WO2020153769A2 - Procédé de production d'huile lourde à induction d'odeurs et de vapeurs nocives réduite, et système associé - Google Patents

Procédé de production d'huile lourde à induction d'odeurs et de vapeurs nocives réduite, et système associé Download PDF

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WO2020153769A2
WO2020153769A2 PCT/KR2020/001130 KR2020001130W WO2020153769A2 WO 2020153769 A2 WO2020153769 A2 WO 2020153769A2 KR 2020001130 W KR2020001130 W KR 2020001130W WO 2020153769 A2 WO2020153769 A2 WO 2020153769A2
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Prior art keywords
heavy oil
carrier gas
harmful components
odor
oil
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English (en)
Korean (ko)
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WO2020153769A3 (fr
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조정모
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Korea Research Institute of Chemical Technology KRICT
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Korea Research Institute of Chemical Technology KRICT
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Priority claimed from KR1020190008759A external-priority patent/KR102201116B1/ko
Priority claimed from KR1020190054083A external-priority patent/KR102299697B1/ko
Priority claimed from KR1020200003205A external-priority patent/KR102365337B1/ko
Application filed by Korea Research Institute of Chemical Technology KRICT filed Critical Korea Research Institute of Chemical Technology KRICT
Priority to CN202080009849.9A priority Critical patent/CN113316628B/zh
Publication of WO2020153769A2 publication Critical patent/WO2020153769A2/fr
Publication of WO2020153769A3 publication Critical patent/WO2020153769A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/50—Mixing liquids with solids
    • B01F23/51—Methods thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C3/00—Working-up pitch, asphalt, bitumen
    • C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • 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
    • C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
    • C10G31/06—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for by heating, cooling, or pressure treatment

Definitions

  • the present invention relates to a method and system for inducing odor and reducing harmful components of heavy oil, and removing heavy odor inducing and harmful components in high-boiling heavy oil generated in a refinery or petrochemical process in advance to remove heavy oil.
  • the present invention relates to a method and system for manufacturing high-quality heavy oils that can effectively solve the problem of discharge of harmful substances such as odor and fine dust that may occur in a process used as a furnace.
  • Heavy oil refers to residue oil composed mostly of high-boiling hydrocarbons with an API level of 29 or less, which is obtained from nature or obtained from downstream of the refinery, petrochemical, and steel industries.
  • the components in the heavy oil are located in the center of agglomerated form of high-polarity asphaltenes, and the resin forms a colloidal state of a core-shell structure that surrounds them to form a boundary layer from non-polar hydrocarbons. It is known that not only macromolecules such as resins and asphaltenes having high polarity, but also a wide variety of low boiling point chemicals are trapped in the colloid of the shell structure.
  • Korean Patent Registration No. KR 0779070 (announced on November 28, 2007), in order to remove odor and dust in the process of manufacturing asphalt concrete using asphalt, dust is produced by installing an intake fan that sucks the odor generated inside the mixer during asphalt production. And a method for removing odor is described, and in Korean Registered Patent Publication KR 1187221 (2012.10.02. Announcement) and Korean Registered Patent Publication KR 1273329 (2013.06.11. Announcement), the Ascon manufacturing department or Ascon is placed on a truck.
  • a technique for removing dust and odors generated during the production of ascon is described by forcibly inhaling other harmful dust generated during the loading process and treating it with a hopper, a centrifugal dust collector, a filtration filter, and a condenser at the bottom.
  • These methods are only indirect air pollution treatment technologies that simply collect and purify only a part of the harmful substances generated during the heating process of asphalt, so there are limitations in preventing the spread of air pollution and cannot be a fundamental solution.
  • the present invention pays attention to the fact that harmful components including odor-producing and fine dust generated in the process using heavy oil as a raw material are mainly low-boiling compounds generated from heavy oil itself, and the low-boiling-point compounds are removed in advance to remove heavy oil. It is intended to provide a method for fundamentally blocking the generation of harmful components in the process of using powder as a raw material.
  • the present invention since the low boiling point compounds in the heavy oil are collected in a large number of colloids of the core-shell structure, which is a complex form of heavy molecules containing asphaltene, an additive capable of highly dispersing the asphaltenes of the low boiling point compounds. It is intended to provide a method of facilitating the removal of low-boiling-point compounds by adding and a technique of utilizing a distillation residue of waste oil as the additive.
  • Waste oil does not normally contain food by-products such as edible oils, oils containing high polychlorinated biphenyls, and other oils that are difficult to recover or recover as fuel oil through refining. Although there are differences by country, in general, waste lubricants are discharged at a specific gravity of 75% or more of waste oil, and include abrasive oil, cutting oil, fuel oil, asphalt oil, electric insulating oil, grease, and rust preventive oil.
  • European Patent No. 0708174 (published April 24, 1996) distills the waste oil from which moisture is removed below 240°C and further separates the distilled residue by solvent extraction, followed by hydrotreating at the rear end. ) The example of improving the yield and the quality of the recovered oil was presented through the process.
  • U.S. Patent No. 9932530 (published on Dec. 17, 2015) provides an example of a process for producing high-quality base oil of waste lubricating oil through one or more hydrogenation pretreatment reaction processes in which waste oil is removed.
  • Their boiling point distribution has a high boiling point characteristic similar to the reduced pressure residue oil occurring at the downstream of the refining process, and because high concentrations of asphaltene dispersants remain, it is quantified and used as an additive for dispersing asphaltenes. It can be effectively applied to the reforming process to induce odor and reduce harmful substances.
  • the present invention in removing the odor inducing odors and harmful components in the heavy oil, by using the distillation residue generated during the purification process of the waste oil to modify the heavy oil and at the same time useful utilization of waste oil Want to provide
  • the present invention includes a heating means for heating the heavy oil stored therein, and the heavy gas reformed to be discharged to the outside along with the odor inducing and harmful components in the heated heavy oil in which the carrier gas supplied therein is heated.
  • Reaction tank A carrier gas supply unit supplying a carrier gas into the heavy oil reforming reactor; A carrier gas dispersion unit for dispersing the carrier gas supplied from the carrier gas supply unit into the heavy oil reforming reaction tank; And a malodor inducing and harmful component separating unit separating odor inducing and harmful components from the carrier gas discharged from the heavy oil reforming reaction tank.
  • the carrier gas circulating unit for re-supplying the carrier gas in which the malodor inducing and harmful components are separated from the malodor inducing and harmful component separating into the heavy oil reforming reaction tank may be further included.
  • the heavy oil reforming reaction tank is characterized in that it heats the heavy oil to a temperature in the process of using the heavy oil as a raw material and a temperature in the range of 330°C or higher.
  • a demister for filtering the heavy oil fine particles contained in the carrier gas before the carrier gas is discharged to the outside of the heavy oil reforming reactor may further include a.
  • the malodor inducing and harmful component separation unit using at least one means of an adsorbent, a scrubber, a separator, a cooler, the malodor inducing and harmful component from the carrier gas discharged from the heavy oil reforming reaction tank Characterized in that to separate.
  • At least one selected from waste catalysts, molecular sieves and NaOH is additionally located between the rear end of the malodor inducing and harmful component separation unit and the inlet of the heavy oil reforming reactor.
  • the heavy oil may be at least one selected from reduced pressure residue oil, pyrolysis oil, coal dry coal tar, asphalt, and natural bitumen.
  • the present invention the heavy oil production system and the heavy oil production system and the odor inducement and harmful components obtained from the asphalt and aggregate reduced asphalt mixing unit; characterized in that it comprises; Provided ascon manufacturing system.
  • the present invention (a) a heavy oil heating step of heating the heavy oil stored in the heavy oil reforming reactor to the reforming reaction temperature; (b) a carrier gas supply step of dispersing and supplying the carrier gas into the heated heavy fraction stored in the heavy oil reforming reactor; (c) the odor induction and toxic component discharge step in which the odor induction and harmful components in the heavy oil heated inside the heavy oil reforming reaction tank are discharged out of the heavy oil reforming reaction tank together with the carrier gas; and It provides a method for manufacturing asphalt with reduced harmful components.
