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WO2022139094A1 - Système de désulfuration d'huile de mazout-c - Google Patents

Système de désulfuration d'huile de mazout-c Download PDF

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Publication number
WO2022139094A1
WO2022139094A1 PCT/KR2021/008487 KR2021008487W WO2022139094A1 WO 2022139094 A1 WO2022139094 A1 WO 2022139094A1 KR 2021008487 W KR2021008487 W KR 2021008487W WO 2022139094 A1 WO2022139094 A1 WO 2022139094A1
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Prior art keywords
oil
bunker
weight
parts
desulfurization catalyst
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PCT/KR2021/008487
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English (en)
Korean (ko)
Inventor
이철
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Lowcarbon Co Ltd
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Lowcarbon Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/04—Metals, or metals deposited on a carrier
    • 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
    • C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
    • C10G29/16—Metal oxides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/207—Acid gases, e.g. H2S, COS, SO2, HCN
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4006—Temperature
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/70—Catalyst aspects
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Definitions

  • the present invention relates to a bunker C oil desulfurization system, characterized in that the bunker C oil and the desulfurization catalyst are burned in a combustion furnace and the bunker C oil is desulfurized at the same time.
  • heavy oil compositions have been used for various purposes in various industrial fields, and according to JIS K2205, type 1 (heavy oil A), type 2 (heavy oil B), and type 3 (heavy oil C, bunker C oil) according to the kinematic viscosity classified into three types.
  • heavy oil A is generally used as fuel oil for heaters for house warming cultivation or heating equipment such as buildings
  • heavy oil B and heavy oil C are generally used as fuel for external combustion equipment such as boilers, large ships, power plants, etc. It is widely used as diesel engine equipment fuel, gas turbine equipment fuel, etc.
  • Heavy oil such as atmospheric distillation residue oil obtained by atmospheric distillation of crude oil contains a large amount of sulfur oxides and nitrates. When these heavy oils are used as fuel oils, SOx and NOx are generated. Therefore, it is necessary to set the sulfur oxides and nitrogen content in the heavy oil to a predetermined value or less due to environmental regulations or the like. By repeatedly performing hydrorefining of heavy oil, the content of sulfur oxides and nitroxides can be sufficiently reduced. However, when hydrorefining treatment is performed under conditions to sufficiently remove sulfur oxides and nitroxides, the catalyst life of the hydrorefining catalyst is short.
  • An object of the present invention is to provide a bunker C oil desulfurization system, characterized in that bunker C oil and a desulfurization catalyst are burned in a combustion furnace while simultaneously desulfurizing bunker C oil.
  • a first oil tank for supplying bunker C oil; a desulfurization catalyst tank for supplying a desulfurization catalyst; a combustion furnace to which the bunker C oil and a desulfurization catalyst are supplied, and the flame of a burner is ejected; an injection nozzle capable of directly injecting a desulfurization catalyst into a flame in the combustion furnace and controlling an injection distance; and a gas discharge unit from which the desulfurized exhaust gas is discharged, wherein the bunker C oil and the desulfurization catalyst are burned in the combustion furnace, and the bunker C oil is desulfurized at the same time.
  • a first oil tank for supplying bunker C oil; a desulfurization catalyst tank for supplying a desulfurization catalyst; a combustion furnace to which the bunker C oil and a desulfurization catalyst are supplied, and the flame of a burner is ejected; a piezoelectric element nozzle for injecting a desulfurization catalyst in an ultra-fine droplet state into the combustion furnace using a piezoelectric element; and a gas discharge unit from which the desulfurized exhaust gas is discharged, wherein the bunker C oil and the desulfurization catalyst are burned in the combustion furnace, and the bunker C oil is desulfurized at the same time.
  • the injection distance of the injection nozzle can be adjusted in the range of 300 to 450 mm.
  • the average droplet size is 1 to 100 ⁇ m when the desulfurization catalyst is directly sprayed into the flame.
  • the injection nozzle may include a main nozzle for injecting a desulfurization catalyst into the combustion furnace; an air inlet for injecting air in the direction of the main nozzle; three sub-nozzles which are inclined at a predetermined angle in the main nozzle and face each other; and a magnetic field generator mounted between the main nozzle and the sub-nozzle to generate a magnetic field.
