Biocides 351

14.3.2.15 Specic Surfactant Classes

Alkylaminomethylenephosphonic acid amphiphilic compounds having the general
formula RR
2
NCH
2
P(O)(OH)
2
, such as octylaminomethylenephosphonic acid, have
been claimed as biocides. It is possible that hydrophobically modifed phosphonate
scale inhibitors with several phosphonate groups might also show biocidal properties
but this was not claimed.
104
Sulfamic acid surfactants such as dodecyl sulfamic acid
have also been claimed by the same group as biocides.
105
14.4 BIOSTATS (CONTROL BIOCIDES
OR METABOLIC INHIBITORS)
Biostats do not necessarily kill bacteria but interfere with their metabolic processes,
controlling their growth. As discussed in the section on organic biocides, isothiazo-
lones are one class of biostats, preventing the formation of iron sulfde scale (via
hydrogen sulfde) by maintaining a low level of SRB and inhibiting their metabolic
activity. Metabolic inhibitors deprive SRB of the ability to produce ATP, and as
a result, cells are unable to grow and/or divide. This inability to grow or divide
may eventually cause the death of some of the SRB; however, the cell death is not
a direct result of exposure to the metabolic inhibitors as it would be for biocides.
Alkylbenzyldimethylammonium salts are also a commercially signifcant class of
biostats. A combination of biocide and biostat has been shown in laboratory stud-
ies to inhibit biogenic sulfde production at signifcantly lower concentrations than
would be required if the biocide or biostat was used alone.
106
Examples of biostats that are not biocides are discussed in this section. They
include:
anthraquinone
azide ions
nitrite and nitrate ions
molybdate or tungstate ions
selenate ions
14.4.1 ANTHRAQUINONE AS CONTROL BIOCIDE
Anthraquinone has been used as a biostat in a number of projects since the late
nineties (Figure 14.20). Anthraquinone is not water-soluble, but 9,10-anthracenediol
O
N
O
C
2
H
5
N
O
CH
3
H
3
C
N
O
H
2
C
N
O
FIGURE 14.19 7-Ethyl bicyclooxazolidine (left), 4,4-dimethyloxazolidine (middle), and
methylene bis-oxazolidine (right).
2009 by Taylor and Francis Group, LLC
352 Production Chemicals for the Oil and Gas Industry
disodium salt is water-soluble and works as if it were anthraquinone.
107
Anthraqui-
nones have been shown to inhibit sulfate respiration in SRBs effectively shutting
down the sulfde-producing mechanism but having little effect on other classes of
bacteria.
108109
One water injection program managed to eliminate continuous injec-
tion of a quaternary biocide with slug doses of the easier-to-handle anthraquinone
product. Slug doses of synergistic acrolein biocide were used in addition.
110111
Batch
treatment of anthraquinone together with THPS biocide has also been shown to be
effective in stopping biogenic sulfde production in produced water tanks in slop-
handling systems.
112113
14.4.2 NITRATE AND NITRITE TREATMENT
Nitrite (NO
3

