JPS63225352A - Production of 2,7-naphthalenedisulfonic acid - Google Patents
Production of 2,7-naphthalenedisulfonic acidInfo
- Publication number
- JPS63225352A JPS63225352A JP5729987A JP5729987A JPS63225352A JP S63225352 A JPS63225352 A JP S63225352A JP 5729987 A JP5729987 A JP 5729987A JP 5729987 A JP5729987 A JP 5729987A JP S63225352 A JPS63225352 A JP S63225352A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- naphthalenedisulfonic acid
- naphthalenedisulfonic
- diamine
- sulfuric 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.)
- Pending
Links
- VILFVXYKHXVYAB-UHFFFAOYSA-N naphthalene-2,7-disulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 VILFVXYKHXVYAB-UHFFFAOYSA-N 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000012452 mother liquor Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- YZMHQCWXYHARLS-UHFFFAOYSA-N naphthalene-1,2-disulfonic acid Chemical compound C1=CC=CC2=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC=C21 YZMHQCWXYHARLS-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 naphthalenedisulfonic acid diamine salt Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 4
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract 2
- 150000003839 salts Chemical class 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 abstract 1
- 150000004982 aromatic amines Chemical class 0.000 abstract 1
- FITZJYAVATZPMJ-UHFFFAOYSA-N naphthalene-2,6-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(S(=O)(=O)O)=CC=C21 FITZJYAVATZPMJ-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000013078 crystal Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 6
- YZBGUDOBFPDWKS-UHFFFAOYSA-N 2-[4-(trifluoromethoxy)anilino]benzoic acid Chemical compound OC(=O)C1=CC=CC=C1NC1=CC=C(OC(F)(F)F)C=C1 YZBGUDOBFPDWKS-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- GPUMPJNVOBTUFM-UHFFFAOYSA-N naphthalene-1,2,3-trisulfonic acid Chemical compound C1=CC=C2C(S(O)(=O)=O)=C(S(O)(=O)=O)C(S(=O)(=O)O)=CC2=C1 GPUMPJNVOBTUFM-UHFFFAOYSA-N 0.000 description 5
- HYFMZOAPNQAXHU-UHFFFAOYSA-N naphthalene-1,7-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(S(=O)(=O)O)=CC=C21 HYFMZOAPNQAXHU-UHFFFAOYSA-N 0.000 description 5
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 2
- HKGOFWIZZIYCOS-UHFFFAOYSA-N naphthalene-2-sulfonic acid;hydrate Chemical compound O.C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 HKGOFWIZZIYCOS-UHFFFAOYSA-N 0.000 description 2
- 150000004986 phenylenediamines Chemical class 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- GNNALEGJVYVIIH-UHFFFAOYSA-N benzene-1,2-diamine;hydrochloride Chemical compound Cl.NC1=CC=CC=C1N GNNALEGJVYVIIH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はそれ自体Ｈ酸等の染顔料中間体として重要であ
るばかりでなく、耐熱性ポリマー原料である２、７−ナ
フタレンジオールの原料としても有用である２、７−ナ
フタレンジスルホン酸の製造方法に関する。[Detailed Description of the Invention] <Industrial Application Field> The present invention is not only important as an intermediate for dyes and pigments such as H acid, but also as a raw material for 2,7-naphthalene diol, which is a raw material for heat-resistant polymers. The present invention also relates to a method for producing 2,7-naphthalenedisulfonic acid, which is also useful.
〈従来技術とその問題点〉
２．７−ナフタレンジスルホン酸はナフタレン、或は、
β−ナフタレンスルホン酸を硫酸、或は、発煙硫酸によ
りスルホン化することにより容易に生成しうるが、２．
６−ナフタレンジスルホン酸、ｌ、６−ナフタレンジス
ルホン酸、１，７−ナフタレンジスルホン酸、ナフタレ
ンジオールホン酸等の副生が避けられず、これらの混合
物の中から純粋な２，７−ナフタレンジスルホン酸を分
離する操作を必要とする。<Prior art and its problems> 2.7-naphthalenedisulfonic acid is naphthalene or
It can be easily produced by sulfonating β-naphthalenesulfonic acid with sulfuric acid or fuming sulfuric acid, but 2.
By-products such as 6-naphthalenedisulfonic acid, 1,6-naphthalenedisulfonic acid, 1,7-naphthalenedisulfonic acid, and naphthalenediolphonic acid are unavoidable, and pure 2,7-naphthalenedisulfonic acid is selected from a mixture of these. requires an operation to separate the
従来、２，７−ナフタレンジスルホン酸の分離はＰＢレ
ポート記載の方法（ＢＩＯＳファイナルレポート陽目５
２）、即ち、ジスルホン酸の硫酸溶液にアルカリ金属塩
、或は、アルカリ土類金属塩を加え、まず溶解度の小さ
い２．６−ナフタレンジスルホン酸塩を析出せしめた母
液より２．７−ナフタレンジスルホン酸塩を分離する方
法により行なわれていた。 しかし、この方法では、ナ
フタレンジスルホン酸塩の溶解度差が顕著ではないため
、効率的な分離ができず、又、無機塩が廃酸中に蓄積さ
れるため、未反応硫酸を再使用できないという欠点があ
った。Conventionally, 2,7-naphthalenedisulfonic acid was separated using the method described in the PB report (BIOS Final Report Yome 5).
