WO2012108584A1 - Method of manufacturing environment-friendly biobunker c oil having low sulfur content using palm oil byproduct - Google Patents

Method of manufacturing environment-friendly biobunker c oil having low sulfur content using palm oil byproduct Download PDF

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Publication number
WO2012108584A1
WO2012108584A1 PCT/KR2011/003106 KR2011003106W WO2012108584A1 WO 2012108584 A1 WO2012108584 A1 WO 2012108584A1 KR 2011003106 W KR2011003106 W KR 2011003106W WO 2012108584 A1 WO2012108584 A1 WO 2012108584A1
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Prior art keywords
palm oil
byproduct
oil
oil byproduct
palm
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PCT/KR2011/003106
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French (fr)
Inventor
Seung Han Woo
Kwang Jin Ha
Cheon Pyo Hong
Mi Nam Lee
Eun Hee Lee
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Deokbun Co., Ltd
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Publication of WO2012108584A1 publication Critical patent/WO2012108584A1/en

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B3/00—Refining fats or fatty oils
    • C11B3/001—Refining fats or fatty oils by a combination of two or more of the means hereafter
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • 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, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B1/00—Production of fats or fatty oils from raw materials
    • C11B1/02—Pretreatment
    • C11B1/04—Pretreatment of vegetable raw material
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • 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
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the present invention relates to a method of manufacturing an environment-friendly biobunker C oil having low sulfur content using a palm oil byproduct, and in particular, to a method of manufacturing an environment-friendly biobunker C oil having low sulfur content in which the method includes: adding an organic solvent to a palm oil byproduct that remains after palm oil is refined from a palm fruit so as to dissolve the palm oil byproduct; bring the dissolved palm oil byproduct in contact with a water removing agent to remove water; centrifuging the palm oil byproduct to remove impurities and removing the organic solvent, thereby completing manufacture of a refined palm oil byproduct; and mixing the refined palm oil byproduct and bunker C oil, thereby completing manufacture of a biobunker C oil, and an environment-friendly biobunker C oil having low sulfur content manufactured by using the method.
  • Palm oil is produced in a great quantity for use in various applications, including food.
  • palm oil is obtained from fruits of fresh oil palm trees ( Elaeis guineensis ).
  • a palm tree produces about one fruit bunch having about 3,000 fruits every month. Palm trees, in general, continuously produce fruits for 25 years, and the continuous production guarantees good supply of palm oil.
  • palm oil In palm oil, a content of palmitic acid, which is a saturated fatty acid, is relatively high and a content of unsaturated fatty acid is relatively low. Thus, palm oil is not easily acidified and long-term preservation thereof is possible. Also, palm oil contains high contents of carotene, and tocotrienol and tocopherol which constitute vitamin E and thus, is nutritionally excellent.
  • Palm oil methyl ester produced from palm oil, that is, palm diesel. Palm oil is converted into palm oil methyl ester through transesterification. Since the palm oil methyl ester has excellent fuel characteristics, it can be used as an alternative to diesel.
  • Palm which is a raw material of a palm oil byproduct, is an economically important crop that provides timber, fuel, building materials, fiber, starch, oil, liquor, etc.
  • palm is used to produce palm raw oil, palm kernel oil, etc.
  • Byproducts obtained from palm are solid at room temperature and thus, are inappropriate as a fuel.
  • the byproducts contain high contents of impurities.
  • the present invention is results of research for selecting an optimal solvent in association with removal of a non-oil component from a solid palm oil byproduct that is produced during a manufacturing process for palm oil, reviewing extraction performance of a solvent, and improving fluidity through mixing with heavy oil.
  • Korean Patent Publication No. 2010-0110331 discloses a method of manufacturing a palm oil product
  • Korean Patent Publication No. 2010-0118865 discloses a method of manufacturing environmental-friendly bio-charcoal using a biomass byproduct.
  • Bunker C oil which is usually used in an industrial boiler, has a high caloric value of 9,900 kcal/kg but its sulfur content is as high as 0.3 to 4.0%, thereby causing pollution problems and limiting its use.
  • the inventors of the present invention searched for a material that is partially alternatively used instead of bunker C oil having the problem as described above, and manufactured an environment-friendly biobunker C oil having low sulfur content by producing a refined palm oil byproduct by refining a palm oil byproduct generated during a manufacturing process for palm oil by using an appropriate solvent and mixing the refined palm oil byproduct with bunker C oil, wherein the refined palm oil byproduct has a calorific value of 9,020 kcal/kg, which is slightly lower than that of bunker C oil, has a very low sulfur content of 0.01%, and is cheaper than bunker C oil.
  • a method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes manufacturing a refined palm oil byproduct by adding an organic solvent and a water removing agent to a palm oil byproduct remaining after palm oil is refined from a palm fruit, and mixing the refined palm oil byproduct with bunker C oil.
