Solid Adsorbent Compositions for Purifying Liquids

Abstract

A composition for purifying a liquid, such as used cooking oil, unrefined edible oils, or biodiesel fuel, that comprises at least one purifying material, such as magnesium silicate, and at least one binder material that is a solid or a semi-solid at room temperature, or is water or a glycol. When the composition is placed in a liquid, and the liquid is heated, the solid composition disintegrates and the at least one purifying material is released in the liquid. Such composition minimizes or eliminates contact with the dust associated with solid adsorbent materials, and provides for a controlled release of the at least one purifying material into the liquid to be purified.

Claims

1. A composition for purifying a liquid, comprising: at least one purifying material; and at least one binder material, wherein said at least one binder material is selected from the group consisting of hydrogenated vegetable oils, saturated vegetable oils, animal fats, waxes, water, glycols, fatty acids, fatty alcohols, fatty acid esters, fatty alcohol esters, and mixtures thereof.

2. The composition of claim 1 wherein said at least one purifying material is selected from the group consisting of metal silicates, silica gel, activated carbon, alkali metal silicates, magnesium phosphate, metal hydroxides, metal oxides, metal carbonates, metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal oxides, sodium sesquicarbonate, bleaching clays, bleaching earths, bentonite clay, diatomaceous earth, alumina, diatomite, and mixtures thereof.

3. The composition of claim 2 wherein said at least one purifying material comprises at least one metal silicate.

4. The composition of claim 3 wherein said at least one metal silicate is selected from the group consisting of magnesium silicate, magnesium aluminum silicate, calcium silicate, aluminum silicate, sodium silicate, and mixtures thereof.

5. The composition of claim 4 wherein said at least one metal silicate comprises magnesium silicate.

6. The composition of claim 1 wherein said at least one binder material is at least one hydrogenated vegetable oil.

7. The composition of claim 1 wherein said at least one binder material is at least one animal fat.

8. The composition of claim 1 wherein said at least one binder material is at least one wax.

9. The composition of claim 1 and further comprising at least one liquid edible oil.

10. The composition of claim 1 wherein said at least one purifying material is present in said composition in an amount of from about 0.1 wt. % to about 99 wt. %.

11. The composition of claim 10 wherein said at least one purifying material is present in said composition in an amount of from about 0.1 wt. % to about 90 wt. %.

12. The composition of claim 1 wherein said at least one binder material is present in said composition in an amount of from about 0.1 wt. % to about 99 wt. %.

13. The composition of claim 12 wherein said at least one binder material is present in said composition in an amount of from about 0.1 wt. % to about 60 wt. %.

14. The composition of claim 9 wherein said at least one liquid edible oil is present in said composition in an amount of from about 0.1 wt. % to about 99 wt. %.

15. The composition of claim 14 wherein said at least one liquid edible oil is present in said composition in an amount of from about 0.1 wt. % to about 60 wt. %.

16. A method of purifying a liquid comprising: contacting said liquid with a composition comprising (i) at least one purifying material and (ii) at least one binder material, wherein said at least one binder material is selected from the group consisting of hydrogenated vegetable oils, saturated vegetable oils, animal fats, waxes, water, glycols, fatty acids and mixtures thereof, and heating said liquid to a temperature effective to effect disintegration of said composition, whereby said at least one purifying material is released from said composition and contacts said liquid, thereby purifying said liquid.

17. The method of claim 16 wherein said at least one purifying material is selected from the group consisting of metal silicates, silica gel, activated carbon, alkali metal silicates, magnesium phosphate, metal hydroxides, metal oxides, metal carbonates, metal bicarbonates, alkaline earth metal hydroxides, alkaline earth metal oxides, sodium sesquicarbonate, bleaching clays, bleaching earths, bentonite clay, diatomaceous earth, alumina, diatomite, and mixtures thereof.

