WO2013066089A1 - Method for catalytic cracking of heavy hydrocarbon resources - Google Patents

Method for catalytic cracking of heavy hydrocarbon resources Download PDF

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WO2013066089A1
WO2013066089A1 PCT/KR2012/009149 KR2012009149W WO2013066089A1 WO 2013066089 A1 WO2013066089 A1 WO 2013066089A1 KR 2012009149 W KR2012009149 W KR 2012009149W WO 2013066089 A1 WO2013066089 A1 WO 2013066089A1
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metal
metals
oil
catalyst
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French (fr)
Korean (ko)
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박종호
전상구
나정걸
정태성
노남선
김종남
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한국에너지기술연구원
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique

Definitions

  • the present invention relates to a pyrolysis method of a heavy carbon source, and more particularly, to a method for obtaining high quality light crude oil by pyrolyzing a heavy carbon source using a catalyst.
  • API weight There are many ways to classify crude oil, and the representative one is based on API weight.
  • it can be divided into light crude oil and heavy crude oil.It is further subdivided into ultra light crude oil, light crude oil, heavy crude oil and ultra heavy crude oil.
  • APIs with a weight of 35 or more are classified as light crude oil and those with a weight less than 35 are heavy crude oil.
  • Heavy carbon sources that can replace light crude oil currently in use include vacuum residue oil, refined residual oil, heavy oil, spent lubricating oil, natural bitumen, bitumen or sand containing them, bunker-C oil, solid biomass and coal. have.
  • problems that heavy carbon sources have in common include high viscosity, high metal content, high sulfur content, and high organic acid concentration.
  • the high viscosity is known to be due to the asphaltenes contained in them, which causes serious problems in transport, so that a low viscosity light oil (diluent) can be added to lower the viscosity, or hardened through hydrocarbon decomposition to lower the viscosity.
  • a low viscosity light oil (diluent) can be added to lower the viscosity, or hardened through hydrocarbon decomposition to lower the viscosity.
  • Technology is being used. Since the method using such a diluent uses expensive light oil, it is uneconomical, and the technology of lowering the viscosity by partially hardening directly in an oil well is being actively developed.
  • the hardening technology through cracking reaction is a process that removes carbon from crude oil through pyrolysis, such as coking process and fluid catalytic cracking process, and hydrogenation, hydrogenation, and hydrogenation process through hydrogenation.
  • the fluidized bed catalytic cracking process promotes the decomposition reaction using an acid catalyst, but the catalyst quickly deactivates a crude oil having a high sulfur content, a high metal content, or a high organic acid (CCR) content such as heavy crude oil. It is known that it is not applicable.
  • U.S. Patent No. 7572362 discloses a pyrolysis process which is one of processes for removing carbon.
  • This pyrolysis process is a process that does not use a catalyst by rapid thermal decomposition using a high temperature sand without involvement of the catalyst during the pyrolysis reaction, so the reaction rate is relatively slow and a large amount of heat supply medium (sand) must be circulated. There is this.
  • the present invention provides a dispersed catalyst that is not deactivated even when applied to a heavy carbon source in order to overcome the problem that the catalyst is inactivated due to caulking, etc. when the catalyst is applied to the conventional heavy carbon source. .
  • the present invention provides a catalytic pyrolysis method of a heavy carbon source capable of obtaining light crude oil at high yield and low cost by promoting a pyrolysis reaction using a dispersed catalyst that is not deactivated even when pyrolysis is performed on the heavy carbon source.
  • the present invention also provides a method for catalytic pyrolysis of heavy carbon sources that can selectively convert the components of asphaltene using a dispersed catalyst and convert them into high quality light crude oil having high storage stability due to low olefin content.
  • the present invention is a catalytic pyrolysis method of a heavy carbon source, characterized by pyrolyzing a heavy carbon source using a dispersed catalyst.
  • the present invention relates to a method for producing light crude oil by pyrolyzing a heavy carbon source
  • the present invention is characterized in that the catalytic pyrolysis method using a catalyst in the thermal decomposition of the heavy carbon source, and more particularly to a dispersed catalyst It is a method that can mass produce high quality light crude oil at low cost in a short time.
  • Heavy carbonaceous materials in the present invention means a carbon source commonly used for the reforming of light crude oil using carbon removal or hydrogenation, such as vacuum residue, oil refinery residue, heavy oil, waste lubricant, natural bitumen, Bitumen or sand, bunker-C oils, solid biomass and coal comprising them.
  • the method of reforming a heavy carbon source into light crude oil is generally divided into a process technology for removing carbon and a process technology through hydrogenation.
  • the catalytic pyrolysis method using a dispersed catalyst according to the present invention is hardened by removing carbon. These processes include processes such as coking and FCC.
  • Dispersion type catalyst refers to a type of catalyst that can be dissolved or uniformly dispersed in a heavy carbon source as a reaction raw material.
  • Such dispersed catalysts may generally be represented as oil-soluble catalysts and water-soluble catalysts, but are not limited thereto.
  • Solid particle catalysts may also be included therein.
  • Oil-soluble catalysts are soluble in heavy carbon sources, such as metal salts of organic acids and organometalic compounds, such as naphthenate, resinate, and octoate. Metal compound is shown.
  • a water soluble catalyst refers to a metal compound that contains one or more metal elements and can be dissolved in water.
  • the solid particle catalyst includes one or more metal elements and represents particles in a solid phase in a solution, and includes metal particles, metal sulfur compounds, metal oxides, metal hydroxides, and the like.
  • the dispersing catalyst according to the present invention is not limited, but is not limited to Group IA metals, Group IIB metals, Group IIIA metals, Group IVA metals, Group VA metals, Group VIA metals, Group VIIA metals, Group VIII A, Group IB metals, and IIIB.
  • Group metals Si, Ge and chlorides, sulfur oxides, nitrates or mixtures thereof and organic complexes thereof, more preferably Group IA metal is Li or K, Group IIB metal is Mg or Ca, Group IIIA
  • the metal is selected from Sc, Y, La or Ac
  • the Group IVA metal is selected from Ti, Zr or Hf
  • the Group VA metal is selected from V or Nb
  • the Group VIA metal is selected from Cr, Mo or W
  • the Group VIIA metal is Mn
  • the Group VIII metal is selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir or Pt
  • the Group IB metal is Cu
  • the Group IIIB metal may be selected from B, Al, Ga or In.
  • organic complex examples include [Fe (CO) 5 ] (pentacarbonyl iron), [Fe (Cp) 2 ] (ferrocene or bis (cyclopentadienyl iron)), [Fe (acac) 3 ] (tree Acetylacetonate), [Mo (CO) 6 ] (hexacarbonylmolybdenum), [Mo (C 5 H 5 ) (CO) 3 ] 2 (cyclopentadienyltricarbonylmolybdenum dimer), [Mo (allyl ) 4 ] (tetraallyl molybdenum), [W (CO) 6 ] (hexacarbonyl tungsten), [W (C 6 H 6 ) 2 ] (bis (benzene) tungsten), [W (But) 3 ] (tri Butyl tungsten), [W (allyl) 4 ] (tetraallyl tungsten), [Ni (CO) 4 ] (tetracarbonylnic
  • the heavy carbon source according to the catalytic pyrolysis method of the heavy carbon source of the present invention is a vacuum residue, oil refined residue, heavy oil, natural bitumen, bitumen; Or sand comprising at least one substance selected from vacuum residue, oil refined residue, heavy oil, natural bitumen and bitumen; It may be selected from one or more mixtures selected from bunker-C oil, solid biomass and coal.
  • the catalytic pyrolysis method of the heavy carbon source of the present invention first comprises mixing the dispersed catalyst with the heavy carbon source, pyrolyzing the mixture of the step and recovering the product produced in the step.
  • the dispersed catalyst may have a metal atom of 10 to 10000 ppm of the dispersed catalyst based on the total weight of the heavy carbon source. If the metal atom of the dispersed catalyst used is less than 10ppm does not exhibit sufficient catalyst activity, it is more than 10000ppm and economically inefficient. More preferably, the metal atom of the dispersed catalyst may be 100 to 500 ppm based on the total weight of the heavy carbon source.
  • the pre-treatment process before the thermal decomposition in the step of mixing the dispersed catalyst with the heavy carbon source may be further carried out a step of mixing the dispersed catalyst and the heavy carbon source sufficiently to increase the thermal decomposition effect.
  • the stirring may be performed at a temperature of 100 ⁇ 200 °C.
