KR960013617B1 - Treatment of waste working oil - Google Patents
Treatment of waste working oil Download PDFInfo
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- KR960013617B1 KR960013617B1 KR1019930022330A KR930022330A KR960013617B1 KR 960013617 B1 KR960013617 B1 KR 960013617B1 KR 1019930022330 A KR1019930022330 A KR 1019930022330A KR 930022330 A KR930022330 A KR 930022330A KR 960013617 B1 KR960013617 B1 KR 960013617B1
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- cutting oil
- waste cutting
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
- C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0208—Separation of non-miscible liquids by sedimentation
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- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Removal Of Specific Substances (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
Description
본 발명은 금속가공시 사용되는 페절삭유를 처리하는 방법에 관한 것이며, 더욱 상세히 설명하면 페절삭유가 함유하고 있는 기름성분을 분리 제거함으로써 폐수증의 기름성분을 없게 하고, 아울러 절삭유중에 함유된 금속성분중 기타 화학물질을 분리 제거하여, 폐절삭유는 폐수 처리하고, 절삭유에 함유된 기름성분과 같은 고형성분을 분리하여 연료 보조재료로 재활용하는 방법에 관한 것이다.The present invention relates to a method for treating waste cutting oil used in metal processing, and more specifically, to remove the oil component contained in the cutting oil to eliminate the oil component of the waste steam, and also the metal component contained in the cutting oil. Heavy chemicals are separated and removed, and the waste cutting oil is treated with wastewater, and the solid components such as oil components contained in the cutting oil are separated and recycled as fuel auxiliary materials.
절삭유는 금속가공공업의 발달로 인해 급격한 사용증가를 보이고 있으며, 1993년을 기준으로 볼 때 년간 9만톤 정도 사용되어 배출되는 것으로 추정되고 있다. 이같은 절삭유는 금속가공 종류에 따라 그 성분이 약간 다르나 대체적으로 15% 이하의 지방성분을 함유한 수용액으로 만들어져 있으며, 이같은 절삭유는 기름 성분과 수용액 성분의 상분리(相分離)를 막기 위해 계면활성제와 같은 화학물질을 혼합시켜, 안정된 에멀젼(emulsion)을 형성하고 있으므로, 금속가공시 윤활작용과 냉각작용 등을 하고 있는 것으로 알려지고 있다.Cutting oil is showing a rapid increase in use due to the development of metal processing industry, and it is estimated that about 90,000 tons are used and discharged per year as of 1993. These cutting oils are slightly different depending on the type of metal processing, but are generally made of an aqueous solution containing less than 15% of fat. Such cutting oils are used as surfactants to prevent phase separation of oil and aqueous components. Since chemical substances are mixed to form a stable emulsion, it is known that lubrication and cooling are performed during metal processing.
이같은 절삭유에는 금속가공시 금속성분 등이 함유된 상태에서 폐기되는데, 이 폐절삭유를 하수구에 방류하였을 때 절삭유에 함유된 기름성분, 계면활성제 같은 화학약품, 금속가공시 함유된 금속성분 등이 그대로 하천에 흘러들어가 하천오염을 일으키고 있다.Such cutting oil is discarded in the state of containing metal components during metal processing. When the waste cutting oil is discharged into the sewer, the oil components contained in the cutting oil, chemicals such as surfactants, and metal components contained in the metal processing are intact. It is flowing into and causing river pollution.
이같은 것을 막기위해 최근에는 역삼투압막(Reversed Osmosis Membrane)법으로 폐절삭유중에 함유된 기름성분, 화학성분 및 금속성분을 제거하는 방법이 보급되어 사용되어지고 있으나 장치비가 비싸고, 또한 막(膜)의 수명이 짧고 고가이며 운전조작이 복잡하다는 것이 결점으로 나타나고 있다.Recently, the reverse osmosis membrane (Reverse Osmosis Membrane) method to remove the oil, chemicals and metals contained in the waste cutting oil has been widely used, but the equipment cost is expensive, and also the membrane The shortcomings are short life, high cost and complicated operation.
본 발명은 이같은 문제점을 해결하고자 화학적인 방법으로 폐절삭유중의 기름성분, 계면활성제 같은 화학물질, 그리고 금속성분 등을 분리제거하여, 폐수처리하고자 하는 것이며, 폐수처리 과정에서 발생하는 부산물을 재활용하기위한 것이다.The present invention is to solve such problems by separating and removing the oil components, chemicals such as surfactants, and metals in the waste cutting oil by a chemical method, and to treat waste water, to recycle by-products generated in the waste water treatment process It is for.