2), that is, an alkali metal salt or an alkaline earth metal salt is added to a sulfuric acid solution of disulfonic acid, and 2.7-naphthalenedisulfone is extracted from the mother liquor from which 2.6-naphthalenedisulfonic acid salt with low solubility is precipitated. This was done by separating the acid salt. However, this method has the drawback that the difference in solubility of naphthalene disulfonate is not significant, so efficient separation is not possible, and unreacted sulfuric acid cannot be reused because inorganic salts accumulate in the waste acid. was there.
この改良方法として、特開昭５４−１６３５６３号およ
び、特開昭５６−７７２５４号では、各ナフタレンジス
ルホン酸異性体について、その溶解度が最も小さくなる
硫酸濃度がそれぞれ異なるという性質を利用し、２，７
−ナフタレンジスルホン酸を直接反応液から、或は、２
，６−ナフタレンジスルホン酸を析出せしめた母液より
晶析する方法が公知である。As an improvement method for this, JP-A-54-163563 and JP-A-56-77254 utilize the property that each naphthalene disulfonic acid isomer has a different sulfuric acid concentration at which its solubility becomes minimum. 7
- Naphthalenedisulfonic acid directly from the reaction solution, or
, 6-naphthalenedisulfonic acid is crystallized from a precipitated mother liquor.
しかし、この方法はナフタレンジスルホン酸異性体間の
溶解度差があまり大きくないため、２．７−ナフタレン
ジスルホン酸の収率が低いばかりか、得られた結晶の純
度も低く、更に、これを原料として用いるためには、特
製工程を必要とするといった欠点があった。However, in this method, the solubility difference between naphthalenedisulfonic acid isomers is not very large, so not only is the yield of 2,7-naphthalenedisulfonic acid low, but the purity of the obtained crystals is also low. It has the disadvantage that a special process is required for its use.
〈発明の目的〉
本発明はかかる従来法の欠点を解決しようどするもので
あフて、２，７−ナフタレンジスルホン酸をナフタレン
などのジスルホン化反応生成物中より効率よく分離する
ことにより、高収率で高純度の２．７−ナフタレンジス
ルホン酸を製造する方法を提供するものである。 本発
明で得られる２、７−ナフタレンジスルホン酸は有機物
純度が９９％以上と高純度であり、又、中和を受けてい
ない為、さらにスルホン化する事により容易にＨ酸の原
料である１、３゜６−ナフタレントリスルホン酸に誘導
することができるものである。<Objective of the Invention> The present invention aims to solve the drawbacks of the conventional methods, and aims to efficiently separate 2,7-naphthalenedisulfonic acid from disulfonation reaction products such as naphthalene, thereby increasing the The present invention provides a method for producing 2,7-naphthalenedisulfonic acid with high yield and purity. The 2,7-naphthalenedisulfonic acid obtained in the present invention has a high organic purity of 99% or more, and since it has not been neutralized, it can be easily used as a raw material for H acid by further sulfonation. , 3°6-naphthalene trisulfonic acid.
〈発明の構成〉
本発明者らはナフタレンジスルホン酸異性体混合物の硫
酸溶液からの晶析による２、７−ナフタレンジスルホン
酸の分離法を詳細に検討した結果、析出する２、７−ナ
フタレンジスルホン酸の収率および、純度は反応生成物
中に混入する１、６−ナフタレンジスルホン酸、１゜７
−ナフタレンジスルホン酸、および、ナフタレントリス
ルホン酸の含有量には殆ど影習されないが、２，６−ナ
フタレンジスルホン酸の含有量には大きく左右されるこ
とを見出した。<Structure of the Invention> As a result of detailed study by the present inventors on a method for separating 2,7-naphthalenedisulfonic acid by crystallization from a sulfuric acid solution of a mixture of naphthalenedisulfonic acid isomers, the precipitated 2,7-naphthalenedisulfonic acid The yield and purity of 1,6-naphthalenedisulfonic acid mixed in the reaction product are 1.7
- It has been found that the content of naphthalene disulfonic acid and naphthalene trisulfonic acid hardly affects the content, but it is greatly affected by the content of 2,6-naphthalene disulfonic acid.
