JP2020164421A - Method for producing terephthalic acid - Google Patents
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- JP2020164421A JP2020164421A JP2019063273A JP2019063273A JP2020164421A JP 2020164421 A JP2020164421 A JP 2020164421A JP 2019063273 A JP2019063273 A JP 2019063273A JP 2019063273 A JP2019063273 A JP 2019063273A JP 2020164421 A JP2020164421 A JP 2020164421A
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 claims abstract description 80
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 abstract description 12
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000243 solution Substances 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 13
- -1 bromine compound Chemical class 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 229920000139 polyethylene terephthalate Polymers 0.000 description 6
- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- 150000005526 organic bromine compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明はｐ−キシレンの酸素による酸化によりテレフタル酸を製造する技術に関する。より具体的には、従来よりも高品質なテレフタル酸を製造する技術に関する。 The present invention relates to a technique for producing terephthalic acid by oxidizing p-xylene with oxygen. More specifically, it relates to a technique for producing higher quality terephthalic acid than before.
少なくとも一個の脂肪族置換基を有する芳香族化合物から、低級脂肪族モノカルボン酸を溶媒として、例えば、マンガンを含む重金属化合物及び臭素化合物の存在下に分子状酸素含有ガスにより液相酸化して対応する芳香族カルボン酸を製造する方法としては、多くの公知文献がある（例えば特許文献１〜９）。
高純度テレフタル酸は、ポリエチレンテレフタレート（ＰＥＴ）やポリブチレンテレフタレート（ＰＢＴ）の原料として重要な成分であり、その品質の高度化の要求が常在している。
Aromatic compounds having at least one aliphatic substituent are subjected to liquid phase oxidation with a molecular oxygen-containing gas in the presence of, for example, a heavy metal compound containing manganese and a bromine compound using a lower aliphatic monocarboxylic acid as a solvent. There are many known documents (for example, Patent Documents 1 to 9) as a method for producing an aromatic carboxylic acid.
High-purity terephthalic acid is an important component as a raw material for polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), and there is a constant demand for higher quality.
特許文献９には、ｐ−トルアルデヒドとｐ−キシレンとを特定の割合で含む原料を酸素で酸化させて特定の条件でテレフタル酸を製造する方法が開示されている。その技術を用いて得られるテレフタル酸を原料とするＰＥＴは、白度が向上することが開示されている。一方で、得られるテレフタル酸の色相（ＯＤ３４０）は特に変化が見られないことが開示されている。 Patent Document 9 discloses a method for producing terephthalic acid under specific conditions by oxidizing a raw material containing p-tolvaldehyde and p-xylene in a specific ratio with oxygen. It is disclosed that PET made from terephthalic acid obtained by using the technique has improved whiteness. On the other hand, it is disclosed that the hue (OD 340 ) of the obtained terephthalic acid does not change in particular.
市場からは、テレフタル酸の色相のさらなる向上と、生産性の向上とを求める要請がある。よって本発明は、色相にさらに優れたテレフタル酸を提供することを課題としてなされたものである。 There is a demand from the market for further improvement of the hue of terephthalic acid and improvement of productivity. Therefore, the present invention has been made with the object of providing terephthalic acid having an even better hue.
本発明者らは上記の課題を有するテレフタル酸の製造法について鋭意検討した結果、原料のｐ−キシレンと特定量のｐ−トルアルデヒドと特定量のｐ−トルイル酸とを含む原料を特定の温度領域にて酸素で酸化させる工程を混合して液相酸化反応を行うことにより、色相に優れたテレフタル酸が得られることを見出し、本発明に到達した。 As a result of diligent studies on a method for producing terephthalic acid having the above-mentioned problems, the present inventors have made a raw material containing p-xylene as a raw material, a specific amount of p-tolualdehyde, and a specific amount of p-toluic acid at a specific temperature. We have found that terephthalic acid having an excellent hue can be obtained by performing a liquid phase oxidation reaction by mixing the steps of oxidizing with oxygen in the region, and have reached the present invention.
