US008O34246 B2

(12) United States Patent (10) Patent No.: US 8,034,246 B2

Gustafsson et al. (45) Date of Patent: Oct. 11, 2011

(54) WASTEWATER MERCURY REMOVAL 3,749,761 A 7, 1973 Dean et al.

PROCESS 4,147,626 A 4/1979 Findlay et al.
4.252,643 A * 2/1981 Knettig et al. ................ 210.662
4,305,827 A * 12/1981 Sasaki ............ ... 210,688
(75) Inventors: Meredith B. Gustafsson, Beaumont, TX 4.374,029 A * 2/1983 Jaisinghani ................... 210,671
(US); Bal K. Kaul, Fairfax, VA (US); 4,814,091 A 3/1989 Napier et al.
Brian S. Fox, Mullica Hill, NJ (US); 4.950.408 A 8, 1990 Duisters et al.
David A. Masciola, Alexandria, VA 5,545,330 A * 8/1996 Ehrlich ......................... 210,703
5,599,515 A 2f1997 Misra et al.
(US); Bowornsak Wanichkul, Bangkok 5,667,694 A 9/1997 Cody et al.
(TH) 5,871,648. A 2/1999 Allen et al.
5.904.853. A 5/1999 Allen et al.
(73) Assignee: ExxonMobil Research & Engineering 6,071.43 A * 6, 2000 et a . . . . . . . . . . . . . . . . . . . . . . 210/651
Company, Annandale, NJ (US)
(Continued)
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS
U.S.C. 154(b) by 963 days. EP O765842 A1 4, 1997
(21) Appl. No.: 11/798,694 (Continued)
(22) Filed: May 16, 2007 OTHER PUBLICATIONS
O O Darrell L. Gallup et al., “Removal of Mercury and Arsenic from
(65) Prior Publication Data Produced Water”, (2006).
US 2008/028347OA1 Nov. 20, 2008
(Continued)
51) Int. Cl.
(51) OF L/24 (2006.01) Primary Examiner — Thomas M Lithgow
CO2F I/52 (2006.01) (74) Attorney, Agent, or Firm — Glenn T. Barrett; Malcolm
CO2F L/56 (2006.01) D. Keen
CO2F L/62 (2006.01)
CO2F 9/02 (2006.01) (57) ABSTRACT
CO2F 9/04 (2006.01) A method for removing ionic, organic and elemental mercury
CO2F 9/08 (2006.01) from aqueous streams such as wastewater streams from
(52) U.S. Cl. ........ 210/703: 210/665; 210/666; 210/669; hydrocarbon processing. The method comprises four primary
210/685; 210/705; 210/729; 210/806; 210/807; removal steps. First, a mercury precipitant is added to the
210/202; 210/266 stream to convert dissolved ionic species of mercury water
(58) Field of Classification Search .................. 210/665, insoluble form. The majority of these precipitated solids, as
210/666,669,685,703,705, 729, 806, 807, well as other forms of particulate mercury, are Subsequently
210/202, 266 removed by means of gas flotation. Following the flotation
See application file for complete search history. step, additional particulate and precipitated ionic mercury
removal is accomplished with media filtration and finally,
(56) References Cited activated carbon acts to remove the remaining dissolved ionic
mercury species as well as elemental and organic forms of
U.S. PATENT DOCUMENTS mercury.
3,736,253 A 5/1973 De Angelis et al.
3,740,331 A 6, 1973 Anderson et al. 20 Claims, 1 Drawing Sheet
13
11 N
 US 8,034.246 B2
Page 2

U.S. PATENT DOCUMENTS OTHER PUBLICATIONS

: 3. A ck 358 SAG et al. ......... 21Of705 EPA Capsule Report, "Aqueous Mercury Treatment”. EPA/625/R-
6,537.443 B1 3/2003 Frankiewicz et al. 97/004 (Jul 1997).
6,635,182 B1 10/2003 Coleman, Jr. International Seasrch Report, PCT/US2008/006066, mailed Sep. 10,
7,029.202 B2 4/2006 Zhuang 2008.
2002.0003112 A1 1/2002 Golden Written Opinion, PCT/US2008/006066, mailed Sep. 10, 2008.
2003/0082084 A1 5, 2003 Cort Singapore Appl. No. 200907584-7. Search Report from the IP Office
2004/OO55962 A1 3/2004 Golden of Singapore, dated Mar. 3, 2011, 5 pgs.
2004/0179984 A1 9/2004 Nagaraj et al. Singapore Appl. No. 200907584-7. Written Opinion from the IP
FOREIGN PATENT DOCUMENTS Office of Singapore, dated Mar. 3, 2011, 4pgs.
