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US006063346A

Ulllted States Patent [19] [11] Patent Number: 6,063,346


Luna [45] Date of Patent: Ma 16 9 2000

[54] PROCESS FOR SCAVENGING HYDROGEN 5,424,051 6/1995 Nagji et al. .


SULFIDE AND MERCAPTAN 5,478,541 12/1995 Samuels et al. .
CONTAMINANTS FROM A FLUID 5,554,349 9/1996 Rivers et al. ......................... .. 423/228
. ~~ 5,744,024
5,698,171 12/1997
4/1998 Sullivan,
Trau?er etIIIal.et al. ................ .. 208/236
[75] Inventor‘ German A‘ Luna’ Punto F110’ 5,750,083 5/1998 Mimura et al. ....................... .. 423/228
Venezuela
_ OTHER PUBLICATIONS
[73] Ass1gnee: Intevep, S. A., Caracas, Venezuela
Webster’s NeW World Dictionary, Third College Edition, p.
[21] Appl. No.: 09/092,379 520, 1988
[22] Filed: Jun. 5, 1998 Primary Examiner—Steven P. Gri?in
7 _ Assistant Examiner—Elin Warn
"""""""""" Attorney, Agent, or Firm—Bachman & LaPointe, P.C.

423/245.1; 208/208 R [57] ABSTRACT


[58] Field of Search ............................. .. 423/220, 244.01, .
4230451 5731 226 228 208/208 R A process for scavenging hydrogen sul?de and mercap'tan
’ ’ ’ ’ 236 240’ contaminants from a ?uid, including the steps of: providing
’ a ?uid containing hydrogen sul?de and mercaptan contami
[56] References Cited nants; mixing the ?uid With a benign contaminant scavenger
so as to provide a ?uid mixture; and subjecting the ?uid
U.S. PATENT DOCUMENTS mixture to scavenging conditions so as to provide a ?uid
4 450 777 5/1984 W01 frum et a1 product containing benign contaminant transformants.
4,569,766 2/1986 K001 et al. .
5,128,049 7/1992 Gatlin .................................... .. 210/752 15 Claims, N0 Drawings
6,063,346
1 2
PROCESS FOR SCAVENGING HYDROGEN thereof, preferably tWo different components, and most
SULFIDE AND MERCAPTAN preferably a combination of a triaZine and an alkyl-carboxyl
CONTAMINANTS FROM A FLUID aZo compound.

