EP0000493B1 - Verfahren zur Herstellung von 1-Amino-8-naphthol-3,6-disulfonsäure (H-Säure). - Google Patents

Verfahren zur Herstellung von 1-Amino-8-naphthol-3,6-disulfonsäure (H-Säure). Download PDF

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Publication number
EP0000493B1
EP0000493B1 EP78100354A EP78100354A EP0000493B1 EP 0000493 B1 EP0000493 B1 EP 0000493B1 EP 78100354 A EP78100354 A EP 78100354A EP 78100354 A EP78100354 A EP 78100354A EP 0000493 B1 EP0000493 B1 EP 0000493B1
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EP
European Patent Office
Prior art keywords
acid
reaction
process according
naphthylamine
weight
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Expired
Application number
EP78100354A
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German (de)
English (en)
French (fr)
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EP0000493A1 (de
Inventor
Willi Dr. Schössler
Horst Dr. Behre
Rolf Dr. Pütter
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Bayer AG
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Bayer AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08

Definitions

  • the present invention relates to a process for the preparation of 1-amino-8-naphthol-3,6-disulfonic acid (H-acid) as the monoalkali salt from 1-naphthylamine-3,6,8-trisulfonic acid by alkaline pressure hydrolysis.
  • H-acid 1-amino-8-naphthol-3,6-disulfonic acid
  • 1-Amino-8-naphthol-3,6-disulfonic acid which is often also referred to as H-acid, is an important intermediate for the production of dyes (see Ullmanns Enzyklopadie der Technischen Chemie, 3rd edition, 12th volume, p . 621).
  • the acidic calcium sodium salt of T-acid (1-naphthylamine-3,6,8-trisulfonic acid) is precipitated, which is filtered off and washed several times.
  • This salt is added to the washing water and soda is added.
  • the chalk that has precipitated is pressed and the salt solution is concentrated.
  • the concentrated trisodium salt solution of the T-acid is reacted with 50% sodium hydroxide solution under pressure.
  • sulfuric acid is added first, then water, and finally the H acid is obtained as the monosodium salt by filtration, washing and drying.
  • T-acid e.g. B. the 1-amino-6-naphthol-3,8-disulfonic acid, a known under the name W-acid isomer of H-acid, and the 1,8-dihydroxy-naphthalene-3,6-disulfonic acid, one under the Chromotropic acid is a known by-product of H-acid.
  • the yield of H acid in the process described above is generally only 70 to 72%, based on the T acid used.
  • a process has now been found for the preparation of monoalkali metal salts of 1-amino-8-naphthol-3,6-disulfonic acid by reacting 1-naphthylamine-3,6,8-trisulfonic acid and / or its salts and / or naphthylamine.
  • Naphthylamine - trisulfonic acid - isomer mixtures can contain other products in addition to the naphthylamine trisulfonic acids.
  • Such products can be, in particular, by-products, decomposition products or unreacted intermediates from the production stages for naphthylamine-trisulfonic acid, for example naphthalene-di-, tri- and tetra-sulfonic acids, nitronaphthalene-mono-, di- and trisulfonic acids, naphthylamine-mono - and disulfonic acids, e.g. B.
  • 1-naphthylamine-3,6- and -5,7-disulfonic acid also dinaphthylsulfone sulfonic acids and their amino and nitro derivatives, and oxidation products of naphthalene and / or naphthalene sulfonic acids, which are formed in the sulfonation and / or nitration can.
  • the 1-naphthylamine-3,6,8-trisulfonic acid or the naphthylamine-trisulfonic acid isomer mixtures can be used in free form, in the form of neutral salts or in the form of acid salts. Mixtures containing free acids and salts can also be used. If all or part of the 1-naphthylamine-3,6,8-trisulfonic acid or the naphthylamine-trisulfonic acid isomer mixtures are present as salts, the alkali and alkaline earth metal salts, in particular the sodium and potassium salts, are preferred.
  • Suitable 1-naphthylamine-3,6,8-trisulfonic acid or salts of this acid for use in the process according to the invention can be obtained by trisulfonating naphthalene, nitriding the resulting mixture, then reducing the nitro-naphthalene-trisulfonic acid mixture present, the acidic Calcium-sodium salt of the T-acid precipitates, this salt is mixed with soda in solution, the precipitated chalk is pressed out and the salt solution is concentrated. These reactions can be carried out according to the FIAT Final Report procedure described at the beginning or in any other way.
  • a naphthylamine-trisulfonic acid isomer mixture suitable for use in the process according to the invention can be obtained in a similar manner if you stop the reaction sequence after the reduction of the nitro-naphthalenetrisulfonic acid mixture has ended.
  • the 1-naphthylamine-3,6,8-trisulfonic acid and / or its salts and / or the naphthylamine-trisulfonic acid isomer mixture and / or its salts can be, for example, in solid form or as an aqueous solution with a content of, for example, 20 to 50% by weight. -%, preferably 30 to 40 wt .-%, calculated as the free acid with the molecular weight 383, are used.
