KR20080025449A - Purification method of biodiesel using heterogenous catalyst - Google Patents

Purification method of biodiesel using heterogenous catalyst Download PDF

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KR20080025449A
KR20080025449A KR1020060089934A KR20060089934A KR20080025449A KR 20080025449 A KR20080025449 A KR 20080025449A KR 1020060089934 A KR1020060089934 A KR 1020060089934A KR 20060089934 A KR20060089934 A KR 20060089934A KR 20080025449 A KR20080025449 A KR 20080025449A
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biodiesel
glycerin
purifying
heterogeneous catalyst
crude
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KR100831072B1 (en
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박돈희
정귀택
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전남대학교산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • 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
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
    • 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
    • C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
    • 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
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Fats And Perfumes (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

A purification method of biodiesel using a heterogenous catalyst is provided to reduce process time, not to produce wastewater, and to shorten a total amount of time required to separation water. A purification method of biodiesel comprises the steps of: preparing crude biodiesel from which glycerin is not sufficiently removed; neutralizing the crude biodiesel with hydrogen ion and hydroxide ion in the presence of a heterogenous catalyst powder fired at 100-500deg.C to a particle size of 0.1-10mm; removing metal ions(I and II); and removing glycerin to obtain pure biodiesel. The heterogenous catalyst is selected from the group consisting of: montmorillonite, zeolite, activated carbon, diatomaceous earth, bentonite, alumina, silicalite, fly ash, high carbon, vermiculite, perlite, pi-complex adsorbent, potassium silicate, calcium carbonate, polymer resin, etc.

Description

불균일계 촉매를 이용한 바이오디젤의 정제방법{Purification method of biodiesel using heterogenous catalyst}Purification method of biodiesel using heterogenous catalyst

도 1은 본 발명이 적용된 바이오디젤의 정제공정도의 일례이다.1 is an example of a process chart of purification of biodiesel to which the present invention is applied.

본 발명은 유지로부터 바이오디젤의 제조공정 중 정제방법에 관한 것으로 보다 상세하게는 과량의 알콜이 제거되고 글리세린이 층분리 된 정제되지 않은 조바이오디젤(crude biodiesel)을 불균질계 촉매하에서 수소화기(H+)와 수산화기(OH-)의 중화 단계, 일가 또는 이가 금속이온(K+, Na+, Ca2+, Mg2 +)의 제거단계, 그리고 글리세린을 제거단계로 이루어진 것을 특징으로 하는 바이오디젤의 정제방법에 관한 것이다.The present invention relates to a purification method during the manufacturing process of biodiesel from fats and oils, and more particularly, to remove crude alcohols in which excess alcohol is removed and glycerin layered under a heterogenous catalyst under a heterogeneous catalyst. H +) and hydroxyl group (OH - neutralization step, a monovalent or divalent metal ion) (K +, Na +, Ca 2+, biodiesel, characterized in that step consisting of removal, and removing the glycerol phase of Mg 2 +) It relates to a purification method of.

