JPS6113460B2 - - Google Patents
Info
- Publication number
- JPS6113460B2 JPS6113460B2 JP851277A JP851277A JPS6113460B2 JP S6113460 B2 JPS6113460 B2 JP S6113460B2 JP 851277 A JP851277 A JP 851277A JP 851277 A JP851277 A JP 851277A JP S6113460 B2 JPS6113460 B2 JP S6113460B2
- Authority
- JP
- Japan
- Prior art keywords
- isomer
- mother liquor
- weight
- amount
- acid
- 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
Links
- 239000012452 mother liquor Substances 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 33
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 31
- 229910017604 nitric acid Inorganic materials 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 25
- 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 claims description 17
- 150000004056 anthraquinones Chemical class 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- MBIJFIUDKPXMAV-UHFFFAOYSA-N 1,8-dinitroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC([N+]([O-])=O)=C2C(=O)C2=C1C=CC=C2[N+](=O)[O-] MBIJFIUDKPXMAV-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- NMNSBFYYVHREEE-UHFFFAOYSA-N 1,2-dinitroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=C([N+]([O-])=O)C([N+](=O)[O-])=CC=C3C(=O)C2=C1 NMNSBFYYVHREEE-UHFFFAOYSA-N 0.000 claims description 2
- XVMVHWDCRFNPQR-UHFFFAOYSA-N 1,5-dinitroanthracene-9,10-dione Chemical compound O=C1C=2C([N+](=O)[O-])=CC=CC=2C(=O)C2=C1C=CC=C2[N+]([O-])=O XVMVHWDCRFNPQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000725 suspension Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 230000007423 decrease Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 239000000986 disperse dye Substances 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 5
- 230000008025 crystallization Effects 0.000 description 5
- 239000012066 reaction slurry Substances 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KFIRODWJCYBBHY-UHFFFAOYSA-N 3-nitrophthalic acid Chemical class OC(=O)C1=CC=CC([N+]([O-])=O)=C1C(O)=O KFIRODWJCYBBHY-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- -1 dinitrate anthraquinone Chemical compound 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UQKJUEALIQRECQ-UHFFFAOYSA-N 1,6-dinitroanthracene-9,10-dione Chemical compound O=C1C2=CC([N+](=O)[O-])=CC=C2C(=O)C2=C1C=CC=C2[N+]([O-])=O UQKJUEALIQRECQ-UHFFFAOYSA-N 0.000 description 1
