JP4184948B2 - 精製テレフタル酸の製造方法 - Google Patents
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Description
(1)(i)ジアルキルベンゼン化合物、(ii)酸化触媒成分を溶解した水性酢酸反応媒体及び(iii)酸素含有ガスを第一加圧酸化ゾーンに供給し(第一加圧酸化反応器内の温度及び圧力は150〜180℃及び約3.5〜13バール(絶対)−bara(約50〜189ポンド/平方インチ−psia)に保持する)、前記ゾーン内でジアルキルベンゼン化合物を液相発熱酸化させ;
(2)第一反応器の上部から、蒸発した水性酢酸反応媒体を含む蒸気並びに二酸化炭素、メタン、不活性成分及び前記蒸気の非凝縮性成分の9容量%未満の酸素を含む酸素枯渇ガス(oxygen−depleted gas)を除去し;
(3)第一反応器の下部から、(i)固体及び溶解テレフタル酸並びに不完全酸化生成物と(ii)酸化触媒を溶解した水性酢酸反応媒体を含む酸化反応生成物(oxidizer product)を除去し;
(4)(i)(3)の酸化反応生成物及び(ii)酸素含有ガスを第二加圧酸化ゾーンに供給し(第二加圧酸化反応器内の温度及び圧力は185〜230℃及び約4.5〜18.3bara(約65〜265psia)に保持する)、前記ゾーン内で前記不完全酸化生成物を液相発熱酸化させ;
(5)第二反応器の上部から、蒸発した水性酢酸反応媒体を含む蒸気並びに二酸化炭素、不活性成分及び前記蒸気の非凝縮性成分の5容量%未満の酸素を含む酸素枯渇ガスを除去し;
(7)工程(6)の(ii)水性酢酸反応媒体からテレフタル酸を分離し、400〜900ppmwの総濃度で4−カルボキシベンズアルデヒド及びp−トルイル酸不純物を含むテレフタル酸を得;
(8)工程(7)において得られたテレフタル酸を、260〜320℃及び溶液を液相に保持するのに充分な圧力において水中に溶解させて、10〜35重量%の溶解テレフタル酸を含む溶液を形成し、そして前記溶液を水素添加触媒の存在下において水素と接触させて、水素添加生成物溶液を生成せしめ;
(9)工程(8)の溶液を、複数の直列接続晶出器を含む結晶化ゾーンに供給し、前記ゾーン内において前記溶液を、圧力及び温度の逐次低下による速度制御蒸発冷却に供して、テレフタル酸を結晶化させ(前記結晶化ゾーンの末端の溶液の圧力は周囲圧力又はそれ以下である);
(10)前記晶出器から蒸発した溶媒を凝縮させ、そして前記凝縮溶媒を前記結晶化ゾーンに、それが得られた晶出器の後の点で戻し;そして
(11)周囲圧力における固液分離によって、テレフタル酸の重量に基づき150ppmw未満のp−トルイル酸を含む固体結晶テレフタル酸を回収する
ことを含む工程による方法を提供する。
添付図1を参照するに、本発明の新規な方法の工程(1)は、反応器12を含む第一酸化ゾーン中で実施されることができる。p−キシレンのようなジアルキルベンゼン化合物、水性酢酸及び適当な酸化触媒を含む供給材料混合物は、導管10を経て第一酸化反応器12に供給する。酢酸反応媒体又は溶媒供給材料は一般的に15重量%以下の水を含む。所望ならば、触媒成分を含む酢酸溶媒及び/又はジアルキルベンゼン化合物は反応器12の側面に沿って複数の点で反応器12に供給されることができる。分子酸素含有ガスは、加圧状態で、円柱状反応器の底部又は底部付近において導管14を経て反応器12に連続供給する。酸素含有ガス、例えば酸素、酸素富化空気又は好ましくは空気は、通常、円柱状反応器の底部又は底部付近に供給する。反応器12への酸素含有ガスの流量は、導管16を経て反応器から出る排ガス中の酸素が2〜9容量%、好ましくは2〜5容量%(溶媒を含まない乾燥ベースで計算)に保たれるように制御する。反応器12中の反応体は、含有される揮発性反応媒体を反応温度において実質的に液体の状態に保持するのに充分な高圧に保持する。反応器12内の温度及び圧力は、150〜180℃及び約3.5〜13バール(絶対)(約50〜189psia)、好ましくは155〜165℃及び約5.2〜6.9バール(絶対)(約75〜100psia)である。
1.1個又はそれ以上の羽根車のような撹拌手段を装着した結晶化ユニット又は容器(晶出器);
2.前記晶出器への供給ライン;
3.前記晶出器からの生成物取り出しライン;
4.前記晶出器から、溶媒蒸気の一部又は全てが凝縮される凝縮器へ通じる溶媒留出物又は蒸気除去ライン;及び
5.凝縮器中で凝縮された液体を供給するための、結晶化ゾーンの下流の点又は部分への溶媒供給ライン。
