JP2997720B2 - Method for producing terephthalic acid - Google Patents
Method for producing terephthalic acidInfo
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- JP2997720B2 JP2997720B2 JP18666890A JP18666890A JP2997720B2 JP 2997720 B2 JP2997720 B2 JP 2997720B2 JP 18666890 A JP18666890 A JP 18666890A JP 18666890 A JP18666890 A JP 18666890A JP 2997720 B2 JP2997720 B2 JP 2997720B2
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- Prior art keywords
- adsorbent
- exhaust gas
- activated carbon
- filled
- adsorption tower
- Prior art date
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Description
【発明の詳細な説明】 産業上の利用分野 本発明はテレフタル酸の製造方法に関し、詳しくは、
酸化反応器中で酢酸を溶剤としてｐ−キシレンを液相で
分子状酸素により酸化してテレフタル酸を製造する方法
において、上記酸化反応器から排出された酸化排ガスに
同伴する有機物と水分とを同時に酸化排ガスから除去す
るテレフタル酸の製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing terephthalic acid,
In a method of producing terephthalic acid by oxidizing p-xylene with molecular oxygen in a liquid phase using acetic acid as a solvent in an oxidation reactor, an organic substance and water accompanying the oxidation exhaust gas discharged from the oxidation reactor are simultaneously produced. The present invention relates to a method for producing terephthalic acid removed from oxidized exhaust gas.
従来の技術 酸化反応器中で酢酸を溶剤とし、コバルト、マンガン
及び臭素を含有する触媒の存在下に、ｐ−キシレンを分
子状酸素によつて液相酸化して、連続的にテレフタル酸
を製造する方法は、従来より工業的に大規模に行なわれ
ている。2. Prior Art Continuous production of terephthalic acid by liquid phase oxidation of p-xylene with molecular oxygen in the presence of a catalyst containing cobalt, manganese and bromine using acetic acid as a solvent in an oxidation reactor This method has been industrially performed on a large scale conventionally.
このような方法において、酸化反応器から排出される
酸化排ガスには、酢酸メチル、酢酸、ｐ−キシレン、有
機臭素化合物、ベンゼン、トルエン、その他の芳香族炭
化水素等の有用物質と水分とが含まれており、これらを
酸化排ガスから回収することは、公害防止対策上、有用
であるのみならず、有用物質の回収再利用を図ることも
できるので、経済的意義も非常に大きい。In such a method, the oxidation exhaust gas discharged from the oxidation reactor contains useful substances such as methyl acetate, acetic acid, p-xylene, organic bromine compounds, benzene, toluene, and other aromatic hydrocarbons, and water. Recovering them from the oxidizing exhaust gas is not only useful in pollution prevention measures, but also has the great economic significance because it can also recover and reuse useful substances.
そこで、重金属化合物と臭素又は臭素含有化合物から
なる触媒の存在下でｐ−キシレンを液相酸化してテレフ
タル酸を製造する方法において、臭化メチルや水分を含
む酸化排ガスを活性炭又はモレキユラーシーブに接触さ
せ、臭化メチルを吸着させた後、脱着して回収する方法
が特公昭64−3860号公報に既に提案されている。また、
酢酸を溶剤とし、コバルト、マンガン及び臭素を含有す
る触媒の存在下に、ｐ−キシレンを分子状酸素によつて
液相酸化して、連続的にテレフタル酸を製造する方法に
おいて、酸化排ガスを冷却して、凝縮性成分を除去した
後、加圧下に繊維状活性炭に接触させ、酸化排ガスに同
伴する有機物を上記活性炭に吸着させ、回収する方法
も、特開平２−32040号公報に記載されている。Accordingly, in a method for producing terephthalic acid by subjecting p-xylene to liquid phase oxidation in the presence of a catalyst comprising a heavy metal compound and bromine or a bromine-containing compound, an oxidizing exhaust gas containing methyl bromide or water is subjected to activated carbon or molecular sieve. A method has been proposed in Japanese Patent Publication No. 3860/1988, in which methyl bromide is adsorbed and then desorbed and recovered. Also,
In a method for continuously producing terephthalic acid by subjecting p-xylene to liquid phase oxidation with molecular oxygen in the presence of a catalyst containing cobalt, manganese and bromine using acetic acid as a solvent, the oxidation exhaust gas is cooled. Then, after removing the condensable components, it is contacted with fibrous activated carbon under pressure, the organic matter accompanying the oxidized exhaust gas is adsorbed on the activated carbon, and a method of recovering is also described in JP-A-2-32040. I have.