  • Pyrolysis of the dispersed catalyst may proceed at 300 ⁇ 800 °C and if it is lower than 300 °C may not appear enough decomposition and over cracking occurs at 800 °C or higher to increase the yield of the gas product is converted to high-quality light crude oil Not effective
  • More preferably pyrolysis may proceed at 450 ⁇ 750 °C.
  • the recovery of the present invention can be recovered by any suitable apparatus and method depending on the liquid or gas of the decomposition product, and modifications possible by those skilled in the art are also possible.
  • the catalytic pyrolysis method of the heavy carbon source according to the present invention can selectively decompose the components of asphaltenes and lower the aromatic content and the olefin content in the cracked oil to obtain high quality light crude oil having improved storage stability.
  • the catalytic pyrolysis method of the heavy carbon source according to the present invention has the advantage that it is possible to promote the pyrolysis rate and lower the pyrolysis reaction temperature by using a dispersed catalyst to obtain a cost reduction effect.
  • Example 1 is a graph comparing the yield of pyrolysis products obtained in Example 2 and Comparative Example 2
  • Example 2 is a graph showing a SARA analysis of the pyrolysis liquid generating oil obtained in Example 2,
  • Example 7 is a graph showing the olefin and paraffin ratio in the gas in the product obtained by the pyrolysis reaction in Example 5 and Comparative Example 4.
  • API specific gravity was measured and SARA analysis was performed to investigate the quality of the liquid product oil obtained in the pyrolysis experiment.
  • the API specificity was measured by Anton Parr's DMA 4500 equipment. SARA analysis was carried out using a TLC-FID apparatus. 15 ⁇ m).
  • the fixed bed pyrolysis reaction system used in the experiment consists of a feedstock feeder, a fixed bed reactor and a product recovery system.
  • the feeder of the reaction raw material was able to maintain the temperature above 150 °C to quantitatively supply
  • the reactor used in the experiment is a continuous fixed bed reactor to load a sus bead in the center of the reactor to maintain a constant reaction temperature and pyrolysis It was made to proceed.
  • nitrogen was supplied together with the reactants, and the residence time of the pyrolysis was controlled to prevent excessive pyrolysis.
  • the mixture was sufficiently stirred at a temperature of 150 ° C. for mixing the dispersed catalyst and the reactant.
  • the catalyst used was ferrocene, which is 1000ppm based on the Fe metal of ferrocene with respect to the total weight of the reaction raw material, which is a heavy carbon source, and the reaction raw material was experimented at 550 ° C using bunker C oil, and the reaction temperature was fixed for 2 hours. Proceeded.
  • the pyrolysis reaction was carried out in the same manner as in Example 1 except that the reaction raw material in Example 1 was used as a vacuum residue instead of bunker C oil and the reaction temperature is 650 °C.
  • the pyrolysis reaction system is a self-contained fluidized bed reactor, which is composed of a reactor, a reactor, and a product recovery system.
  • a piston pump connected to the HPLC pump was used for the metered feed, thermal fluid was used to drive the piston and nitrogen was used as the fluidizing gas.
  • thermal fluid was used to drive the piston
  • nitrogen was used as the fluidizing gas.
  • bed material sand with an average particle size of 230 ⁇ m was used, and the bed layer had a height of 20 cm.
  • the feed of the raw material into the reactor used a nozzle made in-house (FIG. 4).
  • the nozzle is internally mixed and has a double tube shape, and heavy oil flowing through the internal input tube is injected into the reactor by mixing with steam at the end of the input tube.
  • the temperature gradient inside the reactor was recorded by measuring the feed inlet (bottom reactor), reactor center, reactor top, and gas phase temperatures using a four-point thermocouple.
  • CCD camera was installed to observe the flow inside the reactor in real time.
  • a filter made of sus mesh was attached to the gas outlet to prevent outflow of sand as a bed material. The reaction was started after confirming that the sand flow was sufficient, and 80 g of raw material was supplied per batch.
  • a multi-step condensation process is used to recover the liquid product, using a Y-shaped condenser consisting of two condensers maintained at 80 ° C and -5 ° C, respectively, to recover the heavy fraction first and not to be collected in the Y-condenser.
  • the oil droplets were agglomerated and recovered through an electric current collector, which is a secondary condenser, and finally passed through a liquid nitrogen trap to condense residual oil.
  • Non-condensable gases were collected in Yedlar Bag.
  • Bunker C oil was used as a starting material and the reaction was performed at 550 ° C. for 40 minutes using a dispersed catalyst. At this time, the catalyst was used as ferrocene 1000ppm relative to the total weight of the reaction raw material based on Fe metal.
  • Reaction was carried out by using a vacuum residue instead of bunker C oil of Example 3, and the vacuum residue was boiled by maintaining the temperature of the feeder and the input line at 200 °C in consideration of the absence of flowability at room temperature. It did not have to be fluid.
  • the yield of the product was measured by subtracting the amount of water used as steam from the weight of the recovered liquid without using a condenser.
  • Water and pyrolysis oil were separated by means of a separatory funnel to remove water and then analyzed for oil.
  • the amount of coke was calculated by sampling a part of the sand on which coke was deposited and calcining at 750 ° C. for 4 hours to measure the remaining amount of coke.
  • the gas yield was estimated by subtracting the liquid yield and the amount of coke from the weight of the vacuum residue.
  • Example 5 Dispersion Catalytic Pyrolysis Using a Fluidized Bed Reactor
  • the pyrolysis reaction was carried out in the same manner as in Example 4 except that no dispersion catalyst was used.
  • the pyrolysis reaction was carried out in the same manner as in Example 4 except that the reaction temperature was performed at 650 ° C. instead of 550 ° C. and no dispersion catalyst was used.
  • Example 2 and Comparative Example 2 The yields of the pyrolysis products obtained in Example 2 and Comparative Example 2 are shown in FIG. 1 and in the pyrolysis of the vacuum residue, when the dispersion catalyst was used, the liquid yield improved about 16% compared to the pyrolysis without the catalyst.
  • the vacuum residue heavy catalysts containing a very high molecular weight contained a lot of heavy catalysts, which led to a rapid pyrolysis reaction rate, thereby preventing excessive pyrolysis.
  • the API specific gravity of the liquid product oil was measured at 20 ° and 18 ° respectively in the non-catalytic pyrolysis and pyrolysis using the dispersed catalyst, which is related to the yield of the liquid product oil. It is judged that the liquid oil has been recovered.
  • FIG. 5 shows oil recovery rates of the pyrolysis reaction products carried out in Examples 4 and 5, Comparative Example 3 and Comparative Example 4.
  • FIG. 5 shows oil recovery rates of the pyrolysis reaction products carried out in Examples 4 and 5, Comparative Example 3 and Comparative Example 4.
  • the liquid yield and gas yield were 52.4% and 31.6% at 550 ° C, respectively, compared to 22.5% and 63.8% at 600 ° C.
  • the gas yields were 65.4% and 22.0%, respectively, and the recoveries were 48.3% and 42.5% at 650 ° C.
  • Example 7 The olefin / paraffin ratio in the pyrolysis gas produced in Example 5 and Comparative Example 4 is shown in FIG. 7, and it was found that the olefin content was high in the case of the non-catalyst. This means that the reaction proceeded by a different mechanism from the non-catalytic pyrolysis when using the dispersed catalyst, and it can be seen that when the dispersed catalyst is used, the storage stability can be high due to the low olefin content.

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Abstract

The present invention is a method for converting heavy hydrocarbon resources into light crude oil using a dispersed catalyst. A method for catalytic cracking of heavy hydrocarbon resources according to the present invention has advantages of obtaining, with low costs, high quality light crude oil having excellent storability.

Description

중질 탄소원의 촉매 열분해 방법Catalytic Pyrolysis of Heavy Carbon Sources
본 발명은 중질 탄소원의 열분해 방법에 관한 것으로 보다 상세하게는 촉매를 이용하여 중질 탄소원을 열분해하여 높은 질의 경질 원유를 얻기 위한 방법에 관한 것이다.The present invention relates to a pyrolysis method of a heavy carbon source, and more particularly, to a method for obtaining high quality light crude oil by pyrolyzing a heavy carbon source using a catalyst.
원유를 구분하는 방법은 여러 가지가 있는데, 그 대표적인 것이 API 비중에 따라 구분하는 것이다. API를 기준으로 원유를 구분할 때는 경질 원유, 중질 원유로 크게 나눌 수 있으며, 더욱 세분하여 초경질원유, 경질원유, 중질원유, 초중질원유로 세분화하기도 하나 원유를 경질원유와 중질원유로 크게 구분할 때 대개 API 비중이 35이상인 것은 경질 원유, 35이하인 것은 중질 원유로 구분한다.There are many ways to classify crude oil, and the representative one is based on API weight. When classifying crude oil based on API, it can be divided into light crude oil and heavy crude oil.It is further subdivided into ultra light crude oil, light crude oil, heavy crude oil and ultra heavy crude oil. Generally, APIs with a weight of 35 or more are classified as light crude oil and those with a weight less than 35 are heavy crude oil.
