JP5414784B2 - 粗テレフタル酸製造のための酸化反応器 - Google Patents
粗テレフタル酸製造のための酸化反応器 Download PDFInfo
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- JP5414784B2 JP5414784B2 JP2011504915A JP2011504915A JP5414784B2 JP 5414784 B2 JP5414784 B2 JP 5414784B2 JP 2011504915 A JP2011504915 A JP 2011504915A JP 2011504915 A JP2011504915 A JP 2011504915A JP 5414784 B2 JP5414784 B2 JP 5414784B2
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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 description 90
- 238000007254 oxidation reaction Methods 0.000 title claims description 34
- 230000003647 oxidation Effects 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- 239000000376 reactant Substances 0.000 claims description 99
- 239000007788 liquid Substances 0.000 claims description 52
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 50
- 238000010992 reflux Methods 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 78
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 36
- 239000007789 gas Substances 0.000 description 33
- 239000002002 slurry Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 239000013067 intermediate product Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000000061 acid fraction Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
- B01F23/20—Mixing gases with liquids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
パラキシレン+酸素→テレフタル酸
上記の主反応が起きなければならないが、溶媒として用いられる酢酸が酸化して、
酢酸+酸素→酢酸メチル、または
酢酸+酸素→二酸化炭素+水
のような副反応が起きることによって酢酸が損失されるようになる。このような酢酸の酸化形状の原因は、反応器内の構造と低い攪拌効果および酢酸の酸化条件がパラキシレンの酸化条件とほぼ同じ競争反応(competitive reaction)であるため知られている。したがって、空気と酢酸が接触する機会を制限する方法が酢酸の酸化を防ぐ最も良い方法として知られている。
図1に示す既存の反応器を用いて図5Aに概略的に示すように、液体反応物供給パイプ導入部および液体反応物供給パイプの終端は反応器の上部の上部インペラの付近に設け、気体反応物供給パイプ導入部および気体反応物供給パイプの終端は反応器の下部に設け、生成物排出パイプは下部に設けた。
上下インペラ間の間隔を2000mmとし、インペラの直径と上下インペラ間の間隔の比を0.95としたことを除いては実施例1と同じ条件で実施した。
実施例1および比較例1において、反応器内に残っている中間生成物の4−カルボキシベンズアルデヒド(4CBA)の方率を測定して図5に示した。
スラリー全体の生成物である粗テレフタル酸の方率を測定した。粗テレフタル酸の濃度は反応器の上部に上昇しながら高くなった。これは粗テレフタル酸の生成反応が下部インペラ領域から始まって上部インペラ領域で終了するものと説明できる。本願発明では、反応器の上部で一定のスラリー濃度を維持させ、スラリーノズルに粗テレフタル酸スラリーを次のステップ工程へ搬送する。
前記実施例2および比較例1、2において、反応物であるパラキシレンの質量の方率を測定した。図6に示すように、実施例1の上部において液体反応物のパラキシレンの濃度が極めて低く、比較例1と比較してみるときに実施例1の上部は液体反応物のパラキシレンがほとんどないことが分かる。
実施例1および比較例1、2において酢酸の酸化現象を測定した。図7に示すように、実施例1では酢酸の酸化が著しく減少することが観察され、これは本願発明において液体反応物供給パイプの終端断面の中心の高さを気体反応物供給部の終端断面の中心の高さと同一にし、還流パイプの高さの調整によるものである。
実施例1および比較例1、2において、パラキシレン100トンを用いた場合、生成される粗テレフタル酸の生成量(kg)を比較し、その結果を表1に表した。
Claims (8)
- テレフタル酸製造のためのパラキシレン酸化反応器であって、
前記反応器の中心に位置するシャフトと、
複数のブレイドを有し、前記シャフト上に回転自在に設けられた上部インペラと、
複数のブレイドを有し、前記シャフト上に回転自在に設けられ、前記上部インペラおよび前記反応器の底の間に位置する下部インペラと、
前記反応器に液体反応物を供給する液体反応物供給パイプと、
前記反応器に気体反応物を供給する気体反応物供給パイプと、
前記反応器内に形成された生成物を外部に排出させる生成物排出パイプとを含む反応器において、
前記液体反応物供給パイプの終端の断面の中心と前記気体反応物供給パイプの終端の断
面の中心が、反応器の下部から同じ高さに位置し、かつ、前記下部インペラの前記複数のブレイドの上下範囲内に形成される集中攪拌領域に位置し、
前記反応器内における前記気体反応物供給パイプの終端の延長線と前記液体反応物供給パイプの終端の延長線とが、それぞれ前記下部インペラの直径(D)によって形成される円に接するように形成されることを特徴とする反応器。 - 前記上部インペラおよび下部インペラ間の高さの差と前記インペラの直径との比が1.0〜1.5であることを特徴とする請求項1に記載の反応器。
- 前記インペラの直径と前記反応器の直径の比が0.4〜0.5であることを特徴とする請求項1に記載の反応器。
- 前記反応器の底から前記下部インペラまでの高さと前記下部インペラの直径の比が0.5以上であることを特徴とする請求項1に記載の反応器。
- 前記反応器の底から前記生成物排出パイプの高さと、前記上部インペラおよび下部インペラ間の高さとの差の比が1.2〜1.5であることを特徴とする請求項1に記載の反応器。
- 前記反応器は、反応器内に還流を導入する還流パイプをさらに含むことを特徴とする請求項1に記載の反応器。
- 前記還流パイプの終端断面の中心の高さは、前記液体反応物供給パイプの終端断面の中心の高さと同じであることを特徴とする請求項6に記載の反応器。
- 前記反応器内における前記還流パイプの終端は、前記還流パイプの終端の延長線が前記下部インペラの直径(D)によって形成される円に接するように形成されることを特徴とする請求項7に記載の反応器。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2008-0035247 | 2008-04-16 | ||
KR1020080035247A KR100988684B1 (ko) | 2008-04-16 | 2008-04-16 | 조테레프탈산 제조를 위한 산화 반응기 |
