JPH01135741A - Production of adipic acid - Google Patents
Production of adipic acidInfo
- Publication number
- JPH01135741A JPH01135741A JP63136635A JP13663588A JPH01135741A JP H01135741 A JPH01135741 A JP H01135741A JP 63136635 A JP63136635 A JP 63136635A JP 13663588 A JP13663588 A JP 13663588A JP H01135741 A JPH01135741 A JP H01135741A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- reaction
- cyclohexanone
- cyclohexanol
- adipic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 title claims description 38
- 239000001361 adipic acid Substances 0.000 title claims description 19
- 235000011037 adipic acid Nutrition 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 48
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 36
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 19
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 150000002696 manganese Chemical class 0.000 claims abstract description 5
- 150000003681 vanadium Chemical class 0.000 claims abstract 2
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 150000001868 cobalt Chemical class 0.000 claims 1
- 150000001879 copper Chemical class 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 abstract description 8
- 239000010941 cobalt Substances 0.000 abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 239000010949 copper Substances 0.000 abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 4
- 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 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract 1
- 229910002651 NO3 Inorganic materials 0.000 abstract 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract 1
- 159000000021 acetate salts Chemical class 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- -1 aliphatic cyclic compounds Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004880 explosion Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- YYGXPJNJHYORNC-UHFFFAOYSA-N potassium manganese(2+) oxygen(2-) Chemical compound [K+].[O-2].[Mn+2] YYGXPJNJHYORNC-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/50—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
- C07C55/02—Dicarboxylic acids
- C07C55/14—Adipic acid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、脂肪族環式化合物からアジピン酸（Ａｄｌｐ
ｌｃ Ａｃ１ｄ ）を製造する方法、−層詳しくは、シ
クロヘキサノン又はシクロヘキサノール、又は、シクロ
ヘキサノンとシクロヘキサノール混合物を、触媒と酢酸
の溶媒存在下に硝酸により酸化させてアジピン酸を製造
する新しくて進歩した製造方法に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention is directed to the production of adipic acid (Adlp) from aliphatic cyclic compounds.
lc Ac1d), in particular a new and advanced production process in which cyclohexanone or cyclohexanol, or a mixture of cyclohexanone and cyclohexanol, is oxidized with nitric acid in the presence of a catalyst and acetic acid solvent to produce adipic acid. It is about the method.
アジピン酸は、製造工程に応じて脂肪族環式化合物を硝
酸により酸化するか、空気又は酸素により酸化させて製
造されている。例えば、米国特許第３９９７６０１号に
よれば、シクロヘキサノン、シクロヘキサノール又はシ
クロヘキサノンとシクロヘキサノール混合物をバナジウ
ム、銅、コバルト、マンガン塩等の触媒存在下に硝酸酸
化させてアジピン酸を製造している。しかし、この方法
は比較的収率（９２〜９４％）が高く副産物の分離が容
易である長所を有しているが、作業条件がややこしく特
に温度調節に失敗する場合には、爆発する危険がある。Adipic acid is produced by oxidizing an aliphatic cyclic compound with nitric acid or with air or oxygen depending on the production process. For example, according to US Pat. No. 3,997,601, adipic acid is produced by oxidizing cyclohexanone, cyclohexanol, or a mixture of cyclohexanone and cyclohexanol with nitric acid in the presence of a catalyst such as a vanadium, copper, cobalt, or manganese salt. However, although this method has the advantage of relatively high yield (92-94%) and easy separation of by-products, the working conditions are complicated and there is a risk of explosion, especially if temperature control is not achieved. be.
一方、日本国特公昭４６−２６４７号公報によれば、上
記脂肪族環式化合物を銅、コバルト、マンガン塩等の触
媒と酢酸溶媒存在下に空気又は酸素により酸化させてア
ジピン酸を製造している。On the other hand, according to Japanese Patent Publication No. 46-2647, adipic acid is produced by oxidizing the above aliphatic cyclic compound with air or oxygen in the presence of a catalyst such as a copper, cobalt, or manganese salt and an acetic acid solvent. There is.
