WO2022139094A1 - Bunker-c oil desulfurization system - Google Patents

Bunker-c oil desulfurization system Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
oil
bunker
weight
parts
desulfurization catalyst
Prior art date
Application number
PCT/KR2021/008487
Other languages
French (fr)
Korean (ko)
Inventor
이철
Original Assignee
(주)로우카본
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by (주)로우카본 filed Critical (주)로우카본
Publication of WO2022139094A1 publication Critical patent/WO2022139094A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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.

Abstract

The present invention relates to a bunker-C oil desulfurization system, comprising: a first oil tank which supplies bunker-C oil; a desulfurization catalyst tank which supplies a desulfurization catalyst; a combustion furnace to which the bunker-C oil and the desulfurization catalyst are supplied, and the flame of a burner is ejected; a spray nozzle which directly sprays the desulfurization catalyst onto the flame in the combustion furnace, and can adjust an injection distance; and a gas discharge unit through which desulfurized exhaust gas is discharged, wherein the bunker-C oil is desulfurized while the bunker-C oil and the desulfurization catalyst are burned in the combustion furnace.

Description

벙커C유 탈황 시스템Bunker C Oil Desulfurization System
본 발명은 연소로 로(furnace) 내에서 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 하는 벙커C유 탈황 시스템에 관한 것이다.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.
종래부터, 중유 조성물은 각종 산업분야에 있어서 여러 가지의 용도에 사용되고 있고, JIS K2205에 있어서 동점도에 따라 1종(A중유), 2종(B중유) 및 3종(C중유, 벙커C유)의 3 종류로 분류되어 있다. 이들의 중유 조성물 가운데, A중유는 일반적으로 하우스 가온 재배용 난방기나 빌딩 등의 난방기용의 연료유로서 이용되고, B중유 및 C중유는 일반적으로 보일러 등의 외연 기기 연료, 대형선박이나 발전용 등의 디젤 엔진 기기 연료, 가스 터빈 기기 연료 등으로 해서 넓게 이용되고 있다. Conventionally, 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. Among these heavy oil compositions, heavy oil A is generally used as fuel oil for heaters for house warming cultivation or heating equipment such as buildings, and 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.
원유의 상압 증류에 의해서 얻어지는 상압 증류 찌꺼기유 등의 중질유는 황산화물이나 질산화물을 다량으로 포함하고 있다. 이들의 중질유를 연료유로서 사용하는 경우, SOx나 NOx가 발생하므로, 환경상의 규제 등에 의해 중질유 중의 황산화물이나 질소분의 함유량을 정해진 값 이하로 하는 것이 필요하다. 중질유의 수소화 정제를 반복하고 실시함으로써, 황산화물이나 질산화물의 함유량을 충분히 내릴 수도 있지만, 황산화물이나 질산화물을 충분히 제거할 수 있는 조건으로 수소화 정제 처리를 실시한 경우, 수소화 정제 처리 촉매의 촉매 수명이 짧은 등의 문제가 있었다. 또한 수소화 정제의 반응 온도를 고온으로 하여 황과 질소 성분의 제거를 촉진하는 것도 시도되고 있지만, 부반응으로 탄화수소가 축합하여 건조 슬러지가 발생하고 제품의 품질이 저하되거나 촉매에 코크가 퇴적되어 촉매의 활성이 상실되는 문제가 있었다.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. There were problems such as In addition, attempts have been made to promote the removal of sulfur and nitrogen components by raising the reaction temperature of hydrorefining to a high temperature, but as a side reaction, hydrocarbons condense to generate dry sludge, and the quality of the product decreases or coke is deposited on the catalyst to activate the catalyst. There was a problem with this being lost.
이러한 문제를 해결하기 위한 방법으로서 수소 공여성 화합물을 이용하여 중질유 중의 코크 전구체를 수소화하는 방법이 보고되어 있으나(일본공개특허 제1993-117665호), 수소 공여성 용제를 중질유로 혼합하여 고온으로 수소화 처리를 실시하고 있기 때문에, 어느 정도 코크의 생성 억제 효과를 볼 수 있지만, 그 효과는 불충분한 문제가 있다.As a method for solving this problem, a method of hydrogenating a coke precursor in heavy oil using a hydrogen-donating compound has been reported (Japanese Patent Laid-Open No. 1993-117665), but a hydrogen-donating solvent is mixed with heavy oil and hydrogenated at high temperature. Since the treatment is performed, the effect of suppressing the formation of coke can be seen to some extent, but there is a problem that the effect is insufficient.
본 발명은 연소로 로(furnace) 내에서 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 하는 벙커C유 탈황 시스템을 제공하고자 한다.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.
상기와 같은 목적을 달성하기 위한 본 발명은 일 실시예에 따라, 벙커C유를 공급하는 제1 오일탱크; 탈황촉매를 공급하는 탈황촉매탱크; 상기 벙커C유 및 탈황촉매가 공급되고, 버너의 화염이 분출되는 연소로; 상기 연소로 로(furnace) 내의 화염에 탈황촉매를 직접 분사하며, 분사거리의 조절이 가능한 분사 노즐; 및, 탈황된 배기가스가 배출되는 가스 배출부를 포함하고, 상기 연소로 로 내에서 상기 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 한다.According to an embodiment of the present invention for achieving the above object, 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.
또한 일 실시예에 따라, 벙커C유를 공급하는 제1 오일탱크; 탈황촉매를 공급하는 탈황촉매탱크; 상기 벙커C유 및 탈황촉매가 공급되고, 버너의 화염이 분출되는 연소로; 압전소자를 이용하여 초미세 액적 상태의 탈황촉매를 상기 연소로 로(furnace) 내로 분사하는 압전소자노즐; 및, 탈황된 배기가스가 배출되는 가스 배출부를 포함하고, 상기 연소로 로 내에서 상기 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 한다.In addition, according to an embodiment, 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.
또한 일 실시예에 따라, 상기 분사 노즐의 분사거리는 300 내지 450 mm 범위에서 조절이 가능하다.In addition, according to an embodiment, the injection distance of the injection nozzle can be adjusted in the range of 300 to 450 mm.
또한 일 실시예에 따라, 상기 탈황촉매는 화염에 직접 분사 시 평균 액적 크기가 1 내지 100 ㎛인 것이 좋다.In addition, according to an embodiment, it is preferable that the average droplet size is 1 to 100 μm when the desulfurization catalyst is directly sprayed into the flame.
또한 일 실시예에 따라, 상기 분사 노즐은, 상기 연소로 로 내로 탈황촉매를 분사하는 메인노즐; 상기 메인노즐 방향으로 공기를 주입하는 공기 투입구; 상기 메인노즐 내에 소정 각도로 경사지게 위치하며 서로 마주보는 세 개의 서브노즐; 및, 상기 메인노즐과 상기 서브노즐 사이에 장착되어 자기장을 발생시키는 자기장 발생장치를 포함한다.In addition, according to an embodiment, 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.
또한 일 실시예에 따라, 상기 분사 노즐은 상기 세 개의 서브노즐에서 동시에 탈황촉매를 분사하여 분사된 탈황촉매가 부딪치면서 잘게 부숴진 뒤 상기 메인노즐을 통해 분사되도록 한다.In addition, according to an embodiment, 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.
또한 일 실시예에 따라, 상기 초미세 액적 상태의 탈황촉매는 평균 액적 크기가 1 내지 50 ㎛인 것이 좋다.In addition, according to an embodiment, the desulfurization catalyst in the ultrafine droplet state preferably has an average droplet size of 1 to 50 μm.
또한 일 실시예에 따라, 상기 화염의 평균 온도는 150℃ 내지 2,100℃ 범위인 것이 좋다.In addition, according to one embodiment, the average temperature of the flame is preferably in the range of 150 ℃ to 2,100 ℃.