  • an environment-friendly biobunker C oil having low sulfur content manufactured by using the method.
  • An environment-friendly biobunker C oil having low sulfur content according to the present invention has a calorific value, similar to that of bunker C oil, and low sulfur content. Accordingly, the environment-friendly biobunker C oil having low sulfur content is an environment-friendly biofuel that may reduce environmental pollution. Also, the environment-friendly biobunker C oil having low sulfur content is cheaper than bunker C oil, and thus, it is expected that the environment-friendly biobunker C oil having low sulfur content may be used as an alternative to bunker C oil in the industrial boiler market.
  • FIG. 1 is a schematic view illustrating a production process for a conventional palm oil byproduct and a production process for a refined palm oil byproduct according to the present invention: a): a production process for a palm oil byproduct, and b): a production process for a refined palm oil byproduct.
  • FIG. 2 shows images of a palm oil byproduct and a refined palm oil byproduct according to the present invention: a) palm oil byproduct (20°C), b) palm oil byproduct (60°C), and c) refined palm oil byproduct.
  • FIG. 3 shows analysis results of elements contained in a conventional palm oil byproduct and a refined palm oil byproduct according to the present invention.
  • FIG. 4 shows graphs of amounts of solvents and petroleum required to dissolve a palm oil byproduct (1 g): a) a required amount with respect to a solvent, and b) a required amount with respect to petroleum.
  • FIG. 5 shows fluidity change of a palm oil byproduct with respect to an amount of bunker C oil used.
  • FIG. 6 shows a graph of a melting point of a palm oil byproduct with respect to an amount of hexane used.
  • a method of manufacturing an environment-friendly biobunker C oil having low sulfur content in which the method includes:
  • the method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a first phase, filtering a liquid palm oil byproduct prepared by heating a palm oil byproduct remaining after palm oil is refined from a palm fruit, so as to remove a solid material.
  • the palm oil byproduct refers to a solid byproduct remaining in a process of producing palm oil from a palm fruit.
  • the palm oil byproduct is half-solid at room temperature, and is liquid at a temperature of 60°C. So, the palm oil byproduct is heated to at a temperature of about 60°C to prepare a liquid state.
  • the liquid palm oil byproduct is filtered through a fiber filter to remove a solid material that is not dissolved.
  • a manufacturing process for palm oil is known in the art.
  • the method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a second phase, completely dissolving the palm oil byproduct by adding an organic solvent to the liquid palm oil byproduct from which the solid material is removed.
  • the solvent may be hexane, diethyl ether, dichloromethane, methanol, or acetone, but is not limited thereto.
  • the solvent may be hexane.
  • a solvent may be classified as a non-polar solvent, a polar protic solvent, and a polar aprotic solvent.
  • a non-polar solvent examples include pentane, hexane, diethyl ether, cyclohexane, benzene, and toluene.
  • a polar aprotic solvent examples include dichloromethane, ethyl acetate, acetone, and acetonitrile.
  • Examples of a polar protic solvent are methanol, ethanol, an acetic acid, and water.
  • separation capability is decreased in the following order of a non-polar solvent, a polar aprotic solvent, and a polar protic solvent.
  • dichloromethane is not appropriate due to generation of residual chloride, and diethyl ether may not be recovered due to its too low boiling point.
  • Benzene and toluene have high toxicity, and cyclohexane requires a great amount of energy during evaporation due to its high boiling point.
  • hexane is the most appropriate solvent.
  • the dissolving of the palm oil byproduct may be performed at a temperature of 25 to 35°C, for example, 30°C.
  • the dissolving temperature is not limited thereto.
  • the dissolving temperature may be in any temperature range in which hexane as a solvent is liquid and the palm oil byproduct as a solute is solid.
  • the dissolving temperature may be room temperature which does not require heating or a temperature slightly higher than room temperature, in consideration of energy use.
  • a dissolving time may be 0.5 to 1.5 hours, for example, 1 hour, but is not limited thereto. When the dissolving time is 30 minutes, 90% or more of the palm oil byproduct may be dissolved, and when the dissolving time is about 1 hour, the palm oil byproduct may be completely dissolved.
  • An amount of hexane used may be 35 to 55 mL based on 15 to 25 g of the palm oil byproduct, but is not limited thereto.
  • An amount of hexane that is appropriate for complete dissolution may be 2 mL or more based on 1 g of the palm oil byproduct. If the amount of hexane is less than 2 mL based on 1 g of the palm oil byproduct, a dissolution rate of the palm oil byproduct with respect to hexane is low. Accordingly, the amount of hexane may be 2 to 2.5 mL based on 1 g of the palm oil byproduct.