しかし、このような単層の吸着剤による吸着によれ
ば、用いる吸着剤の種類によつては、ある種の物質は有
効に吸着されるが、ある種の物質は有効に吸着されな
い。例えば、酸化排ガスを工業用窒素の代替ガスとして
用いるには、酸化排ガス中の水分を除去することが必要
であるが、水の除去を目的として、シリカゲル等の吸着
剤を用いれば、有機物を除去することが困難であり、他
方、有機物の除去を目的として、活性炭等を用いれば、
水分の除去が困難となる。However, according to the adsorption by such a single-layer adsorbent, depending on the kind of the adsorbent used, some substances are adsorbed effectively, but some substances are not adsorbed effectively. For example, in order to use oxidized exhaust gas as a substitute gas for industrial nitrogen, it is necessary to remove moisture in the oxidized exhaust gas. However, if an adsorbent such as silica gel is used for the purpose of removing water, organic substances can be removed. On the other hand, if activated carbon or the like is used for the purpose of removing organic substances,
It becomes difficult to remove water.
更に、酸化排ガス中の水分の存在は、活性炭の有機物
に対する吸着能を著しく減少させるおそれもある。例え
ば、前述した特公昭64−3860号公報に記載されているよ
うに、活性炭のみを用いて臭化メチルを吸着させるとき
は、水を除去することができないのみならず、水の存在
によつて、活性炭の吸着能が著しく減少するので、実用
的な方法としては採用し難い。Furthermore, the presence of moisture in the oxidizing exhaust gas may significantly reduce the ability of activated carbon to adsorb organic substances. For example, as described in JP-B-64-3860, when methyl bromide is adsorbed by using only activated carbon, not only water cannot be removed, but also the presence of water. In addition, since the ability to adsorb activated carbon is significantly reduced, it is difficult to adopt this method as a practical method.
発明が解決しようとする課題 本発明は、上述したように、テレフタル酸の製造時、
生成する酸化排ガスに同伴する有機物と水の除去回収に
おける従来の方法の問題を解決するためになされたもの
であつて、酸化排ガス中の有機物と水とを同時に効率よ
く除去することができるテレフタル酸の製造方法を提供
することを目的とする。Problems to be Solved by the Invention The present invention, as described above, when producing terephthalic acid,
Terephthalic acid, which has been made to solve the problems of the conventional method of removing and recovering organic substances and water accompanying the generated oxidized exhaust gas, and is capable of simultaneously efficiently removing the organic substances and water in the oxidized exhaust gas. It is an object of the present invention to provide a method for producing the same.
課題を解決するための手段 本発明は、酸化反応器中で酢酸を溶剤としてｐ−キシ
レンを液相で分子状酸素により酸化してテレフタル酸を
製造する方法において、上記酸化反応器から排出された
酸化排ガスを冷却して凝縮性成分を凝縮させた後、第一
層の吸着剤として活性炭を充填し、第二層の吸着剤とし
てシリカ系吸着剤若しくはゼオライト系吸着剤を充填し
た吸着塔に上記酸化排ガスを導入するか、又は第１の吸
着塔に第１の吸着剤として活性炭を充填し、第２の吸着
塔に第２の吸着剤としてシリカ系吸着剤若しくはゼオラ
イト系吸着剤を充填し、上記酸化排ガスを上記第１及び
第２の吸着塔に順次に導入して、上記酸化排ガスに同伴
する有機物と水とを上記吸着剤に吸着させ、酸化排ガス
より除去することを特徴とする。Means for Solving the Problems The present invention relates to a method for producing terephthalic acid by oxidizing p-xylene with molecular oxygen in a liquid phase using acetic acid as a solvent in an oxidation reactor. After cooling the oxidizing exhaust gas to condense the condensable components, the first layer is filled with activated carbon as an adsorbent, and the second layer is adsorbed with a silica-based adsorbent or a zeolite-based adsorbent. Oxidizing exhaust gas is introduced, or the first adsorption tower is filled with activated carbon as a first adsorbent, and the second adsorption tower is filled with a silica-based adsorbent or a zeolite-based adsorbent as a second adsorbent, The oxidizing exhaust gas is successively introduced into the first and second adsorption towers, and organic substances and water accompanying the oxidizing exhaust gas are adsorbed by the adsorbent and removed from the oxidizing exhaust gas.
