KR100789557B1 - Recovery of methyl-4-formylbenzoate and dimethyl terephthalate from by-products in method for processing dimethyl terephthalate - Google Patents
Recovery of methyl-4-formylbenzoate and dimethyl terephthalate from by-products in method for processing dimethyl terephthalate Download PDFInfo
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Abstract
본 발명은 디메틸 테레프탈레이트 제조공정의 부산물로부터 메틸-4-포밀벤조에이트와 디메틸 테레프탈레이트의 분리회수방법에 관한 것으로, 좀 더 상세하게는 p-자일렌(p-xylene)의 산화반응에 의하여 얻은 테레프탈산을 메탄올과 에스테르화 반응시켜 생산하는 디메틸 테레프탈레이트 제조공정에서 발생하는 부산물의 혼합물로부터 메틸-4-포밀벤조에이트 및 디메틸 테레프탈레이트를 각각 순수하게 분리하여 회수하는 방법에 관한 것이다. 본 발명에 따르면, 메틸-4-포밀벤조에이트, 디메틸 테레프탈레이트, 메틸-p-톨루에이트, 및 메틸 벤조에이트 등이 포함된 디메틸 테레프탈레이트 제조공정의 부산물로부터 불순물이 포함된 메틸-4-포밀벤조에이트를 염으로 반응시켜 순수하게 분리하고, 상기 메틸-4-포밀벤조에이트를 제거한 혼합물에서 디메틸 테레프탈레이트를 순수하게 분리해낼 수 있다.The present invention relates to a method for separating and recovering methyl-4-formylbenzoate and dimethyl terephthalate from a by-product of a dimethyl terephthalate manufacturing process. More specifically, the present invention provides a method for separating and recovering p-xylene. The present invention relates to a method of purely separating and recovering methyl-4-formylbenzoate and dimethyl terephthalate from a mixture of by-products generated in a dimethyl terephthalate production process produced by esterifying terephthalic acid with methanol. According to the present invention, methyl-4-formylbenzoate containing impurities from by-products of dimethyl terephthalate manufacturing process including methyl-4-formylbenzoate, dimethyl terephthalate, methyl-p-toluate, methyl benzoate and the like. Eate can be reacted with a salt to separate purely, and dimethyl terephthalate can be separated purely from the mixture from which the methyl-4-formylbenzoate was removed.
메틸-4-포밀벤조에이트, 디메틸 테레프탈레이트, 메틸-p-톨루에이트, 메틸 벤조에이트, 자일렌, 테레프탈산 메탄올Methyl-4-formylbenzoate, dimethyl terephthalate, methyl-p-toluate, methyl benzoate, xylene, terephthalic acid methanol
Description
본 발명은 디메틸 테레프탈레이트 제조공정의 부산물로부터 메틸-4-포밀벤조에이트와 디메틸 테레프탈레이트의 분리회수방법에 관한 것으로, 좀 더 상세하게는 메틸-4-포밀벤조에이트(methyl-4-formylbenzoate: 이하 MFB라 함), 디메틸 테레프탈레이트(dimethyl terephthalate: 이하 DMT라 함), 메틸-p-톨루에이트(methyl-p-toluate: 이하 MPT라 함), 및 메틸 벤조에이트(methylbenzoate: 이하 MBZ라 함) 등이 포함된 DMT 제조 부산물로부터 MFB 및 DMT를 각각 순수하게 분리하여 회수하는 방법에 관한 것이다.The present invention relates to a method for separating and recovering methyl-4-formylbenzoate and dimethyl terephthalate from a by-product of a dimethyl terephthalate manufacturing process, and more particularly, methyl-4-formylbenzoate: MFB), dimethyl terephthalate (hereinafter referred to as DMT), methyl-p-toluate (hereinafter referred to as MPT), and methyl benzoate (hereinafter referred to as MBZ). It relates to a method for purely separating and recovering MFB and DMT, respectively, from the included byproducts of DMT.
