Demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing

- MALCERA, L.L.C.

A demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing can also be used to treat slop oils and clean drill cuttings.

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Description
CROSS-REFERENCE TO RELATED APPLICATIONS

Priority of U.S. Provisional Patent Application Ser. No. 61/799,890, filed 15 Mar. 2013, incorporated herein by reference, is hereby claimed.

All prior patents and patent applications naming me as an inventor are hereby incorporated herein by reference, including the following:

Published U.S. patent applications: US20110174695 A1; US2006/0035793 A1; U.S.2005/0193923 A1; US2009/059046; US2005/26355; PCT International Publication Number WO2006/012622 A2; U.S. patent application Ser. No. 13/302,645; U.S. patent application Ser. No. 13/121,729; U.S. Pat. No. 6,322,621 B1; U.S. Pat. No. 6,783,582 B2; U.S. Pat. No. 7,449,429; and U.S. Pat. No. 8,063,004. However, this is not a continuation, continuation-in-part, or divisional of any prior patent application.

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 processing of fuel, and more particularly to dewatering agents for fuels and cleaning agents for drill cuttings and dewatering and dispersing agents for biofuels.

2. General Background of the Invention

Processing of fuel often involves adding to the fuel dewatering agents for fuels and dewatering and dispersing agents for biofuels. Cleaning agents are often used to clean drill cuttings.

BRIEF SUMMARY OF THE INVENTION

The present invention includes a composition which can be useful for cleaning drill cuttings, processing slop oil, and processing biofuels. The composition preferably includes a demulsifier, a co-additive for demulsifier, a solvent and coupling agent and antifoaming agent, a very powerful demulsifier, a solvent, a chelating dispersant, a surfactant, a fluorinated surfactant, and a dispersant which is an oil soluble and water dispersible anionic surfactant. Preferably there are as well multiple surfactant—degreasing agents (particularly when the composition is used to clean drill cuttings).

Preferably, the demulsifier is at least one from the group consisting of citric acid, acetic acid, ascorbic, formic, other carboxylic acids, sulphamic acid, phosphoric acid, sulfuric acid, and mixtures thereof, the co-additive for demulsifier is at least one from the group consisting of dodecyl benzene sulphonic acid, toluene sulphonic acid, toluene sulphonic acid, xylene sulphonic acid, and any other alkyl benzene sulphonic acid, and mixtures thereof, the solvent and coupling agent and antifoaming agent—hydrotrope is at least one from the group consisting of butyl cellosolve and any other preferably non-toxic alkyl glycol ether, and mixtures thereof,

the very powerful demulsifier is at least one from the group consisting of on the one hand diisopropylnaphthalenesulphonic acid (35-70%), sodium dodecylbenzenesulfonate (10-30%), 1,2,4-trimethylbenzene (5-15%), sulphuric acid (0.5-5%), xylene (0-3%), cumene (0-3%) and on the other hand other alkyl, di-alkyl, tri-alkyl napthlalene sulphonic acids, and mixtures thereof, the solvent is at least one from the group consisting of pine oil and any other terpene type of oil, and mixtures thereof, the chelating dispersant chelates Fe, Al, Ca from about 100 ppm to less than 10 ppm—moves Fe, Al, Ca from oil to water, and comprises an oil-water soluble copolymer of partially sulfonated, maleic anhydride and polystyrene, 25% active, the surfactant lowers surface tension and is at least one from the group consisting of alcohol ethoxylate and any other non-ionic ethoxylated surfactant, and mixtures thereof, the fluorinated surfactant lowers surface tension is at least one from the group consisting of on the one hand 40% fluorosurfactant, 30% isopropyl alcohol, and 30% water and on the other hand a Capstone fluorinated surfactant, such as Capstone N35 or Capstone N65-fluorinated surfactant, which are 25% active, so 4× the amount should be used, and mixtures thereof, the surfactant—degreasing agents are at least one from the group consisting of nonylphenol ethoxylate, POE-4, nonylphenol ethoxylate, POE-6, and nonylphenol ethoxylate, POE-8, and mixtures thereof, the dispersant is an oil soluble and water dispersible anionic surfactant which drops char content from around 2000 ppm to less than 10 ppm and is at least one from the group consisting of isopropylamine dodecyl benzene sulfonatesand other oil soluble and water dispersible anionic surfactants, including other isopropylamine dodecyl benzene sulfonates, and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

