Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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PATENT APPLICATION
Attorney Docket No. A07293US (99348.3)
PCT Attorney Docket No. A07293WO (99348.3W0)
TITLE OF THE INVENTION
PROCESSES FOR RECYCLING SAG-D PROCESS WATER AND
CLEANING DRILL CUTTINGS
INVENTOR: GOLDMAN, Gordon, K., Ph.D., a US citizen, of Metairie, LA, US.
ASSIGNEE: MALCERA, L.L.C., a Louisiana limited liability company, of 4804
Avron
Blvd., Metairie, LA, 70006, US.
CROSS-REFERENCE TO RELATED APPLICATIONS
Priority of US Provisional Patent Application Number 61/101,538, filed 30
September 2008, and incorporated herein by reference, is hereby claimed. This
is not a
continuation or continuation-in-part of any patent application.
All prior patents and patent applications naming me as an inventor are hereby
incorporated herein by reference, including the following:
Published US patent application: Pub. No.: US 2006/0035793 Al; PCT
International Publication Number WO 2006/012622 A2; Patent No. US 6,322,621
Bl,
Patent No. US 6,783,582 B2, Patent No. US 7,449,429, and published patent
application
Pub. No. US 2005/0193923 Al.
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR
DEVELOPMENT
Not applicable
REFERENCE TO A "MICROFICHE APPENDIX"
Not applicable
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to slop oil. More particularly, the present
invention
relates to a new process for treating slop oil and slops from the SAG-D (Steam
Assisted
Gravity-Drainage) very heavy oil-bitumen crude oil production in Alberta and
Saskatchewan provinces in Canada, Russia, Venezuela, Saudi Arabia, and Kern
County,
California.
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2. General Background of the Invention
Part I. Background.
In Northeastern Alberta, Canada, specifically areas such as Athabasca, Cold
Lake,
and Peace River, Canadian and multinational oil companies are investing in a
new
process for extracting very heavy oil aka bitumen (oil sands) from
underground. Whereas
in the past the Athabasca oil sands (tar sands) were extracted by above ground
mining
operations, the new approach is to inject steam, melt the very heavy oil
(bitumen) and
pump it out from the ground as an emulsion of very heavy oil (bitumen) and
water.
The new process is called SAG-D (Steam Assisted Gravity-Drainage).This term
is derived from the concept whereby the Very Heavy Oil (Bitumen) is injected
with
Steam at 250 degrees C.(Centigrade) and 200 psig pressure at a depth of 1000
meters
below ground through a 700 metres slitted steam pipe. The Steam heats the
Bitumen
causing the Bitumen to melt and at the same time the Steam rises to interface
and
condense into the Bitumen forming a very stable Water-Bitumen Emulsion. Five
metres
below the slitted steam injection pipe and horizontal to the steam injection
pipe there
exists a 700 metres slitted production well pipe. The exiting well pipe is
made up of slits
and the emulsion of heated Bitumen and condensed steam flow to the production
well,
assisted by gravity.
The Emulsion of Very Heavy Oil (Bitumen) and Water,flows out of the
production well into a series of tanks for conversion into a pipeline-spec
blend of water-
free petroleum hydrocarbons for transport to refineries in both Canada and the
United
States as well as for shipment overseas to refineries in the Far East (China
and Japan).
After the Emulsion of Bitumen and water flows out of the production well, the
Emulsion is passed through a series of knock out tanks whereby it is separated
from all of
the solids in the Bitumen strata layers under ground and reacted with low or
high flash
petroleum hydrocarbon blending fractions, such as Condensate, Naphtha,
Distillates
and/or Synthetic oils. After the recovered Bitumen is blended with the
hydrocarbon
blending stock, the final blend is passed through a series of skimmers to
reach a final
B.S.&W.of 0.5%. Any liquids above the 0.5 % B.S.&W. are passed on to the Slop
Oil
Tanks for storage to be followed by injection underground as oily waste water
and solids.
Water Recovery:
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Water Recovery (Recycle):
Since water is the major reactant in the SAG-D process, the recovery of water
is
very important. In the areas in Canada where the SAG-D process is being used
water is
not in large supply. Therefore the recovery and recycle of water from the slop
oil residues
is very important.
