PHOSPHORIC ACID PRODUCTION METHODS AND COMPOSITIONS

Abstract

A wet process phosphoric acid production method comprises digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer and a poly(carboxylic acid), or salt thereof, having a weight-average molecular weight of less than 1,000,000 grams per mole (g/mol), are added to the slurry. The poly(carboxylic acid) can be a poly(acrylic acid), or salt thereof, and the defoamer can be a dialkyl sulfosuccinate salt and an aliphatic alcohol or a fatty acid ester. The method enhances separation of phosphoric acid from calcium sulfate crystals in wet process phosphoric acid production by any one of increasing the volume average particle size of the calcium sulfate crystals, increasing filtration rate, and reducing foam formation.

Claims

1. A wet process phosphoric acid production method comprising: digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer and a poly(carboxylic acid), or salt thereof, having a weight-average molecular weight of less than 1,000,000 grams per mole (g/mol), are added to the slurry.

2. The method of claim 1, wherein the defoamer and poly(carboxylic acid), or salt thereof, are added separately to the slurry.

3. The method of claim 1, wherein the defoamer and poly(carboxylic) acid, or salt thereof, are premixed before adding to the slurry.

4. The method of claim 1, wherein the defoamer and poly(carboxylic acid), or salt thereof, are each independently premixed with the phosphate-containing ore, the sulfuric acid, recycled phosphoric acid, or both the sulfuric acid and recycled phosphoric acid, before adding to the slurry.

5. The method of claim 1, wherein the poly(carboxylic acid) or salt thereof, has a weight-average molecular weight of 300 to less than 1,000,000 g/mol.

6. The method of claim 1, wherein the poly(carboxylic acid), or salt thereof, is derived from polymerization of (meth)acrylic acid, maleic acid, a (meth)acrylate salt, a maleate salt, or a combination comprising at least one of the foregoing monomers.

7. The method of claim 1, wherein the poly(carboxylic acid), or salt thereof, is poly(acrylic acid), a salt thereof, or a combination comprising at least one of the foregoing.

8. The method of claim 1, wherein the poly(carboxylic acid), or salt thereof, is a copolymer of acrylic acid and maleic acid, a salt thereof, or a combination comprising at least one of the foregoing.

9. The method of claim 1, wherein the poly(carboxylic acid), or salt thereof, is a copolymer of acrylic acid and a polyethylene glycol ether methacrylate, a salt thereof, or a combination comprising at least one of the foregoing.

10. The method of claim 1, wherein the defoamer is a fatty acid, a fatty acid salt, a fatty acid ester, a sulfonic acid, a sulfonic acid salt, a sulfonic acid ester, an aliphatic alcohol, or a combination comprising at least one of the foregoing defoamers.

11. The method of claim 1, wherein the defoamer comprises a dialkyl sulfosuccinate salt.

12. The method of claim 11, wherein the dialkyl sulfosuccinate salt has the chemical structure: ##STR00003## wherein R.sup.1 and R.sup.2 are each independently a linear or branched C.sub.4-18 alkyl, C.sub.5-18 cycloalkyl, C.sub.7-18 arylalkyl, or C.sub.6-18 aryl, unsubstituted or substituted by hydroxyl or C.sub.1-18 alkoxy; M is lithium, sodium, potassium, or ammonium; and m is 1.

13. The method of claim 11, wherein the defoamer further comprises an aliphatic alcohol.

14. The method of claim 11, wherein the defoamer further comprises a fatty acid, a fatty acid salt, a fatty acid ester, or a combination comprising at least one of the foregoing defoamers.

15. The method of claim 1, wherein a sufficient amount of the poly(carboxylic acid), or salt thereof, is added to the slurry to increase volume average particle size of the calcium sulfate crystals compared to the same method without addition of the poly(carboxylic acid), or salt thereof.

16. The method of claim 1, wherein a sufficient amount of the poly(carboxylic acid), or salt thereof, is added to the slurry to enhance separation of the phosphoric acid from the calcium sulfate crystals compared to the same method without addition of the poly(carboxylic acid), or salt thereof.

17. The method of claim 1, wherein sufficient amounts of the defoamer and the poly(carboxylic acid), or salt thereof, are added to the slurry to reduce foam formation compared to the same method without addition of the defoamer and the poly(carboxylic acid), or salt thereof.

18. The method of claim 15, wherein the sufficient amount of poly(carboxylic acid), or salt thereof, is 0.01 to 10 kg/T P.sub.2O.sub.5.

19. The method of claim 17, wherein the sufficient amount of poly(carboxylic acid), or salt thereof, is 0.01 to 10 kg/T P.sub.2O.sub.5, and the sufficient amount of defoamer is 0.1 to 20 kg/T P.sub.2O.sub.5.

20. A wet process phosphoric acid production method comprising: digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer comprising a dialkyl sulfosuccinate salt and an aliphatic alcohol, and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol, are added to the slurry.

21. A wet process phosphoric acid production method comprising: digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer comprising a dialkyl sulfosuccinate salt and a fatty acid ester, and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol, are added to the slurry.

22. A composition for enhancing the separation of phosphoric acid from calcium sulfate crystals, the composition comprising: a defoamer comprising a dialkyl sulfosuccinate salt and an aliphatic alcohol; and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol.

23. A composition for enhancing the separation of phosphoric acid from calcium sulfate crystals, the composition comprising: a defoamer comprising a dialkyl sulfosuccinate salt and a fatty acid ester; and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Referring now to the Drawings:

[0016] FIG. 1 depicts plots of cumulative particle size distributions of the filter cakes from the digestion of phosphate ore in Ex. 1-4, obtained using a FlowCam. ESD in the x-axis is Equivalent Spherical Diameter. The plots show an increase in particle size upon addition of P(AA-co-MA) (M.sub.w=3000 g/mol) without defoamers during digestion. The increase in particle size depends on dosage and an optimal dosage of 0.6 kg/T P.sub.2O.sub.5 is observed (Ex. 3).

[0017] FIG. 2 depicts plots of cumulative particle size distributions of filter cakes from the digestion of phosphate ore in Ex. 5-8, obtained using a FlowCam. ESD in the x-axis is Equivalent Spherical Diameter.