TABLE 1 A preferred formula for the composition (to be sold as Malcera 1507AK) of the present invention Col. 5 Col. 6 Col. 7 Col. 8 Col. 2 Col. 3 Col. 4 More Most Example Example B Col. 1 Function % by Preferred Preferred Preferred A % by Row Ingredient (Generic name) ((alternatives)) wt. % by wt. % by wt. % by wt. % by wt. wt. 1 Citric Acid demulsifier 30 to 90 40 to 80 45 to 75 50 to 70 59.04 60.5 50% (citric acid 50%/water50%) ((acetic acid, sorbic acid, formic acid, butyric acid, gluconic acid, valeric acid, 2-ethylbutyric acid, 2-ethylhexoic acid, propionic acid, iso pentanoic acid, benzoic acid, and other carboxylic acids; mineral acids, including nitric acid, phosphoric acid, and sulfuric acid; sulfonic acids, including DDBSA-Biosoft 101 and toluene sulfonic acid; fatty acids derived from vegetable oils, including mysistic, palmitic, stearic acid, oleic acid, linoleic acid, lauric acid, and linolenic acid; and mixtures thereof)) 2 Biosoft co-additive for demulsifier (dodecyl  3 to 30  5 to 25  5 to 20  5 to 15 5.4 15 101- benzene sulphonic acid) ((toluene sulphonic DDBSA acid or any other alkyl benzene sulphonic acid, such as toluene sulphonic acid, xylene sulphonic acid and mixtures thereof)) 3 butyl solvent and coupling agent and antifoaming 2 to 8 3 to 8 3.0 to 7.0 3.0 to 5.0 2.4 3.0 cellosolve agent - hydrotrope (butyl cellosolve, aka EB) ((any other alkyl glycol ether, preferably non-toxic)) 4 C-4100 very powerful demulsifier  3 to 25  5 to 20  7 to 15  9 to 12 10.0 9 (diisopropylnaphthalenesulphonic acid (35-70%), sodium dodecylbenzenesulfonate (10-30%), 1,2,4-trimethylbenzene (5-15%), sulphuric acid (0.5-5%), xylene (0-3%), cumene (0-3%)) ((other alkyl, di-alkyl, tri-alkyl napthlalene sulphonic acids)) 5 Pine Oil solvent (pine oil) ((any other terpene type 0.5 to 5   0.5 to 3.0 0.8 to 3.0 1.0 to 3.0 1.2 1.5 of oil)) 6 Versa-TL-4 chelating dispersant - chelates Fe, Al, Ca  1 to 12  2 to 10  2 to 8 2 to 6 5.7 6 from about 100 ppm to less than 10 ppm - moves Fe, Al, Ca from oil to water (an oil-water soluble copolymer of partially sulfonated, maleic anhydride and polystyrene, 25% active) ((Versa-TL-3 diluted with water to 25% active)) 7 Merpol SE surfactant - lowers surface tension (alcohol 0.5 to 3.0 0.5 to 2.5 0.5 to 2.0 0.5 to 1.5 1.1 1.0 ethoxylate) ((any other non-ionic ethoxylated surfactant)) 8 Zonyl FSN fluorinated surfactant - lowers surface 0.01 to 0.3  0.01 to 0.2  0.05 to 0.18 0.05 to 0.15 0.11 0.10 tension (40% fluorosurfactant, 30% isopropyl alcohol, and 30% water) ((or a Capstone fluorinated surfactant, such as Capstone N35 or Capstone N65fluorinated surfactant, which are 25% active, so 4X the amount should be used)) 9 Makon 4 surfactant - degreasing agent (nonylphenol 0.25 to 2.0  0.25 to 1.0  0.25 to 0.70 0.3 to 0.7 0.35 0.5 ethoxylate, POE-4) ((or other nonylphenol ethoxylates, such as Makon 6 or Makon 8)) 10 Makon 6 surfactant - degreasing agent (nonylphenol 0.25 to 2.0  0.25 to 1.0  0.25 to 0.70 0.3 to 0.7 0.35 0.5 ethoxylate, POE-6) ((or other nonylphenol ethoxylates, such as Makon 4 or Makon 8)) 11 Makon 8 surfactant - degreasing agent (nonylphenol 0.25 to 2.0  0.25 to 1.0  0.25 to 0.70 0.3 to 0.7 0.35 0.5 ethoxylate, POE-8) ((or other nonylphenol ethoxylates, such as Makon 4 or Makon 6)) 12 Biosoft N- dispersant - oil soluble and water 2.0 to 20  2.0 to 17  2.0 to 15   2.0 to 13.0 14.0 2.4 411 dispersible anionic surfactant - drops char content from around 2000 ppm to less than 10 ppm (isopropylamine dodecyl benzene sulfonates) ((other oil soluble and water dispersible anionic surfactants, including other isopropylamine dodecyl benzene sulfonates))