18. The method of claim 17 wherein said at least one purifying material comprises a metal silicate.

19. The method of claim 18 wherein said at least one metal silicate is selected from the group consisting of magnesium silicate, magnesium aluminum silicate, calcium silicate, aluminum silicate, and mixtures thereof.

20. The method of claim 19 wherein said at least one metal silicate comprises magnesium silicate.

21. The method of claim 16 wherein said at least one binder material is at least one hydrogenated vegetable oil.

22. The method of claim 16 wherein said at least one binder material is at least one animal fat.

23. The method of claim 16 wherein said at least one binder material is at least one wax.

24. The method of claim 16 wherein said composition further comprises at least one liquid edible oil.

25. The method of claim 16 wherein said at least one adsorbent material is present in said composition in an amount of from about 0.1 wt. % to about 99 wt. %.

26. The method of claim 25 wherein said at least one adsorbent material is present in said composition in an amount of from about 0.1 wt. % to about 90 wt. %.

27. The method of claim 16 wherein said at least one binder material is present in said composition in an amount of from about 0.1 wt. % to about 99 wt. %.

28. The method of claim 27 wherein said at least one binder material is present in said composition in an amount of from about 0.1 wt. % to about 60 wt. %.

29. The method of claim 24 wherein said at least one liquid edible oil is present in said composition in an amount of from about 0.1 wt. % to about 99 wt. %.

30. The method of claim 29 wherein said at least one liquid edible oil is present in said composition in an amount of from about 0.1 wt. % to about 60 wt. %.

31. The method of claim 16 wherein said liquid is heated to a temperature of from about 32° F. to about 500° F.

32. The method of claim 31 wherein said liquid is heated to a temperature of from about 100° F. to about 425° F.

33. The method of claim 32 wherein said liquid is heated to a temperature of from about 200° F. to about 400° F.

34. The method of claim 16 wherein said liquid is used cooking oil.

35. The method of claim 16 wherein said liquid is an unrefined edible oil.

36. The method of claim 16 wherein said liquid is biodiesel fuel.

37. The method of claim 16 wherein said liquid is a dielectric fluid.

38. A composition for purifying a liquid, comprising: at least one purifying material; and at least one frozen liquid.

39. The composition of claim 38 wherein said at least one purifying material is magnesium silicate.

40. The composition of claim 38 wherein said at least one frozen liquid is frozen water.

41. A method of purifying a liquid, comprising: contacting said liquid with a composition comprising at least one purifying material and at least one frozen liquid, wherein said contacting is conducted at a temperature effective to effect melting of said at least one frozen liquid, whereby said at least one purifying material is released from said composition and contacts said liquid to be purified, thereby purifying said liquid to be purified.

42. The method of claim 41 wherein said at least one purifying material is magnesium silicate.

43. The method of claim 41 wherein said at least one frozen liquid is frozen water.

44. The composition of claim 1 wherein said at least one binder material is at least one fatty acid.

45. The composition of claim 1 wherein said at least one binder material is at least one fatty alcohol, wherein said fatty alcohol has at least 12 carbon atoms.

46. The composition of claim 1 wherein said at least one binder material is at least one fatty acid ester of a monohydroxy compound, wherein said fatty acid has at least 10 carbon atoms, wherein said monohydroxy compound has 1 to 20 carbon atoms.

47. The composition of claim 46 wherein said at least one fatty acid has at least 16 carbon atoms.

48. The composition of claim 46 wherein said monohydroxy compound is an alkyl alcohol, alkenyl alcohol, alkynyl alcohol, aralkyl alcohol, aryl alcohol or alkyether alcohol.

49. The composition of claim 1 wherein said at least one binder material is at least one fatty acid ester of a polyhydric alcohol wherein said fatty acid has at least 10 carbon atoms and wherein said polyhydric alcohol is a polyol having a linear, branched or cyclic unit which has at least 2 carbon atoms, and at least 2 hydroxyl groups per molecule.

