JPH0455184B2 - - Google Patents
Info
- Publication number
- JPH0455184B2 JPH0455184B2 JP58242151A JP24215183A JPH0455184B2 JP H0455184 B2 JPH0455184 B2 JP H0455184B2 JP 58242151 A JP58242151 A JP 58242151A JP 24215183 A JP24215183 A JP 24215183A JP H0455184 B2 JPH0455184 B2 JP H0455184B2
- Authority
- JP
- Japan
- Prior art keywords
- dioxyanthraquinone
- alkali metal
- crude
- weight
- temperature
- 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 - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 238000003916 acid precipitation Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- -1 alkali metal salt Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims 3
- 239000012065 filter cake Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 9
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は２，６−ジオキシアントラキノンの高
純度品の製造に関するものであり、特に１，２，
６−トリオキシアントラキノンを含有する粗２，
６−ジオキシアントラキノンの精製方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of highly purified 2,6-dioxyanthraquinone, particularly 1,2,
Crude 2, containing 6-trioxyanthraquinone
The present invention relates to a method for purifying 6-dioxyanthraquinone.
２，６−ジオキシアントラキノンは、染料中間
体のほか耐熱性合成樹脂原料などに用いられてい
る。 2,6-dioxyanthraquinone is used as a dye intermediate and as a raw material for heat-resistant synthetic resins.
２，６−ジオキシアントラキノンの製造方法
は、古くより知られており、たとえばドイツ特許
106505などに記載されているように、通常、アン
トラキノン２，６ジスルホン酸アルカリ金属塩を
水酸化カルシウム水溶液（消石灰水）に加え、加
圧下170〜180℃で24〜30Hrかきまぜて、反応物
を水に投入し、濃塩酸と煮沸し、過、水洗して
２，６−ジオキシアントラキノンの粗製物が得ら
れている。 The method for producing 2,6-dioxyanthraquinone has been known for a long time, for example in the German patent
106505, anthraquinone 2,6 disulfonic acid alkali metal salt is usually added to an aqueous calcium hydroxide solution (slaked lime water) and stirred under pressure at 170 to 180°C for 24 to 30 hours to dissolve the reactant into water. The crude product of 2,6-dioxyanthraquinone was obtained by boiling with concentrated hydrochloric acid, filtering, and washing with water.
しかしながら、こうして得られた粗製物中には
不純物として微量の未反応のアントラキノン２，
６ジスルホン酸や、アントラキノン−２−ヒドロ
キシ−６−スルホン酸などの副生物の外に、少量
の１，２，６トリオキシアントラキノンを含有し
ており純度は85〜90％と低い。 However, the crude product thus obtained contained trace amounts of unreacted anthraquinone 2,
In addition to by-products such as 6-disulfonic acid and anthraquinone-2-hydroxy-6-sulfonic acid, it contains a small amount of 1,2,6-trioxyanthraquinone, and its purity is as low as 85-90%.
これらの不純物は出来得るかぎり除去する必要
があり、特に合成樹脂の原料に用いる場合、１，
２，６−トリオキシアントラキノンは着色などの
原因となり商品価値を損なう。 These impurities need to be removed as much as possible, especially when used as raw materials for synthetic resins, 1.
2,6-trioxyanthraquinone causes coloring and impairs commercial value.
本発明者らは、粗２，６−ジオキシアントラキ
ノンの精製法について鋭意の検討の結果、経済的
に高収率で精２，６−ジオキシアントラキノンを
分離取得できることを見出し、本発明を完成した
ものである。 As a result of intensive studies on the purification method of crude 2,6-dioxyanthraquinone, the present inventors discovered that purified 2,6-dioxyanthraquinone can be economically separated and obtained in high yield, and completed the present invention. This is what I did.
すなわち、本発明は粗２，６−ジオキシアント
ラキノンを、５〜30重量％の濃度のアルカリ金属
水酸化物水溶液に加熱溶解し、ついで冷却して
２，６−ジオキシアントラキノンのアルカリ金属
塩として析出させて、これを10〜70℃で過分解
し、得られた塊を温水に溶解したのち、酸析分
解することを特徴とする２，６−ジオキシアント
ラキノンの精製方法である。 That is, in the present invention, crude 2,6-dioxyanthraquinone is heated and dissolved in an alkali metal hydroxide aqueous solution having a concentration of 5 to 30% by weight, and then cooled to form an alkali metal salt of 2,6-dioxyanthraquinone. This is a method for purifying 2,6-dioxyanthraquinone, which is characterized by precipitating it, overly decomposing it at 10 to 70°C, dissolving the obtained lump in hot water, and then subjecting it to acid precipitation decomposition.