바이오디젤 생산 공정의 기술 경쟁력과 경제성은 에스테르화 공정에 의하여 좌우될 만큼 이 공정이 매우 중요하지만 보다 높은 경제성과 품질에 있어 메탄올 회수 공정, 글리세린 분리 공정 및 세척 공정과 같은 바이오디젤의 후처리 공정들도 매우 중요하다. 에스테르화 하여 얻어진 지방산 메틸에스테르 반응물에는 주요 생성물인 지방산 메틸에스테르와 글리세롤 이외에도 과량의 메탄올, 반응에 사용한 촉매, 반응 중에 생성된 비누화합물 등의 불순물이 존재한다. 지방산 메틸에스테르 이외의 물질들은 불순물로 간주되며, 지방산 메틸에스테르의 품질과 규격에 있어 이러한 불순물들은 적당한 공정을 통하여 회수 또는 제거되어야 한다. 반응액의 단일 상에서 과량의 메탄올을 먼저 회수한 후 지방산 메틸에스테르 층과 글리세린 층을 분리하는 방법과 지방산 메틸에스테르 층과 글리세롤 층을 먼저 분리한 후 메탄올을 분리하는 방법이 적용되고 있다. 최근에는 공정의 효율성과 품질 면에서 앞의 방법을 채택하는 경우가 많다. 메탄올을 회수하는 방법으로는 단증류법, 감압증류법, 분별증류법, 박막증류법 등이 있다. 메탄올이 회수된 반응물에 대해 지방산 메틸에스테르 층과 글리세롤 층으로 상 분리하는 공정이 뒤따른다. 두 층을 분리하는 방법으로는 크게 중력장 상 분리법과 액상/액상 원심 분리법이 있다. 층 분리를 통해 얻어진 지방산 메틸에스테르 층에는 아직 알칼리 촉매와 소량의 비누화합물이 함유되어 있다. 지방산 메틸 에스테르 층을 중화 및 세척하는 공정은 제품의 수율과 세척수의 사용량에 있어 많은 영향을 받는 사용되는 세척수의 양을 줄이면서 효율적으로 지방산 메틸에스테르와 세척수 간의 균일한 혼합이 이루어져야 한다. 세척공정에서 발생하는 지방산 메틸에스테르 층과 물 층은 중력장 상분리 법과 액체/액체 원심 분리법을 통해 분리된다. 분리된 메틸에스테르 층은 건조하여 제품으로 생산 된다. 또한, 분리된 지방산 메틸에스테르는 대량생산 공정에서는 200℃의 증류탑을 통해 고순도의 지방산 메틸에스테르 제품을 생산한다.The technical competitiveness and economics of the biodiesel production process are so important that it depends on the esterification process, but the biodiesel post-treatment processes such as methanol recovery process, glycerin separation process and washing process are more economical and quality. Is also very important. In addition to the fatty acid methyl ester and glycerol, the fatty acid methyl ester reactant obtained by esterification contains impurities such as an excess of methanol, a catalyst used in the reaction, and a soap compound produced during the reaction. Substances other than fatty acid methyl esters are considered as impurities and, in the quality and specification of fatty acid methyl esters, these impurities must be recovered or removed by suitable processes. Excess methanol is recovered first in a single phase of the reaction solution, and a method of separating a fatty acid methyl ester layer and a glycerin layer and a method of separating a fatty acid methyl ester layer and a glycerol layer first and then methanol are applied. In recent years, the former method is often adopted in terms of process efficiency and quality. As a method for recovering methanol, there are a single distillation method, a vacuum distillation method, a fractional distillation method, a thin film distillation method, and the like. This is followed by a phase separation of methanol to the recovered reactants into a fatty acid methylester layer and a glycerol layer. There are two methods for separating the two layers, gravitational field phase separation and liquid / liquid phase centrifugation. The fatty acid methylester layer obtained through the layer separation still contains an alkali catalyst and a small amount of soap compound. The process of neutralizing and washing the fatty acid methyl ester layer should efficiently and uniformly mix the fatty acid methyl ester with the wash water while reducing the amount of wash water used which is highly influenced by the yield of the product and the amount of wash water used. The fatty acid methylester layer and water layer generated in the washing process are separated by gravity field phase separation and liquid / liquid centrifugation. The separated methyl ester layer is dried to produce the product. In addition, the separated fatty acid methyl esters produce high-purity fatty acid methyl ester products through a 200 ° C. distillation column in a mass production process.

본원발명과 관련된 선행기술로서는 대한민국 공개특허 제2006-0029671호(폐 튀김유를 이용한 고순도 바이오디젤을 합성하기 위한 선택성 촉매흡착 정제공정)에서는 조바이오디젤에 실리카, 알루미나, 또는 마그네시아로 조성된 분말을 첨가하여 불순물을 선택적으로 여과하여 제거함으로서 바이오디젤을 제조하는 것을 특징으로 하는 바이오디젤 정제방법이다.In the prior art related to the present invention, Korean Patent Publication No. 2006-0029671 (selective catalytic adsorption and purification process for synthesizing high-purity biodiesel using waste frying oil) adds a powder composed of silica, alumina, or magnesia to crude biodiesel. The biodiesel purification method of manufacturing a biodiesel by selectively filtering and removing impurities.

