Patented Sept.

15, ;'l_:_931_

1,823,440

UNITED STATES

PATENT OFFICE

MELVIN DE GROOTE, OF ST. LOUIS, AND LOUIS '1. MONSON, OF MAPLEWOOD, MISSOURI,
ASSIGNORS, BY, MESNE ASSIGNMENTS, T0 TRETOLITE COMPANY, OF WEBSTER
GROVES, MISSOURI, A CORPORATION OF MISSOURI

FLOODING PROCESS FOR RECOVERIN G FIXED OIL FROM SUBTERRANEAN OIL BEARING
STRATA

No Drawing.

Application ?led March 3, 1930. Serial No. 432,972.

This invention relates to the recovery of mercially feasible, if the oil sand with its en
oil from subterranean oil sands and other oil casement of oil is washed with an aqueous
bearing strata, and has for its main object to treating solution that contains or comprises
provide a practicable, inexpensive process for wood sul?te liquor. The same procedure
5

recovering oil that is held by adsorption on that is used in the ordinary ?ooding process

55

' subterranean oil sands, such, for example, as for reworking abandoned oil ?elds can be em
the sands of exhausted oil ?elds, or the sands ployed to bring the treating solution into con- of oil ?elds that have been tested and aban tact with thesand, due to the fact that the
doned, because they did not-contain a su?i treating solution is of such a nature or char
10 cient quantity of oil to make it commercially acter that it will flush the ?lm of oil off the
60
feasible to attempt to recover the oil by con sand. The liberated oil, after passing

ventional oil-producing methods.

through the sand bed, can be conducted to

Brie?y described, our process consists in the surface of the ground or recovered by any

introducing an aqueous treating solution suitable or conventional method used to pro

containing wood sul?te liquor into a number duce oil.

of oil wells that have ceased to be productive,
Wood sul?te liquor, suitable for use in our

20

and permitting said treating solution to

travel through the oil sand and rise through
a predetermined opening, the treating solu
tion operating to liberate the ?lm or coating
of oil on the particles of sand, and to ?ush

65

process, is easy to obtain and can be produced

or obtained at a relatively low cost. One
available source of supply for such substances
or materials is the liquor that is obtained as a 70

25

waste product in the manufacture of paper

stock by the sul?te process, which sul?te proc
ess, as is well known, consists of cooking wood
chips under pressure in a digester with bisul
?te liquor or bisul?te acid. This bisul?te liq 75
uor or bisul?te acid is obtained by the oxidation of sulfur and subsequent reaction with
particles of sand, and which is commonly milk of lime prepared from a limestone, pref

30

particles of sand. Free oil can be recovered said cooking operation produces a mixture of

the oil off the particles of sand and carry the

oil upwardly to the surface of the ground.
'Oil exists in oil sands in two different
states, i. e., as free oil, that is located in the
voids between the particles of sand, and as
?xed oil, which is held by adsorption on the

referred to as a ?lm of oil that adheres to the

erably calcium-magnesium limestone. The

by the conventional methods of producing wood pulp and an acid wood sul?te liquor.
oil, such as draining the oil in conjunction Subsequently, said mixture is subjected to

80

with liquid or gaseous pressure, or creating treatment so as to separate and recover the
an arti?cial ?uid or gaseous pressure in the wood pulp from the wood sul?te liquor.

An

as, sand bed, so as to dislodge and expel the oil other example of wood sul?te liquor or liquor 85
from the sand bed into the well, and then extract, suitable for use in our process, can
conduct the oil to the surface of the ground be produced or obtained as the direct product
by any suitable means or method. Fixed or principal product of a process consisting
oil. i. e., the coating or ?lm of oil on the sand, of cooking inferior woods not suitable or
cannot be recovered by any of the conven practicable for use in the manufacture of pa 90
tional methods used to produce oil, because per stock with bisul?te liquor or bisul?te acid
it is held as a ?lm surrounding the grains of the kind mentioned, and then recovering
of sand and cannot be dislodged from the the wood sul?te liquor from the unsuitable
sand grains either by ?uid or gaseous pres wood pulp which constitutes the waste prod
sure.
uct of the process. the cooking operation be 95
We have discovered that ?xed oil, i. e., ing carried on under pressure in a digester or
oil that is held in the form of a ?lm by ad other suitable apparatus.
sorption on subterranean oil sands and other
The state, form, or condition of the wood
oil-bearing strata, can be recovered at a sul? sul?te liquor at the time it is mixed with
ciently low cost to make the operation com~ water so as to produce an aqueous treating , 100