本発明によるテレフタル酸の製造方法においては、酸
化反応器中にて、酢酸溶剤中、コバルト化合物、マンガ
ン化合物及び臭素を含有する酸化触媒の存在下に、高温
加圧下に、ｐ−キシレンを分子状酸素含有ガスによつて
酸化する。In the method for producing terephthalic acid according to the present invention, in an oxidation reactor, in the presence of an oxidation catalyst containing a cobalt compound, a manganese compound and bromine in an acetic acid solvent, under high temperature and pressure, p-xylene is molecularly converted. Oxidized by oxygen containing gas.
上記酸化触媒は、反応系内において、コバルトイオ
ン、マンガンイオン及び臭素イオンを生じる触媒であつ
て、通常は、コバルト化合物、マンガン化合物及び臭素
化合物からなるが、これら以外に他の触媒成分を含んで
いてもよい。The oxidation catalyst is a catalyst that generates cobalt ions, manganese ions, and bromine ions in the reaction system, and usually includes a cobalt compound, a manganese compound, and a bromine compound. May be.
酸化剤として用いる分子状酸素含有ガスとしては、酸
素、空気、酸素と不活性ガスの混合物等が用いられる。As the molecular oxygen-containing gas used as the oxidizing agent, oxygen, air, a mixture of oxygen and an inert gas, or the like is used.
本発明によるテレフタル酸の製造方法において、溶剤
に対するｐ−キシレンの割合は１〜50重量％、触媒の使
用量は、それぞれ溶剤に対して、コバルト原子が10〜50
00重量ppm、マンガン原子が10〜5000重量ppm、臭素原子
が10〜10000重量ppmの範囲であることが好ましい。分子
状酸素含有ガスとして空気を用いるときは、ｐ−キシレ
ン1kgに対して、0.5〜15Nm3が用いられる。In the method for producing terephthalic acid according to the present invention, the ratio of p-xylene to the solvent is 1 to 50% by weight, and the amount of the catalyst used is such that 10 to 50 cobalt atoms are contained in the solvent.
It is preferable that the content is 00 ppm by weight, 10 to 5000 ppm by weight of manganese atoms, and 10 to 10000 ppm by weight of bromine atoms. When air is used as the molecular oxygen-containing gas, 0.5 to 15 Nm 3 is used for 1 kg of p-xylene.
酸化反応は、通常、温度150〜260℃、圧力４〜50kg/c
m2G、平均滞留時間10〜200分の条件下に行なわれる。The oxidation reaction is usually performed at a temperature of 150 to 260 ° C and a pressure of 4 to 50 kg / c.
m 2 G, average residence time 10 to 200 minutes.
このようなｐ−キシレンの液相酸化において、酸化反
応器から排出される酸化排ガスには、酸化に用いられた
分子状酸素含有ガスのほかに、溶剤である酢酸の一部が
酸化反応中に分解燃焼して生成する二酸化炭素、一酸化
炭素、酢酸メチル、更には溶剤として用いた酢酸、未反
応ｐ−キシレン、反応によつて生成した水、有機臭素化
合物、ベンゼン、トルエン等が含まれている。In such liquid phase oxidation of p-xylene, the oxidation exhaust gas discharged from the oxidation reactor contains, in addition to the molecular oxygen-containing gas used for the oxidation, part of acetic acid as a solvent during the oxidation reaction. Includes carbon dioxide, carbon monoxide, methyl acetate produced by decomposition and combustion, acetic acid used as a solvent, unreacted p-xylene, water produced by the reaction, organic bromine compounds, benzene, toluene, etc. I have.
酸化排ガス中におけるこれら成分の濃度は、大量に含
まれているものとして、酸素が0.1〜８容量％、二酸化
炭素が0.05〜５容量％、一酸化炭素が0.01〜５容量％程
度である。このほかに除去されるべき有機物として、酢
酸メチルが100〜5000容量ppm、ｐ−キシレンが10〜1000
容量ppm、有機臭素化合物が臭素原子換算で１〜1000容
量ppm、ベンゼンが０〜100容量ppm、トルエンが０〜100
容量ppm程度含まれている。The concentrations of these components in the oxidizing exhaust gas are about 0.1 to 8% by volume, about 0.05 to 5% by volume of carbon dioxide, and about 0.01 to 5% by volume of carbon monoxide, assuming that they are contained in large amounts. In addition, as organic substances to be removed, methyl acetate is 100 to 5000 ppm by volume, and p-xylene is 10 to 1000 ppm.
