Water-Enriching and Water Depleting Compositions and Methods

Abstract

Compositions are disclosed for dewatering mixtures of petroleum and water. The compositions comprise one or more of the following: an unreacted polysaccharide component; and one or both of a polysaccharide component reacted with a hydrophilic component and a polysaccharide component reacted with a hydrophobic component. The compositions may also include viscosifying agents or stabilizers to stabilize the compositions against separation, for example, prior to use. In particularly preferred embodiments the invention is drawn to compositions for breaking an emulsion; such compositions comprising a carbohydrate component containing a cationic starch joined to a hydrophobic moiety, providing the carbohydrate component oil solubility. The composition may optionally comprise one or more additional demulsifier selected from, without limitation, salts (such as a polyaluminum chloride, an aluminum chlorohydrate, an alum, etc.), metal salts (such as iron and zinc salts), dithiocarbamate, tannin, and organic demulsifiers such as poly-DADMAC and similar compounds.

Claims

1. A composition for separating a hydrophobic phase from a water phase in a mixture comprising said hydrophobic phase and said water phase comprising a polysaccharide containing an unreacted polysaccharide component and a polysaccharide reacted with a hydrophilic component.

2. The composition of claim 1 wherein said polysaccharide component contains a polysaccharide reacted with a hydrophobic component.

3. The composition of claim 1 wherein said polysaccharide component contains a polysaccharide reacted with an amphiphilic component.

4. The composition of claim 1 wherein the unreacted polysaccharide component and polysaccharide reacted with a hydrophilic component are contained in a single polysaccharide molecule.

5. The composition of claim 2 wherein the unreacted polysaccharide component, polysaccharide reacted with a hydrophilic component, and a polysaccharide reacted with a hydrophilic component are contained in a single polysaccharide molecule.

6. The composition of claim 3 wherein the unreacted polysaccharide component and the amphiphilic component are contained in a single polysaccharide molecule.

7. The composition of claim 1 wherein the polysaccharide component comprises a starch.

8. The composition of claim 7 wherein the starch comprises about 100% amylopectin.

9. The composition of claim 1 wherein the polysaccharide component comprises a starch and at least one additional polysaccharide.

10. The composition of claim 7 wherein the polysaccharide component comprises at least one polysaccharide other than a starch.

11. The composition of claim 7 wherein the hydrophilic component is derived from a quaternary ammonium reagent.

12. The composition of claim 11 wherein the hydrophilic component is derived from a quaternary ammonium reagent selected from the group consisting of 1-propanaminium, 3-chloro-2-hydroxy-N,N,N-trimethylchloride (Quat 188), hydroxides and halides of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, and benzyl trimethyl ammonium hydroxide, a tetramethyl ammonium halide, a tetraethyl ammonium halide, a tetrabutyl ammonium halide, a benzyl trimethyl ammonium halide, and mixtures and derivatives thereof.

13. The composition of claim 3 wherein the amphiphilic component is derived from a quaternary ammonium reagent.

14. The composition of claim 13 wherein the amphiphilic component is derived from a quaternary ammonium reagent selected from the group consisting of 3-chloro-2-hydroxypropyl-lauryl-dimethylammonium chloride (Quab 342); 3-chloro-2-hydroxypropyl-cocoalkyl-dimethylammonium chloride (Quab 360) and 3-chloro-2-hydroxypropyl-stearyl-dimethylammonium chloride (Quab 426).

15. The composition of claim 12 comprising an amphiphilic component, wherein the amphiphilic component is derived from a quaternary ammonium reagent.

16. The composition of claim 15 wherein the amphiphilic component is derived from a quaternary ammonium reagent selected from the group consisting of 3-chloro-2-hydroxypropyl-lauryl-dimethylammonium chloride (Quab 342); 3-chloro-2-hydroxypropyl-cocoalkyl-dimethylammonium chloride (Quab 360) and 3-chloro-2-hydroxypropyl-stearyl-dimethylammonium chloride (Quab 426).

