Patent Application
20210205731
The invention relates to apparatus and methods for precipitating dissolved materials. Some embodiments provide apparatus and methods for crystallizing materials such as struvite from aqueous solutions such as wastewater or process water. For example, some embodiments relate to apparatus and methods for precipitating dissolved materials to form crystals while controlling fines.
Reactors in general and fluidized bed reactors in particular have been used to remove and recover phosphorous from solutions such as wastewater and process water. Aqueous solutions from some sources contain significant concentrations of phosphorus, often in the form of phosphate. Such aqueous solutions may come from a wide range of sources. These include sources such as leaching from landfill sites, runoff from agricultural land, effluent from industrial processes, industrial process water, municipal wastewater, animal wastes, phosphogypsum pond water, and the like. Such aqueous solutions, if released into the environment without treatment, can result in excess phosphorus levels in the receiving waters.
Various phosphorus removal and recovery technologies exist. Some of the technologies provide fluidized bed reactors for removing phosphorus from aqueous solutions by producing struvite (MgNH4PO4.6H2O) or a struvite analog or a phosphate compound in the form of pellets. Magnesium may be added to the reactor to form struvite. Struvite can be formed by the reaction:
Mg2++NH4++PO43−+6H20↔MgNH4PO4.6H2O
Koch et al., Fluidized Bed Wastewater Treatment, U.S. Pat. No. 7,622,047, describes example reactors and methods that may be applied to remove and recover phosphorus from aqueous solutions.
A difficulty sometimes exhibited in crystallization reactions is that the sizes of particles produced by the reaction may not be as desired. For example, under certain operating conditions, a reactor may produce a large amount of very tiny crystals (“fines”) where larger crystals are desired. Excessive production of fines can result in low capture of phosphate since fines can be carried out with effluent from a crystallization reactor. Crystal sizes are affected by a wide range of factors including flow conditions, chemical composition, temperature, etc. For example, if the load (i.e. the mass of phosphorus (PO4—P) added to a reactor (or portion thereof) per unit of time) is too high, then undesirable fines will be formed. Load limitations impact the volume of aqueous solution that may be treated per unit time, thereby impacting struvite production as a function of time.
References that describe various crystallization processes include: U.S. Pat. Nos. 8,245,625; 7,942,939; WO2006082341; U.S. Pat. Nos. 6,946,572; 6,364,914; WO9837938; U.S. Pat. Nos. 4,666,527; 3,419,899; 2,209,019; 4,159,194; 4,263,010; 5,124,265; 6,660,049; 5,663,456; AU2004320909; WO2012022099; WO2012134255.
There remains a need for effective reactors and methods for removing and recovering dissolved materials from solutions. There remains a particular need for effective reactors and methods suited to making large particles of marginally soluble substances such as struvite, struvite analogs, and calcium phosphate.
The foregoing examples of the related art and limitations related thereto are intended to be illustrative and not exclusive. Other limitations of the related art will become apparent to those of skill in the art upon a reading of the specification and a study of the drawings.
The following embodiments and aspects thereof are described and illustrated in conjunction with apparatus, systems, tools and methods which are meant to be exemplary and illustrative, not limiting in scope. In various embodiments, one or more of the above-described problems have been reduced or eliminated, while other embodiments are directed to other improvements.
Aspects of the present invention relate to apparatus and methods for precipitating dissolved materials. The apparatus and methods have example application to growing crystals of materials such as struvite, struvite analogs, and calcium phosphate.
Apparatus and methods according to some embodiments operate to grow particles while avoiding or minimizing the production of fines, by injecting an aqueous slurry of a low solubility source of magnesium (Mg). By maintaining a low concentration of fines, growth rates of larger particles may be enhanced and the loss of phosphorus by way of fines may be minimized or eliminated.
Some aspects of the invention provide methods in which a reactor is operated under high growth conditions. For example, the high growth conditions may correspond to loading conditions for a substance being produced. In some embodiments loading is above a threshold to achieve a high growth rate of crystals. For example, in some embodiments the loading may be 5 g PO4—P/min/m3 or more or 50 g PO4—P/min/m3 or more or 100 g PO4—P/min/m3 or more or 250 g PO4—P/min/m3 or more in a reactor (or a portion of the reactor).
In some embodiments a supersaturation ratio (ratio of the product of concentrations of constituents of the substance to the product of concentrations corresponding to equilibrium) is above a threshold to achieve a high growth rate of crystals. For example, in some embodiments, the supersaturation ratio for struvite or another material being crystallized may be 2 or more or 3 or more or 5 or more in the reactor. In some embodiments the substance is sparingly soluble in aqueous solution. Concentration of fines may be maintained below a threshold, thereby maintaining a growth rate of larger particles, by injecting an aqueous slurry of a low solubility source of magnesium (Mg) into the reactor (or portion of the reactor) as described herein.
In some embodiments, the method for precipitating dissolved materials from an aqueous solution involves introducing the aqueous solution containing the dissolved materials into a reactor and introducing a source of magnesium (Mg) into the reactor. The source of Mg is introduced in a quantity sufficient to cause the dissolved materials in the aqueous solution to precipitate into crystals. The source of Mg may, for example, be in the form of particles of a Mg-containing material. The source of Mg may, for example, have a solubility in the aqueous solution of less than about 1 g/L and/or the concentration of Mg in the reactor that is available for reaction to yield struvite (including solids in the particles of Mg-containing material) may be less than about 0.03 mol/L.
In some embodiments, the source of Mg is introduced to the reactor as a slurry. The slurry may be prepared by adding water to the source of Mg and soaking the source of Mg for a hydration time before introducing the hydrated slurry into the reactor. The source of Mg may, for example, have a solubility in aqueous solvent of about 5 mg/L to about 500 mg/L, or about 5 mg/L to about 150 mg/L. The concentration of the Mg in the reactor may be about 0.1 mmol/L to about 0.03 mol/L after introduction of the slurry. The source of Mg may, for example, have a particle size of less than 50 μm, or about 10 μm to about 30 μm, or about 100 mesh to about 400 mesh or about 17 SGN to 100 SGN, for example.
In some embodiments, the method further includes maintaining the aqueous solution at a pH greater than about 7. In some embodiments, the pH of the aqueous solution is maintained by adding an acid or a base to the hydrated slurry. In some embodiments, the pH of the aqueous solution is maintained by controlling the amount of the source of Mg present in the aqueous solution. The amount of the source of Mg present in the aqueous solution may be controlled by the steps of: measuring a pH of the aqueous solution in real-time, comparing the measured pH with a target pH (or “setpoint” pH) and adjusting the pH by introducing the source of Mg to the aqueous solution such that the pH of the aqueous solution is controlled to be equal to or close to the target pH. In some embodiments, the source of Mg is introduced into the reactor at a preset timed interval such as intervals of about 30 seconds to about 5 minutes.
In some embodiments, the source of Mg is a low solubility source of Mg. The low solubility source of Mg may, for example, be MgO, Mg(OH)2, or a magnesium carbonate. Examples of magnesium carbonate may include one or more of anhydrous salt magnesite (MgCO3), barringtonite (MgCO3.2H2O), nesquehonite (MgCO3.3H2O), lansfordite (MgCO3.5H2O), artinite (MgCO3.Mg(OH)2.3H2O), hydromagnesite (4 MgCO3Mg(OH)2.4H2O), dypingite (4 MgCO3Mg(OH)2.5H2O), dolomitic lime, and limestone.
In some embodiments, the low solubility source of Mg is MgO. MgO may be prepared in any suitable manner. In some embodiments MgO is prepared at a calcination temperature for a period of time sufficient to produce MgO particles. The calcination temperature may, for example, be in the range of about 600° C. to about 1200° C. The period of time used to produce MgO particles may, for example, be in the range of about 1 to 3 hours. The hydration time may, for example, be between about 15 minutes and about 36 hours.