In the above table, POE is polyoxiethylene.

To make the Malcera 1507AK product, one blends as follows (with preferably constant stirring):

    • put the citric acid in a reactor at ambient temperature (typically around 25 Centigrade);
    • then add Biosoft101,
    • then add EB,
    • then add C-4100,
    • then add Pine Oil,
    • then slowly add Versa TL-4 until no foam is present,
    • then add Merpol SE,
    • then add Zonyl FSN,
    • then add Makon 4,
    • then add Makon 6,
    • then add Makon 8,
    • then add Biosoft N-411.
    • Then continue to stir for 4 hours at ambient temperature.

Preferably, the citric acid is always the first ingredient in the reactor. Preferably, EB, Biosoft 101, and C-4100 are added before Versa TL-4. After that, the ingredients can be added in any order. The goal is to keep all components properly blended without separation as the blending occurs.

However, it is possible to mix ingredients other than citric acid together, then add that mix while stirring to the citric acid (in such a case more EB might be needed).

Malcera sells the above product as Malcera 1507AK.

Malcera 1507AK (optionally without Makon 4, Makon 6, and Makon 8) (or a version with ingredients from columns 1 and or 2 of Table 1) can be used to treat slop oils and tank remnants or sludges to knock out water and to disperse the hydrocarbons into diluents, and to drop solids out of these products. This is usually performed at about 150-200 degrees F. and the concentration is usually 1,000-2,500 ppm.

Malcera 1507AK (or a version with ingredients from columns 1 and or 2 of Table 1) can be used to treat drill cuttings to reduce water content. This is usually performed at about 100 degrees C. and the concentration is usually 5,000-10,000 ppm. The drill cuttings are typically coated with oil based drilling mud emulstions.

Malcera 1507AK (optionally without Makon 4, Makon 6, and Makon 8, but preferably in approximately the amounts listed in column 7 of Table 1) (or a version with ingredients from columns 1 and or 2 of Table 1) can be used to reduce water content and solids content in a biofuels mixture made from the pyrolysis of wood to yield a very clean oil. This clean oil can then be hydrotreated to make gasoline and diesel. When used in a biofuels mixture, typically 500-1000 ppm of Malcera 1507AK is used in the biofuels mixture. The typical temperature is about 150 degrees F. Malcera 1507AK knocks out water so that less than 99.9% of the biofuels mixture is water. A desalter then takes out last up to 0.1% water. Another useful product is commercially available from Malcera as product 507AIG. 507AIG can include the following preferred ranges of components:

    • 508MM—15-30%
    • Diesel—5-20%
    • DDBSA—10-25%
    • 1507AK—balance 25-70%

In use, the doseage ranges could be as follows:

    • 1.) 508MM: 300 to 3,000 P.P.M. (of the material being treated)
    • 2.) 1507AK: 1,000 to 10,000 P.P.M. (of the material being treated)