원유의 채유량이 점차 높아짐에 따라 원유의 품질은 나빠지고 있는 반면 경질 원유에 대한 수요는 계속 증가하고 있다. 이에 따라 저품질 공급원료 즉, 중질 탄소원으로부터 경질 원유를 생산하는 공정에 대한 관심이 커지고 있다.As crude oil production increases, the quality of crude oil is deteriorating, while the demand for light crude oil continues to increase. Accordingly, there is a growing interest in a process for producing light crude oil, that is, light crude oil from a heavy carbon source.
현재 널리 사용되고 있는 경질 원유를 대체할 수 있는 중질 탄소원으로는 감압잔사유, 오일정제잔유, 중유, 폐윤활유, 천연 역청, 역청 또는 이들을 포함하는 모래, 벙커-C유, 고형바이오매스 및 석탄 등이 있다.Heavy carbon sources that can replace light crude oil currently in use include vacuum residue oil, refined residual oil, heavy oil, spent lubricating oil, natural bitumen, bitumen or sand containing them, bunker-C oil, solid biomass and coal. have.
일반적으로 중질 탄소원들이 공통적으로 가지고 있는 문제점으로는, 높은 점도, 높은 금속 함유, 높은 유황성분함유, 높은 유기산 농도 등이다. 높은 점도는 이들 내에 함유된 아스팔텐 성분에 기인하는 것으로 알려져 있으며 이송에 심각한 문제를 야기하기 때문에 점도를 낮추기 위하여 점도가 낮은 경질유(희석제)를 첨가하거나, 탄화수소 분해 반응을 통하여 경질화하여 점도를 낮추는 기술이 사용되고 있다. 이러한 희석제를 사용하는 방법은 고가의 경질유를 사용하기 때문에 비경제적이여서 유정에서 직접 부분 경질화하여 점도를 낮추는 기술 개발이 활발히 진행되고 있다.Generally, problems that heavy carbon sources have in common include high viscosity, high metal content, high sulfur content, and high organic acid concentration. The high viscosity is known to be due to the asphaltenes contained in them, which causes serious problems in transport, so that a low viscosity light oil (diluent) can be added to lower the viscosity, or hardened through hydrocarbon decomposition to lower the viscosity. Technology is being used. Since the method using such a diluent uses expensive light oil, it is uneconomical, and the technology of lowering the viscosity by partially hardening directly in an oil well is being actively developed.
한편 분해 반응을 통한 경질화 기술로는 coking공정, 유동층 촉매분해공정(fluid catalytic cracking)와 같이 열분해를 통하여 원유에서 카본을 제거하는 공정 기술과 수소 첨가를 통한, 수소개질 더 나아가 수첨분해공정이 주류를 이루고 있다. 유동층 촉매분해 공정(FCC공정)은 산촉매를 사용하여 분해반응을 촉진시키는 기술이지만, 중질원유와 같이 황성분이 높거나 금속성분 함량이 높거나 혹은 유기산(CCR)함량이 높은 원유에 대해서는 촉매의 빠른 비활성으로 인해 적용이 불가능한 것으로 알려져 있다. On the other hand, the hardening technology through cracking reaction is a process that removes carbon from crude oil through pyrolysis, such as coking process and fluid catalytic cracking process, and hydrogenation, hydrogenation, and hydrogenation process through hydrogenation. To achieve. The fluidized bed catalytic cracking process (FCC process) promotes the decomposition reaction using an acid catalyst, but the catalyst quickly deactivates a crude oil having a high sulfur content, a high metal content, or a high organic acid (CCR) content such as heavy crude oil. It is known that it is not applicable.
이를 극복하기 위하여 단순한 고온 열분해 반응을 통하여 원유를 분해하는 기술이 소개되고 있다. 일례로 미국공개특허 제 7572362에서는 카본을 제거하는 공정 중의 하나인 열분해 공정을 개시하고 있다. 이 열분해 공정은 열분해 반응 시 촉매의 관여 없이 고온의 샌드를 이용하여 급속가열 분해하는 방식으로 촉매를 사용하지 않는 공정이기 때문에 상대적으로 반응속도가 느려서 많은 양의 열공급 매체(샌드)를 순환하여야하는 단점이 있다.In order to overcome this problem, a technique of decomposing crude oil through a simple high temperature pyrolysis reaction has been introduced. For example, U.S. Patent No. 7572362 discloses a pyrolysis process which is one of processes for removing carbon. This pyrolysis process is a process that does not use a catalyst by rapid thermal decomposition using a high temperature sand without involvement of the catalyst during the pyrolysis reaction, so the reaction rate is relatively slow and a large amount of heat supply medium (sand) must be circulated. There is this.
따라서 이러한 종래의 단점을 해결하기위하여 본 발명은 종래의 중질 탄소원에 촉매를 적용하였을 때 코킹등으로 인해 촉매가 비활성화되는 문제점을 극복하고자 중질 탄소원에 적용하여도 비활성화가 되지 않는 분산형 촉매를 제공한다. Therefore, in order to solve the above disadvantages, the present invention provides a dispersed catalyst that is not deactivated even when applied to a heavy carbon source in order to overcome the problem that the catalyst is inactivated due to caulking, etc. when the catalyst is applied to the conventional heavy carbon source. .
즉, 중질 탄소원에 열분해 시에도 비활성화가 되지 않는 분산형 촉매를 사용하여 열분해 반응을 촉진시켜 경질 원유를 높은 생산량과 저 비용으로 얻을 수 있는 중질 탄소원의 촉매 열분해 방법을 제공한다.In other words, the present invention provides a catalytic pyrolysis method of a heavy carbon source capable of obtaining light crude oil at high yield and low cost by promoting a pyrolysis reaction using a dispersed catalyst that is not deactivated even when pyrolysis is performed on the heavy carbon source.
또한 본 발명은 중질 탄소원을 분산형 촉매를 이용하여 아스팔텐의 성분을 선택적으로 분해하며 올레핀 함량이 낮아 저장안정성이 높은 고품질의 경질 원유로 전환할 수 있는 중질 탄소원의 촉매 열분해 방법을 제공한다.The present invention also provides a method for catalytic pyrolysis of heavy carbon sources that can selectively convert the components of asphaltene using a dispersed catalyst and convert them into high quality light crude oil having high storage stability due to low olefin content.
본 발명은 분산형 촉매를 사용하여 중질 탄소원을 열분해 하는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법이다.The present invention is a catalytic pyrolysis method of a heavy carbon source, characterized by pyrolyzing a heavy carbon source using a dispersed catalyst.
상술한 바와 같이, 본 발명은 중질 탄소원을 열분해하여 경질 원유를 제조하는 방법에 관한 것으로, 본 발명은 중질 탄소원의 열분해시, 촉매를 이용한 촉매 열분해 방법인 특징이 있으며, 보다 특징적으로 분산형 촉매를 사용하여 고품질의 경질 원유를 낮은 비용으로 단시간 내에 대량 생산할 수 있는 방법이다. As described above, the present invention relates to a method for producing light crude oil by pyrolyzing a heavy carbon source, the present invention is characterized in that the catalytic pyrolysis method using a catalyst in the thermal decomposition of the heavy carbon source, and more particularly to a dispersed catalyst It is a method that can mass produce high quality light crude oil at low cost in a short time.
본 발명에서의 중질 탄소원(heavy carbonaceous materials)은 카본 제거 또는 수소 첨가를 이용하여 경질 원유로의 개질에 통상적으로 사용되는 탄소원을 의미하는데 감압잔사유, 오일정제잔유, 중유, 폐윤활유, 천연 역청, 역청 또는 이들을 포함하는 모래, 벙커-C유, 고형바이오매스 및 석탄을 포함한다.Heavy carbonaceous materials (heavy carbonaceous materials) in the present invention means a carbon source commonly used for the reforming of light crude oil using carbon removal or hydrogenation, such as vacuum residue, oil refinery residue, heavy oil, waste lubricant, natural bitumen, Bitumen or sand, bunker-C oils, solid biomass and coal comprising them.