Ppm by volume, 1 to 1000 ppm by volume of organic bromine compound in terms of bromine atom, 0 to 100 ppm by volume of benzene, 0 to 100 ppm of toluene
It contains about ppm by volume.
本発明の方法によれば、このような種々の成分を含む
酸化排ガスを冷却して凝縮性成分を凝縮させた後、第一
層の吸着剤として活性炭を充填し、第二層の吸着剤とし
てシリカ系吸着剤若しくはゼオライト系吸着剤を充填し
た吸着塔に上記酸化排ガスを導入するか、又は第１の吸
着塔に第１の吸着剤として活性炭を充填し、第２の吸着
塔に第２の吸着剤としてシリカ系吸着剤若しくはゼオラ
イト系吸着剤を充填し、上記酸化排ガスを上記第１及び
第２の吸着塔に順次に導入して、上記酸化排ガスに同伴
する有機物と水とを上記吸着剤に吸着させ、酸化排ガス
より除去し、回収する。According to the method of the present invention, after cooling the oxidizing exhaust gas containing such various components and condensing the condensable components, the first layer is filled with activated carbon as an adsorbent, and the second layer is adsorbed as an adsorbent. The oxidized exhaust gas is introduced into an adsorption tower filled with a silica-based adsorbent or a zeolite-based adsorbent, or the first adsorption tower is charged with activated carbon as a first adsorbent, and the second adsorption tower is charged with a second adsorbent. A silica-based adsorbent or a zeolite-based adsorbent is filled as an adsorbent, and the oxidized exhaust gas is sequentially introduced into the first and second adsorption towers, and organic substances and water accompanying the oxidized exhaust gas are adsorbed by the adsorbent. , Removed from the oxidized exhaust gas, and recovered.
更に、本発明によれば、第一層の吸着剤として活性炭
を充填し、第二層の吸着剤としてシリカ系吸着剤を充填
し、第三層の吸着剤として活性炭を充填した吸着塔に上
記酸化排ガスを導入するか、又は第１の吸着塔に第１の
吸着剤として活性炭を充填し、第２の吸着塔に第２の吸
着剤としてシリカ系吸着剤を充填し、第３の吸着塔に第
３の吸着剤として活性炭を充填し、上記酸化排ガスを上
記第１、第２及び第３の吸着塔に順次に導入して、上記
酸化排ガスに同伴する有機物と水とを上記吸着剤に吸着
させ、酸化排ガスより除去することができる。Furthermore, according to the present invention, the first column is filled with activated carbon as an adsorbent, the second layer is filled with a silica-based adsorbent, and the third layer is adsorbed with activated carbon as an adsorbent in the adsorption tower. The oxidizing exhaust gas is introduced, or the first adsorption tower is filled with activated carbon as the first adsorbent, and the second adsorption tower is filled with a silica-based adsorbent as the second adsorbent. Is charged with activated carbon as a third adsorbent, and the oxidized exhaust gas is sequentially introduced into the first, second, and third adsorption towers, and organic substances and water accompanying the oxidized exhaust gas are added to the adsorbent. It can be adsorbed and removed from the oxidizing exhaust gas.
このように、本発明によれば、上記第一層や第１の吸
着剤、第三層や第３の吸着剤として、粒状、粉状又は繊
維状の活性炭が用いられ、第二層又は第２の吸着剤とし
て、シリカゲル等のシリカ系吸着剤やゼオライト系吸着
剤が用いられる。また、本発明によれば、酸化排ガスを
このように吸着剤に接触させる前に、スクラバー等の装
置を通して、水と接触させてもよい。As described above, according to the present invention, granular, powdery or fibrous activated carbon is used as the first layer or the first adsorbent, the third layer or the third adsorbent, and the second layer or the first adsorbent is used. As the second adsorbent, a silica-based adsorbent such as silica gel or a zeolite-based adsorbent is used. According to the present invention, the oxidizing exhaust gas may be brought into contact with water through a device such as a scrubber before being brought into contact with the adsorbent.