Example 1 Column 7 of Table 2

    • 16.7% 508MM
    • 13.3% diesel (could be omitted with heat instead—about 170 degrees F. for a long period of time) (or any liquid petroleum hydrocarbon)
    • 20% of DDBSA
    • 50% 1507AK
    • Where 1507AK is 59.04% Citric Acid, 5.4% Biosoft 101-DDBSA, 2.4% butyl cellosolve, 10.0% C-4100, 1.2% Pine Oil, 5.7% Versa-TL-4, 1.1% Merpol SE, 0.11% Zonyl FSN, 0.35% Makon 4, 0.35% Makon 4, 0.35% Makon 4, 14.0% Biosoft N-411
    • Where 505MM is 49% KP140 (TBEP), 49% vegetable oil, 1.6% Merpol SE, 0.2% Merpol A, and 0.2% Zonyl FSN
    • So,
    • 29.52% Citric Acid, 2.7% Biosoft 101-DDBSA, 1.2% butyl cellosolve, 5.0% C-4100, 0.6% Pine Oil, 2.85% Versa-TL-4, 0.55% Merpol SE, 0.055% Zonyl FSN, 0.175% Makon 4, 0.175% Makon 4, 0.175% Makon 4, 7.0% Biosoft N-411 8.183% KP140 (TBEP), 8.183% vegetable oil, 0.2672% Merpol SE, 0.0334% Merpol A, and 0.0334% Zonyl FSN
    • 20% of DDBSA total—22.7%, Merpol SE total—0.8172%. Zonyl FSN Total—0.0884%
    • 13.3% diesel

Example 2 Column 8 of Table 2

    • 1.) Malcera 508MM=20%
    • 2.) Diesel=15%
    • 3.) DDBSA (Stepan Biosoft 101)=15%
    • 4.) Malcera 1507AK=50%
    • Total=100%
    • Where 1507AK is 59.04% Citric Acid, 5.4% Biosoft 101-DDBSA, 2.4% butyl cellosolve, 10.0% C-4100, 1.2% Pine Oil, 5.7% Versa-TL-4, 1.1% Merpol SE, 0.11% Zonyl FSN, 0.35% Makon 4, 0.35% Makon 4, 0.35% Makon 4, 14.0% Biosoft N-411
    • Where 505MM is 49% KP140 (TBEP), 49% vegetable oil, 1.6% Merpol SE, 0.2% Merpol A, and 0.2% Zonyl FSN
    • So,
    • 29.52% Citric Acid, 2.7% Biosoft 101-DDBSA, 1.2% butyl cellosolve, 5.0% C-4100, 0.6% Pine Oil, 2.85% Versa-TL-4, 0.55% Merpol SE, 0.055% Zonyl FSN, 0.175% Makon 4, 0.175% Makon 4, 0.175% Makon 4, 7.0% Biosoft N-411 9.8% KP140 (TBEP), 9.8% vegetable oil, 0.32% Merpol SE, 0.04% Merpol A, and 0.04% Zonyl FSN
    • Diesel=15%
    • DDBSA (Stepan Biosoft 101)=15%
    • DDBSA (total—17.7%), Merpol SE total—0.87%. Zonyl FSN Total—0.095%

Example 3 Column 9 of Table 2

    • 1.) Malcera 508MM=20%
    • 2.) Diesel=15%
    • 3.) DDBSA (Stepan Biosoft 101)=5%
    • 4.) Malcera 1507AK=60%
    • Total=100%
    • Where 1507AK is 59.04% Citric Acid, 5.4% Biosoft 101-DDBSA, 2.4% butyl cellosolve, 10.0% C-4100, 1.2% Pine Oil, 5.7% Versa-TL-4, 1.1% Merpol SE, 0.11% Zonyl FSN, 0.35% Makon 4, 0.35% Makon 4, 0.35% Makon 4, 14.0% Biosoft N-411
    • 49% KP140 (TBEP), 49% vegetable oil, 1.6% Merpol SE, 0.2% Merpol A, and 0.2% Zonyl FSN
    • So,
    • 35.424% Citric Acid, 3.24% Biosoft 101-DDBSA, 1.44% butyl cellosolve, 6.0% C-4100, 0.72% Pine Oil, 3.42% Versa-TL-4, 0.66% Merpol SE, 0.066% Zonyl FSN, 0.21% Makon 4, 0.21% Makon 4, 0.21% Makon 4, 8.4% Biosoft N-411 9.8% KP140 (TBEP), 9.8% vegetable oil, 0.32% Merpol SE, 0.04% Merpol A, and 0.04% Zonyl FSN
    • Diesel=15%
    • DDBSA (total—8.24%), Merpol SE total—0.98%. Zonyl FSN Total—0.106%