In some embodiments an acid is added to the hydrated slurry before introducing the hydrated slurry into the reactor. The acid may, for example be added in about 0.4:1 molar equivalents. The acid may be a strong acid such as any of hydrochloric acid (HCl) and sulphuric acid (H2SO4) and nitric acid (HNO3). In some embodiments, the acid is a weak acid such as any of acetic acid, citric acid or oxalic acid.
In some embodiments, the source of Mg is reacted with the aqueous solution for a reaction time of about 30 minutes to about 60 minutes.
In some embodiments, the aqueous solution has a phosphorus concentration in the range of about 40 mg/L to about 10,000 mg/L.
In some embodiments, a high solubility source of Mg such as MgCl2 or MgSO4 is introduced in the reactor in addition to introduction of the low solubility source of Mg. The high solubility source of Mg and the low solubility source of Mg may be introduced into the reactor at the same time.
Some aspects of the invention provide a fluidized bed type reactor for precipitating dissolved materials from an aqueous solution. The fluidized bed reactor may comprise a reaction tank and a hydration tank. The reaction tank may include an inlet and an outlet. The hydration tank may be associated with the reaction tank and configured for hydrating a source of magnesium (Mg) in an aqueous solvent and introducing the source of Mg as a hydrated slurry into the reaction tank. In some embodiments, the reactor further includes a control valve. The control valve may be configured to control a flow of the hydrated slurry from the hydration tank to the reaction tank. In some embodiments, the reactor further includes a recycling path. The recycling path may be configured to take a solution from one part of the reaction tank and to return at least a portion of the removed solution to another part of the reaction tank. The recycling path may optionally include a fines treatment tank. In some embodiments, a solids separation device is upstream from the fines treatment tank. The solids separation device may be configured to separate solids from liquid in the recycling path.
In some embodiments, the reactor further includes a pH probe. The pH probe may be configured to measure a pH of the aqueous solvent in the reaction tank. In some embodiments, a controller may be configured to receive an input from the pH probe. The controller may be configured to control the opening and closing of the control valve in response to a deviation of the pH of the aqueous solvent in the reaction tank from a desired pH setpoint.
In some embodiments, the hydration tank includes a first acid injector. The first acid injector may be configured for controllably dosing an acid into the slurry in the hydration tank. In some embodiments, the reactor includes a second acid injector. The second acid injector may be configured for controllably dosing an acid into solution flow in the recycling path. The reactor may also include a base injector. The base injector may be configured for controllably dosing a base into solution flow in the reaction tank. In some embodiments, the base injector is located downstream of the acid injector in the recycling path.
Another aspect provides a method for making struvite or a struvite analog. The method comprises providing a reactor vessel wherein, in at least a portion of the reactor vessel a cross sectional area of the reactor vessel increases with elevation and maintaining a size-segregated fluidized bed of pellets in the portion of the reactor vessel by flowing a solution comprising phosphate upwardly through the portion of the reactor. An upward fluid velocity of the flowing solution decreases with elevation in the portion of the reactor. The method introduces fine particles of a low solubility source of magnesium into the reactor and allows the fine particles to disperse in the fluidized bed. Some of the pellets are removed from the fluidized bed. The fine particles may for example comprise magnesium oxide. The fine particles may, for example have sizes of SGN 100 or less. The fine particles may for example have diameters of 0.1 mm or less.
In the method, pH may be maintained at a pH setpoint which is equal to or greater than pH 7.5 in at least a part of the reactor vessel. The pH setpoint may be at least pH 8 in some cases.
The method may involve recycling the solution in the reactor vessel through a recycle path extending from an elevation in the reactor vessel above the fluidized bed to an elevation in the reactor vessel that is below the fluidized bed. Optionally the method includes comprising capturing or redissolving particles of struvite in the recycle path.
The fine particles of a low solubility source of magnesium may be introduced into the reactor vessel as a slurry of the fine particles. The slurry may be hydrated before it is introduced into the reactor vessel. Hydration may be performed by mixing the fine particles with aqueous solvent (e.g. water) and allowing the particles to remain in contact with the water for a period of at least a few minutes before introducing the slurry into the reactor vessel. The slurry may be injected into the reactor vessel at a location below the fluidized bed. In some cases an acid is mixed with the slurry prior to introducing the slurry into the reactor vessel. A pH at a location in the reactor vessel may be controlled by controlled addition of the slurry. In some cases the slurry buffers at an alkaline pH (e.g. at least pH 7.5 or at least about pH 8).
In addition to the exemplary aspects and embodiments described above, further aspects and embodiments will become apparent by reference to the drawings and by study of the following detailed descriptions.
Exemplary embodiments are illustrated in referenced figures of the drawings. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than restrictive.
Throughout the following description specific details are set forth in order to provide a more thorough understanding to persons skilled in the art. However, well known elements may not have been shown or described in detail to avoid unnecessarily obscuring the disclosure. Accordingly, the description and drawings are to be regarded in an illustrative, rather than a restrictive, sense.
This invention relates to the crystallization of materials from solution. Embodiments provide crystallization reactors and methods as well as apparatus and methods for reducing the concentration of fines in crystallization reactors. Other embodiments provide crystallization reactors and methods for growing crystals of materials that have poor solubility (of which struvite, struvite analogs, and calcium phosphate are examples). The invention may be applied to controlling fines in the crystallization of any of a wide range of chemical substances from solution. Precipitation of struvite from aqueous solutions is used in this disclosure as a non-limiting example application of the invention.
Some embodiments of the invention in the following description relate to crystallization reactors and methods wherein magnesium is added to precipitate phosphorus in wastewater in the form of struvite or struvite analogs or a phosphate compound. For example, some embodiments provide crystallization reactors and methods in which magnesium is added to precipitate phosphorus from wastewater in the form of struvite (MgNH4PO4.6H2O) according to the following reaction:
Mg2++NH4++PO43−+6H20↔MgNH4PO4.6H2O
The struvite may have the form of pellets. The pellets may for example have sizes of about 0.1 mm to 3 mm or more. These examples coincide with embodiments having significant commercial utility. The scope of the invention, however, is not limited to these examples.
The term “aqueous solution” or “solution” is used in the following description and claims to include aqueous solutions such as industrial and municipal wastewater, industrial process water, leachate, runoff, animal wastes, effluent, phospho-gypsum pond water, or the like. Some embodiments provide methods for treating municipal sewage and/or animal waste. Some embodiments provide methods for treating other kinds of wastewater. Some embodiments provide methods for crystallizing materials using feedstock other than wastewater.
The term “load” or “loading” is used in the following description and claims to mean the mass of phosphorus (PO4—P) added to a reactor (or portion of the reactor) per unit of time.
The term “saturation” is used in the following description and claims to mean a solution at its solution equilibrium point that cannot dissolve any more of a solute under present conditions.
The term “supersaturation” is used in the following description and claims to mean a solution containing more of a dissolved solute than could otherwise be dissolved by the solvent under present conditions.
One aspect of the invention relates to apparatus and methods for precipitating dissolved materials, such as struvite, struvite analogs, calcium and phosphate. Some aspects of the invention relate to apparatus and methods for operating a reactor under high growth conditions.
In some embodiments the reactor comprises a fluidized bed reactor. An example fluidized bed reactor 12 is shown in
The aqueous solution flows into reaction tank 18 through inlet 14 and flows out of reaction tank 18 through outlet 16. In some embodiments, reactor 12 comprises a plurality of inlets and/or outlets.