特に本発明方法は、１，２，６−トリオキシア
ントラキノン不純物に対する除去効果は著しく、
５〜30％濃度範囲のアルカリ金属水酸化物におい
て２，６−ジオキシアントラキノンと、１，２，
６−トリオキシアントラキノンの溶解度差を利用
して分解するものである。すなわち１，２，６−
トリオキシアントラキノンの所定濃度のアルカリ
金属水酸化物水溶液中における溶解物は、２，６
−ジオキシアントラキノンより温度に対して鈍感
であり、したがつて所定濃度のアルカリ水溶液中
に加熱溶解させた粗製物を、温度変化させること
により、温度依存性の大きい２，６−ジオキシア
ントラキノンのみをアルカリ金属塩として選択的
に析出させることができ、この析出温度で固液分
解すれば、１，２，６−トリオキシアントラキノ
ンは、アントラキノン−２−ヒドロキシ−６−ス
ルホン酸などの不純物と一緒に母液に溶存させて
去できる。 In particular, the method of the present invention has a remarkable removal effect on 1,2,6-trioxyanthraquinone impurities.
2,6-dioxyanthraquinone and 1,2,
It decomposes using the solubility difference of 6-trioxyanthraquinone. i.e. 1, 2, 6-
The dissolved product of trioxyanthraquinone in an alkali metal hydroxide aqueous solution with a predetermined concentration is 2,6
- It is less sensitive to temperature than dioxyanthraquinone, so by changing the temperature of the crude product heated and dissolved in an alkaline aqueous solution of a predetermined concentration, only 2,6-dioxyanthraquinone, which has a large temperature dependence, can be used. can be selectively precipitated as an alkali metal salt, and if solid-liquid decomposition is performed at this precipitation temperature, 1,2,6-trioxyanthraquinone will be separated together with impurities such as anthraquinone-2-hydroxy-6-sulfonic acid. It can be dissolved in the mother liquor and removed.
次いで得られた２，６−ジオキシアントラキノ
ンアルカリ金属塩の塊を、温水中に溶解し、常
法に従い酸処理して酸析分解すれば、高純度の
２，６−ジオキシアントラキノンが得られる。 Next, the obtained lump of 2,6-dioxyanthraquinone alkali metal salt is dissolved in warm water and subjected to acid treatment and acid precipitation decomposition according to a conventional method to obtain highly pure 2,6-dioxyanthraquinone. .
本発明において、溶媒として用いられるアルカ
リ金属水酸化物は苛性カリ及び苛性ソーダであ
り、その水溶液の濃度は５〜30重量％、好ましく
は８〜20重量％である。この範囲外では、所定温
度での分解時に、２，６−ジオキシアントラキノ
ン金属塩の析出物に不純物が残存するので好まし
くない。アルカリ水溶液溶媒の使用量は、粗２，
６−ジオキシアントラキノンに対し５〜40倍量、
好ましくは10〜20倍量用い、粗２，６−ジオキシ
アントラキノンの加熱溶解時に一度に添加しても
よいが、粗製物を加熱溶解後に、逐次添加して、
溶解させた粗製物のアルカリ濃度を所定濃度に調
整してもよい。 In the present invention, the alkali metal hydroxides used as solvents are caustic potash and caustic soda, and the concentration of the aqueous solution thereof is 5 to 30% by weight, preferably 8 to 20% by weight. Outside this range, impurities remain in the precipitate of the 2,6-dioxyanthraquinone metal salt during decomposition at a predetermined temperature, which is not preferable. The amount of alkaline aqueous solvent used is roughly 2,
5 to 40 times the amount of 6-dioxyanthraquinone,
Preferably, 10 to 20 times the amount is used, and it may be added all at once when heating and dissolving the crude 2,6-dioxyanthraquinone, but it may be added sequentially after heating and dissolving the crude 2,6-dioxyanthraquinone.
The alkaline concentration of the dissolved crude product may be adjusted to a predetermined concentration.