Normally slop oil represents about 1.0% of the produced Bitumen-Petroleum
Hydrocarbon pipeline spec blend that is shipped out of the production areas.
For
example, at the Foster Creek production site in the Athabasca Region of
Northwest
Alberta, where 10,000 metric tons of Bitumen blend are produced daily, the
slop oil
production is normally 100 metric tons. The slop oil produced at Foster Creek
has a water
content of 75 to 85 % and a solids content in the range of 15 to 25%. The
waste
Bitumen-Hydrocarbon blend that remains ranges from 2 to 3 %. Most of the
remaining
waste Bitumen-Hydrocarbon Blend ends up in the solids phase. The solids are a
mixture
of sand and natural clays.
The ratio of clays to sand is typically 0.90/0.1 O.The clays are very fine,
not dense,
and on separation tend to rise above the water layer.
The slop oil is normally in the form of an emulsion. This slop oil emulsion
aka rag
layer typically consists of water, solids, and oil (Bitumen-Hydrocarbon
blend). The key
to recovering the water for recycling to steam is a two step process.
Step 1) Treatment with specific chemicals that will break the emulsion into at
least two
layers, if not three.
Step 2) The physical separation of the water from the solids and heavy oil
(Bitumen-Blend).
BRIEF SUMMARY OF THE INVENTION
To properly treat this waste water and allow it be recycled, it is best to
break the
emulsion first, then mechanical separation can occur. The present invention
involves
breaking the emulsion.
The present invention includes a process for separating water and solids into
two
distinct layers for recycling water for steam production and waste solids
disposal.
The present inventor believes that the best method of mixing treatment
chemicals
and slop oil is to add slop oil to treatment chemicals, though the mixture
could take place
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in the opposite order. When water is used in the treatment, the present
inventor believes
that the best method of mixing treatment chemicals and slop oil is to add slop
oil to a
mixture of treatment chemicals and water, though the mixture could take place
in the
opposite order.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
For a further understanding of the nature, objects, and advantages of the
present
invention, reference should be had to the following detailed description, read
in
conjunction with the following drawings, wherein like reference numerals
denote like
elements and wherein:
Figure 1 is a schematic view of apparatus which can be used in a method of the
present invention.
DETAILED DESCRIPTION OF THE INVENTION
Water Recovery (Recycle) Invention:
The following disclosure describes a process methodology, whereby Slop Oil
generated as byproduct in the SAG-D Very Heavy Oil (Bitumen) production
process is
treated with select chemicals to separate and recover water, solids, and oil
from the slop
oil emulsion.
The process preferably involves the following steps:
mixing a first quantity of water with a first quantity of a first chemical
blend to
create a water/chemical mixture;
heating and stirring the water/chemical mixture (preferably for about 10-30
minutes until the mixture reaches about 50-70degrees C.) (while not preferred,
one could
heat first to the desired temperature, then stir);
adding to the mixture SAG-D slop oil to create a water/chemical/slop oil
mixture;
heating and stirring the water/chemical/slop oil mixture (preferably for about
30-
60 minutes until the mixture reaches about 50-100 degrees C.) (while not
preferred, one
could heat first to the desired temperature, then stir);
ceasing stirring and allowing for the water to separate out, and for the
solids to
separate out as two phases, one in the form of sand will fall to the bottom of
the beaker
and the other as clays will rise to form a layer of clays above the water; on
standing for
a period of time, such as about 60-240 minutes, the layer of clays falls to
the bottom;
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pumping the water off from the solids.
The first chemical blend preferably comprises Malcera 508MM and Malcera
1507A, though it could comprise the acceptable alternatives mentioned below.
Preferably,
the first chemical blend comprises at least 0.01% Malcera 508MM and at least
0.03%
Malcera 1507A. More preferably, the first chemical blend comprises 0.01-0.25 %
Malcera
508MM and 0.03-0.5% Malcera 1507A. Even more preferably, the first chemical
blend
comprises 0.075-0.12% Malcera 508MM and 0.25-0.4% Malcera 1507A. Most
preferably, the first chemical blend comprises about 0.1% Malcera 508MM and
about
0.3% Malcera 1507A.
