Chemistry of inorganic compounds – Sulfur or compound thereof – Elemental sulfur
Reexamination Certificate
2000-02-15
2002-07-09
Griffin, Steven P. (Department: 1754)
Chemistry of inorganic compounds
Sulfur or compound thereof
Elemental sulfur
C423S574100, C423S575000, C423S576200
Reexamination Certificate
active
06416729
ABSTRACT:
FIELD OF INVENTION
This invention relates generally to processes and systems for removing hydrogen sulfide from a gaseous stream. More specifically the invention relates to improvements in a known process and system wherein hydrogen sulfide is removed from a gaseous stream, using a nonaqueous scrubbing liquor in which are dissolved sulfur and a reaction-promoting amine base. In a first aspect of the invention sulfur dioxide is added as an oxidizing gas to the sulfur-amine nonaqueous sorbent (or advantage is taken of SO
2
which may already be present in the gas stream) to obtain better H
2
S removal, lower chemical degradation rates, and lower rates of formation of byproduct sulfur salts. In a further aspect of the invention the gas to be treated is mixed with oxygen and passed through an oxidation catalyst reactor to either effect oxidation of part of the H
2
S to form the required amount SO
2
for reaction with the remaining H
2
S, or to effect partial oxidation of the H
2
S in the feed gas to form elemental sulfur, or to form various combinations of products as desired for the application, prior to scrubbing with the nonaqueous solvent.
DESCRIPTION OF PRIOR ART
Conventional liquid redox sulfur recovery processes use a redox couple dissolved in water to scrub hydrogen sulfide from a gas stream and convert it to sulfur. The redox agent is reduced by the hydrogen sulfide and then is regenerated by contacting with air in a separate vessel. One of the main problems with such processes is dealing with the solid sulfur product, which is formed in an uncontrolled manner. The sulfur formed from aqueous solution is notorious for plugging the absorber or other vessels which is passes through, and it is generally hard to separate and handle. Sulfur formed from nonaqueous solvents has much better handling properties. However, most nonaqueous redox systems have certain disadvantages such as sluggish sulfur formation kinetics or difficulties in regenerating the sorbent with air. In aqueous systems, contact of polysulfides with air primarily produces sulfates and other undesired sulfur oxyanion byproducts which are difficult to purge from the system.
The present inventor's U.S. Pat. No. 5,738,834, the entire disclosure of which is hereby incorporated by reference, discloses a process which uses a sulfur-amine nonaqueous sorbent (SANS) and operating conditions under which sulfur itself can convert hydrogen sulfide to polysulfides which are nonvolatile but which can be readily transformed to sulfur by reaction with an oxidizing agent. This is done in a solvent with a high solubility for sulfur so that solid sulfur formation does not occur in the absorber or in the air-sparged regenerator. Solid sulfur formation can be initiated in process equipment designed to handle solids and can be done under well-controlled conditions. In the SANS process, the sour gas is fed to an absorber (typically countercurrent) where the H
2
S is removed from the gas by a nonaqueous liquid sorbing liquor which comprises an organic solvent for elemental sulfur, dissolved elemental sulfur, an organic base which drives the reaction converting H
2
S sorbed by the liquor to a nonvolatile polysulfide which is soluble in the sorbing liquor, and an organic solubilizing agent which prevents the formation of polysulfide oil—which can tend to separate into a separate viscous liquid layer if allowed to form. The solubilizing agent is typically selected from the group consisting of aromatic alcohols and ethers including alkylarylpolyether alcohol, benzyl alcohol, phenethyl alcohol, 1-phenoxy-2-propanol, 2-phenoxyethanol, alkyl ethers including tri(propylene glycol) butyl ether, tri(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, tri(ethylene glycol) dimethyl ether, benzhydrol, glycols such as tri(ethylene) glycol, and other polar organic compounds including sulfolane, propylene carbonte, and