Process for reducing the level of contaminating mercury in aqueous solutions

• US 3,873,581 A
• Filed: 09/08/1972
• Issued: 03/25/1975
• Est. Priority Date: 10/21/1971
• Status: Expired due to Term

• Current Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Original Assignee: Carl Johannes Berninger, Dennis Osborne Lewis, Joseph William Fitzpatrick
• Inventors: Fitzpatrick, Joseph William, Berninger, Carl Johannes, Lewis, Dennis Osborne
• Primary Examiner(s): Weinberger, Lorraine A.
• Assistant Examiner(s): Skelly, E. Jane
• Application Number:
  US05/287,397
• Time in Patent Office: 928 Days
• Field of Search: 260/370
• US Class Current: 552/234
• CPC Class Codes: C02F 1/283 using coal, charred products, or inorganic mixtures containing them
• CPC Class Codes: C02F 1/288 using composite sorbents, e.g. coated, impregnated, multi-layered
• CPC Class Codes: C02F 1/5272 using specific organic precipitants

Abstract

The mercury content of an aqueous solution contaminated by mercury can be reduced by treating the solution with a mercuryreactive factor and an adsorbent such as activated charcoal.

Claims

1. A PROCESS FOR REMOVING MERCURY FROM AQUEOUS SOLUTIONS OF ANTHRAQUINONE SILFONIC ACIDS AND THEIR AQUEOUS PROCESS EFFUENTS WHICH COMPRIES TREATING THE AQUEOUS SOLUTION OR EFFLUENT WITH A. AT LEAST ONE MERCURY-REACTIVE FACTOR SELECTED FROM THE GROUP CONSISTING OF I. TIN, MAGNESIUM, COPPER, IRON, ZINC, AND ALUMINUM, II. AN ALKALI METAL SULFIDE OR THIOSULFATE, AND A POLYSULFIDE COMPOSITION OBTAINED BY TREATING A POROUS SUBSTRATE WITH SULFUR, SODIUM SULFIDE AND WATER, III. THIOBUREA, DITHIZONE, DITHIOOXAMIDE, THIOACETAMIDE, DITHIOBIURET, DIPHENYLTHIOUREA, THIOSEMICARBAZIDE AND TRITHIOBIURET, IV. AN ALKANE DITHIO OR HYDROXYALKANE DITHIOL CONTAINING 2 TO 12 CARBON ATOMS, V. THIO AND MERCAPTO DERIVATIVES OF C2-C10 ORGANIC ACIDS, VI. THIOPHENOL, TOLUENETHIOL, BENZENDITHIOL, TOLUENEDITHIOL, XYLENE DITHIOL, DITHIOTETEPHTHALIC ACID AND MERCAPTOSALICYCLIC ACID, VII. 2,3-QUINOXALINE DITHIOL, TRITHIOCYANURIC ACID AND 2MERCAPTOBENZTHIAZOLE, VIII. 8-HYDROXYQUINOLINE, 2-NITROSO-1-NAPHTHOL AND FURAN, AND B. AN ABSORBENT SELECTED FROM THE GROUP CONSISTING OF TITANIA, ALUMINA, SILICA, FERRIC OXIDE, STANNIC OXIDE, MAGNESIUM OXIDE, KAOLIN, CARBON ACTIVATED CARBON, ACTIVATED ALUMINA, ACTIVATED CLAY AND DIATOMACEOUS EARTH.

2. A process according to claim 1 in which the adsorbent comprises activated carbon.

3. A process according to claim 1 in which the adsorbent comprises activated carbon which may be impregnated with sulfur, polysulfide composition, thiophene, furan, 8-hydroxyquinoline, 8-mercaptoquinoline, diethyldithiophosphoric acid, dithizone, 2-nitroso-1-naphthol, or 2,3-quinoxalinedithiol.

4. A process according to claim 1 in which the mercury-reactive factor is selected from i. aluminum, zinc and iron, ii. sodium thiosulfate, sodium sulfide, and a polysulfide composition obtained by treating a porous substrate with sulfur, sodium sulfide and water, iii. thiourea, dithizone, dithiooxamide and thioacetamide, iv. 2,3-dimercaptopropanol, v. thioglycollic acid, mercaptoacetic acid, 2-mercaptopropionic acid, mercaptosuccinic acid, 2-amino-3-mercaptopropionic acid and lauryl thioglycolate, vi. thiophenol, toluenethiol, benzenedithiol, toluenedithiol, xylene dithiol, dithioterephthalic acid and mercaptosalicyclic acid, vii. 2,3-quinoxaline dithiol, trithiocyanuric acid and 2-mercaptobenzthiazole, viii. 8-hydroxyquinoline, 2-nitroso-1-naphthol and furan.

5. A process according to claim 4 in which the adsorbent is activated carbon.

6. A process according to claim 5 in which the mercury reactive factor is selected from one or more of aluminum powder, dithiooxamide, sodium thiosulfate, 2-mercaptobenzthiazole, trithiocyanuric acid, dithioterephthalic acid, 2,3-dimercaptopropanol, sodium sulfide, 8-hydroxyquinoline, 2-nitroso-1-naphthol and furan.

