Note: Descriptions are shown in the official language in which they were submitted.
I
~ACKGROU~ OF THE INVENTION
Flailed of the Invention
This invention is concerned with the breaking an
resolution of oil-in-water (O/W) bituminous emulsions by
treatment with water soluble polyethers.
Description of the Related Art
A great volume of hydrocarbons exist in known
deposits of tar sands. These deposits occur at various
places, the Athabasca tar sands in Canada being an example.
The petroleum in a tar sand deposit is an asphaltic bitumen
of a highly viscous nature ranging from a liquid to a semi-
solid. These bituminous hydrocarbons are usually char-
acterized my being very viscous or even non-flowable under
reservoir conditions by the application of driving fluid
pressure.
Where surface mining is not feasible, the bitumen
must be recovered by rendering the tar material mobile in
situ and producing it through a well penetrating the tar
sand deposit. These in-situ methods of recovery include
thermal, both steam and in-situ combustion and solvent tech-
piques. Where steam or hot water methods are used, a probe
let results which aggravates the recovery of the bitumen.
The difficulty encountered is emulsions produced by the in-
situ operations. These emulsions are highly stable O/W Emil-
sons which are made even more stable by the usual presence of clays. Most liquid petroleum emulsions are water in-oil
(Wow? types. These normal W/O emulsions are broken by
methods known in the art. However, the bitumen emulsions
which are O/W types present a much different problem, and
the same emulsifiers used in W/O emulsions will not resolve
~2~5~
the O/W bitumen emulsions.
C. W. W. cowers, J. Caned. Petrol. Tech., 7 (2),
85-90 (196~) describes the uniqueness of emulsions encountered
yin the production of bitumen from tar sands.
U.S. Patent ~,396,499 discloses a emulsification
method utilizing polymers derived from diepoxides and
poly(alkyleneoxy) dominoes.
U.S. Patent 4,321,1~8 discloses a demulsiEication
method utilizing reaction products of poly(alkyleneoxy) glycols
with diisocyanates.
SUMMARY OF THE INVENTION
The invention is a method for recovering petroleum
from O/W bitumen emulsions by resolving or breaking (emulsify-
in) these emulsions by contacting the emulsions at a tempera-
lure of from between about 25 and 160C with water soluble
polyethers prepared by the acid- or base catalyzed reaction of
poly(ethyleneoxy) glycols of 2,000 to 10,000 molecular weight
having the structure
HO (CH2CH20) no
where n = about 40 to about 250 with 0.5-10 weight per cent
diepoxides of <600 molecular weight of the general structure
OH -CH-R'-CH-CH
O O
wherein R' is an aromatic or aliphatic group which may option-
ally contain ether groupings.
DESCRIPTION OF THY PREFERRED EMBODIMENTS
The reaction between the poly(ethyleneoxy) slycols
and the diepoxi~es above may take place either neat or in
inert solvent at temperatures ranging from about 20 to 200C,
preferably 60 to 150C, in the presence of catalysts; for
example, alkali metals, their hydroxides or alkoxides, or in
the presence of Lewis acid catalysts such as BF3 or Sneakily.
The water soluble products of these reactions are
characterized by the presence of substantial quantities (>20%)
of unrequited poly(ethyleneoxy~ glycols as well as higher
molecular weight polyether-containing polyols arising from
ring-opening reactions of the epoxy functionalities with
alcohol groups.
The produced bitumen emulsions may be treated by
the process of our invention in a conventional manner, for
example, in a conventional horizontal treater operated, for
example, from about 25 to 160C and, preferably, from about
50 - 150C at autogenous pressures. The concentration of
the chemical emulsifier described above used in treating
the bitumen in water emulsions may range from about 1 to 200
parts per million and, preferably, from about 30 to 150 parts
per million with the optional addition of an organic delineate
and/or inorganic salt as well as standard flocculent and
mechanical or electrical means of emulsification. The
following examples describe more fully the present process.
However, these examples are given for illustration and are
not intended to limit the invention.
I
E X A M P L E
-
ADDITION OF D.IEPOXIDE TO PUG
Charged a 1-liter resin flask with 200g of a 2,900
molecular weight poly(ethyleneoxy) glycol and 0.5g potassium
hydroxide. The mixture was mechanically stirred at 1 mm Hug
pressure at 100C for one-half hour, nitrogen purged, cooled
to 70C and treated with 10.3g EGO ~28 (commercial dimly-
swaddle ether of Bisphenol A). The mixture was heated under
nitrogen to 120C o'er 15 minutes with good agitation and
maintained at this temperature for 2 hours. Liquid cremate-
graphic analysis of the product on a Toy Soda column showed
peaks at approximately 2,800, 40,000 and 100,000 molecular
weight with a MN of 4,000 and of 17,000.