  • the method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a third phase, removing water from the dissolved palm oil byproduct by bring a water removing agent in contact with the dissolved palm oil byproduct, wherein the water removing agent may be anhydrous sodium sulfate (Na 2 SO 4 ), calcium sulfate (CaSO 4 ), calcium chloride (CaCl 2 ), silica powder, or clay powder.
  • the removing of water in the refining process is performed to prevent incomplete combustion of a fuel oil, and to remove hydrophilic impurities therefrom, in addition to water, thereby improving purity of a fuel oil.
  • the palm oil byproduct contains about 5% of hydrophilic part, and the percentage of hydrophilic part may be further decreased to 1% or less through the refining process.
  • the method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a fourth phase, removing impurities from the water-removed palm oil byproduct by centrifuging, and removing the organic solvent, thereby completing manufacture of a refined palm oil byproduct.
  • the evaporated organic solvent is collected and is used again in the second phase of dissolving of the palm oil byproduct, which is economically very efficient.
  • the method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a fifth phase, mixing the refined palm oil byproduct and bunker C oil, thereby completing manufacture of a biobunker C oil.
  • a mixed ratio of the refined palm oil byproduct to bunker C oil may be a weight ratio of 25 to 50:50 to 75, for example, 30 to 40:60 to 70, but is not limited thereto.
  • An amount of bunker C oil that is appropriate for complete dissolution of 1 g of the refined palm oil byproduct may be 1.1 mL or more. If the amount of bunker C oil is less than 1.1 ml, a solid material may remain and fluidity of the refined palm oil byproduct may be inappropriate.
  • an amount of bunker C oil used needs to be equal to or higher than 50 weight ratio with respect to the refined palm oil byproduct, and if the amount of bunker C oil is equal to or higher than 75 weight ratio with respect to the refined palm oil byproduct, the sulfur decrease effect may not be significantly low. Accordingly, the mixed ratio of the refined palm oil byproduct to bunker C oil as described above may be most appropriate.
  • an example of a method of manufacturing an environment-friendly biobunker C oil having low sulfur content according to the present invention may include:
  • the present invention provides an environment-friendly biobunker C oil having low sulfur content manufactured by using the method according to the present invention.
  • a biobunker C oil according to the present invention is manufactured by mixing a refined palm oil byproduct having relatively very low sulfur content with bunker C oil having relatively high sulfur content, and may be environment-friendly due to its lower sulfur content than bunker C oil.
  • the biobunker C oil according to the present invention may be used as an alternative to bunker C oil that is generally used as a fuel for industrial boilers.
  • the present invention provides an environment-friendly biobunker C oil having low sulfur content, wherein the environment-friendly biobunker C oil contains 1.0 parts by weight or less of water, 25 to 50 parts by weight of a refined palm oil byproduct from which a solid material is removed, and 50 to 75 parts by weight of bunker C oil.
  • the refined palm oil byproduct may contain 1.0 part by weight or less of water and may not contain a solid material.
  • a mixed weight ratio of the refined palm oil byproduct to the bunker C oil may be 25 to 50:50 to 75, for example 30 to 40:60 to 70, but is not limited thereto.
  • a palm oil byproduct was heated to a temperature of 60°C so as to obtain a liquid palm oil byproduct, and then, the liquid palm oil byproduct was poured onto a fiber filter and the fiber filter was squeezed.
  • a palm oil byproduct (20 g) was added to hexane (40 ml), and then, the mixture was stirred in a shaking incubator at a rate of 200 rpm, at a temperature of 30°C for 1 hour, and then completely dissolved by using a Vorltex mixer.
  • 1 g of anhydrous sodium sulfate (Na 2 SO 4 ) was added to the palm oil byproduct that was dissolved in hexane.
  • the palm oil byproduct which was dissolved in hexane and to which the anhydrous sodium sulfate was added was placed in 50 mL conical tube and then centrifuging was performed thereon at a rate of 4000 rpm for 5 minutes. Hexane as a solvent was removed by centrifuging from the refined solution from which impurities were removed, and collected, thereby completing manufacture of a refined palm oil byproduct (FIGS. 1 and 2).
  • FIG. 4 shows a graph of amounts of the solvents required to dissolve 1 g of the palm oil byproduct.
  • organic solvents dissolution effects were decreased in the following order of methanol (1.466 mL/g), dichloromethane (1.496 mL/g), and hexane (1.968 mL/g).
  • methanol and dichloromethane were not used since the resultant refined palm oil byproduct may have relatively low purity.
  • the inventors used hexane as a solvent.
  • bunker A oil (1.134 mL/g)
  • bunker B oil (1.185 mL/g
  • bunker C oil 1.096 mL/g
  • FIG. 5 is images for confirming fluidity of the palm oil byproduct with respect to bunker C oil. Referring to FIG. 5, the higher the amount of the bunker C oil, the higher the fluidity of the palm oil byproduct.
