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WO2012058218A2 - Procédé de production d'une huile de pyrolyse de grande qualité à partir d'une biomasse - Google Patents

Procédé de production d'une huile de pyrolyse de grande qualité à partir d'une biomasse Download PDF

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Publication number
WO2012058218A2
WO2012058218A2 PCT/US2011/057697 US2011057697W WO2012058218A2 WO 2012058218 A2 WO2012058218 A2 WO 2012058218A2 US 2011057697 W US2011057697 W US 2011057697W WO 2012058218 A2 WO2012058218 A2 WO 2012058218A2
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WO
WIPO (PCT)
Prior art keywords
reactor
pyrolysis
psia
torrefaction
ranging
Prior art date
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Ceased
Application number
PCT/US2011/057697
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English (en)
Other versions
WO2012058218A3 (fr
Inventor
Daren Einar Daugaard
Kening Gong
Alexandru Platon
Samuel T. Jones
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ConocoPhillips Co
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ConocoPhillips Co
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 ConocoPhillips Co filed Critical ConocoPhillips Co
Publication of WO2012058218A2 publication Critical patent/WO2012058218A2/fr
Publication of WO2012058218A3 publication Critical patent/WO2012058218A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
    • C10C5/00—Production of pyroligneous acid distillation of wood, dry distillation of organic waste
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2
    • C07C29/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2 by hydration of carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/02—Multi-step carbonising or coking processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/083—Torrefaction
    • 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
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • 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
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203—Naphthenic acids, TAN
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates generally to the conversion of biomass to fuel range hydrocarbons.
  • Biomass is any carbon containing material derived from living or formerly living organisms, such as wood, wood waste, crops, crop waste, waste, and animal waste.
  • Pyrolysis is the chemical decomposition of organic materials by heating in the absence of oxygen or other reagents. Pyrolysis can be used to convert biomass (such as lignocellulosic biomass) into pyrolysis oil or so-called bio-oil. The bio-oils obtained by pyrolysis of biomass or waste have received attention recently as an alternative source of fuel.
  • biomass produces four primary products, namely water, “bio-oil,” also known as “pyrolysis oil,” char, and various gases (H 2 , CO, C0 2 , CH 4 , and other light hydrocarbons) that do not condense, except under extreme conditions.
  • bio-oil also known as “pyrolysis oil”
  • char various gases (H 2 , CO, C0 2 , CH 4 , and other light hydrocarbons) that do not condense, except under extreme conditions.
  • gases H 2 , CO, C0 2 , CH 4 , and other light hydrocarbons
  • Fast pyrolysis is one method for the conversion of biomass to bio-oil.
  • Fast pyrolysis is the rapid thermal decomposition of organic compounds in the absence of atmospheric or added oxygen to produce liquids, char, and gas.
  • Fast pyrolysis affords operation at atmospheric pressure, moderate temperatures, and with low or no water usage.
  • Pyrolysis oil yields typically range from 50-75% mass of input biomass and are heavily feedstock dependent.
  • pyrolysis oil obtained from biomass fast pyrolysis process is chemical complex compounds comprising generally a mixture of water, light volatiles, and non-volatiles. They are in general of relatively low quality. As fuels they have a number of negative properties such as high acidity (lead to corrosion problem), substantial water content (usually in the range of 15% to 30%>), variable viscosity, low heating values (about half that of the diesel fuel), low cetane number, etc. These negative properties are related to the oxygenated compounds contained in bio-oils that result in a 45% oxygen content. In general, the pyrolysis oil has total acidity number (TAN) value of approximately 100. The desired TAN value for transportation fuel is less than 10.
  • TAN total acidity number
  • this invention discloses a process for producing high quality pyrolysis oil from biomass by utilizing a torrefaction pretreatment step for biomass pyrolysis process wherein the pretreatment step improves the quality of the pyrolysis oil by reducing acidity.
  • the disclosed process comprises at least the following steps: a) a step of subjecting a biomass feedstock to a thermal treatment in a reactor A under a torrefaction reaction condition to produce an torrefied biomass feedstock; and b) a step of pyrolyzing the torrefied biomass feedstock in a reactor B under a pyrolysis reaction condition to form a pyrolysis oil product.
  • the torrefaction reaction condition includes a temperature ranging from 180°C to 350°C, a pressure ranging from atmospheric pressure to 500 psia, (but optionally, ranging as low as 0.1 psia) and a residence time ranging from 1 minute to 24 hours.
  • the pyrolysis reaction condition includes a temperature ranging from 375°C to 700°C, a pressure ranging from vacuum conditions (0.1 psia) to 1000 psia., and a residence time ranging from 0.1 to 200 seconds.
  • the pyrolysis oil product according to the current invention has a TAN number between 80 and 200.
  • Embodiments of the invention relate to a process to utilize a torrefaction pretreatment step for biomass pyrolysis process.
  • This pretreatment improves the quality of the pyrolysis oil by reducing acidity.
  • the inventive process shows that as a pretreatment to pyrolysis, resulting pyrolysis oil obtained from torrefied biomass has approximately 25% lower acetic acid than that from untorrefied biomass pyrolysis oil.
  • biomass includes any renewable source (living or formerly living), but does not include oil, natural gas, and/or petroleum. Biomass thus includes but is not limited to wood, paper, crops, animal and plant fats, biological waste, algae, and the like.
