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Sulfur Unit Tailgas treating incinerator
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U.S. Patent Jul. 29, 2014 Sheet 2 of 2 US 8,790,427 B2
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US 8,790,427 B2
1. 2
PROCESS, METHOD, AND SYSTEM FOR gas feed to a dehydrator, the gas feed containing acid gases, a
REMOVING MERCURY FROM FLUIDS first concentration of Volatile mercury and water, contacting
the gas feed with a glycol Solution containing a complexing
CROSS-REFERENCE TO RELATED agent in the dehydrator, generating a dehydrated gas stream
APPLICATIONS with a reduced concentration of water and mercury; and
wherein mercury and water are concurrently removed from
This application claims benefit under 35 USC 119 of U.S. the gas feed for a rich glycol containing at least 50% of the
Provisional Patent Application Nos. 61/697,867 and 61/697, Volatile mercury in the gas feed as non-volatile mercury. In
855 with a filing date of Sep. 7, 2012. one embodiment, the method further comprises: heating the
10 rich amine solution containing mercury and acid gases in a
TECHNICAL FIELD Solvent regeneration process employing at least a stripper and
a reboiler, generating a lean amine containing non-volatile
The invention relates generally to a process, method, and mercury for recycle in an absorber to remove acid gases.
system for removing heavy metals such as mercury from In a second aspect, a method for removing a trace amount
hydrocarbon fluids such as natural gas. of mercury in a natural gas feed is provided. The method
15 comprises: providing a gas feed containing acid gases, a first
BACKGROUND concentration of Volatile mercury and water, contacting the
gas feed with a glycol solution in a dehydrator, the glycol
Exploration and production of deeper, lower quality oil and Solution containing a complexing agent for the glycol solu
gas reserves has challenged refiners and gas processors with tion to concurrently remove the volatile mercury and water
feedstocks having significantly higher Sulfur content, from the gas feed, for a rich glycol containing at least 50% of
increasing corrosion risks and other undesired impurities. the Volatile mercury in the gas feed as non-volatile mercury,
Amine units for amine gas treating (also known as 'gas generating a dehydrated gas stream having a reduced concen
Sweetening or 'acid gas removal) refers to a group of pro tration of water and mercury, removing the non-volatile mer
cesses or units that use aqueous solutions of various alkano cury from the rich glycol by at least one offiltration, centrifu
lamines (commonly referred to simply as amines) for the 25 gation, precipitation, stripping, distillation, adsorption, ion
removal of HS and CO, from gases. The removal is driven by exchange, electrodialysis, a hydrocarbon Steam and separa
either required product specification, e.g., natural gas that tion step, and combinations thereof, generating a recycled
contains less than 4 ppm HS, or by environmental permis glycol stream having a reduced concentration of mercury of
sion requirements, and/or by the minimization of corrosion less than 50% of the non-volatile mercury in the rich glycol.
problem of process equipment. 30 In a third aspect, a method of removing mercury from a gas
Amine treating units are commonly used in refineries as feed is provided, the method comprises the steps of contact
well as in petrochemical plants, natural gas processing plants, ing the gas feed with an absorption solution in an absorber, the
and other industries, for the removal of HS and CO, from absorption solution comprising lean amine and a first com
gases. When Volatile mercury is present in the gases to the plexing agent, wherein the absorption solution concurrently
amine units, it will appear in the products from the units, e.g., 35 removes mercury and acid gases from the gas feed generating
the sweetened gas (after removal of HS and CO) and rich a rich amine solution containing mercury and acid gases and
amine containing H2S and CO. Mercury, CO and H2S are to a treated gas stream containing water vapor and a reduced
be removed from the sweetened gas. Mercury in these prod concentration of acid gases and a second concentration of
ucts can impact the operations downstream from the amine mercury, and wherein the second concentration of mercury is
units. 40 less than 50% of the first concentration of mercury; contact
Glycol dehydrators are sometimes used in to dry natural ing the treated gas stream with a glycol Solution in a dehy
gas, e.g., the Sweetened gas from the amine unit, to specifi drator, wherein the glycol solution contains a second com
cations. The glycol absorbs the moisture forming a dry gas. plexing agent for the glycol solution to concurrently remove
Wet glycol is recycled by vaporizing water at low pressure mercury and water vapor from the treated gas stream, gener
and at elevated temperatures. Methane and other hydrocar 45 ating a rich glycol containing non-volatile mercury and a
bons are somewhat soluble in triethylene glycol, particularly dehydrated gas stream with a reduced concentration of water
at high pressure and ambient temperature. These hydrocar and a third concentration of mercury, wherein the third con
bons are vaporized from the glycol as the pressure is reduced centration of mercury is less than 50% of the second concen
and temperature is increased. If mercury is present in the tration of mercury.
