JPH10330357A - Production of peracid - Google Patents
Production of peracidInfo
- Publication number
- JPH10330357A JPH10330357A JP15571997A JP15571997A JPH10330357A JP H10330357 A JPH10330357 A JP H10330357A JP 15571997 A JP15571997 A JP 15571997A JP 15571997 A JP15571997 A JP 15571997A JP H10330357 A JPH10330357 A JP H10330357A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- peracid
- hydrogen peroxide
- ester
- ester compound
- 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.)
- Pending
Links
- 150000004965 peroxy acids Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 51
- -1 lactone compounds Chemical class 0.000 claims abstract description 35
- 239000003377 acid catalyst Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 14
- 150000001875 compounds Chemical group 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical group OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 125000000217 alkyl group Chemical group 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 244000309464 bull Species 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
- C07C409/26—Peracetic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C407/00—Preparation of peroxy compounds
- C07C407/003—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C409/00—Peroxy compounds
- C07C409/24—Peroxy compounds the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、エステル化合物を
酸化して過酸を製造する方法に関する。本発明の製造方
法により得られる過酸は、エポキシ体、キノン体、ラク
トン体などの製造において酸化剤として用いられる有用
な化合物である。TECHNICAL FIELD The present invention relates to a method for producing a peracid by oxidizing an ester compound. The peracid obtained by the production method of the present invention is a useful compound used as an oxidizing agent in producing an epoxy compound, a quinone compound, a lactone compound and the like.
【０００２】従来より、過酸、特に過酢酸を製造する方
法は種々知られている。例えば、過酸の製法としては、
酸触媒存在下にカルボン酸と過酸化水素を反応させる方
法（J.Am.Chem.Soc.,77卷,4037頁(1955年)；J.Org.Che
m.,27卷,1336頁(1962年);特開昭５３−１１９８１３号
公報など）、過酸化水素とカルボン酸無水物または塩化
物を反応させる方法（Bull.Soc.Chim.France,1959年,14
01頁）、過酸化ジアロイルとナトリウムメトキシドを反
応させる方法（Org.Synth.,Coll.１卷,431頁(1946
年)）、アルデヒドの自動酸化による方法（J.Am.Chem.S
oc.,79卷,5982頁(1957年);J.Org.Chem.,23卷,1923頁(19
58年);Chem,&Ind.,62卷,1962卷など）などがあげられ
る。Conventionally, various methods for producing peracids, particularly peracetic acid, have been known. For example, as a method for producing peracid,
Method of reacting carboxylic acid and hydrogen peroxide in the presence of acid catalyst (J. Am. Chem. Soc., 77th ed., 4037 (1955); J.Org.Che.
m., 27, 1336 (1962); JP-A-53-119813, etc.), a method of reacting hydrogen peroxide with a carboxylic acid anhydride or chloride (Bull.Soc.Chim.France, 1959). ,14
01), a method of reacting diaroyl peroxide with sodium methoxide (Org.Synth., Coll. 1), 431 (1946).
)), Method by autoxidation of aldehyde (J. Am. Chem. S.
oc., 79, p. 5982 (1957); J. Org. Chem., 23, p. 1923 (19).
58); Chem, & Ind., 62, 1962, etc.).
【０００３】これらの方法のなかでも、製造上の容易さ
および経済的観点より、現在では、酸触媒存在下にカル
ボン酸と過酸化水素を反応させる方法が現実的な過酸の
製造方法とされている。しかし、かかる方法は、カルボ
ン酸を溶解する溶媒の選択が難しいという問題があっ
た。そこで、その改良方法として、カルボン酸自体を溶
媒を兼ねる目的で大量に用いる方法が報告されている
（Chem.Pharm.Bull.,34卷(2),445頁(1986年)）。しか
し、この改良方法では、カルボン酸を大量に用いている
ため、製造装置の腐食が促進される不利や、生成系より
過酸を分離する際のカルボン酸と過酸との分離が困難で
あるなどの不利がある。Among these methods, the method of reacting a carboxylic acid with hydrogen peroxide in the presence of an acid catalyst is currently regarded as a realistic peracid manufacturing method from the viewpoint of easiness in production and economic efficiency. ing. However, such a method has a problem that it is difficult to select a solvent in which the carboxylic acid is dissolved. Therefore, as an improved method, a method of using a large amount of carboxylic acid itself for the purpose of also serving as a solvent has been reported (Chem.Pharm.Bull., 34 (2), 445 (1986)). However, in this improved method, since a large amount of carboxylic acid is used, there is a disadvantage that the corrosion of the production apparatus is accelerated, and it is difficult to separate the carboxylic acid and the peracid when separating the peracid from the production system. There are disadvantages such as.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、製造装置の
腐食等の問題が少なく、しかも生成系内から過酸を容易
に分離することができる過酸の容易な製造方法を提供す
ることを目的とする。SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a peracid which has few problems such as corrosion of the production equipment and which can easily separate the peracid from the production system. Aim.