  • Example 5 Measuring of melting point of refined palm oil byproduct with respect to mixing with hexane
  • Example 6 Manufacturing of biobunker C oil through mixing of bunker C oil and refined palm oil byproduct
  • a refined palm oil byproduct according to the present invention and bunker C oil were mixed at a weight ratio of 35% and 65%, thereby completing manufacture of a biobunker C oil, and then a calorific value and sulfur content were measured.
  • Bunker C oil which is used as a fuel for industrial boilers, had a calorific value of 9,900 kcal/kg, and a sulfur content of 0.3 to 4.0%.
  • a biobunker C oil according to the present invention had a calorific value of 9,590 kcal/kg, and a sulfur content of 0.195%.
  • a biobunker C oil according to the present invention was manufactured by appropriately mixing a refined palm oil byproduct having low sulfur content (sulfur content of 0.01%) and bunker C oil having relatively high sulfur content.
  • the biobunker C oil had substantially lower sulfur content than conventional bunker C oil while its calorific value was maintained at a predetermined level.
  • a biobunker C oil according to the present invention discharges lower amount of sulfur than bunker C oil when used in industrial boilers, and thus, may be named as an environment-friendly bio fuel that causes less environmental pollutions. Accordingly, the biobunker C oil according to the present invention is expected to be used as an alternative to bunker C oil in the industrial boiler fuel market.

Abstract

Provided are a method of manufacturing an environment-friendly biobunker C oil having low sulfur content, in which the method includes: filtering a liquid palm oil byproduct prepared by heating a palm oil byproduct remaining after palm oil is refined from a palm fruit, so as to remove a solid material; completely dissolving the palm oil byproduct by adding an organic solvent to the liquid palm oil byproduct from which the solid material is removed; removing water from the dissolved palm oil byproduct by bring a water removing agent in contact with the dissolved palm oil byproduct; removing impurities from the water-removed palm oil byproduct by centrifuging, and removing the organic solvent, thereby completing manufacture of a refined palm oil byproduct; and mixing the refined palm oil byproduct and bunker C oil, thereby completing manufacture of a biobunker C oil, and an environment-friendly biobunker C oil having low sulfur content, manufactured by using the method.

Description

METHOD OF MANUFACTURING ENVIRONMENT-FRIENDLY BIOBUNKER C OIL HAVING LOW SULFUR CONTENT USING PALM OIL BYPRODUCT
The present invention relates to a method of manufacturing an environment-friendly biobunker C oil having low sulfur content using a palm oil byproduct, and in particular, to a method of manufacturing an environment-friendly biobunker C oil having low sulfur content in which the method includes: adding an organic solvent to a palm oil byproduct that remains after palm oil is refined from a palm fruit so as to dissolve the palm oil byproduct; bring the dissolved palm oil byproduct in contact with a water removing agent to remove water; centrifuging the palm oil byproduct to remove impurities and removing the organic solvent, thereby completing manufacture of a refined palm oil byproduct; and mixing the refined palm oil byproduct and bunker C oil, thereby completing manufacture of a biobunker C oil, and an environment-friendly biobunker C oil having low sulfur content manufactured by using the method.
Palm oil is produced in a great quantity for use in various applications, including food. Typically, palm oil is obtained from fruits of fresh oil palm trees (Elaeis guineensis). Usually, a palm tree produces about one fruit bunch having about 3,000 fruits every month. Palm trees, in general, continuously produce fruits for 25 years, and the continuous production guarantees good supply of palm oil.
In palm oil, a content of palmitic acid, which is a saturated fatty acid, is relatively high and a content of unsaturated fatty acid is relatively low. Thus, palm oil is not easily acidified and long-term preservation thereof is possible. Also, palm oil contains high contents of carotene, and tocotrienol and tocopherol which constitute vitamin E and thus, is nutritionally excellent.
Recently, increasing recognition on environmental problems has led to development of technologies for use of plant oil as a fuel. A representative example of plant oil is palm oil methyl ester produced from palm oil, that is, palm diesel. Palm oil is converted into palm oil methyl ester through transesterification. Since the palm oil methyl ester has excellent fuel characteristics, it can be used as an alternative to diesel.
Palm, which is a raw material of a palm oil byproduct, is an economically important crop that provides timber, fuel, building materials, fiber, starch, oil, liquor, etc. In particular, palm is used to produce palm raw oil, palm kernel oil, etc. Byproducts obtained from palm are solid at room temperature and thus, are inappropriate as a fuel. In addition, the byproducts contain high contents of impurities. To solve these problems, there is a need to develop a method of improving fluidity of solid byproducts at room temperature and refining the byproducts by removing impurities.