Inlet 14 may be located, for example, in or near the lower portion of reaction tank 18. Outlet 16 may be located, for example, in or near the upper portion of reaction tank 18. In some embodiments inlet 14 is oriented to face upwardly and a flow of solution introduced from inlet 14 into reaction tank 18 is directed upwardly.
In some embodiments, a method for making a crystalline product includes providing at least one ionic species that reacts to form the crystalline product from a material that yields the ionic species when dissolved where the material has a low solubility. The material may be provided in the form of fine particles. For example, where the product is struvite, the ionic species may be magnesium ions (Mg2+) and the material may be magnesium oxide (MgO) which has a low solubility in water. The MgO may be provided in the form of a slurry of fine particles.
Reactor 12 comprises a hydration tank 40. A low solubility source of Mg is introduced into hydration tank 40 via inlet 42. An aqueous solvent (e.g. water) is introduced into hydration tank 40 via inlet 44. The low solubility source of Mg is hydrated with the aqueous solvent for a period of time sufficient to hydrate the source of Mg to provide a hydrated slurry comprising free Mg2+ ions available in solution for struvite production in reaction tank 18. The hydrated slurry is delivered from hydration tank 40 into reaction tank 18 through inlet 46. Inlet 46 may be located, for example, in or near the lower portion of reaction tank 18. In some embodiments inlet 46 is directed upwardly and flow of a hydrated slurry introduced from inlet 46 into reaction tank 18 is directed upwardly.
Under the right reaction conditions, crystals (e.g., crystals of struvite or other phosphorus-containing compounds in some embodiments) form in reaction tank 18 through precipitation of dissolved materials in the solution (e.g., wastewater solution in some embodiments). Crystals may grow larger over time and may be sorted according to size by differences in fluid velocities in different regions within the reaction tank. For example, in some embodiments fluid flows upward in the reaction tank with a velocity that increases with depth in the reaction tank (decreases with elevation). This may be achieved, for example, by providing a reaction tank having a cross sectional area that increases with elevation above the inlet and/or by providing recycling paths (described elsewhere herein) having outlets at different depths in reaction tank 18.
In such embodiments particles made up of crystals may move downward as they grow in size (e.g., through accretion and/or aggregation with other crystals). The particles may ultimately enter a harvesting zone in reaction tank 18 from which they may be removed for use as fertilizer or other applications.
In some embodiments, reaction tank 18 comprises a substantially vertically-oriented conduit having a harvesting section and two or more vertically-sequential sections above the harvesting section. A cross-sectional area of the conduit may increase moving from the bottom of reaction tank 18 toward the top of reaction tank 18. For example, the cross sectional area may increase between adjacent ones of the sections. The number of sections in the conduit may be varied. In some embodiments the cross-sectional area increases stepwise. In some embodiments the cross-sectional area increases smoothly. In some embodiments, reaction tank 18 is cone-shaped or horn-shaped or otherwise configured to have a cross-sectional area that increases smoothly with elevation above the bottom of reaction tank 18. Tank 18 may be round in cross-section but is not necessarily so. Inlet 14 may be located in or below the harvesting section for example.
Some embodiments of the present invention may comprise a fluidized bed reactor of the type described in Britton, WO publication No. 2012/119260, entitled “Reactor for Precipitating Solutes from Wastewater and Associated Methods” and/or of the type described in Britton, et al., WO publication No. 2015/003265, entitled “Reactor Apparatus and Methods for Fines Control” and/or of the type described in Koch et al., U.S. Pat. No. 7,622,047, entitled “Fluidized Bed Wastewater Treatment”, which are hereby incorporated herein by reference in their entirety for all purposes.
The inventors have determined that, in some applications, it is desirable to be able to maintain control of the size of the product crystals (e.g., crystals of struvite, struvite analogs, or other phosphorus-containing compounds) which form in the reactor through precipitation of dissolved materials. For example, it may be desirable to selectively precipitate and harvest relatively large product crystals and/or pellets (e.g., crystals and/or pellets with a diameter mm), where product crystals aggregate together to form product pellets.
One aspect of the invention relates to apparatus and methods which provide for the control of fines (fines are very small crystals, for example crystals with a diameter 00 μm may be described as “fines”) in a reactor. Many fines in a reactor may have sizes in the range of about 1 μm to about 10 μm.
Fines can have an extremely large ratio of surface area to mass as compared to larger crystals. Where a large number of fines are present in a crystallization reactor, a high proportion of crystal growth can occur on the surface of fines thereby reducing the growth rates of larger crystals. The inventors have realized that fines production in a reactor can result from zones of high supersaturation (exceeding metastable limits and resulting in primary or secondary nucleation) or from accretion of previously formed crystals within the reactor. One could reduce production of fines by operating a reactor with very low supersaturation. However crystals may grow slowly under such conditions. It is desirable to be able to control the accumulation of fines within the reactor, especially when large (e.g., mm) product crystal sizes are desired.
The inventors have realized that a reactor may be operated under increasing loading conditions by increasing the concentrations of one or more of the constituents of the product struvite, struvite analog, or other phosphorus-containing compound. For example, increasing the concentration of free Mg2+ ions may enhance crystal growth.
During struvite crystallizer operation, and especially when operating with feedstock solutions with high concentration of phosphate (>100 mg/L PO4—P feedstocks and particularly >2,000 mg/L PO4—P), and/or extended hydraulic retention times (>1 hrs and particularly >12 hrs) in a fluidized bed reactor (such as reactor 12) it has been found that fines (crystals with a diameter <100 μm) tend to accumulate in the reactor. In some cases, within a period of 6 to 12 hours of operation almost all the crystal formation/growth may occur as fines, either through primary/secondary nucleation, or due to growth occurring primarily on the surface of existing fines retained in the reactor. It is believed that this phenomenon can occur as a result of a combination of increased secondary nucleation in the presence of high levels of fines combined with the overwhelming majority of the crystal surface area in the reactor being on the surface of fines (which have much higher surface area to volume ratios than larger and more desirable crystals with diameters of e.g. 1-5 mm).
The rate at which fines accumulate may be controlled to a certain extent (and the period before which runaway fines production begins could be extended) by reducing the crystallization reaction rate and/or supersaturation ratio and/or loading and/or concentration of magnesium added to the reactor. However, if significant amounts of fines (e.g., >5 mg/L settled fines as measured in the reactor recycling path flow, or turbidity >500 NTU) were present in the reactor, further increase in crystal size distribution or growth of large crystals may be significantly impaired by the presence of a large number of fines.
Typically, struvite crystal recovery processes use soluble sources of Mg, such as magnesium chloride (MgCl2) and/or magnesium sulphate (MgSO4), as a source of free Mg2+ for struvite production. Due to the high solubility of these Mg sources (MgCl2 has a solubility in water of about 54 g/L), introduction of MgCl2 and/or MgSO4 leads almost immediately to an increased concentration of free Mg2+ ions which increase the supersaturation ratio in the localized area where the Mg source was introduced. Thus, zones of high supersaturation may occur in the reactor (or portions of the reactor) thereby producing fines, as described elsewhere herein. For example, when the source of Mg is MgCl2, a portion (e.g. about 10-50%) of the produced struvite crystals may be present as fine particles (i.e. <20 μm in diameter). Such fines are too small to effectively settle and be retained in the reactor, and therefore wash out of the reactor and are lost with the treated effluent (i.e. fines loss).
The inventors have empirically determined that when a source of Mg that has a lower solubility than conventional soluble sources of magnesium (e.g. MgCl2 and/or MgSO4) is used, fines production is eliminated or reduced, even under enhanced loading. Accordingly, one aspect of the invention provides methods which comprise injecting a low solubility source of Mg into the reactor for struvite crystal recovery.
