EP2044011A1 - Procede de preparation de dihydroxybenzenedisulfonates metalliques - Google Patents

Procede de preparation de dihydroxybenzenedisulfonates metalliques

Info

Publication number
EP2044011A1
EP2044011A1 EP07730083A EP07730083A EP2044011A1 EP 2044011 A1 EP2044011 A1 EP 2044011A1 EP 07730083 A EP07730083 A EP 07730083A EP 07730083 A EP07730083 A EP 07730083A EP 2044011 A1 EP2044011 A1 EP 2044011A1
Authority
EP
European Patent Office
Prior art keywords
acid
process according
dihydroxybenzenedisulfonic
sulfuric acid
sulfate
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.)
Withdrawn
Application number
EP07730083A
Other languages
German (de)
English (en)
French (fr)
Inventor
Michel Dury
Hervé Bres
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP2044011A1 publication Critical patent/EP2044011A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
    • C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
    • C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/04—Sodium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
    • C07C309/41—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton
    • C07C309/42—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing singly-bound oxygen atoms bound to the carbon skeleton having the sulfo groups bound to carbon atoms of non-condensed six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/06—Potassium compounds

Definitions

  • the present invention relates to a process for the preparation of metal dihydroxybenzenedisulfonates from corresponding dihydroxybenzenedisulphonic acids.
  • the invention relates more particularly to the alkali metal salts, preferably the sodium or potassium salts.
  • the salts of dihydroxybenzenedisulphonic acids find applications in many fields, in particular photography, water treatment and detergency.
  • the sulfonation of dihydroxybenzene can be carried out using oleum.
  • an aqueous solution of alkali metal hydroxide in particular sodium hydroxide, is used to effect the salification of dihydroxybenzenedisulfonic acid.
  • a filtrate (mother liquors) which comprises sulfuric acid which can be recovered but which is diluted due to the addition of sodium hydroxide in the form of of aqueous solution, and that the salification reaction with soda leads to the formation of water.
  • the present invention provides a process which makes it possible to regenerate more easily the mother liquors containing sulfuric acid resulting from the separation of the metal dihydroxybenzenedisulfonate.
  • the subject of the present invention is a process for the preparation of a metal dihydroxybenzenedisulfonate from a corresponding dihydroxybenzenedisulphonic acid, characterized in that it comprises the reaction of dihydroxybenzenedisulphonic acid present in sulfuric medium with a sufficient amount of a salt. comprising a sulfate or hydrogen sulfate anion.
  • the salification operation according to the invention is carried out on the reaction medium resulting from the preliminary sulphonation step.
  • This type of salification which is a neutralization of the two sulphonic acid functions by a sulphate or hydrogen sulphate salt, makes it possible during this reaction to form sulfuric acid, and thus, after separation, (most often by filtration) of the salt. expected from the reaction medium, to regenerate more easily the mother liquors containing sulfuric acid.
  • the mother liquors resulting from the separation are concentrated in sulfuric acid (> 60%) and can be sent directly to the regeneration, thus making this process without aqueous effluent.
  • the process of the invention is applicable to any dihydroxybenzenedisulfonic acid.
  • the OH group is in the ortho, meta or para position of the other hydroxyl group
  • the sulphonic groups SO 3 H are in the ortho and / or para position relative to the hydroxyl groups.
  • the invention does not exclude the presence of one or two substituents on the benzene ring to the extent that they are not troublesome.
  • More specific examples include, among others, linear or branched alkyl or alkoxy groups having 1 to 20 carbon atoms, preferably 1 to 6 carbon atoms; perfluoroalkyl groups having from 1 to 4 carbon atoms; halogen atoms, preferably chlorine, bromine or fluorine.
  • dihydroxybenzenedisulphonic acids used include disulfonic acids resulting from the sulfonation of hydroquinone (1,4-dihydroxybenzene), pyrocatechol (1,2-dihydroxybenzene), and resorcinol (1, 3-dihydroxybenzene).
  • the preferred dihydroxybenzenedisulphonic acids are 1,2-dihydroxy-3,5-benzenedisulphonic acid, 1,3-dihydroxy-4,6-benzenedisulphonic acid and 1,4-dihydroxy-2,5-benzenedisulfonic acid.
  • the dihydroxybenzenedisulfonic acid is reacted with a salt comprising a sulfate or hydrogen sulfate anion.
  • the sulphate or hydrogen sulphate anion may be employed in any form.
  • It may be a metallic element and more particularly an element of group la or Ib of the periodic table of elements.