  • the spray nozzle simultaneously sprays the desulfurization catalyst from the three sub-nozzles so that the sprayed desulfurization catalyst is crushed while colliding and then sprayed through the main nozzle.
  • the desulfurization catalyst in the ultrafine droplet state preferably has an average droplet size of 1 to 50 ⁇ m.
  • the average temperature of the flame is preferably in the range of 150 °C to 2,100 °C.
  • the desulfurization catalyst is, (a) SiO 2 , Al 2 O 3 , Fe 2 O 3 , TiO 2 , MgO, MnO, CaO, Na 2 O, K 2 O and P 2 O 3 As at least one oxide selected from the group consisting of; (b) at least one metal selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb; And, (c) sodium tetraborate (Na 2 B 4 O 7 ⁇ 10H 2 O), sodium hydroxide (NaOH), sodium silicate (Na 2 SiO 3 ) and hydrogen peroxide (H 2 O 2 ) One selected from the group consisting of The above liquid composition; is included.
  • the oxide is SiO 2 15 to 90 parts by weight, Al 2 O 3 15 to 100 parts by weight, Fe 2 O 3 10 to 50 parts by weight, TiO 2 5 to 15 parts by weight, MgO 20 to 150 parts by weight, MnO 10 to 20 parts by weight, CaO 20 to 200 parts by weight, Na 2 O 15 to 45 parts by weight, K 2 O 20 to 50 parts by weight, and P 2 O 3 5 to 20 parts by weight, wherein the metal is Li 0.0035 to 0.009 parts by weight, Cr 0.005 to 0.01 parts by weight, Co 0.001 to 0.005 parts by weight, Ni 0.006 to 0.015 parts by weight, Cu 0.018 to 0.03 parts by weight, Zn 0.035 to 0.05 0.04 to 0.08 parts by weight of Ga, 0.02 to 0.05 parts by weight of Sr, 0.002 to 0.01 parts by weight of Cd, and 0.003 to 0.005 parts by weight of Pb.
  • the metal is Li 0.0035 to 0.009 parts by weight, Cr 0.005 to 0.01 parts by
  • the size of the oxide and metal particles may be 1 to 2 ⁇ m, and the specific gravity may be 2.5 to 3.0.
  • the liquid composition comprises 20 to 130 parts by weight of sodium tetraborate (Na 2 B 4 O 7 ⁇ 10H 2 O), 15 to 120 parts by weight of sodium hydroxide (NaOH), and sodium silicate (Na 2 SiO 3 ) ) 50 to 250 parts by weight and hydrogen peroxide (H 2 O 2 ) 10 to 50 parts by weight.
  • sodium tetraborate Na 2 B 4 O 7 ⁇ 10H 2 O
  • NaOH sodium hydroxide
  • Na 2 SiO 3 sodium silicate
  • H 2 O 2 hydrogen peroxide
  • the oxide, the metal, and the liquid composition form a metal chelate compound.
  • the bunker C oil desulfurization system is capable of simultaneously burning bunker C oil and desulfurization catalyst by directly injecting a desulfurization catalyst into a flame in a combustion furnace, and simultaneously desulfurizing bunker C oil.
  • the bunker C oil desulfurization system directly injects the desulfurization catalyst to the flame at the point of the highest temperature in the combustion furnace using the injection nozzle, and at this time, the desulfurization rate can be increased by adjusting the injection distance between the flame and the injection nozzle.
  • the bunker C oil desulfurization system according to the present invention can prevent a large amount of sulfur oxides from being discharged into the atmosphere in advance by desulfurizing at the same time as combustion before sulfur oxides are generated in the combustion process of bunker C oil. It has the effect of greatly contributing to resolving the air pollution problem.
  • FIG. 1 shows a bunker C oil desulfurization system according to the present invention.
  • Figure 2 shows a perspective view of the injection nozzle of the bunker C oil desulfurization system according to the present invention.
  • Figure 3 shows a side view of the injection nozzle of the bunker C oil desulfurization system according to the present invention.
  • Figure 4 is a schematic diagram showing a bunker C oil desulfurization system including a piezoelectric element nozzle according to the present invention.
  • FIG. 5 shows a piezoelectric element nozzle according to the present invention.
  • FIG. 6 is a view showing the physical properties of bunker C oil used in an embodiment of the present invention, and is a result of analysis at the Petroleum Technology Research Institute of the Korea National Petroleum Administration.