중질 탄소원을 경질 원유로 개질하는 방법에는 일반적으로 카본을 제거하는 공정 기술과 수소 첨가를 통한 공정 기술로 나누어 질 수 있으며 본 발명에 따른 분산형 촉매를 사용하는 촉매 열분해 방법은 카본을 제거하여 경질화하는 공정을 의미하며 이러한 공정에는 coking이나 FCC와 같은 공정들이 있다.The method of reforming a heavy carbon source into light crude oil is generally divided into a process technology for removing carbon and a process technology through hydrogenation. The catalytic pyrolysis method using a dispersed catalyst according to the present invention is hardened by removing carbon. These processes include processes such as coking and FCC.
분산형 촉매는 반응 원료인 중질 탄소원에 용해되거나 균일하게 혼합되어 분산될 수 있는 형태의 촉매를 나타낸다. Dispersion type catalyst refers to a type of catalyst that can be dissolved or uniformly dispersed in a heavy carbon source as a reaction raw material.
이러한 분산형 촉매는 일반적으로 유용성 촉매 및 수용성 촉매로 나타낼 수 있으나 이에 한정이 있는 것은 아니며 또한 고체입자촉매도 이에 포함될 수 있다. 유용성 촉매는 나프테네이트(naphthenate), 레지네이트(resinate), 옥토에이트(octoate) 등과 같은 금속염 유기산(metal salts of organic acids) 계열 및 유기금속(organometalic compounds) 화합물 계열 등 중질 탄소원에 용해될 수 있는 금속 화합물을 나타낸다. 수용성 촉매는 1개 이상의 금속 원소가 포함하고 있으며 물에 용해될 수 있는 금속 화합물을 나타낸다. 고체입자촉매는 1개 이상의 금속 원소가 포함되어 있으며 용액 중에서 고체상으로 존재하는 입자를 나타내며, 금속입자, 금속황화합물, 금속산화물, 금속수산화물 등을 포함한다.Such dispersed catalysts may generally be represented as oil-soluble catalysts and water-soluble catalysts, but are not limited thereto. Solid particle catalysts may also be included therein. Oil-soluble catalysts are soluble in heavy carbon sources, such as metal salts of organic acids and organometalic compounds, such as naphthenate, resinate, and octoate. Metal compound is shown. A water soluble catalyst refers to a metal compound that contains one or more metal elements and can be dissolved in water. The solid particle catalyst includes one or more metal elements and represents particles in a solid phase in a solution, and includes metal particles, metal sulfur compounds, metal oxides, metal hydroxides, and the like.
본 발명에 따른 분산형 촉매는 한정이 있는 것은 아니나 ⅠA족 금속, ⅡB족 금속, ⅢA족 금속, ⅣA족 금속, ⅤA족 금속, ⅥA족 금속, ⅦA족 금속, ⅤⅢ A족, ⅠB족 금속, ⅢB족 금속, Si, Ge 및 염화물, 황산화물, 질산화물 또는 이들의 혼합물 및 이들의 유기 착체 중에서 선택될 수 있으며 보다 바람직하게 ⅠA족 금속은 Li 또는 K이며, ⅡB족 금속은 Mg 또는 Ca이며, ⅢA족 금속은 Sc, Y, La 또는 Ac에서 선택되며 ⅣA족 금속은 Ti, Zr 또는 Hf에서 선택되며 ⅤA족 금속은 V 또는 Nb이며 ⅥA족 금속은 Cr, Mo 또는 W에서 선택되며 ⅦA족 금속은 Mn이며 ⅤⅢ A족 금속은 Fe, Co, Ni, Ru, Rh, Pd, Os, Ir 또는 Pt에서 선택되며ⅠB족 금속은 Cu이며, ⅢB족 금속은 B, Al, Ga 또는 In에서 선택될 수 있다.The dispersing catalyst according to the present invention is not limited, but is not limited to Group IA metals, Group IIB metals, Group IIIA metals, Group IVA metals, Group VA metals, Group VIA metals, Group VIIA metals, Group VIII A, Group IB metals, and IIIB. Group metals, Si, Ge and chlorides, sulfur oxides, nitrates or mixtures thereof and organic complexes thereof, more preferably Group IA metal is Li or K, Group IIB metal is Mg or Ca, Group IIIA The metal is selected from Sc, Y, La or Ac, the Group IVA metal is selected from Ti, Zr or Hf, the Group VA metal is selected from V or Nb, the Group VIA metal is selected from Cr, Mo or W and the Group VIIA metal is Mn The Group VIII metal is selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir or Pt, the Group IB metal is Cu, and the Group IIIB metal may be selected from B, Al, Ga or In.
또한 상기 유기 착체의 바람직한 예로는 [Fe(CO)5] (펜타카르보닐철), [Fe(Cp)2] (페로센 또는 비스(시클로펜타디에닐철)), [Fe(acac)3] (트리아세틸아세톤산철), [Mo(CO)6] (헥사카르보닐몰리브덴), [Mo(C5H5)(CO)3]2 (시클로펜타디에닐트리카르보닐몰리브덴 이량체), [Mo(알릴)4] (테트라알릴몰리브덴), [W(CO)6] (헥사카르보닐텅스텐), [W(C6H6)2](비스(벤젠)텅스텐), [W(But)3] (트리부틸텅스텐), [W(알릴)4] (테트라알릴텅스텐), [Ni(CO)4] (테트라카르보닐니켈),[Ni(Cp)2] (니켈로센 또는 비스(시클로펜타디에닐)니켈), [Ni(CH3C5H4)2] (비스(메틸시클로펜타디에닐)니켈), [Cr(CO)6] (헥사카르보닐크롬), [Cr(C5H5)(CO)3]2 (시클로펜타디에닐트리카르보닐크롬 이량체), [C6H6Cr(CO)3] (페닐트리카르보닐크롬), [Cr(C6H6)2] (비스(벤젠)크롬), [Cu(acac)2] (디아세틸아세톤산구리), [Cu(hfacac)2] (비스(헥사플루오로아세틸아세톤산)구리), [Co2(CO)8] (옥타카르보닐이코발트), [Pd(알릴)Cp] (알릴 시클로펜타디에닐팔라듐), [Pt(CH3)2(COD)] (디메틸 시클로옥타디엔 백금), [Ru(CO)5] (펜타카르보닐루테늄), [RuCp2] (루테노센)을 들 수 있으나 이에 한정이 있는 것은 아니다.Further preferred examples of the organic complex include [Fe (CO) 5 ] (pentacarbonyl iron), [Fe (Cp) 2 ] (ferrocene or bis (cyclopentadienyl iron)), [Fe (acac) 3 ] (tree Acetylacetonate), [Mo (CO) 6 ] (hexacarbonylmolybdenum), [Mo (C 5 H 5 ) (CO) 3 ] 2 (cyclopentadienyltricarbonylmolybdenum dimer), [Mo (allyl ) 4 ] (tetraallyl molybdenum), [W (CO) 6 ] (hexacarbonyl tungsten), [W (C 6 H 6 ) 2 ] (bis (benzene) tungsten), [W (But) 3 ] (tri Butyl tungsten), [W (allyl) 4 ] (tetraallyl tungsten), [Ni (CO) 4 ] (tetracarbonylnickel), [Ni (Cp) 2 ] (nickelene or bis (cyclopentadienyl) Nickel), [Ni (CH 3 C 5 H 4 ) 2 ] (bis (methylcyclopentadienyl) nickel), [Cr (CO) 6 ] (hexacarbonylchrome), [Cr (C 5 H 5 ) ( CO) 3 ] 2 (cyclopentadienyltricarbonylchrome dimer), [C 6 H 6 Cr (CO) 3 ] (phenyltricarbonylchrome), [Cr (C 6 H 6 ) 2 ] (bis ( benzene) chromium), [Cu (acac) 2 ] ( diacetyl acetoxy Acid copper), [Cu (hfacac) 2 ] ( bis (hexafluoro-acetylacetone acid) copper), [Co 2 (CO) 8] ( octahydro-carbonyl cobalt), [Pd (allyl) Cp] (allyl-cyclohexane Pentadienylpalladium), [Pt (CH 3 ) 2 (COD)] (dimethyl cyclooctadiene platinum), [Ru (CO) 5 ] (pentacarbonylruthenium), [RuCp 2 ] (ruthenocene) However, this is not a limitation.
또한 본 발명의 중질 탄소원의 촉매 열분해 방법에 따른 중질 탄소원은 감압잔사유, 오일정제잔유, 중유, 천연 역청, 역청; 또는 감압잔사유, 오일정제잔유, 중유, 천연 역청 및 역청에서 선택되는 하나 이상의 물질을 포함하는 모래; 벙커-C유, 고형바이오매스 및 석탄에서 선택되는 하나 또는 둘이상의 혼합물에서 선택될 수 있다.In addition, the heavy carbon source according to the catalytic pyrolysis method of the heavy carbon source of the present invention is a vacuum residue, oil refined residue, heavy oil, natural bitumen, bitumen; Or sand comprising at least one substance selected from vacuum residue, oil refined residue, heavy oil, natural bitumen and bitumen; It may be selected from one or more mixtures selected from bunker-C oil, solid biomass and coal.
