JPH0730013B2 - Method for stabilizing perpropionic acid - Google Patents
Method for stabilizing perpropionic acidInfo
- Publication number
- JPH0730013B2 JPH0730013B2 JP26202186A JP26202186A JPH0730013B2 JP H0730013 B2 JPH0730013 B2 JP H0730013B2 JP 26202186 A JP26202186 A JP 26202186A JP 26202186 A JP26202186 A JP 26202186A JP H0730013 B2 JPH0730013 B2 JP H0730013B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- perpropionic acid
- mol
- perpropionic
- stabilizing
- 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.)
- Expired - Fee Related
Links
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 title claims description 39
- 238000000034 method Methods 0.000 title claims description 11
- 230000000087 stabilizing effect Effects 0.000 title claims description 9
- 239000003381 stabilizer Substances 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 9
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 8
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- WJJMNDUMQPNECX-UHFFFAOYSA-N Dipicolinic acid Natural products OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 6
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- -1 alkali metal salt Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 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
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000003352 sequestering agent Substances 0.000 description 2
- 239000005725 8-Hydroxyquinoline Substances 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical class OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229960003540 oxyquinoline Drugs 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- SHNUBALDGXWUJI-UHFFFAOYSA-N pyridin-2-ylmethanol Chemical compound OCC1=CC=CC=N1 SHNUBALDGXWUJI-UHFFFAOYSA-N 0.000 description 1
- LOAUVZALPPNFOQ-UHFFFAOYSA-N quinaldic acid Chemical compound C1=CC=CC2=NC(C(=O)O)=CC=C21 LOAUVZALPPNFOQ-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- 150000003248 quinolines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910021655 trace metal ion Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は過プロピオン酸の安定化方法に関する。TECHNICAL FIELD The present invention relates to a method for stabilizing perpropionic acid.
更に詳しくは容易に分解し易い過プロピオン酸溶液中
に、鉄、ニッケルなどの微量金属イオンが存在する際に
優れた金属イオン封鎖性を示す安定剤を添加する過プロ
ピオン酸の安定化方法に関するものである。More specifically, it relates to a method for stabilizing perpropionic acid in which a stabilizer exhibiting excellent sequestering properties in the presence of trace metal ions such as iron and nickel is added to a perpropionic acid solution that is easily decomposed. Is.
従来の技術 通常、過カルボン酸は微量の金属イオンが存在すると、
その触媒作用により激しく分解を起こすため、種々の金
属封鎖剤の添加が必要になる。従来、過カルボン酸の安
定剤または金属封鎖剤として数多くの特許が出願されて
いる。Conventional Technology Usually, percarboxylic acid is present in the presence of a trace amount of metal ions.
The catalytic action causes severe decomposition, so that it is necessary to add various sequestering agents. Many patents have been filed as stabilizers or sequestering agents for percarboxylic acids.
即ち、例を挙げれば、 （１） ピロ燐酸ソーダ、トリポリ燐酸ソーダなどのポ
リ燐酸塩及びそのエステルを安定剤とするもの（例えば
特公昭38−25658号、特公昭54−7764号など）。That is, for example, (1) those in which polyphosphate salts such as sodium pyrophosphate and sodium tripolyphosphate and esters thereof are used as stabilizers (for example, JP-B-38-25658, JP-B-54-7764, etc.).
（２） ピリジン−２−メタノールと種々の燐酸系化合
物との混合物を安定剤とするもの（例えば特公昭38−10
521号）。(2) Using a mixture of pyridine-2-methanol and various phosphoric acid compounds as a stabilizer (for example, JP-B-38-10).
No. 521).
（３） ピリジンジカルボン酸もしくはそのアルカリ金
属塩またはアンモニウム塩とヘキサメタ燐酸ナトリウム
とを安定剤とするもの（特公昭52−38009号）。(3) A compound containing pyridinedicarboxylic acid or an alkali metal salt or ammonium salt thereof and sodium hexametaphosphate as a stabilizer (Japanese Patent Publication No. 52-38009).
