KR100381453B1 - Method for treating wastewater containing acetic acid and apparatus thereof - Google Patents
Method for treating wastewater containing acetic acid and apparatus thereof Download PDFInfo
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- KR100381453B1 KR100381453B1 KR10-2000-0068123A KR20000068123A KR100381453B1 KR 100381453 B1 KR100381453 B1 KR 100381453B1 KR 20000068123 A KR20000068123 A KR 20000068123A KR 100381453 B1 KR100381453 B1 KR 100381453B1
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
본 발명은 초산을 포함하는 폐수의 처리 방법 및 장치에 관한 것이다.The present invention relates to a method and apparatus for treating wastewater comprising acetic acid.
본 발명에 의하면 활성 탄소와 촉매 층이 있는 반응기를 이용하여, 폐수로부터 초산을 분리 회수하고 정화된 폐수를 재활용할 수가 있는데, 반응기의 활성 탄소층에 흡수된 초산을 메탄올과 혼합한 다음 이온 교환 수지 촉매 층에서 반응시켜 메틸아세테이트와 물을 생성시키며, 메틸아세테이트는 쉽게 분리 포집하여 재활용 한다. 본 발명을 활용하면, 초산, 테레프탈산, 디메틸테레프탈레이트, 이소테레프탈산 등을 생산하는 화학 공장에서 다량으로 발생되는 폐수를 경제적으로 재활용하여 환경 오염을 방지하고 또한 메틸아세테이트를 부산물로 생산할 수 있다.According to the present invention, by using a reactor having an activated carbon and a catalyst layer, acetic acid can be separated and recovered from the wastewater and recycled. The purified wastewater can be recycled. Reaction is carried out in the catalyst bed to produce methyl acetate and water, and methyl acetate is easily separated, collected and recycled. Utilizing the present invention, it is possible to economically recycle wastewater generated in large quantities in a chemical plant producing acetic acid, terephthalic acid, dimethyl terephthalate, isoterephthalic acid, etc. to prevent environmental pollution and also to produce methyl acetate as a by-product.
Description
본 발명은 초산폐수의 처리 방법 및 장치에 관한 것이다. 좀더 상세하게는 활성탄소와 촉매 층이 있는 반응기를 이용하여, 폐수로부터 초산을 분리 회수하고 정화된 폐수는 재활용하며, 회수된 초산은 메탄올과 반응시켜 메틸아세테이트를 제조함으로써 재활용 할 수 있는 폐수의 처리 방법 및 장치에 관한 것이다.The present invention relates to a method and apparatus for treating acetic acid wastewater. More specifically, by using a reactor with activated carbon and a catalyst bed, acetic acid is separated and recovered from the wastewater, and the purified wastewater is recycled, and the recovered acetic acid is reacted with methanol to produce methyl acetate, which can be recycled. And to an apparatus.
본 발명의 처리 대상인 초산을 포함하는 폐수는, 초산을 제조하는 공장 및 테레프탈산 (Terephthalic Acid), 디메틸테레프탈레이트 (DimethylTerephthalate), 이소프탈산 (Isophthalic Acid), 셀룰로즈 아세테이트 (Celloluse Acetate), 에스테르류 (Esters), 아세틱 무수화물 (Acetic Anhydride) 등을 제조하는 많은 화학 공장에서 다량 발생한다. 그런데 낮은 농도의 초산은 경제적으로 분리 활용하기가 매우 어렵기 때문에 대부분 폐수처리장으로 보내지고 있다.Wastewater containing acetic acid to be treated in the present invention is a plant for producing acetic acid and terephthalic acid, dimethyl terephthalate, isophthalic acid, cellulose acetate, esters It occurs in large quantities in many chemical plants that produce acetic anhydride. However, low concentrations of acetic acid are sent to wastewater treatment plants because it is very difficult to separate and use economically.