In some embodiments the methods comprise a step of hydrating a low solubility source of Mg before injecting the resulting hydrated slurry into the reactor (or portion of the reactor). Thus free Mg2+ ions are available to react to form struvite in the reactor. For example, the methods may operate by forming an aqueous slurry of a source which releases Mg2+ ions as it dissolves. The source of Mg can be mixed with an aqueous solvent for a period of time (i.e. the hydration time).
In some embodiments, the hydrated slurry is circulated from a slurry tank around a loop and back to the slurry tank. A fluid velocity in the loop may be kept high enough to avoid settling of particles from the slurry in the loop. The loop may be arranged to pass close to the reactor. Injecting the hydrated slurry into the reactor may comprise diverting some of the hydrated slurry flowing in the loop into the reactor, for example by way of a valve.
In some embodiments the source of Mg is magnesium oxide (MgO). As shown by the reaction below, on hydration MgO forms a MgOH+ complex on the surface of the MgO particle and ultimately results in the formation of 2 mol of OH−(aq):
MgO(surface)+H+(aq)→MgOH+(surface)+OH−(aq)→MgOH+.OH−(surface)→Mg2+(aq)+2OH−(aq)↔Mg(OH)2(s)
The formation of 2OH−(aq) increases and/or maintains the pH of the solution in the reactor to a level suitable for crystal formation and growth and, in some embodiments, reduces and/or eliminates the overall consumption of caustic for crystal precipitation in the reactor. In some embodiments the use of a low solubility source of Mg, such as MgO or Mg(OH2), may replace the need for caustic (e.g. NaOH), thereby reducing or eliminating pH/supersaturation spikes at a caustic injection site in the reactor (or portion of the reactor). This may reduce overall capital and/or operating costs by eliminating or reducing the need for a separate pH control reagent and the need for the associated storage and dosing systems. Further, by eliminating or reducing pH/supersaturation spikes, fines production may be reduced or eliminated. In some embodiments the hydrated slurry buffers at alkaline pH. For example, the inventors have empirically determined that a hydrated slurry formed by hydrating MgO in an aqueous solvent buffers at a pH of about 8.1.
Suitable low solubility sources of Mg may include: MgO, Mg(OH)2, magnesium carbonates (such as the anhydrous salt magnesite (MgCO3), the di-, tri-, and pentahydrates barringtonite (MgCO3.2H2O), nesquehonite (MgCO3.3H2O), and lansfordite (MgCO3.5H2O), respectively, artinite (MgCO3.Mg(OH)2.3H2O), hydromagnesite (4 MgCO3Mg(OH)2.4H2O), dypingite (4 MgCO3Mg(OH)2.5H2O), dolomitic lime, or limestone with suitable Mg content). Such sources are typically less expensive than conventionally used soluble sources of Mg (e.g. MgCl2 and MgSO4). In some embodiments the low solubility source of Mg has a solubility in water (at about 25° C. to about 30° C.) of less than about 1 g/L.
In some embodiments the low solubility source of Mg has a solubility in water (at about 25° C. to about 30° C.) in the range of: about 5 mg/L to about 1 g/L, about 5 mg/L to about 500 mg/L, about 5 mg/L to about 150 mg/L, about 5 mg/L to about 100 mg/L, about 5 mg/L to about 90 mg/L, about 5 mg/L to about 80 mg/L, about 5 mg/L to about 70 mg/L, about 5 mg/L to about 60 mg/L, about 5 mg/L to about 50 mg/L, about 5 mg/L to about 40 mg/L, about 5 mg/L to about 30 mg/L, about 5 mg/L to about 20 mg/L, or about 5 mg/L to about 10 mg/L. For example, MgO has a solubility in water of about 86 mg/L (at 30° C.). Mg(OH)2 has a solubility in water of about 6.4 mg/L (at 25° C.). MgCO3 has a solubility in water of about 139 mg/L (at 25° C.).
Persons skilled in the art will recognize that some solubility variability is common and that the solubility of a source of Mg may differ according to the provider of that Mg source. For example, the solubility of a source of Mg may differ depending on the calcination temperature and/or the calcination time to prepare the Mg source, as described elsewhere herein.
In some embodiments the low solubility source of Mg has a concentration in the reactor of less than about 0.03 mol/L. In some embodiments the low solubility source of Mg has a concentration in the reactor in the range of: about 0.1 mmol/L to about 0.03 mol/L, about 0.1 mmol/L to about 0.02 mol/L, about 0.1 mmol/L to about 4 mmol/L, about 0.1 mmol/L to about 2.5 mmol/L, about 0.1 mmol/L to about 2.2 mmol/L, about 0.1 mmol/L to about 2.0 mmol/L, about 0.1 mmol/L to about 1.7 mmol/L, about 0.1 mmol/L to about 1.5 mmol/L, about 0.1 mmol/L to about 1.2 mmol/L, about 0.1 mmol/L to about 1.0 mmol/L, about 0.1 mmol/L to about 0.7 mmol/L, about 0.1 mmol/L to about 0.5 mmol/L, or about 0.1 mmol/L to about 0.25 mmol/L. For example, when the low solubility source of Mg is MgO, the concentration of Mg in the reactor may be about 2.1 mmol/L or less.
When the low solubility source of Mg is Mg(OH)2, the concentration of Mg in the reactor may be about 0.1 mmol/L or less. When the low solubility source of Mg is MgCO3, the concentration of Mg in the reactor may be about 1.6 mmol/L or less.
In some embodiments the extent of hydration of the low solubility Mg source correlates with phosphorus removal (e.g. struvite crystal production). The extent of hydration may be controlled by one or more of: the duration of hydration time, heating the Mg source and aqueous solvent mixture, and the hydrated slurry concentration. For example, where the Mg source is MgO, hydration time may be controlled to prevent or minimize the formation of solid Mg(OH)2. Mg(OH)2(s) may accumulate on the surface of MgO particles, thereby decreasing the rate of free Mg2+ release and reducing crystal formation in the reactor.
Since Mg(OH)2(s) is less soluble than MgO(S), the period of time to re-dissolve Mg(OH)2(s) in an aqueous solvent to provide free/dissolved Mg2+ for crystal formation is longer. In some embodiments the hydration time for a low solubility source of Mg is controlled to improve crystal production. For example, the inventors have empirically demonstrated that hydrating MgO in an aqueous solvent for about 20 hours resulted in about a 4-8% better yield of struvite than a hydration time of about 15 minutes or about 36 hours. In some embodiments the desired hydration time for MgO is between about 15 minutes and about 36 hours.
In some embodiments the hydration time for MgO is between about 15 minutes and 1 hour. In some embodiments the hydration time for MgO is between about 15 minutes and several hours (e.g. 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours).
Persons skilled in the art will understand that hydration time may be influenced by reaction conditions and/or the source of Mg. For example, temperature and/or pressure and/or the presence of other solutes in an aqueous solvent may impact free Mg2+ release and/or Mg(OH)2(s) formation when the low solubility source of Mg is MgO. For example, an aqueous slurry of MgO warms up as hydration proceeds, especially when acid is added to the slurry. This warming may impact hydration time. Thus, the hydration time for MgO may be greater than 36 hours or less than 15 minutes.
In some embodiments when the low solubility source of Mg is a substance other than MgO, the desired hydration time is greater than 15 minutes. In some embodiments the hydration time is between about 15 minutes and several hours (e.g. 15 minutes to 20 hours). Some non-limiting example hydration times are 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, 28 hours, 29 hours, 30 hours, 31 hours, 32 hours, 33 hours, 34 hours, 35 hours, 36 hours.