即ち本発明は、以下の構成を有するものである。
ｐ−トルアルデヒドとｐ−トルイル酸とｐ−キシレンとを有機酸水の存在下に下記の要件を満たす条件下で酸素と反応させる工程（Ａ）を含むことを特徴とするテレフタル酸の製造方法。
ｉ）ｐ−トルアルデヒドの含有率が８〜１５質量％であり、且つ、ｐ−トルイル酸の含有率が５〜２０質量％である。
ｉｉ）ｐ−トルアルデヒドの含有率とｐ−トルイル酸の含有率の合計が１５〜３５質量％である（ｐ−トルアルデヒドの含有率とｐ−トルイル酸の含有率とｐ−キシレンの含有率との合計を１００質量％とする。）。
ｉｉｉ）反応温度が１２０〜２４０℃である。
（２） 前記工程（Ａ）で使用する酸素量が、全工程で使用する酸素量を１００％とした場合、８０〜９０％であることを特徴とする前記（１）記載のテレフタル酸の製造方法。
That is, the present invention has the following configuration.
A method for producing terephthalic acid, which comprises a step (A) of reacting p-toluic acid, p-toluic acid and p-xylene with oxygen under the conditions satisfying the following requirements in the presence of organic acid water. ..
i) The content of p-toluic acid is 8 to 15% by mass, and the content of p-toluic acid is 5 to 20% by mass.
ii) The total content of p-toluic acid and p-toluic acid is 15 to 35% by mass (p-toluic acid content, p-toluic acid content and p-xylene content). The total of and is 100% by mass.).
iii) The reaction temperature is 120 to 240 ° C.
(2) The production of terephthalic acid according to the above (1), wherein the amount of oxygen used in the step (A) is 80 to 90% when the amount of oxygen used in all the steps is 100%. Method.
本発明を用いれば、色相に優れたテレフタル酸を効率よく製造することが出来る。このようなテレフタル酸は、さらに品質の優れたＰＥＴやＰＢＴを与えることが期待できる。よって、当該ＰＥＴやＰＢＴからは、新たな性質を有する飲料容器や反射シート、離型フィルムなどの製品を提供できる可能性が有る。 According to the present invention, terephthalic acid having an excellent hue can be efficiently produced. Such terephthalic acid can be expected to give PET or PBT of even higher quality. Therefore, there is a possibility that products such as beverage containers, reflective sheets, and release films having new properties can be provided from the PET and PBT.
本発明のテレフタル酸の製造方法においては、特定の割合のｐ−キシレン、ｐ−トルアルデヒド、ｐ−トルイル酸を、有機酸水の存在下、酸素を用いて特定の温度範囲で酸化させる工程（Ａ）を有することを特徴とする。具体的には、下記の条件で行われる工程である。
ｐ−トルアルデヒドの含有率と、ｐ−トルイル酸の含有率と、ｐ−キシレンの含有率との合計を１００質量％とした場合、
ｉ）ｐ−トルアルデヒドの含有率が８〜１５質量％であり、ｐ−トルイル酸の含有率が５〜２０質量％であり、
ｉｉ）ｐ−トルアルデヒドの含有率と、ｐ−トルイル酸の含有率の合計量が、１５〜３５質量％、および
ｉｉｉ）反応温度が１２０〜２４０℃である。
上記の工程（Ａ）を実施することによって、驚くべきことに色相の改良されたテレフタル酸を得ることが出来る。前記色相は、波長が３４０ｎｍのＵＶ光の透過率で評価することが出来る。
In the method for producing terephthalic acid of the present invention, a step of oxidizing p-xylene, p-toluic acid, and p-toluic acid in a specific ratio in a specific temperature range using oxygen in the presence of organic acid water ( It is characterized by having A). Specifically, it is a process performed under the following conditions.
When the total of the content of p-toluic acid, the content of p-toluic acid, and the content of p-xylene is 100% by mass,
i) The content of p-toluic acid is 8 to 15% by mass, and the content of p-toluic acid is 5 to 20% by mass.
ii) The total amount of p-toluic acid content and p-toluic acid content is 15 to 35% by mass, and iii) the reaction temperature is 120 to 240 ° C.
By carrying out the above step (A), it is possible to obtain terephthalic acid having a surprisingly improved hue. The hue can be evaluated by the transmittance of UV light having a wavelength of 340 nm.