또한 일 실시예에 따라, 상기 탈황촉매는, (a) SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O 및 P2O3로 이루어진 군으로부터 선택된 1종 이상의 산화물; (b) Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd 및 Pb로 이루어진 군으로부터 선택된 1종 이상의 금속; 및, (c) 사붕산나트륨(Na2B4O7·10H2O), 수산화나트륨(NaOH), 규산나트륨(Na2SiO3) 및 과산화수소(H2O2)로 이루어진 군으로부터 선택된 1종 이상의 액상 조성물;이 포함된다.In addition, according to an embodiment, 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.
또한 일 실시예에 따라, 상기 산화물은 SiO2 15 내지 90 중량부, Al2O3 15 내지 100 중량부, Fe2O3 10 내지 50 중량부, TiO2 5 내지 15 중량부, MgO 20 내지 150 중량부, MnO 10 내지 20 중량부, CaO 20 내지 200 중량부, Na2O 15 내지 45 중량부, K2O 20 내지 50 중량부 및 P2O3 5 내지 20 중량부로 포함되며, 상기 금속은 Li 0.0035 내지 0.009 중량부, Cr 0.005 내지 0.01 중량부, Co 0.001 내지 0.005 중량부, Ni 0.006 내지 0.015 중량부, Cu 0.018 내지 0.03 중량부, Zn 0.035 내지 0.05 중량부, Ga 0.04 내지 0.08 중량부, Sr 0.02 내지 0.05 중량부, Cd 0.002 내지 0.01 중량부 및 Pb 0.003 내지 0.005 중량부로 포함된다.In addition, according to an embodiment, 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.
또한 일 실시예에 따라, 상기 산화물 및 금속 입자의 크기는 1 내지 2 ㎛이고, 비중은 2.5 내지 3.0인 것이 좋다.In addition, according to an embodiment, the size of the oxide and metal particles may be 1 to 2 μm, and the specific gravity may be 2.5 to 3.0.
또한 일 실시예에 따라, 상기 액상 조성물은 사붕산나트륨(Na2B4O7·10H2O) 20 내지 130 중량부, 수산화나트륨(NaOH) 15 내지 120 중량부, 규산나트륨(Na2SiO3) 50 내지 250 중량부 및 과산화수소(H2O2) 10 내지 50 중량부로 포함된다.In addition, according to an embodiment, 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.
또한 일 실시예에 따라, 상기 탈황촉매는 상기 산화물, 금속 및 액상 조성물이 금속 킬레이트 화합물을 형성한다.In addition, according to an embodiment, in the desulfurization catalyst, the oxide, the metal, and the liquid composition form a metal chelate compound.
본 발명에 따른 벙커C유 탈황 시스템은 연소로의 내의 화염에 탈황촉매를 직접 분사하여 벙커C유 및 탈황촉매를 함께 연소시키는 동시에 벙커C유의 탈황이 가능하다. 특히, 상기 벙커C유 탈황 시스템은 분사 노즐을 이용하여 연소로 내의 온도가 가장 높은 지점의 화염에 탈황촉매를 직접 분사하고, 이때 화염과 분사 노즐의 분사거리를 조절함으로써 탈황율을 높일 수 있다. The bunker C oil desulfurization system according to the present invention 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. In particular, 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.
또한, 본 발명에 따른 벙커C유 탈황 시스템은 벙커C유의 연소 과정에서 황산화물이 생성되기 전에 연소와 동시에 탈황시킴으로써 다량의 황산화물이 대기 중으로 배출되는 것을 미연에 방지할 수 있기 때문에 황산화물로 인한 대기오염 문제 해소에 크게 기여할 수 있는 효과가 있다.In addition, 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.
도 1은 본 발명에 따른 벙커C유 탈황 시스템을 나타낸 것이다.1 shows a bunker C oil desulfurization system according to the present invention.
도 2는 본 발명에 따른 벙커C유 탈황 시스템의 분사 노즐의 사시도를 나타낸 것이다.Figure 2 shows a perspective view of the injection nozzle of the bunker C oil desulfurization system according to the present invention.
도 3은 본 발명에 따른 벙커C유 탈황 시스템의 분사 노즐의 측면도를 나타낸 것이다.Figure 3 shows a side view of the injection nozzle of the bunker C oil desulfurization system according to the present invention.
도 4는 본 발명에 따른 압전소자노즐을 포함하는 벙커C유 탈황 시스템을 나타낸 개략도이다.Figure 4 is a schematic diagram showing a bunker C oil desulfurization system including a piezoelectric element nozzle according to the present invention.
도 5는 본 발명에 따른 압전소자노즐을 나타낸 것이다.5 shows a piezoelectric element nozzle according to the present invention.
도 6은 본 발명의 실시예에서 사용된 벙커C유의 물성을 나타낸 것으로, 한국석유관리원의 석유기술연구소에서 분석한 결과이다.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.
도 7은 본 발명의 실시예에 따른 탈황촉매(LCLS) 분사 및 온도 측정 위치를 나타낸 것이다.7 is a view showing the injection and temperature measurement positions of the desulfurization catalyst (LCLS) according to an embodiment of the present invention.
도 8은 본 발명의 실시예에 따른 탈황촉매(LCLS) 분사 노즐 위치 조절부를 나타낸 것이다.8 is a view showing a desulfurization catalyst (LCLS) injection nozzle position adjusting unit according to an embodiment of the present invention.
도 9는 본 발명의 실시예에 따른 정량펌프와 노즐에서의 분사량 및 분사거리 관계를 나타낸 것이다.9 shows the relationship between the injection amount and the injection distance in the metering pump and the nozzle according to the embodiment of the present invention.
도 10은 본 발명의 실시예에 따른 원유 및 탈황촉매 분사위치에 따른 SO2 농도 변화를 나타낸 것이다.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.
도 11은 본 발명의 실시예에 따른 원유 및 탈황촉매 분사위치에 따른 SO2 농도 변화를 나타낸 것이다.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.
도 12는 본 발명의 실시예에 따른 탈황촉매 농도 조건에 따른 SO2 농도 변화를 나타낸 것이다.12 shows changes in SO 2 concentration according to the concentration conditions of the desulfurization catalyst according to an embodiment of the present invention.
도 13은 본 발명의 실시예에 따른 탈황촉매 농도 조건에 따른 CO 농도 변화를 나타낸 것이다.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.
도 14는 본 발명의 실시예에 따른 탈황촉매 농도 조건에 따른 NOx 농도 변화를 나타낸 것이다.14 is a graph showing the NOx concentration change according to the desulfurization catalyst concentration conditions according to an embodiment of the present invention.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 실시예를 가질 수 있는 바, 특정 실시예들을 도면에 예시하고 상세한 설명에 구체적으로 설명하고자 한다.Since the present invention can have various changes and can have various embodiments, specific embodiments are illustrated in the drawings and will be described in detail in the detailed description.
그러나, 이는 본 발명을 특정한 실시 형태에 대해 한정하려는 것이 아니며, 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다. However, this is not intended to limit the present invention to specific embodiments, and it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention.
본 발명에서, "포함한다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.In the present invention, terms such as "comprises" or "have" are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.
이하, 본 발명에 대하여 구체적으로 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명은 벙커C유를 공급하는 제1 오일탱크; 탈황촉매를 공급하는 탈황촉매탱크; 상기 벙커C유 및 탈황촉매가 공급되고, 버너의 화염이 분출되는 연소로; 상기 연소로 로(furnace) 내의 화염에 탈황촉매를 직접 분사하며, 분사거리의 조절이 가능한 분사 노즐; 및, 탈황된 배기가스가 배출되는 가스 배출부를 포함하고, 상기 연소로 로 내에서 상기 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 하는 벙커C유 탈황 시스템을 제공한다.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. .
