Form of copper sulfide

Patent metadata

Field	Value
Publication number	US-11613708-B2
Application number	US-201816635588-A
Country	US
Kind code	B2
Filing date	Aug 1, 2018
Priority date	Aug 1, 2017
Publication date	Mar 28, 2023
Grant date	Mar 28, 2023

Abstract

Copper sulfide of the formula Cu x S y , wherein x and y are integer or non-integer values, wherein (i) the copper sulfide has a sulfur 2p XPS spectrum with peaks at 162.3 eV (±1 ev), 163.8 eV (±1 ev) and 68.5 eV (±1 ev), characterised in that the peak at 168.5 eV has a lower value of counts per second (CPS) than both the peak at 162.3 eV and the peak at 163.8 eV; and (ii) the copper sulfide has a copper 2p XPS spectrum with peaks at 932.0 eV (±2 ev) and 933.6 eV (±3 eV) and characterised in that the XPS spectrum does not comprise identifiable satellite peaks at 939.8 eV and 943.1 eV (±3 eV).

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;
characterised by a copper 2p X-ray Photoelectron Spectroscopy (XPS) spectrum substantially as shown in FIG. 15 , and a sulfur 2p XPS spectrum substantially as shown in FIG. 16 .

2. A process according to claim 1 , characterised by an X-ray powder diffraction (XRPD) spectrum substantially as shown in FIG. 19 .

3. A process according to claim 1 , characterised by a copper 2p XPS spectrum with peaks at 932.0 eV (±2 ev) and 933.6 eV (±3 eV), and wherein the XPS spectrum does not comprise identifiable satellite peaks at 939.8 eV (±3 eV) and 943.1 eV (±3 eV).

4. A process according to claim 3 , wherein the copper sulfide has a sulfur 2p XPS spectrum with peaks at 162.3 eV (±1 ev), 163.8 eV (±1 ev) and 168.5 eV (±1 ev), characterised in that the peak at 168.5 eV has a lower value of counts per second (CPS) than both the peak at 162.3 eV and the peak at 163.8 eV.

5. A process according to claim 1 , further characterised in that the copper sulfide has an X-ray powder diffraction spectrum comprising peaks at the following 2θ values: 29.54 (±1), 32.21 (±1), 48.24 (±1) and 59.37 (±1).

6. A process according to claim 5 wherein the relative intensities of each peak are as follows:
2θ Relative Intensity
29.54 (±1) 72.42
32.21 (±1) 72.20
48.24 (±1) 100.00
59.37 (±1) 47.00.

7. A process according to claim 5 , wherein the peak at 2θ=32.21 (±1) is the only peak in the spectrum between the peak at 2θ=29.54 (±1) and 2θ=48.21 (±1).

8. A process according to claim 1 , wherein the copper sulfide is in a nanocrystalline form.

9. A process according to claim 1 , wherein the copper sulfide comprises or consists of crystallites with no dimensions bigger than 250 nm.

10. A process according to claim 1 , wherein the copper sulfide comprises or consists of crystallites with a length of from 10 nm to 250 nm and with a width and depth of from 5 nm to 50 nm.

11. A process according to claim 1 , wherein the copper sulfide comprises or consists of crystallites with a round or ovular shape.

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

13. 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.

14. A process according to claim 1 , wherein the mercury-containing hydrocarbon fluid stream is a liquid, comprising 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.

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

16. A process according to claim 1 , wherein the mercury-containing hydrocarbon fluid feed comprises wet natural gas or dry natural gas.

17. A process according to claim 1 , wherein the sorbent comprising copper sulfide does not comprise one or more support materials or one or more binder materials.

18. A process according to claim 1 , wherein the sorbent comprising copper sulphide further comprises one or more support materials or one or more binder materials, the materials comprising activated carbon, silicates, alumina, titanium, zirconia, alumina-silicate, metal aluminate, hydrated metal oxide, mixed metal oxide, cement, zeolite, a ceramic material, clay, cement, polymers, or any combination thereof.

19. 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.

20. A process according to claim 1 , wherein sorbent comprising copper sulfide and mercury-containing hydrocarbon fluid stream are contacted at atmospheric pressure.

21. A process according to claim 1 , wherein the mercury-containing hydrocarbon fluid stream and sorbent comprising copper sulfide are contacted for a period of from 1 to 60 hours.

22. 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 CuxSy, 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;
characterised by a copper 2p X-ray Photoelectron Spectroscopy (XPS) spectrum substantially as shown in FIG. 15 , and a sulfur 2p XPS spectrum substantially as shown in FIG. 16 ; and
wherein the mercury concentration in the mercury-containing hydrocarbon fluid stream is in the range of from 1 to 2000 parts per million by weight.

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

• C10L2270/04

  for turbines, planes, power generation · CPC title

• C10G2300/1074

  Vacuum distillates · CPC title

• C10G2300/1051

  Kerosene having a boiling range of about 180 - 230 °C · CPC title

• C10L3/101

  Removal of contaminants · CPC title

• B01J20/3204

  Inorganic carriers, supports or substrates · CPC title