粗製物の加熱溶解温度は、90℃以上に加熱して
もよいが通常は80〜85℃で30分程度加温すれば充
分である。完溶後は、10〜70℃以下、好ましくは
30〜50℃まで冷却放置すれば、２，６−ジオキシ
アントラキノン塩のみが析出するのでこの温度で
過する。過時の温度が10℃以下では塊に
１，２，６−トリオキシアントラキノンなどの不
純物が残存するので好ましくない。また70℃以上
の熱過では２，６−ジオキシアントラキノンの
ロスが多くなる。 The heating and dissolution temperature of the crude product may be heated to 90°C or higher, but heating at 80 to 85°C for about 30 minutes is usually sufficient. After complete dissolution, the temperature should be 10 to 70℃ or less, preferably
If left to cool to 30 to 50°C, only 2,6-dioxyanthraquinone salt will precipitate, so the temperature is maintained at this temperature. If the temperature is below 10°C, impurities such as 1,2,6-trioxyanthraquinone will remain in the mass, which is not preferable. Furthermore, heating at 70°C or higher results in a large loss of 2,6-dioxyanthraquinone.
分離された塊は次いでアルカリ水洗浄後、通
常70〜75℃の温水に溶解し、この温度で硫酸また
は塩酸を滴下して、PH2以下に調整して酸析後
分解する。 The separated lumps are then washed with alkaline water and then dissolved in warm water, usually at 70 to 75°C, and at this temperature sulfuric acid or hydrochloric acid is added dropwise to adjust the pH to below 2, followed by acid precipitation and decomposition.
このようにして得られた塊は場洗、乾燥すれ
ば、高純度の精２，６−ジオキシアントラキノン
が得られる。 The mass thus obtained is washed in place and dried to obtain purified 2,6-dioxyanthraquinone of high purity.
以下実施例により本発明を具体的に説明する。
％は重量％である。 The present invention will be specifically explained below using Examples.
% is by weight.
実施例 １
２，６−ジスルホン酸2.8％、モノオキシスル
ホン酸0.8％、１，２，６−トリオキシアントラ
キノン6.2％、その他無機物を微量含有する84％
純度の２，６−ジオキシアントラキノン100ｇを、
８％苛性ソーダ水溶液800ｇ中で撹拌下、80〜85
℃まで加熱溶解させ、さらに49％苛性ソーダ水溶
液を137ｇ添加後30〜35℃まで冷却して約1.5時間
放置した。得られた析出物をこの温度で固液分解
した後、塊を15％苛性ソーダ水溶液100c.c.を用
いて洗浄後、70℃の温水１中に溶解させた。次
いで50％硫酸をPH1〜２となるまで滴下し70〜
75℃で約0.5時間かきまぜ保温した。放冷後、
過、湯洗乾燥して、黄色の精２，６−ジオキシア
ントラキノン80ｇを得た。このものは純度が97％
であり、１，２，６−トリオキシアントラキノン
は１％以下、その他微量の不純物が含まれてい
た。Example 1 84% containing 2.8% 2,6-disulfonic acid, 0.8% monooxysulfonic acid, 6.2% 1,2,6-trioxyanthraquinone, and trace amounts of other inorganic substances
100g of pure 2,6-dioxyanthraquinone,
80-85 while stirring in 800g of 8% caustic soda aqueous solution
After heating and dissolving the mixture to 30°C, 137g of a 49% aqueous sodium hydroxide solution was added, and the mixture was cooled to 30 to 35°C and left for about 1.5 hours. After the obtained precipitate was subjected to solid-liquid decomposition at this temperature, the lump was washed with 100 c.c. of a 15% aqueous solution of caustic soda, and then dissolved in 70° C. hot water 1. Next, add 50% sulfuric acid dropwise until the pH reaches 70~2.
The mixture was stirred and kept warm at 75°C for about 0.5 hours. After cooling,
After filtering, washing with hot water and drying, 80 g of yellow pure 2,6-dioxyanthraquinone was obtained. This stuff is 97% pure
It contained less than 1% of 1,2,6-trioxyanthraquinone and trace amounts of other impurities.