우선, 폐절삭유에는 기름성분과 물성분이 혼합되어 있어 이것들의 상분리를 막기 위해 계면활성제를 첨가시켜 안정된 에멀젼을 형성하고 있다. 여기에 염산과 같은 강산을 서서히참가하여 PH3 이하의 산성, 최적 조건으로는 PH1이하로 한 다음 서서히 교반하면 폐절삭유에 함유된 계면활성제에 의해 형성된 마이셀(Micell)이 파괴되면서 유상성분과 수상(수용액)성분의 상분리가 일어난다. 이것을 조금더 확실히 분리하기 위해서는 초음파 발생기를 이용하여 초음파를 가하여 수용액중의 기름성분은 부상시키고 고형성분은 침전하게 한다.First, the waste cutting oil is mixed with an oil component and a water component, and a surfactant is added to form a stable emulsion to prevent phase separation thereof. In this process, a strong acid, such as hydrochloric acid, is gradually added to an acid of PH3 or lower, and optimally to PH1 or lower, and then slowly stirred to destroy micelles formed by the surfactant contained in the waste cutting oil. Phase separation of the components occurs. To separate it more reliably, ultrasonic waves are applied using an ultrasonic generator to float the oil components in the aqueous solution and to precipitate the solid components.
여기에는 절삭유 종류에 따라 조금의 차이가 있으나 대부분 쉽게 분리된다. 여기에 소석회와 같은 무기물질을 0.5%(w/v)이상, 최적 조건으로 1.5%(w/v) 이상 첨가 교반하여 폐절석유의 PH를 10 이상의 알칼리성으로 한 후 정치하면 무기물질외에 고형성분 및 기름성분 등이 응고하고 침전하게된다.There are some differences depending on the type of coolant, but most are easily separated. At least 0.5% (w / v) of inorganic substances such as slaked lime and 1.5% (w / v) of at least optimal conditions are added and stirred to make the pH of the waste stone oil 10 or more alkaline. The oil component will coagulate and settle.
이같이 침전된 고형성분을 제거하기 위해 진공필터(Vaccum-filter)탈수기와 필터프레스(Filter-Press)탈수기 등이 사용되고 있으나, 본 특허에 적합한 탈수기로는 벨트프레스 탈수기를 예로 들 수 있다. 벨트프레스(Belt-Press)탈수기는 여포 사이에 슬러리를 넣어 압착시켜 탈수하게 되므로 탈수여포에서의 케이크(Cake)의 박리성이 무엇보다도 중요하고, 또한 슬러리에 다량 함유된 기름성분 등이 벨트프레스 등과 같은 여포를 이용한 탈수기에 사용시 유분에 의한 여포의 오염이 큰 문제시 되며, 특히 압력하에서 수분이 효과적으로 제거되지 못하고 슬러리와 함께 유분이 여포 사이에 끼어 탈수 효율의 저하는 물론 연속운전이 불가능하므로, 본 특허에서는 소석회 또는 규조토 및 맥반석 등을 병용하여 사용하였다. 그 결과 소석회 대 규조토, 또는 맥반석의 함유 비율이 3 : 1 경우 최적의 효과를 보였다. 그리하여 소석회등 무기질 파우더에 유분이 흡수되어 탈수효과를 증진시켰다. 이같이 분리된 수용액을 활성탄, 이온 교환수지 컬럼을 통과시킴으로써 수용액중에 소량 함유된 기름성분, 화학약품성분, 금속성분 등이 완전히 제거하여 증수 또는 하급 공업용수 등으로 재활용 가능하게 하였다.Vacuum filter (Vaccum-filter) dehydrator and Filter-Press dehydrator, etc. are used to remove the solid components thus precipitated, the belt press dehydrator is an example of a dehydrator suitable for the present patent. Since the belt press dehydrator is dehydrated by inserting a slurry between the follicles, the peelability of the cake in the dehydrated follicles is most important, and the oil component contained in the slurry is important in the belt press and the like. When used in a dehydrator using the same follicles, contamination of the follicles by oil is a big problem. Especially, moisture is not effectively removed under pressure, and oil is trapped between the follicles together with the slurry, which reduces the dehydration efficiency and makes continuous operation impossible. In the patent, calcined lime or diatomaceous earth and elvan rock were used in combination. As a result, when the ratio of slaked lime to diatomaceous earth or elvan was 3: 1, the optimum effect was obtained. Thus, oil is absorbed into mineral powders such as slaked lime to enhance the dehydration effect. The separated aqueous solution was passed through activated carbon and ion exchange resin columns to completely remove oil components, chemical components, metal components, etc. contained in the aqueous solution, and to recycle them to steam or lower industrial water.
