KR20100136060A - Method for preparing of bio-diesel using by-products - Google Patents
Method for preparing of bio-diesel using by-products Download PDFInfo
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- KR20100136060A KR20100136060A KR1020090054236A KR20090054236A KR20100136060A KR 20100136060 A KR20100136060 A KR 20100136060A KR 1020090054236 A KR1020090054236 A KR 1020090054236A KR 20090054236 A KR20090054236 A KR 20090054236A KR 20100136060 A KR20100136060 A KR 20100136060A
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- biodiesel
- catalyst
- products
- diesel
- oil component
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- 239000003225 biodiesel Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000006227 byproduct Substances 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 claims abstract description 23
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 12
- 235000011187 glycerol Nutrition 0.000 claims abstract description 11
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000002378 acidificating effect Effects 0.000 claims abstract description 4
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 102000004190 Enzymes Human genes 0.000 claims description 8
- 108090000790 Enzymes Proteins 0.000 claims description 8
- 239000011942 biocatalyst Substances 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 239000004367 Lipase Substances 0.000 claims description 4
- 102000004882 Lipase Human genes 0.000 claims description 4
- 108090001060 Lipase Proteins 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019421 lipase Nutrition 0.000 claims description 4
- 241000222120 Candida <Saccharomycetales> Species 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 244000005700 microbiome Species 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 241000589513 Burkholderia cepacia Species 0.000 claims description 2
- 241001661345 Moesziomyces antarcticus Species 0.000 claims description 2
- 241000235403 Rhizomucor miehei Species 0.000 claims description 2
- 240000005384 Rhizopus oryzae Species 0.000 claims description 2
- 235000013752 Rhizopus oryzae Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 1
- 229910017604 nitric acid Inorganic materials 0.000 abstract 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 abstract 1
- 235000011007 phosphoric acid Nutrition 0.000 abstract 1
- 238000007670 refining Methods 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 19
- 235000019198 oils Nutrition 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- 235000019482 Palm oil Nutrition 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000021588 free fatty acids Nutrition 0.000 description 1
- 125000005456 glyceride group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002540 palm oil Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
- C12P7/6436—Fatty acid esters
- C12P7/649—Biodiesel, i.e. fatty acid alkyl esters
-
- 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
-
- 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
- C10L1/026—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for compression ignition
-
- 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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
-
- 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
-
- 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)
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- General Chemical & Material Sciences (AREA)
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- Microbiology (AREA)
- Biotechnology (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Fats And Perfumes (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
Description
본 발명은 바이오디젤(Bio-diesel) 부산물을 이용한 바이오디젤 제조방법에 관한 것으로, 더욱 상세하게는 바이오디젤 제조과정에서 발생하는 부산물을 정제하여 글리세린과 오일성분으로 분리한 후 글리세린을 제외하고 남은 오일성분으로부터 바이오디젤을 재생산하는 방법에 관한 것이다.The present invention relates to a biodiesel manufacturing method using biodiesel by-products, and more specifically, by-products generated during the biodiesel manufacturing process are purified and glycerin and The present invention relates to a method for reproducing biodiesel from the remaining oil components except glycerin after separation into oil components.
바이오디젤이란 유채유, 대두유, 팜유와 같은 각종 식물유, 우지와 같은 동물성 지방, 폐식용유 등 다양한 재생 가능한 자원을 촉매 존재 하에 알코올과 반응시켜 생성하는 에스테르화 기름을 말하며, 경유와 물성이 유사하므로 경유에 대체 또는 혼합하여 압축착화 디젤엔진에 사용할 수 있다. 즉, 바이오디젤은 동물성 또는 식물성 지방산이 메탄올과 화학반응에 의해 전환된 경유 대체연료로 정의할 수 있다. Biodiesel is an esterified oil produced by reacting various renewable resources such as rapeseed oil, soybean oil, palm oil, animal fats such as tallow, and edible oil with alcohol in the presence of a catalyst. Can be substituted or mixed for compression ignition diesel engines. In other words, biodiesel may be defined as a diesel fuel which is converted to animal or vegetable fatty acid by chemical reaction with methanol.