일반적으로 초산을 물에서 분리 회수하는 공정은 공비 증류 (Azeotropic Distillation), 통상적 증류 (Conventional Distillation), 액액 추출, 화학처리 및 흡착의 방법을 통해 이루어지고 있다(Z.P.Xu and K.T.Chuang, "Kinetics of Acetic Acid Esterification over Ion Exchange Catalysts", Canadian Journal of Chem. Eng., Vol 74, pp493-500, 1996). 경제적인 이유 때문에 가장 보편적으로 사용되는 방법은 공비 증류 (Azeotropic Distillation) 와 통상적 증류 (Conventional Distillation)를 이용하는 분리 방법이다. 그러나 초산의 농도가 낮은 경우에는 많은 양의 물을 증발시켜야 하므로 분리하는데 소요되는 에너지가 매우 높다는 문제점이 있으며, 그리고 물의 초산 농도를 1% 미만으로 분리하기 위하여는 증류탑 단 수가 많아져야 하기 때문에 막대한 투자비가 소요 된다. 또한 증류분리탑 하부쪽으로 갈수록 초산 농도가 증가함에 따라 용액은 부식성이 강해져 설비 부식의 문제가 발생된다. 따라서 에너지 사용량과 설비 투자비 및 유지비가 많이 드는 문제점이 있다.In general, the process of separating and recovering acetic acid from water is carried out through azeotropic distillation, conventional distillation, liquid extraction, chemical treatment and adsorption (ZPXu and KTChuang, "Kinetics of Acetic"). Acid Esterification over Ion Exchange Catalysts ", Canadian Journal of Chem. Eng., Vol 74, pp 493-500, 1996). For economic reasons, the most commonly used methods are separation methods using azeotropic distillation and conventional distillation. However, when the concentration of acetic acid is low, a large amount of water has to be evaporated, so the energy required for separation is very high, and in order to separate the acetic acid concentration of water to less than 1%, the number of distillation column stages must be enormous. It takes In addition, as the acetic acid concentration increases toward the bottom of the distillation column, the solution becomes more corrosive, causing problems of equipment corrosion. Therefore, there is a problem in that energy consumption, facility investment costs, and maintenance costs are high.
활성 탄소를 이용한 흡착 제거 방법은 폐수 중 유기물을 효율적으로 제거하는 방법으로 잘 알려져 있다(M.K.Lee, P.Y.Yang, and R.A.Wynveen, "Water Purification Unit Development for Field Army Medical Facilities", TechnicalReport, Contract DAMD17-76-C-6063, ER314-7-3, Life Systems, Inc., Cleveland, OH, April 1978). 그러나 활성 탄소가 유기물로 포화되면 더 이상 제거 능력을 상실하므로, 활성 탄소를 교체하여야 한다. 따라서 초산과 같은 유기 화합물을 제거하는데 막대한 양의 활성 탄소가 필요하게 되고, 활성탄 구매에 막대한 비용이 들기 때문에 대규모 설비에는 거의 실용화 되지 않고 있다. 또한 사용된 활성 탄소를 재생(Regeneration) 하는 경제적인 방법이 없기 때문에 다량의 고상 폐기물을 발생하는 단점이 있다.Adsorption removal using activated carbon is well known for the efficient removal of organics from wastewater (MKLee, PYYang, and RAWynveen, "Water Purification Unit Development for Field Army Medical Facilities", Technical Report, Contract DAMD17-76 -C-6063, ER314-7-3, Life Systems, Inc., Cleveland, OH, April 1978). However, once activated carbon saturates with organics, it no longer removes its capacity, so the activated carbon must be replaced. Therefore, a large amount of activated carbon is required to remove organic compounds such as acetic acid, and the cost of purchasing activated carbon is very high, making it practically not practical for large-scale installations. In addition, there is a disadvantage that generates a large amount of solid waste because there is no economic way to regenerate the activated carbon used.
