PROCESSES FOR RECYCLING SAG-D PROCESS WATER AND CLEANING DRILL CUTTINGS

Abstract

A method of treating slop oil and slops from the SAG-D (steam assisted gravity-drainage) very heavy oil-bitumen crude oil production in such locations as Alberta and Saskatchewan provinces in Canada, Russia, Venezuela, Saudi Arabia, and Kern County, Calif., involves mixing the slop oil and slops with chemicals to help separate out water from the slop oil and slops.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

Priority of U.S. Provisional Patent Application No. 61/101,538, filed 30 Sep. 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 A1; PCT International Publication Number WO 2006/012622 A2; U.S. Pat. No. 6,322,621 B1, U.S. Pat. No. 6,783,582 B2, U.S. Pat. No. 7,449,429, and published patent application Pub. No. US 2005/0193923 A1.

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.

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:

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 0.90/0.10. 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 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:

FIG. 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 50-70 degrees 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;

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 # 1.0. 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 0.225 ml (750 P.P.M. (750 parts of Malcera 508MM per million parts of slop oil) of Malcera 508MM and 0.9 ml (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, 300 ml 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.
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 A1 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 U.S. Pat. No. 6,322,621 B1,U.S. Pat. No. 6,783,582 B2 and, US patent application Pub. No. US2005/0193923 A1.

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

1.) Test #1

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 (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 a completely 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 that on standing fell to the bottom and also formed a layer between the water and the oil (Bitumen-Diesel blend).
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.

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 200 ml.

The final mixture was put through a centrifuge at Triflo, a company in Conroe, Tex., US that designs mechanical separation systems.

The present inventor found the following results:

Water=120 ml (60%);

Solids=20 ml (10%);

Oil=60 ml (30%).

What's most interesting in this separation is that the oil tied up in the solids can be 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 500 ml.

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).

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 FIG. 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 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 C.). 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 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 than 185 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 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 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 than 150 and not higher than 185 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 than 185 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 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 than 150 and not higher than 185 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.

A1000 is preferably a blend of citric acid and water, though it could include other acids as mentioned in the specification of my U.S. Pat. No. 6,783,582. The amount of citric acid in A1000 is preferably 25-60%, and the amount of water in A1000 is preferably 75-40%. A1000 is most preferably a blend of 50% citric acid and 50% water.

505-SD is preferably as described in the specification of my U.S. Pat. No. 6,783,582 (and more preferably as described in column 8, line 55 through column 9, line 64 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, and 0.5-3.0% non-ionic surfactants. 508MM is most preferably about 49% KP140 (TBEP), about 49% vegetable oil, and about 2% non-ionic surfactants.

Acceptable alternatives to A1000 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 A1000 or alternatives can be for example 10-70% (or to the limit of solubility of the acid in water).

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.

Claims

1. A method of recovering water from SAG-D slop oil comprising:

mixing a first quantity of water with a first quantity of a chemical blend to create a water/chemical mixture, the chemical blend comprising: (i) Malcera 508MM and Malcera 1507A (ii) acceptable alternatives to Malcera 508MM and Malcera 1507A mentioned herein (iii) Malcera 508MM and acceptable alternatives to Malcera 1507A mentioned herein or (iv) acceptable alternatives to Malcera 508MM mentioned herein and Malcera 1507A;

heating and stirring the water/chemical mixture;

adding to the mixture SAG-D slop oil create a water/chemical/slop oil mixture;

heating the water/chemical/slop oil mixture; and

separating individually the water, the oil, and solids from the water/chemical/slop oil mixture.

2. The method of claim 1, wherein the water/chemical mixture is heated and stirred for at least 10 minutes and the water/chemical/slop oil mixture is heated for at least 30 minutes.

3. The method of claim 1, wherein the water/chemical mixture is heated and stirred until the mixture reaches about 50-70 degrees C. and the water/chemical/slop oil mixture is heated until the mixture reaches about 50-100 degrees C.

4. The method of claim 1, wherein the water/chemical mixture is heated and stirred for about 10-30 minutes and the water/chemical/slop oil mixture is heated for about 30-60 minutes.

5. The method of claim 1, wherein the solids 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.

6. The method of claim 5, wherein on standing for a period of time the layer of clays falls to the bottom.

7. The method of claim 5, wherein on standing for 60-240 minutes the layer of clays falls to the bottom.

8. The method of claim 5, wherein on standing for 60-120 minutes the layer of clays falls to the bottom.

9. The method of any prior claim, wherein the chemical blend comprises Malcera 508MM and Malcera 1507A.

10. The method of claim 9, wherein the chemical blend comprises at least 0.010% Malcera 508MM and at least 0.03% Malcera 1507A.