17. The composition of claim 2 wherein the hydrophobic component is derived from an aliphatic olefin oxide.

18. The composition of claim 7 wherein the hydrophobic component is derived from an aliphatic olefin oxide.

19. The composition of claim 18 wherein the olefin oxide is selected from the group consisting of styrene oxide, ethylene oxide, polyethylene oxide, and aliphatic olefin oxides having, for example, chain lengths of between 10 to 16 carbons, and hydrophobic derivatives thereof, and mixtures thereof.

20. The composition of claim 19 wherein the hydrophilic component is derived from a quaternary ammonium reagent selected from the group consisting of 1-propanaminium, 3-chloro-2-hydroxy-N,N,N-trimethylchloride (Quat 188), hydroxides and halides of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, and benzyl trimethyl ammonium hydroxide, a tetramethyl ammonium halide, a tetraethyl ammonium halide, a tetrabutyl ammonium halide, a benzyl trimethyl ammonium halide, and mixtures and derivatives thereof.

21. The composition of claim 10 wherein the polysaccharide other than a starch is selected form the group consisting of an alginate, a cellulose derivative, a dextrin, a guar, a xanthan, and derivatives thereof.

22. The composition of claim 1 comprising one or more demulsifier selected from the group consisting of a tannin; a water-soluble metal salt of iron, zinc, copper, magnesium, manganese, or aluminum; an acrylate polymer; an acrylamide polymer; a polyacrylamide; a polymer comprising DADMAC, DMAEM, DMAEA, MAPTAC, AMPIQ, DEAEA, DEAEM, DMAE-acrylamide, DMAEM-acrylamide, DEAE-acrylamide, DEAEM-acrylamide, or an acid or quaternized salts thereof; polyethyleneimine, a quaternized condensate amine, and dithiocarbamate.

23. The composition of claim 22 comprising a water soluble metal salt, wherein the water soluble metal salt is selected from the group consisting of an aluminum sulfate, an aluminum chloride, a aluminum chlorohydrate, a sodium aluminate, a polyaluminum chloride, a polyaluminum sulfur chloride, a polyaluminum silicate chloride, a ferric sulfate, a ferrous sulfate, a ferric chloride, a ferric chloride sulfate, a polyferric sulfate, a zinc zeolyte, a zinc sulfate, a zinc oxide, a zinc chloride and a zinc nitrate.

24. The composition of claim 15 comprising one or more demulsifier selected from the group consisting of a tannin; a water-soluble metal salt of iron, zinc, copper, magnesium, manganese, or aluminum; an acrylate polymer; an acrylamide polymer; a polyacrylamide; a polymer comprising DADMAC, DMAEM, DMAEA, MAPTAC, AMPIQ, DEAEA, DEAEM, DMAE-acrylamide, DMAEM-acrylamide, DEAE-acrylamide, DEAEM-acrylamide, or an acid or quaternized salts thereof; polyethyleneimine, a quaternized condensate amine, and dithiocarbamate.

25. The composition of claim 24 comprising a water soluble metal salt, wherein the water soluble metal salt is selected from the group consisting of an aluminum sulfate, an aluminum chloride, a aluminum chlorohydrate, a sodium aluminate, a polyaluminum chloride, a polyaluminum sulfur chloride, a polyaluminum silicate chloride, a ferric sulfate, a ferrous sulfate, a ferric chloride, a ferric chloride sulfate, a polyferric sulfate, a zinc zeolyte, a zinc sulfate, a zinc oxide, a zinc chloride and a zinc nitrate.

26. The composition of claim 12 wherein the starch comprises about 100% amylopectin and a hydrophilic component derived from a quaternary ammonium reagent.

27. The composition of claim 26 further comprising an amphiphilic reagent derived from a quaternary ammonium reagent selected from the group consisting of 3-chloro-2-hydroxypropyl-lauryl-dimethylammonium chloride (Quab 342); 3-chloro-2-hydroxypropyl-cocoalkyl-dimethylammonium chloride (Quab 360) and 3-chloro-2-hydroxypropyl-stearyl-dimethylammonium chloride (Quab 426).

28. A composition comprising: i. an unreacted polysaccharide component; ii. a polysaccharide component reacted with a hydrophilic component; and iii. a polysaccharide component reacted with a component selected from the group consisting of a hydrophobic component and an amphiphilic reagent.