natural gas, a portion can appear in either the dry gas or vent 50 In yet another aspect, a method for removing mercury from
to the atmosphere from glycol dehydrators. a gas feed is provided. The method comprises: providing a gas
Absorbers have been used in the prior art to remove heavy feed containing a first concentration of Volatile mercury and
metals such as mercury from the Sweetened gas to specifica acid gases; contacting the gas feed in an absorber with an
tions, e.g., 0.1 ug/m, with the use of an adsorbent bed of absorption solution comprising lean amine and a first com
carbon, Zeolite, or Supported metals known in the art. The 55 plexing agent comprising Volatile cations selected from
adsorbents are rather expensive and require disposal as a ammonium polysulfide, amine polysulfides, and Sulfanes,
hazardous waste, or shipped to a re-processing facility. wherein the absorption Solution concurrently removes mer
There is still a need for improved methods and systems to cury and non-volatile mercury and acid gases from the gas
remove Volatile mercury from fluids such as natural gas, vent feed; generating a rich amine solution containing acid gases
gas or flue gas, allowing for the optimization of plant opera 60 and at least 50% of the volatile mercury in the gas feed as
tions to minimize the equipment corrosion, mercury emission non-volatile mercury and a treated gas stream with a second
and any HES risks associated with mercury. concentration of acid gases and mercury.
SUMMARY DRAWINGS
65
In one aspect, the invention relates to a method to remove FIG. 1 is a diagram illustrating an embodiment of a gas
mercury from a gas feed. The method comprises: providing a processing plant.
US 8,790,427 B2
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FIG. 2 is a diagram illustrating an embodiment of an amine In the sections that follow, the reference to “amine' is by
unit. way of exemplification only for a solute in which an acid gas
is chemically absorbed and can be Subsequently released.
DETAILED DESCRIPTION Similarly, the reference to “HS is by way of exemplification
only for an acid gas that can be chemically absorbed in a
The following terms will be used throughout the specifi liquid system, e.g., amine, Sour water, and can be subse
cation and will have the following meanings unless otherwise quently released, and does not exclude other acid gases or
indicated. mixtures thereof, e.g., mixture of H2S and CO, mixture of
“Trace amount” refers to the amount of mercury in the SO, NO, chlorine.
natural gas. The amount varies depending on the natural gas 10 Generally, natural gas streams comprise low molecular
source, ranging from a few ug/Nm to up to 30,000 ug/Nm. weight hydrocarbons such as methane, ethane, propane, other
“Volatile mercury” refers to mercury that is present in the paraffinic hydrocarbons that are typically gases at room tem
gas phase of well gas or natural gas. Volatile mercury is perature, etc. Mercury is present in natural gas as Volatile
primarily elemental mercury (Hg) but may also include mercury, including elemental mercury Hg", in levels ranging
Some other mercury compounds (organic and inorganic mer 15 from about 0.01ug/Nm to 5000 g/Nm. The mercury con
cury species). tent may be measured by various conventional analytical
“Mercury sulfide' may be used interchangeably with Hg.S. techniques known in the art, including but not limited to cold
referring to mercurous Sulfide, mercuric Sulfide, and mixtures vapor atomic absorption spectroscopy (CV-AAS), induc
thereof. Normally, mercury sulfide is present as mercuric tively coupled plasma atomic emission spectroscopy (ICP
Sulfide with an approximate Stoichiometric equivalent of one AES), X-ray fluorescence, or neutron activation. If the meth
mole of sulfide ion per mole of mercury ion. Mercury sulfide ods differ, ASTM D 6350 is used to measure the mercury
is not appreciably Volatile, and not an example of Volatile COntent.
mercury. Crystalline phases include cinnabar, metacinnabar The invention relates to an improved method and a system
and hypercinnabar with metacinnabar being the most com to remove heavy metals such as mercury present in natural gas
O. 25 feedstock, e.g., wet gas feed, in a gas processing plant. The
"Sulfane' refers to a hydrogen-sulfur complex of the for term 'gas processing plant may be used interchangeably
mula H2S, where x>-2. For purposes of this disclosure, with “gas production facility.” The mercury removal is car
hydrogen Sulfide is not a sulfane. ried out in the amine treating unit and/or the gas dehydration
“Wet gas' refers to natural gas that contains less methane unit of with the use of a complexing agent.
(e.g., less than 85%) and more ethane and other more com 30 Gas Processing Plant:
plex hydrocarbons. FIG. 1 is a schematic diagram illustrating the various pro
“Amine” refers to amines for use in gas treating, including cesses within a typical natural gas processing plant. Natural
but not limited to monoethanolamine (MEA), diethanola gas collected from gas wells is first processed in step 10 for
mine (DEA), methyldiethanolamine (MDEA), aminoethoxy the removal of liquid water and natural gas condensate, gen
ethanol (diglycoamine) (DGA), triethanolamine (TEA), 35 erating a gas feed which typically contains acid gases and
diisopropylamine (DIPA), proprietary amines known in the water vapor, which is typically referred to as a sour gas. The
art and commercially available, and mixtures thereof. The initial water removal step can be done at the processing plant,
most commonly used amines are the alkanolamines such as or it can be at the collection point.
