JPH0791206B2 - Process for producing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt octahydrate - Google Patents
Process for producing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt octahydrateInfo
- Publication number
- JPH0791206B2 JPH0791206B2 JP62003231A JP323187A JPH0791206B2 JP H0791206 B2 JPH0791206 B2 JP H0791206B2 JP 62003231 A JP62003231 A JP 62003231A JP 323187 A JP323187 A JP 323187A JP H0791206 B2 JPH0791206 B2 JP H0791206B2
- Authority
- JP
- Japan
- Prior art keywords
- ddan
- aqueous solution
- octahydrate
- dihydro
- disodium salt
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paper (AREA)
Description
【発明の詳細な説明】 「産業上の利用分野」 本発明は、パルプ蒸解助剤及び化学品中間原料として有
用は1,4−ジヒドロ−9,10−ジヒドロキシアントラセン
ジナトリウム塩（以下、1,4−ジヒドロ−9,10−ジヒド
ロキシアントラセンをDDA、そのジナトリウム塩をDDAN
と略記する。）の新規な水化物及びその製造法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION “Industrial field of application” The present invention is useful as a pulp cooking aid and an intermediate raw material for chemicals, 1,4-dihydro-9,10-dihydroxyanthracene disodium salt (hereinafter, 1, 4-dihydro-9,10-dihydroxyanthracene is DDA and its disodium salt is DDAN
Is abbreviated. ) New hydrate and its manufacturing method.
「従来の技術」 近年、DDA（1,4−ジヒドロアントラヒドロキノンともい
う。）ジナトリウム塩水溶液（以下、DDAN水溶液とい
う。）は、パルプ蒸解助剤として、日本及び外国でも大
量に使用されるようになってきた。"Prior Art" In recent years, DDA (also referred to as 1,4-dihydroanthrahydroquinone) disodium salt aqueous solution (hereinafter referred to as DDAN aqueous solution) is used as a pulp cooking aid in large amounts in Japan and abroad. Has become.
「発明が解決しようとする問題点」 しかしながら、従来使用されているこのDDAN水溶液は、
ユーザーであるパルプ製造工場が比較的寒冷地に存在す
る関係から、貯蔵時に結晶の析出を避ける程度の濃度、
一般には約20％の水溶液で取り扱われていることもあっ
て、単位重量当たりの輸送費及び貯蔵費が高くつき、又
空気に接触すると酸化されて不溶性のキノン型になり沈
澱するなど、多くの問題点があった。"Problems to be solved by the invention" However, this conventionally used DDAN aqueous solution is
Due to the fact that the pulp mill, which is the user, is located in a relatively cold region, a concentration that prevents the precipitation of crystals during storage,
Generally, it is handled as an aqueous solution of about 20%, so that the transportation and storage costs per unit weight are high, and when it comes into contact with air, it is oxidized and becomes an insoluble quinone type, which causes precipitation. There was a problem.
本発明は、上記の従来の問題点を解決し得る、未だ全く
知られていない取り扱いの容易な固体のDDAN水化物結晶
及びその製造法の提供を目的とする。It is an object of the present invention to provide a solid DDAN hydrate crystal which can solve the above-mentioned conventional problems and which has not been known yet and which is easy to handle and a method for producing the same.