29. The composition of claim 28 having a balance of water solubility and oil solubility to collect at a water-oil interface of an oil/water emulsion to cause coalescence and separation of at least a portion of the oil and water in the emulsion.

30. The composition of claim 28 which further comprises an effective amount of one or more viscosifying agents or stabilizers to substantially prevent or delay separation of the components of the composition.

31. The composition of claim 28 wherein the polysaccharide component referred to in each of (i), (ii) and (iii) is the same polysaccharide component.

32. The composition of claim 31 wherein the polysaccharide component is a starch component.

33. The composition of claim 32 wherein the hydrophilic component is selected from the group consisting of wherein the hydrophilic component is derived from a quaternary ammonium reagent selected from the group consisting of 1-propanaminium, 3-chloro-2-hydroxy-N,N,N-trimethylchloride (Quat 188), hydroxides and halides of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutyl ammonium hydroxide, and benzyl trimethyl ammonium hydroxide, a tetramethyl ammonium halide, a tetraethyl ammonium halide, a tetrabutyl ammonium halide, a benzyl trimethyl ammonium halide, and mixtures and derivatives thereof.

34. The composition of claim 33 comprising a hydrophobic component, wherein the hydrophobic component is selected from the group consisting of styrene oxide, ethylene oxide, polyethylene oxide, and aliphatic olefin oxides having chain lengths of between 10 to 16 carbons.

35. The composition of claim 33 comprising an amphiphilic component, wherein the amphiphilic component is selected from the group consisting of a quaternary ammonium reagent selected from the group consisting of 3-chloro-2-hydroxypropyl-lauryl-dimethylammonium chloride (Quab 342); 3-chloro-2-hydroxypropyl-cocoalkyl-dimethylammonium chloride (Quab 360) and 3-chloro-2-hydroxypropyl-stearyl-dimethylammonium chloride (Quab 426).

36. The composition of claim 34, wherein the mole percent of unreacted polysaccharide component is in the range of about 10 to about 40%; the mole percent of polysaccharide component reacted with a hydrophilic component is in a range of about 25% to about 45%; and the mole percent of polysaccharide component reacted with a hydrophobic component is in a range of about 25% to about 45%.

37. The composition of claim 34, wherein the mole percent of polysaccharide component reacted with a hydrophilic component is within about 10% of the mole % of polysaccharide component reacted with a hydrophobic component.

38. The composition of claim 37, wherein the mole percent of polysaccharide component reacted with a hydrophilic component is within about 5% of the mole % of polysaccharide component reacted with a hydrophobic component.

39. The composition of claim 37, wherein the mole percent of polysaccharide component reacted with a hydrophilic component is within about 2.5% of the mole % of polysaccharide component reacted with a hydrophobic component.

40. The composition of claim 28 comprising comprising one or more demulsifier selected from the group consisting of a tannin; a water-soluble metal salt of iron, zinc, copper, magnesium, manganese, or aluminum; an acrylate polymer; an acrylamide polymer; a polyacrylamide; a polymer comprising DADMAC, DMAEM, DMAEA, MAPTAC, AMPIQ, DEAEA, DEAEM, DMAE-acrylamide, DMAEM-acrylamide, DEAE-acrylamide, DEAEM-acrylamide, or an acid or quaternized salts thereof; polyethyleneimine, a quaternized condensate amine, and dithiocarbamate.

41. The composition of claim 40 comprising a water soluble metal salt, wherein the water soluble metal salt is selected from the group consisting of an aluminum sulfate, an aluminum chloride, a aluminum chlorohydrate, a sodium aluminate, a polyaluminum chloride, a polyaluminum sulfur chloride, a polyaluminum silicate chloride, a ferric sulfate, a ferrous sulfate, a ferric chloride, a ferric chloride sulfate, a polyferric sulfate, a zinc zeolyte, a zinc sulfate, a zinc oxide, a zinc chloride and a zinc nitrate.