MEA, DEA, and MDEA. In amine unit 30, the sour gas feed is purified with the
'Acid gas” refers to the product gas from an amine unit that 40 removal of acid gases by absorption with an amine solution,
contains acidic impurities, e.g., H2S, CO, SO and SO generating a gas stream with reduced concentration of acid
(SO), NO and NO (NO), chlorine, etc. In one embodiment, gases. The acid gases can be routed into a Sulfur recovery unit
the acid gas is chemically absorbed in the liquid (Solution or 15 to recover elemental sulfur. The residual gas is processed
fluid). In another embodiment, the acid gas is dissolved in the in the tail gas treating unit 40.
liquid, e.g., an aqueous amine Solution. 45 The Sweetened gas having a reduced concentration of acid
Amine unit refers to a process or a group of processes gases is routed to dehydrator 40, where a solution Such as
using aqueous solutions of various amines to remove hydro glycol is used to remove water vapor by absorption. In the
gen sulfide (H2S) and carbon dioxide (CO2) from gases. mercury removal unit (MRU) 50, mercury is then removed by
Amine unit can be located in refineries, petrochemical plants, adsorption using activated carbon or other adsorbents known
natural gas processing plants and other industries. It is also 50 in the art. After the MRU, nitrogen is optionally removed in
known as 'gas Sweetening” or “acid gas removal unit. process step 60 in a cryogenic or adsorption process. The
'Acid gas' refers to natural gas or any other gas mixture residue gas from the natural gas liquid (NGL) recovery pro
containing hydrogen Sulfide (H2S), carbon dioxide (CO), or cess 20 is the final purified gas which can be pipelined to the
similar acidic gases. end-user market, or optionally sent to a fractionation train 25
“Sour gas' refers to natural gas or flue gas prior to treat 55 with distillation towers to generate various products Such as
ment, which contains acid gas and trace amounts of mercury propane, butane, C5+, etc. The various gases can also be
as Volatile mercury. sweetened in unit 26 with the removal of mercaptains, prior to
"Richamine' refers to the aqueous amine solution contain being pipelined to the end-user market.
ing absorbed acid gas. In terms of the average distribution of mercury in a typical
“Lean amine” refers to the amine after being regenerated 60 gas processing plant as shown in FIG. 1, it has been shown
by Steam stripping to remove the absorbed acid gases and that out of 100% of mercury entering the plant, 90% goes to
produce regenerated amine Solution for use in the absorberto the amine unit as sour gas feed. Of this 90%, proportionally
treat Sour gas. 70% goes to the Sour gas product stream (i.e., to the Sulfur
"Sweetened gas” or 'Sweet gas' refers to a sour gas stream unit), and 30% stays in the Sweetened gas stream. The sweet
after treatment in an amine unit, after absorption/removal of 65 ened gas stream goes to the gas dehydration unit, e.g., a glycol
acid gas by an amine solution, and flows overhead from the dehydrator, wherein proportionally 20% leaves with the
absorber (scrubber or amine contactor). vented moisture stream, and 80% leaves in the dry gas. If not
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removed with a MRU, mercury can appear in other process Mercury Removal in Dehydrator Unit:
streams. It has been recommended that mercury be removed In another embodiment, mercury removal is carried out in
upstream of the process steps in a gas processing plant. The the dehydrator unit (“dehydrator') in addition to, or in place
invention relates to the removal of heavy metals such as of mercury removal in the amine unit. The dehydrator can be
mercury from feed to a gas processing plant. In one embodi tray columns or packed columns in one embodiment. In a
ment as illustrated in FIG. 1 with the mercury removal unit dehydrator, a liquid desiccant dehydrator Such as glycol
(MRU) being made optional (as dotted lines), mercury serves to absorb water vapor from the gas stream. Glycol has
removal is carried out in the amine unit concurrent with the a chemical affinity for water, upon contact with a stream of
removal of acid gas from the Sour gas feed with the addition natural gas that contains water in a dehydrator (e.g., a con
of a complexing agent to the amine Solution. In another 10 tactor, an absorber, etc.), will serve to steal the water out of
embodiment, mercury removal is carried out concurrently the gas stream. Upon exiting the dehydrator, the glycol stream
with the removal of water in a gas dehydration unit (in addi containing water (and mercury) is referred to as "rich glycol.”
tion to or instead of the amine unit), with the addition of a The glycol solution typically involves either diethylene
complexing agent to the glycol Solution. The complexing glycol (DEG) or triethylene glycol (TEG). In one embodi
agent for the mercury removal can be generated on-site, e.g., 15 ment, the glycol solution is employed in a concentration
manufacture of polysulfide solutions from elemental sulfur ranging from 99.1% up to 99.95% wt, in an amount sufficient
and Sulfidic Solutions, or the manufacture of Sodium sulfide to strip water at a rate of 0.5-6 scf of gas feed/gallon of glycol,
Solutions from Sodium carbonate and Sulfur sources if avail for a dehydrated gas having water specifications of less than
able on site. 1 lb./MMSCF (Million Standard Cubic Feet).