본 발명의 중질 탄소원의 촉매 열분해 방법은, 먼저 분산형 촉매를 중질 탄소원과 혼합하는 단계, 상기 단계의 혼합물을 열분해하는 단계 및 상기 단계에서 생성된 생성물을 회수하는 단계를 포함한다.The catalytic pyrolysis method of the heavy carbon source of the present invention first comprises mixing the dispersed catalyst with the heavy carbon source, pyrolyzing the mixture of the step and recovering the product produced in the step.
상기 분산형 촉매는 중질 탄소원 총 중량에 대하여 분산형 촉매의 금속원자가 10 ~ 10000ppm일 수 있다. 사용되는 분산형 촉매의 금속원자가 10ppm이하이면 충분한 촉매의 활성을 나타내지 못하며 10000ppm이상이며 경제적으로 비효율적이다. 보다 바람직하게는 중질 탄소원 총 중량에 대하여 분산형 촉매의 금속원자가 100 ~ 500ppm일 수 있다.The dispersed catalyst may have a metal atom of 10 to 10000 ppm of the dispersed catalyst based on the total weight of the heavy carbon source. If the metal atom of the dispersed catalyst used is less than 10ppm does not exhibit sufficient catalyst activity, it is more than 10000ppm and economically inefficient. More preferably, the metal atom of the dispersed catalyst may be 100 to 500 ppm based on the total weight of the heavy carbon source.
또한 상기 분산형 촉매를 중질 탄소원과 혼합하는 단계에서 열분해 하기 전의 전처리 과정으로 분산형 촉매와 중질 탄소원이 충분히 혼합하여 열분해 효과를 높이기 위해 교반하는 단계를 더 수행할 수 있다.In addition, the pre-treatment process before the thermal decomposition in the step of mixing the dispersed catalyst with the heavy carbon source may be further carried out a step of mixing the dispersed catalyst and the heavy carbon source sufficiently to increase the thermal decomposition effect.
상기 교반은 100 ~ 200℃의 온도에서 수행될 수 있다.The stirring may be performed at a temperature of 100 ~ 200 ℃.
상기 분산형 촉매의 열분해는 300 ~ 800℃에서 진행될 수 있으며 300℃보다 낮은 경우 충분한 분해가 나타나지 않을 수 있으며 800℃이상에서는 오버크래킹이 일어나 가스생성물의 수율이 높아져 질이 높은 경질 원유로의 전환이 효과적이지 못하다.Pyrolysis of the dispersed catalyst may proceed at 300 ~ 800 ℃ and if it is lower than 300 ℃ may not appear enough decomposition and over cracking occurs at 800 ℃ or higher to increase the yield of the gas product is converted to high-quality light crude oil Not effective
보다 바람직하게 열분해는 450 ~ 750℃에서 진행될 수 있다.More preferably pyrolysis may proceed at 450 ~ 750 ℃.
본 발명의 회수는 분해 생성물의 액체나 기체에 따라 적절한 장치와 방법에 의해 회수 될 수 있으며 통상의 기술자에 의해 가능한 변형 또한 가능하다.The recovery of the present invention can be recovered by any suitable apparatus and method depending on the liquid or gas of the decomposition product, and modifications possible by those skilled in the art are also possible.
본 발명에 따른 중질 탄소원의 촉매 열분해 방법은 아스팔텐의 성분을 선택적으로 분해하고 분해유 중의 아로마틱 함량과 올레핀 함량은 낮추어 저장안정도가 향상된 고품질의 경질 원유를 얻을 수 있다.The catalytic pyrolysis method of the heavy carbon source according to the present invention can selectively decompose the components of asphaltenes and lower the aromatic content and the olefin content in the cracked oil to obtain high quality light crude oil having improved storage stability.
또한 본 발명에 따른 중질 탄소원의 촉매 열분해 방법은 분산형 촉매를 이용하여 열분해 속도를 촉진시키고 열분해 반응 온도를 낮출 수 있어 비용절감의 효과를 얻을 수 있는 장점이 있다.In addition, the catalytic pyrolysis method of the heavy carbon source according to the present invention has the advantage that it is possible to promote the pyrolysis rate and lower the pyrolysis reaction temperature by using a dispersed catalyst to obtain a cost reduction effect.
도 1은 실시예 2와 비교예 2에서 얻은 열분해 생성물의 수율을 비교한 그래프이며1 is a graph comparing the yield of pyrolysis products obtained in Example 2 and Comparative Example 2
도 2는 실시예 2에서 얻은 열분해 액체 생성유의 SARA 분석을 나타낸 그래프이며,2 is a graph showing a SARA analysis of the pyrolysis liquid generating oil obtained in Example 2,
도 3은 비교예 2에서 얻은 열분해 액체 생성유의 SARA 분석을 나타낸 그래프이며,3 is a graph showing a SARA analysis of pyrolysis liquid generating oil obtained in Comparative Example 2,
도 4는 자체 제작한 내부 혼합형 VR 주입 노즐 구조를 나타낸 것이며,4 shows a self-manufactured internal mixed VR injection nozzle structure,
도 5는 실시예 4, 실시예 5, 비교예 3 및 비교예 4에서 얻은 열분해 생성물의 회수율을 나타낸 그래프이며,5 is a graph showing a recovery rate of the pyrolysis products obtained in Examples 4, 5, Comparative Example 3 and Comparative Example 4,
도 6는 반응온도에 따른 기체 조성 변화를 나타낸 그래프이며,6 is a graph showing the change in gas composition according to the reaction temperature,
도 7은 실시예 5와 비교예 4에 열분해 반응으로 얻은 생성물중 가스 내의 올레핀과 파라핀비율을 나타낸 그래프이다.7 is a graph showing the olefin and paraffin ratio in the gas in the product obtained by the pyrolysis reaction in Example 5 and Comparative Example 4.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
열분해 실험에서 얻은 액체 생성유의 품질을 알아보기 위하여 API비중을 측정하고 SARA분석을 실시하였다. API비중은 Anton Parr사의 DMA 4500 장비로 측정하였으며 SARA분석은 TLC- FID 장치를 사용하여 분석하였고 열분해 생성물중 기체 생성물의 조성은 GC/FID(Agilent 6890, column HP AL/KCL (30m × 0.53mm × 15㎛)로 측정하였다.API specific gravity was measured and SARA analysis was performed to investigate the quality of the liquid product oil obtained in the pyrolysis experiment. The API specificity was measured by Anton Parr's DMA 4500 equipment. SARA analysis was carried out using a TLC-FID apparatus. 15 μm).
[실시예1] 고정층 반응기를 이용한 분산형 촉매 열분해Example 1 Distributed Catalytic Pyrolysis Using a Fixed Bed Reactor
실험에 사용된 고정층 열분해 반응 시스템은 반응원료의 공급 장치, 고정층 반응기 그리고 생성물의 회수 시스템으로 구성되어 있다. 반응 원료의 공급 장치는 온도를 150℃이상으로 유지하여 정량 공급이 가능하도록 하였으며, 실험에 사용된 반응기는 연속식 고정층 반응기로 반응온도를 일정하게 유지하기 위하여 반응기 중앙에 sus bead를 장입하고 열분해가 진행되도록 하였다. 열분해된 생성물의 원활한 흐름과 무산소 상태를 유지하기 위하여 질소를 반응물과 함께 공급하였으며, 열분해의 체류시간을 조절하여 과잉 열분해를 방지하도록 하였다. 또한 열분해된 생성물의 회수를 위하여 온도가 다른 2단의 콘덴서를 장착하였으며, 전단과 후단의 콘덴서 온도는 각각 80℃와 -5℃로 하였다. 콘덴서에서 회수되지 않은 경질 원유를 회수하기 위하여 시스템 후단에 액체 질소 트랩을 설치하여 액상 생성물을 최대한 회수하였으며, 비응축성 가스의 분석을 위하여 액체 질소 트랩 전후단에서 가스를 포집하였다.The fixed bed pyrolysis reaction system used in the experiment consists of a feedstock feeder, a fixed bed reactor and a product recovery system. The feeder of the reaction raw material was able to maintain the temperature above 150 ℃ to quantitatively supply, the reactor used in the experiment is a continuous fixed bed reactor to load a sus bead in the center of the reactor to maintain a constant reaction temperature and pyrolysis It was made to proceed. In order to maintain a smooth flow of the pyrolyzed product and to maintain an anoxic state, nitrogen was supplied together with the reactants, and the residence time of the pyrolysis was controlled to prevent excessive pyrolysis. In order to recover the thermally decomposed product, two stages of condenser having different temperatures were mounted, and the temperature of the condenser in the front and rear stages was 80 ° C and -5 ° C, respectively. In order to recover the light crude oil not recovered from the condenser, a liquid nitrogen trap was installed at the rear of the system to recover the liquid product as much as possible, and gas was collected at the front and rear of the liquid nitrogen trap for the analysis of the non-condensable gas.