42. A method of separating a mixture of a hydrophobic phase and an aqueous phase comprising contacting the mixture with a composition of claim 1 at conditions effective to obtain a hydrophobic phase having a reduced content of water, and a separated water product having a reduced content of the hydrophobic phase.

43. The method of claim 42, wherein the composition of claim 1 includes a starch-based component.

44. The method of claim 42, wherein the composition is selected taking into account the composition of the mixture of a hydrophobic phase and an aqueous phase.

45. The method of claim 42, wherein the composition (of claim 1) is a starch derived product having a sufficient hydrophilic/hydrophobic balance effective in use to cause the efficient separation of a clarified water phase and a water depleted hydrophobic phase.

46. A composition for dewatering a mixture of a hydrophobic phase and water comprising a cationic starch having a hydrophobic region and an effective amount of one or more visocsifying agents or stabilizers to prevent or delay separation of the components of the composition.

47. The composition of claim 46 wherein the one or more viscosifying agents is selected from the group consisting of one or more alginates, cellulose derivatives, dextrins, modified starches, guar derivatives, xanthan gum, mixtures thereof and the like.

48. The composition of claim 46, comprising one or more demulsifier selected from the group consisting of a tannin; a water-soluble metal salt of iron, zinc, copper, magnesium, manganese, or aluminum; an acrylate polymer; an acrylamide polymer; a polyacrylamide; a polymer comprising DADMAC, DMAEM, DMAEA, MAPTAC, AMPIQ, DEAEA, DEAEM, DMAE-acrylamide, DMAEM-acrylamide, DEAE-acrylamide, DEAEM-acrylamide, or an acid or quaternized salts thereof; polyethyleneimine, a quaternized condensate amine, and dithiocarbamate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0093] FIG. 1 shows the physical characteristics of a panel of 7 dewatering/clarifying compositions, all of which comprise a starch conjugated with styrene oxide and the cationic quaternary ammonium compound 1-propanaminium, 3-chloro-2-hydroxy-N,N,N-trimethylchloride (Quat 188) in various amounts, ratios and charge densities.

[0094] FIG. 2 shows the physical characteristics of a panel of 6 dewatering/clarifying compositions derived from the composition (Example 4) in FIG. 1 that was the most effective in breaking a particular reverse emulsion. The derivative compounds differed from each other (and from Example 4 of FIG. 1) within a narrower range of styrene oxide and Quat 188 concentrations, ratios and charge densities than the compositions of FIG. 1, and varied the mole percent of unreacted starch as well.

[0095] FIG. 3 shows physical characteristics of 4 dewatering/clarifying compositions derived from the composition (Example 4) in FIG. 1 that was the most effective in breaking a particular reverse emulsion. In these compositions styrene oxide was replaced by olefin oxides of varying aliphatic chain length.

DETAILED DESCRIPTION OF THE EXAMPLES

EXAMPLES 1-7

[0096] A panel of 7 samples are made comprising industrial acid modified corn starch (about 25% amylose and about 75% amylopectin) to which styrene oxide and the cationic quaternary ammonium reagent Quat 188 is conjugated in various amounts, ratios and charge densities. The samples are prepared using a protocol similar to that shown in

EXAMPLE 18.

[0097] FIG. 1 shows the characteristics of each of the seven samples, wherein the viscosity (Visc), charge density (C.D.), mole percent unreacted starch (% UN), mole percent starch reacted with the hydrophobic reagent styrene oxide (% SO), and mole percent starch reacted with the hydrophilic reagent Quat 188 (% CAT) are shown, as well as the ratio of starch reacted with styrene oxide/starch reacted with Quat 188 (ratio SO/Quat).

[0098] Each sample was tested in an emulsion breaking test against aliquots of the same crude oil sample containing water. For the particular sample provided, Example 4, a dewatering composition having a charge density of 0.62, 20% unreacted starch, and 40% each of starch reacted with styrene oxide and Quat 188 was found to be the most effective at breaking the emulsion and clarifying the water phase.

[0099] EXAMPLES 8-13

[0100] A second panel of 6 samples are made using Example 4 as a starting point for further refinement of an optimal dewatering composition for breaking the crude oil/water sample used in FIG. 1.