- OPXXCGAYBFDPHY-UHFFFAOYSA-N 2,6-dinitroanthracene-9,10-dione Chemical compound [O-][N+](=O)C1=CC=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 OPXXCGAYBFDPHY-UHFFFAOYSA-N 0.000 description 1
- XFLONXIGNOXKCG-UHFFFAOYSA-N 2,7-dinitroanthracene-9,10-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)C3=CC([N+](=O)[O-])=CC=C3C(=O)C2=C1 XFLONXIGNOXKCG-UHFFFAOYSA-N 0.000 description 1
- SLAMLWHELXOEJZ-UHFFFAOYSA-N 2-nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、1・5−及び1・8−ジニトロアン
トラキノンの製造方法に関するものである。
1・5−ジニトロアントラキノン(以下、1・
5−体と言う)は分散染料、殊に1・5−ジオキ
シ−4・8−ジアミノ−2−アリールアントラキ
ノン類に属する昇華堅ろう性及び鮮明度の高い青
色分散染料の中間体として有用であり、また、
1・8−ジニトロアントラキノン(以下1・8−
体と言う)は分散染料、殊にモノハロゲン化−
1・8−ジアミノ−4・5−ジオキシアントラキ
ノンを主成分とする鮮明度高くかつ経済性のある
青色分散染料の中間体として有用である。
1・5−及び1・8−体の製造方法については
種々知られているが、その中の一つに、硝酸と硫
酸からなる混酸を使用してアントラキノンのジニ
トロ化を行つたのち、得られたスラリーから1・
5−体ケーキを分離し、次いで分離母液を濃縮し
て1・8−体を晶析分離する方法がある。
しかして、1・5−及び1・8−体の固液分離
は、例えば、遠心分離機、フイルタ−プレス等の
分離機を用いて行われるが、上記の方法で得られ
る1・5−及び1・8−体粒子は、大略20μ程度
と微細であるため、目漏れ目詰り等を起し易く、
従来より、1・5−及び1・8−体粒子の粗大化
が望まれている。
本発明者等は上記実情に鑑み、1・5−及び
1・8−体粒子の粗大化につき種々検討した結
果、前述のジニトロ化反応を、1・8−体を分離
して得た母液の存在下に行うならば著しく粗大化
された1・5−及び1・8−体が得られること知
り本発明を完成した。
すなわち、本発明の要旨は、硝酸に対する硫酸
の重量比が50:50〜65:35の混酸をアントラキノ
ンに対する硝酸モル比が35以上となる量使用して
アントラキノンをジニトロ化し、得られたスラリ
ーを加熱懸濁処理したのち、該スラリーから1・
5−ジニトロアントラキノンのケーキを分離し、
次いで分離母液を濃縮して1・8−ジニトロアン
トラキノンを晶析分離するとともに、1・8−ジ
ニトロアントラキノンを晶析分離して得た母液を
前記ジニトロ化反応に再使用することを特徴とす
る1・5−及び1・8−ジニトロアントラキノン
の製造方法に存する。
以下、本発明を詳細に説明する。
本発明では、硝酸に対する硫酸の重量比(以
下、混酸比と言う)が50:50〜65:35の混酸をア
ントラキノンに対する硝酸モル比が35以上となる
量使用してアントラキノンをジニトロ化する。
アントラキノンに対する硝酸モル比の上限は、
特に限定されるものではないが、使用割合が多過
ぎると1・5−体の溶解量が増加してその回収率
が低下するので、混酸比及び後述する分離温度に
おける1・5−体の溶解量を考慮の上1・5−体
の分離操作が良好にできる範囲で少量とするのが
よく、通常は、アントラキノン1モルに対し150
モル程度以下の範囲から選ばれる。硝酸及び硫酸
は、可及的高濃度のものを使用するのが好まし
く、通常98重量%以上の硝酸及び100重量%硫酸
が用いられる。反応温度は、通常−20〜80℃、好
ましくは10〜50℃の範囲とするのがよい。
ジニトロ化反応で得られる反応混合物は、1・
5−体、1・8−体の他に、2・6−ジニトロア
ントラキノン、2・7−ジニトロアントラキノ
ン、1・6−ジニトロアントラキノン及び1・7
−ジニトロアントラキノン(以下、これをβ体と
言う)等の各種異性体の混合物である。これらの
生成比率は、反応温度などに依存して多少変化す
るが、1・5−体が35〜42重量%、1・8−体が
34〜38重量%、β−体が19〜27重量%であり、残
余はアントラキノン核を持たない副生物である。
上記の各異性体の混酸に対する溶解度は、1・
5−体<1・8−体<β−体の順であり、これら
の溶解度比は混酸組成によつて若干変化するが、
大略1:4〜6:20〜25の範囲内にあり、上記ジ
ニトロ化反応で得られた反応混合物は、生成した
1・5−体の大半を固体として含むスラリーであ
る。1・5−体の固形物は、1・8−体を巻き込
んでおり、これを単に分離するだけでは純度が低
いので、本発明では、反応スラリーを加熱懸濁処
理したのち該スラリーから1・5−体ケーキを分
離し、次いで分離母液を濃縮して溶解力の大きい
硝酸を留去することにより1・8−体を晶析分離
する。
加熱懸濁処理の温度は、50℃より低いと余り効