50. The composition of claim 1 wherein said at least one binder material is at least one fatty acid ester of a polyhydric alcohol wherein said fatty acid has at least 10 carbon atoms, and wherein said polyhydric alcohol is a sugar alcohol.

51. The composition of claim 1 wherein said at least one binder material is at least one fatty acid ester of a polyhydric alcohol wherein said fatty acid has at least 10 carbon atoms, and wherein said polyhydric alcohol is selected from the group consisting polyalkylene glycols, polyglycerols, polymerized pentaerythritols and polymerized hexitols.

52. The composition of claim 1 wherein said at least one binder material is at least one fatty alcohol ester of a carboxylic acid, wherein said fatty alcohol has at least 12 carbon atoms, and wherein said carboxylic acid has at least 2 carbon atoms.

53. The composition of claim 52 wherein said fatty alcohol is selected from a group consisting of lauryl alcohol (dodecanol, 1-dodecanol), tridecyl alcohol (1-tridecanol, tridecanol, isotridecanol), myristyl alcohol (1-tetradecanol), pentadecyl alcohol (1-pentadecanol, pentadecanol), cetyl alcohol (1-hexadecanol), palmitoleyl alcohol (cis-9-hexadecen-1-ol), heptadecyl alcohol (1-n-heptadecanol, heptadecanol), stearyl alcohol (1-octadecanol), nonadecyl alcohol (1-nonadecanol), arachidyl alcohol (1-eicosanol), heneicosyl alcohol (1-heneicosanol), behenyl alcohol (1-docosanol), erucyl alcohol (cis-13-docosen-1-ol), lignoceryl alcohol (1-tetracosanol), ceryl alcohol (1-hexacosanol), 1-heptacosanol, montanyl alcohol, cluytyl alcohol, or 1-octacosanol, 1-nonacosanol, myricyl alcohol, melissyl alcohol, or 1-triacontanol, 1-dotriacontanol (lacceryl alcohol) and geddyl alcohol (1-tetratriacontanol).

54. The composition of claim 1 wherein said at least one purifying material is sodium hydroxide.

55. The composition of claim 4 wherein said at least one metal silicate is sodium silicate.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0093] The invention now will be described with respect to the drawings, wherein:

[0094] FIG. 1 is a graph showing particle size distribution of magnesium silicate particles recovered from an adsorbent composition of the present invention used to purify frying oil, after washing the particles with hexane to remove residual frying oil; and

[0095] FIG. 2 is a graph showing particle size distribution of magnesium silicate not formed into an adsorbent composition of the present invention.

EXAMPLES

[0096] The invention now will be described with respect to the following examples. It is to be understood, however, that the scope of the present invention is not intended to be limited thereby.

[0097] General procedures for the preparation of powder formulations and compressed solid articles are provided below followed by individual examples. The examples include determination of solid adsorbent disintegration times in oil into individual particles.

[0098] The following materials were used in the examples hereinbelow:

[0099] canola oil

[0100] candelilla wax

[0101] corn oil

[0102] soybean oil

[0103] hydrogenated soybean oil

[0104] palm oil

[0105] peanut oil

[0106] sodium silicate

[0107] magnesium silicate (Magnesol® powder, The Dallas Group of America Inc.)

[0108] Magnesol® powder is a magnesium silicate having a pH of from 8.5 to 8.8 in a 5% suspension in deionized water, a mean particle size of from 100 to 120 microns, a molar ratio of silicon dioxide to magnesium oxide of from 2.6 to 2.7, and a surface area of from 500 to 700 square meters per gram.