  • LCLS desulfurization catalyst
  • FIG. 8 is a view showing a desulfurization catalyst (LCLS) injection nozzle position adjusting unit according to an embodiment of the present invention.
  • LCLS desulfurization catalyst
  • Figure 10 shows the change in SO 2 concentration according to the injection position of crude oil and desulfurization catalyst according to an embodiment of the present invention.
  • FIG 11 shows changes in the concentration of SO 2 according to the injection position of crude oil and desulfurization catalyst according to an embodiment of the present invention.
  • FIG 13 shows the change in the CO concentration according to the concentration conditions of the desulfurization catalyst according to the embodiment of the present invention.
  • the present invention is a first oil tank for supplying bunker C oil; a desulfurization catalyst tank for supplying a desulfurization catalyst; a combustion furnace to which the bunker C oil and a desulfurization catalyst are supplied, and the flame of a burner is ejected; an injection nozzle capable of directly injecting a desulfurization catalyst into a flame in the combustion furnace and controlling an injection distance; and a gas discharge unit from which desulfurized exhaust gas is discharged, wherein the bunker C oil and the desulfurization catalyst are burned in the combustion furnace and the bunker C oil desulfurization system is provided, characterized in that the bunker C oil is desulfurized at the same time. .
  • the bunker C oil desulfurization system is capable of simultaneously burning bunker C oil and desulfurization catalyst by directly injecting a desulfurization catalyst into a flame in a combustion furnace, and simultaneously desulfurizing bunker C oil.
  • the bunker C oil desulfurization system can improve the desulfurization efficiency because a large amount of sulfur oxides (SOx) contained in the bunker C oil is removed by contacting it with the flame in the combustion furnace and fine droplets of the desulfurization catalyst.
  • the sulfur (S)-containing material in the bunker C oil is the most present in the flame (hot point) at the position where the combustion of the bunker C oil occurs the most, and when the catalyst is injected into the hot point flame Since the particles of the catalyst are more finely broken and diffusion is easy, the probability of adsorption with the sulfur (S)-containing material can be improved, and as a result, the desulfurization efficiency can be improved.
  • the desulfurization catalyst composed of metal ions has a negative (-) charge property
  • the sulfur (S) element has a positive (+) charge property, so it can be desulfurized by adsorption by electrostatic attraction between cations and anions. .
  • FIG. 1 is a schematic diagram showing a bunker C oil desulfurization system including a spray nozzle according to the present invention.
  • the first oil tank 10 for supplying bunker C oil using the oil pump 14, and the desulfurization catalyst using the desulfurization catalyst pump 22 The desulfurization catalyst tank 20 to supply, the bunker C oil and the desulfurization catalyst are supplied, and connected to the burner 52 to eject the flame of the burner 52, the combustion furnace 50, the combustion furnace 50 furnace (
  • the desulfurization catalyst is directly injected into the flame in the furnace, and the injection nozzle 30 has an adjustable injection distance, and a gas discharge unit 60 through which the desulfurized exhaust gas is discharged.
  • the bunker C oil is supplied from the first oil tank 10 through the oil pump 12 to the combustion furnace 50, and the desulfurization catalyst is transferred from the desulfurization catalyst tank 20 through the desulfurization catalyst pump 22 to the injection nozzle. It is supplied to the combustion furnace 50 through (30). Combustion exhaust gas generated after combustion and desulfurization in the combustion furnace 50 may be discharged through the gas discharge unit 60 and supplied to an analysis device (not shown) for analyzing the exhaust gas.
  • the bunker C oil desulfurization system is characterized in that the bunker C oil is desulfurized at the same time as the bunker C oil and the desulfurization catalyst are burned in the furnace 50 in the furnace.
  • the spraying distance of the spray nozzle 30 may be adjustable in the range of 300 to 450 mm.
  • the injection distance means the distance between the flame and the injection nozzle 30 .
  • the injection distance of the injection nozzle 30 is 300 to 430 mm, 300 to 410 mm, 300 to 380 mm, 300 to 350 mm, 320 to 450 mm, 350 to 450 mm, 380 to 450 mm, 410 to 450 mm, 350 to 410 mm or 380 to 410 mm.
  • the bunker C oil desulfurization system directly injects a desulfurization catalyst to the flame in the combustion furnace 50 using the injection nozzle 30, and at this time, the temperature of the flame showing the highest efficiency is the highest by adjusting the distance between the flame and the injection nozzle.