果がなく、また余り高いと硝酸酸化などの副反応
により製品収率の低下を来すので、通常は50〜90
℃の範囲から、混酸比に依存して選ばれ、例え
ば、混酸比が50:50の場合は75〜90℃、55:45の
場合は65〜90℃、65:35の場合は50〜70℃の範囲
とするのがよい。処理時間は、温度が高いほど短
時間でよく、例えば50℃の場合は3〜15時間、70
℃の場合は1〜10時間、80℃の場合は0.5〜7時
間程度である。
加熱懸濁処理終了後、1・5−体のケーキを反
応スラリーより分離するが、該分離に先立ち反応
スラリーを、1・8−体が晶出しない範囲で、70
℃以下、好ましくは40〜60℃に冷却すると、1・
5−体ケーキ収率が向上し、1・5−体粒子が一
層粗大化されて好ましい。
1・5−及び1・8−体の分離は、例えば、遠
心分離機、フイルタープレス等の従来公知の分離
機を用いて行われ、1・8−体を晶析分離する際
の母液の濃縮は、通常の溶媒蒸発に適用される蒸
発缶を用いて行われる。
濃縮温度は、高温過ぎると硝酸酸化などの副反
応により不純物の生成を招来し、また低温では晶
析される1・8−体の粒径が小さくなるので、通
常は40〜90℃、好ましくは40〜70℃の範囲とする
のがよい。分離母液の濃縮率は、高過ぎるとβ−
体の晶析量が増加して1・8−体の純度が低下
し、また低過ぎるとジニトロ化反応に再使用する
母液中の1・8−体の量が大となり、1・5−体
の純度が低下するばかりか後述する母液のパージ
に伴う1・8−体の損失が大となる。一方、1・
8−体を前述した青色分散染料の中間体として使
用する場合、15重量%以下のβ−体の混入は特に
問題とならない。従つて、分離母液の濃縮は、晶
析する1・8−体中のβ−体含量が15重量%以
下、好ましくは10重量%以下の範囲となるように
行われ、晶析する1.8−体の重量が原料アントラ
キノンに対し30〜45重量%となるように行うのが
有利である。(この場合、1・8−体のβ−体含
量は通常5〜15重量%となる)
本発明は、1・8−体を分離して得た母液をジ
ニトロ化反応に再使用することにより、1・5−
及び1・8−体粒子を粗大化するものである。こ
の母液は、1・5−体、1・8−体、β−体及び
副生物を含む混酸よりなり、その組成は、ジニト
ロ化反応に使用する混酸の組成、その他本発明を
実施する際の種々の条件によつて変化するが、通
常は、混酸比が20:80〜60:40程度、1・5−
体、1・8−体等の含有量が混酸に対し1〜12重
量%程度であり、これらの成分の内訳は、60重量
%程度のβ−体、30重量%程度のアントラキノン
核を持たない副生物及び10重量%程度の1・5−
体と1・8−体である。
母液の使用量は、余り少な過ぎると十分な効果
が得られず、逆に、余り多いと不純物のβ−体が
蓄積して1・5−及び1・8−体の純度低下を来
すので、通常は、硫酸ベースで表わされる使用量
(母液中の硫酸重量/全硫酸重量×100)が10〜95重量
%、好ま
しくは30〜90重量%、更に好ましくは50〜85重量
%の範囲から選ばれ、残余はパージされる。
反応スラリーを加熱懸濁処理したのち、該スラ
リーから分離される1・5−体ケーキの純度は、
ジニトロ化反応に再使用する母液の量によつて影
響され、単に母液再使用率を上げるときは純度は
70〜85重量%に低下するが、加熱懸濁処理時の硝
酸モル比を母液の使用量に応じて調節するなら
ば、1・5−体からの1・8−体の溶出分離が効
率的に行われ、一層高純度の1・5−体、例え
ば、青色分散染料の中間体として要求される90重
量%以上のものも得ることができる。
加熱懸濁時の混酸比、硝酸量及び母液使用量の
関係を第1〜2図に示す。
第1図は、後述の実施例の条件に準じてβ−体
含量が10重量%の1・8−体を晶析分離して得た
母液を使用した場合の混酸比、硝酸量、母液量と
1・5−体の純度との関係を示すグラフであり、
図中、縦軸は硝酸量(原料アントラキノンに対す
るモル比)を、横軸は母液使用量(前記硫酸ベー
スで表示した重量%)を示す。図中、1,2及び
3線は混酸比が(50:50)、(55:45)及び(65:
35)で且つ1・5−体の純度が95重量%の場合を
示し、また、1′,2′及び3′は上記の各混酸比
で1・5−体の純度が90重量%の場合を示す。従
つて、純度90〜95重量%の1・5−体は1と
1′、2と2′又は3と3′で囲まれる条件を採用
することにより得られる。
なお、1〜3及び1′〜3′線は前述の通り、β
−体の含量が10重量%の1・8−体ケーキを分離
した母液を再使用する場合を示すが、1・8−体
中のβ−体の含量を変化させる場合には、これら
の線は幾分変動する。すなわち、β−体の含量が
増加すれば、硝酸量は減少し、またβ−体の含量
が減少すれば硝酸量は増加するが、その変動巾は
β−体の含量の変化が±5重量%であれば硝酸量
は約〓5モル程度である。
第2図は、第1図と同様にして得られたもので
あるが、縦軸は硝酸量を、横軸は重量%で混酸組
成(H2SO4/H2SO4+HNO3×100)を示す
。図中、A,
B,C及びD線は、母液使用量が夫々30、50、85
及び90重量%で1・5−体の純度が95重量%の場
合を示し、またA′,B′,C′及びD′線は、上記の
各母液使用量で1・5−体の純度が90重量%の場
合を示す。第2図も第1図と同様に利用すること
ができる。
前記の加熱懸濁処理時に於ける硝酸モル比の調
