WO2007144344A1 - Procede de preparation de dihydroxybenzenedisulfonates metalliques - Google Patents
Procede de preparation de dihydroxybenzenedisulfonates metalliques Download PDFInfo
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- WO2007144344A1 WO2007144344A1 PCT/EP2007/055758 EP2007055758W WO2007144344A1 WO 2007144344 A1 WO2007144344 A1 WO 2007144344A1 EP 2007055758 W EP2007055758 W EP 2007055758W WO 2007144344 A1 WO2007144344 A1 WO 2007144344A1
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- WIPO (PCT)
- Prior art keywords
- acid
- process according
- dihydroxybenzenedisulfonic
- sulfuric acid
- sulfate
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 40
- CJAZCKUGLFWINJ-UHFFFAOYSA-N 3,4-dihydroxybenzene-1,2-disulfonic acid Chemical class OC1=CC=C(S(O)(=O)=O)C(S(O)(=O)=O)=C1O CJAZCKUGLFWINJ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 109
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012429 reaction media Substances 0.000 claims description 14
- 238000006277 sulfonation reaction Methods 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- XXAXVMUWHZHZMJ-UHFFFAOYSA-N Chymopapain Chemical compound OC1=CC(S(O)(=O)=O)=CC(S(O)(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 3
- 230000008929 regeneration Effects 0.000 claims description 3
- 238000011069 regeneration method Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- VSAZFRKEFQPOIS-UHFFFAOYSA-N 2,5-dihydroxybenzene-1,4-disulfonic acid Chemical compound OC1=CC(S(O)(=O)=O)=C(O)C=C1S(O)(=O)=O VSAZFRKEFQPOIS-UHFFFAOYSA-N 0.000 claims description 2
- 238000010981 drying operation Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Inorganic materials O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 2
- XXAXVMUWHZHZMJ-UHFFFAOYSA-L 4,5-dihydroxybenzene-1,3-disulfonate Chemical compound OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-L 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 claims 1
- MIAUJDCQDVWHEV-UHFFFAOYSA-N benzene-1,2-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1S(O)(=O)=O MIAUJDCQDVWHEV-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 150000001450 anions Chemical class 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000001816 cooling Methods 0.000 description 12
- 239000002244 precipitate Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 7
- 229920000742 Cotton Polymers 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 5
- 229910052939 potassium sulfate Inorganic materials 0.000 description 5
- 235000011151 potassium sulphates Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- ISWQCIVKKSOKNN-UHFFFAOYSA-L Tiron Chemical compound [Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ISWQCIVKKSOKNN-UHFFFAOYSA-L 0.000 description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 4
- DTOOGQLOHKJKHN-UHFFFAOYSA-L dipotassium;4,5-dihydroxybenzene-1,3-disulfonate Chemical compound [K+].[K+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O DTOOGQLOHKJKHN-UHFFFAOYSA-L 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L sodium sulphate Substances [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- -1 alkali metal salts Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000001120 potassium sulphate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- JWNLTHADDXGNHR-UHFFFAOYSA-L dipotassium;2,5-dihydroxybenzene-1,3-disulfonate Chemical compound [K+].[K+].OC1=CC(S([O-])(=O)=O)=C(O)C(S([O-])(=O)=O)=C1 JWNLTHADDXGNHR-UHFFFAOYSA-L 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 0 **c(cc(*)cc1O)c1O Chemical compound **c(cc(*)cc1O)c1O 0.000 description 1
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical class OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-UHFFFAOYSA-N 0.000 description 1
- VWXVJYKCCPSYRD-UHFFFAOYSA-N 4,6-dihydroxybenzene-1,3-disulfonic acid Chemical compound OC1=CC(O)=C(S(O)(=O)=O)C=C1S(O)(=O)=O VWXVJYKCCPSYRD-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000795633 Olea <sea slug> Species 0.000 description 1
- LJSAJMXWXGSVNA-UHFFFAOYSA-N a805044 Chemical compound OC1=CC=C(O)C=C1.OC1=CC=C(O)C=C1 LJSAJMXWXGSVNA-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- TUCIXUDAQRPDCG-UHFFFAOYSA-N benzene-1,2-diol Chemical compound OC1=CC=CC=C1O.OC1=CC=CC=C1O TUCIXUDAQRPDCG-UHFFFAOYSA-N 0.000 description 1
- BVDIIMNJKLBSFI-UHFFFAOYSA-N benzene-1,2-diol phenol Chemical compound OC1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1O BVDIIMNJKLBSFI-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- UGECXIBKSDDQDH-UHFFFAOYSA-L disodium;3,4-dihydroxybenzene-1,2-disulfonate Chemical compound [Na+].[Na+].OC1=CC=C(S([O-])(=O)=O)C(S([O-])(=O)=O)=C1O UGECXIBKSDDQDH-UHFFFAOYSA-L 0.000 description 1
- ZLRROLLKQDRDPI-UHFFFAOYSA-L disodium;4,5-dihydroxybenzene-1,3-disulfonate;hydrate Chemical compound O.[Na+].[Na+].OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O ZLRROLLKQDRDPI-UHFFFAOYSA-L 0.000 description 1