この方法は、紙庫な酸化剤を使用するのが長所であるが
、副産物が多量生成されて、これらを分離精製するため
には、追加装置と共にその分離過程がややこしくなる欠
点があると推定される。The advantage of this method is that it uses a paper-based oxidizing agent, but it is thought to have the disadvantage that a large amount of by-products are produced, and the separation process is complicated by the need for additional equipment to separate and purify them. Ru.
又、これらの外に、実験室的方法（ＯｒｇａｎｌｅＥｘ
ｐｅｒｌａｅｎＬｓ、 Ｄ、Ｃ，１ｌｅａＬｈ ＆ Ｃ
ｏ、 Ｂｏｓｔｏｎ、 １９６４）として、シクロヘキ
サノンをアルカリ溶媒下に酸化マンガンカリウムにより
酸化させてアジピン酸を製造する方法も知られている。In addition to these, laboratory methods (OrganleEx
perlaenLs, D, C, 1leaLh & C
There is also known a method for producing adipic acid by oxidizing cyclohexanone with potassium manganese oxide in an alkaline solvent as described by E. O., Boston, 1964).
〔発明の目的及び構成〕
本発明は公知のアジピン酸の製造方法が有している上述
のような欠点を改善して副産物が少く高収率のアジピン
酸を容易に製造しうる方法を提供することを目的とする
ものであって本発明者等が不断に研究を続けた結果、期
待以上のアジピン酸の製造方法を得るようになった。す
なわち、本発明の技術的特徴は、公知の脂肪族環式化合
物を出発物質にバナジウム、銅、コバルト、マンガン等
の塩形態の触媒と、酢酸溶媒存在下に硝酸酸化させてア
ジピン酸を製造する新しい製造方法である。[Objective and Structure of the Invention] The present invention provides a method for easily producing adipic acid with few by-products and high yield by improving the above-mentioned drawbacks of known methods for producing adipic acid. As a result of continuous research by the present inventors, we have obtained a method for producing adipic acid that exceeds expectations. That is, the technical feature of the present invention is to produce adipic acid by oxidizing a known aliphatic cyclic compound as a starting material with a catalyst in the form of a salt such as vanadium, copper, cobalt, or manganese with nitric acid in the presence of an acetic acid solvent. This is a new manufacturing method.
本発明の製造方法を一層詳しく説明すれば、原料として
使用するシクロヘキサノン、シクロヘキサノールは如何
なる製法により得られた物でも構わないが、工業的には
シクロヘキサノンを液状空気酸化して得た酸化生成物又
は、これから蒸溜分離して得たシクロヘキサノン、シク
ロヘキサノール又はこれらの混合物を例として挙げるこ
とができる。本発明で酸化剤として使用する硝酸も又如
何なる製法により得られたものでも構わないが、工業的
にはアンモニアを空気酸化して得た酸化生成物と水を向
流接触させて得た硝酸又は、これを硝酸と向流接触させ
て得る濃い硝酸等を例として挙げることができる。To explain the production method of the present invention in more detail, cyclohexanone and cyclohexanol used as raw materials may be obtained by any production method, but industrially, cyclohexanone or cyclohexanol obtained by oxidizing cyclohexanone in liquid air or Examples include cyclohexanone, cyclohexanol, and mixtures thereof obtained by distillation. The nitric acid used as an oxidizing agent in the present invention may be obtained by any manufacturing method, but industrially, nitric acid obtained by countercurrently contacting water with the oxidation product obtained by air oxidation of ammonia or , and concentrated nitric acid obtained by bringing this into countercurrent contact with nitric acid.