「問題点を解決するための手段」 本発明者らは、かかる目的を達成すべく鋭意研究を進め
た結果、DDAN水溶液から晶析せしめることによって、新
規で取り扱い容易かつ空気に対し従来の水溶液よりも安
定なDDAN八水化物結晶が得られることを始めて見いだ
し、本発明に到達した。すなわち、本発明は、1,4−ジ
ヒドロ−9,10−ジヒドロキシアントラセンジナトリウム
塩（DDAN）水化物、好ましくはDDAN八水化物、並びに、
DDAN水溶液を冷却晶析すること、好ましくはナフトキノ
ンとブタジエンとのディールス・アルダー反応により得
られた1,4,4a,9a−テトラヒドロアントラキノンを水酸
化ナトリウム水溶液により抽出したDDAN水溶液を冷却晶
析することを特徴とするDDAN水化物の製造法にある。“Means for Solving Problems” The inventors of the present invention have conducted earnest research to achieve such an object, and as a result, by crystallizing from a DDAN aqueous solution, it is new and easy to handle, and is more air-friendly than a conventional aqueous solution. For the first time, they have found that stable DDAN octahydrate crystals can be obtained, and reached the present invention. That is, the present invention provides 1,4-dihydro-9,10-dihydroxyanthracene disodium salt (DDAN) hydrate, preferably DDAN octahydrate, and
Cooling and crystallizing the DDAN aqueous solution, preferably cooling and crystallizing the DDAN aqueous solution obtained by extracting 1,4,4a, 9a-tetrahydroanthraquinone obtained by the Diels-Alder reaction of naphthoquinone and butadiene with an aqueous sodium hydroxide solution. The method for producing a DDAN hydrate is characterized by
本発明のDDAN水化物は、DDANの水溶液を冷却晶析する温
度によって、その水化物の結晶水の量が若干異なるが実
用的には約40℃以下に冷却することにより一般に八水化
物が得られる。The DDAN hydrate of the present invention has a slightly different amount of water of crystallization of the hydrate depending on the temperature at which the DDAN aqueous solution is cooled and crystallized, but practically, the octahydrate is generally obtained by cooling the hydrate to about 40 ° C. or less. To be
このDDAN水化物を得るためのDDANの水溶液は、一般に次
のような公知の方法で製造することができる。The aqueous solution of DDAN for obtaining this DDAN hydrate can be generally produced by the following known method.
1,4−ナフトキノンとフダジエンとを溶媒の存在下又は
不存在下でディールス・アルダー反応させる常法に従っ
て付加反応させ、その付加物（いわゆる1,4,4a,9a−テ
トラヒドロアントラキノン）を水酸化ナトリウム水溶液
で、酸素不存在下70〜150℃、好ましくは80〜100℃、約
10分〜２時間、通常は撹拌下で処理する。このとき、1,
4,4a,9a−テトラヒドロアントラキノンはDDAに異性化す
ると同時にDDANとなって溶解し、その水溶液が得られ
る。1,4-naphthoquinone and fudadiene are subjected to an addition reaction according to a conventional method of Diels-Alder reaction in the presence or absence of a solvent, and the addition product (so-called 1,4,4a, 9a-tetrahydroanthraquinone) is converted into sodium hydroxide. Aqueous solution in the absence of oxygen 70-150 ℃, preferably 80-100 ℃,
Process for 10 minutes to 2 hours, usually with stirring. At this time, 1,
4,4a, 9a-Tetrahydroanthraquinone is isomerized to DDA and at the same time dissolves as DDAN to obtain an aqueous solution thereof.
上記のディールス・アルダー反応は、一般には溶媒の存
在下で行われ、その溶媒としては非水混和性のものが溶
媒の回収の上から好ましい。例えば、ベンゼン、トルエ
ン、オルソキシレン等の芳香族炭化水素、クロロベンゼ
ン等のベンゼン誘導体、その他脂肪族炭化水素やその誘
導体が挙げられる。The above-mentioned Diels-Alder reaction is generally carried out in the presence of a solvent, and a non-water-miscible solvent is preferable in terms of recovery of the solvent. Examples thereof include aromatic hydrocarbons such as benzene, toluene, orthoxylene, benzene derivatives such as chlorobenzene, and other aliphatic hydrocarbons and their derivatives.
本発明においては、このDDAN水溶液に不純物、特にナフ
タレンの接触気相酸化反応によって得られる1,4−ナフ
トキノンを使用することによる不純物や一部酸化された
アントラセン化合物、例えばアントラヒドロキノンのナ
トリウム塩が溶解していても差し支えない。In the present invention, impurities in this DDAN aqueous solution, in particular impurities by using 1,4-naphthoquinone obtained by catalytic gas phase oxidation reaction of naphthalene and partially oxidized anthracene compound, for example, sodium salt of anthrahydroquinone is dissolved. You can do it.