Mercury Removal in Amine Unit: The dehydrated gas having been stripped of most of its
In one embodiment for mercury removal in an amine treat water content has a concentration of less than 100 ug/Nm
ing unit, (lean) amine Scrubbing Solution is used to remove mercury in one embodiment; less than 10 g/Nmmercury in
acid gases such as hydrogen sulfide (H2S) and carbon dioxide a second embodiment; less than 1 ug/Nm in a third embodi
from the Sour feed steam in an absorber, generating a rich ment; and less than 0.1 ug/Nmmercury in a fourth embodi
amine stream. A sufficient amount of a complexing agent is 25 ment. The dehydrated gas is further processed, e.g., nitrogen
added to the absorber for the removal of mercury concur injection, NGL recovery, fractionation, etc.
rently with the removing of acid gases from the sour feed In one embodiment, the complexing agent is added as part
stream by the amine Scrubbing Solution. The complexing of the glycol solution feed to the dehydrator. In another
agent coverts at least a portion of the Volatile mercury in the embodiment, it is added as a separate feed stream to the
Sour gas feed into a non-volatile form, extracted from the gas 30 dehydrator. The complexing agent is added in an amount of
phase into the amine Scrubbing solution. less than 5 Vol.% of total glycol solution to the dehydrator in
The amount of amine in the scrubbing solution feed to the one embodiment; less than 3 Vol.% in a second embodiment;
absorber depends on the amount of acid gases in the natural less than 1 Vol.% in a third embodiment; and less than 0.5 vol.
gas to be treated (acid loadings), and based on the moles of % in a third embodiment.
HS (and/or CO) per mole of amine in solution. In one 35 Complexing Agent:
embodiment, the ratio of absorbed acid gases to amine ranges “Complexing agent” refers to a material or compound that
from 0.3 to 0.9. Examples of amines suitable for use in the is capable of extracting Volatile mercury in natural gas into
scrubbing solution include but are not limited to MEA, DEA, the liquid phase, forming non-volatile mercury complexes.
TEA, DIPA, MDEA, and mixtures thereof. The concentration Examples of non-volatile mercury complexes include HgS
of amines in the scrubbing solution varies depending on the 40 and soluble mercury sulfur compounds (e.g. HgHS or
amine type, and the acid gases for removal, e.g., H2S and CO Hg.S.).
or removing CO only, etc. The amine concentration (as wt.% Examples of complexing agents include but are not limited
of pure amine in the aqueous solution) ranges from 15-65% in to water-soluble Sulfur species, e.g., Sulfides, hydrosulfides,
one embodiment, from 20-55% in a second embodiment, and and polysulfides, for extracting mercury in natural gas into
from 25-45% in a third embodiment. In one embodiment, the 45 the aqueous phase as precipitate (e.g., HgS) or soluble mer
scrubbing solution further comprises absorption promoters cury Sulfur compounds (e.g. HgS). Examples of water
and other additives, e.g., piperazine. soluble Sulfur compounds include amine polysulfides,
The complexing agent is added to the leanamine feed to the Sodium hydrosulfide, potassium hydrosulfide, ammonium
absorber in one embodiment, as a separate feed stream to the hydrosulfide, Sodium sulfide, potassium Sulfide, calcium Sul
absorber in a second embodiment; and as the same feed with 50 fide, magnesium sulfide, ammonium sulfide, Sodium thiocar
the make-up water stream to the absorber in a third embodi bamate, sodium dithiocarbamate, ammonium thiocarbamate,
ment. The complexing agent is added in an amount of less ammonium dithiocarbamate, and mixtures thereof. Aqueous
than 5 Vol.% of total scrubbing solution in the amine absorber Source containing water-soluble Sulfur species can be any of
in one embodiment; less than 3 Vol.% in a second embodi purchased or produced reagent solutions, Sulfidic water, Sul
ment; less than 1 Vol.% in a third embodiment; and less than 55 fidic waste water, kraft caustic liquor, kraft carbonate liquor,
0.5 Vol.% in a third embodiment. etc.
In one embodiment to prevent contamination of the amine Other examples of complexing agents that can be used for
in the amine absorber, the complexing agent contains little if the removal of mercury from the amine unit includes mercap
any non-volatile alkali metals or alkali earth cations (none tans, organic polysulfides (compounds of the general formula
purposely added), e.g., with no Sodium polysulfide or other 60 R—S R' where x is greater than 1 and RandR' are alkyl or
Sodium salts, as the Sodium cation will accumulate in the aryl groups), Sulfanes and combinations thereof.
