WO2017213427A1 - Method for reducing waste water generated from biodiesel purification process and recovering glycerin using filtration process combining polymer filtration membrane, ultra-filtration membrane and reverse osmotic membrane - Google Patents

Method for reducing waste water generated from biodiesel purification process and recovering glycerin using filtration process combining polymer filtration membrane, ultra-filtration membrane and reverse osmotic membrane Download PDF

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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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membrane
glycerin
filtration
filtration membrane
oil
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PCT/KR2017/005939
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French (fr)
Korean (ko)
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김재권
이동환
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(주)대원인터내셔널
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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.

Abstract

The present invention relates to a method for reducing waste water generated from a biodiesel purification process and recovering glycerin using a filtration process combining a polymer filtration membrane, ultra-filtration membrane and reverse osmotic membrane. The present invention provides a separation method characterized by separating oil and glycerin from waste water, containing oil emulsion and glycerin produced during a biodiesel washing process, by means of a filtration process combining a polymer filtration membrane, ultra-filtration membrane and reverse osmotic membrane.

Description

합체여과막, 한외여과막 및 역삼투막을 조합한 여과공정을 이용하여 바이오디젤 세정 공정으로부터 발생하는 폐수를 감용하고, 글리세린을 회수하는 방법 Wastewater generated from the biodiesel cleaning process using a filtration process combining a combined filtration membrane, an ultrafiltration membrane, and a reverse osmosis membrane, and recovering glycerin
본 발명은 바이오디젤 세정 폐수를 여러 가지 분리막을 이용하여 효과적으로 처리하기 방법에 관한 것이다. 보다 구체적으로, 본 발명은 합체여과막, 한외여과막 및 역삼투막을 조합한 여과공정을 이용하여 바이오디젤 세정 공정으로부터 발생하는 폐수를 감용하고, 글리세린을 회수하는 방법에 관한 것이다.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.
고체 비균질 촉매하에서, 동식물성 유지와 메탄올을 반응을 시키면 바이오디젤과 글리세린이 만들어지며, 반응기의 상단에는 바이오디젤이 그 하단에는 글리세린의 층으로 분리된다. 그러나 바이오디젤 층에는 1% 미만의 글리세린과 미량의 금속염이 용해되어 있다. 상층의 바이오디젤은 증류와 수세정을 통하여 정제된다. 증류공정 이후에도 바이오디젤 내에는 상당량의 글리세린이 녹아있기 때문에 반드시 수용액 세정으로 바이오디젤 내에 글리세린을 제거해야 한다. 왜냐하면 바이오디젤 제품은 0.02wt% 이하의 유리 글리세린만 허용되기 때문이다. 수용액 세정을 통하여 다량의 세정 폐수가 발생되게 된다.Under a solid heterogeneous catalyst, 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. However, 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.
세정 폐수에는 오일(O/W) 에멀젼과 글리세린이 혼합되어 있다. 오일 에멀젼은 폐수의 COD를 높일 뿐만 아니라, 천천히 모여져 기름층을 형성하게 되고, 폐수의 생물학적 처리와 물리적 처리 방법에 큰 악영향을 끼친다. 따라서 바이오디젤 세정 폐수는 매우 처리하기 어려고 환경오염의 문제를 야기하고 있다. 그러나 폐수 내의 글리세린과 오일 에멀젼은 별도로 분리하여 농축시키면, 폐수내의 오일은 원료로 재사용하고, 글리세린은 제품으로 판매가 가능하다.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. However, if 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.
상기 문제점을 해결하기 위한 종래기술로서 대한민국 공개특허공보 제10-2008-0062616호에는 필터링 기술을 이용한 조 글리세린의 정제방법을 개시하고 있다. 보다 상세하게 상기 종래기술은 조 글리세린(crude glycerin)과 물의 혼합물을 적어도 하나의 직열로 연결된 나노필터링 막분리 모듈과 상기 모듈과 직열로 연결된 적어도 하나의 역삼투막 막분리 모듈로 구성된 분리막 필터를 통과시켜 정제 글리세린을 제조하는 조 글리세린의 정제방법을 개시한다.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.
본 발명은 상술한 종래기술의 문제점을 해결하기 위해 창안된 것으로, 그 목적은 고농도의 유기폐수 처리비용을 절감하고, 폐기물로 버려지는 자원을 재활용하는 공정을 제공하는 것이다.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.