  • the manufacturing method further comprises: (d) a odor inducing and harmful component separating step of separating degassed odor and harmful components separated from heavy oil from the carrier gas; , (d) separating the offensive odor inducing and harmful components separated from the heavy oil from the carrier gas, and further comprising the step of separating the odor inducing and harmful components, the odor inducing and harmful components in the step (d) is separated
  • the carrier gas can be returned to step (b) above.
  • the heavy oil of step (a) is characterized in that an asphaltene dispersant is added.
  • the asphaltene additive may be a bipolar additive and/or waste oil-derived asphaltene dispersant, wherein the polar group has a dipole moment of 1.1 or more and the non-polar group has a dipole of 0.5 or less, and the waste oil-derived asphaltene dispersant is used in waste oil. It may be a residue of the distillation column after removing solids and moisture and recovering renewable hydrocarbons.
  • the polar group of the bipolar additive is an amine, imide, amide, alcohol, phenol, ester, methacrylate It includes at least one selected from, the non-polar group includes a polymer derived from any one or a combination of ethylene, propylene, isobutylene, diene (styrene), styrene (styrene), the number average of the bipolar additive It is characterized by being 100 to 500,000 in molecular weight (The number average molecular weight).
  • the heavy oil may be at least one selected from reduced pressure residue oil, pyrolysis oil, coal dry coal tar, asphalt, and natural bitumen.
  • the present invention provides a method for manufacturing ascon which has reduced odor inducing and harmful components, characterized in that the heavy oil is asphalt, and the asphalt and aggregate produced by the heavy oil manufacturing method of the present invention are mixed.
  • the heavy oil treated according to the reforming method of the present invention is in a state in which harmful components that may cause harmful substances such as odor and fine dust contained in the oil are reduced, so that the working environment in the industry using heavy oil as a raw material is reduced. Improvement and the generation of harmful substances in the industry can be greatly reduced.
  • the present invention provides evenly dispersing the carrier gas inside the reforming reactor using a gas distribution device, thereby promoting the gaseous mass transfer of low-boiling components in the heavy oil and improving the separation rate of odors and vapors containing harmful components. It has the effect of using the dispersing agent to further improve the rate of separation of the odor-causing and harmful components.
  • the heavy oil modified according to the method of the present invention does not show a significant influence on the properties as a heavy oil raw material because only a small amount of low boiling point components are separated, and thermal decomposition or chemical reaction of molecular structures in the oil does not predominate.
  • the low-cost separating waste fuel (Refuse-derived Fuel) generated in the process of refining waste oil is used as a dispersing agent for removing harmful components of the heavy oil, economic efficiency of the heavy oil reforming process is improved and waste oil is treated. You can save money.
  • FIG. 1 is a view for explaining a process for producing an additive of a reforming process for reducing odor induction and harmful components in heavy oil from waste oil in the present invention.
  • Figure 2 is a diagram showing the dispersion behavior of the asphaltene structure in the heavy oil when the asphaltene additive according to the present invention is added.
  • FIG. 3 is a view for explaining a heavy oil production system for performing a heavy oil production method for removing odor-causing and harmful components according to an embodiment of the present invention.
  • Figure 5 shows the gas chromatogram of the vapor containing odor inducing and harmful components before the modification of the sample used in Comparative Example 5 and Example 11 of the present invention.
  • Figure 6 shows the gas chromatogram of the vapor containing odor-causing and harmful components after the modification of the sample used in Comparative Example 5 and Example 11 of the present invention.
  • Figure 7 compares each of the gas chromatograms measured under the same analytical conditions and the vapor containing odor inducing and harmful components generated after heating the asphalt raw material and the asphalt after modification to the used in Example 14 of the present invention under the same analysis conditions It is shown.
  • the term'odor-causing and harmful components' refers to all substances that cause odor and substances that do not cause odor, but includes harmful substances, and direct fine/ultrafine dust generated during the process using heavy oil as a raw material ( PM2.5 and PM10) and materials for generating the fine/fine dust are also included.
  • the present invention relates to a method for producing heavy oil in which odor induction and harmful components in which harmful components are effectively removed in advance are significantly reduced.
  • the heavy oil is, as a representative example, a vacuum residue, which is the bottom oil of a vacuum distillation column (eg, obtained at about 25 to 100 mmHg and has an equivalent boiling point of about 813.15 K or higher) during the crude oil refining process, Pyrolysis fuel oil generated in the petrochemical industry, coal tar generated from the dry flow of coal, etc., is one of the substances that are generated or ultimately remained downstream of various industries, or black semi-solid or liquid at room temperature Examples include asphalt that exists as or natural bitumen that exists in nature.
  • asphalt is widely used in various industries ranging from road paving materials to small materials such as roof waterproofing materials.
  • road paving it is used in the form of asphalt concrete (ascon) in which aggregates such as sand and gravel are mixed with asphalt.
  • asphalt concrete asphalt concrete
  • aggregates such as sand and gravel are mixed with asphalt.
  • the heavy oil asphalt is heated and mixed with the aggregate in a flowable state. At this time, the heated heavy oil, that is, the generation of odor and harmful vapor components from the asphalt occurs in large quantities and continuously. .
  • the odor-causing and harmful vapor components are mainly volatile organic compounds (VOCs), and the volatile organic compounds generated in the asphalt reservoir include polycyclic aromatic hydrocarbons (PAHs), sulfides (thioethers (RSR ⁇ ) or alkyl mercaptans) including BTX ( R-SH), hydrogen sulfide, sulfide, etc.), various oxides (aldehydes, acetates, ketones), and other nitrogen compounds.
  • PHAs polycyclic aromatic hydrocarbons
  • RSR ⁇ thioethers
  • alkyl mercaptans alkyl mercaptans
  • BTX R-SH
  • hydrogen sulfide sulfide
  • sulfide etc.
  • various oxides aldehydes, acetates, ketones
  • the method for preparing heavy oil with reduced odor inducing and harmful components includes: (a) a heavy oil heating step of heating the heavy oil stored in the heavy oil reforming reactor to a reforming reaction temperature; (b) a carrier gas supply step of dispersing and supplying the carrier gas into the heated heavy fraction stored in the heavy oil reforming reactor; (c) the odor induction and harmful component discharge step in which the odor induction and harmful components in the heavy oil heated inside the heavy oil reforming reaction tank are discharged to the outside of the heavy oil reforming reaction tank together with the carrier gas.
  • the method for preparing heavy oil with reduced odor inducing and harmful components of the present invention after step (c), (d) separating from deodorizing odor inducing and harmful components from the heavy oil and separating from the carrier gas further includes; can do.
  • the carrier gas separated in the step (d) is returned to the step (b) again, and a carrier gas circulation step of reusing the carrier gas for separating and deodorizing odor and harmful components in the heavy oil may be further included.
  • the step (a) is a step of heating the heavy oil to an appropriate reforming temperature so that odor-causing and harmful components can be volatilized.
  • the reforming temperature is preferably in the range above the temperature at which the heavy oil in the reforming reactor melts and the flow of the liquid phase starts to occur in the solid phase, and below the temperature at which the constituents of the heavy oil begin to thermally decompose, more preferably the heavy oil. It is in the range of above the process operating temperature in the process using as raw material and below the denaturation temperature of heavy oil.
  • the modified set temperature may be set at a temperature of 330° C. or less, preferably in the range of 200 to 325° C. in terms of process efficiency and physical properties, more preferably May range from 250 to 315°C.
  • step (a) by adding a dispersant of the constituent substances in the heavy oil together with the heavy oil, it is possible to further accelerate the separation of odor and harmful components in the heavy oil.
  • the components in the heavy oil are located in the center of agglomerated form of high-polarity asphaltenes, and the resin is limited to surround them to form a boundary layer from a non-polar hydrocarbon material in a colloidal state of a core-shell structure.
