JPH02134342A - Decoloring of dilute acetic acid - Google Patents
Decoloring of dilute acetic acidInfo
- Publication number
- JPH02134342A JPH02134342A JP28737988A JP28737988A JPH02134342A JP H02134342 A JPH02134342 A JP H02134342A JP 28737988 A JP28737988 A JP 28737988A JP 28737988 A JP28737988 A JP 28737988A JP H02134342 A JPH02134342 A JP H02134342A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- acetic acid
- dilute acetic
- concentration
- recovered
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 153
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 e.g. Chemical compound 0.000 claims abstract description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 12
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical compound OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 18
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 abstract description 34
- 239000002253 acid Substances 0.000 abstract description 15
- 241001550224 Apha Species 0.000 abstract description 9
- 235000011007 phosphoric acid Nutrition 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 238000004040 coloring Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000004043 dyeing Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 abstract description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 abstract description 2
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 abstract description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 abstract description 2
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 abstract description 2
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 abstract 1
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 150000002978 peroxides Chemical class 0.000 description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 235000011187 glycerol Nutrition 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 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 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001728 carbonyl compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- KZPGKZWAVAXZQU-UHFFFAOYSA-N acetic acid;ethaneperoxoic acid Chemical compound CC(O)=O.CC(=O)OO KZPGKZWAVAXZQU-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium 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
- 239000013065 commercial product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 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 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は回収された稀酢酸の脱色方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for decolorizing recovered dilute acetic acid.
さらに詳しくは、本発明は過ｆｉ￥酸を用いた酸化プロ
セスにおいて、副生じた酢酸から回収される稀酢酸の脱
色方法に関するものである。More specifically, the present invention relates to a method for decolorizing dilute acetic acid recovered from acetic acid produced as a by-product in an oxidation process using perfiry acid.
稀酢酸と通称されている「商品」は染色用の酸、ｐＨ調
整用薬剤などとして利用されており、通常、水分濃度は
７〜１１％程度であり、適用されるプロセスによっては
その他ＱＩＷなどを５〜１０％程度き有している場合も
ある。The "commercial product" commonly known as dilute acetic acid is used as a dyeing acid, a pH adjusting agent, etc., and usually has a water concentration of about 7 to 11%, and depending on the process used, it may contain other substances such as QIW. In some cases, the content is about 5 to 10%.
染色用の酸として便用される稀１１Ｆ酸においては、そ
の使用Ｅ］的から考えて当然のことながら、外観、より
具体的には着色度合いは特に重要な品質管理項「１とな
る。In rare 11F acid, which is conveniently used as an acid for dyeing, appearance, more specifically, the degree of coloring, is a particularly important quality control item ``1'', as is natural considering its use.
そして、湾状の有機１ヒ合物またはそれらの混合物の着
色度合いは通常Ａ Ｐ Ｉ−！ Ａ ｌｉ？ｉで管理さ
れている。Ａ Ｐ ＨＡ値というのは値が小さい程着色
度か低いということである。The degree of coloration of the bay-shaped organic compounds or mixtures thereof is usually A P I-! Ali? It is managed by i. The smaller the APHA value, the lower the degree of coloring.
［従来技術］
過酢酸を用いた酸化反応では反応１１１港中に以下のよ
うに過酢酸が分解して酢酸が生成する。[Prior Art] In an oxidation reaction using peracetic acid, peracetic acid decomposes during reaction 111 as shown below to produce acetic acid.
ＣＨ３ＣＯ０ＯＨ−ＣＨ３ＣＯ０Ｈ＋（０）（過酢酸）
（酢酸）
上記のようにして生成した反応１１ｉ中、さらには、反
応粗液中から回収される酢酸中には適用されるプ１１＋
ニスによって異なる種々の不純物が含まれてくる。CH3CO0OH-CH3CO0H+(0) (peracetic acid)
(Acetic acid) In the reaction 11i produced as described above, and furthermore, in the acetic acid recovered from the reaction crude liquid, the applied polymer 11+
Different varnishes contain various impurities.