  • the desulfurization rate can be increased by spraying the desulfurization catalyst at a high point.
  • the average temperature of the flame ejected from the burner 52 may be characterized in that the range of 150 to 2,100 °C.
  • the average temperature of the flame means an average value of the temperatures of several points from the flame to 450 mm, which is the maximum injection distance of the injection nozzle.
  • the average temperature of the flame may range from 150 to 1,800 °C, 150 to 1,500 °C, 150 to 1,000 °C, 500 to 2,100 °C, 500 to 1,500 °C, or 1,000 to 1,500 °C.
  • the desulfurization catalyst may have an average droplet size of 1 to 100 ⁇ m when directly sprayed into a flame.
  • the average droplet size is 1 to 80 ⁇ m, 1 to 60 ⁇ m, 1 to 40 ⁇ m, 1 to 20 ⁇ m, 10 to 100 ⁇ m, 20 to 100 ⁇ m, 40 to 100 ⁇ m, 60 to 100 ⁇ m, or 80 to 100 ⁇ m.
  • FIGS. 2 and 3 show a perspective view and a side view of the injection nozzle of the bunker C oil desulfurization system according to the present invention.
  • the air inlet 32 may be connected to a separate pipe and an air supply device to supply compressed air, and the desulfurization catalyst in the nozzle may be sprayed to the outside by the supplied compressed air.
  • the air inlet 32 may be connected to a spray nozzle position adjusting unit for adjusting the spray distance of the spray nozzle.
  • the spray nozzle 30 may further include an inverter 37 connected to the magnetic field generator 36 to adjust the magnetic field strength.
  • the magnetic field generating device 36 generates a magnetic field around it by allowing current to flow, and when the desulfurization catalyst is pushed in the direction of the long-term field generating device 36 by the compressed air supplied from the air inlet 32, it becomes a resistance. As a result, it is possible to improve the diffusivity of the desulfurization catalyst particles. By dispersing and spraying the desulfurization catalyst particles, it is possible to prevent clogging of the nozzle.
  • the magnetic field generating device 36 may not be limited as long as it allows current to flow.
  • the spray nozzle 30 simultaneously sprays the desulfurization catalyst from the three sub-nozzles 33, 34, 35 so that the sprayed desulfurization catalyst is crushed while colliding and then sprayed through the main nozzle 31. may be doing
  • the three sub-nozzles (33, 34, 35) may be arranged at the same distance on the same line, and the injection ports of the three sub-nozzles (33, 34, 35) to which the desulfurization catalyst is injected are directed toward the main nozzle (31). By being inclined so as to gather, when the desulfurization catalyst is sprayed, the desulfurization catalyst meets at a point in the center of the three sub-nozzles (33, 34, 35) injection hole, and the particles can be crushed.
  • the crushed desulfurization catalyst may be moved to the main nozzle by the air supplied from the air inlet 32 .
  • the three sub-nozzles 33 , 34 , and 35 may be disposed at an angle of 120° to each other.
  • the present invention is a first oil tank for supplying bunker C oil; a desulfurization catalyst tank for supplying a desulfurization catalyst; a combustion furnace to which the bunker C oil and a desulfurization catalyst are supplied, and the flame of a burner is ejected; a piezoelectric element nozzle for injecting a desulfurization catalyst in an ultra-fine droplet state into the combustion furnace using a piezoelectric element; and a gas discharge unit from which desulfurized exhaust gas is discharged, wherein the bunker C oil and the desulfurization catalyst are burned in the combustion furnace and the bunker C oil desulfurization system is provided, characterized in that the bunker C oil is desulfurized at the same time. .
  • the bunker C oil desulfurization system including a piezoelectric element nozzle except that it includes a piezoelectric element nozzle instead of an injection nozzle in the bunker C oil desulfurization system including the injection nozzle, the same action and effect are equally applied to the same configuration.
  • Figure 4 is a schematic diagram showing a bunker C oil desulfurization system including a piezoelectric element nozzle according to the present invention.
  • the bunker C oil desulfurization system of the present invention uses the first oil tank 10 for supplying bunker C oil using the oil pump 14, and the desulfurization catalyst using the desulfurization catalyst pump 22.