본 발명에 따른 벙커C유 탈황 시스템은 연소로의 내의 화염에 탈황촉매를 직접 분사하여 벙커C유 및 탈황촉매를 함께 연소시키는 동시에 벙커C유의 탈황이 가능하다. 또한, 상기 벙커C유 탈황 시스템은 벙커C유에 포함된 다량의 황산화물(SOx)을 연소로 로 내의 화염과 탈황촉매의 미세 액적과 접촉시켜 제거하기 때문에 탈황 효율을 향상시킬 수 있다.The bunker C oil desulfurization system according to the present invention 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. In addition, 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.
구체적으로, 상기 벙커C유의 연소가 가장 잘 일어나는, 온도가 가장 높은 위치의 화염(핫포인트)에서 벙커C유 내의 황(S) 함유 물질이 가장 많이 존재하고, 핫포인트인 화염에 촉매를 분사하면 촉매의 입자가 더 잘게 부서져 확산이 용이하여 상기 황(S) 함유 물질과 흡착할 확률을 향상시킬 수 있으며, 결과적으로 탈황 효율을 향상시킬 수 있다. 이때의 반응은 금속 이온으로 구성된 탈황촉매는 음(-)전하 성질을 띄고, 황(S) 원소는 양(+)전하 성질을 띄므로 양이온과 음이온의 정전기적 인력에 의해 흡착함으로써 탈황될 수 있다.Specifically, 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. In this reaction, the desulfurization catalyst composed of metal ions has a negative (-) charge property, and the sulfur (S) element has a positive (+) charge property, so it can be desulfurized by adsorption by electrostatic attraction between cations and anions. .
이하에서는 본 발명의 실시예를 도시한 도면들을 참조하여 본 발명에 따른 벙커C유 탈황 시스템에 관하여 보다 상세히 설명하고자 한다.Hereinafter, with reference to the drawings showing an embodiment of the present invention will be described in more detail with respect to the bunker C oil desulfurization system according to the present invention.
도 1은 본 발명에 따른 분사 노즐을 포함하는 벙커C유 탈황 시스템을 나타낸 개략도이다.1 is a schematic diagram showing a bunker C oil desulfurization system including a spray nozzle according to the present invention.
도 1에 나타낸 바와 같이, 본 발명의 벙커C유 탈황 시스템은 오일펌프(14)를 이용하여 벙커C유를 공급하는 제1 오일탱크(10), 탈황촉매펌프(22)를 이용하여 탈황촉매를 공급하는 탈황촉매탱크(20), 상기 벙커C유 및 탈황촉매가 공급되고, 버너(52)와 연결되어 버너(52)의 화염이 분출되는 연소로(50), 상기 연소로(50) 로(furnace) 내의 화염에 탈황촉매를 직접 분사하며, 분사거리의 조절이 가능한 분사 노즐(30), 및 탈황된 배기가스가 배출되는 가스 배출부(60)을 포함한다. 상기 벙커C유는 제1 오일탱크(10)에서 오일펌프(12)를 거쳐 연소로(50)로 공급되고, 상기 탈황촉매는 탈황촉매탱크(20)에서 탈황촉매펌프(22)를 거쳐 분사 노즐(30)을 통해 연소로(50)로 공급된다. 상기 연소로(50)에서 연소 및 탈황된 후 발생하는 연소배가스는 가스 배출부(60)을 통해 배출되어 배출가스를 분석하는 분석장비(미도시)로 공급될 수 있다.1, in the bunker C oil desulfurization system of 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.
상기 벙커C유 탈황 시스템은 상기 연소로(50) 로(furnace) 내에서 상기 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 한다.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.
상기 분사 노즐(30)의 분사거리는 300 내지 450 mm 범위에서 조절이 가능한 것을 특징으로 하는 것일 수 있다. 상기 분사거리는 상기 화염과 분사 노즐(30)의 거리를 의미한다. 예를 들어, 상기 분사 노즐(30)의 분사거리는 300 내지 430 mm, 300 내지 410 mm, 300 내지 380 mm, 300 내지 350 mm, 320 내지 450 mm, 350 내지 450 mm, 380 내지 450 mm, 410 내지 450 mm, 350 내지 410 mm 또는 380 내지 410 mm 범위일 수 있다. 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 . For example, 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.
상기 벙커C유 탈황 시스템은 분사 노즐(30)을 이용하여 연소로(50) 내의 화염에 탈황촉매를 직접 분사하고, 이때 화염과 분사 노즐의 거리를 조절함으로써 가장 높은 효율을 나타내는 화염의 온도가 가장 높은 지점에 탈황촉매를 분사하여 탈황율을 높일 수 있다. 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.
상기 버너(52)에서 분출되는 화염의 평균 온도는 150 내지 2,100℃ 범위인 것을 특징으로 하는 것일 수 있다. 상기 화염의 평균 온도는 화염에서부터 상기 분사 노즐의 최대 분사거리인 450 mm까지 여러 지점의 온도의 평균값을 의미한다. 예를 들어, 상기 화염의 평균 온도는 150 내지 1,800℃, 150 내지 1,500℃, 150 내지 1,000℃, 500 내지 2,100℃, 500 내지 1,500℃ 또는 1,000 내지 1,500℃ 범위일 수 있다.The average temperature of the flame ejected from the burner 52 may be characterized in that the range of 150 to 2,100 ℃. 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. For example, 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.
상기 탈황촉매는 화염에 직접 분사 시 평균 액적 크기가 1 내지 100 ㎛인 것을 특징으로 하는 것일 수 있다. 예를 들어, 상기 평균 액적 크기가 1 내지 80 ㎛, 1 내지 60 ㎛, 1 내지 40 ㎛, 1 내지 20 ㎛, 10 내지 100 ㎛, 20 내지 100 ㎛, 40 내지 100 ㎛, 60 내지 100 ㎛ 또는 80 내지 100 ㎛ 범위일 수 있다. The desulfurization catalyst may have an average droplet size of 1 to 100 μm when directly sprayed into a flame. For example, the average droplet size is 1 to 80 μm, 1 to 60 μm, 1 to 40 μm, 1 to 20 μm, 10 to 100 μm, 20 to 100 μm, 40 to 100 μm, 60 to 100 μm, or 80 to 100 μm.
상기 화염의 온도가 낮은 지점에서는 벙커C유와 탈황촉매의 반응이 쉽게 되도록 표면적이 넓은 작은 액적 크기가 용이하고, 상기 화염의 온도가 높은 지점에서는 상대적으로 액적 크기가 더 커도 벙커C유와 탈황촉매의 반응이 용이할 수 있다.At a point where the flame temperature is low, it is easy to have a small droplet size with a large surface area so that the reaction between the bunker C oil and the desulfurization catalyst is easy, and at a point where the flame temperature is high, even if the droplet size is relatively larger, reaction may be easy.
도 2 및 도 3은 본 발명에 따른 벙커C유 탈황 시스템의 분사 노즐의 사시도 및 측면도를 나타낸 것이다.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.
도 2 및 3을 참조하면, 상기 분사 노즐(30)은, 상기 연소로(50) 로 내로 탈황촉매를 분사하는 메인노즐(31); 상기 메인노즐(31)과 마주보는 위치에서 상기 메인노즐(31) 방향으로 공기를 주입하는 공기 투입구(32); 상기 메인노즐(31) 내에 소정 각도로 경사지게 위치하며 서로 마주보는 세 개의 서브노즐인 제1 서브노즐(33) 제2 서브노즐(34) 및 제3 서브노즐(35); 및, 상기 메인노즐(31)과 상기 서브노즐들(33, 34, 35) 사이에 장착되어 자기장을 발생시키는 자기장 발생장치(36)를 포함할 수 있다. 2 and 3, the injection nozzle 30, the main nozzle 31 for injecting the desulfurization catalyst into the combustion furnace 50; an air inlet (32) for injecting air in the direction of the main nozzle (31) at a position facing the main nozzle (31); a first sub-nozzle 33, a second sub-nozzle 34, and a third sub-nozzle 35, which are three sub-nozzles that are inclined at a predetermined angle in the main nozzle 31 and face each other; and a magnetic field generator 36 mounted between the main nozzle 31 and the sub-nozzles 33 , 34 , and 35 to generate a magnetic field.
상기 공기 투입구(32)는 별도의 배관 및 공기 공급장치가 연결되어 압축공기를 공급하는 것일 수 있고, 공급되는 압축공기에 의해 노즐 내의 탈황촉매가 외부로 분사될 수 있다. 또한, 상기 공기 투입구(32)는 분사 노즐의 분사거리를 조절하는 분사 노즐 위치 조절부가 연결될 수 있다. 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. In addition, the air inlet 32 may be connected to a spray nozzle position adjusting unit for adjusting the spray distance of the spray nozzle.
상기 분사 노즐(30)은 자기장 발생장치(36)와 연결되어 자기장 세기를 조절하는 인버터(37)를 추가 포함할 수 있다.The spray nozzle 30 may further include an inverter 37 connected to the magnetic field generator 36 to adjust the magnetic field strength.