TABLE 2 A preferred formula for the composition (to be sold as Malcera 507AIG) of the present invention Col. 2 Col. 4 Col. 5 Col. 6 Col. 7 Col. 8 Col. 9 Function Col. 3 Preferred More Most Example 1 Example 2 Example 3 Col. 1 (Generic name) % by % Preferred % Preferred % % by % by % by Row Ingredient ((alternatives)) wt. by wt. by wt. by wt. wt. wt. wt. 1 Citric Acid demulsifier  7 to 65 10 to 60 11 to 55 12 to 50 29.52 29.52 35.424 50% (citric acid 50%/water50%) ((acetic acid, sorbic acid, formic acid, butyric acid, gluconic acid, valeric acid, 2-ethylbutyric acid, 2-ethylhexoic acid, propionic acid, iso pentanoic acid, benzoic acid, and other carboxylic acids; mineral acids, including nitric acid, phosphoric acid, and sulfuric acid; sulfonic acids, including DDBSA-Biosoft 101 and toluene sulfonic acid; fatty acids derived from vegetable oils, including mysistic, palmitic, stearic acid, oleic acid, linoleic acid, lauric acid, 2 Biosoft co-additive for demulsifier  3 to 50  5 to 50  5 to 45  5 to 35 22.7 17.7 8.24 101- (dodecyl benzene sulphonic DDBSA acid) ((toluene sulphonic acid or any other alkyl benzene sulphonic acid, such as toluene sulphonic acid, xylene sulphonic acid and mixtures thereof)) 3 butyl solvent and coupling agent and 0.5 to 6   .75 to 6   .75 to 5   .75 to 3.5 1.2 1.2 1.44 cellosolve antifoaming agent - hydrotrope (butyl cellosolve, aka EB) ((any other alkyl glycol ether, preferably non- toxic)) 4 C-4100 very powerful demulsifier 1.0 to 18  1.25 to 20   1.75 to 15   2.25 to 12   5.0 5.0 6.0 (diisopropylnaphthalenesulphonic acid (35-70%), sodium dodecylbenzenesulfonate (10-30%), 1,2,4-trimethylbenzene (5-15%), sulphuric acid (0.5-5%), xylene (0-3%), cumene (0-3%)) ((other alkyl, di-alkyl, tri-alkyl napthlalene sulphonic acids)) 5 Pine Oil solvent (pine oil) ((any other 0.5 to 5   0.5 to 3.0 0.8 to 3.0 1.0 to 3.0 0.6 0.6 0.72 terpene type of oil)) 6 Versa-TL-4 chelating dispersant - chelates  1 to 10  2 to 10 2 to 8 2 to 6 2.85 2.85 3.42 Fe, Al, Ca from about 100 ppm to less than 10 ppm - moves Fe, Al, Ca from oil to water (an oil-water soluble copolymer of partially sulfonated, maleic anhydride and polystyrene, 25% active) ((Versa-TL-3 diluted with water to 25% active)) 7 Merpol SE surfactant - lowers surface 0.5 to 3.0 0.5 to 2.5 0.5 to 2.0 0.5 to 1.5 0.8172 0.87 .98 tension (alcohol ethoxylate) ((any other non-ionic ethoxylated surfactant)) 8 Zonyl FSN fluorinated surfactant - lowers 0.01 to 0.3  0.01 to 0.2  0.05 to 0.18 0.05 to 0.15 0.0884 0.095 0.106 surface tension (40% fluorosurfactant, 30% isopropyl alcohol, and 30% water) ((or a Capstone fluorinated surfactant, such as Capstone N35 or Capstone N65fluorinated surfactant, which are 25% active, so 4X the amount should be used)) 9 Makon 4 surfactant - degreasing agent 0.0625 to 0.0625 to 0.0625 .075 to 0.7  0.175 0.175 0.21 (nonylphenol ethoxylate, 5.0 1.0 to 0.70 POE-4) ((or other nonylphenol ethoxylates, such as Makon 6 or Makon 8)) 10 Makon 6 surfactant - degreasing agent 0.0625 to 0.0625 to 0.0625 .075 to 0.7  0.175 0.175 0.21 (nonylphenol ethoxylate, 5.0 1.0 to 0.70 POE-6) ((or other nonylphenol ethoxylates, such as Makon 4 or Makon 8)) 11 Makon 8 surfactant - degreasing agent 0.0625 to 0.0625 to 0.0625 .075 to 0.7  0.175 0.175 0.21 (nonylphenol ethoxylate, 5.0 1.0 to 0.70 POE-8) ((or other nonylphenol ethoxylates, such as Makon 4 or Makon 6)) 12 Biosoft N- dispersant - oil soluble and 0.5 to 0.5 to 0.5 to  0.5 to 13.0 7.0 7.0 8.4 411 water dispersible anionic 20 17 15 surfactant - drops char content from around 2000 ppm to less than 10 ppm (isopropylamine dodecyl benzene sulfonates) ((other oil soluble and water dispersible anionic surfactants, including other isopropylamine dodecyl benzene sulfonates)) 13 Diesel diluent - ((any liquid 1-30  5 to 20 10-18  12-17 13.3 15 15 petroleum hydrocarbon)) 14 KP140 plasticizing agent 1-30  2-25 3-20  4-15 8.183 9.8 9.8 (TBEP) (tributoxyethylphosphate) ((none)) 15 soybean oil solubilizing agent 1-30 2-25 3-20  4-15 8.183 9.8 9.8 ((other vegetable oils, petroleum hydrocarbons, such as diesel, condensate, crude oil, kerosene, light cycle oil)) 16 Merpol A surfactant - lowers surface 0.01-.20  .02-.15  0.02-.10  0.03-0.50 0.0334 0.04 0.04 brand tension (phosphate ester) ((any nonionic other non-ionic phosphate phosphate ester surfactant, such as ester ethoxylated alcohols, reactions surfactant of cocoacid and polyethylene glycol (PEG), and nonylphenols))