酸化排ガスを吸着塔に導入する際の圧力は、通常、１
〜50kg/cm2G、好ましくは2.5〜50kg/cm2Gである。しか
し、この圧力が高いほど、吸着剤の破過容量が増大する
ので、吸着塔の耐圧性や昇圧コスト等が許す限り、酸化
排ガスを吸着塔に導入する際の圧力は、高いのが好まし
い。The pressure at which the oxidizing exhaust gas is introduced into the adsorption tower is usually 1
~50kg / cm 2 G, preferably 2.5~50kg / cm 2 G. However, the higher the pressure, the greater the breakthrough capacity of the adsorbent. Therefore, the pressure at which the oxidizing exhaust gas is introduced into the adsorption tower is preferably high as long as the pressure resistance of the adsorption tower and the cost of pressure rise allow.
また、吸着塔内での酸化排ガスの空塔速度は、通常、
0.001〜1m/秒、好ましくは0.01〜0.5m/秒の範囲であ
る。酸化排ガスを通気する際の温度は、通常、０〜60
℃、好ましくは10〜50℃の範囲である。The superficial velocity of the oxidizing exhaust gas in the adsorption tower is usually
The range is 0.001 to 1 m / sec, preferably 0.01 to 0.5 m / sec. The temperature at which the oxidizing exhaust gas is aerated is usually from 0 to 60.
° C, preferably in the range of 10 to 50 ° C.
このようにして、酸化排ガスを第一層、第二層（及び
第三層）の吸着剤に順次に接触させ、又は第１、第２
（及び第３）の吸着剤に順次に接触させ、有機物及び水
を吸着させた後、これら有機物及び水を吸着剤から脱着
させる。特に、少量の窒素ガスを用いて脱着させるのが
好ましい。In this way, the oxidizing exhaust gas is brought into contact with the adsorbents of the first layer, the second layer (and the third layer) sequentially, or
After the organic substance and water are adsorbed successively by contact with the (and third) adsorbent, the organic substance and water are desorbed from the adsorbent. In particular, it is preferable to perform desorption using a small amount of nitrogen gas.
特に、本発明においては、前記第一層、第二層（及び
第三層）の吸着剤を充填した同じ吸着塔を二基設置し、
第１の吸着塔に酸化排ガスを導入して、有機物及び水の
吸着を行なわせ、第２の吸着塔では、窒素を通気し、精
製し、この窒素を第１の吸着塔に導入して、有機物及び
水の脱着及び吸着剤の再生を効率よく行なうことができ
る。In particular, in the present invention, two identical adsorption towers packed with the first layer, the second layer (and the third layer) of the adsorbent are installed,
The oxidizing exhaust gas is introduced into the first adsorption tower to adsorb organic substances and water. In the second adsorption tower, nitrogen is passed and purified, and the nitrogen is introduced into the first adsorption tower. Desorption of organic matter and water and regeneration of the adsorbent can be performed efficiently.
脱着した有機物及び水を含む脱着窒素ガスは、通常の
無害化装置、例えば、酸素の存在下に有機物を燃焼させ
る装置や、酸化触媒を用いる有機物の燃焼装置等によつ
て、無害化することができる。また、通常の冷却又は吸
収等の手段によつて、脱着窒素ガス中の有機物を回収す
ることもできる。The desorbed nitrogen gas containing the desorbed organic substances and water can be detoxified by a normal detoxifying apparatus, for example, an apparatus for burning organic substances in the presence of oxygen, or a combustion apparatus for organic substances using an oxidation catalyst. it can. Further, the organic matter in the desorbed nitrogen gas can be recovered by ordinary cooling or absorption.
発明の効果 本発明の方法によれば、酢酸を溶剤としてｐ−キシレ
ンを液相で分子状酸素により酸化してテレフタル酸を製
造する方法において、酸化排ガスに同伴する有機物と水
とを同時に除去することができ、酸化排ガスは、例え
ば、工業用窒素の代替として用いることができ、他方、
除去された有機物は容易に回収し、又は無害化すること
ができる。According to the method of the present invention, in a method for producing terephthalic acid by oxidizing p-xylene with molecular oxygen in a liquid phase using acetic acid as a solvent, an organic substance and water accompanying the oxidized exhaust gas are simultaneously removed. Oxidizing exhaust gases can be used, for example, as a substitute for industrial nitrogen, while
The removed organic matter can be easily recovered or made harmless.