The present invention is results of research for selecting an optimal solvent in association with removal of a non-oil component from a solid palm oil byproduct that is produced during a manufacturing process for palm oil, reviewing extraction performance of a solvent, and improving fluidity through mixing with heavy oil.
Korean Patent Publication No. 2010-0110331 discloses a method of manufacturing a palm oil product, and Korean Patent Publication No. 2010-0118865 discloses a method of manufacturing environmental-friendly bio-charcoal using a biomass byproduct.
The present invention is introduced in response to such requirements. Bunker C oil, which is usually used in an industrial boiler, has a high caloric value of 9,900 kcal/kg but its sulfur content is as high as 0.3 to 4.0%, thereby causing pollution problems and limiting its use. Accordingly, the inventors of the present invention searched for a material that is partially alternatively used instead of bunker C oil having the problem as described above, and manufactured an environment-friendly biobunker C oil having low sulfur content by producing a refined palm oil byproduct by refining a palm oil byproduct generated during a manufacturing process for palm oil by using an appropriate solvent and mixing the refined palm oil byproduct with bunker C oil, wherein the refined palm oil byproduct has a calorific value of 9,020 kcal/kg, which is slightly lower than that of bunker C oil, has a very low sulfur content of 0.01%, and is cheaper than bunker C oil.
According to an aspect of the present invention, there is provided a method of manufacturing an environment-friendly biobunker C oil having low sulfur content, wherein the method includes manufacturing a refined palm oil byproduct by adding an organic solvent and a water removing agent to a palm oil byproduct remaining after palm oil is refined from a palm fruit, and mixing the refined palm oil byproduct with bunker C oil.
According to another aspect of the present invention, there is provided an environment-friendly biobunker C oil having low sulfur content manufactured by using the method.
An environment-friendly biobunker C oil having low sulfur content according to the present invention has a calorific value, similar to that of bunker C oil, and low sulfur content. Accordingly, the environment-friendly biobunker C oil having low sulfur content is an environment-friendly biofuel that may reduce environmental pollution. Also, the environment-friendly biobunker C oil having low sulfur content is cheaper than bunker C oil, and thus, it is expected that the environment-friendly biobunker C oil having low sulfur content may be used as an alternative to bunker C oil in the industrial boiler market.
FIG. 1 is a schematic view illustrating a production process for a conventional palm oil byproduct and a production process for a refined palm oil byproduct according to the present invention: a): a production process for a palm oil byproduct, and b): a production process for a refined palm oil byproduct.
FIG. 2 shows images of a palm oil byproduct and a refined palm oil byproduct according to the present invention: a) palm oil byproduct (20℃), b) palm oil byproduct (60℃), and c) refined palm oil byproduct.
FIG. 3 shows analysis results of elements contained in a conventional palm oil byproduct and a refined palm oil byproduct according to the present invention.
FIG. 4 shows graphs of amounts of solvents and petroleum required to dissolve a palm oil byproduct (1 g): a) a required amount with respect to a solvent, and b) a required amount with respect to petroleum.
FIG. 5 shows fluidity change of a palm oil byproduct with respect to an amount of bunker C oil used.
FIG. 6 shows a graph of a melting point of a palm oil byproduct with respect to an amount of hexane used.
According to an aspect of the present invention, there is provided a method of manufacturing an environment-friendly biobunker C oil having low sulfur content, in which the method includes:
filtering a liquid palm oil byproduct prepared by heating a palm oil byproduct remaining after palm oil is refined from a palm fruit, so as to remove a solid material;
completely dissolving the palm oil byproduct by adding an organic solvent to the liquid palm oil byproduct from which the solid material is removed;
removing water from the dissolved palm oil byproduct by bring a water removing agent in contact with the dissolved palm oil byproduct;
removing impurities from the water-removed palm oil byproduct by centrifuging, and removing the organic solvent, thereby completing manufacture of a refined palm oil byproduct; and
mixing the refined palm oil byproduct and bunker C oil, thereby completing manufacture of a biobunker C oil.
The method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a first phase, filtering a liquid palm oil byproduct prepared by heating a palm oil byproduct remaining after palm oil is refined from a palm fruit, so as to remove a solid material. The palm oil byproduct refers to a solid byproduct remaining in a process of producing palm oil from a palm fruit. The palm oil byproduct is half-solid at room temperature, and is liquid at a temperature of 60℃. So, the palm oil byproduct is heated to at a temperature of about 60℃ to prepare a liquid state. The liquid palm oil byproduct is filtered through a fiber filter to remove a solid material that is not dissolved. A manufacturing process for palm oil is known in the art.
The method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a second phase, completely dissolving the palm oil byproduct by adding an organic solvent to the liquid palm oil byproduct from which the solid material is removed. The solvent may be hexane, diethyl ether, dichloromethane, methanol, or acetone, but is not limited thereto. For example, the solvent may be hexane.