본 발명은 활성 탄소와 촉매 층이 있는 반응기를 이용하여, 폐수로부터 초산을 분리 회수하고 정화된 폐수를 재활용할 수 있는 기술과 관련된다. 반응기의 활성 탄소 층에 흡수된 초산을 메탄올과 혼합한 다음 이온 교환수지 촉매 층에서 반응시키면 메틸아세테이트와 물을 생성시키며, 메틸아세테이트는 쉽게 분리 포집하여 재활용하게 된다.The present invention relates to a technique capable of separating and recovering acetic acid from wastewater using a reactor with activated carbon and a catalyst bed and recycling the purified wastewater. When acetic acid absorbed in the activated carbon layer of the reactor is mixed with methanol and then reacted in an ion exchange resin catalyst layer, methyl acetate and water are produced. The methyl acetate is easily separated, collected and recycled.
본 발명의 목적은 폐수중에 포함되어 있는 낮은 농도의 초산을 경제적인 방법으로 분리 제거할 수 있는 새로운 폐수 처리 기술을 제공하는데 있다. 즉, 투자비 및 에너지 사용량을 대폭 절감하여 경제적으로 폐수를 재활용할 수 있는 새로운 기술을 제공하는 것이다.It is an object of the present invention to provide a new wastewater treatment technology capable of separating and removing low concentrations of acetic acid contained in wastewater in an economical manner. In other words, it provides a new technology that can economically recycle wastewater by drastically reducing investment costs and energy usage.
본 발명의 다른 목적은 초산을 메틸아세테이트로 전환하여 이를 다른 공정에 사용함으로써 부산물을 효율적으로 이용할 수 있는 신 기술을 제공하는 것이다.Another object of the present invention is to provide a new technology that can efficiently use by-products by converting acetic acid to methyl acetate and using it in another process.
도 1은 본 발명장치의 구성도1 is a block diagram of an apparatus of the present invention
-도면의 주요부분에 대한 부호의 설명Explanation of symbols on the main parts of the drawings
1 : 제 1반응기; 2 : 제 2반응기1: first reactor; 2: second reactor
4 : 분리탑; 5 : 응축기4: separation column; 5: condenser
3, 8 : 펌프; 6: 환류 드럼3, 8: pump; 6: reflux drum
7: 재비기 9: 냉각기7: rewash 9: cooler
본 발명은 상부에 흡착제 층 (Adsorption Bed)과 하부에 촉매 층 (Catalyst Bed)을 갖고 있는 반응기 두 대와 반응 생성물인 메틸아세테이트를 분리하는 증류 분리탑으로 구성된 장치를 이용하여, 초산을 분리 회수하고 정화된 물을 재활용하는 방법 및 장치이다. 반응기 상부의 흡착제로 활성 탄소(Activated Carbon)를 사용하고, 하부의 촉매로는 강산성 양이온 교환수지 (Cation Exchange Resin)를 사용한다. 이하 본 발명을 도면에 의거 상세히 설명한다.The present invention separates and recovers acetic acid using an apparatus consisting of two reactors having an adsorption bed at the top and a catalyst bed at the bottom and a distillation separation column separating methyl acetate, the reaction product. A method and apparatus for recycling purified water. Activated carbon is used as an adsorbent on the top of the reactor, and a strong acid cation exchange resin is used as the catalyst on the bottom. Hereinafter, the present invention will be described in detail with reference to the drawings.
도 1을 참조하여, 본 발명의 주요 장치는 제 1반응기(1), 제 2반응기(2), 분리탑(4)으로 구성된다. 제 1반응기(1)와 제 2반응기(2)는 피드(Feed) 라인과 연결이 되어 있어 교대로 운전할 수 있게 되어있고, 반응기와 분리탑 (4) 사이에는 펌프 (3)와 냉각기 (9)가 설치되어 반응 생성물을 분리탑으로 보내게 되어있다. 분리탑 (4) 상부에는 메틸아세테이트 응축기 (5)가 설치되어 있으며, 응축기 (5) 하부에는 환류 드럼 (6)이 설치되어 분리탑 (4) 상부라인에 연결되어 있다. 분리탑 (4) 하부에는 하부 흐름 순환 펌프 (8)와 재비기 (7)가 설치되어 있다.Referring to FIG. 1, the main apparatus of the present invention consists of a first reactor 1, a second reactor 2, and a separation tower 4. The first reactor 1 and the second reactor 2 are connected to a feed line so that they can be operated alternately, and a pump 3 and a cooler 9 between the reactor and the separation tower 4. Is installed to direct the reaction product to the separation column. A methyl acetate condenser (5) is installed at the top of the separation tower (4), and a reflux drum (6) is installed at the lower part of the condenser (5) and connected to the upper line of the separation tower (4). The lower flow circulation pump 8 and the reboiler 7 are installed below the separation tower 4.
