Process for the production of copper sulfide

Patent metadata

Field	Value
Publication number	US-11065577-B2
Application number	US-201816635618-A
Country	US
Kind code	B2
Filing date	Aug 1, 2018
Priority date	Aug 1, 2017
Publication date	Jul 20, 2021
Grant date	Jul 20, 2021

Abstract

A process for preparing a copper sulfide of the formula CuxSy, wherein the process comprises the following steps: (i) reacting an aqueous solution of a copper salt with a molar excess of a sulfiding agent so as to precipitate copper sulfide from the solution; (ii) isolating the copper sulfide precipitate from the reaction mixture; and (iii) drying the copper sulfide precipitate at a temperature of less than 100° C., wherein x and y are integer or non-integer values.

First claim

The invention claimed is:

1. A process for the removal of mercury from a mercury-containing hydrocarbon fluid stream comprising the steps of:
(i) contacting the mercury-containing hydrocarbon fluid stream with a sorbent comprising copper sulfide of the formula Cu x S y , wherein x and y are integer or non-integer values; and
(ii) separating a fluid product from the sorbent, wherein the fluid product has a reduced mercury content compared to the mercury-containing hydrocarbon fluid stream;
wherein the copper sulfide is obtained or obtainable by a process comprising the following steps:
(a) reacting an aqueous solution of a copper salt with a molar excess of a sulfiding agent so as to precipitate copper sulfide from the solution;
(b) isolating the copper sulfide precipitate from the reaction mixture; and
(c) drying the copper sulfide precipitate at a temperature of less than 100° C.

2. A process according to claim 1 , wherein the copper salt and sulfiding agent are contacted in a ratio of from 1:1.01 to 1:1.5.

3. A process according to claim 1 , wherein the molarity of the aqueous copper salt solution is from 0.1 M to 1.5 M.

4. A process according to claim 1 , wherein the copper salt is a copper (II) salt.

5. A process according to claim 1 , wherein the sulfiding agent comprises a sulfide salt.

6. A process according to claim 5 , wherein the sulfide salt is dissolved in aqueous solution.

7. A process according to claim 1 , wherein step i) comprises contacting the aqueous solution of copper salt with a molar excess of an aqueous solution of ammonium sulfide or sodium sulfide; stirring the reaction mixture for a period of time; before allowing the reaction mixture to stand for a period of time.

8. A process according to claim 1 , wherein the step of (i) reacting the aqueous solution of a copper salt and sulfiding agent comprises adding the aqueous copper salt solution to a container comprising an aqueous solution of a sulfiding agent.

9. A process according to claim 1 , wherein the copper salt comprises copper (II) chloride and the sulfiding agent comprises ammonium sulfide or sodium sulfide.

10. A process according to claim 1 , wherein the reaction mixture is stirred for a time period of from 10 minutes to 30 minutes.

11. A process according to claim 1 , wherein the reaction mixture is allowed to stand for a time period of from 5 minutes to 60 minutes.

12. A process according to claim 1 , wherein the sulfiding agent comprises hydrogen sulfide gas.

13. A process according to claim 12 , wherein the hydrogen sulfide gas is mixed with nitrogen, and is present in said nitrogen in an amount of from 50 ppm to 250 ppm nitrogen.

14. A process according to claim 1 , wherein step (ii) of isolating the copper sulfide from the reaction mixture comprises filtering the copper sulfide precipitate from the reaction mixture.

15. A process according to claim 1 , wherein step (iii) of drying the copper sulfide precipitate comprises drying the precipitate for a time period of less than 48 hours.

16. A process according to claim 1 , wherein step (iii) of drying the copper sulfide precipitate comprises drying the precipitate in vacuum at a temperature of less than 100° C.

17. A process according to claim 1 , wherein step (iii) of drying the copper sulfide precipitate comprises drying the precipitate in air at a temperature of less than 70° C.

18. A process according to claim 1 , wherein step (iii) of drying the copper sulfide precipitate comprises drying the precipitate at a temperature of above 15° C.

19. A process according to claim 1 , wherein the process is carried out in the presence or absence of one or more support materials or one or more binder materials.

20. A process according to claim 1 , wherein the mercury is in elemental, particulate, or organic form.

21. A process according to claim 1 , wherein the mercury concentration in the mercury-containing hydrocarbon fluid stream is in the range of from 1 to 2000 parts per million (ppm).

22. A process according to claim 1 , wherein the mercury-containing hydrocarbon fluid stream is a liquid, one or more of:
(i) a liquefied natural gas;
(ii) a light distillate comprising liquid petroleum gas, gasoline, and/or naphtha;
(iii) a natural gas condensate;
(iv) a middle distillate comprising kerosene and/or diesel;
(v) a heavy distillate; and
(vi) a crude oil.

23. A process according to claim 1 , wherein the mercury-containing hydrocarbon fluid stream comprises natural gas and/or refinery gas.

24. A process according to claim 23 , wherein the mercury-containing hydrocarbon fluid feed comprises wet natural gas or dry natural gas.

25. A process according to claim 1 , wherein the sorbent comprising copper sulfide and mercury-containing hydrocarbon fluid stream are contacted at a temperature of from 0° C. to 200° C.

26. A process according to claim 1 , wherein sorbent comprising copper sulfide and mercury-containing hydrocarbon fluid stream are contacted at a pressure of from 0 to 10,000 KPa.

27. A process according to claim 1 , wherein the mercury-containing hydrocarbon fluid stream and sorbent comprising copper sulfide are contacted for a period of up to 5 hours.

Assignees

• Petroliam Nasional Berhad Petronas

Inventors

• Seddon Kenneth
• Srinivasan Geetha
• Rafeen Mohammad Syamzari
• Cheun Kuah Yong
• Hassan Amiruddin
• Razali Adi Aizat
• Wong Sharizal Bin Mohd Azam Shah

Classifications

• B01J20/0237

  Compounds of Cu · CPC title

• B01J20/3204

  Inorganic carriers, supports or substrates · CPC title

• C01G3/12 Primary

  Sulfides · CPC title

• C01P2004/64

  Nanometer sized, i.e. from 1-100 nanometer · CPC title

• B01J20/3042

  Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent · CPC title