Exemplar # 1Ø Slop Oil from Tank T-403 (Encana Integrated Foster Creek
Production Site).
Step 1) Into a 500 ml beaker is added 50 ml of water and 0.225m1(750
P.P.M.(750 parts
of Malcera 508MM per million parts of slop oil) of Malcera 508MM and 0.9m1
(3,000
P.P.M. of Malcera 1507A.
Step 2.) The mixture of chemicals and water is heated with stirring for a
period of 20 to
30 minutes or until the mixture reaches 60 degrees C. (140 degrees F.).
Step 3.) When the mixture reaches temperature, add to the beaker with
chemicals and
water, 300m1 of SAG-D slop oil with mixing and heating.
Step 4.) Allow the mixture of water, slop oil, and chemicals to mix and heat
for an
additional 1.0 hour.
Step 5.) At the end of the mixing period, turn off the stirrer and allow for
the water to
separate out. The solids will separate out as two phases, one in the form as
sand will fall
to the bottom of the beaker and the other as clays will rise to form a layer
above the water.
On standing overnight the layer of clays falls to the bottom.
Step 6.) The water is then pumped off the top from the solids.
Results of separation:
Starting with 300 ml of SAG-D Slop Oil from Foster Creek-Encana Integrated
(Athabasca Area - North Eastern Alberta) production site, the following
amounts of water
and solids (sands and clays) were recovered:
1) Water = 225 ml (75%).The water was observed to be clean.
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2) Solids = 75 ml (35%).The solids were a mixture of sand, clays, and heavy
oil mixed
into the clays. In this specific trial, very little free heavy oil was found
during the
separation. Any heavy oil that came out was bound to the solids.
The chemicals used in this disclosure, Malcera 508MM and 1507A, are described
below, and are the preferred chemicals for use in the process, though other
chemicals can
be used as described in the section below entitled Preferred Chemicals and
Alternative
Chemicals. 1) Malcera 508MM is described in US patent application:
Pub.No.:2006/0035793 Al and P.C.T.International Publication Number WO
2006/012622
A2. 2) Malcera 1507A is preferably a blend of A1000 (described below) and 505-
SD,
which is described in US patent No. 6,322,621 Bl,USPatent No.6,783,582 B2 and,
US
patent application Pub. No.US2005/0193923 Al.
Treatment of SAG-D Slop Oil samples.
The following are the results of the tests the present inventor performed on
samples from Tank T-403A
l.) Test #l
A mixture of 50 ml of water and 1500 P.P.M (0.3 ml) of Malcera 1507A and 500
P.P.M. (0.1 ml) of Malcera 508MM were mixed with a 200 ml sample of liquid
from the
bottle labeled T-403 A. The 200 ml sample (Slop Oil) was added to the beaker
with the
water and chemical in the same manner that was used at the Foster Creek lab.
The mixing
occurred at 60 degrees C. The 200 ml sample was taken from the top of the
bottle without
shaking the bottle. The result was a very good separation of water from the
mixture. The
top oil layer was very viscous and thick.
2.) Test #2
The container labeled T-403 A was shaken vigorously for 3 to 4 minutes. Test
#2
was performed on a 300 ml aliquot of Slop Oil in the following manner. To a
beaker
containing 300 ml of Slop Oil and heated to 60 degrees C was added a water
mixture of
1500 P.P.M. (0.45 ml) of 1507A and 500 P.P.M. (0.15 ml) of 508MM in 100 ml of
water. The mixture was allowed to stir at 60 degrees for a period of 1.0 hour.
At the end
of the 1.0 hr mixing period the stirring was stopped. The result was a mixture
of solids
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(sand and very fine brownish red clays),water, and a large very thick bitumen
oil layer.
The water recovered was less than that observed in test # 1.
Conclusion from test # 2 is that the preferred methodology to be used is the
method used at the Foster Creek lab (that is, the methodology used in test #1
whereby the
sample of slop oil is added to the mixture of water and chemicals).