amine recycle and degrade its performance. In one embodi The amount of complexing agents to be added to the amine
ment, the complexing agent is selected from the group of scrubbing solution and/or the glycol solution is determined
Volatile cations, which can be removed in the regenerator. by the effectiveness of complexing agent employed. The
Examples of volatile cations include but are not limited to 65 complexing agent to be added to the amine Scrubbing solution
ammonium, amines and hydrogen cations, e.g., ammonium can be the same or different from the complexing agent added
polysulfide, amine polysulfides, and Sulfanes. to the glycol solution. The amount is at least equal to the
US 8,790,427 B2
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amount of mercury in the gas on a molar basis (1:1), if not in conditions. Anti-foam agents can be selected from a wide
an excess amount. In one embodiment, the molar ratio ranges range of commercially available products such as silicones,
from 5:1 to 10,000:1. In another embodiment, from 10:1 to e.g., polydimethyl siloxane (PDMS), polydiphenyl siloxane,
5000:1. In yet another embodiment, a molar ratio of sulfur fluorinated siloxane, etc., in an amount of 1 to 500 ppm.
additive to mercury ranging from 50:1 to 2500:1. In one 5 In one embodiment, at least a demulsifier is added in a
embodiment with the use of a water-soluble sulfur compound concentration from 1 to 5,000 ppm. In another embodiment,
as a scrubbing agent, a Sufficient amount of the complexing a demulsifier is added at a concentration from 10 to 500 ppm.
agent is added to the amine Scrubber for a Sulfide concentra In one embodiment, the demulsifier is a commercially avail
tion ranging from 0.05 M to 10M in one embodiment; from able demulsifier selected from polyamines, polyamidoam
0.1M to 5M in a second embodiment; from 0.3M to 4M in a 10 ines, polyimines, condensates of o-toluidine and formalde
third embodiment; and at least 0.5M in a fourth embodiment. hyde, quaternary ammonium compounds and ionic
If the mercury complexing agent is an organic polysulfide, surfactants. In another embodiment, the demulsifier is
Sulfane or mercaptan, the moles of complexing agent are selected from the group of polyoxyethylene alkyl phenols,
calculated on the same basis as the amount of Sulfur present. their Sulphonates and sodium Sulphonates thereof. In another
In one embodiment, the complexing agent is an inorganic 15 embodiment, the demulsifier is a polynuclear, aromatic Sul
polysulfide Such as Sodium polysulfide, for an extraction of fonic acid additive.
mercury from the natural gas according to equation: Hg(g)+ In another embodiment, in addition to the complexing
NaS (aq)+HO->HgSH (aq)+Na2S2(aq)+OH(aq), agent and optionally at least a demulsifier/anti-foam agent, an
where (g) denotes the mercury in the gas phase, and (aq) oxygen scavenger is preferably added to any of the glycol
denotes a species in water. The charges are balanced by other Solution, the amine Solution, and the absorbent. The oxygen
species. Solid HgS is not formed and the mercury remains in Scavenger may be present in an amount ranging from 0.001 to
Solution as an anionic species. In another embodiment, the 1 wt.%, based on the weight of the glycol solution, lean
complexing agent is a compound with a relatively high boil amine, or absorbent. As dissolved oxygen in the amine or
ing point, e.g., not too volatile and above 100° C. in one glycol storage tank would lead to corrosion of iron Surfaces,
embodiment and above 125° C. in another embodiment. If 25 or react with the feed gas making heat stable salts which are
not, the complexing agent would be lost in the stripping difficult to separate in the regeneration step, the oxygen Scav
operation for the removal of adsorbed acid gas from the acid enger removes traces of dissolved oxygen present, minimiz
gas scrubbing solution. In yet another embodiment the com ing corrosion impact.
plexing agent is sodium sulfide. Sodium sulfide and other Examples of oxygen Scavengers include bisulfites, met
complexing agents may promote the removal of mercury 30 abisulfites, hydrazine salts, hydroxylamine salts, guanidine
from gas streams containing high CO concentrations but low salts, N,N-Diethylhydroxylamine, oximes, dithionites, ascor
HS concentrations. In yet another embodiment the complex bic acid, and isoascorbic acid. The anion salts of these oxygen
ing agent is hydrogen sulfide (HS) or a combination of Scavengers can be chlorides, Sulfates, and other Suitable
hydrogen Sulfide and one or more of the above-mentioned anions. The cations associated with the oxygen Scavengers
complexing agents. 35 can be sodium, potassium or Volatile cations as described for
In one embodiment, the complexing agent is added to the the complexing agents. Volatile cations are preferred when
absorber (scrubber) and/or the contactor (dehydrator), allow they are used in an amine unit.
