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Патент USA US3021266

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United States Patent 0 ’
Patented Feb. 13, 1962
plete understanding of the invention, a brief description
of the water ?ooding process is given below.
When an oil well ceases to flow by the natural pres
sure in the formation and/or substantial quantities of
oil can no longer be obtained by the usual pumping
Nalco Chemical Company, a corporation of Delaware
methods, various processes are sometimes used for the
N0 Drawing. Filed June 2, 1958, Ser. No. 738,918
treatment of the oil bearing formation in order to in
13 Claims. (Cl. 162-161)
crease the ?ow of oil. These processes are usually de
The present invention relates to a process for chemi
scribed as secondary recovery processes. One such proc
cally treating aqueous ?uids used in various industrial 10 ess which is frequently used is the water ?ooding process
processes for the purpose of controlling the growth and
wherein water is pumped under pressure into what is
reproduction of microorganisms. More speci?cally, the
called an “injection well,” and oil along with quantities
invention is directed to a new class of microbiocidal
of water that have been displaced from the formation
agents which afford excellent bacteriological control in
are pumped out of an adjacent well which is referred to
the paper making processes and are not rendered inactive
as a “producing well.” The produced oil is then sepa
due to the ‘absorptive properties of cellulose ?bers.
rated from the water that has also been pumped from
Carol H. Bollenback, Palos Park, George R. Hunt, La
Grange, and Jerry J. Svarz, Joliet, Ill., assignors to
, The growth of microorganisms, in industrial process
waters is a problem which occurs in many industries
using large quantities of aqueous ?uids. The problem
the producing well. The reclaimed Water is then pumped
to a storage reservoir from which it can be fed into the
injection well. Supplementary water from other sources
occurs in such industrial systems as cooling towers, paper 20 may ‘also be used in conjunction with the produced water.
mills, the secondary recovery of petroleum in the process
When the storage reservoir is opened to the atmosphere,
known as water ?ooding, water wells, and similarly re
and the oil is subject to aeration, this type of water ?ood
lated industrial fluid systems. Most industrial systems of
ing system is referred to as an “open water ?ooding sys
these types obtain their water supplies from many varied
tern.” If the water is recirculated in a closed system
sources and due to economic considerations, it is cus 25 without substantial aeration, the secondary recovery
tomary to recirculate and reuse the water. This tends
to produce an environment favorable towards the cul
ture and spread of undesirable microorganisms such as
the various species of bacteria and fungi.
One of the most acute bacteriological control prob
lems is found in the production of paper. Microbiologi
cal slime masses which form in the various parts of the
paper making system are recognized as one of the rea
method is frequently referred to as a “closed water ?ood
ing system.”
The water which is introduced into the injection wells
may vary considerably in composition from one ?eld to
another. Frequently it contains relatively large quanti
ties of dissolved salts such as sodium chloride and, there—
fore, can be described as a brine. It may also contain
other salts such as those of calcium, magnesium, barium,
and strontium. Some iron salts may also be present. In
son-s for decreased production, breaks occurring on the
machines, and the occurrence of spots and holes in 35 some cases these salts are added to fresh water to pre
paper. Unless these slime masses are controlled, pro
vent clay minerals from swelling and to seal porous oil
duction is decreased and maintenance costs become ex
sands, but in most cases, their occurrence is natural.
‘In the last few years there have been several commer
In order to curtail microbiological phenomena from
cially available bactericidal preparations sold for the
occurring, it is today a common practice to use chemi 40 speci?c purpose of controlling sulphate reducing bacteria
cal treatment to control and mitigate growth of micro
in water ?ood operations. These preparations have met
organisms which tend to ‘form slimes in the various parts
with varying measures of success, but they have not been
of the paper making plants. Investigations of the slime
found adequate in controlling sulphate reducing bacteria
forming microorganisms have disclosed that numerous
when the brine content of the injection fluid is relatively
varieties Off bacteria and fungi are the source of the prob
high. These high brine water ?ood liquids usually con
lem, and it is often necessary to control these organisms
tain at least 3% or more of dissolved salts and usually
by using several different types of microbiocidal agents.
will contain from 10% to 30% by weight of dissolved
It would be extremely advantageous if a single chemi- '
cal treatment were available which would be able to con
trol the several species of microorganisms commonly oc
curring in paper mill manufacturing processes whereby
these detrimental slime~forming organisms would be con
trolled or reduced.