먼저 분산형 촉매와 반응물의 혼합을 위하여 150℃의 온도에서 충분히 교반하였다. 이때 사용된 촉매는 페로센으로 중질 탄소원인 반응원료 총중량에 대하여페로센의 Fe 금속 기준으로 1000ppm으로 사용하였으며 반응원료는 벙커 C유를 사용하여 550℃에서 실험을 진행하였으며 반응온도를 고정한 상태에서 2시간 동안 진행하였다.First, the mixture was sufficiently stirred at a temperature of 150 ° C. for mixing the dispersed catalyst and the reactant. At this time, the catalyst used was ferrocene, which is 1000ppm based on the Fe metal of ferrocene with respect to the total weight of the reaction raw material, which is a heavy carbon source, and the reaction raw material was experimented at 550 ° C using bunker C oil, and the reaction temperature was fixed for 2 hours. Proceeded.
[실시예2] 고정층 반응기를 이용한 분산형 촉매 열분해 Example 2 Distributed Catalytic Pyrolysis Using a Fixed Bed Reactor
실시예 1에서 반응원료를 벙커 C유 대신 감압잔사유를 사용하고 반응 온도가 650℃인 것을 제외하고는 실시예 1과 동일하게 열분해 반응을 실시하였다.The pyrolysis reaction was carried out in the same manner as in Example 1 except that the reaction raw material in Example 1 was used as a vacuum residue instead of bunker C oil and the reaction temperature is 650 ℃.
[비교예 1]Comparative Example 1
실시예 1에서 페로센촉매를 사용하지 않은 것을 제외하고 실시예 1과 동일하게 열분해반응을 실시하였다.Pyrolysis was carried out in the same manner as in Example 1 except that the ferrocene catalyst was not used in Example 1.
[비교예 2]Comparative Example 2
실시예 2에서 페로센 촉매를 사용하지 않은 것을 제외하고 실시예 2와 동일하게 열분해반응을 실시하였다.Pyrolysis was carried out in the same manner as in Example 2 except that the ferrocene catalyst was not used in Example 2.
[실시예 3] 유동층 반응기를 이용한 분산형 촉매 열분해Example 3 Distributed Catalytic Pyrolysis Using a Fluidized Bed Reactor
열분해 반응 시스템은 자체 제작한 것으로 유동층 반응기로서 크게 반응 원료 및 유동화 가스의 공급 장치, 반응기 그리고 생성물의 회수 시스템으로 구성되어 있다.The pyrolysis reaction system is a self-contained fluidized bed reactor, which is composed of a reactor, a reactor, and a product recovery system.
정량 공급을 위하여 HPLC 펌프와 연결된 피스톤 펌프를 사용하였으며, 열매체유를 사용하여 피스톤을 구동하였으며 질소를 유동화 가스로 사용하였다. Bed material로는 평균 입도 230 ㎛의 모래를 사용하였고, bed 층의 높이는 20㎝이다. A piston pump connected to the HPLC pump was used for the metered feed, thermal fluid was used to drive the piston and nitrogen was used as the fluidizing gas. As the bed material, sand with an average particle size of 230 µm was used, and the bed layer had a height of 20 cm.
원료의 반응기 내 공급은 자체 제작한 노즐(도4)을 이용하였다. 노즐은 내부 혼합형으로서 이중관 형태로 되어 있으며 내부 투입관을 통하여 흐르는 중질유가 투입관 말단에서 스팀과 혼합하여 반응기 내로 분사된다.The feed of the raw material into the reactor used a nozzle made in-house (FIG. 4). The nozzle is internally mixed and has a double tube shape, and heavy oil flowing through the internal input tube is injected into the reactor by mixing with steam at the end of the input tube.
네 지점의 측정점을 갖는 thermocouple을 사용하여 원료 주입부(반응기 하부), 반응기 중심, 반응기 상단, 기체상 온도를 각각 측정함으로써 반응기 내부의 온도 구배를 기록하였다. The temperature gradient inside the reactor was recorded by measuring the feed inlet (bottom reactor), reactor center, reactor top, and gas phase temperatures using a four-point thermocouple.
반응기 내부의 유동을 실시간으로 관찰하고자 CCD카메라를 설치하였다.CCD camera was installed to observe the flow inside the reactor in real time.
가스 outlet에 sus mesh로 제작한 필터를 부착하여 bed material인 모래의 유출이 이루어지지 않도록 하였다. 모래의 유동이 충분히 이루어지는 것을 확인한 다음 반응을 개시하였으며 매 회분당 80g의 원료를 공급하였다.A filter made of sus mesh was attached to the gas outlet to prevent outflow of sand as a bed material. The reaction was started after confirming that the sand flow was sufficient, and 80 g of raw material was supplied per batch.
액체 생성물의 회수를 위하여 다단계의 응축 과정을 거치는데, 각각 80℃와 -5℃로 유지되는 두 개의 컨덴서로 구성된 Y자 형태의 응축기를 사용하여 중질 분획을 우선 회수하고 Y자 응축기에서 포집되지 않는 오일 액적은 2차 응축기인 전기집전기를 통과하여 응집, 회수하였으며, 최종적으로 액체 질소 트랩을 통과하여 잔여 오일을 응축할 수 있도록 하였다. 비응축성 가스는 Yedlar Bag으로 포집하였다. A multi-step condensation process is used to recover the liquid product, using a Y-shaped condenser consisting of two condensers maintained at 80 ° C and -5 ° C, respectively, to recover the heavy fraction first and not to be collected in the Y-condenser. The oil droplets were agglomerated and recovered through an electric current collector, which is a secondary condenser, and finally passed through a liquid nitrogen trap to condense residual oil. Non-condensable gases were collected in Yedlar Bag.
원료물질로는 벙커 C유를 사용하였으며 분산형 촉매를 사용하여 550℃에서 40분 동안 반응을 진행하였다. 이때 사용된 촉매는 페로센으로 Fe 금속 기준으로 반응원료 총중량에 대하여 1000ppm을 사용하였다. Bunker C oil was used as a starting material and the reaction was performed at 550 ° C. for 40 minutes using a dispersed catalyst. At this time, the catalyst was used as ferrocene 1000ppm relative to the total weight of the reaction raw material based on Fe metal.
[실시예 4] 유동층 반응기를 이용한 분산형 촉매 열분해Example 4 Dispersion Catalytic Pyrolysis Using a Fluidized Bed Reactor
실시예 3의 벙커 C유 대신 감압잔사유를 사용하여 반응을 진행하였으며 감압잔사유의 경우 상온에서의 흐름성이 없음을 감안하여 feeder 및 투입라인의 온도를 200℃로 유지함으로써 감압잔사유가 비등하지 않으면서 유동성을 가지도록 하였다. Reaction was carried out by using a vacuum residue instead of bunker C oil of Example 3, and the vacuum residue was boiled by maintaining the temperature of the feeder and the input line at 200 ℃ in consideration of the absence of flowability at room temperature. It did not have to be fluid.
원료물질로 감압잔사유를 사용한 관계로 반응 생성물의 회수에 있어서 응축이 용이한 스팀으로 대체하였다. 즉 반응기 하부에 스팀 제너레이트를 장착하여 스팀을 공급하였다. 기체의 반응기 내 체류시간이 1.5초가 되도록 스팀의 유량을 조절하였다. 그 외의 반응조건은 실시예 3와 동일하게 진행하였다. Due to the use of vacuum residue as a raw material, it was replaced by steam which facilitated condensation in the recovery of the reaction product. That is, the steam was supplied to the bottom of the reactor by supplying steam. The flow rate of steam was adjusted so that the residence time of the gas in the reactor was 1.5 seconds. Other reaction conditions were performed in the same manner as in Example 3.