MFB는 백색의 결정으로 특유의 알데히드 냄새가 나며, 아세톤, 톨루엔, 메틸렌클로라이드 등에 용해되는 성질을 가지고 있으며, 그 자체로는 형광증백제, 방향제 등의 원료와 p-아미노벤조산 등 고부가가치화 물질의 원료 물질로 사용되고 있다. MFB is a white crystal with a characteristic aldehyde odor and dissolves in acetone, toluene, methylene chloride, etc.In itself, MFB is a raw material of fluorescent brighteners, fragrances, and high value-added substances such as p-aminobenzoic acid. It is used as a substance.
이와 같은 MFB를 제조하는 통상적인 방법을 하기 반응식 1에 나타내었다.Conventional methods for preparing such MFBs are shown in Scheme 1 below.
상기 반응식 1에 나타낸 바와 같이, 기존의 통상적인 방법으로 MFB를 제조하기 위해서는 먼저 테레프탈알데히드를 황산촉매하에서 4-포밀벤조산으로 전환시킨 후, 다시 산 촉매 하에서 메탄올을 부가시켜 합성한다. 그러나 이와 같은 방법은 반응 초기 물질인 테레프탈알데히드가 고가이고, 4-포밀벤조산 제조후에 황산을 제거해야하는 등 부가 처리가 필요하며, 이로 인해 분리 및 정제시 수율 저하 등이 발생하고, 이를 다시 메탄올 부가반응시 촉매사용이 요구되어 목적 화합물의 제조 비용이 상승하는 단점이 있다.As shown in Scheme 1, in order to prepare MFB by the conventional conventional method, it is first synthesized by converting terephthalaldehyde into 4-formylbenzoic acid under a sulfuric acid catalyst and then adding methanol under an acid catalyst. However, such a method requires an additional treatment such as terephthalaldehyde, which is an initial reaction material, is expensive, and sulfuric acid should be removed after preparation of 4-formylbenzoic acid, resulting in a decrease in yield during separation and purification. Since the use of a catalyst is required, there is a disadvantage in that the manufacturing cost of the target compound is increased.
이에 본 발명에서는 전술한 종래기술의 문제점을 해결하기 위하여 다양한 연구를 거듭한 결과, DMT 제조공정의 부산물로부터 불순물이 포함된 MFB를 염으로 반응시켜 순수하게 분리하고, 상기 MFB를 제거한 혼합물에서 DMT를 순수하게 분리 및 회수할 수 있었고, 본 발명은 이에 기초하여 완성되었다.Therefore, in the present invention, as a result of various studies to solve the above-described problems of the prior art, MFB containing impurities from the by-products of the DMT manufacturing process are reacted with a salt to separate purely, and the DMT is removed from the mixture from which the MFB is removed. Pure separation and recovery were possible and the present invention was completed based on this.
따라서, 본 발명의 목적은 DMT 제조공정에서 발생하는 부산물로부터 간단한 정제과정을 통하여 저비용으로 활용가치가 높은 고순도의 MFB 및 DMT를 각각 분리회수하는 방법을 제공하는데 있다. Accordingly, it is an object of the present invention to provide a method for separating and recovering high-purity MFB and DMT, respectively, having high utility value at low cost through a simple purification process from by-products generated in a DMT manufacturing process.