본 발명의 일 실시예에 따르면, 합체여과막, 한외여과막 및 역삼투막을 조합한 여과공정을 이용하여, 바이오디젤 수세공정에서 발생하는 오일에멀젼과 글리세린을 함유한 폐수로부터 오일과 글리세린을 분리하는 것을 특징으로 하는 분리방법이 제공된다.According to one embodiment of the present invention, by using a filtration process combined with a coal filtration membrane, an ultrafiltration membrane and a reverse osmosis membrane, 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.
바람직하게, 상기 합체여과막을 이용하여 에멀젼오일을 합체해 순수한 오일을 회수하는 것을 특징으로 한다.Preferably, the coal filtration membrane is used to coalesce the emulsion oil to recover pure oil.
바람직하게, 상기 한외여과막을 이용하여 에멀젼오일과 글리세린 수용액을 분리하는 것을 특징으로 한다.Preferably, the emulsion oil and the aqueous solution of glycerin are separated using the ultrafiltration membrane.
바람직하게, 상기 역삼투막을 이용하여 농축 글리세린과 정제된 물을 회수하는 것을 특징으로 한다.Preferably, using the reverse osmosis membrane to recover the concentrated glycerin and purified water.
본 발명은 서로 특성이 다른 합체여과막, 한외여과막 및 역삼투막을 특성에 맞게 배치함으로써, 처리하기 어려운 오일에멀젼 함유 바이오디젤 세정 폐수를 효과적으로 처리할 수 있다.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.
또한, 본 발명은 폐수를 전혀 발생시키지 않으면서도 물과 기름, 글리세린을 분리하여 회수함으로써 환경보호와 원가를 크게 절감할 수 있다.In addition, the present invention can significantly reduce the environmental protection and cost by separating and recovering water, oil, and glycerin without generating any waste water.
도 1은 본 발명의 일 실시예에 따른 합체여과막, 한외여과막 및 역삼투막을 조합한 여과공정을 이용하여 바이오디젤 세정 공정으로부터 발생하는 폐수를 감용하고, 글리세린을 회수하는 방법을 개략적으로 도시한 도면이다.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. .
이하, 첨부된 도면을 참조하여 본 발명의 실시예를 상세히 설명하면 다음과 같다. 그러나 본 발명은 이하에서 개시되는 실시예에 한정되는 것이 아니라 서로 다른 다양한 형태로 구현될 수 있는 것으로, 이하의 실시예는 본 발명의 개시가 완전하도록 하며, 통상의 지식을 가진 자에게 발명의 범주를 완전하게 알려주기 위해 제공되는 것이다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but can be implemented in various forms, and the following embodiments are intended to complete the disclosure of the present invention, the scope of the invention to those skilled in the art It is provided to inform you completely.
본 발명은 다양한 변경을 가할 수 있고 여러 가지 실시예를 가질 수 있다.The present invention may have various modifications and may have various embodiments.
따라서 본 발명은 본 발명의 사상 및 기술 범위에 포함되는 모든 변경, 균등물 내지 대체물을 포함하는 것으로 이해되어야 한다.Therefore, it is to be understood that the present invention includes all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.
본 출원에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다.The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this application, the terms "comprise" or "have" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.
다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다.Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art. Terms such as those defined in the commonly used dictionaries should be construed as having meanings consistent with the meanings in the context of the related art and shall not be construed in ideal or excessively formal meanings unless expressly defined in this application. Do not.
이하, 본 발명에 따른 바람직한 실시예를 첨부된 도면을 참조하여 상세하게 설명한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
폐수 처리시 발생하는 오일 에멀젼을 합체여과막을 이용하여 수용액과 분리하는 방법이 개시된다. 세정 폐수를 친유성 합체여과막을 통과시키면, 미세한 오일에멀젼이 합체여과막 내부 표면에 방울 형태로 흡착되며, 계속해서 유입되는 다른 오일방울과 부딪쳐 합체된다. 이런 과정이 되풀이됨으로써, 점점 커진 에멀젼 방울은 액상형태의 흐름이 만들어져 합체여과막 내부로 흐르고, 합체여과막을 통과 후 폐수와 분리되어 기름 층으로 모여진다.Disclosed is a method of separating an oil emulsion generated during wastewater treatment from an aqueous solution using a coal filtration membrane. When the rinsing wastewater is passed through the lipophilic coal filtration membrane, 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. By repeating this process, 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.