tributyl phosphate, and mixtures thereof. The sorbing liquor is preferably essentially water insoluble as this offers advantages where water may be condensed in the process. It is also preferable for water to be essentially insoluble in the solvent. The nonaqueous solvent is typically selected from the group consisting of alkyl-substituted naphthalenes, diaryl alkanes including phenylxylyl ethanes such as phenyl-o-xylylethane, phenyl tolyl ethanes, phenyl naphthyl ethanes, phenyl aryl alkanes, dibenzyl ether, diphenyl ether, partially hydrogenated terphenyls, partially hydrogenated diphenyl ethanes, partially hydrogenated naphthalenes, and mixtures thereof. In order to obtain a measurable conversion of sulfur and hydrogen sulfide to polysulfides, the base added to the solvent must be sufficiently strong and have sufficient concentration to drive the reaction of sulfur and hydrogen sulfide to form polysulfides. Most tertiary amines are suitable bases for this use. More particularly, tertiary amines including N,N imethyloctylamine, N,N dimethyldecylamine, N,N dimethyldodecylamine, N,N dimethyltetradecylamine, N,N dimethylhexadecylamine, N-methyldicyclohexylamine, tri-n-butylamine, tetrabutylhexamethylenediamine, N-ethylpiperidine hexyl ether, 1-piperidineethanol, N-methyldiethanolamine, 2-(dibutylamino)ethanol, and mixtures thereof are suitable for use in the said process. It should be noted that while the solvent utilized in the process requires the addition of a base to promote the reaction of sulfur and hydrogen sulfide to form polysulfides, the base and the solvent may be the same compound.
As it is removed, the H
2
S thus reacts with elemental sulfur and a tertiary amine, both dissolved in the sorbent, to form an amine polysulfide. One of the polysulfide-formation reactions in the absorber may be depicted as follows (where B stands for the amine, HB
+
is the protonated amine, g denotes the gas phase, and l denotes the liquid phase).
H
2
S(g)+S
8
(l)+2 B(l)⇄(HB)
2
S
9
(l) (1)
The stoichiometry shown in this equation is representative, although polysulfides of other chain lengths may be formed, and varying degrees of association of the amine and polysulfide may occur, depending on the specific solvent chemistry and operating conditions. The primary solvent is selected to have a high solubility for sulfur (as well as for the amine) so that the sorbent circulation rates can be low, producing small equipment sizes for both the H
2
S absorber and the solution regenerator. Another ingredient is normally added to the sorbent to solubilize the amine polysulfides which might otherwise separate. The sweet gas from the absorber exits the process. The rich sorbent from the absorber may be passed through a reactor to allow further time for polysulfide formation reactions to occur, if desired. The sorbent is flashed down to near atmospheric pressure in one or more stages, producing a small flash gas stream that can either be recycled or used as fuel for local power generation. The sorbent is then contacted with an oxidizing gas such as air in the regenerator to oxidize the polysulfide to elemental sulfur, which remains dissolved in the solvent. This reaction, which also frees the amine for the next sorption cycle, can be depicted as follows.
(HB)
2
S
9
(l)+½ O
2
(g)⇄S
8
(l)−H
2
O(g)+2 B(l) (2)
Under the proper chemical and physical conditions, the efficiencies for simple air regeneration are unexpectedly high and the rates of the air oxidation reaction to sulfur are unexpectedly fast for a nonaqueous system. Tertiary amines produce high regeneration efficiencies. Spent air from the oxidizer contains the product water. The sorbent stream from the oxidizer is cooled in a heat exchanger and fed to the crystallizer where the cooling causes the formation of crystalline sulfur. The sorbent is cooled to a sufficiently low temperature to crystallize enough solid sulfur to balance the amount of hydrogen sulfide absorbed in he absorber. This produces the same overall reaction as in other liquid redox sulfur recovery process.
H
2
S(g)+½ O
2
⇄&fra
Dalrymple Dennis
DeBerry David W.
CrystaTech, Inc.
Klauber & Jackson
Vanoy Timothy C.
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