상기 자기장 발생장치(36)는 전류를 흐르도록 하여 주위에 자기장을 발생시키고, 상기 공기 투입구(32)에서 공급되는 압축공기에 의해 탈황촉매를 장기장 발생장치(36) 방향으로 밀어줄 경우 저항으로 인해 떨어짐으로써 탈황촉매 입자의 확산성을 향상시킬 수 있다. 상기 탈황촉매 입자를 확산시켜 분사함으로써 노즐이 막히는 것을 방지할 수 있다. 상기 자기장 발생장치(36)는 전류를 흐르도록 하는 것이라면 제한되지 않을 수 있다. 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.
상기 분사 노즐(30)은 상기 세 개의 서브노즐(33, 34, 35)에서 동시에 탈황촉매를 분사하여 분사된 탈황촉매가 부딪치면서 잘게 부숴진 뒤 상기 메인노즐(31)을 통해 분사되도록 하는 것을 특징으로 하는 것일 수 있다. 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
상기 세 개의 서브노즐(33, 34, 35)은 동일 선상에서 동일한 간격으로 배치될 수 있으며, 탈황촉매가 분사되는 세 개의 서브노즐(33, 34, 35)의 분사구는 메인노즐(31)을 향해서 모이도록 경사지게 위치함으로써, 탈황촉매가 분사될 경우, 상기 탈황촉매가 세 개의 서브노즐(33, 34, 35) 분사구 중앙의 한 점에서 만나 입자가 잘게 부숴질 수 있다. 잘게 부숴진 탈황촉매는 공기 투입구(32)에서 공급하는 공기에 의해 메인노즐로 이동될 수 있다. 예를 들어, 상기 세 개의 서브노즐(33, 34, 35)은 서로 120°의 각도를 이루며 배치될 수 있다. 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 . For example, the three sub-nozzles 33 , 34 , and 35 may be disposed at an angle of 120° to each other.
또한, 본 발명은 벙커C유를 공급하는 제1 오일탱크; 탈황촉매를 공급하는 탈황촉매탱크; 상기 벙커C유 및 탈황촉매가 공급되고, 버너의 화염이 분출되는 연소로; 압전소자를 이용하여 초미세 액적 상태의 탈황촉매를 상기 연소로 로(furnace) 내로 분사하는 압전소자노즐; 및, 탈황된 배기가스가 배출되는 가스 배출부를 포함하고, 상기 연소로 로 내에서 상기 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 하는 벙커C유 탈황 시스템을 제공한다.In addition, 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. .
압전소자노즐을 포함하는 벙커C유 탈황 시스템은, 상기 분사 노즐을 포함하는 벙커C유 탈황 시스템에서 분사 노즐 대신 압전소자노즐을 포함하는 것을 제외하고는 동일한 구성에 대해서는 동일한 작용 및 효과가 동일하게 적용될 수 있다. 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. can
도 4는 본 발명에 따른 압전소자노즐을 포함하는 벙커C유 탈황 시스템을 나타낸 개략도이다.Figure 4 is a schematic diagram showing a bunker C oil desulfurization system including a piezoelectric element nozzle according to the present invention.
도 4에 나타낸 바와 같이, 본 발명의 벙커C유 탈황 시스템은 오일펌프(14)를 이용하여 벙커C유를 공급하는 제1 오일탱크(10), 탈황촉매펌프(22)를 이용하여 탈황촉매를 공급하는 탈황촉매탱크(20), 상기 벙커C유 및 탈황촉매가 공급되고, 버너(52)와 연결되어 버너(52)의 화염이 분출되는 연소로(50), 압전소자(42)를 이용하여 초미세 액적 상태의 탈황촉매를 상기 연소로(50) 로 내로 분사하는 압전소자노즐(40), 및 탈황된 배기가스가 배출되는 가스 배출부(60)을 포함한다. 상기 벙커C유는 제1 오일탱크(10)에서 오일펌프(12)를 거쳐 연소로(50)로 공급되고, 상기 탈황촉매는 탈황촉매탱크(20)에서 탈황촉매펌프(22)를 거쳐 압전소자노즐(40)을 통해 연소로(50)로 공급된다. 상기 연소로(50)에서 연소 및 탈황된 후 발생하는 연소배가스는 가스 배출부(60)을 통해 배출되어 배출가스를 분석하는 분석장비(미도시)로 공급될 수 있다.As shown in FIG. 4, 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.
도 5는 본 발명에 따른 벙커C유 탈황 시스템의 압전소자노즐(40)을 나타낸 것이다.5 shows the piezoelectric element nozzle 40 of the bunker C oil desulfurization system according to the present invention.
도 5를 참조하면, 상기 압전소자노즐(40)은 연소로(50)와 벤츄리 관으로 연결되고, 상기 연소로(50)와 연결되지 않은 벤츄리 관의 일 측면으로는 공기(air)가 주입되어, 압전소자노즐(40)을 통해 분사되는 탈황촉매를 연소로(50) 방향으로 분사되도록 밀어준다. 상기 벤츄리(Venturi) 관은 배관의 굵기가 점점 좁혀졌다가 다시 천천히 넓어지는 형태의 관을 의미하며, 상기 벤츄리 관은 배관 내의 넓은 통로에서의 높은 압력과 좁아진 통로에서의 낮은 압력과의 차이로 인해 유체가 좁은 통로쪽으로 빨려 들어가면서 생기는 현상을 벤츄리 효과를 나타낸다. 이에 따라, 상기 벤츄리 관에 주입되는 공기와 벤츄리 효과에 의해 압전소자노즐(40)에서 연소로(50) 내로 탈황촉매가 빠른 속도로 분사될 수 있다.5, 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.
상기 압전소자노즐(40)을 이용하여 탈황촉매를 분사하는 경우, 상기 압전소자(42)의 구동에 의해 탈황촉매의 입자가 초미세 액적 상태로 더 잘게 부서져 연소로(50) 내로 분사됨으로써, 탈황촉매의 확산이 용이하고 표면적이 향상되어 연소로(50) 내에서 황(S) 함유 물질과 흡착할 확률을 향상시킬 수 있다. When the desulfurization catalyst is sprayed using the piezoelectric element nozzle 40, 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.
상기 초미세 액적 상태의 탈황촉매는 평균 액적 크기가 1 내지 50 ㎛인 것일 수 있다. 예를 들어, 상기 초미세 액적 상태의 탈황촉매는 평균 액적 크기가 1 내지 40 ㎛, 1 내지 30 ㎛, 1 내지 20 ㎛, 1 내지 10 ㎛, 10 내지 20 ㎛, 10 내지 50 ㎛, 20 내지 50 ㎛, 30 내지 50 ㎛, 40 내지 50 ㎛ 또는 5 내지 15 ㎛일 수 있다.The desulfurization catalyst in the ultrafine droplet state may have an average droplet size of 1 to 50 μm. For example, the desulfurization catalyst in the ultrafine droplet state has an average droplet size of 1 to 40 μm, 1 to 30 μm, 1 to 20 μm, 1 to 10 μm, 10 to 20 μm, 10 to 50 μm, 20 to 50 μm, 30-50 μm, 40-50 μm or 5-15 μm.
상기 압전소자노즐(40)은 압전소자(42)와 탈황촉매가 유입되는 공간 사이에 미세 천공(44)을 포함할 수 있으며, 상기 미세 천공(44)은 상기 탈황촉매 입자보다 작은 크기의 천공으로 구성되어, 상기 미세 천공(44)으로 탈황촉매가 통과하지 못하는 것일 수 있다. 상기 미세 천공(44)은 상기 압전소자(42)에 의해 탈황촉매가 미세 분사되는 동시에 상기 압전소자(42)와 탈황촉매가 접촉하지 않도록 하여 탈황촉매에 의해 압전소자(42)가 부식되는 것을 방지할 수 있다.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.
상기 미세 천공(44)의 평균 천공 크기는 1 내지 10 ㎛일 수 있고, 예를 들어, 1 내지 8 ㎛, 1 내지 6 ㎛, 1 내지 5 ㎛, 1 내지 4 ㎛, 1 내지 2 ㎛, 2 내지 10 ㎛, 4 내지 10 ㎛, 5 내지 10 ㎛, 6 내지 10 ㎛ 또는 8 내지 10 ㎛일 수 있다. The average aperture size of the micro-perforations 44 may be 1 to 10 μm, for example, 1 to 8 μm, 1 to 6 μm, 1 to 5 μm, 1 to 4 μm, 1 to 2 μm, 2 to 10 μm, 4 to 10 μm, 5 to 10 μm, 6 to 10 μm or 8 to 10 μm.
상기 버너(52)에서 분출되는 화염의 평균 온도는 150 내지 2,100℃ 범위인 것을 특징으로 하는 것일 수 있다. 상기 화염의 평균 온도는 화염에서부터 상기 분사 노즐의 최대 분사거리인 450 mm까지 여러 지점의 온도의 평균값을 의미한다. 예를 들어, 상기 화염의 평균 온도는 150 내지 1,800℃, 150 내지 1,500℃, 150 내지 1,000℃, 500 내지 2,100℃, 500 내지 1,500℃ 또는 1,000 내지 1,500℃ 범위일 수 있다.The average temperature of the flame ejected from the burner 52 may be characterized in that the range of 150 to 2,100 ℃. 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. For example, 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.
본 발명의 분사 노즐 또는 압전소자노즐을 포함하는 벙커C유 탈황 시스템에서 사용되는 탈황촉매는 벙커C유의 연소 시 발생하는 황산화물을 제거할 수 있는 촉매로서, SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O 및 P2O3로 이루어진 군으로부터 선택된 1종 이상의 산화물을 포함할 수 있으며, 하기의 일 실시예와 같이 SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O 및 P2O3의 산화물을 모두 포함하여 사용하는 것이 바람직하다.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 .
상기 산화물이 SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O 및 P2O3를 모두 포함할 때의 기본 화학식은 K0.8- 0.9(Al,Fe,Mg)2(Si,Al)4O10(OH)2로 일반적으로 일라이트(illite)라 불리는 광물이며, 일라이트는 기본적으로 두 개의 사면체층 사이에 한 개의 팔면체층이 들어가 결합하는 2:1의 구조를 갖고, 팔면체층은 결합 구조내 양이온 자리 3개 중에서 2개만 양이온으로 채워지는 이팔면체(dioctahedral) 구조가 특징으로 양이온의 부족으로 인해 전체적으로 음(-)전하를 띄고 있으며, 이로 인해 탈황촉매와 혼합된 연소물(C)이 연소 될 때 황산화물(SOx)을 흡착할 수 있다.When 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 It is a mineral commonly called illite, and 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.
