Process for removing mercury from a gas or a liquid by absorption on a copper sulfide containing solid mass

• US 4,094,777 A
• Filed: 12/16/1976
• Issued: 06/13/1978
• Est. Priority Date: 12/18/1975
• Status: Expired due to Term

• Current Assignee: Institut Francais Du Petrole
• Original Assignee: Institut Francais Du Petrole
• Inventors: Sugier, Andre, LA Villa, Florentino
• Primary Examiner(s): Hart, Charles N.
• Assistant Examiner(s): Cintins, Ivars
• Application Number:
  US05/751,452
• Time in Patent Office: 544 Days
• Field of Search: 55/74, 55/54, 55/59, 55/61, 75/101 BE, 75/108, 75/109, 75/121, 210/24, 210/28, 210/30 R, 210/36, 210/38 B, 210/40, 210/42 R, 210/47, 210/32, 210/502, 210/504, 252/416, 423/100, 423/101
• US Class Current: 210/670
• CPC Class Codes: B01D 15/00 Separating processes involving the treatment of liquids with solid sorbents using liquid sorbents B01D11/00; ion exchange processes or materials, sorbent materials in general B01J, e.g. sorbents for chromatography B01J20/281; for investigating or analysing materials G01N30/00; Apparatus therefor
• CPC Class Codes: B01D 2253/1128 Metal sulfides
• CPC Class Codes: B01D 53/02 by adsorption, e.g. preparative gas chromatography solid sorbent compositions B01J20/00, preparation of inorganic compounds or elements C01
• CPC Class Codes: B01D 53/64 Heavy metals or compounds thereof, e.g. mercury
• 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 20/08 comprising aluminium oxide or hydroxide; comprising bauxite
• CPC Class Codes: B01J 20/103 comprising silica
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/3007 Moulding, shaping or extruding
• CPC Class Codes: B01J 20/3028 Granulating, agglomerating or aggregating
• CPC Class Codes: B01J 20/3078 Thermal treatment, e.g. calcining or pyrolizing
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: B01J 20/3204 Inorganic carriers, supports or substrates
• CPC Class Codes: B01J 20/3236 containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
• CPC Class Codes: B01J 20/3433 of sorbents or filter aids other than those covered by B01J20/3408 - B01J20/3425
• CPC Class Codes: B01J 20/3458 in the gas phase
• CPC Class Codes: B01J 2220/56 Use in the form of a bed
• CPC Class Codes: C07C 7/148 by treatment giving rise to a chemical modification of at least one compound
• CPC Class Codes: C07C 9/04 Methane production by treatment of sewage C02F11/04; natural gas, synthetic natural gas C10L3/06
• CPC Class Codes: Y10S 95/90 : Solid sorbent

Abstract

Mercury is removed from a gas or a liquid by absorption on a solid mass, which mass contains a carrier and sulfided copper.

Claims

1. In a process for the elimination of mercury present in a gas or liquid comprising contacting the liquid or gas with an absorption mass in a fixed bed, the improvement wherein the absorption mass consists essentially of:

(a) a solid dispersant or support selected from the group formed by silica, alumina, silica-alumina, silicates, aluminates and silico-aluminates,

(b) copper whereof at least 30% is in the sulphide state and wherein the copper sulphide proportion in the absorption mass, calculated as copper, represents 2 to 65% of the weight of the mass, and

(c) 0-5% of silver in the sulfide state.

2. A process according to claim 1 in which the support is alumina.

3. A process according to claim 1, in which the absorption mass results from the mixture of a copper hydroxide or salt with said support followed by shaping and sulphurization of the latter.

4. A process according to claim 3, in which the absorption mass results from a mixture of a basic copper carbonate with said support.

5. A process according to claim 3, in which sulphurization is performed by means of hydrogen sulphide.

6. A process according to claim 3, in which sulphurization is performed with an aqueous solution of sodium sulphide followed by washing out more than 95% of the sodium.

7. A process according to claim 1, in which the absorption mass results from the impregnation of a support by means of a solution of a soluble copper compound, followed by sulphurization.

8. A process according to claim 7, in which said solution contains both a soluble copper compound and a soluble silver compound.

9. A process according to claim 7, in which sulphurization is performed with an aqueous solution of sodium sulphide followed by washing out more than 95% of the sodium.

10. A process according to claim 7, in which sulphurization is performed by means of hydrogen sulphide.

11. A process according to claim 1, in which the proportion of copper sulphide in the absorption mass, calculated as copper, represents 5 to 50% of the weight of the mass.

12. A process according to claim 1, further comprising regeneration of the absorption mass by heating the mass following a mercury absorption stage.

13. A process according to claim 12, in which the absorption mass is regenerated by heating in the presence of a light hydrocarbon.

14. A process according to claim 13, wherein steam is in mixture with said light hydrocarbon.

15. A process according to claim 1, in which a natural gas containing a major proportion of methane, a minor proportion of C₅ hydrocarbons and a minor proportion of mercury is treated.

16. A process according to claim 1, in which the absorption mass is activated by heating in the presence of a light hydrocarbon.

17. A process according to claim 16, wherein steam is in mixture with said light hydrocarbon.

18. A process according to claim 1, wherein the mass has an average pure diameter of at least equal to 100 A.

19. A process according to claim 1, wherein the mass has a surface area of 20-250 m² /g.

20. A process according to claim 1, wherein at least 80% of the copper is in the sulfide state.

21. A process according to claim 1, wherein natural gas is treated at a rate of 4,000-20,000 V. V. H.