WO WO91073.54 5, 1991 * cited by examiner
U.S. Patent Oct. 11, 2011 US 8.034,246 B2

Fig. 1
 US 8,034,246 B2
1. 2
WASTEWATER MERCURY REMOVAL tate dissolved ionic mercury and remove it by means of gas or
PROCESS air flotation. A technique of this kind is described in U.S. Pat.
No. 6,635,182 (Coleman). Although this method is effective
FIELD OF THE INVENTION at removing the bulk of mercury found in wastewater (ionic
species as Hg"), it cannot remove all mercury species which
This invention relates to methods for removing mercury may be present, including insoluble particulate mercury com
from wastewater streams and, in particular, to methods for pounds, elemental mercury (HgCO)), present either as Such or
removing mercury from wastewater streams from petroleum dissolved in minor amounts in the water, and organic mer
refineries and other petroleum processing installations. cury, principally monomethyl and dimethyl mercury. Where
10 significant amounts of mercury or numerous different species
BACKGROUND OF THE INVENTION are present and effluent limits are low, existing technologies
are not likely to remove the amounts of mercury necessary to
Natural gas and crude oils produced in certain areas of the achieve environmental compliance.
world contain mercury in quantities Sufficient to render their Other proposals for treating aqueous streams to remove
processing problematical. For example, hydrocarbon con 15 mercury and other heavy metals are found in U.S. Pat. No.
densates derived from natural gas produced in certain regions 4,814,091 (Napier), U.S. Pat. No. 5,667,694 (Cody), U.S. Pat.
of southeast Asia may contain over 1000 parts per billion by No. 6,165,366 (Sarangapani) and U.S. Pat. No. 7,092,202
weight (ppbw) of mercury, while crude oils from certain (Zhuang). Prefiltration followed by pH adjustment and sul
regions of Argentina frequently contain well over 2000 ppbw fide precipitation followed by flocculation and posifiltration
of mercury. The produced waters from gas and oil wells with is used in the method of U.S. Pat. No. 4,814,091. The method
elevated levels of mercury may also contain high levels of described in U.S. Pat. No. 5,667,694 uses an organoclay
mercury precluding their discharge to the environment as the sorbent which can then be separated from the water, contain
direct result of contact between the water and the oil orgas in ing the removed metal. A treatment better adapted to continu
the subterranean production interval. Wastewater streams ous use is described in U.S. Pat. No. 6,165.366, which uses
associated with processing the gas and oil may also contain 25 sequential hypochlorite oxidation, filtration and removal of
mercury arising from contact between process water streams organics using activated carbon. In the method described in
and hydrocarbon streams. The contact may take place, for U.S. Pat. No. 7,029.202, alignin derivative is used initially to
example, by the use of water or aqueous treatment streams to form a complex compound with the mercury or other metal
remove other contaminants such as nitrogenous compounds. after which a coagulant is used to form a floc which is then
The mercury may be present in several forms including 30 separated as a sludge. These methods have, however, not
ionic, elemental, particulate and organic. Crude oils, for shown themselves to be sufficient to remove mercury in many
example, may contain elemental mercury but this may be wastewater stream to the levels needed for regulatory com
oxidized in various process units to produce water-soluble pliance.
salts (Hg". Hg") and complexes. Additionally, anaerobic
bacteria can convert Suspended mercury in particulate forms 35 SUMMARY OF THE INVENTION
to water-soluble organic forms so that transfer between the
two solvent species occurs readily. We have now devised a processing technique for removing
The presence of the mercury raises problems of two kinds. mercury from aqueous streams (e.g., wastewater, produced
First, the mercury may attack the metals in processing equip water, process streams) which is effective to remove this
ment by the formation of amalgams; this is a problem which 40 metal regardless of the form in which it is present, be it ionic,
is especially notable with items made of aluminum and alu elemental, particulate or organic, with the objective of achiev
minum alloys, such as the cold boxes in cryogenic plants such ing an effective removal of the mercury contaminant to levels
as the ethylene separators found in petrochemical units and in acceptable for discharge to the environment.
