US20140053455A1 - Demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing - Google Patents
Demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing Download PDFInfo
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- US20140053455A1 US20140053455A1 US13/970,362 US201313970362A US2014053455A1 US 20140053455 A1 US20140053455 A1 US 20140053455A1 US 201313970362 A US201313970362 A US 201313970362A US 2014053455 A1 US2014053455 A1 US 2014053455A1
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- biofuels
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Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G33/00—Dewatering or demulsification of hydrocarbon oils
- C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
Definitions
- 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.
- 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.
- 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.
- a demulsifier 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.
- 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
- Citric Acid demulsifier 30 to 90 40 to 80 45 to 75 50 to 70 59.04 60.5 50% (citric acid 50%/water 50%) ((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
- the citric acid is always the first ingredient in the reactor.
- 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.
- 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) 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) 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) 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.
- 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.
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Description
- This is anon-provisional patent application of U.S. Provisional Patent Application Ser. No. 61/684,414, filed 17 Aug. 2012, which is hereby incorporated herein by reference.
- Priority of U.S. Provisional Patent Application Ser. No. 61/684,414, filed 17 Aug. 2012, 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.
- Not applicable
- Not applicable
- 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.
- 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 N65fluorinated 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 sulfonates and other oil soluble and water dispersible anionic surfactants, including other isopropylamine dodecyl benzene sulfonates, and mixtures thereof.
-
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TABLE 1 A preferred formula for the composition (to be sold as Malcera 1507AK) of the present invention Col. 5 Col. 6 Col. 2 Col. 4 More Most Col. 7 Col. 8 Col. 1 Function Col. 3 Preferred Preferred Preferred Example A Example B Row Ingredient (Generic name) ((alternatives)) % by wt. % by wt. % by wt. % by wt. % by wt. % by 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%/water 50%) ((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 of 0.5 to 5 0.5 to 3.0 0.8 to 3.0 1.0 to 3.0 1.2 1.5 oil)) 6 Versa-TL- chelating dispersant - chelates Fe, Al, Ca 1 to 12 2 to 10 2 to 8 2 to 6 5.7 6 4 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 N65 fluorinated 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 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) 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) 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) 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.
- 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 (26)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US13/970,362 US20140053455A1 (en) | 2012-08-17 | 2013-08-19 | Demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing |
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US201261684414P | 2012-08-17 | 2012-08-17 | |
US13/970,362 US20140053455A1 (en) | 2012-08-17 | 2013-08-19 | Demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing |
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US20140053455A1 true US20140053455A1 (en) | 2014-02-27 |
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US13/970,362 Abandoned US20140053455A1 (en) | 2012-08-17 | 2013-08-19 | Demulsifier and dispersant for treating petroleum crude oils and biofuels prior to desalter and heater treater processing |
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US (1) | US20140053455A1 (en) |
WO (1) | WO2014028935A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090306232A1 (en) * | 2008-06-04 | 2009-12-10 | Williams Duncan E | Anhydride demulsifier formulations for resolving emulsions of water and oil |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2121779A (en) * | 1982-06-12 | 1984-01-04 | British Petroleum Co Plc | Dispersant composition |
US5622921A (en) * | 1993-01-21 | 1997-04-22 | Nowsco Well Service, Inc. | Anionic compositions for sludge prevention and control during acid stimulation of hydrocarbon wells |
US20050193923A1 (en) * | 1999-05-24 | 2005-09-08 | Goldman Gordon K. | System for treating petroleum and petrochemical slop oil and sludge wastes |
US20070243101A1 (en) * | 2004-09-07 | 2007-10-18 | Johnson Louis B | Cleaning composition with agricultural crop solvent and hydrogen peroxide |
US7468346B2 (en) * | 2003-06-30 | 2008-12-23 | Ecolab Inc. | Low foaming washing liquid |
US7651982B2 (en) * | 2004-08-21 | 2010-01-26 | Halliburton Energy Services, Inc. | Methods and aqueous acid solutions for acidizing wells containing sludging and emulsifying oil |
US20110174695A1 (en) * | 2008-09-30 | 2011-07-21 | Malcera, L.L.C. | Processes for recycling sag-d process water and cleaning drill cuttings |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU825582A1 (en) * | 1979-06-22 | 1981-04-30 | Tsni Pi Lesokhim Promy | Method of destroying emulsion of wood pyrolysis liquid products |
AU2010324533A1 (en) * | 2009-11-26 | 2012-06-14 | M-I Australia Pty Ltd | Compositions and methods for inhibiting naphthenate solids formation from liquid hydrocarbons |
-
2013
- 2013-08-19 WO PCT/US2013/055596 patent/WO2014028935A1/en active Application Filing
- 2013-08-19 US US13/970,362 patent/US20140053455A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2121779A (en) * | 1982-06-12 | 1984-01-04 | British Petroleum Co Plc | Dispersant composition |
US5622921A (en) * | 1993-01-21 | 1997-04-22 | Nowsco Well Service, Inc. | Anionic compositions for sludge prevention and control during acid stimulation of hydrocarbon wells |
US20050193923A1 (en) * | 1999-05-24 | 2005-09-08 | Goldman Gordon K. | System for treating petroleum and petrochemical slop oil and sludge wastes |
US7468346B2 (en) * | 2003-06-30 | 2008-12-23 | Ecolab Inc. | Low foaming washing liquid |
US7651982B2 (en) * | 2004-08-21 | 2010-01-26 | Halliburton Energy Services, Inc. | Methods and aqueous acid solutions for acidizing wells containing sludging and emulsifying oil |
US20070243101A1 (en) * | 2004-09-07 | 2007-10-18 | Johnson Louis B | Cleaning composition with agricultural crop solvent and hydrogen peroxide |
US20110174695A1 (en) * | 2008-09-30 | 2011-07-21 | Malcera, L.L.C. | Processes for recycling sag-d process water and cleaning drill cuttings |
Non-Patent Citations (1)
Title |
---|
Trademarks of Biosoft N-411; Biosoft 101, Zonyl FSN; Butyl Cellosolve; Makon 4, 6, 8; Merpol SE; Versa TL * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090306232A1 (en) * | 2008-06-04 | 2009-12-10 | Williams Duncan E | Anhydride demulsifier formulations for resolving emulsions of water and oil |
US9096805B2 (en) * | 2008-06-04 | 2015-08-04 | Nalco Company | Anhydride demulsifier formulations for resolving emulsions of water and oil |
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WO2014028935A1 (en) | 2014-02-20 |
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