PCT/KR2009/001391 WO2009128608A2 (en) | 2008-04-16 | 2009-03-19 | Oxidation reactor for manufacturing of crude terephthalic acid |
Publications (2)
Publication Number | Publication Date |
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JP2011516605A JP2011516605A (ja) | 2011-05-26 |
JP5414784B2 true JP5414784B2 (ja) | 2014-02-12 |
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JP2011504915A Active JP5414784B2 (ja) | 2008-04-16 | 2009-03-19 | 粗テレフタル酸製造のための酸化反応器 |
Country Status (6)
Country | Link |
---|---|
US (1) | US20110033347A1 (ja) |
JP (1) | JP5414784B2 (ja) |
KR (1) | KR100988684B1 (ja) |
CN (1) | CN101990531A (ja) |
TW (1) | TWI405752B (ja) |
WO (1) | WO2009128608A2 (ja) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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JP6848507B2 (ja) * | 2017-02-17 | 2021-03-24 | 住友金属鉱山株式会社 | 加圧反応装置、及びそれを用いた有価金属の浸出処理方法 |
CN107096410A (zh) * | 2017-05-28 | 2017-08-29 | 南京科技职业学院 | 一种可燃气体与氧气混合器 |
KR102256402B1 (ko) * | 2018-10-15 | 2021-05-25 | 한화솔루션 주식회사 | 회분식 반응기 |
CN110354771A (zh) * | 2019-07-24 | 2019-10-22 | 沧州冀春新材料有限公司 | 一种应用于乳液加工的底部进料工艺 |
JP7447471B2 (ja) * | 2019-12-19 | 2024-03-12 | 住友金属鉱山株式会社 | 攪拌装置 |
CN113634197A (zh) * | 2021-08-09 | 2021-11-12 | 嘉兴石化有限公司 | 一种用于pta氧化反应器进料分布的设备 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS4920192B1 (ja) * | 1970-09-07 | 1974-05-23 | ||
JPS5912095B2 (ja) * | 1976-02-24 | 1984-03-21 | 松山石油化学株式会社 | 高純度芳香族ジカルボン酸製造用反応装置 |
JPS52111532A (en) * | 1976-03-11 | 1977-09-19 | Kuraray Yuka Kk | Production of high-purity terephthalic acid |
JPS54109939A (en) * | 1978-02-15 | 1979-08-29 | Mitsui Petrochem Ind Ltd | Oxidation reactor for preparing aromatic carboxylic acid |
JPS5852243A (ja) * | 1981-09-24 | 1983-03-28 | Mitsubishi Gas Chem Co Inc | テレフタル酸の製造法 |
JPS6036439A (ja) * | 1983-08-09 | 1985-02-25 | Mitsubishi Chem Ind Ltd | テレフタル酸の製法 |
JP3232774B2 (ja) * | 1993-05-13 | 2001-11-26 | 三菱化学株式会社 | 高純度のテレフタル酸の製造方法 |
DE69522365T2 (de) * | 1994-05-11 | 2002-05-23 | Praxair Technology Inc | Verbesserungen bei der Oxidation organischer Chemikalien |
KR100374785B1 (ko) * | 2000-06-29 | 2003-03-04 | 학교법인 포항공과대학교 | 액상 산화 반응기 |
JP2004255291A (ja) * | 2003-02-26 | 2004-09-16 | Toray Ind Inc | 攪拌装置 |
US7153480B2 (en) * | 2003-05-22 | 2006-12-26 | David Robert Bickham | Apparatus for and method of producing aromatic carboxylic acids |
US7348452B2 (en) * | 2004-04-22 | 2008-03-25 | Eastman Chemical Company | Liquid phase oxidation of P-xylene to terephthalic acid in the presence of a catalyst system containing nickel, manganese, and bromine atoms |
US7608732B2 (en) * | 2005-03-08 | 2009-10-27 | Eastman Chemical Company | Optimized liquid-phase oxidation |
CN100999458B (zh) * | 2007-01-05 | 2010-08-25 | 中国石化扬子石油化工有限公司 | 生产对苯二甲酸的氧化反应器 |
-
2008
- 2008-04-16 KR KR1020080035247A patent/KR100988684B1/ko active IP Right Grant
-
2009
- 2009-03-18 TW TW098108720A patent/TWI405752B/zh active
- 2009-03-19 WO PCT/KR2009/001391 patent/WO2009128608A2/en active Application Filing
- 2009-03-19 JP JP2011504915A patent/JP5414784B2/ja active Active
- 2009-03-19 US US12/937,550 patent/US20110033347A1/en not_active Abandoned
- 2009-03-19 CN CN2009801225156A patent/CN101990531A/zh active Pending
Also Published As
Publication number | Publication date |
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TWI405752B (zh) | 2013-08-21 |
KR20090109828A (ko) | 2009-10-21 |
KR100988684B1 (ko) | 2010-10-18 |
JP2011516605A (ja) | 2011-05-26 |
TW200948776A (en) | 2009-12-01 |
WO2009128608A2 (en) | 2009-10-22 |
WO2009128608A3 (en) | 2010-11-11 |
US20110033347A1 (en) | 2011-02-10 |
CN101990531A (zh) | 2011-03-23 |
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