Another aspect of the problem of controlling micro
organisms in the paper manufacturing industry is that the
salts and for some unknown reason these high concen
trations of inorganic salts tend to render ineifectual many
of the well-known microbiocides which are effective in
controlling sulphate reducing bacteria under less saline
Similar conditions exist in many other industrial sys
tems where water tends to flow and is subject to con
stant environmental change.
pH variations, dissolved
water used in the paper making process contains quanti
solid contents, and environmental adaptation of micro
ties of cellulosic materials which vary in concentration
organisms tend to make the control of microorganisms
from about 0.1%, of which white water is exemplary,
extremely dif?cult in many industrial systems. Many
all the way up to 15% by weight, which concentrations
commercially available microbiocides, While being some
are fairly common in pulp storage tanks. Many chemical 60 what etfective in systems such as are described above,
microbiocidal agents have the tendency to be selectively
have the disadvantage of being soluble only by careful
absorbed by the ?ber, which means they are no longer
pH control.
capable of e?ectively acting upon the slime masses. To
It would be extremely‘ desirable if a microbiocidal
be really effective in the control of microorganisms in
agent were available which would adequately control
paper mills, it is extremely desirable that a chemical is 65 microorganisms of the type commonly occurring in the
able to control the growth of a number of species of
aqueous systems such as paper mills, Water ?oods, cool
harmful microorganisms but also that such agent should
ing towers, and the like and also would be relatively
not tend to be absorbed on cellulose ?bers.
economical to produce and use. Another advantage
Another specialized and extremely di?icult industrial
would be a chemical microbiocidal agent which would
problem is the control of microorganisms of the sulphate 70 be effective at extremely low dosages. It, therefore, be
reducing bacteria type, which problem is associated with
comes an object of the invention to provide a new and
the process known as water ?ooding.
improved class of microbiocides which are useful in the
For a more com
control of various species of microorganisms of the types
commonly found in industrial process water systems.
Another object is to furnish new chemical microbio
cidal agents which are effective in controlling a large
number of microbiological species at low, economical
A speci?c object is to provide a new classof‘micro
biocidal agents which are effective in controlling the
growth and reproduction of microorganisms of the type
often found in'paper mills and are not subject to sorp
upon the particular system treated, as well as the types
of species found present. In most cases, however, as
little as one-half part per million to 25 parts per million
will give adequate control, although quantities ranging
as high as 500 parts per million may be necessary in some
cases. Small quantities of the chemical are extremely
effective in industrial process systems where the water
is recirculated and reused, which means that the quan
tity of the chemical will gradually build up to a maxi
mum usable and effective treating dosage, which may
be calculated knowing the speci?c factors in each par
tion by cellulose ?bers.
ticular system.
Another speci?c object is to provide a microbiocidal
Most of the halogenated ketones, particularly the hal
agent useful in controlling sulphate-reducing bacteria in
ogenated ketones containing aromatic nuclei, are not par
water ?ooding operations, particularly in the presence
of high brines. Other objects will appear hereinafter. 15 ticularly soluble in water, and it is necessary to further
formulate the materials where concentrated water dis
In accordance with the invention, it has been found
persible' products are desired. The most expeditious
that the growth and reproduction of microorganisms of
manner of formulating these chemicals is to dissolve or
the type commonly found in industrial process waters
suspend the halogenated ketone into a hydrocarbon liq
may be controlled by treating said waters with a small,
uid solvent and to add su?flcient amounts of an emul
yet active, amount of a halogenated ketone which con
tains more than three carbon atoms but less than eight
een carbon atoms in its molecular con?guration. Halo
sifying agent whereby aqueous emulsions may be pre
pared. Thus, for instance concentrated solutions or
genated ketones of this type may be represented by' the
general formula:
suspensions containing from ?ve to twenty‘ percent by
weight of the halogenated ketones containing aromatic
25 groups may be made using such solvents as xylene, tolu
ene, or petroleum aromatic solvent type oils and adding
to such solvents from 0.5 to 3% by weight of a suitable
emulsi?er, such as C6-C2z alkenyl succinic anhydrides
In the above formula R and R’ represent a wide variety
or their alkali metal salts or such materials as ethoxyl
of organic radicals such as alkyl, aryl, alkaryl, and ar 30 ated and/or propoxylated fatty-substituted amines which
alkyl. In addition to being composed exclusively ofhy
contain from three to ?fteen moles of ethylene oxide.