（４） ８ヒドロキシキノリン、キナルジン酸またはそ
の塩及びキノリン誘導体を安定剤とするもの（例えば英
国特許第906970号）。(4) A compound containing 8-hydroxyquinoline, quinaldic acid or a salt thereof, and a quinoline derivative as a stabilizer (for example, British Patent No. 906970).
（５） その他、エチレンジアミン四酢酸塩、ジエチレ
ントリアミン五酢酸塩、ロダンカリ、ポリアミノカルボ
ン酸など（「有機過酸化物、−その化学と工業的利用
−」化学工業社編、164頁記載）。(5) In addition, ethylenediaminetetraacetic acid salt, diethylenetriaminepentaacetic acid salt, rhodancari, polyaminocarboxylic acid, etc. ("Organic peroxide, -its chemistry and industrial use-" edited by Kagaku Kogyo Co., Ltd., p.
発明が解決しようとする問題点 しかしながら本発明者らは上記文献等に見られる安定剤
のほとんどすべてについてその効果を調べたところ次の
事実がわかった。Problems to be Solved by the Invention However, when the present inventors investigated the effects of almost all the stabilizers found in the above-mentioned documents and the like, the following facts were found.
すなわち鉄イオンを数ppm含む反応原料を用い、上記の
各種安定剤を添加して過プロプオン酸の合成試験及び過
プロピオン酸の熱安定性試験を実施したところ、安定剤
として多少効果のあるもの、または全くないものなど様
々であり、結局過プロピオン酸の分解を抑制し、効率良
く過プロピオン酸を製造するに充分な効果を有する安定
剤は皆無であった。That is, using a reaction raw material containing a few ppm of iron ions, when performing the synthetic test of perpropionic acid and the thermal stability test of perpropionic acid by adding the above-mentioned various stabilizers, some effect as a stabilizer, There are various stabilizers, such as those that do not exist at all, and there is no stabilizer that has sufficient effect to suppress the decomposition of perpropionic acid and efficiently produce perpropionic acid.
本発明の目的は、金属を微量含む反応原料を用いて過プ
ロプオン酸を製造する際に、過プロピオン酸の分解を抑
制し、安定化させうる安定剤及び安定化方法を提供する
ことにある。An object of the present invention is to provide a stabilizer and a stabilizing method capable of suppressing and stabilizing the decomposition of perpropionic acid when producing perpropionic acid using a reaction raw material containing a trace amount of metal.
問題点を解決するための手段及び作用 本発明者らは上記欠点を克服すべく鋭意検討した結果、
燐酸と、2,6−ピリジンジカルボン酸と及びヘキサメタ
燐酸ナトリウムとを安定剤として併用すると、金属イオ
ンを含む過プロピオン酸の安定化に非常に効果のあるこ
とが判り、本発明を完成させるに至った。Means and Actions for Solving Problems As a result of intensive investigations by the present inventors to overcome the above-mentioned drawbacks,
It was found that the combined use of phosphoric acid, 2,6-pyridinedicarboxylic acid and sodium hexametaphosphate as a stabilizer is very effective in stabilizing perpropionic acid containing a metal ion, and the present invention has been completed. It was
即ち、本発明は、過プロピオン酸溶液に燐酸と、2,6−
ピリジンジカルボン酸と及びヘキサメタ燐酸ナトリウム
を安定剤として添加することを特徴とする過プロピオン
酸の安定化方法である。That is, the present invention, phosphoric acid in the perpropionic acid solution, 2,6-
A method for stabilizing perpropionic acid, which comprises adding pyridinedicarboxylic acid and sodium hexametaphosphate as stabilizers.
本発明で用いる過プロピオン酸溶液は、プロピオンアル
デヒドの液相自動酸化法、またはプロピオン酸と過酸化
水素との反応等、公知の方法により得られる。The perpropionic acid solution used in the present invention can be obtained by a known method such as a liquid-phase autoxidation method of propionaldehyde or a reaction of propionic acid and hydrogen peroxide.