  • the desulfurization catalyst tank 20 to be supplied, the bunker C oil and the desulfurization catalyst are supplied, and the combustion furnace 50 in which the flame of the burner 52 is ejected is connected to the burner 52, and a piezoelectric element 42 is used. It includes a piezoelectric element nozzle 40 for injecting the desulfurization catalyst in the state of ultrafine droplets into the combustion furnace 50, and a gas discharge unit 60 from which the desulfurized exhaust gas is discharged.
  • the bunker C oil is supplied from the first oil tank 10 through the oil pump 12 to the combustion furnace 50, and the desulfurization catalyst is transferred from the desulfurization catalyst tank 20 to the desulfurization catalyst pump 22 through the piezoelectric element. It is supplied to the combustion furnace 50 through the nozzle (40). Combustion exhaust gas generated after combustion and desulfurization in the combustion furnace 50 may be discharged through the gas discharge unit 60 and supplied to an analysis device (not shown) for analyzing the exhaust gas.
  • FIG 5 shows the piezoelectric element nozzle 40 of the bunker C oil desulfurization system according to the present invention.
  • the piezoelectric element nozzle 40 is connected to the combustion furnace 50 and the venturi tube, and air is injected into one side of the venturi tube not connected to the combustion furnace 50. , pushes the desulfurization catalyst injected through the piezoelectric element nozzle 40 to be injected in the direction of the combustion furnace 50 .
  • the Venturi pipe means a pipe in which the thickness of the pipe is gradually narrowed and then slowly widened again. The phenomenon that occurs when a fluid is sucked into a narrow passage is called the Venturi effect. Accordingly, the desulfurization catalyst may be rapidly injected from the piezoelectric element nozzle 40 into the combustion furnace 50 by the air injected into the venturi tube and the venturi effect.
  • the particles of the desulfurization catalyst are broken down into ultra-fine droplets by driving the piezoelectric element 42 and injected into the combustion furnace 50, thereby desulfurization
  • the diffusion of the catalyst is easy and the surface area is improved, so that the probability of adsorption with the sulfur (S)-containing material in the combustion furnace 50 can be improved.
  • the desulfurization catalyst in the ultrafine droplet state may have an average droplet size of 1 to 50 ⁇ m.
  • the desulfurization catalyst in the ultrafine droplet state has an average droplet size of 1 to 40 ⁇ m, 1 to 30 ⁇ m, 1 to 20 ⁇ m, 1 to 10 ⁇ m, 10 to 20 ⁇ m, 10 to 50 ⁇ m, 20 to 50 ⁇ m, 30-50 ⁇ m, 40-50 ⁇ m or 5-15 ⁇ m.
  • the piezoelectric element nozzle 40 may include a micro-perforation 44 between the piezoelectric element 42 and the space into which the desulfurization catalyst is introduced, and the micro-perforation 44 is a perforation having a size smaller than that of the desulfurization catalyst particles. configured, the desulfurization catalyst may not pass through the micro-perforations 44 .
  • the micro-perforations 44 prevent the piezoelectric element 42 from being corroded by the desulfurization catalyst by preventing the piezoelectric element 42 from contacting the desulfurization catalyst while the desulfurization catalyst is finely sprayed by the piezoelectric element 42 . can do.
  • the average aperture size of the micro-perforations 44 may be 1 to 10 ⁇ m, for example, 1 to 8 ⁇ m, 1 to 6 ⁇ m, 1 to 5 ⁇ m, 1 to 4 ⁇ m, 1 to 2 ⁇ m, 2 to 10 ⁇ m, 4 to 10 ⁇ m, 5 to 10 ⁇ m, 6 to 10 ⁇ m or 8 to 10 ⁇ m.
  • the average temperature of the flame ejected from the burner 52 may be characterized in that the range of 150 to 2,100 °C.
  • the average temperature of the flame means an average value of the temperatures of several points from the flame to 450 mm, which is the maximum injection distance of the injection nozzle.
  • the average temperature of the flame may range from 150 to 1,800 °C, 150 to 1,500 °C, 150 to 1,000 °C, 500 to 2,100 °C, 500 to 1,500 °C, or 1,000 to 1,500 °C.