２．７−ナフタレンジスルホン酸の溶解度が最も小さく
なるのは硫酸濃度が５０％付近であるが、この濃度にお
ける２、６−ナフタレンジスルホン酸の溶解度もまた小
さいため、２゜６−ナフタレンジスルホン酸の同時析出
が避けられない。 そこで、晶析すべきジスルホン酸異
性体混合物中の２．６−ナフタレンジスルホン酸含有量
を予め減少させることを検討した結果、２，７−ナフタ
レンジスルホン酸の収率、および純度を大巾に向上させ
ることができる様になったものである。The solubility of 2.7-naphthalenedisulfonic acid is the lowest at a sulfuric acid concentration of around 50%, but the solubility of 2,6-naphthalenedisulfonic acid at this concentration is also low. Simultaneous precipitation is unavoidable. Therefore, as a result of considering reducing the content of 2,6-naphthalenedisulfonic acid in the disulfonic acid isomer mixture to be crystallized, the yield and purity of 2,7-naphthalenedisulfonic acid were significantly improved. It is now possible to do so.
ジスルホン酸異性体混合物中からの２．６−ナフタレン
ジスルホン酸の除去方法としては、特開昭５４−１６３
５６３号、および、特開昭５６−７７２５４号に公知の
硫酸濃度を調節する事による方法があるが、この場合、
前述のように２，６−ナフタレンジスルホン酸の分離収
率が悪い為、得られる２、７−ナフタレンジスルホン酸
も純度、収率ともに低いという問題がある。A method for removing 2,6-naphthalenedisulfonic acid from a mixture of disulfonic acid isomers is described in JP-A-54-163.
No. 563 and Japanese Unexamined Patent Publication No. 56-77254, there is a known method by adjusting the sulfuric acid concentration, but in this case,
As mentioned above, since the separation yield of 2,6-naphthalenedisulfonic acid is poor, there is a problem that the obtained 2,7-naphthalenedisulfonic acid is also low in both purity and yield.
又、特公昭５９−２６６１９号にはアニリンを用いた２
、６−ナフタレンジスルホン酸の分離方法が公知である
。 しかし、この方法では母液中にかなりの量のアニリ
ンが混入するため、母液からの酸状態での晶析分離を行
なうと母液中にアニリンが移行し、２，７−ナフタレン
ジスルホン酸、硫酸を含む廃酸をリサイクルすることが
不可能であるという欠点があった。In addition, in Special Publication No. 59-26619, 2 using aniline
, 6-naphthalenedisulfonic acid is known. However, in this method, a considerable amount of aniline is mixed into the mother liquor, so when crystallization separation from the mother liquor is performed in an acid state, aniline is transferred to the mother liquor and contains 2,7-naphthalenedisulfonic acid and sulfuric acid. The disadvantage was that it was impossible to recycle the waste acid.
本発明者らは各種ジアミンを用いたスルホン酸の分離方
法の詳細な検討の結果、特にバラフェニレンジアミンあ
るいはその誘導体などを分離剤として用いた場合、分離
剤が２．６−ナフタレンジスルホン酸とのみ硫酸溶液に
殆ど不溶の塩を作るため、２．６−ナフタレンジスルホ
ン酸を完全に分離することができ、これにより、母液中
の２，６−ナフタレンジスルホン酸含有量を極めて低く
抑え、又、分離剤として用いたアミンについては、全く
母液中に混入させないことに成功した。 この結果、２
．６−ナフタレンジスルホン酸塩を分離した母液を濃縮
し、２．７−ナフタレンジスルホン酸の最も溶解度の小
さい５０％付近の硫酸濃度での晶析により、９９％以上
の高純度の２，７−ナフタレンジスルホン酸を７５％以
上の高収率で析出させることができ（この際の廃酸はス
ルホン化工程にリサイクルすることにより、）極めて収
率よく、高純度の２．７−ナフタレンジスルホン酸を製
造する事に成功したものである。As a result of detailed studies on separation methods for sulfonic acids using various diamines, the present inventors found that, in particular, when phenylene diamine or its derivatives were used as a separation agent, the separation agent was only 2,6-naphthalenedisulfonic acid. Since the salt is almost insoluble in the sulfuric acid solution, 2,6-naphthalenedisulfonic acid can be completely separated, thereby keeping the content of 2,6-naphthalenedisulfonic acid in the mother liquor extremely low. Regarding the amine used as the agent, we succeeded in not mixing it into the mother liquor at all. As a result, 2
．． The mother liquor from which 6-naphthalenedisulfonic acid was separated was concentrated and crystallized at a sulfuric acid concentration near 50%, which is the lowest solubility of 2.7-naphthalenedisulfonic acid, to produce 2,7-naphthalene with a purity of over 99%. Disulfonic acid can be precipitated with a high yield of 75% or more (by recycling the waste acid in the sulfonation process), producing highly pure 2,7-naphthalenedisulfonic acid with an extremely good yield. It was successful in doing so.