例えば、過酢酸、アリルアルコール、および水を同時に
反応蒸留塔に仕込み、減圧下、２０〜９０゛Ｃ″Ｃ″酢
酸エチルを留去しながら反応を行うグリセリン製造プラ
ントから回収されるｌｌ！￥酸中には、水、蟻酸のほか
に微量の不純物が含まれている。For example, peracetic acid, allyl alcohol, and water are simultaneously charged into a reactive distillation column and the reaction is carried out under reduced pressure while distilling off ethyl acetate from 20 to 90°C. Acid contains trace amounts of impurities in addition to water and formic acid.
これら微量の不純物としては、ホルムアルデヒド、アセ
トアルデヒド、アクロレイン、その他有ｆｉ物の分解に
より生成する各種アルデヒド類などがある。These trace amounts of impurities include formaldehyde, acetaldehyde, acrolein, and various aldehydes produced by decomposition of other fi substances.
また、原料であるアリルアル；１−ル、およびそのエス
テル類、アリルエーテル、アクリル酸、およびそのエス
テル類等の不飽和化合物、アセトン。In addition, unsaturated compounds such as allyl al;1-l and its esters, allyl ether, acrylic acid, and its esters, and acetone, which are raw materials.
アセチルアセトン、メチルエチルゲ１〜ン、などのカル
ボニル化合物、さらには、製造設備より溶出する鉄、エ
ンゲル。クロム、ナトリウム等微量の金属等らある。Carbonyl compounds such as acetylacetone and methylethylgene, as well as iron and Engel eluted from manufacturing equipment. There are trace amounts of metals such as chromium and sodium.
上記のような不純物が以下のようなｅ色機横により着色
すると考えられる。It is thought that the above impurities cause coloring by the e-color machine as described below.
即ち
■アルデヒド類およびアリル、アクリル１ビニル等の不
飽和化合物相互の縮合反応による有機性着色物質の生成
によるもの、この場合、微量な溶解金属は反応を促進さ
せるための触媒四重きをすると考えられる。In other words, organic colored substances are produced by the condensation reaction between aldehydes and unsaturated compounds such as allyl and acrylic monovinyl. In this case, it is thought that a small amount of dissolved metal acts as a catalyst to promote the reaction. .
■重量金属とカルボニル化合物による金属銘木の生成に
よるもの。■It is caused by the formation of precious metal wood from heavy metals and carbonyl compounds.
これらの不純物を取り除くために蒸留、抽出などの精製
操作を組み合わせて実施されているが、このようにして
回収されただけでは稀酢酸の外観（ＡＰＨＡ＞は放置中
に経時変化し易く、良好な外観を有する稀酢酸を定常的
に得ることは困難であった。In order to remove these impurities, a combination of purification operations such as distillation and extraction is carried out, but if only recovered in this way, the appearance of dilute acetic acid (APHA) tends to change over time while left standing, and it is difficult to obtain a good quality. It has been difficult to regularly obtain dilute acetic acid with this appearance.
なお、上記のグリセリン製造プラントから回ｌｌ！され
る！！１ｌｌＷは生成するグリセリン１モルに対して７
０〜１５０モル％程度の量となる。In addition, from the above-mentioned glycerin manufacturing plant! It will be done! ! 1llW is 7 for 1 mole of glycerin produced.
The amount is about 0 to 150 mol%.
［発明が解決しようとする課題］
外ｆｉ （ＡＰＨＡ＞を支配する要因は、微量な不純物
であり、経済性を考慮した一般的な蒸留、抽出程度を組
み合わせた処理プロセスではこれら１に鼠成分を除去す
ることは極めて困難である。[Problems to be solved by the invention] The factors that control external fi (APHA) are minute amounts of impurities, and in a treatment process that combines general distillation and extraction levels in consideration of economic efficiency, it is difficult to add rat components to these 1. It is extremely difficult to remove.
以上のような状況に鷺み、本発明者らは鋭意検討した結
果、これらの不純物がアルデヒド類またはオレフィン類
からなっていると考えられるので、これらの微量不純物
を酸１ヒすることと、酸化の際の分解を押さえることに
よって、外［（ＡＰＨＡ）の向上を達成できるのではな
いかということに着目して以下のような発明を完成させ
た。In view of the above situation, the inventors of the present invention have conducted intensive studies and found that these impurities are thought to be composed of aldehydes or olefins. Focusing on the idea that it might be possible to improve APHA by suppressing the decomposition during oxidation, the following invention was completed.
