Processing aids for enhanced hydrocarbon recovery from oil sands, oil shale and other petroleum residues

Abstract

A method of improving hydrocarbon recovery from oil sands, oil shale, and petroleum residues includes adding a polymeric or nonpolymeric processing aid capable of sequestering cations, such as the multivalent calcium, magnesium and iron cations. The hydrocarbons are preferably contacted with the processing aid before a primary separation of the hydrocarbons in order to increase bitumen recovery. A processing aid is provided in an effective amount to increase the liberation of the hydrocarbons from inorganic solids, particularly when the source is a poor processing ore. Preferred processing aids include citric acid or a polymeric acid selected from polyacrylic acid, polymethacrylic acid, salts of these acids, partial salts of these acids, and combinations thereof. The processing aids significantly increase the hydrocarbon recovery typically with concentrations less than 50 ppm and the polymeric processing aids can also provide beneficial flocculation of solids in tailings slurry.

1 . A method, comprising: 
 providing a processing aid to sequester cations in an aqueous mixture of hydrocarbons and inorganic solids; and    liberating the hydrocarbons from the inorganic material.    
     
     
         2 . The method of  claim 1 , further comprising separating the aqueous mixture into a hydrocarbon-containing froth portion and a tailings portion.  
     
     
         3 . The method of  claim 1 , further comprising: 
 determining an amount of hydrocarbons in the tailings portion; and    varying the amount the processing aid added to the aqueous mixture to control the amount of hydrocarbons in the tailings portion.    
     
     
         4 . The method of  claim 1 , wherein the hydrocarbons are liberated in the presence of water and a transfer agent.  
     
     
         5 . The method of  claim 1 , wherein the aqueous mixture includes a hydrocarbon-containing source selected from tar sand, oil shale, petroleum residues, and combinations thereof.  
     
     
         6 . The method of  claim 3 , wherein the transfer agent is selected from a caustic, a phosphate, a silicate, a carbonate, and combinations thereof.  
     
     
         7 . The method of  claim 3 , wherein the transfer agent is a caustic selected from sodium hydroxide, potassium hydroxide, and combinations thereof.  
     
     
         8 . The method of  claim 3 , wherein the amount of hydrocarbons is determined by fluorescence.  
     
     
         9 . The method of  claim 4 , wherein the hydrocarbon-containing source is characterized by having a combined concentration of calcium ions, magnesium ions and iron ions that is greater than  40  parts per million.  
     
     
         10 . The method of  claim 1 , wherein the processing aid is a carboxylic acid or a salt or partial salt thereof.  
     
     
         11 . The method of  claim 1 , wherein the processing aid is a carboxylic acid derivative of a nitrogen containing organic compound, or a salt or partial salt thereof.  
     
     
         12 . The method of  claim 1 , wherein the processing aid is a carboxylic acid, a salt of the carboxylic acid, a partial salt of the carboxylic acid, or a combination thereof.  
     
     
         13 . The method of  claim 1 , wherein the processing aid is selected from glycine, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, dicarboxymethyl glutamic acid, diaminocyclohexane-N,N,N′,N′-tetraacetic acid, ethylenebis(oxyethylenenitrilo)tetraacetic acid, hydroxyethyliminodiacetic acid, hydroxyethylethylenediaminetriacetic acid, salts of these acids, partial salts of these acids, and combinations thereof.  
     
     
         14 . The method of  claim 1 , wherein the processing aid is a carbohydrate.  
     
     
         15 . The method of  claim 1 , wherein the processing aid is an organic alcohol.  
     
     
         16 . The method of  claim 1 , wherein the processing aid is an organic amine, a derivative of an organic amine, a salt of an organic amine, or a combination thereof.  
     
     
         17 . The method of  claim 16 , wherein the organic amine is selected from a hydroxy amine, an aromatic amines, derivatives or salts of the amines, and combinations thereof.  
     