【０００５】[0005]
【課題を解決するための手段】本発明者は、前記従来技
術の課題を解決すべく鋭意研究を重ねた。その結果、酸
触媒存在下で、エステル化合物と過酸化水素を混合した
場合には、エステル化合物の酸触媒による加水分解が、
通常のエステル化合物の加水分解に比べて非常に速い反
応速度で起きると同時に、加水分解生成物であるカルボ
ン酸が過酸化水素により酸化されて、過酸を容易に製造
できることを見出し、本発明を完成するに至った。Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems of the prior art. As a result, when an ester compound and hydrogen peroxide are mixed in the presence of an acid catalyst, hydrolysis of the ester compound by the acid catalyst is
The present invention has been found to occur at a very high reaction rate as compared with usual hydrolysis of an ester compound, and at the same time, a carboxylic acid as a hydrolysis product is oxidized by hydrogen peroxide to easily produce a peracid. It was completed.
【０００６】すなわち、本発明は、エステル化合物と過
酸化水素を、酸触媒存在下で混合し、エステル化合物を
酸化することを特徴とする過酸の製造方法に関する。That is, the present invention relates to a method for producing peracid, comprising mixing an ester compound and hydrogen peroxide in the presence of an acid catalyst to oxidize the ester compound.
【０００７】[0007]
【発明の実施の形態】本発明において用いるエステル化
合物は、各種カルボン酸類とアルコール類から得られる
各種のものを特に制限なく使用できる。このようなエス
テル化合物としては、たとえば、一般式（１）：Ｒ1 −
ＣＯＯ−Ｒ2 （式中、Ｒ1 は炭素数１〜３のアルキル
基、またはアミノ基、水酸基もしくはハロゲン基を有す
る炭素数１〜３以下のアルキル基を表し、Ｒ2 は炭素数
１〜６のアルキル基、もしくはアミノ基、水酸基もしく
はハロゲン基を有する炭素数１〜６の置換アルキル基、
またはフェニル基、もしくはアミノ基、水酸基、ハロゲ
ン基もしくはアルキル基を有する置換フェニル基を表
す。）で表される化合物などがあげられる。これらエス
テル化合物としては、Ｒ1 が炭素数１〜３のアルキル
基、Ｒ2 が炭素数１〜６のアルキル基の化合物、すなわ
ち、酢酸、プロピオン酸または酪酸と炭素数１〜６アル
コールとのエステル化合物が好ましい。これらのエステ
ル化合物は１種を単独で用いてもよく、また２種類以上
混合して用いてもよい。２種類以上混合して用いる場合
はその混合比率を任意に設定することができる。DESCRIPTION OF THE PREFERRED EMBODIMENTS As the ester compound used in the present invention, various compounds obtained from various carboxylic acids and alcohols can be used without particular limitation. Examples of such an ester compound include, for example, a compound represented by the general formula (1): R 1-
COO-R 2 (In the formula, R 1 represents an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms having an amino group, a hydroxyl group or a halogen group, and R 2 represents 1 to 6 carbon atoms. An alkyl group, or a substituted alkyl group having 1 to 6 carbon atoms having an amino group, a hydroxyl group or a halogen group,
Or a phenyl group or a substituted phenyl group having an amino group, a hydroxyl group, a halogen group or an alkyl group. ) And the like. Examples of these ester compounds are compounds in which R 1 is an alkyl group having 1 to 3 carbon atoms and R 2 is an alkyl group having 1 to 6 carbon atoms, that is, an ester of acetic acid, propionic acid or butyric acid and an alcohol having 1 to 6 carbon atoms. Compounds are preferred. One of these ester compounds may be used alone, or two or more thereof may be used in combination. When two or more kinds are mixed and used, the mixing ratio can be set arbitrarily.