결국, 본원발명과 같이 불균일계 촉매를 이용하여 바이오디젤을 정제하는 기술은 아직 실제적으로 확립되어 있지 않은 실정이다.As a result, a technology for purifying biodiesel using a heterogeneous catalyst as in the present invention has not been established yet.

본 발명은 정제되지 않은 조바이오디젤을 불균질계 촉매하에서 수소화기(H+)와 수산화기(OH-)의 중화 단계, 일가 또는 이가 금속이온(K+, Na+, Ca2 +, Mg2 +)의 제거 단계, 그리고 글리세린의 제거 단계를 포함하는 바이오디젤의 정제방법으로 바이오디젤을 제조하는 방법 및 이러한 방법에 의해 제조한 바이오디젤의 제공을 목적으로 한다.The invention can extinguisher (H +) and hydroxyl groups (OH -) under the homogeneous light crude biodiesel crude catalyst neutralization step, a monovalent or divalent metal ion (K +, Na +, Ca 2 +, Mg 2 + It is an object of the present invention to provide a method for producing biodiesel by the method of purifying biodiesel, including the step of removing the glycerol, and the step of removing glycerin.

본 발명은 바이오디젤의 정제시 수세공정에 의한 정제방법보다 빠른 시간 내에 생성물을 얻을 수 있다. 한편 본 발명은 수세식 정제방법을 사용한 경우와는 다르게 폐수의 발생이 없고 수분의 분리에 소요되는 시간을 줄일 수 있다.The present invention can obtain the product within a faster time than the purification method by the washing step in the purification of biodiesel. On the other hand, the present invention can reduce the time required for the separation of water without the generation of waste water, unlike when using the flush purification method.

한편 본 발명은 바이오디젤의 정제시 관형반응기(PFR)와 연속교반탱크반응기(CSTR)와 같은 연속공정에서도 이용할 수 있다.On the other hand, the present invention can be used in continuous processes such as tubular reactor (PFR) and continuous stirring tank reactor (CSTR) during the purification of biodiesel.

본 발명은 정제되지 않은 조바이오디젤을 불균질계 촉매하에서 수소화기(H+) 와 수산화기(OH-)의 중화 단계, 일가 또는 이가 금속이온(K+, Na+, Ca2 +, Mg2 +)의 제거 단계, 그리고 글리세린의 제거 단계를 포함하는 바이오디젤의 정제방법에 관한 것이다.The invention can extinguisher (H +) and hydroxyl groups (OH -) under the homogeneous light crude biodiesel crude catalyst neutralization step, a monovalent or divalent metal ion (K +, Na +, Ca 2 +, Mg 2 + It relates to a method for purifying biodiesel comprising the step of removing) and a step of removing glycerin.

본 발명에서 수소화기(H+)와 수산화기(OH-)의 중화 단계와 일가 또는 이가 금속이온(K+, Na+, Ca2 +, Mg2 +)의 제거 단계에 사용한 불균질계 촉매는 수산기(OH-), 바이카보네이트기(HCO3 -) 또는 카보네이트기(CO3 2-)를 포함하는 염기성 이온교환수지이거나; 또는 수소(H+), 칼륨(K+), 나트륨(Na+), 칼슘(Ca2 +), 마그네슘(Mg2 +), 망간(Mn2 +) 또는 아연(Zn2 +) 이온을 포함하는 산성 이온교환수지 중 선택된 어느 하나 또는 여러 종류를 혼합하여 사용할 수 있다.In the present invention, the heterogeneous catalyst used in the neutralization step of the hydrogenation group (H + ) and the hydroxyl group (OH − ) and the removal of monovalent or divalent metal ions (K + , Na + , Ca 2 + , Mg 2 + ) is a hydroxyl group. (OH -), bicarbonate exchanger (HCO 3 -) or a carbonate group (CO 3 2-) or a basic ion exchange resin comprising; Or hydrogen (H + ), potassium (K + ), sodium (Na + ), calcium (Ca 2 + ), magnesium (Mg 2 + ), manganese (Mn 2 + ) or zinc (Zn 2 + ) ions Any one or several kinds of acidic ion exchange resins may be mixed and used.