節は、反応終了後加熱懸濁処理前に行うこともで
きるが、ジニトロ化反応で消費される硝酸の量を
考慮して、ジニトロ化反応時に予め調節するのが
簡便である。
本発明方法は、回分法、連続法のいずれにも適
用することができ、本発明を実施するプロセスの
一例をブロツクダイアグラムで示せば第3図の通
りである。
以上のように、本発明方法によれば、アントラ
キノンのジニトロ化により得られる1・5−体及
び1・8−体の粒径が粗大化されるので、これら
を分離する際の過機の負担が著しく軽減され
る。また、製造工程から排出される廃硫酸量を大
巾に削減するとともに、廃硫酸中に含まれる1・
5−体、1・8−体を有効に回収することができ
る。
次に、本発明を実施例により更に詳細に説明す
るが、本発明はその要旨を越えない限り以下の実
施例に限定されるものではない。
実施例 1〜13
アントラキノン供給用連続式フイーダー、外部
循環式冷却器及び硫酸、硝酸、再使用母液供給用
ポンプを備えた鋼製の撹拌槽式連続反応器に、反
応に際してのHNO3/H2SO4重量比、HNO3/ア
ントラキノンモル比、及び硫酸ベースで表わした
母液再使用率が所定値になるように、アントラキ
ノン、硝酸、硫酸、及び再使用母液(スタートに
あたつてはメークアツプ)を供給し、反応混合物
を抜き出しながら、温度40℃、反応槽滞留時間
0.6時間でジニトロ化反応を行なつた。
抜き出された反応混合物をグラスライニングの
加熱懸濁槽に送り、所定温度で約1時間処理を行
うことによつて、スラリー中の1・5−体ケーキ
の純度を上げた。
加熱懸濁槽から抜き出されたスラリーを、温度
を懸濁槽により約20℃低く設定した滞留時間約3
時間の晶析槽に送り、ここで一部溶解している
1・5−体を晶析させた。
晶析槽から抜き出されたスラリーを、テフロン
製布を装着した過機を用いて過し、十分に
母液の振り切りを行つたのち(このときケーキの
含液率は湿ケーキ基準27〜35重量%)、液を
1・8−体晶析工程に送つた。ケーキ側は付着母
液分による純度低下を防ぐため、母液中の
HNO3:H2SO4比と同じ割合に98%硝酸と100%
硫酸を混合した混液を、対ケーキ1・5倍ふりか
けてケーキ洗浄を行い、ケーキを水洗し、乾燥し
て1・5−体ケーキを得た。
1・8−体の晶析は、外部加熱器を備えた強制
循環式蒸発缶を用いて、温度50〜60℃、滞留時間
1〜1.5時間で、1・5−体液中の硝酸を蒸発
させることにより行なつた。硝酸蒸発量は、目標
とするケーキ純度及び母液再使用率によつても多
少異なるが、HNO3:H2SO4比55:45のとき蒸発
HNO3/仕込アントラキノン=30〜42モル/モ
ル、65:35のとき20〜30モル/モル、50:50のと
き50〜70モル/モルである。晶析槽より抜き出し
たスラリーを1・5−体と同様にして過、水洗
乾燥して1・8−体ケーキを得た。
このようにして得られる1・5−体ケーキ及び
1・8−体ケーキの組成は高速液体クロマトグラ
フを用いて分析した。また、これらのケーキの粒
度測定は通気法によつた。
1・8−体ケーキ分離した母液の組成分析は次
のようにして行なつた。まずサンプルを取つて水
を加え、酸濃度20重量%まで稀釈し、析出する固
型物を過し、洗浄して取出し、この固型物を高
速液体クロマトグラフ分析して1・5−体、1・
8−体、β−体の量を求めた。液及び洗液を合
わせ、中和法で全酸量を、硫酸バリウム法で硫酸
量を求め、HNO3、H2SO4量を算出した。副生物
についてはその内訳の大部分がニトロ安息香酸、
ニトロフタル酸類であること及びこれらの酸類
が、酸濃度20重量%の母液に十分可溶であるとの
知見に立つて、酸溶液の全炭素分析値から、ニト
ロフタル酸で代表した有機物量に近似して求め
た。
以上の方法で第1表に示す実験を行ない、第2
表の結果を得た。これらの実験ではいずれも約
200時間の連続運転において、各製品収量、組成
値、粒径、過性などに実質的な変動はなかつ
た。
比較例 1〜2
比較例1は実施例1〜3に、比較例2は実施例
12〜13にそれぞれ対応して、母液を全く再使用し
ない例である。このとき、1・5−体ケーキの純
度を合わせるためには、仕込時HNO3/アントラ
キノンモル比はそれぞれ61.2モル、89モルであれ
ばよい。
実験条件を第1表に、結果を第2表に示す。
The present invention relates to a method for producing 1,5- and 1,8-dinitroanthraquinone. 1,5-dinitroanthraquinone (hereinafter referred to as 1,
5-isomer) is useful as an intermediate for disperse dyes, especially blue disperse dyes belonging to the 1,5-dioxy-4,8-diamino-2-arylanthraquinones, which have high sublimation fastness and brightness. Also,
1,8-dinitroanthraquinone (hereinafter 1,8-
) are disperse dyes, especially monohalogenated dyes.
