Abstract:
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.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
       [0001]    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. 
         [0002]    Priority of U.S. Provisional Patent Application Ser. No. 61/684,414, filed 17 Aug. 2012, incorporated herein by reference, is hereby claimed. 
         [0003]    All prior patents and patent applications naming me as an inventor are hereby incorporated herein by reference, including the following: 
         [0004]    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. 
     
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT 
       [0005]    Not applicable 
       REFERENCE TO A “MICROFICHE APPENDIX” 
       [0006]    Not applicable 
       BACKGROUND OF THE INVENTION 
       [0007]    1. Field of the Invention 
         [0008]    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. 
         [0009]    2. General Background of the Invention 
         [0010]    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 
       [0011]    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). 
         [0012]    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.   
 
     
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0014]      
         [0000]                                                                                                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.
 
         [0015]    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.   
 
         [0028]    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. 
         [0029]    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). 
         [0030]    Malcera sells the above product as Malcera 1507AK. 
         [0031]    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. 
         [0032]    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. 
         [0033]    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. 
         [0034]    All measurements disclosed herein are at standard temperature and pressure, at sea level on Earth, unless indicated otherwise. 
         [0035]    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.