그러나 오일에멀젼의 농도가 낮으면 방울들이 부딪치는 확률이 낮아, 원활한 합체가 일어나지 않는다. 이러한 문제점을 보완하기 위하여 한외여과막을 도입하여 폐수의 오일에멀젼의 농도를 높임과 동시에 다른 한편에선 폐수 중의 오일에멀젼을 제거한다. 셀룰로오스아세테이트 폴리설폰 등 친수성 성질을 갖는 재료로 제작된 중공사막 형태의 한외여과막은 오일에멀젼이 부착되는 것을 밀어내므로, 세정폐수를 상기 한외여과막에 통과시키면 물과 글리세린은 한외여과막의 표면을 투과하여 통과되고, 표면접근이 거부된 오일에멀젼은 점점 농축되어 순환된다.However, if the oil emulsion concentration is low, there is a low probability that the droplets collide, and smooth coalescence does not occur. In order to compensate for this problem, 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.
도 1은 본 발명의 일 실시예에 따른 합체여과막, 한외여과막 및 역삼투막을 조합한 여과공정을 이용하여 바이오디젤 세정 공정으로부터 발생하는 폐수를 감용하고, 글리세린을 회수하는 방법을 개략적으로 도시한 도면이다.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. .
도 1에 도시된 바와 같이, 한외여과막(1)과 합체여과막(2)을 직렬로 연결하고, 폐수탱크(3)에서 폐수(4)를 한외여과막(1)에 주입하면, 통과할 때 물과 글리세린은 투과액(5)으로 막을 통과하여 배출되고, 에멀젼은 농축이 되어 잔류액(6)으로 배출된다. 잔류액이 합체여과막(2)으로 투입되면 오일에멀젼은 합체가 일어나 오일층(7)으로 쌓여서 배출되어 재사용되며, 오일에멀젼이 남아있는 여과액(8)은 폐수탱크(3)로 순환되어 다시 한외여과막으로 투입된다. 상기 2개의 서로 다른 막공정의 사용은 각각의 공정의 단점을 완벽하게 보완하여 준다. 한외여과막에서 오일에 멀젼의 농도를 높여주어 합체여과막에서 오일에멀젼의 제거를 촉진하고, 합체여과막에서 대부분의 오일에멀젼이 제거됨으로써 한외여과막에 투입되는 오일에멀젼의 농도를 낮추어 주어, 한외여과막의 성능을 높여주면서, 오일에 의한 한외여과막의 오염위험성을 낮추어 준다. 따라서 연속적으로 오일에멀젼을 제거할 수 있다.As shown in FIG. 1, when the ultrafiltration membrane 1 and the coalescence membrane 2 are connected in series, and the wastewater 4 is injected into the ultrafiltration membrane 1 from the wastewater tank 3, water and Glycerin is discharged through the membrane to the permeate (5), the emulsion is concentrated and discharged to the residual (6). When the residual liquid is introduced into the coal filtration membrane (2), the oil emulsion is coalesced, accumulated in the oil layer (7), discharged and reused, and the filtrate (8) in which the oil emulsion remains is circulated to the waste water tank (3) and again It is put into the filtration membrane. The use of the two different membrane processes completely compensates for the disadvantages of each process. 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.
한외여과막 투과액(5)은 오일에멀젼이 없기 때문에, 오일에 의한 역삼투막 막힘의 위험성이 재거되어, 글리세린 농축에 역삼투막을 사용할 수 있다. 한외여과막 투과액(5)은 2단으로 구성된 역삼투막(9,10)을 투과하며, 순수한 물(11)은 다시 공장에서 재사용하고, 농축된 글리세린(12)은 글리세린 정제공정으로 보내져 제품화된다.Since the ultrafiltration membrane permeate 5 has no oil emulsion, the risk of clogging the reverse osmosis membrane by oil is eliminated, and a reverse osmosis membrane can be used for glycerin concentration. 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.
상술한 바와 같이, 본 발명의 일 실시예는 한외여과막(1)과 합체여과막(2)을 직렬로 연결하여 오일에멀젼을 농축하고 오일을 회수하고, 한외여과막(1)과 역삼투막(9,10)을 직렬로 연결하여 오일에멀젼을 제거하고 글리세린을 농축하며, 세정수를 회수할 수 있도록 구성된다.As described above, in one embodiment of the present invention, 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.
한외여과막은 폴리설폰계로 377mm 크기의 할로우 파이버막을 2기를 설치하였으며, 합체여과막으로는 폴리프로필렌 재질로서, 기공의 크기 0.5㎛, 길이 760mm의 카트리지 형태의 합체여과막 3개를 장착한 필터 유니트를 설치하였으며, 역삼투막은 초산셀룰로오스계로 40인치 Dow제품을 설치하였다.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 0.5μm pore size and 760mm length cartridge. The reverse osmosis membrane is a cellulose acetate-based 40 inch Dow product.
폐수를 시간당 150리터로 공급하고 한외여과막, 합체여과막 및 역삼투막 순으로 차례로 가동을 시킨다. 모든 시스템이 정상화된 후 48시간 동안 지속적으로 가동하여 안정화시킨다. 폐수에는 0.8wt%의 글리세린과 0.3wt%의 오일에멀젼이 함유되어 있다. 48시간이 경과 후 합체여과막(2) 상부에서 순수 오일이 하루 평균 10kg이 회수되었고, 상기 (5), (11) 및 (12) 용액에서는 오일에멀젼이 검출되지 않았다. 상기 (5), (11) 및 (12) 용액 내 글리세린 농도는 각각 0.8wt%, 0.005wt%, 7.3wt%로 측정되었다.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.
본 발명으로 인하여 폐수로 발생되는 바이오디젤 세정수를 정제하여 회수된 물을 다시 세정수로 사용하게 되었으며, 최종 세정수의 부피는 9.1배 줄일 수 있었고, 최종 용액(11)은 글리세린 정제 공정으로 보낼 수 있는 글리세린 농도를 유지할 수 있었다.Due to the present invention, 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.

