WO2017213427A1 - Procédé pour la réduction des eaux usées générées par un processus de purification de biodiesel et pour la récupération de glycérine à l'aide d'un processus de filtration combinant une membrane de filtration polymère, une membrane d'ultrafiltration et une membrane osmotique inverse - Google Patents

Procédé pour la réduction des eaux usées générées par un processus de purification de biodiesel et pour la récupération de glycérine à l'aide d'un processus de filtration combinant une membrane de filtration polymère, une membrane d'ultrafiltration et une membrane osmotique inverse Download PDF

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Publication number
WO2017213427A1
WO2017213427A1 PCT/KR2017/005939 KR2017005939W WO2017213427A1 WO 2017213427 A1 WO2017213427 A1 WO 2017213427A1 KR 2017005939 W KR2017005939 W KR 2017005939W WO 2017213427 A1 WO2017213427 A1 WO 2017213427A1
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WO
WIPO (PCT)
Prior art keywords
membrane
glycerin
filtration
filtration membrane
oil
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Application number
PCT/KR2017/005939
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English (en)
Korean (ko)
Inventor
김재권
이동환
Original Assignee
(주)대원인터내셔널
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Publication of WO2017213427A1 publication Critical patent/WO2017213427A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2317/00—Membrane module arrangements within a plant or an apparatus
    • B01D2317/08—Use of membrane modules of different kinds

Definitions

  • the present invention relates to a method for effectively treating biodiesel washing wastewater using various separation membranes. More specifically, the present invention relates to a method for reducing wastewater generated from a biodiesel washing process by using a filtration process combining a combined filtration membrane, an ultrafiltration membrane, and a reverse osmosis membrane, and recovering glycerin.
  • the reaction between animal and vegetable fats and methanol produces biodiesel and glycerin, with biodiesel at the top of the reactor separated by a layer of glycerin at the bottom.
  • biodiesel at the top of the reactor separated by a layer of glycerin at the bottom.
  • less than 1% glycerin and trace metal salts are dissolved in the biodiesel layer.
  • the upper biodiesel is purified by distillation and water washing. Even after the distillation process, a significant amount of glycerin is dissolved in the biodiesel, so the glycerin must be removed in the biodiesel by washing with an aqueous solution. This is because biodiesel products only allow free glycerin below 0.02 wt%. A large amount of washing waste water is generated through the aqueous solution washing.
  • the rinsing wastewater contains an oil (O / W) emulsion and glycerin.
  • Oil emulsions not only increase the COD of the wastewater, but also slowly collect to form an oil layer, which greatly affects the biological and physical treatment methods of the wastewater. Therefore, biodiesel cleaning wastewater is causing environmental pollution problem to be very difficult to treat.
  • glycerin and oil emulsion in waste water are separated and concentrated separately, the oil in waste water can be reused as raw material, and glycerin can be sold as a product.
  • Korean Patent Laid-Open Publication No. 10-2008-0062616 as a prior art for solving the above problems discloses a method for purifying crude glycerin using a filtering technique. More specifically, the prior art is purified by passing a mixture of crude glycerin and water through a membrane filter consisting of a nano-filtering membrane separation module connected to at least one series and at least one reverse osmosis membrane separation module connected to the module in series. Disclosed is a method for purifying crude glycerin to prepare glycerin.
  • the present invention has been made to solve the above-mentioned problems of the prior art, the object of which is to reduce the cost of treating high concentration organic waste water, and to provide a process for recycling the waste resources.
  • the oil and glycerin are separated from the wastewater containing the oil emulsion and glycerin generated in the biodiesel washing process
  • a separation method is provided.
  • the coal filtration membrane is used to coalesce the emulsion oil to recover pure oil.
  • the emulsion oil and the aqueous solution of glycerin are separated using the ultrafiltration membrane.
  • the present invention can effectively treat an oil emulsion-containing biodiesel washing wastewater that is difficult to treat by disposing a coalescence membrane, an ultrafiltration membrane, and a reverse osmosis membrane that have different characteristics from each other.
  • the present invention can significantly reduce the environmental protection and cost by separating and recovering water, oil, and glycerin without generating any waste water.
  • FIG. 1 is a view schematically illustrating a method of reducing wastewater generated from a biodiesel washing process and recovering glycerin using a filtration process combining a coalescence membrane, an ultrafiltration membrane, and a reverse osmosis membrane according to an embodiment of the present invention.
  • the present invention may have various modifications and may have various embodiments.
  • fine oil emulsion is adsorbed in the form of droplets on the inner surface of the coal filtration membrane and coalesces with other oil droplets which continue to flow.
  • the larger emulsion droplets create a liquid-like flow that flows into the coalescence membrane, and after passing through the coalescence membrane, are separated from the wastewater and collected into an oil layer.
  • an ultrafiltration membrane is introduced to increase the concentration of the oil emulsion in the wastewater and at the same time remove the oil emulsion in the wastewater. Since the ultrafiltration membrane in the form of a hollow fiber membrane made of a material having hydrophilic properties such as cellulose acetate polysulfone pushes the oil emulsion to adhere, water and glycerin pass through the surface of the ultrafiltration membrane when the washing waste water passes through the ultrafiltration membrane. The oil emulsion that is passed and whose surface access is denied is gradually concentrated and circulated.
  • FIG. 1 is a view schematically illustrating a method of reducing wastewater generated from a biodiesel washing process and recovering glycerin using a filtration process combining a coalescence membrane, an ultrafiltration membrane, and a reverse osmosis membrane according to an embodiment of the present invention.
  • Increasing the concentration of oil emulsion in the ultrafiltration membrane promotes the removal of the oil emulsion in the coalescence membrane, and removes most of the oil emulsion in the coalescence membrane, thereby lowering the concentration of the oil emulsion introduced into the ultrafiltration membrane, thereby improving the performance of the ultrafiltration membrane. It increases the risk of contamination of the ultrafiltration membrane by oil. Therefore, the oil emulsion can be removed continuously.
  • the ultrafiltration membrane permeate (5) permeates the reverse osmosis membranes (9, 10) consisting of two stages, pure water (11) is reused again in the factory, and the concentrated glycerin (12) is sent to the glycerin purification process to be commercialized.
  • the ultrafiltration membrane 1 and the coalescence membrane 2 are connected in series to concentrate the oil emulsion and recover the oil, and the ultrafiltration membrane 1 and the reverse osmosis membrane 9, 10. Are connected in series to remove the oil emulsion, concentrate the glycerin and recover the washing water.
  • the ultrafiltration membranes were polysulfone-based two hollow fiber membranes of 377mm size, and the coalescence membrane was made of polypropylene, and the filter unit was equipped with three coalescence membranes of 0.5 ⁇ m pore size and 760mm length cartridge.
  • the reverse osmosis membrane is a cellulose acetate-based 40 inch Dow product.
  • the wastewater is supplied at 150 liters per hour, followed by an ultrafiltration membrane, a coalescence membrane, and a reverse osmosis membrane. After all systems have been normalized, run for 48 hours to stabilize.
  • the wastewater contains 0.8 wt% glycerin and 0.3 wt% oil emulsion. After 48 hours, an average of 10 kg of pure oil was recovered from the upper portion of the coal filtration membrane (2), and no oil emulsion was detected in the (5), (11) and (12) solutions.
  • the glycerin concentrations in the solutions (5), (11) and (12) were measured as 0.8 wt%, 0.005 wt%, and 7.3 wt%, respectively.
  • the biodiesel washing water generated as waste water was purified and the recovered water was used again as washing water, and the volume of the final washing water was reduced by 9.1 times, and the final solution 11 was sent to the glycerin purification process. Glycerin concentration could be maintained.