ing the extraction of Volatile mercury from the Sour gas feed A compatible oxygen scavenger is one that does not react
into the scrubbing Solution of rich amine or the glycol solu with the mercury complexing agent and reduce its effective
tion, for a Sweetened gas stream having a reduced concentra 40 ness for mercury capture. Examples of oxygen Scavengers
tion of acid gas as well as a mercury concentration of less than that react with a complexing agent such as polysulfide include
50% of the mercury originally present in one embodiment (at bisulfites and metabisulfite. In one embodiment, the oxygen
least 50% mercury removal). In another embodiment, the Scavenger is selected for compatibility with the mercury com
Sweetened gas contains less than 10% of the original mercury plexing agent. Examples of compatible oxygen Scavengers
level (at least 90% removal). In a third embodiment, less than 45 include: hydrazine salts, guanidine salts, N,N-Diethylhy
5% of the original level (at least 95% removal). The mercury droxylamine, oximes, dithionites, ascorbic acid, and
content in the Sweetened gas stream will depend on the mer isoascorbic acid.
cury content of the feed and the percent removal. The mercury Recovery/Regeneration of Amine Solution:
content is reduced to below 100 g/Nm in one embodiment, In one embodiment for the concurrent mercury removal
less than 10 ug/Nm in a second embodiment, less than 1 50 from the absorber, the resultant rich amine containing non
ug/Nm in a third embodiment, andless than 0.1 ug/Nm in a Volatile mercury and acid gases from the absorber is routed
fourth embodiment. into the regenerator. In the regenerator (a stripper with a
In one embodiment with the addition of complexing agent reboiler), a “lean” amine containing non-volatile mercury is
to the dehydrator, the glycol solution leaving the dehydrator regenerated for recycle? subsequent reuse in the absorber to
unit contains at least 50% of the mercury initially present in 55 remove acid gases. With the regeneration of the lean amine
the gas feed (to the dehydrator). The solution contains at least for use in the absorber unit, mercury will gradually build up
75% of the mercury originally present in a second embodi over time in the system, along with other known Solid and
ment; and at least 90% in the third embodiment. ionic materials which accumulate in acid gas scrubbing solu
Optional Additives: tions and are commonly known as “heat stable salts' or HSS.
In one embodiment in addition to the complexing agent, at 60 In one embodiment, the regenerator overhead gas under
least one of an anti-foam and/or a demulsifier is added to the goes further processing in a Sulfur unit, e.g., to make Sulfuric
glycol Solution. As used herein, the term anti-foam includes acid from the acid gas H2S, or combusted for Subsequent
both anti-foam and defoamer materials, for preventing foam venting. Removal of the mercury in the amine absorber gives
from happening and/or reducing the extent of foaming. Addi an acid gas product with reduced mercury. This enables the
tionally, Some anti-foam material may have both functions, 65 production of sulfuric acid, or elemental sulfur, with reduced
e.g., reducing/mitigating foaming under certain conditions, mercury. In another embodiment, the regenerator overhead
and preventing foam from happening under other operating gas is first routed through a condenser set up for the removal
US 8,790,427 B2
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of water by condensation, then Subsequently sent to a mer acids such as HS and CO as overhead stream 34, wherein
cury removal unit (MRU) for the removal of mercury using the stripping steam is generated from the amine Solution in a
processes and equipment known in the art. reboiler 40 that takes its feed 32 from the regenerator tower
In one embodiment, a portion of the mercury-containing below the Steam stripping section.
amine adsorbent can be continuously or intermittently purged 5 In one embodiment, at least a portion of non-volatile mer
from the amine unit/removed from the scrubber, and replaced cury in the rich amine is also released from the amine Solution
with fresh amine. In yet another embodiment, other remedia in stripper 30 and/or reboiler 40 as volatile mercury that
tion actions include: a) the contaminated amine solution is leaves the process with overhead stream 34. In one embodi
purged (bled) on a continuous or intermittent basis and ment (not shown), the overhead stream is directed to a mer
replaced with fresh amine; b) the entire inventory of amine is 10 cury removal unit, e.g., a mercury removal adsorbent bed, for
replaced; and c) reclaiming the Solution. Reclaiming the Solu the mercury to be removed by adsorption.
tion to remove non-volatile mercury as removed from the Condensing water from the effluent water/acid gas stream
from the top of the regenerator helps minimize water usage.
natural gas feed to the amine unit can be done by a variety of The steam stripping is not complete so residual HS and CO.
processes and systems known in the art for the removal of heat remain in the lean amine solution, along with some non
stable salts, including but not limited to filtration, centrifuga 15
volatile mercury. Many of the acids that are not removed by
tion, precipitation, reduction to elemental mercury followed steam stripping are called Heat Stable Salts (HSS) or, unless
stripping, distillation, adsorption, ion exchange, electrodialy otherwise neutralized, Heat Stable Amine Salts (HSAS).
sis, or transfer to a hydrocarbon steam and separation, and Examples include but are not limited to formate, acetate,
combinations thereof. glycolate, propionate, oxalate, chloride, Sulfate, thiosulfate,
Recovery/Regeneration of Glycol Solution: and thiocyanate. In one embodiment, a portion of the HSS is
In one embodiment after the concurrent removal of water removed with at least a portion of the non-volatile mercury in
and mercury in the dehydrator, the rich glycol bearing non the bleed stream 41.