【０００８】発明において用いる過酸化水素は、通常、
過酸化水素を水または有機溶媒で希釈したもの（以下過
酸化水素溶液）を用いる。希釈に用いることのできる有
機溶媒としては、過酸化水素を溶解でき、過酸化水素に
よって酸化されないアルコール類、ケトン類などが好ま
しい。具体的には、アルコール類としてはメタノール、
エタノール、１−または２−プロパノール、１−、２
−、３−またはtert−ブタノールなどを例示できる。ケ
トン類としてはアセトン、メチルエチルケトン、ジエチ
ルケトン、メチルイソブチルケトン、エチルブチルケト
ンなどを例示できる。その他、これらの化合物が各種官
能基で置換されたものも用いることができる。The hydrogen peroxide used in the invention is usually
A solution obtained by diluting hydrogen peroxide with water or an organic solvent (hereinafter referred to as a hydrogen peroxide solution) is used. As the organic solvent that can be used for dilution, alcohols and ketones that can dissolve hydrogen peroxide and are not oxidized by hydrogen peroxide are preferable. Specifically, methanol as the alcohol,
Ethanol, 1- or 2-propanol, 1-, 2
Examples thereof include-, 3- or tert-butanol. Examples of ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, and ethyl butyl ketone. In addition, those in which these compounds are substituted with various functional groups can also be used.
【０００９】過酸化水素溶液の濃度は、特に制限され
ず、市販の各種濃度のものから９０重量％を超える高濃
度のものまで各種のものを用いることができる。一般的
には、９０重量％を超える高濃度の過酸化水素溶液は、
爆発の危険性が高いことから、安全面を考慮すれば過酸
化水素溶液は、濃度９０重量％以下のもの、さらには濃
度７５重量％以下のものが望ましい。一方、低濃度の過
酸化水素溶液であっても反応には何ら影響を及ぼさない
が、一定量の過酸を生成するのに用いる過酸化水素溶液
の液量を考慮すると過酸化水素溶液は、濃度５重量％以
上のもの、さらには濃度２５重量％以上のものが望まし
い。The concentration of the hydrogen peroxide solution is not particularly limited, and various commercially available ones can be used, and various ones having a high concentration exceeding 90% by weight can be used. Generally, a high-concentration hydrogen peroxide solution exceeding 90% by weight is
Since there is a high risk of explosion, the hydrogen peroxide solution should preferably have a concentration of 90% by weight or less and more preferably have a concentration of 75% by weight or less in consideration of safety. On the other hand, even a low-concentration hydrogen peroxide solution has no effect on the reaction, but considering the amount of the hydrogen peroxide solution used to generate a certain amount of peracid, the hydrogen peroxide solution is It is desirable that the concentration is 5% by weight or more, and further that the concentration is 25% by weight or more.
【００１０】前記エステル化合物と過酸化水素の比率に
特に制限はないが、反応の効率と安全性を考慮すると、
エステル化合物のモル数を過酸化水素のモル数で除した
値が１０００〜１．２となる範囲が望ましい。さらに前
記値は１００以下が望ましく、また２以上が望ましい。The ratio of the ester compound to hydrogen peroxide is not particularly limited, but considering the efficiency and safety of the reaction,
It is desirable that the value obtained by dividing the number of moles of the ester compound by the number of moles of hydrogen peroxide be 1000 to 1.2. Further, the value is preferably 100 or less, and more preferably 2 or more.