[0018] FIG. 3 depicts plots of cumulative particle size distributions of filter cakes from the digestion of phosphate ore in Ex. 12-15, obtained using a FlowCam. ESD in the x-axis is Equivalent Spherical Diameter. The plots show the effect of molecular weight of PAA polymers in combination with IONQUEST D3001 defoamers during digestion of phosphate ore. While low molecular weight polymers promote crystal growth (Ex. 13-14 vs. Ex. 12), high molecular weight polymers depress crystal growth (Ex. 15 vs. Ex. 12).

[0019] FIG. 4 depicts plots of particle size distributions of filter cakes from the digestion of phosphate ore in Ex. 5, 6, and 8, obtained using a FlowCam. ESD in the x-axis is Equivalent Spherical Diameter. The plots show that particle size distribution shifts upwards upon addition of P(AA-co-MA) (M.sub.w=3000 g/mol) and IONQUEST D3001 (FIG. 8), compared to no additive (Ex. 5), and IONQUEST D3001 alone (Ex. 6) during digestion of phosphate ore.

[0020] FIG. 5 depicts visible micrographs collected with FlowCam on filter cake crystals after digestion of phosphate ore. These images show that P(AA-co-MA) (M.sub.w=3000 g/mol) in combination with IONQUEST D3001 (Ex. 8), promotes generation of crystal clusters/aggregates compared to IONQUEST D3001 alone (Ex. 6).

[0021] FIG. 6 depicts photographs of foam levels of slurries after digestion of phosphate ore in Ex. 5-7, with Ex. 6 being dosed with 8 kg/T P.sub.2O.sub.5 IONQUEST D3001 and Ex. 7 being dosed with 7.2 kg/T P.sub.2O.sub.5 IONQUEST D3001 and 0.8 kg/T P.sub.2O.sub.5 P(AA-Na). While IONQUEST D3001 reduced the amount of foam in Ex. 6 relative to Ex. 5, co-addition of P(AA-Na) (M.sub.w=1200) during the digestion step while maintaining the same total amount of additive (Ex. 7) further reduced the amount of foam.

DETAILED DESCRIPTION OF CERTAIN EMBODIMENTS OF THE INVENTION

[0022] The present inventors have developed an improved wet process phosphoric acid production method which enhances separation of phosphoric acid from calcium sulfate crystals. The method comprises digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer and a poly(carboxylic acid), or salt thereof, having a weight-average molecular weight of less than 1,000,000 grams per mole (g/mol) are added to the slurry. Advantageously, adding a defoamer and a poly(carboxylic acid), or salt thereof, having a weight-average molecular weight of less than 1,000,000 g/mol, to wet process phosphoric acid slurry was found to increase volume average particle size of calcium sulfate crystals, enhance separation of phosphoric acid from calcium sulfate crystals by improving filtration rates, and to simultaneously reduce foam formation.

[0023] The defoamer and poly(carboxylic acid), or salt thereof, can be added to the wet process phosphoric acid slurry in a variety of ways. For example the defoamer and poly(carboxylic acid), or salt thereof, can be added separately to the slurry. The defoamer and poly(carboxylic) acid, or salt thereof, can also be premixed before adding to the slurry. Furthermore, in any or all embodiments, the defoamer and poly(carboxylic acid), or salt thereof, can be each independently or in combination premixed with the sulfuric acid, recycled phosphoric acid, or both the sulfuric acid and recycled phosphoric acid, before adding to the slurry. It is desirable to add the defoamer and poly(carboxylic) acid, or salt thereof, during the digestion step.

[0024] Despite teachings to the contrary in the art, the present inventors have surprisingly found that low molecular weight poly(carboxylic acids), or salt thereof, i.e., those having a weight-average molecular weight of less than 1,000,000 g/mol, are effective in increasing the volume average particle size of calcium sulfate crystals in WPA production. For example, the poly(carboxylic acid) or salt thereof, can have a weight-average molecular weight of 300 to less than 1,000,000 g/mol. Within this range, the weight-average molecular weight can be greater than or equal to 500, 700, or 1,000 g/mol and less than or equal to 900,000, 700,000, 500,000, 100,000, 50,000, or 20,000 g/mol. In any or all embodiments according to the invention, the weight-average molecular weight can be 1,000 to 100,000 g/mol. Weight-average molecular weight as reported herein can be measured, for example, by gel permeation chromatography, or other suitable methods routinely known to those skilled in the art.

[0025] The poly(carboxylic acid), or salt thereof, can be an addition polymer of carboxylic acid-functional ethylenically unsaturated monomers. The carboxylic acid-functional ethylenically unsaturated monomer can be, for example, acrylic acid, methacrylic acid, crotonic acid, itaconic acid, an itaconic acid monoester, fumaric acid, a fumaric acid monoester, maleic acid, a maleic acid monoester, or a combination comprising at least one of the foregoing carboxylic acid-functional ethylenically unsaturated monomers. The poly(carboxylic acid) can also be an addition polymer of a carboxylic acid anhydride-functional ethylenically unsaturated monomer, in which the carboxylic acid anhydride functionality can be converted to carboxylic acid functionality, for example maleic anhydride or itaconic anhydride. The carboxylic acid-functional ethylenically unsaturated monomer can be (meth)acrylic acid, i.e., acrylic acid, methacrylic acid, or a combination thereof. The poly(carboxylic acid) can be in the form of an acid, a mixed acid and salt, or a salt. Any organic or inorganic cation can be used as the salt, but inorganic counterions are preferred, for example an alkali metal or an alkaline earth metal. Thus in any or all embodiments, the poly(carboxylic acid), or salt thereof, is derived from polymerization of (meth)acrylic acid, maleic acid, a (meth)acrylate salt, a maleate salt, or a combination comprising at least one of the foregoing monomers. The poly(carboxylic acid), or salt thereof, can be, for example, poly(acrylic acid), poly(acrylic acid) sodium salt, poly(acrylic acid-co-maleic acid), poly(acrylic acid-co-maleic acid) sodium salt, or a combination comprising at least one of the foregoing poly(carboxylic acids). In any or all embodiments, the poly(carboxylic acid), or salt thereof, is poly(acrylic acid), a salt thereof, for example a sodium salt thereof, or a combination comprising at least one of the foregoing. The poly(carboxylic acid), or salt thereof, can also be a copolymer of acrylic acid and maleic acid, a salt thereof, for example a sodium salt thereof, or a combination comprising at least one of the foregoing. The poly(carboxylic acid), or salt thereof, can also be a copolymer of acrylic acid and a polyethylene glycol ether methacrylate, a salt thereof, or a combination comprising at least one of the foregoing.