  • the desulfurization catalyst used in the bunker C oil desulfurization system including the injection nozzle or the piezoelectric element nozzle of the present invention is a catalyst capable of removing sulfur oxides generated during the combustion of bunker C oil, SiO 2 , Al 2 O 3 , Fe 2 O 3 , TiO 2 , MgO, MnO, CaO, Na 2 O, K 2 O and P 2 O 3 may include one or more oxides selected from the group consisting of, as in the following example SiO 2 , Al It is preferable to use all the oxides of 2 O 3 , Fe 2 O 3 , TiO 2 , MgO, MnO, CaO, Na 2 O, K 2 O and P 2 O 3 .
  • the oxide includes all of SiO 2 , Al 2 O 3 , Fe 2 O 3 , TiO 2 , MgO, MnO, CaO, Na 2 O, K 2 O and P 2 O 3
  • the basic chemical formula is K 0.8-0.9 (Al,Fe,Mg) 2 (Si,Al) 4 O 10 (OH) 2
  • illite is basically a single octahedral layer between two tetrahedral layers. It has a 2:1 bonding structure, and the octahedral layer is characterized by a dioctahedral structure in which only 2 of the 3 cation sites in the bonding structure are filled with cations. , this can adsorb sulfur oxides (SO x ) when the combustion product (C) mixed with the desulfurization catalyst is burned.
  • SO x sulfur oxides
  • Each oxide is SiO 2 in the desulfurization catalyst 15 to 90 parts by weight, Al 2 O 3 15 to 100 parts by weight, Fe 2 O 3 10 to 50 parts by weight, TiO 2 5 to 15 parts by weight, MgO 20 to 150 parts by weight, MnO 10 to 20 parts by weight, CaO 20 to 200 parts by weight, Na 2 O 15 to 45 parts by weight, K 2 O 20 to 50 parts by weight, and P 2 O 3 It may be included in 5 to 20 parts by weight.
  • the oxides are mixed and pulverized into fine particles having a particle size of 1 to 2 ⁇ m by a pulverizer before being formed with a desulfurization catalyst, and a specific gravity of 2.5 to 3.0 is used in the form of streaks and silvery white powder.
  • the desulfurization catalyst used in the present invention may include at least one metal selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb, and as , Cr, Co, Ni, Cu, Zn, Ga, Sr, it is preferable to use including all of the metal of Cd and Pb.
  • Each metal is 0.0035 to 0.009 parts by weight of Li, 0.005 to 0.01 parts by weight, Co 0.001 to 0.005 parts by weight, Ni 0.006 to 0.015 parts by weight, Cu 0.018 to 0.03 parts by weight, Zn 0.035 to 0.05 parts by weight, Ga 0.04 to the desulfurization catalyst. to 0.08 parts by weight, Sr 0.02 to 0.05 parts by weight, Cd 0.002 to 0.01 parts by weight, and Pb 0.003 to 0.005 parts by weight.
  • metals are also finely pulverized by a pulverizer to have a particle size of 1 to 2 ⁇ m, and a specific gravity of 2.5 to 3.0 is used in the form of streaks and silvery white powder.
  • the desulfurization catalyst used in the present invention is sodium tetraborate (Na 2 B 4 O 7 ⁇ 10H 2 O), sodium hydroxide (NaOH), sodium silicate (Na 2 SiO 3 ) and hydrogen peroxide (H 2 O 2 ) From the group consisting of It may include one or more selected liquid compositions, and it is preferable to use all of the liquid compositions of sodium tetraborate, sodium hydroxide, sodium silicate and hydrogen peroxide as in the following example.
  • the catalyst for deoxidation according to the present invention serves as a chelating agent while the above-described oxide and liquid composition are mixed and reacted to form a chelated metal chelate compound through coordination with the metal.
  • the liquid composition can be removed by adsorbing on ash generated when the combustion product (C) is burned and reacting with sulfur oxides present in the ash.
  • NaBO 2 is induced from Na 2 B 4 O 7 , which is sodium tetraborate, and through hydrogenation NaBH 4 is generated, and the generated NaBH 4 meets oxygen and sulfur oxide and reacts with sodium sulfate (Na 2 SO 4 ) to remove sulfur oxide, and the reaction process is shown in Schemes 1 and 2 below.
  • each liquid composition may include 20 to 130 parts by weight of sodium tetraborate, 15 to 120 parts by weight of sodium hydroxide, 50 to 250 parts by weight of sodium silicate, and 10 to 50 parts by weight of hydrogen peroxide to the desulfurization catalyst.