本発明の溶媒として使用する酢酸は、原料油１部に対し
て０．１部乃至１００部を添加するか又は硝酸１部に対
して０．０５部乃至５０部を添加するのが望ましい。Acetic acid used as a solvent in the present invention is desirably added in an amount of 0.1 to 100 parts per part of raw oil or 0.05 to 50 parts per part of nitric acid.
本発明で触媒として使用するバナジウム、銅、コバルト
、マンガン等は水溶性塩の形態、具体的にはアンモニウ
ム塩、硝酸塩、酢酸塩を使用することができる。本発明
のシクロヘキサノン、シクロヘキサノール又はこれら混
合物の酸化反応は通常、液状で行い、硝酸は上記原料油
１部に対して２．５部以上、望ましくは３部から１００
部程度を使用する。゛触媒はバナジウム塩の場合、原料
油１部に対して０．００５部から０．０５部、望ましく
はｏ、ｏｏｓ部から０．０３部、銅塩の場合、原料油１
部に対して０．００２部から０．１部、望ましくは０．
００５部から０１０５部、そして、コバルトとマンガン
塩の場合、原料油１部に対して０．００１部から０６０
５部まで、望ましくは、０．００３部から０．０３部程
度を使用する。又、本発明の酢酸溶媒は原料油１部に対
して０．１部乃至１００部、望ましくは０．１部乃至２
５部程度を使用する。酢酸の使用量が少い場合には反応
中湿度調節が難しく、酢酸の使用量が過多な場合には収
率が低下する。Vanadium, copper, cobalt, manganese, etc. used as catalysts in the present invention can be used in the form of water-soluble salts, specifically ammonium salts, nitrates, and acetates. The oxidation reaction of cyclohexanone, cyclohexanol or a mixture thereof in the present invention is usually carried out in liquid form, and nitric acid is added in an amount of 2.5 parts or more, preferably 3 to 100 parts, per 1 part of the above raw material oil.
Use degree.゛If the catalyst is a vanadium salt, 0.005 part to 0.05 part, preferably 0.03 part to 0.03 part, based on 1 part of the raw material oil, if the catalyst is a copper salt, 1 part of the raw material oil.
part to 0.002 part to 0.1 part, preferably 0.002 part to 0.1 part.
0.005 parts to 0.105 parts, and in the case of cobalt and manganese salts, 0.001 parts to 0.60 parts per part of feedstock oil.
Up to 5 parts are used, preferably about 0.003 parts to 0.03 parts. Further, the acetic acid solvent of the present invention is used in an amount of 0.1 part to 100 parts, preferably 0.1 part to 2 parts, per 1 part of raw oil.
Use about 5 parts. When a small amount of acetic acid is used, it is difficult to control the humidity during the reaction, and when an excessive amount of acetic acid is used, the yield decreases.
本発明の原料油酸化反応は通常４５℃〜９０℃で行い望
ましくは５０℃〜８０℃で行うのが良い。The raw material oil oxidation reaction of the present invention is usually carried out at 45°C to 90°C, preferably at 50°C to 80°C.
反応温度が余り低いと反応が進行されない状態で、突然
、−挙に反応するようになるので爆発の危険があり、余
り高いと収率が低下される。又、反応圧力は常圧で５気
圧迄適用し得るが、圧力が高いと収率が低下される。If the reaction temperature is too low, the reaction will suddenly start to occur without proceeding, and there is a danger of explosion; if the reaction temperature is too high, the yield will be reduced. Further, the reaction pressure can be applied at normal pressure up to 5 atm, but if the pressure is high, the yield will be reduced.
本発明の製造方法によるときは既存の硝酸酸化法に比べ
てアジピン酸の収率が約２％以上増加する一方、酸化反
応中の温度調節を容易にして爆発の危険をなくすことが
できる。When using the production method of the present invention, the yield of adipic acid is increased by about 2% or more compared to the existing nitric acid oxidation method, and the temperature during the oxidation reaction can be easily controlled to eliminate the risk of explosion.