Claims (4)

  1. 합체여과막, 한외여과막 및 역삼투막을 조합한 여과공정을 이용하여, 바이오디젤 수세공정에서 발생하는 오일에멀젼과 글리세린을 함유한 폐수로부터 오일과 글리세린을 분리하는 것을 특징으로 하는 분리방법.A separation method comprising separating oil and glycerin from wastewater containing oil emulsion and glycerin generated in the biodiesel washing process using a filtration process combining a coalescence membrane, an ultrafiltration membrane and a reverse osmosis membrane.
  2. 제 1 항에 있어서,The method of claim 1,
    상기 합체여과막을 이용하여 에멀젼오일을 합체해 순수한 오일을 회수하는 것을 특징으로 하는 분리 방법.Separation method characterized in that to recover the pure oil by coalescing the emulsion oil using the coalescence membrane.
  3. 제 1 항에 있어서,The method of claim 1,
    상기 한외여과막을 이용하여 에멀젼오일과 글리세린 수용액을 분리하는 것을 특징으로 하는 분리방법.Separation method characterized in that the emulsion oil and the aqueous solution of glycerin is separated using the ultrafiltration membrane.
  4. 제 3 항에 있어서,The method of claim 3, wherein
    상기 역삼투막을 이용하여 농축 글리세린과 정제된 물을 회수하는 것을 특징으로 하는 분리방법.Separation method, characterized in that for recovering concentrated glycerin and purified water using the reverse osmosis membrane.
PCT/KR2017/005939 2016-06-10 2017-06-08 Method for reducing waste water generated from biodiesel purification process and recovering glycerin using filtration process combining polymer filtration membrane, ultra-filtration membrane and reverse osmotic membrane WO2017213427A1 (en)

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