natural gas treatment installations. The presence of mercury The processing according to an embodiment of the inven
on the equipment may also dictate its treatment as hazardous 45 tion comprises four primary removal steps. First, a mercury
waste when removed from Service. Mercury poisoning may precipitant, which targets dissolved ionic species of mercury
also reduce the life of processing catalysts. and converts them to water-insoluble form is added to the
Second, mercury, as an elemental impurity that cannot be aqueous stream. The majority of these precipitated Solids, as
destroyed but only moved from one stream to another, will well as some particulate mercury and hydrocarbon contami
often enter process water streams. This may occur by direct 50 nants, are then Subsequently removed by means of flotation,
contact with the stream, for example, during washing or from usually operated as dissolved air, induced air, or induced gas
the use of process steam. Recent studies have shown that as flotation. Following the removal of the precipitated solids,
much as 20% of the mercury in the crude can enter a refinery additional particulate and precipitated ionic mercury removal
wastewater stream. In any event, increasingly stringent envi is accomplished by filtration, suitably with a media filter.
ronmental regulations make it necessary to remove the mer 55 Finally, activated carbon acts as a polishing step to remove the
cury from the water before it can be discharged to the envi remaining dissolved ionic mercury species as well as elemen
ronment. Recent environmental limits may place the tal and organic forms of mercury. This combination of pro
discharge target as low as 0.1 ppbw. The difficulty in dealing cessing steps is capable of achieving levels of mercury
with mercury-containing crudes and otherpetroleum streams removal from water that have not previously been thought
is exacerbated by the fact that increasingly, shortages of high 60 possible.
quality crudes have led to the use of Supplies of crude con The method for removing mercury in ionic and non-ionic
taining high levels of mercury. form from an aqueous stream in accordance with one aspect
Currently, few technologies are available for removing of the present invention includes adding a water-soluble mer
mercury from streams of wastewater and produced water. The cury precipitant to the aqueous stream to react with dissolved
main commercial technology available for treating mercury 65 mercury compounds present in the stream to form a water
in water consists of adding one of several commercially insoluble precipitate of a mercury compound. Non-ionic
available precipitants, usually Sulfided polymers, to precipi forms of mercury which may also be present in the aqueous
 US 8,034,246 B2
3 4
stream may include organic mercury compounds and/or process has been proven to be effective at treating streams
elemental mercury. The water-insoluble precipitate of the which contain levels of mercury up to 60,000 ng/l (nanograms
mercury compound is then separated from the aqueous per liter, equal to 60 ppb) through testing; however, it is
stream by means of flotation along with hydrocarbons which anticipated that treating streams having as high as ppm levels
may be present. The separated aqueous Solution is then of mercury is feasible.
passed through a filter to remove residual precipitated mer In accordance with the mercury removal process, the aque
cury compounds and form a filtrate of water with a reduced ous stream containing the mercury species is Subjected to an
level of mercury, The filtrate is then passed over activated initial precipitation step to convert Soluble mercury com
carbon to remove residual dissolved ionic mercury species as pounds in ionic form to an insoluble condition so that the
well as elemental and organic forms of mercury. 10 compounds may be Subsequently removed by physical
The mercury precipitate may comprise a compound which means. To this end, a mercury precipitant, that is, a compound
reacts with the dissolved mercury compounds present in the which will react with dissolved mercury cations, usually
stream to form water-insoluble sulfides of mercury. The mer Hg", is brought into contact with the aqueous stream in this
cury precipitant may suitably comprise an alkali metal Sul step of the process. Contact may be achieved by simply add
fide, an alkali metal polysulfide, an alkaline earth metal Sul 15 ing a solution of the precipitant to the aqueous stream and
fide, an alkaline earth metal polysulfide. Other mercury mixing to ensure adequate contact throughout the body of the
precipitants include thiazoles, alkali metal thiocarbamates, water. While the mixing of the mercury precipitant with the
alkali metal dithiocarbamates, alkali metal Xanthates and water stream may be accomplished by means Such as, for
alkali metal trithiocarbonates. A preferred class of water example, coagulant-type mix tanks, towers with contact
soluble mercury precipitants are the polymeric dithiocarbam trays, countercurrent contactors or other devices intended to
ates. break up the added precipitant solution and distribute it uni
The media filter may comprise a dual media filter, e.g. a formly throughout the mercury-containing water stream,
sand-anthracite. these will generally not be necessary since the reaction
between the precipitant and the dissolved mercury species
DRAWINGS 25 takes place quickly. Normally, it suffices to add a solution of
the precipitant to the aqueous flow stream at normal flow
FIG. 1 is a process Schematic for a mercury removal pro rates, ensuring, however, that good mixing is achieved in
cess in accordance with an embodiment of the present inven order to permit the reaction between the precipitant and the
tion. dissolved ionic mercury to take place. This may be achieved
30 in an area of high turbulence, Such as the Suction side of a
DETAILED DESCRIPTION pump. If, however, a Sump is present at the inlet of the flota
tion tank for mixing in coagulants or floculents, this can
The following preferred embodiments of the invention are conveniently be used as a location for injection of the precipi
described by way of illustration. All stated proportions and tant with good mixing assured prior to the flotation step.