To prepare the hydrated slurry, an aqueous solvent (e.g. water) is added to the low solubility source of Mg. In some embodiments the hydrated slurry contains about 5% to about 30% Mg by weight. In some embodiments the hydrated slurry contains less than about 10% Mg by weight. Since MgO absorbs water on hydration, the hydrated slurry can become “chunky” if too little aqueous solvent is used. Accordingly, a hydrated slurry of MgO having about 25% to about 30% Mg by weight may be too dry and/or viscous and/or thick to readily mix and pump to the reactor (or portion of the reactor). In some embodiments, the amount of soluble Mg in the hydrated slurry is less than about 5 mg/L. In some embodiments, the amount of soluble Mg in the hydrated slurry is about 0.5 mg/L.
If the weight percent of Mg in the hydrated slurry is too low, this may reduce crystal production and/or increase production times and/or consume excess water thereby increasing production costs. In some embodiments the hydrated slurry is more effective when the slurry is relatively dilute (e.g. the slurry contains less than about 10% Mg by weight). For example, crystal production may be increased when the hydrated slurry of Mg(OH)2 is dilute (e.g. contains less than about 5% Mg by weight).
In some embodiments Mg(OH)2 is used as the low solubility source of Mg and is in the form of a slurry. Since the Mg(OH)2 form is already hydrated, further hydration time is not needed. Since Mg(OH)2 is less soluble than MgO, using Mg(OH)2 as a source of magnesium may require more dilute slurries to achieve equivalent performance to slurries of MgO. Accordingly, Mg(OH)2 may be a less effective source of Mg than MgO in terms of struvite recovery and/or loading.
Magnesium carbonates may be used as a source of Mg. However, hydrating magnesium carbonates may result in the production of carbon dioxide (CO2) gas which could cause foaming problems and/or affect slurry pH. CO2 gas is acidic and, accordingly, a caustic agent may be required to neutralize excess acid. Dolomitic lime or limestone may be used as the source of Mg. However, such Mg sources contain calcium (Ca), which may interfere with struvite production and/or may contaminate the resulting product with Ca. Such products may more readily precipitate from wastewater, but may be less desirable as a fertilizer than struvite. However, since MgO, Mg(OH)2, magnesium carbonates, lime, and limestone are a relatively inexpensive, they may be an attractive low solubility source of Mg for producing struvite.
In some embodiments the particle size of the low solubility Mg source is controlled to prevent or minimize the hydrated slurry from plugging orifices or pipes of the reactor, such as manifold orifices or the like. If the particle size exceeds a desired size, the hydrated slurry can plug pipes to the point that flow is impeded and/or causes damage to pumping equipment. In some embodiments the particle size of the low solubility source of Mg is in the range of: about 100 to about 400 mesh, about 100 to about 350 mesh, about 100 to about 300 mesh, about 100 to about 250 mesh, about 100 to about 200 mesh, about 150 to about 200 mesh, about 200 to about 400 mesh, about 250 to about 400 mesh, about 300 to about 400 mesh or about 350 to about 400 mesh. In some embodiments MgO has a particle size of about 200 mesh. In some embodiments, MgO has a particle size of about 400 mesh. In some embodiments, the low solubility source of Mg is a fine powder having a particle size in a range of about 10 to about 50 μm, about 10 to about 40 μm, or about 12 to about 30 μm. In some embodiments, MgO has a particle size in a range of about 17 SGN to about 100 SGN (size guide number). In some embodiments, MgO has a particle size in a range of about 17 SGN to about 30 SGN.
Persons skilled in the art will recognize that the mesh grade of the low solubility Mg source may be affected by the calcination temperature and/or the calcination time to prepare the Mg source. For example, MgO may be prepared by calcinating magnesium carbonate. In some embodiments the calcination temperature is less than about 1,200° C. In some embodiments the calcination temperature is in the range of about 600° C. to about 1,200° C. In some embodiments the calcination time is less than about 3 hours. In some embodiments the calcination time is in the range of about 1 to 3 hours. In some embodiments the calcination time is about 2 hours.
By optimizing the conditions for preparing the low solubility Mg source, the particle size, specific surface area and reactivity may be controlled. For example, in some embodiments a particle size of about 200 mesh is desirable. Such particles may be optimally retained by the reactor without clogging the system used to deliver the low solubility Mg source to the reactor and/or without the need for high-flow pumps.
Without being bound to any particular theory, the inventors believe that employing a low solubility source of Mg may avoid or reduce fines production due to the longer retention time of the slow dissolving low solubility sources of Mg as compared to conventional soluble Mg sources (e.g. MgCl2 and/or MgSO4). The low solubility sources of Mg slowly release free Mg2+ ions into solution such that the distribution of Mg2+ ions throughout the reactor (or portion of the reactor) is substantially uniform. In this way, crystallization is promoted throughout the reactor (or portion of the reactor) and localized areas where Mg concentration is significantly elevated may be minimized or avoided. Thus, the slow rate of dissolution of low solubility Mg sources may prevent or minimize areas where the supersaturation ratio is sufficiently high to cause a large number of fines to be produced.
Another theory is that the presence of a low solubility Mg source assists any fines that are produced in the reactor (or a portion of the reactor) to stick together or to other particles present in solution. The inventors have tested effluent treated by adding a low solubility source of Mg to aqueous solution in a fluidized bed reactor at loading rates between 5 and 250 g PO4−P/min/m3 and failed to observe fine particles or MgO particles in the effluent or recycle fluid. If the reduction or elimination of fines reduction was due exclusively to a longer retention time, then observation of the low solubility Mg source would be expected in the treated effluent and/or recycle fluid. Since the treated effluent and recycle fluid were empirically observed by the inventors to be free of the low solubility Mg source, it is possible that the low solubility Mg source “sticks” to the struvite crystals present in the reactor.
Thus, in some embodiments, the low solubility source of Mg (e.g., MgO) is introduced into a fluidized bed. Particles in the fluidized bed may comprise struvite, a struvite analog, or monoammonium phosphate, for example. The low solubility source of Mg may be provided in the form of particles that would be washed out of the reactor for given fluid flow rates in the reactor. Interaction between the small particles of MgO (or other low solubility source as an ionic species) may retain the small particles in the fluidized bed such that the particles supply Mg2+ (or another ionic species) throughout all or large parts of the fluidized bed. The distributes small particles may replenish available Mg2+ (or another ionic species) as the available Mg2+ is consumed in the production of struvite or another product.
The inventors have empirically determined that the resulting struvite crystals can be relatively pure, with little to no excess Mg observed in product samples. Therefore, the inventors believe that the low solubility source of Mg may be essentially completely dissolved and used to form struvite crystals. Further trials were carried out in which the reactor was fed with tap water essentially free of phosphate and ammonia, and a hydrated MgO slurry, resulting in the injection and dilution of the MgO slurry in the water, but no struvite formation reaction. In this case a substantial portion of the injected MgO slurry was observed in the reactor recycle and effluent. The experiment was repeated both with and without a fluidised bed of struvite particles present in the reactor, with the same results. This indicates that the occurrence of the struvite formation reaction is required to get the hydrated MgO slurry particles to adhere to the fluidised bed.
Without being bound to any particular theory, the inventors believe that formation of a slurry via hydrating a low solubility source of Mg before the source is added to the reactor (or portion of the reactor) may result in the uniform distribution of free Mg2+ ions throughout the reactor volume (or portion of the reactor volume), thereby enhancing loading limitations and/or increasing struvite production and/or reducing fines production. For example, the limited solubility of the low solubility Mg source may allow the localized supersaturation ratio around the point of Mg2+ injection to stay relatively low as compared to cases in which conventional highly soluble Mg sources (e.g. MgCl2 and MgSO4) are injected into a similar reactor.