従って本発明によれば副産物が少い高収率のアジピン酸
を容易に製造することが出来るので工業的に極めて有利
である。Therefore, according to the present invention, it is possible to easily produce adipic acid in high yield with few by-products, which is extremely advantageous industrially.
以下、実施例により本発明の詳細な説明する。 Hereinafter, the present invention will be explained in detail with reference to Examples.
本発明は特許請求の範囲をはずれない限り以下の実施例
に限定することなく多様に変更して使用し得るのである
。The present invention is not limited to the following embodiments and can be modified and used in various ways without departing from the scope of the claims.
実施例１
硝酸１部に対して、酢酸０．０５部を入れた反応器にバ
ナジウムのアンモニウム塩０．００２部、銅の硝酸塩０
．０５部、そしてコバルトとマンガンの酢酸塩を各々０
．００１部溶解させる。この溶液にシクロヘキサノン／
シクロヘキサノール混合物（２４ｇ／２５ｇ）０．３部
を添加し、５０℃〜８０℃で酸化反応させる。３０分後
、反応が完結すると、反応物をガスクロマトグラフィで
分析してアジピン酸の収率を測定した。Example 1 To 1 part of nitric acid, 0.002 part of ammonium salt of vanadium and 0 part of copper nitrate were added to a reactor containing 0.05 part of acetic acid.
．． 05 parts, and 0 each of cobalt and manganese acetate.
．． 001 parts dissolved. Add cyclohexanone/
Add 0.3 part of a cyclohexanol mixture (24g/25g) and carry out an oxidation reaction at 50°C to 80°C. After 30 minutes, when the reaction was completed, the reaction product was analyzed by gas chromatography to determine the yield of adipic acid.
収率：９３．６％
実１！ｌｉ例２
実施例１と同様であるが、硝酸１部に対して酢酸１０部
を入れて酸化反応させた。Yield: 93.6% Fruit 1! Example 2 The same procedure as in Example 1 was carried out, except that 10 parts of acetic acid was added to 1 part of nitric acid to cause an oxidation reaction.
収率：９５．３％
実施例３
実施例１と同様であるが硝酸１部に対して酢酸５０部を
入れ、酸化反応させた。Yield: 95.3% Example 3 Same as Example 1, but 50 parts of acetic acid was added to 1 part of nitric acid to cause an oxidation reaction.
収率：９３．７％
実施例４
実施例２と同様であるが、シクロヘキサノン／シクロヘ
キサノールを５ ｇ ／ ４５ ｇの比率に入れて、酸
化反応させた。Yield: 93.7% Example 4 The same as Example 2, but cyclohexanone/cyclohexanol were added in a ratio of 5 g/45 g and an oxidation reaction was carried out.
収率：９２．１％
実施例５
実施例２と同様であるが、シクロヘキサノン／シクロヘ
キサノールを４５ ｇ ／ ５ ｇの比率に入れて、酸
化反応させた。Yield: 92.1% Example 5 The same as Example 2, but cyclohexanone/cyclohexanol were added in a ratio of 45 g/5 g and an oxidation reaction was carried out.
収率：９６．８％
比較例１
実施例１，２．３と同一であるが酢酸は除外し、硝酸１
部に水０，０５部を入れて酸化反応させた。Yield: 96.8% Comparative Example 1 Same as Examples 1 and 2.3, but acetic acid was excluded, and nitric acid 1
0.05 parts of water was added to the solution to carry out an oxidation reaction.
収率：９０．５％
比較例２
比較例１と同一であるが硝酸１部に対し、水１０部を入
れて酸化反応させた。Yield: 90.5% Comparative Example 2 The same as Comparative Example 1, except that 10 parts of water was added to 1 part of nitric acid to cause an oxidation reaction.
収率：８９．８％
比較ｆ１７３
比較例１．２と同一であるが硝酸１部に対し、水５０部
を入れて酸化反応させた。Yield: 89.8% Comparison f173 Same as Comparative Example 1.2, but oxidation reaction was carried out by adding 50 parts of water to 1 part of nitric acid.