この場合上記の水酸化ナトリウム水溶液中の水酸化ナト
リウムの使用量は、1,4,4a,9a−テトラヒドロアントラ
キノン又はDDAに対して約２モル倍以上、一般に約２〜
４モル倍、好ましくは約2.0〜2.5モル倍、さらに好まし
くは2.1〜2.2モル倍がよい。このとき使用する水酸化ナ
トリウムの水溶液の濃度は、操作温度におけるDDANの溶
解度以下になるような濃度から選ばれるが、一般的に約
15％以上、好ましくは約18〜約30％から選ばれる。In this case, the amount of sodium hydroxide used in the aqueous sodium hydroxide solution is about 2 mol times or more, generally about 2 to 1,4,4a, 9a-tetrahydroanthraquinone or DDA.
The molar ratio is 4 times, preferably about 2.0 to 2.5 times, more preferably 2.1 to 2.2 times. The concentration of the aqueous solution of sodium hydroxide used at this time is selected from the concentration not exceeding the solubility of DDAN at the operating temperature.
It is selected from 15% or more, preferably about 18 to about 30%.
かくして得られるDDANの水溶液は、一般に約30〜約58％
である。The aqueous DDAN solution thus obtained is generally about 30 to about 58%.
Is.
このDDAN水溶液から本発明のDDAN水化物の製造は、該水
溶液を、約70〜90℃から撹拌下又は無撹拌下に徐冷して
約40℃以下、好ましくは30℃以下に冷却してDDAN水化物
を晶析させ、過又は遠心分離機等で分離することによ
って容易に達成される。必要ならば、分離されたDDAN水
化物をウエット状態でも、晶析した状態のまま貯蔵、搬
送することができる。The DDAN hydrate of the present invention can be produced from this DDAN aqueous solution by slowly cooling the aqueous solution from about 70 to 90 ° C with or without stirring to about 40 ° C or less, preferably 30 ° C or less. This is easily achieved by crystallizing the hydrate and separating it with a filter or a centrifugal separator. If necessary, the separated DDAN hydrate can be stored and transported in a crystallized state even in a wet state.
分離された液は循環使用することもできるが、不純物
の蓄積に応じ一部を抜き出して空気酸化することによ
り、DDANをアントラキノンとして回収することもでき
る。The separated liquid can be recycled, but DDAN can be recovered as anthraquinone by extracting a part of the liquid according to the accumulation of impurities and subjecting it to air oxidation.
「実施例」 次に、実施例により、本発明を更に具体的に説明する。
なお本明細書中、「％」は特に断わらない限り重量によ
るものである。"Examples" Next, the present invention will be described in more detail with reference to Examples.
In this specification, “%” is based on weight unless otherwise specified.
実施例１ 1,4,4a,9a−テトラヒドロアントラキノンの50gを含む10
％オルソキシレン溶液を、窒素ガス気流中で、撹拌機、
底部に抜き出しコック及び加熱装置を備えたガラス製反
応器に採り、さらに撹拌下、水酸化ナトリウム20.5gと
水99.5gとからなる水溶液を加えた後、90℃で30分間中
和反応を行った。Example 1 Containing 50 g of 1,4,4a, 9a-tetrahydroanthraquinone 10
% Ortho-xylene solution in a nitrogen gas stream with a stirrer,
It was taken in a glass reactor equipped with an extraction cock and a heating device at the bottom, and further, while stirring, an aqueous solution consisting of 20.5 g of sodium hydroxide and 99.5 g of water was added, and then a neutralization reaction was carried out at 90 ° C. for 30 minutes. .
反応後、撹拌下26℃まで冷却し、DDAN水化物を晶析せし
めた。この結晶を窒素ガス雰囲気下で硝子製過器を用
いて別し、さらに結晶の上から窒素ガス気流を通し
紙上で付着水を除去し、窒素ボックス中で乾燥しオレン
ジ色精糖状の結晶29gを得た。After the reaction, the mixture was cooled to 26 ° C. with stirring to crystallize DDAN hydrate. The crystals were separated using a glass filter under a nitrogen gas atmosphere, and water adhering to the paper was removed by passing a nitrogen gas stream over the crystals, and dried in a nitrogen box to give orange-refined sugar-like crystals (29 g). Obtained.