drocarbons, R and R’ may also be composed of one or
In the case of primarily aliphatic halogenated ketones,
more heterocyclic rings which may contain'such ele
aliphatic hydrocarbon solvents with emulsi?ers would be
ments as oxygen, sulfur, or similar'nonhydrocarbon mem
The materials of the invention are quite frequently
bers. In accordance with the broad conceptpreviouslyi 35
expressed, the total‘number of carbon atomscontained
soluble at use concentrations in industrial process Water
in R and'R’ will be in excess of two carbon atoms but
systems so that chemical briquette absorbents as soda
less than seventeen. The number of halogen atoms that
ash, dextrine, and the like, may be used to prepare solid
are necessary to give the ketone microbiological activity
materials which may be fed using conventional briquette
is not particularly critical, although from one to three 40 feeding equipment.
halogen atoms are preferred with amounts in excess of
this number being relatively unnecessary in terms of ef
fectiveness. It is also preferred that the halogen sub
In order to determine‘the e?icacy of the invention for
stituent be near the carbonyl portion of the molecule
treating various types of industrial process water under
and is not part of an aromatic grouping.
45 a wide variety of conditions, two test methods were
A speci?c group of halogenated ketones of the type
used. These test methods correlate with conditions exist
with which this invention is concerned are illustrated by
ing in many industrial process systems Where micro
General Formula 11 below:
biological problems occur. These test methods are set
forth in detail'below:
This particular type of halogenated ketone is an aryl
Test Method I
In this test the culture medium used consisted of 24
grams of dextrose, 1 gram of Basaminbact (Anheuser
Busch), added ‘to one liter of Chicago tap water and
or aralkyl-substituted ketone which, for some unknown 55 sterilized by autoclaving under 15 pounds of pressure
for 15 ‘minutes. An appropriate amount of 18 to 24
reason, gives somewhat superior results in the control
hour nutrient broth culture of A. aerogenes or A. niger
of microorganisms over and above the results obtained
was mixed with 200 ml. of the culture medium immedi
using other halogenated ketones. In Formula II, R and
ately before starting tests. The amount of culture was
R’ may be selected from such groups as hydrogen, halo
gen or methyl groups, and R" is a lower alkyl group 60 such as to give one million organisms per ml. of medium.
Twenty ml. of the inoculated culture medium was placed
which usually will have from one to three carbon atoms
in each of a series of fermentation tubes with caps which
in chain length, and x and y are integers having various
containedthe appropriate concentration of stock chem
values ranging from zero to three. The best results are
ical to avoid more than a 5% error in ?nal dilution. For
frequently obtained when the number of carbon atoms
contained in R, R’ and R” does not exceed ten. For 65 this purpose the volume of chemical introduced should
be; one ml. or less. The chemical and the inoculated
purposes of illustration, the halogen portion of the mole
medium were mixed gently. A control test was also
cule, Hal, has been depicted as being a generally-occur
run in which the chemical was omitted. In mixing, each
ring substituent as to the entirety of the molecule, al
tube was inverted in such a manner as to‘ ?ll the up
though in a preferred embodiment, it is desirable to have
right, closed end of the tube with the test liquid. The
the halogen substituted at the R or R’ position.
tubes were incubated at 30° C. for 48 hours. At the
Commercial expediency dictates that the halogenated
end of one hour contact and again after 24 hours’ con
ketone of ‘the invention will be a chloro-ketone, although
tact, a loopful of the test mixture was withdrawn from
the bromo- and iodo-ketones work equally well. The
each tube and inoculated in a subculture tube containing
amount of halogenated ketone necessary to achieve con—
trol of -microorganisms will, of course, varydepending 75 10 ml. of sterile nutrient broth. The subculture tubes
were incubated at 37° C. for 48 hours and examined for
growth. The results of these tests indicated 1 and 24'
hour killing ranges. The gas production for inhibition
level was recorded at 48 hours for Aerobacter. Growth
inhibition was recorded for A. niger after ?ve days.
. . .
To sterile 18-m1. screw-capped test tubes, sn?icient
amounts of the chemicals being tested were added to
give the desired concentration of bacteriostat in 18 ml.