実施例 ２
実施例１に用いたのと同じ粗２，６−ジオキシ
アントラキノン100ｇを、８％苛性ソーダ水溶液
1000ｇに添加して80℃に昇温、溶解した。次に実
施例１と同様30〜35℃に冷却、析出物の過及び
10％苛性ソーダ100c.c.で洗浄、塊の温水溶解、
酸析処理、湯洗、乾燥して76ｇの２，６−ジオキ
シアントラキノンを得た。このものの純度は96.5
％で品質も実施例１とほぼ同じであつた。Example 2 100 g of the same crude 2,6-dioxyanthraquinone used in Example 1 was added to an 8% aqueous solution of caustic soda.
It was added to 1000g and heated to 80°C to dissolve. Next, as in Example 1, cool to 30-35℃ to remove the precipitate.
Washing with 10% caustic soda 100c.c., dissolving lumps in warm water,
Acid precipitation treatment, hot water washing, and drying yielded 76 g of 2,6-dioxyanthraquinone. The purity of this stuff is 96.5
% and quality was almost the same as in Example 1.
実施例 ３
実施例１の８％苛性ソーダ水溶液の代りに15％
苛性カリ水溶液1000ｇを用いて70℃に昇温して溶
解し、実施例１の49％苛性ソーダ水溶液137ｇの
代りに固形苛性カリ62.5ｇを逐次添加した以外
は、実施例１と全く同様にして粗２，６−ジオキ
シアントラキノンを精製処理して、精２，６−ジ
オキシアントラキノン75ｇを得た。このものの純
度96.8％で品質も実施例１とほぼ同じであつた。Example 3 15% instead of the 8% caustic soda aqueous solution of Example 1
Using 1000 g of caustic potassium aqueous solution, the temperature was raised to 70°C to dissolve it, and crude 2, The 6-dioxyanthraquinone was purified to obtain 75 g of purified 2,6-dioxyanthraquinone. The purity of this product was 96.8% and the quality was almost the same as in Example 1.
Claims (1)
30重量％の濃度のアルカリ金属水酸化物水溶液に
加熱溶解し、ついで冷却して２，６−ジオキシア
ントラキノンのアルカリ金属塩として析出させ、
これを10〜70℃で固液分離し、得られた濾塊を温
水に溶解したのち、酸析分離することを特徴とす
る２，６−ジオキシアントラキノンの精製方法。 ２ 固液分離時の温度が、30〜50℃である特許請
求の範囲第１項記載の方法。 ３ アルカリ金属水酸化物の濃度が、８〜20重量
％である特許請求の範囲第１項記載の方法。 ４ 粗２，６−ジオキシアントラキノンに対し、
アリカリ金属水酸化物を、10〜20重量倍量用いる
特許請求の範囲第１項記載の方法。[Claims] 1. Crude 2,6-dioxyanthraquinone,
Dissolved by heating in an aqueous alkali metal hydroxide solution having a concentration of 30% by weight, and then cooled to precipitate an alkali metal salt of 2,6-dioxyanthraquinone,
A method for purifying 2,6-dioxyanthraquinone, which comprises performing solid-liquid separation of this at 10 to 70°C, dissolving the obtained filter cake in warm water, and then performing acid precipitation separation. 2. The method according to claim 1, wherein the temperature during solid-liquid separation is 30 to 50°C. 3. The method according to claim 1, wherein the concentration of the alkali metal hydroxide is 8 to 20% by weight. 4 For crude 2,6-dioxyanthraquinone,
2. The method according to claim 1, wherein the alkali metal hydroxide is used in an amount of 10 to 20 times by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24215183A JPS60136533A (en) | 1983-12-23 | 1983-12-23 | Purification of 2,6-dioxyanthraquinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24215183A JPS60136533A (en) | 1983-12-23 | 1983-12-23 | Purification of 2,6-dioxyanthraquinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60136533A JPS60136533A (en) | 1985-07-20 |
| JPH0455184B2 true JPH0455184B2 (en) | 1992-09-02 |
Family
ID=17085078
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24215183A Granted JPS60136533A (en) | 1983-12-23 | 1983-12-23 | Purification of 2,6-dioxyanthraquinone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60136533A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2819599B2 (en) * | 2019-10-15 | 2021-11-18 | Univ Burgos | 2,6-DIHYDROXYANTHRAQUINONE SYNTHESIS PROCEDURE |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5089357A (en) * | 1973-12-14 | 1975-07-17 |
-
1983
- 1983-12-23 JP JP24215183A patent/JPS60136533A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5089357A (en) * | 1973-12-14 | 1975-07-17 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60136533A (en) | 1985-07-20 |
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