상기 목적을 달성하기 위한 본 발명에 따른 DMT 제조공정의 부산물로부터 MFB와 DMT의 분리회수방법은:Separation recovery method of MFB and DMT from the by-product of the DMT manufacturing process according to the present invention for achieving the above object:
p-자일렌(p-xylene)을 출발물질로 사용하여 산화 반응 및 에스테르화 반응을 통한 DMT의 제조시 생성되는 반응부산물로부터 MFB 및 DMT를 각각 순수하게 분리회수하는 방법에 있어서, In a method for purely separating and recovering MFB and DMT from the reaction by-products produced during the production of DMT through oxidation and esterification using p-xylene as a starting material,
(a) MFB 60∼90중량%, DMT 5∼30중량%, MPT 3∼8중량%, 및 MBZ 1∼3중량%를 포함하는 DMT 제조공정의 반응부산물에 물(H2O)을 가하고 80∼95℃의 온도에서 용융시킨 후 중아황산나트륨(Na2S2O5)과 반응시켜 MFB 나트륨염을 생성시키는 단계;(a) Water (H 2 O) was added to the reaction by-product of the DMT manufacturing process, which included 60 to 90% by weight of MFB, 5 to 30% by weight of DMT, 3 to 8% by weight of MPT, and 1 to 3% by weight of MBZ. Melting at a temperature of ˜95 ° C. and then reacting with sodium bisulfite (Na 2 S 2 O 5 ) to produce MFB sodium salt;
(b) 상기 (a) 단계의 반응용액을 여과하여 고상의 DMT를 분리한 후, 정제 및 회수하는 단계; 및(b) filtering the reaction solution of step (a) to separate the solid phase DMT, and then purifying and recovering; And
(c) 상기 (b) 단계에서 얻은 여액에 염기를 가하여 MFB 나트륨염을 분해시킨 후, 생성된 MFB를 유기용제로 정제 및 회수하는 단계;(c) decomposing MFB sodium salt by adding a base to the filtrate obtained in step (b), and then purifying and recovering the resulting MFB with an organic solvent;
를 포함하는 것을 특징으로 한다.Characterized in that it comprises a.
이하, 본 발명을 좀 더 구체적으로 살펴보면 다음과 같다.Hereinafter, the present invention will be described in more detail.
전술한 바와 같이, 본 발명에서는 MFB, DMT, MPT 및 MBZ 등이 포함된 DMT 제조공정의 부산물로부터 간단한 정제과정을 통하여 저비용으로 활용가치가 높은 고 순도의 MFB 및 DMT를 각각 분리회수하는 방법이 제공된다.As described above, the present invention provides a method for separating and recovering high-purity high-purity MFB and DMT, respectively, at low cost through a simple purification process from by-products of a DMT manufacturing process including MFB, DMT, MPT, and MBZ. do.
본 발명에 따른 DMT 제조공정의 부산물은 하기 반응식 2에 나타낸 바와 같은 제조과정에서 생성되는 부산물의 혼합물이다.The by-product of the DMT manufacturing process according to the present invention is a mixture of by-products produced in the manufacturing process as shown in Scheme 2 below.
p-자일렌의 액상 산화반응을 통해서 생성된 산화 반응물 중에는 테레프탈산(terephthalic acid; 이하 TPA라 함) 외에 각종 불순물이 함유되어 있으며, 특히 반응 중간 생성물인 p-포밀벤조산이 상당량 함유되어 있다. 상기 TPA는 과잉의 메탄올로 에스테르화시켜 DMT로 전환시킨 후 고온 분리하여 고체상의 생성 물로 분리한다. 한편, 4-포밀벤조산은 메탄올로 인해 MFB 부산물이 생성된다.In addition to terephthalic acid (hereinafter referred to as TPA), various kinds of impurities are contained in the oxidized reactant produced through the liquid phase oxidation of p-xylene, and particularly, a considerable amount of p-formylbenzoic acid, which is a reaction intermediate product, is contained. The TPA is esterified with excess methanol and converted to DMT, followed by high temperature separation to separate solid product. On the other hand, 4-formylbenzoic acid produces MFB by-products due to methanol.
이와 같은 DMT의 제조 과정에서 생성되는 부산물 성분은 DMT의 제조공정에 따라 달라질 수 있으나, DMT 제조 반응속도를 충분히 증가시키는 경우 얻어지는 부산물의 혼합물을 분석하면 MFB 60∼90중량%, DMT 5∼30중량%, MPT 3∼8중량%, MBZ 1∼3중량%이다. 세계적으로는 이스트만 코닥(Eastman Kodak), 듀퐁(DuPont), SK케미칼 등이 이와 같은 DMT 제조공정을 채택하고 있으며, 발생되는 부산물은 일반적으로 폐기되거나 극히 일부만 활용되고 있는 실정이다.The by-products generated in the manufacturing process of the DMT may vary depending on the manufacturing process of the DMT, but when analyzing the mixture of the by-products obtained when the reaction rate of the DMT is sufficiently increased, MFB 60-90 wt%, DMT 5-30 wt% %, MPT 3-8 weight%, MBZ 1-3 weight%. Globally, Eastman Kodak, DuPont, and SK Chemicals have adopted such a DMT manufacturing process, and the by-products generated are generally discarded or only partially used.