  • Alkali hydroxide solutions for the process according to the invention are, in particular, aqueous potassium or sodium hydroxide solution.
  • the use of potassium hydroxide leads to better yields compared to sodium hydroxide solution, but sodium hydroxide solution is generally cheaper.
  • the use of 6 to 9 moles of alkali metal hydroxide per mole of diazotizable substance is particularly preferred.
  • the concentration of alkali hydroxide in the reaction mixture can be, for example, 10 to 50% by weight (based on the sum of alkali hydroxide plus water plus alcohol). This concentration is preferably 25 to 35%.
  • An essential aspect of the process according to the invention is that it is carried out in the presence of alcohols and / or alcoholates.
  • alcohols in pure form, in a mixture with water or in the form of alcoholates, for example in the form of alkali metal alcoholates can be added to the reaction mixture.
  • Suitable alcohols are those alcoholic compounds which are miscible with water under the reaction conditions and which undergo no or only minor undesirable side reactions with strong alkali. In this case, the formation of alcoholate is not an undesirable side reaction.
  • Aliphatic alcohols with, for example, 1 to 6 carbon atoms are preferred.
  • primary, secondary and tertiary monohydric and polyhydric alcohols can be used, the hydroxyl groups of which can also be wholly or partially etherified.
  • monohydric alcohols come e.g. B. in question: methanol, ethanol, n-propanol, 2-propanol, n-butanol, iso-butanol, tert-butanol.
  • polyhydric alcohols such. B. in question: ethylene glycol, propanediols, butanediols, glycerol, butanetriols, monoglyme, diglyme. Mixtures of alcohols can of course also be used. Methanol is particularly preferably used.
  • the amount of alcohol or alcoholate to be used can be chosen, for example, so that 10 to 80% by weight, preferably 25 to 60% by weight, of alcohol or alcoholate, based on the sum of water plus alcohol, is present.
  • the process according to the invention can be carried out, for example, at temperatures from 150 to 250 ° C., preferably at 180 to 220 ° C., in a closed vessel.
  • the pressure which arises is generally completely sufficient to carry out the process according to the invention in a satisfactory manner.
  • the method according to the invention can also be carried out with pressures other than those which set themselves in closed vessels. For example, pressures in the range from 5 to 100 bar are possible for the process according to the invention.
  • the reaction time essentially depends on the reaction temperature and the alkali hydroxide concentration. It is shorter at relatively high reaction temperatures and at relatively high alkali hydroxide concentrations and longer at relatively low reaction temperatures and relatively low alkali hydroxide concentrations and is generally from 10 minutes to 10 hours. For example, good results are obtained at a reaction temperature of approx. 200 ° C. and an alkali hydroxide concentration of 30% by weight with a reaction time of 45 to 60 minutes.
  • the substances to be used in the process according to the invention are most advantageously introduced into the reaction vessel at a temperature such that the desired reaction temperature is present after the heat of mixture and optionally the heat of neutralization has been released.
  • the substances to be entered can also be brought together at lower temperatures and heated to the desired reaction temperature in the reaction vessel.
  • the reaction mixture After the reaction has ended and before the H acid has been separated off as the monoalkali metal salt, it is advantageous to cool the reaction mixture and / or to dilute it with water.
  • the amount of water to be added depends on the reaction conditions, eg. B. the type of alkali metal hydroxide, its amount and concentration, and according to the amount of alcohol that may still be present. It is advantageous to choose the amount of water so that the alkali sulfite formed in the reaction is dissolved or remains dissolved.
  • the H-acid can be separated off as the monoalkali salt by acidifying the reaction mixture with mineral acids.
  • Sulfuric acid is preferably used for this.
  • Sufficient mineral acid is added to form the sparingly soluble monoalkali salt of H-acid.
  • concentration of the mineral acid and / or by adding water before and / or during the addition of the mineral acid it is expedient to ensure that the inorganic salt which forms, for. As sodium sulfate or potassium sulfate, does not fail.
  • a pH in the range from 0 to 4, preferably 0.5 to 2.5 is set for the separation of the H-acid as the monoalkali salt and by dilution with water and / or by appropriate choice of the concentration the mineral acid, based on the weight of the mixture present in the pressure hydrolysis, which brings in 0.1 to 5 times, preferably 0.5 to 2 times, the amount of water.