각 산화물들은 탈황촉매에 SiO2 15 내지 90 중량부, Al2O3 15 내지 100 중량부, Fe2O3 10 내지 50 중량부, TiO2 5 내지 15 중량부, MgO 20 내지 150 중량부, MnO 10 내지 20 중량부, CaO 20 내지 200 중량부, Na2O 15 내지 45 중량부, K2O 20 내지 50 중량부 및 P2O3 5 내지 20 중량부로 포함될 수 있다.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.
또한, 산화물들은 탈황촉매로 형성되기 전에 미분기에 의해 1 내지 2 ㎛의 입자 크기를 갖는 미립자로 혼합 및 미분되며, 비중은 2.5 내지 3.0으로 조흔색 및 은백색을 띄는 분말 형태로 사용된다. In addition, the oxides are mixed and pulverized into fine particles having a particle size of 1 to 2 μm 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.
본 발명에 사용되는 탈황촉매는 Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd 및 Pb로 이루어진 군으로부터 선택된 1종 이상의 금속을 포함할 수 있으며, 하기의 일 실시예와 같이 Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd 및 Pb의 금속을 모두 포함하여 사용하는 것이 바람직하다.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.
각 금속들은 탈황촉매에 Li 0.0035 내지 0.009 중량부, Cr 0.005 내지 0.01 중량부, Co 0.001 내지 0.005 중량부, Ni 0.006 내지 0.015 중량부, Cu 0.018 내지 0.03 중량부, Zn 0.035 내지 0.05 중량부, Ga 0.04 내지 0.08 중량부, Sr 0.02 내지 0.05 중량부, Cd 0.002 내지 0.01 중량부 및 Pb 0.003 내지 0.005 중량부로 포함될 수 있다.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.
또한, 상기 산화물과 같이 금속들도 미분기에 의해 미분되어 1 내지 2 ㎛의 입자 크기를 가지며, 비중은 2.5 내지 3.0으로 조흔색 및 은백색을 띄는 분말 형태로 사용된다.In addition, like the oxide, metals are also finely pulverized by a pulverizer to have a particle size of 1 to 2 μm, and a specific gravity of 2.5 to 3.0 is used in the form of streaks and silvery white powder.
본 발명에 사용되는 탈황촉매는 사붕산나트륨(Na2B4O7·10H2O), 수산화나트륨(NaOH), 규산나트륨(Na2SiO3) 및 과산화수소(H2O2)로 이루어진 군으로부터 선택된 1종 이상의 액상 조성물을 포함할 수 있으며, 하기의 일 실시예와 같이 사붕산나트륨, 수산화나트륨, 규산나트륨 및 과산화수소의 액상 조성물을 모두 포함하여 사용하는 것이 바람직하다.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.
본 발명에 따른 탈화용 촉매는 상기한 산화물, 액상 조성물이 혼합 및 반응을 진행하면서 킬레이트제 역할을 하여 금속과 배위결합을 통해 킬레이트화된 금속 킬레이트 화합물을 형성한다.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.
또한, 액상 조성물은 연소물(C)이 연소 될 때 발생하는 회분(ash)에 흡착하여 회분 내에 존재하는 황산화물과 반응하여 제거할 수 있다. 사붕산나트륨인 Na2B4O7에서 NaBO2가 유도되며, 수소화를 거쳐 NaBH4가 생성되고, 생성된 NaBH4가 산소와 황산화물을 만나 황산나트륨(Na2SO4)으로 반응하여 황산화물을 제거하게 되며 반응과정은 하기의 반응식 1 및 2와 같다.In addition, 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.
[반응식 1][Scheme 1]
NaBH4 + O3 → Na2O2 + H2O + BNaBH 4 + O 3 → Na 2 O 2 + H 2 O + B
[반응식 2][Scheme 2]
1) Na2O2 + SO3 → Na2SO4 + O1) Na 2 O 2 + SO 3 → Na 2 SO 4 + O
2) Na2O2 + SO2 → Na2SO4 2) Na 2 O 2 + SO 2 → Na 2 SO 4
3) Na2O2 + SO → Na2SO3 3) Na 2 O 2 + SO → Na 2 SO 3
또한, 각 액상 조성물은 탈황촉매에 사붕산나트륨 20 내지 130 중량부, 수산화나트륨 15 내지 120 중량부, 규산나트륨 50 내지 250 중량부 및 과산화수소 10 내지 50 중량부로 포함될 수 있다.In addition, 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.
또한, 탈황촉매를 혼합 및 반응시킨 후, 24 내지 72시간 정치시켜 안정화를 시키며 탈황촉매를 분리하여 액상 형태의 조성물로 사용할 수 있다.In addition, 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.
본 발명에 사용되는 탈황촉매를 400 내지 2,100℃의 온도 범위에서 연소물(C)과 혼합하여 연소 시킬 때 황산화물의 흡착 효과가 활성화될 수 있으나, 600 내지 1,500℃의 온도 범위에서 연소시키는 것이 높은 효율을 나타낼 수 있다.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
또한, 본 발명에 따른 벙커C유 탈황 시스템은 벙커C유의 연소 과정에서 황산화물이 생성되기 전에 연소와 동시에 탈황시킴으로써 다량의 황산화물이 대기 중으로 배출되는 것을 미연에 방지할 수 있기 때문에 황산화물로 인한 대기오염 문제 해소에 크게 기여할 수 있는 효과가 있다.In addition, 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.
이하 본 발명에 따르는 실시예 등을 통해 본 발명을 보다 상세히 설명하나, 본 발명의 범위가 하기 제시된 실시예에 의해 제한되는 것은 아니다.Hereinafter, the present invention will be described in more detail by way of Examples and the like according to the present invention, but the scope of the present invention is not limited by the Examples presented below.
[실시예] [Example]
본 실시예에서는, 탈황촉매를 이용하여 벙커C유의 연소화염에 직접 분사하여 연소과정에서 생성되는 SO2의 농도변화를 측정하여 탈황촉매의 SO2 저감 효과를 확인하였다.In this example, 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.
<제조예: 탈황촉매의 제조><Preparation Example: Preparation of Desulfurization Catalyst>
산화물인 SiO2 150kg, Al2O3 150kg, Fe2O3 100kg, TiO2 50kg, MgO 200kg, MnO 100kg, CaO 200kg, Na2O 150kg, K2O 200kg, P2O3 50kg를 혼합하고 미분기로 미분하여 산화물 미분체를 형성하였다.Oxides SiO 2 150 kg, Al 2 O 3 150 kg, Fe 2 O 3 100 kg, TiO 2 50 kg, MgO 200 kg, MnO 100 kg, CaO 200 kg, Na 2 O 150 kg, K 2 O 200 kg, P 2 O 3 50 kg were mixed and milled. to form an oxide fine powder.
금속인 Li 35g, Cr 50g, Co 10g, Ni 60g, Cu 180g, Zn 350g, Ga 400g, Sr 200g, Cd 20g, Pb 30g을 혼합하고 미분기로 미분하여 금속 미분체를 형성하였다.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.
산화물 미분체 및 금속 미분체는 입자 크기가 1 ~ 2 ㎛가 되도록 반복해서 미분하였다.The fine oxide powder and the fine metal powder were repeatedly pulverized to have a particle size of 1 to 2 μm.
반응로에 3000kg의 물을 투입하고 50 ~ 60℃를 유지한 상태에서 사붕산나트륨(Na2B4O710H2O) 50kg을 투입하여 30분 간 교반한 후, 수산화나트륨(NaOH) 100kg을 투입하여 교반하였고, 10분 후에 앞에서 미분한 산화물 미분체를 100kg 단위, 5분 간격으로 분배하여 투입하고 2시간 이상 교반시켰다. 교반을 계속하면서 온도를 60 ~ 80℃로 상승시키고 규산나트륨(Na2SiO3)을 100kg 투입하였다. 30분 간 교반한 후 앞에서 미분한 금속 미분체를 20g 단위, 3분 간격으로 투입하여 교반하였다. 1시간 동안 교반 후 과산화수소(H2O2) 30kg을 투입하고 30분 간 더 교반한 후 1시간 동안 자연냉각을 실시하였다.3000 kg of water was put into the reactor, and 50 kg of sodium tetraborate (Na 2 B 4 O 7 10H 2 O) was added while maintaining 50 ~ 60 ℃, stirred for 30 minutes, and then 100 kg of sodium hydroxide (NaOH) was added It was added and stirred, and after 10 minutes, the fine oxide powder pulverized before was distributed in units of 100 kg, at intervals of 5 minutes, and stirred for 2 hours or more. While stirring was continued, the temperature was raised to 60 ~ 80 ℃ and sodium silicate (Na 2 SiO 3 ) 100 kg was added. After stirring for 30 minutes, the fine metal powder pulverized before was added in units of 20 g at intervals of 3 minutes and stirred. After stirring for 1 hour, 30 kg of hydrogen peroxide (H 2 O 2 ) was added, followed by further stirring for 30 minutes, followed by natural cooling for 1 hour.
냉각 후 48시간 동안 안정화를 시킨 후, 액상 조성물과 침전된 분말 조성물을 분리시킨 후, 침전된 분말 조성물을 분리한 액상 조성물을 별도의 용기에 이동시켜 액상 상태의 탈황촉매를 제조하였다.After cooling and stabilization for 48 hours, 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.
<실험준비><Experiment Preparation>