한편, 이와 관련하여, 한국 특허공개 제2003-70824호에는 DMT 제조공정의 부산물의 혼합물로부터 p-아미노벤조산을 제조하는 방법이 개시되어 있으나, 부산물의 주요성분인 MFB 및 DMT를 순수하게 분리하는 방법에 대해서는 기술되어 있지 않다.In this regard, Korean Patent Publication No. 2003-70824 discloses a method of preparing p-aminobenzoic acid from a mixture of by-products of a DMT manufacturing process, but a method of purely separating MFB and DMT, which are main components of a by-product. It is not described.
따라서, 본 발명에서는 p-자일렌을 출발물질로 사용하여 산화 반응 및 에스테르화 반응을 통한 DMT의 제조시 생성되는 반응부산물로부터 MFB 및 DMT를 각각 순수하게 분리회수하기 위하여, 우선 상기 반응식 2에 나타낸 DMT 제조공정의 부산물, 즉 MFB 60∼90중량%, DMT 5∼30중량%, MPT 3∼8중량%, MBZ 1∼3중량%를 포함하는 DMT 제조공정의 반응부산물에 물(H2O)을 가하고 80∼95℃의 온도로 가열하여 용융시키고, 여기에 중아황산나트륨(sodium metabisulfite: Na2S2O5)을 투입하여 하기 반응식 3에 나타낸 바와 같이 반응시켜 MFB 나트륨염(MFB-Na-salt)을 생성시킨다. Therefore, in the present invention, in order to purely separate and recover MFB and DMT from the reaction by-products produced during the preparation of DMT through oxidation and esterification using p-xylene as a starting material, Water (H 2 O) in the by-products of the DMT manufacturing process, including by-products of the DMT manufacturing process, ie 60 to 90% by weight of MFB, 5 to 30% by weight of DMT, 3 to 8% by weight of MPT, and 1 to 3% by weight of MBZ. Was added and heated to a temperature of 80-95 ° C. to melt, and sodium bisulfite (Na 2 S 2 O 5 ) was added thereto and reacted as shown in Scheme 3 below to react with MFB sodium salt (MFB-Na-salt). ).
이때, 상기 중아황산나트륨의 사용량은 상기 MFB 당량에 대하여 0.5∼1.0당량인 것이 좋고, 과량으로 사용하는 경우 아황산 가스가 많이 발생되는 한편 MFB 나트륨염의 전환율 증가는 미미하여 비경제적이다.At this time, the amount of sodium bisulfite is preferably 0.5 to 1.0 equivalent to the MFB equivalents, and when used in excess, a lot of sulfite gas is generated, the increase in the conversion rate of MFB sodium salt is insignificant and uneconomical.
이렇게 하여 생성된 MFB 나트륨염은 고상으로 존재하는데, 상기 반응물에 물을 추가 투입하고 고온으로 유지시켜 MFB 나트륨염이 완전히 녹도록 충분한 시간동안 교반시킨다. 충분한 교반 후, 상기 MFB 나트륨염은 수용액상태로 존재하며, 여기에 잔존하는 고체는 DMT이다. 이러한 상태의 반응물을 고온으로 유지한 채 여과하여 고상의 DMT를 걸러낸다.The MFB sodium salt thus produced is in the solid phase, and water is added to the reaction and kept at a high temperature, followed by stirring for a sufficient time to completely dissolve the MFB sodium salt. After sufficient stirring, the MFB sodium salt is in an aqueous solution, the solid remaining here is DMT. The reactants in this state are filtered while maintaining a high temperature to filter out solid DMT.