すなわち本発明は、ナフタレンジスルホン酸異性体混合
物を含有する溶液に、この溶液中において一般式１
（Ｒ１，Ｒ４は同−又は異なり、水素、塩素、フッ素、
臭素、又は、ヨウ素原子、又は、炭素数１〜３のアルキ
ル基である）
で表わされる芳香族ジアミンを生成する化合物を分離剤
として加え、析出した２、６−ナフタレンジスルホン酸
ジアミン塩を濾別し、この母液を濃縮し、硫酸濃度を４
０〜６０％に調整したのち、５０℃以下で２．７−ナフ
タレンジスルホン酸を晶析分離することを特徴とする２
゜７−ナフタレンジスルホン酸の製造方法を提供するも
のである。That is, the present invention provides a solution containing a mixture of naphthalenedisulfonic acid isomers containing the general formula 1 (R1 and R4 are the same or different, hydrogen, chlorine, fluorine,
A compound that produces an aromatic diamine represented by (bromine, iodine atom, or alkyl group having 1 to 3 carbon atoms) is added as a separating agent, and the precipitated 2,6-naphthalenedisulfonic acid diamine salt is separated by filtration. Then, concentrate this mother liquor and reduce the sulfuric acid concentration to 4.
2, characterized in that 2,7-naphthalenedisulfonic acid is crystallized and separated at 50°C or less after adjusting it to 0 to 60%.
A method for producing 7-naphthalenedisulfonic acid is provided.
〈発明の具体的構成〉
以下、本発明を３つの工程にわけて更に詳しく説明する
。<Specific Structure of the Invention> The present invention will be explained in more detail below by dividing it into three steps.
（第１工程）
ナフタレンジスルホン酸異性体混合物を含有する溶液を
生成する工程。 これは次により得られる溶液が好まし
い。(First step) A step of producing a solution containing a mixture of naphthalenedisulfonic acid isomers. This is preferably a solution obtained by the following.
ナフタレン又はβ−ナフタレンスルホン酸を硫酸、或は
発煙硫酸等のスルホン化剤でスルホン化し、２，６−ナ
フタレンジスルホン酸、２．７−ナフタレンジスルホン
酸を主成分とする反応溶液を得るジスルホン化工程。A disulfonation step in which naphthalene or β-naphthalenesulfonic acid is sulfonated with a sulfonating agent such as sulfuric acid or oleum to obtain a reaction solution containing 2,6-naphthalenedisulfonic acid and 2,7-naphthalenedisulfonic acid as main components. .
（第２工程）
上記ジスルホン化反応溶液に対し、所定量の芳香族ジア
ミン、或は、その塩を添加し、２゜６−ナフタレンジス
ルホン酸をジアミン塩として分離する工程。(Second step) A step of adding a predetermined amount of aromatic diamine or its salt to the disulfonation reaction solution and separating 2°6-naphthalenedisulfonic acid as a diamine salt.
（第３工程）
上記第２工程で得られた２、７−ナフタレンジスルホン
酸を主成分とする母液を濃縮した後冷却し、２．７−ナ
フタレンジスルホン酸を析出させる２、７−ナフタレン
ジスルホン酸の単離工程。(Third step) The mother liquor mainly composed of 2,7-naphthalenedisulfonic acid obtained in the second step is concentrated and then cooled to precipitate 2,7-naphthalenedisulfonic acid. isolation process.
第１工程で用いるスルホン化剤のモル倍率は理論量の１
〜３倍の範囲で用いることが好ましい。 反応温度はジ
スルホン化を目的とした標準的な反応温度でよく、一般
的には１４０〜１９０℃の範囲であればよい。The molar ratio of the sulfonating agent used in the first step is 1 of the theoretical amount.
It is preferable to use the amount in the range of ~3 times. The reaction temperature may be a standard reaction temperature for the purpose of disulfonation, and is generally in the range of 140 to 190°C.
第２工程で用いる芳香族ジアミンとは下記一般式１で表
わされる化合物であり、塩酸塩、或は、硫酸塩といった
塩の形でも用いることができる。The aromatic diamine used in the second step is a compound represented by the following general formula 1, and can also be used in the form of a salt such as a hydrochloride or a sulfate.
（Ｒ１〜Ｒ４は同−又は異なり、水素、塩素、フッ素、
臭素、又は、ヨウ素原子、又は、アルキル基である）。(R1 to R4 are the same or different, hydrogen, chlorine, fluorine,
bromine or iodine atom, or an alkyl group).
一般式１で表わされる化合物の中ではＲ１−Ｒ４が水素
であるものが工業的に得られやすく好ましい。Among the compounds represented by the general formula 1, those in which R1 to R4 are hydrogen are preferred because they can be obtained industrially.