percentages are by weight unless indicated to the contrary. 35 When coagulants or flocculants are added in conjunction with
As shown in the FIG. 1, the mercury-containing aqueous a mercury precipitant care must be taken to ensure compat
stream enters a treatment unit for processing according to the ibility. For example, if an anionic precipitant and cationic
present invention by way of line 10 where it meets an injected coagulant are used in conjunction, at least 30 seconds of
aqueous stream of water-soluble mercury precipitant entering mixing should be provided between injection points to avoid
from line 11. Upon mixing of the two streams, which typi 40 adverse interactions between the products. The mercury pre
cally takes place readily in the flow lines, a reaction occurs to cipitant is preferably used in the form of a solution so as to
precipitate dissolved ionic mercury out of solution. The permit easy and effective mixing with the aqueous stream.
stream then passes into a flotation tank 12 in which the pre One class of mercury precipitating agents comprises Sul
cipitated Solids are separated by flotation in the conventional fides which react with the dissolved mercury ions to form
manner. The liquid from the floatation tank then passes 45 insoluble mercury sulfide precipitates. A preferred class of
through line 13 to filter 14 in which residual precipitated ionic sulfide precipitants comprises the water-soluble sulfides such
mercury particles are removed. The resulting filtrate then as hydrogen Sulfide, alkali metal Sulfides such as Sodium
passes through line 15 to vessel 16 for an activated carbon sulfide and the alkali metal polysulfides, alkaline earth metal
polishing step in which remaining dissolved ionic mercury sulfides, alkaline earth metal polysulfides, which are both
together with elemental and organic mercury are removed 50 economic and commercially available. Other materials which
along with residual hydrocarbons. The water, essentially free may be used to precipitate the mercury in sulfide form include
of all mercury species then leaves the treatment unit through the thiazoles, alkali metal thiocarbamates, alkali metal dithio
line 17 and can be followed by other treatment steps which carbamates, alkali metal Xanthates and alkali metal trithiocar
may be necessary or desirable, for example, biotreatment to bonates such as sodium trithiocarbonate (NaCS). The
reduce chemical oxygen demandor, if the stream is by now in 55 appropriate amount of the precipitant may be empirically
compliance with applicable regulations, discharged to the determined.
environment. To satisfy the need for a metal scavenging agent that is less
The present mercury removal process is applicable to aque toxic and also forms a large, fast settling floc, highly efficient
ous streams which contain mercury, including wastewater metal chelating polymers have become commercially avail
and produced water streams. As noted above, such aqueous 60 able and these are useful as mercury precipitants in the
streams are frequently associated with the production and present process. Water soluble polymers of this type include
refining of mercury-containing hydrocarbons and with pro the polydithiocarbamates which may be used effectively in
duction of petrochemical streams made from Such hydrocar the present process with a reduced risk of discharge of either
bons. The aqueous streams may be encountered close to the the mercury itselforofa toxic treating agent. Polymers of this
Zone of production or, conversely, may be encountered at 65 type are described, for example, in U.S. Pat. Nos. 5,500,133;
distant processing sites if the hydrocarbons have not been 5,523,002; 5,658.487; 5,164,095; and 5,510,040 and are cur
treated to remove the mercury before shipping. The present rently marketed by Betz-Dearborn Inc. and Nalco Inc., under
 US 8,034,246 B2
5 6
the respective tradenames of METCLEARTM 2405 and NAL about 50 ppm is used, depending on the nature of the coagu
METTM. Precipitants of this type are preferred for use in the lant or flocculant and in most cases, less than 25 ppm will be
present process in view of their ability to produce a flocculent Sufficient, e.g. 10 ppm.
precipitate which can be readily separated in the Subsequent Following the addition of the precipitant and any coagul
gas flotation step although, again, coagulants and floculents lating or flocculating agent, the aqueous stream and the pre
may be added. In streams containing up to 60 ppb mercury, cipitate of the insoluble mercury compound are transmitted to
the use of the water-soluble polymeric dithiocarbamates in the flotation tank 12 where the majority of the precipitate is
amounts up to 30 ppm has been found adequate for Substantial removed by flotation (which includes and normally, is, dis
mercury removal but in all cases, the necessary amount rela Solved air, induced air, or induced gas flotation). Flotation
tive to the level of ionic mercury contaminant should be 10 techniques and equipment are well known. An example of a
determined empirically or by reference to supplier directions. gas flotation unit similar to those which may be used as a part
The mercury precipitants are normally used at near-neutral of the present process is found in U.S. Pat. No. 6,635,182.