수용액중의 기름성분량을 조사하기 위해 딘 스토크(Dean-Stock)장치를 이용한 수분정량(水分定量)검사를 실시한 결과 기름성분은 전혀 존재하지않았다.In order to investigate the amount of oil in the aqueous solution, a water quantitative test was conducted using a Dean-Stock apparatus.
한편, 소석회등에 의해 침전시킨 고형성분은 탈수기에 의해 케이트(C맏)상으로 만든 후, 여기에 함유된 기름성분을 재활용하고자, 수용액 폐수처리에서 사용이 끝난 활성탄 등 목질계 유기물질을 혼합시켜 건조시킴으로써 연료보조 재료로 사용가능가능하게 하였다.On the other hand, the solid component precipitated by slaked lime, etc. is made into a Kate (C first) phase by a dehydrator and then dried by mixing wood-based organic materials such as activated carbon used in aqueous wastewater treatment to recycle the oil contained therein. Thereby making it usable as a fuel aid material.
실시예 1)Example 1
절삭유 1리터에 12N HCL 1m1를 방울 방울 떨어뜨린 후 5분 동안 교반시켰다.Dropped 12N HCL 1m1 into 1 liter of cutting oil and stirred for 5 minutes.
그러면 소량의 고형성분이 침전되어 일어나고, 소량의 기름성분이 부상하였다. 여기에 24W의 초음파 발생기를 5분 동안 조사한 후 다시 교반하면서 소석회 파우더 15g을 넣어 3분간 교반후 정치시켰다. 소석회 및 기름성분, 화학성분, 금속성분 등은 곧바로 침전되고, 상등액은 투명한 수용액이 되었다. 이 상등액을 필터로 걸러 고형성분을 제거한 후 활성탄 컬럼과 음이온, 양이온 이온 교환수지 컬럼에 차례로 통과시킨 후 수용액 중의 기름성분을 조사한 결과 완전히 제거되었다.Then, a small amount of solid component precipitated out and a small amount of oil component floated. After irradiating the ultrasonic generator of 24 W for 5 minutes, 15 g of hydrated lime powder was added while stirring again, followed by stirring for 3 minutes. Calcined lime, oil, chemicals, metals, etc. immediately precipitated, and the supernatant became a transparent aqueous solution. The supernatant was filtered to remove solid components, and then passed through an activated carbon column, an anion, and a cation ion exchange resin column, and then the oil components in the aqueous solution were completely removed.
실시예 2)Example 2)
실시예1에서 고형성분 및 기름성분을 침지시키기 위해 소석회 대신 소석회와 규조토롤 3 : 1로 혼합한 것 또는 소석회와 맥반석(240메쉬 분말)을 3 : 1로 혼합한 것을 15g첨가하여 교반하면 고형분 침전 속도가 향상되었다.In Example 1, in order to immerse the solid component and the oil component, the mixture of slaked lime and diatomaceous earth roll 3: 1 instead of slaked lime or mixed with slaked lime and ganbanite (240 mesh powder) 3: 1 was added and stirred, and the solids precipitated. Speed has been improved.
한편, 이같은 고형성분을 탈수 과정에서 벨트프레스 필타(Belt-Press Filter)장치의 탈수포에서 케이크의 박리성이 규조토 및 맥반석을 첨가시킨 것이 좋은 효과를 가져다 주었다.On the other hand, the peelability of the cake in the dehydrated fabric of the belt press filter (Belt-Press Filter) in the dehydration process of the solid component, the addition of diatomaceous earth and elvan was good effect.
이같이 제거된 고형성분에 폐수용액 처리시 시용시 끝난 활성탄 등을 혼합시켜, 압축기로 작은 모양의 덩어리를 만든 후 건조시켜 연료 보조 재료로 사용한 결과 열량 향상이 증대되었다.The solid components thus removed were mixed with activated carbon, etc., which had been applied during the treatment of the wastewater solution, and then made into small lumps by a compressor, and then dried and used as a fuel auxiliary material.
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