BACKGROUND OF THE INVENTION DETAILED DESCRIPTION


The invention relates to a process for removal of hydro The invention relates to a process for scavenging hydro
gen sul?de and mercaptan contaminants from a ?uid, espe gen sul?de and mercaptan (thiol) contaminants from a ?uid.
cially from hydrocarbons such as re?nery fuel gas, LPG, The process of the present invention ?nds applicability for
cracked gasoline, straight run gasoline, natural gasoline, and use in treating a large number of ?uids including
10
heavier hydrocarbon distillates including kerosene, fuel oil hydrocarbons, Water, combinations of liquid and/or gaseous
and the like. phases, and the like. Particularly useful ?uids to be treated
Sulfur contaminants in the form of hydrogen sul?de and With the process of the present invention include hydrocar
mercaptan are undesirable for a large number of reasons. For bons such as re?nery fuel gas, LPG, light catalytically
example, hydrogen sul?de can be haZardous to persons cracked gasoline (LCCG), straight run gasoline, natural
15
exposed thereto, and mercaptan is objectionable due to a gasoline and heavier hydrocarbon distillates including
strong odor. Furthermore, these components can be objec kerosene, fuel oil and the like. The ?uid or feedstock in
tionable due to their chemical reaction With other hydrocar accordance With the present invention is preferably charac
bons or fuel system components. teriZed by undesirable amounts of sulfur contaminant, espe
There have been many attempts to provide processes for
cially hydrogen sul?de and mercaptan.
the removal of mercaptan contaminants. Early processes In accordance With the present invention, it has been
included treatment of the hydrocarbon fractions With found that such sulfur contaminants can be neutraliZed
caustic, clays, and hydrotreating. One such process is the and/or removed from a ?uid or feedstock through contact of
UOP Merox process, Which Was announced in 1959 (Oil and the ?uid containing the contaminants With a benign con
Gas Journal, Oct. 26, 1959). This process used a catalyst 25
taminant scavenger Which, When contacted With the ?uid,
Which Was soluble in caustic, or alternatively held on a serves to substantially transform the sulfur contaminants
support, to oxidiZe mercaptans to disul?des in the presence into benign products such as disul?des and polysul?des,
of oxygen and caustic. A main disadvantage of caustic Which are referred to herein as benign contaminant
treatment is that disposal of spent caustic is undesirable for transformants, thereby completely avoiding the need for
environmental reasons. additional treatment and the like and avoiding environmen
tally undesirable treatment compositions such as caustic,
Other chemical processes for the treatment of hydrocar
Which is not benign.
bon feeds containing sulfur compounds and acidic compo
nents have involved purely chemical reactions such as In accordance With the process of the present invention,
scrubbing With mono or diethanolamine or counter current and as used herein, a benign contaminant scavenger is a
extraction using a hot potassium carbonate solution. Amine 35 composition Which serves to cause and/or assist in transfor
systems are, unfortunately, high in operation cost and further mation of hydrogen sul?de and mercaptan Without creating
characteriZed by corrosive nature of the absorbing liquids or itself being a substance in the ?nal product stream Which
used, and the inability to suf?ciently remove mercaptan. is undesirable. Examples of suitable scavengers include
compounds selected from the group consisting of triaZines,
It is therefore the primary object of the present invention
to provide a process for scavenging hydrogen sul?de and
maleimides, formaldehydes, amines, carboxamides, alkyl
mercaptan contaminants from a ?uid Which avoids the need
carboxyl-aZo compounds, cumine-peroxide compounds and
mixtures thereof. Particularly suitable as a contaminant
for caustic treatment.
scavenger in accordance With the present invention is a
It is a further object of the present invention to provide a combined dosage of a hydrogen sul?de scavenger compo
process for scavenging sulfur contaminants from a ?uid nent and a mercaptan scavenger component in different
45
Which effectively scavenges both hydrogen sul?de and mer points of application. Particularly suitable hydrogen sul?de