이상과 같이 구성된 본 발명 장치에 우선, 초산이 함유된 폐수를(A) 제 1반응기(1) 상부에 주입한다. 초산이 활성 탄소층에 흡착 포화되어 제거 능력이 현저히 떨어질 때까지 폐수를 제 1반응기(1)에 계속 투입 한다. 이렇게 초산을 제거하여 정화된 물은 저장 탱크(D)로 보내져 재활용 된다. 제 1반응기(1)의 흡착 제거 능력이 떨어지면 제 1반응기(1) 상부에 주입되는 폐수 피드 라인을 잠그고, 폐수를 제 2반응기(2)로 주입시켜 처리하며, 그 동안 제 1반응기(1)의 활성탄소를 재생(Regeneration) 한다. 이와 같이 반응기 두 대를 교대로 이용하여 폐수 처리를연속적으로 진행시킨다. 반응기 한대가 폐수 처리를 하는 동안 다른 한대는 재생(Regeneration) 된다.First, the wastewater containing acetic acid is injected into the upper part of the 1st reactor 1 to the apparatus of this invention comprised as mentioned above. Wastewater continues to be introduced into the first reactor 1 until acetic acid is adsorbed and saturated in the activated carbon layer and the removal capacity is significantly reduced. The water purified by removing acetic acid is sent to a storage tank (D) for recycling. When the adsorption and removal capacity of the first reactor (1) falls, the wastewater feed line injected above the first reactor (1) is shut off, and the wastewater is injected into the second reactor (2) for treatment, during which the first reactor (1) Regeneration of activated carbon As such, two reactors are alternately used to continuously treat the wastewater. While one reactor is treating the waste water, the other is regenerated.
사용한 흡착탄소층을 재생(Regeneration)하는 과정을 제 2반응기(2)를 예로 들어 설명하겠다. 분리탑(4) 하부로부터 오는 용액에 물(B)과 메탄올(C)을 동시에 주입한 다음, 제 2반응기(2) 상부로 투입하여 활성탄소에 흡착된 초산을 탈착시킨다. 탈착된 초산과 메탄올(Methanol)은 제 2반응기(2) 하부에 충진된 이온교환 수지 촉매층에서 반응 하여 메틸아세테이트와 물을 생성한다. 반응 생성 혼합물은 펌프(3)를 통해 분리탑(4)으로 보내진다. 물보다 비점이 낮은 메틸아세테이트는 분리탑 상부로 분리되며, 하부로는 소량의 잔류 메탄올과 물이 분리되어 반응기로 순환된다. 분리된 메틸아세테이트는 응축기 (5)에서 액체상태로 응축한 다음 환류드럼(6)(Reflux Drum) 하부에서 분배되어 일부는 분리탑 상부로 환류시키고 나머지는 메틸아세테이트 저장 탱크(E)로 보내진다. 분리탑(4) 하부의 액체는 주성분이 물로서 제 2반응기(2)로 환류시켜, 초산 탈착 및 반응 과정을 계속 시킨다.Regeneration of the used adsorption carbon layer will be described using the second reactor 2 as an example. Water (B) and methanol (C) are simultaneously injected into the solution coming from the bottom of the separation tower 4, and then the upper portion of the second reactor 2 is introduced to desorb the acetic acid adsorbed on the activated carbon. Desorbed acetic acid and methanol (Methanol) is reacted in the ion exchange resin catalyst layer packed in the lower part of the second reactor (2) to produce methyl acetate and water. The reaction product mixture is sent to separation tower 4 via pump 3. Methyl acetate, which has a lower boiling point than water, is separated at the top of the separation column, and a small amount of residual methanol and water are separated at the bottom and circulated to the reactor. The separated methyl acetate is condensed in the liquid state in the condenser (5) and then distributed under the Reflux Drum (6), some are refluxed to the top of the separation tower and the other is sent to the methyl acetate storage tank (E). The liquid at the bottom of the separation tower 4 is refluxed as the main component to the second reactor 2 as water, to continue the process of acetic acid desorption and reaction.