본 발명에서 글리세린의 제거를 위해 사용한 불균일계 촉매는 활성백토(산성백토), 제올라이트, 활성탄, 규조토, 벤토나이트, 알루미나, 실리카라이트(silicalite), 석탄회, 고탄소 fly-ach, 분자체, 질석, 퍼라이트, π-착화합결합 흡착제, 필라드클레이, 고분자수지, 규산칼륨, 탄산칼슘 중 선택된 어느 하나 또는 여러 종류를 혼합하여 100～500℃의 온도 범위 내에서 소성 한 후, 0.1～10 mm의 입자로 성형하여 사용할 수 있다.The heterogeneous catalyst used for the removal of glycerin in the present invention is activated clay (acid clay), zeolite, activated carbon, diatomaceous earth, bentonite, alumina, silicalite (silicalite), coal ash, high carbon fly-ach, molecular sieve, vermiculite, perlite , π-complexed adsorbent, filad clay, polymer resin, potassium silicate, calcium carbonate, any one or several kinds of mixtures are mixed and calcined in the temperature range of 100 ~ 500 ℃, and then 0.1 ~ 10 mm It can be molded and used.

또한 불균일계 촉매는 회분식반응기 또는 관형반응기(PFR)에 넣어 바이오디젤을 정제할 수 있다.In addition, the heterogeneous catalyst may be purified in biodiesel in a batch reactor or tubular reactor (PFR).

본 발명에서는 바이오디젤 정제공정의 반응온도는 20℃ 내지 150℃의 범위에서 수행할 수 있다. In the present invention, the reaction temperature of the biodiesel purification process may be performed in the range of 20 ℃ to 150 ℃.

본 발명은 바이오디젤 정제공정으로부터 제조한 바이오디젤 및 혼합유를 포함한다.The present invention includes biodiesel and mixed oils prepared from biodiesel purification processes.

본 발명에 의해 불균일계 촉매를 사용하여 바이오디젤을 정제하면 종래의 바이오디젤 제조방법보다 폐수의 발생량을 낮출 수 있고, 유지와 수분의 분리시간을 줄일 수 있고, 또한 높은 순도의 바이오디젤을 얻을 수 있음을 알 수 있다.Purifying biodiesel using a heterogeneous catalyst according to the present invention can reduce the amount of wastewater generated, reduce the separation time of oil and water, and obtain high-purity biodiesel compared to the conventional biodiesel manufacturing method. It can be seen that.

Claims (6)