또한 스팀을 유동화가스로 사용하였기 때문에 생성물의 회수 시 벙커 C유와는 달리 콘덴서를 사용하지 않고 회수된 액체의 무게에서 스팀으로 사용된 물의 양을 빼서 액체 수율을 측정하였다. 분별 깔때기로 물과 열분해 오일을 층분리하여 물을 제거한 다음 오일에 대한 분석을 수행하였다. 반응 종료 후 코크가 침적된 모래 중 일부를 샘플링하고 750℃에서 4시간 동안 소성하여 강열잔량을 측정함으로써 코크의 양을 계산하였다. 기체 수율은 투입된 감압잔사유 무게에서 액체 수율과 코크량을 빼서 추산하였다.In addition, since steam was used as the fluidizing gas, unlike bunker C oil, the yield of the product was measured by subtracting the amount of water used as steam from the weight of the recovered liquid without using a condenser. Water and pyrolysis oil were separated by means of a separatory funnel to remove water and then analyzed for oil. After completion of the reaction, the amount of coke was calculated by sampling a part of the sand on which coke was deposited and calcining at 750 ° C. for 4 hours to measure the remaining amount of coke. The gas yield was estimated by subtracting the liquid yield and the amount of coke from the weight of the vacuum residue.
[실시예 5] 유동층 반응기를 이용한 분산형 촉매 열분해Example 5 Dispersion Catalytic Pyrolysis Using a Fluidized Bed Reactor
반응온도가 600℃인 것을 제외하고 실시예 4와 동일하게 열분해반응을 실시하였다.Pyrolysis was carried out in the same manner as in Example 4 except that the reaction temperature was 600 ° C.
[비교예 3]Comparative Example 3
분산형 촉매를 사용하지 않은 것을 제외하고 실시예 4와 동일하게 열분해 반응을 실시하였다.The pyrolysis reaction was carried out in the same manner as in Example 4 except that no dispersion catalyst was used.
[비교예 4][Comparative Example 4]
반응온도를 550℃ 대신 650℃에서 진행하고 분산형 촉매을 사용하지 않은 것을 제외하고 실시예 4와 동일하게 열분해 반응을 실시하였다.The pyrolysis reaction was carried out in the same manner as in Example 4 except that the reaction temperature was performed at 650 ° C. instead of 550 ° C. and no dispersion catalyst was used.
실시예 2와 비교예 2에서 얻은 열분해 생성물의 수율을 도 1에 나타내었으며 감압잔사유의 열분해에서는 분산형 촉매를 사용하였을 경우에 촉매를 사용하지 않은 열분해에 비해 약 16%정도의 액체 수율 향상 효과를 관찰할 수 있었다. 감압잔사유의 경우 분자량이 매우 큰 중질유분을 많이 함유하고 있기 때문에 분산형 촉매의 투입은 빠른 열분해 반응 속도를 유도하여 과도한 열분해를 방지하였으며 이러한 효과로 인하여 액체 생성유의 수율을 향상시키는 것으로 판단된다.The yields of the pyrolysis products obtained in Example 2 and Comparative Example 2 are shown in FIG. 1 and in the pyrolysis of the vacuum residue, when the dispersion catalyst was used, the liquid yield improved about 16% compared to the pyrolysis without the catalyst. Could be observed. In the case of the vacuum residue, heavy catalysts containing a very high molecular weight contained a lot of heavy catalysts, which led to a rapid pyrolysis reaction rate, thereby preventing excessive pyrolysis.
또한 열분해 실험에서 회수된 액체 생성유의 품질을 알아보기 위하여 API비중을 측정하였으며 그 결과를 표 1에 나타내었다.In addition, the API specific gravity was measured to determine the quality of the liquid product oil recovered in the pyrolysis experiment, and the results are shown in Table 1.
표 1
무촉매 분산형 촉매
API 비중 20.01 18.03
SARA 분석(wt%) saturated 3.27 5.88
aromatics 82.30 68.59
resins 11.78 24.78
asphaltenes 2.65 0.75
Table 1
No catalyst Dispersed catalyst
API weight 20.01 18.03
SARA analysis (wt%) saturated 3.27 5.88
aromatics 82.30 68.59
resins 11.78 24.78
asphaltenes 2.65 0.75
액체 생성유의 API 비중은 무촉매 열분해와 분산형 촉매을 사용한 열분해에서 각각 20°과 18°정도로 측정되었으며, 이는 액체 생성유의 수율과 관계있는 것으로 무촉매 열분해에서는 과도한 열분해가 진행되어 경질 유분을 많이 함유하는 액체 생성유가 회수된 것으로 판단된다. The API specific gravity of the liquid product oil was measured at 20 ° and 18 ° respectively in the non-catalytic pyrolysis and pyrolysis using the dispersed catalyst, which is related to the yield of the liquid product oil. It is judged that the liquid oil has been recovered.
또한 액체 생성유의 품질을 알아보기 위하여 SARA분석을 실시하였으며 그 결과를 도 2와 도3에 나타내었다. 도 2와 도3에 나타난 바와 같이 무촉매 열분해의 경우 다환 방향족인 아스팔텐이 2.65wt%인 것에 반해 분산형 촉매의 경우 0.75wt%로 매우 적은 것을 알 수 있으며 분산형 촉매의 경우 아로마틱 성분이 줄고 resins성분이 증가된 것을 확인할 수 있었다. 즉, 이러한 결과로 분산형 촉매는 상대적으로 분자량이 큰 물질의 열분해에 효과적으로 작용하는 것으로 나타나며 원유의 품질을 그대로 유지하면서 액체 생성유의 수율을 최대화 할 수 있는 것을 알 수 있다.In addition, SARA analysis was performed to determine the quality of the liquid product oil, and the results are shown in FIGS. 2 and 3. As shown in FIG. 2 and FIG. 3, in the case of non-catalytic pyrolysis, the polycyclic aromatic asphaltenes are 2.65 wt%, whereas the dispersion catalysts are very small at 0.75 wt%, and the aromatic catalysts are reduced in the dispersion catalysts. It was confirmed that the resins component was increased. In other words, it can be seen that the dispersed catalyst effectively acts on the pyrolysis of a relatively high molecular weight material and can maximize the yield of liquid oil while maintaining the quality of crude oil.
실시예 4와 실시예 5 및 비교예 3과 비교예 4에서 실시한 열분해 반응 생성물의 오일 회수율을 도 5에 나타내었다. 도 5에서 보이는 바와 같이 온도가 높을수록 액체 수율과 코크 수율이 줄어든 대신 기체 수율이 증가함을 알 수 있다. 특히 분산형 촉매 사용 시에는 이러한 현상이 두드러져 550℃에서는 액체 수율과 기체 수율이 각각 52.4%와 31.6%인데 비하여 600℃에서는 22.5%와 63.8%을 나타났으며 무촉매 열분해에서는 550℃에서 액체 수율과 기체 수율이 각각 65.4%와 22.0%이었고 650℃의 경우 48.3%와 42.5%의 회수율을 나타내었다. 이러한 결과는 촉매가 열분해 반응을 촉진하여 기체 생성물이 대량 발생하였음을 알 수 있다.5 shows oil recovery rates of the pyrolysis reaction products carried out in Examples 4 and 5, Comparative Example 3 and Comparative Example 4. FIG. As shown in FIG. 5, the higher the temperature, the lower the liquid yield and the coke yield. This is especially the case with dispersed catalysts. The liquid yield and gas yield were 52.4% and 31.6% at 550 ° C, respectively, compared to 22.5% and 63.8% at 600 ° C. The gas yields were 65.4% and 22.0%, respectively, and the recoveries were 48.3% and 42.5% at 650 ° C. These results show that the catalyst promotes the pyrolysis reaction and a large amount of gaseous products are generated.
또한 열분해 가스 조성을 분석한 결과를 도 6에 나타내었으며 도 6에 나타난 바와 같이 반응 온도가 높아질수록 메탄의 함량이 낮아지는 대신 C2와 C3기체의 함량이 늘어난 것을 알 수 있으며 이는 가스 상에서의 overcracking으로 인한 현상으로 판단되어진다.In addition, the results of analyzing the pyrolysis gas composition are shown in FIG. 6, and as shown in FIG. 6, it can be seen that as the reaction temperature is increased, the contents of C 2 and C 3 gas increase instead of the content of methane decreases, which is caused by overcracking in the gas phase. It is considered a phenomenon.
도 5와 도 6의 결과로 분산형 촉매를 사용하면 낮은 온도에서 열분해하여 단시간에 고품질의 경질 원유를 얻을 수 있음을 알 수 있다.As a result of FIG. 5 and FIG. 6, it can be seen that when the dispersed catalyst is used, high-quality light crude oil can be obtained in a short time by pyrolysis at low temperature.