本発明の燐酸と、2,6−ピリジンジカルボン酸と及びヘ
キサメタ燐酸ナトリウムの添加量は、過プロピオン酸溶
液中の金属濃度によって異なるが、例えば鉄イオンとし
て0.5ppm前後の場合、過プロピオン酸溶液に対して総添
加量で50ppm以上の添加で効果を示すが、安定化効果と
経済性面より総添加量で200〜600ppmが好ましい。また
燐酸と、2,6−ピリジンジカルボン酸と及びヘキサメタ
燐酸ナトリウムの併用割合は、重量比で1.0/1.0〜0.01/
1.0〜0.01、好ましくは1.0/0.5〜0.05/0.5〜0.05であ
る。このようにして調整された安定剤含有過プロピオン
酸溶液は、通常のオレフィンのエポキシ化反応、ケトン
の酸化反応、芳香核の開環反応等に何ら支障なく使用す
ることができる。The addition amount of the phosphoric acid of the present invention, 2,6-pyridinedicarboxylic acid, and sodium hexametaphosphate varies depending on the metal concentration in the perpropionic acid solution. On the other hand, the total addition amount of 50 ppm or more is effective, but the total addition amount is preferably 200 to 600 ppm from the viewpoint of stabilizing effect and economical efficiency. Further, the combined ratio of phosphoric acid, 2,6-pyridinedicarboxylic acid and sodium hexametaphosphate is 1.0 / 1.0 to 0.01 / by weight.
It is 1.0 to 0.01, preferably 1.0 / 0.5 to 0.05 / 0.5 to 0.05. The thus-prepared stabilizer-containing perpropionic acid solution can be used without any problems in the usual olefin epoxidation reaction, ketone oxidation reaction, aromatic ring opening reaction, and the like.
実施例 以下実施例により本発明を更に詳細に説明する。Examples The present invention will be described in more detail with reference to Examples below.
（参考例−１） −過プロピオン酸の製造− 塔頂部に還流コンデンサを取付けた10段オルダ−ショウ
蒸留塔付パイレックスガラス製500ml反応器に、60％過
酸化水素水47.6g（0.84モル）、1.0ppmの鉄イオンを含
むプロピオン酸186.3g（2.52モル）、触媒として硼酸3.
3g（0.053モル）、共沸脱水剤として1.2−ジクロルエタ
ン94gを装入した。この反応器をオイルバスにより内温7
0℃、（内圧200mmHg）に加熱した。反応で生成した水及
び過酸化水素に同伴した水は、1,2−ジクロルエタンと
の共沸脱水蒸留により塔頂から分離、除去した。反応時
間は２時間とした。反応終了液中には、過プロピオン酸
が0.492モル（1.64モル／）含まれていた。(Reference Example-1) -Production of perpropionic acid-In a 10-stage Older-Show distillation column equipped Pyrex glass 500 ml reactor equipped with a reflux condenser at the top of the column, 60% hydrogen peroxide solution 47.6 g (0.84 mol), 186.3 g (2.52 mol) of propionic acid containing 1.0 ppm of iron ions, boric acid as a catalyst 3.
3 g (0.053 mol) and 94 g of 1.2-dichloroethane as an azeotropic dehydrating agent were charged. The internal temperature of this reactor is 7
It was heated to 0 ° C. (internal pressure 200 mmHg). Water produced in the reaction and water entrained in hydrogen peroxide were separated and removed from the top of the column by azeotropic dehydration distillation with 1,2-dichloroethane. The reaction time was 2 hours. The reaction completed liquid contained 0.492 mol (1.64 mol /) of perpropionic acid.
また塔頂より分離した留出水中には未反応過酸化水素が
0.033モル含まれており、過プロピオン酸の選択率Ａは6
1モル％であった。In addition, unreacted hydrogen peroxide is contained in the distilled water separated from the top of the tower.