반응기 및 분리탑 하부의 온도는 재비기(7)에 의해 조절된다. 반응기 상부로 주입되는 물(B)의 유량을 조절하여 재비기(7) 하부의 수면 높이를 (Liquid Level) 일정하게 유지하며, 반응 온도를 재비기 온도와 상이하게 유지코자 할 경우 물의 온도를 조절하여 사용할 수 있다. 흡착된 초산의 탈착 (Desorption) 및 반응이 끝나면 제 2반응기(2)의 재생(Regeneration)은 완료되고, 제 1반응기(1)와 교대하여 폐수 처리를 하며, 제 1반응기(1)는 재생 운전을 하게 된다.The temperature of the reactor and bottom of the separation column is controlled by the reboiler (7). By adjusting the flow rate of the water (B) injected into the top of the reactor to maintain a constant water level (Liquid Level) of the bottom of the reboiler (7), if you want to keep the reaction temperature different from the reboiler temperature, the temperature of the water is controlled Can be used. After the desorption and reaction of the adsorbed acetic acid are completed, the regeneration of the second reactor 2 is completed, and the first reactor 1 is alternately treated with wastewater, and the first reactor 1 is operated for regeneration. Will be
초산과 메탄올의 에스테르화 반응은 액체 상태 하에서 이루어지고, 반응의적정 온도는 50~98℃이며, 분리탑 하부 재비기와 물 피드(Feed)의 온도를 조절하여 반응온도를 일정하게 유지한다. 반응온도가 98℃ 이상이면 반응 생성물의 상분리가 일어나고, 50℃ 미만이면 초산의 탈착 및 반응 속도가 낮아지는 문제가 있다. 또한 반응온도가 너무 낮으면 반응물을 냉각(Cooling)해서 반응기에 주입해야 하고, 반응생성물을 분리탑(4)으로 보내 분리할 때 열부하(Heating Load)가 증가해서 에너지 소모가 커지게 된다. 적정반응 체류시간(Residence Time)은 5∼100분이 적당한 바, 그 이유는 체류시간이 너무 크면 반응기 부피가 커져서 투자비가 많이 들고, 체류시간이 너무 작으면 반응처리 용량이 작아져 전환율이 낮아지는 문제가 있기 때문이다.The esterification reaction of acetic acid and methanol is carried out in a liquid state, the proper temperature of the reaction is 50 ~ 98 ℃, the reaction temperature is kept constant by adjusting the temperature of the bottom re-boiler and the water feed (Feed). If the reaction temperature is 98 ° C or higher, phase separation of the reaction product occurs. If the reaction temperature is lower than 50 ° C, there is a problem that the desorption of acetic acid and the reaction rate are lowered. In addition, if the reaction temperature is too low, the reactant must be cooled and injected into the reactor, and the heat load increases when the reaction product is sent to the separation tower 4 to increase energy consumption. The proper residence time (Residence Time) is 5 to 100 minutes. The reason is that if the residence time is too large, the reactor volume becomes large, and the investment cost is high. If the residence time is too small, the reaction treatment capacity becomes small and the conversion rate is low. Because there is.