It is useful as an intermediate for a blue disperse dye which has high definition and is economical, which is mainly composed of 1,8-diamino-4,5-dioxyanthraquinone. Various methods for producing 1,5- and 1,8-isomers are known, but one of them is to dinitrate anthraquinone using a mixed acid consisting of nitric acid and sulfuric acid. 1.
There is a method of separating the 5-isomer cake, then concentrating the separated mother liquor, and crystallizing and separating the 1.8-isomer. Therefore, solid-liquid separation of 1,5- and 1,8-isomers is carried out using a separator such as a centrifuge or a filter press, but the 1,5- and 1,8-isomers obtained by the above method are 1.8-body particles are as small as approximately 20 μm, so they easily cause leakage and clogging.
Conventionally, coarsening of 1.5- and 1.8-body particles has been desired. In view of the above circumstances, the present inventors conducted various studies regarding the coarsening of 1,5- and 1,8-isomer particles. The present invention was completed based on the knowledge that significantly coarsened 1,5- and 1,8-isomers can be obtained if the process is carried out in the presence of the compound. That is, the gist of the present invention is to dinitrate anthraquinone using a mixed acid with a weight ratio of sulfuric acid to nitric acid of 50:50 to 65:35 in an amount such that the molar ratio of nitric acid to anthraquinone is 35 or more, and heat the resulting slurry. After suspension treatment, 1.
Separating the 5-dinitroanthraquinone cake;
Next, the separated mother liquor is concentrated to crystallize and separate 1,8-dinitroanthraquinone, and the mother liquor obtained by crystallizing and separating 1,8-dinitroanthraquinone is reused for the dinitration reaction. - A method for producing 5- and 1,8-dinitroanthraquinone. The present invention will be explained in detail below. In the present invention, anthraquinone is dinitrated by using a mixed acid having a weight ratio of sulfuric acid to nitric acid (hereinafter referred to as mixed acid ratio) of 50:50 to 65:35 in an amount such that the molar ratio of nitric acid to anthraquinone is 35 or more. The upper limit of the molar ratio of nitric acid to anthraquinone is
Although not particularly limited, if the proportion used is too large, the amount of dissolved 1,5-isomer will increase and the recovery rate will decrease, so the dissolution of 1,5-isomer at the mixed acid ratio and the separation temperature described below. Considering the amount, it is best to keep the amount as small as possible to perform a good separation operation of the 1,5-isomer, and usually 150
Selected from a range of about mol or less. It is preferable to use nitric acid and sulfuric acid at as high a concentration as possible, and usually 98% by weight or more nitric acid and 100% by weight sulfuric acid are used. The reaction temperature is generally -20 to 80°C, preferably 10 to 50°C. The reaction mixture obtained in the dinitration reaction is 1.
In addition to the 5- and 1,8-isomers, 2,6-dinitroanthraquinone, 2,7-dinitroanthraquinone, 1,6-dinitroanthraquinone and 1,7
- It is a mixture of various isomers such as dinitroanthraquinone (hereinafter referred to as β-form). The production ratio of these changes slightly depending on the reaction temperature, etc., but 35 to 42% by weight of 1,5-isomer and 1,8-isomer.
The β-isomer accounts for 34-38% by weight, the β-isomer accounts for 19-27% by weight, and the remainder is a by-product that does not have an anthraquinone core. The solubility of each of the above isomers in mixed acid is 1.
The order is 5-form < 1/8-form < β-form, and these solubility ratios vary slightly depending on the mixed acid composition, but
The ratio is approximately 1:4 to 6:20 to 25, and the reaction mixture obtained in the dinitration reaction is a slurry containing most of the produced 1,5-isomer as a solid. The 1,5-isomer solids involve 1,8-isomers, and simply separating them will result in low purity. Therefore, in the present invention, the reaction slurry is heated and suspended, and then the 1,8-isomer is extracted from the slurry. The 5-isomer cake is separated, and the separated mother liquor is then concentrated to distill off nitric acid, which has a large dissolving power, to crystallize and separate the 1.8-isomer. The heating suspension treatment temperature is usually 50 to 90°C, since it is not very effective if it is lower than 50°C, and if it is too high, the product yield will decrease due to side reactions such as nitric acid oxidation.