[0101] In this panel Example 9 is a duplicate of Example 4; as shown in FIG. 2, the remaining samples differed in the mole percentages of starch reacted with styrene oxide (from mol % to 45 mol %) and Quat 188 (from 30 mol % to 45 mol %), the ratios of the hydrophilic and hydrophobic components, and in the mole percent of unreacted starch (from 10 mol % to 40 mol %). The methods of making these samples was essentially as described in Example 18, but adjusted as necessary to account for the different concentrations and ratios of the hydrophobic and hydrophilic components.

[0102] Each sample was tested in the same emulsion breaking test described in Example 1-7, against the same crude oil sample containing water. In this case, Example 12, a dewatering composition having a charge density of 0.67, 30% unreacted starch, and 35% each of starch reacted with styrene oxide and Quat 188 (i.e., a 50:50 ratio) was found to be the most effective at breaking the emulsion and clarifying the water phase. This is the same compound whose synthesis is detailed in Example 18.

EXAMPLES 14-17

[0103] In a third panel, a set of samples based on Examples 4 and 9 were altered to substitute aliphatic olefin oxides of increasing chain length (C10, C12, C14 and C16) for styrene oxide to determine the effect on oil solubility and performance of the aliphatic chain length of the hydrophobic component. In some cases it may be useful for the dewatering composition not to contain styrene oxide, which may linger in the environment.

EXAMPLE 18

[0104] 81.1 grams of industrial acid modified corn starch (about 25% amylose and about 75% amylopectin) (from Cargill, Inc.) was slurried up in 134 ml of water in a 500 ml flask equipped with a mechanical stirrer and a temperature controller and mixed at room temperature until uniform. 20 grams of 50% sodium hydroxide was then added to the mixture and the temperature was increased to 95 F. and held for one hour.

[0105] 18.5 grams of styrene oxide (obtained from Sigma Aldrich Co.) was then added to the mixture which was mixed for an additional 30 minutes. 44.6 grams of Quat 188 (65% (by weight) solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride from Dow Hampshire Chemical Corp. was then added slowly to the mixture and the temperature was increased to 115 F. and held for 6 hours. The charge density of the mixture was then determined. 52 ml of water was then added and the resulting mixture was neutralized to pH 7.1 with 9.5 grams of concentrated hydrochloric acid.

[0106] The mixture had the following properties:

[0107] AppearanceSemi-transparent yellow-brown liquid

[0108] Charge density0.74 meq/gm, before addition of water

[0109] Viscosity2841 cps [0110] DS=degree of substitution, theoretical [0111] DS total0.70 [0112] DSQ1880.35 [0113] DSstyrene oxide0.35

[0114] The reaction product can also be described by the ratio of unreacted starch to starch reacted with Q188 (hydrophilic component (water solubilizing agent)) to starch reacted with styrene oxide (hydrophobic component (oil solubilizing agent)). In this example it was calculated that the starch was 30% unreacted; 35% of the starch reacted with Q188, to impart water solubility; and 35% of the starch reacted with styrene oxide, to impart oil solubility.

[0115] The best or optimum composition, for example, having the best or optimum emulsion breaking properties for a particular crude oil to be dewatered, is determined by adjusting the ratio of the degree of substitution and/or the ratio of unreacted starch (polysaccharide) to starch reacted with oil solubilizing agent to starch reacted with water solubilizing agent with a given crude oil and comparing the results obtained.

[0116] The product noted above (in which 30% by weight of the starch was unreacted, 35% by weight of the starch was reacted with Q188; and 35% of the starch was reacted with styrene oxide) was diluted to 50% with water and tested. The resulting composition gave good water/oil separation in the emulsion breaking test. Residual water in the separated oil was acceptable.

[0117] Products made at different ratios of unreacted starch to starch reacted with Q188 and to starch reacted with styrene oxide will work as oil dewatering/water clarifying agents to varying degrees, depending on the nature of the oil or water sample.