     
         18 . The method of  claim 16 , wherein the organic amine is selected from ethylene diamine, benzotriazole, triethanolamine, 2,2′-dipyridyl, or combinations thereof.  
     
     
         19 . The method of  claim 1 , wherein the processing aid is an organic acid selected from acetic acid, malonic acid, citric acid, isocitric acid, humic acid, vulvic acid, salts of these acids, partial salts of these acids, and combinations thereof.  
     
     
         20 . The method of  claim 1 , wherein the processing aid is a hydroxy organic acid selected from glycolic acid, malic acid, gluconic acid, glucoheptonic acid, tartaric acid, maleic acid, ferulic acid, salicylic acid, salts of these acids, partial salts of these acids, and combinations thereof.  
     
     
         21 . The method of  claim 1 , wherein the processing aid is a polymeric acid selected from polyacrylic acid, polymethacrylic acid, salts of these acids, partial salts of these acids, and combinations thereof.  
     
     
         22 . The method of  claim 1 , wherein the processing aid is a polymer based on monomers of maleic anhydride.  
     
     
         23 . The method of  claim 1 , wherein the processing aid is a salt of a carboxylic acid having cations selected from sodium, potassium, and combinations thereof.  
     
     
         24 . The method of  claim 1 , wherein the processing aid is a phosphoric acid derivative selected from sodium triphosphate, potassium triphosphate, sodium polyphosphate, disodium dihydrogenpyrophosphate, and combinations thereof.  
     
     
         25 . The method of  claim 1 , wherein the processing aid is an organophosphonate selected from methylphosphonic acid, hydroxyethylidine diphosphoric acid, any of the salts or partial salts of these acids, and combinations thereof.  
     
     
         26 . The method of  claim 1 , wherein the processing aid is an organophosphonate based on a nitrogen containing organic compound selected from aminomethanephosphonic acid, nitrilotris(methylene)triphosphonic acid, ethylenediaminetetra(methylenephosphonic acid), diethylene triamine penta(methylene phosphonic acid), hexamethylene-diaminetetra(methylenephosphonic acid), hydroxy containing derivatives thereof, and combinations thereof.  
     
     
         27 . The method of  claim 1 , wherein the processing aid is an organic compound containing both carboxylic and phosphonic functional groups, the organic compound selected from 2-phosphonobutane 1,2,4-tricarboxylic acid, any of the salts or partial salts of these acids, and combinations thereof.  
     
     
         28 . The method of  claim 1 , wherein the processing aid is a polymer selected from a homo polymer, a co-polymer, a salt or partial salt of these polymers, and combinations thereof, wherein the polymer includes a functional group selected from hydroxyl, carboxylic, amine, or combinations thereof.  
     
     
         29 . The method of  claim 1 , wherein the processing aid is a sulfur-containing organic acid selected from 2,3-dimercapto-1-propanol, sulfosalicylic acid, lignosulfonate, a salt or partial salt thereof, and combinations thereof.  
     
     
         30 . The method of  claim 1 , wherein the processing aid is an oxyalkylate derivative of an amine.  
     
     
         31 . The method of  claim 1 , wherein the processing aid is used to control the amount of hydrocarbons in the tailings portion.  
     
     
         32 . The method of  claim 1 , wherein the processing aid is suitable for sequestering cations selected from calcium, magnesium, iron, alumina, silica, titanium, zirconium, and combinations thereof.  
     
     
         33 . The method of  claim 2 , wherein the step of separating includes a mechanical separation.  
     
     
         34 . The method of  claim 33 , wherein the step of separating includes centrifuging.  
     
     
         35 . A method, comprising: 
 contacting a hydrocarbon-containing source selected from tar sand, oil shale, petroleum residues and combinations thereof with water, a transfer agent and a chelating agent during a primary separation of the hydrocarbon-containing source into a hydrocarbon-containing froth portion and a tailings portion.    
     