이러한 바이오디젤을 생산하는 공정은 크게 촉매를 사용하는 공정과 촉매를 사용하지 않는 공정으로 나누어 볼 수 있다. 촉매를 사용하는 공정의 장점은 상온 및 대기압과 유사한 조건에서 제품을 생산할 수 있는 장점을 갖고 있다. 이와는 달 리 촉매를 사용하지 않는 공정은 생산 및 제품의 정제공정이 비교적 단순하며, 일반적으로 초임계 조건을 이용하고 있다. 초임계 조건은 촉매를 사용하는 공정에 비해 메탄올 사용량이 많으며, 고온 고압의 조건이 필요하지만 제품의 정제과정이 필요 없는 큰 장점이 있다. 현재 보급된 상업적인 생산 공정은 대다수가 촉매를 사용하는 공정이며, 초임계 공정에 대한 연구가 활발히 진행되고 있다.The biodiesel production process can be broadly divided into a process using a catalyst and a process not using a catalyst. The advantage of using a catalyst is that it can produce products at conditions similar to room temperature and atmospheric pressure. In contrast, the process without the catalyst is relatively simple in the production and purification of the product, generally using supercritical conditions. Supercritical conditions have a large amount of methanol compared to a process using a catalyst, and the conditions of high temperature and high pressure are required, but there is a big advantage that no purification process of the product is required. Currently, the commercial production process is the majority of the process using the catalyst, the research on the supercritical process is active.
그러나, 대부분이 동물성 또는 식물성 유지나 폐유지를 알코올과 반응시켜 바이오디젤을 생산하는 방법에 대한 연구들이며, 바이오디젤 생산 과정에서 약 10% 이상 발생하는 부산물로부터 바이오디젤을 재생산하는 방법에 대해서는 어떠한 개시나 교시된 바가 없다.Most of these studies, however, are studies on the production of biodiesel by reacting animal or vegetable fats and oils with alcohol, and there is no disclosure on how to reproduce biodiesel from by-products that occur at least 10% during biodiesel production. Nothing has been taught.
이에 본 발명자들은 바이오디젤의 제조과정에서 발생하는 부산물을 이용하고자 예의 노력한 결과, 부산물을 정제하여 글리세린과 오일성분으로 분리한 후 상기 오일성분으로부터 촉매 등을 이용하여 바이오디젤을 재생산하고 본 발명을 완성하였다. Thus, the present inventors have made efforts to use the by-products generated in the manufacturing process of biodiesel, and by-products are purified and separated into glycerin and oil components, and then the biodiesel is reproduced by using a catalyst or the like from the oil components to complete the present invention. It was.
결국, 본 발명의 주된 목적은 바이오디젤 제조과정에서 발생하는 부산물을 이용한 바이오디젤의 제조방법 및 상기 방법으로 제조되는 바이오디젤을 제공하는데 있다.After all, the main object of the present invention is to provide a method for producing biodiesel using by-products generated in the biodiesel manufacturing process and the biodiesel produced by the method.
상기 목적을 달성하기 위하여, 본 발명은 바이오디젤 제조과정에서 발생하는 부산물을 정제하여 글리세린과 오일성분으로 분리하고, 상기 분리된 오일성분으로부터 촉매를 사용하여 바이오디젤을 재생산하는 제조방법 및 상기 방법으로 제조되는 바이오디젤을 제공한다.In order to achieve the above object, the present invention is to prepare a by-product generated in the biodiesel manufacturing process to separate the glycerin and oil components, and to reproduce the biodiesel using a catalyst from the separated oil components and the method It provides a biodiesel produced.
본 발명에 있어서, 상기 촉매는 액체산촉매인 HCl, H2SO4, HNO3, H3PO4, HClO4 또는 CH3COOH, 고체산촉매인 강산성 이온교환수지 등의 산촉매나 NaOH, KOH, Ca(OH)2, K2CO3, 또는 NH4OH 등으로 이루어진 알칼리촉매, 미생물에서 유래한 다양한 리파제(lipase) 등의 화학촉매 또는 생물촉매를 포함한다. In the present invention, the catalyst is an acid catalyst such as HCl, H 2 SO 4 , HNO 3 , H 3 PO 4 , HClO 4 or CH 3 COOH as a liquid acid catalyst, a strong acidic ion exchange resin as a solid acid catalyst, or NaOH, KOH, Ca ( OH) 2 , K 2 CO 3 , or NH 4 OH or the like, and an alkali catalyst, a chemical catalyst or a biocatalyst such as various lipases derived from microorganisms.