  • a step of subjecting a biomass feedstock to a thermal treatment in a reactor under a torrefaction reaction condition to produce a torrefied biomass feedstock there is disclosed a step of subjecting a biomass feedstock to a thermal treatment in a reactor under a torrefaction reaction condition to produce a torrefied biomass feedstock.
  • Torrefaction consists of a slow heating of biomass feedstock in an inert atmosphere to produce a solid with lower hemicellulose content, higher energy density, nearly moisture free ( ⁇ 3 wt%), and low resistance to fracture (brittle).
  • Any standard torrefaction reactor can be used to torrefy the biomass feedstock.
  • Exemplary reactor configurations include without limitations augers reactor, ablative reactor, rotating cones reactor, fluidized-bed reactor, entrained-flow reactor, vacuum moving-bed reactor, transported-bed reactor, and fixed-bed reactor.
  • any standard torrefaction reaction condition can be used to torrefy the biomass feedstock in the torrefaction reactor.
  • a person skilled in the art can readily select a combination of temperature, pressure, and residence time that produces a torrefied product.
  • the torrefaction reaction conditions include a temperature ranging from 180°C to 350°C, a pressure ranging from atmospheric pressure to 500 psia, and a residence time ranging from 1 minute to 24 hours.
  • the torrefaction reaction conditions include a temperature ranging from 220°C to 280°C, a pressure ranging from 11 psia to 30 psia, and a residence time ranging from 5 to 20 minutes.
  • the torrefaction reaction conditions include a temperature ranging from 180°C to 350°C, a pressure ranging from 0.1 psia to 500 psia, and a residence time ranging from 1 minute to 24 hours.
  • torrefaction is carried out in the presence of a catalyst material selected from a group consisting solid acid catalyst such as ZSM5, solid base catalyst such as Hydrotalcite, silica catalyst such as Diatomite, silica-alumina catalyst such as Kaolin, Group B metal oxide catalyst such as Ammonium Molybdate, pyrolytic char and any combination thereof.
  • a catalyst material selected from a group consisting solid acid catalyst such as ZSM5, solid base catalyst such as Hydrotalcite, silica catalyst such as Diatomite, silica-alumina catalyst such as Kaolin, Group B metal oxide catalyst such as Ammonium Molybdate, pyrolytic char and any combination thereof.
  • the torrefaction reaction is carried out in the absence of diatomic oxygen in an inert gas atmosphere such as nitrogen, argon, steam, carbon oxides, etc.
  • the torrefaction reaction is carried out in a reducing gas atmosphere that comprises carbon monoxide.
  • torrefaction may be carried out with other reactants such as hydrogen
  • the torrefied biomass according to various embodiments of the invention may be added to a pyrolysis reactor for further processing.
  • the torrefied biomass is pyrolyzed in a pyrolysis reactor under pyrolysis reaction conditions to form a pyrolysis oil product.
  • Pyrolysis which is the thermal decomposition of a substance into its elemental components and/or smaller molecules, is used in various methods developed for producing hydrocarbons, including but not limited to hydrocarbon fuels, from biomass. Pyrolysis requires moderate temperatures, generally greater than about 325°C, such that the feed material is sufficiently decomposed to produce products which may be used as hydrocarbon building blocks.
  • Embodiments of the inventive process use any standard pyrolysis reactor providing sufficient heat to pyrolyze torrefied biomass feedstock, including without limitation, auger reactor, ablative reactor, a bubbling fluidized bed reactor, circulating fluidized beds/transport reactor, rotating cone pyrolyzer, vacuum pyrolyzer, and the like.
  • any standard pyrolysis reaction condition can be used to pyrolyze the torrefied biomass feedstock in a pyrolysis reactor.
  • a person skilled in the art can readily select a combination of temperature, pressure, and residence time that produces a pyrolyzed product.
  • the pyrolysis reaction condition includes a temperature ranging from 375°C to 700°C, a pressure ranging from vacuum conditions of 0.1 psia up to 1000 psia., and a residence time ranging from 0.1 to 200 seconds.
  • the pyrolysis reaction condition includes a temperature ranging from 425°C to 525°C, a pressure ranging from atmospheric pressure to 300 psia., and a residence time ranging from 0.5 to 2 seconds.
  • a variety of catalysts may be used for the pyrolysis reaction.
  • the pyrolysis reaction is carried out in the presence of a catalyst material selected from a group consisting of solid acid catalyst such as ZSM5, solid base catalyst such as Hydrotalcite, silica catalyst such as Diatomite, silica-alumina catalyst such as Kaolin, Group B metal oxide catalyst such as Ammonium Molybdate, pyrolytic char and any combination thereof.
  • a catalyst material selected from a group consisting of solid acid catalyst such as ZSM5, solid base catalyst such as Hydrotalcite, silica catalyst such as Diatomite, silica-alumina catalyst such as Kaolin, Group B metal oxide catalyst such as Ammonium Molybdate, pyrolytic char and any combination thereof.
  • the pyrolysis oil product obtained according to some embodiments of the present invention has a TAN number between 80 and 200.
  • the pyrolysis oil product obtained according to some other embodiments of the present invention has a TAN number between less than 20 and 50.
  • the pyrolysis oil obtained from biomass fast pyrolysis process is of relatively low quality.
  • pyrolysis oil has TAN value of approximately 100.
  • the desired TAN value for transportation fuel is less than 10.
  • the step of pretreatment of torrefaction can be easily integrated with the pyrolysis step.
  • the pretreatment step improves the quality of the feed quality of pyrolysis step and therefore results in higher quality of pyrolysis oil product including low TAN value.
  • such integrated process reduces the operating cost and capital investment of post treatment process.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