1,823,440

other substances known to have similar pow

solution suitable for use in our process, is

such, for example, as propylated nap immaterial. Said wood sul?te liquor may be ers,
thalene
sulfonic acid and its salts.
used in its natural state, as it comes from the
One highly desirable characteristic of an
digester, i. e., in a more or less dilute acid

treating solution containing wood

state; but we prefer to neutralize it prior to aqueous
sul?te
liquor,
which permits it to be used
use in our process, so that the oil recovered

oils and on oils as

by the process will not have a destructive both on Pennsylvania
is that the products of the ,
phaltic
in
nature,
corrosive action on the pipe lines, tank cars, reaction between the reagent and hard water
or storage tanks in which said oil is sub

water-soluble, and therefore,

sequently con?ned. One simple and ei?cient are usually
is no possibility of a precipitate being
method of accomplishing the neutralization there
formed that will clog the oil'sand and ob
of the wood sul?te liquor is to treat it with

or impede the ?ow of the wash water

caustic soda, caustic potash, ammonium hy struct
and the oil liberated from the particles of
droxide, megnesium oxide, calcium oxide,

sand by the action of the reagent of the

80

calcium carbonate, or any other suitable treating solution.

'
oxide, hydroxide, or carbonate, of any alkali
The principal advantages of our process
forming metal.
are that it will not clog the oil sand on which
In order to reduce the expense of trans the process is employed; it will e?ect the re
porting the wood sul?te liquor to the point covery from abandoned sand beds of oil that
where it is to be used to recover oil from sub contains appreciable quantities of asphaltic
terranean oil sands or other oil-bearing strata, or similar material; and the process is vin

85

said liquor may be concentrated, for example,

to practise to carry out, since wood
to a speci?c gravity of approximately 30 expensive
sul?te liquor is commonly obtained as a by
to 32 Baum. It may even be desiccated
further, in which case it becomes a. brown

product.

90

practising our process, we prefer to use

powder. As herein used, the term wood a In
of 'about'vl'barrel of treating agent
sul?te liquor is intended to mean essentially onratio
the anhydrous basis to 1,000 barrels of
the solid active material and not to include

?ushing water, but in some instances a ratio

the inactive water, which is a diluent or of l to 20,000, or even 1 to 40,000 may be
vehicle only. However, we wish it to be used. The amount of solution employed

understood that by the term above quoted may be equal to the amount of recovered oil,
we intend to include the concentrated liquor, or it may be many times greater. The water
and even the anhydrous solid, and also the may be cold or preheated, if desired. The
unneutralized material and the product or actual mechanical practice is well known
material obtained by neutralizing the acid and we prefer to use the same apparatus that
material with the conventional bases, such has been used in the Pennsylvaniaoil ?elds

as calicum oxide or magnesium oxide, as well to practise the ?ooding process, or any modi
as soda, potash and ammonia.
'
?cations or variations of such an apparatus.

One speci?c example of wood sul?te liquor

40

Having thus described our invention, what

a substance having approximately the fol ters Patent is:

lowing composition:
1. A ?ooding process for recovering ?xed
Speci?c gravity ________ _-__-_ 302 Baum oil from subterranean oil sands and other
Ash ______________________ __

Lime (CaO) ______________ __

Magnesia (MgO) _________ __

6.59%

oil-bearing strata, which consists in washing

1.32%
1.54%

110

2. A ?ooding process for recovering xed

oil from substerranean oil sands and other oil

Soluble solids _____________ __ 51.03%

bearing strata, which consists in washing the

50 Non-tannin _______________ __ 28.80%

sand or stratum with an aqueous treating

115

solution containing: wood sul?te liquor in

l'ltannin ___________________ __ 22.23%

which the metallic base is derived from an

Tannin purity _____________ __ 43.54%

alkali-forming metal.

'

Such material may be used in any conven

3. A ?ooding process for recovering ?xed 12c.
ient strength. dissolved in any kind of water. ' oil from subterranean oil sands and other oil; .
in which it will make a solution substantially
strata, which consists 1nv washing. free from precipitates. It has the desirable bearing
the sand or stratum with an aqueous treat;
characteristic of being capable of dissolving

ing solution, containing wood sul?te liquor

in hard or salty water, or in hard saltywater obtained by' neutralization with a basic jcal
almost as readily asin soft or distilled water, cium compound.
and without undue precepitationg. . -

65

105

the sand or stratum with an aqueous treat

ing . solution containing wood sul?te 1i nor.

034%

Solids ____________________ __ 51.03%

60

100

or extract suitable for use in our process, is we claim as new and desire to secure by Let

45 Iron ___________________ ___.

55

95

'

Our broad idea contemplates the use of

wood sul?te liquor, as hereinde?ned, in any
condition or state. Said wood sul?te liquor
may be used alone, or .it may be used with

"12,5;

MELVIN DE GROOTE"

LOUIS T. MONSON. ?
130 V