본 발명의 제 1반응기(1)와 제 2반응기(2)는 동일하게 설계되어 있다. 반응기 상부에 흡착제로 활성탄소(Activated Carbon)를 충진하고 하부에 촉매로 양이온 교환 수지(Cation Exchange Resin)를 충진 하였다. 활성탄소 흡착제층 과 촉매층 하부에는 각각 지지 스크린(Support Screen)이 장착되어 있어 활성탄소 및 촉매가 누출되지 않도록 설계하였다. 양이온 교환수지 촉매로는 롬앤하스회사(Rohm and Hass) 제품인 앰버리스트(Amberlyst) 15(상표명, 이하 같다), 앰버리스트(Amberlyst) 35 및 미쓰비시사(Mitsubishi Kasei)의 디아이온(Diaion) PK 208H를 사용하였다.The first reactor 1 and the second reactor 2 of the present invention are designed in the same way. In the upper part of the reactor, activated carbon was charged with an adsorbent, and a cation exchange resin was charged with a catalyst at the bottom. Support screens are mounted at the bottom of the activated carbon adsorbent layer and the catalyst layer, respectively, to prevent leakage of the activated carbon and catalyst. Cation exchange resin catalysts include Amberlyst 15 (trade name, hereinafter referred to), Amberlyst 35 and Mitionubishi Kasei's Diaion PK 208H from Rohm and Hass. Used.
메틸아세테이트 분리탑(4)은 통상적으로 사용되는 단순 증류탑으로 각종 단 장착 칼럼(Tray Columns)이나 패킹 칼럼(Packing Columns)을 사용할 수 있다. 본 발명에서 분리탑(4) 이론 단수(No of Theoretical Plates)는 3~15단이 적당한 바,그 이유는 분리 효율과 경제성 측면에서 효율적이기 때문이다.Methyl acetate separation column (4) is a simple distillation column that is commonly used may use a variety of stage column (Tray Columns) or packing columns (Packing Columns). In the present invention, the separation column 4 of the theoretical plates (No of Theoretical Plates) is 3 to 15 steps are suitable because it is efficient in terms of separation efficiency and economics.
이하 본 발명을 실시예를 통하여 더욱 구체적으로 설명한다. 본 실시예는 본 발명의 바람직한 구체예로서 본 발명의 범위를 한정하려는 것은 아니다. 폐수에 함유된 초산을 활성 탄소를 이용하여 흡착 제거 하는 방법은 이미 널리 알려진 기술이므로 실시예에서 생략하였다. 활성 탄소가 초산으로 포화되어 초산 제거 능력을 거의 상실한 반응기를 재생하고, 반응 후 생성된 메틸아세테이트를 분리하는 공정만 아래 실시예에 기술 하였다.Hereinafter, the present invention will be described in more detail with reference to Examples. This example is not intended to limit the scope of the invention as a preferred embodiment of the invention. Adsorption and removal of acetic acid contained in the waste water using activated carbon has been omitted in the examples because it is a well known technique. Only the process of regenerating a reactor in which activated carbon was saturated with acetic acid and almost losing acetic acid removal ability and separating the methyl acetate produced after the reaction was described in the following Examples.
(실시예 1, 2, 3)(Examples 1, 2, 3)
활성 탄소가 초산으로 거의 포화된 제 2반응기(2)를 재생하는 과정 및 방법은 이미 위에서 기술하였다. 분리탑(4) 하부로부터 오는 용액에 물(B)과 메탄올(C)을 동시에 주입한 다음, 제 2반응기(2) 상부로 투입하여 활성탄소에 흡착된 초산을 탈착시킨다. 탈착된 초산과 메탄올(Methanol)은 반응기 하부에 충진된 촉매층에서 반응 하여 메틸아세테이트와 물을 생성한다. 촉매층에 들어가는 반응물 중 초산 및 메탄올의 농도와 반응기 조건, 그리고 분리탑의 운전조건을 표 1에 표시 하였다.The process and method for regenerating the second reactor 2 in which the activated carbon is almost saturated with acetic acid has already been described above. Water (B) and methanol (C) are simultaneously injected into the solution coming from the bottom of the separation tower 4, and then the upper portion of the second reactor 2 is introduced to desorb the acetic acid adsorbed on the activated carbon. Desorbed acetic acid and methanol (Methanol) is reacted in the catalyst layer packed in the bottom of the reactor to produce methyl acetate and water. Table 1 shows the concentrations of acetic acid and methanol, reactor conditions, and operating conditions of the separation column in the catalyst bed.