captan contaminants. scavenger components include each of the above, most
Other objects and advantages of the present invention Will preferably triaZines. Suitable mercaptan scavenger compo
appear hereinbeloW. nents include maleimides, formaldehydes, amines,
SUMMARY OF THE INVENTION
carboxamides, alkyl-carboxyl-aZo compounds, cumine
peroxide compounds and mixtures thereof, preferably an
In accordance With the present invention, the foregoing alkyl-carboxyl-aZo compound or a cumine-peroxide com
objects and advantages are readily attained. pound. A particularly effective contaminant scavenger
According to the invention, a process for scavenging according to the invention is a combination of triaZine and
hydrogen sul?de and mercaptan contaminant from a ?uid 55 alkyl-carboxyl-aZo compound.
such as a hydrocarbon feedstock is provided, Which process As set forth above, the ?uid to be treated in accordance
comprises the steps of: providing a ?uid containing hydro With the present invention may be selected from a Wide
gen sul?de and mercaptan contaminants; mixing said ?uid group of materials, the removal of sulfur contaminants from
With a benign contaminant scavenger so as to provide a ?uid Which is desirable, but it is particularly advantageous to use
mixture; and subjecting said ?uid mixture to scavenging the process of the present invention to treat hydrocarbons.
conditions so as to provide a ?uid product containing benign The ?uid or feed may typically contain contaminant includ
contaminant transformants. ing hydrogen sul?de in an amount of betWeen about 5 ppm
The contaminant scavenger of the present invention is (Wt) and about 200 ppm (Wt), and may contain mercaptan
preferably at least one compound or component selected contaminant in an amount betWeen about 15 ppm (Wt) and
from group consisting of triaZines, maleimides, 65 about 500 ppm (Wt).
formaldehydes, amines, carboxamides, alkyl-carboxyl-aZo Both the hydrogen sul?de scavenger component and the
compounds, cumine-peroxide compounds and mixtures mercaptan scavenger component in accordance With the
6,063,346
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process of the present invention are preferably contacted ing and mercaptan scavenging components and passing this
With the ?uid or feed to be treated, and mixed so as to insure mixture through either the same or a different mixer so as to
substantially homogeneous dispersion of each scavenger provide the ?nally treated ?uid having scavenged levels of
component through the ?uid. In this regard, the contact of hydrogen sul?de and mercaptan. Most preferably, the ?uid
?uid With scavenger may be carried out by mixing the is treated ?rst With hydrogen sul?de scavenger component
scavenger With the ?uid, and passing the resulting mixture and then With mercaptan scavenger component.
through any suitable mixing apparatus such as, for example,
static mixers, dynamic mixers, pumps, heat exchangers, Particularly suitable types of feed or ?uid to be treated in
pipelines, quill injectors, spray noZZle injectors, and com accordance With the present invention include feeds con
binations thereof. 10 taining mercaptan contaminants in the form of RSH,
Contaminant scavenger in accordance With the present Wherein R is a hydrocarbon radical having betWeen about 1
invention is preferably mixed With the feed in a ratio by and about 10 carbon atoms, S is sulfur and H is hydrogen.
Weight of total scavenger to contaminant in the feed of Of course, other types of mercaptans are scavenged in
betWeen about 1:1 and about 10:1, more preferably betWeen accordance With the process of the present invention as Well.
about 1:1 and about 3:1. Further, in accordance With the 15
preferred embodiment of the present invention Wherein the It has also been found that particularly desirable results
scavenger includes a hydrogen sul?de scavenger component can be obtained using the process of the present invention to
such as triaZine and a mercaptan scavenger component such treat a light catalytic cracking gasoline (LCCG) feed con
as an alkyl-carboxyl-aZo compound, the scavenger is pref taining betWeen about 5 and about 200 ppm hydrogen
erably mixed With ?uid or feedstock so as to provide a ratio 20
sul?de and containing betWeen about 15 and about 500 ppm
of triaZine to hydrogen sul?de of betWeen about 1:1 and mercaptan, most preferably by treating the LCCG feed ?rst
