2 /s to 200 mm 2 /s, most preferably from 2 mm 2 /s to 100 mm 2 /s.
  • the density of the fuel oil composition of the present invention is not particularly limited, from the viewpoints of various characteristics of the fuel oil composition, the density thereof at 15°C is preferably 0.70 g/cm 3 or more and 1.00 g/cm 3 or less, more preferably 0.80 g/cm 3 or more and 0.98 g/cm 3 or less.
  • the density of the fuel oil composition is measured by a method described in JIS K 2249 (2011).
  • the fuel oil composition of the present invention can be used without any particular limitation as long as its mode of use is such that a liquid fuel oil is used.
  • the composition may be used as, for example, a fuel oil for an automobile such as a passenger car or a truck, a fuel oil for a ship such as a passenger ship or a cargo ship, a fuel oil for an aircraft such as an airplane or a helicopter, a fuel oil for a railway vehicle, such as a diesel locomotive, a fuel oil for agricultural machinery, or a fuel oil for construction machinery.
  • the composition is preferably used as a fuel oil for a ship out of those fuel oils.
  • Fuel oil base oil A A fuel oil base oil formed of a cracked base oil fraction having a sulfur element content of 0.25% and a kinematic viscosity at 40°C of 25.0 mm 2 /s.
  • Table 1 Total base number (mgKOH/g) Ca element content ratio (mass%) (1) : (2) structure ratio Structure represented by R 1 or R 2 Calcium salicylate 1 560 20% 2.2:1 Alkyl group having 14 to 18 carbon atoms Calcium salicylate 2 390 14% 2.2:1 Alkyl group having 14 to 18 carbon atoms Calcium salicylate 3 278 10% 2.2:1 Alkyl group having 14 to 18 carbon atoms Calcium salicylate 4 860 32% 2.2:1 Alkyl group having 14 to 18 carbon atoms Calcium salicylate 5 420 14% 1.8:1 Alkyl group having 16 to 18 carbon atoms Calcium salicylate 6 700 25% 1.5:1 Alkyl group having 16 to 18 carbon atoms Calcium salicylate 7 668 25% 2.5:1 Alkyl group having 14 to 18
  • Fuel oil compositions were prepared by using fuel oil base oils, calcium salicylate-diluted products, sorbitan esters, and dispersants, which were comparative compounds, described below as shown in Tables 2 to 9 below.
  • calcium element contents derived from the calcium salicylates in the calcium salicylate-diluted products, or the comparative compounds, in the respective fuel oil compositions are also shown in Tables 2 to 9.
  • Fuel oil base oil 1 A fuel oil base oil having a sulfur element content of 0.44% and a kinematic viscosity at 40°C of 5.5 mm 2 /s (mixed base oil containing 20 mass% of heavy oil C having a sulfur element content of 2.1% and 80 mass% of a MGO having a sulfur element content of 0.03%)
  • Fuel oil base oil 2 A fuel oil base oil having a sulfur element content of 0.24% and a kinematic viscosity at 40°C of 4.2 mm 2 /s (mixed base oil containing 10 mass% of heavy oil C having a sulfur element content of 2.1% and 90 mass% of a MGO having a sulfur element content of 0.03%)
  • Fuel oil base oil 3 A fuel oil base oil having a sulfur element content of 0.04% and a kinematic viscosity at 40°C of 3.1 mm 2 /s (mixed base oil containing 0.5 mass% of heavy oil C having a sulfur element content of 2.1% and 99.5 mass% of a MGO having a sulfur element content of 0.03%)
  • Fuel oil base oil 6 A fuel oil base oil having a sulfur element content of 0.36% and a kinematic viscosity at 40°C of 120 mm 2 /s (mixed base oil containing 5 mass% of a VLSFO having a sulfur element content of 0.46% and 95 mass% of a VLSFO having a sulfur element content of 0.35%)
  • Fuel oil base oil 7 A fuel oil base oil formed of a VLSFO having a sulfur element content of 0.46% and a kinematic viscosity at 40°C of 138 mm 2 /s