본 발명은 종래 대부분 폐기되었던 증류 부산물을 재활용함으로써 바이오디젤의 부산물에서 바이오디젤을 재생산하는 방법을 제공하는 효과가 있으며, 상기 방법을 통해 보다 경제적으로 바이오디젤을 제조할 수 있을 뿐만 아니라 바이오디젤의 부산물을 원료로 활용하므로 최종적으로는 바이오디젤의 생산성을 향상시킬 수 있다.The present invention has the effect of providing a method for reproducing biodiesel from the by-products of biodiesel by recycling the distillation by-products that have been mostly discarded, through which the biodiesel can be produced more economically as well as by-products of biodiesel As a raw material, the productivity of the biodiesel can be improved.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 바이오디젤 제조과정에서 발생하는 부산물을 이용한 바이오디젤의 제조방법을 제공한다.The present invention provides a method for producing biodiesel using by-products generated in the biodiesel manufacturing process.
상기 본 발명은, (1) 바이오디젤 제조과정에서 발생하는 부산물을 정제하여 글리세린과 오일성분으로 분리하는 단계; 및 (2) 상기 분리된 오일성분에 알코올과 촉매를 혼합하여 바이오디젤을 재생산하는 단계;를 포함하는 것을 특징으로 한다.The present invention, (1) separating the by-products generated in the biodiesel manufacturing process into glycerin and oil components; And (2) regenerating biodiesel by mixing an alcohol and a catalyst to the separated oil component.
본 발명에서 상기 (1) 단계의 오일성분은 바이오디젤 부산물로부터 글리세린을 분리한 후 남는 약간의 점성이 있는 액체(피치)에 해당하며, 모노글리세라이드, 디글리세라이드가 주를 이루고, 탄화된 바이오디젤과 트리글리세라이드 등이 함유될 수 있다. 또한, 본 발명에서 바이오디젤 부산물을 정제하는 과정은 특별히 한정시킬 필요는 없으며, 업계에서 사용되는 통상적인 바이오디젤의 정제방법이라면 어떠한 방법도 무방하다.In the present invention, the oil component of step (1) corresponds to a slightly viscous liquid (pitch) remaining after separating glycerin from the biodiesel by-product, and is mainly composed of monoglycerides and diglycerides, and carbonized bio Diesel, triglycerides, and the like. In addition, the process of purifying biodiesel by-products in the present invention does not need to be particularly limited, and any method may be used as long as it is a conventional method for purifying biodiesel used in the industry.
또한, 상기 (2) 단계에서의 촉매는 화학촉매 또는 생물촉매를 사용하는 것이 바람직하며, 상기 화학촉매로는 액체산촉매인 HCl, H2SO4, HNO3, H3PO4, HClO4 또는 CH3COOH, 고체산촉매인 강산성 이온교환수지(예를 들면, Amberlyst-15 등) 등의 산촉매나 NaOH, KOH, Ca(OH)2, K2CO3, 또는 NH4OH 등으로 이루어진 알칼리촉매를 사용할 수 있고, 상기 생물촉매는 Candida antarctica, Pseudomonas cepacia, Candida regosa, Mucor miehei, Rhizopus oryzae 등의 미생물에서 유래한 다양한 리파제(lipase)를 사용하는 것이 더욱 바람직하다. 또한, 본 발명은 종래 알려진 다양한 종류의 촉매를 사용할 수 있으며, 상기 촉매는 반응물 총 중량에 대해 0.1 ~ 5중량%로 첨가되는 것이 바람직하다.In addition, it is preferable to use a chemical catalyst or a biocatalyst as the catalyst in step (2), and the chemical catalyst is HCl, H 2 SO 4 , HNO 3 , H 3 PO 4 , HClO 4 or CH which is a liquid acid catalyst. 3 An acid catalyst such as COOH, a strong acidic ion exchange resin (eg, Amberlyst-15), which is a solid acid catalyst, or an alkali catalyst consisting of NaOH, KOH, Ca (OH) 2 , K 2 CO 3 , or NH 4 OH, etc. may be used. The biocatalyst may more preferably use various lipases derived from microorganisms such as Candida antarctica , Pseudomonas cepacia , Candida regosa , Mucor miehei , Rhizopus oryzae, and the like. In addition, the present invention may use a variety of known catalysts, the catalyst is a reactant It is preferably added at 0.1 to 5% by weight relative to the total weight.