General Procedure for Making Powder Formulations

[0109] The edible or frying oils were placed in a container and heated to 70° to 100° C. Hydrogenated soybean oil, wax, or palm oil was placed in another container and heated to 70 to 100° C. (or up to the melting point of the wax or oil). Synthetic magnesium silicate adsorbent powder was charged into a reactor and heated at 50° to 160° C. for 5 to 30 minutes. The oils and waxes were added to the hot powder with mixing. Mixing was continued until the mixture had cooled to room temperature, resulting in a free flowing powder formulation. The powder then was sieved through two sieve screens: No. 35 (500 microns) and No. 40 (425 microns).

General Procedure for Compressing of Powder Formulation

[0110] Each powder formulation to be compressed was weighed into a stainless steel cylindrical pressing die. The die was assembled and placed onto a hydraulic press. The powder was compressed to a pre-determined pressure and held at this pressure until there was no drop in pressure. Pressure was released and the resulting solid adsorbent was released from the pressing die. For small solid adsorbent (2-4 grams) compositions, a 1″ (25 mm) diameter cylindrical pressing die was used. For large solid adsorbent compositions (50-300 grams) a 4″ (102 mm) diameter cylindrical pressing die was used.

General Procedure for Puck Disintegration Testing

[0111] Oil was heated to the desired testing temperature. A puck for testing was placed in the hot oil and allowed to disintegrate fully into fine particles.

Examples 1-6. Solid Adsorbent Formulations with Magnesium Silicate, Canola Oil and Hydrogenated Soybean Oil

[0112] Powder formulations and solid adsorbent formulations were made from magnesium silicate, canola oil, and hydrogenated soybean oil according to the general methods described above. Table 1 shows exemplary compositions and the performance of such solid adsorbent compositions. Disintegration tests of the resulting solid adsorbents were performed at 1185° C. (365° F.) in frying oil. The results are shown in Table 1 below.

TABLE-US-00003 TABLE 1 Disintegration Time (4 g of Solid Adsorbent Hydrogenated Compressed to 1.0 Magnesium Canola Soybean metric Tons) Example Silicate, Oil, Oil, (Frying oil at 185° C.) No. weight % weight % weight % (seconds) 1 50 50 0.0 n.d* 2 50 49.5 0.5 n.d* 3 50 49.0 1.0 35 4 50 47.0 3.0 17 5 50 45.0 5.0 22 6 50 40.0 10.0 16 n.d* = no disintegrations after 5 minutes.

Examples 7-9. Solid Adsorbents with Magnesium Silicate, Peanut Oil and Candelilla Wax

[0113] Powder formulations and solid adsorbent formulations were made from magnesium silicate, peanut oil, and candelilla wax according to the general methods described above. Table 2 shows exemplary solid adsorbent compositions and the performance of such solid compositions compressed at 1.0 metric tons for 15 seconds using a 1″ (25 mm) diameter cylindrical pressing die. Disintegration tests of the resulting solid adsorbents were performed at 185° C. (365° F.) in frying oil. The results are shown in Table 2 below.

TABLE-US-00004 TABLE 2 Disintegration Time (4 g of Solid Adsorbent Compressed to 1.0 Magnesium Peanut Candelilla metric Tons) Example Silicate, Oil, Wax, (Frying oil at 185° C.) No. weight % weight % weight % (seconds) 7 50 49 1 123 8 50 47 3 40 9 50 45 5 19

Examples 10-14. Solid Adsorbents with Magnesium Silicate, Soybean Oil and Hydrogenated Soybean Oil

[0114] Powder formulations and solid adsorbent formulations were made from magnesium silicate, soybean oil, and hydrogenated soybean oil according to the general methods described above with magnesium silicate having been heated to 90° C. and the oils to 80° C. About 270 grams of each powder formulations were compressed into solid adsorbent at 4.5 metric tons for about 2 minutes using a 4″ (76 mm) diameter cylindrical die press. Table 3 shows exemplary solid adsorbent compositions and the disintegration performance. Disintegration tests of the resulting solid adsorbents were performed at 176.7° C. (350° F.) in frying oil. The results are shown in Table 3 below.