After addition of the chemical, the room temperature
media, to which had been added 10 ml. of culture per
liter, was poured carefully into the screw-capped tubes
Test 1ll4eth0ddIl._—ScZ-eenm_g mlybztzon tteis'f for
8” fate re “6mg amen“ 0” tum me m
Sodium lactate (60%) _______________ _;m1__
to completely ?ll them, care being taken that no liquid
Yeast extract _____________ __>________ "gm"
Ascorbic acid _______________________ __gm__
was allowed to over?ow from the tubes. Duplicate tubes
Were prepared in every dilution in addition to a control
L0 10 tube which contains no chemical. The tubes were tightly
capped so that air was excluded.
Mg504-7H20 _______________________ __gm__
K2HPQ,( anhydrous) _________________ "gm"
The tubes were incubated at 37° C. for 7 days and
then observed for results. Growth of the sulfate reducers
was evidenced by intense blackening of the tubes, while
F6604) 201114) 2.61.120 ____ __'________ __gm__
Deionized water
10_() 15 inhibition of growth showed no change in appearance,
The desired concentrations of chemicals were obtained
The ingredients were dissolved by stirring, and the pH
was adjust-ed to 7.2-7.5 with 6 N NaOH.
in the 18-rnl. tubes by adding the following amounts
from the 0.09% solutions.
The media
for use
in autoclaved
the test.
at 15 lb./15 minutes
and was ready 20 concfgératlon
50 """"""""""""""""""""""""
(p‘p'm') '
Amount of solutlon’
" 1'0
The organisms were a culture of sulfate reducers
(Desulfovibrio) that were obtained from the American
Petroleum Institute and were designated as API-A culture. The inocula for the tests were from the third suc- 25
cessive 24-hour transfer, and‘ showed blackening after»
each 24-hour transfer.
Stock solutions of the bacteriostat to be screened were
prepared as 0.9% solutions by weight in ethanol.
“““““““““““““““““““““““““ "
""""""""""""""""""""""""" “
"""""""""""""""""""""""""" "
""""""""""""""""""""""""""" "
1 “““““““““““““““““““““““““ " 0 62
""""""""" "_ ““““““““““““““““ "
With the above-described test methods, several typical
the day of the test, 0.09% solutions by volume were 30 compositions of the invention were tested to determine
prepared in deionized water from the stock solutions and
their‘ activity. These results are set forth in Tables
were the working solutions for the tests.
I and 11.
Gas Tube Inhibition
Results (p.p.m.)
Au 1
I ___________ -_
2-ohloroaeetylturan _______ -.
to“? ‘t?
\ /
An I
IL. ........ _-
4-eh1orobutanone-2 ........ __
III ......... -_
3-ehlorobutanone-2 ________ -_
IV _________ -.
1-ehlorohexanone-2 ________ _.
‘1 ’
(I )
V __________ ._ a-chloro-a-phenyl aeetophe- QCHCI~CQ
VI ......... .. o-trichloroacetophenone_-... ©—(3—0Clt
VII ........ -- benzylacetone dlchlorlde__._ @vCHCl-CHOl-O-Ofh
VIII ....... .- a-chloro-a-phenyl acetone... OCHCl-C-CH;
IX ......... -_ a-ehloro proplophenone-._-_
X .......... _. ?-chloro proplophenone .... __ O-C-CEh-CILCI
(1 )
XI ......... .. p-chlorophenacyl chloride..- Cl®~C~CHzO1
See footnote at end of table.
TABLE I—Continued
Gas‘Tube Inhibition
Results (p.p.m.)
Aa 1‘
An 3'
XII ________ __ p-bromophenaeyl bromide" Br®—-C~CH:Br
XIII _______ ._ m-chlorophenaeyl chloride; . <:>—G~CH,OI
10-25 _
XIV ....... ._
a-ehloroacetophenone ..... -l
XV ________ __
2,4-dich1oroacetophenone._._. ‘ C1
1 Aa=Aer0bacter aeroge'nes.
? An=Asperaillus m'ger.
2;‘ The. method‘of claim 1‘ where the ‘halogenated'ket'one
Inhibition, I
Comp. No.
I 1% Brlne-
lias ‘ the - formula:
.10% Brine.