A solvent may be classified as a non-polar solvent, a polar protic solvent, and a polar aprotic solvent. Examples of a non-polar solvent are pentane, hexane, diethyl ether, cyclohexane, benzene, and toluene. Examples of a polar aprotic solvent are dichloromethane, ethyl acetate, acetone, and acetonitrile. Examples of a polar protic solvent are methanol, ethanol, an acetic acid, and water. Regarding selective dissolution of an organic component, separation capability is decreased in the following order of a non-polar solvent, a polar aprotic solvent, and a polar protic solvent. Among the non-polar solvents, dichloromethane is not appropriate due to generation of residual chloride, and diethyl ether may not be recovered due to its too low boiling point. Benzene and toluene have high toxicity, and cyclohexane requires a great amount of energy during evaporation due to its high boiling point. In this aspect, hexane is the most appropriate solvent.
The dissolving of the palm oil byproduct may be performed at a temperature of 25 to 35℃, for example, 30℃. However, the dissolving temperature is not limited thereto. The dissolving temperature may be in any temperature range in which hexane as a solvent is liquid and the palm oil byproduct as a solute is solid. For example, the dissolving temperature may be room temperature which does not require heating or a temperature slightly higher than room temperature, in consideration of energy use.
A dissolving time may be 0.5 to 1.5 hours, for example, 1 hour, but is not limited thereto. When the dissolving time is 30 minutes, 90% or more of the palm oil byproduct may be dissolved, and when the dissolving time is about 1 hour, the palm oil byproduct may be completely dissolved.
An amount of hexane used may be 35 to 55 mL based on 15 to 25 g of the palm oil byproduct, but is not limited thereto. An amount of hexane that is appropriate for complete dissolution may be 2 mL or more based on 1 g of the palm oil byproduct. If the amount of hexane is less than 2 mL based on 1 g of the palm oil byproduct, a dissolution rate of the palm oil byproduct with respect to hexane is low. Accordingly, the amount of hexane may be 2 to 2.5 mL based on 1 g of the palm oil byproduct.
The method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a third phase, removing water from the dissolved palm oil byproduct by bring a water removing agent in contact with the dissolved palm oil byproduct, wherein the water removing agent may be anhydrous sodium sulfate (Na2SO4), calcium sulfate (CaSO4), calcium chloride (CaCl2), silica powder, or clay powder. The removing of water in the refining process is performed to prevent incomplete combustion of a fuel oil, and to remove hydrophilic impurities therefrom, in addition to water, thereby improving purity of a fuel oil. The palm oil byproduct contains about 5% of hydrophilic part, and the percentage of hydrophilic part may be further decreased to 1% or less through the refining process.
The method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a fourth phase, removing impurities from the water-removed palm oil byproduct by centrifuging, and removing the organic solvent, thereby completing manufacture of a refined palm oil byproduct. The evaporated organic solvent is collected and is used again in the second phase of dissolving of the palm oil byproduct, which is economically very efficient.
The method of manufacturing an environment-friendly biobunker C oil having low sulfur content includes, as a fifth phase, mixing the refined palm oil byproduct and bunker C oil, thereby completing manufacture of a biobunker C oil. A mixed ratio of the refined palm oil byproduct to bunker C oil may be a weight ratio of 25 to 50:50 to 75, for example, 30 to 40:60 to 70, but is not limited thereto. An amount of bunker C oil that is appropriate for complete dissolution of 1 g of the refined palm oil byproduct may be 1.1 mL or more. If the amount of bunker C oil is less than 1.1 ml, a solid material may remain and fluidity of the refined palm oil byproduct may be inappropriate. Accordingly, an amount of bunker C oil used needs to be equal to or higher than 50 weight ratio with respect to the refined palm oil byproduct, and if the amount of bunker C oil is equal to or higher than 75 weight ratio with respect to the refined palm oil byproduct, the sulfur decrease effect may not be significantly low. Accordingly, the mixed ratio of the refined palm oil byproduct to bunker C oil as described above may be most appropriate.
Accordingly, an example of a method of manufacturing an environment-friendly biobunker C oil having low sulfur content according to the present invention may include:
filtering a liquid palm oil byproduct prepared by heating a palm oil byproduct remaining after palm oil is refined from a palm fruit, so as to remove a solid material;
completely dissolving the palm oil byproduct at a temperature of 25 to 35℃ for 0.5 to 1.5 hours by adding hexane to 15 to 25 parts by weight of the liquid palm oil byproduct from which the solid material is removed;
removing water from the dissolved palm oil byproduct by bring 0.5 to 1.5 parts by weight of anhydrous sodium sulfate (Na2SO4) in contact with the dissolved palm oil byproduct;
removing impurities from the water-removed palm oil byproduct by centrifuging, and removing the hexane, thereby completing manufacture of a refined palm oil byproduct; and
mixing the refined palm oil byproduct and bunker C oil at a weight ratio of 25 to 50:50 to 75, thereby completing manufacture of a biobunker C oil.