1.晶出器段の温度を比較的高い、互いにずっと接近した温度に段階付けしながら、従来の技術と同様に、段毎にテレフタル酸を同じ回収率で得ることができる。この運転様式は、テレフタル酸のほとんどが溶液から結晶化する温度範囲内で水素添加後の流れの衝撃冷却を最小にすることができる。より純粋な粗製芳香族ジカルボン酸と共に従来の結晶化温度を使用することにより、従来の温度においてより多くの芳香族ジカルボン酸が溶液から結晶化する。
2.所定の滞留時間及び生産速度に関しては、上流のより高温でより高圧の晶出器の容積は公知の方法によって必要とされる容積よりもはるかに小さくすることができる。これは、最終生成物流中の同じ懸濁固形分を対象としながらも、溶液中のテレフタル酸の初期濃度がはるかに高いためである。晶出器の容積がより小さいため、かなりのコスト削減につながる。
3.溶媒の沸点未満の温度で母液から芳香族ジカルボン酸結晶を分離できるため、分離を行うための加圧型及び閉鎖型の濾過装置の必要がなくなる。このため、効率の良い分離を維持しながら、原価効率がより優れた固液分離装置を使用することができる。
この例は、p−トルイル酸濃度が429ppmwである粗製テレフタル酸を、精製テレフタル酸(150ppm)の純度許容限界未満に精製できることを示す。この例はまた、この基準値が、溶媒の沸点未満の温度においてテレフタル酸を単離することによって達成できることを示す。
最終生成物の純度に対する単離温度の影響を示すこの例においては、実施例1の実験1、2及び3から得られた室温のオートクレーブ充填材料の一部分を別々に、充分に混合される容器に入れた。実施例1に関して行った60℃への再加熱の代わりに、実施例2ではこの部分を95℃に再加熱し、同温度時1時間保持した。固液分離は95℃で行って、固形分のサンプルを得、これをp−トルイル酸濃度に関して分析した。この結果を表Iに示す。表Iからわかるように、より高い95℃の温度で単離すると、より低い60℃の温度で単離された材料よりもp−トルイル酸濃度が低い生成物が得られた。生成物の純度の増加は、固液分離温度を溶媒の沸点未満に維持しながら、単離温度を60℃から上げることよって達成できる。
高圧オートクレーブに、表IIの実験4及び5に示した量の水及び粗製テレフタル酸を装填した。これらのサンプルは粗製テレフタル酸の20%水溶液の近似溶液に相当する。粗製テレフタル酸固形分中のp−トルイル酸の濃度は429.37ppmwであった。サンプルを280℃に再加熱し、固形分の全てを確実に溶解させるために同温度に1時間保持した。サンプルを30℃/時の速度で室温まで冷却した。次いで、実施例1及び2の手法において行ったように、各サンプルの一部を60℃に加熱し且つ同温度で分離させ、また、各サンプルの一部を95℃に加熱し且つ同温度で分離させた。得られた固形分のp−トルイル酸濃度を表IIに示す。
Claims (8)
- テレフタル酸の重量に基づき150重量百万分率(ppmw)未満のp−トルイル酸を含む結晶テレフタル酸の製造及び回収方法であって、
(1)(i)ジアルキルベンゼン化合物、(ii)酸化触媒成分を溶解した水性酢酸反応媒体及び(iii)酸素含有ガスを第一加圧酸化反応器の第一加圧酸化ゾーンに供給し(第一加圧酸化反応器内の温度及び圧力は150〜180℃及び3.5〜13バール(絶対)(bara)(50〜189ポンド/平方インチ−psia)に保持する)、前記ゾーン内でジアルキルベンゼン化合物を液相発熱酸化させ;
(2)第一加圧酸化反応器の上部から、蒸発した水性酢酸反応媒体を含む蒸気並びに二酸化炭素、不活性成分及び前記蒸気の非凝縮性成分の9容量%未満の酸素を含む酸素枯渇ガスを除去し;
(3)第一加圧酸化反応器の下部から、(i)固体及び溶解テレフタル酸並びに不完全酸化生成物と(ii)酸化触媒を溶解した水性酢酸反応媒体を含む酸化反応生成物を除去し;
(4)(i)工程(3)の酸化反応生成物及び(ii)酸素含有ガスを第二加圧酸化反応器の第二加圧酸化ゾーンに供給し(第二加圧酸化反応器内の温度及び圧力は185〜230℃及び4.5〜18.3バール(絶対)(65〜265psia)に保持する)、前記ゾーン内で前記不完全酸化生成物を液相発熱酸化させ;
(5)第二加圧酸化反応器の上部から、蒸発した水性酢酸反応媒体を含む蒸気並びに二酸化炭素、不活性成分及び前記蒸気の非凝縮性成分の5容量%未満の酸素を含む酸素枯渇ガスを除去し;
(6)第二加圧酸化反応器の下部から、(i)固体及び溶解テレフタル酸及び(ii)酸化触媒を溶解した水性酢酸反応媒体を含む第2酸化反応生成物を除去し;
(7)工程(6)の(ii)水性酢酸反応媒体からテレフタル酸を分離して、900ppmw未満の4−カルボキシベンズアルデヒド及びp−トルイル酸を含むテレフタル酸を得;