이때, 상기 여과온도는 MFB 나트륨염은 수용액상태로 존재하고 DMT 만이 고체 상태로 존재하도록 70∼95℃, 좀 더 바람직하게는 85℃인 것이 좋다. 또한, 여과는 충분한 순환이 가능하여 반응물 전체가 3회 이상 여과되도록 충분히 실시하여 불용성의 DMT가 전량 얻어지도록 하는 것이 바람직하다. 이렇게 하여 얻어진 DMT는 소량의 물과 메탄올로 씻어 다른 불순물을 제거하고 고순도의 DMT를 회수한다.At this time, the filtration temperature is 70 ~ 95 ℃, more preferably 85 ℃ so that the MFB sodium salt is present in the aqueous state and only DMT is in the solid state. In addition, the filtration is preferably sufficient to allow sufficient circulation so that the entire reactant is filtered three or more times to obtain the total amount of insoluble DMT. The DMT thus obtained is washed with a small amount of water and methanol to remove other impurities and recover high purity DMT.
한편, 상기 여과과정에서 얻어진 여액은 저온으로 유지하여 MFB 나트륨염을 고체로 생성시킨다. 이와 같이 고체로 생성된 MFB 나트륨염은 여과하여 회수하고, 여액은 유기용제를 사용하여 잔여 불순물을 추출한다. 여기서, 상기 여과과정에서 얻은 MFB 나트륨염 결정은 소량의 유기용제를 사용하여 불순물을 제거한 후 상기에 서 불순물을 제거한 여액과 합친다.On the other hand, the filtrate obtained in the filtration process is kept at a low temperature to produce MFB sodium salt as a solid. The MFB sodium salt thus formed is recovered by filtration, and the filtrate is extracted with residual impurities using an organic solvent. Here, the MFB sodium salt crystals obtained in the filtration process are combined with the filtrate from which impurities are removed after removing impurities using a small amount of organic solvent.
이때 사용되는 유기용제는 톨루엔(toluene), 메틸렌 클로라이드(methylene chloride)등 불순물을 제거할 수 있는 용제가 바람직하며, 메틸렌 클로라이드가 더 바람직하다.At this time, the organic solvent used is a solvent capable of removing impurities such as toluene, methylene chloride (methylene chloride) is preferred, methylene chloride is more preferred.
이로부터 얻어진 MFB 나트륨염 고체 및 여액에 유기용제를 투입하고 염기, 바람직하게는 가성소다(NaOH) 또는 탄산나트륨(Na2CO3)을 천천히 가하여 하기 반응식 4에 나타낸 바와 같이 MFB 나트륨염 분해반응을 거쳐 MFB를 회수한다.An organic solvent was added to the solid and filtrate of MFB sodium salt obtained therefrom, and a base, preferably caustic soda (NaOH) or sodium carbonate (Na 2 CO 3 ) was slowly added, followed by MFB sodium salt decomposition reaction as shown in Scheme 4 below. Recover MFB.
여기서, 상기 염기는 부반응을 최소화하기 위하여 충분한 시간을 두고 천천히 투입하며, 반응기 온도는 약 5∼15℃로 유지하는 것이 좋다. 상기 염기의 사용량은 MFB 당량당 1.0∼3.0당량, 바람직하게는 1.0∼1.5당량인 것이 좋다. 상기 염기의 사용량이 적을 경우 분해 반응이 완전히 진행되지 않고 반응 시간이 지연되며 MFB 회수율이 저하된다.Here, the base is slowly added with sufficient time to minimize side reactions, and the reactor temperature is preferably maintained at about 5 ~ 15 ℃. The amount of the base used is preferably 1.0 to 3.0 equivalents, preferably 1.0 to 1.5 equivalents per MFB equivalent. When the amount of the base used is small, the decomposition reaction does not proceed completely, the reaction time is delayed, and the MFB recovery rate is lowered.