実施例 以下に実施例を挙げて本発明を説明するが、本発明は
これら実施例により何ら限定されるものではない。尚、
以下において、吸着剤として、活性炭は武田薬品工業
（株）製のものを用い、シリカゲルは富士デヴイソン
（株）製のものを用いた。EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. still,
In the following, as the adsorbent, activated carbon manufactured by Takeda Pharmaceutical Co., Ltd. was used, and silica gel manufactured by Fuji Devison Co., Ltd. was used.
実施例１ ｐ−キシレンを触媒の存在下、酢酸溶剤中で空気酸化
して、テレフタル酸を製造した。排出された酸化排ガス
を40℃まで冷却し、凝縮製成分を凝縮させた。この処理
の後の酸化排ガスの圧力は10kg/cm2Gであつた。また、4
0℃に冷却した酸化排ガスには、臭化メチルが25容量pp
m、酢酸メチルが900容量ppm、ｐ−キシレンが80容量pp
m、ベンゼンが９容量ppm、トルエンが４容量ppm含まれ
ており、水分量は、大気圧下の露点値として−４℃であ
つた。Example 1 Terephthalic acid was produced by subjecting p-xylene to air oxidation in an acetic acid solvent in the presence of a catalyst. The discharged oxidizing exhaust gas was cooled to 40 ° C. to condense the condensed components. After this treatment, the pressure of the oxidizing exhaust gas was 10 kg / cm 2 G. Also, 4
25 volume pp methyl bromide in oxidizing exhaust gas cooled to 0 ° C
m, methyl acetate 900 vol ppm, p-xylene 80 vol pp
m, benzene 9 ppm by volume and toluene 4 ppm by volume, and the water content was −4 ° C. as a dew point value under atmospheric pressure.
この酸化排ガスの1Nm3当りに、下から活性炭（第一
層）3g、シリカゲル（第二層）30g及び活性炭（第三
層）3gを層状に吸着塔内に充填した。From the bottom, 3 g of activated carbon (first layer), 30 g of silica gel (second layer) and 3 g of activated carbon (third layer) were packed into the adsorption tower from 1 Nm 3 of the oxidized exhaust gas from below.
この吸着塔の下部から上記酸化排ガスを連続的に導入
し、上部から連続的に取り出した。吸着処理後の酸化排
ガスには、臭化メチルを含む有機物は、ガスクロマトグ
ラフィーで測定し得る１容量ppm以下であつた。また、
水分は、大気圧下の露点値として−70℃以下であつた。The oxidizing exhaust gas was continuously introduced from the lower part of the adsorption tower, and continuously taken out from the upper part. Organic matter containing methyl bromide in the oxidized exhaust gas after the adsorption treatment was 1 ppm by volume or less, which can be measured by gas chromatography. Also,
The moisture was below -70 ° C as the dew point value under atmospheric pressure.
実施例２ 吸着塔に、酸化排ガスの1Nm3当りに、下から活性炭
（第一層）8g及びシリカゲル（第二層）70gを層状に充
填した。Example 2 An adsorption tower was filled with 8 g of activated carbon (first layer) and 70 g of silica gel (second layer) from the bottom per 1 Nm 3 of oxidized exhaust gas in a layered manner.
この吸着塔の下部から前記酸化排ガスを連続的に導入
し、上部から連続的に取り出した。吸着処理後の酸化排
ガス中の臭化メチルを除く有機物は、ガスクロマトグラ
フィーで測定し得る１容量ppm以下であつた。臭化メチ
ルは25容量ppmであつた。また、水分は、大気圧下の露
点値として−70℃以下であつた。The oxidizing exhaust gas was continuously introduced from the lower part of the adsorption tower, and continuously taken out from the upper part. Organic substances other than methyl bromide in the oxidized exhaust gas after the adsorption treatment were 1 ppm by volume or less, which can be measured by gas chromatography. Methyl bromide was 25 ppm by volume. In addition, the moisture was -70 ° C or less as a dew point value under atmospheric pressure.
比較例１ 吸着塔に、酸化排ガスの1Nm3当りに活性炭60gを充填
した。Comparative Example 1 An adsorption tower was filled with 60 g of activated carbon per 1 Nm 3 of oxidized exhaust gas.