Jig-Emil .
where R and'R’ from the group consisting of hydrogen,
halogen, and methyl groups, R" is a lower alkyl group,
x is an integer from zero to three, y is an integer from
Table I showsthe halogenated ketones to-beextremely 35 zero to-three,;and Hal is halogen, with the proviso that
effective in inhibiting the growth of bacteria and fungi.
the total number of carbon atoms contained in R, R’, and
This test strikingly indicates how effective these composi
R” and does not'cxceed ten and that there is at least one
tions are for the treatment of paper mill process waters.
occurrence of halogen in the molecule.
Such organisms as Aerobacter aerogenes and Aspergillus
3. The method of claim 1 where the halogenated
niger are frequently found in many'paper mill systems; 40 ketone is benzylacetone dichloride.
inhibition is accomplished using relatively minor amounts
4. The method of claim 1 where the halogenated
of the halogenated ketones.
ketone is. tx-ChIOITOrOL-PhGIIYIaCCtOHG.
Table II indicates the e?icacy of the compositions
5. The method of claim 1 where the halogenated
used in the practice of the invention to control sulfate
ketone is p-chlorophenacyl chloride.
reducing bacteria in the presence of concentrated brines.
6. The method of claim 1 where the halogenated
It is believed to be well known that most. commercial in
ketone. is vm-chlorophenacyl chloride.
hibitors are completely ineifective in controlling sulfate
. 7. A suspension comprising water which contains from
reducing bacteria when such bacteria grows in the pres
0.1% to 15% by weight of suspended cellulose ?bers and
ence of brines containing 3% or more of the dissolved
a biologicall'y-active~ amount of a halogenated ketone con
taining more than three carbon atoms but less than
The expressions, “microbiocidal agen ” or “microbio
cide,” as used herein is meant to include the killing and/ '
or inhibiting action of chemical substances on such micro
eighteencarbon atoms.
8. A suspension comprising water which contains from
0.1% to 15% by weight of suspended cellulose ?bers and
biologically-active amount of a halogenated ketone of
organisms as, ‘for instance, bacteria, fungi, algae, protozoa,
and the like.
55 the formula:
Having thus described the invention, it is claimed:
1. The method of controlling the growth and repro
duction of microorganisms which comprisesfeeding from
.5-500 parts per million of halogenated ketone of the
where R and R’ from the group consisting of alkyl, aryl,
alkaryl, aralkyl, and heterocyclic rings containing, in addi
tion to carbon, one of ‘the elements from the group con—
sisting of oxygen and sulfur with the proviso that the
total number of carbon atoms contained in R and R’
where R and R’ are from the group'consisting of, alkyl,
is'greater than two but‘less than seventeen, and that there
aryl, alkaryl, aralkyl, and heterocyclic rings containing, 65 is at least one halogen substituent contained in the mole
in addition to carbon, one element from the group con
sisting of oxygen and sulfur, with the proviso that the
9; The suspension. of: claim 8 where the halogenated
total number of carbon atoms contained in R and R’ is
ketone has the formula:
greater than two but less than seventeen, and that there
is at least one halogen substituent contained‘ in the mole 70
cule, said feeding being from a- supply source of. said
halogenated ketone into an aqueous industrial process
- til E R1
system containing bacteria from the group consisting of
where: R and R’ are. from the group consisting of hydro
Aerobacter aerogenes, Aspergillus-niger and Desulfo
75 gen, halogen and methyl groups, R" is a lower alkyl
group, x is an integer from zero to three, y is an integer
from zero to three and Hal is halogen with the proviso
13. The suspension of claim 8 where the halogenated
ketone'is rn-chlorophenacyl chloride.
that the total number of carbon atoms contained in R,
R’, and R" does not exceed ten and that there is at
least one occurrence of halogen in the molecule.
10. The suspension of claim 8 where the halogenated
References Clted m th' ?le of this patent
Peet ________________ __ July 28, 1931
ketone is benzylacetone dichloride.
11. The suspension of claim 8 where the halogenated
ketone is a-chloro-u-phenylacetone.
12. The suspension of claim 8 where the halogenated 10
ketone is p-chlorophenacyl chloride.
Weedon _____________ __ Jan. 11,
Rose et al _____________ __ July 27,
Meuli ______________ __ Aug. 13,
, Wojcik ______________ __ Sept. 23,
Rosher ______________ __ Aug. 25,
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