Method of preparing a solid mass for mercury recovery

• US 5,350,728 A
• Filed: 07/19/1993
• Issued: 09/27/1994
• Est. Priority Date: 10/30/1990
• Status: Expired due to Term

• Current Assignee: Institut Francais Du Petrole and Europeene de Retraitment de Catalyseurs
• Original Assignee: Institut Francais Du Petrole and Europeene de Retraitment de Catalyseurs
• Inventors: Roumieu, Raymond, Berrebi, Georges, Eschard, Francois, Courty, Philippe, Cameron, Charles, Rabehasaina, Hans
• Primary Examiner(s): KONOPKA, PAUL
• Application Number:
  US08/092,924
• Time in Patent Office: 435 Days
• Field of Search: 502/407, 502/412, 502/413, 502/415, 502/417, 502/216, 502/60, 502/77, 502/79, 502/80, 502/414
• US Class Current: 502/415
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• CPC Class Codes: B01J 20/02 comprising inorganic material
• CPC Class Codes: B01J 20/0237 Compounds of Cu
• CPC Class Codes: B01J 20/0285 Sulfides of compounds other than those provided for in B01J20/045
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing

Abstract

A solid mass for the recovery of mercury, comprising a solid mineral support or dispersant, essentially copper and sulphur at least partly in the form of copper sulfide is produced by the following stages:

a) at least one copper compound other than a sulphide is incorporated into a solid mineral dispersant or carrier,

b) the product obtained in stage (a) is calcined in order at least partly to convert the copper compound or compounds which it contains into copper oxide (CuO and/or Cu₂ O),

c) the product obtained in stage (b) or in stage (a) if there has not been a stage (b) is brought into contact with elementary sulphur,

d) the product resulting from stage (c) referred to as the precursor, is subjected to a thermal treatment in a non-oxidizing atmosphere and accompanied by gas scavenging, to a temperature and for a sufficient time to allow the formation of sulphide of the metal(s) present.

Claims

1. In a solid mercury recovery mass comprising a solid mineral aluminous dispersant or support, and copper and sulfur at least partly in the form of copper sulfide, the improvement comprising an improved long-term life of the recovery mass resulting from the production of the mass by the following stages:

(a) incorporating at least one copper compound other than a sulfide into a solid mineral aluminous dispersant or support,

(b) when said copper compound in step (a) is not a copper oxide, calcining the product obtained in stage (a) so as to convert at least in part the copper compound(s) which it contains into copper oxide (CuO and/or Cu₂ O),

(c) bringing the product obtained in stage (b) or in stage (a) when there has not been a stage (b) into contact with elemental sulfur, and

(d) subjecting the product resulting from stage (c) to a heat treatment in a non-oxidizing atmosphere at a temperature and for a time sufficient to convert at least 80% of the copper to the sulfide state.

2. A mass according to claim 1, wherein in in stage (c) the elemental sulfur is used at least partly in solution in an organic solvent.

3. A solid mass according to claim 1, wherein the copper sulfide is about 8 to 25% by weight of the weight of said mass and in which the atomic ratio S:

Cu is from 0.8;

1 to 2;

1.

4. A solid mass according to claim 1, wherein the solid mineral dispersant or support is selected from the group consisting of alumina, a silica-alumina, and an aluminate.

5. A mass according to claim 1, wherein in stage (d), the heat treatment is conducted in an atmosphere of at least one inert gas containing not more than 10% by volume of water vapor.

6. A mass according to claim 1 wherein in stage (a), an aqueous solution of copper nitrate is used.

7. A solid mass according to claim 1, wherein in stage (b) the product resulting from stage (a) is calcined at a temperature of 200°

-1000°

C. in a current of gas at a VVH of about 100 to approx. 20,000 h^-1 for approx. half to approx. 24 hours.

8. A solid mass according to claim 1, wherein in stage (c), the product resulting from stage (b) is impregnated with an organic solution of sulphur or with sulphur in the solid state or with sulphur in the vapour state, condensed on the support.

9. A solid mass according to claim 1, wherein in stage (c), the elemental sulfur is used in solution in at least one organic solvent selected from the group consisting of toluene, benzene, methyl alcohol, acetone, carbon disulfide, a light fuel boiling between about 60°

and 95°

C., hydrocarbon fuel boiling between about 100°

to 160°

C. and containing by volume 10 to 20% aromatic hydrocarbons and a white spirit fuel boiling between about 150° and

250°

C. and containing by volume 14 to 22% aromatic hydrocarbons.

10. A solid mass according to claim 1, wherein the atomic ratio of (A) sulfur to (B) copper is about 0.8:

1 to 2;

1.

11. A solid mass according to claim 10, in which the said atomic ratio is about 0.9:

1 to 1.7;

1.

12. A solid mass according to claim 4, wherein in stage (c), the inert gas contains 1-5% of a reducing agent.

13. A solid mass according to claim 1, wherein an intermediate stage (b'"'"') is incorporated between stage (c) and either stage (b) or stage (a) when there has not been a stage (b), said intermediate step (b'"'"') comprising subjecting the respective product from stage (a) or (b) to a reducing treatment to convert at least 50% of copper oxide present in the product to elemental metal.

14. A solid mass according to claim 13, in which the reducing treatment is performed with hydrogen, an aldehyde, formic acid or hydrazine.

15. A mass according to claim 5 in which 1 to 5% by volume of hydrogen is added to the said gas.

16. A mass according to claim 15, wherein said gas comprises water vapour and hydrogen at a ratio H₂ :

H₂ O of more than 0.1% by volume.

17. A solid mass according to claim 1, in which the heat treatment of stage (d) is carried out at a temperature of about 100°

to 250°

C. with a gas VVH of about 100 to 10,000 h^-1 and for about half to 24 hours.

18. A solid mass according to claim 17, in which the heat treatment is carried out at between 120°

and 230°

C.,

19. A solid mass prepared according to claim 1 in which a silver compound is also incorporated during the course of stage (a).