or slightly alkaline conditions, with values close to 8 being Using flotation, the precipitated mercury compounds are con
typical, although lower and higher pH values can be tolerated. centrated into a sludge which can be removed from the water
The molar amount of the selected precipitant should at least 15 phase and sent for disposal according to conventional Solids
equal the amount of mercury ions to be removed with a slight treatment methods. The flotation step therefore acts to con
excess preferably being present. The use of large excesses of centrate the mercury content of the aqueous stream, along
precipitants such as sodium Sulfide should, however, be with other metals removed in the precipitation/flotation,
avoided as they may lead to the formation of water-soluble including lead, cadmium, nickel and copper. The flotation
mercury sulfide complexes which inhibit removal of mercury step may also remove hydrocarbons which may be present in
by the present process. Additionally, excessive amounts of the water; normally, hydrocarbons present will be carried off
sulfides and other precipitants of this type could exceed the in the float which is carried up to the surface of the water by
amounts permitted in water discharges and since certain of the action of the as bubbles. If volatile hydrocarbons are likely
these precipitants may be toxic in themselves, care must be to be present, a closed flotation tank should be used.
taken to ensure that they are not present in the discharged 25 Additional removal of particulate mercury, too small to be
wastewater. Another reason for not using excessive amounts removed by flotation, is then conducted by media filtration
of precipitant is that residual amounts will tend to be adsorbed following the flotation. To this end, the processed aqueous
upon the carbon and will load up the carbon bed prematurely. stream is removed from flotation tank 12 via line 13 to the
The optimal amount of precipitant should, for this reason, not filtration unit 14. The filtration process can be carried out
exceed the mercury content by more than one order of mag 30 using filters appropriate to the Volume of water passing
nitude. Temperatures during the precipitation step can Suit through the unit and to the need to remove very finely-divided
ably range from 10°–40° C. (about 50°-100° F.) although particles of mercury from the water. Although the use of
temperatures outside this range are not to be excluded. The mechanical filters and membrane microfilters may be con
average residence time in the precipitation step should be templated, media filters will normally be preferred. Media
long enough to enable the reaction to take place through the 35 filtration is carried out using a bed of finely-divided, inert
body of liquid and for the precipitate to form fully. Normally Solid Such as sand or anthracite which retains particulate
from 10 to 20 minutes will be adequate and sufficient. mercury and any residual precipitate not removed by flota
The metal complex precipitates formed by reaction of the tion. The bed particle size should be chosen in accordance
mercury with precipitants such as the Sulfides, polysulfides, with the floc size achieved in the precipitation/flotation step.
mercaptains, thiocarbonates, thiocarbamates and Xanthates 40 Normally, the media filter will have the largest particle size
are usually in the form of fine solids which do not settle or medium on top of the bed with progressively decreasing
filter easily and for this reason, are Susceptible to clogging particle size down through the bed The downflow dual media
and may even pass through most filtration systems. Addition filter is the preferred type in view of its ability to process large
of a coagulant or flocculating agent is normally preferable to quantities of water although other types of filter may also be
achieve efficient removal of these suspended solids in the 45 used. Backwash capabilities should preferably be incorpo
Subsequent gas flotation step, even when using the preferred rated. A dual media filter with sand on bottom (particle size
polymeric dithiocarbamate precipitants. Additionally, coagul 0.4–0.6 mm) and anthracite on top (particle size 0.85-0.95
lant or flocculating agents may be required in services with mm) is particularly preferred although media particle sizes of
high levels of influent free hydrocarbon and/or suspended this magnitude will be suitable with other media filters. Flux
Solids to help remove these contaminants and avoid adverse 50 rates of up to about 3 1/m/min (about 9 gal/ft/min) are
interactions with the mercury precipitant. Suitable coagulants suitable for use in a dual media filter in the present process
and flocculants are organic or inorganic, or a combination of and similar rates would be typical of other media.
the two, and may be polymeric, eitheranionic or cationic and The filtered aqueous stream is again filtered through a bed
usually can be categorized as polyelectrolytes Such as sodium of activated carbon to remove any residual dissolved ionic
aluminate, aluminum trihydrate, and ferric chloride. Poly 55 mercury species as well as elemental and organic forms of
meric organic coagulants and flocculants include the poly mercury. Carbon has been found effective for removing
acrylamides, diallyldimethylammonium chloride (DAD potential trace species (elemental as well as organic) as well
MAC) polymers, DADMAC-polyacrylamides and as to act as a final guard bed for particulate matter. A notable
epichlorohydrin dimethylamine (EPI-DMA) polyamines. If feature of the present technique is that the carbon is more
used, these materials may be added in the conventional 60 selective for mercury than for dissolved organics or chemical
amounts. These coagulants and flocculants are typically oxygen demand (COD) with the result that the bed remains
added to streams prior to treatment by flotation; they may active for mercury removal even after the ability to remove
continue to be used in the present process to promote sepa organics has dissipated, as shown by an increase in the COD
ration of the precipitated mercury compounds. The amount of of the activated carbon filtrate.