또한, 상기 (2) 단계에서 사용되는 알코올은 메탄올, 에탄올, 프로판올, 부탄올 중에서 선택되는 어느 하나 또는 둘 이상의 혼합물일 수 있으며, 오일성분과 각각 70~99중량% 및 1~30중량% 범위의 비율로 혼합되는 것이 바람직하다.In addition, the alcohol used in the step (2) may be any one or a mixture of two or more selected from methanol, ethanol, propanol, butanol, the proportion of the oil component and 70 to 99% by weight and 1 to 30% by weight, respectively It is preferable to mix with.
또한, 본 발명은 30~60℃의 온도 범위에서 3~24시간 동안 반응시키는 것이 바람직하다. Moreover, it is preferable to make this invention react for 3 to 24 hours in the temperature range of 30-60 degreeC.
또한, 본 발명은 통상적인 바이오디젤 제조과정에서 발생하는 부산물을 정제하여 글리세린과 오일성분으로 분리한 후 상기 오일성분으로부터 촉매를 사용하여 재생산한 바이오디젤을 제공한다.In addition, the present invention is purified by-products generated in the conventional biodiesel manufacturing process and the glycerin and After separation into an oil component, a biodiesel regenerated using a catalyst from the oil component is provided.
상기 바이오디젤은 본 발명의 방법에 따라 제조되는 것이 바람직하며, 이때 사용되는 촉매는 화학촉매 또는 생물촉매를 비롯하여 바이오디젤 제조 시 사용할 수 있는 모든 종류의 촉매를 포함한다.The biodiesel is preferably prepared according to the method of the present invention, wherein the catalyst used includes all kinds of catalysts that can be used in the production of biodiesel, including chemical catalysts or biocatalysts.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 당업계에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these examples are for illustrative purposes only and that the scope of the present invention is not construed as being limited by these examples.
실시예 1. 바이오디젤 부산물에서의 오일성분 분리Example 1 Separation of Oil Components from Biodiesel By-Products
본 발명에서는 양 등의 방법(양 영미 외, J. Korean Ind. Eng. Chem., Vol.19, No. 6, 690-692, 2008)에 따라, 중화, 침전, 증류 공정 등을 거쳐 바이오디젤 부산물에서 오일성분을 분리하였다.In the present invention, biodiesel is subjected to neutralization, precipitation, distillation, etc. according to the method of sheep and the like (Yang Yeong-mi et al., J. Korean Ind. Eng. Chem., Vol. 19, No. 6, 690-692, 2008). The oil component was separated from the byproduct.
구체적으로, 애경유화 주식회사에서 제공받은 바이오디젤 부산물을 70~90℃로 가열한 후 5~20중량%의 황산을 가하여 20~30분 동안 고속에서 교반하였다(중화공정). 이때 염의 분리 제거를 용이하게 하기 위하여 바이오디젤 부산물과 동량의 메탄올을 첨가하였으며, 약 18시간 동안 상온에서 방치하였다. Specifically, the biodiesel by-product provided by Aekyung Petrochemical Co., Ltd. was heated to 70-90 ° C., and 5-20% by weight of sulfuric acid was added thereto, followed by stirring at high speed for 20-30 minutes (neutralization process). At this time, in order to facilitate the separation and removal of salts, biodiesel by-products and the same amount of methanol were added and left at room temperature for about 18 hours.
침전이 완료되면 먼저 하부의 염층을 여과하여 분리한 후 원심분리기를 이용하여 글리세린과 오일성분을 분리하였다.When the precipitation was completed, first, the salt layer was separated by filtration, and then glycerin and oil were separated using a centrifuge.
