KR100437562B1 - Method for recovering benzoic acid from waste products generated from terephthalic acid production process with high purity - Google Patents
Method for recovering benzoic acid from waste products generated from terephthalic acid production process with high purity Download PDFInfo
- Publication number
- KR100437562B1 KR100437562B1 KR1019960020325A KR19960020325A KR100437562B1 KR 100437562 B1 KR100437562 B1 KR 100437562B1 KR 1019960020325 A KR1019960020325 A KR 1019960020325A KR 19960020325 A KR19960020325 A KR 19960020325A KR 100437562 B1 KR100437562 B1 KR 100437562B1
- Authority
- KR
- South Korea
- Prior art keywords
- benzoic acid
- terephthalic acid
- waste products
- production process
- products generated
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/04—Monocyclic monocarboxylic acids
- C07C63/06—Benzoic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
본 발명은 폴리에스테르(polyester)의 원료인 테레프탈산(terephthalic acid)을 제조하는 공정에서 생성되는 공정 폐기물 중에 존재하는 여러가지 미반응물과 부생성물들로부터 안식향산(benzoic acid)을 분리회수하는 방법에 관한 것이다.The present invention relates to a method for separating and recovering benzoic acid from various unreacted substances and by-products present in process wastes produced in a process for producing terephthalic acid which is a raw material of polyester.
상기 폐기물에는 여러 종류의 테레프탈산 이성질체와 테레프탈산 합성의 주원료인 파라-자이렌(p-xylene)에 함유되어 있는 에틸벤젠(ethylbenzene)과 톨루엔(toluene) 등의 불순물, 그리고 이들이 산화되어서 생성되는 안식향산과 다른여러 화합물이 혼합되어 있다.The wastes contain various kinds of terephthalic acid isomers and impurities such as ethylbenzene and toluene contained in para-xylene which is a main raw material of terephthalic acid synthesis, and benzoic acid produced by oxidation thereof. Several compounds are mixed.
이러한 폐기물들은 날마다 다량으로 발생되고 있으며, 이들은 소각처리 되거나 폐수처리장에서 활성오니법으로 처리 되고있다. 그런데 소각처리의 경우에는 공해물질이 배출되지 않도록 공해방지설비를 설치해야 하는 어려움이 있다.These wastes are generated in large quantities every day, and these wastes are treated by incineration or activated sludge process in wastewater treatment plant. However, in the case of incineration treatment, it is difficult to install pollution prevention facilities so that pollutants are not discharged.
폐기물의 성분을 분석해 보면 표1에 표시한 바와 같이 여러가지 화합물들이 섞여 있으며 이들중에서 수분을 제외하면 안식향산이 20중량%를 점하고 있다. 또 표1 로 알 수 있는 바와 같이 상기 폐기물에는 유용하게 사용할 수 있는 여러가지 부생성물 및 촉매가 함유되어 있으므로 재활용을 위한 회수공정을 도입하면 폐기물의 양을 줄일 수 있다.As shown in Table 1, various compounds are mixed. Among them, benzoic acid accounts for 20% by weight except moisture. As shown in Table 1, since the waste contains various by-products and catalysts that can be usefully used, the amount of waste can be reduced by introducing a recovery process for recycling.
폐기물 속의 여러 부생성물 중, 가장 많이 함유되어 있는 안식향산은 최근에 와서 사용량이 증가하고 있을 뿐만 아니라 그 용도도 날이 갈수록 다양해지고 있다.Among the various byproducts in waste, benzoic acid, which is the most abundant, is not only increased in usage but also its usage is getting different day by day.
[표 1][Table 1]
안식향산은 안식향산 자체를 그대로 쓰거나 이것의 유도체로 사용되기도 하는데, 기본적으로 방부제와 아닐린 염료, 의약품, 향료, 페인트, 고무, 플라스틱첨가제 등 여러 분야에 널리 이용되고 있다.Benzoic acid is widely used in various fields such as antiseptics, aniline dyes, medicines, perfumes, paints, rubbers, plastic additives and the like.