본 실험에 사용된 벙커C유의 물성은 한국석유관리원의 석유기술연구소에서 분석한 결과인 도 4와 같다. 벙커C유에 포함된 황(S)성분은 1.21%이며, 저위 발열량은 약 9,300kcal/L 이다. 탈황 성능실험을 위한 탈황촉매는 상기 제조예에서 제조된 탈황촉매를 사용하였다. 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. As the desulfurization catalyst for the desulfurization performance test, the desulfurization catalyst prepared in Preparation Example was used.
도 5에 나타낸 바와 같이, 탈황촉매는 화염의 상부에서 압력식 분무노즐을 통해 화염의 상부에서 분무하였으며, 화염과의 간격을 조절할 수 있도록 하였다. 도 5에 나타낸 화염과의 분사 및 온도 측정 위치에 따른 연소로(화염) 온도는 하기 표 1에 나타내었다. As shown in FIG. 5, 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.
[표 1][Table 1]
Figure PCTKR2021008487-appb-I000001
Figure PCTKR2021008487-appb-I000001
탈황촉매는 정량 펌프를 통해 설정된 양이 노즐로 공급되었다. 도 6은 분사 노즐의 분사위치 조절용 배관을 외부에서 나타낸 이미지이다. 도 7은 정량펌프의 다이얼 조절량(%)과 사용 노즐에서의 분사량 및 분사거리를 물을 이용해서 측정한 결과를 나타내었다. 연소실 각부의 온도 측정위치는 도 5에 나타낸 바와 같으며, 탈황촉매에 의해 온도 변화가 있는지를 확인하였다.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.
본 실시예에서 벙커C유 연소로의 탈황성능 및 연소 배가스의 조성을 분석하기 위해 사용된 연소가스 분석장비는 독일의 VarioPlus Ind. MRU Emission Monitoring System을 사용하였다.In this embodiment, 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.
<< 실험예Experimental example 1: 벙커C유 및 탈황촉매 분사 위치에 따른 탈황 실험> 1: Desulfurization experiment according to the location of bunker C oil and desulfurization catalyst injection>
본 실시예에서, 먼저 탈황촉매(LCLS)를 공급하지 않은 상태의 벙커C유에 대하여 배기가스 중의 SO2를 측정한 후에 탈황촉매를 일정량 (55 cc/min) 분사하면서 노즐 위치를 조절하여 SO2의 저감율이 가장 높은 위치를 선택하여 노즐을 고정한 후에 공급되는 탈황촉매의 농도를 조절하면서 연소배가스의 조성을 측정 및 분석하였다. 벙커C유 버너에 공급되는 원유는 펌프압력 24 bar에서 전자유량계로 측정된 공급량은 0.32∼0.35 L/min의 범위에 있음을 확인하였다.In this embodiment, first, after measuring SO 2 in the exhaust gas for bunker C oil in a state in which the desulfurization catalyst (LCLS) is not supplied, a predetermined amount (55 cc/min) of the desulfurization catalyst is sprayed while the nozzle position is adjusted to reduce the SO 2 After fixing the nozzle by selecting the position with the highest reduction rate, 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.
도 8은 우선 1구간에서 벙커C유 원유만을 연소시켜 연소 배가스 중의 SO2 농도를 측정한 후 2구간 이후에는 탈황촉매(LCLS)를 물과 1:1로 희석한 용액을 분사하면서 노즐 위치 변화에 따른 SO2 농도를 측정하여 가장 SO2의 저감율이 높은 지점을 선정하기 위한 결과를 보여준다(1구간: 원유, 2구간: 320 mm, 3구간: 350 mm, 4구간: 380 mm, 5구간: 410 mm, 6구간: 380 mm). 표 2에 측정 구간별 탈황촉매 공급 조건 및 노즐 위치 조건을, 표 3에 측정 구간별 SO2의 평균농도를 나타내었다. 측정된 SO2의 농도는 기준산소농도 6%로 환산한 값이다.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 The result for selecting the point with the highest SO 2 reduction rate is shown by measuring the SO 2 concentration according to the mm, 6 divisions: 380 mm). Table 2 shows the desulfurization catalyst supply conditions and nozzle position conditions for each measurement section, and 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%.
[표 2][Table 2]
Figure PCTKR2021008487-appb-I000002
Figure PCTKR2021008487-appb-I000002
[표 3][Table 3]
Figure PCTKR2021008487-appb-I000003
Figure PCTKR2021008487-appb-I000003
<실험예 2: 탈황촉매 농도 변화에 따른 탈황 실험><Experimental Example 2: Desulfurization experiment according to the change in the concentration of the desulfurization catalyst>
상기 실시예에서 탈황촉매의 SO2 저감 효과가 가장 좋은 위치(분사거리 380 mm)에 노즐을 고정시킨 상태에서 탈황촉매의 농도를 변화시키면서 연소배가스의 각 성분에 대한 배출 농도 변화를 측정하였다.In the above example, while the concentration of the desulfurization catalyst was changed while the nozzle was fixed at the position where the SO 2 reduction effect of the desulfurization catalyst was best (injection distance 380 mm), the change in the emission concentration of each component of the combustion exhaust gas was measured.
표 4에 도 9의 각 측정 구간에 대한 탈황촉매 농도 조건 및 측정시간과 각 농도 조건별 탈황촉매의 분사 시작 후에 연소 배가스 중의 SO2 농도가 안정되는 구간에서의 평균농도를 산정하도록 하였으며, 그 산정시간을 나타내었다. 즉 표 5의 평균농도는 표 4 표시된 평균 산정시간 동안에 측정된 농도로 평균한 값이다.In Table 4, 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.
[표 4][Table 4]
Figure PCTKR2021008487-appb-I000004
Figure PCTKR2021008487-appb-I000004
[표 5][Table 5]
Figure PCTKR2021008487-appb-I000005
Figure PCTKR2021008487-appb-I000005
도 9에 나타낸 바와 같이, A에서 B구간으로, B구간에서 C구간으로 넘어가는 초기에 SO2 농도가 상승하는 부분은 정량펌프에 공급하는 탈황촉매 용기를 교체하는 과정에서 발생하는 일시적 탈황촉매의 공급 단절에 의해 발생하는 현상이다.As shown in FIG. 9, 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.
도 9 내지 도 12에 분사 탈황촉매의 농도 변화에 따른 연소배가스 중의 SO2, CO, O2, NOx 농도 측정 결과(기준산소농도 6%)를 그래프로 나타내었다.9 to 12, SO 2 , CO, O 2 , NOx concentration measurement results (reference oxygen concentration 6%) in the combustion exhaust gas according to the change in the concentration of the spray desulfurization catalyst are graphed.
상기 표 5에 벙커C유 버너 화염에 분사한 탈황촉매(LCLS)의 농도변화에 따른 연소 배가스 성분의 평균농도(기준산소농도 6%)를 나타내었다. 표 5에 나타낸 바와 같이, SO2의 경우에는 탈황촉매(LCLS)와 물의 희석 비율에 따라 배출농도가 확연히 변화함을 알 수 있다. CO의 경우에는 탈황촉매의 농도 변화에 대하여 거의 영향이 없이 연소가 잘 이루어지고 있음을 알 수 있으며 O2의 경우 탈황촉매의 농도 증가에 따라 다소 낮아지고 있다. 반대로 NOx의 경우에는 탈황촉매의 농도 증가에 따라 다소 높아짐을 보이나 온도 변화의 영향에 의한 것으로 보이며, 크게 유의미한 결과는 아닌 것으로 판단된다.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. As shown in Table 5, in the case of SO 2 , it can be seen that the emission concentration is significantly changed according to the dilution ratio of the desulfurization catalyst (LCLS) and water. In the case of 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. Conversely, in the case of 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.
하기 표 6에 벙커C유 원유의 연소 시에 측정된 SO2의 농도에 대하여 각 탈황촉매 공급 농도 조건에서의 SO2의 평균농도와 저감율을 정리하였다. 표 6에 나타낸 바와 같이, 탈황촉매:물=1:1의 경우에 SO2의 저감율은 52.2%, 탈황촉매:물=2:1의 경우에 SO2의 저감율은 73.3%, 탈황촉매:물=3:1의 경우에 SO2의 저감율은 82.8%로 산정되었다.Table 6 below 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. As shown in Table 6, in the case of desulfurization catalyst: water = 1:1, the reduction rate of SO 2 was 52.2%, in the case of the desulfurization catalyst: water = 2:1, the reduction rate of SO 2 was 73.3%, and the desulfurization catalyst: water = In the case of 3:1, the reduction rate of SO 2 was estimated to be 82.8%.
[표 6][Table 6]
Figure PCTKR2021008487-appb-I000006
Figure PCTKR2021008487-appb-I000006
본 발명은 벙커C유 탈황 시스템에 광범위하게 사용될 수 있다.The present invention can be widely used in bunker C oil desulfurization systems.