  • the colloid of the core-shell structure not only macromolecules such as resin and asphaltene having high polarity, but also a large number of various low-boiling chemicals are trapped, and subsequent processes for utilizing heavy oil, such as heavy oil
  • low-boiling chemicals trapped in the colloid of the core-shell structure are discharged at a limited speed, causing environmental pollution such as odor.
  • the bipolar additive should preferably have a polar group having a dipole moment of at least 1.1 debye and a non-polar group having a dipole moment of 0.5 dibye or less in the same molecule, and these groups are structurally symmetrical to form a net dipole moment. It is preferred that no offset occurs.
  • the net upper pole moment is preferably 0.6 division or more. Since the raw material to which these additives are applied is a heavy oil having a hydrophobicity, it is preferable to make the properties of the material itself hydrophobic or oil soluble.
  • the dipole moment of the polar group is not limited thereto, but may be 1.1 dividing or higher, or 1.1 dividing to 10 dividing, 1.1 dividing to 7 dividing, 1.1 dividing to 5 dividing, or 1.1 dividing to 3 dividing.
  • the dipole moment of the non-polar group has a value close to 0 by definition, but is not limited thereto, and may be 0.5 dibe or less, 0.1 dibe or less, or 0.01 dibe or less depending on the relative strength of the dipole moment of the polar group.
  • the net dipole moment of the bipolar additive is not limited to this, but may be 0.6 divi or more, and may be 0.6 divi to 10 dividing, 0.6 dividing to 5 dividing, or 0.6 dividing to 2 dividing.
  • the polar group of the bipolar additive may be exemplified by a functional group derived from nitrogen or oxygen, and the non-polar group may be a linear hydrocarbon or a linear hydrocarbon having a polydispersity index (PI; Mw/Mn) of close to 1
  • PI polydispersity index
  • An example is a structure derived from a form. It is preferable that these bipolar additives do not affect the properties or functions of the heavy oil, and even when a small amount is used compared to the raw material, it is preferable that the dispersion effect of the polar molecules in the heavy oil is remarkable.
  • polar molecules eg, a lipophilic dispersion catalyst
  • hydrophilicity and hydrophobicity eg, an interface
  • the bipolar additive is, for example, selected from a single molecule or a polymer composed of a single or multiple combinations of amine, imide, amide, alcohol, phenol, ester, methacrylate, and the like.
  • the bipolar additive may include polyalkylene succinate imide; Alkyl phenolic dispersants; Polyacrylic dispersants; Urea, imidazoline, imidazole, tetrazole, tetrazoline, tetrazolone, lactam, sulfam, thiourea, triazole, triazolin, pyridone, pyrimidone, dihydropyrimidine, tetrahydropyrimidine, pyrazole, Imidazoline, dihydropyrimidinone, triazine, dihydrotriazine, tetrahydrotriazine, oxadiazole, thiadiazole, dihydrooxadiazole, dihydrothiadiazole, salicylate, etc.
  • the asphaltene dispersant added in step (a) may be a waste oil-derived asphaltene dispersant.
  • the waste oil-derived asphaltene dispersant is a top and bottom residue obtained from the distillation process of waste oil, and may correspond to 5 to 50% by weight based on the input waste oil, and the API degree may be 5 to 30 days.
  • the obtained bottom-bottom residue is used as an additive for high dispersion of asphaltenes by mixing with heavy oil in a temperature range of 30°C to 200°C, where the flowability of heavy oil can be maintained after or without the pretreatment.
  • waste oil does not usually include food by-products such as waste cooking oil, oils containing high polychlorinated biphenyl, and other oils that are difficult to recover or recover as fuel oils through refining.
  • waste lubricants are discharged at a specific gravity of 75% or more of the total amount of waste oil, and include abrasive oil, cutting oil, fuel oil, asphalt oil, electric insulating oil, grease, and anti-rust oil.
  • the feed waste oil 1 undergoes a process 20 for physically separating solids through a physical method such as centrifugation or filtration.
  • the separated solid content 2 is a material having a solid form formed by mechanical friction or oxidation of oil, and may include macromolecules, salts, metals, and the like.
  • the waste oil stream 3 from which the solids have been removed is removed through the low temperature distiller 30 maintained at 240° C. or lower and supplied to the high temperature distiller 40 through the downstream of the tower.
  • the high-temperature distiller 40 it is preferable to separate oils having a boiling point distribution of 240°C to 590°C, and it is efficient to perform distillation under reduced pressure to reduce energy.
  • the hydrocarbon vapor stream 6 at the top of the high-temperature distiller 40 is recovered (7) as a liquid oil through a condenser (50), which can be utilized as an alternative fuel oil, regenerated base oil, etc. according to the characteristics of the oil.
  • the stream 8 at the bottom of the tower is a residue component containing a hydrocarbon oil having a high boiling point, and is distilled to be 5 to 50% by weight based on the waste oil input.
  • Waste oil distillation residue which is the flow (8) at the bottom of the obtained tower, can be used as it is asphalt dispersant derived from waste oil of the present invention, but if necessary, a new dispersant is additionally supplied (9) to have flowability from 30° C. to After mixing in the stirring tank 60 heated to a temperature of 200 °C can be obtained (10) in the form of a well-dispersed mixed additive.
  • the novel dispersant may be the aforementioned bipolar additive.
  • the stirring may use means known in the art.
  • Asphalt is an organic raw material constituting ascon and is tacky and has fluidity when heated to 80°C or higher, but is a black or dark brown semi-solid material having a very high viscosity at room temperature. It is obtained from natural or petroleum refining processes and contains a large amount of high boiling point compounds. It is a heavy oil contained.
  • This oil is a mixture composed of a wide variety of chemical species in addition to the high-boiling-point compounds, and its components can be largely classified into SARA (Saturates, Aromatics, Resins, Asphaltenes).
  • asphaltene has a large molecular weight, high polarity, and constitutes most of heteroatoms (sulfur and vaginal) that can directly cause odor.
  • the components in the asphalt as shown on the left side of FIG. 2, are core-shells that form a boundary layer from non-polar hydrocarbons by restricting them to be centrally located in a condensed form with high polarity asphaltenes. It is known to have a colloidal state of a core-shell structure.
  • the amount of the asphaltene dispersant added may be such that the content of the asphaltene dispersant in the mixture of the heavy oil and the asphaltene dispersant is 0.01 wt% to 5 wt%.
  • the content of the asphaltene dispersant is less than 0.01wt%, the polar molecules in the raw material are not sufficiently dispersed, so the effect may be insignificant. If the weight ratio exceeds 5wt%, the dispersion effect compared to the amount used decreases, and the physical properties of the heavy oil raw material vary. Can.
  • the content of the asphaltene dispersant may be 0.1 wt% to 5 wt%.
  • the step (b) is a carrier gas supply step for dispersing and supplying the carrier gas to the heated heavy oil component stored in the heavy oil reforming reaction tank.
  • the carrier gas dispersed and introduced into the heavy oil reforming reaction tank is bubbled into the heavy oil, and has a low boiling point from a large colloidal cluster formed by mutual forces with heavy molecules such as resin and asphaltenes. It promotes the degassing and mass transfer of the components, and diffuses into the carrier gas and causes saturated odor and vapors containing harmful components to form the carrier gas and the mixed gas, which is the next step by natural and forced convection of the mixed gas.
  • step (c) it is discharged to the outside of the reforming vessel at a faster rate, thereby rapidly reducing the amount of odor and harmful components in the raw materials.
  • step (b) the low-boiling component degassed from the large colloidal cluster due to the carrier gas is transported by the carrier gas before being re-merged into the large colloid phase by mutual attraction with the surrounding resin or asphaltenes. Therefore, it can be irreversibly separated from heavy oil.