3) Test #3
The bottle labeled T-403A was shaken vigorously for 5 minutes, so all of the
solids
on the bottom would be thoroughly distributed throughout the liquid and
acompletely
homogeneously representative sampling of tank-403A would be obtained. The
remaining
500 ml sample of Tank T-403A was added to a large beaker containing 200 ml of
water
plus 500 P.P.M. (0.25 ml) of Malcera 508MM and 4000 P.P.M. (2.0 ml) of Malcera
1507A.The beaker containing the Malcera chemicals plus water was kept at 60 to
65
degrees C with mixing as the 500 ml of Slop Oil was added slowly over a period
of 20
minutes. At the end of the addition of the Slop Oil to the water mixture, the
total mixture
was allowed to stir at 60 degrees C for period of 1.0 hr. During this time 50
ml of diesel
was added to help lower the viscosity of the bitumen layer and help in the
separation.
Diesel could be replaced with any other cutter or diluent blending stock such
as
condensate naphtha, or diesel. At the end of the mixing period the stirrer was
turned off
and the mixture was allowed to cool.
Result (very interesting):
Water recovered:
a.) 200 ml added for mixing chemicals.
b.) 350 ml from the 500 ml of Slop Oil (70%).
Oil (Bitumen-blend) deducting for added diesel:
a.) 75 ml of Bitumen from Slop Oil (15%).
Solids, Most interesting:
a.) 75 ml of Sand and Clay( 15%).
Sand layer was on the bottom layer (greyish white).
Clay was dispersed in the water as very, very finely dispersed solids thaton
standing fell
to the bottom and also formed a layer between the water and the oil (Bitumen-
Diesel
blend).
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Exemplar #2.0 Slop Oil from Tank T-702 (Encana Integrated Foster Creek
Production Site).
The present inventor treated a sample of slop oil from Tank T-702 and got a
very
good separation plus all of the water in the slop oil. The method used was the
exact same
method used at the onsite lab in Foster Creek (that is, slop oil was added to
the mixture
of water and chemicals).
The most interesting observations from this specific test are the following:
1.) After treating the slop oil sample from Tank T-702,the first thing that
occurred
when the stirrer was shut down, was that water started to separate and all of
the solids rose
to the top. The solid layer was a very fluffy and fine clay looking material.
The sand layer
settled to the bottom.
2.) On letting the sample sit for five days, all of the solids that had risen
to the top
settled to the bottom and the water was very clear and clean.
3.) In this sample no flocculant or diluent such as Diesel was mixed into the
original mixture.
4.) The temperature never exceeded 60 degrees C.
5.) The amounts of chemicals used were as follows: 2000 P.P.M. (0.3 ml) of
1507A and 800 P.P.M. (0.12 ml) of 508MM. The chemicals were mixed with 25 ml
of
water. A 150 ml sample of T702 slop oil was used.
6.) The observed solids content was close to 35% (at least in this sample). It
can
be a function of how long one shakes up the sample before treatment. Also no
oil
(Bitumen-Condensate) top layer was observed. But on standing the solids did
seem to
have a blackish oil color.
The present inventor received the following samples from Encana Integrated
facility in Foster Creek, Alberta, Canada:
1.) T-403-A, Slop Oil.
2.) Tank, T-701-D, looks like a concentrate of Rag Layer, is the skimmed oil
from
skim tank D at Encana Integrated facility in Foster Creek, Alberta, Canada.
3.) Tank, T-702, looks like a sample of Bitumen-Water Emulsion. It feels the
heaviest of all three samples. It is combination of skim oil from skim tank A
and oil
removal filter back wash oil/solids/water.
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The slop oil (T-403-A) is made up of the samples from T-701-D and T-702
All samples were treated as slop. These did not include rag layer sample, as
Foster
Creek does not make much rag layer these days.
At Foster Creek the present inventor mixed the 508MM and the 1507A with 500
ml of water, then mixed that mixture with a 500 ml sample of slop oil. He has
since tested
at 50 ml water plus chemicals. At this lower volume the recycle water for the
slop oil
process is greatly reduced, helping to lower processing costs.
The slop oil cannot be separated as is in a centrifuge. The slop oil emulsion
should
first be treated chemically to break out all of the solids, water, and oil.
Then a mechanical
method, such as a centrifuge, is needed to recover the heavy oil blend,
leaving the
remaining two phases to be treated either by gravity settling or by
centrifuge.