  • Fuel oil base oil 8 A fuel oil base oil formed of a VLSFO having a sulfur element content of 0.47% and a kinematic viscosity at 40°C of 475 mm 2 /s
  • Fuel oil base oil 9 A fuel oil base oil formed of a VLSFO having a sulfur element content of 0.44% and a kinematic viscosity at 40°C of 8.1 mm 2 /s
  • Calcium salicylate-diluted product 1 A diluted product having a total base number of 224 mgKOH/g and a calcium element ratio of 8.1%
  • Calcium salicylate-diluted product 2 A diluted product having a total base number of 156 mgKOH/g and a calcium element ratio of 5.5%
  • Calcium salicylate-diluted product 3 A diluted product having a total base number of 111 mgKOH/g and a calcium element ratio of 4.0%
  • Calcium salicylate-diluted product 4 A diluted product having a total base number of 344 mgKOH/g and a calcium element ratio of 12.9%
  • Calcium salicylate-diluted product 5 A diluted product having a total base number of 168 mgKOH/g and a calcium element ratio of 5.6%
  • Calcium salicylate-diluted product 6 A diluted product having a total base number of 280 mgKOH/g and a calcium element ratio of 10.0%
  • Calcium salicylate-diluted product 7 A diluted product having a total base number of 267 mgKOH/g and a calcium element ratio of 10.0%
  • Calcium salicylate-diluted product 8 A diluted product having a total base number of 160 mgKOH/g and a calcium element ratio of 6.3%
  • Calcium salicylate-diluted product 9 A diluted product having a total base number of 170 mgKOH/g and a calcium element ratio of 6.1%
  • Calcium salicylate-diluted product 10 A diluted product having a total base number of 229 mgKOH/g and a calcium element ratio of 8.0%
  • Calcium salicylate-diluted product 11 A diluted product having a total base number of 320 mgKOH/g and a calcium element ratio of 11.0%
  • Calcium salicylate-diluted product 12 A diluted product having a total base number of 63 mgKOH/g and a calcium element ratio of 2.1%
  • Calcium salicylate-diluted product 13 A diluted product having a total base number of 170 mgKOH/g and a calcium element ratio of 6.1%
  • Calcium salicylate-diluted product 14 A diluted product having a total base number of 190 mgKOH/g and a calcium element ratio of 6.7%
  • Calcium salicylate-diluted product 15 A diluted product having a total base number of 279 mgKOH/g and a calcium element ratio of 11.7%
  • Calcium salicylate-diluted product 16 A diluted product having a total base number of 240 mgKOH/g and a calcium element ratio of 9.6%
  • Calcium salicylate-diluted product 17 A diluted product having a total base number of 173 mgKOH/g and a calcium element ratio of 6.2%
  • Low-base number calcium salicylate-diluted product A diluted product of the low-base number calcium salicylate (total base number: 16 mgKOH/g, calcium element ratio: 0.9%)
  • Calcium sulfonate-diluted product A diluted product having a total base number of 300 mgKOH/g and a calcium element ratio of 11.8% (diluted product obtained by mixing calcium sulfonate having a total base number of 750 mgKOH/g and a calcium element ratio of 30%, and the fuel oil base oil A at a mass ratio of 40:60)
  • Alkyl salicylate 5-Methylsalicylic acid
  • Salicylic acid alkyl ester 2-Ethylhexyl salicylate
  • Succinimide-based dispersant Polyisobutene succinimide
  • Phosphoric acid ester-based dispersant An oleyl-4EO phosphoric acid ester
  • Pluronic dispersant A POE-POP block polymer of ethylenediamine
  • Polycarboxylic acid-based dispersant A sodium salt of an olefin/maleic acid copolymerized product