ざらには、芳香族ジアミンの有機酸とのアミド化合物、
例えばモノアセチル体等も使用することができる。 こ
のように、本発明においては、２，６−ナフタレンジス
ルホン酸を含有する溶液中で、特にその水溶液中で上記
一般式１で示される芳香族ジアミンを容易に生成するも
のであればいかなる化合物でもよい。Zara is an amide compound of aromatic diamine with organic acid,
For example, monoacetyl derivatives can also be used. Thus, in the present invention, any compound can be used as long as it easily produces the aromatic diamine represented by the above general formula 1 in a solution containing 2,6-naphthalenedisulfonic acid, especially in an aqueous solution thereof. good.
本発明でのジアミンの使用量は、２，６−ナフタレンジ
スルホン酸含有量に対し、０．５〜１．５倍モル、好ま
しくは、０．９〜１．３倍モル使用するのが良い。The amount of diamine used in the present invention is preferably 0.5 to 1.5 times, preferably 0.9 to 1.3 times, the amount of 2,6-naphthalenedisulfonic acid.
ジアミンは結晶をそのまま添加してもよいし、又、水、
或は、炭素数１〜８のアルコール溶媒の溶液を滴下して
もよい。The diamine may be added directly as a crystal, or may be added with water,
Alternatively, a solution of an alcohol solvent having 1 to 8 carbon atoms may be added dropwise.
ここで用いるジスルホン化反応液の硫酸濃度（硫酸／（
硫酸＋水））は８０％以下、好ましくは６０％以下の範
囲に調整することが望ましい。 ８０％超では２．６−
ナフタレンジスルホン酸バラフェニレンジアミン塩の母
液への溶解度が若干増し、分離率が若干低下する為であ
る。Sulfuric acid concentration (sulfuric acid/(
Sulfuric acid + water)) is desirably adjusted to a range of 80% or less, preferably 60% or less. 2.6- for over 80%
This is because the solubility of naphthalenedisulfonic acid phenylenediamine salt in the mother liquor increases slightly, and the separation rate decreases slightly.
第３工程での母液の濃縮は硫酸濃度が４０〜６０％、更
に好ましくは４５〜５５％になるまで行なえば良く、そ
の方法は常圧下でも減圧下でもよい。 硫酸濃度が４０
％未満でも６０％超でもジスルホン酸の溶解度が増加し
収率が低下するためである。Concentration of the mother liquor in the third step may be carried out until the sulfuric acid concentration reaches 40 to 60%, more preferably 45 to 55%, and the method may be under normal pressure or reduced pressure. Sulfuric acid concentration is 40
This is because the solubility of disulfonic acid increases and the yield decreases if it is less than 60% or more than 60%.
２．７−ナフタレンジスルホン酸の晶析は５０℃以下、
更に好ましくは３０℃以下で行なう。 ５０℃をこえ
る温度ではジスルホン酸の溶解度が大きく収率が低下す
る。 結晶を濾通することにより、純度９９％以上の２
．７−ナフタレンジスルホン酸を収率７５％以−トで単
離することができる。2. Crystallization of 7-naphthalenedisulfonic acid is below 50°C,
More preferably, the temperature is 30°C or lower. At temperatures exceeding 50°C, the solubility of disulfonic acid becomes large and the yield decreases. By filtering the crystals, 2 with a purity of 99% or more is obtained.
．． 7-Naphthalenedisulfonic acid can be isolated with a yield of 75% or more.
〈実施例〉
以下に本発明を実施例および比較例を挙げて具体的に説
明する。<Examples> The present invention will be specifically described below with reference to Examples and Comparative Examples.
（実施例１）
四つ目フラスコに６０％β−ナフタレンスルホン酸永和
物３尋７ｇを入れ、水を除去しながら、１８０℃まで昇
温した。ここに、２４５ｇの濃硫酸を１時間にわたり滴
下後、１８０℃でさらに５時間スルホン化反応を続けた
。 この時、得られた組成は２，６−ナフタレンジスル
ホン酸０．３１モル、２，７−ナフタレンジスルホン１
％ｌ’０．５δモル、１．６−ナフタレンジスルホン酸
０．０２モル、１，７−ナフタレンジスルホン酸０．０
２モル、ナフタレントリスルホン酸０．０６モルおよび
硫酸１．００モルであった。(Example 1) 3 fathoms 7 g of 60% β-naphthalene sulfonic acid hydrate was placed in a fourth flask, and the temperature was raised to 180° C. while removing water. After dropping 245 g of concentrated sulfuric acid over 1 hour, the sulfonation reaction was continued at 180° C. for another 5 hours. At this time, the obtained composition was 0.31 mol of 2,6-naphthalenedisulfonic acid, 1 mol of 2,7-naphthalenedisulfonic acid.