이와같은 이유때문에 안식향산에 대한 제법이나 정제방법이 많이 연구되어 왔다. 알려진 방법으로는 한국특허공고 91-03973 에 소개된바 있는 증류법이 있는데, 이방법은 250-300℃의 고온하에서 1, 2차 증류탑으로 정제해서 안식향산을 얻어내는 방법으로서 고온설비가 필요하다는 단점이 있다. 그리고 미국특허 4092353 의 방법은 아민계의 화합물과 반응 시켜서 증류법이나 승화법을 거친후 가성소다로 처리하는 방법인바, 이 방법은 과정이 복잡하고 유기물질을 첨가하는 등의 문제점이 있다. 또 미국특허 3259651 의 방법은 알카리 수용액을 사용해서 알카리염 상태로 증류하여 안식향산을 얻어내는 방법이다. 그외 100℃ 이하의 물을 써서 추출하는 방법이 일본특허공개 소 48-96541, 일본특허공개 소 61-106535,일본특허공고 소 47-2621 및 일본특허공개 소 51-11728 등에 소개된 바 있다.For this reason, much preparation and purification methods for benzoic acid have been studied. A known method is the distillation method disclosed in Korean Patent Publication No. 91-03973. This method has a disadvantage in that high temperature equipment is required as a method of obtaining benzoic acid by refining it with primary and secondary distillation columns at a high temperature of 250-300 ° C have. In addition, the method of US Pat. No. 4,092,353 is a method of reacting with an amine-based compound, followed by distillation or sublimation, and then treating with caustic soda. However, this method has a complicated process and addition of organic materials. The method of U.S. Patent No. 3259651 is a method of obtaining benzoic acid by distillation in an alkaline salt state using an aqueous alkaline solution. Other methods of extracting water using 100 ° C or less have been disclosed in Japanese Patent Application Laid-Open Nos. 48-96541, 61-106535, 47-2621 and 51-11728.
본 발명자들은 유기물질의 용해도가 용매(물)의 이온강도 (ionic strength) 에 의해 변화한다는 사실에 착안하여, 본 발명을 완성하였다.The inventors of the present invention have completed the present invention in view of the fact that the solubility of an organic material varies depending on the ionic strength of a solvent (water).
즉 본 발명은 염(salt) 으로 용매인 물의 이온강도를 조절하여 폐기물로 부터 93% 이상의 순도를 갖는 안식향산을 회수하는 방법에 관한 것이다.That is, the present invention relates to a method for recovering benzoic acid having a purity of 93% or more from waste by regulating the ionic strength of water as a solvent with a salt.
이하 본 발명은 예시도면에 의거 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
본 발명은 테레프탈산의 제조공정에서 생성된 폐기물을 제 1도에 예시한 바와같은 추출장치에 투입한다음 여기에 염(salt)의 수용액을 첨가하고, 상기혼합물을 40℃~80℃의 항온 조건하에서 10분정도 교반한 다음에 여과하고 결정화 하는 안식향산의 회수방법이다.The present invention relates to a process for the preparation of terephthalic acid, which comprises the steps of charging the waste produced in the process of producing terephthalic acid into an extraction device as illustrated in FIG. 1, adding an aqueous solution of the salt thereto and heating the mixture under constant temperature conditions of 40 ° C. to 80 ° C. Followed by stirring for about 10 minutes, followed by filtration and crystallization.
본 발명에서 폐기물과 염의 수용액간의 비는 중량비로 1 : 3 으로 하는 것이 좋다.In the present invention, the ratio between the waste and the aqueous solution of the salt is preferably 1: 3 by weight.
만약 염의 수용액의 비가 3 미만이면 폐기물이 수용액에 균일하게 녹지 않는다.If the ratio of salt aqueous solution is less than 3, the waste does not dissolve uniformly in the aqueous solution.
또 3을 초과하면 수용액의 양이 많아져서 수율이 떨어지고 침전물을 얻는데 시간이 오래걸린다.If it is more than 3, the amount of the aqueous solution becomes large, and the yield decreases and it takes a long time to obtain the precipitate.
또 본 발명에 사용되는 염의 수용액의 농도는 10%~30% 로 하는것이 좋다.The concentration of the aqueous solution of the salt used in the present invention is preferably 10% to 30%.