この吸着塔の下部から前記酸化排ガスを連続的に導入
し、上部から連続的に取り出した。吸着処理後の酸化排
ガスには、臭化メチルを除く有機物は、ガスクロマトグ
ラフィーで測定し得る１容量ppm以下であつた。臭化メ
チルは25容量ppmであつた。また、水分は、大気圧下の
露点値として−４℃以下であつた。The oxidizing exhaust gas was continuously introduced from the lower part of the adsorption tower, and continuously taken out from the upper part. Organic matter excluding methyl bromide in the oxidized exhaust gas after the adsorption treatment was 1 ppm by volume or less, which can be measured by gas chromatography. Methyl bromide was 25 ppm by volume. Further, the water content was -4 ° C or less as a dew point value under the atmospheric pressure.
比較例２ 吸着塔に、酸化排ガスの1Nm3当りにシリカゲル60gを
充填した。Comparative Example 2 An adsorption tower was filled with 60 g of silica gel per 1 Nm 3 of oxidized exhaust gas.
この吸着塔の下部から前記酸化排ガスを連続的に導入
し、上部から連続的に取り出した。吸着処理後の酸化排
ガス中の水分は、大気圧下の露点値として−60℃以下で
あつたが、臭化メチル、酢酸メチル、ｐ−キシレン、ベ
ンゼン等の有機物の濃度は、吸着処理前の酸化排ガスと
同じであつた。The oxidizing exhaust gas was continuously introduced from the lower part of the adsorption tower, and continuously taken out from the upper part. The moisture in the oxidizing exhaust gas after the adsorption treatment was −60 ° C. or less as the dew point value under the atmospheric pressure, but the concentration of organic substances such as methyl bromide, methyl acetate, p-xylene, and benzene was lower than that before the adsorption treatment. It was the same as the oxidation exhaust gas.
比較例３ 吸着塔に、酸化排ガスの1Nm3当りに、下からシリカゲ
ル（第一層）30gと活性炭（第二層）3gを層状に充填し
た。Comparative Example 3 The adsorption tower was filled with 30 g of silica gel (first layer) and 3 g of activated carbon (second layer) from below in a layered manner per 1 Nm 3 of oxidized exhaust gas.
この吸着塔の下部から前記酸化排ガスを連続的に導入
し、上部から連続的に取り出した。吸着処理後の酸化排
ガス中の臭化メチルを含む有機物は、ガスクロマトグラ
フィーで測定し得る１容量ppm以下であつた。また、水
分は、大気圧下の露点値として−70℃以下であつた。The oxidizing exhaust gas was continuously introduced from the lower part of the adsorption tower, and continuously taken out from the upper part. The organic matter containing methyl bromide in the oxidized exhaust gas after the adsorption treatment was 1 ppm by volume or less, which can be measured by gas chromatography. In addition, the moisture was -70 ° C or less as a dew point value under atmospheric pressure.
しかし、シリカゲルが酸化排ガス中に含まれる水滴に
曝されて、徐々に粉化し、最終的には、粉化したシリカ
ゲルによつて吸着塔が閉塞され、酸化排ガスが流通しな
くなつた。However, the silica gel was exposed to water droplets contained in the oxidized exhaust gas, and gradually became powdered. Eventually, the adsorption tower was blocked by the powdered silica gel, and the oxidized exhaust gas stopped flowing.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中尾 藤正 山口県玖珂郡和木町和木６丁目１番２号 三井石油化学工業株式会社内 (56)参考文献 特開 平２−32040（ＪＰ，Ａ) 特開 平１−99627（ＪＰ，Ａ) 特開 平７−159019（ＪＰ，Ａ) 特開 平２−120212（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C07C 63/26 C07C 51/42 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Fujimasa Nakao 61-2, Waki, Waki-machi, Kuga-gun, Yamaguchi Prefecture Inside Mitsui Petrochemical Industry Co., Ltd. (56) References JP-A-2-32040 (JP, A JP-A-1-99627 (JP, A) JP-A-7-159019 (JP, A) JP-A-2-120212 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C07C 63/26 C07C 51/42
Claims (2)
レンを液相で分子状酸素により酸化してテレフタル酸を
製造する方法において、上記酸化反応器から排出された
酸化排ガスを冷却して凝縮性成分を凝縮させた後、第一
層の吸着剤として活性炭を充填し、第二層の吸着剤とし
てシリカ系吸着剤若しくはゼオライト系吸着剤を充填し
た吸着塔に上記酸化排ガスを導入するか、又は第１の吸
着塔に第１の吸着剤として活性炭を充填し、第２の吸着
塔に第２の吸着剤としてシリカ系吸着剤若しくはゼオラ
イト系吸着剤を充填し、上記酸化排ガスを上記第１及び
第２の吸着塔に順次に導入して、上記酸化排ガスに同伴
する有機物と水とを上記吸着剤に吸着させ、酸化排ガス
より除去することを特徴とするテレフタル酸の製造方