A big problem in separating the slop oil into three distinct layers is that
the specific
gravity of the water and the oil+clays are just to close. The only practical
non-mechanical
method to separate the three phases would be by adding a light hydrocarbon to
the
mixture, such as condensate or diesel. Economically this would not be
practical.
Therefore an inexpensive mechanical method is preferred.
A lab in Canada made an analysis and what they thought was solids was really
hydrocarbons, which is not surprising, as a chemical analysis of the Foster
Creek slop oil
is not as easy as one may think.
Carried out another test on Tank T-702.
The test was carried out in a manner very similar to the last sample except
the
inventor used a larger sample:
The inventor used 25 ml of water plus the same concentration of chemicals
(specifically, 0.3 ml of 1507A and 0.1 ml of 508MM). The sample of slop oil
was 200m1.
The final mixture was put through a centrifuge at Triflo, a company in Conroe,
TX, US
that designs mechanical separation systems.
The present inventor found the following results:
Water = 120m1(60%);
Solids = 20m1(10%);
Oil = 60m1(30%).
What's most interesting in this separation is that the oil tied up in the
solids can be
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separated with a centrifuge. The solids have a tan color which becomes black
when the
solids separate from the slop oil during the Emulsion Breaking process. The
oil looks
thin, but is very thick (bitumen). Thus it bonds to the clays.
From all of the testing, I have learned two things that treating the slop oil
from
SAG-D production is preferably a two-step process.
1.) Chemical method to break the slop oil emulsion.
2.) Followed by a mechanical separation method. So far the best method seems
to a
centrifuge to separate the top layer of heavy oil.
The bottom layers of water and solids are then separated by a two phase
centifuge. The
water is sent to a clarifier to clean out any remaining solids prior to reuse
as water for
steam production.
Another thing that I have learned from all of this testing with samples from
Foster
Creek is that the Malcera products 508MM and 1507A work extremely well in
breaking
the SAG-D slop oil emulsion.
Before one can employ any type of mechanical separation equipment, one must
first break the solids (clay-sand), water, and very heavy oil bitumen-
condensate emulsion.
This is because no equipment can break the emulsion and return clean water,
not even
with the use of a flocculant.
See also www.malcera.com and www.miss-maya-508.com, both incorporated
herein by reference.
Slop oil with a rag layer came from an A.P.I. separator at a B.P.Refinery in
Ohio.
The slop oil contained the following:
Oil= 10%.
Water = 50%.
solids = 40% (mainly coke and very fine silica from the refinery catalyst
support).
The slop oil was treated in the following manner:
The present inventor used the same methodology that he used in Foster Creek.
The chemicals were mixed in 50 ml of water instead of 500m1.
Mixing was performed at 50 degrees C. (125 degrees F.).
Chemicals used at the following concentrations:
Malcera 508MM= 400 P.P.M. (0.04 %) (0.1 ml).
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Malcera 1507A= 1,200 P.P.M. (0.12%) (0.3 ml).
Recovered 100% of the water and oil was recovered by diluting with diesel.
The slop oil and the rag layer at Foster Creek contains no coke, only
naturally
occurring clays and sands, so the chemicals and the process of the present
invention
should work more efficiently and more economically than slop oil from refinery
A.P.I.
separators.
Exemplar # 3 Continuous treatment of slop oil
A test with the Malcera chemical products (508 MM and 1507A) was performed
on slop oil from a SAG-D production site. The test was performed at a
hydrocarbon waste
treatment and recovery facility. The process consists of a large heated feed
tank feeding
the waste liquids into a high temperature heat exchanger. The liquid solid
mass leaving
the heat exchanger is fed to a centrifuge, which separates the mixture of oil,
water and
solids into three distinct and separate components. Prior to feeding the
liquid waste into
the high temperature heat exchanger, chemicals are injected into the feed line
pumping the
waste liquid mass from the heated feed tank (see Figure 1).
The tests with Malcera 508MM and 1507A utilizing the continuous waste
treatment and recovery system were performed in the following manner: The
waste slop
oil had the following analysis:
Feed waste slop oil:
B.S. &W - 88%
Solids - 18%
Interface (rag layer) - 32%
1.) Waste slop oil feed was pumped into the process feedline 12 from the
heated receiving
tank 11.