EXAMPLE 19

[0118] In this case the starch is conjugated to guar gum to determine whether the addition of a second polyssachharide aids in the demulsification of the crude oil sample. 392.9 grams of starch (same type of starch as recited in Example 18) was slurried up in 659 ml of water in a 2 liter flask equipped with a mechanical stirrer and a temperature controller and was mixed until uniform. 31.2 grams of a mixture of 25% by weight guar gum in propylene glycol was added while mixing rapidly. Mixing was continued for one hour. 99.1 grams of an aqueous solution of 50 weight percent sodium hydroxide was then added and the temperature was increased to 95 F. and mixed for one hour. 91 grams of styrene oxide was then added and mixed for 30 minutes. 220 grams of Quat 188 was then added slowly and the temperature was increased to 135 F. and held for 6 hours. 258 ml of water was then added and the product was neutralized to pH 7.5 with 47.8 g of concentrated hydrochloric acid.

[0119] The product had the following properties:

[0120] AppearanceSemi-transparent yellow-brown liquid

[0121] Charge density0.58 meq/gm, before addition of water

[0122] Viscosity1640 cps [0123] Polysaccharide(PS)=starch+guar gum [0124] Ratio of unreacted polysaccharide/polysaccharide reacted with Quat 188/polysaccharide reacted with styrene oxide was 30/35/35 [0125] DS=degree of substitution, theoretical [0126] DStotal0.70 [0127] DSQ1880.35polysaccharide reacted with Q18835% [0128] DSstyrene oxide0.35polysaccharide reacted with styrene oxide35%

[0129] The product was diluted to 50% with water and tested. The diluted product gave good water/oil separation in the emulsion breaking test. Samples made with different ratios worked to varying degrees. The water phase obtained with the guar gum was clearer than with an otherwise identical dewatering composition lacking conjugated guar gum.

EXAMPLE 20

[0130] In this example, the dewatering/clarifying composition is made without styrene oxide, by using the amphophilic component Quab 342. This compound confers somewhat less of a cationic charge to the conjugated starch than does Quat 188, but also possesses an aliphatic side chain, conferring oil solubility. Quat 188 is also used to increase the cationic charge density.

[0131] 66.8 grams of starch (same starch as recited in Example 18) was slurried up in 110 ml of water in a 500 ml flask equipped with a mechanical stirrer and a temperature controller and mixed until uniform. 22.3 grams of 50wt % sodium hydroxide aqueous solution was then added and the temperature was increased to 95 F. and mixed for one hour. 3.2 grams of 50 weight percent sodium hydroxide in water solution was added, followed by 78.7 grams of Quat 188 and 16.5 grams Quab 342.

[0132] Quab 342 is a 38% solution of 3-chloro-2-hydroxypropyl-lauryl-dimethylammonium chloride from SKW QUAB Chemicals, Inc. Quab 342 is a amphiphilic reagent containing a hydrophobic component and a hydrophilic component in the same molecule. It will be understood that other amphilphilic reagents are available and may be used, such as Quab 151, Quab 360, Quab 426 and the like.

[0133] The temperature was increased to 130 F. and held for 6 hours. 150 ml of water was then added. The product was neutralized to pH 7 with 2.2 g of concentrated hydrochloric acid.

[0134] The product had the following properties:

[0135] AppearanceSemi-transparent yellow-brown liquid

[0136] Charge density0.65

[0137] Viscosity12880 cps

[0138] Ratio of unreacted starch/starch reacted with Quat 188/starch reacted with Quab 34220/75/5 [0139] DS=degree of substitution, theoretical [0140] DStotal0.70 Unreacted starch)30% [0141] DSQ1880.35 Starch reacted with Q18835% [0142] DSQ3420.35 Starch reacted with Q34335%

[0143] The product was diluted to 50% with water and tested. The diluted product gave good water/oil separation in the emulsion breaking test. Samples made with different ratios worked to varying degrees.