원료유지로부터 제조한 바이오디젤의 정제공정에 있어서,In the purification process of the biodiesel produced from the raw material holding, 과량의 알콜이 제거되고 글리세린이 층분리 된 정제되지 않은 조바이오디젤을 불균질계 촉매하에서 수소화기(H+)와 수산화기(OH-)의 중화 단계, 일가 또는 이가 금속이온(K+, Na+, Ca2 +, Mg2 +)의 제거 단계, 그리고 글리세린의 제거 단계를 포함하는 바이오디젤의 정제방법.Can extinguisher (H +) and hydroxyl groups (OH -) of the crude biodiesel that excess alcohol removed, and the crude glycerin the delamination under a heterogeneous catalyst neutralization step, a monovalent or divalent metal ion (K +, Na + , Ca 2 + , Mg 2 + ) removal step, and the method of purifying biodiesel comprising the step of removing glycerin. 제1항에 있어서,The method of claim 1, 수소화기(H+)와 수산화기(OH-)의 중화 단계와 일가 또는 이가 금속이온(K+, Na+, Ca2+, Mg2 +)의 제거 단계에 사용한 불균질계 촉매는 수산기(OH-), 바이카보네이트기(HCO3 -) 또는 카보네이트기(CO3 2 -)를 포함하는 염기성 이온교환수지이거나; 또는 수소(H+), 칼륨(K+), 나트륨(Na+), 칼슘(Ca2 +), 마그네슘(Mg2 +), 망간(Mn2 +) 또는 아연(Zn2 +) 이온을 포함하는 산성 이온교환수지 중 선택된 어느 하나 또는 여러 종류를 혼합한 것을 특징으로 하는 바이오디젤의 정제방법.A heterogeneous catalyst used for the removal step of the neutralization step and the monovalent or divalent metal ion (K +, Na +, Ca 2+, Mg 2 +) of the hydroxyl groups (OH - can extinguisher (H +) and hydroxyl group (OH) - ), bicarbonate exchanger (HCO 3 -) or a carbonate group (CO 3 2 -) or a basic ion exchange resin comprising; Or hydrogen (H + ), potassium (K + ), sodium (Na + ), calcium (Ca 2 + ), magnesium (Mg 2 + ), manganese (Mn 2 + ) or zinc (Zn 2 + ) ions A method for purifying biodiesel, characterized in that any one or several selected from acidic ion exchange resins are mixed. 제1항에 있어서,The method of claim 1, 글리세린의 제거 단계에 사용할 수 있는 불균일계 촉매는 활성백토(산성백토), 제올라이트, 활성탄, 규조토, 벤토나이트, 알루미나, 실리카라이트(silicalite), 석탄회, 고탄소 fly-ach, 분자체, 질석, 퍼라이트, π-착화합결합 흡착제, 필라드클레이, 고분자수지, 규산칼륨, 탄산칼슘 중 선택된 어느 하나 또는 여러 종류를 혼합하여 100～1,000℃의 온도 범위 내에서 소성 한 후, 0.1～10 mm의 입자로 성형하여 얻음을 특징으로 하는 바이오디젤의 정제방법.Heterogeneous catalysts that can be used for the removal of glycerin include activated clay (acid clay), zeolite, activated carbon, diatomaceous earth, bentonite, alumina, silicalite (silicalite), coal ash, high carbon fly-ach, molecular sieve, vermiculite, perlite, Any one or several selected from π-complex adsorbent, filad clay, polymer resin, potassium silicate and calcium carbonate are mixed and calcined within a temperature range of 100 to 1,000 ° C, and then molded into particles of 0.1 to 10 mm Purifying method of biodiesel, characterized in that obtained by. 제1항에 있어서,The method of claim 1, 불균질계 촉매는 조바이오디젤 중량에 대하여 1∼50%를 사용함을 특징으로 하는 바이오디젤의 정제방법.A heterogeneous catalyst is a method for purifying biodiesel, characterized in that 1 to 50% by weight of the crude biodiesel. 제 1항에 있어서,The method of claim 1, 불균일계 촉매는 회분식반응기 또는 관형반응기(PFR)에 넣어 반응온도 30℃ 내지 150℃에서 반응하여 바이오디젤을 정제함을 특징으로 하는 바이오디젤의 정제방법.The heterogeneous catalyst is a biodiesel purification method characterized in that the biodiesel is purified by reaction in a batch reactor or tubular reactor (PFR) at a reaction temperature of 30 ℃ to 150 ℃. 특허청구범위 제1항의 방법으로 제조한 바이오디젤 및 혼합유.Biodiesel and mixed oil prepared by the method of claim 1.
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CN108707509A (en) * 2018-07-23 2018-10-26 昆明理工大学 A kind of device and method reducing biodiesel metal ion content
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CN108707509A (en) * 2018-07-23 2018-10-26 昆明理工大学 A kind of device and method reducing biodiesel metal ion content
KR102217064B1 (en) * 2020-08-31 2021-02-18 무진기공 주식회사 Biodiesel purification system capable of performing cleaning or replacement determination of tablet resins using electrical conductivity

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