Volatile mercury and water stripped from the natural gas, is
put through a specialized boiler designed to vaporize only the EXAMPLES
water out of the solution. While water has a boiling point of 25
212° F., glycol does not boil until 400°F. This boiling point The following illustrative examples are intended to be non
differential makes it relatively easy to remove water from the limiting.
rich glycol, allowing it be reused in the dehydration process. Example 1
Depending on the temperature of the distillation, e.g., below
than 150°C., in one embodiment, mercury remains in the rich 30
The example was to investigate the retention of mercury in
glycol bottom, with watergoing overhead in the glycol regen absorbents, a lean amine from a refinery acid gas scrubber
erator. In another embodiment with the distillation at a lower was sampled and analyzed, and found to contain 250 ppb
temperature, e.g., above 150° C. mercury can be removed mercury. The lean amine was stripped with 300 cc/min nitro
from the bottom stream by techniques known in the art Such gen at room temperature for one hour. It was found that the
as ion-exchange or Sub-atmospheric pressure distillation. 35 mercury content of the lean amine was not changed. The lean
In another embodiment, residual mercury in the rich glycol amine was centrifuged at 1500 RPM for 10 minutes. The
can be removed by other processes known in the art, including mercury content of the Supernatant was analyzed and found to
but are not limited to filtration, centrifugation, precipitation, be unchanged.
reduction to elemental mercury followed stripping, distilla In the next step, the lean amine containing mercury was
tion, adsorption, ion exchange, or transfer to a hydrocarbon 40 filtered through a 0.2L filter. The mercury content of the
steam and separation, and combinations. Alternatively a por Supernatant was analyzed and found to be unchanged. It is
tion of the mercury-containing rich glycol stream can be concluded that the mercury which is present in the lean amine
purged from the system. In one embodiment, the non-volatile is a non-volatile mercury species, and is not present in the
mercury complexes can be removed from the regenerated/ form of large particles. Since this mercury species was found
recycled rich glycol with the use of a mercury absorber con 45 in the leanamine from the commercial unit, it was not decom
taining a bed of sulphided absorbent as disclosed in U.S. Pat. posed to solids or volatile elemental mercury by the tempera
No. 7,435,338, the relevant disclosure is incorporated herein tures, pressures and residence times in the amine regeneration
process.
by reference.
Reference will be mad to FIG. 2 of a diagram schematically Example 2
illustrating an embodiment of a system and process for 50
removing mercury from natural gas/flue gas (sourgas feed) in In this example, a sample of volatile Hg" was dissolved in
an amine unit. white oil. This material is used to study the conversion of
In the FIG. 2, (lean) amine scrubbing solution 5 is used to volatile mercury (Hg) into non-volatile mercury (HgS and
remove acid gases from a sour gas feed 1 in absorber 10 other forms). First, five grams of elemental mercury Hg was
generating a rich amine stream. As shown mercury complex 55 placed in an impinger at 100° C. and 0.625 SCF/min of
ing agent 6 is added to the lean scrubbing solution feed to the nitrogen gas was passed over through the impinger to forman
scrubber. Although not shown, mercury complexing agent Hg-Saturated nitrogen gas stream. This gas stream was then
can also be provided as any of a separate feed stream, part of bubbled through 3123 pounds of SuperlaR) white oil held at
the make-up water stream to the scrubber, or combinations 60-70° C. in an agitated vessel. The operation continued for
thereof. In one embodiment (not shown), different complex 60 55 hours until the mercury level in the white oil reached 500
ing agents can be added to the amine unit as different feed ppbw by a LumexTM analyzer. The simulated material was
streams. The mercury complexing agent(s) can be added con drummed and stored.
tinuously or intermittently. Sweetened gas stream 4 with
reduced concentration of acid gas and mercury is removed Example 3
from the scrubber for subsequent treatment with a glycol 65
dehydrator (not shown). The rich amine solution 31 under In this example, volatile mercury was shown to be
goes steam stripping in stripper 30 for the removal of weak absorbed by an aqueous solution of sodium polysulfide. Agas
US 8,790,427 B2
11 12
containing Volatile mercury was prepared by sparging nitro ride solution. This was used to sweep the evolved elemental
gen through the white oil of Example 2 and this gas was mercury to the downstream absorbers.