E X A M P L E II
ADDITION OF EXCESS DIEPOXIDE TO PUG
The procedure of Example I was repeated using 14g
EON 828 (7 wt.%). The product was a water insoluble gel.
This demonstrates that for each poly(ethyleneoxy) glycol
utilized, there exists an upper limit to the amount of dip
epoxide that can be added and still obtain a water soluble
product.
*PEG is poly(ethyleneoxy) glycol. The number following is
the molecular weight.
--4--
~l2~5 ()~
E X A M P L E III
ADDITION OF EON 828 TO PEG-7500
-
The general procedure of Example I was repeated
using (a) PEG-7500 in place of PEG-2900, (b) 7g of EON ~28,
and (c) a reaction temperature raised from 70C to 115C
over a period of 45 minutes. At 115C the reaction was
quenched by addition of 400g of water. Insoluble gel part-
ales were removed, leaving a clear product solution. Liquid
chromatographic analysis showed the product to have Milwaukee-
far weight peaks at approximately 8,000 (80 vol.%) and
~100,000 (20 vol.%) with = 4,280 and = 26,380.
E X A M P L E IV
ADDITION OF EON 828 TO PEG-1450
The general procedure of Example I was repeated
using (a) PEG-1450 in place of PEG-2900, (b) 10g EON 828,
I reaction time of one-half hour at 120C, and (d) final
quenching of reaction by addition of 200g of water. Liquid
chromatographic analysis of the product showed peaks at
approximately 1,650 and 13,000 molecular weight with =
1,450 and = 2,100.
-- 30
~%~
E X A M P L E V
ADDITION OF DIEPOXYOCT~NE TO PEG-7500
.. .. .. .. .. . .. .. . ..
A 1-liter resin flask was charged with 200g of
PEG-7500 and 0.3g KOCH and vacuum stripped at 100C for one-
half hour. To this stirred solution under nitrogen were added5.5g of 1,2,7,8-diepoxyoctane at 100C over 15 minutes. The
mixture was maintained at this temperature for an additional
one and one-half hours followed by quenching with 250g of
water.
E X A M P L E VI
ADDITION OF EON 828 TO JEFF OX FF-200
The general method of Example I was used to add 2
wt.% EON 828 to a 10,000 molecular weight mixed 75 wt.%
ethylene oxide wt.% propylene oxide dill.
E X A M P L E VII
EMULSIFIER TESTING
The following basic testing procedure was employed:
a. A 1 weight per cent aqueous solution of
each chemical was prepared.
b. A 30 ml PYREX test tube equipped with
screw top was charged with 23 ml Emil
soon of 11.5 weight per cent bitumen
content obtained by in-situ steam flood-
in in tar sand pattern located at Ft.
McMurray, Alberta, Canada.
c. 2 ml Wizard Lake crude oil was added as
delineate and the contents of the test
tube were mixed.
d. The contents of the test tube were equal-
- 30 brazed in a 80C oven for 1-2 hours and
mixed again.
sly
en Chemical was added to the hot, dilute
emulsion at the following concentrations:
60, 120 ppm.
f. Contents of the test tubes were mixed,
recalibrated in an oven at 80C for
1 hour and mixed again.
go After 20 hours of standing at 80~C,
measurements were made on the volume of
top and middle layers, and the appear-
ante of the ago phase was noted.
Samples of some top layers were care-
fully removed by pupating and sub-
jetted to Karl-Fischer analysis for
determination of the water content.
I Results of the testing are summarized in the follow-
in table. Emulsion quality varied greatly from run to run
so in each case comparison is made to a run with identical
emulsion using POLYOX~ WISER [4 million molecular weight
poly(ethyleneoxy) glycol], a known emulsion breaker.
Successful examples are given of products derived
from PEG's of 2900 to 7500 molecular weight (a and c, no-
spectively) and from both aromatic and aliphatic diepoxides
(a and c, and i, respectively).
Negative examples are given showing the relative
ineffectiveness of products prepared from (1) low molecular
weight Pus (f) and from polyols containing propyleneoxy
groups in addition to ethyleneoxy groups (Q).
- 30
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