7. A process according to claim 6 in which the mercury reactive factor is aluminum and the adsorbent is activated carbon.

8. A process according to claim 1 in which the solution is treated a second time to further reduce the mercury content.

9. A process according to claim 1 in which the solution treated contains at least one of anthraquinone-1-sulfonate, anthraquinone-1,5-disulfonate or anthraquinone-1,8-disulfonate.

10. In a process for sulfonating anthraquinone in the 1-position wherein mercury and mercury compounds catalyze the reaction, the improvement which comprises treating a solution containing the 1-sulfonated product with a. at least one mercury-reactive factor selected from the group consisting of i. tin, magnesium, copper, iron, zinc and aluminum, ii. an alkali metal sulfide or thiosulfate, and a polysulfide composition obtained by treating a porous substrate with sulfur, sodium sulfide and water, iii. thiourea, dithizone, dithiooxamide, thioacetamide, dithiobiuret, diphenylthiourea, thiosemicarbazide and trithiobiuret, iv. an alkane dithiol or hydroxyalkane dithiol containing 2 to 12 carbon atoms, v. thio and mercapto derivatives of C2-C10 organic acids, vi. thiophenol, toluenethiol, benzenedithiol, toluenedithiol, xylene dithiol, dithioterephthalic acid and mercaptosalicyclic acid, vii. 2,3-quinoxaline dithiol, trithiocyanuric acid and 2-mercaptobenzthiazole, viii. 8-hydroxyquinoline, 2-nitroso-1-naphthol and furan, and b. an adsorbent selected from the group consisting of titania, alumina, silica, ferric oxide, stannic oxide, magnesium oxide, kaolin, carbon, activated carbon, activated alumina, activated clay and diatomaceous earth, and filtering to provide a solution having reduced mercury content.

11. A process according to claim 10 in which the mercury reactive factor and the adsorbent are added just after unreacted anthraquinone is precipated out of solution.

12. A process according to claim 11 in which the mercury reactive factor is aluminum and the adsorbent is activated carbon.

13. A process according to claim 12 in which the mercury reactive factor is aluminum and the adsorbent is activated carbon and the filter cake left after filtration is recycled to the sulfonation reaction.

14. In a process for disulfonating anthraquinone in the Alpha -position wherein mercury and mercury compounds catalyze the reaction, the improvement which comprises treating a solution containing 1,8-disulfonated product with a. at least one mercury-reactive factor selected from the group consisting of i. tin, magnesium, copper, iron, zinc and aluminum, ii. an alkali metal sulfide or thiosulfate, and a polysulfide composition obtained by treating a porous substrate with sulfur, sodium sulfide and water, iii. thiourea, dithizone, dithiooxamide, thioacetamide, dithiobiuret, diphenylthiourea, thiosemicarbazide and trithiobiuret, iv. an alkane dithiol or hydroxyalkane dithiol containing 2 to 12 carbon atoms, v. thio and mercapto derivatives of C2-C10 organic acids, vi. thiophenol, toluenethiol, benzenedithiol, toluenedithiol, xylene dithiol, dithioterephthalic acid and mercaptosalicyclic acid, vii. 2,3-quinoxaline dithiol, trithiocyanuric acid and 2-mercaptobenzthiazole, viii. 8-hydroxyquinoline, 2-nitroso-1-naphthol and furan, and b. an adsorbent selected from the group consisting of titania, alumina, silica, ferric oxide, stannic oxide, magnesium oxide, kaolin, carbon, activated carbon, activated alumina, activated clay and diatomaceous earth, and filtering to recover a solution having reduced mercury content.

15. In a process for disulfonating anthraquinone in the Alpha -position wherein mercury and mercury compounds catalyze the reaction, the improvement which comprises treating a solution containing 1,5-disulfonated product with a. at least one mercury-reactive factor selected from the group consisting of i. tin, magnesium, copper, iron, zinc and aluminum, ii. an alkali metal sulfide or thiosulfate, and a polysulfide composition obtained by treating a porous substrate with sulfur, sodium sulfide and water, iii. thiourea, dithizone, dithiooxamide, thioacetamide, dithiobiuret, diphenylthiourea, thiosemicarbazide and trithiobiuret, iv. an alkane dithiol or hydroxyalkane dithiol containing 2 to 12 carbon atoms, v. thio and mercapto derivatives of C2-C10 organic acids, vi. thiophenol, toluenethiol, benzenedithiol, toluenedithiol, xylene dithiol, dithioterephthalic acid and mercaptosalicyclic acid, vii. 2,3-quinoxaline dithiol, trithiocyanuric acid and 2-mercaptobenzthiazole, viii. 8-hydroxyquinoline, 2-nitroso-1-naphthol and furan, and b. an adsorbent selected from the group consisting of titania, alumina, silica, ferric oxide, stannic oxide, magnesium oxide, kaolin, carbon, activated carbon, activated alumina, activated clay and diatomaceous earth, and filtering to recover a solution having reduced mercury content.