【００１１】本発明において用いる触媒としては、各種
の酸触媒を特に限定なく使用できる。例えば、酸触媒と
しては硫酸、塩酸、硝酸のような一般的な無機酸触媒、
メタンスルフォン酸、パラトルエンスルフォン酸、ベン
ゼンスルフォン酸、スルフォン酸型強酸型イオン交換樹
脂のようなスルフォン酸化合物、スルフォン酸型以外の
強酸型イオン交換樹脂、シリカアルミナ、酸化ニオブ、
酸化チタン、タングステン酸のような金属酸化物、ナフ
ィオン、トリフルオロ酢酸などを例示できる。これら酸
触媒のなかでも強酸が好ましく、特に硫酸や、スルフォ
ン酸基を有する化合物が好ましい。As the catalyst used in the present invention, various acid catalysts can be used without particular limitation. For example, as the acid catalyst, common inorganic acid catalysts such as sulfuric acid, hydrochloric acid, and nitric acid,
Methanesulfonic acid, paratoluenesulfonic acid, benzenesulfonic acid, sulfonic acid compounds such as sulfonic acid type strong acid type ion exchange resin, strong acid type ion exchange resin other than sulfonic acid type, silica alumina, niobium oxide,
Examples thereof include metal oxides such as titanium oxide and tungstic acid, Nafion, and trifluoroacetic acid. Among these acid catalysts, strong acids are preferred, and sulfuric acid and compounds having a sulfonic acid group are particularly preferred.
【００１２】前記酸触媒の使用量は、特に制限されない
が、反応速度および経済面を勘案すると、エステル化合
物の重量に対し、通常、０．００１〜５０重量％程度が
望ましい。反応速度の低下や反応時間を考慮すれば、酸
触媒の使用量の下限は０．１重量％がより望ましく、経
済面からは上限を２０重量％とするのがより望ましい。The amount of the acid catalyst to be used is not particularly limited, but is preferably about 0.001 to 50% by weight, based on the weight of the ester compound, in consideration of the reaction rate and economy. In consideration of a reduction in the reaction rate and the reaction time, the lower limit of the amount of the acid catalyst used is more preferably 0.1% by weight, and the upper limit is more preferably 20% by weight from the viewpoint of economy.
【００１３】本発明の過酸の製造は、酸触媒の存在下
で、前記エステル化合物を過酸化水素により酸化するこ
とにより行なう。かかる反応において、前記エステル化
合物は溶媒としても作用するため、前記エステル化合物
が反応温度において液体の場合には、溶媒の使用は特に
必要とされないが、エステル化合物が固体である場合に
はこれを溶解させる水または有機溶媒を加えることがで
きる。添加できる有機溶媒としては、過酸によって酸化
されないものが好ましい。また、被溶解物がエステル化
合物であることから、極性を有するものが好ましい。具
体的には、過酸化水素溶液に用いたアルコール類、ケト
ン類などがあげられる。なお、エステル化合物が液体で
ある場合においても過酸化水素溶液との相溶性をよくす
る目的で適量の有機溶媒を加えることができる。The production of the peracid of the present invention is carried out by oxidizing the ester compound with hydrogen peroxide in the presence of an acid catalyst. In such a reaction, since the ester compound also acts as a solvent, when the ester compound is a liquid at the reaction temperature, use of a solvent is not particularly required, but when the ester compound is a solid, it is dissolved. Precipitated water or organic solvent can be added. Organic solvents that can be added are preferably those that are not oxidized by peracids. Further, since the substance to be dissolved is an ester compound, those having polarity are preferable. Specific examples include alcohols and ketones used in the hydrogen peroxide solution. Even when the ester compound is liquid, an appropriate amount of an organic solvent can be added for the purpose of improving the compatibility with the hydrogen peroxide solution.
【００１４】本発明の過酸の製造方法における反応温度
は、反応の効率と安全性を考慮すると、通常、反応系が
固化する低温以上でかつ反応系が沸騰する高温以下で行
われることが望まれる。具体的温度は使用するエステル
化合物、有機溶媒によって異なるが、エステル化合物と
して酢酸イソブチルを用いた場合は、酢酸イソブチルの
融点である−９９℃から沸点である１１７℃の範囲で行
われるのが良い。さらに反応効率の面からすれば−３０
℃以上が望ましく、安全性の面からすれば８０℃以下が
望ましい。In consideration of the efficiency and safety of the reaction, the reaction temperature in the method for producing peracid of the present invention is usually desirably carried out at a temperature lower than the temperature at which the reaction system solidifies and at a temperature lower than the temperature at which the reaction system boils. Be done. The specific temperature varies depending on the ester compound used and the organic solvent, but when isobutyl acetate is used as the ester compound, it is preferably carried out within the range of −99 ° C. which is the melting point of isobutyl acetate to 117 ° C. which is the boiling point. Furthermore, from the viewpoint of reaction efficiency, it is -30.