  • the carrier gas is preferably an inert gas having no activity in order to prevent the oxidation of heavy oil, and may be mainly composed of helium, argon, nitrogen gas, etc., but a reforming process is applied instead of a continuous supplying process during the reforming process Oxygen-containing air may be used when the carrier gas is recirculated in a closed system provided as a one-time before or in the early stage.
  • the step (c) is a odor induction and harmful component discharge step in which the odor induction and harmful components in the heavy oil heated inside the heavy oil reforming reaction tank are discharged to the outside of the heavy oil reforming reaction tank together with the carrier gas.
  • the heavy oil fine particles may be collected in advance using a demister or the like to prevent excessive heavy oil loss.
  • the step (d) may be a separation step for separating and deodorizing deodorized and harmful components separated from heavy oils from the carrier gas.
  • the separation means in the step (d) may use a conventional means, for example, by using adsorption, oxidation, scrubbing, or cooling method, it is possible to separate the odor-causing and harmful components from the carrier gas.
  • the carrier gas separated in step (d) can be reused by returning it to the heavy oil reforming reactor in step (b).
  • the duration of the reforming steps (b) and (c) may vary depending on the amount of heavy oil and the amount of carrier gas supplied, but may generally last for 1 to 24 hours.
  • the present invention provides a manufacturing system for producing heavy oil with reduced odor inducing and harmful components.
  • the manufacturing system of the present invention includes a heating means for heating the heavy oil stored therein, and a heavy oil reforming reaction tank discharged to the outside with odor and harmful components in the heated heavy oil in which the carrier gas supplied therein is heated;
  • a carrier gas supply unit supplying a carrier gas into the heavy oil reforming reactor;
  • a carrier gas dispersion unit for dispersing the carrier gas supplied from the carrier gas supply unit into the heavy oil reforming reaction tank;
  • a malodor inducing and harmful component separating unit separating odor inducing and harmful components from the carrier gas discharged from the heavy oil reforming reaction tank. It is configured to include.
  • the manufacturing system of the present invention may be further configured to further include a carrier gas circulation unit for re-supplying the carrier gas from which the malodor inducing and harmful components are separated into the heavy oil reforming reaction tank in the separation of the malodor causing and harmful components.
  • the heavy oil reforming reaction tank may further include a demister for filtering heavy oil fine particles contained in the carrier gas before the carrier gas is discharged outside the heavy oil reforming reaction tank.
  • the odor-causing and harmful component separation unit is for separating odor-causing and harmful components from the carrier gas, and using at least one means of an adsorbent, a scrubber, a separator, and a cooler, from the carrier gas discharged from the heavy oil reforming reaction tank Odor-causing and harmful components can be separated.
  • FIG. 3 is a view for explaining a system for manufacturing a heavy oil with reduced odor induction and harmful components according to an embodiment of the present invention.
  • the heavy oil production system is reduced odor inducing and harmful components according to the present invention
  • the heavy oil reforming reaction tank 100 carrier gas supply unit 120, carrier gas dispersion unit 110, It comprises a malodorous component and a harmful component separation unit 130, it may be configured to further include a carrier gas circulating unit 140.
  • a heavy oil is located in an interior space, and heating means 103, a carrier gas inlet 101, and a carrier gas to deaerate substances containing odor and harmful components from the heavy oil located therein It comprises a discharge port (102).
  • the heavy oil mixture located therein by the heating means 103 is heated to promote separation and mass transfer of low boiling point components from the colloidal phase inside the heavy oil, This is transferred to the reforming reactor 100 in the form of a vapor by the carrier gas supplied inside. From the fluidized heavy oil, deodorized air and vapor containing harmful components are continuously discharged out of the reactor by the carrier gas.
  • a positive electrode additive and/or waste oil-derived asphaltene dispersant is added to the heavy oil of the reforming tank as an asphaltene dispersant, and then mixed mixture is added or the heavy oil raw material and the asphaltene dispersant are added to the reforming tank 100. After putting them together, the heavy oil mixture located inside is heated by the heating means 103. When the asphaltene dispersant is further added, the dispersant causes high dispersion of the asphaltenes in the heavy oil, so the separation of odor and harmful components can be accelerated.
  • the change in properties of the heavy oil does not predominate, and the heavy oil It is advantageous to keep the range below the maximum temperature that can function as.
  • the steam that may be generated in a process in which the heavy oil is used as a raw material or a site utilizing the same (induces odor and Harmful components) in advance.
  • the degree of odor induction and removal of harmful components and the removal rate may increase, but since a large number of hydrocarbons constituting the heavy oil can be decomposed and denatured, dominant thermal decomposition does not occur, but odor is caused and It is necessary to maintain a temperature high enough to cause physical degassing of low-boiling components that make up the harmful components.
  • the duration of the reforming reaction is continued until the target amount of odor induction and harmful components is reached.
  • the duration may vary depending on the amount of heavy oil to be reformed and the supply amount of carrier gas, but can generally last for 1 to 24 hours.
  • the carrier gas supply unit 120 is a means for supplying a carrier gas into the heavy oil reforming reaction tank 100, and may be configured using conventional techniques in the art.
  • the carrier gas when oxygen is included, a characteristic change may occur due to a partial oxidation reaction of the heated raw material. Therefore, it is preferable to be an inert gas having no activity in order to prevent the oxidation of heavy oil, and may be mainly composed of helium, argon, nitrogen gas, etc., but is not a continuous supply method during the reforming process, before the reforming process is applied or Air may be used if provided as a one-time in the initial stage and recirculated in a closed system.
  • the carrier gas supply unit 120 may be a device such as a pressure vessel capable of storing high-pressure gas.
  • the carrier gas dispersion unit 110 is to disperse the carrier gas supplied into the reforming reactor 100 over a wide area, whereby the carrier gas dispersed into the heavy oil reforming reactor 100 is within the oil fraction. Evenly distributed and bubbling, it is possible to more effectively transport and discharge the vapor containing the odor inducing and harmful components vaporized inside the heavy oil to the outside of the reforming reactor.
  • the carrier gas transports and transports vapor containing odor-causing and harmful components vaporized from the inside of the heavy oil, thereby forming a colloidal phase with macromolecules such as high-polarity asphaltenes or resins to degas from the heavy oil. It is possible to remove the harmful components that do not easily occur and can be separated only at a very limited speed and a part of the composition even at a high temperature within a fairly meaningful time.
  • the dispersing unit 110 is a conventional gas such as a dispersion plate in which a plurality of perforated holes are formed and a configuration consisting of a plurality of orifice nozzles from one carrier gas supply coil. It may be configured using at least one means of the dispersing means. In addition, to aid degassing, a method of directly flowing or physically agitating the raw oil component located in the reaction tank may be simultaneously applied.
  • the flow rate of the carrier gas injected from the carrier gas dispersion unit 110 may vary depending on the type of heavy oil, but the ratio of the standard flow rate per unit mass of the heavy oil raw material is 0.05 to 90 sccm/(g of feedstock), preferably May be 0.1 to 10 sccm/(g of feedstock).
  • the heavy oil reforming reaction tank 100 may additionally include a demister 104 therein, and by using the demister 104, before the carrier gas is discharged to the outside of the heavy oil reforming reaction tank 100 Filtering of particulates that may be contained in the carrier gas or excessive loss of high-boiling components can be prevented from boiling of raw materials that may occur during the reforming process.
  • the odor inducing and harmful component separating unit 130 for separating the odor inducing and harmful components is to remove or remove the odor inducing and harmful components from the carrier gas discharged from the reforming reaction tank 100 and remove them.
  • the malodor inducing and harmful component separation unit 130 absorbs malodor inducing and harmful components in the carrier gas using a scrubber, adsorbs using a catalyst or adsorbent, or liquefies using a cooler. It is possible to separate and remove the odor causing and harmful components in the carrier gas.
  • a waste catalyst may be used to adsorb malodor and harmful components by using an adsorbent among the separation means.
  • alumina-based or zeolite-based catalysts discharged from the chemical industry may be used as the used waste catalyst.