(8)工程(7)において得られたテレフタル酸を、260〜320℃及び溶液を液相に保持する46.9〜113バールの圧力において水中に溶解させて、存在するテレフタル酸の重量に基づき900ppmw未満の4−カルボキシベンズアルデヒド及びp−トルイル酸を溶解した、10〜35重量%の溶解テレフタル酸を含む溶液を形成せしめ、そして前記溶液を水素添加触媒の存在下において水素と接触させて、水素添加生成物溶液を生成せしめ;
(9)工程(8)の溶液を、複数の直列接続晶出器を含む結晶化ゾーンに供給し、前記ゾーン内において、前記溶液を圧力及び温度の逐次低下による速度制御蒸発冷却に供して、テレフタル酸を結晶化させ(前記結晶化ゾーンの末端の溶液の圧力は周囲圧力又はそれ以下である);
(10)前記晶出器から蒸発した溶媒を凝縮させ、そしてその凝縮溶媒を前記結晶化ゾーンの、溶媒が蒸発した晶出器の後の点に戻し;そして
(11)周囲圧力における固液分離によって、テレフタル酸の重量に基づき150ppmw未満のp−トルイル酸を含む固体結晶テレフタル酸を回収する
ことを含む工程によって結晶テレフタル酸を製造及び回収する方法。 - 前記工程(1)〜(7)が、
(1)(i)p−キシレン、(ii)酸化触媒成分を溶解した水性酢酸反応媒体及び(iii)酸素含有ガスを第一加圧酸化ゾーンに供給し(第一加圧酸化反応器内の温度及び圧力は150〜180℃及び3.5〜13バール(絶対)(bara)に保持する)、前記ゾーン内でp−キシレン化合物を液相発熱酸化させ;
(2)第一加圧酸化反応器の上部から、蒸発した水性酢酸反応媒体を含む蒸気並びに二酸化炭素、不活性成分及び前記蒸気の非凝縮性成分の9容量%未満の酸素を含む酸素枯渇ガスを除去し;
(3)第一加圧酸化反応器の下部から、(i)固体及び溶解テレフタル酸並びに不完全酸化生成物と(ii)酸化触媒を溶解した水性酢酸反応媒体を含む酸化反応生成物を除去し;
(4)(i)工程(3)の酸化反応生成物及び(ii)酸素含有ガスを第二加圧酸化ゾーンに供給し(第二加圧酸化反応器内の温度及び圧力は185〜230℃及び4.5〜18.3バール(絶対)に保持する)、前記ゾーン内で前記不完全酸化生成物を液相発熱酸化させ;
(5)第二加圧酸化反応器の上部から、蒸発した水性酢酸反応媒体を含む蒸気並びに二酸化炭素、不活性成分及び前記蒸気の非凝縮性成分の0〜1容量%の酸素を含む酸素枯渇ガスを除去し;
(6)第二加圧酸化反応器の下部から、(i)固体及び溶解テレフタル酸及び(ii)酸化触媒を溶解した水性酢酸反応媒体を含む第二酸化反応生成物を除去し;そして
(7)工程(6)の(ii)水性酢酸反応媒体からテレフタル酸を分離して、900ppmw未満の4−カルボキシベンズアルデヒド及びp−トルイル酸を含むテレフタル酸を得る
ことを含む請求項1に記載の方法。 - 前工程(1)を155〜165℃及び5.2〜6.9バール(絶対)においてコバルト、マンガン及び臭素を含む酸化触媒成分を溶解した、水及び酢酸の重量に基づいて4〜6重量%の水を含む水性酢酸反応媒体の存在下に実施し;工程(4)の第二加圧酸化反応器を温度205〜215℃及び圧力13.4〜17.2バール(絶対)に保持し;且つ工程(7)のテレフタル酸が400〜900ppmwの4−カルボキシベンズアルデヒド及びp−トルイル酸を含む請求項2に記載の方法。
- Co:Mn:Brの原子比が5〜40:1.0:4〜40である請求項3に記載の方法。
- 工程(6)の第2酸化反応生成物をフラッシュ蒸発ゾーンに供給し、前記ゾーン内で第2酸化反応生成物の温度及び圧力をフラッシュ蒸発によって低下させる請求項1に記載の方法。
- 工程(6)の第2酸化反応生成物を、温度170〜190℃及び圧力2.4〜5.2バール(絶対)において運転される第一フラッシュ容器及び(ii)温度60〜100℃及び圧力0.3〜0.8バール(絶対)において運転される第二フラッシュ容器を含んでなるフラッシュ蒸発ゾーンに供給し、第2酸化反応生成物の温度及び圧力をフラッシュ蒸発によって低下させる請求項2に記載の方法。
- 工程(8)の溶液が溶解テレフタル酸を25〜35重量%含み;工程(8)の水素添加生成物溶液中に、存在するテレフタル酸の重量に基づき400〜900ppmwのp−トルイル酸が溶解されており;且つ前記の複数の直列接続晶出器が2〜8個の晶出器を含む請求項1に記載の方法。
- 第一晶出器の温度が200〜260℃の範囲であり、最後の晶出器の温度が80〜100℃であり、且つ前記の複数の直列接続晶出器が3〜6個の晶出器を含む請求項7に記載の方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US29561901P | 2001-06-04 | 2001-06-04 | |