[0026] The poly(carboxylic acid), or salt thereof, can be a copolymer of carboxylic acid-functional ethylenically unsaturated monomer and other ethylenically unsaturated monomers. The other ethylenically unsaturated monomer can be an ionic monomer, for example, a sulfonic acid-functional monomer, a phosphoric acid-functional monomer, a phosphonic acid-functional monomer, or a salt thereof. Examples of sulfonic-acid functional monomers include 2-sulfoethyl (meth)acrylate, 3-sulfopropyl (meth)acrylate, styrene sulfonic acid, vinyl sulfonic acid, and 2-(meth)acrylamide-2-methyl propanesulfonic acid. Examples of phosphoric acid-functional monomers include 2-phosphoethyl (meth)acrylate, 2-phosphopropyl (meth)acrylate, 3-phosphopropyl (meth)acrylate, phosphobutyl (meth)acrylate, and 3-phospho-2-hydroxypropyl (meth)acrylate. The phosphoric acid-functional monomer can also be a phosphoric acid ester of an alkoxylated hydroxyalkyl (meth)acrylate, for example a hydroxyethyl or hydroxypropyl (meth)acrylate ethoxylate or propoxylate having 1 to 50 ethoxy or propoxy repeat units. The ionic monomer can also be 2-(N,N-dimethylamino)ethyl (meth)acrylate.

[0027] The other ethylenically unsaturated monomer can be a nonionic monomer. The nonionic monomer can be a hydrophilic non-ionic ethylenically unsaturated monomer, for example hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, polyethylene glycol (meth)acrylate, or (meth)acrylamide. The nonionic monomer can also be a hydrophobic non-ionic monomer, for example an alkyl ester of (meth)acrylic acid, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, and lauryl (meth)acrylate. The nonionic monomer can also be styrene, or a substituted styrene such as -methyl styrene, an -olefin such as ethylene, propylene, 1-decene, and diisobutylene, or butadiene. The nonionic monomer can also be a vinyl monomer such as acrylonitrile, vinyl chloride, vinyl acetate, vinyl butyrate, or a vinyl ester of a branched, tertiary-alkyl alcohol, sold under the tradename VeoVa, for example VeoVa 9 Monomer, VeoVa 10 Monomer, VeoVa 11 Monomer, available from Momentive Specialty Chemicals. In any or all embodiments according to the invention, the poly(carboxylic acid), or salt thereof, can be derived from copolymerization of (meth)acrylic acid with at least one other nonionic (meth)acrylic or vinyl monomer. For example, the poly(carboxylic acid), or salt thereof, can be a copolymer of acrylic acid and a polyethylene glycol ether methacrylate, a salt thereof, or a combination comprising at least one of the foregoing. For example, the polycarboxylic acid, or salt thereof, can be a copolymer of acrylic acid and polyethylene glycol methyl ether methacrylate with 50 ethylene glycol (EO) (MH50), (P(AA-co-MH50)). The AA to MH50 molar ratio can be, for example, 80:20.

[0028] Advantageously, a defoamer is combined with the poly(carboxylic acid), or salt thereof, to control foam in the wet process phosphoric acid process. Controlling foam can be accomplished by either decreasing an amount of foam formed or by preventing foam formation in the first place. Although the low molecular weight poly(carboxylic acids), or salts thereof, disclosed herein have no defoamer activity, the combination of a defoamer and low molecular weight poly(carboxylic acids), or salts thereof, have surprisingly been found to exhibit a synergistic effect on controlling foam.

[0029] The defoamer is a fatty acid, a fatty acid salt, a fatty acid ester, a sulfonic acid, a sulfonic acid salt, an ester of a sulfonic acid or sulfonic acid salt, an aliphatic alcohol, or a combination comprising at least one of the foregoing defoamers. As described above, the defoamer can be in the form of an acid, ester, salt, or mixed acid, ester, or salt. Any organic or inorganic cation can be used as the salt, for example an alkali metal, an alkaline earth metal, an ammonium ion, a quaternary ammonium ion, or a phosphonium ion. In any or all embodiments according to the invention, the defoamer comprises a dialkyl ester of a sulfosuccinate salt, i.e., a dialkyl sulfosuccinate. The dialkyl sulfosuccinate can have the chemical structure:

##STR00001##

wherein R.sup.1 and R.sup.2 are each independently a linear or branched, C.sub.4-18 alkyl, specifically C.sub.4-12 alkyl, more specifically C.sub.4-8 alkyl, C.sub.5-18 cycloalkyl, C.sub.7-18 arylalkyl, or C.sub.6-18 aryl, unsubstituted or substituted by hydroxyl or C.sub.1-18 alkoxy, more specifically C.sub.1-4 alkoxy. In any or all embodiments according to the invention, M is an alkali metal, an alkaline earth metal, an ammonium ion, a quaternary ammonium ion, or a combination comprising at least one of the foregoing cations. When M is an alkaline earth metal, m is 0.5, and when M is an alkali metal or ammonium ion, m is 1. M can be, for example, lithium, sodium, potassium, calcium, or ammonium, specifically lithium, sodium, potassium, or ammonium, and more specifically, sodium. In any or all embodiments according to the invention, R.sup.1 and R.sup.2 are each independently a linear or branched C.sub.4-12 alkyl, specifically C.sub.4-8 alkyl. For example, R.sup.1 and R.sup.2 can each independently be amyl, hexyl, octyl, nonyl, dodecyl, or stearyl. Since these alkyl groups can be branched, octyl can be 2-ethylhexyl. Thus in any or all embodiments according to the invention, R.sup.1 and R.sup.2 are both 2-ethylhexyl, M is sodium, and m is 1. This specific dialkyl sulfosuccinate is known as sodium dioctyl sulfosuccinate.