11. The method of claim 9, wherein the chemical blend comprises 0.010-0.25% Malcera 508MM and 0.030-0.5% Malcera 1507A.

12. The method of claim 9, wherein the chemical blend comprises 0.050-0.25% Malcera 508MM and 0.10-0.50% Malcera 1507A.

13. The method of claim 9, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM and 0.25-0.40% Malcera 1507A.

14. The method of claim 9, wherein the chemical blend comprises about 0.1% Malcera 508MM and about 0.3% Malcera 1507A.

15. The method of any one of claims 1-8, wherein the chemical blend comprises acceptable alternatives to Malcera 508MM and Malcera 1507A mentioned herein.

16. The method of claim 15, wherein the chemical blend comprises 0.010-0.50% Malcera 508MM alternative and 0.03-0.50% Malcera 1507A alternative.

17. The method of claim 15, wherein the chemical blend comprises 0.05-0.25% Malcera 508MM alternative and 0.1-0.5% Malcera 1507A alternative.

18. The method of claim 15, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM alternative and 0.25-0.4% Malcera 1507A alternative.

19. The method of claim 15, wherein the chemical blend comprises about 0.1% Malcera 508MM alternative and about 0.3% Malcera 1507A alternative.

20. The method of any one of claims 15-19, wherein the Malcera 508MM alternative comprises a blend of KP140 (TBEP), non-ionic surfactants, and esterified vegetable oils, e.g. methyl and higher alcohol esters of soy bean, corn, or other vegetable oils.

21. A process for cleaning drill cuttings comprising:

to a first quantity of OBDC containing solids and oil adding 0.05-3.0% by volume 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 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 than 185 degrees F. (66-85 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,

the first chemical blend comprises at least one blend from the group consisting of Malcera 508MM and a Malcera 508MM alternative, and the second chemical blend comprises at least one blend from the group consisting of Malcera 1507A and a Malcera 1507A alternative.

22. The process of claim 21, wherein about 2.0% of the first chemical blend is used and about 2.0% of the second chemical blend is used.

23. A process for cleaning drill cuttings comprising:

to a first quantity of OBDC containing solids and oil adding 0.05-3.0% by volume 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 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 than 185 degrees F. (66-85 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,

the first chemical blend comprises at least one blend from the group consisting of Malcera 508MM and a Malcera 508MM alternative, and the second chemical blend comprises at least one blend from the group consisting of Malcera 1507A and a Malcera 1507A alternative.

24. The process of claim 23, wherein about 2.0% of the first chemical blend is used and about 6.0% of the second chemical blend is used.

25. A process for cleaning drill cuttings comprising:

to a first quantity of OBDC containing solids and oil adding 0.05-3.0% by volume 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 about one to five times as much as the first chemical blend 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 than 185 degrees F. (66-85 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,

the first chemical blend comprises at least one blend from the group consisting of Malcera 508MM and a Malcera 508MM alternative, and the second chemical blend comprises at least one blend from the group consisting of Malcera 1507A and a Malcera 1507A alternative.

26. The process of claim 25, wherein about 2.0% of the first chemical blend is used.

27. The process of any one of claims 21-26, wherein on cooling down to room temperature, the solids begin to settle out by gravity and a top layer of oil looks very homogenous.

28. The process of any one of claims 21-27, wherein there are no lumps or rag layers present.

29. The process of any one of claims 21-28, wherein the solids are observed to be very white and greyish, indicating the complete absence of any heavy hydrocarbons such as asphaltenes or paraffins.

30. The process of any one of claims 21-29, wherein the first chemical blend comprises Malcera 508MM, and the second chemical blend comprises Malcera 1507A.

31. The process of any one of claims 21-30, wherein the first chemical blend comprises a Malcera 508MM alternative, and the second chemical blend comprises a Malcera 1507A alternative.

32. A method of recovering water from SAG-D slop oil comprising:

mixing a first quantity of water with a first quantity of a chemical blend to create a water/chemical mixture;

heating and stirring the water/chemical mixture for about 20-45 minutes until the mixture reaches about 50-70 degrees C.;

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 for about 30-60 minutes until the mixture reaches about 50-70 degrees C.;

ceasing stirring and allowing for the water to separate out, and for solids to separate out;

pumping the water off from the solids.