℃ range, depending on the mixed acid ratio, for example, if the mixed acid ratio is 50:50, it is 75-90℃, if it is 55:45, it is 65-90℃, and if it is 65:35, it is 50-70℃. It is preferable to set it in the range of ℃. The higher the temperature, the shorter the treatment time, for example, 3 to 15 hours at 50℃, 70℃
When the temperature is 1 to 10 hours, the heating time is about 0.5 to 7 hours at 80°C. After the heating suspension treatment, the 1,5-isomer cake is separated from the reaction slurry. Prior to separation, the reaction slurry is heated at 70°C to the extent that the 1,8-isomer does not crystallize.
When cooled to below ℃, preferably 40 to 60℃, 1.
This is preferable because the yield of the 5-body cake is improved and the 1.5-body particles are further coarsened. Separation of 1,5- and 1,8-isomers is carried out using conventionally known separators such as centrifuges and filter presses, and concentration of the mother liquor when crystallizing and separating 1,8-isomers is performed. This is carried out using an evaporator that is used for conventional solvent evaporation. The concentration temperature is usually 40 to 90°C, preferably 40 to 90°C, because if it is too high, impurities will be generated due to side reactions such as nitric acid oxidation, and if it is low, the particle size of the crystallized 1,8-isomer will become small. The temperature is preferably in the range of 40 to 70°C. If the concentration ratio of the separated mother liquor is too high, β-
The amount of crystallized 1,8-isomer increases and the purity of 1,8-isomer decreases.If it is too low, the amount of 1,8-isomer in the mother liquor reused in the dinitration reaction becomes large, resulting in a decrease in the purity of 1,8-isomer. Not only does the purity of the 1.8-isomer decrease, but also the loss of 1,8-isomer increases during the purging of the mother liquor, which will be described later. On the other hand, 1.
When the 8-isomer is used as an intermediate for the above-mentioned blue disperse dye, the contamination of 15% by weight or less of the .beta.-isomer poses no particular problem. Therefore, the separation mother liquor is concentrated so that the β-isomer content in the 1.8-isomer to be crystallized is 15% by weight or less, preferably 10% by weight or less, and the 1.8-isomer to be crystallized is Advantageously, the weight of the anthraquinone is 30 to 45% by weight, based on the anthraquinone starting material. (In this case, the β-isomer content of the 1,8-isomer is usually 5 to 15% by weight.) The present invention is achieved by reusing the mother liquor obtained by separating the 1,8-isomer in the dinitration reaction. , 1・5-
and coarsens 1,8-body particles. This mother liquor consists of a mixed acid containing 1,5-isomer, 1,8-isomer, β-isomer, and by-products, and its composition is different from that of the mixed acid used in the dinitration reaction and other matters when carrying out the present invention. Although it varies depending on various conditions, the mixed acid ratio is usually about 20:80 to 60:40, 1.5-
The content of 1- and 1-8-isomers is about 1 to 12% by weight based on the mixed acid, and the breakdown of these components is about 60% by weight of β-isomer and about 30% by weight of anthraquinone without an anthraquinone nucleus. By-products and about 10% by weight of 1.5-
body and 1.8-body. If the amount of mother liquor used is too small, the sufficient effect will not be obtained, and on the other hand, if it is too large, the impurity β-isomer will accumulate and the purity of 1,5- and 1,8-isomer will decrease. The amount used, expressed on a sulfuric acid basis (weight of sulfuric acid in mother liquor/weight of total sulfuric acid x 100), is usually in the range of 10 to 95% by weight, preferably 30 to 90% by weight, more preferably 50 to 85% by weight. selected and the remainder purged. After the reaction slurry is heated and suspended, the purity of the 1,5-body cake separated from the slurry is:
It is influenced by the amount of mother liquor reused in the dinitration reaction, and when simply increasing the mother liquor reuse rate, the purity is
However, if the nitric acid molar ratio during heating suspension treatment is adjusted according to the amount of mother liquor used, elution and separation of the 1,8-isomer from the 1,5-isomer is efficient. It is possible to obtain even higher purity 1,5-isomers, for example, 90% by weight or more, which is required as an intermediate for blue disperse dyes. The relationship between the mixed acid ratio, the amount of nitric acid and the amount of mother liquor used during heating and suspension is shown in Figures 1 and 2. Figure 1 shows the mixed acid ratio, amount of nitric acid, and amount of mother liquor when using a mother liquor obtained by crystallizing and separating 1,8-isomer with a β-isomer content of 10% by weight according to the conditions of the example described later. It is a graph showing the relationship between and the purity of 1.5-body,
In the figure, the vertical axis shows the amount of nitric acid (molar ratio to the raw material anthraquinone), and the horizontal axis shows the amount of mother liquor used (weight % expressed on the sulfuric acid basis). In the figure, lines 1, 2, and 3 indicate mixed acid ratios of (50:50), (55:45), and (65:
35) and the purity of the 1,5-isomer is 95% by weight, and 1', 2', and 3' are the cases where the purity of the 1,5-isomer is 90% by weight at each of the above mixed acid ratios. shows. Therefore, a 1,5-isomer with a purity of 90 to 95% by weight can be obtained by adopting the conditions surrounded by 1 and 1', 2 and 2', or 3 and 3'. In addition, as mentioned above, the 1-3 and 1'-3' lines are β
The case where the mother liquor separated from the 1,8- body cake with a 1,8- body content is 10% by weight is reused, but when changing the content of the β- body in the 1,8- body, these lines varies somewhat. In other words, if the content of β-isomer increases, the amount of nitric acid decreases, and if the content of β-isomer decreases, the amount of nitric acid increases, but the range of fluctuation is within ±5 weight of the change in the content of β-isomer. %, the amount of nitric acid is about 5 moles. Figure 2 was obtained in the same manner as Figure 1, but the vertical axis shows the amount of nitric acid, and the horizontal axis shows the mixed acid composition (H 2 SO 4 /H 2 SO 4 +HNO 3 ×100) in weight%. shows. In the figure, lines A, B, C, and D indicate that the amount of mother liquor used is 30, 50, and 85, respectively.