%l'0.5δ mol, 1,6-naphthalenedisulfonic acid 0.02 mol, 1,7-naphthalenedisulfonic acid 0.0
2 mol, naphthalene trisulfonic acid 0.06 mol and sulfuric acid 1.00 mol.
このナフタレンジスルホン酸異性体混合物に水５００ｇ
を添加し、９０℃にてバラフェニレンジアミン３３ｇを
水３００ｇに溶解した溶液を滴下した。 同温度にて１
時間かくはん後、室温まで冷却し、析出する結晶を濾通
し、５００ｇの水にて洗浄することにより３７８ｇの２
．６−ナフタレンジスルホン酸バラフェニレンジアミン
塩のウェットケーキを得た。 この母液を硫酸濃度が５
０％になる様に５０〜８０℃で減圧濃縮した後、５０℃
で１時間晶析した後、更に１０℃まで冷却し、析出する
結晶を濾過し、２１５ｇの２．７−ナフタレンジスルホ
ン酸のウェットケーキを得た。 得られた結晶の収率お
よび純度を表１に示す。Add 500 g of water to this naphthalene disulfonic acid isomer mixture.
was added thereto, and a solution of 33 g of rose phenylenediamine dissolved in 300 g of water was added dropwise at 90°C. At the same temperature 1
After stirring for an hour, cool to room temperature, filter the precipitated crystals, and wash with 500 g of water to obtain 378 g of 2
．． A wet cake of 6-naphthalenedisulfonic acid phenylenediamine salt was obtained. This mother liquor has a sulfuric acid concentration of 5
After concentrating under reduced pressure at 50-80℃ to 0%, 50℃
After crystallizing for 1 hour, the mixture was further cooled to 10° C., and the precipitated crystals were filtered to obtain 215 g of a wet cake of 2,7-naphthalenedisulfonic acid. Table 1 shows the yield and purity of the obtained crystals.
（実施例２）
四つロフラスコにナフタレン１２８ｇを入れ、１４０℃
まで昇温した。 ここに、１２０ｇの濃硫酸を１時間に
わたり滴下後、１６０℃まで昇温し、更に２３０ｇの硫
酸を１時間にわたり滴下後、５時間スルホン化反応を続
けた。(Example 2) 128g of naphthalene was placed in a four-loaf flask and heated to 140°C.
The temperature rose to . After 120 g of concentrated sulfuric acid was added dropwise over 1 hour, the temperature was raised to 160° C., and after 230 g of sulfuric acid was added dropwise over 1 hour, the sulfonation reaction was continued for 5 hours.
この時、得られた組成は２．６−ナフタレンジスルホン
酸０．２２モル、２．７−ナフタレンジスルホン酸０．
４８モル、１．６−ナフタレンジスルホン酸０．０３モ
ル、１，７−ナフタレンジスルホン酸０．０５モル、ナ
フタレントリスルホン酸０．０３モル、および硫酸１．
５モルであった。At this time, the obtained composition was 0.22 mol of 2.6-naphthalenedisulfonic acid and 0.22 mol of 2.7-naphthalenedisulfonic acid.
48 mol, 0.03 mol of 1,6-naphthalenedisulfonic acid, 0.05 mol of 1,7-naphthalenedisulfonic acid, 0.03 mol of naphthalene trisulfonic acid, and 1.0 mol of sulfuric acid.
It was 5 moles.
このナフタレンジスルホン酸異性体混合物に水５００ｇ
を添加し、９０℃にてバラフェニレンジアミン２４ｇを
水３００ｇに溶解した溶液を滴下した。 同温度にて１
時間かくはん後、室温まで冷却し、析出する結晶を濾過
し、５００ｇの水にて洗浄することに、より、２６８ｇ
の２，６−ナフタレンジスルホン酸バラフェニレンジア
ミン塩のウェットケーキを得た。Add 500 g of water to this naphthalene disulfonic acid isomer mixture.
was added thereto, and a solution of 24 g of rose phenylenediamine dissolved in 300 g of water was added dropwise at 90°C. At the same temperature 1
After stirring for an hour, cool to room temperature, filter the precipitated crystals, and wash with 500 g of water to obtain 268 g.
A wet cake of phenylenediamine salt of 2,6-naphthalenedisulfonic acid was obtained.
この母液を硫酸濃度が５０％になる様に５０〜８０℃で
減圧濃縮した後、５０℃で１時間晶析した後、更に１０
℃まで冷却し、析出する結晶を濾通し、１９０ｇの２．
７−ナフタレンジスルホン酸のウェットケーキを得た。This mother liquor was concentrated under reduced pressure at 50 to 80°C so that the sulfuric acid concentration was 50%, and then crystallized at 50°C for 1 hour.
℃, the precipitated crystals were filtered, and 190 g of 2.