2.) Downline from the heated receiving tank is a screen filter 14. The purpose
of the
screen filter 14 is to collect all large solid particles from the feedline 12
that would get
trapped in the heat exchanger 15.
3.) Before the waste slop oil is fed to the high temperature heat exchanger
15, a system
16 for injecting chemicals is connected to the feedline. The injection feed
system 16 is
attached to a mixing tank 17 where chemicals are mixed with water and injected
into the
waste slop oil feedline 12. An initial chemical mixture of 1000 P.P.M. of
Malcera 1507A
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and 300 P.P.M. of Malcera 508MM were mixed with water in a mix tank 17
equipped
with a set of two vertical mixers 18 connected to two electrical motors 19.
The mixture
of chemicals and water was injected into the waste slop oil feedline 12. As
the water level
of the chemical water mixture went down, the water level of the mixture was
replenished
by using produced water that separated from the centrifuge 21. By utilizing
the process
production water as makeup water we were able to run the system at a lower
dosage of
chemicals, 168 P.P.M., Malcera 508MM and 250 P.P.M. Malcera 1507A, thereby
lowering the cost of chemicals used per cube (M.T.) of waste slop oil treated.
4.) After the waste slop oil feed is injected with the chemical mixture, the
feed is pumped
through a heat exchanger 15.
5.) The final mixture of waste slop oil and the chemical mixture in water are
pumped
from the heat exchanger 15 into a centrifuge 21, where the solids 22 (sand,
etc.), water 23,
and heavy oil (bitumen) 24 are separated into three distinct components.
Results of the continuous treatment and recovery system for the hydrocarbon
waste
streams were treated with the Malcera chemicals as follows:
1.) Water - B.S. & W. = 100% water, no oil, solids or interface
2.) Solids - clean enough to pass a filter paper test
3. Oil (Bitumen) - B.S. & W. = <1.0%, solids < 0.5%, interface < 0.5%
Drill Cuttings Invention
New Chemical Process for Treating Oil based Dilling Mud Cuttings and Invert
Oil
Drilling Muds.
Description of Process:
Background:
This disclosure describes a process whereby oil based drilling mud cuttings
(OBDC) (aka invert drill cuttings) are treated with a combination of specific
chemicals in
the presence of a hydrocarbon diluent at the temperatures between 150 to 185
degrees f
(66 to 85 degrees Q. resulting in the conversion of the solids (drill
cuttings) to a zero
discharge non-hazardous waste material and in the recovery of 100% of the
petroleum
hydrocarbons from the treated OBDC.
The importance of this invention is that it allows oil exploration companies
to
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dispose of their waste OBDC as a non-hazardous waste, resulting in a major
reduction in
their waste disposal costs. In one specific case, a large Energy Company that
is presently
paying over US$7.0 million in waste disposal costs can realize a savings of
over US$6.8
million by utilizing the chemical separation process described herein.
A preferred process of the present invention for cleaning drill cuttings
comprises:
to a first quantity of OBDC containing solids and oil adding 0.05-3.0 % by
volume
(e.g., 2.0 %) of a first chemical blend with stirring and heating to create a
mixture of
OBDC and chemical blend;
to this mixture adding with stirring and heating a quantity of diluent which
is
approximately the same as the first quantity and 0.05-3.0 % by volume (e.g.,
2.0 %) of a
second chemical blend to create a diluent/OBDC/chemical mixture;
stirring the diluent/OBDC/chemical mixture for a period of at least one hour
at a
temperature of not less than 150 and not higher thanl85 degrees F. (66 to 85
degrees C);
allowing the the diluent/OBDC/chemical mixture to cool down to room (ambient)
temperature (about 70-90 degrees F. (21-32 degrees C)), wherein on cooling
down to room
temperature, the solids begin to settle out by gravity and a top layer of oil
looks very
homogenous.
There are no lumps or rag layers present. The solids are observed to be very
white
and greyish, indicating the complete absence of any heavy hydrocarbons such as
asphaltenes or paraffins.
The first chemical blend preferably comprises Malcera 508MM, and the second
chemical blend preferably comprises Malcera 1507A, though they could comprise
the
acceptable alternatives mentioned below.