  • element for the definition of elements, reference is made hereinafter to the Periodic Table of Elements published in the Bulletin of the Chemical Society of France, No. 1 (1966).
  • Metallic elements of group la include lithium, sodium and potassium and group Ib, copper and silver. However, for economic reasons, it is preferable to use commercially accessible forms.
  • An alkaline metal element belonging to group la is advantageously chosen.
  • It is preferably sodium or potassium sulphate or hydrogen sulphate, or lithium.
  • Sodium or potassium sulphate is particularly preferred.
  • the sulphate or hydrogen sulphate salt is preferably used in solid form in order not to dilute the reaction medium.
  • the amount of sulphate or hydrogen sulphate salt used expressed as the ratio between the number of moles of sulphate or hydrogen sulphate salt and the number of moles of dihydroxybenzenedisulphonic acid varies between 1, 6 and 2.5, preferably between 1, 9 and 2.1 and is preferentially located around
  • the sulphate or hydrogen sulphate salt is introduced into the reaction medium comprising dihydroxybenzenedisulphonic acid or vice versa.
  • the salification reaction is conducted at a temperature between 40 ° C and 80 ° C, preferably between 50 ° C and 60 ° C.
  • the dihydroxybenzenedisulfonic acid is then in salified form, preferably in the form of sodium or potassium salt when the salt chosen is sodium or potassium sulfate or hydrogen sulphate. It can be in hydrated form, most often in the form of monohydrate.
  • the precipitate is separated according to standard solid / liquid separation techniques, preferably by filtration.
  • It may optionally be subjected to a washing operation, for example with the aid of an alcohol, preferably methanol, ethanol or isopropanol.
  • an alcohol preferably methanol, ethanol or isopropanol.
  • the salification reaction is preferably carried out on the dihydroxybenzenedisulphonic acid resulting from the sulphonation step.
  • the dihydroxybenzene corresponding to dihydroxybenzenedisulfonic acid of formula (I) is subjected to a sulfonation step which can be carried out by sulfuric acid or its oleums. It is possible to use an aqueous solution of sulfuric acid having a concentration of between 90 and 100%. It is preferred to use a concentrated solution and the commercial form is preferably chosen at 98% by weight.
  • oleas which correspond to the sulfuric acid loaded with sulfuric anhydride SO 3 , the concentration of which can vary between 10% and 65% by weight.
  • Oleum oils with 20%, 40% or 60% by weight of SO 3 are commercially available.
  • the sulfonation is carried out in the presence of an excess of sulfuric acid.
  • the ratio between the number of moles of sulfuric acid is the number of moles of dihydroxybenzene is preferably at least 3, and more preferably between 4 and 6.
  • the sulfonation is in particular conducted at a temperature above the crystallization temperature of the reaction medium. It is preferably between 50 ° C and 100 ° C.
  • the duration of the sulfonation reaction, and in continuous operation, the overall average residence time are in particular between 1 and 10 hours, more particularly between 1 and 5 hours.
  • dihydroxybenzene is generally introduced into sulfuric acid and then heated to the chosen temperature.
  • Dihydroxybenzenedisulfonic acid is obtained in the presence of an excess of sulfuric acid: the ratio between the number of moles of sulfuric acid and the number of moles of dihydroxybenzene disulfonic acid being greater than 1, preferably between 2 and 4.
  • the reaction medium is diluted by addition of water in order to facilitate stirring after salification.
  • the amount of water introduced is about 5 to 10 moles per mole of dihydroxybenzenedisulfonic acid.
  • the weight ratio of sulfuric acid to metal dihydroxybenzenedisulfonate ranges from 1 to 2.1 and is preferably from 1.6 to 1.7.
  • Another characteristic of the reaction medium is that it comprises only a small amount of water.
  • the weight ratio of water to metal dihydroxybenzenedisulfonate varies between 0.4 and 0.8.
  • Another feature is that there is only a small amount of metal sulfate present.
  • the amount of metal sulfate formed is less than 5% by weight of the resulting metal dihydroxybenzenedisulfonate.
  • the precipitated metal dihydroxybenzenedisulfonate which is preferably sodium dihydroxybenzenedisulfonate is preferably separated by filtration.
  • the process of the invention makes it possible to recover from the separation operation, preferably by filtration, mother liquors having a strong concentration of sulfuric acid greater than 50% by weight, preferably between 60% and 65% by weight.
  • mother liquors can be sent directly to the regeneration unit of sulfuric acid, which is conducted in particular by conventional methods by incineration.
  • the dissolution is exothermic (+40 ° C approximately).
  • the reaction mass is then heated at 85 ° C.-90 ° C. for 5 hours to complete the sulfonation.