실시예 1은 반응물 중 초산의 농도를 1.31%, 초산 대비 메틸아세테이트의 몰비를 1.0, 반응온도는 93℃, 메틸아세테이트 분리탑 재비기(7)의 온도는 99.4℃로 유지하고 실험을 행하였다. 메틸아세테이트 응축기(6)의 온도는 40℃로 유지하고, 환류비 (Reflux Ratio)는 3.0으로 운전 하였다. 촉매로는 강산성 양이온 교환수지인 앰버리스트(Amberlyst)-15를 사용하였다.In Example 1, the concentration of acetic acid in the reaction product was 1.31%, the molar ratio of methyl acetate to acetic acid was 1.0, the reaction temperature was 93 ° C, and the temperature of the methyl acetate separation column reboiler 7 was 99.4 ° C. The temperature of the methyl acetate condenser (6) was maintained at 40 ℃, Reflux Ratio was operated at 3.0. Amberlyst-15, a strongly acidic cation exchange resin, was used as a catalyst.
실시예 2는 반응 피드중 초산의 농도를 1.83%, 반응온도는 90℃, 메틸아세테이트 분리탑 재비기(7)의 온도는 99.1℃로 유지하고 실험을 행하였다. 메틸아세테이트 응축기(6)의 온도는 40℃로 유지하고, 환류비 (Reflux Ratio)는 3.0으로 운전 하였다. 촉매로는 미쓰비시사의 디아이온(Diaion) PK 208H를 사용하였다.In Example 2, the concentration of acetic acid in the reaction feed was 1.83%, the reaction temperature was 90 ° C, and the temperature of the methyl acetate separation column reboiler 7 was maintained at 99.1 ° C. The temperature of the methyl acetate condenser (6) was maintained at 40 ℃, Reflux Ratio was operated at 3.0. As a catalyst, Diaion PK 208H of Mitsubishi Corporation was used.
실시예 3는 반응 피드중 초산의 농도를 2.6%, 반응온도는 80℃, 메틸아세테이트 분리탑 재비기(7)의 온도는 98.9℃로 유지하고 실험 하였다. 촉매로는 앰버리스트(Amberlyst)-35를 사용하였다.In Example 3, the concentration of acetic acid in the reaction feed was 2.6%, the reaction temperature was 80 ° C, and the temperature of the methyl acetate separation column reboiler 7 was maintained at 98.9 ° C. Amberlyst-35 was used as a catalyst.
(표 1) 실시예 운전 조건Table 1 Example Operation Conditions
* 초산 회수율 =100x (회수된 메틸아세테이트 몰 수)/(흡착된 초산 몰 수)* Acetic acid recovery = 100x (moles of methyl acetate recovered) / (moles of acetic acid adsorbed)