It contains 0.033 mol, and the selectivity A of perpropionic acid is 6
It was 1 mol%.
但しＢ＝生成した過プロピオン酸（モル） Ｃ＝反応で消費した過酸化水素（モル） Ａ＝（B/C）×100（モル％） とする。Here, B = perpropionic acid produced (mol) C = hydrogen peroxide consumed in the reaction (mol) A = (B / C) × 100 (mol%).
（参考例−２） 触媒として98％硫酸0.14gを使用する以外は参考例−１
と同様の方法で実施した。反応終了液中には、過プロピ
オン酸が0.502モル（1.670モル／）含まれていた。ま
た分離した留出液中には未反応過酸化水素が0.030モル
含まれており、過プロピオン酸の選択率は62モル％であ
った。Reference Example-1 Reference Example-1 except that 0.14 g of 98% sulfuric acid is used as a catalyst.
It carried out by the method similar to. The reaction-completed liquid contained 0.502 mol (1.670 mol /) of perpropionic acid. The separated distillate contained 0.030 mol of unreacted hydrogen peroxide, and the selectivity of perpropionic acid was 62 mol%.
（参考例−３） 触媒として陽イオン交換樹脂Lewatit SC−102（バイエ
ル社製）15gを使用する以外は参考例−１と同様の方法
で実施した。陽イオン交換樹脂分離後の反応終了液中に
は過プロピオン酸が0.478モル（1.590モル／）含まれ
ていた。また分離した留出液中には、未反応過酸化水素
が0.051モル含まれており、過プロピオン酸の選択率は6
0モル％であった。(Reference example-3) It carried out by the same method as the reference example-1 except having used 15 g of cation exchange resin Lewatit SC-102 (made by Bayer) as a catalyst. After the cation-exchange resin was separated, the reaction-completed liquid contained 0.478 mol (1.590 mol /) of perpropionic acid. The separated distillate contained 0.051 mol of unreacted hydrogen peroxide, and the selectivity of perpropionic acid was 6%.
It was 0 mol%.
（実施例１〜４、比較例１〜13） −過プロピオン酸の加熱分解試験− 窒素シール付の還流冷却器を備えた50mlのパイレックス
ガラス製試験管に、参考例−１、２、及び３で調整した
過プロピオン酸溶液30mlと、各種安定剤を表−１に示す
ように入れ、オイルバスにより70℃で４時間加熱後の過
プロピオン酸の濃度を分析し、この濃度と試験開始時の
濃度とから次式により過プロピオン酸の分解率を算出
し、安定剤の効果を判定した。(Examples 1 to 4 and Comparative Examples 1 to 13) -Heat decomposition test of perpropionic acid-Reference examples -1, 2 and 3 in a 50 ml Pyrex glass test tube equipped with a reflux condenser with a nitrogen seal. Add 30 ml of the perpropionic acid solution prepared in step 1 and various stabilizers as shown in Table-1 and analyze the concentration of perpropionic acid after heating at 70 ° C for 4 hours in an oil bath. The decomposition rate of perpropionic acid was calculated from the concentration and the following formula to determine the effect of the stabilizer.
結果を表−１に示す。The results are shown in Table-1.