     
         36 . The method of  claim 35 , further comprising: 
 determining an amount of hydrocarbons in the tailings portion; and    varying the amount of the chelating agent added to the hydrocarbon-containing source to reduce the amount of hydrocarbons in the tailings portion.    
     
     
         37 . The method of  claim 35 , wherein the tailings portion comprises silica, clay and heavy minerals.  
     
     
         38 . The method of  claim 35 , characterized in that a greater percentage of hydrocarbons in the hydrocarbon-containing source is separated into the froth portion than under the same conditions without the chelating agent.  
     
     
         39 . The method of  claim 35 , further comprising: 
 varying the amount of processing aid to control the amount of hydrocarbons in the tailings portion.    
     
     
         40 . A method, comprising: 
 separating a hydrocarbon-containing source into a hydrocarbon-containing froth portion and a tailings portion; and    contacting the tailings portion with water, a transfer agent and a processing aid to produce a second hydrocarbon-containing froth portion and a second tailings portion.    
     
     
         41 . The method of  claim 40 , wherein the tailings portion comprises silica, clay and heavy minerals.  
     
     
         42 . The method of  claim 40 , further comprising: 
 contacting the hydrocarbon-containing froth portion with water, a transfer agent and a processing aid to produce a substantially solids-free froth portion and a substantially hydrocarbon-free tailings portion.    
     
     
         43 . The method of  claim 40 , wherein the processing aid sequesters cations in the tailings portion.  
     
     
         44 . The method of  claim 1 , wherein the processing aid is a-polymeric processing aid.  
     
     
         45 . The method of  claim 44 , wherein the polymeric processing aid is provided in an amount that is effective to increase the liberation of the hydrocarbons.  
     
     
         46 . The method of  claim 45 , wherein the hydrocarbons and inorganic solids are obtained from a poor processing ore.  
     
     
         47 . The method of  claim 44 , wherein the hydrocarbons and inorganic solids are obtained from oil sand, oil shale, petroleum residue, or a combination thereof.  
     
     
         48 . The method of  claim 44 , further comprising: 
 recovering liberated hydrocarbons from the mixture.    
     
     
         49 . The method of  claim 48 , wherein the recovering liberated hydrocarbons includes forming froth with the hydrocarbons attached to air bubbles.  
     
     
         50 . The method of  claim 48 , further comprising: 
 separating the inorganic solids into a tailings portion.    
     
     
         51 . The method of  claim 50 , further comprising: 
 providing an additional amount of a polymeric processing aid to the tailings portion to flocculate solids.    
     
     
         52 . The method of  claim 51 , wherein the polymeric processing aid provided to the tailings is the same polymeric processing aid provided to the aqueous mixture.  
     
     
         53 . The method of  claim 50 , wherein the polymeric processing aid separates along with the tailing portion to flocculate solids.  
     
     
         54 . The method of  claim 44 , wherein the aqueous mixture is provided with between 1 and 150 ppm of the polymeric processing aid.  
     
     
         55 . The method of  claim 44 , wherein the aqueous mixture is provided with between 10 and 100 ppm of the polymeric processing aid.  
     
     
         56 . The method of  claim 44 , wherein the aqueous mixture is provided with between 15 and 60 ppm of the polymeric processing aid.  
     
     
         57 . The method of  claim 56 , wherein the addition of the polymeric processing aid increases the bitumen recovery by at least 5 percent.  
     
     
         58 . The method of  claim 56 , wherein the addition of the polymeric processing aid increases the bitumen recovery by at least  10  percent.  
     
     
         59 . The method of  claim 44 , wherein the hydrocarbons comprise bitumen and the inorganic solids comprise clay.  
     
     
         60 . The method of  claim 59 , characterized in that the bitumen and clay have a zeta potential distribution that exhibits a common bitumen/clay peak before providing the polymeric processing aid and exhibits separate bitumen and clay peaks after providing the polymeric processing aid.  
     
     
         61 . The method of  claim 44 , wherein the cations include multivalent ions selected from calcium, magnesium, iron and combinations thereof.  
     