  • the malodor inducing and harmful component separation unit 130 in addition to separating and removing the malodor inducing and harmful components, by applying an oxidation catalyst, the malodor inducing from the carrier gas discharged from the asphalt reforming reaction tank 100 and It may also be configured to chemically convert substances containing harmful components directly into substances that are less harmful or have a higher boiling point.
  • the odor-causing and harmful component separation unit 130 may include a discharge port for continuously discharging the separated odor-causing and harmful components.
  • the carrier gas circulation unit 140 is to re-supply the carrier gas from which the oil vapor is separated or removed from the malodor inducing and harmful component separation unit 130 to the reforming reaction tank 100, and the transport through the configuration Since the carrier gas supplied by the gas dispersion unit 110 is not discharged out of the system, it is possible to circulate the reforming reaction tank 100 and the odor inducing and harmful component separation unit 130 by the carrier gas circulation unit 140 There is no need to continuously receive a carrier gas from the outside, and even if air is used as the carrier gas, oxygen present in the air at the beginning of the carrier gas circulation process is consumed through a very small amount of the raw material and oxidation reaction, and only nitrogen remains, so the carrier gas Even if only air is applied, the performance and effect of the modification according to the present invention may be exhibited.
  • the heavy oil in the present invention is asphalt
  • the heavy oil production method in which the malodor and harmful components of the present invention are reduced is an asphalt concrete manufacturing process, for example, an asphalt concrete mixing unit for mixing asphalt with aggregate. It can be configured to include.
  • the heavy oil of AP-5 grade supplied from S-OIL which is used as a raw material for manufacturing ascon, was tested as a heavy oil as a raw material, and modified without adding an asphaltene dispersant to the heavy oil. The reaction was carried out.
  • the properties of the AP-5 grade heavy oils supplied by S-OIL are as shown in Table 1.
  • an elemental analyzer Model: Thermo Scientific Flash EA-2000 Organic Elemental Analyzer, Detector: Thermal Conductivity Detector
  • SARA Saturates, Aromatics, Resins and Asphaltenes
  • Asphalt raw materials are in a solid state at room temperature, and the raw materials are quantified to analyze the characteristics, measure the amount of odor inducement and harmful components, or supply them as raw materials for the reforming reaction. It was used after standing for 3 hours or more to maintain flowability.
  • a process using heavy oil as a raw material for example, in order to collect and analyze odor-causing and harmful components generated during the production of ascon, 100 g of asphalt raw material before or after modification according to the present invention in a 250 ml reactor maintained at 180°C Served for up to 5 hours.
  • a vapor having a low boiling point is diffused to form a vapor concentration, and after a certain period of time, a vapor having a concentration in equilibrium with the liquid exists.
  • the vapor was allowed to stay in a sample loop (1 ml) mounted on a 6-port valve heated to 180°C or higher to prevent condensation, and then changed the flow path at the time of measurement to connect the gas chromatography with a mass spectrum detector (GC-MS ; gas chromatography w/ mass spectrum detector and HP 50+ column) were used to analyze the retention characteristics of the components, and the same analysis conditions (HP 50+ column) were performed using a separate gas chromatography equipped with a flame ionization detector (FID). ) was performed for quantitative analysis of each component.
  • the concentration of gaseous components was calibrated using a standard gas from the Refinery Gas Analyzer (RGA; Agilent 5184-3538, 5184-3543).
  • a high temperature, high pressure reactor (manufacturer: Ari Instrument, model: SCH reactor 500 w/ data gathering tool), which can be equipped with a 500 ml SUS Liner, was used as a reforming reactor.
  • the reforming temperature was detected using a thermocouple and was measured by inserting it into a thermowell to probe the temperature of the internal reforming reactor in close proximity.
  • the internal reforming temperature was supplied to the heat source through a heating furnace where heat transfer could occur through the outer wall, and the control temperature was maintained within ⁇ 1°C in the reforming step of the raw material using a multi-loop PID control program.
  • reforming was performed by supplying the carrier gas from the point of reaching the target temperature.
  • the carrier gas was supplied from within the closed loop by supplying nitrogen gas from the outside or by installing a gas transfer pump (model name: KNF N022ATE) so that the initial gas could be continuously recycled. It was controlled using a mass flow controller (mfc).
  • the gas flowing into the reforming reactor was distributedly supplied using a porous gas dispersion tube located at the bottom.
  • the vapor phase was discharged in the form of a mixture of vapor and carrier gas from the top of the reactor, and a demister of SUS316 was positioned to prevent the loss of high-boiling fraction.
  • the mixed gas was allowed to concentrate and collect only liquefied vapor through the inside of a double-jacketed gas phase condenser and a collection vessel designed to continuously flow coolant below -10°C through the outer tube.
  • the carrier gas was configured to be re-supplied through the gas transfer pump into the reactor.
  • Asphalt raw materials used for the reforming reaction were heated to 80° C. or higher, and 150 g was added to the reaction tank, and the raw materials were initially stirred at a rate of 50 rpm by a magnetic drive, and the stirring speed was changed to 300 rpm when the desired reforming temperature was reached. Did.
  • High-temperature reforming conditions may be advantageous in order to remove odor-causing and harmful components from heavy oil raw materials, but if excessively high temperature conditions are applied, thermal decomposition reactions of the raw materials dominate, so that irreversible characteristics of the raw materials can be significantly changed after reforming. have.
  • the heavy oil is heated to a high temperature and the thermal decomposition reaction proceeds, decomposition of a side alkyl chain outside the heavy molecule, such as asphaltene and resin, generally occurs gradually, and carbon number is caused by recombination between low molecular weight radicals. Is 4 or less, and a large amount of saturated hydrocarbons present in the gas phase at room temperature is generated.
  • high molecular weight radicals generated from thermal decomposition may induce the generation of high boiling point compounds corresponding to coke (toluene insoluble) or coke precursors corresponding to solid by-products by polycondensation. Even the characteristics of the raw material can be greatly changed. Therefore, it is necessary to identify a temperature region in which thermal decomposition does not occur, and search for raw material reforming conditions from this should be preceded. To this end, the following experiment was performed.
  • the boiling point properties of liquid products are measured by measuring the boiling point distribution according to ASTM D7169 (GC-Simdis), and the properties of gaseous products are measured by the amount of pressure change ( ⁇ P; the rate of gas partial pressure compared to the initial pressure) generated by gas during thermal decomposition. Together with the quantitative analysis by gas chromatography, the results are shown in Table 2.
  • the carrier gas supply method is indicated as external supply in Table 3, the carrier gas is continuously supplied from the outside, and after collecting and separating the vapor from the mixed steam discharged from the reforming reactor with a cooler, the carrier gas is not recycled to the reforming reactor. It was discharged to the outside.
  • the recirculation flow rate indicated as 0 sccm means that there is no supply of a carrier gas such as air or nitrogen flow.
  • Example 1 200 Air / Recirculation 100 99.6 26.2
  • Example 2 250 Air / Recirculation 100 99.0 2.6
  • Example 3 300 Air / Recirculation 100 98.1 0.5
  • Example 4 315 Air / Recirculation 100 94.9 0.1
  • Example 5 315 N2 / External supply 100 94.6 0.1
  • Example 6 315 Air / Recirculation 10 98.7 34.1
  • Example 7 315 N2 / External supply 5,000 89.7 0.0
  • Comparative Example 2 315 Air /- 0 99.8 95.5 Comparative
  • Table 3 compares the mass of raw materials recovered by the reforming conditions and the relative generation amount of oil vapor.
  • the amount of recovered raw materials was calculated as the amount of heavy reformed oil recovered from the reforming reactor compared to the initial raw material input.
  • the relative amount of steam generated is represented by converting the relative ratio of the mass of the oil vapor measured from the same process (Experimental Example 1) into the heavy oil material before modification and the heavy oil prepared according to each reforming condition.