The present inventor recently combined 1507AK and 508MM into a new single product by using a coupling agent from 1057AK (Biosoft 101). The new single product to be sold commercially as Malcera 507AIG, helps to process petroleum crude oils and biofuels with no rag layer.

To make the Malcera 507AIG product, one blends as follows (with preferably constant stirring):

    • put Malcera 508MM in a reactor at ambient temperature (typically around 25 Centigrade);
    • then add Diesel,
    • then add Biosoft 101,
    • then add slowly add Malcera 1507AK.

Then continue to stir for 4 to 5 hours at ambient temperature. Preferably, the 508MM is always the first ingredient in the reactor. The diesel or any liquid petroleum hydrocarbon of said mixture may be omitted by contiguously heating the mixture to a temperature of 170° F.

The chemical blend of Malcera 507AIG preferably comprises the following component ranges: 15 to 30% of 508MM, 5 to 20% of Diesel, 10 to 25% of Stepan Biosoft 101, 25 to 75% of 1507AK.

Malcera 507AIG can also have a following composition: 16.7% 508MM, 13.3% diesel or any liquid petroleum hydrocarbon, 20% of Stepan Biosoft 101, and 50% 1507AK.

An optional blending formulation of Malcera 507AIG has the following composition: 20% 508MM, 15% diesel or any liquid petroleum hydrocarbon, 15% of DoDecylBenzeneSulfonic Acid, and 50% 1507AK. This formulation of Malcera 507AIG may be used to break an emulsion before cleaning drill cuttings and can also be used as a substitute for Malcera 1507AK.

Another optional blending formulation of Malcera 507AIG has the following composition: 20% 508MM, 15% diesel or any liquid petroleum hydrocarbon, 5% of Stepan Biosoft 101, and 60% 1507AK. This formulation of Malcera 507AIG may also be used to break an emulsion before cleaning drill cuttings and can also be used as a substitute for Malcera 1507AK.

Malcera 507AIG (optionally without Makon 4, Makon 6, and Makon 8) (or a version with ingredients from columns 1 and or 2 of Table 2) can be used to treat slop oils and tank remnants or sludges to knock out water and to disperse the hydrocarbons into diluents, and to drop solids out of these products. This is usually performed at about 150-200 degrees F. and the concentration is usually 1,000-2,500 ppm.