[0030] As mentioned above, combinations of defoamers can also be effective. Thus in any or all embodiments according to the invention, a defoamer comprising a dialkyl sulfonate salt can further comprise an aliphatic alcohol, for example 2-ethylhexanol. In any or all embodiments according to the invention, the defoamer comprising a dialkyl sulfonate salt can also further comprise a fatty acid, a fatty acid salt, a fatty acid ester, or a combination thereof, for example oleic acid, an oleic acid salt, an oleic ester, or a combination thereof.

[0031] Advantageously, the low molecular weight poly(carboxylic acid), or salt thereof, provides increased volume average particle size of the calcium sulfate crystals in WPA production. Thus, a wet process phosphoric acid production method comprises digesting phosphate-containing ore in a slurry comprising sulfuric acid, and adding a sufficient amount of the poly(carboxylic acid), or salt thereof, to the slurry to increase volume average particle size of the calcium sulfate crystals compared to the same method without addition of the poly(carboxylic acid), or salt thereof.

[0032] Advantageously, the increased volume average particle size of the calcium sulfate crystals obtained in the process results in enhanced separation of phosphoric acid from the calcium sulfate crystals, for example by increasing filtration rate of the phosphoric acid. Thus, a wet process phosphoric acid production method comprises digesting phosphate-containing ore in a slurry comprising sulfuric acid, and adding a sufficient amount of the poly(carboxylic acid), or salt thereof, to the slurry to enhance separation of the phosphoric acid from the calcium sulfate crystals compared to the same method without addition of the poly(carboxylic acid), or salt thereof.

[0033] Advantageously, the combination of defoamer and low molecular weight poly(carboxylic acid), or salt thereof, also provides reduced foam formation. Thus, a wet process phosphoric acid production method comprises digesting phosphate-containing ore in a slurry comprising sulfuric acid, and adding sufficient amounts of the defoamer and the poly(carboxylic acid), or salt thereof, to reduce foam formation compared to the same method without addition of the defoamer and the poly(carboxylic acid), or salt thereof.

[0034] Many factors, including ore type, temperature, agitation, reactor design, acid chemistry, foreign ions, organic species, and viscosity of the phosphoric acid medium can affect the performance of the poly(carboxylic acid), or salt thereof. Therefore a suitable dosage of poly(carboxylic acid), or salt thereof, may depend on any of these variables, but can be determined by no more than routine methods known to those skilled in the art. Dosage is herein expressed in units of kilogram of additive per ton of P.sub.2O.sub.5 in the phosphate ore, and is abbreviated as kg/T P.sub.2O.sub.5. The sufficient amount of the poly(carboxylic acid), or salt thereof, to increase volume average particle size of the calcium sulfate crystals, and to thereby enhance separation of the phosphoric acid from the calcium sulfate crystals, can be in the range of 0.01 to 10 kg/T P.sub.2O.sub.5. Within this range, the sufficient amount of poly(carboxylic acid), or salt thereof, can be greater than or equal to 0.02, 0.05, or 0.1 kg/T P.sub.2O.sub.5 and less than or equal to 5, 4, 3, 2, or 1 kg/T P.sub.2O.sub.5.

[0035] The same factors, including ore type, temperature, agitation, reactor design, acid chemistry, foreign ions, organic species, and viscosity of the phosphoric acid medium can also affect the performance of the combination of defoamer and poly(carboxylic acid), or salt thereof in reducing foam formation. However, the sufficient amount of defoamer to reduce foam formation can be in the range of 0.1 to 20 kg/T P.sub.2O.sub.5. Within this range, the sufficient amount of defoamer can be greater than or equal to 0.2, 0.3, 0.4, or 0.5 kg/T P.sub.2O.sub.5 and less than or equal to 15, 10, 9, 8, 7, or 6 kg/T P.sub.2O.sub.5. Moreover, the sufficient amount of poly(carboxylic acid), or salt thereof, in combination with the defoamer, to reduce foam formation can be the same amount sufficient to increase volume average particle size and to enhance separation of the phosphoric acid from the calcium sulfate crystals disclosed in the preceding paragraph.

[0036] While not intending to limit the scope of the wet process phosphoric acid production method, more specific methods are disclosed herein. For example, a wet process phosphoric acid production method can comprise digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer comprising a dialkyl sulfosuccinate salt and an aliphatic alcohol and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol, are added to the slurry. In another example of the method, a defoamer comprising a dialkyl sulfosuccinate salt and a fatty acid ester, and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol, are added to the slurry.

[0037] As described above, the defoamer and poly(carboxylic) acid can be premixed before adding to the slurry. Thus, in any or all embodiments, a composition comprises a defoamer and a poly(carboxylic acid), or salt thereof, having a weight-average molecular weight of less than 1,000,000 g/mol. For example, a composition for enhancing the separation of phosphoric acid from calcium sulfate crystals, comprises a defoamer comprising a dialkyl sulfosuccinate salt and an aliphatic alcohol; and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol. A composition for enhancing the separation of phosphoric acid from calcium sulfate crystals, can also comprise a defoamer comprising a dialkyl sulfosuccinate salt and a fatty acid ester; and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol.

[0038] This disclosure is further illustrated by the following aspects, which are not intended to limit the claims.

[0039] Aspect 1. A wet process phosphoric acid production method comprising: digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer and a poly(carboxylic acid), or salt thereof, having a weight-average molecular weight of less than 1,000,000 g/mol, are added to the slurry.

[0040] Aspect 2. The method of aspect 1, wherein the defoamer and poly(carboxylic acid), or salt thereof, are added separately to the slurry.

[0041] Aspect 3. The method of aspect 1, wherein the defoamer and poly(carboxylic) acid, or salt thereof, are premixed before adding to the slurry.

[0042] Aspect 4. The method of aspect 3, wherein the defoamer and poly(carboxylic acid), or salt thereof, are each independently premixed with the sulfuric acid, recycled phosphoric acid, or both the sulfuric acid and recycled phosphoric acid, before adding to the slurry.