) and nitrate ions (NO

2

) as found in calcium or sodium nitrate/nitrite

salts are cheap, easy to handle, environment-friendly inorganic chemicals, and
becoming more and more used in the oil industry to inhibit SRB. The corrosion con-
sequences of using nitrate or nitrite in oilfeld brines have been reviewed.
114
Nitrite directly inhibits sulfate reduction by SRB because it is reduced more slowly
than sulfte by the fnal enzyme in the sulfate reduction pathway, dissimilatory sulfte
reductase. Thus, addition of nitrite ions to produced water or seawater injection sys-
tems can control biogenic sulfde formation if present in high-enough concentra-
tion (depending on pH, nitrite, but not nitrate, ions also react directly with any H
2
S
already present to form sulfur and reduced nitrogen compounds). In one feld study,
pulses of nitrite were more effective than the same amount of nitrite added continu-
ously. Nitrite was more effective at inhibiting souring than was glutaraldehyde, and
SRB recovery was delayed longer with nitrite than with glutaraldehyde.
115
Nitrite
injection has also been used successfully in producer wells to scavenge H
2
S and
prevent SRB activity.
116
In one case, oil production increased immediately following
the treatment, probably due to the dissolution of precipitated iron sulfdes in the zone
surrounding the wellbore.
117
There exist nitrate-reducing and sulfde-oxidizing bacteria (hNRB and NR-SOB)
in most oilfelds that can reduce nitrate ions to nitrite ions.
118119
Thus, the upstream
petroleum industry has introduced a nitrate-based microbial treatment technol-
ogy, useful for both the prevention and removal of biogenic sulfde from reservoirs,
produced water, surface facilities, pipelines, and gas-storage reservoirs, as well as
O
O
FIGURE 14.20 Anthraquinone.
2009 by Taylor and Francis Group, LLC
Biocides 353
increasing oil recovery. This reservoir treatment technology works by replacing
SRB with a naturally occurring suite of benefcial microorganisms enhanced by the
introduction of an inorganic nitrate-based formulation.
120
If the reservoir is a poor
source of carbon for SRB (low in small organic acids), injection of nitrate ions will
stimulate growth of hardier denitrifying bacteria (nutrient augmentation), thereby,
dominating the system and inhibiting the growth of SRB. Production of nitrite and
sometimes nitrous oxide (NO) from nitrate ions by the hNRB and NR-SOB will also
directly inhibit SRB growth by acting as toxins. In addition, hNRB and NR-SOB
may produce compounds that raise the oxidation-reduction potential of the environ-
ment to a level that is inhibitory to the growth of SRB.
121129
Calcium or sodium nitrate are environment-friendly and complement the natu-
rally occurring organic acids in the reservoir, selectively stimulating and increas-
ing the targeted nitrate-reducing bacteria. Many North American gas felds have
been treated successfully this way and several felds in the North Sea have already
successfully used this treatment strategy for reducing, but not totally eliminating,
reservoir souring, both by reactive and proactive strategies. It is a simple method for
preventing biogenic sulfde formation, which can mostly eliminate the use of organic
biocides.
130134
For the reasons discussed above, the use of a mixture of nitrate and nitrite
ions may perform superior to a simple nitrate treatment.
135
One study showed that
nitrite treatment alone may be preferable in reservoirs with only SRB present.
136

In addition, the use of a molybdenum compound (molybdate) may also enhance
the treatment effect. Molybdenum is a known enzymatic inhibitor of the hydro-
genase enzyme found in SRB.
137
It should be noted that nitrate/nitrite treatment
may not totally eliminate the use of biocides if they are injected very late in the
system. For example, a deepwater feld offshore Nigeria that has been treated with
calcium nitrate still uses a biocide (THPS) to prevent bioflms in the injection
facilities.
138139
A potentially large advantageous side effect of using nitrate-based
water injection treatments is microbial-enhanced oil recovery (MEOR). Formation
of NR-SOB bioflms in the reservoir may help to release more oil from the rock
surface, which can then migrate to the producer wells. The use of nitrate, together
with other nutrients such as vitamins and phosphate, has been suggested as an
MEOR improvement.
140
Instead of relying on indigenous bacteria, injection of non-SRB bacteria with
nutrients such as nitrate ions has also been carried out, eliminating, in one case, the
use of hazardous acrolein biocide.
141
A novel class of bacteria that oxidize sulfde as
well as oil organics with nitrate has been reported.
142
There is still a lot to learn about
nitrite/nitrate treatments, such as the relative effectiveness of nitrate versus nitrite
ions and determining which of the several mechanisms of reducing biogenic sulfde
production is dominant.
14.4.3 OTHER BIOSTATS
Azide salts such as sodium azide (NaN
3
) have long been known as biostats and have
been suggested for use in preventing biofouling of wells.
143
Sodium azide acts as a
2009 by Taylor and Francis Group, LLC