and 90% by weight, the purity of 1,5-isomer is 95% by weight, and the A', B', C', and D' lines indicate the purity of 1,5-isomer at the above-mentioned amounts of mother liquor used. is 90% by weight. FIG. 2 can also be used in the same way as FIG. 1. Adjustment of the nitric acid molar ratio during the above-mentioned heating suspension treatment can be carried out after the completion of the reaction and before the heating suspension treatment, but considering the amount of nitric acid consumed in the dinitration reaction, It is convenient to adjust in advance. The method of the present invention can be applied to either a batch method or a continuous method, and an example of the process for carrying out the present invention is shown in a block diagram as shown in FIG. 3. As described above, according to the method of the present invention, the particle size of the 1,5-isomer and 1,8-isomer obtained by dinitration of anthraquinone becomes coarse, so that the strain on the filter when separating these is increased. is significantly reduced. In addition, we will greatly reduce the amount of waste sulfuric acid discharged from the manufacturing process, and the amount of 1.
5-bodies and 1.8-bodies can be effectively recovered. Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples unless the gist thereof is exceeded. Examples 1 to 13 A steel stirred tank continuous reactor equipped with a continuous feeder for anthraquinone, an external circulation cooler, and a pump for feeding sulfuric acid, nitric acid, and reused mother liquor was charged with HNO 3 /H 2 during the reaction. Anthraquinone, nitric acid, sulfuric acid, and reused mother liquor (make-up at the start) are added so that the SO 4 weight ratio, HNO 3 /anthraquinone molar ratio, and mother liquor reuse rate expressed on a sulfuric acid basis become the specified values. Temperature 40℃, reaction tank residence time while feeding and withdrawing the reaction mixture.
The dinitration reaction was carried out in 0.6 hours. The extracted reaction mixture was sent to a glass-lined heated suspension tank and treated at a predetermined temperature for about 1 hour, thereby increasing the purity of the 1,5-body cake in the slurry. The slurry extracted from the heated suspension tank is kept at a temperature of approximately 20℃ lower in the suspension tank for a residence time of approximately 3.