  • Comparing the results of Comparative Example 1 and Examples 1 to 4 it can be seen that the effect of the temperature applied to the modification on the performance of removing odor and harmful components in heavy oil.
  • the reforming temperature is maintained at a temperature lower than the manufacturing temperature of the asphalt as the heavy oil is used as a raw material, for example, at 150°C as in Comparative Example 1, very limited odor induction and reduction of harmful components are possible.
  • the effect of reducing the generation of oil vapor compared to the raw material before modification is less than 3%, which is very insignificant.
  • the relative generation amount of oil vapor could be greatly reduced even by the 12-hour reforming reaction, which is a relatively short treatment time.
  • an excessively high carrier gas supplied (Comparative Example 4)
  • a large amount of raw material is discharged to the outside, and the hydrocarbon component condensed into the vapor collection unit located outside the reforming tank also contains a large amount of high boiling point components.
  • Tables 4 and 5 show the vapors recovered from the low-temperature separation of gaseous components located outside the reformer using gas chromatography equipped with a mass spectrum detector in performing reforming according to Comparative Examples 1 and 4, respectively.
  • the composition and composition are analyzed, and the concentration of each component extracted from the initial input heavy oil mass is converted and charted based on the mass balance.
  • Each of the extracted components has various types such as saturated hydrocarbons and oxides (aldehydes, ketones, alcohols, carboxylic acids, etc.) that do not contain odor and harmful components, but aromatic and odor-causing components that are considered harmful components. Only phosphorus sulfides are listed.
  • Table 4 shows representative components and concentrations of compounds and aromatic compounds containing sulfur present in the vapor separated from Comparative Example 1.
  • Table 5 shows the representative components and concentrations of the compound and the aromatic compound containing sulfur and performing the compositional analysis of the separated vapor in Example 4.
  • an initial boiling point means an initial boiling point
  • a final boiling point means a final boiling point
  • Table 6 is a table showing the difference between the boiling point distribution and the elemental ratio of the heavy oil before or after the reforming, which is applied to the reforming process by varying the reforming temperature.
  • Example 1 and Example 4 heavy oils are exposed to the manufacturing process conditions of ascons using the heavy oils as raw materials, but rarely generate odor or vapors containing harmful components, whereas the It can be seen that the change is not greatly observed.
  • elemental analysis of the initial raw material before modification and the heavy oil raw material modified according to the examples no significant change in composition ratio was observed.
  • Example 4 in which the reduction amount of oil vapor was very large, it was found that the sulfur content was slightly decreased.
  • the odor induction and harmful components generated in the process using heavy oil as a raw material are very small, It can be expected as low boiling point components with a slow separation rate in the oil and a fast diffusion rate in the atmosphere.
  • the heavy oil is modified according to the method of the present invention, it can be seen that only the sulfur compound in the low-boiling region, that is, a malodor-causing component that may occur in a process using heavy oil as a raw material, for example, ascon manufacturing process, is selectively removed. have.
  • the method for improving the heavy oil content of the present invention which includes the process of promoting the separation rate in the oil content and separating and concentrating the generated vapor separately from the outside, can provide the heavy oil with which odor induction and harmful components have been effectively reduced or completely removed. Do.
  • the modified heavy oil should not cause a large change in the composition of the heavy oil.
  • the composition and content of heavy molecules constituting heavy oil concentration of asphaltenes or resins
  • Table 7 shows the results obtained by measuring the viscosity displacement over a temperature range of 110 to 170° C. with a rheometer (manufacturer: Thermo Scientific, model: HAAKE RheoStress 6000) for the initial raw material before reforming and the raw materials subjected to the reforming.
  • asphalt As a heavy oil produced from the refining process of crude oil, asphalt is classified into AP-5 (infiltration degree 60-80) and AP-3 (infiltration degree 80-100) according to the penetration degree.
  • the raw material before modification is asphalt corresponding to the AP-5 grade, and after heating to a temperature of 100° C. or higher, the raw material condition of the AP-5 grade based on the performance grade when the viscosity characteristic change is 20% or less. Can meet.
  • Odors and harmful components that occur during the reforming process of heavy oil raw materials are mostly composed of low boiling point compounds, and waste catalysts, adsorbents, absorbents, oxidizers, scrubbers, separators to prevent re-introduced into the reforming tank when recirculating carrier gas
  • the back can be further positioned.
  • waste catalyst Ni(5.2 wt.%)-Mo(24.8 wt.%)/alumina
  • G company 100g of waste catalyst (Ni(5.2 wt.%)-Mo(24.8 wt.%)/alumina) for petroleum refining supplied from G company, except that it is additionally located between the odor inducing and harmful component separation part and the carrier gas inlet was modified under the same conditions as in Example 4.
  • Table 8 shows the observation of changes in the performance of heavy oil reforming after removing the low boiling point components that may be partially present in the carrier gas recirculated into the reforming tank according to Examples 4 and 8-10.
  • Example 4 315 Air/Recirculation - 100 94.9 0.1
  • Example 8 315 Air/Recirculation Waste catalyst for oil refining 100 94.5 0.0
  • Example 9 315 Air/Recirculation Molecular sieve 13X 100 94.6 0.0
  • Example 10 315 Air/Recirculation NaOH 100 95.1 0.0
  • Example 8 As shown in Table 8, the experiments were carried out in the same manner as in Example 4, but in the case of Examples 8 to 10 in which a waste catalyst for petroleum refining or a molecular sieve 13X or NaOH was additionally installed between the odor inducing and harmful component separation and the carrier gas inlet. On the other hand, the relative amount of steam generated was zero, although there was no significant change in raw material recovery.
  • the change of the relative generation amount as described above shows a very significant result considering that the odor is often appealed even when a very small amount of the inducer is present, and the amount of oil vapor generated in a relatively short time. It means that it can be a way to reduce.
  • Example 11 and Comparative Example 5 is intended to show the effect of using a bipolar additive as an asphaltene dispersant in the method of reducing malodor and harmful components according to the present invention.
  • Example 11 except that no bipolar additive was added, the same procedure as in Example 11 was performed, and in order to analyze the effects of the reforming reaction, samples before and after the reforming reaction were analyzed by the same measurement method as Experimental Example 1.
  • Table 9 the vapor phase chromatogram of the vapor collected after continuously heating the raw material for 5 hours is shown in FIG. 5(a), the vapor phase chromatogram of the vapor collected under the same measurement conditions for the sample after reforming. Is shown in Figure 6 (a).
  • the equilibrium time in Table 9 below refers to the time in which the flask was heated at 180°C in Experimental Example 1, and the measured value for each equilibrium time is one-millionth of the total concentration of the vapor component formed in the gas phase space (wppm). ).
  • Table 9 is a chart comparing the amount of harmful vapors generated for the raw materials before and after the modification according to the introduction of the additives.
  • the difference in degassing behavior of the vapor (oil vapor) when the raw material (Comparative Example 5) and the bipolar material (No. 11) added with no additives to the heavy oil to which the reforming process was not applied were heated and maintained at 180° C. The rate and amount of occurrence) were observed. It can be seen that low-boiling components, which are expected to be trapped in the asphaltene structure, are vaporized very quickly in the initial phase (within 2 hours) and the deaerated mass is also observed in a very high amount in the raw material in which the bipolar material is present.
  • the amount of vapor generated after reforming in both the Examples and Comparative Examples was reduced by the reforming process at 300° C., but when the bipolar additive was added as in Example 11 of the present invention, it was not added. It can be seen that compared to Comparative Example 5, the amount of steam generated after the modification was reduced to about 1/60. This is about 1/300 of the amount of oil vapor generated from the heavy oil before reforming (compared to the amount of steam generated from the raw material before reforming in Example 5 and the raw material after reforming in Example 11), and the concentration of the heated closed gas phase space is also less than 100 wppm. It can be seen that the amount of vapor generated at the level is significantly reduced, and in reality, even if the raw material being heated to a high temperature of 180° C. or more is opened to the atmosphere, the odor that can be detected does not occur.