[0043] Aspect 5. The method of any of aspects 1 to 4, wherein the poly(carboxylic acid) or salt thereof, has a weight-average molecular weight of 300 to less than 1,000,000 g/mol.

[0044] Aspect 6. The method of any of aspects 1 to 5, wherein the poly(carboxylic acid), or salt thereof, is derived from polymerization of (meth)acrylic acid, maleic acid, a (meth)acrylate salt, a maleate salt, or a combination comprising at least one of the foregoing monomers.

[0045] Aspect 7. The method of any of aspects 1 to 6, wherein the poly(carboxylic acid), or salt thereof, is poly(acrylic acid), a salt thereof, or a combination comprising at least one of the foregoing.

[0046] Aspect 8. The method of any of aspects 1 to 6, wherein the poly(carboxylic acid), or salt thereof, is a copolymer of acrylic acid and maleic acid, a salt thereof, or a combination comprising at least one of the foregoing.

[0047] Aspect 9. The method of any of aspects 1 to 6, wherein the poly(carboxylic acid), or salt thereof, is a copolymer of acrylic acid and a polyethylene glycol ether methacrylate, a salt thereof, or a combination comprising at least one of the foregoing.

[0048] Aspect 10. The method of any of aspects 1 to 9, wherein the defoamer comprises a fatty acid, a fatty acid salt, a fatty acid ester, a sulfonic acid, a sulfonic acid salt, a sulfonic acid ester, an aliphatic alcohol, or a combination comprising at least one of the foregoing defoamers.

[0049] Aspect 11. The method of any of aspects 1 to 10, wherein the defoamer comprises a dialkyl sulfosuccinate salt.

[0050] Aspect 12. The method of aspect 11, wherein the dialkyl sulfosuccinate salt has the chemical structure:

##STR00002##

wherein R.sup.1 and R.sup.2 are each independently a linear or branched C.sub.4-18 alkyl, C.sub.5-18 cycloalkyl, C.sub.7-18 arylalkyl, or C.sub.6-18 aryl, unsubstituted or substituted by hydroxyl or C.sub.1-18 alkoxy; M is lithium, sodium, potassium, or ammonium; and m is 1.

[0051] Aspect 13. The method of aspect 12, wherein R.sup.1 and R.sup.2 are both 2-ethylhexyl, and M is sodium.

[0052] Aspect 14. The method of any of aspects 11 to 13, wherein the defoamer further comprises an aliphatic alcohol.

[0053] Aspect 15. The method of aspect 14, wherein said aliphatic alcohol comprises 2-ethylhexanol.

[0054] Aspect 16. The method of any of aspects 11 to 13, wherein the defoamer further comprises a fatty acid, a fatty acid salt, a fatty acid ester, or a combination comprising at least one of the foregoing defoamers.

[0055] Aspect 17. The method of any of aspects 11 to 13, wherein the defoamer further comprises a tall oil fatty acid, a tall oil fatty acid salt, an oleic acid, an oleic acid salt, or a combination comprising at least one of the foregoing defoamers.

[0056] Aspect 18. The method of any of aspects 1 to 17, wherein each salt is independently a lithium salt, a sodium salt, a potassium salt, an ammonium salt, or a combination comprising at least one of the foregoing salts.

[0057] Aspect 19. The method of any of aspects 1 to 18, wherein a sufficient amount of the poly(carboxylic acid), or salt thereof, is added to the slurry to increase volume average particle size of the calcium sulfate crystals compared to the same method without addition of the poly(carboxylic acid), or salt thereof.

[0058] Aspect 20. The method of any of aspects 1 to 19, wherein a sufficient amount of the poly(carboxylic acid), or salt thereof, is added to the slurry to enhance separation of the phosphoric acid from the calcium sulfate crystals compared to the same method without addition of the poly(carboxylic acid), or salt thereof.

[0059] Aspect 21. The method of any of aspects 1 to 20, wherein sufficient amounts of the defoamer and the poly(carboxylic acid), or salt thereof, are added to the slurry to reduce foam formation compared to the same method without addition of the defoamer and the poly(carboxylic acid), or salt thereof.

[0060] Aspect 22. The method of any of aspects 19 to 21, wherein the sufficient amount of poly(carboxylic acid), or salt thereof, is 0.01 to 10 kg/T P.sub.2O.sub.5.

[0061] Aspect 23. The method of aspect 21, wherein the sufficient amount of poly(carboxylic acid), or salt thereof, is 0.01 to 10 kg/T P.sub.2O.sub.5, and the sufficient amount of defoamer is 0.1 to 20 kg/T P.sub.2O.sub.5.

[0062] Aspect 24. A wet process phosphoric acid production method comprising: digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer comprising a dialkyl sulfosuccinate salt and an aliphatic alcohol, and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol, are added to the slurry.

[0063] Aspect 25. A wet process phosphoric acid production method comprising: digesting phosphate-containing ore in a slurry comprising sulfuric acid, whereby phosphoric acid and calcium sulfate crystals are formed; and separating the phosphoric acid from the calcium sulfate crystals; wherein a defoamer comprising a dialkyl sulfosuccinate salt and a fatty acid ester, and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol, are added to the slurry.

[0064] Aspect 26. A composition for enhancing the separation of phosphoric acid from calcium sulfate crystals, the composition comprising: a defoamer and a poly(carboxylic acid), or salt thereof, having a weight-average molecular weight of less than 1,000,000 g/mol.

[0065] Aspect 27. A composition for enhancing the separation of phosphoric acid from calcium sulfate crystals, the composition comprising: a defoamer comprising a dialkyl sulfosuccinate salt and an aliphatic alcohol; and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol.

[0066] Aspect 28. A composition for enhancing the separation of phosphoric acid from calcium sulfate crystals, the composition comprising: a defoamer comprising a dialkyl sulfosuccinate salt and a fatty acid ester; and a poly(acrylic acid), or salt thereof, having a weight-average molecular weight of 300 to less than 1,000,000 g/mol.

EXAMPLES

[0067] The following examples are provided to assist one skilled in the art to further understand certain embodiments of the present invention. These examples are intended for illustration purposes and should not be construed as limiting the scope of the present invention.