상술한 바에 따라 염기 투입을 완료하고 충분히 교반한 후, 용제층을 분리하고 용제를 증발시켜 순수한 MFB를 얻는다. 한편, 상기 용제층과 분리된 수용액으로부터는 수분을 제거하여 고순도의 아황산나트륨(Na2SO3)을 분리한다.After completion of the base addition and stirring well as described above, the solvent layer is separated and the solvent is evaporated to obtain pure MFB. Meanwhile, water is removed from the aqueous solution separated from the solvent layer to separate sodium sulfite (Na 2 SO 3 ) of high purity.
이하, 실시예를 들어 본 발명을 더욱 상세하게 설명하나, 하기 실시예는 본 발명을 예시하기 위한 것으로서, 본 발명이 하기 실시예에 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for illustrating the present invention, and the present invention is not limited to the following Examples.
[실시예 1]Example 1
DMT 제조공정 부산물인 MFB 75중량%, DMT 17중량%, MPT 5중량%, MBZ 1중량% 및 기타 미량의 불순물을 포함하는 혼합물 100중량부에 대하여 물 200중량부를 투입한 후 80∼85℃로 가열하여 용융시킨다. 충분한 시간동안 교반한 후, 여기에 상기 MFB 당량에 대하여 0.75당량의 중아황산나트륨을 투입하여 MFB 나트륨염으로 전환시킨다. 이때 MFB 나트륨염을 99% 수율로 획득하였다.200 parts by weight of water is added to 80 parts by weight of 100 parts by weight of a mixture containing 75% by weight of MFB, 17% by weight of DMT, 5% by weight of MPT, 1% by weight of MBZ, and other trace impurities. Heated to melt. After stirring for a sufficient time, 0.75 equivalents of sodium bisulfite is added to the MFB equivalents to convert it to MFB sodium salt. At this time MFB sodium salt was obtained in 99% yield.
상기 반응물에 600중량부의 물을 추가 투입하고 80∼85℃로 유지하여 MFB 나트륨염을 완전히 용해시킨 후 여과하여 DMT 결정을 수득하였다. 이로부터 얻어진 DMT를 85℃의 물 40중량부와 메탄올 40중량부로 씻어내어, 순도 98%, 수율 96%의 DMT를 얻어냈다.600 parts by weight of water was further added to the reaction, and maintained at 80 to 85 ° C. to completely dissolve the MFB sodium salt, followed by filtration to obtain DMT crystals. The DMT obtained therefrom was washed with 40 parts by weight of water at 85 ° C. and 40 parts by weight of methanol to obtain DMT having a purity of 98% and a yield of 96%.
한편, 여과 후 DMT를 제거한 여액은 10℃로 냉각시켜 MFB 나트륨염으로 고체화시킨 후 여과하였다. 여과된 MFB 나트륨염 고체는 메틸렌 클로라이드 40중량부로 씻어서 불순물을 제거하고, 여액은 메틸렌 클로라이드 40중량부를 투입하여 불순물을 제거하고 수층만 회수하여 상기에서 얻은 MFB 나트륨염과 합친다.On the other hand, the filtrate from which DMT was removed after filtration was cooled to 10 ° C., solidified with MFB sodium salt, and filtered. The filtered MFB sodium salt solid was washed with 40 parts by weight of methylene chloride to remove impurities, and the filtrate was added with 40 parts by weight of methylene chloride to remove impurities, and only the aqueous layer was recovered and combined with the obtained MFB sodium salt.
이로부터 얻은 MFB 나트륨염 수용액에 메틸렌 클로라이드 40중량부를 넣고 알카리인 30% 가성소다 1.05당량을 2시간에 걸쳐 천천히 투입하였다. 이때 반응온도는 10℃로 유지하였으며, 이로부터 순도 99%, 수율 95.7%의 MFB를 수득하였다.40 parts by weight of methylene chloride was added to the aqueous solution of sodium MFB, and 1.05 equivalents of alkaline 30% caustic soda was slowly added over 2 hours. At this time, the reaction temperature was maintained at 10 ℃, to obtain a MFB of 99% purity, 95.7% yield.