上記のｐ−トルアルデヒドの含有率の好ましい下限値は１０質量％であり、より好ましくは１２質量％である。一方、好ましい上限値は１４質量％である。
上記のｐ−トルイル酸の含有率の好ましい下限値は７質量％であり、より好ましくは８質量％である。一方、好ましい上限値は１５質量％である。
上記のｐ−トルアルデヒドの含有率と、ｐ−トルイル酸の含有率の合計量の好ましい下限値は１８質量％であり、より好ましくは２０質量％である。一方、好ましい上限値は３２質量％、より好ましくは２９質量％である。
The preferable lower limit of the content of p-tolvaldehyde is 10% by mass, more preferably 12% by mass. On the other hand, the preferable upper limit value is 14% by mass.
The preferable lower limit of the content of p-toluic acid is 7% by mass, more preferably 8% by mass. On the other hand, the preferable upper limit value is 15% by mass.
The preferable lower limit of the total amount of the content of p-toluic acid and the content of p-toluic acid is 18% by mass, more preferably 20% by mass. On the other hand, the preferable upper limit value is 32% by mass, more preferably 29% by mass.
前記のｐ−トルアルデヒドやｐ−トルイル酸は、工程（Ａ）の前段の酸化工程で製造されたものであってもよいし、他の方法で製造されたものを反応装置内に導入することもできる。例えば、ｐ−キシレンからテレフタル酸を製造する工程の中で、未反応物として回収されるｐ−トルイル酸などを利用してもよい。
なお本発明の方法によって使用するｐ−トルアルデヒドはＨＦ・ＢＦ３触媒によってトルエンと一酸化炭素とのガッターマンコッホ反応で合成したものが好適に用いられるが、それ以外の製法によるものであっても何等制約は受けない。ＨＦ・ＢＦ３触媒によって製造したｐ−トルアルデヒドはその反応の特性からｏ−トルアルデヒドが約５％含まれるので、その異性体混合物を蒸留または晶析によってｏ−異性体を除去したｐ−トルアルデヒドが通常原料として使用されるが、場合によってはｏ−異性体を含むｐ−トルアルデヒドをそのまま原料として使用することもできる。
前記工程（Ａ）が、上記の条件の範囲内であれば、色相に優れたテレフタル酸を製造するのに有利である。
The p-toluic acid and p-toluic acid may be those produced in the oxidation step in the previous step of the step (A), or those produced by another method may be introduced into the reactor. You can also. For example, p-toluic acid recovered as an unreacted product may be used in the process of producing terephthalic acid from p-xylene.
As the p-tolvaldehyde used by the method of the present invention, one synthesized by a guttermannkoch reaction of toluene and carbon monoxide with a HF / BF 3 catalyst is preferably used, but other production methods are used. Is not subject to any restrictions. Since p-tolvaldehyde produced by the HF / BF 3 catalyst contains about 5% o-tolvaldehyde due to the characteristics of the reaction, p-tolude from which the o-isomer has been removed by distillation or crystallization of the isomer mixture has been obtained. Aldehyde is usually used as a raw material, but in some cases, p-tolvaldehyde containing an o-isomer can be used as a raw material as it is.
If the step (A) is within the above conditions, it is advantageous to produce terephthalic acid having an excellent hue.
前記工程（Ａ）を実施する温度の好ましい下限値は１４０℃、より好ましくは１６０℃、さらに好ましくは１８５℃である。一方、好ましい上限値は２２０℃、より好ましくは２００℃、さらに好ましくは１９５℃である。 The preferable lower limit of the temperature at which the step (A) is carried out is 140 ° C., more preferably 160 ° C., and even more preferably 185 ° C. On the other hand, the preferable upper limit value is 220 ° C., more preferably 200 ° C., and even more preferably 195 ° C.
この工程（Ａ）は、出来る限りｐ−キシレンからテレフタル酸を製造する工程の全体の中では、前半に実施することが好ましくは、特には、最初の反応工程とすることが好ましい。
この理由は現在のところ不明であるが、本発明者らは以下の様に推定している。
色相に影響を及ぼす物質は、
原料のラジカル分解物の１種であろうと推測される。上記の工程（Ａ）の条件で反応を行うことによって、「１、前記の色相悪化成分の生成の反応選択性が低下する」、「２、色相悪化成分が、主として前記３成分が関係する段階で生成し、その生成量が本願の条件であれば低減できる」、「３．前記１項と前記２項の両方の要因の組み合わせ」等が挙げられる。
This step (A) is preferably carried out in the first half of the whole step of producing terephthalic acid from p-xylene as much as possible, and in particular, it is preferably the first reaction step.