[0068] The performance of low molecular weight poly(carboxylic acid) homo- or co-polymers and their salts, applied by themselves or in combination with conventional defoamers, for increasing the average particle sizes of gypsum crystals, controlling the foam, and enhancing the filtration rate of phosphoric acid slurry is measured via bench-scale digestion and a vacuum filtration test. The general procedures are outlined below. Those skilled in the art will appreciate that different volumes, ratios, and addition rates may be used to generate different phosphoric acid slurries.

General Procedure for Bench-scale Digestion of Phosphate Ores

[0069] A 500-mL jacketed reactor connected with a thermal bath for keeping temperature at around 80 C. was used for digestion of phosphate ore in powder form. The reactor was also connected to a cooling condenser to avoid water evaporation during the digestion. Phosphoric acid and sulfuric acid were added to the reactor continuously through two peristaltic pumps (MasterFlex L/S). The phosphate ore powder was manually added roughly continuously at a corresponding rate. In one embodiment, the feed rate of sulfuric acid (52.4%) was 3.67 g/minute; the feed rate of phosphoric acid (37.1%) was 7.67 g/minute; and the feed rate of phosphate ore was 2 g/minute. The total feed time was around 30 minutes. After feeding acids and ore, the digestion was continued for an additional 2 to 3 hours to fully digest the ore. When reagents of interest (such as poly(carboxylic acid), or salts thereof, and defoamers) were used, appropriate amount of reagents were first mixed with the aforementioned phosphoric acid feed and then pumped into the reactor continuously. The reagents alternatively could have been added directly into slurry or be first mixed with sulfuric acid, or phosphate ore powder. During the whole process, the digestion slurry was stirred with an overhead stirrer (Glas-Col Precision Speed Controlled Stirrer) equipped with a propeller-type impeller running at 300 rpm.

Filtration Test for Phosphoric Acid Slurries

[0070] 210 g of phosphoric acid slurry after digestion was transferred to a filtration funnel with a 45-m polypropylene net filter (Millipore PP4504700) and vacuum filtration was started immediately. Filtration time reported herein is the time when the surface of the filter cake was free of phosphoric acid.

Method for Analysis of Particle Sizes in Filter Cake

[0071] Volume average particle size and volume average particle size distribution of the filter cake were determined using FlowCam, a dynamic imaging particle analysis instrument. In this analysis, 1 to 2 mg of dried filter cake particles were first dispersed in 6 mL of propylene glycol. An appropriate amount of the particle dispersion was then transferred to a pipet tip reservoir connected to a flow cell (FC300) supported on a cell holder. The dynamic imaging process was started afterwards and images of tens of thousands of particles were taken. At the end, these images were analyzed with the FlowCam software, generating results such as volume average particle size, volume average particle size distribution, aspect ratio, and aspect ratio distribution.

Examples 1-25. Digestion of Phosphate Ore a with or without Crystal Growth Modifiers

[0072] Poly(acrylic acid) polymers (PAA), poly(acrylic acid-co-maleic acid) polymers (P(AA-co-MA)), and their salts (such as sodium polyacrylate (P(AA-Na)) of various molecular weights were purchased from Sigma-Aldrich, St. Louis, Mo., or Polyscience, Inc., Warrington, Pa. A copolymer of acrylic acid (AA) and polyethylene glycol methyl ether methacrylate (with 50 EO, MH50), with an AA to MH50 molar ratio of 80:20 (P(AA-co-MH50) was obtained from Solvay S.A. The weight-average molecular weights herein are those reported by the above vendors. The method of measuring the reported weight-average molecular weights is not provided by the vendors. However, weight-average molecular weight can be measured, for example, by gel permeation chromatography.

[0073] Defoamers CYBREAK 675HFP (mixture of sulfosuccinate surfactants and aliphatic alcohols) and IONQUEST D3001 (alkali salt of sulfosuccinic acid dialkyl esters and fatty acid esters) were obtained from Solvay SA. Defoamer #3 was a mixture of sodium dioctyl sulfosuccinate (70% in propylene glycol), fatty acid esters, a glycol ether, and 2-ethylhexanol in a 4:4:1:1 ratio. Defoamer #4 was a mixture of oleic acid and 2-ethylhexanol in a 9:1 weight ratio. The efficacy of these polymers, by themselves and in combination with defoamers, in promoting crystal growth and enhancing filtration rate was studied using the aforementioned digestion procedure, filtration test, and particle size analysis method. Results from digestion of phosphate ores from various sources are shown in Table 1-5. Each table represents a different set of tests. Ex. 1, 5, 12, 16, 21, and 26 were controls without any defoamer or poly(carboxylic acid), or salt thereof. Cumulative particle size distributions of the filter cakes Ex. 1-4, 5-8, and 12-15 are provided in FIGS. 1, 2, and 3, respectively. Particle size distribution of the filter cakes of Ex. 5, 6, and 8 are provided in FIG. 4.

TABLE-US-00001 TABLE 1 Dosage Effect of P(AA-co-MA) on Particle Size and Filtration Rate Without Defoamer Vol. Ave. Phosphate Dosage Filtration Particle Size Ex. Ore Type Reagents (kg/T P.sub.2O.sub.5) Defoamer Time (s) (m) 1.sup.a A None None 89 45.4 2 A P(AA-co-MA) 0.3 None 69 56.4 (M.sub.w = 3000) 3 A P(AA-co-MA) 0.6 None 50 59.7 (M.sub.w = 3000) 4 A P(AA-co-MA) 1.2 None 62 52.9 (M.sub.w = 3000) .sup.aComparative Example.

TABLE-US-00002 TABLE 2 Dosage and Molecular Weight Effects of PAA, P(AA-Na), and P(AA-MA) On Particle Size and Filtration Rate with IONQUEST D3001 Defoamer Vol. Av. Dosage Dosage Filtration Particle Phosphate (kg/T (kg/T Time Size Ex. Ore Type Reagent P.sub.2O.sub.5) Defoamer P.sub.2O.sub.5) (s) (m) 5.sup.a B None None 20 58.5 6.sup.a B None IONQUEST 8 20 97.4 D3001 7 B P(AA-Na) 0.8 IONQUEST 7.2 14 109.1 (M.sub.w = 1200) D3001 8 B P(AA-MA) 0.8 IONQUEST 7.2 12 109.0 (M.sub.w = 3000) D3001 9 B PAA 0.45 IONQUEST 4.1 14 104.8 (M.sub.w = 100k) D3001 10 B P(AA-Na) 2 None 34 (M.sub.w = 1200) 11.sup.a,b B P(AA-Na) 0.8 IONQUEST 7.2 19 (M.sub.w = 1200) D3001 .sup.aComparative Examples. .sup.bPAA and defoamer were dosed to slurry after the digestion step and before the filtration step.