한편, 상기 MFB를 회수한 후 폐수에서 H2O를 제거하여 70% 수율로 Na2SO3를 회수하였다. Meanwhile, after recovering the MFB, H 2 O was removed from the wastewater to recover Na 2 SO 3 in 70% yield.
[실시예 2]Example 2
메틸렌 클로라이드 대신 톨루엔을 동량 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 실시하여 MFB를 획득하였다. 이때, DMT의 순도는 98%, 수율은 95%이었으며, MFB의 순도는 99%, 수율은 95.1%이었다.MFB was obtained by the same method as Example 1 except for using the same amount of toluene instead of methylene chloride. At this time, the purity of DMT was 98%, the yield was 95%, the purity of MFB was 99%, the yield was 95.1%.
이상 상술한 바와 같이, 본 발명에 따른 MFB 및 DMT 분리회수방법은 기존에 알려진 바 없는 새로운 공정으로서, DMT 제조공정에서 부생하는, 종래에는 대부분 폐기되고 일부 한정적인 용도로만 사용되던 부산물로부터 고부가가치 물질인 MFB와 DMT를 간단한 분리과정을 통하여 분리/회수할 수 있다. 또한, 기존의 MFB 제조방법의 제조비용 상승의 문제를 해결하고, 활용가치가 극미한 부산물을 활용하여 고부가가치가 가능한 MFB 및 DMT를 고순도로 분리/정제할 수 있는 장점이 있다.As described above, the MFB and DMT separation recovery method according to the present invention is a new process that has not been known in the prior art, a high value-added material from by-products, which are by-products produced in the DMT manufacturing process, which have been mostly discarded and used only for some limited purposes. MFB and DMT can be separated and recovered through a simple separation process. In addition, there is an advantage that can solve the problem of increasing the manufacturing cost of the existing MFB manufacturing method, and separate / refined MFB and DMT with high purity by using by-products having a very low value.
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| KR20180052323A (en) * | 2016-11-10 | 2018-05-18 | 주식회사 오크켐텍 | METHOD OF PREPARING p-PHENYLENEDIAMINE |
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| CN114163619B (en) * | 2021-12-27 | 2023-03-31 | 江苏恒科新材料有限公司 | Polyester chip with low b value and preparation method thereof |
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| US4760165A (en) | 1985-11-13 | 1988-07-26 | Teijin Petrochemical Industries, Ltd. | Recovering useful components at least containing dimethyl terephthalate from high-boiling byproducts occurring in the production of dimethyl terephthalate |
| KR0124964B1 (en) * | 1993-12-24 | 1997-12-01 | 강박광 | Process for carboxybenzaldehyde from residue of dimethylterephthalate |
| KR100208120B1 (en) | 1997-05-07 | 1999-07-15 | 조민호 | Recovery method of mfb from the process of dmt production |
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| US4760165A (en) | 1985-11-13 | 1988-07-26 | Teijin Petrochemical Industries, Ltd. | Recovering useful components at least containing dimethyl terephthalate from high-boiling byproducts occurring in the production of dimethyl terephthalate |
| KR0124964B1 (en) * | 1993-12-24 | 1997-12-01 | 강박광 | Process for carboxybenzaldehyde from residue of dimethylterephthalate |
| KR100208120B1 (en) | 1997-05-07 | 1999-07-15 | 조민호 | Recovery method of mfb from the process of dmt production |
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| KR101341449B1 (en) | 2011-01-25 | 2013-12-13 | 주식회사 네이퓨 | Preparation of p-Chloromethylbenzoic acid and Benzoic acid from by-products in method for processing dimethyl terephthalate |
| KR20180052323A (en) * | 2016-11-10 | 2018-05-18 | 주식회사 오크켐텍 | METHOD OF PREPARING p-PHENYLENEDIAMINE |
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