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  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Nanotechnology (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne un procédé pour la réduction des eaux usées générées par un processus de purification de biodiesel et pour la récupération de glycérine à l'aide d'un processus de filtration combinant une membrane de filtration polymère, une membrane d'ultrafiltration et une membrane osmotique inverse. La présente invention concerne un procédé de séparation caractérisé par la séparation d'huile et de glycérine d'eaux usées, contenant une émulsion d'huile et de la glycérine produites pendant un processus de lavage de biodiesel, au moyen d'un processus de filtration combinant une membrane de filtration polymère, une membrane d'ultrafiltration et une membrane osmotique inverse.
PCT/KR2017/005939 2016-06-10 2017-06-08 Procédé pour la réduction des eaux usées générées par un processus de purification de biodiesel et pour la récupération de glycérine à l'aide d'un processus de filtration combinant une membrane de filtration polymère, une membrane d'ultrafiltration et une membrane osmotique inverse WO2017213427A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2016-0072664 2016-06-10
KR1020160072664A KR20170140484A (ko) 2016-06-10 2016-06-10 합체여과막, 한외여과막 및 역삼투막을 조합한 여과공정을 이용하여 바이오디젤 세정 공정으로부터 발생하는 폐수를 감용하고, 글리세린을 회수하는 방법

Publications (1)

Publication Number Publication Date
WO2017213427A1 true WO2017213427A1 (fr) 2017-12-14

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WO (1) WO2017213427A1 (fr)

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KR102116369B1 (ko) 2018-11-26 2020-05-28 무진기공주식회사 바이오디젤 제조 공정에서 글리세린 분리방법
KR102429866B1 (ko) * 2020-05-18 2022-08-05 해양환경공단 소형 선박 선저폐수 기름 여과 장치

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR200333688Y1 (ko) * 2003-08-29 2003-11-17 이준호 오일 정제 장치
KR100877384B1 (ko) * 2008-06-30 2009-01-07 바이오원 (주) 필터링 기술을 이용한 조 글리세린의 정제방법
KR20110058967A (ko) * 2009-11-27 2011-06-02 제이씨케미칼(주) 바이오디젤 증류를 위한 증류장치 및 이를 이용한 증류방법
KR20130050135A (ko) * 2011-11-07 2013-05-15 (주)웸스 바이오디젤 생산 공정에서 발생하는 유기성 부산물 중 ｂｔｅｘ의 정제방법 및 ｂｔｅｘ가 정제된 유기성 부산물을 이용한 하폐수의 질소 제거 방법
KR20150016475A (ko) * 2013-08-01 2015-02-12 주식회사 엘지화학 내구성이 우수한 폴리아미드계 수처리 분리막 및 그 제조방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR200333688Y1 (ko) * 2003-08-29 2003-11-17 이준호 오일 정제 장치
KR100877384B1 (ko) * 2008-06-30 2009-01-07 바이오원 (주) 필터링 기술을 이용한 조 글리세린의 정제방법
KR20110058967A (ko) * 2009-11-27 2011-06-02 제이씨케미칼(주) 바이오디젤 증류를 위한 증류장치 및 이를 이용한 증류방법
KR20130050135A (ko) * 2011-11-07 2013-05-15 (주)웸스 바이오디젤 생산 공정에서 발생하는 유기성 부산물 중 ｂｔｅｘ의 정제방법 및 ｂｔｅｘ가 정제된 유기성 부산물을 이용한 하폐수의 질소 제거 방법
KR20150016475A (ko) * 2013-08-01 2015-02-12 주식회사 엘지화학 내구성이 우수한 폴리아미드계 수처리 분리막 및 그 제조방법

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