  • reaction mass After cooling to 50 ° C., the reaction mass is treated with 221 g of water and then with 371 g of potassium hydrogen sulphate.
  • the salt obtained is filtered on a B ⁇ chner filter equipped with a cotton cloth, then washed with 3 times 1 15 g of isopropanol and then dried under reduced pressure (50 - 60 mm Hg). 60 ° C.
  • the washings are concentrated by heating (at about 110 ° C.) until the isopropanol is removed and the resulting residue is mixed with the mother liquors.
  • This mixture containing about 651 g of sulfuric acid (more than 65%) can be regenerated to 98% sulfuric acid, and can be recycled to the synthesis.
  • reaction mass is then heated at 85-90 ° C for 5 hours to complete the sulfonation.
  • reaction mass After cooling to 50 ° C, the reaction mass is supplemented with 221 g of water and 237.4 g of potassium sulfate.
  • Beaker provided with a cotton cloth, washed with 3 times 1 15 g of isopropanol, and then dried under reduced pressure (50 - 60 mm of mercury) at 60 ° C.
  • the residue is mixed with the mother liquors.
  • This mixture containing about 526 g of sulfuric acid (more than 61%) can be regenerated to 98% sulfuric acid, and can be recycled to the synthesis.
  • the dissolution is exothermic (+ 40 ° C approximately).
  • reaction mass is then heated at 85-90 ° C for 5 hours to complete the sulfonation.
  • reaction mass After cooling to 50 ° C., the reaction mass is treated with 220 g of water and then with 384.8 g of sodium hydrogen sulphate monohydrate.
  • the salt obtained is filtered on a B ⁇ chner filter equipped with a cotton cloth, washed with 3 times 1 15 g of isopropanol and then dried under reduced pressure (50 - 60 mm Hg) at 60 ° C. ° C.
  • the residue is mixed with the mother liquors.
  • This mixture containing about 657 grams of sulfuric acid (greater than 63%) can be regenerated to 98% sulfuric acid, and can be recycled to the synthesis.
  • the dissolution is exothermic (+ 40 ° C approximately).
  • reaction mass is then heated at 85-90 ° C for 5 hours to complete the sulfonation.
  • reaction mass After cooling to 50 ° C, the reaction mass is supplemented with 220 g of water and 227.6 g of sodium sulfate monohydrate.
  • the sodium 1,2-dihydroxy-3,5-benzenedisulfonate formed precipitates from the reaction mass.
  • the salt formed is filtered on a B ⁇ chner filter equipped with a cotton cloth, washed with 3 times 1 15 g of isopropanol and then dried under reduced pressure (50 - 60 mm Hg) at 60 ° C. ° C.
  • Mother liquors with a sulfuric acid concentration of 66.6% are collected. After concentration of the washings, the residue is mixed with the mother liquors.
  • Example 4 is reproduced with the difference that the salification is carried out not with sodium sulphate but as in the prior art, using an aqueous solution of soda.
  • 682 g of 98% sulfuric acid are charged, and then 150 g of pyrocatechol are dissolved at room temperature.
  • the dissolution is exothermic (+ 40 ° C approximately).
  • reaction mass is then heated at 85-90 ° C for 5 hours to complete the sulfonation. After cooling to 50 ° C., the reaction mass is treated with 231.9 g of an aqueous solution of sodium hydroxide at 47% by weight.
  • the sodium 1,2-dihydroxy-3,5-benzenedisulfonate formed precipitates from the reaction mass.
  • the salt formed is filtered on a B ⁇ chner filter equipped with a cotton cloth, washed with 3 times 1 15 g of isopropanol and then dried under reduced pressure (50 - 60 mm Hg) at 60 ° C. ° C.
  • the residue is mixed with the mother liquors.
  • This mixture contains about 400.4 g of sulfuric acid, which corresponds to a concentration of 46.6%.
  • the dissolution is exothermic (+ 35 ° C approximately).
  • the reaction mass is then heated at 85-90 ° C for 5 hours to complete the sulfonation.
  • reaction mass After cooling to 50 ° C, the reaction mass is supplemented with 221 g of water and 237.4 g of potassium sulfate.
  • the potassium 1,4-dihydroxy-3,5-benzenedisulfonate formed precipitates from the reaction mass.
  • the salt obtained is filtered on a B ⁇ chner filter equipped with a cotton cloth, washed with 3 times 1 15 g of ethanol and then dried under reduced pressure (50 - 60 mm Hg) at 60 ° C. ° C. 392.9 g of potassium 1,4-dihydroxy-3,5-benzenedisulphonate are thus obtained, titrating 91.5% by HPLC.
  • This mixture containing about 528 g of sulfuric acid (more than 60%) can be regenerated to 98% sulfuric acid, or even recycled to the synthesis.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP07730083A 2006-06-13 2007-06-12 Procede de preparation de dihydroxybenzenedisulfonates metalliques Withdrawn EP2044011A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0605242A FR2902096B1 (fr) 2006-06-13 2006-06-13 Procede de preparation de dihydroxybenzenedisulfonates metalliques
PCT/EP2007/055758 WO2007144344A1 (fr) 2006-06-13 2007-06-12 Procede de preparation de dihydroxybenzenedisulfonates metalliques