  • Acetylene-based dispersant A POE-POP block polymer of acetylenediol Table 2 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Fuel oil base oil Fuel oil base oil 1 Balance Fuel oil base oil 2 Balance Balance Balance Balance Balance Balance Fuel oil base oil 3 Balance Calcium salicylate-diluted product 1 0.10% 0.10% 0.10% 0.04% 0.30% 0.50% 1.0% Calcium salicylate-diluted product 2 0.30% Calcium salicylate-diluted product 3 0.30% Calcium salicylate-diluted product 4 Calcium salicylate-diluted product 5 Calcium salicylate-diluted product 6 Calcium salicylate-diluted product 7 Calcium salicylate-diluted product 8 Calcium salicylate-diluted product Calcium salicylate-diluted product 9 Calcium salicylate-diluted product 10 Calcium salicylate-diluted product 10 Calcium salicylate-diluted product 11 Calcium salicylate-diluted product 12 Calcium salicylate-diluted product 13 Calcium salicylate-diluted product 14 Calcium salicylate-diluted product 15 Calcium salicylate-diluted product Calcium salicylate-diluted product 16 Calcium sal
  • the fuel oil compositions prepared in Examples 1 to 41 and Comparative Examples 1 to 20 were evaluated for their sludge dispersion-deposition characteristics by a spot test method described in ASTM D 4740 (2014). Specifically, each of the fuel oil compositions heated to 90°C was dropped onto filter paper (test paper), and was held at 100°C for 1 hour. After that, a spot test evaluation was performed by evaluating the state of a spot on the filter paper in accordance with the following evaluation indices. In this evaluation, an evaluation index 1 means that the evaluated composition is most excellent in sludge dispersibility (suppression of the deposition of sludge), and the evaluation index 1 or an evaluation index 2 means that the composition has practicality. The results were shown in Tables 2 to 9 above.
  • the fuel oil composition of the present invention is excellent in sludge dispersibility, and is hence excellent in suppression of the deposition of sludge at the time of its storage or at the time of its use.
  • Blending examples of fuel oil compositions prepared by using the following fuel oil base oils, calcium salicylate-diluted products, sorbitan esters, and other additives are shown in Tables 10 to 15.
  • Fuel oil base oil 1 A fuel oil base oil having a sulfur element content of 0.44% and a kinematic viscosity at 40°C of 5.5 mm 2 /s (mixed base oil containing 20 mass% of heavy oil C having a sulfur element content of 2.1% and 80 mass% of a MGO having a sulfur element content of 0.03%)
  • Fuel oil base oil 2 A fuel oil base oil having a sulfur element content of 0.24% and a kinematic viscosity at 40°C of 4.2 mm 2 /s (mixed base oil containing 10 mass% of heavy oil C having a sulfur element content of 2.1% and 90 mass% of a MGO having a sulfur element content of 0.03%)
  • Fuel oil base oil 3 A fuel oil base oil having a sulfur element content of 0.04% and a kinematic viscosity at 40°C of 3.1 mm 2 /s (mixed base oil containing 0.5 mass% of heavy oil C having a sulfur element content of 2.1% and 99.5 mass% of a MGO having a sulfur element content of 0.03%)
  • Fuel oil base oil 4 A fuel oil base oil having a sulfur element content of 0.03% and a kinematic viscosity at 40°C of 3.1 mm 2 /s (100 mass% of a MGO having a sulfur element content of 0.03%)
  • Fuel oil base oil 5 A fuel oil base oil having a sulfur element content of 0.30% and a kinematic viscosity at 40°C of 90 mm 2 /s (mixed base oil containing 20 mass% of an ULSFO having a sulfur element content of 0.08% and 80 mass% of a VLSFO having a sulfur element content of 0.35%)
  • Fuel oil base oil 6 A fuel oil base oil having a sulfur element content of 0.36% and a kinematic viscosity at 40°C of 120 mm 2 /s (mixed base oil containing 5 mass% of a VLSFO having a sulfur element content of 0.46% and 95 mass% of a VLSFO having a sulfur element content of 0.35%)