TABLE-US-00005 TABLE 3 Magnesium Soybean Hydrogenated Disintegration Time, Example Silicate, Oil, Soybean Oil, Oil at 350□□ F. No. weight % weight % weight % (seconds) 10 50 50 0 nd 11 50 47 3 217 12 50 45 5 174 13 50 43 7 195 14 50 41 9 198 nd = no disintegration

[0115] A portion of the filter cake formed as a result of treating frying oil at 350° F. (176.7° C.) with the solid adsorbent of Example 12 compressed to 4.5 metric tons was collected after the oil was filtered. About 50 grams of the filter cake were collected and placed in a beaker, after which 100 grams of hexane were added. The hexane/filter cake mixture was stirred for about 5 minutes and filtered over a Whatman® filter paper No. 1 using a Buchner funnel attached to a filter flask in vacuo. The filter cake was washed further with two additional portions of 100 grams of hexane and dried in a 105° C. oven for 1 hour, thereby providing an off-white powder.

[0116] Particle size analysis was performed on the powder from the washings using a Laser Diffraction Particle Size Analyzer (Beckman Coulter LS 13 320). As shown in FIG. 1, the recovered magnesium silicate particles were found to be intact showing good particle size distribution which was not significantly different from particle size distribution of the original magnesium silicate powder shown in FIG. 2. These results show that the preparation of a solid composition of the present invention from magnesium silicate particles does not affect the integrity of the particles significantly.

Examples 15-17. Solid Adsorbent Formulations Made with Magnesium Silicate, and Mixtures of Corn Oil, Soybean Oil and Hydrogenated Soybean Oil

[0117] Solid adsorbent formulations were made from magnesium silicate and varying amounts of corn oil, soybean oil and hydrogenated soybean oil according to general methods described above. The powder formulation was made into solid adsorbents using 4.0 grams of material compressed at 1.0 metric ton for 15 seconds. The resulting solid composition disintegrated into particles upon treatment with frying oil at 185° C. (365° F.) and the results are shown in Table 4.

TABLE-US-00006 TABLE 4 Hydro- Disinte- genated gration Magnesium Corn Soybean Soybean Time, Oil at Example Silicate, Oil, Oil, Oil, 365□ F. No. weight % weight % weight % weight % (seconds) 15 50 25 25 0 nd 16 50 23.5 23.5 3 32 17 50 23 23 4 42

Example 18. Solid Adsorbent Formulation with Magnesium Silicate, Canola Oil and Palm Oil

[0118] A powder formulation and corresponding solid adsorbent formulation were made from 50% magnesium silicate, 35% canola oil, and 15% palm oil by weight according to the general methods described above. In this instance, magnesium silicate was heated to 150° C., canola oil to 80° C., and palm oil to 110° C. prior to mixing into a free-flowing powder. The powder formulation was made into a solid adsorbent using 4.0 grams of material compressed at 1.0 metric ton for 15 seconds. The resulting solid composition disintegrated into particles in 53 seconds upon treatment with frying oil at 185° C. (365° F.).

Example 19. Solid Adsorbent Formulation with Magnesium Silicate, Sodium Silicate, Canola Oil and Hydrogenated Soybean Oil

[0119] A powder formulation and corresponding solid adsorbent formulation were made from 50% magnesium silicate, 10% sodium silicate, 35% canola oil, and 5% hydrogenated soybean oil by weight according to the general methods described above. The powder formulation was made into a solid adsorbent using 4.0 grams of material compressed at 0.5 metric tons for 15 seconds. The resulting solid composition disintegrated into particles in 33 seconds upon treatment with frying oil at 185° C. (365° F.).