33. The method of claim 32, wherein the solids 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.

34. The method of claim 33, wherein on standing for 180-240 minutes the layer of clays falls to the bottom.

35. The method of any prior claim, wherein the chemical blend comprises Malcera 508MM and Malcera 1507A.

36. The method of claim 35, wherein the chemical blend comprises 0.05-0.25% Malcera 508MM and 0.1-0.5% Malcera 1507A.

37. The method of claim 35, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM and 0.25-0.4% Malcera 1507A.

38. The method of claim 35, wherein the chemical blend comprises about 0.1% Malcera 508MM and about 0.3% Malcera 1507A.

39. The method of any one of claims 32-34, wherein the chemical blend comprises acceptable alternatives to Malcera 508MM and Malcera 1507A mentioned herein.

40. The method of claim 39, wherein the chemical blend comprises 0.05-0.25% Malcera 508MM alternative and 0.1-0.5% Malcera 1507A alternative.

41. The method of claim 39, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM alternative and 0.25-0.4% Malcera 1507A alternative.

42. The method of claim 39, wherein the chemical blend comprises about 0.1% Malcera 508MM alternative and about 0.3% Malcera 1507A alternative.

43. The method of any one of claims 39-42, wherein the Malcera 508MM alternative comprises a blend of KP140 (TBEP), non-ionic surfactants, and esterified vegetable oils, e.g. methyl and higher alcohol esters of soy bean, corn, or other vegetable oils.

44. A process for cleaning drill cuttings comprising:

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 than 185 degrees F. (66-85 degrees C.);

allowing the diluent/OBDC/chemical mixture to cool down to room (ambient) temperature (about 70-90 degrees F. (21-32 degrees C.)).

45. A process for cleaning drill cuttings comprising:

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 than 185 degrees F. (66-85 degrees C.);

allowing the diluent/OBDC/chemical mixture to cool down to room (ambient) temperature (about 70-90 degrees F. (21-32 degrees C.)).

46. A process for cleaning drill cuttings comprising:

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 about one to five times as much as the first chemical blend 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 than 185 degrees F. (66-85 degrees C.);

allowing the diluent/OBDC/chemical mixture to cool down to room (ambient) temperature (about 70-90 degrees F. (21-32 degrees C.)).

47. The process of any one of claims 44-46, wherein on cooling down to room temperature, the solids begin to settle out by gravity and a top layer of oil looks very homogenous.

48. The process of any one of claims 44-47, wherein there are no lumps or rag layers present.

49. The process of any one of claims 44-48, wherein the solids are observed to be very white and greyish, indicating the complete absence of any heavy hydrocarbons such as asphaltenes or paraffins.

50. The process of any one of claims 44-49, wherein the first chemical blend comprises Malcera 508MM, and the second chemical blend comprises Malcera 1507A.

51. The process of any one of claims 44-50, wherein the first chemical blend comprises a Malcera 508MM alternative, and the second chemical blend comprises a Malcera 1507A alternative.

52. A method of recovering water from SAG-D slop oil comprising:

mixing a first quantity of water with a first quantity of a chemical blend to create a water/chemical mixture, the chemical blend comprising: (i) Malcera 508MM and Malcera 1507A (ii) acceptable alternatives to Malcera 508MM and Malcera 1507A mentioned herein (iii) Malcera 508MM and acceptable alternatives to Malcera 1507A mentioned herein or (iv) acceptable alternatives to Malcera 508MM mentioned herein and Malcera 1507A;

heating and stirring the water/chemical mixture;

injecting the water/chemical mixture into a feed line;

adding to the mixture SAG-D slop oil in the feed line to create a water/chemical/slop oil mixture;

heating the water/chemical/slop oil mixture; and

separating individually the water, the oil, and solids from the water/chemical/slop oil mixture.

53. The method of claim 52, wherein the SAG-D slop oil is passed through a screen filter before being added to the water/chemical mixture.

54. The method of claim 52, wherein the water, the oil, and the solids are separated using a centrifuge.

55. The method of claim 52, wherein the water and chemical blend are mixed in a mixing tank before entering the feed line.

56. The method of claim 52, wherein the SAG-D slop oil is in a heated feed tank before entering the feed line.

57. The method of claim 52, wherein the water/chemical/slop oil mixture is heated in a heat exchanger.

58. The method of claim 52, wherein the feed line is passed through a heat exchanger.

59. The method of claim 56, wherein the heated feed tank is about 150 cubic meter capacity.

60. The method of claim 52, wherein the SAG-D slop oil is heated until the mixture reaches about 85° C.

61. The method of claim 52, wherein the water/chemical/slop mixture is heated until the mixture reaches about 95-98° C.

62. The method of claim 52, wherein the water/chemical mixture is heated to until the mixture reaches about 60° C.

63. The method of claim 52, wherein as the water level of the chemical/water mixture goes down, the water level of the mixture was replenished by using a produced water that was previously separated.