     
         62 . The method of  claim 44 , wherein the processing aid is suitable for sequestering cations selected from calcium, magnesium, iron, alumina, silica, titanium, zirconium, and combinations thereof.  
     
     
         63 . The method of  claim 44 , wherein the aqueous mixture includes greater than 10 parts-per-million of multivalent ions selected from calcium, magnesium, iron and combinations thereof.  
     
     
         64 . The method of  claim 44 , wherein the aqueous mixture includes greater than 30 parts-per-million of multivalent ions selected from calcium, magnesium, iron and combinations thereof.  
     
     
         65 . The method of  claim 44 , wherein the aqueous mixture has a combined concentration of calcium ions, magnesium ions and iron ions that is greater than 40 parts per million.  
     
     
         66 . The method of  claim 65 , further comprising: 
 reducing the concentration of unsequestered multivalent ions in the aqueous mixture to less than 30 parts-per-million.    
     
     
         67 . The method of  claim 44 , wherein the polymeric processing aid is oil soluble.  
     
     
         68 . The method of  claim 44 , wherein the polymeric processing aid is water soluble.  
     
     
         69 . The method of  claim 44 , wherein the polymeric processing aid is a hydrolysis product or salt capable of sequestering calcium.  
     
     
         70 . The method of  claim 44 , wherein the polymeric processing aid comprises an acrylic acid-based polymer or a polymer based on a substituted polyacrylic acid.  
     
     
         71 . The method of  claim 70 , wherein the polymeric processing aid comprises polyacrylic acid or polymethacrylic acid.  
     
     
         72 . The method of  claim 44 , wherein the polymeric processing aid comprises an acrylamid-based polymer or a polymer based on a substituted acrylamide.  
     
     
         73 . The method of  claim 72 , wherein the polymeric processing aid comprises polyacrylamide or polymethacrylamid.  
     
     
         74 . The method of  claim 44 , wherein the polymeric processing aid comprises a polymer, copolymer or terpolymer based on monomers selected from acrylic acid, acrylamide, acrylonitrile, or substituted derivatives of these monomers.  
     
     
         75 . The method of  claim 44 , wherein the polymeric processing aid hydrolyzes under conditions of the aqueous mixture.  
     
     
         76 . The method of  claim 74 , wherein the polymeric processing aid is a derivative selected from sulfonates, phosphates, phosphonates, betaines, sulfobetaines, and combinations thereof.  
     
     
         77 . The method of  claim 74 , wherein the polymeric processing aid is a salt selected from amine salts, ammonium salts, phosphonium salts, thiouronium salts, and combinations thereof.  
     
     
         78 . The method of  claim 73 , wherein the polymeric processing aid has a hypophosphite in the polymer backbone.  
     
     
         79 . The method of  claim 78 , wherein the hypophosphite backbone is formed by reacting the polyacrylic acid or the polymethacrylic acid with hypophosphorous acid.  
     
     
         80 . The method of  claim 44 , wherein the polymeric processing aid comprises a methylene sulfonate modified polyacrylamide, a methylene sulfonate modified polymethacrylamide, a hydroxamic acid modified polyacrylamide, or a hydroxamic acid modified polymethacrylamide.  
     
     
         81 . The method of  claim 44 , wherein the polymeric processing aid is a polyacrylamide.  
     
     
         82 . The method of  claim 81 , wherein the polyacrylamide is prepared by the reaction of polyacrylonitrile with water.  
     
     
         83 . The method of  claim 81 , wherein the polyacrylamide has a molecular weight between 1 and 50 million with between 20 and 30 percent ionic character.  
     
     
         84 . The method of  claim 81 , wherein the polyacrylamide forms a polycarboxylic acid at alkaline pH.  
     
     
         85 . The method of  claim 44 , wherein the polymeric processing aid is a hydrolysed polyacrylamide polymer characterized by an ability to sequester cations and an ability to flocculate solids.  
     