し発明の構成〕
すなわち、本発明は
「稀酢酸に対して１００〜２５００ Ｐ Ｐ １１の濃
度になるように過酸化水素または過カルボン酸を添加し
、さらに、該過酸化水素水または過カルボン酸に対して
１〜１１００ｐｐの濃度になるようにリン酸系化合！Ｉ
Ｎまたはそれらのアルカリ金属塩またはアルカリ土類金
属塩を添加することを特徴とする稀酢酸の脱色方法」
である。[Structure of the Invention] That is, the present invention involves adding hydrogen peroxide or percarboxylic acid to dilute acetic acid to a concentration of 100 to 2500 P P 11, and further adding hydrogen peroxide or percarboxylic acid to dilute acetic acid. Phosphoric acid compound to a concentration of 1 to 1100pp against
A method for decolorizing dilute acetic acid characterized by adding N or an alkali metal salt or alkaline earth metal salt thereof.
以下に本発明の「稀酢酸の脱色方法」を８１ Ｌ ＜説
明する。The "method for decolorizing dilute acetic acid" of the present invention will be explained below.
本発明のポイントは、もともとＡ Ｐ Ｉｆ Ａの値か
大なる、すなわち、品質の悪い稀酢酸の品質を改善する
ため、および、品質の良い稀酢酸の外観（Ａ Ｐ ＨＡ
）を放：η中にも一定範囲内に保つため、過カルボン
酸または過酸化水素のような過酸化物を１００〜２５０
０ｐｐｍ添加し、さらに、過酸化物に対して１〜１１０
０ｐｐのリン酸系化合物を添加するところにある。The point of the present invention is to improve the quality of dilute acetic acid of poor quality by originally having a large value of A P If A, and to improve the appearance of dilute acetic acid of good quality (A P HA
) to maintain a certain range during release: η, a peroxide such as percarboxylic acid or hydrogen peroxide is added to
Added 0 ppm and further added 1 to 110 ppm to peroxide.
This is where 0pp of phosphoric acid compound is added.
本発明は、特に、過酢酸を用いて酸化反応を行なうプラ
ントにおいて生成する酢酸を含んだ■液から精製して得
た回収稀酢酸に、１００〜２５００ｐｐｍ濃度になるよ
うに過カルボン酸または過酸化水素のような過酸化物を
添加し、さらに過カルボン酸または過酸化水素に対して
１〜１００Ｐｐ ｎ＋のリン酸系化合物を添加すること
によって回収稀酢酸の外観（Ａ Ｐ ＨＡ ’）の向上
を計るとともに、良好な外観を有する稀酢酸の安定的な
製造を可能とし、さらに、品質の保全手段として優れた
方法である。In particular, the present invention is directed to adding percarboxylic acid or peroxidation to the recovered dilute acetic acid obtained by purifying the acetic acid-containing solution produced in a plant that performs an oxidation reaction using peracetic acid to a concentration of 100 to 2,500 ppm. The appearance (A P HA') of recovered dilute acetic acid can be improved by adding a peroxide such as hydrogen and further adding a phosphoric acid compound of 1 to 100 Pp n+ per percarboxylic acid or hydrogen peroxide. This method enables the stable production of dilute acetic acid with a good appearance, and is also an excellent method for maintaining quality.
ここで脱色処理の対象となる稀酢酸の原料■凍となる副
生物は、エポキシ化大豆油やエポキシ化亜麻仁油のよう
なエポキシ化植物油、アリルアルコールを主原料とする
グリセリン製造プロセスなど、過酢酸を用いた酸化反応
プラントから副生ずる酢酸である。The raw material for dilute acetic acid that is subject to the decolorization process. The by-products that are frozen include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil, and peracetic acid, such as glycerin manufacturing processes that use allyl alcohol as the main raw material. Acetic acid is a by-product from an oxidation reaction plant using
上記の副生酢酸中には適用されるプロセスによって異な
るが、水、蟻酸、プロピオン酸、酢酸メチル、アクリル
酸、アクリル酸エチルなどの不純物が含まれてくる。The above-mentioned by-product acetic acid contains impurities such as water, formic acid, propionic acid, methyl acetate, acrylic acid, and ethyl acrylate, depending on the applied process.