EXAMPLE 21

[0144] 65.1 grams of industrial acid modified corn starch (as recited in Example 1) was slurried up in 110 ml of water in a 500 ml flask equipped with a mechanical stirrer and a temperature controller and mixed until uniform. Then, 6.8 grams of a mixture of 25% guar gum in propylene glycol was added while mixing rapidly. Mixing was continued for one hour. 22.3 grams of 50% by weight sodium hydroxide in water was then added and the temperature was increased to 95 F. and mixed for one hour. 7.1 grams of 50% sodium hydroxide in water was added, followed by 93.4 grams Quat 188 and 9.9 g Quab 342. The temperature was increased to 130 F. and held for 6 hours. The product was neutralized to pH 7 with 2.6 g of concentrated hydrochloric acid.

[0145] The product had the following properties:

[0146] AppearanceSemi-transparent yellow-brown liquid

[0147] Charge density1.23

[0148] Viscosity13640 cps

[0149] Ratio of unreacted polysaccharide/Quat 188/Quab 3428/89/3 [0150] DS=degree of substitution [0151] DStotal0.92 Unreacted polysaccharide8% [0152] DSQ1880.89 polysaccharide reacted with Q18889% [0153] DSQ3420.03 polysaccharide reacted with Q3423%

[0154] The product was diluted to 50% with water and tested. It gave good water/oil separation in the emulsion breaking test. Samples made with different ratios worked to varying degrees. The water phase was clearer than obtained without guar gum.

[0155] When diluted with water the mixtures of the type shown in Examples 1-4 can separate, especially at elevated temperatures.

[0156] Various substances may be added to improve flow or prevent freezing. Such substances include, without limitation, alcohols, glycols and the like and combinations thereof.

[0157] In addition, the products obtained in accordance with the examples have been found to be able to be stabilized against separation by the addition of viscosifying agents. Such agents may, without limitation, include one or more of the following: alginates, carboxymethyl cellulose, dextrins, modified starches, guar gum, hydroxyproyl guar, hydroxyethyl cellulose, xanthan gums.

[0158] The use of viscosifying agents (stabilizers) is an important aspect of the present invention in that such agents can be used so that the products can be produced at a location remote from the location at which such products are used. Thus, the products need not be produced at each individual place where the crude oil is to be dewatered.

[0159] In certain applications, and for use with different oil or water samples, stabilizers such as one or more antioxidants, chelating agents, coupling agents, density modifiers, dispersants, emulsifiers, solvents and surfactants, or mixtures thereof, may be useful as part of the dewatering/clarifying compositions.

[0160] The following Examples 22-25 illustrate the use and effectiveness of certain of the viscosifying agents.

EXAMPLE 22

[0161] Product from Example 1850.0% (by wt.) [0162] Water50.0% (by wt.) [0163] Separates after standing at 135 F. for 1 week [0164] Product from Example 1850.0% (by wt.) [0165] Water49.2% (by wt.) [0166] Dextrin0.8% (by wt.)viscosfying agent [0167] No separation at 135 F. after 4 weeks [0168] Viscosity158 cps [0169] Dextrin from Tate and Lyle, Stadex 128

EXAMPLE 23

[0170] Product from Example 1950% (by wt.) [0171] Water50% [0172] Separates after standing at 135 F. for 1 week [0173] Product from Example 1950% (by wt.) [0174] Water49.6% (by wt.) [0175] Sodium carboxymethylcellulose (CMC)0.4% [0176] No separation at 135 F. [0177] Viscosity552 cps [0178] Sodium carboxycellulose, Aqualon CMC 7MF from Ashland

EXAMPLE 24

[0179] Product from Example 2130.0% (by wt.) [0180] Water70% (by wt.) [0181] Separates after standing at 135 F. for 1 week [0182] Product from Example 2130.0% (by wt.) [0183] Water69.6% (by wt.) [0184] Wel-Zan XG0.4% (by wt.) [0185] No separation at 135 F. [0186] Viscosity1696 cps

[0187] Examples of viscosifying agents or stabilizers include, without limitation, alginates, cellulose derivatives, dextrins, modified starches, guar derivatives, xanthan gum, mixtures thereof and the like.

EXAMPLE 25

[0188] Product from Example 2450%-75% (by wt.) [0189] Aluminum chlorhydrate, 25%-50% (by wt.)

[0190] This product was tested as an oil/water emulsion breaker. In these tests, this product provided good water/oil separation.