A wet cake of 7-naphthalenedisulfonic acid was obtained.
得られた結晶の収率および純度を表１に示す。Table 1 shows the yield and purity of the obtained crystals.
（実施例３）
四つ目フラスコにナフタレン１２８ｇを入れ、１４０℃
まで昇温した。 ここに、１２０ｇの濃硫酸を１時間に
わたり滴下後、１６０℃まで昇温し、更に２３０ｇの硫
酸を１時間にわたり滴下後、５時間スルホン化反応を続
けた。(Example 3) Put 128g of naphthalene into a fourth flask and heat to 140°C.
The temperature rose to . After 120 g of concentrated sulfuric acid was added dropwise over 1 hour, the temperature was raised to 160° C., and after 230 g of sulfuric acid was added dropwise over 1 hour, the sulfonation reaction was continued for 5 hours.
この時、得られた組成は２．６−ナフタレンジスルホン
酸０．２４モル、２．７−ナフタレンジスルホン酸０．
４７モル、１．６−ナフタレンジスルホン酸０．０３モ
ル、１，７−ナフタレンジスルホン酸０．０６モル、ナ
フタレントリスルホン酸０．０３モルおよび硫酸１．５
モルであった。At this time, the obtained composition was 0.24 mol of 2.6-naphthalenedisulfonic acid and 0.24 mol of 2.7-naphthalenedisulfonic acid.
47 mol, 0.03 mol of 1,6-naphthalenedisulfonic acid, 0.06 mol of 1,7-naphthalenedisulfonic acid, 0.03 mol of naphthalene trisulfonic acid and 1.5 mol of sulfuric acid.
It was a mole.
このナフタレンジスルホン酸異性体混合物に水５００ｇ
を添加し、９０℃にてバラフェニレンジアミン塩酸塩４
３ｇを水３００ｇに溶解した溶液を滴下した。 同温度
にて１時間かくはん後、室温まで冷却し、析出する結晶
を濾通し、５００ｇの水にて洗浄することにより、２９
３ｇの２．６−ナフタレンジスルホン酸バラフェニレン
ジアミン塩のウェットケーキを得た。 この母液を硫酸
濃度が５０％になる様に５０〜８０℃で減圧濃縮した後
、５０℃で１時間晶析した後、更に１０℃まで冷却し、
析出する結晶を濾過し、１８７ｇの２．７−ナフタレン
ジスルホン酸のウェットケーキを得た。Add 500 g of water to this naphthalene disulfonic acid isomer mixture.
of phenylenediamine hydrochloride 4 at 90°C.
A solution of 3 g dissolved in 300 g of water was added dropwise. After stirring at the same temperature for 1 hour, it was cooled to room temperature, and the precipitated crystals were filtered and washed with 500 g of water.
3 g of a wet cake of 2,6-naphthalenedisulfonic acid bulk phenylene diamine salt was obtained. This mother liquor was concentrated under reduced pressure at 50 to 80°C so that the sulfuric acid concentration was 50%, and then crystallized at 50°C for 1 hour, and then further cooled to 10°C.
The precipitated crystals were filtered to obtain 187 g of a wet cake of 2.7-naphthalenedisulfonic acid.
得られた結晶の収率および純度を表１に示す。Table 1 shows the yield and purity of the obtained crystals.
（比較例）
四つロフラスコに６０％β−ナフタレンスルホン酸水和
物３４７ｇを入れ、水を除去しながら、１８０℃まで昇
温した。 ここに、２４５ｇの濃硫酸を１時間にわたり
滴下後、１８０℃で更に５時間スルホン化反応を続けた
。この時、得られた組成は２．６−ナフタレンジスルホ
ン酸０．３１モル、２，７−ナフタレンジスルホン酸０
．５６モル、１．６−ナフタレンジスルホンＭ Ｏ，０
２モル、１，７−ナフタレンジスルホン酸０．０２モル
、ナフタレントリスルホン酸０．０６モルおよび硫酸１
．００モルてあった。(Comparative Example) 347 g of 60% β-naphthalenesulfonic acid hydrate was placed in a four-bottle flask, and the temperature was raised to 180° C. while removing water. After dropping 245 g of concentrated sulfuric acid over 1 hour, the sulfonation reaction was continued at 180° C. for another 5 hours. At this time, the obtained composition was 0.31 mol of 2,6-naphthalenedisulfonic acid, 0 mol of 2,7-naphthalenedisulfonic acid.
．． 56 mol, 1,6-naphthalenedisulfone M O,0
2 moles, 0.02 moles of 1,7-naphthalenedisulfonic acid, 0.06 moles of naphthalenetrisulfonic acid and 1 mol of sulfuric acid.
．． There were 00 moles.