Claims (13)

  1. 벙커C유를 공급하는 제1 오일탱크;a first oil tank supplying bunker C oil;
    탈황촉매를 공급하는 탈황촉매탱크;a desulfurization catalyst tank for supplying a desulfurization catalyst;
    상기 벙커C유 및 탈황촉매가 공급되고, 버너의 화염이 분출되는 연소로;a combustion furnace to which the bunker C oil and a desulfurization catalyst are supplied, and the flame of a burner is ejected;
    상기 연소로 로(furnace) 내의 화염에 탈황촉매를 직접 분사하며, 분사거리의 조절이 가능한 분사 노즐; 및,an injection nozzle capable of directly injecting a desulfurization catalyst into a flame in the combustion furnace and controlling an injection distance; and,
    탈황된 배기가스가 배출되는 가스 배출부를 포함하고,Including a gas discharge unit from which the desulfurized exhaust gas is discharged,
    상기 연소로 로 내에서 상기 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 하는 벙커C유 탈황 시스템.The bunker C oil desulfurization system, characterized in that 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.
  2. 벙커C유를 공급하는 제1 오일탱크;a first oil tank supplying bunker C oil;
    탈황촉매를 공급하는 탈황촉매탱크;a desulfurization catalyst tank for supplying a desulfurization catalyst;
    상기 벙커C유 및 탈황촉매가 공급되고, 버너의 화염이 분출되는 연소로;a combustion furnace to which the bunker C oil and a desulfurization catalyst are supplied, and the flame of a burner is ejected;
    압전소자를 이용하여 초미세 액적 상태의 탈황촉매를 상기 연소로 로(furnace) 내로 분사하는 압전소자노즐; 및,a piezoelectric element nozzle for injecting a desulfurization catalyst in an ultra-fine droplet state into the combustion furnace using a piezoelectric element; and,
    탈황된 배기가스가 배출되는 가스 배출부를 포함하고,Including a gas discharge unit from which the desulfurized exhaust gas is discharged,
    상기 연소로 로 내에서 상기 벙커C유 및 탈황촉매를 연소시키는 동시에 벙커C유의 탈황이 이루어지는 것을 특징으로 하는 벙커C유 탈황 시스템.The bunker C oil desulfurization system, characterized in that 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.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 분사 노즐의 분사거리는 300 내지 450 mm 범위에서 조절이 가능한 것을 특징으로 하는 벙커C유 탈황 시스템.The bunker C oil desulfurization system, characterized in that the injection distance of the injection nozzle can be adjusted in the range of 300 to 450 mm.
  4. 제 1 항에 있어서,The method of claim 1,
    상기 탈황촉매는 화염에 직접 분사 시 평균 액적 크기가 1 내지 100 ㎛인 것을 특징으로 하는 벙커C유 탈황 시스템.The bunker C oil desulfurization system, characterized in that the desulfurization catalyst has an average droplet size of 1 to 100 μm when directly sprayed into the flame.
  5. 제 1 항에 있어서,The method of claim 1,
    상기 분사 노즐은,The spray nozzle is
    상기 연소로 로 내로 탈황촉매를 분사하는 메인노즐;a main nozzle for injecting a desulfurization catalyst into the combustion furnace;
    상기 메인노즐 방향으로 공기를 주입하는 공기 투입구; an air inlet for injecting air in the direction of the main nozzle;
    상기 메인노즐 내에 소정 각도로 경사지게 위치하며 서로 마주보는 세 개의 서브노즐; 및,three sub-nozzles which are inclined at a predetermined angle in the main nozzle and face each other; and,
    상기 메인노즐과 상기 서브노즐 사이에 장착되어 자기장을 발생시키는 자기장 발생장치를 포함하는 벙커C유 탈황 시스템.Bunker C oil desulfurization system including a magnetic field generator mounted between the main nozzle and the sub-nozzle to generate a magnetic field.
  6. 제 5 항에 있어서,6. The method of claim 5,
    상기 분사 노즐은 상기 세 개의 서브노즐에서 동시에 탈황촉매를 분사하여 분사된 탈황촉매가 부딪치면서 잘게 부숴진 뒤 상기 메인노즐을 통해 분사되도록 하는 것을 특징으로 하는 벙커C유 탈황 시스템.bunker C oil desulfurization system, characterized in that the spray nozzle sprays the desulfurization catalyst from the three sub-nozzles at the same time so that the sprayed desulfurization catalyst is crushed and then sprayed through the main nozzle.
  7. 제 2 항에 있어서,3. The method of claim 2,
    상기 초미세 액적 상태의 탈황촉매는 평균 액적 크기가 1 내지 50 ㎛인 것을 특징으로 하는 벙커C유 탈황 시스템.The desulfurization catalyst in the ultrafine droplet state has an average droplet size of 1 to 50 μm.
  8. 제 1 항 또는 제 2 항에 있어서,3. The method according to claim 1 or 2,
    상기 화염의 평균 온도는 150 내지 2,100℃ 범위인 것을 특징으로 하는 벙커C유 탈황 시스템.Bunker C oil desulfurization system, characterized in that the average temperature of the flame is in the range of 150 to 2,100 ℃.
  9. 제 1 항 또는 제 2 항에 있어서,3. The method according to claim 1 or 2,
    상기 탈황촉매는,The desulfurization catalyst is
    (a) SiO2, Al2O3, Fe2O3, TiO2, MgO, MnO, CaO, Na2O, K2O 및 P2O3로 이루어진 군으로부터 선택된 1종 이상의 산화물; (a) at least one oxide selected from the group consisting 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 ;
    (b) Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd 및 Pb로 이루어진 군으로부터 선택된 1종 이상의 금속; 및,(b) at least one metal selected from the group consisting of Li, Cr, Co, Ni, Cu, Zn, Ga, Sr, Cd and Pb; and,
    (c) 사붕산나트륨(Na2B4O7·10H2O), 수산화나트륨(NaOH), 규산나트륨(Na2SiO3) 및 과산화수소(H2O2)로 이루어진 군으로부터 선택된 1종 이상의 액상 조성물;이 포함되는 것을 특징으로 하는 벙커C유 탈황 시스템.(c) at least one liquid selected from the group consisting of 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 ) Composition; bunker C oil desulfurization system, characterized in that it is included.
  10. 제 9 항에 있어서,10. The method of claim 9,
    상기 산화물은 SiO2 15 내지 90 중량부, Al2O3 15 내지 100 중량부, Fe2O3 10 내지 50 중량부, TiO2 5 내지 15 중량부, MgO 20 내지 150 중량부, MnO 10 내지 20 중량부, CaO 20 내지 200 중량부, Na2O 15 내지 45 중량부, K2O 20 내지 50 중량부 및 P2O3 5 내지 20 중량부로 포함되며,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 It is included in an amount of 20 to 200 parts by weight of CaO, 15 to 45 parts by weight of Na 2 O, 20 to 50 parts by weight of K 2 O, and 5 to 20 parts by weight of P 2 O 3 ,
    상기 금속은 Li 0.0035 내지 0.009 중량부, Cr 0.005 내지 0.01 중량부, Co 0.001 내지 0.005 중량부, Ni 0.006 내지 0.015 중량부, Cu 0.018 내지 0.03 중량부, Zn 0.035 내지 0.05 중량부, Ga 0.04 내지 0.08 중량부, Sr 0.02 내지 0.05 중량부, Cd 0.002 내지 0.01 중량부 및 Pb 0.003 내지 0.005 중량부로 포함되는 것을 특징으로 하는 벙커C유 탈황 시스템.The metal is 0.0035 to 0.009 parts by weight of Li, 0.005 to 0.01 parts by weight of Cr, 0.001 to 0.005 parts by weight of Co, 0.006 to 0.015 parts by weight of Ni, 0.018 to 0.03 parts by weight of Cu, 0.035 to 0.05 parts by weight of Zn, 0.04 to 0.08 parts by weight of Ga Part, 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 Bunker C oil desulfurization system, characterized in that it is included.
  11. 제 9 항에 있어서,10. The method of claim 9,
    상기 산화물 및 금속 입자의 크기는 1 내지 2 ㎛이고, 비중은 2.5 내지 3.0인 것을 특징으로 하는 벙커C유 탈황 시스템.The oxide and metal particles have a size of 1 to 2 μm, and a specific gravity of 2.5 to 3.0.
  12. 제 9 항에 있어서,10. The method of claim 9,
    상기 액상 조성물은 사붕산나트륨(Na2B4O7·10H2O) 20 내지 130 중량부, 수산화나트륨(NaOH) 15 내지 120 중량부, 규산나트륨(Na2SiO3) 50 내지 250 중량부 및 과산화수소(H2O2) 10 내지 50 중량부로 포함되는 것을 특징으로 하는 벙커C유 탈황 시스템.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), 50 to 250 parts by weight of sodium silicate (Na 2 SiO 3 ) and Hydrogen peroxide (H 2 O 2 ) Bunker C oil desulfurization system, characterized in that it contains 10 to 50 parts by weight.
  13. 제 9 항에 있어서,10. The method of claim 9,
    상기 탈황촉매는 상기 산화물, 금속 및 액상 조성물이 금속 킬레이트 화합물을 형성하는 것을 특징으로 하는 벙커C유 탈황 시스템.The desulfurization catalyst is a bunker C oil desulfurization system, characterized in that the oxide, metal and liquid composition form a metal chelate compound.
PCT/KR2021/008487 2020-12-23 2021-07-05 Bunker-c oil desulfurization system WO2022139094A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020200182525A KR102264355B1 (en) 2020-12-23 2020-12-23 Bunker C oil desulfurization system
KR10-2020-0182525 2020-12-23

