Process for capturing sulfur dioxide from a gas stream

• US 9,919,262 B2
• Filed: 11/05/2014
• Issued: 03/20/2018
• Est. Priority Date: 11/07/2013
• Status: Active Grant

• Current Assignee: Shell Oil Company (Shell Plc)
• Original Assignee: Shell Oil Company (Shell Plc)
• Inventors: Ouimet, Michel, Infantino, Mlina
• Primary Examiner(s): Lawrence, Frank
• Application Number:
  US15/034,360
• Publication Number:
  US 20160263519A1
• Time in Patent Office: 1,231 Days
• Field of Search: 95187, 95235, 4232421, 4232422, 4232423, 4232427
• CPC Class Codes: B01D 2252/20 Organic absorbents
• CPC Class Codes: B01D 2252/2026 Polyethylene glycol, ethers or esters thereof, e.g. Selexol
• CPC Class Codes: B01D 2252/2041 Diamines
• CPC Class Codes: B01D 2252/20415 Tri- or polyamines
• CPC Class Codes: B01D 2252/20426 Secondary amines
• CPC Class Codes: B01D 2252/20431 Tertiary amines
• CPC Class Codes: B01D 2252/20436 Cyclic amines
• CPC Class Codes: B01D 2252/20447 containing a piperazine-ring
• CPC Class Codes: B01D 2252/20457 containing a pyridine-ring
• CPC Class Codes: B01D 2252/504 Mixtures of two or more absorbents
• CPC Class Codes: B01D 53/1425 Regeneration of liquid absorbents
• CPC Class Codes: B01D 53/1475 Removing carbon dioxide
• CPC Class Codes: B01D 53/1481 Removing sulfur dioxide or sulfur trioxide
• CPC Class Codes: B01D 53/1493 Selection of liquid materials for use as absorbents
• CPC Class Codes: Y02A 50/20 Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
• CPC Class Codes: Y02C 20/40 of CO2

Abstract

A process for removing sulfur dioxide from a feed gas stream, which comprises (i) contacting the feed gas stream with an aqueous lean absorbing medium comprising a chemical solvent comprising a regenerable absorbent, a physical solvent, and one or more heat stable salts. The regenerable absorbent is an amine. The ratio of the wt % of the physical solvent over that of the regenerable absorbent is 0.5 to 2.5. The ratio of the wt % of heat stable salts over that of the regenerable absorbent is 0.29 to 0.37. The pH of the lean absorbing medium is 6 or less. With the process SO2 can be selectively removed. When the absorbing medium is stripped, a reduced amount of energy is required as compared to known processes.

Claims

1. A process for removing sulfur dioxide from a feed gas stream, which process comprises:

(i) contacting the feed gas stream with an aqueous lean absorbing medium to absorb sulfur dioxide and to form a sulfur dioxide lean treated gas stream and a spent absorbing medium;

wherein the aqueous lean absorbing medium comprises;

(a) a chemical solvent comprising a regenerable absorbent,

(b) a physical solvent, and

(c) one or more heat stable salts;

wherein the regenerable absorbent is an amine;

wherein the ratio of the weight percentage of the physical solvent in the lean absorbing medium over that of the regenerable absorbent is in the range of from 0.5 to 2.5;

wherein the ratio of the weight percentage of heat stable salts in the lean absorbing medium over that of the regenerable absorbent is in the range of from 0.29 to 0.37; and

wherein the pH of the lean absorbing medium is 6 or less.

2. The process according to claim 1, wherein the process further comprises:

(ii) stripping, absorbed sulfur dioxide from the spent absorbing medium to produce a regenerated aqueous absorbing medium and a gaseous sulfur dioxide;

and optionally

(iii) recycling the regenerated aqueous absorbing medium from step (ii) to step (i).

3. The process according to claim 1, wherein the absorbing medium is present in a single liquid phase during step (i).

4. The process according to claim 2, wherein the absorbing medium is present in a single liquid phase during step (ii).

5. The process according to claim 2, wherein step (ii) is performed in a reboiler,

forced circulation reboiler, fired reboiler, falling film reboiler, direct steam reboiler, or thermosyphon.

6. The process according to claim 2, wherein at least 97 vol % of the spent absorbing medium formed in step (i) is stripped in step (ii).

7. The process according to claim 1, wherein the regenerable absorbent is a diamine or polyamine which in half salt form has a pK_a value for the free nitrogen atom of 3.0 to 5.5, preferably 3.5 to 4.7, at a temperature of 20°

C. in an aqueous medium.

8. The process according to claim 1, wherein the regenerable absorbent is a diamine represented by the formula:

9. The process according to claim 1, wherein the regenerable absorbent is a tertiary amine represented by the formula:

10. The process according to claim 1, wherein the regenerable absorbent is piperazine, hydroxyethyl piperazine, bis-hydroxyethyl piperazine, hydroxyethylethylenediamine, bis-hydroxyethylethylenediamine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 2-[2-aminoethyl]pyridine, 2-aminomethylpyridine, 3-amino 5-methylpyrazole, 3-aminopyrazole, 3-methylpyrazole, N,N,N′

,N′

-tetraethyldiethylenetriamine, N,N,N′

,N′

-tetramethyldiethylenetriamine, 2-piperazinone 1,4-bis[2-hydroxyethyl], or a combination thereof.

11. The process according to claim 1, wherein the lean absorbing medium additionally comprises an organic acid and/or an anorganic acid.

12. The method according to claim 1, wherein the physical solvent has a vapour pressure less than 0.1 mmHg at 20°

C. with a boiling point equal to or higher than 240°

C.

13. The process according to claim 1, wherein the physical solvent is a polyol, a polycarbonate, an N-formyl morpholine, or a combination thereof.

14. The process according to claim 1, wherein the physical solvent is polyethyleneglycol dimethylether (PEGDME), tetraethyleneglycol dimethylether (TetraEGDME), tetraethylene glycol (TetraEG), triethyleneglycol monomethylether (TriEGMME), or a combination thereof.

15. The process according to claim 1, wherein the physical solvent is polyethyleneglycol dimethylether (PEGDME), and

wherein the regenerable absorbent is

4-[hydroxyethyl]piperazine (Hep), or

1,4-bis[hydroxyethyl]piperazine (DiHep), or

3-aminopyrazole, or

a mixture of 4-[hydroxyethyl]piperazine (Hep) and

1,4-bis[hydroxyethyl]piperazine (DiHep).