TABLE-US-00003 TABLE 3 Molecular Weight Effect of PAA Homo- and Co-polymers On Particle Size and Filtration Rate with IONQUEST D3001 Defoamer Dosage Dosage Vol. Ave. Phosphate (kg/T (kg/T Filtration Particle Ex. Ore Type Reagent P.sub.2O.sub.5) Defoamer P.sub.2O.sub.5) Time (s) Size (m) 12.sup.a C Blank None 100 26.4 13 C P(AA-co- 0.6 IONQUEST 6 20 55.5 MH50) 80/20 D3001 (M.sub.w = 15.4k) 14 C PAA 0.6 IONQUEST 6 18 47.1 (M.sub.w = 450k) D3001 15 C PAA 0.6 IONQUEST 6 180 24.5 (M.sub.w = 1,000k) D3001 .sup.aComparative Example.

TABLE-US-00004 TABLE 4 Dosage Effect of P(AA-Na) on Particle Size and Filtration Rate With CYBREAK 675 HFP Defoamer) Dosage Dosage Vol. Ave. Phosphate (kg/T (kg/T Filtration Particle Ex. Ore Type Reagents P.sub.2O.sub.5) Defoamer P.sub.2O.sub.5) Time (s) Size (gm) 16.sup.a D None None 112 42.2 17 D P(AA-Na) 0.18 None 58 52.8 (M.sub.w = 1200) 18.sup.a D None CYBREAK 1.2 99 38.3 675 HFP 19 D P(AA-Na) 0.06 CYBREAK 0.6 104 43.1 (M.sub.w = 1200) 675 HFP 20 D P(AA-Na) 0.12 CYBREAK 1.2 40 52.9 (M.sub.w = 1200) 675 HFP .sup.aComparative Examples.

TABLE-US-00005 TABLE 5 Dosage Effect of P(AA-Na) on Filtration Rate with Defoamer #3 and Defoamer #4) Phosphate Dosage Dosage Filtration Foam Ex. Ore Type Reagents (kg/T P.sub.2O.sub.5) Defoamer (kg/T P.sub.2O.sub.5) Time (s) Volume (mL) 21.sup.a E None None 80 40 22.sup.a E None Defoamer #3.sup.b 6.0 40 20 23 E PAA 0.6 Defoamer #3.sup.b 5.4 21 5 (M.sub.w = 100,000) 24.sup.a E None Defoamer #4.sup.c 6.0 30 10 25 E PAA 0.6 Defoamer #4.sup.c 5.4 22 5 (M.sub.w = 100,000) .sup.aComparative Examples. .sup.bDefoamer #3 was Sodium dioctyl sulfosuccinate (70% in propylene glycol), fatty acid esters, glycol ether, and 2-ethyl hexanol in 4:4:1:1 ratio. .sup.cDefoamer #4 was 90% Oleic acid + 10% 2-ethylhexanol.

TABLE-US-00006 TABLE 6 Dosage Effect of PAA after Digestion on Filtration Rate Without Defoamer Phosphate Dosage Filtration Ex. Ore Type Reagents (kg/T P.sub.2O.sub.5) Defoamer Time (s) 26.sup.a F None None 31 27.sup.a,b F P(AA) 0.18 None 32 .sup.aComparative Example. .sup.bPAA was dosed to slurry after the digestion step and before the filtration step.

[0074] It is known in the art (e.g. in U.S. Pat. No. 5,009,873) that high molecular weight (M.sub.w>1,000,000) is necessary for a polymer to be effective in promoting crystal growth. Low molecular weight polymers (M.sub.w<1,000,000) are generally used as dispersants or antiscalants to depress crystal growth and agglomeration. Thus it was surprising that low molecular weight poly(carboxylic acid) homo- and co-polymers and their salts, alone and in combination with defoamers, can increase the particle size of crystals during digestion of phosphate ores from various sources and thereby improve filtration rate. Increase in particle size and improved filtration rate were not observed when a high molecular weight PAA (M.sub.w1,000,000) was used. To the contrary, as shown in Comparative Ex. 15, high molecular weight PAA was detrimental to crystal growth and filtration rate. The dosage level of low molecular weight poly(carboxylic acid) polymers and salts thereof can affect particle size and filtration rate. While both a low dosage of about 0.06 to 0.3 kg/T P.sub.2O.sub.5 (as in Ex. 19 and 2, respectively) and a high dosage of about 1.2 kg/T P.sub.2O.sub.5 (as in Ex. 4) provide some improvement in particle size and filtration rate, particle size and filtration rate can be optimal between these limits. Optimal dosage can depend on the specific ore and digestion process used.

[0075] The comparisons of Ex. 7 to Ex. 11 and of Ex. 27 to Ex. 26 indicate that the poly(carboxylic acid), or salt thereof, alone or in combination with defoamers, should be dosed during the digestion step to obtain increased particle size and reduced filtration rate. If they are dosed after the digestion step, as in Ex. 11 and 27, there was no improvement in filtration rate compared to the controls (Ex. 6 and 26, respectively).