The reason for this is currently unknown, but the present inventors presume as follows.
Substances that affect hue are
It is presumed that it is one of the radical decomposition products of the raw material. By carrying out the reaction under the conditions of the above step (A), "1. The reaction selectivity of the formation of the hue-deteriorating component is lowered", "2. The stage in which the hue-deteriorating component is mainly related to the above-mentioned three components". If the amount of production is the condition of the present application, it can be reduced. ”,“ 3. Combination of the factors of both the above item 1 and the above item 2 ”and the like.
本発明における触媒としては公知の触媒を制限なく用いることが出来る。一般的にはマンガン、コバルトおよび臭素を含む化合物が用いられる。複数の化合物を含む組成物も、勿論、例示出来る。
例えば、マンガンおよびコバルト金属塩としては無機酸塩、有機酸塩のいずれも使用可能であり、反応溶媒に可溶な化合物として使用することが望ましい。
マンガン塩の量については充分な触媒効果を得るためにはマンガン金属塩として計算して５０質量ｐｐｍ以上のマンガン濃度とするのが良いが、マンガン濃度が１０００質量ｐｐｍを越えると黒色化することがある。
コバルト塩はコバルト原子として５０〜２０００質量ｐｐｍの範囲が望ましい。
臭素化合物としてはアンモニウム、ナトリウム、カリウム等の無機塩あるいは臭化水素等が使用される。またテトラブロムエタン、テトラブロムｐーキシレンなどの有機臭素化合物も使用もできる。臭素化合物の使用量は臭素原子として溶媒に対して１００〜４０００質量ｐｐｍの範囲で使用することが望ましい。
As the catalyst in the present invention, a known catalyst can be used without limitation. Generally, compounds containing manganese, cobalt and bromine are used. Of course, a composition containing a plurality of compounds can also be exemplified.
For example, as the manganese and cobalt metal salts, either inorganic acid salts or organic acid salts can be used, and it is desirable to use them as compounds soluble in the reaction solvent.
Regarding the amount of manganese salt, in order to obtain a sufficient catalytic effect, it is better to calculate it as a manganese metal salt and set the manganese concentration to 50 mass ppm or more, but if the manganese concentration exceeds 1000 mass ppm, it may turn black. is there.
The cobalt salt preferably has a cobalt atom in the range of 50 to 2000 mass ppm.
As the bromine compound, inorganic salts such as ammonium, sodium and potassium, hydrogen bromide and the like are used. In addition, organic bromine compounds such as tetrabromethane and tetrabrom p-xylene can also be used. The amount of the bromine compound used is preferably in the range of 100 to 4000 mass ppm with respect to the solvent as the bromine atom.
本発明において、溶媒として用いられる有機酸水としては、通常低級脂肪族モノカルボン酸が使用される。このような化合物としては酢酸、プロピオン酸、酪酸などが挙げられる。特に酢酸が好ましい。
溶媒である有機酸水の使用量は原料に対して質量比で２倍以上あれば充分である。溶媒量に上限を規定することにあまり意味はないが、溶媒量が多すぎると前述した溶媒の分解物の影響が出る場合があるので、少ないほうが好ましい傾向がある。好ましい上限値は、原料に対して４〜５倍である。
In the present invention, as the organic acid water used as a solvent, a lower aliphatic monocarboxylic acid is usually used. Examples of such a compound include acetic acid, propionic acid, butyric acid and the like. Acetic acid is particularly preferable.
It is sufficient that the amount of organic acid water used as a solvent is twice or more by mass ratio with respect to the raw material. It does not make much sense to specify the upper limit of the amount of solvent, but if the amount of solvent is too large, the above-mentioned decomposition products of the solvent may have an effect, so a smaller amount tends to be preferable. The preferred upper limit is 4 to 5 times that of the raw material.