about 6:1, more preferably betWeen about 2:1 and about 5 :1, With a hydrogen sul?de scavenging component and then
and to provide a ratio of alkyl-carboxyl-aZo compound to
With a mercaptan scavenging component in accordance With
mercaptan by Weight of betWeen about 1:1 and about 2.5 :1.
25 the present invention, so as to substantially transform the
It has been found that by contacting the scavenger of the hydrogen sul?de contaminant into a benign polysul?de
present invention With the ?uid or feedstock to be treated,
product, and to transform the mercaptan contaminant into a
the contaminant as Well as the scavenger components react
benign disul?de product so as to provide a substantially
or interact so as to provide ?nal products Which are benign
or acceptable from environmental, safety and process stand
hydrogen sul?de and mercaptan free gasoline.
30
points. The hydrogen sul?de and mercaptan contaminants The folloWing examples illustrate the bene?cial results
are converted to disul?des and/or polysul?des in the ?nal obtained in accordance With the process of the present
products of the process Which are not haZardous or harmful
invention.
to process equipment and Which can be more easily disposed
of.
35
As set forth above, it is preferable that the scavenger of EXAMPLE 1
the present invention be provided having a hydrogen sul?de
scavenging component and a mercaptan scavenging This example demonstrates the scavenger ability of a
component, and that the feed be treated sequentially With benign hydrogen sul?de scavenger. The ?uid used Was a
these components, most preferably sequentially ?rst With the 40 LCCG having an HZS content of 30 ppm (Wt) and a RSH
hydrogen sul?de scavenging component and second With the content of 65 ppm (Wt). The LCCG Was treated using
mercaptan scavenging component. This is due to the fact triaZine as a hydrogen sul?de scavenger at a ratio by Weight
that it has been found, in accordance With the present of triaZine to hydrogen sul?de of 5:1, 4:1, 2:1, 1:1, at
invention, that a smaller amount of each component of the ambient temperature With no additional mixing. Table 1
scavenger can be utiliZed to provide excellent results in 45 beloW sets forth the results achieved in terms of % HZS
scavenging both hydrogen sul?de and mercaptan, as Will be
removal at each ratio.
set forth beloW. This advantageously provides for excellent
reduction in levels of contaminant, While also advanta
TABLE 1
geously reducing the amount of scavenger needed to treat a
particular batch or stream of ?uid or feedstock. 50 Ratio % H25 removal
Although excellent results can be obtained using the
1:1 8%
contaminant scavenger of the present invention at a Wide 2:1 29%
variety of conditions, it has been found that best results are 4:1 76%
obtained When scavenging is carried out at a temperature 5:1 100%
betWeen about 25° C. and about 180° C., more preferably 55
betWeen about 40° C. and about 130° C. and most preferably
betWeen about 100° C. and about 130° C. As shoWn signi?cant HZS removal is achieved at 5: 1 ratio.
It has also been determined in accordance With the present
invention that When the scavenger component of the present
EXAMPLE 2
invention is to include both a hydrogen sul?de scavenging 60
component and a mercaptan scavenging component, that the
contacting step may suitably be carried out by mixing one This example further demonstrates the scavenger ability
component of the hydrogen sul?de scavenging and mercap of a hydrogen sul?de scavenger treating the same LCCG
tan scavenging components With the ?uid and passing the feed as treated in Example 1, but at different temperatures,
mixture through a ?rst mixer to provide a partially treated 65 and still at the ratios of 5:1, 4:1, 2:1, 1:1. The results
?uid, and subsequently mixing the partially treated ?uid obtained for various temperatures at these ratios are set forth
With the other component of the hydrogen sul?de scaveng beloW in Tables 2—5.
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EXAMPLE 4
TABLE 2
Ratio 1:1 This example further demonstrates the scavenger ability
Temperature % H25 removal 5 of the same benign mercaptan scavenger to treat the same
LCCG feed as treated in Example 3, but at different
27° C. 8%
38° C. 9.5% temperatures, and still at the ratios of 10:1, 5:1, 2.5:1 and
120° C. 33% 1.25:1. The results obtained for various temperatures at
these ratios are set forth beloW in Tables 7—10.
10