過プロピオン酸の分解率（モル％） ＝〔（ａ−ｂ）/a〕×100 a:試験開始時の過プロピオン酸濃度（モル／） b:試験終了時の過プロピオン酸濃度（モル／） （実施例５） −過プロピオン酸の合成試験− 安定剤として85％燐酸0.08g（原料に対して240ppm）、
2,6−ピリジンジカルボン酸0.04g、ヘキサメタ燐酸ナト
リウム0.04g（共に原料に対して120ppm）添加する以外
は参考例−１と同様の方法で実施した。反応終了液中に
は過プロピオン酸が0.759モル（2.530モル／）含まれ
ていた。また塔頂より分離した留出水中には未反応過酸
化水素が0.024モル含まれており、過プロピオン酸の選
択率は93モル％であった。この過プロピオン酸溶液につ
いて安定剤を添加せずに実施例１〜４と同様に加熱分解
試験を実施した。Decomposition rate of perpropionic acid (mol%) = [(ab) / a] × 100 a: Perpropionic acid concentration at the start of the test (mol /) b: Perpropionic acid concentration at the end of the test (mol /) (Example 5) -Synthesis test of perpropionic acid-0.08 g of 85% phosphoric acid as a stabilizer (240 ppm with respect to the raw material),
The same procedure as in Reference Example 1 was carried out except that 0.04 g of 2,6-pyridinedicarboxylic acid and 0.04 g of sodium hexametaphosphate were added (120 ppm based on the raw material). The reaction completed liquid contained 0.759 mol (2.530 mol /) of perpropionic acid. The distilled water separated from the top of the column contained 0.024 mol of unreacted hydrogen peroxide, and the selectivity of perpropionic acid was 93 mol%. This perpropionic acid solution was subjected to a thermal decomposition test in the same manner as in Examples 1 to 4 without adding a stabilizer.
試験終了後の過プロピオン酸濃度は2.441モル／であ
り、過プロピオン酸の分解率は3.52モル％であった。The perpropionic acid concentration after the test was 2.441 mol /, and the decomposition rate of perpropionic acid was 3.52 mol%.
参考例−１と比較して、本発明に係る安定剤を合成前に
添加しても、過プロピオン酸の熱安定性及び合成収率に
効果のあることが判る。As compared with Reference Example-1, it can be seen that even if the stabilizer according to the present invention is added before the synthesis, it is effective for the thermal stability of perpropionic acid and the synthesis yield.
発明の効果 本発明は、各実施例において明らかのように、過プロピ
オン酸の安定剤として、燐酸と、2,6−ピリジンカルボ
ン酸と及びヘキサメタ燐酸ナトリウムとを併用すること
により優れた相乗効果を示し、過プロピオン酸の熱安定
性及び合成収率を向上させるので、その産業上の利用価
値は大きい。EFFECTS OF THE INVENTION As apparent from each of the examples, the present invention provides excellent synergistic effect by using phosphoric acid, 2,6-pyridinecarboxylic acid, and sodium hexametaphosphate together as a stabilizer of perpropionic acid. Since it improves the thermal stability and synthetic yield of perpropionic acid, its industrial utility value is great.
Claims (1)
ジンジカルボン酸と及びヘキサメタ燐酸ナトリウムとを
安定剤として添加することを特徴とする過プロピオン酸
の安定化方法。1. A method for stabilizing perpropionic acid, which comprises adding phosphoric acid, 2,6-pyridinedicarboxylic acid and sodium hexametaphosphate as stabilizers to a perpropionic acid solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26202186A JPH0730013B2 (en) | 1986-11-05 | 1986-11-05 | Method for stabilizing perpropionic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26202186A JPH0730013B2 (en) | 1986-11-05 | 1986-11-05 | Method for stabilizing perpropionic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63119458A JPS63119458A (en) | 1988-05-24 |
| JPH0730013B2 true JPH0730013B2 (en) | 1995-04-05 |
Family
ID=17369917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26202186A Expired - Fee Related JPH0730013B2 (en) | 1986-11-05 | 1986-11-05 | Method for stabilizing perpropionic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730013B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4317420C1 (en) * | 1993-05-26 | 1994-11-03 | Degussa | Stabilized percarboxylic acid solutions and process for their preparation |
| US8034759B2 (en) * | 2008-10-31 | 2011-10-11 | Ecolab Usa Inc. | Enhanced stability peracid compositions |
-
1986
- 1986-11-05 JP JP26202186A patent/JPH0730013B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63119458A (en) | 1988-05-24 |
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