本発明において、酸化剤として用いられる酸素としては、通常分子状酸素あるいは分子状酸素含有ガスが使用されるが、空気を使用するのが経済的に有利である。
本発明において、工程（Ａ）において使用される酸素の量は、ｐ−キシレンからテレフタル酸を製造する全工程において反応に使用する酸素を１００％とした場合、好ましくは８０〜９０％である。このような酸素使用料の割合の範囲内であれば、色相に優れたテレフタル酸を得る上で有利であると考えられる。
上記の反応は、通常、液相で行われることが多い。反応が液相において行われるために、原料および溶媒を液相に保つよう通常加圧する場合もある。
反応圧力は、通常、１〜５０気圧の範囲が用いられる。
In the present invention, molecular oxygen or molecular oxygen-containing gas is usually used as the oxygen used as the oxidizing agent, but it is economically advantageous to use air.
In the present invention, the amount of oxygen used in the step (A) is preferably 80 to 90% when the oxygen used in the reaction is 100% in all the steps of producing terephthalic acid from p-xylene. If it is within the range of the ratio of the oxygen usage fee, it is considered to be advantageous in obtaining terephthalic acid having an excellent hue.
The above reaction is usually carried out in a liquid phase. Since the reaction takes place in the liquid phase, it may also be usually pressurized to keep the raw materials and solvent in the liquid phase.
The reaction pressure is usually in the range of 1 to 50 atm.
本発明における液相酸化反応は半連続あるいは連続で行われるが、原料の供給速度、空気供給速度、連続法の場合にはさらに反応液の反応槽中での滞留時間等の反応条件はｐ−キシレンからテレフタル酸を合成する場合の公知の技術範囲内とほぼ同様である。
工程（Ａ）に要する時間は、好ましくは０．６〜１．２時間である。好ましい下限値は０．７時間である。一方、好ましい０．９時間である。このような時間の範囲内であれば、色相に優れたテレフタル酸を得る上で有利である。
The liquid phase oxidation reaction in the present invention is carried out semi-continuously or continuously, but the reaction conditions such as the supply rate of the raw material, the air supply rate, and in the case of the continuous method, the residence time of the reaction solution in the reaction vessel are p-. It is almost the same as within the known technical range when synthesizing terephthalic acid from xylene.
The time required for the step (A) is preferably 0.6 to 1.2 hours. The preferred lower limit is 0.7 hours. On the other hand, it is preferably 0.9 hours. Within such a time range, it is advantageous to obtain terephthalic acid having an excellent hue.
本発明において、前記の工程（Ａ）以外の反応工程の条件は任意であり、公知の条件を制限なく適用することが出来る。 好ましくは、工程（Ａ）よりも反応温度が高い工程や、反応時間が長い工程でもよいし、反応温度が低く、反応時間が短い工程を含む方法であってもよい。本発明においては、前記の条件よりも穏やかな条件の工程を組み合わせることが好ましい。
前記の工程（Ａ）以外の液相酸化の反応温度の好ましい範囲は１５０〜１６０℃である。
In the present invention, the conditions of the reaction step other than the above step (A) are arbitrary, and known conditions can be applied without limitation. Preferably, a step having a higher reaction temperature than the step (A), a step having a long reaction time, or a method including a step having a low reaction temperature and a short reaction time may be used. In the present invention, it is preferable to combine steps under milder conditions than the above conditions.
The preferred range of the reaction temperature for liquid phase oxidation other than the step (A) is 150 to 160 ° C.
テレフタル酸は通常、さらに水添精製工程を経て高純度テレフタル酸とすることもできる。この水添工程には、活性炭に担持されたパラジウム触媒などの公知の方法を制限なく使用することが出来る。
この様な高純度テレフタル酸を本願発明の方法を適用して製造すると、色相に優れたテレフタル酸を得ることが出来る。本願において、色相は波長３４０ｎｍの紫外光線の透過率で評価することが出来る。
本発明の製造方法で得られるテレフタル酸は、前記の通り、色相に優れているので、ＰＥＴ樹脂やＰＢＴ樹脂とした場合、その製品となる飲料容器、繊維、離型フィルムなどの用途において、従来にはない特性を付与することが期待される。例えば、透明性や剛性、強度などに特徴を有する製品となることが期待される。
Terephthalic acid can usually be further subjected to a hydrogenation purification step to obtain high-purity terephthalic acid. In this hydrogenation step, a known method such as a palladium catalyst supported on activated carbon can be used without limitation.