TABLE 3 TABLE 7
Ratio 1.25:1
Ratio 2:1
Temperature % RSH removal
Temperature % H25 removal 15
27° C. 58.4%
27° C. 29%
38° C. 64.9%
38° C. 37%
50° C. 65.6%
120° C. 49%

20

TABLE 4 TABLE 8
Ratio 2.5:1
Ratio 4:1
Temperature % RSH removal
Temperature % H25 removal 25
27° C. 64.4%
27° C. 76%
38° C. 68.5%
38° C. 78%
50° C. 70.4%
120° C. 94%

30

TABLE 5 TABLE 9
Ratio 5:1
Ratio 5:1
Temperature % RSH removal
Temperature % H25 removal 35
27° C. 69.8%
27° C. 100%
38° C. N/A
380 C. 100%
50° C. 74.6%
1200 C. 100%

As shown above, carrying out the contacting step at 4°


TABLE 10
increased temperature provided better results using a loWer
ratio of H25 scavenger to hydrogen sul?de. Ratio 10:1

EXAMPLE 3 Temperature % RSH removal


45
This example demonstrates the scavenger ability of a 27° C. 71.4%
38° C. 75.3%
benign mercaptan scavenger. The ?uid used Was a LCCG 50° C. 78.9%
having a HZS content of 30 ppm (Wt) and a RSH content of
65 ppm (Wt). The LCCG Was treated using alkyl-carboxyl
aZo compound, speci?cally using bis-(isopropylacetate) 50
am, as a mercaptan scavenger at a ratio by Weight of As shoWn above, carrying out the contacting step at
scavenger to mercaptan of 10:1, 5:1, 2.5:1, 1.25:1, at ambi increased temperature provided better results using a loWer
ent temperature With no additional mixing. Table 6 beloW
ratio of mercaptan scavenger to mercaptan.
sets forth the results achieved in terms of % RSH removal
at each ratio. 55

EXAMPLE 5
TABLE 6
Ratio % RSH removal
To further illustrate the advantageous use of a scavenger
1.25:1 58.4% 60
2.5:1 64.4% containing both hydrogen sul?de and mercaptan scavenger
5:1 69.8% components, the same LCCG feed Was treated, at ambient
10:1 71.4% conditions using: only HZS scavenger (triaZine), then only
mercaptan scavenger (bis-(isopropylacetate)-aZo
As shoWn, alkyl-carboxyl-aZo compound provides reduc- 65 compound), and then both scavengers sequentially using
tion in RSH levels With gradual increase in removal at higher HZS scavenger ?rst followed by mercaptan scavenger.
ratios. Tables 11—12 beloW set forth the results obtained.
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What is claimed is:
TABLE 11 1. A process for scavenging hydrogen sul?de and mer
Ratio % H25 Removal % RSH Removal
captan contaminants from a ?uid, comprising the steps of:

2:1 H25 29.0% 0%


25:1 RSH 75.5% 64.4% providing a ?uid containing hydrogen sul?de and mer
2:1 H25 + 2.5:1 RSH 85.0% 64.4% captan contaminants;
mixing said ?uid With a benign contaminant scavenger
comprising a hydrogen sul?de scavenger component
TABLE 12 10
and a mercaptan scavenger component Wherein said
Ratio % H25 Removal % RSH Removal hydrogen sul?de scavenger component and said mer
captan scavenger component are different from each
5:1 H25 100.0% 0%
25:1 RSH 75.5% 64.4%
other and are selected from the group consisting of
5:1 H25 + 2.5:1 RSH 100.0% 92.3% triaZines, maleimides, formaldehydes, amines,
carboxamides, alkylcarboxyl-aZo compounds, and
cumine-peroxide compounds so as to provide a ?uid
As shown, at each of the combinations of ratios provided,
better results Were obtained using a sequential application of mixture; and
hydrogen sul?de scavenger followed by mercaptan 20
subjecting said ?uid mixture to scavenging temperature
scavenger, Which provides excellent removal of both H25 conditions so as to provide a ?uid product containing
and mercaptan (RSH). benign contaminant transformants Wherein said prod
uct is substantially free of said hydrogen sul?de and
EXAMPLE 6
mercaptan contaminants.
This example illustrates the advantageous use of a scav 25 2. Aprocess according to claim 1 Wherein said mixing and
enger containing both hydrogen sul?de (triaZine) and mer subjecting steps are carried out sequentially ?rst With one of
captan scavenger components (bis-(isopropylacetate)-aZo said hydrogen sul?de scavenger component and said mer
compound). The same LCCG from Example 5 Was treated,
captan scavenger component so as to provide a partially
at different temperatures, using: only HZS scavenger, then
treated ?uid, and then With the other of said hydrogen sul?de
only mercaptan scavenger, and then both scavengers sequen 30
tially. Tables 13—14 beloW set forth the results obtained. scavenger component and said mercaptan scavenger com
ponent so as to provide said ?uid product.
TABLE 13 3. A process according to claim 2, Wherein said one
component is said hydrogen sul?de scavenger component
Temperature 38° C. 35 and Wherein said other component is said mercaptan scav
Ratio % H25 Removal % RSH Removal enger component.
2:1 H25 37.0% 0% 4. Aprocess according to claim 2, Wherein said hydrogen
2.5:1 RSH 85.8% 68.5% sul?de scavenger component comprises a compound
2:1 H25 + 2.5:1 RSH 100.0% 76.0% selected from the group consisting of triaZines, maleimides,
40
formaldehydes, amines, carboxamides, alkyl-carboxyl-aZo
compounds, cumine-peroxide compounds and mixtures
TABLE 14 thereof, and Wherein said mercaptan scavenger component
Temperature 50° C.
comprises a compound different from said hydrogen sul?de
45 scavenger component and selected from the group consist
Ratio % H25 Removal % RSH Removal ing of maleimides, formaldehydes, amines, carboxamides,
5:1 H25 100.0% 0% alkyl-carboxyl-aZo compounds, cumine-peroxide com
2.5:1 RSH 100.0% 70.4% pounds and mixtures thereof.
5:1 H25 + 2.5:1 RSH 100.0% 83.0%
50 5. Aprocess according to claim 2, Wherein said hydrogen
sul?de scavenger component is present at a ratio by Weight
As in Example 5, the example also shoWs that the of scavenger to hydrogen sul?de contaminant of betWeen
sequential treatment in accordance With the process of the about 1:1 and about 6:1, and Wherein said mercaptan scav
present invention using ?rst hydrogen sul?de scavenger enger component is present at a ratio by Weight of scavenger
folloWed by mercaptan scavenger provides for excellent 55 to mercaptan of betWeen about 1:1 and about 2.5:1.
results as compared to the use of each scavenger 6. Aprocess according to claim 1, Wherein the subjecting
individually, and reduced ratios of each scavenger can be step is carried out at a temperature betWeen about 20° C. and
used to provide for excellent results, particularly at high about 180° C.
temperatures.
7. Aprocess according to claim 1, Wherein the subjecting
This invention may be embodied in other forms or carried 60
step is carried out at a temperature betWeen about 40° C. and
out in other Ways Without departing from the spirit or
about 130° C.
essential characteristics thereof. The present embodiment is
therefore to be considered as in all respects illustrative and 8. Aprocess according to claim 1, Wherein the subjecting
not restrictive, the scope of the invention being indicated by step is carried out at a temperature betWeen about 100° C.
the appended claims, and all changes Which come Within the 65 and about 130° C.
meaning and range of equivalency are intended to be 9. A process according to claim 1, Wherein the ?uid
embraced therein. comprises a hydrocarbon.
6,063,346
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10. A process according to claim 1, wherein the ?uid is carbon radical having betWeen about 1 and about 10 carbon
Water. atoms, S is sulfur and H is hydrogen.
11. A process according to claim 1, Wherein the ?uid is 14. A process according to claim 1, Wherein the ?uid
selected from the group consisting of liquids, gases, and contains hydrogen sul?de in an amount betWeen about 5
miXtures thereof.
ppm and about 200 ppm, and mercaptan in an amount
12. A process according to claim 1, Wherein the ?uid is
betWeen about 15 ppm and about 500 ppm.
selected from the group consisting of gasoline, LCG, LCCG
or miXtures thereof, and Wherein the ?uid product comprises 15. A process according to claim 1, Wherein said benign
a substantially hydrogen sul?de and mercaptan free gaso contaminant transformants are selected from the group con
line. 10 sisting of disul?des, polysul?des and mixtures thereof.
13. A process according to claim 1, Wherein the ?uid
contains mercaptan in the form RSH Wherein R is a hydro * * * * *