     
         86 . The method of  claim 44 , wherein the polymeric processing aid is a polymer with a nitrogen functionality.  
     
     
         87 . The method of  claim 86 , wherein the polymeric processing aid is a polyetheramine that has been reacted with methylchloride or salted with a polyacid.  
     
     
         88 . The method of  claim 44 , wherein the polymeric processing aid is a triethanolamine-based polymer having a molecular weight up to 150,000.  
     
     
         89 . The method of  claim 44 , wherein the polymeric processing aid is a polymeric acid selected from polyacrylic acid, polymethacrylic acid, salts of these acids, partial salts of these acids, and combinations thereof.  
     
     
         90 . The method of  claim 44 , wherein the polymeric processing aid is a polymer based on monomers of maleic anhydride.  
     
     
         91 . The method of  claim 44 , wherein the polymeric processing aid is a polymer selected from a homo polymer, a co-polymer, a salt or partial salt of these polymers, and combinations thereof, wherein the polymer includes a functional group selected from hydroxyl, carboxylic, amine, or combinations thereof.  
     
     
         92 . The method of  claim 44 , wherein the polymeric processing aid is added into a pipeline transporting the aqueous mixture.  
     
     
         93 . The method of  claim 44 , wherein the polymeric processing aid is added into a separation vessel.  
     
     
         94 . The method of  claim 44 , wherein the liberation is performed at a pH between about 7 and about 10.  
     
     
         95 . The method of  claim 44 , wherein the liberation is performed at a pH between about 8 and about 9.  
     
     
         96 . The method of  claim 44 , wherein the liberation is performed at a pH between about 8.2 and about 8.7.  
     
     
         97 . The method of  claim 44 , wherein the liberation is performed at a pH between about 8.2 and about 8.5.  
     
     
         98 . The method of  claim 52 , further comprising: 
 adjusting the pH of the aqueous mixture to between about  8  and about  9 .    
     
     
         99 . The method of  claim 1 , further comprising: 
 supplying a transfer agent to the aqueous mixture.    
     
     
         100 . The method of  claim 99 , wherein the transfer agent is selected from a caustic, a phosphate, a silicate, a carbonate, and combinations thereof.  
     
     
         101 . The method of  claim 99 , wherein the transfer agent is a caustic.  
     
     
         102 . The method of  claim 99 , wherein the transfer agent is a caustic selected from sodium hydroxide, potassium hydroxide, and combinations thereof.  
     
     
         103 . The method of  claim 99 , wherein the transfer agent is sodium hydroxide.  
     
     
         104 . The method of  claim 44 , wherein the polymeric processing aid is provided as an aqueous solution.  
     
     
         105 . The method of  claim 44 , characterized in that a reduction in the multivalent ion concentration allows greater bubble attachment of the hydrocarbons.  
     
     
         106 . The method of  claim 48 , further comprising: 
 monitoring the efficiency of the hydrocarbon recovery; and    varying the amount of polymeric processing aid added to the aqueous mixture to control the efficiency.    
     
     
         107 . The method of  claim 49 , characterized in that a reduction in the cation concentration allows greater bubble attachment of the hydrocarbons.  
     
     
         108 . A formulation for liberating hydrocarbons from an aqueous mixture of hydrocarbons and inorganic solids, comprising: 
 an aqueous solution of citric acid and antifreeze.    
     
     
         109 . The formulation-of  claim 108 , wherein the citric acid comprises at least 50 weight percent of the solution.  
     
     
         110 . The formulation of  claim 109 , wherein the antifreeze comprises between 1 and 25 weight percent methanol.  
     
     
         111 . The method of  claim 81 , wherein the polyacrylamide has between 60 and 85 percent anionic character.  
     
     
         112 . The method of  claim 81 , wherein the polyacrylamide is cationic.  
     
     
         113 . The method of  claim 50 , wherein the polymeric processing aid flocculates solids in the tailings portion.