EXAMPLE 26

[0191] It will be understood that the compositions of the present invention may be used in conjunction with additional demulsifiers, salts and the like in a final product. In choosing an effective, or the most effective, product for use in dewatering or clarifying a crude oil or water sample of interest, a sample of may be tested with a number of products having compositions within the scope of this invention. Such testing can be conducted expeditiously and provide a basis for identifying the most effective and efficient product for the sample of interest.

[0192] It is also important to note that certain products in accordance with the present invention have been found to be effective in dewatering a relatively large number of crude oils. Thus, these certain products may be given priority in testing when seeking to identify a product in accordance with the present invention that is effective, e.g., highly effective, in dewatering a given crude oil.

[0193] Non-limiting examples of dewatering/water clarifying compositions of the present invention are shown below.

TABLE-US-00002 Product Formula Weight % A GFT 5013 20% ACS 2070 80% B GFT 5045 50% DelPac XG 50% C GFT 5013 50% DelPac XG 50% D GFT 5100 60% Floquat FL 5323 40% E GFT 5100 F GFT 5013 G GFT 5045

Where:

[0194] GFT 5013=48.5 wt % water; 42.4 wt % modified corn starch (100% amylopectin) substituted with Quat 188; 9.1 wt % NaCl.

[0195] GFT 5100=78.2 wt % water; 19.3 wt % modified corn starch (100% amylopectin) substituted with Quat 188; 2.5 wt % NaCl.

[0196] GFT 5045=58.7 wt % water; 34.8 wt % modified corn starch (100% amylopectin) substituted with Quat 188 and Quab 342; 6.5 wt % NaCl.

[0197] ACS 2070=polyaluminum chloride solution (Aluminum Chemical Specialties, LLC) 11 wt % aluminum, 70% basicity, specific gravity 1.3.

[0198] DelPac XG=aluminum chlorohydrate solution (USALCO, LLC) A1203 24%, basicity 83%, specific gravity 1.3.

[0199] Floquat FL 5323=30% by weight acidified tannin substances (SNF, Inc.)

[0200] Products may contain from about 1% to 100% of a cationic starch as disclosed herein either containing or lacking an additional hydrophobic component. Some such products may comprise 1% to 100% of a cationic starch in combination with 99% to 1% of a metal salt solution. Such products may be used as is, or may be blended with other ingredients before use. The products will be useful to remove water from an oil phase, remove water from an oil phase, and/or clarify a water phase.

[0201] The foregoing examples are simply for the purpose of illustrating various compositions incorporating elements disclosed in the present specification, which shall be interpreted to include any and all figures, charts, tables, descriptions, data, and other attachments filed herewith.

[0202] To the extent that a plurality of inventions may be disclosed herein, any such invention shall be understood to have disclosed herein alone, in combination with other features or inventions disclosed herein, or lacking any feature or features not explicitly disclosed as essential for that invention. For example, the inventions described in this specification can be practiced within elements of, or in combination with, other any features, elements, methods or structures described herein unless inconsistent with the specification, taken as a whole. Additionally, features illustrated herein as being present in a particular example are intended, in other examples of the present invention, to be explicitly lacking from the invention, or combinable with features described elsewhere in this patent application, in a manner not otherwise illustrated in this patent application or present in that particular example, unless inconsistent with the specification, taken as a whole. The scope of the invention shall be determined solely by the language of the claims.

[0203] Thus, the various descriptions of the invention provided herein illustrate presently preferred examples of the invention; however, it will be understood that the invention is not limited to the examples provided, or to the specific configurations and relation of elements unless the claims specifically indicate otherwise. Based upon the present disclosure a person of ordinary skill in the art will immediately conceive of other alternatives to the specific examples given, such that the present disclosure will be understood to provide a full written description of each of such alternatives as if each had been specifically described.

[0204] Claim terms shall be intrinsically defined not only by a specific definition in the specification, but also with reference to the Figures as understood by a person of ordinary skill in the art in light of the present disclosure.

[0205] Every publication and patent document cited herein is each hereby individually incorporated by reference in its entirety for all purposes to the same extent as if each were so individually denoted.