Publications (1)

Publication Number Publication Date
EP2044011A1 true EP2044011A1 (fr) 2009-04-08

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ID=37709448

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07730083A Withdrawn EP2044011A1 (fr) 2006-06-13 2007-06-12 Procede de preparation de dihydroxybenzenedisulfonates metalliques

Country Status (10)

Country Link
US (1) US8263803B2 (ja)
EP (1) EP2044011A1 (ja)
JP (1) JP5431923B2 (ja)
KR (1) KR101196690B1 (ja)
CN (1) CN101466664B (ja)
CA (1) CA2654109C (ja)
FR (1) FR2902096B1 (ja)
NO (1) NO20085191L (ja)
RU (1) RU2468004C2 (ja)
WO (1) WO2007144344A1 (ja)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8492581B2 (en) 2009-08-21 2013-07-23 Amyris, Inc. Sulfonation of polyhydroxyaromatics
CN109678764A (zh) * 2018-12-05 2019-04-26 湖北广辰药业有限公司 一种羟苯双磺酸及其钙盐和制备方法
CN110092736A (zh) * 2018-12-05 2019-08-06 湖北广辰药业有限公司 一种减少羟苯双磺酸钙杂质含量的羟苯磺酸钙制备方法
EP4357424A1 (en) 2022-10-20 2024-04-24 Agfa Nv Industrial inkjet printing methods
EP4357426A1 (en) 2022-10-20 2024-04-24 Agfa Nv Aqueous pigmented inkjet inks

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US3547988A (en) * 1968-02-05 1970-12-15 Eastman Kodak Co Process for the preparation of dialkali dihydroxybenzene disulfonates
US3772379A (en) * 1971-10-28 1973-11-13 Eastman Kodak Co Preparation of dialkali dihydroxybenzene disulfonates
JPS58157760A (ja) * 1982-03-11 1983-09-19 Mitsubishi Gas Chem Co Inc ｍ−キシレン−４−スルホン酸の製造法
JPS6366158A (ja) * 1986-09-05 1988-03-24 Kiresuto Giken:Kk １，２−ジヒドロキシベンゼン−３，５−ジスルホン酸アルカリの精製方法
JP2002512219A (ja) * 1998-04-20 2002-04-23 ロデイア・シミ 新規なスルホン化されたオキシアルキレン化ジフェノール誘導体およびスルホン化されたポリアルキレン化ジフェノール誘導体ならびそれらに対応する塩
ES2208124B1 (es) * 2002-11-29 2005-10-01 Laboratorios Del Dr. Esteve, S.A. Uso de los compuestos 2,5-dihidroxibencenosulfonicos para la fabricacion de un medicamento.
CN1696112A (zh) * 2005-06-08 2005-11-16 天津大学 对硝基甲苯邻磺酸钠的制备方法

Non-Patent Citations (1)

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Title
See references of WO2007144344A1 *

Also Published As

Publication number Publication date
FR2902096A1 (fr) 2007-12-14
CA2654109A1 (fr) 2007-12-21
JP5431923B2 (ja) 2014-03-05
NO20085191L (no) 2009-03-13
JP2009539928A (ja) 2009-11-19
FR2902096B1 (fr) 2011-03-18
KR20090018936A (ko) 2009-02-24
RU2468004C2 (ru) 2012-11-27
RU2009100840A (ru) 2010-07-20
US20100056823A1 (en) 2010-03-04
KR101196690B1 (ko) 2012-11-08
CN101466664A (zh) 2009-06-24
CA2654109C (fr) 2013-08-06
WO2007144344A1 (fr) 2007-12-21
CN101466664B (zh) 2012-10-31
US8263803B2 (en) 2012-09-11

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