만약 10% 미만이면 안식향산의 순도가 낮아진다.If it is less than 10%, the purity of benzoic acid is lowered.
또 30% 를 초과하면 물에 대한 염화나트륨 (NaCl) 의 용해도가 한계에 도달하여 염 (salt) 의 침전과 함께 침전하므로 안식향산만을 걸러내기가 어려워진다.If it exceeds 30%, solubility of sodium chloride (NaCl) in water reaches the limit and precipitates together with precipitation of salt, so that it becomes difficult to filter only the benzoic acid.
본 발명에 사용되는 염(salt)은 염화나트륨(NaCl) 또는 염화칼륨(KCl), 등이다.The salt used in the present invention is sodium chloride (NaCl) or potassium chloride (KCl), and the like.
실시예 1Example 1
300g의 폐기물을 제 1 도와 같은 추출장치에 (1.5L) 넣고 NaCl 수용액 900g 과 섞어서 폐기물 : 수용액의 비가 1 : 3 이 되도록 하고, 항온 순환기를 사용하여 60℃의 항온 조건하에서 10분간 교반 시킨 후 유리 필터 (glass filter) 로 여과하고 상온에서 결정화 시켰다. 결정을 여과한 후 HPLC로 성분분석을 하여 그 결과를 표2에 표시하였다.300 g of waste was put into an extraction device (1.5 L) as in the first embodiment and mixed with 900 g of NaCl aqueous solution so that the ratio of waste to aqueous solution was 1: 3. The mixture was stirred for 10 minutes under constant temperature condition at 60 캜 using a thermostat circulator, Filtered with a glass filter and crystallized at room temperature. The crystals were filtered and analyzed by HPLC. The results are shown in Table 2.
실시예 2-5Example 2-5
표2에 표시된 바와같이 수용액농도만 다르게 하고 실시예1 과 동일하게 실시하여 그 결과를 표2에 표시하였다.The results are shown in Table 2, in the same manner as in Example 1, except that the concentration of the aqueous solution was different as shown in Table 2.
비교예 1-3Comparative Example 1-3
표2 에 표시된 바와 같이 수용액농도만 다르게 하고 실시예 1 과 동일하게 실시하였다.The same procedure was followed as in Example 1 except that the concentration of the aqueous solution was different as shown in Table 2.
성분분석 및 정량방법Component analysis and quantification method
모든 시료를 메탄올에 용해시킨 다음에 2% 초산 수용액과 아세토니트릴(acetonitrile)을 8 : 2의 비율로 섞어서 만든 흐름상을 45℃에서 1ml/min의 유속으로 흘려보내면서 자외선 검출기 (230nm)를 사용하여 성분분석 및 정량을 하였다.Ultraviolet detector (230 nm) was used to dissolve all the samples in methanol and then flow the mixture at a flow rate of 1 ml / min at 45 ° C. in a stream of 2% acetic acid solution and acetonitrile in a ratio of 8: 2 The components were analyzed and quantified.