C. or higher is desirable, and from the viewpoint of safety, 80.degree. C. or lower is desirable.
【００１５】反応は殆どの場合に短時間で終了するが、
完全に反応を終結させるためにはさらに反応時間を延ば
すことができる。通常、反応時間は５分〜２４時間程度
である。The reaction is completed in a short time in most cases.
To complete the reaction, the reaction time can be further extended. Usually, the reaction time is about 5 minutes to 24 hours.
【００１６】こうして得られた過酸は、生成系から、蒸
留、水または溶剤抽出（エステル化合物と混合しない極
性の有機溶剤）、カラム分離等の手段により分離でき
る。The peracid thus obtained can be separated from the production system by means such as distillation, water or solvent extraction (a polar organic solvent which does not mix with the ester compound), and column separation.
【００１７】なお、本発明の製造方法に用いる装置は、
前記の反応温度に耐え、かつ過酸化水素および過酸の急
激な分解を引き起こす物質、例えば金属分、高分子、化
学物質などの付着しないものが安全上望ましい。反応器
の材質も前記の反応温度に耐え、かつ過酸化水素および
過酸の急激な分解を引き起こす材料で作られていなけれ
ば特に制限はない。また、撹拌設備のあるものが望まし
い。The apparatus used in the manufacturing method of the present invention is
From the viewpoint of safety, substances that can withstand the above reaction temperatures and that cause rapid decomposition of hydrogen peroxide and peracid, such as metal components, polymers, and chemical substances, are not attached. The material of the reactor is not particularly limited as long as it is not made of a material that withstands the above-mentioned reaction temperature and causes rapid decomposition of hydrogen peroxide and peracid. Further, a device having a stirring device is desirable.
【００１８】[0018]
【発明の効果】本発明では、過酸の原料としてカルボン
酸を用いていないため、製造装置の腐食等の問題を最小
限に止めることができる。また、製造された過酸は、エ
ステル化合物中に存在するため、エステル化合物と過酸
の性質の違いを利用して生成系内から容易に過酸を分離
することができる。According to the present invention, since carboxylic acid is not used as a raw material for peracid, problems such as corrosion of manufacturing equipment can be minimized. Further, since the produced peracid is present in the ester compound, the peracid can be easily separated from the production system by utilizing the difference in properties between the ester compound and the peracid.
【００１９】[0019]
【実施例】以下に実施例をあげて本発明をさらに具体的
に説明するが、本発明はこれら実施例に限定されるもの
ではない。なお、％は特記しない限りいずれも重量基準
である。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. All percentages are by weight unless otherwise specified.
【００２０】実施例１ 還流管を備えた１００ｍｌのガラス製三つ口フラスコに
酢酸ブチル２０ｇ（１９２ミリモル）、酸触媒としてメ
タンスルフォン酸０．５ｇを加えた。室温（２５℃）に
て電磁撹拌を行いながら６０％過酸化水素水１．３９ｇ
（２４．５ミリモル）を５分かけて滴下した。その後、
室温にて電磁撹拌を行いながら５時間放置した。この反
応液を０．１規定過マンガン酸カリウムで滴定し過酸化
水素量を定量した。続いて、よう素滴定法にて過酢酸量
を定量した。その結果、過酸化水素の残存量は３．３６
ミリモル、過酢酸の生成量は、２１．１４ミリモル（過
酢酸の収率は８６モル％）であった。Example 1 20 g (192 mmol) of butyl acetate and 0.5 g of methanesulfonic acid as an acid catalyst were added to a 100 ml glass three-necked flask equipped with a reflux tube. 60% hydrogen peroxide water 1.39g while performing electromagnetic stirring at room temperature (25 ° C)
(24.5 mmol) was added dropwise over 5 minutes. afterwards,
The mixture was left for 5 hours at room temperature with magnetic stirring. This reaction solution was titrated with 0.1 N potassium permanganate to quantify the amount of hydrogen peroxide. Then, the amount of peracetic acid was quantified by the iodine titration method. As a result, the remaining amount of hydrogen peroxide was 3.36.