Also, the present invention provides an environment-friendly biobunker C oil having low sulfur content manufactured by using the method according to the present invention. A biobunker C oil according to the present invention is manufactured by mixing a refined palm oil byproduct having relatively very low sulfur content with bunker C oil having relatively high sulfur content, and may be environment-friendly due to its lower sulfur content than bunker C oil. The biobunker C oil according to the present invention may be used as an alternative to bunker C oil that is generally used as a fuel for industrial boilers.
Also, the present invention provides an environment-friendly biobunker C oil having low sulfur content, wherein the environment-friendly biobunker C oil contains 1.0 parts by weight or less of water, 25 to 50 parts by weight of a refined palm oil byproduct from which a solid material is removed, and 50 to 75 parts by weight of bunker C oil. The refined palm oil byproduct may contain 1.0 part by weight or less of water and may not contain a solid material. A mixed weight ratio of the refined palm oil byproduct to the bunker C oil may be 25 to 50:50 to 75, for example 30 to 40:60 to 70, but is not limited thereto.
Hereinafter, examples of the present invention will be described in detail. However, the examples are for illustrative purpose only and do not limit the scope of the present invention.
Example 1: Filtering of palm oil byproduct
A palm oil byproduct was heated to a temperature of 60℃ so as to obtain a liquid palm oil byproduct, and then, the liquid palm oil byproduct was poured onto a fiber filter and the fiber filter was squeezed.
Example 2: Manufacturing of refined palm oil byproduct
A palm oil byproduct (20 g) was added to hexane (40 ml), and then, the mixture was stirred in a shaking incubator at a rate of 200 rpm, at a temperature of 30℃ for 1 hour, and then completely dissolved by using a Vorltex mixer. 1 g of anhydrous sodium sulfate (Na2SO4) was added to the palm oil byproduct that was dissolved in hexane. The palm oil byproduct which was dissolved in hexane and to which the anhydrous sodium sulfate was added was placed in 50 mL conical tube and then centrifuging was performed thereon at a rate of 4000 rpm for 5 minutes. Hexane as a solvent was removed by centrifuging from the refined solution from which impurities were removed, and collected, thereby completing manufacture of a refined palm oil byproduct (FIGS. 1 and 2).
Elements of the obtained refined palm oil byproduct and a conventional palm oil byproduct were analyzed. As a result, it was found that carbon, oxygen, and hydrogen dominate for the byproducts, and an amount of sulfur contained therein was very low of 0.01% (FIG. 3).
Example 3: Measuring of amount of solvent for extracting palm oil byproduct
In order to measure an amount of a solvent needed to extract a palm oil byproduct, 1 g of the palm oil byproduct was placed in each of glass bottles. Dichloromethane, methanol, acetone, hexane, gasoline, diesel, kerosene, bunker A oil, bunker B oil, and bunker C oil were each added in small amounts to the 1 g of the palm oil byproduct so as to identify an amount of a solvent that was required for dissolving 1 g of palm oil byproduct.
FIG. 4 shows a graph of amounts of the solvents required to dissolve 1 g of the palm oil byproduct. Among organic solvents, dissolution effects were decreased in the following order of methanol (1.466 mL/g), dichloromethane (1.496 mL/g), and hexane (1.968 mL/g). Among the three organic solvents, methanol and dichloromethane were not used since the resultant refined palm oil byproduct may have relatively low purity. The inventors used hexane as a solvent. Also, among various petroleum, heavy oil, such as bunker A oil (1.134 mL/g), bunker B oil (1.185 mL/g), and bunker C oil (1.096 mL/g), were most effective for dissolving the palm oil byproduct. Among the three oils, the bunker C oil has the highest effects.
Example 4: Confirming of fluidity due to mixing of petroleum
In order to confirm fluidity of the palm oil byproduct with respect to mixing with petroleum, 200, 400, 600, 800, and 1000㎕ of each of disel, bunker A oil, bunker B oil, and bunker C oil were added to 1 g of the palm oil byproduct. FIG. 5 is images for confirming fluidity of the palm oil byproduct with respect to bunker C oil. Referring to FIG. 5, the higher the amount of the bunker C oil, the higher the fluidity of the palm oil byproduct.