  • the desulfurization catalyst After mixing and reacting the desulfurization catalyst, it is allowed to stand for 24 to 72 hours for stabilization, and the desulfurization catalyst can be separated and used as a liquid composition.
  • the desulfurization catalyst used in the present invention When the desulfurization catalyst used in the present invention is mixed with the combustion product (C) in the temperature range of 400 to 2,100 ° C., the adsorption effect of sulfur oxides may be activated, but combustion in the temperature range of 600 to 1,500 ° C. is highly efficient can indicate
  • the bunker C oil desulfurization system according to the present invention can prevent a large amount of sulfur oxides from being discharged into the atmosphere in advance by desulfurizing at the same time as combustion before sulfur oxides are generated in the combustion process of bunker C oil. It has the effect of greatly contributing to resolving the air pollution problem.
  • the desulfurization catalyst was directly injected into the combustion flame of bunker C oil to measure the concentration change of SO 2 generated in the combustion process to confirm the SO 2 reduction effect of the desulfurization catalyst.
  • Metals Li 35g, Cr 50g, Co 10g, Ni 60g, Cu 180g, Zn 350g, Ga 400g, Sr 200g, Cd 20g, and Pb 30g were mixed and pulverized with a fine grinder to form a fine metal powder.
  • the fine oxide powder and the fine metal powder were repeatedly pulverized to have a particle size of 1 to 2 ⁇ m.
  • the liquid composition and the precipitated powder composition were separated, and the liquid composition from which the precipitated powder composition was separated was moved to a separate container to prepare a desulfurization catalyst in a liquid state.
  • bunker C oil used in this experiment The physical properties of bunker C oil used in this experiment are as shown in FIG.
  • the sulfur (S) component contained in bunker C oil is 1.21%, and the low calorific value is about 9,300 kcal/L.
  • the desulfurization catalyst for the desulfurization performance test the desulfurization catalyst prepared in Preparation Example was used.
  • the desulfurization catalyst was sprayed from the top of the flame through a pressure-type spray nozzle at the top of the flame, and the distance from the flame could be adjusted.
  • the combustion furnace (flame) temperature according to the injection and temperature measurement positions with the flame shown in FIG. 5 is shown in Table 1 below.
  • a set amount of the desulfurization catalyst was supplied to the nozzle through a metering pump.
  • 6 is an image showing the pipe for adjusting the injection position of the injection nozzle from the outside.
  • 7 shows the results of measuring the dial adjustment amount (%) of the metering pump, the injection amount and the injection distance from the nozzle used, using water.
  • the temperature measurement positions of each part of the combustion chamber are as shown in FIG. 5, and it was confirmed whether there was a temperature change by the desulfurization catalyst.
  • the flue gas analysis equipment used to analyze the desulfurization performance and the composition of the combustion flue gas of the bunker C oil combustion furnace is Germany's VarioPlus Ind. MRU Emission Monitoring System was used.
  • a predetermined amount (55 cc/min) of the desulfurization catalyst is sprayed while the nozzle position is adjusted to reduce the SO 2
  • the composition of the combustion exhaust gas was measured and analyzed while controlling the concentration of the desulfurization catalyst supplied. It was confirmed that the supply amount of crude oil supplied to the bunker C oil burner measured by an electromagnetic flowmeter at a pump pressure of 24 bar was in the range of 0.32 to 0.35 L/min.
  • FIG. 8 is a view showing changes in nozzle position while first burning only bunker C oil crude oil in section 1 to measure SO 2 concentration in combustion flue gas, and then spraying a solution diluted 1:1 with water and desulfurization catalyst (LCLS) after section 2
  • LCLS desulfurization catalyst
  • Table 2 shows the desulfurization catalyst supply conditions and nozzle position conditions for each measurement section
  • Table 3 shows the average concentration of SO 2 for each measurement section.
  • the measured concentration of SO 2 is a value converted to a reference oxygen concentration of 6%.
  • the average concentration of the desulfurization catalyst concentration conditions and measurement time for each measurement section of FIG. 9 and the SO 2 concentration in the combustion flue gas after the start of injection of the desulfurization catalyst for each concentration condition is calculated in the section where the concentration is stable, and the calculation time was indicated. That is, the average concentration in Table 5 is an average of the concentrations measured during the average calculation time shown in Table 4.