실시예 5와 비교예 4에서 생성된 열분해 가스 내 올레핀/파라핀 비율을 도 7에 도시하였으며 무촉매의 경우 올레핀 함량이 높은 것으로 나타났다. 이는 분산형 촉매를 사용할 경우 무촉매 열분해와 다른 기작으로 반응이 진행되었음을 의미하며 분산형 촉매를 사용한 경우 올레핀 함량이 낮아 저장안정성이 높은 장점을 가질 수 있음을 알 수 있다.The olefin / paraffin ratio in the pyrolysis gas produced in Example 5 and Comparative Example 4 is shown in FIG. 7, and it was found that the olefin content was high in the case of the non-catalyst. This means that the reaction proceeded by a different mechanism from the non-catalytic pyrolysis when using the dispersed catalyst, and it can be seen that when the dispersed catalyst is used, the storage stability can be high due to the low olefin content.

Claims (8)

  1. 분산형 촉매를 사용하여 중질 탄소원을 열분해 하는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법.A catalytic pyrolysis method for a heavy carbon source, characterized in that the heavy carbon source is pyrolyzed using a dispersed catalyst.
  2. 제 1항에 있어서,The method of claim 1,
    분산형 촉매는 유용성 촉매, 수용성 촉매 또는 고체입자촉매인 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법.The dispersed catalyst is a catalyst for pyrolysis of a heavy carbon source, characterized in that the oil-soluble catalyst, the water-soluble catalyst or the solid particle catalyst.
  3. 제 1항에 있어서,The method of claim 1,
    분산형 촉매는 ⅠA족 금속, ⅡB족 금속, ⅢA족 금속, ⅣA족 금속, ⅤA족 금속, ⅥA족 금속, ⅦA족 금속, ⅤⅢ A족, ⅠB족 금속, ⅢB족 금속, Si, Ge 및 염화물, 황산화물, 질산화물 또는 이들의 혼합물 및 이들의 유기 착체중에서 선택되는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법. Disperse catalysts include Group IA metals, Group IIB metals, Group IIIA metals, Group IVA metals, Group VA metals, Group VIA metals, Group VIII metals, Group VIII A metals, Group IB metals, Group IIIB metals, Si, Ge and chlorides, A process for catalytic pyrolysis of heavy carbon sources, characterized in that it is selected from sulfur oxides, nitric oxides or mixtures thereof and organic complexes thereof.
  4. 제 3항에 있어서,The method of claim 3,
    ⅠA족 금속은 Li 또는 K이며, ⅡB족 금속은 Mg 또는 Ca이며, ⅢA족 금속은 Sc, Y, La 또는 Ac에서 선택되며, ⅣA족 금속은 Ti, Zr 또는 Hf에서 선택되며, ⅤA족 금속은 V 또는 Nb이며, ⅥA족 금속은 Cr, Mo 또는 W에서 선택되며, ⅦA족 금속은 Mn이며, ⅤⅢ A족 금속은 Fe, Co, Ni, Ru, Rh, Pd, Os, Ir 또는 Pt에서 선택되며,ⅠB족 금속은 Cu이며, ⅢB족 금속은 B, Al, Ga 또는 In에서 선택되는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법.Group IA metal is Li or K, Group IIB metal is Mg or Ca, Group IIIA metal is selected from Sc, Y, La or Ac, Group IVA metal is selected from Ti, Zr or Hf, and Group VA metal is V or Nb, Group VIA metal is selected from Cr, Mo or W, Group VIIA metal is Mn, Group VIII A metal is selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir or Pt And the Group IB metal is Cu and the Group IIIB metal is selected from B, Al, Ga or In.
  5. 제 3항에 있어서,The method of claim 3,
    유기 착체는 [Fe(CO)5] (펜타카르보닐철), [Fe(Cp)2] (페로센 또는 비스(시클로펜타디에닐철)), [Fe(acac)3] (트리아세틸아세톤산철), [Mo(CO)6] (헥사카르보닐몰리브덴), [Mo(C5H5)(CO)3]2 (시클로펜타디에닐트리카르보닐몰리브덴 이량체), [Mo(알릴)4] (테트라알릴몰리브덴), [W(CO)6] (헥사카르보닐텅스텐), [W(C6H6)2](비스(벤젠)텅스텐), [W(But)3] (트리부틸텅스텐), [W(알릴)4] (테트라알릴텅스텐), [Ni(CO)4] (테트라카르보닐니켈),[Ni(Cp)2] (니켈로센 또는 비스(시클로펜타디에닐)니켈), [Ni(CH3C5H4)2] (비스(메틸시클로펜타디에닐)니켈), [Cr(CO)6] (헥사카르보닐크롬), [Cr(C5H5)(CO)3]2 (시클로펜타디에닐트리카르보닐크롬 이량체), [C6H6Cr(CO)3] (페닐트리카르보닐크롬), [Cr(C6H6)2] (비스(벤젠)크롬), [Cu(acac)2] (디아세틸아세톤산구리), [Cu(hfacac)2] (비스(헥사플루오로아세틸아세톤산)구리), [Co2(CO)8] (옥타카르보닐이코발트), [Pd(알릴)Cp] (알릴 시클로펜타디에닐팔라듐), [Pt(CH3)2(COD)] (디메틸 시클로옥타디엔 백금), [Ru(CO)5] (펜타카르보닐루테늄) 및 [RuCp2] (루테노센) 로부터 선택되는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법.The organic complex is [Fe (CO) 5 ] (pentacarbonyl iron), [Fe (Cp) 2 ] (ferrocene or bis (cyclopentadienyl iron)), [Fe (acac) 3 ] (triacetylacetonate), [Mo (CO) 6 ] (hexacarbonylmolybdenum), [Mo (C 5 H 5 ) (CO) 3 ] 2 (cyclopentadienyltricarbonylmolybdenum dimer), [Mo (allyl) 4 ] (tetra Allyl molybdenum), [W (CO) 6 ] (hexacarbonyl tungsten), [W (C 6 H 6 ) 2 ] (bis (benzene) tungsten), [W (But) 3 ] (tributyl tungsten), [ W (allyl) 4 ] (tetraallyl tungsten), [Ni (CO) 4 ] (tetracarbonylnickel), [Ni (Cp) 2 ] (nicklocene or bis (cyclopentadienyl) nickel), [Ni (CH 3 C 5 H 4 ) 2 ] (bis (methylcyclopentadienyl) nickel), [Cr (CO) 6 ] (hexacarbonylchrome), [Cr (C 5 H 5 ) (CO) 3 ] 2 (Cyclopentadienyltricarbonylchrome dimer), [C 6 H 6 Cr (CO) 3 ] (phenyltricarbonylchrome), [Cr (C 6 H 6 ) 2 ] (bis (benzene) chrome), [Cu (acac) 2 ] (diacetylacetonate copper), [Cu (hfacac) 2 ] (bis (Hexafluoroacetylacetonic acid) copper), [Co 2 (CO) 8 ] (octacarbonyl isobalt), [Pd (allyl) Cp] (allyl cyclopentadienylpalladium), [Pt (CH 3 ) 2 (COD)] (dimethyl cyclooctadiene platinum), [Ru (CO) 5 ] (pentacarbonylruthenium) and [RuCp 2 ] (ruthenocene).
  6. 제 1항에 있어서,The method of claim 1,
    중질 탄소원은 감압잔사유, 오일정제잔유, 중유, 폐윤활유, 천연 역청, 역청 또는 이들을 포함하는 모래, 벙커-C유, 고형바이오매스 및 석탄에서 선택되는 하나 또는 둘이상 선택되는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법.The heavy carbon source is one or more selected from the group consisting of vacuum residue oil, refined residual oil, heavy oil, spent lubricating oil, natural bitumen, bitumen or sand, bunker-C oil, solid biomass and coal containing them. Catalytic Pyrolysis of Carbon Sources.
  7. 제 1항에 있어서,The method of claim 1,
    분산형 촉매는 중질 탄소원 총 중량에 대하여 분산형 촉매의 금속원자가 10 ~ 10000ppm으로 포함되는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법.The dispersed catalyst is a catalytic pyrolysis method of a heavy carbon source, characterized in that 10 to 10000ppm metal atoms of the dispersed catalyst relative to the total weight of the heavy carbon source.
  8. 제 1항에 있어서,The method of claim 1,
    열분해는 300 ~ 800℃에서 진행되는 것을 특징으로 하는 중질 탄소원의 촉매 열분해 방법.Pyrolysis is a catalytic pyrolysis method of a heavy carbon source, characterized in that proceeds at 300 ~ 800 ℃.
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