The amount of production of mmol and peracetic acid was 21.14 mmol (the yield of peracetic acid was 86 mol%).
【００２１】実施例２〜１０、比較例１〜２ 実施例１において、エステル化合物の種類、酸触媒の種
類および反応温度のうち少なくともひとつを表１に示す
ように変えた他は実施例１と同様の操作を行い、また実
施例１と同様にして過酸化水素と過酸を確認した。過酸
の収率を表１に示す。Examples 2 to 10 and Comparative Examples 1 and 2 Example 1 was the same as Example 1 except that at least one of the type of ester compound, the type of acid catalyst and the reaction temperature was changed as shown in Table 1. The same operation was performed, and hydrogen peroxide and peracid were confirmed in the same manner as in Example 1. The yield of peracid is shown in Table 1.
【００２２】なお、実施例において得られた過酸は、安
定剤としてジオクチル二水素ピロリン酸エステルを加え
た後減圧蒸留することで原料のエステル化合物から容易
に分離できた。The peracids obtained in the examples could be easily separated from the starting ester compounds by adding dioctyl dihydrogen pyrophosphate ester as a stabilizer and then distilling under reduced pressure.
【００２２】[0022]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ // Ｃ０７Ｂ 61/00 ３００ Ｃ０７Ｂ 61/00 ３００ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code FI // C07B 61/00 300 C07B 61/00 300
Claims (3)
存在下で混合し、エステル化合物を酸化することを特徴
とする過酸の製造方法。1. A method for producing a peracid, which comprises mixing an ester compound and hydrogen peroxide in the presence of an acid catalyst to oxidize the ester compound.
または酪酸と炭素数１〜６のアルコールとのエステル化
合物である請求項１記載の製造方法。2. The method according to claim 1, wherein the ester compound is an ester compound of acetic acid, propionic acid or butyric acid and an alcohol having 1 to 6 carbon atoms.
有する化合物である請求項１または２記載の製造方法。3. The method according to claim 1, wherein the acid catalyst is a compound having a sulfuric acid or a sulfonic acid group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15571997A JPH10330357A (en) | 1997-05-28 | 1997-05-28 | Production of peracid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15571997A JPH10330357A (en) | 1997-05-28 | 1997-05-28 | Production of peracid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10330357A true JPH10330357A (en) | 1998-12-15 |
Family
ID=15612000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15571997A Pending JPH10330357A (en) | 1997-05-28 | 1997-05-28 | Production of peracid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10330357A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014072143A1 (en) | 2012-11-08 | 2014-05-15 | Evonik Industries Ag | Method for producing equilibrium peracetic acid and equilibrium peracetic acid obtainable by the method |
| CN107602435A (en) * | 2016-07-12 | 2018-01-19 | 上海利康消毒高科技有限公司 | The method that glyceryl triacetate prepares Peracetic acid |
-
1997
- 1997-05-28 JP JP15571997A patent/JPH10330357A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014072143A1 (en) | 2012-11-08 | 2014-05-15 | Evonik Industries Ag | Method for producing equilibrium peracetic acid and equilibrium peracetic acid obtainable by the method |
| JP2015535297A (en) * | 2012-11-08 | 2015-12-10 | エボニック インダストリーズ アクチエンゲゼルシャフトＥｖｏｎｉｋ Ｉｎｄｕｓｔｒｉｅｓ ＡＧ | Method for producing equilibrium peracetic acid and equilibrium peracetic acid obtained by said method |
| CN107602435A (en) * | 2016-07-12 | 2018-01-19 | 上海利康消毒高科技有限公司 | The method that glyceryl triacetate prepares Peracetic acid |
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