Purification process

• US 10,252,211 B2
• Filed: 05/30/2012
• Issued: 04/09/2019
• Est. Priority Date: 09/29/2011
• Status: Active Grant

• Current Assignee: Johnson Matthey PLC
• Original Assignee: Johnson Matthey PLC
• Inventors: Baptist, Colin, Cahill, Claire, Cousins, Matthew John, Davis, David, Wilson, Michelle Taylor, Young, Christopher John
• Primary Examiner(s): Robinson, Renee
• Assistant Examiner(s): Mueller, Derek N
• Application Number:
  US14/346,880
• Publication Number:
  US 20140296607A1
• Time in Patent Office: 2,505 Days
• 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 15/10 characterised by constructional or operational features
• CPC Class Codes: B01D 15/1871 placed in series
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2256/24 Hydrocarbons
• CPC Class Codes: B01D 2257/204 Inorganic halogen compounds
• CPC Class Codes: B01D 2257/2045 Hydrochloric acid
• CPC Class Codes: B01D 2257/206 Organic halogen compounds
• CPC Class Codes: B01D 2257/2064 Chlorine
• CPC Class Codes: B01D 2259/402 using two beds
• CPC Class Codes: B01D 2259/414 using different types of adsorbents
• 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: C01B 7/0718 by adsorption
• CPC Class Codes: C01B 7/093 Hydrogen bromide
• CPC Class Codes: C07C 7/12 by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
• CPC Class Codes: Y02P 20/151 Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Abstract

A process for removing halogen compounds, particularly chlorine compounds, from a process fluid, includes the steps of (i) passing a process fluid containing hydrogen halide over a first sorbent to remove hydrogen halide and generate a hydrogen halide depleted process fluid and then, (ii) passing the hydrogen halide depleted process fluid over a second different sorbent to remove organic halide compounds therefrom. A purification system suitable for removing hydrogen halide and organic halide compounds from process fluids is also described.

Claims

1. A purification system for removing halogen compounds from process fluids, comprising:

a feed source of a process fluid containing hydrogen halide,

a first sorbent comprising an alkalized alumina or an alkalized zinc-alumina, wherein the first sorbent is in the form of pellets, granules, or extrudates; and

a second sorbent comprising a mixed transition alumina and that is in the form of granulated or extruded shaped units comprising 1 wt %-10 wt % binder;

wherein;

the first sorbent is positioned between the feed source and the second sorbent, and the purification system is controlled to direct the flow of the feed gas through the purification system from the feed source to the first sorbent and then to the second sorbent, such that the second sorbent is positioned downstream from the first sorbent, relative to the directed flow of the process fluid.

2. The purification system according to claim 1, further comprising a third sorbent downstream of the second sorbent, wherein the third sorbent removes hydrogen halide from the process fluid.

3. The purification system according to claim 2, wherein the third sorbent is the same as the first sorbent.

4. The purification system according to claim 1, wherein the sorbents are placed in the same vessel.

5. The purification system according to claim 1, wherein the first sorbent is formed from a calcined intimate mixture of:

a) an alumina component that is alumina and/or hydrated alumina,

b) an optional zinc component that is a zinc oxide, zinc hydroxide, zinc carbonate, zinc bicarbonate and/or basic zinc carbonate,

c) a basic metal component that is at least one compound of at least one alkali or alkaline earth metal, and

d) 5 to 20% by weight of a binder.

6. The purification system according to claim 5, wherein the first sorbent comprises a zinc component with a basic metal to zinc atomic ratio in the range of from 0.5x to 2.5x and a basic metal to aluminum atomic ratio in the range of from 0.5x to 1.5x where x is the valency of the basic metal.

7. The purification system according to claim 5, wherein the first sorbent has a basic metal oxide content of at least 10%, by weight after ignition of a sample at 900°

C.

8. The purification system according to claim 5, wherein the basic metal component is a compound of lithium, sodium, potassium, beryllium, magnesium, calcium, strontium, or barium.

9. The purification system according to claim 5, wherein the basic metal component is a compound of sodium or calcium.

10. The purification system according to claim 5, wherein the zinc component is zinc oxide, zinc carbonate, or basic zinc carbonate.

11. The purification system according to claim 5, wherein the binder comprises a hydraulic cement, or a clay.

12. The purification system according to claim 1, wherein the first sorbent comprises a calcined mixture of (i) hydrated alumina, (ii) sodium bicarbonate, (iii) zinc oxide or basic zinc carbonate, and (iv) a clay binder in which the alkali metal to zinc atomic ratio is above 0.8.

13. The purification system according to claim 12, wherein the alkali metal to zinc atomic ratio is in the range from about 0.8 to 2.2.

14. The purification system according to claim 1, wherein the first sorbent has a BET surface area of at least 10 m²/g.

15. The purification system according to claim 4, wherein the first sorbent has a BET surface area above 50 m²/g.

16. The purification system according to claim 1, wherein the first sorbent has a BET surface area above 90 m²/g.

17. The purification system according to claim 1, wherein the transition alumina is a gamma alumina, delta-alumina, theta-alumina, eta-alumina or chialumina, or a mixture thereof.

18. The purification system according to claim 1, wherein the transition alumina is formed by calcination of aluminum hydroxides and has a BET surface area in the range 50 to 400 m²/g.

19. The purification system according to claim 1, wherein the fast sorbent comprises acidic sites and forms one or more organic halide compound.

20. The purification system according to claim 1, wherein the first sorbent comprises an alkalized zinc-alumina.

21. A process for removing halogen compounds from a process fluid in a system of claim 1, comprising the steps of (i) passing the process fluid containing the hydrogen halide over the first sorbent to remove hydrogen halide and generate a hydrogen halide depleted process fluid, and (ii) passing the hydrogen halide depleted process fluid over the second sorbent to remove the organic halide compounds therefrom.

22. The process according to claim 21, wherein the process fluid is a hydrogen gas stream comprising ≥

50% vol hydrogen.

23. The process according to claim 21, wherein the process fluid is a gas stream comprising a hydrocarbon.

24. The process according to claim 21, wherein the process fluid is a liquid hydrocarbon stream.

25. The process according to claim 21, wherein the halogen compounds are bromine compounds or chlorine compounds.

26. The process according to claim 21, wherein the hydrogen halide content of the process fluid fed to the first sorbent is in the range 0.1-20 ppm.

27. The process according to claim 23, wherein the first sorbent comprises acidic sites that form one or more organic halide compounds.

28. The process according to claim 21, wherein the process fluid from which organic halide compounds has been removed is passed over a third sorbent to remove residual or formed hydrogen halide.

29. The process according to claim 28, wherein the third sorbent is the same as the first sorbent.

30. The process according to claim 21, operated at a temperature in the range 0-300°

C.

31. The process according to claim 21, operated at a pressure in the range 1 to 100 bar abs.