[0076] FIG. 5 depicts visible micrographs collected with FlowCam on filter cake crystals after digestion of phosphate ore. These images show that P(AA-co-MA) (M.sub.w=3,000), in combination with IONQUEST D3001, promotes generation of crystal clusters/aggregates. These data are contrary to the expectation that low molecular weight polymers disperse particles and prevent them from forming aggregates. In addition, it is also unexpected that defoamer efficacy (e.g. CYBREAK 675 HFP and IONQUEST D3001) are also improved when co-dosed with low molecular weight poly(carboxylic acid)s or salts thereof during digestion of phosphate ores. Controlling foam can be effected by either decreasing the amount of foam or preventing the formation of foam. FIG. 6 depicts photographs of foam levels of slurries after digestion of phosphate ore in Ex. 5-7, with Ex. 6 being dosed with 8 kg/T P.sub.2O.sub.5 IONQUEST D3001, and Ex. 7 being dosed with 0.8 kg/T P.sub.2O.sub.5 P(AA-Na) and 7.2 kg/T P.sub.2O.sub.5 IONQUEST D3001. While IONQUEST D3001 reduced the amount of foam in Ex. 6 relative to Ex. 5, co-addition of P(AA-Na) (M.sub.w=1200) during the digestion step (Ex. 7) further reduced the amount of foam. However, low molecular weight poly(carboxylic acid)s or salts thereof, by themselves, have no defoamer activity. Foam volumes of Ex. 21-25 are listed in Table 5. Comparison of Ex. 23 to Ex. 22 and of Ex. 25 to Ex. 24 also shows the advantageous effect of the low molecular weight poly(carboxylic acid)s or salts thereof on foaming when used in combination with a defoamer. Moreover, the combination of defoamer and low molecular weight poly(carboxylic acid) provide an unexpected synergistic effect on controlling foam. As shown in Table 5, 6.0 kg/T P.sub.2O.sub.5 Defoamer #3 (Ex. 22) provides 20 mL of foam, while the combination of 5.4 kg/T P.sub.2O.sub.5 Defoamer #3 and 0.6 kg/T P.sub.2O.sub.5 PAA (Ex. 23, same total amount of additives) provides 5 mL of foam. Similarly, 6.0 kg/T P.sub.2O.sub.5 Defoamer #4 (Ex. 24) provides 10 mL of foam, while the combination of 5.4 kg/T P.sub.2O.sub.5 Defoamer #4 and 0.6 kg/T P.sub.2O.sub.5 PAA (Ex. 25, same total amount of additives) provides 5 mL of foam. The synergistic effect of the combination of defoamer and low molecular weight poly(carboxylic acid) on foam control is unexpected.

[0077] In summary, the data in Tables 1-6 and in FIGS. 1-6 show that addition of effective amounts of a defoamer and a low molecular weight poly(carboxylic acid), or salt thereof, during the digestion of phosphate bearing ores increases volume average particle size, enhances filtration rate, and controls foam.

[0078] As used herein, the term (meth)acrylic acid denotes acrylic acid, methacrylic acid, or a combination of acrylic acid and methacrylic acid. The acronym PAA refers to polyacrylic acid in particular. Similarly, the term (meth)acrylate denotes acrylate, methacrylate, or a combination of acrylate and methacrylate.

[0079] A used herein a salt can be an alkali metal salt, an alkaline earth metal salt, an ammonium salt, or a quaternary ammonium salt. The salt can be, for example, a lithium salt, a sodium salt, a potassium salt, a calcium salt, or an ammonium salt. In any or all embodiments, the salt is a sodium salt.

[0080] As used herein, low molecular weight refers to a weight-average molecular weight of less than 1,000,000 grams per mole (g/mol), and high molecular weight refers to a weight-average molecular weight of greater than or equal to 1,000,000 g/mol. For example, the phrase, low molecular weight poly(carboxylic acid) refers to a poly(carboxylic acid) having a weight-average molecular weight of less than 1,000,000 g/mol.

[0081] Dosage is herein expressed in units of kilogram of additive per ton of P.sub.2O.sub.5 in the phosphate ore, and is abbreviated as kg/T P.sub.2O.sub.5.

[0082] The invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather, these embodiments are provided so that this disclosure will satisfy applicable legal requirements. As used herein and in the appended claims, the singular forms include plural referents unless the context clearly dictates otherwise.

[0083] Those skilled in the art will appreciate that while preferred embodiments are discussed in more detail herein, multiple embodiments of the methods and compositions described herein are contemplated as being within the scope of the present invention. Thus, it should be noted that any feature described with respect to one aspect or one embodiment of the invention is combinable or interchangeable with another aspect or embodiment of the invention unless otherwise stated. It will be understood by those skilled in the art that any description of the invention, even though described in relation to a specific embodiment or drawing, is applicable to and interchangeable with other embodiments of the present invention.

[0084] Furthermore, for purposes of describing the present invention, where an element, component, or feature is said to be included in and/or selected from a list of recited elements, components, or features, those skilled in the art will appreciate that in the related embodiments of the invention described herein, the element, component, or feature can also be any one of the individual recited elements, components, or features, or can also be selected from a group including any two or more of the explicitly listed elements, components, or features. Additionally, the omission of any element, component, or feature recited in a list may also be considered part of the present disclosure.

[0085] Those skilled in the art will further understand that any recitation herein of a numerical range with lower and upper endpoints includes all numbers subsumed within the recited range (including fractions), whether explicitly recited or not, as well as the endpoints of the range and equivalents. Thus, 1 to 5 includes 1, 2, 3, 4, and 5 when referring to, for example, a number of elements, and can also include, for example, 1.5, 2, 2.75, and 3.8 when referring to, values of parameters. Disclosure of a narrower range or more specific group in addition to a broader range or larger group is not a disclaimer of the broader range or larger group. All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. For example, ranges of up to 25 wt. %, or, more specifically, 5 wt. % to 20 wt. %, are inclusive of the endpoints and all intermediate values of the ranges, including 5 wt. % to 25 wt. %, etc.

[0086] The methods and compositions herein can alternatively comprise, consist of, or consist essentially of, any appropriate steps or components separately disclosed herein. The methods and compositions can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps or materials that are otherwise not necessary to the achievement of the function or objectives of the methods and compositions.

[0087] Combinations is inclusive of blends, mixtures, alloys, reaction products, and the like. Or means and/or unless clearly stated otherwise. A and/or B means A, B, or a combination of A and B.

[0088] Unless specified to the contrary herein, all test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the priority application.

[0089] Unless defined otherwise herein, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this application belongs.

[0090] All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. However, if a term in the present disclosure contradicts or conflicts with a term in the incorporated reference, the term from the present disclosure takes precedence over the conflicting term from the incorporated reference.