coagulant or flocculant is generally in line with existing prac 65 The type of carbon most preferred in this step is granular
tices for removing Suspended solids since the amount of activated carbon with an average particle size from 0.8 to 1.0
precipitated mercury compound is not great. Typically, up to mm although particle sizes both above and below this range
 US 8,034,246 B2
7 8
may be found suitable. A preferred type of carbon is standard mercury to simulate the wastewater expected when running
bituminous coal based activated carbon. Carbons of this kind high mercury crude. The test wastewater was spiked in the
are widely available commercially from Suppliers such as testing with 30 wppb ionic mercury (mercury chloride) and
Calgon Carbon Corporation, Pittsburgh Pa., Fresh Water Sys treated with various amounts of the mercury precipitant, GE
tems, Greenville S.C. and Res-Kem Corp Media, Pa. Flow Betz MetClear (MR 2405), before being passed to a settling
rates over the granular carbon beds using a downflow regime tank to permit some removal of the precipitated Solids. In
can typically be 1 to 2 l/m/min (about 3-5 gal/ft/min). A some tests a cationic coagulant, GE Betz Klaraid (CDP
minimum of two activated carbon columns in series is pre 1337), was added to minimize interaction between free-hy
ferred with operation in a lead/polish configuration. In this 10
drocarbon/suspended solids and MetClear as well as improve
configuration, leadbed breakthrough can be tolerated, allow settling of the pin floc produced. The effluent from the settling
ing the lead bed to stay on-line longer and become more tank was then filtered through a media filter comprising sand
heavily loaded. The polish bed removes any residual mercury and anthracite. Mercury levels were measured before the
allowing for mercury-free effluent. After the leadbed is spent, precipitant addition and before and after the media filter. The
it is replaced with fresh carbon and then becomes the polish 15 six week test confirmed that at optimal chemical dosing rates,
bed. The use of powder activated carbon (PAC) in a slurry 96% mercury removal could be achieved using the mercury
contact reactor with the PAC removed in a subsequent solids precipitant. With the addition of the media filter, over 99%
separation stage would be less preferred both in terms of cost removal of dissolved ionic mercury was achieved with all
and the ability to remove particulates without the additional levels in the treated wastewater being below the detection
solids separation stage. Another option would be PAC addi limit of 0.1 wppb. The addition of the air flotation step could
tion to an existing activated sludge biological treatment unit. be expected to improve filter operation (increase filter run
Pilot tests were conducted to confirm the effectiveness of
the mercury precipitant and media filter on the removal of length) by superior removal of the precipitated solids prior to
mercury on wastewater from a petroleum refinery by spiking entry to the filter bed.
the effluent from the IAF (Induced Air Floatation) unit with The results are shown in Table 1 below.
TABLE 1
Removal of Ionic Mercury (30 ppb) by Precipitation. Filtration
MetClear Flocculant Hg before Hg after Removal: Removal: Removal:
ppm ppm DMF, ppb DMF, ppb MetClear DMF MetClear + DMF
5 O 4 86.7%
5 O 0.4 O.1 98.7% 75.0% 99.7%
5 O O.6 98.0%
5 O O.6 O.2 98.0% 66.7% 99.3%
5 O 0.7 97.7%
5 O 1.1 96.3%
5 O 1.6 O.2 94.7% 87.5% 99.3%
5 O 0.4 98.7%
5 O O.1 O.1 99.7% O.0% 99.7%
5 O O.1 O.1 99.7% O.0% 99.7%
5 O O.3 O.2 99.0% 33.3% 99.3%
5 O O.6 O.9 98.0% SO.0% 97.0%
5 O 1.1 96.3%
5 O O.2 O.1 99.3% SO.0% 99.7%
5 O O.1 O.1 99.7% O.0% 99.7%
5 O 0.4 O.1 98.7% 75.0% 99.7%
5 O O.S O.S 98.3% O.0% 98.3%
25 O O.2 O.1 99.3% SO.0% 99.7%
25 O 12.8 1.4 57.3% 89.1% 95.3%