得られた結晶の一部を採り、KF05型カールフィッシャー
法（酸化されない状態で結晶水分が測定される。）によ
りこの結晶中の結晶水量を測定したところ36％であり、
八水塩としての含有量を示した。A part of the obtained crystal was taken, and the amount of water of crystallization in this crystal was measured by the KF05 type Karl Fischer method (the water content of the crystal is measured in the state of not being oxidized).
The content as octahydrate is shown.
一方、同じ結晶7.915gを200mlのビーカーに採り、水約9
0gを加え、90℃に加熱した後、空気で十分に酸化し、ア
ントラキノン（以下、AQと略記する。）4.100gを得た。Meanwhile, take 7.915 g of the same crystal in a 200 ml beaker,
After adding 0 g and heating at 90 ° C., it was sufficiently oxidized by air to obtain 4.100 g of anthraquinone (hereinafter abbreviated as AQ).
この結晶をDDANの八水化物として、その分子式はC14H10
O2Na2−8H2Oであり、その中の酸化により理論的に得ら
れるアントラキノン（AQ）分子量の計算値のDDAN八水化
物結晶分子量の計算値に対する理論比をとると、AQ分子
量/DDAN八水化物分子量の理論比＝208/400＝0.520とな
る。This crystal is used as DDAN octahydrate, and its molecular formula is C 14 H 10
O 2 Na 2 −8H 2 O, and the theoretical ratio of the calculated molecular weight of anthraquinone (AQ) theoretically obtained by oxidation in it to the calculated molecular weight of DDAN octahydrate is calculated as AQ molecular weight / DDAN The theoretical ratio of molecular weight of octahydrate = 208/400 = 0.520.
これに対して、上記の酸化実験により得られたアントラ
キノン（AQ）分としての含量の原料DDAN水化物結晶の採
取量に対する実験比は、所得AQ/原料結晶＝4.100/7.915
＝0.518となり、実質的に上記の八水化物に対する理論
比と一致した。On the other hand, the experimental ratio of the content as anthraquinone (AQ) content obtained by the above oxidation experiment to the collected amount of the raw DDAN hydrate crystals was calculated as income AQ / raw crystal = 4.100 / 7.915
= 0.518, which is substantially in agreement with the above theoretical ratio for octahydrate.
実施例２ ナフタレンを接触気相酸化することにより生成した反応
生成ガスを水洗捕集して得たフタル酸と1,4−ナフトキ
ノンの水性スラリーからオルソキシレンで1,4−ナフト
キノンを抽出した。該1,4−ナフトキノン溶液を約80℃
の温水で洗浄し、得られた1,4−ナフトキノンのオルソ
キシレン溶液を使用して常法に従ってブタジエンとのデ
ィールス・アルダー反応を行った。反応終了後、過剰の
ブタジエンを留去して得た反応液（組成:1,4,4a,9a−テ
トラヒドロアントラキノン45.04g、不純物2.57g、オル
ソキシレン52.39g）の81.1gを反応器に採り、ついで19.
2％の水酸化ナトリウム水溶液106.3gを85℃で撹拌下に
加え、1,4,4a,9a−テトラヒドロアントラキノンをDDAN
として水層に完全に抽出し、オルソキシレンを分液し
た。得られたDDAN水溶液を、撹拌下、75℃から30℃まで
45分間（−１℃／分）を要して冷却、さらに30℃で５分
間撹拌しながら保持し、晶析した結晶を窒素ガス雰囲気
下で別し、赤色ルビー色の精糖状結晶54.9gを得た。Example 2 1,4-naphthoquinone was extracted with ortho-xylene from an aqueous slurry of phthalic acid and 1,4-naphthoquinone obtained by washing and collecting a reaction product gas generated by catalytic vapor-phase oxidation of naphthalene. The 1,4-naphthoquinone solution at about 80 ° C
The resulting solution of 1,4-naphthoquinone in ortho-xylene was used to carry out Diels-Alder reaction with butadiene according to a conventional method. After the reaction was completed, 81.1 g of a reaction solution obtained by distilling off excess butadiene (composition: 1,4,4a, 9a-tetrahydroanthraquinone 45.04 g, impurities 2.57 g, orthoxylene 52.39 g) was taken in a reactor, Then 19.