** 는 분리탑 (4) 상부 축출물중의 농도를 나타낸다.** indicates the concentration in the effluent from the top of the separation column 4.
상기와 같은 본 발명의 특징은 폐수 중에 포함되어 있는 낮은 농도의 초산을 경제적인 방법으로 분리하고 정화된 폐수를 재활용함으로써 환경 오염을 원천적으로 방지하는 청정 기술이다. 따라서 막대한 폐수처리 비용을 절감하고, 또한 분리된 초산을 메틸아세테이트로 전환하여 타 공정에 사용함으로써 부산물을 효율적으로 생산 활용하는 것이다. 상기한 환경오염의 원척적 방지 및 자원 (물과 메틸아세테이트) 재활용 외에, 본 발명은 사용한 활성탄소를 재생 재활용하고 에너지를 절감함으로서 투자비 및 운전비용을 대폭 절감하였다는 특징이 있다.The characteristics of the present invention as described above is a clean technology that prevents environmental pollution by fundamentally separating the low concentration of acetic acid contained in the waste water in an economical manner and recycling the purified waste water. Therefore, a significant waste water treatment cost is reduced, and by converting the separated acetic acid into methyl acetate and using it in another process, the by-products are efficiently produced and utilized. In addition to the above-mentioned primary prevention of environmental pollution and recycling of resources (water and methyl acetate), the present invention is characterized by drastically reducing investment and operating costs by regeneratively recycling used carbon and saving energy.
초산을 포함하는 폐수는, 초산을 제조하는 공장 및 테레프탈산 (Terephthalic Acid), 디메틸테레프탈레이트 (Dimethyl Terephthalate), 이소프탈산 (Isophthalic Acid), 셀룰로즈 아세테이트 (Celloluse Acetate), 에스테르류 (Esters), 아세틱 무수화물 (Acetic Anhydride) 등을 제조하는 많은 화학 공장에서 다량 발생한다. 현재 한국에는 약 20여개의 이와 같은 화학공장이 있으며, 전세계적으로는 수백개에 달한다. 낮은 농도의 초산은 경제적으로 분리 활용하기가 매우 어렵기 때문에 현재 거의 모든 공장에서 이와 같은 폐수를 폐수처리장으로 보내고 있다. 본 발명을 상기 화학 공장에 적용하면, 환경 오염 방지는 물론 폐수처리 비용 절감 및 자원 재활용을 통해 지대한 경제적 효과가 예상된다.Wastewater, including acetic acid, is a factory that produces acetic acid and terephthalic acid, dimethyl terephthalate, isophthalic acid, cellulose acetate, esters, and acetic anhydride. It occurs in large quantities in many chemical plants that produce cargoes (Acetic Anhydride). There are currently about 20 such chemical plants in Korea, with hundreds worldwide. Low concentrations of acetic acid are very difficult to economically separate and use, and now almost all factories send such waste water to wastewater treatment plants. When the present invention is applied to the chemical plant, a great economic effect is expected through environmental pollution prevention, wastewater treatment cost reduction, and resource recycling.
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| KR100725588B1 (en) | 2006-04-11 | 2007-06-08 | 한밭대학교 산학협력단 | Treatment of wastewater containing acetic acid |
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| CN106831471B (en) * | 2017-01-20 | 2019-03-12 | 福州大学 | A method of removing a small amount of acid or glacial acetic acid and refining DMF |
| CN107311856A (en) * | 2017-08-13 | 2017-11-03 | 河南省煤气(集团)有限责任公司义马气化厂 | A kind of purification recovery system of acetic acid waste liquid |
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| JPH11228486A (en) * | 1997-12-01 | 1999-08-24 | Teijin Ltd | Recovery of acetic acid from acetic acid-containing wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1561742A1 (en) * | 2004-02-05 | 2005-08-10 | 3M Innovative Properties Company | Method of recovering fluorinated acid surfactants from adsorbent particles loaded therewith |
| WO2005077880A1 (en) * | 2004-02-05 | 2005-08-25 | 3M Innovative Properties Company | Method of recovering fluorinated acid surfactants from adsorbent particles loaded therewith |
| KR100725588B1 (en) | 2006-04-11 | 2007-06-08 | 한밭대학교 산학협력단 | Treatment of wastewater containing acetic acid |
| KR100926797B1 (en) | 2007-12-04 | 2009-11-12 | 금호석유화학 주식회사 | The recovery method of Alcohols or Ethers from waste water by Activated carbon fiber Adsorption Towers |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20020038070A (en) | 2002-05-23 |
| CN1159231C (en) | 2004-07-28 |
| CN1354139A (en) | 2002-06-19 |
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