Publications (1)

Publication Number Publication Date
WO2022139094A1 true WO2022139094A1 (en) 2022-06-30

Family

ID=76417382

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2021/008487 WO2022139094A1 (en) 2020-12-23 2021-07-05 Bunker-c oil desulfurization system

Country Status (2)

Country Link
KR (1) KR102264355B1 (en)
WO (1) WO2022139094A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102264355B1 (en) * 2020-12-23 2021-06-14 (주)로우카본 Bunker C oil desulfurization system

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030006429A (en) * 2001-07-12 2003-01-23 박현 The reduction method of nitrogen oxides and sulfur oxides using hydrogen peroxide solution and calcium oxide solution
KR20100064351A (en) * 2008-12-04 2010-06-14 주식회사 유니코정밀화학 Composition for removing sox in exhausted gas
WO2012064084A2 (en) * 2010-11-08 2012-05-18 Oh Mi Hye Liquid-combustion catalyst composition including mixed metal-complex ionic compound
KR101836047B1 (en) * 2017-09-18 2018-03-08 이철 Desulfurization system using a catalyst for desulfurization
KR102264355B1 (en) * 2020-12-23 2021-06-14 (주)로우카본 Bunker C oil desulfurization system

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05117665A (en) 1991-10-28 1993-05-14 Idemitsu Kosan Co Ltd Catalytic hydrogenation of heavy hydrocarbon oil

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030006429A (en) * 2001-07-12 2003-01-23 박현 The reduction method of nitrogen oxides and sulfur oxides using hydrogen peroxide solution and calcium oxide solution
KR20100064351A (en) * 2008-12-04 2010-06-14 주식회사 유니코정밀화학 Composition for removing sox in exhausted gas
WO2012064084A2 (en) * 2010-11-08 2012-05-18 Oh Mi Hye Liquid-combustion catalyst composition including mixed metal-complex ionic compound
KR101836047B1 (en) * 2017-09-18 2018-03-08 이철 Desulfurization system using a catalyst for desulfurization
KR102264355B1 (en) * 2020-12-23 2021-06-14 (주)로우카본 Bunker C oil desulfurization system

Also Published As

Publication number Publication date
KR102264355B1 (en) 2021-06-14

Similar Documents

Publication Publication Date Title
WO2019054659A1 (en) Desulfurization system using desulfurization catalyst
WO2019054658A1 (en) Desulfurization catalyst, method for producing same, and method for desulfurization using same
WO2022139094A1 (en) Bunker-c oil desulfurization system
CN1116422C (en) Coherent jet injector lance
WO2017185858A1 (en) Serial flash furnace and smelting method thereof
US20090202717A1 (en) Anti-Fouling Coatings for Combustion System Components Exposed to Slag, Ash and/or Char
WO2021091076A1 (en) Pretreatment desulfurization method for ship fuel oil using pretreatment desulfurization agent
WO2012064084A2 (en) Liquid-combustion catalyst composition including mixed metal-complex ionic compound
WO2021091078A1 (en) Marine engine pretreatment desulfurization control and monitoring system
CN102076399A (en) Combustion of co and combustibles in steel furnace offgases
KR102254998B1 (en) Pre-treatment method for desulfurizing a marine fuel oil using the pre-treatment catalyst for desulfurization
KR102255054B1 (en) Pre-treatment system for desulfurizing a marine fuel oil using the pre-treatment catalyst for desulfurization
WO2024019288A1 (en) Method for manufacturing combustion aid for addition before fossil fuel combustion and desulfurization catalyst
WO2021091077A1 (en) Ship fuel oil pretreatment desulfurization system using pretreatment desulfurization agent
WO2022139095A1 (en) Fugitive dust reducing agent and method for reducing fugitive dust using same
WO2023282364A1 (en) Ship fuel oil pretreatment desulfurization system using pretreatment desulfurization agent
WO2023282363A1 (en) Method for pretreatment desulfurization of ship fuel oil by using pretreatment desulfurization agent
WO2022225153A1 (en) Method for desulfurizing marine fuel oil by using mixed desulfurizing agent prepared for reforming high-sulfur fuel oil (hsfo) to low-sulfur fuel oil (lsfo)
WO2024019446A1 (en) Method for producing carbon dioxide absorbent and desulfurization catalyst
WO2012047065A2 (en) Adhesive composition for steel manufacturing having functions for accelerating combustion and lowering melting point
WO2023282360A1 (en) Method for emulsifiying fuel oil and desulfurization agent for reducing sulfur oxide
WO2023140439A1 (en) System for carbon dioxide capture and carbon recycling for steel mill
WO2013103234A1 (en) Fuel additive composition containing liquid crystal state of borate ions, and preparation method thereof
GB2029956A (en) Method and burner apparatus for heating a non ferrous material charge with liwuid fuel
KR100553548B1 (en) Fuel Additive and Method for Removing White Plume from Flue Gas Using it

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21911164

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21911164

Country of ref document: EP

Kind code of ref document: A1