106.3 g of a 2% aqueous sodium hydroxide solution was added with stirring at 85 ° C., and 1,4,4a, 9a-tetrahydroanthraquinone was added to DDAN.
Was completely extracted into the aqueous layer, and orthoxylene was separated. The obtained DDAN aqueous solution is stirred to 75 ℃ to 30 ℃.
It takes 45 minutes (-1 ° C / min) to cool, and the mixture is kept at 30 ° C for 5 minutes with stirring, and the crystallized crystals are separated under a nitrogen gas atmosphere to give 54.9 g of red ruby-colored sugar-like crystals. Obtained.
この結晶の一部を採り、アルコール洗いしたのち、実施
例１と同様に分析してDDAN八水化物であることを確認し
た。A part of this crystal was collected, washed with alcohol, and analyzed in the same manner as in Example 1 to confirm that it was DDAN octahydrate.
実施例３ 実施例１及び２で得られたDDAN八水化物の各々100gを、
窒素ガス気流中にて各々300mlの四つ口フラスコに採
り、常温の脱酸素水160gを加え、撹拌しながら溶解させ
ると、完全に均一な20％DDAN水溶液が得られた。Example 3 100 g of each of the DDAN octahydrates obtained in Examples 1 and 2
In a nitrogen gas stream, each was placed in a 300 ml four-necked flask, 160 g of room temperature deoxidized water was added, and dissolved with stirring to obtain a completely uniform 20% DDAN aqueous solution.
この水溶液は従来のDDAN水溶液と同様にパルプ蒸解助剤
として有効であった。This aqueous solution was effective as a pulp cooking aid as well as the conventional DDAN aqueous solution.
「発明の効果」 本発明のDDAN八水化物は、新規な赤色ルビー状の結晶で
あり、従来の水溶液に比べて酸化に対する安定性がよ
く、固体状であることからタンク等の特殊な容器や運搬
上特別なタンクローリーを必要とせず、かつDDANの相対
的濃度が高いことによる運送費の軽減など、という工業
的価値ある顕著な効果を奏することができる。"Effects of the Invention" The DDAN octahydrate of the present invention is a novel red ruby-like crystal, has better stability against oxidation than conventional aqueous solutions, and has a solid state, so that it can be used in special containers such as tanks and the like. It does not require a special tank truck for transportation, and has a significant industrial value such as reduction of transportation cost due to high relative concentration of DDAN.
Claims (1)
トラセンジナトリウム塩の30〜58％水溶液を、70〜90℃
から徐冷して40℃以下に冷却して晶析することを特徴と
する1,4−ジヒドロ−9,10−ジヒドロキシアントラセン
ジナトリウム塩八水化物の製造法。1. A 30 to 58% aqueous solution of 1,4-dihydro-9,10-dihydroxyanthracene disodium salt at 70 to 90 ° C.
A method for producing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt octahydrate, characterized by comprising slowly cooling to 40 ° C. or lower and crystallizing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62003231A JPH0791206B2 (en) | 1987-01-12 | 1987-01-12 | Process for producing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt octahydrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62003231A JPH0791206B2 (en) | 1987-01-12 | 1987-01-12 | Process for producing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt octahydrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63174943A JPS63174943A (en) | 1988-07-19 |
| JPH0791206B2 true JPH0791206B2 (en) | 1995-10-04 |
Family
ID=11551675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62003231A Expired - Fee Related JPH0791206B2 (en) | 1987-01-12 | 1987-01-12 | Process for producing 1,4-dihydro-9,10-dihydroxyanthracene disodium salt octahydrate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791206B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57191389A (en) * | 1981-03-23 | 1982-11-25 | Kanzaki Paper Mfg Co Ltd | Recovery of digesting aid |
| JPS57171933A (en) * | 1981-04-16 | 1982-10-22 | Kawasaki Kasei Chem Ltd | Preparation of aqueous solution of alkali salt of 1,4- dihydroanthrahydroquinone as pulp digesting assistant |
| JPS6197492A (en) * | 1984-10-18 | 1986-05-15 | 川崎化成工業株式会社 | High concentrated pulp digestion aid aqueous solution |
-
1987
- 1987-01-12 JP JP62003231A patent/JPH0791206B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63174943A (en) | 1988-07-19 |
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