この溶液に水を加え、硫酸濃度を７０％に調整した後２
５℃迄冷却し、析出する２、６−ナフタレンジスルホン
酸を濾過した後、母液の硫酸濃度を５０％に成るように
更に水を加え、１０℃迄冷却し析出する結晶を濾過し、
９７ｇの２．７−ナフタレンジスルホン酸のウェットケ
ーキを得た。得られた結晶の収率および純度を表１に示
す。After adding water to this solution and adjusting the sulfuric acid concentration to 70%,
After cooling to 5°C and filtering the precipitated 2,6-naphthalenedisulfonic acid, water was further added to make the sulfuric acid concentration of the mother liquor 50%, and the mixture was cooled to 10°C and the precipitated crystals were filtered.
97 g of 2,7-naphthalenedisulfonic acid wet cake was obtained. Table 1 shows the yield and purity of the obtained crystals.
表１２，７−ナフタレンジスルホン酸の収率及び純度
〈発明の効果〉
以上述べたところから明らかなように、本発明方法によ
れば、まずナフタレンジスルホン酸混合物溶液から２．
６−ナフタレンジスルホン酸を効率よく除去し、その母
液より、２．７−ナフタレンジスルホン酸を晶析させる
ので、２．７−ナフタレンジスルホン酸を効率よくうる
ことができる。Table 12. Yield and purity of 7-naphthalenedisulfonic acid <Effects of the invention> As is clear from the above, according to the method of the present invention, 2.
Since 6-naphthalenedisulfonic acid is efficiently removed and 2.7-naphthalenedisulfonic acid is crystallized from the mother liquor, 2.7-naphthalenedisulfonic acid can be efficiently obtained.
特許出願人 川崎製鉄株式会社 同 出願人 株式会社Patent applicant: Kawasaki Steel Corporation Same applicant: Co., Ltd.
Claims (1)
溶液に、この溶液中において一般式 I ▲数式、化学式
、表等があります▼（ I ） （Ｒ＾１〜Ｒ＾４は同一又は異なり、水素、塩素、フッ
素、臭素、又は、ヨウ素原子、又は、炭素数１〜３のア
ルキル基である） で表わされる芳香族ジアミンを生成する化合物を分離剤
として加え、析出した２，６−ナフタレンジスルホン酸
ジアミン塩を濾別し、この母液を濃縮し、硫酸濃度を４
０〜６０％に調整したのち、５０℃以下で２，７−ナフ
タレンジスルホン酸を晶析分離することを特徴とする２
，７−ナフタレンジスルホン酸の製造方法。(1) In a solution containing a mixture of naphthalenedisulfonic acid isomers, there is a general formula I ▲mathematical formula, chemical formula, table, etc.▼(I) (R^1 to R^4 are the same or different, hydrogen, 2,6-naphthalenedisulfonic acid diamine precipitated by adding a compound that produces an aromatic diamine represented by (chlorine, fluorine, bromine, or iodine atom, or an alkyl group having 1 to 3 carbon atoms) as a separating agent. The salts were filtered off, the mother liquor was concentrated, and the sulfuric acid concentration was reduced to 4.
2, characterized in that 2,7-naphthalenedisulfonic acid is crystallized and separated at 50°C or lower after being adjusted to 0 to 60%.
, 7-naphthalenedisulfonic acid manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5729987A JPS63225352A (en) | 1987-03-12 | 1987-03-12 | Production of 2,7-naphthalenedisulfonic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5729987A JPS63225352A (en) | 1987-03-12 | 1987-03-12 | Production of 2,7-naphthalenedisulfonic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63225352A true JPS63225352A (en) | 1988-09-20 |
Family
ID=13051676
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5729987A Pending JPS63225352A (en) | 1987-03-12 | 1987-03-12 | Production of 2,7-naphthalenedisulfonic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63225352A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993061A (en) * | 2012-07-30 | 2013-03-27 | 枣庄市泰瑞精细化工有限公司 | Preparation method of 2,7-sodium naphthalenedisulfonate product using transforming production of 1,6-naphthalenedisulfonic mother liquid |
| CN115433110A (en) * | 2022-08-30 | 2022-12-06 | 安徽生源化工有限公司 | Method for preparing 2, 7-sodium naphthalenedisulfonate by recycling naphthol-containing wastewater |
-
1987
- 1987-03-12 JP JP5729987A patent/JPS63225352A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102993061A (en) * | 2012-07-30 | 2013-03-27 | 枣庄市泰瑞精细化工有限公司 | Preparation method of 2,7-sodium naphthalenedisulfonate product using transforming production of 1,6-naphthalenedisulfonic mother liquid |
| CN115433110A (en) * | 2022-08-30 | 2022-12-06 | 安徽生源化工有限公司 | Method for preparing 2, 7-sodium naphthalenedisulfonate by recycling naphthol-containing wastewater |
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