  • the portion in which the SO 2 concentration rises at the initial stage passing from section A to section B and from section B to section C is the temporary desulfurization catalyst generated in the process of replacing the desulfurization catalyst container supplied to the metering pump. This is a phenomenon caused by a supply cut.
  • Table 5 shows the average concentration (standard oxygen concentration of 6%) of the combustion exhaust gas component according to the change in the concentration of the desulfurization catalyst (LCLS) sprayed to the bunker C oil burner flame.
  • LCLS desulfurization catalyst
  • Table 5 shows the average concentration (standard oxygen concentration of 6%) of the combustion exhaust gas component according to the change in the concentration of the desulfurization catalyst (LCLS) sprayed to the bunker C oil burner flame.
  • SO 2 dilution ratio of the desulfurization catalyst
  • CO it can be seen that combustion is well performed with little effect on the change in the concentration of the desulfurization catalyst, and in the case of O 2 , it is somewhat lowered as the concentration of the desulfurization catalyst increases.
  • NOx it slightly increases with the increase in the concentration of the desulfurization catalyst, but it seems to be due to the effect of temperature change, and it is judged that the result is not significantly significant.
  • Table 6 summarizes the average concentration and reduction rate of SO 2 in each desulfurization catalyst supply concentration condition with respect to the concentration of SO 2 measured during the combustion of bunker C crude oil.
  • the reduction rate of SO 2 was 52.2%
  • the reduction rate of SO 2 was 73.3%
  • the desulfurization catalyst: water In the case of 3:1, the reduction rate of SO 2 was estimated to be 82.8%.
  • the present invention can be widely used in bunker C oil desulfurization systems.

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Abstract

La présente invention concerne un système de désulfuration d'huile de mazout-C, comprenant : un premier réservoir d'huile qui fournit de l'huile de mazout-C ; un réservoir de catalyseur de désulfuration qui fournit un catalyseur de désulfuration ; un four de combustion auquel l'huile de mazout-C et le catalyseur de désulfuration sont fournis, et la flamme d'un brûleur est éjectée ; une buse de pulvérisation qui pulvérise directement le catalyseur de désulfuration sur la flamme dans le four de combustion, et permet de régler une distance d'injection ; et une unité de décharge de gaz à travers laquelle le gaz d'échappement désulfuré est déchargé, l'huile de mazout-C étant désulfurée pendant qu'elle est brûlée dans le four de combustion avec le catalyseur de désulfuration
PCT/KR2021/008487 2020-12-23 2021-07-05 Système de désulfuration d'huile de mazout-c Ceased WO2022139094A1 (fr)

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KR20030006429A (ko) * 2001-07-12 2003-01-23 박현 과산화수소수 및 산화칼슘용액을 이용한 질소산화물 및황산화물의 저감방법
KR20100064351A (ko) * 2008-12-04 2010-06-14 주식회사 유니코정밀화학 소결 배가스 중의 황산화물 제거용 조성물
WO2012064084A2 (fr) * 2010-11-08 2012-05-18 Oh Mi Hye Composition de catalyseur de combustion liquide incluant un composé ionique complexe métallique mixte
KR101836047B1 (ko) * 2017-09-18 2018-03-08 이철 탈황용 촉매를 이용한 탈황 시스템
KR102264355B1 (ko) * 2020-12-23 2021-06-14 (주)로우카본 벙커c유 탈황 시스템

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JPH05117665A (ja) 1991-10-28 1993-05-14 Idemitsu Kosan Co Ltd 重質炭化水素油の接触水素化処理方法

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KR20030006429A (ko) * 2001-07-12 2003-01-23 박현 과산화수소수 및 산화칼슘용액을 이용한 질소산화물 및황산화물의 저감방법
KR20100064351A (ko) * 2008-12-04 2010-06-14 주식회사 유니코정밀화학 소결 배가스 중의 황산화물 제거용 조성물
WO2012064084A2 (fr) * 2010-11-08 2012-05-18 Oh Mi Hye Composition de catalyseur de combustion liquide incluant un composé ionique complexe métallique mixte
KR101836047B1 (ko) * 2017-09-18 2018-03-08 이철 탈황용 촉매를 이용한 탈황 시스템
KR102264355B1 (ko) * 2020-12-23 2021-06-14 (주)로우카본 벙커c유 탈황 시스템

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