[표 2][Table 2]
제 1 도는 본 발명에 사용되는 추출장치의 개략도.FIG. 1 is a schematic view of an extraction device used in the present invention; FIG.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019960020325A KR100437562B1 (en) | 1996-06-07 | 1996-06-07 | Method for recovering benzoic acid from waste products generated from terephthalic acid production process with high purity |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019960020325A KR100437562B1 (en) | 1996-06-07 | 1996-06-07 | Method for recovering benzoic acid from waste products generated from terephthalic acid production process with high purity |
Publications (2)
Publication Number | Publication Date |
---|---|
KR980002002A KR980002002A (en) | 1998-03-30 |
KR100437562B1 true KR100437562B1 (en) | 2004-10-02 |
Family
ID=37348920
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1019960020325A KR100437562B1 (en) | 1996-06-07 | 1996-06-07 | Method for recovering benzoic acid from waste products generated from terephthalic acid production process with high purity |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR100437562B1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100445352B1 (en) * | 1997-04-16 | 2004-11-03 | 주식회사 삼양사 | Method for recovering benzoic acid with high purity from waste products generated from terephthalic acid production process |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4339601A (en) * | 1979-01-26 | 1982-07-13 | Union Carbide Corporation | Terephthalic acid derivatives and process for preparing them |
US4375553A (en) * | 1981-09-28 | 1983-03-01 | Occidental Research Corporation | Process for producing benzene carboxylic acid salts from aromatic materials |
EP0115101A2 (en) * | 1983-01-03 | 1984-08-08 | Stamicarbon B.V. | Process for the purification of benzoic acid |
EP0261892A2 (en) * | 1986-09-26 | 1988-03-30 | Mitsui Petrochemical Industries, Ltd. | The production of aromatic carboxylic acids |
WO1990001823A1 (en) * | 1988-08-15 | 1990-02-22 | Pacific Scientific Company | Polyphase electronically commutated reluctance motor |
-
1996
- 1996-06-07 KR KR1019960020325A patent/KR100437562B1/en not_active IP Right Cessation
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4339601A (en) * | 1979-01-26 | 1982-07-13 | Union Carbide Corporation | Terephthalic acid derivatives and process for preparing them |
US4375553A (en) * | 1981-09-28 | 1983-03-01 | Occidental Research Corporation | Process for producing benzene carboxylic acid salts from aromatic materials |
EP0115101A2 (en) * | 1983-01-03 | 1984-08-08 | Stamicarbon B.V. | Process for the purification of benzoic acid |
EP0261892A2 (en) * | 1986-09-26 | 1988-03-30 | Mitsui Petrochemical Industries, Ltd. | The production of aromatic carboxylic acids |
WO1990001823A1 (en) * | 1988-08-15 | 1990-02-22 | Pacific Scientific Company | Polyphase electronically commutated reluctance motor |
Also Published As
Publication number | Publication date |
---|---|
KR980002002A (en) | 1998-03-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JPH1045655A (en) | Production of fluorene derivative | |
KR100437562B1 (en) | Method for recovering benzoic acid from waste products generated from terephthalic acid production process with high purity | |
EP0015427A1 (en) | Process for producing 2-chloro-6-nitrobenzonitrile | |
DE4333642A1 (en) | Process for the preparation of formylimidazoles | |
US6310239B1 (en) | Process for manufacturing terephthalic acid | |
CN1238356C (en) | Method for extracting tetrodotoxin | |
EP1642881B1 (en) | Process for producing 5-iodo-2-methylbenzoic acid | |
KR100437563B1 (en) | METHOD FOR RECOVERING TEREPHTHALIC ACID WITH HIGH PURITY FROM WASTE GENERATED IN PRODUCTION PROCESS OF TEREPHTHALIC ACID BY CONTROLLING pH | |
CS231971B2 (en) | Purification method for mercaptobenzothiazole | |
US4324665A (en) | Process for recovering bromine from waste liquid | |
RU2083280C1 (en) | Method of isolation of precious metal from inorganic and/or organic residue | |
CN1237575A (en) | Liquid-phase hydrogenation new technological process for preparation of P-aminophenol by using P-nitrophenol | |
US3842115A (en) | Process for purifying diaminomaleonitrile | |
CN1100037C (en) | Process for preparing tetramethyl guanidine | |
KR100193680B1 (en) | Recovery and Purification of Benzoic Acid from Wastes in Terephthalic Acid Manufacturing Process | |
SU674986A1 (en) | Method of obtaining calcium chloride | |
CN114315703B (en) | Preparation method of high-purity vitamin B6 | |
CN111704272B (en) | Method for treating hydroquinone-containing sewage and recovering resources | |
US3522268A (en) | Process for separation and recovery of oxazole | |
JP3291987B2 (en) | Purification method of O, S-dimethyl-N-acetylphosphoramidothioate | |
CN101941898B (en) | Purification method of vitamin K3 | |
KR100476116B1 (en) | Ultra high purity benzoic acid recovery method using halogen-based organic solvent | |
JPS6317066B2 (en) | ||
JPH05194313A (en) | Production of 2,6-dihydroxybenzoic acid | |
KR19990007800A (en) | Method for preparing streptogamine |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20070530 Year of fee payment: 4 |
|
LAPS | Lapse due to unpaid annual fee |