25 O 2.3 92.3%
25 O 2.9 90.3%
25 O 3.2 2.4 89.3% 25.0% 92.0%
25 O 2.3 92.3%
25 O 2.6 91.3%
25 O 2.6 3.0 91.3% 15.4% 90.0%
25 O 5.4 1.7 82.0% 68.5% 94.3%
30 O 6.2 3.6 79.3% 41.9% 88.0%
30 O 4.7 2.2 84.3% 53.2% 92.7%
30 O 3.3 O6 89.0% 81.8% 98.0%
30 O 1.6 O.2 94.7% 87.5% 99.3%
30 10 O.1 O.1 99.7% O.0% 99.7%
30 10 O.3 O.1 99.0% 66.7% 99.7%
30 10 O.2 O.S 99.3% 150.0% 98.3%
30 10 O.1 O.2 99.7% 100.0% 99.3%
30 10 0.7 O.1 97.7% 85.7% 99.7%
30 10 O.S O.1 98.3% 80.0% 99.7%
30 10 1.2 O.1 96.0% 91.7% 99.7%
30 10 0.4 O.1 98.7% 75.0% 99.7%
30 10 O.1 O.1 99.7% O.0% 99.7%
15 10 1.6 O.1 94.7% 93.8% 99.7%
15 10 1.6 O.1 94.7% 93.8% 99.7%
15 10 O.S O.1 98.3% 80.0% 99.7%
15 10 O.S O.1 98.3% 80.0% 99.7%
 US 8,034,246 B2
10
The use of activated carbon is an effective guard for organic demand (COD) is shown in Table 4 below, obtained in certain
mercury was also confirmed by pilot plant testing. In the tests, of the runs identified in Table 3 above. The results show that
the IAF wastewater was spiked with organic mercury (as COD is not reduced to the same extent as the organic mercury,
mercury alkyl dithiocarbamate) at 30 ppb and 60 ppb to indicating that there is a selectivity for mercury removal.
simulate the expected aqueous stream composition associ
ated with high mercury content crude and gases. The spiked TABLE 4
wastewater was processed through a dual media filtration unit
of sand and anthracite as above followed by a single activated COD
Effluent from Carbon Column
carbon column. Mercury levels were measured before pass
ing through the media filter, before passing through the car 10 COD COD
bon column, and after the carbon column. Additionally, before after
chemical oxygen demand (COD) levels were also measured Run
No.
DMF,
mg/l
Carbon,
mg/l
% COD
Reduction
to determine whether COD or mercury would be selectively
adsorbed. It was discovered that complete mercury removal 17 387 194 SO%
was maintained even after COD breakthrough (breakthrough 15 18 346 205 41%
19 267 159 40%
of dissolved organic compounds). In this seven week test, 2O 351 190 46%
outlet mercury levels of less than 0.1 wppb (detection limit) 21 174 243 -40%
were consistently achieved and the carbon life was proven to 23 275 192 30%
be sufficient for commercial operation. 24
25
214
276
197
215
8%
22%
The results of testing using 30 ppb of added organic mer
cury are given in Table 2 below.
Isotherm tests were conducted using dissolved ionic mer
TABLE 2 cury (mercury chloride), organic mercury (diethylmercury),
Organic Hg (30 ppb) Removal over Dual Media Filter, Carbon 25
and elemental mercury to confirm the effectiveness on differ
ent forms of mercury. The tests confirmed that carbon was
Hg shown to have the ability to remove each of the dissolved
before Hg after Hg after forms of mercury, although the carbon capacities differ
Run DMF, DMF, Carbon, Removal: Removal: Total
No. ppb ppb ppp DMF Carbon Removal depending on the species.
1 S.1 O.9 O. 82.40% 88.90% 98.00% 30
2 1.2 O.09 O. 92.50% -11.10% 91.70% The invention claimed is:
3 0.1 0.1 0. O.OO% O.00% O.OO% 1. A method for removing mercury in ionic and non-ionic
4 O4125 O1 O. 75.80% O.00% 75.80% form from aqueous streams, comprising:
5 O.1625 O.1 O. 38.50% O.00%. 38.50%
6 O.3625 O.1 O. 72.40% O.00% 72.40% (i) adding a mercury precipitant to the aqueous stream to
7 1.35 O.1 O. 92.60% O.00% 92.60% 35 react with dissolved ionic mercury compounds present
8 1.065 O.3625 O. 66.00% 72.40% 90.60%
9 1 0.0875 O. 91.30% - 14.30% 90.00%
in the stream to form a water-insoluble precipitate of a
10 1.4 O.S O. 64.30% 80.00% 92.90%
mercury compound,
11 1.5 0.4 O. 73.30% 75.00% 93.30% (ii) separating the precipitated mercury compounds from
12 0.7 O.3 O. 57.10% 66.70% 85.70% the water of the stream by means of gas flotation,
13
14
O.1
O.8
O.1
O.1
O.