US10/161,571 US7196215B2 (en) | 2001-06-04 | 2002-05-31 | Process for the production of purified terephthalic acid |
PCT/US2002/017498 WO2002098836A1 (en) | 2001-06-04 | 2002-06-04 | Process for the production of purified terephthalic acid |
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JP2004531573A JP2004531573A (ja) | 2004-10-14 |
JP2004531573A5 JP2004531573A5 (ja) | 2005-12-22 |
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US (1) | US7196215B2 (ja) |
EP (1) | EP1395543B1 (ja) |
JP (1) | JP4184948B2 (ja) |
KR (1) | KR100896382B1 (ja) |
CN (1) | CN1258512C (ja) |
AT (1) | ATE464281T1 (ja) |
BR (1) | BR0205510B1 (ja) |
CA (1) | CA2417691C (ja) |
DE (1) | DE60235979D1 (ja) |
MX (1) | MXPA03010973A (ja) |
RU (1) | RU2292332C2 (ja) |
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- 2002-06-04 MX MXPA03010973A patent/MXPA03010973A/es active IP Right Grant
- 2002-06-04 JP JP2003501827A patent/JP4184948B2/ja not_active Expired - Lifetime
- 2002-06-04 BR BRPI0205510-4B1A patent/BR0205510B1/pt active IP Right Grant
- 2002-06-04 EP EP02739637A patent/EP1395543B1/en not_active Expired - Lifetime
- 2002-06-04 WO PCT/US2002/017498 patent/WO2002098836A1/en active Application Filing
Also Published As
Publication number | Publication date |
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JP2004531573A (ja) | 2004-10-14 |
KR100896382B1 (ko) | 2009-05-08 |
US7196215B2 (en) | 2007-03-27 |
CA2417691C (en) | 2009-09-29 |
CA2417691A1 (en) | 2002-12-12 |
US20020193630A1 (en) | 2002-12-19 |
WO2002098836A1 (en) | 2002-12-12 |
RU2003137848A (ru) | 2005-04-20 |
MXPA03010973A (es) | 2004-02-27 |
EP1395543B1 (en) | 2010-04-14 |
KR20030020966A (ko) | 2003-03-10 |
BR0205510B1 (pt) | 2013-06-25 |
CN1258512C (zh) | 2006-06-07 |
EP1395543A1 (en) | 2004-03-10 |
BR0205510A (pt) | 2003-06-24 |
DE60235979D1 (de) | 2010-05-27 |
CN1512978A (zh) | 2004-07-14 |
RU2292332C2 (ru) | 2007-01-27 |
ATE464281T1 (de) | 2010-04-15 |
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