bubbled through a 10 wt % solution of sodium polysulfide at The glass reactor was connected to two absorbers in series,
room temperature. Mercury was transferred from the white each of which contained 200 ml of solution. The absorbers
oil to the polysulfide solution. The mercury content of the were equipped with a glass frit to produce small bubbles. The
stripped oil was reduced below the limit of detection, while bubbles contacted the absorbing solution for about one sec
>70% of the mercury initially in the oil was measured in the ond. The first absorber contained the test solution. The second
polysulfide solution. The extent of mercury capture in this contained 3% sodium polysulfide in water. The 3% sodium
bubbler experiment was not optimized, but the test showed 10
polysulfide solution was prepared by dilution of a 30% solu
the ability of complexing agents such as sodium polysulfide tion of sodium polysulfide. This second absorber was a scrub
to capture mercury from a gas stream in a non-volatile form ber to remove the last traces of mercury from the nitrogen to
that is soluble in the polysulfide solution. provide mercury mass closures. Analysis of the exit gas from
the second absorber by both Lumex and Jerome techniques
Examples 4-16 15 found no detectable mercury.
Samples of the liquids in the reactor and two absorbers and
To study the conversion of volatile mercury to non-volatile gas leaving the reactor and leaving the two absorbers were
mercury, 20 ml of the material from Example 2 was placed in drawn at periodic intervals over a ninety-minute period and
a series of Vials. The mercury analysis of the samples aver analyzed for mercury by Lumex. Mercury balances over 57
aged 359 ppbw, indicating some loss of mercury over the runs average 98.6%. The reaction of the mercury chloride in
years that the sample was stored. the three neck flask is rapid, and the elemental mercury was
A number of complexing agents were added to the vials stripped rapidly as well. After a typical ninety-minute period
and the initial mercury content was measured by LumexTM the conversion and displacement of mercury in the reactor
mercury analyzer (detection limit of -50 ppbw). A nylon averaged 94%.
stopper equipped with a small vent hole was place on top of 25 The efficiency of the test solutions was calculated by com
each vial. The vials were then heated in an oil bath overnight. paring the amount of mercury taken up in the first reactor
In the morning each vial is shaken. Then each vial was purged absorber to the amount taken up in both absorbers. If no
with N for one hour at 90° C. with a gas flow to produce a mercury was taken up in the first reactor with the test solution,
steady bubbling (about 300 ml/hr). The final mercury content the efficiency was Zero percent. If all the mercury was taken
in each vial was then measured. The comparison of the initial 30
up in the first reactor, the efficiency was 100%. At the end of
and final mercury contents were used to judge the conversion the experiments no evidence of precipitated HgS was
of volatile elemental mercury into a non-volatile form (% Hg observed in the absorbers. The solutions were clear.
fixed). Results are summarized in Table 1. These complexing
agents convert Volatile mercury to a non-volatile form that Examples 18-21
would be removed from the treated gas when incorporated in 35
an amine Scrubber.
The experiments were to evaluate the Hguptake in various
TABLE 1.
Solutions without the complexing agent according to the pro
cedures in Example 17. The results are shown in Table 2. A
Final 56% MEG solution was prepared by mixing 56 wt.% mono
Amount Temp. Time, Hg, 96 Hg 40 ethylene glycol (MEG) in DI water. MEG solutions are typi
Example Agent added o C. Hrs ppbw Fixed cally used to prevent the formation of hydrates in gas pipe
4 None O 90 24 O O
lines that also contain water. A 45% MDEA solution was
5 Di-Phenyl disulfide 0.1 g 90 24 2O 6 prepared by mixing 45 percent Methyl diethanolamine in DI
6 Di-n-propyl disulfide 0.1 ml 90 24 O O water. MDEA solutions are typically used in acid gas scrub
7 Di-tert-nonyl 0.1 ml 90 24 2 1 45 bers which remove hydrogen sulfide, carbon dioxide and
polysulfide
8 1-Hexyl mercaptain 0.1 ml 90 24 243 68 other acidic gases from natural gas. 100% TEG was pure
9 Thiophene 0.1 ml 90 24 O O triethylene glycol. TEG is used to dehydrate gases.
10 None O 90 72 O O
11 Di-Phenyl disulfide 0.1 g 90 72 48 13 TABLE 2
12 Di-n-propyl disulfide 0.1 ml 90 72 O O 50
13 Di-tert-nonyl 0.1 ml 90 72 3 1 Example Solvent Efficiency 9%
polysulfide
14 1-Hexyl mercaptain 0.1 ml 90 72 240 67 18 DIWater O
15 Thiophene 0.1 ml 90 72 23 7 19 56% MEG O
16 1-Hexyl mercaptain 0.1 ml 2O 24 10 3 2O 45%. MIDEA O
55 21 100% TEG O