- HFCSXCKLARAMIQ-UHFFFAOYSA-L disodium;sulfate;hydrate Chemical compound O.[Na+].[Na+].[O-]S([O-])(=O)=O HFCSXCKLARAMIQ-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- JXHZRQHZVYDRGX-UHFFFAOYSA-M sodium;hydrogen sulfate;hydrate Chemical compound [OH-].[Na+].OS(O)(=O)=O JXHZRQHZVYDRGX-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical group OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 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
Classifications
-
- 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
- C07C303/02—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
- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/304,887 US8263803B2 (en) | 2006-06-13 | 2007-06-12 | Preparation of metallic dihydroxybenzene-disulfonates |
CN2007800220052A CN101466664B (zh) | 2006-06-13 | 2007-06-12 | 制备二羟基苯二磺酸金属盐的方法 |
JP2009514780A JP5431923B2 (ja) | 2006-06-13 | 2007-06-12 | ジヒドロキシベンゼンジスルホン酸金属塩を調製するための方法 |
RU2009100840/04A RU2468004C2 (ru) | 2006-06-13 | 2007-06-12 | Способ получения дигидроксибензолдисульфонатов металлов |
EP07730083A EP2044011A1 (fr) | 2006-06-13 | 2007-06-12 | Procede de preparation de dihydroxybenzenedisulfonates metalliques |
KR1020087029725A KR101196690B1 (ko) | 2006-06-13 | 2007-06-12 | 금속 디하이드록시벤젠디설포네이트의 제조 방법 |
CA2654109A CA2654109C (fr) | 2006-06-13 | 2007-06-12 | Procede de preparation de dihydroxybenzenedisulfonates metalliques |
NO20085191A NO20085191L (no) | 2006-06-13 | 2008-12-12 | Fremgangsmate for fremstilling av metalliske dihydroksybenzendisulfonater |
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 |
FR0605242 | 2006-06-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2007144344A1 true WO2007144344A1 (fr) | 2007-12-21 |
Family
ID=37709448
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2007/055758 WO2007144344A1 (fr) | 2006-06-13 | 2007-06-12 | Procede de preparation de dihydroxybenzenedisulfonates metalliques |
Country Status (10)
Country | Link |
---|---|
US (1) | US8263803B2 (fr) |
EP (1) | EP2044011A1 (fr) |
JP (1) | JP5431923B2 (fr) |
KR (1) | KR101196690B1 (fr) |
CN (1) | CN101466664B (fr) |
CA (1) | CA2654109C (fr) |
FR (1) | FR2902096B1 (fr) |
NO (1) | NO20085191L (fr) |
RU (1) | RU2468004C2 (fr) |
WO (1) | WO2007144344A1 (fr) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8492581B2 (en) | 2009-08-21 | 2013-07-23 | Amyris, Inc. | Sulfonation of polyhydroxyaromatics |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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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 (fr) | 2022-10-20 | 2024-04-24 | Agfa Nv | Procédés d'impression à jet d'encre industrielle |
EP4357426A1 (fr) | 2022-10-20 | 2024-04-24 | Agfa Nv | Encres pour jet d'encre pigmentées aqueuses |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO1999054292A1 (fr) * | 1998-04-20 | 1999-10-28 | Rhodia Chimie | Nouveaux derives de diphenols sulfones et oxy- ou polyoxyalkylenes et leurs sels correspondants |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
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 |
-
2006
- 2006-06-13 FR FR0605242A patent/FR2902096B1/fr not_active Expired - Fee Related
-
2007
- 2007-06-12 RU RU2009100840/04A patent/RU2468004C2/ru not_active IP Right Cessation
- 2007-06-12 CA CA2654109A patent/CA2654109C/fr not_active Expired - Fee Related
- 2007-06-12 JP JP2009514780A patent/JP5431923B2/ja not_active Expired - Fee Related
- 2007-06-12 US US12/304,887 patent/US8263803B2/en not_active Expired - Fee Related
- 2007-06-12 CN CN2007800220052A patent/CN101466664B/zh not_active Expired - Fee Related
- 2007-06-12 KR KR1020087029725A patent/KR101196690B1/ko not_active IP Right Cessation
- 2007-06-12 EP EP07730083A patent/EP2044011A1/fr not_active Withdrawn
- 2007-06-12 WO PCT/EP2007/055758 patent/WO2007144344A1/fr active Application Filing
-
2008
- 2008-12-12 NO NO20085191A patent/NO20085191L/no unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
WO1999054292A1 (fr) * | 1998-04-20 | 1999-10-28 | Rhodia Chimie | Nouveaux derives de diphenols sulfones et oxy- ou polyoxyalkylenes et leurs sels correspondants |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8492581B2 (en) | 2009-08-21 | 2013-07-23 | Amyris, Inc. | Sulfonation of polyhydroxyaromatics |
Also Published As
Publication number | Publication date |
---|---|
KR101196690B1 (ko) | 2012-11-08 |
CN101466664A (zh) | 2009-06-24 |
US20100056823A1 (en) | 2010-03-04 |
RU2468004C2 (ru) | 2012-11-27 |
KR20090018936A (ko) | 2009-02-24 |
EP2044011A1 (fr) | 2009-04-08 |
JP5431923B2 (ja) | 2014-03-05 |
JP2009539928A (ja) | 2009-11-19 |
US8263803B2 (en) | 2012-09-11 |
FR2902096A1 (fr) | 2007-12-14 |
CA2654109C (fr) | 2013-08-06 |
NO20085191L (no) | 2009-03-13 |
CN101466664B (zh) | 2012-10-31 |
CA2654109A1 (fr) | 2007-12-21 |
FR2902096B1 (fr) | 2011-03-18 |
RU2009100840A (ru) | 2010-07-20 |
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