  • the monoalkali salt of the H-acid can be separated off in a customary manner, for example by filtration. It is advantageous, before the monoalkali salt of the H acid to be separated off, to cool the temperature, for example by Evaporative cooling, set to less than 80 ° C and the separation at a temperature of less than 80 ° C.
  • the separation is preferably carried out at a temperature in the range from 20 to 60 ° C.
  • the monoalkali salt of H-acid present after the separation is usually washed with water and dried, for example in vacuo.
  • the alcohol can be separated off at various points during the working up of the reaction mixture. It is possible to separate the alcohol from an alkaline, neutral or acidic solution before or after the H-acid has been separated off as the monoalkali salt.
  • the alcohol is preferably separated from alkaline or neutral solution and by distillation. It is particularly preferred to distill off the alcohol directly from the reaction mixture, optionally after cooling and / or dilution with water, via a column. If low-boiling alcohols, for example methanol, are used, it may be sufficient to start the distillation without external heat input by depressurization. If the alcohol used separates from the reaction mixture at temperatures lower than the reaction temperature by forming its own phase, it is possible to separate the alcohol by a simple phase separation after cooling the reaction mixture.
  • the separated alcohol is preferably reused in the process according to the invention. It is then only necessary to add any alcohol portions lost during the alkaline pressure hydrolysis and / or during the workup.
  • the process according to the invention provides the advantage over the known processes for the preparation of 1-amino-8-naphthol-3,6-disulfonic acid (H-acid) as the monoalkali salt that higher yields can be achieved and the formation of by-products, in particular the formation of 1-Amino-6-naphthol-3,8-disulfonic acid (W acid) and the formation of 1,8-dihydroxynaphthalene-3,6-disulfonic acid (chromotropic acid) is significantly reduced.
  • W acid 1-Amino-6-naphthol-3,8-disulfonic acid
  • chromotropic acid 1,8-dihydroxynaphthalene-3,6-disulfonic acid
  • the reduced content of the W-acid which is sparingly soluble in acidic solution, also means that the monoalkali salt of the H-acid can be isolated in a particularly pure form without intensive washing which is associated with losses in yield.
  • T-acid tripotassium salt content 13.4 g nitrite / 100 g, 74.7% by weight T-acid with a molecular weight of 383; a total of 69 g nitrite
  • 325 g water and 315 g methanol are in I-nickel autoclaves heated to 210 ° C.
  • 480 g of 70% strength by weight potassium hydroxide solution (6.0 mol of KOH) at 210 ° C. are pressed in using nitrogen as in Example 1.
  • a temperature of 220 ° C. is established, and a 30% by weight KOH solution results, based on water + methanol.
  • the reaction mixture is kept at 220 ° C. for 17 minutes and cooled to 150 ° C.
  • T-acid trisodium salt content 15.3 g of nitrite / 100 g, 85.1% by weight of T-acid with a molecular weight of 383; a total of 0.69 g of nitrite
  • the composition of the reaction mixtures was determined by means of high-pressure liquid chromatography. The alcohols used and the contents of the various acids in the reaction mixture are shown in Table 3 below.
  • the reaction mixture is kept at 200 ° C. for 45 minutes, cooled, diluted with 500 g of water and the methanol is distilled off.
  • the hot reaction solution is pH-controlled, acidified at pH 1 to 1.5 with about 1000 g of 50% strength by weight sulfuric acid, refluxed for 1 hour to remove sulfur dioxide completely, cooled to 40 ° C. under evaporative cooling and 2 hours at 40 ° C kept.
  • the product is filtered at 40 ° C, washed with a total of 500 g of water and dried at 80 ° C in a vacuum.
  • the yield is 62%, based on the T-acid isomer mixture, or 78% based on T-acid.
  • the H-acid quality was determined by high pressure liquid chromatography as follows:
  • the stated contents relate to free acids.
  • the salts mentioned in Example 1 are in fact present. Reaction products from the isomeric naphthylamine-trisulfonic acids are not contained in the isolated product.
  • the product is washed with a total of 5.4 kg of water and dried in vacuo at 80 ° C.
  • the yield is 65%, based on the T-acid isomer mixture, or 78%, based on T-acid.
  • the H-acid quality was determined by high pressure liquid chromatography as follows:
  • the contents of the specified organic acids are calculated on free acids. In fact, the salts given in Example 1 are present.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP78100354A 1977-07-16 1978-07-11 Verfahren zur Herstellung von 1-Amino-8-naphthol-3,6-disulfonsäure (H-Säure). Expired EP0000493B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772732291 DE2732291A1 (de) 1977-07-16 1977-07-16 Verfahren zur herstellung von 1-amino-8-naphthol-3,6-disulfonsaeure (h-saeure)
DE2732291 1977-07-16