In some embodiments method 100 comprises an optional step 130 of adding an acid to the hydrated slurry. The acid can be added to the tank in which the low solubility Mg source slurry is hydrated or stored. The addition of acid may increase the yield of struvite in the treatment of high strength wastewater (e.g., wastewater which contains high amounts of fats, oils, and greases (FOG) or other organic components). It has been found that addition of approximately a 0.4:1 mol ratio of H+ to Mg is effective in increasing the yield of struvite. When the low solubility Mg source is MgO, the acid provides H+(aq) to drive formation of the MgOH+ complex in the first step of the hydration mechanism depicted elsewhere herein.
The inventors have empirically determined that adding a suitable amount of acid to the hydrated slurry may increase the rate of struvite crystal production and/or overall struvite conversion efficiency, thereby resulting in a higher yield of struvite crystals and/or allowing increased reactor loading.
For example, adding an acid in a 0.2:1 molar equivalent ratio of H+:Mg increased struvite crystal yield by about 10-20%. In some embodiments an amount of acid is added to the hydrated slurry to neutralize about 20% of any hydroxide formed by hydrating the low solubility source of Mg. Suitable acids include strong acids, such as hydrochloric acid (HCl), sulphuric acid (H2SO4), nitric acid (HNO3) etc., and weak acids, such as acetic acid, citric acid, oxalic acid, etc. Acids that interfere with struvite production (e.g. phosphoric acid (H3PO4)) and/or acids that are too weak to break up MgO particles (or other low solubility Mg source particles) are avoided in some embodiments.
In one embodiment, the acid comprises sulfuric acid. For example, the acid may be 93%-98% sulfuric acid. Sulfuric acid is readily available at wet process phosphoric acid plants and thus is convenient to use when operating this method at or near a wet process phosphoric acid plant. Sulfuric acid is generally one of the more cost effective commercially available acids.
In another embodiment, the acid comprises acetic acid (or other volatile fatty acid or blend of volatile fatty acids), which is useful as a source of volatile fatty acids required for the uptake of phosphate from wastewater in treatment plants using enhanced biological phosphorus removal. Therefore, applying acetic acid or volatile fatty acids to the wastewater in the recycling path creates an additional level of synergy.
In some embodiments, in step 120, the acid is dosed to the hydrated slurry. For example, the acid may be added in liquid form to a slurry hydration tank. Weak acids, such as citric acid, that are available in dry form could be added as a powder to the hydration tank, or pre-mixed with MgO prior to hydration.
In some embodiments, in step 110 and/or step 120, the pH of the hydrated slurry is controlled by adding an appropriate amount of acid.
Reactor design and/or reaction conditions may impact fines and/or struvite production and/or operation economies when the source of Mg is a low solubility source. For example, in some embodiments the hydrated slurry is injected close to the bottom of the reactor (or portion of the reactor), as described elsewhere herein.
Since hydrated slurries, such as hydrated slurries of MgO, can be prone to scaling and plugging, a recycling path may be used to adjust fluid flow rates within the hydrated slurry mixing and pumping system. The relatively high fluid velocity in the recycling path may prevent or minimize scaling and plugging by the low solubility Mg source.
In the embodiment illustrated in
The illustrated recycling path 30 has an inlet end 30A and an outlet end 30B. In the
Recycling path 30 is connected to withdraw solution from reaction tank 18 and to return solution to reaction tank 18. In some embodiments, recycling path 30 returns solution to reaction tank 18 below a location at which the solution is received from reaction tank 18. In some embodiments, recycling path 30 shares inlet 14 and/or outlet 16 (e.g., inlet end 30A of recycling path 30 is in direct fluid communication with outlet 16, and/or outlet end 30B of recycling path 30 is in direct fluid communication with inlet 14). In other embodiments, recycling path 30 has one or more inlet ends separate from outlet 16 and/or one or more outlet ends into reaction tank 18 separate from inlet 14.
Where solubility of a substance being precipitated is pH-dependent, reactor 12 may comprise an acid injector 32 to apply an acid to the solution flow. Acid may be injected for example into recycling path 30. Injection of acid lowers the pH of the solution in recycling path 30 or in reactor 12 as a whole. A recycling path 30 with an acid injector 32 may act as a fines destruct loop, selectively dissolving fines that are small enough to be held in suspension in the reactor recycling path flow. Most of the larger crystals remain in reaction tank 18 (e.g., in the fluidized bed in the reaction tank).
In some embodiments, the acid applied in recycling path 30 may lower the pH not only in recycling path 30, but also in reaction tank 18. It is possible that the reduction of pH locally in recycling path 30 may be greater than the reduction of pH in reaction tank 18 which is further away from acid injector 32. Because the fines have a high surface area to volume ratio relative to the larger crystals, the fines have a tendency to dissolve faster on a % mass basis than the larger crystals. In some embodiments, pH is increased in the recycling path (e.g. by neutralizing the acid by injecting a base) before the recycling path rejoins tank 18.
In some embodiments, reaction tank 18 may comprise a base injector which injects a base (e.g., a substance which increases the concentration of OH− ions in the solution and/or increases the pH of the solution) into the solution in reaction tank 18 to increase or maintain the pH of the solution. An example base injector 40A is schematically illustrated in
In some embodiments, the pH of the solution in reaction tank 18 is maintained at a relatively high pH (as compared to some prior struvite precipitation processes—e.g., a pH 7 or ≥7.5)). In some cases pH of 8 or 9 or more is maintained in all or part of the reaction tank. The inventors have determined that maintaining certain struvite formation reactions at a higher pH may help to drive the equilibrium reaction to completion. This in turn improves the efficiency of phosphate removal. Specifically, the inventors have found that increasing the pH of the reaction using MgO as the source of Mg in the struvite formation reaction can achieve nearly a complete removal (98%) efficiency of phosphate from a given wastewater sample. Typical efficiency of phosphate removal using conventional struvite formation reactions is significantly lower.
The rate of addition of the hydrated slurry into reaction tank 18 can impact the efficiency of phosphate removal. The inventors have found that the pH of the solution in reaction tank 18 may be used as an indicator of the amount of the hydrated slurry (or specifically the concentration of the low solubility Mg source) present in the solution in the reactor at a given time. In some embodiments, the pH is maintained by adjusting the flow of the hydrated slurry into reaction tank 18 (or conversely, injection of the hydrated slurry into reaction tank is controlled based on pH in reaction tank 18). It is also possible to control addition of the hydrated slurry to maintain a desired molar ratio of Mg:P in the reactor.
In some embodiments, the pH of the solution in reaction tank 18 is controlled by the addition of the hydrated slurry. In some embodiments, reactor 12 comprises a control valve 31 between reactor tank 18 and hydration tank 40. Control valve 31 controls the flow of the hydrated slurry out of hydration tank 40 and into reaction tank 18. In some embodiments, control valve 31 is connected to a controller 35. Controller 35 may receive input from a pH probe 33. pH probe 33 measures the pH of the solution in reaction tank 18. Controller 35 may control the opening and closing of control valve 31 in response to the pH of the solution in reaction tank 18. In some embodiments, pH probe 33 transmits real-time pH measurements of the solution in reaction tank 18 to controller 35. Control valve 31 may open to allow the flow of the hydrated slurry into reaction tank 18 in response to a deviation in the pH of the solution from a target pH. In some embodiments, the target pH is at a pH greater than one that is conventionally maintained in struvite precipitation processes. In such embodiments, control valve 31 may open to allow the flow of the hydrated slurry into reaction tank 18 in response to a decrease in pH of the solution from the target pH. The increase of hydrated slurry that flows through the fluidized bed of reaction tank 18 results in an increase in the pH of the solution. In some embodiments, control valve 31 may be set to open at intervals of about 30 seconds to about 5 minutes.