La présente invention concerne un procédé utilisant une étape de prétraitement de torréfaction pour un procédé de pyrolyse de biomasse. Ce prétraitement améliore la qualité de l'huile de pyrolyse grâce à la réduction de son acidité. Le procédé de l'invention qui consiste en un traitement préalable avant pyrolyse permet d'obtenir, à partir d'une biomasse torréfiée, une huile de pyrolyse contenant 25 % d'acide acétique en moins qu'une huile de pyrolyse obtenue à partir d'une biomasse non torréfiée.
PCT/US2011/057697 2010-10-29 2011-10-25 Procédé de production d'une huile de pyrolyse de grande qualité à partir d'une biomasse Ceased WO2012058218A2 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US40799410P 2010-10-29 2010-10-29
US61/407,994 2010-10-29
US13/280,982 2011-10-25
US13/280,982 US20120108860A1 (en) 2010-10-29 2011-10-25 Process for producing high quality pyrolysis oil from biomass

Publications (2)

Publication Number Publication Date
WO2012058218A2 true WO2012058218A2 (fr) 2012-05-03
WO2012058218A3 WO2012058218A3 (fr) 2012-06-21

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US (1) US20120108860A1 (fr)
WO (1) WO2012058218A2 (fr)

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CN104479766A (zh) * 2014-12-17 2015-04-01 河南理工大学 一锅法制备藻类绿色柴油的新方法
WO2015196841A1 (fr) * 2014-06-24 2015-12-30 华南农业大学 Procédé de pyrolyse et de carbonisation continue d'une biomasse d'origine agricole et forestière
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WO2015196841A1 (fr) * 2014-06-24 2015-12-30 华南农业大学 Procédé de pyrolyse et de carbonisation continue d'une biomasse d'origine agricole et forestière
US10253263B2 (en) 2014-06-24 2019-04-09 South China Agricultural University Method of continuous pyrolysis and carbonization of agricultural and forestry biomass
CN104263390A (zh) * 2014-09-22 2015-01-07 中国水产科学研究院南海水产研究所 一种海藻与水生外来入侵植物协同微波热解多联产利用的方法
CN104479766A (zh) * 2014-12-17 2015-04-01 河南理工大学 一锅法制备藻类绿色柴油的新方法
WO2016190759A1 (fr) * 2015-05-25 2016-12-01 23 Rs Coras Sp Z O.O. Procédé de transformation catalytique de déchets de graisses en combustibles liquides
WO2017099495A1 (fr) * 2015-12-08 2017-06-15 연세대학교 원주산학협력단 Procédé de production de bio-huile à l'aide d'un procédé de torréfaction et de pyrolyse rapide
KR101772165B1 (ko) * 2015-12-08 2017-08-28 연세대학교 원주산학협력단 반탄화 및 급속열분해 공정을 이용한 바이오오일 제조방법
KR20180079148A (ko) * 2016-12-30 2018-07-10 대한민국(산림청 국립산림과학원장) 바이오 오일 제조를 위한 전처리 일체형 반응기
KR101887028B1 (ko) * 2016-12-30 2018-08-10 대한민국 바이오 오일 제조를 위한 전처리 일체형 반응기

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