Publications (2)

Publication Number Publication Date
EP0000493A1 EP0000493A1 (de) 1979-02-07
EP0000493B1 true EP0000493B1 (de) 1980-01-09

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EP78100354A Expired EP0000493B1 (de) 1977-07-16 1978-07-11 Verfahren zur Herstellung von 1-Amino-8-naphthol-3,6-disulfonsäure (H-Säure).

Country Status (6)

Country Link
US (1) US4178308A (enrdf_load_stackoverflow)
EP (1) EP0000493B1 (enrdf_load_stackoverflow)
JP (1) JPS5419954A (enrdf_load_stackoverflow)
BR (1) BR7804546A (enrdf_load_stackoverflow)
DE (2) DE2732291A1 (enrdf_load_stackoverflow)
IT (1) IT1105430B (enrdf_load_stackoverflow)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2716030C3 (de) * 1977-04-09 1981-07-16 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Monoalkalisalzes der 1-Amino-8-naphthol-3,6-disulfonsäure
US4325889A (en) * 1978-08-04 1982-04-20 Bayer Aktiengesellschaft Process for the preparation of 1-amino-8-naphthol-3,6-disulphonic acid (H-acid)
DE2843680A1 (de) * 1978-10-06 1980-04-24 Bayer Ag Verfahren zur herstellung von 1-amino-8-naphthol-4,6-disulfonsaeure (k-saeure)
DE3118147A1 (de) 1981-05-07 1982-12-02 Bayer Ag, 5090 Leverkusen Verfahren zur isolierung von h-saeure und k-saeure
CN1057521C (zh) * 1997-08-16 2000-10-18 吉林化学工业股份有限公司染料厂 1－氨基－8－奈酚－3.6二磺酸单钠盐生产工艺的改进
US8045165B2 (en) 2008-03-21 2011-10-25 Abbott Point Of Care, Inc. Method and apparatus for determining a focal position of an imaging device adapted to image a biologic sample
JP2011516833A (ja) 2008-03-21 2011-05-26 アボット・ポイント・オブ・ケア 蛍光消光及び／又は蛍光退色を用いて個々の細胞又は粒状物質を分析するための方法及び装置
JP5539309B2 (ja) 2008-03-21 2014-07-02 アボット ポイント オブ ケア インコーポレイテッド 赤血球中に含まれるヘモグロビンの固有色素を利用して血液試料の赤血球指数を決定するための方法及び装置
JP5184697B2 (ja) 2008-03-21 2013-04-17 アボット ポイント オブ ケア インコーポレイテッド 血小板を個々に、及び凝集塊として検出及び計数するための方法及び装置
CN102807513B (zh) * 2012-08-23 2013-12-18 楚源高新科技集团股份有限公司 一种利用h酸母液回收生产变色酸钠盐的工艺
CN103113269B (zh) * 2013-01-23 2015-07-22 绍兴奇彩化工有限公司 1,8-二硝基-3,6-萘二磺酸盐加氢还原方法
CN107986997A (zh) * 2017-12-08 2018-05-04 荆门市熊兴化工有限公司 一种用于h酸生产过程中的碱熔方法
CN115201363B (zh) * 2022-07-06 2024-02-09 广东众和高新科技股份公司 一种检测1,8-二氨基-3,6-萘二磺酸含量的液相色谱分析方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US458286A (en) * 1891-08-25 Werke
US540412A (en) * 1895-06-04 Moritz ulrich and johann bammann
US511708A (en) * 1893-12-26 Gesellschaft fur aotlif fabrikation
US1670406A (en) * 1925-05-09 1928-05-22 Newport Co Process of preparing h-acid
IT1078453B (it) * 1976-06-16 1985-05-08 American Cyanamid Co Perfezionamento nella sintesi di acido ammino-idrossinaftalene-solfonico
US4130581A (en) * 1977-10-03 1978-12-19 American Cyanamid Company Preparing J acid by fusion using phenolic fluxing agent

Also Published As

Publication number Publication date
EP0000493A1 (de) 1979-02-07
JPS6136509B2 (enrdf_load_stackoverflow) 1986-08-19
US4178308A (en) 1979-12-11
IT7850300A0 (it) 1978-07-14
JPS5419954A (en) 1979-02-15
DE2732291A1 (de) 1979-02-01
BR7804546A (pt) 1979-03-20
DE2857516D1 (en) 1980-02-14
IT1105430B (it) 1985-11-04

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