Process Description:
The process is further described by the following procedure:
Exemplar # 1.0:
Step 1.) Into a 1,500 ml beaker is placed 500 ml of a sample of OBDC from the
Chesapeake Energy Company Drilling operations in Eastern Arkansas. (Ref #
1.0).
Step 2.) To the sample of OBDC is added 10 ml (2.0 %) of Malcera 508MM with
stirring
and heating.
Step 3.) To the same beaker with the sample of OBDC and 508MM is added with
stirring
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and heating 500 ml of Diesel (high flash diluent or cutter stock) and 10 ml
(2.0 %) of
Malcera 1507A.
Step 4.) The mixture in the beaker is allowed to stir for a period of at least
one hour at a
temperature of not less thanl50 and not higher thanl85 degrees F (66 to 85
degrees C).
Step 5.) At the end of the one hour heating and mixing period, the heating and
stirring are
stopped and the mixture is allowed to cool down to room (ambient) temperature.
Step 6.). On cooling down to room temperature, the solids begin to settle out
by gravity
and the top layer of oil looks very homogenous. There are no lumps or rag
layers present.
The solids are observed to be very white and greyish, indicating the complete
absence of
any heavy hydrocarbons such as asphaltenes or paraffins.
Ref #1.0: The chemical analysis of the Chesapeake OBDC indicates that it
contains 85%
oil (of which 60% is crude oil and 40% is diesel; the crude oil is about 50%
asphaltenes
and 50% paraffins), and 15% solids (drill cuttings).
An even more preferred process of the present invention for cleaning drill
cuttings
comprises:
to a first quantity of OBDC containing solids and oil adding 0.05-3.0 % by
volume
(e.g., 2.0 %) of a first chemical blend with stirring and heating to create a
mixture of
OBDC and chemical blend;
to this mixture adding with stirring and heating a quantity of diluent which
is
approximately the same as the first quantity and 0.15-9.0 % by volume (e.g.,
6.0 %) of a
second chemical blend to create a diluent/OBDC/chemical mixture;
stirring the diluent/OBDC/chemical mixture for a period of at least one hour
at a
temperature of not less than 150 and not higher thanl 85 degrees F. (66 to 85
degrees C);
allowing the diluent/OBDC/chemical mixture to cool down to room (ambient)
temperature (about 70-90 degrees F. (21-32 degrees C)), wherein on cooling
down to room
temperature, the solids begin to settle out by gravity and a top layer of oil
looks very
homogenous.
There are no lumps or rag layers present. The solids are observed to be very
white
and greyish, indicating the complete absence of any heavy hydrocarbons such as
asphaltenes or paraffins.
The first chemical blend preferably comprises Malcera 508MM, and the second
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chemical blend preferably comprises Malcera 1507A, though they could comprise
the
acceptable alternatives mentioned below.
Process Description:
The process is further described by the following procedure:
Exemplar # 1.0:
Step 1.) Into a 1,500 ml beaker is placed 500 ml of a sample of OBDC from the
Chesapeake Energy Company Drilling operations in Eastern Arkansas. (Ref #
1.0).
Step 2.) To the sample of OBDC is added 10 ml (2.0 %) of Malcera 508MM with
stirring
and heating.
Step 3.) To the same beaker with the sample of OBDC and 508MM is added with
stirring
and heating 500 ml of Diesel (high flash diluent or cutter stock) and 30 ml
(6.0 %) of
Malcera 1507A.
Step 4.) The mixture in the beaker is allowed to stir for a period of at least
one hour at a
temperature of not less thanl50 and not higher thanl85 degrees F (66-85
degrees C).
Step 5.) At the end of the one hour heating and mixing period, the heating and
stirring are
stopped and the mixture is allowed to cool down to room (ambient) temperature.
Step 6.). On cooling down to room temperature, the solids begin to settle out
by gravity
and the top layer of oil looks very homogenous. There are no lumps or rag
layers present.
The solids are observed to be very white and greyish, indicating the complete
absence of
any heavy hydrocarbons such as asphaltenes or paraffins.