法。1. A method for producing terephthalic acid by oxidizing p-xylene with molecular oxygen in a liquid phase using acetic acid as a solvent in an oxidation reactor, wherein oxidized exhaust gas discharged from the oxidation reactor is cooled. After condensing the condensable components, whether the oxidized exhaust gas is introduced into an adsorption tower filled with activated carbon as an adsorbent for the first layer and filled with a silica-based adsorbent or a zeolite-based adsorbent as an adsorbent for the second layer. Alternatively, the first adsorption tower is filled with activated carbon as a first adsorbent, the second adsorption tower is filled with a silica-based adsorbent or a zeolite-based adsorbent as a second adsorbent, and the oxidized exhaust gas is discharged through the first adsorber. A method for producing terephthalic acid, comprising sequentially introducing the organic matter and water accompanying the oxidized exhaust gas into the first and second adsorption towers, adsorbing the organic matter and water on the adsorbent, and removing the organic substance and water from the oxidized exhaust gas.
レンを液相で分子状酸素により酸化してテレフタル酸を
製造する方法において、上記酸化反応器から排出された
酸化排ガスを冷却して凝縮性成分を凝縮させた後、第一
層の吸着剤として活性炭を充填し、第二層の吸着剤とし
てシリカ系吸着剤を充填し、第三層の吸着剤として活性
炭を充填した吸着塔に上記酸化排ガスを導入するか、又
は第１の吸着塔に第１の吸着剤として活性炭を充填し、
第２の吸着塔に第２の吸着剤としてシリカ系吸着剤を充
填し、第３の吸着塔に第３の吸着剤として活性炭を充填
し、上記酸化排ガスを上記第１、第２及び第３の吸着塔
に順次に導入して、上記酸化排ガスに同伴する有機物と
水とを上記吸着剤に吸着させ、酸化排ガスより除去する
ことを特徴とするテレフタル酸の製造方法。2. A method for producing terephthalic acid by oxidizing p-xylene with molecular oxygen in a liquid phase using acetic acid as a solvent in an oxidation reactor, wherein oxidized exhaust gas discharged from the oxidation reactor is cooled. After condensing the condensable components, the first column is filled with activated carbon as an adsorbent, the second layer is filled with a silica-based adsorbent, and the third layer is adsorbed with activated carbon as an adsorbent. Introducing the oxidizing exhaust gas, or filling the first adsorption tower with activated carbon as a first adsorbent,
A second adsorber is filled with a silica-based adsorbent as a second adsorbent, a third adsorber is charged with activated carbon as a third adsorbent, and the oxidized exhaust gas is subjected to the first, second and third adsorbents. A terephthalic acid production method, wherein organic substances and water accompanying the oxidized exhaust gas are successively introduced into the adsorption tower to be adsorbed by the adsorbent and removed from the oxidized exhaust gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18666890A JP2997720B2 (en) | 1990-07-12 | 1990-07-12 | Method for producing terephthalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18666890A JP2997720B2 (en) | 1990-07-12 | 1990-07-12 | Method for producing terephthalic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0474153A JPH0474153A (en) | 1992-03-09 |
| JP2997720B2 true JP2997720B2 (en) | 2000-01-11 |
Family
ID=16192574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18666890A Expired - Fee Related JP2997720B2 (en) | 1990-07-12 | 1990-07-12 | Method for producing terephthalic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2997720B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101342439B (en) * | 2007-07-09 | 2014-01-01 | 中国石油化工股份有限公司 | Hydrocarbons recovery method |
-
1990
- 1990-07-12 JP JP18666890A patent/JP2997720B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101342439B (en) * | 2007-07-09 | 2014-01-01 | 中国石油化工股份有限公司 | Hydrocarbons recovery method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0474153A (en) | 1992-03-09 |
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