収率：８８．６％ 出願人代理人 佐 藤 −雄Yield: 88.6% Applicant's representative: Mr. Sato
Claims (1)
シクロヘキサノンとシクロヘキサノール混合物に、酢酸
溶媒と触媒存在下に硝酸酸化させることを特徴とするア
ジピン酸の製造方法。 ２、酢酸を原料１部に対して０．１部乃至 １００部を添加して反応させることを特徴とする請求項
１記載のアジピン酸の製造方法。 ３、触媒として、バナジウム塩の場合、原料１部に対し
て０．００５部乃至０．０５部を、コバルト塩またはマ
ンガン塩は０．００１部乃至０．０５部を、そして、銅
塩は０．００２部乃至０．１部を添加して反応させるこ
とを特徴とする請求項１記載のアジピン酸の製造方法。 ４、４５℃〜９０℃の反応温度で反応させることを特徴
とする請求項１記載のアジピン酸の製造方法。 ５、１気圧乃至３気圧の反応圧力で反応させることを特
徴とする請求項１記載のアジピン酸の製造方法。[Claims] 1. A method for producing adipic acid, which comprises oxidizing cyclohexanone or cyclohexanol alone or a mixture of cyclohexanone and cyclohexanol with nitric acid in the presence of an acetic acid solvent and a catalyst. 2. The method for producing adipic acid according to claim 1, characterized in that the reaction is carried out by adding 0.1 part to 100 parts of acetic acid to 1 part of the raw material. 3. As a catalyst, in the case of vanadium salt, 0.005 part to 0.05 part per 1 part of raw material, cobalt salt or manganese salt, 0.001 part to 0.05 part, and copper salt, 0. 2. The method for producing adipic acid according to claim 1, wherein the reaction is carried out by adding 0.002 parts to 0.1 parts. 4. The method for producing adipic acid according to claim 1, wherein the reaction is carried out at a reaction temperature of 45°C to 90°C. 5. The method for producing adipic acid according to claim 1, wherein the reaction is carried out at a reaction pressure of 1 atm to 3 atm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019870012932A KR910002280B1 (en) | 1987-11-17 | 1987-11-17 | Preparation of Adipic Acid |
| KR12932/1987 | 1987-11-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01135741A true JPH01135741A (en) | 1989-05-29 |
| JP2581759B2 JP2581759B2 (en) | 1997-02-12 |
Family
ID=19266076
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63136635A Expired - Lifetime JP2581759B2 (en) | 1987-11-17 | 1988-06-02 | Method for producing adipic acid |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2581759B2 (en) |
| KR (1) | KR910002280B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1325901A1 (en) * | 2002-01-04 | 2003-07-09 | Council of Scientific and Industrial Research | An improved process for the preparation of adipic acid |
| JP2012510491A (en) * | 2008-12-01 | 2012-05-10 | ロディア オペレーションズ | Method for producing adipic acid |
| CN108084012A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method that peroxyester prepares adipic acid |
-
1987
- 1987-11-17 KR KR1019870012932A patent/KR910002280B1/en not_active IP Right Cessation
-
1988
- 1988-06-02 JP JP63136635A patent/JP2581759B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1325901A1 (en) * | 2002-01-04 | 2003-07-09 | Council of Scientific and Industrial Research | An improved process for the preparation of adipic acid |
| JP2012510491A (en) * | 2008-12-01 | 2012-05-10 | ロディア オペレーションズ | Method for producing adipic acid |
| CN108084012A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method that peroxyester prepares adipic acid |
| CN108084012B (en) * | 2016-11-22 | 2019-12-31 | 中国科学院大连化学物理研究所 | A kind of method that oxidizes cyclohexanone to prepare adipic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| KR890008066A (en) | 1989-07-08 |
| JP2581759B2 (en) | 1997-02-12 |
| KR910002280B1 (en) | 1991-04-11 |
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