Malcera 507AIG (or a version with ingredients from columns 1 and or 2 of Table 2) can be used to treat drill cuttings to reduce water content. This is usually performed at about 100 degrees C. and the concentration is usually 5,000-10,000 ppm. The drill cuttings are typically coated with oil based drilling mud emulstions.

Malcera 507AIG (optionally without Makon 4, Makon 6, and Makon 8, but preferably in approximately the amounts listed in column 7 of Table 2) (or a version with ingredients from columns 1 and or 2 of Table 2) can be used to reduce water content and solids content in a biofuels mixture made from the pyrolysis of wood to yield a very clean oil. This clean oil can then be hydrotreated to make gasoline and diesel. When used in a biofuels mixture, typically 500-1000 ppm of Malcera 507AIG is used in the biofuels mixture. The typical temperature is about 150 degrees F. Malcera 507AIG knocks out water so that less than 99.9% of the biofuels mixture is water. A desalter then takes out last up to 0.1% water.

    • 1.) 508MM: 300 to 3,000 P.P.M.
    • 2.) 1507AK: 1,000 to 10,000 P.P.M.

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. The vegetable oil is preferably soybean oil, and the surfactant is preferably a mixture of 1.6% Merpol SE brand nonionic ethoxylated alcohol surfactant, 0.2% Merpol A brand nonionic phosphate ester surfactant, and 0.2% Zonyl FSN brand nonionic fluoroalcohol surfactant

Other surface active agents, which may be used in place of or in combination with the exemplary polyethylene-oxide-based, nonionic surfactants, are outlined below.

Types of Nonionic Surfactants H.L.B. # 1. Ethoxylated Alcohols tridecyl alcohol ethoxylate (6 EO) 11.4 (where EO is ethylene oxide) tridecyl alcohol ethoxylate (9 EO) 13.3 tridecyl alcohol ethoxylate (12 EO) 14.5 tridecyl alcohol ethoxylate (15 EO) 15.3 Witco Chemicals' tridecyl alcohol ethoxylate 12.4 Stepan Chemicals' tridecyl alcohol ethoxylate 12.4 alcohol ethoxylate (3 EO) 8.0 alcohol ethoxylate (6 EO) 11.8 alcohol ethoxylate (8 EO) 13.2 alcohol ethoxylate (10 EO) 14.1 C8-C10 alcohol ethoxylate (6 moles) 12.5 C8-C10 alcohol ethoxylate (8 moles) 13.6 2. Reactions of Cocoacid + Polyethylene Gylcol (PEG) PEG30-glyceryl cocoate 15.9 PEG80-glyceryl cocoate 18.0 PEG 30 mixture-glyceryl cocoate 15.9 PEG 20-glyceryl tallowate 13.0 PEG80-glyceryl tallowate 18.0 PEG200-glyceryl tallowate 19.0 PEG2 cocamine 6.2 PEG5 cocamine 11.0 PEG10 cocamine 13.8 PEG15 cocamine 15.4 PEG15 cocamine mixture 15.4 It is noted that, as the amount of ethoxylation increases, the H.L.B. # increases, and the cationic character changes to more nonionic. PEG2 tallow amine 5.1 PEG2 tallow amine mixture 5.1 PEG5 tallow amine 9.2 PEG10 tallow amine 12.6 PEG15 tallow amine 14.4 PEG20 tallow amine 15.4 3. Other Commercially Available, Nonionic Surfactants Nonylphenol (5 EO) 6.8 Nonlyphenol (10 EO) 11.0 Nonylphenol (12 EO) 12.2 Nonylphenol (15 EO) 13.5 Nonylphenol (18 EO) 19.5 3. Other Currently Non-Commercially Available, Nonionic Surfactants a. nonionic surfactant formed from a-diol condensation products; b. polyhydroxyl nonionic compounds; c. nonionic surfactant formed by the reaction of an ethoxylated Schiff base with a methyl alkyl ketone; d. i-alkyl-polyethylene-polyamines reacted with maleric acid semiamide— nonionic compound with antibiocide properties; e. nonionic surfactant derived from polyethoxylated alcohols + vinyl-alkyl ethers; f. biodegradable glycidol surfactant (nonionic), e.g., alcohol + gylcidol (with catalyst) producing nonionic surfactant (biodegradable); g. multiblock polyacetal copolymer surfactants, e.g., poly-propylene oxide or poly-ethylene oxide + dialkyl ether; h. urea-ethoxamer nonionic inclusion compounds, e.g., urea + polyethoxylated long chain alcohols; i. nonionic phosphate alcohol surfactants; j. polyglycol ethers + polyglycol 6000 + epichlorohydrine derived nonionic surfactants; k. nonionic fluorosurfactant; etc.