  • the dispersion degree of asphaltenes that is, through the control of the structure of the colloid on the heavy macromolecule, provided an environment in which only low-boiling oil vapor components can be selectively separated from the macromolecule aggregate. That is, when a combination of a bipolar additive and a reforming condition that promotes material transfer is applied, a process using heavy oil as a raw material, for example, it is possible to effectively remove harmful components that may occur continuously in the manufacturing process of Ascon in advance. It is the result to explain.
  • Table 10 below is a table showing the difference in elemental composition of heavy oil before and after the modification according to Comparative Example 5 and Example 11.
  • the constituent organic elements and their contents were analyzed using an elemental analyzer (Model: Thermo Scientific Flash EA-2000 Organic Elemental Analyzer, Detector: Thermal Conductivity Detector).
  • an elemental analyzer Model: Thermo Scientific Flash EA-2000 Organic Elemental Analyzer, Detector: Thermal Conductivity Detector.
  • the heavy oil used in Examples 12-14 and Comparative Example 6 was used as SKE or AP-5 grade heavy oil supplied from Hyundai Oilbank.
  • the flow 30 in which impurities and moisture are separated was separated into a liquefied hydrocarbon oil stream 41 and a distillation residue oil stream 50 through high temperature distillation. Waste oil was separated by taking three refinery products with different removal processes and impurities.
  • Waste oil 1 is prepared according to a physical filtration method using a filter in removing solids before the distillation step, waste oil 2 is prepared through centrifugation, and waste oil 3 induces salt precipitation after introducing coagulant sulfuric acid and uses a decanter. It is prepared by removing the sludge containing the precipitated salt.
  • the waste oil from which the impurities were removed was heated from 240° C. to 10° C. per minute to reach a boiling point of up to 590° C.
  • separation was performed such that the liquefied hydrocarbon oil and the distilled residue were 80-90% and 10-20%, respectively, by weight. From the waste oil 1 to 3, the residue obtained from the bottom flow through the distillation process was taken to prepare samples 1 to 3, and the distillate obtained from the top flow was taken to prepare samples 4 to 6.
  • Elemental analysis (elemental analysis; model: Thermo Scientific Flash 2000, detector: Thermal Conductivity Detector), X-ray fluorescence analysis; model: Thermo/ARL QUANT'X ), inductively coupled plasma-atomic emission spectrometry (ICP-AES; model name: Thermo Fisher Scientific iCAP 6500Duo), using the ASTM D7169 (GC-Simdis) method for the non-point distribution, Conradson carbon residue ; CCR) is shown in Table 11 below the results of the analysis using the ASTM D189 method.
  • ASTM D7169 GC-Simdis
  • the mass% represents the cumulative mass of the volatile components below each boiling point
  • the initial boiling point (IBP) refers to the initial boiling point
  • the final boiling point (FBP) refers to the final boiling point
  • the column top distillation has a relatively narrow boiling point distribution (230-585°C), while the column bottom residual (190-700°C) has a relatively high and wide area boiling point distribution. It can be observed.
  • the residual portion at the bottom of the tower is composed of a large amount of hydrocarbon compounds corresponding to a boiling point of 500°C or higher, similar to asphalt as a heavy oil.
  • Base oil is a high-boiling oil (reduced gas oil) obtained from crude oil. It is a colorless transparent mineral oil or PAO (poly- ⁇ -olefin) obtained through isomerization reaction after removing unsaturated double bonds or cyclic compounds through a purification process such as a hydrogenation process. ), polyol esters, wax cracking hydrocarbons and other synthetic oils are used.
  • the high-boiling hydrocarbon material is the main component of the distillation residue at the bottom of the distillation residue and is very similar to the boiling point distribution of heavy oils even in the non-point distribution, so even when used as an additive, it has no significant effect on the change in raw material properties. It may not.
  • top bottom residue when used as an asphaltene dispersant, when solid hydrocarbons such as coke are present in the bottom bottom residue, it may affect the viscosity or flowability of the heavy oil, and the top bottom residue When as measured by ASTM D189, the amount of carbon that can be solidified upon heating may be too high when the residual amount of recalcitrant residual carbon is 50% or more, making it difficult to utilize as an additive.
  • Table 13 shows the results of measuring the amount of residual non-decomposable carbon for the distillation residue in Experimental Example 4.
  • Each of the distillation residues quantified by the above analysis method was prepared as a waste oil-derived asphaltene dispersant, that is, as an additive in a heavy oil reforming method for reducing odor and harmful vapor.
  • Table 16 below shows the results of measuring the dispersion degree of asphaltenes using Turbiscan (manufacturer: Formulation, model name MA2000) according to ASTM D7061-04 for each of the samples prepared according to Experimental Example 4.
  • ASTM D7061-04 adds n-heptane, a non-polar solvent, to a heavy oil dissolved in a polar solvent to optically measure the relative dispersion according to sedimentation or phase separation of asphaltenes, and converts it to separability number to dynamically stabilize the oil. It is a standardization method for evaluating (stability). Separation water can be calculated as the standard deviation value for the change in average permeability measured every minute up to 15 minutes of stabilization time.
  • a heavy oil raw material As a heavy oil raw material, a heavy oil of AP-5 grade supplied from Hyundai Oil Bank was used, and after adding the distillation residue (top and bottom residue) in Experimental Example 4 to the heavy oil to be 5000 wppm, its dispersion effect was observed.
  • the heavy oil When analyzing the properties of the heavy oil, measuring the incidence of odor and harmful components, supplying it as a raw material for the reforming reaction, or adding a bipolar additive, the heavy oil is pre-heated to 80°C or more in a sealed container. It was used after standing in an oven for 3 hours or more to maintain flowability.
  • Sample classification No additives Sample 1 Sample 2 Sample 3 Separation water 8.5 0.7 1.5 1.4
  • Table 17 shows the results of measuring the dispersion degree of asphaltenes of heavy oils according to the concentration of sample 1 in the dispersant derived from waste oil of Experimental Example 4. Even when the additive was diluted to a concentration of 1,000 wppm or less, there was a partial effect of dispersing asphaltenes, but when the concentration of the additive was 5,000 wppm or more, a very extreme dispersion effect of asphaltenes was observed.
  • a reforming tank composed of the same principle as in Experimental Example 2, 15 kg of heavy oil with a reduced amount of odor and harmful components was prepared.
  • a reforming reactor a high-temperature and high-pressure reactor (manufacturer Buchi Pilot Plant) made of 50L Hastelloy-C was used, and the heat source was supplied through heat medium oil (Dowtherm RP) flowing through the outer wall of the reactor.
  • Air compressor maximum flow rate of supply 20L/min
  • the condenser was subjected to a large-scale reforming reaction according to the method of Experimental Example 2, except that a shell & tube type heat exchanger was used. It was carried out.
  • Example 12 the same procedure as in Example 12 was performed except that 10,000 wppm of waste oil-derived asphaltene dispersant (Sample 1 in Experimental Example 4) was added.
  • Example 12 The same procedure as in Example 12 was performed except that the asphaltene dispersant was not added in Example 12.
  • the equilibrium time in Table 18 below refers to the time in which the flask was heated at 180°C in Experimental Example 1, and the measured value for each equilibrium time is one-millionth of the total concentration of the vapor component formed in the gas phase space (wppm). ).
  • Table 18 is a chart comparing the amount of harmful vapors generated for the raw materials before and after modification according to the introduction of the asphaltene dispersant.
  • high oil vapor concentrations of 70,000 to 80,000 wppm in the gas phase were formed under conditions after 1 hour that seemed to have reached equilibrium composition, but the heavy oil raw materials that have undergone the reforming process according to the present invention are oil vapor It can be seen that the amount of generated is greatly reduced.