  • Fuel oil base oil 7 A fuel oil base oil formed of a VLSFO having a sulfur element content of 0.46% and a kinematic viscosity at 40°C of 138 mm 2 /s
  • Fuel oil base oil 8 A fuel oil base oil formed of a VLSFO having a sulfur element content of 0.47% and a kinematic viscosity at 40°C of 475 mm 2 /s
  • Fuel oil base oil 9 A fuel oil base oil formed of a VLSFO having a sulfur element content of 0.44% and a kinematic viscosity at 40°C of 8.1 mm 2 /s
  • Calcium salicylate-diluted product 3 A diluted product having a total base number of 111 mgKOH/g and a calcium element ratio of 4.0%
  • Calcium salicylate-diluted product 9 A diluted product having a total base number of 170 mgKOH/g and a calcium element ratio of 6.1%
  • Calcium salicylate-diluted product 11 A diluted product having a total base number of 320 mgKOH/g and a calcium element ratio of 11.0%
  • Calcium salicylate-diluted product 16 A diluted product having a total base number of 240 mgKOH/g and a calcium element ratio of 9.6%
  • Antimicrobial or microbicidal agent 1 POE lauryl amine
  • Antimicrobial or microbicidal agent 2 Hexahydro-1,3,5-tris(2-hydroxyethyl)-triazine
  • Antimicrobial or microbicidal agent 3 1,2-Benzisothiazolin-3-one
  • Rust inhibitor 2 A tetrapropenylsuccinic acid ester
  • Antioxidant 1 2,6-Ditertiarybutylphenol
  • Antioxidant 2 N,N'-Dioctyl-p-phenylenediamine
  • Antioxidant 3 Distearyl ⁇ , ⁇ '-thiodibutylate
  • Antiwear agent 1 Oleic acid
  • Antiwear agent 2 An octylic acid-type phosphoric acid ester
  • Antiwear agent 3 Zinc dibutyl dithiophosphate
  • Fluidity improver 1 An ethylene-vinyl acetate copolymer
  • Fluidity improver 2 A methyl methacrylate-hexadecyl acrylate copolymer
  • Fluidity improver 3 A behenic acid ester of an EO adduct of triethanolamine Table 10 Blending example 1 Blending example 2 Blending example 3 Blending example 4 Blending example 5 Blending example 6 Blending example 7 Blending example 8 Blending example 9 Blending example 10 Fuel oil base oil oil Fuel oil base oil 1 Balance Balance Balance Balance Fuel oil base oil 2 Balance Balance Balance Balance Fuel oil base oil 3 Fuel oil base oil 4 Fuel oil base oil 5 Fuel oil base oil 6 Calcium salicylate Calcium salicylate-diluted product 3 0.10% 0.10% Calcium salicylate-diluted product 9 0.10% 0.10% Calcium salicylate-diluted product 11 0.05% 0.30% 0.05% 0.10% Calcium salicylate-diluted product 16 0.10% 0.10% Antimicrobial or microbicidal agent Antimicrobial or microbicidal agent 1 0.01% 0.01% 0.01% 0.005% Antimicrobial or microbicidal agent 2 0.01% 0.01% 0.01% Antimicrobial or microbicidal agent 3 0.01% 0.01% 0.03% Rust inhibitor
  • the fuel oil composition excellent in suppression of the deposition of sludge at the time of its storage or at the time of its use.
  • the fuel oil composition excellent in combustibility, storage stability, oxidation stability, wear resistance, uniformity, safety, environmental compatibility, startability, low-temperature fluidity, handleability, and the like.

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EP20779052.8A 2019-03-28 2020-03-23 Composition d'huile combustible Withdrawn EP3950891A4 (fr)

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JP (1) JPWO2020196386A1 (fr)
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JP3089075B2 (ja) 1991-12-13 2000-09-18 日石三菱株式会社 自動変速機油組成物
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CN113646414A (zh) 2021-11-12
TW202102655A (zh) 2021-01-16
JPWO2020196386A1 (fr) 2020-10-01
US20220195321A1 (en) 2022-06-23
EP3950891A4 (fr) 2022-11-30
WO2020196386A1 (fr) 2020-10-01
TWI828889B (zh) 2024-01-11
KR20210144749A (ko) 2021-11-30

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