これらの不純物が含まれている副生＃酸は通常蒸留、抽
出などの操作を組み合わせて処理することによりこれら
の不純物を所定範囲まで除去し、回収稀酢酸として製品
化される。The by-product #acid containing these impurities is usually treated with a combination of operations such as distillation and extraction to remove these impurities to a predetermined range, and then it is commercialized as recovered dilute acetic acid.
以上のような組み合わせ操作で回収された稀酢酸の外観
（Ａ Ｐ ｌ−Ｉ Ａ ）は種々の条件によって変動し
た状態で得られる。The appearance of the dilute acetic acid (A P l-I A ) recovered by the above combination operations varies depending on various conditions.
さらにこのＡＰＨＡの値は放置しておくと経時的に増加
する。Furthermore, if left untreated, the APHA value will increase over time.
すなわち、稀酢酸の品質が悪化するということである。In other words, the quality of dilute acetic acid deteriorates.
本発明で用い得る過酸化物の中で先ず過カルボン酸の具
体的な事例としては過＠酸、過ｉ’ｒｔ酸、過プロピオ
ン酸、過室２ｇ、香酸などがある。Among the peroxides that can be used in the present invention, specific examples of percarboxylic acids include per@acid, peri'rt acid, perpropionic acid, peroxyacid, and aromatic acid.
中でも本発明の処理の対象となる稀酢酸の発生プロセス
において過酢酸を用いており、また、希酢酸が水と酢酸
を主成分としているため、過酢酸を用いるのが最も理に
適っている。Among them, peracetic acid is used in the process of generating dilute acetic acid, which is the target of the treatment of the present invention, and since dilute acetic acid has water and acetic acid as its main components, it is most logical to use peracetic acid.
その理由は前記の反応式から明らかなように、脱色処理
に用いた過酢酸の分解により生成する酢酸も稀酢酸中の
有効成分となるからである。The reason for this is that, as is clear from the above reaction formula, acetic acid produced by decomposition of peracetic acid used in the decolorization treatment also becomes an active ingredient in dilute acetic acid.
本発明の方法に用い得るもう一つの過酸化物としては過
酸化水素がある。Another peroxide that can be used in the method of the invention is hydrogen peroxide.
また、過酸化物と併用するリン酸系化合物としてはオル
トリン酸、メタリン酸、ピロリン酸、トリポリリン酸、
２−エチルヘキシルトリポリリン酸およびそれらのアル
カリ金属ｔｉｔたはアルカリ土類金属塩がある。In addition, phosphoric acid compounds used in combination with peroxide include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid,
2-ethylhexyl tripolyphosphoric acid and their alkali metal or alkaline earth metal salts.
過酸化物の添加量は処理の対象となる稀酢酸に対して１
００〜２５００ ｐ ｐ ｍが好適である。The amount of peroxide added is 1 per dilute acetic acid to be treated.
00 to 2500 ppm is suitable.
添加量が１１００ＰＰより少ないと、外観（Ａ）） Ｈ
Ａ ）の向上が充分には計れない。If the amount added is less than 1100PP, the appearance (A)) H
The improvement in A) cannot be fully measured.
また、添加量を２５００ｐｐｍより多くしても稀酢酸中
に含まれる不純物が過酸１ヒ物を消費しきれないため残
存過酸化物濃度が高くなり、製品品質上好ましくない。Furthermore, even if the amount added is greater than 2,500 ppm, the impurities contained in dilute acetic acid will not be able to fully consume the peroxide, resulting in a high residual peroxide concentration, which is unfavorable in terms of product quality.
添加量は、回収稀酢酸の外１１１１（ＡＰＨＡ）によっ
て任意に決められるが、通常は２５００ｐｐｍより多い
と残存過酸化物濃度が高くなるだけでなく、固型物が生
成したりすることもあるので好ましくない。The amount added can be determined arbitrarily according to the recovered dilute acetic acid 1111 (APHA), but normally, if it is more than 2500 ppm, not only will the residual peroxide concentration become high, but also solid substances may be generated. Undesirable.