64. The method of claim 52, wherein the water, the oil, and the solids are separated into three distinct components using a centrifuge.

65. The method of any one of claims 52-64, wherein the method is substantially continuous.

66. The method of any one of claims 52-64, wherein the method is continuous.

67. The method of claim 52, wherein the chemical blend comprises at least 0.010% Malcera 508MM and at least 0.03% Malcera 1507A.

68. The method of claim 52, wherein the chemical blend comprises 0.010-0.25% Malcera 508MM or Malcera 508MM alternative and 0.030-0.5% Malcera 1507A or Malcera 1507A alternative.

69. The method of claim 52, wherein the chemical blend comprises 0.050-0.25% Malcera 508MM or Malcera 508MM alternative and 0.10-0.50% Malcera 1507A or Malcera 1507A alternative.

70. The method of claim 52, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM or Malcera 508MM alternative and 0.25-0.40% Malcera 1507A or Malcera 1507A alternative.

71. A method of recovering water from SAG-D slop oil comprising:

mixing a first quantity of water with a first quantity of a chemical blend to create a water/chemical mixture, the chemical blend comprising: (i) Malcera 508MM and Malcera 1507A (ii) acceptable alternatives to Malcera 508MM and Malcera 1507A mentioned herein (iii) Malcera 508MM and acceptable alternatives to Malcera 1507A mentioned herein or (iv) acceptable alternatives to Malcera 508MM mentioned herein and Malcera 1507A;

heating and stirring the water/chemical mixture;

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;

ceasing stirring and allowing for the water to separate out, and for solids to separate out;

pumping the water off from the solids.

72. The method of claim 1, wherein the water/chemical mixture is heated and stirred for at least 10 minutes and the water/chemical/slop oil mixture is heated and stirred for at least 30 minutes.

73. The method of claim 1, wherein the water/chemical mixture is heated and stirred until the mixture reaches about 50-70 degrees C. and the water/chemical/slop oil mixture is heated and stirred until the mixture reaches about 50-100 degrees C.

74. The method of claim 1, wherein the water/chemical mixture is heated and stirred for about 10-30 minutes and the water/chemical/slop oil mixture is heated and stirred for about 30-60 minutes.

75. The method of claim 1, wherein the solids 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.

76. The method of claim 5, wherein on standing for a period of time the layer of clays falls to the bottom.

77. The method of claim 5, wherein on standing for 60-240 minutes the layer of clays falls to the bottom.

78. The method of claim 5, wherein on standing for 60-120 minutes the layer of clays falls to the bottom.

79. The method of any prior claim, wherein the chemical blend comprises Malcera 508MM and Malcera 1507A.

80. The method of claim 1, wherein the chemical blend comprises at least 0.010% Malcera 508MM and at least 0.03% Malcera 1507A.

81. The method of claim 1, wherein the chemical blend comprises 0.010-0.25% Malcera 508MM and 0.030-0.5% Malcera 1507A.

82. The method of claim 1, wherein the chemical blend comprises 0.050-0.25% Malcera 508MM and 0.10-0.50% Malcera 1507A.

83. The method of claim 1, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM and 0.25-0.40% Malcera 1507A.

84. The method of claim 1, wherein the chemical blend comprises about 0.1% Malcera 508MM and about 0.3% Malcera 1507A.

85. The method of any one of claims 1-8, wherein the chemical blend comprises acceptable alternatives to Malcera 508MM and Malcera 1507A mentioned herein.

86. The method of claim 15, wherein the chemical blend comprises 0.010-0.50% Malcera 508MM alternative and 0.03-0.50% Malcera 1507A alternative.

87. The method of claim 15, wherein the chemical blend comprises 0.05-0.25% Malcera 508MM alternative and 0.1-0.5% Malcera 1507A alternative.

88. The method of claim 15, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM alternative and 0.25-0.4% Malcera 1507A alternative.

89. The method of claim 15, wherein the chemical blend comprises about 0.1% Malcera 508MM alternative and about 0.3% Malcera 1507A alternative.

90. The method of any one of claims 15-19, wherein the Malcera 508MM alternative comprises a blend of KP140 (TBEP), non-ionic surfactants, and esterified vegetable oils, e.g. methyl and higher alcohol esters of soy bean, corn, or other vegetable oils.

91. The invention(s) substantially as shown and/or described herein.