The chemicals used in this disclosure, Malcera 1507AK, 508MM, and 517AIG are described above, 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 1507AK is preferably a blend of citric acid, Biosoft101, butyl cellosolve (EB), C-4100, Pine Oil, Versa TL-4, Merpol SE, Zonyl FSN, Makon 4, Makon 6, Makon 8, and Biosoft N-411. Malcera is also described in PCT Patent International Publication Number WO2010/039844A2. 3) 517AIG is preferably a blend 508MM, diesel or any liquid petroleum hydrocarbon, DoDecylBenzeneSulfonic Acid, and 1507AK.

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

1-147. (canceled)

148. 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 1507AK (ii) acceptable alternatives to Malcera 508MM and Malcera 1507AK mentioned herein (iii) Malcera 508MM and acceptable alternatives to Malcera 1507AK mentioned herein or (iv) acceptable alternatives to Malcera 508MM mentioned herein and Malcera 1507AK;
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.

149. The method of claim 148, 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.

150. The method of claim 148, 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.

151. The method of claim 148, wherein the chemical blend comprises Malcera 508MM and Malcera 1507AK.

152. The method of claim 151, wherein the chemical blend comprises at least 0.010% Malcera 508MM and at least 0.03% Malcera 1507AK.

153. The method of claim 151, wherein the chemical blend comprises 0.010-0.25% Malcera 508MM and 0.030-0.5% Malcera 1507AK.

154. The method of claim 148, wherein the chemical blend comprises acceptable alternatives to Malcera 508MM and Malcera 1507AK mentioned herein.

155. The method of claim 154, wherein the chemical blend comprises 0.010-0.50% Malcera 508MM alternative and 0.03-0.50% Malcera 1507AK alternative.

156. The method of claim 154, wherein the chemical blend comprises 0.05-0.25% Malcera 508MM alternative and 0.1-0.5% Malcera 1507AK alternative.

157. The method of claim 154, wherein the chemical blend comprises 0.075-0.12% Malcera 508MM alternative and 0.25-0.4% Malcera 1507AK alternative.

158. 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 1507AK and a Malcera 1507AK alternative.

159. The process of claim 158, wherein about 2.0% of the first chemical blend is used and about 2.0% of the second chemical blend is used.

160. A composition including the ingredients listed in Rows 1-12 of Column 1 and/or Column 2 of Table 2 in the specification, wherein at least one ingredient is included from each row.

161. The composition of claim 160, wherein the ingredients are those listed in Column 1.

162. The composition of claim 160, wherein the ingredients are in the ranges listed in Column 3.

163. The composition of claim 160, wherein the ingredients are in the ranges listed in Column 4.

164. The composition of claim 160, wherein the ingredients are in the ranges listed in Column 5.

165. The composition of claim 160, wherein the ingredients are in the ranges listed in Column 6.

166. The composition of claim 160, wherein the ingredients are about in the amount listed in Column 7.

167. The composition of claim 160, wherein the ingredients are about in the amount listed in Column 8.

Patent History
Publication number: 20150027926
Type: Application
Filed: Mar 17, 2014
Publication Date: Jan 29, 2015
Applicant: MALCERA, L.L.C. (NEW ORLEANS, LA)
Inventor: Gordon K. Goldman (Encino, CA)
Application Number: 14/216,171
Classifications
Current U.S. Class: With Treating Agent (208/188); Physical Separation Agents (252/60); Work Handled In Bulk Or Groups (134/25.1)
International Classification: C10G 33/04 (20060101);