When such high-purity terephthalic acid is produced by applying the method of the present invention, terephthalic acid having an excellent hue can be obtained. In the present application, the hue can be evaluated by the transmittance of ultraviolet rays having a wavelength of 340 nm.
As described above, the terephthalic acid obtained by the production method of the present invention has an excellent hue. Therefore, when it is used as a PET resin or PBT resin, it is conventionally used in applications such as beverage containers, fibers, and release films. It is expected to give characteristics that are not found in. For example, it is expected to be a product having characteristics such as transparency, rigidity, and strength.
実施例１
ｐ−キシレンとｐ−キシレンの質量に対してｐ−トルアルデヒド１５質量％（ｐ−キシレンとｐ−トルアルデヒドとｐ−トルイル酸の合計量を１００質量％とした場合、１２質量％）、ｐ−トルイル酸１０質量％（ｐ−キシレンとｐ−トルアルデヒドとｐ−トルイル酸の合計量を１００質量％とした場合、８質量％）を加え、これらの合計質量の４．８倍の質量の酢酸水（酢酸９６．３質量％）に溶解させる。液中にＣｏ ７７０質量ｐｐｍ、Ｍｎ ３８５質量ｐｐｍ、Ｂｒ １３９５質量ｐｐｍ相当の触媒を添加して、オートクレーブへ連続供給しながら空気を液中に吹き込みながら、内温１８８℃／１．２５ＭＰａにコントロールしながら反応させた。また原料の供給量は滞留時間が４５分となるように調整した。オートクレーブから生成したスラリーを回収、冷却後に固液（粗テレフタル酸と反応液残渣）を濾過分離して粗テレフタル酸を２Ｎ水酸化カリウム水溶液で溶解後に３４０ｎｍでの光線透過率を分析した結果４４％であった。
Example 1
15% by mass of p-toluic acid with respect to the mass of p-xylene and p-xylene (12% by mass when the total amount of p-xylene, p-toluic acid and p-toluic acid is 100% by mass), p -Add 10% by mass of toluic acid (8% by mass when the total amount of p-xylene, p-toluic acid and p-toluic acid is 100% by mass), and add 4.8 times the total mass of these. Dissolve in aqueous acetate (96.3% by mass). A catalyst equivalent to Co 770 mass ppm, Mn 385 mass ppm, and Br 1395 mass ppm was added to the liquid, and the internal temperature was controlled to 188 ° C / 1.25 MPa while continuously supplying air to the autoclave and blowing air into the liquid. I made it react. The amount of raw material supplied was adjusted so that the residence time was 45 minutes. The slurry generated from the autoclave was recovered, cooled, the solid solution (crude terephthalic acid and the reaction solution residue) was filtered and separated, the crude terephthalic acid was dissolved in a 2N potassium hydroxide aqueous solution, and the light transmittance at 340 nm was analyzed. Met.
比較例１
原料をすべてｐ−キシレンで同様の操作を実施した場合、３４０ｎｍでの光線透過率は１７％であった。
Comparative Example 1
When all the raw materials were subjected to the same operation with p-xylene, the light transmittance at 340 nm was 17%.
Claims (2)
ｉ）ｐ−トルアルデヒドの含有率が８〜１５質量％であり、且つ、ｐ−トルイル酸の含有率が５〜２０質量％である。
ｉｉ）ｐ−トルアルデヒドの含有率とｐ−トルイル酸の含有率の合計が１５〜３５質量％である（ｐ−トルアルデヒドの含有率とｐ−トルイル酸の含有率とｐ−キシレンの含有率との合計を１００質量％とする。）。
ｉｉｉ）反応温度が１２０〜２４０℃である。 A method for producing terephthalic acid, which comprises a step (A) of reacting p-toluic acid, p-toluic acid and p-xylene with oxygen under the conditions satisfying the following requirements in the presence of organic acid water. ..
i) The content of p-toluic acid is 8 to 15% by mass, and the content of p-toluic acid is 5 to 20% by mass.
ii) The total content of p-toluic acid and p-toluic acid is 15 to 35% by mass (p-toluic acid content, p-toluic acid content and p-xylene content). The total of and is 100% by mass.).
iii) The reaction temperature is 120 to 240 ° C.
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