また、併用するリン酸系化合物は過酸化物に対してｌｐ
ｐｍ〜１００ ｐ ｐ ｍ程度の濃度になるように添加
するのが有効である。In addition, the phosphoric acid compound used in combination is lp for peroxide.
It is effective to add it to a concentration of about pm to 100 ppm.
併用するリン酸系化合物の添加量がｉｐｐｍより少ない
場合、併用しても効果は発揮されず、１１００ｐｐより
多くしても製品に対する悪影響が出てくる場合があるの
で好ましくない。If the amount of the phosphoric acid compound used in combination is less than ippm, no effect will be exhibited even if it is used in combination, and if it is more than 1100 ppm, it may have an adverse effect on the product, which is not preferable.
過酸化物および併用されるリン酸系化合物との添加の順
序は特に制限される訳ではなく、両名をあらかじめ混合
しておいても良いし、別々にどちらを先に添加しても良
い。The order of addition of the peroxide and the phosphoric acid compound used in combination is not particularly limited, and both may be mixed in advance, or either may be added separately first.
なお、リン酸系化合物は過カルボン酸および過酸化水素
水の安定剤として過カルボン酸および過酸化水素水の製
造工程、または、運搬・っ保管中にも用いられている。Note that phosphoric acid compounds are used as stabilizers for percarboxylic acids and hydrogen peroxide solutions in the manufacturing process of percarboxylic acids and hydrogen peroxide solutions, and during transportation and storage.
［発明の効果］
本発明の脱色方法によれば、過酢酸を用いた酸化プラン
１−から副生ずる酢酸から回収される稀酢酸の外観、特
に、着色度合い（Ａ ＰＨＡ ＞を良好に保つことがで
きる。[Effects of the Invention] According to the decolorization method of the present invention, it is possible to maintain a good appearance, especially the degree of coloration (A PHA >) of dilute acetic acid recovered from acetic acid by-produced from oxidation plan 1- using peracetic acid. can.
したがって、稀酢酸の用途を制限されずに用いることが
できる。Therefore, dilute acetic acid can be used without any restrictions.
次に本発明の稀酢酸の脱色方法を実施例により説明する
が、本発明が以下の実施例に限定されるものではない。Next, the method for decolorizing dilute acetic acid of the present invention will be explained with reference to examples, but the present invention is not limited to the following examples.
「実施例−１」
過酢酸の３０％酢酸エチル溶液、アリルアルコール、お
よび水をモル比で過Ｉ！ｌｌ：酸／アリルアルコール／
水−１／１．３／２５になるように調′膓して同時に仕
込み、約１２０ ’Ｔ’ ｏ ｒ ｒの減圧下２０〜９
０°Ｃで酢酸エチルを留去しながら約１時間反応を行な
いグリセリンを合成した。"Example-1" A 30% solution of peracetic acid in ethyl acetate, allyl alcohol, and water were mixed in a molar ratio of peracetic acid! ll: acid/allylic alcohol/
Water - Adjust to 1/1.3/25 and add at the same time, and boil under reduced pressure of about 120'
The reaction was carried out for about 1 hour while ethyl acetate was distilled off at 0°C to synthesize glycerin.
得られたグリセリン粗液の低沸点成分を約１１４°Ｃで
留去さぜ、さらに約１１０℃で低沸点成分を精製するこ
とにより表−１に示される回収希酢酸を得た。The low boiling point components of the obtained glycerin crude liquid were distilled off at about 114°C, and the low boiling point components were further purified at about 110°C to obtain recovered dilute acetic acid shown in Table 1.
なお、回収された酢酸は生成したグリセリン１モルに対
して約７５モル％の１であった９表−１
回収稀＃酸の組成と外観（Ａ Ｐｌｌ Ａ ）表−１に
示されるような組成比を有する回収稀酢酸に対して６０
％過酸化水素水を５００ｐｐｍになるように添加して２
時間放置後測定した結果、外観（Ａ Ｐ ＨＡ ＞は２
３まで向上した。In addition, the recovered acetic acid was approximately 75 mol % 1 based on 1 mol of glycerin produced. 9 Table-1 Composition and appearance of recovered dilute acid (A Pll A) 60 to recovered dilute acetic acid with a ratio of
% hydrogen peroxide solution to 500 ppm.