  • Example 13 When comparing the amount of oil vapor generated with respect to the modified heavy oil by adding 5,000 wppm (Example 12) and 10,000 wppm (Example 13) to the raw material (Comparative Example 6) without any asphaltene dispersant and waste oil-derived asphaltene dispersant, respectively, additives It can be seen that the case of adding is much more effective in reducing the amount of steam generated. Particularly, Example 13, in which the waste oil-derived asphaltene dispersant was added at a concentration of 10,000 wppm (a measurement result of Turbiscan according to ASTM D7061-04 of Experimental Example 5) so that the value of the separation water of the heavy oil was close to 0, Example 13 was carried out for modification of the vapor.
  • Table 19 below is a table showing the difference in the elemental ratio of the asphalt raw material before modification and after the modification according to Examples 6 and Examples 12 and 13.
  • the constituent organic elements and their contents were analyzed using an elemental analyzer (Model: Thermo Scientific Flash EA-2000 Organic Elemental Analyzer, Detector: Thermal Conductivity Detector). It can be seen that the asphalt modified according to Examples 12 and 13 and Comparative Example 6 shows almost the same composition ratio in the element ratio as compared with before modification. From this, it can be predicted that the properties of the asphalt will not change significantly even by the modification according to the method of the present invention using the waste oil distillation residue as an asphaltene dispersant.
  • the reforming reaction was carried out as follows in order to verify that the reduction effect of the odor-causing and harmful vapor-containing oil vapor was the same even by the large-scale reforming process.
  • About 15.3 kg of AP-5 grade asphalt supplied from Hyundai Oilbank was introduced with waste oil-derived asphaltene dispersant (sample 1 of Experimental Example 4) to be 5,000 wppm, and at the same time, a similar asphaltene dispersion effect (when used alone in the same environment)
  • ESCA organic additive
  • Emacs Solution organic additive
  • the reforming reaction proceeded at 230°C.
  • the carrier gas of the gas phase the initial gas contained in the reforming tank was continuously supplied and used.
  • the flow recirculated into the reforming tank was supplied by concentrating and separating odors and harmful components at a low temperature by an external condenser. While maintaining the flow rate of the gas at 5-20 slm, the raw material was reformed for 6 hours. After that, the circulation of the carrier gas was stopped, and the temperature in the reforming tank was lowered to 120° C. or less in a state in which the system was sealed, and then the modified heavy oil raw material was taken.
  • the equilibrium time in Table 20 below refers to the time in which the flask was heated at 180°C in Experimental Example 1, and the measured value for each equilibrium time is one-millionth of the total concentration of the vapor component formed in the gas phase space (wppm). ).
  • the amount of oil vapor generated before and after the modification showed a large difference, and when the amount of oil vapor was used as a mixed additive (asphalt dispersant derived from waste oil and asphaltene dispersant prepared by organic synthesis), the amount of oil vapor was generated before modification. It can be seen that it is reduced by about 1/30 of the raw material. From this, it can be seen that even when the asphaltene-derived asphaltene dispersant is partially introduced, it is a result explaining that it is effective in reducing odor and harmful substances.
  • Table 21 is a result of measuring the composition ratio of the elements before and after the large-scale modification.
  • the asphalt raw material modified in bulk according to Example 14 shows almost the same composition ratio in the element ratio as compared with before modification, and the asphalt is also modified by adding the waste oil derived asphaltene dispersant according to the method of the present invention. It can be inferred that the nature of the image has not changed significantly.
  • heavy oils modified with a large capacity according to the present invention also significantly reduce odor-inducing and harmful components, and the properties of heavy oils are hardly changed even by modification, so that heavy oils prepared according to the present invention as in the ascon manufacturing process are used. It can be seen that in the process used as a raw material, odor induction and harmful components are effectively suppressed, while physical properties of the final product can be taken in the same way.
  • the present invention relates to a technology capable of preventing the occurrence of odor and harmful components in a process using the heavy oil as a raw material by removing the odor induction and harmful components of the heavy oil generated in the petrochemical process in advance. As such, there is industrial availability.
  • the technique according to the present invention is to control the asphaltene molecules in the heavy oil to remove low-boiling harmful vapors.
  • heavy oil was observed to have no significant change in properties before and after reforming, but in terms of energy and physical properties management, the technology according to the present invention is first applied to the heavy oil produced downstream of the refinery process and various modified additives are added. Therefore, the method of manufacturing AP-5 grade asphalt may be more useful industrially.

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  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé de production d'huile lourde dans lequel des substances présentes dans l'huile lourde qui provoquent une pluralité d'odeurs et de constituants nocifs, notamment des poussières fines, sont éliminées à l'avance, afin d'empêcher la génération d'odeurs et de constituants nocifs, notamment des poussières fines, qui peuvent se produire au cours d'un processus utilisant de l'huile lourde chauffée en tant que matière première, et un système associé. Le procédé de production comprend : une étape de chauffage d'huile lourde consistant à chauffer une huile lourde stockée dans un réacteur de reformage d'huile lourde à une température de réaction de reformage ; une étape d'alimentation en gaz vecteur consistant à disperser et à fournir un gaz vecteur dans l'huile lourde chauffée stockée dans le réacteur de reformage d'huile lourde ; et une étape d'évacuation de constituants nocifs et d'odeurs induites consistant à évacuer, conjointement avec le gaz vecteur, des odeurs induites et des constituants nocifs présents dans l'huile lourde chauffée dans le réacteur de reformage d'huile lourde vers l'extérieur du réacteur de reformage d'huile lourde. De plus, le système comprend : le procédé de production d'huile lourde présentant une induction d'odeurs et de constituants nocifs réduite ; le réacteur de reformage d'huile lourde ; une unité d'alimentation en gaz vecteur ; une unité de dispersion de gaz vecteur ; et une unité de séparation d'odeurs induites et de constituants nocifs.
PCT/KR2020/001130 2019-01-23 2020-01-22 Procédé de production d'huile lourde à induction d'odeurs et de vapeurs nocives réduite, et système associé Ceased WO2020153769A2 (fr)

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KR1020190054083A KR102299697B1 (ko) 2019-05-09 2019-05-09 양극성 첨가제를 이용한 악취 및 유해물질이 저감된 아스팔트 제조 공정
KR10-2019-0054083 2019-05-09
KR10-2020-0003205 2020-01-09
KR1020200003205A KR102365337B1 (ko) 2020-01-09 2020-01-09 폐유 증류 잔사물을 이용한 악취 및 유해증기가 저감된 중질유분 제조 기술

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JPH05277337A (ja) * 1992-03-31 1993-10-26 Watanabegumi:Kk 再生アスファルト混合物プラント用の排気脱臭方法
JP2003342908A (ja) * 2002-05-27 2003-12-03 Nippon Hodo Co Ltd アスファルト混合物の臭気低減方法
KR20050047045A (ko) * 2005-04-07 2005-05-19 주식회사 과학기술분석센타 하이브리드식 실시간 제어형 악취 정화처리방법 및 그시스템
DE102005047889A1 (de) * 2005-10-06 2007-04-12 Air & D - Sarl Verfahren zum Reduzieren von übelriechenden Substanzen in Tankbehältern
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CN102294128A (zh) * 2010-06-24 2011-12-28 上海景凯环保科技有限公司 一种炼油停工吹扫气化学脱臭成套装置
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KR101699454B1 (ko) * 2015-07-15 2017-01-24 홍익대학교 산학협력단 공기 중의 유해물질을 분리하기 위한 분리 장치 및 분리된 유해물질을 감지하기 위한 센서 시스템
KR101796869B1 (ko) * 2016-07-20 2017-11-13 한국화학연구원 양극성 첨가제를 이용한 중질유 전환 방법
WO2017160017A1 (fr) * 2016-03-18 2017-09-21 한국화학연구원 Procédé de conversion d'huile lourde au moyen d'une dispersion à haute teneur en asphaltènes
CN105841168A (zh) * 2016-03-23 2016-08-10 江苏新世纪江南环保股份有限公司 一种炼化装置恶臭VOCs气体的一体化处理方法
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