Example 5: Measuring of melting point of refined palm oil byproduct with respect to mixing with hexane
In order to measure a melting point of refined palm oil byproduct with respect to mixing with hexane, 2 mL of refined palm oil byproduct that became liquid by heating was placed in each of five glass bottles, and then the bottles were placed at room temperature to solidify the refined palm oil byproducts. 0, 20, 50, 100 and 200㎕ of hexane was added to the solidified refined palm oil byproduct. The five glass bottles each containing the refined palm oil byproduct were placed in an oven and the temperature was increased to change the state of the refined palm oil byproduct into a liquid state. Then, the oven was turned off and the temperature was decreased and a temperature at which the refined palm oil byproduct was solidified was measured. As a result, it was confirmed that the higher the amount of the hexane used, the lower the melting point of the refined palm oil byproduct (FIG. 6).
Example 6: Manufacturing of biobunker C oil through mixing of bunker C oil and refined palm oil byproduct
A refined palm oil byproduct according to the present invention and bunker C oil were mixed at a weight ratio of 35% and 65%, thereby completing manufacture of a biobunker C oil, and then a calorific value and sulfur content were measured. Bunker C oil, which is used as a fuel for industrial boilers, had a calorific value of 9,900 kcal/kg, and a sulfur content of 0.3 to 4.0%. On the other hand, a biobunker C oil according to the present invention had a calorific value of 9,590 kcal/kg, and a sulfur content of 0.195%.
A biobunker C oil according to the present invention was manufactured by appropriately mixing a refined palm oil byproduct having low sulfur content (sulfur content of 0.01%) and bunker C oil having relatively high sulfur content. The biobunker C oil had substantially lower sulfur content than conventional bunker C oil while its calorific value was maintained at a predetermined level.
A biobunker C oil according to the present invention discharges lower amount of sulfur than bunker C oil when used in industrial boilers, and thus, may be named as an environment-friendly bio fuel that causes less environmental pollutions. Accordingly, the biobunker C oil according to the present invention is expected to be used as an alternative to bunker C oil in the industrial boiler fuel market.

Claims (8)

  1. A method of manufacturing an environment-friendly biobunker C oil having low sulfur content, the method comprising:
    filtering a liquid palm oil byproduct prepared by heating a palm oil byproduct remaining after palm oil is refined from a palm fruit, so as to remove a solid material;
    completely dissolving the palm oil byproduct by adding an organic solvent to the liquid palm oil byproduct from which the solid material is removed;
    removing water from the dissolved palm oil byproduct by bring a water removing agent in contact with the dissolved palm oil byproduct;
    removing impurities from the water-removed palm oil byproduct by centrifuging, and removing the organic solvent, thereby completing manufacture of a refined palm oil byproduct; and
    mixing the refined palm oil byproduct and bunker C oil, thereby completing manufacture of a biobunker C oil.
  2. The method of claim 1, wherein the organic solvent is hexane, diethyl ether, dichloromethane, methanol, or acetone.
  3. The method of claim 1, wherein the dissolving of palm oil byproduct is performed at a temperature of 25 to 35℃.
  4. The method of claim 1, wherein the water removing agent is anhydrous sodium sulfate (Na2SO4), calcium sulfate (CaSO4), calcium chloride (CaCl2), silica powder, or clay powder.
  5. The method of claim 1, wherein in the mixing, the refined palm oil byproduct is mixed with bunker C oil at a weight ratio of 25 to 50:50 to 75.
  6. A method of manufacturing an environment-friendly biobunker C oil having low sulfur content, the method comprising:
    filtering a liquid palm oil byproduct prepared by heating a palm oil byproduct remaining after palm oil is refined from a palm fruit, so as to remove a solid material;
    completely dissolving the palm oil byproduct at a temperature of 25 to 35℃ for 0.5 to 1.5 hours by adding hexane to 15 to 25 parts by weight of the liquid palm oil byproduct from which the solid material is removed;
    removing water from the dissolved palm oil byproduct by bring 0.5 to 1.5 parts by weight of anhydrous sodium sulfate (Na2SO4) in contact with the dissolved palm oil byproduct;
    removing impurities from the water-removed palm oil byproduct by centrifuging, and removing the hexane, thereby completing manufacture of a refined palm oil byproduct; and
    mixing the refined palm oil byproduct and bunker C oil at a weight ratio of 25 to 50:50 to 75, thereby completing manufacture of a biobunker C oil.
  7. An environment-friendly biobunker C oil having low sulfur content, manufactured by using the method of any one of claims 1-6.
  8. An environment-friendly biobunker C oil having low sulfur content, comprising 1.0 parts by weight or less of water, 25 to 50 parts by weight of a refined palm oil byproduct from which a solid material is removed, and 50 to 75 parts by weight of bunker C oil.
PCT/KR2011/003106 2011-02-09 2011-04-27 Method of manufacturing environment-friendly biobunker c oil having low sulfur content using palm oil byproduct WO2012108584A1 (en)

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