The mixture was sent to a crystallization tank, where the partially dissolved 1,5-isomer was crystallized. The slurry extracted from the crystallization tank is passed through a filter equipped with a Teflon cloth, and the mother liquor is thoroughly shaken off. %), the liquid was sent to a 1.8-body crystallization step. On the cake side, in order to prevent purity from decreasing due to adhering mother liquor,
98% nitric acid and 100 % HNO3 : H2SO4 ratio in the same proportions
The cake was washed by sprinkling 1.5 times the amount of sulfuric acid on the cake, and the cake was washed with water and dried to obtain a 1.5-body cake. For crystallization of 1,8-body, nitric acid in 1,5-body fluid is evaporated using a forced circulation evaporator equipped with an external heater at a temperature of 50 to 60℃ and a residence time of 1 to 1.5 hours. This was done by doing this. The amount of nitric acid evaporated varies somewhat depending on the target cake purity and mother liquor reuse rate, but when the HNO 3 :H 2 SO 4 ratio is 55:45,
HNO3 /charged anthraquinone=30 to 42 mol/mol, 20 to 30 mol/mol at 65:35, and 50 to 70 mol/mol at 50:50. The slurry extracted from the crystallization tank was filtered, washed with water and dried in the same manner as for the 1,5-body to obtain a 1,8-body cake. The compositions of the 1,5-body cake and 1,8-body cake thus obtained were analyzed using high performance liquid chromatography. The particle size of these cakes was measured by the aeration method. The composition analysis of the mother liquor from which the 1,8-body cake was separated was carried out as follows. First, a sample is taken, water is added to dilute it to an acid concentration of 20% by weight, the precipitated solid substance is filtered, washed and taken out, and this solid substance is analyzed by high performance liquid chromatography to determine the 1,5-isomer, 1・
The amounts of 8-isomer and β-isomer were determined. The solution and washing solution were combined, and the total acid amount was determined by the neutralization method, the sulfuric acid amount was determined by the barium sulfate method, and the amounts of HNO 3 and H 2 SO 4 were calculated. Most of the by-products are nitrobenzoic acid,
Based on the knowledge that these acids are nitrophthalic acids and are sufficiently soluble in a mother liquor with an acid concentration of 20% by weight, the amount of organic matter represented by nitrophthalic acid was approximated from the total carbon analysis value of the acid solution. I asked. The experiments shown in Table 1 were conducted using the above method, and the second
Obtained the results in the table. In both of these experiments, approximately
During 200 hours of continuous operation, there was no substantial change in the yield, composition, particle size, permeability, etc. of each product. Comparative Examples 1-2 Comparative Example 1 is applicable to Examples 1-3, Comparative Example 2 is applicable to Example
Corresponding to cases 12 and 13, these are examples in which the mother liquor is not reused at all. At this time, in order to match the purity of the 1,5-body cake, the HNO 3 /anthraquinone molar ratio at the time of preparation should be 61.2 mol and 89 mol, respectively. The experimental conditions are shown in Table 1, and the results are shown in Table 2.
【表】【table】
第1〜2図は、反応スラリーを加熱懸濁処理す
る際の、混酸比、硝酸量、母液使用量、析出する
1・5−体ケーキの純度の関係を示すグラフであ
り、第3図は、本発明を実施するプロセスの一例
を示すブロツクダイアグラムである。
Figures 1 and 2 are graphs showing the relationship between the mixed acid ratio, the amount of nitric acid, the amount of mother liquor used, and the purity of the precipitated 1.5-body cake when the reaction slurry is heated and suspended. , is a block diagram illustrating an example of a process for implementing the present invention.
Claims (1)
をアントラキノンに対する硝酸モル比が35以上と
なる量使用してアントラキノンをジニトロ化し、
得られたスラリーを加熱懸濁処理したのち、該ス
ラリーから1・5−ジニトロアントラキノンのケ
ーキを分離し、次いで分離母液を濃縮して1・8
−ジニトロアントラキノンを晶析分離するととも
に、1・8−ジニトロアントラキノンを分離して
得た母液を前記ジニトロ化反応に再使用すること
を特徴とする1・5−及び1・8−ジニトロアン
トラキノンの製造方法。1 Dinitration of anthraquinone using a mixed acid with a weight ratio of nitric acid to sulfuric acid of 50:50 to 65:35 in an amount such that the molar ratio of nitric acid to anthraquinone is 35 or more,
After heating and suspending the obtained slurry, a cake of 1,5-dinitroanthraquinone was separated from the slurry, and then the separated mother liquor was concentrated to obtain 1,8
- Production of 1,5- and 1,8-dinitroanthraquinone, characterized by crystallizing and separating dinitroanthraquinone and reusing the mother liquor obtained by separating 1,8-dinitroanthraquinone in the dinitration reaction. Method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP851277A JPS5395955A (en) | 1977-01-28 | 1977-01-28 | Preparation of 1,5-and 1,8-dinitroanthraquinone |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP851277A JPS5395955A (en) | 1977-01-28 | 1977-01-28 | Preparation of 1,5-and 1,8-dinitroanthraquinone |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5395955A JPS5395955A (en) | 1978-08-22 |
JPS6113460B2 true JPS6113460B2 (en) | 1986-04-14 |
Family
ID=11695172
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP851277A Granted JPS5395955A (en) | 1977-01-28 | 1977-01-28 | Preparation of 1,5-and 1,8-dinitroanthraquinone |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5395955A (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102746692B (en) * | 2012-06-18 | 2014-04-23 | 绍兴奇彩化工有限公司 | Preparation method for disperse blue 2BLN |
CN102746691A (en) * | 2012-06-18 | 2012-10-24 | 绍兴奇彩化工有限公司 | Technique for separating disperse blue 2BLN mother liquor |
-
1977
- 1977-01-28 JP JP851277A patent/JPS5395955A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS5395955A (en) | 1978-08-22 |
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