O.
O.00%
87.50%
O.00%
O.00%
O.00%
87.50%
40 (iii) passing the water separated from the stream through a
15 O.2 O.1 O. SO.00% O.00% SOOO% media filter to remove particulate mercury and residual
16 O.1 O.3 O. -200.00%. 66.70% O.00% particulate material and so form a filtrate of water with a
reduced level of mercury,
The results obtained with the addition of 60 ppb organic (iv) passing the filtrate over activated carbon to remove
45 residual mercury.
mercury are shown in Table 3 below. 2. A method according to claim 1 in which the non-ionic
forms of mercury present in the aqueous stream comprise
TABLE 3 organic mercury compounds.
Organic Hg (60 ppb) Removal over Dual Media Filter, Carbon 3. A method according to claim 1 in which the non-ionic
50 forms of mercury present in the aqueous stream comprise
Hg elemental mercury.
before Hg after Hg after 4. A method according to claim 1 in which the mercury
Run DMF, DMF, Carbon, Removal: Removal: Total
No. ppb ppb ppb DMF Carbon Removal precipitant comprises a compound which reacts with the dis
Solved mercury compounds present in the stream to form
17 O.S 0.4 O.1 20.00% 75.00% 80.00%
18 O.S O.3 O.1 40.00% 66.70% 80.00%
55 water-insoluble sulfides of mercury.
19 1.3 O.1 O.1 92.30% O.00% 92.30% 5. A method according to claim 4 in which the mercury
2O O.1 O.1 O.1 O.00% O.00% O.00% precipitant comprises an alkali metal Sulfide, an alkali metal
21 1.2 O.1 O.1 91.70% O.00% 91.70% polysulfide, an alkaline earth metal Sulfide, an alkaline earth
22
23
1
0.7
O.2
O.6
O.1
O.3
80.00%
14.30%
SO.00%
50.00%
90.00%
57.10%
metal polysulfide.
24 O.6 0.7 O.2 -16.70% 71.40% 66.70%
60 6. A method according to claim 1 in which the mercury
25 O.3 O.8 O4 - 166.70% 50.00% -33.30% precipitant comprises a thiazole, an alkali metal thiocarbam
26 O.3 0.4 O.3 -33.30%. 25.00% O.00% ate, an alkali metal dithiocarbamate, an alkali metal Xanthate
27 O.2 O.2 O.00% O.00%
28 0.4 O.2 SO.00% SO.00%
or an alkali metal trithiocarbonate compound which reacts
with the dissolved mercury compounds present in the stream
65 to form a water-insoluble compound of mercury.
The selectivity of the carbon for mercury removal in pref 7. A method according to claim 1 in which the mercury
erence to the removal of organics creating chemical oxygen precipitant comprises a water-soluble polymeric dithiocar
 US 8,034,246 B2
11 12
bamate which reacts with the dissolved mercury compounds 14. A method according to claim 1 in which the media filter
present in the stream to form a water-insoluble compound of comprises a dual media filter.
mercury. 15. A method according to claim 14 in which the dual
8. A method according to claim 1 in which the pH is media filter comprises a sandbed on an anthracite bed.
maintained in the range from about 6 to about 9 when the 16. A method according to claim 15 in which the dual
mercury precipitant is added to the aqueous stream. media filter comprises sand with a particle size of 0.4–0.6 mm
9. A method according to claim 8 in which the temperature sandon bottom and anthracite with a particle size of 0.85-0.95
is maintained in the range from 10°–40°C. when the mercury mm on top of the sand.
precipitant is added to the aqueous stream. 17. A method according to claim 14 in which the flux rate
10. A method according to claim 8 in which the a coagulant 10 through the filter is up to about 3 1/m/min.
or floculant is added to the stream when the precipitate is 18. A method according to claim 1 in which the activated
formed.
11. A method according to claim 10 in which the amount of carbon comprises granular activated carbon with an average
coagulant of floculant is less than 25 ppm. particle size from 0.8 to 1.0 mm.
12. A method according to claim 7 in which the aqueous 19. A method according to claim 18 in which the activated
stream comprises mercury in an amount up to 60 ppbw and 15 carbon comprises bituminous coal based activated carbon.
the amount of the added water-soluble polymeric dithiocar 20. A method according to claim 18 in which the flow rates
bamate is up to 50 ppmw. over the granular carbon is 1 to 2 l/m/min.
13. A method according to claim 12 in which the amount of
the added water-soluble polymeric dithiocarbamate is up to
30 ppmw.