Example 20. Solid Adsorbent Composition with Magnesium Silicate. Soybean Oil and Water

[0120] A powder formulation and corresponding solid adsorbent composition were made from magnesium silicate (50%) and soybean oil (40%) by mixing the silicate with oil at 90° C. and allowing the mixture to cool to room temperature. Water (10%) then was added to the powder mixture and mixed thoroughly. The powder formulation was made into a solid adsorbent using 4.0 grams of material compressed at 1.0 metric ton for 15 seconds. The resulting solid composition disintegrated into particles in 40 seconds upon treatment with frying oil at 185° C. (365° F.).

Example 21. Frozen Solid Adsorbent Composition with Magnesium Silicate and Water

[0121] Water was used as a liquid to form a magnesium silicate concentrated slurry. 7 grams of magnesium silicate powder was mixed with 10 grams of water for a few minutes to provide 17 grams of a wet powder formulation with a water content of around 60%. The sample was placed in a plastic container (5 cm in diameter) to make a cylindrical solid shape. The container with the wet powder was frozen at a refrigerator temperature of −10° C. for 2 hours. The frozen formulation kept a cylindrical shape after being removed from the container and did not contain any cracks. This frozen solid was used in a disintegration test in which 200 g of frying oil was heated to 185° C. (365° F.). The resulting solid composition disintegrated into particles in 180 seconds upon contact with oil.

Example 22 Solid Adsorbent Formulation with Magnesium Silicate, Soybean Oil and Stearic Acid

[0122] A powder formulation and corresponding solid adsorbent formulation were made from 50% magnesium silicate, 47% soybean oil and 3% stearic acid by weight according to the general methods described above. In this instance magnesium silicate was heated to 90° C., and soybean oil and stearic acid were heated to 80° C. prior to mixing into a free-flowing powder. The powder formulation was made into a solid adsorbent using about 270 grams of material compressed at 8.0 metric tons for 120 seconds. The resulting solid composition disintegrated into particles in 148 seconds upon contact with frying oil at 185° C. (365° F.).

Examples 23, 24, 25, 26, and 27

[0123] Solid Adsorbent Compositions Made from Magnesium Silicate, Oils, and Fatty Binders (Stearyl Alcohol, Ethyl Stearate, Glyceryl Monostearate, Polyethylene Oxide Stearate or Sorbitan Monostearate)

[0124] Powder formulations and corresponding solid adsorbent formulations were made from magnesium silicate, frying oils and binders given in Table 5 below according to general methods described above. In this instance magnesium silicate was heated to 90° C., the oils and the binders (stearyl alcohol, ethyl stearate, glyceryl monostearate, polyethylene oxide stearate or sorbitan monostearate) were heated to 80° C. prior to mixing into a free-flowing powder. The powder formulations were made into solid adsorbents using about 4.0 grams of material compressed at 1.0 metric ton for 15 seconds. The resulting solid compositions disintegrated into particles upon treatment with hot frying oil at 176.7° C. (350° F.). The formulation compositions, in weight percent, and disintegration times are given in Table 5 below.

TABLE-US-00007 TABLE 5 Materials Example 23 Example 24 Example 25 Example 26 Example 27 Magnesium Silicate Powder 50.0 50.0 50.0 50.0 50.0 Canola Oil 12.5 25.0 Corn Oil 12.5 25.0 Peanut Oil 25.0 Soybean Oil 45.0 Stearyl Alcohol 25.0 Ethyl Stearate 25.0 Glyceryl Monostearate 5.0 Polyethylene oxide Stearate 25.0 Sorbital Monostearate 20.0 Solid Adsorbent Composition Performance Solid Adsorbent, grams 4.0 4.0 4.0 4.0 4.0 Compression Force, mT 1.0 1.0 1.0 1.0 1.0 Disintegration Time, Sec (350° F.) 45 19 22 38 40

[0125] The disclosures of all patents and publications, including published patent applications, are incorporated herein by reference to the same extent as if each patent and publication were incorporated individually by reference.

[0126] It is to be understood, however, that the scope of the present invention is not to be limited to the specific embodiments described above. The invention may be practiced other than as particularly described and still be within the scope of the accompanying claims.