In an example embodiment as illustrated in
In some embodiments, a soluble Mg source (e,g., MgCl2) may be injected into reaction tank 18 in addition to introducing the hydrated slurry containing a low solubility Mg source. The soluble Mg source may optionally be injected into reaction tank 18 concurrently with the hydrated slurry. The soluble Mg source may be injected into reaction tank 18 via the same inlet as or a different inlet from the injection of the low solubility Mg source.
Reaction time may impact struvite production and/or fines and/or operation economies when the source of Mg is a low solubility source. Due at least in part to the limited solubility of a low solubility Mg source, reaction times to achieve desired phosphorus removal are generally longer than those observed for conventional soluble Mg sources (e.g. MgCl2 and MgSO4). The low solubility of the low solubility Mg source allows the Mg source to slowly release free Mg2+ ions over time. For example, reaction times of about 6 minutes are typical for soluble Mg sources. For low solubility Mg sources, reaction times of about 30 to about 60 minutes may be required to achieve desired phosphorus removal.
Reaction time may be controlled by decreasing the flow rate of aqueous solution into the reactor. By increasing the reaction time, the low solubility Mg source may be able to uniformly distribute throughout the reactor volume (or portion of the reactor volume). This may allow the localized supersaturation ratio around the point of hydrated slurry injection to stay relatively low as compared to conventional soluble Mg sources (e.g. MgCl2 and MgSO4), while maintaining a relatively high supersaturation throughout a substantial portion of the reactor (or portion of the reactor) as the low solubility Mg source particles continue to dissolve thereby replenishing the free Mg2+ concentration throughout the fluidized bed.
Loading may impact struvite production and/or fines formation and/or operation economies when the source of Mg is a low solubility source. For example, a fluidized bed type reactor may be operated under high growth conditions (i.e. high loading conditions) when a low solubility source of Mg is added to an aqueous solution in the reactor (or portion of the reactor). In some embodiments loading is above a threshold to achieve a high growth rate of crystals. For example, the inventors have empirically observed that loading may 5 g PO4—P/min/m3 or more or 50 g PO4—P/min/m3 or more or 100 g PO4—P/min/m3 or more or 250 g PO4—P/min/m3 or more in a reactor (or a portion of the reactor). In some instances the loading of PO4—P may be increased by a multiple of 2, 5, 7, 10, 17, 20, 25 or more while producing commercially acceptable particles of struvite by switching from injecting a high solubility source of Mg to injecting a lower solubility source of Mg as described herein (e.g. when a 10% by weight aqueous slurry of MgO is used) in comparison, to a similar case where conventional soluble Mg sources (i.e. MgCl2 or MgSO4) are used (typically as 1% to 32% solutions of MgCl2 or MgSO4). Accordingly, loading may be increased very significantly, for example by a multiple of 5 or more or 10 or more or 25 or times by employing a low solubility Mg source as described herein as compared to a case where a highly soluble Mg source is used.
In some embodiments an aqueous solution having a relatively high concentration of phosphorus (i.e. about 2,000 to about 10,000 mg/L PO4—P) may be fed to the reactor at a relatively low flowrate to maintain reactor loading. In some embodiments an aqueous solution having a lower concentration of phosphorus (i.e. about 40 to about 600 mg/L PO4—P) may be fed to the reactor. In some embodiments the reactor (or a portion of the reactor) has a hydraulic limitation (i.e. a maximum upflow velocity and/or a minimum hydraulic retention time (HRT)) which may limit maximum loading. For example, in some embodiments, reaction tank 18 of reactor 12 comprises a substantially vertically-oriented conduit having a harvesting section and two or more vertically-sequential sections above the harvesting section. In such embodiments the reactor may be operated at an upflow velocity of about 250 cm/minute in a harvest section of the reaction tank and 60 cm/minute in one or more of the vertically-sequential sections above the harvesting section. In some embodiments, fines may be separated from the solution in a recycling path and concentrated through settling, filtration, centrifugation, or other solids separation techniques, and the concentrated fines solids sent to a fines treatment tank where they are dissolved in a reduced pH solution (e.g. an acidic solution) before being returned to the reaction tank and/or to the recycle path. The fines treatment tank may be operated at an upflow velocity of about 7 cm/minute. The fines treatment tank may be used to capture fines and/or low solubility Mg source particles and return the low solubility Mg source to the reaction tank and/or the recycle path to be dissolved for crystal production. Where the low solubility source of Mg particles settle fast enough to be retained in the reactor, or are otherwise agglomerated into growing struvite particles, then the low solubility source of Mg may be retained for a period of time that is longer than the HRT of aqueous solution flowing through the reactor, possibly eliminating or reducing HRT as a limiting factor on reactor loading and leaving the upflow velocity as a limit.
Samples of aqueous solution (dewatering liquors from municipal wastewater treatment plant anaerobic digesters) were reacted with various low solubility sources of Mg to determine the impact of low solubility Mg source type on phosphorus (P) removal (%) as a function of reaction time (minutes). The results of the tests are shown in in
In each case a 10% solution of MgO slurry was prepared. If acid was utilized, then 93% sulfuric acid was dosed to the MgO slurry at a 0.4:1 mol H per mol Mg. The MgO slurry was then left to hydrate for 15 minutes, before being dosed at a 1:1 Mg:P to a jar of dewatering liquor. The jar was left to react for 60 minutes, and then the soluble concentrations in the jar were recorded to determine the removals. After 20 hours of hydration, another jar of dewatering liquor was dosed with the MgO slurry at an Mg:P ratio of 1:1, left to react for 60 minutes, and then the soluble concentrations in the jar were recorded.
The following hydrated slurries were prepared in water: (i) 10% by weight MgO, hydration time=20 hours; (ii) 10% by weight MgO, hydration time=15 minutes; (iii) 10% by weight MgO with 0.2:1 mol H2SO4:MgO, hydration time=19 hours; and (iv) 10% by weight MgO with 0.2:1 mol H2SO4:MgO, hydration time=15 minutes. Each hydrated slurry was added to a sample of an aqueous (dewatering liquors from municipal wastewater treatment plant anaerobic digesters) and the solutions were mixed for 60 minutes.
The solutions were analyzed for P, N, and Mg content. At least 80% of the phosphorus (P) content of each aqueous solution was removed by the hydrated slurries as indicated in Table 3. P removal (%) was higher where the hydrated slurry contained 0.2:1 mol H2SO4:MgO (i.e. slurries (iii) and (iv)) and where the slurry had a longer hydration time (i.e. slurries (i) and (iii)). The Mg content analysis indicated that less Mg was available for P removal for slurries (ii) and (iv).
Acid was added to the MgO hydrated slurries prepared in Example 4. The final ratios were as follows: (i) 0.49:1 mol H2SO4:MgO; (ii) 0:1 mol H2SO4:MgO; (iii) 0.20:1 mol H2SO4:MgO; and (iv) 0.94:1 mol H2SO4:MgO. Each hydrated slurry was added to a sample of an aqueous solution (dewatering liquors from municipal wastewater treatment plant anaerobic digesters). Additional acid was added to the samples with hydrated slurries (i) and (iv) to lower the pH below 9.
Without being bound to any particular theory, the inventors believe that additional acid was needed to lower pH because the mechanism to produce Mg(OH)2 from MgO includes the intermediate production of Mg2+(aq) and OH−(aq). The Mg2+(aq) ions are available for crystal production and the OH−(aq) ions remain free in solution available to form MgOH+/OH−(surface) and promote the production of additional Mg2+(aq) and OH−(aq), thereby causing the pH to continue to rise until Mg(OH)2(s) is formed.
