Process for removing heavy metals from process streams

• US 9,908,084 B2
• Filed: 07/10/2013
• Issued: 03/06/2018
• Est. Priority Date: 07/26/2012
• Status: Expired due to Fees

• Current Assignee: Johnson Matthey PLC
• Original Assignee: Johnson Matthey PLC
• Inventors: Fish, Andrew, Foster, Andrea Lara, Lunn, Matthew David Gwydion, Mansfield, Rachel
• Primary Examiner(s): Zimmer, Anthony J
• Assistant Examiner(s): IQBAL, SYED TAHA
• Application Number:
  US14/414,959
• Publication Number:
  US 20150182911A1
• Time in Patent Office: 1,700 Days
• CPC Class Codes: B01D 2253/104 Alumina
• CPC Class Codes: B01D 2253/106 Silica or silicates
• CPC Class Codes: B01D 2253/1128 Metal sulfides
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/20 Carbon monoxide
• CPC Class Codes: B01D 2257/602 Mercury or mercury compounds
• 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 20/28011 Other properties, e.g. density, crush strength
• CPC Class Codes: B01J 20/2803 Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
• CPC Class Codes: B01J 20/3028 Granulating, agglomerating or aggregating
• CPC Class Codes: B01J 20/3085 Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• CPC Class Codes: C01B 2203/0465 Composition of the impurity
• CPC Class Codes: C01B 3/56 by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: C10G 25/003 Specific sorbent material, not covered by C10G25/02 or C10G25/03
• CPC Class Codes: C10G 45/22 with hydrogen dissolved or suspended in the oil

Abstract

A process for removing heavy metals from process fluids includes passing a heavy-metal-containing process fluid, including a reductant selected from hydrogen and carbon monoxide, at an inlet temperature ≦125° C. over a sorbent including

• (i) 4-75% by weight of one or more sulphided copper compounds selected from sulphided basic copper carbonate, sulphided copper hydroxide, sulphided copper oxide or mixtures of these,
• (ii) optionally a support material, and
• (iii) a binder and the binder content of the sorbent is in the range 5-30% by weight,
  wherein essentially all of the sulphided copper is in the form of CuS and the total metal sulphide content of the sorbent, other than copper sulphide, is ≦5% wt.

Claims

1. A process for removing heavy metals from process fluids, comprising passing a heavy-metal-containing process fluid comprising a reductant that is hydrogen or carbon monoxide at an inlet temperature of 125°

C. or less over a sorbent having a form of extrudates or granules, wherein the sorbent comprises;

(i) 5-50% by weight of sulfided basic copper carbonate powder,

(ii) a powdered support material, and

(iii) 5-30% by weight of a binder,

wherein essentially all of the sulfided copper is in the form of CuS and the total metal sulfide content of the sorbent, other than copper sulfide, is 5% wt or less.

2. The process according to claim 1, wherein the sorbent comprises a support material that is alumina, hydrated alumina, titania, zirconia, silica or aluminosilicate, or a mixture of two or more of these.

3. The process according to claim 1, wherein the sorbent comprises a first binder and a second binder, wherein the first binder is a cement binder and the second binder is a high aspect ratio binder having an aspect ratio of greater than 2.

4. The process according to claim 3, wherein the first binder is a calcium aluminate cement binder.

5. The process according to claim 3, wherein the second binder is an aluminosilicate clay.

6. The process according to claim 3, wherein the relative amounts of the first and second binder are in the range of 1:

1 to 3;

1.

7. The process according to claim 1, wherein the total metal sulfide content of the sorbent, other than copper sulfide, is 0.5% wt or less.

8. The process according to claim 1, wherein the sulfur density of the sorbent is in the range of 50 to 200 kg S/m³.

9. The process according to claim 1, wherein the process fluid is a liquid hydrocarbon stream containing dissolved hydrogen and/or carbon monoxide.

10. The process according to claim 1, wherein the process fluid is a gaseous stream containing hydrogen and/or carbon monoxide.

11. The process according to claim 10, wherein the gaseous stream comprises a reductant in the range of 1-100 vol %.

12. The process according to claim 10, wherein the process fluid is a synthesis gas stream.

13. The process according to claim 10, wherein the process fluid is a refinery vent stream, a refinery cracker stream, a blast furnace gas, a reducing gas, or a hydrogen-rich gas stream.

14. The process according to claim 1, wherein the process fluid inlet temperature is 100°

C. or less.

15. The process according to claim 1, wherein the process fluid further comprises water in the range of 0.02 to 1 vol %.

16. The process according to claim 10, wherein the gaseous stream comprises a reductant in the range of 5-95 vol %.

17. The process according to claim 10, wherein the gaseous stream comprises a reductant in the range of 1-49 vol %.

18. The process according to claim 10, wherein the gaseous stream comprises a reductant in the range of 50-95 vol %.

19. The process according to claim 1, wherein the process fluid inlet temperature is 95°

C. or less.

20. The process according to claim 1, wherein the sulfided basic copper carbonate powder has an average particle size D₅₀ in a range of 10-100 μ

m, and the powdered support material has a particle size of 5-65 μ

m.