실시예 2. 생물촉매를 사용한 바이오디젤의 제조Example 2. Preparation of Biodiesel Using Biocatalyst
상기 실시예 1에서 수득한 오일성분 75~95중량%와 메탄올 15~25중량% 및 촉매로 노보자임(Novozyme)사에서 구입한 Candida antarstica Lipase를 전체 중량에 대해 1중량% 첨가하고 35℃에서 진탕하면서 18시간 반응시켰다.75 to 95% by weight of the oil component obtained in Example 1, 15 to 25% by weight of methanol and 1% by weight of Candida antarstica Lipase purchased from Novozyme as a catalyst were added to the total weight and shaken at 35 ° C. The reaction was carried out for 18 hours.
반응이 완료된 원료는 분리조에서 수분을 제거한 다음 감압진공증류 과정을 거치면서 나머지 수분을 제거함과 동시에 순수한 바이오디젤을 분리하였다. 이 과정을 거치는 동안 반응물은 어두운(Dark) 색상에서 투명한(Clear) 색상으로 바뀌게 된다.After the reaction was completed, the raw material was removed from the separation tank, followed by vacuum distillation under reduced pressure to remove the remaining water and at the same time pure biodiesel was separated. During this process, the reactants change from dark to clear.
분리한 바이오디젤의 순도를 GC로 분석한 결과, 99중량% 이상이었다.The purity of the separated biodiesel was analyzed by GC, and the result was more than 99% by weight.
실시예 3. 화학촉매를 사용한 바이오디젤의 제조Example 3 Preparation of Biodiesel Using a Chemical Catalyst
상기 실시예 1에서 수득한 오일성분을 메탄올과 각각 85중량% 및 15중량% 비율로 혼합하고, 황산을 총 중량을 기준으로 2~3중량%를 더 가한 후 55~60℃에서 6시간 반응시켰다.The oil component obtained in Example 1 was mixed with methanol in an amount of 85% by weight and 15% by weight, respectively, and sulfuric acid was further added in an amount of 2 to 3% by weight based on the total weight and reacted at 55 to 60 ° C for 6 hours. .
메틸에스테르화율을 확인한 후 이상이 없으면 다음 과정으로 진행하고, 아직 반응이 완전히 일어나지 않은 경우에는 1~2시간 더 반응시켰다.After checking the methyl esterification rate, if there is no abnormality, the process proceeds to the next process, and if the reaction has not yet occurred, the reaction is further performed for 1 to 2 hours.
반응이 완료되면 메탄올을 회수한 후 수세하고, 수세한 후에는 분리조에서 수분을 제거한 다음 감압증류하여 색상과 순도를 점검하였다. After the reaction was completed, the methanol was recovered and washed with water. After washing, the water was removed from the separation tank and distilled under reduced pressure to check color and purity.
하기 표 1은 본 발명에 따른 바이오디젤 부산물에서 화학적 촉매 및 생물학적 촉매를 이용하여 재생산한 바이오디젤을 품질을 나타낸 결과표이다.Table 1 is a result table showing the quality of biodiesel reproduced using a chemical catalyst and a biological catalyst in the biodiesel by-product according to the present invention.
상기 표 1에서 보는 바와 같이, 본 발명의 재생산된 바이오디젤의 메틸에스테르의 순도는 각각 생물촉매 99% 및 화학촉매 98%로, 바이오디젤 국제품질규격기준인 메틸에스테르 순도 96% 이상을 만족하는 것을 확인할 수 있었다.As shown in Table 1, the purity of the methyl ester of the regenerated biodiesel of the present invention is 99% biocatalyst and 98% chemical catalyst, respectively, which satisfies the 96% or more purity of the methyl ester of biodiesel quality standard. I could confirm it.
이상, 본 발명의 내용의 특정한 부분을 상세히 기술하였는바, 당업계의 통상의 지식을 가진 자에게 있어서, 이러한 구체적인 기술은 단지 바람직한 실시양태일 뿐이며, 이에 의해 본 발명의 범위가 제한되는 것이 아닌 점은 명백할 것이다. 따라서, 본 발명의 실질적인 범위는 첨부된 청구항들과 그것들의 등가물에 의하여 정의된다고 할 것이다. As described above, specific portions of the contents of the present invention have been described in detail, and for those skilled in the art, these specific techniques are merely preferred embodiments, and the scope of the present invention is not limited thereto. Will be obvious. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.
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