Without being bound to any particular theory, the inventors believe that the sample containing hydrated slurry (iii) did not require additional acid since the MgO had likely fully converted to Mg(OH)2 and, accordingly, the pH of the solution was controlled by the dissolution of Mg(OH)2 and precipitation of struvite. The sample containing hydrated slurry (iv) required additional acid because the hydrated slurry had likely formed an initial layer of Mg(OH)2 and additional Mg2+(aq) and OH−(aq) ions were released into solution as additional MgOH+.OH−(surface) was formed. The sample containing hydrated slurry (i), which is believed to have been less hydrated than the sample containing hydrated slurry (iii), required additional acid. It is likely that some unreacted MgO was hydrating during struvite production. Since hydrated slurry (ii) did not contain acid, was hydrated for a shorter duration of time (i.e. 15 minutes), and the temperature was kept at room temperature, it is believed that the water did not have sufficient time to diffuse within the MgO particles. Accordingly, the initial surface layer of Mg(OH)2 could still have been forming and would have been available to react with the struvite. Once the struvite reaction completed, a number of unreacted MgO sites would have remained (which would explain the low final Mg concentration observed).
A 32% by weight aqueous solution of MgCl2 was prepared and added to an aqueous solution (dewatering liquors from municipal wastewater treatment plant anaerobic digesters) such that the Mg:P ratio (mol:mol) was 1:1. The pH of the resulting solution was increased to 7.9 by adding 0.5 mL of NaOH(aq) and the solution was mixed for 60 minutes. The pH rose to 8.24 during the 60 minute mixing time. P removal was 92% and the solution contained 32 mg/L Mg, 10.8 mg/L P, 621 mg/L NH3—N.
The differences in reactivity between different sources of MgO were compared.
Each hydrated slurry was added to a sample of an aqueous solution (dewatering liquors from municipal wastewater treatment plant anaerobic digesters) and P removal (%) was determined. P removal (%) was greater for the MgO from Supplier 2 over MgO from Supplier 1. This indicates that the Supplier 2 MgO hydrated slurries were likely Mg limited and that the Supplier 1 MgO source is likely less reactive than the Supplier 2 MgO source. However, the Supplier 1 MgO source was more sensitive to hydration time and added acid. P removal % was greater where the hydration time was longer (i.e. −20 hours vs. <15 minutes). P removal % was greater where acid was added to the MgO slurry. It is worth noting that the Supplier 1 MgO slurries were all hydrated at a lower temperature than the Supplier 2 MgO slurries, since the heat of reaction of the Supplier 2 MgO and water was greater than that of the Supplier 1 MgO slurries. Also, the final pH of the Supplier 1 MgO slurry and aqueous solution mixture was about 0.1 lower than the pH of the Supplier 2 MgO slurry and aqueous solution mixture. Accordingly, secondary addition of acid was not required for the mixtures containing a Supplier 1 MgO slurry. This may imply the presence of fewer MgOH+ sites for reaction and/or that the Supplier 1 MgO slurry particles have a smaller surface area than the Supplier 2 MgO slurry particles. Since overshooting pH appears to be less of a concern using a Supplier 1 MgO slurry, the Supplier 1 MgO may be preferable for use in struvite recovery.
Aqueous slurries of Supplier 2 MgO and Supplier 1 MgO were prepared and afforded various hydration. An aqueous MgO slurry that was hydrated for 48 hours appeared dried out, indicating that the MgO had likely entirely converted to Mg(OH)2(s). Aqueous slurries of Supplier 2 MgO and Supplier 1 MgO were prepared having the following hydration times: 15 minutes, about 20 hours, and 36 hours. Each slurry was added to a sample of an aqueous solution containing P (dewatering liquors from municipal wastewater treatment plant anaerobic digesters) and P removal (%) was compared. The results are shown in
The effect of temperature on hydration was tested by heating aqueous MgO slurries prepared from Supplier 2 MgO and Supplier 1 MgO in the presence and absence of acid. Hydration time was 15 minutes. As shown in
The effect of reaction time on P removal (%) was tested for Supplier 2 MgO and Supplier 1 MgO aqueous slurries prepared with and without acid (10% MgO slurries with and without 0.2:1 H2SO4:MgO molar dose). A fluidized bed reactor of the type described in Britton, WO publication No. 2012/119260, entitled “Reactor for Precipitating Solutes from Wastewater and Associated Methods” was used. The reactor had a volume of approximately 168 m3 to the bottom of the recycle manifold. As shown in
NaOH was added to increase the pH of each mixture above 8 and P removal (%) was determined after reaction times of 6.5 minutes, 15 minutes, and 60 minutes. The Mg:P (mol:mol) ratio was 1.25:1 for each sample. P removal (%) was also determined for a MgCl2 sample with added NaOH to increase pH above 8. The results are shown in
MgO slurries showed increasing P removal performance with increased reaction time, and with acid addition; approaching the performance of soluble Mg sources (MgCl2) and caustic at 60 minutes of reaction time.
Full scale commercial fluidized bed reactors were used to test the use of a low solubility Mg source, specifically MgO, in the precipitation of wastewater. Two full scale demonstration experiments were performed. Different sources of MgO were used in the two experiments. In the first experiment, the source of MgO was a fine powder of calcinated magnesite with a particle size distribution where about 90% of the particles are smaller than 75 μm. A target MgO concentration of about 12% by weight of MgO was maintained in the reaction tank. The loading was about 65 kg of PO4—P per day. The pH of the solution in the reaction tank was in the range of from about 7.5 to about 8.1. The flow of the MgO hydrated slurry into the reaction tank was controlled by maintaining a molar Mg:P ratio in the reaction tank. Samples from the reaction tank were collected and analyzed to determine the amount of solids produced from the reaction and the amount of dissolved Mg remained in the supernatant of the sample. The percent of total solids and the amount of dissolved Mg detected in the collected samples were 18.75% and 0.566 mg/L respectively.
In the second experiment, the source of MgO was a fine powder of calcinated magnesite with a particle size of about 200 mesh (with about 96% pass through). A target MgO concentration of about 20% by weight of MgO was maintained in the reaction tank. The loading was about 195 kg of PO4—P per day. The flow of the MgO hydrated slurry into the reaction tank was controlled by maintaining the pH at about 7.9 to about 8. Samples from the reaction tank were collected and analyzed to determine the amount of solids produced from the reaction and the amount of dissolved Mg remained in the supernatant of the sample. The percent of total solids and the amount of dissolved Mg detected in the collected samples were 30.21% and 1.36 mg/L respectively.
The results from these experiments illustrate that low amounts of free Mg are present when the reaction is complete. This suggests that the majority of the Mg that was added to the reaction tank was used to form struvite.
While a number of exemplary aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub-combinations thereof. It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations as are consistent with the broadest interpretation of the specification as a whole.
Unless the context clearly requires otherwise, throughout the description and the
Specific examples of systems, methods, and apparatus have been described herein for purposes of illustration. These are only examples. The technology provided herein can be applied to systems other than the example systems described above. Many alterations, modifications, additions, omissions, and permutations are possible within the practice of this invention. This invention includes variations on described embodiments that would be apparent to the skilled addressee, including variations obtained by: replacing features, elements and/or acts with equivalent features, elements and/or acts; mixing and matching of features, elements and/or acts from different embodiments; combining features, elements and/or acts from embodiments as described herein with features, elements and/or acts of other technology; and/or omitting combining features, elements and/or acts from described embodiments.
It is therefore intended that the following appended claims and claims hereafter introduced are interpreted to include all such modifications, permutations, additions, omissions, and sub-combinations as may reasonably be inferred. The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/CA2019/050667 | 5/16/2019 | WO | 00 |
| Number | Date | Country | |
|---|---|---|---|
| 62672563 | May 2018 | US |