As a result of measurement after standing for a period of time, the appearance (A P HA > is 2
It improved to 3.
これを室内暗所で３週間放置した後も外ｆｉｔ！＜ＡＰ
ＨＡ ）は３３であった。Even after leaving this indoors in a dark place for 3 weeks, it still fits outside! <AP
HA) was 33.
用いた６０％過酸化水素水は、予め、ピ１′？リン酸カ
リウムが過酸化水素に対して１０ ｐ ｌ） ｒ口添加
されたものであった。The 60% hydrogen peroxide solution used was preliminarily prepared with P1'? Potassium phosphate was added to the hydrogen peroxide in an amount of 10 pl).
なお、Ａ Ｐ ）−Ｉ Ａ測定はＡＳＴＭ （Ａｍｅ
ｒ ｉ ｃａｎ ５ｏｃｉｅｔｙ ｆｏｒ Ｔｅ
ｓｔｉｎｇＭａｔｅｒｉａｌｓ）Ｄ １２０９（
１９８０年版） Ｓｔ、ａｎｄａｒｄ ’Ｉ”ｅｓ
ｔ Ｍｅｔｂｏｄ ｆｏｒ ｃｏｌｏｒ ｌｉ
ｑｕｉｄｓ（ｐｌａｔｉｎｕｍ、ｃｏｂａｌｔ ５ｃ
ａｌｅ）に基づいて実施した。In addition, the A P )-I A measurement is performed according to ASTM (Ame
r i can 5ociety for Te
stingMaterials) D 1209 (
1980 edition) St, andard 'I”es
t Metbod for color li
quids (platinum, cobalt 5c
ale).
「実施例−２」
回収稀酢酸に過酢酸を２５００ｐｐｍ添加した以外は実
施例−１と同じ条件で処理を行い、以下のような結果を
得た。"Example-2" The treatment was carried out under the same conditions as in Example-1 except that 2500 ppm of peracetic acid was added to the recovered dilute acetic acid, and the following results were obtained.
なお、過酢酸中には、予め、２−エチルヘキシルトリポ
リリン酸ソーダーが過酢酸に対して７０ｐ ｐ ｒｎに
なるように調整して添加した。Note that sodium 2-ethylhexyl tripolyphosphate was added to the peracetic acid in advance at a concentration of 70 p p rn relative to the peracetic acid.
外観＜ Ａ Ｐ ＨＡ ＞は、２５まで向上し、室内暗
所で３＃間放置した後も外Ｉｔｌｌ （Ａ Ｐ ＨＡ
）は１８であった。Appearance <AP HA> improved to 25, and even after being left indoors in a dark place for 3 days, it remained outside (AP HA).
) was 18.
「実施例−３」
回収稀１Ｉｌｌ：酸に６０％過酸化水素水を１ ｏｏｏ
ｐＰ １１１添加した以外は、実施例−１と同じ条件で
処理して以下のような結果をな。"Example-3" Recovery rare 1Ill: Add 60% hydrogen peroxide solution to acid 1ooo
The treatment was carried out under the same conditions as in Example 1, except that pP 111 was added, and the following results were obtained.
外Ｈ（Ａ Ｐ ＨＡ ）は、１７まで向上し、室内暗所
でｌＩ Ｅ１間放置した？裔も、外観（Ａｌ）ＩＩＡ＞
は１９あった。Outside H (APHA) improved to 17 and was left indoors in a dark place for 1 hour? Descendants, appearance (Al) IIA>
There were 19.
「比較例−１」
回１！ｙ、稀酢酸に、過酢酸を５０ Ｐ Ｐ Ｉｎ添加
した以外は実施例−２と同じ条件で処理を行い、以下の
ような結果を得た。“Comparative Example-1” 1st time! y. The treatment was carried out under the same conditions as in Example 2, except that 50 P P In of peracetic acid was added to dilute acetic acid, and the following results were obtained.