Ref #1.0: The chemical analysis of the Chesapeake OBDC indicates that it
contains 85%
oil (of which 60% is crude oil and 40% is diesel; the crude oil is about 50%
asphaltenes
and 50% paraffins), and 15% solids (drill cuttings).
In a preferred process of the present invention for cleaning drill cuttings,
the
amount of Malcera 1507A is 1-5 times, and preferably about 3 times, the amount
of
Malcera 508MM
Preferred Chemicals and Alternative Chemicals:
1507A is preferably a blend of A1000 and 505-SD. The amount of A1000 in
1507A is preferably 40-70%, and the amount of 505-SD in 1507A is preferably 60-
30%.
1507A is most preferably a blend of 65% A1000 and 35% 505-SD.
A 1000 is preferably a blend of citric acid and water, though it could include
other
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acids as mentioned in the specification of my US Patent No. 6,783,582. The
amount of
citric acid in Al 000 is preferably 25-60%, and the amount of water in Al 000
is preferably
75-40%. Al000 is most preferably a blend of 50% citric acid and 50% water.
505-SD is preferably as described in the specification of my US Patent No.
6,783,582 (and more preferably as described in column 8, line 55 through
column 9,
line64 thereof). Alternatives to 505-SD include a blend of alkyl sulfonates
(such as
benzenesulfonic acids blend), non-ionic surfactants (such as
polyetheralkenyols and other
surface reducing surfactants), butyl cellusolve (or any diethylene,
triethylene, or
tetraethylene glycol ether derivative, but preferably non-toxic), pine oil (or
any other
terpene derivative (such as d,limonene oil) or other naturally occurring non-
petroleum
source, such as d,limonene oil (such as oil from citrus rinds) or other
hydrocarbon
solubolizing oil such as derived from pine trees or derivatives of pine oil -
purity of the
pine oil is not critical), KP 140, polymer (dispersing and chelating agent -
such as a
copolymer of malaic acid and sulfonated polystyrene) and vegetable oil
(preferably
soybean oil due to price and availability or esterified vegetable oil or
animal-based oil,
such as lanolin or lard (such animal-based oils should be esterified) or a
synthetic oil such
as mineral oil or a polyester mineral oil or a petrochemical based mineral
oil)
508MM is preferably a blend of KP140 (TBEP), vegetable oil, and non-ionic
surfactants. The non-ionic surfactants component can comprise 0.5-3.0%
polyethylene
glycol non-ionic surfactant, 0.1-0.5 % fluoroalkyl polyethylene glycol
surfactant, and 0.1-
0.5% phosphate derivative of a polyethylene glycol surfactant; preferably they
comprise
about 80% polyethylene glycol non-ionic surfactant, about 10% fluoroalkyl
polyethylene
glycol surfactant, and about 10% phosphate derivative of a polyethylene glycol
surfactant.
508MM is preferably a blend of 1.5-98% KP140 (TBEP), 98.0-1.5% vegetable oil,
and0.5-3.0% non-ionic surfactants. 508MM is most preferably about 49% KP140
(TBEP), about 49% vegetable oil, and about 2% non-ionic surfactants .
Acceptable alternatives to Al000 include glutaric acid, tannic acid, formic
acid,
oxalic acid, alkyl benzene sulfonic acids, and their derivatives and mixtures
thereof (or
any organic acid that has a pH in the range of 2-4) (or a non-corrosive
inorganic acid -
such as phosphoric acid or sulfamic acid). The percentages of acid to water in
Al000 or
alternatives can be for example 10-70% (or to the limit of solubility of the
acid in water).
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Acceptable alternatives to 505-SD include mixtures of TBEP or butyl cellosolve
with modified surfactant mixtures of mono, di, tri, and tetra glycol ethers
and/or esterified
organic acid solvents, e.g., esterified derivatives of glutaric acid.
Acceptable alternatives to 508MM include a blend of KP140 (TBEP), non-ionic
surfactants, and esterified vegetable oils, e.g. methyl and higher alcohol
esters of soybean,
corn, or other vegetable oils.
All measurements disclosed herein are at standard temperature and pressure, at
sea
level on Earth, unless indicated otherwise.
The foregoing embodiments are presented by way of example only; the scope of
the present invention is to be limited only by the following claims.
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