外ｍ１（Ａ Ｐ ＨＡ ） ハ、５５で、室内開所で４
０間放置した後も、外観（Ａ Ｐ Ｉｔ Ａ ）は６ｏ
であった。Outside m1 (AP HA) Ha, 55, indoor opening 4
Even after leaving it for 0 minutes, the appearance (A P It A) remains 6o.
Met.
［比較例−２ｊ
回収稀酢酸に、過酸化水素）Ｋを５０ ｐ ｐｍ添加し
た以外は実施例−１と同じ条１′１で処理を行い、以ド
のような結果を得た。Comparative Example 2j The same procedure as in Example 1 was carried out except that 50 ppm of K (hydrogen peroxide) was added to the recovered dilute acetic acid, and the following results were obtained.
外１！！！（ＡＰＨＡ）は、５５で、室内暗所で’ｌ
Ｅ１間放置した後も、外観（Ａ Ｐ ＨＡ ＞は５５で
あった。Outside 1! ! ! (APHA) is 55 and indoors in the dark.
Even after being left for E1, the appearance (A P HA > was 55).
「実施例−１」、「実施例−２」、「実施例３」で得ら
れた結果から、所定の濃度の過酸化物とリン酸系化合物
を添加しておけばＡ Ｐ ｌ−Ｉ Ａの値が一時的に改
善されるだけでなく、放置しておいてもＡＰＩＩＡｇｉ
はほとんど増加していくことはなく、本発明の方法が回
収稀酢酸の品質管理上有効であることが明らかである。From the results obtained in "Example-1", "Example-2", and "Example 3", if peroxide and phosphoric acid compound are added at predetermined concentrations, A P l-I A Not only does the value of APIIAgi improve temporarily, but even if left alone, APIIAgi
It is clear that the method of the present invention is effective for quality control of recovered dilute acetic acid.
一方、「比較例−１」および「比較例−２」で得られた
結果から、添加する過酸化物の濃度が１００ ｐ ｐ
Ｉｎより少ない場合には効果がないだけでなく、放置し
ておくとＡ Ｐ Ｉ（Ａ値が増加、すなわち、品質が悪
化していくことが明らかである。On the other hand, from the results obtained in "Comparative Example-1" and "Comparative Example-2", it was found that the concentration of added peroxide was 100 p p
It is clear that if the amount is less than In, not only is there no effect, but if left as is, the A value increases, that is, the quality deteriorates.
Claims (1)
うに過酸化水素または過カルボン酸を添加し、さらに、
該過酸化水素水または過カルボン酸に対して１〜１００
ｐｐｍの濃度になるようにリン酸系化合物またはそれら
のアルカリ金属塩またはアルカリ土類金属塩を添加する
ことを特徴とする稀酢酸の脱色方法。Add hydrogen peroxide or percarboxylic acid to a concentration of 100 to 2500 ppm relative to dilute acetic acid, and further,
1 to 100 for the hydrogen peroxide solution or percarboxylic acid
A method for decolorizing dilute acetic acid, which comprises adding a phosphoric acid compound or an alkali metal salt or alkaline earth metal salt thereof to a concentration of ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28737988A JPH07107013B2 (en) | 1988-11-14 | 1988-11-14 | Decolorization method of dilute acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28737988A JPH07107013B2 (en) | 1988-11-14 | 1988-11-14 | Decolorization method of dilute acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02134342A true JPH02134342A (en) | 1990-05-23 |
| JPH07107013B2 JPH07107013B2 (en) | 1995-11-15 |
Family
ID=17716593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28737988A Expired - Lifetime JPH07107013B2 (en) | 1988-11-14 | 1988-11-14 | Decolorization method of dilute acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07107013B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387713A (en) * | 1991-01-05 | 1995-02-07 | Bp Chemicals Limited | Process for purification of carboxylic acids |
-
1988
- 1988-11-14 JP JP28737988A patent/JPH07107013B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5387713A (en) * | 1991-01-05 | 1995-02-07 | Bp Chemicals Limited | Process for purification of carboxylic acids |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07107013B2 (en) | 1995-11-15 |
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